C-amidoalkylation of pyrroles with N-trifluoromethylsulfonyl and N-arylsulfonyl polychloroaldehyde imines

Article abstract of DOI:10.1134/S1070428009090097

N-(Trifluoromethylsulfonyl) and N-arylsulfonyl polychloroacetaldehyde imines reacted with pyrrole, 1-alkyl-, 1-benzyl-, and 1-(4-nitrophenyl)- substituted pyrroles, and bis-pyrroles to give the corresponding 2-[1-(sulfonylamino)polychloroethyl]-1H-pyrroles or mixtures of 2- and 3-[1-(sulfonylamino)polychloroethyl]-1H-pyrroles, depending on the nature of the Schiff base and substituent on the pyrrole nitrogen atom and reaction conditions. The first synthesis of 2,5-disubstituted NH-pyrrole by reaction of pyrrole with Schiff bases was described.

Full text of DOI:10.1134/S1070428009090097

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2009, Vol. 45, No. 9, pp. 1365–1374. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.V. Kondrashov, E.V. Rudyakova, G.N. Rozentsveig, I.B. Rozentsveig, K.A. Chernyshev, L.B. Krivdin, G.G. Levkovskaya, 2009,
published in Zhurnal Organicheskoi Khimii, 2009, Vol. 45, No. 9, pp. 1379–1387.
C-Amidoalkylation of Pyrroles with N-Trifluoromethylsulfonyl
and N-Arylsulfonyl Polychloroaldehyde Imines
E. V. Kondrashov, E. V. Rudyakova, G. N. Rozentsveig, I. B. Rozentsveig, K. A. Chernyshev,
L. B. Krivdin, and G. G. Levkovskaya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: evgeny_irich@irioch.irk.ru
Received September 9, 2008
Abstract—N-(Trifluoromethylsulfonyl) and N-arylsulfonyl polychloroacetaldehyde imines reacted with pyr-
role, 1-alkyl-, 1-benzyl-, and 1-(4-nitrophenyl)-substituted pyrroles, and bis-pyrroles to give the corresponding
2-[1-(sulfonylamino)polychloroethyl]-1H-pyrroles or mixtures of 2- and 3-[1-(sulfonylamino)polychloroethyl]-
1H-pyrroles, depending on the nature of the Schiff base and substituent on the pyrrole nitrogen atom and
reaction conditions. The first synthesis of 2,5-disubstituted NH-pyrrole by reaction of pyrrole with Schiff bases
was described.
DOI: 10.1134/S1070428009090097
We previously reported [1] on the reactions of
4-chloro-N-(2,2,2-trichloroethylidene)benzenesulfon-
amide with pyrrole and 1-methyl-1H-pyrrole and syn-
thesized the corresponding 2-[2,2,2-trichloro-1-(4-
chlorophenylsulfonylamino)ethyl]pyrroles as C-amido-
alkylation products. The reactions occurred both in the
presence of BF3·Et2O as catalyst and in the absence of
it; in the latter case, the process required a longer time.
The yield of the alkylation product from unsubstituted
pyrrole did not exceed 37% [1]. We recently found [2]
that pyrrole reacts with N-(2,2,2-trichloroethylidene)-
trifluoromethanesulfonamide to give both 2-mono- and
2,5-disubstituted products.
substances. We previously demonstrated that (2,2,2-tri-
chloro-1-sulfonylaminoethyl)-substituted indoles can
be converted into N-substituted indolylglycines, which
may be regarded as biologically active heteroauxin
derivatives modified with a sulfonylamino group [4].
Obviously, analogous processes may be typical of
structurally related pyrrole derivatives.
Thus development of procedures for the introduc-
tion of amino(polyhalo)ethyl substituents into a pyr-
role ring could open convenient synthetic approaches
to new functionalized pyrroles as precursors of N-sul-
fonyl-substituted pyrrolylaminoacetic acids, aminocar-
bonyl compounds, and heterocyclic systems. The im-
portance of this problem is beyond doubt.
With a view to reveal relations between the struc-
ture of Schiff bases, their reactivity, and direction of
their reactions with hetarenes [3], we continued our
studies on reactions of pyrrole derivatives with Schiff
bases containing strong electron-withdrawing groups.
In the present work we examined reactions of pyrrole
and N-substituted pyrroles with N-(2,2,2-trichloro-
ethylidene)- and N-(2,2-dichloro-2-phenylethylidene)-
trifluoromethane- and -arenesulfonamides. The prod-
ucts of these reactions are characterized by unique
combination of a pyrrole ring and aminosulfonyl and
trichloromethyl groups which undoubtedly determine
their ability to undergo further chemical transforma-
tions and significance as potential biologically active
Schiff bases Ia–If were synthesized according to
the procedures developed previously from the corre-
sponding N,N-dichloro sulfonamides and trichloroeth-
ylene or phenylacetylene [5–7]. Schiff bases Ia–Ic
were brought into reactions with pyrroles without
isolation from the reaction mixture; reactions of Schiff
bases Id–If with pyrroles were carried out in carbon
tetrachloride. Pyrroles IIb–IIf were prepared by al-
kylation of pyrrole (IIa) at the nitrogen atom according
to the procedure reported previously for the synthesis
of 1-methyl-1H-indole [8]. As alkylating agents we
used benzyl chloride, 4-nitrofluorobenzene, 1,6-di-
chlorohexane, and 1,4-bis(chloromethyl)benzene, and
1365

KONDRASHOV et al.
reacted with an equimolar amount of pyrrole (IIa)
1366
Scheme 1.
under analogous conditions to give a mixture of mono-
and disubstituted pyrroles IIIa and IX at a ratio of
(2–4):1 [2] (Scheme 3). Pure 2,5-disubstituted deriva-
tive IX was also obtained by adding a solution of pyr-
role to 2 equiv of Ia, other conditions being equal [2].
RHlg
N
NaOH
DMSO
R
IIb–IId
N
H
Cl
Z
Cl
IIa
N
Z
N
Scheme 3.
IIe, IIf
F3CSO2N=CHCCl3
+
N
H
R = H (a); R = Me, Hlg = I (b); R = PhCH2, Hlg = Cl (c); R =
4-O2NC6H4, Hlg = F (d); Z = (CH2)6 (e), p-CH2C6H4CH2 (f).
Ia
IIa
the alkylation was carried out in DMSO in the pres-
ence of alkali [9] (Scheme 1).
F3CSO2NH
NHSO2CF3
CCl3
CH2Cl2, –78°C
N
H
Cl3C
The reactions of Schiff bases Ia–If with pyrrole
(IIa) and N-substituted pyrroles IIb–IId were per-
formed by adding an equimolar amount of the corre-
sponding pyrrole to reaction mixture containing Schiff
base Ia–Ic or to a solution of Schiff base Id–If in
carbon tetrachloride. The yields of amidoalkylation
products III–VIII were 70–90% (Scheme 2).
IX
N-Sulfonyl imines Id–If derived from dichloro-
(phenyl)acetaldehyde possess less electrophilic CH=N
bond. These compounds reacted with pyrrole (IIa) at
room temperature without appreciable tarring, and the
corresponding monosubstituted products VIa–VIIIa
were formed in 83–95% yield.
Scheme 2.
