Dithiocarbamate as an efficient intermediate for the synthesis of 2-(alkylthio)thiazol-4(5H)-ones

Article abstract of DOI:10.1080/17415993.2016.1194421

An effective approach for the synthesis of 2-(alkylthio)thiazol-4(5H)-ones from alkyl dithiocarbamates and chloroacetyl chloride in the presence of NaHCO₃ has been developed. Good to excellent yields of products, simple reaction conditions and

Full text of DOI:10.1080/17415993.2016.1194421

Journal of Sulfur Chemistry
ISSN: 1741-5993 (Print) 1741-6000 (Online) Journal homepage: http://www.tandfonline.com/loi/gsrp20
Dithiocarbamate as an efficient intermediate for
the synthesis of 2-(alkylthio)thiazol-4(5H)-ones
Azim Ziyaei Halimehjani, M. Ali Alaei, Farzaneh Soleymani Movahed, Negin
Jomeh & Mohammad R. Saidi
To cite this article: Azim Ziyaei Halimehjani, M. Ali Alaei, Farzaneh Soleymani Movahed,
Negin Jomeh & Mohammad R. Saidi (2016): Dithiocarbamate as an efficient intermediate
for the synthesis of 2-(alkylthio)thiazol-4(5H)-ones, Journal of Sulfur Chemistry, DOI:
10.1080/17415993.2016.1194421
To link to this article: http://dx.doi.org/10.1080/17415993.2016.1194421
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Date: 17 June 2016, At: 01:18

JOURNAL OF SULFUR CHEMISTRY, 2016
http://dx.doi.org/10.1080/17415993.2016.1194421
Dithiocarbamate as an efficient intermediate for the synthesis
of 2-(alkylthio)thiazol-4(5H)-ones
Azim Ziyaei Halimehjania, M. Ali Alaeib, Farzaneh Soleymani Movahedb,
Negin Jomehb and Mohammad R. Saidib
aFaculty of Chemistry, Kharazmi University, Tehran, Iran; bDepartment of Chemistry, Sharif University of
Technology, Tehran, Iran
ABSTRACT
ARTICLE HISTORY
Received 24 April 2016
Accepted 23 May 2016
An effective approach for the synthesis of 2-(alkylthio)thiazol-4(5H)-
ones from alkyl dithiocarbamates and chloroacetyl chloride in the
presence of NaHCO3 has been developed. Good to excellent yields
of products, simple reaction conditions and general applicability are
the most important advantages of this protocol.
KEYWORDS
Dithiocarbamate;
2-(alkylthio)thiazol-4(5H)-ones;
heterocycles; chloroacetyl
chloride; carbon disulfide
1. Introduction
Five-membered heterocyclic compounds containing two heteroatoms in their structure,
such as thiazoles, thiazolidines, thiazolidinones and thiazolinones, are important scaf-
folds associated with the structure of many biological active compounds.[1] These com-
pounds have been extensively used in drug discovery with antibacterial,[2] antifungal,[3]
antitubercular,[4] anticancer,[5] anticonvulsant,[6] antiviral,[7] cardiotonic,[8] anti-
inflammatory [9] and antidiabetic activities.[10] It has been well documented that the bio-
logical activities of 1,3-thiazolidinones vary with changing functional groups in the ring.
For this purpose, various functional groups such as amino, arylazo, sulfamoylphenylazo,
phenylhydrazono and other heterocyclic and homocyclic rings have been introduced into
the structure of 1,3-thiazolidinones.[1] Among the different types of 1,3-thiazolidinones,
CONTACT Azim Ziyaei Halimehjani
ziyaei@khu.ac.ir
Faculty of Chemistry, Kharazmi University, 49 Mofateh St.,
Tehran, Iran
Supplemental data for this article can be accessed here. http://dx.doi.org/10.1080/17415993.2016.1194421
© 2016 Informa UK Limited, trading as Taylor & Francis Group

