Regioselectivity in the reactions of N-(polychloroethylidene)-sulfonamides with 1H-pyrrole and 1-methyl-1H-pyrrole

Article abstract of DOI:10.1134/S1070428008090145

N-(2,2,2-Trichloroethylidene)arenesulfonamides react with 1H-pyrrole and 1-methyl-1H-pyrrole to give the corresponding N-[2,2,2-trichloro-1-(1H-pyrrol-2- yl)ethyl]arenesulfonamides. The reaction of N-(2,2,2-trichloroethylidene) trifluoromethanesulfonamide with pyrrole leads to a mixture of 2-mono-and 2,5-disubstituted pyrroles, whereas in the reaction with 1-methyl-1H-pyrrole only the 2-substituted compound is formed. N-(2,2-Dichloro-2-phenylethylidene)- 4-methylbenzenesulfonamide reacts with 1H-pyrrole to form N-[2,2-dichloro-2- phenyl-1-(1H-pyrrol-2-yl)ethyl]-4-methylbenzenesulfonamide, and its reaction with 1-methyl-1H-pyrrole gives a mixture of 2-and 3-monosubstituted derivatives. The results of quantum-chemical calculations of the initial reactants and products indicate that the process is orbital-controlled. A good agreement is observed between the experimental data and theoretical conclusions concerning the dependence of the reaction regioselectivity on the nature of substituents in the electrophile molecule.

Full text of DOI:10.1134/S1070428008090145

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 9, pp. 1332–1337. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.B. Rozentsveig, B.A. Shainyan, E.V. Kondrashov, E.V. Rudyakova, G.N. Rozentsveig, K.A. Chernyshev, G.G. Levkovskaya, 2008,
published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 9, pp. 1348–1353.
Regioselectivity in the Reactions of N-(Polychloroethylidene)-
sulfonamides with 1H-Pyrrole and 1-Methyl-1H-pyrrole
I. B. Rozentsveig, B. A. Shainyan, E. V. Kondrashov, E. V. Rudyakova, G. N. Rozentsveig,
K. A. Chernyshev, and G. G. Levkovskaya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: i_roz@irioch.irk.ru
Received January 28, 2008
Abstract—N-(2,2,2-Trichloroethylidene)arenesulfonamides react with 1H-pyrrole and 1-methyl-1H-pyrrole to
give the corresponding N-[2,2,2-trichloro-1-(1H-pyrrol-2-yl)ethyl]arenesulfonamides. The reaction of N-(2,2,2-
trichloroethylidene)trifluoromethanesulfonamide with pyrrole leads to a mixture of 2-mono- and 2,5-disubsti-
tuted pyrroles, whereas in the reaction with 1-methyl-1H-pyrrole only the 2-substituted compound is formed.
N-(2,2-Dichloro-2-phenylethylidene)-4-methylbenzenesulfonamide reacts with 1H-pyrrole to form N-[2,2-di-
chloro-2-phenyl-1-(1H-pyrrol-2-yl)ethyl]-4-methylbenzenesulfonamide, and its reaction with 1-methyl-1H-pyr-
role gives a mixture of 2- and 3-monosubstituted derivatives. The results of quantum-chemical calculations of
the initial reactants and products indicate that the process is orbital-controlled. A good agreement is observed
between the experimental data and theoretical conclusions concerning the dependence of the reaction regio-
selectivity on the nature of substituents in the electrophile molecule.
DOI: 10.1134/S1070428008090145
Reactions of N-(polychloroethylidene)arenesulfon-
amides with pyrroles open convenient synthetic ap-
proaches to important compounds whose molecules in-
clude a pyrrole fragment and aminosulfonyl and poly-
haloalkyl groups [1, 2] that are responsible for their
biological activity and possibility for further chemical
modifications. In continuation of our systematic
studies on the reactivity of azomethine systems activat-
ed by strong electron-withdrawing substituents toward
hetarenes [1], in the present work we examined amido-
alkylation of pyrroles with Schiff bases derived from
trifluoromethane- and arenesulfonamides, on the one
hand, and trichloroacetaldehyde and dichloro(phenyl)-
acetaldehyde, on the other.
