Reduction of N-(Polychloroethylidene)- and N-(1-Hydroxypolychloroethyl) arenesulfonamides with adamantane in the presence of superacids

Article abstract of DOI:10.1134/S1070428011040087

N-(2,2,2-Trichloroethylidene)-, N-(2,2-dichloro-2-phenylethylidene)-, and N-(1-hydroxy-2-polychloroethyl) arenesulfonamides reacted with adamantane in carbon tetrachloride in the presence of oleum or concd. H₂SO ₄-P₄O

Full text of DOI:10.1134/S1070428011040087

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2011, Vol. 47, No. 4, pp. 520–522. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © G.N. Rozentsveig, A.V. Popov, I.B. Rozentsveig, G.G. Levkovskaya, 2011, published in Zhurnal Organicheskoi Khimii, 2011,
Vol. 47, No. 4, pp. 523–525.
Reduction of N-(Polychloroethylidene)- and N-(1-Hydroxy-
polychloroethyl)arenesulfonamides with Adamantane
in the Presence of Superacids
G. N. Rozentsveig, A. V. Popov, I. B. Rozentsveig, and G. G. Levkovskaya
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: gelya2010@irioch.irk.ru
Received July 12, 2010
Abstract—N-(2,2,2-Trichloroethylidene)-, N-(2,2-dichloro-2-phenylethylidene)-, and N-(1-hydroxy-2-poly-
chloroethyl)arenesulfonamides reacted with adamantane in carbon tetrachloride in the presence of oleum or
concd. H2SO4–P4O10 mixture to give the corresponding N-(2-polychloroethyl)arenesulfonamides as a result of
reduc-tion of the azomethine and OH group, respectively.
DOI: 10.1134/S1070428011040087
N-Arylsulfonyl-substituted polychlorinated alde-
hyde imines possess an activated CH=N bond and are
convenient building blocks for the preparation of vari-
ous acyclic and cyclic sulfonamide derivatives [1, 2].
We previously developed efficient preparative proce-
dures for the synthesis of N-(2,2,2-trichloroethyli-
dene)- and N-(2,2-dichloro-2-phenylethylidene)arene-
sulfonamides I and II via radical reactions of N,N-di-
chloroarenesulfonamides with trichloroethylene and
phenylacetylene [1–4], so that these important reagents
became accessible. We perform systematic studies on
reactions of polyhalogenated aldehyde imines in the
presence of strong acids. For instance, oleum as super-
acid [5] is capable of protonating electron-deficient
azomethine group in N-sulfonyl imines to generate
amidoalkyl carbocations. Among possible further
transformations of the latter, C-amidoalkylation of aro-
matic and heteroaromatic compounds was studied most
thoroughly [6–9].
in the presence of H2SO4, P4O10, or phosphoric acid
taken separately. N-(Polychloroethyl)arenesulfon-
amides IIIa, IIIb, IVa, and IVb were also obtained
from N-(1-hydroxy-2-polychloroethyl)arenesulfon-
amides Va, Vb, VIa, and VIb under analogous con-
ditions (in the presence of adamantane and oleum or
H2SO4–P4O10 mixture).
It is known that in the presence of acids adaman-
tane can formally act as hydride ion donor in reactions
with cycloalkenes, alcohols, and ketones [10, 11].
However, analogous behavior of adamantane toward
Schiff bases was not reported previously. According to
[12], hydride transfer reactions of carbonyl compounds
with branched hydrocarbons in the presence of super-
acids are possible only with dicationic intermediates
possessing superelectrophilic properties, but no such
reactions occur with monocations. By analogy, we
presumed that protonation of Schiff bases Ia, Ib, IIa,
and IIb gives superelectrophilic dications A. Protona-
tion of hemiaminals Va, Vb, VIa, and VIb is accom-
panied by elimination of water, leading to the same
dicationic species. The driving force for the subsequent
formation of N-polychloroethyl sulfonamides IIIa,
IIIb, IVa, and IVb via reaction of dications A with
adamantanes is likely to be formation of more stable
adamantyl cation.
In the present work we examined transformations
of imines Ia, Ib, IIa, and IIb in the presence of super-
acids and found that these compounds are capable of
reacting with adamantane to give products of reduction
of the CH=N group, the corresponding N-(polychloro-
ethyl)arenesulfonamides III and IV (Scheme 1). The
reactions successfully occurred in the presence of
oleum or a mixture of concentrated sulfuric acid with
phosphoric anhydride; however, no reduction occurred
The structure of compounds III and IV was con-
1
13
firmed by H and C NMR and IR spectroscopy and
520

