THE SYNTHESIS AND REACTIONS OF SOME
SATURATED AND UNSATURATED
EUGENE C. STUMP, JR.
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
The author wishes to express his appreciation to those whose
contributions, both direct and indirect, have aided in the completion
of this research to Dr. Paul Tarrant, Director of this research
and Chairman of the Supervisory Committee, whose advice, enthusiasm
and guidance were the essential factors in the undertaking and
completion of this work; to Dr. W. S. Brey, Jr. for the interpretation
of nuclear magnetic resonance spectra; to the members of the
Supervisory Committee for donating their time, advice and assistance;
to Mr. M. D. Eckart for assistance in the preparation of certain
intermediates and to the Office of the Quartermaster General, U. S.
Army, and Wright Air Development Division, U. S. Air Force, for
financial support of this research.
Special thanks are due the author's wife for her encouragement,
understanding and help in the preparation of this dissertation.
TABLE OF CONTENTS
ACKNOWLED~ENTS * * * * * *
LIST OF TABLES * * . .
INTRODUCTION. . . * *
DISCUSSION. . . . . . .
EXPERIMENTAL . * * * *
A. Radical Additions to Allyl Ethers * *
1. Additions to Alyl Ethyl Ether *
24 Additions to Allyl 2-Chloro-1,l,2-
trifluoroethyl Ether *. *
B. Radical Additions to Vinyl Ethers .
li Additions to Vinyl Ethyl Ether *
2. Additions to Vinyl 2,2,2-Trifluoroe
Ether ** * *. *
* * *
* 0* *
Ci Reactions of P-Bromoethers * * 9 * *
D, Reactions of c-Bromoethers and Derivatives .* *
1, Reductions with Lithium Aluminum Hydride *
24 Reactions of the Reduced Ethers * .
3. Reactions with Alcohols * * e *
4. Reactions with Orignard Reagent * *
5. Other Reactions * * * *
E. Miscellaneous Reactions * * * * *
1. Synthesis of 2-(2,2,2-Trifluoroethoxy)-
butadiene * * * *
2. Reaction of Trifluoroethanol with
Methylacetylene .... .... 66
F. Preparation of Starting Materials . .. & 67
IV, SUMMARY . o . *. ., .. . 68
V. BIBLIOGRAPHY . . . . . . . .. . 70
BIOGRAPHICAL NOTE * * * 73
LIST OF TABLES
I. Properties of the Compounds Prepared . . *. . 29
II Analyses of the Compounds Prepared . . . . .
The advent of synthetic rubber during World War II signaled
the beginning of this nation's attempts to prepare elastomers for
specialty uses. As aircraft began to fly higher and faster, it became
apparent that new materials must be developed to withstand the rigors
of the Space Age. The Office of the Quartermaster General, anticipating
the need for these specialty components, established at the University
of Florida and elsewhere in 1951 a program of research and development
for the purpose of finding elastomeric materials which have an
exceptional combination of high thermal stability, resistance to
swelling in a variety of fuels and fluids, and low temperature
flexibility for unimpaired use in Arctic regions and at high altitudes.
A promising approach to the solution of this .problem was the
modification of monomers by the introduction of fluorine atoms into
the molecule. Such an approach was considered theoretically sound
since a number of fluorine-containing materials such as Teflon
polytetrafluoroethylenee] had demonstrated their enhanced thermal
stability and chemical resistance. Consequently, Lovelace (30,44)
initiated research in this laboratory by attempting the synthesis of
some fluorobutadienes, which he accomplished by the peroxide catalyzed
addition of perhaloalkanes to certain olefins. This work was extended
by Lilyquist (29) and Gillman (13,43). The syntheses of 1,1,2- and
1,1,3-trifluorobutadiene will serve as examples:
CF BrCFClBr + CHeoCH2H -2 roxide-" CBrCFC1CH2Br
CF2=CFCH=CH al, CF BrCFC1CHCH2 
CF2Br2 + CH2=CFCH peroxide CF2BrCH2CFBrCH
tri-n-butyl I amine
Polymerization of these monomers and evaluation studies of the
resulting polymers showed that the introduction of fluorine into the
molecule had indeed brought about an increase in low temperature
flexibility and swell resistance. Therefore, additional research in
the preparation of other new fluorine-containing monomers seemed
Tomasino (46) utilized free radical addition reactions for
the preparation of a number of unsaturated fluorine-containing silanes
and siloxanes while Johnson (22) studied the cyclo-alkylation reaction
between some fluoroalkanes and butadiene.
Since it was known that pendant groups on the polymer backbone
prevent crystalliiity to some degree, it was felt that alkoy-
substituted structures, with a. flexible ether linkage, should be
investigated. Monomers containing both fluorine and an ether linkage
night then provide both increased swell resistance and low temperature
The research discussed in this dissertation was undertaken as
a part of the Quartermaster program and describes the preparation of
some new aliphatic fluoroethers, both saturated and unsaturated.
Although they have been the subject of considerable attention,
aliphatic fluoroethers have been conveniently prepared by only two
general methods. Hanford and Rigby (17) found that alcohols may be
added to fluoro-olefins of the type CF2=CX2, where one X is hydrogen
or halogen and the other X is halogen
CF2=CX2 + ROH ROa CX2T CF20R 
This procedure was applicable to both mono- and dihydroVy
alcohols and was unusual in that the addition was nucleophilic and
base catalyzed as compared to the usual acid catalyzed electrophilic
additions to olefins. This reaction has been the subject of
investigation by a number of workers and has been extended to include
a wide variety of alcohols and fluoro-olefins. Tarrant and Brown (42)
added methyl, ethyl, i-propyl and t-butyl alcohol to CF2=CFC1, CF2 =CC1
and CF2=CHC1. Park and co-workers (32,33) have added alcohols to
some perhalopropenes and obtained both saturated and unsaturated
ethers. When CF^CC1=CC1, and CF CC1=CFC1 were reacted with a series
of alcohols the unsaturated ethers, CF3CC1=CCO1R and CF3CC1=CFOR,
respectively, were obtained. Saturated ethers were found to be
produced with additions to CF CC1=CF2, CF3CFCC12, CF FCF2 and
CF2C1CF=CC12, leading to the empirical statement that for the formation
of a saturated ether the perhalopropene nust have either a CF2 group
alpha to the ether linkage after addition of the alkanol or a fluorine
atom attached to the carbon on the internal vinylic position of the
olefin. Knunyants (26) reported the addition of alcohols to
perfluoropropene to give ethers of the type CF3CFHCF2OR.
The other method commonly used for the preparation of saturated
fluoroethers is the reaction of alkali metal alcoholates with fluorine-
containing alkyl halides. This reaction was investigated at an early
date by Swarts (41) who, in attempting to prepare fluoro-olefins,
reacted CF2BrCHBr2 with ethanolic potassium hydroxide and obtained
CHBr2CF2C2 5. Similarly, the reaction of CF2BrCH2Br with sodium
ethylate produced CHBrCF20C2H5. This reaction was thought to be a
common Williamson displacement until certain unusual reactions of this
type were investigated by Tarrant and Young (45). These workers found
that C3 CF C1 and C2ClC0BF2, when reacted with sodium ethoxide in
ethanol, both gave a single product identified as ethyl acetate, formed
by the unstable intermediate ether CULCF2 O2H 5 A simple displacement
of chlorine by the ethoxide group would have given CH3CF2OC2H5 and
CF2HCI20C2H5, respectively. Similarly, the product in the reactions
of CHF2CIC12 and CHF2CHFC1 was found to be CH2C1CF2OCZHS To account
for these results it was proposed that intermediate fluoro-olefins
were formed which then reacted with alcohol to give ethers by the
first method described.
CI3 CF2C1 NaOEt
CH2C1CHF ethanol H2 2
CF=CH2 + C2H0 -. C2 OCF2CH 2 153
C2HOCF25 CH + C2HSOH C2H OCF2CH3 + C2HO0 
Even though it appears that most reactions of this type are not simple
Williamson displacements, a few instances have been reported in which
this must have been the case. Benning and Park (5) claimed the
preparation of CF CH20C2H5 from CP3CHaCl and sodium ethylate.
A similar synthesis of fluoroethers has been reported by
Bentley (6) who found that the treatment of CF2BrCFC1Br with methanolic
potassium hydroxide gave CFCH1F20CH as the principal product. He
explained this unusual result by showing that FCF=CFC1 was first formed
and then added a molecule of alcohol as shown:
CH30 + CF BrCFClBr Br(CF2CFC1) + CH OBr 
Br(CF2CFC1) -- CF2CFC1 + Br [81
CH30 + CF2=CFC1 -- CIL0CFCFC1 [9
CL0CF2CFC1 + CHOH -- CFC1HCF2OCH3 + CH 0 
Parentheses are employed in the equations since it was not established
which bromine was removed from the perhaloalkane in equation [7).
Unsaturated fluoroethers may be prepared in s similar manner
by the base-catalyzed addition of alcohols to fluoroalkynes. Chaney (8)
reported the addition of ethanol to CF CCCF3 to give CF3CH=C(OC2H5)CF3
while Haszeldine (18) and Henne (20) reacted CF C=CH with methanol and
ethanol, respectively, to give CF CH=CHOCI and CF CH=CHOC2 5.* luoro-
alcohols may also be added to acetylenes to give vinyl fluoroalkyl ethers.
By reacting several fluoroalcohols with acetylene, Shukys (36,37) prepared
CH 2CHOCH F, C CHOCH2CF F and CH2COCH2CFHCFF. Vinyl 2,2,2-
trifluoroethyl ether has also been prepared by pyrolysis of
Brey (7) prepared a number of vinyl fluoroalkyl ethers by the
reaction of ethylene oxide with fluoroalcohols, followed by replacement
of the hydroxy group with chlorine and subsequent dehydrochlorination.
CH T 2 + RCH20H KOH R CH2OCH2C 2OH
KOH fC2H CI 
CH2z H2 2R alcohol RCH2H2CCl ll
[Rf = perfluoroalkyl group]
Another route to vinyl fluoroalkyl ethers consists of the
addition of ethylene glycol to a fluoro-olefin followed by replacement
of the hydroxy group with halogen and dehydrohalogenation (7,27).
HOCH2CH2OH + CF22:CX -- HO 2CH 0CF2CX1H
CHgH C C [1KOH [12
CH2=CHOCF2CX2 alcohol CH2XC H2OC2 CX2H [123
Since present methods for their synthesis are relatively few
in number, it was the objective of this research to study new methods
of preparing unsaturated fluoroethers.
Nomenclature used in this dissertation is the same as that
employed by Chemical Abstracts except when referring to a- and F-
bromoethers. In many instances formulas have been given rather than
the name of the compound in order to avoid cumbersome nomenclature.
In planning the synthesis of unsaturated fluoroethers several
factors had to be considered. First, it would be desirable to use
readily available starting materials. Next, in order to avoid any
complicated fluorination processes, these materials should already
contain the desired amount of fluorine. In addition, any necessary
intermediates should be such that they could easily be reacted to
give the desired olefinic or diolefinic structure.
A procedure which seemed to fulfill these requirements was
found by Lovelace (30) who prepared a number of fluorobutadienes by
a synthesis involving the free-radical addition of certain fluorine-
containing perhaloalkanes to the carbon-carbon double bond of an
olefin. The adduct could then be dehydrohalogenated to the fluorine
substituted diene. A typical reaction sequence has been presented
in the Introduction. It was felt that this procedure could be
applied to the preparation of unsaturated fluoroethers by the free
radical addition of perhaloalkanes containing fluorine to an alkenyl
alkyl ether. The following equations illustrate a typical reaction:
CF2Br2 + CH2CRCHCOC2H5 Bz CF2BrCHCHBrCH2OC2H5 [1l
CF2BrCH0BrC 2H -5 KOH 2=CCH=CHOC2 [2
Another example of the preparation of a substituted diene by
this method is shown below.
