Russian Journal of General Chemistry, Vol. 74, No. 4, 2004, pp. 633 634. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 4, 2004,
pp. 693 694.
Original Russian Text Copyright
2004 by Rakhimov, Nalesnaya, Vostrikova.
LETTERS
TO THE EDITOR
A New Method for Preparing Polyfluorinated Ethers
A. I. Rakhimov, A. V. Nalesnaya, and O. V. Vostrikova
Volgograd State Technical University, Volgograd, Russia
Institute of Chemical Problems of Ecology, Russian Academy of Natural Sciences, Volgograd, Russia
Received August 11, 2003
Polyfluorinated ethers are prepared by various
methods described in detail in [1 3]. We have devel-
oped a new method based on reactions of saturated
monohydric alcohols and phenol with polyfluoroalkyl
chlorosulfinates in the presence of tertiary amines.
Alcohols and phenol were taken as complexes with an
equimolar amount of triethylamine:
20 C and was kept at this temperature for 5 h. The
precipitate of triethylammonium chloride was filtered
off, the solvent was distilled off, and the product was
vacuum-distilled. Yield of Ib 2.8 g (42%), bp 104 C
(13 mm Hg), n2D0 1.3705, d420 1.4234, MRD 43.59,
calculated 41.98. IR spectrum, , cm : 1154 (COC),
1180 (CF2), 2892 (CH2O), 2980 (CH2, CH3). Com-
1
pounds II V were prepared similarly.
ROH NEt3 + RFCH2OS(O)Cl
1,1,3-Trihydroperfluoropropoxybutane IIa.
ROCH2RF + SO2 + Et3N HCl,
I V
Yield 45%, bp 102 C (4 mm Hg), n2D0 1.3700, d420
1.4165, MRD 45.99, calculated 46.63. IR spectrum, ,
1
R = Pr (I), Bu (II), n-C5H11 (III), RF (IV), Ph (V); RF =
HCF2CF2 (a), H(CF2CF2)2 (b).
cm : 1171 (COC), 1206 (CF2), 2912 (OCH2), 2963
(CH2), 2997 (CH3).
1,1,3-Trihydroperfluoropropoxypentane IIIa.
A solution of polyfluoroalkyl chlorosulfinate was
added at a temperature from 10 to 5 C to a complex
of an alcohol (or phenol) with triethylamine, prepared
in advance, after which the reaction mixture was al-
lowed to stand for 5 6 h at room temperature (solvent
pentane or hexane). The resulting salt, triethylammo-
nium chloride, is insoluble in this solvent and imme-
diately precipitates. The resulting ether was purified
by vacuum distillation; yield 39 51%. The alcohols
and phenol should be thoroughly dried before the
reaction, since polyfluoroalkyl chlorosulfinates are
readily hydrolyzed.
Yield 49%, bp 88 C (2 mm Hg), n2D0 1.3996, d420
1.0371, MRD 47.18, calculated 41.49. IR spectrum, ,
1
cm : 1137 (COC), 1214 (CF2), 2885 (OCH2), 2963
(CH2, CH3).
Bis(1,1,5-trihydroperfluoropentyl) ether IVb.
Yield 39%, bp 138 C (16 mm Hg), n2D0 1.3385, d420
1.7344, MRD 53.69, calculated 52.27. IR spectrum, ,
1
cm : 1137 (COC), 1176 (CF2), 2928 (CH2).
1-Phenoxy-1,1,3-trihydroperfluoropropane Va.
Yield 43%, bp 53 C (3 mm Hg), n2D0 1.4508, d420
1.4378 (published data: mp 186 C, n2D0 1.4388, d420
1.8992 [2]), MRD 38.94, calculated 42.59. IR spec-
The structure of the resulting ethers was proved by
IR spectroscopy and hydrolysis. For the known com-
pounds (Va, Vb), the constants were compared with
the published data.
1
trum, , cm : 2932 (CH2), 1604, 1504 (Ph), 1239,
1032 (COC), 1192 (CF2).
1-Phenoxy-1,1,5-trihydroperfluoropentane Vb.
1,1,5-Trihydroperfluoropentoxypropane Ib. A
1.4-g portion of propanol was mixed with 2.5 g of tri-
ethylamine in 20 ml of pentane, and the solution was
cooled to 5 C. A solution of 7.7 g of 1,1,5-trihydro-
perfluoropentyl chlorosulfinate in 15 ml of pentane
was added in portions, so as to maintain the tempera-
ture within the range from 5 to 10 C. After mixing
the reactants, the mixture was allowed to warm up to
Yield 51%, bp 68 C (3 mm Hg), n2D0 1.3980, d420
1.5760 {published data: bp 85 86 C (4.5 5 mm),
n2D0 1.4060, d420 1.4587 [2]}, MRD 47.48, calculated
1
52.37. IR spectrum, , cm : 2932 (CH2), 1604, 1504
(Ph), 1239, 1032 (COC), 1192 (CF2).
The IR spectra were recorded on a Specord M-82
spectrophotometer (thin films).
1070-3632/04/7404-0633 2004 MAIK Nauka/Interperiodica
Rakhimov
