review article synthesis and reactions of five-membered...

Review ArticleSynthesis and Reactions of Five-Membered Heterocycles UsingPhase Transfer Catalyst (PTC) Techniques

Ahmed M El-Sayed1 Omyma A Abd Allah1

Ahmed M M El-Saghier1 and Shaaban K Mohamed23

1 Department of Chemistry Faculty of Science Sohag University Sohag 82524 Egypt2 Chemistry and Environmental Division Manchester Metropolitan University Manchester M1 5GD UK3Chemistry Department Faculty of Science Minia University El-Minia 61519 Egypt

Correspondence should be addressed to Omyma A Abd Allah omymatif66yahoocom

Received 1 May 2013 Revised 15 September 2013 Accepted 28 October 2013 Published 25 February 2014

Academic Editor Jorge F Fernandez-Sanchez

Copyright copy 2014 Ahmed M El-Sayed et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Phase transfer catalysts (PTCs) have been widely used for the synthesis of organic compounds particularly in both liquid-liquid andsolid-liquid heterogeneous reaction mixtures They are known to accelerate reaction rates by facilitating formation of interphasetransfer of species and making reactions between reagents in two immiscible phases possible Application of PTC instead oftraditional technologies for industrial processes of organic synthesis provides substantial benefits for the environment On the basisof numerous reports it is evident that phase-transfer catalysis is the most efficient way for generation and reactions of many activeintermediates In this review we report various uses of PTC in syntheses and reactions of five-membered heterocycles compoundsand their multifused rings

1 Introduction

Organic synthesis is an essential way to get chemical prod-ucts having practical applications such as pharmaceuti-cals plant protection agents dyes photographic sensitizersand monomers Transformations of starting materials intodesired final products usually require number of chemi-cal operations in which additional reagents catalysts andsolvents are employed Thus during any synthetic methodbesides the desired products many waste materials areproduced because transformations of reactants into productsare neither quantitative nor selective processes This wastecould be regenerated destroyed or disposed This will leadto consuming much energy and creating heavy burden onthe environment Therefore it is of a great importance todevelop and use synthetic methodologies that minimizeor eliminate such problems One of the most commonand efficient methodologies that fulfill this requirement isemploying phase-transfer catalyses techniques [1ndash4] Themost significant advantages of use of PTCs in industrialapplications are [5]

(1) elimination of organic solvents(2) elimination of dangerous inconvenient and expen-

sive reagents such as NaH and NaNH2

(3) increasing the reactivity and selectivity of the activespecies

(4) improving the yield and purity of products to theoptimum records

(5) simplifying the whole synthetic process and makingit safer and objective

(6) reducing industrial wastes and overall costs and sav-ing energy which gives a positive impact on economicand environmental interests

(7) accelerating and performing mimic reactions in anefficient mode

11 Fundamentals of Phase Transfer Catalysis (PTC) Firstphase transfer catalysis was discovered by Jarrouse and Hebdin 1951 when they observed that the quaternary ammonium

Hindawi Publishing CorporationJournal of ChemistryVolume 2014 Article ID 163074 47 pageshttpdxdoiorg1011552014163074

2 Journal of Chemistry

+

+

OHPhCH2NEt3Cl

NaOH

PhCH2NEt3Cl

NaOH

ClOCH2Ph

C2H5Cl C2H5

CN

CN

(1)

(2)

Figure 1

PhCH2CN + NaOH

PhCHCN Na + QX

PhCHCN Na + H2O

PhCHCN Q + NaX

org

org org org org

org org

PhCHCN Q + R-X CHC N + QX

int

int

aq

aq

+

++

+

minus

minus +

+

minus

minus

minus

minus PhR

Figure 2

ClCH2R

BrCH(COOEt)2

N

Ph

NH2

NC

RN

NH

CO2Et

CO2EtPh

NC

3

PhNH-CH = C(CN)2

2andashc

R a = CO2Et b = CONH2 c = COPh

Figure 3

4 5

PTCN

CN

O

Ar

NH2

6

ArNHCOCH2Cl + CH2(CN)2

Figure 4

salt and benzyltriethylammonium chloride accelerated two-phase reaction of benzyl chloridewith cyclohexanol (Figure 1(1)) and the two-phase alkylation reaction of phenylacetoni-trile with benzyl chloride or ethyl chloride [6] (Figure 1 (2))

In addition numerous publications and patents [7ndash12]have been reported during the period of 1950ndash1965 PTCstechniques have been further developed byMakosza et al forthe purpose of obtaining more efficient and pure yield [13ndash16]

12 Mechanism of Phase-Transfer Catalysis All phase-transfer catalyzed reactions involve at least two steps

(1) transfer of one reagent from its ground phase into thesecond phase as an intermediate

(2) reaction of the transferred reagent with the non-transferred reagent for example the alkylation ofphenylacetonitrile with alkyl halide using aqueousNaOH as a base and tetrabutylammonium halide

Journal of Chemistry 3

NH2

PhN

CNCN

NQ

CN

Y

Ph NH

CN

CN

CN

PhN CNCN

PhN CNCN

Y

Y

Y

Q

Q

Organic layer

K2CO3 solid surface

HX +

HXQXXCH2Y

Ph-N

Ph-N

Scheme 1

(QX) as a catalyst can be formulated as shown inFigure 2

The concept of phase-transfer catalysis is not limited toanion transfer but is muchmore general so that in principleone could also transfer cations free radicals or wholemolecule Phase transfer catalysis is classified as liquid-liquidliquid-solid liquid-gas solid-gas or solid-solid systems

2 Application of Phase Transfer Catalysisin Synthesis of Five-Membered Ring ofHeterocyclic Compounds

21 Synthesis of Five-Membered Ring Heterocycles Con-taining One Heteroatom Treatment of anilinomethylene-malononitrile 1 with ethyl chloroacetate chloroaceta-midephenacyl chloride or diethyl bromomalonate in 1 1 1molar ratio (dioxanK

2CO3tetrabutylammonium bromide

(TBAB)) afforded the corresponding substituted pyrroles 2andashc and 3 respectively [17] (Figure 3)

The catalytic cycle which explains the reaction pathwaycan be simplified as in Scheme 1

A simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitriles 6 was achievedby reaction of N-aryl-2-chloroacetamide 4 andmalononitrile5 under solid-liquid PTC condition (CH

3CNK

2CO318-

crown-6) at room temperature [18] (Figure 4)3-Amino-4-ethoxycarbonyl-1-phenyl-5-thioxo-25-dihy-

dro-2-pyrrolidene malononitrile 9a was prepared via reac-tion of malononitrile 5 phenyl isothiocyanate 7 and ethox-ymethylenemalononitrile 8a in 1 1 1 molar ratio under

the PTC mixture of dioxanK2CO3(TBAB) Replacing

of ethyl ethoxymethylenecyanoacetate 8b with 8a gaveethyl[3-amino-4-ethoxy-carbonyl-1-phenyl-5-thioxo-25-di-hydro-2-pyrrolidene]cyanoacetate 9b and 10 under the sameexperimental conditions [19] (Figure 5)

Moreover the reaction of ethyl cyanoacetate 11 withphenyl isothiocyante 7 and ethoxymethylenemalononitrile8a or ethyl ethoxymethylenecyanoacetate 8b in 1 1 1 molarratio under same PTC experimental conditions affordedthe corresponding pyrrole derivatives 12a b and 13 [19](Figure 6)

Reaction of methyl 25-dibromopentanoate 14 with tri-chloroacetamide 15 under solid-liquid technique (CH

3CN

K2CO3TEBACl) yielded methyl N-trichloroacetyl-2-pyr-

rolidine carboxylate 16 [20] (Figure 7)Substituted pyrrolidines 19 were synthesized via the

13-dipolar cycloaddition reaction between imino esters 17(derived from alanine and glycine with alkanes) and alkylacrylate 18 in a mixture of THF or toluene KOH and TBACl[21] (Figure 8)

14-Di(malononitrilemethyleneamino)benzene 20 wasallowed to react with ethyl chloroacetate chloroacetamidephenacyl chloride or diethyl bromomalonate in 1 2molar ratios under solid-liquid PTC technique to give thecorresponding 14-bi(1-pyrrolyl) benzene derivatives 21andashcand 22 [17] (Figure 9)

Pyrrolidine derivatives 24were obtained with thiophenes25 from the reaction of diethyl cyanomalonate 23with phenylisothiocyanate 7 and chloroacetonitrile or chloroacetamideusing the PTC of (DMFK

2CO3TBAB) [22] (Figure 10)


PTCNC CN NC CN

CH2(CN)2 + PhNCS5 7 S NH PhN SH

Ph

PTC NC NH2NC NH2

EtOCH = C(CN) X+ CN

SNCN

PhNS

8a bPh X

CN

109a b

X a = CN b = COOEt

Figure 5

CNCH2COOEt + PhNCS PTC EtOOC CN

NHPh

S

EtOOC CN

SHPhN

PhN

PTC PTC EtOCH=C(CN)2

N

EtOOC EtOOC

EtOOC

CN

CN

CNS S

Ph

N

EtOOC

CN CN

COOEtCOOEt

COOEt

S

Ph

EtOCH=C(CN)(COOEt)

S

NH2

NH2

NH2 NH2

HydrolysisminusPhNH2

O

H2OK2CO3

+

12a

11

8a8b

12b

13

7

Figure 6

NPTC COOCH3

14

16

15 COCCl3

Br(CH2)3CH(Br)COOCH3 + Cl3CCONH2

Figure 7

One-pot reaction of malononitrile 5 carbon disulphideand chloroacetamide in 1 1 1 molar ratio under solid-liquid PT catalysis (benzeneK

2CO3TBAB) has furnished

3-amino-2-carboxyamido-4-cyano-5-mercaptothiophene 26[23] (Figure 11) Also treatment of malononitrile 5 with

CS2and ethyl chloroacetate under the same experimental

conditions gave the corresponding thiophene derivative 27[23] (Figure 11)

Different thiophene compounds (24 and 28ndash30)preparedfrom reaction of diethyl cyanomalonate 23 with carbon


N

RO N

R

O

NH

17 18 19KOHKOH

COORCOORCOOR

R4N XR4N X R1R1

R1

minus

+

+ minus+

Figure 8

HN NH

NC

NC CN

CNPTC

NN

RRNH2

N

CNNC

NNHHN

NC CN

R = CO2Et CONH2 COPh20

22

2BrCH(CO2Et)2

H2N

CO2EtEtO2CCO2EtEtO2C

2ClCH2R

21andashc

Figure 9

EtO2C

Et EtEt

EtEtEtO

OO

O

OO

O OO

O

OOH

NCPhNCS PTC

PTC

SHSH

PhY

ZX

S

EtO2C

YN

ZX

S

25

24a b X= CO2Et Y = CN Z = NH2

24c X = CN Y = CONH2 Z =OHX = CO2Et Y = CN Z = NH2

+

+

CN CN

PhN

PhN

PhNH

XCH2Y

24andashc

Figure 10

CH2(CN)2 + CS2 + ClCH2CONH2PTC

PTC

S SH

H2N

H2NOC

CN

S

H2N CN

5

5

26

CH2(CN)2 + CS2 + ClCH2COOEtEtO2C SCH2CO2Et

27

Figure 11


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X

24a b 25a-b X = CO2C2H5 Y = CN Z = NH2

24c 25c X = CO2C2H5 Y = CONH2 Z = NH2

XCH2Y

XCH2Y

a Y = COPh b Y = CN c Y = CONH2

23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12

disulphide or phenyl isothiocyanate 7 along with differentactive halocompounds under solid-liquid phase condition(dioxanK

2CO3TBAB) have been reported byAbdAllah and

El-Sayed [22] (Figure 12)2-Thiophenylidenes 31ndash33 were obtained through the

reaction of either malononitrile 5 or ethyl cyanoacetate 11with carbon disulphide along with ethoxymethylenemal-ononitrile 8a or ethyl ethoxymethylenecyanoacetate 8busing liquid-solid technique (dioxanK

2CO3TBAB) [19]

(Figure 13)In this reaction the yield of products was found to be a

temperature dependent Thus at low temperature (40∘C) itaffords the aminothiophene derivative 32a in high yield whileat high temperature hydroxythiophene 32b or 33b was thesolely product but in low yield

The reaction of pyridosultam 34 with 3-chloropropylthiocyanate under the experimental condition (tolueneaqNaOHTBAB) yielded the corresponding dihydrothiophenederivative 35 [24] (Figure 14)

4-Amino-5-cyano-2-hydroxy-3-furancarboxylic acid 37and compound 38were synthesized by treating 1-phenyl-35-pyrazolinedione 36 with bromomalononitrile under solid-liquid condition (dioxanK

2CO3TBAB) (Figure 15) [25]

The reaction pathway for the formation of unexpectedcompound 37was assumed to proceed via catalytic hydrolysisof compound 38 into the furan derivative 37 and phenylhydrazine [25] (Figure 16)

Condensation of salicylaldehyde 39 and its derivativeswith various esters of chloroacetic acids 40 in the pres-ence of TBAB led to the synthesis of benzo[b]furans 41under solventless and microwave irradiation technique [26](Figure 17)

Liquid-liquid PTC reaction of 4-chlorobutyronitrile 42with nonenolizable aldehydes 43 via sequence of an addi-tion cyclization reaction gave tetrahydrofuran-3-carbonitrilederivative 44 [27] (Figure 18)

Fused bis-aroylbenzodifurans 46 have been synthesizedby condensing 24-diacetyl resorcinol 45 with various p-substituted phenacyl bromides [28] (Figure 19)

Methyl or ethyl 3-amino-4-arylthiophenes-2-carbox-ylates 48andashf were synthesized by Thorpe reaction throughthe treatment of 3-hydroxy-2-arylacrylonitriles 47andashf andmethyl or ethyl thioglycolates with hydrochloric acid byusing different PTC conditions (solid-liquid or liquid-liquid)The solid-liquid PTC conditions using 18-crown-6 alongwith potassium hydroxide as a catalyst are the method withexcellent yieldsThe reactions were carried out in acetonitrileat RT [29] (Figure 20)

In Japp-Klingemann reaction the indole derivatives 52have been prepared as indicated in Figure 21 The additionof a suitable PTC catalyst to the reaction could signifi-cantly improve the reaction process Firstly aryl amines49 were diazotized and reacted under alkaline conditionsethyl 2-[2-(13-dioxo-13-dihydro-2H-isoindol-2-yl)ethyl]-3-oxobutanoate 50 using PTC-promoted Japp-Klingemann


PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC

32a b X a = CN b = COOEt 33b

11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44

ClCH2CH2CH2CN + Ar-CHO

Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC

X = H Cl NO2 CH3 OCH3 OCH3 Br

COCH2Br+ 2X

45

46

Figure 19

CNR

H OH

1 HSCH2COOR1 HCl2 KOH ArCN 18-C-6

H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3

c benzo[b]furyl-2d thinyl-2e dimethyl 25-thinylf C6H5

R1RCOOMeCOOMeCOOMeCOOMeCOOMeCOOEt

60ndash70∘C

Figure 20

reaction to form the ring-opened aryl hydrazones 51 Thesearyl hydrazones were cyclized and converted into the corre-sponding indole derivatives 52 by adding hydrochloric acidin ethanol [30] (Figure 21)

