Efficient synthesis of 3-acyl-5-arylmethylene-4-oxothiazolidine-2-thiones

Article abstract of DOI:10.1023/A:1015514217370

An efficient procedure was suggested for preparing 3-acyl-5-arylmethylene- 4-oxothiazolidine-2-thiones.

Full text of DOI:10.1023/A:1015514217370

Russian Journal of Applied Chemistry, Vol. 75, No. 1, 2002, pp. 164 165. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 1,
002, pp. 164 165.
Original Russian Text Copyright
2
2002 by Aronova, Ginak.
BRIEF
COMMUNICATIONS
Efficient Synthesis
of 3-Acyl-5-arylmethylene-4-oxothiazolidine-2-thiones
E. B. Aronova and A. I. Ginak
St. Petersburg State Technological Institute, St. Petersburg, Russia
Received June 27, 2001
Abstract An efficient procedure was suggested for preparing 3-acyl-5-arylmethylene-4-oxothiazolidine-2-
thiones.
3
-Acyl-5-arylmethylene-4-oxothiazolidine-2-thiones
of solid ambident substrates with gaseous electro-
philes are selective and are not complicated by degra-
dation.
are intermediates in synthesis of practically important
substances: pesticides, drugs, dyes, vulcanizing agents,
antioxidants, etc. [1]. These compounds are prepared
in solutions by reactions of appropriate acyl chlorides
with 5-arylmethylene-4-oxothiazolidine-2-thiones in
the presence of bases [2, 3]. The reactions are accom-
panied by hydrolysis with ring cleavage, which de-
creases the yield of the target products by 25 40%
and complicates their isolation from reaction mixtures.
Synthesis of 3-acyl-5-arylmethylene-4-oxothiazoli-
dine-2-thiones by cyclization from appropriate amides
and carbon disulfide [4] is multistage and gives poor
yields. Therefore, we suggest in this paper a procedure
for preparing 3-acyl-5-arylmethylene-4-oxothiazoli-
dine-2-thiones by direct acylation of solid alkali metal
salts of 5-arylmethylene-4-oxothiazolidine-2-thiones
with vapors of appropriate acyl chlorides (see table).
It is known [5] that nucleophilic substitution reactions
The reaction was performed in a tubular reactor
(1 cm in diameter, 10 cm high) equipped with control-
lable (70 250 C) electric heating. Acyl chloride vapor
mixed with an inert gas (nitrogen, argon) was passed
through a substrate bed. The reaction progress was
monitored by TLC. After reaction completion, excess
acyl chloride was removed in a vacuum.
The acylation pathway was judged from the hydrol-
ysis products. Addition of the acyl group to the nitro-
gen atom in the heterocycle follows from formation
of the initial 5-arylmethylene-4-oxothiazolidine-2-thi-
one in hydrolysis, according to the scheme
O
Na N C O
R C
+
S C C CHC H R
6
4
Cl
S
Yields after recrystallization Y, decomposition points Tdec, and elemental analyses of oxothiazolidinethiones Ia Ij
Found, %/Calculated, %
Compound
Y, %
Tdec, C
Formula
N
S
Ia
Ib
Ic
Id
Ie
If
Ig
Ih
Ii
66.2
74.5
71.1
72.8
73.6
76.7
69.2
74.5
67.2
68.1
132 132.5
154 155
147 148
137 138
176 177
155 156
184 185
211 212
219 220
215 216
5.40/5.32
4.31/4.35
3.88/3.94
4.04/4.08
4.36/4.13
3.83/4.13
4.16/3.94
4.05/3.89
7.97/7.60
7.12/7.56
23.24/24.35
19.99/19.71
18.47/18.04
19.48/18.68
18.13/18.89
18.15/18.89
18.02/18.04
16.92/17.82
17.97/17.40
17.01/17.31
C H NO S
12 9 2 2
C H NO S
1
7
11
2 2
C H NO S
1
8
13
3 2
C H NO S F
1
7
10
2 2
C H NO S
1
8
13
2 2
C H NO S
1
8
13
2 2
C H NO S
18 13 3 2
C H NO S Cl
1
6
10
2 2
C H N O S
1
9 16 2 2 2
Ij
C H N O S
17 10 2 4 2
1
070-4272/02/7501-0164$27.00 2002 MAIK Nauka/Interperiodica

EFFICIENT SYNTHESIS OF 3-ACYL-5-ARYLMETHYLENE-4-OXOTHIAZOLIDINE-2-THIONES
165
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 1 2002