Hydrohalogenation of N-[arylsulfonylimino(phenyl)methyl]-1,4-benzoquinone monoimines having alkyl substituents in the quinoid ring

Article abstract of DOI:10.1134/S1070428011070116

Hydrohalogenation of N-[arylsulfonylimino(phenyl)methyl]-2,5(3,5)-dimethyl- 1,4-benzoquinone monoimines follows exclusively the 1,4-addition pattern, whereas N-[arylsulfonylimino(phenyl)methyl]-2,6-dimethyl-1,4-benzoquinone monoimines take up hydrogen halides according to the 6,3-addition scheme.

Full text of DOI:10.1134/S1070428011070116

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 7, pp. 1035–1044. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, V.V. Pirozhenko, O.P. Ledeneva, A.A. Santalova, 2011, published in Zhurnal Organicheskoi
Khimii, 2011, Vol. 47, No. 7, pp. 1020–1028.
Hydrohalogenation of N-[Arylsulfonylimino(phenyl)methyl]-
1,4-benzoquinone Monoimines Having Alkyl Substituents
in the Quinoid Ring
A. P. Avdeenkoa, S. A. Konovalovaa, V. V. Pirozhenkob, O. P. Ledenevaa, and A. A. Santalovaa
a Donbass State Machine-Building Academy, ul.Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
Received November 23, 2010
Abstract—Hydrohalogenation of N-[arylsulfonylimino(phenyl)methyl]-2,5(3,5)-dimethyl-1,4-benzoquinone
monoimines follows exclusively the 1,4-addition pattern, whereas N-[arylsulfonylimino(phenyl)methyl]-2,6-di-
methyl-1,4-benzoquinone monoimines take up hydrogen halides according to the 6,3-addition scheme.
DOI: 10.1134/S1070428011070116
Hydrohalogenation of N-substituted p-quinone
monoimines was studied in sufficient detail [1–9].
Hydrohalogenation of N-aryl- [1, 2], N-arylsulfonyl-
[4, 5], N-aroyl-, N-acetyl- [6, 7], and some N-[aryl-
sulfonylimino(phenyl)methyl]-1,4-benzoquinone
monoimines was reported [8]. It was found that ad-
dition of the first hydrogen halide molecule to quinone
imines possessing at least one vacant ortho position
with respect to the carbonyl group generally follows
the 1,4-addition pattern [1, 2, 4–8]. Only hydro-
chlorination of N-(4-methylphenyl)-1,4-benzoquinone
imine occurred as 6,3-addition [3].
quinoid ring and size of the halogen atom. Quinone
imines having no substituents in the quinoid ring take
up first two hydrogen halide molecules according to
the 1,4-addition scheme, and the subsequent addition
follows 6,3-addition pattern to produce 4-amino-N-
arylsulfonyl-2,3,6-trichloro(or 2,6-dibromo)phenols
[4, 5] and 4-amino-N-[arylsulfonylimino(phenyl)-
methyl]-2,3,5,6-tetrachloro(or 2,3,6-tribromo)phenols
[8]. The latter products contained the maximum pos-
sible number of chlorine atoms in the case of hydro-
chlorination.
We previously succeeded in effecting 6,3-addition
of one hydrogen halide molecule in the hydrochlorina-
tion of 2,6-dimethyl-substituted N-arylsulfonyl- and
N-[arylsulfonylimino(phenyl)methyl]-1,4-benzoqui-
Successive hydrohalogenation–oxidation–hydro-
halogenation gives different products, depending on
the substituents on the nitrogen atom and in the
Scheme 1.
O
OH
O
R1
R1
Hlg
R1
Hlg
[O]
HHlg
R2
R2
R2
HHlg
N
NSO2Ar
HN
NSO2Ar
N
NSO2Ar
Ph
Ia–Ic, IIa–IIc, IIIa–IIIc
Ph
Ph
IVa–IVc, Va–Vc, VIa–VIc
VIIa–VIIc, VIIIa–VIIIc, IXa–IXc
Xa–Xc, XIa–XIc, XIIa–XIIc
XIIIa–XIIIc, XIVa–XIVc, XVa–XVc
Ar = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c); I, IV, VII, X, XIII, R1 = R2 = Me; II, V, VIII, XI, XIV, R1 = i-Pr, R2 = Me;
III, VI, IX, XII, XV, R1 = Me, R2 = i-Pr; IV–VI, X–XII, Hlg = Cl; VII–IX, XIII–XV, Hlg = Br.
1035

AVDEENKO et al.
1036
none imines [6, 8]. N-[Arylsulfonylimino(phenyl)-
methyl]-2,6-dimethyl-1,4-benzoquinone imines are ca-
pable of taking up in succession two hydrogen chloride
molecules, whereas their hydrobromination even under
severe conditions was unsuccessful: only the initial
compounds and their hydrolysis products were isolated
[8]. Successive hydrohalogenation–oxidation–hydro-
halogenation of N-arylsulfonyl- and N-aroyl(or acetyl)-
2,5-dialkyl-1,4-benzoquinone monoimines afforded
only products containing one halogen atom in the
6-position [6, 7, 9].
possible number of halogen atoms in the quinoid ring.
It should be noted that hydrohalogenation of N-[aryl-
sulfonylimino(phenyl)methyl]-2,5-dialkyl-1,4-benzo-
quinone imines was not studied previously. Only
hydrohalogenation of the corresponding N-phenyl-
2,6(3,5)-dimethyl derivatives was reported [8].
N-[Arylsulfonylimino(phenyl)methyl]-2,5-dialkyl-
1,4-benzoquinone imines Ia–Ic, IIa–IIc, and IIIa–IIIc
were synthesized by oxidation of the corresponding
2,5-dialkyl-4-amino-N-[arylsulfonylimino(phenyl)-
methyl]phenols with lead tetraacetate in acetic acid.
Hydrochlorination of 2,5-dimethyl- (Ia–Ic), 2-iso-
propyl-5-methyl- (IIa–IIc), and 5-isopropyl-2-methyl-
1,4-benzoquinone imines (IIIa–IIIc) was carried out
by passing gaseous hydrogen chloride through a solu-
tion of quinone imine I–III in chloroform, and their
hydrobromination was performed in acetic acid by
adding excess 40% hydrobromic acid. According to the
1H NMR data, the only products were the correspond-
ing 2,5-dialkyl-4-amino-N-[arylsulfonylimino(phenyl)-
methyl]-6-halophenols IV–IX (Scheme 1). No 6,3-ad-
dition products were detected.
N-[Arylsulfonylimino(phenyl)methyl]-1,4-benzo-
quinone imines may be regarded as N-aroyl-1,4-benzo-
quinone imine derivatives in which the oxygen atom in
the =NC=O carbonyl group is replaced by an arylsul-
fonylimino group (ArSO2N=), i.e., these compounds
are structurally analogous [10]. On the other hand, the
redox potential of N-[arylsulfonylimino(phenyl)meth-
yl]-1,4-benzoquinone imines is intermediate between
those of N-arylsulfonyl- and N-aroyl-1,4-benzoquinone
imines [11–13]. It is known that this parameter is
important in the hydrhalogenation process; therefore,
in many cases N-[arylsulfonylimino(phenyl)methyl]-
1,4-benzoquinone imines exhibit reactivity typical of
both N-arylsulfonyl- and N-aroyl-1,4-benzoquinone
imines [14, 15].
Aminophenols IV–IX were oxidized with lead
tetraacetate in acetic acid to obtain the corresponding
1
quinone imines X–XV. The H NMR spectra of com-
pounds Xa–Xc, XIIa–XIIc, XIIIa–XIIIc, and XVa–
XVc contained a quartet due to 3-H in the region
δ 6.38–6.48 ppm, while quinone imines XIa–XIc and
XIVa–XIVc displayed a singlet from 5-H at δ 6.38–
6.40 ppm. These data confirmed the assumed structure
The present work was aimed at studying hydrohalo-
genation of alkyl-substituted N-[arylsulfonylimino-
(phenyl)methyl]-1,4-benzoquinone imines and obtain-
ing their halogen derivatives containing the maximum
Scheme 2.
