Synthesis and 13C NMR spectra of N-substituted p-quinonimines: III. N-arylthio- and N-arylsulfonyl-1,4-benzoquinonimines with enhanced electron-donor character of quinoid ring

Article abstract of DOI:10.1023/B:RUJO.0000045891.38918.40

Incorporation of alkyl substituents into quinonimine fragments of N-arylthio- and N-arylsulfonyl-1,4-benzoquinonimines results in virtually equal changes in the chemical shifts of the carbon atoms from this fragment compared to those of unsubstituted and

Full text of DOI:10.1023/B:RUJO.0000045891.38918.40

Russian Journal of Organic Chemistry, Vol. 40, No. 8, 2004, pp. 1121-1128. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 8, 2004,
pp. 1169-1176.
Original Russian Text Copyright Ó 2004 by Pirozhenko, Avdeenko, Yusina, Konovalova.
Synthesis and 13C NMR Spectra of N-Substituted
p-Quinonimines: III.* N-Arylthio-
and N-Arylsulfonyl-1,4-benzoquinonimines with Enhanced
Electron-donor Character of Quinoid Ring
V.V. Pirozhenko1, A.P. Avdeenko2, A.L. Yusina2, and S.A. Konovalova2
1Institute of Organic Chemistry, National Academy of Sciences of the Ukraine, Kiev, Ukraine
2Donbass Machine-building Academy, Kramatorsk, 84313 Ukraine
å-mail: chimist@dgma.donetsk.ua
Received January 22 , 2003
Abstract—Incorporation of alkyl substituents into quinonimine fragments of N-arylthio- and N-arylsulfonyl-1,4-
benzoquinonimines results in virtually equal changes in the chemical shifts of the carbon atoms from this fragment
compared to those of unsubstituted and chloroderivatives. The substituents in the benzene ring also similarly
affect the spectra of both groups of alkyl-substituted compounds. The pattern observed is due to the lack of a
unique conjugation system, and the alterations revealed in the spectra might be caused by the changes in the
geometry of the molecules.
any significant changes in the chemical shifts of carbon
atoms at variation of substituents in the benzene ring. To
check the validity of this assumption we synthesized
several series of N-arylthio- and N-aryl-sulfonyl-1,4-
benzoquinonimines with electron-donor substituents in
the quinonimine fragment, and their 13C NMR spectra
were measured. We chose as electron-donor substituents
alkyl groups Me, i-Pr, and t-Bu. To facilitate the
assignment of signals in the NMR spectra compounds
I–IX were synthesized symmetrically substituted in the
quinonimine fragment.
The data obtained by analysis of 13C NMR spectra
are presented in Table 1. Introduction of methyls into 2
and 6 positions of the quinonimine fragment affected
virtually in the same manner the chemical shifts of carbon
atoms in the spectra of both types of compounds [N-aryl-
thio- (I) and N-arylsulfonyl- (II) -2,6-dimethyl-1,4-benzo-
quinonimines]: The signals from C3 and C5 were dis-
placed upfield whereas the other carbon signals shifted
downfield. The displacement in both cases also proved
to be equal. Moreover, in the spectra of both groups
compounds the changes in the chemical shifts of carbons
belonging to the benzene ring also were the same: the
introduction of methyl groups into the 2 and 6 positions
shifted downfield the signal from atom C1', and the degree
We formerly carried out a comparative investigation
of 13C NMR spectra of N-arylsulfonyl- and N-arylthio-
1,4-benzoquinonimines substituted by chlorine in the
quinonimine fragment. The study demonstrated that both
the substituents in the benzene ring and chlorine atoms
in the quinonimine moiety affected virtually in the same
manner the chemical shifts of carbon atoms in the spectra
of both groups of compounds [1]. Moreover, the changes
in the chemical shifts proved to be similar when
compared with those in the spectra of unsubstituted
quinonimines [2] suggesting a conclusion on insignificant
conjugation of the sulfur atom with the p-system of the
quinonimine fragment.
Chlorosubstituted compounds were chosen in order
to increase the electron-withdrawing character of the
quinonimine fragment since in this case it was
presumable that the interaction of the thioaryl part of the
molecule with the quinonimine moiety would be
enhanced. However it is still probable that the results
obtained may mean the attainment of the maximum
possible conjugation of the bivalent sulfur already in
the unsubstituted N-arylthio-1,4-benzoquinonimines.
Therefore further increase in the electron-with-drawing
character of the quinonimine fragment did not provide
* For Communication II see [1].
1070-4280/04/4008-1121Ó2004 MAIK “Nauka/Interperiodica”

1122
PIROZHENKO et al.
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R = MeO (a), Me (b), H (c), Cl (d), NO2 (e).
of the shift was virtually independent of the character of
substituents in the benzene ring. The identical transmis-
sion of electronic effects from one part of the molecule
to another is also clear from the similar character of
changes in the chemical shifts of carbon signals belonging
to the quinonimine fragment on variation of substituents
in the benzene ring. For instance, on going from the
electron-donor substituents (R = OMe) to electron-
withdrawing ones (R = NO2) the chemical shift of C4
carbon changed in both groups of compounds by 1.7 ppm.
Note that this value altered by virtually the same amount
at varying the substituents character in the benzene ring
both of unsubstituted [2] and 2,6-dichloro-substituted
compounds [1].
that observed in the other types of 2,6-disubstituted
benzoquinonimines [1, 3]. As expected the largest shift
of signals from atoms C1, C2, C4, and C6 in the series
Me, i-Pr, t-Bu as compared to the spectra of unsubstituted
compounds was observed for quinonimines IVa–e with
tert-butyl substituents whereas for atoms C3 and C5 the
maximal displacement occurred in quinonimine V with
isopropyl substituents (cf. 13C NMR spectra of com-
pounds IId, III, and IVd, Table 1). The same relations
were observed also in the N-arylthio derivatives: N-4-
chlorophenylthio-2,6-diisopropyl-1,4-benzoquinon-
imine (V), N-4-chlorophenylthio-2,6- di-tert-butyl-1,4-
benzoquinonimine (VI) [cf. 13C NMR spectra of com-
pounds Id, V, and VI, Table 1].
The increase in donor properties of substituents
attached to positions 2, 6 of the quinonimine fragment
[N-arylsulfonyl-2,6-diisopropyl-1,4-benzoquinonimines
(IIIa–e) and N-arylsulfonyl-2,6-di-tert-butyl-1,4-
benzoquinonimines (IVa–e)] does not result in
considerably different changes of the chemical shifts of
the benzene ring carbons as compared with 2,6-dimethyl
derivatives. The effect of the properties of substituents
at the benzene ring on the chemical shifts of carbons
belonging to the quinonimine fragment also is similar to
The observed pattern of changes in the carbon
chemical shifts in going from unsubstituted and chlorine-
containing 1,4-benzoquinonimines to the alkyl-sub-
stituted compounds, and also the similarity in transmis-
sion of the electronic effects from the benzene ring to
the quinonimine part of the molecule for all types of 2,6-
disubstituted benzoquinonimines in both groups of
compounds confirmes the former conclusion [1] on the
lack of conjugation between the p-systems of quinon-
imine and benzene fragments in N-arylthio derivatives.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

SYNTHESIS AND 13C NMR SPECTRA OF N-SUBSTITUTED p-QUINONIMINES: III.
