Synthesis and transformations of bis(polychloroethylideneaminosulfonyl)- and bis(polychloroethylideneaminosulfonyl)-substituted derivatives of biphenyl, diphenyl oxide, and diphenylmethane

Article abstract of DOI:10.1134/s1070428008020061

Reactions of N,N,N',N'-tetrachlorobiphenyl-4,4'-disulfonamide, 4,4'-methylenebis(N,N-dichlorobenzenesulfonamide), and 4,4'-oxybis(N,N- dichlorobenzenesulfonamide) with 1,2-dichloroethylene and trichloroethylene open convenient synthetic approach to highly

Full text of DOI:10.1134/s1070428008020061

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2008, Vol. 44, No. 2, pp. 218−224. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © I.B. Rosentsveig, I.V. Ushakova, A.N. Mirskova, G.G. Levkovskaya, 2008, published in Zhurnal Organicheskoi Khimii, 2008,
Vol. 44, No. 2, pp. 227−233.
Synthesis and Transformations
of Bis(polychloroethylideneaminosulfonyl)-
and Bis(polychloroethylaminosulfonyl)-Substituted Derivatives
of Biphenyl, Diphenyl Oxide, and Diphenylmethane
I. B. Rosentsveig, I. V. Ushakova, A. N. Mirskova, and G. G. Levkovskaya
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: i_roz@irioch.irk.ru
Received January 29, 2007
Abstract—Reactions of N,N,N',N'-tetrachlorobiphenyl-4,4'-disulfonamide, 4,4'-methylenebis(N,N-
dichlorobenzenesulfonamide), and 4,4'-oxybis(N,N-dichlorobenzenesulfonamide) with 1,2-dichloroethylene and
trichloroethylene open convenient synthetic approach to highly electrophilic bissulfonylimines of dichloroacetic
aldehyde and chloral: N,N'-bis(polychloroethylidene)biphenyl-4,4'-disulfonamides, 4,4'-methylenebis[N-
(polychloroethylidene)benzenesulfonamides] and 4,4'-oxybis[N-(polychloroethylidene)benzenesulfonamides]. The
synthetic opportunities of the bisazomethines obtained were demonstrated by examples of their reactions with
water, methanol, chloroacetamide, and toluene where products of O-, N-nucleophiles addition to the azomethine
bond and products of C-amidoalkylation of aromatic compound with imines were formed.
DOI: 10.1134/S1070428008020061
The synthetic importance of imines of polyhalo-
geneted aldehydes and ketones originates from the
presence in their structure of an activated azomethine
group. The considerable polarization of the C=N bond
by strong electron-withdrawing substituents notably
activates the electrophilic properties of the azomethine
carbon, and this fact is successfully used to solve versatile
synthetic problems. Thus N-sulfonyl-, -carbonyl-, -alk-
oxycarbonyl-, and -phosphonylimines of polyhalo-
carbonyl compounds are active in reactions with O-, N-,
S-, and P-nucleophiles and polynucleophiles, these imines
are reactive amidoalkylating agents, heterodienes and
heterodienophiles,; therefore synthetic approaches have
been developed to a wide range of polyfunctional
nitrogen-containing acyclic and heterocyclic compounds,
among them many of a doubtless practical interest [1].
and N-sulfonylimines of polyhaloaldehydes, for the
process stops at the stage of intermediate hydroxyamidals
(Scheme 1) whose dehydration is either difficult or
impossible because of strong electron-withdrawing sub-
stituents [1]. Therefore an urgent problem is a develop-
ment of alternative preparation methods for imines
containing electron-withdrawing sulfonyl and polyhalo-
methyl substituents at the azomethine moiety.
One of the most convenient synthetic approaches to
the polychloroaldehydes sulfonylimines is based on the
reaction of sulfonic acids N,N-dichloroamides with
1,2-polychloroethenes. The advantages of the method
(simple experiment, high yields, cheap commercial
reagents, unique possibility to obtain a number of
azomethine derivatives of polychloroaldehydes) we
demonstrated formerly by preparation of arenesulfonyl
and trifluoromethylsulfonylimines of chloral and
dichloroacetic aldehyde [1–5].
The classic procedure of azomethines preparation,
condensation of carbonyl compounds with amino group
containing substances, is hardly acceptable for N-acyl-
Scheme 1.
RSO2NHCHRHlg
OH
C RHlg
H
O
2
RSO2N CHRHlg
_H2O
RSO NH +
2
218

SYNTHESIS AND TRANSFORMATIONS OF BIS(POLYCHLOROETHYLIDENEAMINOSULFONYL)-...
219
In this study we continued the systematic investigation
of reactions between N,N-dichloroamides and polyhalo-
ethenes, synthesized previously unknown 4,4'-bis(N,N-
dichloroaminosulfonyl)-substituted derivatives of
biphenyl (Ia), diphenylmethane (Ib), and diphenyl oxide
(Ic), and examined their reactions with 1,2-dichloro-
ethylene and trichloroethylene in order to find synthetic
approach to new bisazomethine compounds. The interest
attracted by these imines is caused by the presence in
their structure of two activated azomethine groups that
can be used in preparation of formerly unknown
functionalized halogen-containing polyamide ensembles,
in particular, of oligomer and macroheterocyclic
structure.
The reaction proceeds by the radical mechanism for
it does not occur in the presence of the inhibitors of
radical processes.
