Regiospecific synthesis of dithiocarbamates via a markovnikov addition reaction

Article abstract of DOI:10.1055/s-0032-1318504

A simple, efficient, and regiospecific method for the synthesis of dithiocarbamates by the one-pot, three-component Markovnikov addition reaction of an amine, carbon disulfide, and N-vinylpyrrolidone is described. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0032-1318504

PAPER
▌1483
paper
Regiospecific Synthesis of Dithiocarbamates via a Markovnikov Addition
Reaction
Regiospecific Synthesis of Dithiocarbamates
Azim Ziyaei Halimehjani,* Hamed Pasha Zanussi, Mohammad Amin Ranjbari
Faculty of Chemistry, Kharazmi University, 49 Mofateh St., Tehran, Iran
Fax +98(21)88820992; E-mail: ziyaei@khu.ac.ir
Received: 21.01.2013; Accepted after revision: 06.03.2013
reasons, the synthesis of dithiocarbamate derivatives with
different substitution patterns at the thiol chain by a con-
venient and safe method has become a field of increasing
interest in synthetic organic chemistry during the past few
years. The Markovnikov addition reaction is a powerful
tool for the formation of a carbon–heteroatom bond. We
have previously reported a facile, highly efficient, and en-
vironmentally benign procedure for the one-pot synthesis
of dithiocarbamates with the Markovnikov addition reac-
tion in water using alkyl vinyl ethers as the electrophile.17
It is worthwhile noting that electron-rich alkenes, such as
enamides, which have proven to be useful reagents that
are widely utilized in organic synthesis,18 have seldom
been considered as convenient candidates for alkylation,
probably due to their weak electrophilicity. Dithiocarba-
mic acids are good nucleophiles and react with different
electrophiles, including alkyl halides, epoxides, and α,β-
unsaturated carbonyl compounds;19 however, to the best
of our knowledge, there are no reports on the synthesis of
dithiocarbamates using an enamide as electrophile.
Abstract: A simple, efficient, and regiospecific method for the syn-
thesis of dithiocarbamates by the one-pot, three-component
Markovnikov addition reaction of an amine, carbon disulfide, and
N-vinylpyrrolidone is described.
Key words: dithiocarbamates, Markovnikov addition, regiospeci-
ficity, multicomponent reactions
Development of strategically important processes which
are environmentally benign with efficient and green pro-
cedures, leading to the formation of new, useful com-
pounds via simple methodology and workup with low
toxicity materials, is currently receiving considerable at-
tention.1 Compared to reactions with solvent, solvent-free
reactions result in reduced pollution and decreased han-
dling and labor costs due to simplification of experimental
procedures and workup techniques. These factors would
be especially important during industrial production and
are in agreement with the goals of green chemistry.2
Multicomponent reactions (MCRs) are flexible reactions
for the rapid generation of complex molecules, often with
biologically relevant scaffold structures. Therefore, the
design of novel MCRs with green procedures has attracted
great attention from research groups working in various
areas, such as drug discovery, organic synthesis, and ma-
terials science.3
With the increasing interest in the development of envi-
ronmentally benign reactions, atom-economic processes,
and catalyst-free conditions, MCRs are ideal processes in
organic chemistry. With these goals in mind and in con-
tinuation of our research toward the synthesis of novel di-
thiocarbamates, herein we report an efficient, novel, and
environmentally benign procedure for the synthesis of di-
thiocarbamates via the Markovnikov addition reaction by
simple mixing of an amine, carbon disulfide, and N-vinyl-
pyrrolidone (1), with excellent yields of the products 2
(Scheme 1).
