2-[4-(2-thienyl)-1,3-thiazol-2-yl]ethanenitrile in heterocyclic synthesis of biological interist

Article abstract of DOI:10.1080/104265090885048

Thiazolylacetonitrile was used in the synthesis of coumarin, pyrazolo[4,3-d]pyrimidines, 1,3,4-thiadiazolines, aminothiophenes, and thiazoles in a good yields. Also, pyrazolo[4,5-d]triazolino[4,5-a]pyrimidines, pyrazolo[4,5-d]thiazolino[3,2-a]pyrimidines, and pyrazolo[4,5-d]tetrazolino[1,5- a]pyrimidines were synthesized from pyrazolo[4,5-d]pyrimidine. Structures of the newly synthesized were elucidated by elemental analysis, spectral data, and alternative synthesis routes whenever possible. Some synthesized compounds were tested for their antimicrobial activity. Copyright Taylor & Francis Inc.

Full text of DOI:10.1080/104265090885048

This article was downloaded by: [Temple University Libraries]
On: 17 May 2013, At: 22:18
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH,
UK
Phosphorus, Sulfur, and Silicon
and the Related Elements
Publication details, including instructions for
authors and subscription information:
http://www.tandfonline.com/loi/gpss20
2-[4-(2-Thienyl)-1,3-thiazol-2-
yl]ethanenitrile in Heterocyclic
Synthesis of Biological Interist
Abdou O. Abdelhamid a & Ali A. Al-Atoom a
a Department of Chemistry, Cairo University, Giza,
Egypt
Published online: 01 Feb 2007.
To cite this article: Abdou O. Abdelhamid & Ali A. Al-Atoom (2005): 2-[4-(2-
Thienyl)-1,3-thiazol-2-yl]ethanenitrile in Heterocyclic Synthesis of Biological Interist,
Phosphorus, Sulfur, and Silicon and the Related Elements, 180:7, 1629-1646
To link to this article: http://dx.doi.org/10.1080/104265090885048
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-
and-conditions
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan,
sub-licensing, systematic supply, or distribution in any form to anyone is
expressly forbidden.
The publisher does not give any warranty express or implied or make any
representation that the contents will be complete or accurate or up to
date. The accuracy of any instructions, formulae, and drug doses should be
independently verified with primary sources. The publisher shall not be liable
for any loss, actions, claims, proceedings, demand, or costs or damages

whatsoever or howsoever caused arising directly or indirectly in connection
with or arising out of the use of this material.

Phosphorus, Sulfur, and Silicon, 180:1629–1646, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090885048
2-[4-(2-Thienyl)-1,3-thiazol-2-yl]ethanenitrile in
Heterocyclic Synthesis of Biological Interist
Abdou O. Abdelhamid
Ali A. Al-Atoom
Department of Chemistry, Cairo University, Giza, Egypt
Thiazolylacetonitrile was used in the synthesis of coumarin, pyrazolo[4,3-
d]pyrimidines, 1,3,4-thiadiazolines, aminothiophenes, and thiazoles in
a
good yields. Also, pyrazolo[4,5-d]triazolino[4,5-a]pyrimidines, pyrazolo[4,5-
d]thiazolino[3,2-a]pyrimidines, and pyrazolo[4,5-d]tetrazolino[1,5-a]pyrimidines
were synthesized from pyrazolo[4,5-d]pyrimidine. Structures of the newly syn-
thesized were elucidated by elemental analysis, spectral data, and alternative
synthesis routes whenever possible. Some synthesized compounds were tested for
their antimicrobial activity.
Keywords 1,3,4-thiadiazolines; Pyrazolo[4,3-d]pyrimidines; pyrazolo[4,5-d]-triazolino-
[4,5-a]pyrimidines; pyrazolo[4,5-d]thiazolino[3,2-a]pyrimidines; pyrazolo-[4,5-d]tetra-
zolino[1,5-a]pyrimidines
INTRODUCTION
A large number of thiazole derivatives has been found to exhibit
pharmacological activity.1,2 They also were used as an anthelmintic,3
fungicidal,4 and antifungal activity, inhibiting in vivo the growth of
Xanthomonas oryzae,5 and ingredient of herbicides.6 As an extension
of our study7−9 and as a part of our program aiming at the synthesis
of different thiadiazoles, we report herein the utility of 2-[4-(2-thienyl)-
1,3-thiazol-2-yl]ethanenitrile in heterocyclic synthesis.
RESULTS AND DISCUSSION
2-bromo-1-(2-thienyl)ethan-1-one10 (1) reacted with cyanothioac-
etamide (2) in ethanol under reflux to give 2-[4-(2-thienyl)-1,3-thiazol-
2-yl]ethanenitrile (3). Structure 3 was confirmed by elemental analysis,
Received June 23, 2004; accepted August 2, 2004.
Address correspondence to Abdou O. Abdelhamid, Department of Chemistry, Faculty
of Science, Cairo University, Giza, Egypt. E-mail: abdou abdelhamid@yahoo.com
1629

1630
A. O. Abdelhamid and A. A. Al-Atoom
spectral data, and chemical transformation. 1H NMR (δ ppm) spectrum
showed signals at δ = 4.15 (s, 2H, CH2CN), 7.06–7.46 (m, 4H, thiazole
C-5 and thiophene). Its IR (cm−1) revealed bands at 3101 (C H), 2198
(CN), and 1620 (C C).
Compound 3 reacted with each of salicylaldehyde and benzaldehyde
to give 3-(4-(2-thienyl)-1,3-thiaozl-2-yl)-2H-chromen-2-imine (4) and
(2E)-2-(4-(2-thienyl)(1,3-thiazol-2-yl))-3-phenylprop-2-enenitrile
(6),
respectively (Scheme 1). Structures of 4 and 6 were established on the
basis of elemental analysis, spectral data, chemical transformation,
1
and alternative synthesis. H NMR spectrum of 4 showed signals at
δ =6.68–7.41 (m, 9H) and 8.42 (s, 1H). Its IR (cm−1) spectrum revealed
bands at 3150 (NH), 3057 (CH), and 1559 (C C). 13C NMR spectrum of
4 showed signals at δ = 115, 116, 121, 124, 125, 127, 128, 129, 130, 136,
SCHEME 1

