Reactions with hydrazonoyl halides 421: Synthesis of some new 2,3-dihydro-1,3,4-thiadiazoles, 2,3-dihydro-1,3,4-selenadiazoles and triazolino[4,3-a]pyrimidines

Article abstract of DOI:10.1080/104265090508091

2,3-Dihydro-1,3,4-thiadiazoles, 2,3-dihydro-1,3,4-selenadiazoles, unsymmetrical azines and triazolino[4,3-a]pyrimidines were prepared from reaction of (2Z)-3-aza-2-bromo-1-naphto[1,2-d]furan-2-yl-3-(phenylamino)prop-2- en-1-one (6) with each of potassium

Full text of DOI:10.1080/104265090508091

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Reactions with Hydrazonoyl
Halides 421: Synthesis
of Some New 2,3-
Dihydro-1,3,4thiadiazoles, 2,3-
Dihydro-1,3,4-selenadiazoles
and Triazolino[, ]pyrimidines
Abdou O. Abdelhamid a & Mohamed A. M. Alkhodshi
a
a Department of Chemistry, Faculty of Science, Cairo
University , Giza, 12316, Egypt
Published online: 01 Feb 2007.
To cite this article: Abdou O. Abdelhamid & Mohamed A. M. Alkhodshi
(2005) Reactions with Hydrazonoyl Halides 421: Synthesis of Some New
2,3-Dihydro-1,3,4thiadiazoles, 2,3-Dihydro-1,3,4-selenadiazoles and
Triazolino[, ]pyrimidines, Phosphorus, Sulfur, and Silicon and the Related Elements,
180:1, 149-161, DOI: 10.1080/104265090508091
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Phosphorus, Sulfur, and Silicon, 180:149–161, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090508091
Reactions with Hydrazonoyl Halides 421:
Synthesis of Some New 2,3-Dihydro-1,3,4-
thiadiazoles, 2,3-Dihydro-1,3,4-selenadiazoles
and Triazolino[4,3-a]pyrimidines
Abdou O. Abdelhamid
Mohamed A. M. Alkhodshi
Department of Chemistry, Faculty of Science, Cairo University,
Giza 12316, Egypt
2,3-Dihydro-1,3,4-thiadiazoles, 2,3-dihydro-1,3,4-selenadiazoles, unsymmetrical
azines and triazolino[4,3-a]pyrimidines were prepared from reaction of (2Z)-3-aza-
2-bromo-1-naphto[1,2-d]furan-2-yl-3-(phenylamino)prop-2-en-1-one (6) with each
of potassium thiocyanate, potassium selenocyanate, alkyl carbodithioate, ethyl 6-
methyl-2-methylthio-4-substituted 3,4-dihydropyrimidine-5-carboxylate or (ethyl
4-methyl-6-substituted 2-thione-1,3,6-trihydropyrimidine-5-carboxylate). All com-
pounds were elucidated on the basis of elemental analysis, spectral data, and alter-
native synthesis method whenever possible.
Keywords 1,3-dipolar cycloaddition; 1,3,4-selenadiazoles; 1,3,4-thiadiazoles; hydra-
zonoyl bromide; nitrilimine; triazolo[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 hydrazonoyl halides have been widely for the syn-
thesis of heterocyclic compounds.6–10 We report here the synthesis of
triazolo[4,3-a]pyrimidines, 2,3-dihydro-1,3,4-thiadiazoles, 2,3-dihydro-
1,3,4-selenadiazoles, and unsymmetrical azines.
RESULTS AND DISCUSSION
Reaction of 2-bromo-1-naphtho[1,2-d]furan-2-ylethan-1-one (2) with
dimethylsulfide in boiling ethanol under reflux afforded 1-naphtho[1,2-
d]furan-2-yl-2-oxoethylsulfonium bromide (3). Structure of the latter
product was established by elemental analysis, spectral data, and
Received May 7, 2004; accepted June 16, 2004.
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry, Faculty
of Science, Cairo University, Giza 12316, Egypt. E-mail: abdou abdelhamid@yahoo.com
149