It was shown previously that 4-chloro-N-(2,2,2-tri-
chloroethylidene)benzenesulfonamide regioselectively
reacts with pyrrole and 1-substituted pyrroles in the
absence of a catalyst or in the presence of boron tri-
fluoride–ether complex, yielding up to 60% of the cor-
responding 2-monosubstituted derivatives, 4-chloro-N-
[2,2,2-trichloro-1-(1-R-1H-pyrrol-2-yl)ethyl]benzene-
sulfonamides [2]. In the recent publication [4] we
reported on unusual reaction of highly electrophilic
N-(2,2,2-trichloroethylidene)trifluoromethanesulfon-
amide (I) with pyrrole, which gave either 2-mono- or
2,5-disubstituted pyrrole in up to 80% yield, depending
on the conditions.
We failed to obtain disubstituted product in the
reaction of pyrrole with N-(2,2,2-trichloroethylidene)-
benzenesulfonamide (II) even using 2 equiv of the
latter, i.e., under the conditions ensuring formation of
It is known that electrophilic reagents react with
pyrroles at both α- and β-positions of the pyrrole ring.
For example, the reaction of 1-methyl-1H-pyrrole with
ethyl (4-tolylsulfonylimino)acetate in the presence of
CuPF6 gives a mixture of 2- and 3-[ethoxycarbonyl-
(p-tolylsulfonylamino)methyl]-substituted 1-methyl-
pyrroles with an overall yield of 89% [3]. Analogous
reaction with 2-acetyl-1H-pyrrole results in the forma-
tion of the corresponding 4-substituted derivative.
Scheme 1.
H
N
PhSO2
SO2Ph
+
N
CCl3
N
N
H
H
CCl3
II
III
1332

REGIOSELECTIVITY IN THE REACTIONS OF N-(POLYCHLOROETHYLIDENE)...
1333
Scheme 2.
H
N
Cl
Cl
4-MeC6H4SO2
SO2C6H4Me-4
Ph
+
N
N
H
N
Ph
H
Cl
N
Cl
IV
V
Scheme 3.
H
H
N
N
SO2C6H4Me-4
Ph
SO2C6H4Me-4
Ph
Me
IV
+
+
N
N
Me
Cl
Cl
Me
Cl
Cl
VII
VI
2,5-disubstituted pyrrole from compound I [4]. In-
stead, 2-substituted pyrrole III was isolated in 74%
yield (Scheme 1).
C3, respectively (coupling through 2 and 3 bonds). The
COSY spectrum of VI revealed correlation between
3-H and 4-H in the pyrrole ring, as well as between
4-H and 5-H. These findings confirm the structure of
VI as 2-substituted pyrrole. In the HMBC spectrum of
VII, the 3-CH proton showed three cross peaks with
C3, C2, and C4, while protons in the methyl group dis-
played correlations with C2 and C5. The COSY spec-
trum of VII contained only one cross peak for protons
in the pyrrole ring, which corresponded to coupling
N-(2,2-Dichloro-2-phenylethylidene)-4-methylben-
zenesulfonamide (IV) is less reactive than compounds
I and II toward pyrrole and 1-methyl-1H-pyrrole
[2, 4]; this follows from the fact that its reactions are
less exothermic. No disubstituted pyrroles were formed
in the reaction with compound IV. The reaction of IV
with pyrrole gave 82% of 2-substituted derivative V
(Scheme 2), as in the reactions of pyrrole with
N-(2,2,2-trichloroethylidene)benzenesulfonamide (II)
and 4-chloro-N-(2,2,2-trichloroethylidene)benzenesul-
fonamide [2]. However, compound IV reacted with
1-methyl-1H-pyrrole to produce a mixture of isomeric
2- and 3-substituted 1-methyl-1H-pyrroles VI and VII
at a ratio of 4:1 (overall yield 81%; Scheme 3).
1
between 4-H and 5-H. The other signals in the H and
13C NMR spectra of isomers VI and VII were assigned
using HSQC 1H–13C correlation technique.
We succeeded in isolating isomer VI as individual
substance by fractional crystallization, and special
experiments proved that 2-substituted pyrrole VI is not
converted into 3-substituted isomer VII even on pro-
longed heating in boiling carbon tetrachloride.
