A one-pot three-component synthesis of dithiocarbamates starting from vinyl pyridines and vinyl pyrazine under solvent- and catalyst-free conditions

Article abstract of DOI:10.1016/j.tet.2016.05.025

A novel and efficient one-pot three-component reaction for the synthesis of dithiocarbamates at room temperature under solvent- and catalyst-free conditions, starting from readily available amines, CS₂and vinyl pyridines and vinyl pyrazine is reported. Excellent yield, green reaction conditions, and complete regioselectivity toward anti-Markovnikov adducts are particular advantages of this work.

Full text of DOI:10.1016/j.tet.2016.05.025

Accepted Manuscript
A one-pot three-component synthesis of dithiocarbamates starting from vinyl pyridines
and vinyl pyrazine under solvent- and catalyst-free conditions
Azim Ziyaei Halimehjani, Jürgen Martens, Torben Schlüter
PII:
S0040-4020(16)30410-0
10.1016/j.tet.2016.05.025
TET 27752
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 27 February 2016
Revised Date: 28 April 2016
Accepted Date: 9 May 2016
Please cite this article as: Halimehjani AZ, Martens J, Schlüter T, A one-pot three-component synthesis
of dithiocarbamates starting from vinyl pyridines and vinyl pyrazine under solvent- and catalyst-free
conditions, Tetrahedron (2016), doi: 10.1016/j.tet.2016.05.025.
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Azim Ziyaei Halimehjani, Jürgen Martens, and Torben Schlüter

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Tetrahedron
journal homepage: www.elsevier.com
A one-pot three-component synthesis of dithiocarbamates starting from vinyl
pyridines and vinyl pyrazine under solvent- and catalyst-free conditions
Azim Ziyaei Halimehjani,*,a Jürgen Martensb, and Torben Schlüterb
a Faculty of Chemistry, Kharazmi University, P. O. Box 15719-14911, 49 Mofateh St., Tehran, Iran. E-mail: ziyaei@khu.ac.ir; Fax: +98 (21) 88820992; Tel:
+98 (21) 88848949.
b Institut für Chemie, Carl von Ossietzky Universität Oldenburg, P. O. Box 2503, Carl-von-Ossietzky-Str. 9–11, 26111 Oldenburg, Germany
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A novel and efficient one-pot three-component reaction for the synthesis of dithiocarbamates at
room temperature under solvent– and catalyst–free conditions, starting from readily available
amines, CS2 and vinyl pyridines and vinyl pyrazine is reported. Excellent yield, green reaction
conditions, and complete regioselectivity toward anti–Markovnikov adducts are particular
advantages of this work.
Available online
2009 Elsevier Ltd. All rights reserved
.
Keywords:
Dithiocarbamate
Solvent-free
Catalyst-free
Vinyl pyrazine
Vinyl pyridines
1. Introduction
the classical methods by using the direct condensation of amines,
carbon disulfide, and various electrophiles such as alkyl halides,10
α,β–unsaturated carbonyl compounds,11 electron-rich alkenes
such as ethyl vinyl ethers12 and N–vinyl amides,13 carbonyl
compounds,14 orthoformates15a and epoxides.15 Compounds
containing dithiocarbamate moieties have shown various
biological activities as herbicides, fungicides, and pesticides in
agriculture,16 antitumor, anticancer and antibacterial activities in
medicine,17 as radio–pharmaceutical agents for medical
imaging,18 as ligands in coordination chemistry,19 for sulfur
vulcanization in rubber manufacturing,20 radical chain transfer
agents in reversible addition–fragmentation chain transfer
(RAFT) polymerizations21 and as intermediates in organic
synthesis.22 Due to the wide application of dithiocarbamates, the
synthesis of these compounds with different substitution patterns
at the thiol chain by a convenient and safe method has become a
field of increasing interest in synthetic organic chemistry during
the past few years.
Multicomponent reactions (MCRs), without any doubt,
provide one of the most efficient and effective methods in the
sustainable and diversity–oriented synthesis of biologically active
compounds.1 Beside the famous MCRs reported to date, the
design of novel MCRs with green procedures has attracted great
attention from different branches of chemistry for the synthesis
of novel materials. Performing the MCRs under solvent– and
catalyst–free conditions is completely in agreement with the
goals of green chemistry by reducing the pollution, decreasing
handling and labor cost, and reducing the number of steps for
producing the catalyst or removing the catalyst from the reaction
media.2
Multicomponent reactions based on CS2 provide an
efficient tool for the synthesis of diverse of functional groups
such as dithiocarbamates,3 dithiocarbonates (xanthates),4
trithiocarbonates,5 dithioesters,6 heterocycles,7 etc.8 Reaction of
amines with CS2 provides dithiocarbamic acids as intermediates,
the analogues of carbamic acids in which both oxygen atoms are
replaced by sulfurs, which are good mononucleophiles from their
sulfur atom or a potential bisnucleophile from their sulfurs and
nitrogen group.9 Recently, several efficient procedures for the
synthesis of dithiocarbamates have been developed by our group
and others to overcome most of the drawbacks associated with
2. Results and discussion
In continuation of our research toward the synthesis of
novel dithiocarbamates and their applications in organic
synthesis, herein we report an efficient, novel, and

2
Tetrahedron
ACCEPTED MANUSCRIPT
environmentally benign procedure for the synthesis of
yields. In addition, (R)–thiazolidine–4–carboxylic acid methyl
dithiocarbamates via one-pot three-component reactions of
amines, CS2 and vinyl pyridines or vinyl pyrazine at room
temperature under solvent– and catalyst–free conditions as
outlined in Scheme 1.
ester as an ester of an unnatural amino acid gave 75% isolated
yield (entry 18).
Reactions of aromatic amines with CS2 usually do not
proceed without a base. Surprisingly, we observed that aromatic
amines can be successfully applied in this protocol with excellent
yields (entries 15 and 27–29). The vinyl pyridine plays an
additional role in this reaction as catalyst to promote the reaction
of aromatic amines with CS2. The structure of products was
confirmed by IR, 1H and 13C NMR and HRMS analysis. In
addition, the structure of compound 3e was confirmed by single
crystal X–ray diffraction and ORTEP representations are shown
in Figure 1 (CCDC no. 1438807).
