Cascade synthesis of new aryl 2-phenylallyl sulfones from α-methylstyrene and aromatic mono- and bis-sulfonyl chlorides

Article abstract of DOI:10.1134/S1070428010030085

Addition products of arenesulfonyl chlorides to α-methylstyrene in the presence of catalytic amounts of copper(II) chloride and triethylamine hydrochloride underwent fast dehydrochlorination (according to Hofmann's rule) on heating in boiling acetonitrile to give the corresponding aryl 2-phenylallyl sulfones with high selectivity. This reaction underlay a one-pot procedure for the synthesis of new compounds that attract interest as potential biologically active substances, monomers, and cross-linking agents for polymeric materials from accessible starting compounds.

Full text of DOI:10.1134/S1070428010030085

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 3, pp. 352–354. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.A. Pudikova, N.P. Gerasimova, Yu.A. Moskvichev, E.M. Alov, A.S. Danilova, O.S. Kozlova, 2010, published in Zhurnal
Organicheskoi Khimii, 2010, Vol. 46, No. 3, pp. 360–362.
Cascade Synthesis of New Aryl 2-Phenylallyl
Sulfones from α-Methylstyrene and Aromatic Mono-
and Bis-sulfonyl Chlorides
A. A. Pudikova, N. P. Gerasimova, Yu. A. Moskvichev, E. M. Alov,
A. S. Danilova, and O. S. Kozlova
Yaroslavl State Technical University, Moskovskii pr. 88, Yaroslavl, 150023 Russia
e-mail: pudikovaaa@ystu.ru
Received July 9, 2008
Abstract—Addition products of arenesulfonyl chlorides to α-methylstyrene in the presence of catalytic
amounts of copper(II) chloride and triethylamine hydrochloride underwent fast dehydrochlorination (according
to Hofmann’s rule) on heating in boiling acetonitrile to give the corresponding aryl 2-phenylallyl sulfones with
high selectivity. This reaction underlay a one-pot procedure for the synthesis of new compounds that attract
interest as potential biologically active substances, monomers, and cross-linking agents for polymeric materials
from accessible starting compounds.
DOI: 10.1134/S1070428010030085
Radical addition of alkane- and arenesulfonyl
chlorides to various alkenes and alkadienes in the
presence of copper chlorides was studied in detail for
the first time by Asscher and Vofsi in 1960s [1]. Later
on, this general and convenient method for the prepa-
ration of β-halo sulfones, as well as of α,β-unsaturated
sulfones via subsequent dehydrochlorination, has been
extensively developed in a number of studies. Addi-
tions of sulfonyl chlorides and iodides to activated and
nonactivated alkenes [1–8], conjugated dienes and
trienes [2], allenes [3], acetylenes [9, 10], styrenes
having various substituents in the aromatic ring [3],
β-methylstyrene [4], etc., have been reported. How-
ever, there are no published data on analogous reac-
tions with α-methylstyrene.
In the present work we examined addition of vari-
ous aromatic mono- and bis-sulfonyl chlorides Ia–Im
to α-methylstyrene under standard conditions for the
reactions of sulfonyl chlorides with alkenes, including
substituted styrenes [3, 4]. The reactions were carried
out by heating the reactants in boiling acetonitrile in
the presence of copper(II) chloride and triethylamine
hydrochloride. The latter was used to transform copper
salt into a more readily soluble coordination com-
pound. Some unexpected results were obtained. The
addition of arenesulfonyl chlorides Ia–Im to α-methyl-
styrene was accompanied by dehydrochlorination of
the primary adducts, β-chloro sulfones IIa–IIm. Lib-
eration of hydrogen chloride was observed throughout
the reaction, and the only final products were unsatu-
Scheme 1.
CH2
Ph
ArSO2
–HCl
Me
Me
CuCl2, Et2N·HCl, MeCN
IIIa–IIIi
ArSO2Cl
+
ArSO2
H2C
Ph
Ph
Cl
Me
Ia–Ii
IIa–IIi
ArSO2
Ph
IV
Ar = Ph (a), 4-MeC6H4 (b), 3,4-Me2C6H3 (c), 2,3,5,6-Me4C6H (d), 4-ClC6H4 (e), 3,4-Cl2C6H3 (f), 2,5-Cl2C6H3 (g),
2-O2NC6H4 (h), 2-naphthyl (i);
352

CASCADE SYNTHESIS OF NEW ARYL 2-PHENYLALLYL SULFONES
353
Scheme 2.