In recent years, dithiocarbamates (DTCs) and their syn-
thesis with a green procedure have received great atten-
tion, because of their indisputable applications. These
synthetic compounds play important roles in both re-
search and industry. For example, dithiocarbamates have
been used in agriculture as pesticides and fungicides, for
sulfur vulcanization in rubber manufacturing,4,5 and as
radical chain-transfer agents in reversible addition–frag-
mentation chain-transfer (RAFT) polymerizations.6 They
have also been extensively used as intermediates in organ-
ic synthesis,7 for the protection of amino groups in peptide
synthesis,8 in the synthesis of thioureas,9 isothiocya-
nates,10 2-imino-1,3-dithiolane,11 cynamides,12 and ionic
liquids,13 and in amide bond formation.14 They show wide
biological activities, such as antitumor, anticancer, and
antibacterial activities.15 They are also efficient ligands in
surface science and nanomaterials chemistry.16 For these
R
O
N
S
70 °C
O
+
+
NH
N
CS2
R
70–90%
N
R
S
R
1
2
Scheme 1
We began our investigation with the one-pot, three-com-
ponent reaction of diethyl amine, carbon disulfide, and N-
vinylpyrrolidone (NVP, 1) in various organic solvents at
room temperature; the product was obtained in poor yield.
Increasing the temperature to 50–70 °C resulted in in-
creased yields in most solvents (Table 1). The best yield
was obtained in N,N-dimethylformamide and the reaction
also gave a high yield in an ionic liquid medium (1-butyl-
SYNTHESIS 2013, 45, 1483–1488
Advanced online publication: 09.04.2013
0
0
3
9
-
7
8
8
1
1
4
3
7
-
2
1
0
X
DOI: 10.1055/s-0032-1318504; Art ID: SS-2013-N0061-OP
© Georg Thieme Verlag Stuttgart · New York

1484
A. Ziyaei Halimehjani et al.
PAPER
Table 1 Effect of Solvent on the Markovnikov Addition Reaction of Dithiocarbamic Acid to NVP (1)a
O
N
S
solvent
CS2
+
+
Et2NH
O
N
S
NEt2
2a
1
Solvent
H2Ob
n.r.f
MeCNb
45
Acetoneb
MeOHb
46
DMFc
75
THFb
73
ILc,d
70
Neatc
90
Yielde (%)
66
a Reaction conditions: Et2NH (4 mmol), CS2 (5 mmol), NVP (3 mmol).
b Reflux conditions.
c The reaction was carried out at 70 °C.
d IL = 1-butyl-3-methylimidazolium chloride.
e Isolated yields.
f No reaction.
Table 2 Diversity in the Markovnikov Addition Reaction of Dithio-
carbamic Acids to NVP (1)
3-methylimidazolium chloride). It was not possible to car-
ry out the reaction in water. Surprisingly, we found that an
excellent yield of product was obtained when the starting
materials were mixed without any organic solvent. Thus,
by simple mixing of the amine (4 mmol), carbon disulfide
(5 mmol), and NVP (3 mmol), the desired product was ob-
tained in excellent yield, without using any catalyst, at
70 °C. The purification procedure for this reaction is very
simple: the product precipitated upon treatment of the re-
action mixture with water, and can be collected by filtra-
tion. The reaction is regiospecific toward the
Markovnikov adduct.
O
N
S
R1R2NH
Entry
1
CS2
O
+
+
N
S
NR1R2
1
2
Product
Yielda (%)
O
S
N
82
After optimization of the reaction conditions, the general-
ity of these conditions was examined by using different
amines. As shown in Table 2, primary aliphatic amines
such as propylamine, allylamine, cyclohexylamine, ben-
zylamine, furfurylamine, and 1-phenylethylamine were
used in this process, with high yields (entries 1–6). Differ-
ent secondary amines such as dimethylamine, diethyl-
amine, pyrrolidine, piperidine, morpholine, and azepane
gave excellent yields (entries 7–12). Highly hindered
amines such as tert-butylamine and 1-aminoadamantane
did not give any addition product; also, aromatic amines
are not suitable for this reaction. We have only used NVP
as the electrophile in this reaction; other enamides were
not examined.