Previous work
S
CH3COOH
S
R
+
Na
S
N
R
R
N
S
N
R
N
1a
2
This work
Z
X
Z
Solvent-free
Y
S
R
Y
+
+
CS2
HN
R
Catalyst-free
rt
S
N
R
X
R
1a-c
3
1a: X=N and Y, Z=CH
1b: Y=N and X, Z=CH
1c: X, Z=N and Y=CH
Scheme 1. A one-pot three-component synthesis of
ditiocarbamates
Figure 1. ORTEP image of X–ray crystal structure of 3e.
A literature survey revealed that the reaction of
dithiocarbamic acid salts with 2–vinylpyridine 1a in acetic acid
as solvent and promoter gave the corresponding dithiocarbamic
acid esters as outlined in Scheme 1.23 According to our
experience in the field of dithiocarbamates, we hypothesized that
while the reaction of an amine with CS2 provides the
dithiocarbamic acid as intermediate, it is acidic enough to
activate the 2–vinylpyridine 1a for nucleophilic attack. For this
purpose, we investigated a one-pot three-component reaction of
diethylamine, CS2 and 1a as a model reaction at room
temperature under solvent– and catalyst–free conditions. We
observed that a quantitative yield of 3a was obtained. While the
reaction gives similar yields in polar and nonpolar organic
solvents (hexane, CH2Cl2, THF, acetone, DMF and methanol)
and water, performing the reaction under solvent–free conditions
was selected as optimum due to the simplicity and reaction rate.
In addition, although the nucleophilicity of dithiocarbamate salts
in basic media is more than under neutral conditions, the reaction
of diethylamine with CS2 and 1a in basic media did not proceed.
Furthermore, reaction of commercially available sodium
diethyldithiocarbamate with 1a under solvent-free condition gave
no desired product.
2–Vinylpyridine, 4–vinylpyridine and 2–vinylpyrazine
worked equally well in this protocol to give the corresponding
dithiocarbamates with pyridine or pyrazinyl group in the
structure. 1–vinylimidazole was also evaluated without any
desired product formation (entry 30).
It has been well documented that the biological activity
of a compound can be improved by increasing the number of
dithiocarbamate moieties in the structure.26 For this purpose, bis
(dithiocarbamate) (entry 22) was prepared in 69% yield via the
one–pot,
pseudo–five–component
reaction
of
1,3–
propanediamine, CS2 and 4–vinylpyridine in solvent–free
conditions at room temperature.
A proposed mechanism for this reaction is given in
Scheme 2. It is proposed that the initial event is the reaction of
diethylamine with CS2 to produce the corresponding
dithiocarbamic acid 4 which then protonates the 2–vinylpyridine
to afford 5. Nucleophilic attack of the sulfur anion 6 on 5 results
in formation of the corresponding product 3a. Since the reaction
of the corresponding sodium dithiocarbamate salt with
vinylpyridine was not observed, the proposed mechanism shows
that the acidic hydrogen of the dithiocarbamic acid is essential
for the reaction.
With optimized conditions in hand, the scope of this
reaction was investigated using different primary and secondary
amines and vinyl containing compounds (Table 1). As shown in
Table 1, primary aliphatic amines such as ethylamine,
isopropylamine, butylamine, isobutylamine, allylamine, (R)–
phenylethylamine, benzylamine and 4–methoxybenzylamine
gave excellent yields. A primary amine containing a hydroxyl
group, 3–aminopropanol, was applied in this reaction with
excellent yield (entry 11). Dithiocarbamate 3q derived from
biologically active tryptamine24 was prepared in excellent yield
(entry 17). Propargylamine gave the corresponding product 3n in
good yield with 2-(2-(4,5-dihydro-5-methylenethiazol-2-
ylthio)ethyl)pyridine 3n' as an inseparable side product (3n:3n',
86:14) and 24% of 4–methylene–thiazolidine–2–thione25 (entry
14). Different secondary amines such as pyrrolidine, piperidine,
morpholine, diethylamine, and diallylamine gave excellent
S
CS2
HN
N
+
HS
4
N
1a
1. Michael addition
2. proton transfer
S
S
N
S
N
S
N
N
H
3a
5
6
Scheme 2. A proposed mechanism

3
Table 1 Diversity in the synthesis of dithiocarbamates
ACCEPTED MANUSCRIPT
Yield (%)a
19
N
N
Entry amine
Michael acceptor
Product
N
N
S
S
pyrrolidine
quant.b, 27
quant. b
quant. b
S
1
diethylamine
S
N
N
3s
N
S
N
isopropylamine
20
3a
quant.b
S
N
H
2
3
piperidine
pyrrolidine
S
S
3t
N
N
N
S
S
N
N
N
3b
3c
N
21
pyrrolidine
S
quant. b
69% c
quant. b
N
N
S
3u
N
N
N
N
N
N
S
S
N
1,3-propane
22
N
S
N
N
S
diamine
78% b
3v H
H
S
4
5
6
morpholine
allylamine
N
N
N
S
N
3d
O
N
N
N
N
S
23
24
butylamine
98% b
S
S
N
quant. b
quant. b
H
3w
S
N
3e
H
S
diethylamine
quant. b
S
S
N
ethylamine
S
3f
N
3x
H
N
N
25
26
S
7
8
diethylamine
butylamine
91% b
95% b
S
quant. b
quant. b
N
isopropylamine
isobutylamine
N
S
N
N
N
N
N
S
N
3y
H
3g
S
N
N
N
N
S
S
N
H
S
N
3h
H
3z
9
S
quant. b
N
N
N
N
butylamine
OCH3
OCH3
OCH3
N
S
4-
93% c
N
S
3i
N
H
S
N
27
28
methoxyaniline
H
3aa
S
10
11
quant. b
quant. b
N
N
S
diallylamine
N
N
4-
95% c
95% c
N
N
S
3j
N
S
N
H
methoxyaniline
3ab
3-
S
aminopropanol
S
OH
S
N
4-
H
N
N
S
N
3k
29
30
methoxyaniline
H
3ac
S
benzylamine
98% b
quant. b
76% b
N
S
12
13
N
N
N
S
3l
N
N
N
pyrrolidine
0%
H
S
3ad
N
4-
S
a Isolated yield. b isolated pure after work-up. c isolated by column
chromatography.
methoxybenzyl
amine
N
N
N
S
N
H
3m
OCH3
S
S
14
propargyl
amine
N
N
S
S
N
H
3n
3n:3n,, 86:14
3. Conclusion
N
3n'
In conclusion, a novel and environmentally benign procedure
for the synthesis of dithiocarbamates from readily available
amines, CS2 and vinyl pyridines or vinyl pyrazine was developed.
