Reactions of N-arylsulfonylquinone imines with enamines

Article abstract of DOI:10.1134/S1070428011080094

Depending on the reaction conditions N-arylsulfonyl-1,4-quinone imines with enamines led to the formation of the products of 1,4-addition, derivatives of benzo- and naphthofuran, indole, and benzindole.

Full text of DOI:10.1134/S1070428011080094

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 8, pp. 1169−1180. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.P. Avdeenko, S.A. Konovalovaa, O.N. Mikhailichenko, A.L. Yusina, A.A. Santalova, G.V. Palamarchyk, R.I. Zubatyuk, O.V. Shishkin,
K.S. Burmistrov, 2011, published in Zhurnal Organicheskoi Khimii, 2011, Vol. 47, No. 8, pp. 1151−1162.
Reactions of N-Arylsulfonylquinone Imines with Enamines
A. P. Avdeenkoa, S. A. Konovalovaa, O. N. Mikhailichenkoa,
A. L. Yusinaa, A. A. Santalovaa, G. V. Palamarchykb, R. I. Zubatyukb,
O. V. Shishkinb, and K. S. Burmistrovc
aDonbass State Machine-Building Academy, Kramatorsk, 84313 Ukraine
е-mail: chimist@dgma.donetsk.ua
bInstitute of Single Crystals, National Academy of Sciences of Ukraine, Kharkov, Ukraine
cUkrainian State University of Chemical Engineering, Dnepropetrovsk, Ukraine
Received November 23, 2010
Abstract—Depending on the reaction conditions N-arylsulfonyl-1,4-quinone imines with enamines led to the
formation of the products of 1,4-addition, derivatives of benzo- and naphthofuran, indole, and benzindole.
DOI: 10.1134/S1070428011080094
A multitude of publications describe the reactions of
p-benzoquinone with enamines resulting in heterocyclic
compounds: benzofuran (I) [1–4] or indole (II) [2, 3,
5–9] derivatives which are mostly biologically active sub-
stances [4, 10, 11]. The structure of the reaction products
depends on the structure of initial compounds (it is the
most strongly affected by the substituent at the nitrogen
atom of the enamine) [2, 6, 8] and the conditions of the
reaction [2, 8, 12].
acid in chloroform or acetone only indole derivatives
were obtained (II, X = TsNH, R1 = COOEt, R2 = Me,
Y = 4-MeC6H4, Ph, 4-MeOC6H4) [13, 14, 16], N-tosyl-
1,4-naphthoquinone imine in acetone formed only the
open-chain product of 1,4-addition [17]. The formation
of indole derivatives is favored by the presence of an
aryl substituent at the nitrogen atom of the enamine [13].
Benzofuran derivatives were obtained at the hydrolysis of
the addition products of the esters of 3-alkyl- and 3-aryl-
aminocrotonic acids [18, 19] to N-tosyl-1,4-benzoquinone
monoimine. No research concerned the effect on the di-
rection of this reaction of the substituents in the quinoid
ring of the N-arylsulfonyl-1,4-quinone imines. It was for-
merly established that in the reactions of p-benzoquinone
with enamines the substituents in the quinoid ring govern
the direction of this reaction [4, 6, 7, 9].
R1
R1
X
X
R2
R2
O
N
Y
I
II
The goal of this study was the establishment of the
effect of the reaction condition and the structure of N-
arylsulfonyl-1,4-quinone imines, in particular, of the
position and the character of the substituent in the quinoid
ring, on the direction of their reactions with the acetylac-
etone imine and the esters of 3-arylaminocrotonic acid .
Several papers consider the reactions of N-arylsulfo-
nyl-1,4-quinone imines with enamines, in particular, with
imines of acetylacetone and ethyl 3-arylaminocroton-
ates [13–16]. The reaction of N-tosyl-1,4-benzoquinone
imine with acetylacetone imine in methanol or acetic
acid resulted in a heterocyclic derivative (I, X = TsNH,
R1 = COMe, R2 = Me) [15, 16], in acetone another
structure was obtained (II, X = TsNH, R1 = COMe, R2 =
Me, Y = 4-MeC6H4) [16]. In reactions of N-tosyl-1,4-
benzoquinone imine with esters of 3-arylaminocrotonic
The reaction of N-arylsulfonyl-1,4-benzoquinone
monoimines IIIа–IIIo with p-tolylaminopent-3-en-2-one
(IVа) and esters of 3-arylaminocrotonic acid IVb, IVc
was carried out in acetone, acetic acid, dichloroethane,
1169

AVDEENKO et al.
1170
Scheme 1.
Me
OH
SO2NH
OEt
O
CO(Me)2
MeO
NH Me
V
R3
4
R4
3
X
SO2NH
2
,
(CH2Cl)2
CHCl3
5
Me
1
R2
R3
R1
Y
R2
6
N
7
R1
H
R4
SO2N
X
O
Me
NH
VIа–VIu
Y
Z
R3
R4
4
IIIа–IIIp
3
SO2NH
R2
X
2 Me
CH3COOH
5
1
O
Z
6
7
IVа–IVc
R1
VIIа–VIIi
R2
R1
SO2NH
OH
(CH2Cl)2
3
3
R
R
Cl
VIIIа, VIIIb
VIIIa, VIIIb
III, R1 = R2 = R3 = Y = H, X = Me (a); R1 = Cm, R2 = R3 = Y = H, X = ОMe (b), Me (с), R1 = Me, R2 = R3 = Y = H, X =
OMe (d), Me (e), Н (f), Cl (g); R1 = Me, R2 = R3 = X = H, Y = NO2 (h); R1 = R3 = Y = H, R2 = Cl, X = Me (i); R1 = R3 =
Y = H, R2 = Me, X = ОMe (j), Н (k); R1 = R2 = Me, R3 = X = Н, Y = Н (l), NO2 (m); R1 = R3 = Me, R2 = X = Y = Н (n);
R1 = i-Pr, R3 = Me, R2 = X = Y = Н (o); R2 = R3 = Me, R1 = X = Y = Н (p); IV, R4 = COMe, Z = Me (a); R4 = COOEt, Z =
Me (b), OMe (с); VI, R1 = R2 = R3 = Y = H, X = Me: R4 = COMe, Z = Me (a); R4 = COOEt, Z = Me (b), OMe (с); R1 =
Cl, R2 = R3 = Y = H: X = ОMe, R4 = COMe, Z = Me (d); X = Me, R4 = COOEt, Z = Me (e); X = Me, R4 = COOEt, Z =
OMe (f); R1 = Me, R2 = R3 = Y = H: X = OMe, R4 = COMe, Z = Me (g); X = Me, R4 = COMe, Z = Me (h); X = Н, R4 =
COMe, Z = Me (i); X = Н, R4 = COOEt, Z = Me (j), ОMe (k); X = Cl, R4 = COMe, Z = Me (l); R1 = Me, R2 = R3 = X =
H, Y = NO2, R4 = COMe, Z = Me (m); R1 = R3 = Y = H, R2 = Cm, X = Me: R4 = COOEt, Z = Me (n); R4 = COOEt, Z =
OMe (o); R1 = R3 = Y = H, R2 = Me: X = ОMe, R4 = COMe, Z = Me (p); X = Н, R4 = COMe, Z = Me (q); X = Н, R4 =
COOEt, Z = Me (r), ОMe (s); R1 = R2 = Me, R3 = X = Н, Y = NO2: R4 = COMe, Z = Me (t); R4 = COOEt, Z = ОMe (u);
VII, R1 = R2 = R3 = H, X = Me, R4 = COMe (a), COOEt (b); R1 = Cl, R2 = R3 = H: X = ОMe, R4 = COMe (с), COOEt
(d); X = Me, R4 = COMe (e); R1 = Me, R2 = R3 = X = H, R4 = COMe (f), COOEt (g); R1 = R3 = H, R2 = Cl, X = Me, R4 =
COMe (h); R1 = R3 = X = H, R2 = Me, R4 = COMe (i); R1 = R2 = Me, R3 = X = Н, R4 = COMe (j), COOEt (k); R2 = R3 =
Me, R1 = X = Н, R4 = COMe (l), COOEt (m); VIII, R1 = R3 = Me, R2 = Н (а); R1 = i-Pr, R2 = Н, R3 = Me (b).
and chloroform. As a result depending on the structure
of initial quinone imine IIIа–IIIo and the reaction condi-
tions we obtained the product of 1,4-addition V, deriva-
tives of indole VIа–VIu, of benzofuranа VIIа–VIIm,
and aminophenols VIIIа, VIIIb (Scheme 1).
isolation of the product of 1,4-addition V. In chloroform
and dichloroethane indole derivatives VIа–VIu were iso-
lated, in acetic acid, benzofuran derivatives VIIа–VIIm
that previously never had been obtained in one-stage
process. Hence practically from all quinone imines with
a free С=С bond in the quinoid ring IIIа–IIIm in reac-
tion with enamines IVа–IVc we obtained both indole
VIа–VIu and benzofuran VIIа–VIIm derivatives, and
In acetone most often noncrystalline oily compounds
were obtained. In a single instance, in the reation of
quinone imine IIIf with crotonate IVa we succeeded in
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REACTIONS OF N-ARYLSULFONYLQUINONE IMINES WITH ENAMINES
1171
the structure of the reaction product was governed by the
solvent nature.
compared with the average value of 1.419 Å [20]. Yet it
should be noted that the bond lengths S1–N1 1.622(2) and
S1–C9 1.756(2) Å correspond to average values 1.633
(bond distance S–N in the fragment C–SO2–NH–C) and
1.758 Å (bond distance C–S in the fragment CAr–SO2–N1)
respectively.
