Reactions of hydrazonoyl halides 331: Synthesis of some new 2,3-dihydro-1,3,4-thiadiazoles containing pyrazol-3-yl, indolin-2-one-2-yl and indan-1,3-dione-2-yl moieties

Article abstract of DOI:10.1080/10426500214563

Some new 2,3-dihydro-1,3,4-thiadiazoles containing pyrazol-3-yl, indolin-2-one-2-yl and indan-1,3-dione-2-yl moieties in a good yields obtained from the reaction of hydrazonoyl halides with thiocarbamate and carbodithioate in ethanolic triethylamine respe

Full text of DOI:10.1080/10426500214563

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Phosphorus, Sulfur, and Silicon and the Related
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Reactions of Hydrazonoyl Halides 33 1 : Synthesis of
Some New 2,3-Dihydro-1,3,4-thiadiazoles Containing
Pyrazol-3-yl, Indolin-2-one-2-yl and Indan-1,3-dione-2-
yl Moieties
Abdou O. Abdelhamid a , Soad M. Abdelgawad b & Sohad F. El-Sharnoby c
a Department of Chemistry, Faculty of Science , Cairo University , Giza, 12316, Egypt
b Department of Chemistry, Faculty of Science (Girls Branch) , Azhar University , Cairo,
Egypt
c Agriculture Research Center , Giza, Egypt
Published online: 27 Oct 2010.
To cite this article: Abdou O. Abdelhamid , Soad M. Abdelgawad & Sohad F. El-Sharnoby (2002) Reactions of Hydrazonoyl
Halides 33 1 : Synthesis of Some New 2,3-Dihydro-1,3,4-thiadiazoles Containing Pyrazol-3-yl, Indolin-2-one-2-yl and
Indan-1,3-dione-2-yl Moieties, Phosphorus, Sulfur, and Silicon and the Related Elements, 177:11, 2699-2709, DOI:
10.1080/10426500214563
To link to this article: http://dx.doi.org/10.1080/10426500214563
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Phosphorus, Sulfur and Silicon, 2002, Vol. 177:2699–2709
C
Copyright 2002 Taylor & Francis
1042-6507/02 $12.00 + .00
DOI: 10.1080/10426500290110676
REACTIONS OF HYDRAZONOYL HALIDES 331:
SYNTHESIS OF SOME NEW
2,3-DIHYDRO-1,3,4-THIADIAZOLES CONTAINING
PYRAZOL-3-YL, INDOLIN-2-ONE-2-YL AND
INDAN-1,3-DIONE-2-YL MOIETIES
Abdou O. Abdelhamid,a Soad M. Abdelgawad,b
and Sohad F. El-Sharnobyc
Department of Chemistry, Faculty of Science, Cairo University,
Giza 12316, Egypt;a Department of Chemistry, Faculty
of Science (Girls Branch), Azhar University, Cairo, Egypt;b
and Agriculture Research Center, Giza, Egyptc
(Received February 24, 2002; accepted April 12, 2002)
Some new 2,3-dihydro-1,3,4-thiadiazoles containing pyrazol-3-yl,
indolin-2-one-2-yl and indan-1,3-dione-2-yl moieties in a good yields
obtained from the reaction of hydrazonoyl halides with thiocarbamate
and carbodithioate in ethanolic triethylamine respectively. In contrast,
pyrazolylthiourea reacts with hydrazonoyl halides under the same con-
dition afford corresponding hydrazonoyl sulfide derivatives.
Keywords: 2,3-Dihydro-1,3,4-thiadiazole; carbodithioate; hydrazonoyl
halides; nitrile imine
INTRODUCTION
Many pyrazoles have been reported be use as antipyretic and analgesic
4
drugs,2 bactericides, and fungicides.5 Isatin derivatives have been
8
used in the development of colour photographic recording materials6
12
of blood coagulation,9
of liquid crystal components for display
devices,13
and in the inhibition of corrosion of aluminum,16 Fe-Ni
15
alloys17 and of iron.18 On the other hand; thiadiazoles are known to
21
be highly biologically active reagents.19
Based on these findings, it
was of interest to synthesis some 2,3-dihydro-1,3,4-thiadiazoles directly
with pyrazol-3-yl or indolin-2-one-2-yl or indan-1,3-dione-2-yl moieties
are expected to posses potential biological activities.
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
2699

