Compliancy of 1,4-naphthoquinone for the synthesis of new heterocyclic quinone compounds containing imino linkage

Article abstract of DOI:10.1080/10426500701242921

Some new -lactam, thiazolidinone derivatives were synthesized by reaction of new Schiff bases with compounds 4 and oxazoles, pyrazoles, pyrimidines, and pyrimidinethion were also synthesized by reaction of an arylidino system with hydroxyl amine hydrochlo

Full text of DOI:10.1080/10426500701242921

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Compliancy of 1,4-
Naphthoquinone for the
Synthesis of New Heterocyclic
Quinone Compounds
Containing Imino Linkage
N. A. A. El Kanzi a , A. K. Khalafallah a , Abu El
Hamd a , H. Mohamed a & Soleiman A. Soleiman a
a Chemistry Department, Faculty of Science, South
Valley University, Aswan, Egypt
Published online: 07 Jun 2007.
To cite this article: N. A. A. El Kanzi , A. K. Khalafallah , Abu El Hamd , H.
Mohamed & Soleiman A. Soleiman (2007) Compliancy of 1,4-Naphthoquinone for
the Synthesis of New Heterocyclic Quinone Compounds Containing Imino Linkage,
Phosphorus, Sulfur, and Silicon and the Related Elements, 182:7, 1483-1496, DOI:
10.1080/10426500701242921
To link to this article: http://dx.doi.org/10.1080/10426500701242921
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Phosphorus, Sulfur, and Silicon, 182:1483–1496, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701242921
Compliancy of 1,4-Naphthoquinone for the Synthesis of
New Heterocyclic Quinone Compounds Containing Imino
Linkage
N. A. A. El Kanzi
A. K. Khalafallah
Abu El Hamd
H. Mohamed
Soleiman A. Soleiman
Chemistry Department, Faculty of Science, South Valley University,
Aswan, Egypt
Some new β-lactam, thiazolidinone derivatives were synthesized by reaction of new
Schiff bases with compounds 4 and oxazoles, pyrazoles, pyrimidines, and pyrim-
idinethion were also synthesized by reaction of an arylidino system with hydroxyl
amine hydrochloride, hydrazines, urea, and thiourea, which we expected to have
biological activities such as bactericidal and fungicidal or other applications of
certain interest.
Keywords Arylidino derivatives; isolated β-lactams; oxazoles; pyrazoles; pyrimidines;
pyrimidinethion; Schiff bases; thiazolidinone derivatives
INTRODUCTION
Three membered rings containing nitrogen, oxygen, and sulphur atoms
as the heteroatom are called aziridine, oxirane, and thiirane, respec-
tively. A duly examination of the literature for fused three membered
heterocycles with other hetero rings indicated that such systems too
reave one class of antibiotics.1 Also β-lactam and related derivatives
exhibit antibacterial activities.2−7 Thiazole derivatives and β-lactam
rings were known and used as potent antibiotics,8 antibiotic activity,9
and inhibitory activity.10 Diverse biological activities, such as bacterici-
dal, pesticidal, fungicidal, insecticidal, anticonvulsant, tuberculostatic,
anti-inflammatory, and antithydroidal have been found to be associ-
ated with thiazolidinone derivatives.11 Thus, our initial strategy in this
Received May 29, 2006; accepted December 11, 2006.
Address correspondence to A. K. Khalafallah, Chemistry Department, Faculty of Sci-
ence, South Valley University, Answan, Egypt. E-mail: magdi5aziz@yahoo.com
1483