1123
Table 1. Chemical shifts of carbon atoms (dC, ppm) in the 13C NMR spectra of N-arylthio- (I, V, VI, VII, X)
and N-arylsulfonyl- (II–IV, VIII, IX, XI) -1,4-benzoquinoniminesa
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,,,Dꢀ ꢂꢃꢎꢀꢇꢃꢁ ꢂꢎꢍꢀꢌꢍꢁ ꢂꢋꢋꢀꢇꢏꢁ ꢂꢌꢎꢀꢂꢋꢁ ꢂꢇꢋꢀꢍꢇꢁ ꢂꢎꢍꢀꢌꢂꢁ ꢂꢋꢇꢀꢂꢂꢁ ꢂꢇꢈꢀꢌꢃꢁ ꢂꢂꢍꢀꢇꢈꢁ ꢂꢌꢋꢀꢎꢎꢁ ꢇꢂꢀꢎꢋꢐꢁꢇꢏꢀꢂꢂꢐꢁ ꢎꢎꢀꢌꢃꢁ
ꢅ±ꢄꢀꢌꢂꢉꢁ ꢅꢆꢂꢈꢀꢎꢇꢉꢁ ꢅ±ꢏꢀꢇꢏꢉꢁ ꢅꢆꢂꢀꢃꢌꢉꢁ ꢅ±ꢌꢀꢏꢄꢉꢁ ꢅꢆꢂꢈꢀꢄꢈꢉꢁ ꢅꢆꢄꢀꢈꢏꢉꢁ ꢅ±ꢄꢀꢋꢄꢉꢁ ꢅ±ꢄꢀꢂꢂꢉꢁ ꢅ±ꢄꢀꢋꢍꢉꢁ ꢇꢏꢀꢃꢍꢁ
,,,Eꢀ ꢂꢃꢎꢀꢇꢍꢁ ꢂꢎꢍꢀꢏꢂꢁ ꢂꢋꢋꢀꢇꢂꢁ ꢂꢌꢎꢀꢍꢎꢁ ꢂꢇꢋꢀꢎꢇꢁ ꢂꢎꢍꢀꢌꢃꢁ ꢂꢋꢏꢀꢎꢃꢁ ꢂꢇꢏꢀꢍꢎꢁ ꢂꢇꢈꢀꢌꢃꢁ ꢂꢍꢍꢀꢋꢏꢁ ꢇꢂꢀꢎꢋꢐꢁꢇꢏꢀꢄꢈꢐꢁ ꢇꢂꢀꢎꢋꢁ
ꢅ±ꢄꢀꢎꢏꢉꢁ ꢅꢆꢂꢈꢀꢎꢎꢉꢁ ꢅ±ꢏꢀꢄꢍꢉꢁ ꢅꢆꢂꢀꢃꢂꢉꢁ ꢅ±ꢌꢀꢌꢍꢉꢁ ꢅꢆꢂꢈꢀꢂꢋꢉꢁ ꢅꢆꢄꢀꢃꢌꢉꢁ ꢅ±ꢄꢀꢂꢈꢉꢁ ꢅ±ꢄꢀꢂꢄꢉꢁ ꢅ±ꢄꢀꢎꢍꢉꢁ ꢇꢏꢀꢃꢎꢁ
,,,Fꢀ ꢂꢃꢎꢀꢇꢂꢁ ꢂꢎꢍꢀꢃꢈꢁ ꢂꢋꢋꢀꢂꢇꢁ ꢂꢌꢎꢀꢏꢌꢁ ꢂꢇꢋꢀꢌꢋꢁ ꢂꢎꢍꢀꢃꢎꢁ ꢂꢍꢄꢀꢎꢋꢁ ꢂꢇꢏꢀꢍꢂꢁ ꢂꢇꢈꢀꢄꢈꢁ ꢂꢋꢋꢀꢋꢃꢁ ꢇꢂꢀꢎꢌꢐꢁꢇꢏꢀꢂꢎꢐꢁ
ꢅ±ꢄꢀꢎꢇꢉꢁ ꢅꢆꢂꢈꢀꢌꢋꢉꢁ ꢅ±ꢏꢀꢇꢄꢉꢁ ꢅꢆꢂꢀꢃꢌꢉꢁ ꢅ±ꢌꢀꢌꢂꢉꢁ ꢅꢆꢂꢈꢀꢇꢋꢉꢁ ꢅꢆꢄꢀꢃꢋꢉꢁ ꢅ±ꢄꢀꢇꢋꢉꢁ ꢅ±ꢄꢀꢄꢌꢉꢁ ꢅ±ꢄꢀꢋꢏꢉꢁ ꢇꢏꢀꢃꢃꢁ
,,,Gꢀ ꢂꢃꢎꢀꢂꢎꢁ ꢂꢎꢎꢀꢇꢇꢁ ꢂꢋꢇꢀꢈꢃꢁ ꢂꢌꢌꢀꢄꢌꢁ ꢂꢇꢋꢀꢌꢇꢁ ꢂꢎꢎꢀꢂꢃꢁ ꢂꢋꢈꢀꢄꢈꢁ ꢂꢇꢃꢀꢈꢎꢁ ꢂꢇꢈꢀꢋꢈꢁ ꢂꢍꢄꢀꢄꢂꢁ ꢇꢂꢀꢎꢎꢐꢁꢇꢏꢀꢇꢇꢐꢁ
ꢅ±ꢄꢀꢍꢃꢉꢁ ꢅꢆꢂꢈꢀꢏꢇꢉꢁ ꢅ±ꢏꢀꢇꢋꢉꢁ ꢅꢆꢂꢀꢃꢇꢉꢁ ꢅ±ꢌꢀꢌꢌꢉꢁ ꢅꢆꢂꢈꢀꢋꢂꢉꢁ ꢅꢆꢄꢀꢃꢏꢉꢁ ꢅ±ꢄꢀꢂꢌꢉꢁ ꢅ±ꢄꢀꢂꢌꢉꢁ ꢅ±ꢄꢀꢎꢇꢉꢁ ꢇꢏꢀꢈꢍꢁ
,,,Hꢀ ꢂꢃꢍꢀꢈꢃꢁ ꢂꢎꢎꢀꢃꢋꢁ ꢂꢋꢇꢀꢌꢇꢁ ꢂꢌꢌꢀꢃꢍꢁ ꢂꢇꢋꢀꢏꢈꢁ ꢂꢎꢎꢀꢏꢈꢁ ꢂꢍꢌꢀꢂꢇꢁ ꢂꢇꢃꢀꢏꢃꢁ ꢂꢇꢍꢀꢇꢌꢁ ꢂꢎꢄꢀꢍꢃꢁ ꢇꢂꢀꢎꢌꢐꢁꢇꢏꢀꢋꢍꢐꢁ
ꢅ±ꢄꢀꢍꢍꢉꢁ ꢅꢆꢇꢄꢀꢄꢍꢉꢁ ꢅ±ꢏꢀꢂꢎꢉꢁ ꢅꢆꢂꢀꢃꢄꢉꢁ ꢅ±ꢌꢀꢎꢏꢉꢁ ꢅꢆꢂꢈꢀꢌꢋꢉꢁ ꢅꢆꢄꢀꢈꢍꢉꢁ ꢅ±ꢄꢀꢂꢏꢉꢁ ꢅ±ꢄꢀꢄꢃꢉꢁ ꢅꢆꢄꢀꢋꢄꢉꢁ ꢇꢃꢀꢄꢌꢁ
±ꢁ
±ꢁ
±ꢁ
,9Dꢀ ꢂꢃꢌꢀꢋꢎꢁ ꢂꢎꢏꢀꢇꢍꢁ ꢂꢋꢋꢀꢍꢌꢁ ꢂꢌꢎꢀꢍꢏꢁ ꢂꢇꢋꢀꢏꢌꢁ ꢂꢎꢏꢀꢇꢍꢁ ꢂꢋꢇꢀꢇꢎꢁ ꢂꢇꢏꢀꢌꢃꢁ ꢂꢂꢍꢀꢇꢈꢁ ꢂꢌꢋꢀꢎꢇꢁ ꢇꢈꢀꢍꢌꢐꢁꢋꢄꢀꢃꢃꢐꢁ ꢎꢎꢀꢌꢏꢁ
ꢅꢆꢄꢀꢍꢌꢉꢁ ꢅꢆꢇꢇꢀꢂꢇꢉꢁ ꢅ±ꢏꢀꢄꢃꢉꢁ ꢅꢆꢇꢀꢇꢄꢉꢁ ꢅ±ꢌꢀꢋꢌꢉꢁ ꢅꢆꢇꢂꢀꢏꢇꢉꢁ ꢅꢆꢂꢀꢂꢂꢉꢁ ꢅ±ꢇꢀꢋꢄꢉꢁ ꢅ±ꢄꢀꢂꢂꢉꢁ ꢅ±ꢄꢀꢋꢏꢉꢁ ꢋꢎꢀꢈꢂꢐꢁꢋꢌꢀꢍꢍꢁ
,9Eꢀ ꢂꢃꢌꢀꢋꢈꢁ ꢂꢎꢏꢀꢋꢋꢁ ꢂꢋꢋꢀꢍꢂꢁ ꢂꢌꢎꢀꢃꢇꢁ ꢂꢇꢋꢀꢈꢂꢁ ꢂꢎꢏꢀꢋꢋꢁ ꢂꢋꢏꢀꢏꢋꢁ ꢂꢇꢏꢀꢍꢎꢁ ꢂꢇꢈꢀꢏꢋꢁ ꢂꢂꢍꢀꢋꢋꢁ ꢇꢈꢀꢎꢄꢐꢁꢋꢎꢀꢈꢂꢐꢁ ꢇꢂꢀꢌꢎꢁ
ꢅꢆꢄꢀꢎꢃꢉꢁ ꢅꢆꢇꢇꢀꢂꢏꢉꢁ ꢅ±ꢌꢀꢃꢍꢉꢁ ꢅꢆꢇꢀꢂꢃꢉꢁ ꢅ±ꢌꢀꢇꢎꢉꢁ ꢅꢆꢇꢂꢀꢏꢃꢉꢁ ꢅꢆꢂꢀꢄꢂꢉꢁ ꢅ±ꢄꢀꢂꢈꢉꢁ ꢅ±ꢄꢀꢄꢎꢉꢁ ꢅ±ꢄꢀꢎꢃꢉꢁ
ꢋꢌꢀꢍꢈꢁ
,9Fꢀ ꢂꢃꢌꢀꢇꢏꢁ ꢂꢎꢏꢀꢍꢋꢁ ꢂꢋꢋꢀꢇꢏꢁ ꢂꢌꢌꢀꢄꢂꢁ ꢂꢇꢋꢀꢈꢋꢁ ꢂꢎꢏꢀꢍꢋꢁ ꢂꢍꢄꢀꢌꢇꢁ ꢂꢇꢏꢀꢋꢃꢁ ꢂꢇꢈꢀꢄꢇꢁ ꢂꢋꢋꢀꢇꢏꢁ ꢇꢈꢀꢍꢋꢐꢁꢇꢈꢀꢎꢄꢐꢁ
ꢅꢆꢄꢀꢎꢍꢉꢁ ꢅꢆꢇꢇꢀꢂꢏꢉꢁ ꢅ±ꢏꢀꢄꢎꢉꢁ ꢅꢆꢇꢀꢂꢂꢉꢁ ꢅ±ꢌꢀꢋꢂꢉꢁ ꢅꢆꢇꢂꢀꢃꢂꢉꢁ ꢅꢆꢄꢀꢈꢇꢉꢁ ꢅ±ꢄꢀꢇꢌꢉꢁ ꢅ±ꢄꢀꢂꢋꢉꢁ ꢅ±ꢄꢀꢍꢃꢉꢁ ꢋꢎꢀꢈꢌꢐꢁꢋꢌꢀꢍꢈꢁ
,9Gꢀ ꢂꢃꢌꢀꢂꢍꢁ ꢂꢎꢏꢀꢌꢏꢁ ꢂꢋꢋꢀꢄꢃꢁ ꢂꢌꢌꢀꢇꢌꢁ ꢂꢇꢋꢀꢈꢂꢁ ꢂꢎꢏꢀꢌꢏꢁ ꢂꢋꢈꢀꢄꢍꢁ ꢂꢇꢃꢀꢃꢎꢁ ꢂꢇꢈꢀꢋꢍꢁ ꢂꢋꢈꢀꢈꢌꢁ ꢇꢈꢀꢍꢌꢐꢁꢋꢎꢀꢈꢌꢐꢁ
±ꢁ
±ꢁ
