Reactions of N-substituted 2,6(3,5)-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

Article abstract of DOI:10.1134/S1070428009010084

The regioselectivity in the reactions of N-arylsulfonyl-2,6-dialkyl-1,4- benzoquinone imines with arenesulfinic acids (1,6-, 6,1-, or 6,3-addition) is determined by steric factor, while in the reactions of N-aroyl-1,4-benzoquinone imines electronic effect

Full text of DOI:10.1134/S1070428009010084

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 1, pp. 48–67. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.P. Avdeenko, S.A. Konovalova, D.A. Roman’kov, K.S. Burmistrov, V.M. Nichvoloda, O.V. Shishkin, R.I. Zubatyuk, G.V. Pala-
marchuk, 2009, published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 1, pp. 55–74.
Reactions of N-Substituted 2,6(3,5)-Dialkyl-1,4-benzoquinone
Imines with Arenesulfinic Acids
A. P. Avdeenkoa, S. A. Konovalovaa, D. A. Roman’kova, K. S. Burmistrovb, V. M. Nichvolodab,
O. V. Shishkinc, R. I. Zubatyukc, and G. V. Palamarchukc
a Donbass State Machine-Building Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Ukrainian State University of Chemical Technology, Dnepropetrovsk, Ukraine
c Institute of Single Crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine
Received February 6, 2008
Abstract—The regioselectivity in the reactions of N-arylsulfonyl-2,6-dialkyl-1,4-benzoquinone imines with
arenesulfinic acids (1,6-, 6,1-, or 6,3-addition) is determined by steric factor, while in the reactions of N-aroyl-
1,4-benzoquinone imines electronic effect of substituents in the quinoid ring is crucial. The reactions of
N-arylsulfonyl-3,5-dimethyl-1,4-benzoquinone imines with arenesulfinic acids follow mainly the 1,4-addition
pattern. N-(N-Arylsulfonylbenzimidoyl)-1,4-benzoquinone imines are capable of reacting in a way similar to
both N-arylsulfonyl and N-aroyl derivatives.
DOI: 10.1134/S1070428009010084
Reactions of various N-substituted 1,4-benzo-
quinone imines with arenesulfinic acids have been
extensively studied [1, 2]. These reactions were found
to follow four alternative patterns: 1,4-, 1,6-, 6,1-, and
6,3-addition, where the first number denotes the atom
that takes up a proton (or other electrophile), and the
second denotes the atom that takes up the corre-
sponding acid anion (or other nucleophile); the atom
numbering is shown below [2]:
dition product from 2,6-dimethyl-N-(4-tolylsulfonyl)-
1,4-benzoquinone imine should be expected. More-
over, its fraction should be greater than in the reactions
with 2,6-diisopropyl- and 2,6-di-tert-butyl-substituted
analogs, for steric shielding of the oxygen atom in the
former is minimal. Nevertheless, no 1,6-addition prod-
uct was detected previously [2]. It should also be noted
1
that the H NMR spectra of the products were meas-
ured in different solvents, so that comparison of the
spectral patterns and signal assignment were consider-
ably complicated. In the present work we made an at-
tempt to eliminate existing discrepancies in the de-
scription of reactions of 2,6-dialkyl-N-arylsulfonyl-
1,4-benzoquinone imines with arenesulfinic acids.
X
N
O
5
6
2
1
3
4
While studying reactions of 2,6-dialkyl-N-(p-tolyl-
sulfonyl)-1,4-benzoquinone imines with sodium
4-methylbenzenesulfinate we found that the regio-
selectivity in this process is determined by steric factor
(among others) [2]. Depending on the size of the sub-
stituents in positions 2 and 6 of the quinoid ring, the
most typical are 1,6- (for N-arylsulfonyl-2,6-diiso-
propyl-1,4-benzoquinone imines) and 6,1-additions
(for N-arylsulfonyl-2,6-di-tert-butyl-1,4-benzoquinone
imines), while 2,6-dimethyl-N-(4-tolylsulfonyl)-1,4-
benzoquinone imine gives rise to 6,1- and 6,3-addition
products. However, taking into account steric effect of
substituents in the quinoid ring, formation of 1,6-ad-
The redox potential of quinone imines strongly
depends on the substituent on the nitrogen atom, and it
considerably affects the direction of nucleophilic addi-
tion to these compounds [3] since such reactions can
formally be regarded as irreversible reduction proc-
esses. In the addition of a nucleophile at the quinone
imine ring, the difference between its redox potential
and that of p-benzoquinone is crucial, for this differ-
ence determines the structure of primary intermediate.
Among known p-quinone imines, N-aroyl-1,4-benzo-
quinone imines are characterized by the highest redox
potentials; therefore, such substrates should be expect-
48

REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
49
The results of the reactions of N-substituted
1,4-benzoquinone imines I–IX with arenesulfinic acids
Xa–Xc are shown in Scheme 1, and the addition prod-
uct ratios (with no account taken of the reduction prod-
ucts) are summarized in Table 1.
ed to react with nucleophiles in a different way than
N-arylsulfonyl derivatives. The latter occupy an inter-
mediate place between N-aroyl-1,4-benzoquinone
imines and p-benzoquinones with respect to their red-
ox potentials.
While analyzing the reaction mixtures obtained
from N-arylsulfonyl derivatives, 4-amino-N,N-bis-
(arylsulfonyl)-2,6-dimethyl(isopropyl, tert-butyl)phe-
nols XXa, XXIIa, and XXVa, which were isolated as
individual substances, were used as reference. These
compounds possess two equivalent substituents on the
nitrogen atom, and they display similar sets of signals
N-(N-Arylsulfonylbenzimidoyl)-1,4-benzoquinone
imines possess a bulky substituent on the nitrogen
atom, which should hinder their reactions with nucleo-
philes according to the 6,1-addition scheme, whereas
their redox potentials are intermediate between those
of N-aroyl and N-arylsulfonyl analogs [3]. The reac-
tivity of N-aroyl-1,4-benzoquinone imines and
N-(N-arylsulfonylbenzimidoyl)-1,4-benzoquinone
imines has been studied insufficiently. Their reactions
with arenesulfinic acids have not been reported.
1
in the H NMR spectra; therefore, we succeeded in
identifying 1,6-, 6,1-, and 6,3-addition products on the
basis of only spectral data. Comparison of the 1H NMR
spectra of the product mixtures and individual com-
pounds showed that aromatic protons in the amino-
phenol fragment of N-arylsulfonyl derivatives charac-
teristically resonate at δ 6.56–6.69 (6,1-addition),
6.94–7.17 (1,6-addition), or 7.60–7.65 ppm (6,3-ad-
dition).
The present study was aimed at elucidating the
relation between the redox potential of quinone imines
(which is related in turn to electron-acceptor properties
of the substituent on the nitrogen atom) and the regio-
selectivity in the addition of arenesulfinic acids to
N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenz-
imidoyl)-2,6(3,5)-dialkyl-1,4-benzoquinone imines.
In the case of N-aroyl derivatives, assignment of
signals from protons in the aminophenol ring in the
1,6- and 6,1-addition products was somewhat difficult.
The reactions of N-arylsulfonyl-2,6(3,5)-dialkyl-
1,4-benzoquinone imines Ia, Ib, IVa, IVb, VIIa,
VIIb, XLa, and XLb, N-aroyl-2,6(3,5)-dialkyl-1,4-
benzoquinone imines IIa–IIc, Va–Vc, VIIIa, VIIIb,
and XLIa–XLIe, and N-(N-arylsulfonylbenzimidoyl)-
2,6(3,5)-dialkyl-1,4-benzoquinone imines IIIa–IIId,
VIa, VIb, IXa, IXb, and XLIIa–XLIIe with sodium
arenesulfinates Xa–Xc were carried out in acetic acid
at a reactant ratio of 1:2. While planning experiments,
the substituents in the para position of the aromatic
fragments in the initial quinone imines and arenesul-
finates (mainly Me and MeO groups) were selected so
that to ensure unambiguous signal assignment in the
1H NMR spectra.
1
Even comparison of the H NMR and IR spectra of
individual compounds and product mixtures did not
allow us to draw unambiguous conclusions. Therefore,
the structure of the products obtained from N-aroyl-
2,6-dialkyl-1,4-benzoquinone imines and arenesulfinic
acids was determined by X-ray analysis of single crys-
tals of 4-(4-methoxybenzoylamino)-2,6-dimethyl-
phenyl 4-methylbenzenesulfonate (XIIb) (Fig. 1) and
4-(chlorobenzoylamino)-2,6-diisopropylphenyl
4-methoxybenzenesulfonate (XVc) (Fig. 2).
Due to the presence of substituents in positions 2
and 6 of the central ring in molecules XIIb and XVc
the ordinary O–S bond is almost orthogonal to the aro-
matic ring plane [the torsion angles S1O3C8C9 (XIIb)
and S1O2C11C10 (XVb) are 77.4(2) and –92.8(3)°, re-
spectively]. As a result, conjugation between the lone
electron pair on the oxygen atom and the aromatic
π-system is broken, and the O3–C8 (XIIb) and O2–C11
bonds (XVb) are extended to 1.423(2) and 1.437(4) Å,
respectively, relative to the standard value 1.401 Å
[average C–O bond length in esters C*–C(=O)–O–C*]
[2]. Extension of the C16–N1 bond in molecule XIIb to
1.413(2) Å and of the N1–C7 bond in molecule XVc to
1.419(4) Å relative to the average value 1.353 Å [4]
should also be noted. Molecules of XIIb and XVc in
crystal are linked to infinite chains through inter-
molecular hydrogen bonds N–H···O between the
1
The product mixtures were analyzed by H NMR
spectroscopy before recrystallization (after precipita-
tion from the reaction solution with water). With
a view to reliably determine the product structure and
1
assign signals in the H NMR spectra, a part of the
product mixture obtained in each experiment was
recrystallized, and both recrystallized product and that
precipitated with water from the mother liquor were
1
examined by H NMR spectroscopy. As a result, we
succeeded in identifying even those compounds whose
fraction in the product mixture did not exceed a few
percent. In some cases, repeated recrystallization was
necessary to isolate individual compounds with a suf-
ficient purity.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

AVDEENKO et al.
50
Scheme 1.
H
N
R1
O
X
O
S
1,6
O
R1
R3
R2
XIa–XIc, XIIa–XIIe, XIIIa–XIIIe,
XIVa–XIVd, XVa–XVc, XVIa–XVIe,
XVIIa, XVIIb, XVIIIa, XVIIIb, XIXa–XIXe
R3
R2
X
N
SO2
6,1
R1
R1
X
HO
N
O
XXa–XXc, XXIa–XXId, XXIIa–XXIId
XXIIIa–XXIIIc, XXIVa–XXIVe, XXVa, XXVb
XXVIa, XXVIb, XXVIIa–XXVIIe
SO2Na
R2
AcOH
+
R1
R1
R3
R3
R2
X
NH
Ia, Ib, IIa–IIc, IIIa–IIId, IVa, IVb
Va–Vc, VIa, VIb, VIIa, VIIb
VIIIa, VIIIb, IXa, IXb
Xa–Xc
6,3
R1
SO2
HO
R1
XXVIIIa–XXVIIIc, XXIXa–XXIXd, XXXa–XXXe
X
NH
R1
[H]
R2
R1
OH
XXXIa–XXXIc, XXXIIa–XXXIId, XXXIIIa–XXXIIIc
XXXIVa, XXXIVb, XXXVa–XXXVc, XXXVIa
XXXVIb, XXXVIIa, XXXVIIb
I, X = SO2, R1 = Me, R2 = Me (a), Cl (b); II, X = CO, R1 = R2 = Me (a), R1 = Me, R2 = MeO (b), H (c); III, X = C(=NSO2Ar), R1 =
Me, R2 = H, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b), 4-ClC6H4 (c), 4-BrC6H4 (d); IV, X = SO2, R1 = i-Pr, R2 = Me (a), Cl (b); V, X =
CO, R1 = i-Pr, R2 = Me (a), MeO (b), Cl (c); VI, C(=NSO2Ar), R1 = i-Pr, R2 = H, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b); VII, X = SO2,
R1 = t-Bu, R2 = Me (a), MeO (b); VIII, X = CO, R1 = t-Bu, R2 = Me (a), Cl (b); IX, X = C(=NSO2Ar), R1 = t-Bu, R2 = H, Ar =
4-MeC6H4 (a), 4-MeOC6H4 (b); X, R3 = Me (a), MeO (b), Cl (c); XI, X = SO2, R1 = R2 = R3 = Me (a), R1 = R3 = Me, R2 = Cl (b),
R1 = Me, R2 = Cl, R3 = MeO (c); XII, X = CO, R1 = R2 = Me, R3 = MeO (a), R1 = R3 = Me, R2 = MeO (b), R1 = Me, R2 = MeO, R3 =
Cl (c), R1 = Me, R2 = H, R3 = MeO (d); XIII, X = C(=NSO2Ar), R1 = Me, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a), Ar = 4-MeOC6H4,
R3 = MeO (b), Ar = 4-MeOC6H4, R3 = Me (c), Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XIV, X = SO2, R1 =
i-Pr, R2 = R3 = Me (a), R2 = Me, R3 = MeO (b), R2 = Cl, R3 = Me (c), R2 = Cl, R3 = MeO (d); XV, X = CO, R1 = i-Pr, R2 = Me, R3 =
MeO (a), R2 = MeO, R3 = Me (b), R2 = Cl, R3 = MeO (c); XVI, X = C(=NSO2Ar), R1 = i-Pr, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a),
Ar = 4-MeOC6H4, R3 = MeO (b), Ar = 4-MeOC6H4, R3 = Me (c), Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XVII,
X = SO2, R1 = t-Bu, R2 = R3 = Me (a), R2 = MeO, R3 = Me (b); XVIII, X = CO, R1 = t-Bu, R2 = Cl, R3 = MeO (a), R2 = Me, R3 =
MeO (b); XIX, X = C(=NSO2Ar), R1 = t-Bu, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a), Ar = 4-MeOC6H4, R3 = MeO (b), Ar =
4-MeOC6H4, R3 = Me (c), Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XX, X = SO2, R1 = R2 = R3 = Me (a), R1 =
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
51
Scheme 1. (Contd.)