150
A. O. Abdelhamid and M. A. M. Alkhodshi
chemical transformation. Thus, treatment of 3 with N-nitroacetanilide
(4)11 in ethanol at room temperature gave (2Z)-3-aza-2-bromo-1-
naphto[1,2-d]furan-2-yl-3-(phenylamino)prop-2-en-1-one (6) (Scheme
1). Spectral data, microanalytical analysis, and chemical transforma-
tion confirmed the structure 6. 1H NMR spectrum of 6 showed signals
at δ = 6.48–7.42 (m, 10H), 7.59 (d, 1H), 7.67 (s, 1H), and 9.34 (s, br., 1H).
Its IR (cm−1) spectrum revealed bands at 3241 (NH), 3049 (C H), 1665
(CO), 1642 (C N), and 1582 (C C).
Treatment of hydrazonoyl bromide 6 with potassium thiocyanate in
ethanol at room temperature afforded product which gave analytical
and spectral in accord with their formation as: 2-imino-3-phenyl(1,3,4-
thiadiazolin-5-yl)naphto[1,2-d]furan-2-ylketone (8a). The IR spectrum
of 8 revealed the absence bands at 2156 (ν SCN) and showed bands at
1
3319 (NH), 3056 (C H), 1627 (CO conjugated). Its HNMR spectrum
showed signals at δ = 6.46–7.42 (m, 10H), 7.59 (s, 1H), 7.69 (d, 1H)
and 8.08 (s, 1H). Upon shaking with D2O a new singlet appeared at
δ = 4.55 assignable to DOH proton and multiplicity signals at δ = 6.46–
7.60 equivalent to 12 protons. Such results indicate that the reaction of
6 with potassium thiocyanate proceed through the hydrazone 7, which
cyclized readily under the reaction conditions to give 8a (Scheme 1).
Thus, benzenediazonium chloride reacted with (2-naphtho[1,2-d]furan-
2-ylcarbonyl)thiocarbonitrile (13) in ethanolic sodium acetate solution
at 0◦C gave product identical in all respects (mp., mixed mp., and
spectra) with 8a.
Nitrosation of 8a with sodium nitrite in acetic acid solution gave 2-
(azanitrosomethylene)-3-phenyl(1,3,4-thiadiazoline-5-yl)naphtho[1,2-
d]furan-2-ylketone (9a). The IR spectrum of 9a showed no NH band,
but contained common bands at 3057 (C H), 1631.7 (CO), 1583 (C C),
and 1485 (NO). Compound 9a decomposed to 5-(naphtho[1,2-d]furan-
2-ylcarbonyl)-3-phenyl-1,3,4-thiadiazolin-2-one (10a) via boiling in
xylene. The IR spectrum of 10a revealed absorption bands at 3061
(C H), 1691, 1633 (CO’s), and 1583 (C C) cm−1
.
Acylation of 8a with acetic anhydride or benzoyl chloride in pyridine
yielded 1-aza-1-[5-(naphtho[1,2-d]furan-2-ylcarbonyl)-3-phenyl(1,3,4)
thiadiazolin-2-yliden)]acetone (11a) and 2-aza-2-[5-(naphto[1,2-d]-
furan-2-ylcarbonyl)-3-phenyl(1,3,4)thiadiazolin-2-yliden)]-1-phenyl-
ethan-1-one (12a), respectively. Both elemental analysis and spectral
data were consistent with the assigned structure of products 11a and
12a. 1H NMR spectrum of 11a showed signals at δ = 2.38 (s, 3H),
6.64–7.67 (m, 12H).
Similar, reaction of hydrazonoyl bromide 6 with potassium sleno-
cyanate afforded 2-imino-3-phenyl(1,3,4-selenadiazolin-5-yl)naphtho-
[1,2-d]furan-2-ylketone (8b). Also, compound 8b was nitrosation and