Apparently azomethines IIa, IIb–IVa, IVb result
from a chain radical process starting with the formation
of amidyl radical A. Radical A adds further to dichloro-
ethylene or trichloroethylene giving a radical-adduct B
carrying on the chain propagation with the formation of
saturated adduct C unstable under the reaction conditions
whose dehydrochlorination yields the final azomethine
(Scheme 3). Previously this path of imines formation was
proved by similar transformations of N,N-dichloroamides
of arenesulfonic acids and trifluoromethanesulfonic acid
[7].
Dichloroamides Ia–Ic were obtained by chlorination
of the corresponding disulfonic acids bisamides.
The application to the process of cis- or trans-isomer
of 1,2-dichloroethylene or the isomers mixture does not
affect the course of the reaction. The tetrachloroethylene
does not enter into these reactions.
It was established that the boiling of a mixture contain-
ing dichloroamide Ia–Ic and 10–20-fold excess of
1,2-polychloroethene under an argon atmosphere for 7–
9 h led to the formation of N,N'-bis(polychloroethylid-
ene)biphenyl-4,4'-disulfonamides IIa and IIb, 4,4'-
methylenebis[N-(polychloroethylidene)benzenesulfon-
amides] IIIa and IIIb, and 4,4'-oxybis[N-(polychloro-
ethylidene)benzenesulfonamides] IVa and IVb in high
yields. The reaction was accompanied by chlorine libera-
tion; the latter added to the corresponding polychloro-
ethene (Scheme 2).
The formation of bisazomethines IIa, IIb–IVa, IVb
was confirmed by NMR and IR spectroscopy. The
comparison of the spectral characteristics of compounds
obtained in this study and those of previously investigated
sulfonylimines of chloral and dichloacetic aldehyde
reveals their analogy [3, 5, 7] thus also supporting the
structures of compounds IIa, IIb–IVa, IVb. The signals
of the hydrogen and carbon atoms of the azomethine
1
groups appear in the H and 13C NMR spectra in the
region 8.3–8.5 and 164–166 ppm respectively. Beside
these signals the NMR spectra of azomethine compounds
IIa, IIb–IVa, IVb contain signals corresponding to the
aromatic and polychloromethyl fragments.
It was established in this study that dichloroamides
Ia–Ic could not be involved in the chlorination of 1,2-di-
chloroethylene to trichloroethylene. Therefore their
reactions with 1,2-dichloroethylene did not lead to the
formation of side products trichloroethylidene- and
trichloroethylamides in contrast to formerly investigated
arenesulfonic acids N,N-dichloroamides [6].
Some chemical modifications of compounds IIa, IIb–
IVa, IVb (Scheme 4) also reliably prove their structure
and provide a possibility to a certain extent to estimate
Scheme 3.
Scheme 2.
RSO2NCl2
RSO2NCl
SO2NCl2
SO2NH2
SO2NH2
_Cl2
NaOCl, Cl2
Ar
A
Ar
SO2NCl2
ClH
X
_
ClHC CClX
Ià Ic
RSO2N CHC
Cl Cl
SO2N
SO2N
CHCXCl2
CHCXCl2
ClHC CClX
,
B
Ar
_Cl2
_Cl2HCCCl2X
RSO2NCl2
_RSO2NCl
RSO2N CHCXCl2
_
IIà, IIb IVà, IVb
Cl Cl
C
Ar = 4-C6H4C6H4-4' (Ia, IIa, IIb), 4-C6H4CH2C6H4-4'
(Ib, IIIa, IIIb), 4-C6H4OC6H4-4' (Ic, IVa, IVb); X = Cl
(a), H (b).
RSO2N CHCXCl2
_Cl2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008

ROSENTSVEIG et al.
220
Scheme 4.
OH
SO2NHCHCXCl2
Ar
SO2NHCHCXCl2
OH
Me
_
Và, Vb VIIà, VIIb
OMe
Me
H2O
SO2NHCHCXCl2
SO2NHCHCCl3
SO2NHCHCCl3
MeOH
_
Ar
Ar
IIà, IIb IVà, IVb
SO2NHCHCXCl2
OMe
O
ClCH2CNH2
VIIIa, IXà, IXb, Xà, Xb
NHC(O)CH2Cl
SO2NHCHCCl3
Me
_
XIIIa XVa
Ar
SO2NHCHCCl3
NHC(O)CH2Cl
XIa, XIIa
Ar = 4-C6H4C6H4-4' (Va, Vb, VIIIa, XIa, XIIIa), 4-C6H4CH2C6H4-4' (VIa, VIb, IXa, IXb, XIVa), 4-C6H4OC6H4-4'
(VIIa, VIIb, Xa, Xb, XIIa, XVa); X = Cl (a), H (b).
The described chemical transformations were carried
out aiming at preparation of potential biologically active
substances and semiproducts for further reactions.
Polyfunctionsl halogen-containing ethylamides of sul-
fonic acids are initial compounds for preparation of
amino acids [8], amidine derivatives of amino acids [9],
and heterocyclic compounds [10, 11]. They are interest-
ing as potential ligands, strong NH-acids, possible
reagents for asymmetric synthesis and supramolecular
chemistry.
the synthetic prospects of imines containing the
azomethine groups activated by electron-withdrawing
substituents.
Compounds IIa, IIb–IVa, IVb show high activity in
reactions with O-, N-nucleophiles. They quicly add the
atmospheric moisture giving in a quantitative yield
hemiaminals Va, Vb–VIIa, VIIb. The structure of
hydroxyethylamides Va, Vb–VIIa, VIIb was proved also
by an independent synthesis by reaction of the
corresponding bissulfonic acids diamides with chloral.
By an example of reaction with methanol proceeding
with heat evolution the activity of imines IIa, IIb–IVa,
IVb toward alcohols was demonstrated; the reaction
products were alkoxyaminals VIIIa, IXa, IXb, Xa, Xb.
