Fluorocarbon compounds and processes for preparation thereof

Novel fluorinated (poly)sulfates, halosulfonates, halohydrins and expoxides, as well as novel processes for producing them are disclosed.

FIELD OF THE INVENTION 
Novel fluorinated halosulfonates, (poly)sulfates, halohydrins and epoxides, 
which are useful as monomers and chemical intermediates, are prepared by 
reacting (perfluoroalkyl)ethylenes with a combination of sulfur trioxide 
and a halogen, and further reacting the products of that reaction. 
BACKGROUND OF THE INVENTION 
U.S. Pat. No. 3,562,310 describes the preparation of compounds of the 
formula [R(CH.sub.2)m]2(OSO.sub.2).sub.p O by the reaction of 
R(CH.sub.2).sub.m I with sulfur trioxide (SO.sub.3), wherein m is 1, 2 or 
3, p is an integer of 2 to 6, and R is perfluoroalkyl. The hydrolysis of 
these polysulfates to the corresponding alcohol is also described. No 
mention is made of the use of halogen with the SO.sub.3, nor of the use of 
a fluorinated olefin in a reaction with SO.sub.3. 
U.S. Pat. No. 4,362,672 describes the preparation of difluorohaloacetyl 
fluoride by the reaction of CF.sub.2 =CFY with SO.sub.3 and bromine or 
iodine to produce an intermediate compound containing the group XCF.sub.2 
CFYOSO.sub.2 wherein X is I or Br and Y is F, Cl, Br or I. The 
difluorohaloacetyl fluoride is obtained by decomposing the intermediate 
thermally, optionally in the presence of catalysts. In this patent only 
fully halogenated (but otherwise unsubstituted) ethylenes are reacted. 
This is in contrast to the present invention where the 
(perfluoroalkyl)ethylenes that react with the SO.sub.3 /halogen 
combination contain no vinylic halogen. 
C. G. Krespan and D. A. Dixon, J. Org. Chem., Vol 51, pp. 4460-4466 (1986) 
describe the reaction of SO.sub.3 with perfluoro-2-butene. In this paper 
the olefin is fully fluorinated and no halogen is used in combination with 
the SO.sub.3. 
Two publications describe the preparation of halohydrins of 
mono(perfluoroalkyl)ethylenes, and (usually) their subsequent reaction 
with base to form the corresponding epoxides. Reaction of the 
mono(perfluoroalkyl)ethylenes with hypohalous acids (U.S. Pat. No. 
2,700,686), or with bromine and acetic acid the presence of mercuric ion 
[C. Coudures, et al., J. Fluorine Chem., Vol. 24, pp. 93-104 (1984)] are 
methods of making the mono(perfluoroalkyl)ethylene halohydrins. Other 
publications such as U.S.S.R. Patent 390,084 [Chem. Abs., Vol. 80, 27084u 
(1974)] and E. T. McBee and T. M. Burton, J. Am. Chem. Soc., Vol. 74, pp, 
3022-3023 (1952) describe the preparation of the halohydrins and epoxides 
of mono(perfluoroalkyl)ethylenes by other methods. A short "review" of 
early work on forming epoxides nominally derived from mono(perfluoroalkyl) 
-ethylenes is found in D. D. Smith, et al., Ind. Eng. Chem., Vol. 49, pp. 
1241-1246 (1957). This Smith paper also describes the polymerization of 
such epoxides and the use of the polymers as low load lubricants. None of 
these publications uses SO.sub.3, and none mentions the preparation of 
bis(perfluoroalkyl)ethylene halohydrins or epoxides. 
It is an object of this invention to provide novel halosulfonates and 
sulfates useful as intermediates in the production of mono- and 
bis(perfluoroalkyl)ethylene halohydrins and epoxides, and to provide novel 
bis(perfluoroalkyl)ethylene halohydrins and epoxides. It is a further 
object of this invention to provide an easy and inexpensive process for 
the preparation of mono(perfluoroalkyl)ethylene and novel 
bis(perfluoroalkyl) ethylene halohydrins and epoxides, and the 
intermediate sulfates and halosulfonates, by the reaction of mono- and 
bis(perfluoroalkyl)ethylenes with SO.sub.3 and a halogen, and other 
subsequent reactions to produce the desired products Mono- and 
bis(perfluoroalkyl) ethylene epoxides are useful as chemical intermediates 
and monomers. 
