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Fluorocarbon - aromatic hydrocarbon compounds

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Fluorocarbon - aromatic hydrocarbon compounds
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Clark, Reginald F
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Gainesville, Fla.
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iii, 65 leaves. : ; 28 cm.

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Fluorocarbons ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Fluorocarbons. ( fast )
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bibliography ( marcgt )
non-fiction ( marcgt )
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Academic theses ( lcgft )

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Thesis:
Thesis--University of Florida, 1956.
Bibliography:
Includes bibliographical references (leaves 61-63).
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Manuscript copy.
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Vita.

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Full Text
FLUOROCARBON-AROMATIC
HYDROCARBON COMPOUNDS
By
REGINALD F. CLARK
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
August, 1956


TABLE OF CONTENTS
Page
LIST OF TABLES Ui
INTRODUCTION 1
Historical Development of Fluorochemicals 1
Fluorocarbon Chemistry 3
Aromatic Compounds ....... 6
Statement of the Problem 13
EXPERIMENTAL PROCEDURES 15
Fluorocarbon Carboxylic Acid Chlorides. 15
Fluorocarbon Aromatic Ketones. ... 16
2,4-Dinitrophenylhydrazones .... 22
Semicarbazone 22
Fluorocarbon Acid Anhydrides .... 23
Aromatic Esters of Fluorocarbon Acids . 23
Friedel-Crafts Alkylation 33
Aromatic Metallic Reactions .... 34
Aromatic Fluorocarbon Ethers .... 40
DISCUSSION 44
Organic Aromatic Ketones 44
Fluorocarbon Aromatic Ketones. ... 45
Aromatic Esters of Fluorocarbon Acids . 48
Alkforyl Aromatic Compounds .... 51
Aromatic Fluorocarbon Ethers .... 54
Conclusions .56
SUMMARY 57
BIBLIOGRAPHY 61
ACKNOWLEDGEMENTS 64
BIOGRAPHICAL NOTE 65


LIST OF TABLES
Table Page
I Fluorocarbon Acid Chlorides .... 17
II Fluorocarbon Aromatic Ketones. ... 20
III2,4-Dinitrophenylhydrazones of Fluoro¬
carbon Aromatic Ketones 24
IV Fluorocarbon Acid Anhydrides .... 25
V Aromatic Esters of Fluorocarbon Acids . 29
iii


INTRODUCTION
It is usually recognized at the present time that
organic chemistry is one of the largest and most extensive¬
ly investigated branches of the science of chemistry; how¬
ever, in the last decade a new field of chemistry has de¬
veloped with a potentiality to surpass organic chemistry in
number of compounds and investigational endeavor. It is
identified as fluorocarbon chemistry. As the name implies,
fluorocarbons are compounds, analogous to hydrocarbons, but
with fluorine atoms in the positions occupied by hydrogen
atoms in hydrocarbons.
On the basis of our present knowledge, it has been
predicted that the present one million organic compounds
12
would serve as patterns for about 10 fluorocarbons, fluoro¬
carbon derivatives and fluorocarbon organic hybrids.
Historical Development of Fluorochemicals
It was not until 1886 that Moissan 18 first iso¬
lated elementary fluorine by the electrolysis of anhydrous
hydrogen fluoride and potassium fluoride. Since that time,
chemists have been extremely interested in the violent re¬
action between it and carbonaceous material. Moissan made
1


2
many attempts without too much success to utilize this re¬
action for the preparation of compounds of fluorine and car-
14
hon. In 1926, Leheau and Damiens obtained methforane
OO
from this reaction, and in 1930, Ruff and Keim isolated
and identified ethforane from this same reaction. During
Op 0*1
this period other investigators * produced ethforane
and ethforene by various experiments, but it was not until
25
1937 that Simons and Block discovered that the reaction
between carbon and fluorine could be controlled by cataly¬
zation with mercury or mercury salts. The first series of
fluorocarbons, possessing an entirely new set of properties,
was discovered by this method and thus established the foun¬
dation for an entirely new field of chemistry.
During World War II atomic energy research needed
large quantities of fluorocarbons for use in problems con¬
cerned with the separation of uranium isotopes, and due to
this large demand, several processes were developed to pro¬
duce fluorocarbons.
In the years 1941-1943, two major processes were
developed. The first was catalytic fluorination of hydro¬
carbons using silver, copper or mercury metal and salts as
the catalysts, and the second was the metallic fluoride pro¬
cess. The metallic fluoride process utilizes the reaction
between a metal fluoride, such as silver difluoride or co¬
balt trifluoride, and an organic compound. A short time


3
later an electrochemical method was invented "by Simons ,
which produces fluorocarbons without the use of elementary
fluorine. By this method an electric current is passed
through liquid consisting of an organic substance and liq¬
uid hydrogen fluoride, which causes the formation of the
product which may or may not and usually does not have the
structure of the original organic substance. This electro¬
chemical process is the most economical, versatile and sim¬
plest method for obtaining fluorocarbons and some fluorocar¬
bon derivatives.
Fluorocarbon Chemistry
The properties of the fluorocarbons and their de¬
rivatives are providing many opportunities in advancing and
testing theories of chemical and physical behavior. From
the very start, the unusual physical properties of the
fluorocarbon liquids were noted. Values for surface tension,
diamagnetic susceptibilities, index of refraction, Verdet
constants, energies of vaporization per gram, ultrasonic
velocity and other physical properties are very low com¬
pared to organic liquids, and in some cases are the lowest
ever recorded. Liquified inert gases would be an excellent
standard for solubility and liquid state studies; however,
their availability and low boiling points make their use
prohibitive. Experimental data has shown that fluorocarbons


4
approach the inert gases as closely as can he expected of
any known polyatomic substances and this with their avail¬
ability and variety should make them the best secondary
standard for liquid state and solubility studies. It is
evident that future studies of the physical properties in
the fluorocarbon domain will contribute significantly to
the theoretical development of the liquid state and other
related philosophical interests.
The chemical properties of fluorocarbon compounds
are vastly different from those expected by analogy with
organic compounds. For example, fluorocarbons are thermal¬
ly stable and extremely resistant to oxidation, whereas, in
hydrocarbons the opposite is true. Fluorocarbon oxides and
nitrides, which have the skeletal arrangement of organic
ethers and amines respectively, are found to be completely
void of the chemical properties usually associated with
these organic compounds.
Some fluorocarbon compounds, however, undergo many
reactions found in organic chemistry. For example, fluoro¬
carbon carboxylic acids can be esterified with organic al¬
cohols and fluorocarbon carboxylic acid chlorides react
with aromatic compounds in a Friedel-Crafts reaction to
produce ketones.
It is quite apparent that the empirical rules of
organic chemistry do not always apply to fluorocarbon


5
compounds. This is easier seen when it is considered that
the rules of organic synthesis are the result of the accu¬
mulation and organization of years of experimental data,
and that this data is inadvertently classified according to
the properties of the functional groups. Usually the prop¬
erties of these functional groups are independent of the
organic radical to which they are attached. This has made
the distinction between the properties of a functional
group and the organic compound containing that group quite
vague.
On the basis of existing experimental results, it
has been shown that the effect of a fluorocarbon radical on
a functional group is vastly different than that of an or¬
ganic radical. It is this large difference in chemical
properties which will necessitate the accumulation of a
large amount of experimental data in order to formulate
the chemical properties and methods of synthesis related
to the fluorocarbon compounds.
From time to time, there will undoubtedly be some
similarity to the chemistry of organic compounds, but it is
only through experimental results that similarities and
differences will be resolved.
This present work is submitted in the hope that
the experimental results will contribute to the organiza¬
tion of the chemistry of fluorocarbon compounds.


6
Aromatic Compounds
Aromatic character or aromaticity has always been
associated with certain types of reactions more or less
peculiar to benzene and its derivatives. Among these are
nitration, sulfonation, mercuration, the Friedel-Crafts re¬
actions and halogenation; however, all of these reactions
are encountered in the aliphatic series and, as such, the
line of demarcation between aromatic and aliphatic organic
compounds is so ill defined that no simple definition has
been agreed upon.
Today, aromatic compounds comprise a major portion
of the commercial chemical sales and are utilized as start¬
ing materials, intermediates or finished products in mil¬
lions of tons yearly. These aromatic compounds find their
way into everyday use as dyes, plastics, coatings, paints,
food preservatives, drugs and numerous other applications.
Aromatic compounds containing a fluorocarbon radi¬
cal or a fluorocarbon derivative have been studied with
great interest with respect to the differences or simi¬
larities in chemical behavior in contrast to similar aro¬
matic organic compounds.
In order to understand this contrast in chemical
properties, an examination of the properties of some of the
aromatic organic compounds is necessary.


7
If toluene is vigorously oxidized, the methyl
group rather than the benzene ring is affected. The pro¬
duct is benzoic acid.
C6H5CH3 + 3 [O] ———* C6H5COOH -f H20
27
It has also been shown by Simons and McArthur
that toluene may be oxidized to o-cresol by oxygen in the
presence of hydrogen fluoride.
C6H5CH3+ 02 —0-CH3C6H4OH
If toluene is chlorinated in the presence of fer¬
ric chloride, substitution in the aromatic nucleus occurs,
yielding a mixture of ortho and para chiorotoluenes.
C6H5CH3 4- Cl2 -FgCl3-> o-CH3C6H4C1 + p-CH3C6H5Cl + 2HC1
However, if toluene is chlorinated in the presence
of strong light, substitution in the methyl group occurs.
C6H5CH3 H- Cl2 -^^raviplet-light^ c6h5ch2C1 + HC1
C6H5CH2C1 -H Cl2 -^íraviolet light> c6H5CHC12 + HC1
C6H5CHC12 â– + Cl2 -al^rajiplet_light^ c6H5CC13 + HC1
Either one, two or three hydrogen atoms can be re¬
placed by regulating the amount of chlorine used. The pro¬
ducts are benzyl chloride, benzal chloride and benzotri-
chloride.
When the methyl group of toluene is halogenated
to produce benzotrichloride, the chemical properties under¬
go a pronounced change, whereas, the methyl group of toluene
is unaffected by dilute acids, benzotrichloride is


8
hydrolyzed easily by warming with dilute acids to produce
benzoyl chloride, and, finally, benzoic acid.
C6H5CCl3 C6H5C0C1 -f- 2HC1 —C6H5COOH 4- HC1
Because of its high yields and simplicity, this
reaction is used commercially to produce benzoic acid of
high purity.
When benzotrichloride is treated with hydrogen
13 34
fluoride or antimony trifluoride * , the simplest aro¬
matic compound containing a fluorocarbon radical is pro¬
duced, benzotrifluoride.
C6H5CC13
BOB’
-» C6H5CF3-|- 3HC1
With this change to benzotrifluoride, the chemical
properties with respect to oxidation and substitution are
also changed.
Benzotrifluoride cannot be oxidized by any usual
reagents; however, if an amino group is introduced into the
aromatic ring, it is rendered susceptible to oxidation and
long treatment with chromic acid yields trifluoroacetic acid.
C6H5CF3 m-CF3C6H4N02
h2so4
HC1
m-CF3C6H4NH2 —> CF3C00H
This reaction demonstrates the stability of the
CF3 group to oxidation. In toluene, either the methyl
group or the ring can be oxidized, whereas, in benzotri-
fluoride only the aromatic ring can be oxidized, and only


9
after activation.
Certain ring-substituted, derivatives of benzotri-
fluoride may be easily made. When benzotrifluoride is halo-
genated, the halogen atom enters the ring meta to the tri-
fluoromethyl and not ortho or para, as in toluene.
C6H5CF3 4- Brg ——- ■> m-CF3C6H4Br 4- HBr
This orientation is also true for nitration and sulfonation.
Where the methforyl group is desired ortho or para
to some other group, a different approach must be used. In
some cases, the group desired may be introduced in the ortho
or para position of toluene, which may then be chlorinated
and treated with hydrogen fluoride to give the substituted
benzotrifluoride. Ring-substituted nitro and chloro com¬
pounds have been made by this method. For other types,
Jones 10 has made a number of phenols, fluorides, chlorides,
bromides and iodides by the diazonium transformation of or¬
tho and para aminobenzotrifluoride.
Compounds containing more than one methforyl group
g
are readily prepared. German chemists have prepared the
three isomeric bis(methforyl)benzenes, and also tris(meth-
foryl)benzene.
The procedure for preparing such compounds is quite
involved, as the following example will reveal.


10
m-CH3C6H4CH3 m-CCl3C6H4CHCl2 m-CF3C6H4CHF2-£i£.
m-CF3C6H4CF2Cl 111-CF3C6I4CF3
28
Simons and Ramler made an attempt to introduce
the pentafluoroethyl group into benzene by the use of the
Friedel-Crafts reaction between trifluoroacetyl chloride
and benzene. They obtained trifluoroacetophenone, which,
when treated with phosphorous pentachloride, gave CgH5CCl2-
CF3. This compound failed to react with antimony trifluo-
ride to give pentafluoroethylbenzene. Simons and Herman
later showed that it was not possible to replace the alpha
chlorine atoms in C6H5CCI2CF3 by the usual fluorinating
agents. They were successful in preparing a small amount
of the pentafluoroethyl benzene with active silver fluoride
made by using elemental fluorine. This established the
existence of an alkforyl radical on aromatic compounds
larger than trifluoromethyl.
McBee and Pierce have since reported that
l-ethforyl-4-methforylbenzene may be obtained from the cor¬
responding chloro compound by fluorination with a mixture
of antimony trifluoride and antimony pentachloride.
The preparation of fluorocarbon aromatic ketones
has been limited to the trifluoromethyl ketones of benzene
28
and toluene. As mentioned previously, Simons and Ramler
prepared trifluoroacetophenone using a Friedel-Crafts re¬
action, and Jones 11 prepared o-tolyl trifluoromethyl


11
ketone by the reaction of organometallie derivatives of
benzyl chloride with trifluoromethylnitrile or trifluoro-
acetyl chloride, followed by rearrangement. Trifluoro-
acetophenone undergoes a haloform reaction and reacts with
phosphorous pentachloride but fails to form a cyanohydrin.
As yet, there have been no fluorocarbon phenyl
15
ethers produced. McBee and Bolt have prepared various
chlorofluoroethyl and chlorofluoropropyl aromatic ethers by
reacting CHCI2CF2CI, CH2CICF2CI and CF3CHCICF3 with sodium
35
aryloxides. Tarrant and Brown have also prepared sev¬
eral chlorofluoroethyl aromatic ethers using fluoro or
chlorofluoroethenes with phenol and potassium hydroxide.
Since fluorocarbon aromatic compounds usually are
more resistant to oxidation and bacterial action than aro¬
matic compounds, they should have a large potential in dyes
and coatings.
The Germans first used dyes containing fluorine in
the 1930»s.
Some of
their
dye bases are
as follows:
NH2
NH2
C
1
Sj|S02C2H5
r^l) cf3
Jcf3
F3C
V-
J)nh2
kJ
Cl
Fast Orange GGD Fast Golden Orange GR Fast Scarlet VD


12
These bases were generally coupled with Napthol AS.
An example is as follows:
The red coloration of the Natzi flag was due to a
dye of this type and proved to he very resistant to fading
by light.
Indanthrenblue CLB produced during World War II for
the Luftwaffe has the following formula:
cf3
Dyes containing the trifluoroethoxy group have
also been prepared by the Germans. They found that the ex¬
change of a trifluoroethoxy group for an alkoxyl group
caused the colors to assume a lighter hue.
There has been considerable activity towards pre¬
paring styrene derivatives and subsequent polymers contain-
on
ing fluorine. Renoll reports the preparation of


13
m-methforylstyrene toy the use of the Grignard reagent as
follows:
m-CF3C6H4JBr MS > m-CF3C6H4MgBr JSSaSgO.»
m-CF3C6H4CH0HCH3 —£205..-» m-CF3C6H4CH = CH2
This monomer, when heated at 105°, gives a hard
colorless polymer, and when used in films, is flexible and
21
resistant to sunlight and heat
Statement of the Problem
It can toe seen that the aromatic compounds con¬
taining a fluorocarbon radical possess certain desirable
properties, which should find wide applications if the
chemistry of these compounds were further developed. The
fluorocarbons are very resistant to oxidation and bacterial
activity, and on this basis we can assume that it is the
fluorocarbon radical on aromatic compounds which imparts
these properties to the molecule. Since a direct method
of attaching alkforyl groups to aromatic nuclei has not yet
been reported, except by chlorination of an alkyl side
chain followed by exchange reactions, an attempt was made
to find a method to introduce an alkforyl group directly
into the aromatic nuclei and to investigate other types of
fluorocarbon aromatic compounds. These may be outlined as
follows:


14
1. A study of the Friedel-Crafts type reaction
between aromatic compounds and fluorocarbon acid chlorides
with respect to the preparation and properties of the
fluorocarbon aromatic ketones. Several aromatic nuclei as
well as different fluorocarbon groups were used.
2. The preparation and study of the chemical
and physical properties of the aromatic esters of fluoro¬
carbon acids.
3. The reactions of some fluorocarbon halides with
benzene, using Friedel-Crafts alkylation methods.
4. The investigation of the reactions of several
organic aromatic metallic compounds with fluorocarbon
iodides and the preparation of aromatic alkforyl derivatives.
5. A study of the reactions of aryloxides with
fluorocarbon iodides.
6. The preparation and study of the chemical and
physical properties of difluoromethyl phenyl ether.


EXPERIMENTAL PROCEDURES
Fluorocarbon carboxylic acids—The fluorocarbon
carboxylic acids were obtained from the Minnesota Mining
and Manufacturing Company. They were purified by fraction¬
ation through a 50 cm. column, 8 mm. inside diameter,
packed with l/l6 in. glass helices. This fractionation
column was used in all subsequent experiments.
Fluorocarbon Carboxylic Acid Chlorides
Preparation—The acid chlorides were prepared by
the dropwise addition of the acids to an equivalent of
phosphorous pentachloride. The reaction may be expressed
as follows:
Rf COOH -f PC15 — » Rf COCI 4- POCI3 •+- HC1
The first two members were collected from the reaction mix¬
ture in a trap cooled in Dry Ice-acetone and transferred to
a low temperature fractionation column for purification.
The other members of the series were fractionated directly
from the reaction mixture. The yield of acid chloride for
all members of the series was approximately quantitative.
Analysis—The acid chlorides were hydrolyzed quan¬
titatively in dilute sodium hydroxide, and the resulting
15


16
solution adjusted to a pH 7 with nitric acid. The chloride
ion was then determined volumetrically by Mohr’s method.
The physical properties and analyses of the acid
chlorides are summarized in Table I.
Fluorocarbon Aromatic Ketones
Preparation—The fluorocarbon aromatic ketones
were prepared according to one of the three following pro¬
cedures:
Procedure A—Acid chlorides boiling below 40°. In
a 250 ml. flask equipped with magnetic stirrer, thermometer
and a ary Ice-acetone Dewar type reflux condenser, were
placed two moles of the aromatic compound and one-half
mole of aluminum chloride and cooled to -10°. One-quarter
mole of the acid chloride was bubbled through the mixture
over a period of six hours. The flask was allowed to warm
to 0° with the initial introduction of the acid chloride
and maintained at 0° during the entire addition, after
which the flask was warmed to 10° and stirred for two ad¬
ditional hours until there was no longer any evolution of
hydrogen chloride. The reaction mixture was poured into an
ice-hydrochloric acid mixture and ether added for extrac¬
tion. The ether extractions were dried over calcium
chloride and fractionated at reduced pressure.