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1631
143, 154, 163, and 164. Also, compound 4 was converted to coumarin
derivative 5 by hydrochloric acid and its IR spectrum revealed bands at
3039 (CH), 1708 (CO), and 1539 (C C) (no bands at region 3400–3150
due to the absence of NH group). 1H NMR (δ ppm) spectrum of 6
showed one signal at δ =7.00–7.41 (m, ArH’s). Its IR (cm−1) spectrum
revealed bands at 3057 (CH), 2191 (CN), and 1595 (C C). Thus,
2-(aminothioxomethyl)-3-phenylprop-2-enenitrile11 (7) reacted with
2-bromo-1-(2-thienyl)ethan-1-one9 (1) in boiling ethanol to give a
product identical in all respects (mp., mixed mp., and spectra) with 6.
Treatment of 3 with the appropriate arenediazonium chlorides
in ethanolic sodium acetate solution at 0◦C afforded (2E)-3-aza-
3-(arylamino)-2-(4-(2-thienyl)-1,3-thiazol-2-yl)prop-2-enenitrile 8a and
8b. Structure 8 was confirmed by elemental analysis, spectral data, al-
ternative route, and chemical transformation. 1H NMR spectrum of 8b
showed signals at δ = 2.35 (s, 3H), 7.11–7.424 (m, 8H) and 14.06 (s, br.,
1H). Its 13C NMR showed signals at δ = 24, 116, 119, 123, 125, 127,
129, 130, 136, 140, 143, and 155.
On the other hand, treatment the appropriate (2E)-2-amino-
thioxomethyl-3aza-3-(arylamino)prop-2-enenitrile12 9a,b with 1 in boil-
ing ethanol under reflux afford products identical in all respects (mp.,
mixed mp. and spectra) with 8a and 8b, respectively.
Compound 8a reacted with each of ethyl chloroacetate, chloroace-
tone, and chloroacetonitrile in boiling N,N-dimethylformamide
solution containing potassium carbonate. Triethylamine afforded
ethyl
4-amino-1-phenyl-3-(4-(2-thienyl)(1,3-thiazol-2-yl)pyrazole-5-
carboxylate (10a), 1-[4-amino-1-phenyl-3-(4-(2-thienyl)(1,3-thiazol-
2-yl)pyrazol-5-yl]ethane-1-one (10b), and 4-amino-1-phenyl-3-(4-(2-
thienyl)-1,3-thiazol-2-yl)pyrazole-5-carbonitrile (10c), respectively.
Structures 10a–c were elucidated on the basis on elemental analysis
and spectral data. 1H NMR spectrum of 10a showed signals at δ = 1.20
1
(t, 3H), 4.24 (q, 2H), 5.87 (s, br., 2H) and 7.07–7.48 (m, 9H). H NMR
spectrum of 10b showed signals at δ = 2.55 (s, 3H), 5.39 (s, br., 2H)
and 7.00–7.57 (m, 9H). IR spectrum of 10b revealed bands at 3471,
3352 (NH2), 3097 (CH), 1631 (CO), and 1581 (C C). IR spectrum of
10c revealed bands at 3444 (NH2), 3352 (CH), 2215 (CN), and 1598
(C C). Compound 10c reacted with each formic acid or formamide
to give 1-phenyl-3-(4-(2-thienyl)(1,3-thiazol-2-yl))-6-hydropyrazolo[4,5-
d]pyrimidine-7-one (11a) and 1-phenyl-3-(4-(2-thienyl)(1,3-thiazol-2-
yl))-6-hydropyrazolo[4,5-d]pyrimidine-7-ylamine (11b), respectively
(Scheme 1 and Tables II and III).
Moreover, treatment of 3 with each of phenyl isothiocyanate or
carbon disulfide followed with iodomethane gave 3-(phenylamino)-
2-(4-(2-thienyl)(1,3-thiazol-2-yl))-3-thioxopropanenitrile (12), and

1632
A. O. Abdelhamid and A. A. Al-Atoom
TABLE I Response of Various Microorganisms to Some Synthesized
Compounds in Vitro (Culture). W: Low Activity (1–5 mm) (+); M:
Moderate Activity (6–10 mm) (++); S: High Activity (11–15 mm)
(+ + +); I: Inhibitor
Diameter of the Zone of Inhibition
Staplyococcus
aureus
(ATCC25923)
Streptococcus
pyogenes
ATCC19615
Pseudomonas
syringae PV
phasealicola
Comp.
no.
Aspergillus
niger
Fusarium
oxysporum
5
10a
10b
10c
18a
18d
18e
20
M
W
—
M
—
—
—
M
—
—
M
—
—
M
—
W
—
W
—
—
—
W
W
M
W
W
—
M
—
—
W
M
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
24b
332
34
3-methylthio-2-(4-(2-thienyl) (1,3-thiazol-2-yl))-3-thioxopropanenitrile
(13), respectively (Scheme 2). Structures 12 and 13 were confirmed
on the basis of elemental analysis, spectral data, and chemical
transformation. Thus, 13C NMR of 13 showed signals at δ = 23, 56,
115, 116, 126, 127, 128, 140, 143, 166, and 230 ppm. Treatment of
C-ethoxycarbonoyl-N-phenylhydrazonoyl chloride (14a) with 12 in
ethanolic triethylamine solution afforded one isolable product accord-
ing to tlc and spectral data. Thus, 1H NMR spectrum showed signals at
δ = 1.46 (t, 3H), 4.50 (q, 2H) and 7.09–7.63 (m, 9H). 13C NMR showed
signals at δ = 14, 61, 89, 115, 116, 119, 125, 128, 129, 130, 140, 143,
146, 149, 153, 154, and 161 ppm. Its IR spectrum revealed bands at
3101 (CH), 2183 (CN), 1712 (CO), and 1542 (C C). The product was
formulated as ethyl 2-[cyano(4-(2-thienyl)(1,3-thiazol-2-yl)methylene]-
3-phenyl-1,3,4-thiadiazolin-5-carboxylate (18a).
Also, compound 13 reacted with 14a in ethanolic triethylamine to
give an identical product (mp., mixed mp. and spectra) with 18a. On
the above data the structure 19 was ruled out (Scheme 2).
Two possible pathways can account for the formation of 18a: (First)
1,3-addition of the thiol tautomer 12 to the nitrilium imide 15a, (which
prepared in situ by treatment of hydrazonoyl chloride 14a with triethy-
lamine), can give the thiohydrazonate ester 16a, which undergoes nu-
cleophilic cyclization to yield 17a, which affords 18a by loss of aniline.