The short heating resulted in addition to the activated
azomethine group of even weak N-nucleophiles like
chloroacetamide providing polyamide systems XIa and
XIIa.
The structure of functionalized arenesulfonamides V–
XV was proved by IR and NMR spectroscopy and con-
firmed by elemental analysis.
In the IR spectra of compounds V–XV characteristic
absorption bands are observed of NH and SO2 groups,
in the spectra of hemiaminals Va, Vb–VIIa, VIIb, of
OH groups.
1
In the H and 13C NMR spectra of bissulfonamides
Imines IIa, IIb–IVa, IVb proved to be relatively
active C-amidoalkylating agents capable of reacting with
aromatic compounds. They reacted with toluene in the
presence of oleum providing in good yields,
trichloroethylamides XIIIa–XVa. The substitution at the
amidoalkylation occurred specifically into the para-
position of the aromatic ring.
derivatives V–XV signals are present from NHCH
fragments with the coupling constant 3JCH–NH 10–12 Hz,
and also signals of polyhalomethyl and aromatic
fragments in keeping with the assumed structures.
The synthesized sulfonamides derivatives II–XV are
colorless crystalline substances, readily soluble in highly
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SYNTHESIS AND TRANSFORMATIONS OF BIS(POLYCHLOROETHYLIDENEAMINOSULFONYL)-...
221
polar organic solvents (acetone, DMSO), sparingly
soluble in aromatic solvents and halogeneted
hydrocarbons, insoluble in aliphatic hydrocarbons and
in water.
was boiled under constant argon flow till the end of
chlorine evolution (7–9 h). For isolation of pure bisimine
IIa the reaction mixture was maintained at ~ 0°C for
24 h, the formed precipitate of compound IIa was
separated by decanting, washed with CCl4, and dried in
a vacuum desiccator over P2O5. In the syntheses bisimine
IIa was used without isolation from the reaction mixture.
Yield 5.60 g (98%), mp 139–141°C. IR spectrum, ν,
cm–1: 1160, 1345 (SO2), 1640 (C=N), 3100 (CHarom).
1H NMR spectrum (CDCl3), δ, ppm: 7.82, 8.11 AA'BB'
(8H, 4,4'-C6H4C6H4), 8.52 s (2H, N=CH). 13C NMR spec-
trum (CDCl3), δ, ppm: 92.15 (CCl3), 128.22, 129.51,
140.10, 146.27 (4,4'-C6H4C6H4), 164.80 (N=CH).
EXPERIMENTAL
1H and 13C NMR spectra were registered on a spec-
trometer Bruker DPX-400 (operating frequencies 400.13
and 100.61 MHz respectively), internal reference HMDS.
IR spectra were recorded on a spectrophotometer Specord
75IR from KBr pellets.
N,N,N',N'-Tetrachlorobiphenyl-4,4'-disulfon-
amide (Ia). Through a solution of 4.0 g (100 mmol) of
NaOH in 50 ml of water was passed chlorine till the end
of heat evolution. Then to the reaction mixture 6.24 g
(20 mmol) of biphenyl-4,4'-disulfonamide was added,
and at continuous passing of chlorine the mixture was
stirred for 3 h maintaining the temperature below 10°C.
The precipitate of compound Ia was filtered off, washed
with water till negative reaction for chloride ion, dried,
and recrystallized from chloroform or dichloro-methane.
Yield 7.65 g(85%), mp 125°C. IR spectrum, ν, cm–1:
Compounds IIb, IIIa, IIIb, IVa, and IVb were
obtained by the same procedure.
N,N'-Bis(2,2-dichloroethylidene)biphenyl-4,4'-
disulfonamide (IIb) was obtained from 4.50 g (10 mmol)
of compound Ia and 20 g (200 mmol) of dichloro-
ethylene. Yield 4.80 g (96%), mp 157–159°C. IR
spectrum, ν, cm–1: 1150, 1340 (SO2), 1640 (C=N), 3100
1
(CHarom). H NMR spectrum (CDCl3), δ, ppm: 6.12 d
3
(2H, CHCl2, J 6.8 Hz), 7.79, 8.05 AA'BB' (8H, 4,4'-
3
C6H4C6H4), 8.40 d (2H, N=CH, J 6.8 Hz). 13C NMR
1
1160, 1360 (SO2), 3100 (CHarom). H NMR spec-trum
spectrum (CDCl3), δ, ppm: 66.91 (CHCl2), 128.49,
129.30, 139.15, 145.12 (4,4'-C6H4C6H4), 165.84
(N=CH).
(CDCl3), δ, ppm: 7.98, 8.22 AA'BB' (8H, 4,4'-C6H4C6H4).
Found, %: C 31.75; H 2.02; Cl 30.76; N 5.93; S 14.11.
C12H8Cl4N2O4S2. Calculated, %: C 32.02; H 1.79;
Cl 31.50; N 6.22; S 14.24.
4,4'-Methylenebis[N-(2,2,2-trichloroethylidene)-
benzenesulfonamide] (IIIa) was obtained from 4.64 g
(10 mmol) of compound Ib and 26 g (200 mmol)
trichloroethylene. Yield 5.70 g (97%), mp 160–161°C.
IR spectrum, ν, cm–1: 1140, 1320 (SO2), 1630 (C=N),
4,4'-Methylenebis(N,N-dichlorobenzene-
sulfonamide) (Ib) was similarly obtained from 6.52 g
(20 mmol) of 4,4'-methylenedibenzenesulfonamide.
