First example of synthesis of N,N′-bis(trichloroethylidene)- arenedisulfonamides

Full text of DOI:10.1007/s11178-005-0353-1

Russian Journal of Organic Chemistry, Vol. 41, No. 9, 2005, pp. 1392–1393. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 9, 2005,
pp. 1420–1421.
Original Russian Text Copyright © 2005 by Ushakova, Rozentsveig, Mirskova, Levkovskaya.
SHORT
COMMUNICATIONS
Dedicated to Full Member of the Russian Academy of Sciences
N.S. Zefirov on His 70th Anniversary
First Example of Synthesis of N,N'-Bis(trichloroethylidene)-
arenedisulfonamides
I. V. Ushakova, I. B. Rozentsveig, A. N. Mirskova, 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 June 7, 2005
We previously developed methods for the synthesis
of N-sulfonyl-substituted polyhalogenated aldehyde
imines via reaction of N,N'-dichlorosulfonamides with
polyhaloethenes [1, 2]. In the present communication
we report for the first time on the application of the
same approach to the preparation of N,N'-bis(trichloro-
ethylidene)-p,p'-biphenyl- and p,p'-oxydibenzenedisul-
fonamides. For this purpose, p,p'-biphenyldisulfon-
amide and p,p'-oxydibenzenedisulfonamide were chlo-
rinated in the presence of sodium hydroxide to obtain
the corresponding N,N,N',N'-tetrachloro derivatives Ia
and Ib, and the latter were brought into reaction with
trichloroethylene. As a result, we obtained in high
yields N,N'-bis(trichloroethylidene)-p,p'-biphenyldisul-
fonamide (IIa) and N,N'-bis(trichloroethylidene)-p,p'-
oxydibenzenedisulfonamide (IIb). Molecules of IIa
and IIb possess highly electrophilic azomethine
groups; therefore, these compounds attract interest
from the viewpoint of their further transformations.
contact with atmospheric moisture. It seems to be
reasonable to use Schiff bases IIa and IIb without
isolation from the reaction mixture to avoid formation
of hydroxy derivatives IIIa and IIIb as impurity.
Halogenated Schiff bases having several CH=N
bonds activated by electron-withdrawing substituents
may be convenient starting compounds in the synthesis
of polyfunctional cyclic or acyclic haloalkylamide
ensembles containing pharmacophoric fragments,
which are promising as strong NH acids, ligands, and
reagents for asymmetric synthesis and supramolecular
chemistry.
N,N,N',N'-Tetrachlorodisulfonamides Ia and Ib
were prepared by chlorination of alkaline solutions of
the corresponding disulfonamides [3].
N,N'-Bis(2,2,2-trichloroethylidene)-p,p'-biphenyl-
disulfonamide (IIa). A mixture of 4.50 g (0.01 mol) of
compound Ia and 18 ml (0.20 mol) of trichloro-
ethylene was heated under reflux in a continuous
stream of argon until chlorine no longer evolved (10–
12 h). According to the 1H NMR data, product IIa was
formed in quantitative yield. IR spectrum, ν, cm–1:
The high reactivity of bis-imines IIa and IIb is
demonstrated by exothermic addition of oxygen-cen-
tered nucleophiles. Compounds IIa and IIb vigorously
react with methanol, and they take up water even upon
O
S
O
S
Cl2, NaOH
ClCH=CCl2
NH2SO2
X
SO2NH2
Cl2NSO2
X
SO2NCl2
Cl3C CH
N
X
N
CH CCl3
O
O
Ia, Ib
IIa, IIb
O
S
O
H
OR
CH CCl3
ROH
H
Cl3C CH
OR
N
X
S
N
O
O
IIIa, IIIb, IV
I–III, X = p-C6H4C6H4-p (a), p-C6H4OC6H4-p (b); III, R = OH; IV, R = MeO, X = p-C6H4OC6H4-p.
1070-4280/05/4109-1392 © 2005 Pleiades Publishing, Inc.