SUMMARY OF THE INVENTION 
This invention concerns novel (poly)sulfate and halosulfonate compounds of 
the formula 
EQU R.sup.2 R.sup.3 FCCHXCHR.sup.1 (OSO.sub.2).sub.n Z 
wherein each R.sup.2 and R.sup.3 is independently fluorine or 
perfluoroalkyl, R.sup.1 is H or --CFR.sup.2 R.sup.3, X is chlorine, 
bromine or iodine, and Z is selected from the group consisting of 
chlorine, bromine and --OCHR.sup.1 CHXCFR.sup.2 R.sup.3, and n is an 
integer from 1 to 6. 
This invention further concerns halohydrins of the formula 
EQU R.sup.2 R.sup.3 CHXCH(OH)CFR.sup.2 R.sup.3 
wherein R.sup.2, R.sup.3 and X are as defined above and epoxides of the 
formula 
##STR1## 
wherein R.sup.2 and R.sup.3 are defined as above. Also provided is a 
process for the production of fluorinated sulfates and halosulfonates 
comprising reacting SO.sub.3 and a halogen selected from the group 
consisting of chlorine, bromine and iodine with a (perfluoroalkyl)ethylene 
of the formula R.sup.2 R.sup.3 FCCH.dbd.CHR.sup.1, wherein R.sup.1, 
R.sup.2 and R.sup.3 are as defined above. The halohydrins, sulfates and 
halosulfonates are useful as intermediates for the preparation of 
fluorinated epoxides, which in turn are useful as chemical intermediates 
and monomers. 
DETAILS OF THE INVENTION 
This invention concerns (poly)sulfates and halosulfonate compounds of the 
formula 
EQU R.sup.2 R.sup.3 FCCHXCHR.sup.1 (OSO.sub.2).sub.n Z 
wherein each R.sup.2 and R.sup.3 is independently fluorine or 
perfluoroalkyl, R.sup.1 is H or --CFR.sup.2 R.sup.3, X is chlorine, 
bromine or iodine, and Z is selected from the group consisting of 
chlorine, bromine and --OCHR.sup.1 CHXCFR.sup.2 R.sup.3, and n is an 
integer from 1 to 6. Such sulfates and halosulfonates are made by the 
reaction of SO.sub.3 and halogen (excluding fluorine) with 
(perfluoroalkyl) -ethylenes (infra) of the formula R.sup.2 R.sup.3 
FCCH.dbd.CHR.sup.1 wherein R.sup.1, R.sup.2 and R.sup.3 are as defined 
above. The sulfates and halosulfonates are useful as intermediates in the 
synthesis of the corresponding epoxides. It is preferred that n is 2 to 4. 
It is also preferred when R.sup.2 is fluorine, and especially preferred 
when R.sup.2 is fluorine and R.sup.3 is n-perfluoroalkyl. It is most 
preferred that when R.sup.2 is fluorine, R.sup.3 is n-perfluoroalkyl and 
R.sup.1 is either hydrogen or --CF.sub.2 R.sup.4 wherein R.sup.4 is 
n-perfluoroalkyl. It is also preferred that all perfluoroalkyl groups 
individually contain up to 12 carbon atoms each. In preferred compounds Z 
and X are chlorine and bromine, and in especially preferred compounds Z 
and X are chlorine. In another preferred compound Z is --OCHR.sup.1 
CHXCFR.sup.2 R.sup.3. 
By the term "perfluoroalkyl" (including "n-perfluoroalkyl") herein is 
included a perfluoroalkyl group in which up to 2 fluorine atoms may be 
substituted by hydrogen and/or chlorine. Perfluoroalkyl groups also 
include branched structures and may contain ether oxygens between alkyl 
segments. 
