Synthesis of 3-substituted benzpyrid-4-imino-2-oxlme derivatives

Article abstract of DOI:10.1002/jccs.200500018

Pyrazolone, Isoxazolone, Pyrimidinone, Pyrimidinothione, thiazolidinone and β-lactamincorporating 2- oximino benzpyrid-4-one derivatives have been syn the sized by cyclocondensation addition reaction and cycloaddition of hydrazine hydrate, phenyl hydrazin

Full text of DOI:10.1002/jccs.200500018

Journal of the Chinese Chemical Society, 2005, 52, 119-124
119
Synthesis of 3-Substituted Benzpyrid-4-imino-2-oxime Derivatives
H. A. Soleiman, A. I. M. Koraiem and N. Y. Mahmoud*
Chemistry Department, Aswan Faculty of Science, South Valley University, Aswan, Egypt
Pyrazolone, Isoxazolone, Pyrimidinone, Pyrimidinothione, thiazolidinone and b-lactam incorporating
2-oximino benzpyrid-4-one derivatives have been synthesized by cyclocondensation addition reaction and
cycloaddition of hydrazine hydrate, phenyl hydrazine, hydroxylamine, urea, thiourea, mercapto acetic acid,
and chloroacetylchloride, respectively.
Keywords: Substituted heterocyclic compounds; Synthesis.
INTRODUCTION
New molecules fused and isolated heterocyclic com-
addition product(c), follwingly dehydration process to give
3-acetyl benzpyrid-4-imino-2-oxime (equation 1).
O
O
pounds are biologically interesting and their chemistry has
received considerable interest,1-7 as has their use synthetic
drugs.8-12 This is principally due to the unique physical and
chemical properties of such compounds, which enable their
wide application as plant growth regulators.13 The com-
pounds described in this work are composed of four-, five-,
and six-membered heterocyclic systems containing nitrogen,
oxgyen, and sulfur atoms. However various styryl and Schiff
base compounds incorporating the benzpyrid-4-imino-2-
oxime residue have been synthesized and studied by us.
Therefore, several fused and isolated pyrazolo-, pyrimidino-,
oxazolo-, thiazolo-, and b-lactam and their derivatives have
been synthesized.
O
O
CH3
H
H2N
+ BH
N
H
NOH
N
H
NOH
N
H
NOH
(A)
d-
O
C
O
O
CH3
NH2
d+
O
O
-NH2+BH
CH3
CH3
NH2
NOH
N
N
H
NOH
H
(B)
NH3
NH
O
CH3
OH
H2N
O
N
H
NOH
CH3
NOH
(1)
N
H
Equation 1
(C)
RESULT AND DISCUSSION
The methyl group in compound (1) condensed with dif-
ferent aromatic aldehydes in ethanol under piperidine as
catalysit to yield the corresponding N-chalcone benzpyrid-
4-imino-2-oxime derivatives (2a-e) (Scheme I). The chalcone
derivatives (2a-e) when interacted with hydrazine hydrate in
the presence of acetic acid in ethanol as solvent and/or phen-
ylhdyrazine in ethanol as solvent under piperidine as catalyst,
respectively, gave the required N-acetylpyrazolo-, and/or N-
phenylpyrazolo-, (3a-e), (4a-e), respectively (Scheme I). When
the chalcone derivatives interacted with hydroxylamine hy-
drochloride in ethanol as solvent, with sodium hydroxide as
catalyst, they gave the required N-isooxazolino benzpyrid-
4-imino derivatives (5a-e) (Scheme I). The chalcone deriva-
tives (2a-e) when interacted with urea and/or thiourea in etha-
nol as solvent, with sodium hydroxide as catalyst, gave the
In a recent paper, we reported that the synthesis of 3-
acetyl benzpyrid-4-imino-2-oxime was obtained by acetyla-
tion of an active methylene group in the compound benz-
pyrid-4-one-2-oxime14 when heated with acetamide in an oil
bath at 200-220.15 The formation of compound (1) was sug-
gested to proceed as a reaction related to the mixed Claisen
condensation using nonenolizable acetamide as basic cyclat-
ing agents to generate heterocyclic ketone enolate ions (A).