TABLE I
Compound
CF3COCI36
c2f5coci
c3f7coci17
c4f9coci
C5F11C0C1
Fluorocarhon Acid Chlorides
Analysis
B.p. °C
M 25
SB—
ñ 25
<¿4—
Theory
to
Found
to
-27
-
-
-
-
5.0-5.5
-
-
19.43
19.42
38.0-39.0
1.288
1.55
-
-
67.5-68.0
1.315
1.59
12.52
12.50
85.8-86.0
1.327
1.66
10.67
10.64


18
Procedure B—Acid chlorides Boiling above 40°.
One-half mole of aluminum chloride and two moles of an aro¬
matic compound were placed in a 250 ml. flask, which was
equipped with a magnetic stirrer, thermometer and a water
condenser. The flask was warmed to 50° and the acid chlo¬
ride was added dropwise during a period of four hours. The
reaction mixture was cooled to room temperature, poured in¬
to an ice-hydrochloric acid mixture and ether added for ex¬
traction. The ether extractions were dried over calcium
chloride and fractionated.
Procedure C—The apparatus was the same as in
Procedure B. Aluminum Bromide was substituted for alumi¬
num chloride. The aluminum Bromide was prepared By adding
Bromine dropwise to small pieces of aluminum metal contain¬
ing one piece of aluminum amalgam. During the addition of
Bromine, the mixture was cooled in an ice Bath. A mixture
of one-quarter mole acid chloride and one mole aromatic
compound was then added dropwise to the aluminum Bromide
during a period of two hours. The reaction was maintained
at 50°. After the reaction was completed, Procedure B was
followed.
Analysis—The ketones were analyzed By a method
similar to the method of Kimball and Tufts . A weighted
amount of the ketone was placed in a Parr Bomb with a one
gram piece of metallic sodium and the Bomb flushed with


19
hydrogen. The homh was heated at a dull red heat for six
hours. The homh was cooled, the excess sodium was des¬
troyed with methanol and the contents of the homh were
washed quantitatively into a beaker.
The fusion mixture was then filtered through a
previously weighted sintered glass crucible to remove the
carhon for the carhon determination.
The water solution was quantitatively transferred
to a 500 ml. volumetric flask. A 50 ml. aliquot was taken
and titrated for fluoride with standard thorium nitrate hy
the method of Willard and Winter 38.
The physical properties, yields and analyses of
the ketones are summarized on Table II.
Solubility—The ketones are insoluble in water and
concentrated sulfuric acid and soluble in ether, ethanol,
benzene and butforyl oxide.
Degradation—-The ketones reacted vigorously with
a solution of concentrated potassium hydroxide to give a
haloform type splitting reaction, yielding a monohydro¬
fluorocarbon. Upon acidification, the sole organic pro¬
duct was an aromatic acid. In every case, benzoic acid,
p-toluic acid or 2,4-dimethylbenzoic acid was obtained and
identified by its melting point and neutral equivalent.
The monohydrofluorocarbons were identified by their physi¬
cal properties and molecular weight. The molecular weights


TABLE II
Fluorocarbon Aromatic Ketones
Pro-
ComDound cedure
Yield
B . o . °C
M.n.°C
nn25
d425
Theory Found
%C %C
Theory Found
%F %F
CF3C0C6H5 28
A
-
152
-
1.4583a
1.2791
a
-
-
-
C2F5C0C6H5
A
44.2
161.2
-
1.4245
1.372
48.2
47.9
42.5
42.1
c4f9coc6h5
B
32.8
188.5
-
1.3990
1.517
40.8
40.7
52.8
52.3
C5F11C0C6H5
B
43.6
204
-
1.3910
1.538
38.5
38.2
55.8
55.7
P—CFgCOCgH^CHg
A
32.4
179.2
3.5
1.4664
1.240
57.5
57.4
33.0
33.2
p-c2f5coc6h4ch3
A
43.8
181.4
4.0
1.4380
1.317
50 .4
50.4
39.9
39.8
p-CgF^COCgH^CHg
A
27.1
193
0.5
1.4230
1.384
46.2
46.1
46.2
45.9
P •"C^FgCOCgH^Hg
B
21.0
211
-16.5
1.4126
1.445
42.9
42.8
50.6
50.3
P-C5F11C0C6H4CH3
B
65.5
217.3
-13.5
1.4039
1.504
40.4
40.5
55.3
55.3
2,4-(CH3)2C6H3C0C5F1;l
C
81.0
217
-
1.4421
1.438
50.5
50.5
52.0
51.9
a Determined at 20°C


21
were obtained by Regnault’s method.
Reaction with phosphorous pentachloride—Tri-
fluoromethyl phenyl ketone reacts with phosphorous penta¬
chloride under reflux conditions to give 1,1,1-trifluoro-
2.2-dichloro-2-phenylethane with a yield of 48.5% 28. The
reaction of the ketones with phosphorous pentachloride was
attempted using a similar method of Cohen, Wolosinski and
O
Schewrer , whereby the ketone was refluxed in an excess of
phosphorous pentachloride for twenty-four hours, and after
cooling, treating the reaction mixture with a quantity of
acetone equivalent to the excess phosphorous pentachloride
to convert all the phosphorous pentachloride to phosphorous
oxychloride. Any products formed could then be fraction¬
ated directly from the phosphorous oxychloride.
A mixture of 20 g. (0.062 mole) of butforyl
phenyl ketone and 20.8 g. (0.10 mole) of phosphorous penta¬
chloride was refluxed for six hours at 190°. The mixture
was cooled and acetone was added slowly until there was no
excess phosphorous pentachloride. The mixture was then
poured slowly into a cold dilute solution of sodium carbon¬
ate. This solution was adjusted to a pH 7 with dilute hy¬
drochloric acid and steam distilled. The distillate was
extracted with ethyl ether, dried over anhydrous magnesium
sulfate and fractionated. There was recovered ethyl ether,
2.2-dichloropropane, a small forerun and unreacted butforyl


22
phenyl ketone.
This experiment was repeated using butforyl phenyl
ketone and p-propforyl tolyl ketone hut increasing the re¬
flux time to twenty-four hours; however, the desired di¬
chloride could not he produced.
2.4-Dinitrophenvlhydrazone s
Preparation—A solution of 2,4-dinitrophenylhy-
drazine was prepared hy adding 0.5 g. of 2,4-dinitro-
phenylhydrazine to 10 ml. of 50% sulfuric acid followed hy
the addition of 10 ml. of 95% ethanol. To this solution,
0.5 g. of ketone was added and was allowed to stand for one
week instead of the usual few hours. The crystals were
filtered and recrystallized three times from ethanol and
water. The highest yields of the 2,4-dinitrophenylhydra-
zones were obtained when a solution of 50% sulfuric acid
was used.
Semicarbazone
The semicarbazone was prepared by refluxing a so¬
lution of 1.5 g. of semicarbazide hydrochloride, 8 ml. of
water, 5 ml. of ethanol and 1.0 g. of ketone for one hour,
after which the solvents were removed under vacuum. The
solution must be refluxed at least one hour to obtain an
appreciable yield of semicarbazone. The semicarbazone was
recrystallized from ethyl ether after being decolorized


23
with activated charcoal.
The physical properties and analyses of the de¬
rivatives are reported in Table III.
Fluorocarbon Acid Anhydrides
Preparation—The acid anhydrides were prepared by
heating the.corresponding fluorocarbon carboxylic acid with
an excess of phosphorous pentoxide. The reaction may be
expressed as follows:
6RfC00H + P2O5 * 3(RfC0)20 -J-2H3PO4
All members of the series were fractionated directly from
the reaction mixture. The yield of acid anhydrides for all
members of the series was approximately quantitative.
Analysis--The acid anhydrides were hydrolyzed in
water and the resulting solution was titrated with stan¬
dard sodium hydroxide using phenolphthalein as the indica¬
tor.
For the fluoride analysis of the acid anhydrides,
the method under analysis of the fluorocarbon aromatic ke¬
tones was used.
The physical properties and analyses of the anhy¬
drides are listed in Table IV.
Aromatic Esters of Fluorocarbon Acids
Preparation—Several reactions were attempted in
order to prepare these compounds.


TABLE III
2.4-Dinitrophenylhydrazones of Fluorocarbon Aromatic Ketones
Compound
M.p. °C
Theory
%N
Found
foN
2,4-Dinitrophenylhydrazone
of
cf3coc6h5 28
94.5-95.5
-
-
2, 4-Dinitrophenylhydrazone
of
c2f5coc6h5
119-120
13.86
13.80
2,4-Dinitrophenylhydrazone
of
c4f9coc6h5
135-136
11.11
11.07
2,4-Dinitrophenylhydrazone
of
CgFuCOCgHg
144-145
10.11
10.06
2,4-Dinitrophenylhydrazone
of
P-CF3C0C6H4CH3
187-188
15.22
15.02
2,4-Dinitrophenylhydrazone
of
p-c2f5coc6h4ch3
162-163
13.40
16.61
2,4-Dinitrophenylhydrazone
of
p-c3f7coc6h4ch3
141-142
11.97
12.14
2,4-Dinitrophenylhydrazone
of
p-C^ qC0C6H4CH3
152-153
10.81
10.78
2,4-Dinitrophenylhydrazone
of
p-c5f11coc6h4ch3
160-161
9.86
9.81


TABLE IV
Fluorocarbon Acid. Anhydrides
Analysis
Compound
B.p. °C
nn25
d,2^
Theory
%F
Found
%F
(CF3C0)2033
39.5-40.5
1.269
1.490
-
-
(CgP500)80
71.5-72.0
1.273
1.571
76.16
75.86
(c3f7co)2o17
107-107.5
1.285a
1.665a
-
-
(c4f9co)2o
137-137.5
1.288
1.706
67.05
66.78
(c5f11co)2o
175-176
1.295
1.769
68.51
68.38
a Determined at 20°C


26
The first was the reaction between sodium phen-
oxide and trifluoroacetyl chloride.
C6H50Na -f CF3COCI -> CF3C00C6H5 -f- NaCl
In a 250 ml. three necked flask equipped with a
magnetic stirrer, thermometer, inlet tube and Dry Ice-
acetone Dewar type reflux condenser, were placed 58 g.
(0.5 mole) of anhydrous sodium phenoxide and 150 ml. of an¬
hydrous hexane. The mixture was heated to 50° with stir¬
ring, and 34.8 g. (0.26 mole) of trifluoroacetyl chloride
was slowly added beneath the surface over a period of two
hours. At the end of this time, the condenser was allowed
to warm to room temperature and the unreacted trifluoro¬
acetyl chloride was collected in a trap cooled in Dry Ice-
acetone. 26 g. (0.19 mole) of trifluoroacetyl chloride was
recovered. The reaction mixture was filtered and the resi¬
due washed with hexane. The filtrate was fractionated, and
after removal of hexane, yielded 9.8 g. of phenyl trifluo-
roacetate, b.p. 146.5-147.0°. This is a yield of 20.2%
based on trifluoroacetyl chloride used.
The second reaction attempted to prepare the es¬
ters was between phenol and trifluoroacetie acid with the
addition of a small amount of sulfuric acid as a catalyst.
In a 100 ml. flask were placed 27.4 g. (0.29 mole)
phenol, 26.5 g. (0.23 mole) trifluoroacetie acid and 8 ml.
concentrated sulfuric acid. The mixture was refluxed at


27
75° for three hours. Fractionation yielded 25.2 g. of tri-
fluoroaeetie acid, h.p. 73-74° and it was concluded that no
ester was produced.
The third reaction attempted to produce the esters
was the reaction between phenol and a large excess of tri-
fluoroacetic acid.
C6H50H +- x‘s CFgCOOH > CF3C00C6H54- CF3C00H*H20
OO
(azetrope)
In a 250 ml. flask were placed 50 g. (0.53 mole)
phenol with 114 g. (1.0 mole) trifluoroacetic acid and the
mixture refluxed at 75° for four hours. The reflux con¬
denser was replaced by a fractionating column and the mix¬
ture fractionated. The fractionation yielded 100 g. tri-
fluoroacetic acid, b.p. 73-74°, 6.9 g. azetrope of tri-
fluoroacetic acid and water, b.p. 104-105° and 14.6 g.
phenyl trifluoroacetate, b.p. 146-147°. This is a 15%
yield of ester based upon the amount of phenol used.
The fourth reaction was one between an acid anhy¬
dride and phenol. For the first member of the series, the
reaction may be expressed as follows:
C6H50H 4- (CF3CG)20 > CF3C00C6H5 4- CFgCOOH
In a 100 ml. flask were placed 11.2 g. (0.12 mole)
of phenol. 21 g. (0.1 mole) of trifluoroacetic anhydride
was added dropwise to the phenol with stirring. The mix¬
ture became warm with the addition of the anhydride. The


28
mixture was heated to 120° for one hour and fractionated.
Fractionation yielded 18.0 g. of phenyl trifluoroacetate,
h.p. 146-147°. This is a 95% yield based upon the trifluoro-
acetic anhydride used.
The other members of the series were prepared by
the same method. In the case of the preparation of phenyl
valerforate, after the anhydride was added to the phenyl,
the reaction mixture was fractionated to remove valerforic
acid and the residue washed three times with 50 ml. por¬
tions of hot water to remove any excess phenol. The re¬
maining ester was dried over anhydrous magnesium sulfate
and fractionated. This extra step was necessary since
phenyl valerforate and phenol have the same boiling point.
A thioester was also prepared using thiophenol and
trifluoroacetic anhydride.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois.
The physical properties and analyses of the esters
are summarized in Table IV.
Solubility—The esters were soluble in ethyl ether,
ethyl alcohol, benzene and dibutforyl oxide. The esters
were found slightly soluble in water, 50% sulfuric acid,
10% sodium bicarbonate and concentrated sulfuric acid.
Reaction with sodium hydroxide—With 10% sodium
hydroxide the esters underwent saponification. The rate of


TABLE V
Aromatic Esters of Fluorocarbon Acids
Compound
Yield 9
% B.p. °C
M.p. °C
»D85
T) 25
O4
Theory
ÚC
Found
°/oG
Theory Found
%H %H
CP3C00C6H5
95
146.5-147.0
-8.5
1.4183
1.276
50.54
51.00
2.65
2.49
C^FgCOOCgHg
94
153.0-153.5
-23.0
1.4078
1.324
45.01
45.26
2.10
2.03
CgFrjfCOOCgHg
96
162.5-163.0
-27.0
1.4156
1.350
41.39
41.42
1.74
1.69
c4f 9C00C6H5
92
179-180
-25.0
1.3888
1.438
38.84
39.00
1.48
1.47
c5f1iCooc6h5
95
196-197
-18.0
1.3715
1.533
36.94
36.81
1.29
1.18
cf3cosc6h5
92
174-175
-
1.4160
1.245
46.60
46.83
2.44
2.31


30
saponification decreased proportionately from phenyl tri-
fluoroacetate to phenyl caproforate.
Attempted reactions with the esters—Organic aro¬
matic esters are known to undergo a Fries rearrangement
when treated with aluminum chloride to produce ortho and
para hydroxyl ketones 4.
In a 200 ml. flask were placed 28.3 g. (0.15 mole)
of phenyl trifluoroacetate, 20 g. (0.15 mole) aluminum chlo¬
ride and 100 ml. anhydrous nitrobenzene. The mixture was
heated to 40° with stirring for twenty-four hours, then,
after cooling, poured in an ice-hydrochloric acid mixture
and extracted with ethyl ether. Upon fractionation, only
unreacted phenyl trifluoroacetate and the nitrobenzene was
obtained.
The experiment was repeated but increasing the
temperature to 120°; however, no reaction occurred and only
starting material was recovered.
Reaction with phosphorous pentachloride—A mixture
of 28.3 g. (0.15 mole) phenyl trifluoroacetate and 33.3 g.
(0.16 mole) phosphorous pentachloride was heated to reflux
for one week. Anhydrous acetone was added to decompose the
excess phosphorous pentachloride and the mixture was frac-
tioned. Fractionation yielded a small amount of 2,2-di-
chloropropane, phosphorous oxychloride, 20.8 g. of liquid
boiling at 75-76° (30 mm.) and a dark colored residue


31
remained. A small sample of this material boiling at 75-76°
(30 mm.) was observed to be partially soluble in water. The
water solution was acidic when tested with litmus. Bromine
water was added to the water solution and a white solid
formed. The solid, after recrystallization from alcohol and
water, was identified as tribromophenol, m.p. 95-96°.
This original liquid was added to 100 ml. of 20%
potassium hydroxide and steam distilled to remove phenol.
The steam distillate was separated and dried. Fractionation
yielded 15.8 g. of liquid boiling at 85-86° (30 mm.),
181-182° (760 mm.), nD30 1.4564, d430 1.392.
A sodium fusion on this liquid revealed chlorine
and fluorine to be present. An infra red spectrum on this
compound showed no absorption due to hydroxyl, carbonyl or
disubstituted benzene; however, it did contain an absorption
band corresponding to an aromatic ether.
The liquid was believed to be phenoxy-2,2,2-tri-
fluoro-l,l-dichloroethane. The molar refractivity for this
ether calculated from the density and refractive index is
47.88; the value calculated from the sum of atomic refrac-
tivities is 46.61.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for CgHgOCCl^CF^
Cl, 28.94. Found: Cl,29.00.


