Russian Journal of General Chemistry, Vol. 72, No. 3, 2002, pp. 390 391. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 3, 2002,
pp. 419 420.
Original Russian Text Copyright
2002 by Sharutin, Sharutina, Bondar’, Pakusina, Adonin, Starichenko.
Synthesis of Tetra- and Triarylantimony Fluorobenzoates
V. V. Sharutin, O. K. Sharutina, E. V. Bondar’,
A. P. Pakusina, N. Yu. Adonin, and V. F. Starichenko
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received August 3, 2000
Abstract Pentaarylantimonies Ar5Sb (Ar = Ph, p-Tol) was reacted with triarylantimony bis(perfluorobenzo-
ate) and bis(3,4,5-trifluorobenzoate) in toluene at elevated temperature to obtain tetraarylantimony fluoro-
benzoates in 90% yield. Triarylantimony bis(fluorobenzoates) were prepared in an yield of up to 98% from
triarylstibine and fluorobenzoic acid by oxidative addition in ether in the presence of hydrogen peroxide.
It is known that pentaarylantimonies react with
antimony derivatives of the general formula Ar3SbX2,
where X are oxygen-containing ligands, to form
pentavalent antimony derivatives Ar4SbX [1 4]. It
was shown that functional substituents in an acylate
substituent X prevent this disproportionation reaction.
Thus, the reaction of triphenylantimony disalicylate
with pentaphenylantimony does not lead to tetra-
phenylantimony salicylate [3]. The problem of a more
wide use of the above reaction for preparing Ar4SbX
derivatives might be solved only by having studied
reaction of pentaarylantimonies with symmetrical
antimony derivatives of the general formula Ar3SbX2
with X containing other functional groups.
stibine, fluorobenzoic acid, and hydrogen peroxide in
ether solution at room temperature.
Ar3Sb + 2HOC(O)R + H2O2
Ar3Sb[OC(O)R]2 + 2H2O.
Triarylantimony bis(fluorobenzoates) crystallized
as the ether slowly evaporated (12 24 h).
The yields, melting points, and elemental analyses
of the products are listed in the table.
Hence, the disproportionation of aryl derivatives
of pentavalent antimony, involving pentaaryl anti-
mony and symmetrical aryl antimony derivatives, is
of a greater utility than had been considered.
We have studied reactions of pentaarylantimonies I
with triarylantimony bis(fluorobenzoates) II. It was
shown that the reactions proceed already at 20 C in
aromatic hydrocarbons and result in formation of tetra-
arylantimony fluorobenzoates III as coarse crystals.
EXPERIMENTAL
The IR spectra were recorded on a Hitachi-215
spectrometer for suspensions in Vaseline oil between
NaCl plates.
Triphenylantimony bis(pentafluorobenzoate)
(IIa). To a solution of 1.12 g of triphenylstibine in
10 ml of ether, 1.35 g of pentafluorobenzoic acid and
0.36 ml of 30% aqueous hydrogen peroxide were
added. The resulting mixture was kept for 12 h at
20 C. Crystals formed and were filtered off and dried
to obtain 2.38 g (97%) of triphenylantimony bis(penta-
fluorobenzoate), mp 173 C (decomp.). IR spectrum,
Ar5Sb + Ar3Sb[OC(O)R]2
II
2Ar4SbOC(O)R,
I
III
Ar = C6H5, R = C6F5 (a); Ar = C6H4CH3-4; R = C6F5 (b);
Ar = C6H5, R = C6H2F3-3,4,5 (c); Ar = C6H4CH3-4;
R = C6H2F3-3,4,5 (d).
For the reactions to compete requires heating (1h,
90 C). The IR spectra and melting points of the result-
ing tetraarylantimony fluorobenzoates agree with
analogous physicochemical characteristics of com-
pounds prepared from pentaarylantimony and fluoro-
benzoic acid.
1
, cm : 1672 v.s, 1340 v.s, 1260 v.s, 1100 s,
1065 m, 990 v.s, 920 s.
Tetraphenylantimony pentafluorobenzoate
(IIIa). a. A mixture of 0.91 g of pentaphenylantimony,
1.40 g of triphenylantimony bis(pentafluorobenzoate),
and 15 ml of toluene were heated for 1 h at 90 C. The
solvent was removed, and the dry residue was crystal-
lized from toluene heptane, 1:1, to give 2.00 g
(86%) of tetraphenylantimony pentafluorobenzoate,
Ar5Sb + HOC(O)R
Ar4SbOC(O)R.
The starting triarylantimony bis(fluorobenzoates)
were prepared according to Thepe [5] from triphenyl-
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