R3 = Me, R2 = Cl (b), R1 = Me, R2 = Cl, R3 = MeO (c); XXI, X = CO, R1 = R2 = Me, R3 = MeO (a), R1 = R3 = Me, R2 = MeO (b),
R1 = Me, R2 = MeO, R3 = Cl (c), R1 = Me, R2 = H, R3 = MeO (d); XXII, X = SO2, R1 = i-Pr, R2 = R3 = Me (a), R2 = Me, R3 =
MeO (b), R2 = Cl, R3 = Me (c), R2 = Cl, R3 = MeO (d); XXIII, X = CO, R1 = i-Pr, R2 = Me, R3 = MeO (a), R2 = MeO, R3 = Me (b),
R2 = Cl, R3 = MeO (c); XXIV, X = C(=NSO2Ar), R1 = i-Pr, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a), Ar = 4-MeOC6H4, R3 = MeO (b),
Ar = 4-MeOC6H4, R3 = Me (c), Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XXV, X = SO2, R1 = t-Bu, R2 = R3 =
Me (a), R2 = MeO, R3 = Me (b); XXVI, X = CO, R1 = t-Bu, R2 = Cl, R3 = MeO (a), R2 = Me, R3 = MeO (b); XXVII, X =
C(=NSO2Ar), R1 = t-Bu, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a), Ar = 4-MeOC6H4, R3 = MeO (b), Ar = 4-MeOC6H4, R3 = Me (c),
Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XXVIII, X = SO2, R1 = R2 = R3 = Me (a), R1 = R3 = Me, R2 = Cl (b),
R1 = Me, R2 = Cl, R3 = MeO (c); XXIX, X = CO, R1 = R2 = Me, R3 = MeO (a), R1 = R3 = Me, R2 = MeO (b), R1 = Me, R2 = MeO,
R3 = Cl (c), R1 = Me, R2 = H, R3 = MeO (d); XXX, X = C(=NSO2Ar), R1 = Me, R2 = H, Ar = 4-MeC6H4, R3 = MeO (a), Ar =
4-MeOC6H4, R3 = MeO (b), Ar = 4-MeOC6H4, R3 = Me (c), Ar = 4-ClC6H4, R3 = MeO (d), Ar = 4-BrC6H4, R3 = Me (e); XXXI, X =
CO, R1 = Me, R2 = Me (a), MeO (b), H (c); XXXII, X = C(=NSO2Ar), R1 = Me, R2 = H, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b),
4-ClC6H4 (c), 4-BrC6H4 (d); XXXIII, X = CO, R1 = i-Pr, R2 = Me (a), MeO (b), Cl (c); XXXIV, X = C(=NSO2Ar), R1 = i-Pr, R2 =
H, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b); XXXV, X = SO2, R1 = t-Bu, R2 = Me (a), MeO (b), Cl (c); XXXVI, X = CO, R1 = t-Bu,
R2 = Me (a), Cl (b); XXXVII, X = C(=NSO2Ar), R1 = t-Bu, R2 = H, Ar = 4-MeC6H4 (a), 4-MeOC6H4 (b).
amide groups of the neighboring molecules [XIIb:
N1–H1A···O4′; x, 1 – y, –0.5 + z; H···O 2.14 Å, ∠NHO
154°; XVc: N1–H1A···O1′; 1.5 – x, y, 0.5 + z; H···O
2.09 Å, ∠NHO 154°].
the aminophenol ring, δ, ppm: 1,6-adducts, 7.25–7.72;
6,1-adducts, 6.68–6.96, and 6,3-adducts, 7.66–7.71.
Thus our experiments showed that that all reactions
of 1,4-benzoquinone imines I–IX with arenesulfinic
acids are accompanied by formation of the correspond-
ing 1,6-addition products (addition at the oxygen
atom). We were the first to obtain 1,6-addition prod-
ucts not only from N-arylsulfonyl-2,6-diisopropyl-1,4-
benzoquinone imines [4-amino-N,O-bis(arylsulfonyl)-
2,6-diisopropylphenols XIVa–XIVd] but also from
N-arylsulfonyl-2,6-dimethyl-1,4-benzoquinone imines
[4-amino-N,O-bis(arylsulfonyl)-2,6-dimethylphenols
XIa–XIc] and N-arylsulfonyl-2,6-di-tert-butyl-1,4-
benzoquinone imines [4-amino-N,O-bis(arylsulfonyl)-
2,6-di-tert-butylphenols XVIIa and XVIIb]. Com-
pounds XIa–XIc, XVIIa, and XVIIb were not isolated
previously. Addition products at the nitrogen atom
(6,1-addition pattern) were isolated in all cases, except
for N-(N-arylsulfonylbenzimidoyl)-2,6-dimethyl-1,4-
benzoquinone imines IIIa–IIId.
On the basis of the X-ray diffraction data, we were
able to determine specificity of the spectral patterns of
the addition products of arenesulfinates to N-aroyl-2,6-
dialkyl-1,4-benzoquinone imines. Protons in the amino-
phenol ring of 1,6-addition products are characterized
by chemical shifts of δ 7.53–7.91 ppm, those in
6,1-addition products resonate in the region δ 6.67–
6.82 ppm, and analogous protons in 6,3-adducts appear
at δ 7.82–7.83 ppm. Compounds XIIa–XIId, XVa,
XVc, and XVIa–XVIc display in the IR spectra NH
absorption band at 3310–3350 cm–1.
1
According to the H NMR data, addition products
of arenesulfinates to 2,6-dialkyl-N-(N-arylsulfonyl-
benzimidoyl)-1,4-benzoquinone imines are charac-
terized by the following chemical shifts of protons in
C21
C22
O4
C1
C17
C20
C16
C14
C2
C12
C7
C13
C18
C23
C11
C3
C19
N1
C6
C4
C8
O3
C10
C5
C9
S1
O2
O1
C15
Fig. 1. Structure of the molecule of 2,6-dimethyl-4-(4-methoxybenzoylamino)phenyl 4-methylbenzenesulfonate (XIIb) according to
the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

AVDEENKO et al.
52
Table 1. Product composition in the reactions of 2,6-dialkyl-1,4-benzoquinone imines I–IX with sodium arenesulfinates
Xa–Xc (Scheme 1)
Fraction of addition products, %
X
R1
R3
R4
1,6
6,1
6,3
SO2
SO2
SO2
CO
CO
CO
CO
Me
Me
Cl
Me
44
40
43
52
0.62.5
68
71
95
93
94
89
94
51
53
52
49
69
71
67
89
84
84
35
45
87
77
65
80
60
26
24
22
14
11
23
14
–
30
36
35
34
0.26.5
09
15
05
07
06
11
06
–
Me
Me
Me
Cl
MeO
MeO
Me
Me
Me
MeO
MeO
H
Me
Me
Cl
Me
MeO
MeO
MeO
MeO
Me
C(=NSO2C6H4Me-4)
Me
H
C(=NSO2C6H4Cl-4)
Me
H
–
C(=NSO2C6H4OMe-4)
Me
H
–
C(=NSO2C6H4OMe-4)
Me
H
–
C(=NSO2C6H4Br-4)
Me
H
Me
–
SO2
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
Me
Me
Cl
Me
49
47
48
51
31
29
33
11
16
16
65
55
13
23
35
20
40
SO2
MeO
Me
–
SO2
–
SO2
Cl
MeO
MeO
Me
–
CO
Me
MeO
Cl
–
CO
–
CO
MeO
MeO
MeO
Me
–
C(=NSO2C6H4Me-4)
C(=NSO2C6H4OMe-4)
C(=NSO2C6H4OMe-4)
SO2
H
–
H
–
H
–
Me
MeO
Me
Cl
Me
–
SO2
Me
–
CO
MeO
MeO
MeO
MeO
Me
–
CO
–
C(=NSO2C6H4Me-4)
C(=NSO2C6H4OMe-4)
C(=NSO2C6H4OMe-4)
H
–
H
–
H
–
In going from 2,6-dimethyl- (Ia and Ib) to 2,6-di-
tert-butyl-sustituted N-arylsulfonyl-1,4-benzoquinone
imines VIIa and VIIb, the ratio of 1,6- and 6,1-addi-
tion products changes from 2 :1 do 2:3, indicating
steric effect of the substituents in positions 2 and 6 of
the quinoid ring on the addition of arenesulfinic acids
to these compounds.
arenesulfonates XIIa–XIId, XVa–XVc, XVIIIa, and
XVIIIb, were formed as the major products, and the
reaction mixtures also contained reduction products
XXXIa–XXXIc, XXXIIIa–XXXIIIc, XXXVIa, and
XXXVIb. Analysis of the product ratio showed that,
unlike N-arylsulfonyl-1,4-benzoquinone imines, steric
factor is not determining in the addition of arenesul-
finates to N-aroyl-2,6-dialkyl-1,4-benzoquinone
imines: as the size of the substituents in positions 2
and 6 of the quinoid ring of compounds IIa–IIc, Va–
Vc, VIIIa, and VIIIb increases, the fraction of the
In the reactions with N-aroyl-2,6-dialkyl-1,4-benzo-
quinone imines IIa–IIc, Va–Vc, VIIIa, and VIIIb, the
corresponding 1,6-addition products, 4-(N-aroyl-
amino)-2,6-dimethyl(isopropyl-, tert-butyl)phenyl
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
53
C16
C15
C26
C14
C22
C9
C21
C10
C3
C2
C23
Cl1
O4
C1
N1
O5
C8
C7
C4
C20
S1
C6
C11
O1
C5
C24
O2
O3
C12
C13
C25
C17
C18
C19A
C19
C18A
Fig. 2. Structure of the molecule of 4-(4-chlorobenzoylamino)-2,6-diisopropylphenyl 4-methoxybenzenesulfonate (XVc) according
to the X-ray diffraction data.
corresponding 1,6-addition also increases (Table 1).
This may be interpreted in terms of deactivation of the
reaction center (nitrogen atom) by strong electron-
withdrawing ArCO group and activation of the oxygen
atom due to effect of donor alkyl groups in positions 2
and 6; here, increase in the donor properties of substit-
uents in the series Me > i-Pr > t-Bu is accompanied by
increase in the fraction of the 1,6-addition product.
and IIIa–IIId. The absence of analogous compounds
among products of addition to quinone imines IV–IX
may be rationalized in terms of steric effect of bulky
isopropyl and tert-butyl groups in the quinoid ring.
In most cases, we isolated reduction products of the
initial quinone imines, N-arylsulfonyl-, N-aroyl-, and
N-(N-arylsulfonylbenzimidoyl)aminophenols XXXI–
XXXVII, and their fraction in the reaction mixtures
increased in parallel with the redox potential of the
initial quinone imines [3].
N-(N-Arylsulfonylbenzimidoyl)-1,4-benzoquinone
imines IIIa–IIId, VIa, VIb, IXa, and IXb are struc-
tural analogs of N-aroyl-1,4-benzoquinone imines [5].
They occupy an intermediate place between N-arylsul-
fonyl and N-aroyl derivatives with respect to electron-
withdrawing effect of the substituent on the nitrogen
atom and redox potential. Our experimental results
showed that they behave similarly to both N-arylsul-
fonyl and N-aroyl analogs. As in N-aroyl-1,4-benzo-
quinone imines, the main reaction center in N-(N-aryl-
sulfonylbenzimidoyl) derivatives is the oxygen atom.
On the other hand, the fraction of 1,6-addition products
decreases as the size of the substituents in positions 2
and 6 of the quinoid ring increases, as in the reactions
with N-arylsulfonyl derivatives. It should be noted that
quinone imines IIIa–IIId did not give rise to addition
products at the nitrogen atom, while the fraction of the
6,3-addition products was ~6–11%, presumably due to
considerable steric hindrances created by the bulky
CPh(=NSO2Ar) substituent on the nitrogen atom.
The reaction mixtures obtained from quinone
imines Va–Vc, VIa, VIb, VIIIa, VIIIb, IXa, and IXb
and arenesulfinic acids also contained 3,5-dialkyl-4-
Scheme 2.
O
AcOH, Δ
Va–Vc, VIa, VIb
VIIIa, VIIIb, IXa, IXb
R1
R1
O
A
R1
Xa–Xc
HO
O
S
R2
O
R1
O
XXXVIIIa–XXXVIIIc, XXXIXa, XXXIXb
XXXVIII, R1 = i-Pr, R2 = Me (a), MeO (b), Cl (c);
XXXIX, R1 = t-Bu, R2 = Me (a), MeO (b).
6,3-Addition products were isolated only in the
reactions with 2,6-dimethyl derivatives Ia, Ib, IIa–IIc,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

AVDEENKO et al.
54
Scheme 3.
R1
Me
O
O
H
N
S
1,4
X
Me
OH
R2
XLIIIa–XLIIIc, XLIVa–XLIVe, XLVa–XLVe
R2
Me
Me
R1
Me
H
N
N
O
Xa, Xb, AcOH
1,6
X
R1
X
S
O
Me
O
O
XLa, XLb, XLIa–XLIe, XLIIa–XLIe
XLVIa–XLVIc, XLVIIa–XLVIIe, XLVIIIa–XLVIIIe
R2
O
S
N
O Me
6,1
R1
X
Me
OH
XLIXa–XLIXc, La–Le
XL, X = SO2, R1 = Me (a), MeO (b); XLI, X = CO, R1 = Me (a), MeO (b), Cl (c), Br (d), H (e); XLII, X = C(=NSO2Ar), R1 = H,
Ar = Ph (a), 4-MeC6H4 (b), 4-MeOC6H4 (c), 4-ClC6H4 (d), 4-BrC6H4 (e); XLIII, X = SO2, R1 = Me, R2 = MeO (a), R1 = MeO, R2 =
Me (b), R1 = R2 = MeO (c); XLIV, X = CO, R1 = Me, R2 = MeO (a), R1 = Cl, R2 = MeO (b), R1 = Br, R2 = MeO (c), R1 = MeO, R2 =
Me (d), R1 = H, R2 = Me (e); XLV, X = C(=NSO2Ar), R1 = H, Ar = 4-MeC6H4, R2 = MeO (a), Ar = 4-MeOC6H4, R2 = MeO (b), Ar =
4-BrC6H4, R2 = MeO (c), Ar = 4-ClC6H4, R2 = MeO (d), Ar = Ph, R2 = Me (e); XLVI, X = SO2, R1 = Me, R2 = MeO (a), R1 = MeO,
R2 = Me (b), R1 = R2 = MeO (c); XLVII, X = CO, R1 = Me, R2 = MeO (a), R1 = Cl, R2 = MeO (b), R1 = Br, R2 = MeO (c), R1 =
MeO, R2 = Me (d), R1 = H, R2 = Me (e); XLVIII, X = C(=NSO2Ar), R1 = H, Ar = 4-MeC6H4, R2 = MeO (a), Ar = 4-MeOC6H4, R2 =
MeO (b), Ar = 4-BrC6H4, R2 = MeO (c), Ar = 4-ClC6H4, R2 = MeO (d), Ar = Ph, R2 = Me (e); XLIX, X = SO2, R1 = Me, R2 =
MeO (a), R1 = R2 = MeO (b); L, X = CO, R1 = Me, R2 = MeO (a), R1 = Cl, R2 = MeO (b), R1 = Br, R2 = MeO (c), R1 = MeO,
R2 = Me (d), R1 = H, R2 = Me (e).
hydroxyphenyl arenesulfonates XXXVIIIa–
XXXVIIIc, XXXIXa, and XXXIXb formed via
addition of arenesulfinic acids to 1,4-benzoquinones A
resulting in turn from hydrolysis of the initial quinone
imines (Scheme 2). 1,4-Benzoquinones A were not
detected in the reaction mixtures. The structure of
compounds XXXVIIIa–XXXVIIIc, XXXIXa, and
XXXIXb was confirmed by independent synthesis
from 2,6-diisopropyl(tert-butyl)-1,4-benzoquinones A
and arenesulfinates Xa–Xc, as well as by elemental
and N-(N-arylsulfonylbenzimidoyl)-3,5-dimethyl-1,4-
benzoquinone imines XLIIa–XLIIe with sodium
arenesulfinates Xa and Xb, and the product ratios are
collected in Table 2. The structure of the 1,6- and
6,1-addition products derived from N-arylsulfonyl
derivatives XLa and XLb (compounds XLVIa–XLVIc
and XLIXa–XLIXc) was proved by analysis of the
1H NMR spectra recorded from the filtrates obtained
after recrystallizattion of the product mixtures. As
described above for N-arylsulfonyl-2,6-dimethyl-1,4-
benzoquinone imines, signals in their 1H NMR spectra
were assigned on the basis of the 1H NMR spectrum of
6,1-addition product XLIXc having two equivalent
substituents on the nitrogen atom.