32
Solubility—The ether was soluble in ethyl alcohol,
ethyl ether and benzene. This ether was insoluble in water.
Reactions of phenoxy-2,2,2-trifluoro-l,l-dichloro-
ethane—To 3 g. (0.012 mole) phenoxy-2,2,2-trifluoro-l,l-
dichloroethane was added a solution of 7 g. (0.024 mole) po¬
tassium dichromate and 30 ml. of 50% sulfuric acid. The mix¬
ture was heated at 100° for twelve hours. At the end of this
time the mixture was cooled, poured on ice and extracted
with ethyl ether. After removal of the ethyl ether, 3 g. of
starting material were recovered.
To a 50 ml. Erlenmeyer flask containing 3 g. (0.012
mole) phenoxy-2,2,2-trifluoro-l,l-dichloroethane, were
added 20 ml. of 80% sulfuric acid and the mixture heated to
100° for twelve hours. There appeared to be less ether at
this time, and the heating was continued for an additional
twelve hours. The acid solution was dark in color and no
phenyl ether remained after this added period. The solu¬
tion was cooled and poured on ice, which yielded a clear
aqueous solution. This aqueous solution was extracted with
three 10 ml. portions of ethyl ether. The ethyl ether ex¬
tractions were combined, dried over anhydrous magnesium sul¬
fate and the ether removed by distillation. A small amount
of liquid remained possessing a phenolic odor. Bromination
of this liquid yielded a tribromophenol, m.p. 94-95°, which,
when mixed with an authentic sample, gave no melting point


33
depression.
Friedel-Crafts Alkylation
Fluorocarbon halides—The fluorocarbon iodides
3
were prepared using the method of Crawford and Simons
whereby silver salts of the fluorocarbon acids are decom¬
posed in the presence of iodine.
The ethforyl chloride was obtained from the E. I.
duPont de Nemours and Company.
Attempted alkylation with ethforyl chloride—In a
500 ml. three necked flask equipped with a stirrer, gas in¬
let tube and Dry Ice-acetone Dewar type reflux condenser,
were placed 250 ml. (3.21 moles) benzene and 27 g. (0.203
mole) aluminum chloride. The mixture was heated to reflux
and 50 g. (0.203 mole) ethforyl chloride were added over a
period of four hours. At the end of this time the mixture
was cooled and 49.5 g. of ethforyl chloride were recovered.
Attempted alkylation with propforyl iodide—This
experiment was repeated except using 60 g. (0.203 mole) of
propforyl iodide in place of the ethforyl chloride. With
the initial addition of the iodide, the mixture turned dark
in color. The heat was discontinued and the addition of
iodide regulated to keep the mixture at 60°. Hydrogen
iodide was liberated during the entire period of addition.
When the hydrogen iodide ceased, the mixture was cooled and
poured on an ice-hydrochloric acid solution. Two layers


34
formed and the benzene layer was separated and steam dis¬
tilled. During the steam distillation free iodine was
liberated. The organic distillate was separated, dried
over anhydrous magnesium sulfate and fractionated. Frac¬
tionation yielded 40 g. propforyl iodide, benzene and 9.6 g.
iodobenzene. There was a large amount of tarry residue in
the steam distillation flask. Both the residue and the acid
solution contained fluorine.
Aromatic Metallic Reactions
Phenyl magnesium iodide with propforyl iodide—In
a three-necked flask equipped with thermometer, condenser
and stirrer, were prepared 50 g. (0.22 mole) of phenyl mag¬
nesium iodide in 300 ml. of anhydrous ether. To this solu¬
tion 39.6 g. (0.1 mole) of propforyl iodie were added drop-
wise over a period of two hours. The mixtured turned
orange, then dark red and stirring was continued for eight
additional hours. The mixture was then hydrolyzed with
250 ml. of lce-10% hydrochloric acid solution. The ether
layer was separated and the water layer extracted with
three 20 ml. portions of ethyl ether. The ether layer and
extracts were combined, dried with anhydrous magnesium sul¬
fate and fractionated. 10.6 g. hexforane, b.p. 57-58°, ben¬
zene, iodobenzene and a small amount of high boiling pot
residue were obtained. This residue was found to contain
fluorine but could not be rectified or identified as the


35
quantity was very small.
Phenyl sodium with propforyl iodide—Phenyl sodium
was prepared from chlorobenzene, sodium and toluene accord¬
ing to standard organic procedures. To a solution of 25 g.
(0.25 mole) of phenyl sodium in 200 ml. of toluene were
added dropwise 20 g. (0.198 mole) of propforyl iodide. The
mixture turned light red and stirring was continued at room
temperature for twenty-four hours. The mixture was neutral¬
ized with 10% hydrochloric acid and extracted with ether.
The ether extractions were dried over anhydrous
magnesium sulfate and fractionated. Fractionation yielded
ether, toluene and 9.2 g. of material boiling from 110-184°.
There were no plateaus in this fractionation. A sodium fu¬
sion on this material revealed fluorine, chlorine and iodine
to be present. After fractionation there remained a tarry
pot residue which could not be rectified. A sodium fusion
on this residue revealed fluorine, chlorine and iodine.
Phenyl lithium with propforyl iodide—Phenyl lith¬
ium was prepared from bromobenzene and lithium metal in an¬
hydrous ethyl ether by standard procedures To a solu¬
tion of 18 g. (0.214 mole) of phenyl lithium in 250 ml. of
anhydrous ethyl ether cooled to 0°, were added 20 g. (0.198
mole) of propforyl iodide. The mixture turned dark red and
stirring was continued for twenty-four hours while the
flask was maintained at 0-5°. Cold dilute hydrochloric


36
acid was then added slowly until the mixture was acidic. The
ether layer was separated and the water layer was extracted
with three portions of ethyl ether. The water layer was
tested and found to contain fluoride ion. The ether layer
and extractions were combined, dried with anhydrous magne¬
sium sulfate and fractionated. After removal of the ethyl
ether, fractionation yielded bromobenzene, b.p. 156-157°,
and 7.1 g. of material with a boiling range of 158-168°.
There was a considerable amount of tarry residue left,
which, upon steam distillation, yielded 6.2 g. of a white
crystalline solid with a m.p. of 75-76°. This solid was
identified as diphenyl, and when mixed with an authentic
sample, gave no melting point depression. The material boil¬
ing at 158-168° contained fluorine and bromine but could not
be identified. The bromobenzene was from the excess used in
the preparation of phenyl lithium.
p-tolyl lithium with propforyl iodide—p-tolyl
lithium was prepared from p-bromotoluene by the same method
as in the previous experiment. 20 g. (0.198 mole) of prop¬
foryl iodide were added to a solution of 25 g. (0.255 mole)
of p-tolyl lithium in 200 ml. of anhydrous ethyl ether. The
solution was kept in an ice bath, and the propforyl iodide
was added dropwise over a period of two hours. The mixture
turned light orange and stirring was continued for twenty-
four hours. Dilute hydrochloric acid was added until the


37
mixture was acidic and the two layers separated. The water
layer was extracted with ethyl ether and the ether layer and
extracts combined, dried over anhydrous magnesium sulfate
and fractionated. After removal of the ethyl ether, frac¬
tionation yielded p-bromotoluene, 1.2 g. of material boil¬
ing at 106-107° (49 mm.), 190-192° (760 mm.), 8.6 g. at
108-115° (49 mm.) and 4.2 g. of a material that solidified
in the receiver. A dark colored residue remained in the
flask. The material boiling from 108-115° (49 mm.) could
not be identified. A sodium fusion revealed fluorine and
iodine to be present. The material that solidified was
identified as p-iodotoluene, b.p. 211-212°, m.p. 35-36°.
The colored residue was steam distilled and yielded 3.2 g.
of p,p’-bitolyl, m.p. 121°. The material that distilled
at 106-107° (49 mm.) was thought to be p-propforyltoluene
after a sodium fusion revealed fluorine as the only halogen
present. An infrared spectrum was obtained on the liquid,
and, after comparison with known para substituted toluene
derivatives, it was assumed that the compound was para
substituted. An analysis gave C. 46.31, H. 2.98; calculated
for CH3C6H4C3P7 C. 46.18, H. 2.69.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois.
o-chloromercuriphenol with fluorocarbon iodides—
A glass vial of 120 ml. capacity was constructed from Vycor


38
#7910 glass and. attached to a graded seal of Yycor to Pyrex
in order to provide a convenient method of sealing. In this
tube were placed 33 g. (0.1 mole) o-chloromercuriphenol and
40 g. (0.202 mole) methforyl iodide. The tube was sealed
and shaken under a 2540 X ultraviolet lamp for twenty-four
hours. The white solid turned red during this irradiation.
At the end of this time the vial was cooled in Dry Ice-ace¬
tone and 26.2 g. of methforyl iodide distilled into a trap.
The vial was sealed to an all glass vacuum system and any
volatile material was transferred to a trap cooled in
liquid air. The vial was removed and the contents washed
out with hexane. After filtering and evaporating the hexane,
4.3 g. of o-iodophenol remained, m.p. 43-44°. The residue
was extracted first with water and then with ether. The
water extract contained mercuric chloride, the ether ex¬
tract contained mercuric iodide and a dark residue remained.
The residue was extracted with ethyl alcohol to remove
o-chloromercuriphenol. A sodium fusion on the remaining
material disclosed fluorine and chlorine present hut further
identification was not possible. The trap cooled in liquid
air was removed from the vacuum system and allowed to warm
to room temperature. A solid remained in the trap, which,
after distillation, yielded 2.3 g. of o-methforylphenol,
b.p. 145-146, m.p. 44-45°. Bromination gave a white solid,
m.p. 48-49°. Jones reports for o-methforylphenol,


39
b.p. 147, m.p. 46°, and for the dibromomethforylforylphenol,
m.p. 50°. This reaction may he expressed as follows:
o-H0C6H4HgCl+ CF3I » o-HOC6H4I -h o-HOCgl^CFg +* Hgl2 + HgCl2
o-chloromercuriphenol and propforyl iodide—The
above experiment was repeated using propforyl iodide. A
mixture of 33 g. (0.1 mole) o~chloromercuriphenol and 60 g.
(0.206 mole) propforyl iodide was added to a 250 ml. Vycor
vial. The vial was sealed and exposed to ultraviolet light
for forty-eight hours. The vial became coated with a layer
of red solid. The vial was opened and 48 g. propforyl
iodide was recovered. The vial was sealed to a vacuum sys¬
tem and any volatile material removed. The solid material
in the vial was extracted with hexane and filtered. Evapo¬
ration of the filtrate did not yield o-iodophenol as in the
previous experiment. The residue was extracted with water,
ethyl ether and alcohol. The three extractions yielded
mercuric chloride, mercuric iodide and o-chloromercuriphenol,
respectively. A very small amount of dark residue remained.
After the liquid air trap was removed and the contents
warmed to room temperature, a liquid remained. Distillation
yielded 3.1 g. of a liquid boiling at 174-175°. The liquid
is assumed to be o-propforylphenol. This compound turns
dark in color after exposure to air and light.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for O-C3F7C0H4.OH;


40
C. 27.49, H. 1.92. Found: C. 27.53, H. 2.21.
Solubility—o-propforylphenol is soluble in ethyl
ether, alcohol and benzene. It is only slightly soluble in
water.
Aromatic Fluorocarbon Ethers
Potassium phenoxide with alkforyl iodides—In a
200 ml. copper pressure vessel were placed 66 g. (0.5 mole)
anhydrous potassium phenoxide and 50 g. (0.392 mole) meth-
foryl iodide. The vessel was heated to 150° for twelve
hours. At the end of this time the vessel was cooled and
opened. Only unreacted starting material was recovered.
This experiment was repeated using 66 g. (0.5 mole)
potassium phenoxide, 200 ml. anhydrous acetone and 50 g.
(0.392 mole) methforyl iodide in a 800 ml. copper pressure
vessel. The vessel was heated to 150° with rocking for
twelve hours. At the end of this time the vessel was cooled
and vented into a liquid air trap. There was collected 21
g. of material, which, when fractionated in a low tempera¬
ture column, had a boiling point of -85° to -83° and a
molecular weight of 69.6. On this basis it is assumed to be
fluoroform with a theoretical molecular weight of 70. Acetone,
unreacted starting material and a small amount of phenolic
tars remained in the reaction vessel.
When this experiment was performed with propforyl
iodide, 1-hydropropforane was obtained, indicating the


41
reaction proceeded in the same manner as the previous ex¬
periment.
Potassium phenoxide with dihromodifluoromethane—
In a 200 ml. copper pressure vessel were placed 33 g. (0.25
mole) anhydrous potassium phenoxide and 42 g. (0.2 mole)
dihromodifluoromethane. The vessel was heated to 100° with
rocking for twenty-four hours. At the end of this time the
vessel was cooled and opened. Starting material was the on¬
ly material recovered.
In a 500 ml. three necked flask equipped with a
magnetic stirrer, a Dry Ice-acetone cooled reflux condenser
and a gas inlet tube, were placed 74 g. (0.56 mole) anhy¬
drous potassium phenoxide and 400 ml. of anhydrous acetone.
This mixture was stirred and dihromodifluoromethane was
huhhled through the solution. After five minutes the mixture
turned red and the temperature rose rapidly to 55°. The ad¬
dition of dihromodifluoromethane was then regulated to keep
the temperature helow 50° until 118 g. (0.56 mole) were
added. The mixture was stirred for an additional twelve
hours at room temperature. At the end of this time a mix¬
ture of acetone and excess dihromodifluoromethane was dis¬
tilled from the solution. After removal of 300 ml. of
liquid, an equal volume of water was added and the mixture
was steam distilled. The distillate separated into two
layers. The lower layer was separated from the upper


42
aqueous layer, dried over anhydrous magnesium sulfate and
fractionated. Fractionation yielded 13.2 g. of difluoro-
methyl phenyl ether distilling at 60-67° at 30 mm., ISO-
MO0 at 763 mm., d254 1.171, n25D 1.4460. The molar re-
fractivity of difluoromethyl phenyl ether calculated from
the density and refractive index is 32.58; the value calcu¬
lated from the sum of atomic refractivities is 32.35.
To the excess dibromodifluoromethane and acetone
distilled from the original reaction mixture, two liters
of cold water were added and the dibromodifluoromethane
which separated was collected, dried and used for subsequent
experiments. The amount of dibromodifluoromethane recovered
was 50 g. The yield of difluoromethyl phenyl ether, based
on the dibromodifluoromethane used, was 28.3%.
This experiment was repeated substituting phenol
and solid potassium hydroxide for potassium phenoxide. This
change resulted in a decrease of the yield to 16.3%.
Solubility—Difluoromethyl phenyl ether is a color¬
less liquid with a very pungent odor, soluble in ethyl ether,
ethyl alcohol, benzene and this ether is insoluble in water.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for CgHgOCFgH;
C. 58.33; H. 4.20. Found: C. 58.37, H. 4.48.
Degradation—To 5 g. (0.035) mole) difluoromethyl
phenyl ether in a 50 ml. Erlenmeyer flask were added 10 ml.


43
of 50% sulfuric acid. As soon as the flask was shaken a
violet semi-solid mass was formed and hydrogen fluoride
was liberated. After the evolution of hydrogen fluoride
subsided, the mixture was neutralized with 20% sodium hy¬
droxide solution and filtered. The residue could not be
readily identified. The filtrate, however, after acidifi¬
cation and extraction with ethyl ether, yielded 1.1 g. of
phenol.
To a 50 ml. flask containing 2 g. (0.087 mole)
of sodium metal in 20 ml. of anhydrous ethyl ether, were
added 5 g. (0.035 mole) difluoromethyl phenyl ether. The
mixture was refluxed for twelve hours, after which the ex¬
cess sodium was slowly decomposed by adding ethyl ether
saturated with water. After acidifying the mixture with 20%
hydrochloric acid, the ether layer was separated, dried and
distilled, yielding 2.1 g. of unreacted difluoromethyl
phenyl ether and 1.6 g. of phenol. The dilute hydrochloric
acid layer contained a large amount of fluoride ion.


DISCUSSION
Organic Aromatic Ketones
Organic aromatic ketones have heen known and used
for many years. They can he prepared hy various methods.
The following equations represent some methods which are
applicable to all members of the group if yield is not of
primary importance.
1. C6H5CH0HR GOL» C6H5C0R -I- H20
2. C6H5MgX •+ RCOOEt g-ther^ c6H5C0R + EtOMgX
3. CgHgMgX ■+ RCN » C6H5C(:N Mg X)R
—» C6H5C0R -+ MgX2 + NH4X
4. C6H5CC12R H20 C6H5C0R +- 2HC1
PbO
5. CgHg H- RCOC1 Algia» CgHgCOR +- HC1
6. C6H5MgX -+• RCOC1 e-^.er> C6H5C0R +- MgXCl
7. C6H6-+• (RC0)20 43-PI3.» c6H5C0R 4- RCOOH
8. C6H50C0R Algia.» 0-H0C6H4C0R and p-H0C6H4C0R
The most widely used reaction for aromatic com¬
pounds is the Friedel-Crafts method listed as equation 5 or
7 above. The yields for the most part are very good.
44


45
Fluorocarbon Aromatic Ketones
OQ
Simons and Rambler utilized this reaction in
preparing the first fluorocarbon aromatic ketone, tri-
fluoroacetophenone. They found in a Friedel-Crafts acyla¬
tion of benzene with a fluorocarbon acid chloride that
there were no side reactions involving the fluorine in the
trifluoromethyl group. This was unusual in that Henne and
Newman observed that aluminum chloride reacts with or¬
ganic fluorides to produce aluminum fluoride and an organic
chloride.
Trifluoroacetophenone undergoes a haloform type
reaction in the presence of dilute potassium hydroxide to
yield fluoroform and potassium benzoate.
C6H5COCF3 -+- 10%K0H > CF3H + C6H5C00K
This reaction is unusual for an aromatic ketone
but is frequently encountered with aliphatic ketones. In a
similar reaction of aliphatic ketones, trifluoroacetophe¬
none formed a sodium bisulfite addition complex.
OQ
Simons and Rambler also found that a 2,4-dini-
trophenylhydrazone could be readily formed by standard pro¬
cedures and as in organic ketones, the carbonyl oxygen
could be replaced by chlorine, thus trifluoroacetophenone
reacted with phosphorous pentachloride under reflux condi¬
tions to form l,l,l,-trifluoro-2,2-dichloro-2-phenylethane.


46
Since trifluoroacetophenone had some properties
found in organic analogs and some properties peculiar to
aromatic ketones, it was decided to investigate other fluo¬
rocarbon aromatic ketones utilizing a Priedel-Crafts reac¬
tion and including other aromatic nuclei as well as other
fluorocarbon acid chlorides.
Since only trifluoroacetyl chloride and but-
foryl chloride x' had been previously prepared, it was
necessary to prepare three new fluorocarbon acid chlorides.
The reaction between the fluorocarbon carboxylic acids and
phosphorous pentachloride was the method used.
Rf COOH -4- PC15 » Rf COCI -+* P0C13 + HC1
The yields of the fluorocarbon acid chlorides were
approximately quantitative for all acids used. The ketones
were prepared using aluminum chloride or aluminum bromide
as the acylating agent in the Friedel-Crafts reaction and
an excess of the aromatic compound as the solvent. The pro¬
cedures were modified to facilitate using the different
acid chlorides.
The use of benzene and toluene as the aromatic
nuclei did not have any significant effect on the yield of
the ketones; however, in the case of toluene there was only
one isomer prepared. In every instance only the para ke¬
tone was produced and no trace of an ortho ketone could be
detected. The one experiment in which aluminum bromide was


47
used resulted in almost doubling the yield of ketone.
The ketones were found to undergo a haloform type
splitting reaction with concentrated base to give a mono-
hydrofluorocarbon and a salt of an aromatic acid. This may
be expressed by the following equation:
ArCGRf 4- KOI! » ArCOOK 4- RfH
This degradation served as a convenient method for proof of
the structure of the ketones. The aromatic acids obtained
upon acidification of the metallic salt did not require any
further purification.
In the preparation of the 2,4-dinitrophenylhydra-
zones it was found that the standard organic procedures did
not give any derivatives. It was necessary to modify the
standard procedure by increasing the sulfuric acid concen¬
tration and the reaction time.
Sodium bisulfite addition products could not be
formed; hox^ever, Simons and Rambler disclosed that the
first member of this ketone series did form a bisulfite
addition product, which, upon reaction with sulfuric acid,
regenerated the ketone.
They also reported that the carbonyl oxygen could
be replaced by chlorine by refluxing trifluoroacetophenone
with phosphorous pentachloride. This reaction could not be
performed with any of the other ketones.