2
A. ZIYAEI HALIMEHJANI ET AL.
2-(alkylthio)thiazol-4(5H)-ones were less investigated which may be due to the lack of effi-
cient procedures for the synthesis of these compounds. The only reported route for the
synthesis of these compounds is the reaction of rhodanine with alkyl halides catalyzed
by a base.[11,12] Additionally, 2-(alkylthio)thiazol-4(5H)-ones are efficient intermedi-
ates for the synthesis of 2-aminothiazol-4(5H)-ones, which are an important category of
biologically active compounds.[12–15]
Dithiocarbamates are versatile synthetic intermediates which have been exten-
sively applied for the preparation of thioureas,[16] isothiocyanates,[17] 2-imino-
1,3-dithiolanes,[18] cyanamides,[19] heterocyclic rings,[20–23] the protection of
aldehydes,[24] amide bond formation[25] and protection of amino groups in peptide
synthesis.[26] In addition to their synthetic utility, these compounds also have found wide
application in agriculture,[27,28] medicine[29,30] and coordination chemistry.[31,32]
2. Results and discussion
Considering the mentioned advantages of thiazolidinones, in this study we have focused
our attention for the synthesis of 2-(alkylthio)thiazol-4(5H)-ones on the reaction of simply
prepared dithiocarbamates and chloroacetyl chloride in the presence of NaHCO3.
Dithiocarbamates were synthesized by the one-pot three-component reaction of aque-
ous ammonia, carbon disulfide and alkyl halides or α,β-unsaturated carbonyl compounds
as outlined in Scheme 1.[33,34] According to the best of our knowledge, there is no report
for the reaction of dithiocarbamates and chloroacetyl chloride for the synthesis of 2-
(alkylthio)thiazol-4(5H)-ones in the literature.[35] For this purpose, we investigated the
reaction of benzyldithiocarbamate with chloroacetyl chloride at room temperature in ace-
tonitrile for 12 h as a model reaction (Scheme 2). We observed the formation of a low
yield (20%) using this protocol. We observed that by using NaHCO3 as a base in the
reaction medium, the yield was increased to 50% consistent with release of hydrochloric
acid during the reaction. Also, we observed that by increasing the reaction temperature
from rt to about 81°C (reflux temperature of acetonitrile), the yield was improved to
80%. Varying the reaction time from 12 to 24 h does not have any effect on the reaction
yield.
Scheme 1. Synthesis of dithiocarbamates.

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3
Scheme 2. Synthesis of 2-(alkylthio)thiazol-4(5H)-ones.
After optimization of the reaction conditions, the generality of the reaction was inves-
tigated using different S-alkyldithiocarbamates. We determined that different alkyl groups
containing double bond, aryl and ester moieties can be applied in this protocol to afford
the corresponding 2-(alkylthio)thiazol-4(5H)-ones in good to excellent yields (65–90%).
Also long chain alkyl groups give similar results under this protocol. The results are sum-
marized in Table 1. Attempts to synthesize similar products using methyl chloroacetate,
ClCH2COOCH3, were not successful.
Structures of the products were confirmed by IR, 1H NMR, 13C NMR, CHN analysis,
and mass spectroscopy. The 1H NMR spectra of the products showed a characteristic sin-
glet between 3.80 and 4.20 ppm for the CH2 in the thiazol ring. The distinctive carbons of
the carbonyl and the iminium moieties of the ring were observed between 201.0 and 203.5
and 187.0–189.0 ppm, respectively. Characteristic bands in IR spectrum were observed in
the range of 1720 and 1690 cm−1 for the carbonyl and the imine bonds, respectively.
A proposed mechanism for this reaction is given in Scheme 3. Initially, the Cl attached
to the methylene is displaced by nucleophilic attack of the sulfur atom in the thiocarbonyl
group in dithiocarbamate 1, and the HCl product was neutralized by an equivalent amount
of NaHCO3, to give the intermediate 4. Then, intramolecular addition of the nitrogen to
the acyl halide afforded the corresponding adduct 3. The released HCl in this step was also
neutralized by the second equivalent of NaHCO3. To investigate the priority of the attack
by nitrogen or sulfur, we carried out the reaction of dithiocarbamate with benzoyl chloride
under similar conditions. No reaction was observed with benzoyl chloride under the same
conditions. This finding encouraged us to propose the sulfur attack as the initial step in
this reaction.
3. Conclusion
In conclusion, an effective and novel procedure for the synthesis of 2-(alkylthio)thiazol-
4(5H)-ones from readily synthesized S-alkyl dithiocarbamates and chloroacetyl chloride in
the presence of NaHCO3 is developed. Simple reaction conditions, good to excellent yields
of products, and general applicability are the most important advantages of this protocol.

