Reactions with hydrazonoyl halides 40: Synthesis of some new 1,3,4-thiadiazoles, pyrrolo[3,4-c]pyrazoles, pyrazoles, and pyrazolo[3,4-d] pyridazines

Article abstract of DOI:10.1081/SCC-200048444

Pyrazoles, pyrazolo[3,4-d]pyridazines, pyrrolo[3,4-d]pyrazole-4,6-diones, and 2,3-dihydro-1,3,4-thiadiazoles were synthesized via reactions of hydrazonoyl bromide with each of (2E)-3-(dimethylamino)prop-2-enoyl]benzo[f]2H-chromen-3- one, N-arylmaleimides, and alkyl carbodithioates.

Full text of DOI:10.1081/SCC-200048444

This article was downloaded by: [University of Wisconsin - Madison]
On: 19 August 2013, At: 23:37
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Synthetic Communications: An
International Journal for Rapid
Communication of Synthetic
Organic Chemistry
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/lsyc20
Reactions with Hydrazonoyl
Halides 40: Synthesis of Some
New 1,3,4‐Thiadiazoles,
Pyrrolo[3,4‐c]pyrazoles,
Pyrazoles, and
Pyrazolo[3,4‐d]pyridazines
Chahid Moustapha a b , Nadia A. Abdel‐Riheem a
&
Abdou O. Abdelhamid a
a Department of Chemistry, Faculty of Science, Cairo
University, Giza, 12316, Egypt
b Department of Chemistry, University of Tichrien,
Syria
Published online: 28 Jul 2007.
To cite this article: Chahid Moustapha , Nadia A. AbdelRiheem & Abdou
O. Abdelhamid (2005) Reactions with Hydrazonoyl Halides 40: Synthesis
of Some New 1,3,4‐Thiadiazoles, Pyrrolo[3,4‐c]pyrazoles, Pyrazoles, and
Pyrazolo[3,4‐d]pyridazines, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 35:2, 249-261, DOI: 10.1081/
SCC-200048444
To link to this article: http://dx.doi.org/10.1081/SCC-200048444
PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the
information (the “Content”) contained in the publications on our platform.
However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness,
or suitability for any purpose of the Content. Any opinions and views
expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the
Content should not be relied upon and should be independently verified with
primary sources of information. Taylor and Francis shall not be liable for any
losses, actions, claims, proceedings, demands, costs, expenses, damages,
and other liabilities whatsoever or howsoever caused arising directly or
indirectly in connection with, in relation to or arising out of the use of the
Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden. Terms & Conditions of access and use can be found at
http://www.tandfonline.com/page/terms-and-conditions

Synthetic Communicationsw, 35: 249–261, 2005
Copyright # Taylor & Francis, Inc.
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1081/SCC-200048444
Reactions with Hydrazonoyl Halides 40:
Synthesis of Some New 1,3,4-Thiadiazoles,
Pyrrolo[3,4-c]pyrazoles, Pyrazoles, and
Pyrazolo[3,4-d]pyridazines
*
Chahid Moustapha, Nadia A. Abdel-Riheem, and
Abdou O. Abdelhamid
Department of Chemistry, Faculty of Science, Cairo University,
Giza, Egypt
Abstract: Pyrazoles, pyrazolo[3,4-d]pyridazines, pyrrolo[3,4-d]pyrazole-4,6-diones,
and 2,3-dihydro-1,3,4-thiadiazoles were synthesized via reactions of hydrazonoyl
bromide with each of (2E)-3-(dimethylamino)prop-2-enoyl]benzo[f]2H-chromen-3-
one, N-arylmaleimides, and alkyl carbodithioates.
Keywords: Maleimides, pyrazolo[3,4-d]pyridazines, pyrrolo[3,4-d]pyrazoles,
2,3-dihydro-1,3,4-thiadiazoles, 1,3-dipolar cycloaddition, hydrazonoyl halides
INTRODUCTION
Coumarin derivatives constitute an important class of heterocyclic compounds
with anticoagulant,[1,2] anticoagulant rodenticide,[3] insecticide,[4] and anti-
bacterial[5,6] pharmacolgical properties. On the other hand, 1,3,4-thiadiazole
derivatives have become a very useful compound in medicine, agriculture,
and in many fields of technology.[7] We report here the synthesis of some
Received in the UK January 19, 2004
*
Present address: Department of Chemistry, University of Tichrien, Syria.
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry,
Faculty of Science, Cairo University, Giza 12316, Egypt. E-mail: abdou_
abdelhamid@yahoo.com