REDUCTION OF N-(POLYCHLOROETHYLIDENE)- AND N-(1-HYDROXY-...
521
Scheme 1.
ArSO2
Cl
Cl
ClCH=CCl2
95–100%
N
Cl
Ia, Ib
ArSO2NCl2
ArSO2
Cl
Cl
PhC
≡
CH
N
90–95%
Ph
IIa, IIb
Ia, Ib, IIa, IIb
ArSO2
Cl
Cl
ArSO2
Cl
Cl
Oleum or H2SO4–P4O10
AdH
–Ad+, –H+
N
H
N
OH
H
H
X
X
ArSO2
Cl
Cl
N
A
IIIa, IIIb, IVa, IVb
H
(65–72%)
X
Va, Vb, VIa, VIb
III, V, X = Cl; IV, VI, X = Ph; Ar = Ph (a), 4-ClC6H4 (b); Ad = adamantyl.
1
elemental analysis. Their H NMR spectra contained
signals from protons in the aromatic ring, a triplet from
the NH proton at δ 8.5–9.0 ppm and a doublet from the
CH2 protons at δ ~3.9 ppm (2H). Compounds IIIa,
IVa, and IVb were not reported previously. 4-Chloro-
N-(2,2,2-trichloroethyl)benzenesulfonamide (IIIb) was
described in [13]. It was synthesized by addition of
N,N,4-trichlorobenzenesulfonamide to 1,1-dichloro-
ethylene and subsequent reduction of intermediate
N–Cl derivatives. The spectral parameters and melting
point of a sample of IIIb obtained in the present work
coincided with those reported in [13].
involving elimination of sulfonamide molecule, as we
showed previously [16]. The reduction procedure with
the use of adamantane is free from the above disadvan-
tages, so that it can be successfully applied to halogen-
containing Schiff bases and their functionalized deriva-
tives, and synthetic potential of these important re-
agents can be considerably extended.
EXPERIMENTAL
The IR spectra were recorded in KBr on a Bruker
1
IFS-25 spectrometer. The H and 13C NMR spectra
were measured on a Bruker DPX-400 spectrometer at
400.13 and 101.61 MHz, respectively, using DMSO-d6
as solvent and tetramethylsilane as reference.
We have found only one publication describing
reduction of the azomethine group in the series of
sulfonylimines derived prom polychlorocarbonyl com-
pounds: Davis et al. [14] reported that treatment of
cyclic camphor sulfonylimines with NaBH4 gave the
corresponding camphorsultams. The authors also noted
that similar reaction with bromine-containing analogs
involved dehydrobromination instead of reduction of
the C=N group. Safronova et al. [15] described the
reaction of N-(hexafluoroprop-2-ylidene)benzamide
with triethylamine; the latter acted as hydride ion
donor and reduced the Schiff base to N-(1-trifluoro-
methyl-2,2,2-trifluoroethyl)benzamide. N-Sulfonyl
imines derived from chlorinated aldehydes or ketones
failed to react in a similar way [1].
N-(Polychloroethylidene)arenesulfonamides Ia, Ib,
IIa, and IIb were synthesized, by radical reaction of
N,N-dichloroarenesulfonamides with trichloroethylene
or phenylacetylene according to the procedures report-
ed previously [1–4]. Hemiaminals Va, Vb, VIa, and
VIb were prepared as described in [17, 18].
N-(2,2,2-Trichloroethyl)benzenesulfonamide
(IIIa). a. A mixture of 2.87 g (0.01 mol) of N-(2,2,2-
trichloroethylidene)benzenesulfonamide (Ia), 1.36 g
(0.01 mol) of adamantane, 0.50 ml (0.01 mol) of
96% H2SO4, and 0.28 g (0.001 mol) of P4O10 in 25 ml
of carbon tetrachloride was vigorously stirred over
a period of 5 h. The mixture was then treated with
20 ml of water, and the precipitate was filtered off,
washed with 50 ml of 10% aqueous ammonia, dried in
air, and recrystallized from CHCl3. Yield 2.08 g (72%).
Obviously, the use of metal hydrides or organo-
metallic reagents as reducing agents for halogen-
containing N-sulfonyl imines is complicated due to
various side processes with participation of haloalkyl
groups. The action of alkaline reagents on hemiaminals
like V and VI could give rise to transformations
b. Compound IIIa was synthesized in a similar way
from 3.05 g (0.01 mol) of N-(2,2,2-trichloro-1-hy-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011

