Decomposition of 2-propenoyl azide derivatives. Synthesis and larvicidal activity of novel products

Article abstract of DOI:10.1002/(SICI)1521-4184(199803)331:3<91::AID-ARDP91>3.0.CO;2-E

Decomposition of 2-propenoyl azide (1c) with nitrogen, oxygen, and sulfur nucleophiles affords the azido displacement products. Ring closure of some of these products produces the heterocyclic systems pyrimidone (3), oxadiazine (6), oxadiazole (8), benzimidazole (10), benzothiazole (12), and benzoxazinone (14). The larvicidal activity of some of these products against Culex pipiens was evaluated.

Full text of DOI:10.1002/(SICI)1521-4184(199803)331:3<91::AID-ARDP91>3.0.CO;2-E

Full Papers
Decomposition of 2-Propenoyl Azide Derivatives. Synthesis and
Larvicidal Activity of Novel Products
Sayed Ahmed Shiba
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt
Key Words: 2-Propenoyl azide; larvicides; pesticides; Culex pipiens
(Scheme 1). Treatment of 7a with phosphoryl chloride
Summary
yielded the 1,3,4-oxadiazole derivative (8) (Scheme 1).
o-Phenylene diamine reacted with 1c to give the di-dis-
placement product, i.e. the N,N′-(dipropenoyl)-1,2-diamino-
benzene derivative (9) (Scheme 2).
Cyclization of 9 upon treatment with phosphoryl chloride
gave the intermediate (A), which hydrolyzed to give a mix-
ture of 1H-benzimidazole (10) and acid (1a) (Scheme 2).
On the other hand, decomposition of azide (1c) with 2-ami-
nothio-phenol yielded only the monosubstituted S-propenoy-
late derivative (11) (Scheme 2), which upon heating without
solvent justat itsmelting point, underwent ring closure to give
the 1,3-benzothiazole derivative (12) (Scheme 2).
Decomposition of 2-propenoyl azide (1c) with nitrogen, oxygen,
and sulfur nucleophiles affords the azido displacement products.
Ring closure of some of these products produces the heterocyclic
systems pyrimidone (3), oxadiazine (6), oxadiazole (8), benzimid-
azole (10), benzothiazole (12), and benzoxazinone (14). The larv-
icidal activity of some of these products against Culex pipiens was
evaluated.
Introduction
[1–4]
In keeping with the high level of interest shown
in the
Reaction of 1c with anthranilic acid produced the N-pro-
penoyl derivative (13) (Scheme 2). Treatment of 13 with
acetic anhydride yielded the corresponding 3,1-benzoxazin-
4-one derivative (14) (Scheme 2). Furthermore, decomposi-
tion of azide (1c) with 2-aminophenol gave a mixture of the
expected mono- and di-displacement products 15 and 16,
respectively (Scheme 2). Similarly, decomposition of 1c with
alcohols or phenol yielded the alkyl and/or aryl 2-propenoyl-
ate derivatives (17a–d) in quantitative yields (Scheme 2).
In all of the previous reactions, the decomposition of the
synthesis of some new acrylonitrile derivatives bearing het-
erocyclic moieties of characteristic pesticidal and insecticidal
[5]
[6]
activities, such as pyrimidinethiones , oxadiazine
,
[7,8]
[9,10]
[11]
oxadiazoles
,benzimidazoles
, benzothiazoles , as
[12]
well as diarylureas , this paper reports on the reactivity of
(E)-2-cyano-3-(2′-thienyl)-2-propenoyl chloride (1b) and its
azide (1c) towards some nitrogen, sulfur, and oxygen nucleo-
philes with the aim of studying 1) the mode of decomposition
of acyl azide (1c) (azido or Curtius), 2) whether replacement
of the anisyl moiety (as aromatic) by the thienyl moiety (as
heterocycle) enhances the activity of the new acrylonitrile
[1]
azide (1c) proceeds by an azido-displacement ; the same
products were obtained from the reaction of the acid chloride
(1b) with the same reagents.
derivatives against larvae of Culex pipiens relative to values
[1]
found in the previous study
.
