Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 3, pp. 383–393. © Pleiades Publishing, Ltd., 2009.

Original Russian Text © A.P. Avdeenko, S.A. Konovalova, D.A. Roman’kov, O.N. Ludchenko, I.L. Marchenko, 2009, published in Zhurnal Organicheskoi

Khimii, 2009, Vol. 45, No. 3, pp. 395–405.

Reaction of N-Substituted 2,5-Dialkyl-1,4-benzoquinone Imines

with Arenesulfinic Acids

A. P. Avdeenko, S. A. Konovalova, D. A. Roman’kov, O. N. Ludchenko, and I. L. Marchenko

Donbass State Machine-Building Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine

e-mail: chimist@dgma.donetsk.ua

Received February 14, 2008

Abstract—Reactions of N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-2,5-dialkyl-1,4-benzo-

quinone imines with sodium arenesulfinates in acetic acid gave the corresponding 1,4-, 6,1-, and 1,6-addition

products. Variation of the size and donor power of substituents in positions 2 and 5 of the quinoid ring almost

does not affect the ratio of the addition products, which is determined mainly by the nature of substituent on the

nitrogen atom.

DOI: 10.1134/S1070428009030063

The present work continues our studies on reactions

of various N-substituted 1,4-benzoquinone imines with

arenesulfinic acids. We previously [1] examined reac-

tions of symmetrical alkyl-substituted 1,4-benzoqui-

none imines with sodium arenesulfinates in acetic acid

and found that the substituent on the nitrogen atom in

initial quinone imines strongly affects their reactivity.

In the reactions with N-arylsulfonyl derivatives, the

addition pattern is determined by steric factor, i.e., by

the size of substituents in the quinoid ring. The addi-

tion of sodium arenesulfinates to N-aroyl-1,4-benzo-

quinone imines, in which the substituent on the nitro-

gen atom is the strongest electron acceptor, is governed

by the nature and position of substituents in the quin-

oid ring. N-(N-Arylsulfonylbenzimidoyl)-1,4-benzo-

quinone imines were found to occupy an intermediate

place between N-aroyl and N-arylsulfonyl derivatives.

ing filtrates and mother liquors were also examined.

We thus succeeded in identifying products whose

fraction in the reaction mixture did not exceed a few

percent. The results are summarized in table. It was

found that reactions of quinone imines I–IX with

sodium arenesulfinates X gave the corresponding 1,4-,

6,1-, and 1,6-addition products. No 6,3-adduct analo-

gous to those obtained from 2,6-dimethyl-1,4-benzo-

quinone imines [1] were detected.

The product structure was determined by analysis

1

of their H NMR spectra with account taken of our

previous data [1]. As reference structures for N-aryl-

sulfonyl derivatives we used compounds XI–XIII

having only one proton in the aminophenol ring and

sulfonimides XXIX–XXXI with two equivalent sub-

stituents on the nitrogen atom. In most cases, 1,4-addi-

tion products were isolated as individual substances.

Compounds XIVb, XVc, and XVIb were oxidized to

the corresponding quinone imines XXXIV–XXXVI

with lead tetraacetate in acetic acid (Scheme 2), for

¹H NMR spectra of quinone imines are more inform-

ative than the spectra of aminophenols.

The goal of the present work was to compare the

reactivities of analogous 2,5-substituted N-aroyl-,

N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-

1,4-benzoquinone imines I–IX toward sodium arene-

sulfinates Xa–Xc. The substrates and reagents were

selected in such a way that the substituents in the para

position of their aryl fragments (mainly methyl and

methoxy groups) ensured unambiguous signal assign-

1

In the H NMR spectrum of quinone imine

XXXIV, signal from the only proton in the quinoid

ring resonated as a quartet at δ 6.67 ppm, one methyl

group gave a doublet at δ 1.88 ppm, and protons in

the other methyl group appeared as a singlet at

1

ment in the H NMR spectra of the products. The

reactions were carried out in acetic acid using 2 equiv

of sodium arenesulfinate X (Scheme 1). The product

mixtures were analyzed by ¹H NMR spectroscopy both

before and after recrystallization, and the correspond-

1

δ 2.92 ppm. The H NMR spectrum of quinone imine

XXXV contained a broadened singlet at δ 6.61 ppm

from the proton in the quinoid ring, a multiplet at

383

AVDEENKO et al.

384

Scheme 1.

R²

O

H

N

S

X

1,4

OH

R⁴

R¹

R³

XIa–XIc, XIIa–XIIc, XIIIa–XIIIc

XIVa–XIVd, XVa–XVd, XVIa–XVId

XVIIa–XVIIc, XVIIIa–XVIIIc, XIXa–XIXc

R²

H

N

X

N

O

X

O

R²

SO₂Na

S

R³

AcOH

1,6

O

+

R¹

R⁴

R³

XXa–XXc, XXIa–XXIc, XXIIa–XXIIc

Ia, Ib, IIa, IIb, IIIa, IIIb

IVa–IVd, Va–Vd, VIa–VId

Xa–Xc

XXIIIa–XXIIId, XXIVa–XXIVd, XXVa–XXVd

VIIa, VIIb, VIIIa, VIIIb, IXa, IXb

XXVIa–XXVIc, XXVIIa–XXVIIc, XXVIIIa–XXVIIIc

R⁴

R³

X

N

SO₂

R²

6,1

R¹

HO

XXIXa–XXIXc, XXXa–XXXc

XXXIa–XXXIc, XXXIIa, XXXIIb

XXXIId, XXXIIIa, XXXIIIb, XXXIIId

I–III, XI–XIII, XX–XXII, XXIX–XXXI, X = SO₂; IV–VI, XIV–XVI, XXIII–XXV, XXXII, XXXIII, X = CO; VII–IX, XVII–

XIX, XXVI–XXVIII, X = C(=NSO₂Ar); I, IV, VII, XI, XIV, XVII, XX, XXIII, XXVI, XXIX, XXXII, R¹= R²= Me; II, V, VIII,

XII, XV, XVIII, XXI, XXIV, XXVII, XXX, XXXIII, R¹= i-Pr, R²= Me; III, VI, IX, XIII, XVI, XIX, XXII, XXV, XXVIII,

XXXI, R¹= Me, R²= i-Pr; I–III, R³= Me (a), MeO (b); IV–VI, R³= H (a), Cl (b), MeO (c), Me (d); VII–IX, R³= H (a, b), Ar =

4-MeC₆H₄(a), 4-MeOC₆H₄(b); X, R⁴= Me (a), MeO (b), Cl (c); XI–XIII, XX–XXII, XXIX–XXXI, R³= Me (a), MeO (b, c), R⁴=

MeO (a, c), Cl (b); XIV–XVI, XXIII–XXV, XXXII, XXXIII, R³= H (a), Cl (b), MeO (c), Me (d), R⁴= Me (a), MeO (b, d), Cl (c);

XVII–XIX, XXVI–XXVIII, R³= H (a, b, c), Ar = 4-MeC₆H₄(a), 4-MeOC₆H₄(b, c), R⁴= MeO (a, b), Me (c).

Scheme 2.

R¹

O

S

R⁴

O

[O]

XIVb, XVc, XVIb

N

O

R²

R³

XXXIV–XXXVI

XXXIV, R¹= R²= Me, R³= Cl, R⁴= MeO; XXXV, R¹= i-Pr, R²= Me, R³= MeO, R⁴= Cl;

XXXVI, R¹= Me, R²= i-Pr, R³= Cl, R⁴= OMe.

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

REACTION OF N-SUBSTITUTED 2,5-DIALKYL-1,4-BENZOQUINONE IMINES

385

Product composition in the reactions of 2,5-dialkyl-1,4-benzoquinone imines I–IX with sodium arenesulfinates Xa–Xc

(Scheme 1)

Fraction of addition products, %

X

R¹

R²

R³

R⁴

1,4

6,1

1,6

SO₂

CO

Me

i-Pr

Me

i-Pr

Me

MeO

H

MeO

Cl

93

95

90

79

64

94

76

80

78

79

90

91

93

82

67

89

79

69

71

73

75

80

79

70

54

87

79

74

73

72

3

2

04

03

07

16

29

06

20

22

21

08

06

05

12

23

11

15

31

29

27

16

14

30

46

13

21

26

27

28

MeO

Me

3

5

Cl

MeO

Cl

7

MeO

Me

H

–

MeO

Me

4

C(=NSO₂C₆H₄Me-4)

–

C(=NSO₂C₆H₄OMe-4)

H

–

C(=NSO₂C₆H₄OMe-4)

H

–

SO₂

Me

MeO

H

MeO

Cl

2

SO₂

3

SO₂

MeO

Me

2

CO

6

CO

Cl

MeO

Cl

100

–

CO

MeO

Me

H

CO

MeO

Me

6

C(=NSO₂C₆H₄Me-4)

–

C(=NSO₂C₆H₄OMe-4)

H

–

C(=NSO₂C₆H₄OMe-4)

H

–

SO₂

Me

MeO

H

MeO

Cl

9

SO₂

6

SO₂

MeO

Me

7

CO

–

CO

Cl

MeO

Cl

–

CO

MeO

Me

H

–

CO

MeO

Me

–

C(=NSO₂C₆H₄Me-4)

C(=NSO₂C₆H₄OMe-4)

–

H

–

H

–

δ 2.81–2.91 ppm from the isopropyl CH group, and

a singlet at δ 2.93 ppm from the methyl group. Qui-

none imine XXXVI displayed in the H NMR spec-

more reactive toward arenesulfinate ions. In the reac-

tions with N-(N-arylsulfonylbenzimidoyl) benzoqui-

none imines VII–IX, the main factor determining their

reactivity is steric hindrances created by the substituent

on the nitrogen atom [bulky ArSO₂N=C(Ph) group], so

that no addition products at the nitrogen atom were

isolated. In all cases, the size and electron-donor prop-

erties of the alkyl groups in positions 2 and 5 of the

quinoid ring do not affect the product ratio to an appre-

ciable extent, and the main factor is the nature and size

of the substituent on the nitrogen atom.