This invention further concerns halohydrins of the formual 
EQU R.sup.2 R.sup.3 CHXCH(OH)CFR.sup.2 R.sup.3 
wherein R.sup.2, R.sup.3 and X are as defined above. It is preferred when 
each R.sup.2 is fluorine, and especially preferred when each R.sup.2 is 
fluorine and each R.sup.3 is n-perfluoroalkyl. It is also preferred when 
all perfluoroalkyl groups individually contain up to 12 carbon atoms each. 
It is preferred when X is chlorine and bromine, and especially preferred 
when X is chlorine. Such halohydrins may be reacted with base to form 
epoxides, which are useful as chemical intermediates (infra). 
This invention concerns epoxides of the formula 
##STR2## 
wherein each R.sup.2 and each R.sup.3 is independently fluorine or 
perfluoroalkyl. It is preferred when each R.sup.2 is fluorine, and 
especially preferred when each R.sup.2 is fluorine and each R.sup.3 is 
n-perfluoroalkyl. It is also preferred when all perfluoroalkyl groups 
individually contain up to 12 carbon atoms each. Such epoxides are novel, 
and can be hydrolyzed to the corresponding glycol (see Experiment 2), 
which is useful as a monomer (see U.S. Pat. No. 3,337,644). Such epoxides 
are made by the reaction of the corresponding halohydrin (supra) with a 
base, as illustrated in the Examples. These reactions are analogous to 
those of halohydrins derived from mono(perfluoroalkyl)ethylenes with 
bases; the latter reactions are well known to those skilled in the art. 
It is obvious from the above discussion that in order to produce the above 
sulfates and halosulfonates it is necessary to react a mono- or 
bis(perfluoroalkyl) -ethylene with SO.sub.3 and a halogen. The halohydrins 
described above can be made by hydrolysis of the sulfates or 
halosulfonates derived from bis(perfluoroalkyl) ethylenes, while the 
epoxides can be made from the halohydrins by reaction with base. Thus, it 
is simpler to specify preferred species of the above compounds by the 
ethylene from which they were derived and in some cases the halogen used 
in the SO.sub.3 /halogen reaction with the ethylene. The chemistry of 
typical reactions, and the products obtained form them, are illustrated by 
the equations in the Examples. 
Thus sulfates may be made from (perfluoro-n-butyl) -ethylene, 
1,2-bis(perfluoro-n-butyl)ethylene, 3,3,3-trifluoropropene (can also be 
called trifluoromethylethylene), 1,2-bis(trifluoromethyl)ethylene, 
(perfluorododecyl)ethylene, (6-H-perfluorohexyl)ethylene, 
(3-oxaperfluorohexyl)ethylene, (perfluoro-3-methylbutyl) -ethylene, 
(3,6,9-trioxaperfluoro-5,8-dimethyldodecyl) -ethylene, 
(3,4-dichloroperfluorobutyl)ethylene, (perfluoroethyl)ethylene, 
(1-trifluoromethyl-2-perfluoroethyl)ethylene, 
1,2-bis(perfluoroethyl)ethylene and 
[1-perfluoroethyl-2-(2-H-tetrafluoroethyl)]-ethylene. 
The halosulfonates may be made from chlorine and bromine and 
(perfluoro-n-butyl)ethylene, 1,2-bis(perfluoro-n-butyl)ethylene, 
3,3,3-trifluoropropene [can also be called (trifluoromethyl)ethylene], 
1,2-bis(trifluoromethyl)ethylene, (perfluorododecyl) -ethylene, 
(6-H-perfluorohexyl)ethylene, (3-oxa-perfluorohexyl)ethylene, 
(perfluoro-3-methylbutyl) -ethylene, 
(3,6,9-trioxaperfluoro-5,8-dimethyldodecyl) -ethylene, 
(3,4-dichloroperfluorobutyl)ethylene, (perfluoroethyl)ethylene, 
(1-trifluoromethyl-2-perfluoroethyl)ethylene, 
1,2-bis(perfluoroethyl)ethylene and 
[1-perfluoroethyl)-2-(2'-tetrafluoroethyl]ethylene. Chlorine is a 
preferred halogen 
The halohydrins may be made from chlorine, bromine or iodine and 
1,2-bis(perfluoro-n-butyl)ethylene, 1,2-bis(trifluoromethyl)ethylene and 
1,2-bis(perfluoroethyl) ethylene. Chlorine and bromine are preferred 
halogens, and chlorine is especially preferred. 