2700
A. O. Abdelhamid et al.
RESULTS AND DISCUSSION
N-phenyl-N-(5-phenylpyrazol-3-yl)thiourea (1) reacts with C-ethoxy-
carbonyl-N-phenylhydrazonoyl chloride (2a) to give isolable product.
Its structure was confirmed on the basis of analytical and spec-
troscopic data. Thus, IR (cm 1) spectrum showed bands at 3330
(NH) and 1701 (CO) and its 1H NMR ( ppm) spectrum showed
signals at
= 1.22 (t, 6H), 4.20 (q, 4H), 7.01–7.47 (m, 10H) and
10.83 (s, br., 2H). Based on these data the product formulated
as ethyl 2-[2-aza-1-(ethoxycarbonyl)-2-(phenylamino)vinylthio]-3-aza-
3-(phenyl-amino)prop-2-enoate (7a). Structure 7 was further confirmed
by independent synthesis. Thus, cyanothioacetamide treated with 2a to
produce a product22 proved to be identical in all respects (m.p., mixed
m.p., and spectra) with 7a. The formation of 7 can be explained via
elimination hydrogen chloride to give the intermediate 3, which read-
ily to give 6. Compound 6 reacts with 2a to give the final product 7a.
On the above date the structures 4 and 5 were ruled out (cf. Scheme 1).
SCHEME 1

Reactions of Hydrazonoyl Halides
2701
Also, compound 1 react with C-acetyl-N-phenylhydrazonoyl chloride
(8a) in N,N-dimethylformamide containing potassium hydroxide to give
product, identified as (3E)-4-aza-3-{1-[aza(phenylamino)methylene]-
2-oxopropylthio}-4-(phenylamino)but-3-en-2-one (12a). Structure 12a
was confirmed on the basis of analytical and spectroscopic data. Thus,
IR (cm 1) spectrum of 12a revealed bands at 3425 (NH) and 1658 (CO).
Its 1H NMR ( ppm) spectrum showed signals at = 2.53 (s, 6H), 7.06–
7.43 (m, 10H) and 11.55 (s, br., 2H). Unequivocal support for the struc-
ture 12a, it showed no depression in mixed m.p. with authentic sample23
(which prepared from reaction of N-phenylcyanothioacetamide with 8a)
(cf. Scheme 2).
SCHEME 2
On the other hand, treatment of potassium [(3-phenylpyrazol-
5-yl)amino]methanedithioate (13)24 with methyl iodide afforded
3-[(methylthio)thiocarbonoylamino]-5-phenylpyrazole (14). Its struc-
ture was confirmed on the basis of elemental analyses, spectral data,
and chemical transformation (cf. Experimental part). Compound 14
react with C-ethoxycarbonyl-N-Phenylhydrazonoyl chloride (2a) in
ethanol containing triethylamine gave 2,3-dihydro-1,3,4-thiadiazole
4a. The structure was deduced from their spectral and elemental analy-
sis. IR (cm 1) spectrum revealed bands at 3330 (NH) and 1710 (CO). Its
1H NMR ( ppm) spectrum showed signals at = 1.44 (t, 3H, CH2CH3),
4.33 (q, 2H, CH2CH3), 6.4 (s, IH, pyrazole C-4), 7.21–7.47 (m, 10H,

2702
A. O. Abdelhamid et al.
ArH’s), and 8.42 (s, IH, NH). The formation of thiadiazole 4a can be
explained via elimination of methanethiol from cycloadduct 16, which
is assumed to be formed from 1,3-dipolar cycloaddition of nitrile imide
(generate in situ by treatment of 2a with triethylamine) to C S double
bond of 14 (pathway A) or by its stepwise path involving substitution
via 1,3-addition of thiol 14 to nitrile imide to give a cyclic hydrazone 15
(pathway B), which transformed to cyclic intermediate 16. Cyclization
of the latter is achieved by elimination of methanethiol to afford the
final product 4a. All attempts to isolate either intermediate hydrazone
15 or cycloadduct 16 were unsuccessful (cf. Scheme 3)
SCHEME 3

