Note: Descriptions are shown in the official language in which they were submitted.
3~
The present invention relates to a method for the preparation of a
class of fluorine containing ethers.
This application is divided from applicant's copending Canadian
application Serial No. 379,~2~ filed June 10~ 1981, the latter relating to
a compound represented by the general formula
Y(CF2)a-(CFRf)b-CFRf -O- ~F-CF2-~ - (F-CF2~ - CF-C=O
~F2X Jn ~F2X ~m CF2X
where
a = O or an integer greater than O;
b = O or an integer greater than O;
m = O or an integer greater than zero;
n = ~ero or an integer greater than 7ero;
Rf and Rf are each indeper.dently selected from the group
consisting of F, Cl, perfluoroalkyl and
fluorochloroalkyl;
X = F, Cl, Br or mixtures thereof when n > l;
X' = Cl, Br or mixtures thereof;
Y is an acid group or an acid derivative easily convertible to
an acid group;
Z = F, Cl, Br, OH, NRR' or OA;
R and R' are independently selected from the group consisting
of hydrogen, an alkyl having one or more carbon atom
and aryl;
~8~3~
A = alkali metal, quaternary nitrogen, or R.
The present invention concerns the preparation of specific
compou]lds within the broad compound definition set forth above.
United States Patent 3,301,893 teaches reacting
with
F
Rf
to form compounds represented by the general formula
YS2 ~ CF ~ CF2 ~ - ~F ~ CF2 ~ ~ - CF - C = 0
Rf X n X
3~
where
R~ i5 F or perfluoroalkyl radicals hav.ing from
1 to lO carbon atoms;
S X is F or a trifluoromethyl radical, or
mi~tures thereof, where there is more than one X;
Y is a radical selected from the group con-
sisting of fluorine, amino, hydroxyl and OMe
radical where Me is a radical selected from the
, group consisting of the ammonium radical, alkali
¦ metals and other monovalent metals; and
! n is a number from O to 12.
U.S. Patent 3,536,733 teaches the preparation
¦ of compounds represented by the general formula
~ /~
YCF - CF2
where Y is F or CF3.
~ British patent 1,518,387 teaches the following
reactions.
CH30CCF2CF2~ + CF3CF-CF2 >
CH30CCF2CF2CF20CFCF2OCFC Na2CO3
CF3 CFF
.
~ 28,978-F ~3-
. ~ .
~.,
.~
34~3
CH3 0 C-CF2-CF2-CF2-O-CF-CF2-O-CF=CF2
CF3
U.S. 3,282,875 teaches pyrolyzing compounds
having the general ormulas
10FSO2 - CFCF20 -~CF - CF2 - ~ - CF - C = O
, Rf ~ Jn CF3
and
OX
15FSO2 - CFCF20 ~CF - CF2 - O~- CF - C - O
.
Rf ~ ~ n CF3
` to form compounds represented by the general formula
3, MSO2 CF - CF2 - O -~CF - CF2 - O~- CF = CF2
! , . , I
~ 20 Rf ~ Jn
where
Rf is F or a perfluoroalkyl radical having
from 1-10 carbon atoms;
25Y is F or a trifluoromethyl radical;
n is an integex of 1-3, inclusive;
. M is F, hydroxyl radical, amino radical or
s OMe; and
^' Me is an alkali metal or quaternary nitrogen
30radical.
X is alkali metal
.
~. 28,978-F ~ -4-
3~
The present invention resides in a method for preparing
compounds of the formula
F
Y~CF2)a - ~cFR~b-cFRf-o-(cF-cF2-o~-cF=c=o
~ F2X ~n CF2X~
which comprises reacking compounds of the formula
/o\
X'CF2 - CF - CF2
with compound of the formula
Rf
Y(CF2)a - ~CFRf~b - C = O
for a time and a temperature sufficient to form said compound;
wherein
a = O or an integer greater than O;
b = O or an integer greater than O;
n - zero or an integer greater than zero;
Rf and Rf are each independently selected from the
group consisting of F, Cl, perfluoroalkyl
and fluorochloroalkyl;
X' is independently Cl or Br;
Y is an acid group or an acid derivative easily
con~ertible to an acid group.
-- 5 --
Z'
Preferably, Y may be S02-Z', C-0, P=0 or C-N or
(Z )2
other appropriate groups (as Z is defined above).
The present invention, together with that disclosedand claimed
in aforementioned application Serial No. 379,~24, will now be further discussed.