O
OH
O
Me
Me
Me
Me
Me
Me
[O]
HCl
Cl
Cl
N
NSO2Ar
HN
NSO2Ar
N
NSO2Ar
Ph
XVIa, XVIb
Ph
XVIIa, XVIIb
Ph
XVIIIa, XVIIIb
OH
O
N
Me
Me
Me
Me
[O]
HCl
Cl
Cl
NSO2Ar
Cl
Cl
HN
NSO2Ar
Ph
XIXa, XIXb
Ph
XXa, XXb
Ar = 4-MeC6H4 (a), 4-ClC6H4 (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011

HYDROHALOGENATION OF N-[ARYLSULFONYLIMINO(PHENYL)METHYL]-...
1037
Scheme 3.
O
OH
O
Hlg
Hlg
HHlg
[O]
Me
Me
Me
Me
Me
Me
N
NSO2Ar
HN
NSO2Ar
N
NSO2Ar
Ph
Ph
Ph
XXIa, XXIb
XXIIa, XXIIb, XXIIIa, XXIIIb
XXIVa, XXIVb, XXVa, XXVb
OH
O
Hlg
Hlg
Hlg
Hlg
HHlg
[O]
Me
Me
Me
Me
HN
NSO2Ar
N
NSO2Ar
Ph
XXVIa, XXVIb, XXVIIa, XXVIIb
Ph
XXVIIIa, XXVIIIb, XXIXa, XXIXb
Ar = 4-MeC6H4 (a), 4-ClC6H4 (b).
1
XXVIIIa, XXVIIIb, XXIXa, and XXIXb (Scheme 3).
Successful hydrohalogenation of the above substrates
is ensured by the absence of substituents in both ortho
positions of the quinoid ring, which are more reactive
toward hydrogen halides as nucleophiles.
of the products. In the H NMR spectra of XIa–XIc
and XIVa–XIVc we observed a broadened doublet at
δ 1.04–1.06 ppm with a coupling constant J of 18.6–
20.4 Hz due to protons in the isopropyl groups. Our
attempt to subject quinone imines X–XV to further
hydrohalogenation even under severe conditions (on
heating in DMF) resulted in their reduction, and only
the corresponding 6-halophenols IV–IX were isolated
from the reaction mixtures (Scheme 1).
Thus hydrohalogenation of N-[arylsulfonylimino-
(phenyl)methyl]-2,5-dialkyl-1,4-benzoquinone imines
is strictly regioselective, and it follows exclusively the
1,4-addition pattern. We failed to introduce the second
hydrogen halide molecule to obtain 6,3-addition prod-
ucts. Hydrochlorination of 2,6-dimethyl-substituted
derivatives gives 6,3-addition products, and chlorine
atoms can be introduced in both ortho positions with
respect to the C=N carbon atom.
We also extended the substrate series via introduc-
tion of a donor or acceptor substituent into the para-
position of the arylsulfonyl fragment in N-[arylsul-
fonylimino(phenyl)methyl]-2,6(3,5)-dimethyl-1,4-ben-
zoquinone imines, expecting that such substitution
could affect the hydrohalogenation process [3]. By
consecutive hydrochlorination–oxidation–hydrochlori-
nation of 2,6-dimethyl derivatives XVIa and XVIb we
succeeded in adding two hydrogen chloride molecules
(Scheme 2) and obtaining aminophenols XVIIa,
XVIIb, XIXa, and XIXb and quinone imines XVIIIa,
XVIIIb, XXa, and XXb. However, no hydrobromina-
tion of the same substrates occurred even under severe
conditions, presumably for steric reasons. As a result,
only the initial quinone imines and their hydrolysis
products were isolated.
We found previously that introduction of methyl
groups into the quinoid ring of quinone imines con-
siderably reduces their redox potential [16] and that the
magnitude of this reduction is larger for 2,6-dimethyl
derivatives than for their 2,5-dimethyl analogs. The
presence of a halogen atom in the quinoid ring in-
creases the redox potential [17], but its effect is much
weaker than the effect of methyl substituent. There-
fore, the redox potential of quinone imines X–XV
should be higher than that of quinone imines XVIII.
As a result, reduction of quinone imines X–XV is more
favorable than their hydrohalogenation. We can con-
clude that the hydrohalogenation of N-[arylsulfonyl-
imino(phenyl)methyl]-1,4-benzoquinone imines is
controlled by steric factors and competition between
two processes, hydrohalogenation and reduction.
As might be expected, stepwise hydrohalogenation
of 3,5-dimethyl-substituted analogs XXIa and XXIb
afforded aminophenols XXIIa, XXIIb, XXIIIa,
XXIIIb, XXVIa, XXVIb, XXVIIa, and XXVIIb and
quinone imines XXIVa, XXIVb, XXVa, XXVb,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011

AVDEENKO et al.
16.2 Hz), 2.19 d (3H, 2-Me, J = 1.2 Hz), 2.94–3.03 m
1038
EXPERIMENTAL
(1H, CHMe2), 6.35 s (1H, 6-H), 6.59 q (1H, 3-H, J =
1.2 Hz), 7.43–7.99 m (10H, Harom). Found, %: N 7.00,
7.16; S 7.59, 7.78. C23H22N2O3S. Calculated, %:
N 6.89; S 7.89.
1
The H NMR spectra were recorded on a Varian
VXR-300 spectrometer (300 MHz) from solutions in
CDCl3. The chemical shifts were determined relative
to tetramethylsilane. The reaction mixtures were ana-
lyzed by TLC on Silufol UV-254 plates; spots were
applied as solutions in chloroform, benzene–hexane
(10:1) was used as eluent, and the chromatograms
were developed under UV light.
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (IIb). Yield 86%, mp 105–107°C;
1
published data [15]: mp 102–104°C. H NMR spec-
trum, δ, ppm: 1.01 d (6H, CHMe2, J = 20.7 Hz), 2.20 d
(3H, 2-Me, J = 0.9 Hz), 2.43 s (3H, MeC6H4), 2.93–
3.02 m (1H, CHMe2), 6.33 s (1H, 6-H), 6.59 q (1H,
3-H, J = 1.2 Hz), 7.29 d (2H, 3′-H, 5′-H, J = 8.4 Hz),
7.42–7.79 m (5H, C6H5), 7.85 d (2H, 2′-H, 6′-H,
J = 8.4 Hz).
Initial N-[arylsulfonylimino(phenyl)methyl]-1,4-
benzoquinone imines Ia–Ic, IIa–IIc, IIIa–IIIc, XVIa,
XVIb, XXIa, and XXIb were synthesized by oxida-
tion of the corresponding N-substituted p-amino-
phenols with lead tetraacetate in acetic acid [18].
4-[Arylsulfonylimino(phenyl)methylamino]phenols
were prepared in turn by acylation of 4-aminophenols
with N-arylsulfonylbenzimidoyl chlorides in DMF–
AcOH (1:3) in the presence of anhydrous sodium
acetate according to the procedure described in [18].
N′-(4-Chlorophenylsulfonyl)-N-(5-isopropyl-2-
methyl-4-oxocyclohexa-2,5-dien-1-ylidene) benzene-
carboximidamide (IIc). Yield 88%, mp 123.5–124°C.
