synthesis of biologically active nitrogen and...
TRANSCRIPT
Chapter III
Environmentally Benign Synthesis of
Bis (indolyl) methanes in Water
Catalyzed by Polystyrenesulphonic
acid
This work is communicated to Catalysis Letters
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
88
CHAPTER - 3
Environmentally Benign Synthesis of Bis(indolyl)methanes in Water Catalyzed by Polystyrenesulphonic acid.
3.1 INTRODUCTION AND LITERATURE SURVEY
Bis (indolyl) alkanes and their derivatives constitute an important group
of biologically active metabolites of terrestrial and marine origin. In the recent
years bis (indolyl) methanes and bis (indolyl) ethanes has been found in marine
sources. Bisindole metabolites bearing imidazole or a piperazine nucleus has
been isolated from various genera of sponges.
Bis (indolyl)methanes and their derivatives exhibit diverse biological
activities which affect central nervous system[1] and used as tranquilizers.[2] The
important indole derivative, 9H-pyrralo[1,2-a]indole called fluorazine[3] [1] is
an important compound because of its anticholinergic activity [4] and for the
inhibition of GABA transport and Na+/ K+-ATPase.[5] Several synthetic routes
to 9H-pyrralo[1,2-a]indoles have been inscripted in literature[6] however, most
of them have been directed towards the synthesis of mitomycin antibiotics .
Another important family of bis (indolyl)methanes are
cytonortopsentins[7] [2], which exhibit in-vitro cytotoxicity. Moreover, some
other bis(indolyl) alkaloids in which imidazole moiety of nortopsentins was
replaced by thiazole [3], pyrimidine [4], pyrazine [5] and pyrazinone [6] rings
have been reported[8] 2, 4 -Bis(indolyl) thiazole analogue [7] exhibited
cytotoxic activities against a wide range of human tumor cell lines at
micromolar concentrations.[9] Similar antitumor properties reported by
N
Me
R
R'
OMe
MeO
[1]
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
89
dragmacidin D.[10] Recently Lee and co-workers found that 1,1,3-tri(3-
indolyl)cyclohexane inhibits cancer cell of xenograft model[11] [8].
NH
R'
N
NHO
NH
R
[6]
NH
S
NH
R'R'
[7]
NH
N
N
NH2
Br
[8]
3.2 METHODS OF SYNTHESIS The lead indole derivatives reported in the literature are bis (indolyl) and
tris (indolyl)alkanes. Their method of synthesis involves both one step as well
as multistep synthesis. Fischer in 1886 prepared 3,3-bis(indolyl)methanes [9]
NH
N
NH
NHR R'
[2] Nortopsentin A R = R1 = Br
Nortopsentin B R = Br, R1 = H
Nortopsentin C R= H, R1 = Br
NR
N
S
NR
RR
2 2
1
[3]
NR
N
N
NR
R3
2 2
[4]
N R
N
N
NR
R3
2
2
[5]
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
90
for the first time which was a mere acid catalyzed Friedel-Crafts reaction
between indole and carbonyl compounds, generally aldehydes and ketones
(Scheme 3.1).The acid catalyzed reaction of an electron rich heterocyclic
compounds such as indole and pyroles with p-dimethylaminobenzaldehyde is
known as the Ehrlich test[13] Generally 3,3`-BIM`s are synthesized by an
analogous reaction to the Ehrlich test, where indole reacts with aliphatic or
aromatic aldehydes or ketones in the presence of an acid catalyst to produce
azafulvene[14] [10]. The enamine can undergo further addition reaction with a
second indole molecule to produce BIM`s (Scheme 3.2). The synthetic utility
of this synthetic route to obtain wide structurally diversed BIM`s has been
rooted in recent years.
NH R R'
O
NH
NH
R R'
Acid catalyst2 +
R = alkyl or aryl.
Rl = H or alkyl
[9] Scheme 3.1
NH
R
O
H
H+
R
OH
NH
H
-H+NH
R
OH H+
-H2O
R
NH
NH
NH
R
NH
H
- H+
NH
R
NH
+ ++
+
+
10
Scheme 3.2
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
91
Shrihari et al[15] have demonstrated that phosphomolybdic acid (PMA)
together with silica (SiO2) works efficiently for the one pot three component
reaction of aldehyde, excess N-methylaniline and indole to yield 3-substituted
indole derivatives [11] (scheme 3.3).
.
HN
R
O
H NH
PMA/SiO2N
NH
R+ +
[11]
Scheme 3.3
BIM`s derivatives of ferrocene [13] has been reported by the reaction
between ferrocene aldehyde or ketone [12] in the presence of ZnCl2[16] as a
catalyst .The resultant derivatives formed with low yields (Scheme 3.4).