250
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
new pyrrolo[3,4-d]pyrazoles, pyrazoles, pyrazolo[3,4-d]pyridazines, and 2,3-
dihydro-1,3,4-thiadiazoles.[8]
RESULTS AND DISCUSSION
Treatment of N-nitrosoacetanilide[9,10] with benzo[f]2H-chromen-3-oyl
methane-dimethylsulfonium bromide (3) in ethanol at room temperature
gave (2Z)-3-aza-2-bromo-1-(3-oxobenzo[f]2H-chromen-2-yl)-3(phenylami-
no)prop-2-en-1-one (6). Spectral data, microanalysis, and chemical transform-
ation confirmed its structure. Thus, compound 6 reacts with each of alkyl
carbodithioate 7a and 8a[11–13] in ethanolic triethylamine at room temperature
afforded the same isolable product (mp, mixed mp, and spectra) and
formulated as 1-f[2-((2Z)-1,2-diaza-3-phenylprop-2-enylidene)-3-phenyl-
1,3,4-thiadiazolin-5-yl)]carbonylgbenzo[f]2H-chromen-3-one (11a).
Structure 11a was confirmed by elemental analyses and spectral data.
For example, IR spectrum of 11a revealed absorption band at n ¼ 1710,
1665 cm21 (CO’s) group. Its 1H NMR spectrum showed signals at
d ¼ 7.42–8.43 (m, 17H, ArH’s and vinyl CH55) and 9.21 (s, 1H, coumarin
C-4). The formation of 11a is assumed to proceed via 1,3 addition of thiol
tautomer of carbodithioate 7a (or 8a) to nitrilum imide (generated in situ by
treatment of 6 with triethylamine) can give 9a, nucleophilic cyclization to
yield 10a. Alternatively, 1,3-cycloaddition of nitrilium imide to the C55S of
carbodithioate 7a (or 8a) can give 10a directly and then afforded 11a by
loss of alkyl mercaptane (Scheme 1).
By similar route, the appropriate 7b–g (or 8b–g) reacts with hydrazonoyl
bromide 6 in ethanolic triethylamine to give unsymmetrical azines 11b–g,
respectively (Scheme 1).
Treatment of hydrazonoyl bromide 6 with the appropriate N-aryl-
maleimide[14] 12a–c in refluxing toluene containing triethylamine yielded
2-Aryl-4-[(3-oxobenzo[f]2H-chromen-2-yl]-6-phenyl-3a,6a-dihydro-2,5,6-
triazapentalen-1,3-diones 13a–c, respectively (Scheme 2). Structure 13 was
inferred from their spectral and elemental analysis. Thus, IR spectra of 13
(a–c) revealed bands near at 1790–1720 cm21 and 1710–1690 cm21
(22CO22NR22CO) and 1665 (CO). 1H NMR (d ppm) spectrum of 13a
showed signals at d ¼ 5.15 (d, 1H), 5.87 (d, 1H), 7.05–8.61 (m, 16H,
ArH’s) and 9.36 (s, 1H, coumarin C-4). More evidence on the correct
structure 13 came from its oxidation by p-chloranil in xylene gave 5-Aryl-
3-[(3-oxobenzo[f]2H-chromen-2-yl)carbonyl]-1-phenyl-3-pyrrolino[3,4-c]-
pyrazole-4,6-diones 14a–c, respectively (Scheme 2). Structure 14 was
1
elucidated on the basis of elemental analysis and H NMR spectra. The
signals between region d ¼ 5–6 ppm disappeared in the spectra of 14a–c
due to oxidation.

Reactions with Hydrazonoyl Halides 40
251
Scheme 1.
Scheme 2.