±ꢁ
±ꢁ
±ꢁ
ꢅꢆꢄꢀꢎꢂꢉꢁ ꢅꢆꢇꢇꢀꢂꢏꢉꢁ ꢅ±ꢏꢀꢂꢋꢉꢁ ꢅꢆꢇꢀꢄꢇꢉꢁ ꢅꢆꢌꢀꢋꢏꢉꢁ ꢅꢆꢇꢂꢀꢃꢄꢉꢁ ꢅꢆꢄꢀꢃꢇꢉꢁ ꢅ±ꢄꢀꢇꢌꢉꢁ ꢅ±ꢄꢀꢇꢂꢉꢁ ꢅ±ꢄꢀꢎꢏꢉꢁ
,9Hꢀ ꢂꢃꢌꢀꢄꢄꢁ ꢂꢎꢃꢀꢋꢎꢁ ꢂꢋꢇꢀꢏꢌꢁ ꢂꢌꢏꢀꢄꢄꢁ ꢂꢇꢍꢀꢄꢃꢁ ꢂꢎꢃꢀꢋꢎꢁ ꢂꢍꢌꢀꢂꢏꢁ ꢂꢇꢃꢀꢏꢂꢁ ꢂꢇꢍꢀꢇꢇꢁ ꢂꢎꢄꢀꢍꢇꢁ ꢇꢈꢀꢍꢌꢐꢁꢋꢌꢀꢂꢄꢐꢁ
ꢅꢆꢄꢀꢎꢃꢉꢁ ꢅꢆꢇꢇꢀꢎꢌꢉꢁ ꢅ±ꢏꢀꢄꢂꢉꢁ ꢅꢆꢂꢀꢈꢌꢉꢁ ꢅ±ꢌꢀꢇꢃꢉꢁ ꢅꢆꢇꢇꢀꢂꢈꢉꢁ ꢅꢆꢄꢀꢈꢈꢉꢁ ꢅ±ꢄꢀꢇꢍꢉꢁ ꢅ±ꢄꢀꢂꢇꢉꢁ ꢅꢆꢄꢀꢇꢍꢉꢁ ꢋꢌꢀꢌꢂꢁ
9ꢀ ꢂꢃꢌꢀꢂꢍꢁ ꢂꢎꢄꢀꢍꢎꢁ ꢂꢋꢇꢀꢂꢋꢁ ꢂꢎꢎꢀꢋꢏꢁ ꢂꢂꢈꢀꢈꢃꢁ ꢂꢍꢌꢀꢌꢏꢁ ꢂꢋꢌꢀꢂꢏꢁ ꢂꢇꢌꢀꢌꢏꢁ ꢂꢇꢈꢀꢇꢈꢁ ꢂꢋꢋꢀꢋꢏꢁ ꢇꢂꢀꢃꢏꢐꢁꢇꢌꢀꢋꢎꢐꢁ
ꢅ±ꢂꢀꢋꢋꢉꢁ ꢅꢆꢇꢂꢀꢌꢄꢉꢁ ꢅ±ꢌꢀꢈꢋꢉꢁ ꢅꢆꢂꢀꢇꢄꢉꢁ ꢅ±ꢌꢀꢃꢄꢉꢁ ꢅꢆꢂꢍꢀꢌꢈꢉꢁ ꢅꢆꢄꢀꢏꢄꢉꢁ ꢅ±ꢄꢀꢂꢂꢉꢁ ꢅ±ꢄꢀꢂꢎꢉꢁ ꢅ±ꢄꢀꢌꢇꢉꢁ ꢇꢌꢀꢎꢈꢁ
ꢋꢌꢀꢎꢍꢁ
9,ꢀ ꢂꢃꢏꢀꢇꢍꢁ ꢂꢎꢇꢀꢃꢋꢁ ꢂꢋꢇꢀꢍꢋꢁ ꢂꢎꢎꢀꢌꢍꢁ ꢂꢇꢄꢀꢌꢇꢁ ꢂꢍꢈꢀꢄꢇꢁ ꢂꢋꢌꢀꢋꢌꢁ ꢂꢇꢌꢀꢃꢌꢁ ꢂꢇꢈꢀꢋꢂꢁ ꢂꢋꢋꢀꢍꢄꢁ ꢇꢈꢀꢎꢇꢐꢁꢋꢎꢀꢈꢋꢁ
ꢅ±ꢄꢀꢇꢋꢉꢁ ꢅꢆꢇꢋꢀꢈꢈꢉꢁ ꢅ±ꢌꢀꢌꢋꢉꢁ ꢅꢆꢂꢀꢍꢏꢉꢁ ꢅ±ꢌꢀꢂꢌꢉꢁ ꢅꢆꢂꢏꢀꢄꢍꢉꢁ ꢅꢆꢄꢀꢃꢈꢉꢁ ꢅꢆꢄꢀꢄꢃꢉꢁ ꢅ±ꢄꢀꢂꢋꢉꢁ ꢅ±ꢄꢀꢎꢈꢉꢁ
ꢁ
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1124
PIROZHENKO et al.
Table 1. (Contd).
&RPSGꢀꢁ
QRꢀꢁ
9,,Dꢀ ꢂꢃꢏꢀꢂꢌꢁ
ꢅ±ꢄꢀꢎꢎꢉꢁ
9,,Eꢀ ꢂꢃꢏꢀꢂꢏꢁ
ꢅ±ꢄꢀꢋꢃꢉꢁ
9,,Fꢀ ꢂꢃꢏꢀꢄꢌꢁ
ꢅ±ꢄꢀꢎꢎꢉꢁ
9,,Gꢀ ꢂꢃꢏꢀꢄꢇꢁ
ꢅ±ꢄꢀꢍꢎꢉꢁ
& ꢁ
& ꢁ
aꢂꢇꢈꢁ aꢂꢍꢎꢁVKꢁ ꢂꢎꢇꢀꢋꢈꢁ aꢂꢍꢎꢁVKꢁ aꢂꢇꢈꢁ ꢂꢋꢂꢀꢏꢌꢁ ꢂꢇꢏꢀꢇꢄꢁ ꢂꢂꢍꢀꢈꢈꢁ ꢂꢎꢈꢀꢈꢈꢁ
ꢅ±ꢂꢀꢂꢈꢉꢁ ꢅꢆꢋꢀꢈꢃꢉꢁ ꢅ±ꢇꢀꢇꢍꢉꢁ ꢅꢆꢄꢀꢄꢍꢉꢁ ꢅ±ꢄꢀꢋꢈꢉꢁ
aꢂꢇꢈꢁ ꢂꢍꢂ±ꢂꢍꢎꢁ ꢂꢎꢇꢀꢍꢈꢁ ꢂꢍꢂ±ꢂꢍꢎꢁ aꢂꢇꢈꢁ ꢂꢋꢏꢀꢇꢍꢁ ꢂꢇꢍꢀꢏꢌꢁ ꢂꢇꢈꢀꢈꢍꢁ ꢂꢋꢏꢀꢈꢈꢁ
VKꢁ ꢅ±ꢂꢀꢂꢎꢉꢁ VKꢁ ꢅꢆꢋꢀꢎꢃꢉꢁ ꢅ±ꢂꢀꢍꢃꢉꢁ ꢅ±ꢄꢀꢄꢋꢉꢁ ꢅ±ꢄꢀꢍꢏꢉꢁ
aꢂꢇꢈꢁ ꢂꢍꢂ±ꢂꢍꢎꢁꢅ±ꢂꢀꢄꢄꢉꢁ ꢂꢍꢂ±ꢂꢍꢎꢁ aꢂꢇꢈꢁ ꢂꢍꢄꢀꢍꢃꢁ ꢂꢇꢍꢀꢎꢂꢁ ꢂꢇꢈꢀꢇꢍꢁ ꢂꢇꢏꢀꢏꢏꢁ
VKꢁ VKꢁ ꢅꢆꢋꢀꢎꢂꢉꢁ ꢅ±ꢂꢀꢂꢍꢉꢁ ꢅ±ꢄꢀꢄꢂꢉꢁ ꢅ±ꢄꢀꢋꢂꢉꢁ
aꢂꢋꢂꢁ ꢂꢍꢃꢁVKꢁ ꢂꢎꢋꢀꢂꢍꢁ ꢂꢍꢇꢁVKꢁ aꢂꢇꢏꢁ ꢂꢋꢃꢀꢃꢍꢁ ꢂꢇꢎꢀꢌꢋꢁ ꢂꢇꢈꢀꢍꢂꢁ ꢂꢋꢋꢀꢏꢂꢁ ꢇꢄꢀꢄꢁVKꢐꢁꢇꢇꢀꢄꢁ
ꢅ±ꢂꢀꢄꢋꢉꢁ ꢅꢆꢋꢀꢋꢏꢉꢁ ꢅ±ꢂꢀꢂꢎꢉꢁ ꢅ±ꢄꢀꢄꢋꢉꢁ ꢅ±ꢄꢀꢇꢃꢉꢁ VKꢁ
ꢂꢇꢏꢀꢃꢁ ꢂꢍꢃꢀꢇꢁ ꢂꢎꢍꢀꢌꢍꢁ ꢂꢍꢇꢀꢇꢁ ꢂꢋꢇꢀꢇꢁ ꢂꢍꢃꢀꢂꢏꢁ ꢂꢇꢋꢀꢈꢄꢁ ꢂꢇꢍꢀꢍꢎꢁ ꢂꢍꢏꢀꢄꢄꢁ ꢇꢄꢀꢄꢁVKꢐꢁꢁꢇꢋꢀꢄꢁ ±ꢁ
& ꢁ
& ꢁ
& ꢁ
& ꢁ
& ꢁ
& ꢁ
& ꢁ
& ꢁ
$ONꢁ
5ꢁ
ꢇꢂꢀꢃꢁVKꢁ
ꢎꢎꢀꢎꢍꢁ
ꢇꢂꢀꢋꢁVKꢁ
ꢇꢂꢀꢏꢁVKꢁ
ꢇꢂꢀꢂꢌꢁ
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9,,Hꢀ ꢂꢃꢌꢀꢃꢇꢁ
ꢅ±ꢄꢀꢋꢈꢉꢁ ꢅ±ꢂꢀꢏꢈꢉꢁ ꢅꢆꢃꢀꢍꢉꢁ ꢅ±ꢄꢀꢏꢂꢉꢁ
ꢅ±ꢄꢀꢎꢉꢁ ꢅꢆꢇꢀꢃꢍꢉꢁ ꢅ±ꢄꢀꢍꢌꢉꢁ ꢅꢆꢄꢀꢄꢈꢉꢁ ꢅꢆꢄꢀꢇꢇꢉꢁ
VKꢁ
9,,,Dꢀ ꢂꢃꢌꢀꢂꢄꢁ ꢂꢋꢋꢀꢎꢂꢁ ꢂꢍꢌꢀꢈꢌꢁ ꢂꢌꢍꢀꢋꢈꢁ ꢂꢍꢌꢀꢈꢌꢁ ꢂꢋꢋꢀꢎꢂꢁ ꢂꢋꢍꢀꢍꢂꢁ ꢂꢇꢃꢀꢏꢇꢁ ꢂꢂꢍꢀꢄꢏꢁ ꢂꢌꢋꢀꢄꢋꢁ
ꢅꢆꢄꢀꢇꢂꢉꢁ ꢅ±ꢂꢀꢃꢂꢉꢁ ꢅꢆꢂꢂꢀꢌꢋꢉꢁꢅꢆꢂꢀꢂꢇꢉꢁ ꢅꢆꢂꢂꢀꢌꢋꢉꢁ ꢅ±ꢂꢀꢃꢂꢉꢁ ꢅꢆꢋꢀꢇꢏꢉꢁ ꢅ±ꢂꢀꢇꢌꢉꢁ ꢅ±ꢄꢀꢋꢋꢉꢁ ꢅ±ꢄꢀꢃꢌꢉꢁ
9,,,Eꢀ ꢂꢃꢌꢀꢄꢏꢁ ꢂꢋꢋꢀꢌꢄꢁ ꢂꢍꢏꢀꢄꢇꢁ ꢂꢌꢍꢀꢏꢇꢁ ꢂꢍꢏꢀꢄꢇꢁ ꢂꢋꢋꢀꢌꢄꢁ ꢂꢋꢈꢀꢍꢍꢁ ꢂꢇꢌꢀꢎꢌꢁ ꢂꢇꢈꢀꢎꢋꢁ ꢂꢍꢋꢀꢌꢈꢁ
