• TABLE OF CONTENTS
HIDE
 Title Page
 Table of Contents
 List of Tables
 Acknowledgement
 Introduction
 Discussion
 Infrared spectra
 General considerations
 Experimental
 Summary
 Bibliography
 Biographical data






Group Title: synthesis of some fluorine-containing cyclobutanes by cycloalkylation
Title: The Synthesis of some fluorine-containing cyclobutanes by cycloalkylation
CITATION PDF VIEWER THUMBNAILS PAGE IMAGE ZOOMABLE
Full Citation
STANDARD VIEW MARC VIEW
Permanent Link: http://ufdc.ufl.edu/UF00098003/00001
 Material Information
Title: The Synthesis of some fluorine-containing cyclobutanes by cycloalkylation
Physical Description: iv, 66 l. : ; 28 cm.
Language: English
Creator: Johnson, Robert William, 1927-
Publication Date: 1959
Copyright Date: 1959
 Subjects
Subject: Organofluorine compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis--University of Florida.
Bibliography: Bibliography: l. 64-65.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00098003
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000421889
oclc - 11021083
notis - ACG9887

Downloads

This item has the following downloads:

PDF ( 2 MBs ) ( PDF )


Table of Contents
    Title Page
        Page i
    Table of Contents
        Page ii
    List of Tables
        Page iii
    Acknowledgement
        Page iv
    Introduction
        Page 1
        Page 2
        Page 3
    Discussion
        Page 4
        Page 5
        Page 6
        Page 7
        Page 8
        Page 9
        Page 10
        Page 11
        Page 12
        Page 13
        Page 14
    Infrared spectra
        Page 15
        Page 16
    General considerations
        Page 17
        Page 18
        Page 19
        Page 20
        Page 21
        Page 22
        Page 23
    Experimental
        Page 24
        Page 25
        Page 26
        Page 27
        Page 28
        Page 29
        Page 30
        Page 31
        Page 32
        Page 33
        Page 34
        Page 35
        Page 36
        Page 37
        Page 38
        Page 39
        Page 40
        Page 41
        Page 42
        Page 43
        Page 44
        Page 45
        Page 46
        Page 47
        Page 48
        Page 49
        Page 50
        Page 51
        Page 52
        Page 53
        Page 54
        Page 55
        Page 56
        Page 57
        Page 58
        Page 59
        Page 60
        Page 61
        Page 62
    Summary
        Page 63
    Bibliography
        Page 64
        Page 65
    Biographical data
        Page 66
        Page 67
        Page 68
Full Text










THE SYNTHESIS OF SOME

FLUORINE-CONTAINING CYCLOBUTANES

BY CYCLOALKYLATION










By
ROBERT WILLIAM JOHNSON, JR.


A DISSERTATION PRESENTED TO THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY











UNIVERSITY OF FLORIDA
June, 1959










TABLE OF CONTENTS


LIST OF TABLES . . . . . . . . . . . .

ACNOL ETS . . . . . . . . . . .

I. INTRODUCTION . . . . . . . . . . . .

II. DISCUSSION . . . . . . . . . . . . .

III. INFRARED SPECTRA . . . . . . . . . . .

IV. GENERAL CONSIDERATIONS . . . . . . . . .

V. EXPERIMENTAL . . . . . . . . . . . .

A. Reactions of 1.3-Butadiene with Fluorolefins . .

B. Reactions of Styrene with Fluoroilefine . . . .

C. Reactions of Chlorotrifluoroethylene with Olefine .

D. Miscellaneous Addition Reaction . . . . . .

E. Reactions of Addition Product . . . . . .

VI. SUMMAR . . . . . . . . . . . . .

VII. BIBLIOGRAPHY . . . . . . . . . . . .

BIOGRAPHICAL DATA . . . . . . . . . .


Page

iii

iv

1

4

15

17

24

25

36

41

54

58

63

64

66










LIST OF TABLES


Table Page

I. Properties of the Compounds Prepared 19

II. Analyses of the Compounds Prepared 22










ACKNOWLEDGMENTS


"From the nature of things, ideas do not corm from prosperity,

affluemee and contentment, but rather from the blackness of despair.

not in the bright light of day or in the footlight's glare but rather

in the quiet, undisturbed hours of midnight or early morning when one

is alone to think!.......

Dr. Frederick Banting





The author wishes to express his appreciation to many people

for their contributions to the completion of this research problem.

He gratefully acknowledges the advice and assistance of Dr. Paul Tarrant.

chairman of the Supervisory Committee and director of this research.

Special thanks is given to Dr. W. 5. Brey, Jr. for interpretation of

the lMr data. For their valuable suggestions and building certain

apparatus, thanks are due to Mr. P. J. Thompson and Mr. Calvin Workinger.

This research was carried out under a grant financed by the

Office of the Quartermaster General, U.S. Army, whose support the

author now acknowledges.










I INTRODUCTION


The Office of the Quartermaster General established and is

currently sponsoring a long-range Arctic Rubber Program for the purpose

of discovering and developing elastomers which have the desired low-

temperature properties, resistance to swelling when in contact with

hydrocarbon fuels and resistance to deterioration by oxidizing agents.

Fluorine-containing compounds such as polytetrafluoroethylene

and polychlorotrifluoroethylene have shown extraordinary inertness

and range of usefulness. Several fluorobutadienes, when polymerized,

have shown remarkable low temperature flexibility along with good

solvent resistance. The most promising of these are homopolymers of

1,1.2-trifluorobutadiene and 1.1.3-trifluorobutadiene and a copolymer

of the two dienes.

In looking for new methods for preparing fluorobutadienes

attention was directed to work done by Coffran and by Anderson.

Cofftan (7) prepared a series of cyclobutane derivatives in which

tetrafluoroethylene was reacted with a variety of olefins. Some

typical reactions are as follows:

CF2=CF2 + CHCH2=CHCH=H2 CH2-CHCH=CH2
I I



CFC2 + CH2 3 -- CH2-CHF
C2-F2










CF2CFF2 + CH=CHCN CH2-CHCN
I I
CF2-CF2

It was observed that the co-diuerization reaction occurred at a lower

temperature than the dinerization of tetrafluoroethylene and without

the formation of open-chain polymers.

Anderson (1) has prepared fluorinated butadienes containing

functional groups by the novel method illustrated below:

CF2=CF2 + CrECC02CH3 -- -- CF -CCO2CH

CF2-CH

CO2CH3
CF-CCO2 pyrolyi CF2CCH=CF2
CI 2 2 3 F2 =C 2
CF2-CH

These methods of preparation can also be applied to a number

of compounds reported in this dissertation. Typical examples are as

follows:

CF2=CFC1 + CH2=CHCH C^ -CHCH

CF2-CFC1

CH2-CH3 + methanolic KOH ----* C2-CH -

CF2-CFC1 CF2-CF

CH

CF2=CPFCCH-

By using excess alcoholic potassium hydroxide, ethers could be

prepared:










CH2-CHCH3 + methanolic KOH -- CH2-CCH3

CF2-CFC1 CF2-COCH

OCH3 CH-

CF2=C-----C=CH2 si

Because of the variety and usefulness of compounds that are

obtained from the co-dimerization of fluoroolefins with hydrocarbon

olefins, it seemed desirable to prepare a series of such compounds

and to study their mode of formation. The products of the co-

dimerization reactions are substituted cyclobutanes and in some

cases substituted cyclohexenes are also formed.

The co-dimerization reactions reported in this dissertation

are all thermal initiated reactions in the temperature range of

100-310o, and then necessary, in the presence of a polymerization

inhibitor.