252
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
Next, methyl carbodithioate 16, which was prepared from 2-acetylben-
zo[f]2H-chromen-3-one (1) with methyl hydrazinecarbodithioate[15,16] in
2-propanol, reacted with C-ethoxycarbonyl-N-phenylhydrazonoyl chloride
15a to afford a product 19a via elimination of methyl mercaptane
(Scheme 3). Structure 19a was elucidated on the basis of elemental analysis
and spectral data. Thus, IR spectrum of 19a revealed bands at 2939 (CH),
1
1710, 1665 (CO’s) and 1620 (C55N). Its HNMR spectrum showed signals
at d ¼ 1.43 (t, 3H, CH3CH2), 2.57 (s, 3H, CH3), 4.12 (q, 2H, CH2CH3), and
7.25–8.93 (m, 11H, ArH’s) and 9.36 (s, 1H, coumarin C-4).
Similarly, the appropriate hydrazonoyl halides 15b–d react with 16 in
ethanolic triethylamine to give the corresponding azines 19b–d, respectively.
Compounds 19b–d were confirmed on the basis of elemental analysis,
spectral data, and alternative synthesis method. Thus, compound 20[17]
reacts with compound 1 in 2-propanol to give a product identical in all
respects (mp, mixed mp, and spectra) with 19a (Scheme 3).
Scheme 3.

Reactions with Hydrazonoyl Halides 40
253
In addition, hydrazonoyl bromide 6 reacts with 5-phenyl-1,3,4-
oxadiazole-2-thione (21) in boiling chloroform containing triethylamine to
afford N-faza[5-(3-oxobenzo[f]2H-chromen-2-yl]-3-phenyl(1,3,4-thiadiazo-
lin-2-ylidene)]methylgbenzamide (24). Structure 24 was elucidated on the
basis of elemental analysis, spectral data, and alternative synthesis. 1H
NMR spectrum of 24 showed signals at d ¼ 7.05–8.37 (m, 16H, ArH’s)
and 9.70 (s, 1H, coumarin C-4), 11.21 (s, 1H, NH). Thus, reaction of hydrazo-
noyl bromide 6 with the appropriate alkyl benzoylhydrazinecarbodithioate
25 (a,b) in ethanolic triethylamine solution gave a product identical in all
respects (mp, mixed mp, and spectra) with 24 (via elimination alkyl mercap-
tane from intermediate 27) (Scheme 4).
In the light of the foregoing results, the mechanism outlined in Scheme 4
seems to be the most plausible pathway for formation of 24 from the
reaction of 6 with 21. The reaction involves initial formation of thio-
hydrazonoate 22, which undergoes intermolecular cyclization as soon as it
is formed to yield the spirothiadiazole intermediate 23 or via 1,3-dipolar
cycloaddition of nitrilum imide (which was prepared in situ from 1 with
triethylamin) to C55S double bond of 21. The formation of 22 and
23 are similar to the reaction of hydrazonoyl chloride with 5-phenyl-
1,3,4-thiadiazole-2(3H)-thione[18] and 1-phenyl-1,4-dihydrotetrazole-5-
thione.[19] Ring-chain tautomerism of the spiro intermediate 23 leads to the
end product 24.
Scheme 4.

254
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
Treatment of (2E)-3-(dimethylamino)prop-2-enoyl]benzo[f]2H-chrome-
n-3-one (28), which was prepared from compound 1 with dimethylforma-
mide-dimethylacetal in dry xylene, with 15a in refluxing toluene containing
triethylamine yielded ethyl 2-oxo-2-f3-[(3-oxobenzo[f]2H-chromen-2-yl)-
carbonyl-1-phenylpyrazol-4-ylgacetate (32a) (Scheme 5).
Structure 32 was inferred from their spectral, elemental analysis, and
1
chemical transformation. Thus, H NMR spectrum of 32a showed signals at
Scheme 5.

