chapter -2 synthesis of coumarin/1-azacoumarin...

Literature review of Dithiocarbamates

Karnatak Science College, Dharwad 52

Chapter -2

Synthesis

Of

Coumarin/1-azacoumarin

Dithiocarbamate

Derivatives



Literature Review on Dithiocarbamates:

A) Synthesis of dithiocarbamates:

Y.-C. Duan et al.,1 were designed a series of novel 1,2,3-triazole-dithiocarbamate

hybrids, synthesized and evaluated for anticancer activity against four selected human

tumor cell lines (MGC-803, MCF-7, PC-3, EC-109).

W. Huang et al.,2 were designed and synthesized a series of chromone derivatives

bearing diverse dithiocarbamate moieties via a three-component reaction protocol.

Run-Tao Li et al.,3 have been designed and synthesized a series of 4(3H)-quinazolinone

derivatives with dithiocarbamate side chains by using K3PO4 as a catalyst.

N NN

S N

S

N O

O

R

O OH O

N NN

S N

S

N O

O

N NN

S N

S

N O

O

O

R

O O

O

O

S N

SR

O

O

COOEt

SN

S

O

O

R S N

S

HN

N

O

H3C

CH2BrHN

N

O

H3C

S NR1

R2

S

CS2, K3PO4

DMF, RT, 2h



Vijjulatha. M et al.,4 were reported novel dithiocarbamates with benzimidazole and

chalcone scaffold. They have been designed, synthesized and evaluated for their

antimitotic activity.

Runtao Li et al.,5 have been reported a variety of 4-N atom substituted derivatives with a

variety of 1-N-substituted piperazines, were reacted with carbon disulfide and 3-cyano-

3,3- diphenyl-propyl bromide in the presence of anhydrous potassium phosphate at room

temperature.

M. S. Behalo and A. A. Aly6 were developed a one-pot three component synthesis of

alkyl/aryl-dithiocarbamic acid-3-oxo-3-(phenoxathiin-2-yl)-1-phenyl/(4-chloro phenyl)

propyl esters was achieved from the reaction of 3-phenyl/(4-chlorophenyl)-1-

(phenoxathiin-2-yl)propenones, amine, and carbon disulfide.

N

HN

S N

S

R 2

R 1 O SN

S R 1

R 2

HN NH

CN

BrCS2

CN

SN

S

HN

K3PO4

Acetone, RT

O

SPh

SO NH

S



Cao, Shengli et al.,7 have been synthesized (6,8-diaminonaphthalen-2-yl)methyl 4-(4-

(trifluoromethyl)phenyl) piperazine-1-carbodithioates as anti tumor agents.

W. Luo et al.,8 have been reported [3-(1-Oxo-1,3-dihydro-1H-isoindol-2-yl)-2,6-

dioxopiperidin-1-yl] methylcyclohexyldithiocarbamates. The synthesis involved

utilization of a novel condensation approach, a one-pot reaction involving addition,

iminium rearrangement and elimination, to generate the phthalimidine ring required for

the creation of compounds.

G. Turan-Zitouni et al.,9 have been described some 1-[(N,N-disubstituted

thiocarbamoylthio) acetyl]-3,5-diaryl-2-pyrazolines derivatives which were synthesized

by reacting 1-(chloroacetyl)-3,5-diaryl-2-pyrazolines with appropriate potassium salts of

secondary amine dithiocarbamic acids.

NH2

NH2

SN

S

N

F3C

N

N

O

O

O C l

N

N

O

O

OS

N

S

R 2

R 1

C S 2 , C H 3 C N , N 2

rt , 4 2 -4 6 h

R1 HBHA

HX

COC H2Br

R2

R1 HBHA

HX

COC H2S

R2

R3

S

AcetoneSK C R3

S



Weiliang Bao et al.,10 have been developed a method for the synthesis of aryl and vinyl

dithiocarbamates under Ullmann coupling reaction of sodium dithiocarbamates with aryl

iodides and vinyl bromides catalyzed by CuI/N,N-dimethylglycine proceeds in DMF at

110 ºC to give corresponding dithiocarbamates.

Bakare and Oladapo11 have been developed the Preparation of emetine

derivatives(2(1H)-isoquinolinecarbodithioic acid, 1-[[(2R,3R,11bS) -3-ethyl-1, 3, 4, 6, 7,

11b- hexahydro-9, 10dimethoxy-2H-benzo[a]quinolizin-2-yl]methyl] -3, 4-di hydro-6, 7-

dimethoxy-phenylmethyl ester), prodrugs containing same, and methods of treating

conditions using same.