1H NMR spectrum, δ, ppm: 1.01 d (6H, CHMe2, J =
7.7 Hz), 2.22 d (3H, Me, J = 1.2 Hz), 2.92–3.01 m
(1H, CHMe2), 6.33 s (1H, 6-H), 6.59 q (1H, 3-H, J =
1.2 Hz), 7.29 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.46–
7.79 m (5H, C6H5), 7.84 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: N 5.87, 6.03; S 6.75, 6.94. C25H26ClN2O3S.
Calculated, %: N 5.96; S 6.82.
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-N′-(phenylsulfonyl)benzenecarboximidamide
(Ia). Yield 79%, mp 121–123°C; published data [19]:
1
mp 120–121°C. H NMR spectrum, δ, ppm: 1.94 d
(3H, 5-Me, J = 1.2 Hz), 2.21 d (3H, 2-Me, J = 1.5 Hz),
6.42 q (1H, 6-H, J = 1.5 Hz), 6.61 q (1H, 3-H, J =
1.5 Hz), 7.42–8.19 m (10H, Harom).
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(phenylsulfonyl)benzenecarbox-
1
N-(2,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-N′-(4-methylphenylsulfonyl)benzenecarbox-
imidamide (Ib). Yield 84%, mp 134–136°C; published
imidamide (IIIa). Yield 79%, mp 122°C. H NMR
spectrum, δ, ppm: 1.26–1.33 d.d (6H, CHMe2, J =
15.6 Hz), 1.93 d (3H, Me, J = 1.2 Hz), 3.17–3.26 m
(1H, CHMe2), 6.41 q (1H, 6-H, J = 1.5 Hz), 6.59 s
(1H, 3-H), 7.43–7.99 m (10H, Harom). Found, %:
N 6.87, 7.03; S 7.75, 7.96. C23H22N2O3S. Calculated,
%: N 6.89; S 7.89.
1
data [15]: mp 131.5–132°C. H NMR spectrum, δ,
ppm: 1.92 d (3H, 5-Me, J = 1.2 Hz), 2.23 d (3H, 2-Me,
J = 1.5 Hz), 2.42 s (3H, MeC6H4), 6.38 q (1H, 6-H, J =
1.5 Hz), 6.61 q (1H, 3-H, J = 1.2 Hz), 7.28 d (2H,
3′-H, 5′-H, J = 8.7 Hz), 7.42–7.81 m (5H, C6H5),
7.85 d (2H, 2′-H, 6′-H, J = 8.7 Hz).
N-(2-Isopropyl-5-methyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (IIIb). Yield 87%, mp 85–86°C;
N′-(4-Chlorophenylsulfonyl)-N-(2,5-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene)benzenecarbox-
imidamide (Ic). Yield 89%, mp 112–113°C. H NMR
spectrum, δ, ppm: 1.95 d (3H, 5-Me, J = 1.5 Hz),
2.24 d (3H, 2-Me, J = 1.5 Hz), 6.42 q (1H, 6-H, J =
1.5 Hz), 6.62 q (1H, 3-H, J = 1.2 Hz), 7.44–7.80 m
(5H, C6H5), 7.48 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.93 d
(2H, 2′-H, 6′-H, J = 8.4 Hz). Found, %: N 6.53, 6.76;
S 7.59, 7.78. C21H17ClN2O3S. Calculated, %: N 6.78;
S 7.77.
1
published data [15]: mp 78–80°C. H NMR spectrum,
1
δ, ppm: 1.27–1.33 d.d (6H, CHMe2, J = 5.1 Hz),
1.91 d (3H, 5-Me, J = 1.2 Hz), 2.42 s (3H, MeC6H4),
3.18–3.27 m (1H, CHMe2), 6.37 q (1H, 6-H, J =
1.5 Hz), 6.58 s (1H, 3-H), 7.29 d (2H, 3′-H, 5′-H, J =
8.4 Hz), 7.42–7.79 m (5H, C6H5), 7.86 d (2H, 2′-H,
6′-H, J = 8.4 Hz).
N′-(4-Chlorophenylsulfonyl)-N-(2-isopropyl-5-
methyl-4-oxocyclohexa-2,5-dien-1-ylidene)benzene-
carboximidamide (IIIc). Yield 91%, mp 140–141°C.
1H NMR spectrum, δ, ppm: 1.27–1.34 d.d (6H,
CHMe2, J = 5.7 Hz), 1.95 d (3H, 5-Me, J = 1.5 Hz),
3.17–3.26 m (1H, CHMe2), 6.42 q (1H, 6-H, J =
N-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(phenylsulfonyl)benzenecarbox-
imidamide (IIa). Yield 81%, mp 125–125.5°C.
1H NMR spectrum, δ, ppm: 1.02 d (6H, CHMe2, J =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011

HYDROHALOGENATION OF N-[ARYLSULFONYLIMINO(PHENYL)METHYL]-...
1039
1.5 Hz), 6.59 s (1H, 3-H), 7.44–7.79 m (5H, C6H5),
7.49 d (2H, 3′-H, 5′-H, J = 9.0 Hz), 7.93 d (2H, 2′-H,
6′-H, J = 9.0 Hz). Found, %: N 6.18, 6.32; S 7.25,
7.36. C23H21SlN2O3S. Calculated, %: N 6.35; S 7.27.
N-(3-Chloro-4-hydroxy-2,5-dimethylphenyl)-N′-
(4-methylphenylsulfonyl)benzenecarboximidamide
(IVb). Yield 77%, mp 213–215°C. Found, %: Cl 8.11,
8.27; N 6.60, 6.77; S 7.25, 7.43. C22H21ClN2O3S. Cal-
culated, %: Cl 8.27; N 6.63; S 7.48.
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-N′-(4-methylphenylsulfonyl)benzenecarbox-
imidamide (XVIa). Yield 88%, mp 169–170°C; pub-
lished data [14]: mp 172–174°C. 1H NMR spectrum, δ,
ppm: 2.05 s (6H, 3-Me, 5-Me), 2,43 s (3H, MeC6H4),
6.73 br.s (2H, 2-H, 6-H), 7.30 d (2H, 3′-H, 5′-H, J =
8.7 Hz), 7.40–7.82 m (5H, C6H5), 7.86 d (2H, 2′-H,
6′-H, J = 8.7 Hz).
N-(3-Chloro-4-hydroxy-2,5-dimethylphenyl)-N′-
(4-chlorophenylsulfonyl)benzenecarboximidamide
(IVc). Yield 60%, mp 232°C. Found, %: Cl 15.67,
15.82; N 6.13, 6.24; S 7.09, 7.25. C21H18Cl2N2O3S.
Calculated, %: Cl 15.78; N 6.23; S 7.14.
N-(3-Chloro-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(phenylsulfonyl)benzenecarboximid-
amide (Va). Yield 98%, mp 183–184°C. Found, %:
Cl 8. 11, 8. 26; N 6. 30, 6. 54; S 7. 19, 7. 38.
C23H23ClN2O3S. Calculated, %: Cl 8.00; N 6.32; S 7.24.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene)benzenecarbox-
imidamide (XVIb). Yield 84%, mp 175–177°C; pub-
lished data [14]: mp 175–177°C. 1H NMR spectrum, δ,
ppm: 2.07 s (6H, Me), 6.74 s (2H, 2-H, 6-H), 7.42–
7.81 m (5H, C6H5), 7.49 d (2H, 3′-H, 5′-H, J = 8.1 Hz),
7.92 d (2H, 2′-H, 6′-H, J = 8.1 Hz)..
N-(3-Chloro-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(4-methylphenylsulfonyl)benzenecar-
boximidamide (Vb). Yield 96%, mp 172–174°C.
Found, %: Cl 7.55, 7.69; N 6.20, 6.47; S 7.13, 7.25.
C24H25ClN2O3S. Calculated, %: Cl 7.76; N 6.13; S 7.02.