We failed to obtain from 2,5-dialkyl-1,4-benzoquinone
monoimines IIIn, IIIo the product of reactions with
enamines, compounds V, VI, or VII. The reactions in
dichloroethane yielded white crystalline substances
1
whose Н NMR spectrum contained the aryl fragment
The special feature of the crystal structure of
compound VIIIa is the formation of bifurcate hydrogen
bond involving the hydrogen atom of the hydroxy group:
intramolecular О1–Н10···Сl1 (Н10···Сl1 2.43 Å, О1–
Н10···Сl1 121 deg) and intermolecular О1–H10···О2' (1–x,
–0.5+y, 0.5–z) (H10···О2 2.27 Å, О1–H10···О2 139 deg).
ArSO2, two alkyl groups, one hydrogen atom, NH and
OH groups. According to IR spectra these compounds
contained NH and OH groups and no carbonyl groups.
In reactions of 2,5-dimethyl-N-phenylsulfonyl-1,4-benzo-
quinone monoimine (IIIn) with enamines IVа–IVc in all
three experiments notwithstanding the enamine structure
the same reaction product was isolated, the reaction of
3-isopropyl-6-methyl-N-phenylsulfonyl-1,4-benzoqui-
none monoimine (IIIo) with enamines IVа–IVc also
independent of the enamine structure yielded the same
compound. In order to establish the structure of com-
pounds obtained the reaction product of quinone imine
IIIn and acetylacetone imine IVа was subjected to XRD
analysis on a single crystal. The compound unexpectedly
proved to be 4-amino-2,5-dimethyl-N-phenylsulfonyl-6-
chlorophenol (VIIIа) (see the figure).
The N1–S1 bond of the sulfamide group of compound
VIIIa is directed normal to the planes of the benzene
rings [torsion angles C2C1N1S1 –92.5(2), C10C9S1N1
–94.0(2) deg]. This results in the total absence of the n-π
conjugation between the unshared electron pair of the
atom N1 and the benzene ring С1···С6. As a result of the
absent conjugation the nitrogen atom has a pyramidal
configuration (the sum of bond angles at the atom N1 is
345.4 deg) and the bond С1–N1 is extended to 1.444(2) Å
The structure of aminophenol VIIIb was established
by analogy of the spectral characteristics with those of
compound VIIIa and also by an independent synthesis,
for previously aminophenols VIIIa, VIIIb had been
obtained by the halogenation and hydrohalogenation of
quinone monoimines IIIn, IIIo [21]. It was presumable
basing on the data obtained that the dichloroethane was
involved into the reaction. To check this assumption we
boiled quinone monoimines IIIn, IIIo in dichloroethane
with distillation off the solvent but without addition of
enamine. As a result aminophenols VIIIa, VIIIb were
also obtained in low yield (~20%).
We purified dichloroethane by fractional distillation on
potassium hydroxide after keeping it on this alkali [22].
However at the action of the alkali dichloroethane might
be converted into vinyl chloride with hydrogen chloride
liberation. Apparently the formed amount of HCl was
sufficient to initiate the hydrochlorination leading to the
formation of aminophenols VIIIa, VIIIb. Therefore the
Structure of 4-amino-2,5-dimethyl-N-phenylsulfonyl-6-chlorophenol (VIIIа) according to XRD analysis.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

AVDEENKO et al.
1172
chloroethane and chloroform formed 2-methyl-1-aryl-5-
tosylamino-3-ethoxycarbonyl-1H-benzo[g]indoles XIа,
XIb, in acetic acid 2-methyl-5-(tosylamino)naphtho-
[1,2-b]furans XIIа, XIIb were obtained. In reaction with
enamine IVc in acetone a mixture of compounds Xb and
XIb was isolated, and we failed to obtain naphthol Xb in
individual state.According to 1Н NMR spectra compounds
Xа, Xb contain NH and ОН groups, fragments Ts and
ArN, compounds XIа, XIb, group NH and fragments Ts
andArN, and compounds XIIа, XIIb have group NH and
special requirements should be applied to dichloroethane
used in the reactions with enamines: The drying agents
should not lead to hydrogen chloride liberation from
dichloroethane.
The reaction of quinone monoimines IIIn, IIIo
with enamines in dichloroethane purified by procedure
[23] with the use of phosphorus(V) oxide resulted in
recovering initial quinone monoimines.
In the reaction of 3,5-dimethyl-N-phenyl-sulfonyl-
1,4-benzoquinone monoimine (IIIp) in acetic acid only
benzofuran derivatives VIIl, VIIm were obtained. We
failed to isolate indole derivatives for in chloroform and
dichloroethane formed uncrystallizable oily substances.
fragment Ts, and also signals of hydrogen atoms Н4,6–9
.
The reaction of N,N'-ditosyl-1,4-benzoquinone
diimines XIIIа, XIIIb with enamines IVа–IVc afforded
indole derivatives VIа, VIc, VIn, VIo (Scheme 3), iso-
lated before from reactions of benzoquinone monoimines
IIIa, IIIi with enamines IVа–IVc (Scheme 1). Therewith
indole derivatives VIа, VIc were obtained from unsubsti-
tuted in the quinoid ring N,N'-ditosyl-1,4-benzoquinone
diimine (XIIIа) and benzoquinone monoimine IIIa, and
compounds соеdинения VIn, VIo, from N,N'-ditosyl-
2-chloro-1,4-benzoquinone diimineа (XIIIb) and N-
tosyl-3-chloro-1,4-benzoquinone monoimine (IIIi). The
latter data show that the primary addition of enamine to
quinone imine XIIIb occurs precise in the para-position
with respect to the chlorine atom in the quinoid ring ap-
parently due to steric factors (position 6 is shielded by Ts
group, position 3, by chlorine atom). At the subsequent
cyclization TsNH is the leaving group.
The substituents in the quinoid ring of the initial qui-
none imine affect to some extent the reaction rate and
the ease of the products isolation. In the presence of an
acceptor substituent (chlorine atom) in the quinoid ring
(quinone imines IIIb, IIIc, IIIi) the reaction proceeded
relatively readily, very soon a crystalline precipitate
separated, but in the case of quinone imine IIIa unsub-
stituted in the quinoid ring, and of quinone imines with
alkyl substituents in the quinoid ring IIId–IIIh, IIIj–IIIp
the reaction was slower and the isolation of the reaction
products was significantly more difficult.
The structure of compounds V–VII was established
from the spectral data. In the 1Н NMR spectra of com-
pounds VIа–VIu the proton signals are present from the
aryl fragment ArSO2 and aryl fragment ArN, the set of
signals from hydrogen and alkyl groups in the positions
2, 4, 6, and 7 of indole with the characteristic chemical
shift values, and of NH and R4 groups. In the 1Н NMR
spectra of compounds VIIа–VIIm proton signals appear
only from the aryl fragmentArSO2, the set of signals from
hydrogen and alkyl groups in the positions 2, 4, 6, and 7
of benzofuran, and of groups NH and R4.
Thus basing on the published data and experiments
performed in this study it is presumable that the reaction
of N-arylsulfonyl-1,4-quinone imines with enamines pro-
ceeds along Scheme 4. Firstly in all events 1,4-addition
of enamine to quinone imine occurs with the formation
of compounds V, X which may exist in two tautomeric
forms А and B (Scheme 4). Then depending on reaction
conditions the process either stops (as occurs in acetone),
or proceeds further via cyclization in two directions.
In the IR spectra of compounds VIа–VIu, VIIа–VIIm
absorption bands are present in the region 3160–3280
(NH), 1670–1690 (COOEt), and 1620–1630 (COMe)
cm–1, and the absorption bands characteristic of ОН group
in the region 3350–3450 сm–1 are absent.
In keeping with the experiment the derivatives of
benzo(naphtho)furan VII, XII form only in proton-con-
taining solvents. Enamines relatively readily undergo the
protonation both at the nitrogen atom where a large elec-
tron density is localized and at the β-carbon atom bearing
partial negative charge, and this favors fast hydrolysis of
these compounds to an amine and a carbonyl compound
[24]. Therefore the formation of benzo(naphtho)furan
VII, XII may be assigned to the acid hydrolysis of the
enamine fragment. The products of addition of enamines
We studied also the reaction of N-tosyl-1,4-naphtho-
quinone monoimine (IX) with p-tolylaminacetylacetone
(IVа) and esters of 3-arylaminocrotonic acid IVb, IVc
(Scheme 2). Like in event of benzoquinone monoimines
III naphthoquinone imine IX in acetone gave products
of 1,4-addition, 2-[2-arylamino-1-(ethoxycarbonyl)
prop-1-enyl]-4-tosylamino-1-naphthols Xа, Xb, in di-
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REACTIONS OF N-ARYLSULFONYLQUINONE IMINES WITH ENAMINES
1173
Scheme 2.