The formation of a mixture of isomers VI and VII
1
was proved by H and 13C NMR spectroscopy. The
To interpret our experimental results we performed
quantum-chemical calculations of the electrophiles,
i.e., N-(polychloroethylidene) sulfonamides I, II, and
VIII, isomeric 2- and 3-monosubstituted products III,
IX, X, and XI–XIII, and isomeric disubstitution prod-
ucts XIV–XVI. Insofar as compounds XIV–XVI
possess two asymmetric carbon atoms, calculations
were performed for each diastereoisomer couple. The
calculations were performed in terms of the density
functional theory (DFT) using B3LYP/6-311G(d,p)
basis set with full geometry optimization with the aid
of Gaussian 03 software [5].
1H and 13C NMR spectra of the product mixture ob-
tained from compound IV and 1-methyl-1H-pyrrole
contained two sets of signals from aromatic protons
and carbon nuclei and those present in the 1-methyl-
pyrrole fragment. Furthermore, the NHCH moiety
1
gave rise to two doublets of doublets in the H NMR
spectrum, which is typical of N-polychloroethyl sul-
fonamides [2, 4]. The presence of 2- and 3-substituted
pyrrole ring in molecules VI and VII, respectively,
was unambiguously proved by two-dimensional NMR
1
techniques. The assignment was made using H–13C
n
correlation (HMBC) optimized for JCH = 10 Hz (cou-
It is well known that the α-position in the pyrrole is
more reactive than the β-position, though the differ-
ence in their reactivities is minimal as compared to
other five-membered heterocycles, thiophene and furan
[6]. Reduction in the reactivity of N-sulfonyl imines in
the series I > II > VIII is well consistent with increase
pling through 2–3 chemical bonds).
In the HMBC spectrum of VI we observed cross
peaks for protons in the 1-methyl group, on the one
hand, and C2 and C5, on the other. The CH proton
showed two cross peaks due to coupling with C2 and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

ROZENTSVEIG et al.
1334
F3CSO2
PhSO2
PhSO2
N
CCl3
N
CCl3
N
CCl2Ph
SO2Ph
I
II
VIII
H
H
H
N
N
N
SO2CF3
SO2Ph
N
H
N
N
H
H
CCl3
CCl3
CCl2Ph
IX
III
X
Cl3C
Cl3C
PhCl2C
NH
NH
SO2Ph
NH
SO2CF3
SO2Ph
N
H
N
H
N
H
XI
XII
XIII
Cl3C
Cl3C
SO2CF3
SO2CF3
N
H
N
H
H
N
H
N
H
H
N
N
F3CSO2
SO2CF3
F3CSO2
SO2CF3
N
H
N
H
N
H
Cl3C
CCl3
Cl3C
CCl3
XIV
XV
XVI
alize the regioselectivity in the reaction of I with
pyrrole we analyzed the structure of frontier molecular
orbitals in IX which acts as nucleophile in the reaction
with I. The maximal contribution to the highest
occupied molecular orbital of IX is that of the C5 atom
(31.4% against 8.3% of C3 and 11.2% of C4). Taking
into account that the process is orbital-controlled,
2,5-disubstituted product should be formed, as is ob-
served experimentally.
The 1H NMR spectrum of 2,5-bis[2,2,2-trichloro-1-
(trifluoromethylsulfonylamino)ethyl]pyrrole (XIV)
contained a singlet from the CCl3CH proton
(δ 5.25 ppm), a doublet from 3-H and 4-H (δ 6.47 ppm,
4JNH,CH = 2.3 Hz), a broadened singlet from the pyrrole
NH proton (δ 11.07 ppm) and a singlet from the
SO2NH proton (δ 11.62 ppm); in addition, singlets at
δ 5.22 ppm (CCl3CH) and 11.73 ppm (SO2NH) were
present due to the minor diastereoisomer. In the
13C NMR spectrum, signals at δC 66.65 (CH), 100.74
(CCl3), 109.38 (C3, C4), 119.07 (CF3, JCF = 322.5 Hz),
and 124.05 ppm (C2, C5) were assigned to the major
diastereoisomer, while the minor one displayed signals
at δC 100.68 and 109.23 ppm due to the CCl3 carbon
atom and C3/C4, respectively. The diastereoisomer
ratio was ~6:1. On the basis of the NMR data it was
impossible to determine whether racemic mixture of
optically active diastereoisomers (RR + SS) or meso
form (RS) of XIV prevails. Therefore, we compared
their energies calculated at the B3LYP/6-311G(d,p)
level. The meso form (RS) in the gas phase is slightly
in the energy of the lowest unoccupied molecular or-
bital in the same series: –0.117, –0.100, and –0.085 eV,
respectively, but there is no correlation with the charge
on the C=N carbon atom (0.131, 0.103, and 0.138,
respectively). These findings suggest that the reactions
of imines I, II, and VIII as electrophiles are orbital-
controlled.