Decomposition of (E)-2-cyano-3-(2′-thienyl)-2-propenoyl
azide (1c) with thiourea in toluene under reflux proceeded
normally, involving not only mono-and di-displacement (2
Larvicidal Activity
and 5), but also the pyrimidinone derivative (3) as well as the Materials and Methods
imide derivative (4) (Scheme 1).
The biological activity of 12 compounds against Culex
The formation of 3, 4, and/or 5 from the mono-displacement
product (2) can be explained by addition of the free amino
group of 2 to the double bond of the α,β-unsaturated nitrile to
give 3, while further nucleophilic displacement by the amino
pipiens larvae was determined using the WHO test tech-
[13]
nique . Culex pipiens larvae used in this study were col-
lected from Banha City, Quliubia Gov, Egypt. They were
reared in an insectary for one generation by standard tech-
nique. The larvae were fed on a mixture of dog biscuit, dried
milk, and yeast. Late third and early fourth instar larvae were
kept in appropriate concentrations of a compound water
mixture for a period of 24 h. Six different concentrations of
the selected compounds were used in the bioassay tests. In
each test, 25 mosquito larvae, put in glass jar with 250 ml tap
water, were treated with the compounds.
group of the intermediate amide [R-CO-NH ] of 1c or 2 with
2
the elimination of (HN ) and/or (NH ) afforded 4 and 5,
3
3
respectively.
Ring closure of 5 on heating at 170 °C without solvent
yielded the 1,3,5-oxadiazine-4-thione derivative (6b)
(Scheme 1). Decomposition of azide (1c) with urea and/or
thiourea at 170 °C afforded the 1,3,5-oxadiazin-4-one
(thione) (6a and 6b) by diazido displacement with subsequent
cyclization (Scheme 1).
Acid hydrazides, namely, phenylacetic hydrazide and/or
p-toluene-sulfonyl hydrazide reacted with azide (1c) to give
the 2-propenoic hydrazide derivatives (7a and 7b) mula
Each test was replicated four times according to the stand-
[13]
ard testing procedure recommended by the WHO
(1975).
The dead larvae were removed and mortality was calculated.
Total percent mortality was corrected using Abbott‘s for-
[14]
(1925).
Arch. Pharm. Pharm. Med. Chem.
© WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998
0365-6233/98/0303/0091 $17.50 +.50/0

92
Shiba
Y
Y
C
S
C
T,ref.
S
O
O
C
S
C
CN
N
N
NH
NH
2
NH
NH
2
2
2
R C
X
R
R
NH
NH
+
2
170
C
R
R
HN
O
+
O
( 2 )
( 1 )
NH
( 3 )
( 6 )
S
a) X=OH
b) X=Cl
a) Y=O
b) Y=S
O
C
O
C) X=N
3
R
NH
+
C
NH CS
2
2
R`-NHNH
( 4 )
( 5 )
2
170
O
C
R
NH NH R`
( 7)
a) R` = CO CH C H
( 6b )
2
6
5
b) R` = SO C H CH ( )
4
3
2
6
4
POCl
3
R
N
N
O
C H
6
5
( 8 )
S
CN
R =
H
Scheme 1
NH
NH
SH
2
2
2
O
NH
N
NHCOR
NHCOR
2
,
-H O
NH
R
R C X
2
S
SCOR
(11)
(12)
(1b,c)
( 9 )
NH
2
NH
2
R`OH
POCl
3
COOH
OH
O
NH
NHCOR
COOH
2
N
N
R C OR`
R
OCOR
COR
(13)
( A )
(17)
(15)
a) R` = CH(CH Cl)
2
2
Ac O
2
hyd.,H O
2
+
b) R` = C(CH ) C CH
3 2
c) R` = C(CH ) CH=CH
3 2
2
N
R
N
R
N
NHCOR
OCOR
d) R` = C H Cl( )
4
6
4
O
O
H
(16)
(14)
(10)
+
O
S
CN
R =
R C OH
H
(1a)
Scheme 2
Arch. Pharm. Pharm. Med. Chem. 331, 91–96 (1998)

2-Propenoyl Azide Decomposition Products
93
Table 1: Data of compounds prepared.
—————————————————————————————————————————————
Cpd.
No.