OEt
Me
O
C
3
2
Z
NH
1
4
OH
TsNH
TsNH
Me2CO
8
5
6
7
Xа, Xb
O
OEt
C
4
3
IVа_IVc
TsN
2
O
5
H2O
+
Me
1
,
(CH2Cl)2
CHCl3
6
7
N
9
8
IX
XIа, XIb Z
R
4
3
TsNH
ArNH2
+
2 Me
5
CH3COOH
1
O
6
7
9
8
XIIа, XIIb
X, XI, Z = Me (a), OMe (b); XII, R = COMe (a), COOEt (b).
to quinone imines V, X may exist as two boundary tauto-
meric forms А and B, and their protonation products, as
tautomers C and D (Scheme 4). The protonation makes
favorable conditions for the hydrolysis of the enamine
fragment, and in the absence of water in the reaction
mixture the role of the “hydrolyzing” agent is played by
the ОН group of aminophenol. As a result intermediate
E is formed which in its turn is converted into the final
benzo(naphtho)furan VII, XII.
In order to test this assumption we carried out the re-
actions of quinone monoimines IIIc, IIIl with enamines
IVa, IVb also in formic acid and in chloroformе with
added small amount of one of acids (benzoic, 4-tolylsul-
finic, trifluoroacetic, hydrochloric, and sulfuric). In all
cases we obtained benzo(naphtho)furan VII, XII. The
most suitable acids were acetic and formic where the
purest substances were obtained in high yields (up to
90%). With strong acids (sulfuric, hydrochloric, trifluo-
roacetic) the yield of reaction products notably decreased
(15–30%), since among the reaction products the quantity
of impurities grew probably due to the hydrolysis of the
initial enamines.
Scheme 3.
R
NTs IVа_IVc
TsN
XIIIа, XIIIb
The derivatives of indole VI or benzoindole XI were
obtained in aprotic solvents (chloroform, dichloroethane).
The formation of these products may be ascribed to the
TsNH2
VIа,VIcв, VIn, VIp
III, R = H (a), Cl (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

AVDEENKO et al.
1174
Scheme 4.
Y
_
Me
Y
H
Me
Y
Me
+
NH Ar'
N Ar'
NH Ar'
OH
ArSO2NH
OH
OH
ArSO2NH
ArSO2NH
А (V, X)
B (V, X)
H+
H
Y
Me
Y
Me
+
+
NH Ar'
NH2 Ar'
OH
ArSO2NH
OH
ArSO2NH
D
C
Y
Y
H
Me
Me
+
O
NH Ar'
O
ArSO2NH
ArSO2NH
_
_H+
,
Ar'NH2
H
E
VII, XII
generation of intermediate F followed by its conversion
into indole VI or benzoindole XI (Scheme 5). Therewith
in the case of N,N'-bisarylsulfonyl-1,4-benzoquinone
diimines the leaving group is ArSO2NH of the quinone
diimine, and in the case of monoimines, water molecule.
EXPERIMENTAL
1Н NMR spectra were measured on a spectrometer
Varian VXR-300 (300 MHz), internal reference TMS,
in DMSO-d6 (V, VId, VIg−VIi, VIl, VIm, VIIа–VIId,
Scheme 5.
Y
Y
Me
Y
H
Me
Ar'
Me
Ar'
NH Ar'
RH
ArSO2NH
N
N
ArSO2NH
ArSO2NH
_H2R
RH
V, X
F
VI, XI
R = O, NSO2Ar.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

REACTIONS OF N-ARYLSULFONYLQUINONE IMINES WITH ENAMINES
1175
VIIg, VIIj–VIIm, XIIb), in CDCl3 (VIа, VIc, XIb), in
filtered off.
acetone-d6 (VIb, VIe, VIf, VIj, VIk, VIn–VIu, VIIe,
VIIf, Xа, Xb, XIа, XIIа). IR spectra were recorded on a
spectrophotometer UR-20 in pellets with KBr. The purity
of quinone imines was checked by TLC on Silufol UV-
254 plates. Chloroform was used as solvent, eluent etha-
nol–chloroform, 1 : 10, development under UV radiation.
b. Quinone imine (1.5 mmol) was dissolved in 10 ml
of acetone or chloroform, and 1.7 mmol of enamine
was added, the solution at once turned dark-brown. The
solvent was evaporated, and a light-colored precipitate
formed. If the precipitate did not form, several drops
of ethanol was added, and the mixture was stirred. The
separated crystals were filtered off.
Crystals of compound VIIIа monoclinic, C14H14Cl-
NO3S, at 293 K a 8.705(1), b 18.440(2), c 9.808(1) Å,
β 112.57(1) deg, V 1453.8(3) Å3, Mr 311.77, Z 4, space
group P21/с, dcalc 1.424 g/cm3, μ(MoKα) 0.41 mm–1,
F(000) 648. The parameters of unit cell and intensities
of 7181 reflections (2525 independent, Rint 0.012) were
measured on a diffractometer Xcalibur-3 (MoKα radiation,
ССD-detector, graphite monochromator, ω-scanning,
2θmax 50 deg).
c. To a dispersion or a solution of 1.5 mmol of quinone
imine in 10 ml of glacial acetic acid was added 1.7 mmol
of enamine, the solution at once turned dark-brown. Some
time later (from several minutes to several hours) light-
colored precipitate separated. In some cases to promote
the precipitation water was added dropwise to the reaction
mixture. The precipitate was filtered off.
All compounds obtained were recrystallized from
ethanol or aqueous ethanol.
The structure was solved by the direct method using
program package SHELX-97 [25]. The positions of hy-
drogen atoms were revealed from the difference synthesis
of the electron density and refined in the rider model with
The characteristics of compound VIIa are consistent
with the data in [16], of compounds VIIIa, VIIIb, in [27].
Ethyl 2-{2-hydroxy-3-methyl-5-[(phenylsulfonyl)
amino]phenyl}-3-[(4-methoxyphenyl)amino]but-2-
enoate (V). Yield 20%, mp 215–218°С. 1Н NMR spec-
trum, δ, ppm: 1.01 t (3Н, СН2Mе, J 6.6 Hz), 1.38 s (3Н,
C=C–Me), 2.05 s (3Н, 3-Mе), 3.76 s (3Н, MеО), 3.95 q
(2Н, СН2Mе), 6.45 d (1Н, Н4, J4,6 0.9 Hz), 6.72 d (1Н,
Н6), 6.96 d (2Н, Н3',5', 4-MеOС6Н4, J 9.0 Hz), 7.11 d
(2Н, Н2',6', 4-MеOС6Н4, J 9.0 Hz), 7.49–7.64 m (5Н, Ph),
8.04 s (1Н, NH), 9.61 br.s (1Н, NH), 11.03 s (1Н, ОН).
Found, %: С 62.95, 62.87; Н 5.41, 5.68; N 5.69, 5.75.
C26H28N2O6S. Calculated, %: C 62.89; Н 5.68; N 5.64.
U
iso = nUeq of the nonhydrogen atom connected to this
hydrogen (n = 1.5 for hydroxy and methyl groups, 1.2
for the other hydrogen atoms). The structure was refined
by F2 in full-matrix least-squares procedure in the aniso-
tropic approximation for nonhydrogen atoms till wR2
0.105 for 3677 reflections [R1 0.036 for 2099 reflections
with F > 4σ(F), S 1.08]. Atomic cooldinates, geometric
parameters of the molecule, and the crystallographic
data are deposited in Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:
+44 1223 336033; e-mail: deposit@ ccdc.cam.ac.uk) and
available at the number CCDC 751259.
3-Acetyl-2-methyl-1-(4-methylphenyl)-5-tosyl-
amino-1H-indole (VIа). Yield 65%, mp 221–222°С.
1Н NMR spectrum, δ, ppm: 2.36 s (3Н, 4-MеС6Н4SO2),
2.47 s (3Н, 4-MеС6Н4N), 2.53 s (3Н, 2-Mе), 2.57 s
(3Н, СОMе), 6.84 br.s (1Н, NH), 6.88 d (1Н, Н7,
1,4-Quinone monoimines IIIа, IIId–IIIp, IX were
synthesized by procedure [26], 1,4-benzoquinone
monoimines IIIb, IIIc, by procedure [27], N,N'-ditosyl-
1,4-benzoquinone diimine (XIIIа), by method [28], N,N '-
ditosyl-2-chloro-1,4-benzoquinone diimine (XIIIb), by
method [29], acetylacetone p-tolylamine (IVа) and esters
of 3-arylaminocrotonic acid IVb, IVc were obtained as
described in [30].
J
7,6 8.4 Hz), 7.01 d (1Н, Н6, J6,4 2.1 Hz), 7.15 d (2Н, Н3',5'
,
4-MеС6Н4N, J 8.1 Hz), 7.36 d (2Н, Н2',6', 4-MеС6Н4N,
J 8.1 Hz), 7.19 d (2Н, Н3'',5'', 4-MеС6Н4SO2, J 8.1 Hz),
7.63 d (2Н, Н2'',6'', 4-MеС6Н4SO2, J 8.1 Hz), 7.67 d (1Н,
Н4). Found, %: С 69.35, 69.68; Н 5.45, 5.76; N 6.59, 6.35.