1

trum a quartet at δ 6.54 ppm from 6-H, and a doublet

at δ 1.85 ppm from the methyl protons. These findings

unambiguously indicate that the arylsulfonyl group in

XXXIV–XXXVI occupies ortho position with respect

to the carbonyl carbon atom in the quinoid ring.

Analysis of the results given in table shows that the

second ortho position in the quinoid ring of N-arylsul-

fonyl-2,5-dialkyl-1,4-benzoquinone imines I–III is

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

AVDEENKO et al.

mp 81–83°C. Found, %: N 4.70, 4.86. C₁₈H₁₉NO₃.

386

EXPERIMENTAL

Calculated, %: N 4.71.

1

The H NMR spectra were measured on a Varian

VXR-300 spectrometer at 300 MHz from solutions in

acetone-d₆(XI–XIII, XX–XXII, XXIX–XXXI),

DMSO-d₆(XIV–XIX, XXIII–XXVIII, XXXII,

XXXIII), and CDCl₃(XXXIV–XXXVI); the chemical

shifts were measured relative to TMS. Analytical thin-

layer chromatography was performed on Silufol UV-

254 plates; samples were applied from solutions in

chloroform, benzene–hexane (10 : 1) was used as

eluent, and spots were visualized under UV light.

4-Chloro-N-(2-isopropyl-5-methyl-4-oxocyclo-

hexa-2,5-dien-1-ylidene)benzamide (VIb). Yield

61%, mp 96–98°C. Found, %: N 4.53, 4.78.

C₁₇H₁₆ClNO₂. Calculated, %: N 4.64.

N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-4-methoxybenzamide (VIc). Yield

54%, mp 81–82°C. Found, %: N 4.42, 4.61.

C₁₈H₁₉NO₃. Calculated, %: N 4.71.

N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-

dene)-N′-(4-methylphenylsulfonyl)benzimidamide

(VIIa). Yield 90%, mp 131.5–132°C. Found, %:

N 7.07, 7.35; S 8.11, 8.34. C₂₂H₂₀N₂O₃S. Calculated,

%: N 7.14; S 8.17.

Initial quinone imines I–III were synthesized ac-

cording to the procedure reported in [2] by oxidation

of the corresponding aminophenols with sodium di-

chromate in acetic acid. Quinone imines IV–IX and

XXXIV–XXXVI were obtained as described in [3] by

oxidation of the corresponding aminophenols with lead

tetraacetate in acetic acid. The properties of com-

pounds Ia–IIIa [4], IVa, IVd, Va, Vd, VIa, and VId

[5] were consistent with published data. Sodium arene-

sulfinates Xa–Xc were prepared as reported in [6].

N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-

dene)-N′-(4-methoxyphenylsulfonyl)benzimidamide

(VIIb). Yield 93%, mp 106–108°C. Found, %: N 6.66,

6.93; S 7.91 7.98. C₂₂H₂₀N₂O₄S. Calculated, %:

N 6.86; S 7.85.

N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-N′-(4-methylphenylsulfonyl)benz-

imidamide (VIIIa). Yield 93%, mp 102–104°C.

Found, %: N 6.62, 6.75; S 7.54, 7.76. C₂₄H₂₄N₂O₃S.

Calculated, %: N 6.66; S 7.62.

N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-

dene)-4-methoxybenzenesulfonamide (Ib). Yield

72%, mp 111–112°C. Found, %: N 4.47, 4.83; S 10.23,

10.47. C₁₅H₁₅NO₄S. Calculated, %: N 4.59; S 10.50.

N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-4-methoxybenzenesulfonamide (IIb).

Yield 81%, mp 85–86°C. Found, %: N 4.09, 4.32;

S 9.42, 9.45. C₁₇H₁₉NO₄S. Calculated, %: N 4.20;

S 9.62.

N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-N′-(4-methoxyphenylsulfonyl)benz-

imidamide (VIIIb). Yield 88%, mp 74–76°C. Found,

%: N 6.45, 6.61; S 7.37, 7.44. C₂₄H₂₄N₂O₄S. Calculat-

ed, %: N 6.42; S 7.35.

N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-4-methoxybenzenesulfonamide (IIIb).

Yield 79%, mp 96–98°C. Found, %: N 4.02, 4.19;

S 9.63, 9.71. C₁₇H₁₉NO₄S. Calculated, %: N 4.20;

S 9.62.

N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-N′-(4-methylphenylsulfonyl)benz-

imidamide (IXa). Yield 74%, mp 78–80°C. Found, %:

N 6.63, 6.84; S 7.55, 7.69. C₂₄H₂₄N₂O₃S. Calculated,

%: N 6.66; S 7.62.

4-Chloro-N-(2,5-dimethyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)benzamide (IVb). Yield 69 %, mp 127–

129°C. Found, %: N 5.00, 5.24. C₁₅H₁₂ClNO₂. Cal-

culated, %: N 5.12.

N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-N′-(4-methoxyphenylsulfonyl)benz-

imidamide (IXb). Yield 87%, mp 86–88°C. Found, %:

N 6.45, 6.69; S 7.46, 7.83. C₂₄H₂₄N₂O₄S. Calculated,

%: N 6.42; S 7.35.

N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-

dene)-4-methoxybenzamide (IVc). Yield 41%,

mp 106–107°C. Found, %: N 5.23, 5.44. C₁₆H₁₅NO₃.

Calculated, %: N 5.20.

Reaction of quinone imines I–IX with sodium

arenesulfinates Xa–Xc (general procedure). A solu-

tion of 2 mmol of quinone imine I–IX in 20 ml of

glacial acetic acid was heated to the boiling point,

4 mmol of sodium arenesulfinate Xa–Xc was added,

and the mixture was heated until it became colorless,

cooled, and diluted with water until complete precip-

itation. The colorless precipitate was filtered off and

4-Chloro-N-(5-isopropyl-2-methyl-4-oxocyclo-

hexa-2,5-dien-1-ylidene)benzamide (Vb). Yield 23%,

mp 71–73°C. Found, %: N 4.47, 4.58. C₁₇H₁₆ClNO₂.

Calculated, %: N 4.64.

N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-

en-1-ylidene)-4-methoxybenzamide (Vc). Yield 51%,

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

REACTION OF N-SUBSTITUTED 2,5-DIALKYL-1,4-BENZOQUINONE IMINES

387

washed first with cold and then with warm water.

A part of the product was recrystallized from acetic

acid, the mother liquor was diluted with water, and the

precipitate was filtered off. All three samples were

analyzed by ¹H NMR spectroscopy.

(6H, Me₂CH, J = 6.9 Hz), 2.01 s (3H, 2-CH₃), 3.10–

3.23 m (1H, 5-CH), 3.80 s and 3.87 s (3H each, MeO),

6.76 s (1H, 6-H), 7.04–7.43 d.d (4H, C₆H₄, J =

8.4 Hz), 7.17–7.75 d.d (4H, C₆H₄, J = 8.7 Hz), 9.26 s

(1H, OH), 10.61 s (1H, NH).

N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-

2,5-dimethylphenyl]-4-methylbenzenesulfonamide

(XIa). Yield 69%, mp 149–151°C. ¹H NMR spectrum,

δ, ppm: 1.76 s (3H, 5-CH₃), 2.19 s (3H, 2-CH₃), 2.34 s

(3H, CH₃C₆H₄), 3.97 s (3H, MeO), 7.18 s (1H, 6-H),

7.17–7.78 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.20–

7.36 d.d (4H, CH₃C₆H₄, J = 8.7 Hz), 8.31 s (1H, OH),

10.92 s (1H, NH). Found, %: N 2.79, 3.12; S 13.54,

13.98. C₂₂H₂₃NO₆S₂. Calculated, %: N 3.03; S 13.89.

N-[4-Hydroxy-2-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-5-methylphenyl]-4-methylbenzenesulfon-

1

amide (XIIIa). Yield 55%, mp 172–173°C. H NMR

spectrum, δ, ppm: 1.03 d (6H, Me₂CH, J = 6.9 Hz),

2.02 s (3H, 5-CH₃), 2.46 s (3H, CH₃C₆H₄), 3.67–

3.80 m (1H, 2-CH), 3.93 s (3H, MeO), 6.79 s (1H,

6-H), 7.19–7.81 d.d (4H, MeC₆H₄, J = 8.7 Hz), 7.45–

7.73 d.d (4H, MeOC₆H₄, J = 8.1 Hz), 8.98 s (1H, OH),

11.15 s (1H, NH). Found, %: N 2.69, 2.91; S 12.96,

13.28. C₂₄H₂₇NO₆S₂. Calculated, %: N 2.86; S 13.10.

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-2,5-

dimethylphenyl]-4-methoxybenzenesulfonamide

(XIb). ¹H NMR spectrum, δ, ppm: 1.87 s (3H, 5-CH₃),

2.09 s (3H, 2-CH₃), 3.80 s (3H, MeO), 6.97–7.30 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 7.09 s (1H, 6-H), 7.70–

7.79 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.43 s (1H, OH),

10.24 s (1H, NH).