Dirk J.M. Vanderzande et al.,12 have been performed Polymerizations via the

dithiocarbamate precursor route, using lithium hexamethyldisilazide (LHMDS) as a base,

to obtain high molecular weight precursor polymers.

I

N S-Na+

S

CuI/ligand/base

Solvent/22h

S N

S

N

H 3C O

H 3C O

S

S P h

H

Et

H

H 3C O

H 3C O

R

R

S

R

O

O

S N

S

SN

S

R O

R O

.H 2 O

O

O

S N

S

SN

S

R O

R O

. H 2 O

O R

O R



Julie Banerji et al.,13 have been achieved a new, expeditious, efficient and eco-friendly

method for the synthesis of organic dithiocarbamates at room temperature using basic

nano crystalline MgO catalyst in aqueous condition.

S.L. Cao et al.,14 were designed and synthesized a series of N-((2-methyl-4(3H)-

quinazolinon-6-yl) methyl) dithiocarbamates and were evaluated for their cytotoxic

activity against five human cancer cell lines.

Kaliyamoorthy Alagiri and Kandikere Ramaiah Prabhu15 were developed a catalyst-

free regio- and stereo specific synthesis of b-sulfonamido dithiocarbamates: Efficient

ring-opening reactions of N-Tosyl aziridines by dialkyldithiocarbamates.

RNH

R1

XCS2R

N

R1

SX

S

NPMgO

RT, Water

HN

N

O

H3C

NH2.HCl

HN

N

O

H3C

NH

SR

S

CS2, K3PO4, RX

DMF, RT, 2-12h

NH

CH3CN, 0-80OC

3h

TsN

CS2

S

NHTs

N

S

TsN

R2R1

NaS N

S

SN

S

R1

NHTs

R2

CH3CN

80OC



Krishna Nand Singh et al.,16 have been exploited the combined role of microwave

superoxide and the synthesis of organic dithiocarbamates under non-aqueous medium

employing amines, carbon disulfide and methyl iodide.

Kyung Woon Jung et al.,17 were synthesized dithio derivatives via a three way coupling

was performed to combine diols, diamines, and amino alcohols with carbon disulfide and

halides in the presence of a cesium base and TBAI.

Saidi et al.,18 have been reported one pot synthesis of dithiocarbamates based upon

amines, CS2, and alkyl halides without using a catalyst under solvent-free conditions.

I. Kaur and S.K. Verma19 were polymerized and grafted the monomer onto cotton

fabric by the living radical polymerization method using benzyl N,N-diethyl

thiocarbamate as iniferter and sur-iniferter respectively.

RNH2 CS2

KO2/Et4NBr

CH3I, DMFMW

R

HN S

S

CH3

Y Z Y Z SR

S

nn

RX, Cs2CO3, CS2

TBAI, DMF, 0OC, rt

1. Y=Z=NH2 2. Y=OH, Z= NH23. Y=NH2, Z=NH 4. Y=OH, Z=NH

R1R2NHCS2, rt

3-12h R2

NS

S

R3

R1

R3X

Benzylchloride S N

S

NH NaOH/tolueneCS2 NaS N

S

C2H5OH



Kyung Woong Jung et al.,20 have been reported a protocol for a one-pot, three-

component coupling of various amines with an alkyl halide via a carbon disulfide bridge

using Cs2CO3 and TBAI.

W.-D. RUDORF et al.,21 were synthesized unsymmetrical S,S’’-dialkyl N-

(arenesulfonyl) carbon dithioimidates in a one-pot reaction by successive alkylation of

disodium salts or by using methyl N-(arenesulfonyl) dithiocarbamates as the starting

material.

Mohammad Reza Saidi et al.,22 have been synthesized dithiocarbamates using amines

and carbon disulfide with α,β- unsaturated compounds were carried out in water.

A.N. Vasiliev et al.,23 have been synthesized potassium (1,1-dioxothiolan-3-yl)-

dithiocarbamate and optimized.

