Reactions of hydrazonoyl halides 351: Synthesis of some new 1,2,4-triazolino[4,3-a]pyrimidines, 2,3-dihydro-1,3,4-thiadiazoles and 2,3-dihydro-1,3,4-selenadiazoles

Article abstract of DOI:10.1080/10426500307853

Hydrazonoyl halides have been caused to react with each of ethyl 4-(2H-benzo[3,4-d]1,3-dioxolen-5-yl)-6-methyl-2-methylthio-3,4- dihydropyrimidin-5-carboxylate, potassium thiocyanate (or thiourea), potassium selenocyanate, and alkyl carbodithioate in the presence of triethylamine to give 4,3-dihydro-1,2,4-triazolino[4,3-a]pyrimidine, 1,3,4-thiadiazoline, 1,2,4-selenadiazoline, and unsymmetrical azine derivatives in good yields. Structures of the new compounds were elucidated on the basis of elemental analyses, spectral data, and alternative methods of synthesis whenever possible.

Full text of DOI:10.1080/10426500307853

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Phosphorus, Sulfur, and Silicon and the Related
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Reactions of Hydrazonoyl Halides 35 1 : Synthesis of
Some New 1,2,4-Triazolino[4,3-a]pyrimidines, 2,3-
Dihydro-1,3,4-thiadiazoles and 2,3-Dihydro-1,3,4-
selenadiazoles
Nora M. Rateb a , Nadia A. Abdel-Riheem a , Ali A. Al-Atoom a & Abdou O. Abdelhamid a
a Cairo University, Giza, Egypt
Published online: 27 Oct 2010.
To cite this article: Nora M. Rateb , Nadia A. Abdel-Riheem , Ali A. Al-Atoom & Abdou O. Abdelhamid (2003): Reactions of
Hydrazonoyl Halides 35 1 : Synthesis of Some New 1,2,4-Triazolino[4,3-a]pyrimidines, 2,3-Dihydro-1,3,4-thiadiazoles and 2,3-
Dihydro-1,3,4-selenadiazoles, Phosphorus, Sulfur, and Silicon and the Related Elements, 178:5, 1101-1114
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Phosphorus, Sulfur and Silicon, 2003, Vol. 178:1101–1114
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1042-6507/03 $12.00 + .00
DOI: 10.1080/10426500390208947
REACTIONS OF HYDRAZONOYL HALIDES 351:
SYNTHESIS OF SOME NEW
1,2,4-TRIAZOLINO[4,3-a]PYRIMIDINES,
2,3-DIHYDRO-1,3,4-THIADIAZOLES AND
2,3-DIHYDRO-1,3,4-SELENADIAZOLES
Nora M. Rateb, Nadia A. Abdel-Riheem, Ali A. Al-Atoom,
and Abdou O. Abdelhamid
Cairo University, Giza, Egypt
(Received September 10, 2002; accepted October 9, 2002)
Hydrazonoyl halides have been caused to react with each of
ethyl 4-(2H-benzo[3,4-d]1,3-dioxolen-5-yl)-6-methyl-2-methylthio-3,4-
dihydropyrimidin-5-carboxylate, potassium thiocyanate (or thiourea),
potassium selenocyanate, and alkyl carbodithioate in the presence of tri-
ethylamine to give 4,3-dihydro-1,2,4-triazolino[4,3-a]pyrimidine, 1,3,4-
thiadiazoline, 1,2,4-selenadiazoline, and unsymmetrical azine deriva-
tives in good yields. Structures of the new compounds were elucidated
on the basis of elemental analyses, spectral data, and alternative meth-
ods of synthesis whenever possible.
Keywords: 1,3,4-selenadiazolines; 1,3,4-thiadiazolines; hydrazonoyl
halides; triazolo[4,3-a]pyrimidine
Hydrazonoyl halides have been used widely as important tools for
the synthesis of heterocyclic compounds.2–5 In continuation of our in-
terest in the chemistry of hydrazonoyl halides,6–10 we report herein
their utility in the convenient and efficient synthesis of triazolino[4,3-
a]pyrimidine and 1,3,4-thiadiazole derivatives.
The reaction of equimolar amount of ethyl 4-(2H-benzo[3,
4-d ]1,3-dioxolen-5-yl)-6-methyl-2-methylthio-3,4-dihydropyrimidin-5-
carboxylate (4), C-methoxycarbonyl-N-phenylhydrazonoyl chloride (1a)
and sodium ethoxide in boiling ethanol furnished exclusively the cor-
responding methyl 4-(2H-benzo[d]1,3-dioxolen-5-yl)-5-ethoxycarbon-
yl)-6-methyl-1-phenyl-4,3-dihydro-1,2,4-triazolino-[4,3-a]pyrimidine-3-
carboxylate (7a) in excellent yield. Structure 7a was elucidated on the
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry, Faculty
of Science, Cairo University, Giza 12316, Egypt. E-mail: Abdou@main-scc.cairo.eun.eg
1101