CF2BrCFClBr + CH=C ii25 BOCH CF2BrCFClHCHCBrOH5 [31
CF2BrCFClCH CHBrOCPH -KOH- CF2BrFClCIl=CHOC2HS C
CF2BrCFClCHCHOC2H5 alcohol. CF=CFCH=cHOcH25 5
In order to investigate the free-radical additions to alkenyl
alkyl ethers the following perhaloalkanes were selected: bromotrichloro-
methane, dibromodifluoromethane and 1,2-dibromo-2-chloro-l,1,2-
trifluoroethane (CF2BrCFClBr]. All were commercially available.
Bromotrichloromethane was selected for use as a guide to the possible
success of the initial addition step since its high reactivity in this
type reaction had previously been demonstrated (47). Alkenyl ethers
chosen for this study were allyl ethyl ether, vinyl ethyl ether,
allyl 2-chloro-l,l,2-trifluoroethyl ether and vinyl 2,2,2-trifluoroethyl
ether. The first two ethers in this list were commercially available
while the last two could be easily prepared in high conversion in the
laboratory by one step syntheses. The alkenyl fluoroalkyl ethers also
would make a comparison possible to determine the effect of fluorine
on properties of the adducts.
Free radical additions to unsaturated compounds have received
an extensive investigation since Kharasch (24) first reported that
carbon tetrachloride and chloroform reacted with octene-l in the
presence of free radicals to give 1,l,1,3-tetrachlorononane and
Reactions of this type are believed to follow the mechanism
proposed by Kharasch (25) as shown, using bromotrichloromethane as the
II II A
RCOOCR R* + RCOO0 + 0C0 
R* + CC1Br -- RBr + *CC1 
c01 + RCMH=H2 --. *CHRCH2CC1 
*CHRCHCC13 + CC1 Br -- RCHBrCH2CCI + *CCl 
Homolytic scission of the carbon-bromine bond can also be
accomplished by irradiation with ultraviolet light, in which case
equations  and 17] would be replaced by equation .
CC1 Br + hv -- -CC + Br* 
An interesting side reaction is frequently observed, resulting in the
formation of higher molecular weight adducts known as telomers. The
telomerization process is a result of the competition of the olefin
with the perhaloalkane to react with the intermediate radical .CHRCH0CC13
and results in adducts with a ratio of olefin to perhaloalkane greater
*CHRCH2CC13 + RCH=CH -. CHRRCHRCHRCHCC1l
Br* + RCHBrCH CHRCH2CCl 
High-boiling material found in the additions to allyl ethers may be
accounted for by this telomerization reaction.
Another interesting aspect of this type reaction is the
direction of addition. The attacking species, .CC13 in the example given,
could theoretically bond to either carbon of the double bond. A general
empirical rule is that the radical will usually add to the carbon with
the most hydrogen atoms. In the case of a vinyl group, attack would
then be on the terminal carbon. Considering steric hindrance, this
appears reasonable. Also, the more stable secondary radical would be
formed rather than a primary radical. That radical attack took place
on the terminal carbon in the series of ethers under investigation
was established by nuclear magnetic resonance studies of selected
adducts and derivatives. For example, the dibromodifluoromethane
adduct to an allyl ether could have one of two structures, depending
on the direction of attack:
Theory predicts that the fluorine resonance peaks would be
split into a triplet in structure [A] and into a doublet in structure
[B]. Triplet splitting was observed, leaving no doubt as to the
direction of addition in these reactions.
Direction of addition to vinyl ethers was proved in a similar
manner. Dibromodifluoromethane was added to vinyl ethyl ether and the
adduct reduced with lithium aluminum hydride. Ease of reduction of
the bromine atom was evidence that the adduct had the structure
CF2BrCHI2CHBrOC2 rather than CH2BrCH0C0 H since it was found that the
B-bromine atom was not reduced under conditions which resulted in the
reduction of an c-bromine atom. Identification of the reduced product
as CF2BrCH2CH20C25 proved that radical attack had been at the terminal
A cursory examination of the literature revealed no examples
of free radical additions to allyl ethers, although Hall and Jacobs (16)
had reported the addition of carbon tetrachloride to the diethyl acetal
of acrolein to give CC013CH2CHCH(OC2H )2 in 18% yield. The additions
of the three perhaloalkanes to the two allyl ethers were all carried
out at 90-950 using a benzoyl peroxide initiator. In each case the
one-to-one addition product, a P-bromoether, was isolated in
conversions ranging from 26% to 50%. Appreciable quantities of higher-
boiling material were observed and assumed to be telomers. Since
these compounds were of very high molecular weight their isolation and
identification was not attempted. Furthermore, adducts greater than
one-to-one would not give a structure leading to desirable compounds.
Properties of the adducts obtained from allyl ethers as shown in the
following reactions are given in Table I.
CC1 Br + CH=CCHC R B2--0--2 CG1CHCHBrCHOR 
CF2Br + CH2 HCH20R B2 CF2BrCHCHBrCHOR 
CF2BrCFClBr + CH2=CHH2OR ----22 CF2BrCFClCH2CHBrCH2OR 
[R = C215 and CF2CFClH]
In order to prepare olefinic ethers from the B-bromoethers it
was necessary to find a suitable method of eliminating hydrogen halide
from them. Alcoholic potassium hydroxide was found to be of limited
value due a side reaction with compounds which could be dehydrohalogenated
to give a CF2-CIf- group. For example, the reaction of CF2BrCI2CIBrCH OC2 5
with ethanolic potassium hydroxide gave only ethyl Y-ethoxy crotonate.
The formation of this product may be explained by the following series
F2 HC H .... KOH O H5 [16
CFBrC BrCH2BO 25 ethanol C-F2CHCHBrCIH2C0 5 15]
CF=CRHCrCH2BOC ~5 ethanolH C2SHFCHCHBrCHOC2H5 [16
2150CF2CH2CHBrCH2OC 2H5 ethanol C2HOCCI=CH 2 II5 17
In equation , the initial elimination involves the removal of
bromine from the CF2Br- group. That this actually occurs will be shown
later. A molecule of alcohol then adds to the CF2=CH- group to give
an a,a-difluoroether which hydrolyzes readily to the ester. Elimination
of the second bromine also occurs during the reaction, probably after
the formation of the a,a-difluoro compound. Addition of an alcohol
to a fluoro-olefin is a well known reaction and has already been
described. Also, a,a-difluoroethers of the type ROCF2CH2R have been
shown to be very unstable and to hydrolyze readily to an ester (48).
Assignment of structure of the compound was based on comparison of
physical properties with those reported and on its infrared spectrum,
which showed strong absorption at 5.78 microns, characteristic of
a, -unsaturated esters. An additional peak, resulting from carbon-
carbon double bond stretching, was observed at 6.00 microns.
The most effective method of dehydrohalogenation, both in
terms of conversion and freedom from undesirable side reactions, was
found to be reaction of the ether with finely powdered potassium
hydroxide in a mineral oil dispersion. By use of this method several
mono- and diolefins were prepared from the f-bromoethers. Adducts
prepared from allyl ethyl ether gave only the mono-olefins under
typical reaction conditions.
CF2BrCH2CHBrCH2OC H KOH CF=?HCHBrWC2 H5 [18)
CFBFCr1FlCH CHBrCH Cg H5 KOH CFPBrCFClCHoCHgoCg5 [190
The product shown in equation [183 is unusual in that elimination
occurred with loss of the bromine atom from the CF2Br- group. This
was shown to be the structure of the dehydrobrominated compound by
elemental analysis and by its infrared spectrum. A vapor phase
chromatogram showed that this compound was contaminated with another
component, possibly the diolefin, which would account for the high
values for carbon-hydrogen analysis. Nevertheless, it was apparent
that the reaction had proceeded to give essentially the monodehydro-
brominated compound. An infrared spectrum showed a single strong,
sharp absorption peak at 5.72 microns. Lilyquist (29) has assigned
the 5,65-5.73 nicron region to the CF2=CH- group. Ordinarily, the
bromine atom of the CF2Br- group would be expected to be the more
unreactive of the two bromine atoms due to the strong negative inductive
effect exhibited by the fluorine atom. It has been reported (40),
however, that 0-haloethers are remarkable for their lack of chemical
reactivity and that 1-bromoethers may be distilled from solid sodium
hydroxide without appreciable decomposition.
The adduct of CF2BrCFC1Br to allyl ethyl ether, equation ,
was also found to give the monodehydrohalogenated compound.
Debydrobromination with elimination of the f-bromine atom was observed
in this instance. Elimination of a proton could have been from
either the a or r carbon atom. The structure in which the proton
was eliminated from the r carbon has been assigned this compound on
the basis of its infrared spectrum, which exhibited a sharp medium
peak at 5.97 microns. This orientation of elimination was not
surprising, however, in view of the increased acidity of the r-hydrogen
caused by the inductive effect of the adjacent -CFC1- group.
Dehydrohalogenations of bromotrichloronethane adducts led to
complicated mixtures which could not easily be separated by fractional
distillation, as indicated by vapor phase chromatograms of several
analytical fractions. Since these adducts were not of direct interest,
their reactions were not given further study.
Both mono- and diolefins were obtained in the dehydrohalogenation
of adducts from allyl 2-chloro-l,l,2-trifluoroethyl ether.
CF =CHCHCHOCF2CFC1H + CF =CHCHBrCH2OCF2CFCIH 
KOH I ethanol
CF2BrCF CHCI CHOCF2CFClH (22]
When reacted with excess base the dibromodifluoromethane adduct, as
shown in equation , gave two products. The lower boiling component
was identified as the diene on the basis of elemental analysis and
its infrared spectrum, which exhibited two strong, sharp peaks in the
carbon-carbon double bond region at 5.75 microns and 6.01 microns.
These absorptions are attributed to the CF2=C1- and -CI1=CH- groups,
respectively. The higher boiling component was identified as the mono-
olefin resulting from removal of bromine from the CF2Br- group. An
infrared spectrogram of this compound showed a single peak in the
carbon-carbon double bond region at 5*73 microns, characteristic of
the CF2=CH- group.
When reacted with an equivalent amount of base, the CF2BrCFC0Br
adduct, equation , gave a single compound resulting from the
elimination of one equivalent of hydrogen bromide. As before, the
structure resulting from ,vr-elimination has been assigned on the basis
of infrared absorption and the removal of the most acidic hydrogen.
A single absorption peak was observed at 5.93 microns. This is a
higher frequency absorption than that normally displayed by the group
-CIIzCHI=CI2O- but one which might be expected from the structure
-CFC1CH=CH-. This shift to higher frequencies resulting from the
substitution of fluorine for hydrogen on a carbon atom adjacent to a
double bond has been observed by Lilyquist (29). For this reason,
the mono-olefin was assigned the structure resulting from elimination
of a l-hydrogen atom.
Further reaction of the mono-olefin with ethanolic potassium
hydroxide, equation , produced the diene, as evidenced by elemental
analysis and its infrared spectrum which showed two peaks in the
carbon-carbon double bond region at 5.91 microns and 6.06 microns and
a carbon-hydrogen stretching absorption at 3.23 microns. Assuming
the structure of the reactant to be the B,r-unsaturated compound, the
diene is formed by a 1,4-elimination.
