A convenient route to 1,3,4-thiadiazoles, thiazolidinone, thiazoles, pyridones, coumarins, triazolo[5,1-c]triazines, and pyrazolo[5,1-c]triazines incorporating pyrazolone moiety and their use as antimicrobial agents

Article abstract of DOI:10.1080/10426500802446546

Condensation of 4-acetyl-5-methyl-2-phenyl-2,4-dihydropyrazol-3-one (1) with hydrazine derivatives (2a-d) afforded hydrazone derivatives (3a-d), which reacted with alkyl halides 4a-c to give bis(alkylthio)methylene derivatives (5a-e). Also, 3a,b reacted w

Full text of DOI:10.1080/10426500802446546

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A Convenient Route to 1,3,4-
Thiadiazoles, Thiazolidinone,
Thiazoles, Pyridones,
Coumarins, Triazolo[5,1-
c]triazines, and Pyrazolo[5,1-
c]triazines Incorporating
Pyrazolone Moiety and Their
Use as Antimicrobial Agents
Mahmoud Mohamed Abdelall a
a Chemistry Department, Faculty of Science, Al-
Azhar University, Nasr City, Cairo, Egypt
Version of record first published: 04 Sep 2009
To cite this article: Mahmoud Mohamed Abdelall (2009): A Convenient Route to
1,3,4-Thiadiazoles, Thiazolidinone, Thiazoles, Pyridones, Coumarins, Triazolo[5,1-
c]triazines, and Pyrazolo[5,1-c]triazines Incorporating Pyrazolone Moiety and
Their Use as Antimicrobial Agents, Phosphorus, Sulfur, and Silicon and the Related
Elements, 184:9, 2208-2226
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Phosphorus, Sulfur, and Silicon, 184:2208–2226, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802446546
A Convenient Route to 1,3,4-Thiadiazoles, Thiazolidinone,
Thiazoles, Pyridones, Coumarins, Triazolo[5,1-c]triazines,
and Pyrazolo[5,1-c]triazines Incorporating Pyrazolone
Moiety and Their Use as Antimicrobial Agents
Mahmoud Mohamed Abdelall
Chemistry Department, Faculty of Science, Al-Azhar University,
Nasr City, Cairo, Egypt
Condensation of 4-acetyl-5-methyl-2-phenyl-2,4-dihydropyrazol-3-one (1) with hy-
drazine derivatives (2a–d) afforded hydrazone derivatives (3a–d), which reacted
with alkyl halides 4a–c to give bis(alkylthio)methylene derivatives (5a–e). Also,
3a,b reacted with hydrazonyl halides 6a–d to give 1,3,4-thiadiazole (7a–d). Cy-
clization of 3c with ethyl bromoacetate and haloketones gave thiazolidinone and
thiazole derivatives (8, 10a,b) respectively. Treatment of hydrazone (3d) with benzy-
lidine malononitrile 13a,b gave pyridine (14a,b). In addition, cyclocondensation of
3d with phenolic aldehydes furnished coumarin derivatives (16a–c). Coupling of 3d
with heterocyclic diazonium salts gave triazol[5,1-c]triazine (20) and pyrazolo[5,1-
c]triazine (22). Some of the prepared products showed potent antimicrobial activity.
Keywords Pyrazolone; pyrazolotriazine; pyridine; thiadiazole; thiazole; triazolotriazine
INTRODUCTION
Heterocyclic compounds containing the pyrazolone1,2 moiety are known
to exhibit potent fungicidal activity,3–6 and, as a result of which, the
present study incorporates the synthesis of some new compounds hav-
ing a pyrazolone ring. It has also been noted that pyrazolone and
its derivatives possess significant fungicidal activity against the rice
blast pathogen Pyricularia oryzae and the brown leaf spot pathogen
Helminthosporium oryzae.7–12
Received 16 April 2008; accepted 2 September 2008.
Address correspondence to Mahmoud Mohamed Abdelall, Chemistry Department,
Faculty of Science, Al-Azhar University, Nasr City, Cairo, Egypt. E-mail: abdelall sci@
yahoo.com
2208

A Convenient Route Incorporating Pyrazolone Moiety
2209
RESULTS AND DISCUSSION
On the basis of the fungicidal activity of heterocyclic compounds
containing the pyrazolone1–4 moiety, it was thought of interest to
synthesize heterocyclic compounds (3–22) containing this ring system.
Condensation of 4-acetyl-5-methyl-2-phenyl-2,4-dihydropyrazol-3-one
(1)2 with hydrazine derivatives142a–d in hot ethanol afforded hydra-
zone derivatives 3a–d, which formed as hydroxyl pyrazole (enol form)
and gave characteristic colorations with alcoholic (FeCl3) solution and
were soluble in alkali. The 1H NMR of 3b revealed two singlet signals
at δ 2.43 and 2.61 ppm due to two methyl protons at the 4 and 3
positions, a singlet at 4.58 due to the methylene of benzylthio group,
in addition to aromatic protons the region 7.22–7.92 ppm and a broad
singlet signal at 11.66 ppm due to (NH and enolic OH) (Scheme 1).
SCHEME 1
Treatment of 3a,b with alkyl halides 4a–c gave the corresponding
bis alkylthio derivatives 5a,b, respectively. Also, alkylation of 3a,b
with ethylbromoacetate 4c afforded the corresponding methylthio (ben-
zylthio) ethoxycarbonylmethyl thiomethylene derivatives 5d,e respec-
tively (Scheme 2).
1H NMR spectrum for compounds 5a–e showed a broad absorption
signal corresponding to the bonded OH proton resonating at δ 14.15–
14.19 ppm.
Interaction of alkyl dithioester (3a,b) with hydrazonyl halides 6a–
d14,16 in ethanol containing triethylamine at reflux temperatures gave
4,5-dihydro-1,3,4-thiadiazoles (7a–d) (Scheme 3). The above results
showed that the formation of 7 takes place through the elimination