1102
N. M. Rateb et al.
1
basis of analytical, spectral data, and alternative synthesis route. H
NMR spectrum showed signals at 1.23 (t, 3H, CH2CH3), 2.51 (s,
3H, CH3), 3.96 (s, 3H, OCH3), 4.12 (q, 2H, CH2CH3), 5.88 (s, 2H,
CH2), 6.64 (s, 1H, CH), and 6.87–8.20 (m, 8H, ArH’s). IR spectrum
revealed peaks at 1735 (CO’s esters), 1666 (C N) and 1604 C C).
Moreover, ethyl 6-(2H-benzo[3,4-d]1,3-dioxolen-5-yl)-4-methyl-2-
thioxo-1,3,6-trihydropyrimidine-5-carboxylate (3) reacted with 1a in
boiling chloroform in the presence of triethylamine gave the identical
product in all respects (m.p., mixed m.p., and spectra) with compound
7a. The formation of 7a can be explained by a stepwise path involving
substitution to give amidrazone 5a, which readily cyclized to give
intermediate 6a. The intermediate 6a can be formed via 1,3-dipolar
cycloaddition of nitrile imide 2a (which formed in situ by the treatment
of hydrazonoyl chloride 1a with triethylamine) to C N of pyrimidine
4. The intermediate 6a was converted to 7a via elimination of methyl
mercaptan (cf. Scheme 1).
SCHEME 1
Similarly, the appropriate 3 or 4 reacted with the appropriate hy-
drazonoyl halides 1b–g to give the corresponding 1,2,4-triazolino[4,5-
a]pyrimidines 7b–g respectively.

1
Reactions of Hydrazonoyl Halides 35
1103
Bromination of, ((1E)2-(2H-benzo[3,4-d]1,3-dioxolen-5-yl)-1-azav-
inyl)(4-nitrophenyl-1-aza-amine (8) in acetic acid gave ((1E)-2-(2H-
benzo[3,4-d]1,3-dioxolen-5-yl)-aza-2-bromovinyl)(4-nitrophenyl)amine
(9) (72%). Structure of 9 was confirmed on the basis of microanalyses,
spectral data, and its reactions with different reagents. 1HNMR
spectrum of 9 showed signals at 4.30 (s, 2H, CH2) and 7.28–8.19
(m, 8H, ArH’s and NH). Compounds 9 reacted with potassium thio-
cyanate and potassium selenocyanate in ethanol to give 11a and
11b respectively. The structures 11a and 11b were confirmed on
the basis of elemental analyses, spectral data, alternative synthesis
route, and the reaction of each with nitrous acid and acetic anhydride
(or benzoyl chloride). The 1HNMR spectrum of 11a showed signals
at 6.62 (s, 2H, CH2) and 7.00–8.31 (m, 8H, ArH’s and NH). The
IR spectra of 11a and 11b revealed bands at 3380 (NH) and no
absorption bands in the region 2000–2200 due to the absence of
SCN or SeCN groups.11 Thus treatment of 9 with thiourea in boiling
ethanol gave identical product in all respects (mp, mixed mp and
spectra) with 11a. These results indicated that both the reaction
of 9 with potassium thiocyanate or thiourea proceed through the
intermediate 10 or (12 and 13), which cyclized readily to give 11a (cf.
Scheme 2).
Acylation of 11a and 11b with acetic anhydride (and with benzoyl
chloride in pyridine) afforded N-acetyl 14a,b and N-benzoyl 15a,b re-
spectively. Both spectral data and elemental analyses confirmed the
1
structures of the products 14a,b and 15a,b. HNMR spectrum of 14a
showed signals at 2.43 (s, 3H, CH3CO), 6.07 (s, 2H, CH2), and 6.88–
8.39 (m, 7H, ArH’s). IR spectra of 14a,b and 15a,b revealed bands at
1
1650 cm (RCON ).
Nitrosation of 11a and 11b with nitrous acid gave the nitroso deriva-
tives 16a and 16b respectively. The UV of the latter revealed two com-
mon maxima in the region 510–570 nm and 365–340 nm assigned to
n-n and
-
transition of the nitrosoimino groups.
Compounds 16a and 16b, upon being boiled in xylene, decomposed to
the corresponding 2,3-dihydrothiadiazolinones 17a and 17b. IR spectra
of 17a and 17b revealed an absorption band near 1680 cm 1. 1H NMR
spectrum of 17a showed signals at 6.18 (s, 2H, CH2) and 7.13–8.43
(m, 7H, ArH’s).
Treatment of 9 with phenylthiourea in ethanol afforded 21 (66%).
Structure of 21 was elucidated on the basis of elemental analyses, spec-
tral data, and an alternative synthesis method. Thus treatment of 9
with methyl phenylthiocarbamate12 in ethanolic triethylamine gave
identical product in all respects m.p., mixed m.p., and spectra) with
21. Scheme 3 explains the formation of 21.