ꢅꢆꢄꢀꢇꢌꢉꢁ ꢅ±ꢂꢀꢏꢌꢉꢁ ꢅꢆꢂꢂꢀꢃꢂꢉꢁꢅꢆꢂꢀꢄꢃꢉꢁ ꢅꢆꢂꢂꢀꢃꢂꢉꢁ ꢅ±ꢂꢀꢏꢌꢉꢁ ꢅꢆꢇꢀꢏꢇꢉꢁ ꢅ±ꢂꢀꢄꢃꢉꢁ ꢅ±ꢄꢀꢇꢎꢉꢁ ꢅ±ꢂꢀꢇꢇꢉꢁ
9,,,Fꢀ ꢂꢃꢌꢀꢂꢂꢁ ꢂꢋꢋꢀꢌꢃꢁ ꢂꢍꢌꢀꢃꢈꢁ ꢂꢌꢍꢀꢈꢈꢁ ꢂꢍꢌꢀꢃꢈꢁ ꢂꢋꢋꢀꢌꢃꢁ ꢂꢍꢇꢀꢎꢃꢁ ꢂꢇꢌꢀꢎꢇꢁ ꢂꢇꢃꢀꢃꢈꢁ ꢂꢋꢇꢀꢏꢇꢁ
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9,,,Gꢀ ꢂꢃꢎꢀꢈꢎꢁ ꢂꢋꢋꢀꢏꢍꢁ ꢂꢍꢌꢀꢌꢇꢁ ꢂꢌꢎꢀꢇꢏꢁ ꢂꢍꢌꢀꢌꢇꢁ ꢂꢋꢋꢀꢏꢍꢁ ꢂꢍꢂꢀꢄꢄꢁ ꢂꢇꢏꢀꢈꢌꢁ ꢂꢇꢈꢀꢂꢎꢁ ꢂꢋꢈꢀꢂꢈꢁ
ꢅꢆꢄꢀꢋꢇꢉꢁ ꢅ±ꢂꢀꢈꢎꢉꢁ ꢅꢆꢂꢂꢀꢋꢏꢉꢁꢅꢆꢂꢀꢄꢋꢉꢁ ꢅꢆꢂꢂꢀꢋꢏꢉꢁ ꢅ±ꢂꢀꢈꢎꢉꢁ ꢅꢆꢇꢀꢏꢃꢉꢁ ꢅ±ꢂꢀꢂꢎꢉꢁ ꢅ±ꢄꢀꢍꢄꢉꢁ ꢅ±ꢂꢀꢋꢍꢉꢁ
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ꢅ±ꢄꢀꢍꢂꢉꢁ ꢅꢆꢍꢀꢏꢄꢉꢁ ꢅꢆꢌꢀꢃꢎꢉꢁ ꢅꢆꢍꢀꢇꢈꢉꢁ ꢅꢆꢌꢀꢃꢎꢉꢁ ꢅꢆꢍꢀꢏꢄꢉꢁ ꢅꢆꢋꢀꢌꢎꢉꢁ ꢅ±ꢂꢀꢂꢃꢉꢁ ꢅ±ꢄꢀꢍꢄꢉꢁ ꢅ±ꢂꢀꢄꢏꢉꢁ
,;Eꢀ ꢂꢃꢎꢀꢍꢍꢁ ꢂꢍꢄꢀꢄꢌꢁ ꢂꢍꢇꢀꢂꢂꢁ ꢂꢌꢏꢀꢃꢎꢁ ꢂꢍꢇꢀꢂꢂꢁ ꢂꢍꢄꢀꢄꢌꢁ ꢂꢍꢄꢀꢄꢇꢁ ꢂꢇꢌꢀꢎꢈꢁ ꢂꢇꢈꢀꢍꢄꢁ ꢂꢍꢋꢀꢇꢌꢁ ꢂꢇꢀꢃꢄꢐꢁꢂꢌꢀꢃꢋꢁ ꢇꢂꢀꢎꢇꢁ
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,;Fꢀ
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ꢂꢃꢏꢀꢌꢂꢁ ꢂꢇꢃꢀꢎꢈꢁ ꢂꢋꢈꢀꢂꢃꢁ ꢂꢎꢋꢀꢃꢃꢁ ꢂꢇꢌꢀꢌꢃꢁ ꢂꢋꢂꢀꢏꢎꢁ ꢂꢋꢌꢀꢈꢏꢁ ꢂꢇꢎꢀꢌꢎꢁ ꢂꢇꢈꢀꢇꢎꢁ ꢂꢇꢃꢀꢄꢃꢁ
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;,Dꢀ ꢂꢃꢎꢀꢃꢈꢁ ꢂꢋꢎꢀꢂꢇꢁ ꢂꢍꢄꢀꢎꢍꢁ ꢂꢌꢋꢀꢇꢏꢁ ꢂꢋꢄꢀꢂꢇꢁ ꢂꢋꢎꢀꢎꢇꢁ ꢂꢋꢂꢀꢂꢍꢁ ꢂꢇꢈꢀꢈꢃꢁ ꢂꢂꢍꢀꢍꢄꢁ ꢂꢌꢋꢀꢃꢈꢁ
;,Eꢀ ꢂꢃꢎꢀꢃꢂꢁ ꢂꢋꢎꢀꢂꢌꢁ ꢂꢍꢄꢀꢇꢎꢁ ꢂꢌꢋꢀꢌꢍꢁ ꢂꢋꢄꢀꢂꢌꢁ ꢂꢋꢎꢀꢎꢎꢁ ꢂꢋꢌꢀꢏꢇꢁ ꢂꢇꢏꢀꢌꢍꢁ ꢂꢇꢈꢀꢏꢃꢁ ꢂꢍꢍꢀꢈꢂꢁ
;,Fꢀ
;,Gꢀ ꢂꢃꢎꢀꢌꢋꢁ ꢂꢋꢎꢀꢎꢄꢁ ꢂꢍꢄꢀꢇꢂꢁ ꢂꢌꢍꢀꢇꢍꢁ ꢂꢋꢄꢀꢇꢃꢁ ꢂꢋꢎꢀꢃꢏꢁ ꢂꢋꢃꢀꢇꢇꢁ ꢂꢇꢈꢀꢂꢂꢁ ꢂꢇꢈꢀꢎꢎꢁ ꢂꢍꢄꢀꢎꢋꢁ
;,Hꢀ ꢂꢃꢎꢀꢍꢇꢁ ꢂꢋꢎꢀꢏꢈꢁ ꢂꢋꢈꢀꢏꢏꢁ ꢂꢌꢎꢀꢄꢍꢁ ꢂꢋꢄꢀꢋꢌꢁ ꢂꢋꢌꢀꢂꢌꢁ ꢂꢍꢎꢀꢂꢃꢁ ꢂꢇꢃꢀꢈꢎꢁ ꢂꢇꢍꢀꢋꢍꢁ ꢂꢎꢄꢀꢂꢃꢁ
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ꢁ
a The changes in the chemical shift values of carbons compared to those of the respective atoms in the spectra of quinoneimines unsubstituted
in the ring are given in parentheses. For compounds VIIIa–e and IXa–e chemical shifts of atoms C2, C6 and C3, C5 are compared with the
corresponding averaged chemical shifts of atoms C2, C6 and C3, C5 of quinonimines unsubstituted in the ring.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

SYNTHESIS AND 13C NMR SPECTRA OF N-SUBSTITUTED p-QUINONIMINES: III.
1125
In the preceding study [1] we demonstrated that at
incorporation of chlorine atoms into positions 3 and 5 of
the quinoid ring the changes in carbon chemical shifts