Yield 8.17 g (88%), mp 113–116°C. IR spectrum, ν, cm–1:
1
2930 (CHAlk), 3150 (C–Harom). H NMR spectrum
1
1150, 1360 (SO2), 3100 (CHarom). H NMR spectrum
(CDCl3), δ, ppm: 4.15 s (2H, CH2), 7.36, 7.91 AA'BB'
(8H, 4,4'-C6H4CH2C6H4), 8.47 C (2H, N=CH). 13C NMR
spectrum (CDCl3), δ, ppm: 42.35 (CH2), 93.18 (CCl3),
129.67, 130.07, 137.24, 145.57 (4,4'-C6H4CH2C6H4),
164.30 (N=CH).
(CDCl3), δ, ppm: 4.28 s (2H, CH2), 7.48, 8.06 AA'BB'
(8H, 4,4'-C6H4CH2C6H4). Found, %: C 33.25; H 2.22;
Cl 30.76; N 5.93; S 14.11. C13H10Cl4N2O4S2. Calculated,
%: C 33.64; H 2.17; Cl 30.55; N 6.04; S 13.81.
4,4'-Oxybis(N,N-dichlorobenzenesulfonamide)
(Ic) was similarly obtained from 6.56 g (20 mmol) of
4,4'-oxidibenzenesulfonamide. Yield 8.11 g (87%), mp
68–70°C. IR spectrum, ν, cm–1: 1160, 1360 (SO2), 3090
(CHarom). 1H NMR spectrum (CDCl3), δ, ppm: 7.30, 8.15
AA'BB' (8H, 4,4'-C6H4OC6H4). Found, %: C 31.05; H 1.92;
Cl 30.76; N 5.96; S 14.13. C12H8Cl4N2O5S2. Calculated,
%: C 30.92; H 1.73; Cl 30.42; N 6.01; S 13.76.
4,4'-Methylenebis[N-(2,2-dichloroethylidene)-
benzenesulfonamide] (IIIb) was obtained from 4.64 g
(10 mmol) of compound Ib and 20 g (200 mmol) of
dichloroethylene. Yield 5.0 g (97%), mp 154–155°C. IR
spectrum, ν, cm–1: 1145, 1330 (SO2), 1630 (C=N), 2920
(CHAlk), 3150 (CHarom). 1H NMR spectrum (CDCl3), δ,
3
ppm: 4.14 s (2H, CH2), 6.15 d (2H, CHCl2, J 6.4 Hz),
7.36, 8.35 AA'BB' (8H, 4,4'-C6H4CH2C6H4), 8.35 d (2H,
N=CH, 3J 6.4 Hz).
N,N'-Bis(2,2,2-trichloroethylidene)biphenyl-4,4'-
disulfonamide (IIa). A mixture of 4.50 g (10 mmol) of
compound Ia and 26 g (200 mmol) of trichloroethylene
4,4'-Oxibis[N-(2,2,2-trichloroethylidene)-
benzenesulfonamide] (IVa) was obtained from 4.66 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008

ROSENTSVEIG et al.
222
synthesized by procedure a from 2.93 g (5 mmol) of
bisimine IIIa in the yield 3.00 g (97%) and by method b
from 3.26 g (10 mmol) of 4,4'-methylenedibenzene-
sulfonamide in the yield 5.40 g (87%), mp 163–165°C.
IR spectrum, ν, cm–1: 1140, 1330 (SO2), 3250 (NH), 3400
(10 mmol) of compound Ic and 26 g (200 mmol) of
trichloroethylene. Yield 5.50 g (95%), mp 175°C. IR
spectrum, ν, cm–1: 1145, 1330 (SO2), 1630 (C=N). 1H NMR
spectrum (CDCl3), δ, ppm: 7.22, 8.01 AA'BB' (8H, 4,4'-
C6H4OC6H4), 8.50 s (2H, N=CH). 13C NMR spectrum
(CDCl3), δ, ppm: 93.87 (CCl3), 119.87, 131.46, 138.89,
161.46 (4,4'-C6H4OC6H4), 164.42 (N=CH).
1
(OH). H NMR spectrum (DMSO-d6), δ, ppm: 4.12 s
(2H, CH2), 5.20 d (2H, CH, 3JCH–NH 9.3 Hz) 7.48, 7.84
AA'BB' (8H, 4,4'-C6H4CH2C6H4), 8.85 d (2H, NH,
4,4'-Oxybis[N-(2,2-dichloroethylidene)benzene-
sulfonamide] (IVb) was obtained from 4.66 g (10 mmol)
of compound Ic and 20 g (200 mmol) of dichloroethylene.
Yield 5.0 g (97%), mp 145–147°C. IR spectrum, ν,
cm–1: 1145, 1330 (SO2), 1635 (C=N). 1H NMR spectrum
(CDCl3), δ, ppm: 6.12 d (2H, CHCl2, 3J 6.5 Hz), 7.94,
8.06 AA'BB' (8H, 4,4'-C6H4OC6H4), 8.35 d (2H, N=CH,
3J 6.5 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 67.80
(CHCl2), 120.61, 132.12, 137.18, 161.80 (4,4'-
C6H4OC6H4), 166.39 (N=CH).
3JCH–NH 9.3 Hz). 13C NMR spectrum (DMSO-d6), δ, ppm:
41.18 (CH2), 85.70 (NCH), 102.34 (CCl3), 127.11,
129.27, 139.91, 145.26 (4,4'-C6H4CH2C6H4). Found, %:
C 32.60; H 2.67; Cl 34.60; N 5.01; S 10.41.
C17H16Cl6N2O6S2. Calculated, %: C 32.87; H 2.60;
Cl 34.25; N 4.51; S 10.32.