1104
N. M. Rateb et al.
SCHEME 2
Compound 9 reacted with the appropriate dithioesters 24a–o in
ethanolic triethylamine at room temperature to give the correspond-
ing 2,3-dihydro-1,3,4-thiadiazole derivatives 27a–o, respectively (cf.
Scheme 4). Structure of 27 was confirmed on the basis of elemental anal-
1
yses, spectral data, and an alternative synthesis route. Thus, HNMR
spectrum of 27a showed signals at 6.07(s, 2H, CH2) and 6.87–8.54 (m,
13H, ArH’s and vinyl CH ). Products 27a–o are assumed to be formed
via elimination of alkanethiol from the corresponding cycloadduct 26,

1
Reactions of Hydrazonoyl Halides 35
1105
SCHEME 3
formed from 1,3-dipolar cycloaddition of nitrile imide 18 (formed in situ
from 9 and triethylamine) to the C S of the alkyl dithioester. The for-
mation of 27 also can be explained by 1,3-addition of thiol tautomer of
24 with nitrile imide 18 to afford a cyclic hydrazone 25, which was read-
ily cyclized to give intermediate 26 and which subsquently eliminated
an alkanethiol to give the final products 27a–o (cf. Scheme 4).
Moreover, treatment of hydrazonoyl bromide 9 with the appropriate
alkyl benzoylhydrazinecarbodithioates in ethanolic triethylamine gave
2,3-dihydro-1,3,4-thiadiazole derivative 30. Structure of 30 was con-
firmed on the basis of elemental analysis, spectral data, and an alterna-
tive synthesis route. 1HNMR spectrum showed signals at 6.09 (s, 2H,

1106
N. M. Rateb et al.
SCHEME 4
CH2), 6.14–8.54 (m, 12H, ArH’s), and 11.39 (s, br., 1H, NH). Thus,
hydrazonoyl bromide 9 reacted with 5-phenyl-1,3,4-oxadiazol-2-thione
in chloroform containing triethylamine to afford an identical product
in all respects (mp, mixed mp and spectra) with 30 (cf. Scheme 5).
EXPERIMENTAL
All melting points were determined on an electrothermal appara-
tus and are uncorrected. IR spectra were recorded (KBr) discs on a
Shimadzu FT-IR 8201 PC spectrophotometer. 1HNMR spectra were
recorded in CDCl3 and (CD3)2SO solution on a Varian Gemini 300 MHz
spectrometer, and chemical shifts were expressed in
units using