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1633
SCHEME 2
Second, 1,3-cycloaddition of the nitrilium imide 15a to the C S of 17a
can give 18a directly (cf. Scheme 2).
Similarly, the appropriate hydrazonoyl halides 14b–g reacted with
each of thioanilide 12 or carbodithioate 13 gave the corresponding 2,3-
dihydro-1,3,4-thiadiazoles 18b–g, respectively (Scheme 2).
Treatment of amino ester 10a with ammonium thiocyanate
in acetic acid under reflux afforded 1-phenyl-3-(4-(2-thienyl)
(1,3-thiazol-2-yl))-5-thioxo-4,6-dihydropyrazolo[4,5-d]pyrimidine-7-one
(20). Methylation of 20 with iodomethane in presence of sodium
ethoxide gave 5-methylthio-1-phenyl-3-(4-(2-thienyl)(1,3-thiazol-2-
yl))-6-hydropyrazolo[4,5-d]pyrimidine-7-one (21). 1H NMR spectrum
of 21 showed signals at δ = 3.70 (s, 3H) and 6.06–7.81 (m, 10H). Its
IR spectrum revealed bands at 3355 (NH), 3101 (CH), 1712 (CO),
and 1585 (C C). 13C NMR spectrum of 21 showed signals at δ = 13,

1634
A. O. Abdelhamid and A. A. Al-Atoom
TABLE II Characterization Data of the Newly Synthesized
Compounds
% Analyses calcd./found
Compd.
no.
m.p. ◦
solvent
C
Yield (%)
color
Mol. formula
mol. wt
C
H
N
S
3
49–51
EtOH
189–91
Dioxan
174–76
EtOH
75
Brown
72
Pale brown
80
Pale brown
85
Yellow
80
Yellow
68
Yellow
84
Yellow
58
Yellow
67
Olive
70
Yellow
60
Olive
65
Brown
50
C9H6N2S2
206.30
52.40
52.50
61.91
61.82
61.72
61.80
62.28
62.43
58.04
58.13
59.23
59.11
57.56
57.39
58.99
59.08
58.43
58.31
57.28
57.42
57.43
57.26
56.28
56.41
44.57
44.40
54.78
54.80
55.86
55.72
59.36
59.30
61.25
61.10
55.44
55.36
64.59
64.63
55.73
55.69
52.79
52.66
53.88
54.01
2.93
2.80
3.25
3.53
2.91
2.88
3.42
3.29
3.25
3.18
3.73
3.68
4.07
4.00
3.85
3.77
3.17
3.28
2.94
3.07
3.21
3.13
3.25
3.13
2.72
2.88
3.22
3.13
2.96
2.90
3.11
3.23
3.00
3.10
2.54
2.56
3.10
3.25
3.56
3.40
2.71
2.84
3.09
3.20
13.58
13.70
9.03
9.16
4.50
4.42
9.52
9.36
18.05
17.98
17.27
17.15
14.13
14.22
15.29
15.19
20.04
20.15
18.55
18.37
22.32
22.42
12.31
12.50
9.45
31.09
31.10
20.66
20.52
20.59
20.48
21.78
21.60
20.66
20.72
19.77
19.64
16.17
16.25
18.35
18.27
18.35
18.20
16.99
17.10
17.03
17.21
28.17
28.33
43.26
43.41
21.93
22.01
23.55
23.35
19.81
19.68
20.47
20.59
26.91
26.79
26.91
27.00
21.25
21.05
23.49
23.37
22.71
22.61
4
C16H10N2OS2
310.40
C16H9NO2S2
311.38
C16H10N2S2
294.40
C15H10N4S2
310.40
5
6
90–92
EtOH
8a
183–85
AcOH
185–87
AcOH
108–10
EtOH
180–82
AcOH
140–42
AcOH
252–58
AcOH
259–62
AcOH
178–79
AcOH
210–12
DMF
245–47
AcOH
304–306
DMF
264–66
DMF
267–68
DMF
285–87
DMF
8b
C16H12N4S2
324.43
10a
10b
10c
11a
11b
12
C
19H16N4O2S2
396.49
C18H14N4OS2
366.47
C17H11N5S2
349.44
C18H11N5OS2
377.45
C
18H12N6S2
376.46
C
16H11N3S3
341.48
13
C11H8N2S4
296.46
C20H14N4O2S3
438.55
Yellow
74
9.62
18a
18b
18c
18d
18e
18f
18g
20
12.78
12.67
13.71
13.58
14.42
14.33
11.91
12.02
11.76
11.84
11.76
11.61
12.38
12.50
17.10
16.95
16.54
16.65
Reddish Red
65
Orange
55
Reddish Red
70
Orange Red
75
C
C
C
19H12N4OS3
408.53
24H15N5OS3
485.61
24H14N4OS3
470.60
C22H12N4OS4
476.62
C28H16N4OS3
520.66
C21H16N4O2S2
452.58
C18H11N5OS3
409.51
Reddish Red
80
289–291
DMF
235–37
AcOH
>330
Dioxan
207–10
Dioxan
Brown
82
Yellow
85
Yellow
72
Yellow
21
C
19H13N5OS3
423.53
(Continued on next page)