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N. A. A. El Kanzi et al.
research project was divested to the synthesis of different structural
formulas corresponding to the isolated β-lactams, thiazolidinone
derivatives, pyrazoles, oxazoles, pyrimidines, and pyrimidinethion.
RESULTS AND DISCUSSION
The known importance of these heterocyclic compounds with respect
to various types of biological effects promysted us to synthesize new
heterocyclic compounds depending upon our previous research in this
field.12−14 Thus, 1, 4-naphthoquinone 1 was reacted with acetamide and
mercaptoacetic acid in ethanol at reflux in the presence of piperidine
to give 2-amido-2-methyl-2-H-naphtho[2, 3-b][1, 4]thiazine-5, 10-dione,
3-carboxylic acid 4. The formation of 4 was assumed to proceed via the
intermediate 2, which cyclizes to 4, (c.f., Scheme 1). The IR spectrum of
4 revealed the presence of absorption bands at 1665, 3421, 3069 cm−1
1
assigned to CO, NH, OH groups, respectively. The H-NMR spectrum
(DMSO-d6) were showed a singlet at δ 1.02 assigned for methyl group,
a singlet at δ 3.43 for a methyl group of the acetyl group, δ 6.01 for
(CH-S), multaiplets at δ 7.10–8.10 for aromatic protons, and a broad
singlet at δ 9.01 for (NH) protons, respectively, with lack of a peak due
to an NH2 group. The mass spectrum of compound 4 showed m/z at
346 (M+, 346). The compound 4 contains methyl groups which ren-
der it susceptible to react with different nitroso compounds such as β-
nitrosoα-naphthol, α-nitrosoβ-naphthol, P-nitrsophenol, and P-nitrso-
N,Ndimethyl-aniline in the presence of piperidine as catalyst to give the
corresponding Schiff base derivatives 7a–d (Scheme 1). The reaction of
7a–d with an equimolar ratio of chloroacetylchloride in a mixture of
DMF and ethanol in the presence of piperidine as a catalyst afforded
β-lactam derivatives 8a–d (Scheme 1). Cycloaddition reaction of thio-
glycolic acid to the previously prepared Schiff base compounds 7a–d in
a mixture of ethanol and DMF in the presence of piperidine as catalyst
afforded thiazolidinone derivatives 9a–d (Scheme 1). The active methyl
group in the new compound 4 condensed with different aromatic alde-
hydes in a mixture of ethanol and DMF under piperidine as a catalyst to
yield the corresponding arylidino 10a–c. The arylidino derivatives 10a–
c, when interacted with hydrazine, hydrate in the presence of acetic acid
in ethanol as solvents under piperidine as catalyst, respectively, gave
the required N-acetylpyrazolo 11a–d, and/or N-phenylpyrazolo deriva-
tives 12a–d, respectively (Scheme 2). The arylidino derivatives 10a–
c when interacted with hydroxylamine hydrochloride in a mixture of
ethanol and DMF as solvent under the effect of sodium hydroxide as cat-
alyst, gave the required isooxazolino derivatives 13a–c.The arylidino

1485

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N. A. A. El Kanzi et al.
SCHEME 2
derivatives 10a–c, when interacted with urea and/or thiourea in a mix-
ture of ethanol and DMF as solvent under the effect of sodium hydroxide
as catalyst, gave the required pyrimidino derivatives 14a–c or, under
the effect of hydrochloric acid as catalyst, gave the required pyrim-
idinethion derivatives 15a–c.
The activity of the carbonyl group in compound 4 renders it available
to react with different aromatic amine such as aniline, P-chloroaniline,
and P-nitroaniline in the presence of a mixture of ethanol and DMF

1487

1488
N. A. A. El Kanzi et al.
as a solvent and piperidine catalyst to give new Schiff base derivatives
16a–c (Scheme 3). The reaction of 16a–c with equimolar ratios of
chloroacetylchloride in mixture of ethanol and DMF in the presence
of piperidine catalyst afforded lactam derivatives 17a–c (Scheme 3).
Cycloaddition reaction of thioglycolic acid to the previously prepared
Schiff bases 16a–c proceeded successfully. Thus thioglycolic acid added
to Schiff bases 16a–c in a mixture of ethanol and DMF in the presence
of piperidine as catalyst and afforded thiazolidinone derivatives 18a–c
(Scheme 3).
EXPERIMENTAL
All melting points were uncorrected. IR spectra were recorded on a pye
Unicam SP 1100 spectrophotometer using KBr disks. 1HNMR spec-
tra were recorded on a Varian EM390 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 a HP
Ms6988 spectrometer. Analytical data were determined with a CE 440
Elemental Analyzer-Automatic Indicator at Cairo University.
Synthesis of 2-Amido-2-methyl-2-H-naphtho[2, 3-b][1,
4]thiazine-5, 10-dione, 3-carboxylic acid 4
A solution of acetamide (0.59 g, 0.01 mol) and mercaptoaceticacid (0.92
g, 0.01 mol) was treated with 1,4-naphthoquinone (1.58 g, 0.01 mol)
in ethanol in the presence of piperidine as catalyst and refluxed for
15 h. The reaction mixture was filtered from unreacted materials. The
filtered was poured into ice water acidified by concentrated hydrochloric
acid. A reddish brown precipitate separated from the filtrate and was
washed several times with water. It was crystallized from ethanol and
dimethyl formamide to give compound 8a–d, mp 290◦C (c.f., Table I).
Synthesis of 2-diazaamido-2-methyl-2-H-naphthol[2, 3-b][1,
4]thiazine-5, 10-dione, 3-carboxylic acid 7a–d
Compound 4 (3.46 g, 0.01 mol) and nitroso compounds (1.73 g, 1.73 g,
1.50 g, 0.01 mol) in an equimolar ratio were dissolved in ethanol and
dimethylformamide, and 0.5 ml of piperidine as catalyst was added.
The mixture was refluxed about 9 h. The reaction mixture was allowed
to cool at room temperature, then filtered, washed several times with
water, dried, collected, and crystallized from ethanol to give 7a–d (c.f.,
Table I).

