Reactions of hydrazonoyl halides 541: Synthesis and reactivity of 3-aza-2-bromo-1-(3-oxo benzo[f]chromen-2-yl-3-(arylamino)prop-2-en-1-one

Article abstract of DOI:10.1080/10426500701521548

2-(5-imino-4-aryl-4,5-dihydro-[1,3,4]-thiadiazole-2-(carbonyl)benzo[f] chro-men-2-one, 2-(2-amino-5-arylazothiazol-4-yl)benzo[f]chromen-3-one and ethyl 6-methyl-3-oxo-benzo [f]chromen-2-yl)-1,4-dihydro-[1,2,4]triazolo[4,3-a] pyrimidine-5-carboxy- late were synthesized from hydrazonoyl bromides. Structures of the newly synthesized compounds were established by elemental analysis, spectral data and alternative synthesis route whenever possible. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426500701521548

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Phosphorus, Sulfur, and Silicon
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Reactions of Hydrazonoyl
Halides 54: Synthesis and
Reactivity of 3-aza-2-bromo-1-
(3-oxo benzo[f]chromen-2-
yl-3-(arylamino)prop-2-en-1-
one
Abdou O. Abdelhamid a & Hassen M. Abdelaziz b
a Department of Chemistry, Faculty of Science ,
Cairo University , Giza, Egypt
b Department of Chemistry, Faculty of Science ,
Beni-Suef University , Beni-Suef, Egypt
Published online: 03 Dec 2007.
To cite this article: Abdou O. Abdelhamid & Hassen M. Abdelaziz (2007) Reactions
of Hydrazonoyl Halides 54: Synthesis and Reactivity of 3-aza-2-bromo-1-(3-oxo
benzo[f]chromen-2-yl-3-(arylamino)prop-2-en-1-one, Phosphorus, Sulfur, and Silicon
and the Related Elements, 182:12, 2791-2800, DOI: 10.1080/10426500701521548
To link to this article: http://dx.doi.org/10.1080/10426500701521548
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Phosphorus, Sulfur, and Silicon, 182:2791–2800, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701521548
Reactions of Hydrazonoyl Halides 541: Synthesis and
Reactivity of 3-aza-2-bromo-1-(3-oxobenzo[ f]chromen-2-
yl-3-(arylamino)prop-2-en-1-one
Abdou O. Abdelhamid
Department of Chemistry, Faculty of Science, Cairo University, Giza,
Egypt
Hassen M. Abdelaziz
Department of Chemistry, Faculty of Science, Beni-Suef University,
Beni-Suef, Egypt
2-(5-imino-4-aryl-4,5-dihydro-[1,3,4]-thiadiazole-2-(carbonyl)benzo[f]chro-men-2-
one, 2-(2-amino-5-arylazothiazol-4-yl)benzo[f]chromen-3-one and ethyl 6-methyl-3-
oxo-benzo [f]chromen-2-yl)-1,4-dihydro-[1,2,4]triazolo[4,3-a]pyrimidine-5-carboxy-
late were synthesized from hydrazonoyl bromides. Structures of the newly
synthesized compounds were established by elemental analysis, spectral data and
alternative synthesis route whenever possible.
Keywords
2,3-Dihydrothiadiazoles; 5-arylazothiazole; hydrazonoyl bromides;
triazolino[4,3-a]pyrimidines
INTRODUCTION
1,3,4-Thiadiazoles have activities on many biological systems
such as: antitumor,2 hypoglycemic properties,3 antihistamine,4 and
anticholinergic.5 Also, 1,2,4-Triazolo[4,3-a]pyrimidines have been
found to exhibit antiviral, antifungal, antimicrobial, herbicidal, plant
regulator, antitumor, antihypertensive, cardiovascular, and anxiolytic
activities.6 Also, hydrazonoyl halides have been widely used for the syn-
thesis of heterocyclic compounds.7−11 We report, herein, the synthesis
of some new 1,3,4-thiadiazoles, 5-arylazothiazoles, and triazolino[4,3-
a]pyridazines.
Received May 5, 2007; Accepted May 24, 2007.