1
Reactions of Hydrazonoyl Halides 35
1107
SCHEME 5
tetramethylsilane (TMS) as an internal reference. Elemental analy-
ses were carried out at the Microanalytical Center of Cairo University.
Hydrazonoyl halides13–21 1a–g and alkyl carbodithioates22,23 were pre-
pared as previously reported.
Synthesis of Ethyl 6-(2H-Benzo[3,4-d]1,3-dioxolen-5-yl)-
4-methyl-2-thioxo-1,3-6-trihydropyrimidine-5-
carboxylate (3)
A mixture of ethyl acetoacetate (0.1 mol, 13 g), thiourea (0.11 mol,
8.2 g) and piperinal (0.1 mol, 15 g) in ethanol (30 ml) containing a
catalytic amount of concentrated hydrochloric acid (10 drops) was re-
fluxed for 3 h. The reaction mixture then was allowed to stand at room

1108
N. M. Rateb et al.
TABLE I Characterization Data of the Newly Synthesized Compounds
% Analyses calcd./found
Compd.
no.
Yield (%)
color
Mol. formula
mol. wt.
M.p., C
C
H
N
S
3
175–176
78
Pale brown
78
Pale brown
70
Pale brown
68
Pale yellow
72
Yellow
75
Yellow
69
Yellow
65
Brown
63
Brown
70
Brown
63
Brown
65
Brown
60
Yellow
68
Brown
70
Orange
68
Brown
65
C15H16N2O4S
320.37
C16H18N4O4S
334.38
C24H22N4O6
462.47
56.24
56.40
57.47
57.70
62.33
62.50
63.02
62.90
66.53
66.70
64.57
64.80
68.49
68.70
63.02
63.50
70.96
71.20
46.18
46.30
52.63
52.80
46.29
46.50
53.12
53.30
47.35
47.50
59.19
59.40
53.56
53.70
48.52
48.70
43.08
43.20
52.48
52.60
46.17
46.30
60.28
60.40
59.32
59.60
55.17
55.30
5.03
4.90
5.43
5.30
4.80
5.00
5.08
5.10
4.81
5.00
4.97
5.10
4.76
4.90
4.31
4.60
4.69
4.90
2.77
2.50
2.94
3.00
2.59
2.70
3.15
3.40
2.80
3.00
3.16
3.20
2.86
3.00
2.44
2.60
2.17
2.30
2.64
2.80
2.32
2.50
3.37
3.50
3.39
3.60
3.01
3.20
8.74
8.50
8.38
8.50
10.01
10.10
9.59
4
230–231
148–149
162–164
200–201
185–186
174–175
162–164
172–173
140–143
173–175
147–150
262–263
223–225
262–264
243–245
165–167
185–187
288–290
208–210
170–172
266–268
213–215
9.70
7a
12.11
12.90
11.76
11.50
13.38
13.50
12.55
12.70
11.02
10.80
10.89
11.00
10.03
10.30
11.54
11.70
16.37
16.50
14.39
14.50
14.58
14.70
12.99
13.00
12.55
12.70
11.36
11.60
18.86
19.00
16.75
16.50
12.24
12.00
10.77
10.50
13.39
13.60
15.72
15.90
16.08
16.30
7b
C25H24N4O6
476.49
C29H25N5O5
523.55
C24H22N4O5
446.47
7c
7d
7e
C29H24N4O5
508.54
7f
C27H22N4O5S
6.23
6.40
514.56
C33H26N4O5
558.59
C14H10BrN3O4
364.16
7g
9
11a
11b
14a
14b
15a
15b
16a
16b
17a
17b
21
C15H10N4O4S
9.37
9.50
342.34
C15H10N4O4Se
389.23
C17H12N4O5S
384.37
8.34
8.50
C17H12N4O5Se
431.27
C22H14N4O5S
7.18
7.30
446.44
C22H14N4O5Se
493.34
C
15H9N5O5S
371.33
8.63
8.80
Rose
60
Pink
65
Yellow
55
Brown
65
Red
65
Pale brown
62
Yellow
C
15H9N5O5Se
418.23
C15H9N3O5S
343.32
9.34
9.50
C15H9N3O5Se
390.22
C21H14N4O4S
418.43
7.66
7.80
7.20
7.40
7.36
7.50
27a
27b
C22H15N5O4S
445.46
C20H13N5O5S
435.42
(Continued on next page)