Mp °C
IR
M. formula
(MW) a
NH,OH
C≡N
C=O
C=S
—————————————————————————————————————————————
1b
2
105–106
205–206
196–198
189–190
242–245
315–318
302–303
180–182
182–183
155–157
233–236
216–218
210
2205
1740
2215
2205
2215
2210
2222
2216
C8H4ClNOS
(197.65)
3359
3180
3345
1690
1685
1675
1670
1685
——
1695
1680
——
1668
——
1686
——
1685
1770
1740
1730
1740
1730
1735
1735
1137
1130
——
1150
——
1145
——
——
——
——
——
——
——
——
——
——
——
——
——
——
——
C9H7N3OS2
(237.31)
3
C9H7N3OS2
(237.31)
4
3310
3280
——
——
C16H9N3O2S2
(339.39)
5
C17H10N4O2S3
(398.47)
6a
6b
7a
7b
8
C17H8N4O2S3
(364.40)
C17H8N4OS3
(380.46)
3295
3265
3280
2215
1658
2220
C16H13N3O2S
(311.36)
C15H13N3O3S2
(347.42)
——
3435
3485
2218
2211
2218
2222
2218
C16H11N3OS
(293.35)
9
C22H14N4O2S2
(430.51)
10
C14H9N3S
(251.31)
11
3360
3320
——
C14H10N2OS2
(286.38)
12
182–184
252–255
232–234
177–179
190–192
103–104
140–141
154–155
173.5
C14H8N2S2
(268.36)
13
3600
2215
1660
2210
C15H10N2O3S
(298.32)
2750 (br)
——
14
C15H8N2O2S
(280.31)
15
3480
2220
C14H10N2O2S
(270.31)
16
3419
2220
——
2215
1695
2205
C22H13N3O3S2
(431.50)
17a
17b
17c
17d
C11H9Cl2NO2S
(290.18)
——
——
——
2218
2215
2210
C13H11NO2S
(245.30)
C13H13NO2S
(247.32)
C14H8ClNO2S
(289.70)
—————————————————————————————————————————————
a C,H,N analyses were ± 0.4% of calculated values.
Arch. Pharm. Pharm. Med. Chem. 331, 91–96 (1998)

94
Shiba
Table 2: 13C-NMR of prepared compounds.
—————————————————————————————————————————————————————————————–
Cpd.no.
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
Others
—————————————————————————————————————————————————————————————–
1b
2
129.59
128.81
128.46
139.13
135.56
135.75
140.56
139.49
139.46
135.44
137.43
136.08
149.99
146.07
———
100.51
99.01
114.91
116.19
116.30
163.30
163.43
163.06
——————-
188.02, (C=S)
3
———
177.50 (C=S),46.52 (CH),
51.20 (CH)
4
129.49
129.14
136.61
136.55
139.48
138.21
129.81
136.34
147.75
147.51
100.19
100.20
116.32
115.40
163.75
163.29
—————————
7a
41.26 (CH2),126.36
128.36,128.50, 139.34
(Ar-C).
7b
8
129.15
128.56
136.21
136.28
139.19
138.37
136.36
135.48
146.63
144.81
99.98
98.98
116.18
116.01
160.21
———
21.50 (CH3),129.45,
130.33,136.95,145.97,
(Ar-C).
39.94 (CH2),126.36,
128.36,128.86,139.34,
160.56 (Ar-C).
9
128.75
128.53
135.81
135.44
138.42
139.08
135.66
135.30
144.63
146.95
101.68
100.20
116.47
115.40
160.34
———
125.91,130.79, (Ar-C).
10
128.66,128.80,139.31,
(Ar-C),143.80 (C=N).
11
16
128.07
135.49
138.41
135.67
143.96
100.23
115.34
157.21
119.73,123.33,124.33,
127.26,131.16,136.16,
136.80 (Ar-C).
128.56
128.93
135.44
135.46
138.08
140.60
135.61
137.79
144.17
148.35
101.81
97.53
115.65
116.27
160.25
160.45
123.20,125.41,126.32,
129.21,137.79,142.47, (Ar-C).