4,4'-Methylenebis[N-(2,2-dichloro-1-hydroxy-
ethyl)benzenesulfonamide] (VIb) was synthesized by
procedure a from 2.58 g (5 mmol) of bisimine IIIb. Yield
2.62 g (95%), mp 133–135°C. IR spectrum, ν, cm–1:
1150, 1320 (SO2), 3250 (NH), 3400 (OH). 1H NMR spec-
trum (DMSO-d6), δ, ppm: 4.11 s (2H, CH2), 5.00 d.d
N,N '-Bis(2,2,2-trichloro-1-hydroxyethyl)biphenyl-
4,4'-disulfonamide (Va). a. In an open air was kept for
5 h 2.86 g (5 mmol) of bisimine IIa, and therewith
disulfonamide Va formed in a quantitative yield 3.03 g.
3
3
(2H, NCH, JCH–CH 4.0, JCH–NH 8.3 Hz), 5.97 d (2H,
3
b. A mixture of 3.12 g (10 mmol) of 1,1'-biphenyl-
4,4'-disulfonamide, 4.41 g (30 mmol) of chloral, 50 ml
of CCl4, and 0.1–0.2 ml of concn. H2SO4 was stirred for
3 h at 60°C. The precipitate formed in the reaction was
filtered off, washed with water till neutral washings, and
dried in a vacuum desiccator over P2O5. Yield 5.46 g
(90%), mp 172ºC. IR spectrum, ν, cm–1: 1140, 1330
CHCl2, JCH–CH 4.0 Hz), 7.44, 7.79 AA'BB' (8H, 4,4'-
C6H4CH2C6H4), 8.55 d (2H, NH, JCH–NH 8.3 Hz).
3
13C NMR spectrum (DMSO-d6), δ, ppm: 41.05 (CH2),
75.51 (CHCl2), 81.34 (NCH), 126.68, 129.78, 140.88,
145.17 (4,4'-C6H4CH2C6H4). Found, %: C 36.80; H 3.21;
Cl 25.62; N 5.03; S 11.73. C17H18Cl4N2O6S2. Calculated,
%: C 36.97; H 3.29; Cl 25.68; N 5.07; S 11.61.
1
(SO2), 3250 (NH), 3450 (OH). H NMR spectrum
4,4'-Oxybis[N-(2,2,2-trichloro-1-hydroxyethyl)-
benzenesulfonamide] (VIIa) was synthesized by
procedure a from 2.94 g (5 mmol) of bisimine IVa in the
yield 3.10 g (98%) and by procedure b from 3.28 g
(10 mmol) of 4,4'-oxydibenzenesulfonamide in the yield
5.73 g (92%), mp 183ºC. IR spectrum, ν, cm–1: 1145, 1330
(DMSO-d6), δ, ppm: 5.24 d (2H, NCH, 3JCH–NH 9.2 Hz),
7.96, 8.02 AA'BB' (8H, 4,4'-C6H4C6H4), 9.02 d (2H, NH,
3JCH–NH 9.2 Hz). Found, %: C 31.55; H 2.29; Cl 35.56;
N 4.43; S 10.71. C16H14Cl6N2O6S2. Calculated, %: C 31.65;
H 2.32; Cl 35.04; N 4.61; S 10.56.
1
N,N'-Bis(2,2-dichloro-1-hydroxyethyl)biphenyl-
4,4'-disulfonamide (Vb) was synthesized by procedure
a from 2.50 g (5 mmol) of bisimine IIb. Yield 2.65 g
(98%), mp 151–153ºC. IR spectrum, ν, cm–1: 1145, 1330
(SO2), 3220 (NH), 3470 (OH). H NMR spectrum
[CD3C(O)CD3], δ, ppm: 5.46 d (2H, NCH,
3JCH–NH 9.6 Hz), 7.23, 8.02 AA'BB' (8H, 4,4'-
C6H4OC6H4), 7.77 d (2H, NH, 3JCH–NH 9.6 Hz). 13C NMR
spectrum [CD3C(O)CD3], δ, ppm: 86.83 (NCH), 102.55
(CCl3), 119.98, 130.63, 138.42, 160.43 (4,4'-
C6H4OC6H4). Found, %: C 30.75; H 2.18; Cl 34.48;
N 4.64; S 10.52. C16H14Cl6N2O7S2. Calculated, %:
C 30.84; H 2.26; Cl 34.14; N 4.50; S 10.29.
1
(SO2), 3230 (NH), 3450 (OH). H NMR spectrum
3
(DMSO-d6), δ, ppm: 5.06 d.d (2H, NCH, JCH–CH 4.0,
3
3JCH–NH 8.9 Hz), 6.02 d (2H, CHCl2, JCH–CH 4.0 Hz),
7.94, 7.98 AA'BB' (8H, 4,4'-C6H4C6H4), 8.72 d (2H, NH,
3JCH–NH 8.9 Hz). 13C NMR spectrum (DMSO-d6), δ, ppm:
74.90 (CHCl2), 80.73 (NCH), 127.45, 127.55, 141.89,
142.22 (4,4'-C6H4C6H4). Found, %: C 35.56; H 2.91;
Cl 26.77; N 5.03; S 12.26. C16H16Cl4N2O6S2. Calculated,
%: C 35.70; H 3.00; Cl 26.35; N 5.20; S 11.91.