Synthesis of dimethyl phosphinyl substituted tetra-hydropyrroles 55 via 13-cycloaddition reaction of the azome-thine 53 to electron deficient alkenes such as 120572120573-unsaturatedketones (eg benzylideneacetophenone 54) esters and

nitriles took place in high yield and low diastereoselectivityin phase-transfer catalysis conditions (solid potassium car-bonate triethylbenzylammonium chloride (TEBA)) in aceto-nitrile as a solvent [31] (Figure 22)

When Schiff base 53 and ethyl cinnamate 56 reactedunder different phase-transfer catalysis conditions (10 equiv-alents of aqueous NaOH (50)TEBADMSO) the esterof pyrrolidinecarboxylic acid 57 has not been formed


NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23

instead the acid itself 58 was obtained as a mixture of twodiastereoisomers [31] (Figure 23)

22 Synthesis of Five-Membered Ring Heterocycles Contain-ing Two Heteroatoms (4Z)-4-(4-amino-13-dithiol-2-ylid-ene)-5-methyl-2-phenyl-24-dihydro-3H-pyrazol-3-one

derivative 60 was the product of a reaction of 3-methyl-1-phenyl-2-pyrazoline-5-one 59 with CS

2and chloroac-

etonitrile in equimolar ratio under solid-liquid technique(benzeneK


Similarly 1-phenyl-35-pyrazolidinedione 36 was treatedwith CS

2and ethyl chloroacetate under the same condition


N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3

+ Br(CH2)nCH2Br(CH2)nCH2Br

Figure 28

X-CH2-N-NHAr [CH2=N-N]-Ar

RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C

SO2CH2NC + RCHO PTCO

N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y

a X Y = CN b X = CN Y = CO2Etc X Y = CO2Et d X = COPh Y = COCH3

e COCH3 Y = CO2Et f X = COPh Y = CO2Etg X Y = COCH3

Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33

(benzeneK2CO3TBAB) to give the corresponding (4Z)-4-

(4-oxo-13-dithiolan-2-ylidene)-1-phenylpyrazolidine-35-dione 61 [25] (Figure 25)

The addition reaction of ethyl 34-diamino-5-cyanot-hieno[23-b]thiophene-2-carboxylate 62 to carbon disul-fide followed by cyclization reaction through the treat-ment with chloroacetonitrile or ethyl chloroacetate underPTC conditions (K

2CO3 TBAB dioxane) furnished 34-

bis(4-amino-2-thioxo-13-thiazol-3(2H)-yl)-5-propanoylthi-eno[23-b]thiophene-2-carbonitrile 63 and 34-bis(4-oxo-2-thioxo-13-thiazolidin-3-yl)-5-propanoylthieno[23-b]thio-phene-2-carbonitrile 64 in satisfactory yields [32] (Figure26)

Moreover the addition reaction of compound 62 tocarbon disulfide followed by cycloalkylation reaction with12-dibromoethane at 1 1 1 molar ratio under same PTCconditions afforded the corresponding bis-13-dithiolan-2-ylidene 65 [32] (Figure 27)

Treatment of triazepene compound 66 with dibromidesusing liquid-liquid condition (benzeneNaOHTBAB) fur-nished pyrazole derivatives 67a b [33] (Figure 28)

13-Dipolar cycloaddition of various substituted nitril-imines 68 to the appropriate alkenyl dipolarophiles 69 inaqueous media and in presence of a surfactant afforded anumber of 1-aryl-5-substituted-45-dihydropyrazoles 70 [34](Figure 29)

Preparation of 5-substituted oxazoles 74 or imidazoles75 was achieved by reaction of p-tolylsulphonylmethyl iso-cyanide 71 with aldehydes 72 R

1CH=NR

2or 73 (R

1 R2=

substituted phenyl heteroaryl and alkyl) under liquid-liquidcondition [35 36] (Figure 30)

The interaction of 3-chloro-3-methyl-1-butyne 76 with46-dimethyl-5-arylazo-2-thiopyrimidine 77 under liq-uid-liquid phase (benzeneaq KOHBTEACl) afforded 46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidinyl-(5H)-thiones 78 [37] (Figure 31)

Reaction of 5-phenylmethylene thiohydantoin 79 with12-dibromoethane 80 under liquid-liquid conditions (ben-zeneaq NaOHTBAB) afforded 23-dihydro-6-phenylmeth-ylene-5-oxo-imidazo[23-b]thiazole 81 [38] (Figure 32)

A variety of 4-thiazolidinone derivatives 83andashgwere suc-cessfully synthesized via in situ formation of ketene-NS-acetals 82andashg which in turn was reacted with ethylchloroethyl acetate chloroacetamide or chloroacetyl chlo-ride followed by ring closure to afford the desired 4-thiazolidinones 83andashg [39] (Figure 33)

One of the medicinal applications for PTC techniques issynthesis of sibenadet hydrochloride 87 which is a potentdrug used for treatment of chronic obstructive pulmonarydisease This bioactive molecule was synthesized by O-alkylation of phenylethanol 84 with the alkyl bromide 85under PTC condition to form the alkylated product 86 in97 yield Reaction of 86 with benzothiazole derivative ledto formation of the desired product 86 [40] (Figure 34)

Treatment of an equimolar amount of 2-mercapto-quinazolin-4(3H)-one 88 and dihalocompounds such as 12-dibromoethane and chloroacetyl chloride underwent S- and


OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97

Sibenadet hydrochloride

84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3

R = OMe (a) OEt (b) Me (c) H (d) Br (e)

106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42

+ CS2 + ClCH2CO2C2H5

S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2

CH2(CN)2 + PhNCS + ClCH2CO2EtEtO2C CO2Et

S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112

+ CS2 + ClCH2RminusH2O

R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47

N-cyclo-alkylation by using PTC conditions giving 23-di-hydro-5H-[13]thiazolo[23-b]quinazolin-5-one 89 and 5H-[13]-thiazolo-[23-b]quinazoline-35(2H)-dione 90 respec-tively [41] (Figure 35)

The PTC reaction of 3-phenyl-2-thiohydantoin 91 withdihalocompounds namely ethylene dibromide or 13-dibro-mopropane with CS

2 yielded 13-dithioxane derivative 92a

or 5-(13-dithian-2-ylidene)-3-phenyl-2-thioxoimidazolidin-4-one derivative 92b respectively [42] (Figure 36)

Treatment of the thiourea 93 and urea 94 derivativeswith ethyl bromoacetate under PTC condition using TBABas a catalyst and benzeneanhydrous K

2CO3as liquid-solid

phases gave imidazolidinediones 95a b via ring closurepathway [43] (Figure 37)

23 Synthesis of Five-Membered Ring Heterocycles ContainingThree Heteroatoms Alkylation of (2Z5Z)-5-benzylidene-2-(hydroxyimino)imidazolidin-4-one 96 with methylenebromide in benzeneaq NaOH in presence of TBAB as acatalyst gave 2-phenyl-23-dihydro-6-phenylmethylene-5-oxo-imidazo[21-c]-124-triazole 97 On the other handalkylation of the oxime derivative of 5-phenylmethylenethiohydantoin 98 with methylene bromide gave 3-(1H)-6-phenylmethylene-5-oxo-imidazo[21-c]-124-oxadiazoles99a b [38] (Figure 38)

Anastrozole 101 which acts as selective aromatase inhib-itor and is employed effectively in treatment of advancedbreast cancer in postmenopausal women has been syn-thesized in good yield by methylation reaction of 35-bis(cyanomethyl)toluene 100 usingmethyl chloride and 50aq NaOHTEBA as a PTC condition [40] (Figure 39)

24 Synthesis of Five-Membered Ring Heterocycles Con-taining Four Heteroatoms 5-Alkyl and 5-arylthiotetrazoles104 were synthesized in good yield from reaction of

alkyl(aryl)thiocyanates 102 with azide 103 under PTC con-ditions [44] (Figure 40)

Functionally substituted tetrazoles have been synthe-sized from the corresponding NN1015840N10158401015840-triarylbenzene-135-tricarboxamides 105 via sequential transformation of thesecompounds into imidoyl chlorides and treatment of thelatter with sodium azide under conditions of phase-transfercatalysis As a result a number of heterocyclic structures106andash106e containing three tetrazole rings have been isolated[45] (Figure 41)

3 Synthesis of Fused Five-MemberedRing Heterocycles

Functionally substituted thieno(23-b)thiophenes 107a bwere synthesized in a one-pot reaction of malononitrile 5CS2 and 120572-halocarbethoxy or 120572-halonitrile electrophiles in

1 1 2 molar ratios using (benzeneK2CO3TBAB) as a PTC

condition [23] (Figure 42)Another different thienothiophene 109 was synthesized

via the reaction of acetylacetone 108 with CS2and ethyl

chloroacetate in 1 1 2 molar ratio under the same experi-mental conditions [46] (Figure 43)

Thieno(23-b)pyrrole derivative 110 was obtained bytreating malononitrile 5 with phenyl isothiocyante 7 andethyl chloroacetate in 1 1 2 molar ratio using (benzeneK2CO3TBAB) as a phase transfer catalyst [23] (Figure 44)

Likewise under the same conditions 3-methyl-1-phenyl-2-pyrazoline-5-one 63 was subjected to react with CS

2and

chloroacetonitrile in 1 1 1 molar ratio where 6-cyano-46-dihydro-3-methyl-1-phenylthieno(34-c)pyrazol-4-thione 111was obtained in good yield [23] (Figure 45)

1-Phenyl-35-pyrazolinedione 36 was allowed to reactwith CS

2along with chloroacetonitrile or ethyl chloroacetate


NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5

Y = CO2C2H5 CO2CH3 CO2CH2H5

H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br

Y = COOEt CN PhCO CONH2

NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49

under the same conditions to give the corresponding thioxo-thienopyrazolone derivatives 112 [25] (Figure 46)

Reaction of 4-hydroxydithiocoumarin 113 with allylbromide 114 under liquid-liquid technique (CH

2Cl2aq

NaOHTBAB or TBACl) gave 2-methyl-23-dihydro-4H-thieno[23-b]benzothiopyran-4-one 115 [47] (Figure 47)

Treating of pyridazinium ylides 116 with N-phenyl-maleimide maleic and fumaric esters resulted in the

cycloadduct products 117ndash120 with high stereospecificity inthe presence of KF and trioctylmethylammonium chlorideor without solvent in the presence of aliquat 336 as phasetransfer catalyst [48] (Figure 48)

Under solid-liquid technique (dioxanK2CO3TBAB)

bis-thieno(18)naphthyridines 122 were prepared by reac-tion of 45-diamino-36-dicyano-(18)naphthyridine-27-dithiol 121 with ethyl chloroacetate chloroacetonitrile


N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51

phenacyl bromide or chloroacetamide in 1 2 molar ratioor from reaction of 45-diamino-27-dichloro-36-dicy-ano(18)naphthyridine 123 with two equivalents of ethylmercaptoacetate [49] (Figure 49)

Similarly 4-amino-35-dicyano-2-mercapto-6-methylthi-opyridine 124 was reacted with ethyl chloroacetate chloro-acetonitrile phenacyl bromide or chloroacetamide in 1 1molar ratio using the same PTC condition to give the cor-responding thieno(23-b)pyridines 125 or pyrrolo(23-d)thieno(23-b)pyridines 126 [49] (Figure 50)

Using solid-liquid technique (dioxanK2CO3TBAB)

2-ylidenemalononitrile and ethyl 2-ylidenecyanoacetate ofboth 23-dihydrobenzothiazole 127 and 23-dihydrobenzox-azole 128 were allowed to react with chloroacetonitrileethyl chloroacetate or phenacyl bromide in equimolar ratio

which afforded the corresponding substituted pyr-rolo[21-b]benzothiazoles 129 or substituted pyrrolo[21-b]ben-zoxazoles 130 respectively [42] Similarly (3-amino-2-(13-dihydro-2H-benzimidazol-2-ylidene)propanenitrile malo-nonitrile 131a or ethyl 3-amino-2-(13-dihydro-2H-benzim-idazol-2-ylidene)propanoate 131b were treated under thesame PTC conditions where the corresponding pyrrolo[23-b]pyrrolo[12-f]benzoimidazoles 132 were obtained [50](Figure 51)

Reaction of 27-dichloro-18-naphthyridine derivative 133with ethyl glycinate hydrochloride in 1 1 molar ratio undersolid-liquid technique (dioxanK

2CO3TBAB) afforded the

corresponding bis-pyrrolo(18)naphthyridine derivative 134[49] (Figure 52)


N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH

COOEtEtOOC+ HClH2NCH2COOEt

133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC

ClCH2CO2Et(1 1 2)PTC

(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b

a X = CN b X = COOEt a Y = NH2 b Y = OH

PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3

R = 4-ClC6H4 4-MeOC6H4minus

151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153

R = p-Cl-C6H4 p-MeOC6H4

p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br

155 156R = p-Cl-C6H4minus pndashMeOC6H4minus

Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61

Thieno(23-b) thiopyran derivatives 136 were obtainedfrom reaction of the thiopyran derivative 135 with ethylchloroacetate in 1 1 molar ratio (dioxanK

2CO3TBAB)

while on carrying out the same reaction under the sameconditions but in 1 2 molar ratio gave the correspondingthienopyrrolothiopyran derivatives 137 [51] (Figure 53)

Treatment of 3-amino-1-phenyl-2-pyrazoline-5-one 138with CS

2along with chloroacetonitrile ethyl chloroacetate

or phenacyl bromide in 1 1 1 and 1 1 2 molar ratios using[dioxanK

2CO3TBAB] as a PTC gave the corresponding

thienopyrazoles 139ndash143 145 and respectively 144 146 and147 fused thiazines [52] (Figure 54)

Thieno(34-b)pyrrole derivative 148 was obtained byreacting ethyl thiophene-2-ylidenecyanoacetate derivative31b with phenacyl bromide in a heterogeneous mixture of(dioxanK

2CO3TBAB) as a PTC [19] (Figure 55)

In the same manner pyridin-2-ylidenemalononitriles149a b were reacted with phenacyl bromide under the samereaction condition and yielded the corresponding thieno(23-b)pyridine derivatives 150a b [18] (Figure 56)

26-Dibenzoyl-5-methyl-3-(substituted styryl)benzo[12-b54-b]difurans 152 were synthesized from reaction of cin-namoylbenzofurans 151 with phenacyl bromide under liq-uid-liquid technique (benzeneaq K

2CO3TBAHSO

4) [53]

(Figure 57)Similarly 26-dibenzoyl-35-distyrylbenzo(12-b541015840-b)

difurans 154were prepared by condensing substituted dichal-cones 153 with phenacyl bromide under the same precedingPTC conditions [54] (Figure 58)