The epoxides may be derived from 1,2-bis(perfluoron-butyl) ethylene, 
1,2-bis(trifluoromethyl)ethylene and 1,2-bis(perfluoroethyl)ethylene. 
Preferred ethylenes used for the synthesis of the above sulfates, 
halosulfonates, halohydrins and epoxides (disubstituted ethylenes in the 
cases of the halohydrins and epoxides) are (trifluoromethyl)ethylene, 
1,2-bis(trifluoromethyl)ethylene, (perfluoroethyl)-ethylene, 
1,2-bis(perfluoroethyl)ethylene, (perfluorobutyl) ethylene and 
1,2-bis(perfluorobutyl)ethylene. 
A process for the production of fluorinated sulfates and/or halosulfonates 
comprises reacting SO.sub.3 and a halogen selected from the group 
consisting of chlorine, bromine and iodine with a (perfluoroalkyl) 
-ethylene of the formula R.sup.2 R.sup.3 FCCH.dbd.CHR.sup.1, wherein 
R.sup.1, R.sup.2 and R.sup.3 are as defined above. In preferred 
(perfluoroalkyl)-ethylenes each R.sup.2 is fluorine, and in especially 
preferred (perfluoroalkyl)ethylenes each R.sup.2 is fluorine and each 
R.sup.3 is n-perfluoroalkyl. In most preferred (perfluoroalkyl)ethylenes 
R.sup.2 is fluorine, R.sup.3 is n-perfluoroalkyl and R; is either hydrogen 
or --CF.sub.2 R.sup.3, wherein R.sup.3 is n-perfluoroalkyl. Preferred 
(perfluoroalkyl) ethylenes (those preferred above, or others) have 
perfluoroalkyl groups individually containing up to 12 carbon atoms. 
The SO.sub.3 used in the reaction may be added as a pure compound or 
dissolved in sulfuric acid, a solution commonly called oleum. Although no 
upper limit on the molar ratio of SO.sub.3 to (perfluoroalkyl)ethylene is 
known, a preferred molar ratio of SO.sub.3 to (perfluoroalkyl) -etnylene 
is about 1.0 to about 10, especially preferred about 1.5 to about 5, most 
preferably about 3 to about 4. The effect of adding "excess" SO.sub.3 on 
the value of "n" is discussed in connection with other fluorinated 
(poly)sulfates in L. G. Anello and R. F. Sweeny, J. Org. Chem., Vol. 35, 
p. 120 (1970), which is hereby included by reference. It is believed the 
instant process is similarly affected by SO.sub.3 levels. 
The halogen used in the reaction is usually added as the pure halogen. 
Chlorine and bromine are preferred halogens, and chlorine is especially 
preferred. Depending on the physical form of the halogen, it may be added 
as a gas, liquid or solid. The molar ratio of halogen to 
(perfluoroalkyl)ethylene is about 0.25 to about 4, preferably about 0.5 to 
about 1.0. Although the ingredients may be mixed in any order, it is 
preferred to mix the SO.sub.3 and halogen first, and then add the 
(perfluoroalkyl)ethylene. Precautions should be taken to control the 
temperature while the reagents are mixed. 
(Perfluoroalkyl)ethylenes useful in this process include, but are not 
limited to (perfluoro-n-butyl) -ethylene, 
1,2-bis(perfluoro-n-butyl)ethylene, 3,3,3-trifluoropropene (can also be 
called trifluoromethylethylene), 1,2-bis(trifluoromethyl)ethylene, 
(perfluorodecyl) ethylene, (6-H-perfluorohexyl)ethylene, 
(3-oxa-perfluorohexyl)ethylene, (perfluoro-3-methylbutyl) -ethylene, 
(3,6,9-trioxaperfluoro-5,8-dimethyldodecyl) -ethylene, 
(3,4-dichloroperfluorobutyl)ethylene, (perfluoroethyl)ethylene, 
(1-trifluoromethyl-2-perfluoroethyl)ethylene, 
1,2-bis(perfluoroethyl)ethylene and 
[1-perfluoroethyl-2-(2-H-tetrafluoroethyl)]-ethylene. 
