Reaction of N-aryl-1,4-benzoquinone imines with sodium arenesulfinates

Article abstract of DOI:10.1134/S1070428014120070

N-Aryl-1,4-benzoquinone imines reacted with sodium arenesulfinates to give products of orbital-controlled nucleophilic 1,4- and 6,3-addition.

Full text of DOI:10.1134/S1070428014120070

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 12, pp. 1757–1762. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, A.A. Santalova, V.V. D’yakonenko, G.V. Palamarchuk, O.V. Shishkin, 2014, published in Zhurnal
Organicheskoi Khimii, 2014, Vol. 50, No. 12, pp. 1776–1781.
Reaction of N-Aryl-1,4-Benzoquinone Imines
with Sodium Arenesulfinates
S. A. Konovalovaa, A. P. Avdeenkoa, A. A. Santalovaa, V. V. D’yakonenkob,
G. V. Palamarchukb, and O. V. Shishkinb, c
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute for Single Crystals, National Academy of Sciences of Ukraine,
pr. Lenina 60, Kharkiv, 61001 Ukraine
c Karazin Kharkiv National University, pl. Svobody 4, Kharkiv, 61022 Ukraine
Received June 14, 2014
Abstract—N-Aryl-1,4-benzoquinone imines reacted with sodium arenesulfinates to give products of orbital-
controlled nucleophilic 1,4- and 6,3-addition.
DOI: 10.1134/S1070428014120070
The regioselectivity of nucleophilic addition to
N-aryl-1,4-benzoquinone imines is determined by
electrophilicity of the substrate, nucleophilicity of the
reagent, and hardness of the latter. Hard nucleophiles
(Cl–, Br–) add to N-(4-methoxyphenyl)-1,4-benzo-
quinone imine in protic medium at the ortho position
to the nitrogen atom according to the 6,3-addition
scheme [1–3]. Introduction of electron-withdrawing
substituents into the N-aryl fragment increases electro-
philicity of quinone imine, and the addition pattern of
hard nucleophiles changes from 6,3 to 1,4 [4].
Soft nucleophiles [ArNH2, ArS–, Ar(Alk)SO2–] are
capable of adding to N-aryl-1,4-benzoquinone imines
in both aprotic and protic media. N-Phenyl- and
N-(4-methylphenyl)-1,4-benzoquinone imines with
free ortho position with respect to the carbonyl carbon
atom were reported to react with sodium arenesul-
finates in acetic acid to give only 1,4-addition products
[5]. However, no 1H NMR spectra of the products were
given, and the reaction mixtures were not analyzed by
1H NMR, so that other possible products could remain
not detected. Reactions of sodium arenesulfinates with
N-aryl-1,4-benzoquinone imines containing electron-
withdrawing substituents in the para position of the
aryl fragment were not studied previously. Taking the
above state into account, in the present work we
examined reactions of N-aryl-1,4-benzoquinone imines
Ia–Id with sodium arenesulfinates IIa–IIc.
The reactions were carried out in acetic acid using
2 equiv of the nucleophile. Sodium arenesulfinates IIa
and IIb contained methyl or methoxy group in the
para position of the benzene ring to facilitate inter-
1
pretation of the H NMR spectra. In order to detect all
possible products, a part of the crude product precip-
itated from the reaction mixture was recrystallized
from acetic acid, the mother liquor was diluted with
water, the precipitate was filtered off, and the three
1
samples were analyzed by H NMR. We thus suc-
ceeded in detecting compounds whose amount in the
reaction mixture did not exceed a few percent.
The reactions of N-phenyl-, N-(4-methylphenyl)-,
and N-(2-nitrophenyl)-1,4-benzoquinone imines Ia–Ic
with sodium arenesulfinates IIa–IIc afforded exclu-
sively 1,4-addition products IIIa–IIIi, in keeping with
the data of [5, 6] (Scheme 1). However, introduction of
two electron-withdrawing nitro groups into the N-aryl
fragment (compound Id) changed the reaction direc-
tion, and N-(2,4-dinitrophenyl)-1,4-benzoquinone
imine (Id) reacted with sodium arenesulfinates IIa and
IIb to give mixtures of 1,4- and 6,3-addition products
IIIh/IVa and IIIi/IVb, respectively, at ratios of
84:16 and 85:15.
1
The H NMR spectra of 1,4-addition products IIIa,
IIIb, and IIId–IIIi contained a doublet signal from
3-H at δ 7.59–7.89 ppm with a meta coupling constant,
the 5-H signal was a doublet of doublets at δ 7.15–
1757

KONOVALOVA et al.
Scheme 1.
1758
R2
R1
OH
1,4-Addition
N
H
SO2C6H4R3-4
R2
R1
O
SO2Na
IIIa–IIIi
+
R3
R2
R1
OH
N
6,3-Addition
Ia–Id
IIa–IIc
N
H
SO2C6H4R3-4
IVa, IVb
I, R1 = R2 = H (a); R1 = H, R2 = Me (b); R1 = O2N, R2 = H (c); R1 = R2 = O2N (d); II, R3 = Me (a), MeO (b), Cl (c); III, R1 = R2 = H,
R3 = Me (a), MeO (b); R1 = H, R2 = Me, R3 = Me (c), MeO (d); R1 = O2N, R2 = H, R3 = Me (e), MeO (f), Cl (g); R1 = R2 = O2N,
R3 = Me (h), MeO (i); IV, R1 = R2 = O2N, R3 = Me (a), MeO (b).
7.50 ppm, and the 6-H proton resonated at δ 6.80–
6.99 ppm. In the 1H NMR spectra of 6,3-addition prod-
ucts IVa and IVb, the doublet signal (meta coupling)
from 2-H was observed at δ 7.65–7.67 ppm, the 6-H
signal appeared as a doublet of doublets at δ 7.16–
7.21 ppm, and the 5-H doublet (ortho coupling) was
located at δ 7.34 ppm. It is seen that signals from
protons in the aminophenol fragment of 1,4-addition
products IIIa, IIIb, and IIId–IIIi shift considerably
downfield as the acceptor power of the substituent in
the N-aryl ring increases. 6,3-Addition products IVa
and IVb are characterized by downfield position of
the 6-H signal and upfield position of the 5-H signal
relative to the corresponding signals of regioisomers
IIIh and IIIi, which is consistent with published
data [6].
The structure of the 6,3-addition products was
unambiguously proved by X-ray analysis of 4-(2,4-di-
nitrophenylamino)-3-(4-methoxybenzenesulfonyl)-
phenol (IVb) which was isolated in the pure state by
several recrystallizations (see figure). According to the
X-ray diffraction data, the substituents on C8 and C13
in molecule IVb are oriented almost orthogonally to
the C8–C13 aromatic ring plane [the torsion angles
C9C8S1C5 and C8C13N1C14 are –109.4(2) and
–111.3(2)°, respectively]. The dinitrophenyl and
methoxyphenyl fragments are almost coplanar to each
other (the dihedral angle between the corresponding
mean-square planes is 10.4°), and the shortest distance
between carbon atoms is 3.43 Å. Such arrangement of
the benzene rings and the presence of polar substit-
uents therein suggest fairly strong stacking interaction
which should stabilize the observed conformation.
C3
O1
C4
C2
Compounds IIIa, IIIc, and IIIi were oxidized with
lead tetraacetate to the corresponding 1,4-benzoqui-
none imine derivatives Va–Vc, and the latter were
brought into reaction with sodium arenesulfinates IIa
and IIb (Scheme 2). Addition of the second sodium
arenesulfinate molecule to quinone imines Va and Vb
resulted in the formation of only 1,4-addition products
VIa and VIb, which confirmed the data of [7]. How-
ever, from quinonimine Vc and sodium 4-methoxyben-
zenesulfinate IIb we obtained a mixture of 6,3- and
1,6-addition products VII and VIII at a ratio of 65:35.
O3
C1
O4
C9
S1
C5
O2
C7
O7
C10
C8
C6
C16
C15
C13
C17
N3
C11
C12
N1
C14
O5
C18
C19
O8
1
Compound VII showed in the H NMR spectrum
N2
O6
singlets at δ 8.17 (3-H) and 7.80 ppm (6-H). The
1H NMR spectrum of VIII contained a doublet at
δ 7.86 ppm (3-H, meta coupling), a doublet of doublets
at δ 7.41–7.44 ppm (5-H), and a doublet at δ 7.47 ppm
(6-H, ortho coupling).
Structure of the molecule of 4-(2,4-dinitrophenylamino)-3-
(4-methoxybenzenesulfonyl)phenol (IVb) according to the
X-ray diffraction data. Non-hydrogen atoms are shown as
thermal vibration ellipsoids with a probability of 30%.
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REACTION OF N-ARYL-1,4-BENZOQUINONE IMINES WITH SODIUM ARENESULFINATES
1759
Scheme 2.
SO2C6H4R3-4
R2
R1
OH
1,4-Addition
N
H
SO2C6H4R3-4
VIa, VIb
SO2C6H4OMe-4
OH
R1
H
N
O2N
[O]
IIa, IIb
6,3-Addition
IIIa, IIIc, IIIi
N
H
R2
O
NO2
SO2C6H4OMe-4
SO2C6H4R3-4
VII
Va–Vc
SO2C6H4OMe-4
O2N
OSO2C6H4OMe-4
1,6-Addition
N
H
NO2
VIII
V, R1 = R2 = H, R3 = Me (a); R1 = H, R2 = R3 = Me (b); R1 = R2 = O2N, R3 = MeO (c);
VI, R1 = R2 = H, R3 = Me (a); R1 = H, R2 = R3 = Me (b).
The results of this study led us to conclude that
N-phenyl- and N-(4-methylphenyl)-1,4-benzoquinone
imines Ia and Ib possessing relatively small redox
potentials [2] react with sodium arenesulfinates to give
only 1,4-addition products due to orbital control of the
reaction, whereas single-electron transfer mechanism
is hardly probable because of high LUMO energies,
–331.42 and –324.12 kJ/mol for compounds Ia and Ib,
respectively.
The formation of mixtures of 1,4- and 6,3-addition
products in the reactions of N-(2,4-dinitrophenyl)-1,4-
benzoquinone imine with sodium arenesulfinates is
also consistent with the orbital control of nucleophilic
addition. Introduction of two strong electron-with-
drawing substituents into the N-aryl fragment changes
contributions of carbon atoms of the quinoid ring to
the LUMO toward increased contribution of C3.
According to the results of quantum chemical calcula-
tions, the orbital coefficients of C2, C3, C5 and C6 in
the LUMO are, respectively, 0.0785, 0.0808, 0.1271,
and 0.1885 for quinone imine Ib and 0.3667, 0.6288,
0.1222, and 0.2500 for Id.
tion of electron-withdrawing ArSO2 group into the
quinoid ring increases the redox potential [7] and
reduces the LUMO energy.
EXPERIMENTAL
1
The H NMR spectra were recorded on a Varian
VXR-300 spectrometer at 300 MHz relative to
tetramethylsilane as internal reference. The purity of
quinone imines Ia–Id and Va–Vc was checked by
TLC on Silufol UV-254 plates; samples were applied
from solutions in chloroform, benzene–hexane (10:1)
was used as eluent; and spots were visualized under
UV light.
The X-ray diffraction data for compound IVb were
obtained on an Xcalibur-3 diffractometer (MoKα radia-
tion, CCD detector, graphite monochromator, ω-scan-
ning, 2θmax = 60°). Monoclinic crystals; unit cell pa-
rameters (21°C): a = 7.947(3), b = 36.290(3), c =
7.371(2) Å; β = 117.59(2); V = 1884.0(2) Å3;
M 445.40; Z = 4; space group P21/c; dcalc = 1.570 g×
cm–3; μ(MoKα) = 0.229 mm–1; F(000) = 920. Total of
22421 reflection intensities were measured, including
5454 independent reflections (Rint = 0.07). The struc-
ture was solved by the direct method using SHELXTL
[9]. The positions of hydrogen atoms were determined
from the difference electron density maps and were
refined according to the riding model (Uiso = nUeq,
The reaction of even more electron-deficient
N-(2,4-dinitrophenyl)-2-(4-methoxybenzenesulfonyl)-
1,4-benzoquinone imine (Vc) with sodium 4-methoxy-
benzenesulfinate resulted in the formation of 6,3- and
1,6-addition products. The latter is most likely to be
formed via radical ion mechanism [8] since introduc-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

KONOVALOVA et al.
1760
where n = 1.5 for methyl groups, and n = 1.2 for other
hydrogen atoms). The structure was refined against F2
by the full-matrix least-squares procedure in aniso-
tropic approximation for non-hydrogen atoms; final
divergence factors wR2 = 0.032 for 5454 reflections
and R1 = 0.035 for 1646 reflections with F > 4σ(F);
goodness of fit S = 0.718. The coordinates of atoms
and complete tables of bond lengths and bond angles
were deposited to the Cambridge Crystallographic
Data Centre (entry no. CCDC 995309).
7.50 d (2H, 2″-H, 6″-H, J = 8.1 Hz), 7.92 d (2H, 3″-H,
5″-H, J = 8.1 Hz). Found, %: N 3.96, 4.21; S 9.33,
9.62. C19H15NO3S. Calculated, %: N 4.15; S 9.50.
2-(4-Methylbenzenesulfonyl)-4-(4-methylphenyl-
imino)cyclohexa-2,5-dien-1-one (Vb). Yield 65%,
1
mp 147–148°C. H NMR spectrum (CDCl3), δ, ppm:
Z isomer (45%): 2.41 s (3H, Me), 6.58 d (1H, 6-H, J =
9.9 Hz), 7.01 d (1H, 3-H, J = 2.1 Hz), 7.42 d (2H,
2″-H, 6″-H, J = 8.4 Hz), 7.48 d (2H, 2′-H, 6′-H, J =
8.7 Hz), 7.84 d (2H, 3″-H, 5″-H, J = 8.4 Hz), 7.87 d
(2H, 3′-H, 5′-H, J = 8.7 Hz), 8.04–8.16 d.d (1H, 5-H,
J = 2.4 Hz); E isomer (55%): 2.39 s (3H, Me), 6.70 d
(1H, 6-H, J = 10.2 Hz), 6.98–7.12 d.d (1H, 5-H, J =
2.4 Hz), 7.35 d (1H, 3-H, J = 2.1 Hz), 7.46 d (2H,
2″-H, 6″-H, J = 8.1 Hz), 7.48 d (2H, 2′-H, 6′-H, J =
8.7 Hz), 7.94 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 7.96 d
(2H, 3′-H, 5′-H, J = 8.7 Hz). Found, %: N 3.78,
4.08; S 8.95, 9.23. C20H17NO3S. Calculated, %:
N 3.99; S 9.12.
Quantum chemical calculations were performed
using Firefly QC suite [10] based in part on the
GAMESS (US) code [11]. All geometric parameters of
1,4-benzoquinone imine molecules were optimized at
the DFT B3LYP/6-31+G(d) level of theory.
Quinone imines Ia–Ic were synthesized by oxida-
tion of the corresponding 4-aminophenols with lead
dioxide in benzene, quinone imine Id was prepared by
oxidation of 4-(2,4-dinitrophenylamino)phenol with
lead tetraacetate in acetic acid as described in [12], and
quinone imines Va–Vc were obtained according to the
procedure reported in [5]. Compounds Ia, Ib, and IIIc
were described previously [12, 13]. Sodium arenesul-
finates IIa–IIc were synthesized according to [14].
4-(2,4-Dinitrophenylamino)-2-(4-methoxyben-
zenesulfonyl)cyclohexa-2,5-dien-1-one (Vc). Yield
1
79%, mp 135–136°C. H NMR spectrum (CDCl3), δ,
ppm: 3.89 s (3H, MeO), 6.63 br.s (1H, 6-H), 7.01 d
(2H, 2″-H, 6″-H, J = 8.4 Hz), 7.02 d (1H, 6′-H, J =
8.4 Hz), 7.34 d (1H, 3-H, J = 2.4 Hz), 8.03 br.s (1H,
5-H), 8.05 d (2H, 3″-H, 5″-H, J = 8.4 Hz), 8.51–
8.54 d.d (1H, 5′-H, J = 2.4, 9.0 Hz), 9.06 d (1H, 3′-H,
J = 2.1 Hz). Found, %: N 9.56, 9.66; S 7.28, 7.36.
C19H13N3O8S. Calculated, %: N 9.48; S 7.23.
4-(2-Nitrophenylimino)cyclohexa-2,5-dien-1-one
(Ic). Yield 80%, mp 110–111°C; published data [12]:
1
mp 112–113°C. H NMR spectrum (CDCl3), δ, ppm:
6.55 d (1H, 6-H, J = 9.9 Hz), 6.74 d (1H, 2-H, J =
10.2 Hz), 6.79 d (1H, 3′-H, J = 8.1 Hz), 6.87 d (1H,
4′-H), 7.36 d (2H, 3-H, 5-H, J = 7.8 Hz), 7.63 t (1H,
5′-H), 8.15 d (1H, 6′-H, J = 7.8 Hz). Found, %:
N 12.04, 12.39. C12H8N2O3. Calculated, %: N 12.28.
Reaction of quinone imines Ia–Id and Va–Vc
with sodium arenesulfinates IIa–IIc (general proce-
dure). Sodium arenesulfinate IIa–IIc, 4 mmol, was
added in one portion to a solution of 2 mmol of
quinone imine Ia–Id or Va–Vc in 20 mL of glacial
acetic acid heated to 70°C. When the mixture turned
colorless, it was cooled, and water was added until
complete precipitation. The colorless solid was filtered
off and washed first with cold and then with warm
water. A part of the crude product was recrystallized
from acetic acid. The mother liquor was diluted with
water, and the precipitate was filtered off. The three
crystalline samples were analyzed by 1H NMR.
4-(2,4-Dinitrophenylimino)cyclohexa-2,5-dien-1-
one (Id). Yield 80%, mp 160–161°C; published data
1
[15]: mp 161.5–162°C. H NMR spectrum (CDCl3), δ,
ppm: 6.68 br.s (2H, 2-H, 6-H), 6.72 s (2H, 3-H, 5-H),
7.02 d (1H, 6′-H, J = 8.7 Hz), 8.46–8.50 d.d (1H, 5′-H,
J = 2.1, 9.0 Hz), 9.02 d (1H, 3′-H, J = 2.4 Hz). Found,
%: N 15.21, 15.52. C12H7N3O5. Calculated, %: N 15.38.
2-(4-Methylbenzenesulfonyl)-4-(phenylimino)-
cyclohexa-2,5-dien-1-one (Va). Yield 90%, mp 124–
1
126°C; published data [5]: mp 126–127°C. H NMR
spectrum (CDCl3), δ, ppm: Z isomer (55%): 2.44 s
(3H, Me), 6.49 d (1H, 6-H, J = 10.5 Hz), 6.94 d (1H,
3-H, J = 2.4 Hz), 7.31–7.53 m (5H, Ph), 7.43 d (2H,
2″-H, 6″-H, J = 8.4 Hz), 8.02 d (2H, 3″-H, 5″-H, J =
8.4 Hz), 8.06–8.26 d.d (1H, 5-H, J = 2.4, 10.5 Hz);
E isomer (45%): 2.43 s (3H, Me), 6.63 d (1H, 6-H, J =
9.9 Hz), 7.14–7.18 d.d (1H, 5-H, J = 2.4, 9.9 Hz),
7.31–7.53 m (5H, Ph), 7.34 d (1H, 3-H, J = 2.4 Hz),
2-(4-Methylbenzenesulfonyl)-4-(phenylamino)-
phenol (IIIa). Yield 92%, mp 82–84°C; published data
1
[5]: mp 83–84°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.37 s (3H, Me), 6.76–7.21 m (5H, Ph), 6.95 d
(1H, 6-H, J = 8.4 Hz), 7.24–7.26 d.d (1H, 5-H, J = 3,
7.8 Hz), 7.34 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.65 d
(1H, 3-H, J = 3 Hz), 7.79 d (2H, 3″-H, 5″-H, J =
8.7 Hz), 8.10 s (1H, NH), 10.20 br.s (1H, OH). Found,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

REACTION OF N-ARYL-1,4-BENZOQUINONE IMINES WITH SODIUM ARENESULFINATES
1761
%: N 3.85, 3.98; S 8.89, 9.14. C19H17NO3S. Calculat-
ed, %: N 4.12; S 9.42.
7.50 t (1H, 5′-H), 7.69 d (2H, 2″-H, 6″-H, J = 8.4 Hz),
7.84 d (1H, 3-H, J = 1.8 Hz), 7.94 d (2H, 3″-H, 5″-H,
J = 8.4 Hz), 8.12 d (1H, 6′-H, J = 8.1 Hz), 9.39 s (1H,
NH), 10.98 s (1H, OH). Found, %: N 7.15, 7.18;
S 7.85, 7.99. C18H13ClN2O5S. Calculated, %: N 6.92;
S 7.92.
2-(4-Methoxybenzenesulfonyl)-4-(phenylamino)-
1
phenol (IIIb). Yield 86%, mp 82–84°C. H NMR
spectrum (DMSO-d6), δ, ppm: 3.83 s (3H, MeO),
6.76–7.22 m (5H, Ph), 6.96 d (1H, 6-H, J = 7.8 Hz),
7.11 d (2H, 2″-H, 6″-H, J = 9.0 Hz), 7.23–7.26 d.d
(1H, 5-H, J = 2.7, 7.8 Hz), 7.65 d (1H, 3-H, J =
2.7 Hz), 7.87 d (2H, 3″-H, 5″-H, J = 9.0 Hz), 8.10 s
(1H, NH), 10.28 br.s (1H, OH). Found, %: N 3.85,
3.98; S 8.89, 9.14. C19H17NO4S. Calculated, %:
N 3.94; S 9.02.
4-(2,4-Dinitrophenylamino)-2-(4-methylben-
zenesulfonyl)phenol (IIIh). Yield 65%, mp 193–
1
193.5°C. H NMR spectrum (DMSO-d6), δ, ppm:
2.39 s (3H, 4″-Me), 6.99 d (1H, 6-H, J = 8.4 Hz),
7.02 d (1H, 6′-H, J = 8.4 Hz), 7.41 d (2H, 2″-H, 6″-H,
J = 8.1 Hz), 7.47–7.50 d.d (1H, 5-H, J = 2.1, 8.4 Hz),
7.83 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 7.89 d (1H, 3-H,
J = 2.1 Hz), 8.21–8.24 d.d (1H, 5′-H, J = 2.7, 8.4 Hz),
8.90 d (1H, 3′-H, J = 2.1 Hz), 10.14 s (1H, NH),
11.59 s (1H, OH). Found, %: N 9.62, 9.90; S 7.50,
7.16. C19H15N3O7S. Calculated, %: N 9.79; S 7.47.
2-(4-Methoxybenzenesulfonyl)-4-(4-methyl-
phenylamino)phenol (IIId). Yield 81%, mp 144–
1
146°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.22 s
(3H, 4′-Me), 3.83 s (3H, MeO), 6.80 d (1H, 6-H, J =
8.7 Hz), 6.88 d (2H, 2′-H, 6′-H, J = 7.8 Hz), 7.04 d
(2H, 3′-H, 5′-H, J = 7.8 Hz), 7.10 d (2H, 2″-H, 6″-H,
J = 9.0 Hz), 7.15–7.18 d.d (1H, 5-H, J = 2.7, 8.7 Hz),
7.59 d (1H, 3-H, J = 2.7 Hz), 7.85 d (2H, 3″-H, 5″-H,
J = 9.0 Hz), 7.96 br.s (1H, NH), 10.09 s (1H, OH).
Found, %: N 3.86, 3.77; S 8.84, 8.46. C20H19NO4S.
Calculated, %: N 3.79; S 8.68.
4-(2,4-Dinitrophenylamino)-2-(4-methoxyben-
zenesulfonyl)phenol (IIIi). Yield 69%, mp 205–
1
206°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.84 s
(3H, MeO), 6.99 d (1H, 6-H, J = 9.0 Hz), 7.01 d (1H,
6′-H, J = 8.7 Hz), 7.13 d (2H, 2″-H, 6″-H, J = 9.0 Hz),
7.46–7.49 d.d (1H, 5-H, J = 2.1, 8.7 Hz), 7.87 d (1H,
3-H, J = 2.1 Hz), 7.88 d (2H, 3″-H, 5″-H, J = 9.0 Hz),
8.20–8.23 d.d (1H, 5′-H, J = 2.1, 8.4 Hz), 8.89 d (1H,
3′-H, J = 2.1 Hz), 10.14 s (1H, NH), 11.07 s (1H, OH).
Found, %: N 9.48, 9.69; S 7.21, 7.48. C19H15N3O8S.
Calculated, %: N 9.43; S 7.20.
2-(4-Methylbenzenesulfonyl)-4-(2-nitrophenyl-
amino)phenol (IIIe). Yield 79%, mp 163–164°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.39 s (3H,
4″-Me), 6.85 t (1H, 4′-H), 6.94 d (1H, 6-H, J =
7.8 Hz), 6.97 d (1H, 3′-H, J = 9.0 Hz), 7.40 d (2H,
2″-H, 6″-H, J = 8.1 Hz), 7.43–7.46 d.d (1H, 5-H,
J = 1.8, 8.4 Hz), 7.81 d (2H, 3″-H, 5″-H, J = 8.1 Hz),
7.50 t (1H, 5′-H), 7.82 d (1H, 3-H, J = 1.8 Hz), 8.12 d
(1H, 6′-H, J = 8.4 Hz), 9.39 s (1H, NH), 10.83 s
(1H, OH). Found, %: N 7.35, 7.17; S 8.06, 8.38.
C19H16N2O5S. Calculated, %: N 7.29; S 8.34.
4-(2,4-Dinitrophenylamino)-3-(4-methylben-
1
zenesulfonyl)phenol (IVa). H NMR spectrum
(DMSO-d6), δ, ppm: 2.13 s (3H, 4″-Me), 6.20 d (1H,
6′-H, J = 9.0 Hz), 7.11 d (2H, 2″-H, 6″-H, J = 8.1 Hz),
7.18–7.21 d.d (1H, 6-H, J = 2.1, 9.0 Hz), 7.34 d (1H,
5-H, J = 8.4 Hz), 7.51 d (2H, 3″-H, 5″-H, J = 8.1 Hz),
7.67 d (1H, 2-H, J = 2.7 Hz), 7.84–7.87 d.d (1H, 5′-H,
J = 3, 8.4 Hz), 8.82 d (1H, 3′-H, J = 3.0 Hz), 9.83 s
(1H, NH), 10.67 br.s (1H, OH).
2-(4-Methoxybenzenesulfonyl)-4-(2-nitrophenyl-
amino)phenol (IIIf). Yield 89%, mp 150–151°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 3.84 s (3H,
MeO), 6.85 t (1H, 4′-H), 6.95 d (1H, 6-H, J = 8.7 Hz),
6.97 d (1H, 3′-H, J = 8.4 Hz), 7.12 d (2H, 2″-H, 6″-H,
J = 7.8 Hz), 7.42–7.45 d.d (1H, 5-H, J = 1.8, 8.4 Hz),
7.50 t (1H, 5′-H), 7.81 d (1H, 3-H, J = 1.8 Hz), 7.88 d
(2H, 3″-H, 5″-H, J = 7.8 Hz), 8.12 d (1H, 6′-H, J =
8.7 Hz), 9.38 s (1H, NH), 10.82 s (1H, OH). Found, %:
N 7.12, 6.94; S 8.14, 8.29. C19H16N2O6S. Calculated,
%: N 7.00; S 8.01.
4-(2,4-Dinitrophenylamino)-3-(4-methoxyben-
zenesulfonyl)phenol (IVb). Yield 8%, mp 254–255°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 3.61 s (3H,
MeO), 6.21 d (1H, 6′-H, J = 9.0 Hz), 6.82 d (2H, 2″-H,
6″-H, J = 8.7 Hz), 7.16–7.19 d.d (1H, 6-H, J = 2.4,
9.0 Hz), 7.34 d (1H, 5-H, J = 8.7 Hz), 7.55 d (2H,
3″-H, 5″-H, J = 8.7 Hz), 7.65 d (1H, 2-H, J = 2.1 Hz),
7.85–7.88 d.d (1H, 5′-H, J = 2.7, 8.7 Hz), 8.84 d
(1H, 3′-H, J = 2.7 Hz), 9.82 s (1H, NH), 10.60 br.s
(1H, OH). Found, %: N 9.55, 9.73; S 7.41, 7.32.
C19H15N3O8S. Calculated, %: N 9.43; S 7.20.
2-(4-Chlorobenzenesulfonyl)-4-(2-nitrophenyl-
amino)phenol (IIIg). Yield 90%, mp 178–179°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 6.86 t (1H,
4′-H), 6.97 d (1H, 6-H, J = 8.4 Hz), 6.99 d (1H, 3′-H,
J = 8.4 Hz), 7.47–7.50 d.d (1H, 5-H, J = 1.8, 8.4 Hz),
4-(2,4-Dinitrophenylamino)-2,5-bis(4-methoxy-
benzenesulfonyl)phenol (VII). Yield 51%, mp 174–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 12 2014

KONOVALOVA et al.
1762
1
3. Toropin, N.V. and Burmistrov, K.S., Zh. Org. Khim.,
176°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.63 s
(3H, MeO), 3.84 s (3H, MeO), 6.79 d (1H, 6′-H, J =
8.4 Hz), 6.94 d (2H, 2″-H, 6″-H, J = 8.4 Hz), 7.09 d
(2H, 2′′′-H, 6′′′-H, J = 8.7 Hz), 7.65 d (2H, 3″-H, 5″-H,
J = 8.4 Hz), 7.80 s (1H, 6-H), 7.82–7.85 d.d (1H, 5′-H,
J = 2.7, 8.7 Hz), 7.83 d (2H, 3′′′-H, 5′′′-H, J = 8.7 Hz),
8.17 s (1H, 3-H), 8.85 d (1H, 3′-H, J = 2.4 Hz), 10.28 s
(1H, NH), 10.94 s (1H, OH). Found, %: N 7.00,
6.87; S 10.14, 10.40. C26H21N3O11S2. Calculated, %:
N 6.83; S 10.42.
1983, vol. 19, p. 1546.
4. Burmistrov, K.S. and Yurchenko, A.G., Zh. Org. Khim.,
1985, vol. 21, p. 575.
5. Burmistrov, S.I., Toropin, N.V., and Burmistrov, K.S.,
Vopr. Khim. Khim. Tekhnol., 1980, no. 61, p. 36.
6. Burmistrov, S.I. and Toropin, N.V., Zh. Org. Khim.,
1985, vol. 21, p. 1544.
7. Burmistrov, K.S., Doctoral (Chem.) Dissertation,
Dnepropetrovsk, 1990.
8. Konovalova, S.A., Avdeenko, A.P., Vasil’eva, V.M., and
Yusina, A.L., Russ. J. Org. Chem., 2014, vol. 50,
p. 1422.
4-(2,4-Dinitrophenylamino)-2-(4-methoxyben-
zenesulfonyl)phenyl 4-methoxybenzenesulfonate
(VIII). Yield 40%, mp 152–153°C. 1H NMR spectrum
(DMSO-d6), δ, ppm: 3.65 s (3H, MeO), 3.85 s (3H,
MeO), 6.89 s (1H, 6′-H), 6.75 d (2H, 2″-H, 6″-H, J =
8.4 Hz), 7.14 d (2H, 2′′′-H, 6′′′-H, J = 8.7 Hz), 7.41–
7.44 d.d (1H, 5-H, J = 3, 9.0 Hz), 7.47 d (1H, 6-H, J =
8.4 Hz), 7.53 d (2H, 3″-H, 5″-H, J = 8.4 Hz), 7.86 d
(1H, 3-H, J = 2.1 Hz), 7.89–7.92 d.d (1H, 5′-H, J =
2.3, 9.0 Hz), 7.91 d (2H, 3′′′-H, 5′′′-H, J = 8.7 Hz),
8.89 d (1H, 3′-H, J = 2.4 Hz), 10.18 s (1H, NH).
F o u n d , % : N 6 . 6 7 , 6 . 9 5 ; S 1 0 . 3 1 , 1 0 . 5 8.
C26H21N3O11S2. Calculated, %: N 6.83; S 10.42.
9. Sheldrick, G.M., SHELXTL PLUS. PC Version. A system
of Computer Programs for the Determination of Crystal
Structure from X-Ray Diffraction Data. Rev.5.1, 1998.
10. Granovsky, A.A., Firefly version 7.1.G. http://
classic.chem. msu.su/gran/firefly/index.html
11. Schmidt, M.W., Baldridge, K.K., Boatz, J.A.,
Elbert, S.T., Gordon, M.S., Jensen, J.J., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, S., Windus, T.L.,
Dupuis, M., and Montgomery, J.A., Jr., J. Comput.
Chem., 1993, vol. 14, p. 1347.
12. Burmistrov, K.S. and Burmistrov, S.I., Ukr. Khim. Zh.,
1978, vol. 44, p. 832.
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Nichvoloda, V.N., Ukr. Khim. Zh., 1992, vol. 58, p. 68.
1. Burmistrov, K.S. and Yurchenko, A.G., Zh. Org. Khim.,
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1922, vol. 2, p. 89.
2. Burmistrov, K.S., Toropin, N.V., Vakulenko, A.V.,
Yurchenko, A.G., and Markov, V.I., Vopr. Khim. Khim.
Tekhnol., 2000, no. 2, p. 30.
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