1
analyses and 1H NMR data. In the H NMR spectra of
these compounds, the CH proton in the isopropyl
groups resonated at δ 3.14–3.29 ppm, which is typical
of 6,1-addition products.
Scheme 3 shows the results of the reactions of
The structure of N-aroyl-3,5-dimethyl-1,4-benzo-
N-arylsulfonyl- (XLa, XLb), N-aroyl- (XLIa–XLIe),
quinone imines could not be assigned unambiguously
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
55
Table 2. Product composition in the reactions of 3,5-dimethyl-1,4-benzoquinone imines XL–XLII with sodium arenesul-
finates Xa and Xb (Scheme 3)
Fraction of addition products, %
X
R1
R2
1,4
6,1
1,6
SO2
SO2
SO2
CO
CO
CO
CO
CO
CO
CO
Me
MeO
MeO
Me
Me
Me
MeO
Cl
MeO
Me
91
81
83
12
27
10
35
24
29
26
81
81
79
82
90
05
15
14
77
45
79
39
55
51
56
–
04
04
03
11
28
11
26
21
20
18
19
19
21
18
10
MeO
Me
MeO
Cl
Me
MeO
Me
H
Br
MeO
Me
C(=NSO2Ph)
H
C(=NSO2C6H4Me-4)
C(=NSO2C6H4Cl-4)
C(=NSO2C6H4Br-4)
C(=NSO2C6H4OMe-4)
H
MeO
MeO
MeO
MeO
–
H
–
H
–
H
–
1
on the basis of the H NMR data. Therefore, one of
these compounds, N-(2,6-dimethyl-4-hydroxyphenyl)-
4-methoxyphenylsulfonyl)-4-meth-ylbenzamide (La)
was examined by X-ray diffraction (Fig. 3).
molecular contacts H7C ···C16 2.74 Å (the sum of the
corresponding van der Waals radii is 2.87 Å [6]),
C4 ···C18 2.99 Å (3.42 Å), C5 ···H18 2.58 Å (2.87 Å),
and S1 ···C8 3.44 Å (3.58 Å), while the bond angles
C4C3C7 123.2(2)°, C4C5C8 122.70(19)°, and C16C17C18
126.62(19)° are increased as compared to C2C3C7
119.2(2)°, C6C5C8 118.72(19)°, and C16C17C22
The amide nitrogen atom in molecule La bears
three bulky substituents, which induce considerable
steric strain. As a result, there are shortened intra-
O1
C1
C2
C3
C7
C6
C11
C10
O3
O4
C4
C12
C5
S1
C9
N1
C15
C8
C18
C13
C17
C16
C19
C23
C14
O2
C22
O5
C20
C21
Fig. 3. Structure of the molecule of N-(4-hydroxy-2,6-dimethylphenyl)-N-(4-methoxyphenylsulfonyl)-4-methylbenzamide (La)
according to the X-ray diffraction data.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

AVDEENKO et al.
56
dition products is similar to that found in the reactions
with N-aroyl derivatives. The absence of addition
products at the nitrogen atom is likely to result from
considerable steric hindrances due to the presence of
substituents in positions 3 and 5 of the quinoid ring
and bulky substituent on the nitrogen atom.
115.56(18)°, respectively. Steric strain in molecule La
leads to rupture of conjugation between the π-electron
system of the phenol ring and lone electron pair on
the nitrogen atom [the torsion angle C4C3N1C16 is
–72.4(3)°]. Molecules La in crystal give rise to chains
along the crystallographic (100) axis due to intermo-
lecular hydrogen bonds O1–H1A···O3′ (0.5 + x, 0.5 – y,
0.5 + z) (H···O 1.99 Å, ∠OHO 168.8°).
Thus in the present work we determined the
following general relations holding in the reactions of
symmetrically substituted 1,4-benzoquinone imines
with arenesulfinic acids:
Addition products of arenesulfinates to 3,5-di-
methyl-1,4-benzoquinone imines are characterized by
the following chemical shifts of aromatic protons in
the aminophenol fragment: 1,4-adducts: δ 6.84–
6.85 ppm for N-arylsulfonyl derivatives and δ 6.68–
6.82 ppm for N-aroyl- and N-(N-arylsulfonylbenz-
imidoyl) derivatives; 6,1-adducts: δ 6.56 ppm for
N-arylsulfonyl and δ 6.44–6.48 ppm for N-aroyl
derivatives; 1,6-adducts: δ 6.71 ppm for N-arylsulfonyl
and δ 6.82–6.86 ppm for N-aroyl and N-(N-arylsul-
fonylbenzimidoyl) derivatives. In the IR spectrum of
La, the OH group gave rise to absorption at 3450 cm–1.
1,4-Addition products XLIIIa–XLIIIc characteristi-
cally displayed absorption bands at 3210–3250 (NH)
and 3290–3300 cm–1 (OH).
(1) N-Substituted 1,4-benzoquinone imines react
with arenesulfinic acids according to 1,6-, 6,1-, 6,3-,
and 1,4-addition patterns, and the regioselectivity of
the addition is determined by the reactivity ratio of the
N, C2/C6, C3/C5, and O centers in the quinoid ring;
(2) The most reactive centers in N-arylsulfonyl-1,4-
benzoquinone imines with respect to arenesulfinates
are positions 2 and 6 in the quinoid ring; when these
positions are occupied, the addition direction is deter-
mined by steric factor, i.e., by the size of substituents
therein;
(3) The addition of arenesulfinates to N-aroyl-1,4-
benzoquinone imines (in which the substituent on the
nitrogen atom is the strongest electron acceptor among
the examined ones) is governed by electronic effect of
the substituents in the quinoid ring: electron-donating
substituents favor addition at the nearest reaction
center, nitrogen or oxygen atom;
The reactions of N-arylsulfonyl-3,5-dimethyl-1,4-
benzoquinone imines XLa and XLb with arenesul-
finates afforded mainly 1,4-addition products XLIIIa–
XLIIIc. In the reactions with N-aroyl-3,5-dimethyl-
1,4-benzoquinone imines XLIa–XLIe the major prod-
ucts were compounds La–Le formed via addition at
the nitrogen atom. The direction of arenesulfinate addi-
tion to N-aroyl-1,4-benzoquinone imines depends on
the electronic properties of substituents in the quinoid
ring. The presence of electron-donating substituents in
positions 3 and 5 of the quinoid ring makes the
nitrogen atom more reactive toward arenesulfinates
(Table 2). If alkyl groups are present in positions 2 and
6 of the quinoid ring (quinone imines IIa–IIc, Va–Vc,
VIIa, and VIIb), the oxygen atom becomes more reac-
tive. It should be noted that the fraction of the 1,4-ad-
dition products derived from N-aroyl derivatives is
considerably smaller than that in the reactions with
N-arylsulfonyl derivatives, i.e., positions 2 and 6 in the
quinoid ring of 3,5-dimethyl-substituted N-arylsul-
fonyl-1,4-benzoquinone imines are more reactive than
those in the corresponding N-aroyl derivatives.
(4) N-(N-Arylsulfonylbenzimidoyl)-1,4-benzoqui-
none imines whose redox potential and electronic
properties of the substituent on the nitrogen atom are
intermediate between those of analogous N-arylsul-
fonyl- and N-aroyl-1,4-benzoquinone imines exhibit
reactivity typical of both N-arylsulfonyl and N-aroyl
derivatives.
On the basis of the above stated we can conclude
that increase in the electron-withdrawing properties of
the substituent on the nitrogen atom is accompanied by
change of the effect of the substituents in the quinoid
ring on the addition of arenesulfinic acids: in going
from N-arylsulfonyl to N-aroyl derivatives, steric fac-
tor becomes less important whereas electronic effect of
the substituents and their position become crucial.
EXPERIMENTAL
The reactions of N-(N-arylsulfonylbenzimidoyl)-3,5-
dimethyl-1,4-benzoquinone imines XLIIa–XLIIe with
arenesulfinates Xa and Xb gave only 1,6- and 1,4-ad-
dition products, the latter prevailing (as with N-aryl-
sulfonyl derivatives), while the fraction of the 1,6-ad-
1
The H NMR spectra were recorded on a Varian
VXR-300 spectrometer at 300 MHz from solutions in
acetone-d6 (compounds XI, XIV, XVII, XX, XXII,
XXV, XXVIII, XXXV, XLIII, XLVI, and XLIX),
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
57
DMSO-d6 (XII, XIII, XV, XVI, XVIII, XIX, XXI,
XXIII, XXIV, XXVI, XXVII, XXIX–XXXIV,
XXXVI–XXXIX, XLIV, XLV, XLVII, XLVIII, L),
or CDCl3 (XLb, XLIId) using tetramethylsilane as
reference. The IR spectra were measured in KBr on
a UR-20 instrument. Thin-layer chromatography was
performed on Silufol UV-254 plates; spots were ap-
plied from solutions in chloroform, benzene–hexane
(10 :1) was used as eluent, and the chromatograms
were developed under UV light.
tions with F > 4σ(F), S = 0.959]; structure La: wR2 =
0.109 (3992 reflections) and R1 = 0.042 (2860 reflec-
tions with F > 4σ(F), S = 1.086]. The complete sets of
crystallographic data for compounds XIIb, XVc, and
La (coordinates of atoms and geometric parameters of
molecules) were deposited to the Cambridge Crystallo-
graphic Data Center (entry nos. CCDC 666669, CCDC
666671, and CCDC 666670, respectively).
Quinone imines I, IV, and VII were synthesized
according to the procedure described in [8] by oxida-
tion of the corresponding aminophenols with sodium
dichromate in acetic acid. Quinone imines II, III, V,
VI, IX, and XL–XLII were prepared as reported in [9]
by oxidation of the corresponding aminophenols with
lead tetraacetate in acetic acid, and quinone imines
VIII were obtained by oxidation of N-aroylaminophe-
nols with diacetoxy-λ3-iodanylbenzene as described in
[10]. The properties of compounds Ia, Ib [11], IIa–IIc
[12], IIId [5], IVa, IVb [13], Va–Vc [14], VIIa, VIIb
[15], VIIIa, VIIIb [10], XLa [16], XLIa–XLIe [12],
and XLIIe [5] were consistent with published data.
Sodium arenesulfinates Xa–Xc were synthesized as
described in [17].
The X-ray diffraction data for compounds XIIb,
XVc, and La were acquired on an Xcalibur-3 diffrac-
tometer at 293 K (MoKα irradiation, CCD detector,
graphite monochromator, ω scanning, 2θmax = 50°).
Compound XIIb: monoclinic crystals, C23H23NO5S;
unit cell parameters: a = 14.7415(9), b = 16.8436(8),
c = 9.7969(5) Å; β = 118.886(6)°; V = 2129.9(2) Å3;
Mr = 425.48; Z = 4; space group Cc; dcalc = 1.327 g ×
cm–3; µ(MoKα) = 0.186 mm–1; F(000) = 896. Total of
7032 reflections were measured, 3236 of which were
independent (Rint = 0.024).
Compound XVc: rhombic crystals, C26H29ClNO5S;
a = 26.432(1), b = 9.579(1), c = 10.055(1) Å; V =
2545.8(2) Å3; Mr = 503.01; Z = 4; space group Pca21;
dcalc = 1.312 g/cm3; µ(MoKα) = 0.269 mm–1; F(000) =
1060. Total of 17558 reflections were measured, 5658
of which were independent (Rint = 0.065).
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methylphenylsulfonyl)benzimidamide
(IIIa). Yield 88%, mp 172–174°C. Found, %: N 7.01,
7.23; S 8.03, 8.27. C22H20N2O3S. Calculated, %:
N 7.14; S 8.17.
Compound La: rhombic crystals, C23H23NO5S; a =
12.1988(3), b = 13.4836(4), c = 25.8824(8) Å; V =
4257.2(2) Å3; Mr = 425.48; Z = 4; space group Pbca;
dcalc = 1.328 g/cm3; µ(MoKα) = 0.187 mm–1; F(000) =
1792. Total of 24160 reflections were measured, 3724
of which were independent (Rint = 0.028).
N-(3,5-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methoxyphenylsulfonyl)benzimidamide
(IIIb). Yield 84%, mp 140–142°C. Found, %: N 6.82,
6.97; S 7.54, 7.78. C22H20N2O4S. Calculated, %:
N 6.86; S 7.85.
N′-(4-Chlorophenylsulfonyl)-N-(3,5-dimethyl-4-
oxocyclohexa-2,5-dienylidene)benzimidamide (IIIc).
Yield 84%, mp 175–177°C. Found, %: N 6.79, 6.94;
S 7.49, 7.82. C21H17SlN2O3S. Calculated, %: N 6.78;
S 7.77.
The structures were solved by the direct method
using SHELXTL software package [7]. The positions
of hydrogen atoms were determined by difference syn-
thesis of electron density and were refined using the
riding model with Uiso = nUequiv (where Uequiv refers to
the non-hydrogen atom to which the given hydrogen
atom is attached; n = 1.5 for methyl hydrogen atoms
and 1.2 for other hydrogen atoms). The structures were
refined with respect to F2 by the full-matrix least-
squares procedure in anisotropic approximation for
non-hydrogen atoms. In the refinement of structure
XVc, the C–C bond lengths in the disordered isopropyl
group were restricted to 1.52(1) Å. The final diver-
gence factors were as follows: structure XIIb: wR2 =
0.069 (3202 reflections) and R1 = 0.047 [2990 reflec-
tions with F > 4σ(F), S = 1.037]; structure XVc: wR2 =
0.089 (5638 reflections) and R1 = 0.047 [2632 reflec-
N-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methylphenylsulfonyl)benzimidamide
(VIa). Yield 65%, mp 101–103°C. Found, %: N 6.21,
6.44; S 7.04, 7.19. C26H28N2O3S. Calculated, %:
N 6.24; S 7.15.
N-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methoxyphenylsulfonyl)benzimidamide
(VIb). Yield 66%, mp 115–117°C. Found, %: N 6.05,
6.42; S 6.73, 6.99. C26H28N2O4S. Calculated, %:
N 6.03; S 6.90.
N-(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methylphenylsulfonyl)benzimidamide
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AVDEENKO et al.
58
(IXa). Yield 88%, mp 156–157°C. Found, %: N 5.76,
5.88; S 6.58, 6.73. C28H32N2O3S. Calculated, %:
N 5.88; S 6.73.
2,6-Dimethyl-4-(4-methylphenylsulfonylamino)-
phenyl 4-methylbenzenesulfonate (XIa). H NMR
spectrum, δ, ppm: 7.52–7.83 d.d (4H, C6H4, J =
8.1 Hz), 7.35–7.71 d.d (4H, C6H4, J = 8.7 Hz), 6.94 s
(2H, 3-H, 5-H), 2.49 s and 2.38 s (3H each, MeC6H4),
2.01 s (6H, 2-Me, 6-Me).
1
N-(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methoxyphenylsulfonyl)benzimidamide
(IXb). Yield 78%, mp 147–148°C. Found, %: N 5.47,
5.64; S 6.39, 6.48. C28H32N2O4S. Calculated, %:
N 5.69; S 6.51.