Reactions with Hydrazonoyl Halides
151
SCHEME 1

152
A. O. Abdelhamid and M. A. M. Alkhodshi
acylation to afford 2,3-dihydro-1,3,4-selenadiazoles (9–12)b, respec-
tively (Scheme 1).
Hydrazonoyl bromide 6 was reacted with methyl phenylthio-
carbamate12 (14a) in ethanolic triethylamine solution gave 2-(azaphe-
nylmethylene)-3-phenyl(1,3,4-thiadiazolin-5-yl)-naphtho[1,2-d]furan-
2-ylketone (17) (Scheme 2). Structure 17 was confirmed on the basis of
spectral data, elemental analysis, and alternative synthesis method.
Thus, 1H NMR spectrum of 17 showed signals at δ = 6.46–7.01 (m,
ArH’s). Thus, ethyl phenylthiocarbamate (14b) reacted with 6 in
ethanolic triethylamine to give identical product in all respects (mp.,
mixed mp., and spectra) with 17.
In the light of the forgoing results, the mechanism outlined in
Scheme 2 seems to be the most plausible pathway for the formation
of 17 from the reaction of the 6 with 14. The reaction involves ini-
tial formation of thiohydrazonate 15, which undergoes intermolecu-
lar cyclization as soon as it is formed to yield the intermediate 16 or
via 1,3-dipolar cycloaddition of nitrilimine 18, (which prepared in situ
from 6 with triethylamine) to C S double bond of 14. The formation of
15 and 16 are similar to the reaction of hydrazonoyl chloride with 1-
phenyl-1,4-dihydrotetrazole-5-thione13 and 5-phenyl-1,3,4-thiadiazole-
2(3H)-thione.14
By similar route, the hydrazonoyl bromide 6 reacted with 3-{aza-
[(methylthioxomethyl)amino]methylene}indoline-2-one15 to give un-
symmetrical azines 19 (Scheme 2).
Also, treatment of [(1E)-1-aza-phenylvinyl)amino]methylthiome-
thane-1-thione16 20a with hydrazonoyl bromide 6 in ethanolic triethy-
lamine at room temperature, gave 2-((E)-1,2-diaza-3-phenylprop-2-
enylidene)-3-phenyl(1,3,4-thiadiazolin-5-yl)naphtho[1,2-d]furan-2-yl
ketone 24a (Scheme 3). Structure 24a was confirmed by elemental
analysis, spectral data and alternative route synthesis. 1H NMR
spectra of 24a showed signals at δ = 6.46–7.59 (m, 17H) and 8.10 (s,
1H). Thus, treatment of 6 with 21a in ethanolic triethylamine gave
product identical in all respects (mp. mixed mp., and spectra) with
24a. By the same way, compound 6 reacted with the appropriate
alkyl carbodithioates17–19 20–21(b–k) in ethanol containing triethy-
lamine afforded 2,3-dihydro-1,3,4-thiadiazoles 24(b–k), respectively
(Scheme 3).
Similarly, hydrazonoyl bromide 6 reacted with each of [((1E,3E)-
1-aza-4-phenylbuta-1,3-dienyl)amino]methyl-thiomethane-1-thione20
(20l), ({(1E)-1-aza-2-[4-(methylethyl)phenyl]vinyl}amino)methylthio-
methane-1-thione20 (20m) and [((1E)-2-(2H-benzo[3,4-d]1,3-dioxolan-
5-yl)-1-azavinyl)amino]methylthiomethane-1-thione20 (20n) to give
unsymmetrical azines 24(l-n), respectively (Scheme 3).