The reaction is run at about 0.degree. C. to about 100.degree. C., 
preferably about 15.degree. C. to about 70.degree. C. The reaction may 
require from about 10 min. to several hours, depending upon the reactants 
and temperature chosen. Pressure is not critical, although with a gaseous 
halogen such as chlorine, elevated pressures may be used to achieve higher 
temperatures and higher concentrations. Autogenous pressure, usually about 
0.1 to about 100 atm. is often used. It is preferred to agitate the 
reaction mass during the reaction. 
Although it is preferred to use no solvent, a solvent that is inert under 
reaction conditions may be used if desired. 
The reaction vessel may be made of any material that is inert under the 
reaction conditions. Glass or Hastelloy.RTM. (trademark of Stoody Deloro 
Stellite, Inc.) are suitable. 
Starting materials should be reasonably dry, and moisture should be 
excluded during the reaction. It is sometimes convenient to use an inert 
atmosphere such as nitrogen or argon to exclude moisture. 
The sulfate and halosulfonate product(s) of the reaction may be isolated by 
methods well known to those skilled in the art, such as crystallization or 
distillation. Alternately, if "downstream" products are desired, the crude 
sulfates and halosulfonates may be hydrolyzed without isolation. Such 
methods are illustrated in the following Examples.

EXAMPLES 
Example 1 
##STR3## 
Sulfur trioxide (9.6 g, 0.12 mol) was stirred at 25.degree. C. while 32.1 g 
(0.13 mol) of (perfluorobutyl)ethylene was added. No indication of 
reaction was noted, so 30.5 g (0.12 mol) of iodine was added, whereupon an 
exotherm carried to 45.degree. C. and then abated. The mixture was stirred 
overnight at 25.degree. C., then at 50.degree. C for 30 min. Evolved gases 
were shown by IR analysis to be mainly SO.sub.2. Removal of volatiles by 
warming at 0.15 mm gave 5.3 g of recovered olefin and some iodine. The 
solidified residue was broken up, stirred with water, filtered and 
air-dried to give 29.2 g (58% based on SO.sub.3) of bis 
(3,3,4,4,5,5,6,6,6-nonafluoro-2-iodohexyl) -sulfate (1), mp 
45.degree.-48.degree. C. Recrystallization from methanol-water gave an 
analytical sample, mp 48.degree.-51.degree. C. IR(CDCl.sub.3): 2984 and 
2900 (sat'd CH), 1421 (possibly - SO.sub.2 -), 1250-1140 cm.sup.-1 
(SO.sub.2, CF, C-O). NMR(CDCl.sub.3): .sup.1 H and .sup.19 F spectra 
compatible with structure 1. Anal Calcd. for C.sub.12 H.sub.6 F.sub.18 
I.sub.2 O.sub.4 S: C,17.12; H, 0.72; I, 30.14; S, 3.81. Found: C,17.21; H, 
0.65; I, 29.98; S, 4.11. 
Example 2 
##STR4## 
A mixture of 203 g (0.80 mol) of iodine and 394 g (1.6 mol) of 
(perfluorobutyl)ethylene was stirred while 250 g (3.125 mol) of SO.sub.3 
was added dropwise over 10 hr. Off-gases condensed in a -80.degree. C. 