RNH2 R1X R

HN S

S

R1

CS2, Cs2CO3, TBAI

DMF, rt, 0OC

ArSO2-NH2NaOH

CS2ArSO2 N C

S-Na+

S-Na+

R1-X

R2-CH2-X

(CH3)2SO4

HCl

ArSO2HN C

SCH3

S

ArSO2 N C

S-R1

S-CH2-R2

NaOCH3/CH3OH orNaH/DMF

R2-CH2-X

HN

COOCH3N S COOCH3

S

CS2Water

rt

S

NH2

OO

CS2 C2H5O -

-C 2H5OH S

HN

OO

S -

S



Mohammad R. Saidi et al.,24 have been reported the synthesis of dithiocarbamates at

room temperature.

N. Azizi et al.,25 were reported a highly efficient and large-scale preparative procedure

for the preparation of S-alkyl dithiocarbamates with a one-pot reaction of amines, CS2,

and alkyl halides.

Akram Ashouri et al.,26 have been developed a procedure for one-pot synthesis of

dithiocarbamates with Markovnikov addition reaction in water.

Zemei Ge et al.,27 reported an efficient synthesis of formylmethyl piperidine-1-

carbodithioate diethyl acetal and analogs .

Ph Ph

O HN

N S Ph

OS PhCS2, neat

0OC to rt, 8h

R2

N

R1

SOR4

S

RT, Water,8-14h

R3

O

R2

NH

R1

BrOR4

R3

O

CS2

OCS2NH NS O

S

H2O

R2

NH

R1

CS2

BrCH2CH(OC2H5)2

O

O

BrH2CH2C

O

O

NS2H2CCH2C

NCS2CH2CH3(OC2H5)2

R1

R2

R1

R2

K3PO4/CH3COCH3

rt



Run-tao Li et al.,28 have been developed a method for the preparation of dithiocarbamic

acid esters by Michael addition of electron-deficient alkenes with amines and CS2 in solid

media alkaline Al2O3.

N. Azizi et al.,29 have been reported an efficient preparation of dithiocarbamate

derivatives from the one-pot reaction of amines, carbon disulfide, and unsaturated enones

or alkyl halides in water under ultrasound irradiation.

Vishnu L. Sharma et al.,30 were designed piperidine dithiocarbamate hybrids of 2-(2-

methyl-5-nitro-1H-imidazol-1-yl) ethane (8−20) to potentiate the MTZ framework

against drug resistance and sperm. New compounds were 1.2−12.1 times more effective

against MTZ-susceptible and -resistant strains of TV. All of the compounds exhibited

high safety toward cervical (HeLa) cells and Lactobacillus. Thirty-eight compounds were

scrutinized by CoMFA and CoMSIA techniques of 3D quantitative structure−activity

relationship. Good predictive rpred2 values for CoMFA and CoMSIA models reflected

the robustness of the predictive ability.

RR1NH R2 XCS2, water

10min NR1R S

R2S

ArNH2 CS2Ar

HN S

S

CR1

R2 R2

R1

alkaline Al2O3

10-30h

NN

S N

S

OR

CH3

NO2

N

N

S N

S

O

CH3

NO2

O

S N

S

R2

R1



Lajos Fodor et al.,31 have been synthesized indolylmethyl dithiocarbamates and some

analogues, using C-(1H-Indol-2-yl)- methylamine.

G. R. Bardajee et al.,32 were developed an efficient, versatile, and environmentally

benign method for the synthesis of dithiocarbamates under solvent-free conditions. The

Michael addition of electron deficient alkenes with alkyl or aryl amines and CS2 in the

presence of OH−/silica in a one-pot three-component reaction protocol gave the

corresponding dithiocarbamates in good to excellent yields.

Kapanda et al.,33 were obtained {[(dialkylamino)-carbothioyl]thio} methylene

(dialkylamino)methanedithioate,dithiocarbamate,dialkylcarbamoyl)methylenedialkylCarb

amodithioates,(dialkylthiocarbamoyl)methylenedialkylcarbamodithioate,bis(dialkylthioca

rbamoyl)sulfide, and dithiobisamines derivatives as Potent and Selective Monoglyceride

Lipase Inhibitors.