The compounds of the process of the present invention are
intermediates which may be further reacted to form a novel class of monomers,
which, in turn, may then b0 polymerized and used in the preparation of chem-
ically stable ion exchange resins or membranes.
When the polymers ultimately derived from the intermediates of
the invention are formed into sheets for use as membranes such as in chlor-
alkali cells, it is desirable to choose Z so thatthe polymers formed are
thermoplastic to allow fabrication by conventional means, such as melt extru-
sion. After fabrication they can be easily converted to the acid or alkali
me~al salt of the acid. As an example, when Y = SO2F ~Z=F), the intermediate
is converted to an olefin monomer still having the -SO2F group. The monomer
is then copolymerized to form a polymer containing the SO2F group that can be
formed into sheets by various plastic fabrication techniques. After fabrication,
the Sn2F group is easily converted to the alkali metal salt of the corresponding
sulfonic acid, -SO2ONa ~Z = ONa), which can be converted to the sulfonic acid,
-S020H ~Z=OH), by reaction with acids, such as mineral acids. -S02F + NaOH --~
-SO2ONa + NaF C -SO2OH + NaCl. When Y is chosen as -C=N, a nitrile, the
above conditions are met since it is well known thatnitriles are converted to
carboxylic acids by hydrolysis.
When the polymers derived from the olefins from the present
intermediates are to be used in particle or powder form, such as for
acid catalyst, it is not critical in the choice of Z since
fabrication is not as large a factor. In this case, Z can con~eniently be
any of the radicals listed. It can be -011 so as to directly have Y
as an acid group or it can be any group rendering Y convertable
to an acid group by further reaction.
X is chosen from the halogens Cl, Br or F, while X' is
chosen from Cl or Br. While iodine would also be useful for X or
X', formations of theethersby the chemistry taught herein is hampered
by side reactions causing low or nonexistant yields to the desired
compounds .
When X' = Cl or Br and X = F, Cl or Br, new uses and novel
and surprising new chemistry results from using the intermediates
for additional chemical reactions. The prior art teaches that when
Y = S02F, n = 0, M=0, and X' = F ~United States Patent No. 3,560,56~)
reaction of the intermediate with a base does not produce the
desired vinyl ether monomer,but rather a cyclic sulfone coinpound.
Surprisingly, when n = 0, M = 0, Y = S02F and X' = Cl or Br, reaction
of the intermediate with a base produces the desired vinyl ether
product in one step. In addition to this benefit, choosing X or X'
= Cl or Br in compounds where m or n> 0 resultsin introducing a
potential reaction site into polymers ultimately derived from monomers
made from these intermediates. When m or n > 0 both an acid site for ion
excnange or catalyst ~Y) and a reaction site for further reaction can
be obtained by having X or X' = Cl
3~1
or Br. In general, metallation reagents such as alkyl alkali metals
can be used for reactions on these reaction sites.
There is an additional benefit for having X' = Cl or Br.
In this case it is helpful to have Cl or Br in this position for
the subsequent reactions and uses for these compounds.
l`he variables in the structures have preferred values
as follows: n = 0 - 6, m = O - 6, a = O - 3, b = O - 3. Preferred
is n = O - 3 and m = O - 3. Most preferably n = O or l and m = O or l.
Preferably X = Cl, X' = Cl and Y = Z'SO2. More preferably Y = Z'SO2
and Z' = F. Rf and R'f are preferably F.
In decarboxylations of the prior art, compounds of the
terminal functionality shown below are common.
-O-CF- C=O
CF3
These materials generally require high tempera~ure and
activators such as ZnO or silica to achieve reasonable yields
to the desired vinyl ethers.
~0-CF-C=0 heat ~0-CF=CF
, Activator 2
CF3
3~,~
When X' is Cl or Br in the present invention,
decarboxylation of these intermediates to vinyl ethers has
been found to proceed under mild conditions and in excellent
yields.
In the process of the present invention, the reactions are
carried out in the presence of a fluoride ion yielding compound
metal fluoride-catalyst (MF) at a temperature and a time
sufficient to cause a reaction, preferably from -20C to 50C,
in the liquid state, desirably in a liquid solvent for the inter-
mediate fluoroalkoxide Y(CF~)a - (CFRf)b - CFR~ 0 M formed
between the acid fluoride or ketone
R~
Y(CF2)a - (CFRf)b - C = O
and the metal or ammonium fluoride, fluorine ion yielding
catalyst (MF). The reactions proceed generally according
to the equation
(n)X'CF2-CF-CF2 ~ Y(CF2)a (CFR~)b-C=0 --
~
Y(CF2)a~(CFRf)b -CFRf -0- ~ F-CF2 -~ -CF-C=0
\CF2X ' ~ CF2X
Conversion of acid halides such as the acid fluorides
dsscribed herein to carboxylic acids and
39t~
--lU--
derivatives by reaction with nucleophiles is well known
to those skilled in the art. For example, conversion
of the acid fluoride to the corresponding carboxylic
acid is easily accomplished by reaction with water.