The β-carbon atom in the pyrrole molecule pos-
sesses larger electron density, while the contribution of
the α-carbon atom to the highest occupied molecular
orbital is much greater than that of the β-carbon atom.
Therefore, orbital-controlled reactions with electro-
philes I, II, and VIII should occur at the α-position,
which is observed experimentally. The structure of
isomeric α- and β-substituted products is shown in
Fig. 1. The total energies of α-substituted compounds
III, IX, and X are lower than those of isomeric β-sub-
stitution products XI–XIII, which also favors forma-
tion of the former. However, it should be noted that the
energy difference ΔE between 2- and 3-substituted
isomers strongly depends on the initial imine. The ΔE
values for trichloroacetaldehyde imine derivatives
IX/XI and III/XII are 7.2 and 13.6 kcal/mol, respec-
tively, whereas the energy difference between isomeric
2- and 3-[2,2-dichloro-2-phenyl-1-(phenylsulfonyl-
amino)ethyl]pyrroles X and XIII is as small as
0.6 kcal/mol.
The high reactivity of imine I ensures facile forma-
tion of disubstituted product XIV. In order to ration-
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REGIOSELECTIVITY IN THE REACTIONS OF N-(POLYCHLOROETHYLIDENE)...
1335
IX, rCH···OS = 2.402 Å
XI, rCH···OS = 2.425 Å
III, rCH···OS = 2.347 Å
XII, rCH···OS = 2.390 Å
X, rCH···OS = 2.397 Å
XIII, rCH···OS = 2.427 Å
Fig. 1. Molecular structures of 2- and 3-substituted pyrroles III and X–XIII according to B3LYP/6-311G(d,p) calculations. Intra-
molecular hydrogen bonds are shown with dashed lines.
(2R,5S)-XIV, rCH···OS = 2.368 (2R), 2.331 Å (5S)
(2S,5S)-XIV, rSO···HN = 2.085, rCH···OS = 2.331 Å
Fig. 2. Molecular structures of (2S,5S)- and (2R,5S)-diastereoisomers of 2,5-bis[2,2,2-trichloro-1-(trifluoromethylsulfonylamino)-
ethyl]pyrrole (XIV) according to B3LYP/6-311G(d,p) calculations. Intramolecular hydrogen bonds are shown with dashed lines.
more favorable (by 1.6 kcal/mol), but its dipole mo-
ment (1.82 D) is lower than the dipole moment of the
(RR)-diastereoisomer or identical (SS)-diastereoisomer
(2.88 D). This means that the relative stability may
depend on the solvent nature. SCRF (self-consistent
reaction field) calculations of the structures optimized
by the B3LYP/6-311G(d,p) method showed that the
ΔE value in methylene chloride (i.e., in the same
solvent as in experimental studies) is 2.5 kcal/mol in
favor of the meso form (like in the gas phase). Taking
into account the above data we presumed that the
(RS)-diastereoisomer is the major component, and ra-
cemic mixture of optically active (RR)- and (SS)-dia-
stereoisomers is the minor component.
According to the calculations, intramolecular hy-
drogen bonds are formed in both diastereoisomers. The
meso-form (RS) is characterized by CH···OS hydrogen
bonds in both side chains, while in the (SS)-diastereo-
isomer analogous CH···OS hydrogen bond is formed
in one side chain, and the other side chain is involved
in NH···OS hydrogen bond with participation of the
pyrrole NH proton (Fig. 2).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

ROZENTSVEIG et al.