NH

NH2

NH

HN S

S

R1

CHCl3, Et3N, DMAP

CS2., O0C, rt, 2h

RNH

R1

EWGCS2R

N

R1

SEWG

S

OH-/silica

solvent-free10 h, 70OC

R 1

N HR 2

R 1N

R 2

SS

N

R 1

R 2

R 1

N

R 2

S -

S

+ H N

R 1N

R 2

S N

SS

R 1

R 2

R 1N

R 2

S N

SS

R 1

R 2S

R 1

N

R 2

S

S

R 3

R 1N

R 2

N

OS

R 1

R 2S

R 1

N

R 2

N

SS

R 1

R 2S



Y. Shi et al.,34 were synthesized Au(III) complexes with cyclic amine-based

dithiocarbamate ligands, characterized and evaluated in vitro.

Yasuhide Nakayama et al.,35 were reported a novel thermoresponsive aqueous anti-

thrombogenic coating material comprising a heparin bio-conjugate with a six-branched,

star-shaped poly(2-(dimethylaminoethyl)-methacrylate) (6B-PDMAEMA), which has

both thermo responsive and cationic characters, was developed to reduce the

thrombogenic potential of blood-contacting materials such as synthetic polymers or

tissue-engineered tissues in cardiovascular devices. 6B-PDMAEMA with Mn of ca. 24

kDa was designed as a prototype compound by initiator-transfer agent-terminator

(iniferter)-based living radical photo polymerization from hexakis (N,N-

diethyldithiocarbamylmethyl)benzene.

Suresh Kumar Kailasaabc and Hui-Fen Wu36 were proposed for one-pot synthesis of

dopamine dithiocarbamatefunctionalized gold nanoparticles (DDTC-Au NPs). They also

demonstrated the use of DDTC-Au NPs as affinity probes for selective enrichment of

phosphopeptides from the solutions of microwave tryptic digested casein proteins.

Compared with a conventional matrix, DDTC-Au NPs exhibited a high

desorption/ionization efficiency for accurate quantification of small molecules including

X N

SNa

S

X N

HS

SH

Au

Cl

Cl20OC

K[AuCl4] KCl NaCl

(CH2Br)6SNa C NEt2

S

EtOH[H2C S C

S

N(CH2CH3)2]6



amino acid (glutathione), drugs (desipramine and enrofloxacin) and peptides

(valinomycin and gramicidin D) and successfully utilized as novel affinity probes for

straightforward and rapid identification of phosphopeptides from casein proteins (a-, b-

casein and nonfat milk), showing a great potentiality to the real-time analysis.

J. Sreeramulu et al.,37 have been developed a new method for the preparation of a series

of novel bidentate dithiocarbamate ligand of 2-Amino2-methyl 1-propanol (AMPDTC).

The synthetic sodium salt of 2-Amino2-methyl 1-propanol dithiocarbamate ligand is

followed by the reaction of Copper and Manganese Chlorides to get corresponding

complexes.

Malachowski.W.P. et al.,38 have been studied a screen of indole-based structures

revealed the natural product brassinin to be a moderate inhibitor of indoleamine 2,3-

dioxygenase (IDO), a new cancer immunosuppression target. A structure-activity study

was undertaken to determine which elements of the brassinin structure could be modified

to enhance potency.

OH

OH

NH2

OH

OH

HN

SS

CS2 + EtOH

OH

HO

HN

S

SGold NPs

Dopamine Dopamine dithiocarbamate

Functionalized Au NPs with dithiocarbamate



Varga et al.,39 have been reported the synthesis of N,N-di (R1, R2)-S-ethyl

thiocarbamates, 4-(R-mercaptothiocarbonyl)-1,4-oxaza-spiro-(4,5)-decanes as a

herbicides.

M. A.-H. Zahran et al.,40 were synthesized a novel series of

methylthiomethylthalidomides acting as anticancer agents and the enhanced antitumor

activity.

B). Application of Dithiocarbamates

Choon-Hong Tan et al.,41 were derived an amino-indanol chiral guanidine was

developed as an efficient Brønsted base catalyst for the desymmetrization of meso-

aziridines with both thiols and carbamodithioic acids as nucleophiles, which provided

1,2-difunctionalized ring-opened products in high yields and enantioselectivities.

NH N

H

CS2., O 0C

Cl

R1 NH2CH 2Cl2

SHN

S

R1

N

O

S

S

RN

R 1 S

S

R 2

N

N

O

O

O

O S



Bhisma K. Patel et al.,42 have been demonstrated the multifaceted use of

diacetoxyiodobenzene (DIB) for various synthetically useful organic transformations.

The desulfurization ability of diacetoxyiodobenzene has been explored in the preparation

of isothiocyanates from the corresponding dithiocarbamate salt.