48
It appears that trifluoroacetophenone, the first
member of the series, undergoes reactions that are quite
different from the rest of the series. Trifluoroacetophe-
none undergoes several reactions of aliphatic organic ke¬
tones, but the higher members of the series are quite inert
except to alkali.
Aromatic Esters of Fluorocarbon Acids
In organic chemistry there are several types of
aromatic esters that can be prepared. They are represented
by the following equations:
1. ArCOOH â– + ROH _> ArCOOR
2. ArOH -+- RCOOH RCOOAr
3. ArCOOH ~h ArOH » ArCOOAr
In fluorocarbon chemistry there have not been any
alcohols prepared of the type RpOH, so aromatic esters of
fluorocarbon acids are the only type of aromatic ester pos¬
sible. This type is represented by equation 2 above.
The organic esters, RCOOAr, are usually prepared
by one of the following methods. The preparation of phenyl
acetate will serve as examples.
1. c6h5oh -i- ch3cooh ch3cooc6h5 + h2o
2. CgHgONa-h CHgCOCl » CHgCOOCgHg + NaCl
3. c6h5oh + (ch3co)2 —» ch3cooc6h5 + CH3C00H
The first and second reactions are the methods most
generally used. This type of organic aromatic esters has


49
not "been used in large quantities. The chief use 4 of
these esters is in the preparation of hydroxyl aromatic ke¬
tones by the Pries reaction. This reaction is a variant of
the Friedel-Crafts method of acylation. It consists of the
conversion of an ester of a phenol to the corresponding
ortho or para hydroxy ketone, or a mixture of both, hy
treatment with aluminum chloride.
C6H50C0R o-H0C6H4C0R and p-HOCgH4COR
This procedure is convenient and of wide applica¬
bility when an organic aromatic compound cannot he acylated
hy any other method.
Several methods were attempted to prepare the aro¬
matic esters of fluorocarbon acids; however, only one gave
favorable results.
The reactions and yields in the case of trifluo-
roacetic acid were as follows:
1. C6H50Na 4* CF3COCI â–º CF3C00C6H5 -1- NaCl
20% yield
2. CgHgOH 4 CFgCOOH SgSO^. n0 Reaction
3. C6H50H 4 x* s CF3COOH » CF3C00C6H5 -j-
15% yield
CF3COOH H20 (azetrope) 33
4. C6H50H 4- (CF3C0)20 > CF3C00C6H5 4 CF3COOH
95% yield


50
The esters of the other fluorocarbon acids were
prepared by the last method and the yields averaged close to
95%.
It is unusual that the first two methods do not
give satisfactory results, as these methods are used exten¬
sively in organic chemistry and in fluorocarbon chemistry
to prepare aliphatic esters of fluorocarbon acids.
The esters were only slightly soluble in water, 10%
sodium bicarbonate and sulfuric acid. They were not hy¬
drolyzed by heating with mineral acids, but underwent sa¬
ponification with 10% sodium hydroxide. The resistance to
hydrolysis with mineral acids is in direct contrast to or¬
ganic esters and aliphatic fluorocarbon esters which are
easily hydrolyzed in the presence of mineral acids. The
rate of saponification decreased proportionately from
phenyl trifluoroacetate to phenyl caproforate.
The esters did not undergo the Fries reaction as
do the organic analogs to produce ortho and para hydroxy ke¬
tones.
Phenyltrifluoroacetate reacted with phosphorous
pentachloride to produce an <=*,<*. -dichloro ether, phenoxy-
2,2,2-trifluoro-l,l-dichloroethane.
CF3C00C6H5 -+ PC15 » CF3CC120C6H5 4- P0C13
This reaction demonstrates the stability and an unusual
property of the aromatic esters of fluorocarbon acids.


51
Organic esters react with phosphorous pentachlo-
ride to form organic chlorides and acid chlorides.
RCOOR1 ■+ PC15 » RC0C1 -f R'Cl 4- P0C13
Phenoxy-2,2,2-trifluoro-l,l-dichloroethane is a
very stable compound that can he distilled at atmospheric
pressure without discoloring and resists the action of
chromic acid at 100°. The ether, however, was attacked by
prolonged treatment with hot 80% sulfuric acid to yield
phenol.
Alkforvi Aromatic Compounds
The preparation of alkforyl aromatic compounds has
been limited to benzotrifluoride and ethforylbenzene. Since
this type of compound is expected to have a large future po¬
tential, an attempt was made to prepare the higher members
of the alkforyl aromatic compounds or their derivatives.
The first attempts to prepare the alkforyl aro¬
matic compounds were adaptations of organic chemical re¬
actions. Previous experiments have shown that Friedel-
Crafts acylation works very well in fluorocarbon chemistry,
so a Friedel-Crafts alkylation reaction using fluorocarbon
halides and aromatic compounds might produce the desired
final product.
Ethforyl chloride failed to react with benzene in
a Friedel-Crafts reaction. This is not surprising, as
ethforyl chloride is a very inert chemical that does not


52
enter into chemical reactions like organic chlorides.
The reaction of propforyl iodide with benzene
using aluminum chloride as a catalyst leads to iodobenzene,
iodine, inorganic fluoride and fluorine containing tars. It
appears that the fluorocarbon iodides react in an opposite
manner to the organic halides. It is believed that under
ionic reaction conditions, the fluorocarbon iodides form
R^ and I+, whereas, organic iodides form R+ and I”. This re¬
action lends some support to this idea.
The reaction of an aromatic Grignard compound and
propforyl iodide yielded upon acidification only hexforane
and iodobenzene in significant quantities. The reaction
probably proceeds through an exchange to produce a fluoro¬
carbon Grignard reagent followed by coupling with excess
fluorocarbon iodide. It may be expressed as follows:
C6H5MgI + C3F7I > C6H5I -h C3F7MgI C3E3X»
C6F14 + Mgl2 + C6H5I
The product obtained from phenyl sodium and prop¬
foryl iodide could not be identified, inasmuch as it had a
wide boiling range. Some propforylbenzene might have been
prepared, but the excess chlorobenzene used in preparing
the phenyl sodium made separation impossible.
When phenyl lithium was allowed to react with
propforyl iodide, there was a considerable amount of di¬
phenyl produced indicating coupling between aromatic nuclei


53
occurred. The fluorine containing fraction obtained could
not he separated from bromobenzene.
Upon substituting p-tolyl lithium for phenyl
lithium, the coupling reaction was decreased and it was pos
sible to isolate a small sample of an alkforyl aromatic com
pound. By infrared spectra comparison with known substi¬
tuted toluene derivatives, it is assumed that the propforyl
toluene is para substituted; however, in the absence of
chemical reactions, this infrared spectra data cannot be
used for absolute proof of structure.
The reaction between fluorocarbon iodides and
o-chloromercuriphenol yields o-alkforylphenols. This reac¬
tion is similar to a reaction used in organic chemistry to
prepare o-iodophenol.
o-H0C6H4HgCl 4- I2 „ o-H0C6H4I + Hgl2 + HgCl2
When methforyl iodide was used, both o-methforyl-
phenol and o-iodophenol were obtained; however, when prop¬
foryl iodide was used with o-chloromercuriphenol, only
o-propforylphenol was prepared and there was no trace of
o-iodophenol.
This reaction works well for both alkforyl iodides
used; however, during the course of the reaction, the vial
becomes coated with mercuric iodide and the reaction is no
longer activated by the ultraviolet light. This necessi¬
tates the frequent changing of vials if any significant


54
quantity of product is desired.
Aromatic Fluorocarbon Ethers
There have been no organic fluorocarbon ethers pre¬
pared in which the fluorocarbon group contained only fluo¬
rine; however, ethers have been prepared where the fluoro¬
carbon group contained chlorine atoms or hydrogen atoms.
Compounds of the type R^,ORf where R^ are fluorocarbon radi¬
cals are very stable and are completely void of the chemical
properties associated with organic ethers of the type ROR.
It was desired to produce an aromatic fluorocarbon
ether, since this compound might be very stable, and as such,
might become a very useful starting material.
The reaction between potassium phenoxide and a
fluorocarbon iodide was attempted to produce such an ether.
The only fluorine containing material obtained was fluoro-
forrn in the case of methforyl iodide and 1-hydropropforane
when propforyl iodide was used. The potassium phenoxide in
acetone reacts in a manner similar to potassium hydroxide
when treated with a fluorocarbon iodide. Banus, Emeleus
and Haszeldine 1 report the reaction of methforyl iodide with
solutions of potassium hydroxide in alcohol, acetone or
ethyl ether yielded fluoroform.
The second reaction attempted to produce the
desired type of ethers was between potassium phenoxide
and dibromodifluoromethane. It was hoped that phenyl


55
bromodifluorornethy1 ether could he produced and the bromine
atom replaced with fluorine to give trifluoromethyl phenyl
ether; however, the reaction between potassium phenoxide and
dibromodifluoromethane in acetone gave difluoromethyl phenyl
ether. Since there was no reaction between potassium phen¬
oxide and dibromodifluoromethane when heated in the absence
of a solvent or between acetone and dibromodifluoromethane,
it is believed that the hydrogen present in the difluoro¬
methyl group came from the acetone solvent. These reac¬
tions may be expressed as follows:
C6H50K -f- CFgBrg —— No Reaction
CF2Br2 + CH3GOCH3 £— No Reaction
CgHgOK 4- CF2Br2
CH3COCH3
C6H50CP2H
This ether is the only stable one containing the
QO
difluoromethyl group. Swarts , together with Henne and
tv
Smook , have prepared ethyl difluoromethyl ether but report
it is very unstable, and both had difficulty obtaining even
the boiling point of this compound.
Difluoromethyl phenyl ether decomposes in the pres¬
ence of mineral acids and is unaffected by alkalis.
Proof of the structure of difluoromethyl phenyl
ether was difficult, since there were no known reactions
available. It was necessary to cleave the ether to produce
phenol, in order to prove the CgHgO group was present. Both
sulfuric acid and sodium metal were satisfactory for this


56
purpose. No reactions could "be devised to determine the
CF^H or CFgHO group. The use of the molar refraction, car¬
bon and hydrogen analyses, together with the degradation to
phenol, were considered proof of the structure of the ether.
Conclusions
As can he seen from the previous discussion, fluoro
carbon aromatic compounds differ widely from their organic
analogs. It is usually the exception rather than the rule
that applies to fluorocarbon aromatic compounds when the
rules and procedures of organic chemistry are utilized. Be¬
cause of this, it is necessary to accumulate a large amount
of experimental data, in order to formulate organized rules
applicable to fluorocarbon aromatic compounds.
It is with this view in mind that the preceding
work is presented, in the hope that the experimental re¬
sults will contribute to the chemistry of fluorocarbon aro¬
matic compounds, and as such, will lead to the organization
and understanding of fluorocarbon chemistry.


SUMMARY
The preparation and some of the physical and chemi¬
cal properties of thirty-two previously unreported fluoro¬
carbon compounds is presented. Ten distinct molecular
species are represented by these compounds. They may be
summarized as follows:
1. A series of fluorocarbon aromatic ketones were
prepared by a Friedel-Crafts reaction between a fluorocarbon
acid chloride and an aromatic compound. Some of their chemi¬
cal and physical properties were determined. With benzene
the ketones were of the type:
0
rcc6h5
The compounds prepared were for R equal to the following:
C2f5C4F9~ 311(1 C5F11“*
Using toluene as the aromatic compound, the ketones
were of the type:
0
II
p-rcc6h4ch3
The compounds prepared were for R equal to the following:
CF3“> C2F5"' C3F7"' C4F9~ 311(1 C5F11“*
57


58
Using meta-xylene as the aromatic compound and
caproforyl acid chloride, the ketone was:
0
2,4-(CH3)2c6H3Cc5P11
The ketones did not entirely follow the first mem¬
ber of the series, trifluoroacetophenone, in their chemical
reactions. The ketones split in the presence of dilute
alkali to form a metallic salt of an organic acid and a
monohydrofluorocarhon. They formed 2,4-dinitrophenylhy-
drazones as does trifluoroacetophenone, "but a sodium bisul¬
fite addition complex could not be prepared and the car¬
bonyl oxygen could not be replaced by chlorine as does the
first member of the series, trifluoroacetophenone.
2. A series of 2,4-dinitrophenylhydrazones were
prepared and some of their physical properties determined.
These compounds have the following structure:
2,4-(N02)C6H3NHN = R
The compounds prepared were for R equal to the following:
C2F5CC6H5' C4F9CC6H5> C5F11CC6H5' P-^gCCgH^Hg,
p-C2F5CC6H4CH3, p-C3F7CC6H4CH3, p-C4F9CC6H4CH3and
P"C5F11CC6H4CH3 *
3. A series of aromatic esters of fluorocarbon
acids were prepared and some of their chemical and physical
properties determined. The esters were of the following
type:


59
O
II
rcoc6h5
The compounds prepared were for R equal to the following:
CF3-, CgFg-, C3F7-, C4F9- and CgF]^-.
These compounds were found to he resistant to acid hydrol¬
ysis hut saponified readily hy dilute alkali. The first
member of the series reacted with phosphorous pentachloride
replacing the carhonyl oxygen with two chlorine atoms and
forming an e<,oc-dichloro phenyl ether.
4. An aromatic thio ester of trifluoroacetic acid
was prepared and some of its physical properties determined.
It is believed to have the following structure:
0
cf3csc6h5
5. Phenoxy-2,2,2-trifluoro-l,l-dichloroethane was
prepared and some of its physical and chemical properties
determined. This phenyl ether was found to he very stable,
and only after prolonged treatment with 80% sulfuric acid
did the ether split to phenol.
6. Difluoromethyl phenyl ether was prepared and
some of its physical and chemical properties determined. At
the present time this ether is the only stable difluoro¬
methyl ether.
7. p-propforyl toluene was prepared and some of
its physical properties determined.


60
8. o-propforyl phenol was prepared and some of its
physical and chemical properties determined.
9. Propforic, valerforic and caproforic acid chlo¬
rides were prepared. Some of their physical properties and
uses in Friedel-Crafts acylations are reported.
10. Propforic, valerforic and caproforic acid an¬
hydrides were prepared. Some of their physical properties
were determined and their use in esterification of aromatic
phenols is reported.


BIBLIOGRAPHY
1. Banus, J., Emeleus, H. J., and Haszeldine, R. N., J.
Chem. Soc. 60, (1951).
2. Cohen, S. G., Wolosinki, H. T., and Scheurer, P. J.,
J. Am. Chem. Soc. 71, 3439 (1949).
3. Crawford, G. H., and Simons, J. H., J. Am. Chem. Soc.
75. 5737 (1953).
4. Fuson, R. C., "Advanced Organic Chemistry", John Wiley
and Sons, Inc., New York, 1950, p.344.
5. Grosse, A. V., and Cady, G. H., Ind. Eng. Chem. 39.
367 (1947).
6. Henne, A. L., and Newman, M. S., J. Am. Chem. Soc. 60.
1697 (1938).
7. Henne, A. L., and Smook, M. S., J. Am. Chem. Soc. 72.
4378 (1950).
8. I. G. Farbenind. A.-G., French Patent 745,293
(May 8, 1933).
9. I. G. Farbenind. A.-G., German Patent 575,593
(May 22, 1933).
10. Jones, R. G., J. Am. Chem. Soc. 69. 2346 (1947).
11* Ibid.. 70. 143 (1948).
12. Kimball, R. H., and Tufts, L. E., Anal. Chem. 19,
150 (1946).
13. Kinetic Chemicals, Inc., Brit. Patent 391,168
(April 12, 1933).
14. Lebeau, P., and Damiens, H., Compt. rend. 183.
1340 (1926).
61


62
15. MeBee, E. T., and Bolt, R. 0., Ind. Eng. Chem. 39,
412 (1947).
16. McBee, E. T.. and Pierce, 0. R., Ind. Eng. Chem. 39.
397 (1947).
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
Minnesota Mining and Manufacturing Company, Technical
Bulletin, "Heptafluorobutyric Acid” (1949).
Moissan, H., Compt. rend. 102. 1453 (1886).
Nes, W. R., and Burger, A., J. Am. Chem. Soc. 72.
5409 (1950).
Renoll, M. W., J. Am. Chem. Soc. 68, 1159 (1946).
Renoll, M. W., U. S. Patent 2,414,330 (January 14, 1947).
Ruff, 0., and Bretschneider, 0., Z. anorg. allgem.
Chem. 210. 173 (1933).
Ruff, 0., and Keim, R., Z. anorg. allgem. Chem. 192.
249 (1930).
Shirley, D. A., ''Preparation of Organic Intermediates”,
John Wiley and Sons, Inc., New York, 1951, p.260.
Simons, J. H. and Block, L. P., J. Am. Chem. Soc. 59.
1407 (1937).
Simons, J. H., and Herman, D. F., J. Am. Chem. Soc. 65.
2064 (1943).
Simons, J. H., and McArthur, R. E., Ind. Eng. Chem. 39.
364 (1947).
Simons, J. H., and Rambler, E. 0., J. Am. Chem. Soc. 65,
389 (1943).
Simons, J. H., and co-workers, Trans. Electrochem. Soc.
95. 47 (1949).
Swarts, F., Bull, classe sci. Acad. roy. Belg. 8,
343 (1922).
Ibid.. 20. 782 (1934).
Swarts, F., Bull. soc. chem. Belg., 120 (1910).


63
33. Ibid.. 48. 176 (1939).
34. Swarts, F., Chem. Zentr. II, 26 (1898).
35. Tarrant, P., and Brown, H. C., J. Am. Chem. Soc. 73.
5831 (1951).
36. Tinker, J. M., U. S. Patent 2,257,868 (October 7, 1941).
37. Whitmore, F. C., "Organic Chemistry", D. van Nostrand
Company, Inc., New York, 1937, p.439.
38. Willard, H. H., and Winter, 0. B., Ind. Eng. Chem.
Anal. Ed. 5, 7 (1933).