Also under the same PTC conditions dibenzoylbenzod-ifurans 156 were obtained from the reaction of substitutedresorcinols 155 with phenacyl bromide [55] (Figure 59)

Moreover 26-diaroylnaphthoyl-35-dialkylphenylben-zo[12-b54-b1015840]difurans 158 were synthesized by condensing24-diacyldiaroylresorcinols 157 with various p-substituted120572-bromo ketones [56] (Figure 60)

Treatment of 3-methyl-1-phenyl-2-pyrazolin-5-one 63with bromomalononitrile in 1 1 molar ratio yielded 5-amino-4-cyano-3-methyl-1-phenylfuro(23-c)pyrazoline 159[23] (Figure 61)

Furo(15)benzodiazepin derivative 161 was obtainedby reaction of 14-dimethyl-3H-(15)benzodiazepin-2-one160 with chloroacetonitrile under solid-liquid condition(dioxanK


By reaction of 4-methyl-13-dihydro-2H-1-benzazepin-2-one 162 with chloroacetonitrile or phenacyl bromideunder the solid-liquid phase transfer catalyst (dioxanK2CO3TBAB) the corresponding pyrrolo[12-a](15)benzo-

diazepine 163 was obtained [58] (Figure 63)Synthesis of 26-di(1-acetyl-2-oxopropylidene)dithiolo

[45-b4101584051015840-e]-48-benzoquinone 166 was achieved inone-pot reaction under solid-liquid technique (benzeneK2CO3TBAB) starting from acetylacetone CS

2to give 165

which in turn reacted with tetrabromo p-benzo-quinone 164in 2 1 molar ratio [59] (Figure 64)

Treatment of 4-arylidene-1-phenyl-35-pyrazolinediones167 with SS-acetal derivatives using solid-liquid tech-nique (dioxanK

2CO3TBAB) yielded the corresponding

pyrazolino-(13)-dithiolane derivatives 168 [25] (Figure 65)Some condensed heterocyclic systems 171 were obtained

by reacting 3-phenyl-4-amino-s-triazole-5-thiol 169 as adianionic compound containing N and S poles with somedi- and tetrahaloderivatives 170 as well as 120572-haloketones and120572-halonitrile derivatives under solid-liquid technique [60](Figure 66)

2-Aminoprop-1-ene-113-tricarbonitrile 172 was reactedwith CS

2or PhNCS along with 3-methyl-1-phenyl-2-pyr-

azoline-5-one 63 or 2-iminothiazolidin-4-one 173 (dioxanK2CO3TBAB) to give the corresponding fused pyrazoles 174

and thiazoles 175 respectively [61] (Figure 67)The reaction of 13-dihydro-4-methyl(15)benzodiazepin-

2-one 176 with chloroacetonitrile using solid-liquid


N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph

+ CS2 + XCH2CN PTCHN

Ar

Ph

CN minusH2OHN

CNPh

Ar

X = CN COOEtX = CN CO2Et167168

Ar = p-ClC6H4 p-NO2C6H4

Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180

+ (Ph3PCH2ndashCH=CHndashCH3)Clminus minus

Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71

technique (dioxanK2CO3TBAB) gave the corresponding

oxazolo-(15)benzodiazepin derivative 177 [57] (Figure 68)When 7-(methoxyimino)-4-methyl-2H-chromene-28-

(7H)-dione 178 was treated with crotyltriphenylphospho-nium chloride (CTPPCl) 179 (CH

2Cl2Li(OH)CTPPCl) the

corresponding chromeno-oxazolone 180 was obtained inwhich one of the reactants (CTPPCl) acts also as a catalyst[62] (Figure 69)

The triazepine 181 was treated with 12-dibromoethaneunder liquid-liquid technique (benzeneaq NaOHBTEACl)to afford the corresponding 6-methyl-8-phenyl-23-dihy-dro[13]thiazolo[32-d][124]triazepine-5(6H)-thione 182[33] (Figure 70)

4 Synthesis of Spiro Five-MemberedRing Heterocycles

Synthesis of spirorhodanine heterocycles 184ndash187 wasachieved by treating 55-dibromo-3-phenyl-2-thioxo-13-thi-azolidin-4-one 183 with different bidentates or with mixtureof CS2and some active methylene compounds under solid-

liquid condition (dioxanK2CO3TBAB) [63] (Figure 71)

Reaction of 4-ethoxymethylene-1-phenyl-35-pyrazoli-dinedione 188withCS

2andmalononitrile 5 or ethyl cyanoac-

etate 11 using solid-liquid technique (dioxanK2CO3TBAB)

yielded the corresponding spiro-13-dithiolane derivatives189 [25] (Figure 72)

1-Benzoyl-33-dibromo-4-phenyl-(15)benzodiazepin-2-one 190 was reacted with different dinucleophiles underPTC condition (dioxanK

2CO3TBAB) to furnish the corre-

sponding spiroheterocycles attached to benzodiazepine moi-ety 191ndash193 [64] (Figure 73)

5 Uses of Phase Transfer Catalysis Techniquesin Reactions of Five-Membered Heterocycles

51 Alkylation and Acylation

511 N-Alkylation or Acylation Diez-Barra et al [65] studiedthe alkylation of pyrrole 194 by PTC technique in absenceof the solvent The study revealed that the N versus C ratiois not affected by the nature of the catalyst The nature ofthe leaving groups have a significant influence where N-alkylation increases in the sequence I lt Br lt Cl lt OTs(Figure 74)

N-alkyl pyrroliden-25-diones 200 [66 67] were syn-thesized via reaction of pyrroliden-25-diones with differentalkylating reagents under phase transfer catalysis condition(tolueneK

2CO3TBAHSO

4) according to (Figure 75)

N-allylindoles 203were easily carried out via N-allylationof the proper indoles 201 with the suitable allyl halides 202


N

O

O

S

S

N

O

O

XHN

OEt

Ph

+ CS2 + NCCH2X PTCHN

Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh

PhX = NH SY = O S NH

COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O

NH + XCH2CH=CHCH2OR CH2CH=CHCH2OR

198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400

201 202 203R R998400 = H CH3 R998400998400 = H CH3 CH2CH2OCH3 CHO CH2COOCH3

R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H

204 205a b 206andashc

+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2

Bu4NHSO4 CH3PPh3BraqNaOH

207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78

The reaction was accomplished in diethyl ether via a phasetransfer process in which 18-crown-6 was employed as thetransfer agent and t-BuOK as the base [68] (Figure 76)

2-Substituted 1-allylpyrroles 206andashc were easily preparedfrom reaction of 2-formylpyrrole or 2-acetylpyrrole 204 witheither 3-chlorobut-1-ene 205a or 3-chloro-2-methylprop-1-ene 205b respectively under phase transfer conditions(tolueneNaOHTBAHSO

4) [69] (Figure 77)

Treatment of pyrroles 204 with 12-dichloroethane inpresence of 50 NaOH and TBAB as a catalyst yieldedthe corresponding N-chloroethyl-pyroles 207 in excellentyield which was transformed into 12-divinylpyrroles 208

via its reaction with sodamide using solid-liquid technique(THFNaNH

2CH3Ph3Br) [70] (Figure 78)

Synthesis of a series of N-alkylpyrrolidino[59]fullereneswas achieved via the combination of PTC without sol-vent and microwave irradiation technique Thus 2-phe-nylpyrrolidinofullerene 209 was treated with benzyl p-ni-trobenzyl p-methyloxy-carbonylbenzyl n-octyl or allyl bro-mides in microwave oven in presence of K

2CO3and TBAB

to yield the corresponding N-alkylpyrrolidino[59]fullerenes210 [71] (Figure 79)

13-Bis[2-(aryl)indol-1-yl]propanes 213 and 13-bis[3-(aryl)-5-(aryl)pyrazol-1-yl]-propanes 214 were prepared


NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar

NH + Br(CH2)3Br + HN

211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H

CNCNCNDimethyl carbonate

K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81

from reaction of appropriate 2-arylindoles 211 and 45-dihy-dropyrazoles 212 respectively with 13-dibromopropane vialiquid-liquid technique using TBAHS as a catalyst benzeneas the organic phase and 50 KOH as an aq phase [72](Figure 80)

Indole-2-acetonitrile 215 was treated with (CH3)2CO3in

a mixture of [DMFTBABK2CO3] to afford 1-methylindole-

2-acetonitrile 216a and 2-(1-methylindole-3-yl)propionitrile216b [73] (Figure 81)

Alkylation of indole 217 23-dimethylindole 218 withchlorodifluromethane under liquid-liquid technique(CH2Cl2aq NaOHBzTEACl) afforded the corresponding

1-alkylated derivatives 219 and 220 respectively [74](Figure 82)

Barraja et al heated 2-substituted-3-bromoindoles 221with excess of different nucleophiles solid KOH anddibenzo-18-crown as a phase transfer catalyst to afford thecorresponding 3-substituted indoles 222 in a satisfactoryincrease of yield [75] (Figure 83)

Carbazole 223 was alkylated with 16-dibromohexane in1 1 molar ratio to give N-alkyl derivative 224 in a mixture of(benzeneNaOHTBAB) [76] (Figure 84)

Alkylation of pyrazole 225 with cyclopentyl or cyclo-hexyl bromides without solvent with PTC system (KOH


NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R

R = HmiddotCH3 R1 = Ph 2-NO2C6H5 2-NH2C6H5 CO2Et

Nu = SAr O-Ar NR(Ar cylic)

221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84

TBAB) afforded the corresponding 1-cyclopentyl or 1-cyclo-hexylpyrazoles 226a b respectively Likewise treatment ofpyrazole with 12-dibromoethane in 1 1 or 2 1 molar ratioafforded 1-bromoethylpyrazole or 12 bispyrazolylethane 227228 [76](Figure 85) Also alkylation reaction of 1H-pyrazole225with linear or branched alkyl halide in liquid-liquid PTCsystem gave 1-alkyl-1H-pyrazole 229 [77] (Figure 85)

The reaction of 3-tert-butylpyrazole 230 with dibromo-methane afforded bis(tert-butylpyrazol-1-yl)methane [CH

2(3-

t-BuPz)2] 231 However the reaction of 3-isopropylpyra-

zole 232 with dibromomethane under the same con-dition yielded three isomers namely bis(5-isopropylpyra-zol-1-yl)methane[CH

2(5-isoPrPz)

2] 233 (3-isopropylpyra-

zol-1-yl-51015840-isopropylpyrazol-11015840-yl)methane[CH2(3-iPrPz- 51015840-

isoPrPz)2] 234 and bis(3-isopropylpyrazol-1-yl) methane

[CH2(3-iPrPz)

2] 235 [78] (Figure 86)

N-Substituted-35-diarylpyrazolines 237 and 238 wereprepared via liquid-liquid system in (CHCl

3or benzeneaq

KOHTBAB) using alkyl and allyl halides respectively asalkylating agents for pyrazoles 236 [79] (Figure 87)

N-Alkylation reactions of 49-dihydro-9-methyl-41010-trioxo-1(2H)-pyrazolo[34-c][21]-benzothiazepine 239 withdimethyl sulphate diethyl sulphate benzyl bromide benzylchloride phenacyl bromide phenacyl chloride or cyclo-hexyl bromide under the liquid-liquid PTC condition of(tolueneNaOH(25)BTEACl TBAB or TBAHSO

4) pro-

duced 1- and 2-alkylated isomers 240a b The ratios betweenthese two isomers were calculated [80] (Figure 88)

A number of 4-substituted pyrazolo[34-d]pyrimidines241 have been reacted with (2-acetoxyethoxy)methyl bro-mide using liquid-liquid and solid-liquid techniques Theinfluences of the solvent and catalyst have been studied [8182] (Figure 89)


NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br

R = linear or branched alkyl C1ndashC6

n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86

Imidazole 243 was alkylated with different alkyl halidesunder solid-liquid PTC in absence of solvent where theN-alkyl imidazoles 244a and imidazolium salts 244b wereobtained [83] (Figure 90)

1-Alkyl(C4ndashC14)imidazoles 245 were obtained from the

alkylation of imidazole 243 with the appropriate n-bro-moalkane via PTC technique (benzeneKOHTBAI) [84](Figure 91)

1-Alkyl-2-methyl-2-imidazolines 247 were obtained ingood to excellent yields by alkylation of 2-methyl-2-imid-azoline 246with organic halides in the absence of solvent [85](Figure 92)

Using the PTC condition such as (CH2Cl2KOHTEBA)

a mixture (1 1) of N-alkylated 5-nitroimidazoles 250a b or6-nitrobenzimidazoles 251a b was obtained by the reactionof 5-nitroimidazoles 248 or 6-nitrobenzimidazoles 249 with


NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4

(1H-isomer) (2H-isomer)

239 240a 240b

Figure 88

N

N N

R

N

N N

N

R

NH + CH3CO2CH2CH2OCH2Br CH2O(CH2)2CO2CH3

241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX

RX = EtI nndashBuCl BnCl

243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr

R = CH3(CH2)n n = 3ndash13243

245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1

+ CH3(CH2)nCH2Br(CH2)nCH3

R2

Or TBAB Na2CO3 CH3CN

253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262

TBAB K2CO3 CH3CN+ CH3(CH2)nBr (CH2)nCH3

Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3

K2CO3 KOH CH3CNBu4NBr

R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102

methyl iodide or benzyl chloride respectively in a satisfac-tory yield [86] (Figure 93)

Different imidazole compounds such as 2-methylim-idazole 252a and 2-methyl-4-nitro imidazole 252b werereacted with different alkyl bromides 253 in an alkalinemedia at reflux temperature and in the presence of tetraethy-lammonium iodide (TEAI) or TBAB as PTC and afforded 1-alkyl imidazole derivatives 254 which exhibited a variety ofvaluable pharmacological properties [87] (Figure 94)

N-Alkyl-2-acetylbenzimidazoles 257 have been obtainedin over 90 yield by alkylating 2-acetylbenzimidazole 256using the PTCmixture of (CH

3CNK

2CO3TEBACl) at room

temperature [88] (Figure 95)2-Phenylbenzimidazole 258 was alkylated with chlorod-

ifluromethane under liquid-liquid condition (CH2Cl2aq

NaOHBzTEACl) to give 1-difluoromethyl-2-phenylbenz-imidazole 259 [75] (Figure 96)

The N-alkylated imidazole derivatives 262 were achievedby treating compounds 260 with different alkyl bromide

261 under PTC condition (TBABK2CO3CH3CN) [89]

(Figure 97)Competitive N versus O benzylation of 55-dimethyl-

3-isoxazolidinone 263 using (CH2Cl2NaOH) using dif-

ferent PTC catalysts was studied The ratio of N-O-alkylations 264a264bwas 23 formost cases of catalysts [90](Figure 98)