Conversion to esters or amides is accomplished by
reaction with alcohols or amines, respecti~ely. The
carboxylic acids ~Z = OH) are easily converted to acid
chlorides or bromides (Z - Cl, Br) by reaction with
appropriate halogenation agents such as PC15 or PBr5.
Reactions of the carboxylic acid fluoride proceed
according to the following eguation:
F Z'
~ C=O -~ PZ' ~ ~ C=o + PF
where
Z' = OH, NRR' or OR;
R and R' are independently selected from the
group consisting of hydrogen, an alkyl
having one or more than one carbon atom
and aryl;
P is a cation or capable of forming
a cation, such as Na , K , H , etc.
It is of course to be understood that in the
reaction of the acid fluorides or ketones with the
epoxides the ratio of reactants, the temperature of
reaction, the amount of catalyst, as well as the amount
and kind of solvent, influence the course, speed and
direction of the reaction. Naturally the ratio of
reactants bears more directly on the value of m and n
in the generic formula than the other factors noted.
For example, employing 1 or more moles of acid halide
compound per mole of perhalofluoro epoxide results in a
28,978 F ~10-
9341~
product rich in the n=0 product, i.e., greater than 1.5 n=0 to n=l,
respectively and if the ratio is 2 to 1, respectively, the n=0
product, respectively, is about 92 to 1, respectively, whereas
employing greater than 1 mole epoxide compound per mole of acid
fluoride compound, i.e., 2 to 1, respectively, results in a product
having a 3:9:1 ratio of n=2: n=l:n=0 products. The ratio of
reactants thus can range, for practical purposes, from about 2 ~o 3
moles of ~he acylfluoride or ketone per mole of the halofluoro
epoxide to 1 to 20 moles of the epoxide per mole of the acyl fluoride,
the high acyl fluoride to epoxide producing predominantly the n=0
and the high epoxide to acyl fluoride producing the n=2=12 ether,
respectively, and mixtures thereof.
Solvents employed should be non-reactive (e.g., do not contain
hydroxyl groups) and have at 1east a solubility for the reactants and
the intermediate fluoroalkoxide formed between the acyl fluoride or
ketone compound and the catalyst. Whether or not the products are
significantly soluble in the solvent is a matter of choice and can be
used as a controlling factor for selectively controlling the n value
in the final product. For example, if a high n value is desired, it is
advantageous that the product having at least n=0 to 1 be soluble in the
solvent to give the intermediates (n=0 and n=l) time to react to produce
the final n=l, 2 or higher product. In addition, the amount of solvent
can be adjusted to accomplish somewhat similar results. Generally, when
the ratio of the weight of solvent to the weight of the acid fluoride
is from about 0.3:1 to about 0.8:1, formation of the n=0 product is
maximized. As the weight ratio increases, higher n values are
obtained. Although there is no theoretical maximum
amount of solvent which may be used, one may quickly
determine the weight ratio to be used depending upon
the value of the n that he desires. Suitable solvents
which may be employed to take advantage of the solu-
bility plus amount factor are, for example, tetraglyme,
di~lyme, glyme, acetonitrile, or nitrobenzene. Exemplary
of a preferred solvent is te-traglyme which has a suitable
solvency for the intermediate, but in a weight to
weight ratio has limited solubility for the product n=0
and therefore can be used advantageously to precipitate
the n=0 product (remove it from the reactlon media),
effectively controlling (minimizing) the production of
higher n values, yet if higher n values are desired,
greater quantities of the solvent can be employed to
dissolve the product n=0 or an amount sufficient to
maintain a quantity thereof in the reaction medium`to
permit the epoxide to further react with the n=0 product
to produce higher n value products. By controlling the
amount, again it is possible to salt-out the inter-
mediate n-values as a function of their solubility and
quantity in the solvent-reaction media.
