Synthesis of some new 2-substituted thiazolid-4-ones

Full text of DOI:10.1515/znb-1986-0128

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134
Synthesis of Some New 2-Substituted
Thiazolid-4-ones
(NH^COj ♦ 2 HSCH2C00H
C = 0
Mansour I. Younesa, Maher F. El-Zohryb,
and Saoud A. Metwallyb *
1 a -d
a Chemistry Department, Faculty of Science,
Assiut University, Qena, Egypt
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CH>
H2°
rJL
X
/c*
b Chemistry Department, Faculty of Science,
Assiut University, Assiut, Egypt
R'
N '
H
r
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SNH2 Ho ' "°_
Z. Naturforsch. 41b, 134-135 (1986);
received March 8/August 14, 1985
2a-d
3a-
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R'
2-Substituted Thiazolid-4-ones, Synthesis
2-Substituted thiazolid-4-ones were prepared by
interaction of thioglycolic acid with certain acyl de-
rivatives in presence of ammonium carbonate and
dry benzene. The reaction mechanism is discussed.
a
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-
b
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o
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c
CH3-
c h 3
CL
Introduction
H3C ||
I
d
Thiazolid-4-ones are biologically active com-
pounds and in particular exhibit a wide variety of
pharmacological properties, including anticonvul-
sant, antipyretic, analgesic and antibacterial effects
[1—5], The majority of thiazolid-4-one known are
2,3-disubstituted derivatives and were synthesised by
the addition of a variety of thiols to Schiffs bases or
by the interaction of monochloroacetic acid with
thiocarbamides prepared from the reaction of aryl-
thiocyanates and aralkylamines [6, 7]. In the present
study we started the preparation of thiazolid-4-one
derivatives which are fully substituted in the 2-posi-
tion. This will enables us to get other substituent in
the 3-position using other simple reaction routes.
S
t S
,
Scheme 1.
pyrazolin-5-one ( le ) as acyl derivative no thiazolid-
4-one derivative was isolated. This may be explained
on the basis of the strong enolisation of l e to 4.
ChU
,CH,
H,C-
I-UC-
n- n^ 0
Results and D iscussion
le
The biological importance of thiazolid-4-one de-
rivatives prompted us to prepare some new 2-substi-
tuted thiazolid-4-one derivatives by phenyl, and 3-
methyl-2-pyrazolin-5-onyl groups. Thus aceto-
phenone ( la ) , benzophenone ( lb ), 2-acetylpyridine
(lc ), l-acetyl-3-methyl-2-pyrazolin-5-one (Id ) and
The identities of the formed 2-substituted
thiazolid-4-one derivatives were established by ele-
mental analysis, IR, and mass spectra.
4-acetyl-l-phenyl-3-methyl-2-pyrazolin-5-one
(le)
were reacted with thioglycolic acid in dry benzene in
presence of ammonium carbonate to give the corre-
sponding 2-substituted thiazolid-4-one derivatives
(3 a —d) (Scheme 1). The addition product (2) could
not be isolated. Using 4-acetyl-l-phenyl-3-methyl-2-
Experim ental
Melting points are uncorrected. Analytical data
were carried out at Technische Hochschule Darm-
stadt, West Germany. Mass spectra were obtained
using an AE1 MS 12 mass spectrometer operating
at 70 eV and the direct insertion technique was
* Reprint requests to Prof. Dr. S. A. Metwally.
used with
a probe temperature range between
150—200 °C. The IR spectra were obtained on a pye
Unicam SP-1000 Spectrometer.
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l-Acetyl-3-methyl-2-pyrazolin-5-one (Id) and 4- crystallized from benzene/petroleum ether 40—60 °C
acetyl-l-phenyl-3-methyl-2-pyrazolin-5-one
(le)
mixture 1:3. m.p. 185—187 °C.
were prepared according to literature procedures [9]
and they showed analytical and spectral data in
agreement with their structures.
C^H13NOS (255)
Calcd C 70.58 H 5.09 N 5.49,
Found C 70.33 H 5.12 N 5.47.
MS: m/e = 255 (M+); IR (KBr): v 3330 (NH),
1670 (C = 0 ) cm-1.