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-2-iso-

propyl-5-methylphenyl]-4-methoxybenzenesulfon-

1

amide (XIIIb). H NMR spectrum, δ, ppm: 1.06 d

(6H, Me₂CH, J = 6.6 Hz), 1.95 s (3H, 5-CH₃), 3.59–

3.73 m (1H, 2-CH), 3.87 s (3H, MeO), 6.57 s (1H,

6-H), 7.17–7.73 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.73–

7.85 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.04 s (1H, OH),

10.53 s (1H, NH).

N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,5-

dimethylphenyl]-4-methoxybenzenesulfonamide

(XIc). ¹H NMR spectrum, δ, ppm: 1.77 s (3H, 5-CH₃),

2.11 s (3H, 2-CH₃), 3.79 s and 3.87 s (3H each, MeO),

6.94–7.39 d.d (4H, C₆H₄, J = 9.0 Hz), 7.08 s (1H,

6-H), 7.14–7.72 d.d (4H, C₆H₄, J = 9.0 Hz), 9.38 s

(1H, OH), 10.52 s (1H, NH).

N-[4-Hydroxy-2-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-5-methylphenyl]-4-methoxybenzenesul-

1

fonamide (XIIIc). H NMR spectrum, δ, ppm: 1.00 d

(6H, Me₂CH, J = 6.6 Hz), 1.95 s (3H, 5-CH₃), 3.63–

3.77 m (1H, 2-CH), 3.86 s and 3.87 s (3H each, MeO),

6.52 s (1H, 6-H), 7.17–7.74 d.d and 7.17–7.77 d.d

(4H each, C₆H₄, J = 8.7 Hz), 8.96 s (1H, OH), 10.85 s

(1H, NH).

N-[4-Hydroxy-5-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-2-methylphenyl]-4-methylbenzenesulfon-

1

amide (XIIa). Yield 70%, mp 146–148°C. H NMR

spectrum, δ, ppm: 1.06 d (6H, Me₂CH, J = 6.9 Hz),

2.02 s (3H, 2-CH₃), 2.37 s (3H, CH₃C₆H₄), 3.20–

3.34 m (1H, 5-CH), 3.96 s (3H, MeO), 6.99 s (1H,

6-H), 7.19–7.81 d.d (4H, MeOC₆H₄, J = 8.1 Hz), 7.25–

7.42 d.d (4H, MeC₆H₄, J = 8.7 Hz), 8.18 s (1H, OH),

10.97 s (1H, NH). Found, %: N 2.64, 2.77; S 13.07,

13.54. C₂₄H₂₇NO₆S₂. Calculated, %: N 2.86; S 13.10.

N-[4-Hydroxy-2,5-dimethyl-3-(4-methylphenyl-

sulfonyl)phenyl]benzamide (XIVa). Yield 55%,

mp 209–210°C. H NMR spectrum, δ, ppm: 2.21 s

(6H, 2-CH₃, 5-CH₃), 2.41 s (3H, CH₃C₆H₄), 7.41 s

(1H, 6-H), 7.45–7.57 m (5H, Ph), 7.80–7.93 d.d

(4H, C₆H₄, J = 8.1 Hz), 9.81 s (1H, OH), 10.41 br.s

(1H, NH). Found, %: N 3.28, 3.48; S 7.86, 7.98.

C₂₂H₂₁NO₄S. Calculated, %: N 3.54; S 8.11.

1

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-5-iso-

propyl-2-methylphenyl]-4-methoxybenzenesulfon-

amide (XIIb). ¹H NMR spectrum, δ, ppm: 0.95 d (6H,

Me₂CH, J = 6.9 Hz), 2.07 s (3H, 2-CH₃), 3.07–3.21 m

(1H, 5-CH), 3.81 s (3H, MeO), 6.78 s (1H, 6-H), 7.02–

7.45 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.72–7.82 d.d

(4H, ClC₆H₄, J = 8.7 Hz), 9.29 s (1H, OH), 10.34 s

(1H, NH).

4-Chloro-N-[4-hydroxy-3-(4-methoxyphenylsul-

fonyl)-2,5-dimethylphenyl]benzamide (XIVb). Yield

1

42%, mp 177–178°C. H NMR spectrum, δ, ppm:

2.20 s (6H, CH₃), 3.85 s (3H, MeO), 7.39 s (1H, 6-H),

7.17–7.86 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.58–

7.95 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.93 s (1H, OH),

10.45 br.s (1H, NH). Found, %: N 3.02, 3.28; S 7.05,

7.39. C₂₂H₂₀ClNO₅S. Calculated, %: N 3.14; S 7.19.

N-[4-Hydroxy-5-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-2-methylphenyl]-4-methoxybenzenesul-

fonamide (XIIc). H NMR spectrum, δ, ppm: 0.97 d

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-2,5-di-

methylphenyl]-4-methoxybenzamide (XIVc). Yield

1

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AVDEENKO et al.

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1

67%, mp 168–170°C. H NMR spectrum, δ, ppm:

2.18 s (3H, 5-H₃), 2.27 s (3H, 2-CH₃), 3.82 s (3H,

MeO), 7.39 s (1H, 6-H), 7.04–7.93 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.72–7.91 d.d (4H, ClC₆H₄, J =

8.4 Hz), 9.73 s (1H, OH), 10.09 br.s (1H, NH). Found,

%: N 3.06, 3.23; S 7.02, 7.16. C₂₂H₂₀ClNO₅S. Calcu-

lated, %: N 3.14; S 7.19.

7.88 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.29–7.88 d.d

(4H, MeC₆H₄, J = 8.1 Hz), 9.11 s (1H, OH), 10.95 s

(1H, NH). Found, %: N 3.06, 3.19; S 7.03, 7.09.

C₂₅H₂₇NO₅S. Calculated, %: N 3.09; S 7.07.

N-[4-Hydroxy-2-isopropyl-5-methyl-3-(4-methyl-

phenylsulfonyl)phenyl]benzamide (XVIa). Yield

1

48%, mp 167–168°C. H NMR spectrum, δ, ppm:

N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,5-

dimethylphenyl]-4-methylbenzamide (XIVd). Yield

49%, mp 196–197°C. H NMR spectrum, δ, ppm:

2.23 s (3H, 5-CH₃), 2.24 s (3H, 2-CH₃), 2.38 s (3H,

CH₃C₆H₄), 3.91 s (3H, MeO), 7.46 s (1H, 6-H), 7.17–

7.87 d.d (4H, MeC₆H₄, J = 9.0 Hz), 7.29–8.87 d.d

(4H, MeOC₆H₄, J = 8.4 Hz), 9.03 s (1H, OH), 10.83 s

(1H, NH). Found, %: N 3.28, 3.44; S 7.50, 7.81.

C₂₃H₂₃NO₅S. Calculated, %: N 3.29; S 7.54.

0.90 d (6H, Me₂CH, J = 6.9 Hz), 2.21 s (3H, 5-CH₃),

2.41 s (3H, CH₃C₆H₄), 3.58–3.72 m (1H, 2-CH), 7.27 s

(1H, 6-H), 7.48–7.59 m (5H, Ph), 7.75–7.91 d.d (4H,

C₆H₄, J = 8.7 Hz), 9.60 s (1H, OH), 10.66 br.s

(1H, NH). Found, %: N 3.12, 3.41; S 7.27, 7.63.

C₂₄H₂₅NO₄S. Calculated, %: N 3.31; S 7.57.

1

4-Chloro-N-[4-hydroxy-2-isopropyl-3-(4-meth-

oxyphenylsulfonyl)-5-methylphenyl]benzamide

1

(XVIb). H NMR spectrum, δ, ppm: 0.94 d (6H,

Me₂CH, J = 6.9 Hz), 2.21 s (3H, 5-CH₃), 3.61–3.75 m

(1H, 2-CH), 3.86 s (3H, MeO), 7.27 s (1H, 6-H), 7.19–

7.82 m (4H, MeOC₆H₄, J = 9.0 Hz), 7.60–7.93 d.d

(4H, ClC₆H₄, J = 8.4 Hz), 9.73 s (1H, OH), 10.90 s

(1H, NH).