Nucleophilic addition reaction of ethanolic solution of the
latter enolate formed ions to the carbonyl group of acid amide
(acyl transfer) forming the suggested intermediate compound
(B), which undergo through thermal basic condition dissoci-
ates by expelling an amino group which attracted proton ion
from BH+ to afford the corresponding suggested nucleophilic

120 J. Chin. Chem. Soc., Vol. 52, No. 1, 2005
Soleiman et al.
Schiff base in ethanol in the presence of piperidine as catalyst
afforded thiazolidinone derivatives (9a-c) (Scheme II). The re-
action of (8a-c) with equimolar ratios of chloroacetylchloride
in ethanol in the presence of triethylamine as catalyst af-
forded b-lactam derivatives (10a-c) (Scheme II).
Scheme I
CHO
NH
O
X
CH
X
C
H
1
N
H
NOH
2a-e
/pip
COH3
EtOH
NH
N
N
H2NNH2.H2O
G.AcOH
X
N
H
NOH
EXPERIMENTAL
3a-e
Ph
NH
N
N
H2NNHPh
EtOH/pip
All melting points were uncorrected. IR spectra were
X
recorded on a Pye Unicam SP 1100 spectrophotometer using
N
NOH
4a-e
H
1
KBr disc. H-NMR spectra were recorded on a Varian EM-
NH
O
N
390 MHZ Spectrophotometer using DMSO d6 as a solvent and
TMS as an internal standard. Chemical shifts are expressed as
ppm, units. Mass spectra were recorded on an HP Ms 6988
spectrometer. Analytical data were determined with a CE 440
Elemental Analyzer-Automatic Injector at Cairo University.
H2NOH.HCl
NaOH
X
N
H
NOH
5a-e
A
A=O, S
NH
NH
N
A
H2NCNH2
X
Synthesis of 3-acetyl benzpyrid-4-imino-2-oxime (1)
A mixture of benzpyrid-4-one-2-oxime and acetamide
were heated in an oil bath at (200-220) for 2 hours and kept
over night in a refrigerator.15 The semi-solid mass was ex-
tracted with benzene and purified from ethanol to give 3-
acetyl benzpyrid-4-imino-2-oxime (c.f. Table 2).
N
NOH
6, 7a-e
H
Where a, X=H; b, X=P.OH; c, X=P.Cl; d, X=P.OCH3 ; e,X=O.NO2
required N-pyrimidino benzpyrid-4-imino derivatives (6a-e
)
and/or N-pyrimidinothiono benzpyrid-4-imino derivatives
(7a-e) (Scheme I).
N-acetylbenzpyrid-4-imino-2-oxime (1) was condensed
with nitroso compounds such as p-nitrosophenol, b(a)-ni-
troso-a-(b)-naphthol, in the presence of piperidine as cata-
Synthesis of N-Chalcone benzpyrid-4-imino-2-oxime de-
rivatives (2a-e
)
To a solution of 1 (2.17 g, 0.01 mol) and aromatic alde-
hydes (1.06 g-1.51 g, 0.01 mol) in absolute ethyl alc, two
drops of piperidine were added. The reaction mixture was
refluxed for 6-8 hrs then left to cool and poured on cold water.
