Synthesis and reactions of 4-benzoyl-1,5-diaryl-1h-pyrazole-3-carbonyl chlorides with various semi- and thiosemicarbazides

Article abstract of DOI:10.1002/jhet.306

(Chemical Equation Presented) The 1H-pyrazole-3-carboxylic acids 2 were converted via reactions of their acid chlorides 3 with some semi- and thiosemicarbazide derivatives into the corresponding new phenylsemi- and thiosemicarbazides 4a-e, 6, 5-(pyrazol-3-yl)-4H-1,2,4-triazol-3-thiones 5a,b, and 2-(pyrazol-3-yl)-1,3,4-thiadiazol 7 derivatives, in good yields (45-97%, respectively). The reactions of 4a,c,e with Lawesson reagent lead to the products 6 and 7 formation. The structures of these newly synthesized compounds were determined. from the IR, ¹H- and ¹³C-NMR spectroscopic data and elemental analyses.

Full text of DOI:10.1002/jhet.306

472
Synthesis and Reactions of 4-Benzoyl-1,5-diaryl-1H-pyrazole-3-
carbonyl Chlorides with Various Semi- and Thiosemicarbazides
Vol 47
Elif Korkusuz and Ismail Yıldırım*
Department of Chemistry, Erciyes University, Kayseri 38039, Turkey
*E-mail: ismaily@erciyes.edu.tr
Received June 16, 2009
DOI 10.1002/jhet.306
Published online 23 February 2010 in Wiley InterScience (www.interscience.wiley.com).
The 1H-pyrazole-3-carboxylic acids 2 were converted via reactions of their acid chlorides 3 with
some semi- and thiosemicarbazide derivatives into the corresponding new phenylsemi- and thiosemicar-
bazides 4a–e, 6, 5-(pyrazol-3-yl)-4H-1,2,4-triazol-3-thiones 5a,b, and 2-(pyrazol-3-yl)-1,3,4-thiadiazol 7
derivatives, in good yields (45-97%, respectively). The reactions of 4a,c,e with Lawesson reagent lead
to the products 6 and 7 formation. The structures of these newly synthesized compounds were deter-
1
mined from the IR, H- and 13C-NMR spectroscopic data and elemental analyses.
J. Heterocyclic Chem., 47, 472 (2010).
INTRODUCTION
zoyl-1,5-diphenyl-1H-pyrazole-3-carboxylic acid (2a)
and -acid chloride (3a) with some semi- and thiosemicar-
bazide derivatives and to extend our investigations
related to preparing new heterocycles, which include the
pyrazole ring in their structure. Here, we report the chem-
ical behavior of 3 toward various semi- and thiosemicar-
bazides (see Scheme 1). As a result of these reactions,
new phenylsemi- and thiosemicarbazides 4a–e, 6, 5-(sub-
stituted pyrazol-3-yl)-4H-1,2,4-triazol-3-thiones 5a,b,
and 2-(substituted pyrazol-3-yl)-1,3,4-thiadiazol 7 deriva-
tives were synthesized, and their structures were identi-
fied by spectroscopic and elemental analyses.
2,3-Furandiones in general are considered as conven-
ient and versatile synthons in heterocyclic synthesis
[1,2]. A convenient method for their synthesis, the
mechanism of reactions, and semiempirical (AM1 and
PM3) and ab initio (DFT) calculations on the interaction
of 4-benzoyl-5-phenyl-2,3-dihydro-2,3-furandione (1)
with several semicarbazones, ureas, thioureas, and ani-
lides have been reported recently [3–7]. The reactions of
2,3-furandione 1 and various hydrazines or hydrazones
result in new pyrazole-3-carboxylic acids, pyrazolopyri-
dazinones, and some of their derivatives. The pyrazole
carboxylic acids can be easily transformed into the cor-
responding acid chloride, ester, or amide derivatives by
the general chemical procedures [8–13]. Pyrazole deriv-
atives are generally well-known nitrogen containing het-
erocycles, and various procedures have been developed
for their syntheses [14–17].