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry, Faculty
of Science, Cairo University, Giza 12613, Egypt. E-mail: abdou abdelhamid@yahoo.com
2791

2792
A. O. Abdelhamid and H. M. Abdelaziz
SCHEME 1
RESULTS AND DISCUSSION
Treatmentment of 3-aza-2-bromo-1-(3-oxobenzo[f]chromen-2-yl-3-
(phenylamino)- prop-2-en-1-one12 (1a) with potassium thiocyanate in
ethanol gave analytical and spectral in accord with their formulation
2-(5-imino-4-phenyl-4,5-dihydro-[1,3,4]-thiadiazole-2-(carbonyl) benzo
[ f ]-chromen-2-one (3a). IR spectrum of 3a revealed the absence bands
at 2156 (SCN) and showed bands at 3185 (NH), 1736 and 1666 (CO’s).
1
Its HNMR spectrum showed signals at δ = 7.27–9.38 (m, 12H) and
12.44 (s, 1H) upon shaking with D2O a new signal singlet appeared at
δ = 4.55 ppm assignable to DOH proton and multiplicity signals at δ =
7.27–9.38 ppm. Such results indicate that the reaction of 1 with potas-
sium thiocyanate proceed through the hydrazone 2 which cyclized read-
ily under the reaction condition to give 3a (Scheme 1). Thus, benzene-
diazonium chloride reacted with 2-(2-thiocyanato)benzo[ f ]chromen-3-
one (4) in ethanolic sodium acetate solution at 0–5◦C, gave a product
identical in all respects (mp. mixed mp. and spectra) with 3a. Thus,
acylation of 3a with acetic anhydride or benzoyl chloride in pyridine
yielded N-acetyl or N-benzoyl derivatives 5a or 6a, respectively. Both
elemental analysis and spectral data were consistent with the assigned
structures of 5a and 6a. IR spectrum of 5a revealed bands at 1728, 1658
(CO’s), and 1627 (C N). Its 1HNMR spectrum of 5a showed signals at
δ = 2.36 (s, 3H, NCOCH3), 7.23–8.25 (m, 11H, ArH’s), and 9.16 (s, 1H,
C-4).
Similarly, treatment of the appropriate hydrazonoyl bromide 1b–
e with potassium thiocyanate, (or treatment of the appropriate

Hydrazonoyl Halides 54
2793
SCHEME 2
diazonium aromatic amine with 4 in ethanolic sodium acetate), to give
the thiadiazoline 3b–e. Also, acylation of 3b–e with acetic anhydride
and benzoyl chloride gave N-acetyl and N-benzoyl derivatives (5, 6)b–e,
respectively.
Treatment of the 1a with thiourea in boiling ethanol gave 2-(2-amino-
5-phenylazothiazol-4-yl)benzo[ f ]chromen-3-one (8a) (Scheme 2). The
structure of the product was supported by its elemental analysis, spec-
tral data, and alternative synthesis route. Thus, IR spectrum of 8a
reveled bands at 3321, 3139 (NH2), 1708 (CO), and 1612 (C N). Its
1HNMR spectrum showed signals at δ = 5.02 (s, br, 2H, NH2), 7.25–
8.00 (m, 11H, ArH’s), and 9.31 (s, 1H, C-4). Thus, 2-(2-aminothiazol-
4-yl)benzo[ f ]chromen-3-one (10), which prepared via reaction of 3-
bromoacetylbenzo[ f ]chromen-2-one (9) with thiourea, reacted with
benzenediazonium chloride in ethanol and sodium acetate as a buffer
solution at 0◦C gave product identical in all respects (m.p., mixed m.p.,
and spectra) with 8a.
Similarly treatment of the appropriate 1b–e with thiourea in boiling
ethanol gave 2-(2-amino-5-arylazothiazol-4-yl)benzo[ f ]chromen-3-one
derivatives 8b–e, respectively.