The solid product so formed was collected by filtration and
crystallized from ethanol to give (2a-e) (c.f. Tables 1, 2).
lyst to give the corresponding Schiff base derivatives (8a-c
)
(Scheme II). Cycloaddition reaction of thioglycolic acid to
the previously prepared Schiff base compounds (8a-c) pro-
ceeded successfully. Thus, thioglycolic acid when added to
Scheme II
Synthesis of N-acetyl pyrazolino-benzpyrid derivatives
(3a-e
)
To a solution of chalcones (2a-e) (3.05 g - 3.51 g, 0.01
mol) in ethanol as solvent, hydrazine hydrate (0.01 mol) was
added followed by glacial acetic acid (10 mL), and the reac-
tion mixture was refluxed for (8-10) hrs. The reaction mix-
ture was concentrated and coold. These materials were tri-
turated with water, precipitates were separated, filtrated,
washed several times with water and crystallized from etha-
nol to give (3a-e) (c.f. Tables 1, 2).
Synthesis of N-phenylpyrazolino-benzpyrid derivatives
(4a-e
)
To a solution of chalcones (2a-e) (3.05 g - 3.51 g, 0.01

Synthesis of 3-Substituted Benzpyrid-4-imino-2-oxime Derivatives
J. Chin. Chem. Soc., Vol. 52, No. 1, 2005 121
Table 1. Characterization of compounds (1-10)
Comp.
Analysis% Calc. (Found)
Colour
m.p. °C Yield % Mol. Formula
MS (m/z)
No.
C
H
N
1
Pale yellow
Yellow
165-167
200-202
169-171
178-180
65
74
68
73
75
65
63
33
31
45
48
62
71
65
68
43
58
28
68
65
25
65
42
51
46
65
53
33
C11H11N3O2
C18H15N3O2
C18H15N3O3
C18H14N3O2Cl
C18H17N3O3
C18H14N4O4
C20H19N5O2
C20H20N5O3
C20H18N5O2Cl
C21H21N5O3
C20H18N6O4
C24H21N5O
60.82
(60.75)
70.81
(7.57)
67.28
(67.06)
63.62
(63.50)
64.47
(64.84)
61.71
(61.51)
66.48
(66.27)
63.49
(63.30)
60.75
(60.54)
64.45
(64.25)
59.11
(58.95)
72.91
(72.75)
70.07
(69.92)
67.05
(66.96)
70.58
(70.45)
65.45
(65.33)
67.50
(67.27)
64.28
(64.08)
60.93
(60.55)
65.14
(65.10)
61.89
(61.73)
65.70
(65.76)
62.82
(62.76)
59.76
(59.71)
63.66
5.06
(5.01)
4.91
(4.81)
4.67
(4.37)
4.12
(4.10)
5.07
(5.07)
4.00
(4.04)
5.26
(5.26)
5.01
(5.02)
4.55
(4.57)
5.37
(5.36)
4.43
(4.43)
5.31
(5.31)
5.10
(5.14)
4.66
(4.65)
5.41
(5.25)
4.55
(4.55)
5.00
(5.10)
4.76
(4.75)
4.23
(4.20)
5.14
(5.14)
4.29
(4.28)
4.89
(4.89)
4.68
(4.68)
4.19
(4.19)
5.31
19.35
(19.38)
13.77
(13.80)
13.08
(13.07)
12.37
(12.33)
12.53
(12.50)
16.00
(16.05)
19.39
(19.38)
19.38
(19.36)
18.51
(18.53)
17.69
(17.68)
21.48
(21.44)
17.72
(17.71)
17.03
(17.05)
16.29
(16.27)
16.47
(16.45)
19.09
(19.06)
17.50
(17.54)
16.66
(16.46)
15.79
(15.75)
16.00
(16.04)
20.05
(20.01)
20.17
(20.15)
19.28
(19.25)
18.34
(18.32)
18.56
217
305
321
339.5
335
350
361
378
395.5
391
406
395
411
429.5
425
440
320
336
354.5
350
349
347
363
381.5
377
392
363
379
2a
2b
2c
2d
2e
3a
3b
3c
3d
3e
4a
4b
4c
4d
4e
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
7a
7b
Brown
Yellow
Greenish yellow 199-201
Brown
Pale brown
Brown
187-189
186-188
178-180
168-170
162-164
165-167
188-190
189-191
186-188
149-151
185-187
182-184
240-242
164-166
158-160
180-182
236-238
Pale yellow
Brown
Dark brown
Dark yellow
Pale brown
Brown
C24H21N5O2
C24H20N5OCl
C25H23N5O2
C24H20N6O3
C18H16N4O2
C18H16N4O3
C18H15N4O2Cl
C19H18N4O3
C18H15N5O3
C19H17N5O2
C19H17N5O3
C19H16N5O2Cl
C20H20N5O2
C19H16N6O4
C19H17N5OS
C19H17N5O2S
Pale brown
Orange
Brown
Brown
Yellow
Pale brown
Brown
Pale brown
Yellowish green 251-253
Orange
Pale yellow
Pale brown
Yellow
191-193
246-248
234-236
245-247
197-199
(63.61)
58.20
(58.27)
62.82
(62.76)
60.18
(5.31)
4.08
(4.08)
4.68
(4.69)
4.48
(18.51)
21.42
(21.41)
19.28
(19.33)
18.46
Dark brown
(60.10)
(4.48)
(18.42)

122 J. Chin. Chem. Soc., Vol. 52, No. 1, 2005
Soleiman et al.