II DISCUSSION


In the course of some investigations on the reactions of

fluoroblefina with dienes, it was observed that either a four-membered

or a six-membered ring was produced. For example, Coffman (7) reacted

tetrafluoroethylene with butadiene and obtained only the cyclobutane

derivative:

CF2=CF2 + CH2=CHCH=CH2 ---- C2-CHCH=CH2
1 1
CF2-CF2

McBee (19), on the other hand, reacted perfluoropropene with butadiene

and reported that the reaction proceeded in a Diels-Alder fashion to

give a cyclohexene derivative:

/CH2
CF2=CFCF3 + CH2=CHCH=CH2 -- CI1 CFCF3

C1I CF,
CH2

Many other olefins have been reacted with butadiene to give the Diels-

Alder product, a substituted cyclohexene. However, no reaction has

been reported in which both a four-membered and a six-membered ring

were formed simultaneously in the reaction.

The following are some observations on the formation of

four-membered versus six-nembered rings. Ethylene reacts with

butadiene to give cyclohexene (15). Tetrafluoroethylene reacts with

butadiene to give l-vinyl-2,23,3,-tetrafluorocyclobutane (7).

Considering only these two reactions, it appears that cyclobutane
4









formation should be favored if the hydrogens on ethylene were replaced

by strong electronegative groups. This observation seems to be only

partly true. The other criterion appears to be steric in nature.

For example, tetracyanoethylene, (NC)2C=C(CN)2, reacts with butadiene

to give a substituted cyclohexene instead of forming the cyclobutane

derivative (20). However, when the system demands it, the cyclobutane
ring is formed (4).

O--CC=CH2 + C(CN)2 ----- -C-C=C
11 I II H I
--C-C=CH2 C(CN)2 0-C-C--C(CN)2
I I
CH2-C(CN)2

As can be seen, if the cyclohexene were formed then the highly unstable

cyclobutadiene would have formed simultaneously.

Acrylonitrile reacts with butadiene to give only the Diels-Alder

2\
product, CH CH2 (22), thus showing that the steric requirement
CH ,CHCN
CH2

alone does not suffice in the formation of the cyclobutane ring. Like

ethylene, it reacts with butadiene to form a six-membered ring.

However, acrylonitrile forms a cyclic dimer, CH2-CHCN, when heated to
I I
CH2-CHCN

190-300 in the presence of a polymerization inhibitor (8), whereas
neither ethylene nor tetracyanoethylene (6) form cyclic dimers when

heated to temperatures even greater than this.










It has also been observed that the co-dimerization of

tetrafluoroethylene with reactants containing a terminal methylene

group occurs more readily than with 1,2-disubstituted ethylene such

as 2-buterr or trichloroethyleme (7).

Thus, from the preceding discussion, it seeme that in order

to form the cyclobutane ring from a cycloalkylation reaction in

reasonable yields, the following steric requirement must be met:

Only hydrogen or fluorine atoms can be attached to

the double-bonded terminal carbon of both olefina; for

example, both of the reactants must have one of the groups

present: CH2=C. CHFC. CF2=C.

It has also been observed in cyclic dimerizatlon reactions

that some diners were formed only in a head-to-head manner (13) while

other diners were formed both in a head-to-head and in a head-to-tail

manner (12):

CF2=CFC1 ---- CF-CFC

CF2-CFCl

CF2=CFCF --- CF2-CFCF + CF2-CFCF,

CF2-CFCF3 CF3CP--CF2

Essentially two types of transition state have been proposed

for the process:

An open chain diradical structure (A) in which the

nost stable diradical would be formed (28) and a cycle

delocalized (four centered) structure (B) (14).










CF2=CFC1 CF2-CFC1 (A)

CF2-CFC1

CF=CFC1 ---CFC CF ---CFC1 (B)
.2 2..... ....

CF2-CFC1 CFC1--CF2
1 2

Transition state (A) should be favored over that of (B) because of

the following reason. Only one product is formed, that being 1,2-

dichloroperfluorocyclobutane (13). If the reaction proceeded through

transition state (B) it would seem likely that some 1,3-dichloroper-

fluorocyclobutane from structure 2 would have formed. Increasing

the reaction temperature, which would favor a more random formation,

causes only a break-down of the cyclobutane ring without any of the

1,3-type structure being observed (21).

The more stable free radical can be predicted on the basis

of an empirical rule (17). If the radical R. is added to the olefin

a b

C= C and if 2 (EAR)aa, < ( (EAR)bb,, where E is the Pauling
I I
a' b'

electronegativity and AR is the atomic refraction of a, a', b, b',

then the orientation will be a b The radical R* attacks the

R-C---C

a' b'

olefinic carbon with the lowest (EAR) of its substituents and thus

forms the more stable free radical. Listed below are the EAR values

of some of the common elements:









Atom H F Cl B I C

EAR 2.31 4.80 18.0 24.9 33.4 6.0

The (EAR) for -CFC1- is 22.8 compared to 9.6 for -CF2 .

This indicates that the -CFCl- is much more stable than the -CF2*.

In the dinerization of perfluoropropene, it has been observed

that both the head-to-head and head-to-tail structures are formed (12).

Only the open-chain diradical transition state will be considered in

accounting for the observed products. The three transition states

for this dimerization are:

CF2-CFCF3 CF2-CFCF3 CF2-CFCF3
S -* I | 1
CF2-CFCF3 CF CP-CF2 CF2-CFCF

(A) (B) (C)
The 2 (EAR) for -CFCF3 is 10.8 compared to 9.6 for -CF2*. a difference

of only 1.2. Therefore: the ctabi.lities of the diradicals would be

approximately equal. Transition state (A) would be slightly favored

over (B), which in turn, would be slightly favored over (C).

Transition states (A) and (C) would give rise to the sane product,

a 1,2-type structure, while (B) would give a 1,3-type structure. Even

when the difference of the L. (EAR) values is as much as 2.5. as in

the following example, two different free radicals are formed (11):

CF 3 + CdF-CF2 -- CF2CHFCF2- + F3CF2CHF-

EAR 7.1 9.6 80% 20&

Thus, in the dimerization of perfluoropropene. it is not too surprising

even at the lower temperatures that both the 1.2- and the 1.3-type

structures are formed with the 1,2-type structure predominating.









Higher temperatures favor a more random type of attack and the more

stable product, and the 1,3-type structure is predominately formed (12).

The above discussions were presented as a basis for the mode

of formation for this type of reaction and in discussing the structures

of products presented herein, frequent use of the tern "mode of

formation" will be made.

The addition of chlorotrifluoroethylene to isoprene can give

rise to six different products (not counting cis-trans isomers):

CH CH
S3 1 3 /C2
CHI2-CCHCH2 CH2--CCH=CH CH -C CF2
I 2 I 2 I3 2
CF2-CFC1 CFC1-CF2 CH CFC1
C2 H2
2

Xa Xb Xc


CH CH,
1 3 1 3 CH
CH2-CHC=CH2 CH2--CHC=CH2 CH -C CFC1
1 2 1 1 2 1 2 3 11 1
CF2-CFC1 CFC1-CF2 CH /CF2
CH2

Xd Xe Xf

Only structure Xa fits all of the experimental data. Its failure to

react with alcoholic potassium hydroxide is a strong indication that

there is no hydrogen on the carbon atom adjacent to the carbon atom

holding the chlorine. DMR results show the absence of a six-membered

ring and the presence of two kinds of four-membered ring structures

which are cis-trans isomers of structure Xa.










1,1-Dichlorodifluoroethylene reacted with butadiene to give

only the cyclobutane structure. ?P- results show that only one kind

of four-membered ring structure was present. This material has been

assigned the structure CH,-HCHCH=C2, IV, on the basis that it would
I I
CF2-CC12

arise from the more stable diradical as previously discussed, and

because of its similarity to Xa.