2210
M. M. Abdelall
SCHEME 2
SCHEME 3
of alkyl mercaptan from the cyclic intermediate (A) (Scheme 3). The
structures of 7 were deduced from their spectral data and elemental
analysis.
Compounds 7a–d are soluble in NaOH solution and give coloration
with alcoholic FeCl3. The 1H NMR spectrum for 7a exhibited three
singlet signals at δ 2.43, 2.51, and 2.63 ppm due to 3CH3 groups at
position 4, 3 and on the thiadiazole ring, and aromatic multiplets at
7.18–7.98 ppm.
The behavior of the thiocarbamoyl functional group in compound
3c towards some α-halocarbonyl reagents was investigated. Thus,
compound 3c, when treated with one equivalent of ethyl bromoac-
etate in boiling ethanol in the presence of fused sodium acetate,

A Convenient Route Incorporating Pyrazolone Moiety
2211
underwent a cyclization thus giving the thiazolidinone derivative 8.
However, 3c reacted with two moles of ethyl bromoacetate to give
N-ethoxycarbonylthiazolidinone derivative 9, which was obtained from
1
treatment of 8 with ethyl bromoacetate (Scheme 4). The H NMR of
8 revealed two singlet signals at 2.30 and 2.48 ppm due to 2CH3 at
position 4, 3 and one singlet at 3.66 ppm due to CH2 of thiazolidinone,
in addition to aromatic multiplets and NH at 7.02–8.07 and a broad
peak from OH at 13.8 ppm.
SCHEME 4
Interaction of 3c with haloketones in ethanol at reflux temperature
in the presence of fused sodium acetate afforded thiazole derivatives
10a,b, which, when subjected to coupling reaction with benzene di-
azonium chloride in ethanol/sodium acetate, gave phenylazothiazole
derivatives11a,b. The latter compounds were prepared directly from
the cyclocondensation reaction of 3c with hydrazonyl halides 6a,d in
ethanol/triethylamine under reflux (Scheme 4).
Also the reactivity of 3d towards some electrophilic reagents
was studied. Thus, condensation of 3d with aromatic aldehydes
in hot ethanol/piperidine furnished the novel acrylonitriles (12a,b)
(Scheme 5).
Treatment of the latter compounds with malononitrile in
ethanol/piperidine furnished the aminopyridine derivatives 14a,b
(Scheme 5). The IR spectrum of 14a revealed ν (NH2) at 3320, v (CN)
at 2188, and v (CO) 1660 cm−1, while the mass spectra of 14a,b showed
the corresponding molecular ion peaks at m/e 479 and 492, respectively.
Further support for the proposed structure 14 comes from their in-
dependent synthesis through the addition of acetonitrile derivative 3d

2212
M. M. Abdelall
SCHEME 5
to the activated double bond in benzylidene malononitrile derivatives
13a,b under Michael reaction conditions (identical spectral data, mp,
and mmp determinations; Scheme 5).
Treatment of 3d with salicyldehyde derivatives 15a–c in ethanol/
piperidine at reflux temperature afforded the coumarin derivatives
16a–c; in addition, 3d condensed with 2-hydroxy-1-naphthaldehyde
under the same reaction conditions to give benzo[5,6]coumarin deriva-
tive 17 (Scheme 6). The IR spectrum of 16a–c revealed characteristic
carbonyl absorptions at 1710, 1706, and 1700 cm−1, respectively. The
1H NMR of 16b revealed three singlet signals at δ 2.46, 2.65, and 4.01
ppm due to 2CH3 groups in the pyrazole ring at position 4, 3 and the
methoxy group of coumarin ring in addition to aromatic multiples at
6.64–8.01 and a broad OH peak at 14.11 ppm.
Moreover, coupling of 3d with aryldiazonium salts in ethanolic
◦
sodium acetate solution at 0 C afforded the arylhydrazone deriva-
tives 18a–c (Scheme 6). The IR spectra of 18b revealed absorption
bands at 3220, 2214, and 1690 cm−1 due to NH, CN, and CO groups,
1
respectively, and its H NMR revealed two singlet signals at 2.40 and
2.50 due to 2CH3 at position 4, 3 and one singlet signal at 3.76 due to
OCH3 aromatic multiplets at 6.96–8.00, in addition to 2NH at 10.80 and
12.09 ppm.
Coupling of 3d with the diazotized heterocyclic amines gives ex-
cellent building blocks for the synthesis of poly condensed hetero-
cyclic derivatives. Thus, coupling of 3d with 1,2,4-triazole-3-diazonium

A Convenient Route Incorporating Pyrazolone Moiety
2213
SCHEME 6
chloride gave the 1,2,4-triazolo[5,1-c]-1,2,4-triazine derivative 20 via
the nonisolable hydrazone intermediate 19 (Scheme 7).
The IR spectrum of the isolated product showed absorption bands
at (3440, 3278, 3140, and 1688 cm−1) due to (NH2, NH, and CO) func-
tional groups. Its mass spectrum showed the molecular ion peak at
(m/e = 392). A similar interaction of 3d with pyrazole-5-diazonium
chloride afforded high yields of the pyrazolo[5,1-c]-1,2,4-triazine 22 via
the nonisolable hydrazone intermediate 21 (Scheme 7).
BIOLOGICAL ACTIVITY
Compounds 8, 9, and 12b showed very high activity (IZ > 20 mm)
against Bacillus NCTC and Staphylococcus ATCC, with Citrofloxacin
as reference. This activity was expected to occur through the thiazo-
lidinone and benzylidine moieties, and be highly active with Gram-
negative bacteria. Compounds 3b,10a, and 18c showed highly active