17a
17b
128.84
128.63
136.16
135.22
137.94
137.21
135.89
136.01
147.79
146.83
98.14
99.73
115.08
115.60
161.78
160.85
42.31 (CH2),73.89 ( CH)
28.87 (CH3),73.37 CH
74.24 (-C-), 83.72 (-C)
17c
17d
128.60
128.93
137.08
136.45
137.47
138.21
136.08
131.90
146.15
148.39
100.59
98.50
113.74
115.35
161.21
163.50
26.34 (CH3),63.34 (CH2).
83.65, ( CH)
122.71, 129.66, 139.95 (Ar-C).
—————————————————————————————————————————————————————————————–
The results listed in Table 3 show the relative toxicity of 12
compounds. The most effective compounds are nos. 6b, 17a,
and 5. Apparently, the thienyl moiety is not always a good
mimic of aryl moieties.
Table 3: Larvicidal activity of prepared compounds and conventional insec-
ticides against larvae of Culex pipiens.
——————————————————————————————
Compound No.
LC 50 (ppm)
Relative potency
——————————————————————————————
2
8
15
4
0.00002
0.00001
0.00004
0.000005
0.0003
Acknowledgment
3
The author is indebted to Prof. Dr. P. Margaretha (Institute of Organic
Chemistry, University of Hamburg, Germany) for his valued co-operation
and great help for performance of spectral and elemental analyses of the
compounds produced and also for Prof. Dr. R.F. Abou-Bakr (Entomology
Department, Faculty of Science, Ain Shams University, Cairo, Egypt for
performing the insecticidal activity tests.
5
6a
6b
8
32
0.5
42
11
18
22
38
2
0.000004
0.000014
0.000008
0.000007
0.000004
0.00008
0.000013
1
10
12
14
Experimental
15
All melting points are uncorrected. IR spectra are measured on a Pye
Unicam SP 200G spectrometer by the KBr wafer technique. 1H-NMR and
13C-NMR spectra determined on a Bruker AC-250 and Bruker AMX-400
spectrometer. All chemical shifts(δ) are expressed in ppm. Massspectra were
determined on a Finnigan-MAT-311 A mass spectrometer (70 eV).
17a
17d
12
Permithren
0.00015
——————————————————————————————
Arch. Pharm. Pharm. Med. Chem. 331, 91–96 (1998)

2-Propenoyl Azide Decomposition Products
95
1H-NMR (acetone-d6) of 7a: 2.77 (s,2H,CH2), 7.35 (m,7H,2-H+NH+Ar-
H), 7.95 (d,1H,1-H), 8.08 (d,1H,3-H), 8.50 (s,1H,4-H), 9.45 (sbr,1H,NH).
MS of 7a m/z: [M+1]+ 312 (3%), 225 (5%), 193 (3%), 162 (30%), 134
(12%), 118 (42%), 91 (100%).
2-Cyano-3-(2′-thienyl)-2-propenoyl chloride (1b)
A mixture of acid[15] (1a) (5g) and thionyl chloride (20 mL) was heated
on a water bath for 6 h. Excess thionyl chloride was distilled off until dryness;
the residue was collected and washed with petroleum ether 40–60 °C to give
1b as yellow crystals in 89% yield.– 1H-NMR (CDCl3) of 1b:7.34 (t,1H,2-
H), 8.00 (d,1H,1-H), 8.08 (d,1H,3-H), 8.48 (s,1H,4-H). MS of 1b: m/z: M+
(197, 42%), M + 2 (199, 6%), 162 (100%), 134 (42%), 107 (47%), 84 (9%).
1H-NMR (CDCl3) of 7b: 2.4 (s,3H,CH3), 7.30 (m,5H,2-H+Ar-H), 7.75
(d,1H, 1-H), 7.82 (d,1H,3-H), 7.90 (sbr,1H,NH), 8.20 (s,1H,4-H), 8.39
(sbr,1H,NH).
MS of 7b: m/z: M.+ (347, 3%), 192 (10%), 162 (100%), 84 (38%).
2-Cyano-3-(2′-thienyl)-2-propenoyl azide (1c)
2-Benzyl-5-([1′-cyano-2′-(2′′-thienyl)]-ethen-1′-yl)-1,3,4-oxadiazole (8)
To a solution of 1b (0.01 mol) in dry acetone (50 ml) was added portion-
wise at 0 °C a sodium azide (0.02 mol) suspension in water (5 ml). After
complete addition, the reaction mixture was stirred for a further 30 min and
then poured onto cold water (50 ml). The precipitated solid was filtered off,
washed with cold water (2×5 ml), and dried under reduced pressure to give
1c (without crystallization) as yellow solid in 88% yield, mp 82 °C (de-
comp.).