On the other hand, treatment of 1a with ethyl 6-methyl-3,4-
dihydro-4-phenylpyrimidine-5-carboxylate13 (11) in boiling chloroform
containing triethylamine under reflux gave ethyl 6-methyl-3-oxo-
benzo[ f ]chromen-2-yl)-1,4-dihydro-[1,2,4]triazolo[4,3-a]pyrimidine-
5-carboxylate (16a) in good yield (Scheme 3). The structure of the
product was supported by its elemental analysis, spectral data and
1
alternative synthesis. HNMR spectra of 16a showed signals at δ =
1.25 (t, 3H, CH3CH2O), 2.47 (s, 3H, CH3), 4.28 (q, 2H, CH3CH2O), 5.98

2794
A. O. Abdelhamid and H. M. Abdelaziz
SCHEME 3
(s, 1H, pyrimidine C-4), 7.35–8.30 (m, 14H), 8.51 (s, 1H), 8.73 (d, 1H),
9.60 (s, 1H). Thus, treatment of 1a with 17 in boiling ethanolic sodium
methoxide under reflux afforded product identical in all respects (m.p.,
mixed m.p. and spectra) with 16a.
Two possible pathways can account for the formation of 16a via 1,3-
addition of thiol toutomer of 11 to nitrilimine 12, which prepared in situ
by treatment of 1a with triethylamine, can give the thiohydrazonate
ester 13, which undergoes neucleophilic cyclization to yield spiro com-
pound 14. Alternatively, 1,3-cyloaddition of nitrilimine 12 to CS double
bond of 11 can give directly 14. The intermediate 14 gave the final
product 16a through the intermediate 15 with elimination of hydrogen
sulfide (Scheme 3).
Analogously, treatment of 1b–e with pyrmidine-2-thione derivative
11 or 15 gave triazolino[4,3-a]pyrimidine 16b–e, respectively.
EXPERIMENTAL
All melting points were determined on an electrothermal melting
point Gallen-Kamp apparatus are uncorrected. IR (cm−1) spectra were
recorded on KBr disk on a FTIR-8201 PC Schimadzu spectrophotome-
1
ter. HNMR spectra were recorded in CDCl3 or (CD3)2SO on Gemini

Hydrazonoyl Halides 54
2795
200 MHz and varian 300 MHz spectrometer using TMS as internal
reference and chemical shifts are express as δ ppm units. Mass spec-
troscopy was recorded in on a GC-MS QP 1000 EX Schimadzu. Ele-
mental analysis was performed at the Microanalytical center in Cairo
University.
Synthesis and Reactivity of 3-Aza-2-bromo-1-(3-
oxobenzo[f]chromen-2-yl-3-(arylamino)prop-2-en-1-one 1a–e
A
solution of dimethyl[3-oxo-2-(3-oxo-6,10b-dihydro-3H-benzo[ f ]
chromen-2-yl)ethyl]sulfonium (3.77g, 10 mmole)
bromide12
and the appropriate N-nitrosoarylacetamide (11 mmole) in
ethanol (30 mL) was stirred at room temperature for 3 h, left
overnight, and diluted with water. The resulting solid was col-
lected and recrystallized from ethanol to give 1a–e, respectively
(Tables I and II).
2-(5-Imino-4-aryl-4,5-dihydro-[1,3,4]-thiadiazol-2-yl)carbonyl-
3H-benzo[f]chromen-one 3a–e
Method (A)
A mixture of the appropriate 1a–e (10 mmole) and potassium thio-
cyanate (1.24g, 12 mmole) in ethanol (20 mL) was refluxed for 30 min.
The resulting solid was collected and recrystallized from dioxan to give
3a–e, respectively (Tables I and II).
Method (B)
The appropriate diazotized aromatic amines (10 mmole) were added
to a cold solution of 4 (2.95 g, 10 mmole) and sodium acetate (1.3 g,
10 mmole) in ethanol (30 mL) while stirring at 0–5◦C. The reaction
mixture was left in an ice-chest for 6 h. The resulting solid was col-
lected, washed with water, and recrystallized from dioxan to give 3a–e,
respectively.
2-(2-Thiocyantoacetyl)benzo[f]chromen-3-one (4)
A mixture of 2-(2-bromoacetyl)-6,10b-dihydro-3H-benzo[ f ]chromen-3-
one (9) (3.17 g, 10 mmole) in ethanol (20 mL) and potassium thiocyanate
(0.97g, 10 mmole) in water (5 mL) was added while stirring for about
3 h. The solid product formed was filtered off and recrystallized from
dioxan to give 4 (Tables I and II).