4-(4-Chlorophenylsulfonylamino)-2,6-dimethyl-
1
phenyl 4-methylbenzenesulfonate (XIb). H NMR
spectrum, δ, ppm: 7.60–7.83 d.d (4H, ClC6H4, J =
8.4 Hz), 7.52–7.83 d.d (4H, MeC6H4, J = 8.1 Hz),
6.94 s (2H, 3-H, 5-H), 2.49 s (3H, MeC6H4), 2.02 s
(6H, 2-Me, 6-Me).
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-4-methoxybenzenesulfonamide (XLb). Yield
74%, mp 117–118°C. H NMR spectrum, δ, ppm:
7.18–7.91 d.d (4H), 6.55 s (2H), 3.88 s (3H, MeO),
2.24 s (6H, Me). Found, %: N 4.62, 4.68; S 10.48,
10.62. C15H15NO4S. Calculated, %: N 4.59; S 10.50.
1
4-(4-Chlorophenylsulfonylamino)-2,6-dimethyl-
phenyl 4-methoxybenzenesulfonate (XIc). 1H NMR
spectrum, δ, ppm: 7.59–7.84 d.d (4H, ClC6H4, J =
8.7 Hz), 7.19–7.87 d.d (4H, MeOC6H4, J = 8.1 Hz),
6.94 s (2H, 3-H, 5-H), 2.95 s (3H, MeO), 2.03 s (6H,
2-Me, 6-Me).
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(phenylsulfonyl)benzimidamide (XLIIa).
Yield 69%, mp 134–136°C. Found, %: N 7.34, 7.45;
S 8.40, 8.67. C21H18N2O3S. Calculated, %: N 7.40;
S 8.47.
2,6-Dimethyl-4-(4-methylbenzoylamino)phenyl
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methylphenylsulfonyl)benzimidamide
(XLIIb). Yield 61%, mp 122–124°C. Found, %:
N 7.06, 7.28; S 8.01, 8.15. C22H20N2O3S. Calculated,
%: N 7.14; S 8.17.
4-methoxybenzenesulfonate (XIIa). Yield 40%,
mp 165–167°C. H NMR spectrum, δ, ppm: 10.13 s
1
(1H, NH), 7.33–7.86 d.d (4H, MeC6H4, J = 8.4 Hz),
7.23–7.90 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.54 s (2H,
3-H, 5-H), 3.90 s (3H, MeO), 2.38 s (3H, MeC6H4),
2.05 s (6H, 2-Me, 6-Me). Found, %: N 3.25, 3.36;
S 7.48, 7.83. C23H23NO5S. Calculated, %: N 3.29;
S 7.54.
N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dienyli-
dene)-N′-(4-methoxyphenylsulfonyl)benzimidamide
(XLIIc). Yield 84%, mp 113–115°C. Found, %:
N 6.75, 6.92; S 7.57, 7.78. C22H20N2O4S. Calculated,
%: N 6.86; S 7.85.
2,6-Dimethyl-4-(4-methoxybenzoylamino)phenyl
4-methylbenzenesulfonate (XIIb). Yield 45%,
1
N′-(4-Chlorophenylsulfonyl)-N-(2,6-dimethyl-
4-oxocyclohexa-2,5-dienylidene)benzimidamide
(XLIId). Yield 68%, mp 175°C. 1H NMR spectrum, δ,
ppm: 7.45–7.63 m (5H, Ph), 7.31–7.80 d.d (4H),
6.46 br.s (2H), 2.12 s (6H, Me). Found, %: N 6.63,
6.81; S 7.82, 7.98. C21H17ClN2O3S. Calculated, %:
N 6.78; S 7.77.
mp 230–232°C. H NMR spectrum, δ, ppm: 10.07 s
(1H, NH), 7.54–7.87 d.d (4H, MeC6H4, J = 8.1 Hz),
7.06–7.95 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.53 s (2H,
3-H, 5-H), 3.84 s (3H, MeO), 2.46 s (3H, MeC6H4),
2.04 s (6H, 2-Me, 6-Me). Found, %: N 3.17, 3.28;
S 7.44, 7.59. C23H23NO5S. Calculated, %: N 3.29;
S 7.54.
Reactions of quinone imines I–IX and XL–XLII
with sodium arenesulfinates Xa–Xc (general proce-
dure). A solution of 2 mmol of quinone imine I–IX or
XL–XLII in 20 ml of glacial acetic acid was heated to
the boiling point, and 4 mmol of the corresponding
sodium arenesulfinate Xa–Xc was added in one
portion. When the solution turned colorless, it was
cooled, and water was added until complete precipita-
tion. The colorless precipitate was filtered off and
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. The three portions of the
product were analyzed by 1H NMR spectroscopy.
2,6-Dimethyl-4-(4-methoxybenzoylamino)phenyl
4-chlorobenzenesulfonate (XIIc). Yield 48%,
1
mp 207–208°C. H NMR spectrum, δ, ppm: 10.07 s
(1H, NH), 7.82–8.02 d.d (4H, MeC6H4, J = 8.1 Hz),
7.06–7.95 d.d (4H, 4-MeOC6H4, J = 8.7 Hz), 7.55 s
(2H, 3-H, 5-H), 3.84 s (3H, MeO), 2.06 s (6H,
MeC6H4). Found, %: N 3.09, 3.18; S 7.15, 7.32.
C22H20ClNO5S. Calculated, %: N 3.14; S 7.19.
4-Benzoylamino-2,6-dimethylphenyl 4-methoxy-
benzenesulfonate (XIId). Yield 50%, mp 149–151°C.
1H NMR spectrum, δ, ppm: 10.21 s (1H, NH), 7.51–
7.92 m (5H, Ph), 7.23–7.94 d.d (4H, C6H4, J = 9.0 Hz),
7.54 s (2H, 3-H, 5-H), 3.90 s (3H, MeO), 2.05 s (6H,
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
59
Me). Found, %: N 3.33, 3.42; S 7.77, 7.96.
C22H21NO5S. Calculated, %: N 3.40; S 7.79.
6.99 s (2H, 3-H, 5-H), 3.02–3.15 m (2H, CH in i-Pr),
2.49 s and 2.37 s (3H each, MeC6H4), 0.99 d (12H, Me
in i-Pr, J = 6.9 Hz).
2,6-Dimethyl-4-[(4-methylphenylsulfonylimino)-
(phenyl)methylamino]phenyl 4-methoxybenzenesul-
2,6-Diisopropyl-4-(4-methylphenylsulfonyl-
amino)phenyl 4-methoxybenzenesulfonate (XIVb).
1H NMR spectrum, δ, ppm: 7.22–7.90 d.d (4H,
MeOC6H4, J = 8.4 Hz), 7.34–7.67 d.d (4H, MeC6H4,
J = 7.8 Hz), 6.99 s (2H, 3-H, 5-H), 3.02–3.17 m (2H,
CH in i-Pr), 3.96 s (3H, MeO), 2.37 s (3H, MeC6H4),
1.00 d (12H, Me in i-Pr, J = 6.9 Hz).
1
fonate (XIIIa). Yield 77%, mp 185–187°C. H NMR
spectrum, δ, ppm: 10.53 s (1H, NH), 7.23–7.88 d.d
(4H, MeOC6H4, J = 8.7 Hz), 7.32–7.61 d.d (4H,
MeC6H4, J = 7.8 Hz), 7.49–7.63 m (5H, Ph), 7.28 s
(2H, 3-H, 5-H), 3.90 s (3H, MeO), 2.36 s (3H,
MeC6H4), 1.91 s (6H, 2-Me, 6-Me). Found, %: N 4.87,
5.10; S 11.31, 11.48. C29H28N2O6S2. Calculated, %:
N 4.96; S 11.36.
4-(4-Chlorophenylsulfonylamino)-2,6-diiso-
propylphenyl 4-methylbenzenesulfonate (XIVc).
1H NMR spectrum, δ, ppm: 7.54–7.86 d.d (4H,
MeC6H4, J = 8.1 Hz), 7.59–7.76 d.d (4H, ClC6H4, J =
8.4 Hz), 6.98 s (2H, 3-H, 5-H), 3.02–3.15 m (2H, CH
in i-Pr), 2.50 s (3H, MeC6H4), 0.99 d (12H, Me i-Pr,
J = 6.9 Hz).
4-[(4-Methoxyphenylsulfonylimino)(phenyl)-
methylamino]-2,6-dimethylphenyl 4-methoxyben-
zenesulfonate (XIIIb). Yield 79%, mp 177–179°C.
1H NMR spectrum, δ, ppm: 10.48 s (1H, NH), 7.22–
7.88 d.d (4H, MeOC6H4, J = 9.3 Hz), 7.03–7.64 d.d
(4H, MeOC6H4, J = 8.7 Hz), 7.46–7.60 m (5H, Ph),
7.29 s (2H, 3-H, 5-H), 3.90 s (3H, MeO), 3.81 s (3H,
MeO), 1.92 s (6H, 2-Me, 6-Me). Found, %: N 4.83,
4.91; S 10.89, 10.96. C29H28N2O7S2. Calculated, %:
N 4.82; S 11.04.
4-(4-Chlorophenylsulfonylamino)-2,6-diiso-
propylphenyl 4-methoxybenzenesulfonate (XIVd).
1H NMR spectrum, δ, ppm: 7.59–7.76 d.d (4H, ClC6H4,
J = 8.4 Hz), 7.23–7.74 d.d (4H, MeOC6H4, J =
9.0 Hz), 6.98 s (2H, 3-H, 5-H), 3.05–3.17 m (2H, CH
in i-Pr), 3.96 s (3H, MeO), 1.00 d (12H, Me in i-Pr,
J = 6.6 Hz).
4-[(4-Methoxyphenylsulfonylimino)(phenyl)-
methylamino]-2,6-dimethylphenyl 4-methylben-
zenesulfonate (XIIIc). Yield 74%, mp 199–200°C.
1H NMR spectrum, δ, ppm: 10.46 s (1H, NH), 7.53–
7.85 d.d (4H, MeC6H4, J = 8.1 Hz), 7.03–7.64 d.d (4H,
MeOC6H4, J = 8.7 Hz), 7.48–7.60 m (5H, Ph), 7.30 s
(2H, 3-H, 5-H), 3.81 s (3H, MeO), 2.46 s (3H,
MeC6H4), 1.92 s (6H, 2-Me, 6-Me). Found, %: N 4.76,
4.94; S 11.23, 11.29. C29H28N2O6S2. Calculated, %:
N 4.96; S 11.36.
2,6-Diisopropyl-4-(4-methylbenzoylamino)phen-
yl 4-methoxybenzenesulfonate (XVa). Yield 51%,
1
mp 217–219°C. H NMR spectrum, δ, ppm: 10.09 s
(1H, NH), 7.25–7.93 d.d (4H, MeOC6H4, J = 9.0 Hz),
7.34–7.90 d.d (4H, MeC6H4, J = 8.1 Hz), 7.70 s (2H,
3-H, 5-H), 3.90 s (3H, MeO), 3.02–3.16 m (2H, CH in
i-Pr), 2.39 s (3H, MeC6H4), 1.07 d (12H, Me in i-Pr,
J = 6.6 Hz). Found, %: N 2.74, 2.90; S 6.57, 6.83.
C27H31NO5S. Calculated, %: N 2.91; S 6.66.
4-[(4-Chlorophenylsulfonylimino)(phenyl)-
methylamino]-2,6-dimethylphenyl 4-methoxyben-
1
zenesulfonate (XIIId). H NMR spectrum, δ, ppm:
2,6-Diisopropyl-4-(4-methoxybenzoylamino)-
1
10.65 s (1H, NH), 7.23–7.89 d.d (4H, MeOC6H4, J =
8.7 Hz), 7.58–7.71 d.d (4H, ClC6H4, J = 8.4 Hz), 7.49–
7.62 m (5H, Ph), 7.26 s (2H, 3-H, 5-H), 3.91 s (3H,
MeO), 1.92 s (6H, 2-Me, 6-Me).
phenyl 4-methylbenzenesulfonate (XVb). H NMR
spectrum, δ, ppm: 10.09 s (1H, NH), 7.50–7.88 d.d
(4H, MeC6H4, J = 8.4 Hz), 7.07–7.97 d.d (4H, MeO-
C6H4, J = 9.0 Hz), 7.68 s (2H, 3-H, 5-H), 3.85 s (3H,
MeO), 2.99–3.12 m (2H, CH in i-Pr), 2.46 s (3H,
MeC6H4), 1.067 d (12H, Me in i-Pr, J = 6.9 Hz).
4-[(4-Bromophenylsulfonylimino)(phenyl)-
methylamino]-2,6-dimethylphenyl 4-methylben-
1
zenesulfonate (XIIIe). H NMR spectrum, δ, ppm:
4-(4-Chlorobenzoylamino)-2,6-diisopropylphen-
10.66 s (1H, NH), 7.54–7.85 d.d (4H, MeC6H4, J =
8.4 Hz), 7.63–7.72 d.d (4H, BrC6H4, J = 8.7 Hz), 7.49–
7.60 m (5H, Ph), 7.25 s (2H, 3-H, 5-H), 2.46 s (3H,
MeC6H4), 1.91 s (6H, 2-Me, 6-Me).
yl 4-methoxybenzenesulfonate (XVc). Yield 49%,
mp 195–197°C. H NMR spectrum, δ, ppm: 10.31 s
1
(1H, NH), 7.25–7.93 d.d (4H, MeOC6H4, J = 9.0 Hz),
7.62–8.00 d.d (4H, ClC6H4, J = 8.4 Hz), 7.68 s (2H,
3-H, 5-H), 3.90 s (3H, MeO), 3.02–3.15 m (2H, CH in
i-Pr), 1.07 d (12H, Me in i-Pr, J = 6.9 Hz). Found, %:
N 2.78, 2.91; S 6.38, 6.52. C26H28ClNO5S. Calculated,
%: N 2.79; S 6.39.
2,6-Diisopropyl-4-(4-methylphenylsulfonyl-
amino)phenyl 4-methylbenzenesulfonate (XIVa).
1H NMR spectrum, δ, ppm: 7.54–7.85 d.d (4H, C6H4,
J = 8.4 Hz), 7.34–7.67 d.d (4H, C6H4, J = 8.1 Hz),
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AVDEENKO et al.
60
2,6-Di-tert-butyl-4-(4-methylbenzoylamino)phen-
yl 4-methoxybenzenesulfonate (XVIIIb). H NMR
spectrum, δ, ppm: 10.11 s (1H, NH), 7.35–7.90 d.d
(4H, MeC6H4, J = 9.0 Hz), 7.24–7.81 d.d (4H, MeO-
C6H4, J = 8.4 Hz), 7.91 s (2H, 3-H, 5-H), 3.89 s (3H,
MeO), 2.40 s (3H, MeC6H4), 1.32 s (18H, t-Bu).
2,6-Diisopropyl-4-[(4-methylphenylsulfonyl-
1
imino)(phenyl)methylamino]phenyl 4-methoxyben-
zenesulfonate (XVIa). Yield 69%, mp 191–192.5°C.