ROZENTSVEIG et al.
522
droxyethyl)benzenesulfonamide (Va). Yield 1.94 g
(67%), mp 175–177°C. H NMR spectrum, δ, ppm:
131.28, 134.41, 139.99 (Carom). Found, %: C 46.05;
H 3.35; Cl 29.31; N 3.88; S 8.85. C14H12Cl3NO2S. Cal-
culated, %: C 46.11; H 3.32; Cl 29.17; N 3.84; S 8.79.
1
3.89 d (2H, CH2, J = 6.6 Hz), 7.62–7.89 m (5H, Ph),
13
8.98 t (1H, NH, J = 6.6 Hz). C NMR spectrum, δC,
REFERENCES
ppm: 60.30 (CH2), 98.21 (CCl3), 128.35, 129.28,
137.48, 140.05 (Ph). Found, %: C 33.39; H 2.81;
Cl 36.56; N 4.65; S 11.39. C8H8Cl3NO2S. Calculated,
%: C 33.30; H 2.79; Cl 36.86; N 4.85; S 11.11.
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amide (IIIb) was synthesized in a similar way from
3.21 g (0.01 mol) of 4-chloro-N-(2,2,2-trichloroethyli-
dene)benzenesulfonamide (Ib) (a) or from 3.39 g
(0.01 mol) of 4-chloro-N-(2,2,2-trichloro-1-hydroxy-
ethyl)benzenesulfonamide (Vb) (b). Yield 2.20 g
(68%) (a), 2.10 g (65%) (b); mp 180–182°C; published
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1
data [13]: mp 179°C. H NMR spectrum, δ, ppm:
3.90 d (2H, CH2, J = 6.7 Hz), 7.63 d.d and 7.85 d.d
(2H each, C6H4, J = 8.6 Hz), 8.98 t (1H, NH, J =
6.7 Hz). 13C NMR spectrum, δC, ppm: 60.32 (CH2),
98.30 (CCl3), 128.33, 129.30, 137.52, 140.03 (C6H4).
Found, %: C 29.81; H 2.20; Cl 43.85; N 4.28; S 9.97.
C8H7Cl4NO2S. Calculated, %: C 29.75; H 2.18;
Cl 43.90; N 4.34; S 9.93.
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N-(2,2-Dichloro-2-phenylethyl)benzenesulfon-
amide (IVa) was synthesized in a similar way from
3.28 g (0.01 mol) of N-(2,2-dichloro-2-phenylethyli-
dene)benzenesulfonamide (IIa) (a) or 3.46 g
(0.01 mol) of N-(2,2-dichloro-1-hydroxyethyl)ben-
zenesulfonamide (VIa) (b). Yield 2.34 g (71%) (a),
10. Shokova, E.A. and Klop, V.V., Neftekhimiya, 1975,
vol. 15, no. 1, p. 82.
1
2.21 g (67%) (b); mp 192–193°C. H NMR spectrum,
11. Bagrii, E.I., Adamantany: poluchenie, primenenie,
svoistva (Adamantanes: Synthesis, Application, and
Properties), Moscow: Nauka, 1989.
δ, ppm: 3.89 d (2H, CH2, J = 6.9 Hz), 7.35–7.73 m
13
(10H, Harom, J = 6.9 Hz), 9.02 d (1H, NH). C NMR
spectrum, δC, ppm: 60.12 (CH2), 94.87 (CCl2), 127.95,
128.46, 129.01, 130.39, 131.45, 132.34, 134.49,
140.12 (Carom). Found, %: C 50.98; H 3.98; Cl 21.45;
N 4.28; S 9.69. C14H13Cl2NO2S. Calculated, %:
C 50.92; H 3.97; Cl 21.47; N 4.24; S 9.71.
12. Olah, G.A. and Klumpp, D.A., Superelectrophiles and
Their Chemistry, Hoboken, NJ: Wiley, 2008.
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Sulfur Silicon Relat. Elem., 1996, vol. 115, p. 85.
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4-Chloro-N-(2,2-dichloro-2-phenylethyl)ben-
zenesulfonamide (IVb) was synthesized in a similar
way from 3.63 g (0.01 mol) of 4-chloro-N-(2,2-di-
chloro-2-phenylethylidene)benzenesulfonamide (IIb)
(a) or 3.81 g (0.01 mol) of 4-chloro-N-(2,2-dichloro-1-
hydroxy-2-phenylethyl)benzenesulfonamide (VIb) (b).
Yield 2.67 g (73%) (a), 2.37 g (65%) (b); mp 187–
Arm. Khim. Zh., 1979, vol. 32, p. 315.
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1
189°C. H NMR spectrum, δ, ppm: 3.87 d (2H, CH2,
J = 6.8 Hz), 7.39–7.78 m (9H, Harom), 8.51 d (1H, NH,
J = 6.8 Hz). 13C NMR spectrum, δC, ppm: 60.09 (CH2),
94.79 (CCl2), 127.75, 128.05, 129.08, 130.18, 130.98,
18. Drozdova, T.I. and Mirskova, A.N., Russ. J. Org.
Chem., 2001, vol. 37, p. 284.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 4 2011