2796
A. O. Abdelhamid and H. M. Abdelaziz
TABLE I Characterization Data of the Newly Synthesized
Compounds
calcd./found %
Comp.
no
M.p.◦C
solvent
Color
yield %
Mol. formula
(mol. wt)
C
H
N
S
1b
1c
1d
1e
3a
3b
3c
3d
3e
4
196–97
Yellow
79%
Yellow
70%
Yellow
75%
Red
70%
Orange
85%
Orange-red
80%
Brown
75%
Red
80%
Brown
78%
Yellow
90%
Brown
78%
Brown
80%
Brown
75%
Brown
82%
Brown
70%
Brown
68%
Red
65%
Brown
69%
Brown
75%
Brown
70%
Yellow
80%
C22H15BrN2O3
435.28
60.71 3.47
60.54 3.26
58.55 3.35
58.39 3.16
6.44
6.25
6.21
6.05
6.15
5.98
9.01
8.85
—
Dioxan
191–93
Dioxan
200–202
Dioxan
184–85
Dioxan
213–15
Dioxan-EtOH
233–35
Dioxan-EtOH
228–30
Dioxan-EtOH
256–56
Dioxan
264–65
Dioxan
178–80
Dioxan
189–90
EtOH
203–205
EtOH
193–95
EtOH
220–223
EtOH
198–200
EtOH
183–85
EtOH
197–98
EtOH
180–81
EtOH
195–96
EtOH
C
22H15BrN2O4
451.28
—
—
—
C21H12BrClN2O3 55.35 2.65
455.70
21H13BrN3O5
466.25
55.24 2.47
54.10 2.59
53.95 2.47
66.15 3.28 10.52 8.03
65.99 3.15 10.46 7.89
66.81 3.66 10.16 7.76
66.67 3.48 10.03 7.58
C
C
22H13N3O3S
399.43
C23H15N3O3S
413.64
C
23H15N3O4S
429.46
64.33 3.52
64.17 3.42
9.78
9.57
9.69
9.48
7.47
7.38
7.39
7.18
C22H12ClN3O3S 60.90 2.79
433.88
22H12N4O5S
444.43
60.75 2.65
59.46 2.72 12.61 7.22
59.29 2.56 12.48 7.11
65.07 3.07
64.87 2.98
65.30 3.42
65.12 3.37
66.92 3.76
66.78 3.58
C
C
16H9NO3S
295.32
4.74 10.86
4.62 10.79
9.52
9.43
9.23
9.07
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
8a
8b
C
C
24H15N3O4S
441.47
25H17N3O4S
455.50
7.26
7.09
7.04
6.89
C25H17N3O5S
471.50
C24H14ClN3O4S 60.57 2.97
63.69 J3.63 J8.91 6.80
63.45 3.57
8.76
8.83
8.76
6.66
6.74
6.63
475.91
24H14N5O6S
486.47
60.41 2.84
59.26 2.90 11.52 6.59
59.08 2.75 11.42 6.38
69.17 3.40
69.05 3.12
69.62 3.70
69.49 3.58
67.53 3.59
67.46 3.47
C
C
C
29H17N3O4S
503.54
30H19N3O4S
517.57
8.35
8.19
8.12
8.07
7.88
7.68
7.81
7.73
6.37
6.21
6.20
6.03
6.01
5.88
5.96
5.88
C30H19N3O5S
533.57
C29H16ClN3O4S 64.74 3.00
537.99
29H16N4O6S
548.54
64.59 2.75
208–10
EtOH
228–30
EtOH
239–41
Dioxan
C
63.50 2.94 10.21 5.85
62.98 2.82 10.19 5.69
66.32 3.54 14.06 8.01
66.27 3.42 13.98 7.99
66.97 3.91 13.85 7.77
66.87 3.85 13.76 7.58
C
C
22H14N4O2S
398.45
23H16N4O2S
412.47
Yellow
85%

Hydrazonoyl Halides 54
2797
TABLE I Characterization Data of the Newly Synthesized
Compounds (Continued)
Calcd./Cound %
Comp.