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1635
TABLE II Characterization Data of the Newly Synthesized
Compounds (Continued)
% Analyses calcd./found
Compd. m.p. ◦
no. solvent
C
Yield (%)
color
Mol. formula
mol. wt
C
H
N
S
22a
240–42
Dioxan
250–52
Dioxan
220–22
Dioxan
>320
DMF
>320
DMF
290–92
DMF
220–22
AcOH
254–56
AcOH
135–37
EtOH
170–73
EtOH
274–76
EtOH
68
Colorless
70
Yellow
60
Yellow
45
Gray
70
Gray
80
Gray
65
Yellow
55
Yellow
C22H16N5O3S3 53.42 3.26 14.16 19.45
494.61 53.28 3.32 14.26 19.61
21H14N5O2S3 54.29 3.04 15.08 20.71
22b
22c
23a
23b
23c
24a
24b
25
C
464.57
C20H11N6OS3
447.54
54.45 3.13 14.96 20.55
53.68 2.48 18.78 21.49
53.82 2.62 18.93 21.34
C20H11N5O2S3 53.44 2.47 15.58 21.40
449.54
C21H13N5OS3
447.56
C20H12N6OS3
448.36
53.34 2.60 15.44 21.27
56.36 2.93 15.65 21.49
56.20 3.02 15.81 21.66
53.58 2.67 18.74 21.45
53.46 2.81 18.58 21.63
C
28H19N7O3S2 59.46 3.39 17.33 11.34
565.64 59.30 3.28 17.23 11.48
C27H17N7O2S2 60.55 3.20 18.31 11.97
535.61
C18H13N7OS2
407.48
C18H10N8OS2
418.46
60.71 3.38 18.16 12.00
53.06 3.22 24.06 15.74
53.15 3.37 24.18 15.86
51.66 2.41 26.78 15.32
51.49 2.60 26.90 15.10
50.63 2.66 11.07 25.34
50.50 2.51 10.85 25.12
75
Yellow
70
26
Yellowish brown
27
85
C
16H10KN3S3
379.57
Pale brown
28a
28b
28c
28d
29a
29b
29c
29d
30a
30c
30d
185–87
AcOH
234–36
AcOH
255–57
Dioxan
190–92
AcOH
254–55
AcOH
251–52
Dioxan
261–63
AcOH
268–70
Dioxan
121–23
EtOH
73
Olive
80
Olive
60
Gold
85
Olive
62
Green
60
Olive
50
Brown
45
Olive
C
20H17N3O2S3 56.18 4.01
427.57 56.27 4.14
9.83
9.74
22.50
22.63
C19H15N3OS3
397.54
C18H12N4S3
380.51
C
C
C
57.41 3.80 10.57 24.20
57.32 3.93 10.67 24.30
56.82 3.18 14. 72 25.28
56.92 3.33 14.69 25.45
24H17N3OS3
459.61
62.72 3.73
62.70 3.71
9.14
9.22
20.93
21.08
18H11N3OS3
381.50
56.67 2.91 11.01 25.21
56.83 3.06 10.92 25.35
19H13N3S3
379.53
60.13
3.45 11.07 25.35
60.00 3.59 11.24 25.52
56.82 3.18 14.72 25.28
56.91 3.23 14.66 25.11
C18H12N4S3
380.51
C24H15N3S3
441.60
65.28 3.42
65.38 3.58
9.52
9.40
9.83
9.68
21.78
21.91
22.50
22.62
35
Pale yellow
45
Brown
55
C20H17N3O2S3 56.18 4.01
427.57
C18H12N4S3
380.51
56.33 4.18
56.82 3.18 14.72 25.28
56.99 3.36 14.85 25.42
191–92
EtOH
136–37
EtOH
C
24H17N3OS3
459.61
62.72 3.73
62.88 3.72
9.14
9.06
20.93
20.76
Yellowish green
(Continued on next page)

1636
A. O. Abdelhamid and A. A. Al-Atoom
TABLE II Characterization Data of the Newly Synthesized
Compounds (Continued)
% Analyses calcd./found
Compd.0
no.
m.p. ◦
solvent
C
Yield (%)
color
Mol. formula
mol. wt
C
H
N
S
31
32
33
34
143–45
EtOH
266–68
Dioxan
160–63
EtOH
35
Yellow
60
Olive
30
Olive
60
Yellow
C22H19N3O3S3
469.61
56.27
56.43
58.51
58.62
57.38
57.38
59.83
59.99
4.08
4.16
3.97
4.08
3.90
4.06
3.59
3.75
8.95
8.82
9.31
9.23
9.56
9.71
10.00
9.87
20.48
20.37
21.30
21.41
21.88
21.58
22.82
22.66
C22H17N3O2S3
451.59
C21H17N3O2S3
439.58
C21H15N3OS3
421.56
262–64
Dioxan
107, 115, 120, 126, 127, 128, 129, 130, 140, 141, 143, 156, 159, and
193 ppm. Compound 20 reacted with each of ethyl chloroacetate,
chloroacetone, chloroacetonitrile, or the appropriate hydrazonoyl
halides 14a,b to give S-alkyl derivative 22a–c and 1,3-disubstituted
7-phenyl-5-(4-(2-thienyl(1,3-thiazol-2-yl))-8a-hydopyrazolo[4,5-d]1,2,4-
triazolino[1,5-a]pyrimidine-5-one 24a,b, respectively (Scheme 3).
Structure 22 was elucidated by elemental analysis, spectral data, and
chemical transformation. Thus, 1H NMR spectra of 22b showed signals
at δ = 1.99 (s, 3H), 3.72 (s, 2H), 5.68 (s, br., 1H) and 7.05–7.86 (m, 9H).
13C NMR spectrum showed signals at δ = 18, 101, 107, 115, 120, 125,
126, 127, 128, 129, 141, 143, 153, and 163 ppm. Compounds 22a–c
were converted to pyrazolo[4,5-d]1,3-thiazolino[2,3-a]pyrimidin-5-one
derivatives 23a–c by boiling in a mixture of acetic acid and sulfuric acid
under reflux. Structures 23a–c were confirmed by elemental analysis
and spectral data (cf. Experimental). Compound 20 reacted with the
appropriate hydrazonoyl chlorides 14a,b and triethylamine in boiling
chloroform under reflux to give pyrazolo[4,5-d]1,2,4-triazolino[4,5-
a]pyrimidine-8-one derivatives 24a,b, respectively (Scheme 3).
Structure 24 was elucidated by elemental analysis, spectral data and
1
alternative synthesis route. H NMR spectrum of 24a showed signals
at δ = 1.48 (t, 3H), 4.58 (q, 2H), 7.06–7.11 (m, 1H), 7.27–7.62 (m, 9H),
7.81–85 (d, 2H) and 8.46–8.50 (d, 2H). Its 13C NMR spectrum showed
signals at δ = 14, 62, 107, 115, 116, 118, 120, 125, 126, 127, 128, 129,
1
139, 141, 143, 146, 154, 158, 159, and 163 ppm. H NMR spectrum of
24b showed signals at δ = 2.64 (s, 3H), 7.10–7.13 (m, 1H), 7.27–7.65
(m, 9H), 7.79–8.31 (d, 2H) and 8.48–8.52 (d, 2H). Its 13C NMR spectrum
showed signals at δ = 21, 107, 115, 116, 118, 120, 126, 127, 128, 129,
139, 141, 143, 146, 154, 163, and 194 ppm. Also, treatment of 14a

