Anisole alkylation with N-arenesulfonylimines of dichloro(phenyl)acetaldehyde and derivatives thereof

Article abstract of DOI:10.1023/A:1012457430488

N-[1-4-Methoxyphenyl-2-phenyl-2,2-dichloroethyl]arenesulfonamides are formed in reaction of N-(2-phenyl-2,2-dichloroethylidene)-4-chlorobenzenesulfonamide and N-(2-phenyl-2,2-dichloroethylidene)-4-methylbenzenesulfonamide with anisole catalyzed by boron t

Full text of DOI:10.1023/A:1012457430488

Russian Journal of Organic Chemistry, Vol. 37, No. 6, 2001, pp. 819 821. Translated from Zhurnal Organicheskoi Khimii, Vol. 37, No. 6, 2001,
pp. 866 868.
Original Russian Text Copyright
2001 by Drozdova, Mirskova.
Anisole Alkylation with N-Arenesulfonylimines
of Dichloro(phenyl)acetaldehyde and Derivatives Thereof
T. I. Drozdova and A. N. Mirskova
Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
Received June 6, 2000
Abstract N-[1-4-Methoxyphenyl-2-phenyl-2,2-dichloroethyl]arenesulfonamides are formed in reaction of
N-(2-phenyl-2,2-dichloroethylidene)-4-chlorobenzenesulfonamide and N-(2-phenyl-2,2-dichloroethylidene)-
4-methylbenzenesulfonamide with anisole catalyzed by boron trifluoride etherate, and in reaction of anisole
with 1,1-di(arenesulfonamido)-2-phenyl-2,2,-dichloroethanes in the presence of concentrated sulfuric acid.
The prospects of N-sulfonylimines of chloral and
dichloroacetic anhydride in C-amidoalkylation of
aromatic and heterocyclic compounds were discussed
in review [1]. Yet the amidoalkylating activity of
N-sulfonylimines from dichloro(phenyl)acetaldehyde
is poorly understood: a single example is described,
that of reaction between the dichloro(phenyl)acet-
aldehyde N-sulfonylimine with anisole [2].
does not afford the C-amidoalkylation products in a
notable yield (5 7%). The heating to 65 70 C
accelerates the process, and the yield of compounds
IIa, b in reaction of imines Ia, b with anisole
amounts to 12 15% in 2 3 h, to 40 46% in 6 8 h,
and to 62 67% in 10 14 h. Still longer heating
(16 18 h) results in decreased yield for tarring occurs
that hampers the isolation of compounds IIa, b.
In extension of our studies on amidoalkylating
activity of N-arenesulfonylimines of polyhalo-
aldehydes and their derivatives we investigated the
anisole C-amidoalkylation with imines of dichloro-
(phenyl)acetaldehyde and looked for amidoalkylating
agents among the derivatives thereof.
In [3 5] was reported on application as amido-
alkylating agents of 2,2,2-trichloroethylarenesulfon-
amides containing functional groups in position 1,
ArSO2NHCH (Nu)CCl3 [Nu = OH, OEt, OC(O)Me,
NHSO2Ar]. These compounds in the presence of
concn. H2SO4 reacted with benzene, toluene, phenol,
2-chlorothiophenol, anisole, naphthalene to afford
amidoalkylation products. Yet the 1-functionalized
We established that the reaction of N-(2-phenyl-
2,2-dichloroethylidene)-4-chlorobenzenesulfonamide
derivatives
of
dichloro(phenyl)acetaldehyde,
and
N-(2-phenyl-2,2-dichloroethylidene)-4-methyl-
ArSO2NHCH(Nu)CCl2Ph, prepared by reaction of
N,N-dichloroarenesulfonamides with phenylacetylene
and by nucleophilic addition at the azomethine bond
in the N-arenesulfonylimines [6] were not tested
before in the C-amidoalkylation.
benzenesulfonamide (Ia, b) with anisole occurred at
heating in benzene in the presence of boron trifluoride
etherate furnishing N-[1-4-methoxyphenyl-2-phenyl-
2,2-dichloroethyl]-4-chlorobenzene-
(IIa)
and
-4-methylbenzenesulfonamides (IIb) in up to 67%
yield.
1,1-Di(arenesulfonamido)-2-phenyl-2,2-dichloro-
ethanes (IIIa c) react with anisole in the presence of
concn. sulfuric acid at 0 5 C affording C-amido-
alkylation products IIa c and arenesulfonamides
IVa c.
X = Cl (a), Me (b).
The yield of reaction products IIa, b depends on
reaction time and temperature. For instance, the reac-
tion at room temperature (18 20 C) within 20 25 h
X = Cl (a), Me (b), H (c).
1070-4280/01/3706-0819$25.00 2001 MAIK Nauka/Interperiodica