Heterocyclic Quinone Compounds
1489
TABLE I Characterization of Compounds
Compound
number
Solvent of
crystallization
Melting Yield
Molecular
formula
Molecular
weight
Mass
spectra
point
%
4
7a
7b
7c
7d
8a
8b
8c
8d
9a
9b
9c
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
EtOH/DMF
290
115
120
125
122
260
260
250
270
360
360
320
340
250
220
190
260
230
200
230
235
225
200
210
215
220
225
227
215
220
220
240
242
245
210
215
212
230
235
240
85% C16H14O5N2S
75% C26H19O6N3S
75% C26H19O6N3S
80% C22H17O6N3S
346.06
501.1
501.1
348(M+2)
502(M+1)
502(M+1)
452(M+1)
478
579(M+2)
579(M+2)
530
451.09
478.13
577.07
577.07
530.10
554.10
575.08
575.08
525.06
552.11
434.09
450.09
479.08
490.97
506.96
535.45
524.15
540.15
569.14
449.11
465.1
75%
65% C28H20O7N3SCl
65% 28H20O7N3SCl
C24H22O5N4S
C
67% C24H17O7N3SCl
70% C26H23O6N4SCl
554
575
575
525
70%
73% C28H21O7N3S2
75% 24H19O7N3S2
C
28H21O7N3S2
C
9d
72% C26H24O6N4S2
80% C23H18O5N2S
552
10a
10b
10c
11a
11b
11c
12a
12b
12c
13a
13b
13c
14a
14b
14c
15a
15b
15c
16a
16b
16c
17a
17b
17c
18a
18b
18c
432(M-2)
449(M-1)
479
449(M+3)
508(M+1)
535
82%
78% C23H17O7N3S
85% 25H22O5N4S
85% C25H22O6N4S
82% 25H21O7N5S
C23H18O6N2S
C
C
70% C29H24O4N4S
68% C29H24O5N4S
524
540
569
449
465
494
70%
75% C23H19O5N3S
73% 23H18O6N3S
C
29H23O6N5S
C
70% C23H18O7N4S
78% C24H20O5N4S
494.1
476.11
492.11
521.1
491.1
507.1
537.1
421.1
455.1
466.1
497.1
531.04
542.1
495.1
529.05
540.1
478(M+2)
73%
70% C24H19O7N5S
75% 24H20O4N4S2
C24H20O6N4S
492
521
491
507
537
C
75% C24H20O5N4S2
73% C24H19O6N5S2
76%
C
22H19O4N3S
423(M+2)
74% C22H18O4N3SCl
73% C22H18O6N4S
455
466
497
531
542
495
529
540
72%
70% C24H19O5N3SCl2
70% 24H19O7N4SCl
75% C24H21O5N3S2
72% 24H20O5N3S2Cl
70% C24H19O7N4S2
C
24H20O5N3SCl
C
C
Synthesis of New β-Lactam Derivatives 8a–d
A solution of 7a–d (5.01 g, 0.01 mol) chloroacetylchloride (1.13 g,
0.01mol) in a mixture of ethanol and dimethylformamide in the