ACKNOWLEDGMENTS
The author wishes to express his gratitude to
Dr. J. H. Simons for the encouragement and advice pro¬
vided during this investigation.
Also, the author wishes to express his thanks
to the other members of his supervisory committee for their
assistance and encouragement.
The author also wishes to acknowledge the sponsor¬
ship of the Minnesota Mining and Manufacturing Company with¬
out which this work would not have been possible.
64


BIOGRAPHICAL NOTE
Reginald F. Clark was "born on February 24, 1927 in
Millerton, New York.
In 1944, he enlisted in the U. S. Army and was
honorably discharged in 1946. During this period he at¬
tended Princeton University, Princeton, New Jersey, under
the Army Specialized Training Program.
He entered the University of Illinois, Urbana,
Illinois, in 1947 and received a Bachelors of Science degree
in 1951.
In 1951, he entered the Graduate School of the
University of Florida. He was a Graduate Assistant from
1951 to 1954 and held an Industrial Fellowship from 1954 to
1956.
In July 1956, he was appointed to the faculty of
the University of Florida.
Mr. Clark is a member of the American Chemical
Society, Gamma Sigma Epsilon and Sigma Xi.
65


COMMITTEE REPORT
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 Science and
to the Graduate Council, and was approved as partial fulfill¬
ment of the requirements for the degree of Doctor of Philos¬
ophy.
August 11, 1956.
Supervisory Committee:
Dean, College of Arts and Science
Dean, Graduate School


Full Text
FLUOROCARBON-AROMATIC
HYDROCARBON COMPOUNDS
By
REGINALD F. CLARK
A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
August, 1956

TABLE OF CONTENTS
Page
LIST OF TABLES Ui
INTRODUCTION 1
Historical Development of Fluorochemicals 1
Fluorocarbon Chemistry 3
Aromatic Compounds ....... 6
Statement of the Problem 13
EXPERIMENTAL PROCEDURES 15
Fluorocarbon Carboxylic Acid Chlorides. 15
Fluorocarbon Aromatic Ketones. ... 16
2,4-Dinitrophenylhydrazones .... 22
Semicarbazone 22
Fluorocarbon Acid Anhydrides .... 23
Aromatic Esters of Fluorocarbon Acids . 23
Friedel-Crafts Alkylation 33
Aromatic Metallic Reactions .... 34
Aromatic Fluorocarbon Ethers .... 40
DISCUSSION 44
Organic Aromatic Ketones 44
Fluorocarbon Aromatic Ketones. ... 45
Aromatic Esters of Fluorocarbon Acids . 48
Alkforyl Aromatic Compounds .... 51
Aromatic Fluorocarbon Ethers .... 54
Conclusions .56
SUMMARY 57
BIBLIOGRAPHY 61
ACKNOWLEDGEMENTS 64
BIOGRAPHICAL NOTE 65

LIST OF TABLES
Table Page
I Fluorocarbon Acid Chlorides .... 17
II Fluorocarbon Aromatic Ketones. ... 20
III2,4-Dinitrophenylhydrazones of Fluoro¬
carbon Aromatic Ketones 24
IV Fluorocarbon Acid Anhydrides .... 25
V Aromatic Esters of Fluorocarbon Acids . 29
iii

INTRODUCTION
It is usually recognized at the present time that
organic chemistry is one of the largest and most extensive¬
ly investigated branches of the science of chemistry; how¬
ever, in the last decade a new field of chemistry has de¬
veloped with a potentiality to surpass organic chemistry in
number of compounds and investigational endeavor. It is
identified as fluorocarbon chemistry. As the name implies,
fluorocarbons are compounds, analogous to hydrocarbons, but
with fluorine atoms in the positions occupied by hydrogen
atoms in hydrocarbons.
On the basis of our present knowledge, it has been
predicted that the present one million organic compounds
12
would serve as patterns for about 10 fluorocarbons, fluoro¬
carbon derivatives and fluorocarbon organic hybrids.
Historical Development of Fluorochemicals
It was not until 1886 that Moissan 18 first iso¬
lated elementary fluorine by the electrolysis of anhydrous
hydrogen fluoride and potassium fluoride. Since that time,
chemists have been extremely interested in the violent re¬
action between it and carbonaceous material. Moissan made
1

2
many attempts without too much success to utilize this re¬
action for the preparation of compounds of fluorine and car-
14
hon. In 1926, Leheau and Damiens obtained methforane
OO
from this reaction, and in 1930, Ruff and Keim isolated
and identified ethforane from this same reaction. During
Op 0*1
this period other investigators * produced ethforane
and ethforene by various experiments, but it was not until
25
1937 that Simons and Block discovered that the reaction
between carbon and fluorine could be controlled by cataly¬
zation with mercury or mercury salts. The first series of
fluorocarbons, possessing an entirely new set of properties,
was discovered by this method and thus established the foun¬
dation for an entirely new field of chemistry.
During World War II atomic energy research needed
large quantities of fluorocarbons for use in problems con¬
cerned with the separation of uranium isotopes, and due to
this large demand, several processes were developed to pro¬
duce fluorocarbons.
In the years 1941-1943, two major processes were
developed. The first was catalytic fluorination of hydro¬
carbons using silver, copper or mercury metal and salts as
the catalysts, and the second was the metallic fluoride pro¬
cess. The metallic fluoride process utilizes the reaction
between a metal fluoride, such as silver difluoride or co¬
balt trifluoride, and an organic compound. A short time

3
later an electrochemical method was invented "by Simons ,
which produces fluorocarbons without the use of elementary
fluorine. By this method an electric current is passed
through liquid consisting of an organic substance and liq¬
uid hydrogen fluoride, which causes the formation of the
product which may or may not and usually does not have the
structure of the original organic substance. This electro¬
chemical process is the most economical, versatile and sim¬
plest method for obtaining fluorocarbons and some fluorocar¬
bon derivatives.
Fluorocarbon Chemistry
The properties of the fluorocarbons and their de¬
rivatives are providing many opportunities in advancing and
testing theories of chemical and physical behavior. From
the very start, the unusual physical properties of the
fluorocarbon liquids were noted. Values for surface tension,
diamagnetic susceptibilities, index of refraction, Verdet
constants, energies of vaporization per gram, ultrasonic
velocity and other physical properties are very low com¬
pared to organic liquids, and in some cases are the lowest
ever recorded. Liquified inert gases would be an excellent
standard for solubility and liquid state studies; however,
their availability and low boiling points make their use
prohibitive. Experimental data has shown that fluorocarbons

4
approach the inert gases as closely as can he expected of
any known polyatomic substances and this with their avail¬
ability and variety should make them the best secondary
standard for liquid state and solubility studies. It is
evident that future studies of the physical properties in
the fluorocarbon domain will contribute significantly to
the theoretical development of the liquid state and other
related philosophical interests.
The chemical properties of fluorocarbon compounds
are vastly different from those expected by analogy with
organic compounds. For example, fluorocarbons are thermal¬
ly stable and extremely resistant to oxidation, whereas, in
hydrocarbons the opposite is true. Fluorocarbon oxides and
nitrides, which have the skeletal arrangement of organic
ethers and amines respectively, are found to be completely
void of the chemical properties usually associated with
these organic compounds.
Some fluorocarbon compounds, however, undergo many
reactions found in organic chemistry. For example, fluoro¬
carbon carboxylic acids can be esterified with organic al¬
cohols and fluorocarbon carboxylic acid chlorides react
with aromatic compounds in a Friedel-Crafts reaction to
produce ketones.
It is quite apparent that the empirical rules of
organic chemistry do not always apply to fluorocarbon

5
compounds. This is easier seen when it is considered that
the rules of organic synthesis are the result of the accu¬
mulation and organization of years of experimental data,
and that this data is inadvertently classified according to
the properties of the functional groups. Usually the prop¬
erties of these functional groups are independent of the
organic radical to which they are attached. This has made
the distinction between the properties of a functional
group and the organic compound containing that group quite
vague.
On the basis of existing experimental results, it
has been shown that the effect of a fluorocarbon radical on
a functional group is vastly different than that of an or¬
ganic radical. It is this large difference in chemical
properties which will necessitate the accumulation of a
large amount of experimental data in order to formulate
the chemical properties and methods of synthesis related
to the fluorocarbon compounds.
From time to time, there will undoubtedly be some
similarity to the chemistry of organic compounds, but it is
only through experimental results that similarities and
differences will be resolved.
This present work is submitted in the hope that
the experimental results will contribute to the organiza¬
tion of the chemistry of fluorocarbon compounds.

6
Aromatic Compounds
Aromatic character or aromaticity has always been
associated with certain types of reactions more or less
peculiar to benzene and its derivatives. Among these are
nitration, sulfonation, mercuration, the Friedel-Crafts re¬
actions and halogenation; however, all of these reactions
are encountered in the aliphatic series and, as such, the
line of demarcation between aromatic and aliphatic organic
compounds is so ill defined that no simple definition has
been agreed upon.
Today, aromatic compounds comprise a major portion
of the commercial chemical sales and are utilized as start¬
ing materials, intermediates or finished products in mil¬
lions of tons yearly. These aromatic compounds find their
way into everyday use as dyes, plastics, coatings, paints,
food preservatives, drugs and numerous other applications.
Aromatic compounds containing a fluorocarbon radi¬
cal or a fluorocarbon derivative have been studied with
great interest with respect to the differences or simi¬
larities in chemical behavior in contrast to similar aro¬
matic organic compounds.
In order to understand this contrast in chemical
properties, an examination of the properties of some of the
aromatic organic compounds is necessary.

7
If toluene is vigorously oxidized, the methyl
group rather than the benzene ring is affected. The pro¬
duct is benzoic acid.
C6H5CH3 + 3 [O] ———* C6H5COOH -f H20
27
It has also been shown by Simons and McArthur
that toluene may be oxidized to o-cresol by oxygen in the
presence of hydrogen fluoride.
C6H5CH3+ 02 —0-CH3C6H4OH
If toluene is chlorinated in the presence of fer¬
ric chloride, substitution in the aromatic nucleus occurs,
yielding a mixture of ortho and para chiorotoluenes.
C6H5CH3 4- Cl2 -FgCl3-> o-CH3C6H4C1 + p-CH3C6H5Cl + 2HC1
However, if toluene is chlorinated in the presence
of strong light, substitution in the methyl group occurs.
C6H5CH3 H- Cl2 -^^raviplet-light^ c6h5ch2C1 + HC1
C6H5CH2C1 -H Cl2 -^íraviolet light> c6H5CHC12 + HC1
C6H5CHC12 â– + Cl2 -al^rajiplet_light^ c6H5CC13 + HC1
Either one, two or three hydrogen atoms can be re¬
placed by regulating the amount of chlorine used. The pro¬
ducts are benzyl chloride, benzal chloride and benzotri-
chloride.
When the methyl group of toluene is halogenated
to produce benzotrichloride, the chemical properties under¬
go a pronounced change, whereas, the methyl group of toluene
is unaffected by dilute acids, benzotrichloride is

8
hydrolyzed easily by warming with dilute acids to produce
benzoyl chloride, and, finally, benzoic acid.
C6H5CCl3 C6H5C0C1 -f- 2HC1 —C6H5COOH 4- HC1
Because of its high yields and simplicity, this
reaction is used commercially to produce benzoic acid of
high purity.
When benzotrichloride is treated with hydrogen
13 34
fluoride or antimony trifluoride * , the simplest aro¬
matic compound containing a fluorocarbon radical is pro¬
duced, benzotrifluoride.
C6H5CC13
BOB’
-» C6H5CF3-|- 3HC1
With this change to benzotrifluoride, the chemical
properties with respect to oxidation and substitution are
also changed.
Benzotrifluoride cannot be oxidized by any usual
reagents; however, if an amino group is introduced into the
aromatic ring, it is rendered susceptible to oxidation and
long treatment with chromic acid yields trifluoroacetic acid.
C6H5CF3 m-CF3C6H4N02
h2so4
HC1
m-CF3C6H4NH2 —> CF3C00H
This reaction demonstrates the stability of the
CF3 group to oxidation. In toluene, either the methyl
group or the ring can be oxidized, whereas, in benzotri-
fluoride only the aromatic ring can be oxidized, and only

9
after activation.
Certain ring-substituted, derivatives of benzotri-
fluoride may be easily made. When benzotrifluoride is halo-
genated, the halogen atom enters the ring meta to the tri-
fluoromethyl and not ortho or para, as in toluene.
C6H5CF3 4- Brg ——- ■> m-CF3C6H4Br 4- HBr
This orientation is also true for nitration and sulfonation.
Where the methforyl group is desired ortho or para
to some other group, a different approach must be used. In
some cases, the group desired may be introduced in the ortho
or para position of toluene, which may then be chlorinated
and treated with hydrogen fluoride to give the substituted
benzotrifluoride. Ring-substituted nitro and chloro com¬
pounds have been made by this method. For other types,
Jones 10 has made a number of phenols, fluorides, chlorides,
bromides and iodides by the diazonium transformation of or¬
tho and para aminobenzotrifluoride.
Compounds containing more than one methforyl group
g
are readily prepared. German chemists have prepared the
three isomeric bis(methforyl)benzenes, and also tris(meth-
foryl)benzene.
The procedure for preparing such compounds is quite
involved, as the following example will reveal.

10
m-CH3C6H4CH3 m-CCl3C6H4CHCl2 m-CF3C6H4CHF2-£i£.
m-CF3C6H4CF2Cl 111-CF3C6I4CF3
28
Simons and Ramler made an attempt to introduce
the pentafluoroethyl group into benzene by the use of the
Friedel-Crafts reaction between trifluoroacetyl chloride
and benzene. They obtained trifluoroacetophenone, which,
when treated with phosphorous pentachloride, gave CgH5CCl2-
CF3. This compound failed to react with antimony trifluo-
ride to give pentafluoroethylbenzene. Simons and Herman
later showed that it was not possible to replace the alpha
chlorine atoms in C6H5CCI2CF3 by the usual fluorinating
agents. They were successful in preparing a small amount
of the pentafluoroethyl benzene with active silver fluoride
made by using elemental fluorine. This established the
existence of an alkforyl radical on aromatic compounds
larger than trifluoromethyl.
McBee and Pierce have since reported that
l-ethforyl-4-methforylbenzene may be obtained from the cor¬
responding chloro compound by fluorination with a mixture
of antimony trifluoride and antimony pentachloride.
The preparation of fluorocarbon aromatic ketones
has been limited to the trifluoromethyl ketones of benzene
28
and toluene. As mentioned previously, Simons and Ramler
prepared trifluoroacetophenone using a Friedel-Crafts re¬
action, and Jones 11 prepared o-tolyl trifluoromethyl

11
ketone by the reaction of organometallie derivatives of
benzyl chloride with trifluoromethylnitrile or trifluoro-
acetyl chloride, followed by rearrangement. Trifluoro-
acetophenone undergoes a haloform reaction and reacts with
phosphorous pentachloride but fails to form a cyanohydrin.
As yet, there have been no fluorocarbon phenyl
15
ethers produced. McBee and Bolt have prepared various
chlorofluoroethyl and chlorofluoropropyl aromatic ethers by
reacting CHCI2CF2CI, CH2CICF2CI and CF3CHCICF3 with sodium
35
aryloxides. Tarrant and Brown have also prepared sev¬
eral chlorofluoroethyl aromatic ethers using fluoro or
chlorofluoroethenes with phenol and potassium hydroxide.
Since fluorocarbon aromatic compounds usually are
more resistant to oxidation and bacterial action than aro¬
matic compounds, they should have a large potential in dyes
and coatings.
The Germans first used dyes containing fluorine in
the 1930»s.
Some of
their
dye bases are
as follows:
NH2
NH2
C
1
Sj|S02C2H5
r^l) cf3
Jcf3
F3C
V-
J)nh2
kJ
Cl
Fast Orange GGD Fast Golden Orange GR Fast Scarlet VD

12
These bases were generally coupled with Napthol AS.
An example is as follows:
The red coloration of the Natzi flag was due to a
dye of this type and proved to he very resistant to fading
by light.
Indanthrenblue CLB produced during World War II for
the Luftwaffe has the following formula:
cf3
Dyes containing the trifluoroethoxy group have
also been prepared by the Germans. They found that the ex¬
change of a trifluoroethoxy group for an alkoxyl group
caused the colors to assume a lighter hue.
There has been considerable activity towards pre¬
paring styrene derivatives and subsequent polymers contain-
on
ing fluorine. Renoll reports the preparation of

13
m-methforylstyrene toy the use of the Grignard reagent as
follows:
m-CF3C6H4JBr MS > m-CF3C6H4MgBr JSSaSgO.»
m-CF3C6H4CH0HCH3 —£205..-» m-CF3C6H4CH = CH2
This monomer, when heated at 105°, gives a hard
colorless polymer, and when used in films, is flexible and
21
resistant to sunlight and heat
Statement of the Problem
It can toe seen that the aromatic compounds con¬
taining a fluorocarbon radical possess certain desirable
properties, which should find wide applications if the
chemistry of these compounds were further developed. The
fluorocarbons are very resistant to oxidation and bacterial
activity, and on this basis we can assume that it is the
fluorocarbon radical on aromatic compounds which imparts
these properties to the molecule. Since a direct method
of attaching alkforyl groups to aromatic nuclei has not yet
been reported, except by chlorination of an alkyl side
chain followed by exchange reactions, an attempt was made
to find a method to introduce an alkforyl group directly
into the aromatic nuclei and to investigate other types of
fluorocarbon aromatic compounds. These may be outlined as
follows:

14
1. A study of the Friedel-Crafts type reaction
between aromatic compounds and fluorocarbon acid chlorides
with respect to the preparation and properties of the
fluorocarbon aromatic ketones. Several aromatic nuclei as
well as different fluorocarbon groups were used.
2. The preparation and study of the chemical
and physical properties of the aromatic esters of fluoro¬
carbon acids.
3. The reactions of some fluorocarbon halides with
benzene, using Friedel-Crafts alkylation methods.
4. The investigation of the reactions of several
organic aromatic metallic compounds with fluorocarbon
iodides and the preparation of aromatic alkforyl derivatives.
5. A study of the reactions of aryloxides with
fluorocarbon iodides.
6. The preparation and study of the chemical and
physical properties of difluoromethyl phenyl ether.

EXPERIMENTAL PROCEDURES
Fluorocarbon carboxylic acids—The fluorocarbon
carboxylic acids were obtained from the Minnesota Mining
and Manufacturing Company. They were purified by fraction¬
ation through a 50 cm. column, 8 mm. inside diameter,
packed with l/l6 in. glass helices. This fractionation
column was used in all subsequent experiments.
Fluorocarbon Carboxylic Acid Chlorides
Preparation—The acid chlorides were prepared by
the dropwise addition of the acids to an equivalent of
phosphorous pentachloride. The reaction may be expressed
as follows:
Rf COOH -f PC15 — » Rf COCI 4- POCI3 •+- HC1
The first two members were collected from the reaction mix¬
ture in a trap cooled in Dry Ice-acetone and transferred to
a low temperature fractionation column for purification.
The other members of the series were fractionated directly
from the reaction mixture. The yield of acid chloride for
all members of the series was approximately quantitative.
Analysis—The acid chlorides were hydrolyzed quan¬
titatively in dilute sodium hydroxide, and the resulting
15

16
solution adjusted to a pH 7 with nitric acid. The chloride
ion was then determined volumetrically by Mohr’s method.
The physical properties and analyses of the acid
chlorides are summarized in Table I.
Fluorocarbon Aromatic Ketones
Preparation—The fluorocarbon aromatic ketones
were prepared according to one of the three following pro¬
cedures:
Procedure A—Acid chlorides boiling below 40°. In
a 250 ml. flask equipped with magnetic stirrer, thermometer
and a ary Ice-acetone Dewar type reflux condenser, were
placed two moles of the aromatic compound and one-half
mole of aluminum chloride and cooled to -10°. One-quarter
mole of the acid chloride was bubbled through the mixture
over a period of six hours. The flask was allowed to warm
to 0° with the initial introduction of the acid chloride
and maintained at 0° during the entire addition, after
which the flask was warmed to 10° and stirred for two ad¬
ditional hours until there was no longer any evolution of
hydrogen chloride. The reaction mixture was poured into an
ice-hydrochloric acid mixture and ether added for extrac¬
tion. The ether extractions were dried over calcium
chloride and fractionated at reduced pressure.