FIRST EXAMPLE OF SYNTHESIS OF N,N'-BIS(TRICHLOROETHYLIDENE)...
1393
1
1150, 1335 (SO2); 1635 (C=N). H NMR spectrum
160.43 (C6H4). Found, %: C 30.95; H 2.31; Cl 34.28;
N 4.67; S 10.41. C16H14Cl6N2O7S2. Calculated, %:
C 30.84; H 2.26; Cl 34.14; N 4.50; S 10.29.
(CDCl3), δ, ppm: 7.98 and 8.22 (8H, AA'BB' system,
Harom), 8.85 s (2H, N=CH).
N,N'-Bis(2,2,2-trichloroethylidene)-p,p'-oxydi-
N,N'-Bis(2,2,2-trichloro-1-methoxyethyl)-p,p'-
oxydibenzenedisulfonamide (IV) was synthesized as
described above for IIIa using compound IIb and
methanol instead of water. Yield 86%, mp 143–146°C.
IR spectrum, ν, cm–1: 1140, 1330 (SO2); 3250 (NH).
1H NMR spectrum (CDCl3), δ, ppm: 3.60 s (3H,
OCH3), 4.97 d (1H, NCH, J = 12 Hz), 5.69 d (1H, NH,
J = 12 Hz), 7.10 and 7.94 (8H, AA'BB' system, Harom).
13C NMR spectrum (CDCl3), δC, ppm: 58.49 (OCH3);
92.69 (NCH); 99.03 (CCl3); 119.34, 129.94, 136.26,
159.78 (C6H4). Found, %: C 33.32; H 2.85; Cl 32.92;
N 4.43; S 9.97. C18H18Cl6N2O7S2. Calculated, %:
C 33.20; H 2.79; Cl 32.67; N 4.30; S 9.85.
benzenedisulfonamide (IIb) was synthesized in a si-
milar way. IR spectrum, ν, cm–1: 1145, 1330 (SO2);
1630 (C=N). 1H NMR spectrum (CDCl3), δ, ppm: 7.24
and 8.02 (8H, AA'BB' system, Harom), 8.50 s (2H, N=CH).
13C NMR spectrum (CDCl3), δC, ppm: 96.47 (CCl3);
119.74, 130.07, 136.61, 160.77 (C6H4); 159.08 (N=C).
N,N'-Bis(2,2,2-trichloro-1-hydroxyethyl)-p,p'-bi-
phenyldisulfonamide (IIIa). Water, 1 ml (0.05 mol),
was added to the reaction mixture containing Schiff
base IIa, and the resulting mixture was shaken for 20–
30 min. The precipitate was filtered off and dried.
Yield 90%, mp 176–178°C. IR spectrum, ν, cm–1:
1
1
The H and 13C NMR spectra were recorded from
1140, 1330 (SO2); 3250 (NH); 3450 (OH). H NMR
spectrum (DMSO-d6), δ, ppm: 5.24 d (1H, NCH, J =
11 Hz), 7.90 and 8.01 (8H, AA'BB' system, Harom),
9.02 d (1H, NH, J = 11 Hz). Found, %: C 31.73; H 2.38;
Cl 35.33; N 4.75; S 10.69. C16H14Cl6N2O6S2. Calcu-
lated, %: C 31.65; H 2.32; Cl 35.04; N 4.61; S 10.56.
5–10% solutions on a Bruker DPX-400 spectrometer
at 400.6 and 100.61 MHz, respectively, using hexa-
methyldisiloxane as internal reference. The IR spectra
were measured in KBr on a Specord 75IR instrument.
N,N'-Bis(2,2,2-trichloro-1-hydroxyethyl)-p,p'-
oxydibenzenedisulfonamide (IIIb) was synthesized
as described above for IIIa. Yield 95%, mp 182–
185°C. IR spectrum, ν, cm–1: 1145, 1330 (SO2); 3230
REFERENCES
1. Levkovskaya, G.G., Drozdova, T.I., Rozentsveig, I.B., and
Mirskova, A.N., Usp. Khim., 1999, vol. 68, p. 638.
1
(NH); 3480 (OH). H NMR spectrum (acetone-d6), δ,
2. Mirskova, A.N., Drozdova, T.I., Levkovskaya, G.G., and
ppm: 5.46 d (1H, NCH, J = 11 Hz), 7.24 and 7.99
(8H, AA'BB' system, Harom), 7.77 d (1H, NH, J =
11 Hz). 13C NMR spectrum (acetone-d6), δC, ppm:
86.83 (NCH); 102.55 (CCl3); 119.80, 130.63, 138.42,
Voronkov, M.G., Usp. Khim., 1989, vol. 58, p. 417.
3. Promyshlennye khlororganicheskie produkty (Large-Scale
Organochlorine Products), Oshin, L.A., Ed., Moscow:
Khimiya, 1978, p. 387.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005