N-(2,2,2-trichloroethylidene)- and N-(2,2-dichloro-2-phenylethylidene)-4-methoxybenzenesulfonamides from 4-methoxy-N,N-dichlorobenzenesulfonamide, trichloroethylene, and phenylacethylene

Article abstract of DOI:10.1134/S1070428017110264

Reaction of 4-methoxy-N,N-dichlorobenzenesulfonamide with trichloroethylene and phenylacetylene underlies an effective method developed for the synthesis of highly reactive 4-methoxy-N-(2,2,2-trichloroethylidene)- and 4-methoxy-N-(2,2-dichloro)-2-phenylet

Full text of DOI:10.1134/S1070428017110264

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 11, pp. 1753–1755. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © Yu.A. Aizina, I.B. Rozentsveig, A.V. Popov, G.G. Levkovskaya, 2017, published in Zhurnal Organicheskoi Khimii, 2017, Vol. 53,
No. 11, pp. 1714–1716.
SHORT
COMMUNICATIONS
N-(2,2,2-Trichloroethylidene)- and
N-(2,2-Dichloro-2-phenylethylidene)-4-methoxybenzenesulfonamides
from 4-Methoxy-N,N-dichlorobenzenesulfonamide,
Trichloroethylene, and Phenylacethylene
a,b
a
a
a
Yu. A. Aizina , I. B. Rozentsveig , A. V. Popov , and G. G. Levkovskaya *
a
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*
e-mail: ggl@irioch.irk.ru
b
Irkutsk National Research Technical University, Irkutsk, Russia
Received June 12, 2017
Abstract—Reaction of 4-methoxy-N,N-dichlorobenzenesulfonamide with trichloroethylene and phenyl-
acetylene underlies an effective method developed for the synthesis of highly reactive 4-methoxy-N-(2,2,2-
trichloroethylidene)- and 4-methoxy-N-(2,2-dichloro)-2-phenylethylidene)benzenesulfonamides, valuable
reagents for the preparation of new difficultly accessible derivatives of the sulfonamide series.
DOI: 10.1134/S1070428017110264
Highly electrophilic halogen-substituted sulfonyl-
imines are valuable reagents for the production of a variety
of derivatives of the sulfonamide series [1–7]. The deve-
lopment of methods for the synthesis of activated aryl-
sulfonylimines of halocarbonyl compounds is an urgent
task. We are developing one of the most effective app-
roaches to the synthesis of imines of this type, under-
lain by the reaction of N,N-dichlorosulfonamides with 1,2-
polyhaloethenes or phenylacetylene [2, 3, 8–14]. This
approach allows the synthesis of sulfonylimines of poly-
haloaldehydes in a single preparative step in high yields.
In extension of the research on the development
of the synthesis of highly reactive N-(polyhalo-
ethylidene)arenesulfonamides we chlorinated the
4-methoxybenzenesulfonamide 1 and for the first
time we studied the interaction of the obtained
4-methoxyphenyl-N,N-dichlorosulfonamide
2
with
trichloroethylene and phenylacetylene (Schemes 1,
2). Previously, dichloroamide 2 was obtained in
a lower yield (76%) by chlorination of sulfonamide 1
with a triple amount of calcium hypochlorite
[15].
Scheme 1.
CH O
CH
O
3
CH O
3
3
Cl, NaOH
ClHC CCl2
O
S
O
O Cl
N
S
_
_
NCl
_
o
_
NH2
H O, NaCl
2
90 92 C, 8 10 h
CCl
3
2
S
O
O
O
Cl
1
2
A
CH O
CH O
3
3
HOH
O
S
O
3
O
S
O
4
H
N
_
_
N
CCl3
Cl , C HCl
5
CCl
3
2
2
OH
1
753