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1637
SCHEME 3
with 21 in ethanolic triethylamine afforded an identical product in all
respects (mp., mixed mp., and spectra) with 24a.
Compound 21 reacted with hydrazine hydrate in boiling ethanol
under reflux and yielded 5-hydrazino-1-phenyl-3-(4-(2-thienyl)(1,3-
thiazol-2-yl))-6-hydropyrazolo-[5,4-d]pyrimidin-7-one (25). Compound
25 reacted with nitrous acid to give 7-phenyl-5-(4-(2-thienyl)-
(1,3-thiazol-2-yl))-8a-hydro-3H-pyrazolo[4,5-d]1,2,3,4-tetrazolino[1,5-
a]pyrimidin-8-one (26) (cf. Scheme 3).
Finally, treatment of potassium salt of 3-(phenylamino-3-sulfanyl-
2-4-(2-thienyl)(1,3-thiazol-2-yl))prop-2-enenitrile (27), which prepared
via reaction of phenyl isothiocyanate and 3 in potassium ethoxide
solution, with each of ethyl chloroacetate, chloroacetone, chloroacetoni-
trile, or phenacyl bromide in ethanol afforded [3-amino-2-substituted

1638
A. O. Abdelhamid and A. A. Al-Atoom
SCHEME 4
5-(phenylamino)(4-(4-thienyl)(1,3-thiazol)(2-thienyl)(1,3-thiazol-2-yl)
thiophenes] 28a–d, respectively (Scheme 4). Structure 28 was eluci-
dated by elemental analysis and spectral data. Thus, 1H NMR spectra
of 28a showed signals at δ = 1.36 (t, 3H), 4.28 (q, 2H), 5.10 (s, br., 2H),
7.09–7.48 (m, 9H) and 11.80 (s, br., 1H). Its 13C NMR showed signals
at δ = 14, 61, 115, 116, 118, 122, 126, 127, 128, 130, 131, 140, 143, 144,
153, and 160 ppm. Whereas, each of ethyl 2-chloro-3-oxoprpanoate
and 3-chloropentan-2,4-dione was reacted by a similar route to give
aminothiophenes 28a and 28b, respectively.
In contrast, compound 3 reacted with phenyl isothiocyanate in N,N-
dimethylformamide containing potassium hydroxide and followed by
ethyl chloroactate afforded thiazole 29a and S-alkyl 30a. 1H NMR spec-
tra of 29a showed signals at δ = 3.99 (s, 2H,C-2 thiazole), and 7.09–
7.63 (m, 9H, ArH’s). 1H NMR spectra of 30a showed signals at δ = 1.22
(t, 3H), 3.35 (s, 2H), 4.10 (q, 2H), 7.03–7.05 (m, 1H), 7.07–7.50 (m, 8H)
and 12.52 (s, br., 1H). Similarly, 3 reacted with chloroacetyl chloride by
the same route and gave a product identical in all respects (mp., mixed
mp., and spectra) with 29a (Scheme 4).
Compound 27 reacted with each of chloroactone, phenacylbromide,
chloroacetonitrile, ethyl 3-chloro-2-oxopropanoiate, or 3-chloropentan-
2,4-dione in N,N-dimethylformamide and gave, in each case, S-alkyl

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1639
and thiazole derivatives 29b–d, 32, and 34, respectively (Scheme 4).
Boiling S-alkyl derivatives 30c,d, 31, and 33 in ethanol containing a cat-
alytical amount of piperidine afforded corresponding thiophene amines
28a–c.
Biological Activities
The tested microorganisms were gram +ve bacteria [Staphylococcus
aureus (ATCC25923) and Streptococcus pyogenes (ATCC19615)] and
gram −ve bacteria (pseudomonas syrinagae PV phasealicola). In addi-
tion to some fungal-plant pathogens (Aspergillus niger and Fusarium
oxysporum) were tested. Sensitivity of the selected microorganisms to
some synthesized compounds were determined in vitro culture on two
concenterations (100, 200 µg/mL) that were dissolved in CHCl3. The
tests were carried out using the filter paper and hole plate method.13
Studies on the biological activity of compounds, 5, 10a, 10b, 10c,
18a, 18b, 18d, 18e, 20, 24a, 24b, 32, and 34 led to the fact that these
compounds have a weak-to-moderate biological activity against of the
tested bacteria in Table I. All the tested compounds showed negative
antifungal activities.
EXPERIMENTAL
All melting points were determined on an electrothermal apparatus and
were 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 spec-
trometer and chemical shifts were expressed in δ units using TMS
as an internal reference. Mass spectra were recorded on a GC-MS
QP1000 EX Shimadzu. Elemental analysis were carried out at the Mi-
croanalytical Center of the Cairo University. 2-Bromoacetylthiopene9
and hydrazonoyl halides14−20 14a–g were prepared as previously
reported.
2-[4-(2-Thienyl)-1,3-thiazol-2-yl] Ethanenitrile 3
A mixture of 2-Bromoacetylthiophene (1), (20.5 g, 100 mmol) and cyan-
othioacetamide (10 g, 100 mmol) in ethanol (25 mL) was refluxed for
2 h. The reaction mixture was poured onto ice-cold water (50 mL) and
added 5 drops of conc. ammonium hydroxide (25%). The resulting solid
was collected, washed with water, and recrystallized from ethanol to
give thiazolylacetonitrile 3 (Tables II and III).