Reactions of Hydrazonoyl Halides
2703
Similarly, the 3-[(methylthio)thiocarbonaylamino]-5-phenylpyrazole
(14) reacted with the appropriate hydrazonoyl halides 2b, (8, 17)a, b,
18–20, in ethanolic triethylamine to give the corresponding 2,3-dihydro-
1,3,4-thiadiazole 4b, (10, 22)a, b, and 23–25, respectively (cf. Scheme 3).
The potential reactivity of compounds 27(a25, b) [which prepared
from reaction of isatin with alkyl hydrazinecarbodithioate (26a, b)]
toward hydrazonoyl halides to afford 2,3-dihydro-1,3,4-thiadiazoles
derivatives. Thus, 27a reacted with C-ethoxyl-N-phenylhydrazonoyl
chloride (2a) in ethanol containing triethylamine to afford 2,3-dihydro-
1,3,4-thiadiazole derivatives 30a.
Structure of 30a was confirmed on the basis of analytical, spectro-
scopic data and alternative synthesis methods. Thus IR (cm 1) spec-
1
trum revealed bands at 3147 (NH) and 1720, 1705 (CO’s). H NMR
( ppm) spectrum showed signals at = 1.44 (t, 3H), 4.34(q, 2H), 7.21–
7.74 (m, 9H), and 10.71 (s, br., 1H). On the other hand, the reaction
of 27b with 2a in ethanol containing triethylamine afforded product
identical in all respects (m.p., mixed m.p., and spectra) with 30a.
Unequivocal support on the structure of 30a obtained by reaction of
2-hydrazino-2,3-dihydro-1,3,4-thiadiazole26 (31) with isatin (25) gave
identical product in all respect (m.p., mixed m.p., and spectra) with
30a (cf. Scheme 4). The formation of unsymmetrical azine 30 can be
explained via elimination alkyl thiol (RSH) from cycloadduct 29, which
assumed to be formed from 1,3-dipolar cycloaddition or 1,3-addition of
nitrile imine to CS or thiol of 27.
Similarly, the appropriate hydrazonoyl halides 2b, (8, 17)a, b, 18,
19, 21 react with the appropriate 27a, b in ethanol containing triethy-
lamine to give the corresponding unsymmetrical azine 30b, (32, 33)a, b,
and 34–36 respectively. All compounds synthesized are elucidated its
structure on the basis elemental analysis and spectroscopic data (cf.
Experimental part).
Finally, indon-1,2,3-trione (37) reacts with the appropriate alkyl
hydrazinecarbodthioate (26a, b) to give the corresponding 2-{aza-
[alkylthiothioxomethyl)-amino]methyelne}indi-one-1,3-dione (38a, b),
respectively. The structure of 38 was confirmed on the basis of an-
alytical, spectroscopic data, and chemical transformation. Thus, IR
(cm 1) spectra of 38 revealed bands at 3330 (NH), 1728, and 1698
1
(COs). H NMR ( ppm) spectrum of 38a showed signals at 2.95 (s,
3H) and 7.22–7.46 (m, 4H). Thus, the appropriate of 40a, b reac-
tions with C-ethoxycarbonoyl-N-phenylhydrazonoyl chloride (2a) in
ethanol containing triethylamine to afford products has molecular for-
mula C20H14N4O4S. IR (cm 1) spectrum revealed bands near 1740–
1
1715 (CO’s). H NMR spectrum showed signals ( ppm) at 1.36 (t, 3H,
CH2CH3), 4.42 (q, 2H, CH2CH3) and 7.35–8.05 (m, 9H, ArH’s). Based on