820
DROZDOVA, MIRSKOVA
820
We found that the duration of the reaction effected the
yield of products IIa c. For instance, in 6 h alongside
the C-amidoalkylation products IIa c (yield 58%)
were obtained arenesulfonamides IVa c (yield 28
31%) and initial unreacted compounds IIIa c. When
the reaction was carried out for 11 12 h the yield of
anisole derivatives IIa c grew to 71 75%. We did
not found any notable dependence of the reaction
products yield on the character of substituent in the
para-position of the arylsulfonyl group in the initial
amides IIIa c.
of the compounds are located between 112.64 (4
position of the anisole ring) and 158.90 ppm (4
position in the arenesulfonyl group). The spectral
characteristics of compound IIc are identical to the
data obtained in the study of products in the reaction
between dichloro(phenyl)acetaldehyde N-benzene-
sulfonylimine (Ia, b) with anisole [6].
The formation of arenesulfonamides IVa c in the
course of the reaction was proved by IR spectro-
scopy. In the IR spectra of the compounds are
present the absorption bands in the regions 3230
and 3240 (NH2), 1170, 1340 (O=S=O), 1480
Compounds IIa c at room temperature are stable
against acid hydrolysis. However the heating over
30 C in acidic medium results in hydrolysis of these
compounds to arenesulfonamides IVa c.
1
(C=C arom), 3080 cm (=CH arom), and in the
1H NMR spectra (DMSO-d6) appear signals 7.46 s
(NH2), 7.69 d and 7.82 d (Ar H), identical to
those characteristic of authentic arenesulfonamides
IVb, c. The melting points of the compounds also are
consistent with the data of the authentic substances.
The 13C NMR spectrum of compound IVb
(DMSO-d6) contains the signals of carbon atoms of
the benzene ring at 143.06 (C4), 136.69 (C3), 129.15
(C2), 127.72 ppm (C1).
Lightly colored crystalline compounds IIa c are
well soluble in dimethyl sulfoxide, acetone, sparingly
soluble in tetrachloromethane, chloroform, ethyl
ether, benzene, and insoluble in water. The composi-
tion and structure of compounds IIa, b were proved
by elemental analysis, NMR and IR spectra.
In the IR spectra of compounds IIa, b are present
the absorption bands of the stretching and bending
vibrations of bonds in the regions 3260 3265 (NH),
1165 1170, 1340 (O=S=O), 3060 3080 (=CH),
1480, 1500 (C=C), 2820, 2940 (C H), 790 810
(C Cl) cm , and no bands of the initial amidoalkylat-
ing agents are observed.
Thus
N-[1-(4-methoxyphenyl)-2-phenyl-2,2-di-
chloroethyl]arenesulfonamides (IIa c) can originate
depending on the reaction conditions not only from
dichloro(phenyl)acetaldehyde N-arenesulfonylimines
(Ia, b) but also from the derivatives thereof, 1,1-di-
(arenesulfonamido)-2-phenyl-2,2-dichloroethanes
(IIIa c).
1
The high regioselectivity of the reaction was
1
1
EXPERIMENTAL
revealed by H NMR spectroscopy. In the H NMR
spectrum of compounds IIa c recorded in DMSO-d6
were observed doublets at 8.65 and 8.80 ppm (NH),
and 5.12 and 5.16 ppm (CH) with a characteristic
IR spectra were registered on spectrophotometer
1
UR-20 from KBr pellets in 400-4000 cm region.
3
1H NMR spectra were recorded on spectrometer Jeol
FX-90Q (90 MHz) in DMSO-d6, internal reference
HMDS.
coupling constant JNH CH 10 Hz. The benzene ring
multiplets appear at 7.35 7.60 ppm, those from the
protons in the arene rings of the arenesulfonyl groups
[7.26 d and 7.43 d (3J 8.4 Hz)] and from the protons
of the anisole ring [6.51 d and 6.91 d (3J)] correspond
to a A2ß2 spin system. This splitting of proton signals
evidences formation of para-substituted reaction
products. No reaction occurs at the ortho- and
meta-positions in anisole as shows the lack of the
N-(2-Phenyl-2,2-dichloroethylidene)arenesulfon-
amides (Ia, b) were synthesized by procedure [6, 7].
1, 1-Di(arenesulfonamido)-2-phenyl-2, 2-di-
chloroethanes (IIIa c) were obtained by reaction of
N,N-dichloroarenesulfonamides with phenylacetylene
along procedure described before [6].
1
corresponding signals in the H NMR spectra. The
N-[1-(4-Methoxyphenyl)-2-phenyl-2,2-dichloro-
ethyl]parachlorophenylsulfonamide (IIa). (a) To a
solution of 7.3 g of compound Ia in anhydrous benz-
ene was added 2 4 drops of boron trifluoride etherate
and 2 ml of anisole. The mixture was heated for 14 h
to 65 70 C. The precipitated crystals of the product
were filtered off, washed with chloroform, and dried.
We obtained 6.3 g (67%) of compound IIa, mp
185 186 C.
signal of methyl group attached to anisole ring
appears downfield (3.46 ppm) with respect to the
signal of methyl protons belonging to the aromatic
ring in compound IIb (3.32 ppm, s).
In the 13C NMR spectrum of compound IIa
recorded in DMSO-d6 are observed signals of carbon
nuclei at 95.67 (CCl2) and 55.19 (CH) ppm. The
signals of carbon atoms from the aromatic fragments
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001