1
Reactions of Hydrazonoyl Halides 35
1109
TABLE I Characterization Data of the Newly Synthesized Compounds
(Continued)
% Analyses calcd./found
Compd.
no.
Yield (%)
color
Mol. formula
mol. wt.
M.p., C
C
H
N
S
27c
27d
27e
27f
27g
27h
27i
260–263
63
Pale brown
65
Yellow
67
Brown
65
Brown
60
Orange
58
Yellow
63
Brown
60
Pale brown
68
Yellow
58
Yellow
61
Brown
56
Yellow
50
C20H13N5O4S2
451.49
C21H14N6O4S
446.45
C23H17N5O4S
459.49
53.21
53.00
56.50
56.70
60.12
60.00
56.12
56.30
45.18
45.30
57.39
57.60
61.14
61.40
56.44
56.60
61.59
61.80
56.73
56.90
57.66
57.90
58.53
58.70
61.85
62.00
57.26
57.40
2.90
3.00
3.16
3.30
3.73
3.50
3.36
3.60
3.25
3.50
3.50
3.70
3.63
3.80
3.09
3.30
4.34
4.50
4.05
4.20
4.38
4.70
4.69
4.90
3.94
4.00
3.28
3.40
15.51
15.30
18.82
19.00
15.24
15.00
15.58
15.80
15.04
15.20
18.25
18.40
14.85
15.00
14.31
14.50
14.36
14.60
16.54
16.70
16.01
16.30
15.51
15.70
14.42
14.60
15.18
15.30
14.20
14.00
7.18
7.40
6.98
7.10
7.13
7.00
13.78
13.90
6.96
7.00
6.80
6.90
6.55
6.70
6.58
6.80
7.57
7.70
7.33
7.50
7.10
7.30
6.60
6.80
6.95
7.00
297–299
215–217
240–242
230–233
260–263
198–200
178–180
180–182
218–220
210–211
180–183
195–197
275–277
C21H15N5O5S
449.45
C21H15N5O4S2
465.51
C22H16N6O4S
460.47
C24H17N5O4S
471.50
27j
C23H15N5O6S
489.47
27k
27l
C25H21N5O4S
487.54
C20H17N5O4S
423.45
27m
27n
27o
30
C21H19N5O4S
437.48
C22H21N5O4S
451.51
C25H19N5O4S
485.53
C22H15N5O5S
461.46
Yellow
75
Orange
temperature overnight, whereby the solid precipitate so formed was col-
lected by filtration, washed with ethanol, and crystallized from ethanol
to give 3 (cf. Tables I and II).
Synthesis of Ethyl 4-(2H-Benzo[3,4-d]1,3-dioxolen-5-yl)-
6-methyl-2-methythio-3,4-dihydropyrimidine-5-
carboxylate (4)
Iodomethane (0.005 mol) was added portionwise with stirring to a mix-
ture of compound 3 (1.6 g, 0.005 mmol) and sodium ethoxide solution
(prepared by dissolving sodium metal [0.005 mmol, 0.11 g-atom]) in
ethanol (15 ml) for 4 h. The reaction mixture was left overnight at room
temperature and then the precipitate was collected and crystallized
from ethanol to give 4 (cf. Tables I and II).

