Conjugated addition reaction of amine, carbon disulfide to electrophilic alkenes in the presence of anhydrous potassium phosphate

Article abstract of DOI:10.1081/SCC-100105674

Different kinds of β-electron-withdraw group substituted ethyl dithiocarbamates (3) were prepared by the conjugated addition of an amine (1) and carbon disulfide to electrophilic alkenes (2) in the presence of anhydrous potassium phosphate under mild condition in good yields.

Full text of DOI:10.1081/SCC-100105674

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CONJUGATED ADDITION REACTION OF AMINE,
CARBON DISULFIDE TO ELECTROPHILIC ALKENES
IN THE PRESENCE OF ANHYDROUS POTASSIUM
PHOSPHATE
Baoguo Guo* a , Zemei Ge a , Tieming Cheng a & Runtao Li b
a School of Pharmaceutical Sciences, Peking University, Beijing, 100 083, P. R. China
b School of Pharmaceutical Sciences, Peking University, Beijing, 100 083, P. R. China
Published online: 16 Aug 2006.
To cite this article: Baoguo Guo* , Zemei Ge , Tieming Cheng & Runtao Li (2001): CONJUGATED ADDITION REACTION
OF AMINE, CARBON DISULFIDE TO ELECTROPHILIC ALKENES IN THE PRESENCE OF ANHYDROUS POTASSIUM PHOSPHATE,
Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:19,
3021-3025
To link to this article: http://dx.doi.org/10.1081/SCC-100105674
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SYNTHETIC COMMUNICATIONS, 31(19), 3021–3025 (2001)
CONJUGATED ADDITION REACTION
OF AMINE, CARBON DISULFIDE TO
ELECTROPHILIC ALKENES IN THE
PRESENCE OF ANHYDROUS
POTASSIUM PHOSPHATE
Baoguo Guo,* Zemei Ge, Tieming Cheng,
and Runtao Liy
School of Pharmaceutical Sciences, Peking University,
Beijing, 100 083, P. R. China
ABSTRACT
Different kinds of b-electron-withdraw group substituted
ethyl dithiocarbamates (3) were prepared by the conjugated
addition of an amine (1) and carbon disulfide to electrophilic
alkenes (2) in the presence of anhydrous potassium phosphate
under mild condition in good yields.
In the previous papers,1–4 we have reported an efficient one-pot method
for the preparation of dithiocarbamate by the reaction of an amine and
carbon disulfide with alkyl halide in the presence of anhydrous potassium
phosphate. The anhydrous potassium phosphate plays an important part in
this method. As an extension of this method, we were interested to explore the
*Visiting scholar from Department of Chemistry, Shangqiu Teachers’ College.
yCorresponding author.
3021
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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3022
GUO ET AL.
application of anhydrous potassium phosphate in the conjugated addition
reaction of an amine and carbon disulfide to electrophilic alkenes to form
b-electron-withdrawing group substituted ethyl dithiocarbamates in this
paper.
Two methods for the preparation of b-electron-withdrawing group
substituted ethyl dithiocarbamates have been reported.5–7 Our results were
listed in Table 1. The structures of 3a–j conformed to ‘‘lectures’’ report and
1
the data of IR and H NMR were listed in Table 2. It can be found from
Table 1. Synthesis of Compounds 3

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CONJUGATED ADDITION REACTION
3023
1
Table 2. IR and H NMR Data of Compounds 3a–j
IR (KBr
or film) n (cmꢀ1
Compd.
)
1H NMR (CDCl3/TMS, d)
3a
2248
1203
1.28 (6H, t, J ¼ 7.2, CH3), 2.88 (2H, t, J ¼ 5.4,
CH2CN), 3.53 (2H, t, J ¼ 5.4, -SCH2), 3.73 (2H,
q, J ¼ 7.2, -CH2N-), 4.00 (2H, q, J ¼ 7.2, -CH2N-)
3b
3c
2249
1228
1.72 (6H, br, -(CH2)3-), 2.89 (2H, t, J ¼ 6.6,
CH2CN), 3.55 (2H, t, J ¼ 6.6, -SCH2), 3.88 (2H,
br, -CH2N-), 4.28 (2H, br, -CH2N-)
3359
2249
1199
0.98 (3H, t, J ¼ 7.2, CH3), 1.37 (2H, m, CH3CH2-),
1.56 (2H, m, -CH2CH2N-), 2.90 (2H, t, J ¼ 6.6,
CH2CN), 3.47 (2H, t, J ¼ 6.6, -SCH2), 3.60 (1H,
m, CH2N-), 4.08 (1H, m, CH2N-), 5.54, 5.81 (1H,
2br, -NH and -SH)
3d
2251
1203
747
2.90 (2H, t, J ¼ 6.6, CH2CN), 3.53 (2H, t, J ¼ 6.6,
-SCH2), 4.60 (2/5H, d, J ¼ 4.8, -CH2NCS-), 4.28
(8/5H, d, J ¼ 5.4, -CH2NC( ¼SH)S-), 7.16, 7.76
(1H, 2br, -NH and -SH), 7.34 (5H, m, Ar)
3e
3f
2241
1201
2.90 (4H, t, J ¼ 6.6, CH2CN), 3.58 (4H, t, J ¼ 6.6,
-SCH2), 4.08 (4H, br, pip), 4.42 (4H, br, pip)
3386
1653
1201
1.28 (6H, t, J ¼ 7.2, CH3), 2.71 (2H, t, J ¼ 6.9,
CH2CO-), 3.59 (2H, t, J ¼ 6.9, -SCH2), 3.72 (2H,
q, J ¼ 7.2, -CH2N-), 4.04 (2H, q, J ¼ 7.2, -CH2N-),
5.55 (1H, br, -NH), 5.78 (1H, br, -NH)
3g
3h
3i
3358
1646
1222
1.70 (6H, br, -(CH2)3-), 2.71 (2H, t, J ¼ 6.9,
CH2CO-), 3.60 (2H, t, J ¼ 6.9, -SCH2), 3.88 (2H,
br, -CH2N-), 4.29 (2H, br, -CH2N-), 5.75 (2H, br,
-NH2)
1730
1205
1.28 (9H, m, 3 ꢁ CH3), 2.79 (2H, t, J ¼ 6.6,
CH2CO-), 3.56 (2H, t, J ¼ 6.6, -SCH2), 3.72 (2H,
q, J ¼ 6.9, -CH2N-), 4.04 (2H, q, J ¼ 7.2, -CH2N-),
4.15 (2H, q, J ¼ 7.2, CH3CH2-)
1725
1229
1.28 (3H, t, J ¼ 7.2, -CH3), 1.70 (6H, br,
-(CH2)3-), 2.80 (2H, t, J ¼ 6.9, CH2CO-), 3.58 (2H,
t, J ¼ 6.9, -SCH2), 3.87 (2H, br, -CH2N-), 4.15 (2H,
q, J ¼ 7.2, -CH2CH3), 4.28 (2H, br, -CH2N-)
3j
1550
1225
744
1.68 (6H, br, -(CH2)3-), 3.81 (2H, br, -CH2N-), 4.18,
4.32 (2H, 2br, -CH2N-), 4.87 (1H, dd, J ¼ 10.5, 13.2,
-SCH-), 5.34 (1H, dd, J ¼ 13.5, 4.8, -CHNO2), 5.74
(1H, dd, J ¼ 13.5, 4.8, -CHNO2), 7.33 (5H, m, Ar)