Performing the reaction under solvent– and catalyst–free
conditions at ambient temperature, excellent yield, green reaction
aniline
15
16
S
60%c
N
N
N
N
S
N
H
3o
(R)-1-
phenylethyl
amine
S
H
conditions,
a
simple work-up procedure and complete
CH3
quant. b
regiospecifity toward anti–Markovnikov adducts are the main
advantages of this work which makes it a useful and attractive
strategy in combinatorial chemistry.
S
N
H
3p
tryptamine
NH
S
17
18
88% c
75% c
N
N
N
S
N
H
3q
4. Experimental
(R)-
S
CO2Me
S
4.1. General. All reagents and solvents were analytically pure
and were purchased from Merck or Fluka and used as received.
Melting points were obtained on a melting apparatus of
thiazolidine-4-
carboxylic acid
methyl ester
N
S
N
3r

4
Tetrahedron
159.8, 192.6 ppm; HRMS (ES+) calcd for C H N S Na
Laboratory Devices and are uncorrected. IR spectra were
ACCEPTED MANUSCRIPT
12 16
2 2
(M+Na)+ 275.0653, found 275.0657.
4.2.4. 2-(Pyridin-2-yl)ethyl morpholine-4-carbodithioate (3d):
recorded on a Bruker Tensor 27 spectrometer equipped with a
“Golden Gate” diamond-ATR (attenuated total reflection) unit.
1H and 13C NMR spectra of isolated products were recorded on a
o
Yellow solid; m. p. 75.3-77.5 C; IR (KBr) ν 1583, 1408, 1229,
1
Bruker AMX R 500 (measuring frequency: H NMR = 500.1
1109, 999, 767 cm-1; H NMR (500 MHz, CDCl3) δ 3.24 (2H, t,
1
MHz, 13C NMR = 125.8 MHz) or a Bruker Avance III 500
(measuring frequency: 1H NMR = 499.9 MHz, 13C NMR = 125.7
MHz) in CDCl3 or DMSO-d6 solution. Mass spectra were
obtained on a Waters Q-TOF Premier (ESI) spectrometer.
J= 7.4 Hz, CH2), 3.75-3.78 (6H, m, 2 OCH2 and SCH2), 3.98 (2H,
brs, NCH2), 4.35 (2H, brs, NCH2), 7.15-7.18 (1H, m, ArH), 7.28
(1H, d, J= 7.8 Hz, ArH), 7.64 (1H, td, J= 7.6 and 1.9 Hz, ArH),
8.56 (1H, d, J= 4.9 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3)
δ 36.0, 37.3, 50.8 (2C), 66.2 (2C), 121.6, 123.3, 136.4, 149.3,
159.6, 197.6 ppm; HRMS (ES+) calcd for C12H16N2OS2Na
(M+Na)+ 291.0602, found 291.0599.
4.2. Typical procedure for the synthesis of dithiocarbamates
In a test tube equipped with a magnetic stir bar, 2-vinylpyridine
(3 mmol, 0.323 mL) and carbon disulfide (4 mmol, 0.24 mL)
were added. The mixture was cooled in an ice bath and
diethylamine (3.3 mmol, 0.34 mL) was added dropwise. Then,
the ice bath was removed and the mixture was stirred vigorously
at room temperature for 6 h. In most of the cases, completion of
the reaction can be simply observed by solidification of the
reaction mixture. After completion, the reaction was quenched
with 0.1 M aqueous NaHCO3 solution (10 mL). In the case of
solid compounds, the products were simply collected by filtration
and washing with water. For oily compounds, the products were
extracted with ethyl acetate (2×20 mL) and the combined organic
layers were washed with water (20 mL) and dried over anhydrous
MgSO4. The solvent was evaporated under reduced pressure to
give the products in high purity. If needed, the products were
purified by flash column chromatography (silica gel, ethyl
acetate: petroleum ether; 3:7). In the case of bisdithiocarbamate
(Table 1, entry 22), 3 mmol (0.25 mL) of 1,3-propanediamine
was reacted with 6.5 mmol of 4-vinyl pyridine (0.7 mL) and 8
mmol (0.48 mL) of carbon disulfide. The products were
4.2.5. 2-(Pyridin-2-yl)ethyl allylcarbamodithioate (3e): Yellow
solid; m. p. 57-59 oC; IR (KBr) ν 3158, 1641, 1568, 1438, 1379,
1321, 1257, 1003, 919 cm-1; H NMR (500 MHz, CDCl3) δ 3.25
1
(2H, t, J=7.8 Hz, CH2), 3.64 (2H, t, J= 7.3 Hz, SCH2), 4.42 (2H,
t, J= 6.4 Hz, CH2), 5.25-5.33 (2H, m, CH2=), 5.91-5.99 (1H, m,
CH=), 7.17 (1H, dd, J= 7.3 and 4.9 Hz, ArH), 7.28 (1H, d, J= 7.8
Hz, ArH), 7.63-7.67 (1H, m, ArH), 8.10 (1H, brs, NH), 8.56 (1H,
d, J= 4.9 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 34.5,
38.1, 49.8, 118.7, 122.2, 123.9, 132.6, 137.1, 149.5, 159.7, 198.1
ppm; HRMS (ES+) calcd for C11H14N2S2Na (M+Na)+ 261.0496,
found 261.0499.
4.2.6.
2-(Pyridin-2-yl)ethyl
ethylcarbamodithioate
(3f):
o
Yellow solid; m. p. 82-84 C; IR (KBr) ν 3170, 1587, 1536,
1378, 1153, 1000, 955, 876 cm-1; H NMR (500 MHz, CDCl3) δ
1
1.31 (3H, t, J= 7.4 Hz, CH3), 3.23 (2H, t, J= 7.3 Hz, CH2), 3.64
(2H, t, J= 7.4 Hz, SCH2), 3.74-3.83 (2H, m, NCH2), 7.17 (1H, t,
J= 6.4 Hz, ArH), 7.26 (1H, d, J= 7.8 Hz, ArH), 7.64 (1H, tt, J=
7.6 and 2.0 Hz, ArH), 7.82 (1H, brs, NH), 8.56 (1H, d, J= 4.9 Hz,
ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 13.9, 34.5, 38.2, 42.5,
122.1, 123.8, 137.0, 149.6, 159.9, 197.4 ppm; HRMS (ES+) calcd
for C10H14N2S2Na (M+Na)+ 249.0496, found 249.0494.
characterized by their IR, H and 13C NMR spectra and HRMS
analyses.