Manas Chakrabarty et al.,43 have been synthesized 2- alkylthio-6-benzene sulfonyl

thiazolo[5,4-e]indoles using N-(1 - benezensulfonylindol-3 -yl)dithiocarbamates.

Kitano et al.,44 produce polymers that could be adsorbed on to gold surfaces, they

synthesized via RAFT polymerization degradable linear polymers using a bifunctional

degradable chain transfer agent (CTA) bearing a disulfide bond. The degradable CTA

used was cysteamino-benzyl N,N-diethyldithiocarbamate (Cys-BDC), whereas 1-(6_-

methacryloylaminohexyl)-2-Nacetoamido- 2-deoxy d-glucopyranoside (MHGlcNAc)

was employed as monomer.

NO2

NO2

N

O

NO2

NO2

NH

O

S

NBn2

S

OMe

NH

2Bn2NH

10 mol%

ether, -20OCCS2

HN S -.Et+NH

S

NCSPhI(OAC)2

Et3N

N

S O 2P h

HNR S

SN

SO 2P h

S

N

R S

N B S , C H 2C l2 ,-1 0 O C , 5 -1 0 m in

D B U , s ti r , 3 0 m in



Bhisma K. Patel et al.,45 have been developed a method for the preparation of

isothiocyanates from the corresponding Dithiocarbamic acid salts by using molecular

iodine.

Lajos Fodor et al.,46 have been synthesized 2-methylthio-1,3- thiazino[5,6-b]indole and

their analogues using 2-(S-methyldithiocarbamoylaminomethyl)indole.

Bazavova. I.M. et al.,47 have been prepared Pyrazoles of the general formula by heating

p-RC6H4-NH.CS2CH3 with diethyl malonate followed by cyclization with hydrazine or

by condensation of α-carbethoxythioamide with hydrazine.

HN S-.Et+NH

S

NCSIodine

Et3N

NHN

H

HN S

S

R1

N

S

SR1

CH2Cl2, PhMe3NBr3rt, 5min

Et3N, rt, 10min

RC6H4HN C SMe

S

CH2(COOEt)2

EtOOCCH2CSNHC6H4R

N2H4.H2O

NH

NO

NHC6H4R

OOH

HOHO NHAc

OH2C

HN C C

O

CH3

CH2

6

OOH

HOHO NHAc

OH2C

HNCC

O

CH3H2C

6

SCH2

H2C C N

SHN

O

S2

Cys-BDS

TD hv



Alexander M. Jacobine and Gary H. Posner,48 were prepared 5-(Z)-Alkylidene-2-

thioxo-1,3-thiazolidin-4-ones (rhodaninederivatives) by reaction of in situ generated

dithiocarbamates with recently reported racemic α-chloro-β,γ-alkenoate esters.

Manas Chakrabarty et al.,49 have been synthesized novel 2- alkylamino- and 2-

alkylthiothiazolo[5,4-e]- and -[4,5-g]indazoles and their 6-alkyl and 8-alkyl derivatives in

a three-step route involving the regioselective cyclisation of thioureidoindazoles and

indazolyl dithiocarbamates as the key steps.

Dominique Lorcy et al.,50 reported the bis(dithiocarbamate) salt was synthesized by

adding carbon disulfide to a solution of ethylenediamine and triethylamine followed by

cyclization and dehydration in the presence of sulfuric acid led to bis-(1,3-thiazoline-2-

thiones).

RO

O

Cl

R

SN R1

O

S

-S

S

NHR1

NH

HNRS

S

NH

S

N

RS

Br2-AcOH, THF

rt, 30-45min

NHN

HRS

S

NHN

S

RS

Br2-AcOH, THF

rt, 30-45min

-S NH

NH

S-

SS

+HNEt3 +HNEt3 H2SO4 S

N N

S

R1

R2

R1

R2

S S

R1COCHClR2



Bhisma K. Patel et al.,51 were reported an improved procedure for the synthesis of

isothiocyanates from the corresponding dithiocarbamic acid salts via a desulfurization

strategy using molecular iodine and sodium bicarbonate in water/ethyl acetate biphasic

medium.