C25H24N2O3S. Calculated, %: С 69.42; Н 5.59; N 6.48.
Reactions of N-substituted 1,4-quinone imines
IIIа–IIIp, IX, XIIIа, XIIIb with enamines IVа–IVc.
2-Methyl-1-(4-methylphenyl)-5-tosylamino-
3-ethoxycarbonyl-1H-indole (VIb). Yield 75%,
mp 199–200°С. 1Н NMR spectrum, δ, ppm: 1.40 t (3Н,
СН2Mе, J 7.2 Hz), 2.34 s (3Н, 4-MеС6Н4SO2), 2.46 s
(3Н, 4-MеС6Н4N), 2.51 s (3Н, 2-Mе), 4.33 q (2Н,
СН2Mе), 6.85 d (1Н, Н7, J7,6 9.0 Hz), 7.05 d (1Н, Н6,
а. Quinone imine (1.5 mmol) was boiled for 1 h with
1.7 mmol of enamine in 40 ml of dichloroethane, then
the mixture was evaporated in a vacuum. To the brown
residue several drops of ethanol was added, and then
light-colored crystals started to form. The crystals were
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

AVDEENKO et al.
1176
J6,4 2.1 Hz), 7.30 d (2Н, Н3',5', 4-MеС6Н4N, J 8.1 Hz),
7.46 d (2Н, Н2',6', 4-MеС6Н4N, J 8.1 Hz), 7.30 d (2Н,
2-Methyl-1-(4-methoxyphenyl)-5-tosylamino-7-
chloro-3-ethoxycarbonyl-1H-indole (VIf). Yield 55%,
mp 208–209°С. 1Н NMR spectrum, δ, ppm: 1.40 t (3Н,
СН2Mе, J 7.2 Hz), 2.36 s (3Н, 4-MеС6Н4), 2.40 s (3Н,
2-Mе), 3.90 s (3Н, MеО), 4.34 q (2Н, СН2Mе), 7.08 d
(1Н, Н6, J6,4 1.8 Hz), 7.08 d (2Н, Н3',5', 4-MеОС6Н4,
J 9.0 Hz), 7.32 d (2Н, Н2',6', 4-MеОС6Н4, J 9.0 Hz), 7.33 d
Н3'',5'', 4-MеС6Н4SO2, J 8.4 Hz), 7.68 d (2Н, Н2'',6''
,
4-MеС6Н4SO2, J 8.4 Hz), 7.99 d (1Н, Н4), 8.80 br.s (1Н,
NH). Found, %: С 67.49, 67.79; Н 5.53, 5.78; 6.01,
6.10. C26H26N2O4S. Calculated, %: C 67.51; Н 5.67;
N 6.06.
(2Н, Н3'',5'', 4-MеС6Н4, J 8.1 Hz), 7.72 d (2Н, Н2'',6''
,
2-Methyl-1-(4-methoxyphenyl)-5-tosylamino-
4-MеС6Н4, J 8.1 Hz), 8.04 d (1Н, Н4), 9.01 br.s (1Н, NH).
Found, %: С 60.84, 60.78; Н 4.75, 5.02; N 5.40, 5.55.
C26H25ClN2O5S. Calculated, %: C 60.87; Н 4.91; N 5.46.
3-ethoxycarbonyl-1H-indole (VIc). Yield 42%, mp
1
178–179°С. Н NMR spectrum, δ, ppm: 1.39 t (3Н,
СН2Mе, J 7.2 Hz), 2.35 s (3Н, 4-MеС6Н4), 2.53 s
(3Н, 2-Mе), 3.89 s (3Н, MеО), 4.36 q (2Н, СН2Mе),
6.81 br.s (1Н, NH), 6.85 d (1Н, Н7, J7,6 9.0 Hz), 6.99 d
(1Н, Н6, J6,4 1.8 Hz), 7.04 d (2Н, Н3',5', 4-MеОС6Н4,
J 9.0 Hz), 7.18 d (2Н, Н2',6', 4-MеОС6Н4, J 9.0 Hz),
7.18 d (2Н, Н3'',5'', 4-MеС6Н4, J 7.8 Hz), 7.64 d (2Н,
Н2'',6'', 4-MеС6Н4, J 7.8 Hz), 7.73 d (1Н, Н4). 13С NMR
spectrum, δ, ppm: 12.93 (2-Me), 14.57 (CH2Me), 21.45
(4-MeC6H4), 55.67 (OMe), 59.60 (CH2Me), 105.07
(C3), 110.95 (C6), 115.10 (C3''), 116.16 (C4), 118.89 (C7),
126.87 (C3a), 127.49 (C2'), 128.88 (C7a), 129.24 (C2''),
129.49 (C3'), 131.14 (C1''), 136.26 (C1'), 136.82 (C2),
143.32 (C5), 146.76 (C4'), 160.04 (C4''), 165.84 (C=O).
Found, %: С 65.10, 65.82; Н 5.35, 5.61; N 5.81, 5.92.
C26H26N2O5S. Calculated, %: C 65.25; Н 5.48; N 5.85.
3-Acetyl-2,7-dimethyl-1-(4-methylphenyl)-5-(4-
methoxyphenylsulfonyl)amino-1H-indole (VIg). Yield
43%, mp 233–235°С. 1Н NMR spectrum, δ, ppm: 1.65 s
(3Н, 7-Mе), 2.31 s (3Н, 4-MеС6Н4), 2.35 s (3Н, 2-Mе),
2.42 s (3Н, СОMе), 3.77 s (3Н, MеО), 6.67 br.s (1Н, Н6),
7.03 d (2Н, Н3',5', 4-MеС6Н4, J 6.6 Hz), 7.36 d (2Н, Н2',6'
,
4-MеС6Н4, J 6.6 Hz), 7.26 d (2Н, Н3'',5'', 4-MеОС6Н4,
J 6.0 Hz), 7.68 d (2Н, Н2'',6'', 4-MеОС6Н4, J 6.0 Hz),
7.79 br.s (1Н, Н4), 9.87 s (1Н, NH). Found, %: С 67.54,
67.50; Н 5.55, 5.78; N 6.00, 6.10. C26H26N2O4S. Calcu-
lated, %: C 67.51; Н 5.67; N 6.06.
3-Acetyl-2,7-dimethyl-1-(4-methylphenyl)-5-tosyl-
amino-1H-indole (VIh). Yield 39%, mp 260–263°С.
1Н NMR spectrum, δ, ppm: 1.65 s (3Н, 7-Mе), 2.31 s
(6Н, 4-MеС6Н4N, 4-MеС6Н4SO2), 2.42 s (3Н, 2-Mе),
3-Acetyl-2-methyl-1-(4-methylphenyl)-5-(4-me-
thoxyphenylsulfonyl)amino-7-chloro-1H-indole (VId).
Yield 56%, mp 246–248°С. 1Н NMR spectrum, δ, ppm:
2.33 s (3Н, 4-MеС6Н4), 2.41 s (3Н, 2-Mе), 2.51 s (3Н,
СОMе), 3.78 s (3Н, MеО), 6.93 d (1Н, Н6, J6,4 1.2 Hz),
2.46 s (3Н, СОMе), 6.67 br.s (1Н, Н6), 7.27 d (2Н, Н3',5'
,
4-MеС6Н4N, J 6.0 Hz), 7.36 d (2Н, Н2',6', 4-MеС6Н4N,
J 6.0 Hz), 7.31 d (2Н, Н3'',5'', 4-MеС6Н4SO2, J 6.0 Hz),
7.63 d (2Н, Н2'',6'', 4-MеС6Н4SO2, J 6.0 Hz), 7.79 br.s
(1Н, Н4), 9.97 s (1Н, NH). Found, %: С 69.90, 69.88;
Н 5.76, 5.99; N 6.20, 6.28. C26H26N2O3S. Calculated, %:
C 69.93; Н 5.87; N 6.27.
7.26 d (2Н, Н3',5', 4-MеС6Н4, J 6.6 Hz), 7.69 d (2Н, Н2',6'
,
4-MеС6Н4, J 6.6 Hz), 7.06 d (2Н, Н3'',5'', 4-MеОС6Н4,
J 6.0 Hz), 7.34 d (2Н, Н2'',6'', 4-MеОС6Н4, J 6.0 Hz),
7.99 d (1Н, Н4), 10.16 s (1Н, NH). Found, %: С 62.10,
62.25; Н 4.65, 4.91; N 5.89, 5.74. C25H23ClN2O4S. Cal-
culated, %: C 62.17; Н 4.80; N 5.80.