O
R
FeNH
ZnCl2Solid state
NH
NH
R
Fe+
[12] [13]
Scheme 3.4
Nucleophilic attack of indole on carbonyl carbon of aldehyde is more
facile than carbonyl carbon of ketone it may be due to steric hindrance.
Formation of BIM`s derived from ketones required more energy. Use of
microwave irradiation was reported for indole and diethylketomalonate in the
presence of montmorillonite K-10 clay[17] to give the corresponding indol-3`-
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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92
ylcarbinols [14] and respective BIM`s [15] with 20-45% and 5-35% yields
(Scheme 3.5).
NH
COOEt
COOEtO K clay
MWNH
OH COOEt
COOEt
NH
NH
COOEtEtOOC
2 + 10
+
[14] [15]
Scheme 3.5
Furanose and allose 3, 3`-BIM`s derivatives[18] [16, 17] were produced
from the reaction of indole and the corresponding aldehyde in the presence of
HClO4 in good yields (Scheme 3.6).
NH
NH
O
OO
OMe
NH
NH
O
O
O
BTSO
[16] [17]
Scheme 3.6
In case of conjugated aldehydes like crotonaldehyde reaction never stops
at BIM stage but further Michael addition of third indole molecule takes place
on carbon-carbon double bond to offer compound [18] in good yields. In this
reaction three molecules of the indole get consumed. Both Lewis as well as
protic acid catalyst gives better yield of the products (Scheme 3.7). Amongst
them cerric ammonium nitrate[19] offered good yields of the product.
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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93
NH
NH
NH
NH
OCAN mol%
CH3CN rt+ 10
,
[18]
Scheme 3.7
C-Glucosylation of indole was attempted by Sato et al.[20] In this method
10 mol % Sc (OTf)3 was used as a reusable catalyst. Best yield of the products
[19] were obtained for 0.1 equivalent amount of catalyst and 80 0C reaction
temperature .It took 11 hrs. for completion (Scheme 3.8).
NH
H OHHOHOHHOHH
CH2OH
CHO
HOH
H OHOH HOH H
CH2OH
NH
NH
EtOH :H2O
Sc(OTf)3
+ 1 :1
[19]
Scheme 3.8
Strategy of BIM synthesis served as a profitable subject for the synthesis
of polycyclic compound. This method covers the synthesis of aza-crown ether
through the condensation of indole [20] with anisaldehyde in the presence of
H4[Si (W3O10)3] as a catalyst.[21] The reaction proceeds at room temperature in
acetonitrile as a solvent, affording crown ether bearing indole [21] in moderate
yields (Scheme 3.9).
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
94
N N
OO
O
ArCHO H4(SiW3O10)3 mol%
CH3CNNN
Ar
OO
O
+ 20
, rt, 45min
[20] [21]
Scheme 3.9
Bergmann and his associates[22] have successfully synthesized
pentacyclic compound [22] from Friedel-Crafts reaction between 1,2 bis(1H-
indol-2-yl) ethane [23] and either aldehyde and ketone under acidic condition
(TFA or p-TsOH) in good yields (Scheme 3.10).
NHN
H
O
RR
TFA or PTSA
EtOH refluxNHN
H
R R
+ 12
1 2
[22] [23]
Scheme 3.10
Bis (indolyl) nitroethanes[23] are important synthetic intermediate for
synthesis of some naturally occurring analogues. In this synthesis, Michael
addition of indole takes place on activated 3-(2-nitrovinyl)indole [24] on silica
gel under microwave irradiation to give high yields Michael adduct [25].
(Scheme 3.11) Reaction could takes place at room temperature but takes longer
time to complete .
NH
NO2
NH
Silica gel
MW, minor, rt, N
H
NO2
NH
+7-108-14 hr
[24] [25]
Scheme 3.11
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
95
Some miscellaneous methods demonstrated for the synthesis of BIM`s
where quite diversion found in utility of indole and an aldehyde as a reactant.
Synder and Eliel[24] applied Fischer indole synthesis for the synthesis of N-
substituted BIMs [26] in acidic condition which offered the compound in
moderate yields (Scheme 3.12).