Me
O
O
S
Me
CH2
O
S
O
S
CH2
MeCN, CuCl2
Et2N· HCl
Me
S
ClSO2
X
SO2Cl
+
2
Ph
Cl
X
Ph
Ph
X
Ph
–HCl
H2C
Ph
Cl
S
O
O
O
O
Ij–Im
IIj–IIm
IIIj–IIIm
O
O
O
O
O
O
S
S
O
X =
(j),
(k),
(l),
(m).
Cl
Cl
Me
Me
Me
Me
dure). A mixture of 0.05 mol of arenesulfonyl chloride
Ia–Im, 0.05 or 0.15 mol of α-methylstyrene (in the
reactions with sulfonyl chlorides Ia–Ii and bis-sulfonyl
chlorides Ij–Im, respectively), 0.5 mol of anhydrous
copper(II) chloride, 0.75 mol of triethylamine hydro-
chloride, and 25 ml of acetonitrile was heated for 3 h
under reflux. The mixture was cooled and poured into
20 ml of cold methanol, and the precipitate was filtered
off, dried, and recrystallized from ethanol.
rated sulfones IIIa–IIIm (Schemes 1, 2). According to
published data, in all analogous reactions studied
previously dehydrohalogenation of the primary adduct
was a separate step which was carried out by the action
of triethylamine in benzene at room temperature [1–4].
Elimination of hydrogen chloride from adducts
IIa–IIm followed Hofmann’s rather than Saytzeff’s
rule, and the products were less substituted allylic sul-
fones IIIa–IIIm instead of expected more substituted
vinyl sulfones like IV. The product structure was con-
firmed by the 1H NMR and IR spectra.
(2-Phenylprop-2-en-1-ylsulfonyl)benzene (IIIa).
Yield 75%, mp 43–45°C. IR spectrum, ν, cm–1: 1622
1
(C=C); 1306, 1140 (SO2); 895 (C=CH2). H NMR
Thus, using a series of aromatic sulfonyl chlorides
and α-methylstyrene, we have demonstrated the pos-
sibility for synthesizing new unsaturated sulfones in
a one-pot process. The newly synthesized sulfones
attract interest from the viewpoints of both their sub-
sequent transformations (e.g., in the synthesis of poly-
meric materials) and potential biological activity. Com-
puter-assisted screening of the synthesized compounds
using PASS program showed with a probability of 0.95
that they may inhibit different exchange processes in
living organisms and exhibit protective effect on
mucous membranes, as well as carminative, anti-
arthritic, and other kinds of biological activity.
spectrum, δ, ppm: 3.75 s (2H, CH2), 5.05 s and 5.65 s
(1H each, =CH2), 7.25–7.85 m (10H, Harom). Found, %:
C 69.81; H 5.49; S 12.41. C15H14O2S. Calculated, %:
C 69.77; H 5.43; S 12.40.
1-Methyl-4-(2-phenylprop-2-en-1-ylsulfonyl)ben-
zene (IIIb). Yield 77%, mp 91–93°C. IR spectrum, ν,
cm–1: 1624 (C=C); 1313, 1135 (SO2); 899 (C=CH2). 1H
NMR spectrum, δ, ppm: 2.35 s (3H, CH3), 4.57 s (2H,
CH2), 5.14 s and 5.65 s (1H each, =CH2), 7.25–7.65 m
(9H, Harom). Found, %: C 70.63; H 5.72; S 11.77.
C16H16O2S. Calculated, %: C 70.59; H 5.88; S 11.76.
1,2-Dimethyl-4-(2-phenylprop-2-en-1-ylsulfonyl)-
benzene (IIIc). Yield 63%, mp 78–80°C. IR spectrum,
ν, cm–1: 1625 (C=C); 1308, 1119 (SO2); 880, 909
EXPERIMENTAL
1
(C=CH2). H NMR spectrum, δ, ppm: 2.25 d (6H,
1
The H NMR spectra were recorded on a Bruker
CH3), 4.53 s (2H, CH2), 5.19 s and 5.60 s (1H each,
C=CH2), 7.25–7.50 m (8H, Harom). Found, %: C 71.42;
H 6.19; S 11.01. C17H18O2S. Calculated, %: C 71.33;
H 6.29; S 11.19.
