Synthesis of 5-alkyl(benzyl)idene-3-hydroxymethyl-2-thioxothiazolidin-4- ones [3]

Full text of DOI:10.1023/B:RUGC.0000016044.85332.dc

Russian Journal of General Chemistry, Vol. 73, No. 10, 2003, pp. 1663 1664. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 10, 2003,
pp. 1758 1759.
Original Russian Text Copyright
2003 by Ginak, Aronova, Rutto.
LETTERS
TO THE EDITOR
Synthesis of 5-Alkyl(benzyl)idene-3-hydroxymethyl-
2-thioxothiazolidin-4-ones
A. I. Ginak, E. B. Aronova, and M. V. Rutto
St. Petersburg State Institute of Technology, St. Petersburg, Russia
Received December 24, 2002
3-Hydroxymethylthiazolidinones are practically
important compounds which are usually obtained by
reaction of thiazolidin-4-ones with formaldehyde in
organic solvents in the presence of a catalytic amount
of an amine. The reaction is reversible, and in some
cases the yields of the target products are low [1].
thioxothiazolidin-4-one (III). Yield 97%, mp 75 C,
Rf 0.37. Found, %: N 6.27; S 27.82. C9H13NO2S2.
Calculated, %: N 6.06; S 27.72.
3-Hydroxymethyl-5-(1-methylpentylidene)-2-
thioxothiazolidin-4-one (IV). Yield 97%, mp 55 C,
Rf 0.39. Found, %: N 5.62; S 25.80. C10H15NO2S2.
Calculated, %: N 5.71; S 26.14.
With the goal of extending the synthetic potential
of solid-phase reactions we made an attempt to
prepare 3-hydroxymethylthiazolidin-4-ones by reac-
tion of gaseous formaldehyde with crystalline salts
derived from thiazolidin-4-ones. As examples we
selected ammonium salts of 2-thioxothiazolidin-4-one.
3-Hydroxymethyl-5-cyclohexylidene-2-thioxo-
thiazolidin-4-one (V). Yield 98%, mp 122 C, Rf
0.32. Found, %: N 6.02; S 26.22. C10H13NO2S2. Cal-
culated, %: N 5.76; S 26.35.
Initial 2-thioxothiazolidin-4-one alkylammonium
salt was placed in a glass tube, and gaseous formalde-
hyde was passed through the tube until the substrate
was converted completely into final product I X.
The progress of the reaction was monitored by TLC
[2], following the disappearance of the spot belonging
to the initial compound.
3-Hydroxymethyl-5-(1-methylhexylidene)-2-
thioxothiazolidin-4-one (VI). Yield 97%, mp 54 C,
Rf 0.35. Found, %: N 5.41; S 24.70. C11H17NO2S2.
Calculated, %: N 5.40; S 24.72.
3-Hydroxymethyl-5-(1-methylheptylidene)-2-
thioxothiazolidin-4-one (VII). Yield 98%, mp 40 C,
Rf 0.47. Found, %: N 5.13; S 23.41. C12H19NO2S2.
Calculated, %: N 5.12; S 23.45.
N CH2OH
C=S
O=C
RR C=C
S
I, R = Me, R = Me; II, R = Me, R = Et; III, R = Me, R =
Pr; IV, R = Me, R = Bu; V, RR = (CH2)5; VI, R = Me,
R = C5H11; VII, R = Me, R = C6H13; VIII, R = Me, R =
Ph; IX, R = H, R = Ph; X, R = H, R = p-MeC6H4.
3-Hydroxymethyl-5-( -methylbenzylidene)-2-
thioxothiazolidin-4-one (VIII). Yield 97%, mp
127 C, Rf 0.45. Found, %: N 5.52; S 23.88.
C12H9NO2S2. Calculated, %: N 5.28; S 24.17.
3-Hydroxymethyl-5-isopropylidene-2-thioxothia-
zolidin-4-one (I). Yield 98%, mp 114 C, Rf 0.34.
Found, %: N 7.11; S 31.72. C7H9NO2S2. Calculated,
%: N 6.89; S 31.55.
5-Benzylidene-3-hydroxymethyl-2-thioxothiazo-
lidin-4-one (IX). Yield 98%, mp 153 C, Rf 0.18.
Found, %: N 5.29; S 25.24. C11H9NO2S2. Calculated,
%: N 5.57; S 25.52.
3-Hydroxymethyl-5-(1-methylpropylidene)-2-
thioxothiazolidin-4-one (II). Yield 98%, mp 65 C,
Rf 0.30. Found, %: N 6.70; S 29.80. C8H11NO2S2.
Calculated, %: N 6.45; S 29.51.
3-Hydroxymethyl-5-(p-methylbenzylidene)-2-
thioxothiazolidin-4-one (X). Yield 98%, mp 162 C,
Rf 0.18. Found, %: N 5.19; S 23.78. C12H11NO2S2.
Calculated, %: N 5.28; S 24.19.
3-Hydroxymethyl-5-(1-methylbutylidene)-2-
1070-3632/03/7310-1663$25.00 2003 MAIK Nauka/Interperiodica

1664
GINAK et al.
ACKNOWLEDGMENTS
REFERENCES
1. Borisova, M.A., Ginak, A.I., Ivanova, T.L., and
Sochilin, E.G., Zh. Org. Khim., 1971, vol. 7, no. 7,
p. 1498.
2. Ginak, A.I., V’yunov, K.A., Volkova, A.A., and
Sochilin, E.G., Zh. Prikl. Khim., 1971, vol. 44, no. 6,
p. 2123.
This study was financially supported by the
Ministry of Education of the Russian Federation and
by the St. Petersburg Authorities (project for young
candidates of sciences, no. PD 02-1.3-359).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 10 2003