trap were warmed slowly to 25.degree. C. while ca. 32 mL of SO.sub.2 
evaporated; residual liquid was returned to the reaction mixture, and the 
whole was stirred overnight. Volatiles were removed by warming to 
50.degree. C. at 2 mm, leaving a partly solid residue. The residue was 
stirred with a solution of 350 mL of conc. H.sub.2 SO.sub.4 in 1 L. of 
water at 75.degree.-80.degree. C. for 5 hr. The mixture was cooled, 
filtered, and the organic layer of the filtrate was fractionated to give 
163.2 g (26%) of 3,3,4,4,5,5,6,6,6-nonafluoro-2-iodohexanol-1(2), bp 
56.degree.-62.degree. C. (3.5 mm), mp 30.degree.-31.degree. C. IR (neat): 
3400 (OH), 2952 and 2896 (sat'd CH), 1250-1100 cm.sup. -1 (CF,C-O). NMR 
(CDCl.sub.3): .sup.1 H and .sup.19 F fit structure 2. Anal: Calcd. for 
C.sub.6 H.sub.4 F.sub.9 IO: C, 18.48; H, 1.03; I, 32.54. Found: C, 18.20; 
H, 0.94; I, 31.20, 31.05. 
Example 3 
##STR5## 
To a mixture of 32 g (16.7 mL, 0.4 mol) of sulfur trioxide and 16.0 g (0.10 
mol) of bromine was added dropwise 49.2 g (0.20 mol) 
of(perfluorobutyl)ethylene. An exotherm and steady gas evolution subsided 
as the mixture was stirred after completion of the addition. Addition of 
another 16 g (0.10 mol) of bromine caused only a minor amount of further 
reaction. The mixture was stirred overnight and then evacuated at 20 mm to 
remove excess bromine. The stirred mixture was treated with 200 mL of 
water (cautiously at first), then heated at 80.degree. C. for 13.5 hr. 
Fractionation gave 45.7 g (67%) of 
3,3,4,4,5,5,6,6,6-nonafluoro-2-bromohexanol-1 (3), bp 64.degree. C. (10 
mm). IR (neat): 3401 (broad, OH), 2954 and 2898 (sat'd CH), 1250-1100 
cm.sup.-1 (CF, C-O). NMR (CDCl.sub.3): .sup.1 H and .sup.19 F spectra fit 
the assigned structure. MS: spectrum of the compound and its 
trimethylsilyl derivative accord with structure 3. 
Further fractionation gave 14.7 g (20%) of 
bis(3,3,4,4,5,5,6,6,6-nonafluoro-2-bromohexyl)sulfate (4), bp 
98.degree.-102.degree. C. (0.02 mm). IR (neat): 2999 (sat'd CH), 1423 
(SO.sub.2), 1250-1100 cm.sup.-1 (CF, C-O, SO.sub.2). NMR (CDCl.sub.3): 
.sup.1 H and .sup.19 F spectra fit the assigned structure. Anal. Calcd. 
for C.sub.12 H.sub.6 Br.sub.2 F.sub.18 O.sub.4 S: C, 19.27; H, 0.81; Br, 
21.36; S, 4.29. Found: C, 19.22; H, 0.77; Br, 21.08; S, 4.72. 
Example 4 
##STR6## 
To a mixture of 16.0 g (0.10 mol) of bromine and 32.0 g (0.4 mol, 16.7 mL) 
of sulfur trioxide was added 46 4 g (0.10 mol) of 
1,2-bis(perfluorobutyl)ethylene. The mixture was then stirred at 
40.degree.-50.degree. C. for 2 hr. while gas evolution nearly ceased. 
After having stirred overnight at 25.degree. C., the mixture was treated 
cautiously with 200 mL of water and stirred for 3 hr. Upon stirring 
overnight, the organic layer redeveloped a strong bromine color and the 
earliest GC product peaks grew while the next nearly disappeared; the 
latter product is presumed to be the bromosulfonate. The upper aqueous 
layer was extracted with 50 mL of CH.sub.2 Cl.sub.2, the combined extract 
and product layer were washed with 50 mL of water, dried over CaSO.sub.4, 
filtered and distilled. There was thus obtained 43.6g. (78%) of 
perfluoro(6-bromo-5H,6H-decan-5-ol) (5), bp 80.degree.-83.degree. C. (9.5 
mm). IR (neat): 3495 (broad, OH), 2996 (sat'd CH), 1250-1100 cm.sup.-1 
(CF,C-O). NMR (CDCl.sub.3): .sup.1 H and .sup.19 F spectra are compatible 
with a mixture of 2 racemates of 5. MS: spectra of the product and of its 
trimethylsilyl derivative fit structure 5. Anal. Calcd. for C.sub.10 
H.sub.3 BrF.sub.18 O: C, 21.41; H, 0.54; Br, 14.24. Found: C, 21.24; H, 
0.54; Br, 13.93. 