ANISOLE ALKYLATION WITH N-ARENESULFONYLIMINES
821
(b) To 1.1 g of compound IIIb was added excess
anisole (7.5 ml) and 2.5 ml of concn. sulfuric acid.
The reaction mixture was maintained for 11 12 h at
0 5 C while vigorous stirring. On completing the
reaction the mixture was diluted with cold water and
neutralized with a water solution of sodium carbonate.
The insoluble reaction product was filtered off,
washed with water till neutral, and dried in vacuum-
desiccator over P2O5. We obtained 0.75 g (75%)
slightly colored crystalline compound, mp 185 186 C.
Found, %: C 53.18; H 3.67; Cl 21.97; N 2.67; S
6.74. C21H18Cl3NO3S. Calculated, %: C 53.58; H
3.85; Cl 22.59; N 2.98; S 6.81.
Arenesulfonamides IVa, b were separated from
the reaction mixture at treating with acid the filtrate
obtained by procedure b; the melting points were
consistent with the published data [8].
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N-[1-(4-Methoxyphenyl)-2-phenyl-2,2-dichloro-
ethyl]paramethylphenylsulfonamide (IIb) was pre-
pared along procedure a from 6.8 g of amidoalkylat-
ing agent Ib in amount of 5.5 g (62%), mp 181
183 C, and along procedure b (amindoalkylating
agent IIIb) in amount 0.67 g (72%), mp181 183 C.
Found, %: C 57.98; H 4.67; Cl 15.18; N 2.87; S
6.98. C22H21Cl2NO3S. Calculated, %: C 58.67; H
4.70; Cl 15.74; N 3.11; S 7.12.
N-[1-(4-Methoxyphenyl)-2-phenyl-2,2-dichloro-
ethyl]benzenesulfonamide (IIc) was prepared along
procedure b from compound IIIc in amount 0.6 g
(71%). Found, %: C 57.33; H 4.32; Cl 16.11; N
3.19; S 7.13. C21H19Cl2NO3S. Calculated, %: C
57.80; H 4.39; Cl 16.25; N 3.21; S 7.35.
8. Promyshlennye khlororganicheskie produkty (Industrial
Organochloro Compounds), Oshina, L.A., Moscow:
Khimiya, 1978.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 6 2001