Synthesis of 2-substituted thiazolid-4-ones
(general procedure)
2-Methyl-2-(2-pyridyl)thiazoIid-4-one (3c)
A solution of the acetyl or benzoyl derivative
(0.1 mole), thioglycolic acid (0.1 mole) and am-
monium carbonate (0.12 mole) in dry benzene was
refluxed on water bath and the liberated water was
removed using a water separator. The reaction mix-
ture is removed. At the end of the reflux time, the
product was precipitated. The reaction mixture was
cooled to room temperature and the product was
collected by filteration then recrystallized from the
proper solvent.
2-Acetylpyridine (11.2 ml, 0.1 mole), thioglycolic
acid (9.2 g, 0.1 mole) and ammonium carbonate
(11.5 g, 0.12 mole) were reacted according to the
general procedure to give 10.8 g (55.6%) of 3c, crys-
tallized from benzene/petroleum ether 40—60 °C
mixture 1:1, m.p. >300 °C.
C9HwN2OS (194)
Calcd C 55.67 H 5.15 N 14.43,
Found C 55.46 H 5.09 N 14.51.
MS: m/e = 194 (M+); IR (KBr): v 3295 (NH),
1685 (C = 0 ) cm-1.
2-Methyl-2-phenylthiazolid-4-one (3 a)
A
mixture of acetophenone (la ) (11.9 ml,
0.1 mole), thiogycolic acid (9.2 g, 0.1 mole) and am- 2-M ethyl-2-(l—3-methyl-2-pyrazolin-5-onyl)-
monium carbonate (11.5 g, 0.12 mole) in 100 ml dry
benzene was allowed to react according to the gener-
al procedure to give 10.2 g (52.8%) of 3a, crystal-
lized from benzene/petroleum ether (40—60 °C) mix-
ture 1:3, m.p. 145 °C.
thiazolid-4-one (3d)
A solution of l-acetyl-3-methyl-2-pyrazolin-5-one
(14 g, 0.1 mole), thioglycolic acid (7.1 ml, 0.1 mole)
and ammonium carbonate (11.5 g, 0.12 mole) were
reacted in dry benzene (150 ml) according to the
general procedure to give 12.4 g of 3d (58.2%) crys-
tallized from ethanol, m.p. >300 °C.
C10HnNOS (193)
Calcd C 55.67 H 5.15 N 14.13,
Found C 55.46 H 5.09 N 14.51.
C8HnN30 2S (213)
MS: m/e = 193 (M+); IR (KBr): v 3290 (NH),
1675 (C = 0 ) cm“1.
Calcd C 45.07 H 5.16 N 19.71,
Found C 45.17 H 5.12 N 19.81.
MS: m/e = 213 (M+); IR (KBr): v 3295 (NH),
1710 (C = 0 ) cm"1.
2,2-Diphenylthiazolid-4-one (3 b)
The reaction of benzophenone (18.2 g, 0.1 mole),
thioglycolic acid (9.2 g, 0.1 mole) and ammonium
carbonate (11.5 g, 0.12 mole) according to the previ-
ous general procedure gave 14.5 g (56.68%) of 3b,
Appreciation is expressed to Prof. Dr. Klaus Hafner,
Institut für Organische Chemie, Technische Hochschule
Darmstadt, West Germany, for elemental and spectral an-
alyses.
[5] S. S. Parmer. C. Dwivedi, A. Chaudhari. and T. K.
Gupta. J. Med. Chem. 15, 99 (1972).
[1] S. P. Singh, S. S. Parmar, K. Raman, and V. I. Sten-
berg, Chem. Rev. 81, 175 (1981).
[2] U.S. Patent No. 4053471; Ref. Zh. Khim. 11098p
[6] A. R. Suvry, J. Am. Chem. Soc. 71, 3354 (1949).
[7] H. D. Troutman and L. M. Long, J. Am. Chem. Soc.
70, 3436 (1948).
[8] S. Chaloupka, H. Heimgartner, H. Schmid, H. Link,
P. Schonholzer, and K. Bernauer, Helv. Chim. Acta
59, 2566 (1976).
(1978).
[3] West German patent application No. 2614189; Ref.
Zh. Khim. 130106p (1978).
[4] Cephalosparine, in E. H. Flynn (ed.): “Penicillins
Chemistry” Biology, Academic Press, New York
1972.
[9] M. Ridi and Papini, Gazz. Chim. Ital. 77, 9104 (1947).
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