3-Acetyl-2,7-dimethyl-1-(4-methylphenyl)-5-phe-
nylsulfonylamino-1H-indole (VIi). Yield 51%, mp 231–
1
232°С. Н NMR spectrum, δ, ppm: 1.65 s (3Н, 7-Mе),
2-Methyl-1-(4-methylphenyl)-5-tosylamino-7-
chloro-3-ethoxycarbonyl-1H-indole (VIe). Yield 62%,
mp 241–242°С. 1Н NMR spectrum, δ, ppm: 1.40 t (3Н,
СН2Mе, J 7.2 Hz), 2.36 s (3Н, 4-MеС6Н4SO2), 2.39 s
(3Н, 2-Mе), 2.45 s (3Н, 4-MеС6Н4N), 4.34 q (2Н,
2.31 s (3Н, 4-MеС6Н4), 2.42 s (3Н, 2-Mе), 2.46 s (3Н,
СОMе), 6.67 br.s (1Н, Н6), 7.27 d (2Н, Н3',5', 4-MеС6Н4,
J 6.0 Hz), 7.36 d (2Н, Н2',6', 4-MеС6Н4, J 6.0 Hz), 7.51–
7.76 m (5Н, Ph), 7.79 br.s (1Н, Н4), 10.04 s (1Н, NH).
Found, %: С 69.45, 69.50; Н 5.43, 5.77; N 6.45, 6.51.
C25H24N2O3S. Calculated, %: C 69.42; Н 5.59; N 6.48.
СН2Mе), 7.09 d (1Н, Н6, J6,4 1.8 Hz), 7.29 d (2Н, Н3',5'
,
4-MеС6Н4N, J 8.4 Hz), 7.38 d (2Н, Н2',6', 4-MеС6Н4N,
J 8.4 Hz), 7.33 d (2Н, Н3'',5'', MеС6Н4SO2, J 7.8 Hz),
7.72 d (2Н, Н2'',6'', 4-MеС6Н4SO2, J 7.8 Hz), 8.05 d
(1Н, Н4), 9.01 br.s (1Н, NH). Found, %: С 62.80, 62.75;
Н 4.97, 5.18; N 5.62, 5.70. C26H25ClN2O4S. Calculated,
%: C 62.83; Н 5.07; N 5.64.
2,7-Dimethyl-1-(4-methylphenyl)-5-phenylsulfo-
nylamino-3-ethoxycarbonyl-1H-indole (VIj). Yield
69%, mp 230–232°С. 1Н NMR spectrum, δ, ppm: 1.39 t
(3Н, СН2Mе, J 7.2 Hz), 1.74 s (3Н, 7-Mе), 2.37 s (3Н,
4-MеС6Н4), 2.47 s (3Н, 2-Mе), 4.31 q (2Н, СН2Mе),
6.79 d (1Н, Н6, J6,4 1.2 Hz), 7.31 d (2Н, Н3',5', 4-MеС6Н4,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

REACTIONS OF N-ARYLSULFONYLQUINONE IMINES WITH ENAMINES
1177
СН2Mе), 6.93 s (1Н, Н7), 7.32 d (2Н, Н3',5', 4-MеС6Н4N,
J 8.1 Hz), 7.47 d (2Н, Н2',6', 4-MеС6Н4N, J 8.1 Hz), 7.32 d
J 7.8 Hz), 7.41 d (2Н, Н2',6', 4-MеС6Н4, J 7.8 Hz),
7.49–7.84 m (5Н, Ph), 7.91 d (1Н, Н4), 8.78 s (1Н, NH).
Found, %: С 67.54, 67.48; Н 5.45, 5.78; N 6.02, 6.00.
C26H26N2O4S. Calculated, %: C 67.51; Н 5.67; N 6.06.
(2Н, Н3'',5'', 4-MеС6Н4SO2, J 8.1 Hz), 7.68 d (2Н, Н2'',6''
,
4-MеС6Н4SO2, J 8.1 Hz), 8.26 s (1Н, Н4), 8.38 s (1Н,
NH). Found, %: С 62.80, 62.78; Н 4.98, 5.10; N 5.60,
5.65. C26H25ClN2O4S. Calculated, %: C 62.83; Н 5.07;
N 5.64.
2,7-Dimethyl-1-(4-methoxyphenyl)-5-phenylsul-
fonylamino-3-ethoxycarbonyl-1H-indole (VIk). Yield
35%, mp 215–217°С. 1Н NMR spectrum, δ, ppm: 1.39 t
(3Н, СН2Mе, J 7.2 Hz), 1.75 s (3Н, 7-Mе), 2.37 s (3Н,
2-Mе), 3.91 s (3Н, MеО), 4.31 q (2Н, СН2Mе), 6.78 d
(1Н, Н6, J6,4 1.2 Hz), 7.12 d (2Н, Н3',5', 4-MеОС6Н4,
J 9.0 Hz), 7.35 d (2Н, Н2',6', 4-MеОС6Н4, J 9.0 Hz),
7.49–7.85 m (5Н, Ph), 7.91 d (1Н, Н4), 8.80 s (1Н,
NH). 13С NMR spectrum, δ, ppm: 21.81 (2-Me), 23.88
(CH2Me), 27.95 (7-Me), 64.84 (OMe), 68.75 (CH2Me),
114.19 (C3), 122.35 (C4), 122.42 (C6), 124.08 (C3''),
130.19 (C7), 131.63 (C3a), 137.04 (C2'), 137.33 (C7a),
138.65 (C2''), 140.36 (C3'), 140.80 (C4'), 141.35 (C1''),
142.25 (C1'), 143.46 (C2), 156.80 (C5), 170.19 (C4''),
174.82 (C=O). Found, %: С 65.20, 65.29; Н 5.34, 5.59;
N 5.81, 5.84. C26H26N2O5S. Calculated, %: C 65.25;
Н 5.48; N 5.85.
2-Methyl-1-(4-methoxyphenyl)-5-tosylamino-6-
chloro-3-ethoxycarbonyl-1H-indole (VIo). Yield 63%,
mp 188–190°С. 1Н NMR spectrum, δ, ppm: 1.40 t (3Н,
СН2Mе, J 7.2 Hz), 2.37 s (3Н, 4-MеС6Н4), 2.51 s (3Н,
2-Mе), 3.91 s (3Н, MеО), 4.36 q (2Н, СН2Mе), 6.92 s
(1Н, Н7), 7.17 d (2Н, Н3'5', 4-MеОС6Н4, J 8.4 Hz), 7.37 d
(2Н, Н2',6', 4-MеОС6Н4, J 8.4 Hz), 7.32 d (2Н, Н3'',5''
,
4-MеС6Н4, J 8.1 Hz), 7.67 d (2Н, Н2'',6'', 4-MеС6Н4,
J 8.1 Hz), 8.25 s (1Н, Н4), 8.37 s (1Н, NH). Found,
%: С 60.84, 60.80; Н 4.85, 4.98; N 5.43, 5.47.
C26H25ClN2O5S. Calculated, %: C 60.87; Н 4.91; N 5.46.
3-Acetyl-2,6-dimethyl-1-(4-methylphenyl)-5-(4-
methoxyphenylsulfonyl)amino-1H-indole (VIp). Yield
71%, mp 224–226°С. 1Н NMR spectrum, δ, ppm: 2.22 s
(3Н, 6-Mе), 2.40 s (3Н, 4-MеС6Н4), 2.47 s (3Н, 2-Mе),
2.49 s (3Н, СОMе), 3.88 (3Н, MеО), 6.79 s (1Н, Н7),
7.05 d (2Н, Н3'',5'', 4-MеОС6Н4, J 6.6 Hz), 7.31 d (2Н,
Н3',5', 4-MеС6Н4, J 8.4 Hz), 7.46 d (2Н, Н2',6', 4-MеС6Н4,
J 8.4 Hz), 7.66 d (2Н, Н2'',6'', 4-MеОС6Н4, J 6.6 Hz),
7.70 s (1Н, Н4), 8.23 s (1Н, NH). Found, %: 67.52, 67.60;
Н 5.54, 5.78; N 6.01, 6.07. C26H26N2O4S. Calculated, %:
C 67.51; Н 5.67; N 6.06.
3-Acetyl-2,7-dimethyl-1-(4-methylphenyl)-5-(4-
chlorophenylsulfonyl)amino-1H-indole (VIl). Yield
85%, mp 266–268°С. 1Н NMR spectrum, δ, ppm: 1.66 s
(3Н, 7-Mе), 2.32 s (3Н, 4-MеС6Н4), 2.42 s (3Н, 2-Mе),
2.45 s (3Н, СОMе), 6.67 br.s (1Н, Н6), 7.28 d (2Н, Н3',5'
,
4-MеС6Н4, J 6.0 Hz), 7.37 d (2Н, Н2',6', 4-MеС6Н4,
J 6.0 Hz), 7.62 d (2Н, Н3'',5'', 4-СlС6Н4, J 6.3 Hz), 7.73 d
(2Н, Н2'',6'', 4-ClС6Н4, J 6.3 Hz), 7.79 br.s (1Н, Н4),
10.11 s (1Н, NH). Found, %: С 64.35, 64.28; Н 4.77, 5.07;
N 6.02, 6.05. C25H23ClN2O3S. Calculated, %: C 64.30;
Н 4.96; N 6.00.