1336
One of the most interesting results of the reactions
5.72 g (0.02 mol) of compound II and 50 ml of anhy-
drous carbon tetrachloride, cooled to –15°C. After
30 min, the cooling bath was removed, and the mixture
was stirred for 5 h at room temperature and was kept
for 12 h in the cold. The precipitate was filtered off
and washed with 50 ml of 10% aqueous ammonia.
Yield 2.62 g (74%), mp 178–182°C. IR spectrum, ν,
of N-(polychloroethylidene) sulfonamides with pyr-
roles is the formation of [2,2-dichloro-1-(1-methyl-1H-
pyrrol-2-yl)-2-phenylethyl]-4-methylbenzenesulfon-
amide (VI) as the major product and N-[2,2-dichloro-
1-(1-methyl-1H-pyrrol-3-yl)-2-phenylethyl]-4-methyl-
benzenesulfonamide (VII) as the minor product from
N-[2,2-dichloro-2-phenylethylidene]-4-methylben-
zenesulfonamide (IV) and 1-methyl-1H-pyrrole
(Scheme 3). β-Substituted product is formed only in
the reaction with the least reactive electrophile among
the examined ones. This result is consistent with the
theoretical data. The difference in the energies of α-
and β-substituted isomers X and XIII is very small,
0.6 kcal/mol against 7.2 and 13.6 kcal/mol for isomer
couples IX/XI and III/XII, respectively. This means
that the probabilities for formation of isomers X and
XIII are almost similar from the viewpoint of thermo-
dynamics. In addition, the lowest unoccupied molec-
ular orbital of imine IV as electrophile (as well as the
LUMO of imine VIII) has a higher energy than those
of I and II (ELUMO = –0.117, –0.100, –0.085, and
–0.083 eV for compounds I, II, VIII, and IV, respec-
tively), while the positive charge on the C=N carbon
atom is maximal (0.131, 0.103, 0.138, and 0.137 a.u.
for I, II, VIII, and IV, respectively). Increase of the
gap between the HOMO of pyrrole and LUMO of
electrophile should lead to reduction in the contribu-
tion of orbital control and increase in the contribution
of charge control and hence to increased probability of
β-substitution, in keeping with the experimental data.
1
cm–1: 3420, 3230 (NH); 1320, 1160 (SO2). H NMR
3
spectrum, δ, ppm: 5.25 d (1H, NCH, J = 9.0 Hz),
5.78 m (1H, 4-H), 6.17 m (1H, 3-H), 6.53 m (1H, 5-H),
7.32 m (1H, p-H) 7.44 m (2H, m-H), 7.60 m (2H, o-H),
3
8.86 d (1H, NH, J = 9.0 Hz), 10.69 s (1H, 1-H).
13C NMR spectrum, δC, ppm: 66.26 (NCH), 102.26
(CCl3), 107.57 (C4), 108.68 (C3), 117.73 (C5), 123.92
(C2), 126.16 (Co), 128.51 (Cm), 132.07 (Cp), 140.69
(Ci). Found, %: C 41.03; H 3.26; Cl 30.66; N 7.52;
S 9.22. C12H11Cl3N2O2S. Calculated, %: C 40.76;
H 3.14; Cl 30.07; N 7.92; S 9.07.
N-[2,2-Dichloro-2-phenyl-1-(1H-pyrrol-2-yl)-
ethyl]-4-methylbenzenesulfonamide (V). A mixture
of 1.71 g (5 mmol) of compound IV, 0.47 g (7 mmol)
of pyrrole, and 15 ml of anhydrous carbon tetra-
chloride was stirred for 45 min. The precipitate was
filtered off, washed with 50 ml of 10% aqueous ammo-
nia, dried, and recrystallized from chloroform. Yield
1.67 g (82%), mp 182–184°C. IR spectrum, ν, cm–1:
1
3400, 3210 (NH); 1305, 1140 (SO2). H NMR spec-
trum, δ, ppm: 2.26 s (3H, CH3), 5.25 d (1H, NCH, 3J =
10.0 Hz), 5.67 m (1H, 4-H), 5.77 m (1H, 3-H), 6.38 m
(1H, 5-H), 7.07 d (2H, m-H in C6H4), 7.33 d (2H, o-H
in C6H4), 7.35 m (2H, m-H in C6H5), 7.39 m (1H, p-H
in C6H5), 7.55 m (2H, o-H in C6H5), 8.22 d (1H, NH,
Thus our experimental data and the results of
quantum-chemical calculations indicate that reactions
of N-sulfonylpolychloroacetaldehyde imines with pyr-
roles are orbital-controlled and that they give mainly
the corresponding α-substituted pyrrole derivatives,
though least reactive electrophiles could give rise to
isomeric β-substituted products.
