Reactions with hydrazonoyl halides 53:1 Synthesis and antimicrobial activity of triazolino[4,3-a]pyrimidines and 5-arylazothiazoles

Article abstract of DOI:10.1080/10426500701501292

6-(2-Naphtyl)-1-phenyl-4-3,5-disubstituted 4,3a-triazolino[4,3-a] pyrimidines, [2(1-(2-naphthyl)-5-substitued (1-pyrazolin-3-yl)-4-phenyl(thiazol- 5-yl)phenyldiazine and 1-(2-aza-2-[4-phenyldiazenyl)-(1,3-thiazol-2-yl)]amino} vinyl)-naphthalene-2-ol were

Full text of DOI:10.1080/10426500701501292

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Reactions with Hydrazonoyl
Halides 53:1 Synthesis and
Antimicrobial Activity of
Triazolino[4,3-a]pyrimidines
and 5-Arylazothiazoles
Abdou O. Abdelhamid a , Zeineb H. Ismail b , Marwa
S. El Gendy b & Moustafa M. Ghorab c
a Department of Chemistry, Faculty of Science, Cairo
University, Giza, Egypt
b Department of Chemistry, Faculty of Science (Girls
Branch), Al-Azhar University, Cairo, Egypt
c Department of Drug Radiation Research, National
Center of Radiation Research and Technology, Naser
City, Cairo, Egypt
Version of record first published: 23 Aug 2007.
To cite this article: Abdou O. Abdelhamid , Zeineb H. Ismail , Marwa S. El Gendy
& Moustafa M. Ghorab (2008): Reactions with Hydrazonoyl Halides 53:1 Synthesis
and Antimicrobial Activity of Triazolino[4,3-a]pyrimidines and 5-Arylazothiazoles,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:10, 2409-2418
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Phosphorus, Sulfur, and Silicon, 182:2409–2418, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701501292
Reactions with Hydrazonoyl Halides 53:1 Synthesis
and Antimicrobial Activity of Triazolino[4,3-a]pyrimidines
and 5-Arylazothiazoles
Abdou O. Abdelhamid
Department of Chemistry, Faculty of Science, Cairo University,
Giza, Egypt
Zeineb H. Ismail
Marwa S. El Gendy
Department of Chemistry, Faculty of Science (Girls Branch), Al-Azhar
University, Cairo, Egypt
Moustafa M. Ghorab
Department of Drug Radiation Research, National Center of Radiation
Research and Technology, Naser City, Cairo, Egypt
6-(2-Naphtyl)-1-phenyl-4-3,5-disubstituted 4,3a-triazolino[4,3-a]pyrimidines, [2-
(1-(2-naphthyl)-5-substitued
(1-pyrazolin-3-yl)-4-phenyl(thiazol-5-yl)phenyldia-
zine and 1-(2-aza-2-{[4-phenyldiazenyl)-(1,3-thiazol-2-yl)]amino}vinyl)-naphtha-
lene-2-ol were synthesized via reactions of hydrazonoyl halides with 4-(2-naphthyl)-
6-substituted 3,4-dihydropyrimidine-2-thione, Amino(3-(2-naphthyl)-5-substituted
pyrazolin-2-ylmethane-1-thione, and 2-hydroxynaphthalenecarbaldehyde-thiosem-
icarbazone. All structures of the newly synthesized compounds were elucidated
by elemental analysis, spectral data, and alternative synthesis methods whenever
possible. Some of the new compounds were tested towards bacteria. In general, all
tested compounds were capable of highly inhibiting the growth of gram positive of
bacteria and gram negative.
Keywords 2,3-Dihydro-1,3,4-thiadiazoles; arylazothiazoles; hydrazonoyl halides; pyra-
zolines; triazolino[4,3-a]pyrimidines
INTRODUCTION
1,2,4-Triazolo[4,3-a]pyrimidines have been found to exhibit antivi-
ral, antifungal, antimicrobial, herbicidal, plant regulator, antitumor,
Received March 16, 2007; accepted May 17, 2007.
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry, Faculty
of Science, Cairo University, Giza 12316, Egypt. E-mail: abdou abdelhamid@yahoo.com
2409

