Literature review of Dithiocarbamates Karnatak Science College, Dharwad 52 Chapter -2 Synthesis Of Coumarin/1-azacoumarin Dithiocarbamate Derivatives
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 52
Chapter -2
Synthesis
Of
Coumarin/1-azacoumarin
Dithiocarbamate
Derivatives
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 53
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 54
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 55
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 56
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 57
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 58
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 59
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 60
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 61
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 62
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 63
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 64
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 65
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 66
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 67
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 68
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 69
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 70
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 71
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 72
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 73
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 74
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 75
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
Literature review of Dithiocarbamates
Karnatak Science College, Dharwad 76
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