7c
Pale yellow
Pale yellow
Brown
204-206
210-212
200-202
195-197
131-133
158-160
42
48
61
73
75
68
54
48
75
43
56
58
C19H16N5OSCl
C20H19N5O2S
C19H16N6O3S
C17H14N4O3
57.35
(57.30)
61.06
(61.17)
55.88
(55.82)
63.34
(63.22)
67.74
(67.59)
67.74
(67.65)
57.61
(57.53)
61.92
(61.78)
61.92
4.02
(4.02)
4.83
(4.80)
3.92
(3.92)
4.34
(4.32)
4.83
(4.83)
4.83
(4.83)
4.04
(4.03)
4.48
(4.48)
4.48
17.61
(17.63)
17.81
(17.80)
20.58
(20.53)
17.39
(17.38)
15.06
(15.02)
15.06
(15.02)
14.14
(14.13)
12.55
(12.51)
12.55
397.5
7d
7e
393
408
8a
Black
322
8b
8c
Dark violet
Violet
C21H18N4O3
372
C21H18N4O3
372
9a
Greenish black 205-207
Reddish violet 138-140
C19H16N4O4S
C23H20N4O4S
C23H20N4O4S
C19H15N4O4Cl
C23H19N4O4Cl
C23H19N4O4Cl
396
9b
9c
446
Pale violet
Black
162-164
> 300
446
(61.72)
57.88
(57.72)
61.58
(61.45)
61.58
(4.48)
3.76
(3.76)
4.23
(4.23)
4.23
(12.52)
14.05
(14.04)
12.48
(12.32)
12.48
10a
10b
10c
398.5
448.5
448.5
Reddish violet 150-152
Dark violet 145-147
(61.51)
(4.23)
(12.44)
mol) in ethanol as solvent phenylhydrazine (0.01 mol) was
added in the presence of a few drops of piperidine as catalyst,
and the reaction mixture was refluxed for (8-10) hrs. The re-
action mixture was concentrated, triturated with cold water;
the crystals were separated. It was filtrated, washed several
Synthesis of N-thiopyrimidino benzpyrid derivatives
(7a-e
)
Chalcones (2a-e) (3.05 g - 3.51 g, 0.01 mol) were re-
fluxed with thiourea (0.76 g, 0.01 mol) in the presence of so-
dium hydroxide as catalyst and ethanol as solvent for (6-8)
hrs. The reaction mixture was filtrated from unreacted mate-
rials; the filtrate was concentrated to one - third of its volume
triturated with water. Where by the products were separated,
filtrated, washed several times with water and crystallized
from ethanol to give (7a-e) (c.f. Tables 1, 2).
times with water, and crystallized from ethanol to give (4a-e
(c.f. Tables 1, 2).