1490
N. A. A. El Kanzi et al.
TABLE II Selected HNMR Spectra Data for the New Compounds
Listed in Table I
Compound
number
1H-NMR d6 (DMSO)
4
δ1.77(s,CH3), δ 3.74 (s,COCH3), δ 4.5 (s,NH), δ 7.01–9 (m,7H, Aromatic
protons, CH,NH,OH)
7a
7b
7c
7d
8a
8b
8c
8d
9a
9b
9c
9d
δ1.63(s,CH3), δ 3.54 (s,CH), δ 6.01 (s,NH), δ 7.11–8.07 (m,13H, Aromatic
protons, CH,NH,OH), δ 9.673 (s, Carboxylic OH)
δ1.60(s,CH3), δ 3.50 (s,CH), δ 6.02 (s,NH), δ 7.0–8.2 (m,13H, Aromatic
protons, CH,NH,OH), δ 9.723 (s, Carboxylic OH)
δ1.4(s,CH3), δ 3.7 (s,CH), δ 5.8 (s,NH), δ 7.2–8.3 (m,11H, Aromatic
protons, CH,NH,OH), δ 9.9 (s, Carboxylic OH)
δ1.5(s,CH3), δ 2.34 (s,6H,2CH3), δ 3.56 (s,CH), δ 5.6 (s,NH), δ 7.1–8.0
(m,10H, Aromatic protons, CH,NH,), δ 9.92 (s, Carboxylic OH)
δ1.64(s,CH3), δ 2.92 (s,CH), δ 3.41 (s,CH), δ 5.23 (s,NH), δ 7.05–8.7
(m,13H, Aromatic protons, CH,NH,OH), δ 8.85 (s, Carboxylic OH)
δ1.45(s,CH3), δ 2.83 (s,CH), δ 3.35 (s,CH), δ 5.41 (s,NH), δ 7.1–8.8 (m,13H,
Aromatic protons, CH,NH,OH), δ 8.9 (s, Carboxylic OH)
δ1.53(s,CH3), δ 2.9 (s,CH), δ 3.3 (s,CH), δ 5.52 (s,NH), δ 7–8.3 (m,11H,
Aromatic protons, CH,NH,OH), δ 8.98 (s, Carboxylic OH)
δ1.56(s,CH3), δ 2.3 (s,6H,2CH3), δ 2.98 (s,CH), δ 3.54 (s,CH), δ 5.64 (s,NH),
δ 7–8 (m,10H, Aromatic protons, CH,NH,), δ 9.5 (s, Carboxylic OH)
δ1.62(s,CH3), δ 2.9 (s,CH), δ 3.42 (s,CH2), δ 5.24 (s,NH), δ 7.5–8.19
(m,13H, Aromatic protons, CH,NH,OH), δ 8.21 (s, Carboxylic OH)
δ1.62(s,CH3), δ 2.89 (s,CH), δ 3.42 (s,CH2), δ 5.23 (s,NH), δ 7.5–8.2
(m,13H, Aromatic protons, CH,NH,OH), δ 8.32 (s, Carboxylic OH)
δ1.63(s,CH3), δ 2.9 (s,CH), δ 3.43 (s,CH2), δ 5.23 (s,NH), δ 7.5–8.18
(m,11H, Aromatic protons, CH,NH,OH), δ 8.4 (s, Carboxylic OH)
δ1.66(s,CH3), δ 2.65 (s,6H,2CH3), δ 2.95 (s,CH), δ 3.45 (s,CH2), δ 5.4
(s,NH), δ 7.1–8.3 (m,10H, Aromatic protons, CH,NH,), δ 8.5
(s,Carboxylic OH)
10a
10b
10c
11a
11b
δ1.61(s,CH3), δ 3.41 (s,NH), δ 5.99 (s,CH), δ 6.49 (s,CH), δ 7.37 (s,SCH), δ
7.45–82 (m,10H, Aromatic protons, NH), δ 10.05 (s, OH)
δ1.6(s,CH3), δ 3.8 (s,NH), δ 6.31 (s,CH), δ 6.89 (s,CH), δ 7.35 (s,SCH), δ
7.43–8 (m,10H, Aromatic protons, NH,OH), δ 10.24 (s,Carboxylic OH)
δ1.8(s,CH3), δ 4.2 (s,NH), δ 6.65 (s,CH), δ 6.9 (s,CH), δ 7.3 (s,SCH), δ
7.4–8.01 (m,9H, Aromatic protons, NH), δ 10.47 (s, OH)
δ1.45(s,CH3), δ 1.65 (s,COCH3), δ 1.7 (s,CH2), δ 2.4 (s,CH), δ 3.7(s,NH), δ
7.03-8.54 (m,11H,Aromatic protons, CH,NH), δ 10.12 (s,OH)
δ1.53(s,CH3), δ 1.54 (s,COCH3), δ 1.8 (s,CH2), δ 2.45 (s,CH), δ 3.73 (s,NH),
δ 7.32–8.57 (m,11H, Aromatic protons, CH,NH,OH), δ 10.2
(s,Carboxylic OH)
11c
12a
12b
12c
δ1.6(s,CH3), δ 1.7 (s,COCH3), δ 1.8 (s,CH2), δ 2.5 (s,CH), δ 3.8 (s,NH), δ
7.3–8.6 (m,10H, Aromatic protons, CH,NH), δ 10.3 (s, OH)
δ1.47(s,CH3), δ 1.9 (s,CH2), δ 2.6 (s,CH), δ 4.01(s,NH), δ 7.1–8.7 (m,11H,
Aromatic protons, CH,NH), δ 10.01 (s, OH)
δ1.46(s,CH3), δ 1.95 (s,CH2), δ 2.75 (s,CH), δ 4.3 (s,NH), δ 7.3–8.87
(m,11H, Aromatic protons, CH,NH,OH), δ 10.12 (s, Carboxylic OH)
δ1.48(s,CH3), δ 1.98 (s,CH2), δ 2.8 (s,CH), δ 4.5 (s,NH), δ 7.4–8.89 (m,10H,
Aromatic protons, CH,NH), δ 10.3 (s, OH)