2410
A. O. Abdelhamid et al.
antihypertensive, cardiovascular, and anxiolytic activities.2 Also, many
interesting papers, which have appeared lately, report on func-
tionalization of thioamides and their use in organic synthesis, in-
cluding regio- and stereoselective heterocyclization reactions. In
particular, this concerns the thioamides, which have another re-
active center in the molecule and therefore may serve as conve-
nient building blocks.3 We report herein the reactivity of hydrazonoyl
halides towards 4-(2-naphthyl)-6-substituted 3,4-dihydropyrimidine-2-
thione, Amino(3-(2-naphthyl)-5-substituted pyrazolin-2-ylmethane-1-
thione and 2-hydroxynaphthalenecarbaldehydethiosemicarbazone.
RESULTS AND DISCUSSION
1-(2-Naphthyl)-3-phenylprop-2-en-1-one (3a) was reacted with thiourea
in ethanolic potassium hydroxide gave 4-(2-naphthyl)-6-phenyl-3,4-
dihydropyrimidine-2-thione (4a). Structure 4a was elucidated by ele-
1
mental analysis, spectra data, and chemical transformation. H NMR
spectrum of 4a showed signals at δ = 4.59 (s, 1H, pyrimidine), 7.06–8.88
(m, 14H, Aromatic protons and 2NH). Its MS spectrum showed peaks
at m/z = 316 [M+]. Thus, C-ethoxyycarbonyl-N-phenylhydrazonoyl
chloride was reacted with 4a in chloroform in presence of triethy-
lamine afforded ethyl 6-(2-naphtyl)-1,4-diphenyl-4,3a-triazolino[4,3-
a]pyrimidine-3-carboxylate (9a). Structure 9a was confirmed by ele-
mental analysis, spectral data and alternative synthesis (Scheme 1).
1H NMR spectrum of 9a showed signals at δ = 1.44 (t, 3H, J = 7Hz,
CH3CH2), 4.46 (q, 2H, J = 7H, CH2CH3), 4.95 (s, 1H, pyrimidine H-
4), and 7.00–8.16 (m, 18H, aromatic protons). Thus, 2-methylthio-6-(2-
naphthyl)-4-phenyl-3,4-dihydropyrimidine (11a), which prepared via
methylation of 4a with iodomethane in presence of sodium methoxide,
in boiling sodium ethoxide under reflux gave identical product (mp.,
mixed mp., and spectra) with 9a. Analogously, 4a and 4b were reacted
with the appropriate hydrazonoyl halides 5a–f in boiling chloroform
under reflux afforded triazolino[4,3-a]pyrimidines 9b–f and 10a–f, re-
spectively.
In the light of the foregoing results, the mechanism outlined in
Scheme 1 seems to be the most plausible pathway for the forma-
tion of 9 from the reaction of the hydrazonoyl halides 5 with the
dihydropyrimidine-2-thione 4. The reaction involves initial formation
of thiohydrazonates 7, which undergoes intermolecular cyclization as
soon as it is formed to give the spiro intermediate 8. Ring chain tau-
tomerism of spiro intermediate leads to the end products 9 via elimina-
tion of hydrogen sulfide (Scheme 1).

Reactions with Hydrazonoyl Halides 53
2411
SCHEME 1
Treatment of thiosemicarbazide with 1-(2-naphthyl)-3-phenylprop-
2-en-1-one (3a) to give amino(3-(2-naphthyl)-5-phenylpyrazolin-2-
ylmethane-1-thione (12a). Structure 12a was elucidated by elemen-
tal analysis, spectral data and chemical transformation (Scheme 2).
1HNMR spectrum of 12a showed signals at δ = 3.25 (dd, 1H, J = 18.1,
5.8 Hz, CH2(pyraz), 3.82 ((dd, 1H, J = 18.1, 12.2 Hz, CH2(pyraz), 5.54
((dd, 1H, J = 12.2, 5.8 Hz, CH2(pyraz), 6.82–8.10 (m, 14H, aromatic pro-
tons and NH2). 12a was reacted with C-benzoyl-N-phenylhydrazonoyl
bromide 5d, in boiling ethanolic triethylamine under reflux to af-
ford [2-(1-(2-naphthyl)-4-phenyl-(1-pyrazolin-3-yl)-4-phenyl(thiazol-5-
yl)phenyldiazine (13a). Structure 13a was confirmed by elemental
analysis, spectral data and alternative synthesis. Thus, treat-
ment of benzenediazonium chloride with 2-(1-(2-naphthyl)-4-phenyl-
(1-pyrazolin-3-yl))-4-phenylthiazole (15), which prepared via reaction
of ω-bromoacetophenone with 12a in ethanol, in pyridine gave product
identical in all respects (mp. mixed mp. and spectra) with 13a.