4
A. ZIYAEI HALIMEHJANI ET AL.
Table 1. Diversity in the synthesis of 2-(alkylthio)thiazol-4(5H)-one.a,b
aIsolated yield.
bReaction conditions: dithiocarbamate (1 mmol), chloroacetyl chloride (1 mmol) and NaHCO3 (2 mmol), 12 h, reflux.
This new reaction can be applied as an efficient alternative procedure to the rhodanine
protocol for the synthesis of 2-(alkylthio)thiazol-4(5H)-ones.
4. Experimental
4.1. General
The reagents and solvents were of analytical grade. The NMR spectra were recorded on
Bruker 500 MHz spectrometer. FT-IR spectra were recorded on ABB Bomem, MB 100
spectrometer. Electron impact (70 eV) mass spectra were recorded on an Agilent Technol-
ogy (HP) 5973 mass spectrometer with quadrupole analyzer. Reactions were monitored

JOURNAL OF SULFUR CHEMISTRY
5
Scheme 3. Proposed mechanism.
by thin-layer chromatography (TLC) using Merck TLC silica gel 60 F254 plates. Elemental
analyses were conducted with a Perkin-Elmer 2004 (II) CHN analyzer.
4.2. General procedure for the preparation of 2-(alkylthio)thiazol-4(5H)-ones
Dithiocarbamate (1 mmol) and NaHCO3 (0.168 g, 2 mmol) were mixed in acetonitrile
(5 mL). Then, chloroacetyl chloride (0.08 mL, 1 mmol) was added and the mixture was
refluxed for 12 h at 81°C. Then, water (10 mL) was added and the product was extracted
by ethyl acetate (3 × 10 mL). The organic layers were combined and dried with anhy-
drous MgSO4. Finally, evaporation of the solvent afforded the corresponding crude
2-(alkylthio)thiazol-4(5H)-ones as a yellow oil. The purification was accomplished by
column chromatography (silicagel, n-hexane /ethyl acetate; 4:1).
2-(Methylthio)thiazol-4(5H)-one (3a): IR (KBr) 1724, 1695, 1438, 1385, 1188, 1023,
1
955 cm−1; H NMR (500 MHz, CDCl3) δ 2.70 (3H, s), 3.97 (2H, s) ppm; 13C NMR
(125 MHz, CDCl3) δ 16.8, 40.2, 187.9, 203.2 ppm; MS (EI): m/z 147 (M+), 123, 91(100),
77, 69, 55, 45.
2-(Ethylthio)thiazol-4(5H)-one (3b): IR (KBr) 1736, 1699, 1458, 1168, 999 cm−1; 1H
NMR (500 MHz, CDCl3) δ 1.31 (3H, t, J = 7.5 Hz), 3.21 (2H, q, J = 7.5 Hz), 3.89 (2H, s)
ppm; 13C NMR (125 MHz, CDCl3) δ 14.7, 29.0, 39.9, 188.2, 202.6 ppm; Anal. Calcd for
C5H7NOS2: C, 37.24; H, 4.38; N, 8.69. Found: C, 37.20; H, 4.45; N, 8.42.
2-(Allylthio)thiazol-4(5H)-one (3c): IR (KBr) 1736, 1695, 1620, 1462, 1164, 983 cm−1
;
1H NMR (500 MHz, CDCl3) δ 4.00 (2H, s), 4.06 (2H, d, J = 12.0 Hz), 5.24 (1H, d,
J = 5.0 Hz), 5.36 (1H, d, J = 7.5 Hz), 5.92 (1H, m) ppm; 13C NMR (125 MHz, CDCl3)
δ (ppm): 37.0, 40.1, 120.6, 131.3, 187.9, 202.0 ppm; Anal. Calcd for C6H7NOS2: C, 41.59;
H, 4.07; N, 8.08. Found: C, 41.28; H, 4.35; N, 8.32
2-(sec-butylthio)thiazol-4(5H)-one (3d): IR (KBr) 1736, 1689, 1458, 1160, 983,
806 cm−1; 1H NMR (500 MHz, CDCl3) δ 1.04 (3H, t, J = 7.5 Hz), 1.46 (3H, d, J = 7.0 Hz),
1.78–1.82 (2H, m), 3.95 (2H, s), 4.08 (1H, m) ppm; 13C NMR (125 MHz, CDCl3) δ 11.6,
21.1, 29.7, 39.6, 47.6, 188.3, 202.4 ppm; Anal. Calcd for C7H11NOS2: C, 44.41; H, 5.86; N,
7.40. Found: C, 44.52; H, 5.75; N, 8.32
2-(isopentylthio)thiazol-4(5H)-one (3e): IR (KBr, cm−1) 1740, 1708, 1466, 1394, 1164,
1
1059, 818; H NMR (500 MHz, CDCl3) δ 0.93 (6H, d, J = 6.5 Hz), 1.61–1.73 (3H, m),
3.31–3.34 (2H, t, J = 7.5 Hz), 3.97 (2H, s) ppm; 13C NMR (125 MHz, CDCl3) δ 22.6, 27.9,
32.8, 37.8, 39.9, 188.2, 202.8 ppm. Anal. Calcd for C8H13NOS2: C, 47.26; H, 6.44; N, 6.89.