RESULTS AND DISCUSSION
Treatment of the yellow furandione 1 with arylhydra-
zines under reflux in benzene for 1–6 h, the correspond-
ing white coloured 1H-pyrazole-3-carboxylic acids 2 [8]
were obtained. The compounds 2 can easily be trans-
formed into the corresponding 1H-pyrazole-3-carboxylic
acid chloride 3 by usual chemical procedures [9]. Sub-
stituted 2,3-furandione 1, -acid 2 and -acid chloride 3,
which are used as an important initial materials in the
synthesis of the target heterocycles, were prepared using
the literature procedures (2b and 3b were synthesized
by us, yet) [1,8,9,15] (see Scheme 1).
Pyrazole derivatives are very important organic com-
pounds because they are widely used in pharmaceuticals
and agrochemicals. Their excellent control activities in
regard to various plant diseases are studied [18,19].
They can also be used as antifungal [20], antibacterial
[21], antimicrobial [22,23], and anti-inflammatory agents
[24–28]. The possible biological properties of the pyra-
zol, pyridazinone, pyrazolopyridazinone [29], and oxazin
derivatives make it attractive to study these compounds.
In view of these important properties, we decided
both to prove reproducibility of the reaction of 4-ben-
The compounds 3 treatment with various semi- and
thiosemi-carbazide derivatives in boiling benzene or xy-
lene gave the corresponding new structures 4,5 as main
C
V
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Synthesis and Reactions of 4-Benzoyl-1,5-Diaryl-1H-pyrazole-3-carbonyl
Chlorides with Various Semi- and Thiosemicarbazides
473
Scheme 1
such as 190.56 (t, PhCO), 159.98, 158.23 (two s,
C¼¼O), 159.50 (CAOCH3), 144.28, 143.45 (C-3, C-5),
118.40 (C-4), and 55.90 ppm (q, OCH3). Finally, the
elemental analysis data along with spectroscopic data
(details see Experimental) confirm the structure of 4b.
Interaction of the pyrazole-3-carboxylic acid chlorides
3 with some semi- and thiosemicarbazide derivatives at
reflux results in the corresponding new products 4a–e.
Surprisingly, using thiosemicarbazide in reaction with 3,
the 5-(substituted pyrazol-3-yl)-4H-1,2,4-triazol-3-thione
derivatives 5a,b were obtained exclusively. At this
point, the reaction of 3 with thiosemicarbazide in boil-
ing benzene for 4 h with no catalytic amounts of pyri-
dine or triethylamine gave the product 5a, which was
obtained in 65% yield by recrystallizing from n-butanol
(see Scheme 1). The moderate to good yield of the reac-
tion can be explained by the chemical behavior of acid
chlorides, similar to the behavior of the compound 3 to-
ward N-nucleophiles [8–13]. The formation of 5 can
easily be explained by a nucleophilic attack on the car-
bonyl group of the acid chloride 3. It appears, that this
process can be followed by elimination of a molecule of
hydrogen chloride, and finally, loss of a molecule of
water, to give 5, whose formation is confirmed by TLC
using authentic specimens of 5 and strongly supported
by the results of all analytical and spectroscopic meas-
urements. A Beilstein test did not give a green colour
for compound 5. The IR spectrum of 5a showed charac-
teristic absorption bands between 3500 and 2900 cmꢀ1
product. The progress of the reactions was monitored by
thin-layer chromatography until complete consumption
of the starting materials. The compounds 4a–e, 5a,b
were obtained in excellent yields (70–97%), except 5a