N
H
S
2a
O
O
S
S
N
N
2
3
73
80
N
H
S
2b
2c
N
H
S
S
It has been shown that the fungicidal activity of a com-
pound can be increased by increasing the number of di-
thiocarbamate moieties in the structure.20 For this
purpose, bis(dithiocarbamates) were synthesized with the
one-pot, three-component cascade Markovnikov addition
reaction using diamines such as piperazine, ethylenedi-
amine, and 1,3-benzenedimethanamine, carbon disulfide,
and NVP, in good to high yields (Table 3, entries 1–3).
O
N
4
5
83
85
N
H
S
2d
O
S
N
N
S
H
O
2e
Synthesis 2013, 45, 1483–1488
© Georg Thieme Verlag Stuttgart · New York

PAPER
Regiospecific Synthesis of Dithiocarbamates
1485
Table 2 Diversity in the Markovnikov Addition Reaction of Dithio-
carbamic Acids to NVP (1) (continued)
acid 3 which can protonate the electron-enriched alkene
NVP (1) to afford 5. Subsequent nucleophilic attack of the
dithiocarbamate anion 4 on 5 results in the product 2. This
proposal shows that the hydrogen of the dithiocarbamic
acid is necessary for the reaction to progress and also ex-
plains why the reaction does not proceed in the case of
N1,N1-dimethylethane-1,2-diamine (Table 3, entry 4) and
in basic media (the reaction is not possible in the presence
of NaOH or Et3N as base).
O
N
S
R1R2NH
CS2
O
+
+
N
S
NR1R2
1
2
Entry
Product
Yielda (%)
O
S
N
O
N
S
6
80
N
H
S
1
R1R2NH
CS2
+
R1R2N
SH
3
2f
O
S
N
S
+
O
N
O
N
S
7
8
70
90
R1R2N
S
–
Me2N
S
S
NR1R2
2g
H
4
5
2
Scheme 2
O
S
N
Et2N
S
In conclusion, we have described a simple and mild pro-
tocol for the synthesis of a new class of dithiocarbamates
by the one-pot, three-component Markovnikov addition
reaction of an amine, carbon disulfide, and N-vinylpyrrol-
idone. The reaction can be carried out in the absence of
any solvent and catalyst. Other advantages of this proce-
dure are the high to excellent yields, regiospecificity to-
ward the Markovnikov adduct, and simple workup. The
synthesized compounds are similar to those reported by
Sathiyanarayanan and co-workers,21 and they may have
biological activities.
2h
O
S
N
9
87
90
N
S
2i
2j
O
S
N
10
N
S
Melting points were determined with a Branstead Electrothermal
9200 apparatus and are uncorrected. IR spectra were recorded on a
Perkin-Elmer FT RX1 spectrophotometer over the range 400–4000
1
cm–1. H and 13C NMR spectra were determined for solutions in
O
S
N
CDCl3 with TMS as internal standard on a Bruker AMX 300 MHz
instrument. Elemental analyses were conducted with a Perkin-
Elmer 2004 (II) CHN analyzer.
11
12
88
85
N
S
O
Dithiocarbamates via Markovnikov Addition; General Proce-
dure
2k
To a mixture of 1-vinylpyrrolidin-2-one (0.32 mL, 3.0 mmol) and
CS2 (0.18 mL, 5.0 mmol), an amine (4.0 mmol) was added. The re-
action mixture was stirred vigorously at 70 °C for 6 h, then was
quenched with H2O (10 mL). The precipitated product was collect-
ed by filtration and washed several times with H2O. In most cases,
pure product was obtained. Further purification was by recrystalli-
zation (EtOH). In the case of diamines (3 mmol), CS2 (0.42 mL, 7
mmol) and 1-vinylpyrrolidin-2-one (0.64 mL, 6 mmol) were used.
It should be noted that in large-scale syntheses, the excess CS2 was
removed by simple distillation from the reaction mixture. The prod-
ucts were characterized by their IR, 1H NMR, and 13C NMR spectra,
and CHN analyses.
O
S
N
N
S
2l
a Isolated yields.