The formation of pyrroles IIIa and IX and their
R1SO2N=CHCCl2X
+
mixture was confirmed by the NMR data and elemen-
N
1
tal analyses. In the H NMR spectrum of IIIa, signals
R2
from the pyrrole ring protons were split into multiplets
Ia–If
IIa–IId
4
with the following coupling constants: J5, 3 = 1.5,
3J5,4 = 2.7, 3J3,4 = 3.4 Hz. The 13C NMR spectrum con-
tained four signals from carbon atoms in the pyrrole
ring. Disubstituted pyrrole IX displayed in the 1H NMR
spectrum a doublet from the pyrrole ring protons with
NHSO2R1
N
CCl2X
R2
IIIa–IIId, IVa, IVb, Va–Vd
VIa–VIc, VIIa–VIIc, VIIIa–VIIIc
4
a coupling constant J1,3 of 2.6 Hz. Only two signals
from carbon atoms in the pyrrole ring were observed in
the 13C NMR spectrum of IX. The spectrum recorded
without decoupling from protons contained a doublet
signal from C3 and C4 and a singlet from C2 and C5.
Compound IX showed in the 1H–13C HMBC spectrum
cross peaks due to coupling of C2 and C5 with the
CHCCl3 proton and protons in positions 3 and 4. In the
1H NMR spectra of both IIIa and IX, protons in the
CF3SO2NHCH gave rise to two singlets.
I, X = Cl, R1 = CF3 (a), Ph (b), 4-ClC6H4 (c); X = Ph, R1 =
Ph (d), 4-MeC6H4 (e), 4-ClC6H4 (f); III, X = Cl, R1 = CF3,
R2 = H (a), Me (b), PhCH2 (c), 4-O2NC6H4 (d); IV, X = Cl,
R1 = Ph, R2 = H (a), Me (b); V, X = Cl, R1 = 4-ClC6H4, R2 =
H (a), Me (b), PhCH2 (c), 4-O2NC6H4 (d); VI, X = R1 = Ph,
R2 = H (a), Me (b), PhCH2 (c); VII, X = Ph, R1 = 4-MeC6H4,
R2 = H (a), Me (b), PhCH2 (c); VIII, X = Ph, R1 = 4-ClC6H4,
R2 = H (a), Me (b), PhCH2 (c).
The reactions of unsubstituted pyrrole (IIa) with
Schiff bases Ia–Ic were accompanied by considerable
heat evolution which favored formation of tars. Tarring
may be avoided by cooling the reaction mixture to –60
to –78°C. For example, we succeeded in isolating pure
2-substituted pyrrole IIIa by adding a mixture contain-
ing Schiff base Ia to 4 equiv of pyrrole (IIa) on
cooling to –60°C. On the other hand, compound Ia
We failed to find conditions ensuring formation of
2,5-disubstituted pyrrole derivatives in reactions with
arenesulfonamides Ib–If. In all cases, the process
stopped at the stage of formation of the corresponding
2-monosubstituted derivatives IVa–VIIIa. We found
no published data on the synthesis of 2,5-disubstituted
pyrroles like IX via amidoalkylation of pyrroles.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

C-AMIDOALKYLATION OF PYRROLES
1367
Scheme 4.
XCl2C
NHSO2R
NHSO2R
+
RSO2N=CHCCl2X
+
N
N
N
CCl2X
Me
Me
Me
Ia, Ic, If
IIb
IIIb–Vb, VIIIb
X–XIII
Ia, IIIb, X, X = Cl, R = CF3; Ib, IVb, XI, X = Cl, R = Ph; Ic, Vb, XII, X = Cl, R = 4-ClC6H4;
If, VIIb, XIII, X = Ph, R = 4-MeC6H4.
On the other hand, N-(2,2,2-trichloroethylidene)-
and N-(2,2-dichloro-2-phenylethylidene)sulfonamides
Ia–If reacted with N-methylpyrrole to give mixtures of
2- and 3-substituted N-methylpyrroles, whose ratio de-
pended on the reaction conditions and structure of the
initial Schiff base (Scheme 4). An example of analo-
gous nonselective C-amidoalkylation of pyrroles was
reported in [10]: N-methylpyrrole reacted with ethyl
(4-methylsulfonylimino)acetate in THF at –78°C to
give a mixture of the corresponding 2- and 3-substi-
tuted 1-methylpyrroles either in equal amounts or with
prevalence of the latter.
tra contained two set of signals from aromatic and
pyrrole rings. In addition, two sets of doublets typical
of NH–CH fragment [1, 5] were observed in the
1H NMR spectra. Furthermore, the substitution pattern
in the pyrrole ring was unambiguously proved by two-
1
dimensional H–13C HMBC technique optimized for
nJCH = 10 Hz (coupling through 2–3 bonds).
No 3-substituted pyrroles were detected in the reac-
tions of N-benzylpyrrole (IIc) with Schiff bases Ia and
Ic–If. Introduction of an electron-withdrawing substit-
uent into position 1 of the pyrrole ring reduces its
nucleophilicity, which does not favor reactions with
less electrophilic dichloro(phenyl)acetaldehyde imines
Id–If. 1-(4-Nitrophenyl)-1H-pyrrole (IId) failed to
react with Schiff bases Id–If on heating for 3 h at 70°C
even in the presence of BF3 ·Et2O.
The isomer ratio depends on the initial Schiff base
and reaction temperature. Schiff bases Ia–Ic derived
from trichloroacetaldehyde reacted with N-methylpyr-
role at room temperature to produce mixtures of 2- and
3-substituted derivatives at a molar ratio of 5:1 to
20:1. Raising the temperature favored formation of
3-substituted isomers X–XII. We succeeded in obtain-
ing individual 2-substituted N-methylpyrroles IIIb–Vb
only when the reaction was carried out at –15°C.
However, 4-chloro-N-(2,2,2-trichloroethylidene)-
benzenesulfonamide (Ic) did react with pyrrole IId,
but only on prolonged heating in the presence of BF3·
Et2O; as a result, 2-substituted pyrrole Vd was formed,
but we failed to isolate it as individual substance.
According to the NMR data, the reaction mixture was
likely to contain 1,1-bis[1-(4-nitrophenyl)-1H-pyrrol-
2-yl]-2,2,2-trichloroethane (XIV) which could be
formed via concurrent reaction of sulfonamide Vd
with initial pyrrole IId. The formation of products like
compound XIV was observed by us previously in
C-amidoalkylation of arenes under severe conditions
that promoted elimination of the sulfonamide group
[11, 12] (Scheme 5).
Less reactive N-(2,2-dichloro-2-phenylethylidene)-
sulfonamides Id–If reacted with N-methylpyrrole only
at elevated temperature, and in all cases mixtures of
2- and 3-(2,2-dichloro-2-phenyl-1-sulfonylaminoethyl)-
pyrroles were formed at a ratio of 10:1 to 4:1. Pure
2-substituted products VIb–VIIIb can be isolated by
fractional crystallization (they separated first from the
reaction mixture) or fractional recrystallization of the
isomer mixture from carbon tetrachloride. By special
experiment with compound VIIIb as an example we
showed that 2-substituted pyrroles are not converted
into 3-substituted isomers on prolonged heating in
carbon tetrachloride.
Scheme 5.
BF3 ·Et2O, 80°C
Ib
+
IId
Vd
Isomer mixtures formed in the reactions of Schiff
bases Ia–Ic and If with N-methylpyrrole were exam-
+
N
N
1
13
ined in detail by H and C NMR (see Experimental).
The NMR data confirmed formation of 2- (IIIb–Vb,
VIIIb) and 3-substituted pyrroles (X–XIII). The spec-
4-O2NC6H4
C6H4NO2-4
CCl3
XIV
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

KONDRASHOV et al.