2214
M. M. Abdelall
SCHEME 7
(IZ 15∼20 mm) against Bacillus NCTC, Staphylococcus ATCC, and Es-
cherichia coli ATCC. Compounds 5e, 5c, 14, and 20 showed moderate
activity against Bacillus NCTC, Staphylococcus, Escherichia coli, and
Pseudomonas ATCC. Compound 16c exhibited less activity with Gram-
positive bacteria. However, compounds 3d, 8, 9, 10a, 12b, and 18c
exhibited moderate activity against the fungi Candida albicans; com-
pound 20 showed less activity, and the remaining compounds showed
no inhibition zone with Candida albicans (Table I).
The high activity against Gram-negative bacteria was exerted by
compounds (10, 11, 14b) with the thiazolidinone 10, 11 and cinamoni-
trile 14b moieties and 20c with the acetonitrilehydrazone moiety. The
moderate activity against C. albicans was exhibited by compounds (10,
11, 14b) and compounds (3b, 12b) with acetonitrile and thiazole moi-
eties, respectively.
EXPERIMENTAL
All melting points are uncorrected. IR spectra (KBr) were recorded
1
on a FTIR 5300 spectrometer (ν , cm−1). The H NMR spectra were
recorded in DMSO-d6 at 300 MHz on a Varian Gemini NMR spec-
trometer (δ , ppm) using TMS as an internal standard. Mass spectra
were obtained on GC Ms-QP 1000 EX mass spectrometer at 70 eV.

A Convenient Route Incorporating Pyrazolone Moiety
2215
TABLE I Antibacterial and Antifungal Activities
Gram-
Gram-
positive
negative
Unicellular Filamentous
fungi
B. subtilis S. aureus E. coli P. aeruginosa C. albicans
fungi
A. niger
Comp. No.
3b
5c
5e
8
9
10a
12b
14a
+ + +
++
+ + +
++
++
++
++
++
++
++
−
−
−
−
−
−
−
−
−
−
−
−
−
++
++
++
−
+ + ++
+ + ++
+ + +
+ + ++
++
+ + ++ + + +
+ + + + + +
+ + +
+ + +
++
++
++
++
++
−
+ + +
++
+ + ++ + + +
+ + +
++
++
+
++
−
f16c
18c
20
+
−
−
+ + +
++
+ + + + + +
+ + +
++
++
+
++
++
Citrofloxacin
+ + ++
+ + ++ + + +
+ + +
−
(30 Mg mL−1
)
− no inhibition zone.
+ inhibition zone (5–10 mm).
++ inhibition zone (10–15 mm).
+ + + inhibition zone (15–20 mm).
+ + ++ inhibition zone (> 20 mm).
Elemental analyses were carried out by the Microanalytical Research
Center, Faculty of Science, Cairo University. 4-Acetyl-2-pyrazolin-5-
one [2], Nꢀ-[1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)ethylid-
ene]hydrazinecarbodithioic acid methyl ester, acetyl thiosemicar-
bazone 3c,15 and benzylidene malononitrile17,18 were prepared accord-
ing to the procedures reported in the literature.
Synthesis of (3b,d)
A mixture of 4-acetylpyrazolone 1 (0.01 mol) and hydrazine derivative
2b benzylhydrazinecarbodithioate or 2d cyano acetohydrazide (0.01
mol) in ethanol (50 mL) was refluxed for 1 h, then left to cool. The
product was filtered and washed with ethanol several times and finally
recrystallized from the proper solvents.
3b: Nꢀ-[1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)
ethylidene]hydrazi-necarbodithioic Acid Benzyl Ester
Yield 84%, recrystallized from benzene, yellow crystals, (mp, 181–
183◦C), IR (KBr), v = 3210 (NH), 1594 (C N) cm−1, 1H NMR (CDCl3),

2216
M. M. Abdelall
δ = 2.43 (s, 3H, CH3 at position-4), 2.61 (s, 3H, CH3 pyrazolone at
position-3), 4.58 (s, 2H, CH2), 7.22–7.92 (m, 10H, Ar), and 11.66 ppm
(br, NH), MF, (C20H20N4OS2), calculated: C, 60.58; H, 5.08; N, 14.13;
Found: C, 60.56; H, 5.00; N, 14.11.
3d: Cyanoacetic Acid [1-(5-Hydroxy-3-methyl-1-phenyl-1H-
pyrazol-4-yl)-ethylidene]hydrazide
Yield 78%, recrystallized from ethanol, pale yellow crystals, (mp,
218–220◦C), IR (KBr), v = 3222 (NH), 3058 (CH-Ar), 2918 (CH-Al),
1
2220 (CN), 1656 (CO) cm−1, H NMR (DMSO-d6)δ = 2.34 (s,3H,CH3
at position-4), 2.37 (s, 3H, CH3 pyrazolone at position-3), 3.87 (s, 2H,
CH3), 7.15 (m, 1H, Ar-p-H), 7.38 (m, 2H, Ar-m-H), 7.94 (d, 2H, Ar-o-H),
and 11.08 (br,1H, NH) MF. (C14H15N5O2). Calculated: C, 60.60; H, 5.09;
N, 23.56; Found C, 60.57; H, 5.06; N, 23.55.
Synthesis of 5a–e: General Procedure
To a solution of 3a and/or 3b (0.01 mol) in ethanol (50 mL), alkylating
agent methyl iodide, benzyl chloride, ethyl bromoacetate (0.01 mol), and
triethylamine (0.5 mL) were added. The reaction mixture was refluxed
for 2 h, and the solid that formed was collected by filtration, washed
with ethanol, and recrystallized from the proper solvent.
5a: Yield 72 %, pale yellow crystals from ethanol, mp (195–196◦C),
1
IR (KBr) v = 3430 (OH), 2918 (CH-Al.), 1620 (C N) cm−1, H NMR
(CDCl3)δ = 2.44 (s, 3H, CH3 at position-4), 2.52 (s, 3H, CH3 pyrazolone
at position-5), 2.61 (s,3H, SCH3), 2.64 (s,3H, SCH3), 7.15 (m, 1H, Ar-p-
H), 7.36 (m, 2H, Ar-m-H), 8.01 (d, 1H, Ar-o-H), 14.18 (br, 1H, OH) MF
(C15H18N4OS2). Calculated: C, 53.87; H, 5.42; N, 16.75; Found C, 53.86;
H, 5.40; N, 16.72.
5b: Yield 73%, yellow crystals from ethanol, mp (136–138◦C), IR
(KBr), v = 3438(OH), 3020 (CH-Ar), 2916 (CH-Al), 1598 (C N) cm−1
,
1H NMR (CDCl3)δ = 2.42 (s, 3H, CH3 at position-4), 2.48 (s, 3H, CH3
of pyrazolone at position-3), 4.25 (s, 2H, SCH2), 4.30 (s, 2H, SCH2),
7.14–8.02 (m, 15H, Ar-H) and 14.15 (br, H, OH), MF ( C26H26N4OS2).
Calculated: C, 66.64; H, 5.39; N, 11.51, Found: C, 66.62; H, 5.36; N,
11.50.
5c: Yield 73%, yellow crystals from benzene (mp 146–148◦C), IR
(KBr) v = 3428 (OH), 2924 (CH-Al.), 1616 (C N) cm−1
,
1H NMR
(CDCl3)δ = 2.41 (s, 3H, CH3 at position-4), 2.45 (s, 3H, CH3 pyrazolone
at position-3), 2.53 (s,3H, SCH3), 4.31 (s,2H, CH2), 7.13–8.02 (m, 10H,
Ar-H), 14.19 (br, 1H, OH), MF (C21H22N4OS2). Calculated C, 61.43; H,
5.40; N, 13.65; Found C, 61.40; H, 5.37; N, 13.64.