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)-N′-(4-methylphenylsulfonyl)benzenecarbox-
imidamide (XXIa). Yield 79%, mp 131–132°C; pub-
lished data [14]: mp 122–124°C. 1H NMR spectrum, δ,
ppm: 2.08 s (6H, 2-Me, 6-Me), 2.43 s (3H, MeC6H4),
6.49 s (2H, 3-H, 5-H), 7.32 d (2H, 3′-H, 5′-H, J =
8.1 Hz), 7.44–7.79 m (5H, C6H5), 7.86 d (2H, 2′-H,
6′-H, J = 8.1 Hz).
N-(3-Chloro-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(4-chlorophenylsulfonyl)benzenecarbox-
imidamide (Vc). Yield 89%, mp 176–178°C. Found,
%: Cl 14.70, 14.93; N 5.88, 6.12; S 6.75, 6.83.
C23H22Cl2N2O3S. Calculated, %: Cl 14.85; N 5.87;
S 6.72.
N-(3-Chloro-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(phenylsulfonyl)benzenecarboximid-
amide (VIa). Yield 88%, mp 168–170°C. Found, %:
Cl 7. 88, 8. 06; N 6. 13, 6. 35; S 7. 42, 7. 56.
C23H23ClN2O3S. Calculated, %: Cl 8.00; N 6.32; S 7.24.
N′-(4-Chlorophenylsulfonyl)-N-(2,6-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene)benzenecarbox-
imidamide (XXIb). Yield 82%, mp 173–175°C; pub-
lished data [14]: mp 175–176°C. 1H NMR spectrum, δ,
ppm: 2.10 s (6H, Me), 6.51 s (2H, 3-H, 5-H), 7.47–
7.78 m (5H, C6H5), 7.48 d (2H, 3′-H, 5′-H, J = 8.4 Hz),
7.93 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
N-(3-Chloro-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(4-methylphenylsulfonyl)benzenecar-
boximidamide (VIb). Yield 74%, mp 176–177°C.
Found, %: Cl 7.48, 7.66; N 6.00, 6.27; S 7.15, 7.39.
C24H25ClN2O3S. Calculated, %: Cl 7.76; N 6.13; S 7.02.
Hydrochlorination of N-[arylsulfonylimino-
(phenyl)methyl]-1,4-benzoquinone imines (general
procedure). Dry gaseous hydrogen chloride was
passed over a period of 25–35 min through a solution
of 0.01 mol of quinone imine I–III, X–XII, XVI,
XVIII, XXI, or XXIV in 5 ml of anhydrous chloro-
form. The solution turned lighter, and a colorless solid
separated. The precipitate was filtered off, washed with
a small amount of acetic acid, dried, and recrystallized
from acetic acid.
N-(3-Chloro-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(4-chlorophenylsulfonyl)benzenecarbox-
imidamide (VIc). Yield 62%, mp 167–169°C. Found,
%: Cl 14.84, 15.06; N 6.02, 6.33; S 6.59, 6.78.
C23H22Cl2N2O3S. Calculated, %: Cl 14.85; N 5.87;
S 6.72.
N-(2-Chloro-4-hydroxy-3,5-dimethylphenyl)-N′-
(4-methylphenylsulfonyl)benzenecarboximidamide
(XVIIa). Yield 59%, mp 262°C. Found, %: Cl 8.01,
8.34; N 6.72, 6.95; S 7.15, 7.34. C22H21ClN2O3S. Cal-
culated, %: Cl 8.27; N 6.53; S 7.48.
N-(3-Chloro-4-hydroxy-2,5-dimethylphenyl)-N′-
(phenylsulfonyl)benzenecarboximidamide (IVa).
Yield 85%, mp 210°C. Found, %: Cl 8.49, 8.66;
N 6.53, 6.70; S 7.49, 7.75. C21H19ClN2O3S. Calculated,
%: Cl 8.54; N 6.75; S 7.73.
N-(2-Chloro-4-hydroxy-3,5-dimethylphenyl)-N′-
(4-chlorophenylsulfonyl)benzenecarboximidamide
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AVDEENKO et al.
1040
(XVIIb). Yield 77%, mp 222–224°C. Found, %:
Cl 15.28, 15.43; N 6.09, 6.37; S 7.51, 7.77.
C21H18Cl2N2O3S. Calculated, %: Cl 15.78; N 6.23;
S 7.14.
N-(2,6-Dichloro-4-hydroxy-3,5-dimethylphenyl)-
N′-(4-methylphenylsulfonyl)benzenecarboximid-
amide (XIXa). Yield 77%, mp 230–232°C. Found, %:
Cl 15.01, 15.22; N 6.08, 6.34; S 6.97, 7.14.
C22H20Cl2N2O3S. Calculated, %: Cl 15.30; N 6.05;
S 6.92.
N′-(4-Chlorophenylsulfonyl)-N-(2,6-dichloro-
4-hydroxy-3,5-dimethylphenyl)benzenecarboximid-
amide (XIXb). Yield 68%, mp 268.5–269°C. Found,
%: Cl 21.68, 21.83; N 5.49, 5.67; S 6.30, 7.42.
C21H17Cl3N2O3S. Calculated, %: Cl 21.98; N 5.79;
S 6.63.
N-(3-Chloro-4-hydroxy-2,6-dimethylphenyl)-N′-
(4-methylphenylsulfonyl)benzenecarboximidamide
(XXIIa). Yield 66%, mp 28°C. Found, %: Cl 8.31,
8.54; N 6.39, 6.52; S 7.19, 6.48. C22H21ClN2O3S. Cal-
culated, %: Cl 8.27; N 6.53; S 7.48.
N-(3-Chloro-4-hydroxy-2,6-dimethylphenyl)-N′-
(4-chlorophenylsulfonyl)benzenecarboximidamide
(XXIIb). Yield 76%, mp 276–27°C. Found, %:
Cl 15.62, 15.79; N 5.98, 6.19; S 7.23, 7.44.
C21H18Cl2N2O3S. Calculated, %: Cl 15.78; N 6.23;
S 7.14.
N-(3,5-Dichloro-4-hydroxy-2,6-dimethylphenyl)-
N′-(4-methylphenylsulfonyl)benzenecarboximid-
amide (XXVIa). Yield 71%, mp 29°C. Found, %:
Cl 15.02, 15.27; N 6.30, 6.47; S 6.49, 6.68.
C22H20Cl2N2O3S. Calculated, %: Cl 15.30; N 6.05;
S 6.92.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dichloro-
4-hydroxy-2,6-dimethylphenyl)benzenecarboximid-
amide (XXVIb). Yield 78%, mp 305–307°C. Found,
%: Cl 21.62, 21.80; N 5.37, 5.69; S 6.24, 6.51.
C21H17Cl3N2O3S. Calculated, %: Cl 21.98; N 5.79;
S 6.63.
Chloro-substituted N-[arylsulfonylimino-
(phenyl)methyl]-1,4-benzoquinone imines X–XII,
XVIII, XX, XXIV, and XXVIII (general procedure).
Lead tetraacetate, 6.5 mmol, was added at room tem-
perature under vigorous stirring to 5 mmol of amino-
phenol IV–VI, XVII, XIX, XXII, or XXVI in 10 ml
of acetic acid. The reaction was accompanied by heat
evolution, so that the mixture was cooled. When the
reaction was complete, 2 ml of ethylene glycol was
added, the mixture was stirred for 2 min, and the
yellow precipitate was filtered off, washed with meth-
anol, dried, and recrystallized from acetic acid.
N-(3-Chloro-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(phenylsulfonyl)benzenecarbox-
imidamide (Xa). Yield 96%, mp 173–174°C. 1H NMR
spectrum, δ, ppm: 2.14 d (3H, 5-Me, J = 1.2 Hz),
2.37 s (3H, 2-Me), 6.48 q (1H, 6-H, J = 1.8 Hz), 7.43–
7.98 m (10H, Harom). Found, %: Cl 8.40, 8.56; N 6.43,
6.77; S 7.29, 7.45. C21H17ClN2O3S. Calculated, %:
Cl 8.59; N 6.78; S 7.77.