1368
Scheme 6.
Cl3C
NHSO2R
Cl3C
NHSO2CF3
N
F3CSO2NH
CCl3
Ia, Ic
+
IIe, IIf
N
Z
N
+
N
RSO2NH
CCl3
XVIa, XVIb, XVIIa, XVIIb
XVIII
F3CSO2NH
CCl3
N
+
N
Cl3C
NHSO2CF3
XIX
R = CF3 (a), 4-ClC6H4 (b); XVI, X = (CH2)6; XVII, X = p-CH2C6H4CH2.
The most electrophilic among the examined Schiff
bases, (2,2,2-trichloroethylidene)trifluoromethanesul-
fonamide (Ia) reacted with pyrrole IId at room tem-
perature in the absence of a catalyst to afford a mixture
of amidoalkylation products at positions 2 and 3 (ratio
10:1, overall yield 85%). Individual amide IIId was
isolated by treatment of the reactions mixture with
aqueous alkali: N-{2,2,2-trichloro-1-[1-(4-nitrophenyl)-
1H-pyrrol-3-yl]ethyl}trifluoromethanesulfonamide
(XV) is better soluble than 2-substituted isomer IIId.
approximately 3 :1. Insofar as the probability for
formation of 3,3′-isomer is not high (substitution at the
2-position is preferred), its fraction in the product mix-
ture is insignificant, and signals belonging to com-
1
pound XIX in the H NMR spectrum are overlapped
by those of isomers XVIIa and XVIII. Carbon signals
of compound XIX can be detected only after pro-
longed accumulation.
Analogous pattern was observed in the reaction of
4-chlorobenzenesulfonamide Ic with pyrrole IIf. The
ratio of 2,2′- and 2,3′-substituted isomers was 5 :1
(according to the 1H NMR data). The reaction of Schiff
base Ic with pyrrole IIe was more selective, and we
detected no isomeric C-amidoalkylation products.
While continuing development of synthetic ap-
proaches to polyfunctional pyrrole derivatives, Schiff
bases Ia and Ic were brought into reactions with
N,N′-bridged bis-pyrroles IIe and IIf. The reactions
were carried out at room temperature using 2 equiv of
Schiff base. Taking into account the lack of regioselec-
tivity in the reactions of Schiff bases Ia–If with
N-methylpyrrole, the formation of three possible iso-
mers may be expected (Scheme 6). Trifluoromethane-
sulfonamide Ia reacted with pyrroles IIe and IIf in
a nonselective fashion, yielding a mixture of 2,2′-,
2,3′-, and 3,3′-disubstituted products, the 2,2′-isomer
considerably prevailing. All three isomers were detect-
ed by NMR in the reaction mixture obtained from
Schiff base Ia and pyrrole IIf.
Thus we have synthesized a series of N-(poly-
chloroethyl) sulfonamides containing one or two pyr-
role rings and shown that the regioselectivity in the
reactions of N-sulfonyl polychloroacetaldehyde imines
with pyrrole and 1-substituted pyrroles is determined
by the nature of initial Schiff base, substituent on the
nitrogen atom in the pyrrole molecule, and reaction
conditions. N-(2,2,2-Trichloroethylidene)trifluoro-
methanesulfonamide reacts at one or both α-positions
of the pyrrole ring. N-Sulfonyl trichloro- and dichloro-
(phenyl)acetaldehyde imines react with N-methylpyr-
role, yielding mixtures of 2- and 3-substituted isomers.
1
The H and 13C NMR spectra, apart from signals
belonging to symmetrically substituted bis-pyrrole
XVIIa, contained a set of signals assignable to 3-sub-
stituted pyrrole rings, additional CF3SO2NHCHCCl3
fragment, and unsymmetrically substituted p-CH2-
C6H4CH2 fragment in molecule XVIII. According to
EXPERIMENTAL
The IR spectra were recorded in KBr on a Bruker
1
IFS-25 spectrophotometer. The H and 13C NMR
1
the H NMR data, the isomer ratio XVIIa:XVIII is
spectra were measured from solutions in DMSO-d6 or
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

C-AMIDOALKYLATION OF PYRROLES
1369
CDCl3 on a Bruker DPX-400 spectrometer at 400.13
and 101.61 MHz, respectively. The chemical shifts
were determined relative to tetramethylsilane with an
accuracy of ±0.01 ppm. The coupling constants JHH
and JCF were determined with an accuracy of ±0.1 Hz.
1,6-Bis[2-(2,2,2-trichloro-1-trifluoromethyl-
sulfonylaminoethyl)-1H-pyrrol-1-yl]hexane (XVIa).
1H NMR spectrum, δ, ppm: 1.12 m (4H, CH2), 1.63 m
(4H, CH2), 3.90 d.t (4H, CH2), 5.24 s (2H, CH),
6.01 m (2H, 4-H), 6.51 m (2H, 3-H), 6.82 m (2H, 5-H),
10.97 br.s (2H, NH). 13C NMR spectrum, δC, ppm:
25.81 (CH2), 30.27 (CH2), 46.51 (CH2), 64.70 (CH),
101.46 (CCl3), 107.49 (C4), 110.36 (C3), 119.11 q
Initial Schiff bases Ia [5], Ib, Ic [6], Id, Ie, and If
[7] were synthesized by known methods. Pyrroles IIb–
IIf were prepared as described in [9].
1
(CF3, JCF = 322.3 Hz), 122.81 (C5), 124.06 (C2).
Reaction of N-(2,2,2-trichloroethylidene)tri-
fluoromethanesulfonamide (Ia) with N-methylpyr-
role. A solution of 0.01 mol (0.81 g) of N-methylpyr-
role in 3 ml of carbon tetrachloride was added to
0.01 mol of Schiff base Ia. The addition was accom-
panied by evolution of heat, and the flask was cooled
with water. The mixture was kept for 6 h at room
temperature and evaporated under reduced pressure
(1 mm). According to the NMR data, the residue was
a mixture of amides IIIb and X at a ratio of 9:1. Over-
all yield 3.06 g (85%). Individual compound IIIb was
obtained when the reaction was carried out at –15°C
(the product was isolated by recrystallization of the
residue from hexane).
Found, %: C 31.28; H 2.90; Cl 27.18; N 7.17; S 8.23.
C20H22Cl6F6N4O4S2. Calculated, %: C 31.07; H 2.87;
Cl 27.51; N 7.25; S 8.29.
The reaction of N-(2,2,2-trichloroethylidene)tri-
fluoromethanesulfonamide (Ia) with 1,4-bis[(1H-
pyrrol-1-yl)methyl]benzene was carried out in a simi-
lar way using 0.01 mol of Schiff base Ia and 1.18 g
(0.005 mol) of pyrrole IIf. According to the NMR data,
the residue was a mixture of compounds XVIIa,
XVIII, and XIX; overall yield 3.49 g (88%); ratio
XVIIa:XVIII ≈ 3:1.