A Convenient Route Incorporating Pyrazolone Moiety
2217
5d: Yield 68%, pale yellow crystals from ethanol (mp 147–149◦C),
IR (KBr) v = 2502 (OH) 2980 (CH-Al), 1730 (CO ester group), 1618
1
(C N) cm−1, H NMR (CDCl3)δ = 1.29 (t, 3H, CH3CH2), 2.42 (s,3H,
CH3 at position-4), 2.55 (s, 3H, CH3 of pyrazolone at position-3), 2.66
(s, 3H, SCH3), 3.81 (s, 2H, SCH2), 4.23 (q, 2H, CH3-CH2), 7.15 (m, 1H,
Ar-p-H), 7.37 (m, 2H, Ar-m-H), 7.98 (d, 2H, Ar-o-H), 14.17 (br, 1H, NH),
MF (C18H22N4O3S2). Calculated: C, 53.18; H, 5.45; N, 13.78, Found: C,
53.16; H, 5.42; N, 13.75.
5e: Yield 70%, yellow crystals from ethanol, mp (140–142◦C), IR
(KBr) v = 3410 (OH), 3050 (CH-Ar), 2912 (CH-Al.), 1726 (CO of es-
1
ter group), 1590 (C N) cm−1, H NMR (CDCl3)δ = 1.29 (t, 3H, CH3-
CH2), 2.42 (s, 3H, CH3 at position-4), 2.43 (s, 3H, CH3 of pyrazolone
at position-3), 3.75 (s, 2H,SCH2), 4.23 (q, 2H, CH3-CH2), 4.34 (s,
2H, SCH2), 7.12–8.02 (m, 10H, Ar-H) and 14.18 (br, 1H, OH), MF
(C24H26N4O3S2). Calculated: C, 59.73; H, 5.43; N, 11.61, Found: C,
59.70; H, 5.41; N, 11.60.
Synthesis of 1,3,4-Thiadiazole (7a–d)
To a mixture of 3a,b (0.01 mol) and appropriate hydrazonyl halide 6a–d
(0.01 mol) in ethanol (50 mL), triethylamine (0.5 mL) was added, and
the reaction mixture was refluxed for 2 h. The resulting product was
collected by filtration and recrystallized from the proper solvent.
7a: 1-(5-{[1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)
ethylidene]hydra-zono}-4-phenyl-4,5-dihydro[1,3,4]thiadiazol-
2-yl)ethanone
Yield 74%, orange crystals, recrystallized from a mixture of
ethanol/benzene, mp 249–251◦C, IR (KBr), v = 3100 (CH-Ar.), 2924
(CH-Al), 1682 (CO of acetyl group) cm−1, 1H NMR (CDCl3) 2.43 (s, 3H,
CH3 at position-4), 2.51 (s, 3H, CH3 of pyrazolone at position-3), 2.63 (s,
3H, CH3CO), 7.18-7.98 (m, 10H, Ar-H), MF (C22H20N6O2S). Calculated:
C, 61.10; H, 4.66; N, 19.43, Found: C, 61.09; H, 4.64; N, 19.41.
7b: 5-{[1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)
ethylidene]hydra-zono}-4-o-tolyl-4,5-dihydro[1,3,4]thiadiazole-
2-carboxylic Acid Ethyl Ester
Yield 69%, yellow crystals, recrystallized from benzene, mp 196–
198◦C, IR (KBr), v = 3362 (OH), 3050 (CH-Ar), 2924 (CH-Al), 1710 (CO
1
of ester group) cm−1, H NMR (CDCl3) 1.43 (t, 3H, CH3-CH2), 2.28 (s,
3H, CH3 of o-position), 2.34 (s, 3H, CH3 at position-4), 2.39 (s, 3H, CH3
of pyrazolone at position-3), 4.48 (q, 2H, CH3-CH2), 7.16–7.98 (m, 9H,

