Reaction of N-acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines with sodium arenesulfinates

Article abstract of DOI:10.1134/S1070428014090097

N-Acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines having no substituent in the 2- and/or 6-position of the quinoid ring react with sodium arenesulfinates preferentially according to the 1,4-addition pattern. The presence of an ArSO

Full text of DOI:10.1134/S1070428014090097

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 9, pp. 1283–1291. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © S.A. Konovalova, A.P. Avdeenko, V.V. Pirozhenko, O.P. Ledeneva, A.A. Santalova, 2014, published in Zhurnal Organicheskoi
Khimii, 2014, Vol. 50, No. 9, pp. 1300–1308.
Reaction of N-Acetyl- and N-[1-(Arylsulfonylimino)ethyl]-
1,4-benzoquinone Imines with Sodium Arenesulfinates
S. A. Konovalovaa, A. P. Avdeenkoa, V. V. Pirozhenkob, O. P. Ledenevac, and A. A. Santalovaa
a Donbass State Engineering Academy, ul. Shkadinova 72, Kramatorsk, 84313 Ukraine
e-mail: chimist@dgma.donetsk.ua
b Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
ul. Murmanskaya 5, Kiev, 02660 Ukraine
c Ukrainian Engineering and Pedagogical Academy, Slavyansk, Ukraine
Received February 7, 2014
Abstract—N-Acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone imines having no substituent in the
2- and/or 6-position of the quinoid ring react with sodium arenesulfinates preferentially according to the
1,4-addition pattern. The presence of an ArSO2N group favors radical ion reaction with formation of
1,6-addition products.
DOI: 10.1134/S1070428014090097
We previously showed that N-aryl- [1], N-aroyl-
[2–4], N-arylsulfonyl- [2–7], and N-[α-(arylsulfonyl-
imino)benzyl]-1,4-benzoquinone imines [2–4] react
with sodium arenesulfinates to give four types of prod-
ucts. It was presumed that nucleophilic addition of
arenesulfinate ion under charge or orbital control leads
to the formation of 1,4- and 6,3-addition products and
that 1,6- and 6,1-additions follow radical ion mecha-
nism [2–4, 7]. The latter path becomes preferential for
1,4-benzoquinone imines characterized by a higher
redox potential [2–4], and 1,4-addition is most typical
of N-arylsulfonyl and N-[alkyl(or trifluoromethyl)sul-
fonyl] derivatives [2–4, 7] which contain a strong elec-
tron-withdrawing substituent on the nitrogen atom.
N-Acetyl- and N-[1-(arylsulfonylimino)ethyl]-1,4-
benzoquinone imines are methyl analogs of N-aroyl
and N-[(N-arylsulfonyl)benzimidoyl] derivatives. Re-
placement of the aryl group at the carbonyl carbon
atom in N-aroyl and N-[1-(arylsulfonylimino)benzyl]-
derivatives by methyl group changes their reactivity
[8]. Reactions of N-acetyl- or N-[1-(arylsulfonyl-
imino)ethyl]-1,4-benzoquinone imines with sodium
arenesulfinates have not been studied previously.
the nucleophile. When the reaction mixture turned
colorless, it was diluted with water until complete
precipitation. A part of the solid product was filtered
off and dried, and the other part was recrystallized.
Both these parts, as well as the products isolated from
1
the filtrate, were analyzed by H NMR to identify all
possible products.
In the reactions of N-[1-(arylsulfonylimino)ethyl]-
(Ia–If) and N-acetyl-1,4-benzoquinone imines (IIa,
IIb) with sodium arenesulfinates ІІІa–IIIc we isolated
only 1,4-addition products IVa–IVk and Va–Vd
1
(Scheme 1). Their H NMR spectra contained two
doublets (IVa–IVc) or one singlet (IVd–IVk, Va–Vd)
from protons in the aminophenol fragment, singlets
from the NH and OH protons, and doublets from the
former arenesulfinate, which indicated 1,4-addition of
sulfinates III.
3-Methyl-1,4-benzoquinone imines VIa and VIb
reacted with sodium arenesulfinates ІІІa and IIIb to
give mixtures of 1,4- (VIIa–VIIc, VIIIa–VIIIc) and
6,3-addition products (IXa–IVc) (Scheme 2; see
1
table). Signals in their H NMR spectra were assigned
on the basis of published data [2–4]. 1,4-Addition
products displayed two singlets at δ 6.72–6.76 and
7.74–7.76 ppm (VIIa–VIIc) or two doublets at δ 6.75–
6.79 and 7.24–7.29 ppm with a vicinal coupling con-
stant 3J of 8.7 Hz (VIIIa–VIIIc); 6,3-addition products
IXa–IXc were characterized by two broadened singlets
The goal of the present work was to reveal specific
features of the reaction of alkyl-substituted N-acetyl-
and N-[1-(arylsulfonylimino)ethyl]-1,4-benzoquinone
imines with sodium arenesulfinates. The reactions
were carried out in boiling acetic acid using 2 equiv of
1283

KONOVALOVA et al.
1284
Scheme 1.
O
N
OH
O
O
R1
R2
SO2Na
AcOH
R1
R2
S
+
R3
R4
R3
R4
Me
HN
Me
X
X
Ia–If, IIa, IIb
IIIa–IIIc
IVa–IVk, Va–Vd
I, X = 4-MeC6H4SO2N (a, c, e), 4-ClC6H4SO2N (b, d, f); R1 = Me, R2 = R3 = H (a, b); R1 = R2 = Me, R3 = H (c, d); R2 = R3 = Me,
R1 = H (e, f); ІІ, X = O: R1 = R2 = Me, R3 = H (a); R1 = Me, R2 = H, R3 = i-Pr (b); ІІІ, R4 = Me (a), MeO (b), Cl (c); IV, X =
4-MeC6H4SO2N (a, b, d, e, h, i), 4-ClC6H4SO2N (c, f, g, j, k); R1 = Me, R2 = R3 = H, R4 = Me (a, c), MeO (b); R1 = R2 = Me, R3 =
H, R4 = Me (d, f), MeO (e, g); R1 = H, R2 = R3 = Me, R4 = Me (h, j), MeO (i, k); V, X = O: R1 = R2 = Me, R3 = H, R4 = Me (a),
MeO (b); R1 = Me, R2 = H, R3 = i-Pr, R4 = Me (c), MeO (d).
at δ 6.61–6.62 and 7.09–7.12 ppm. The spectra of
IXa–IXc revealed an appreciable upfield shift of the
singlet signal from the methyl protons in the imidoyl
fragment (δ 2.71 ppm) as a result of considerable
shielding of that methyl group by the arylsulfonyl sub-
stituent in position 6 of the aminophenol fragment.