13
3J = 10.0 Hz), 10.19 s (1H, 1-H). C NMR spectrum,
δC, ppm: 21.57 (CH3), 65.03 (NCH), 94.80 (CCl2),
108.24 (C4), 110.31 (C3), 118.33 (C5), 124.65 (C2),
127.15 (Co in C6H4), 127.28 (Co in C6H5), 128.25 (Cm
in C6H5), 129.46 (Cm in C6H4), 129.61 (Cp in C6H5),
137.00 (Ci in C6H4), 139.56 (Ci in C6H5), 143.48 (Cp in
C6H4). Found, %: C 56.02; H 4.36; Cl 16.99; N 6.32;
S 7.22. C20H20Cl2N2O2S. Calculated, %: C 55.75;
H 4.43; Cl 17.32; N 6.84; S 7.83.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Bruker
1
IFS-25 spectrometer. The H and 13C NMR spectra
Reaction of N-(2,2-dichloro-2-phenylethylidene)-
4-methylbenzenesulfonamide (IV) with 1-methyl-
1H-pyrrole. A mixture of 1.71 g (5 mmol) of com-
pound IV, 0.57 g (7 mmol) of 1-methyl-1H-pyrrole,
and 15 ml of anhydrous carbon tetrachloride was
heated for 5 h under reflux with stirring. The mixture
was then kept in the cold, and the precipitate was
filtered off, washed with 50 ml of 10% aqueous ammo-
nia, and dried. According to the NMR data, the product
was a mixture of N-[2,2-dichloro-1-(1-methyl-1H-pyr-
were measured from solutions in DMSO-d6 on Bruker
DPX-400 and Bruker Avance-400 spectrometers at
1
400.13 MHz for H and 100.62 MHz for 13C using
tetramethylsilane as reference. Initial compounds I [7],
II [2], IV [8], IX, and XIV [4] were synthesized ac-
cording to known procedures.
N-[2,2,2-Trichloro-1-(1H-pyrrol-2-yl)ethyl]ben-
zenesulfonamide (III). Pyrrole, 0.67 g (0.01 mol),
was added dropwise under stirring to a mixture of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008

REGIOSELECTIVITY IN THE REACTIONS OF N-(POLYCHLOROETHYLIDENE)...
rol-2-yl)-2-phenylethyl]-4-methylbenzenesulfonamide
REFERENCES
1337
(VI) and N-[2,2-dichloro-1-(1-methyl-1H-pyrrol-3-yl)-
2-phenylethyl]-4-methylbenzenesulfonamide (VII) at
a ratio of 4:1. Overall yield 1.72 g (81%). Isomer VI
was isolated as individual substance by fractional crys-
tallization of the isomer mixture from carbon tetra-
chloride, yield 0.49 g.
1. Levkovskaya, G.G., Drozdova, T.I., Rozentsveig, I.B., and
Mirskova, A.N., Usp. Khim., 1999, vol. 68, p. 638.
2. Mirskova, A.N., Drozdova T.I., Levkovskaya, G.G., Ku-
kharev, B.F., Kalikhman, I.D., and Voronkov, M.G.,
Zh. Org. Khim., 1989, vol. 25, p. 1312.
3. Johannsen, M., Chem. Commun., 1999, p. 2233.
Compound VI. mp 140–142°C. IR spectrum, ν,
1
cm–1: 3230 (NH); 1320, 1150 (SO2). H NMR spec-
4. Kondrashov, E.V., Rozentsveig, I.B., and Levkov-
skaya, G.G., Russ. J. Org. Chem., 2007, vol. 43, p. 1747.