2218
M. M. Abdelall
Ar-H), 13.7 (br, 1H, OH), M.F. (C24H24N6O3S), Calculated: C, 60.49; H,
5.08; N, 17.64, Found: C, 60.47; H, 5.05; N, 17.61.
7c: 4-(4-Chlorophenyl)-5-{[1-(5-hydroxy-3-methyl-1-phenyl-1H-
pyrazol-4-yl)-ethylidene]hydrazono}-4,5-dihydro[1,3,4]
thiadiazole-2-carboxylic Acid Ethyl Ester
Yield 72%, yellow crystals, recrystallized from benzene, mp 254–
256◦C, IR (KBr), v = 3090 (CH-Ar.), 2924 (CH-Al), 1742 (CO of es-
1
ter group) cm−1, H NMR 1.43 (t, 3H, CH3-CH2), 2.44 (s, 3H, CH3 at
position-4), 2.51 (s, 3H, CH3 of pyrazolone at position-3), 4.46 (q, 2H,
CH3-CH2), 7.19–7.96 (m, 9H, Ar-H), MF (C23H21ClN6O3S). Calculated:
C, 55.59; H, 4.26; N, 16.91, Found: C, 55.57; H, 4.24; N, 16.90.
7d: (5-{[1-(5-Hydroxy-3-methyl-1-phenyl-1H-pyrazol-4-
yl)ethylidene]hydra-zono}-4-phenyl-4,5-dihydro[1,3,4]
thiadiazol-2-yl)phenylmethanone
Yield 75%, red crystals, recrystallized from
a mixture of
ethanol/benzene, mp 248–250◦C, IR (KBr), v = 3060 (CH-Ar.), 2925
(CH-Al), 1625 (C N) cm−1, MS m/z, 495 (M++1), 494 (M+) for
(C26H22N6OS). Calculated: C, 65.57; H, 4.48; N, 16.99, Found: C, 65.55;
H, 4.47; N, 16.97.
Synthesis of (8)
A mixture of 3c (0.01 mol), ethyl bromoacetate (0.01 mol), and fused
sodium acetate (0.02 mol) in ethanol (50 mL) was refluxed for 1 h. The
product obtained was collected by filtration, washed with water, and
recrystallized from a mixture of DMF/EtOH to give 8 as pale yellow
◦
crystals, yield 85%, mp 320–322 C, IR (KBr), v = 3432 (OH), 3390
(NH), 3050 (CH-Ar), 2964 (CH-Al), 1620 (CO) cm−1, 1H-NMR (DMSO-
d6) 2.30 (s, 3H, CH3 at position-4), 2.48 (s, 3H, CH3 of pyrazolone at
position-3), 3.66 (s, 2H, CH2), 7.02-8.07 (m, 5H Ar-H and NH) and
13.80 (br, 1H, OH), MF (C15H15N5O2S), Calculated: C, 54.70; H, 4.59;
N, 21.26, Found: C, 54.68; H, 4.57; N, 21.24.
Synthesis of (2-{[1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-
1H-pyrazol-4-yl)-ethylidene]hydrazono}-4-oxothiazolidin-3-yl)
acetic Acid Ethyl Ester (9)
Method A: A mixture of 8 (0.01 mol), fused sodium acetate (0.02
mol), and ethyl bromoacetate (0.01 mol) in ethanol (50 mL) was

A Convenient Route Incorporating Pyrazolone Moiety
2219
refluxed for 1 h. After cooling, the solid that formed was collected
and recrystallized from ethanol to give 9 (65% yield), as pale yellow
crystals, mp 230–232◦C).
Method B: A mixture of 3c (0.01 mol), ethyl bromoacetate (0.02 mol),
and fused sodium acetate (0.02 mol) in ethanol (50 mL) was refluxed for
2 h. After cooling, the obtained product was collected and recrystallized
from benzene to give 9 (68% yield), mp, mixed mp with product from
procedure (A) gave no depression.
IR (KBr), v = 3060 (CH-Ar.), 2984 (CH-Al.), 1728 (CO of ester),
1
1620 (CO of thiazolidinone) cm−1, H-NMR (CDCl3) 1.31 (t, 3H, CH3-
CH2), 2.43 (s, 3H, CH3 at position-4), 2.50 (s, 3H, CH3 of pyrazolone at
position-3), 4.06 (s, 2H, CH2 of thiazolidinone), 4.28 (q, 2H, CH3-CH2),
4.52 (s, 2H, NCH2), 7.27 (m, 1H, Ar-p-H), 7.40 (m, 2H, Ar-m-H), 7.98
(d, 2H, Ar-o-H), MF (C19H21N5O3S), Calculated: C, 54.93; H, 5.09; N,
16.86, Found: C, 54.91; H, 5.07; N, 16.83.
Synthesis of 5-Methyl-4-{1-[(4-substituted-3H-thiazol-2-
ylidene)hydrazono]-ethyl}-2-phen-yl-2,4-dihydropyrazol-3-one
(10a,b)
A mixture of 3c (0.01 mol) and chloroacetone and/or phenacyl bromide
(0.01 mol) in ethanol (40 mL) was refluxed for 1 h. The solid product that
formed was collected by filtration and recrystallized from the proper
solvent.
10a: 5-Methyl-4-{1-[(4-methyl-3H-thiazol-2-
ylidene)hydrazono]ethyl}-2-phen-yl-2,4-dihydropyrazol-3-one
Yield 72%, red crystals, from benzene, mp (270–272◦C); IR (KBr), v =
3396 (OH), 3194 (NH), 3045 (CH-Ar.), 2960 (CH-Al.) cm−1; MS (m/z),
327 (M+ , 0.32%), 272, 231, 215 (100%) for (C16H17N5OS), Calculated:
C, 58.70; H, 5.23; N, 21.39, Found: C, 58.68; H, 5.20; N, 21.37.
10b: 5-Methyl-2-phenyl-4-{1-[(4-phenyl-3H-thiazol-2-
ylidene)hydrazono]eth-yl}-2,4-dihydropyrazol-3-one
Yield 70%, red crystals, from benzene, mp (247–250◦C), IR (KBr),
v = 3466 (OH), 3250 (NH), 3050 (CH-Ar), 2980 (CH-Al), 1H NMR
(CDCl3) 2.45 (s, 3H, CH3 at position-4), 2.67 (s, 3H, CH3 of pyrazolone
at position-5), 4.60 (br, 1H, NH), 7.17–8.51 (m, 10H, Ar-H) and 14.53
(br, 1H, OH), MF (C21H19N5OS), Calculated: C, 64.76; H, 4.92; N, 17.98,
Found: C, 64.75; H, 4.91; N, 17.97.