The reaction of N-[1-(arylsulfonylimino)ethyl]-2,6-
dimethyl-1,4-benzoquinone imines Xa and Xb with
sodium arenesulfinates ІІІa and IIIc afforded only
1,6-addition products XIIa and XIIb, whereas
N-acetyl-2,6-dimethyl-1,4-benzoquinone imine (XI)
gave rise to mixtures of 1,6- (XIIIa, XIIIb) and
6,3-adducts (XIVa, XIVb); the yields of XIVa and
XIVb were 15 and 10%, respectively (Scheme 3). We
succeeded in isolating pure compounds XIIIb and
XIVa after recrystallization of the reaction mixture. In
the reactions with quinone imines Xa and Xb the
reaction mixtures also contained their reduced deriva-
tives, the corresponding aminophenols.
The structure of XII–XIV was determined on the
1
basis of the H NMR spectra. The spectra of XIIa,
XIIb, XIIIa, and XIIIb characteristically contained
Reactions of N-acyl-, N-[α-(arenesulfonylimino)benzyl], and N-[1-(arenesulfonylimino)ethyl]-1,4-benzoquinone imines with
sodium arenesulfinates
O
R1
R2
R1
Z
SO2Na
+
R4
N
X
Addition products, %
R1
R2
X
Z
R4
1,4 (VII/VIII)
6,3
6,1
1,6
H
H
H
Me
Me
Me
H
H
H
H
H
H
H
4-MeC6H4SO2N Me
4-ClC6H4SO2N Me
4-ClC6H4SO2N Me
Me
Me
MeO
Me
Cl
Me
Cl
Me
MeO
MeO
Me
66/16
47/17
35/50
18
36
60
15
10
–
–
–
–
–
–
–
–
–
085
090
100
100
063 [2]
052 [2]
095 [2]
089 [2]
Me
Me
Me
Me
Me
Me
Me
Me
O
O
Me
Me
–
–
–
–
–
–
–
–
4-MeC6H4SO2N Me
4-ClC6H4SO2N Me
–
–
–
11 [2]
14 [2]
–
O
O
4-MeOC6H4
4-MeC6H4
26 [2]
34 [2]
05 [2]
11 [2]
4-MeC6H4SO2N Ph
4-MeC6H4SO2N Ph
H
–
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

REACTION OF N-ACETYL- AND N-[1-(ARYLSULFONYLIMINO)ETHYL]-1,4-...
1285
Scheme 2.
OH
SO2C6H4R2-4
1,4-Addition
Me
HN
Me
NSO2C6H4R1-4
VIIa–VIIc
O
N
OH
SO2C6H4R2-4
AcOH
1,4-Addition
+
IIIa, IIIb
Me
Me
Me
Me
HN
NSO2C6H4R1-4
NSO2C6H4R1-4
VIa, VIb
VIIIa–VIIIc
OH
6,3-Addition
Me
SO2C6H4R2-4
Me
HN
NSO2C6H4R1-4
IXa–IXc
VI, R1 = Me (a), Cl (b); VII–IX, R1 = R2 = Me (a); R1 = Cl, R2 = Me (b), MeO (c).
Scheme 3.
OSO2C6H4R-4
Me
Me
1,6-Addition
O
N
HN
Me
Me
Me
Me
AcOH
X
+
IIIa, IIIb
XIIa, XIIb, XIIIa, XIIIb
OH
Me
Me
6,3-Addition
X
Xa, Xb, XI
SO2C6H4R-4
Me
HN
O
XIVa, XIVb
X, X = 4-MeC6H4SO2N (a), 4-ClC6H4SO2N (b); XI, X = O; XII, R = Me, X = 4-MeC6H4SO2N (a), 4-ClC6H4SO2N (b);
XIII, X = O, R = Me (a), Cl (b); XIV, R = Me (a), Cl (b).
singlets from 3-H and 5-H at δ 7.27–7.32 ppm and
from the NH proton at δ 9.92–10.49 ppm, while com-
pounds XIVa and XIVb displayed singlets from 6-H at
δ 7.37–7.38 ppm and from the NH and OH protons at
δ 8.78–8.88 and 9.51–9.62 ppm, respectively.
Compounds IIc and XV failed to take up arenesul-
finate ions. In the reactions of these compounds with
sodium arenesulfinates IIIa and IIIc we isolated sub-
stituted hydroquinone derivatives XVIIIa, XVIIIb,
XIXa, and XIXb (Scheme 4). Analysis of the 1H NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

KONOVALOVA et al.
1286
Scheme 4.
O
N
O
OH
R1
R2
R1
R1
R1
R1
R1
H2O
IIIa, IIIc
–MeCONH2
R2
Me
O
OSO2C6H4R3-4
O
IIc, XV
XVI, XVII
XVIIIa, XVIIIb, XIXa, XIXb
IIc, R1 = H, R2 = Me; XV, R1 = i-Pr, R2 = H; XVI, R1 = Me; XVII, R1 = i-Pr; XVIII, R1 = R3 = Me (a); R1 = Me, R3 = Cl (b);
XIX, R1 = i-Pr, R3 = Me (a), Cl (b).
Scheme 5.
·
–
O
N
O
N
Me
Me
Z
Me
Me
Z
·
+ 4-MeC6H4SO2
+
4-MeC6H4SO2
X
X
Xc, XI, XX, XXI
Xc, X = PhSO2N, Z = Me; XI, X = O, Z = Me; XX, X = PhSO2N, Z = Ph; XXI, X = O, Z = Ph.
data showed that these compounds are products of
addition of sodium arenesulfinates to the correspond-
ing 1,4-benzoquinones XVI and XVII which were
formed as a result of hydrolysis of initial quinone
imines IIc and XV. Compounds XIXa and XIXb were
identical to the products synthesized previously by
reaction of N-aroyl- and N-[1-(arylsulfonylimino)-
ethyl]-2,6-diisopropyl-1,4-benzoquinone imines with
sodium arenesulfinates [2].