(45%), after evaporation of the organic solvents and
recrystallization from proper solvent (like methanol or
butanol, see Experimental part). The reaction of the
compound 3b with 1-phenylsemicarbazide led to the for-
mation of 4b, under reflux in xylene for 8 h, in 76%
yield without opening the pyrazole ring. To make the
reaction selective, we had to determine its parameters,
in other words, the reaction pathway, leading to such
results. The excellent yield of the reaction can be
explained by the chemical behavior of the compound 3
toward H-active nucleophiles, such as semi- and thiose-
micarbazides. It should start with a nucleophilic attack
of the nitrogen atoms’ lone pair electrons of the semi-
carbazide to the antibonding (p*) orbital at the carbonyl
carbon at C3 position of the pyrazol ring. Simultaneous
attack of the other nitrogen atoms of the semicarbazide
to the carbonyl carbon of the 3 could form some by-
products. We assume that the reaction occurs under ther-
modynamic control. The by-products formed in this way
are removed when the raw products are treated with
diethyl ether. Previously, analogs reactions have been
reported with hydrazines, ureas, diamines, aminophe-
nols, and the corresponding open chain compounds [9–
13]. In the IR spectrum of compound 4b, the ANH
absorption bands were observed between 3480 and 3300
cmꢀ1, and the C¼¼O absorption was at 1682 cmꢀ1. The
1H-NMR signals were found at d equal to 9.09 ppm (s,
1H, NH), 7.68–6.92 (m, 19H, ArH), 6.20 (b, 2H, NH2),
and 3.77 ppm (s, 3H, OCH3), and 13C NMR signals at d
1
(b, NH), and at 1662 cmꢀ1 (s, CO). The H-NMR sig-
nals were found to be at d equal to 10.49 (b, 1H, NH),
9.34 (b, 1H, NH), 7.77–7.08 ppm (m, 15H, ArH), and
the 13C-NMR signals at d such as 191.70 (t, PhC¼¼O),
159.84 (C¼¼S), 154.68–114.88 (arom. C’s), 144.27,
143.66 (C-3, C-5), and 123.08 ppm (C-4).
To examine, if that kind of chemistry can be
extended to somewhat modified systems, several
attempts to change functional groups in 4 have now
been made, e.g. transformation of carbonyl groups into
the corresponding C¼¼S-moieties using the Lawesson
reagent [2,4-bis-(4-methoxyphenyl) 1,3,2,4-dithiadiphos-
phetane-2,4-disulfide] [30–33]. According to the usual
experimental procedures applied to achieve sulfuriza-
tion of carbonyls with aid of the Lawesson reagent
(LR) [30–33], the phenylsemicarbazide derivatives 4a,
4c, or 4e and LR were refluxed in dry xylene on an oil
bath for 16 or 24 h, thus, forming a yellow solution.
After cooling, white coloured crystals (6) or yellow
needles (7) could be obtained in moderate yields (39–
20%). Surprisingly, the outcome of these experiments
did not follow the expected routes, but novel, potential,
and biologically active pyrazole derivated heterocycles
were obtained from those reactions as shown in
Scheme 2.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

474
E. Korkusuz and I. Yıldırım
Vol 47
14H, ArH), 3.86 ppm (s, 3H, OCH3); 13C-NMR (100 MHz,
CDCl3): d 183.34 (t, PhC¼¼O), 170.15 (s, COOH), 159.75
(MeOAPh), 158.75 (NAPh), 143.90, 143.12 (C-3, C-5),
139.82 (CAPh), 134.99, 134.25, 132.03, 130.51, 128.90,
128.63, 128.44, 128.13, 128.10, 127.60, 127.28, 127.25
(CAPh), 116.50 (s, C-4), 114.02, 114.00 (CAPh), 55.53 ppm
(q, OCH3). Anal. Calcd. for C24H18N2O4 (398.41): C, 72.35;
H, 4.55; N, 7.03. Found: C, 72.13; H, 4.72; N, 6.94.