A series of fluoro6lefins of the type CF2=CFX, where X was Cl,

Br, I. C;, CF3, CH2CHBr and H, wore reacted with butadiene and the

mode of formation studied. The ease of reaction seemed to vary with

the electronegativity of X, the order of decreasing reactivity being

Cl> C1 > Br> I >CF 3 > HCH2Br > H. This approximate order of

reactivity is based on the conversion to products when these fluoro-

olefins were reacted with butadiene and styrene.

Chlorotrifluoroethylene, bromotrifluoroethylene and iodotri-

fluoroethylene reacted with butadiene to give only the cyclobutane

structure. For each of these reaction products IPR results show the

presence of two kinds of cyclobutane structures, which are probably

cis-trana isomers of the 1,2-type structure. This would be expected

since the 1,2-type structure arises from the more stable diradical.

These materials have been assigned the structures

CH2--CHC=CH2 CH2-C1CHCH C2 and CH2-CHCH=CH2
I I I I I I
CF2-CFC1 CF2-CFBr CF2-CFI

I II III










Perfluoropropene, perfluoroacrylonitrile and 4-bromo-1,,12-

trifluoro-1-butene reacted with butadiene to give in each case both

the cyclohexene ring and the cyclobutane ring structures. IMR results

show that only one kind of cyclobutane structure was present.

The addition products of perfluoropropene to butadiene have

been assigned the structures

i/ Cil
CH CFCF and CH2-CHCH=CH
11 I 3 I2 I2 2
CH CFZ CF -CFCFa

2

Va Vb

The 1,2-type structure is preferred over the 1,3-type structure since

it arises from the more stable diradical. Since there is only one

kind of four-men-bered ring structure, Vb exists either with the

trifluoromethyl group cis or trans to the vinyl group. No reason can

be given here as to which structure is present or why a cyclohexene

ring was formed in this case.

The addition products of perfluoroacrylonitrile to butadiene

and of 4-bromo-11l,2-trifluoro-l-butene to butadiene have been

assigned the structures

CH CH2
CH CFCN C(H2-C{HCH=CH2 CH CFCH2CH2Br
11 I II I
CH CF2 CF2-CFCHI CH CF2
CH2 CH


VIb Vla










and CH2-CHCH=CH2

CF2-CFCH2CH2Br

VIIb

The 1,2-type structures for YIb and VIIb are preferred over the

1.3-type structure for reasons previously given.

The addition of trifluoroethylene to butadiene gave a mixture

of two components as shown by its gas chromatogram. One peak has been

identified as being due to 4-vinylcyclohexene, a product of the

Diels-Alder dimerization of butadiene. The other peak has not been

identified since the 4-vinylcyclohexene interferes with the methods

of analysis used in identifying compounds of similar structure.

The addition of 2,3-dichlorohexafluoro-2-butene to butadiene

gave a material. IX, t.hich has been assigned the structure


CH CCICF3 on the basis of its composition and its reaction

CH CC1CF3
CH2

with alcoholic potassium hydroxide to give the known (5) 1,2-bis-


OCCF
(trifluoromethyl)bensane, [ '3 The reason that a cyclohexene



ring was formed in preference to a cyclobutane ring was probably due

to steric effects. The dimerization of 1,2-dichloredifluoroethylenu

does not give CFC1-CFC1. but rather an open chain diner.
I I
CFC1-CFC1

CFC12CFCICF-CFC1 (10). This is not due to the instability of the










cyclic diner because it has been prepared by a different route.

The addition of chlorotrifluoroethylene to isobutylene gave

a material, XIX, which has been assigned the structure CH2-C(CH3)2
1 i
CF2-CFC1

on the basis of its mode of formation, NMR spectrum and its failure

to react with alcoholic potassium hydroxide. A structure in which

a hydrogen on a carbon atom adjacent to a carbon holding the chlorine

would be expected to react with alcoholic potassium hydroxide.

The addition of chlorotrifluoroethylene to acrylonitrile gave

a material, XXII, which has been assigned the structure CH2-CHCN
I I
CF2-CFC1

on the basis of its mode of formation, NMR spectrum and its ease of

reaction with alcoholic potassium hydroxide. Further evidence

supporting this structure is found in the work of Barney and Cairns (2).

They carried out the following reactions:

160o
CH2=CHCN + CF2=CFC1 CH-CHCN
I I
CF2-CFC1


H, H20



H2CH2C02H

CF2CO2H

No acid containing chlorine was found as would be expected if a

1.3-type structure were present.




14




The addition of chlorotrifluoroethylene to methacrylonitrile

gave a material, XXIII, which has been assigned the structure



CH2-CC:I on the basis of its mode of formation, riIR spectrum and its

CF2-CFCI

failure to react with alcoholic potassium hydroxide. A structure

in which a hydrogen on a carbon atom adjacent to a carbon holding the

chlorine would be expected to react with alcoholic potassium hydroxide.

Other reactions and structure proofs are given in the

Experinental section of this dissertation.










III INFRARED SPECTRA


One of the most valuable means of detection of double bonds

through infrared spectra is the examination of the region near 3.3

microns. Tallent (27) reported data for the =CH stretching bands for

several representative olefinic systems using sodium chloride optics.

He assigned the peak at 3.23-3.25 microns to the =CH stretch for a

terminal methylene and the peak at 3.29-3.32 microns to the =CH

stretch in a six-membered system. In the present investigation for

compounds assigned the general structure CH2-CHCH=CH2, a peak occurs
| I
CF2-CFX

at 3.20 microns which is believed to be due to the =CH stretch for

a terminal methylene. There is also a peak at 3.28-3.29 microns

possibly due to the =CH stretch in a six-membered ring. However, on

bromination of this material the peak at 3.20 microns disappears

while the one at 3.28-3.29 microns is still present. Roberts (24)

has shown that the frequencies of the CH2 bands increase as the ring

size becomes smaller. He examined the CH2 vibrations of three-, four-,

five- and six-membered rings substituted with a single chlorine, and

found that the value for the six-membered ring was normal, 3.43 microns.

for the five-membered ring very nearly so, 3.39 microns, for the

four-membered ring the wavelength decreased to 3.34 microns, while

for the three-membered ring the wavelength decreased considerably to

3.24 microns. Thus, the band at 3.28-3.29 may be due to C, vibrations

15










of the cyclobutane systems presented herein. However, it has also

been observed for the compound, CF2 rCH2CFBrCH,. that there is a shift

of the CH stretching frequency toward lower wavelengths and this

compound absorbs in this region at 3.35 microns. It vould be difficult

to make positive assignments in this region for the cyclobutane

system until a number of closely related materials have been examined

using a high-dispersion lithium fluoride prism.

Ihilson (29) assigned band at 10.87 and 11.07 microns in

cyclobutane to t.ro CH2 rocking frequencies. Derfer (9) made the

observation that seven substituted cyclobutanes all absorbed in the

narrow range 10.87-10.99 microns. They pointed out that if the

assignment to CH2 modes was correct, this band would not be expected

to appear in fully substituted materials. Reid (23) examined a

series of eight substituted cyclobutanes in which all the carbon

atoms were substituted and found all of these to absorb between 11.26

and 11.52 microns. Marrison (18) has pointed out that neither

methylene-nor perfluorocyclobutane absorbs in the 10.87-10.99 microns

region.

Host of the compounds described in the Experimental section

that are believed to have the cyclobutane structure absorb in the

range 10.90-11.10 microns.