1110
N. M. Rateb et al.
TABLE II Spectroscopic Data of Some Newly Synthesized Compounds
Compound
No.
(ppm)
3
1.25 (t, 3H, CH2CH3), 2.51 (s, 3H, CH3), 4.10 (q, 2H, CH2CH3), 5.89
(s, 2H, CH2), 6.64 (s, 1H, CH), 7.25–8.20 (m, 3H, ArH’s), 9.61 (s, 1H, NH),
and 10.35 (s, 1H, NH)
4
1.20 (t, 3H, CH2CH3), 2.50 (s, 3H, CH3), 2.8 (s, 3H, CH3), 4.10 (q, 2H,
CH2CH3), 5.89 (s, 2H, CH2), 6.64 (s, 1H, CH), 7.25–8.20 (m, 3H, ArH’s),
and 9.60 (s, 1H, NH)
7a
7b
7c
7d
1.23 (t, 3H, CH2CH3), 2.51 (s, 3H, CH3), 3.96 (s, 3H, OCH3), 4.12 (q, 2H,
CH2CH3), 5.88 (s, 2H, CH2), 6.64 (s, 1H, CH), and 6.87–8.20
(m, 8H, ArH’s)
1.25 (t, 3H, CH2CH3), 1.37 (t, 3H, CH2CH3) 2.51 (s, 3H, CH3), 4.12
(q, 2H, CH2CH3), 4.42 (q, 2H, CH2CH3), 5.89 (s, 2H, CH2), 6.64–8.20
(m, 9H, ArH’s and CH pyrimidine)
1.24 (t, 3H, CH2CH3), 2.54 (s, 3H, CH3), 4.12 (q, 2H, CH2CH3),
5.87 (s, 2H, CH2), 6.64 (s, 1H, CH pyrimidine), and 7.01–8.39 (m, 14H,
ArH’s and NH)
1.25 (t, 3H, CH2CH3), 2.51 (s, 3H, CH3), 2.54 (s, 3H, CH3), 4.42 (q, 2H,
CH2CH3), 5.88 (s, 2H, CH2), 6.63 (s, 1H, pyrimidine CH), and 6.90–8.23
(m, 8H, ArH’s)
7e
7f
1.22 (t, 3H, CH2CH3), 2.55 (s, 3H, CH3), 4.12 (q, 2H, CH2CH3), 5.83
(s, 2H, CH2), 6.56 (s, 1H, pyrimidine CH), 6.83–8.24 (m, 13H, ArH’s)
1.23 (t, 3H, CH2CH3), 2.54 (s, 3H, CH3), 4.12 (q, 2H, CH2CH3), 5.84
(s, 2H, CH2), 6.59–8.26 (m, 12H, ArH’s, and pyrimidine CH)
1.25 (t, 3H, CH2CH3), 2.57 (s, 3H, CH3), 4.11 (q, 2H, CH2CH3), 5.80
(s, 2H, CH2), 6.56–8.67 (m, 16H, ArH’s, and pyrimidine CH)
4.30 (s, 2H, CH2) and 7.28–8.19 (m, 8H, ArH’s, and NH)
6.62 (s, 2H, CH2) and 7.00–8.31 (m, 8H, ArH’s, and NH)
4.30 (s, 2H, CH2) and 7.28–819 (m, 8H, ArH’s, and NH, exchangeable)
2.43 (s, 3H, CH3CO), 6.07 (s, 2H, CH2), and 6.88–8.39 (m, 7H, ArH’s)
2.43 (s, 3H, CH3CON ), 6.08 (s, 2H, CH2), and 7.26–8.39 (m, 7H, ArH’s)
6.08 (s, 2H, CH2) and 6.95–8.46 (m, 12H, ArH’s)
7g
9
11a
11b
14a
14b
15a
15b
16a
16b
17a
17b
27a
27c
27e
27g
27h
27i
6.08 (s, 2H, CH2) and 6.95–8.46 (m, 12H, ArH’s)
6.09 (s, 2H, CH2) and 6.85–8.19 (m, 7H, ArH’s)
6.09 (s, 2H, CH2) and 6.85–8.19 (m, 7H, ArH’s)
6.18 (s, 2H, CH2) and 7.13–8.43 (m, 7H, ArH’s)
6.05 (s, 2H, CH2) and 6.85–8.24 (m, 7H, ArH’s)
6.07 (s, 2H, CH2) and 6.87–8.54 (m, 13H, ArH’s, and vinyl CH
6.08 (s, 2H, CH2) and 6.88–8.62 (m, 11H, ArH’s, and vinyl CH
)
)
2.48 (s, 3H, CH3), 6.13 (s, 2H, CH2), and 6.99–8.52 (m, 12H, ArH’s)
2.51 (s, 3H, CH3), 6.09 (s, 2H, CH2), and 6.86–8.52 (m, 10H, ArH’s)
2.45 (s, 3H, CH3), 6.07 (s, 2H, CH2), and 6.53–8.54 (m, 11H, ArH’s)
6.13 (s, 2H, CH2) and 6.87–7.55 (m, 12H, ArH’s), 8.29 (d, 1H, CH CH ),
8.50 (s, 1H, vinyl CH), and 8.51 (d, 1H, CH CH
)
27k
27l
1.26 (d, 6H, (CH3)2CH), 2.95 (sept, 1H, (CH3)2CH ), 6.09 (s, 2H, CH2),
and 6.09–8.50 (m, 12H, ArH’s, and CH vinyl)
2.55 (t, 4H), 2.6 (pent. 4H), 6.07 (s, 2H, CH2), and 7.87–8.52 (m, 7H, ArH’s)