The results of our present study and those obtained
in [2–4] show that 2,6-dimethyl derivatives Xa, Xb,
and XI demonstrate the strongest difference in the re-
activity of N-substituted 1,4-benzoquinone imines (see
table, R1 = Me, R2 = H). 6,1-Addition products were
formed only from N-aroyl-1,4-benzoquinone imines
(X = O, Z = 4-MeOC6H4, 4-MeC6H4), and the contri-
bution of 6,3-addition decreased in going from aryl-
(Z = Ph, 4-MeOC6H4, 4-MeC6H4) to methyl-substitut-
ed derivatives (Z = Me). No 6,3-addition products
were detected in the reactions with methylimidoyl ana-
logs (X = 4-MeC6H4SO2N, 4-ClC6H4SO2N, Z = Me).
radical anion species from the initial 1,4-benzoquinone
imine and increases the contribution of the radical ion
path. To verify this assumption we calculated the
change in the energy of the system (ΔE) upon genera-
tion of radical ions from initial model quinone imines
Xc, XI, XX, and XXI during their reactions with
sodium 4-methylbenzenesulfinate (Scheme 5). The
formation of radical anion from quinone imines Xc and
XX turned out to be more favorable (ΔE = 105.73 and
93.17 kJ/mol, respectively) than from quinone imines
XI and XXI (ΔE = 124.07 and 113.80 kJ/mol, respec-
tively), which was fully consistent with the experi-
mental data (see table).
Thus, the experimental data and results of quantum
chemical calculations showed that the presence of
an ArSO2N group in N-[α-(arylsulfonylimino)benzyl]-
or N-[1-(arylsulfonylimino)ethyl]-2,6-dimethyl-1,4-
benzoquinone imines favors their reaction with sodium
arenesulfinates to follow radical ion path, which is
determined by decrease of the energy of formation of
intermediate radical ion from the initial quinone imine.
These compounds gave rise to the largest number of
1,6-addition products.
We previously presumed that 1,6- and 6,1-addition
products are formed according to radical ion mecha-
nism. Taking into account that just these adducts were
mainly obtained from imidoyl derivatives (X =
4-MeC6H4SO2N, 4-ClC6H4SO2N), introduction of
an ArSO2N fragment favors more facile formation of
Among the examined quinone imines, only N-aroyl
derivatives (X = O, Z = 4-MeOC6H4, 4-MeC6H4) re-
acted with sodium arenesulfinates to give 6,1-addition
products (see table). The most probable reason for the
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

REACTION OF N-ACETYL- AND N-[1-(ARYLSULFONYLIMINO)ETHYL]-1,4-...
1287
lack of analogous adducts in the reactions with
N-imidoyl quinone imines X and XX is steric hin-
drances created by bulky sybstituents on the nitrogen
atom. Methyl groups in the ortho positions with
respect to the carbonyl carbon atom in N-acetyl-1,4-
benzoquinone imine XI are likely to stabilize the
radical center on the oxygen atom to a greater extent
than in N-aroyl derivative XXI, so that 1,6-addition
products are mainly formed.
the boiling point, 4 mmol of sodium arenesulfinate
IIIa–IIIc was added, and the mixture was heated for
5 min under reflux and left to stand for 12 h at room
temperature. When the mixture turned colorless, water
was added until complete precipitation. The colorless
precipitate was filtered off and washed first with cold
and then with warm water. A part of the crude product
was recrystallized from glacial acetic acid. The mother
liquor was diluted with water, and the precipitate was
filtered off. All three portions of the solid product were
analyzed by 1H NMR.
EXPERIMENTAL
General procedure for the reaction of quinone
imines XI and XV with sodium arenesulfinates IIIa
and IIIc. Sodium arenesulfinate IIIa or IIIc, 4 mmol,
was added to a solution of 2 mmol of quinone imine
XI or XV in 20 mL of glacial acetic acid, the mixture
was heated to the boiling point, kept boiling for 5 min,
and left to stand for 6 h at room temperature. When the
mixture turned colorless, an ice–water mixture was
added until a solid began to separate from the solution.
The colorless precipitate was filtered off, and a part of
it was recrystallized from glacial acetic acid. The
mother liquor was diluted with water, and the precip-
itate was filtered off. All three portions of the solid
product were analyzed by 1H NMR.
1
The H NMR spectra were recorded on a Varian
VXR-300 spectrometer at 300 MHz using tetramethyl-
silane as internal reference. Thin-layer chromatog-
raphy was performed on Silufol UV-254 plates; spots
were applied from solutions in chloroform, the 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 [9] based in part on
the program code of GAMESS (US) [10]. The molec-
ular structures were calculated in terms of the density
functional theory with the B3LYP potential using
standard 6-31+G(d) basis set.
Initial N-[1-(arylsulfonylimino)ethyl]-1,4-benzo-
quinone imines Ia–If, VIa, VIb, Xa, and Xb were
synthesized by oxidation of the corresponding N-sub-
stituted 4-aminophenols with lead(IV) acetate in
glacial acetic acid according to the procedure
described in [11] and were recrystallized from glacial
acetic acid.
N-Acetyl-1,4-benzoquinone imines IIa–IIc and XI
were prepared by oxidation of the corresponding
N-(4-hydroxyphenyl)acetamides with silver(I) oxide in
chloroform as reported in [11], and N-acetyl-1,4-
benzoquinone imine (XV) was obtained by oxidation
of the corresponding N-(4-hydroxyphenyl)acetamide
with 4-(diacetoxy-λ3-iodanyl)toluene in dichloroethane
according to [12]. The spectral parameters and elemen-
tal analyses of quinone imines Ib, Id–If, Xa, Xb [8],
IIb [13], IIc, and XI [14] were reported previously.
Sodium arenesulfinates IIIa–IIIc were prepared as
described in [15].
N′-(4-Methylbenzenesulfonyl)-N-(3-methyl-4-
oxocyclohexa-2,5-dien-1-ylidene)acetimidamide
1
(Ia). Yield 58%, mp 140–142°C. H NMR spectrum
(CDCl3), δ, ppm: E isomer (79%): 2.07 br.s (3H,
3-Me), 2.27 s (3H, Me), 2.43 s (3H, MeC6H4), 6.66 d
(1H, 5-H, J = 10.2 Hz), 6.71 q (1H, 2-H), 6.89–
6.93 d.d (1H, 6-H, J = 10.2, 2.7 Hz), 7.30 d (2H, 2′-H,
6′-H, J = 8.4 Hz), 7.78 d (2H, 3′-H, 5′-H, J = 8.4 Hz);
Z isomer (21%): 2.05 br.s (3H, 3-Me), 2.43 s (3H,
MeC6H4), 2.70 br.s (3H, Me), 6.64 d (1H, 5-H, J =
10.2 Hz), 6.81 q (1H, 2-H), 6.97–7.01 d.d (1H, 6-H,
J = 10.2, 2.7 Hz), 7.30 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.86 d (2H, 3′-H, 5′-H, J = 8.4 Hz). Found, %: N 8.57,
8.89; S 10.08, 10.24. C16H16N2O3S. Calculated, %:
N 8.85; S 10.14.