1H NMR spectrum, δ, ppm: 10.47 s (1H, NH), 7.23–
7.88 d.d (4H, MeOC6H4, J = 8.7 Hz), 7.33–7.88 d.d
(4H, MeC6H4, J = 8.4 Hz), 7.51–7.70 m (5H, Ph),
7.47 s (2H, 3-H, 5-H), 3.89 s (3H, MeO), 2.88–3.01 m
(2H, CH in i-Pr), 2.36 s (3H, MeC6H4), 0.82 d (12H,
Me in i-Pr, J = 6.9 Hz). Found, %: N 4.50, 4.62;
S 10.35, 10.47. C33H36N2O6S2. Calculated, %: N 4.51;
S 10.33.
2,6-Di-tert-butyl-4-[(4-methylphenylsulfonyl-
imino)(phenyl)methylamino]phenyl 4-methoxyben-
1
zenesulfonate (XIXa). H NMR spectrum, δ, ppm:
10.43 s (1H, NH), 7.71–7.80 d.d (4H, MeOC6H4, J =
7.8 Hz), 7.36–7.56 d.d (4H, MeC6H4, J = 8.1 Hz),
7.71 s (2H, 3-H, 5-H), 7.65–7.76 m (5H, Ph), 3.88 s
(3H, MeO), 2.37 s (3H, MeC6H4), 1.12 s (18H, t-Bu).
2,6-Diisopropyl-4-[(4-methoxyphenylsulfonyl-
imino)(phenyl)methylamino]phenyl 4-methoxyben-
zenesulfonate (XVIb). Yield 60%, mp 179–180.5°C.
1H NMR spectrum, δ, ppm: 10.43 s (1H, NH), 7.22–
7.88 d.d (4H, MeOC6H4, J = 8.7 Hz), 7.04–71 d.d (4H,
MeOC6H4, J = 8.7 Hz), 7.52–7.68 m (5H, Ph), 7.47 s
(2H, 3-H, 5-H), 3.89 s and 3.81 s (3H each, MeO),
2.89–3.03 m (2H, CH in i-Pr), 0.85 d (12H, Me in i-Pr,
J = 6.6 Hz). Found, %: N 4.25, 4.37; S 10.01, 10.17.
C33H36N2O7S2. Calculated, %: N 4.40; S 10.07.
2,6-Di-tert-butyl-4-[(4-methoxyphenylsulfonyl-
imino)(phenyl)methylamino]phenyl 4-methoxyben-
1
zenesulfonate (XIXb). H NMR spectrum, δ, ppm:
10.39 s (1H, NH), 7.71–7.77 d.d (4H, MeOC6H4, J =
9.0 Hz), 7.04–7.22 d.d (4H, MeOC6H4, J = 8.7 Hz),
7.72 s (2H, 3-H, 5-H), 7.53–7.66 m (5H, Ph), 3.88 s
and 3.82 s (3H each, MeO), 1.14 s (18H, t-Bu).
2,6-Di-tert-butyl-4-[(4-methoxyphenylsulfonyl-
2,6-Diisopropyl-4-[(4-methoxyphenylsulfonyl-
imino)(phenyl)methylamino]phenyl 4-methylben-
zenesulfonate (XVIc). Yield 62%, mp 195–196°C.
1H NMR spectrum, δ, ppm: 10.42 s (1H, NH), 7.66–
7.84 d.d (4H, MeC6H4, J = 8.1 Hz), 7.04–7.70 d.d (4H,
MeOC6H4, J = 9.0 Hz), 7.52–7.60 m (5H, Ph), 7.49 s
(2H, 3-H, 5-H), 3.81 s (3H, MeO), 2.86–3.00 m (2H,
CH in i-Pr), 2.45 s (3H, MeC6H4), 0.84 d (12H, Me in
i-Pr, J = 6.9 Hz. Found, %: N 4.52, 4.60, S 10.34,
10.45. C33H36N2O6S2. Calculated, %: N 4.51; S 10.33.
imino)(phenyl)methylamino]phenyl 4-methylben-
zenesulfonate (XIXc). H NMR spectrum, δ, ppm:
10.38 s (1H, NH), 7.66–7.76 d.d (4H, MeOC6H4, J =
8.4 Hz), 7.05–7.52 d.d (4H, MeC6H4, J = 8.7 Hz),
7.69 s (2H, 3-H, 5-H), 7.51–7.76 m (5H, Ph), 3.82 s
(3H, MeO), 2.44 s (3H, MeC6H4), 1.14 s (18H, t-Bu).
1
N-(4-Hydroxy-3,5-dimethylphenyl)-4-methyl-
N-(4-methylphenylsulfonyl)benzenesulfonamide
(XXa). 1H NMR spectrum, δ, ppm: 7.46–7.77 d.d (8H,
C6H4, J = 8.7 Hz), 6.60 s (2H, 2-H, 6-H), 2.49 s (6H,
MeC6H4), 2.16 s (6H, 3-Me, 5-Me).
2,6-Di-tert-butyl-4-(4-methylphenylsulfonyl-
amino)phenyl 4-methylbenzenesulfonate (XVIIa).
1H NMR spectrum, δ, ppm: 7.47–7.65 d.d (4H,
MeC6H4, J = 9.0 Hz), 7.37–7.57 d.d (4H, MeC6H4, J =
8.4 Hz), 17 s (2H, 3-H, 5-H), 2.47 s and 2.37 s (3H
each, MeC6H4), 1.31 s (18H, t-Bu).
4-Chloro-N-(4-hydroxy-3,5-dimethylphenyl)-
N-(4-methylphenylsulfonyl)benzenesulfonamide
(XXb). 1H NMR spectrum, δ, ppm: 7.79–7.91 d.d (4H,
ClC6H4, J = 9.0 Hz), 7.35–7.48 d.d (4H, MeC6H4, J =
7.8 Hz), 6.64 s (2H, 2-H, 6-H), 2.49 s (3H, MeC6H4),
2.17 s (6H, 3-Me, 5-Me).
2,6-Di-tert-butyl-4-(4-methoxyphenylsulfonyl-
amino)phenyl 4-methylbenzenesulfonate (XVIIb).
1H NMR spectrum, δ, ppm: 7.47–7.69 d.d (4H,
MeC6H4, J = 8.7 Hz), 7.05–7.62 d.d (4H, MeOC6H4,
J = 9.0 Hz), 7.17 s (2H, 3-H, 5-H), 3.84 s (3H, MeO),
2.47 s (3H, MeC6H4), 1.31 s (18H, t-Bu).
4-Chloro-N-(4-hydroxy-3,5-dimethylphenyl)-
N-(4-methoxyphenylsulfonyl)benzenesulfonamide
1
(XXc). Yield 16%, mp 214°C (decomp.). H NMR
spectrum, δ, ppm: 7.82–7.91 d.d (4H, ClC6H4, J =
9.0 Hz), 7.16–7.71 d.d (4H, MeOC6H4, J = 8.7 Hz),
6.64 s (2H, 2-H, 6-H), 3.90 s (3H, MeO), 2.17 s (6H,
3-Me, 5-Me). Found, %: N 2.84, 2.99; S 13.07, 13.28.
C21H20ClNO6S2. Calculated, %: N 2.91; S 13.31.
2,6-Di-tert-butyl-4-(4-chlorobenzoylamino)phen-
1
yl 4-methoxybenzenesulfonate (XVIIIa). H NMR
spectrum, δ, ppm: 10.27 s (1H, NH), 7.63–8.01 d.d
(4H, ClC6H4, J = 8.4 Hz), 7.24–7.81 d.d (4H, MeO-
C6H4, J = 8.7 Hz), 7.89 s (2H, 3-H, 5-H), 3.89 s (3H,
MeO), 1.33 s (18H, t-Bu).
N-(4-Hydroxy-3,5-dimethylphenyl)-N-(4-meth-
oxyphenylsulfonyl)-4-methylbenzamide (XXIa).
1H NMR spectrum, δ, ppm: 8.65 s (1H, OH), 7.07–
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
61
1
7.81 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.16–7.38 d.d
(4H, MeC6H4, J = 8.7 Hz), 6.78 s (2H, 2-H, 6-H),
3.87 s (3H, MeO), 2.38 s (3H, MeC6H4), 2.06 s (6H,
3-Me, 5-Me).
(XXIId). H NMR spectrum, δ, ppm: 7.74–7.91 d.d
(4H, ClC6H4, J = 9.0 Hz), 7.18–7.82 d.d (4H, MeO-
C6H4, J = 9.3 Hz), 6.59 s (2H, 2-H, 6-H), 3.96 s (3H,
MeO), 3.24–3.36 m (2H, CH in i-Pr), 1.10 d (12H, Me
in i-Pr, J = 6.9 Hz).
N-(4-Hydroxy-3,5-dimethylphenyl)-4-methoxy-
N-(4-methylphenylsulfonyl)benzamide (XXIb).
1H NMR spectrum, δ, ppm: 8.67 s (1H, OH), 7.49–
7.73 d.d (4H, MeOC6H4, J = 8.4 Hz), 6.81–7.43 d.d
(4H, MeC6H4, J = 8.4 Hz), 6.79 s (2H, 2-H, 6-H),
3.72 s (3H, MeO), 2.42 s (3H, MeC6H4), 2.06 s (6H,
3-Me, 5-Me).
N-(4-Hydroxy-3,5-diisopropylphenyl)-N-(4-meth-
oxyphenylsulfonyl)-4-methylbenzamide (XXIIIa).
1H NMR spectrum, δ, ppm: 8.49 s (1H, OH), 7.16–
7.75 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.04–7.45 d.d
(4H, MeC6H4, J = 8.4 Hz), 6.67 s (2H, 2-H, 6-H), 3.87 s
(3H, MeO), 3.14–3.27 m (2H, CH in i-Pr), 2.20 s (3H,
MeC6H4), 0.99 d (12H, Me in i-Pr, J = 6.6 Hz).
N-(4-Chlorophenylsulfonyl)-N-(4-hydroxy-3,5-
dimethylphenyl)-4-methoxybenzamide (XXIc).
1H NMR spectrum, δ, ppm: 8.69 s (1H, OH), 7.64–
7.84 d.d (4H, ClC6H4, J = 8.1 Hz), 7.52–7.72 d.d (4H,
MeOC6H4, J = 8.7 Hz), 6.82 s (2H, 2-H, 6-H), 3.73 s
(3H, MeO), 2.08 s (6H, 3-Me, 5-Me).
N-(4-Hydroxy-3,5-diisopropylphenyl)-4-meth-
oxy-N-(4-methylphenylsulfonyl)benzamide
(XXIIIb). H NMR spectrum, δ, ppm: 8.50 s (1H,
OH), 6.76–7.45 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.43–
7.70 d.d (4H, MeC6H4, J = 8.4 Hz), 6.67 s (2H, 2-H,
6-H), 3.70 s (3H, MeO), 3.12–3.25 m (2H, CH in
i-Pr), 2.42 s (3H, MeC6H4), 1.00 d (12H, Me in
i-Pr, J = 6.9 Hz).
1
N-(4-Hydroxy-3,5-dimethylphenyl)-N-(4-meth-
1
oxyphenylsulfonyl)benzamide (XXId). H NMR
spectrum, δ, ppm: 8.62 s (1H, OH), 7.74–7.78 d.d
(4H, MeOC6H4, J = 8.7 Hz), 7.51–7.92 m (5H, Ph),
6.79 s (2H, 2-H, 6-H), 3.88 s (3H, MeO), 2.07 s (6H,
3-Me, 5-Me).
4-Chloro-N-(4-hydroxy-3,5-diisopropylphenyl)-
N-(4-methoxyphenylsulfonyl)benzamide (XXIIIc).
1H NMR spectrum, δ, ppm: 8.51 s (1H, OH), 7.17–
7.80 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.27–7.43 d.d
(4H, ClC6H4, J = 9.0 Hz), 6.80 s (2H, 2-H, 6-H), 3.88 s
(3H, MeO), 3.11–3.24 m (2H, CH in i-Pr), 0.99 d
(12H, Me in i-Pr, J = 6.9 Hz).
N-(4-Hydroxy-3,5-diisopropylphenyl)-4-methyl-
N-(4-methylphenylsulfonyl)benzenesulfonamide
1
(XXIIa). Yield 38%, mp 200–202°C. H NMR spec-
trum, δ, ppm: 7.48–7.76 d.d (8H, C6H4, J = 8.4 Hz),
6.56 s (2H, 2-H, 6-H), 3.23–3.36 m (2H, CH in i-Pr),
2.49 s (6H, MeC6H4), 1.09 s (12H, Me in i-Pr, J =
6.9 Hz). Found, %: N 2.58, 2.71; S 12.48, 12.70.
C26H31NO5S2. Calculated, %: N 2.79; S 12.78.
N-(4-Hydroxy-3,5-diisopropylphenyl)-N-(4-meth-
oxyphenylsulfonyl)-N′-(4-methylphenylsulfonyl)-
benzimidamide (XXIVa). 1H NMR spectrum, δ, ppm:
8.39 s (1H, OH), 7.14–7.72 d.d (4H, MeOC6H4, J =
8.4 Hz), 7.00–7.42 d.d (4H, MeC6H4, J = 8.7 Hz),
7.47–7.73 m (5H, Ph), 6.68 s (2H, 2-H, 6-H), 3.93 s
(3H, MeO), 3.14–3.27 m (2H, CH in i-Pr), 2.44 s (3H,
MeC6H4), 0.89 d (12H, Me in i-Pr, J = 6.9Hz).
N-(4-Hydroxy-3,5-diisopropylphenyl)-4-methoxy-
N-(4-methylphenylsulfonyl)benzenesulfonamide
1
(XXIIb). H NMR spectrum, δ, ppm: 7.48–7.77 d.d
(4H, MeC6H4, J = 8.4 Hz), 7.17–7.80 d.d (4H, MeO-
C6H4, J = 9.0 Hz), 6.57 s (2H, 2-H, 6-H), 3.96 s (3H,
MeO), 3.24–3.36 m (2H, CH in i-Pr), 2.49 s (3H,
MeC6H4), 1.09 d (12H, Me in i-Pr, J = 6.9 Hz).
N-(4-Hydroxy-3,5-diisopropylphenyl)-N,N′-bis-
(4-methoxyphenylsulfonyl)benzimidamide
(XXIVb). H NMR spectrum, δ, ppm: 8.42 s (1H,
1
4-Chloro-N-(4-hydroxy-3,5-diisopropylphenyl)-
N-(4-methylphenylsulfonyl)benzenesulfonamide
(XXIIc). Yield 34%, mp 200–202°C. H NMR spec-
trum, δ, ppm: 7.74–7.90 d.d (4H, ClC6H4, J = 8.7 Hz),
7.50–7.78 d.d (4H, MeC6H4, J = 8.4 Hz), 6.59 s (2H,
2-H, 6-H), 3.25–3.37 m (2H, CH in i-Pr), 2.50 s (3H,
MeC6H4), 1.10 d (12H, Me in i-Pr, J = 6.9 Hz). Found,
%: N 2.69, 2.85; S 11.94, 12.41. C25H28ClNO5S2. Cal-
culated, %: N 2.68; S 12.28.
OH), 7.16–7.71 d.d (4H, MeOC6H4, J = 8.4 Hz), 7.01–
7.49 d.d (4H, MeOC6H4, J = 8.7 Hz), 7.50–7.74 m
(5H, Ph), 6.68 s (2H, 2-H, 6-H), 3.93 s and 3.84 s (3H
each, MeO), 3.13–3.27 m (2H, CH in i-Pr), 0.91 d
(12H, Me in i-Pr, J = 6.9 Hz).
