Reactions of triarylbismuth bis(arenesulfonates)

Article abstract of DOI:10.1023/A:1013216810752

Reactions of triphenylbismuth with sodium salts, acids, alkalies, and zinc are studied. In the first three cases Bi-O bond cleavage takes place, while zinc reduces the starting bismuth compounds to triphenylbismuth.

Full text of DOI:10.1023/A:1013216810752

Russian Journal of General Chemistry, Vol. 71, No. 8, 2001, pp. 1236 1237. Translated from Zhurnal Obshchei Khimii, Vol. 71, No. 8, 2001,
pp. 1310 1311.
Original Russian Text Copyright
2001 by Sharutin, Sharutina, Egorova, Ettenko.
Reactions of Triarylbismuth Bis(arenesulfonates)
V. V. Sharutin, O. K. Sharutina, I. V. Egorova, and E. N. Ettenko
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received April 20, 2000
Abstract Reactions of triphenylbismuth with sodium salts, acids, alkalies, and zinc are studied. In the first
three cases Bi O bond cleavage takes place, while zinc reduces the starting bismuth compounds to triphenyl-
bismuth.
Triphenylbismuth bis(arenesulfonates) have been
potassium hydroxide or sodium alcoholate of al-
synthesized by reaction of triphenylbismuth carbonate coholic triphenylbismuth bis(arenesulfonates) results
with benzene and 4-methylbenzenesulfonic acids [1]
and also by oxidative addition of triphenylbismuth to
2,4- and 2,5-dimethylbenzenesulfonic acids in the
presence of hydrogen peroxide [2, 3]. At the same
time, the reactivity of triphenylbismuth bis(arenesul-
fonates) has scarcely been studied. The only precedent
is the reaction of triphenylbismuth bis(benzenesul-
fonate) and bis(4-methylbenzenesulfonate) with alkali
metal chlorides, leading to formation of triphenyl-
bismuth dichloride [1].
in formation of triphenylbismuth dihydroxide and
potassium(sodium) arenesulfonate.
Ph3Bi(OSO2Ar)2 + 2NaOH
Ph3Bi(OH)2 + 2ArSO2ONa,
Ar = C6H3Me2-2,5.
Substitution of arenesulfonyl groups on the bis-
muth atom also takes place in reactions of triphenyl-
bismuth bis(2,4- and bis(2,5-dimethylbenzenesul-
fonates) with sodium salts NaX in alcohol in-
dependent of the nature of X. With acetone instead of
ethanol, the reaction pathway is the same.
We showed that treatment with sulfuric acid of
triphenylbismuth bis(arenesulfonates) gives rise to
Bi O bond cleavage. Triphenylbismuth sulfate and
arenesulfonic acid were quantitatively isolated from
the reaction mixture.
Ph3Bi(OSO2Ar)2 + 2NaX
Ph3BiX2 + 2ArSO2ONa,
Ar = C6H3Me2-2,5; X = Cl, Br, F, NO3, OC(O)Me,
OC(O)Ph.
Ph3Bi(OSO2Ar)2 + H2SO4
Ph3BiSO4 + 2ArSO2OH,
The yield of bismuth salts Ph3BiX2 reaches 98%
(see table).
Ar = C6H3Me2-2,4.
The Bi O bonds are also easily cleaved under the
action of alkalis. Hence, treatment with aqueous
Zinc easily reduces triphenylbismuth bis(arenesul-
fonates) to triphenylbismuth. The second reaction
Products and yields of reactions of triphenylbismuth bis(arenesulfonates) with salts, sulfuric acid, and zinc
Initial compounds
Reaction products (%)
Ph3Bi(OSO2C6H3Me2-2,4)2 + NaF
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaF
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaCl
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaBr
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaNO3
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaOC(O)CH3
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaOC(O)Ph
Ph3Bi(OSO2C6H3Me2-2,4)2 + H2SO4
Ph3Bi(OSO2C6H3Me2-2,4)2 + KOH
Ph3Bi(OSO2C6H3Me2-2,5)2 + NaOH
Ph3Bi(OSO2C6H3Me2-2,4)2 + Zn
Ph3BiF2 (87), NaOSO2C6H3Me2-2,4 (98)
Ph3BiF2 (93), NaOSO2C6H3Me2-2,5 (97)
Ph3BiCl2 (97), NaOSO2C6H3Me2-2,5 (92)
Ph3BiBr2 (89), NaOSO2C6H3Me2-2,5 (92)
Ph3Bi(NO3)2 (88), NaOSO2C6H3Me2-2,5 (95)
Ph3Bi(O2CCH3)2 (92), NaOSO2C6H3Me2-2,5 (97)
Ph3Bi(O2CPh)2 (98), NaOSO2C6H3Me2-2,5 (97)
Ph3BiSO4 (94), HOSO2C6H3Me2-2,4 (96)
Ph3Bi(OH)2 (62), KOSO2C6H3Me2-2,4 (98)
Ph3Bi(OH)2 (72), NaOSO2C6H3Me2-2,5 (91)
Ph3Bi (96), Zn[OSO2C6H3Me2-2,4]2 (95)
Ph3Bi (95), Zn[OSO2C6H3Me2-2,5]2 (95)
Ph3Bi(OSO2C6H3Me2-2,5)2 + Zn
1070-3632/01/7108-1236$25.00 2001 MAIK Nauka/Interperiodica