Heterocyclic Quinone Compounds
1491
TABLE II Selected HNMR Spectra Data for the New Compounds
Listed in Table I (Continued)
Compound
number
1H-NMR d6 (DMSO)
13a
δ1.23(s,CH3), δ 1.43(s,CH2), δ 1.8 (s,CH), δ 3.5 (s,NH), δ 7.2–8.5 (m,11H,
Aromatic protons, CH,NH), δ 10.2 (s,OH)
13b
13c
14a
14b
δ1.3(s,CH3), δ 1.45(s,CH2), δ 1.9 (s,CH), δ 3.7 (s,NH), δ 7.5–8.7 (m,11H,
Aromatic protons,NH,OH), δ 10. 24 (s, Carboxylic OH)
δ1.42(s,CH3), δ 1.48 (s,CH2), δ 2.2 (s,CH), δ 3.85 (s,NH), δ 7.7–8.75
(m,10H, Aromatic protons, CH,NH), δ 10.26 (s,OH)
δ1.25(s,CH3), δ 1.6 (s,CH2), δ 2.03 (s,CH), δ 3.6 (s,NH), δ 3.85 (s,NH), δ
7.23–8.47 (m,11H, Aromatic protons,CH,NH), δ 10.4 (s,OH)
δ1.27(s,CH3), δ 1.65 (s,CH2), δ 2.12 (s,CH), δ 3.67 (s,NH), δ 3.89 (s,NH), δ
7.4–8.7 (m,11H, Aromatic protons, CH,NH,OH), δ 10.45 (s,Carboxylic
OH)
14c
15a
15b
δ1.29(s,CH3), δ 1.7 (s,CH2), δ 2.3 (s,CH), δ 3.8 (s,NH), δ 3.9 (s,NH), δ
7.6–8.9 (m,10H, Aromatic protons, CH,NH), δ 10.6 (s,OH)
δ1.05(s,CH3), δ 1.5 (s,CH2), δ 1.9 (s,CH), δ 3.5 (s,NH), δ 3.8 (s,NH), δ
7.4–8.6 (m,11H, Aromatic protons, CH,NH), δ 10.32 (s,OH)
δ1.08(s,CH3), δ 1.56 (s,CH2), δ 1.95 (s,CH), δ 3.84 (s,NH), δ 4.2 (s,NH), δ
7.65–8.85 (m,11H, Aromatic protons, CH,NH,OH), δ 10.45 (s,
Carboxylic OH)
15c
16a
16b
16c
17a
17b
17c
18a
18b
18c
δ1.1(s,CH3), δ 1.63 (s,CH2), δ 1.98 (s,CH), δ 3.95 (s,NH), δ 4.5 (s,NH), δ
7.68–8.88 (m,10H, Aromatic protons,CH,NH), δ 10.5 (s,OH)
δ1.2(s,CH3), δ 1.85 (s,CH3), δ 3.54 (s,NH), δ 7.34–8.23 (m,11H, Aromatic
protons, CH,NH), δ 9.57 (s,OH)
δ1.25(s,CH3), δ 1.9 (s,CH3), δ 3.98 (s,NH), δ 7.6–8.5 (m,10H, Aromatic
protons, CH,NH), δ 9.7 (s,OH)
δ1.4(s,CH3), δ 2.3 (s,CH3), δ 4.24 (s,NH), δ 7.7–8.5 (m,10H, Aromatic
protons, CH,NH), δ 10.15 (s,OH)
δ1.6(s,CH3), δ 1.75 (s,CH3), δ 2.8 (s,CH), δ 3.7 (s,NH), δ 7.43–8.45 (m,11H,
Aromatic protons, CH, NH), δ 9.85 (s,OH)
δ1.7(s,CH3), δ 1.85 (s,CH3), δ 2.9 (s,CH), δ 3.9 (s,NH), δ 7.5–8.6 (m,10H,
Aromatic protons, CH, NH), δ 9.9 (s,OH)
δ1.8(s,CH3), δ 1.9 (s,CH3), δ 2.98 (s,CH), δ 3.98 (s,NH), δ 7.6–8.634
(m,10H, Aromatic protons, CH, NH), δ 9.95 (s,OH)
δ1.68(s,CH3), δ 1.832 (s,CH3), δ 2.04 (s,CH2), δ 4.02 (s,NH), δ 7.45–8.23
(m,11H, Aromatic protons, CH,NH), δ 10.2 (s,OH)
δ1.8(s,CH3), δ 1.867 (s,CH3), δ 2.34 (s,CH2), δ 4.21 (s,NH), δ 7.5–8.3
(m,10H, Aromatic protons, CH,NH), δ 10.25 (s,OH)
δ1.85(s,CH3), δ 1.92 (s,CH3), δ 2.5 (s,CH2), δ 4.3 (s,NH), δ 7.6–8.5 (m,10H,
Aromatic protons, CH,NH), δ 10.28 (s,OH)
presence of a few drops of piperidine was refluxed for 10–12 h. The
filtrate was evaporated under reduced pressure, poured into ice water
where the product was separated, filtered, washed, several times with
water, and crystallized from ethanol and dimethylformamide (c.f.,
Table I).

