Russian Journal of Organic Chemistry, Vol. 38, No. 12, 2002, p. 1812. Translated from Zhurnal Organicheskoi Khimii, Vol. 38, No. 12, 2002, p. 1871.
Original Russian Text Copyright 2002 by Maksimenko, Sadekov.
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Reaction of Diaryl Telluroxides with HBF4
A. A. Maksimenko and I. D. Sadekov
Research Institute of Physical and Organic Chemistry, Rostov State University,
pr. Stachki 194/2, Rostov-on-Don, 344090 Russia
Received March 11, 2001
We previously showed [1] that diaryl telluroxides
react with an equimolar amount of perchloric acid
Diphenyltellurium difluoride (IIa). A solution of
8.1 g of 33% HBF4 (containing 0.03 mol of the acid)
was added dropwise with stirring and cooling on
an ice bath to a solution of 2.98 g (0.01 mol) of di-
phenyl telluroxide in 15 ml of 2-propanol. When the
addition was complete, crystals of difluoride IIa were
filtered off, washed with ether, and dried. Yield 2.5 g
(78%). Colorless crystals, mp 153 154 C (from
methanol; published data [3]: mp 154 C.
Bis(4-methylphenyl)tellurium difluoride (IIb),
yield 75%, colorless crystals, mp 163 164 C (from
methanol; published data [7]: mp 163 C; bis(4-
methoxyphenyl)tellurium difluoride (IIc), yield 66%,
colorless crystals, mp 129 130 C (from methanol);
published data [6]: mp 131 C; and bis(4-ethoxy-
phenyl)tellurium difluoride (IId), yield 71%, colorless
crystals, mp 170 171 C (from benzene petroleum
ether); published data [4]: mp 169 170 C, were syn-
thesized in a similar way.
to give diaryl(hydroxy)telluronium perchlorates
+
Ar2Te(OH) ClO4 in high yields. However, we failed
to obtain in a similar way the corresponding tetra-
fluoroborates. The reaction of diphenyl telluroxide
(Ia) with HBF4 at a molar ratio of 1:1 in a mixture
of 2-propanol with water gave 47% of diphenyltel-
lurium difluoride (IIa). In the presence of 3 equiv of
HBF4 the yield of difluoride IIa attained 78%. The
reactions of telluroxides Ia Id with HBF4 are accom-
panied by decomposition of the BF4 ion, and the
mechanism of this process is not clear.
R = H (a), 4-Me (b), 4-MeO (c), 4-EtO (d).
Decomposition of BF4 ion was observed previously
[2] in the reaction of 3-chlorotelluro-1,3-diphenyl-2-
propen-1-one ClTe(Ph)C CHCOPh with AgBF4,
which resulted in formation of 33% of the correspond-
ing fluoride FTe(Ph)C CHCOPh. The reaction of
diaryl telluroxides with HBF4 supplements previously
known methods for preparation of diaryl tellurides:
exchange reactions of dihalodiaryltellurium with AgF
[3, 4], oxidation of diaryl ditellurides with fluorine [5]
or sulfur tetrafluoride [6], and reaction of diaryl tellur-
oxides with HF [7].
The melting points of products IIa IId coincided
with those reported in the literature. Compounds
IIb IId characteristically show in the 1H NMR
spectra a double AA BB pattern, which is consistent
with their structure.
REFERENCES
1. Sadekov, I.D. and Maksimenko, A.A., Zh. Obshch.
Khim., 1977, vol. 47, no. 11, pp. 2536 2541.
2. Detty, M.R., Murray, B.J., Smith, D.L., and Zum-
bulyadis, N., J. Am. Chem. Soc., 1983, vol. 105, no. 4,
pp. 875 882.
3. Emeleus, H.J. and Heal, H.G., J. Chem. Soc., 1946,
no. 8, pp. 1126 1131.
4. Berry, F.J., Kustan, E.H., Roshani, M., and
Smith, B.C., J. Organomet. Chem., 1975, vol. 99,
no. 1, pp. 115 117.
5. Ruppert, J., Chem. Ber., 1979, vol. 112, no. 8,
pp. 3023 3030.
6. Sadekov, I.D., Bushkov, A.Ya., Markovskii, L.N., and
Minkin, V.I., Zh. Obshch. Khim., 1976, vol. 46, no. 7,
p. 1660.
7. Sadekov, I.D., Bushkov, A.Ya., Pavlova, V.L.,
Yur’eva, V.S., and Minkin, V.I., Zh. Obshch. Khim.,
1977, vol. 47, no. 6, pp. 1305 1313.
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This study was financially supported by the Ministry of
Education of the Russian Federation (St. Petersburg, project
no. 2000-5-117).
1070-4280/02/3812-1812$27.00 2002 MAIK Nauka/Interperiodica
Maksimenko