Reactions with Hydrazonoyl Halides
153
SCHEME 2
Treatment of hydrazonoyl bromide
6 with the appropriate
ethyl 6-methyl-2-methylthio-4-substituted 3,4-dihydropyrimidine-5-
carboxylates21 25a–f in boiling chloroform under reflux gave
triazolino[4,3-a]pyrimidines in a good yields 27a–f, respectively
(Scheme 4). Structure of 27 was elucidated on the basis of elemental
analysis, spectral data, and alternative synthesis route. Thus, 1H NMR
spectrum of 27a showed signals at δ = 1.23 (t, 3H), 2.56 (s, 3H), 4.09
(q, 2H), 7.05 (s, 1H), 7.16–7.25 (m, 3H), 7.44–7.72 (m, 8H), 8.05 (s, 1H),
and 8.24 (d, 2H). Its IR spectrum revealed bands at 1702 (CO ester),
1650 (CO conjugated) and 1615 (C N).
Thus, hydrazonoyl bromide 6 reacts with ethyl 4-methyl-6-phenyl-
2-thione-1,3,6-trihydropyrimidine-5-carboxylate21 28a in boiling chlo-
roform to give product identical in all respects (mp., mixed mp., and
spectra) with 27a.
Two possible pathways can account for the formation 27: 1) 1,3-
addition of the thiol, tautomer 27 to the nitrilium imide 18, which gener-
ated in situ by treatment of hydrazonoyl bromide 6 with triethylamine,
can give the thiohydrazonate ester 29 which undergoes nucleophilic cy-
clization to yield spiro compounds 30. The latter intermediate 30 ring

154
A. O. Abdelhamid and M. A. M. Alkhodshi
SCHEME 3
open to 31 which cyclized to yield 27 by loss hydrogen sulfide; and 2)
1,3-cycloaddition of nitrilium imide 18 to C S double bond of 28 can
give directly 30 (Scheme 4).
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
CDCl3 and (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. Elemental analyses were carried out at the Microan-
alytical Center of the Cairo University.

Reactions with Hydrazonoyl Halides
155
SCHEME 4

156
A. O. Abdelhamid and M. A. M. Alkhodshi
2-Bromo-1-naphtho[1,2-d]furan-2-ylethan-1-one (2)
Bromine (16g, 5 ml, 100 mmol) was added dropwise to solution of 1-
naphtho[1,2-d]furan-2-ylethan-1-one (1) (21 g, 100 mmol) in a mixture
of dioxane-ether (50 ml each) with stirring. The reaction mixture was
poured to ice-cold water (150 ml) and the solid was collected and crys-
tallized from ethanol to give 2 (Table I).
1-Naphtho[1,2-d]furan-2-oyldimethylsulfonium bromide (3)
A
mixture of 2-Bromo-1-naphtho[1,2-d]furan-2-ylethan-1-one (2)
(14.9 g, 50 mmol) and dimethylsulphide (3.1 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 I).
3-Aza-2-bromo-1-naphto[1,2-d]furan-2-yl-3-(phenylamino-2-
en-1-one (6)
A mixture of sulfonium bromide 3 (17.5 g, 50 mmol) and N-nitroso-N-
phenylacetamide (9.9 g, 60 mmol) in ethanol (100 ml) was stirred for
2 h. The yellow solid was collected and crystallized from ethanol to give
6 (Table I).
Synthesis of 2-Imino-3-phenyl(1,3,4-thiadiazolin-5-yl)-
naphtho[1,2-d]furan-2-ylketone (8a) and 2-imino-3-
phenyl(1,3,4-selenadiazolin-5-yl)naphtho[1,2-d]furan-2-
ylketone (8b)
Method A: A mixture of 6 (1.96 g, 5 mmol) and the appropriate of
potassium thiocyanate (0.58 g, 6 mmol) (or potassium selenocyanate
(0.86 g, 6 mmol)) in ethanol (25 ml) was stirred at room tempera-
ture for 3 h. The resulting solid was collected, washed with water,
and crystallized from dioxan to give 8a and 8b, respectively (Tables I
and II).
Method B: The appropriate benzenediazonium chloride (5 mmol),
which prepared from diazotised aniline (0.46 g, 5 mmol) as usual way,
was added dropwise to a cold solution of ethanol (50 ml), containing
a (2-naphtho[1,2-d]furan-2-ylcarbonyl)thiocarbonitrile (13), which pre-
pared via reaction of 2-Bromo-1-naphtho[1,2-d]furan-2-ylethan-1-one
(2) with potassium thiocyanate, (1.34 g, 5 mmol) and sodium acetate
(1.3 g, 10 mmol), while stirring at 0–5◦C. The resulting solid was col-
lected and crystallized from dioxan gave 8a.