Found: C, 46.95; H, 6.36; N, 6.90.
2-(3-Methylbut-3-enylthio)thiazol-4(5H)-one (3f): IR (KBr) 1740, 1696, 1626, 1450,
1333, 1220, 1152, 1059, 898 cm−1; 1H NMR (500 MHz, CDCl3) δ 1.30 (2H, m), 1.89 (3H,

6
A. ZIYAEI HALIMEHJANI ET AL.
s), 3.99–4.03 (4H, m), 4.99 (1H, s), 5.09 (1H, s) ppm; 13C NMR (125 MHz, CDCl3) δ 18.4,
26.1, 33.1, 40.0, 116.6, 140.4, 188.1, 202.6 ppm. Anal. Calcd for C8H11NOS2: C, 47.73; H,
5.51; N, 6.96. Found: C, 47.45; H, 5.36; N, 6.91.
2-(3-Methylbut-2-enylthio)thiazol-4(5H)-one (3g): IR (KBr) 1732, 1695, 1620, 1458,
1164, 991 cm−1; 1H NMR (500 MHz, CDCl3) δ 1.70 (3H, s), 1.73 (3H, s), 3.96–3.97 (4H,
m), 5.31 (1H, t, J = 8.0 Hz) ppm; 13C NMR (125 MHz, CDCl3) δ (ppm): 18.4, 26.1, 33.1,
40.0, 116.6, 140.4, 188.1, 202.6 ppm; MS (EI): m/z 201 (M)+, 187, 168, 146, 133, 114, 101,
86, 69, 55, 41 (100).
2-(Hexylthio)thiazol-4(5H)-one (3h): IR (KBr) 1732, 1708, 1458, 1168, 995 cm−1; 1H
NMR (500 MHz, CDCl3) δ 0.86 (3H, t, J = 7.0 Hz), 1.26–1.32 (4H, m), 1.38–1.42 (2H, m),
1.78 (2H, m), 3.31 (2H, t, J = 7.5 Hz), 3.96 (2H, s) ppm; 13C NMR (125 MHz, CDCl3) δ
14.4, 22.9, 28.7, 29.2, 31.6, 34.7, 39.9, 188.2, 202.8 ppm. Anal. Calcd for C9H15NOS2: C,
49.73; H, 6.96; N, 6.44. Found: C, 49.43; H, 6.77; N, 6.31.
2-(Octylthio)thiazol-4(5H)-one (3i): IR (KBr) 1740, 1712, 1466, 1160, 987 cm−1;1H
NMR (500 MHz, CDCl3) δ 0.88 (3H, t, J = 7.0 Hz), 1.23–1.44 (10H, m), 1.73–1.79 (2H,
m), 3.31 (2H, t, J = 7.5 Hz), 3.97 (2H, s) ppm; 13C NMR (125 MHz, CDCl3) δ 14.5, 23.0,
29.0, 29.4, 30.1, 30.6, 32.1, 34.7, 39.9, 188.1, 202.8 ppm; MS (EI): m/z 245 (M+), 198, 149,
133, 113, 86, 71, 57, 41 (100).
2-(Benzylthio)thiazol-4(5H)-one (3j): IR (KBr) ν 1732, 1695, 1414, 1196, 1063,
794 cm−1; 1H NMR (500 MHz, CDCl3) δ 3.99 (2H, s), 4.53 (2H, s), 7.25–7.33 (5H, m) ppm;
13C NMR (125 MHz, CDCl3) δ 37.9, 40.2, 129.5, 131.0, 134.0, 134.5, 187.7, 201.6 ppm; MS
(EI): m/z 222 (M-1+), 168, 123, 91 (100), 65, 45.
