An efficient synthesis of aryldithiocarbamic acid esters from Michael addition of electron-deficient alkenes with arylamines and CS2 in solid media alkaline Al2O3

Article abstract of DOI:10.1016/j.tet.2008.11.084

An efficient synthesis of dithiocarbamic acid esters from Michael addition of electron-deficient alkenes with arylamines and CS₂ in solid media alkaline Al₂O₃ was presented. This method was suitable for a wide range of amines and a variety of Michael receptors. Specially, a series of aryldithiocarbamic acid esters was obtained from arylamines through this method. The protocol offers clean reactions and high yields with simple experimental procedures. Besides, the alkaline Al₂O₃ could be reused.

Full text of DOI:10.1016/j.tet.2008.11.084

Tetrahedron 65 (2009) 1005–1009
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Tetrahedron
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An efficient synthesis of aryldithiocarbamic acid esters from Michael addition
of electron-deficient alkenes with arylamines and CS2 in solid media
alkaline Al2O3
,
,
b
b
a,b,
*
Shuai Xia a b, Xin Wang b , Ze-mei Ge , Tie-ming Cheng , Run-tao Li
*
a State Key Laboratory of Natural and Biomimetic Drugs, Peking University, Beijing 100191, PR China
b Department of Chemical Biology, School of Pharmaceutical Sciences, Peking University, Beijing 100191, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 3 October 2008
Received in revised form 25 November 2008
Accepted 26 November 2008
Available online 30 November 2008
An efficient synthesis of dithiocarbamic acid esters from Michael addition of electron-deficient alkenes
with arylamines and CS2 in solid media alkaline Al2O3 was presented. This method was suitable for
a wide range of amines and a variety of Michael receptors. Specially, a series of aryldithiocarbamic acid
esters was obtained from arylamines through this method. The protocol offers clean reactions and high
yields with simple experimental procedures. Besides, the alkaline Al2O3 could be reused.
Ó 2008 Elsevier Ltd. All rights reserved.
1. Introduction
electrophilic reagents. More recently, Saidi’s group has reported
that the one-pot reaction could be performed without catalyst in
Besides being widely used as fungicides to protect crops from
fungal diseases,1 dithiocarbamic acid esters have a number of other
applications such as in photochemistry,2 catalysis in the sulfur
vulcanization of rubber,3 detection and analysis of biological NO
produced endogenously from NO synthases,4 and polymerization.5
Furthermore, functionalized carbamates are an important class of
compounds and their medicinal and biological properties warrant
study.6 Dithiocarbamic acid esters were recently reported as potent
anticancer agents7 and cell apoptosis inhibitors.8
Because of the reasons mentioned above, the synthesis of di-
thiocarbamates has received considerable attention. In the past,
dithiocarbamic acid esters could be prepared from the reaction of
amines with expensive and toxic reagents, such as thiophosgene
and isothiocyanate.9 Recently, a one-pot reaction of amines with
CS2 and electrophilic reagents has been developed. Much effort has
been focused on the exploration of reaction conditions for one-pot
reaction.10 Various bases, for instance, NaOH, NaOC2H5, Et3N,
Cs2CO3, and guanidine as well as different solvents such as DMF,
DMSO, and methanol, have been used to catalyze or improve the
reaction. Ranu and co-workers sped up the Michael reaction to
generate dithiocarbamate derivatives by using ionic liquid.11 Our
group has recently found that anhydrous K3PO4 was a very effective
base, and various classes of dithiocarbamic acid esters have been
prepared in the presence of anhydrous K3PO4.10h Meanwhile, we
extended this method to the epoxides and electrophilic alkenes as
water12 or solvent free.13 However, it is still a challenge to syn-
thesize aryldithiocarbamic acid esters from arylamines, because
few previous reports used aryl amines as substrates to participate
in the synthesis of dithiocarbamates through Michael addition re-
actions since their low reactivity. In addition, yields for those
reactions were generally low.13b Therefore, the need for the
development of more general and environmentally benign
methods remains. Herein, we wish to report an efficient synthesis
of aryldithiocarbamic acid esters from Michael addition of aryl-
amines, CS2, and electrophilic alkenes in solid media alkaline Al2O3.
2. Results and discussion
During the course of developing new methodologies for the
preparation of dithiocarbamic acid esters and related compounds,
we have noticed that alkaline Al2O3 could boost the Michael re-
action of aniline with CS2 and methyl acrylate. This result arose our
interest to develop an efficient procedure for the synthesis of
aryldithiocarbamic acid esters.