Reactions with Hydrazonoyl Halides 40
255
d ¼ 1.27 (t, 3H), 4.27 (q, 2H), 7.26–8.13 (m, 11H), 8.5 (s, 1H, pyrazole C-5)
and 9.22 (s, 1H, coumarin C-4). In addition, compound 32a was converted to
2-(7-hydroxy-2-phenylpyrazolo[3,4-d]pyridazin-4-yl)benzo[f]2H-chromen-
3-one (34a) by its treatment with hydrazine hydrate in boiling ethanol.
Structure 34 was elucidated on the basis of elemental analysis, spectral
data, and alternative synthesis route. 1H NMR spectrum of 34a showed
signals at d ¼ 7.33–7.62 (m, 11 H, ArH’s), 8.23 (s, 1H, pyrazole C-5), 9.22
(s, 1H, coumarin C-4), and 11.12 (s, br., 1H, NH). Compound 32d reacted
with hydrazine hydrate in boiling ethanol to give identical product in all
respects (mp, mixed mp, and spectra) with 34a. Formation of 32 can be
explained via reaction of nitrile imide 29, which formed in situ from the
appropriate hydrazonoyl halides 15a–d and triethylamine, with 28 to afford
cyclo adduct intermediate 30 or 31 and then eliminate dimethylamine to
give pyazole as final product 32 or pyrazole 33. The latter was ruled out on
the basis of the formation of pyrazolo[3,4-d]pyridazine 34. Other
pyrazolo[3,4-d]pyridazines 34b,c were obtained in a good yield from
boiling the appropriate pyrazoles 32b,c with hydrazine in boiling ethanol.
Structures 34b,c were elucidated on the basis of elemental analysis and
spectral data.
Finally, 3-f(1E)-2-aza-1-methyl-2-[(methylthiothioxomethyl]vinylg-2H-
chromen-2-one (35), which was prepared from methyl hydrazinecarbo-
dithioate with 3-acetyl-2-chromen-2-one in 2-propenol, reacted with 15a to
afford ethyl 2-[(2Z)-1,2-diaza-3-(2-oxo(2H-chromen-3-yl)but-2-enylidene]-
3-phenyl-1,3,4-thiadiazoline-5-carboxylate (36a) (Scheme 6). Structure 36a
was elucidated on the basis of elemental analysis, spectral data and alternative
Scheme 6.

256
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
1
method. H NMR spectrum of 36a showed signals at d ¼ 1.39 (t, 3H), 2.5
(s, 3H), 4.4 (q, 2H), 7.26–7.63 (m, 8H), 8.04 (s, 1H) and 8.11 (s, 1H). Its
mass spectrum revealed peaks m/z ¼ 434, 267, 207, 172, 143, 115, 102,
91, 78.
EXPERIMENTAL
All melting points were determined on an electrothermal apparatus and are
uncorrected. IR spectra were recorded (KBr discs) on a Shimadzu FT-IR
1
8201 PC spectrophotometer. H NMR spectra were recorded in CDCl3 and
(CD3)2SO solutions on a Varian Gemini 300 MHz spectrometer and
chemical shifts are expressed in d units using TMS as an internal reference.
Mass spectra were recorded on a GC-MS QP1000 EX Shimadzu. Elemental
analyses were carried out at the Microanalytical Center of the Cairo univer-
sity. Hydrazonoyl halides,[20–23] 2-acetylbenzo[f]2H-chromen-3-one,[24,25]
and 3-(2-bromoacetyl)-2H-chromen-2-one[26] were prepared as previously
reported.
2-(2-Bromoacetyl)benzo[f]2H-chromen-3-one (2)
Bromine (16 g, 5 mL, 100 mmol) was added dropwise to a solution of 2-acet-
ylbenzo[f]2H-chromen-3-one (1) (23.8 g, 100 mmol) in a mixture of dioxan-
ether (50 mL each) with stirring. The reaction mixture was poured into
ice-cold water (150 mL), and the solid was collected and crystallized from
ethanol to give 2-(2-bromoacetyl)benzo[f]2H-chromen-3-one (2) (Table 1).
Benzo[f]2H-chromen-3-oyl Methane Dimethyl Sulfonium Bromide (3)
A mixture of 2-(2-bromoacetyl)benzo[f]2H-chromen-3-one (2) (15.85 g,
50 mmol) and dimethylsulphide (3.2 g, 50 mmol) in ethanol was refluxed for
30 min. The reaction mixture was cooled and diluted with ether (50 mL) for
complete precipitation. The crude solid was collected to give 3 (Table 1).
(2Z)-3-Aza-2-bromo-1-(3-oxobenzo[f]2H-chromen-2-yl)-
3(phenylamino)prop-2-en-1-one (6)
A mixture of sulfonium bromide 3 (18.9 g, 50 mmol) and N-nitroso-N-pheny-
lacetamide (10 g, 60 mmol) in ethanol (100 mL) was stirred for 2 hr. The
yellow solid was collected and crystallized from acetic acid to give 6
(Table 1).

