Regioselective reaction of tellurium tetrabromide with 1-hexene and methanol

Full text of DOI:10.1134/S1070428013110237

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 11, pp. 1703−1704. © 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. 1719−1720.
SHORT
COMMUNICATIONS
Regioselective Reaction of Tellurium Tetrabromide
with 1-Hexene and Methanol
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/S1070428013110237
Published information on the reactions of tellurium
tetrabromide with alkenes [1] and alkynes [2] is scanty.
The known feature of tellurium tetrabromide is its low
solubility in most organic solvents resulting often in in-
complete conversion of this reagent. The purification of
reaction products from tellurium tetrabromide is a com-
plicated problem. Tellurium tetrabromide is well soluble
in methanol but this solvent has not been virtually used in
the reactions of tellurium tetrabromide apparently because
of the apprehension of the alcoholysis of the Te–Br bond.
equals 191 Hz. This means that tellurium atom is bonded
to the terminal carbon atom of 1-hexene.
The results obtained open new opportunities in the
chemistry of tellurium tetrabromide which may find a
wide application to the synthesis of organotellurium
compounds. It should be noted that tellurium tetrabro-
mide in contrast to tellurium tetrachloride is an available
compound readily formed by reaction of tellurium with
bromine at room temperature.
2
-Methoxyhexyltellurium tribromide (I). Resinous
No published information exists on the reactions of
tellurium tetrabromide with 1-hexene. In continuation of
research on the reactions of tellurium [3] and selenium [4]
halides with unsaturated compounds we performed the
reaction between tellurium tetrabromide with 1-hexene in
methanol. The reaction proceeds chemo- and regioselec-
tively with the selective formation in a quantitative yield
1
dark substance. Н NMR spectrum, δ, ppm: 0.82 t (3Н,
СН ), 1.15–1.41 m (5Н, С Н , ОСНСН ), 1.84 m (1Н,
3
2
4
2
ОСНСН ), 3.21 s (3Н, ОСН ), 3.65 m (1Н, ТеСН ), 3.85
2
3
2
13
m (1Н, ТеСН ), 4.02 m (1Н, ОСН). С NMR spectrum,
2
δ, ppm: 14.35 (CH ), 22.46 (CH ), 27.11 (CH ), 34.93
3
2
2
1
(
CH ), 56.03 (OCH ), 60.87 (Br TeСH , J 191 Hz),
2
3
3
2
Te,C
7
8.48 (OCH). Found, %: С 17.78; Н 2.98; Br 69.26, Te
of the product of TeBr addition to the hexane molecule
4
26.84. C H Br OТe. Calculated, %: С 17.42; Н 3.13;
7 15 3
in keeping with Markovnikoff rule, 2-methoxyhexyltel-
lurium tribromide (I). The quantitative yield of compound
I was obtained by heating the reagents at 40–60°С dur-
ing 8 h. We did not observe bisadduct formation and the
possible alcoholysis of the Te–Br bond.
Br 69.68; Te 26.45.
NMR spectra were registered on a spectrometer DPX-
1
4
(
00 at operating frequencies 400.13 ( Н) and 100.61
С) MHz, from solutions in DMSO-d , internal refer-
1
3
6
ence HMDS.
MeO
MeOH
TeBr4
ACKNOWLEDGMENTS
Bu
_
o
2
5 64 C
Bu
TeBr3
I
The study was carried out in the framework of the
program of the Basic research of the Department of the
RussianAcademy of Sciences and under the financial sup-
port of the Russian Foundation for Basic Research (grants
nos. 12-03-01098 and 13-03-00400). The investigations
for proving the structure were carried out on the equip-
The composition and structure of compound I were
1
confirmed by the data of elemental analysis and by H,
13
C NMR spectra. The direct coupling constant of the
tellurium atom with the carbon atom of the СН group
2
1
703

1704
POTAPOV et al.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 11 2013