N-[4-Hydroxy-5-isopropyl-2-methyl-3-(4-methyl-

phenylsulfonyl)phenyl]benzamide (XVa). Yield

58%, mp 208–209°C. H NMR spectrum, δ, ppm:

1.20 d (6H, Me₂CH), 2.16 s (3H, 2-CH₃), 2.40 s (3H,

CH₃C₆H₄), 3.28–3.41 m (1H, 5-CH), 7.42 s (1H, 6-H),

7.47–7.57 m (5H, Ph), 7.80–7.94 d.d (4H, MeC₆H₄,

J = 8.1 Hz), 9.87 s (1H, OH), 10.55 br.s (1H, NH).

Found, %: N 3.28, 3.46; S 7.52, 7.85. C₂₄H₂₅NO₄S.

Calculated, %: N 3.31; S 7.57.

1

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-2-iso-

propyl-5-methylphenyl]-4-methoxybenzamide

1

(XVIc). Yield 56%, mp 188–189°C. H NMR spec-

trum, δ, ppm: 0.94 d (6H, Me₂CH, J = 6.9 Hz), 2.19 s

(3H, 5-CH₃), 3.82 s (3H, MeO), 3.61–3.75 m (1H,

2-CH), 7.26 s (1H, 6-H), 7.04–7.90 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.74–7.89 d.d (4H, ClC₆H₄, J =

8.4 Hz), 9.44 s (1H, OH), 10.37 br.s (1H, NH). Found,

%: N 3.05, 3.17; S 6.59, 6.80. C₂₄H₂₄ClNO₅S. Calcu-

lated, %: N 2.96; S 6.76.

4-Chloro-N-[4-hydroxy-5-isopropyl-3-(4-meth-

oxyphenylsulfonyl)-2-methylphenyl]benzamide

1

(XVb). H NMR spectrum, δ, ppm: 1.20 d (6H,

Me₂CH, J = 6.9 Hz), 2.16 s (3H, 2-CH₃), 3.25–3.39 m

(1H, 5-CH), 3.86 s (3H, MeO), 7.40 s (1H, 6-H), 7.18–

7.85 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.58–7.95 d.d

(4H, 4-ClC₆H₄, J = 8.7 Hz), 9.94 s (1H, OH),

10.65 br.s (1H, NH).

N-[4-Hydroxy-2-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-5-methylphenyl]-4-methylbenzamide

1

(XVId). H NMR spectrum, δ, ppm: 1.05 d (6H,

N-[3-(4-Chlorophenylsulfonyl)-4-hydroxy-5-

isopropyl-2-methylphenyl]-4-methoxybenzamide

(XVc). Yield 62%, mp 164–166°C. ¹H NMR spectrum,

δ, ppm: 1.17 d (6H, Me₂CH, J = 6.9 Hz), 2.20 s (3H,

2-CH₃), 3.24–3.38 m (1H, 5-CH), 3.82 s (3H, MeO),

7.41 s (1H, 6-H), 7.03–7.92 d.d (4H, MeOC₆H₄, J =

9.0 Hz), 7.74–7.92 d.d (4H, ClC₆H₄, J = 9.0 Hz),

9.75 s (1H, OH), 10.19 br.s (1H, NH). Found, %:

N 3.01, 3.24; S 6.70, 6.84. C₂₄H₂₄ClNO₅S. Calculated,

%: N 2.96; S 6.76.

Me₂CH, J = 7.2 Hz), 2.15 s (3H, 5-CH₃), 2.41 s (3H,

CH₃C₆H₄), 3.10–3.24 m (1H, 2-CH), 3.96 s (3H,

MeO), 7.34 s (1H, 6-H), 7.21–7.83 d.d (4H, MeO-

C₆H₄, J = 8.4 Hz), 7.32–7.91 d.d (4H, MeC₆H₄, J =

8.1 Hz), 8.07 s (1H, OH), 9.06 br.s (1H, NH).

N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,5-

dimethylphenyl]-N′-(4-methylphenylsulfonyl)benz-

1

imidamide (XVIIa). H NMR spectrum, δ, ppm:

2.13 s (3H, 5-CH₃), 2.21 s (3H, 2-CH₃), 2.33 s (3H,

CH₃C₆H₄), 3.85 s (3H, MeO), 7.34 br.s (1H, 6-H),

7.15–7.82 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.16–

7.54 m (5H, Ph), 7.18–7.53 d.d (4H, CH₃C₆H₄, J =

8.1 Hz), 10.17 s (1H, OH), 10.43 br.s (1H, NH).

N-[4-Hydroxy-5-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-2-methylphenyl]-4-methylbenzamide

1

(XVd). Yield 54%, mp 173–174°C. H NMR spec-

trum, δ, ppm: 1.24 d (6H, Me₂CH, J = 6.9 Hz), 2.24 s

(3H, 2-CH₃), 2.39 s (3H, CH₃C₆H₄), 3.33–3.47 m (1H,

5-CH), 3.91 s (3H, MeO), 7.53 s (1H, 6-H), 7.17–

N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,5-

dimethylphenyl]-N′-(4-methoxyphenylsulfonyl)-

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REACTION OF N-SUBSTITUTED 2,5-DIALKYL-1,4-BENZOQUINONE IMINES

389

1

benzimidamide (XVIIb). H NMR spectrum, δ, ppm:

2.13 s (3H, 5-CH₃), 2.19 s (3H, 2-CH₃), 3.79 s and

3.85 s (3H each, MeO), 6.91–7.47 d.d and 7.14–

7.80 d.d (4H each, MeOC₆H₄, J = 8.4 Hz), 7.40–

7.82 m (5H, Ph), 7.33 br.s (1H, 6-H), 10.07 br.s (1H,

OH), 10.38 br.s (1H, NH).

N-[4-Hydroxy-2-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-5-methylphenyl]-N′-(4-methoxyphenylsul-

fonyl)benzimidamide (XIXb). Yield 45%, mp 157–

1

158°C. H NMR spectrum, δ, ppm: 0.88 d (6H,

Me₂CH, J = 6.6 Hz), 2.21 s (3H, 5-CH₃), 3.60–3.73 m

(1H, 2-CH), 3.78 s and 3.86 s (3H, MeO), 6.86–

7.46 d.d and 7.16–7.79 d.d (4H each, C₆H₄, J =

8.4 Hz), 7.22–7.52 m (5H, Ph), 7.34 br.s (1H, 6-H),

9.99 s (1H, OH), 10.92 br.s (1H, NH). Found, %:

N 4.40, 4.62; S 10.56, 10.60. C₃₁H₃₂N₂O₇S. Calculat-

ed, %: N 4.60; S 10.53.

N-[4-Hydroxy-2,5-dimethyl-3-(4-methylphenyl-

sulfonyl)phenyl]-N′-(4-methoxyphenylsulfonyl)-

1

benzimidamide (XVIIc). H NMR spectrum, δ, ppm:

2.13 s (3H, 5-CH₃), 2.20 s (3H, 2-CH₃), 2.40 s (3H,

CH₃C₆H₄), 3.80 s (3H, MeO), 6.91–7.43 d.d (4H,

MeOC₆H₄, J = 8.4 Hz), 7.34 br.s (1H, 6-H), 7.42–

7.74 m (5H, Ph), 7.48–7.73 d.d (4H, CH₃C₆H₄, J =

8.1 Hz), 10.06 s (1H, OH), 10.31 br.s (1H, NH).

N-[4-Hydroxy-2-isopropyl-5-methyl-3-(4-methyl-

phenylsulfonyl)phenyl]-N′-(4-methoxyphenylsul-

fonyl)benzimidamide (XIXc). Yield 46%, mp 192–

1

N-[4-Hydroxy-5-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-2-methylphenyl]-N′-(4-methylphenylsul-

fonyl)benzimidamide (XVIIIa). H NMR spectrum,

δ, ppm: 1.08 d (6H, Me₂CH, J = 6.9 Hz), 2.17 s (3H,

2-CH₃), 2.33 s (3H, CH₃C₆H₄), 3.18–3.31 m (1H,

5-CH), 3.84 s (3H, MeO), 7.40 br.s (1H, 6-H), 7.14–

7.83 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.18–7.84 m

(5H, Ph), 7.19–7.48 d.d (4H, CH₃C₆H₄, J = 8.1 Hz),

10.08 s (1H, OH), 10.62 br.s (1H, NH).

194°C. H NMR spectrum, δ, ppm: 0.87 d (6H,

Me₂CH, J = 6.6 Hz), 2.21 s (3H, 5-CH₃), 2.41 s (3H,

CH₃C₆H₄), 3.57–3.71 m (1H, 2-CH), 3.79 s (3H,

MeO), 6.86–7.43 d.d (4H, MeOC₆H₄, J = 8.4 Hz),

7.36 br.s (1H, 6-H), 7.43–7.52 m (5H, Ph), 7.46–

7.73 d.d (4H, CH₃C₆H₄, J = 8.1 Hz), 9.99 br.s (1H,

OH), 10.84 br.s (1H, NH). Found, %: N 4.57, 4.65;

S 10.63, 10.78. C₃₁H₃₂N₂O₆S₂. Calculated, %: N 4.73;

S 10.82.