Zhenhua Chen and Derrick L. J. Clive,52 have been synthesized unusual seven-

membered heterocycles incorporating Nitrogen and Sulfur by intramolecular conjugate

displacement. Baylis-Hillman alcohols derived from methyl acrylate or acrylonitrile and

carrying an N-Boc group β to the hydroxyl (CH(OH)CHNBoc) can be converted into

unusual seven membered heterocycles containing both Nitrogen and Sulfur by O-

acylation (AcCl or EtOCOCl), N-deprotection (CF3COOH), and reaction with CS2.

Tamejiro Hiyama et al.,53 have been prepared trifluoromethyl aminopyridines and

pyrimidines starting from dithiocarbamates.

HN S-.Et+NH

S

HN

aq. NH3

I2/Et3N, EtOAc

N

Boc

MeO2C

AcO

N

MeO2C

AcO

-S

S

TFA, Et3NCS2

SN

MeO2C

S

N

X

N S CH 3

S

R

N

X

NCF3

R

N

X

NC F3

R

BrD BH ,TB AH 2F 3CH 2Cl2 , reflu x

D BH ,TBA H 2F3CH 2Cl2 , 0OC



Didier Gigmes et al.,54 were synthesized highly labile SG1-based alkoxyamines using

the photodecomposition of both azo compounds and dithiocarbamates.

Patrick Metzner et al.,55 have been investigated the oxidation reaction of various

dithiocarbamates demonstrated that the corresponding sulfines are formed.

A.M. Alafeefy et al.,56 have been prepared 5-(1-(2-Phenylquinazolin-4-yl)piperidin-4-

yl)-1,3,4-thiadiazole-2(3H)-thione starting from Potassium 2-(1-(2-phenylquinazolin-4-

yl)piperidine-4-carbonyl)-hydrazine carbodithioate.

G. Jaramillo-Soto et al.,57 were used benzyl-N,N-dimethyldithiocarbamate (RAFT D) as

a ROFT controller in styrene polymerization.

HOOC S N

Et

Et

S

N

-OOC

N

COO-

N P(O)(OEt)2

O

COOH

hv

SG1

R2R1N

S

SR3 R2R1N

S

SR3

O

m-CPBA, NaHCO3

CH2Cl2, 0OC, 24h

N

N

N

N

N

N

HNO

NH

S -K +

SS

H N

N

S

9 8% H 2S O 4

S C N

S



D. Hua et al.,58 have been studied the controlled/living free-radical polymerizations of

methyl acrylate under thermal condition using benzyl 9H-carbazole-9-carbodithioate

(BCCDT) as control agent.

Peng-Fei Zhang and Zhen-Chu Chen,59 have been obtained 2-Mercaptothiazoles by

hypervalent iodine oxidation of acetophenones with [hydroxyl (tosyloxy) iodo] benzene,

followed by treatment with potassium thiocyanate to offer corresponding α-

thiocyanatoacetophenones and cyclization of α- thiocyanatoacetophenones using

Ammoniumdithiocarbamate (NH2CSSNH4).

San H. Thang et al.,60 we have discovered a new class of “switchable” RAFT agents, N-

(4-pyridinyl)-N-methyldithiocarbamates, that provide excellent control over

polymerization of LAMs and, after addition of 1 equiv of a protic or Lewis acid, become

effective in controlling polymerization of MAMs, allowing the synthesis of poly(MAM)-

block-poly(LAM) with narrow molecular weight distributions.

N C

S

SHC

H 2C

HC

H 2C

H 2C

C

O C H 3

C

O C H 3

O On

N

S

S

BC CD T

RCOCH2R1

PhIOH

OTsCH3CN, reflux

R C C

O

CHR1

OTs

NH2CSSNH4

CH3CN + H2O, refluxS

N

SH

R

R1

N

NS

S

NCH

N

NS

S

H

OO

NC n

O

O

RAFT



Nishat, Haq, and Siddiqi61 were derived first row-transition metal complexes of the type

[M(L1)2], [M’(L1)3] and [M2(L2)2], where M=Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and

M’=Cr(III), Fe(III) from The sodium salts of pyrimidinetrione dithiocarbamate (NaL1)

and pyrimidinetrione dithiocarbamate (Na2L2).

Mamoru Koketsu et al.,62 were synthesized several dithiocarbamates and

selenothiocarbamates by the reaction of N,N-dimethylthiocarbamoyl chloride with the

corresponding thiolates and selenolates.

G. Bian et al.,63 have been developed a method for the preparation of Isothiocyanates

from imines or Dithiocarbamates Using Chlorosilanes such asMe3SiCl, Me2SiCl3,

MeSiCl3, and SiCl4, as decomposition reagents in Dichloromethane.