Firstly, aniline or tetrahydropyrrole was chosen to react with CS2
and methyl acrylate to screen the solid media. As shown in Table 1,
alkaline Al2O3 exhibited the best effect among screened four kinds
of solid media, i.e., silica gel, bentonite, Celite, and alkaline Al2O3.
After optimizing the conditions, we then examined the gener-
ality of these conditions to other substrates by using different
arylamines and a,b-unsaturated compounds. The results are sum-
marized in Table 2. All the reactions were performed smoothly
under optimized conditions by stirring all reagents together in the
* Corresponding authors. Tel.: þ8610 82801504; fax: þ8610 82716956.
E-mail addresses: xinwang@bjmu.edu.cn (X. Wang), lirt@bjmu.edu.cn (R.-t. Li).
0040-4020/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2008.11.084

1006
S. Xia et al. / Tetrahedron 65 (2009) 1005–1009
Table 1
Table 3
The screen of solid media
The Michael addition reactions of aliphatic amines as Michael donors
Solid media
r.t., 20h
R2
N
OMe
R2R1N
S
OMe
CS2
R1R2NH
R4
alkaline Al2O3
1.5-30h
S
O
O
S
CS2
NH
R1R2
R3
R1 = Ph, R2 = H;
R1R2 = -C4H8-
R1
R4
S
R3
2
Solid media
Yield %
Entry
R3CH]CHR4
OMe
R1R2NH
Product
Yielda
95
%
NH2
NH
NH
1
2
3
4
2a
Silica gel
Bentonite
Celite
Trace
Trace
Trace
88
84
61
58
95
O
O
O
O
O
OMe
OMe
OMe
OMe
NH
N
Alkaline Al2O3
2b
2c
2d
78
95
94
NH2
presence of alkaline Al2O3. Using methyl acrylate as Michael re-
ceptor, all tested arylamines, except 4-nitroaniline, gave the
expected products in good to excellent yields (Table 2, entries 1–6,
64–93%). When methyl acrylate was used instead of acrylonitrile as
(n-Bu)2NH
5
Ph
2e
2f
80
91
75
93
92
81
95
NH2
NH
Table 2
The Michael addition reactions of aryl amines as Michael donors
6
CN
CN
CN
CN
CN
CN
H
R4
alkaline Al2O3
10-30h
N
S
CS2
ArNH2
R3
NH
R4
Ar
7
2g
2h
2i
S
R3
N
1
8
NH2
Entry
R3CH]CHR4
ArNH2
Product
Yielda
88
%
OMe
O
9
(n-Bu)2NH
1
2
3
4
5
1a
NH2
O
10
11
Ph
2j
NH2
NH
OMe
O
1b
1c
1d
1e
93
92
85
80
NH2
NH2
2k
OMe
O
NH
12
2l
76
O
OMe
O
NH
NH
NO2
13
14
2m
2n
92
71
NH2
NH2
Ph
Ph
O
OMe
O
Ph
O
NH
15
2o
70
OMe
O
6
1f
64
Ph
NH2
a
Isolated yields.
O2N
OMe
O
7
8
9
1g
1h
1i
0
30
58
Michael receptor, moderate yields were obtained (Table 2, entries
8–10). The property and the position of substituted groups in
arylamines obviously influence the reactivity. Electron-donating sub-
stitute is favored to the reaction (Table 2, entries 2 and 3). Increasing
of steric hindrance might lead the decreasing of yield (entry 6).
To explore the scope of the reaction, we also investigated the
reaction of aliphatic amines and CS2 with Michael acceptors. As
shown in Table 3, all the aliphatic amines, including primary
amines, acyclic or cyclic secondary amines, could afford the
corresponding products in high yields when reacted with a vari-
ety of Michael acceptors such as methyl acrylate, acrylonitrile,
cyclohexenone, 2-nitrovinylbenzene, chalcone, and 4-phenyl
butene-2-one.
NH2
NH2
CN
CN
O
NH2
NH2
10
1j
52
CN
a
Isolated yields.

S. Xia et al. / Tetrahedron 65 (2009) 1005–1009
1007
Table 4
4.4. Methyl 3-(p-tolylcarbamothioylthio)propanoate (1c)
White powder; mp 79–80 ꢀC. 1H NMR (300 MHz, CDCl3):
(s, 3H, CH3), 2.81 (t, 2H, J¼6.9 Hz, CH2CO), 3.54 (t, 2H, J¼6.9 Hz,
CS2CH2), 3.71 (s, 3H, OCH3), 7.19–7.29 (m, 5H, C6H5), 8.84 (br, 1H,
NH). Anal. Calcd for C12H15NO2S2: C, 53.50; H, 5.61; N, 5.12. Found:
C, 53.76; H, 5.63; N, 4.79.