trum, δ, ppm: 2.26 s (3H, CH3C6H4), 2.78 s (3H,
3
5. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E.,
Robb, M.A., Cheeseman, J.R., Montgomery, Jr., J.A.,
Vreven, T., Kudin, K.N., Burant, J.C., Millam, J.M.,
Iyengar, S.S., Tomasi, J., Barone, V., Mennucci, B.,
Cossi, M., Scalmani, G., Rega, N., Petersson, G.A., Na-
katsuji, H., Hada, M., Ehara, M., Toyota, K., Fukuda, R.,
Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Ki-
tao, O., Nakai, H., Klene, M., Li, X., Knox, J.E.,
Hratchian, H.P., Cross, J.B., Bakken, V., Adamo, C.,
Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O.,
Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W.,
Ayala, P.Y., Morokuma, K., Voth, G.A., Salvador, P.,
Dannenberg, J.J., Zakrzewski, V.G., Dapprich, S., Da-
niels, A.D., Strain, M.C., Farkas, O., Malick, D.K.,
Rabuck, A.D., Raghavachari, K., Foresman, J.B.,
Ortiz, J.V., Cui, Q., Baboul, A.G., Clifford, S., Cioslow-
ski, J., Stefanov, B.B., Liu, G., Liashenko, A., Pis-
korz, P., Komaromi, I., Martin, R.L., Fox, D.J., Keith, T.,
Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challa-
combe, M., Gill, P.M.W., Johnson, B., Chen, W.,
Wong, M.W., Gonzalez, C., and Pople, J.A., Gaussian
03, Revision C.02, Wallingford CT: Gaussian, 2004.
1-CH3), 4.90 d (1H, NCH, J = 9.7 Hz), 5.72 m (1H,
4-H), 6.23 m (1H, 3-H), 6.24 m (1H, 5-H), 7.08 d (2H,
m-H in C6H4), 7.34 d (2H, m-H in C6H5), 7.35 m (3H,
o-H in C6H4, p-H in C6H5), 7.48 m (2H, o-H in C6H5),
3
13
8.58 d (1H, NH, J = 9.7 Hz). C NMR spectrum, δC,
ppm: 20.86 (CH3C6H4), 32.67 (1-CH3), 61.88 (NCH),
95.69 (CCl2), 106.54 (C4), 109.67 (C3), 121.65 (C5),
126.08 (C2), 126.12 (Co in C6H4), 127.50 (Co in C6H5),
127.82 (Cm in C6H5), 128.77 (Cm in C6H4), 129.31 (Cp
in C6H5), 137.81 (Ci in C6H5), 139.30 (Ci in C6H4),
141.99 (Cp in C6H4). Found, %: C 56.53; H 4.36;
Cl 16.66; N 6.32; S 7.22. C20H20Cl2N2O2S. Calculated,
%: C 56.74; H 4.76; Cl 16.75; N 6.62; S 7.57.
1
Compound VII. H NMR spectrum, δ, ppm: 2.28 s
(3H, CH3C6H4), 3.26 s (3H, 1-CH3), 5.05 d (1H, NCH,
3J = 9.7 Hz), 5.52 m (1H, 4-H), 6.10 m (1H, 2-H),
6.21 m (1H, 5-H), 7.12 d (2H, m-H in C6H4), 7.32 m
(2H, m-H in C6H5), 7.37 m (1H, p-H in C6H5), 7.42 d
(2H, o-H in C6H4), 7.50 m (2H, o-H in C6H5), 8.25 d
3
13
(1H, NH, J = 9.7 Hz). C NMR spectrum, δC, ppm:
20.87 (CH3C6H4), 35.29 (1-CH3), 64.73 (NCH), 96.36
(CCl2), 108.36 (C4), 117.15 (C3), 120.45 (C5), 121.99
(C2), 126.01 (Co in C6H5), 126.48 (Co in C6H4), 127.23
(Cm in C6H5), 128.51 (Cm in C6H4), 128.96 (Cp in
C6H5), 138.57 (Ci in C6H5), 140.45 (Ci in C6H4), 141.74
(Cp in C6H4).
6. Belen’kii, L.I., Khim. Geterotsikl. Soedin., 1980, p. 1587.
7. Rozentsveig, I.B., Levkovskaya, G.G., Kondrashov, E.V.,
Evstaf’eva, I.T., and Mirskova, A.N., Russ. J. Org.
Chem., 2001, vol. 37, p. 1559.
8. Drozdova, T.I. and Mirskova, A.N., Russ. J. Org. Chem.,
2001, vol. 37, p. 284.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 9 2008