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GUO ET AL.
Table 1 that in the presence of anhydrous potassium phosphate, primary
or secondary amine (1) can react easily with carbon disulfide and dif-
ferent kinds of electrophilic alkenes (2) to give corresponding b-electron-
withdrawing group substituted ethyl dithiocarbamates (3) at room
temperature in good yield. The reaction was carried out at one-pot and
most of the reactions were completed within 0.5 to 4 h. The electron-with-
drawing groups Y of electrophilic alkenes (3) can be -CN, -CO2Et,
-CONH2 or -NO2 and the X of electrophilic alkenes (3) can be hydrogen
or aromatic group. When the CH3CH¼CHCHO, CH3CH¼CHCO2Et,
CH2¼CCH3CO2Et or PhCH¼CHCOCH3 was used as electrophilic alkenes,
the reaction was difficult. The high steric effect may be the main reason.
In conclusion, a new one-pot synthetic method for the b-electron-with-
drawing group substituted ethyl dithiocarbamates was found.
EXPERIMENTAL
Melting points were determined on X4 microscope and were
uncorrected. IR spectra were recorded on Perkin-Elmer 298 instrument
(KBr disk or liquid film). 1H NMR spectra were performed on a
VXR 300 (300 MHz) instrument in DCCl3. Thin layer chromatography
was carried out on pre-coated GF254 silica gel plates. The column chromato-
graphy was performed using G60 H silica gel. Anhydrous potassium
phosphate was obtained from dehydration of H3PO4ꢂ7H2O. The other
reagents and solvents were of commercial quality from freshly opened
containers.
General procedure. To a stirred solution of amine 1 (3 mmol) and
anhydrous potassium phosphate (0.64 g, 3 mmol) in methanol (15 mL) was
added carbon disulfide (20 drops, ꢃ9 mmol) at <10ꢄC. After the mixture
was stirred at this temperature for 0.5 h, the electrophilic alkene 2 (3 mmol)
was added. Then the reaction was continued at room temperature
and was monitored by TLC(GF 254, petroleum ether–ethyl acetate). At
the completion of the reaction, the precipitate was filtered off.
Evaporation of the solvent and flash chromatography of the residue on
silica gel (gradient elution, petroleum ether–ethyl acetate) afforded pure
target compound 3.
REFERENCES
1. Li, R.T.; Ding, P.Y.; Han, M.; Cai, M.S. Synth. Commun. 1998, 28, 295.
2. Li, R.T.; Cai, M.S. Synth. Commun. 1999, 29, 65.

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3025
3. Ge, Z.M.; Li, R.T.; Cheng, T.M.; Cai, M.S. Synth. Commun. 1999,
29, 3191.
4. Li, R.T.; Ge, Z.M.; Cheng, T.M. Chemical Journal of Chinese
University 1999, 20, 1897.
5. Delaby, R.; Damines, R.; Seyden-penne, M.R. Compt. Rend. 1954, 239,
1645. CA 49:7491b.
6. Delaby, R.; Damines, R.; Seyden-penne, M.R. Compt. Rend. 1956, 242,
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8. Mustafaev, N.P.; Efendieva, Kh. K.; Gasanzade, G.R. Zh. Org. Khim.
1977, 13, 985. CA 87:52725.
Received in the Netherlands December 10, 2000

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