2-((Naphthalen-3-yl)methylthio)thiazol-4(5H)-one (3k): IR (KBr) 1736, 1704, 1458,
1
1188, 1080, 971, 774 cm−1; H NMR (500 MHz, CDCl3) δ 4.03 (2H, s), 5.10 (2H, s),
7.42–7.61 (4H, m), 7.84–8.00 (3H, m) ppm; 13C NMR (125 MHz, CDCl3) δ 36.9, 40.1,
123.6, 125.9, 126.7, 127.3, 129.0, 129.5, 129.9, 133, 131.7, 134.4, 187.9, 202.0 ppm. Anal.
Calcd for C14H11NOS2: C, 61.51; H, 4.06; N, 5.12. Found: C, 61.73; H, 4.18; N, 5.01.
Methyl 3-(4,5-dihydro-4-oxothiazol-2-ylthio)propanoate (3l): IR (KBr) 1744, 1699,
1474, 1192, 983 cm−1;1H NMR (500 MHz, CDCl3) δ 2.71 (2H, t, J = 7.0 Hz), 3.38 (2H,
t, J = 7.0 Hz), 3.55 (3H, s), 3.89 (2H, s) ppm; 13C NMR (125 MHz, CDCl3) δ 29.3, 33.8,
40.0, 52.3, 171.8, 187.8, 201.9 ppm; MS (EI): m/z 220 (M+1)+, 187, 159, 146, 133, 86, 54
(100), 46.
Methyl 3-(4,5-dihydro-4-oxothiazol-2-ylthio)-2-methylpropanoate (3m); IR (KBr)
1732, 1695, 1466, 1164, 987 cm−1; 1H NMR (500 MHz, CDCl3) δ 1.29 (3H, d, J = 7.1 Hz),
2.95 (1H, m), 3.45 (1H, dd, J = 13.6 and 8.2 Hz), 3.54 (1H, dd, J = 13.5, 5.6 Hz), 3.70
(3H, s), 3.97 (2H, s) ppm; 13C NMR (125 MHz, CDCl3) δ (ppm): 17.1, 36.5, 39.6, 40.1,
52.4, 174.8, 187.7, 202.1. MS (EI): m/z 234 (M+1)+ (100), 202, 173, 133, 101, 86, 69, 59,
46, 41.
Ethyl 3-(4,5-dihydro-4-oxothiazol-2-ylthio)propanoate (3n): IR (KBr) 1728, 1699,
1458, 1165, 983, 737 cm−1; 1H NMR (500 MHz, CDCl3) δ 1.10 (3H, t, J = 7.2 Hz), 2.68
(2H, t, J = 6.7 Hz), 3.37 (2H, t, J = 6.7 Hz), 3.88 (2H, s), 3.98 (2H, q, J = 7.1 Hz) ppm;
13C NMR (125 MHz, CDCl3) δ 14.4, 29.2, 33.9, 39.9, 61.2, 171.2, 187.7, 201.8 ppm; MS
(EI): m/z 234 (M+1)+ (100), 220, 188, 160, 133, 101, 86, 72, 55, 46.
Butyl 3-(4,5-dihydro-4-oxothiazol-2-ylthio)propanoate (3o): IR (KBr) 1736, 1699,
1462, 1168, 987 cm−1; 1H NMR (500 MHz, CDCl3) δ 0.92 (3H, t, J = 7.4 Hz), 1.35 (2H,
m), 1.62 (2H, m), 2.84 (2H, t, J = 6.7 Hz), 3.54 (2H, m, J = 6.7 Hz), 3.98 (2H, s), 4.10 (2H,

JOURNAL OF SULFUR CHEMISTRY
7
t, J = 6.7 Hz) ppm; 13C NMR (125 MHz, CDCl3) δ 14.0, 19.4, 29.3, 30.9, 34.1, 40.0, 65.2,
171.4, 187.8, 202.0 ppm; MS (EI): m/z 262 (M+1)+, 188, 159, 132, 114, 86, 55, 46, 41.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
We are grateful to the Research Council of the Sharif University of Technology for financial support.
We also thank the Faculty of Chemistry of Kharazmi University for supporting this work.
References
[1] Jain AK, Vaidya A, Ravichandran V, Kashaw SK, Agrawal RK. Recent developments and biolog-
ical activities of thiazolidinone derivatives: a review. Bioorg Med Chem. 2012;20:3378–3395.