2704
A. O. Abdelhamid et al.
SCHEME 4
the above data the product was formulated as: ethyl 2-[1,2-diaza-z-(1,3-
dioxindan-2-ylidene-3-phenyl-1,3,4-thiadiazdine-5-carboxylate (41a).
Unequivocal support on the structure obtained from the study of
the products reaction of 2-hydrazino-2,3-dihydro-1,3,4-thiadiazole 31
with indain-1,2,3-trione in ethanol, gave identical properties (m.p.,
mixed m.p., and spectra) with 41a (cf. Scheme 5). The formation
of 41 can be explained via elimination of alkyl mercaptan from cy-
cloaddition 40, which assumed to be formed from 1,3-dipalor cycload-
dition or 1,3-addition of nitrile imine (which prepared in situ from
hydrazonoyl chloride 2a with triethylamine), to carbodithioate 38
(cf. Scheme 5).
Simiar, the appropriate hydrazonoyl halides 2b, (8, 17)a, b, 18–20
react with the appropriate 38a, b in ethanol containing triethy-
lamine to give the corresponding 2,3-dihydro-1,3,4-thiadiazole deriva-
tives 41b,(42, 43)a, b, and 44–46, respectively (cf. Scheme 5).

Reactions of Hydrazonoyl Halides
2705
TABLE I Characterization Data of the Newly Synthesized Compounds
% Analyses calcd./found
Compd.
no.
Yield m.p. ( C)
Mol. formula
mol. wt.
R
(%)
solvent
C
H
N
S
4a
4b
OC2H5
85
98–100
Pet. ether
95
Pet. ether
115
C20H17N5O2S 61.36 4.37 17.89
391.45 61.30 4.30 17.80
C21H19N5O2S 62.20 4.72 17.27
8.19
8.10
7.90
7.90
8.87
8.80
8.54
8.50
OC2H5
CH3
80
80
75
—
405.47
C19H15N5OS
361.42
C20H17N5OS
375.45
62.20 4.70 17.20
63.14 4.18 19.37
63.10 4.10 19.30
63.98 4.56 18.65
53.90 4.50 18.60
10a
10b
14
EtOH
139
CH3
EtOH
168–70
Benzene
113–115
EtOH
75–77
Pet. ether
58–60
Pet. ether
80–82
Pet. ether
50
Pet. ether
221–23
EtOH
256
AcOH
295
AcOH
298–300
AcOH
270–72
AcOH
330–33
AcOH
350–52
AcOH
295
—
C11H11N2S2
249.34
52.98 4.49 16.85 25.72
52.50 4.40 16.80 25.70
22a
22b
23
NHC6H5
NHC6H5
C6H5
65
60
80
70
65
89
85
80
85
75
70
65
70
80
75
88
92
80
C24H18N6OS
438.51
C25H20N6OS
452.54
C24H17N5OS
423.49
C28H19N5OS
473.55
65.73 4.13 19.16
65.70 4.10 19.10
66.35 4.45 18.57
66.30 4.40 18.50
68.07 4.05 16.53
68.00 4.00 16.50
71.01 4.04 14.78
71.00 4.00 14.70
7.31
7.30
7.08
7.00
7.57
7.50
6.77
6.74
24
2-C10H7
2-C4H3S
CH2C6H5
OC2H5
OC2H5
CH3
25
C22H15N5OS2 61.52 3.52 16.30 14.92
429.52 61.50 3.50 16.30 14.50
C16H13N3OS2 58.69 4.00 12.83 19.58
327.43 58.60 4.00 12.80 19.50
C19H15N5O3S 58.00 3.84 17.80
393.42 58.00 3.80 17.80
C20H17N5O3S 58.95 4.20 17.19
407.45 58.90 4.20 17.20
C18H13N5O2S 59.49 3.60 19.27
363.39 59.40 3.60 19.29
C19H15N5O2S 60.46 4.00 18.55
377.42 60.40 4.00 18.50
C23H16N6O2S 62.71 3.66 19.08
440.48 62.70 3.60 19.00
C24H18N6O2S 63.42 3.99 18.49
454.51 63.40 3.90 18.40
C23H15N5O2S 64.92 3.55 16.46
425.47 65.00 3.30 16.50
C27H17N5O2S 68.05 3.60 14.72
475.53 68.00 3.80 14.60
C21H13N5O3S 60.71 3.15 16.85
415.44 60.50 3.30 16.80
27b
30a
30b
32a
32b
33a
33b
34
8.15
8.10
7.87
7.80
8.82
8.80
8.49
8.40
7.28
7.20
7.05
7.00
7.53
7.20
6.74
6.70
7.71
7.60
CH3
NHC6H5
NHC6H5
C6H5
AcOH
317
AcOH
270
AcOH
108–110
EtOH
35
2-C10H7
2-C4H3O
CH3
36
38a
38b
41a
C11H8N2O2S2 49.98 3.05 10.59 24.25
264.32 49.90 3.00 10.50 24.20
CH2C6H5
OC2H5
130–132 C17H12N2O2S2 59.98 3.55
8.22 18.83
8.20 18.80
EtOH
190–92
AcOH
340.41
59.90 3.50
C20H14N4O4S 59.11 3.47 13.78
406.42 59.10 3.40 13.70
7.89
7.80
(Continued on next page)