NCH3
NH2O OR ORO
O OAcOH
HCI NHO2CCO2H
NCH3CH3
+
[26]
Scheme 3.12
One pot synthesis of BIM`s through annulation/Friedel Crafts alkylation
from alkynes [27] and aldehydes. The mechanism towards the formation of
BIMs [28] is supposed to be formation of bisindole prior to the Friedel-Crafts
step. This transformation is well catalyzed by FeCl3–PtCl2 and AuCl[25]
(Scheme 3.13)
Ph
NH2
R
CHO
FeCI3-PtCI2CH2CI2
NH
NH Ph Ph
+
2
, 80 C0
8h
[27] [28]
Scheme 3.13
Conversion of ketones into alkanes [29] by the use of lithium aluminum
hydride and reverse oxidation reaction to regain ketone were demonstrated by
Bergman et al [26] (Scheme 3.14).
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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96
NH
N
H
O
NH
N
H
LAH
DDQ
[29]
Scheme 3.14
Use of Gallium (III) halide as a catalyst for the effective transformation of
indole and phenyl acetylene into bis(indolyl)phenylethanes [30] was
demonstrated by J. S. Yadav et al.[27] The reaction went to completion in 6 hr
and the product was obtained in 86% yields (Scheme 3.15).
N
H NH
N
H
CH3% GaCl3, BaBr3
R'Ph
C6H5CH3, rt+
10
[30]
Scheme 3.15
Besides to the conventional and microwave methods researchers prefer
ultrasonic irradiation for single step synthesis. Xiao-Fei Zeng and co-
workers[28] have developed a simple, novel and efficient synthetic protocol for
synthesis of unsymmetrical BIMs [31] using catalytic amount of CAN under
ultrasonic irradiation at room temperature (Scheme 3.16).The superiority of
this method behinds the use of cheap and non toxic CAN as a catalyst.
N
H
ROH
NH
N
H
R
NH
CAN
U S EtOHR' R'+
[31]
Scheme 3.16
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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97
Among the several methods reported in the literature for the synthesis of
BIMs, the reaction between an Indole and an aldehyde is most popular with
good synthetic utility. This transformation is catalyzed effectively by Lewis
acid as well as protic acid catalyst. Use of ionic liquid as good alternative for
toxic solvents, offers bis (indolyl) alkanes in good yields. The factors that
prompted to search newer methods with low cost of catalyst, higher yield of the
product, reaction rates, simplicity of the workup process and green chemistry.
Cerric compounds like Cerric ammonium nitrate (CAN),[29]
CeCl3.7H2O/glycerine,[30] nanoceria (CeO2) supported on vinyl pyridine
polymer[31] are effective Lewis acids which promote the bis (indolyl) alkane
formation. The use of natural clay like montmorilonite clay K-10[32] and
bentonite clay[33] have been made by Bhattacharya and Banerji. Habib
Firouzabadi et al have reported ZrOCl2·8H2O/silica gel[34] and Aluminum
dodecatungstophosphate (AlPW12O40)[35] as water tolerant Lewis acid as a
catalyst for bis (indolyl) alkanes. Silica supported acid catalysts like NaHSO4-
SIO2,[36] HBF4-SiO2,
[37] HClO4-SiO2,[18] catalyzed reaction for BIMs offering
good yields. Recently, a new type of water-usable catalyst, namely, “Lewis
acid-surfactant-combined catalyst (LASC)” has shown high efficiencies in
various organic transformations.[38] It was reported that metal codicil sulfates,
can be efficiently employed in the synthesis of 3,3′-BIMs.[39-42]
Dodecylbenzenesulfonic acid (DBSA)[43] and dodecylsulfonic acid (DSA)[44-45]
also promote BIM formation from aldehydes and indoles in water.
In addition to microwave (MW),46 sonochemistry,[47] and ionic liquids
raised as green solvent a most wanted alternative to toxic, volatile solvents. J.
S. Yadav et al explored the utility of 1-bytyl-3-methylimidazolium
tetrafluoroborate ([bmim]BF4) and 1-bytyl-3-methylimidazolium
hexafluorophosphate ([bmim]PF6).[48]
Many of the above mentioned methodologies are associated with the
drawbacks like longer reaction time, high expenditure on catalyst, which causes
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
98
environmental pollution. These factors alarmed to search out chief,
environmentally benign protocol for BIMs.