1
4.2.1.
2-(Pyridin-2-yl)ethyl diethylcarbamodithioate (3a):
Yellow viscous oil; IR (KBr) ν 1485, 1415, 1267, 1205, 1140,
985 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.25-1.30 (6H, t, J= 7.4
Hz, 2CH3), 3.21 (2H, t, J= 7.8 Hz, CH2), 3.68-3.76 (4H, m, NCH2
and SCH2), 4.04 (2H, t, J= 7.3 Hz, NCH2), 7.15 (1H, t, J= 7.3 Hz,
ArH), 7.28 (1H, d, J= 7.6 Hz, ArH), 7.61 (1H, t, J= 7.8 Hz, ArH),
8.55 (1H, t, J= 4.7 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ
11.6, 12.4, 36.2, 37.4, 46.6, 49.4, 121.5, 123.3, 136.4, 149.2,
159.8, 195.4 ppm; HRMS (ES+) calcd for C12H19N2S2 (M+H)+
255.0990, found 255.0985.
4.2.7.
2-(Pyridin-2-yl)ethyl isopropylcarbamodithioate (3g):
o
Yellow solid; m. p. 62.5-64 C; IR (KBr) ν 3147, 1553, 1371,
1164, 991, 917 cm-1; H NMR (500 MHz, CDCl3) δ 1.30 (6H, d,
1
J= 6.5 Hz, 2CH3), 3.21 (2H, t, J= 7.3 Hz, CH2), 3.62 (2H, t, J=
7.3 Hz, SCH2), 4.74-4.81 (1H, m, NCH), 7.16 (1H, dd, J= 7.8
and 5.0 Hz, ArH), 7.27 (1H, d, J= 7.8 Hz, ArH), 7.51 (1H, brs,
NH), 7.64 (1H, td, J= 7.6 and 1.9 Hz, ArH), 8.56 (1H, dd, J= 5.0
and 1.9 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 22.1,
34.4, 38.2, 49.3, 122.1, 123.8, 137.0, 149.6, 159.9, 196.2 ppm;
HRMS (ES+) calcd for C11H17N2S2 (M+H)+ 241.0828, found
241.0835.
4.2.2.
2-(Pyridin-2-yl)ethyl piperidine-1-carbodithioate (3b):
o
Yellow solid; m. p. 44.5-47 C; IR (KBr) ν 1474, 1429, 1228,
1117, 1007, 984 cm-1; H NMR (500 MHz, CDCl3) δ 1.71-1.74
1
(6H, m, 3CH2), 3.23 (2H, t, J= 7.3 Hz, CH2), 3.73 (2H, t, J= 7.3
Hz, SCH2), 3.88 (2H, brs, NCH2), 4.32 (2H, brs, NCH2), 7.14-
7.17 (1H, m, ArH), 7.29 (1H, d, J= 7.8 Hz, ArH), 7.63 (1H, td,
J= 7.6 and 1.9 Hz, ArH), 8.56 (1H, d, J= 4.9 Hz, ArH) ppm; 13C
NMR (125 MHz, CDCl3) δ 24.3, 25.4, 25.9, 36.2, 37.5, 51.2,
52.8, 121.5, 123.3, 136.4, 149.3, 159.8, 195.5 ppm; HRMS (ES+)
calcd for C13H18N2S2Na (M+Na)+ 289.0809, found 289.0802.
4.2.8.
2-(Pyridin-2-yl)ethyl isobutylcarbamodithioate (3h):
o
Yellow solid; m. p. 60-62 C; IR (KBr) ν 3128, 1554, 1378,
1256, 1152, 1065, 1001, 887 cm-1; 1H NMR (500 MHz, CDCl3) δ
1.00 (6H, d, J= 6.8 Hz, 2CH3), 2.02-2.10 (1H, m, CH), 3.22 (2H,
t, J= 7.2 Hz, CH2), 3.59-3.64 (4H, m, SCH2 and NCH2), 7.15-
7.19 (1H, m, ArH), 7.25 (1H, d, J= 7.8 Hz, ArH), 7.64 (1H, td,
J= 7.6 and 1.9 Hz, ArH), 7.88 (1H, brs, NH), 8.56 (1H, d, J= 4.9
Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 20.5, 28.1, 34.5,
38.2, 54.9, 122.0, 123.8, 136.9, 149.6, 159.9, 197.9 ppm; HRMS
(ES+) calcd for C12H18N2S2Na (M+Na)+ 277.0809, found
277.0803.
4.2.3.
2-(Pyridin-2-yl)ethyl pyrrolidine-1-carbodithioate (3c):
Light brown solid; m. p. 57-59 oC; IR (KBr) ν 1595, 1437, 1166,
1011, 949 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.95-2.01 (2H, m,
CH2), 2.05-2.10 (2H, m, CH2), 3.21 (2H, t, J= 7.3 Hz, CH2), 3.63
(2H, t, J= 7.0 Hz, SCH2), 3.71 (2H, t, J= 7.8 Hz, NCH2), 3.95
(2H, t, J= 7.0 Hz, CH2N), 7.13-7.15 (1H, m, ArH), 7.28 (1H, d,
J= 7.8 Hz, ArH), 7.62 (1H, td, J= 7.6 and 1.9 Hz, ArH), 8.56
(1H, d, J= 5.0 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ
24.2, 26.0, 35.5, 37.6, 50.6, 54.9, 121.5, 123.3, 136.4, 149.2,
4.2.9. 2-(Pyridin-2-yl)ethyl butylcarbamodithioate (3i): Yellow
solid; m. p. 91-93 oC; IR (KBr) ν 3149, 1539, 1358, 1153, 1003,
920 cm-1; H NMR (500 MHz, CDCl3) δ 0.97 (3H, t, J= 7.3 Hz,
1
CH3), 1.40-1.44 (2H, m, CH2), 1.62-1.71 (2H, m, CH2), 3.21 (2H,
t, J= 7.1 Hz, CH2), 3.63 (2H, t, J= 7.6 Hz, SCH2), 3.74-3.78 (2H,

5
m, NCH ), 7.17-7.19 (1H, m, ArH), 7.26 (1H, d, J= 7.8 Hz,
4.2.15. 2-(Pyridin-2-yl)ethyl phenylcarbamodithioate (3o):
ACCEPTED MANUSCRIPT
2
ArH), 7.64 (1H, td, J= 7.6 and 1.6 Hz, ArH), 7.86 (1H, brs, NH),
Colorless solid; m.p. 132-134.5 oC; IR (KBr) ν 2692 (NH), 1594,
8.56 (1H, d, J= 4.9 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3)
δ 14.2, 20.4, 30.8, 34.5, 38.2, 47.4, 122.1, 123.8, 136.9, 149.6,
159.9, 197.5 ppm; HRMS (ES+) calcd for C12H19N2S2 (M+H)+
255.0984, found 255.0989.