Scheme 2
CONCLUSION
4-Benzoyl-5-phenyl-1-p-methoxyphenyl-1H-pyrazole-3-car-
bonyl chloride (3b). Compound 2b (0.40 g, 1 mmol) and thi-
onyl chloride (1 mL, 13.8 mmol) were refluxed on a steam bath
for 6 h. After cooling, the crude precipitate formed was filtered
off and recrystallized from xylene or toluene, yield 0.31 g
(68%), mp 177ꢁC; IR (ATR): 3060, 3013 (arom. CH), 2967–
2870 (aliph. CH), 1761, 1648 (s, CO), 1595–1454 (phenyl and
pyrazole rings C. . .C, C. . .N), 1250 cmꢀ1 (CAO); 1H-NMR (400
MHz, DMSO-d6): d 7.80–6.74 (m, 14H, ArH), 3.78 ppm (s, 3H,
OCH3). 13C-NMR (100 MHz, DMSO-d6): d 191.35 (t, J ¼ 4.4
Hz, PhCO), 162.75 (s, COCl), 159.61 (MeOAPh), 143.44,
142.58 (C-3, C-5), 138.15 (CAPh), 133.81, 132.05, 130.08,
129.59, 129.49, 129.06, 128.83, 128.30, 127.75, 127.60
(CAPh), 122.97 (s, C-4), 114.60 (CAPh), 55.90 ppm (q,
OCH3). Anal. Calcd. for C24H17N2O3Cl (416.86): C, 69.15; H,
4.11; N, 6.72. Found: C, 69.23; H, 4.29; N, 6.60.
This article reported the facile synthesis of new phe-
nylsemi- and thiosemicarbazides 4a–e, 6, 5-(substituted
pyrazol-3-yl)-4H-1,2,4-triazol-3-thiones 5a,b, and 2-
(substituted pyrazole-3-yl)-1,3,4-thiadiazol 7 derivatives
from the nucleophilic substitution or recyclization of a
pyrazole-3-carbonyl chlorides 3 with various semi- and
thiosemicarbazides. The products were easily purified
and obtained with a good yield and characterized by
spectroscopic techniques as well as microanalyses. All
newly synthesized compounds are soluble in most of or-
ganic solvents, but their limited solubility in most of
inorganic solvents could be a drawback for subsequent
applications. However, it may happen these compounds
possess interesting biological properties [18–29] that
would deserve further investigations. These functional-
ized products are amenable to further transformations,
and we anticipate that they may have important applica-
tions in medicinal and synthetic organic chemistry.
1-[(4-Benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]-1-
phenylsemicarbazide (4a). Acid chloride 3a (0.39 g, 1 mmol)
and 1-phenylsemicarbazide (0.15 g, 1 mmol) were refluxed in
xylene on an oil bath for 2 h. After cooling, the crude precipi-
tate that formed was filtered off and recrystallized from metha-
nol, yield 0.44 g (88%) of 4a, mp 232–233ꢁC; IR (KBr):
3488, 3334, 3256 (NHꢀOH and NH2), 3057 (aromatic CH),
1
1713, 1658 (s, CO), 1597–1452 cmꢀ1 (C. . .C, C. . .N); H-NMR
EXPERIMENTAL
(300 MHz, DMSO-d6): d 9.10 (s, 1H, NH), 7.58–7.10 (m,
20H, ArH), 6.19 ppm (b, 2H, NH2); 13C-NMR (75 MHz,
DMSO-d6): d 190.50 (t, J ¼ 4.3 Hz, PhCO), 159.13 (s, C¼¼O),
158.21 (C¼¼O), 155.83 (NAPh), 143.42, 142.54 (C-3, C-5),
138.95 (CAPh), 134.52, 133.18, 132.11, 131.86, 130.53,
129.59, 129.03, 128.82, 128.67, 128.56, 128.26, 126.08
(CAPh), 122.51, 119.94 ppm (C-4). Anal. Calcd. for
C30H23N5O3 (501.54): C, 71.84; H, 4.62; N, 13.96. Found: C,
72.03; H, 4.79; N, 13.64.