1492
N. A. A. El Kanzi et al.
TABLE III Selected IR Spectra, Elemental Analysis for the New
Compounds Listed in Table I
Calculated % Found %
Comp.
–1
no.
IR υmaxCm
C
H
N
S
Cl
4
1591 (2CO), 1665 (NHCO), 1727
(COOH), 3069–3450 (NH,OH)
1589 (2CO), 1628 (NHCO), 1665
(COOH), 3061–3400 (NH,OH)
1590 (2CO), 1630 (NHCO), 1667
(COOH), 3063–3403 (NH,OH)
1593 (2CO), 1632 (NHCO), 1670
(COOH), 3063–3405 (NH,OH)
1559 (2CO), 1638 (NHCO), 1673
(COOH), 3065–3410 (NH,OH)
1590 (2CO), 1631 (NHCO), 1667
55.65 4.28 8.89 9.85
55.45 4.15 8.65 9.50
62.54 3.82 8.39 6.40
62.17 3.25 8.11 6.23
62.32 3.82 8.39 6.40
62.10 3.34 8.15 6.25
58.58 3.80 9.32 7.12
58.18 3.26 9.10 6.85
60.29 4.64 11.72 6.71
59.99 4.28 11.22 6.11
—
—
—
—
—
—
—
—
—
—
7a
7b
7c
7d
8a
58.28 3.49 7.28 5.56 6.14
(COOH), 2921 (CHCl), 3066–3450 (NH,OH) 57.98 3.15 7.05 5.35 5.74
1591 (2CO), 1632 (NHCO), 1668 58.28 3.49 7.28 5.56 6.14
(COOH), 2922 (CHCl), 3066–3450 (NH,OH) 58.08 3.15 7.15 5.40 5.74
1592 (2CO), 1632 (NHCO), 1670 54.38 3.23 7.93 6.05 6.69
(COOH), 2923 (CHCl), 3067–3452 (NH,OH) 54.17 2.85 7.55 5.95 6.50
1594 (2CO), 1634 (NHCO), 1670 56.36 4.18 10.11 5.79 6.40
(COOH), 2925 (CHCl), 3070–3455 (NH,OH) 55.97 3.99 9.98 5.56 5.99
8b
8c
8d
9a
1590 (2CO),1630 (NHCO), 1667
(COOH), 3063–3445(NH,OH)
1590 (2CO),1631 (NHCO), 1668
(COOH), 3063–3445(NH,OH)
1591 (2CO),1632 (NHCO), 1669
(COOH), 3064–3447(NH,OH)
1592 (2CO),1632 (NHCO), 1670
(COOH), 3065–3450(NH,OH)
1588 (2CO),1662 (NHCO), 1723
(COOH), 3064–3440 (NH,OH)
1588 (2CO),1661 (NHCO), 1723
(COOH), 3060–3440 (NH,OH)
1589 (2CO),1663 (NHCO), 1725
(COOH), 3066–3442 (NH,OH)
1590 (2CO), 1685 (COCH3), 1730
(COOH), 3060–3430 (NH,OH)
1591 (2CO), 1686 (COCH3), 1731
(COOH), 3063–3432 (NH,OH)
1592 (2CO), 1688 (COCH3), 1733
(COOH), 3063–3435 (NH,OH)
1589 (2CO), 1727 (COOH), 3055–
3460 (NH,OH)
58.48 3.68 7.31 11.15
57.99 3.38 6.92 10.75
58.48 3.68 7.31 11.15
57.99 3.38 6.92 10.75
54.90 3.65 8.00 12.21
54.69 3.45 7.74 11.15
56.56 4.38 10.15 11.61
56.24 3.99 9.85 11.41
63.64 4.18 6.45 7.39
63.38 3.98 6.36 7.16
61.38 4.03 6.22 7.12
61.08 3.94 5.85 6.86
59.66 3.58 8.77 6.69
59.45 3.26 8.52 6.39
61.16 4.52 11.41 6.53
59.96 4.22 11.09 6.25
59.23 4.37 11.05 6.32
58.94 4.07 10.85 5.96
56.08 3.95 13.08 5.99
55.88 3.73 12.76 5.79
66.45 4.61 10.69 6.12
66.15 4.51 10.44 5.85
64.49 4.48 10.37 5.94
64.21 4.13 10.03 5.65
61.20 4.08 12.31 5.63
60.96 3.78 12.11 5.33
61.15 4.26 9.36 7.14
60.83 3.95 9.05 6.84
—
—
—
—
—
9b
9c
9d
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
—
10a
10b
10c
11a
11b
11c
12a
12b
12c
13a
1589 (2CO), 1728 (COOH), 3050–
3460 (NH,OH)
1590 (2CO), 1729 (COOH), 3056–
3465 (NH,OH)
1588 (2CO), 1721 (COOH), 3060–
3465 (NH,OH)

