Russian Journal of Organic Chemistry, Vol. 40, No. 9, 2004, pp. 1375–1376. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 9, 2004,
pp. 1422–1423.
Original Russian Text Copyright © 2004 by Martynov, Amosova.
SHORT
COMMUNICATIONS
Chlorovinylation of Diphenyl Dichalcogenides
with Dichloroacetylene—A New Method of Synthesis
of 1,2-Dichlorovinyl Phenyl Chalcogenides
A. V. Martynov and S. V. Amosova
Favorskii Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: martynov@irioch.irk.ru
Received March 9, 2004
1,2-Dichlorovinyl chalcogenides Ia–Ic of the gen-
eral formula RXCCl=CHCl [R = Ar, Alk; X = S (a),
Se (b), Te (c)] can be prepared by nucleophilic re-
placement of chlorine in trichloroethylene [1–5] or
tetrachloroethane [6] by thiolate ion, addition of
selenols [7, 8] to dichloroacetylene, phase-transfer
reaction of benzeneselenol with trichloroethylene
[9, 10], and addition of sulfenyl chlorides to chloro-
acetylene [5]. 1,2-Dichlorovinyl selenides are also
formed together with other compounds in phase-
transfer reactions of organic diselenides with tri- and
tetrachloroethylenes, catalyzed by ammonium salts
[11]. However, none of the above procedures can be
applied to obtain tellurenyl derivatives, for tellurols are
extremely unstable due to their high sensitivity to
oxidation [12]. Only in the reaction of diphenyl
ditelluride (IIc) with dichloroacetylene–ether complex,
1,2-dichlorovinyl phenyl telluride (Ic) was detected by
1H NMR spectroscopy and gas chromatography–mass
spectrometry [13]. Individual dichlorovinyl tellurides
have not been isolated so far.
the corresponding disulfide IIa and diselenide IIb,
trans-1,2-dichlorovinyl sulfide (Ib) and trans-1,2-di-
chlorovinyl selenide (Ib) are formed, respectively.
The trans configuration of the double bond in
1
chalcogenides I follows from the H NMR spectra of
sulfide Ia and selenide Ib, which are fully identical to
those reported in [6, 7]. Telluride Ic is resistant to the
action of such dehydrochlorinating agent as a 50% so-
lution of NaOH in benzene [14]. It is known that
sodium ethoxide abstracts hydrogen chloride only from
cis-1,2-dichlorovinyl phenyl selenide [10].
trans-1,2-Dichlorovinyl phenyl telluride (Ic).
Excess LiAlH4 was added with stirring under argon to
a solution of 1 g (2.4 mmol) of ditelluride IIc in 20 ml
of THF until the solution turned colorless, and 20 ml
of a 30% solution of dichloroacetylene in ether (pre-
pared as described in [15]) was then added dropwise
under stirring. After 3 h, the mixture was carefully
treated with water to neutralize excess lithium tetra-
hydridoaluminate, the ether layer was separated, the
aqueous layer was extracted with ether, and the extract
was combined with the organic layer and dried over
CaCl2. The solvent was distilled off, and the residue
was distilled under reduced pressure to isolate 0.47 g
(32%) of 1,2-dichlorovinyl phenyl telluride (Ic) as
a light orange liquid with bp 117–118°C (1.5 mm),
We have found that trans-1,2-dichlorovinyl tellu-
ride (Ic) is formed by reaction of dichloroacetylene–
ether complex with lithium benzenetellurolate gen-
erated from diphenyl ditelluride by the action of
lithium tetrahydridoaluminate. This reaction is general
for all diphenyl dichalcogenides (X = S, Se, Te). From
1
nD23 = 1.6625. H NMR spectrum, δ, ppm: 7.86 m and
7.26 m (5H, C6H5), 6.64 s (1H, =CH). Found, %:
C 33.26, 33.18; H 2.10, 2.22; Cl 20.33, 20.10;
Te 43.61, 42.89. C8H6Cl2Te. Calculated, %: C 31.96;
H 2.01; Cl 23.58; Te 42.44.
(1) LiAlH4/THF
(2) ClC CCl·Et2O
(3) H2O
PhX
Cl
Cl
H
Ph
X
X
Ph
C
C
IIa–IIc
Ia–Ic
The still residue (obtained after separation of
1,2-dichlorovinyl phenyl telluride) was 0.47 g of
X = S (a), Se (b), Te (c).
1070-4280/04/4009-1375 © 2004 MAIK “Nauka/Interperiodica”
Martynov