Reactions with Hydrazonoyl Halides
157
TABLE I Characterization Data of The Newly Synthesized
Compounds
Analyses, calcd./found
Comp.
no.
Yield %
colour
Mol. formula
mol. Wt
Mp. ◦
120
C
C
H
N
S
2
77
C14H9BrO2
289.13
58.16 3.14
58.00 320
EtOH
3
152–54
EtOH
202–204
EtOH
70
C
16H15BrO2S 54.71 4.30
351.26 54.90 4.20
C20H13N2BrO2 61.09 3.33
393.24 61.10 3.40
9.13
9.00
Pale yellow
82
Yellow
6
7.12
7.30
8a
180–82
Dioxan
173–75
Dioxan
132–35 dec.
Acetone
140–42 dec.
Acetone
258–60
AcOH
226–28
AcOH
243–45
AcOH
203–204
AcOH
266–68
AcOH
78
Yellow
74
C21H13N3O2S 67.91 3.53 11.13
371.42 67.71 3.68 11.21
21H13N3O2Se 60.30 3.13 10.05
418.31 60.42 3.00 10.15
C21H12N4O3S 62.99 3.02 13.99
400.42 63.12 2.94 14.12
21H12N4O3Se 56.39 2.70 12.53
447.31 56.76 2.97 12.35
C21H12N2O3S 67.73 3.25
372.40 67.61 317
21H12N2O3Se 60.16 2.88
419.30 59.92 3.14
8.63
8.51
8b
C
Yellowish brown
9a
85
8.01
8.20
Yellowish brown
9b
83
C
Yellowish brown
10a
10b
11a
11b
12a
12b
13
77
Orange
72
Brown
86
Yellow
78
Yellow
7.52
7.41
6.68
6.86
8.61
8.52
C
C
23H15N3O3S 66.82 3.66 10.16
413.45 66.67 3.54 10.05
23H15N3O3Se 60.01 3.28
460.35 59.22 3.22
28H17N3O3S 70.72 3.60
475.52 70.60 3.57
C28H17N3O3Se 64.37 3.28
7.76
7.65
C
9.13
917
64
C
8.84
8.75
8.04
8.10
5.24 12.00
5.35 11.84
6.74
6.91
Pale brown
266–68
AcOH
165–67
EtOH
68
Pale brown
522.42
15H9NO2S
267.31
64.10 3.56
67.40 3.39
67.28 3.27
69
C
Yellowish brown
17
234–36
AcOH
>350
AcOH
252–54
AcOH
250–52
AcOH
237–40
AcOH
248–50
AcOH
292–94
AcOH
87
C
C
C
27H17N3O2S 72.46 3.82
447.52 72.62 3.74
9.39
9.27
7.16
7.04
6.22
6.12
6.76
6.57
6.56
6.57
Brownish yellow
19
83
Orange
89
29H17N5O3S 67.56 3.32 13.58
515.55 67.79 3.12 13.74
28H18N4O2S 70.87 3.82 11.81
474.54 70.79 3.80 11.74
C29H20N4O2S 71.29 4.13 11.47
488.57 70.99 4.28 11.62
24a
24b
24c
24d
24e
24f
Reddish orange
84
Orange
82
Red
78
Red
81
C
26H16N4O2S2 64.98 3.36 11.66 13.34
480.57 64.80 3.43 11.46 13.45
C26H16N4O3S 67.23 3.47 12.06
464.50 67.28 3.36 12.20
27H17N5O2S 68.20 3.60 14.73
475.53 67.98 3.87 14.62
27H17N5O2S 68.20 3.60 14.73
475.53 67.95 3.90 14.82
6.90
7.12
6.74
7.12
6.74
6.52
C
C
Brownish red
82
Brownish red
270–74
AcOH
(Continued on next page)