TABLE I
Compound
CF3COCI36
c2f5coci
c3f7coci17
c4f9coci
C5F11C0C1
Fluorocarhon Acid Chlorides
Analysis
B.p. °C
M 25
SB—
ñ 25
<¿4—
Theory
to
Found
to
-27
-
-
-
-
5.0-5.5
-
-
19.43
19.42
38.0-39.0
1.288
1.55
-
-
67.5-68.0
1.315
1.59
12.52
12.50
85.8-86.0
1.327
1.66
10.67
10.64

18
Procedure B—Acid chlorides Boiling above 40°.
One-half mole of aluminum chloride and two moles of an aro¬
matic compound were placed in a 250 ml. flask, which was
equipped with a magnetic stirrer, thermometer and a water
condenser. The flask was warmed to 50° and the acid chlo¬
ride was added dropwise during a period of four hours. The
reaction mixture was cooled to room temperature, poured in¬
to an ice-hydrochloric acid mixture and ether added for ex¬
traction. The ether extractions were dried over calcium
chloride and fractionated.
Procedure C—The apparatus was the same as in
Procedure B. Aluminum Bromide was substituted for alumi¬
num chloride. The aluminum Bromide was prepared By adding
Bromine dropwise to small pieces of aluminum metal contain¬
ing one piece of aluminum amalgam. During the addition of
Bromine, the mixture was cooled in an ice Bath. A mixture
of one-quarter mole acid chloride and one mole aromatic
compound was then added dropwise to the aluminum Bromide
during a period of two hours. The reaction was maintained
at 50°. After the reaction was completed, Procedure B was
followed.
Analysis—The ketones were analyzed By a method
similar to the method of Kimball and Tufts . A weighted
amount of the ketone was placed in a Parr Bomb with a one
gram piece of metallic sodium and the Bomb flushed with

19
hydrogen. The homh was heated at a dull red heat for six
hours. The homh was cooled, the excess sodium was des¬
troyed with methanol and the contents of the homh were
washed quantitatively into a beaker.
The fusion mixture was then filtered through a
previously weighted sintered glass crucible to remove the
carhon for the carhon determination.
The water solution was quantitatively transferred
to a 500 ml. volumetric flask. A 50 ml. aliquot was taken
and titrated for fluoride with standard thorium nitrate hy
the method of Willard and Winter 38.
The physical properties, yields and analyses of
the ketones are summarized on Table II.
Solubility—The ketones are insoluble in water and
concentrated sulfuric acid and soluble in ether, ethanol,
benzene and butforyl oxide.
Degradation—-The ketones reacted vigorously with
a solution of concentrated potassium hydroxide to give a
haloform type splitting reaction, yielding a monohydro¬
fluorocarbon. Upon acidification, the sole organic pro¬
duct was an aromatic acid. In every case, benzoic acid,
p-toluic acid or 2,4-dimethylbenzoic acid was obtained and
identified by its melting point and neutral equivalent.
The monohydrofluorocarbons were identified by their physi¬
cal properties and molecular weight. The molecular weights

TABLE II
Fluorocarbon Aromatic Ketones
Pro-
ComDound cedure
Yield
B . o . °C
M.n.°C
nn25
d425
Theory Found
%C %C
Theory Found
%F %F
CF3C0C6H5 28
A
-
152
-
1.4583a
1.2791
a
-
-
-
C2F5C0C6H5
A
44.2
161.2
-
1.4245
1.372
48.2
47.9
42.5
42.1
c4f9coc6h5
B
32.8
188.5
-
1.3990
1.517
40.8
40.7
52.8
52.3
C5F11C0C6H5
B
43.6
204
-
1.3910
1.538
38.5
38.2
55.8
55.7
P—CFgCOCgH^CHg
A
32.4
179.2
3.5
1.4664
1.240
57.5
57.4
33.0
33.2
p-c2f5coc6h4ch3
A
43.8
181.4
4.0
1.4380
1.317
50 .4
50.4
39.9
39.8
p-CgF^COCgH^CHg
A
27.1
193
0.5
1.4230
1.384
46.2
46.1
46.2
45.9
P •"C^FgCOCgH^Hg
B
21.0
211
-16.5
1.4126
1.445
42.9
42.8
50.6
50.3
P-C5F11C0C6H4CH3
B
65.5
217.3
-13.5
1.4039
1.504
40.4
40.5
55.3
55.3
2,4-(CH3)2C6H3C0C5F1;l
C
81.0
217
-
1.4421
1.438
50.5
50.5
52.0
51.9
a Determined at 20°C

21
were obtained by Regnault’s method.
Reaction with phosphorous pentachloride—Tri-
fluoromethyl phenyl ketone reacts with phosphorous penta¬
chloride under reflux conditions to give 1,1,1-trifluoro-
2.2-dichloro-2-phenylethane with a yield of 48.5% 28. The
reaction of the ketones with phosphorous pentachloride was
attempted using a similar method of Cohen, Wolosinski and
O
Schewrer , whereby the ketone was refluxed in an excess of
phosphorous pentachloride for twenty-four hours, and after
cooling, treating the reaction mixture with a quantity of
acetone equivalent to the excess phosphorous pentachloride
to convert all the phosphorous pentachloride to phosphorous
oxychloride. Any products formed could then be fraction¬
ated directly from the phosphorous oxychloride.
A mixture of 20 g. (0.062 mole) of butforyl
phenyl ketone and 20.8 g. (0.10 mole) of phosphorous penta¬
chloride was refluxed for six hours at 190°. The mixture
was cooled and acetone was added slowly until there was no
excess phosphorous pentachloride. The mixture was then
poured slowly into a cold dilute solution of sodium carbon¬
ate. This solution was adjusted to a pH 7 with dilute hy¬
drochloric acid and steam distilled. The distillate was
extracted with ethyl ether, dried over anhydrous magnesium
sulfate and fractionated. There was recovered ethyl ether,
2.2-dichloropropane, a small forerun and unreacted butforyl

22
phenyl ketone.
This experiment was repeated using butforyl phenyl
ketone and p-propforyl tolyl ketone hut increasing the re¬
flux time to twenty-four hours; however, the desired di¬
chloride could not he produced.
2.4-Dinitrophenvlhydrazone s
Preparation—A solution of 2,4-dinitrophenylhy-
drazine was prepared hy adding 0.5 g. of 2,4-dinitro-
phenylhydrazine to 10 ml. of 50% sulfuric acid followed hy
the addition of 10 ml. of 95% ethanol. To this solution,
0.5 g. of ketone was added and was allowed to stand for one
week instead of the usual few hours. The crystals were
filtered and recrystallized three times from ethanol and
water. The highest yields of the 2,4-dinitrophenylhydra-
zones were obtained when a solution of 50% sulfuric acid
was used.
Semicarbazone
The semicarbazone was prepared by refluxing a so¬
lution of 1.5 g. of semicarbazide hydrochloride, 8 ml. of
water, 5 ml. of ethanol and 1.0 g. of ketone for one hour,
after which the solvents were removed under vacuum. The
solution must be refluxed at least one hour to obtain an
appreciable yield of semicarbazone. The semicarbazone was
recrystallized from ethyl ether after being decolorized

23
with activated charcoal.
The physical properties and analyses of the de¬
rivatives are reported in Table III.
Fluorocarbon Acid Anhydrides
Preparation—The acid anhydrides were prepared by
heating the.corresponding fluorocarbon carboxylic acid with
an excess of phosphorous pentoxide. The reaction may be
expressed as follows:
6RfC00H + P2O5 * 3(RfC0)20 -J-2H3PO4
All members of the series were fractionated directly from
the reaction mixture. The yield of acid anhydrides for all
members of the series was approximately quantitative.
Analysis--The acid anhydrides were hydrolyzed in
water and the resulting solution was titrated with stan¬
dard sodium hydroxide using phenolphthalein as the indica¬
tor.
For the fluoride analysis of the acid anhydrides,
the method under analysis of the fluorocarbon aromatic ke¬
tones was used.
The physical properties and analyses of the anhy¬
drides are listed in Table IV.
Aromatic Esters of Fluorocarbon Acids
Preparation—Several reactions were attempted in
order to prepare these compounds.

TABLE III
2.4-Dinitrophenylhydrazones of Fluorocarbon Aromatic Ketones
Compound
M.p. °C
Theory
%N
Found
foN
2,4-Dinitrophenylhydrazone
of
cf3coc6h5 28
94.5-95.5
-
-
2, 4-Dinitrophenylhydrazone
of
c2f5coc6h5
119-120
13.86
13.80
2,4-Dinitrophenylhydrazone
of
c4f9coc6h5
135-136
11.11
11.07
2,4-Dinitrophenylhydrazone
of
CgFuCOCgHg
144-145
10.11
10.06
2,4-Dinitrophenylhydrazone
of
P-CF3C0C6H4CH3
187-188
15.22
15.02
2,4-Dinitrophenylhydrazone
of
p-c2f5coc6h4ch3
162-163
13.40
16.61
2,4-Dinitrophenylhydrazone
of
p-c3f7coc6h4ch3
141-142
11.97
12.14
2,4-Dinitrophenylhydrazone
of
p-C^ qC0C6H4CH3
152-153
10.81
10.78
2,4-Dinitrophenylhydrazone
of
p-c5f11coc6h4ch3
160-161
9.86
9.81

TABLE IV
Fluorocarbon Acid. Anhydrides
Analysis
Compound
B.p. °C
nn25
d,2^
Theory
%F
Found
%F
(CF3C0)2033
39.5-40.5
1.269
1.490
-
-
(CgP500)80
71.5-72.0
1.273
1.571
76.16
75.86
(c3f7co)2o17
107-107.5
1.285a
1.665a
-
-
(c4f9co)2o
137-137.5
1.288
1.706
67.05
66.78
(c5f11co)2o
175-176
1.295
1.769
68.51
68.38
a Determined at 20°C

26
The first was the reaction between sodium phen-
oxide and trifluoroacetyl chloride.
C6H50Na -f CF3COCI -> CF3C00C6H5 -f- NaCl
In a 250 ml. three necked flask equipped with a
magnetic stirrer, thermometer, inlet tube and Dry Ice-
acetone Dewar type reflux condenser, were placed 58 g.
(0.5 mole) of anhydrous sodium phenoxide and 150 ml. of an¬
hydrous hexane. The mixture was heated to 50° with stir¬
ring, and 34.8 g. (0.26 mole) of trifluoroacetyl chloride
was slowly added beneath the surface over a period of two
hours. At the end of this time, the condenser was allowed
to warm to room temperature and the unreacted trifluoro¬
acetyl chloride was collected in a trap cooled in Dry Ice-
acetone. 26 g. (0.19 mole) of trifluoroacetyl chloride was
recovered. The reaction mixture was filtered and the resi¬
due washed with hexane. The filtrate was fractionated, and
after removal of hexane, yielded 9.8 g. of phenyl trifluo-
roacetate, b.p. 146.5-147.0°. This is a yield of 20.2%
based on trifluoroacetyl chloride used.
The second reaction attempted to prepare the es¬
ters was between phenol and trifluoroacetie acid with the
addition of a small amount of sulfuric acid as a catalyst.
In a 100 ml. flask were placed 27.4 g. (0.29 mole)
phenol, 26.5 g. (0.23 mole) trifluoroacetie acid and 8 ml.
concentrated sulfuric acid. The mixture was refluxed at

27
75° for three hours. Fractionation yielded 25.2 g. of tri-
fluoroaeetie acid, h.p. 73-74° and it was concluded that no
ester was produced.
The third reaction attempted to produce the esters
was the reaction between phenol and a large excess of tri-
fluoroacetic acid.
C6H50H +- x‘s CFgCOOH > CF3C00C6H54- CF3C00H*H20
OO
(azetrope)
In a 250 ml. flask were placed 50 g. (0.53 mole)
phenol with 114 g. (1.0 mole) trifluoroacetic acid and the
mixture refluxed at 75° for four hours. The reflux con¬
denser was replaced by a fractionating column and the mix¬
ture fractionated. The fractionation yielded 100 g. tri-
fluoroacetic acid, b.p. 73-74°, 6.9 g. azetrope of tri-
fluoroacetic acid and water, b.p. 104-105° and 14.6 g.
phenyl trifluoroacetate, b.p. 146-147°. This is a 15%
yield of ester based upon the amount of phenol used.
The fourth reaction was one between an acid anhy¬
dride and phenol. For the first member of the series, the
reaction may be expressed as follows:
C6H50H 4- (CF3CG)20 > CF3C00C6H5 4- CFgCOOH
In a 100 ml. flask were placed 11.2 g. (0.12 mole)
of phenol. 21 g. (0.1 mole) of trifluoroacetic anhydride
was added dropwise to the phenol with stirring. The mix¬
ture became warm with the addition of the anhydride. The

28
mixture was heated to 120° for one hour and fractionated.
Fractionation yielded 18.0 g. of phenyl trifluoroacetate,
h.p. 146-147°. This is a 95% yield based upon the trifluoro-
acetic anhydride used.
The other members of the series were prepared by
the same method. In the case of the preparation of phenyl
valerforate, after the anhydride was added to the phenyl,
the reaction mixture was fractionated to remove valerforic
acid and the residue washed three times with 50 ml. por¬
tions of hot water to remove any excess phenol. The re¬
maining ester was dried over anhydrous magnesium sulfate
and fractionated. This extra step was necessary since
phenyl valerforate and phenol have the same boiling point.
A thioester was also prepared using thiophenol and
trifluoroacetic anhydride.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois.
The physical properties and analyses of the esters
are summarized in Table IV.
Solubility—The esters were soluble in ethyl ether,
ethyl alcohol, benzene and dibutforyl oxide. The esters
were found slightly soluble in water, 50% sulfuric acid,
10% sodium bicarbonate and concentrated sulfuric acid.
Reaction with sodium hydroxide—With 10% sodium
hydroxide the esters underwent saponification. The rate of

TABLE V
Aromatic Esters of Fluorocarbon Acids
Compound
Yield 9
% B.p. °C
M.p. °C
»D85
T) 25
O4
Theory
ÚC
Found
°/oG
Theory Found
%H %H
CP3C00C6H5
95
146.5-147.0
-8.5
1.4183
1.276
50.54
51.00
2.65
2.49
C^FgCOOCgHg
94
153.0-153.5
-23.0
1.4078
1.324
45.01
45.26
2.10
2.03
CgFrjfCOOCgHg
96
162.5-163.0
-27.0
1.4156
1.350
41.39
41.42
1.74
1.69
c4f 9C00C6H5
92
179-180
-25.0
1.3888
1.438
38.84
39.00
1.48
1.47
c5f1iCooc6h5
95
196-197
-18.0
1.3715
1.533
36.94
36.81
1.29
1.18
cf3cosc6h5
92
174-175
-
1.4160
1.245
46.60
46.83
2.44
2.31

30
saponification decreased proportionately from phenyl tri-
fluoroacetate to phenyl caproforate.
Attempted reactions with the esters—Organic aro¬
matic esters are known to undergo a Fries rearrangement
when treated with aluminum chloride to produce ortho and
para hydroxyl ketones 4.
In a 200 ml. flask were placed 28.3 g. (0.15 mole)
of phenyl trifluoroacetate, 20 g. (0.15 mole) aluminum chlo¬
ride and 100 ml. anhydrous nitrobenzene. The mixture was
heated to 40° with stirring for twenty-four hours, then,
after cooling, poured in an ice-hydrochloric acid mixture
and extracted with ethyl ether. Upon fractionation, only
unreacted phenyl trifluoroacetate and the nitrobenzene was
obtained.
The experiment was repeated but increasing the
temperature to 120°; however, no reaction occurred and only
starting material was recovered.
Reaction with phosphorous pentachloride—A mixture
of 28.3 g. (0.15 mole) phenyl trifluoroacetate and 33.3 g.
(0.16 mole) phosphorous pentachloride was heated to reflux
for one week. Anhydrous acetone was added to decompose the
excess phosphorous pentachloride and the mixture was frac-
tioned. Fractionation yielded a small amount of 2,2-di-
chloropropane, phosphorous oxychloride, 20.8 g. of liquid
boiling at 75-76° (30 mm.) and a dark colored residue

31
remained. A small sample of this material boiling at 75-76°
(30 mm.) was observed to be partially soluble in water. The
water solution was acidic when tested with litmus. Bromine
water was added to the water solution and a white solid
formed. The solid, after recrystallization from alcohol and
water, was identified as tribromophenol, m.p. 95-96°.
This original liquid was added to 100 ml. of 20%
potassium hydroxide and steam distilled to remove phenol.
The steam distillate was separated and dried. Fractionation
yielded 15.8 g. of liquid boiling at 85-86° (30 mm.),
181-182° (760 mm.), nD30 1.4564, d430 1.392.
A sodium fusion on this liquid revealed chlorine
and fluorine to be present. An infra red spectrum on this
compound showed no absorption due to hydroxyl, carbonyl or
disubstituted benzene; however, it did contain an absorption
band corresponding to an aromatic ether.
The liquid was believed to be phenoxy-2,2,2-tri-
fluoro-l,l-dichloroethane. The molar refractivity for this
ether calculated from the density and refractive index is
47.88; the value calculated from the sum of atomic refrac-
tivities is 46.61.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for CgHgOCCl^CF^
Cl, 28.94. Found: Cl,29.00.