In a somewhat similar manner, the catalyst
amount functions as a control of the end product n
~alue. While the source of the fluoride ion is not
critical, the amount of catalyst will to a significant
measure establish the reactivity of the acid fluoride
and thus determine the rate of reaction of the acid
fluoride with the epoxide. Significant amounts of the
catalyst, up to stoichiometric amounts based on the
acld fluoride or ketone, will favor epoxide reacting on
the feed acid fluoride. Whereas lesser catalytic
amounts, with respect to the acid fluoride will favor
28,978-F -12-
3~1!3
the reaction of the epoxlde with the n=O acid fluoride
product forming higher n products. ~s has been noted,
substantially any fluoride ionizable at the reaction
conditions may be used as a catalyst, however, CsF and
- KF are the most preferred but AgF, tetra alkyl ammonium
fluoride as well as others listed ~y Evans, et al.,
J. Org. Chem. 33 1837 (1968) may be employed with
satisfactory results.
The temperature of the reaction also ef~
fectuates a controlling factor on the end product
obtained. For example, low temperatures such as -20C
favor n=O products and higher temperatures, 500r and
above, favor higher n values.
In summary, the following table illustrates
the effect each parameter of the reaction has on the n
value of the final product.
n = O -~ n = 12
Ratio of
ketone or acyl
fluoride
to epoxide 3/1 1/20
Solvent amt. small large
Temp. low high
Catalyst high low
EXAMPLES
EXAMPLE 1
90 ml of dry tetraglyme and 39.5 gms of
anhydrous CsF were added to a 500 ml 3-neck flask
28,978-F -13-
~8~3~1~
equipped with a stirrer, thermometer, reflux condenser
at a temperature of -78C, and an inlet port. Downstream
of the reactor were liquid N2 cold traps maintained at
a temperature of 78C. A slight back pressure was
maintained on the system with dry N2.
The reactor was cooled to 0C to 5C and 126
grams of fluorosulfonyldifluoroacetylfluoride
FSO2 - CF2 - C = O,
were added slowly over a 20 minute period and tnen
allowed to mix for another 20-30 minutes to ensure
formation of the alkoxide.
~O\
64.3 grams of ClCF2 - CF - CF2 were added
slowly over an hour and 45 minutes while maintaining
the reactor temperature at 0 to 5C. After the epoxide
addition, the contents were allowed to mix for an
additional hour. The temperature was allowed to rise
to room temperature. When stirring ceased, two separate
layers formed. The bottom layer was drawn off and
weighed 104.7 yrams. VPC (Vapor Phase Chromatography)
analysis of this product showed 92% n=O product and
- 7.85% lights or product formed by reaction of the
epoxide with itself.
- Conversion of the epoxide was essentially
~omplete. Yield of epoxide to the n=O product was
75.3%.
The products were analyzed further by GC-MS
(Gas Chromatography-Mass Spectrophotometry) and the
following compounds were identified:
28,978-F --14-
3~
F as the light
I material
Cl(CF2)3 - O - CF - C - O
CF~Cl
F as the n=0
product
FSO2(CF2)2 - O - CF - C = O
CF2Cl
Products were analyzed further by IR. The
-COF groups present at 1870-1880 wave no., -FSO2 group
at 1460 and 1240 wave nos.; and -SF at 810 wave number
for n=O product.
; 15
The products had retention times of 1.35 and
2.74 minutes, respectively, on a VPC uslng six feet
columns of 20% Viton~ on Celite~. Column temperature
of 60C.
EXAMPLE 2
35 ml of dry tetraglyme and 15.6 gms CsF
were added to a 3-neck 100 ml flask equipped with a
stirrer, ~hermometer, ~-78C) reflux condenser and an
inlet port. Downstream of the reactor were two (-78C)
~ cold traps in series. A slight back pressure was
- maintained with dry N2. Tetraglyme and CsF were mixed
for 45 min. to 1 hour.
- The reactor was cooled to 0C to 5C and
49.32 grams of fluorosulfonyl difluoro acetyl fluoride
FSO2 - CF2 - C = O
F
28,978-F -~15-
~L~8q:~3~
. ," --1~
were added slowly over a 20 minute period, allowed to
mix at 0 to 5C for 2 hours and then the temperature
was raised slowly to xoom temperature to ensure the
formation of the alkoxide. After cooling the reactor
to 0C, 25 grams of chloropentafluoropropylene oxide,
/Q~
ClCF2 - CF - CF2, were added slowly over a 3-4 hour
period. After the epoxide addition was complete, the
contents were mixed for an additional hour. The temp-
lo erature was allowed to rise to room temperature. When
stirring wa~ stopped, two liguid phases separated.38.94 gms of the heavy or bottom layer was collected.