Alkylation of 124-triazole 265 and benzotriazole 267has been performed either in basic media under solventfree PTC conditions or in absence of base by conventionaland microwave heating Several parameters affecting theselectivity have been studied [91] Arylation of 1H-123-benzotriazole 267 with activated aryl halides in a medium ofaromatic hydrocarbons under PTC condition using inorganicbases and acetyltrimethylammonium bromide as a phasetransfer catalyst was studied Both N(1)- and N(2)-arylatedproducts 269a and 269b respectively have been isolatedTheir ratio has depended on the nature of the employed baseand the reactivity of arylating agent [92] (Figure 99)


N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288

Pyrazole imidazole 1 2 4-triazole indazole benzotriazole

NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b

R = Me PhCH2 CH2 CH = CH2 X = Br I-

Figure 104

Treatment of benzotriazole 267 with chlorodiflurometh-ane under liquid-liquid conditions (CH

2Cl2aq NaOH

BzTEACl) has afforded 1-(difluoromethyl)-1H-benzotriazole270 [74] (Figure 100)

Reaction of 4-substituted-123-triazol 271 with alkylbromide 272 under basic condition using PTC Bu

4NBr

produced N-substituted 123-triazole derivatives 273andashc [93](Figure 101)

The alkylation of 5-benzyl-1H-tetrazole 274 under liquid-liquid technique such as (CH

2Cl2aq NaOHBzTEACl) gave

a mixture of 5-benzyl-1-difluoromethyl-1235-tetrazole 275a

in 23 and 4-benzyl-1-difluoromethyl-1235-tetrazole 275bin 15 [74] (Figure 102)

A series of 5-alkylthio-1-aryltetrazoles 277were preparedby alkylation reaction of the corresponding 1-aryltetrazole-5-thiols 276 with alkyl bromides under solid-liquid PTCtechnique [94] whereas without solvent and also underPTC technique several N-p-nitrophenylazoles 279ndash288weresynthesized by direct arylation of the corresponding azolocompound 278 with p-fluoronitrobenzene [95] while thealkylation reaction of 1-aryltetrazol-5-ones 289 with dibro-moalkanes under both liquid-liquid and solid-liquid PTC


N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R

PTC+ ClCH2CH2NH2R998400 R998400

CH2CH2NH2

70∘C

301ndash303 304ndash306

301 304 R= R998400 = H 302 305 R = CH3 R998400 = H (a) R998400 = CH3 R = H (b) 303 306 R= R998400 = CH3

Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH


301 304 307 R= R1 = H 302 305 308 R = H R1 = Me R = Me R1 = H 303 306 309 R R1 = Me

Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317

CH2Cl2TBABBenzyl bromideNaOH

Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320

Arminus Arminus ArminusBrCH2CH2Br

321andashh

R = Me Et CH2CHO CH2CO2Et CH(CO2Et)2COMe CO2Et p-NO2-C6H4-N = N

Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115

systems provided a convenient route to prepare bis-tetrazolonderivatives 290 and 4-bromoalkyl derivatives 291 [96](Figure 103)

N-Acetylated adenosine 292 was alkylated with ben-zyl bromide methyl iodide or allyl bromide in the pres-ence of tetrabutylammonium bromide as a PTC catalyst inCH2Cl2NaOH to give the correspondingN-alkyl-6-N-acetyl

adenosines 293a b [97] (Figure 104)N-alkylation reaction of adenine 294 took place with

different alkyl halides under the phase transfer conditionsusing microwave irradiation assistance [98] (Figure 105)

5-Aryloxymethyl-2-[(2-chlorophenyl)oxyacetylamido]-134-thiadiazoles 280 are synthesized from reaction of2-chlorophenyloxyacetyl chloride 297with 5-aryloxymethyl-2-amino-134-thiadiazoles 296under liquid-liquid conditionusing PEG-400 as a catalyst [99] (Figure 106)

N-Alkylation of 3-phenyl-2-thiohydantoin-5-arylidenederivative 299 has been carried out by using monohalocom-pounds such as allyl bromide as an alkylating agentThe reac-tionwas proceeded through nucleophilic displacement underPTC conditions of solid-liquid phases such as a mixture ofanhydrous potassium carbonate dioxane and TBAB as aheterogeneous catalyst The corresponding alkylated product300 was obtained in a good yield [42] (Figure 107)

Alkylation reaction of pyrazoles 301ndash303 with 2-chloroethylamine under the condition of phase-transfercatalysis was carried out in a liquid-solid system usingbenzene as an organic solvent and BTEAC as a catalystReaction between equimolar amounts of reactants led topoor yields (20ndash40) of the alkylated products 304ndash306 due

to concurrent dehydrochlorination of 2-chloroethylamineThe yield was considerably decreased in going from pyrazole(301) to 35 dimethylpyrazole (303) whereas the maximalyield of alkylated products (70ndash80) was obtained byusing one of the following ratios pyrazole NaOH 2-chloroethylamine 1 2 2 3-(5)methylpyrazole NaOH 2chloroethylamine 1 3 3 or 35-dimethylpyrazole NaOH 2-chloroethylamine 1 5 5 [100] (Figure 108)

In the N-alkylation reaction of pyrazole 3-(5)-meth-ylpyrazole and 35-dimethylpyrazole 301ndash303 with dichlo-roethane (DCE) the dehydrochlorination of the obtained 1-(120573-chloroethyl)pyrazoles has been carried out to give the cor-responding productsN-vinylpyrazoles 307ndash309 (Figure 9) inlow yield Attempts to carry out the reaction under standardconditions (waterbenzeneNaOHTEBAC) did not lead tothe desired result The yield of all products was sharplyincreased when benzene was replaced with an excess ofdichloroethane The reaction investigation showed that theease of alkylation depends strongly on the basicity of the pyra-zole The introduction of an electron-donating substituent(eg Me) into the molecule of pyrazole 301 increases theelectron density at the ldquopyrazolerdquo nitrogen atoms As a resultdeprotonation was hindered and the base was consumed inelimination of dichloroethane It must also be mentionedthat a 5- to 7-folds excess of dichloroethane was necessary toobtain optimal yields on alkylation of compounds 301ndash303[101] (Figure 109)

512 O-Alkylation or Acylation 25-Didodecyloxymethyl-furan 311 was obtained via alkylation of 25-dihydroxym-


N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1

328a b(a) R1 = H R = Et(b) R1 = R = PhCH2

Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus

Arminus ArminusArminus

HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C

334andashe 335andashe

Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127

ethylfuran 310 with dodecyl bromide without solvent using(KOHaliquat) as a catalyst while alkylation of furfurylalcohol 312 with 112-dibromododecane under the same PTCconditions produced the corresponding furanic diether 313[102] (Figure 110)

Similarly 2-furfuryl alcohol 312 was subjected to reactwith alkyl dihalides 314 using (benzeneKOHpolyethyleneglycol (PEG-400)) to yield the corresponding difurfuryldiethers 315 [102] (Figure 110)

4-(benzyloxy)-2-[(2E)-but-2-en-1-yloxy]-5-methoxytet-rahydrofuran-3-ol 317 was obtained from benzylation of2-O-methyl-5-O-crotyl-120572120573-D-ribofuranoside 316 usingbenzyl bromide in aq solution of NaOHCH

2Cl2and TBAB

as a catalyst [103] (Figure 111)

513 S-Alkylation PTC alkylation of arylidene derivative318 using dihalocompounds such as ethylene dibromide

or 13-dibromopropane afforded the thioalkylated dimers319a b respectively via s-alkylation pathway followed bydimerization reaction [42] (Figure 112)

514 C-Alkylation Reaction of 2-thiono-N(m-tolyl)thiazoli-din-4-one 320 with methyl bromide ethyl bromide chloro-acetaldehyde ethyl chloroacetate diethyl malonate acetylchloride ethyl chloroformate or p-nitrobenzenediazoniumtetrafluoroborate under solid-liquid system and using theheterogeneous mixture of (dioxanK

2CO3TBAB) as a PTC

yielded the corresponding 5-substituted thiazolidin-4-ones321andashh and yielded the corresponding spiro thiazolidin-4-one derivatives 322 when reacted with 12-dibromoethaneunder the same PTC condition [104] (Figure 113)

4-Benzyl-2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 324was prepared via the alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester 323 with benzyl


S

NO

S

ArCHOPTC S

NO

S

385384

ArminusArminus Arminus

Ar = Ph p-MeO-C6H4 2-Thienyl- 2-turyl--

Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus

Ar998400 = p-OMe-C6H4 Ar = m-Me-C6H4

Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B

+ RS-SRR = Me minusSO2

minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132

bromide using (tolueneKOH(s)Cinchona alkaloids) as aPTC [105] (Figure 114)

2-Thioxo-357-trisubstituted-1-(235-tri-O-benzoyl-120573-D-ribofuranosyl)pyrido[23-d]-pyrimidin-4(1H)-ones 327 havebeen prepared via phase transfer ribosylation of 2-thioxo-357-trisubstituted pyrido[23-d]pyrimidin-4(1H)-ones 325with 235-tri-O-benzoyl-120573-D-ribofuranosyl bromide 326 inbiphase solvents such as CH

2Cl250 aq NaOH using TBAB

as a catalyst [106] (Figure 115)In the presence of dioxane as a solvent under PTC con-

ditions one-pot reaction of 3-phenyl-2-thiohydantoin 91with CS

2and halocompounds such as ethyl bromide or

benzyl chloride afforded 5-[bis(ethylsulfanyl)methylidene]-2-(ethylsulfanyl)-3-phenyl-35-dihydro-4H-imidazol-4-one328a and 5-[bis(benzylsulfanyl)methylidene]-2-(benzylsulf-anyl)-3-phenyl-35-dihydro-4H-imidazol-4-one 328b respec-tively [42] (Figure 116)

Acylation of imidazolones 318 using chloroacetyl chlo-ride under PTC conditions yielded the corresponding acy-lated arylidene derivative 329 [42] (Figure 117)

515 Miscellaneous Alkylation 5-Bromorhodanine deriva-tive 330 was effectively used as an alkylating agent for somemono- or dianionic moieties containing S N or O under


solid-liquid phase transfer catalysis conditions Thus with4-hydroxy-2-mercaptopyrimidine where possible S N orO sites are available the reaction afforded the S-substitutedproduct With 2-aminobenzothiazole or piperazine the reac-tion yielded the corresponding N-substituted 331a b or thedisubstituted products 332 [104] (Figure 118)

In a plan to study C- versusO-alkylation of the pyrazolinederivatives 3-methyl-1-phenyl-2-pyrazolin-5-one 333 wastreated under PTC condition with different bromoorganiccompounds such as benzyl bromide 13-dibromopropanemethyl bromoacetate bromoacetaldehyde or diethylacetalas alkylating agents either in the absence or the presenceof carbon disulphide and afforded numerous of C- or O-alkylated derivatives 334andashe 335andashe [107] (Figure 119)

Reaction of 6-hydroxy-34-dihydroquinoline 337 and 1-cyclohexyl-5-(4-bromo-butyl)-1234-tetrazole 336 in a het-erogeneous mixture of tolueneH

2O K2CO3and TBACl

as a catalyst gave 6-[4-(1-cyclohexyl-1234-tetrazol-5-yl)butoxyl]-34-dihydrocarbostyril 338 in 99 purity [108](Figure 120)

52 Sulphonylation 45-Dihydro-35-diaryl-1-(4-fluoro-phenylsulphonyl)pyrazoles 341 and 2-aryl-1-(4-fluor-phenylsulphonyl)indoles 343were prepared from reaction of4-fluorophenylsulphonyl chloride 339 with the appropriate45-dihydro-35-diarylpyrazoles 340 or 2-arylindoles 342via solid-liquid phase (THFKOHTBAB) [107] (Figure 121)

N-Sulphonylation product 346 was prepared throughtreating 2-chloro-66-difluro-13-dioxolo[45-f]benzimida-zole 344 with 35-dimethylisoxazole-4-sulphonyl chloride345 via PTC protocol (tolueneaq K

2CO3TBAB) [109]

(Figure 122)

53 N-Carbonylation Carbonyldiimidazole 349 was pre-pared in 87 yield via reaction of imidazole 347 withphosgene 348 under PTC condition (chlorobenzeneNaOHtributylhexadecylphosphonium bromide (TBHDPB)) [110](Figure 123)

54 N-Phosphorylation Reaction of 13-thiazolidin-2-one350 with S-sec-Bu-O-Et chlorophosphorothiolate 351 in thepresence of NaOH and N-dodecyl-N-methylephedriniumbromide gave s-sec-Bu O-Et(2-oxo-3-thiazolidinyl) phos-phothiolate 352 in 84 yield [111] (Figure 124)

55 Elimination Reactions 120573-Elimination of bromomethylcyclic ketyl acetals 353 was carried out under solid-liquidphase (THFButOKAliquat 336) to prepare the correspond-ing cyclic ketene acetals 354 [112] (Figure 125)

Reaction of 6-chloro-2-chloromethyl-3-nitroimidazo[12-b]pyridazine 355 with 3 equivalents of nitroalkaneanion derivative 356 under liquid-liquid PTC protocol(CH2Cl2H2OTBA(OH)) gave 3-nitroimidazo[12-b]pyrid-

azines 357 bearing trisubstituted ethylenic double bondderivatives in a good yield [113] (Figure 126)

Vinylation of indole 358with ClCH2CH2Br was achieved

under PTC condition (tolueneKOH18-crown-6) andafforded the corresponding N-vinyl derivative 359 Similarly

under the same reaction conditions NS-divinyl derivatives362 and 363 were prepared from 3-mercaptoindole 360and 2-mercaptobenzimidazole 361 respectively [109](Figure 127)

56 Condensation Reactions Arylidenethiazolidin-4-ones385 were synthesized from condensation reaction of 2-thiono-N-(m-tolyl)thiazolidin-4-one 384 with aromatic orheteroaldehydes under solid-liquid PTC technique [104](Figure 128)

57 Addition Reactions Reaction of 2-thioxo-N-(m-tolyl)thiazolidin-4-one 386 with formaldehyde or some arylid-enemalononitriles via PTC technique (dioxaneK

2CO3

TBAB) afforded the corresponding 5-hydroxymethyl deriv-ative 387 or Michael type adduct 388 respectively Whilethe addition reaction of cyanoacetamide to 5-(p-methox-ybenzylidene)-2-thioxo-N-(m-tolyl)thiazolidin-4-one 389followed by condensation reaction under the same tec-hnique gave 7-anisyl-6-cyano-2-thioxo-3-(m-tolyl)thiazolo[45-b]pyridin-5-one 390 [104] (Figure 129)

58 Ring Expansion Treatment of 5-alkyl(aryl)-3H-pyr-rolin-2-ones 391with dichlorocarbene using (CHCl

3NaOH

BTEAB) at 20ndash30∘C afforded the intermediates 1-alkyl-66-dichloro-2-azabicyclo[310]hexan-3-ones which directlyrearranged and dehydrochlorinated to give 6-alkyl(aryl)-1-phenyl-5-oxohydropyridin-2-ones 392 [110] (Figure 130)

Also ring transformation of indole derivatives 393 hasbeen induced by dichlorocarbene (aq KOHTBABSO