The proposed mechanism for the formation of the
Markovnikov adducts is given in Scheme 2. Reaction of
an amine with carbon disulfide gives the dithiocarbamic
1-(2-Oxopyrrolidin-1-yl)ethyl Propylcarbamodithioate (2a)
Yield: 0.605 g (82%); yellow solid; mp 76–78 °C.
© Georg Thieme Verlag Stuttgart · New York
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1486
A. Ziyaei Halimehjani et al.
Table 3 Synthesis of Bis(dithiocarbamates) via the Markovnikov Addition Reaction
Entry Diamine Product
PAPER
Yielda (%)
S
O
N
S
N
NH
N
S
N
1
79
HN
O
S
S
2m
O
H
N
S
N
NH2
N
N
S
S
N
H
2
35
H2N
O
S
2n
O
O
H
N
H
N
S
N
3
4
70
H2N
NH2
S
S
2o
Me2N
–
n.r.b
NH2
a Isolated yields.
b No reaction.
IR (KBr): 3185, 2961, 1662, 1552, 1420, 951, 890 cm–1.
1-(2-Oxopyrrolidin-1-yl)ethyl Benzylcarbamodithioate (2d)
Yield: 0.732 g (83%); white solid; mp 93–96 °C.
1H NMR (300 MHz, CDCl3): δ = 0.99 (t, J = 7.4 Hz, 3 H), 1.50 (d,
J = 7.2 Hz, 3 H), 1.74 (m, 2 H), 2.13 (m, 2 H), 2.49 (m, 2 H), 3.44–
3.67 (m, 4 H), 5.92 (q, J = 7.2 Hz, 1 H), 9.46 (br s, 1 H).
13C NMR (75 MHz, CDCl3): δ = 11.4, 17.4, 17.8, 21.1, 31.0, 42.0,
49.1, 53.5, 176.4, 192.2.
IR (KBr): 3158, 2952, 1654, 1536, 1284, 1094, 937 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.49 (d, J = 7.1 Hz, 3 H), 2.06 (m,
2 H), 2.25 (m, 1 H), 2.43 (m, 1 H), 3.43 (m, 1 H), 3.57 (m, 1 H), 4.94
(m, 2 H), 5.90 (q, J = 7.2 Hz, 1 H), 7.37 (m, 5 H), 9.81 (br s, 1 H).
13C NMR (75 MHz, CDCl3): δ = 17.4, 17.7, 30.8, 42.0, 50.2, 53.6,
127.6, 128.3, 128.4, 136.2, 176.5, 192.8.
Anal. Calcd for C10H18N2OS2: C, 48.75; H, 7.36; N, 11.37. Found:
C, 48.75; H, 7.44; N, 11.36.
Anal. Calcd for C14H18N2OS2: C, 57.11; H, 6.16; N, 9.51. Found: C,
57.24; H, 6.18; N, 9.60.
1-(2-Oxopyrrolidin-1-yl)ethyl Allylcarbamodithioate (2b)
Yield: 0.534 g (73%); yellow solid; mp 73–76 °C.
IR (KBr): 3170, 2960, 1660, 1552, 1204, 1057, 924 cm–1.
1-(2-Oxopyrrolidin-1-yl)ethyl Furan-2-ylmethylcarbamodi-
thioate (2e)
1H NMR (300 MHz, CDCl3): δ = 1.52 (d, J = 7.1 Hz, 3 H), 2.15 (m,
2 H), 2.49 (m, 2 H), 3.46 (m, 1 H), 3.60 (m, 1 H), 4.35 (m, 2 H), 5.29
(m, 2 H), 5.94 (m, 2 H), 9.58 (br s, 1 H).
Yield: 0.724 g (85%); yellow solid; mp 84–86 °C.
IR (KBr): 3136, 2971, 1664, 1552, 1205, 1083, 924, 742 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.50 (d, J = 7.2 Hz, 3 H), 2.10 (m,
2 H), 2.44 (m, 2 H), 3.43 (m, 1 H), 3.57 (m, 1 H), 4.82–5.00 (m, 2
H), 5.92 (q, J = 7.2 Hz, 1 H), 6.37–6.38 (m, 2 H), 7.42 (s, 1 H), 9.78
(br s, 1 H).