The yield of the reactions using recycled alkaline Al2O3
alkaline Al2O3
(n-Bu)2N
S
d
¼2.37
CN
CS2
(n-Bu)2NH
CN
3h
S
Entry
Yield %
1
93
91
90
88
2a
3b
4c
4.5. Methyl 3-(o-tolylcarbamothioylthio)propanoate (1d)
a
The first reuse.
The second reuse.
The third reuse.
Colorless oil. 1H NMR (300 MHz, CDCl3):
2H, J¼6.9 Hz, CH2CO), 3.52 (t, 2H, J¼6.9 Hz, CS2CH2), 3.69 (s, 3H, OCH3),
7.26–7.29 (m, 4H, C6H5), 8.69 (br, 1H, NH). Anal. Calcd for C12H15NO2S2:
C, 53.50; H, 5.61; N, 5.12. Found: C, 53.63; H, 5.69; N, 5.18.
d
¼2.29 (s, 3H, CH3), 2.80 (t,
b
c
Finally, recyclability of alkaline Al2O3 was examined through the
reaction of dibutyl amine, CS2, and acrylonitrile in alkaline Al2O3.
After the reaction completed, the product was washed off with ethyl
acetate from solid reaction mixture, and then the recovered alkaline
Al2O3 was dried and reused. It was found from Table 4 that alkaline
Al2O3 was recycled for three times without obvious loss of yield.
4.6. Methyl 3-(m-tolylcarbamothioylthio)propanoate (1e)
Colorless oil. 1H NMR (300 MHz, CDCl3):
d¼2.37 (s, 3H, CH3),
2.81 (t, 2H, J¼6.9 Hz, CH2CO), 3.54 (t, 2H, J¼6.9 Hz, CS2CH2), 3.70 (s,
3H, OCH3), 7.06–7.31 (m, 4H, C6H5), 8.87 (br, 1H, NH). Anal. Calcd for
C12H15NO2S2: C, 53.50; H, 5.61; N, 5.12. Found: C, 53.21; H, 5.29; N,
5.03.
3. Conclusion
In summary, we have developed a novel and efficient method
for the preparation of dithiocarbamic acid esters by Michael addi-
tion of electron-deficient alkenes with amines and CS2 in solid
media alkaline Al2O3. A wide range of amines, especially aryl
amines, reacted with CS2 and an array of Michael receptors to afford
the Michael addition products in high yields. Notably, the reaction
is clean and the alkaline Al2O3 could be reused without complex
work up, which is required for ‘green chemistry’.
4.7. Methyl 3-(2,6-dimethylphenylcarbamothioylthio)-
propanoate (1f)
Colorless oil. 1H NMR (300 MHz, CDCl3):
d¼2.26 (s, 6H, 2CH3),
2.76 (t, 2H, J¼6.9 Hz, CH2CO), 3.46 (t, 2H, J¼6.9 Hz, CS2CH2), 7.34–
7.44 (m, 3H, C6H5), 8.90 (br, 1H, NH). Anal. Calcd for C13H17NO2S2: C,
55.09; H, 6.05; N, 4.94. Found: C, 55.20; H, 5.97; N, 5.16.
4.8. 2-Cyanoethyl phenylcarbamodithioate (1h)
4. Experimental section
4.1. General methods
White powder; mp 70–71 ꢀC.1H NMR (300 MHz, CDCl3):
2H, J¼6.9 Hz,CH2CN), 3.53 (t, 2H, J¼6.9 Hz,CS2CH2), 3.66(s, 3H, OCH3),
7.26–7.43(m,5H,C6H5),9.60(br,1H, NH).Anal.CalcdforC10H10N2S2:C,
54.02; H, 4.53; N, 12.60. Found: C, 53.81; H, 4.46; N, 12.55.
d
¼2.88(t,
The mixture of amine (0.5 mmol), carbon disulfide (0.5 mmol),
and alkaline Al2O3 (0.5 g, commercial available, HF254 for TLC, pH:
9–10) was stirred at room temperature for 5 min. After the Michael
acceptor (0.5 mmol) was added, the whole mixture was stirred
vigorously for 1.5–30 h. Then, the solid mixture was washed with
ethyl acetate (10 mL), and alkaline Al2O3 was filtered off. The or-
ganic solvent was removed under reduced pressure to give the
desired product. The crude product was purified by re-
crystallization or column chromatography over silica gel. The al-
kaline Al2O3 could be recycled.
