1070-4272/02/7507-1162$27.00C2002 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 75, No. 7, 2002, pp. 1162!1165. Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 7,
2002, pp. 1185!1188.
Original Russian Text Copyright + 2002 by Rakhimov, Vostrikova.
AND POLYMERIC MATERIALS
Polyfluoroalkyl Chlorosulfites as New Polyfluorinating Agents
A. I. Rakhimov and O. V. Vostrikova
Volgograd State Technical University, Volgograd, Russia
Institute of Chemical Problems of Ecology, Russian Academy of Natural Sciences, Volgograd, Russia
Received January 17, 2002
Abstract-The interaction of polyfluorinated alcohols with triethylamine and the kinetics of the reaction
of the resulting triethylamine complexes with thionyl chloride were studied, the mechanism of formation of
polyfluoroalkyl chlorosulfites was considered, and the optimal reaction conditions were found. The alkylating
power of polyfluoroalkyl chlorosulfites was studied in reactions with alkali metal halides (to obtain poly-
fluorohaloalkanes), in synthesis of acrylic and methacrylic acid esters, and in synthesis of polyfluoroalkyl
ethers (with polyfluoroalkyl 1-adamantyl ethers as example).
Polyfluoroalkyl chlorosulfites have been studied
poorly. These compounds were prepared by the reac-
tion of perfluoroalkyl hypochlorites with thionyl
OCl + SOCl
OS(O)Cl + Cl
In a later study , these compounds were prepared
by the reaction of polyfluoro alcohols with thionyl
chloride in the presence of triethylamine:
OH + SOCl
In contrast to alkyl chlorosulfites, which are inter-
mediates in reactions of alcohols with thionyl chloride
and readily eliminate SO
to form chloroalkanes,
polyfluoroalkyl chlorosulfites are stable compounds
distillable without decomposition.
In this work, we studied the interaction of polyflu-
orinated alcohols with triethylamine and the reaction
of the resulting complexes with thionyl chloride, with
the aim to optimize the preparation of polyfluoroalkyl
sulfites, which are of interest as polyfluorinating
agents in syntheses of polyfluorohaloalkanes and of
esters and ethers containing polyfluoroalkyl groups.
Calorimetric studies were performed with a DAK-
1-2M isothermal differential calorimeter. An ampule-
Reported at the 3rd International Conference [Chemistry,
Technology, and Applications of Fluoro Compounds] (St. Pe-
tersburg, July 639, 2001).
in-ampule glass microreactor was placed in a calori-
metric cell equipped with a device for breaking the
inner ampule (a thin-walled sphere). After the re-
quired temperature was attained, the thin-walled
sphere was broken, and the thermokinetic curve was
recorded with an LKS 4003 device; this curve was
processed to calculate the heat release rate and to
determine the rate constants using the kinetic model.
The heat of formation of the alcohol3triethylamine
complex was determined in the bulk at 30oC and
equimolar ratio of the alcohol and amine. Three rep-
licate runs were performed, and the thermokinetic
curves were processed by the trapezium method.
The error of the calorimetric measurements was
The kinetics of formation of polyfluoroalkyl chlo-
rosulfites was studied at 25, 30, and 35oC. The initial
concentrations of the alcohol3amine complex and
thionyl chloride were 0.18 M.
Procedures for synthesis and identification of poly-
fluoroalkyl chlorosulfites are reported elsewhere .
The reaction was performed in chloroform; the com-
plex of a polyfluorinated alcohol (0.05 mol) with
triethylamine (0.05 mol) was added to a solution of
0.075 mol of thionyl chloride, cooled to 340oC; in the
process, the mixture was not allowed to warm up
above 315oC. After adding the whole amount of the
complex, the mixture was warmed up to 20oC. The
precipitate of triethylamine hydrochloride was filtered
off, excess thionyl chloride was distilled off at atmos-
pheric pressure, and the residue was vacuum-distilled.
The yields and constants of polyfluoroalkyl chlorosul-
fites obtained by the reaction