13C NMR (75 MHz, CDCl3): δ = 17.4, 17.9, 31.0, 42.1, 49.6, 53.7,
118.3, 131.5, 176.5, 192.7.
Anal. Calcd for C10H16N2OS2: C, 49.15; H, 6.60; N, 11.46. Found:
C, 49.26; H, 6.73; N, 11.44.
13C NMR (75 MHz, CDCl3): δ = 17.4, 17.8, 30.8, 42.1, 43.3, 53.7,
1-(2-Oxopyrrolidin-1-yl)ethyl Cyclohexylcarbamodithioate
(2c)
109.0, 110.4, 142.4, 149.1, 176.6, 193.1.
Anal. Calcd for C12H16N2O2S2: C, 50.68; H, 5.67; N, 9.85. Found:
C, 50.79; H, 5.60; N, 9.88.
Yield: 0.686 g (80%); white solid; mp 104–107 °C.
IR (KBr): 3252, 2921, 1667, 1530, 1392, 1088, 928 cm–1.
1-(2-Oxopyrrolidin-1-yl)ethyl 1-Phenylethylcarbamodithioate
1H NMR (300 MHz, CDCl3): δ = 1.26–1.42 (m, 5 H), 1.52 (d,
J = 7.2 Hz, 3 H), 1.65–1.83 (m, 3 H), 2.11–2.16 (m, 4 H), 2.46–2.53
(m, 2 H), 3.44 (m, 1 H), 3.62 (m, 1 H), 4.38 (m, 1 H), 5.89 (q, J = 7.0
Hz, 1 H), 9.21 (br s, 1 H).
13C NMR (75 MHz, CDCl3): δ = 17.5, 17.8, 24.9, 25.0, 25.2, 31.1,
31.2, 31.5, 42.0, 53.3, 56.2, 176.1, 190.7.
(2f)
Yield: 0.740 g (80%); yellow solid; mp 127–130 °C.
IR (KBr): 3286, 2988, 1669, 1654, 1547, 1281, 1086, 966, 701
cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.50 (d, J = 7.0 Hz, 3 H), 1.71 (d,
J = 7.0 Hz, 3 H), 2.00–2.18 (m, 3 H), 2.44 (m, 1 H), 3.40 (m, 1 H),
3.55 (m, 1 H), 5.82 (m, 1 H), 5.99 (m, 1 H), 7.25–7.44 (m, 5 H), 9.53
(br s, 1 H).
Anal. Calcd for C13H22N2OS2: C, 54.51; H, 7.74; N, 9.78. Found: C,
54.53; H, 7.92; N, 9.75.
Synthesis 2013, 45, 1483–1488
© Georg Thieme Verlag Stuttgart · New York

PAPER
Regiospecific Synthesis of Dithiocarbamates
1487
13C NMR (75 MHz, CDCl3): δ = 17.5, 20.6, 30.9, 41.9, 53.5, 54.0,
IR (KBr): 2919, 1698, 1416, 1260, 1169, 1044, 943 cm–1.
55.6, 125.5, 126.8, 127.4, 128.3, 176.3, 191.3.
1H NMR (300 MHz, CDCl3): δ = 1.51 (m, 4 H), 1.65–1.78 (m, 7 H),
1.97 (m, 2 H), 2.33 (m, 2 H), 3.37–3.53 (m, 2 H), 3.78 (m, 2 H),
4.06–4.15 (m, 2 H), 6.08 (m, 1 H).
Anal. Calcd for C15H20N2OS2: C, 58.41; H, 6.54; N, 9.08. Found: C,
58.72; H, 6.36; N, 9.27.
13C NMR (75 MHz, CDCl3): δ = 17.9, 19.7, 25.8, 26.2, 26.3, 27.1,
31.0, 45.4, 52.6, 54.9, 60.2, 174.5, 193.5.