1493, 1352, 961, 696 cm-1; H NMR (500 MHz, CDCl3) δ 3.14
1
(2H, t, J= 7.3 Hz, CH2), 3.65 (2H, t, J= 7.4 Hz, SCH2), 7.23-7.26
(2H, m, ArH), 7.31 (1H, d, J= 7.8 Hz, ArH), 7.37-7.41 (2H, m,
ArH), 7.63 (2H, brs, ArH), 7.71 (1H, td, J= 7.6 and 1.9 Hz, ArH),
8.52 (1H, dd, J= 5.1 and 1.8 Hz, ArH), 11.65 (1H, brs, NH) ppm;
13C NMR (125 MHz, CDCl3) δ 33.7, 36.5, 121.7, 123.1, 123.9,
126.0, 128.7, 136.5, 139.6, 149.0, 159.2, C=S (not observed)
ppm; HRMS (ES+) calcd for C14H15N2S2 (M+H)+ 275.0677,
found 275.0667.
4.2.10. 2-(Pyridin-2-yl)ethyl diallylcarbamodithioate (3j):
Viscous pale yellow oil; IR (KBr) ν 1643, 1593, 1470, 1435,
1
1228, 995, 928 cm-1; H NMR (500 MHz, CDCl3) δ 3.24 (2H, t,
J= 7.4 Hz, CH2), 3.73 (2H, t, J= 7.7 Hz, SCH2), 4.33 (2H, brs,
NCH2), 4.70 (2H, brs, NCH2), 5.20-5.28 (4H, m, 2CH2=), 5.80-
5.94 (2H, m, 2CH=), 7.15-7.17 (1H, m, ArH), 7.27 (1H, d, J= 7.8
Hz, ArH), 7.64 (1H, td, J= 7.6 and 1.9 Hz, ArH), 8.56 (1H, , J=
4.9 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 37.0, 37.7,
54.0, 56.8, 118.8, 119.0, 121.9, 123.7, 130.9, 131.5, 136.8, 149.8,
160.1, 198.3 ppm; HRMS (ES+) calcd for C14H18N2S2Na
(M+Na)+ 301.0809, found 301.0816.
4.2.11. 2-(Pyridin-2-yl)ethyl 3-hydroxypropylcarbamodithioate
(3k): Viscous yellow oil; IR (KBr) ν 3192, 1557, 1386, 1052,
1008, 910 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.90-1.96 (2H, m,
CH2), 3.23 (2H, t, J= 7.4 Hz, SCH2), 3.50 (2H, t, J= 7.3 Hz,
OCH2), 3.82-3.88 (2H, m, NCH2), 3.95-3.99 (2H, m, NCH2),
7.18-7.20 (1H, m, ArH), 7.27 (1H, d, J= 7.8 Hz, ArH), 7.66 (1H,
td, J= 7.6 and 1.8, ArH), 8.55 (1H, d, J= 4.9 Hz, ArH), 8.75 (1H,
brs, NH) ppm; 13C NMR (125 MHz, CDCl3) δ 30.7, 34.5, 38.3,
46.2, 61.3, 122.4, 124.1, 137.4, 149.4, 159.6, 197.1 ppm; HRMS
(ES+) calcd for C11H16N2OS2Na (M+Na)+ 279.0602, found
279.0599.
4.2.16. 2-(Pyridin-2-yl)ethyl
(R)-1-
phenylethylcarbamodithioate (3p): Colorless solid; m.p. 97-99
oC; IR (KBr) ν 3151, 1543, 1373, 1130, 1017, 953, 757, 697 cm-
1; H NMR (500 MHz, CDCl3) δ 1.65 (3H, d, J= 6.9 Hz, CH3),
1
3.21 (2H, t, J= 7.3 Hz, CH2), 3.66 (2H, t, J= 7.2 Hz, SCH2),
5.85-5.91 (1H, m, NCH), 7.14-7.42 (7H, m, ArH), 7.64 (1H, td,
J= 7.6 and 1.8 Hz, ArH), 7.97 (1H, brs, NH), 8.43 (1H, d, J= 4.8
Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 21.0, 34.5, 38.1,
56.1, 122.1, 123.8, 126.9, 128.1, 129.2, 137.0, 142.0, 149.6,
159.8, 196.8 ppm; HRMS (ES+) calcd for C16H18N2S2Na
(M+Na)+ 325.0809, found 325.0817.
4.2.17. 2-(Pyridin-2-yl)ethyl
2-(1H-indol-3-
yl)ethylcarbamodithioate (3q): Colorless solid; m.p. 103-105 oC;
IR (KBr) ν 3159, 1523, 1221, 1006, 945, 731, 703 cm-1; 1H NMR
(500 MHz, CDCl3) δ 3.14-3.20 (4H, m, 2CH2), 3.58 (2H, t, J=
7.4 Hz, SCH2), 4.06-4.10 (2H, m, NCH2), 6.98-7.39 (6H, m,
ArH), 7.58-7.67 (2H, m, ArH), 8.11 (1H, brs, NH), 8.43 (1H, dd,
J= 5.0 and 1.6 Hz, ArH), 8.74 (1H, brs, NH) ppm; 13C NMR (125
MHz, CDCl3) δ 24.0, 34.2, 37.6, 47.4, 111.4, 112.2, 118.7,
119.5, 121.8, 122.1, 122.3, 123.5, 127.3, 136.4, 136.8, 148.9,
159.4, 197.1 ppm; HRMS (ES+) calcd for C18H19N3S2Na
(M+Na)+ 364.0918, found 364.0919.