differ from those observed in the 2,6-dichloro-1,4-
benzoquinonimines. This effect we attributed to the
specific structural features of 3,5-disubstituted 1,4-benzo-
quinonimines (at two substituents in the ortho-position
in respect to the imino group the bond angle-C=N–S
increased [4]). It was interesting to establish what
difference in the chemical shifts would arise on
introducing alkyl substituents into positions 3 and 5
instead positions 2 and 6. It should be noted that
introduction of substituents into the 3 and 5 positions of
the quinonimine fragment results in decreasing the barrier
to the Z,E-isomerization of the studied benzoquinon-
imine*. Consequently the signals from atoms C2, C3, C5,
C6 in the 13C NMR spectra of N-arylthiobenzoquinon-
imines are notably broadened, and the barrier for N-aryl-
sulfonylbenzoquinonimine is decreased still stronger
resulting in magnetic equivalence of atoms C2, C6 and
C5, C3 whose resonances appear as singlets.
effects of substituents. These changes in geometry are
also responsible for the already mentioned reduced
magnetic nonequivalence of C3 and C5 atoms in the
3,5-disubstituted compounds.
It should also be pointed out that like the case of
3,5-dichloro-substituted 1,4-benzoquinonimines the
largest shift of the C1' atom was observed in the para-
methoxy derivatives and the smallest shift occurred in
the para-nitro compounds. Similar changes in the
chemical shifts of the benzene ring carbon signals of
compounds substituted by chlorine as well as methyl
group in the quinonimine fragment confirm the conclu-
sion on the lack of conjugation between the p-systems
of the quinonimine and benzene fragments.
We also investigated N-arylsulfonyl-2,3,5,6-tetra-
methyl-1,4-benzoquinonimines (IXa–e). The presence
of four methyl groups resulted in the downfield shift of
signals from atoms C2–C6 as was observed also in the
other types of alkyl-substituted benzoquinonimines. At
the same time the carbonyl carbon peak shifted upfield.