Reactions with Hydrazonoyl Halides 40
257
Table 1. Characterization data of the newly synthesized compounds
% Analyses, calcd./found
Compd. Mp., 8C
Yield %
colour
Mol. formula
(mol. wt.)
no.
solvent
C
H
N
S
2
168–70
AcOH
62
Yellowish
green
93
C15H9O3Br
317.1346
56.81
56.50
2.86
2.60
3
163–65
Dioxan
170–72
EtOH
C17H15O3SBr
379.269
C21H13N2O3Br 59.88
53.84
53.90
3.98
4.10
3.11
3.00
8.46
8.50
Yellow
68
6
6.65
6.50
Yellow
85
421.246
C29H18N4O3S
502.548
60.10
69.31
69.10
11a
11b
245–247
AcOH
3.61 11.15
3.50 11.30
6.38
6.50
Orange
78
224–225
AcOH
C27H16N4O3S2 63.77
63.80
3.17 11.02 12.61
3.00 11.20 12.50
Reddish
brown
78
508.576
11c
253–255
AcOH
C27H16N4O4S
492.510
65.85
65.90
3.27 11.37
3.40 11.10
6.51
6.40
Reddish
brown
78
11d
11e
11f
202–204
AcOH
C28H18N5O3S
504.543
66.66
66.80
69.76
69.60
3.59 13.88
3.40 13.70
3.90 10.84
3.80 10.90
6.36
6.40
6.21
6.10
Brown
85
240–241
AcOH
C30H20N4O3S
516.574
Brown
75
233–235
AcOH
C28H18N4O3S2 64.53
522.602
3.47 10.72 12.27
3.60 10.60 12.30
Reddish
brown
75
64.20
11g
13a
13b
13c
14a
14b
14c
16
230–231
AcOH
288–291
DMF
C28H18N4O4S
506.536
66.40
66.20
72.51
72.40
72.86
72.60
3.58 11.06
3.70 10.90
6.33
6.10
Brown
88
C31H19N3O5
513.503
3.73
3.70
4.01
4.00
3.31
3.10
3.11
3.10
3.64
3.40
2.95
2.80
4.12
4.00
8.18
8.30
7.97
8.10
7.67
7.70
6.65
6.50
8.00
7.90
7.70
7.50
Orange
88
280–282
DMF
C32H21N3O5
527.529
Brown
88
292–295
DMF
.310
C31H18N3O5Cl 67.95
Brown
65
547.949
C31H17N3O5
421.246
68.10
59.88
60.00
73.14
73.20
DMF
Black
65
295–298
DMF
.310
C32H19N3O5
525.515
Black
65
C31H16N3O5Cl 68.20
545.934 68.10
C17H14N2O2S2 59.63
342.437 59.50
C26H20N4O4S2 64.45
484.528 64.50
DMF
Black
70
232–235
AcOH
269–271
AcOH
8.18 18.73
8.20 18.60
Yellow
78
Yellow
19a
4.16 11.56
4.10 11.80
6.62
6.50
(continued)