1
N-(4-Hydroxy-3,5-diisopropylphenyl)-N-(4-meth-
ylphenylsulfonyl)-N′-(4-methoxyphenylsulfonyl)-
benzimidamide (XXIVc). 1H NMR spectrum, δ, ppm:
8.42 s (1H, OH), 7.44–7.79 m (5H, Ph), 7.39–7.76 d.d
(4H, MeC6H4, J = 8.7 Hz), 7.24–7.46 d.d (4H, MeO-
C6H4, J = 9.0 Hz), 6.70 s (2H, 2-H, 6-H), 3.84 s (3H,
4-Chloro-N-(4-hydroxy-3,5-diisopropylphenyl)-
N-(4-methoxyphenylsulfonyl)benzenesulfonamide
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AVDEENKO et al.
62
MeO), 3.13–3.26 m (2H, CH in i-Pr), 2.40 s (3H,
MeC6H4), 0.91 d (12H, Me in i-Pr, J = 6.9 Hz).
N-[4-Hydroxy-3,5-dimethyl-2-(4-methylphenyl-
sulfonyl)phenyl]-4-methylbenzenesulfonamide
1
(XXVIIIa). H NMR spectrum, δ, ppm: 7.65 s (1H,
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-methyl-
N-(4-methylphenylsulfonyl)benzenesulfonamide
6-H), 7.32–7.75 d.d (4H, MeC6H4, J = 7.8 Hz), 7.28–
7.38 d.d (4H, MeC6H4, J = 8.7 Hz), 2.41 s and 2.44 s
(3H each, MeC6H4), 2.32 s (3H, 3-Me), 2.10 s (3H,
5-Me).
1
(XXVa). Yield 35%, mp 173–174°C. H NMR spec-
trum, δ, ppm: 7.48–7.74 d.d (8H, C6H4, J = 8.1 Hz),
6.68 s (2H, 2-H, 6-H), 2.49 s (6H, MeC6H4), 1.82 s
(18H, t-Bu). Found, %: N 2.54, 2.73; S 12.02, 12.23.
C28H35NO5S2. Calculated, %: N 2.64; S 12.11.
4-Chloro-N-[4-hydroxy-3,5-dimethyl-2-(4-meth-
ylphenylsulfonyl)phenyl]benzenesulfonamide
1
(XXVIIIb). H NMR spectrum, δ, ppm: 7.60–7.82 d.d
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-meth-
oxy-N-(4-methylphenylsulfonyl)benzenesulfon-
(4H, ClC6H4, J = 8.7 Hz), 7.62 s (1H, 6-H), 7.32–
7.72 d.d (4H, MeC6H4, J = 8.7 Hz), 2.42 s (3H,
MeC6H4), 2.34 s (3H, 3-Me), 2.10 s (3H, 5-Me).
1
amide (XXVb). H NMR spectrum, δ, ppm: 7.17–
7.79 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.20–7.75 d.d
(4H, MeC6H4, J = 8.4 Hz), 6.69 s (2H, 2-H, 6-H), 3.96 s
(3H, MeO), 2.49 s (3H, MeC6H4), 1.33 s (18H, t-Bu).
4-Chloro-N-[4-hydroxy-2-(4-methoxyphenylsul-
fonyl)-3,5-dimethylphenyl]benzenesulfonamide
1
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-chloro-
N-(4-methoxyphenylsulfonyl)benzamide (XXVIa).
1H NMR spectrum, δ, ppm: 9.23 s (1H, OH), 7.52–
7.89 d.d (4H, ClC6H4, J = 8.7 Hz), 6.99–7.49 d.d (4H,
MeOC6H4, J = 8.7 Hz), 6.76 s (2H, 2-H, 6-H), 3.87 s
(3H, MeO), 1.39 s (18H,).
(XXVIIIc). H NMR spectrum, δ, ppm: 7.61–7.82 d.d
(4H, ClC6H4, J = 8.7 Hz), 7.60 s (1H, 6-H), 7.02–
7.34 d.d (4H, MeOC6H4, J = 8.4 Hz), 3.95 s (3H,
MeO), 2.33 s (3H, 3-Me), 2.12 s (3H, 5-Me).
N-[4-Hydroxy-2-(4-methoxyphenylsulfonyl)-3,5-
dimethylphenyl]-4-methoxybenzamide (XXIXa).
1H NMR spectrum, δ, ppm: 10.61 s (1H, NH), 8.81 s
(1H, OH), 7.83 s (1H, 6-H), 7.36–7.73 d.d (4H,
MeC6H4, J = 8.7 Hz), 7.06–7.85 d.d (4H, MeOC6H4,
J = 8.4 Hz), 3.80 s (3H, MeO), 2.38 s (3H, MeC6H4),
2.29 s (3H, 3-Me), 2.26 s (3H, 5-Me).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-
N-(4-methoxyphenylsulfonyl)-4-methylbenzamide
1
(XXVIb). H NMR spectrum, δ, ppm: 9.28 s (1H,
OH), 7.09–7.78 d.d (4H, MeC6H4, J = 8.4 Hz), 6.99–
7.48 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.75 s (2H, 2-H,
6-H), 3.87 s (3H, MeO), 2.38 s (3H,), 1.39 s (18H,
t-Bu).
N-[4-Hydroxy-3,5-dimethyl-2-(4-methylphenyl-
sulfonyl)phenyl]-4-methoxybenzamide (XXIXb).
1H NMR spectrum, δ, ppm: 10.52 s (1H, NH), 8.80 s
(1H, OH), 7.82 s (1H, 6-H), 7.35–7.67 d.d (4H,
MeC6H4, J = 8.1 Hz), 7.08–7.91 d.d (4H, MeOC6H4,
J = 8.74 Hz), 3.84 s (3H, MeO), 2.35 s (3H, MeC6H4),
2.27 s (3H, 3-Me), 2.25 s (3H, 5-Me).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-
N-(4-methoxyphenylsulfonyl)-N′-(4-methylphenyl-
1
sulfonyl)benzimidamide (XXVIIa). H NMR spec-
trum, δ, ppm: 9.04 s (1H, OH), 7.50–7.84 m (5H, Ph),
7.09–7.77 d.d (4H, MeC6H4, J = 8.7 Hz), 7.00–
7.48 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.96 s (2H, 2-H,
6-H), 3.86 s (3H, MeO), 2.37 s (3H, MeC6H4), 1.19 s
(18H, t-Bu).
N-[2-(4-Chlorophenylsulfonyl)-4-hydroxy-3,5-di-
methylphenyl]-4-methoxybenzamide (XXIXc).
1H NMR spectrum, δ, ppm: 10.30 s (1H, NH), 8.88 s
(1H, OH), 7.83 s (1H, 6-H), 7.39–7.67 d.d (4H,
ClC6H4, J = 8.4 Hz), 7.09–7.89 d.d (4H, MeOC6H4,
J = 8.7 Hz), 3.84 s (3H, MeO), 2.28 s (3H, 3-Me),
2.22 s (3H, 5-Me).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N,N′-bis-
(4-methoxyphenylsulfonyl)benzimidamide
1
(XXVIIb). H NMR spectrum, δ, ppm: 9.04 s (1H,
OH), 7.50–7.80 m (5H, Ph), 7.17–7.78 d.d (4H, MeO-
C6H4, J = 8.7 Hz), 7.00–7.49 d.d (4H, MeOC6H4, J =
8.7 Hz), 6.95 s (2H, 2-H, 6-H), 3.86 s and 3.80 s (3H
each, MeO), 1.19 s (18H, t-Bu).
N-[4-Hydroxy-2-(4-methoxyphenylsulfonyl)-3,5-
1
dimethylphenyl]benzamide (XXIXd). H NMR
spectrum, δ, ppm: 10.62 s (1H, NH), 8.81 s (1H, OH),
7.82 s (1H, 6-H), 7.50–7.60 m (5H, Ph), 7.05–7.83 d.d
(4H, MeOC6H4, J = 8.4 Hz), 3.83 s (3H, MeO), 2.28 s
(3H, 3-Me), 2.26 s (3H, 5-Me).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N′-
(4-methoxyphenylsulfonyl)-N-(4-methylphenylsul-
fonyl)benzimidamide (XXVIIc). H NMR spectrum,
δ, ppm: 9.04 s (1H, OH), 7.42–7.77 m (5H, Ph), 7.16–
7.95 d.d (4H, MeOC6H4, J = 8.7 Hz), 7.21–7.82 d.d
(4H, MeC6H4, J = 8.4 Hz), 6.94 s (2H, 2-H, 6-H), 3.80 s
(3H, MeO), 2.38 s (3H, MeC6H4), 1.19 s (18H, t-Bu).
1
N-[4-Hydroxy-2-(4-methoxyphenylsulfonyl)-
3,5-dimethylphenyl]-N′-(4-methylphenylsulfonyl)-
1
benzimidamide (XXXa). H NMR spectrum, δ, ppm:
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
63
10.40 s (1H, NH), 9.03 s (1H, OH), 7.71 s (1H, 6-H),
7.45–7.62 m (5H, Ph), 7.39–7.67 d.d (4H, MeC6H4,
J = 8.7 Hz), 6.94–7.78 d.d (4H, MeOC6H4, J =
8.4 Hz), 3.89 s (3H, MeO), 2.36 s (3H, MeC6H4),
2.31 s (3H, 3-Me), 2.01 s (3H, 5-Me).
8.09 s (1H, OH), 7.31 s (2H, 2-H, 6-H), 7.06–7.83 m
(5H, Ph), 2.17 s (6H, 3-Me, 5-Me).
N-(4-Hydroxy-3,5-dimethylphenyl)-N′-(4-methyl-
1
phenylsulfonyl)benzimidamide (XXXIIa). H NMR
spectrum, δ, ppm: 10.27 s (1H, NH), 8.30 s (1H, OH),
7.45–7.55 m (5H, Ph), 7.31–7.58 d.d (4H, C6H4, J =
7.8 Hz), 7.10 s (2H, 2-H, 6-H), 2.36 s (3H, MeC6H4),
2.05 s (6H, 3-Me, 5-Me).
N-[4-Hydroxy-2-(4-methoxyphenylsulfonyl)-3,5-
dimethylphenyl]-N′-(4-methoxyphenylsulfonyl)-
1
benzimidamide (XXXb). H NMR spectrum, δ, ppm:
10.36 s (1H, NH), 9.06 s (1H, OH), 7.69 s (1H, 6-H),
7.47–7.65 m (5H, Ph), 7.20–7.49 d.d (4H, MeOC6H4,
J = 8.4 Hz), 6.91–7.72 d.d (4H, MeOC6H4, J =
8.4 Hz), 3.93 s and 3.76 s (3H each, MeO), 2.01 s (3H,
3-Me), 1.87 s (3H, 5-Me).
N-(4-Hydroxy-3,5-dimethylphenyl)-N′-(4-meth-
oxyphenylsulfonyl)benzimidamide (XXXIIb).
1H NMR spectrum, δ, ppm: 10.22 s (1H, NH), 8.28 s
(1H, OH), 7.46–7.60 m (5H, Ph), 7.23–7.61 d.d (4H,
MeOC6H4, J = 8.1 Hz), 7.10 s (2H, 2-H, 6-H), 3.80 s
(3H, MeO), 2.05 s (6H, 3-Me, 5-Me).
N-[4-Hydroxy-3,5-dimethyl-2-(4-methylphen-
ylsulfonyl)phenyl]-N′-(4-methoxyphenylsulfonyl)-
N′-(4-Chlorophenylsulfonyl)-N-(4-hydroxy-3,5-
1
1
benzimidamide (XXXc). H NMR spectrum, δ, ppm:
dimethylphenyl)benzimidamide (XXXIIc). H NMR
10.34 s (1H, NH), 9.03 s (1H, OH), 7.66 s (1H, 6-H),
7.49–7.68 m (5H, Ph), 7.37–7.64 d.d (4H, MeC6H4,
J = 8.7 Hz), 7.19–7.49 d.d (4H, MeOC6H4, J =
8.4 Hz), 3.78 s (3H, MeO), 2.40 s (3H, MeC6H4),
2.14 s (3H, 3-Me), 1.87 s (3H, 5-Me).
spectrum, δ, ppm: 10.40 s (1H, NH), 8.31 s (1H, OH),
7.49–7.62 m (5H, Ph), 7.24–7.58 d.d (4H, ClC6H4,
J = 8.1 Hz), 7.07 s (2H, 2-H, 6-H), 2.05 s (6H, 3-Me,
5-Me).
N′-(4-Bromophenylsulfonyl)-N-(4-hydroxy-3,5-
dimethylphenyl)benzimidamide (XXXIId). 1H NMR
spectrum, δ, ppm: 10.39 s (1H, NH), 8.31 s (1H, OH),
7.53–7.66 m (5H, Ph), 7.24–7.60 d.d (4H, BrC6H4,
J = 8.1 Hz), 7.08 s (2H, 2-H, 6-H), 2.04 s (6H, 3-Me,
5-Me).
N′-(4-Chlorophenylsulfonyl)-N-[4-hydroxy-2-(4-
methoxyphenylsulfonyl)-3,5-dimethylphenyl]benz-
1
imidamide (XXXd). H NMR spectrum, δ, ppm:
10.48 s (1H, NH), 9.06 s (1H, OH), 7.67 s (1H, 6-H),
7.49–7.66 m (5H, Ph), 7.48–7.85 d.d (4H, ClC6H4,
J = 8.4 Hz), 6.98–7.70 d.d (4H, MeOC6H4, J =
8.4 Hz), 3.89 s (3H, MeO), 1.99 s (3H, 3-Me), 1.90 s
(3H, 5-Me).
N-(4-Hydroxy-3,5-diisopropylphenyl)-4-methyl-
1
benzamide (XXXIIIa). H NMR spectrum, δ, ppm:
9.86 s (1H, NH), 8.34 s (1H, OH), 7.42 s (2H, 2-H,
6-H), 7.22–7.93 d.d (4H, MeC6H4, J = 8.7 Hz), 3.23–
3.36 m (2H, CH), 2.39 s (3H, MeC6H4), 1.17 d (12H,
Me in i-Pr, J = 6.9 Hz).
N′-(4-Bromophenylsulfonyl)-N-[4-hydroxy-3,5-
dimethyl-2-(4-methylphenylsulfonyl)phenyl]benz-
1
imidamide (XXXe). H NMR spectrum, δ, ppm:
10.49 s (1H, NH), 9.05 s (1H, OH), 7.50–7.84 d.d
(4H, BrC6H4, J = 8.4 Hz), 7.48–7.66 m (5H, Ph), 7.36–
7.63 d.d (4H, MeC6H4, J = 8.7 Hz), 7.68 s (1H, 6-H),
2.38 s (3H, MeC6H4), 1.99 s (3H, 3-Me), 1.91 s
(3H, 5-Me).
N-(4-Hydroxy-3,5-diisopropylphenyl)-4-methoxy-
benzamide (XXXIIIb). H NMR spectrum, δ, ppm:
9.77 s (1H, NH), 7.71 s (1H, OH), 7.41 s (2H, 2-H,
6-H), 7.04–7.95 d.d (4H, MeOC6H4, J = 9.0 Hz), 3.27–
3.42 m (2H, CH in i-Pr), 3.83 s (3H, MeO), 1.15 d
(12H, Me in i-Pr, J = 6.9 Hz).