Unusual results were obtained in the attempted dehalogenation
of CF2BrCFClCH2CHBrCHOCFCFC1IH with zinc in isopropanol. The only
compound isolated was identified as isopropyl chlorofluoroacetate,
indicating cleavage of the carbon-oxygen bond. Evidence supporting
this has been reported by Dykstra (10), who prepared olefins from
P-bromoethers by reaction with zinc and alcohol. The formation of
an ester could be accounted for by the following series of reactions
BrZnOCF2CFC1H + CF2BrCFC1CHC=CH2 
BrZnOCF2CFCIH -- ZnBrF + F-CCFC1H [241
F-CCFClI + cI-3corIIC --. CFGIHCOCH(CL)2 + HF 
The olefin formed in equation  could then be dehalogenated to give
CF2=FCH2H=CHC2, This diolefin was not isolated in the above reaction
since no attempt was made to identify low boiling fractions from the
distillation. However, this compound was shown to be produced in
the following reaction with the ethyl ether:
zinc I ethanol
CF2=CFCH2CH=CH2 + BrZnOC 2H 
The structure was identified by comparison of its infrared spectrum
with that of an authentic sample made by the method of Tarrant and
A number of investigators have shown the reactivity of vinyl
ethers in free radical additions. Glickman (14) added carbon
tetrachloride to a number of vinyl ethers and obtained 1,3,3,3-
tetrachloropropyl ethers in high yield. Similar additions have been
reported by Levas (28) and Shostakovskii (34).
Attempts to carry out radical additions to vinyl ethyl ether
in an autoclave using benzoyl peroxide initiator at 95 resulted in
every case in decomposition of product as evidenced by heavy fuming
and formation of a black, spongy polymer. This thermal instability,
characteristic of a-h4aloalkyl ethers (39), necessitated the use of a
procedure in which materials could be reacted at temperatures lower
than those used in benzoyl peroxide catalyzed initiation. Such a
procedure was found in the use of ultraviolet irradiation as a free
radical initiator. Addition reactions of vinyl ethyl ether are shown
CC1 Br + CH2=CHOC25 -u.v CCl- C CCHBrOC2HS [271
CF BrZ + CH2=CHOC2H uv' CF BrCH2CIIrOC25 28
CF2BrCFClBr + CH=CCHOCg u CF2BrCFClCHiCHBrOC2H5 [29
An additional advantage of this procedure is the absence of
contaminants resulting from the decomposition of benzoyl peroxide.
It was subsequently found that ultraviolet catalyzed additions could
be made to allyl ethers in conversions comparable to those from
peroxide catalyzed reactions. The ultraviolet initiated procedure
is preferred since it eliminates the handling of heavy equipment and
gives a purer product.
Adducts from vinyl ethyl ether, described in Table I, fumed
heavily on exposure to moist air and decomposed with evolution of
hydrogen halide at temperatures between 70-856 during distillation.
Consequently, only CF2BrCH2CHBrOC2H5 could be satisfactorily fractionated
due to its lower boiling point, although apparent boiling points for
the bromotrichloromethane and CF2BrUFClBr adducts are reported.
These adducts, although not isolated, could be reacted to give stable
derivatives which could be identified and will be described later.
Satisfactory analysis of the c-bromoalkyl ethyl ethers was impossible
due to their rapid decomposition. These compounds were also found to
be extremely reactive hydrolytically. Upon basic hydrolysis
CCl~CH2CHBrOC2H5 was found to give appreciable quantities of a highly
lachrymatory material, identified as dichloroacrolein, CC12=CHCHO.
Hydrolysis of the dibromodifluoromethane and CF2BrCFC1Br adducts
resulted in vigorous reactions leading to the formation of extremely
lachrymatory compounds which were not identified, partially because
of their tendency to polymerize to viscous liquids. Similar results
were observed by Durrell (9) in the additions of the same perhaloalkanes
to vinyl acetate.
Adducts obtained from the addition of perhaloalkanes to vinyl
2,2,2-trifluoroethyl ether exhibited a marked increase in thermal and
hydrolytic stability over that of the vinyl ethyl ether adducts. They
showed little tendency to hydrolyze in moist air, could be stored several
months without decomposition and gave good analytical results. The
thermal stability of these compounds was so greatly enhanced that a 62 g.
sample of CF2BrCH2CBrCHB CF3 was recovered unchanged after passing
through a hot tube at 2200.
The reactivity of the bromine atom in alkyl c-bromoalkyl ethers
may be attributed to the possibility of resonance involving an oxonium
+ .. +
RCH-O-R' RCH=0-R' e30)
Physical evidence supporting this has been presented by Brey (7) who
noted a doublet in the infrared spectra of vinyl alkyl ethers arising
from the existence of rotational isomers. To explain the presence of
rotational isomers Batuev (3) postulated a resonance structure for vinyl
ethers, CH2-CH0-R, for which rotation of the alkyl group about the
carbon-oxygen bond would be hindered, resulting in the isomers:
CHs=C (/R and CH =C
However, when R' is a CF3CH2- group the negative [electron withdrawing]
inductive effect of the three fluorine atoms is evidently strong enough
to inhibit drastically the ability of the oxygen atom to donate its
unshared electrons in the formation of the oxonium structure. Brey
found only a single carbon-carbon double bond stretching bond in
vinyl a,a-difluoroethers. This result was attributed to the strong
inductive effect of the a-fluorine atoms which prevented resonance of
the oxygen electrons with the double bond. However, the inductive
effect of fluorine in the beta position, insulated from the oxygen
atom by a methylene group, is not sufficient to overcome the resonance,
as evidenced by the appearance of doublet in the carbon-carbon double
bond stretching region in the spectra of all vinyl 0-fluoroethers
The comparative unreactivity of the a-bromoethers reported
here is unusual in that this effect is transmitted through the
methylene group. Thus, this appears to be a case in which the
resonance forms are not inhibited enough to change the physical
[i.e., infrared absorption] properties but are inhibited sufficiently
to cause a marked change in chemical reactivity.
Additions of the perhaloalkanes to vinyl 2,2,2-trifluoroethyl
ether may be described by the following reactions:
CCl Br + CH2=COCHCF3 u.v CC CHCHB'I C CF 31
CF2Br2 + CH2=CHOCH2CF3 u.v- CF2BrCH2CHBrOCH2CFP [323
CF2BrCFC1Br + CH2=CHOCHOCFH
In contrast to the additions of perhaloalkanes to allyl ethers,
it was found that additions to vinyl others resulted in high conversions
[72-91%] to the one-to-one adducts. Itoreover, very little telomerization
occurred as evidenced by the very small amount of high boiling material
remaining after distillation of the reaction products, even though
smaller ratios of perhaloalkane to ether were used.
In order to prepare unsaturated compounds from these
a-bromoethers, several attempts were made to eliminate hydrogen
bromide to give an a,O-unsaturated ether. Although it has been
reported that certain c-haloethers may be dehydrohalogenated to
CH2BrCHBrOC2H5 pyi CHBr=cHoCH5 (12) 
CHC120CHClOCf5 ag CCl2=CHOC 2 (15) 
CICHclOC2I5I pyridine CH2=COC2H5 (21) 
it was found that reaction of pyridine with CF2BrCH2CHBrOC2H, resulted
only in the formation of high boiling material and not the desired
unsaturated ether, CF2BrCH~HOC2HS. Reactions with aqueous base
resulted in rupture of the carbon-oiygen bond, as previously mentioned,
apparently to give an unsaturated aldehyde.
Preparation of 1-alkenyl ethers has been reported by Erickson
and Woskow (11), who prepared a number of acetates and subjected them
RCH2CH(OOCCI13)OR' I--. RCH=CHOR' + CI3COOH 
It was thought that a reaction of this type as shown below would
lead to the desired unsaturated fluoroether.
CF2BrCH2CHBrOCH5 + CHCOONa
CF2BrCH2CH(OOCCH )oc2*H5 + NaBr [38
CFCBrCH2CH(00CCH3)02H5 -- CFBrCIc HOCH11 + CIrCOoH 
Attempts to prepare the acetate, however, were unsuccessful and
resulted in a complicated decomposition involving the elimination of
A method of converting the ca-bromoethers to unsaturated
fluoroethers was found in the reduction of the c-bromine atom,
equations  and , followed by dehydrohalogenation or
dehalogenation of the products.
CF2BrCH2CHBrOR CF2BrCI2CH2OR 
CF2BrCFC1CHiCHBrOR -LAl CF2BrCFClCII2CH OR 
[R =0 C5H5 and CH2CF3]
Although the reduction of CClCH2CHBrOC2H5 resulted in the
formation of several impurities as shown by a vapor phase chromatogram,
the desired CCl3 CH22 OC2H5 was shown to be a product of the reaction
by its conversion to C HSOOCH CH C2OC H5 with ethanolic potassium
hydroxide. The ester, rather than the acid, was prepared as a
derivative because of the availability of an authentic sample of
ethyl O-ethoxy propionate.
The unsaturated fluoroether derivatives were prepared as
COH YCH2OH2OR 4OH
CF2 2CI0R cminera oil CF2=CH2OR .2]
FCF2BrCFCCHCHZOR 7alchol: CF2 =CFCH2 H20R [33
[R = c2n5 and CH CF
Structure of the products in equations  and  was
proved by nuclear magnetic resonance studies while structures of the
unsaturated ethers, equations  and , were confirmed by
infrared data. Characteristic carbon-carbon double bond stretching
absorption peaks were observed in the 5.72-5*73 micron region for the
compounds containing the CF2=CH- group and in the 5.53-5.54 micron
region for the compounds containing the CF2=CF- group.
Properties of the reduced ethers and unsaturated ethers are
given in Table I.
Another method of preparing a,0-unsaturated ethers from
a-bromoethers was examined. A number of workers (31,38) have reported
the preparation of vinyl and alkyl substituted vinyl ethers by
pyrolysis of acetals using various catalysts. In order to investigate
the use of this reaction, the a-bromoethers shown in equations ,
C29),  and [333 were reacted with the appropriate alcohol to give
the acetals shown:
CF2BrCH2CHBrOC2H5 + CZH50
CF2BrCH2CH(OC2H5). + Br 
CF2BrCFClCH2CHBrOC2f5 + C2H5OH
CF2BrCFC1CHCH( 00215)2 + lBr 45)
CF2BrCHCHBrOCH2CPF + CF3CHOH
CF2B rCHi2CH(OCH2CF3)2 + HBr (46]
CFBrCFClCH 2ChBrOCIICF, + CF3CH2OH
CF2BrCFC1CH2CH(OCH CF3)2 + HBr 
That the acetal structures were actually formed was shown by
nuclear magnetic resonance studies. For example, an IlR spectrun of
CF2BrCH2(OCH(OCH3C)2 showed the expected fluorine triplet, a hydrogen
triplet due to the hydrogen in 0- a sextet due to the hydrogen in
CF2BrCHi- and a quadruplet due to the ethylene hydrogen of the ethyl
group. The latter peaks were all split into doublets, possibly because
of nonequivalence due to spatial arrangement. It was further shown
that the area under the peaks due to methylene hydrogen of the ethyl
group had twice the area under the methylene hydrogen peaks due to
hydrogen in the CF2BrCH2- group.
Furthermore, frequency shifts and additional infrared absorption
peaks were observed in the nine micron region when the acetal spectra
were compared with the spectra of the a-bromoethers. This region has
been assigned to the single bond carbon-oxygen stretching vibration (4).
The acetal CF2BrClCH(OC2H5)2 was selected for the attempted
pyrolysis reactions. Since anhydrous monosodium phosphate had been
found to be particularly effective in this type reaction (31), a
one-half inch inside diameter column was packed with 13 g. of this
material and heated to 3000. The aeetal was passed over the catalyst
bed but was recovered unchanged. Attempts to pyrolyze this acetal
by passage through a glass-packed hot tube at 4000 were also unsuccessful.