4,4'-Oxybis[N-(2,2-dichloro-1-hydroxyethyl)-
benzenesulfonamide] (VIIb) was synthesized by
procedure a from 2.60 g (5 mmol) of bisimine IVb. Yield
2.65 g (96%), mp 110–113°C. IR spectrum, ν, cm–1: 1150,
1340 (SO2), 3250 (NH), 3450 (OH). 1H NMR spectrum
(DMSO-d6), δ, ppm: 5.01 d.d (2H, CH–N, 3JCH–CH 4.2,
4,4'-Methylenebis[N-(2,2,2-trichloro-1-
hydroxyethyl)benzenesulfonamide] (VIa) was
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SYNTHESIS AND TRANSFORMATIONS OF BIS(POLYCHLOROETHYLIDENEAMINOSULFONYL)-...
223
3
3JCH–NH 8.8 Hz), 6.00 d (2H, CHCl2, JCH–CH 4.2 Hz),
7.22, 7.91 AA'BB' (8H, 4,4'-C6H4OC6H4), 8.62 d (2H,
NH, 3JCH–NH 8.8 Hz). 13C NMR spectrum (DMSO-d6),
δ, ppm: 75.31 (CHCl2), 81.11 (CHN), 119.40, 129.79,
138.08, 159.13 (C6H4OC6H4). Found, %: C 34.65; H 2.88;
Cl 25.52; N 4.98; S 11.48. C16H16Cl4N2O7S2. Calculated,
%: C 34.67; H 2.91; Cl 25.59; N 5.05; S 11.57.
ppm: 40.89 (CH2), 56.18 (OCH3), 72.54 (CHCl2), 88.35
(NCH), 127.52, 129.61, 140.35, 145.91 (4,4'-
C6H4CH2C6H4). Found, %: C 39.08; H 3.58; Cl 24.15;
N 4.64; S 11.12. C19H22Cl4N2O6S2. Calculated, %: C 39.32;
H 3.82; Cl 24.44; N 4.83; S 11.05.
4,4'-Oxybis[N-(2,2,2-trichloro-1-methoxyethyl)-
benzenesulfonamide] (Xa) was obtained from bisimine
IVa. Yield 5.20 g (80%), mp 80–82°C. IR spectrum, ν,
cm–1: 1140, 1320 (SO2), 3280 (NH). 1H NMR spectrum
[CD3C(O)CD3], δ, ppm: 3.59 s (6H, OCH3), 4.97 d (2H,
NCH, 3JCH–NH 9.7 Hz), 5.70 d (2H, NH, 3JCH–NH 9.7 Hz),
7.10, 7.94 AA'BB' (8H, 4,4'-C6H4OC6H4). 13C NMR
spectrum [CD3C(O)CD3], δ, ppm: 58.49 (OCH3), 92.69
(NCH), 99.03 (CCl3), 119.60, 129.23, 136.26, 159.78
(4,4'-C6H4OC6H4). Found, %: C 33.12; H 2.71; Cl 32.88;
N 4.07; S 9.35. C18H18Cl6N2O7S2. Calculated, %: C 33.20;
H 2.79; Cl 32.67; N 4.30; S 9.85.
N,N'-Bis(2,2,2-trichloro-1-methoxyethyl)bi-
phenyl-4,4'-disulfonamide (VIIIa). To a solution of
bisimine IIa in trichloroethylene obtained as described
above was poured 4 ml (100 mmol) of anhydrous
methanol. The reaction mixture was left standing for
24 h, evaporated in a vacuum, and the residue was
recrystallized from a mixture acetone–chloroform, 1:1,
and dried in a vacuum desiccator over P2O5. Yield
4.70 g (74%), mp 93–95°C. IR spectrum, ν, cm–1: 1160,
1330 (SO2), 3280 (NH). 1H NMR spectrum (DMSO-d6),
δ, ppm: 3.30 s (6H, OCH3), 5.10 d (2H, NCH, 3JCH–NH
9.0 Hz), 7.94, 8.05 AA'BB' (8H, 4,4'-C6H4C6H4), 8.78 d
(2H, NH, 3JCH–NH 9.0 Hz). 13C NMR spectrum (DMSO-
d6), δ, ppm: 58.36 (OCH3), 93.11 (CH), 100.41 (CCl3),
127.04, 128.87, 141.75, 145.83 (4,4'-C6H4C6H4). Found,
%: C 34.25; H 3.02; Cl 33.20; N 4.37; S 10.18.
C18H18Cl6N2O6S2. Calculated, %: C 34.04; H 2.86;
Cl 33.49; N 4.41; S 10.09.
4,4'-Oxybis[N-(2,2-dichloro-1-methoxyethyl)-
benzenesulfonamide] (Xb) was obtained from bisimine
IVb. Yield 4.36 g (75%), mp 75–77°C. IR spectrum, ν,
cm–1: 1140, 1320 (SO2), 3250 (NH). 1H NMR spectrum
[CD3C(O)CD3], δ, ppm: 3.41 s (6H, OCH3), 5.01 d (2H,
NCH, 3JCH–NH 3.6 Hz), 6.12 d (2H, CHCl2, 3JCH–CH 3.6
Hz), 7.35, 8.10 AA’BB’ (8H, 4,4'-C6H4OC6H4). 13C NMR
spectrum [CD3C(O)CD3], δ, ppm: 56.96 (OCH3), 73.29
(CHCl2), 89.17 (NCH), 119.85, 128.72, 130.43, 158.67
(4,4'-C6H4OC6H4). Found, %: C 36.85; H 3.28; Cl 24.15;
N 4.67; S 10.58. C18H20Cl4N2O7S2. Calculated, %:
C 37.13; H 3.46; Cl 24.35; N 4.81; S 11.01.
Compounds IXa, IXb, Xa, and Xb were similarly
obtained.
