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

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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

^aChemistry 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

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.¹Also β-lactam and related derivatives

exhibit antibacterial activities.²⁻⁷Thiazole derivatives and β-lactam

rings were known and used as potent antibiotics,⁸antibiotic activity,⁹

and inhibitory activity.¹⁰Diverse 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.¹¹Thus, 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.¹²⁻¹⁴Thus, 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 NH₂group. 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

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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

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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

290

115

120

125

122

260

250

270

360

320

340

250

220

190

260

230

200

230

235

225

200

210

215

220

225

227

215

220

240

242

245

210

215

212

230

235

240

85% C₁₆H₁₄O₅N₂S

75% C₂₆H₁₉O₆N₃S

80% C₂₂H₁₇O₆N₃S

346.06

501.1

348(M+2)

502(M+1)

452(M+1)

478

579(M+2)

530

451.09

478.13

577.07

530.10

554.10

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

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

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

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 υ_maxCm

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 υ_maxCm

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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Article Doi

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

DOI: 10.1080/10426500701242921

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Full text of DOI:10.1080/10426500701242921

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