4H)

to produce 3-haloquinoline 394 in a good yield Alsounder similar conditions reaction of 3-formyl-2-(3-chloro-4-fluorophenyl)indole 395 with dichlorocarbene gave 3-chloro-4-[22-dichloro-3-oxiranyl]-2-(31015840-chloro-41015840-fluoro-phenyl)quinoline 396 The evolved HCl gas has beeneliminated during the reaction [111] (Figure 131)

59 Ring Opening Treatment of benzosultams 400 with dif-ferent disulphides under PTC technique (CH

3CNK

2CO3

TBAHSO4) gave the corresponding 2-methylamino-benzal-

dehyde dithioacetals 401 [24] (Figure 132)

Abbreviations

PTC Phase transfer catalysisTEBACl Triethylbenzylammonium chlorideTHF TetrahydrofuranTBAB Tetrabutylammonium bromideDMF DimethylformamideRT Room temperatureDMSO Dimethyl sulfoxideBTEACl Benzyltriethylammonium chlorideTBACl Tetrabenzylammonium chlorideTBAHSO

4 Tetrabutylammonium hydrogen sulphate

CTPPCl Crotyltriphenylphosphonium chlorideTBAHS Tetrabutylammonium hydrogen sulphatet-BuPz Tert-butyl pyrazoleIPrPz Isopropylpyrazole


TEAI Tetraethylammonium iodidePEG Polyethylene glycolDCE DichloroethaneTBHDPB Tributylhexadecylphosphonium bromideTBA(OH) Tetrabutylammonium hydroxideBTEAB Benzyltriethylammonium bromide

Conflict of Interests

The authors declare that they have no conflict of interests

References

[1] M Makosza and M Fedorynski ldquoCatalysis in two-phasesystems phase transfer and related phenomenardquo Advances inCatalysis vol 35 pp 375ndash422 1987

[2] E V Dehmlow and S S Dehmlow Phase-Transfer CatalysisChemie Weinheim Germany 3rd edition 1993

[3] C M Starks C L Liotta and M Halpern Phase TransferCatalysis Fundamentals Applications and Industrial Perspec-tives Chapman and Hall New York NY USA 1994

[4] R R Nadendla Indian Pharmacist vol 2 p 13 2003[5] MMakosza ldquoPhase-transfer catalysis A general greenmethod-

ology in organic synthesisrdquo Pure and Applied Chemistry vol 72no 7 pp 1399ndash1403 2000

[6] J Jarrouse and C R Hebd Seances Acad Sci Ser C vol 232 p1424 1951

[7] H Rath and U Einsele ldquoUber die chemischeModifizierung derZellulose durch AlkylierungrdquoMelliand Textilber vol 40 p 5261959

[8] F Bayer German Patent 959 497 1957[9] N V Gavaert ldquoPhoto producerdquo Belgiam Patent 602 793 1961[10] M A Iskenderov V V Korshak and S V Vinogradova

Vysokomol Soedin vol 4 p 637 1962[11] W S Port British Patent 912 104 1962[12] R W Kay British Patent 916 772 1963[13] S Desikan and L K Doraiswamy ldquoEnhanced activity of

polymer-supported phase transfer catalystsrdquo Chemical Engi-neering Science vol 55 no 24 pp 6119ndash6127 2000

[14] T Shioiri ldquoChiral phase transfer catalysisrdquo in Handbook ofPhase-Transfer Catalysis Y Sasson and R Neumann Edschapter 14 Blackie Academic amp Professional London UK 1997

[15] M Makosza ldquoTwo-phase reactions in the chemistry of carban-ions and halocarbenes A useful tool in organic synthesisrdquo Pureand Applied Chemistry vol 43 p 439 1975

[16] M Makosza and I Krylowa ldquoRemarks on the mechanism ofphase-transfer catalyzed carbanion generation in two-phasesystemsrdquo Tetrahedron vol 55 pp 6395ndash6402 1999

[17] H Abdel-Ghany AM El-Sayed andA K El-Shafei ldquoSynthesisof pyrrole pyridinone and pyrimidinone derivatives using PTCconditionsrdquo Synthetic Communications vol 25 no 8 pp 1119ndash1131 1995

[18] C G Dave and V A Parikh ldquoHeterocyclization using phasetransfer catalysis a simple and convenient synthesis of 2-amino-1-aryl-5-oxo-45-dihydro-1H-pyrrole-3-carbonitrilesrdquoSynthetic Communications vol 31 no 9 pp 1301ndash1306 2001

[19] A M El-Sayed Trends in Heterocycles vol 9 p 33 2003[20] D Albanese D Landini and M Penso ldquoSynthesis of 2-amino

acids via selective mono-N-alkylation of trichloroacetamide

by 2-bromo carboxylic esters under solid-liquid phase-transfercatalysis conditionsrdquo Journal of Organic Chemistry vol 57 no5 pp 1603ndash1605 1992

[21] J Casas R Grigg C Najera and J M Sansano ldquoThe effectof phase-transfer catalysis in the 13-dipolar cycloadditionreactions of azomethine ylides - Synthesis of substituted pro-lines using AgOAc and inorganic base in substoichiometricamountsrdquo European Journal of Organic Chemistry no 10 pp1971ndash1982 2001

[22] O A Abd Allah and A M El-Sayed ldquoApplication of phasetransfer catalysis in heterocyclic synthesis synthesis of somenew polyfunctional thiophenes thiopyrans pyridines andoxazinesrdquo Phosphorus Sulfur and Silicon and Related Elementsvol 177 no 5 pp 1291ndash1301 2002

[23] A K El-Shafei H Abdel-Ghany A A Sultan and M M El-Saghier ldquoSynthesis of thieno (23-b) thiophenes and relatedstructuresrdquo Phosphorus Sulfur and Silicon and the RelatedElements vol 73 pp 15ndash25 1992

[24] H Modrzejewska and K Wojciechowski ldquoSynthesis and reac-tions of 3-alkylsulfanyl-13-dihydro-21-benzisothiazole 22-dioxidesrdquo Tetrahedron vol 61 no 37 pp 8848ndash8854 2005

[25] A Khodairy ldquoSynthesis of fused and spiro heterocyclic com-pounds derived from 35-pyrazolidinedione derivativesrdquo Phos-phorus Sulfur and Silicon and Related Elements vol 160 pp159ndash180 2000

[26] D Bogdal and M Warzala ldquoMicrowave-assisted preparationof benzo[b]furans under solventless phase-transfer catalyticconditionsrdquo Tetrahedron vol 56 no 44 pp 8769ndash8773 2000

[27] M Makosza J Przyborowski R Klajn and A Kwast ldquoSim-ple synthesis of 2-substituted tetrahydrofuran-3-carbonitrilesrdquoSynlett no 12 pp 1773ndash1774 2000

[28] K S Krishna Murthy B Rajitha and M KanakalingeswaraRao ldquoSynthesis of biologically active angularly fused bisaroyl-benzodifurans by PTC and solvent free microwave irradiationrdquoIndian Journal of Chemistry B vol 42 no 2 pp 425ndash428 2003

[29] R D Shah ldquoPhase transfer catalysis assisted thorpe reaction forthe synthesis of 3-aminothiophene-2-carboxylatesrdquo E-Journalof Chemistry vol 8 no 1 pp 368ndash372 2011

[30] W He B-L Zhang Z-J Li and S-Y Zhang ldquoPTC-promotedJapp-Klingmann reaction for the synthesis of indole deriva-tivesrdquo Synthetic Communications vol 35 no 10 pp 1359ndash13682005

[31] T Cholakova Y Zagraniarsky S Simova S Varbanov and ADobrev ldquoA simple synthesis of dimethylphosphinyl-substitutedtetrahydropyrrolesrdquo Phosphorus Sulfur and Silicon and theRelated Elements vol 180 no 7 pp 1721ndash1728 2005

[32] A Khodairy and A M El-Saghier ldquoThieno[23-b]thiophenespart 7 Someheterocyclization reactionswith ethyl 34-diamino-5-cyanothieno[23-b]thiophene-2-carboxylaterdquo Acta ChimicaSlovenica vol 58 no 2 pp 360ndash366 2011

[33] M Y Ait Itto A Hasnaoui A Riahi and J-P LavergneldquoRegioselective synthesis of new biheterocyclic triazepinesrdquoTetrahedron Letters vol 38 no 12 pp 2087ndash2090 1997

[34] G Molteni A Ponti and M Orlandi ldquoUncommon aqueousmedia for nitrilimine cycloadditions I Synthetic and mech-anistic aspects in the formation of 1-aryl-5-substituted-45-dihydropyrazolesrdquoNew Journal of Chemistry vol 26 no 10 pp1340ndash1345 2002

[35] B W LeBlanc and B S Jursic ldquoPreparation of 5-alkylthioand 5-arylthiotetrazoles from thiocyanates using phase transfercatalysisrdquo Synthetic Communications vol 28 no 19 pp 3591ndash3599 1998


[36] A Ogihara H Sakai N Matsui and H Miyazaki PCTInternational Applications WO0276958 (ClC32 ) 2002

[37] P Sharma A Kumar and M Sharma ldquoGeneration of46-dimethyl-5-[2-(2-methylprop-1-enyl)-1H-benzimidazol-1-yl]pyrimidine-2(5H) -thiones under kinetically controlledphase transfer catalysis conditionsrdquo Journal of MolecularCatalysis A vol 237 no 1-2 pp 191ndash198 2005

[38] A M Youssef Egyptian Journal of Chemistry vol 45 p 7772002

[39] M F Farhat A M M El-Saghier M A Makhlouf K MKreddan and A B Elmezoughi ldquoKetene NS-acetals in hete-rocyclic synthesis part 1 synthesis of N-phenyl-2-ylidene and25-diylidene-4-thiazolidinone derivativesrdquo Journal of SulfurChemistry vol 28 no 6 pp 563ndash572 2007

[40] M Fedorynski M Jezierska-Zięba and B Kąkol ldquoPhase trans-fer catalysis in pharmaceutical industrymdashwhere are werdquo ActaPoloniae Pharmaceutica vol 65 pp 647ndash654 2008

[41] A K Khalil ldquoPhase-transfer catalyzed alkylation and cycloalky-lation of 2-mercaptoquinazolin-4(3H)-onerdquo Phosphorus Sulfurand Silicon and the Related Elements vol 180 no 11 pp 2533ndash2541 2005

[42] M K Abou El-Regal A A Abdalha M A El-Kassaby and AT Ali ldquoSynthesis of new thiohydantoin derivatives under phasetransfer catalysisrdquoPhosphorus Sulfur and Silicon and the RelatedElements vol 182 no 4 pp 845ndash851 2007

[43] S El-Metwally and A K Khalil ldquoReactions of 13-diphenyl-2-pyrazolin-5-one and 4-amino-15-dimethyl-2- phenyl-1H-pyrazol-3(2H)-one Synthesis of some new pyrazoles and pyra-zolonesrdquo Acta Chimica Slovenica vol 57 no 4 pp 941ndash9472010

[44] O Atsushi S Hiroshi M Nobuo and M Hidekazu PCTInternational Applications WO 0276 958 2002

[45] MV Zatsepina T V Artamonova andG I Koldobskii ldquoTetra-zoles LII Synthesis of functionally substituted tetrazoles frombenzene-135-tricarboxylic acid derivativesrdquo Russian Journal ofOrganic Chemistry vol 44 no 4 pp 577ndash581 2008

[46] A M M El-Saghier ldquoSimple one-pot synthesis of thieno[23-b]thiophene derivatives under solid-liquid PTC conditionsUseful starting material for the synthesis of biological activecompoundsrdquo Bulletin of the Chemical Society of Japan vol 66no 7 pp 2011ndash2015 1993

[47] K C Majumdar S Saha and A T Khan ldquoIndian Journal ofChemistry Brdquo vol 33 p 216 1994

[48] R M Butnariu and I I Mangalagiu ldquoNew pyridazine deriva-tives Synthesis chemistry and biological activityrdquo Bioorganicand Medicinal Chemistry vol 17 no 7 pp 2823ndash2829 2009

[49] A M El-Sayed ldquoOnemdashpot synthesis of pyridines thienopy-ridines pyrrolothienopyridines and (18)naphthyridines underphase-transfer catalysis conditionsrdquo Phosphorus Sulfur andSilicon and Related Elements vol 163 pp 29ndash40 2000

[50] A K El-Shafei A M Soliman A A Sultan and A MM El-Saghier ldquoSynthesis of some new fused heterocyclescontaining a bridgehead nitrogen atom under ptc conditionsmdasha new application of cyanoketene ss-acetalsrdquo Gazzetta ChimicaItaliana vol 125 p 115 1995

[51] A Khodairy and A M El-Sayed ldquoSynthetic studies on thesynthesis of pyridine 120572-pyran 120572-thiopyran and Thienoth-iopyranopyrrol derivatives using PTC techniquerdquo SyntheticCommunications vol 31 no 4 pp 475ndash486 2001

[52] G A El-Saraf A M El-Sayed and A M M El-SaghierldquoOne-pot PTC synthesis of polyfused pyrazolesrdquo HeteroatomChemistry vol 14 no 3 pp 211ndash217 2003

[53] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoAn efficient synthesis of dibenzoyl dialkyl benzodifurans underphase transfer catalysis conditions and their antifeedant activ-ityrdquo Indian Journal of Heterocyclic Chemistry vol 8 no 1 pp51ndash54 1998

[54] P Sampath Rao K Vishnu Vardhan Reddy and D AshokldquoSynthesis of 26-dibenzoyl-35-distyryl benzo (12-b 54-b1015840)-difurans as potential antifeedantsrdquo Indian Journal of Hetero-cyclic Chemistry vol 7 no 4 pp 293ndash294 1998


[56] K S Krishna Murthy B Rajitha M Kanakalingeswara Rao TRaja Komuraiah and S M Reddy ldquoFacile synthesis of biolog-ically active linear bisaroyl benzodifurans by ptc and solventfree microwave irradiationrdquo Heterocyclic Communications vol8 no 2 pp 179ndash186 2002

[57] A M El-Sayed H Abdel-Ghany and A M M El-SaghierldquoA novel synthesis of pyrano(23-c)- 13-oxazino(23 b)-124- triazolo(34-b)- oxazolo(23-b)- furano(32-c)- and 3-substituted- (15)benzodiazepin-2-onesrdquo Synthetic Communica-tions vol 29 no 20 pp 3561ndash3572 1999

[58] A Khodairy H Abdel-Ghany A M El-Sayed and H SalahldquoSynthesis of new fused and spiro 15-benzodiazepinesrdquo Journalof the Chinese Chemical Society vol 50 no 6 pp 1195ndash11982003

[59] A M Soliman A A Sultan and A K El-Shafei ldquoSyn-thesis of some new dispiro[dipyrano-(2410158406410158401015840)bidithiolo(45-b4101584051015840-e)-48-benzoquinones]rdquoMonatshefte fur Chemie Chem-ical Monthly vol 126 no 5 pp 615ndash619 1995