Several attempts were made to prepare alkoxy substituted
fluorobutadienes. It was hoped that a reaction sequence of the
following type would result in the desired structure:
CF2BrCH2CHBrOCH2CF3 + CHJiJgBr
CFBrHC H(CH3)OCHGCF3 + MgBr2 [48)
CF2BrCHCH(CH3)OCH2 CF + C1
CF2BrCHCC1(CH )OCH CF + HC1
CF2BrCH2CC1(C3)OCH2CF3 KOI, CF2=CIC(OCHCF3)=C12 [50o
Substitution of the r-bromine by methyl was successful with
CF2BrCH.CHBrOC2II but not with CGFBrCHICHBrOCgCF 3. This again
demonstrates the relative unreactivity of the a-bromoalkyl 2,2,2-
trifluoroethyl ethers, due to the inhibition of the ability of the
oxygen atom to donate its unshared electrons in the formation of the
oxonium structure. Chlorination of the methyl substituted product,
CF23BrC C(CII( )OC21 5, was not attempted since it was believed that
the c-carbon of the ethyl group would be easily chlorinated as well
as the desired position. This ether was dehydrobrominated, however,
to ethyl 3,3-difluoro-l-methylallyl ether.
Another route to the preparation of CF2BrCH2CX(CH3)0CH0CF3,
where X = Cl or Br, was investigated.
CF2Br2 + CH2C(CHf)C0C C F
Synthesis of 1-methylvinyl 2,2,2-trifluoroethyl ether by the base
catalyzed reaction of trifluoroethanol with methylaoetylene was not
satisfactory as only a snall amount of low boiling material was
obtained. A higher boiling product of this reaction was identified
as (C13)2C(OCH2CF3)2 by elemental analysis and nuclear magnetic
resonance studies. This product could be accounted for by the reaction
of the desired methylvinyl ether with a molecule of trifluoroethanol.
Cl2=C(CH )oCI2 cF + CF3CHo2H KOH (CH3)2C(OCH2CF ) 
It was subsequently shown that dibromodifluoromethane did not add under
normal ultraviolet irradiation to 1-methylvinyl ethyl ether, prepared
from ethanol and methylacetylene as reported by Shostakovskii (35).
A successful synthesis of a fluoroalkoxy substituted butadiene
is outlined below:
CH=CHCIICH + CCI 0f
CH2=CCH(OCHI2CF3)CH2Cl a 1KOH CH CHC(OCH2CF3)=CH2 [55
Acid catalyzed reaction of 3,4-epoybutene-1 with alcohols has been
shown by Kadesch (23) and Bartlett and Ross (2) to result in cleavage
of the allylic, secondary carbon-ozygen bond rather than that of the
non-allylic, primary carbon-oyrgen bond. The reaction described in
equation [533 should then give the primary alcohol* This was
substantiated by an examination of its infrared spectrum, which
showed medium absorption at 9.60 microns, characteristic of primary
alcohols, The remaining sequence was carried out without difficulty
to give the desired 2-(2,2,2-trifluoroethoxy)-butadiene, It was
necessary to inhibit this monomer with hydroquinone since it was
observed that a sample of this compound spontaneously polymerized to
a white, crumb-like elastomer.
Although no attempt has been made to assign specific bands,
all fluoroethers described in this dissertation exhibited at least
one strong, broad infrared absorption peak in the region 8.5-9.0
PROPERTIES OF THE COPOUNDS PREPARED
Conpound % B.P. Pressure 23 23
Conversion (OC) (mm. Hg) "D
CC13C2CHIBrCH2OC2H5 29 69 0.5 1.4940 1.535
CF2Brl2CHgBrCH2OC2I5 31 55 2 1.4510 1.670
2g2rCF FlCCH2CBrCHH2OCx2 26 75 1.5 1.4534 1.743
CC13CH CHBrCH OCFCFCFCH 50 99 2 1.4645 1.759
CF2BrcH CHBrCH 200CCFC1H 46 65 2 1.4301 1.911
CF2BrCFClHCHCHBrCH 00CFC1iH 47 78.5 0.6 1.4350 1.902
CCC13CH2CHBOC25 51 0.7 1.4835 1.395
CF2BrCH2CHB3rOC2H 83 53.5 5 1.4490 1.734
CF2BrCFCICH2CHBrO0C2H 71 1 a a
CC0013HCBrocH2CF3 91 45 0.4 1.4488 1.739
CF 2BrcCCHBrOCH2CF3 72 29 1.5 1.4052 1.901
CF2BrCFCl CH2rCH OCCF3 72 55 0.5 1.4188 1.935
C2HsOOCCH=CHCH0C 2I5 42 59 0.9 1.4332 0.987
CFf=ClcHBrCz OC2Y 5 27 56 24 1.4282 1.393
TABLE I (continued)
Compound % B.P. Pressure 23 d23
Conversion (C) (am. Hg) n
CF Brp2CFCC=CCIH2OC5H. 27 54 1.2 1.4358 1.518
CF =IIClECHOCF CFCIH 5 62 70 1.3820 1.390
CF =CICIBrCHOPCF2CFClI 25 112 70 1.4083 1.687
CF BrCFCCCH=CHCH00CFC1FI 56 57 0.7 1.4152 1.738
CF2BrCF=CHHCI=CHOCFCFCUI 24 41 0.7 1.4255 1.669
CF2BrCHC~~oCH25 2b 36 20 1.4026 1.410
CF2BrCFC1CHCH200HC 33b 42 3 1.4185 1.526
CC13CHbCOC2H 4b 67 7.5 1.4615 1.305
CF2BroCH2CH2OHCF3 24 56 40 1.3604 1.613
CF2BrCFCl"CCH2C IOCCCF3 0 43 2.5 1.3840 1.705
CF2=CHHO2CzY 36 67 760 1.3548 1.007
CF2=CFCH2Cy0OC2H5 35 96 760 1.3555 1.069
CF2=CHCHOCH2CF3 45 81 760 1.3207 1.299
CF2=CFCCH2CH20 CF3 42 103 760 1.3302 1.307
TABLE I (continued)
Compound % B.P. Pressure 23 23
Conversion (oC) (mm. Hg) n
CF2BrC'2CHn(oc211), 75 64 14 1.4057 1.325
CF2BrCFlCHGCH(OC2H5) 38 52 0.5 1.4190 1.440
CFBrCH2CH(OCH2CF3)2 21 78 20 1.3512 1.670
CF2BrCFOC1HCH(C0(oCCF3 )2 67 50 0.5 1.3745 1.754
CF2BrCH CH(cH3)OC25 19b 55 41 1.4020 1.335
CF=CCH(CI3)OC2' 45 76 760 1.3588 0.969
CH2=CHClc (OCHCF3)CC2H 38 86 55 1.3797 1.198
CH=c CSH(OCCF)CH2Cl 60 66 55 1.3852d 1.209d
CH]=C(OCHCF3)CH=C-g 38 93 760 1.3778' 1.116
(C3)2c(oc2CF3)2 10 123 760 1.3270 1.261
a. iure sample not isolated
b. Based on vinyl ethyl ether
c. Based on vinyl 2,2,2-trifluoroethyl ether
d. At 200
e. At 210
ANALYSES OF THE CO:IPOUIDS PREPARED
CC13CI. CIIBrCII 0CZH5
CFBrCH CHBrCH c H5
CFBrc.FCCII C HBrCI2 C H5
C1 23 C2ocF2c 2l2
CF2BrC L CIBrCC r 0CF2CFFC1
CC1 Cl2CIB23rOC 115
CF ErCrcitCI CHarOC T-5
3 2 2 5
cc lci ,HBrocItCF3
CF.BrCFC1CH IICBrOCH CF
cFI=cicrc1r H cC IT 5
33.35 39.70 33.51 34.68 4.22 4.51
--- -- 284.4
--- ---- 296.0
120.8a 119.4 362.5
-- -- 371.9
-- -- 384.5
56.70e 54.95 281.9
81.09a 81.80 324.4
47.59E 47.25 335.9
-- -- 402.6
-- -- 158.2
---- ---- 215.1
_1 __ _I ___ ____ __ __ ~_ _ ~___
TABLE II (continued)
CF BrCFC1CIn=CHCI OC Hl
ClC --2 CH? OC2c5
CF2BrCF CH 20oc2CF 3
C Y r l* c a oz r Jf
CCl CII CH2OCIFCF
CF =CFCH CHInOC 1
CF2=CCH 2I oc2CF3
CF2 =CMCzIOCC ICF3
C2=M HX2 CF 3
-- -- 281.7
-- -- 222.6
-- -- 303.5
166.8a 167.0 333.5
39.46e 39.60 203.0
134.7a 133.0 269.5
55.54d 55.45 191.5
31.09 30.83 257.0
161.8a 163.5 323.5
43.33d 43.33 2455
-- -- 122.1
-- -- 154.1
-- -- 208.1
TABLE II (continued)
CF~BrcHCCHC(oC F3) 2
CH:=ccH(oc F ,C3)ccH
32.34P 30.57 247.1
--- --- 313.6
-- -- 355.1
36.820 37.15 217.1
-- -- 136.2
-- --- 170.1
18.80d 18.69 188.6
--- -- 152.1
--- -- 240.2
a. Silver equivalent
b. Sample decomposes
c. % Bromine
d. % Chlorine
_ __ __ _~I ____
All temperatures reported in this dissertation are uncorrected
and are given in degrees Centigrade. Distillations were generally
carried out using a 20 centimeter electrically heated, jacketed
column packed with one-eighth inch glass helices. Pressures under
10 millimeters were measured by a McLeod gauge while pressures above
10 millimeters were measured by a Zimmerli gauge.
Refractive indices were determined with an Abbe refractometer
at the temperature indicated. Densities were determined with a one
millimeter pycnometer. Molar refractions were calculated using the
Lorenz-Lorentz equation. Values for the atomic refractions were
taken from Lange's "Handbook of Chemistry," seventh edition, page
1052. In all eases the value 1.100 was used as the atomic refraction
Infrared spectra were obtained using a Perkin-Elmer model 21
double-beam, recording infrared spectrophotometer and a Perkin-Elmer
model 137 B Infracord spectrophotometer. Only those absorption peaks
which are indicative of the structure of a compound are reported.
All absorptions are reported in microns.
Qualitative vapor phase chromatographic [VPC] separations
were obtained using a Perkin-Elmer model 154 vapor fractometer with
helium as the carrier gas. When pure samples could not be obtained
by distillation, preparative scale separations were frequently
performed using an apparatus constructed by Dr. R. D. Richardson
consisting of a one-inch diameter column, 20 feet in length and
packed with material prepared from 0.5 g. dinonyl phthalate per
1.0 g. Johns-Manville Chromosorb. Nitrogen was used as the carrier
gas in this column.
Nuclear magnetic resonance [IR] spectra were obtained by a
Varian High Resolution Nuclear Magnetic Resonance Spectrometer
model 4302 operating at 56.4 negacycles and were interpreted by
Dr. W. S. Brey, Jr.
All high pressure reactions were carried out in a 1.5 liter
stainless steel autoclave manufactured by the American Instrument
All analyses were performed by Galbraith Laboratories,
Knoxville, Tennessee or by Drs. G. Wfeiler and F. Strauss, Oxford,
Molecular weights were determined using the freezing point
depression method with benzene as solvent.
The term "conversion" is defined as the amount of product
divided by the amount theoretically obtainable in a reaction.
Reactants used in this research were purchased when available.