1
Reactions of Hydrazonoyl Halides 35
1111
Synthesis of 1,2,4-Triazolino[4,3-a]pyrimidines 7a-g
Method A
A mixture of the appropriate hydrazonoyl halides 1a–g (0.005 mol),
compound 3 (1.6 g, 0.005 mol), and triethylamine (0.75 ml, 0.005 mol)
in chloroform (20 ml) was refluxed for 10 h. The reaction mixture was
evaporated under reduced pressure; the oil residue was triturated with
ethanol (10 ml). The resulting solid collected and crystallized from
ethanol to give 7a–g respectively (cf. Tables I and II).
Method B
Equimolar amounts (0.005 mol) of the appropriate hydrazonoyl
halides 1a–g, compound 4, and sodium ethoxide in ethanol (20 ml) was
refluxed for 3 h. The reaction mixture was cooled; the resulting solid
was collected and crystallized from ethanol to give identical products in
all respects (m.p., mixed m.p., and spectra) with corresponding products
obtained by Method A.
Synthesis of ((1E)-2-(2H-Benzo[3,4-d]1,3-dioxolen-5-yl)-
1-aza-2-bromovinyl)(4-nitrophenyl)amine (9)
A solution of bromine (16g, 5 ml, 0.1 mol) in acetic acid (10 ml) was
added dropwise while stirring to a solution of piperinal-4-nitrophenyl-
hydrazone (8) (g, 28.5 mol) in acetic acid (100 ml) at room temperature.
The reaction mixture was stirred for 2 h, the resulting solid was
collected and crystallized from ethanol to give 9 (cf. Tables I and II).
Synthesis of 5-(2H-Benzo[d ]1,3-dioxolen-5-yl)-
3-(4-nitrophenyl)-1,3,4-thiadiazolin-2-imine (11a) and
5-(2H-benzo[d ]1,3-dioxolen-5-yl)-3-(4-nitrophenyl)-1,3,4-
selenadiazolin-2-imine (11b)
Method A
A mixture of 9 (0.005 mol) and potassium thiocyanate or potassium
selenocyanate (0.005 mol) in ethanol (30 ml) was stirred at room tem-
perature for 4 h. The crude precipitate was collected, washed with water,
and then crystallized from ethanol to give 11a and 11b respectively (cf.
Tables I and II).
Method B
A mixture of equimolar amount of 9 and thiourea (0.005 mol) in
ethanol (20 ml) was refluxed for 30 min. The resulting solid after cooling
was collected, washed with water, and crystallized from ethanol to give