258
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
Table 1. Continued
% Analyses, calcd./found
Compd. Mp., 8C
Yield %
colour
Mol. formula
(mol. wt.)
no.
solvent
C
H
N
S
19b
277–278
AcOH
78
Yellow
65
C25H18N4O3S
454.503
66.07
66.20
69.76
69.60
67.79
67.90
67.17
67.00
73.71
73.50
3.99 12.33
4.10 12.50
3.90 10.85
3.70 10.90
3.98 13.17
4.10 13.30
3.50 10.81
3.70 10.70
7.06
7.20
6.21
6.10
6.03
6.30
6.18
6.30
19c
19d
24
252–255
AcOH
C30H20N4O3S
516.574
Red
65
248–250
AcOH
C30H21N5O3S
531.588
Page
78
275–277
AcOH
C29H18N4O4S
518.547
Yellow
67
28
200–202
EtOH
C18H15NO3
293.297
5.15
5.00
4.78
4.80
Pale
Yellow
80
32a
32b
211–213
AcOH
C26H18N2O5
438.434
71.23
71.30
4.14
4.00
6.39
6.50
Pale
yellow
88
218–221
AcOH
C25H16N2O4
408.408
73.52
73.60
3.95
4.10
6.86
6.60
Pale
yellow
84
32c
32d
34a
205–208
AcOH
C30H18N2O4
470.479
76.59
67.70
74.22
74.10
70.93
71.10
3.85
3.60
3.94
4.00
5.95
6.10
8.66
8.50
Yellow
75
231–233
AcOH
C30H19N3O4
485.493
Yellow
82
260–263
AcOH
C24H14N4O3
406.396
3.47 13.79
3.60 13.60
Pale
Yellow
86
34b
298–300
Dioxan
C25H16N4O2
404.423
74.25
74.20
3.99 13.85
3.80 13.90
Pale
Yellow
87
34c
35
273–276
Dioxan
207–210
EtOH
C30H18N4O2 77.24
466.493 77.10
C13H12N2O2S2 53.41
3.89 12.01
3.90 12.20
Yellow
87
4.14
4.30
9.58 21.94
9.70 22.00
Orange
86
292.378
C22H18N4O4S
434.469
53.30
60.82
60.90
62.37
62.40
66.94
66.80
64.85
64.90
36a
36b
36c
36d
153–154
AcOH
4.17 12.90
4.00 13.10
3.99 13.85
4.10 13.70
3.89 12.01
4.00 11.90
3.98 14.54
4.10 14.40
7.38
7.50
7.93
8.10
6.87
6.70
6.66
6.80
Yellow
90
233–235
AcOH
C21H16N4O3S
404.444
Yellow
90
256–258
AcOH
C26H18N4O3S
466.514
Orange
86
Yellow
242–243
AcOH
C26H19N5O3S
481.528

Reactions with Hydrazonoyl Halides 40
259
2,3-Dihydro-1,3,4-thiadiazoles 11a–g, 19a–d, 24, and 36a–d
General Method
Triethylamine (0.75 mL, 5 mmol) was added dropwise with stirring to a
mixture of the appropriate alkyl carbodithioates 7a (or 8b), 16 (or 20), or
25a (or 25b) or 35 (5 mmol) and the appropriate hydrazonoyl halides 6,
15a–d (5 mmol) in ethanol (20 mL). The resulting solid, which formed after
30 min, was collected and crystallized from acetic acid to give the corres-
ponding 2,3-dihydro-1,3,4-thiadiazoles 11a–g, 19a–d, 24 and 36a–d,
respectively, in a good yield (Tables 1 and 2).
Synthesis of 2,3-Dihydrothiadiazole 24 (Alternative Synthesis Method)
Triethylamine (0.75 mL, 5 mmol) was added to boiling solution con-
taining a mixture of equimolar amount of 5-phenyl-1,3,4-oxadiazol-2-thione
21 and hydrazonoyl bromide 6 (5 mmol each) in ethanol (20 mL) and
reflux was continued for 10 hr. The solvent was evaporated under reduced
pressure, and then the residue solid was crystallized from acetic acid to give
product identical in all respect (mp, mixed mp, and spectra) with sample
obtained from previous method.
Table 2. 1H NMR spectra of some selected synthesized compounds
Compd No.
1H NMR (d)
11b
11c
11e
11f
11g
7.07–8.13 (m, 14H), 8.53 (s, 1H) and 9.18 (s, 1H).
6.51 (s, 1H), 6.83 (m, 1H), 7.25–8.26 (m, 13H) and 9.19 (s, 1H).
2.49 (s, 3H), 7.37–8.64 (m, 16H) and 9.72 (s, 1H).
2.46 (s, 3H), 7.05–8.13 (m, 14H) and 9.18 (s, 1H).
2.38 (s, 3H), 6.49 (s, 1H), 6.89 (m, 1H), 7.25–8.24 (m, 12H) and
8.20 (s, 1H).
13b
13c
2.36 (s, 3H), 5.30 (d, 1H), 5.55 (d, 1H), 7.09–7.65 (m, 12H),
7.93 (d, 1H), 8.08 (d, 1H), 8.11 (d, 1H) and 9.36 (s, 1H).
5.15 (d, 1H), 5.87 (d, 1H), 7.04–7.82 (m, 12H), 8.12 (d, 1H),
8.34 (d, 1H), 8.56 (d, 1H) and 9.36 (s, 1H).
14b
19b
28
2.36 (s, 3H), 7.07–8.11 (m, 15H) and 9.01 (s, 1H).
2.57 (s, 3H), 2.66 (s, 3H), 7.25–8.36 (m, 13 H) and 8.98 (s, 1H).
2.99 (s, 3H), 3.19 (s, 3H), 6.4 (d, 1H), 7.40–7.70 (m, 3H),
7.86–8.03 (m, 3H), 9.39 (d, 1H) and 9.42 (s, 1H).
2.67 (s, 3H), 7.28–8.07 (m, 10H), 8.33 (d, 1H), 8.44 (s, 1H) and
9.38 (s, 1H).
32b
32d
36b
7.00–8.39 (m, 16H), 8.50 (s, 1H), 9.18 (s, 1H) and 9.26 (s, 1H).
2.51 (s, 3H), 2.65 (s, 3H), 7.26-7.63 (m, 7H), 8.06 (d, 2H) and
8.14 (s, 1H).
36d
2.51 (s, 3H), 7.19–7.64 (m, 12H), 8.03 (d, 2H), 8.15 (s, 1H) and
8.50 (s, br., 1H).

