International Journal of Organic Chemistry, 2012, 2, 135-142
http://dx.doi.org/10.4236/ijoc.2012.22021 Published Online June 2012 (http://www.SciRP.org/journal/ijoc)
An Efficient and Convenient Synthesis of Certain
2-Thioxothiazole,2-oxo-1,2-dihydropridine,
2-Oxo-2H-pyran,2,4-diaminothiophene and
Pyrazolo[5,1-c][1,2,4]triazine Derivatives Containing
Antipyrine Moiety
Seif-Eldin Nasr Ayyad
1,2
, Fathy Muhammad Abdelaziz El-Taweel
2*
, Abdel-Ghani Ali Elagamey
2
,
Tahani Mahmoud El-Mashad
2
1
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, KSA
2
Department of Chemistry, Faculty of Science, New Damietta Branch, Mansoura University, New Damietta, Egypt
Email:
*
fathyeltaweel@yahoo.com
Received February 18, 2012; revised March 9, 2012; accepted March 23, 2012
ABSTRACT
2-Thioxothiazole derivatives 5a-c were prepared by reacting a mixture of 1a-c, CS
2
/KOH and 4-(2-chloroacetyl)-1,
5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one (3). Reacting 2-cyano-N-(4-(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-
pyrazol-4-yl)-2-thioxothiazol-3(2H)-yl)acetamide (5c) with mercaptoacetic acid, arylidenemalononitriles 8 and (E)-
3-(dimethylamino)-1-(furan-2-yl)prop-2-en-1-one (12) give 4-oxo-4,5-dihydrothiazole 6, 2-oxo-1,2-dihydropyridine 10
and 2-oxo-2H-pyran 15 respectively. Heating a mixture of 5c, malononitrile and elemental sulfur yield 2,4-diaminothio-
phene 19. Coupling of 5c with the diazotized aminopyrazole 20 and aryldiazonium salts 23 give pyrazolo[5,1-c][1,2,4]
triazines 22 and arylhydrazones 25 respectively.
Keywords: Thioxothiazoles; Pyridine; Thiophene; Pyrazolotriazines
1. Introduction
Diverse pharmacological properties have been associated
with thiazole derivatives [1-3]. These pharmacological
activities have been attracted special attention to prepare
a new class of thiazole derivatives carrying antipyrinyl
moiety because of their applications in the field of phar-
maceuticals [4-6] and antibacterials [7-9]. The present
work reports the synthesis of certain thiazole derivatives
containing antipyrine moiety using readily available start-
ing materials.
2. Experimental
All melting points are uncorrected and have been meas-
ured on a Griffin & George MBF010T (London) appa-
ratus. Recorded yields correspond to the pure products.
IR (KBr) spectra were recorded on a Perkin Elmer SP-
880 spectrometer and from samples of sufficient solubil-
ity.
1
H-NMR spectra were measured on a Varian 270 MHz
spectrometer on DMSO-d
6
as solvent and TMS as an inter-
nal standard. Chemical shifts are reported in δ units (ppm).
Microanalyses were performed on a LECO CHN-932
elemental analyzer and carried out in the Microanalytical
Data Units at Cairo and Mansoura Universities.
General procedure for preparation of 4,4’-(2-thioxo-
thiazole-3,4-(2H)-diyl)bis(1,5-dimethyl-2-phenyl-1H-
pyrazol-3(2H)-one)(5a),2-(4-chlorophenoxy)-N-(-(1,5-di-
methyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)-2-
thioxothiazol-3(2H)-yl)acetamide(5b) and 2-cyano-N-(4-
(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-
yl)-2-thioxothiazol-3(2H)-yl)acetamide(5c)
A solution of 4-amino-1,5-dimethyl-2-phenyl-1H-pyra-
zol-3(2H)-one (1a) or 2-(chlorophenoxy)acetohydrazide (1b)
or 2-cyanoacetohydrazide (1c) (0.01 mol) in dimethyl-
formamide (30 mL) containing potassium hydroxide (0.01
mol) and (0.01 mol) of carbon disulfide was stirred at
room temperature for 6 h. To this solution (0.01 mol) of
4-(2-chloroacetyl)-1,5-dimethyl-2-phenyl-1H-pyrazol-3
(2H)-one (2) was added, then the solution was stirred
again overnight, poured on ice and neutralized with dilute
hydrochloric acid. The precipitates formed were collected
by filtration and crystallized from ethanol to give 5a-c
respectively.
4,4’-(2-Thioxothiazole-3,4-(2H)-diyl)bis(1,5-dimethyl
*
Corresponding author.
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