2706
A. O. Abdelhamid et al.
TABLE I Characterization Data of the Newly Synthesized Compounds
(Continued)
% Analyses calcd./found
Compd.
no.
Yield m.p. ( C) Mol. formula
R
(%)
solvent
mol. wt.
C
H
N
S
41b
42a
42b
43a
43b
44
OC2H5
80
180–82
AcOH
140
AcOH
170
AcOH
185
AcOH
190
AcOH
145
AcOH
125–27
AcOH
195
C21H16N4O4S 59.99 3.83 13.32
420.45 59.90 3.80 13.30
C19H12N4O3S 60.63 3.21 14.88
376.39 60.60 3.20 14.80
C20H14N4O3S 61.53 3.61 14.35
390.42 61.50 3.60 24.30
C24H15N5O3S 63.57 3.33 15.44
453.48 63.50 3.30 15.40
C25H17N5O3S 64.23 3.66 14.98
467.50 64.00 3.60 14.90
C24H14N4O3S 65.74 3.22 12.78
438.46 65.70 3.20 12.70
C28H16N4O3S 68.84 3.30 11.47
488.50 68.80 3.30 11.40
C22H12N4O4S 61.67 2.82 13.08
425.43 61.60 2.80 13.00
7.62
7.60
5.81
8.50
8.21
8.20
7.07
7.00
6.86
6.80
7.31
7.30
6.56
6.50
7.48
7.40
CH3
85
75
72
75
70
80
75
CH3
C6H5NH
C6H5NH
C6H5
45
2-C10H7
2-C4H3O
46
AcOH
SCHEME 5