[2] Soltero-Higgin M, Carlson EE, Phillips JH, Kiessling LL. Identification of inhibitors for UDP-
galactopyranose mutase. J Am Chem Soc. 2004;126:10532–10533.
[3] Kavitha CV, Basappa S, Swamy N, et al. Synthesis of new bioactive venlafaxine analogs: novel
thiazolidin-4-ones as antimicrobials. Bioorg Med Chem. 2006;14:2290–2299.
[4] Kucukguzel SG, Oruc EE, Rollas S, Sahin F, Ozbek A. Synthesis, characterization and biological
activity of novel 4-thiazolidinones, 1,3,4-oxadiazoles and some related compounds. Eur J Med
Chem. 2002;37:197–206.
[5] Havrylyuk D, Mosula L, Zimenkovsky B, Vasylenko O, Gzella A, Lesyk R. Synthesis and anti-
cancer activity evaluation of 4-thiazolidinones containing benzothiazole moiety. Eur J Med
Chem. 2010;45:5012–5021.
[6] Kaur H, Kumar S, Vishwakarma P, Sharma M, Saxena KK, Kumar A. Synthesis and antipsy-
chotic and anticonvulsant activity of some new substituted oxa/thiadiazolylazetidinonyl/
thiazolidinonylcarbazoles. Eur J Med Chem. 2010;45:2777–2783.
[7] Sudo K, Matsumoto Y, Matsushima M, Fujiwara M, Konno K, Shimotohno K, Shigeta S, Yokota
T. Novel hepatitis C virus protease inhibitors: thiazolidine derivatives. Biochem Biophy Res
Commun. 1997;238:643–647.
[8] Andreani A, Rambaldi M, Leoni A, et al. Synthesis and cardiotonic activity of imidazo
[2,l-b]thiazoles bearing a lactam ring. Eur J Med Chem. 1996;31:383–387.
[9] Nasr MNA, Said SA. Novel 3,3a,4,5,6,7-hexahydroindazole and arylthiazolylpyrazoline deriva-
tives as anti-inflammatory agents. Arch Pharm. 2003;336:551–559.
[10] Ohishi Y, Mukai T, Nagahara M, Yajima M, Kajikawa N, Miyahara K, Takano TT. Prepara-
tions of 5-alkylmethylidene-3-carboxymethylrhodanine derivatives and their aldose reductase
inhibitory activity. Chem Pharm Bull. 1990;38:1911–1919.
[11] Pulici M, Quartieri F. Traceless solid-phase synthesis of 2-amino-5-alkylidene-thiazol-4-ones.
Tetrahedron Lett. 2005;46:2387–2391.
[12] Song Y, Connor DT, Doubleday R, et al. Synthesis, structure−activity relationships, and in
vivo evaluations of substituted Di-tert-butylphenols as a novel class of potent, selective, and
orally active cyclooxygenase-2 inhibitors. 1. Thiazolone and oxazolone series. J Med Chem.
1999;42:1151–1160.
[13] Mukhopadhyay C, Ray S. Rapid and straightforward one-pot expeditious synthesis of 2-amino-
5-alkylidene-thiazol-4-ones at room. Tetrahedron Lett. 2011;52:6431–6438.
[14] Anderluh M, Jukic M, Petric R. Three-component one-pot synthetic route to 2-amino-5-
alkylidene-thiazol-4-ones. Tetrahedron. 2009;65:344–350.
[15] Taylor Jr EC, Wolinsky J, Lee H-H. The reaction of α-cyanobenzyl benzenesulfonate with
dithiocarbamates. J Am Chem Soc. 1954;76:1870–1872.
[16] Ziyaei Halimehjani A, Pourshojaei Y, Saidi MR. Highly efficient and catalyst-free synthesis of
unsymmetrical thioureas under solvent-free conditions. Tetrahedron Lett. 2009;50:32–34.

8
A. ZIYAEI HALIMEHJANI ET AL.
[17] Wong R, Dolman SJ. Isothiocyanates from tosyl chloride mediated decomposition of in situ
generated dithiocarbamic acid salts. J Org Chem. 2007;72:3969–3971.
[18] Ziyaei-Halimehjani A, Maleki H, Saidi MR. Regiospecific iodocyclization of S-allyl dithio-
carbamates: synthesis of 2-imino-1,3-dithiolane and 2-iminium-1,3-dithiolane derivatives.
Tetrahedron Lett. 2009;50:2747–2749.