4,4'-Methylenebis[N-(2,2,2-trichloro-1-methoxy-
ethyl)benzenesulfonamide] (IXa) was obtained from
bisimine IIIa. Yield 4.54 g (70%), mp 84–86°C. IR
N,N'-{Biphenyl-4,4'-diylbis[sulfonylimino-(2,2,2-
trichloroethane-1,1-diyl)]}bis(2-chloroacetamide)
(XIa). To a solution of imine IIa in trichloroethylene
was added 3.76 g (40 mmol) of chloroacetamide
preliminary dried for 5 h in a vacuum over P2O5 at 90–
100°C. The reaction mixture was stirred for 8 h at 70–
80°C. The precipitate was filtered off, washed with
20 ml of chloroform, and dried. Yield 4.77 g (65%),
mp 168–170°C. IR spectrum, ν, cm–1: 1145, 1330 (SO2),
1670 (C=O), 3230 br.s (NH), 3330 br.s (NH). 1H NMR
spectrum (DMSO-d6), δ, ppm: 3.93 AB (4H, CH2Cl),
spectrum, ν, cm-1: 1140, 1340 (SO2), 3250 (NH). H
1
NMR spectrum (DMSO-d6), δ, ppm: 3.23 s (6H, OCH3),
3
4.14 s (2H, CH2), 4.95 d (2H, NCH, JCH–NH 9.0 Hz),
7.40, 7.86 AA’BB’ (8H, 4,4'-C6H4CH2C6H4), 8.78 d (2H,
NH, 3JCH–NH 9.0 Hz). 13C NMR spectrum (DMSO-d6),
δ, ppm: 40.90 (CH2), 57.71 (OCH3), 93.12 (NCH),
100.06 (CCl3), 127.52, 129.61, 140.35, 145.91 (4,4'-
C6H4CH2C6H4). Found, %: C 30.75; H 3.15; Cl 32.48;
N 4.44; S 10.21. C19H20Cl6N2O6S2. Calculated, %:
C 35.15; H 3.11; Cl 32.77; N 4.31; S 9.88.
5.91 d.d (2H, NCH, 3JCH–NHC(O) 9.0, 3JCH–NHSO 9.5 Hz),
2
4,4'-Methylenebis[N-(2,2-dichloro-1-methoxy-
ethyl)benzenesulfonamide] (IXb) was obtained from
bisimine IIIb. Yield 4.17 g (72%), mp 65–67°C. IR spec-
trum, ν, cm–1: 1145, 1330 (SO2), 3250 (NH). 1HNMR spec-
trum [CD3C(O)CD3], δ, ppm: 3.71 s (6H, OCH3), 4.64 s
(2H, CH2), 5.34 d (2H, NCH, JCH–CH 3.6 Hz), 6.43 d
(2H, CHCl2, 3JCH–CH 3.6 Hz), 7.90, 8.33 AA'BB' (8H, 4,4'-
C6H4CH2C6H4). 13C NMR spectrum [CD3C(O)CD3], δ,
3
8.95 d (2H, NHSO2, JCH–NHSO 9.5 Hz), 9.19 d [2H,
NHC(O), JCH–NHC(O) 9.0 Hz], 7.87, 7.95 AA'BB' (8H,
2
3
4,4'-C6H4C6H4). 13C NMR spectrum (DMSO-d6), δ, ppm:
42.21 (CH2Cl), 85.73 (CHN), 102.15 (CCl3), 128.33,
129.53, 142.25, 146.31 (C6H4C6H4), 165.22 (C=O).
Found, %: C 31.71; H 2.42; Cl 37.15; N 7.34; S 8.48.
C20H18Cl8N4O6S2. Calculated, %: C 31.69; H 2.39;
Cl 37.41; N 7.39; S 8.46.
3
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ROSENTSVEIG et al.
224
N,N'-{Oxybis[4,1-phenylenesulfonylimino-(2,2,2-
4,4'-Oxybis{N-[2,2,2-trichloro-1-(4-methyl-
phenyl)ethyl]benzenesulfonamide} (XVa) was
prepared similarly from bisimine IVa. Yield 5.40 g
(70%), mp 184–186°C. IR spectrum, ν, cm–1: 1145, 1330
trichloroethane-1,1-diyl)]}bis(2-chloroacetamide)
(XIIa) was prepared similarly from bisimine IVa. Yield
4.64 g (60%), mp 142–144°C. IR spectrum, ν, cm–1:
1145, 1330 (SO2), 3230 (NH), 3350 (NH), 1660 (C=O).
1H NMR spectrum (DMSO-d6), δ, ppm: 3.99 AB (4H,
1
(SO2), 3230 (NH). H NMR spectrum (DMSO-d6), δ,
ppm: 2.18 s (6H, CH3), 5.13 s (2H, NCH), 6.93, 7.32
AA'BB' (8H, C6H4CH3), 6.64, 7.56 AA'BB' (8H, 4,4'-
CH2Cl), 5.88 d.d (2H, NCH, 3JCH–NHC(O) 9.3, 3J
CH–NHSO2
C6H4OC6H4). 13C NMR spectrum (DMSO-d6), δ, ppm:
20.72 (CH3), 71.32 (NCH), 101.70 (CCl3), 118.23,
127.91, 129.03, 129.75, 130.72, 135.81, 137.93, 158.19
(Ar). Found, %: C 46.15; H 3.22; Cl 27.35; N 4.07;
S 8.03. C30H26Cl6N2O5S2. Calculated, %: C 46.71;
H 3.40; Cl 27.58; N 3.63; S 8.31.