3-Acetyl-2,6-dimethyl-1-(4-methylphenyl)-5-
phenylsulfonylamino-1H-indole (VIq). Yield 52%,
1
mp 200–202°С. Н NMR spectrum, δ, ppm: 2.19 s
3-Acetyl-2,7-dimethyl-1-(4-methylphenyl)-5-(3-
nitrophenylsulfonyl)amino-1H-indole (VIm). Yield
74%, mp 132–135°С. 1Н NMR spectrum, δ, ppm: 1.66 s
(3Н, 7-Mе), 2.31 s (3Н, 4-MеС6Н4), 2.42 s (3Н, 2-Mе),
(3Н, 6-Mе), 2.37 s (3Н, 4-MеС6Н4), 2.47s (3Н, 2-Mе),
2.48 s (3Н, СОMе), 6.79 s (1Н, Н7), 7.30 d (2Н, Н3',5'
,
4-MеС6Н4, J 8.1 Hz), 7.46 d (2Н, Н2',6', 4-MеС6Н4,
J 8.4 Hz), 7.53–7.78 m (5Н, Ph), 7.65 s (1Н, Н4), 8.39 s
(1Н, NH). Found, %: С 69.48, 69.35; Н 5.45, 5.65;
N 6.49, 6.41. C25H24N2O3S. Calculated, %: C 69.42;
Н 5.59; N 6.48.
2.46 s (3Н, СОMе), 6.67 br.s (1Н, Н6), 7.27 d (2Н, Н3',5'
,
4-MеС6Н4, J 6.0 Hz), 7.36 d (2Н, Н2',6', 4-MеС6Н4,
J 6.0 Hz), 7.79 br.s (1Н, Н4), 7.84 t (1Н, Н5'', J 6.3 Hz),
8.10–8.11 d.d (1Н, Н6'', J 0.9 Hz), 8.44–8.45 d.d (1Н,
Н4'', J 0.9 Hz), 8.52 br.s (1Н, Н2''), 10.32 s (1Н, NH).
Found, %: С 62.90, 62.85; Н 4.76, 4.98; N 8.85, 8.87.
C25H23N3O5S. Calculated, %: C 62.88; Н 4.85; N 8.80.
2,6-Dimethyl-1-(4-methylphenyl)-5-phenylsulfo-
nylamino-3-ethoxycarbonyl-1H-indole (VIr). Yield
49%, mp 222–224°С. 1Н NMR spectrum, δ, ppm: 1.32 t
(3Н, СН2Mе, J 6.9 Hz), 2.20 s (3Н, 6-Mе), 2.47 s (3Н,
4-MеС6Н4), 2.50 s (3Н, 2-Mе), 4.27 q (2Н, СН2Mе),
6.78 s (1Н, Н7), 7.31 d (2Н, Н3',5', 4-MеС6Н4, J 8.7 Hz),
7.46 d (2Н, Н2',6', 4-MеС6Н4, J 8.7 Hz), 7.53–7.75 m
(5Н, Ph), 7.77 s (1Н, Н4), 8.29 s (1Н, NH). Found, %:
2-Methyl-1-(4-methylphenyl)-5-tosylamino-6-
chloro-3-ethoxycarbonyl-1H-indole (VIn). Yield 36%,
mp 173–174°С. 1Н NMR spectrum, δ, ppm: 1.41 t (3Н,
СН2Mе, J 7.2 Hz), 2.39 s (3Н, 4-MеС6Н4SO2), 2.47 s
(3Н, 2-Mе), 2.53 s (3Н, 4-MеС6Н4N), 4.36 q (2Н,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

AVDEENKO et al.
1178
1
С 67.48, 67.45; Н 5.56, 5.78; N 6.02, 6.08. C26H26N2O4S.
Calculated, %: C 67.51; Н 5.67; N 6.06.
219–220°С. Н NMR spectrum, δ, ppm: 2.53 s (3Н,
2-Mе), 2.78 s (3Н, СОMе), 3.77 s (3Н, MеО), 7.05 d (2Н,
Н3',5', 4-MеОС6Н4, J 8.7 Hz), 7.14 d (1Н, Н6, J6,4 1.2 Hz),
7.68 d (2Н, Н2',6', 4-MеОС6Н4, J 8.7 Hz), 7.76 d (1Н, Н4),
10.30 с (1Н, NH). Found, %: 54.80, 54.95; Н 4.01, 4.15;
N 3.59, 3.52. C18H16ClNO5S. Calculated, %: C 54.89;
Н 4.09; N 3.56.
2,6-Dimethyl-1-(4-methoxyphenyl)-5-phenylsul-
fonylamino-3-ethoxycarbonyl-1H-indole (VIs). Yield
59%, mp 212–214°С. 1Н NMR spectrum, δ, ppm: 1.32 t
(3Н, СН2Mе, J 7.2 Hz), 2.20 s (3Н, 6-Mе), 2.49 s (3Н,
2-Mе), 3.92 s (3Н, MеО), 4.27 q (2Н, СН2Mе), 6.77 s
(1Н, Н7), 7.17 d (2Н, Н3',5', 4-MеС6Н4, J 8.7 Hz), 7.35 d
(2Н, Н2',6', 4-MеС6Н4, J 8.7 Hz), 7.53–7.76 m (5Н, Ph),
7.76 s (1Н, Н4), 8.29 s (1Н, NH). Found, %: С 65.28,
65.20; Н 5.35, 5.55; N 5.81, 5.88. C26H26N2O5S. Calcu-
lated, %: C 65.25; Н 5.48; N 5.85.
2-Methyl-5-tosylamino-7-chloro-3-ethoxycarbon-
yl-1-benzofuran (VIId). Yield 29%, mp 185–186°С.
1Н NMR spectrum, δ, ppm: 1.37 t (3Н, СН2Mе, J 7.2 Hz),
2.32 s (3Н, 4-MеС6Н4), 2.71 s (3Н, 2-Mе), 4.31 q (2Н,
СН2Mе), 7.15 d (1Н, Н6, J6,4 1.2 Hz), 7.36 d (2Н, Н3',5'
,
4-MеС6Н4, J 7.8 Hz), 7.65 d (2Н, Н2',6', 4-MеС6Н4,
J 7.8 Hz), 7.66 d (1Н, Н4), 10.47 br.s (1Н, NH).
Found, %: С 55.85, 55.98; Н 4.33, 4.46; N 3.37, 3.50.
C19H18ClNO5S. Calculated, %: C 55.95; Н 4.45; N 3.43.
3-Acetyl-2,6,7-trimethyl-5-(3-nitrophenylsulfonyl)
amino-1-(4-methylphenyl)-1H-indole (VIt). Yield
74%, mp 232–234°С. 1Н NMR spectrum, δ, ppm: 1.74 s
(3Н, 7-Mе), 2.20 s (3Н, 6-Mе), 2.33 s (3Н, 4-MеС6Н4),
2.35 s (3Н, 2-Mе), 2.48 s (3Н, СОMе), 7.29 d (2Н, Н3',5'
,
3-Acetyl-2-methyl-5-tosylamino-7-chloro-1-ben-
1
4-MеС6Н4, J 8.1 Hz), 7.44 d (2Н, Н2',6', 4-MеС6Н4,
J 8.1 Hz), 7.53 s (1Н, Н4), 7.91 t (1Н, Н5'', J 7.8 Hz),
8.14 d (1Н, Н6'', J 0.9 Hz), 8.52 d (1Н, Н2''), 8.53 d (1Н,
Н4'', J 0.9 Hz), 8.74 br.s (1Н, NH). Found, %: С 63.58,
63.59; Н 5.10, 5.25; N 8.59, 8.51. C26H25N3O5S. Calcu-
lated, %: C 63.53; Н 5.13; N 8.55.
zofuran (VIIe). Yield 85%, mp 255–256°С. Н NMR
spectrum, δ, ppm: 2.35 s (3Н, 4-MеС6Н4), 2.56 s (3Н,
2-Mе), 2.82 с (3Н, СОMе), 7.29 d (1Н, Н6, J6,4 1.8 Hz),
7.32 d (2Н, Н3',5', 4-MеС6Н4, J 7.8 Hz), 7.69 d (2Н, Н2',6'
,
4-MеС6Н4, J 7.8 Hz), 7.85 d (1Н, Н4), 9.12 br.s (1Н, NH).
Found, %: С 57.25, 57.19; Н 4.17, 4.31; N 3.65, 3.69.
C18H16ClNO4S. Calculated, %: C 57.22; Н 4.27; N 3.71.
2,6,7-Trimethyl-1-(4-methoxyphenyl)-5-(3-nitro-
phenylsulfonyl)amino-3-ethoxycarbonyl-1H-indole
(VIu). Yield 75%, mp 178–180°С. 1Н NMR spectrum,
δ, ppm: 1.23 t (3Н, СН2Mе, J 7.2 Hz), 1.78 s (3Н, 7-Mе),
2.22 s (3Н, 6-Mе), 2.36 s (3Н, 2-Mе), 3.92 s (3Н, MеО),
4.19 q (2Н, СН2Mе), 7.14 d (2Н, Н3',5', 4-MеОС6Н4,
J 8.7 Hz), 7.34 d (2Н, Н2',6', 4-MеОС6Н4, J 8.7 Hz), 7.51 s
(1Н, Н4), 7.91 t (1Н, Н5'', J 7.5 Hz), 8.12 d (1Н, Н6'',
J 0.9 Hz), 8.52 d (1Н, Н2''), 8.54 d (1Н, Н4'', J 0.9 Hz),
8.73 s (1Н, NH). Found, %: С 60.35, 60.39; Н 5.01, 5.15;
N 7.78, 7.86. C27H27N3O7S. Calculated, %: C 60.32;
Н 5.06; N 7.82.