158
A. O. Abdelhamid and M. A. M. Alkhodshi
TABLE I Characterization Data of The Newly Synthesized
Compounds (Continued)
Analyses, calcd./found
Comp.
no.
Yield %
Colour
Mol. formula
Mol. Wt
Mp. ◦
C
C
H
N
S
24g
24h
24i
260–64
AcOH
240–43
AcOH
260–64
AcOH
257–60
AcOH
84
Orange
79
Orange
76
Yellow
78
C29H20N4O2S
488.57
71.29 4.13 11.47
71.33 4.06 11.52
71.69 4.41 11.15
71.76 4.42 11.22
6.56
6.77
6.38
6.27
6.13
6.18
C30H22N4O2S
502.59
C29H19ClN4O2S 66.60 3.66 10.71
523.01
27H18N4O2S2
494.59
66.51 3.57 10.65
65.57 3.67 11.33 12.97
65.73 3.72 11.24 12.85
24j
C
Reddish orange
24k
24l
227–30
AcOH
240–42
AcOH
267–69
AcOH
270–72
AcOH
238–40
AcOH
215–18
AcOH
250–51
AcOH
247–49
AcOH
189–90
EtOH
212–14
AcOH
244–45
AcOH
226–27
AcOH
84
Red
78
Red
74
Red
78
Orange
65
Brown
72
C27H18N4O3S
478.53
C30H20N4O2S
500.58
67.77 3.79 11.71
67.53 4.02 11.91
71.98 4.03 11.19
71.76 4.16 11.22
67.17 3.50 10.80
67.33 3.62 10.91
72.07 4.68 10.85
71.91 4.70 10.58
69.01 4.45 12.38
68.81 4.64 12.15
69.51 4.75 12.01
69.68 4.78 12.21
72.35 4.31 10.81
72.48 4.26 10.89
6.70
6.80
6.41
6.32
6.18
6.00
6.21
6.10
7.09
7.12
6.86
6.68
6.22
6.34
24m
24n
24o
24p
24r
27a
27b
27c
27d
27e
27f
C29H18N4O4S
518.55
C31H24N4O2S
516.62
C
C
C
26H20N4O2S
452.53
27H22N4O2S
466.56
31H22N4O2S
514.61
Brownish red
81
Red
72
Red
76
Orange
68
Orange
64
Orange
71
Orange
68
C34H26N4O4
73.63 4.73 10.10 11.54
73.52 4.57 10.00 11.34
554.61
C35H28N4O4
568.63
C35H28N4O5
584.63
73.93 4.96
9.85 11.25
73.82 4.87 10.00 11.34
71.91 4.83
71.80 4.87
69.33 4.28
69.12 4.37
74.48 5.41
74.52 5.34
70.23 4.38
70.21 4.45
9.58 13.68
9.74 13.86
9.51 10.86
9.72 11.00
9.37 10.73
9.48 10.81
9.36 16.04
9.32 16.24
C
34H25ClN4O4
589.05
C
37H32N4O4
596.69
215–17
AcOH
C
35H26N4O6
598.62
Orange
Synthesis of (2-Naphtho[1,2-d]furan-2-ylcarbonyl)-
thiocarbonitrile (13)
Equimolar quantities of each of 2-Bromo-1-naphtho[1,2-d]furan-2-
ylethan-1-one (2) and potassium thiocyanate (50 mmol each) in ethanol
(50 ml) was boiled under reflux for 30 min. The reaction mixture was
poured onto ice-cold water (100 ml), the resulting solid was collected
and crystallized from ethanol to give 13 (Tables I and II).