2220
M. M. Abdelall
Syhthesis of 5-Methyl-4-[1-(4-substituted-5-phenylazo-3H-
thiazol-2-ylidene-azo)ethyl]-2-phenyl-2,4-dihydropyrazol-3-one
(11a,b)
Method A: To a cold solution of 10a,b (0.01 mol) in ethanol containing
sodium acetate (3 g), benzene diazonium chloride (0.01 mol) was added,
[prepared by diazotization of aniline (0.012 mol) in conc. HCl (6 mL)
◦
with sodium nitrite (0.97g in 5 mL H2O) at 0 C] portion-wise over
(30 min) with constant stirring. After comp◦lete addition, the reaction
mixture was stirred for a further 1 h at 0 C. The solid product was
filtered off, washed with water, and recrystallized from a mixture of
ethanol/benzene to give 11a,b.
Method B: To a mixture of 3c (0.01 mol) and the appropriate hy-
drazonyl halide (6a,d) (0.01 mol) in ethanol (50 mL), triethylamine (0.5
mL) was added, and the reaction mixture was refluxed for 2 h. The
isolated product was collected by filtration and recrystallized to give a
product that was identical in mp, mixed mp, and spectra with 11 a,b,
respectively, which was obtained from method A.
11a: 5-Methyl-4-[1-(4-methyl-5-phenylazo-3H-thiazol-2-
ylidene-azo)ethyl]-2-phenyl-2,4-dihydropyrazol-3-one
Mp 253–255 ◦C, IR (KBr), v = 3150 (NH), 3020 (CH-Ar.), 2954 (CH-
Al.), cm−1, 1H NMR (CDCl3) 2.45 (s, 3H, CH3 at position-4), 2.67 (s, 3H,
CH3 of pyrazolone at position-5), 2.72 (s, 3H, CH3 of thiazole), 7.24–
7.98 (m, 11H, Ar-H and NH), MF (C22H21N7OS), Calculated: C, 61.23;
H, 4.91; N, 22.72, Found: C, 61.20; H, 4.90; N, 22.71.
11b: 5-Methyl-2-phenyl-4-[1-(4-phenyl-5-phenylazo-3H-thiazol-
2-ylideneazo)-ethyl]-2,4-dihydropyrazol-3-one
Mp 220–222◦C, IR (KBr), v = 3310 (OH), 3200 (NH), 3058 (CH-Ar.),
1
2980 (CH-Al.) cm−1, H NMR (CDCl3) 2.44 (s, 3H, CH3 at position-4),
2.53 (s, 3H, CH3 of pyrazolone at position-5), 7.19–8.33 (m, 11H, Ar-H
and NH), and 14.07 (br, 1H, OH) M.F. (C27H23N7OS), Calculated: C,
65.70; H, 4.70; N, 19.86, Found: C, 65.68; H, 4.69; N, 19.83.
Synthesis of 2-Cyano-3-(substituted)acrylic Acid [1-(3-Methyl-
5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)
ethylidene]hydrazide (12a,b)
To a solution of 3d (0.01 mol) in ethanol (50 mL), the appropriate aro-
matic aldehyde was added as well as a few drops of piperidine. The reac-
tion mixture was refluxed for 2 h, then allowed to cool. The precipitate

A Convenient Route Incorporating Pyrazolone Moiety
2221
that formed was filtered off, washed with ethanol, and recrystallized
from ethanol to afford the corresponding 12a,b.
12a: 2-Cyano-3-(4-methoxyphenyl)acrylic Acid [1-(3-Methyl-5-
oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylidene]hydrazide
Yield 65%, orange crystals, mp 224–226◦C, IR (KBr), v = 3400 (OH),
3350 (NH), 3050 (CH-Ar), 2952 (CH-Al), 2212 (CN) cm−1 1H NMR
,
(CDCl3), 2.46 (s, 3H, CH3 at position-4), 2.73 (s, 3H, CH3 of pyra-
zolone at position-3), 3.82 (s, 3H, CH3O), 6.87–8.04 (m, 11H, Ar-H CH
of benzylidine and NH) and 13.90 (br, 1H, OH), MF (C23H21N5O3),
Calculated: C, 66.49; H, 5.09; N, 16.86, Found: C, 66.47; H, 5.05; N,
16.83.
12b: 2-Cyano-3-(4-dimethylaminophenyl)acrylic acid
[1-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-
yl)ethylidene]hydrazide
Yield 68%, yellow crystals, mp 208–210◦C, IR (KBr), v = 3420 (NH),
3050 (CH-Ar), 2942 (CH-Al), 228 (CN) cm−1, 1H NMR (CDCl3), 2.46 (s,
3H, CH3 at position-4), 2.71 (s, 3H, CH3 of pyrazolone at position-3),
3.02 (s, 6H, N(CH3)2), and 6.62–8.02 (m, 11H, Ar-H, NH and CH of
benzylidine). MF (C24H24N6O2), Calculated: C, 67.27; H, 5.65; N, 19.61,
Found: C, 67.25; H, 5.63; N, 19.60.
Synthesis of 6-Amino-4-(4-substitutedphenyl)-1-[1-(3-methyl-
5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylideneamino]-
2-oxo-1,2-dihydropy-ridine-3,5-dicarbonitrile (14a,b)
Method A: To a solution of the appropriate 12a,b (0.01 mol) in ethanol
(40 mL), malononitrile (0.01 mol) and few drops of piperidine were
added. The reaction mixture was heated under reflux for 2 h, then
left to cool. The precipitate was collected by filtration, washed with
ethanol, and recrystallized from ethanol/DMF to give the corresponding
pyridine-2-one derivatives 14a,b.
Method B: To a solution of 3d (0.01 mol) in ethanol (40 mL), the ap-
propriate benzylidinemalononitrile (0.01 mol) and few drops of piperi-
dine were added. The reaction mixture was heated under reflux for
2 h, then left to cool to room temperature. The solid product that
formed was collected by filtration, washed with ethanol, and then
recrystallized from ethanol/DMF to give products identical in all re-
spects (mp, mixed mp, and spectra) with those 14a,b obtained from
method A.