N-(3-Chloro-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (Xb). Yield 85%, mp 158–160°C.
1H NMR spectrum, δ, ppm: 2.00 d (3H, 5-Me, J =
1.8 Hz), 2.38 s (3H, 2-Me), 2.43 s (3H, MeC6H4),
6.45 q (1H, 6-H, J = 1.5 Hz), 7.31 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 7.42–7.79 m (5H, C6H5), 7.84 d (2H, 2′-H,
6′-H, J = 8.1 Hz),. Found, %: Cl 8.09, 8.26; N 6.33,
6.57; S 7.29, 7.44. C22H19ClN2O3S. Calculated, %:
Cl 8.30; N 6.56; S 7.51.
N-(3-Chloro-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-chlorophenylsulfonyl)benzene-
carboximidamide (Xc). Yield 94%, mp 168–170°C.
1H NMR spectrum, δ, ppm: 2.03 d (3H, 5-Me, J =
1.5 Hz), 2.10 s (3H, 2-Me), 6.48 q (1H, 6-H, J =
1.5 Hz), 7.44–7.78 m (5H, C6H5), 7.48 d (2H, 3′-H,
5′-H, J = 8.7 Hz), 7.92 d (2H, 2′-H, 6′-H, J = 8.7 Hz).
Found, %: Cl 15.69, 15.82; N 6.30, 6.47; S 7.19, 7.34.
C21H16Cl2N2O3S. Calculated, %: Cl 15.85; N 6.26;
S 7.17.
N-(3-Chloro-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(phenylsulfonyl)ben-
zenecarboximidamide (XIa). Yield 78%, mp 168.5–
1
170°C. H NMR spectrum, δ, ppm: 1.04 d (6H,
CHMe2, J = 20.4 Hz), 2.35 s (3H, Me), 2.99–3.08 m
(1H, CHMe2), 6.41 s (1H, 6-H), 7.43–7.97 m (10H,
Harom). Found, %: Cl 7.69, 7.84; N 6.01, 6.35; S 7.29,
7.58. C23H21ClN2O3S. Calculated, %: Cl 8.04; N 6.35;
S 7.27.
N-(3-Chloro-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-methylphenylsul-
fonyl)benzenecarboximidamide (XIb). Yield 41%,
1
mp 146–148°C. H NMR spectrum, δ, ppm: 1.03 d
(6H, CHMe2, J = 22.8 Hz), 2.36 s (3H, 2-Me), 2.43 s
(3H, MeC6H4), 2.96–3.07 m (1H, CHMe2), 6.39 s (1H,
6-H), 7.30 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.42–7.79 m
(5H, C6H5), 7.84 d (2H, 2′-H, 6′-H, J = 8.4 Hz). Found,
%: Cl 7.53, 7.89; N 5.62, 5.84; S 6.91, 7.08.
C24H23ClN2O3S. Calculated, %: Cl 7.79; N 6.16; S 7.05.
N-(3-Chloro-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-chlorophenylsul-
fonyl)benzenecarboximidamide (XIc). Yield 53%,
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HYDROHALOGENATION OF N-[ARYLSULFONYLIMINO(PHENYL)METHYL]-...
1041
1
1
mp 141–143°C. H NMR spectrum, δ, ppm: 1.05 d
195°C. H NMR spectrum, δ, ppm: 2.02 d (3H, 5-Me,
J = 1.5 Hz), 2.30 s (3H, 3-Me), 6.56 q (1H, 6-H, J =
1.8 Hz), 7.42–7.81 m (5H, C6H5), 7.50 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.94 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: Cl 15.60, 15.73; N 6.29, 6.48; S 7.05, 7.32.
C21H16Cl2N2O3S. Calculated, %: Cl 15.85; N 6.26;
S 7.17.
(6H, CHMe2, J = 18.3 Hz), 2.39 s (3H, Me), 3.00–
3.10 m (1H, CHMe2), 6.41 s (1H, 6-H), 7.44–7.79 m
(5H, C6H5), 7.47 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.92 d
(2H, 2′-H, 6′-H, J = 8.7 Hz). Found, %: Cl 14.80,
15.22; N 5.36, 5.74; S 6.81, 6.97. C23H20Cl2N2O3S.
Calculated, %: Cl 14.92; N 5.89; S 6.75.
N-(2,6-Dichloro-3,5-dimethyl-4-oxocyclohexa-
2,5-dien-1-ylidene)-N′-(4-methylphenylsulfonyl)-
benzenecarboximidamide (XXa). Yield 70%,
N-(3-Chloro-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(phenylsulfonyl)ben-
zenecarboximidamide (XIIa). Yield 78%, mp 128–
1
1
mp 172–173°C. H NMR spectrum, δ, ppm: 2.10 s
130°C. H NMR spectrum, δ, ppm: 1.52 d (6H,
(3H, 3-Me), 2.24 s (3H, 5-Me), 2.42 s (3H, MeC6H4),
7.29 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.42–7.79 m (5H,
C6H5), 7.87 d (2H, 2′-H, 6′-H, J = 8.7 Hz). Found, %:
Cl 15.09, 15.32; N 6.18, 6.47; S 6.51, 6.89.
C22H18Cl2N2O3S. Calculated, %: Cl 15.37; N 6.07;
S 6.95.
CHMe2, J = 7.2 Hz), 1.98 d (3H, Me, J = 1.2 Hz),
3.72–3.82 m (1H, CHMe2), 6.42 q (1H, 6-H, J =
1.2 Hz), 7.44–8.02 m (10H, Harom). Found, %: Cl 7.79,
8.14; N 6.25, 6.49; S 7.53, 7.80. C23H21ClN2O3S. Cal-
culated, %: Cl 8.04; N 6.35; S 7.27.
N-(3-Chloro-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-methylphenylsul-
fonyl)benzenecarboximidamide (XIIb). Yield 75%,
N′-(4-Chlorophenylsulfonyl)-N-(2,6-dichloro-3,5-
dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)ben-
zenecarboximidamide (XXb). Yield 74%, mp 175–
1
mp 153–154°C. H NMR spectrum, δ, ppm: 1.52 d
1
176°C. H NMR spectrum, δ, ppm: 2.26 s (6H, Me),
(6H, CHMe2, J = 6.9 Hz), 1.96 d (3H, 5-Me, J =
1.2 Hz), 2.43 s (3H, MeC6H4), 3.72–3.82 m (1H,
CHMe2), 6.38 q (1H, 6-H, J = 1.2 Hz), 7.31 d (2H,
3′-H, 5′-H, J = 7.8 Hz), 7.43–7.78 m (5H, C6H5),
7.88 d (2H, 2′-H, 6′-H, J = 7.8 Hz). Found, %: Cl 7.51,
7.83; N 6.05, 6.49; S 7.22, 7.53. C24H23ClN2O3S. Cal-
culated, %: Cl 7.79; N 6.16; S 7.05.
7.43–7.79 m (5H, C6H5), 7.47 d (2H, 3′-H, 5′-H, J =
9.0 Hz), 7.91 d (2H, 2′-H, 6′-H, J = 9.0 Hz). Found, %:
Cl 22.10, 22.34; N 5.78, 5.91; S 6.73, 6.82.
C21H15Cl3N2O3S. Calculated, %: Cl 22.08; N 5.81;
S 6.66.