32
Solubility—The ether was soluble in ethyl alcohol,
ethyl ether and benzene. This ether was insoluble in water.
Reactions of phenoxy-2,2,2-trifluoro-l,l-dichloro-
ethane—To 3 g. (0.012 mole) phenoxy-2,2,2-trifluoro-l,l-
dichloroethane was added a solution of 7 g. (0.024 mole) po¬
tassium dichromate and 30 ml. of 50% sulfuric acid. The mix¬
ture was heated at 100° for twelve hours. At the end of this
time the mixture was cooled, poured on ice and extracted
with ethyl ether. After removal of the ethyl ether, 3 g. of
starting material were recovered.
To a 50 ml. Erlenmeyer flask containing 3 g. (0.012
mole) phenoxy-2,2,2-trifluoro-l,l-dichloroethane, were
added 20 ml. of 80% sulfuric acid and the mixture heated to
100° for twelve hours. There appeared to be less ether at
this time, and the heating was continued for an additional
twelve hours. The acid solution was dark in color and no
phenyl ether remained after this added period. The solu¬
tion was cooled and poured on ice, which yielded a clear
aqueous solution. This aqueous solution was extracted with
three 10 ml. portions of ethyl ether. The ethyl ether ex¬
tractions were combined, dried over anhydrous magnesium sul¬
fate and the ether removed by distillation. A small amount
of liquid remained possessing a phenolic odor. Bromination
of this liquid yielded a tribromophenol, m.p. 94-95°, which,
when mixed with an authentic sample, gave no melting point

33
depression.
Friedel-Crafts Alkylation
Fluorocarbon halides—The fluorocarbon iodides
3
were prepared using the method of Crawford and Simons
whereby silver salts of the fluorocarbon acids are decom¬
posed in the presence of iodine.
The ethforyl chloride was obtained from the E. I.
duPont de Nemours and Company.
Attempted alkylation with ethforyl chloride—In a
500 ml. three necked flask equipped with a stirrer, gas in¬
let tube and Dry Ice-acetone Dewar type reflux condenser,
were placed 250 ml. (3.21 moles) benzene and 27 g. (0.203
mole) aluminum chloride. The mixture was heated to reflux
and 50 g. (0.203 mole) ethforyl chloride were added over a
period of four hours. At the end of this time the mixture
was cooled and 49.5 g. of ethforyl chloride were recovered.
Attempted alkylation with propforyl iodide—This
experiment was repeated except using 60 g. (0.203 mole) of
propforyl iodide in place of the ethforyl chloride. With
the initial addition of the iodide, the mixture turned dark
in color. The heat was discontinued and the addition of
iodide regulated to keep the mixture at 60°. Hydrogen
iodide was liberated during the entire period of addition.
When the hydrogen iodide ceased, the mixture was cooled and
poured on an ice-hydrochloric acid solution. Two layers

34
formed and the benzene layer was separated and steam dis¬
tilled. During the steam distillation free iodine was
liberated. The organic distillate was separated, dried
over anhydrous magnesium sulfate and fractionated. Frac¬
tionation yielded 40 g. propforyl iodide, benzene and 9.6 g.
iodobenzene. There was a large amount of tarry residue in
the steam distillation flask. Both the residue and the acid
solution contained fluorine.
Aromatic Metallic Reactions
Phenyl magnesium iodide with propforyl iodide—In
a three-necked flask equipped with thermometer, condenser
and stirrer, were prepared 50 g. (0.22 mole) of phenyl mag¬
nesium iodide in 300 ml. of anhydrous ether. To this solu¬
tion 39.6 g. (0.1 mole) of propforyl iodie were added drop-
wise over a period of two hours. The mixtured turned
orange, then dark red and stirring was continued for eight
additional hours. The mixture was then hydrolyzed with
250 ml. of lce-10% hydrochloric acid solution. The ether
layer was separated and the water layer extracted with
three 20 ml. portions of ethyl ether. The ether layer and
extracts were combined, dried with anhydrous magnesium sul¬
fate and fractionated. 10.6 g. hexforane, b.p. 57-58°, ben¬
zene, iodobenzene and a small amount of high boiling pot
residue were obtained. This residue was found to contain
fluorine but could not be rectified or identified as the

35
quantity was very small.
Phenyl sodium with propforyl iodide—Phenyl sodium
was prepared from chlorobenzene, sodium and toluene accord¬
ing to standard organic procedures. To a solution of 25 g.
(0.25 mole) of phenyl sodium in 200 ml. of toluene were
added dropwise 20 g. (0.198 mole) of propforyl iodide. The
mixture turned light red and stirring was continued at room
temperature for twenty-four hours. The mixture was neutral¬
ized with 10% hydrochloric acid and extracted with ether.
The ether extractions were dried over anhydrous
magnesium sulfate and fractionated. Fractionation yielded
ether, toluene and 9.2 g. of material boiling from 110-184°.
There were no plateaus in this fractionation. A sodium fu¬
sion on this material revealed fluorine, chlorine and iodine
to be present. After fractionation there remained a tarry
pot residue which could not be rectified. A sodium fusion
on this residue revealed fluorine, chlorine and iodine.
Phenyl lithium with propforyl iodide—Phenyl lith¬
ium was prepared from bromobenzene and lithium metal in an¬
hydrous ethyl ether by standard procedures To a solu¬
tion of 18 g. (0.214 mole) of phenyl lithium in 250 ml. of
anhydrous ethyl ether cooled to 0°, were added 20 g. (0.198
mole) of propforyl iodide. The mixture turned dark red and
stirring was continued for twenty-four hours while the
flask was maintained at 0-5°. Cold dilute hydrochloric

36
acid was then added slowly until the mixture was acidic. The
ether layer was separated and the water layer was extracted
with three portions of ethyl ether. The water layer was
tested and found to contain fluoride ion. The ether layer
and extractions were combined, dried with anhydrous magne¬
sium sulfate and fractionated. After removal of the ethyl
ether, fractionation yielded bromobenzene, b.p. 156-157°,
and 7.1 g. of material with a boiling range of 158-168°.
There was a considerable amount of tarry residue left,
which, upon steam distillation, yielded 6.2 g. of a white
crystalline solid with a m.p. of 75-76°. This solid was
identified as diphenyl, and when mixed with an authentic
sample, gave no melting point depression. The material boil¬
ing at 158-168° contained fluorine and bromine but could not
be identified. The bromobenzene was from the excess used in
the preparation of phenyl lithium.
p-tolyl lithium with propforyl iodide—p-tolyl
lithium was prepared from p-bromotoluene by the same method
as in the previous experiment. 20 g. (0.198 mole) of prop¬
foryl iodide were added to a solution of 25 g. (0.255 mole)
of p-tolyl lithium in 200 ml. of anhydrous ethyl ether. The
solution was kept in an ice bath, and the propforyl iodide
was added dropwise over a period of two hours. The mixture
turned light orange and stirring was continued for twenty-
four hours. Dilute hydrochloric acid was added until the

37
mixture was acidic and the two layers separated. The water
layer was extracted with ethyl ether and the ether layer and
extracts combined, dried over anhydrous magnesium sulfate
and fractionated. After removal of the ethyl ether, frac¬
tionation yielded p-bromotoluene, 1.2 g. of material boil¬
ing at 106-107° (49 mm.), 190-192° (760 mm.), 8.6 g. at
108-115° (49 mm.) and 4.2 g. of a material that solidified
in the receiver. A dark colored residue remained in the
flask. The material boiling from 108-115° (49 mm.) could
not be identified. A sodium fusion revealed fluorine and
iodine to be present. The material that solidified was
identified as p-iodotoluene, b.p. 211-212°, m.p. 35-36°.
The colored residue was steam distilled and yielded 3.2 g.
of p,p’-bitolyl, m.p. 121°. The material that distilled
at 106-107° (49 mm.) was thought to be p-propforyltoluene
after a sodium fusion revealed fluorine as the only halogen
present. An infrared spectrum was obtained on the liquid,
and, after comparison with known para substituted toluene
derivatives, it was assumed that the compound was para
substituted. An analysis gave C. 46.31, H. 2.98; calculated
for CH3C6H4C3P7 C. 46.18, H. 2.69.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois.
o-chloromercuriphenol with fluorocarbon iodides—
A glass vial of 120 ml. capacity was constructed from Vycor

38
#7910 glass and. attached to a graded seal of Yycor to Pyrex
in order to provide a convenient method of sealing. In this
tube were placed 33 g. (0.1 mole) o-chloromercuriphenol and
40 g. (0.202 mole) methforyl iodide. The tube was sealed
and shaken under a 2540 X ultraviolet lamp for twenty-four
hours. The white solid turned red during this irradiation.
At the end of this time the vial was cooled in Dry Ice-ace¬
tone and 26.2 g. of methforyl iodide distilled into a trap.
The vial was sealed to an all glass vacuum system and any
volatile material was transferred to a trap cooled in
liquid air. The vial was removed and the contents washed
out with hexane. After filtering and evaporating the hexane,
4.3 g. of o-iodophenol remained, m.p. 43-44°. The residue
was extracted first with water and then with ether. The
water extract contained mercuric chloride, the ether ex¬
tract contained mercuric iodide and a dark residue remained.
The residue was extracted with ethyl alcohol to remove
o-chloromercuriphenol. A sodium fusion on the remaining
material disclosed fluorine and chlorine present hut further
identification was not possible. The trap cooled in liquid
air was removed from the vacuum system and allowed to warm
to room temperature. A solid remained in the trap, which,
after distillation, yielded 2.3 g. of o-methforylphenol,
b.p. 145-146, m.p. 44-45°. Bromination gave a white solid,
m.p. 48-49°. Jones reports for o-methforylphenol,

39
b.p. 147, m.p. 46°, and for the dibromomethforylforylphenol,
m.p. 50°. This reaction may he expressed as follows:
o-H0C6H4HgCl+ CF3I » o-HOC6H4I -h o-HOCgl^CFg +* Hgl2 + HgCl2
o-chloromercuriphenol and propforyl iodide—The
above experiment was repeated using propforyl iodide. A
mixture of 33 g. (0.1 mole) o~chloromercuriphenol and 60 g.
(0.206 mole) propforyl iodide was added to a 250 ml. Vycor
vial. The vial was sealed and exposed to ultraviolet light
for forty-eight hours. The vial became coated with a layer
of red solid. The vial was opened and 48 g. propforyl
iodide was recovered. The vial was sealed to a vacuum sys¬
tem and any volatile material removed. The solid material
in the vial was extracted with hexane and filtered. Evapo¬
ration of the filtrate did not yield o-iodophenol as in the
previous experiment. The residue was extracted with water,
ethyl ether and alcohol. The three extractions yielded
mercuric chloride, mercuric iodide and o-chloromercuriphenol,
respectively. A very small amount of dark residue remained.
After the liquid air trap was removed and the contents
warmed to room temperature, a liquid remained. Distillation
yielded 3.1 g. of a liquid boiling at 174-175°. The liquid
is assumed to be o-propforylphenol. This compound turns
dark in color after exposure to air and light.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for O-C3F7C0H4.OH;

40
C. 27.49, H. 1.92. Found: C. 27.53, H. 2.21.
Solubility—o-propforylphenol is soluble in ethyl
ether, alcohol and benzene. It is only slightly soluble in
water.
Aromatic Fluorocarbon Ethers
Potassium phenoxide with alkforyl iodides—In a
200 ml. copper pressure vessel were placed 66 g. (0.5 mole)
anhydrous potassium phenoxide and 50 g. (0.392 mole) meth-
foryl iodide. The vessel was heated to 150° for twelve
hours. At the end of this time the vessel was cooled and
opened. Only unreacted starting material was recovered.
This experiment was repeated using 66 g. (0.5 mole)
potassium phenoxide, 200 ml. anhydrous acetone and 50 g.
(0.392 mole) methforyl iodide in a 800 ml. copper pressure
vessel. The vessel was heated to 150° with rocking for
twelve hours. At the end of this time the vessel was cooled
and vented into a liquid air trap. There was collected 21
g. of material, which, when fractionated in a low tempera¬
ture column, had a boiling point of -85° to -83° and a
molecular weight of 69.6. On this basis it is assumed to be
fluoroform with a theoretical molecular weight of 70. Acetone,
unreacted starting material and a small amount of phenolic
tars remained in the reaction vessel.
When this experiment was performed with propforyl
iodide, 1-hydropropforane was obtained, indicating the

41
reaction proceeded in the same manner as the previous ex¬
periment.
Potassium phenoxide with dihromodifluoromethane—
In a 200 ml. copper pressure vessel were placed 33 g. (0.25
mole) anhydrous potassium phenoxide and 42 g. (0.2 mole)
dihromodifluoromethane. The vessel was heated to 100° with
rocking for twenty-four hours. At the end of this time the
vessel was cooled and opened. Starting material was the on¬
ly material recovered.
In a 500 ml. three necked flask equipped with a
magnetic stirrer, a Dry Ice-acetone cooled reflux condenser
and a gas inlet tube, were placed 74 g. (0.56 mole) anhy¬
drous potassium phenoxide and 400 ml. of anhydrous acetone.
This mixture was stirred and dihromodifluoromethane was
huhhled through the solution. After five minutes the mixture
turned red and the temperature rose rapidly to 55°. The ad¬
dition of dihromodifluoromethane was then regulated to keep
the temperature helow 50° until 118 g. (0.56 mole) were
added. The mixture was stirred for an additional twelve
hours at room temperature. At the end of this time a mix¬
ture of acetone and excess dihromodifluoromethane was dis¬
tilled from the solution. After removal of 300 ml. of
liquid, an equal volume of water was added and the mixture
was steam distilled. The distillate separated into two
layers. The lower layer was separated from the upper

42
aqueous layer, dried over anhydrous magnesium sulfate and
fractionated. Fractionation yielded 13.2 g. of difluoro-
methyl phenyl ether distilling at 60-67° at 30 mm., ISO-
MO0 at 763 mm., d254 1.171, n25D 1.4460. The molar re-
fractivity of difluoromethyl phenyl ether calculated from
the density and refractive index is 32.58; the value calcu¬
lated from the sum of atomic refractivities is 32.35.
To the excess dibromodifluoromethane and acetone
distilled from the original reaction mixture, two liters
of cold water were added and the dibromodifluoromethane
which separated was collected, dried and used for subsequent
experiments. The amount of dibromodifluoromethane recovered
was 50 g. The yield of difluoromethyl phenyl ether, based
on the dibromodifluoromethane used, was 28.3%.
This experiment was repeated substituting phenol
and solid potassium hydroxide for potassium phenoxide. This
change resulted in a decrease of the yield to 16.3%.
Solubility—Difluoromethyl phenyl ether is a color¬
less liquid with a very pungent odor, soluble in ethyl ether,
ethyl alcohol, benzene and this ether is insoluble in water.
Analysis—Analysis performed by Clark Analytical
Laboratory, Urbana, Illinois. Calculated for CgHgOCFgH;
C. 58.33; H. 4.20. Found: C. 58.37, H. 4.48.
Degradation—To 5 g. (0.035) mole) difluoromethyl
phenyl ether in a 50 ml. Erlenmeyer flask were added 10 ml.

43
of 50% sulfuric acid. As soon as the flask was shaken a
violet semi-solid mass was formed and hydrogen fluoride
was liberated. After the evolution of hydrogen fluoride
subsided, the mixture was neutralized with 20% sodium hy¬
droxide solution and filtered. The residue could not be
readily identified. The filtrate, however, after acidifi¬
cation and extraction with ethyl ether, yielded 1.1 g. of
phenol.
To a 50 ml. flask containing 2 g. (0.087 mole)
of sodium metal in 20 ml. of anhydrous ethyl ether, were
added 5 g. (0.035 mole) difluoromethyl phenyl ether. The
mixture was refluxed for twelve hours, after which the ex¬
cess sodium was slowly decomposed by adding ethyl ether
saturated with water. After acidifying the mixture with 20%
hydrochloric acid, the ether layer was separated, dried and
distilled, yielding 2.1 g. of unreacted difluoromethyl
phenyl ether and 1.6 g. of phenol. The dilute hydrochloric
acid layer contained a large amount of fluoride ion.

DISCUSSION
Organic Aromatic Ketones
Organic aromatic ketones have heen known and used
for many years. They can he prepared hy various methods.
The following equations represent some methods which are
applicable to all members of the group if yield is not of
primary importance.
1. C6H5CH0HR GOL» C6H5C0R -I- H20
2. C6H5MgX •+ RCOOEt g-ther^ c6H5C0R + EtOMgX
3. CgHgMgX ■+ RCN » C6H5C(:N Mg X)R
—» C6H5C0R -+ MgX2 + NH4X
4. C6H5CC12R H20 C6H5C0R +- 2HC1
PbO
5. CgHg H- RCOC1 Algia» CgHgCOR +- HC1
6. C6H5MgX -+• RCOC1 e-^.er> C6H5C0R +- MgXCl
7. C6H6-+• (RC0)20 43-PI3.» c6H5C0R 4- RCOOH
8. C6H50C0R Algia.» 0-H0C6H4C0R and p-H0C6H4C0R
The most widely used reaction for aromatic com¬
pounds is the Friedel-Crafts method listed as equation 5 or
7 above. The yields for the most part are very good.
44

45
Fluorocarbon Aromatic Ketones
OQ
Simons and Rambler utilized this reaction in
preparing the first fluorocarbon aromatic ketone, tri-
fluoroacetophenone. They found in a Friedel-Crafts acyla¬
tion of benzene with a fluorocarbon acid chloride that
there were no side reactions involving the fluorine in the
trifluoromethyl group. This was unusual in that Henne and
Newman observed that aluminum chloride reacts with or¬
ganic fluorides to produce aluminum fluoride and an organic
chloride.
Trifluoroacetophenone undergoes a haloform type
reaction in the presence of dilute potassium hydroxide to
yield fluoroform and potassium benzoate.
C6H5COCF3 -+- 10%K0H > CF3H + C6H5C00K
This reaction is unusual for an aromatic ketone
but is frequently encountered with aliphatic ketones. In a
similar reaction of aliphatic ketones, trifluoroacetophe¬
none formed a sodium bisulfite addition complex.
OQ
Simons and Rambler also found that a 2,4-dini-
trophenylhydrazone could be readily formed by standard pro¬
cedures and as in organic ketones, the carbonyl oxygen
could be replaced by chlorine, thus trifluoroacetophenone
reacted with phosphorous pentachloride under reflux condi¬
tions to form l,l,l,-trifluoro-2,2-dichloro-2-phenylethane.

46
Since trifluoroacetophenone had some properties
found in organic analogs and some properties peculiar to
aromatic ketones, it was decided to investigate other fluo¬
rocarbon aromatic ketones utilizing a Priedel-Crafts reac¬
tion and including other aromatic nuclei as well as other
fluorocarbon acid chlorides.
Since only trifluoroacetyl chloride and but-
foryl chloride x' had been previously prepared, it was
necessary to prepare three new fluorocarbon acid chlorides.
The reaction between the fluorocarbon carboxylic acids and
phosphorous pentachloride was the method used.
Rf COOH -4- PC15 » Rf COCI -+* P0C13 + HC1
The yields of the fluorocarbon acid chlorides were
approximately quantitative for all acids used. The ketones
were prepared using aluminum chloride or aluminum bromide
as the acylating agent in the Friedel-Crafts reaction and
an excess of the aromatic compound as the solvent. The pro¬
cedures were modified to facilitate using the different
acid chlorides.
The use of benzene and toluene as the aromatic
nuclei did not have any significant effect on the yield of
the ketones; however, in the case of toluene there was only
one isomer prepared. In every instance only the para ke¬
tone was produced and no trace of an ortho ketone could be
detected. The one experiment in which aluminum bromide was

47
used resulted in almost doubling the yield of ketone.
The ketones were found to undergo a haloform type
splitting reaction with concentrated base to give a mono-
hydrofluorocarbon and a salt of an aromatic acid. This may
be expressed by the following equation:
ArCGRf 4- KOI! » ArCOOK 4- RfH
This degradation served as a convenient method for proof of
the structure of the ketones. The aromatic acids obtained
upon acidification of the metallic salt did not require any
further purification.
In the preparation of the 2,4-dinitrophenylhydra-
zones it was found that the standard organic procedures did
not give any derivatives. It was necessary to modify the
standard procedure by increasing the sulfuric acid concen¬
tration and the reaction time.
Sodium bisulfite addition products could not be
formed; hox^ever, Simons and Rambler disclosed that the
first member of this ketone series did form a bisulfite
addition product, which, upon reaction with sulfuric acid,
regenerated the ketone.
They also reported that the carbonyl oxygen could
be replaced by chlorine by refluxing trifluoroacetophenone
with phosphorous pentachloride. This reaction could not be
performed with any of the other ketones.