IV GEIURAL C0riSIDERAITIC'N


All temperatures reported in this dissertation are on the

Centigrade scale and are uncorrected. The distillations were carried

out using a 25 centimeter electrically-heated jacketed column packed

with one-eighth inch glass helices. Pressures during distillation

under 10 millimeters were determined by a McLeod gauge; pressures

above 10 millimeters were read from a Zimmerli gauge.

Refractive indices were determined with an Abbe refractometer

at the temperatures indicated. Densities were determined at the

temperature indicated using a one milliliter pyenometer calibrated

against water at 20 Centigrade and corrected to water at 40

Centigrade. Molar refractions were calculated using the Lorenz-Lorentz

equation. The values for the atomic refractions were taken from Lange's

"Handbook of Chemistry," sixth edition, page 1025. In all cases the

value 1.1000 was used for the atomic refraction of fluorine.

The gas chromritography apparatus was built by Mr. Calvin

Workinger, Mr. Eugene Barker and the author. The detector, a thermal

conductivity cell, Model 9285, was purchased from the Gow-Mac

Instrument Company. The column, 20 feet of one-fourth inch aluminum

tubing packed with material prepared from 0.6 gram dinonyl phthlate

per 1.0 gram Johns-Manville Chromosorb, 35-80 mesh size. The tubing

was then coiled; the diameter of the coil was about 5 inches. Helium

was used as the carrier gas in all cases.




18





The infrared spectra were obtained by a Perkin-Elmer Model 21

double bean, recording, infrared spectrophotometer.

The nuclear magnetic resonance spectra were obtained by a

Varian High Resolution Nuclear Magnetic Resonance Spectrometer

operating at 56.4 megacycles and were interpreted by Dr. W. S. Brey, Jr.

The autoclave used in this research was obtained from the

American Instrument Company.

All analyses were carried out by Galbraith Laboratories.

Knoxville. Tennessee and by Drs. G. ':eiler and F. B. Strauss of

Oxford, England.
















N '






4 N







N \0 V N.
N 0r a W






* o
f ru r-l i-


Nl H HI I
C Nr %


\0 CL
* Q"


cc


0 o 4 C0 V
CM ~ d C ( iN


"aaR

NMA
H H H
9 0% '0
4 & N
H) H" H


H A
SN
9 r4



ft


o H &4 Hl N
NI N N ON N


"o


o
1 0




('0 N
C' f


oo
u-> 0






N *
00 o '


moons;d
\O\O4t


U t ~0
Q- iu 0 H H e

CN2C1N CMN O N N N N N N N

+ + + + + + + + + + + + + +
N NPNNNNN


P N5 '0 0 ?

Fj d a 6" di "r 530 "r 5


H ~


0.r

* I
0.0
.0


Co
.4V

'E 1


MW





0


0.


a








.1.

fJs


x>















R UN N U" 0 UN tC'- N n Ch
S 0c' 4 C- 0, mC A
VS N (NS ("N N -r ("N 4 t 3


l O cOm 0 C 0 0 CNl (N o
U1 r1 O N N (") H H N





L4 N N CV N C c' N C-







0.'-


C-0 I -


H s-IH r-4




0 0 *: 0 N W -t 0 % 0 M0

r *- N -t R0 \ '0





H
2 r H r4 H H r
o oH








u NC) 004 V 0

S. it t 3
N U N 1N N N N N
U N ( U U U U U


5+ + + + 4 +



SNNN H


NM NfM N NNNNg CN PL VJC













N~ ~ UW '
'''00, 0,

-ti 0' ~ \ 0' O\4

w n w t
H 4







N m,

CP l cl C4 N
NO





H r




a: -
.)l N' N N N O 3c N -










V~ a0 0~ 0
~~ w'C- O 4 nq








0 0
0N









94N m m 0
0





0 0 0 C)~

,~n,~4-4


0z HHHHi









TABLE II
ANALYSES OF THE COMPOUNDS PREPARED

Compd. 'RD % Carbon % Hydrogen
Number [Calod.] [Found] [Calcd.] [Found) [Calcd.] [Found]

I 32.59 33.35 42.25 42.12 3.55 3.72
II 35.49 35.65 33.51 33.94 2.81 3.06

III 40.52 40.95 27.50 28.06 2.31 2.81
IV 37.46 37.20 38.53 38.55 3.23 3.11
V 32.34 32.88 41.19 43.11 2.64 3.76

VI 32.09 32.45 52.18 52.41 3.75 3.96
VII 44.72 44.80 39.53 40.20 4.15 4.55
VIII -- -- 52.94 60.35 5.18 6.76
I ----- ----- 33.47 33.64 2.11 2.22
1 37.21 37.02 45.55 45.97 4.37 4.47

XI 47.93 48.21 54.44 54.63 3.64 3.91

XII 50.82 51.10 45.31 45.48 3.04 3.41
XIII 55.86 56.28 38.48 39.34 2.58 2.68

XIV 47.43 48.09 62.56 62.58 3.82 4.05
XV 27.97 28.34 --- --- ---
XVI 40.82 39.97 -- -- --

XVII 28.44 28.55 37.87 37.74 3.81 3.85
XVIII 33.30 33.41 34.31 34.53 3.46 3.68

XIX 33.06 33.05 41.75 41.57 4.68 4.84

xx 33.30 33.71 31.11 31.79 2.61 2.91
XXI 34.71 34.90 35.57 36.14 2.98 3.26
XXII 28.19 28.75 35.42 35.77 1.78 1.90










TABLE II (continued)


C D.
[Calcd.] [Found]


Compd.
Number

XXIII

XXIV

Xxv

XXVI

XXVII

XXVIII

XXIX



XXXI
xxxIII

XXXIII


33.01
28.88

48.25

56.74

53.01

48.25

43.25


36.55

35.90

36.44


% Carbon
[Caled.] [Found]

39.26 39.54


21.81

17.08

20.78


24.35

53.75

59.25

44.87

47.19


22.28

17.62

20.80


24.48

51.86

59.03
44.80

47.18


% Hydrogen
(Calcd.] (Found]

2.75 2.94


1.83

1.43

1.74


2.38

3.73

5.59
1.88

4.53


1.94

1.53

2.03


2.74

3.43

5.92

2.16

4.68


33.81

27.69

48.59

56.51

52.97
48.34

43.24


36.48

35.54

35.63










V EXPERIENTAL


In general all cycloalkylation reactions were carried out in

either a three-tenths liter stainless steel reaction vessel fitted

with a valve, pressure gauge, and blow-out assembly or in a 120 al.,

sealed, thik-walled Pyrex glass tube. The polymerization inhibitor

was in all eases p-terthutylcatechol. If the reactants were gases

at room temperature, they were condemned either in a thick-walled

glass tube and weighed or were condensed in a cold trap cooled to

Dry Ioe temperature, weighed and poured into the autoclave which was

cooled to Dry Ice temperature. The autoclave was then sealed, fitted

with a high pressure valve, rocked and heated at the desired

temperature. After the heating process the reaction vensel was

cooled, and opened, and any anreacted material was collected in a

cold trap cooled to Dry lce temperature. The remaining liquid

material was subjected to fractional distillation.

Ozonolysis reactions were carried out as follows:

About 4-5 drops of the sample was dissolved in exactly

5 ml. of the ethyl acetate-acetic acid solution. The solution was

cooled to about -20 (by means of an ice-hydrochloric acid mixture

in a Deuar flask), and ozone was passed through the solutions for

fifteen to twenty minutes. A 2 ml. aliquot of this solution was

placed in a 250 ml. flask containing a solution of 30 ml. of the

fuchain-aldehyde reagent and either 15 ml. of 24 hydrochloric acid

solution and 45 ml. of water or 60 ml. water.