1,4-Bis[2-(2,2,2-trichloro-1-trifluoromethylsul-
fonylaminoethyl)-1H-pyrrol-1-ylmethyl]benzene
(XVIIa). 1H NMR spectrum, δ, ppm: 5.17 d and 5.26 d
N-[2,2,2-Trichloro-1-(1-methyl-1H-pyrrol-2-yl)-
ethyl]trifluoromethanesulfonamide (IIIb). Yield
2
(4H, AB, CH2, J = 15.4 Hz), 5.40 s (2H, CH), 6.10 m
(2H, 4-H), 6.64 m (2H, 3-H), 6.75 m (2H, 5-H), 7.16 s
(4H, C6H4), 10.97 s (2H, NH). 13C NMR spectrum, δC,
ppm: 50.03 (CH2), 64.60 (CH), 101.35 (CCl3), 107.85
1
2.56 g (71%), mp 124–125°C. H NMR spectrum, δ,
ppm: 3.64 s (3H, CH3), 5.22 s (1H, CH), 6.03 m (1H,
4-H), 6.57 m (1H, 3-H), 6.81 m (1H, 5-H), 11.12 br.s
(1H, NH). 13C NMR spectrum, δC, ppm: 33.78 (CH3),
64.56 (CH), 101.10 (CCl3), 107.19 (C4), 110.28 (C3),
1
(C4), 110.84 (C3), 119.01 q (CF3, JCF = 322.4 Hz),
123.56 (C5), 124.83 (C2), 128.02 (C2″, C3″, C5″, C6″ in
C6H4), 136.54 (C1′, C4′ in C6H4). Found, %: C 33.50;
H 2.31; Cl 26.64; N 7.12; S 8.15. C22H18Cl6F6N4O4S2.
Calculated, %: C 33.31; H 2.29; Cl 26.82; N 7.06;
S 8.08.
1
119.16 q (CF3, JCF = 322.4 Hz), 124.08 (C5), 124.56
(C2). Found, %: C 26.91; H 2.27; Cl 29.15; N 7.64;
S 9.04. C8H8Cl3F3N2O2S. Calculated, %: C 26.72;
H 2.24; Cl 29.58; N 7.79; S 8.92.
N-[2,2,2-Trichloro-1-(1-{4-[3-(2,2,2-trichloro-1-
trifluoromethylsulfonylaminoethyl)-1H-pyrrol-1-
yl]methylbenzyl}-1H-pyrrol-2-yl)ethyl]trifluoro-
N-[2,2,2-Trichloro-1-(1-methyl-1H-pyrrol-3-yl)-
1
ethyl]trifluoromethanesulfonamide (X). H NMR
1
spectrum, δ, ppm: 3.60 s (3H, CH3), 5.13 d (1H, CH,
methanesulfonamide (XVIII). H NMR spectrum
3J = 7.8 Hz), 6.32 m (1H, 4-H), 6.64 m (1H, 5-H),
(DMSO-d6), δ, ppm: 5.14 d and 5.29 d (4H, AB, CH2,
2J = 15.5 Hz), 5.39 s (2H, CH), 6.09 m (1H, 4-H),
6.38 m (1H, 4′-H), 6.65 m (1H, 3-H), 6.74 m (1H,
3′-H), 6.75 m (1H, 5-H), 6.81 m (1H, 2′-H), 7.01 d and
7.13 d (4H, AA′BB′, C6H4), 10.75 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 50.03 (CH2), 52.04
(CH2′), 64.60 (CH), 67.78 (CH′), 101.35 (CCl3),
102.12 (CCl3′), 107.85 (C4), 109.13 (C4′), 110.84 (C3),
115.64 (C3′), 119.01 q (CF3, 1JCF = 322.4 Hz), 119.20 q
3
6.99 m (1H, 2-H), 10.74 br.s (1H, NH, J = 7.8 Hz).
13C NMR spectrum, δC, ppm: 35.87 (CH3), 67.68 (CH),
102.23 (CCl3), 108.77 (C4), 115.19 (C3), 119.16 q
(CF3, 1JCF = 322.4 Hz), 121.61 (C5), 122.72 (C2).
Reaction of N-(2,2,2-trichloroethylidene)tri-
fluoromethanesulfonamide (Ia) with 1,6-bis(1H-
pyrrol-1-yl)hexane. The reaction mixture was treated
in a similar way. Pyrrole IIe, 1.08 g (0.005 mol), was
added to 0.01 mol of Schiff base Ia. According to the
NMR data, the residue contained compound XVIa
with an impurity of 2,3′-substituted isomer (ratio 5:1).
Overall yield 3.17 g (82%).
1
(CF3′, JCF = 322.4 Hz), 121.30 (C5′), 122.59 (C2′),
123.66 (C5), 124.77 (C2), 126.82 (C2″, C6″ in C6H4),
127.85 (C3″, C5″ in C6H4), 136.37 (C1″ in C6H4), 138.20
(C4″ in C6H4).
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KONDRASHOV et al.
1370
1,4-Bis[3-(2,2,2-trichloro-1-trifluoromethylsul-
N-{1-[1-(4-Nitrophenyl)-1H-pyrrol-3-yl]-2,2,2-
trichloroethyl}trifluoromethanesulfonamide (XV).
1H NMR spectrum, δ, ppm: 5.33 s (1H, CH), 6.74 m
(1H, 2-H), 7.60 m (1H, 4-H), 7.95 m (1H, 5-H), 7.82 d
and 8.34 d (4H, AA′BB′, C6H4), 10.97 br.s (1H, NH).
fonylaminoethyl)-1H-pyrrol-1-ylmethyl]benzene
(XIX). 13C NMR spectrum, δC, ppm: 52.04 (CH2),
67.78 (CH), 102.12 (CCl3), 109.13 (C4), 115.64 (C3),
1
119.20 q (CF3, JCF = 322.4 Hz), 121.30 (C5), 122.59
(C2), 126.58 (C2″, C3″, C5″, C6″ in C6H4), 138.04 (C1″,
C4″ in C6H4).
13C NMR spectrum, δC, ppm: 67.32 (CH), 101.54
1
(CCl3), 112.73 (C2), 119.20, 119.26 q (CF3, JCF
=
322.1 Hz), 119.57 (C4), 120.02 (C3), 120.63 (C5),
125.70, 144.10, 144.48.
N-[1-(1-Benzyl-1H-pyrrol-2-yl)-2,2,2-trichloro-
ethyl]trifluoromethanesulfonamide (IIIc). A solution
of 1.57 g (0.01 mol) of N-benzylpyrrole in 4 ml of
carbon tetrachloride was added to 0.01 mol of Schiff
base Ia, and the mixture was stirred for 6 h at room
temperature. The precipitate was filtered off, washed
with cold hexane, and dried under reduced pressure.
N-[2,2,2-Trichloro-1-(1H-pyrrol-2-yl)ethyl]-
benzenesulfonamide (IVa). A solution of 0.67 g
(0.01 mol) of pyrrole (IIa) in 5 ml of carbon tetra-
chloride was added dropwise to 2.86 g (0.01 mol) of
Schiff base Ib in 25 ml of anhydrous carbon tetra-
chloride under stirring at –15°C. After 30 min, the
mixture was allowed to warm up to room temperature,
stirred for 5 h, and kept for 12 h in the cold. The
precipitate was filtered off, washed with 50 ml of
10% aqueous ammonia, and dried. Yield 2.62 g (74%),
mp 178–182°C. IR spectrum, KBr, ν, cm–1: 3420, 3230
1
Yield 4.01 g (92%), mp 132°C. H NMR spectrum, δ,
2
ppm: 5.18 d and 5.29 d (2H, AB, CH2, J = 15.8 Hz),
5.38 s (1H, CH), 6.12 m (1H, 4-H), 6.63 m (1H, 3-H),
6.85 m (1H, 5-H), 7.16–7.40 m (5H, C6H5), 10.95 s
(1H, NH). 13C NMR spectrum, δC, ppm: 50.41 (CH2),
64.52 (CH), 101.39 (CCl3), 107.72 (C4), 110.84 (C3),
1
118.92 q (CF3, JCF = 322.4 Hz), 123.80 (C5), 124.67
1
(NH); 1320, 1160 (SO2). H NMR spectrum, δ, ppm:
(C2), 127.62, 127.64, 128.52, 137.06. Found, %:
C 38.84; H 2.73; Cl 23.93; N 6.34; S 7.17.