9.5 Hz), 7.31, 7.84 AA'BB' (8H, 4,4'-C6H4OC6H4), 8.89 d
(2H, NHSO2, JCH–NH 9.5 Hz), 9.13 d [2H, NHC(O),
3
3JCH–NH 9.3 Hz]. 13C NMR spectrum (DMSO-d6), δ, ppm:
41.70 (CH2Cl), 85.66 (CHNH), 100.16 (CCl3), 128.26,
129.38, 139.71, 158.31 (4,4'-C6H4OC6H4), 166.02
(C=O). Found, %: C 31.08; H 2.39; Cl 36.59; N 7.27;
S 8.32. C20H18Cl8N4O7S2. Calculated, %: C 31.03;
H 2.34; Cl 36.64; N 7.24; S 8.28.
The study was carried out under a financial support
of the Russian Foundation for Basic Research (grant no.
05-03-97202).
N,N'-Bis[2,2,2-trichloro-1-(4-methylphenyl)ethyl]-
biphenyl-4,4'-disulfonamide (XIIIa). To a solution of
bisimine IIa in trichloroethylene was poured 0.5 ml of
oleum (5–15% SO3) and 15–20 ml of anhydrous toluene.
The reaction mixture was stirred for 5 h, diluted with
50 ml of water, the precipitate was filtered off, washed
with 50 ml of 25% aqueous ammonia, dried, and
additionally recrystallized from acetone. Yield 5.66 g
(75%), mp 130–132°C. IR spectrum, ν, cm−1: 1150, 1330
REFERENCES
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., and
Voronkov, M.G., Usp. Khim., 1989, vol. 58, p. 417.
3. Rozentsveig, I.B., Levkovskaya, G.G., Rybalova, T.N., and
Mirskova, A.N., Zh. Org. Khim., 2001, vol. 37, p. 97.
4. Rozentsveig, I.B., Levkovskaya, G.G., Kondrashov, E.V.,
Evstaf’eva, I.T., and Mirskova, A.H., Zh. Org. Khim.,
2001, vol. 37, p. 1635.
1
(SO2), 3250 (NH). H NMR spectrum [CD3C(O)CD3],
δ, ppm: 2.16 s (6H, C6H4CH3), 5.22 s (2H, NCH), 6.96,
7.38 AA’BB’ (8H, C6H4CH3), 7.43, 7.67 AA'BB' (8H, 4,4'-
C6H4C6H4). 13C NMR spectrum [CD3C(O)CD3], δ, ppm:
20.23 (C6H4CH3), 72.19 (NCH), 101.44 (CCl3), 127.31,
127.50, 127.57, 128.27, 129.74, 138.54, 140.39, 143.07
(Ar). Found, %: C 47.75; H 3.51; Cl 27.98; N 3.68;
S 8.65. C30H26Cl6N2O4S2. Calculated, %: C 47.70; H 3.47;
Cl 28.16; N 3.71; S 8.49.
5. Kondrashov, E.V., Rozentsveig, I.B., Levkovskaya, G.G.,
and Mirskova, A.N., Mendeleev Commun., 2003, vol. 13,
p. 25.
6. Rozentsveig, I.B., Evstaf’eva, I.T., Levkovskaya, G.G.,
Mirskova,A.H., andAlbanov,A.N., Zh. Org. Khim., 2000,
vol. 36, p. 847.
7. Kondrashov, E.V., Rozentsveig, I.B., Levkovskaya, G.G.,
and Kanitskaya, L.V., Zh. Org. Khim., 2003, vol. 39,
p. 1490.
8. Rozentsveig, I.B., Levkovskaya, G.G., Mirskova,A.N., and
Kashik, T.V., Zh. Org. Khim., 2000, vol. 36, p. 1813.
9. Rozentsveig, I.B., Levkovskaya, G.G., Rozentsveig, G.N.,
Mirskova, A.N., Krivdin, L.B., Larina, L.I., and Alba-
nov, A.I., Tetrahedron Lett., 2005, vol. 46, p. 8889.
10. Rozentsveig, G.N., Rozentsveig, I.B., Levkovskaya, G.G.,
and Mirskova, A.N. , Zh. Org. Khim., 2003, vol. 39,
p. 1875.
11. Drach, B.S., Brovarets, V.S., and Smolii, O.B., Sintez
azotsoderzhashchikh geterotsiklicheskikh soedinenii na
osnove amidoalkiliruyushchikh agentov (Synthesis of
Nitrogen Heterocyclic Compounds Using of Amido-
alkylating Agents), Kiev: Naukova Dumka, 1992, p. 174.
4,4'-Methylenebis{N-[2,2,2-trichloro-1-(4-methyl-
phenyl)ethyl]benzenesulfonamide} (XIVa) was
prepared similarly from bisimine IIIa. Yield 5.77 g
(75%), mp 108–110°C. IR spectrum, ν, cm–1: 1150, 1340
1
(SO2), 3250 (NH). H NMR spectrum [CD3C(O)CD3],
δ, ppm: 2.23 s (6H, C6H4CH3), 3.91 s (2H, CH2), 5.18 s
(2H, NCH), 6.97, 7.34 AA'BB' (8H, C6H4CH3), 7.02, 7.53
AA'BB' (8H, 4,4'-C6H4CH2C6H4). 13C NMR spectrum
[CD3C(O)CD3], δ, ppm: 21.22 (CH3), 41.35 (CH2), 72.94
(NCH), 102.50 (CCl3), 128.00, 129.14, 129.83, 130.52,
132.12, 139.47, 139.95, 145.84 (Ar). Found, %: C 47.95;
H 3.65; Cl 27.68; N 3.59; S 8.55. C30H26Cl6N2O4S2.
Calculated, %: C 48.39; H 3.67; Cl 27.65; N 3.64;
S 8.33.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 44 No. 2 2008