A mixture of 7a (1g) and phosphoryl chloride (10 mL) was heated on a
water bath for 2 h. After cooling, the reaction mixture was added to crushed
ice (50g). The precipitated solid was collected, washed with water
(2×20 mL), dried, and re-crystallized from chloroform to give 8 as red
crystals in 70% yield.
1H-NMR (DMSO-d6) of 8: 2.20 (s,2H,CH2), 7.05 (m,6H,2-H+Ar-H), 7.77
(d, 1H,1-H), 7.83 (d,1H,3-H), 8.33 (s,1H,4-H).
MS of 8: m/z: M•+ (293,2%), [M–1]+ (292, 12%), 220 (8%), 193 (13%),
162 (28%), 134 (12%), 118 (40%), 91 (100%).
N-[2-Cyano-3-(2′-thienyl)-2-propenoyl]thiourea (2),5-cyano-6-(2′-thienyl)-
2-thioxo-hexahydropyrimidin-4-one (3), bis[2-cyano-3-(2′-thienyl)-2-
propenoyl]amine (4) and N,N′-bis[2-cyano-3-(2′-thienyl)-2-propenoyl]-
thiourea (5)
N,N′-Bis[2-cyano-3-(2′-thienyl)-2-propenoyl]-1,2-diaminobenzene (9)
A mixture of 1c or 1b (0.01 mol) and o-phenylene diamine (0.01 mol) in
toluene (50 mL) was refluxed for 30 min. The solid precipitated during
refluxing wascollectedand crystallized from toluene/ ethanol mixture togive
9 as yellow crystals in 72% yield.
A mixture of 1c or 1b (0.01 mol) and thiourea (0.01 mol) in toluene
(50 mL) was refluxed for 30 min. The separated solid was filtered off and
re-crystallized from ethanol to give 2 as yellow crystals in 30% yield. The
solid precipitated on concentration of the filtrate was collected and triturated
with a toluene/petroleum ether (60–80 °C) mixture and toluene to give 3 as
yellow crystals in 15% yield, 4 as yellow crystals in 5% yield, and 5 as yellow
crystals in 9% yield.
1H-NMR (DMSO-d6) of 9: 7.52 (m,4H,Ar-H), 7.82 (t,2H,2×2-H), 8.17
(d,2H, 2×1-H), 8.32 (d,2H,2×3-H), 8.80 (s,2H,2×4-H), 10.00 (sbr,2H,2×NH).
MS of 9: m/z: M•+ (430,10%), 268 (18%), 250 (19%), 225 (2%),162
(100%), 134 (44%), 90 (11%).
1H-NMR (DMSO-d6) of 2:7.33 (t,1H,2-H), 7.82 (d,1H,1-H), 8.02 (d,1H,3-
H), 8.42 (s,1H,4-H),8.80 (sbr,1H,NH), 9.12 (sbr,1H,NH), 9.82 (sbr,1H,NH).
MS of 2: m/z: M+ (237, 8%), [M–1]+ (236,11%), 204 (3%), 179 (78%),
162 (100%), 134 (83%), 58 (42%).
2-([1′-cyano-2′-(2′′-thienyl)]ethen-1′-yl)-1H-benzimidazole (10)
A mixture of 9 (1 g) and phosphoryl chloride (10 mL) was heated on a
water bath for 4 h. The mixture was added after cooling to crushed ice
(50 g).The precipitated solid was filtered off, washed with water (2×10 mL),
dried, and crystallized from toluene to give 10 as yellow crystals in 52%
yield, the insoluble residue was crystallized from ethanol to give 1a which
identified by mp, m. mp, and spectral data.
1H-NMR (DMSO-d6) of 3: 5.30 (d,1H,CH), 5.65 (d,1H,CH), 7.22 (t,1H,2-
H), 7.82 (d,1H,1-H), 8.05(d,1H,3-H), 11.10(sbr,1H,NH), 11.50 (sbr,1H-NH).