The alterations in the chemical shifts of the benzene ring
in this series of compounds are similar to those observed
in the 3,5-dimethyl-substituted benzoquinonimines.
Furthermore, the pattern of these changes is like that
observed in the spectra of 3,5- and 2,3,5,6-chloro
derivatives of arylsulfonyl-1,4-benzoquinonimines [1]
testifying again to the conclusion on the origin of this
changes lying in the geometrical and not electronic
reasons. This statement is also supported by comparison
of parameters of correlation equations that we calculated
analogously to [1]:
The incorporation of methyl groups into positions 3
and 5 (quinonimines VIIa–e and VIIIa–e) differently
affects the chemical shifts of C1 and C4 in N-arylthio
(VIIa–e) and N-arylsulfonyl (VIIIa–e) derivatives.
Whereas in the spectra of the latter the changes are similar
to those observed in the 2,6-dimethyl-substituted
compounds, in the spectra of the N-arylthio derivatives
the signals of C1 and C4 are strongly shifted upfield. The
changes in the chemical shifts of C2, C3, C5, and C6 atoms
occur in the same fashion. In the 3,5-dimethyl derivatives
of the N-arylthio-1,4-benzoquinonimines the magnetic
nonequivalence of atoms C3 and C5 is considerably
reduced leading to closer chemical shift values of the
corresponding signals compared to the spectra of
unsubstituted and 2,6-dichloro-substituted compounds.
Analogous effect was jbserved in 3,5-dichloro-
substituted N-arylthiobenzoquinonimines [1]. Note that
alkyl substituents introduced into positions 3 and 5
produce a considerable downfield shift of the signal from
C1' atom of the benzene ring as is also observed in the
chloroderivatives of 1,4-benzoquinonimines [1]. In all
likelihood the changes in chemical shifts here also are
caused primarily by the altered geometry of molecules
at incorporation of substituents into the ortho-position
with respect to the imine carbon: The observed effect is
due to increase in the CNS angle and not to electronic
d C1' = a + bdC.