C14H12Cl3F3N2O2S. Calculated, %: C 38.60; H 2.78;
Cl 24.41; N 6.43; S 7.36.
3
5.25 d (1H, CH, J = 9.0 Hz), 5.78 m (1H, 4-H),
6.17 m (1H, 3-H), 6.53 m (1H, 5-H), 7.32–7.60 m (5H,
3
C6H5), 8.86 d (1H, NH, J = 9.0 Hz), 10.69 s (1H,
1-H). 13C NMR spectrum, δC, ppm: 66.26 (CH),
102.26 (CCl3), 107.57 (C4), 108.68 (C3), 117.73 (C5),
123.92 (C2), 126.16, 128.51, 132.07, 140.69. 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.
Reaction of N-(2,2,2-trichloroethylidene)tri-
fluoromethanesulfonamide (Ia) with N-(4-nitro-
phenyl)pyrrole. Carbon tetrachloride, 4 ml, was added
to 0.01 mol of Schiff base Ia, 1.88 g (0.01 mol) of pyr-
role IId was added with shaking, and the mixture was
kept for 2 days at room temperature. The precipitate
was filtered off and washed with hexane on a filter.
According to the NMR data, the product was a mixture
of compounds IIId and XV at a ratio of 10:1. Overall
yield 3.97 g (85%). To isolate pure compound IIId,
the mixture was shaken with a small amount of hot
15% aqueous NaOH and filtered, the residue was
washed with 10% hydrochloric acid, and the precip-
itate was filtered off and dried.
Reaction of N-(2,2,2-trichloroethylidene)ben-
zenesulfonamide (Ib) with N-methylpyrrole.
N-Methylpyrrole, 0.81 g (0.01 mol), was added to
0.01 mol of Schiff base Ib, and the mixture spontane-
ously warmed up. The mixture was then heated to
80°C over a period of 3 h and evaporated under
reduced pressure, and the residue was recrystallized
from carbon tetrachloride. According to the NMR data,
the product was a mixture of amides IVb and XI at
a ratio of 5:1; overall yield 3.07 g (84%).
N-{2,2,2-Trichloro-1-[1-(4-nitrophenyl)-1H-pyr-
rol-2-yl]ethyl}trifluoromethanesulfonamide (IIId).
Individual compound IVb was obtained when a so-
lution of N-methylpyrrole in carbon tetrachloride was
added dropwise under stirring to a solution of Schiff
base Ib in the same solvent, cooled to –15°C. The mix-
ture was then kept for 12 h at room temperature and
treated as described above.
1
Yield 3.03 g (65%), mp 212°C. H NMR spectrum, δ,
ppm: 5.29 s (1H, CH), 6.39 m (1H, 5-H), 6.92 m (1H,
3-H), 7.16 m (1H, 4-H), 7.54 d, 8.42 d (4H, AA′BB′,
C6H4), 11.34 br.s (1H, NH). 13C NMR spectrum, δC,
ppm: 64.79 (CH), 100.76 (CCl3), 110.17 (C5), 113.51
1
(C3), 119.25 q (CF3, JCF = 322.1 Hz), 124.05 (C2),
125.47, 125.51 (C4), 127.18, 144.35, 146.67. Found,
%: C 33.27; H 1.91; Cl 22.85; N 8.89; S 6.93.
C13H9Cl3F3N3O4S. Calculated, %: C 33.46; H 1.94;
Cl 22.79; N 9.00; S 6.87.
N-[2,2,2-Trichloro-1-(1-methyl-1H-pyrrol-2-yl)-
ethyl]benzenesulfonamide (IVb). Yield 2.70 g (74%),
1
mp 129–132°C. H NMR spectrum, δ, ppm: 3.36 s
3
(3H, CH3), 5.03 d (1H, CH, J = 9.9 Hz), 5.80 m (1H,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

C-AMIDOALKYLATION OF PYRROLES
1371
4-H), 6.38 m (1H, 3-H), 6.48 m (1H, 5-H), 7.37 m (2H,
S 8.11. C13H12Cl4N2O2S. Calculated, %: C 38.83;
H 3.01; Cl 35.27; N 6.97; S 7.97.
m-H), 7.48 m (1H, p-H), 7.60 m (2H, o-H), 9.07 d (1H,
3
NH, J = 9.9 Hz). 13C NMR spectrum, δC, ppm: 33.57
4-Chloro-N-[2,2,2-trichloro-1-(1-methyl-1H-pyr-
(CH3), 63.92 (CH), 102.06 (CCl3), 106.80 (C4), 109.68
(C3), 123.00 (C5), 125.19 (C2), 126.13, 128.63, 132.27,
140.22. Found, %: C 42.54; H 3.48; Cl 28.11; N 7.54;
S 8.83. C13H13Cl3N2O2S. Calculated, %: C 42.47;
H 3.56; Cl 28.93; H 7.62; S 8.72.
1
rol-3-yl)ethyl]benzenesulfonamide (XII). H NMR
spectrum, δ, ppm: 3.34 s (3H, CH3), 4.94 d (1H, CH,
3J = 10.1 Hz), 6.02 m (1H, 4-H), 6.40 m (1H, 5-H),
6.54 m (1H, 2-H), 7.44 d and 7.60 d (4H, AA′BB′,
C6H4), 8.78 d (1H, NH, 3J = 10.1 Hz). 13C NMR spec-
trum, δC, ppm: 34.94 (CH3), 67.61 (CH), 103.31
(CCl3), 108.99 (C4), 121.62 (C3), 123.32 (C5), 125.42
(C2), 128.82, 128.96, 137.35, 139.42.
N-[2,2,2-Trichloro-1-(1-methyl-1H-pyrrol-3-yl)-
1
ethyl]benzenesulfonamide (XI). H NMR spectrum,
3
δ, ppm: 3.39 s (3H, CH3), 4.97 d (1H, CH, J =
10.2 Hz), 6.04 m (1H, 4-H), 6.40 m (1H, 5-H), 6.56 m
N-[1-(1-Benzyl-1H-pyrrol-2-yl)-2,2,2-trichloro-
ethyl]-4-chlorobenzenesulfonamide (Vc) was synthe-
sized as described above for compound IIIc from
Schiff base Ic and 1.57 g (0.01 mol) of N-benzylpyr-
(1H, 2-H), 7.37 m (2H, m-H), 7.48 m (1H, p-H),
3
7.63 m (2H, o-H), 8.71 d (1H, NH, J = 10.2 Hz).
13C NMR spectrum, δC, ppm: 35.49 (CH3), 67.15 (CH),
103.11 (CCl3), 108.56 (C4), 115.89 (C3), 121.08 (C5),
122.71 (C2), 126.48, 128.33, 131.96, 140.98.