REACTIONS OF TRIARYLBISMUTH BIS(ARENESULFONATES)
1237
product is the zinc salt of the corresponding acid. The
yields of the products are close to quantitative.
Crystals formed and were filtered off, washed with
water and ethanol, and dried to obtain 0.31 g (94%)
of triphenylbismuth sulfate, mp >280 C. IR spectrum,
1
Ph3Bi(OSO2Ar)2 + Zn
Ph3Bi + (ArSO2O)2Zn,
, cm : 1250 v.s, 1120 v.s, 980 v.s. The aqueous-
ethanolic extracts were evaporated in a dessicator with
concentrated sulfuric acid to obtain 0.26 g (96%) of
2,4-dimethylbenzenesulfonic acid, mp 47 C.
Ar = C6H3Me2-2,4, C6H3Me2-2,5.
The starting compounds were prepared by oxida-
tive addition of triphenylbismuth with arenesulfonic
acids in the presence of hydrogen peroxide [2, 3].
Reaction of triphenylbismuth bis(2,4-dimethyl-
benzenesulfonate) with potassium hydroxide. A
solution of 0.07 g of potassium hydroxide in 10 ml of
ethanol was added to 0.50 g of triphenylbismuth bis-
(2,4-dimethylbenzenesulfonate) in 10 ml of ethanol.
A precipitate formed and was washed with water and
ethanol, and dried to obtain 0.18 g (62%) of tri-
Thus, we established that Bi O bonds in triphenyl-
bismuth bis(arenesulfonates) are easily cleaved under
the action of sulfuric acid, bases, salts, and metallic
zinc.
1
phenylbismuth dihydroxide. IR spectrum, , cm :
EXPERIMENTAL
3440 v.s, 3050 s, 1640 s, 1560 s, 1470 s, 1430 s,
1005 s, 990 s, 830 s, 730 v.s, 690 v.s. mp >250 C.
The obtained triphenylbismuth dihydroxide was
treated with ethanolic hydrochloric acid. The solvent
was removed, and the residue was extracted with
toluene and then with ethanol. The toluene extracts
were evaporated to obtain triphenylbismuth dihydro-
chloride, mp 158 C. Evaporation of the ethanol ex-
tracts gave 0.27 g (98%) of potassium 2,4-dimethyl-
The IR spectra were recorded on a Hitachi-215
spectrometer (suspension in Vaseline oil).
The reactions were carried out in evacuated glass
ampules by the following typical procedures.
Reaction of triphenylbismuth bis(2,5-dimethyl-
benzenesulfonate) with sodium fluoride. A solution
of 1.5 g of triphenylbismuth bis(2,5-dimethylbenze-
nesulfonate) in ethanol was mixed with a solution of
0.16 g of sodium fluoride in water. A finely dispersed
precipitate formed. The solvent was removed, and the
residue was extracted with toluene. The toluene was
evaporated to leave 0.82 g (93%) of triphenylbismuth
difluoride, mp 125 C. The weight of the toluene-
insoluble sodium 2,5-dimethylbenzenesulfonate with
mp >250 C was 0.75 g (97%). The IR spectra of the
obtained compounds were identical with those of the
authentic samples.
1
benzenesulfonate, mp >250 C. IR spectrum, , cm :
1200 v.s, 1095 s, 1030 v.s.
Reaction of triphenylbismuth bis(2,5-dimethyl-
benzenesulfonate) with zinc. A mixture of 0.35 g of
triphenylbismuth bis(2,5-dimethylbenzenesulfonate)
and 0.50 g of zinc powder in 10 ml of acetone was
kept for 24 h at room temperature. Colorless crystals
formed. The solvent was removed, and the residue
was extracted with petroleum ether and ethanol. The
ether extract was evaporated to obtain 0.18 g (95%)
of triphenylbismuth, mp 77 C. Evaporation of the
ethanol solution gave 0.18 g (95%) of zinc bis(2,5-
dimethylbenzenesulfonate), mp > 250 C. IR spectrum,
Reaction of triphenylbismuth bis(2,5-dimethyl-
benzenesulfonate) with sodium acetate. A mixture
of 0.70 g of triphenylbismuth bis(2,5-dimethylben-
zenesulfonate) and 0.14 g of sodium acetate in 20 ml
of toluene was heated for 15 min at 90 C. The finely
dispersed precipitate was washed with toluene and
dried to obtain 0.35 g (97%) of sodium 2,5-dimethyl-
benzenesulfonate, mp >250 C. Removal of the solvent
and crystallization from chloroform gave 0.44 g
(92%) of triphenylbismuth diacetate, mp 187 C (with
decomposition). The IR spectra of the obtained com-
pounds were identical with those of the authentic
samples.
1
, cm : 1145 v.s, 1100 v.s, 960 s. This IR spectrum
is identical to the IR spectrum of zinc bis(2,5-di-
methylbenzenesulfonate) prepared from zinc and 2,5-
dimethylbenzenesulfonic acid.
REFERENCES
1. Ruther, R., Huber, F., and Preut, H., Z. Anorg. Allg.
Chem., 1986, vol. 539, no. 1, pp. 110 126.
2. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., Sen-
churina, V.S., Zakharova, A.N., and Bel’skii, V.K., Zh.
Obshch. Khim., 1999, vol. 69, no. 9, pp. 1470 1473.
3. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., Khar-
sika, A.N., Lodochnikova, O.A., Gubaidullin, A.T., and
Litvinov, I.A., Izv. Ross. Akad. Nauk, Ser. Khim., 1999,
no. 12, pp. 2350 2354.
Reaction of triphenylbismuth bis(2,4-dimethyl-
benzenesulfonate) with sulfuric acid. A mixture of
0.50 g of triphenylbismuth bis(2,4-dimethylbenzene-
sulfonate) and 10 ml of ethanol was treated with
0.13 ml of 98% sulfuric acid (1:4 molar ratio).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 8 2001