Analyses by VPC showed 87.86% of n=0 product, 5~ un-
reacted reactants, and 4.2% of a higher molecular wt.
product. This gave an essentially compl~te conversion
of the epoxide and a 68.9% yield of epoxide to the n=0
product.
The unreacted reactant (FS02CF2CFO) was
distilled off the product.
35 ml of tetraglyme and 8 gm CsF were mixed
for 40 minutes. The heavies from the above distillation
were added slowly over a 20 minute period and mixed for
1 hour at 0C to 5C. The reactor was warmed to room
temperature to ~nsure formation of the alkoxide. After
cooling again to 0C to 5C, 19.6 grams of
/o\
ClCF2 - CF - CF2
were added slowly over a 2-3 hour period, and then
allowed to mix at 0C to 5C for another hour. The
reactor was warmed to room temperature. After stirring
was stopped, two separate layers formed. 35.67 grams
28,978-F -16-
,
3~
-17-
of bottom or product layer was collected. Analyses by
VPC showed 12.8~ n=0 product, 57.4% n=1, and 6.8% n=2
product. Thus, of the n = o product that reacted,
S 45 9% was converted to the n=l product.
The following products were identified by
mass spectrometer:
FS02(CF2)2 - 0 - CF - C = 0 n = 0
CF2Cl
-
F
lS FSO2 - (CF2)2 - 0 - CF - CF2 - 0 - CF - C = 0 n = 1
CF2Cl CF2Cl
F
FS02 - (CF2)2 - 0 - ~F - CF2 - 0~- CF - C = 0 n = 2
.
~F2Cl ~ 2 CF2cl
Mass spectroscopy fragmentation pattern
reported consistent with this structure of n=2.
The infraréd showed the characteristic S02F
and -C F0 bands, VPC retention times using the column
described in Example 1 with a temperature program of 4
i min. at 60C, followed by a rise to 220C at 16/min.
were 2.72, 5.74, and 8.18 minutes, respectively.
;
28,978-F -17-
~L8~3~1~
, ,.. , --1~--
EXAMPLE 3
:
75gm of FSO2(CF2)2 - O - CF - C = O
CF2 Cl
was added dropwise to a 500 ml vessel containing 200 gm
tetraglyme and 15.2 gm CsF. The vessel was fitted with a
cold fingex condenser and two traps on the effluent;
one dry ice acetone and the other liquid nitrogen. The
acid fluoride was ~tirred for one hour after the
addition was completed and then
/O~
ClCF2 - CF - F2
was added at a rate such that no reflux was observed on
; the cold finger. A total of 18.3 gm was added, keeping
the temperature below 35C. After completing the
addition, the mixture was stirred for an hour. The
vessel contents were poured into a separatory funnel
under dry nitrogen blanket and the lower product layer
was allowed to settle out. The product layer was
drained off and analyzed chromatographically as: 1 part
n=3, 1.1 parts n=2, 12 parts n=1, 4.6 parts residual
n=o .
EXAMPLE 4
30 ml of dry tetraglyme and 14.15 gms (.0932
mole) CsF were added to a 100 ml 3-neck flask equipped
with a stirrer, thermometer, (-78C) reflux condenser,
and an inlet port. Downstream of the reactor were two
(-78C) cold traps in series. A slight back pressure was
28,978-F -18-
.
3~
. .
-19-
maintained on the system with dry N2. Tetraglyme and
CsF were mixed for at least 45 minutes.
The reactor was cooled to -20C and 16.83 gm
(.093 moles) of
FS02 - CF2 ~ C - O
F
o
added. The temperature was brought up to 20-25 C and
30.2 gm of
lS ClCF2 - CF - CF2
were added in increments of 2 to 3 grams over a 4 houx
period while maintaining the reactor at 25-28C. After
the epoxide addition, the contents were stirred for an
2~ additional 1.5 hours. When stirring ceased, two separate
layers formed and were separated with a separatory
funnel. 28 gm of product (bottom layer) were
collected. Analysis by VPC showed 13.4% n=0 product,
33.8% n=l product, and 4.3% n=2 product. In addition,
there were products (dimers and trimers) of the
epoxide.