1
N-(4-Hydroxy-3,5-dimethylphenyl)-4-methyl-
1
benzamide (XXXIa). H NMR spectrum, δ, ppm:
4-Chloro-N-(4-hydroxy-3,5-diisopropylphenyl)-
1
9.80 s (1H, NH), 8.04 s (1H, OH), 7.30–7.85 d.d (4H,
C6H4, J = 8.1 Hz), 7.30 s (2H, 2-H, 6-H), 2.37 s (3H,
MeC6H4), 2.17 s (6H, 3-Me, 5-Me).
benzamide (XXXIIIc). H NMR spectrum, δ, ppm:
10.01 s (1H, NH), 8.31 s (1H, OH), 7.41 s (2H, 2-H,
6-H), 7.18–7.99 d.d (4H, ClC6H4, J = 8.7 Hz), 3.19–
3.33 m (2H, CH in i-Pr), 1.16 d (12H, Me in i-Pr,
J = 6.9 Hz).
N-(4-Hydroxy-3,5-dimethylphenyl)-4-methoxy-
1
benzamide (XXXIb). H NMR spectrum, δ, ppm:
9.74 s (1H, NH), 8.26 s (1H, OH), 7.29 s (2H, 2-H,
6-H), 7.03–7.93 d.d (4H, C6H4, J = 8.7 Hz), 3.83 s
(3H, MeO), 2.16 s (6H, 3-Me, 5-Me).
N-(4-Hydroxy-3,5-diisopropylphenyl)-N′-
(4-methylphenylsulfonyl)benzimidamide (XXXIVa).
1H NMR spectrum, δ, ppm: 10.24 s (1H, NH), 8.09 s
(1H, OH), 7.47–7.73 m (5H, Ph), 7.35–7.79 d.d (4H,
MeC6H4, J = 7.8 Hz), 7.25 s (2H, 2-H, 6-H), 3.14–
N-(4-Hydroxy-3,5-dimethylphenyl)benzamide
(XXXIc). 1H NMR spectrum, δ, ppm: 9.75 s (1H, NH),
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AVDEENKO et al.
64
3.28 m (2H, CH in i-Pr), 2.35 s (3H,), 0.94 d (12H, Me
in i-Pr, J = 6.9 Hz).
itate was filtered off, washed first with cold and then
with warm water, and recrystallized from glacial acetic
acid.
N-(4-Hydroxy-3,5-diisopropylphenyl)-N′-(4-
methoxyphenylsulfonyl)benzimidamide (XXXIVb).
1H NMR spectrum, δ, ppm: 10.18 s (1H, NH), 8.06 s
(1H, OH), 7.49–7.72 m (5H, Ph), 7.26 s (2H, 2-H,
6-H), 7.24–7.60 d.d (4H, MeOC6H4, J = 7.8 Hz), 3.13–
3.27 m (2H, CH), 3.85 s (3H, MeO), 0.96 d (12H, Me
in i-Pr, J = 6.9 Hz).
4-Hydroxy-3,5-diisopropylphenyl 4-methylben-
zenesulfonate (XXXVIIIa). Yield 66%, mp 105–
1
106°C. H NMR spectrum, δ, ppm: 8.32 s (1H, OH),
7.45–7.67 d.d (4H, MeC6H4, J = 7.8 Hz), 6.45 s (2H,
2-H, 6-H), 3.14–3.27 m (2H, CH in i-Pr), 2.40 s (3H,
MeC6H4), 0.99 d (12H, Me in i-Pr, J = 6.6 Hz). Found,
%: S 9.02, 9.36. C19H25O4S. Calculated, %: S 9.17.
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-methyl-
benzenesulfonamide (XXXVa). 1H NMR spectrum, δ,
ppm: 8.38 s (1H, NH), 6.66 s (1H, OH), 7.31–7.47 d.d
(4H, MeC6H4, J = 8.1 Hz), 6.91 s (2H, 2-H, 6-H),
2.37 s (3H,), 1.32 s (18H, t-Bu).
4-Hydroxy-3,5-diisopropylphenyl 4-methoxy-
benzenesulfonate (XXXVIIIb). Yield 63%, mp 110–
1
112°C. H NMR spectrum, δ, ppm: 8.31 s (1H, OH),
7.15–7.70 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.45 s (2H,
2-H, 6-H), 3.85 s (3H, MeO), 3.14–3.27 m (2H, CH in
i-Pr), 1.00 d (12H, Me in i-Pr, J = 6.6 Hz). Found, %:
S 8.57, 8.89. C19H25O4S. Calculated, %: S 8.80.
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-meth-
1
oxybenzenesulfonamide (XXXVb). H NMR spec-
trum, δ, ppm: 8.33 s (1H, NH), 6.00 s (1H, OH), 7.02–
7.62 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.92 s (2H, 2-H,
6-H), 3.85 s (3H, MeO), 1.33 s (18H, t-Bu).
4-Hydroxy-3,5-diisopropylphenyl 4-chloroben-
1
zenesulfonate (XXXVIIIc). H NMR spectrum, δ,
ppm: 8.38 s (1H, OH), 7.39–7.69 d.d (4H, ClC6H4, J =
7.8 Hz), 6.48 s (2H, 2-H, 6-H), 3.17–3.29 m (2H, CH),
1.00 d (12H, Me in i-Pr, J = 6.6 Hz).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-methyl-
benzamide (XXXVIa). H NMR spectrum, δ, ppm:
9.85 s (1H, NH), 8.31 s (1H, OH), 7.58 s (2H, 2-H,
6-H), 7.41–7.78 d.d (4H, MeC6H4, J = 7.8 Hz), 2.38 s
(3H, MeC6H4), 1.24 s (18H, t-Bu).
1
3,5-Di-tert-butyl-4-hydroxyphenyl arenesulfo-
nates XXXIXa and XXXIXb (general procedure).
A solution of 0.01 mol of 2,6-di-tert-butyl-1,4-benzo-
quinone and 0.03 mol of sodium arenesulfinate Xa or
Xb in 30 ml of acetic acid was heated under reflux for
several hours until it became colorless. The mixture
was cooled and poured into water, and the precipitate
was filtered off, washed with cold and warm water,
and recrystallized from glacial acetic acid.
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-4-meth-
1
oxybenzamide (XXXVIb). H NMR spectrum, δ,
ppm: 9.79 s (1H, NH), 8.28 s (1H, OH), 7.59 s (2H,
2-H, 6-H), 7.42–7.83 d.d (4H, MeOC6H4, J = 8.1 Hz),
3.83 s (3H, MeO), 1.23 s (18H, t-Bu).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-N′-(4-
methylphenylsulfonyl)benzimidamide (XXXVIIa).
1H NMR spectrum, δ, ppm: 10.24 s (1H, NH), 8.23 s
(1H, OH), 7.50–7.82 m (5H, Ph), 7.40 s (2H, 2-H,
6-H), 7.34–7.48 d.d (4H, MeC6H4, J = 8.7 Hz), 2.37 s
(3H, MeC6H4), 1.24 s (18H, t-Bu).
3,5-Di-tert-butyl-4-hydroxyphenyl 4-methylben-
zenesulfonate (XXXIXa). 1H NMR spectrum, δ, ppm:
7.20 s (1H, OH), 7.21–7.67 d.d (4H, MeC6H4, J =
8.7 Hz), 6.55 s (2H, 2-H, 6-H), 2.42 s (3H, MeC6H4),
1.24 s (18H, t-Bu).
N-(3,5-Di-tert-butyl-4-hydroxyphenyl)-
N′-(4-methoxyphenylsulfonyl)benzimidamide
3,5-Di-tert-butyl-4-hydroxyphenyl 4-methoxy-
benzenesulfonate (XXXIXb). Yield 58%, mp 150–
1
(XXXVIIb). H NMR spectrum, δ, ppm: 10.19 s (1H,
1
152°C. H NMR spectrum, δ, ppm: 7.21 s (1H, OH),
NH), 8.20 s (1H, OH), 7.42–7.77 m (5H, Ph), 7.40 s
(2H, 2-H, 6-H), 7.23–7.89 d.d (4H, MeOC6H4, J =
8.7 Hz), 3.82 s (3H, MeO), 1.24 s (18H, t-Bu).
7.16–7.70 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.55 s
(2H, 2-H, 6-H), 3.85 s (3H, MeO), 1.25 s (18H,
t-Bu). Found, %: S 8.15, 8.32. C21H28O5S. Calculated,
%: S 8.17.
4-Hydroxy-3,5-diisopropylphenyl arenesulfo-
nates XXXVIIIa–XXXVIIIc (general procedure).
A solution of 0.01 mol of 2,6-diisopropyl-1,4-benzo-
quinone in 20 ml of acetic acid was heated to the
boiling point, 0.02 mol of sodium arenesulfinate Xa–
Xc was added, and the mixture was heated for 20–
30 min under reflux until it turned colorless. The mix-
ture was cooled and poured into water, and the precip-
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,6-
dimethylphenyl]-4-methylbenzenesulfonamide
1
(XLIIIa). Yield 70%, mp 179–180.5°C. H NMR
spectrum, δ, ppm: 10.58 s (1H, NH), 8.15 s (1H, OH),
7.21–7.44 d.d (4H, MeC6H4, J = 8.4 Hz), 7.19–
7.79 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.84 s (1H, 5-H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
65
3.98 s (3H, MeO), 2.37 s (3H, MeC6H4), 2.20 s (3H,
2-Me), 1.81 s (3H, 6-Me). Found, %: N 2.87, 2.94;
S 13.77, 13.90. C22H23NO6S2. Calculated, %: N 3.03;
S 13.89.
5-H), 3.83 s (3H, MeO), 2.41 s (3H, MeC6H4), 2.39 s
(3H, 2-Me), 2.11 s (3H, 6-Me).
N-[4-Hydroxy-2,6-dimethyl-3-(4-methylphenyl-
1
sulfonyl)phenyl]benzamide (XLIVe). H NMR spec-
N-[4-Hydroxy-2,6-dimethyl-3-(4-methylphenyl-
trum, δ, ppm: 10.45 s (1H, NH), 9.71 s (1H, OH),
7.49–7.77 d.d (4H, MeC6H4, J = 8.4 Hz), 7.19–7.52 m
(5H, Ph), 6.75 s (1H, 5-H), 2.43 s (3H, MeC6H4),
2.39 s (3H, 2-Me), 2.12 s (3H, 6-Me).
sulfonyl)phenyl]-4-methoxybenzenesulfonamide
1
(XLIIIb). Yield 60%, mp 185–186°C. H NMR spec-
trum, δ, ppm: 10.54 s (1H, NH), 8.10 s (1H, OH),
7.50–7.74 d.d (4H, MeC6H4, J = 8.7 Hz), 6.91–
7.50 d.d (4H, 4-MeOC6H4, J = 9.0 Hz), 6.85 s (1H,
5-H), 3.88 s (3H, MeO), 2.49 s (3H, MeC6H4), 2.19 s
(3H, 2-Me), 1.88 s (3H, 6-Me). Found, %: N 3.08,
3.13; S 13.76, 13.95. C22H23NO6S2. Calculated, %:
N 3.03; S 13.89.
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,6-
dimethylphenyl]-N′-(4-methylphenylsulfonyl)benz-
1
imidamide (XLVa). H NMR spectrum, δ, ppm:
10.61 s (1H, NH), 10.02 s (1H, OH), 7.16–7.25 d.d
(4H, MeC6H4, J = 7.8 Hz), 7.14–7.58 m (5H, Ph),
7.10–7.79 d.d (4H, MeOC6H4, J = 8.4 Hz), 6.71 s (1H,
5-H), 3.84 s (3H, MeO), 2.48 s (3H, MeC6H4), 2.32 s
(3H, 2-Me), 2.13 s (3H, 6-Me).
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,6-
dimethylphenyl]-4-methoxybenzenesulfonamide
1
(XLIIIc). Yield 62%, mp 173–175°C. H NMR spec-
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-2,6-
dimethylphenyl]-N′-(4-methoxyphenylsulfonyl)-
benzimidamide (XLVb). Yield 90%, mp 146–148°C.
1H NMR spectrum, δ, ppm: 10.53 s (1H, NH), 9.91 s
(1H, OH), 7.42–7.57 m (5H, Ph), 7.09–7.78 d.d (4H,
MeOC6H4, J = 9.0 Hz), 6.87–7.28 d.d (4H, MeOC6H4,
J = 9.0 Hz), 6.72 s (1H, 5-H), 3.84 s and 3.78 s (3H
each, MeO), 2.45 s (3H, 2-Me), 2.13 s (3H, 6-Me).
Found, %: N 4.86, 5.11; S 11.05, 11.28. C29H28N2O7S2.
Calculated, %: N 4.82; S 11.04.
trum, δ, ppm: 10.59 s (1H, NH), 8.10 s (1H, OH),
7.19–7.80 d.d (4H, MeOC6H4, J = 8.4 Hz), 6.92–
7.49 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.84 s (1H, 5-H),
3.96 s and 3.88 s (3H each, MeO), 2.20 s (3H, 2-Me),
1.87 s (3H, 6-Me). Found, %: N 2.91, 3.01; S 13.14,
13.34. C22H23NO7S2. Calculated, %: N 2.93; S 13.43.
N-[4-Hydroxy-3-(4-methoxyphenylsulfonyl)-
2,6-dimethylphenyl]-4-methylbenzamide (XLIVa).
1H NMR spectrum, δ, ppm: s 10.46 s (1H, NH), 9.64 s
(1H, OH), 7.33–7.88 d.d (4H, MeC6H4, J = 8.4 Hz),
7.20–7.84 d.d (4H, MeOC6H4, J = 9.0 Hz), 6.76 s (1H,
5-H), 3.84 s (3H, MeO), 2.41 s (3H, MeC6H4), 2.38 s
(3H, 2-Me), 2.11 s (3H, 6-Me).
N′-(4-Bromophenylsulfonyl)-N-[4-hydroxy-3-(4-
methoxyphenylsulfonyl)-2,6-dimethylphenyl]benz-
1
imidamide (XLVc). H NMR spectrum, δ, ppm:
10.71 s (1H, NH), 10.19 s (1H, OH), 7.46–7.58 m
(5H, Ph), 7.29–7.57 d.d (4H, BrC6H4, J = 8.7 Hz),
7.10–7.78 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.72 s
(1H, 5-H), 3.85 s (3H, MeO), 2.48 s (3H, 2-Me), 2.13 s
(3H, 6-Me).
4-Chloro-N-[4-hydroxy-3-(4-methoxyphenylsul-
fonyl)-2,6-dimethylphenyl]benzamide (XLIVb).
1H NMR spectrum, δ, ppm: 10.47 s (1H, NH), 9.80 s
(1H, OH), 7.61–8.00 d.d (4H, ClC6H4, J = 9.0 Hz),
7.13–7.84 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.77 s
(1H, 5-H), 3.84 s (3H, MeO), 2.42 s (3H, 2-Me), 2.12 s
(3H, 6-Me).
N′-(4-Chlorophenylsulfonyl)-N-[4-hydroxy-3-(4-
methoxyphenylsulfonyl)-2,6-dimethylphenyl]benz-
1
imidamide (XLVd). H NMR spectrum, δ, ppm:
4-Bromo-N-[4-hydroxy-3-(4-methoxyphenylsul-
fonyl)-2,6-dimethylphenyl]benzamide (XLIVc).