N-(3-Chloro-2,6-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (XXIVa). Yield 88%, mp 159–
N-(3-Chloro-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-chlorophenylsul-
fonyl)benzenecarboximidamide (XIIc). Yield 72%,
1
160°C. H NMR spectrum, δ, ppm: 2.10 d (3H, 6-Me,
1
J = 0.9 Hz), 2.25 s (3H, 2-Me), 2.44 s (3H, MeC6H4),
6.61 q (1H, 5-H, J = 1.2 Hz), 7.32 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 7.44–7.76 m (5H, C6H5), 7.84 d (2H, 2′-H,
6′-H, J = 8.4 Hz). Found, %: Cl 8.09, 8.34; N 6.58,
6.71; S 7.51, 7.76. C22H19ClN2O3S. Calculated, %:
Cl 8.30; N 6.56; S 7.51.
mp 159°C. H NMR spectrum, δ, ppm: 1.52 d (6H,
CHMe2, J = 6.9 Hz), 2.00 d (3H, Me, J = 1.8 Hz),
3.72–3.82 m (1H, CHMe2), 6.43 q (1H, 6-H, J =
1.8 Hz), 7.44–7.77 m (5H, C6H5), 7.68 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.88 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: Cl 14.50, 14.73; N 5.62, 5.81; S 6.79, 6.94.
C24H20Cl2N2O3S. Calculated, %: Cl 14.92; N 5.89;
S 6.75.
N-(3-Chloro-2,6-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-chlorophenylsulfonyl)benzene-
carboximidamide (XXIVb). Yield 78%, mp 170–
N-(2-Chloro-3,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (XVIIIa). Yield 56%, mp 194–
1
171°C. H NMR spectrum, δ, ppm: 2.11 d (3H, 6-Me,
J = 1.2 Hz), 2.29 s (3H, 2-Me), 6.63 q (1H, 5-H, J =
1.2 Hz), 7.45–7.76 m (5H, C6H5), 7.67 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.86 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: Cl 15.69, 15.84; N 6.07, 6.19; S 7.22, 7.43.
C21H16Cl2N2O3S. Calculated, %: Cl 15.85; N 6.26;
S 7.17.
1
196°C. H NMR spectrum, δ, ppm: 1.99 d (3H, 5-Me,
J = 1.5 Hz), 2.29 s (3H, 3-Me), 2,42 s (3H, MeC6H4),
6.54 q (1H, 6-H, J = 1.8 Hz), 7.30 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 7.41–7.82 m (5H, C6H5), 7.87 d (2H, 2′-H,
6′-H, J = 8.1 Hz). Found, %: Cl 8.32, 8.51; N 6.04,
6.37; S 7.49, 7.63. C22H19ClN2O3S. Calculated, %:
Cl 8.30; N 6.56; S 7.51.
N-(2-Chloro-3,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-chlorophenylsulfonyl)benzene-
carboximidamide (XVIIIb). Yield 78%, mp 193–
N-(3,5-Dichloro-2,6-dimethyl-4-oxocyclohexa-
2,5-dien-1-ylidene)-N′-(4-methylphenylsulfonyl)-
benzenecarboximidamide (XXVIIIa). Yield 53%,
1
mp 216–218°C. H NMR spectrum, δ, ppm: 2.26 s
(6H, 2-Me, 6-Me), 2.44 s (3H, MeC6H4), 7.32 d (2H,
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AVDEENKO et al.
1042
3′-H, 5′-H, J = 8.4 Hz), 7.44–7.76 m (5H, C6H5), 7.84 d
(2H, 2′-H, 6′-H, J = 8.4 Hz). Found, %: Cl 15.09,
15.32; N 6.18, 6.47; S 6.51, 6.89. C22H18Cl2N2O3S.
Calculated, %: Cl 15.37; N 6.07; S 6.95.
C24H25BrN2O3S. Calculated, %: Br 15.94; N 5.59;
S 6.39.
N-(3-Bromo-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(4-chlorophenylsulfonyl)benzenecar-
boximidamide (VIIIc). Yield 86%, mp 155–156°C.
Found, %: Br 15.09, 15.31; N 5.42, 5.67; S 6.24, 6.38.
C23H22BrClN2O3S. Calculated, %: Br 15.31; N 5.37;
S 6.14.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dichloro-2,6-
dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)ben-
zenecarboximidamide (XXVIIIb). Yield 81%,
1
mp 218–220°C. H NMR spectrum, δ, ppm: 2.29 s
(6H, Me), 7.46–7.75 m (5H, C6H5), 7.69 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.86 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: Cl 21.87, 22.09; N 5.64, 5.83; S 6.21, 6.49.
C21H15Cl3N2O3S. Calculated, %: Cl 22.08; N 5.81;
S 6.66.
N-(3-Bromo-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(phenylsulfonyl)benzenecarboximid-
amide (IXa). Yield 73%, mp 153°C. Found, %:
Br 16.44, 16.62; N 5.37, 5.49; S 6.78, 6.90.
C23H23BrN2O3S. Calculated, %: Br 16.39; N 5.75;
S 6.58.
N-(3-Bromo-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(4-methylphenylsulfonyl)benzenecar-
boximidamide (IXb). Yield 70%, mp 147–149°C.
Found, %: Br 15.70, 15.83; N 5.41, 5.69; S 6.07, 6.31.
C24H25BrN2O3S. Calculated, %: Br 15.94; N 5.59;
S 6.39.
N-(3-Bromo-4-hydroxy-2-isopropyl-5-methyl-
phenyl)-N′-(4-chlorophenylsulfonyl)benzenecar-
boximidamide (IXc). Yield 72%, mp 149.5–150°C.
Found, %: Br 15.42, 15.66; N 5.19, 5.38; S 6.06, 6.27.
C23H22BrClN2O3S. Calculated, %: Br 15.31; N 5.37;
S 6.14.
N-(3-Bromo-4-hydroxy-2,6-dimethylphenyl)-N′-
(4-methylphenylsulfonyl)benzenecarboximidamide
(XXIIIa). Yield 73%, mp 260.5–262°C. Found, %:
Br 16.42, 16.70; N 5.89, 6.14 S 6.39, 6.58.
C22H21BrN2O3S. Calculated, %: Br 16.88; N 5.92;
S 6.77.
N-(3-Bromo-4-hydroxy-2,6-dimethylphenyl)-N′-
(4-chlorophenylsulfonyl)benzenecarboximidamide
(XXIIIb). Yield 74%, mp 250–251°C. Found, %:
Br 16.03, 16.29; N 5.75, 5.94; S 6.32, 6.48.
C21H18BrClN2O3S. Calculated, %: Br 16.18; N 5.67;
S 6.49.
N-(3,5-Dibromo-4-hydroxy-2,6-dimethylphenyl)-
N′-(4-methylphenylsulfonyl)benzenecarboximid-
amide (XXVIIa). Yield 91%, mp 273–274°C. Found,
%: Br 28.73, 28.94; N 5.16, 5.33; S 5.41, 5.60.
C22H20Br2N2O3S. Calculated, %: Br 28.94; N 5.07;
S 5.81.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dibromo-4-
hydroxy-2,6-dimethylphenyl)benzenecarboximid-
amide (XXVIIb). Yield 95%, mp 290–291.5°C.
Found, %: Br 27.60, 27.82; N 4.53, 4.79; S 5.61, 5.88.
C21H17Br2ClN2O3S. Calculated, %: Br 27.90; N 4.89;
S 5.60.
Hydrobromination of N-[arylsulfonylimino-
(phenyl)methyl]-1,4-benzoquinone imines (general
procedure). A solution of 0.01 mol of quinone imine
I–III, XIII–XV, XXI, or XXV in 10 ml of acetic acid
was heated to 50–60°C, and 2 ml of 40% hydrobromic
acid was added in portions under stirring. The mixture
turned lighter and was diluted with water, and the
colorless precipitate was filtered off and recrystallized
from acetic acid.
N-(3-Bromo-4-hydroxy-2,5-dimethylphenyl)-N′-
(phenylsulfonyl)benzenecarboximidamide (VIIa).