4.2.12. 2-(Pyridin-2-yl)ethyl benzylcarbamodithioate (3l):
o
Colorless solid; m.p. 94-96 C; IR (KBr) ν 3156, 1553, 1433,
1006, 925 cm-1; 1H NMR (500 MHz, CDCl3) δ 3.26 (2H, t, J= 7.1
Hz, CH2), 3.64 (2H, t, J= 7.1 Hz, SCH2), 4.96 (2H, d, J= 5.1 Hz,
NCH2), 7.12-7.41 (7H, m, ArH), 7.65 (1H, dt, J= 7.6 and 1.8 Hz,
ArH), 8.19 (1H, brs, NH), 8.31 (1H, dd, J= 5.0 and 1.8 Hz, ArH)
ppm; 13C NMR (125 MHz, CDCl3) δ 34.4, 38.1, 51.6, 122.1,
123.8, 128.5, 128.7, 129.3, 136.7, 137.0, 149.5, 159.6, 197.8
ppm; HRMS (ES+) calcd for C15H16N2S2Na (M+Na)+ 311.0653,
found 311.0652.
4.2.18.
(R)-Methyl
3-((2-(pyridin-2-
(3r):
yl)ethylthio)(thiocarbonyl))thiazolidine-4-carboxylate
Viscous yellow oil; IR (KBr) ν 1739, 1593, 1375, 1172, 996, 756
cm-1; H NMR (500 MHz, CDCl3) δ 3.10-3.19 (3H, m, CH2 and
1
SCH2 in ring), 3.29-3.41 (1H, m, SCH2 in ring), 3.62-3.71 (5H,
m, SCH2 and OCH3), 4.63 (1H, d, J= 9.2 Hz, NCH2S), 4.84 (1H,
d, J= 9.2 Hz, NCH2S), 5.70 (1H, dd, J=7.2 and 3.2 Hz, NCH),
7.07 (1H, dd, J= 7.5 and 5.0 Hz, ArH), 7.15 (1H, d, J= 7.8
Hz,ArH), 7.54 (1H, td, 7.6 and 4.8 Hz, ArH), 8.47 (1H, d, J= 4.9
Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 32.4, 36.4, 36.8,
51.2, 53.2, 68.4, 121.6, 123.2, 136.4, 149.3, 159.3, 169.0, 196.0
ppm; HRMS (ES+) calcd for C13H16N2O2S3Na (M+Na)+
351.0272, found 351.0280.
4.2.13. 2-(Pyridin-2-yl)ethyl 4-methoxybenzylcarbamodithioate
o
(3m): Colorless solid; m.p. 87-88.5 C; IR (KBr) ν 3138, 1510,
1251, 1029, 910 cm-1; 1H NMR (500 MHz, CDCl3) δ 3.22 (2H, t,
J= 7.2 Hz, CH2), 3.64 (2H, d, J= 7.2 Hz, SCH2), 3.87 (3H, s,
OCH3), 4.88 (2H, d, J= 4.8 Hz, NCH2), 6.90 (2H, d, J=8.6 Hz,
ArH) 7.13-7.29 (4H, m, ArH), 7.65 (1H, td, J= 7.6 and 1.8 Hz,
ArH), 8.05 (1H, brs, NH), 8.35 (1H, dd, J= 5.6 and 1.7 Hz, ArH)
ppm; 13C NMR (125 MHz, CDCl3) δ 34.4, 38.1, 51.1, 55.8,
114.7, 122.1, 123.8, 128.7, 130.2, 137.0, 149.5, 159.7, 159.8,
197.6 ppm; HRMS (ES+) calcd for C16H18N2OS2Na (M+Na)+
341.0758, found 341.0746.
4.2.19. 2-(Pyridin-4-yl)ethyl pyrrolidine-1-carbodithioate (3s):
Yellow solid; m.p. 74-75.5 C; IR (KBr) ν 1597, 1415, 1168,
o
1009, 809 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.98-2.12 (4H, m,
2CH2), 3.04 (2H, t, J= 7.6 Hz, CH2), 3.57 (2H, t, J= 7.6 Hz,
SCH2), 3.64 (2H, t, J= 6.9 Hz, NCH2), 3.94 (2H, t, J= 7.0 Hz,
NCH2), 7.24 (2H, dd, J= 4.6 and 1.5 Hz, ArH), 8.54 (2H, d, J=
4.4 and 1.6 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 24.2,
26.0, 34.7, 36.0, 50.6, 55.0, 124.0, 148.9, 149.8, 191.9 ppm;
HRMS (ES+) calcd for C12H16N2S2Na (M+Na)+ 275.0643, found
275.0647.
4.2.14. 2-(Pyridin-2-yl)ethyl
prop-2-ynylcarbamodithioate
o
(3n): Colorless solid; m.p. 96-100 C; IR (KBr) ν 3294, 3157,
2087, 1568, 1474, 1378, 1314, 1256, 1099, 1003, 931 cm-1; H
1
NMR (500 MHz, CDCl3) δ 2.38 (1H, t, J= 2.6 Hz, CH), 3.26
(2H, t, J= 7.1 Hz, CH2), 3.65 (2H, t, J= 7.1 Hz, SCH2), 4.55 (2H,
dd, J= 4.8 and 2.6 Hz, NCH2), 7.16-7.26 (2H, m, ArH), 7.66 (1H,
td, J= 7.6 and 1.8 Hz, ArH), 8.51 (1H, brs, NH), 8.60 (1H, dd, J=
5.5 and 1.7 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 33.9,
36.4, 37.5, 73.0, 78.0, 121.8, 123.5, 136.8, 149.1, 159.1, 197.8
ppm; HRMS (ES+) calcd for C11H12N2S2Na (M+Na)+ 259.0340,
found 259.0333.