1
role. Yield 4.09 g (86%), mp 165–168°C. H NMR
spectrum, δ, ppm: 5.02 s (2H, CH2), 5.26 d (1H, CH,
3J = 9.8 Hz), 5.95 m (1H, 4-H), 6.47 m (1H, 3-H),
6.64 m (1H, 5-H), 7.03–7.27 m (5H, C6H5), 7.41 d and
1,6-Bis{2-[2,2,2-trichloro-1-(4-chlorophenylsul-
fonylamino)ethyl]-1H-pyrrol-1-yl}hexane (XVIb)
was synthesized in a similar way from 0.01 mol of
Schiff base Ic and 1.08 g (0.005 mol) of bis-pyrrole
3
7.47 d (4H, AA′BB′, C6H4), 9.25 d (1H, NH, J =
9.8 Hz). 13C NMR spectrum, δC, ppm: 50.65 (CH2),
64.41 (CH), 107.98 (C4), 110.75 (C3), 123.45 (C5),
125.87 (C2), 128.03, 128.14, 128.40, 129.00, 129.25,
137.53, 137.58, 140.43. Found, %: C 47.54; H 3.24;
Cl 29.74; N 5.72; S 6.75. C19H16Cl4N2O2S. Calculated,
%: C 47.72; H 3.37; Cl 29.65; N 5.86; S 6.70.
1
IIe. Yield 3.36 g (78%), mp 198–200°C. H NMR
spectrum, δ, ppm: 1.06 m (4H, CH2), 1.41 m (4H,
CH2), 3.72 m (4H, CH2), 5.14 s (2H, CH), 5.92 m (2H,
4-H), 6.45 m (2H, 3-H), 6.66 m (2H, 5-H), 7.46 d and
7.62 d (8H, AA′BB′, C6H4), 9.30 br.s (2H, NH).
13C NMR spectrum, δC, ppm: 26.15 (CH2), 30.62
(CH2), 46.57 (CH2), 64.30 (CH), 102.61 (CCl3), 107.59
(C4), 110.30 (C3), 122.35 (C5), 125.11 (C2), 128.42,
129.23, 137.56, 140.40. Found, %: C 42.11; H 3.56;
Cl 32.79; N 6.62; S 7.34. C30H30Cl8N4O4S2. Calculat-
ed, %: C 41.98; H 3.52; Cl 33.04; N 6.53; S 7.47.
Reaction of 4-chloro-N-(2,2,2-trichloroethyli-
dene)benzenesulfonamide (Ic) with N-(4-nitro-
phenyl)pyrrole (IId). Pyrrole IId, 1.88 g (0.01 mol),
was added under shaking to 0.01 mol of Schiff base Ic,
5 drops of freshly distilled boron trifluoride–ether
complex were then added, and the mixture was heated
for 8 h at 80°C. The precipitate was filtered off and
washed with carbon tetrachloride and aqueous ammo-
nia. The NMR spectra of the product (3.75 g) con-
tained signals of amide Vd and compound XIV.
The reaction of 4-chloro-N-(2,2,2-trichloroethyli-
dene)benzenesulfonamide (Ic) with N-methylpyr-
role was performed in a similar way using 0.01 mol of
Schiff base Ic and 0.81 g (0.01 mol) of N-methyl-
pyrrole, and individual compound Vb was isolated as
described above for IVb. According to the NMR data,
the residue was a mixture of sulfonamides Vb and XII
at a ratio of 8:1; overall yield 2.86 g (71%).
4-Chloro-N-{1-[2,2,2-trichloro-1-(4-nitrophenyl)-
1H-pyrrol-2-yl]ethyl}benzenesulfonamide (Vd).
3
1H NMR spectrum, δ, ppm: 5.16 d (1H, CH, J =
9.8 Hz), 6.25 m (1H, 5-H), 6.80 m (1H, 3-H), 7.00 m
(1H, 4-H), 7.34 d and 8.41 d (4H, AA′BB′, C6H4NO2),
7.58 d and 7.78 d, (4H, AA′BB′, C6H4Cl), 9.58 d (1H,
4-Chloro-N-[2,2,2-trichloro-1-(1-methyl-1H-
pyrrol-2-yl)ethyl]benzenesulfonamide (Vb). Yield
3
NH, J = 9.8 Hz). 13C NMR spectrum, δC, ppm: 63.81
1
3.34 g (83%), mp 146–148°C. H NMR spectrum, δ,
(CH), 101.60 (CCl3), 109.84 (C5), 113.07 (C3), 124.69
(C2), 125.27, 125.68 (C4), 127.03, 128.34, 129.20,
137.55, 139.94, 144.13, 146.41.
ppm: 3.40 s (3H, CH3), 5.01 d (1H, CH, 3J = 10.2 Hz),
5.78 m (1H, 4-H), 6.29 m (1H, 3-H), 6.50 m (1H, 5-H),
7.42 d and 7.57 d (4H, AA′BB′, C6H4), 9.14 d (1H, NH,
3J = 10.2 Hz). 13C NMR spectrum, δC, ppm: 34.15
(CH3), 64.51 (CH), 102.25 (CCl3), 107.37 (C4), 110.19
(C3), 123.56 (C5), 125.51 (C2), 128.56, 129.21, 137.69,
139.49. Found, %: C 38.56; H 2.97; Cl 35.38; N 6.84;
2,2,2-Trichloro-1,1-bis[1-(4-nitrophenyl)-1H-
pyrrol-2-yl]ethane (XIV). 1H NMR spectrum, δ, ppm:
4.92 (CH), 6.33 m (1H, 5-H), 6.95 m (1H, 3-H),
6.97 m (1H, 4-H), 7.37 d and 8.12 d (4H, AA′BB′,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

KONDRASHOV et al.
1372
C6H4). 13C NMR spectrum, δC, ppm: 52.29 (CH),
102.34 (CCl3), 109.84 (C5), 112.77 (C3), 124.15 (C4),
124.76, 128.04, 128.47 (C2), 144.19, 146.38.
6.28 m (1H, 3-H), 6.41 m (1H, 5-H), 7.39–7.81 m
3
(15H, C6H5), 8.78 d (1H, NH, J = 9.9 Hz). 13C NMR
spectrum, δC, ppm: 49.86 (CH2), 61.85 (CH), 96.06
(CCl2), 106.99 (C4), 110.07 (C3), 121.88 (C5), 126.12
(C2), 127.04, 127.67, 127.93, 128.01, 128.36, 128.88,
129.15, 129.46, 136.31, 137.67, 139.52, 140.32.
Found, %: C 61.43; H 4.38; Cl 14.46; N 5.48; S 6.87.
C25H22Cl2N2O2S. Calculated, %: C 61.86; H 4.57;
Cl 14.61; N 5.77; S 6.60.
N-[2,2-Dichloro-2-phenyl-1-(1H-pyrrol-2-yl)-
ethyl]benzenesulfonamide (VIa). A solution of 3.28 g
(0.01 mol) of Schiff base Id and 0.94 g (0.014 mol) of
pyrrole (IIa) in 10 ml of anhydrous carbon tetrachlo-
ride was stirred for 15 min. The mixture was kept in
the cold until a solid separated, and the precipitate was
filtered off, washed with 50 ml of 10% aqueous am-
monia, and dried. Yield 4.00 g (95%), mp 162–163°C.
IR spectrum (KBr), ν, cm–1: 3410, 3230 (NH); 1320,
N-[2,2-Dichloro-2-phenyl-1-(1H-pyrrol-2-yl)-
ethyl]-4-methylbenzenesulfonamide (VIIa) was syn-
thesized as described above for compound VIa from
3.42 g (0.01 mol) of Schiff base Ie and 0.94 g
(0.014 mol) of pyrrole (IIa). Yield 3.92 g (90%),
mp 182–184°C. IR spectrum (KBr), ν, cm–1: 3400,
1
1170 (SO2). H NMR spectrum, δ, ppm: 5.24 d (1H,
3
CH, J = 10.0 Hz), 5.66 m (1H, 4-H), 5.79 m (1H,
3-H), 6.36 m (1H, 5-H), 7.32–7.58 m (10H, C6H5),
3
1
8.48 d (1H, NH, J = 10.0 Hz), 10.21 br.s (1H, NH).