3.3 PRESENT WORK
The mechanism of BIMs reveals that, the reaction can be promoted by
protic as well as Lewis acid catalysts. With an increasing environmental
concerns and regulatory constrains chemists are devoted to the area of green
chemistry which has attained the status of a major scientific discipline,[49]
which involves minimize the amount of toxic waste and by-product from
chemical processes, elimination of hazardous reagent and easy separation
methods. In the development of new processes ecological impact must also be
taken into account. Solvents are central feature, as they are generally used in
large quantities, Such a consideration has prompted synthetic organic chemists
to explore the potential of water as a solvent for organic synthesis. Toward this
end, considerable efforts have been devoted to develop and use nontraditional
solvents for chemical synthesis.[50] Such unconventional medium include
among others are solvent-free condition,[51] supercritical carbon dioxide,[52]
ionic liquids, perfluorinated solvents,[53] and last but not least water. There is
widespread current debate over the relative “greenness” of these individual
reaction media, but water can undoubtedly be considered the cleanest solvent
available. The use and release of clean water clearly will have the least impact
to the environment. Recently R. S. Varma et al have reported the
polystyrenesulphonic acid (PSSA) catalyzed greener synthesis of 1,3-dioxanes
and hydrazones in aqueous medium using microwave (MW) irradiation.[54-56]
We wish to report a greener and highly efficient route for the synthesis of bis-
indolyl methane using inexpensive and commercially available
polystyrenesulphonic acid (PSSA) as a catalyst (Scheme 3.17).
NH
NH
NH
Ar
Ar
O
HPSSA
Water, rt2 +
Scheme 3.17
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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99
3.4 RESULTS AND DISCUSSION In order to study the catalytic efficiency of polystyrenesulphonic acid,
we carried out a controlled reaction with an aromatic aldehyde (1mmol) and an
indole (2 mmol) without polystyrensulphonic acid (PSSA) and stirred for
several hours. A sticky reaction mixture was obtained with the formation of bis
(indolyl) methane in very low yield. In another experiment, aldehyde and
indole were taken in 5 mL water to which two drops of PSSA were added and
the reaction mixture stirred at room temperature till completion of reaction as
monitored by TLC. The reaction proceeded cleanly and desired pink red
coloured bis-(indolyl) methane was isolated in good yield.
In order to study the generality of this procedure, a series of bis (indolyl)
methanes were synthesized (Table 3.1). Several aryl aldehydes with electron
withdrawing and donating functional groups undergo efficient formation of the
bis (indolyl)methanes in short reaction time. The product, bis (indolyl)
methanes were obtained in good yields and were separated simply by filtration
on vacuum pump. As reaction proceeds in water with good yields of the
product, we were not interested to examine the feasibility of the reaction in
other organic solvents. This encouraged us to employ same methodology with
ketones. In case of cyclohexanone, product obtained with good yield but it
takes longer time for completion whereas reaction with aromatic ketones like
acetophenone reaction, very low yield of the product was obtained. Poor
reactivity of ketones may be due to the steric hindrance of the alkyl group. The
formation of the desirable BIMs was detected by their melting points and by
IR, 1H NMR, 13C NMR spectroscopic methods.
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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Table 3.1. Reaction time and Yields of bis-(indolyl)methanes
Entry Compound Time
(min).
Yield (a)
( %)
1.
NNH H
65
90
2.
NNH H
Me
60
87
3.
NNH H
OMe
70
85
4.
NNH H
OMe
OMe
70
85
5.
NH
NH
NMeMe
85
82
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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6.
NN
N
H H
Cl
Me
85
70
7.
NH
NNH H
70
80
8.
NNH H
NO2
55
90
11.
NNH H
Cl
55
92
12.
NN
N
H H
Cl
90
75
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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13.
NN
N
H H
Cl
OMe
90
77
a -Refers to yield of the pure and isolated compounds.
Spectral Analysis
The IR spectrum of various compounds reveals that the disappearance of
stretching frequency of carbonyl group at 1690 cm-1 which indicated that
condensation of both indole molecules. N-H Stretching frequency is quite
immaterial as far as BIMs formation is concern. In 1H NMR spectrum, the
signal for aldehyde proton at δ 9.8 disappeared while a singlet corresponding to
one proton at δ 5.6 indicated the methine proton. Appearance of this signal in 1H NMR spectrum clearly confirms the formation of BIMs. Rest aromatic
protons and two NH protons of two indole molecule appeared at downfield
shift in between δ 6.0-8.0. A singlet of two NH protons observed at δ 8, while
aromatic protons shows complex multiplet pattern. The structure elucidation of
the compounds has been explained from its 13C NMR spectral data, as there is
only one methine carbon signal observed at δ 35 while remaining aromatic
carbons of indole and benzene ring are observed in the range of δ 110 to 150.