[60] A A Sultan ldquoSynthesis of some condensed s-triazole hete-rocycles using phase-transfer catalysis techniquerdquo PhosphorusSulfur and Silicon and the Related Elements vol 105 pp 123ndash1271995

[61] A M M El-Saghier ldquoA novel one-pot synthesis of polyfunc-tionally substituted thiopyrano(23-b)pyridine and pyrido(23-b)pyridine derivatives under solid-liquid phase-transfer catal-ysisrdquo Phosphorus Sulfur and Silicon and Related Elements vol177 no 5 pp 1213ndash1221 2002

[62] C Bezergiannidou-Baloucts K E Litinas E M Xenikaki andD N Nicolaides ldquoReactions of 7-(Methoxyimino)-4-methyl-2H-chromene-28(7H)-dione with Phosphorus Ylides Synthe-sis of 2-Substituted 6-Methyl-8H-benzopyrano[78-d]oxazol-8-onesrdquo Liebigs AnnalenDer Chemie vol 1993 pp 1175ndash1177 1993

[63] H A Ghany ldquoSynthesis of new spiro heterocyclic compoundsderived from rhodanine derivativesrdquo Phosphorus Sulfur andSilicon and Related Elements vol 122 pp 173ndash180 1997

[64] H Abdel-Ghany A M El-Sayed A Khodairy and H SalahldquoSynthesis of new 3-substituted and spiro 15-benzodiazepin-2-ones under phase-transfer catalysis conditionsrdquo SyntheticCommunications vol 31 no 16 pp 2523ndash2535 2001

[65] EDiez-Barra A de laHoz A Loupy andA Sanchez-MigallonldquoSelective alkylation of pyrrole by phase transfer catalysis in theabsence of solventrdquo Journal of Heterocyclic Chemistry vol 31 pp1715ndash1717 1994

[66] A Nakmura and K Takamoto Japanese Kokai Tokkyo Koho JP171379 (ClC07D41712) 2003

[67] A Nakamura and K Takamoto Japanese Kokai Tokkyo KohoJP 138 079 (ClC07D20948) 2002


[68] G Guazzelli and R Settambolo ldquo4-Indolylbutanals from rho-dium-catalyzed hydroformylation of allylindoles as precursorsof benzofused indolizinesrdquo Tetrahedron Letters vol 48 no 34pp 6034ndash6038 2007

[69] R Settambolo S Miniati and R Lazzaroni ldquoOne pot hydro-formylationintramolecular aldol condensation reactions of 1-allyl-2-carbonylpyrroles a new entry into hydroindolizinessynthesisrdquo Synthetic Communications vol 33 no 17 pp 2953ndash2961 2003

[70] R Settambolo M Mariani and A Caiazzo ldquoSynthesis of 12-and 13-divinylpyrrolerdquo Journal of Organic Chemistry vol 63no 26 pp 10022ndash10026 1998

[71] P De La Cruz A De La Hoz L M Font F Langa and M CPerez-Rodrıguez ldquoSolvent-free phase transfer catalysis undermicrowaves in fullerene chemistry A convenient preparation ofN-alkylpyrrolidino[60]fullerenesrdquo Tetrahedron Letters vol 39no 33 pp 6053ndash6056 1998

[72] I Almena E Dıez-Barra A De La Hoz J Ruiz A Sanchez-Migallon and J Elguero ldquoAlkylation and arylation of pyrazolesunder solvent-free conditions conventional heating versusmicrowave irradiationrdquo Journal of Heterocyclic Chemistry vol35 no 6 pp 1263ndash1268 1998

[73] Inc Hoffman La-Roch NJ NutelyUnited States Patent PatentNo US 6326501 B1 2001

[74] A Jonczyk E Nawrot and M Kisielewski ldquoReactions ofsome nitrogen heterocycles with chlorodifluoromethane underconditions of phase-transfer catalysisrdquo Journal of FluorineChemistry vol 126 no 11-12 pp 1587ndash1591 2005

[75] P Barraja P Diana A Carbone and G Cirrincione ldquoNucle-ophilic reactions in the indole series displacement of bromineunder phase transfer catalysisrdquo Tetrahedron vol 64 no 51 pp11625ndash11631 2008

[76] C Barrett B Choudhury A Natansohn and P Rochon ldquoAzo-carbazole polymethacrylates as single-component electroopticmaterialsrdquoMacromolecules vol 31 no 15 pp 4845ndash4851 1998


[78] F L Tang Z H Wang W L Jia Y M Xu and J TWang ldquoSynthesis of diorganotin derivatives containing asym-metric disubstituted bis(pyrazol-1-yl)methanes X-ray crystalstructures of (3-isopropylpyrazol-1-yl-51015840 -isopropylpyrazol-1-yl)methane diphenyltin(IV) dibromide and bis(5-isopropyl-pyrazol-1-yl)methane diphenyltin(IV) dibromiderdquo Polyhedronvol 19 pp 381ndash387 2000

[79] V N Pathak C K Oza R Pathak et al ldquoFluorophenylsulpho-nylation of 45-dihydro-35-diarylpyrazoles and 2-arylindolesvia solid-liquid phase transfer catalysisrdquo Indian Journal ofHeterocyclic Chemistry vol 7 no 3 pp 241ndash242 1998

[80] E Arranz J A Dıaz E Morante C Perez and S Vega ldquoPrepa-ration and regiochemical assignments of new pyrazolo[34-c][21] benzothiazepinesrdquo Journal of Heterocyclic Chemistry vol33 no 1 pp 151ndash156 1996

[81] M L Taha H B Lazrek J L Barascut and J L ImbachldquoSynthesis of some 4-substituted 1-[(2-hydroxyethoxy)methyl]-pyrazolo[34-d]pyrimidinesrdquo Bulletin des Societes ChimiquesBelges vol 105 pp 279ndash285 1996

[82] H B Lazrek M Taourirte J L Barascut and J L ImbachBulletin Des Societes Chimiques Belges vol 105 p 391 1996

[83] E Diez-Barra A De La Hoz A Sanchez-Migallon and JTejeda ldquoAlkylation of imidazole by solid-liquid phase transfercatalysis in the absence of solventrdquo Synthetic Communicationsvol 23 no 13 pp 1783ndash1786 1993

[84] X Chen X Wang H Wang H Lian Y Pan and Y ShildquoN-alkylation of 2-methyl-2-imidazolines by phase transfercatalysis without solventrdquo Synthetic Communications vol 29no 17 pp 3025ndash3030 1999

[85] X Chen XWang HWang H Lian Y Pan and Y Shi ldquoChem-Inform abstract N-Alkylation of 2-Methyl-2-imidazolines byphase transfer catalysis without solventrdquo Cheminform vol 30no 43 1999

[86] E V Dehmlow R Richter and A B Zhivich Journal ofChemical Research S vol 504 1993

[87] S Khabnadideh Z Rezaei A Khalafi-Nezhad R BahrinajafiR Mohamadi and A A Farrokhroz ldquoSynthesis of N-alkylatedderivatives of imidazole as antibacterial agentsrdquo Bioorganic andMedicinal Chemistry Letters vol 13 no 17 pp 2863ndash2865 2003

[88] K Ramaiah P K Dubey D Eswara Rao et al ldquoSynthesisand spectral properties of a variety of 2-styrylbenzimidazolesrdquoIndian Journal of Chemistry B vol 39 no 12 pp 904ndash914 2000


[90] E V Dehmlow J Bollhofer and G Thye ldquoJournal of ChemicalResearch Srdquo vol 113 2001

[91] A Abenhaim ldquoSelective alkylations of 124-triazole and benzo-triazole in the absence of solventrdquoHeterocycles vol 38 no 4 p793 1994

[92] I P Beletskaya D V Davydov M S Gorovoi and S VKardashov ldquoSelective N(1)-arylation of benzotriazole with acti-vated aryl halides under conditions of phase transfer catalysisrdquoRussian Chemical Bulletin vol 48 no 8 pp 1533ndash1536 1999

[93] C G Oliva N Jagerovic P Goya et al ldquoN-substituted-123-triazoles Synthesis characterization and evaluation ascannabinoid ligandsrdquoArkivoc vol 2010 no 2 pp 127ndash147 2010

[94] K Waisser J Kunes A Hrabalek M Machacek and ZOdlerova ldquoNew groups of potential antituberculotics 5-Alkylthio-1-aryltetrazolesrdquo Collection of Czechoslovak ChemicalCommunications vol 61 p 791 1996

[95] M L Cerrada J Elguero J De La Fuente C Pardo and MRamos ldquoSynthesis of p-nitrophenylazoles by phase transfercatalysis without solventrdquo Synthetic Communications vol 23no 14 pp 1947ndash1952 1993

[96] Y V Poplavskaya L V Alam and G I Koldobskii ldquoTetrazolesXLI Alkylation of 1-aryltetrazol-5-onesrdquo Russian Journal ofOrganic Chemistry vol 36 no 12 pp 1793ndash1799 2000

[97] K Aritomo T Wada and M Sekine ldquoAlkylation of 6-N-acylated adenosine derivatives by the use of phase transfercatalysisrdquo Journal of the Chemical Society no 14 pp 1837ndash18441995

[98] H Rodrıguez R Perez M Suarez A Lam N Cabrales and ALoupy ldquoAlkylation of some pyrimidine and purine derivativesusing microwave-assisted methodsrdquo Heterocycles vol 55 no 2pp 291ndash302 2001

[99] L Zheng W Xi-cun Y Jing-ya and Z Kexueban Journal ofNorthwest Normal University vol 37 p 54 2001

[100] O S Attaryan A O Baltayan R E Sagatelyan and KT Takmazyan ldquoSynthesis of 1-(2-aminoethyl)pyrazoles underphase-transfer catalysisrdquo Russian Journal of General Chemistryvol 78 no 1 pp 136ndash138 2008


[101] O S Attarian S G Matsoyan and S S Martirosyan ldquoSynthesisof N-vinylpyrazolesrdquoChemistry of Heterocyclic Compounds vol41 no 4 pp 452ndash455 2005

[102] M Majdoub A Loupy A Petit and S Roudesli ldquoCouplingfocused microwaves and solvent-free phase transfer catalysisapplication to the synthesis of new furanic diethersrdquo Tetrahe-dron vol 52 no 2 pp 617ndash628 1996

[103] T M Slaghek A H van Oijen A A M Maas J P Kamerlingand J F G Vliegenthart ldquoSynthesis of structural elements of thecapsular polysaccharides of Streptococcus pneumoniae types6A and 6Brdquo Carbohydrate Research vol 207 no 2 pp 237ndash2481990

[104] A K El-Shafei A M El-Sayed A A Sultan and H Abdel-Ghany Gazzetta Chimica Italiana vol 120 p 197 1990

[105] S-S Jew Y-J Lee J Lee et al ldquoHighly enantioselectlvephase-transfer-catalytic alkylation of 2-phenyl-2-oxazoline-4-carboxylic acid tert-butyl ester for the asymmetric synthesisof 120572-alkyl serinesrdquo Angewandte Chemie - International Editionvol 43 no 18 pp 2382ndash2385 2004

[106] T Tamura andE Ryukoku JapaneseKokai TokkyoKoho JP 128688 (Cl CO7F 96539) 2003

[107] S A Shiba N S Harb M El-Kassaby M A Hassan and NM Abouelregal ldquoFacile synthesis of 4-substituted 2-pyrazolin-5-ones under phase transfer catalysisrdquo Phosphorus Sulfur andSilicon and the Related Elements vol 104 pp 15ndash20 1995

[108] USPTO Applicaton 20090176826mdashClass 514312 (USPTO)[109] E Abele O Dzenitis K Rubina and E Lukevics ldquoSynthesis of

N- and S-vinyl derivatives of heteroaromatic compounds usingphase-transfer catalysisrdquo Chemistry of Heterocyclic Compoundsvol 38 no 6 pp 682ndash685 2002

[110] A Yu Egorova V A Sedavkina and Z Y Temofeyeva ldquoInter-action of 15-substituted pyrrolin-2-ones with dichlorocarbeneunder phase transfer catalysis conditionsrdquoMolecules vol 5 pp1082ndash1084 2000

[111] C I Krishna J Renuka and S Arora Journal of the IndianChemical Society vol 70 p 567 1993

[112] W J Bailey and L-L Zhou ldquoA new elimination with phase-transfer catalysis for cyclic ketene acetalsrdquo Tetrahedron Lettersvol 32 no 12 pp 1539ndash1540 1991

[113] T Terme C Galtier J Maldonado M P Crozet A Gueiffierand P Vanelle ldquoSynthesis of 2-substituted-3-nitroimidazo[12-b]pyridazines as potential biologically active agentsrdquo Journal ofHeterocyclic Chemistry vol 39 no 1 pp 173ndash177 2002

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


+

+

OHPhCH2NEt3Cl

NaOH

PhCH2NEt3Cl

NaOH

ClOCH2Ph

C2H5Cl C2H5

CN

CN

(1)

(2)

Figure 1

PhCH2CN + NaOH

PhCHCN Na + QX

PhCHCN Na + H2O

PhCHCN Q + NaX

org

org org org org

org org

PhCHCN Q + R-X CHC N + QX

int

int

aq

aq

+

++

+

minus

minus +

+

minus

minus

minus

minus PhR

Figure 2

ClCH2R

BrCH(COOEt)2

N

Ph

NH2

NC

RN

NH

CO2Et

CO2EtPh

NC

3

PhNH-CH = C(CN)2

2andashc

R a = CO2Et b = CONH2 c = COPh

Figure 3

4 5

PTCN

CN

O

Ar

NH2

6

ArNHCOCH2Cl + CH2(CN)2

Figure 4

salt and benzyltriethylammonium chloride accelerated two-phase reaction of benzyl chloridewith cyclohexanol (Figure 1(1)) and the two-phase alkylation reaction of phenylacetoni-trile with benzyl chloride or ethyl chloride [6] (Figure 1 (2))

In addition numerous publications and patents [7ndash12]have been reported during the period of 1950ndash1965 PTCstechniques have been further developed byMakosza et al forthe purpose of obtaining more efficient and pure yield [13ndash16]

12 Mechanism of Phase-Transfer Catalysis All phase-transfer catalyzed reactions involve at least two steps

(1) transfer of one reagent from its ground phase into thesecond phase as an intermediate

(2) reaction of the transferred reagent with the non-transferred reagent for example the alkylation ofphenylacetonitrile with alkyl halide using aqueousNaOH as a base and tetrabutylammonium halide


NH2

PhN

CNCN

NQ

CN

Y

Ph NH

CN

CN

CN

PhN CNCN

PhN CNCN

Y

Y

Y

Q

Q

Organic layer

K2CO3 solid surface

HX +

HXQXXCH2Y

Ph-N

Ph-N

Scheme 1









3CNK

2CO318-







3CN








PTCNC CN NC CN


Ph

PTC NC NH2NC NH2

EtOCH = C(CN) X+ CN

SNCN

PhNS

8a bPh X

CN

109a b

X a = CN b = COOEt

Figure 5


NHPh

S

EtOOC CN

SHPhN

PhN


N

EtOOC EtOOC

EtOOC

CN

CN

CNS S

Ph

N

EtOOC

CN CN

COOEtCOOEt

COOEt

S

Ph

EtOCH=C(CN)(COOEt)