Reactions of Hydrazonoyl Halides
2707
TABLE II Spectroscopic Data of the Newly Synthesized Compounds
Compd.
no.
1
IR (cm
)
1H NMR ( ppm)
4a
3330 (NH) and
1707 (CO)
1.44 (t, 3H, CH2CH3), 4.44 (q, 2H, CH2CH3),
6.4 (s, IH, pyrazole (C-40), 7.21–7.92 (m, 11 H,
ArHs and NH)
4b
3261 (NH) and
1708 (CO).
1.44 (t, 3H, CH2CH3), 2.3 (s, 3H, 4-CH3C6H4),
4.44 (q, 2H, CH2CH3), 6.4 (s, IH, pyrazole (C-40),
7.21–7.92 (m, 10 H, ArHs and NH)
1.22 (t, 6H), 4.20 (q, 4H), 7.01–7.47 (m, 10H)
and 10.83 (s, br., 2H).
10
3330 (NH) and
1701.6 (CO)
14
3247 (NH) and
1681 (CO)
2.38 (s, 3H), 6.4 (s, 1H), 7.07–7.48 (m, 10H)
and 10.68 (s, 1H).
22a
22b
24
3244 (NH) and 1676
6.42 (s, 1H), 7.22–7.52 (m, 15H), 9.22 (s, 1H)
and 10.67 (s, 1H).
2.33 (s, 3H), 6.42 (s, 1H), 7.22–7.52 (m, 9H),
9.22 (s, 1H) and 10.67 (s, 1H).
3240 (NH) and 1672
3240 (NH) and
1673 (CO)
6.42 (s, 1H), 7.17–7.66 (m, 18H).
27a
27b
30a
30b
3340 (NH) and
1703 (CO)
3340 (NH) and
1703 (CO)
3147 (NH) and 1720,
1705 (COs)
3140 (NH) and
1747 (COs)
2.92 (s, 3H), 6.82–7.53 (m, 4H), 10.71 (s, 1H) and
11.0 (s, 1H).
2.66 (s, 2H), 6.82–7.53 (m, 9H), 10.71 (s, 1H) and
11.0 (s, 1H).
1.38 (t, 3H, CH2CH3), 4.34 (q, 2H, CH2CH3),
7.21–7.74 (m, 9H) and 10.70 (s, br., 1H)
1.34 (t, 3H, CH2CH3), 2.48 (s, 3H, 4-CH3C6H4),
4.42 (q, 2H, CH2CH3), and 6.83–7.87 (m, 9H,
ArHs and NH proton).
32a
32b
38a
38b
41a
41b
3134 (NH), 1712,
1691 (CO)
3161 (NH), 1714,
1693 (CO)
3330 (NH), 1728
and 1698 (COs)
3330 (NH), 1728
and 1698 (COs)
1728,1698 (COs)
2.33 (s, 3H), 7.21–7.74 (m, 9H) and 10.70 (s, br., 1H)
2.33 (s, 3H), 244 (s, 3H), 7.21–7.74 (m, 8H) and
10.70 (s, br., 1H).
2.95 (s, 3H), 7.22–7.46 (m, 4H) and 10.55 (s, 1H)
2.65 (s, 2H), 7.22–7.46 (m, 9H) and 10.55 (s, 1H)
1.36 (t, 3H, CH2CH3), 4.42 (q, 2H, CH2CH3)
and 7.35–8.05 (m, 9H, ArHs)
1740, 1720 (COs)
1.36 (t, 3H, CH2CH3), 2.45 (s, 3H), 4.42 (q, 2H,
CH2CH3) and 7.35–8.05 (m, 8H, ArHs)
2.32 (s, 3H), and 7.35–8.05 (m, 9H, ArHs)
2.32 (s, 3H), 2.42 (s, 3H), and 7.35–8.05 (m, 8H,
ArHs)
42a
42b
1728, 1689 (COs)
1728, 1689 (COs)
45
1728, 1690 (COs)
7.26–8.33 (m, ArHs)

2708
A. O. Abdelhamid et al.
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 spectrome-
ter and chemical shifts were expressed in units using TMS as internal
reference. Elemental analyses were carried out at the Microanalytical
Center of the Cairo University.
Syntheses of 2,3-Dihydro-1,3,4-thadiazoles
(4, 10, 22)a, b, and 23--25
Equimolar amounts of the appropriate 3-amino-5-phenylpyrazole,
potassium hydroxide, carbon hydroxide (5 mmol, each) in N,N-di-
methylformamide (15 ml) was stirred at room temperature for 3 h until
the potassium hydroxide dissolved, and then methyl iodide (0.5 ml) was
added. Each hydrazonoyl hydrazonoyl halides (2, 8, 17)a, b, 18, 19, 21
(5 mmol) was added to the solution with stirring and then triethyamine
(0.75 ml) was added. The resulting solid was collected, washed, and then
crystallized from acetic acid to afford thiadiazoles (4, 10, 22)a, b, and
23–25, respectively (cf. Tables I and II).
Syntheses of 2,3-Dihydro-1,3,4-thadiazoles (30, 32, 33,
41--43)a, b, 34--36, and 44--46
Triethylamine (0.75 ml, 5 mmol) was added to a mixture of the appro-
priate (5 mmol) and the appropriate hydrazonoyl bromide (2, 8, 17)a, b,
18–20 (5 mmol) and the appropriate alkyl carbodithioates (29, 40)a, b
(5 mmol) in ethanol (20 ml) while stirring. The reaction was stirred
for 30 min at room temperature. The formed precipitate was collected,
washed with ethanol, and crystallized from acetic acid to give 1,3,4-
thiadiazolines (30, 32, 33, 41–43)a, b, 34–36, and 44–46 respectively.
REFERENCES
[1] a) Part 32: A. O. Abdelhamid, M. M. M. Sallam, and S. A. Amer, Heteroatom Chem.,
12, 468 (2001); b) H. Stetter and E. Rauscher, Chem. Ber., 93, 2054 (1960).
[2] A. J. Ryan, P. G. Welling, and S. E. Wright, Food Cosmet. Toxicol., 7(4), 287 (1970).
[3] A. Ebnother, E. Jucker, and A. Lindeman, Helv. Chim. Acta, 42, 1201 (1959).
[4] A. Burger, Medicinal Chemistry (Interscience, New York, 1945).
[5] K. Kueffner, P. Marx, and W. Laessig, Ger. Offen. DE 3,217,877 (17 Nov. 1983),
pp. 53 [Chem. Abstr., 100, 183105 (1984)].