2222
M. M. Abdelall
14a: 6-Amino-4-(4-methoxyphenyl)-1-[1-(3-methyl-5-oxo-1-
phenyl-4,5-dihy-dro-1H-pyrazol-4-yl)ethylideneamino]-2-oxo-
1,2-dihydropyridine-3,5-dicarbonitrile
Pale yellow crystals, mp >300◦C, yield 68%, IR (KBr), v = 3388,
3320 (NH2), 3030 (CH-Ar), 2918 (CH-Al), 2188 (CN), 1660 (CO) cm−1
.
MS (m/z) (M+ 479) for (C26H21N7O3), Calculated: C, 65.13; H, 4.41; N,
20.45, Found: C, 65.11; H, 4.40; N, 20.43.
14b: 6-Amino-4-(4-dimethylaminophenyl)-1-[1-(3-methyl-5-
oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylideneamino]-2-
oxo-1,2-dihydropyridine-3,5-dicarbonitrile
Yellow crystals, mp >300◦C, yield 72%, IR (KBr), v = 3390, 3250
(NH2), 3185 (CH-Ar), 2920 (CH-Al), 2204 (CN). MS (m/z) (M+ 492) for
(C27H24N8O2), Calculated: C, 65.84; H, 4.91; N, 22.75, Found: C, 65.82;
H, 4.90; N, 22.73.
Synthesis of Coumarin Derivatives 16a–c and 17
To a mixture of the appropriate salicyldehyde derivatives 15a–c and/or
2-hydroxy-1-naphthaldehyde (0.01 mol) and 3d (0.01 mol) in ethanol
(50 mL), a few drops of piperidine were added, and the reaction mixture
was heated under reflux temperature for 1 h, then left to cool at room
temperature. The obtained solid was collected by filtration and recrys-
tallized from the proper solvent to give 16a–c and 17, respectively.
16a: 2-Oxo-2H-chromene-3-carboxylic Acid [1-(3-Methyl-5-oxo-
1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylidene]hydrazide
Yield 76%, red crystals from ethanol, mp 248–250◦C), IR (KBr), v =
3430 (OH), 3346 (NH), 3100 (CH-Ar), 2975 (CH-Al), 1710 (CO of lac-
tone), 1614 (CO) cm−1, 1H NMR (CDCl3), 2.45 (s, 3H, CH3 at position-
4), 2.64 (s, 3H, CH3 of pyrazolone at position-3), 6.64–7.99 (m, 10H,
Ar-H and NH), 8.76 (s, 1H, coumarin H-4), 14.10 (br, 1H, OH), MF
(C22H18N4O4), Calculated: C, 65.66; H, 4.51; N, 13.92, Found: C, 65.63;
H, 4.50; N, 13.90.
16b: 8-Methoxy-2-oxo-2H-chromene-3-carboxylic Acid
[1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-
yl)ethylidene]hydrazide
Yield 78%, orange crystals, from benzene, mp 230–232◦C), IR (KBr),
v = 2450 (OH), 3326 (NH), 3100 (CH-Ar), 2926 (CH-Al), 1706 (CO of
1
lactone) cm−1, H NMR (CDCl3) 2.46 (s, 3H, CH3 at position-4), 2.65
(s, 3H, CH3 of pyrazolone at position-3), 4.01 (s, 3H, OCH3), 6.64–8.01

A Convenient Route Incorporating Pyrazolone Moiety
2223
(m, 9H, Ar-H and NH), 8.75 (s, 1H, coumarin H-4), and 14.11 (br, 1H,
OH), MF (C23H20N4O5), Calculated: C, 63.88; H, 4.66; N, 12.96, Found:
C, 63.87; H, 4.64; N, 12.94.
16c: 8-Ethoxy-2-oxo-2H-chromene-3-carboxylic acid
[1-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-
yl)ethylidene]hydrazide
Yield 74%, orange crystals, from ethanol, mp 240–242◦C, IR (KBr),
v = 3304 (NH), 3050 (CH-Ar), 2928 (CH-Al), 1700 (CO of lactone) cm−1
,
1H NMR (CDCl3), 1.54 (t, 3H, CH3-CH2), 2.45 (s, 3H, CH3 at position-
4), 2.62 (s, 3H, CH3 of pyrazolone at position-3), 4.23 (q, 2H, CH3-CH2),
6.70–8.00 (m, 9H, Ar-H and NH), and 8.73 (s, 1H, coumarin H-4), MF
(C24H22N4O5), Calculated: C, 64.57; H, 4.97; N, 12.55, Found: C, 64.55;
H, 4.95; N, 12.53.
17: 3-Oxo-3H-benzo[f]chromene-2-carboxylic Acid
[1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-
yl)ethylidene]hydrazide
Yield 80%, red crystals, from dioxane, mp 215–216◦C, IR (KBr), v =
3348 (NH), 3062 (CH-Ar), 2960 (CH-Al), 1708 (CO of lactone) cm−1, 1H
NMR (DMSO-d6), 2.48 (s, 3H, CH3 at position-4), 2.71 (s, 3H, CH3 of
pyrazolone), 7.14–8.64 (m, 12H, Ar-H and NH), and 9.77 (s, 1H ben-
zocoumarin H-4), MF (C26H20N4O4), Calculated: C, 69.02; H, 4.46; N,
12.38, Found: C, 69.00; H, 4.44; N, 12.36.
Synthesis of Cyano(aryl-hydrazono)acetic Acid [1-(3-Methyl-5-
oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylidene]hydrazide
(18a–c)
To a stirred solution of 3d (0.01 mol) in ethanol (50 mL) and sodium
acetate (3 g), the appropriate aryldiazonium salt (0.01 mol) was added
[prepared by diazotization of 0.01 mol of aromatic amine (0.012 mol)
in concentrated HCl (6 mL) with sodium nitrite (0.97 g) in 5mL H2O)
at 0◦C] portion wise over 30 min with constant stirring after complete
addition. The reaction mixture was stirred for a further 1 h at 0 ◦C, the
solid product was filtered off, washed with water, dried, and recrystal-
lized from the proper solvent.
18a: Cyano(phenyl-hydrazono)acetic Acid [1-(3-Methyl-5-oxo-
1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylidene]hydrazide
Yield 82%, pale yellow crystals, from ethanol/benzene, mp 271–
273◦C, IR (KBr), v = 3230 (NH), 3068 (CH-Ar), 2980 (CH-Al), 2216 (CN),