1-[(4-Benzoyl-5-phenyl-1-p-methoxyphenyl-1H-pyrazol-3-yl)
carbonyl]-1-phenylsemicarbazide (4b). Acid chloride 3b
(0.42 g, 1 mmol) and 1-phenylsemicarbazide (0.15 g, 1 mmol)
were refluxed in xylene on an oil bath for 8 h. After evapora-
tion, the oily residue obtained was treated with dry ether. The
crude product formed was filtered off and recrystallized from a
mixture of benzene-cyclohexane (1:3), yield 0.40 g (76%) of
4b, mp 129ꢁC; IR (ATR): 3480, 3383, 3309 (NHꢀOH and
NH2), 3065, 2912, 2849 (arom. and aliph. CH), 1682 (s br,
CO’s), 1590–1447 (C. . .C, C. . .N), 1248 cmꢀ1 (CAO); 1H-
NMR (400 MHz, DMSO-d6): d 9.09 (s, 1H, NH), 7.68–6.92
(m, 19H, ArH), 6.20 (b, 2H, NH2), 3.77 ppm (s, 3H, OCH3);
13C-NMR (100 MHz, DMSO-d6): d 190.56 (t, J ¼ 4.2 Hz,
PhCO), 159.98 (s, C¼¼O), 159.50 (MeOAPh), 158.23 (C¼¼O),
155.30 (NAPh), 144.28, 143.45 (C-3, C-5), 141.15 (CAPh),
138.17, 134.21, 132.10, 131.93, 130.55, 130.08, 129.49,
128.92, 128.76, 128.15, 127.96, 127.59, 126.79 (CAPh),
124.91, 118.40 (C-4), 116.61 (CAPh), 55.90 ppm (q, OCH3).
Anal. Calcd. for C31H25N4O4 (517.55): C, 71.94; H, 4.87; N,
10.83. Found: C, 72.03; H, 4.77; N, 10.68.
Melting points are uncorrected and recorded on Electrother-
mal 9200 digital melting point apparatus. Microanalyses were
performed on a Leco-932 CHNS-O Elemental Analyser. A
Jasco 460 Plus FTIR and a Shimadzu FTIR-8400 model spec-
trophotometers were used for IR spectra (in the range of 400–
4000 cmꢀ1 region), using KBr pellets or ATR techniques. The
1H-and 13C-NMR spectra were measured with Bruker 300
MHz and Bruker Avance III 400 MHz spectrometers and the
chemical shifts were recorded in ppm units. After completion
of the reactions, solvents were evaporated with rotary evapora-
tor (Buchi RE model 111). The reactions were followed by
TLC using DC Alufolien Kieselgel 60 F254 Merck and Camag
TLC lamp (254/366 nm). Solvents and all other chemical
reagents were purchased from Merck, Sigma, Aldrich and
Fluka and used directly without further purification. Solvents
were dried by refluxing with the appropriate drying agents and
distilled before use.