1112
N. M. Rateb et al.
identical product in all respects (m.p., mixed m.p., and spectra) with
11a.
Acylation of 11a and 11b
The appropriate 11a or 11b (0.5 g) was stirred in acetic anhydride
(10 ml) for 10 min. The reaction mixture was left for 3 h at room
temperature. The solid so formed was collected and crystallized
from acetic acid to give 1-[5-(2H-benzo[d]1,3-dioxolen-5-yl)-3-(4-
nitrophenyl)-1,3,4-thiadiazolin-2-ylidene]-1-azaacetone (14a) and 1-[5-
(2H-benzo[d]1,3-dioxolen-5-yl)-3-(4-nitrophenyl)-1,3,4-selenodiazolin-
2-ylidene]-1-azaacetone (14b) respectively (cf. Tables I and II).
Benzoylation of 11a and 11b
A mixture of equimolar amounts (0.005 mol) of 11a or 11b and
benzoyl chloride in pyridine (10 ml) was heated at 80 C for 10 min.
The reaction mixture was poured into ice-cold water and acidi-
fied with hydrochloric acid. The resulting product was collected,
washed with boiling water, and then crystallized from acetic acid
to afford 2-[5-(2H-benzo[d]1,3-dioxolen-5-yl)-3-(4-nitrophenyl)-1,3,4-
thiadiazolin-2-ylidene]-2-aza-1-phenylethan-1-one (15a) and 2-[5-(2H-
benzo[d]1,3-dioxolen-5-yl)-3-(4-nitrophenyl)-1,3,4-selenodiazolin-2-yli-
dene]-2-aza-1-phenylethan-1-one (15b) respectively (cf. Tables I and II).
Synthesis of 5-(2H-Benzo[d]1,3-dioxolen-5-yl)-
2-(azanitrosomethylene)-3-(4-nitrophenyl)-
1,3,4-thiadiazoline (16a) and 5-(2H-Benzo[d]1,3-
dioxolen-5-yl)-2-(azanitrosomethylene)-
3-(4-nitrophenyl)-1,3,4-selenadiazoline (16b)
A solution of 11a (or 11b) (0.005 mol) in acetic acid (30 ml) was
treated with a saturated solution of sodium nitrite (20 ml) while stir-
ring (30 min). The solid so formed was collected and crystallized from
acetone (cf. Tables I and II).
Synthesis of 5-(2H-Benzo[d]1,3-dioxolen-5-yl)
-3-(4-nitrophenyl)-1,3,4-thiadiazolin-2-one (17a) and
5-(2H-Benzo[d]1,3-dioxolen-5-yl)-3-(4-nitrophenyl)-
1,3,4-selenadiazolin-2-one (17b)
The appropriate nitroso derivatives 16a (or 16b) (0.005 mol) were re-
fluxed in xylene (30 ml) for 30 min and then left overnight at room

1
Reactions of Hydrazonoyl Halides 35
1113
temperature. The solvent was removed and the mixture was triturated
with ethanol. The so formed solid was collected by filtration and then
crystallized from ethanol (cf. Tables I and II).
Synthesis of 5-(2H-Benzo[d]1,3-dioxolen-5-yl)-
3-(4-nitrophenyl)-N-phenylimino-2,3-dihydro-1,3,4-
thiadiazole (21) and Unsymmetrical Azines 27a–o
Triethylamine (0.75 ml, 0.005 mol) was added while stirring at room
temperature to a solution of the hydrazonoyl bromide 9 (0.005 mol) and
the appropriate methyl phenyldithiocarbamate (or phenylthiourea) or
alkyl carbodithioates 24a–o (0.005 mol) in ethanol (20 ml). The reaction
mixture was stirred for 2 h, the so formed solid was collected and crys-
tallized from acetic acid to give 21 or 27a–o respectively (cf. Tables I
and II).
Synthesis of 2,3-Dihydro-1,3,4-thiadiazole Derivative 30
Method A
Triethylamine (0.75 ml, 0.005 mol) was added while stirring at room
temperature to a mixture of the hydrazonoyl bromide 9 (1.8 g, 0.005 mol)
and benzoylhydrazinecarbodithioate in ethanol (20 ml). The reaction
mixture was stirred for 2 h. The so formed solid was collected and crys-
tallized from acetic acid (cf. Tables I and II).
Method B
A mixture of hydrazonoyl bromide 9 (1.8 g, 0.005 mol), 5-phenyl-
1,3,4-oxadiazol-2-thione (0.89 g, 0.005 mol) and triethylamine (0.75 ml,
0.005 mol) in chloroform (20 ml) was refluxed for 10 h; the solvent
then was evaporated under reduced pressure. The oil residue was trit-
urated with ethanol (10 ml); the resulting solid was collected and crys-
tallized from acetic acid to give identical product in all respects (m.p.,
mixed m.p., and spectra) with compound 30 which was obtained from
Method A.
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