)
Synthesis of N-isooxazolino-benzpyrid derivatives (5a-e
)
Chalcones (2a-e) (3.05 g - 3.51 g, 0.01 mol) were re-
fluxed with hydroxylamine hydrochloride (0.069 g, 0.01
mol) in the presence of sodium hydroxide as catalyst and eth-
anol as solvent for (2-3) hrs. The reaction mixture was fil-
trated from unreacted materials; the filtrate was triturated
with cold water whereby the products were separated, fil-
trated, washed several times with water, and crystallized
from ethanol give (5a-e) (c.f. Tables 1, 2).
Synthesis of N-azaryl benzpyrid-4-imino-2-oxime deriva-
tives (8a-c
)
Compound 1 (2.17 g, 0.01 mol) and nitroso compounds
(1.23 g - 1.73 g, 0.01 mol) in equimolar ratios were dissolved
in ethanol, and a few drops of piperidine as catalyst were
added; the mixture was refluxed about 10 h. The reaction
mixture was allowed to cool at room temperature then fil-
trated, washed several times with water, dried and collected,
and crystallized from methanol to give (8a-c) (c.f. Tables 1, 2).
Synthesis of N-pyrimidino benzpyrid derivatives (6a-e
)
Chalcones (2a-e) (3.05 g - 3.51 g, 0.01 mol) were re-
fluxed with urea (0.6 g, 0.01 mol) in the presence of sodium
hydroxide as catalyst and ethanol as solvent for (6-8) hrs. The
reaction mixture was filtrated from unreacted materials; the
filtrate was concentrated to one - third of its volume and
triturated with water, whereby the products were separated,
filtrated, washed several times with water, and crystallized
from ethanol to give (6a-e) (c.f. Tables 1, 2).
Synthesis of N-thiazol benzpyrid-4-imino-2-oxime deriva-
tives (9a-c
)
A solution was made of (8a-c) (3.22 g - 3.72 g, 0.01 mol)
and thioglycolic acid (0.92 g, 0.01 mol) in ethanol in the pres-
ence of few drops of piperidine. The mixture was refluxed for
8-10 hrs. The filtrate was evaporated to one - third of its vol-

Synthesis of 3-Substituted Benzpyrid-4-imino-2-oxime Derivatives
Table 2. IR, 1H-NMR spectral data of compounds (1-10)
J. Chin. Chem. Soc., Vol. 52, No. 1, 2005 123
Comp.
IR (cm)-1
No.
1H-NMR (d-ppm)
1
3654 (OH), 3093 (NH), 1699 (C=O),
1656 (C=NOH)
2.1 (S, 1H, CH sat; 3H, COCH3), 7.1-8.5 (m, 5H, aromatic protons; C=NH), 11 (S,
1H, NH; 1H, N=OH)
2a
2b
2c
2d
2e
3a
3b
3c
3d
3e
4a
4b
4c
4d
4e
5a
5b
5c
5d
5e
6a
6b
6c
6d
6e
7a
3053-3481 (OH, NH), 1698 (C=O),
1652 (C=NOH)
3053-3481 (OH, NH), 1698 (C=O),
1652 (C=NOH)
3053-3481 (OH, NH), 1698 (C=O),
1652 (C=NOH)
3053-3481 (OH, NH), 1698 (C=O),
1652 (C=NOH)
3053-3481 (OH, NH), 1698 (C=O),
1652 (C=NOH)
3428 (OH), 3093 (NH), 1686 (C=O),
1590, 1423 (C=N)
3428 (OH), 3093 (NH), 1686 (C=O),
1590, 1423 (C=N)
3428 (OH), 3093 (NH), 1686 (C=O),
1590, 1423 (C=N)
3428 (OH), 3093 (NH), 1686 (C=O),
1590, 1423 (C=N)
3428 (OH), 3093 (NH), 1686 (C=O),
1590, 1423 (C=N)
3160-3570 (OH, NH), 1670 (C=O),
1640, 1430 (C=N)
3160-3570 (OH, NH), 1670 (C=O),
1640, 1430 (C=N)
3160-3570 (OH, NH), 1670 (C=O),
1640, 1430 (C=N)
3160-3570 (OH, NH), 1670 (C=O),
1640, 1430 (C=N)
3160-3570 (OH, NH), 1670 (C=O),
1640, 1430 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1651, 1588 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1651, 1588 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1651, 1588 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1651, 1588 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1651, 1588 (C=N)
3428 (OH), 3250 (NH), 1684 (C=O),
1528, 1590 (C=N)
3428 (OH), 3250 (NH), 1684 (C=O),
1528, 1590 (C=N)
3428 (OH), 3250 (NH), 1684 (C=O),