4-Benzoyl-5-phenyl-1-p-methoxyphenyl-1H-pyrazole-3-car-
boxylic acid (2b). A mixture of furandione 1 (0.28 g, 1 mmol)
and 4-methoxyphenylhydrazine hydrochloride (0.17 g,
1
mmol) was refluxed in 30 mL of dry benzene for 6 h by add-
ing 2–3 drops pyridine. After cooling, the precipitate was fil-
tered off and treated with dry ether to give a crude solid that
was recrystallized from methanol. The yield 0.25 g (63%) of
2b, mp 232ꢁC; IR (ATR): 3400–2400 (b, OH, COOH), 3065,
3030 (arom. CH), 2951–2897 (aliph. CH), 1674 (s br, CO’s),
1604–1464 (phenyl and pyrazole rings C. . .C, C. . .N), 1248
cmꢀ1 (CAO); 1H-NMR (400 MHz, CDCl3): d 7.69–6.81 (m,
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Synthesis and Reactions of 4-Benzoyl-1,5-Diaryl-1H-pyrazole-3-carbonyl
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475
mp 208ꢁC; IR (KBr): 3600–2900 cmꢀ1 (b, NH, peak max.:
3468, 3339, 3182), 3055 (arom. CH), 1662 (s, CO), 1602–
1497 (C. . .N, C. . .C), 1367 cmꢀ1 (C¼¼S); 1H-NMR (400 MHz,
DMSO-d6): d 10.49 (b, 1H, NH), 9.34 (b, 1H, NH), 7.77–7.08
ppm (m, 15H, ArH); 13C-NMR (100 MHz, DMSO-d6): d
191.70 (t, J ¼ 4.5 Hz, PhCO), 159.84 (C¼¼S), 154.68 (NAPh),
144.27, 143.66, 143.25 (C-3, C-5 or C-50 exchangeable),
140.23 (CAPh), 139.21, 138.18, 136.39, 135.24, 133.67,
132.26, 131.75, 130.41, 129.68, 129.31, 128.91, 128.27,
127.74, 125.32 (CAPh), 123.08 (C-4), 117.18, 114.88 ppm
(CAPh). Anal. Calcd. for C24H17N5OS (423.49): C, 68.07; H:
4.05; N: 16.54; S: 7.57. Found: C, 67.90; H, 4.25; N, 16.40; S.
7.30.
5-(4-Benzoyl-5-phenyl-1-p-methoxyphenyl-1H-pyrazol-3-yl)-
4H-1,2,4-triazol-3-thione (5b). Acid chloride 3b (0.50 g, 1.2
mmol) and thiosemicarbazide (0.11 g, 1.2 mmol) were refluxed
in xylene for 8 h. After cooling, the crude precipitate was fil-
tered off and recrystallized from a mixture of carbon tetra-
chloride and cyclohexane (1:3), yield 0.45 g (83%) of 5b, mp
140ꢁC; IR (ATR): 3320, 3156 (NH), 3057, 2935 (CAH), 2450
(w, tautomeric SH), 1670 (s, CO), 1598–1452 (C. . .C, C. . .N),
1362 cmꢀ1 (C¼¼S); 1H-NMR (400 MHz, DMSO-d6): d 12.58
(s, 1H, NHꢀSH), 10.36 (b, 1H, NH), 7.76–6.92 (m, 14H,
ArH), 3.76 ppm (s, 3H, OCH3); 13C-NMR (100 MHz, DMSO-
d6): d 191.30 (t, J ¼ 4.6 Hz, PhCO), 161.93 (C¼¼S), 159.81
(MeOAPh), 156.63 (NAPh), 144.07, 143.47, 142.21 (C-3, C-5
or C-50 exchangeable), 140.68 (CAPh), 138.15, 137.87,
134.73, 133.82, 132.19, 131.87, 130.32, 129.74, 129.28,
128.86, 128.33, 127.85, 126.39 (CAPh), 122.10 (C-4), 116.80,
114.60, (CAPh), 55.93 ppm (q, OCH3). Anal. Calcd. for
C25H19N5O2S (453.52): C, 66.21; H: 4.22; N: 15.44; S: 7.07.
Found: C, 66.08; H, 4.25; N, 15.15; S. 7.33.