Yield 63%, mp 210–212°C. Found, %: Br 17.40,
17.63; N 6.25, 6.41; S 6.58, 6.79. C21H19BrN2O3S. Cal-
culated, %: Br 17.39; N 6.10; S 6.98.
N-(3-Bromo-4-hydroxy-2,5-dimethylphenyl)-N′-
(4-methylphenylsulfonyl)benzenecarboximidamide
(VIIb). Yield 79%, mp 190–191°C. Found, %:
Br 16.53, 16.77; N 5.32, 5.49; S 6.08, 6.31.
C22H21BrN2O3S. Calculated, %: Br 16.88; N 5.92;
S 6.77.
N-(3-Bromo-4-hydroxy-2,5-dimethylphenyl)-N′-
(4-chlorophenylsulfonyl)benzenecarboximidamide
(VIIc). Yield 58%, mp 270–272°C. Found, %:
Br 15.79, 16.03; N 5.44, 5.62; S 6.38, 6.50.
C21H18BrClN2O3S. Calculated, %: Br 16.18; N 5.67;
S 6.49.
N-(3-Bromo-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(phenylsulfonyl)benzenecarboximid-
amide (VIIIa). Yield 93%, mp 152–154°C. Found, %:
Br 16.07, 16.29; N 5.42, 5.63; S 6.19, 6.37.
C23H23BrN2O3S. Calculated, %: Br 16.39; N 5.75;
S 6.58.
N-(3-Bromo-4-hydroxy-5-isopropyl-2-methyl-
phenyl)-N′-(4-methylphenylsulfonyl)benzenecar-
boximidamide (VIIIb). Yield 84%, mp 156–158°C.
Found, %: Br 15.61, 15.84; N 5.67, 5.90; S 6.24, 6.43.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011

HYDROHALOGENATION OF N-[ARYLSULFONYLIMINO(PHENYL)METHYL]-...
1043
Bromo-substituted N-[arylsulfonylimino-
(phenyl)methyl]-1,4-benzoquinone imines XIII–XV,
XXV, and XXIX (general procedure). Lead tetra-
acetate, 6.5 mmol, was added under vigorous stirring
at room temperature to 5 mmol of aminophenol VII–
IX, XXIII, or XXVII in 10 ml of acetic acid. The
reaction was accompanied by heat evolution, so that
the mixture was cooled. When the reaction was com-
plete, 2 ml of ethylene glycol was added, and the
mixture was stirred for 2 min. The yellow precipitate
was filtered off, washed with methanol, dried, and
recrystallized from acetic acid.
N-(3-Bromo-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(phenylsulfonyl)benzenecarbox-
imidamide (XIIIa). Yield 87%, mp 210.5–212°C.
1H NMR spectrum, δ, ppm: 2.02 d (3H, 5-Me, J =
1.2 Hz), 2.41 s (3H, 2-Me), 6.47 q (1H, 6-H, J =
1.5 Hz), 7.43–7.97 m (10H, Harom). Found, %: Br 17.42,
17.69; N 5.33, 5.68; S 7.29, 7.44. C21H17BrN2O3S.
Calculated, %: Br 17.47; N 6.13; S 7.01.
fonyl)benzenecarboximidamide (XIVb). Yield 91%,
mp 136–138°C. H NMR spectrum, δ, ppm: 1.03 d
1
(6H, CHMe2, J = 18.6 Hz), 2.41 s (3H, 2-Me), 2.43 s
(3H, MeC6H4), 2.99–3.08 m (1H, CHMe2), 6.38 q (1H,
6-H, J = 1.2 Hz), 7.31 d (2H, 3′-H, 5′-H, J = 8.1 Hz),
7.42–7.78 m (5H, C6H5), 7.84 d (2H, 2′-H, 6′-H, J =
8.1 Hz). Found, %: Br 16.12, 16.49; N 5.73, 5.88;
S 6.27, 6.59. C24H23BrN2O3S. Calculated, %: Br 16.00;
N 5.61; S 6.42.
N-(3-Bromo-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-chlorophenylsul-
fonyl)benzenecarboximidamide (XIVc). Yield 95%,
1
mp 157–158°C. H NMR spectrum, δ, ppm: 1.04 d
(6H, CHMe2, J = 10.5 Hz), 2.43 s (3H, Me), 3.01–
3.10 m (1H, CHMe2), 6.40 q (1H, 6-H, J = 1.2 Hz),
7.43–7.78 m (5H, C6H5), 7.50 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 7.92 d (2H, 2′-H, 6′-H, J = 8.7 Hz).
Found, %: Br 15.26, 15.49; N 5.27, 5.63; S 6.01, 6.30.
C23H20BrClN2O3S. Calculated, %: Br 15.37; N 5.39;
S 6.17.
N-(3-Bromo-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (XIIIb). Yield 79%, mp 190–
N-(3-Bromo-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(phenylsulfonyl)ben-
zenecarboximidamide (XVa). Yield 75%, mp 134–
136°C. 1H NMR spectrum, δ, ppm: 1.52–1.56 d.d (6H,
CHMe2, J = 7.5 Hz), 1.98 d (3H, Me, J = 1.2 Hz),
3.74–3.84 m (1H, CHMe2), 6.40 q (1H, 6-H, J =
0.9 Hz), 7.44–8.02 m (10H, Harom). Found, %: Br 16.08,
16.34; N 5.29, 5.50; S 6.71, 6.93. C23H21BrN2O3S. Cal-
culated, %: Br 16.46; N 5.77; S 6.61.
1
191.5°C. H NMR spectrum, δ, ppm: 2.00 d (3H,
5-Me, J = 1.5 Hz), 2.41 s (3H, 2-Me), 2.43 s (3H,
MeC6H4), 6.43 q (1H, 6-H, J = 1.8 Hz), 7.31 d (2H,
3′-H, 5′-H, J = 8.1 Hz), 7.43–7.78 m (5H, C6H5), 7.84 d
(2H, 2′-H, 6′-H, J = 8.1 Hz). Found, %: Br 16.82,
17.04; N 5.69, 5.94; S 6.83, 7.02. C22H19BrN2O3S.
Calculated, %: Br 16.95; N 5.94; S 6.80.
N-(3-Bromo-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-methylphenylsul-
fonyl)benzenecarboximidamide (XVb). Yield 88%,
N-(3-Bromo-2,5-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-chlorophenylsulfonyl)benzene-
carboximidamide (XIIIc). Yield 99%, mp 225.5–
1
mp 94°C. H NMR spectrum, δ, ppm: 1.52–1.56 d.d
1
227°C. H NMR spectrum, δ, ppm: 2.04 d (3H, 5-Me,
(6H, CHMe2, J = 9.6 Hz), 1.96 d (3H, 5-Me, J =
1.2 Hz), 2.42 s (3H, MeC6H4), 3.74–3.83 m (1H,
CHMe2), 6.38 q (1H, 6-H, J = 1.2 Hz), 7.43–7.78 m
(5H, C6H5), 7.47 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.88 d
(2H, 2′-H, 6′-H, J = 8.1 Hz). Found, %: Br 15.87,
16.04; N 5.39, 5.62; S 6.37, 6.50. C24H23BrN2O3S. Cal-
culated, %: Br 16.00; N 5.61; S 6.42.
J = 1.5 Hz), 2.44 s (3H, 2-Me), 6.47 q (1H, 6-H, J =
1.5 Hz), 7.44–7.78 m (5H, C6H5), 7.50 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.44–7.78 m (5H, Ph), 7.92 d (2H,
2′-H, 6′-H, J = 8.4 Hz). Found, %: Br 16.09, 16.34;
N 5.68, 5.92; S 6.33, 6.52. C21H16BrClN2O3S. Cal-
culated, %: Br 16.25; N 5.70; S 6.52.
