1294
MANNAFOV, BERDNIKOV
benzeneselenol and 0.54 g (3 mmol) of ethynyl p-tolyl
sulfone in 6 ml of methanol-d4. Yield 0.76 g (75%).
1H NMR spectrum, , ppm: 2.37 s (3H), 7.53 t (1H,
J = 1.5 Hz), 7.2 8.0 m (9H).
Reaction of benzeneselenol with ethynyl p-tolyl
sulfone. A solution of 0.47 g (3 mmol) of benzene-
selenol and an equimolar amount of ethynyl p-tolyl
sulfone in 10 ml of carbon tetrachloride was kept for
5 days. The product composition was determined from
1
the H NMR data.
Reaction of benzeneselenol-d1 with ethynyl
p-tolyl sulfone. The reaction was carried out as
described above using 3 mmol of deuterated benzene-
selenol. The product composition was determined
1
from the H NMR data.
Variation of the chemical shifts of the ethynyl carbon
atoms in ethynyl p-tolyl sulfone in going from methanol
to carbon tetrachloride.
(E)-1-Phenylseleno-2-p-tolylsulfonylethene (IV).
Triethylamine, 0.77 ml (5.5 mmol), was added to
a solution of 0.79 g (5 mmol) of benzeneselenol and
1.09 g (5 mmol) of (E)-2-chlorovinyl p-tolyl sulfone
in 14 ml of benzene. After 5 h, the precipitate of tri-
ethylamine hydrochloride was filtered off, the solvent
was distilled off from the filtrate under reduced pres-
sure, and the residue was recrystallized from carbon
tetrachloride, the difference between
and
not
C
C
only is smaller than in methanol but it has the op-
posite sign: 1.7 and 3.2 ppm, respectively.
EXPERIMENTAL
1
tetrachloride. Yield 75%, mp 108 109 C. H NMR
The 1H NMR spectra of compounds IIIa IIIg were
recorded on a Varian-200 spectrometer from solutions
in chloroform-d or carbon tetrachloride using HMDS
as internal reference. The 13C NMR spectra of ethynyl
p-tolyl sulfone were measured in carbon tetrachloride
and methanol.
spectrum, , ppm: 2.43 s (3H), 6.13 (1H), 8.03
3
(1H, JAB = 14.5 Hz), 7.1 7.7 m (9H). Found, %:
C 53.62; H 4.02. C15H14O2SSe. Calculated, %:
C 53.41; H 4.18.
Ethynyl p-tolyl sulfone was synthesized by the
procedure described in [6]. 13C NMR spectrum,
,
C
Benzeneselenol-d1. A mixture of 5 g of benzene-
selenol and 15 ml of D2O was stirred for 10 h. The
organic layer was separated and treated again with
D2O. The procedure was repeated in total four times.
The product was dried over magnesium sulfate and
distilled. Yield 4.2 g (83%), bp 62 C (10 mm).
According to the H NMR data, the concentration of
residual proton on the selenium atom was no larger
than 5% ( 1.33 ppm, s).
ppm: in CCl4: 20.76 (CH3); 143.87, 128.78, 126.91,
138.18 (Carom); 80.45 (C ); 78.75 (C ); in MeOH:
20.22 (CH3); 147.98, 129.76, 126.90, 137.82 (Carom),
79.82 (C ); 83.00 (C ).
REFERENCES
1
1. Mannafov, T.G., Berdnikov, E.A., and Tantashe-
va, F.R., Zh. Org. Khim., 1994, vol. 30, no. 1, p. 73.
2. Comasseto, J.V., J. Organomet. Chem., 1983, vol. 253,
(Z)-1-Arylseleno-2-arylsulfonylethenes IIIa IIIf.
A solution of 0.01 mol of appropriate aryl ethynyl
sulfone in 15 ml of methanol was added to a solution
of 0.01 mol of substituted benzeneselenol in 8 ml of
methanol. After 4 h, the solvent was distilled off
under reduced pressure, and the residue was recrystal-
lized from hexane, isopropyl alcohol, or their mixture.
Yield 78 88%. The melting points and analytical data
are given in table.
no. 2, p. 131.
3. Comasseto, J.V. and Ferretra, J.T.B., J. Organomet.
Chem., 1981, vol. 216, no. 3, p. 287.
4. Tsoi, L.A., Patsaev, A.K., Ushanov, V.Zh., and
Vyaznikovtsev, L.V., Zh. Org. Khim., 1984, vol. 20,
no. 10, p. 2081.
5. Kushnarev, D.F., Kalabin, G.A., Mannafov, T.G.,
Mullin, V.A., Larin, M.F., and Pestunovich, V.A.,
Zh. Org. Khim., 1976, vol. 12, no. 7, p. 1482.
(Z)-2-Deutero-1-phenylseleno-2-p-tolylsulfonyl-
ethene (IIIg). The reaction was carried out as
described above using 0.47 g (3 mmol) of deuteraded
6. Bhattacharya, S.N., Josiah, B.M., and Walton, D.R.M.,
Organomet. Chem. Syn., 1971, vol. 1, no. 2, p. 145.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003