260
C. Moustapha, N. A. Abdel-Riheem, and A. O. Abdelhamid
2-Aryl-4-[(3-oxobenzo[f]2H-chromen-2-yl]-6-phenyl-3a,6a-dihydro-
2,5,6-triazapentalen-1,3-diones 13a–c
Equimolar amounts of hydrazonoyl bromide 6, appropriate N-arylmaleimide
12a–c and triethylamine (5 mmol) were refluxed in dry toluene 3 hr. The
hot solution was filtered off, and the filtrate was evaporated and triturated
with petroleum ether (40–608C). The resulting solid was collected and
crystallized from acetic acid to give 13a–f, respectively (Tables 1 and 2).
5-Aryl-3-[(3-oxobenzo[f]2H-chromen-2-yl)carbonyl]-1-phenyl-3-
pyrrolino[3,4-c]-pyrazole-4,6-diones 14a–c
Equimolar amounts of the appropriate of 13a–c and p-chloranil (5 mmol) in
xylene (25 mL) was refluxed for 48 hr. The reaction mixture was cooled,
washed with sodium hydroxide (0.1 N) and then with water. The solution
was evaporated and triturated with petroleum ether (40–608C). The
resulting solid was collected and crystallized from acetic acid to give
14a–c, respectively (Tables 1 and 2).
2-f(1Z)-2-aza-1-methyl-2-
[(methylthiothioxomethyl)amino]vinylgbenzo[f]-
2H-chromen-3-one (16) and 3-f(1E)-2-aza-1-methyl-2-
[(methylthiothioxomethyl]vinylg-2H-chromen-2-one (35)
Equimolar amounts of the appropriate of 2-acetylbenzo[f]2H-chromen-3-one
or 2-acetyl-2H-chromen-2-one and methyl hydrazinecarbodithioate (5 mmol)
in 2-propanol (40 mL) were refluxed for 30 min. The reaction mixture was
cooled, and the solid formed was collected and crystallized from ethanol to
give 16 and 35, respectively (Tables 1 and 2).
(2E)-3-(Dimethylamino)prop-2-enoyl]benzo[f]2H-chromen-3-one (28)
A mixture of 2-acetylbenzo[f]2H-chromen-3-one (23.8 g, 100 mmol) and
DMF-DMA (11.9 g, 110 mmol) in dry xylene (40 mL) was refluxed for 4 hr.
The resulting solid, which formed after cooling, was collected and crystallized
from dioxan (Tables 1 and 2).
3-[(3-Substituted–1-phenylpyrazol-4-yl)carbonyl]benzo[f]2H-
chromen-3-one (32a–d)
Equimolar amounts of each the appropriate hydrazonoyl halides 15a–d, 28
and triethylamine (5 mmol) were refluxed in dry toluene (20 mL) for 3 hr.
The hot solution was filtered off, and the filtrate was evaporated and triturated
with petroleum ether (40–608C). The resulting solid was collected and
crystallized from acetic acid to give 32a–d, respectively (Tables 1 and 2).