Reactions of Hydrazonoyl Halides
2709
[6] A. G. Abolin, E. I. Balabanov, B. P. Bespalov, B. M. Rumyantsev, V. V. Titov, and
G. I. Yudina, Zh. Nauch. Prikl. Fotogr., 26, 182 (1981).
[7] A. Sugai, Kokai Tokkyo Koho JP 9040644 (10 Feb. 1997) [Chem. Abstr., 126, 218539z
(1997)].
[8] H. Anraku, Eur. Pat. Appl. EP 241, 314 (14 Oct. 1987), pp. 45 (1987) [Chem. Abstr.,
109, 4559f (1988)].
[9] H. Anraku, Kokai Tokkyo Koho JP 62240616 1987, pp. 1 (1987) [Chem. Abstr., 108,
183284m (1988)].
[10] H. Anraku, Jpn. Kokai Tokkyo Koho JP 63 82. 361 (13 Apr. 1988), p. 7 [Chem. Abstr.,
110, 228133w (1989)].
[11] H. Anraku, U.S. Pat. 5413786, pp. 12 (1995); [Chem. Abstr., 122, 1115b (1995)].
[12] M. Ozutsumi, Y. Ohnishi, Y. Miyazawa, and M. Gonda, Japan Kokai, 75 57, 48 19
(May 1975), p. 6 [Chem. Abstr., 85, 134048k 1976].
[13] A. V. Ivashchenko, V. T. Lazareva, and V. G. Rumyantsev, Chem. Heterocycl. Compd.
(Engl. Transl.), 18, 190 (1982).
[14] S. Yamamiya, Y. Abe, H. Nishikatsu, and S. Sasaki, JP 4023869, p. 1 (1992) [Chem.
Abstr., 117, 9825q (1992)].
[15] D. D. N. Singh, M. M. Singh, R. S. Chaudhary, and C. V. J. Agarwal, Appl. Elec-
trochem., 587 (1980).
[16] T. Kawana, A. Hirano, T. Matsuda, H. Kimura, and H. Yatagai, JP 61082325, 1986,
p. 1 [Chem. Abstr., 102, 176804z (1985)].
[17] Y. S. Mohamed, A. E. M. N. Gohar, F. F. Abdel-Latif, and M. Z. A. Badr, Pharmazie,
40, 312 (1991).
[18] P. N. Bharagava and S. C. Sharma, Bull. Soc. Jpn., 35 (1926).
[19] S. K. Mallick, A. R. Martin, and R. G. Lingard, J. Med. Chem., 14, 528 (1971).
[20] A. Andolsek, B. Stanovinik, M. Tisler, M. Likar, and P. Schauer, J. Med. Chem., 14,
53 (1971).
[21] H. Graubaum, J. Prakt. Chem., 335, 88 (1993).
[22] A. O. Abdelhamid and S. E. Abdou, Sulfur Letter, 6, 41 (1987).
[23] A. O. Abdelhamid, S. E. Abdou, and F. H. El-Shiaty, Phosphorus and Sulfur, 88, 217
(1994).
[24] R. M. Mohareb, H. F. Zohdi, and W. W. Wardakhan, Monatsheftejur Chemie, 126,
1391 (1995).
[25] Y. P. Kovtun and N. N. Romanov, Khim. Geteroskit Soedin, 211 (1985).
[26] H. F. Zohdi, N. M. Rateb, M. M. M. Sallam, and A. O. Abdelhamid, J. Chem. Res.,
(S) 742; (M) 3329 (1998).