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-
ylidene)-N′-(4-methylbenzenesulfonyl)acetimid-
amide (Ic). Yield 70%, mp 171–173°C. 1H NMR spec-
trum (CDCl3), δ, ppm: E isomer (78%): 2.07 br.s (3H,
3-Me), 2.12 br.s (3H, 2-Me), 2.28 s (3H, Me), 2.43 s
(3H, MeC6H4), 6.56 d (1H, 5-H, J = 9.6 Hz), 6.69 d
(1H, 6-H, J = 9.6 Hz), 7.29 d (2H, 2′-H, 6′-H, J =
9.0 Hz), 7.77 d (2H, 3′-H, 5′-H, J = 9.0 Hz); Z isomer
(22%): 2.03 br.s (3H, 3-Me), 2.12 br.s (3H, 2-Me),
2.70 br.s (3H, Me), 2.42 s (3H, MeC6H4), 6.56 d (1H,
5-H, J = 9.6 Hz), 6.92 d (1H, 6-H, J = 9.6 Hz), 7.29 d
General procedure for the reaction of quinone
imines Ia–If, IIa–IIc, VIa, VIb, Xa, and Xb with
sodium arenesulfinates IIIa–IIIc. A solution of
2 mmol of quinone imine Ia–If, IIa–IIc, VIa, VIb,
Xa, or Xb in 20 mL of glacial acetic acid was heated to
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014

KONOVALOVA et al.
1288
(2H, 2′-H, 6′-H, J = 9.0 Hz), 7.86 d (2H, 3′-H, 5′-H,
J = 9.0 Hz). Found, %: N 8.13, 8.42; S 9.46, 9.74.
C17H18N2O3S. Calculated, %: N 8.48; S 9.70.
N-(2,3-Dimethyl-4-oxocyclohexa-2,5-dien-1-yli-
dene)acetamide (IIa). Yield 57%, mp 73–74°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.07 br.s (3H,
3-Me), 2.11 br.s (3H, 2-Me), 2.31 s (3H, Me), 6.54 d
(1H, 6-H, J = 9.6 Hz), 6.81 d (1H, 5-H, J = 9.6 Hz).
Found, %: N 7.99, 8.23. C10H11NO2. Calculated, %:
N 7.90.
N-[4-Hydroxy-3-methyl-5-(4-methylbenzenesul-
fonyl)phenyl]-N'-(4-methylbenzenesulfonyl)acet-
imidamide (IVa). Yield 67%, mp 216–217°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.08 s (3H,
3-Me), 2.37 s (3H, 4′-Me), 2.37 s (3H, 4″-Me), 2.47 s
(3H, Me), 7.35 d (2H, 2″-H, 6″-H, J = 7.8 Hz), 7.36 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.51 d (1H, 2-H, J =
1.2 Hz), 7.68 d (2H, 3″-H, 5″-H, J = 7.8 Hz), 7.76 d
(2H, 3′-H, 5′-H, J = 8.1 Hz), 8.05 d (1H, 6-H, J =
1.2 Hz), 9.67 s (1H, NH), 10.38 s (1H, OH). Found, %:
N 5.80, 6.02; S 13.47, 13.60. C23H24N2O5S2. Calculat-
ed, %: N 5.93; S 13.57.
N-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-
5-methylphenyl]-N′-(4-methylbenzenesulfonyl)acet-
imidamide (IVb). Yield 75%, mp 150–152°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.05 s (3H,
5-Me), 2.37 s (3H, 4′-Me), 2.46 s (3H, Me), 3.82 s
(3H, MeO), 7.14 d (2H, 2″-H, 6″-H, J = 8.4 Hz),
7.37 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.53 d (1H, 6-H,
J = 1.2 Hz), 7.79 d (2H, 3″-H, 5″-H, J = 8.4 Hz),
7.79 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.98 d (1H, 2-H,
J = 1.2 Hz), 9.94 br.s (1H, NH), 10.35 br.s (1H, OH).
Found, %: N 5.51, 5.84; S 13.00, 13.21. C23H24N2O6S2.
Calculated, %: N 5.73; S 13.13.
3-Me), 2.03 s (3H, 2-Me), 2.35 s (3H, 4′-Me), 2.38 s
(3H, 4″-Me), 2.46 s (3H, Me), 7.31 d (2H, 2′-H, 6′-H,
J = 8.1 Hz), 7.36 d (2H, 2″-H, 6″-H, J = 8.1 Hz),
7.61 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.64 s (1H, 6-H),
7.70 d (2H, 3″-H, 5″-H, J = 8.1 Hz), 9.64 s (1H, NH),
10.16 s (1H, OH). Found, %: N 5.72, 5.94; S 13.15,
13.32. C24H26N2O5S2. Calculated, %: N 5.76; S 13.18.
N-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-
2,3-dimethylphenyl]-N′-(4-methylbenzenesulfonyl)-
acetimidamide (IVe). Yield 65%, mp 139–140°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.02 s (3H,
3-Me), 2.04 s (3H, 2-Me), 2.35 s (3H, 4′-Me), 2.45 s
(3H, Me), 3.83 s (3H, MeO), 7.08 d (2H, 2″-H, 6″-H,
J = 9.0 Hz), 7.32 d (2H, 2′-H, 6′-H, J = 9.0 Hz), 7.61 d
(2H, 3′-H, 5′-H, J = 9.0 Hz), 7.62 s (1H, 6-H), 7.76 d
(2H, 3″-H, 5″-H, J = 9.0 Hz), 9.62 br.s (1H, NH),
10.11 s (1H, OH). Found, %: N 5.50, 5.64; S 12.70,
12.84. C24H26N2O6S2. Calculated, %: N 5.57; S 12.76.
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-2,3-
dimethyl-5-(4-methylbenzenesulfonyl)phenyl]acet-
imidamide (IVf). Yield 63%, mp 209–210°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.04 br.s (6H,
2-Me, 3-Me), 2.38 s (3H, 4″-Me), 2.48 s (3H, Me),
7.36 d (2H, 2″-H, 6″-H, J = 8.1 Hz), 7.58 d (2H, 2′-H,
6′-H, J = 7.8 Hz), 7.64 s (1H, 6-H), 7.67 d (2H, 3″-H,
5″-H, J = 8.1 Hz), 7.74 d (2H, 3′-H, 5′-H, J = 7.8 Hz),
9.69 br.s (1H, NH), 10.42 br.s (1H, OH). Found, %:
N 5.61, 5.69; S 12.44, 12.69. C23H23ClN2O5S2. Calcu-
lated, %: N 5.53; S 12.65.
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-5-
(4-methoxybenzenesulfonyl)-2,3-dimethylphenyl]-
acetimidamide (IVg). Yield 42%, mp 127–129°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.02 s (3H,
3-Me), 2.04 s (3H, 2-Me), 2.48 s (3H, Me), 3.83 s (3H,
MeO), 7.08 d (2H, 2″-H, 6″-H, J = 8.4 Hz), 7.58 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.63 s (1H, 6-H), 7.73 d
(2H, 3″-H, 5″-H, J = 8.4 Hz), 7.74 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 9.63 br.s (1H, NH), 10.23 br.s (1H, OH).