1

N-[4-Hydroxy-5-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-2-methylphenyl]-N′-(4-methoxyphenylsul-

fonyl)benzimidamide (XVIIIb). H NMR spectrum,

δ, ppm: 1.08 d (6H, Me₂CH, J = 6.9 Hz), 2.16 s (3H,

2-CH₃), 3.18–3.32 m (1H, 5-CH), 3.79 s and 3.85 s

(3H each, MeO), 6.89–7.83 m (5H, Ph), 6.90–7.48 d.d

and 7.15–7.82 d.d (4H each, C₆H₄, J = 8.4 Hz),

7.38 br.s (1H, 6-H), 10.03 s (1H, OH), 10.53 br.s

(1H, NH).

2,5-Dimethyl-4-(4-methylphenylsulfonylamino)-

phenyl 4-methoxybenzenesulfonate (XXa). ¹H NMR

spectrum, δ, ppm: 1.84 s (3H, 2-CH₃), 1.91 s (3H,

5-CH₃), 2.41 s (3H, CH₃C₆H₄), 3.95 s (3H, MeO),

6.82 s (1H, 6-H), 7.02 s (1H, 3-H), 7.16–7.75 d.d (4H,

MeOC₆H₄, J = 8.7 Hz), 7.25–7.46 d.d (4H, CH₃C₆H₄,

J = 8.7 Hz), 8.78 s (1H, NH).

1

4-(4-Methoxyphenylsulfonylamino)-2,5-dimeth-

1

ylphenyl 4-chlorobenzenesulfonate (XXb). H NMR

N-[4-Hydroxy-5-isopropyl-2-methyl-3-(4-methyl-

phenylsulfonyl)phenyl]-N′-(4-methoxyphenylsul-

spectrum, δ, ppm: 1.84 s (3H, 2-CH₃), 1.90 s (3H,

5-CH₃), 3.95 s (3H, MeO), 6.84 s (1H, 6-H), 7.05 s

(1H, 3-H), 7.06–7.45 d.d (4H, MeOC₆H₄, J = 9.0 Hz),

7.76–7.89 d.d (4H, ClC₆H₄, J = 8.7 Hz), 8.69 s

(1H, NH).

1

fonyl)benzimidamide (XVIIIc). H NMR spectrum,

δ, ppm: 1.08 d (6H, Me₂CH, J = 6.9 Hz), 2.15 s (3H,

2-CH₃), 2.39 s (3H, CH₃C₆H₄), 3.16–3.30 m (1H,

5-CH), 3.79 s (3H, MeO), 6.89–7.76 m (5H, Ph), 6.90–

7.44 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.39 br.s (1H,

6-H), 7.45– 7.76 d.d (4H, CH₃C₆H₄, J = 8.1 Hz),

10.01 s (1H, OH), 10.47 br.s (1H, NH).

4-(4-Methoxyphenylsulfonylamino)-2,5-dimethyl-

phenyl 4-methoxybenzenesulfonate (XXc). ¹H NMR

spectrum, δ, ppm: 1.83 s (3H, 2-CH₃), 1.91 s (3H,

5-CH₃), 3.95 s (6H, MeO), 6.82 s (1H, 6-H), 7.00–

7.42 d.d (4H, C₆H₄, J = 9.0 Hz), 7.03 s (1H, 3-H),

7.07–7.69 d.d (4H, C₆H₄, J = 8.7 Hz), 8.74 s (1H, NH).

N-[4-Hydroxy-2-isopropyl-3-(4-methoxyphenyl-

sulfonyl)-5-methylphenyl]-N′-(4-methylphenylsul-

1

fonyl)benzimidamide (XIXa). H NMR spectrum, δ,

2-Isopropyl-5-methyl-4-(4-methylphenylsulfonyl-

amino)phenyl 4-methoxybenzenesulfonate (XXIa).

¹H NMR spectrum, δ, ppm: 1.00 d (6H, Me₂CH, J =

6.6 Hz), 3.23–3.37 m (1H, 2-CH), 2.10 s (3H, 5-CH₃),

2.49 s (3H, CH₃C₆H₄), 3.96 s (3H, MeO), 6.85 s (1H,

6-H), 6.90 s (1H, 3-H), 7.16–7.77 d.d (4H, MeOC₆H₄,

ppm: 0.88 d (6H, Me₂CH, J = 6.6 Hz), 2.21 s (3H,

5-CH₃), 2.31 s (3H, CH₃C₆H₄), 3.61–3.74 m (1H,

2-CH), 3.85 s (3H, MeO), 7.14–7.55 m (5H, Ph), 7.15–

7.80 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.17–7.48 d.d

(4H, CH₃C₆H₄, J = 8.1 Hz), 7.37 br.s (1H, 6-H),

10.06 s (1H, OH), 10.93 s (1H, NH).

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AVDEENKO et al.

390

7.61–7.97 d.d (4H, ClC₆H₄, J = 8.1 Hz), 9.95 s

J = 8.7 Hz), 7.23–7.48 d.d (4H, CH₃C₆H₄, J = 8.7 Hz),

8.81 s (1H, NH).

(1H, NH).

4-(4-Methoxybenzoylamino)-2,5-dimethylphenyl

4-chlorobenzenesulfonate (XXIIIc). H NMR spec-

trum, δ, ppm: 1.99 s (3H, 2-CH₃), 2.16 s (3H, 5-CH₃),

3.76 s (3H, MeO), 6.93 s (1H, 6-H), 7.27 s (1H, 3-H),

7.08–7.65 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.79–

7.95 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.92 s (1H, NH).

2-Isopropyl-4-(4-methoxyphenylsulfonylamino)-

5-methylphenyl 4-chlorobenzenesulfonate (XXIb).

¹H NMR spectrum, δ, ppm: 1.00 d (6H, Me₂CH, J =

6.6 Hz), 2.08 s (3H, 5-CH₃), 3.21–3.35 m (1H, 2-CH),

3.95 s (3H, MeO), 6.83 s (1H, 6-H), 6.89 s (1H, 3-H),

7.00–7.42 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.70–

7.86 d.d (4H, ClC₆H₄, J = 8.4 Hz), 8.65 s (1H, NH).

1

2,5-Dimethyl-4-(4-methylbenzoylamino)phenyl

1

2-Isopropyl-4-(4-methoxyphenylsulfonylamino)-

5-methylphenyl 4-methoxybenzenesulfonate (XXIc).

¹H NMR spectrum, δ, ppm: 0.99 d (6H, Me₂CH, J =

6.6 Hz), 2.09 s (3H, 5-CH₃), 3.24–3.36 m (1H, 2-CH),

3.95 s (6H, MeO), 6.85 s (1H, 6-H), 6.92 s (1H, 3-H),

7.02–7.39 d.d and 7.19–7.82 d.d (4H each, C₆H₄, J =

8.7 Hz), 8.76 s (1H, NH).

4-methoxybenzenesulfonate (XXIIId). H NMR

spectrum, δ, ppm: 2.01 s (3H, 2-CH₃), 2.23 s (3H,

5-CH₃), 2.40 s (3H, 4-CH₃C₆H₄), 3.94 s (3H, MeO),

6.93 s (1H, 6-H), 7.34 s (1H, 3-H), 7.15–7.83 d.d (4H,

MeOC₆H₄, J = 8.7 Hz), 7.31–7.90 d.d (4H, MeC₆H₄,

J = 8.4 Hz), 8.96 s (1H, NH).

4-Benzoylamino-2-isopropyl-5-methylphenyl

1

5-Isopropyl-2-methyl-4-(4-methylphenylsulfonyl-

amino)phenyl 4-methoxybenzenesulfonate (XXIIa).

¹H NMR spectrum, δ, ppm: 1.03 d (6H, Me₂CH, J =

6.6 Hz), 2.02 s (3H, 2-CH₃), 2.41 s (3H, CH₃C₆H₄),

3.23–3.36 m (1H, 5-CH), 3.95 s (3H, MeO), 6.84 s

(1H, 6-H), 6.97 s (1H, 3-H), 7.19–7.82 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.47–7.76 d.d (4H, CH₃C₆H₄, J =

8.4 Hz), 8.73 s (1H, NH).

4-methylbenzenesulfonate (XXIVa). H NMR spec-

trum, δ, ppm: 0.99 d (6H, Me₂CH, J = 6.9 Hz), 2.15 s

(3H, 5-CH₃), 2.44 s (3H, CH₃C₆H₄), 2.88–3.02 m

(1H, 5-CH), 6.93 s (1H, 6-H), 7.32 s (1H, 3-H), 7.40–

7.60 m (5H, Ph), 7.81–7.97 d.d (4H, CH₃C₆H₄, J =

9.0 Hz), 9.90 s (1H, NH).

4-(4-Chlorobenzoylamino)-2-isopropyl-5-methyl-

phenyl 4-methoxybenzenesulfonate (XXIVb).