DRX-500 spectrometer (500.13 MHz) from solutions
in DMSO-d6 using tetramethylsilane as internal refer-
ence. The IR spectra were measured from samples
dispersed in mineral oil on an RX-1 spectrometer with
Fourier transform. The purity of the products was
checked by TLC on Silufol UV-254 plates using
heptane–ethyl acetate as eluent.
1,2,4,5-Tetramethyl-3-(2-phenylprop-2-en-1-yl-
sulfonyl)benzene (IIId). Yield 51%, mp 97–100°C. IR
spectrum, ν, cm–1: 1621 (C=C); 1299, 1138 (SO2); 911
1
(C=CH2). H NMR spectrum, δ, ppm: 2.25 d (12H,
Initial mono- and bis-sulfonyl chlorides were syn-
thesized according to [11, 12].
CH3), 4.57 s (2H, CH2), 5.29 s and 5.65 s (1H each,
=CH2), 7.19–7.39 m (6H, Harom). Found, %: C 72.58;
H 6.89; S 10.25. C19H22O2S. Calculated, %: C 72.61;
H 7.00; S 10.19.
Reaction of α-methylstyrene with aromatic
mono- and bis-sulfonyl chlorides (general proce-
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PUDIKOVA et al.
354
3,3′-Bis(2-phenylprop-2-en-1-ylsulfonyl)diphenyl
1-Chloro-4-(2-phenylprop-2-en-1-ylsulfonyl)ben-
sulfone (IIIk). Yield 50%, mp 139–142°C. IR spec-
zene (IIIe). Yield 76%, mp 117–118°C. IR spectrum,
ν, cm–1: 1623 (C=C); 1316, 1129 (SO2); 897 (C=CH2).
1H NMR spectrum, δ, ppm: 4.65 s (2H, CH2), 5.20 s
and 5.62 s (1H each, =CH2), 7.24–7.41 m (5H, Harom),
7.67 m (4H, Harom). Found, %: C 61.14; H 4.34;
S 10.44. C15H13ClO2S. Calculated, %: C 61.54; H 4.44;
S 10.94.
trum, ν, cm–1: 1618 (C=C); 1315, 1172 (SO2); 895
1
(C=CH2). H NMR spectrum, δ, ppm: 4.81 s (2H,
CH2), 5.19 s and 5.52 s (1H each, =CH2), 7.10–8.30 m
(18H, Harom). Found, %: C 62.49; H 4.29; S 16.66.
C30H26O6S3. Calculated, %: C 62.28; H 4.49; S 16.61.
4,4′-Dichloro-3,3′-bis(2-phenylprop-2-en-1-ylsul-
fonyl)diphenyl sulfone (IIIl). Yield 47%, mp 83–
86°C. IR spectrum, ν, cm–1: 1625 (C=C); 1324, 1136
(SO2); 891 (C=CH2). 1H NMR spectrum, δ, ppm: 4.90 s
(2H, CH2), 5.40 s and 5.58 s (1H each, =CH2), 7.00–
8.06 m (16H, Harom). Found, %: C 55.61; H 3.55;
S 14.85. C30H24Cl2O6S3. Calculated, %: C 55.64;
H 3.71; S 14.84.
1,2-Dichloro-4-(2-phenylprop-2-en-1-ylsulfonyl)-
benzene (IIIf). Yield 78%, mp 123–125°C. IR spec-
trum, ν, cm–1: 1622 (C=C); 1322, 1119 (SO2); 894
1
(C=CH2). H NMR spectrum, δ, ppm: 4.54 s (2H,
CH2), 5.57 s and 5.80 s (1H each, =CH2), 7.25–7.45 m
(5H, Harom), 7.50–7.95 m (3H, Harom). Found, %:
C 55.13; H 3.76; S 9.62. C15H12Cl2O2S. Calculated, %:
C 55.05; H 3.67; S 9.76.
3,3′,4,4′-Tetramethyl-5,5′-bis(2-phenylprop-2-
en-1-ylsulfonyl)diphenyl sulfone (IIIm). Yield 44%,
mp 173–175°C. IR spectrum, ν, cm–1: 1625 (C=C);
1311, 1128 (SO2); 910 (C=CH2). 1H NMR spectrum, δ,
ppm: 2.21 s and 2.55 s (6H each, CH3), 4.70 s (2H,
CH2), 5.28 s and 5.47 s (1H each, =CH2), 7.00–8.00 m
(14H, Harom). Found, %: C 64.37; H 5.31; S 14.99.
C34H34O6S3. Calculated, %: C 64.35; H 5.36; S 15.14.