2412
A. O. Abdelhamid et al.
SCHEME 2
Similarly, treatment of the appropriate hydrazonoyl halides 5c,d
with the appropriate 12a,b afforded phenylazothiazoles 13b, 14a and
14b.
However,
2-hydroxynaphthalenecarbaldehydethiosemicarbazone
(17) was reacted with the appropriate hydrazonoyl halides to
give 5-aryazothiazole derivatives (Scheme 3). Compound 17 was
SCHEME 3

Reactions with Hydrazonoyl Halides 53
2413
reacted with hydrazonoyl bromide 6d in boiling ethanol containing
triethylamine under reflux to give 1-(2-aza-2-{[4-phenyldiazenyl)-
(1,3-thiazol-2-yl)]amino}vinyl)naphthalene-2-ol (18). Structure 18
was elucidated by elemental analysis, spectral data and alternative
synthesis. Thus, treatment of benzenediazonium chloride with 3-
(2-aza-2-[(4-phenylthiazol-2-yl)amino]vinyl)-naphthalin-2-ol (19) in
pyridine afforded product identical in all respects (mp., mixed mp., and
spectra) with 18a.
Biological Activity
The tested microorganisms were gram +ve bacteria [Staphylococcus
aureus(ATCC25923) and Streptococcus pyrogenes (ATCC19615)] and
gram –ve bacteria (Pseudomonas syrinage PV phasealicola). In addi-
tion, some fungal pathogens (Aspergillus niger and Fusarium oxys-
porum) were also tested. Sensitivity of the selected microorganisms
to some synthesized compounds was determined in vitro at two concen-
trations (100, 400 (mg/mL) in CHCl3. The tests were carried out using
the filter paper and hole plate method.4
Studies on the biological activity of compounds 3a, 3b, 9a, 10b, 10d,
and 11 led to the fact that these compounds have moderate biologi-
cal activity against the tested bacteria, and only weak activity against
fungi. Also, it can be observed (Table I) that compounds 12a, 14a, 16,
and 18a, have only a weak effect on bacteria. Compounds 9e, 12a, 14a,
and 17 showed weak antifungal activity but compounds 15, 16, 18a,
and 19 showed moderate antifungal activity.
EXPERIMENTAL
All melting points were determined on an electrothermal apparatus and
are uncorrected. IR spectra were recorded (KBr discs) on a Shimadzu
1
FT-IR 8201 PC spectrophotometer. H NMR spectra were recorded in
CDCl3and (CD3)2SO solutions on a Varian Gemini 300 MHz spectrom-
eter and chemical shifts are expressed in δ units using TMS as an in-
ternal reference. Mass spectra were recorded on a GC-MS QP 1000 EX
Shimadzu. Elemental analyses were carried out at the Microanalytical
Canter of the Cairo University. Hydrazonoyl halides,5−8 3a,9 and 3b10
were prepared as previously reported.
Synthesis of 4-(2-Naphthyl)-6-substituted 3,4-
Dihydropyrimidine-2-thione 4a,b
A mixture of the appropriate chalcones 3a,b (10 mmol), thiourea
(0.76 g, 10 mmol) and potassium hydroxide (10%, 5 mL) in ethanol

2414
A. O. Abdelhamid et al.
TABLE I Response of Various Microorganisms to Some
Synthesized Compounds in vitro Culture
Comp. no.
S.a.
S.p.
P.s.
A.n.
F.o.
3a
3b
9a
9e
10b
10d
11
12a
13a
13b
14a
15
16
17
18a
19
Control
M
M
—
—
W
W
—
W
W
W
—
—
W
W
W
W
S
M
M
M
W
W
W
W
W
W
W
W
W
W
W
W
W
S
W
W
—
—
M
M
M
—
M
M
W
M
W
W
—
—
S
W
W
W
W
—
W
W
—
—
—
—
—
—
—
W
W
S
W
W
W
—
W
W
W
M
W
W
W
M
M
W
M
M
S
Diameter of the zone inhibition: W: low activity (3–5 mm) (+); M:
moderate (6–15 mm) (++); S: strong activity (>15 mm)(+ + +). The
antibiotic which used as control was (Chlorumphinecol).
(20 mL) was refluxed 6 h. The resulting solid was collected and re-
crystallized from ethanol to give pyrazolines 4a and4b, respectively
(Tables II and III).
6-(2-Naphtyl)-1-phenyl-4-3,5-disubstituted 4,3a-triazolino
[4,3-a]pyrimidines 9a–f and 10a–c
Method A. A mixture of the appropriate hydrazonoyl halides 5a–f
(5 mmol), the appropriate pyrimidine-2-thione 4a,b (5 mmol) and tri-
ethylamine (0.5 g, 0.7 m mL, 5 mmol) in chloroform was boiled under
reflux 10 h. Chloroform was removed under reduced pressure then trit-
urated with petroleum ether 40–60◦C. The resulting solid was collected
and recrystallized from ethanol to give 9a–f and 10a–c, respectively
(Tables II and III).
Method B. A mixture of the appropriate hydrazonoyl halides 5a–f
(5 mmol), the appropriate 11a,b (5 mmol) and triethylamine (0.5 g,
0.7 m mL, 5 mmol) in ethanol was boiled under reflux 3 h. The solid
was collected and recrystallized from ethanol gave identical product
with corresponding from Method A.