1528, 1590 (C=N)
3428 (OH), 3250 (NH), 1684 (C=O),
1528, 1590 (C=N)
2.3 (S, 1H, CH sat), 7-8.7 (m, 12H aromatic protons; olefinic protons; C=NH), 9.9
(S, 1H, NOH), 11 (S, 1H, NH)
2.3 (S, 1H, CH sat), 7-8.7 (m, 11H aromatic protons; olefinic protons; C=NH), 9.9
(S, 2H, OH), 11 (S, 1H, NH)
2.3 (S, 1H, CH sat), 7-8.7 (m, 11H aromatic protons; olefinic protons; C=NH), 9.9
(S, 1H, NOH), 11 (S, 1H, NH)
2.3 (S, 1H, CH sat; 3H, OCH3), 7-8.7 (m, 11H, aromatic protons; olefinic protons;
C=NH), 9.9 (S, 1H, NOH), 11 (S, 1H, NH)
2.3 (S, 1H, CH sat), 7-8.7 (m, 11H aromatic protons; olefinic protons; C=NH), 9.9
(S, 1H, NOH), 11 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.32 (S, 3H, COCH3), 7.1-8.4 (m, 10H
aromatic protons; C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.32 (S, 3H, COCH3), 7.1-8.4 (m, 9H aromatic
protons; C=NH), 10 (S, 2H, OH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.32 (S, 3H, COCH3), 7.1-8.4 (m, 9H aromatic
protons; C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.32 (S, 3H, COCH3), 3.7 (S, 3H OCH3), 7.1-
8.4 (m, 9H aromatic protons; C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.32 (S, 3H, COCH3), 7.1-8.4 (m, 9H aromatic
protons; C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.3 (S, 2H, CH2), 2.4 (S, 2H, CH sat), 7.1-8.4 (m, 15H aromatic protons; C=NH),
10.2 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.3 (S, 2H, CH2), 2.4 (S, 2H, CH sat), 7.1-8.4 (m, 14H aromatic protons; C=NH),
10.2 (S, 2H, OH), 11.7 (S, 1H, NH)
1.3 (S, 2H, CH2), 2.4 (S, 2H, CH sat), 7.1-8.4 (m, 14H aromatic protons; C=NH),
10.2 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.3 (S, 2H, CH2), 2.4 (S, 2H, CH sat), 3.4 (S, 3H, OCH3), 7.1-8.4 (m, 14H aromatic
protons; C=NH), 10.2 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.3 (S, 2H, CH2), 2.4 (S, 2H, CH sat), 7.1-8.4 (m, 14H, aromatic protons; C=NH),
10.2 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.3 (S, 2H, CH sat), 7.1-8.4 (m, 10H, aromatic protons; C=NH),
9.8 (S, 1H, NOH), 11.3 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.3 (S, 2H, CH sat), 7.1-8.4 (m, 9H, aromatic protons; C=NH), 9.8
(S, 2H, OH), 11.3 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.3 (S, 2H, CH sat), 7.1-8.4 (m, 9H, aromatic protons; C=NH), 9.8
(S, 1H, NOH), 11.3 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.3 (S, 2H, CH sat), 3.3 (S, 3H, OCH3), 7.1-8.4 (m, 9H, aromatic
protons; C=NH), 9.8 (S, 1H, NOH), 11.3 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.3 (S, 2H, CH sat), 7.1-8.4 (m, 9H, aromatic protons; C=NH), 9.8
(S, 1H, NOH), 11.3 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1(S, 2H, CH sat), 7-8.6 (m, 10H, aromatic protons; 1H, NH;
C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; 1H, NH;
C=NH), 10 (S, 2H, OH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; C=NH), 10 (S,
1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.4 (S, 3H, OCH3), 7-8.6 (m, 9H, aromatic
protons; 1H, NH; C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
1.1 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; 1H, NH;
C=NH), 10 (S, 1H, NOH), 11.7 (S, 1H, NH)
3428 (OH), 3250 (NH), 1684 (C=O),
1528, 1590 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1588, 1651 (C=N)
1.2 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 10H, aromatic protons; 1H, NH;
C=NH), 9.8 (S, 1H, NOH), 11.5 (S, 1H, NH)

124 J. Chin. Chem. Soc., Vol. 52, No. 1, 2005
Soleiman et al.