no
M.p.◦C
solvent
Color
yield %
Mol. formula
(mol. wt)
C
H
N
S
8c
250–52
EtOH-H2O
>300
EtOH-DMF
>300
DMF
253–55
EtOH
233–35
EtOH
297–99
EtOH
285–87
EtOH
Yellow
90%
Yellow
85%
Red
80%
Yellow
90%
Brown
70%
Brown
65%
Red
C23H16N4O3S
428.47
64.47 3.76
64.38 3.68
61.04 3.03
60.96 3.29
59.59 2.95
59.50 2.89
65.29 3.42
65.17 3.38
72.15 4.50
72.07 4.38
72.47 4.73
72.38 4.61
70.58 4.61
70.40 4.57
68.13 4.08
68.04 4.00
66.98 4.02
66.85 3.98
13.08
13.00
12.94
12.76
15.79
15.68
9.52
9.48
9.62
9.57
9.39
9.24
9.15
9.06
9.08
8.97
11.16
11.03
7.48
7.37
7.41
7.34
7.23
7.08
10.89
10.73
—
8d
C
22H13ClN4O2S
432.89
8e
C22H13N5O4S
443.44
10
C
16H10N2O2S
443.44
16a
16b
16c
16d
16e
C
35H26N4O5
582.62
C36H28N4O5
596.65
—
—
—
—
C
36H28N4O6
612.65
65%
Brown
60%
Orange
62%
>300
EtOH
>300
Dioxan-EtOH
C35H25ClN4O5
617.07
C
35H25N5O7
627.62
3-Aryl-2-{[2-(1-aza-2-oxorylidene)-1,3,4-thiadiazolin-5-
yl]carbonyl}benzo[f]-2H-chromen-3-one 5a–e and
3-Aryl-2-aza-2{-5-[(3-oxobenzo[f]-2H-chromen-2-yl)carbonyl}-
1,3,4-thiadiazole-2-ylidene]-1-phenyl-1-one 6a–e
An appropriate of 3a–e (5 mmole) and acetic anhydride (10 mL), or ben-
zoyl chloride (0.7g, 5 mmole) in pyridine (10 mL), was heated under re-
flux for 15 min. The reaction mixture was cool and poured over crushed
ice (50g), (acidified in case of benzoylation by hydrochloric acid); then,
the crude solid was collected and recrystallized from ethanol to give
5a–e and 6a–e, respectively (Tables I and II).
2-(2-Amino-1,3-thiazol-4-yl) benzo[f]-2H- chromen-3-one (10)
A mixture of 2-(2-bromoacetyl))-6,10b-dihydrobenzo[ f ]-2H-chromen-3-
one (9) (3.17 g, 0.01 mol) and thiourea (0.76 g, 10 mmole) in ethanol
(20 mL) was refluxed for 1 h. The resulting solid was collected, washed
with boiling water containing sodium acetate and, recrystallized from
ethanol to give 10 (Tables I and II).

2798
A. O. Abdelhamid and H. M. Abdelaziz
TABLE II IR Spectra, 1HNMR Spectra, and Mass Spectra of the
Newly Synthesis Compounds
Comp. No.
Spectral data
1b
IR: 3440 (NH); 1728, 1681 (CO).
1HNMR [(CD3)2SO]: δ = 2.23 (s, 3H, CH3), 7.58–9.29 (m, 11H, ArH‘s) and
12.42 (s, 1H, NH).
IR: 3417 (NH); 1728, 1681 (CO).
1c
1HNMR [(CD3)2SO]: δ = 3.65 (s, 3H, OCH3), 7.61-9.34 (m, 11H, ArH‘s) and
12.44 (s, 1H, NH).
IR: 3425 (NH); 1728, 1681 (CO).
1d
1e
1HNMR [(CD3)2SO]: δ = 7.60- 9.32 (m, 11H, ArH‘s) and 12.43 (s, 1H, NH).