Reactions with Hydrazonoyl Halides
159
TABLE II 1H NMR Spectra of Some Selected Synthesized Compounds
Comp. no.
1H NMR (δ)
19
6.83–8.55(m, 16H) and 8.91 (s, 1H).
24b
24g
24h
24i
24j
24k
24l
2.39 (s, 3H), 7.20–8.21 (m, 15H), 8.40 (s, 1H) and 8.64 (s, 1H).
2.45 (s, 3H), 7.26–8.18 (m, 16H) and 8.66 (s, 1H)
2.39 (s, 3H), 2.48 (s, 3H), 7.20–8.20 (m, 15H) and 8.66 (s, 1H).
2.045 (s, 3H), 7.26–8.17 (m, 15H) and 8.63 (s, 1H).
2.47 (s, 3H), 7.03–8.19 (m, 14H), 8.65 (s, 1H).
2.39 (s, 3H), 6.48 (t, 1H), 6.88 (d, 1H), 7.26–8.17 (m, 12H) and 8.16 (s, 1H).
5.61 (d, 1H), 6.24 (t, 1H), 6.46 (d, 2H), 6.62 (d, 1H), 7.01 (t, 2H), 7.19–7.59
(m, 12H) and 8.64 (s, 1H).
24m
24n
24o
24p
24r
27a
27b
27c
27d
27e
6.00 (s, 2H), 6.84–8.32 (m, 15H) and 8.63 (s, 1H).
1.26 (d, 6H), 2.92 (sept., 1H), 7.26–8.43 (m, 16H) and 8.64 (s, 1H).
1.79 (t, 4H), 2.54 (quant., 4H), 7.24–8.22 (m, 11H) and 8.63 (s, 1H).
1.68 (d, 4H), 2.43 (t, 4H), 2.68 (t, 2H), 6.46–7.59 (m, 11H) and 8.53 (s, 1H).
1.89 (d, 2H), 2.79 (t, 2H), 2.99 (d, 2H), 6.46–7.59 (m, 15H) and 8.63 (s, 1H).
1.24 (t, 3H), 2.50 (s, 3H), 4.09 (q, 2H) and 7.05–8.47 (m, 18H).
1.24 (t, 3H), 2.19 (s, 3H), 2.57 (s, 3H), 4.09 (q, 2H) and 6.98–8.51 (m, 17H).
1.24 (t, 3H), 2.59 (s, 3H), 3.66 (s, 3H), 4.09 (q, 2H) and 6.69–8.52 (m, 17H).
1.24 (t, 3H), 2.57 (s, 3H), 4.09 (q, 2H) and 7.04–8.55 (m, 17H).
1.08 (d, 6H), 1.21 (t, 3H), 2.58 (s, 3H), 2.71 (sept., 1H), 4.06 (q, 2H) and
7.03–8.51 (m, 17H).
27f
1.29 (t, 3H), 2.57 (s, 3H), 4.11 (q, 2H), 5.82 (s, 2H) and 6.59–8.45 (m, 16H).
Synthesis of 2-(Azanitrosomethylene)-3-phenyl(1,3,4-
thiadiazoline-5-yl)naphtho[1,2-d]furan-2-ylketone (9a) and
2-(azanitrosomethylene)-3-phenyl(1,3,4-selenadiazoline-5-
yl)naphtho[1,2-d]furan-2-ylketone (9b)
A cold saturated solution of sodium nitrite (10 ml) was added dropwise
a solution of 8a or 8b (1 g) in acetic acid (20 ml) in an ice bath while
stirring. The reaction mixture was stirred for 30 min. The resulting
TABLE III 13C NMR Spectra of Some Selected Synthesized
Compounds
Comp. no.
13C NMR (δ)
8a
19
178, 163, 160, 155, 154, 152, 146, 129, 128, 126, 125, 123, 121, 115.
178, 164, 163, 161, 160, 155, 154, 147, 139, 131, 130, 129, 128, 125, 124, 123,
122, 120, 118, 115.
24g
27a
181, 164, 161, 155, 154, 147, 140, 130, 129, 128, 125, 124, 123, 121, 118, 115,
111, 12.
179, 165, 163, 160, 155, 154, 146, 142, 130, 129, 127, 126, 125, 124, 123, 121,
118, 115, 112, 60, 41, 17.