S

NH2

NH2

NH2 NH2


O

H2OK2CO3

+

12a

11

8a8b

12b

13

7

Figure 6

NPTC COOCH3

14

16

15 COCCl3


Figure 7








N

RO N

R

O

NH

17 18 19KOHKOH

COORCOORCOOR

R4N XR4N X R1R1

R1

minus

+

+ minus+

Figure 8

HN NH

NC

NC CN

CNPTC

NN

RRNH2

N

CNNC

NNHHN

NC CN


22

2BrCH(CO2Et)2

H2N


2ClCH2R

21andashc

Figure 9

EtO2C

Et EtEt

EtEtEtO

OO

O

OO

O OO

O

OOH

NCPhNCS PTC

PTC

SHSH

PhY

ZX

S

EtO2C

YN

ZX

S

25



+

+

CN CN

PhN

PhN

PhNH

XCH2Y

24andashc

Figure 10


PTC

S SH

H2N

H2NOC

CN

S

H2N CN

5

5

26


27

Figure 11


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X



XCH2Y

XCH2Y


23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12





2CO3TBAB) [19]













PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH2

PhN

CNCN

NQ

CN

Y

Ph NH

CN

CN

CN

PhN CNCN

PhN CNCN

Y

Y

Y

Q

Q

Organic layer

K2CO3 solid surface

HX +

HXQXXCH2Y

Ph-N

Ph-N

Scheme 1









3CNK

2CO318-







3CN








PTCNC CN NC CN


Ph

PTC NC NH2NC NH2

EtOCH = C(CN) X+ CN

SNCN

PhNS

8a bPh X

CN

109a b

X a = CN b = COOEt

Figure 5


NHPh

S

EtOOC CN

SHPhN

PhN


N

EtOOC EtOOC

EtOOC

CN

CN

CNS S

Ph

N

EtOOC

CN CN

COOEtCOOEt

COOEt

S

Ph

EtOCH=C(CN)(COOEt)

S

NH2

NH2

NH2 NH2


O

H2OK2CO3

+

12a

11

8a8b

12b

13

7

Figure 6

NPTC COOCH3

14

16

15 COCCl3


Figure 7








N

RO N

R

O

NH

17 18 19KOHKOH

COORCOORCOOR

R4N XR4N X R1R1

R1

minus

+

+ minus+

Figure 8

HN NH

NC

NC CN

CNPTC

NN

RRNH2

N

CNNC

NNHHN

NC CN


22

2BrCH(CO2Et)2

H2N


2ClCH2R

21andashc

Figure 9

EtO2C

Et EtEt

EtEtEtO

OO

O

OO

O OO

O

OOH

NCPhNCS PTC

PTC

SHSH

PhY

ZX

S

EtO2C

YN

ZX

S

25



+

+

CN CN

PhN

PhN

PhNH

XCH2Y

24andashc

Figure 10


PTC

S SH

H2N

H2NOC

CN

S

H2N CN

5

5

26


27

Figure 11


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X



XCH2Y

XCH2Y


23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12





2CO3TBAB) [19]













PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


PTCNC CN NC CN


Ph

PTC NC NH2NC NH2

EtOCH = C(CN) X+ CN

SNCN

PhNS

8a bPh X

CN

109a b

X a = CN b = COOEt

Figure 5


NHPh

S

EtOOC CN

SHPhN

PhN


N

EtOOC EtOOC

EtOOC

CN

CN

CNS S

Ph

N

EtOOC

CN CN

COOEtCOOEt

COOEt

S

Ph

EtOCH=C(CN)(COOEt)

S

NH2

NH2

NH2 NH2


O

H2OK2CO3

+

12a

11

8a8b

12b

13

7

Figure 6

NPTC COOCH3

14

16

15 COCCl3


Figure 7








N

RO N

R

O

NH

17 18 19KOHKOH

COORCOORCOOR

R4N XR4N X R1R1

R1

minus

+

+ minus+

Figure 8

HN NH

NC

NC CN

CNPTC

NN

RRNH2

N

CNNC

NNHHN

NC CN


22

2BrCH(CO2Et)2

H2N


2ClCH2R

21andashc

Figure 9

EtO2C

Et EtEt

EtEtEtO

OO

O

OO

O OO

O

OOH

NCPhNCS PTC

PTC

SHSH

PhY

ZX

S

EtO2C

YN

ZX

S

25



+

+

CN CN

PhN

PhN

PhNH

XCH2Y

24andashc

Figure 10


PTC

S SH

H2N

H2NOC

CN

S

H2N CN

5

5

26


27

Figure 11


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X



XCH2Y

XCH2Y


23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12





2CO3TBAB) [19]













PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

RO N

R

O

NH

17 18 19KOHKOH

COORCOORCOOR

R4N XR4N X R1R1

R1

minus

+

+ minus+

Figure 8

HN NH

NC

NC CN

CNPTC

NN

RRNH2

N

CNNC

NNHHN

NC CN


22

2BrCH(CO2Et)2

H2N


2ClCH2R

21andashc

Figure 9

EtO2C

Et EtEt

EtEtEtO

OO

O

OO

O OO

O

OOH

NCPhNCS PTC

PTC

SHSH

PhY

ZX

S

EtO2C

YN

ZX

S

25



+

+

CN CN

PhN

PhN

PhNH

XCH2Y

24andashc

Figure 10


PTC

S SH

H2N

H2NOC

CN

S

H2N CN

5

5

26


27

Figure 11


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X



XCH2Y

XCH2Y


23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12





2CO3TBAB) [19]













PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NCH O

OOO

CS2

NC

O OO

O

NC

O OO

O

S S

SH

SH

Y

PTC

PTC

S

S Y

PTC

PTC

S S YS

NH2

YS

OH

CN

CN

N

NH

S

NC

PhNCS

PTC

EtO2CEtO2C

CO2Et

CO2Et

COPh

Ph

Ph

PhN

PhN

PhNS

NCEtO2C EtO2C EtO2C

S

EtO2CCO2EtEtO2C

OH

Y

Z ZX X



XCH2Y

XCH2Y


23

7

28andashc 29andashc

30 25andashc 24

+

++

Figure 12





2CO3TBAB) [19]













PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


PTCK2CO3

DioxaneTBAB

NC

SHS

CNPTC

EtOCH=C(CN)(X)

HCN

PTC

S

S

NC

X

X

CN

SX

CN

HS

NC NH

HS

NC

CNS

31a b

X a = CN b = COOEt

EtOCH=C(CN)(X)

+

PTCEtOOC

S SH

CN

PTC

CN

EtOOC

EtOOC

SX

HCN

S

S S

NH2

NH2

X

OH

S S

NC

CNCNCOOEt

PTC


11

8a b

8a b

5

NCCH2COOEt + CS2

CH2(CN)2 + CS2

Figure 13

NSO2 SO2

N

Me

ClPTC

S

N

N

Me

SN

NH

Me

+

33 34 35

NCSminusSO2

Figure 14

CNHOOC CN

BrCH(CN)2 + HN NH2

NH2

O

ONPTC

HOO

HN

O

ON

Ph Ph36 37 38

Figure 15

CNO

NH2

NH2NH2N

HOOC

HNNO

O

CN

Ph

3738

Ph

H2NH2OOHminus

H2OOHminus

CN

OHO

HOOC

+ PhNHNH2

Figure 16


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OH

CHOR + ClCH2COOR1

PTCMicrowave

O

R

39 40 41

COOR1

Figure 17

Ar-CH-OH

NC-CH-CH2-CH2Cl

O Ar

CN

42 43 44


Figure 18

CH3O

OHHO

H3C

O

K2CO3TBAHSO4 O

OO

CH3

O

X

X

H3CEDC


COCH2Br+ 2X

45

46

Figure 19

CNR

H OH


H S COOR1COOR1

CNR

S

R NH2

47andashf 48andashf

a phb 4-O-CH3



60ndash70∘C

Figure 20






NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH2

R

HClHNO2

N+

NCl

R

NCH3O

COOC2H5

CH3

COOC2H5

COOC2H5

O O

NN

HNO

O

R

NH

N

O

O

HCl

49

50

5152 R

0ndash5∘C

Figure 21

+

N

HCOPh

COPhH5C6

PH3CH3C

H3CH3C

OCl

53

54

NPh

PO

Cl

55

Figure 22

N C6H4-Cl-4PH3CH3C

H3C

H3C

H3C

H3C

O

PhCOOEt

+

NH

NH

H5C6

H5C6

C6H4-Cl-4

C6H4-Cl-4

COOEt

P

COOH

PO

O

NaOHH2OCH3CN

NaOHTEBA H2ODMSO

53

56

57

58

Figure 23




2and chloroac-






N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

OPh

PTCNN

CH3

O

Ph

S

SN

H2N

59 60

+ CS2 + ClCH2CN

H3C

Figure 24

N O

O

Ph

+ + ClCH2COOEtHNHN

HN

HN

O

O

Ph

S

COOEt

S

N N

O

O

Ph

SH

EtOOCH2CS

N

O

OPh

S

S

O

36

61

minusEtOH

CS2

Figure 25

SS COOEt

NC

NH2

NH2

NH2

NH2

SS

COOEt

NCN

S

N

S

SS

CS2ClCH2CNPTC

PTC

CS2ClCH2COOEt

S

S

COOEt

NCN S

N

SO

SS O

62

63

64

Figure 26


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


S

SS

S

S

S COOEt

COOEt

NC

NH2

NH2

PTC

N

N

NC

SS

CS2Br(CH2)2Br

6562

Figure 27

PhPh

NN

O PTC

N

NHN

H3Cn = 0 1 a n = 067a b b n = 1

66

S

CH3


Figure 28


RndashCH=CH2

N

NR

Ar70

69

68

minus+

Figure 29

H3C

H3C


N

N

N

SO2

SO2H3C

H3C

R

PTC

R1

71 72

7371

74

75 R2

SO2CH2NC + R1CH=NR2

Figure 30

Me

ClMe

CH + N=NN

N

H3C

S

CH3

PTCN

N

NN

CH3

CH3

S

CH3

H3C

RR

76 77 78

Figure 31


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Br

BrPTC+

79 80 81

N

S

NO

H

PhNH

HNS

H

PhO

Figure 32

X

Y

+ PhNCSKOHDioxan

XYPhHN

KS

N

S

O Ph

X

Y



Cl

Z

OZ = Cl OEt or NH2

82andashg 83andashg

Figure 33










1CH=NR

2or 73 (R

1 R2=








OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OH

+ H2CBr

NaOHH2OTBAHSO4

OCH2

97


84 8586

87 O

S NH

S

OHO

OO

NH middotHCl

Figure 34

NH

NH

O

SH

ClCH2COCl

Br(CH2)2Br

PTC89

88

O

N

NH

NH

S

OO

N

S

90

Figure 35

Ph

NO

O

SN

CS2 Br(CH2)2Br H

NH

NH

PTC

Ph

S

S

N

Ph

S

N

O

91

CS2Br(CH2)3Br

S

S

SPTC

92b

92a

Figure 36


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


H3C

H3CH3C

H3CNH

NH Ph

X

NN

Ph

O

NN

Ph

O

NN

R

XO

BrCH2COOEtPTCTBAB

93 X = S 95a bX a = S b = O94 X = O

Figure 37

NHPh

N

HN

H

Ph H O

+

Br

Br

Br

Br

PTC

PTC

PhH

H

N

O

N NN Ph

OH

96

N

O

OO

O

O

N

NNN

N

Ph

NHN H

H

HN HN

PhPh

97

98 99a 99b

+ +

Figure 38

CNNC

CH3

CNNC

N NN

H3C

H3CH3C

H3C

CH3

CH3CH3 CH3

CH3

CH3Cl 50 NaOH aq

TEBA

Anastrozole

100

101

CNNC

Figure 39

SN

R(Ar)

N

NN N

N N

NR(Ar)S

PTC

+

++

102 103 104

Figure 40


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


+

NN

NN

NN

N N

N

NN

N

R

R

R

105

NCl

N

ClN

Cl

R

R

R

Bu4NBrCHCl3-H2ONaN3


106andashe

Figure 41

NC CN+ CS2 + XCH2Y

SS

H2N

Y Y

NH2

aY = COOEtb Y = CN

5107a b

PTC

X = Cl Br

Figure 42


S S

H3C

C2H5O2C CO2C2H5

CH3

H3COC COCH3

109108

Figure 43

H2N NH2


S NPh

110

5 7

Figure 44

NN

O

NN

O

S

S

NN

PhPh

Ph

S

S

NC

NC

63 111

CH3CH3

CH3

+ CS2 + ClCH2CN

Figure 45


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


HNN

O

O

Ph

HNN

O

O

Ph

S

S

R HN

N

S

O

R

S

Ph36 112


R = CN COOEt

Figure 46

S S S

O

S

OH

Br PTCCH3+

113 115114

Figure 47






2CO3as liquid-solid















2and





NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NN

OAr

N

O

O

Ph

NN

N

O

O

OAr

Ph

NN

OAr

H

HNN

OAr

HH

NN

OAr

H

H

HZ

NN

OAr

PTC

X

X

X

X

or

Or

Z

X Y

116

117

118a 118b

119

120

Brminus

CO2CH3

CO2CH3

CO2CH3

X = CO2CH3

Z = CN CO2C2H5

X = H CO2C2H5


H3CO2C

+

H(CO2C2H5)

Figure 48

NN

NH2 NH2

SHHS

NH2 NH2NH2

NH2NH2

CNNC+ 2XCH2Y PTC

N NS S

H2N

Y Y

X = Cl Br


NN ClCl

CNNC

+ 2HSCH2COOEt PTC

121 122

123

Figure 49



2Cl2aq







N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

NH2

NH2

NH2

SY


NC

NH

SH

NH2

CNNC+ XCH2Y

PTC

N

N S

H2N

Y

Y

X = Cl Br

PTC1 2

1 1

124

125

126

H3CS

H3CS

H3CS

Figure 50

NH2

NH2

PTC

PTC

X = Cl Br

Y

HN

Z Y

NZ

R

R

NH

Z

HN

R

N

N

Y

Z = CN CO2C2H5

Z = CN CO2C2H5

R = CN CO2C2H5 COPh

R = CN CO2C2H5 COPh

Y = S OX = Cl Br

CH2NH2

Y = NH2 OH

127 128 129 130

131a b

132

+ XCH2R

+ XCH2R

CH2NH2

Figure 51










N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N N N N

NH2

Cl Cl

NH2 NH2 NH2 NH2CNNC

PTC

NH

NH


133 134

H2N

Figure 52

SZ

HS

PTC

PTC

S

S

NH

Ph(p-Cl)