The chemicals, other than those ordinarily found in laboratory stock,
with the sources of supply are listed below:
Allyl ethyl ether Distillation Products Industries
Vinyl ethyl ether Union Carbide Chemicals Company
3,4-Epoxybutane-l Columbia Southern Chemical Corporation
Dibromodifluoromethane Kinetics Chemicals Division,
E. I. du Pont de Nemours and Company
Lithium aluminum hydride
Dow Chemical Company
Feninsular ChemResearch, Incorporated
PennSalt Chemicals Corporation
Wallace and Tiernan, Incorporated
Metal Hydrides, Incorporated
General Chemical Division,
Allied Chemical and Dye Corporation
Hooker Electrochemical Company
A. Radical Additions to Allyl Ethers
All free radical additions to allyl ethers were carried out
using benzoyl peroxide as initiator. In the additions of dibromodi-
fluoromethane the reactions were run in a 1.5 liter autoclave, while
additions of bromotrichloromethane and CF2BrCFC1Br were carried out
both in an autoclave and in glassware at atmospheric pressure. The
method giving the higher conversion is described.
In distilling the addition products, it was observed that
benzoic acid, resulting from peroxide decomposition, was frequently
present as an impurity. Consequently, all reaction products were
thoroughly washed with sodium bicarbonate solution prior to fractionation.
Appreciable amounts of higher boiling material were formed in
these additions. The presence of these high molecular weight compounds
may be explained by a telomerization reaction to give two-to-one and
higher adducts, accounting for the low conversions to the desired
1. Additions to AllyI Ethyl Ether
A solution of 20 g. benzoyl peroxide in
1000 g. (5.0 moles) bromotrichloromethane was placed in a 2 liter
three-necked flask fitted with stirrer, condenser and dropping funnel.
The flask contents were heated to 900 and a solution of 20 g. benzoyl
peroxide, 168 g. (1*95 moles) allyl ethyl ether and 600 g. (3.0 moles)
bromotrichloromethane was added dropwise over a three hour period.
The flask contents were stirred an additional two hours at 90 and
stripped of unreacted starting material. The remainder was washed
with sodium bicarbonate solution and the crude product separated and
dried. Fractional distillation gave 173 g. (29% conversion) of
CC15CH2CHBrCH2002H5. An analytical fraction had the following
properties b.p. 690/0.5 mm., n3 1.4940, d23 1.535.
Anal. Calcd. for C6H0lBrC130: I:R, 53.92; C, 25.34, 4H, 3.54.
Found: 1%D, 54.10; C, 25.10; %%, 3.58.
A 1.5 liter autoclave fitted with a valve,
pressure gauge and rupture disc assembly was charged with 81'0 g.
(4.0 noles) dibromodifluoromethane, 66.5 g. (0.77 mole) allyl ethyl
ether and 10 g. benzoyl peroxide. It was then heated with rocking
for five hours at 900. The unreacted starting materials were stripped
and the remainder washed with sodium bicarbonate solution. The
crude product was separated and dried. Fractional distillation gave
64 g. (31% conversion) of CF2BrCH2CHBrCH2OC2 H5 An analytical fraction
had the following properties : b.p. 550/2 nam., n3 1.4510, d23 1.670.
Anal. e Calcd. for CC610Brr2oF20 I 1,, 47.08; %C, 24.34; %H, 3.41.
Found t 1-., 47.71;; %Cs, 23.98; H, 3.51.
A solution of 10 g. benzoyl peroxide, 650 g.
(2.35 moles) CF2BrCFC1Br and 48 g. (0.56 mole) allyl ethyl ether was
sealed in an autoclave and reacted at 95 for five hours. Fractional
distillation gave 53 g. (26% conversion) of CF BrCFClICHCIBrC 20C2H5
An analytical fraction had the following properties: b.p. 750/1,5 mm.,
3 1.4534, d23 1.743.
Anal Caled. for C70oBr2C1lF0: 1%R 56.56; C, 23.20; aH, 2.78.
Found 1,D, 56.25; %c, 23.97; %IH 3.23.
2. Additions to Allyl 2-Chloro-l,l,2-trifluoroethyl Ether
A solution of 15 g. benzoyl peroxide, 595 g.
(3.0 moles) bromotrichloromethane and 175 g. (1.0 mole) CH2=CHCHOCF2-
CFClH were reacted in an autoclave at 950 for six hours. The material
was worked up as before and fractionally distilled to give 186 g.
(50% conversion) of CCl3CH22CHBrCHI2OCFCFClH. An analytical fraction
had the following properties: b.p. 990/2 mm., 23 1.4645, d23 1.759.
Anal. Calcd. for C6o6BrCl 430: 1f, 58,78; %C, 19.38; %H, 1.63.
Found: 1 %, 58.57; %C, 20.32; %~, 1.80.
An autoclave was charged with 845 g. (4.0 moles)
dibromodifluoromethane, 175 g. (1.0 mole) CH =CHCH2OCF2CFClH and 8 g.
benzoyl peroxide. It was heated and rocked at 950 for three hours.
The autoclave contents were treated as before and fractionally
distilled to give 175 g. (46% conversion) of CF2BrCH2ClIBrCHOCF CFCFlI
An analytical sample had the following properties b.p. 65/2 mm.,
n3 1.4301, d23 1.911.
Al. Called. for C6gHBr2C1FOt: MR, 51.95; %C, 19.10. H, 1.72.
Found MRD, 51.91; %C, 18.75; %,H 1.58.
A solution of 4 g. benzoyl peroxide in 260 g.
(1.5 moles) CH2=CICH20CF2CFC1H and 553 g. (2.0 moles) CF2BrCFClUr was
added with stirring to a flask containing g g. benzoyl peroxide in
1100 g. (4.2 moles) CF2BrCFC1Br at 900. Addition was completed in
two hours and stirring at 90 was continued for one hour. The
material was handled as previously described and fractionated to
give 314 g. (47% conversion) of OF2BrCFC1CH2CHBrCH20CF CFC1H. An
analytical sample had the following properties: b.p. 78.50/0.6 am.,
n2 1.4350, d23 1.902.
Anal. Called. for C7H Br2C12F60: 1R, 61.43; %C, 18.64; %H, 1.34.
Found: m1% 61.72; 0C, 19.25; %H, 1.51.
B. Radical Additions to Vinyl Ethers
A Pyrex tube fitted with a Vycor immersion well was used to
carry out the additions. The volume of the outer Pyrex tube with
inversion well in place was 7$0 ml. A vent at the top of the outer
tube allowed for pressure changes. The Vycor immersion well with
standard taper 60/50 joint was double walled, with inlet and outlet
tube to provide for air or water cooling. A type 608 A-36 quartz
mercury are lamp with 2.9 inch arc length was suspended in the immersion
well to provide ultraviolet irradiation. A type 7620 ballasting
control was used with the lamp. Vycor immersion well, quartz lamp
and ballasting control were obtained from H-anovia Chemical and
Manufacturing Company, Newark, Few Jersey.
All successful additions to vinyl ethers were carried out in
the described apparatus at 0%, Optimum conversions were obtained
after ten-thirteen hours irradiation. A magnetic stirring bar provided
circulation of the solution throughout the reaction tube.
1. Additions to Vinyl Ethyl Ether
A solution of 475 g. (2.4 moles) bromotri-
chloromethane and 158 g. (2.2 moles) vinyl ethyl ether were placed
in the reaction vessel already described and irradiated at 00 with
stirring for twelve hours. The unreacted material was stripped at
reduced pressure and the remainder fractionated to give a cut,
b.p. 510/0.7 mm. Although this sample decomposed too rapidly to
allow analysis and a proper determination of its physical properties,
it was assigned the structure CCl1CH2CH:rrOCOH on the basis of its
reduction with LiAtH to CC13CCI2CH20C 5 and hydrolysis to CCl=CHCHO
[Section lXI D].
A solution of 720 go (3.45 moles) dibromodi-
fluoromethane and 144 g. (2.0 moles) vinyl ethyl ether were reacted
as previously described for ten and one-half hours. The unreacted
starting material was stripped at reduced pressure and the remainder
fractionated to give 362 g. (83% conversion)of CF2BrCH2CHBrOC2 5.
An analytical fraction had the following properties; b.p. 53.5/5 mm.,
n3 1.4490, 23 1.734.
Anal. Calcd. for Ce,%Br F2or 1MD, 42.46; %C, 21.30;
WH, 2.86; %Br, 56,70.
Found: 1MR,, 43.61 %C, 23.26;
%H, 3.52; Br, 54.95.
Decomposition of the compound by elimination
of hydrogen bromide from the molecule would account for the high
carbon-hydrogen and low bromine analysis. Assignment of the above
structure is based on its reduction to CF2BrCFH2CH20C2j [Section III D.
A solution of 600 g. (2.17 moles) CF2BrCFClDr
and 144 g. (2*0 moles) vinyl ethyl ether was reacted as before for
twelve hours. Unreacted material was stripped and the remainder
subjected to distillation. A few grams of product [apparent b.p.
710/1 mm.] were collected when the pot material began to decompose
at 850. The structure CF2BrCFC1CH2CHBrOC2H5 was assigned this
compound on the basis of its reduction to CF2BrCFCCIH2CH2OC2 5
[Section III D].
2. Additions to Vinyl 2,2,2-Trifluoroethyl Ether
A solution of 397 g. (2.0 moles) bromotrichloro-
methane and 200 g. (1.59 moles) CH=CHOCH1CF3 was irradiated by
ultraviolet light for eleven hours as previously described. Unreacted
material was stripped at reduced pressure and the remainder fractionally
distilled to give 470 g. (91% conversion) of CC13CH2CIIBrOC12CF. An
analytical fraction had the following properties: b.p. 450/0.4 maM.,
3 1.4488, d23 1.739.
Anal. Called. for C5.HBrClF 30t: M, 49-30; %C, 18.50; fH, 1.56;
silver equivalent, 81.09.
Found: N%, 50.02; %C, 18.58- %H, 1.63;
silver equivalent, 81.80.
A solution of 560 g. (2.68 moles) dibromodi-
fluoronethane and 126 g. (1.0 mole) CHi=CHOCH2CF3 was reacted for
thirteen hours and worked up as before. On fractionation 241 g.
(72 conversion) of CFBrCII2CHBrOCH2CF were obtained. An analytical
sample had the following properties: bp. 290/1.5 nm., n23 1.4052,
Anal. Called. for C5 H Br2gF o 0 Iy, 42.46; tC, 17.87;
%H, 1.50; %Br, 47.58.
Found: iR%, 43.10; Cj, 17.87;
IH, 1.77; %Br, 47.25.
A solution of 700 g. (2.54 moles) CF2BrCFC1Br
and 200 g. (1.59 moles) CHH2=COCH2CF3 was irradiated for thirteen
hours and worked up as previously described. Fractional distillation
provided 457 g. (72% conversion) of CFgBrCFClCHCHBrOCH CF3. A center
fraction had the following properties: b.p. 55/5 mm., D3 1.4188,
Anal. Calcd. for C6H5Br2CIF60: 1MR, 51.95; %C, 17.90; %H, 1.2,
Found: I- 52.41; %, 18.06; %H, 1.5;
C. Reactions of frBromoethers
1. Dehydrohalogenation of CF2BrCCHBrCH2rC 2H5
a. With Alcoholio Potassium WIdroxide
Forty-four grams (0.149 mole) of the above
ether were added over a thirty minute period to a stirred, refluxing
solution of 30 g. (0.53 mole) potassium hydroxide in 200 ml. 95%
ethanol. The solution was stirred at reflux an additional two hours
and the ethanol stripped. Fractionation of the remaining solution
gave 10 g. (42% conversion) of ethyl W -ethoxy crotonate,
C2 HOO CH1-CH2C00H5. An analytical sample had the following
properties: b.p. 590/0.9 mm. and 900/12 mm., n3 1.4332, d23 0.987.
Reported for ethyl Y-ethoxy crotonate: b.p. 86-870/12 Mr., 1.4375,
Anal. Calcd. for C8Hl 03 M.Wt., 158.2; 1MR, 41.97; %C, 60.74;
Found M1.Wt., 164; MD 41.78; %c, 58.60;
A vapor phase chromatogram revealed the presence
of several minor components which may explain the divergent analysis.