MS of 3: m/z: M+ (237, 18%), [M-SH]+ (204, 12%) 192 (4%), 178 (12%),
162 (100%), 134 (50%), 108 (16%), 91 (55%).
1H-NMR (acetone-d6) of 4: 7.35 (t,1H,2-H), 7.38(t,1H,2-H), 7.83 (d,1H,1-
H), 7.92 (d,1H,1-H), 8.03 (d,1H,3-H), 8.09 (d,1H,3-H), 8.45 (s,1H,4-H), 8.49
(s, 1H,4-H), 9.55 (sbr,1H,NH).
1H-NMR (CDCl3) of10: 7.38 (m,4H,Ar-H), 7.90 (t,1H,2-H), 8.10 (d,1H,1-
H), 8.18 (d,1H,3-H), 8.35 (s,1H,4-H), 8.92 (s,1H,NH).
MS of 4: m/z: M.+ (339, 15%), [M-1]+ (338,12%), 298 (3%), 205 (2%), 191
(10%), 177 (12%), 162 (100%), 134 (65%), 97 (99%), 84 (10%).
S-(2′-Aminophenyl)2-cyano-3-(2′′-thienyl)-2-thiopropenoylate (11)
A mixture of 1c or 1b (0.01 mol) and 2-aminothiophenol (0.01 mol) in
toluene (50 mL) was refluxed for 1 h. The solid separated during reflux was
collected and identified as aminothiophenol hydrochloride. The filtrate was
concentrated and the precipitated solid was collected and crystallized from
a petroleum-ether (60–80 °C)/toluene mixture to give 11 as yellow crystals
in 25% yield.
2,6-Bis[ (2′-thienyl-1′-cyano)-ethene-1′-yl]-1,3,5-oxadiazin-4-one (thione)
(6a and b)
A mixture of 1c or 1b (0.01 mol) and urea or thiourea (0.01 mol) was heated
at 170 °C without solvent for 2h. After cooling the solid was triturated with
ethanol, the solid separated was filtered, washed withethanol andcrystallized
from toluene to give 6a and 6b as brown crystals in 86% and 65% yield
respectively.
1H-NMR (CDCl3) of 11: 7.05 (t,1H,Ar-H), 7.22 (d,1H,Ar-H), 7.35
(m,2H,2-H+Ar-H), 7.51 (d,1H,Ar-H), 7.84 (d,1H,3-H), 7.82 (d,1H,1-H),
8.39 (s,1H, 4-H), 8.45 (sbr,1H,NH), 9.10 (s,1H,NH).
MS of 11: m/z: M+ (268, 2%), [M–1]+ (289, 20%), 268 (4%), 267 (19%),
242 (20%), 162 (100%), 150 (20%), 134 (55%).
Conversion of 5 into 6b
The solid compound 5 (1g) was heated without solvent at 170 °C for
30 min. After cooling, the solid was triturated with toluene under reflux and
filtered. The solid separated from filtrate, was collected and identified as 6b
(96% yield) by mp, m. mp, TLC, and spectral data.
2-([1′-Cyano-2′-(2′′-thienyl)]-ethen-1′-yl)-1,3-benzothiazole (12)
Thio ester 11 (1 g) was heated without solvent at 210 °C for 2 h. The mass
residue was crystallized from toluene to give 12 as yellow crystals in 85%
yield. MS of 12: m/z: M•+ (268, 23%), [M–1]+ 268 (100%), 134 (75%), 108
(40%), 82 (34%).
N-(Phenylacetyl and/ or p-toluenesulfonyl)-2-cyano-3-(2′-thienyl)-2-
propenoic hydrazides (7a and b)
A mixture of 1c or 1b (0.01 mol), acid hydrazides, namely, phenylacetic
hydrazide and/or p-toluene sulfonyl hydrazide (0.01 mol) and triethylamine
(0.01 mol) in toluene (50 mL) was refluxed for 30 min. The solvent was
removed and the residue was triturated with cold dilute hydrochloric acid
(20 mL, 10%). The solid produced was collected, washed with water
(2×10 mL), dried, and crystallized from ethanol to give 7a and b as colourless
crystals in 65 and 90% yield respectively.