Ph(p-Cl)

Ph(p-Cl)

+ ClCH2CO2C2H5

C2H5O2C

C2H5O2C

CO2C2H5

1 1

1 2Z = CN CHO PhCO

Y = NH2 H Ph

135

136

137

CN

NH

SN S

Y

YH2N

Figure 53

N

O

NPh

Ph

N N

SS

Ph

PhN

S

NH

S

HO

Ph

Ph

SNC

NN

S

N

N N

S

Ph Ph

N N

SPhOC

Ph N N

SPhOC

S

NPh

Ph

N N

SS

NC

PTCNH

OS

NN

S

S

N N

S

PhOC

138

139

140

+

+

+

141 142

147

146

143

145

144

ClCH2CN

C2H5O2CClCH2CO2Et

PhCOCH2Br

(1 1 1)PTC

ClCH2CN(1 1 2)PTC

(1 1 1)PTC


(1 1 1)PTC

PhCOCH2Br

(1 1 2)PTC

CS2

NH2

NH2

NH2

NH2

NH2EtO2C EtO2C

COPh

SCH2COPh

NH2

NH2

SCH2COPh

Figure 54


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


SSS

NH

S

PTC

EtOOCCOOEt

CN

CN

NC NH2NH2

COPh+ PhCOCH2Br

14831b

Figure 55

PTC CNCN

CNCN

NH2NH2

PhOC+ PhCOCH2Br

150a b


PhPh149a b

HSNS

X

N

Y

Figure 56

OO OH R

O

O OO O

R

+ PhCOCH2Br

CH3 CH3


151 152

Figure 57

R R

OO

OHHO OO

R

OO

R

+ PhCOCH2Br

154153


p

Figure 58

HO

R

O

OH

R

O

OO OO

R R

+ PhCOCH2Br


Figure 59


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OO

X OO

OO

+

HO OH

R(Ar)

(Ar)R

COCH2Br

(Ar)R

R(Ar)

ArAr

157 158

Figure 60

NN

OPTC

N

N O

CN

PhPh

63 159

H3C

NH2

H3C

+ BrCH(CN)2

Figure 61


2CO3TBAB)











2CO3TBAHSO

4) [53]











2to give 165












N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

NO

N

NO

H3CNH2

H3C

+ ClCH2CN

161160CH3CH3

Figure 62

N

NHO

N

NO

+ ClCH2CN

NH2

162 163CH3

CH3

PTCDioxan

Figure 63

O

O O

O

S

SS

S+

Br

Br

Br

Br

KS

KS

PTC

COCH3

COCH3

COCH3

COCH3

H3COC

H3COC

164165 166

Figure 64

N

O

O N

O

O

S

S

X

S

S

NX

O

HN

Ar

Ph


Ar

Ph

CN minusH2OHN

CNPh

Ar



Figure 65

N

NN

O

O

NN

N

NH

N

NN

HN

S

S

O

O

+

NH2

SHPh

Ph

Ph

Br

Br

Br

Br

PTC

171169 170

Figure 66


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

N

O

S

O

S N

NN

X

S

S NX

H2N CN

CNNC + X=C=S

CH3

Ph

NH

NH

CN

NH2

NH2

CNNH2

NH2

NH

H3C

HN

X = S NPh172

174

175

63

173

Ph

Figure 67

N

HN

O

N

NO

CH3

+ ClCH2CNPTC

CH3

NH2

167 177

Figure 68

OO

O

NO

OO

Me

MeON

PTC

Me

H3C178

179180


Figure 69

N

N

S

SN

NN

S

S+ BrCH2CH2Br

181 182

NH

Ph

H3C

Ph

H3C

Figure 70


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

SS

O

HN

X

N

SS

O

YN

SS

O

Z

X

SN

SS

O

N

SN

SS

O

BrBr

Ph

PTC

NH2

XH

YH

ZH

HSCH2CH2XH

H2NNHCSNH2

Ph

Ph

X = O S NH

Y = Z = NH O

Ph

X = NH O

HN

Ph

NH2

183

184

185

186

187

Figure 71





















2CO3TBAHSO




N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

O

O

S

S

N

O

O

XHN

OEt

Ph


Ph

CN

X = CN COOEt188189

5 or 11

Figure 72

N

NO

X

YN

NO

X

YN

NO

N

S

NHN

NO

COPh

Br

BrPh

XH

YH

XH

YH

H2NNHCSNH2

COPh


COPh

Ph

X = NH SY = O S NH

COPh

Ph

NH2

190

191

192

193

Figure 73

NH

N

RNH

R

NH

R+ +

RXPTC

161 162 163 164

Figure 74

O

O

N

O

O


198 199 200

Figure 75


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

+R

X

N

R

R998400998400

CH2

R998400

R998400

R998400998400

CH2R998400998400998400 R998400998400998400


R998400998400998400 = H 5-CH3 7-CH3 X =

Figure 76

NH

O N

O

R1

R2

R3R1 R2

R3

Cl

a R1 = H R2 = CH3

b c R1 = CH3 R2 = CH3 R3 = H


+

Figure 77

NH

O

R

NO

R

N

R(CH2)Cl2 THF NaNH2


207 208204Cl

R = H

(a) R = H(b) R = CH3

Figure 78



4) [69] (Figure 77)





2CO3and TBAB




NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

Ph

PTCMW N-R∙

Ph

209 210

R-Br

Figure 79

N

N

NNH

N

N

NN

+2

Ar Ar

Ar

Ar


211 213

Ar

Ar

Br

Br

Ar998400Ar998400

Ar998400

Ar

214212

(CH2)3

Figure 80

NH

NH N

H


K2CO3 TBAB

215 216a 216b

DMF 126∘C 26 h

Figure 81











NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

NH N

N+

+

ClCHF2

CH3

CH3

ClCHF2

CHF2

CH3

CH3

CHF2

217 219

218 220

Figure 82

N

Br

R1

R

+ NuH

N

Nu

R1

R



221 222

Figure 83

NH

N

+ Br(CH2)6Br

(CH2)6Br223224

Figure 84



2(3-



2(5-isoPrPz)




[CH2(3-iPrPz)

2] 235 [78] (Figure 86)


3or benzeneaq



4) pro-




NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

N NN

NH

N

NN

NN

NH

NN

N

R

+( )

( )Br

+ BrCH2CH2Br

NN

+ RX

n = 2 3

1 1

2 1

225

225

226

227

228

229

226a b

CH2CH2

CH2CH2Br


n

n

Figure 85

NH

N NN

NN

NN

NN

NN

NN

NH

N NN

NN

+

+

i-Pr

CH2

CH2

CH2

i-Pr i-Pr

CH2

i-Pr

i-Pri-Pr

i-Pr

230231

232 233 234

235

ButButBut

+ CH2Br2

+ CH2Br2

Figure 86








NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

N

NH

N

N

N

R

N

N

ArAr

+ RX

+ CH2 =CH-CH2-X

Ar

Ar

Ar Ar

Ar

Ar

236 237

236 238

Figure 87

NS

NN

O

NS

N

N

R

O

RNS

N

N

R

OR

OO OO

+

H

O

OCH3

RX or R2SO4


239 240a 240b

Figure 88

N

N N

R

N

N N

N

R


241 242

Figure 89

NH

N

N

N

R

NH

N

R

+

+

+ RX


243 244a 244b

Figure 90


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

N

N

N

R

+ RBr


245

Figure 91

+ RX PTC

246 247

N

N

RN

H

HNH

CH3CH3

Figure 92

N

NH

N

N

N

N

N

NH

N

N

N

N

+

+

250b

249 251a

250a

251b

O2N

O2N

248

O2NO2N

O2NO2N

CH3

CH3

CH2Ph

CH2Ph

+ PhCH2Cl

+ CH3I

Figure 93

N NH N N

R

R252a b 254

R1


R2


253

a R1 = CH3 R2 = Hb R1 = CH3 R2 = NO2

TEAI NaOH C6H5CH3

Figure 94

NH

N

O N

N

OR

256 257

CH3

+ RXK2CO3TEBACl

CH3

CH3CN

Figure 95


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

NH

Ph PTCN

Ph

258 259

+ ClCHF2

CHF2

Figure 96

N NH

R

N N

R

260 261 262


Figure 97

O NH

O

O N

O

PhO N

O

Ph

+

263 264a 264b

H3C

H3C

H3C

H3C

H3C

H3C+ PhCH2Cl

Figure 98

NN

NH

NN

NR

267 268

NN

NH

NN

N

NN

N+

267 269a 269b

N

N NH

N

N NR

265 266

+ RX

+ RX

+ ArX Arminus

Arminus

Figure 99


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NN

NH

NN

N

267 270

+ ClCHF2

CHF2

Figure 100

NNH

N N N

RN

NN

RN

NN R

271272

273a 273b 273c

+ +

CH3

CH3

CH3CH3


R = alkyl benzyl

+ RBr

Figure 101

NN

NNHPh

NN

N

NPh

NN

N

NPh

+

274 275a 275b

+ ClCHF2

CHF2

CHF2

Figure 102




3CNK

2CO3TEBACl) at room











N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

NH

N

N

S N

NN

N

SR

xN

x

x

x

H

xN

x

x

x

+

F

N

NH

N

N

OPTC

N

N

NN

O

N

N NN

O

+N

N

N

O

Br

290 291289

278

276 277

Arminus

Arminus

ArminusArminus

Arminus

Arminus

+ RX

279ndash288


NO2

NO2

+ Br-(CH2)n- Br

n

n

Figure 103

O

OSMDBTTBMSO

TBMSO NN

N N

NHCOMeRXPTC

O

OSMDBTTBMSO

TBMSO NN

N N

NRCOMe

+

O

OSMDBTTBMSO

TBMSO NN

N N

NCOMe

R

292 293a293b


Figure 104


2Cl2aq NaOH



4NBr








N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

N N

NH

PTCMW

N

N N

N

R

294 295

+ RX

NH2NH2

Figure 105

S

N NArO

+ O

O

Cl S

N N

NHArO

OO

Cl

296 297 298

NH2

CH3

Figure 106

NPh

MeO

S

O

OMe

H

PTC

299300

NHPh

MeO

S

O

OMe

HCH2=CH-CH2Br

CH2

Figure 107

NNH

R

NN

R


CH2CH2NH2

70∘C



Figure 108

NH

NR

PTC

NNR

PTC

NNR

R1

R1R1

ClCH2CH2Cl

CH2CH2Cl

minusHCl

CH = CH



Figure 109


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


OOH

OH

HOO

310 311

O OO

O

312 313

OO

O

315

314

+ 2C12H25Br OC12H25

+ Br (CH2)12Br

X(CH2)nX

n = 1 4 5 X = Brn

12

H25C12O

Figure 110

OOMe

H

OH

Crotyl OO

OMe

H

O BenzylHOHO

Crotyl O

316 317


Figure 111

N NH

S

O

H

Ph

OMe

OMe

HN N

O

H

OMe

OMe

PhN NH

O

Ph

H

OMe

MeO

PTC

318 319a b

S-(CH2)n-S

Br(CH2)nBr

Figure 112

S

N

O

SS

N

O

S

S

N

O

S

RRX

322 320


321andashh


Figure 113


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

O Br

N

O+

323 324

CO2 t-Bu CO2 t-Bu

Figure 114

N

N

NH

S

O O

Br

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

+

O

N

HHO

H H

O

Ph

O

O

Ph

O

O

Ph

N

N

S

O

325 326 327

R1

R1

R2

R2

R3

R3

Figure 115












N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


N

NH

SO

Ph

N

N

O

Ph

SR

SR

PTC

91

RXCS2SR1


Figure 116

N NH

S

O

H

Ph

OMe

OMe

318

N N

S

O

H

Ph

OMe

OMe

329

ClCH2COCl

COCH2Cl

Figure 117

S

N

S N

NS

NOS

SSBr

O

PiperazineS SHet

O

N

N

OHHS

N

S b

332330 331ab

CH2

Arminus


HetminusH+

HetH = a NH2

Figure 118

NN O

Ph

NN

O

Ph

R

NN R

Ph

+

333

+ RX

H3CH3CH3C


Figure 119

NN

N N

+NH

O

NN

N NO

O

336 337 338

(CH2)4BrHO

NH4

( )

Figure 120


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

N + F

N

SOO

F340 339 341

NH

+ SO 2ClFNS

OO

F339 343342

SO2Cl

ArminusArminus

Arminus

ArminusArminus

Arminus

Arminus

Figure 121

O

O

F

F NO

NH

N

O

O

S

ON

OO

ClF

F+PTC

344 345

346

SO2Cl

H3C

H3C

CH3

CH3

Figure 122

NNH +

Cl

Cl

O

NN

O

NN

347 348 349

Figure 123

S

NH

O+ Cl P

O

OEt

S O

P

OEtO

350 351 352

S-sec-Bu

P-S-sec-Bu

Figure 124

R

353

O

O Br

R

354

O

O

CH2

Figure 125


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NN

N Cl

Cl

-

356PTC N

N

N

Cl

CH3CH3

NN

N

Cl

355 357

CH3

NO2NO2

NO2

NO2

CH3M+

O2N H3CH3C

minusHNO2

Figure 126

NH

PTC

N

NH

PTC

N

S

PTC N

NS

N

NH

361

360

358 359

362

363

+ ClCH2CH2BrSH

H2C

CH2

+ ClCH2CH2Br

+ ClCH2CH2Br

SH

H2C

H2C

CH2

Figure 127




2Cl2and TBAB





2CO3TBAB) as a PTC




S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


S

NO

S

ArCHOPTC S

NO

S

385384



Figure 128

S

NO

S

HCHOPTC

PTC

S

NO

SHO

S

NO

S

CN

NC

387

388

S

NO

S PTC

N N

S

OS

390

386

389

Arminus

Arminus

Arminus

ArminusArminus


Ar998400

Ar998400

Ar998400

Ar998400CH=C(CN)2

Ar998400 = Ph 4-N(Me)2-C6H4

CNCH2CONH2

-

- -

Figure 129

OR

PhN O

O

R

Ph

OR

Ph

Cl

Cl

N O

Cl

R

Ph

391 392

CHCl3NaOH

Figure 130


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


NH

R

R

NaOHN

R

Cl

R

NH

R

CHO

NaOHN

Cl

R

OCl

Cl393

394

395 396

+ CHCl3

+ CHCl3

TBAHSO4

TBAHSO4

Figure 131

NS

O

OMe

PTC NS

O

OMe

SMe

NMe

SMe

Way A

NMe

SMe

SO

minus

NSO

SMe

O

NS

OMe

SMeMeS

N

Me

SMe

SMe

401

400

Way B


minusSO2

CH3

minusSMe

minusSMe

Ominus

Ominus

Figure 132














2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





2O K2CO3and TBACl




2CO3TBAB) [109]

(Figure 122)











2CO3



3NaOH



4H)



3CNK

2CO3



Abbreviations








References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





References




























































































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

review article synthesis and reactions of five-membered...

Documents