SYNTHESIS, STRUCTURE AND REACTIONS OF -OXOBIS(ARENESULFONATOTRIARYLBISMUTH) 1363
oxide. -Oxobis[(2,4-dimethylbenzenesulfonato)tri-p-
tolylbismuth], 0.50 g, was treated with a solution of
0.10 g of potassium hydroxide in 10 ml of ethanol.
After 24 h, the solvent was removed, and the preci-
pitate that formed was extracted with petroleum ether
to give 0.14 g (93%) of tri-p-tolylbismuth, mp 120 C.
The residual part of the precipitate was extracted
with ethanol to give 0.16 g (94%) of potassuium
acetate. A mixture of 0.70 g of -oxobis[(4-methyl-
benzenesulfonato)triphenylbismuth], 0.21 g of sodium
trichloroacetate, and 30 ml of toluene was heated for
2 h at 80 90 C, cooled, and filtered to obtain 0.22 g
(100%) of sodium 4-methylbenzenesulfonate, mp
>250 C. The solvent was removed from the filtrate,
and the solid residue was extracted with petroleum
ether to obtain 0.23 g (92%) of triphenylbismuth, mp
78 C. The colorless crystalline residue, 0.40 g, was
triphenylbismuth bis(trichloroacetate), yield 93%, mp
2,4-dimethylbenzenesulfonate, mp
>
280 C. Its
1
IR spectrum ( , cm : 1225 m, 1180 v.s, 1100
v.s, 1020 v.s, 500 m) is identical to that of
potassium 2,4-dimethylbenzenesulfonate prepared
from 2,4-dimethylbenzenesulfonic acid and potas-
sium hydroxide. Tri-p-tolylbismuth dichloride,
0.17 g (81%), was isolated by treatment of the
ethanol-insoluble precipitate with ethanolic hydro-
gen chloride, mp 147 C.
1
157 C. Its IR spectrum ( , cm : 1660 v.s, 1260
v.s, 1140 s, 980 s, 960 w, 520 v.s) was iden-
tical to that of a compound prepared from triphenyl-
bismuth, trichloroacetic acid, and hydrogen peroxide
in ether at a 1:2:1 molar ratio.
Reaction of -oxobis[(4-methylbenzenesul-
fonato)triphenylbismuth] with sodium chloride. A
solution of 1.00 g of sodium chloride in 30 ml of
water was added to a solution of 0.60 g of -oxobis-
[(4-methylbenzenesulfonato)triphenylbismuth] in
10 ml of acetone. The crystals that formed were
washed with water and dried to obtain 0.43 g (91%)
of -oxobis(chlorotriphenylbismuth), mp 119 C.
Reaction of -oxobis[(2,5-dimethylbenzenesul-
fonato)tri-p-tolylbismuth] with zinc. Zinc, 0.10 g,
was added to a solution of 0.50 g of -oxobis[(2,5-
dimethylbenzenesulfonato)tri-p-tolylbismuth] in 10 ml
of acetone. The resulting mixture was heated to the
boil. After 24 h, the solvent was removed. The preci-
pitate that formed was extracted in succession with
petroleum ether and ethanol to obtain 0.34 g (94%) of
tri-p-tolylbismuth, mp 120 C, and 0.15 g (94%) of
zinc bis(2,5-dimethylbenzenesulfonate), mp > 250 C.
Reaction of -oxobis[(2,5-dimethylbenzenesul-
fonato)tri-p-tolylbismuth] with sodium chloride
was performed in a similar way to obtain 0.43 g
(91%) of
162 C.
-oxobis(chlorotri-p-tolylbismuth), mp
1
The IR spectrum of the latter ( , cm : 1175 v.s,
1096 v.s, 1025 v.s) was identical to that of a com-
pound prepared from 2,5-dimethylbenzenesulfonate
and zinc.
Reaction of -oxobis[(2,5-dimethylbenzenesul-
fonatotriphenylbismuth) with pentaphenylanti-
mony. A mixture of 0.40 g of -oxobis[(2,5-dime-
thylbenzenesulfonato)triphenylbismuth], 0.32 g of
pentaphenylantimony, and 30 ml of toluene was kept
for 12 h at 20 C. The solvent was removed, and the
residue was recrystallized from water to obtain 0.31 g
(79%) of tetraphenylantimony 2,5-dimethylbenzene-
sulfonate, mp 125 C. The water-insoluble residue was
extracted with toluene to obtain 0.20 g (71%) of tri-
phenylbismuth, mp 78 C.
Reaction of -oxobis[(2,4-dimethylbenzenesul-
fonato)tri-p-tolylbismuth] with sodium acetate.
A solution of 0.10 g of sodium acetate in 15 ml of
water was added to a solution of 0.50 g of -oxobis-
[(2,4-dimethylbenzenesulfonato)tri-p-tolylbismuth] in
10 ml of acetone. The precipitate that formed was
filtered off, dried, and extracted in succession with
petroleum ether and water. Evaporation of petroleum
ether gave 0.14 g (93%) of tri-p-tolylbismuth, mp
120 C. From the aqueous solution, sodium 2,4-di-
methylbenzenesulfonate, 0.14 g (93%), mp > 250 C,
ACKNOWLEDGMENTS
1
was isolated. Its IR spectrum ( , cm : 1200 v.s,
The work was financially supported by the Russian
Foundation for Basic Research (project no. 99-07-
90133).
1160 s, 1100 v.s, 1020 v.s) is identical to that of
a compound prepared from 2,4-dimethylbenzenesul-
fonic acid and sodium acetate. The water-insoluble
precipitate was recrystallized from toluene to obtain
0.19 g (90%) of tri-p-tolylbismuth diacetate, mp
REFERENCES
1
163 C. IR spectrum, , cm : 1595 s, 1330 m,
1. Sharutin, V.V., Sharutina, O.K., Pavlushkina, I.I., Ego-
rova, I.V., Pakusina, A.P., Krivolapov, D.B., Gubaidul-
lin, A.T., and Litvinov, I.A., Zh. Obshch. Khim., 2000,
vol. 70, no. 12, pp. 2000 2004.
1220 m, 1200 s, 1195 w, 1160 w, 1000 s, 800 w,
450 w.
Reaction of -oxobis[(4-methylbenzenesul-
fonato)tri-phenylbismuth] with sodium trichloro-
2. Ruther, R., Huber, F., and Preut, H., J. Organomet.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 9 2004
Sharutin