IR: 3420 (NH); 1725, 1680 (CO’s), 1519,1346 (NO2).
1HNMR [(CD3)2SO]: δ = 7.60-9.32 (m, 11H, ArH‘s) and 12.43 (s, 1H,
NH).
IR: 3185 (NH); 1736, 1666 (CO’s).
3a
3b
3c
1HNMR (CDCl3): δ = 7.27-9.38 (m, 12H, ArH‘s) and 12.44 (s, 1H).
Ms: [399] M+
IR: 3.143 (NH); 1732, 1650 (CO);
1HNMR (CDCl3): 2.54 (s, 3H, CH3); 7.02-9.51 (m, 12H, ArH‘s and NH)
Ms: [413] M+
IR: 3.158 (NH); 1739, 1604 (CO).
1HNMR (CDCl3): δ = 3.80 (s, 3H, OCH3); 6.93–9.10 ppm (m, 12H, ArH‘s
and NH).
Ms: [429] M+
IR: 3290 (NH); 1735, 1624(CO);
3d
3e
4
1HNMR (CDCl3): δ = 7.26-9.11 (m, ArH‘s and NH)
Ms: [433] M+
IR: 3398 (NH); 1735, 1624 (CO) and 1558, 1338 (NO2
δ = 7.36-9.39 (m, ArH‘s and NH)
)
1HNMR [(CD3)2SO]:
IR: 2152 (SCN); 1728, 1681 (CO).
1HNMR (CDCl3): δ = 4.72 (s, 2H, CH2) δ = 7.27 – 9.53 (m, 7H, ArH‘s) Ms:
[293] M+
5a
5b
5c
IR: 1728, 1658 (CO).
1HNMR (CDCl3): δ = 2.36 (s, 3H, N=COCH3), 7.23-8.25 (m, 11H, ArH‘s )
and 9.16 (s, 1H- C4).
IR: 1728, 1658 (CO). 1HNMR (CDCl3): δ = 2.38 (s, 3H, CH3), 2.40 (s, 3H,
N=COCH3), 7.20- 9.17 (m, 11H, ArH‘s)
IR: 1724, 1658 (CO).
1HNMR (CDCl3): δ = 2.38 (s, 3H, N=COCH3), 3.70 (s, 3H, OCH3);
7.20–9.16 (m, 11H, ArH‘s)
IR: 1724, 1658 (C=O).
6c
6e
1HNMR (CDCl3): δ = 3.70; (s, 3H, OCH3); 7.20-9.16 ppm (m, 16H, ArH‘s).
IR: 1732, 1656, 1624 (CO) and 1519, 1346 (NO2)
1HNMR (CDCl3): δ = 6.91-9.16 (m, ArH‘s)
IR: 3321, 3139 (NH2), 1708 (CO).
8a
1HNMR (CDCl3): δ = 5.02 (s, br, 2H, NH2), 7.25-8.00 (m, 11H, ArH‘s) and
9.31 (s, 1H, C-4).
IR: 3321, 3129 (NH2); 1708 (CO), 1624 (C=N).

Hydrazonoyl Halides 54
2799
TABLE II IR Spectra, 1HNMR Spectra, and Mass Spectra of the
Newly Synthesis Compounds (Continued)
Comp. No.
Spectral data
8b
1HNMR (CDCl3): δ = 2.35 (s, 3H, CH3), 5.38 (s, br, 2H, NH2); 7.25–9.31 (m,
11H, ArH‘s )
IR: 3363, 3159 (NH2); 1677 (CO), 1630 (C=N)
1HNMR (CDCl3): δ = 3.85 (s, 3H, OCH3) 5.15 (s, br, 2H, NH2), 6.96-9.65
(m,11H, ArH‘s )
8c
IR: 3440, 3286 (NH2); 1675 (CO).
8d
8e
1HNMR (CDCl3): δ = 5.54 (s, br, 2H, NH2), 7.04-8.04 (m, 11H, ArH‘s )
IR: 3325, 3286 (NH2); 1675 (CO) and 1550, 1338 (NO2) 1HNMR [(CD3)2SO]:
δ = 5.54 (s, br, 2H, NH2), 7.04-8.04 (m, 11H, ArH‘s)
IR: 3355, 3159 (NH2), 1693 (CO).