F o u n d , % : N 5 . 3 1 , 5 . 4 7 ; S 1 2 . 0 5 , 1 2 . 3 8.
C23H23ClN2O6S2. Calculated, %: N 5.36; S 12.26.
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-
3-methyl-5-(4-methylbenzenesulfonyl)phenyl]acet-
imidamide (IVc). Yield 69%, mp 208–210°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.08 s (3H,
3-Me), 2.38 s (3H, MeC6H4), 2.48 s (3H, Me), 7.38 d
(2H, 2″-H, 6″-H, J = 8.4 Hz), 7.47 d (1H, 2-H, J =
1.5 Hz), 7.63 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.68 d
(2H, 3″-H, 5″-H, J = 8.4 Hz), 7.88 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 8.04 d (1H, 6-H, J = 1.5 Hz), 9.72 s (1H,
NH), 10.52 br.s (1H, OH). Found, %: N 5.47, 5.69;
S 13.16, 13.34. C22H21ClN2O5S2. Calculated, %:
N 5.68; S 13.01.
N-[4-Hydroxy-2,6-dimethyl-3-(4-methylbenzene-
sulfonyl)phenyl]-N'-(4-methylbenzenesulfonyl)acet-
imidamide (IVh). Yield 41%, mp 244–245°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 1.42 s (3H,
Me), 2.01 s (3H, 2-Me), 2.33 s (3H, 6-Me), 2.35 s (3H,
4′-Me), 2.38 s (3H, 4″-Me), 6.65 s (1H, 5-H), 7.31 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.39 d (2H, 2-H, 6-H, J =
8.1 Hz), 7.52 d (2H, 3-H, 5-H, J = 8.1 Hz), 7.72 d (2H,
3″-H, 5″-H, J = 8.1 Hz), 9.92 s (1H, NH), 10.56 br.s
(1H, OH). Found, %: N 5.70, 5.92; S 12.94, 13.15.
C24H26N2O5S2. Calculated, %: N 5.76; S 13.18.
N-[4-Hydroxy-2,3-dimethyl-5-(4-methylbenzene-
sulfonyl)phenyl]-N′-(4-methylbenzenesulfonyl)acet-
imidamide (IVd). Yield 68%, mp 211–212°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.02 s (3H,
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REACTION OF N-ACETYL- AND N-[1-(ARYLSULFONYLIMINO)ETHYL]-1,4-...
1289
N-[4-Hydroxy-3-(4-methoxybenzenesulfonyl)-
2,6-dimethylphenyl]-N'-(4-methylbenzenesulfonyl)-
acetimidamide (IVi). Yield 48%, mp 234–235°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.01 s (3H,
2-Me), 2.33 s (3H, 6-Me), 2.35 s (3H, 4′-Me), 2.42 s
(3H, Me), 3.84 s (3H, MeO), 6.68 s (1H, 5-H), 7.10 d
(2H, 2″-H, 6″-H, J = 8.1 Hz), 7.29 d (2H, 2′-H, 6′-H,
J = 8.7 Hz), 7.51 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 7.78 d
(2H, 3″-H, 5″-H, J = 8.1 Hz), 9.84 br.s (1H, NH),
10.57 br.s (1H, OH). Found, %: N 5.21, 5.41; S 12.46,
12.68. C24H26N2O6S2. Calculated, %: N 5.57; S 12.76.
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-2,6-
dimethyl-3-(4-methylbenzenesulfonyl)phenyl]acet-
imidamide (IVj). Yield 44%, mp 227–229°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.00 s (3H,
2-Me), 2.34 s (3H, 6-Me), 2.38 s (3H, 4″-Me), 2.47 s
(3H, Me), 6.67 s (1H, 5-H), 7.37 d (2H, 2″-H, 6″-H,
J = 7.5 Hz), 7.57 d (2H, 2′-H, 6′-H, J = 8.1 Hz), 7.64 d
(2H, 3″-H, 5″-H, J = 7.5 Hz), 7.70 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 10.20 br.s (1H, NH), 10.86 br.s (1H, OH).
F o u n d , % : N 6 . 9 3 , 7 . 1 8 ; S 1 2 . 5 4 , 1 2 . 7 0.
C23H23ClN2O5S2. Calculated, %: N 5.53; S 12.65.
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-3-
(4-methoxybenzenesulfonyl)-2,6-dimethylphenyl]-
acetimidamide (IVk). Yield 49%, mp 226–227°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.01 s (3H,
2-Me), 2.32 s (3H, 6-Me), 2.45 s (3H, Me), 3.84 s (3H,
MeO), 6.68 s (1H, 5-H), 7.09 d (2H, 2″-H, 6″-H, J =
8.7 Hz), 7.56 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.62 d
(2H, 3″-H, 5″-H, J = 8.7 Hz), 7.77 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 9.96 br.s (1H, NH), 10.53 br.s (1H, OH).
F o u n d , % : N 5 . 0 9 , 5 . 3 2 ; S 11 . 9 2 , 1 2 . 3 9.
C23H23ClN2O6S2. Calculated, %: N 5.36; S 12.26.
N-[4-Hydroxy-2-isopropyl-5-methyl-3-(4-methyl-
benzenesulfonyl)phenyl]acetamide (Vc). Yield 74%,
1
mp 210–211°C. H NMR spectrum (DMSO-d6), δ,
ppm: 0.86 d [6H, CH(CH3)2, J = 6.9 Hz], 1.96 s (3H,
Me), 2.16 s (3H, 5-Me), 2.40 s (3H, MeC6H4), 3.55–
3.64 m [1H, CH(CH3)2], 7.15 s (1H, 6-H), 7.47 d (2H,
2′-H, 6′-H, J = 8.1 Hz), 7.74 d (2H, 3′-H, 5′-H, J =
8.1 Hz), 9.05 s (1H, NH), 10.83 br.s (1H, OH). Found,
%: N 4.00, 4.17; S 8.68, 8.83. C19H23NO4S. Calculat-
ed, %: N 3.88; S 8.87.
N-[4-Hydroxy-2-isopropyl-3-(4-methoxyben-
zenesulfonyl)-5-methylphenyl]acetamide (Vd). Yield
1
30%, mp 172–173°C. H NMR spectrum (DMSO-d6),
δ, ppm: 0.87 d [6H, CH(CH3)2, J = 6.0 Hz], 1.96 s
(3H, Me), 2.17 s (3H, 5-Me), 3.56–3.65 m [1H,
CH(CH3)2], 3.85 s (3H, MeO), 7.16 d (2H, 2′-H, 6′-H,
J = 8.1 Hz), 7.19 s (1H, 6-H), 7.80 d (2H, 3′-H, 5′-H,
J = 8.1 Hz), 9.07 br.s (1H, NH), 10.84 br.s (1H, OH).