24










This is a method for determining methylene groups by

ozonolysis (26). The resulting ozonide is reductively cleaved in a

fuchsin-aldehyde reagent containing excess sulfur dioxide. The color

produced by the resulting formaldehyde is compared with that produced

by similar treatment of a compound known to have a terminal methylene

group. The fuchsin-aldehyde reagent used is desensitized by the

addition of hydrochloric acid and does not give a color with aldehydes

other than formaldehyde.


A. Reactions of 1.3-Butadiene wth Fluoroblefins

1. Chlorotrifluoroethylene (3)

The autoclave was charged with 60 g. (0.52 mole) of

chlorotrifluoroethylene, 35 g. (0.65 mole) of butadiene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking

for twenty hours at 1000. Fractional distillation of the resulting

liquid material gave 81 g. (92% conversion) of material, I, b.p. 1150,
21 21
n21 1.3960. d4 1.2282. Anal. Calcd. for C6HF3Cl: MRD. 32.59;

%C. 42.25; %H, 3.55. Found: 1MR. 33.35; %C, 42.12; %H. 3.72.



Proposed Structure of I

CH -CHCH=CH
121 2
CF2-CFC1

Evidence supporting proposed structure:

1. Mode of formation and elemental analyses.

2. Infrared absorptions.









(a) No band in the region of 5.60C; CF2=CF- group

absent.

(b) Band at 3.20u; CH2=C$ group present.

(c) Band at 11.05,; cyclobutane structure present.

(d) Dibromide of I gave band at 11.05i; cyclobutane

structure present.

(3) Ozonolysis of I gave CH20, thus showing CH2=CC group

present.

(4) I with alcoholic potassium hydroxide gave a material that

polymerized on standing thus indicating a conjugated diene

was formed. This supports the above 1,2-type structure.

(5) A gas chromatogram of I showed only one peak. DMR results

show the absence of the cyclohexene structure and the

presence of two kinds of four-membered ring structures

which are probably cis-trans isomers of the above 1,2-type

structure.



2. Bromotrifluoroethylene

The autoclave was charged with 80 g. (0.50 mole) of

bromotrifluoroethylene. 30 g. (0.56 mole) of butadiene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking for

twenty hours at 1400. Fractional distillation of the resulting liquid

material gave 65 g. (61% conversion) of material, II, b.p. 70*/89 m..
22 1.4209. d2 1.53-3. Anal. Calcd. for C6H Br: %RD. 35.49;


%C. 33.51; "H. 2.81. Found: IRD. 35.65; %C. 33.98; VH. 3.36.










Proposed Structure of II

.CH2-CICH=CH2
I 1
CF2-CFBr

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.604; CF2=CF- group

absent.

(b) Band at 3.204; CH2=C group present.

(c) Band at 10.97i; cyclobutane structure present.

(3) Ozonolysis of II gave CH20, thus showing CH2=C group
present.

(4) A gas chromatogram of II showed only one peak. N~ results

show the absence of the cyclohexene structure and the

presence of two kinds of four-membered ring structures

which are probably cis-trans isoers of the above 1,2-type

structure.


3. lodotrifluoroethylene

A mixture of 20 g. (0.097 mole) of iodotrifluoroethylene,

8 g. (0.15 mole) of butadiene and 1 g. of inhibitor was heated in a

sealed tube for sixteen hours at 1250. Fractional distillation of the

resulting liquid material gave 14 g. (56% conversion) of material. III.

b.p. 88-89/82 mm., n1 1.700, d1 1.7851. Anal. Called. for CgH6F3I:

MRD. 40.52; %c. 27.50; %H. 2.31. Found: MR,. 40.95; %c. 28.06; H, 2.81.









Proposed Structure of III

CH,-CHCH=CH2
I I
CF2-CFI

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.601; CF2=CF- group

absent.

(b) Band at 3.20; CH2=C0 group present.

(e) Band at 11.04; cyclobutane structure present.

(d) Dibromide of III gave a band at 11.00; cyclobutane

structure present.

(3) Ozonolysis of III gave CH20, thus showing CH2=C group

present.

(4) A gas chronatogran of III showed two peaks. The ratio

of the areas under the peaks was about 3:2. MR results

show the absence of the cyclohexene structure and the

presence of two kinds of four-membered ring structures

which are probably cis-trans isomers of the above 1.2-type

structure.



1l,l-Dichloro-2,2-difluoroethylenr

The autoclave was charged with 65 g. (0.49 mole) of

11.-dichloro-2.2-difuoroethylene, 30 g. (0.56 mole) of butadiene and

2 g. of inhibitor. The autoclave was then sealed and heated while

rocking for sixteen hours at 1250. Fractional distillation of the









resulting liquid material gave 69 g. (76% conversion) of material, IV.

b.p. 144. n21 1.4352, d 1.3131. Anl. Cald. for C6H6F2C12

MR, 37.46; %C. 38.53; %H, 3.23. Found: f%. 37.20; 0C, 38.55;

XH. 3.11.


Proposed Structure of IV

CH2.-CHC11CCH,

CF2-CC12

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.80p; CF2=CC1- group

absent.

(b) Band at 3.204; CH2=C' group present.

(c) Band at 10.98p: cyclobutane structure present.

(3) Ozonolysis of IV gave CH20, thus showing CHI2=C group
present.

(4) A gas chromatogram of IV showed only one peak. IR results

show the absence of the cyclohexene structure and the

presence of one kind of four-membered ring structure.

No cis-trans isomerization is possible for the above

structure.


5. Perfluoropropene (19)

The autoclave was charged with 60 g. (0.40 mole) of









perfluoropropene, 30 g. (0.56 mole) of butadiene and 2 g. of inhibitor.

The autoclave was then sealed and heated while rocking for sixteen hours

at 175. Fractional distillation of the resulting liquid material gave

21 g. (26 conversion) of material, V, b.p. 97,0 n22 1.47, d2 1.3171.



Proposed Structures of V



CH2-ClCHCH2 and CH CFCF3
I II I
CF2-CFCF3 CH CF



Evidence supporting proposed structures:

(1) Mode of formation and physical properties which agreed

with compound of known composition.

(2) Infrared absorptions and interpretations.

(a) No band in the region of 5.60j; CFt=CF- group

absent.

(b) Band at 3.20i; CH2=cC group present.

(3) Ozonolysis of V gave CH20. thus showing CH2=C( group

present.

(4) A gas chromatogram of V showed two peaks. The ratio of

the areas under the peaks was about 2:1. WR results

show the presence of both the cyclohexene structure and

the cyclobutane structure in the amount of one part

cyclohexene to three parts cyclobutane. It was also

noted that only one kind of four-amebered ring structure

was present. It could not be determined from the IMR









spectrum whether the trifluoromethyl group was cis or trans

with respect to the vinyl group.


6. Perfluoroacrylonitrile (16)

A mixture of 14 g. (0.13 mole) of perfluoroacrylonitrile,

10 g. (0.19 mole) of butadiene and 0.5 g. of inhibitor was heated in a

sealed tube for fifteen hours at 1500. Fractional distillation of the

resulting liquid material gave 8 g. (38% conversion) of material, VI,

b.p. 140, n1 1.3885, d1 1.1705. Anal. Calcd. for C06F3N:

MRD. 32.09; %c, 52.18; iH, 3.75. Found: MRD, 32.45; %C, 52.41;

%H, 3.96.


Proposed Structures of VI

Sc
CH2-CHCH=CH2 and CH CFCN
I 2 i II I
CF2-CFCN CH CF2
CH2

Evidence supporting proposed structures:

(1) Mode of formation and elemental analyses.
(2) Infrared absorptions.
(a) No band in the region of 5.60p; CF2=CF- group

absent.