Reactions with Hydrazonoyl Halides 53
2415
TABLE II Spectral Data of Some Newly Synthesized Compounds
Comp. no
4a
Spectral data
1H NMR: 4.59 (s, 1H, pyrimidine), 7.06–8.88 (m, 15H, Aromatic protons
and 2NH).
IR: 3442(NH) and 1544 (C S).
MS: 316 (72.7%), 313 (100%), 256(28.0%), 239(36.4%), 189(24.2%), 127
(22.0%), 77 (28.8%).
9a
9b
1H NMR: 1.44 (t, 3H, J = 7Hz, CH3CH2), 4.46 (q, 2H, J = 7H, CH2CH3),
4.59 (s, 1H, pyrimidine H-4), and 7.00–8.16 (m, 18H, aromatic protons).
IR: 3050 (CH), 1736(C O ester), and 1576 (C C).
1H NMR: 3.79 (s, 3H, OCH3); 4.86 (s, 1H, pyrimidine H-4) and 7.01–7.58
(m, 18H, ArH’s).
IR: 1704 (C O ester) and 1544 (C N).
10a
10c
11a
12a
1H NMR: 1.38 (t, 3H, CH2CH3), 5.34 (q, 2H, CH2, CH3), 4.61 (s, 1H,
pyrimidine H-4), and 7.05–8.57 (m, 16H, ArH’s).
1H NMR: 2.55 (s, 3H, CH3), 4.82(s, 1H, pyrimidine H-4), and 7.10–8.51 (m,
16 H, ArH’s).
1H NMR: 2.52 (s, 3H, SCH3), 4.86 (s, 1H, pyrimidine H–4), 7.24–8.23 (m,
13H, ArH’s), and 8.65 (s, 1H, NH).
1H NMR: 3.25 (dd, 1H, J = 18.1, 5.8 Hz, CH2(pyraz), 3.82 ((dd, 1H, J = 18.1,
12.2 Hz, CH2(pyraz)), 5.54 ((dd, 1H, J = 12.2, 5.8 Hz, CH2(pyraz)),
6.82–8.10 (m, 14H, aromatic protons and NH2).
IR: 3272,3220 (NH2) and 1582 (C S).
12b
13b
IR: 3420,3252 (NH2) and 1584 (C S).
1H NMR: 2.44 (s, 3H, CH3), 3.25 (dd, 1H, J = 18.1, 5.8 Hz, CH(pyraz)), 3.82
((dd, 1H, J = 18.1, 12.2 Hz, CH2(pyraz)), 5.54 ((dd, 1H, J = 12.2, 5.8 Hz,
CH2(pyraz)), 6.82–8.10 (m, 17H, aromatic protons).
IR: 3028, 2930 (CH), and 1534 (C C).
MS: 473(M+, 39.3%), 272 (32.5%), 247(71.2%), 189(87.1%), 123(50.9%),
123(50.3%), 93(50.3%), 92 (76.7%), 77 (100.0%).
IR: 30420 (CH) and 1590 (C C).
MS: 541 (54.7%), 153 (41.9%), 77(100.0%), 51(45.3%).
IR: 2922(CH) and 1552(C C).
14a
15
MS: 431 (100%), 430 (95.2%), 174 (59.3%), 152 (81.5%), 126 (47.1%), 103
(47.2%), 77(52.8%).
17
18b
IR: 3444(OH), (NH), 3246, 3164(NH2), and 1608 (C S).
1H NMR: 2.55 (s, 3H, CH3), 7.20–7.98(m, 11H, ArH’s), 8.50–8.54 (d, 1H,
CH), 9.60(s, 1H, NH), and 10.80 (s, 1H, OH).
IR: 3422(OH), 321(NH) and 1598(C C).
19
MS: 345 (59.2%), 328 (100.0%), 176(82.2%), 134 (82.1%), 115(36.1%).
2-Methylthio-6-(2-naphthyl)-4-substituted
3,4-Dihydropyrimidine 11a and 11b
A solution of the appropriate 11a,b (5 mmol), sodium methoxide
(0.7 g, 5 mmol) in ethanol (20 mL) was stirred at room temperature,
and then iodeomethane (072 g, 5 mmol) was added. The reaction mix-
ture was stirred for 2 h at room temperature and the solid which formed