4.9. 2-Cyanoethyl 4-methoxyphenylcarbamodithioate (1i)
White powder; mp 97–98 ꢀC. 1H NMR (300 MHz, CDCl3):
d¼2.88
(t, 2H, J¼6.9 Hz, CH2CN), 3.49 (t, 2H, J¼6.9 Hz, CS2CH2), 3.83 (s, 3H,
OCH3), 6.87–6.95 (m, 2H, C6H5), 7.16–7.26 (m, 2H, C6H5), 9.05 (br,
1H, NH). Anal. Calcd for C11H12N2OS2: C, 52.35; H, 4.79; N, 11.10.
Found: C, 52.49; H, 4.81; N, 11.13.
4.10. 2-Cyanoethyl 2,6-dimethylphenyl carbamodithioate (1j)
4.2. Methyl 3-(phenylcarbamothioylthio)propanoate (1a)13b
White powder; mp 108–109 ꢀC. 1H NMR (300 MHz, CDCl3):
Colorless oil. 1H NMR (300 MHz, CDCl3):
d
¼2.79 (t, 2H, J¼6.9 Hz,
d
¼2.28 (s, 6H, 2CH3), 2.86 (t, 2H, J¼6.9 Hz, CH2CN), 3.43 (t, 2H,
CH2CO), 3.51 (t, 2H, J¼6.9 Hz, CS2CH2), 3.66 (s, 3H, OCH3), 7.26–7.43
J¼6.9 Hz, CS2CH2), 7.10–7.28 (m, 3H, C6H5), 8.89 (br, 1H, NH). Anal.
Calcd for C12H14N2S2: C, 57.56; H, 5.64; N, 11.19. Found: C, 57.50; H,
5.77; N, 11.06.
(m, 5H, C6H5), 9.60 (br, 1H, NH).
4.3. Methyl 3-(4-methoxyphenylcarbamothioylthio)-
propanoate (1b)
4.11. 3-(Pyrrolidine-1-carbothioylsulfanyl)-propionic acid
methyl ester (2a)13b
White powder; mp 91–92 ꢀC. 1H NMR (300 MHz, CDCl3):
d¼2.80
(t, 2H, J¼6.9 Hz, CH2CO), 3.52 (t, 2H, J¼6.9 Hz, CS2CH2), 3.70 (s, 3H,
OCH3), 3.80 (s, 3H, OCH3), 6.88–6.93 (m, 2H, C6H5), 7.27 (br, 2H,
C6H5), 9.28 (br, 1H, NH). Anal. Calcd for C12H15NO3S2: C, 50.50; H,
5.30; N, 4.91. Found: C, 50.38; H, 5.32; N, 4.79.
White powder; mp 46–47 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼1.94–2.12 (m, 4H, CH2CH2), 2.83 (t, 2H, J¼6.6 Hz, CH2CO), 3.58 (t,
2H, J¼6.6 Hz, CS2CH2), 3.64 (t, 2H, J¼6.9 Hz, CH2N), 3.71 (s, 3H,
OCH3), 3.93 (t, 2H, J¼6.9 Hz, CH2N).

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S. Xia et al. / Tetrahedron 65 (2009) 1005–1009
4.12. 3-(4-Methyl-piperazine-1-carbothioylsulfanyl)-
propionic acid methyl ester (2b)
4.20. Benzyl-dithiocarbamic acid 2-cyano-ethyl ester (2j)17
White powder; mp 52–53 ꢀC (lit. 54 ꢀC). 1H NMR (300 MHz,
White powder; mp 50–51 ꢀC. 1H NMR (300 MHz, CDCl3):
(s, 3H, CH3N), 2.51 (s, 4H, NCH2, NCH2), 2.82 (t, 2H, J¼6.6 Hz,
CH2CO), 3.59 (t, 2H, J¼6.6 Hz, CS2CH2), 3.71 (s, 3H, OCH3), 3.95 (br,
2H, CH2N CS2), 4.36 (br, 2H, CH2N CS2). 13C NMR (75 MHz; CDCl3):
d¼2.34
CDCl3):
d
¼2.87 (t, 2H, J¼6.6 Hz, CH2CN), 3.53 (t, 2H, J¼6.6 Hz,
CS2CH2), 4.89 (d, 2H, J¼5.1 Hz, PhCH2N), 7.33–7.42 (m, 5H, C6H5).