(b) Band at 3.19%; CH2=C0 group present.

(c) Band at 10.9134; cyclobutane structure present.

(3) Ozonolysis of VI gave CH20, thus showing CH2=C( group
present.









(4) A gas chromatogram of VI showed tio peaks. The ratio of

the areas under the peaks was about 3:2. IMr results

show the presence of both the cyclohexene structure and

the cyclobutane structure in the ratio of 1:1. It was

also noted that only one kind of four-membered ring

structure was present. It could not be determined from

the MH spectrum whether the cyanide group was cis or

trans with respect to the vinyl group.



7. I-Broxmo-,1, 2- tri fluoro-l-butene

The autoclave was charged with 95 g. (0.50 mole) of

4-bromo-l.l,2-trifluoro-l-butene, 30 g. (0.56 mole) of butadiene and

2 g. of inhibitor. The autoclave was than sealed and heated while

rocking for nineteen hours at 1600. Fractional distillation of the

resulting liquid material gave 43 g. (354 conversion) of material. VII,

b.p. 100/37 m. n21 1.4471. d1 l.476. Anal. Calcd. for CgH10FBr:

MR. 44.72; %C. 39.53; H. 4.15. Fourd: MRD, 44.80; ;C. 40.20;

%-. '.63.



Proposed Structure of VII



CI 2-CHCHCH, and CH CFCH CHBr
I II I 1
CF2-CFCH2CH2Br CH CF2
012

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.










(2) Infrared absorptions.

(a) No band in the region of 5.601; CF2=CF- group

absent.

(b) Band at 3.2011; CH2=C group present.

(c) Band at 1l.02p; cyclobutane structure present.

(3) Ozonolysis of VII gave CH20, thus showing CH2=C' group

present.

(4) A gas chromatogram of the dehydrobreminated material, XXXI,

showed two peaks. The ratio of the areas under the peaks

was about 3:2. M results on XXXI show the presence of

both the cyclohexene structure and the cyclobutane

structure in the ratio of 1:1. It was also noted that

only one kind of four-membered ring structure was present.

It could not be determined from the NKR spectrum whether

one vinyl group was cis or trans with respect to the other

vinyl group.



8. Trifluoroethylene

The autoclave was charged with 41 g. (0.50 mole) of

trifluoroethylene, 27 g. (0.50 mole) of butadiene and 2 g. of inhibitor.

The autoclave was then sealed and heated while rocking for twelve hours

at 150. Fractional distillation of the resulting liquid material gave

8 g. of material, VIII, b.p. 110-1180. A gas chromatogram of this

material showed two peaks, one of which was due to 4-vinylcyclohexene.

The other peak was assumed to be due to the addition product from the

fluoro6lefin and butadiene. MMR results were inconclusive concerning









the structures of this material.


9. 2.3-Diohlorohexafluoro-2-butene
The autoclave was charged with 116.5 g. (0.50 nole)

of 2,3-dichlorohexafluoro-2-butene. 32 g. (0.59 mole) of butadiene

and 2 g. of inhibitor. The autoclave was then sealed and heated while

rocking for twenty-four hours at 140-1500. Fractional distillation

of the resulting liquid material gave 31 g. (22% conversion) of

material. IX, b.p. 1060/71 ms., n.p. 46. Anal. Calcd. for CH6F6C12:

%C. 33.47; %i. 2.11. Found: C,. 33.64; %H, 2.22.


Proposed Structure of IX

/c"2\
CH CC1CFl
II I
CH N CC1CF


Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) Bard at 3.25i; C in cyclohexene present.
(b) No band at 3.20%; CH2=C( group absent.

(3) Ozonolysis of LX failed to give CH20. thus showing CH2-C
absent.

(4) IX reacted with alcoholic potassium hydroxide to give

XXXII. the structure of which was proven to be 1.2-bis-

(trifluoromethyl)benrone (5).










10. 1.2-Dichlorotetrafluorocyclobutene

A mixture of 18 g. (0.093 mole) of 1,2-dichlorotetra-

fluorocyelobutene, 11 g. (0.20 mole) of butadiene and 1 g. of inhibitor

was heated in a sealed tube for sixteen hours at 1800. Fractional

distillation of the resulting liquid material gave 0.5 g. of material,

b.p. 160-1900. Upon fusing with sodium, a positive test for chloride

ion was obtained. This is the only evidence supporting that addition

took place to give the probable product, CH2 C0
HC C--CF
II I I 2
HC 0---CF2
CH2 Cl



11. 1.2-Dichlorohexafluorocyclopentene

A mixture of 4 g. (0.016 mole) of 1.2-dichlorohexa-

fluorocyclopentene, 5 g. (0.093 mole) of butadiene and 1 g. of inhibitor

was heated in a sealed tube for sixteen hours at 160e. The unreacted

material was distilled off leaving 6.5 g. higher boiling material which

contained a considerable amount of 4-vinylcyclohexane. The higher

boiling material was treated with excess alcoholic potassium hydroxide,

washed with water several times, and dried over calcium chloride. The

wash water was acidified and gave a positive test for chloride ion with

silver nitrate. The organic material was diluted with isoSctane and its

ultraviolet absorption spectrum showed a maximum at 280.5mi. This is

the region in which substituted benzenes absorb. Therefore, there is

some indication that addition took place and that the compound formed









was CH 01 .
CH C-CF2

I 2 CF2
CH C-CF I--
72 2
0CH C1



12. 2-Chloro-l, l-difluoroethylene

The autoclave was charged kith 60 g. (0.61 mole) of

2-chloro-l.l-difluoroethylene. 30 g. (0.56 mole) of butadiene and 2 g.

of inhibitor. The autoclave was then sealed and heated vbile rocking

for sixteen hours at 175. Fractional distillation of the resulting

liquid material gave 32 g. of material, b.p. 125-129". A gas

chromatogram showed two peaks. The ratio of the areas under the

peaks was about 9:1. The larger peak was found to be due to

4-virrlcyclohexene. The other peak was assumed to be due to the

addition product from the fluorodlefin and butadiene.




B. Reactions of Styrene with Fluoroolefins

1. Chlorotrifluoroethylene (25)

The autoclave was charged with 50 g. (0.43 mole) of

chlorotrifluoroethylene. 50 g. (0.48 mole) of styrene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking

for twenty-two hours at 1000. Fractional distillation of the resulting

liquid material gave 63.5 g. (67A conversion) of material. XI,
21 21
b.p. 109-1100/20 mm.. n. 1.4829, d4 1.3071. Anal. Calcd. for

Co10 8F3C: Rp.D 47.93; IC. 54.44; %P, 3.64. Found: MRD. 48.21;









ZC, 54.63; %H. 3.91.


Proposed Structure of XI

CH2-CHC H6

CF2-CFCl

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.6p; CF2=CF- group

absent.

(b) Band at 11.05p; cyclobutane structure present.

(3) NMR spectrum of XI is in agreement with the proposed

structure; however, because of several additional peaks

that were present and were not due to the above 1,2-type

structure, XI may be a mixture of the 1,2- and 1,3-type

structures. Roberts (25) mentioned only the 1,2-type

structure and gives some chemical evidence supporting

it but makes no mention of the 1,3-type structure.



No gas chromatogram was obtained from XI because of

its high boiling point.



2. 3romotrifluoroethylene

The autoclave was charged with 80.5 g. (0.50 mole)

of bromotrifluoroethylene, 52 g. (0.50 mole) of styrene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking










for sixteen hours at 1250. Fractional distillation of the resulting

liquid material gave 57 g. (43% conversion) of material, XII,

b.p. 65*/0.5 .. n21 1.5026, d21 1.5312. Anal. Calcd. for C1 HgFBr:

MR.D 50.82; %c. 45.31; %H. 3.04. Found: MRD. 51.10; %c. 45.48;

%H. 3.41.