3210 (NH); 1305, 1140 (SO2). H NMR spectrum, δ,
3
13C NMR spectrum, δC, ppm: 64.03 (CH), 95.43
(CCl2), 107.19 (C4), 108.35 (C3), 116.93 (C5), 124.35
(C2), 124.82, 125.96, 128.02, 129.31, 129.54, 137.68,
139.67, 142.48. Found, %: C 54.38; H 4.11; Cl 17.45;
N 7.15; S 8.28. C18H16Cl2N2O2S. Calculated, %:
C 54.69; H 4.08; Cl 17.94; N 7.09; S 8.11.
ppm: 2.26 s (3H, CH3), 5.25 d (1H, NCH, J =
10.0 Hz), 5.67 m (1H, 4-H), 5.77 m (1H, 3-H), 6.38 m
(1H, 5-H), 7.07–7.55 m (9H, C6H4, C6H5), 8.22 d (1H,
3
NH, J = 10.0 Hz), 10.19 s (1H, NH). 13C NMR spec-
trum, δC, ppm: 21.57 (CH3), 65.03 (CH), 94.80 (CCl2),
108.24 (C4), 110.31 (C3), 118.33 (C5), 124.65 (C2),
127.15, 127.28, 128.25, 129.46, 129.61, 137.00, 139.56,
143.48. 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.
In the synthesis of compounds VIb and VIc the
reaction mixtures were treated in a similar way.
N-[2,2-Dichloro-1-(1-methyl-1H-pyrrol-2-yl)-2-
phenylethyl]benzenesulfonamide (VIb). A solution
of 3.28 g (0.01 mol) of Schiff base Id and 1.14 g
(0.014 mol) of N-methylpyrrole in 10 ml of anhydrous
carbon tetrachloride was stirred for 2 h on heating
under reflux. Yield 4.30 g (97%), mp 158–159°C. IR
spectrum (KBr), ν, cm–1: 3240 (NH); 1390, 1170
Reaction of N-(2,2-dichloro-2-phenylethylidene)-
4-methylbenzenesulfonamide (Ie) with N-methyl-
pyrrole. A solution of 3.42 g (0.01 mol) of Schiff base
Ie and 1.14 g (0.014 mol) of N-methylpyrrole in 30 ml
of anhydrous carbon tetrachloride was heated for 5 h
under reflux with stirring. The mixture was then kept
in the cold until a solid separated, and the precipitate
was filtered off, washed with 50 ml of 10% aqueous
ammonia, and dried. According to the NMR data, the
product was a mixture of amides VIIb and XIII at
a molar ratio of 4:1; overall yield 3.44 g (81%). Com-
pound VIIb was isolated as individual substance by
fractional crystallization of the reaction mixture.
1
(SO2). H NMR spectrum, δ, ppm: 2.82 s (3H, CH3),
3
4.92 d (1H, CH, J = 10.0 Hz), 5.69 m (1H, 4-H),
6.17 m (1H, 3-H), 6.25 m (1H, 5-H), 7.31–7.78 m
(10H, C6H5), 8.76 d (1H, NH, 3J = 10.0 Hz). 13C NMR
spectrum, δC, ppm: 33.74 (CH3), 63.00 (CH), 96.42
(CCl2), 107.65 (C4), 110.76 (C3), 122.81 (C5), 125.41
(C2), 126.11, 127.45, 127.65, 128.56, 129.28, 137.63,
139.02, 140.34. Found, %: C 55.38; H 4.38; Cl 17.64;
N 6.56; S 7.95. C19H18Cl2N2O2S. Calculated, %:
C 55.75; H 4.43; Cl 17.32; N 6.84; S 7.83.
N-[2,2-Dichloro-1-(1-methyl-1H-pyrrol-2-yl)-2-
phenylethyl]-4-methylbenzenesulfonamide (VIIb).
Yield 2.67 g (65%), mp 140–142°C. IR spectrum
(KBr), ν, cm–1: 3230 (NH); 1320, 1150 (SO2). 1H NMR
spectrum, δ, ppm: 2.26 s (3H, CH3C6H4), 2.78 s (3H,
N-[1-(1-Benzyl-1H-pyrrol-2-yl)-2,2-dichloro-2-
phenylethyl]benzenesulfonamide (VIc). A solution of
3.28 g (0.01 mol) of Schiff base Id and 2.20 g
(0.014 mol) of N-benzylpyrrole in 5 ml of anhydrous
carbon tetrachloride was stirred for 30 min on heating
under reflux. Yield 3.90 g (71%), mp 178–180°C. IR
spectrum (KBr), ν, cm–1: 3250 (NH); 1320, 1160
3
NCH3), 4.90 d (1H, CH, J = 9.7 Hz), 5.72 m (1H,
4-H), 6.23 m (1H, 3-H), 6.24 m (1H, 5-H), 7.08–
3
7.48 m (9H, Harom), 8.58 d (1H, NH, J = 9.7 Hz).
13C NMR spectrum, δC, ppm: 20.86 (CH3C6H4), 32.67
(NCH3), 61.88 (CH), 95.69 (CCl2), 106.54 (C4),
109.67 (C3), 121.65 (C5), 126.08 (C2), 126.12, 127.50,
1
(SO2). H NMR spectrum, δ, ppm: 4.33 s (2H, CH2),
3
5.08 d (1H, CH, J = 9.9 Hz), 5.86 m (1H, 4-H),
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C-AMIDOALKYLATION OF PYRROLES
1373
127.82, 128.77, 129.31, 137.81, 139.30, 141.99.
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.
4-Chloro-N-[2,2-dichloro-1-(1-methyl-1H-pyr-
rol-2-yl)-2-phenylethyl]benzenesulfonamide (VIIIb)
was synthesized as described above for compound VIb
from 3.62 g (0.01 mol) of Schiff base If and 1.14 g
(0.014 mol) of N-methylpyrrole. Yield 4.10g (86%),
mp 153–156°C (decomp.). IR spectrum (KBr), ν, cm–1:
N-[2,2-Dichloro-1-(1-methyl-1H-pyrrol-3-yl)-2-
phenylethyl]-4-methylbenzenesulfonamide (XIII).
1H NMR spectrum, δ, ppm: 2.28 s (3H, CH3C6H4),
1
3280 (NH); 1330, 1170 (SO2). H NMR spectrum, δ,
ppm: 2.78 s (3H, CH3), 4.91 d (1H, CH, 3J = 10.2 Hz),
3
3.26 s (3H, NCH3), 5.05 d (1H, CH, J = 9.7 Hz),
5.69 m (1H, 4-H), 6.22 m (1H, 3-H), 6.22 d (1H, 5-H),
5.52 m (1H, 4-H), 6.10 m (1H, 2-H), 6.21 m (1H, 5-H),
3
7.27–7.49 m (9H, C6H4, C6H5), 8.67 d (1H, NH, J =
3
7.12–7.50 m (9H, C6H4, C6H5), 8.25 d (1H, NH, J =
10.2 Hz). 13C NMR spectrum, δC, ppm: 32.65 (CH3),
61.89 (CH), 95.63 (CCl2), 106.54 (C4), 109.67 (C3),
121.73 (C5), 126.04 (C2), 127.15, 127.92, 128.02,
128.95, 129.42, 137.68, 139.08, 140.52. Found, %:
C 51.15; H 3.72; Cl 23.62; N 6.35; S 7.31.