Here dC1'' is the chemical shift of atom C1' in benzo-
quinonimines under study, dC is the chemical shift of a
Table 2. Parameters of correlation equations of chemical shift
values of C1' atom in relation to the nature of substituent R in
N-substituted 1,4-benzoquinonimines (n = 5)
&RPSGꢀ9QRꢀ
9
D
9
E
9
59
,
ꢁꢂꢃꢀꢄꢅ
ꢁꢄꢈꢀꢄꢊ
ꢁꢄꢈꢀꢂꢆ
ꢁꢄꢈꢀꢋꢊ
ꢁꢄꢈꢀꢃꢅ
ꢁꢄꢅꢀꢂꢁ
ꢁꢄꢅꢀꢌꢈ
9
9
9
9
9
9
9
ꢁꢀꢅꢆ9ꢇꢈꢀꢈꢄꢉ
ꢁꢀꢈꢅ9ꢇꢈꢀꢈꢊꢉ
ꢁꢀꢈꢈ9ꢇꢈꢀꢈꢊꢉ
ꢈꢀꢆꢄ9ꢇꢈꢀꢈꢄꢉ
ꢁꢀꢁꢃ9ꢇꢈꢀꢈꢅꢉ
ꢈꢀꢆꢌ9ꢇꢈꢀꢈꢋꢉ
ꢈꢀꢆꢊ9ꢇꢈꢀꢈꢋꢉ
9
9
9
9
9
9
9
ꢈꢀꢆꢆꢃ
ꢈꢀꢆꢆꢄ
ꢈꢀꢆꢆꢋ
ꢈꢀꢆꢃꢄ
ꢈꢀꢆꢆꢆ
ꢈꢀꢆꢆꢊ
ꢈꢀꢆꢆꢊ
9
9
9
9
9
9
9
,,
,,,
,9
9,,
9,,,
,;
* The results of the study on conformational stability of substituted
benzoquinonimines will be published elsewhere.
9
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1126
PIROZHENKO et al.
carbon atom in the para-position of a monosubstituted
benzene C6H5R (Table 2).
Scheme 1.
3UꢂL
3UꢂL
As seen from the data in Table 2 in the case of N-aryl-
thio-1,4-benzoquinonimines in going from unsubstituted
to 2,6-disubstituted compounds the character of
variations in the b factor is nearly independent of the
substituent nature and is the same for quinonimines
substituted in the quinonimine fragment both by chlorine
and methyl group. Analogous similarity in alterations
of this factor is also observed for 3,5-disubstituted
N-arylthio-1,4-benzoquinonimines. Therewith we
believe that the significant decrease in the factor in the
latter case is due to the change in the interaction character
between the sulfur atom and the benzene ring originating
first of all from structural reasons caused by the presence
of substituents in the ortho-position with respect to
nitrogen, i.e., by increased bond angle CNS. Note that
whereas for arylthio derivatives of benzoquinonimines
the value of the b factor depends on the presence of
substituents at the quinonimine fragment, for arylsulfonyl
derivatives, as seen from Table 2, the corresponding value
is practically constant and notwithstanding the
substituents nature and their location is equal to unity
within the error limits thus revealing the barrier character
of the SO2 group. The dependence of the b factor in
N-arylthio-1,4-benzoquinonimines on the presence of
substituents at the quinonimine fragment although
confirms the absence of a unique conjugation system in
these compounds yet as we guess indicates that the
bivalent sulfur somehow interacts with the quinonimine
and aryl fragments.
$U62 &Oꢀꢁ
+ 1
2+
3UꢂL
1D+&2
+&O
$U62 1+
2+
3UꢂL
3Eꢃ2$Fꢄ
,,,D FꢀꢁH
Scheme 2.
Hr
Hr
Hr
Hr
!ꢀ6ꢁTP 8yꢀꢂ
C I
IC
Hr
6ꢁTP IC
Hr
Hr
IhC8P
!ꢀC8y
ICTP 6ꢁ
Hr
,;DꢀꢁF H
Scheme 3.
QiꢃP6pꢄ
In conclusion we present here refined assignments of
the carbon chemical shifts for N-arylthio- (Xa–e) and
N-arylsulfonyl- (XIa–e) -1,4-benzoquinonimine unsub-
stituted in the quinonimine fragment previously
published in [2]. These data were used here in calculating
the changes in the chemical shifts of carbons in
compounds I–IX substituted in the quinonimine
fragment. The data for N-4-methoxyphenylsulfonyl-1,4-
benzoquinonimine (XIa) were obtained for the first time.
$U6&Oꢀꢀꢁꢀꢀ+ 1
2+
$ON
2
(W 1
+&O
,D Hꢀꢁ9ꢀꢁ9,ꢀꢁ9,,D H
$U6 1+
2+
N-Arylsulfonyl-2,6-diisopropyl-1,4-benzoquinon-
imines (IIIa–c, e) were prepared for the first time from
the corresponding N-arylsulfonyl-2,6-diisopropyl-1,4-
aminophenols by oxidation with lead tetraacetate in
acetic acid along procedure described in [5]. Initial
N-arylsulfonyl-2,6-diisopropyl-1,4-aminophenols were
obtained from 2,6-diisopropyl-1,4-aminophenol and
appropriate arenesulfonyl chlorides in water in the
presence of sodium hydrogen carbonate (Scheme 1) by
procedure [6].
$ON
Scheme 4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

SYNTHESIS AND 13C NMR SPECTRA OF N-SUBSTITUTED p-QUINONIMINES: III.