4.21. Diisopropyl-dithiocarbamic acid 2-cyano-ethyl
ester (2k)18
d
¼31.5, 33.7, 45.6, 51.8, 54.3, 172.4, 196.2. Anal. Calcd for
C10H18N2O2S2: C, 45.77; H, 6.91; N, 10.68. Found: C, 45.80; H, 6.78;
N, 10.54.
White powder; mp 96–97 ꢀC (lit. 103–104.5 ꢀC). 1H NMR
(300 MHz, CDCl3):
d
¼1.23–1.41 (m, 12H, 4CH3), 2.89 (t, 2H,
4.13. 3-Isopropylthiocarbamoylsulfanyl-propionic acid
methyl ester (2c)
J¼6.6 Hz, CH2CN), 3.55 (t, 2H, J¼6.6 Hz, CS2CH2), 4.14 (br, 1H, CH),
4.91 (br, 1H, CH). EIMS: m/z (%)¼230 (Mþ, 100), 177 (59), 176 (51),
130 (40), 100 (28), 40 (83).
Colorless oil. 1H NMR (300 MHz, CDCl3):
d¼1.28 (d, 6H, J¼6.6 Hz,
2CH3), 2.79 (t, 2H, J¼6.6 Hz, CH2CO), 3.50 (t, 2H, J¼6.6 Hz, CS2CH2),
3.71 (s, 3H, OCH3), 4.67–4.74 (m, 1H, CH), 6.88 (br, 1H, NH). Anal.
Calcd for C8H15NO2S2: C, 43.41; H, 6.83; N, 6.33. Found: C, 43.47; H,
6.58; N, 6.23.
4.22. Pyrrolidine-1-carbodithioic acid 3-oxo-cyclohexyl
ester (2l)12b
White powder; mp 62–63 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼1.87–2.46 (m, 10H, CH2CH2, CH2CH2CH2CO), 2.54 (dd, 1H, J¼9.6,
4.14. 3-Dibutylthiocarbamoylsulfanyl-propionic acid methyl
ester (2d)14
14.4 Hz, 1H of CH2CO), 2.89 (dd, 1H, J¼4.8, 14.4 Hz, 1H of CH2CO),
3.62 (t, 2H, J¼6.9 Hz, CH2N), 3.91 (t, 2H, J¼6.9 Hz, CH2N), 4.36–4.42
(m, 1H, CS2CH).
Colorless oil. 1H NMR (300 MHz, CDCl3):
d
¼0.93–0.98 (m, 6H,
2CH3), 1.31–1.39 (m, 4H, 2CH2), 1.64–1.72 (m, 4H, 2CH2), 2.81 (t, 2H,
J¼6.6 Hz, CH2CO), 3.56 (t, 2H, J¼6.6 Hz, CS2CH2), 3.63 (t, 2H,
J¼7.8 Hz, CH2N), 3.70 (s, 3H, OCH3), 3.94 (t, 2H, J¼7.8 Hz, CH2N).
4.23. Pyrrolidine-1-carbodithioic acid 2-nitro-1-phenyl-ethyl
ester (2m)19
White powder; mp 113–114 ꢀC. 1H NMR (300 MHz, CDCl3):
4.15. 3-Benzylthiocarbamoylsulfanyl-propionic acid methyl
ester (2e)15
d
¼1.94–2.12 (m, 4H, CH2CH2), 3.52–3.66 (m, 2H, CH2N), 3.92 (t, 2H,
J¼6.9 Hz, CH2N), 4.89 (dd, 1H, J¼10.5, 13.5 Hz, 1H of CH2NO2), 5.33
(dd, 1H, J¼5.1, 13.5 Hz, 1H of CH2NO2), 5.78 (dd, 1H, J¼5.1, 10.5 Hz,
CS2CH), 7.30–7.41 (m, 5H, C6H5).
White powder; mp 63–64 ꢀC (lit. 64–66 ꢀC). 1H NMR (300 MHz,
CDCl3):
d
¼2.81 (t, 2H, J¼6.6 Hz, CH2CO), 3.54 (t, 2H, J¼6.6 Hz,
CS2CH2), 3.70 (s, 3H, OCH3), 4.90 (d, 2H, J¼5.1 Hz, PhCH2N), 7.31–
4.24. Pyrrolidine-1-carbodithioic acid 3-oxo-1,3-diphenyl-
propyl ester (2n)13b
7.40 (m, 5H, C6H5).