1640
A. O. Abdelhamid and A. A. Al-Atoom
TABLE III Spectra of Some Newly Synthesized Compound
Comp.
no.
Spectral data
5
6
8a
13CNMR: 121, 125, 126, 127, 128, 129, 130, 136, 143, 150, 154, 163, and 164
IR: 3093 (CH), 2210 (CN), and 1554 (C C).
1HNMR: 7.11-7.47 (m, 9H, ArH’s), and 14.06 (s, br. NH).
IR: 3101 (CH), 2214 (CN), 1596 (C C).
8b
10a
IR: 3448 (NH), 3119 (CH), 2217 (CN), and 1595 (C C).
13CNMR: 14, 61, 115, 120, 123, 126, 127, 128, 129, 130, 136, 140, 143, 160,
and 162.
IR: 3458, 3339 (NH2), 3092 (CH), 1709 (CO), and 1593 (C C).
13CNMR: 27, 115, 120, 125, 126, 127, 128, 129, 130, 133, 140, 143, 162, and 196.
13CNMR: 114, 115, 120, 125, 129, 130, 133, 139, 140, 143, and 162.
IR: 3097 (CH), 1697 (CO), 1600 (C C).
10b
10c
11a
11b
12
IR: 3467 (NH2), 3085 (CH), 1608 (C C).
1HNMR: 2.25 (s, 3H, SCH3), 7.03–7.50 (m, 9H, ArH’s), and 12.53 (s, br., NH).
IR: 3421, 3359 (NH), 3062 (CH), 2183 (CN), and 1523 (C C).
IR: 3089 (CH), 2202 (CN), 1594 (C C).
13
18b
1HNMR: 2.64 (s, 3H, CH3), and 7.09–7.67 (m, 9H, ArH’s).
13CNMR: 23, 89, 115, 116, 118, 126, 127, 128, 130, 140, 146, 149, 153, 154,
and 194.
IR: 3092(CH), 2194(CN), 1678 (CO), and 1595 ( C C) .
IR: 3386 (NH), 3062 (CH), 2191 (CN), 1674 (CO), and 1582 (C C).
IR: 3099 (CH), 2189 (CN), 1676 (CO), and 1584 (C C).
IR: 3102 (CH), 2192 (CN), 1671 (CO), and 1607 (C N).
IR: 3102 (CH), 2191 (CN), 1672 (CO), 1622 (C N).
1HNMR: 1.49 (t, 2H, CH2CH3), 2.48 (s, 3H, CH3), 4.5 (q, 2H, CH2CH3),
and 7.08–7.50 (m, 8H, ArH’s).
18c
18d
18e
18f
18g
IR: 3094 (CH), 2188 (CN), 1730 (CO).
20
21
22a
22b
22c
IR: 3355 (NH), 3101 (CH), 1712 (CO), and 1523 (C C).
IR: 3457 (NH), 3112 (CH), 1691 (CO), and 1593 (C C).
IR: 3448 (NH), 3097 (CH), 1741 (CO), and 1679 (CO).
IR: 3382 (NH), 3089 (CH), 1678 (CO), and 1569 (C C).
1HNMR: 3.71 (s, 2H, CH2CN), and 7.26–7.49 (m, 10H, ArH’s),
IR: 3446 (NH), 3101 (CH), 2247 (CN), 1685 (CO), and 1575 (C C).
IR: 3095 (CH), 1682 (CO), 1573 (C C).
IR: 3101 (CH), 1654 (CO), and 1596 (C C).
IR: 3494, 3371 (NH2), 3070 (CH), 1708 (CO), and 1589 (C C).
IR: 3099 (CH), 1720 (CO), 1583 (C C).
23a
23b
23c
24a
24b
25
26
28a
28b
IR: 3101 (CH), 1710 (CO), 1609 (C C).
IR: 3423, 3338 (NH2), 3097 (CH), 1641 (CO), and 1597 (C C).
IR: 3367 (NH), 3101 (CH), 1689 (CO), and 1596 (C C).
IR: 3441, 3394 (NH2), 3101 (CH), 1720 (CO), and 1573 (C C).
1HNMR: 2.33 (s, 3H, CH3), 7.10–7.48 (m, 11H, ArH’s and NH2),
and 11.99 (s, br., NH).
IR: 3433, 3317 (NH2), 3101 (CH), 1658 (CO), and 1596 (C C).
IR: 3438, 3349 (NH2), 3100 (CH), 2179 (CN), and 1566(C C).
IR: 3420, 3238 (NH2), 3053 (CH), 1592 (CO), 1559 (C C).
(Continued on next page)
28c
28d

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1641
TABLE III Spectra of Some Newly Synthesized Compound
(Continued)
Comp.
no.
Spectral data
29a
29b
IR: 3096 (CH), 2197 (CN), 1728, 1631 (CO), and 1594 (C C).
1HNMR: 1.92 (s, 3H, CH3), 6.38 (s, 1H, thiazol), and 7.04–7.65 (m, 9H, ArH’s).
13C NMR: 19, 80, 109, 115, 116, 118, 119, 126, 128, 130, 140, 141, 143, 153,
and 160.
IR: 3093 (CH), 2167 (CN), 1596 (C C).
29c
1HNMR: 7.12–7.69 (m, 10H, ArH’s), 8.3 (s, br., 1H), and 10.15 (s, br., 1H).
IR: 3290 (NH), 3093 (CH), 2183 (CN), and 1593 (C C).
IR: 3390 (NH), 2100 (CH), 2184 (CN), 1708 (CO), and 1571 (C C).
IR: 3093 (CH), 2175 (CN), 1666 (CO), and 1573 (C C).
33
34
3-(4-(2-Thienyl)-1,3-thiaozl-2-yl)-2H-chromen-2-imine (4)
and (2E)-2-(4-(2-thienyl)(1,3-thiazol-2-yl))-3-phenylprop-2-
enenitrile (6)
Method A: Thiazolylacetonitrile 3 (1.03 g, 5 mmol) and salicylaldehyde
or benzaldehyde (5 mmol) in ethanol (20) containing catalytic amount of
piperidine were stirred at room temperature for 2 h. The resulting solid
was collected and recrystallized to give 4 and 6, respectively (Tables II
and III).
Method B: Equimolar amounts of 2-(aminothioxomethyl)-3-phenyl-
prop-2-enenitrile and 1 (5 mmol) in ethanol (15 mL) was boiled under
reflux for 2 h. The resulting solid was collected and crystallized and
gave the identical product (mp., mixed mp, and spectra) with 6.
3(4-(Thienyl)-1,3-thiazol-2-yl)-2H-chromen-2-one (5)
A mixture of 4 (0.5 g) and hydrochloric acid (5 mL, 6 M) was stirred at
room temperature for 1 h. The resulting solid was collected and recrys-
tallized from ethanol to give substituted coumarin 5 (Tables II and III).
(2E)-3-aza-3-(arylamino)-2-(4-(2-thienyl)1,3 Thiazol-2-yl)
Prop-2-enentitrile 8a,b
Method A: The appropriate arenediazonium chlorides (5 mmol) was
added dropwise to a cold ethanol solution, containing thiazolyacetoni-
trile 3 (1.03 g, 5 mmol) and sodium acetate (1 g), (50 mL) at 0–5◦C while
stirring. The mixture was stirred for 3 h at 0–5◦C. The resulting solid
was collected and crystallized from dioxan to give 8a,b (Tables II and
III).