7b
7c
3447 (OH), 3250 (NH), 1684 (C=O),
1588, 1651 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1588, 1651 (C=N)
1.2 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; 1H, NH;
C=NH), 9.8 (S, 2H, OH), 11.5 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; 1H, NH;
C=NH), 9.8 (S, 1H, NOH), 11.5 (S, 1H, NH)
7d
7e
3447 (OH), 3250 (NH), 1684 (C=O),
1588, 1651 (C=N)
3447 (OH), 3250 (NH), 1684 (C=O),
1588, 1651 (C=N)
1.2 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 3.3 (S, 3H, COCH3), 7-8.6 (m, 9H, aromatic
protons; 1H, NH; C=NH), 9.8 (S, 1H, NOH), 11.5 (S, 1H, NH)
1.2 (S, 2H, CH2), 2.1 (S, 2H, CH sat), 7-8.6 (m, 9H, aromatic protons; 1H, NH;
C=NH), 9.8 (S, 1H, NOH), 11.5 (S, 1H, NH)
8a
3652 (OH), 3183 (NH), 1694 (C=O),
1584, 1652 (C=N)
2.7 (S, 1H, CH sat), 4.2 (S, 1H, CH=N), 6.6-8.3 (m, 9H, aromatic protons; C=NH), 9,
8.9 (S, 2H, OH), 11 (S, 1H, NH)
8b
8c
3652 (OH), 3183 (NH), 1694 (C=O),
1584, 1652 (C=N)
3652 (OH), 3183 (NH), 1694 (C=O),
1584, 1652 (C=N)
2.7 (S, 1H, CH sat), 4.2 (S, 1H, CH=N), 6.6-8.3 (m, 11H, aromatic protons; C=NH),
9, 8.9 (S, 2H, OH), 11 (S, 1H, NH)
2.7 (S, 1H, CH sat), 4.2 (S, 1H, CH=N), 6.6-8.3 (m, 11H, aromatic protons; C=NH),
9, 8.9 (S, 2H, OH), 11 (S, 1H, NH)
9a
3580 (OH), 3223 (NH), 1682 (C=O),
1560, 1640 (C=N)
2.6 (S, 1H, CH sat), 3.5 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.5-8 (m, 9H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
9b
9c
3580 (OH), 3223 (NH), 1682 (C=O),
1560, 1640 (C=N)
3580 (OH), 3223 (NH), 1682 (C=O),
1560, 1640 (C=N)
2.6 (S, 1H, CH sat), 3.5 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.5-8 (m, 11H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
2.6 (S, 1H, CH sat), 3.5 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.5-8 (m, 11H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
10a
10b
10c
3492 (OH), 3250 (NH), 1675 (C=O),
1543, 1631 (C=N)
3492 (OH), 3250 (NH), 1675 (C=O),
1543, 1631 (C=N)
3492 (OH), 3250 (NH), 1675 (C=O),
1543, 1631 (C=N)
2.4 (S, 1H, CH sat), 3.6 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.7-8 (m, 9H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
2.4 (S, 1H, CH sat), 3.6 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.7-8 (m, 11H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
2.4 (S, 1H, CH sat), 3.6 (S, 2H, CH2), 3.8 (S, 1H, CH=N), 6.7-8 (m, 11H, aromatic
protons; C=NH), 9.5, 9 (S, 2H, OH), 11 (S, 1H, NH)
3. El-Maghraby, M. A.; Khalafallah, A. K.; Hassan, M. E.;
Soleiman, H. A. J. Chin. Chem. Soc. 1988, 35, 278.