Additional evidence leading to the assignment
of the above structure was obtained from an infrared spectrum which
showed strong absorption at 5.78 microns, characteristic of a,0-
unsaturated esters (4).
b. With Solid Potassium Hydroxide
A slurry of 22 g. (0.35 mole) potassium
hydroxide in 100 ml. mineral oil was heated to 600 and 35 g. (0.12 mole)
CF2BrCIHCHBrCH2OC H5 added with rapid stirring over thirty minutes at
20 amm pressure. Pressure was then reduced to 0.5 mm. and the
temperature raised to 1000. Crude product (21.5 g.) was collected
in a Dry-Ice-acetone cold trap, dried and fractionated to give
7 g. (27% conversion) of CF2=CHCHBrCH2OC2I5, b.p. 56/24 mm.,
3 1.4282, d23 1.393.
Anal. Called. for Cg69BrP20g : II, 38.85; %c, 33.51; %H, 4.22.
Found: MRD, 39.70; %C, 34.68; %H, 4.51.
An infrared spectrum showed a single strong,
sharp absorption peak at 5.72 microns. Lilyquist (29) has observed
that a number of olefins containing a CF2=CH- group show carbon-carbon
double bond absorption in the range of 5.65-5.73 microns.
2. Dehydrohalogenation of CF2BrCFC1CH2CHBrCH2OC28H
A slurry of 15.5 g. (0.25 mole) potassium hydroxide
in 150 ml. mineral oil was heated to 1000 and 46 g. (0.13 mole) of
the above ether were added with vigorous stirring over a one hour
period. The mixture was stirred at 1000 an additional one and one-
half hours and the product stripped under vacuum into a trap cooled
to -750. Crude product (27 g.) was dried over Drierite and fractionated
to give 9.5 g. (27% conversion) of CFgBrCFClCCHCH OC H5. An
analytical sample had the following properties: b.p. 54/1.2 mm.,
n3 1.4358, d23 1.518.
Anal. Called. for CHBrCIF 0: !.Ht. 281.7; I %, 48.33;
0C, 29.87; %H, 3.22.
Found: M.Wt., 304; mRD, 48.46;
%C, 29.80; %H, 3.15.
An infrared spectrogram showed a single absorption
peak in the carbon-carbon double bond region at 5.97 microns.
3. Dehydrohalogenation of CF2BrCH2CHBrCH2OCF2CFC1H
A slurry of 47 g. (0.75 mole) potassium hydroxide in
300 ml. mineral oil was reacted at 1000 as previously described with
99 g. (0.26 mole) of the above ether. Crude product (65 g.) was
collected in a cold trap, dried over anhydrous calcium chloride and
separated into two fractions by distillation.
The first fraction consisted of 2.5 g* (5% conversion)
of CF2=CHCH=CHOCF2CFC1H. This cut had the following properties:
b.p. 62o/70 mM., n3 1.3820, 23 1*390.
Anal. Calcd. for C6HCJlF50Y M.Wt., 222.6; 14%, 35.48;
%c, 32.26; A 1.94.
Found: il.Wt., 234; 1 -, 37.25;
%C, 32.38; AH, 1,81.
The high molar refractivity observed may be due to
optical exaltation. An infrared spectrum of this compound revealed
two strong, sharp peaks in the carbon-carbon double bond region. One
peak, at 5.75 microns, can be attributed to the CF =CH- group while
the higher wave length absorption at 6.01 microns is due to the
The second fraction, weighing 19 g. (25% conversion),
was identified as CF2=CHCBrCH2O2CFCCH. This cut had the following
properties b.p. 1120/70 mm., n3 14083, d23 1.687.
Anal. Called. for C6HSCLBrFO )I.wt., 303.5; 1% 43.72
%C, 23.71; %H, 1.66.
Found M.Wt., 295;1 I, 44.43;
%C, 23.77; %t, 1.92.
An infrared spectrum showed a single peak in the
carbon-carbon double bond region at 5*73 microns, indicating the
4. Dehydrohalogenation of CF2BrCFC1CH2CHBrCH2OCFCFC1H
A solution of 8.4 g. (0.15 mole) potassium hydroxide
in 100 ml. 95% ethanol was added over a twenty minute period to 60 g.
(0.14 mole) of the above ether in 50 ml. ethanol, After addition was
completed the solution was stirred for two hours at 600, decanted from
the solid salt, washed, separated and dried. Fractionation provided
29 g. (56% conversion) of CF3BrCFClCHCHCH OCCFClH. An analytical
sample had the following properties b*p. 57/0.7 ma., n3 1.4152,
Anal. Calcd. for C7H5BrCl2F60gt iD, 53.20; %C, 22.69; %H, 1*36.
Found: 1I%, 53.30; %C, 23.09; %H, 1.82.
An infrared spectrum showed a single absorption peak
in the carbon-carbon double bond region at 5-93 microns.
5. Dehydrohalogenation of CF2BrCFClCH=CICCOCF2CFCIH
A solution of 1.7 g. (0.03 mole) potassium hydroxide
in 25 ml. ethanol was reacted with 10.4 g. (0.028 mole) of the ether
as described above. The mixture was worked up as before and fractionated
to give 2.2 g. (24% conversion) of CF BrCF=CHM=CHCOCF2CFClH. This
sample had the following properties: b.p. 410/0.7 amn., n3 1.4255,
Anal. Calcd. for C7H4Br01F60: M.Wt., 333.5- IMR, 47.87;
%C, 25.21; %H, 1.21; silver
Found Ml.Wt. 344; 1%, 51.05;
%C, 25.16; %H, 1.48; silver
An infrared spectrum exhibited two peaks in the
carbon-carbon double bond region at 5.91 microns and 6.06 microns
and a carbon-hydrogen stretching absorption at 3*23 microns.
6. Dehalogenation of CF2BrCFCCH2CHBrCH2OC2H5
Fourteen grams (0.2 mole) powdered zinc, 0.5 g. zinc
chloride and 75 ml. ethanol were heated to reflux and 36 g. (0.1 mole)
of the above ether added dropwise to the stirred mixture. The mixture
was stirred for three hours and decanted. The solution was washed
with water and the crude product dried and fractionated to give a
single compound whose infrared spectrum was identical to a speotrum
of an authentic sample of CF2=CFCH2CHCH2 (43).
7. Dehalogenation of CF2BrCFC1CH2CHBrCH2OCFGCFClH
A mixture of 23 g. (0.35 mole) powdered zinc, 1.0 g.
zinc chloride and 150 ml. isopropanol was heated to reflux and 80 g.
(0.177 mole) of the above ether added dropwise with stirring. After
addition the mixture was stirred for three hours and worked up as
described above. On fractionation a sample, b.p. 47-490/19 am,, was
obtained whose infrared spectrum was identical to that of an authentic
sample of CFC1HC00CH(CH,)2.
D. Reactions of a-Bromoethers and Derivatives
1. Reductions with Lithiun Aluminum Hydride
a. CFPBrCH2CHBrOC H
A solution of 10 g. (0.26 mole) lithium
aluminum hydride in 175 ml. anhydrous ethyl ether was added to the
crude ether remaining after stripping the unreacted material from the
addition of 550 g. dibromodifluoromethane to 100 g. (1.4 moles)
vinyl ethyl ether by the method described in Section III B. Addition
of the lithium aluminum hydride solution was carried out at 00 and
was necessarily slow due to the extremely vigorous reaction* After
addition was complete, the mixture was stirred an additional one and
one-half hours at room temperature and 200 ml. water added. The
mixture was extracted with ethyl ether, separated and dried over
anhydrous calcium chloride. Low boiling material was stripped and
the remainder fractionated to give 60 g. (21% conversion based on
vinyl ethyl ether) of CF2BrCH2CH20C2 H5 An analytical sample had
the following properties: b.p. 360/20 mm., n3 1.4026, d23 1.410.
Anal Calod. for CSIBrqF2O lI.Wt,, 203.0; MR4, 34.71( C0, 2958;
%H, 4.47; %Br, 39.46.
Found: M.Wt., 205; 1 35.10; %C, 29.64;
%H, 4.58; OBr, 39.60.
11TR spectra are consistent with the assigned
b. CFgBrCFlCH2CHBrOC2 H
A solution of 19 g. (0.5 mole) lithium
aluminum hydride in 225 ml, ethyl ether was reacted with crude
CF2BrCFC1CH2CHBrOC2H5, prepared from two moles vinyl ethyl ether,
as described immediately above. The mixture was worked up as before
to give 175 g. (33% conversion based on vinyl ethyl ether) of
CF2BrCFC1CH CI2OC H5. An analytical sample had the following
properties: b.p. 420/3 nm., n23 1.4185, d2 1.526.
Anal. Called. for C69BrC F30t 45.181 %C, 26.74; %H, 3.37;
silver equivalent, 134.7.
Found ?R, 44.48; %0, 26.77; eH, 3.43;
silver equivalent, 133.0.
c. CCICH2CHBrOC 21
A solution of 24 g. (0.63 mole) lithium
aluminum hydride in 350 ml. ethyl ether was reacted with crude
CC3 CH2CHBrOC 2I, prepared from 2.0 moles vinyl ethyl ether, as
previously described. The mixture was worked up as before to give
208 g. material, boiling range 55-64/15 mm. A vapor phase chromatogram
showed that this sample consisted of three components with the higher
boiling material richer in the major component. An infrared absorption
pea: was observed at 6.22 microns, indicating an unsaturated impurity.
The sample was washed with water, separated, dried and refractionated
with a 65 cm. column packed with protruded nickel packing to give a
chromatographically pure sample with the following properties:
b.p* 670/7.5 mm., i3 1.4615, d23 1.305.
Anal. Caled. for C59C30:o 1%, 41.53; %cs 31.34; %H, 4.74;
Found: 1R%, 40.50; %C, 31.54; %H, 4.88:
Assignment of structure was based upon
conversion of the compound to ethyl O-ethoxypropionate by ethanolic
potassium hydroxide. An infrared spectrogram exhibited two strong,
broad peaks at 12.80 microns and 14.40 microns.
A solution of 13 g. (0.34 mole) lithium
aluminum hydride in 175 ml. ethyl ether was reacted with crude
CF2BrCH2CHBrOCH2CF3, prepared from 1.0 mole of CIIHCICH2CF3, as
previously described. Reaction was decidedly less violent than
with CF2BrCH2CHBrOC2H5. The mixture was worked up as before to give
62 g. (24% conversion based on CH2=CIIOCHZCF3) of CF2BrCH2HCH2OCF .
An analytical sample had the following properties t b.p. 560/40 rm.,
n'3 1.3604, d23 1.613.
Anal. Calcd. for CYIBrFS 0 J.wt., 257.0; 1i%, 34.71
%c, 23.36; %H, 2.35; 5Br, 31.09.
Found: I.Wt., 250; 14 35.20;
%C, 23.50; %H, 2.45; %Br, 30.83.
In the manner previously described, 13 g.
(0,34 mole) lithium aluminum hydride in 175 ml. ethyl ether were
reacted with crude CF2BrCFClCHCHBrOCH2CF prepared from 1.27 moles
CH2=CHOCHICF3 The mixture was handled as before and fractionated
to give 86 g. (21% conversion based on the vinyl ether) of
CF2BrCFC1CH2CH2OCH2CF An analytical cut had the following properties:
b.p* 430/2.5 m., n3 1.3840, d23 1.705.
Anal. Calcd. for CgI6BrCLFOt I 9 R, 44.18; %C, 22.28; %1, 1.87;
silver equivalent, 161.7.
Found: 11%, 44.51; %c, 22.41; ;'I, 1.98;
silver equivalent, 163.5.