1,4-Dichloro-2-(2-phenylprop-2-en-1-ylsulfonyl)-
benzene (IIIg). Yield 59%, mp 97–99°C. IR spectrum,
ν, cm–1: 1628 (C=C); 1321, 1130 (SO2); 897 (C=CH2).
1H NMR spectrum, δ, ppm: 4.84 s (2H, CH2), 5.39 s
and 5.62 s (1H each, =CH2), 7.10–7.36 m (5H, Harom),
7,61–7.74 m (3H, Harom). Found, %: C 55.15; H 3.72;
S 9.51. C15H12Cl2O2S. Calculated, %: C 55.05; H 3.67;
S 9.76.
REFERENCES
1-Nitro-2-(2-phenylprop-2-en-1-ylsulfonyl)ben-
zene (IIIh). Yield 48%, mp 125–127°C. IR spectrum,
ν, cm–1: 1627 (C=C); 1537, 1369 (NO2); 1324, 1143
(SO2); 898 (C=CH2). 1H NMR spectrum, δ, ppm: 4.90 s
(2H, CH2), 5.39 s and 5.73 s (1H each, =CH2), 7.22–
7.47 m (5H, Harom), 7.78–8.06 m (4H, Harom). Found,
%: C 59.33; H 3.80; N 4.59; S 10.40. C15H12NO2S.
Calculated, %: C 59.41; H 3.96; N 4.62; S 10.56.
1. Asscher, M. and Vofsi, D., J. Chem. Soc., 1964, p. 4962.
2. Truce, W.E., Goralski, C.T., Christensen, L.W., and
Bavry, R.H., J. Org. Chem., 1970, vol. 35, p. 4217.
3. Truce, W.E. and Goralski, C.T., J. Org. Chem., 1971,
vol. 36, p. 2536.
4. Orochov, A., Asscher, M., and Vofsi, D., J. Chem. Soc.,
Perkin Trans. 2, 1973, p. 1000.
5. Inomata, K., Sasaoka, S., and Kobayashi, T., Bull.
Chem. Soc. Jpn., 1987, vol. 60, p. 1767.
6. Liu, L.K., Chi, Y., and Kwan-Yue Jen, J. Org. Chem.,
1980, vol. 45, p. 406.
7. Cristol, S.J. and Davies, D.I., J. Org. Chem., 1964,
vol. 29, p. 1282.
8. Konyushkin, L.D., Derzhinskii, A.R., and Prilezhae-
va, E.N., Izv. Akad. Nauk SSSR, Ser. Khim., 1977, p. 938.
9. Amiel, Y., J. Org. Chem., 1971, vol. 36, p. 3691.
10. Truce, W.E., Heuring, D.L., and Wolf, G.C., J. Org.
Chem., 1974, vol. 39, p. 238.
11. Moskvichev, Yu.A., Sapunov, V.A., and Mironov, G.S.,
2-(2-Phenylprop-2-en-1-ylsulfonyl)naphthalene
(IIIi). Yield 52%, mp 112–114°C. IR spectrum, ν,
cm–1: 1627 (C=C); 1304, 1122 (SO2); 904 (C=CH2).
1H NMR spectrum, δ, ppm: 4.70 s (2H, CH2), 5.19 s
and 5.60 s (1H each, =CH2), 7.15–7.43 m (5H, Harom),
7.65–8.04 m (7H, Harom). Found, %: C 73.91; H 4.98;
S 10.11. C19H16O2S. Calculated, %: C 74.03; H 5.19;
S 10.39.
4,4′-Bis(2-phenylprop-2-en-1-ylsulfonyl)diphenyl
ether (IIIj). Yield 45%, mp 140–144°C. IR spectrum,
ν, cm–1: 1623 (C=C); 1293, 1131 (SO2); 1244 (C–O);
Zh. Prikl. Khim., 1980, vol. 53, p. 1619.
1
889 (C=CH2). H NMR spectrum, δ, ppm: 4.65 s (2H,
12. Organikum. Organisch-chemisches Grundpraktikum,
Berlin: Wissenschaften, 1976, 15th edn. Translated
under the title Organikum, Moscow: Mir, 1979, vol. 1,
p. 405.
CH2), 5.30 s and 5.65 s (1H each, =CH2), 7.05–7.80 m
(18H, Harom). Found, %: C 67.95; H 4.87; S 12.01.
C30H26O5S2. Calculated, %: C 67.92; H 4.90; S 12.07.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 3 2010