Proposed Structure of XII

CH-CHC H
CF2-CFBr

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.6p; CF2=CF- group

absent.

(b) Band at 11.10; cyclobutane structure present.

(3) Because of its similarity to XI, XII is also believed to

have the 1,2-type structure with the possibility that

some 1,3-type structure is also present.



No gas chromatogram was obtained from XII because of

its high boiling point.



3. Iodotrifluoroetkylene

A mixture of 20 g. (0.097 mole) of iodotrifluoroethylene.

20 g. (0.19 mole) of styrene and 1 g. of inhibitor was heated in a

sealed tube for sixteen hours at 1250. Fractional distillation of the









resulting liquid material gave 10 g. (33% conversion) of material, XIII,
21 21
b.p. 82-830/0.5 mm., rni 1.5408. d1 1.7346. Anal. Calod. for C,0HgF3I:

MRI. 55.86; %C, 38.48; %H, 2.58. Found: MRp, 56.28; %C, 39.34;
%H, 2.68.


Proposed Structure of XIII

CH,-CHC6H5
I 1
CF2-CFI

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.64; CF2=CF- croup

absent.

(b) Band at 11.141; cyclobutane structure present.

(3) Because of its similarity to XI, XIII is also believed

to have the 1,2-type structure with the possibility that

some 1,3-type structure is also present.


No gas chromatogram was obtained from XIII because

of its high boiling point.


4. Perfluoroacryloni trile

A mixture of 8.5 g. (0.079 mole) of perfluoroacrylo-

nitrile, 20 g. (0.19 mole) of styrene and 1 g. of inhibitor was heated

in a sealed tube for fourteen hours at 100. Fractional distillation

of the resulting liquid material gave 9.5 g. (57% conversion) of










material. XIV. b.p. 75-76o/3 am.. 22 1.4743. d 2 1.2340. Anal. Calcd.

for Cl.8F3I!: 1RD. 47.43; %C. 62.56; %H, 3.82. Found: MRD. 48.09;

%C. 62.58; %H. 4.05.



Proposed Structure of XIV

CH,2-CHCH,
I I
CF2-CFCN

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.6-; CF2=CF- group

absent.

(b) Band at 10.98i; cyclobutane structure present.

(c) Band at 4.48p; -5i group present.

(3) Because of its similarity to XI. XIV is also believed to

have the 1.2-type structure with the possibility that

some 1,3-type structure is also present.



No gas chromatogram was obtained from XIV because of

its high boiling point.

5. Perfluoropropene

A mixture of 15 g. (0.10 mole) of perfluoropropene,

17 g. (0.16 mole) of styrene and 1 g. of inhibitor was heated in a

sealed tube for fourteen hours at 125". There vere recovered 14 g.

of perfluoropropene and 17 g. of viscous material (polystyrene).










Thus, perfluoropropene failed to react with styrene under above

conditions.



6. Trifluoroethylene

The autoclave was charged with 45 g. (0.55 mole) of

trifluoroethylene, 25 g. (0.24 mole) of styrene and 2 g. of inhibitor.

The autoclave was then sealed and heated while rocking for sixteen

hours at 1250. There were recovered 40 g. of trifluoroethylene, 22 g.

of styrene and 3 g. of viscous material remained in the distillation

pot. Thus, trifluoroethylene failed to react with styrene under the

above conditions.




C. Reactions of Ctlorotrifluoroethylene idth Olefins

1. Propene

The autoclave was charged with 18 g. (0.43 mole) of

propene, 55 g. (0.47 mole) of chlorotrifluoroethylene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking for

eighteen hours at 275. Fractional distillation of the liquid material

from two identical runs gave 48 g. (35,$ conversion) of material, XVII.

b.p. 99-1000. n1 1.3702, 1 1.2582. Anal. Calcd. for C5H6F3Cl1

MRD. 28.44; %C, 37.87; ,H. 3.81. Found: -RD, 28.55; %C. 37.74;

%H. 3.85.










Proposed Structure of XVII

CH2-CHCH
CF2-CFCl

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.60.; CF2=CF- group

absent.

(b) No band in the region of 6.10p; C=C absent.

(e) band at 10.94p; cyclobutane structure present.

(3) MR results show the presence of two kinds of four-

membered ring structures which are probably cis-trans

isomers of the above 1,2-type structure. Because of

its similarity to XIX. XVII is also believed to nave

only the 1.2-type structure.



2. Isobutylene

The autoclave was charged with 15 g. (0.31 mole) of

isobutylene. 30 g. (0.26 mole) of chlorotrifluoroethylene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking

for three hours at 310*. Fractional distillation of the resulting

liquid material gave 9 g. (20;1 conversion) of material. XIX, b.p.

l1-115. D 1.3 27, d25 1.2140. Aal. Called. for C6 HF Cl:

IfD. 33.06; %C. 41.75; H,. 4.68. Found: MRD. 33.05; ,C. 41.57;
%H. 4.85.










Proposed Structure of XIX

CH2-C(CH )2
CF2-CFC1

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorption.

(a) No band in the region of 5.60p; CF2=CF- group

absent.

(b) No band in the region of 6.10p; C=C absent.

(c) Band at 11.07p; cyclobutane structure present.

(3) NkR spectrum of XIX is in agreement with the proposed

structure and indicates that no other structures are

present.

(4) XIX failed to react with alcoholic potassium hydroxide,

thus indicating that the -CH2- group is not adjacent to

the -CFC1- group.



3. Allyl Chloride

The autoclave was charged with 25.5 g. (0.33 mole) of

allyl chloride and 40 g. (0.34 mole) of chlorotrifluoroethylene. The

autoclave was then sealed and heated while rocking for two hours at

2400. Some charring occurred and hydrochloric acid was evolved upon

opening the autoclave. Fractional distillation of the resulting liquid

material gave 5 g. (7.8% conversion) of material, XX. b.p. 142-1440,
21 1.4130. d1 1.4275. Anal. Called. for C HF3C12: MRD, 33.30;

%C, 31.11; %H, 2.61. FEund: MRD, 33.71; %C. 31.79; %H, 2.91.










Proposed Structure of IX

CH2-CHCH2C1
CF2-CFC1

Evidence supporting proposed structure:

(1) Mode of formation and molar refraction.

(2) Infrared absorption.

(a) No band in the region of 5.60n; CF2=CF- group

absent.

(b) No band in the region of 6.109; C=C absent.

(c) Band at 10.87p; cyclobutane structure present.

(3) Because of its similarity to XIX, XX is also believed to

have only the 1,2-type structure.



4. Allyl Alcohol

The autoclave was charged with 29 g. (0.50 mole) of

allyl alcohol, 60 g. (0.52 mole) of chlorotrifluoroethylene and 2 g.

of inhibitor. The autoclave was then sealed and heated while rocking

for eighteen hours at 1800. Upon distillation of the resulting liquid

residue no material boiling higher than allyl alcohol was obtained.

Thus, chlorotrifluoroethylene failed to react with allyl alcohol

under the above conditions.



5. cis-2-Butene

The autoclave was charged with 17.5 g. (0.31 mole) of

cis-butene and 34 g. (0.29 mole) of chlorotrifluoroethylene. The

autoclave was then sealed and heated while rocking for four hours at 2500.










Upon distillation of the resulting liquid residue no material boiling

higher than the dimer of chlorotrifluoroethylene was obtained. Thus,

chlorotrifluoroethylene failed to react with cis-2-butene under the

above conditions.