1-(2-Oxopyrrolidin-1-yl)ethyl Dimethylcarbamodithioate (2g)
Yield: 0.487 g (70%); white solid; mp 118–120 °C.
IR (KBr): 2934, 1686, 1507, 1262, 1050, 980 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.75 (d, J = 7.0 Hz, 3 H), 2.05 (m,
2 H), 2.40 (m, 2 H), 3.35–3.62 (m, 8 H), 6.08 (q, J = 7.0 Hz, 1 H).
13C NMR (75 MHz, CDCl3): δ = 18.1, 19.8, 31.2, 41.5, 44.9, 45.8,
61.2, 174.8, 194.7.
Anal. Calcd for C13H22N2OS2: C, 54.51; H, 7.74; N, 9.78. Found: C,
54.83; H, 8.20; N, 9.56.
Bis[1-(2-oxopyrrolidin-1-yl)ethyl] Piperazine-1,4-dicarbodi-
thioate (2m)
Yield: 1.09 g (79%); yellow solid; mp 162–165 °C.
IR (KBr): 2984, 1697, 1461, 1276, 1157, 1043, 999 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.76 (d, J = 7.03 Hz, 6 H), 2.09
(m, 4 H), 2.37 (m, 4 H), 3.46 (m, 2 H), 3.61 (m, 2 H), 4.07 (br s, 4
H), 4.36 (br s, 4 H), 6.15 (q, J = 7.0 Hz, 2 H).
13C NMR (75 MHz, CDCl3): δ = 18.1, 19.9, 31.1, 45.6, 48.5 (br s, 2
C), 60.9, 174.9, 195.4.
Anal. Calcd for C9H16N2OS2: C, 46.52; H, 6.94; N, 12.06. Found:
C, 46.67; H, 7.08; N, 11.85.
1-(2-Oxopyrrolidin-1-yl)ethyl Diethylcarbamodithioate (2h)
Yield: 0.702 g (90%); white solid; mp 76–80 °C.
IR (KBr): 2970, 1701, 1494, 1197, 1044, 912 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.29 (m, 6 H), 1.76 (d, J = 7.0 Hz,
3 H), 2.05 (m, 2 H), 2.42 (m, 2 H), 3.46 (m, 1 H), 3.60–3.74 (m, 3
H), 3.99 (m, 2 H), 6.13 (q, J = 7.0 Hz, 1 H).
13C NMR (75 MHz, CDCl3): δ = 11.5, 12.5, 18.2, 20.0, 31.3, 45.9,
46.8, 49.0, 60.8, 174.8, 193.2.
Anal. Calcd for C18H28N4O2S4: C, 47.93; H, 6.13; N, 12.16. Found:
C, 47.58; H, 6.18; N, 12.25.
2.
Bis[1-(2-oxopyrrolidin-1-yl)ethyl]ethylenediamine-1,2-dicarbo-
dithioate (2n)
Anal. Calcd for C11H20N2OS2: C, 50.73; H, 7.74; N, 10.76. Found:
C, 50.95; H, 8.07; N, 10.73.
Yield: 0.456 g (35%); yellow solid; mp 150–152 °C.
IR (KBr): 3313, 3183, 2978, 1664, 1527, 1264, 1069, 949 cm–1.
1-(2-Oxopyrrolidin-1-yl)ethyl Pyrrolidine-1-carbodithioate (2i)
1H NMR (300 MHz, CDCl3): δ = 1.53 (d, J = 7.1 Hz, 6 H), 2.10–
2.18 (m, 4 H), 2.49–2.61 (m, 4 H), 3.43–3.61 (m, 4 H), 4.08–4.16
(m, 4 H), 6.00–6.15 (m, 2 H), 9.78 (br s, 2 H).
Yield: 0.673 g (87%); white solid; mp 106–109 °C.