1
754
AIZINA et al.
Scheme 2.
HC CPh
CH O
CH O
3
3
O
S
O
S
O
5
NCl2
_
o
_
N
CCl Ph
2
90 92 C, 8 10 h
O
2
The reaction of dichloroamide 2 with trichloroethy-
The presence of an electron-donor substituent in the
aromatic ring of compounds 3–5 makes it possible to
consider them as promising for further studies in the
reactions of intramolecular heterocyclization.
lene was carried out by boiling for 8–10 h at a reagent
ratio of 1 : 6‒8. Similar conditions were applied in the
preparation of other arylsulfonylimines of poly-
chloroaldehydes [8–14].
4
-Methoxy-N,N-dichlorobenzenesulfonamide (2).
4
-Methoxy-N-(2,2,2-trichloroethylidene)benzene-
The mixture prepared from 1.60 g (40 mmol) of NaOH
and 1.87 g (10 mmol) of 4-methoxybenzenesul-
fonamide 1 in 30 mL of water was filtered, and
chlorine was bubbled through the filtrate until the
absorption ceased, and the reaction mixture was kept at
room temperature for 30 minutes. The precipitate of
dichloroamide 2 was filtered off, washed with water,
sulfonamide 3 was isolated in 80% yield. Imine 3 is
apparently formed as a result of a chain radical reaction
proceeding through the formation of an unstable adduct
A, which under the reaction conditions is easily
dechlorinated (Scheme 1).The possibility of compound
A formation in such processes is shown in [9]. Due to
the addition of chlorine to trichlorethylene a second
reaction product, pentachloroethane, is formed.
and dried. Yield 2.48 g (97%), mp 48°C (mp 52°C
–1
[
1
15]). IR spectrum, ν, cm : 2949‒3019 (C‒H ), 1164,
Ar
1
268 (SO ). H NMR spectrum (CDCl ), δ, ppm: 3.95
Previously the synthesis of imine 3 in the reaction
of unstable 4-methoxy-N-sulfinylbenzenesulfonamide
with chloral was reported [16], but data on the
physicochemical properties of compound 3 were not
revealed and its yield was not indicated.
2
3
13
s (3H, CH ), 7.11 d, 8.02 d (4H, C H ). C NMR spec-
3
6
4
trum (CDCl ), δ, ppm: 55.85 (OCH ), 114.49, 119.57,
3
3
1
2
3
33.85, 165.68 (C H ). Found, %: С 32.82; H 2.52; Сl
6 4
6.64; N 5.57; S 8.75. C H Cl NO S. Calculated, %: С
7
7
2
3
2.83; H 2.75; Сl 27.69; N 5.47; S 12.52.
Imine 3 adds water with self-heating and forms N-
(
1-hydroxy-2,2,2-trichloroethyl)-4-methoxybenzene-
4-Methoxy-N-(2,2,2-trichloroethylidene)benze-
sulfonamide 4 in a quantitative yield (Scheme 1).
Compound 4 is also formed when the imine 3 is stored
for several hours in air as a result of the latter's
reaction with atmospheric moisture.
nesulfonamide (3). The mixture of 2.56 g (10 mmol)
of dichloroamide 2 and 10.50 g (80 mmol) of
trichloroethylene was boiled for 8–10 h in an argon
atmosphere until the chlorine evolution ceased (test
with KI starch paper). The solution was kept for 24 h
at 5°C, the precipitate of imine 3 was rapidly filtered
off in a vacuum on a glass frit filter, washed on the
filter with an anhydrous hexane, and dried in a vacuum
desiccator at a reduced pressure over P O . Yield
To synthesize 4-methoxy-N-(2-phenyl-2,2-di-
chloroethylidene)benzenesulfonamide 5, we brought
dichloroamide 2 in the reaction with phenylacetylene
(
Scheme 2). The reaction was carried out under
2
5
1
conditions which made it possible to obtain in a similar
process a maximum yield of arylsulfonylimines of
phenyldichloroacetic aldehyde [17].
2
.53 g (80%), mp 118‒121°C (hydroscopic). H NMR
spectrum (CDCl ), δ, ppm: 3.98 s (3H, CH ), 7.00 d,
3
3
1
3
7
.81 d (4H, C H ), 7.94 s (1H, N=СH). C NMR
6 4
The structure of compounds 1–5 is proved by
spectral methods and is confirmed by elemental
analysis data. Hemiaminal 4 was obtained by authentic
synthesis from chloral and sulfonamide 1. In the IR
spectra of sulfonamides 1–5 absorption bands appear
corresponding to the assumed structures. The relative
spectrum (CDCl ), δ, ppm: 55.41 (CH ), 71.78 (CCl ),
3
3
3
1
00.42, 113.73, 127.88, 131.14, 133.72, 162.74
(
C H ), 142.05 (CH=N). Found, %: С 34.27; H 2.81;
6
4
Сl 33.09; N 4.58; S 10.01. C H Cl NO S. Calculated,
9
8
3
3
%: С 34.14; H 2.55; Сl 33.60; N 4.42; S 10.13.
1
integral intensities and position of the signals in H and
N-(1-Hydroxy-2,2,2-trichloroethyl)-4-methoxy-
benzenesulfonamide (4). a. Imine 3, 1.58 g (5 mmol)
was stored in open air for 24 h. Yield 1.67 g (98%).
1
3
C NMR spectra of compounds 1–5 fully correspond
to their formulas.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 11 2017

N-(2,2,2-TRICHLOROETHYLIDENE)- AND N-(2,2-DICHLORO-2-PHENYLETHYLIDENE)-...
1755
b. A mixture of 1.87 g (10 mmol) of 4-methoxyben-
zenesulfonamide 1, 1.48 g (10 mmol) of chloral, and
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7
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The structure of prepared compounds was studied
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of Baykal analytical center for collective use Siberian
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 11 2017