1H NMR spectrum, δ, ppm: 10.49 s (1H, NH), 9.81 s
(1H, OH), 7.45–7.91 d.d (4H, BrC6H4, J = 8.4 Hz),
7.13–7.84 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.76 s
(1H, 5-H), 3.84 s (3H, MeO), 2.42 s (3H, 2-Me), 2.11 s
(3H, 6-Me).
10.78 s (1H, NH), 10.18 s (1H, OH), 7.47–7.58 m
(5H, Ph), 7.36–7.43 d.d (4H, ClC6H4, J = 8.7 Hz),
7.10–7.78 d.d (4H, MeOC6H4, J = 8.4 Hz), 6.72 s
(1H, 5-H), 3.84 s (3H, MeO), 2.48 s (3H, 2-Me), 2.12 s
(3H, 6-Me).
N-[4-Hydroxy-2,6-dimethyl-3-(4-methylphenyl-
sulfonyl)phenyl]-N′-(phenylsulfonyl)benzimidamide
(XLVe). 1H NMR spectrum, δ, ppm: 10.65 s (1H, NH),
10.05 s (1H, OH), 7.46–7.57 m (5H, Ph), 7.37–
7.70 d.d (4H, MeC6H4, J = 8.4 Hz), 7.36–7.57 m (5H,
Ph), 6.68 s (1H, 5-H), 2.48 s (3H, MeC6H4), 2.39 s
(3H, 2-Me), 2.12 s (3H, 6-Me).
N-[4-Hydroxy-2,6-dimethyl-3-(4-methylphenyl-
sulfonyl)phenyl]-4-methoxybenzamide (XLIVd).
1H NMR spectrum, δ, ppm: 10.43 s (1H, NH), 9.68 s
(1H, OH), 7.47–7.78 d.d (4H, MeC6H4, J = 8.7 Hz),
7.05–7.95 d.d (4H, MeC6H4, J = 8.7 Hz), 6.76 s (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009

AVDEENKO et al.
3,5-Dimethyl-4-(4-methylphenylsulfonylamino)-
phenyl 4-methoxybenzenesulfonate (XLVIa).
1H NMR spectrum, δ, ppm: 7.55–7.66 d.d (4H, MeO-
C6H4, J = 8.7 Hz), 7.37–7.75 d.d (4H, MeC6H4, J =
8.4 Hz), 6.71 s (2H, 2-H, 6-H), 3.95 s (3H, MeO),
2.43 s (3H, MeC6H4), 1.97 s (6H, 3-Me, 5-Me).
66
1
sulfonate (XLVIIIa). H NMR spectrum, δ, ppm:
10.10 s (1H, NH), 7.40–7.54 m (5H, Ph), 7.32–
7.76 d.d (4H, MeC6H4, J = 8.7 Hz), 7.18–7.80 d.d
(4H, MeOC6H4, J = 8.7 Hz), 6.84 s (2H, 2-H, 6-H),
3.88 s (3H, MeO), 2.32 s (3H, MeC6H4), 2.13 s (6H,
3-Me, 5-Me).
4-(4-Methoxyphenylsulfonylamino)-3,5-dimethyl-
phenyl 4-methylbenzenesulfonate (XLVIb). 1H NMR
spectrum, δ, ppm: 7.47–7.60 d.d (4H, MeOC6H4, J =
8.7 Hz), 7.07–7.76 d.d (4H, MeC6H4, J = 8.4 Hz),
6.71 s (2H, 2-H, 6-H), 3.91 s (3H, MeO), 2.49 s (3H,
MeC6H4), 1.99 s (6H, 3-Me, 5-Me).
4-[(4-Methoxyphenylsulfonylimino)(phenyl)-
methylamino]-3,5-dimethylphenyl 4-methoxyben-
zenesulfonate (XLVIIIb). 1H NMR spectrum, δ, ppm:
10.00 s (1H, NH), 7.42–7.51 m (5H, Ph), 7.09–
7.78 d.d (4H, MeOC6H4, J = 8.7 Hz), 6.88 s (2H, 2-H,
6-H), 3.88 s and 3.79 s (3H each, MeO), 2.13 s (6H,
3-Me, 5-Me).
4-(4-Methoxyphenylsulfonylamino)-3,5-dimethyl-
phenyl 4-methoxybenzenesulfonate (XLVIc).
1H NMR spectrum, δ, ppm: 7.27–7.43 d.d (4H, MeO-
C6H4, J = 9.0 Hz), 6.97–7.59 d.d (4H, MeOC6H4, J =
8.7 Hz), 6.71 s (2H, 2-H, 6-H), 3.91 s and 3.90 s (3H
each, MeO), 1.98 s (6H, 3-Me, 5-Me).
4-[(4-Bromophenylsulfonylimino)(phenyl)meth-
ylamino]-3,5-dimethylphenyl 4-methoxybenzenesul-
fonate (XLVIIIc). 1H NMR spectrum, δ, ppm: 10.25 s
(1H, NH), 7.50 m (5H, Ph), 7.48–7.82 d.d (4H, MeO-
C6H4, J = 8.7 Hz), 7.25–7.48 d.d (4H, BrC6H4, J =
8.7 Hz), 6.86 s (2H, 2-H, 6-H), 3.88 s (3H, MeO),
2.13 s (6H, 3-Me, 5-Me).
3,5-Dimethyl-4-(4-methylbenzoylamino)phenyl
1
4-methoxybenzenesulfonate (XLVIIa). H NMR
spectrum, δ, ppm: 9.69 s (1H, NH), 7.33–7.88 d.d (4H,
MeC6H4, J = 8.4 Hz), 7.12–7.84 d.d (4H, MeOC6H4,
J = 8.7 Hz), 6.82 s (2H, 2-H, 5-H), 3.89 s (3H, MeO),
2.38 s (3H, MeC6H4), 2.11 s (6H, 3-Me, 5-Me).
4-[(4-Chlorophenylsulfonylimino)(phenyl)meth-
ylamino]-3,5-dimethylphenyl 4-methoxybenzenesul-
fonate (XLVIIId). 1H NMR spectrum, δ, ppm: 10.24 s
(1H, NH), 7.47–7.58 m (5H, Ph), 7.18–7.82 d.d (4H,
MeOC6H4, J = 9.0 Hz), 6.91–7.43 d.d (4H, ClC6H4,
J = 8.4 Hz), 6.86 s (2H, 2-H, 6-H), 3.88 s (3H, MeO),
2.13 s (6H, 3-Me, 5-Me).
4-(4-Chlorobenzoylamino)-3,5-dimethylphenyl
1
4-methoxybenzenesulfonate (XLVIIb). H NMR
spectrum, δ, ppm: 9.85 s (1H, NH), 7.61–8.00 d.d (4H,
ClC6H4, J = 9.0 Hz), 7.20–7.84 d.d (4H, MeOC6H4,
J = 8.7 Hz), 6.83 s (2H, 2-H, 6-H), 3.89 s (3H, MeO),
2.12 s (6H, 3-Me, 5-Me).
3,5-Dimethyl-4-[(phenyl)(phenylsulfonylimino)-
methylamino]phenyl 4-methylbenzenesulfonate
1
(XLVIIIe). H NMR spectrum, δ, ppm: 10.26 s (1H,
NH), 7.46–7.60 m (10H, Ph), 7.11–7.20 d.d (4H,
MeC6H4, J = 8.1 Hz), 6.84 s (2H, 2-H, 6-H), 2.44 s
(3H, MeC6H4), 2.13 s (6H, 3-Me, 5-Me).
4-(4-Bromobenzoylamino)-3,5-dimethylphenyl
4-methoxybenzenesulfonate (XLVIIc). H NMR
spectrum, δ, ppm: 9.86 s (1H, NH), 7.45–7.91 d.d (4H,
BrC6H4, J = 8.4 Hz), 7.20–7.84 d.d (4H, MeOC6H4,
J = 9.0 Hz), 6.83 s (2H, 2-H, 6-H), 3.89 s (3H, MeO),
2.11 s (6H, 3-Me, 5-Me).
1
N-(4-Hydroxy-2,6-dimethylphenyl)-4-methoxy-
N-(4-methylphenylsulfonyl)benzenesulfonamide
1
(XLIXa). H NMR spectrum, δ, ppm: 7.48–7.87 d.d
(4H, MeC6H4, J = 8.4 Hz), 7.17–7.91 d.d (4H, MeO-
C6H4, J = 9.0 Hz), 6.56 s (2H, 3-H, 5-H), 3.97 s (3H,
MeO), 2.49 s (3H, MeC6H4), 1.78 s (6H, 3-Me, 5-Me).
4-(4-Methoxybenzoylamino)-3,5-dimethylphenyl
4-methylbenzenesulfonate (XLVIId). H NMR spec-
trum, δ, ppm: 9.56 s (1H, NH), 7.50–7.80 d.d (4H,
MeC6H4, J = 8.4 Hz), 6.83 s (2H, 2-H, 6-H), 6.77–
7.96 d.d (4H, MeOC6H4, J = 8.7 Hz), 3.83 s (3H,
MeO), 2.43 s (3H, MeC6H4), 2.11 s (6H, 3-Me, 5-Me).
1
N-(4-Hydroxy-2,6-dimethylphenyl)-4-methoxy-
N-(4-methoxyphenylsulfonyl)benzenesulfonamide
1
(XLIXb). H NMR spectrum, δ, ppm: 7.17–7.92 d.d
(8H, C6H4, J = 9.0 Hz), 6.56 s (2H, 3-H, 5-H), 3.96 s
(6H, MeO), 1.79 (6H, 2-Me, 6-Me).
4-Benzoylamino-3,5-dimethylphenyl 4-methyl-
benzenesulfonate (XLVIIe). H NMR spectrum, δ,
1
ppm: 9.76 s (1H, NH), 7.41–7.80 d.d (4H, MeC6H4,
J = 8.4 Hz), 7.34–7.62 m (5H, Ph), 6.84 s (2H, 2-H,
6-H), 2.44 s (3H,), 2.12 s (6H, 3-Me, 5-Me).
N-(4-Hydroxy-2,6-dimethylphenyl)-N-(4-meth-
oxyphenylsulfonyl)-4-methylbenzamide (La). Yield
30%, mp 210.5–211°C. H NMR spectrum, δ, ppm:
1
3,5-Dimethyl-4-[(4-methylphenylsulfonylimino)-
(phenyl)methylamino]phenyl 4-methoxybenzene-
9.65 s (1H, OH), 7.19–8.01 d.d (4H, MeOC6H4, J =
9.0 Hz), 7.03–7.11 d.d (4H, MeC6H4, J = 8.4 Hz),
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REACTIONS OF N-SUBSTITUTED 2,6(3,5)-DIALKYL-1,4-BENZOQUINONE IMINES
67
Nichvoloda, V.M., Vopr. Khim. Khim. Tekhnol., 2001,
no. 3, p. 29.
2. Nichvoloda, V.M., Burmistrov, K.S., and Markov, V.I.,
Zh. Org. Khim., 1985, vol. 21, p. 1069.
3. Burmistrov, K.S. and Burmistrov, S.I., Zh. Org. Khim.,
1980, vol. 16, p. 1487.
4. Burgi, H.-B. and Dunitz, J.D., Structure Correlation,
6.45 s (2H, 3-H, 5-H), 3.89 s (3H, MeO), 2.21 s
(3H, MeC6H4), 2.04 s (6H, 3-Me, 5-Me). Found, %:
N 3.33, 3.41; S 7.47, 7.66. C23H23NO5S. Calculated,
%: N 3.29; S 11.04.
4-Chloro-N-(4-hydroxy-2,6-dimethylphenyl)-
N-(4-methoxyphenylsulfonyl)benzamide (Lb).
1H NMR spectrum, δ, ppm: 9.69 s (1H, OH), 7.20–
8.03 d.d (4H, MeOC6H4, J = 9.0 Hz), 7.20–7.31 d.d
(4H, ClC6H4, J = 8.4 Hz), 6.47 s (2H, 3-H, 5-H), 3.89 s
(3H, MeO), 2.05 s (6H, 3-Me, 5-Me).
Weinheim: VCH, 1994, vol. 2, p. 741.
5. Avdeenko, A.P., Pirozhenko, V.V., Yagupol’skii, L.M.,
and Marchenko, I.L., Russ. J. Org. Chem., 2001,
vol. 37, p. 991.
4-Bromo-N-(4-hydroxy-2,6-dimethylphenyl)-N-
(4-methoxyphenylsulfonyl)benzamide (Lc). 1H NMR
spectrum, δ, ppm: 9.71 s (1H, OH), 7.20–8.02 d.d (4H,
MeOC6H4, J = 9.0 Hz), 7.13–7.75 d.d (4H, BrC6H4,
J = 8.4 Hz), 6.46 s (2H, 3-H, 5-H), 3.89 s (3H, MeO),
2.04 s (6H, 3-Me, 5-Me).
6. Zefirov, Yu.V. and Zorkii, P.M., Usp. Khim., 1989,
vol. 58, p. 713.
7. Sheldrick, G.M., SHELXTL PLUS. PC Version. A Sys-
tem of Computer Programs for the Determination of
Crystal Structure from X-Ray Diffraction Data. Rev.5.1,
1998.
8. Burmistrov, S.I. and Titov, E.A., Zh. Obshch. Khim.,
N-(4-Hydroxy-2,6-dimethylphenyl)-4-methoxy-
N-(4-methylphenylsulfonyl)benzamide (Ld).
1H NMR spectrum, δ, ppm: 9.55 s (1H, OH), 7.19–
7.96 d.d (4H, MeOC6H4, J = 8.7 Hz), 7.05–7.41 d.d
(4H, MeC6H4, J = 8.4 Hz), 6.48 s (2H, 3-H, 5-H),
3.70 s (3H, MeO), 2.43 s (3H, MeC6H4), 2.05 s (6H,
3-Me, 5-Me).
1952, vol. 22, p. 999.
9. Adams, R. and Looker, J.H., J. Am. Chem. Soc., 1951,
vol. 73, p. 1145.
10. Pirozhenko, V.V. and Avdeenko, A.P., Russ. J. Org.
Chem., 1995, vol. 31, p. 1514.
11. Avdeenko, A.P., Russ. J. Org. Chem., 2000, vol. 36,
p. 522.
12. Avdeenko, A.P., Konovalova, S.A., and Ludchen-
ko, O.N., Vopr. Khim. Khim. Tekhnol., 2006, no. 6,
p. 36.
13. Pirozhenko, V.V., Avdeenko, A.P., Yusina, A.L., and
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N-(4-Hydroxy-2,6-dimethylphenyl)-N-(4-methyl-
phenylsulfonyl)benzamide (Le). H NMR spectrum,
δ, ppm: 9.64 s (1H, OH), 7.96–7.99 d (4H, MeC6H4,
J = 8.1 Hz), 7.20–7.55 m (5H, Ph), 6.44 s (2H, 3-H,
5-H), 2.44 s (3H, MeC6H4), 2.06 s (6H, 3-Me, 5-Me).
1
14. Burmistrov, K.S. and Burmistrov, S.I., Vopr. Khim.
Khim. Tekhnol., 1979, vol. 55, p. 120.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 1 2009