Found, %: N 3.59, 3.89; S 8.53, 8.64. C19H23NO5S.
Calculated, %: N 3.71; S 8.50.
N-(2-Methyl-4-oxocyclohexa-2,5-dien-1-ylidene)-
N′-(4-methylbenzenesulfonyl)acetimidamide (VIa).
1
Yield 64%, mp 151–152°C. H NMR spectrum
(CDCl3), δ, ppm: E isomer (74%): 2.15 br.s (3H,
2-Me), 2.29 s (3H, Me), 2.43 s (3H, MeC6H4), 6.53–
6.56 d.d (1H, 5-H, J = 9.3, 1.5 Hz), 6.56 br.s (1H,
3-H), 6.73 d (1H, 6-H, J = 9.3 Hz), 7.30 d (2H, 2′-H,
6′-H, J = 8.4 Hz), 7.78 d (2H, 3′-H, 5′-H, J = 8.4 Hz);
Z isomer (26%): 2.09 br.s (3H, 2-Me), 2.43 s (3H,
MeC6H4), 2.71 br.s (3H, Me), 6.53–6.56 d.d (1H, 5-H,
J = 9.3, 1.5 Hz), 6.56 br.s (1H, 3-H), 6.97 d (1H, 6-H,
J = 9.3 Hz), 7.31 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.86 d
(2H, 3′-H, 5′-H, J = 8.4 Hz). Found, %: N 8.55, 8.72;
S 10.15, 10.26. C16H16N2O3S. Calculated, %: N 8.85;
S 10.14.
N-[4-Hydroxy-2,3-dimethyl-5-(4-methylbenzene-
sulfonyl)phenyl]acetamide (Va). Yield 55%, mp 180–
1
N′-(4-Chlorobenzenesulfonyl)-N-(2-methyl-4-
181°C. H NMR spectrum (DMSO-d6), δ, ppm: 1.97 s
oxocyclohexa-2,5-dien-1-ylidene)acetimidamide
(3H, Me), 2.14 s (3H, 2-Me), 2.16 s (3H, 3-Me), 2.39 s
(3H, MeC6H4), 7.32 s (1H, 6-H), 7.46 d (2H, 2′-H,
6′-H, J = 8.1 Hz), 7.78 d (2H, 3′-H, 5′-H, J = 8.1 Hz),
9.34 s (1H, NH), 10.35 s (1H, OH). Found, %: N 4.06,
4.29; S 9.53, 9.81. C17H19NO4S. Calculated, %:
N 4.20; S 9.62.
1
(VIb). Yield 46%, mp 152–153°C. H NMR spectrum
(CDCl3), δ, ppm: E isomer (75%): 2.17 br.s (3H,
2-Me), 2.31 s (3H, Me), 6.58 br.s (1H, 3-H), 6.58–
6.61 d.d (1H, 5-H, J = 10.2, 1.5 Hz), 6.76 d (1H, 6-H,
J = 10.2 Hz), 7.50 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.85 d (2H, 3′-H, 5′-H, J = 8.4 Hz); Z isomer (25%):
2.09 br.s (3H, 2-Me), 2.74 br.s (3H, Me), 6.55–6.58 d.d
(1H, 5-H, J = 10.2, 1.5 Hz), 6.58 br.s (1H, 3-H), 6.96 d
(1H, 6-H, J = 10.2 Hz), 7.50 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.92 d (2H, 3′-H, 5′-H, J = 8.4 Hz). Found, %:
N 7.99, 8.30; S 9.48, 9.77. C15H13ClN2O3S. Calculated,
%: N 8.32; S 9.52.
N-[4-Hydroxy-5-(4-methoxybenzenesulfonyl)-
2,3-dimethylphenyl]acetamide (Vb). Yield 68%,
1
mp 191–192°C. H NMR spectrum (DMSO-d6), δ,
ppm: 1.97 s (3H, Me), 2.14 s (3H, 2-Me), 2.16 s (3H,
3-Me), 3.85 s (3H, MeO), 7.16 d (2H, 2′-H, 6′-H, J =
8.4 Hz), 7.30 s (1H, 6-H), 7.84 d (2H, 3′-H, 5′-H, J =
8.4 Hz), 9.31 s (1H, NH), 10.39 s (1H, OH). Found, %:
N 4.15, 4.33; S 9.05, 9.39. C17H19NO5S. Calculated,
%: N 4.01; S 9.18.
N-[4-Hydroxy-2-methyl-5-(4-methylbenzenesul-
fonyl)phenyl]-N′-(4-methylbenzenesulfonyl)acet-
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KONOVALOVA et al.
1290
1
imidamide (VIIa). H NMR spectrum (DMSO-d6), δ,
ppm: 2.09 s (3H, 2-Me), 2.35 s (3H, 4′-Me), 2.37 s
(3H, 4″-Me), 2.47 s (3H, Me), 6.76 s (1H, 3-H), 7.32 d
(2H, 2′-H, 6′-H, J = 8.1 Hz), 7.35 d (2H, 2″-H, 6″-H,
J = 8.7 Hz), 7.64 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.68 d
(2H, 3″-H, 5″-H, J = 8.7 Hz), 7.75 s (1H, 6-H),
10.09 br.s (1H, NH), 10.85 br.s (1H, OH).
(2H, 2′-H, 6′-H, J = 8.4 Hz), 7.71 d (2H, 3″-H, 5″-H,
J = 8.7 Hz), 7.98 d (2H, 3′-H, 5′-H, J = 8.4 Hz),
10.25 br.s (1H, NH), 10.69 br.s (1H, OH).