¹H NMR spectrum, δ, ppm: 1.00 d (6H, Me₂CH, J =

6.9 Hz), 2.14 s (3H, 5-CH₃), 2.91–3.04 m (1H, 2-CH),

3.89 s (3H, MeO), 6.94 s (1H, 6-H), 7.21–7.89 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 7.31 s (1H, 3-H), 7.60–

7.99 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.97 s (1H, NH).

5-Isopropyl-4-(4-methoxyphenylsulfonylamino)-

2-methylphenyl 4-chlorobenzenesulfonate (XXIIb).

¹H NMR spectrum, δ, ppm: 1.02 d (6H, Me₂CH, J =

6.6 Hz), 2.00 s (3H, 2-CH₃), 3.20–3.34 m (1H, 5-CH),

3.95 s (3H, MeO), 6.80 s (1H, 6-H), 6.92 s (1H, 3-H),

7.12–7.75 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.69–

7.80 d.d (4H, ClC₆H₄, J = 8.7 Hz), 8.62 s (1H, NH).

2-Isopropyl-4-(4-methoxybenzoylamino)-5-

methylphenyl 4-chlorobenzenesulfonate (XXIVc).

¹H NMR spectrum, δ, ppm: 1.00 d (6H, Me₂CH, J =

6.9 Hz), 2.15 s (3H, 5-CH₃), 2.79–2.93 m (1H, 2-CH),

3.84 s (3H, MeO), 6.94 s (1H, 6-H), 7.03–7.67 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 7.32 s (1H, 3-H), 7.75–

7.96 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.79 s (1H, NH).

5-Isopropyl-4-(4-methoxyphenylsulfonylamino)-

2-methylphenyl 4-methoxybenzenesulfonate

1

(XXIIc). H NMR spectrum, δ, ppm: 1.02 d (6H,

Me₂CH, J = 6.6 Hz), 2.02 s (3H, 2-CH₃), 3.22–3.35 m

(1H, 5-CH), 3.95 s (6H, MeO), 6.83 s (1H, 6-H), 6.95 s

(1H, 3-H), 7.14–7.72 d.d (4H, C₆H₄, J = 8.7 Hz), 7.20–

7.81 d.d (4H, C₆H₄, J = 9.0 Hz), 8.70 s (1H, NH).

2-Isopropyl-5-methyl-4-(4-methylbenzoylamino)-

phenyl 4-methoxybenzenesulfonate (XXIVd).

¹H NMR spectrum, δ, ppm: 1.05 d (6H, Me₂CH, J =

6.9 Hz), 2.26 s (3H, 5-CH₃), 2.41 s (3H, CH₃C₆H₄),

3.00–3.13 m (1H, 2-CH), 3.95 s (3H, MeO), 6.96 s

(1H, 6-H), 7.05 s (1H, 3-H), 7.18–7.86 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.34–7.92 d.d (4H, MeC₆H₄, J =

8.4 Hz), 9.04 s (1H, NH).

4-Benzoylamino-2,5-dimethylphenyl 4-methyl-

1

benzenesulfonate (XXIIIa). H NMR spectrum, δ,

ppm: 1.97 s (3H, 2-CH₃), 2.16 s (3H, 5-CH₃), 2.45 s

(3H, CH₃C₆H₄), 6.93 s (1H, 6-H), 7.27 s (1H, 3-H),

7.45–7.60 m (5H, Ph), 7.80–7.96 d.d (4H, CH₃C₆H₄,

J = 8.7 Hz), 9.86 s (1H, NH).

4-(4-Chlorobenzoylamino)-2,5-dimethylphenyl

4-methoxybenzenesulfonate (XXIIIb). H NMR

4-Benzoylamino-5-isopropyl-2-methylphenyl

4-methylbenzenesulfonate (XXVa). H NMR spec-

1

spectrum, δ, ppm: 1.97 s (3H, 2-CH₃), 2.15 s (3H,

5-CH₃), 3.89 s (3H, MeO), 6.93 s (1H, 6-H), 7.19 s

(1H, 3-H), 7.24–7.83 d.d (4H, MeOC₆H₄, J = 8.7 Hz),

trum, δ, ppm: 0.94 d (6H, Me₂CH, J = 6.9 Hz), 2.10 s

(3H, 2-CH₃), 2.98–3.11 m (1H, 5-CH), 2.44 s (3H,

CH₃C₆H₄), 6.59 s (1H, 6-H), 7.19 s (1H, 3-H), 7.42–

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REACTION OF N-SUBSTITUTED 2,5-DIALKYL-1,4-BENZOQUINONE IMINES

391

1

7.64 m (5H, Ph), 7.78–7.94 d.d (4H, C₆H₄, J = 8.4 Hz),

9.86 s (1H, NH).

oxybenzenesulfonate (XXVIIa). H NMR spectrum,

δ, ppm: 0.89 d (6H, Me₂CH, J = 6.9 Hz), 2.13 s (3H,

5-CH₃), 2.33 s (3H, CH₃C₆H₄), 2.79–2.93 m (1H,

2-CH), 3.87 s (3H, MeO), 6.92 s (1H, 6-H), 7.12 s

(1H, 3-H), 7.17–7.82 d.d (4H, MeOC₆H₄, J = 8.4 Hz),

7.24–7.61 d.d (4H, CH₃C₆H₄, J = 8.4 Hz), 7.32–7.56 m

(5H, Ph), 10.13 s (1H, NH).

4-(4-Chlorobenzoylamino)-5-isopropyl-2-methyl-

phenyl 4-methoxybenzenesulfonate (XXVb).

¹H NMR spectrum, δ, ppm: 0.95 d (6H, Me₂CH, J =

6.9 Hz), 2.11 s (3H, 2-CH₃), 2.96–3.10 m (1H, 5-CH),

3.88 s (3H, MeO), 6.61 s (1H, 6-H), 7.19 s (1H, 3-H),

7.22–7.83 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.60–

7.97 d.d (4H, ClC₆H₄, J = 8.7 Hz), 9.95 s (1H, NH).

2-Isopropyl-4-[(4-methoxyphenylsulfonylimino)-

(phenyl)methylamino]-5-methylphenyl 4-methoxy-

benzenesulfonate (XXVIIb). H NMR spectrum, δ,

ppm: 0.89 d (6H, Me₂CH, J = 6.9 Hz), 2.12 s (3H,

5-CH₃), 2.78–2.91 m (1H, 2-CH), 3.78 s and 3.88 s

(3H each, MeO), 6.92 s (1H, 6-H), 6.93–7.40 d.d

(4H, MeOC₆H₄, J = 8.4 Hz), 7.12 s (1H, 3-H), 7.17–

7.79 d.d (4H, MeOC₆H₄, J = 8.7 Hz), 7.28–7.64 m

(5H, Ph), 10.14 s (1H, NH).

1

5-Isopropyl-4-(4-methoxybenzoylamino)-2-

methylphenyl 4-chlorobenzenesulfonate (XXVc).

¹H NMR spectrum, δ, ppm: 0.87 d (6H, Me₂CH, J =

6.9 Hz), 2.13 s (3H, 2-CH₃), 2.98–3.12 m (1H, 5-CH),

3.83 s (3H, MeO), 6.60 s (1H, 6-H), 7.05–7.50 d.d

(4H, MeOC₆H₄, J = 8.7 Hz), 7.20 s (1H, 3-H), 7.80–

7.93 d.d (4H, ClC₆H₄, J = 8.74 Hz), 9.69 s (1H, NH).

2-Isopropyl-4-[(4-methoxyphenylsulfonylimino)-

(phenyl)methylamino]-5-methylphenyl 4-methyl-

benzenesulfonate (XXVIIc). H NMR spectrum, δ,

ppm: 0.89 d (6H, Me₂CH, J = 6.9 Hz), 2.12 s (3H,

5-CH₃), 2.43 s (3H, CH₃C₆H₄), 2.79–2.92 m (1H,

2-CH), 3.77 s (3H, MeO), 6.93–7.41 d.d (4H, MeO-

C₆H₄, J = 8.4 Hz), 6.94 s (1H, 6-H), 7.12 s (1H, 3-H),

7.29–7.65 m (5H, Ph), 7.30–7.72 d.d (4H, CH₃C₆H₄,

J = 8.1 Hz), 10.09 s (1H, NH).

5-Isopropyl-2-methyl-4-(4-methylbenzoylamino)-

phenyl 4-methoxybenzenesulfonate (XXVd).

¹H NMR spectrum, δ, ppm: 1.13 d (6H, Me₂CH, J =

6.9 Hz), 2.15 s (3H, 2-CH₃), 2.23 s (3H, CH₃C₆H₄),

2.91–3.05 m (1H, 5-CH), 3.92 s (3H, MeO), 6.81 s

(1H, 6-H), 6.97 s (1H, 3-H), 7.16–8.07 d.d (4H, CH₃-

C₆H₄, J = 8.4 Hz), 7.26–7.88 d.d (4H, MeOC₆H₄, J =

8.7 Hz), 8.64 s (1H, NH).

1

2,5-Dimethyl-4-[(4-methylphenylsulfonylimino)-

(phenyl)methylamino]phenyl 4-methoxybenzene-

sulfonate (XXVIa). ¹H NMR spectrum, δ, ppm: 1.86 s

(3H, 2-CH₃), 2.13 s (3H, 5-CH₃), 2.33 s (3H, CH₃-

C₆H₄), 3.88 s (3H, MeO), 6.93 s (1H, 6-H), 7.16 s

(1H, 3-H), 7.17–7.79 d.d (4H, MeOC₆H₄, J = 8.7 Hz),

7.25–7.58 d.d (4H, CH₃C₆H₄, J = 8.1 Hz), 7.48–7.72 m

(5H, Ph), 10.21 br.s (1H, NH).