Products were analyzed further by GC-MS and
the following compounds were identified:
F
Cl(CF2)3 - O - CF - C = 0
CF~Cl
28,978-F -19-
~3L8~8
.. . ,~ ~
FSO2(CF2)z - O - CF - C = o
CF2Cl
F
Cl(CF2)3 - O - CF - CF2 - 0 CF - C = 0
CF2Cl CF2Cl
F
FS02 - ~CF2)2 - 0 - CF - CF2 - 0 - CF - C = 0
CF2Cl CF2Cl
lS F
FSO2 - (CF2)2 - 0 ~ F - CF2 - ~- CF - C - 0
~F2Cl 2 CFz
EXAMPLE 5
200 ml of dry tetraglyme and 15.19 gms (O.10 moles) of
CsF were added to a 500 ml 3-neck fla~k equipped with a
stirrer, thermometer, (-78C) reflux condenser, and an
inlet port. Two ~-78C) cold traps in series were
located downstream of the reflux condenser. A slight
back pressure was maintained on the system with dry N2.
- After stirring for 1 hour, the reactor was cooled to
-5C, and 51.22 gms (0.20 moles) of methyl perfluoro-
glutaryl fluoride
0 . F
CH30C(CF2)3C=0
28,978-F --~0-
3~
., .
wexe added dropwise. The reactants in the reactor were
stirred overnight at room temperature. Reactor was
cooled to ~5C and 18.25 gms (0.10 moles) of chloropenta-
fluoro propylene oxide
/o\
ClCF2 - CF - CF2
were added slowly. After the epoxide addition was
complete, samples were taken after 30 min. and 1.5 hr.
and analyzed by VPC. The temperature was then raised
to room temperature over one hour period and sample
analyzed by VPC.
The products were distilled out of the reactor
under 30" vacuum while heating to 160C. The overhead
temperature was 65C at this point. 49.38 gm of the
product was collected in the first cold trap and 2.5 gms
was collected in the second trap. The products were
analyzed by VPC.
The material caught in the first cold trap
was distilled in a microcolumn to remove the unreacted
methylperfluoroglutaryl fluoride. All material boiling
up to 145C was removed in this manner. Everything
- heavier was retained in the pot and weighed 18.44
grams. Heavies were analyzed by VPC, mass spec~roscopy
and I.R. ~Infra Red).
Peaks on the VPC were 7.21, 7.62, 8.86, and
10.47 minutes. Mass spectroscopy showed that the 7.21
peak had the structure
28,978-F -21-
3~
O F
"
CH30-C-CF2 CF2-CF2-CF2-O-CF-C=O
CF2C1
the 8.86 peak had the structure
O F
CH30-C-CF2-CF2-CFz-CF2-O-CF-CF2-O-CF-C=O
CF2Cl CF2Cl
IR analysis showed bands at 2960, 1860, and
1770-1780 Cm1. The 1860 Cm 1 band is the -COF group and
o
the 1770-1780 Cm 1 is the ester -C- group. The 2960 Cm 1
is due to the CH3 group.
Example 6
25 ml of tetraglyme and 6.4 gms of CsF were
added to a 50 ml, 3 neck flask equipped with a stirring
bar, thermometer, reflux condenser, and an inlet port.
Two (-78C) cold traps in series were located downstream
of the reflux condenser. A slight backpressure was
maintained on the system with dry N2. The tetraglyme
and CsF were allowed to mix for 1 hour at room tempera-
ture, lowered to 10C-20C, and 48 grams of FSO2CF2CFO
were added and allowed to mix for 1 hour. The mixture was
~O
- cooled to 0C and 25 grams of CF3CF-CF2 were added over
an hour and 20 minute period, while maintaining a
temperature of 0C to 10C. After mixing at this
temperature for 2 hours, the temperature was increased
to room temperature. The product was separated as a
clear, dense, bottom layer. 50.5 grams were recovered
which was determined to be 80.16%
28,978-F -22-
3~
23-
FSO2CF2CF2OCFCFO
CF3
by VPC analysis.
The lower boiling components were removed
leaving a mixture containing 88.6% of the desired acid
fluoride.
5 ml of tetraglyme and 1.7 gms CsF were added
to a 50 ml 3 neck flask equipped as above and the
mixture was stirred for 30 minutes. 5 grams of distilled
FSO2CF2CF2OCFCFO were added and mixed at 10-20C for
CF3
1 hour. 1.4 gms of ClCF2CF-CF2 were added while main-
taining a temperature of 0 to 10C, and held at this
temperature for 1 hour. The temperature was increased
to room temperature, 5 ml of tetraglyme added, and the
product separated from the solvent. 3.0 gr~ns of
product were obtained and analyzed as 63.98%
FSO2CF2CF2OCFCF2OCFCFO
CF3 CF2Cl
having a 6.47 minutP retention on the VPC and confirmed
by I.R. and mass spectroscopy.
28,978-F -23-