N-[4-Hydroxy-2-methyl-6-(4-methylbenzenesul-
fonyl)phenyl]-N′-(4-methylbenzenesulfonyl)acet-
1
imidamide (IXa). H NMR spectrum (DMSO-d6), δ,
ppm: 2.35 s (3H, 2-Me), 2.38 s (3H, 4′-Me), 2.38 s
(3H, 4″-Me), 2.71 s (3H, Me), 6.61 br.s (1H, 3-H),
7.12 br.s (1H, 5-H), 7.32 d (2H, 2′-H, 6′-H, J =
8.1 Hz), 7.46 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.63 d
(2H, 3′-H, 5′-H, J = 8.1 Hz), 7.87 d (2H, 3″-H, 5″-H,
J = 8.7 Hz), 9.56 br.s (1H, NH), 10.85 br.s (1H, OH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-2-
methyl-5-(4-methylbenzenesulfonyl)phenyl]acet-
1
imidamide (VIIb). H NMR spectrum (DMSO-d6), δ,
ppm: 2.10 s (3H, 2-Me), 2.37 s (3H, 4″-Me), 2.48 s
(3H, Me), 6.72 s (1H, 3-H), 7.36 d (2H, 2″-H, 6″-H,
J = 8.4 Hz), 7.57 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.65 d
(2H, 3″-H, 5″-H, J = 8.4 Hz), 7.74 d (2H, 3′-H, 5′-H,
J = 8.7 Hz), 7.76 s (1H, 6-H), 10.10 br.s (1H, NH),
10.80 br.s (1H, OH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-
2-methyl-6-(4-methylbenzenesulfonyl)phenyl]acet-
1
imidamide (IXb). H NMR spectrum (DMSO-d6), δ,
ppm: 2.37 s (3H, 2-Me), 2.38 s (3H, 4″-Me), 2.71 s
(3H, Me), 6.62 br.s (1H, 3-H), 7.09 br.s (1H, 5-H),
7.57 d (2H, 2″-H, 6″-H, J = 8.4 Hz), 7.58 d (2H, 2′-H,
6′-H, J = 8.7 Hz), 7.99 d (2H, 3″-H, 5″-H, J = 8.4 Hz),
8.00 d (2H, 3′-H, 5′-H, J = 8.7 Hz), 9.60 br.s (1H, NH),
10.86 br.s (1H, OH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-5-
(4-methoxybenzenesulfonyl)-2-methylphenyl]acet-
1
imidamide (VIIc). H NMR spectrum (DMSO-d6), δ,
ppm: 2.09 s (3H, 2-Me), 2.46 s (3H, Me), 3.83 s (3H,
MeO), 6.72 s (1H, 3-H), 7.08 d (2H, 2″-H, 6″-H, J =
8.7 Hz), 7.59 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.71 d
(2H, 3″-H, 5′-H, J = 8.7 Hz), 7.74 s (1H, 6-H), 7.76 d
(2H, 3′-H, 5′-H, J = 8.4 Hz), 10.10 br.s (1H, NH),
10.78 br.s (1H, OH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-
2-(4-methoxybenzenesulfonyl)-6-methylphenyl]-
acetimidamide (IXc). 1H NMR spectrum (DMSO-d6),
δ, ppm: 2.37 s (3H, 6-Me), 2.71 s (3H, Me), 3.82 s
(3H, MeO), 6.62 br.s (1H, 5-H), 7.09 br.s (1H, 3-H),
7.47 d (2H, 2″-H, 6″-H, J = 8.7 Hz), 7.59 d (2H, 2′-H,
6′-H, J = 8.4 Hz), 7.76 d (2H, 3′-H, 5′-H, J = 8.4 Hz),
7.99 d (2H, 3″-H, 5″-H, J = 8.7 Hz), 9.60 br.s (1H,
NH), 10.78 br.s (1H, OH).
N-[4-Hydroxy-2-methyl-3-(4-methylbenzenesul-
fonyl)phenyl]-N′-(4-methylbenzenesulfonyl)acet-
imidamide (VIIIa). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.37 s (3H, 2-Me), 2.38 s (3H, 4′-Me), 2.39 s
(3H, 4″-Me), 2.42 s (3H, Me), 6.75 d (1H, 5-H, J =
8.7 Hz), 7.24 d (1H, 6-H, J = 8.4 Hz), 7.29 d (2H,
2′-H, 6′-H, J = 8.1 Hz), 7.34 d (2H, 2″-H, 6″-H, J =
8.7 Hz), 7.55 d (2H, 3′-H, 5′-H, J = 8.1 Hz), 7.70 d
(2H, 3″-H, 5″-H, J = 8.7 Hz), 10.06 br.s (1H, NH),
10.68 br.s (1H, OH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-
2-methyl-3-(4-methylbenzenesulfonyl)phenyl]acet-
imidamide (VIIIb). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.37 s (3H, 2-Me), 2.38 s (3H, 4″-Me), 2.45 s
(3H, Me), 6.76 d (1H, 5-H, J = 8.7 Hz), 7.27 d (1H,
6-H, J = 8.4 Hz), 7.36 d (2H, 2″-H, 6″-H, J = 8.4 Hz),
7.58 d (2H, 2′-H, 6′-H, J = 8.7 Hz), 7.65 d (2H, 3″-H,
5″-H, J = 8.4 Hz), 8.00 d (2H, 3′-H, 5′-H, J = 8.7 Hz),
10.31 br.s (1H, NH), 10.70 br.s (1H, OH).
2,6-Dimethyl-4-[1-(4-methylbenzenesulfonyl-
imino)ethylamino]phenyl 4-methylbenzenesulfonate
1
(XIIa). H NMR spectrum (DMSO-d6), δ, ppm: 1.97 s
(6H, 2-Me, 6-Me), 2.38 (3H, 4′-Me), 2.45 s (3H, Me),
2.45 s (3H, 4″-Me), 7.30 s (2H, 3-H, 5-H), 7.38 d (2H,
2′-H, 6′-H, J = 7.5 Hz), 7.53 d (2H, 2″-H, 6″-H, J =
7.8 Hz), 7.74 d (2H, 3′-H, 5′-H, J = 7.5 Hz), 7.86 d
(2H, 3″-H, 5″-H, J = 7.8 Hz), 10.40 br.s (1H, NH).
4-[1-(4-Chlorobenzenesulfonylimino)ethyl-
amino]-2,6-dimethylphenyl 4-methylbenzenesulfo-
1
nate (XIIb). H NMR spectrum (DMSO-d6), δ, ppm:
1.97 s (6H, 2-Me, 6-Me), 2.45 s (3H, Me), 2.47 s (3H,
4″-Me), 7.27 s (2H, 3-H, 5-H), 7.53 d (2H, 2″-H, 6″-H,
J = 8.1 Hz), 7.65 d (2H, 2′-H, 6′-H, J = 8.4 Hz), 7.86 d
(2H, 3″-H, 5″-H, J = 8.1 Hz), 7.86 d (2H, 3′-H, 5′-H,
J = 8.4 Hz), 10.49 br.s (1H, NH).