NNH H
Me
2-[1H-indol-3-yl(4-methylphenyl)methyl]-1H-indole (Table 3.1, entry
2) in its IR spectrum exhibited N-H stretching band at 3411 cm-1.There was
absence of stretching band of conjugated carbonyl near at 1690 cm-1
(Spectrum 3.1). 1H NMR spectrum of the same compound shows singlet at δ
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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103
2.3, which indicates the presence of methyl group attached to aromatic ring, a
singlet for methine proton observed at downfield shift at δ 5.8. The aromatic
protons gave complex multiplet for thirteen protons at δ 6.9 to 7.4, while a
singlet for two protons attached to C-2 shows upfield shift at δ 5.8 is due to
vicinity of nitrogen atom from indole, it appears at δ 5.8. The downfield shift
for N-H proton gives a broad singlet at δ 7.8 (Spectrum 3.2). 13C NMR
spectrum of the molecule shows the signal at δ 21.78, 39.78, 110.99, 119.17,
119.92, 121.85, 123.53, 127.12, 128.56, 135.46, 136.71 (Spectrum 3.3).
NNH H
OMe
Bis(indolyl)methanes synthesized from p-anisaldehyde (Table 3.1,
entry 3) gave a pink coloured solids showed IR stretching band for N-H at
3360 cm-1(Spectrum 3.4).; A singlet appeared at δ 3.7 for three protons of
methoxy group whereas methine proton appeared as singlet at δ 5.8. Multiplet
for aromatic protons observed between δ 6.658-7.735 representing twelve
protons and two NH protons of bis (indolyl) methanes encountered at δ 8.0.
(Spectrum 3.5).
NNH H
OMe
OMe
2-[1H-indol-3-yl(2, 3-dimethoxylphenyl)methyl]-1H-indole (Table 3.1,
entry 4) has methyl protons of dishielded methoxy group observed at δ 3.7 and
3.8 while methine proton resonate at δ 5.8. Rest aromatic protons were
observed between δ 6.6-7.4. The two NH protons of each indole nucleus
appeared at δ 7.8 (Spectrum 3.6).
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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NH
NH
NMeMe
In 1H NMR spectrum of [1H-indole-3-yl(4-N,N
dimethylaminophenyl)methyl]-1H-indole (Table 3.1, entry 5) a singlet at δ
2.909 indicates equivalent protons of two methyl group attached to nitrogen
atom. A methine proton resonate at δ 5.803 whereas aromatic protons displayed
in the form of multiplet between δ 6.670-7.419. Two N-H protons of indole
nucleus showed broad singlet at δ 7.877 (Spectrum 3.7).
3.5 EXPERIMENTAL
Materials and Methods
All aryl aldehydes and indole were purchased from S. D. fine and
spectrochem Co. and were used without further purification.
Instrumental details and their operational conditions
NMR analysis
NMR analysis was performed on Brucker–Avance 300 MHz, NMR
spectrophotometer. For 1H NMR analysis, CDCl3 was used as solvent and
tetramethylsilane as an internal standard, the chemical shifts are reported in
ppm. Multiplicities are indicated by ‘s’ (singlet), ‘d’ (doublet), ‘t’ (triplet), ‘q’
(quartet), ‘m’ (multiplet) and ‘bs’ (broad singlet). The coupling constant (J) are
reported in Hz.
IR Analysis
Infrared spectra were recorded on Perkin Elmer 1310 FT-IR spectrometer with
KBr pellets.
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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105
General Experimental procedure
To the mixture of aryl aldehyde (1 mmol), indole (2mmol), 2-3 drops of
polystyrenesulphonic acid in water (5 mL) were added and the mixture stirred
at room temperature for the appropriate reaction time .The product was isolated
by simple filtration and further purified by column chromatography using
solvent system [ethyl acetate / petroleum ether (1:9)] to get desired bis (indolyl)
methanes in high yields.
3.6 CONCLUSION
We have demonstrated a simple, ecofriendly and elegant protocol for the
synthesis of bis(indolyl)methanes using polystyrenesulphonic acid, which
proceeds very efficiently in water without any use of flammable, volatile
organic solvent. As reaction occurs in the water which excludes the
cumbersome separation methods thus it avoids the exposure to the harmful
solvents. Therefore the use of polystyrensulphonic acid as a catalyst renders
this method environmentally benign.
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
acid.
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CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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3.7 REFERENCES
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[3] Kasey, W.; Black, D. S.; Kumar, N. Tet.Lett. 2009, 50,574.
[4] Azarashvili, A..A. Neurosci. Behave. Physiol. 1997, 27, 341.
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[16] Jiben, M.; Daming, D.; Yongmei, W. Chin. Chem. Lett. 1992, 3, 247.
CHAPTER 3 Environmentally Benign Synthesis of Bis(indolylmethanes) in Water Catalyzed by Polystyrensulphonic
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[17] Pindur, U.; Kim, M. H. Tetrahedron 1989, 45, 6427.
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