2224
M. M. Abdelall
1692 (CO)cm−1, MS 401 (M+ 56%), 402 (M++1) 14.4%, 199 (88.4), 77
(100) for (C23H18N7O2), Calculated: C, 62.83; H, 4.77; N, 24.42, Found:
C, 62.80; H, 4.75; N, 24.40.
18b: Cyano[(4-methoxyphenyl)hydrazono]acetic Acid
[1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-
yl)ethylidene]hydrazide
◦
Yield 85%, yellow crystals, from ethanol/benzene, mp 240–242 C,
IR (KBr), v = 3220 (NH), 3076 (CH-Ar), 2960 (CH-Al), 2214 (CN), 1690
1
(CO) cm−1, H NMR (DMSO-d6), 2.40 (s, 3H, CH3 at position-4), 2.50
(s, 3H, CH3 of pyrazolone), 3.76 (s, 3H, OCH3), 6.96–8.00 (m, 9H, Ar-
H), 10.80 (s, 1H, NH), 12.09 (s, 1H, NH of hydrazo), MF (C22H21N7O3),
Calculated: C, 61.24; H, 4.91; N, 22.73, Found: C, 61.22; H, 4.90; N,
22.71.
18c: Cyano-(p-tolylhydrazono)acetic Acid [1-(3-Methyl-5-oxo-1-
phenyl-4,5-dihydro-1H-pyrazol-4-yl)ethylidene]hydrazide
Yield 75%, pale yellow crystals, from ethanol/DMF, mp (262–264 ◦C),
IR (KBr), v = 3230 (NH), 3072 (CH-Ar), 2950 (CH-Al), 2216 (CN), 1690
1
(CO) cm−1, H NMR (DMSO-d6), 2.29 (s, 3H, CH3 p-substituted), 2.36
(s, 3H, CH3 at position-4), 2.43 (s, 3H, CH3 of pyrazolone), 7.13–7.99
(m, 9H, Ar-H), 10.82 (s, 1H, NH), and 12.08 (s, 1H, NH hydrazone), MF
(C22H21N7O2), Calculated: C, 63.60; H, 5.09; N, 23.60, Found: C, 63.58;
H, 5.07; N, 23.57.
Synthesis of 4-Amino[1,2,4]triazolo[5,1-c][1,2,4]triazine-3-
carboxylic Acid [1-(3-Methyl-5-oxo-1-phenyl-4,5-dihydro-1H-
pyrazol-4-yl)ethylidene]hydrazide (20) and 4-Amino-8-cyano-
7-methylsulfanylpyrazolo[5,1-c][1,2,4]triazine-3-carboxylic
Acid [1-(3-methyl-5-oxo-1-phenyl-4,5-dihydro-1H-pyrazol-4-yl)-
ethylidene]hydrazide (22)
General procedure: To a stirred cold solution of 3d (0.01 mol) in
pyridine (25 mL), the triazole and/or pyrazole diazonium salt (0.01 mol)
was added portion wise over a period of 30 min. The reaction mixture
was kept in an icebox overnight, then diluted with water. The solid that
precipitated was filtered off, washed with water, and recrystallized from
the proper solvent.
20: Yield 63%, brown crystals from DMF, mp >300◦C, IR (KBr), v =
3450, 3278, 3140 (NH2, NH), 1688 (CO), MS 393 (M++1) 23%, 392
(M+, 100%), for (C17H16N10O2), Calculated: C, 52.04; H, 4.11; N, 35.70,
Found: C, 52.02; H, 4.10; N, 35.68.

A Convenient Route Incorporating Pyrazolone Moiety
2225
22: Yield (60%), brown crystals, from ethanol/benzene, mp >300◦C),
IR (KBr), v = 3460, 3280, 3136 (NH2, NH), 2224 (CN), 1664 (CO), MS,
448 (M+, 100%), for (C20H18N9O2S), Calculated: C, 51.94; H, 3.92; N,
30.29, Found: C, 51.92; H, 3.91; N, 30.27.
ANTIMICROBIAL ACTIVITY
Most of new prepared compounds have been tested for their antimi-
crobial using citrofloxacin (30 µg mL−1) as a reference compound. The
compounds were tested against Gram-positive bacteria (Bacillus sub-
tilis NCTC 10400, Staphylococcus aureus ATCC 25923), Gram-negative
bacteria (Escherichia coli ATCC 25922, Pseudomonas aeruginosa ATCC
10415), and fungi (Candida albicans TMRU 3669, Asperigillus nlger
ATCC 6265) by the agar diffusion technique. The tested compounds
were dissolved in N,N-dimethylformamide to obtain a solution of 1000
µ g mL−1. The bacteria and fungi cultures were maintained on nutri-
ent agar and Czapek–Dox agar media, respectively. DMF showed no
inhibition zones. The agar media were incubated with different micro-
◦
organisms. After 24 h of incubation at 30 C for bacteria and 48 h of
incubation at 28 ◦C for fungi, the diameter of inhibition zone (mm) was
measured. The minimal inhibitory concentration (MIC) of the active
compounds was measured by a twofold serial dilution method.19 The
results are illustrated in Table I.
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M. M. Abdelall
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