C19H17Cl3N2O2S. Calculated, %: C 51.42; H 3.86;
Cl 23.97; N 6.31; S 7.22.
9.7 Hz). 13C NMR spectrum, δC, ppm: 20.87 (CH3-
C6H4), 35.29 (NCH3), 64.73 (CH), 96.36 (CCl2),
108.36 (C4), 117.15 (C3), 120.45 (C5), 121.99 (C2),
126.01, 126.48, 127.23, 128.51, 128.96, 138.57,
140.45, 141.74.
N-[1-(1-Benzyl-1H-pyrrol-2-yl)-2,2-dichloro-2-
phenylethyl]-4-methylbenzenesulfonamide (VIIc)
was synthesized as described above for compound VIc
from 3.42 g (0.01 mol) of Schiff base Ie and 2.20 g
(0.014 mol) of N-benzylpyrrole. Yield 4.04 g (72%),
mp 160–161°C. IR spectrum (KBr), ν, cm–1: 3250
N-[1-(1-Benzyl-1H-pyrrol-2-yl)-2,2-dichloro-2-
phenylethyl]-4-chlorobenzenesulfonamide (VIIIc)
was synthesized as described above for compound VIc
from 3.62 g (0.01 mol) of Schiff base If and 2.20 g
(0.014 mol) of N-benzylpyrrole. Yield 2.55 g (88%),
mp 163–165°C. IR spectrum (KBr), ν, cm–1: 3240
1
(NH); 1330, 1130 (SO2). H NMR spectrum, δ, ppm:
2.27 s (3H, CH3), 4.35 s (2H, CH2), 5.11 d (1H, CH,
3J = 10.1 Hz), 5.86 m (1H, 4-H), 6.40 m (1H, 3-H),
6.82 m (1H, 5-H), 7.26–7.63 m (14H, C6H4, C6H5),
8.79 d (1H, NH, 3J = 10.1 Hz). 13C NMR spectrum, δC,
ppm: 20.76 (CH3), 49.28 (CH2), 61.52 (CH), 95.88
(CCl2), 106.85 (C4), 109.76 (C3), 121.38 (C5), 125.98
(C2), 126.98, 127.52, 127.85, 128.10, 128.61, 128.83,
129.16, 129.37, 136.41, 137.70, 139.64, 140.05.
Found, %: C 62.23; H 4.81; Cl 14.52; N 5.34; S 6.38.
C26H24Cl2N2O2S. Calculated, %: C 62.53; H 4.84;
Cl 14.20; N 5.61; S 6.42.
1
(NH); 1340, 1160 (SO2). H NMR spectrum, δ, ppm:
3
4.32 s (2H, CH2), 5.15 d (1H, CH, J = 10.0 Hz),
5.85 m (1H, 4-H), 6.34 m (1H, 3-H), 6.86 m (1H, 5-H),
3
7.28–7.58 m (14H, C6H4, C6H5), 8.86 d (1H, NH, J =
10.0 Hz). 13C NMR spectrum, δC, ppm: 49.17 (CH2),
61.89 (CH), 95.91 (CCl2), 107.11 (C4), 110.40 (C3),
121.49 (C5), 126.24 (C2), 127.54, 127.98, 128.03,
128.14, 128.40, 128.92, 129.00, 129.25, 136.54,
137.58, 139.39, 140.16. Found, %: C 57.23; H 4.17;
Cl 20.65; N 5.28; S 6.23. C25H21Cl3N2O2S. Calculated,
%: C 57.76; H 4.07; Cl 20.46; N 5.39; S 6.17.
4-Chloro-N-[2,2-dichloro-2-phenyl-1-(1H-pyrrol-
2-yl)ethyl]benzenesulfonamide (VIIIa) was synthe-
sized as described above for compound VIa from
3.62 g (0.01 mol) of Schiff base If and 0.94 g
(0.014 mol) of pyrrole (IIa). Yield 3.78 g (83%),
mp 194–195°C. IR spectrum (KBr), ν, cm–1: 3390,
Reaction of 4-chloro-N-(2,2,2-trichloroethyli-
dene)benzenesulfonamide (Ic) with 1,4-bis(1H-pyr-
rol-1-ylmethyl)benzene (IIf). The reaction was
carried out as described above for compounds IVb and
XI from 1.18 g (0.005 mol) of pyrrole IIf and 0.01 mol
of Schiff base Ic. According to the NMR data, the
residue was a mixture of amide XVIIb and its
2,3′-substituted isomer at a ratio of 5:1. Overall yield
3.79 g (86%).
1
3230 (NH); 1300, 1150 (SO2). H NMR spectrum, δ,
ppm: 5.25 d (1H, CH, 3J = 10.3 Hz), 5.63 m (1H, 4-H),
5.78 m (1H, 3-H), 6.34 m (1H, 5-H), 7.26–7.56 m (9H,
C6H4, C6H5), 8.38 d (1H, NH, 3J = 10.3 Hz), 10.22 br.s
(1H, NH). 13C NMR spectrum, δC, ppm: 64.09 (CH),
95.65 (CCl2), 107.08 (C4), 108.35 (C3), 116.93 (C5),
124.28 (C2), 124.90, 125.88, 127.55, 128.99, 129.11,
137.15, 139.06, 140.91. Found, %: C 50.08; H 3.42;
Cl 24.54; N 6.37; S 7.29. C18H15Cl3N2O2S. Calculated,
%: C 50.31; H 3.52; Cl 24.75; N 6.52; S 7.46.
1,4-Bis{3-[2,2,2-trichloro-1-(4-chlorophenylsul-
fonylamino)ethyl]-1H-pyrrol-1-ylmethyl}benzene
1
(XVIIb). H NMR spectrum, δ, ppm: 4.99 s (4H,
CH2), 5.24 d (2H, CH, 3J = 9.5 Hz), 5.94 m (2H, 4-H),
6.47 m (2H, 3-H), 6.55 m (2H, 5-H), 6.94 s (4H,
C6H4), 7.43 d and 7.51 d (4H each, AA′BB′, C6H4),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 9 2009

KONDRASHOV et al.
1374
3
9.24 d (2H, NH, J = 9.5 Hz). 13C NMR spectrum, δC,
ppm: 49.72 (CH2), 63.90 (CH), 102.02 (CCl3), 107.52
(C4), 110.27 (C3), 122.74 (C5), 125.42 (C2), 127.78,
127.92, 128.74, 136.44, 137.03, 139.92. Found, %:
C 49.58; H 3.02; Cl 32.12; N 6.47; S 7.19.
C32H26Cl8N4O4S2. Calculated, %: C 43.76; H 2.98;
Cl 32.29; N 6.38; S 7.30.
5. 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.
6. Mirskova, A.N., Levkovskaya, G.G., Drozdova, T.I.,
Kalikhman, I.D., and Voronkov, M.G., Zh. Org. Khim.,
1982, vol. 18, p. 452.
7. Drozdova, T.I. and Mirskova, A.N., Russ. J. Org.
Chem., 2001, vol. 37, p. 284.
8. Pozharskii, A.F., Anisimova, V.A., and Tsupak, E.B.,
Prakticheskie raboty po khimii geterotsiklov (Labora-
tory Works on the Chemistry of Heterocycles), Rostov-
on-Don: Rostov. Gos. Univ., 1988, p. 22.
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