Arylation of aryl- and diarylbismuth arenesulfonates with pentaarylantimony

Article abstract of DOI:10.1023/A:1023463212564

Pentaarylantimony Ar₃Sb (Ar = Ph, p-Tol) arylates diarylbismuth arylsulfonates Ar₂BiOSO₂Ar' (Ar' = C₆H ₄Me-4; C₆H₃Me₂-2,4, C ₆H₃Me₂-2,

Full text of DOI:10.1023/A:1023463212564

Russian Journal of General Chemistry, Vol. 72, No. 12, 2002, pp. 1925 1926. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 12, 2002,
pp. 2033 2034.
Original Russian Text Copyright
2002 by Sharutin, Egorova, Pavlushkina, Ivanenko.
Arylation of Aryl- and Diarylbismuth Arenesulfonates
with Pentaarylantimony
V. V. Sharutin, I. V. Egorova, I. I. Pavlushkina, and T. K. Ivanenko
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received February 12, 2001
Abstract Pentaarylantimony Ar3Sb (Ar = Ph, p-Tol) arylates diarylbismuth arylsulfonates Ar2BiOSO2Ar
(Ar = C6H4Me-4; C6H3Me2-2,4, C6H3Me2-2,5) in ether at 20 C (48 h) to form triarylbismuth in yields of up
to 95%. The second reaction product is tetraarylantimony arenesulfonate. The reaction of pentaphenylanti-
mony with phenylbismuth bis(arenesulfonate) PhBi(OSO2Ar )2 under the same conditions leads to formation
of diphenylbismuth arenesulfonate and tetraphenylantimony arenesulfonate in yields of up to 90%.
It is khown that radical redistribution reactions are
characteristic of pentaarylantimony and pentaphenyl-
bismuth. These compounds are effective arylating
agents for organic derivatives of tin(IV), antimony(V),
and bismuth(V) [1 8]. Proceeding with studies on
arylating properties of pentaarylantimony we have
investigated its reactions with aryl- and diarylbis-
muth(III) arenesulfonates.
effective arylating agent not only for bismuth(V), but
also for bismuth(III) organic derivatives.
EXPERIMENTAL
The IR spectra were recorded on a Hitachi-215
spectrometer for suspensions in Vaseline oil between
NaCl plates.
It was shown that the reaction of pentaarylanti-
mony with diphenylbismuth arenesulfonate involves
redistribution of radicals between the antimony and
bismuth atoms to give triarylbismuth and tetraaryl-
antimony arenesulfonates in yields of up to 95%.
Reaction of diphenylbismuth 4-methylbenzene-
sulfonate with pentaphenylantimony. A mixture of
1.10 g of pentaphenylantimony and 1.16 g of diphenyl-
bismuth 4-methylbenzenesulfonate in 20 ml of ether
was kept for 48 C at 20 C. Coarse crystals formed
and were filtered off, washed with hexane, dried, and
weighted. Tetraphenylantimony 4-methylbenzenesul-
fonate, 120 g (93%) was obtained, mp 165 C. The IR
spectrum of this compound is identical to the IR spec-
trum of a compound prepared from pentaphenylanti-
mony and 4-methylbenzenesulfonic acid. The ethereal
and hexane solutions were evaporated, and the solid
residue was recrystallized from ethanol. Triphenyl-
bismuth, 0.92 g (96%), was obtained, mp 78 C.
Ar5Sb + Ar2BiOSO2Ar
Ar3Bi + Ar4SbOSO2Ar ,
Ar = Ph, p-Tol; Ar = C6H4Me-4, C6H3Me2-2,4,
C6H3Me2-2,5.
The reactions between the above-mentioned rea-
gents proceed in ether at 20 C for 48 h. Therewith,
disappearance of crystals of the starting diarylbismuth
arenesulfonate and crystallization of tetraarylantimony
arenesulfonate take place.
Reaction of di-p-tolylbismuth 4-methylbenzene-
sulfonate with penta-p-tolylantimony. A mixture of
1.15 g of penta-p-tolylantimony and 1.12 g of di-p-
tolylbismuth 4-methylbenzenesulfonate in 20 ml of
ether was kept for 48 h at 20 C. Coarse crystals
formed and were filtered off, washed with hexane,
dried, and weighted. Tetra-p-tolylantimony 4-methyl-
benzenesulfonate, 1.30 g (99%) was obtained, mp
143 C. The IR spectrum of this compound is identical
to the IR spectrum of a compound prepared from
penta-p-tolylantimony and 4-methylbenzenesulfonic
acid. The ethereal and hexane solutions were evapo-
rated, and the solid residue was re crystallized from
The reaction of pentaphenylantimony with phenyl-
bismuth bis(arenesulfonate) under similar conditions
results in quantitative formation of tetraphenylanti-
mony arenesulfonate and diphenylbismuth arenesul-
fonate.
Ph5Sb + PhBi(OSO2Ar )2
+ Ph4SbOSO2Ar ,
Ph2BiOSO2Ar
Ar = C6H4Me-4, C6H3Me2-2,4, C6H3Me2-2,5.
Hence, it was shown that pentaarylantimony is an
1070-3632/02/7212-1925$27.00 2002 MAIK Nauka/Interperiodica

1926
SHARUTIN et al.
ethanol. Tri-p-tolylbismuth, 0.93 g (97%), was ob-
tained, mp 118 C.
benzenesulfonate (95%), mp 190 C, and tetraphenyl-
antimony 4-methylbenzenesulfonate (93%), mp 165 C,
were obtained.
Reaction of phenylbismuth bis(2,5-dimethylben-
zenesulfonate) with pentaphenylantimony. A mix-
ture of 1.15 g of pentaphenylantimony and 1.49 g of
phenylbismuth bis(2,5-dimethylbenzenesulfonate) in
30 ml of ether was kept for 48 h at 20 C. The solvent
was removed, and the residue extracted with toluene.
The crystals insoluble in toluene were filtered off and
dried. Diphenylbismuth 2,5-dimethylbenzenesulfonate,
1.20 g (97%), was obtained, mp 215 C. The IR spec-
trum of this compound was identical to the IR spec-
trum of the diphenylbismuth 2,5-dimethylbenzenesul-
fonate prepared from triphenylbismuth and 2,5-di-
methylbenzenesulfonic acid. After evaporation of the
toluene, 1.32 g (95%) of tetraphenylantimony 2,5-di-
methylbenzenesulfonate was obtained, mp 142 C. The
IR spectrum of this compound was identical to the IR
spectrum of the tetraphenylantimony 2,5-dimethyl-
benzenesulfonate prepared from pentaphenylantimony
and 2,5-dimethylbenzenesulfonic acid.
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Reaction of phenylbismuth bis(2,4-dimethyl-
benzenesulfonate) with pentaphenylantimony was
performed in a similar way. Diphenylbismuth 2,4-di-
methylbenzenesulfonate (98%), mp 210 C, and tetra-
phenylantimony 2,4-dimethylbenzenesulfonate (98%),
mp 209 C, were obtained.
7. Sharutin, V.V., Sharutina, O.K., Tarasova, T.A., Khar-
sika, A.N., and Bel’skii, V.K., Zh. Obshch. Khim., 1999,
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Reaction of phenylbismuth bis(4-methylbenzene-
sulfonate) with pentaphenylantimony was per-
formed in a similar way. Diphenylbismuth 4-methyl-
8. Sharutin, V.V., Sharutina, O.K., Senchurin, V.S., Ko-
valeva, T.A., Shcherbakov, V.I., and Gladyshev, E.N.,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 12 2002