Russian Journal of Organic Chemistry, Vol. 39, No. 6, 2003, p. 900. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 6, 2003,
p. 949.
Original Russian Text Copyright
2003 by Rakhimov, Nalesnaya, Vostrikova.
SHORT
COMMUNICATIONS
O-Polyfluoroalkylation of Phenol with Polyfluoroalkyl
Chlorosulfites
A. I. Rakhimov, A. V. Nalesnaya, and O. V. Vostrikova
Volgograd State Technical University, Volgograd, Russia
Institute of Chemical Problems of Ecology, Volgograd, 400066 Russia
Received November 6, 2002
Polyfluoroalkyl phenyl ethers were previously
prepared by a reaction of bromobenzene with
alcoholates of polyfluorinated alcohols in pyridine in
the presence of copper [1]. No published reports on
synthesis of polyfluoroalkyl phenyl ethers by direct
polyfluoroalkylation of phenol were found.
1-Phenoxy-1,1,3-trihydroperfluoropropane (III).
With 3.71 g (0.04 mol) of triethylamine was mixed
3.45 g (0.04 mol) of phenol till complete dissolution,
the mixture was diluted with 15 ml of pentane, cooled
to 10 C, and at this temperature while stirring was
added a solution of 7.87 g (0.04 mol) of polyfluor-
alkyl chlorosulfite (I) in 20 ml of pentane maintaining
the temperature at the same level. The reaction mix-
ture was left standing at room temperature for 24 h.
The triethylamine hydrochloride was filtered off, the
pentane was distilled off, and the product was distill-
ed in a vacuum. Yield of ether III 3.24 g, 42.5 %,
bp 53 54 C (p 3 mm Hg), nD20 1.4508, d240 1.4378.
Similarly from 2.51 g (0.03 mol) of phenol, 2.70 g
(0.03 mol) of triethylamine, and 8.4 f (0.03 mol) of
polyfluoroalkyl chlorosulfite (II) was prepared ether
IV. Yield 4.29 g (51%), bp 68 75 C (p 3 mm Hg),
nD20 1.3980, d240 1.5762.
We established that polyfluoroalkyl chlorosulfites
I, II react with a complex of phenol with triethyl-
amine furnishing polyfluoroalkyl ethers of phenol.
The reaction is likely to occur via six-membered
transition state. Besides polyfluoroalkyl phenyl ethers
III and IV form also SO2 and triethylamine hydro-
chloride.
IR spectra of phenol ethers obtained were recorded
on spectrometer Specord-M82 from thin films. The
1
following absorption bands were present (cm ):
2932, stretching vibrations of a methylene group;
1604 and 1504, stretching vibrations of the aromatic
ring; 1239, asymmetric stretching vibration of the
C O C bond, 1032, symmetric stretching vibration
of the C O C bond, 1192, stretching vibrations of
CF2 groups.
n = 1 (I, III), 2 (II, IV).
REFERENCES
The structure of ethers obtained was confirmed by
IR spectra and hydrolysis. The acid hydrolysis of the
ethers gives rise to phenol and trihydroperfluoro-
alkanol.
1. Shelud,ko, E.V. and Kalibabchuk, I.I., Zh. Org.
Khim., 1979, vol. 15, p. 1661; Shelud,ko, E.V., Dokl.
Akad. Nauk SSSR, 1978, p. 1008.
1070-4280/03/3906-0900$25.00 2003 MAIK Nauka/Interperiodica
Rakhimov