N-[2-Cyano-3-(2′-thienyl)-2-propenoyl] anthranilic acid (13)
A mixture of 1c or 1b (0.01 mol) and anthranilic acid (0.01 mol) in toluene
(50 mL) was refluxed for 1 h. The solid precipitated during refluxing was
filtered off and crystallized from ethanol to give 13 as yellow crystals in 88%
yield. MS of 13: m/z: M•+ (298, 6%), 280 (60%), 254 (35%), 177 (22%), 162
(100%), 136 (72%), 91 (53%).
Arch. Pharm. Pharm. Med. Chem. 331, 91–96 (1998)

96
Shiba
MS of 17c: m/z: M•+ (247, 22%), 179 (42%), 162 (25%), 134 (8%), 108
(9%), 69 (100%).
2-([1′-Cyano-2′-(2′′-thienyl)]-ethen-1′-yl)-3,1-benzoxazin-4-one (14)
1H-NMR (CDCl3)of 17d:7.15 (d,2H,Ar-H),7.42 (d,2H,Ar-H), 7.35
(t,1H,2-H), 7.82 (d,1H,1-H), 7.92 (d,1H,3-H), 8.50 (s,1H,4-H).
MS of 17d: m/z: M•+ (289, 3%), 179 (12%), 162 (100%), 134 (38%), 108
(5%), 84 (3%).
Compound 13 (1 g) in acetic anhydride (5 mL) was heated on a water bath
for 30 min. The reaction mixture was poured onto crushed ice (30 g). The
precipitated solid was filtered off, washed with water (2×10 mL), dried, and
crystallized from an ethanol/acetic acid mixture to give 14 as yellow crystals
in 97% yield.
2′-Aminophenyl 2-cyano-3-(2′′-thienyl)-2-propenoylate (15) and
2′-[N-(2′′-cyano-3′′-(2′′′-thienyl)-2′-propenoyl)]aminophenyl
2-cyano-3-(2′-thienyl)-2-propenoylate (16)
References
[1] S.A. Shiba, Phosphorus, Sulfur and Silicon 1996, 114, 29.
[2] S.A. Shiba, A.F.M. Fahmy, H.A. Abdel-Hamid, M.S. Massoud, Egypt
J. Chem. 1993, 36, 409 [C.A. 1996, 124,117177h].
A mixture of 1c or 1b (0.01 mol) and 2-aminophenol (0.01 mol) in toluene
(50 mL) was refluxed for 30 min. The solid separated immediately was
collected and crystallized from toluene/ethanol mixture to give 16 as yellow
crystals in 35% yield, the filtrate was concentrated and the precipitated solid
was collected and crystallized from toluene to give 15 as yellow crystals in
12% yield.
[3] H.A. Abdel-Hamid, A.F.M. Fahmy, S.A. Shiba, N.A. El-Hawary,
Egypt. J. Chem. 1993, 36,363 [C.A. 1996, 124,117240y].
[4] H.A. Abdel-Hamid, A.F.M. Fahmy, S.A. Shiba, N.A. El-Hawary,
1H-NMR (acetone-d6) of 15: 7.25 (m,5H,2-H+Ar-H), 8.00 (m,3H,1-H+3-
H+ NH), 8.44 (s,1H,4-H), 8.80 (sbr,1H,NH).
Egypt. J. Chem. 1993, 36,167 [C.A. 1995, 123, 32975w].
MS of 15: m/z: M•+ not detected, 253 (3%), 251 (25%), 162 (100%), 134
(48%), 108 (10%), 91 (46%).
[5] T. Mita, A. Numata, S. Ishii, M. Kudo, Y. Inoe, T. Myake, Jpn. Kokai
Tokkyo Koho Jpn. 08 27 ,120 [96 27,120] (Cl C07D 239/22) 30 Jan
1996 [C.A. 1996, 124, 343323j].
1H-NMR (DMSO-d6) of 16: 7.50 (m,6H,2×2-H+Ar-H), 8.06 (d,1H,1-H),
8.25 (d,1H,1-H), 8.29 (d,1H,3-H), 8.40 (d,1H,3-H), 8.62 (s,1H,4-H), 8.95
(s,1H,4-H), 10.22 (sbr,1H,NH).