5-Isopropyl-2-methyl-4-[(4-methylphenylsul-

fonylimino)(phenyl)methylamino]phenyl 4-meth-

1

oxybenzenesulfonate (XXVIIIa). H NMR spectrum,

δ, ppm: 0.91 d (6H, Me₂CH, J = 6.9 Hz), 2.05 s (3H,

2-CH₃), 2.31 s (3H, CH₃C₆H₄), 2.87–3.00 m (1H,

5-CH), 3.87 s (3H, MeO), 6.58 s (1H, 6-H), 7.13 s

(1H, 3-H), 7.17–7.77 d.d (4H, MeOC₆H₄, J = 8.4 Hz),

7.24–7.59 d.d (4H, CH₃C₆H₄, J = 8.1 Hz), 7.31–7.56 m

(5H, Ph), 10.26 s (1H, NH).

4-[(4-Methoxyphenylsulfonylimino)(phenyl)-

methylamino]-2,5-dimethylphenyl 4-methoxyben-

1

zenesulfonate (XXVIb). H NMR spectrum, δ, ppm:

5-Isopropyl-4-[(4-methoxyphenylsulfonylimino)-

(phenyl)methylamino]-2-methylphenyl 4-methoxy-

1.88 s (3H, 2-CH₃), 2.11 s (3H, 5-CH₃), 3.78 s and

3.88 s (3H each, MeO), 6.92 s (1H, 6-H), 6.93–

7.38 d.d (4H, MeOC₆H₄, J = 8.1 Hz), 7.16 s (1H, 3-H),

7.17–7.79 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.51–

7.70 m (5H, Ph), 10.14 br.s (1H, NH).

1

benzenesulfonate (XXVIIIb). H NMR spectrum, δ,

ppm: 0.91 d (6H, Me₂CH, J = 6.9 Hz), 2.05 s (3H,

2-CH₃), 2.86–3.00 m (1H, 5-CH), 3.77 s and 3.87 s

(3H each, MeO), 6.56 s (1H, 6-H), 6.91–7.41 d.d

(4H, MeOC₆H₄, J = 8.7 Hz), 7.14 s (1H, 3-H), 7.18–

7.77 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.21–7.54 m

(5H, Ph), 10.21 s (1H, NH).

4-[(4-Methoxyphenylsulfonylimino)(phenyl)-

methylamino]-2,5-dimethylphenyl 4-methylben-

1

zenesulfonate (XXVIc). H NMR spectrum, δ, ppm:

1.86 s (3H, 2-CH₃), 2.10 s (3H, 5-CH₃), 2.44 s (3H,

CH₃C₆H₄), 3.78 s (3H, MeO), 6.92 s (1H, 6-H), 6.94–

7.36 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.11 s (1H, 3-H),

7.31–7.70 d.d (4H, CH₃C₆H₄, J = 8.1 Hz), 7.54–7.69 m

(5H, Ph), 10.16 s (1H, NH).

5-Isopropyl-4-[(4-methoxyphenylsulfonylimino)-

(phenyl)methylamino]-2-methylphenyl 4-methyl-

benzenesulfonate (XXVIIIc). H NMR spectrum, δ,

ppm: 0.90 d (6H, Me₂CH, J = 6.9 Hz), 2.04 s (3H,

2-CH₃), 2.44 s (3H, CH₃C₆H₄), 2.86–2.99 m (1H,

5-CH), 3.77 s (3H, MeO), 6.56 s (1H, 6-H), 6.91–

7.41 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 7.14 s (1H, 3-H),

1

2-Isopropyl-5-methyl-4-[(4-methylphenylsul-

fonylimino)(phenyl)methylamino]phenyl 4-meth-

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

AVDEENKO et al.

392

7.20–7.50 m (5H, Ph), 7.34–7.70 d.d (4H, CH₃C₆H₄,

J = 8.1 Hz), 10.19 br.s (1H, NH).

2.49 s (3H, CH₃C₆H₄), 2.94–3.08 m (1H, 2-CH), 3.96 s

(3H, MeO), 6.36 s (1H, 3-H), 6.64 s (1H, 6-H), 7.16–

7.74 d.d (4H, CH₃C₆H₄, J = 8.7 Hz), 7.26–7.49 d.d

(4H, MeOC₆H₄, J = 8.4 Hz), 8.40 s (1H, OH).

N-(4-Hydroxy-2,5-dimethylphenyl)-4-methoxy-

N-(4-methylphenylsulfonyl)benzenesulfonamide

1

(XXIXa). H NMR spectrum, δ, ppm: 1.84 s (3H,

4-Chloro-N-(4-hydroxy-2-isopropyl-5-methyl-

phenyl)-N-(4-methoxyphenylsulfonyl)benzenesul-

5-CH₃), 1.94 s (3H, 2-CH₃), 2.49 s (3H, CH₃C₆H₄),

3.96 s (3H, MeO), 6.52 s (1H, 3-H), 6.72 s (1H, 6-H),

7.19–7.43 d.d (4H, CH₃C₆H₄, J = 8.7 Hz), 7.27–

7.84 d.d (4H, MeOC₆H₄, J = 8.4 Hz), 8.33 s (1H, OH).

1

fonamide (XXXIb). H NMR spectrum, δ, ppm:

0.76 d (6H, Me₂CH, J = 6.9 Hz), 2.02 s (3H, 5-CH₃),

2.92–3.05 m (1H, 2-CH), 3.96 s (3H, MeO), 6.35 s

(1H, 3-H), 6.60 s (1H, 6-H), 7.05–7.41 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.67–7.83 d.d (4H, ClC₆H₄, J =

8.4 Hz), 8.23 s (1H, OH).

4-Chloro-N-(4-hydroxy-2,5-dimethylphenyl)-

N-(4-methoxyphenylsulfonyl)benzenesulfonamide

1

(XXIXb). H NMR spectrum, δ, ppm: 1.84 s (3H,

5-CH₃), 1.95 s (3H, 2-CH₃), 3.96 s (3H, MeO), 6.55 s

(1H, 3-H), 6.74 s (1H, 6-H), 7.08–7.49 d.d (4H, MeO-

C₆H₄, J = 8.7 Hz), 7.72–7.87 d.d (4H, ClC₆H₄, J =

8.4 Hz), 8.19 s (1H, OH).

N-(4-Hydroxy-2-isopropyl-5-methylphenyl)-

4-methoxy-N-(4-methoxyphenylsulfonyl)benzene-

sulfonamide (XXXIc). H NMR spectrum, δ, ppm:

0.77 d (6H, Me₂CH, J = 6.9 Hz), 2.01 s (3H, 5-CH₃),

2.94–3.07 m (1H, 2-CH), 3.96 s (6H, MeO), 6.34 s

(1H, 3-H), 6.62 s (1H, 6-H), 7.15–7.79 d.d (8H, C₆H₄,

J = 8.7 Hz), 8.34 s (1H, OH).

1

N-(4-Hydroxy-2,5-dimethylphenyl)-4-methoxy-

N-(4-methoxyphenylsulfonyl)benzenesulfonamide

1

(XXIXc). H NMR spectrum, δ, ppm: 1.83 s (3H,

5-CH₃), 1.94 s (3H, 2-CH₃), 3.96 s (6H, MeO), 6.52 s

(1H, 3-H), 6.71 s (1H, 6-H), 7.23–7.81 d.d (8H, C₆H₄,

J = 8.7 Hz), 8.29 s (1H, OH).

N-(4-Hydroxy-2,5-dimethylphenyl)-N-(4-methyl-

phenylsulfonyl)benzamide (XXXIIa). ¹H NMR spec-

trum, δ, ppm: 1.91 s (3H, 5-CH₃), 2.03 s (3H, 2-CH₃),

2.34 s (3H, CH₃C₆H₄), 6.49 s (1H, 3-H), 7.05 s (1H,

6-H), 7.20–7.35 m (5H, Ph), 7.43–7.88 d.d (4H, C₆H₄,

J = 8.7 Hz), 9.65 s (1H, OH).

N-(4-Hydroxy-5-isopropyl-2-methylphenyl)-

4-methoxy-N-(4-methylphenylsulfonyl)benzenesul-

fonamide (XXXa). ¹H NMR spectrum, δ, ppm: 0.84 d

(6H, Me₂CH, J = 6.9 Hz), 1.99 s (3H, 2-CH₃), 2.49 s

(3H, CH₃C₆H₄), 2.84–2.98 m (1H, 5-CH), 3.96 s (3H,

MeO), 6.33 s (1H, 3-H), 6.75 s (1H, 6-H), 7.20–

7.35 d.d (4H, CH₃C₆H₄, J = 8.7 Hz), 7.31–7.90 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 8.30 s (1H, OH).