Abdolali Alizadeh and Javad Mokhtari,64 were reported the synthesis of 2’,3’-dihydro-

2’-thioxospiro[indole-3,6’-[1,3] thiazin]-2(1H)-one derivatives through a condensation

reaction in MeOH.

NHN

O O

OS-Na+

S

NN

O O

OS-Na+

S

+Na-S

S

NaL1 Na2L2

(CH3)2N Cl

S

R E M(CH3)2N ER

S

E=S, SeM=Li or Na

R1 NH2 R1 N C SCS2/base, CH2Cl2

R24-nSiCl3

METHOD-AR1 NH2 R1 N

HSH-Base+

S

R1 N C SR2

4-nSiCl3CS2/base, Toluene

Base, CH2Cl2

METHOD-B



Koji Ishizu et al.,65 Silica (SiO2)-crosslinked polystyrene (PS) particles possessing

photofunctional N,N-diethyldithiocarbamate (DC) groups on their surface were prepared

by the free-radical emulsion copolymerization of a mixture of SiO2 (diameter Dn ¼ 192

nm), styrene, divinyl benzene, 4- vinylbenzyl N,N-diethyldithiocarbamate (VBDC), and

2- hydroxyethyl methacrylate with a radical initiator under UV irradiation.

Dejian Huang et al.,66 were synthesized complexes of Ni(II) with dithiocarbamate

ligands derived from the ortho and para isomers of sulforhodamine B fluorophores and

demonstrated they are highly selective in reactions with nitrogen dioxide (NO2).

Waldemar Adam et al.,67 were reported the direct molybdenum-catalyzed sulfuration of

a variety of isonitriles with elemental sulfur or propene sulfide as sulfur donors affords

NH

O

R1

Ph

O

RNH

SH

S

NH

O

R1

Ph

OS

S NHR

NH

N

SR1

O

SR

MeOH, 6-8h

reflux

SiO2

St, VBDC,DVB, HEMA

H2O/EtOHSiO2 DCCD

DC

DCDC

DCCD

CD

SiO2 DCCD

DC

DCDC

DCCD

CD

MMA, CuCl/bpy

Colloidalsilica

SPS SPM

SO3-

O2S N

NH

SO3-

O2S N

N CS2Na

SO3-

O2S N

N

HS

SH

Ni

CS2

NaOH Ni(NO3)2



the corresponding isothiocyanates in good yields and under mild reaction conditions.

Rince Wong and Sarah J. Dolman68 have been reported a facile and general protocol

for the preparation of isothiocyanates from alkyl and aryl amines is reported. This method

relies on a tosyl chloride mediated decomposition of a dithiocarbamate salt that is

generated in situ by treatment of an amine with carbon disulfide and triethylamine.

Clegg et al.,69 were used the bimetallic aluminum (salen) complex [Al(salen)]2O and

tetrabutylammonium bromide (or tributylamine) to catalyze the reaction between

epoxides and carbon disulfide. In most cases, at 50oC, the reaction produces 1,3-

oxathiolane-2-thiones, while at 90 oC, 1,3-dithiolane-2-thiones are the main product.

RNCMo(O)(S2CNEt2)2

S

CH2Cl2, 20-25OC, 70hRNCS

R NH2

R

HN S

S

R NCS

Cl2CS or equivalent

base

CS2,Et3N, 1h TsCl,THF, rt, 1h

Et3NH

SO

S

R

(sa len )A l- o -A l(sa le n )

B u 3N(sa len )A l-o -A l(sa le n )B u B r +

O

R

O

R

C S 2

(sa len )A l-o -A l(sa len )O

RSN B u 3

S



Diliën et al.,70 have been developed an Efficient Acid-Induced Conversion of

Dithiocarbamate Precursor Polymers into Conjugated Materials.

Nakayama, et al.,71 were developed the Preparation of four-branched polymers as gene

transfer material coated on culture dish surface.

Carbamodithioic acid, N,N-diethyl-, C,C',C'',C'''-[1,2,4,5-benzenetetrayltetrakis

(methylene)] ester

S

C8H17

SC(S)NEt2 S

C8H17

S

C8H17

Et2N(S)CSSC(S)NEt2

n n

NaHMDG

S

SS

S

S

NEt2

S

NEt2

Et2N

S

Et2N

S



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