10
Ms: [294] M+
16a
IR: 3363, 3159 (NH2); 1677 (CO).
1HNMR [(CD3)2SO]: δ = 1.25 (t, 3H, CH3CH2); 2.47 (s, 3H, CH3); 4.28 (q,
2H, CH3CH2); 5.98 (s, 1H, CH); 7.35- 8.30 (m,14H, ArH‘s ), 8.51 (s, 1H),
8.73 (d, 1H), 9.60 (s, 1H).
16b
16c
IR: 1701 (CO).
1HNMR [(CD3)2SO]: δ = 1.28 (t, 3H, CH3CH2); 2.39(s, 3H, CH3); 2.46 (s, H,
CH3); 4.18 (q, 2H, CH3CH2); 5.79 (s, 1H, CH); 7.36- 9.60 (m,16H, ArH‘s )
IR: 1701 (CO).
1HNMR [(CD3)2SO]: δ = 1.28 (t, 3H, CH3CH2); 2.48 (s, 3H, CH3); ); 3.79 (s,
3H, OCH3); 4.33 (q, 2H, CH3CH2); 5.98 (s, 1H, CH); 7.61- 9.86 (m,13H,
ArH‘s), 8.51 (s, 1H) , 8.72 (d, 1H) and 9.60 (s, 1H)
IR: 1701 (CO).
16d
16e
1HNMR [(CD3)2SO]: δ = 1.28 (t, 3H, CH3CH2); 2.48 (s, 3H, CH3); 4.33 (q,
2H,CH3CH2); 5.89 (s, 1H, CH); 7.61- 9.40 (m,16H, ArH‘s)
IR: 1701 (CO).
1HNMR [(CD3)2SO]: δ = 1.05 (t, 3H, CH3CH2); 2.35 (s, 3H, CH3); ); 4.45 (q,
2H, CH3CH2); 5.98 (s, 1H, CH); 7.60- 9.49 (m, 16H, ArH‘s)
2-{2-Amino-5-aryldiazenyl-1,3-thiazol-4-
yl}benzo[f]-2H-chromen-3-one 8 a–e
Method (A)
A mixture of the appropriate hydrazonyl bromides 1a–e (10 mmole)
and thiourea (0.76 g, 10 mmole) in ethanol (20 mL) was heated under
reflux for 2 h. The resulting solid was collected and recrystallized from
the proper solvent to give 8a–e, respectively (Tables I and II).
Method (B)
An appropriate of diazotized aromatic amines (0.01mol) was added
dropwise to a solution of 10 (2.94 g, 10 mmole) and sodium acetate (1.3
g, 10 mmole) in ethanol (30 mL) at 0–5◦C for 30 min while stirring. The
reaction mixture was stirred for 6 h. The resulting solid was collected,

2800
A. O. Abdelhamid and H. M. Abdelaziz
washed with water, and recrystallized from proper solvent to give 8a–e,
respectively (Tables I and II).
Ethyl 4-aryl-6-methyl—3-(3-oxobrnzo[f]-2H-chromen-2-yl)-
4,7a-dihy-dro-7-phenyl-[1,2,4] triazolo[4,3-a]
primidine-5-carboxylate 16 a–e
Method (A)
An equimolar amounts of hydrazonyl bromides 1a–e (10 mmole)
and pyrimidne-2-thione 11 (2.76 g, 10 mmole) and triethylamine (1 g,
10 mmole) in chloroform (20 mL) was refluxed for 10 h. The reaction
mixture was evaporated under vacuum. The resulting solid was
collected and recrystallized from ethanol to give 16a–e, respectively
(Tables I and II).
Method (B)
A mixture of the appropriate hydrazonyl bromides 1a–e (10 mmole),
17 (3.01 g, 10 mmole) and sodium ethoxide (0.7 g, 10 mmole) in ethanol
(20 mL) was refluxed for 3 h. The reaction mixture was cooled and the
resulting solid was collected and recrystallized from ethanol to give
16a–e, respectively (Tables I and II).
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