Nine grams (0.24 mole) lithium aluminum
hydride were reacted as before with crude CC3CH2RCBrOCH2CF3, prepared
from 1.0 mole CH=CHOCH2CF3. The mixture was handled as previously
described and fractionated to give 50 g. (21% conversion based on
the vinyl ether) of CCl3CH2CH20CIFCF,. An analytical cut had the
following properties: b.p. 540/6 mm., n23 1.4119, d23 1.460.
Anal. Calcd. for C56C13F30: RD, 41.53; %c, 24.47;
eo, 2.46; gC1, 43.33.
Found: 1IR, 42.10; %C, 24.52;
IH, 2.45; %Cl, 43.33.
2. Reactions of the Reduced Ethers
a. Dehydrobromination of CF2BrCH CHOC0H5
A slurry of 9.5 g. (0.15 mole) powdered
potassium hydroxide and 50 ml. mineral oil was heated to 1000 and
23 g. (0.113 mole) of CFgBrCH2CH20OC2H were added dropwise with
vigorous stirring. The reaction products were stripped at reduced
pressure into a cold trap. The crude material was then dried over
calcium chloride and fractionated to give 4.5 g. (360 conversion)
of CF2=CHCH20C2H5. An analytical sample had the following properties :
b.p. 670, n3 1.3548, d23 1.007.
Anal. Calcd. for C5GFP201 i!.Xt., 122.1; I, 26.47;
%C, 49.18; SH, 6.63.
Found: t ,t., 130; 1%9, 26.56;
%c, 49.18; %H, 6.58.
An infrared spectrum showed a very strong
absorption peak in the carbon-carbon double bond region at 5.73 microns.
b. Dehalogenation of CF2BrCFC1CH2CH2OC21H
A mixture of 19.5 g. (0.30 mole) powdered zinc,
0.5 g. zinc chloride and 100 ml. absolute ethanol was heated to reflux
and 60 g. (0.223 mole) of CF2BrCFClCH2CI20C2H were added with
stirring over a one hour period. The mixture was stirred at reflux
an additional two hours and the liquid decanted, washed with water
and separated. The wash water was extracted with ethyl ether which
was combined with the organic layer, dried and fractionated to give
17 g. material, b.p. 72-780, and 4.5 g. material b.p. > 780. A vapor
phase chromatogram revealed that the former contained 50% ethyl ether
and 50% CF2=CFCH2CII2C025, while the latter fraction consisted of
approximately 90% CF2=CFCH2CH2OC2,5 The high boiling fraction was
purified by passing through the preparative VPF column to give a
chromatographically pure analytical cut with the following properties:
b.p, 960, n3 1.3555, 23 1.069.
Anal. Calcd. for C6 F30 t II.t., 154.1;1 1, 31.08;
%c, 46;77 %H, 5.89.
Found: M1.Wt, 154; iR 31.41;
%C, 46,51} ^H 5.99.
An infrared spectrum exhibited a strong, sharp
absorption peak at 5.54 microns, characteristic of the CF,=CF-
group (29,19). Conversion was 35%-
co Dehydrobromination of CF2BrCH CIIOCH2 CF.
A slurry of 9.5 g. (0.152 mole) powdered
potassium hydroxide in 50 ml. mineral oil was heated to 1000 and 32 g.
(0.125 mole) of CF2BrCHCH2oCHICPF were added dropwise with vigorous
stirring. The material was handled as before to give 25 g, of
crude material which was dried and distilled over a twenty degree
boiling range. An analytical sample of CF2=CHCH2OCR CF was obtained
using the preparative scale VPC column. The following properties
were observed: b.p. 810, n3 1.3207, d23 1,299.
Anal. Called. for C5 15F5: 5 .Wt., 176.1a 11%, 26.47;
5C, 34.101 %H, 2.86.
Found: M.Wt., 175; Ii', 27.05;
%C, 34. 25; %r, 3*14*
An infrared spectrum showed a strong, sharp
absorption peak assigned to the CF2=CH- group at 5.72 microns.
Conversion was 45%.
d. Dehalogenation of CF.BrCFC1CH2CGHCF
A mixture of 13 g. (0.2 mole) powdered zinc,
0.5 g. zine chloride and 75 ml, methanol was heated to reflux and
45 g. (0.139 mole) of the above ether added dropwise with stirring.
After addition was complete, the mixture was refluxed with stirring
for two hours, decanted, washed with water and the crude product
(19 g.) separated, dried over calcium chloride and distilled to give
12 g* (42- conversion) of CF ,CFCFCH2CHOCH0CF3. A chronatographically
pure sample, obtained as previously described, had the following
properties: bp. 1030, n3 1.3302, d23 1.307.
Anal. Calcd. for C646F60: 'M.Wt., 208.1; 1%D, 31.08;
%c, 34.581 %H, 2.73.
Found: HT.Ut,- 208; 1%, 32,50;
4~, 34.63; iH, 2.91.
An infrared spectrum exhibited a distinctive
CF2=CF- absorption peak at 5.53 microns.
e. Hydrolysis of CC3lCH2CH200C2i
A solution of 80 g. (1.2 moles) potassium
hydroxide in 200 ml, 95% ethanol was heated to reflux followed by
the dropwise addition of 70 g. (0.37 mole) of CC13CH2CH2 OC2 5 The
mixture was stirred at reflux for twenty hours, decanted and washed
with water. The insoluble organic layer was separated, dried and
fractionated to give a single product b.p. 66/17 mm ., 1.4059,
d23 0.960. 1% called. for C2H500CCH CH20C H5, 37.82. 14 found,
37.48. Physical constants reported for ethyl "-ethoxy propionate:
b.p. 67/17 mm., n~5 1,4070, d25 0.949.
An infrared spectrogram was identical with
that of an authentic sample.
3. Reactions with Alcohols
Absolute ethanol (300 ml.) was placed in a
one liter three-necked flask fitted with stirrer, condenser and
dropping funnel. To the stirred ethanol were added 175 g. (0.62 mole)
of CF2BrCH2CHBrOC2H5. Addition required one hour and was accompanied
by evolution of heat. The solution was stirred an additional one and
one-half hours at room temperature, washed thoroughly with water and
the crude product (150 g.) separated, dried over Drierite and
fractionated to give 122 g. of material with boiling range 62-670/14 mm.
An analytical sample, shown by a vapor phase chromatogram to contain
one major and three minor components, had the following properties:
b.p. 640/14 am*, n3 1.4057, d23 1.325.
Anal Caled. for CL,3BrF202 %, 45.58; C, 33.99;
%H, 5.30; %Br, 32.34.
Found: MRhD 45.13; %0, 37.30;
~, 5.64; 5Br, 30.57.
The major component has been assigned the
structure CF2BrCH2CH(OC2H5)2 on the basis of NMR spectra for hydrogen
An infrared spectrum showed two strong, broad
absorption peaks in the 9.0-9.5 micron region and no absorption in
the carbonyl or carbon-carbon double bond regions.
Conversion was approximately 75%*
b. CF2BrCFCICH CHBrOC Hq
Two hundred seventy grams (0.77 mole) of the
above ether were reacted with 300 ml. absolute ethanol as before and
stirred an additional three hours at room temperature. The material
was worked up as previously described and fractionated to give 90 g.
(38% conversion) of CF2BrCFCICH2CH(0C2HS)2. An analytical out had the
following properties: b.p. 52/0.5 mm., 3 1.4190, d23 1.440.
Anal. Called. for C8H3BrC1F302: RD, 55.06; %C, 30.63* %H, 4.18.
Found: 1IRD, 54.95; %c, 31.01; %H, 4.43.
An infrared spectrum showed two strong, broad
peaks in the 8.9-9.4 micron region. No carbonyl or carbon-carbon
double bond absorption was observed.
HMR spectra for hydrogen and fluorine were
consistent with the assigned structure,
Trifluoroethanol (100 ml.) and 58 g. (0.17 mole)
of the subject ether were combined and stirred at room temperature
with slow evolution of heat for sixteen hours and at 750 for six hours.
White fumes were evolved and the flask was etched, indicating elimination
of hydrogen fluoride. After working up the crude material and
fractionating it, a center out showed both carbonyl and carbon-carbon
double bond absorption in its infrared spectrum.
The desired acetal was successfully prepared
in the following manner. Trifluoroethanol (200 ml.) and 84 g. (0.25
mole) of the subject ether were combined and stirred for forty-eight
hours at room temperature. During this period the flask was swept with
nitrogen and was backed by a cold trap. The solution was washed with
water and the crude material (64 g.) dried over Drierite and
fractionated to give 17.5 g. (21% conversion) of CF2BrCH2CH(OCH2CF3)2.
An analytical sample had the following properties t b.p. 78/20 mm.,
n3 1.3512, d23 1.670.
Anal. Called. for C79lrFg02: MR%, 45.58; $C, 23.68; A%, 1.97.
Found: 1 %, 46.08; %C, 23.818 %H, 2.25.
An infrared spectrum showed a strong, broad
peak from 8.9-9.3 microns. No carbonyl or carbon-carbon double bond
absorption was observed.
d. CF2BrCFC1CH2CHBrOC H2CF
Trifluoroethanol (200 ml.) and 100 g. (0.25
mole) of the subject ether were combined and stirred with no evidence
of reaction. The solution was heated to 50-600 for two and one-half
hours and began to evolve white fumes which gave a positive bromide
ion test in water. Stirring was resumed at room temperature for
twenty-four hours, during which the flask was swept with nitrogen.
The solution was washed with water and the crude material (96 g.)
separated, dried and fractionated to give 70 g. (67% conversion) of
CF2BrCFCl1H2CH(OCHCF )2. An analytical sample had the following
properties: b.p. 500/0.5 mm., n3 1.3745, d2 1.754*
Anal. Called. for C8H7BrC1F902g: .D, 55.06; %C, 22.80; %H, 1.67.
Found: 1MI' 54.92; 0C, 23.06; %H, 1.88.
An infrared spectrum showed a strong, broad
peak from 9.1-9.3 microns.
4. Reactions with Grignard Reagent
a. CF2Br2CH BrOCHC2
The above ether was prepared from 2.84 moles
vinyl ethyl ether and was used without distillation. It was placed
in a three-necked flask fitted with addition funnel, stirrer and
condenser and cooled to 00. Two moles methylmagnesium bromide in
ethyl ether were then added dropwise over a one hour period. The
reaction was very vigorous and necessitated continued cooling. After
addition was complete, the mixture was stirred for one hour at 00 and
for four hours at room temperature. The mixture was filtered and
the organic layer separated, dried and fractionated to give 80 g.
(19% conversion based on the vinyl ethyl ether) of CF2BrCH2CH(CIH)0C 5.
An analytical sample had the following properties: b.p. 550/41 am.,
3 1.4020, d23 1.335.
Anal. Called. for C6 HBrF20: M.Wt., 217.1; MRD 39.32;
SC, 33.20; %H, 5.11; Br, 36.82.
Found: M.Wt., 212; M~, 39.50;
%C, 33.48; SH 5.27; %Br, 37.15.
An infrared spectrum showed no earbonyl or
carbon-carbon double bond absorption.
(1) Dehydrobromination of CFZBrCH2CH(CH3)0OC2
A slurry of 22 g. (0.35 mole) of
potassium hydroxide in 200 ml. mineral oil was heated to 1000 followed
by the dropwise addition of 50 g. (0.23 mole) of the above ether.
The mixture was stirred at 1000 an additional two hours and the product
stripped under reduced pressure into a cold trap. The crude material
(25 g.) was dried and fractionated to give 14 g. (45% conversion) of
CF2=CHCH(CH)OC2H5. An analytical sample had the following properties:
b.p. 790, n-3 1.3588, d23 0.969w
Anal. Called. for C6110F20: l%, 31.08; %C, 52.93; %H, 7.40.
Found: M%, 30.97; %C, 52.93; %H, 7.53.