Heterocyclic Quinone Compounds
1493
TABLE III Selected IR Spectra, Elemental Analysis for New
Compounds Listed in Table I (Continued)
Calculated % Found %
Comp.
–1
no.
IR υmaxCm
C
H
N
S
Cl
13b
1589 (2CO), 1723 (COOH), 3063–
3465 (NH,OH)
1589 (2CO), 1725 (COOH), 3060–
3460 (NH,OH)
59.40 3.67 11.34
59.26 3.35 11.14
55.91 3.67 11.34
55.75 3.36 10.99
60.55 4.23 11.77
60.32 3.84 11.52
58.58 4.10 11.39
58.24 3.78 11.16
55.32 3.67 13.44
54.98 3.35 13.24
58.70 4.10 11.41 13.06
58.46 3.83 11.24 12.96
56.85 3.98 11.05 12.64
56.65 3.58 10.85 12.34
53.67 3.57 13.04 11.94
53.47 3.27 12.82 11.76
6.89
6.66
6.49
6.25
6.73
6.44
6.51
6.25
6.15
5.75
—
—
—
—
—
—
—
13c
14a
14b
14c
15a
15b
15c
16a
16b
16c
17a
17b
17c
18a
18b
18c
1592 (2CO),1667 (NHCO), 1732
(COOH), 3065–3435 (NH,OH)
1591 (2CO),1666 (NHCO), 1731
(COOH), 3064–3435 (NH,OH)
1593 (2CO),1668 (NHCO), 1733
(COOH), 3067–3437 (NH,OH)
1589 (2CO),1245 (CS), 1729
(COOH), 3061–3451 (NH,OH)
1589 (2CO),1244 (CS), 1730
(COOH), 3062–3453 (NH,OH)
1590 (2CO),1242 (CS), 1731
(COOH), 3063–3454 (NH,OH)
1589 (2CO),1443(CN), 1667
(COOH), 3063–3405 (NH,OH)
1588 (2CO),1445(CN), 1669
(COOH), 3063–3410 (NH,OH)
1592 (2CO),1446(CN), 1670
(COOH), 3065–3415 (NH,OH)
1591 (2CO), 1668 (COOH), 1720
(CO), 2923 (CHCl), 3066–3450 (NH,OH) 57.76 3.79
1593 (2CO), 1670 (COOH), 1722 54.28 3.61
(CO), 2925 (CHCl), 3068–3455 (NH,OH) 53.97 3.35
1594 (2CO), 1671 (COOH), 1725
(CO), 2925 (CHCl), 3068–3460 (NH,OH) 52.88 3.35 10.15
1589 (2CO), 1676 (COOH,CO),
3060–3443 (NH,OH)
1592 (2CO), 1678 (COOH,CO),
3065–3445 (NH,OH)
—
—
—
—
—
—
—
—
—
—
62.75 4.55
62.32 4.36
58.06 3.99
57.87 3.74
9.98
9.65
9.23
8.99
7.61
7.36
7.04 7.79
6.82 7.24
6.88
6.45
6.44 7.14
6.25 6.95
6.04 13.35
5.85 13.15
5.91 6.54
5.71 6.24
56.69 3.89 12.56
56.48 3.63 11.89
—
—
57.99 4.06
8.45
8.16
7.91
7.63
53.18 3.53 10.34
58.22 4.28
57.88 3.96
54.49 3.81
54.17 3.61
8.49 12.95
8.29 12.66
7.94 12.12 6.70
7.65 11.82 6.36
—
—
1594 (2CO), 1679 (COOH,CO),
3066–3446 (NH,OH)
53.37 3.55 10.37 11.87
53.16 3.25 10.16 11.58
—
—
Synthesis of New Thiazolidinone Derivatives 9a–d
A solution of 7a–d (5.01 g, 0.01 mol) and thioglycolic acid (0.92 g, 0.01
mol) in a mixture of ethanol and dimethylformamide in the presence
of a few drops of piperidine was refluxed for 8–10 h. The filtrate was
evaporated under reduced pressure, poured into ice water where the
product was separated, filtered, washed several times with water, and
crystallized from the proper solvent to give 9a–d (c.f., Table I).