3-Acetyl-2,7-dimethyl-5-phenylsulfonylamino-1-
benzofuran (VIIf). Yield 35%, mp 222–224°С. 1Н NMR
spectrum, δ, ppm: 2.39 s (3Н, 7-Mе), 2.51 s (3Н, 2-Mе),
2.76 s (3Н, CОMе), 7.03 d (1Н, Н6, J6,4 1.2 Hz), 7.47–
7.80 m (5Н, Ph), 7.67 d (1Н, Н4), 8.88 br.s (1Н, NH).
Found, %: С 62.90, 62.88; Н 4.85, 5.03; N 4.05, 4.03.
C18H17NO4S. Calculated, %: C 62.96; Н 4.99; N 4.08.
2,7-Dimethyl-5-phenylsulfonylamino-3-ethoxy-
carbonyl-1-benzofuran (VIIg). Yield 40%, mp 185–
186°С. 1Н NMR spectrum, δ, ppm: 1.34 t (3Н, СН2Mе,
J 6.6 Hz), 2.34 s (3Н, 7-Mе), 2.67 s (3Н, 2-Mе), 4.29 q
(2Н, СН2Mе), 6.90 br.s (1Н, Н6), 7.48 br.s (1Н, Н4),
7.51–7.76 m (5Н, Ph), 10.21 br.s (1Н, NH). Found, %:
С 61.15, 61.18; Н 5.01, 5.23; N 3.70, 3.68. C19H19NO5S.
Calculated, %: C 61.11; Н 5.13; N 3.75.
2-Methyl-5-tosylamino-3-ethoxycarbonyl-1-ben-
1
zofuran (VIIb). Yield 35%, mp 130–132°С. Н NMR
spectrum, δ, ppm: 1.35 t (3Н, СН2Mе, J 6.9 Hz), 2.31 s
(3Н, 4-MеС6Н4), 2.68 s (3Н, 2-Mе), 4.30 q (2Н, СН2Mе),
7.03–7.06 d.d (1Н, Н6, J6,7 8.4, J6,4 0.9 Hz), 7.31 d (2Н,
Н3',5', 4-MеС6Н4, J 7.8 Hz), 7.47 d (1Н, Н7), 7.61 d
(2Н, Н2',6', 4-MеС6Н4, J 7.8 Hz), 7.65 d (1Н, Н4), 10.21
br.s (1Н, NH). Found, %: С 61.08, 61.18; Н 5.03, 5.20;
N 3.80, 3.68. C19H19NO5S. Calculated, %: C 61.11;
Н 5.13; N 3.75.
3-Acetyl-2-methyl-5-tosylamino-6-chloro-1-benzo-
furan (VIIh). Yield 80%, mp 176–178°С. 1Н NMR spec-
trum, δ, ppm: 2.37 s (3Н, 4-MеС6Н4), 2.49 s (3Н, 2-Mе),
2.76 s (3Н, CОMе), 7.34 d (2Н, Н3',5', 4-MеС6Н4,
J 8.1 Hz), 7.57 d (2Н, Н2',6', 4-MеС6Н4, J 8.1 Hz),
7.78 s (1Н, Н7), 7.81 s (1Н, Н4), 9.86 br.s (1Н, NH).
Found, %: С 57.12, 57.21; Н 4.17, 4.30; N 3.75, 3.79.
C18H16ClNO4S. Calculated, %: C 57.22; Н 4.27; N 3.71.
3-Acetyl-2-methyl-5-(4-methoxyphenylsulfonyl)
amino-7-chloro-1-benzofuran (VIIc). Yield 68%, mp
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

REACTIONS OF N-ARYLSULFONYLQUINONE IMINES WITH ENAMINES
1179
3-Acetyl-2,6-dimethyl-5-phenylsulfonylamino-1-
benzofuran (VIIi). Yield 50%, mp 193–195°С. 1Н NMR
spectrum, δ, ppm: 2.10 s (3Н, 6-Mе), 2.43 s (3Н, 2-Mе),
2.73 s (3Н, CОMе), 7.40 s (1Н, Н7), 7.49 s (1Н, Н4),
7.52–7.66 m (5Н, Ph), 9.59 br.s (1Н, NH). Found, %:
С 62.85, 62.94; Н 4.88, 5.03; N 4.10, 4.15. C18H17NO4S.
Calculated, %: C 62.96; Н 4.99; N 4.08.
Found, %: С 67.85, 67.98; Н 5.61, 5.78; N 5.25, 5.34.
C30H30N2O5S. Calculated, %: C 67.90; Н 5.70; N 5.28.
2-[2-(4-Methoxyphenyl)amino-4-tosylamino-1-
(ethoxycarbonyl)prop-1-enyl]-1-naphthol (Xb). Yield
1
45%. Н NMR spectrum, δ, ppm: 1.04 t (3Н, СН2Mе,
J 6.9 Hz), 1.61 s (3Н, C=C–Mе), 2.33 s (3Н, 4-MeC6H4),
3.82 s (3Н, MеО), 3.95–4.06 m (2Н, СН2Mе), 6.86 s
(1Н, Н3), 6.98 d (2Н3',5', 4-MeOС6Н4, J 8.7 Hz), 7.25
3-Acetyl-2,6,7-trimethyl-5-phenylsulfonylamino-1-
benzofuran (VIIj). Yield 75%, mp 209–210°С. 1Н NMR
spectrum, δ, ppm: 2.07 s (3Н, 7-Mе), 2.32 s (3Н, 6-Mе),
2.37 s (3Н, 2-Mе), 2.73 s (3Н, СОMе), 7.23 s (1Н, Н4),
7.52–7.65 m (5Н, Ph), 9.59 s (1Н, NH). Found, %:
С 63.88, 63.90; Н 5.29, 5.42; N 3.95, 3.99. C19H19NO4S.
Calculated, %: C 63.85; Н 5.36; N 3.92.
d (2Н, Н2',6', 4-MeОC6H4, J 8.7 Hz), 7.25 d (2Н, Н3'',5''
,
4-MeC6H4, J 8.4 Hz), 7.41 d (1Н, Н8, J8,7 5.7 Hz), 7.42 d
(1Н, Н5, J5,6 5.7 Hz), 7.59 d (2Н, Н2'',6'', 4-MeC6H4,
J 8.4 Hz), 8.13 t (1Н, Н7), 8.24 t (1Н, Н6), 8.22 s (1Н,
NH), 8.60 br.s (1Н, NH), 11.33 br.s (1Н, ОН). Found, %:
С 65.90, 65.85; Н 5.49, 5.57; N 5.15, 5.10. C30H30N2O6S.
Calculated, %: C 65.92; Н 5.53; N 5.12.
2,6,7-Trimethyl-5-phenylsulfonylamino-3-eth-
oxycarbonyl-1-benzofuran (VIIk). Yield 88%,
mp 174–175°С. 1Н NMR spectrum, δ, ppm: 1.23 t (3Н,
СН2Mе, J 6.9 Hz), 2.11 s (3Н, 7-Mе), 2.33 s (3Н, 6-Mе),
2.69 s (3Н, 2-Mе), 4.21 q (2Н, СН2Mе), 7.11 s (1Н,
Н4), 7.53–7.65 m (5Н, Ph), 9.58 s (1Н, NH). Found, %:
С 62.05, 62.07; Н 5.39, 5.48; N 3.68, 3.65. C20H21NO5S.
Calculated, %: C 62.00; Н 5.46; N 3.62.
2-Methyl-1-(4-methylphenyl)-5-tosylamino-3-
ethoxycarbonyl-1H-benzo[g]indole (XIа). Yield 53%,
mp 245–246°С. 1Н NMR spectrum, δ, ppm: 1.33 t (3Н,
СН2Mе, J 6.9 Hz), 2.40 s (3Н, 4-MеС6Н4SO2), 2.46 s (3Н,
4-MеС6Н4N), 2.55 s (3Н, 2-Mе), 4.30 q (2Н, СН2Mе),
7.07 d (1Н, Н9, J9,8 7.8 Hz), 7.13 t (1Н, Н8), 7.32 t (1Н,
Н7), 7.35 d (2Н, Н3',5', 4-MеС6Н4SO2, J 8.1 Hz), 7.42 d
(2Н, Н3'',5'', 4-MеС6Н4N, J 8.1 Hz), 7.55 d (2Н, Н2'',6''
,
3-Acetyl-2,4,6-trimethyl-5-phenylsulfonyl-amino-
1-benzofuran (VIIl). Yield 25%, mp 158–159°С.
1Н NMR spectrum, δ, ppm: 1.77 s (3Н, 6-Mе), 1.93 s (3Н,
4-Mе), 2.07 s (3Н, 2-Mе), 2.24 s (3Н, СОMе), 6.82s (1Н,
Н7), 7.57–7.68 m (5Н, Ph), 9.43 br.s (1Н, NH). Found, %:
С 63.80, 63.78; Н 5.25, 5.41; N 3.95, 3.98. C19H19NO4S.
Calculated, %: C 63.85; Н 5.36; N 3.92.
