Reaction of N,N′-dibenzyldithiooxamide with benzoylacetylene

Full text of DOI:10.1134/s107036320802028x

ISSN 1070-3632, Russian Journal of General Chemistry, 2008, Vol. 78, No. 2, pp. 327 328.
Original Russian Text T.V. Nizovtseva, T.N. Komarova, A.S. Nakhmanovich, V.N. Elokhina, 2008, published in Zhurnal Obshchei Khimii, 2008,
Vol. 78, No. 2, pp. 342 343.
Pleiades Publishing, Ltd., 2008.
LETTERS
TO THE EDITOR
Reaction of N,N -Dibenzyldithiooxamide with Benzoylacetylene
T. V. Nizovtseva, T. N. Komarova, A. S. Nakhmanovich, and V. N. Elokhina
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
Received May 4, 2007
DOI: 10.1134/S107036320802028X
Reactions of thioamides with activated acetylenes
normally involve the sulfur and nitrogen atoms and
give rise to substituted 1,3-thiazolines [1,2] and 1,3-
thiazines [3,4]. It is also known that reactions of thio-
amides with acetylenedicarboxylic acid and its esters
in benzene and acetonitrile form substituted 1,3-
thiazolin-4-ones [3, 4]. However, reactions of ac-
tivated acetylenes with dithioamides still remain
poorly studied.
at 20 C, were the E,Z and Z,Z isomers of bis(benzoyl-
vinyl) sulfide [8].
In continuation of our research on reactions of
-acetylenic ketones with N,S-ambifunctional nucleo-
philes we have studied the reaction of N,N -dibenzyl-
dithiooxamide with benzoylacetylene. We anticipated
that, like in [8], N,N -dibenzyldithiooxamide in MeOH
and MeCN would act as a thiylating agent to afford
the isomeric E,Z- and Z,Z-bis(benzoylvinyl) sulfides.
However, N,N -dibenzyldithiooxamide failed to react
with benzoylacetylene under these conditions. At the
same time, under electrophilic conditions, that is, in
acetic acid in the presence of an equimolar amount of
58% perchloric acid at 20 C, substituted 1,3-thiazol-
idiniminum perchlorate III was obtained in a good
yield (74%).
We earlier described the synthesis of 4-amino-
(anilino)-2-benzoylmethyl-1,3-dithiin-6-iminium
perchlorates by the reaction of diamide and dianilide
of dithiomalonic acid with acetylenic ketones in
glacial AcOH in the presence of perchloric acid [5 7].
The only products of the reaction of dithiooxamide
with benzoylacetylene in MeOH, MeCN, or benzene
O
Ph
Ph
H
N
Ph
+
HN
Ph
S
S
S
HClO4
AcOH
N
S
Ph
Ph
Ph
N
H
S
NH
S
N
ClO4
H
II
O
Ph
HClO4
H
I
A
Ph
O
III
Apparently, the reaction proceeds via intermediate
formation of ketovinyl sulfide perchlorate A via addi-
tion of the SH group of dithiooxamide to the activated
triple bond of benzoylacetylene, followed by intra-
molecular cyclization to form product III.
[2-(Benzoylmethyl)-3-benzyl-4-thioxo-5-1,3-
thiazolidin-5-yl]benzyliminium perchlorate (III).
To a solution of 0.37 g (1.2 mmol) of N,N -dibenzyl-
dithiooxamide in 20 ml of acetic acid, 0.14 ml
(1.2 mmol, recalculated to 100% acid) of 58% per-
327

328
NIZOVTSEVA et al.
chloric acid was added, and a solution of 0.16 g
(1.2 mmol) of benzoylacetylene in 15 ml of acetic
acid was then slowly added under stirring. The reac-
tion mixture was stirred for 7 h at 20 C. Reaction
progress was monitored by TLC (eluent benzene
ether, 3:1) until the spot of benzoylacetylene dis-
appeared. The reaction mixture was cooled to 0 C,
the precipitate that formed was filtered off, washed
with cold water and ether, and dried in a vacuum to
obtain 0.48 g (74%) of compound III, mp 93 95 C.
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1
IR spectrum, , cm : 3173 (NH), 1707 (C=O), 1520
(C=N), 1230 (C=S), 1075 (ClO4), 685 (C S). 1H
NMR spectrum, , ppm: 4.11 s (2H, CH2Ph), 4.16
4.40 d.d (2H, CH2NH), 5.26 d (1H, CH), 7.15 8.02 m
(15H, 3Ph), 11.01 s (1H, NH). 13C NMR spectrum,
, ppm: 187.56 (C=O), 172.19 (C=S), 160.02 (C=N),
119.14 138.64 (Ph), 42.52; 43.47 (CH2Ph), 21.13
(CH). Found %: C 56.12; H 4.40; Cl 6.78; N 5.21;
S 11.95. C25H23ClN2S2O5. Calculated %: C 56.55;
H 4.34; Cl 6.69; N 5.28; S 12.08.
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The IR spectra were recorded on a Specord IR-75
1
instrument in KBr pellets. The H and 13C NMR
spectra were taken at 55 C on a Bruker DPX 400
spectrometer (400.13 and 100.62 MHz, respectively)
in DMSO-d6, internal reference HMDS.
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 78 No. 2 2008