Reaction of dithiooxamide with benzoylacetylene

Full text of DOI:10.1134/S1070363206040281

ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 4, pp. 659 660.
Pleiades Publishing, Inc., 2006.
Original Russian Text
pp. 694 695.
T.V. Nizovtseva, T.N. Komarova, A.S. Nahmanovich, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 4,
LETTERS
TO THE EDITOR
Reaction of Dithiooxamide with Benzoylacetylene
T. V. Nizovtseva, T. N. Komarova, and A. S. Nahmanovich
Favorskii Irkutsk Institute of Chemistry, Siberian Branch,
Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033 Russia
Received November 2, 2005
DOI: 10.1134/S1070363206040281
Previously we described the synthesis of 4-amino-
(anilino)-2-(benzoylmethyl)-1,3-dithiin-6-iminium
perchlorate by the reaction of dithiomalonamide and
dithiomalonanilide with c acylacetylenes and 1-bro-
mo-2-acylacetylenes in glacial AcOH in the presence
of perchloric acid [1, 2].
acetylene in methanol, benzene, and acetonitrile at
20 C to form the E,Z and Z,Z isomers of bis(benzoyl-
vinyl) sulfide (I). The reaction of dithiooxamide with
benzoylacetylene was also performed under micro-
wave activation in DMF for 1 2 min. In this case, bis-
(benzoylvinyl) sulfide (I) was isolated in 64% yield,
along with unidentified reaction products.
We found that dithiooxamide reacts with benzoyl-
N_
)
H
(
_
|
|
S
Ph
COPh
H
H2N
S
MeOH
H2N
+
H
NH2
H
O
S
S
A
Ph
Ph
COPh
H
H
COPh
HS
S
O
O
H2N CS CN
H
B
I
The reactions of dithiooxamide with benzoylace-
tylene in benzene, acetonitrile, or glacial AcOH at
65 70 C provide 1,2-bis(benzoylvinylsulfanyl)ethane-
diimine (II) in 17 30% yields.
O
S
S
S
HN
HN
H2N
S
Ph
O
Ph
Ph
C6H6
===
===
+ 2
H
NH2
O
II
Bis(benzoylvinyl) sulfide (I). A solution of 2.6 g
of benzoylacetylene in 20 ml of methanol was added
to a solution of 1.2 g of dithiooxamide in 30 ml of
methanol. The mixture was stirred for 8 h at 20 C and
cooled to 0 C. The precipitate that formed was filtered
off, dried in a vacuum, and recrystallized from me-
thanol benzene, 1:1, to obtain 1.17 g of sulfide I,
yield 38%, mp 143 145 C (E,Z isomer). IR spectrum,
659

660
NIZOVTSEVA et al.
1
, cm : 1640 (C=O), 1523 (C=C), 957 (trans-
CH=CH), 733 (CS), 695 (cis-CH=CH). Found, %: C
73.34; H 4.71; S 10.54. C18H14O2S. Calculated, %: C
73.47; H 4.76; S 10.88.
tain 0.84 g of compound II, yield 22%, mp 148
1
150 C (E,Z isomer). IR spectrum, , cm : 3385
(=NH), 1640 (C=O), 1535 (C=C), 950 (trans-
CH=CH), 740 (CS), 690 (cis-CH=CH). 1H NMR
spectrum, , ppm: 7.52 8.00 m (5H, C6H5), 8.07
The reaction in benzene gave 0.71 g of sulfide I,
yield 23%, mp 194 195 C (Z,Z isomer). IR spectrum,
8.09 d (2H, CH=CH, J 9.3 Hz), 8.81 8.83 d (2H,
,
CH=CH, J 9.3 Hz), 9.02 (2H, 2NH). Found, %:
C 63.28; H, 4.15; N 7.44; S 16.68. C20H16N2O2S2.
Calculated, %: C 63.16; H 4.21; N 7.37; S 16.84.
1
, cm : 1638 (C=O), 1545 (C=C), 730 (CS), 696
(cis-CH=CH). Found, %: C 73.52; H 4.81; S 10.95.
C18H14O2S. Calculated, %: C 73.47; H 4.76; S 10.88.
The reaction under the same conditions in glacial
The reaction in acetonitrile in the presence of Et3N
gave 0.65 g of compound I, yield 21%, mp 194
195 C (Z,Z isomer).
acetic acid gave 1.37 g of compound II, yield 36%,
1
mp 172 174 C (Z,Z isomer). IR spectrum, , cm :
3380 (=NH), 1680 (C=O), 1580 (C=C), 760 (CS), 690
The reaction of dithiooxamide with benzoylace-
tylene in DMF under microwave activation (360 W,
1 2 min) gave 1.97 g of sulfide I, yield 64%, mp
143 145 C (E,Z isomer).
(cis-CH=CH).
The IR spectra were obtained on a Specord IR-75
instrument in KBr. The H NMR spectrum is re-
corded on a Bruker-400 spectrometer in DMSO-d6,
1
1,2-Bis(benzoylvinylsulfanyl)ethanediimine (II).
A solution of 2.6 g of benzoylacetylene in 30 ml of
benzene was added to a solution of 1.2 g of dithio-
oxamide in 20 ml of benzene. The mixture was heated
at 65 70 C with stirring for 3 h and then kept for 4
days at 20 C with intermittent stirring. Reaction
progress was followed by TLC, eluent benzene ether,
3:1. Benzene was partially evaporated, the residue
was poured to a stirred cold ether. The precipitate that
formed was filtered off and dried in a vacuum to ob-
internal reference HMDS.
REFERENCES
1. Nizovtseva, T.V., Komarova, T.N., Nakhmano-
vich, A.S., and Lopyrev, V.A., Khim. Geterotsikl.
Soedin., 2002, no. 9, p. 1293.
2. Nizovtseva, T.V., Komarova, T.N., Nakhmano-
vich, A.S., Larina, L.I., Lopyrev, V.A., and Kalistrato-
va, E.F., Zh. Org. Khim., 2002, vol. 38, no. 8, p. 1256.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 4 2006