1-[(4-Benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]-4-
phenylthiosemicarbazide (4c). Acid chloride 3a (0.30 g, 0.8
mmol) and 4-phenylthiosemicarbazide (0.13 g, 0.8 mmol)
were refluxed in benzene for 1 h. After cooling, the crude
precipitate that formed was filtered off and recrystallized
from n-butanol to give 0.27 g of 4c (68%), mp 250–251ꢁC;
IR (KBr): 3393, 3209 (NHꢀOH ve NH), 3065 (arom. CH),
2415 (w, tautomeric SH), 1674 (CO), 1610–1460 (C. . .C,
C
. . .N), 1360 cmꢀ1 (C¼¼S); 1H-NMR (400 MHz, DMSO-d6):
d 12.61 (s, 1H, NHꢀSH), 10.02 (b, 1H, NH), 9.72 (b, 1H,
NH), 7.54–6.92 ppm (m, 20H, ArH); 13C-NMR (100 MHz,
DMSO-d6): d 191.50 (t, J ¼ 4.4 Hz, PhCO), 161.63 (C¼¼S),
158.26 (C¼¼O, amide), 156.60 (NAPh), 145.17, 142.56 (C-3,
C-5 exchangeable), 140.24 (CAPh), 138.86, 137.06, 133.96,
130.46, 129.11, 128.99, 128.91, 128.60, 128.18, 127.87,
127.71, 126.13 (CAPh), 123.17 (C-4), 117.08, 116.88 ppm
(CAPh). Anal. Calcd. for C30H23N5O2S (517.60): C, 69.61;
H, 4.48; N, 13.53; S, 6.19. Found: C, 69.88; H, 4.80; N,
13.91; S, 6.00.
1-[(4-Benzoyl-5-phenyl-1-p-methoxyphenyl-1H-pyrazol-3-yl)
carbonyl]-4-phenylthiosemicarbazide (4d). Acid chloride 3b
(0.42 g, 1 mmol) and 4-phenylthiosemicarbazide (0.17 g, 1
mmol) were refluxed in xylene for 6 h. After evaporation, the
oily residue obtained was treated with dry ether. The crude
product formed was filtered off and recrystallized from n-buta-
nol to give 0.38 g of 4d (70%), mp 202ꢁC; IR (ATR): 3400–
3100 (NHꢀOH and NH), 3065, 2966, 2873 (CAH), 2450 (w,
tautomeric SH), 1674 (s br, CO’s), 1604–1475 (C. . .C, C. . .N),
1370 cmꢀ1 (C¼¼S); 1H-NMR (400 MHz, DMSO-d6): d 12.59
(s, 1H, NHꢀSH), 10.39 (b, 1H, NH), 9.96 (t, 1H, NH), 7.74–
6.92 (m, 19H, ArH), 3.76 ppm (s, 3H, OCH3); 13C-NMR (100
MHz, DMSO-d6): d 191.30 (t, J ¼ 4.2 Hz, PhCO), 160.06
(C¼¼S), 159.85 (MeOAPh), 159.61 (C¼¼O, amide), 156.62
(NAPh), 144.07, 142.19 (C-3, C-5 exchangeable), 140.68
(CAPh), 138.15, 137.63, 134.74, 133.63, 132.19, 131.03,
130.17, 129.58, 129.22, 128.85, 128.56, 128.33, 128.13,
127.85, 127.77, 126.39 (CAPh), 122.09 (C-4), 117.86, 116.88,
114.52 (CAPh), 55.90 ppm (q, OCH3). Anal. Calcd. for
C31H25N4O3S (533.62): C, 69.77; H, 4.72; N, 10.50; S, 6.01.
Found: C, 69.85; H, 4.80; N, 10.32; S, 6.14.
1-[(4-Benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]-4-
phenylsemicarbazide (4e). Acid chloride 3a (0.30 g, 0.8
mmol) and 4-phenylsemicarbazide (0.15 g, ꢂ0.8 mmol) were
refluxed in benzene for 4 h. After cooling, the crude precipi-
tate was filtered off and recrystallized from n-butanol, yield
0.40 g (97%) of 4e, mp 219ꢁC; IR (KBr): 3435, 3329
(NHꢀOH), 3060 (arom. CH), 1696, 1641 (s, CO), 1601–1478
cmꢀ1 (C. . .C, C. . .N); 1H-NMR (300 MHz, CDCl3/DMSO-d6):
d 9.79 (s, 1H, NH), 8.37 (s, 1H, NH), 7.99 (s, 1H, NH), 7.71–
6.85 ppm (m, 20H, ArH); 13C-NMR (75 MHz, CDCl3/DMSO-
d6): d 190.26 (t, J ¼ 4.3 Hz, PhCO), 159.51, 154.52
(HNC¼¼O), 143.16, 142.70 (C-3, C-5), 138.48, 137.87, 137.09,
132.21, 128.87, 128.46, 128.21, 127.88, 127.76, 127.68,
127.47, 126.96, 124.65 (CAPh), 121.37, 121.18, 117.62 ppm
(C-4). Anal. Calcd. for C30H23N5O3 (501.54): C, 71.84; H,
4.62; N, 13.96. Found: C, 71.47; H, 4.77; N, 14.21.