4. El-Maghraby, M. A.; Khalafallah, A. K.; Hassan, M. A.;
Soleiman, H. A. J. Chin. Chem. Soc. 1986, LXIII, 910.
5. Solieman, H. A.; Khalafallah, A. K.; Abdelzaher, H. M. J.
Chin. Chem. Soc. 2000, 47, 1267.
ume; ice-water was added, whereby the product was sepa-
rated, filtrated, washed several times with water and crystal-
lized from methanol to give (9a-c) (c.f. Tables 1, 2).
Synthesis of N-b-lactam benzpyrid-4-imino-2-oxime de-
rivatives (10a-c
)
6. Solieman, H. A.; AbdEl-latif, F. M.; Khalil, M. A.; Elazab, I.
H. Phosphorus, Sulfur and Silicon 2002, 177, 1001.
7 Solieman, H. A.; Khalafallah, A. K.; Shindy, H. A. Indian J.
Chem. 2003, 42B, 1159.
8 Taylor, E. C. J. Heterocycl. Chem. 1990, 27, 1.
9. Tominaga, Y.; Kohra, S.; Honkawa, H.; Hosomi, A. J.
Heterocycles 1989, 29, 1409.
A solution was made of (8a-c) (3.22 g - 3.72 g, 0.01 mol)
chloroacetylchloride (1.12 g, 0.01 mol) in ethanol in the
presence of a few drops of triethylamine. The mixture was
refluxed for 8-10 h. The filtrate was evaporated to one - third
of its volume; ice-water was added, whereby the product was
separated, filtrated, washed several times with water, and
crystallized from methanol to give (10a-c) (c.f. Tables 1, 2).
10. Tominaga, Y.; Motokwa, S.; Shiroshita, Y.; Hosomi, A. J.
Heterocycl. Chem. 1987, 24, 1365.
11. Robins, R. K.; Stivastava, P. C.; Revankar, G. R. Lectures in
Heterocyclic Chemistry VI: Novel Nitrogen Heterocycles as
Potential Medicinal Agents; Hetero Corporation: Tampa, FL
1982; p. 93.
Received February 20, 2004.
12. Tominaga, Y.; Koyhra, S.; Okuda, H.; Ushirogouchi, A.;
Matsuda, Y.; Kobayshi, G. Chem. Pharm, Bull. 1984, 32,
122.
REFERENCES
13. Yam, Z. Sligehoru, Japan koka; 1975, 75, 158, 542, Appl.
1994, 74, 65, 99.
14. Soleiman, H. A.; Koraiem, A. I. M.; Mahmoud, N. Y. J.
Chin. Chem. Soc. 2004, 51(3), 553.
15. Mohanty, S. K.; Sridhar, R.; Padmanvan, S. Y. Indian. J.
Chem. 1977, 158, 1146.
1. Khalafallah, A. K.; Hassan, M. E.; Soleiman, H. A. Indian
Chem. Soc. 1992, 69, 318.
2. Khalafallah, A. K.; Selim, M. A.; Abu-Elhamd, R. M.;
El-Magharby, M. A.; Soleiman, H. A.; Raslam, M. A. Indian
J. Chem. 1995, 34B, 1066.