The residue from the distillation was 96% pure 6, the sulfate of 5. IR 
(neat): 2986 (sat'd CH), 1433 (SO.sub.2), 1250-1100 cm.sup.-1 (CF, C-O, 
SO.sub.2). NMR (CDCl.sub.3): .sup.1 H and .sup.19 F are compatible with 
structure 6. MS: FAB+gives the expected M+peak. 
Example 5 
##STR7## 
A mixture of 1036 g (2.6 mol on SO.sub.3 basis) of 20% oleum and 80 g (0.50 
mol) of bromine was stirred under a -80.degree. C. condenser while 68 g 
(0.71 mol) of 3,3,3- trifluoropropene was passed in batchwise so as to 
keep the pot temperature at 9.degree.-17.degree. C. The addition required 
4 hr., after which time the bromine color was nearly gone. The reaction 
mixture was extracted with 100 mL of small amount of sulfate 8 (identified 
by GC/MS and NMR) along with bromohydrin 7. The reaction mixture was then 
added dropwise to 2 L. of water, and the resulting mixture was extracted 
with 2.times.500 mL of CH.sub.2 Cl.sub.2. Distillation of the combined 
extracts gave 47.7 g of 2-bromo-3,3,3-trifluoropropanol-1 (7), bp 
60.degree.-61.degree. C. (50 mm). IR (neat): 3393 (OH), 2950 and 2894 
(sat'd CH), 1250-1150 cm.sup.-1 (CF, C-O). NMR (CDCl.sub.3): .sup.1 H and 
.sup.19 F spectra fit bromohydrin 7. The aqueous acid mixture was heated 
at 90.degree. C. for 30 min., cooled, and reextracted with 2.times.500 mL 
of CH.sub.2 Cl.sub.2. Fractionation of these extracts afforded an 
additional 42.3 g of pure 7, bp 60.degree.-62.degree. C. (50 mm). The 
total yield of 7 was thus 90.0 g (66%). 
Exmaple 6 
##STR8## 
A portion of 20% oleum (200 g, ca. 0.5 mol of SO.sub.3 present) was stirred 
under a -80.degree. C. condenser while chlorine (35.5 g, 22 mL at 
-80.degree. C., 0.5 mol) and (perfluorobutyl)ethylene (131 g, 050 mol) 
were added during 2 hr. portionwise and alternately in a manner to 
maintain some chlorine color and a pot temperature of 
10.degree.-15.degree. C. The mixture was then stirred vigorously for 2 hr. 
while an exotherm to 37.degree. C. occurred slowly and subsided. Analysis 
of the upper organic layer by GC/MS indicated the presence of both the 
sulfate and chlorosulfonate of chlorohydrin 10, in addition to 10 and 
dichloride 9. The entire mixture was added slowly and dichloride 9. The 
entire mixture was added slowly with stirring to 1 L. of water, and the 
whole was refluxed (75.degree.-80.degree. C.) for 1 hr. The organic layer 
was dried over MgSO.sub.4, filtered and distilled to give 71.8 g (45%) of 
1,2-dichloro-3,3,4,4,5,5,6,6,6-nonafluorohexane (9) bp 
73.degree.-79.degree. C. (100 mm), followed by 38.0 g (25%) of 2-chloro-3, 
3,4,4,5,5,6,6,6-nonafluoro-hexanol-1 (10), bp 96.degree.-97.degree. C. 