Reactions with Hydrazonoyl Halides 40
261
2-(7-Substituted-2-phenylpyrazolo[3,4-d]pyridazin-4-yl)benzo[f]2H-
chromen-3-ones 34a–c
A mixture of the appropriate pyrazoles 32a–d (1 g) and hydrazine hydrate
(2 mL) in ethanol (20 mL) was refluxed for 2 hr. The resulting solid was
collected and crystallized to give 34a–c, respectively (Tables 1 and 2).
REFERENCES
1. Anderson, D. M.; Shelley, S.; Crick, N.; Buraglio, M. J. Clin. Pharmacol. 2002,
42, 1358.
2. Tassies, D.; Freire, C. J.; Monteagudo; Ordinas, A.; Reverter, J. C. Haematolgica
1992, 87, 1185.
3. Stone, W. B.; Okoniewski, J. C.; Stedelin, J. R. J. Wildlife Dis. 1999, 35, 187.
4. Weick, J.; Thorn, R. S. J. Econ. Entomol. 2002, 95, 227.
5. Lafitte, D.; Lamour, V.; Tsvetkov, P. O.; Makarov, A. A.; Klich, M.; Deprez, P.;
Moras, D.; Briand, C.; Gilli, R. Biochemistry 2002, 41, 7217.
6. Mitscher, L. A. Principles of Medicinal Chemistry, 5th Ed.; Foye, W. O.,
Lemke, T. L., Williams, D. A., Eds.; Williams and Wikins: Baltimore, 2002;
pp. 819–864.
7. Kornis, D. I. Comperhensive Heterocyclic Chemistry; Katritzky, A. R.,
Ress, C. W., Scriven, E. F. V., Eds.; Pergamon: Oxford, 1996; Vol. 4.
8. Abdelhamid, A. O.; Al-Atoom, A. A. Phosphorus, Sulfur, Silicon and Relat Elmnt
2004, 179, 2221.
9. Fischer, O. Chem. Ber. 1878, 9, 463.
10. Wechester, H. S. Ann. 1902, 325, 237.
11. Korosi, J. Ger. Offen. 1,934,809 29, Jan. 1970[CA: 1970, 72, 100333s].
12. Pei, S. G.; Shirodkar, P. Y. Ind. Drugs 1988, 25, 1531[CA: 1988, 109, 170166v].
13. Sandstrom, J. Arkiv Kemi. 1952, 4, 297[CA: 1952, 47, 9271].
14. Searle, N. E U.S. Pat. 2 444 536, 1948Chem. Abstr. 1948, 42, 7340.
15. Klayman, D. L.; Bartosevichm, J. F.; Griffin, T. S.; Mason, C. J.; Scovill, J. P.
J. Med. Chem. 1979, 22, 855.
16. Korosi, J. Ger. Offen. 1, 934, 899 29, Jan. 1970[Chem. Abstr. 1970, 72, 100334s].
17. Zohdi, H. F.; Rateb, N. M.; Sallam, M. M.M.; Abdelhamid, A. O. J. Chem. Res.
1998 (S), 742(M) 3329.
18. Huisgen, R.; Grashey, R.; Seidel, M.; Knupfer, H.; Schmidt, R. Liebigs Ann. Chem.
1962, 658, 169.
19. Butler, R. N.; NiBhradaigh, E. P.; Fitzgerald, K. J. J. Chem. Res. 1993 (S), 306(M)
1948.
20. Eweiss, N. F.; Osman, A. J. Heterocycl. Chem. 1980, 17, 1713.
21. Favrel, G.; Chrz, J. Bull. Soc. Chim. France 1927, 41, 1603.
22. Shawali, A. S.; Abdelhamid, A. O. Bull. Chem. Soc. Japn. 1976, 49, 321.
23. Shawali, A. S.; Osman, A. Tetrahedron 1971, 27, 2528.
24. Murthi, G. S. S.; Baska, M. J. Indian Chem. Soc. 1993, 70, 170.
25. Shockravi, A.; Shargi, H.; Valizadeh, H.; Heravic, M. M. Phosphorus, Sulfur,
Silicon and Relat Elmnt. 2002, 177, 2555.
26. Koelsch, C. F. J. Am. Chem. Soc. 1950, 72, 2993.