1642
A. O. Abdelhamid and A. A. Al-Atoom
Method B: A mixture of the appropriate (2E)-2-aminothioxomethyl)-
3aza)-3-(arylamino)prop-2-enenitrile 9a,b and 1 (5 mmol each) in acetic
acid (30 mL) was boiled under reflux for 2 h. The resulting solid, which
formed after cooling, was collected and crystallized from acetic acid to
afford a product identical in all respects (mp., mixed mp., and spectra)
with products obtained in method A.
Aminopyrazoles 10a–c
Equimolar amounts of 8a and the appropriate of ethyl chloroac-
etate and chloroacetone, or chloroacetonitrile (5 mmol) in N,N-
dimethylformamide (30 mL) containing potassium carbonate anhy-
drous (1.5 g) was heated under reflux at 110–120◦C for 2 h. The
reaction mixture was cooled at room temperature and triethylamine
(1 mL) was added dropwise while stirring. The reaction mixture was
boiled at 90◦C for 1 h and poured onto ice-cold water (100 mL). The
resulting solid was collected and recrystallized to give aminopyrazoles
10a–c (Tables II and III).
Pyrazolo[3,4-d]pyrimidines 11a and 11b
Aminopyrazole 10c (1.25 g, 5 mmol) and formic acid (10 mL, 99%) or for-
mamide (2 mL) in N,N-dimethylformamide (10 mL) was heated under
reflux for 5 h then poured onto on ice-cold water (50 ml). The resulting
solid was collected and crystallized to afford 11a and 11b, respectively
(Tables II and III).
3-(Phenylamino)-2-(4-(2-thienyl)(1,3-thiazol-2-yl))-3-
thioxopropanenitrile (12)
Phenyl isothiocyanate (0.65 g (0.6 ml), 5 mmol) was added to a mix-
ture of thiazolylacetonitrile 3 (1.03 g, 5 mmol) and potassium hydroxide
(0.28 g, 5 mmol) in N,N-dimethylformamide (15 mL) while stirring at
room temperature until potassium hydroxide dissolve completely, and
the reaction mixture continued stirring for 1 h. The reaction mixture
was poured onto water (30 mL) and acidified with acetic acid. The re-
sulting solid was collected and recrystallized from acetic acid to give 12
(Tables II and III).
Synthesis of 3-Methythio-2-(4-(2-thienyl)(1,3-thiazol-2-yl)-3-
thioxopropane-nitrile 13
A mixture of thiazolylacetonitrile 3 (1.03 g, 5 mmol), potassium hydrox-
ide (0.28 g (5 mmol) and carbon disulfide (0.39 g, (0.29 mL), 5 mmol) in

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1643
N,N,-dimethylformamide (15 mL) was stirred for 6 h at room temper-
ature. Iodometane (0.71 g, 5 mmol) was added dropwise to the above
mixture and stirred for 1 h. The resulting solid was collected and crys-
tallized from acetic acid to give 13 (Tables II and III).
2,3-Dihydro-1,3,4-thiadiazoles 18a–g
Method A: Phenyl isothiocyanate (0.65 g, (0.65 mL), 5 mmol) was added
to a mixture of thiazolylacetonitrile (1.03 g, 5 mmol) 2 and potassium
hydroxide (0.28 g, 5 mmol) in N,N-dimethylformamide (15 mL) while
stirring at room temperature until potassium hydroxide dissolve com-
pletely and the reaction mixture was continued stirring for further
30 min. The appropriate hydrazonoyl halides 14a–g (5 mmol) was added
and stirring was continued for 3 h. The resulting solid was collected and
recrystallized from the appropriate solvent to afford 18a–g (Tables II
and III).
Method B: Triethylamine (0.5 g, (0.75 mL), 5 mmol) was added drop-
wise to a mixture of the appropriate hydrazonoyl halides 14a–g and 13
(1.9 g, 5 mmol) in ethanol (20 mL) while stirring. Stirring was continued
for 1 h and the resulting solid was collected and crystallized and gave
identical products in all respects (mp., mixed mp., and spectra) with
those obtained in method A.
5-Thio-1,4,5,6-tetrahydropyrazolo[4,3-d]pyrimidin-7-one (20)
Equimolar amounts of aminopyrazole 10a and ammonium thiocyanate
(5 mmol) in acetic acid (10 mL) were heated under reflux for 5 h, then
poured onto ice-cold water. The resulting solid was collected and crys-
tallized to give 20 (Tables II and II).
S-Alkyl Derivatives 21 and 22a–c
1-phenyl-3-(4-thiophen-2-ylthiazol-2-yl)-5-thio-1,4,5,6-tetrahydropyra-
zolo-[4,3-d]pyrimidin-7-one (20) (2.04 g, 5 mmol) potassium hydroxide
(0.28 g, 5 mmol) in N,N-dimethylformamide (15 mL) was stirred at room
temperature for 6 h. The appropriate iodomethane, ethyl chloroacetate,
chloroacetone, or chloroacetonitrile (5 mmol) was added dropwise while
stirring and stirred was continued for 2 h. The resulting solid, which
formed after dilution with water, was collected and crystallized to give
21 and 22a–c, respectively (Tables II and III).
Pyrazolo[4,5-d]1,3-thiazolino[3.2-a]pyrmidin-8-one 23a–c
An appropriate 22a–c (0.5 g) in a mixture of glacial acetic acid (10 mL)
and sulfuric acid (3 mL, 18 M) was heated under reflux for 6 h, then