1-[(4-Benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)carbonyl]-1-
phenylthiosemicarbazide (6). 4a (0.50 g, 1.1 mmol) and LR
(0.54 g, 1.3 mmol) were refluxed in xylene on an oil bath for
16 h. Than the solvent was evaporated and remaining oily resi-
due was treated with dry diethyl ether to give a crude product
that was recrystallized from xylene. Yield 0.20 g (39%) of 6,
mp 263ꢁC; IR (KBr): 3600–2950, (b, NH, peak max.: 3446,
3220, 3196), 3055 (arom. CH), 1690, 1637 (CO), 1594–1472
(C. . .C, C. . .N), 1364 cmꢀ1 (C¼¼S); 1H-NMR (300 MHz,
CDCl3): d 7.80 (d, 1H, NH), 7.77 (d, 1H, NH), 7.66–6.86 (m,
20H, ArH and 1H, NH). Anal. Calcd. for C30H23N5O2S
(517.60): C, 69.61, H, 4.48, N, 13.53, S, 6.19. Found: C,
69.47, H: 4.63; N: 13.76, S: 6.04.
5-Anilino-2-(4-benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)-1,3,4-
thiadiazol (7). 4e (0.50 g, 1 mmol) and LR (0.54 g, 1.3
mmol) were refluxed in xylene on an oil bath for 24 h. Than
the solvent was evaporated and remaining oily residue was
treated with dry diethyl ether to give a crude product that was
recrystallized from xylene. Yield 0.11 g (20%) of 7, mp
323ꢁC; IR (KBr): 3196 (NH), 3058 (arom. CH), 1640 (CO),
1
1594–1491 cmꢀ1 (C. . .C, C. . .N); H-NMR (300 MHz, DMSO-
d6): d 14.27 (s, 1H, NH), 7.46–6.97 ppm (m, 20H, ArH);13C-
NMR (75 MHz, DMSO-d6): d 175.44 (t, J ¼ 4.2 Hz, PhCO),
149.00 (N¼¼CAS), 148.60 (SACANH), 141.60, 139.21,
137.65, 133.98, 131.07, 130.10, 129.93, 129.51, 129.25,
129.17, 128.84, 128.74, 128.58, 128.26, 128.08, 127.92,
126.96, 126.42, 126.06, 111.49 ppm (arom. C’s). Anal. Calcd.
for C30H21N5OS (499.59): C, 72.12; H, 4.24; N, 14.02; S,
6.42. Found: C, 72.40; H, 4.50; N, 13.80; S, 6.71.
5-(4-Benzoyl-1,5-diphenyl-1H-pyrazol-3-yl)-4H-1,2,4-tria-
zol-3-thione (5a). Acid chloride 3a (0.50 g, 1.3 mmol) and
thiosemicarbazide (0.12 g, 1.3 mmol) were refluxed in benzene
for 4 h. After cooling, the crude precipitate was filtered off
and recrystallized from n-butanol, yield 0.36 g (65%) of 5a,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

476
E. Korkusuz and I. Yıldırım
Vol 47
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Acknowledgments. The authors wish to dedicate this article to
Yunus Akc¸amur, who passed away at 2007. This study was
financially supported by Research Foundation of Erciyes
University.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet