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

Article abstract of DOI:10.1134/S1070428014090103

N-Arylcarbamoyl-1,4-benzoquinone imines possessing at least one free ortho position with respect to the carbonyl carbon atom in the quinoid ring react with sodium arenesulfinates according to the nucleophilic 1,4-addition pattern with complete regioselect

Full text of DOI:10.1134/S1070428014090103

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 9, pp. 1292–1300. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, A.G. Sergeeva, Yu.V. Menafova, 2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50,
No. 9, pp. 1309–1317.
Reaction of N-Arylcarbamoyl-1,4-benzoquinone Imines
with Sodium Arenesulfinates
S. A. Konovalova, A. P. Avdeenko, A. G. Sergeeva, and Yu. V. Menafova
Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
Received December 4, 2013
Abstract—N-Arylcarbamoyl-1,4-benzoquinone imines possessing at least one free ortho position with respect
to the carbonyl carbon atom in the quinoid ring react with sodium arenesulfinates according to the nucleophilic
1,4-addition pattern with complete regioselectivity. If both ortho positions are occupied, the reaction gives
a mixture of products where the major ones are 1,6- and 6,1-adducts formed according to the radical ion
mechanism.
DOI: 10.1134/S1070428014090103
Reactions of N-substituted 1,4-benzoquinone
imines with sodium arenesulfinates lead to the forma-
tion of 1,6-, 6,1-, 6,3-, and 1,4-addition products [1–7].
It was found previously that the reaction direction is
largely determined by the nature of substituent on the
nitrogen atom [4–7], as well as by the nature and
position of substituents in the quinoid ring [1, 3–7].
Increase of the electron-withdrawing power of the
substituent on the nitrogen atom increases the redox
potential [3, 7, 8], which favors generation of quinone
imine radical anion and hence radical ion reaction path
with formation of 1,6- and 6,1-addition products [2, 3,
6–8]. The maximum yield of the latter was attained in
the reactions with N-aroyl-substituted 1,4-benzoqui-
none imines [4, 5, 7] characterized by the highest
redox potential [8]. N-Arenesulfonyl derivatives react
mainly according to the 1,4-addition pattern involving
direct nucleophilic addition of sulfinate ion [4–7]. It
should be noted that the ability to form radical ion
species may be estimated from the LUMO energy of
quinone imine; reduction of the LUMO energy favors
single-electron transfer. This is especially important
for those quinone imines whose redox potential was
not determined.
carbamoyl-1,4-benzoquinone imine is –370.67 kJ/mol,
and it occupies an intermediate place between the
LUMO energies of N-benzoyl (–364.97 kJ/mol) and
N-benzenesulfonyl analogs (–383.93 kJ/mol). Taking
the aforesaid into account, we presumed that the reac-
tivity of N-arylcarbamoyl-1,4-benzoquinone imines
toward sodium arenesulfinates should be intermediate
between the reactivities of N-aroyl and N-arenesul-
fonyl derivatives. The present work was aimed at
verifying this assumption.
The reactions of quinone imines Ia–Iv with sodium
arenesulfinates IIa–IIc were carried out at a reactant
ratio of 1 :2 in acetic acid at room temperature. In
order to detect all products formed the reaction mix-
tures were analyzed after complete precipitation with
water. A part of the solid product thus obtained was
1
recrystallized, and H NMR spectra of both parts, as
well as of the product isolated from the mother liquor,
were recorded.
Quinone imines Ia–Ip having at least one free
ortho position with respect to the quinoid carbonyl
carbon atom reacted with sodium arenesulfinates to
give only 1,4-addition products IIIa–IIIy (Scheme 1).
Compounds IIIj–IIIm, IIIo, IIIp, IIIr–IIIt, and IIIw
were oxidized with lead(IV) acetate in acetic acid to
the corresponding quinone imines IVj–IVm, IVo,
We previously synthesized new N-arylcarbamoyl-
1,4-benzoquinone imines [9], and their redox poten-
tials have not yet been measured. On the one hand, the
presence of a carbonyl group on the imino nitrogen
atom could make these compounds comparable in
reactivity with N-aroyl derivatives [4, 5, 7]. On the
other hand, the calculated LUMO energy of N-phenyl-
1
IVp, IVr–IVt, and IVw since the H NMR spectra of
the latter were more informative.
The 1H NMR spectra of IIIa–IIIy contained signals
from the OH, N1H, and N2H protons in the regions
1292

REACTION OF N-ARYLCARBAMOYL-1,4-BENZOQUINONE IMINES
1293
Scheme 1.
R2
R2
H
N
2H
N
1 H
N
X
Y
N
R1
O
SO2Na
X
Y
R1
AcOH
+
O
O
R3
Z
R3
OH
SO2C6H4Z-4
Ia–Ip
IIa–IIc
IIIa–IIIy
R2
H
N
X
Y
N
R1
O
[O]
O
R3
SO2C6H4Z-4
IVj–IVm, IVo, IVp, IVr–IVt, IVw
I, R1 = R2 = R3 = X = H: Y = H (a), Me (b); R1 = Me, R2 = R3 = X = Y = H (c); R1 = R3 = X = H, R2 = Y = Me (d); R1 = R2 = Me:
R3 = X = Y = H (e); R3 = X = H, Y = Me (f); R3 = Y = H, X = Me (g); R3 = Y = H, X = Cl (h); R1 = R3 = Me: R2 = X = Y = H (i);
R2 = X = H, Y = Me (j); R1 = Me, R3 = i-Pr: R2 = X = Y = H (k); R2 = X = H, Y = Me (l); R1 = i-Pr, R3 = Me: R2 = X = Y = H (m);
R2 = X = H, Y = Me (n); R2 = R3 = Me: R1 = X = Y = H (o); R2 = X = H, Y = Me (p); II, Z = H (a), Me (b), MeO (c); III, IV, R1 =
R2 = R3 = X = H: Y = H, Z = Me (a); Y = H, Z = MeO (b); Y = Me, Z = MeO (c); R2 = R3 = X = Y = H, R1 = Me: Z = H (d), Z =
Me (e), Z = MeO (f); R1 = R3 = X = H, R2 = Y = Me, Z = MeO (g); R1 = R2 = X = H, R3 = Y = Me, Z = MeO (h); R1 = R2 = Me, R3 =
H: X = Y = H, Z = Me (i); X = Y = H, Z = MeO (j); X = Me, Y = H, Z = Me (k); X = Me, Y = H, Z = MeO (l); X = Cl, Y = H, Z =
Me (m); X = H, Y = Me, Z = MeO (n); R1 = R3 = Me, R2 = X = H: Y = Z = H (o); Y = H, Z = MeO (p); Y = Me, Z = MeO (q); R1 =
Me, R3 = i-Pr, R2 = X = H: Y = H, Z = Me (r); Y = H, Z = MeO (s); Y = Me, Z = MeO (t); R1 = i-Pr, R3 = Me, R2 = X = H: Y = Z =
H (u); Y = Me, Z = MeO (v); R2 = R3 = Me, R1 = X = H: Y = H, Z = Me (w); Y = H, Z = MeO (x); Y = Me, Z = MeO (y).
δ 8.94–10.79, 7.22–8.69, and 7.74–9.22 ppm, respec-
tively. Quinone imines IVj–IVm, IVo, IVp, IVr–IVt,
and IVw displayed in the spectra broadened singlets
due to NH proton at δ 7.03–7.65 ppm and signals from
protons in the quinoid ring at δ 8.10–8.19 (s, IVj–
IVm), 6.94–6.99 (s, IVr–IVt), and 7.13–7.14 ppm (q,
IVo, IVp). Protons in the methyl groups attached to the
quinoid ring resonated at δ 1.92–1.98 and 2.12–2.17
(IVj–IVm), 1.91–1.94 and 2.85–2.86 (IVo, IVp), and
2.23 and 2.81 ppm (IVw). Multiplet signal from the
CHMe2 proton in IVr–IVt was located at δ 4.66–
4.78 ppm, and the methyl proton signal was a doublet
at δ 1.87–1.89 ppm. These data unambiguously indi-
cated that the ArSO2 group in compounds IV occupies
ortho position with respect to the quinoid carbonyl
carbon atom.
Ve, VIa–VIe, and VIIa–VIIc (Scheme 2, see table),
whose structure was determined on the basis of the
NMR spectra with account taken of published data for
structurally related compounds [4]. 1,6-Addition prod-
1
ucts Va–Ve characteristically showed in the H NMR
spectra a singlet at δ 7.19–7.34 from 3-H and 5-H. The
2-H and 6-H protons in the spectra of the 6,1-addition
products resonated as a singlet at δ 6.97–6.99 (VIa–
VIc) or 6.59–6.60 ppm (VId, VIe), and the 6-H signal
of 6,3-addition products VIIa–VIIc appeared as a sin-
glet in a weaker field, at δ 7.39–7.41 ppm. The singlet
from the methoxy protons in the 4-MeOC6H4SO2
group was observed at δ 3.89 (Va–Ve, VIa–VIe) or
3.72 ppm (VIIa–VIIc). The CHMe2 signal was
a multiplet at δ 2.96–3.08 (Vd, Ve) or 3.12–3.22 ppm
(VId, VIe).
The reaction of quinone imine Id with sodium
4-metoxybenzenesulfinate (IIc) gave a mixture of two
1,4-addition products IIIg and IIIh at a ratio of 68:32,
i.e., the para position with respect to the methyl group
was more reactive. In keeping with our previous data,
the addition of arenesulfinates to analogous N-aroyl
and N-arenesulfonyl derivatives was completely regio-
selective: it involved the para position with respect to
the methyl group in the quinoid ring [7].
As follows from the data in table, the major prod-
ucts obtained from quinone imines Iq–It were 1,6-ad-
ducts Va–Ve, which was typical of analogous N-aroyl
derivatives [4]. In going from dimethyl- (Iq, Ir) to
diisopropyl-substituted compounds (Is, It) the yield of
the 1,6-addition product increases in parallel with the
donor properties of the substituents. As with N-aroyl
quinone imines, 6,3-addition products were detected
only in the reactions with dimethyl derivatives Iq and
Ir. In the reactions of di-tert-butyl-substituted quinone
imines Iu and Iv we isolated 2,6-di-tert-butyl-1,4-
Compounds Iq–It reacted with arenesulfinates IIa–
IIc to afford 1,6-, 6,1-, and 6,3-addition products Va–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

KONOVALOVA et al.
1294
Scheme 2.
2H
N
H
1N
R
1,6-Addition
O
Y
OSO2C6H4Z-4
R
Va–Ve
SO2C6H4Z-4
N
H
N
H
N
R
N
R
O
AcOH 6,1-Addition
+
IIa–IIc
O
O
Y
OH
Y
R
R
VIa–VIe
Iq–It
SO2C6H4Z-4
R
H
H
2 N
1 N
6,3-Addition
O
Y
OH
R
VIIa–VIIc
I, R = Me: Y = H (q), Me (r); R = i-Pr: Y = Me (s), O2N (t); V–VII, R = Me: Y = H, Z = Me (a); Y = Me, Z = H (b);
Y = Me, Z = MeO (c); R = i-Pr: Y = Z = Me (d); Y = O2N, Z = Me (e).
Scheme 3.
O
H
N
H
N
N
Bu-t
NH2
t-Bu
Bu-t
H2O
+
IIb, IIc
+
O
O
Y
O
Y
Bu-t
O
Iu, Iv
I, Y = H (u), Me (v).
benzoquinone and N-substituted urea (Scheme 3)
which were formed as a result of hydrolysis of the
initial quinone imines.
Thus, N-arylcarbamoyl-1,4-benzoquinone imines
having at least one free ortho position with respect to
the carbonyl carbon atom react with sodium arenesul-
finates exclusively according to the direct nucleophilic
1,4-addition scheme, i.e., in a way similar to N-arene-
sulfonyl derivatives [4, 7]. The reactivity of N-aryl-
carbamoyl-2,6-dialkyl-1,4-benzoquinone imines ap-
proaches that of N-aroyl derivatives [4] which give rise
mainly to 1,6- and 6,1-addition products according to
the radical ion mechanism. Introduction of alkyl
groups into positions 2 and 6 of the quinoid ring con-
siderably increases the LUMO energy [ELUMO(Iq) =
–348.168 kJ/mol], so that the radical ion path leading
to 1,6- and 6,1-addition products becomes more favor-
able than nucleophilic 6,3-addition.
Reactions of quinone imines Iq–It with sodium arenesul-
finates IIa–IIc
Product fraction, %
Initial quinone Sodium arene-
imine no.
sulfinate no.
V (1,6) VI (6,1) VII (6,3)
EXPERIMENTAL
Iq
Ir
Ir
Is
It
IIb
IIa
IIc
IIb
IIb
49
57
61
89
82
17
13
17
11
18
34
30
22
–
1
The H NMR spectra were measured on a Varian
VXR-300 spectrometer at 300 MHz using tetramethyl-
silane as internal reference. The IR spectra were re-
corded in KBr on a UR-20 spectrometer. The progress
of reactions and the purity of products were monitored
–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

REACTION OF N-ARYLCARBAMOYL-1,4-BENZOQUINONE IMINES
1295
by TLC on Silufol UV-254 plates; spots were applied
from solutions in chloroform, plates were eluted with
benzene–hexane (10:1), and the chromatograms were
developed under UV light.
Quantum chemical calculations were performed
using Firefly QC software package [10] based in part
on the GAMESS code (US) [11]. The molecular struc-
tures were optimized at the DFT B3LYP/6-31+G(d)
level of theory.
Compounds Ia–Iv were synthesized by oxidation of
the corresponding 1-(4-hydroxyphenyl)-3-arylureas
[9]. The properties of compounds Ia, Ic–Ie, Ii, Ik–Im,
Io–Ir, Iu [9], Ib, Ig, Ih, and Ij [12] were consistent
with published data. Sodium arenesulfinates IIa–IIc
were prepared as described in [13].
1.14 q [12H, CH(CH3)2, J = 6.3 Hz], 3.06–3.15 m [2H,
CH(CH3)2], 6.78 br.s (1H, 6-H), 7.09 br.s (1H, 2-H),
7.49 br.s (1H, NH), 7.74 d (2H, 2′-H, 6′-H, J = 8.7 Hz),
8.26 d (2H, 3′-H, 5′-H, J = 8.7 Hz). Found, %:
N 11.76, 11.85. C19H21N3O4. Calculated, %: N 11.82.
1-(3,5-Di-tert-butyl-4-oxocyclohexa-2,5-dien-
1-ylidene)-3-(4-methylphenyl)urea (Iv). Yield 42%,
1
mp 122–124°C. H NMR spectrum (CDCl3), δ, ppm:
1.28 d (18H, t-Bu, J = 10.5 Hz), 2.34 s (3H, 4′-CH3),
6.82 br.s (1H, 6-H), 7.08 br.s (1H, 2-H), 7.15 br.s (1H,
NH), 7.17 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.43 d (2H,
3′-H, 5′-H, J = 8.7 Hz). Found, %: N 7.97, 7.99.
C22H28N2O2. Calculated, %: N 7.95.
Reaction of quinone imines Ia–Iv with sodium
arenesulfinates IIa–IIc. Quinone imine Ia–Iv,
2 mmol, was dispersed in 5–8 mL of glacial acetic
acid, 4 mmol of sodium arenesulfinate was added in
one portion, and the mixture was stirred at room tem-
perature until it became colorless. The mixture was
diluted with water until complete precipitation, and 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 precip-
itate was filtered off. All three samples (the crude
product before and after recrystallization and the prod-
uct isolated from the mother liquor) were analyzed by
1H NMR.
1-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-
1-ylidene)-3-(4-methylphenyl)urea (If). Yield 59%,
1
mp 112–113°C. H NMR spectrum (CDCl3), δ, ppm:
2.04 s (3H, 3-Me), 2.17 s (3H, 2-Me), 2.33 s (3H,
4′-CH3), 6.51 d (1H, 5-H, J = 10.2 Hz), 7.09 br.s (1H,
NH), 7.15 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.22 d (1H,
6-H, J = 10.2 Hz), 7.43 d (2H, 3′-H, 5′-H, J = 8.1 Hz).
Found, %: N 10.96, 10.99. C16H16N2O2. Calculated, %:
N 10.44.
1-(5-Isopropyl-2-methyl-4-oxocyclohexa-2,5-
dien-1-ylidene)-3-(4-methylphenyl)urea (In). Yield
1
65%, mp 122–124°C. H NMR spectrum (CDCl3), δ,
ppm: 1.09 d [6H, CH(CH3)2, J = 6.9 Hz], 2.17 s (3H,
2-Me), 2.33 s (3H, 4′-CH3), 2.95–3.03 m [1H,
CH(CH3)2], 6.53 br.s (1H, 3-H), 6.91 br.s (1H, NH),
6.95 s (1H, 6-H), 7.18 d (2H, 2′-H, 6′-H, J = 8.1 Hz),
7.44 d (2H, 3′-H, 5′-H, J = 8.1 Hz). Found, %: N 9.40,
9.48. C18H20N2O2. Calculated, %: N 9.45.
1-[4-Hydroxy-3-(4-methylbenzenesulfonyl)-
phenyl]-3-phenylurea (IIIa). Yield 95%, mp 197–
1
198°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.38 s
(3H, 4′-CH3), 6.83 d (1H, 5-H, J = 9 Hz), 6.94–7.46 m
(5H, Ph), 7.39 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.44–
7.47 d.d (1H, 6-H, J = 2.7, 8.7 Hz), 7.78 d (2H, 3′-H,
5′-H, J = 8.1 Hz), 8.10 d (1H, 2-H, J = 2.7 Hz), 8.61 s
(1H, N1H), 8.71 s (1H, N2H), 10.33 s (1H, OH).
Found, %: N 7.28, 7.45. C20H18N2O4S. Calculated, %:
N 7.33.
1-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dien-
1-ylidene)-3-(4-methylphenyl)urea (Is). Yield 45%,
1
mp 135–136°C. H NMR spectrum (CDCl3), δ, ppm:
1.13 d [12H, CH(CH3)2, J = 6.3 Hz], 2.33 s (3H,
4′-CH3), 3.03–3.19 m [2H, CH(CH3)2], 6.79 s (1H,
6-H), 7.13 s (1H, 2-H), 7.15 d (2H, 2′-H, 6′-H, J =
7.8 Hz), 7.32 br.s (1H, NH), 7.44 d (2H, 3′-H, 5′-H, J =
7.8 Hz). Found, %: N 8.62, 8.67. C20H24N2O2. Calcu-
lated, %: N 8.64.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-
phenyl]-3-phenylurea (IIIb). Yield 57%, mp 208–
1
209°C. H NMR spectrum (DMSO-d6), δ, ppm: 3.83 s
(3H, CH3O), 6.82 d (1H, 5-H, J = 7.8 Hz), 6.94–
7.47 m (5H, Ph), 7.11 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.44–7.47 d.d (1H, 6-H, J = 2.4, 7.8 Hz), 7.84 d (2H,
3′-H, 5′-H, J = 8.4 Hz), 8.08 d (1H, 2-H, J = 2.4 Hz),
8.63 s (1H, N1H), 8.73 s (1H, N2H), 10.32 br.s (1H,
OH). Found, %: N 6.97, 7.15. C20H18N2O5S. Calculat-
ed, %: N 7.03.
1-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dien-
1-ylidene)-3-(4-nitrophenyl)urea (It). Yield 57%,
1
mp 158–159°C. H NMR spectrum (CDCl3), δ, ppm:
* Hereinafter, unprimed locants refer to protons in the quinone
imine fragment; in case of ambiguity, primed locants refer to
protons in the aromatic ring on the nitrogen atom, and double-
primed locants, to those in the aromatic ring formerly belonging
to arenesulfinate.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-
phenyl]-3-(4-methylbenzenesulfonyl)urea (IIIc).
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KONOVALOVA et al.
1296
1
Yield 88%, mp 239–240°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.24 s (3H, 4′-CH3), 3.83 s (3H,
CH3O), 6.80 d (1H, 5-H, J = 9 Hz), 7.08 d (2H, 2′-H,
6′-H, J = 8.7 Hz), 7.10 d (2H, 2″-H, 6″-H, J = 9 Hz),
7.34 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.42–7.45 d.d (1H,
6-H, J = 2.7, 9 Hz), 7.84 d (2H, 3″-H, 5″-H, J = 9 Hz),
8.08 d (1H, 2-H, J = 2.7 Hz), 8.49 s (1H, N1H), 8.66 s
(1H, N2H), 10.31 br.s (1H, OH). Found, %: N 6.67,
6.81. C21H20N2O5S. Calculated, %: N 6.79.
J = 8.7 Hz), 7.09 d (2H, 2″-H, 6″-H, J = 9 Hz), 7.35 d
(2H, 3′-H, 5′-H, J = 8.7 Hz), 7.41 d (1H, 6-H, J =
8.7 Hz), 7.83 d (2H, 3″-H, 5″-H, J = 9 Hz), 7.86 s (1H,
N1H), 8.70 s (1H, N2H), 10.35 s (1H, OH).
1-[4-Hydroxy-2,3-dimethyl-5-(4-methylbenzene-
sulfonyl)phenyl]-3-phenylurea (IIIi). Yield 32%,
1
mp 186–188°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.08 s (3H, 3-Me), 2.15 s (3H, 2-Me), 2.37 s (3H,
4′-CH3), 6.92–7.48 m (5H, Ph), 7.38 d (2H, 2′-H, 6′-H,
J = 8.4 Hz), 7.80 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.97 s
(1H, 6-H), 8.14 s (1H, N1H), 8.99 s (1H, N2H),
9.37 br.s (1H, OH). Found, %: N 6.77, 6.95.
C22H22N2O4S. Calculated, %: N 6.82.
1-[5-(Benzenesulfonyl)-4-hydroxy-3-methyl-
phenyl]-3-phenylurea (IIId). Yield 63%, mp 189–
1
190°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.13 s
(3H, 3-Me), 6.95–7.47 m (5H, Ph), 7.41 d (1H, 2-H,
J = 2.1 Hz), 7.58–7.93 m (5H, PhSO2), 8.01 d (1H,
6-H, J = 2.1 Hz), 8.66 s (1H, N1H), 8.71 s (1H, N2H),
9.34 br.s (1H, OH). Found, %: N 7.24, 7.45.
C20H18N2O4S. Calculated, %: N 7.33.
1-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-2,3-
dimethylphenyl]-3-phenylurea (IIIj). Yield 73%,
1
mp 209–216°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.07 s (3H, 3-Me), 2.12 s (3H, 2-Me), 3.81 s (3H,
CH3O), 6.92–7.47 m (5H, Ph), 7.09 d (2H, 2′-H, 6′-H,
J = 8.7 Hz), 7.85 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.93 s
(1H, 6-H), 8.09 s (1H, N1H), 8.97 s (1H, N2H),
9.35 br.s (1H, OH). Found, %: N 6.45, 6.61.
C22H22N2O5S. Calculated, %: N 6.57.
1-[4-Hydroxy-3-methyl-5-(4-methylbenzenesul-
fonyl)phenyl]-3-phenylurea (IIIe). Yield 70%,
1
mp 211–212°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.12 s (3H, 3-Me), 2.38 s (3H, 4′-CH3), 6.93–
7.49 m (5H, Ph), 7.38 d (1H, 2-H, J = 2.4 Hz), 7.39 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.80 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 7.99 d (1H, 6-H, J = 2.4 Hz), 8.88 s (1H,
N1H), 8.93 s (1H, N2H), 9.51 br.s (1H, OH). Found, %:
N 6.98, 7.15. C21H20N2O4S. Calculated, %: N 7.07.
1-[4-Hydroxy-2,3-dimethyl-5-(4-methylbenzene-
sulfonyl)phenyl]-3-(3-methylphenyl)urea (IIIk).
1
Yield 75%, mp 203–205°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.07 s (3H, 3-Me), 2.14 s (3H,
2-Me), 2.27 s (3H, 4″-CH3), 2.37 s (3H, 3′-CH3), 6.76–
6.78 d.d (1H, 4′-H, J = 7.2, 1.2 Hz), 7.11–7.16 t (1H,
5′-H), 7.22–7.25 d.d (1H, 6′-H, J = 7.2, 1.2 Hz),
7.33 br.s (1H, 2′-H), 7.39 d (2H, 2″-H, 6″-H, J =
8.1 Hz), 7.78 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 7.99 s
(1H, 6-H), 8.18 s (1H, N1H), 8.99 s (1H, N2H), 9.27 s
(1H, OH). Found, %: N 6.51, 6.68. C23H24N2O4S. Cal-
culated, %: N 6.60.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-
5-methylphenyl]-3-phenylurea (IIIf). Yield 85%,
1
mp 169–171°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.13 s (3H, 5-Me), 3.83 s (3H, CH3O), 6.94–
7.47 m (5H, Ph), 7.12 d (2H, 2′-H, 6′-H, J = 9 Hz),
7.38 d (1H, 6-H, J = 2.4 Hz), 7.86 d (2H, 3′-H, 5′-H,
J = 9 Hz), 7.95 d (1H, 2-H, J = 2.4 Hz), 8.61 s (1H,
N1H), 8.66 s (1H, N2H), 9.21 s (1H, OH). Found, %:
N 6.73, 6.85. C21H20N2O5S. Calculated, %: N 6.79.
1-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-2,3-
dimethylphenyl]-3-(3-methylphenyl)urea (IIIl).
1-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-2-
1
methylphenyl]-3-(4-methylphenyl)urea (IIIg). Yield
Yield 85%, mp 192–193°C. H NMR spectrum
1
68%. H NMR spectrum (DMSO-d6), δ, ppm: 2.18 s
(DMSO-d6), δ, ppm: 2.08 s (3H, 3-Me), 2.13 s (3H,
2-Me), 2.27 s (3H, 3′-CH3), 3.82 s (3H, CH3O), 6.75–
6.78 d.d (1H, 4′-H, J = 7.5, 1.2 Hz), 7.09–7.16 t (1H,
5′-H), 7.10 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.22–
7.25 d.d (1H, 6′-H, J = 7.5, 1.2 Hz), 7.33 br.s (1H,
2′-H), 7.85 d (2H, 3″-H, 5″-H, J = 8.7 Hz), 7.96 s (1H,
6-H), 8.68 s (1H, N1H), 8.97 s (1H, N2H), 9.65 s (1H,
OH). Found, %: N 6.28, 6.45. C23H24N2O5S. Calculat-
ed, %: N 6.36.
(3H, 2-Me), 2.25 s (3H, 4′-CH3), 3.82 s (3H, CH3O),
6.70 s (1H, 3-H), 7.09 d (2H, 2′-H, 6′-H, J = 8.7 Hz),
7.09 d (2H, 2″-H, 6″-H, J = 9 Hz), 7.35 d (2H, 3′-H,
5′-H, J = 8.7 Hz), 7.82 d (2H, 3″-H, 5″-H, J = 9 Hz),
7.87 s (1H, N1H), 8.22 s (1H, 6-H), 8.81 s (1H, N2H),
10.30 s (1H, OH).
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-2-
methylphenyl]-3-(4-methylphenyl)urea (IIIh). Yield
1
32%. H NMR spectrum (DMSO-d6), δ, ppm: 2.23 s
1-(3-Chlorophenyl)-3-[4-hydroxy-2,3-dimethyl-
5-(4-methylbenzenesulfonyl)phenyl]urea (IIIm).
(3H, 2-Me), 2.25 s (3H, 4′-CH3), 3.83 s (3H, CH3O),
6.95 d (1H, 5-H, J = 8.7 Hz), 7.09 d (2H, 2′-H, 6′-H,
1
Yield 80%, mp 201–202°C. H NMR spectrum
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REACTION OF N-ARYLCARBAMOYL-1,4-BENZOQUINONE IMINES
1297
(DMSO-d6), δ, ppm: 2.07 s (3H, 3-Me), 2.14 s (3H,
2-Me), 2.37 s (3H, 4″-CH3), 6.99–7.02 d.d (1H, 4′-H,
J = 7.2, 1.2 Hz), 7.28 d (1H, 6′-H, J = 7.2, 1.2 Hz),
7.28–7.33 t (1H, 5′-H), 7.40 d (2H, 2″-H, 6″-H, J =
8.4 Hz), 7.79 d (2H, 3″-H, 5″-H, J = 8.4 Hz), 7.96 s
(1H, 6-H), 8.13 s (1H, N1H), 9.13 s (1H, N2H), 9.68 s
(1H, OH). Found, %: N 6.21, 6.38. C22H21ClN2O4S.
Calculated, %: N 6.30.
CH(CH3)2], 6.89–7.42 m (5H, Ph), 7.36 s (1H, 6-H),
7.36 s (1H, N1H), 7.48 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.75 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 8.92 s (1H, N2H),
10.73 s (1H, OH). Found, %: N 6.27, 6.48.
C24H26N2O4S. Calculated, %: N 6.39.
1-[4-Hydroxy-2-isopropyl-3-(4-methoxybenzene-
sulfonyl)-5-methylphenyl]-3-phenylurea (IIIs). Yield
1
62%, mp 226–228°C. H NMR spectrum (DMSO-d6),
1-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-
2,3-dimethylphenyl]-3-(4-methylphenyl)urea (IIIn).
δ, ppm: 0.95 d [6H, CH(CH3)2, J = 7.2 Hz], 2.15 s
(3H, 5-Me), 3.68–3.78 m [1H, CH(CH3)2], 3.84 s (3H,
CH3O), 6.88–7.42 m (5H, Ph), 7.15 d (2H, 2′-H, 6′-H,
J = 9 Hz), 7.27 s (1H, 6-H), 7.67 s (1H, N1H), 7.79 d
(2H, 3′-H, 5′-H, J = 9 Hz), 9.22 s (1H, N2H), 10.75 s
(1H, OH). Found, %: N 6.05, 6.27. C24H26N2O5S.
Calculated, %: N 6.16.
1
Yield 82%, mp 230–231°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.07 s (3H, 3-Me), 2.14 s (3H,
2-Me), 2.24 s (3H, 4′-CH3), 3.82 s (3H, CH3O), 7.08 d
(2H, 2′-H, 6′-H, J = 8.7 Hz), 7.09 d (2H, 2″-H, 6″-H,
J = 8.7 Hz), 7.34 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.83 d
(2H, 3″-H, 5″-H, J = 8.7 Hz), 7.97 s (1H, 6-H), 8.69 s
(1H, N1H), 8.96 s (1H, N2H), 9.63 s (1H, OH). Found,
%: N 6.28, 6.41. C23H24N2O5S. Calculated, %: N 6.36.
1-[4-Hydroxy-2-isopropyl-3-(4-methoxybenzene-
sulfonyl)-5-methylphenyl]-3-(4-methylphenyl)urea
1
(IIIt). Yield 48%, mp 256–257°C. H NMR spectrum
1-[3-(Benzenesulfonyl)-4-hydroxy-2,5-dimethyl-
(DMSO-d6), δ, ppm: 0.94 d [6H, CH(CH3)2, J =
7.2 Hz], 2.18 s (3H, 5-Me), 2.21 s (3H, 4′-CH3), 3.62–
3.72 m [1H, CH(CH3)2], 3.85 s (3H, CH3O), 7.04 d
(2H, 2′-H, 6′-H, J = 7.8 Hz), 7.18 d (2H, 2″-H, 6″-H,
J = 8.7 Hz), 7.29 d (2H, 3′-H, 5′-H, J = 7.8 Hz), 7.33 s
(1H, 6-H), 7.33 s (1H, N1H), 7.80 d (2H, 3″-H, 5″-H,
J = 8.7 Hz), 8.85 s (1H, N2H), 10.79 s (1H, OH).
Found, %: N 5.85, 6.07. C25H28N2O5S. Calculated, %:
N 5.98.
phenyl]-3-phenylurea (IIIo). Yield 76%, mp 211–
1
212°C. H NMR spectrum (DMSO-d6), δ, ppm: 2.19 s
(3H, 5-Me), 2.24 s (3H, 2-Me), 6.91–7.42 m (5H,
PhNH), 7.57 s (1H, 6-H), 7.63–7.92 m (5H, PhSO2),
7.89 s (1H, N1H), 8.80 s (1H, N2H), 10.23 s (1H, OH).
Found, %: N 6.48, 6.64. C21H20N2O4S. Calculated, %:
N 7.07.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-2,5-
dimethylphenyl]-3-phenylurea (IIIp). Yield 78%,
1-[3-(Benzenesulfonyl)-4-hydroxy-5-isopropyl-
1
mp 217–219°C. H NMR spectrum (DMSO-d6), δ,
2-methylphenyl]-3-phenylurea (IIIu). Yield 58%,
1
ppm: 2.18 s (3H, 5-Me), 2.22 s (3H, 2-Me), 3.85 s (3H,
CH3O), 6.90–7.42 m (5H, Ph), 7.16 d (2H, 2′-H, 6′-H,
J = 8.7 Hz), 7.53 s (1H, 6-H), 7.84 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 7.87 s (1H, N1H), 8.79 s (1H, N2H),
10.36 s (1H, OH). Found, %: N 6.48, 6.64.
C22H22N2O5S. Calculated, %: N 6.57.
mp 241–243°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.19 d [6H, CH(CH3)2, J = 7.2 Hz], 2.20 s (3H,
2-Me), 3.24–3.33 m [1H, CH(CH3)2], 6.91–7.43 m
(5H, Ph), 7.61 s (1H, 6-H), 7.65–7.92 m (5H, PhSO2),
7.94 s (1H, N1H), 8.84 s (1H, N2H), 10.42 s (1H, OH).
Found, %: N 5.91, 6.07. C23H24N2O4S. Calculated, %:
N 6.60.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-2,5-
dimethylphenyl]-3-(4-methylphenyl)urea (IIIq).
1-[4-Hydroxy-5-isopropyl-3-(4-methoxybenzene-
sulfonyl)-2-methylphenyl]-3-(4-methylphenyl)urea
1
Yield 85%, mp 228–229°C. H NMR spectrum
1
(DMSO-d6), δ, ppm: 2.19 s (3H, 5-Me), 2.22 s (3H,
2-Me), 2.22 s (3H, 4′-CH3), 3.85 s (3H, CH3O), 7.05 d
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.16 d (2H, 2″-H, 6″-H,
J = 9 Hz), 7.29 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.54 br.s
(1H, 6-H), 7.82 s (1H, N1H), 7.84 d (2H, 3″-H, 5″-H,
J = 9 Hz), 8.66 s (1H, N2H), 10.32 s (1H, OH). Found,
%: N 6.31, 6.46. C23H24N2O5S. Calculated, %: N 6.36.
(IIIv). Yield 32%, mp 211–213°C. H NMR spectrum
(DMSO-d6), δ, ppm: 1.18 d [6H, CH(CH3)2, J =
6.9 Hz], 2.18 s (3H, 2-Me), 2.22 s (3H, 4′-CH3), 3.25–
3.34 m [1H, CH(CH3)2], 3.85 s (3H, CH3O), 7.05 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.18 d (2H, 2″-H, 6″-H,
J = 8.7 Hz), 7.29 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.56 s
(1H, 6-H), 7.84 d (2H, 3″-H, 5″-H, J = 8.7 Hz), 7.86 s
(1H, N1H), 8.70 s (1H, N2H), 10.48 s (1H, OH).
Found, %: N 5.96, 6.05. C25H28N2O5S. Calculated, %:
N 5.98.
1-[4-Hydroxy-2-isopropyl-5-methyl-3-(4-methyl-
benzenesulfonyl)phenyl]-3-phenylurea (IIIr). Yield
1
54%, mp 257–258°C. H NMR spectrum (DMSO-d6),
δ, ppm: 0.93 d [6H, CH(CH3)2, J = 7.2 Hz], 2.19 s
(3H, 5-Me), 2.40 s (3H, 4′-CH3), 3.60–3.70 m [1H,
1-[4-Hydroxy-2,6-dimethyl-3-(4-methylbenzene-
sulfonyl)phenyl]-3-phenylurea (IIIw). Yield 94%,
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KONOVALOVA et al.
1298
1
mp 247–248°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.13 s (3H, 2-Me), 2.38 s (3H, 4′-CH3), 2.44 s
(3H, 6-Me), 6.64 s (1H, 5-H), 6.88–7.44 m (5H, Ph),
7.22 s (1H, N1H), 7.38 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.76 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 7.92 s (1H, N2H),
9. 16 s (1H, OH). Found, %: N 6. 77, 6. 80.
C22H22N2O4S. Calculated, %: N 6.82.
1-[5-(4-Methoxybenzenesulfonyl)-2,3-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene]-3-(3-methyl-
phenyl)urea (IVl). Yield 37%, mp 180–181°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.98 s (3H,
3-Me), 2.17 s (3H, 2-Me), 2.39 s (3H, 3′-CH3), 3.87 s
(3H, CH3O), 6.98 d (2H, 2″-H, 6″-H, J = 8.7 Hz),
6.98–7.45 m (4H, 3-CH3C6H4), 7.37 br.s (1H, NH),
8.01 d (2H, 3″-H, 5″-H, J = 8.7 Hz), 8.17 s (1H, 6-H).
Found, %: N 6.31, 6.40. C23H22N2O5S. Calculated,
%: N 6.39.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-2,6-
dimethylphenyl]-3-phenylurea (IIIx). Yield 97%,
1
mp 230–236°C. H NMR spectrum (DMSO-d6), δ,
ppm: 2.12 s (3H, 2-Me), 2.44 s (3H, 6-Me), 3.83 s (3H,
CH3O), 6.64 s (1H, 5-H), 6.88–7.44 m (5H, Ph), 7.09 d
(2H, 2′-H, 6′-H, J = 9 Hz), 7.23 s (1H, N1H), 7.82 d
(2H, 3′-H, 5′-H, J = 9 Hz), 7.84 s (1H, N2H), 9.07 s
(1H, OH). Found, %: N 6.61, 6.65. C22H22N2O5S. Cal-
culated, %: N 6.57.
1-(3-Chlorophenyl)-3-[2,3-dimethyl-5-(4-meth-
ylbenzenesulfonyl)-4-oxocyclohexa-2,5-dien-1-
ylidene]urea (IVm). Yield 42%, mp 155–156°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.94 s (3H,
3-Me), 2.14 s (3H, 2-Me), 2.43 s (3H, 4″-CH3), 7.12–
7.52 m (4H, ClC6H4), 7.33 d (2H, 2″-H, 6″-H, J =
8.4 Hz), 7.71 br.s (1H, NH), 7.94 d (2H, 3″-H, 5″-H,
J = 8.4 Hz), 8.10 s (1H, 6-H). Found, %: N 6.35, 6.39.
C22H19ClN2O4S. Calculated, %: N 6.32.
1-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-2,6-
dimethylphenyl]-3-(4-methylphenyl)urea (IIIy).
1
Yield 93%, mp 234–236°C. H NMR spectrum
(DMSO-d6), δ, ppm: 2.12 s (3H, 2-Me), 2.22 s (3H,
4′-CH3), 2.43 s (3H, 6-Me), 3.83 s (3H, CH3O), 6.66 s
(1H, 5-H), 7.03 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.10 d
(2H, 2″-H, 6″-H, J = 8.7 Hz), 7.30 s (1H, N1H), 7.31 d
(2H, 3′-H, 5′-H, J = 8.4 Hz), 7.74 s (1H, N2H), 7.83 d
(2H, 3″-H, 5″-H, J = 8.7 Hz), 8.94 s (1H, OH). Found,
%: N 6.30, 6.39. C23H24N2O5S. Calculated, %: N 6.36.
Compounds IVj–IVm, IVo, IVp, IVr–IVt, and
IVw were synthesized by oxidation of the correspond-
ing 1-(4-hydroxyphenyl)-3-arylureas III with lead
tetraacetate in acetic acid according to the procedure
described in [9].
1-[3-(Benzenesulfonyl)-2,5-dimethyl-4-oxocyclo-
hexa-2,5-dien-1-ylidene]-3-phenylurea (IVo). Yield
1
47%, mp 175–177°C. H NMR spectrum (CDCl3), δ,
ppm: 1.91 d (3H, 5-Me, J = 1.5 Hz), 2.86 s (3H,
2-Me), 7.13 q (1H, 6-H), 7.14–7.58 m (5H, PhNH),
7.34 br.s (1H, NH), 7.58–8.07 m (5H, PhSO2). Found,
%: N 7.05, 7.07. C21H18N2O4S. Calculated, %: N 7.10.
1-[3-(4-Methoxybenzenesulfonyl)-2,5-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene]-3-phenylurea
1
(IVp). Yield 43%, mp 137–139°C. H NMR spectrum
(CDCl3), δ, ppm: 1.94 d (3H, 5-Me, J = 1.5 Hz), 2.85 s
(3H, 2-Me), 3.89 s (3H, CH3O), 7.01 d (2H, 2′-H, 6′-H,
J = 9 Hz), 7.10 br.s (1H, NH), 7.14 q (1H, 6-H), 7.14–
7.58 m (5H, Ph), 8.00 d (2H, 3′-H, 5′-H, J = 9 Hz).
Found, %: N 6.54, 6.62. C22H20N2O5S. Calculated, %:
N 6.60.
1-[5-(4-Methoxybenzenesulfonyl)-2,3-dimethyl-
4-oxocyclohexa-2,5-dien-1-ylidene]-3-phenylurea
1
(IVj). Yield 55%, mp 149–151°C. H NMR spectrum
(CDCl3), δ, ppm: 1.92 s (3H, 3-Me), 2.12 s (3H,
2-Me), 3.85 s (3H, CH3O), 6.96 d (2H, 2′-H, 6′-H, J =
8.7 Hz), 7.13–7.56 m (5H, Ph), 7.23 br.s (1H, NH),
7.97 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 8.10 s (1H, 6-H).
Found, %: N 6.57, 6.64. C22H20N2O5S. Calculated, %:
N 6.60.
1-[6-Isopropyl-3-methyl-5-(4-methylbenzenesul-
fonyl)-4-oxocyclohexa-2,5-dien-1-ylidene]-3-phenyl-
urea (IVr). Yield 17%, mp 184–186°C. 1H NMR spec-
trum (CDCl3), δ, ppm: 1.51 d [6H, CH(CH3)2, J =
6.6 Hz], 1.87 d (3H, 3-Me, J = 1.2 Hz), 2.44 s (3H,
4′-CH3), 4.66–4.75 m [1H, CH(CH3)2], 6.99 br.s (1H,
2-H), 7.12–7.57 m (5H, Ph), 7.27 br.s (1H, NH), 7.34 d
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.91 d (2H, 3′-H, 5′-H,
J = 8.4 Hz). Found, %: N 6.35, 6.43. C24H24N2O4S.
Calculated, %: N 6.42.
1-[6-Isopropyl-5-(4-methoxybenzenesulfonyl)-
3-methyl-4-oxocyclohexa-2,5-dien-1-ylidene]-
3-phenylurea (IVs). Yield 21%, mp 189–190°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.52 d [6H,
1-[2,3-Dimethyl-5-(4-methylbenzenesulfonyl)-
4-oxocyclohexa-2,5-dien-1-ylidene]-3-(3-methyl-
phenyl)urea (IVk). Yield 41%, mp 187–188°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.97 s (3H,
3-Me), 2.17 s (3H, 2-Me), 2.39 s (3H, 3′-CH3), 2.42 s
(3H, 4″-CH3), 6.98–7.45 m (4H, 3-CH3C6H4), 7.33 d
(2H, 2″-H, 6″-H, J = 8.1 Hz), 7.45 br.s (1H, NH),
7.95 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 8.19 s (1H, 6-H).
Found, %: N 6.61, 6.65. C23H22N2O4S. Calculated,
%: N 6.63.
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REACTION OF N-ARYLCARBAMOYL-1,4-BENZOQUINONE IMINES
1299
2,6-Diisopropyl-4-[3-(4-methylphenyl)ureido]-
CH(CH3)2, J = 6.3 Hz], 1.88 d (3H, 3-Me, J = 1.5 Hz),
3.88 s (3H, CH3O), 4.66–4.75 m [1H, CH(CH3)2],
6.99 br.s (1H, 2-H), 7.01 d (2H, 2′-H, 6′-H, J =
8.7 Hz), 7.13–7.57 m (5H, Ph), 7.16 br.s (1H, NH),
7.99 d (2H, 3′-H, 5′-H, J = 8.7 Hz). Found, %: N 6.20,
6.24. C24H24N2O5S. Calculated, %: N 6.19.
1
phenyl 4-methylbenzenesulfonate (Vd). H NMR
spectrum (DMSO-d6), δ, ppm: 1.04 d [12H, CH(CH3)2,
J = 10.2 Hz], 2.24 s (3H, 4′-CH3), 2.46 s (3H, 4″-CH3),
2.96–3.07 m [2H, CH(CH3)2], 7.08 d (2H, 2′-H, 6′-H,
J = 7.8 Hz), 7.28 s (2H, 3-H, 5-H), 7.34 d (2H, 3′-H,
5′-H, J = 7.8 Hz), 7.54 d (2H, 2″-H, 6″-H, J = 8.4 Hz),
7.87 d (2H, 3″-H, 5″-H, J = 8.4 Hz), 8.60 s (1H, N1H),
8.77 s (1H, N2H).
1-[6-Isopropyl-5-(4-methoxybenzenesulfonyl)-
3-methyl-4-oxocyclohexa-2,5-dien-1-ylidene]-
3-(4-methylphenyl)urea (IVt). Yield 18%, mp 194–
1
2,6-Diisopropyl-4-[3-(4-nitrophenyl)ureido]-
195°C. H NMR spectrum (CDCl3), δ, ppm: 1.53 d
1
phenyl 4-methylbenzenesulfonate (Ve). H NMR
[6H, CH(CH3)2, J = 6.9 Hz], 1.89 d (3H, 3-Me, J =
1.2 Hz), 2.34 s (3H, 4′-CH3), 3.89 s (3H, CH3O), 4.68–
4.78 m [1H, CH(CH3)2], 6.94 s (1H, 2-H), 7.02 d (2H,
2″-H, 6″-H, J = 8.4 Hz), 7.03 br.s (1H, NH), 7.17 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.44 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 8.00 d (2H, 3″-H, 5″-H, J = 8.4 Hz).
Found, %: N 5.98, 6.05. C25H26N2O5S. Calculated, %:
N 6.00.
spectrum (DMSO-d6), δ, ppm: 1.05 d [12H, CH(CH3)2,
J = 10.2 Hz], 2.46 s (3H, 4″-CH3), 2.96–3.08 m [2H,
CH(CH3)2], 7.34 s (2H, 3-H, 5-H), 7.55 d (2H, 2′-H,
6′-H, J = 8.4 Hz), 7.73 d (2H, 2″-H, 6″-H, J = 7.8 Hz),
7.88 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 8.19 d (2H, 3″-H,
5″-H, J = 7.8 Hz), 9.35 s (1H, N1H), 9.81 s (1H, N2H).
1-(4-Hydroxy-3,5-dimethylphenyl)-1-(4-methyl-
benzenesulfonyl)-3-phenylurea (VІa). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 2.14 s (6H, 3-Me, 5-Me),
2.40 s (3H, 4′-CH3), 6.89–7.46 m (5H, Ph), 6.99 s (2H,
2-H, 6-H), 7.53 d (2H, 2′-H, 6′-H, J = 9 Hz), 7.86 d
(2H, 3′-H, 5′-H, J = 9 Hz), 8.13 s (1H, NH), 8.52 s
(1H, OH).
1-[2,6-Dimethyl-5-(4-methylbenzenesulfonyl)-
4-oxocyclohexa-2,5-dien-1-ylidene]-3-phenylurea
(IVw). Yield 36%, mp 157–158°C. 1H NMR spectrum
(CDCl3), δ, ppm: 2.23 br.s (3H, 2-Me), 2.44 s (3H,
4′-CH3), 2.81 s (3H, 6-Me), 6.21 q (1H, 3-H), 7.12–
7.54 m (5H, Ph), 7.33 d (2H, 2′-H, 6′-H, J = 7.8 Hz),
7.65 br.s (1H, NH), 7.89 d (2H, 3′-H, 5′-H, J = 7.8 Hz).
Found, %: N 6.59, 6.62. C22H20N2O4S. Calculated, %:
N 6.86.
1-(Benzenesulfonyl)-1-(4-hydroxy-3,5-dimethyl-
1
phenyl)-3-(4-methylphenyl)urea (VІb). H NMR
spectrum (DMSO-d6), δ, ppm: 2.13 s (6H, 3-Me,
5-Me), 2.23 s (3H, 4′-CH3), 6.98 s (2H, 2-H, 6-H),
7.06 d (2H, 2′-H, 6′-H, J = 9 Hz), 7.27 d (2H, 3′-H,
5′-H, J = 9 Hz), 7.50–7.99 m (5H, Ph), 8.33 s (1H,
NH), 8.59 s (1H, OH).
2,6-Dimethyl-4-(3-phenylureido)phenyl
1
4-methylbenzenesulfonate (Va). H NMR spectrum
(DMSO-d6), δ, ppm: 2.01 s (6H, 2-Me, 6-Me), 2.45 s
(3H, 4′-CH3), 6.89–7.46 m (5H, Ph), 7.19 s (2H, 3-H,
5-H), 7.53 d (2H, 2′-H, 5′-H, J = 9 Hz), 7.86 d (2H,
3′-H, 5′-H, J = 9 Hz), 8.65 s (1H, N1H), 8.69 s
(1H, N2H).
1-(4-Hydroxy-3,5-dimethylphenyl)-1-(4-me-
thoxybenzenesulfonyl)-3-(4-methylphenyl)urea
1
(VІc). H NMR spectrum (DMSO-d6), δ, ppm: 2.13 s
(6H, 3-Me, 5-Me), 2.24 s (3H, 4′-CH3), 3.89 s (3H,
CH3O), 6.97 s (2H, 2-H, 6-H), 7.05 d (2H, 2″-H, 6″-H,
J = 9 Hz), 7.21 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.30 d
(2H, 3′-H, 5′-H, J = 8.1 Hz), 7.84 d (2H, 3″-H, 5″-H,
J = 9 Hz), 8.14 s (1H, NH), 8.41 s (1H, OH).
2,6-Dimethyl-4-[3-(4-methylphenyl)ureido]-
1
phenyl benzenesulfonate (Vb). H NMR spectrum
(DMSO-d6), δ, ppm: 1.99 s (6H, 2-Me, 6-Me), 2.23 s
(3H, 4′-CH3), 7.06 d (2H, 2′-H, 6′-H, J = 9 Hz), 7.20 s
(2H, 3-H, 5-H), 7.35 d (2H, 3′-H, 5′-H, J = 9 Hz),
7.70–7.99 m (5H, Ph), 9.01 s (1H, N1H), 9.05 s
(1H, N2H).
1-(4-Hydroxy-3,5-diisopropylphenyl)-1-(4-meth-
ylbenzenesulfonyl)-3-(4-methylphenyl)urea (VІd).
1H NMR spectrum (DMSO-d6), δ, ppm: 1.00 d [12H,
CH(CH3)2, J = 10.2 Hz], 2.46 s (3H, 4′-CH3), 3.12–
3.22 m [2H, CH(CH3)2], 6.60 s (2H, 2-H, 6-H), 7.22 d
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.66 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 7.67 d (2H, 2″-H, 6″-H, J = 8.1 Hz),
8.21 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 9.35 s (1H, NH),
9.52 s (1H, OH).
2,6-Dimethyl-4-[3-(4-methylphenyl)ureido]-
phenyl 4-methoxybenzenesulfonate (Vc). 1H NMR
spectrum (DMSO-d6), δ, ppm: 2.01 s (6H, 2-Me,
6-Me), 2.24 s (3H, 4′-CH3), 3.89 s (3H, CH3O), 7.08 d
(2H, 2″-H, 6″-H, J = 9 Hz), 7.17 s (2H, 3-H, 5-H),
7.22 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.32 d (2H, 3′-H,
5′-H, J = 8.1 Hz), 7.88 d (2H, 3″-H, 5″-H, J = 9 Hz),
8.56 s (1H, N1H), 8.58 s (1H, N2H).
1-(4-Hydroxy-3,5-diisopropylphenyl)-3-(4-nitro-
phenyl)-1-(4-methylbenzenesulfonyl)urea (VІe).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

KONOVALOVA et al.
1300
1H NMR spectrum (DMSO-d6), δ, ppm: 1.00 d [12H,
CH(CH3)2, J = 10.2 Hz], 2.46 s (3H, 4″-CH3), 3.12–
3.21 m [2H, CH(CH3)2], 6.59 s (2H, 2-H, 6-H), 7.31 d
(2H, 2″-H, 6″-H, J = 8.4 Hz), 7.95 d (2H, 3″-H, 5″-H,
J = 8.4 Hz), 7.67 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 8.21 d
(2H, 3′-H, 5′-H, J = 8.1 Hz), 9.50 s (1H, NH), 9.97 s
(1H, OH).
2. Nichvoloda, V.M., Alaev, Yu.N., Luk’yanenko, L.V.,
Markov, V.I., and Burmistrov, K.S., Zh. Org. Khim.,
1986, vol. 22, p. 1111.
3. Burmistrov, K.S., Nichvoloda, V.M., Markov, V.I., and
Romanchenko, V.A., Zh. Org. Khim., 1986, vol. 22,
p. 1306.
4. Avdeenko, A.P., Konovalova, S.A., Roman’kov, D.A.,
Burmistrov, K.S., Nichvoloda, V.M., Shishkin, O.V.,
Zubatyuk, R.I., and Palamarchuk, G.V., Russ. J. Org.
Chem., 2009, vol. 45, p. 48.
1-[4-Hydroxy-3,5-dimethyl-2-(4-methylbenzene-
1
sulfonyl)phenyl]-3-phenylurea (VІІa). H NMR
spectrum (DMSO-d6), δ, ppm: 2.22 s (3H, 5-Me),
2.28 s (3H, 4′-CH3), 2.42 s (3H, 3-Me), 6.89–7.46 m
(5H, Ph), 7.40 s (1H, 6-H), 7.53 d (2H, 2′-H, 6′-H, J =
9 Hz), 7.86 d (2H, 3′-H, 5′-H, J = 9 Hz), 8.63 s (1H,
N1H), 8.67 s (1H, N2H), 9.45 s (1H, OH).
5. Avdeenko, A.P., Konovalova, S.A., Roman’kov, D.A.,
Ludchenko, O.N., and Marchenko, I.L., Russ. J. Org.
Chem., 2009, vol. 45, p. 383.
6. Avdeenko, A.P., Konovalova, S.A., Mikhailichen-
ko, O.N., Shelyazhenko, S.V., Pirozhenko, V.V., and
Yagupol’skii, L.M., Russ. J. Org. Chem., 2012, vol. 48,
p. 221.
1-[2-(Benzenesulfonyl)-4-hydroxy-3,5-dimethyl-
1
phenyl]-3-(4-methylphenyl)urea (VІІb). H NMR
7. Konovalova, S.A., Avdeenko, A.P., and Marchen-
spectrum (DMSO-d6), δ, ppm: 2.21 s (3H, 5-Me),
2.23 s (3H, 4′-CH3), 2.41 s (3H, 3-Me), 7.27 d (2H,
2′-H, 6′-H, J = 9 Hz), 7.40 s (1H, 6-H), 7.59–7.89 m
(5H, Ph), 7.80 d (2H, 3′-H, 5′-H, J = 9 Hz), 9.00 s (1H,
N1H), 9.04 s (1H, N2H), 9.36 s (1H, OH).
ko, I.L., Russ. J. Org. Chem., 2014, vol. 50, p. 973.
8. 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.
9. Avdeenko, A.P., Konovalova, S.A., Sergeeva, A.G.,
Zubatyuk, R.I., Palamarchuk, G.V., and Shishkin, O.V.,
Russ. J. Org. Chem., 2008, vol. 44, p. 1765.
1-[4-Hydroxy-2-(4-methoxybenzenesulfonyl)-3,5-
dimethylphenyl]-3-(4-methylphenyl)urea (VІІc).
1H NMR spectrum (DMSO-d6), δ, ppm: 2.20 s (3H,
5-Me), 2.24 s (3H, 4′-CH3), 2.41 s (3H, 3-Me), 3.72 s
(3H, CH3O), 7.01 d (2H, 2′-H, 6′-H, J = 8.7 Hz),
7.06 d (2H, 2″-H, 6″-H, J = 9 Hz), 7.28 d (2H, 3′-H,
5′-H, J = 8.7 Hz), 7.39 s (1H, 6-H), 7.74 d (2H, 3″-H,
5″-H, J = 9 Hz), 8.60 s (1H, N1H), 8.62 s (1H, N2H),
9.36 s (1H, OH).
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.H., Koseki, S.,
Matsunaga, N., Nguyen, K.A., Su, Sh., Windus, T.L.,
Dupuis, M., and Montgomery, J.A., Jr., J. Comput.
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12. Konovalova, S.A., Avdeenko, A.P., Sergeeva, A.G., and
Marchenko, I.L., Russ. J. Org. Chem., 2014, vol. 50,
p. 346.
REFERENCES
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014