4.16. Pyrrolidine-1-carbodithioic acid 2-cyano-ethyl
ester (2f)13b
White powder; mp 125–126 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼1.91–2.09 (m, 4H, CH2CH2), 3.55–3.65 (m, 2H, CH2N), 3.75 (dd,
1H, J¼9.6, 17.1 Hz, 1H of CH2COPh), 3.92 (t, 2H, J¼6.9 Hz, CH2N), 4.14
(dd, 1H, J¼4.5, 17.1 Hz, 1H of CH2COPh), 5.76 (dd, 1H, J¼4.5, 9.6 Hz,
CS2CH), 7.19–7.99 (m, 10H, 2C6H5).
White powder; mp 76–77 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼1.96–2.16 (m, 4H, CH2CH2), 2.90 (t, 2H, J¼6.6 Hz, CH2CN), 3.54 (t,
2H, J¼6.6 Hz, CS2CH2), 3.67 (t, 2H, J¼6.9 Hz, CH2N), 3.92 (t, 2H,
J¼6.9 Hz, CH2N).
4.25. Pyrrolidine-1-carbodithioic acid 3-oxo-1-phenyl-butyl
ester (2o)
4.17. 4-Methyl-piperazine-1-carbodithioic acid 2-cyano-ethyl
ester (2g)
White powder; mp 105–106 ꢀC. 1H NMR (300 MHz, CDCl3):
White powder; mp 43–44 ꢀC. 1H NMR (300 MHz, CDCl3):
d¼2.36
d
¼1.94–2.06 (m, 4H, CH2CH2), 2.14 (s, 3H, COCH3), 3.17 (dd, 1H,
J¼9.6, 16.2 Hz, 1H of CH2CO), 3.46–3.58 (m, 3H, 1H of CH2CO, CH2N),
3.89–3.94 (m, 2H, CH2N), 5.60 (dd, 1H, J¼5.1, 9.6 Hz, CS2CH), 7.22–
(s, 3H, CH3N), 2.52 (s, 4H, NCH2, NCH2), 2.89 (t, 2H, J¼6.6 Hz,
CH2CN), 3.56 (t, 2H, J¼6.6 Hz, CS2CH2), 3.96 (br, 2H, CH2N CS2), 4.36
(br, 2H, CH2NHCS2). Anal. Calcd for C9H15N3S2: C, 47.13; H, 6.59; N,
18.32. Found: C, 47.31; H, 6.60; N, 18.10.
7.43 (m, 5H, C6H5). 13C NMR (75 MHz; CDCl3):
d
¼24.1, 26.0, 29.8,
49.8, 50.2, 50.5, 54.8, 127.7, 128.2, 128.6, 139.2, 190.9, 205.7. Anal.
Calcd for C15H19NOS2: C, 61.39; H, 6.53; N, 4.77. Found: C, 61.17; H,
6.40; N, 4.66.
4.18. Isopropyl-dithiocarbamic acid 2-cyano-ethyl ester (2h)16
White powder; mp 99–100 ꢀC (lit. 96 ꢀC). 1H NMR (300 MHz,
Acknowledgements
CDCl3):
d
¼1.29 (d, 6H, J¼6.6 Hz, 2CH3), 2.86 (t, 2H, J¼6.6 Hz,
This work was supported by the funds of Natural Science
Foundation of China (NSFC20672009) and the Major State Basic
Research Development Program (Grant no. 2004CB719900).
CH2CN), 3.50 (t, 2H, J¼6.6 Hz, CS2CH2), 4.63–4.74 (m, 1H, CH), 7.02
(br, 1H, NH).
4.19. Dibutyl-dithiocarbamic acid 2-cyano-ethyl ester (2i)14
Supplementary data
Colorless oil. 1H NMR (300 MHz, CDCl3):
d
¼0.94–1.00 (m, 6H,
2CH3), 1.32–1.41 (m, 4H, 2CH2), 1.65–1.75 (m, 4H, 2CH2), 2.89 (t, 2H,
J¼6.6 Hz, CH2CN), 3.53 (t, 2H, J¼6.6 Hz, CS2CH2), 3.65 (t, 2H,
J¼7.8 Hz, CH2N), 3.93 (t, 2H, J¼7.8 Hz, CH2N).
1H NMR spectra for all the products were supported. Supple-
mentary data associated with this article can be found in the online
version, at doi:10.1016/j.tet.2008.11.084.

S. Xia et al. / Tetrahedron 65 (2009) 1005–1009
1009
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