4-Chloro-N-(4-hydroxy-2,5-dimethylphenyl)-

N-(4-methoxyphenylsulfonyl)benzamide (XXXIIb).

¹H NMR spectrum, δ, ppm: 1.87 s (3H, 5-CH₃), 2.03 s

(3H, 2-CH₃), 3.89 s (3H, MeO), 6.51 s (1H, 3-H), 7.03 s

(1H, 6-H), 7.18–7.90 d.d (4H, MeOC₆H₄, J = 9.0 Hz),

7.67–7.82 d.d (4H, ClC₆H₄, J = 8.4 Hz), 9.70 s

(1H, OH).

4-Chloro-N-(4-hydroxy-5-isopropyl-2-methyl-

phenyl)-N-(4-methoxyphenylsulfonyl)benzenesul-

fonamide (XXXb). ¹H NMR spectrum, δ, ppm: 0.85 d

(6H, Me₂CH, J = 6.9 Hz), 2.00 s (3H, 2-CH₃), 2.82–

2.95 m (1H, 5-CH), 3.96 s (3H, MeO), 6.38 s (1H,

3-H), 6.77 s (1H, 6-H), 7.15–7.43 d.d (4H, MeOC₆H₄,

J = 8.7 Hz), 7.72–7.91 d.d (4H, ClC₆H₄, J = 8.4 Hz),

8.18 s (1H, OH).

N-(4-Hydroxy-2,5-dimethylphenyl)-N-(4-meth-

oxyphenylsulfonyl)-4-methylbenzamide (XXXIId).

¹H NMR spectrum, δ, ppm: 8.68 s (1H, OH), 7.14–

7.98 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.03–7.46 d.d

(4H, MeC₆H₄, J = 8.7 Hz), 7.01 s (1H, 6-H), 6.59 s

(1H, 3-H), 3.94 s (3H, MeO), 2.24 s (3H, CH₃C₆H₄),

2.10 s (3H, 2-CH₃), 1.96 s (3H, 5-CH₃).

N-(4-Hydroxy-5-isopropyl-2-methylphenyl)-

4-methoxy-N-(4-methoxyphenylsulfonyl)benzene-

N-(4-Hydroxy-5-isopropyl-2-methylphenyl)-

N-(4-methylphenylsulfonyl)benzamide (XXXIIIa).

¹H NMR spectrum, δ, ppm: 1.08 d (6H, Me₂CH, J =

6.9 Hz), 2.00 s (3H, 2-CH₃), 2.34 s (3H, CH₃C₆H₄),

2.96–3.10 m (1H, 5-CH), 6.52 s (1H, 3-H), 6.76 s (1H,

6-H), 7.20–7.37 m (5H, Ph), 7.43–7.84 d.d (4H, CH₃-

C₆H₄, J = 8.7 Hz), 9.60 s (1H, OH).

1

sulfonamide (XXXc). H NMR spectrum, δ, ppm:

0.84 d (6H, Me₂CH, J = 6.9 Hz), 2.00 s (3H, 2-CH₃),

2.84–2.97 m (1H, 5-CH), 3.96 s (6H, MeO), 6.36 s

(1H, 3-H), 6.74 s (1H, 6-H), 7.28–7.86 d.d (8H,

4-MeOC₆H₄, J = 8.7 Hz), 8.27 s (1H, OH).

N-(4-Hydroxy-2-isopropyl-5-methylphenyl)-

4-methoxy-N-(4-methylphenylsulfonyl)benzenesul-

4-Chloro-N-(4-hydroxy-5-isopropyl-2-methyl-

phenyl)-N-(4-methoxyphenylsulfonyl)benzamide

1

fonamide (XXXIa). H NMR spectrum, δ, ppm:

1

0.77 d (6H, Me₂CH, J = 6.9 Hz), 2.02 s (3H, 5-CH₃),

(XXXIIIb). H NMR spectrum, δ, ppm: 1.08 d (6H,

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REACTION OF N-SUBSTITUTED 2,5-DIALKYL-1,4-BENZOQUINONE IMINES

393

Me₂CH, J = 6.9 Hz), 1.98 s (3H, 2-CH₃), 2.97–3.11 m

(1H, 5-CH), 3.80 s (3H, MeO), 6.54 s (1H, 3-H),

6.75 s (1H, 6-H), 7.27–7.81 d.d (4H, MeOC₆H₄, J =

8.7 Hz), 7.64–7.85 d.d (4H, ClC₆H₄, J = 8.4 Hz),

9.64 s (1H, OH).

ClC₆H₄, J = 8.7 Hz). Found, %: N 2.64, 2.95; S 6.72,

6.90. C₂₄H₂₂ClNO₅S. Calculated, %: N 2.97; S 6.79.

4-Chloro-N-[2-isopropyl-3-(4-methoxyphenylsul-

fonyl)-5-methyl-4-oxocyclohexa-2,5-dien-1-ylidene]-

benzamide (XXXVI). Yield 66%, mp 142–143°C.

¹H NMR spectrum, δ, ppm: 1.58 d (6H, Me₂CH, J =

6.9 Hz), 1.85 s (3H, 5-CH₃), 3.89 s (3H, MeO), 4.76–

4.90 m (1H, 2-CH), 6.54 s (1H, 6-H), 7.03–8.03 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 7.50–7.79 d.d (4H,

ClC₆H₄, J = 8.4 Hz). Found, %: N 2.73, 3.08; S 6.57,

6.86. C₂₄H₂₂ClNO₅S. Calculated, %: N 2.97; S 6.79.

N-(4-Hydroxy-5-isopropyl-2-methylphenyl)-

N-(4-methoxyphenylsulfonyl)-4-methylbenzamide

1

(XXXIIId). H NMR spectrum, δ, ppm: 1.20 d (6H,

Me₂CH, J = 6.9 Hz), 2.09 s (3H, 2-CH₃), 2.23 s (3H,

CH₃C₆H₄), 3.09–3.23 m (1H, 5-CH), 3.95 s (3H,

MeO), 6.63 s (1H, 3-H), 6.84 s (1H, 6-H), 7.20–

7.35 d.d (4H, MeC₆H₄, J = 8.4 Hz), 7.31–7.96 d.d (4H,

MeOC₆H₄, J = 8.7 Hz), 8.69 s (1H, OH).

REFERENCES

4-Chloro-N-[3-(4-methoxyphenylsulfonyl)-2,5-di-

methyl-4-oxocyclohexa-2,5-dien-1-ylidene]benz-

amide (XXXIV). Yield 74%, mp 175–177°C. ¹H NMR

spectrum, δ, ppm: 1.88 s (3H, 5-CH₃), 2.92 s (3H,

2-CH₃), 3.89 s (3H, MeO), 6.67 s (1H, 6-H), 7.03–

8.04 d.d (4H, MeOC₆H₄, J = 9.0 Hz), 7.48–7.81 d.d

(4H, ClC₆H₄, J = 8.4 Hz). Found, %: N 3.02, 3.46;

S 7.01, 7.34. C₂₂H₁₈ClNO₅S. Calculated, %: N 3.16;

S 7.22.

1. Avdeenko, A.P., Konovalova, S.A., Roman’kov, D.A.,

Burmistrov, K.S., Nichvoloda, V.M., Shishkin, O.V.,

Zubatyuk, R.I., and Palamarchuk, G.V., Russ. J. Org.

Chem., 2009, vol. 45, p. 48.

2. Burmistrov, S.I. and Titov, E.A., Zh. Obshch. Khim.,

1952, vol. 22, p. 999.

3. Adams, R. and Looker, J.H., J. Am. Chem. Soc., 1951,

vol. 73, p. 1145.

4. Avdeenko, A.P. and Konovalova, S.A., Russ. J. Org.

Chem., 2006, vol. 42, p. 669.

N-[3-(4-Chlorophenylsulfonyl)-5-isopropyl-2-

methyl-4-oxocyclohexa-2,5-dien-1-ylidene]-4-meth-

oxybenzamide (XXXV). Yield 68%, mp 93–95°C.

¹H NMR spectrum, δ, ppm: 0.92 d (6H, Me₂CH, J =

6.9 Hz), 2.79–2.93 m (1H, 5-CH), 2.93 s (3H, 2-CH₃),

3.89 s (3H, MeO), 6.61 s (1H, 6-H), 6.98–8.03 d.d

(4H, MeOC₆H₄, J = 9.0 Hz), 7.53–7.82 d.d (4H,

5. Avdeenko, A.P., Konovalova, S.A., and Ludchenko, O.N.,

Vopr. Khim. Khim. Tekhnol., 2006, no. 5, p. 60.

6. Organic Syntheses, Blatt, A.H., Ed., New York: Wiley,

1941, collect. vol. 1, p. 492. Translated under the title

Sintezy organicheskikh preparatov, Moscow: Inostran-

naya Literatura, 1949, collect. vol. 1, p. 394.

RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 3 2009

Article Doi

Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

DOI: 10.1134/S1070428009030063

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