[6] M.A. Dekeyser, W.A. Harrison, P.T. McDonald, G.W. Jr. Angle,
S.M.M. Ismail, R.G.H. Downer, ACS Symp. Ser. 1995, 589,183 [C.A.
1995, 122, 308609u, 1995].
MS of 16: m/z: M•+ (431, 5%), 296 (3%), 270 (6%), 252 (25%), 11 (18%),
162 (100%), 134 (38%), 90 (12%).
[7] U. Kraatz, W. Kraemer, J. Hartwig, C. Erdelen (Bayer A.-G.) Ger.of-
fen. DE 4,314,037 (Cl C07D271/10), 03 Nov. 1994 [C.A. 1995, 122,
P81377r].
Alkyl and/or Aryl 2-cyano-3-(2′-thienyl)-2-propenoylates (17a-d)
General procedure:
[8] M.I. Richard, B.D. Philip, PCT Int. Appl Wo 95 05, 368 (Cl. C07 D
271/07) 23 Feb. 1995.[C.A. 1995, 123,9445q].
A mixture of 1c or 1b (0.01 mol), alcohols and/or phenols, viz. 1,3-di-
chloro-2-propanol, 2-methyl-3-butyn-2-ol, 2-methyl-3-buten-2-ol, and/or
p-chlorophenol (0.01 mol), respectively and triethylamine (0.01 mol) in
toluene (30 mL) was refluxed for 2–4 h. The solvent was removed and the
residue was neutralized with cold dilute hydrochloric acid (20 mL, 10%).
The precipiated solid was collected, washed with water (2×10 mL), dried and
crystallized from petroleum-ether 60–80 °C to give 17a–c as yellow crystals
in 92–95% yield and 17d as brown crystals in 60% yield.
1H-NMR (CDCl3) of 17a: 3.85 (d,4H,2×CH2), 5.32 (t,1H,CH), 7.29 (t, 1H,
2-H), 7.85 (d,1H,1-H), 7.90 (d,1H,3-H), 8.46 (s,1H,4-H).
MS of 17a: m/z: M•+ (290, 10%), 179 (98%), 162 (100%), 134 (43%), 108
(10 %);
[9] Baasner, H. Hagemann, M. Heil, F. Lieb, H. Uhr, C. Erdelen (Bayer
A.-G.) Ger offen DE 4,413, 659 (Cl C0 7D 235/10), 28 Sep. 1995 [C.A.
1996, 124, P55953x, 1996].
[10] D.L. Brandon, R.G. Binder, A.H. Bates, W.C. Jr. Montague, New
Front Agrochem. Immunoassay 1995, 77 [C.A. 1996, 124.R 168130u].
[11] G.A. Cain, P.J. Gilligan, S.W. Jan, Eur.Pat Appl. EP 449,187 (Cl.
C07D211/22), 02 Oct. 1991.[C.A. 1992, 116, P20945d].
[12] J. Drabek, Ger. offen. DE4, 034, 706 (Cl. C07C 275/54), 08 May
1991.[C.A. 1991, 115, 158743x].
1H-NMR (CDCl3) of 17b: 1.80 (s,6H,2×CH3), 2.62 (s,1H,CH), 7.23 (t,1H,
2-H) 7.80 (d,1H,1-H), 7.81 (d,1H,3-H), 8.39 (s,1H,4-H).
[13] WHO, Mimeographed document, WHO, VBC 1975, 175.
MS of 17b: m/z: M•+ (245, 40%), 179 (100%), 162 (80%), 134 (39%), 108
(12%).
[14] W.S. Abbott, A method of computing the effectiveness of an insecticide,
J. Econ. Entomol. 18, 265.
1H-NMR (CDCl3) of 17c: 1.60 (s,6H,2×CH3), 5.15 (d,1H,CH2), 5.30
(d,1H, CH2), 6.15 (dd,1H,CH), 7.35 (t,1H,2-H), 7.75 (d,1H,1-H), 7.80
(d,1H,3-H), 8.38 (s,1H,4-H).
[15] F.Fillnore, C.Lilan, J. Am. Chem. Soc. 1986, 108, 4504.
Received: September 22, 1997 [FP252]
Arch. Pharm. Pharm. Med. Chem. 331, 91–96 (1998)