[19] Jamir L, Sinha UB, Nath J, Patel BK. Environmentally benign one-pot synthesis of cyanamides
from dithiocarbamates using I2 and H2O2. Synth Commun. 2012;42:951–958.
[20] Ziyaei Halimehjani A, Marjani K, Ashouri AA. One-pot, three-component synthesis of
thiazolidine-2-thiones. Tetrahedron Lett. 2012;53:3490–3492.
[21] Ziyaei Halimehjani A, Ashouri A, Marjani K. Dithiocarbamates as an efficient intermediate for
the synthesis of symmetrical substituted 2,5-diamino-1,3,4-thiadiazoles in water. J Heterocycl
Chem. 2012;49:939–942.
[22] Aryanasab F, Ziyaei Halimehjani A, Saidi MR. Dithiocarbamate as an efficient intermediate for
the synthesis of 2-amino-1,3,4-thiadiazoles in water. Tetrahedron Lett. 2010;51:790–792.
[23] Ziyaei Halimehjani A, Hasani L, Alaei MA, Saidi MR. Dithiocarbamates as an efficient
intermediate for the synthesis of 2-(alkylsulfanyl)thiazoles in water. Tetrahedron Lett.
2016;57:883–886.
[24] Ziyaei Halimehjani A, Hajiloo Shayegan M, Hashemi MM, Notash B. Investigation of the
reaction of dithiocarbamic acid salts with aromatic aldehydes. Org Lett. 2012;14:3838–3841.
[25] Ziyaei Halimehjani A, Ranjbari MA, Pasha Zanussi H. Synthesis of a new series of
dithiocarbamate-linked peptidomimetics and their application in Ugi reactions. RSC Adv.
2013;3:22904–22908.
[26] Greene TW, Wuts PGM. Protective groups in organic synthesis. 3rd ed. New York (NY): Wiley-
Interscience 1999.
[27] Marinovich M, Viviani B, Capra V, et al. Facilitation of acetylcholine signaling by the dithio-
carbamate fungicide propineb. Chem Res Toxicol. 2002;15:26–32.
[28] Bergendorff O, Hansson C. Spontaneous formation of thiuram disulfides in solutions of
iron(III) dithiocarbamates. J Agric Food Chem. 2002;50:1092–1096.
[29] Gaspari P, Banerjee T, Malachowski WP, et al. Structure−activity study of brassinin derivatives
as indoleamine 2,3-dioxygenase inhibitors. J Med Chem. 2006;49:684–692.
[30] Ronconi L, Maccato C, Barreca D, Saini R, Zancato M, Fregona D. Gold(III) dithiocarbamate
derivatives of N-methylglycine: an experimental and theoretical investigation. Polyhedron.
2005;24:521–531.
[31] Macias B, Villa MV, Chicote E, Martin-Velasco S, Castineiras A, Borras J. Copper complexes
with dithiocarbamates derived from natural occurring amino acids. Crystal and molecular
structure of [Cu(en)(EtOH)(H2O)3][Cu(dtc-pro)2]. Polyhedron. 2002;21:1899–1904.
[32] Ziyaei-Halimehjani A, Torabi S, Amani V, Notash B, Saidi MR. Synthesis and characterization
of metal dithiocarbamate derivatives of 3-((pyridin-2-yl)methylamino)propanenitrile: crys-
tal structure of [3-((pyridin-2-yl)methylamino)propanenitrile dithiocarbamato] nickel(II).
Polyhedron. 2015;102:643–648.
[33] Ziyaei Halimehjani A, Airamlounezhad S. Zrcl4/TMSCl as an efficient catalyst for synthesis of
4,6-substituted 2-alkylthio-6H-1,3-thiazines. J Heterocycl Chem. 2014;51:1147–1150.
[34] Azizi N, Aryanasab F, Torkian L, Ziyaei A, Saidi MR. One-Pot synthesis of dithiocarbamates
accelerated in water. J Org Chem. 2006;71:3634–3635.
[35] Synthesis of targent heterocycles using thioacyl isocyanate (masked dithiocaramates) and
isocyanides (an isoelectronic synthon of chloroacetyl chloride) is reported in: Schenk H,
Über Thioacyl-isocyanate, IV. Mercapto-thiocarbonyl-isocyanate und ihre Umlagerung zu
Mercapto-carbonyl-senfölen. Chem Ber. 1966;99:1258–1265.