4.2.20. 2-(Pyridin-4-yl)ethyl isopropylcarbamodithioate (3t):
o
Yellow solid; m.p. 103-105 C; IR (KBr) ν 3148, 1604, 1556,
1
1376, 1168, 996, 802 cm-1; H NMR (500 MHz, CDCl3) δ 1.21
(6H, d, J= 6.6 Hz, 2CH3), 2.92 (2H, t, J= 7.3 Hz, CH2), 3.45 (2H,

6
Tetrahedron
t, J= 7.8 Hz, SCH ), 4.64-4.71 (1H, m, NCH), 7.13 (2H, dd, J=
196.8 ppm; HRMS (ES+) calcd for C11H18N3S2 (M+H)+
ACCEPTED MANUSCRIPT
2
4.4 and 1.6 Hz, ArH), 7.49 (1H, brs, NH), 8.45 (2H, dd, J= 4.4
and 1.7 Hz, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 21.6,
34.9, 35.0, 49.0, 124.1, 149.0, 149.6, 195.3 ppm; HRMS (ES+)
calcd for C11H16N2S2Na (M+Na)+ 263.0643, found 263.0647.
4.2.21. 2-(Pyrazin-2-yl)ethyl pyrrolidine-1-carbodithioate (3u):
Brown solid; m.p. 64-66 oC; IR (KBr) ν 1462, 1439, 1333, 1157,
1007, 945 cm-1; 1H NMR (500 MHz, CDCl3) δ 1.97-2.11 (4H, m,
2CH2), 3.27 (2H, t, J= 7.2 Hz, CH2), 3.63 (2H, t, J= 6.9 Hz,
SCH2), 3.73 (2H, t, J= 7.4 Hz, NCH2), 3.95 (2H, t, J= 7.0 Hz,
NCH2), 8.44 (1H, d, J= 2.6 Hz, ArH), 8.52-8.54 (2H, m, ArH)
ppm; 13C NMR (125 MHz, CDCl3) δ 24.2, 25.9, 34.7, 34.8, 50.6,
54.5 142.6, 144.1, 145.0, 155.5, 192.1 ppm; HRMS (ES+) calcd
for C11H16N3S2 (M+H)+ 254.0786, found 254.0786.
256.0937, found 256.0944.
4.2.27. 2-(Pyrazin-2-yl)ethyl
4-
methoxyphenylcarbamodithioate (3aa): Cream solid; m.p. 94.5-
o
97.5 C; IR (KBr) ν 3135, 1606, 1510, 1335, 1247, 1023, cm-1;
1H NMR (500 MHz, CDCl3) δ 3.27 (2H, t, J= 7.3 Hz, CH2), 3.71
(2H, t, J= 7.2 Hz, SCH2), 3.84 (3H, s, OCH3), 6.92 (2H, m, ArH),
7.29 (2H, brs, ArH), 8.40 (1H, d, J= 2.6 Hz, ArH), 8.52-8.54
(2H, m, ArH), 9.40 (1H, brs, NH) ppm; 13C NMR (125 MHz,
CDCl3) δ 34.5, 34.7, 55.5, 114.4, 128.1, 142.6, 144.1, 144.9,
155.2, 158.9, two carbons were not observed ppm; HRMS (ES+)
calcd for C14H15N3OS2Na (M+Na)+ 328.0554, found 328.0560.
4.2.28. 2-(Pyridin-4-yl)ethyl 4-methoxyphenylcarbamodithioate
o
(3ab): Cream solid; m.p. 111-113.5 C; IR (KBr) ν 2741 (NH),
o
1
4.2.22. Bisdithiocarbamate (3v): Colorless solid; m.p. 131 C
1606, 1507, 1363, 1249, 1035, 974 cm-1; H NMR (500 MHz,
(decomposed); IR (KBr) ν 3176, 1606, 1567, 1385, 1327, 1103,
CDCl3) δ 3.04 (2H, t, J= 7.7 Hz, CH2), 3.55 (2H, t, J= 7.7 Hz,
SCH2), 3.85 (3H, s, OCH3), 6.85-7.50 (6H, m, ArH), 8.53-8.56
(2H, m, ArH), 9.70 (1H, brs, NH) ppm; 13C NMR (125 MHz,
CDCl3) δ 34.5, 35.8, 55.5, 114.3, 114.7, 124.0, 126.9, 148.9,
149.7, 158.5, C=S not observed; HRMS (ES+) calcd for
C15H16N2OS2Na (M+Na)+ 327.0602, found 327.0595.
1
1000, 953, 801 cm-1; H NMR (500 MHz, CDCl3) δ 1.87-1.93
(2H, m, CH2), 2.94 (4H, t, J= 7.1 Hz, 2CH2), 3.48 (4H, t, J= 7.3
Hz, 2SCH2), 3.61 (4H, t, J=7.2 Hz, 2NCH2), 7.29 (4H, dd, 4.4
and 1.6 Hz, ArH), 8.48 (4H, d, J= 4.3 and 1.7 Hz, ArH), 10.00
(2H, brs, NH) ppm; 13C NMR (125 MHz, CDCl3) δ 26.2, 33.9,
34.1, 44.5, 124.0, 148.8, 149.5, 195.6 ppm; HRMS (ES+) calcd
for C19H24N4S4Na (M+Na)+ 459.0782, found 459.0786.
4.2.29. 2-(Pyridin-2-yl)ethyl 4-methoxyphenylcarbamodithioate
(3ac): Cream solid; m.p. 122-124 oC; IR (KBr) ν 2500-3200
1
4.2.23. 2-(Pyridin-4-yl)ethyl butylcarbamodithioate (3w):
(NH), 1508, 1349, 1244, 992, 828 cm-1; H NMR (500 MHz,
o
Yellowish solid; m.p. 88-89.5 C; IR (KBr) ν 3170, 1606, 1562,
CDCl3) δ 3.24 (2H, t, J= 7.4 Hz, CH2), 3.69 (2H, t, J= 7.4 Hz,
SCH2), 3.84 (3H, s, OCH3), 6.87-7.33 (6H, m, ArH), 7.63-7.68
(1H, m, ArH), 8.53-8.55 (1H, m, ArH), 9.34 (1H, brs, NH) ppm;
13C NMR (125 MHz, CDCl3) δ 37.4, 55.4, 114.3, 114.8, 121.6,
123.4, 126.9, 136.4, 136.6, 149.2, 159.4, two carbons were not
observed; HRMS (ES+) calcd for C15H16N2OS2Na (M+Na)+
327.0602, found 327.0607.