An infrared spectrogram exhibited
typical CF2=CH- absorption at 5.74 microns.
b. CFPBrCH2CHBrOCH CF
Two attempts to replace the c-bromine atom with
a methyl group via the Grignard reaction were unsuccessful. The reaction
was run as described above as well as at reflux temperature. In both
cases only high boiling material, which decomposed with heavy fuming,
5. Other Reactions
a. Hydrolysis of CC13CH CHBrOC2 H
A crude sample of the above ether was placed in
an Erlenmeyer flask fitted with a tube leading to a dilute solution of
potassium hydroxide, which was inadvertently sucked back into the ether.
The organic phase was separated, dried and fractionated to give 26 g.
(21% conversion based on vinyl ethyl ether) of extremely lachrymatory
material identified as CCl2=CHCHO. The following properties were
observed: b.p. 62-650/83 mm., 0 1.5105, d20 1.447. M% ealed. for
CCl2=CHCHO, 25*33- nD found, 25.80. Reported for f, -dichloroacrolein:
b.p. 124-125o, n7.5 1.5090; d17.5 1.395.
An infrared spectrogram showed the following
Wave length (microns) Conclusions
3.28 (medium) =CH
3.5 CH stretch in aldehyde
3.65 (weak) J
5.90 (v. strong) a, P-Unsaturated aldehyde
6.27 (V. strong) C=C conjugated with carbonyl
12,05 (v. strong)
b. CF2BrCH2CHlBrOC25 with Sodium Acetate
Sixty-four grams (0.78 mole) of anbydrous sodium
acetate were added in 3-4 g. portions with stirring to 200 g. (0.71 mole)
of the subject ether at 40-50* After addition was complete, the mixture
was stirred for twelve hours at 40 and the temperature raised to 1250
After one hour a vigorous reaction occurred causing a large quantity
(65 g.) of material to distill over into a cold trap. This material was
distilled to give a fraction, b.p. 19-200, which reacted violently with
water and gave acetanilide on reaction with aniline. This low boiling
material was probably acetyl fluoride, b.p. 200. An infrared spectrum of
the higher boiling material indicated it to be a mixture of acetic acid
All glassware used in the reaction was etched,
evidence that hydrogen fluoride was evolved in the decomposition.
c. Pyrolysis of CFBrCCHBrOCCFr
A Pyrex column four inches long with one-half
inch inside diameter was packed with small glass beads and heated to 2200.
Sixty-two grams of the subject ether were passed through the tube at 35 m.
pressure over a period of one hour. The entire amount was recovered
d. Pyrolysis of CF2BrCH2C1(002H5)2
(1) With NaH2PO4 at 300
The column described above was packed
with 13 g. of anhydrous monosodium phosphate and heated to 3000,
Seventy-five grams of the subject acetal were passed over the catalyst
bed at 8 mm. pressure over a period of thiry minutes. Seventy-four
grams material were recovered and identified as starting material.
(2) At 4000
A Pyrex tube, twelve inches long with
three-fourths inch I.D., was packed with short lengths of Pyrex glass
rod and heated to 4000. Forty grams of the acetal were passed through
the column at 10-20 mm. pressure over a period of one hour. An
infrared spectrum of the recovered material showed no absorption
peaks in the carbon-carbon double bond region.
E. Miscellaneous Reactions
1. Synthesis of 2-(2.2 2-Trifluoroethoxy--butadiene
a. Preparation of CH2=CHCH(OCHi0CF )CH OH
A solution of 0.5 g. sulfuric acid in 530 g.
(5.30 moles) trifluoroethanol was heated to reflux and 50 g. (0.71
mole) 3,&-epoxybutene-1 added dropwise with stirring over a one hour
period. Stirring at reflux was continued for two hours, followed by
the addition of 10 g. potassium carbonate. The solution was stirred
overnight at room temperature, the unreacted material stripped and
the remainder fractionated to give 46 g. (38' conversion) of
CH2=H-CH(OCCH2cCF3)C0 OH, An analytical fraction had the following
properties: b.p. 860/55 nm., r23 1.3797, d23 1.198.
Anal. Calod. for C69Fo0 '= M%, 32.61; %C, 42.351 O%, 5.33.
Found: 1Rd 32.92: C0, 42.37; %H, 5.46.
An infrared spectrogram showed the following
Wave length (microns)
b. Preparation of
CH stretch in terminal CH2=
CH2 in plane deformation in vinyl group
0-0-C or C-F
A solution of 47.5 g. (0.6 mole) of pyridine
and 102 g. (0.6 mole) of CH2=CHCH(OCH2CF3)CH20H was cooled to 0 and
116 g. (0.98 mole) of thionyl chloride added dropwise with stirring.
The mixture was then heated with stirring at 75 for two hours,
washed with dilute hydrochloric acid and extracted with ethyl
ether, dried and fractionated to give 68 g. (60% conversion) of
CI2=CHCH(OCIHCF)CH Cl. An analytical sample had the following
properties: b.p. 660/55 mm., n 1.3852, d0 1.209.
Anal. Calcd. for C6H8lF30: 1M%, 35.95; %C, 38.21;
%H, 5.28; %Cl, 18.80.
Found 14 36.60; %C, 38.13;
%H, 4*31; Ol, 18.69.
An infrared spectrogram showed the following
Wave length (microns) Conclusions
6.10 (weak) C=C stretching
7.00 (medium) Vinyl group
7.83 (v. strong) CF3
8.62 (vo strong) C-0-C or 0-F
8.90 (v. strong) 0-0-C
13.17 (medium) 0-C1
c. Preparation of CH2= C(OCHICF3)CHCH2
A solution of 40 g. (0.64 mole) of potassium
hydroxide in 220 ml. methanol was heated to reflux and 65 g. (0*345
mole) of CH2=CHCH(OCH2CF3)CH2Cl added and stirred for one and one-half
hours. The salt was removed by filtration and the solution washed
with water to give an insoluble organic layer which was separated,
dried and fractionated to give 20 g. (38% conversion) of CHC(OCH2CF3)-
CH=C~I Rydroquinone (0.1 g.) was added to the material before
distillation to prevent polymerization. A chromatographically pure
sample had the following properties t b.p. 35/95 amm and 930/760 mm.,
16 1*3778, d2 1.116.
Anal. Calcd. for C6H30:s 4%p, 30.62; %C, 47.37; %t, 4.64.
Found t 14%, 31.41; %C, 47.62; AH, 4.79.
Optical exaltation may account for the high
value observed for the molar refractivity.
An infrared spectrogram showed the following
Wave lenrrth (microns) Conclusions
6.08 (weak) CC
6.26 (strong) Conjugated C=C
6.97 (medium) Vinyl group
7.87 (v. strong) CF3
8.57 (v. strong) C-0-C or C-F
8.87 (strong) 0-0-C
2. Reaction of Trifluoroethanol with Methylacetylene
An autoclave was charged with 200 g. (2.0 moles)
of trifluoroethanol, 80 g. (2.0 moles) of methylacetylene and 10 g.
of potassium hydroxide and reacted at 225 for eighteen hours.
Unreacted methylacetylene (65 g.) was bled into a trap and the
remainder fractionated to give 17 g. of material, b.p. 57-72.
A vapor phase chromatogram showed that this fraction consisted of
three components, the major one being trifluoroethanol. The material
was washed thoroughly with water and the organic layer separated,
dried and fractionated to give 1 g. of material, identified as
(CH3)2C(OCH2CF3)2, with the following properties b.po 120-126,
n3 1.3270, d23 1.261.
Anal. Calcd. for C7Ho0F602: !D%, 37.81; %C, 35.01; H, 4.20.
Found: tRD, 38.50; %C, 35.21; AH, 4.36.
MIR spectra of hydrogen and fluorine were consistent
with the proposed structure.
Conversion, based on chromatographic analysis,was
F. Preparation of Starting Materials
1. Preparation of Ally3 2-Chloro-l,l,2-trifluoroetl.l Ether
A solution of 157 g. (2.7 moles) allyl alcohol and
300 g. KOH in 300 nl. water was placed in a large pyrex tube fitted
with stirrer, condenser and fritted-glass gas addition tube.
Chlorotrifluoroethylene was sparged into the stirred solution until
no further increase in volume was observed. The solution was washed
thoroughly with water and the immiscible layer separated and dried
over Drierite. Distillation gave the desired product, bp. 108-1090,
in 67% conversion (318 g.).
2. Preparation of Vinvl 2,2,2-Trifluoroethyl Ether
A solution of 50 g. potassium hydroxide in 300 g.
(3.0 moles) trifluoroethanol was sealed in an autoclave, which was
then charged with acetylene to a pressure of 300 psi. The autoclave
was heated with rocking at 1350 for five hours and at 1500 for five
hours. Distillation of the contents gave the desired ether, b.p.
40-42, in approximately 90% conversion.
A study has been made of the peroxide and ultraviolet catalyzed
free radical addition of bromotrichloromethane, dibromodifluoromethane
and 1,2-dibromo-2-chloro-ll,,2-trifluoroethane to alkenyl alkyl ethers.
The alkenyl ethers selected for this work were allyl ethyl ether, allyl
2-chloro-l,l,2-trifluoroethyl ether, vinyl ethyl ether and vinyl
One-to-one addition products were obtained in each case, with
radical attack occurring at the terminal methylene carbon atom.
Adducts of allyl ethers were obtained in low (26-50%)
conversion with formation of appreciable amounts of high boiling
material assumed to be telomers, while adducts of vinyl ether were
formed in high (72-91%) conversion with little telomerization.
The addition products and/or their derivatives were converted
to unsaturated fluoroethers by dehydrohalogenation and dehalogenation
reactions. Dehydrohalogenations were best accomplished with powdered
potassium hydroxide in mineral oil, since undesirable side reactions
occurred when the CF2=CH- group was formed in alcoholic base.
The a-bromoalkyl ethyl ethers were found to be highly reactive
and thermally unstable, while the a-bromoalkyl 2,2,2-trifluoroethyl
ethers exhibited markedly lower reactivity and higher thermal stability.
This observation may be explained by the negative [electron withdrawing]
inductive effect of the fluorine atoms which inhibits the ability of the
oxygen atom to participate in the resonance forms shown when R' is -CLCF3.
+ .. +
A 2-substituted fluoroalkoxy butadiene was prepared and found
to homopolymerize readily to a white, crumb-like elastomer.
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Eugene Curtis Stump, Jr. was born May 19, 1930 in Charleston,
West Virginia. He attended local schools in that city and graduated
from Stonewall Jackson High School in May, 1948.
He entered West Virginia University in September, 1948 and
received the B.S. degree in Chemistry in June, 1952. After graduation
he entered the U. S. Air Force as a lieutenant and was sent to
Columbia University under the Air Force Institute of Technology
program where he received the M.A. degree in Organic Chemistry,
in December, 1953. From September, 1953 to September, 1956, the
author served as project engineer in the Materials Laboratory,
Wright Air Development Center and upon his release from the service
in September, 1956 entered the graduate school of the University
of Florida, where he held a research assistantship sponsored jointly
by the Office of the Quartermaster General, U. S. Army, and
Wright Air Development Division, U. S. Air Force.
The author is a member of the American Chemical Society,
Phi Lambda Upsilon, Alpha Chi Sigma and Gamma Sigma Epsilon.
This dissertation was prepared under the direction of the
chairman of the candidate's supervisory committee and has been
approved by all members of that committee. It was submitted to the
Dean of the College of Arts and Sciences and to the Graduate Council,
and was approved as partial fulfillment of the requirements for the
degree of Doctor of Philosophy.
August 13, 1960
Dean, College of Arts and Sciences
Dean, Graduate School
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TITLE: The synthesis and reactions of some saturated and unsaturated
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