N-(3-Bromo-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(phenylsulfonyl)ben-
zenecarboximidamide (XIVa). Yield 85%, mp 157–
N-(3-Bromo-2-isopropyl-5-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-chlorophenylsul-
fonyl)benzenecarboximidamide (XVc). Yield 79%,
1
1
159°C. H NMR spectrum, δ, ppm: 1.04 d (6H,
mp 132–133°C. H NMR spectrum, δ, ppm: 1.47–
CHMe2, J = 10.2 Hz), 2.40 s (3H, Me), 2.99–3.09 m
(1H, CHMe2), 6.40 q (1H, 6-H, J = 0.9 Hz), 7.43–
7.97 m (10H, Harom). Found, %: Br 16.58, 16.82;
N 5.44, 5.79; S 6.23, 6.50. C23H21BrN2O3S. Calculat-
ed, %: Br 16.46; N 5.77; S 6.61.
1.51 d.d (6H, CHMe2, J = 10.5 Hz), 2.00 d (3H, Me,
J = 1.6 Hz), 3.73–3.84 m (1H, CHMe2), 6.42 q (1H,
6-H, J = 1.5 Hz), 7.44–7.77 m (5H, C6H5), 7.49 d (2H,
3′-H, 5′-H, J = 8.1 Hz), 7.94 d (2H, 2′-H, 6′-H, J =
8.1 Hz). Found, %: Br 14.92, 15.20; N 5.37, 5.64;
S 6.11, 6.38. C23H20BrClN2O3S. Calculated, %:
Br 15.37; N 5.39; S 6.17.
N-(3-Bromo-5-isopropyl-2-methyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene)-N′-(4-methylphenylsul-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011

AVDEENKO et al.
1044
1985, vol. 21, p. 1544; Toropin, N.V., Burmistrov, K.S.,
N-(3-Bromo-2,6-dimethyl-4-oxocyclohexa-2,5-di-
Burmistrov, S.I., and Zaichenko, N.L., Zh. Org. Khim.,
1986, vol. 22, p. 999; Burmistrov, K.S., Toropin, N.V.,
and Burmistrov, S.I., Zh. Org. Khim., 1993, vol. 29,
p. 1170.
en-1-ylidene)-N′-(4-methylphenylsulfonyl)benzene-
carboximidamide (XXVa). Yield 83%, mp 188–
189°C. H NMR spectrum, δ, ppm: 2.09 d (3H, 6-Me,
J = 1.2 Hz), 2.30 s (3H, 2-Me), 2.44 s (3H, MeC6H4),
6.65 q (1H, 5-H, J = 1.2 Hz), 7.32 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 7.44–7.77 m (5H, C6H5), 7.85 d (2H, 2′-H,
6′-H, J = 8.7 Hz). Found, %: Br 16.89, 17.14; N 5.83,
6.02; S 6.59, 6.84. C22H19BrN2O3S. Calculated, %:
Br 16.95; N 5.94; S 6.80.
1
3. Toropin, N.V. and Burmistrov, K.S., Zh. Org. Khim.,
1983, vol. 19, p. 1546; Burmistrov, K.S. and Yurchen-
ko, A.G., Zh. Org. Khim., 1985, vol. 21, p. 575.
4. Avdeenko, A.P. and Velichko, N.V., Zh. Org. Khim.,
1993, vol. 29, p. 1167.
5. Avdeenko, A.P. and Velichko, N.V., Zh. Org. Khim.,
N-(3-Bromo-2,6-dimethyl-4-oxocyclohexa-2,5-di-
en-1-ylidene)-N′-(4-chlorophenylsulfonyl)benzene-
carboximidamide (XXVb). Yield 93%, mp 208–
1992, vol. 28, p. 1257.
6. Avdeenko, A.P., Konovalova, S.A., and Ludchen-
ko, O.N., Russ. J. Org. Chem., 2009, vol. 45, p. 1799;
Avdeenko, A.P., Konovalova, S.A., Ludchenko, O.N.,
Palamarchuk, G.V., and Shishkin, O.V., Russ. J. Org.
Chem., 2009, vol. 45, p. 1651.
7. Avdeenko, A.P., Konovalova, S.A., Ludchenko, O.N.,
Ledeneva, O.P., and Vakulenko, A.V., Russ. J. Org.
Chem., 2011, vol. 47, p. 214.
1
209.5°C. H NMR spectrum, δ, ppm: 2.10 d (3H,
6-Me, J = 1.2 Hz), 2.31 s (3H, 2-Me), 6.63 q (1H, 5-H,
J = 1.2 Hz), 7.45–7.76 m (5H, C6H5), 7.66 d (2H, 3′-H,
5′-H, J = 9.0 Hz), 7.85 d (2H, 2′-H, 6′-H, J = 9.0 Hz).
Found, %: Br 15.90, 16.24; N 5.71, 5.89; S 6.23, 6.40.
C21H16BrClN2O3S. Calculated, %: Br 16.25; N 5.70;
S 6.52.
8. Avdeenko, A.P., Marchenko, I.L., and Konovalo-
va, S.A., Russ. J. Org. Chem., 2001, vol. 37, p. 72.
9. Avdeenko, A.P. and Konovalova, S.A., Russ. J. Org.
Chem., 2006, vol. 42, p. 669.
10. Avdeenko, A.P., Pirozhenko, V.V., Yagupol’skii, L.M.,
and Marchenko, I.L., Russ. J. Org. Chem., 2001,
vol. 37, p. 991.
11. Burmistrov, K.S., Toropin, N.V., Vakulenko, A.V.,
Yurchenko, A.G., and Markov, V.I., Vopr. Khim. Khim.
Tekhnol., 2000, no. 2, p. 30.
N-(3,5-Dibromo-2,6-dimethyl-4-oxocyclohexa-
2,5-dien-1-ylidene)-N′-(4-methylphenylsulfonyl)-
benzenecarboximidamide (XXIXa). Yield 79%,
1
mp 234–236°C. H NMR spectrum, δ, ppm: 2.30 s
(6H, 2-Me, 6-Me), 2.44 s (3H, MeC6H4), 7.32 d (2H,
3′-H, 5′-H, J = 8.4 Hz), 7.44–7.76 m (5H, C6H5), 7.84 d
(2H, 2′-H, 6′-H, J = 8.4 Hz). Found, %: Br 29.09,
29.34; N 5.17, 5.48; S 5.93, 6.11. C22H18Br2N2O3S.
Calculated, %: Br 29.04; N 5.09; S 5.83.
12. Petrova, S.A., Burmistrov, K.S., Kolodyazhnyi, M.V.,
and Ksenzhek, O.S., Elektrokhimiya, 1979, vol. 15,
p. 1666.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dibromo-
2,6-dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)-
benzenecarboximidamide (XXIXb). Yield 84%,
13. Avdeenko, A.P., Burmistrov, K.S., Dubina, V.L., and
1
mp 238–240°C. H NMR spectrum, δ, ppm: 2.34 s
Skripets, V.I., Ukr. Khim. Zh., 1980, vol. 46, p. 1081.
(6H, Me), 7.46–7.76 m (5H, C6H5), 7.52 d (2H, 3′-H,
5′-H, J = 8.4 Hz), 7.92 d (2H, 2′-H, 6′-H, J = 8.4 Hz).
Found, %: Br 28.17, 28.39; N 4.75, 4.93; S 5.61, 5.80.
C21H15Br2ClN2O3S. Calculated, %: Br 28.00; N 4.91;
S 5.62.
14. 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.
15. Avdeenko, A.P., Konovalova, S.A., Roman’kov, D.A.,
Ludchenko, O.N., and Marchenko, I.L., Russ. J. Org.
Chem., 2009, vol. 45, p. 383.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 7 2011