48
It appears that trifluoroacetophenone, the first
member of the series, undergoes reactions that are quite
different from the rest of the series. Trifluoroacetophe-
none undergoes several reactions of aliphatic organic ke¬
tones, but the higher members of the series are quite inert
except to alkali.
Aromatic Esters of Fluorocarbon Acids
In organic chemistry there are several types of
aromatic esters that can be prepared. They are represented
by the following equations:
1. ArCOOH â– + ROH _> ArCOOR
2. ArOH -+- RCOOH RCOOAr
3. ArCOOH ~h ArOH » ArCOOAr
In fluorocarbon chemistry there have not been any
alcohols prepared of the type RpOH, so aromatic esters of
fluorocarbon acids are the only type of aromatic ester pos¬
sible. This type is represented by equation 2 above.
The organic esters, RCOOAr, are usually prepared
by one of the following methods. The preparation of phenyl
acetate will serve as examples.
1. c6h5oh -i- ch3cooh ch3cooc6h5 + h2o
2. CgHgONa-h CHgCOCl » CHgCOOCgHg + NaCl
3. c6h5oh + (ch3co)2 —» ch3cooc6h5 + CH3C00H
The first and second reactions are the methods most
generally used. This type of organic aromatic esters has

49
not "been used in large quantities. The chief use 4 of
these esters is in the preparation of hydroxyl aromatic ke¬
tones by the Pries reaction. This reaction is a variant of
the Friedel-Crafts method of acylation. It consists of the
conversion of an ester of a phenol to the corresponding
ortho or para hydroxy ketone, or a mixture of both, hy
treatment with aluminum chloride.
C6H50C0R o-H0C6H4C0R and p-HOCgH4COR
This procedure is convenient and of wide applica¬
bility when an organic aromatic compound cannot he acylated
hy any other method.
Several methods were attempted to prepare the aro¬
matic esters of fluorocarbon acids; however, only one gave
favorable results.
The reactions and yields in the case of trifluo-
roacetic acid were as follows:
1. C6H50Na 4* CF3COCI â–º CF3C00C6H5 -1- NaCl
20% yield
2. CgHgOH 4 CFgCOOH SgSO^. n0 Reaction
3. C6H50H 4 x* s CF3COOH » CF3C00C6H5 -j-
15% yield
CF3COOH H20 (azetrope) 33
4. C6H50H 4- (CF3C0)20 > CF3C00C6H5 4 CF3COOH
95% yield

50
The esters of the other fluorocarbon acids were
prepared by the last method and the yields averaged close to
95%.
It is unusual that the first two methods do not
give satisfactory results, as these methods are used exten¬
sively in organic chemistry and in fluorocarbon chemistry
to prepare aliphatic esters of fluorocarbon acids.
The esters were only slightly soluble in water, 10%
sodium bicarbonate and sulfuric acid. They were not hy¬
drolyzed by heating with mineral acids, but underwent sa¬
ponification with 10% sodium hydroxide. The resistance to
hydrolysis with mineral acids is in direct contrast to or¬
ganic esters and aliphatic fluorocarbon esters which are
easily hydrolyzed in the presence of mineral acids. The
rate of saponification decreased proportionately from
phenyl trifluoroacetate to phenyl caproforate.
The esters did not undergo the Fries reaction as
do the organic analogs to produce ortho and para hydroxy ke¬
tones.
Phenyltrifluoroacetate reacted with phosphorous
pentachloride to produce an <=*,<*. -dichloro ether, phenoxy-
2,2,2-trifluoro-l,l-dichloroethane.
CF3C00C6H5 -+ PC15 » CF3CC120C6H5 4- P0C13
This reaction demonstrates the stability and an unusual
property of the aromatic esters of fluorocarbon acids.

51
Organic esters react with phosphorous pentachlo-
ride to form organic chlorides and acid chlorides.
RCOOR1 ■+ PC15 » RC0C1 -f R'Cl 4- P0C13
Phenoxy-2,2,2-trifluoro-l,l-dichloroethane is a
very stable compound that can he distilled at atmospheric
pressure without discoloring and resists the action of
chromic acid at 100°. The ether, however, was attacked by
prolonged treatment with hot 80% sulfuric acid to yield
phenol.
Alkforvi Aromatic Compounds
The preparation of alkforyl aromatic compounds has
been limited to benzotrifluoride and ethforylbenzene. Since
this type of compound is expected to have a large future po¬
tential, an attempt was made to prepare the higher members
of the alkforyl aromatic compounds or their derivatives.
The first attempts to prepare the alkforyl aro¬
matic compounds were adaptations of organic chemical re¬
actions. Previous experiments have shown that Friedel-
Crafts acylation works very well in fluorocarbon chemistry,
so a Friedel-Crafts alkylation reaction using fluorocarbon
halides and aromatic compounds might produce the desired
final product.
Ethforyl chloride failed to react with benzene in
a Friedel-Crafts reaction. This is not surprising, as
ethforyl chloride is a very inert chemical that does not

52
enter into chemical reactions like organic chlorides.
The reaction of propforyl iodide with benzene
using aluminum chloride as a catalyst leads to iodobenzene,
iodine, inorganic fluoride and fluorine containing tars. It
appears that the fluorocarbon iodides react in an opposite
manner to the organic halides. It is believed that under
ionic reaction conditions, the fluorocarbon iodides form
R^ and I+, whereas, organic iodides form R+ and I”. This re¬
action lends some support to this idea.
The reaction of an aromatic Grignard compound and
propforyl iodide yielded upon acidification only hexforane
and iodobenzene in significant quantities. The reaction
probably proceeds through an exchange to produce a fluoro¬
carbon Grignard reagent followed by coupling with excess
fluorocarbon iodide. It may be expressed as follows:
C6H5MgI + C3F7I > C6H5I -h C3F7MgI C3E3X»
C6F14 + Mgl2 + C6H5I
The product obtained from phenyl sodium and prop¬
foryl iodide could not be identified, inasmuch as it had a
wide boiling range. Some propforylbenzene might have been
prepared, but the excess chlorobenzene used in preparing
the phenyl sodium made separation impossible.
When phenyl lithium was allowed to react with
propforyl iodide, there was a considerable amount of di¬
phenyl produced indicating coupling between aromatic nuclei

53
occurred. The fluorine containing fraction obtained could
not he separated from bromobenzene.
Upon substituting p-tolyl lithium for phenyl
lithium, the coupling reaction was decreased and it was pos
sible to isolate a small sample of an alkforyl aromatic com
pound. By infrared spectra comparison with known substi¬
tuted toluene derivatives, it is assumed that the propforyl
toluene is para substituted; however, in the absence of
chemical reactions, this infrared spectra data cannot be
used for absolute proof of structure.
The reaction between fluorocarbon iodides and
o-chloromercuriphenol yields o-alkforylphenols. This reac¬
tion is similar to a reaction used in organic chemistry to
prepare o-iodophenol.
o-H0C6H4HgCl 4- I2 „ o-H0C6H4I + Hgl2 + HgCl2
When methforyl iodide was used, both o-methforyl-
phenol and o-iodophenol were obtained; however, when prop¬
foryl iodide was used with o-chloromercuriphenol, only
o-propforylphenol was prepared and there was no trace of
o-iodophenol.
This reaction works well for both alkforyl iodides
used; however, during the course of the reaction, the vial
becomes coated with mercuric iodide and the reaction is no
longer activated by the ultraviolet light. This necessi¬
tates the frequent changing of vials if any significant

54
quantity of product is desired.
Aromatic Fluorocarbon Ethers
There have been no organic fluorocarbon ethers pre¬
pared in which the fluorocarbon group contained only fluo¬
rine; however, ethers have been prepared where the fluoro¬
carbon group contained chlorine atoms or hydrogen atoms.
Compounds of the type R^,ORf where R^ are fluorocarbon radi¬
cals are very stable and are completely void of the chemical
properties associated with organic ethers of the type ROR.
It was desired to produce an aromatic fluorocarbon
ether, since this compound might be very stable, and as such,
might become a very useful starting material.
The reaction between potassium phenoxide and a
fluorocarbon iodide was attempted to produce such an ether.
The only fluorine containing material obtained was fluoro-
forrn in the case of methforyl iodide and 1-hydropropforane
when propforyl iodide was used. The potassium phenoxide in
acetone reacts in a manner similar to potassium hydroxide
when treated with a fluorocarbon iodide. Banus, Emeleus
and Haszeldine 1 report the reaction of methforyl iodide with
solutions of potassium hydroxide in alcohol, acetone or
ethyl ether yielded fluoroform.
The second reaction attempted to produce the
desired type of ethers was between potassium phenoxide
and dibromodifluoromethane. It was hoped that phenyl

55
bromodifluorornethy1 ether could he produced and the bromine
atom replaced with fluorine to give trifluoromethyl phenyl
ether; however, the reaction between potassium phenoxide and
dibromodifluoromethane in acetone gave difluoromethyl phenyl
ether. Since there was no reaction between potassium phen¬
oxide and dibromodifluoromethane when heated in the absence
of a solvent or between acetone and dibromodifluoromethane,
it is believed that the hydrogen present in the difluoro¬
methyl group came from the acetone solvent. These reac¬
tions may be expressed as follows:
C6H50K -f- CFgBrg —— No Reaction
CF2Br2 + CH3GOCH3 £— No Reaction
CgHgOK 4- CF2Br2
CH3COCH3
C6H50CP2H
This ether is the only stable one containing the
QO
difluoromethyl group. Swarts , together with Henne and
tv
Smook , have prepared ethyl difluoromethyl ether but report
it is very unstable, and both had difficulty obtaining even
the boiling point of this compound.
Difluoromethyl phenyl ether decomposes in the pres¬
ence of mineral acids and is unaffected by alkalis.
Proof of the structure of difluoromethyl phenyl
ether was difficult, since there were no known reactions
available. It was necessary to cleave the ether to produce
phenol, in order to prove the CgHgO group was present. Both
sulfuric acid and sodium metal were satisfactory for this

56
purpose. No reactions could "be devised to determine the
CF^H or CFgHO group. The use of the molar refraction, car¬
bon and hydrogen analyses, together with the degradation to
phenol, were considered proof of the structure of the ether.
Conclusions
As can he seen from the previous discussion, fluoro
carbon aromatic compounds differ widely from their organic
analogs. It is usually the exception rather than the rule
that applies to fluorocarbon aromatic compounds when the
rules and procedures of organic chemistry are utilized. Be¬
cause of this, it is necessary to accumulate a large amount
of experimental data, in order to formulate organized rules
applicable to fluorocarbon aromatic compounds.
It is with this view in mind that the preceding
work is presented, in the hope that the experimental re¬
sults will contribute to the chemistry of fluorocarbon aro¬
matic compounds, and as such, will lead to the organization
and understanding of fluorocarbon chemistry.

SUMMARY
The preparation and some of the physical and chemi¬
cal properties of thirty-two previously unreported fluoro¬
carbon compounds is presented. Ten distinct molecular
species are represented by these compounds. They may be
summarized as follows:
1. A series of fluorocarbon aromatic ketones were
prepared by a Friedel-Crafts reaction between a fluorocarbon
acid chloride and an aromatic compound. Some of their chemi¬
cal and physical properties were determined. With benzene
the ketones were of the type:
0
rcc6h5
The compounds prepared were for R equal to the following:
C2f5C4F9~ 311(1 C5F11“*
Using toluene as the aromatic compound, the ketones
were of the type:
0
II
p-rcc6h4ch3
The compounds prepared were for R equal to the following:
CF3“> C2F5"' C3F7"' C4F9~ 311(1 C5F11“*
57

58
Using meta-xylene as the aromatic compound and
caproforyl acid chloride, the ketone was:
0
2,4-(CH3)2c6H3Cc5P11
The ketones did not entirely follow the first mem¬
ber of the series, trifluoroacetophenone, in their chemical
reactions. The ketones split in the presence of dilute
alkali to form a metallic salt of an organic acid and a
monohydrofluorocarhon. They formed 2,4-dinitrophenylhy-
drazones as does trifluoroacetophenone, "but a sodium bisul¬
fite addition complex could not be prepared and the car¬
bonyl oxygen could not be replaced by chlorine as does the
first member of the series, trifluoroacetophenone.
2. A series of 2,4-dinitrophenylhydrazones were
prepared and some of their physical properties determined.
These compounds have the following structure:
2,4-(N02)C6H3NHN = R
The compounds prepared were for R equal to the following:
C2F5CC6H5' C4F9CC6H5> C5F11CC6H5' P-^gCCgH^Hg,
p-C2F5CC6H4CH3, p-C3F7CC6H4CH3, p-C4F9CC6H4CH3and
P"C5F11CC6H4CH3 *
3. A series of aromatic esters of fluorocarbon
acids were prepared and some of their chemical and physical
properties determined. The esters were of the following
type:

59
O
II
rcoc6h5
The compounds prepared were for R equal to the following:
CF3-, CgFg-, C3F7-, C4F9- and CgF]^-.
These compounds were found to he resistant to acid hydrol¬
ysis hut saponified readily hy dilute alkali. The first
member of the series reacted with phosphorous pentachloride
replacing the carhonyl oxygen with two chlorine atoms and
forming an e<,oc-dichloro phenyl ether.
4. An aromatic thio ester of trifluoroacetic acid
was prepared and some of its physical properties determined.
It is believed to have the following structure:
0
cf3csc6h5
5. Phenoxy-2,2,2-trifluoro-l,l-dichloroethane was
prepared and some of its physical and chemical properties
determined. This phenyl ether was found to he very stable,
and only after prolonged treatment with 80% sulfuric acid
did the ether split to phenol.
6. Difluoromethyl phenyl ether was prepared and
some of its physical and chemical properties determined. At
the present time this ether is the only stable difluoro¬
methyl ether.
7. p-propforyl toluene was prepared and some of
its physical properties determined.

60
8. o-propforyl phenol was prepared and some of its
physical and chemical properties determined.
9. Propforic, valerforic and caproforic acid chlo¬
rides were prepared. Some of their physical properties and
uses in Friedel-Crafts acylations are reported.
10. Propforic, valerforic and caproforic acid an¬
hydrides were prepared. Some of their physical properties
were determined and their use in esterification of aromatic
phenols is reported.

BIBLIOGRAPHY
1. Banus, J., Emeleus, H. J., and Haszeldine, R. N., J.
Chem. Soc. 60, (1951).
2. Cohen, S. G., Wolosinki, H. T., and Scheurer, P. J.,
J. Am. Chem. Soc. 71, 3439 (1949).
3. Crawford, G. H., and Simons, J. H., J. Am. Chem. Soc.
75. 5737 (1953).
4. Fuson, R. C., "Advanced Organic Chemistry", John Wiley
and Sons, Inc., New York, 1950, p.344.
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367 (1947).
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4378 (1950).
8. I. G. Farbenind. A.-G., French Patent 745,293
(May 8, 1933).
9. I. G. Farbenind. A.-G., German Patent 575,593
(May 22, 1933).
10. Jones, R. G., J. Am. Chem. Soc. 69. 2346 (1947).
11* Ibid.. 70. 143 (1948).
12. Kimball, R. H., and Tufts, L. E., Anal. Chem. 19,
150 (1946).
13. Kinetic Chemicals, Inc., Brit. Patent 391,168
(April 12, 1933).
14. Lebeau, P., and Damiens, H., Compt. rend. 183.
1340 (1926).
61

62
15. MeBee, E. T., and Bolt, R. 0., Ind. Eng. Chem. 39,
412 (1947).
16. McBee, E. T.. and Pierce, 0. R., Ind. Eng. Chem. 39.
397 (1947).
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
Minnesota Mining and Manufacturing Company, Technical
Bulletin, "Heptafluorobutyric Acid” (1949).
Moissan, H., Compt. rend. 102. 1453 (1886).
Nes, W. R., and Burger, A., J. Am. Chem. Soc. 72.
5409 (1950).
Renoll, M. W., J. Am. Chem. Soc. 68, 1159 (1946).
Renoll, M. W., U. S. Patent 2,414,330 (January 14, 1947).
Ruff, 0., and Bretschneider, 0., Z. anorg. allgem.
Chem. 210. 173 (1933).
Ruff, 0., and Keim, R., Z. anorg. allgem. Chem. 192.
249 (1930).
Shirley, D. A., ''Preparation of Organic Intermediates”,
John Wiley and Sons, Inc., New York, 1951, p.260.
Simons, J. H. and Block, L. P., J. Am. Chem. Soc. 59.
1407 (1937).
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2064 (1943).
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364 (1947).
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Swarts, F., Bull, classe sci. Acad. roy. Belg. 8,
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Swarts, F., Bull. soc. chem. Belg., 120 (1910).

63
33. Ibid.. 48. 176 (1939).
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5831 (1951).
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Anal. Ed. 5, 7 (1933).

ACKNOWLEDGMENTS
The author wishes to express his gratitude to
Dr. J. H. Simons for the encouragement and advice pro¬
vided during this investigation.
Also, the author wishes to express his thanks
to the other members of his supervisory committee for their
assistance and encouragement.
The author also wishes to acknowledge the sponsor¬
ship of the Minnesota Mining and Manufacturing Company with¬
out which this work would not have been possible.
64

BIOGRAPHICAL NOTE
Reginald F. Clark was "born on February 24, 1927 in
Millerton, New York.
In 1944, he enlisted in the U. S. Army and was
honorably discharged in 1946. During this period he at¬
tended Princeton University, Princeton, New Jersey, under
the Army Specialized Training Program.
He entered the University of Illinois, Urbana,
Illinois, in 1947 and received a Bachelors of Science degree
in 1951.
In 1951, he entered the Graduate School of the
University of Florida. He was a Graduate Assistant from
1951 to 1954 and held an Industrial Fellowship from 1954 to
1956.
In July 1956, he was appointed to the faculty of
the University of Florida.
Mr. Clark is a member of the American Chemical
Society, Gamma Sigma Epsilon and Sigma Xi.
65

COMMITTEE REPORT
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 Science and
to the Graduate Council, and was approved as partial fulfill¬
ment of the requirements for the degree of Doctor of Philos¬
ophy.
August 11, 1956.
Supervisory Committee:
Dean, College of Arts and Science
Dean, Graduate School