(100 mm). IR (neat): 3387 (strong, OH), 2955 and 2899 (sat'd CH), 
1250-1100 cm.sup.-1 (CF, C-O). NMR (CDCl.sub.3): .sup.1 H and .sup.19 F 
spectra are compatible with assigned structure. MS: spectra as is and of 
the trimethylsilyl derivative support structure 10. Anal. Calcd. for 
C.sub.6 H.sub.4 ClF.sub.9 O: C, 24.14; H, 1.35; Cl, 11.88. Found: C, 
24.02; H, 1.37; Cl, 12.01. 
EXPERIMENT 1 
##STR9## 
A mixture of 106 g (0.27 mol) of iodohydrin 2 and 25 mL of ether (to 
liquefy the iodohydrin) was added over a 30-min. period to 300 g (4.05 
mol) of molten KOH.H.sub.2 O which was being stirred at 150.degree. C. The 
pot temperature rose to 160.degree. C. and distillate was collected at bp 
50.degree.-90.degree. C. After distillation had ceased, application of 
light vacuum gave a small additional amount of distillate. Volatile 
products were washed with 50 mL of water, dried over Mg SO.sub.4, filtered 
and distilled to afford 48.4 g (68%) of (perfluorobutyl) -oxirane (11), bp 
46.degree.-47.degree. C. (100 mm), identified by G. C. and by comparison 
of the IR spectrum with that of a known sample, prepared by reaction of 
F(CF.sub.2).sub.4 CHBrCH.sub.2 OCOCH.sub.3 with hot base. 
Epoxide 11 was similarly produced by treatment of bromohydrin 3 and of 
chlorohydrin 10 with hot base. 
Example 7 
##STR10## 
Bromohydrin 5 (65 g, 0.116 mol) was added dropwise but rather rapidly to 
100 g (1.35 mol) of KOH.H.sub.2 O which was stirring at 140.degree. C. 
under 25 mm pressure. Distillate was taken, bp 40.degree.-70.degree. C. 
(25 mm), while the pot temperature was kept at 140.degree.-145.degree. C., 
then raised to 155.degree. C. (.about.10 mm) after addition had been 
completed. The crude product was washed with 50 mL of water, dried over 
MgSO.sub.4, filtered and distilled to give 31.3 g (56% conv., 77% yield) 
of 2,3-bis(perfluorobutyl)oxirane (12), bp 60.degree.-61.degree. C. (25 
mm). IR (neat): 3056 (sat'd. CH, weak), 1250-1100 cm.sup.-1 (CF). NMR 
(CDCl.sub.3): .sup.1 H and .sup.19 F show a 77:13 ratio of epoxide 12 
stereoisomers. MS fits the epoxide 12 structure, including the 
mass-measured M+. Anal. Calcd. for C.sub.10 H.sub.2 F.sub.18 O: C, 25.02; 
H, 0.42. Found: C, 22.21, 22.52; H, 0.38, 0.36. 
The distillation residue was 17.5 g (27%) of recovered bromohydrin 5. 
EXPERIMENT 2 
Hydrolysis of an Epoxide 
The following experiment demonstrates ring-opening of a 
2,3-bis(perfluoroalkyl)ethylene oxide with trifluoromethanesulfonic acid 
to give the corresponding glycol monotrifluoromethanesulfonate. The latter 
provides the glycol on hydrolysis. 
##STR11## 
A homogeneous mixture of 19.0 g (0.040 mol) of 
2,3-bis(perfluorobutyl)ethylene oxide and 17.7 g (0.118 mol) of 
trifluoromethanesulfonic acid was heated at 155.degree. C. in a sealed 
heavy-walled tube for 40 hr. GC showed the epoxide had reacted to give a 
single product in about 30% conversion. Analysis by GC/MS confirmed the 
structure as monoester; m/e 611 (M+-F), 481 (M+-CF.sub.3 SO.sub.2 O). The 
trimethylsilyl derivative established the presence of one hydroxyl group; 
m/e 687 (M+-CH.sub.3 O. 
Although preferred embodiments of the invention have been described 
hereinabove, it is to be understood that there is no attempt to limit the 
invention to the precise constructions herein disclosed, and it is to be 
further understood that the right is reserved to all changes coming within 
the scope of the invention as defined by the appended claims.