4-MеС6Н4N, J 8.1 Hz), 7.69 d (2Н, Н2',6', 4-MеС6Н4SO2,
J 8.1 Hz), 8.03 s (1Н, Н4), 8.35 d (1Н, Н6, J6,7 8.4 Hz),
8.78 br.s (1Н, NH). Found, %: С 70.28, 70.30; Н 5.47,
5.56; N 5.50, 5.41. C30H28N2O4S. Calculated, %: C 70.29;
Н 5.51; N 5.46.
2-Methyl-1-(4-methoxyphenyl)-5-tosylamino-3-
ethoxycarbonyl-1H-benzo[g]indole (XIb). Yield 61%,
mp 232–234°С. 1Н NMR spectrum, δ, ppm: 1.34 t (3Н,
СН2Mе, J 7.2 Hz), 2.37 s (3Н, 4-MеС6Н4), 2.47 s (3Н,
2-Mе), 3.95 s (3Н, MеО), 4.32 q (2Н, СН2Mе), 6.73 br.s
(1Н, NH), 7.05 d (1Н, Н9, J9,8 8.4 Hz), 7.12 t (1Н,
Н8), 7.11 d (2Н, Н3',5', 4-MеОС6Н4, J 7.5 Hz), 7.13 d
2,4,6-Trimethyl-5-phenylsulfonylamino-3-eth-
oxycarbonyl-1-benzofuran (VIIm). Yield 75%,
mp 185–186°С. 1Н NMR spectrum, δ, ppm: 1.28 t (3Н,
СН2Mе, J 6.9 Hz), 2.01 s (3Н, 6-Mе), 2.11 s (3Н, 4-Mе),
2.58 s (3Н, 2-Mе), 4.27 q (2Н, СН2Mе), 7.26 s (1Н, Н7),
7.54–7.69 m (5Н, Ph), 9.43 br.s (1Н, NH). Found, %:
С 62.01, 62.05; Н 5.38, 5.50; N 3.65, 3.68. C20H21NO5S.
Calculated, %: C 62.00; Н 5.46; N 3.62.
(2Н, Н3'',5'', 4-MеС6Н4, J 8.1 Hz), 7.23 d (2Н, Н2',6'
,
4-MеОС6Н4, J 7.5 Hz), 7.32 t (1Н, Н7, J7,6 8.4 Hz),
7.67 d (2Н, Н2'',6'', 4-MеС6Н4, J 8.1 Hz), 7.91 s (1Н, Н4),
8.19 d (1Н, Н6). 13С NMR spectrum, δ, ppm: 12.47 (2-
Me), 14.37 (CH2Me), 21.28 (4-MeC6H4), 55.54 (OMe),
59.48 (CH2Me), 106.25 (C4), 109.56 (C3), 115.30 (C3''),
120.52 (C2'), 122.36 (C5a), 123.97 (C2''), 125.49 (C10),
126.21 (C9a), 127.51 (C7,8), 128.43 (C3a), 129.29 (C3'),
129.66 (C6,9), 130.05 (C1''), 131.60 (C5), 137.01 (C1'),
143.09 (C2), 145.15 (C4'), 160.31 (C4''), 165.57 (C=O).
Found, %: С 68.25, 68.15; Н 5.29, 5.39; N 5.35, 5.40.
C30H28N2O5S. Calculated, %: C 68.16; Н 5.34; N 5.30.
4-Tosylamino-2-[2-tosylamino-1-(ethoxycarbonyl)
prop-1-enyl]-1-naphthol (Xа). Yield 61%, mp 232–
234°С. 1Н NMR spectrum, δ, ppm: 1.05 t (3Н, СН2Mе,
J 6.9 Hz), 1.66 s (3Н, C=C–Mе), 2.34 s (6Н, 4-MeC6H4N,
4-MeC6H4SO2), 3.95–4.06 m (2Н, СН2Mе), 6.85 s (1Н,
Н3), 7.10 d (2Н, Н3',5', 4-MeC6H4N, J 8.1 Hz), 7.25 d
(2Н, Н2',6', 4-MeC6H4N, J 8.1 Hz), 7.26 d (2Н, Н3'',5''
,
4-MeC6H4SO2, J 8.1 Hz), 7.41 d (1Н, Н8, J8,7 5.7 Hz),
7.42 d (1Н, Н5, J5,6 5.7 Hz), 7.60 d (2Н, Н2'',6'', 4-MeC6H-
4SO2, J 8.1 Hz), 8.13 t (1Н, Н7), 8.25 t (1Н, Н6), 8.26
s (1Н, NН), 8.61 br.s (1Н, NH), 11.33 br.s (1Н, ОН).
3-Acetyl-2-methyl-5-tosylaminonaphtho[1,2-b]-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011

AVDEENKO et al.
1180
1
10. Grinev, A.N., Shvedov, V.I., Panisheva, E.K., Bogdano-
va, N.S., Nikolaeva, I.S., and Pershin, G.N., Khim.-Farm.
Zh., 1971, no. 5, p. 3.
furan (XIIа). Yield 74%, mp 230–231°С. Н NMR
spectrum, δ, ppm: 2.37 s (3Н, 4-MеС6Н4), 2.51 s (3Н,
2-Mе), 2.88 s (3Н, СОMе), 7.30 d (2Н, Н3',5', 4-MеС6Н4,
J 8.1 Hz), 7.52 t (1Н, Н8, J 6.0 Hz), 7.64 d (2Н, Н2',6'
,
11. Shvedov, V.I., Kurilo, G.N., and Grinev,A.N., Khim.-Farm.
Zh., 1970, no. 4, p. 7.
4-MеС6Н4, J 8.1 Hz), 7.67 t (1Н, Н7), 7.81 s (1Н, H4),
8.23 d (1Н, Н9, J9,8 8.4 Hz), 8.27 d (1Н, Н6, J6,7 8.1 Hz),
8.93 s (1Н, NH). Found, %: С 67.10, 67.17; Н 4.78,
4.91; N 3.67, 3.55. C22H19NO4S. Calculated, %: C 67.16;
Н 4.87; N 3.56.
12. Grinev, A.N., Ermakova, V.N., Vrotek, E., and
Terent’ev,A.P., Zh. Obshch. Khim., 1959, vol. 29, p. 2777.
13. Bogdanov, G.N., Titov, E.A., Shtol’ko, V.N., and
Grishchenko,A.S., Izv. Akad. Nauk SSSR, Ser. Khim., 1972,
p. 2814.
2-Methyl-5-tosylamino-3-ethoxycarbonyl-
naphtho[1,2-b]furan (XIIб). Yield 49%, mp 188–
189°С. 1Н NMR spectrum, δ, ppm: 1.37 t (3Н, СН2Mе,
J 7.2 Hz), 2.35 s (3Н, 4-MеС6Н4), 2.83 s (3Н, 2-Mе),
4.35 q (2Н, СН2Mе), 6.86 br.s (1Н, NH), 7.17 d (2Н,
Н3',5', 4-MeC6H4, J 8.1 Hz), 7.46 t (1Н, Н8, J8,7 Hz), 7.57 t
(1Н, Н7), 7.71 s (1Н, Н4), 7.64 d (2Н, Н2',6', 4-MeC6H4,
J 8.1 Hz), 8.05 d (1Н, Н9, J9,8 8.4 Hz), 8.19 d (1Н, Н6,
J6,7 8.1 Hz). 13С NMR spectrum, δ, ppm: 14.20 (2-Me),
14.26 (CH2Me), 21.38 (4-MeC6H4), 60.27 (CH2Me),
109.99 (C4), 118.83 (C3), 119.79 (C10), 120.90 (C5a),
123.52 (C7,8), 125.68 (C3a), 126.75 (C6,9), 127.43 (C2'),
127.95 (C9a), 129.39 (C3'), 136.37 (C1'), 143.44 (C5),
147.74 (C4'), 162.86 (C2), 164.05 (C=O). Found, %:
С 65.21, 65.15; Н 4.95, 5.10; N 3.38, 3.25. C23H21NO5S.
Calculated, %: C 65.23; Н 5.00; N 3.31.
14. Titov, E.A. and Grishchenko, A.S., Khim, Khim. Tekhnol.,
1972, vol. 15, p. 239.
15. Titov, E.A. and Grishchenko, A.S., Khim. Khim. Tekhnol.,
1973, vol. 16, p. 1055.
16. Lyubchanskaya, V.M., Panisheva, E.K., Savina, S.A.,
Alekseeva, L.M., Shashkov, A.S., and Granik, V.G., Izv.
Akad. Nauk, Ser. Khim., 2005, p. 1640.
17. Titov, E.A., Grishchenko, A.S., Prikhod’ko, V.I., and
Kost, A.N., Zh. Org. Khim., 1974, vol. 10, p. 583.
18. Titov, E.A., Grishchenko,A.S., Gura, L.A., and Kost,A.N.,
Khim. Geterotsikl. Soedin., 1973, p. 1451.
19. Titov, E.A. and Grishchenko, A.S., Vopr. Khim. Khim.
Tekhnol., 1972, no. 25, p. 40.
20. Burgi, H.-B. and Dunitz, J.D., Structure Correlation,
Weinheim: VCH, 1994, vol. 2, p. 741.
21. Avdeenko, A.P. and Konovalova, S.A., Zh. Org. Khim.,
2006, vol. 42, p. 689.
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