One-pot synthesis of unsymmetrical divinyltellane from TeCl4, phenylacetylene, and 1-hexyne

Full text of DOI:10.1134/S1070428013110250

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1707−1708. © Pleiades Publishing, Ltd., 2013.
Original English Text © V.A. Potapov, M.V. Musalova, M.V. Musalov, S.V. Amosova, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 11,
pp. 1723−1724.
SHORT
COMMUNICATIONS
One-Pot Synthesis of Unsymmetrical Divinyltellane
from TeCl , Phenylacetylene, and 1-Hexyne
4
V. A. Potapov, M. V. Musalova, M. V. Musalov, and S. V. Amosova
Faworsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
Irkutsk, 664033 Russia
e-mail: amosova@irioch.irk.ru
Received August 28, 2013
DOI: 10.1134/S1070428013110250
Organotellurium compounds containing a vinyl group
are important semiproducts for organic synthesis [1].
These compounds can be obtained both by the nucleophil-
ic addition of telluride anions to a triple bond [1, 2] and
by the addition of tellurium halides to alkynes [1, 3, 4].
(Z)-(2-phenyl-2-chlorovinyl)]tellane (II) was obtained
in 95% yield in two stages from TeCl , phenylacetylene,
4
and 1-hexyne.
The reaction between TeCl and phenylacetylene
4
proceeded selectively at boiling equimolar amounts of
The addition of tellurium tetrahalides to alkynes
leads to the formation of trihalo(2-halovinyl)tellanes or
to (Z)- or (Е)-dihalo[bis(2-halovinyl)]tellanes depend-
ing on the reaction conditions and the reagents ratio [1,
reagents in a mixture of solvents СС1 –C H , 9 : 1 with
4
6
6
the formation of trichloro-(Z)-(2-phenyl-2-chlorovinyl)
tellane (I) in a nearly quantitative yield. Then to the reac-
tion mixture solution of 1-hexyne in benzene was added.
The regio- and stereoselective addition of tellane I to
1-hexyne occurred at boiling the reagents in the mixture
of solvents ССl –C H , 1 : 1, affording a previously un-
3
, 4]. Presumably the monoadducts may be used in the
addition reaction to another alkyne, but the information
on the synthesis of unsymmetrical divinyltellanes from
tellurium tetrahalides and two different alkynes is absent
from the literature.
4
6
6
known dichloro[(Z)-(2-chlorohex-1-enyl)-(Z)-(2-phenyl-
2-chlorovinyl)]tellane (II) in an overall yield 95%.
In continuation of our systematic research on the addi-
tion of chalcogen halides [4, 5] to unsaturated compounds
we performed a one-pot regio- and stereoselective syn-
Structure, configuration, and composition of com-
1
13
pound II were established with the help of H, C NMR,
in particular, NOESY, spectra, and the elemental analysis
data. The synthesis of monoadduct I from phenylacety-
thesis of an unsymmetrical divinyltellane from TeCl and
4
two different alkynes. Dichloro[(Z)-(2-chlorohex-1-enyl)-
lene and ТеСl was described in [3].
4
Ph
Ph
Cl
Bu
Cl
_
CCl C H
BuC CH
Boiling
4
6
6
TeCl4
PhC СН
Boiling
Cl
TeCl3
Te
Cl Cl
I
II
Dichloro[(Z)-(2-chlorohex-1-enyl)-(Z)-(2-phenyl- δ, ppm: 13.61 (CH ), 20.81 (CH ), 28.86 (CH ), 38.72
3
2
2
2
1
-chlorovinyl)]tellane (II). Light gray substance, mp (CH ), 123.62 (=СНТе), 124.42 (=СНТе), 127.03 (Ph),
94–197°С (decomp.). Н NMR spectrum, δ, ppm: 0.89 t 129.18 (Ph), 131.63 (Ph), 133.36 (Ph), 144.54 (=СCl),
2
1
(
(
(
3Н, СН ), 1.32 m (2Н, СН ), 1.57 m (2Н, СН ), 2.64 m 149.94 (=СCl). Found, %: С 36.82; Н 3.43; Сl 30.93;
3 2 2
2Н, СН ), 7.54 m (3Н, Ph), 7.81 m (2Н, Ph), 8.38 s Te 28.56. C H Сl Тe. Calculated, %: С 37.06; Н 3.55;
2
14 16
4
1
3
1Н, =СНТе), 9.15 s (1Н, =СНТе). С NMR spectrum, Cl 31.26; Te 28.13.
1
707

1708
POTAPOV et al.
NMR spectra were registered on a spectrometer DPX-
00 at operating frequencies 400.13 ( Н) and 100.61
Molecules, 2012, vol. 17, p. 5770; Musalova, M.V., Po-
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Larina, L.I., and Amosova, S.V., Russ. J. Org. Chem.,
1
4
(
13
С) MHz, from solutions in DMSO-d , internal refer-
6
ence HMDS.
ACKNOWLEDGMENTS
The study was carried out under the financial support
of the Russian Foundation for Basic Research (grants
nos. 12-03-01098 and 11-03-00810). The investigations
for proving the structure were carried out on the equip-
ment of the Baikal analytical center in general use of
the Siberian Department of the Russian Academy of
Sciences.
5
2
010, vol. 46, p. 753; Potapov, V.A., Kurkutov, E.O., and
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013