1
1381, 1150, 998, 919 cm-1; H NMR (500 MHz, CDCl3) δ 0.97
(3H, t, J= 7.4 Hz, CH3), 1.38-1.46 (2H, m, CH2), 1.64-1.70 (2H,
m, CH2), 3.02 (2H, t, J= 7.3 Hz, CH2), 3.53 (2H, t, J= 7.8 Hz,
SCH2), 3.75-3.79 (2H, m, NCH2), 7.22 (2H, dd, J= 4.5 and 1.6
Hz, ArH), 7.80 (1H, brs, NH), 8.54 (2H, dd, J= 4.4 and 1.6 Hz,
ArH) ppm; 13C NMR (125 MHz, CDCl3) δ 13.6, 19.9, 30.3, 35.0,
36.7, 47.2, 124.0, 148.9, 149.7, 196.7 ppm; HRMS (ES+) calcd
for C12H18N2S2Na (M+Na)+ 277.0809, found 277.0802.
Acknowledgments
4.2.24. 2-(Pyridin-4-yl)ethyl diethylcarbamodithioate (3x):
o
We are grateful to the Faculty of Chemistry of Kharazmi
University for supporting this work. We also thank Dr. Marc
Schmidtmann for X-ray analysis.
Pale yellow solid; m.p. 63-65 C; IR (KBr) ν 1603, 1494, 1417,
1
1276, 1202, 1008, 914 cm-1; H NMR (500 MHz, CDCl3) δ 1.30
(6H, t, J= 7.1 Hz, 2CH3), 3.02 (2H, t, J= 7.6 Hz, CH2), 3.56 (2H,
t, J= 7.8 Hz, SCH2), 3.74 (2H, q, J= 7.1 Hz, NCH2), 4.05 (2H, q,
J= 7.1 Hz, NCH2), 7.23 (2H, dd, J= 4.4 and 1.6 Hz, ArH), 8.54
(2H, dd, J= 4.4 and 1.6, ArH) ppm; 13C NMR (125 MHz, CDCl3)
δ 11.6, 12.4, 34.6, 36.6, 46.7, 49.5, 124.0, 149.0, 149.8, 194.7
ppm; HRMS (ES+) calcd for C12H18N2S2Na (M+Na)+ 277.0809,
found 277.0805.
References and notes
1. (a) Kobayashi, S. Chem. Soc. Rev. 1999, 28, 1–15; (b) Tejedor, D.;
Gonzalez-Cruz, D.; Santos-Expoasito, A.; Marrero-Tellado, J. J.;
de Armas, P.; Garcyaa-Tellado, F. Chem. Eur. J. 2005, 11, 3502–
3510; (c) Dömling, A.; Wang, W.; Wang, K. Chem. Rev. 2012,
112, 3083–3135; (d) Dömling, A. Chem. Rev. 2006, 106, 17–89.
2. (a) Linthorst, J. A. Foundations Chem. 2010, 12, 55–68; (b)
Anastas, P. T.; Williamson, T. C. Green Chemistry: Designing
Chemistry for the Environment; ACS publications: Washington
DC, 1996; (c) Anastas, P. T.; Warner, J. C. Green Chemistry:
Theory and Practice; Oxford Science Publications: Oxford, 1998;
(d) Anastas, P. T.; Williamson, T. C. Green Chemistry: Frontiers
in Chemical Synthesis and Processes; Oxford University Press:
Oxford, 1998; (e) Clark, J. H. Green Chem. 1999, 1, 1–8.
3. (a) Greene, T. W.; Wuts, P. G. M. Protecting Groups in Organic
Synthesis, 3rd ed.; Wiley Interscience, New York, 1999; (b)
Rudorf, W. D. J. Sulfur Chem. 2007, 28, 295–339; (c) Aly, A. A.;
Brown, A. B.; Bedaira, T. M. I.; Ishak, E. A. J. Sulfur Chem.
2012, 33, 605–617.
4.2.25. 2-(Pyrazin-2-yl)ethyl diethylcarbamodithioate (3y):
yellow Oil; IR (KBr) ν 1486, 1417, 1268, 1205, 1018, 912, 727
1
cm-1; H NMR (500 MHz, CDCl3) δ 1.27-1.31 (6H, m, 2CH3),
3.28 (2H, t, J= 7.2 Hz, CH2), 3.71-3.76 (4H, m, NCH2 and
SCH2), 4.06 (2H, q, J= 7.2 Hz, NCH2), 7.45 (1H, d, J= 2.6 Hz,
ArH), 8.53-8.55 (2H, m, ArH) ppm; 13C NMR (125 MHz,
CDCl3) δ 11.6, 12.4, 34.6, 35.4, 46.7, 49.5, 142.6, 144.1, 145.0,
155.5, 194.8 ppm; HRMS (ES+) calcd for C11H18N3S2 (M+H)+
256.0942, found 256.0940.
4.2.26. 2-(Pyrazin-2-yl)ethyl
butylcarbamodithioate
(3z):
o
Colorless solid; m.p. 79-81 C; IR (KBr) ν 3189, 1541, 1401,
1
1325, 1059, 1023, 922 cm-1; H NMR (500 MHz, CDCl3) δ 0.95
4. S. Z. Zard, Xanthates and Related Derivatives as Radical
Precursors. Encyclopedia of Radicals in Chemistry, Biology and
Materials, Wiley, New York, 2012.
5. (a) Kiasat, A. R.; Kazemi, F.; Savari, A. Synth. Commun. 2008,
38, 1057–1063; (b) Godt Jr, H. C.; Wann, R. E. J. Org. Chem.
1961, 26, 4047–4051.
(3H, t, J= 7.4 Hz, CH3), 1.37-1.45 (2H, m, CH2), 1.61-1.69 (2H,
m, CH2), 3.25 (2H, t, J= 7.1 Hz, CH2), 3.68-3.79 (4H, m, SCH2
and NCH2), 7.28 (1H, brs, NH), 8.46 (1H, d, J= 2.4 Hz, ArH),
8.53-8.56 (2H, m, ArH) ppm; 13C NMR (125 MHz, CDCl3) δ
13.6, 19.9, 30.3, 33.8, 34.5, 47.1, 142.6, 144.1, 145.0, 155.2,

7
6. (a) Page, P. C. B. Organo-sulfur Chemistry I, Springer, Berlin,
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