2416
A. O. Abdelhamid et al.
TABLE III 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
4a
128–30
(EtOH)
178–80
(EtOH)
142–44
(EtOH)
249–50
AcOH)
180–82
(EtOH)
125–27
(EtOH)
215–17
(EtOH)
208–10
(EtOH)
142–45
(EtOH)
136–38
(EtOH)
138–40
(EtOH)
204–206
(EtOH)
158–60
(EtOH)
215–17
(EtOH)
114–16
(EtOH)
126–28
(EtOH)
170–72
(EtOH)
100–102
(EtOH)
108–10
(EtOH)
150–53
(EtOH)
167–70
(EtOH)
136–39
(EtOH)
240–42
(AcOH)
Yellow
60
Yellow
60
Yellow
65
White
60
Black
50
Orange
70
Yellow
70
Red
60
Orange
60
Yellow
50
Brown
50
Orange
50
Yellow
50
Red
50
White
64
White
50
Yellow
60
Yellow
60
Yellow
70
Yellow
50
Red
70
C20H16N2S
(316.42)
75.91
75.70
67.04
6715
5.09
4.90
4.37
4.20
5.11
5.00
4.83
4.95
5.01
4.95
4.79
4.97
4.84
4.95
4.34
4.43
4.63
4.58
4.33
4.12
4.49
5.12
4.34
4.43
4.41
4.24
3.30
3.25
5.49
5.74
4.79
5.64
5.16
5.26
4.48
4.47
4.70
4.62
4.89
4.98
4.83
4.68
4.41
4.62
4.90
5.12
8.85
8.64
8.68
10.13
10.20
19.88
20.00
—
4b
C
18H14N2S2
(322.44)
8.86
9a
C30H24N4O2
76.25
76.37
75.96
76.10
78.71
78.50
80.93
80.75
78.59
78.65
62.78
62.87
70.27
70.42
69.98
69.78
72.30
72.50
75.27
75.45
73.12
73.25
69.74
69.65
76.33
76.52
76.82
76.50
72.47
72.65
64.06
64.26
76.23
76.32
73.54
73.65
80.13
80.22
67.61
67.47
77.92
77.85
11.85
11.95
12.21
12.40
12.66
12.54
11.10
11.25
13.47
13.62
10.97
1079
11.70
11.85
12.06
12.25
12.42
12.57
10.97
11.22
13.32
13.52
10.84
10.96
8.48
(472.52)
C29H22N4O2
(458.50)
C29H22N4O
(442.51)
9b
—
—
—
—
9c
9d
C
34H24N4O
(504.58)
9e
C
34H25N5O
(519.59)
9f
C
32H22N4OS
(510.60)
6.70
6.62
6.69
7.12
6.90
7.10
7.14
7.24
6.27
6.35
6.09
6.25
12.42
12.53
9.70
9.59
19.05
19.00
9.67
9.52
19.00
18.85
5.98
5.85
6.76
6.85
13.36
13.57
13.36
13.58
7.42
7.49
10a
10b
10c
10d
10e
10f
11a
11b
12a
12b
13a
13b
14a
14b
15
C
28H22N4O2S
(478.55)
C27H20N4O2S
(464.52)
C
C
C
27H20N4OS
(448.53)
32H22N4OS
(510.60)
32H23N5OS
(525.61)
C30H20N4OS2
(516.65)
C21H18N2S
330.46
8.65
8.32
8.20
C
19H16N2S2
336.47
C
20H17N3S
(331.43)
12.98
13.12
12.45
12.35
13.07
13.24
14.78
14.87
14.60
14.80
14.60
14.49
9.73
C
18H15N3S2
(337.45)
C34H25N5S
(535.66)
C
29H23N5S
(373.59)
C
32H23N5S2
(541.61)
Brown
60
Yellow
80
C27H21N5S2
(479.61)
C28H21N3S
(431.55)
9.56
(Continued on next page)