160
A. O. Abdelhamid and M. A. M. Alkhodshi
solid was collected, washed with water, and crystallized from acetone
to give 9a and 9b, respectively (Tables I and II).
Synthesis of 5-(Naphtho[1,2-d]furan-2-ylcarbonyl)-3-phenyl-
1,3,4-thiadiazolin-2-one (10a) and 5-(naphtha-
[1,2-d]furan-2-ylcarbonyl)-3-phenyl-1,3,4-thiadiazolin-2-
one (10b)
A solution of 9a, 9b (0.5 g) in xylene (20 ml) was refluxed for 15 min
and then, the solvent was evaporated under reduced pressure. The
residue oil was triturated with petroleum ether (40–60◦C) and the
solid formed was collected and crystallized from acetic acid to give
1,3,4-thiadiazolinone 10a and 1,3,4-selenadiazolinone 10b, respec-
tively (Tables I and II).
Acylation of 1,3,4-Thiadazoline 8a and 1,3,4-
selenadiazoline 8b
Acetylation. A mixture of 8a or 8b (1 g) in acetic acid (10 ml) and
acetic anhydride (5 ml) was warmed for 5 min at 70◦C. The reaction
mixture was poured onto ice water (40 ml). The solid was collected and
crystallized to give the N-acetyl derivatives 11a and 11b, respectively
(Tables I and II).
Benzoylation. 8a or 8b (0.5 g) and benzoyl chloride (3 ml) in pyridine
(15 ml) were refluxed for 10 min, poured onto ice water (50 ml) and
acidified with hydrochloric acid. The resulting product was collected
and washed several time with boiling water. The resulting solid was
crystallized from acetic acid to give the N-benzoyl derivatives 12a and
12b, respectively (Tables I and II).
Synthesis of Thiadiazolines 17, 19 and 24a–r
Triethylamine (0.5 g (0.75 ml), 5 mmol) was added dropwise with
stirring to a mixture of the appropriate alkyl carbodithioates 14a (or
14b), or 20a–r (or 21a–r) (5 mmol) and compound 6 (1.9 g, 5 mmol) in
ethanol (20 ml). The resulting solid, which formed after 30 min, was
collected and crystallized from acetic acid and gave the corresponding
thiadiazolines 17, 19, and 24a–r, respectively in a good yield (Tables I
and II).
Synthesis of 1,2,4-Triazolo[4,3-a]pyrimidines 27a–f
Method A. An equimolar amount of each of the hydrazonoyl bro-
mide 6, the appropriate 25a–f and sodium ethoxide (5 mmol) in ethanol
(20 ml) was refluxed for 3 h. The reaction mixture was cooled and the

Reactions with Hydrazonoyl Halides
161
resulting solid was collected and crystallized to give 27a–f, respectively
(Tables I and II).
Method B. A mixture of the appropriate hydrazonoyl bromide 6
(5 mmol) and the appropriate pyrimidin-2-thione 28a–f (1.68 g, 5 mmol)
in chloroform (20 ml) containing triethylamine (0.5 g (0.75 ml), 5 mmol)
was refluxed for 10 h. Chloroform was evaporated under reduced pres-
sure and the residue solid was crystallized to give products identical in
all respects (mp., mixed mp., and spectra) with corresponding products
obtained by method A.
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