1127
Table 3. Yields, melting point, and elemental analyses of N-arylthio-1,4-benzoquinonimines Ia–e, V, VI, VIIa–e and N-aryl-
sulfonyl-1,4-benzoquinonimines IIIa–e, IXa, c–e alkyl-substituted in quinonimine ring
PSꢐꢁƒ&ꢁꢅVROYHQWꢁIRUꢁ
FU\VWDOOL]DWLRQꢉꢁꢁ
&RPSGꢀꢁQRꢀꢁ <LHOGꢐꢁ#ꢁ
)RXQGꢁ6ꢐ#ꢁ
)RUPXODꢁ
&DOFXODWHGꢁ6ꢐ#ꢁ
ꢋꢍꢁ
ꢋꢄꢁ
ꢇꢈꢁ
ꢇꢂꢁ
ꢋꢄꢁ
ꢋꢍꢁ
ꢇꢈꢁ
ꢇꢎꢁ
ꢇꢏꢁ
ꢋꢂꢁ
ꢇꢃꢁ
ꢇꢇꢁ
ꢇꢈꢁ
ꢋꢈꢁ
ꢇꢋꢁ
ꢋꢍꢁ
ꢇꢇꢁ
ꢇꢄꢁ
ꢇꢏꢁ
ꢋꢎꢁ
ꢇꢎꢁ
ꢁꢁꢃꢎ±ꢃꢌꢁꢅ& + ꢉꢁ
ꢂꢂꢀꢌꢃꢐꢁꢂꢂꢀꢏꢇꢁ
ꢂꢇꢀꢋꢏꢐꢁꢂꢇꢀꢍꢇꢁ
ꢂꢋꢀꢇꢄꢐꢁꢂꢋꢀꢇꢍꢁ
ꢂꢂꢀꢎꢎꢐꢁꢂꢂꢀꢎꢈꢁ
ꢂꢂꢀꢄꢍꢐꢁꢂꢂꢀꢂꢂꢁ
ꢃꢀꢃꢄꢐꢁꢃꢀꢃꢇꢁ
ꢈꢀꢂꢎꢐꢁꢈꢀꢇꢍꢁ
ꢈꢀꢌꢍꢐꢁꢈꢀꢏꢄꢁ
ꢃꢀꢏꢏꢐꢁꢃꢀꢈꢍꢁ
ꢃꢀꢂꢏꢐꢁꢃꢀꢂꢈꢁ
& + 12 6ꢁ
& + 126ꢁ
& + 126ꢁ
ꢂꢂꢀꢏꢇꢁ
ꢂꢇꢀꢍꢎꢁ
ꢂꢋꢀꢂꢏꢁ
ꢂꢂꢀꢎꢋꢁ
ꢂꢂꢀꢄꢏꢁ
ꢃꢀꢃꢌꢁ
ꢈꢀꢇꢃꢁ
ꢈꢀꢌꢏꢁ
ꢃꢀꢏꢎꢁ
ꢃꢀꢇꢂꢁ
,Dꢀ
,Eꢀ
,Fꢀ
,Gꢀ
ꢂꢂꢂ±ꢂꢂꢇꢁꢅ& + ꢉꢁ
ꢂꢍꢏ±ꢂꢍꢃꢁꢅ&+ &2 +ꢉꢁ
ꢂꢋꢏ±ꢂꢋꢃꢁꢅ& + ꢉꢁ
ꢂꢎꢎ±ꢂꢎꢌꢁꢅ&+ &2 +ꢉꢁ
ꢁꢁꢏꢃ±ꢏꢈꢁꢅ& + ꢉꢁ
& + &O126ꢁ
& + 1 2 6ꢁ
& + 12 6ꢁ
& + 12 6ꢁ
& + 12 6ꢁ
& + &O12 6ꢁ
& + 1 2 6ꢁ
& + &O126ꢁ
& + &O126ꢁ
& + 12 6ꢁ
& + 126ꢁ
,Hꢀ
,,,Dꢀ
,,,Eꢀ
,,,Fꢀ
,,,Gꢀ
,,,Hꢀ
9ꢀ
ꢁꢁꢃꢄ±ꢃꢂꢁꢅ& + ꢉꢁ
ꢁꢁꢏꢄ±ꢏꢂꢁꢅ& + ꢉꢁ
ꢂꢄꢃ±ꢂꢄꢈꢁꢅ& + ꢉꢁ
ꢂꢍꢌ±ꢂꢍꢏꢁꢅ& + ꢉꢁ
ꢂꢇꢂ±ꢂꢇꢇꢁꢅ&+ &2 +ꢉꢁ
ꢂꢂꢇ±ꢂꢂꢋꢁꢅ&+ &2 +ꢉꢁ
ꢂꢋꢎ±ꢂꢋꢌꢁꢅ&+ &2 +ꢉꢁ
ꢂꢇꢎ±ꢂꢇꢌꢁꢅ& + ꢉꢁ
ꢂꢏꢃ±ꢂꢏꢈꢁꢅ& + ꢉꢁ
ꢂꢃꢌ±ꢂꢃꢏꢁꢅ& + ꢉꢁ
ꢇꢇꢏ±ꢇꢇꢃꢁꢅ& + ꢉꢁ
ꢂꢂꢌ±ꢂꢂꢏꢁꢅ& + ꢉꢁ
ꢁꢁꢈꢈ±ꢂꢄꢄꢁꢅ& + ꢉꢁ
ꢂꢂꢃ±ꢂꢂꢈꢁꢅ& + ꢉꢁ
ꢂꢎꢇ±ꢂꢎꢋꢁꢅ& + ꢉꢁ
ꢈꢀꢌꢃꢐꢁꢈꢀꢏꢍꢁ
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ꢈꢀꢎꢈꢁ
ꢃꢀꢃꢎꢁ
9,ꢀ
ꢂꢂꢀꢌꢈꢐꢁꢂꢂꢀꢏꢎꢁ
ꢂꢇꢀꢋꢄꢐꢁꢂꢇꢀꢍꢍꢁ
ꢂꢋꢀꢇꢄꢐꢁꢂꢋꢀꢇꢎꢁ
ꢂꢂꢀꢎꢍꢐꢁꢂꢂꢀꢎꢏꢁ
ꢂꢂꢀꢄꢄꢐꢁꢂꢂꢀꢄꢋꢁ
ꢈꢀꢎꢌꢐꢁꢈꢀꢌꢋꢁ
ꢂꢄꢀꢍꢏꢐꢁꢂꢄꢀꢎꢇꢁ
ꢈꢀꢍꢄꢐꢁꢈꢀꢍꢎꢁ
ꢈꢀꢄꢈꢐꢁꢈꢀꢂꢍꢁ
ꢂꢂꢀꢏꢇꢁ
ꢂꢇꢀꢍꢎꢁ
ꢂꢋꢀꢂꢏꢁ
ꢂꢂꢀꢎꢋꢁ
ꢂꢂꢀꢄꢏꢁ
ꢈꢀꢌꢍꢁ
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9,,Dꢀ
9,,Eꢀ
9,,Fꢀ
9,,Gꢀ
9,,Hꢀ
,;Dꢀ
,;Fꢀ
,;Gꢀ
,;Hꢀ
& + 126ꢁ
& + &O126ꢁ
& + 1 2 6ꢁ
& + 12 6ꢁ
& + 12 6ꢁ
& + &O12 6ꢁ
& + 1 2 6ꢁ
ꢁ
(300 MHz and 200 MHz respectively) from solutions in
CDCl3. Chemical shifts are presented relative to TMS
N-Arylsulfonyl-2,3,5,6-tetramethyl-1,4-benzoquinon-
imines (IXa, c–e) were synthesized for the first time
along procedure described in [7] for quinonimine IXb
(Scheme 2).
1
with accuracy for 13C NMR spectra ±0.05 and for H
NMR spectra ±0.005 ppm.
N-Arylsulfonyl-1,4-benzoquinonimines IIa–e, IVa–
e, and VIIIa–e were first described in [8, 9] and were
prepared along these procedures.
N-arylthio-1,4-benzoquinonimines alkyl-substituted
in the quinoid ring (Ia–e, V, VI, VIIa–e) were prepared
for the first time by acylation of alkyl-substituted para-
aminophenols with appropriate arenesulfenyl chlorides
in the presence of triethylamine. In the course of the
reaction the intermediate N-arylthio-1,4-aminophenols
were oxidized by the air oxygen to the corresponding
N-arylthio-1,4-benzoquinonimines (Scheme 3).
N-arylthio-1,4-benzoquinonimines alkyl-sub-
stituted in the quinoid ring Ia–e, V, VI, VIIa–e. To a
suspension of 2 mmol of alkyl-substituted p-amino-
phenol in 20 ml of anhydrous ethyl ether were added
equimolar amounts of an appropriate arenesulfenyl
chloride and triethylamine. The separated precipitate of
triethylamine hydrochloride was filtered off, the filtrate
was evaporated under the reduced pressure of a water-
jet pump. The formed precipitate of N-arylthio-1,4-
benzoquinonimine was washed with methanol and acetic
acid. Inasmuch as the product contained a considerable
quantity of diaryldisulfide impurity, it was purified by
several recrystallizations from a suitable solvent. The
characteristics of N-arylthio-1,4-benzoquinonimines Ia–
e, V, VI, VIIa–e are given in Table 3.
The yield of products was very low, and besides a lot
of diaryldisulfides was found in the reaction mixture,
apparently due to the competing reaction along
Scheme 4.
EXPERIMENTAL
1
13C and H NMR spectra were registered on
spectrometers Varian VXR-300 and GEMINI-200
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004

1128
PIROZHENKO et al.
5. Adams, R. and Looker, J.H., J. Am. Chem. Soc., 1951,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 8 2004