Russian Journal of General Chemistry, Vol. 74, No. 2, 2004, p. 310. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 2, 2004, pp. 343 344.
Original Russian Text Copyright
2004 by Sharutin, Egorova, Tsiplukhina.
LETTERS
TO THE EDITOR
New Method of Synthesis of Tetraphenylbismuth Aroxides
V. V. Sharutin, I. V. Egorova, and T. V. Tsiplukhina
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received May 5, 2003
It is known that bismuth compounds of the general
formula Ph4BiOR (R = SiPh3, C6F5, C6Cl5) are syn-
thesized from pentaphenylbismuth and hydroxyl-
containing compounds [1, 2]. We devised a new
method of synthesis of tetraphenylbismuth aroxides,
involving reaction of pentaphenylbismuth with tri-
phenylbismuth diaroxides. The method was exempli-
fied by the synthesis of 2,4,6-tribromophenoxy- and
(2,4,6-trichlorophenoxy)tetraphenylbismuth in yields
of up to 46% from triphenylbismuth diaroxides and
pentaphenylbismuth.
resulting mixture was left to stand at 20 C for 24 h.
The solvent was removed, and the residue was treated
with 20 ml of hexane to isolate 0.67 g (54%) of bis-
(2,4,6-tribromophenoxy)triphenylbismuth, mp 118 C.
The residue was treated with 20 ml of toluene to iso-
late 0.15 g (22%) triphenylbismuth dibromide, mp
125 C.
Bis(2,4,6-trichlorophenoxy)triphenylbismuth was
obtained in a similar way, yield 48%, mp 113 C.
Reaction of pentaphenylbismuth with 2,4,6-tri-
bromophenol. A mixture of 0.50 g of pentaphenyl-
bismuth and 0.28 g of tribromophenol in 20 ml of
benzene was stirred for 1 2 min. The solution got
yellow. It was diluted with 10 ml of hexane, filtered,
and the solvent was removed to obtain 0.56 g (80%)
of (2,4,6-tribromophenoxy)tetraphenylbismuth, mp
133 C.
Ph5Bi + Ph3Bi(OAr)2
2Ph4BiOAr,
Ar = C6H2Br3-2,4,6, C6H2Cl3-2,4,6.
The reactions were performed at room temperature
in an aromatic hydrocarbon. Therewith, the solution
changed color from violet (characteristic of penta-
phenylbismuth solutions) to yellow within 2 min.
The melting points and IR spectra of the synthesized
tetraphenylbismuth aroxides were coincident with
those of the same compounds synthesized from penta-
phenylbismuth and phenols.
(2,4,6-Trichlorophenoxy)tetraphenylbismuth was
obtained in a similar way, yield 83%, mp 132 C.
Reaction of pentaphenylbismuth with bis(2,4,6-
tribromophenoxy)triphenylbismuth. A mixture of
0.16 g of pentaphenylbismuth and 0.29 g of bis(2,4,6-
tribromophenoxy)triphenylbismuth in 20 ml of
benzene was stirred for 1 2 min. The solution got
yellow. It was diluted with 10 ml of hexane, filtered,
and the solvet was removed to obtain 0.20 g (46%) of
(2,4,6-tribromophenoxy)tetraphenylbismuth.
The starting triphenylbismuth diaroxides were
prepared by a procedure previously applied to the
synthesis of triphenylbismuth diacylates [3]. Like in
the referred work, the oxidative addition of phenols
to triphenylbismuth successfully proceeds in the
presence of hydrogen peroxide in ether, providing the
target products in 54% yields.
(2,4,6-Trichlorophenoxy)tetraphenylbismuth was
obtained in a similar way, yield 38%, mp 132 C.
Ph3Bi + 2HOAr + H2O2
Ph3Bi(OAr)2 + 2H2O,
The IR spectra were measured on a Hitachi-215
spectrophotometer (suspension in mineral oil between
NaCl plates).
Ar = C6H2Br3-2,4,6, C6H2Cl3-2,4,6.
According to preliminary X-ray diffraction data,
the bismuth atoms in bis(2,4,6-tribromophenoxy)tri-
phenylbismuth and (2,4,6-tribromophenoxy)tetra-
phenylbismuth have a trigonal bipyramidal coordina-
tion, and the aroxyl ligands are axial.
REFERENCES
1. Razuvaev, G.A., Osanova, N.A., and Sharutin, V.V.,
Dokl. Akad. Nauk SSSR, 1975, vol. 225, no. 3, p. 581.
2. Hoppe, S. and Whitmire, K.H., Organometallics, 1998,
no. 17, p. 1347.
3. Gushchin, A.V., Doctoral (Chem.) Dissertation, Nizhny
Novgorod, 1998.
Bis(2,4,6-tribromophenoxy)triphenylbismuth.
To a mixture of 0.50 g of triphenylbismuth and 0.76 g
of 2,4,6-tribromophenol in 15 ml of ether, 0.13 ml of
31% aqueous hydrogen peroxide was added. The
1070-3632/04/7402-0310 2004 MAIK Nauka/Interperiodica
Sharutin