Reactions with Hydrazonoyl Halides 53
2417
TABLE III Characterization Data of the Newly Synthesized
Compounds (Continued )
Calcd. / Found %
Comp.
no.
M.p.◦C
(Solvent)
Color yield
%
Mol. Formula
(Mol. Wt.)
C
H
N
S
16
220–22
(AcOH)
271–73
(AcOH)
245–47
(EtOH)
216–18
(AcOH)
220–22
(AcOH)
Yellow
80
Yellow
80
Brown
60
Red
60
C26H19N3S2
(437.57)
C12H11N3OS
(245.28)
71.36
71.63
58.76
58.67
69.47
69.54
65.10
64.85
69.54
69.32
4.37
4.57
4.51
4.35
4.26
4.58
4.42
4.36
4.37
4.58
9.60
9.42
14.65
14.56
13.07
13.25
7.13
7.15
8.28
8.45
9.28
17
17.13
17.15
15.58
15.28
18.07
18.24
12.16
12.34
18a
18b
19
C26H19N5OS
(449.54)
C21H17N5OS
(387.47)
Yellow
70
C20H15N3OS
(345.40)
9.35
was collected and recrystallized from ethanol to afford 11a and 11b, re-
spectively (Tables II and III).
Amino(3-(2-naphthyl)-5-substituted Pyrazolin-2-
ylmethane-1-thione (12a)
A mixture of the appropriate chalcones 3a,b (10 mmol), thiosemicar-
bazide (0.91 g, 10 mmol) in acetic acid (20 mL) was boiled under reflux
for 2 h. The resulting solid was collected and recrystallized from ethanol
to give pyrazolines 12a and12b, respectively (Tables II and III).
[2-(1-(2-Naphthyl)-5-substitued (1-pyrazolin-3-yl)-4-
phenyl(thiazol-5-yl)phenyldiazine 13a,b and 14a,b
A mixture of the appropriate 12a,b (5 mmol), the appropriate hydra-
zonoyl halides (5 mmol) and triethylamine (0.75 mL, 5 mmol) in ethanol
(20 mL) was heated under reflux 4 h. The resulting solid was collected
and recrystallized from ethanol to give 13a,b and14a,b, respectively
(Tables II and III).
2-(1-(2-Naphthyl)-5-substitued (1-pyrazolin-3-yl))-4-
phenylthiazole 15 and 16
A mixture of the appropriate 12a,b (5 mmol) and phenacylbromide
(1 g, 5 mmol) in ethanol (20 mL) was heated under reflux 2 h then poured
onto ice cold water (50 mL) containing ammonium hydroxide (2 drops).
The resulting solid was collected and recrystallized from ethanol to give
15 and16, respectively (Tables II and III).
2-Hydroxynaphthalenecarbaldehydethiosemicarbazone (17)
A mixture of 2-hydroxynaphtalenecarbadehyde (1.8 g, 10 mmol),
thiosemicarbazide (0.91 g, 10 mmol) ethanol (20 mL) and acetic acid

2418
A. O. Abdelhamid et al.
(3 drops) was stirred at room temperature 30 min. The resulting solid
was collected and recrystallized from ethanol to give thiosemicarbazone
17 (Tables II and III).
1-(2-Aza-2-{[4-phenyldiazenyl)-(1,3-thiazol-2-yl)]amino}vinyl)
naphthalene-2-ol 18a,b
A mixture of 17 (1.22 g, 5 mmol), the appropriate hydrazonoyl halides
5c,d (5 mmol) and triethylamine (0.75 mL, 5 mmol) in ethanol (20 mL)
was heated under reflux 4 h. The resulting solid was collected and re-
crystallized from ethanol to give 18a,b, respectively (Tables II and III).
3-(2-Aza-2-[(4-phenylthiazol-2-yl)amino]vinyl)naphthalin-2-ol
(19)
A mixture of the appropriate 17 (1.22 g, 5 mmol) and phenacylbro-
mide (1 g, 5 mmol) in ethanol (20 mL) was heated under reflux 3 h then
poured onto ice cold water (50 mL) containing ammonium hydroxide (2
drops). The resulting solid was collected and recrystallized from ethanol
to give 19 (Tables II and III).
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