1644
A. O. Abdelhamid and A. A. Al-Atoom
poured onto ice-cold water (30 mL). The resulting solid was collected
and crystallized to give 23a–c, respectively (Tables II and III).
Pyrazolo[4,5-d]1,2,4-triazolino[4,5-a]pyrimidin-8-one 24a,b
Equimolar amounts of 21, 14a, or 14b and sodium ethoxide (5 mmol,
each) in ethanol (20 mL) was boiled under reflux for 3 h. The resulting
solid was collected and crystallized to give 24a and 24b, respectively
(Tables II and III).
5-Hydrazino-6-pyrazolo[4,5-d]pyrimidine-7-one 25
A mixture of 21 (2.12 g, 5 mmol) and hydrazine hydrate (1 mL, 99%) in
ethanol (20 mL) was heated under reflux for 3 h. The resulting solid,
which formed after cooling, was collected, washed, and crystallized to
give 25 (Table I).
Synthesis of 7-Pheny1-5-(4-(2-thienyl) (1,3-thiazol-2-yl)-8a-
hydro-3H-pyrazolo-[4,5-d]1,2,3,4-tetrazolino[1,5-a]
Pyrimidin-8-one 26
Saturated sodium nitrite solution was added to a cold mixture of 25 (1 g)
in glacial acetic acid (20 mL) while stirring. The reaction mixture was
kept at 0◦C for 1 h and the resulting solid was collected and crystallized
to give 26 (Tables II and III).
Potassium Salt of 3-(Phenylamino-3-sulfanyl-2-4-(2-
thienyl)(1,3-thiazol-2-yl))prop-2-enenitrile (27)
Potassium ethoxide (5 mmol) was added dropwise to a mixture of thia-
zolylacetonitrile 3 (1.03 g, 5 mmol) and phenyl isothiocyanate (0.65 g,
(0.6 mL), 5 mmol) in (10 mL) absolute ethanol at room temperature.
Diethyl ether (30 mL) was added to the reaction mixture to complete
precipitation and the resulting solid was collected and crystallized from
ethanol to give 27 (Table I).
S-Alkyl 30a,c,d, 31, 33 and Thiazole Derivatives
29a–b, 32 and 34
Phenyl isothiocyanate (0.6 mL, 5 mmol) was added to mixture of
thiazolylacetonitrile 3 (1.03 g, 5 mmol) and potassium hydroxide
(0.28, 5 mmol) in N,N dimethylformamide (15 mL) while stirring

2-[4-(2-Thienyl)-1,3-Thiazol-2-yl]Ethanenitrile
1645
at room temperature until potassium hydroxid dissolve completely.
The reaction mixture continued stirring for further 30 min, then we
added the appropriate ethyl chloroacetate, chloroacetonitrile, phenacyl-
bromide, 3-chloropentan-2,4-dione or ethyl 2-chloro-3-oxopropanoate
(5 mmol each) while continuously stirring 1 hr. The resulting solid
was collected and crystallized to give S-alkyl 30a,c,d, 31, and 33,
and thiazole derivatives 29a–d, 32, and 34, respectively (Tables II
and III).
3-Amino Thiophene derivatives 28a–d
Method A: The appropriate S-alkyl derivatives 30a–d (5 mmol) in
ethanol (15 mL) containing catalytic amount of piperidine was heated
under reflux for 30 min. The resulting solid was collected and crystal-
lized to give 28a–d (Tables II and III).
Method B: Potassium ethoxide (5 mmol) was added dropwise to a
mixture of thiazolylacetonitrile 3 (1.03 g, 5 mmol) and phenyl isothio-
cyanate (0.65 g, (0.6 mL), 5 mmol) in (10 mL) absolute ethanol at room
temperature. The resulting solid was collected and crystallized to give
28a–d.
REFERENCES
[1] P. A. Lowe, In Heterocyclic Chemistry, H. Suschitzky and O. Meth-Cohn (eds.), Chem-
ical Society, London, vol. 1, pp. 119–139 (1980).
[2] J. V. Metzger, Thiazoles and their Benzo Derivatives. In Comprehensive Heterocyclic
Chemistry, A. R. Katritzky and C. W. Rees (eds.), Pergamon Press, vol. 6, pp. 328
(1984).
[3] H. D. Brown, US Pat. 3 278 547, 1966; [Chem. Abstr. 65, 18593 (1966)].
[4] S. P. Singh and S. Segal, Indian J. Chem., 27B, 941 (1988).
[5] Y. Usui, Yakugaku Zasshi, 89, 099 (1969) [Chem. Abstr. 71, 69601 (1969).]
[6] P. Goursot and E. F. Jr. Westrum, J. Chem. Eng. Data, 14, 1 (1969).
[7] A. O. Abdelhamid, H. A. Emam, and N. A. Abdel-Reheem, J. Chem. Res., (S) 532,
(M) 2323 (1999).
[8] A. O. Abdelhamid and G. S. Mohamed, Phosphorus, Sulfur, and Silicon, 115, 152
(1999).
[9] H. F. Zohdi, N. M. Rateb, M. M. M. Sallam, and A. O. Abdelhamid, J. Chem. Res.,
(S) 742, (M) 4429 (1998).
[10] W. T. Flowers, J. F. Robinson, D. R. Taylor, and A. E. Tipping, J. Chem. Soc. Perkin
I, 356 (1981).
[11] J. S. A. Brunskill, A. De, and O. F., Ewing, J. Chem. Soc; Perkin Trans I, 356 (1981).
[12] K. Gewald, and U. Hain, J. Prakt. Chem., 317, 329 (1975).
[13] C. Lefert, H. Siripumchidbouree, S. Hamspons, S. Workman, D. Sigee, H. A. S. Epton,
et al., J. Appl. Bact., 78, 97 (1955).
[14] G. Fravel, Bull. Soc. Chim. Fr., 31, 150 (1904).
[15] N. E. Eweiss and A. Osman, Tetrahedron Lett., 1169 (1979).

1646
A. O. Abdelhamid and A. A. Al-Atoom
[16] A. S. Shawali and A. O. Abdelhamid, Bull. Chem. Soc. Jpn., 49, 321 (1976).
[17] A. S. Shawali and A. Osman, Tetrahedron, 27, 2517 (1971).
[18] A. O. Abdelhamid, and F. H. H. El-Shiatey, Phosphorus, Sulfur, Silicon, and Related
Element, 39, 45 (1988).
[19] H. M. Hassaneen, A. S. Shawali, N. E. Elwan, and N. M. Abounada, Sulfur Letters,
14, 41 (1972).
[20] R. H. Wiley and G. H. Garboe, J. Am. Chem. Soc., 78, 624 (1956).