IR (KBr): 2949, 1696, 1443, 1250, 1159, 1000, 949 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.71 (d, J = 7.0 Hz, 3 H), 1.92–
2.06 (m, 6 H), 2.36 (m, 2 H), 3.54–3.59 (m, 4 H), 3.87 (m, 2 H), 6.10
(m, 1 H).
13C NMR (75 MHz, CDCl3): δ = 18.0, 19.9, 24.0, 25.8, 31.1, 45.7,
50.5, 54.5, 59.9, 174.6, 190.2.
13C NMR (75 MHz, CDCl3): δ = 17.6, 18.1, 31.1, 42.4, 45.5, 54.2,
176.8, 194.0.
Anal. Calcd for C16H26N4O2S4: C, 44.21; H, 6.03; N, 12.89. Found:
C, 43.93; H, 5.75; N, 13.39.
Bis(dithiocarbamate) 2o
Yield: 1.07 g (70%); yellow solid; mp 138–141 °C.
IR (KBr): 3246, 1667, 1532, 1082, 944 cm–1.
Anal. Calcd for C11H18N2OS2: C, 51.13; H, 7.02; N, 10.84. Found:
C, 50.98; H, 7.02; N, 10.82.
1-(2-Oxopyrrolidin-1-yl)ethyl Piperidine-1-carbodithioate (2j)
1H NMR (300 MHz, CDCl3): δ = 1.54 (d, J = 7.13 Hz, 6 H), 2.08–
2.49 (m, 8 H), 3.45 (m, 2 H), 3.59 (m, 2 H), 4.89–5.04 (m, 4 H), 5.97
(q, J = 7.1 Hz, 2 H), 7.30–7.42 (m, 4 H), 9.89 (br s, 2 H).
Yield: 0.734 g (90%); white solid; mp 57–60 °C.
IR (KBr): 2952, 1694, 1481, 1242, 978 cm–1.
1H NMR (300 MHz, CDCl3): δ = 1.71–1.75 (m, 9 H), 2.04 (m, 2 H),
2.40 (m, 2 H), 3.42–3.64 (m, 2 H), 3.86 (br s, 2 H), 4.29 (br s, 2 H),
6.14 (q, J = 7.0 Hz, 1 H).
13C NMR (75 MHz, CDCl3): δ = 18.1, 19.9, 24.1, 25.3, 25.9, 31.3,
45.8, 51.4, 52.3, 60.7, 174.8, 193.0.
13C NMR (75 MHz, CDCl3): δ = 17.6, 17.9, 31.0, 42.2, 50.1, 53.9,
127.6, 127.9, 128.7, 136.7, 176.6; C=S not observed.
Anal. Calcd for C22H30N4O2S4: C, 51.73; H, 5.92; N, 10.97. Found:
C, 51.71; H, 5.82; N, 11.03.
Anal. Calcd for C12H20N2OS2: C, 52.90; H, 7.40; N, 10.28. Found:
C, 52.71; H, 7.40; N, 10.40.
Acknowledgment
We are grateful to the Faculty of Chemistry, Kharazmi University
(Tarbiat Moallem University) for supporting this work.
1-(2-Oxopyrrolidin-1-yl)ethyl Morpholine-4-carbodithioate
(2k)
Yield: 0.723 g (88%); white solid; mp 108–110 °C.
IR (KBr): 2924, 1695, 1458, 1267, 1112, 994 cm–1.
Supporting Information for this article is available online at
1H NMR (300 MHz, CDCl3): δ = 1.69 (d, J = 7.01 Hz, 3 H), 1.98–
2.06 (m, 2 H), 2.33–2.38 (m, 2 H), 3.37–3.71 (m, 6 H), 3.87 (br s, 2
H), 4.25 (br s, 2 H), 6.03–6.16 (m, 1 H).
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References
13C NMR (75 MHz, CDCl3): δ = 17.9, 19.7, 31.0, 45.4, 50.4 (2 C),
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1-(2-Oxopyrrolidin-1-yl)ethyl Azepane-1-carbodithioate (2l)
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2013, 45, 1483–1488

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