N′-(4-Chlorobenzenesulfonyl)-N-[4-hydroxy-3-
(4-methoxybenzenesulfonyl)-2-methylphenyl]acet-
imidamide (VIIIc). 1H NMR spectrum (DMSO-d6), δ,
ppm: 2.37 s (3H, 2-Me), 2.46 s (3H, Me), 3.83 s (3H,
MeO), 6.79 d (1H, 5-H, J = 8.7 Hz), 7.08 d (2H, 2″-H,
6″-H, J = 8.7 Hz), 7.29 d (1H, 6-H, J = 8.1 Hz), 7.59 d
4-Acetylamino-2,6-dimethylphenyl 4-methyl-
1
benzenesulfonate (XIIIa). H NMR spectrum
(DMSO-d6), δ, ppm: 1.99 s (6H, 2-Me, 6-Me), 2.02 s
(3H, Me), 2.44 s (3H, 4′-Me), 7.31 s (2H, 3-H, 5-H),
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REACTION OF N-ACETYL- AND N-[1-(ARYLSULFONYLIMINO)ETHYL]-1,4-...
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7.52 d (2H, 2′-H, 6′-H, J = 6.3 Hz), 7.85 d (2H, 3′-H,
5′-H, J = 6.3 Hz), 9.92 s (1H, NH).
4-Hydroxy-3,5-diisopropylphenyl 4-chloroben-
zenesulfonate (XIXb). Yield 50%, mp 119–120°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 0.99 d [12H,
CH(CH3)2, J = 5.1 Hz], 3.17–3.24 m [2H, CH(CH3)2],
6.47 s (2H, 2-H, 6-H), 7.38 d (2H, 2′-H, 6′-H, J =
6.3 Hz), 7.56 d (2H, 3′-H, 5′-H, J = 6.3 Hz), 8.38 br.s
(1H, OH). Found, %: S 8.34, 8.72. C18H21ClO4S. Cal-
culated, %: S 8.69.
4-Acetylamino-2,6-dimethylphenyl 4-chloro-
1
benzenesulfonate (XIIIb). H NMR spectrum
(DMSO-d6), δ, ppm: 2.03 s (3H, Me), 2.01 s (6H,
2-Me, 6-Me), 7.32 s (2H, 3-H, 5-H), 7.79 d (2H, 2′-H,
6′-H, J = 6.3 Hz), 7.99 d (2H, 3′-H, 5′-H, J = 6.3 Hz),
9.93 s (1H, NH).
N-[4-Hydroxy-3,5-dimethyl-2-(4-methylbenzene-
REFERENCES
1
sulfonyl)phenyl]acetamide (XIVa). H NMR spec-
1. Burmistrov, K.S., Nichvoloda, V.M., Markov, V.I., and
Romanchenko, V.A., Zh. Org. Khim., 1986, vol. 22,
p. 1306.
2. 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.
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Ludchenko, O.N., and Marchenko, I.L., Russ. J. Org.
Chem., 2009, vol. 45, p. 383.
trum (DMSO-d6), δ, ppm: 1.98 s (3H, 3-Me), 2.20 s
(3H, 5-Me), 2.30 s (3H, Me), 2.37 s (3H, 4′-Me),
7.37 s (1H, 6-H), 7.39 d (2H, 2′-H, 6′-H, J = 8.4 Hz),
7.68 d (2H, 3′-H, 5′-H, J = 8.4 Hz), 8.78 br.s (1H, NH),
9.62 s (1H, OH).
N-[2-(4-Chlorobenzenesulfonyl)-4-hydroxy-3,5-
1
dimethylphenyl]acetamide (XIVb). H NMR spec-
trum (DMSO-d6), δ, ppm: 1.96 s (3H, 3-Me), 2.21 s
(3H, 5-Me), 2.34 s (3H, Me), 7.38 s (1H, 6-H), 7.66 d
(2H, 2′-H, 6′-H, J = 6.9 Hz), 7.81 d (2H, 3′-H, 5′-H,
J = 6.9 Hz), 8.88 br.s (1H, NH), 9.51 s (1H, OH).
4. Konovalova, S.A., Avdeenko, A.P., and Marchen-
ko, I.L., Russ. J. Org. Chem., 2014, vol. 50, p. 973.
5. Nichvoloda, V.M., Burmistrov, K.S., and Markov, V.I.,
N-(3,5-Diisopropyl-4-oxocyclohexa-2,5-dien-
1-ylidene)acetamide (XV). Yield 53%, mp 34–35°C.
1H NMR spectrum (CDCl3), δ, ppm: 1.12 d [12H,
CH(CH3)2, J = 6.9 Hz], 2.31 s (3H, Me), 3.05–3.14 m
[2H, CH(CH3)2], 6.64 br.s (2H, 2-H, 6-H). Found, %:
N 6.05, 6.18. C14H19NO2. Calculated, %: N 6.00.
4-Hydroxy-3,5-dimethylphenyl 4-methylben-
zenesulfonate (XVIIIa). Yield 71%, mp 159–160°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.09 s (6H,
3-Me, 5-Me), 2.37 s (3H, 4′-Me), 6.58 br.s (2H, 2-H,
6-H), 7.39 d (2H, 2′-H, 6′-H, J = 7.5 Hz), 7.70 d (2H,
3′-H, 5′-H, J = 7.5 Hz), 9.50 br.s (1H, OH). Found, %:
S 10.52, 10.88. C15H16O4S. Calculated, %: S 10.97.
Zh. Org. Khim., 1985, vol. 21, p. 1069.
6. 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.
7. 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.
8. Konovalova, S.A., Avdeenko, A.P., Ledeneva, O.P.,
Yusina, A.L. Pirozhenko, V.V., Shishkin, O.V., and
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classic.chem.msu.su/gran/firefly/index.html
4-Hydroxy-3,5-dimethylphenyl 4-chlorobenzene-
sulfonate (XVIIIb). Yield 75%, mp 82–83°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 2.07 s (6H,
3-Me, 5-Me), 6.62 br.s (2H, 2-H, 6-H), 7.39 d (2H,
2′-H, 6′-H, J = 8.1 Hz), 7.57 d (2H, 3′-H, 5′-H, J =
8.1 Hz), 9.82 br.s (1H, OH). Found, %: S 9.73, 10.18.
C14H13ClO4S. Calculated, %: S 10.25.
4-Hydroxy-3,5-diisopropylphenyl 4-methylben-
zenesulfonate (XIXa). Yield 60%, mp 113°C.
1H NMR spectrum (DMSO-d6), δ, ppm: 0.98 d [12H,
CH(CH3)2, J = 5.1 Hz], 2.40 s (3H, 4′-Me), 3.16–
3.23 m [2H, CH(CH3)2], 6.44 s (2H, 2-H, 6-H), 7.45 d
(2H, 2′-H, 6′-H, J = 6.3 Hz), 7.67 d (2H, 3′-H, 5′-H,
J = 6.3 Hz), 8.32 s (1H, OH). Found, %: S 8.81, 9.17.
C19H24O4S. Calculated, %: S 9.20.
10. 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.,
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 9 2014