1494
N. A. A. El Kanzi et al.
Synthesis of 2-Arylidenoamino-2-methyl, 2-H-naphtho[2,
3-b][1, 4]thiazine-5, 10-dione, 3-carboxylic Acid Derivatives
10a–c
A solution of 4 (3.46 g, 0.01 mol) and aromatic aldehydes (1.06 g, 1.22 g,
1.51 g, 0.01 mol) in a mixture of ethanol and dimethylformamide in
the presence of two drops of piperidine as catalyst was refluxed for 7–8
h. The mixture was concentrated and then left to cool and pour onto
ice water acidified by concentrated hydrochloric acid. The solid product
so formed was collected by filtration and crystallized from the proper
solvent to give 10a–c (c.f., Table I).
Synthesis of Acetyl Pyrazolino Derivatives 11a–c
To a solution of arylidino 10a–c (4.34 g, 4.50 g, 4.79 g, 0.01 mol) in a
mixture of ethanol and dimethylformamide as solvent, hydrazine hy-
drate (0.5 g, 0.01) was added followed by glacial acetic acid (10 ml). The
reaction mixture was refluxed for 10–12 h. The reaction mixture was
concentrated and filtered. These substances were triturated with wa-
ter and the precipitates were separated, filtered, washed several times
with water, dried, collected, and crystallized from the proper solvent to
give 11a–c (c.f., Table I).
Synthesis of 3-aryl-4-phenylpyrazolino Derivatives 12a–c
To a solution of arylidino 10a–c (4.34 g, 4.50 g, 4.79 g, 0.01 mol) in a
mixture of ethanol and dimethylformamide as solvent, added phenyl
hydrazine (1.08 g, 0.01 mol) in the presence of 0.5 ml of piperidine
as catalyst. The reaction mixture was refluxed for 9–11 h. The reac-
tion mixture was concentrated, cooled, poured onto water acidified by
concentrated hydrochloric acid. The solid substances were collected by
filtration, washed with water for several times, and crystallized from
the proper solvent to give 12a–c (c.f., Table I).
Synthesis of 3-arylisoxazolo Derivatives 13a–c
A solution of arylidino 10a–c (4.34 g, 4.50 g, 4.79 g, 0.01 mol) was re-
fluxed with hydroxylamine hydrochloride (0.69 g, 0.01 mol) in the pres-
ence of sodium hydroxide as catalyst and a mixture of ethanol and
dimethylformamide as solvent for 6–8 h. The reaction mixture was fil-
tered hot, the filtrate was concentrated and poured onto ice water, where
the products were separated, filtered, washed several times with water,
and crystallized from the proper solvent to give 13a–c (c.f., Table I).

Heterocyclic Quinone Compounds
1495
Synthesis of 3-arylpyrimidino Derivatives 14a–c
A solution of arylidino 10a–c (4.34 g, 4.50 g, 4.79 g, 0.01 mol) was re-
fluxed with urea (0.6 g, 0.01 mol) in the presence of sodium hydroxide
as catalyst and a mixture of ethanol and dimethylformamide as solvent
for 8–10 h. The reaction mixture was filtered from unreacted materi-
als, and the filtrate was concentrated and poured on to ice water, and
the products were separated, filtered, washed several times with water,
and crystallized from the proper solvent to give 14a–c (c.f., Table I).
Synthesis of 3-arylthiopyrimidino Derivatives 15a–c
A solution of arylidino 10a–c (4.34 g, 4.50 g, 4.79 g, 0.01 mol) was re-
fluxed with thiourea (0.67 g, 0.01 mol) in the presence of hydrochloric
acid as catalyst and a mixture of ethanol and dimethylformamide as
solvent for 8–10 h. The reaction mixture was filtered hot, cooled, the
filtrate was concentrated, poured onto ice/water, and the products were
separated, filtered, washed several times with water, and crystallized
from the proper solvent to give 15a–c (c.f., Table I).
Synthesis of New Schiff Base Derivatives 16a–c
Compound 4 (3.46 g, 0.01 mol) and aromatic amine ( 0.93 g, 1.27 g,
1.38 g, 0.01 mol) in an equimolar ratio were dissolved in ethanol and
dimethylformamide and 0.5 ml of piperidine as catalyst was added. The
mixture was refluxed about 10 h. The reaction mixture was allowed
to cool at room temperature, then filtered, washed several times with
water, dried, collected, and crystallized from the proper solvent to give
16a–c (c.f., Table I).
Synthesis of New β-Lactam Derivatives 17a–c
A solution of (4.21 g, 4.55 g, 4.66 g, 0.01 mol) of chloroacetylchloride (1.13
g, 0.01 mol) in a mixture of ethanol and dimethylformamide in the pres-
ence of a few drops of piperidine was refluxed for 12–14 h. The filtrate
was evaporated under reduced pressure, poured into ice/water where
the product was separated, filtered, washed several times with water
and crystallized from the proper solvent to give 17a–c (c.f., Table I).
Synthesis of New Thiazolidinone Derivatives 18a–c
A solution of 16a–c (4.21 g, 4.55 g, 4.66 g, 0.01 mol) and thioglycolic
acid (0.92 g, 0.01 mol) in a mixture of ethanol and dimethylformamide

1496
N. A. A. El Kanzi et al.
in the presence of a few drops of piperidine was refluxed for 11–13 h. The
filtrate was evaporated under reduced pressure, poured into ice/water
where the product was separated, filtered, washed several times with
water, and crystallized from the proper solvent to give 18a–c (c.f.
Table I).
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