6. Methyl Acrylate

The autoclave was charged with 43 g. (0.50 mole) of

methyl acrylate, 60 g. (0.52 mole) of chlorotrifluoroethylene and 2 g.

of inhibitor. The autoclave was then sealed and heated while rocking

for eighteen hours at 1400. Fractional distillation of the resulting

liquid material gave 48 g. (47% conversion) of material, XXI, b.p.

820/42 m., n9 1.3980, d 9 1.3947. Am-. Calcd. for CH F C102

MR%. 34.71; %C, 35.57; H, 2.98. Found: MH, 34.90; %c. 36.14;

%H, 3.26.


Proposed Structure of XXI

CH2-C02CH3
2 23
CF2-CFCl

Evidence supporting proposed structures:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.60p; CF2=CF- group

absent.

(b) Band at 5.70i; 'C=0 group present.

(c) Band at 11.05p; cyclobutane structure present.










(3) XXI reacted readily with alcoholic potassium hydroxide.

This would be expected if the hydrogen atom being

eliminated d is activated by a group such as a carbonyl.

This observation is in agreement with the proposed

structure.

(4) ?MR results show the presence of two kinds of four-

membered ring structures which are probably cis-trans

isoaers of the above 1,2-type structure. Because of its

similarity to XIX, XXI is also believed to have only

the 1,2-type structure.



7. Acrylonltrile (2)

The autoclave was charged with 25 g. (0.47 mole) of

acrylonitrile, 55 g. (0.47 mole) of chlorotrifluoroethylene and 2 g.

of inhibitor. The autoclave was then sealed and heated while rocking

for eighteen hours at 155". Fractional distillation of the resulting

liquid material gave 52 g. (69% conversion) of material. XXII,

b.p. 82/40 mn.. nD0 1.4012, d0 1.4332. Anal. Calcd. for C H F CCI:

R.D, 28.19; %C. 35.42; QH. 1.78. Found: RD,. 28.75; %C. 35.77;

.H, 1.90.



Proposed Structure of XXII

CH2-CHCN
CF,-CFC1

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.










(2) Infrared absorptions.

(a) No band in the region of 5.60A; CF2=CF- group

absent.

(b) Band at 4.43,; -0EN group present.

(c) Band at 11.00; cyclobutane structure present.

(3) XXII reacted readily with alcoholic potassium hydroxide.

This would be expected if the hydrogen atom being

eliminated is activated by a group such as a nitrile.

This observation is in agreement with the proposed

structure.

(4) NMR results show the presence of two kinds of four-

membered ring structures which are probably cis-trans

isomers of the above 1,2-type structure. Because of its

similarity to XIX, XXII is also believed to have only

the 1,2-type structure.



8. Methacrylonitrile

The autoclave was charged with 33.5 g. (0.50 mole) of

methacrylonitrile, 60 g. (0.52 mole) of chlorotrifluoroethylene and

2 g. of inhibitor. The autoclave was then sealed and heated while

rocking for sixteen hours at 140-150. Fractional distillation of the

resulting liquid material gave 28 g. (31% conversion) of material,
21.401. 20
XXIII. b.p. 80/34 mm. 14013 d4 1.3513. Anal. Called. for

C6H5F3ClN: M#. 32.81; %C. 39.26; %H, 2.75. Found: MD,% 33.01;

%C. 39.54; %H. 2.94.










Proposed Structure of XXII

CH
1 3
CH2-CCM
I I
CF2-CFG

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) rio band in the region of 5.60&; CF2=CF- group

absent.

(b) Band at 4.43p; -(EN group present.

(c) Band at 11.024; cyclobutane structure present.

(3) XXIII failed to react with alcoholic potassium hydroxide.

This would be expected if there were no hydrogen atom

on the carbon adjacent to the -CFC1- group. This

observation is in agreement with the proposed structure

and thus eliminate the possibility of the 1,3-type

structure being present.

(4) MMR results show the presence of two kinds of four-

membered ring structures which are probably cis-trans

isomers of the above 1,2-type structure.



9. Maleic Anhydride

The autoclave was charged with 25 g. (0.26 mole) of

maleic anhydride. 55 g. (0.47 mole) of chlorotrifluoroethylene and

50 ml. of benzene. The autoclave was then sealed and heated while

rocking for sixteen hours at 175- The volatile material was removed










under reduced pressure leaving 24 g. of unreacted maleic anhydride,

m.p. 55-560. Thus, chlorotrifluoroethylene failed to react with

maleic anhydride under the above conditions.



10. Cinnxlic Acid

The autoclave was charged with 20 g. (0.14 mole) of

cinnamic acid, 55 g. (0.47 mole) of chlorotrifluoroethylene and 60 ml.

of glacial acetic acid. The autoclave was sealed and heated while

rocking for sixteen hours at 1750. There were recovered 48 g. of

unreacted chlorotrifluoroethylene and 20 g. of cinnamic acid,

m.p. 297-2980. Thus, chlorotrifluoroethylene failed to react with

cinnamic acid under the above conditions.



11. Isoprene

The autoclave was charged with 34 g. (0.50 mole) of

isoprene, 60 g. (0.52 mole) of hilorotrifluoroethylene and 2 g. of

inhibitor. The autoclave was then sealed and heated while rocking

for twelve hours at 125*. Fractional distillation of the resulting

liquid material from three identical runs gave 175 g. (64% conversion)
20 20
of material, X, b.p. 1340, n0 1.4049, d2 1.2210. Anal. Calcd. for

C8F3 Cl: MRD. 37.21; SC. 45.55; 5H. 4.37. Found: MRN. 37.02;

%C. 45.97; %H, 4.47.










Proposed Structure of X

CH3

ICH-CCH=CH2
1 1
CF2-CFC1

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.60o; CF2=CF- group

absent.

(b) Band at 3.204i CH2=C group present.

(c) Band at 11.09i; cyolobutane structure present.

(3) Ozonolysis of X gave CH20. thus showing CHQ2='C group

present.

(4) X failed to react with alcoholic potassium hydroxide, thus

favoring the 1.2-type structure and showing that no

1,3-type structure was present.

(5) IMR results show the absence of the cyclohexene structure

and the presence of two kinds of four-membered ring

structures which are cis-trans isomers of the above

1,2-type structure.



12. 1.3-Cyclopentadiene

A mixture of 11 g. (0.17 mole) of cyclopentadiene,

20 g. (0.17 mole) of chlorotrifluoroethylene and 1 g. of inhibitor

was heated in a sealed tube for sixteen hours at 115U Nineteen gram










of unreacted chlorotrifluoroethylene was recovered from the reaction

mixture. Thus, chlorotrifluoroethylene failed to react with cyclo-

pentadiene under the above conditions.



13. Furn

A mixture of 13 g. (0.19 mole) of furan, 14 g.

(0.12 mole) of chlorotrifluoroethylene and 1 g. of inhibitor was

heated for sixteen hours at 1250. Fourteen grams of unreacted

chlorotrifluoroethylene was recovered from the reaction mixture. Thus,

chlorotrifluoroethylene failed to react with furan under the above

conditions.



14. Anthracene

A mixture of 3 g. (0.169 mole) of anthracene, 12 g.

(0.10 mole) of chlorotrifluoroethylene and 20 ml. of benzene was

heated in a sealed tube for sixteen hours at 2000. Ten grams of

unreacted chlorotrifluoroethylene was recovered. The benzene was

evaporated off and the remaining solid was recrystallized from

aqueous ethanol to give 0.1 g. of an orange solid, m.p. 164-165*.

Upon fusion with sodium, a negative test for chloride ion was obtained.

No further attempt to identify this material was made.



15. Allene

The autoclave was charged with 20 g. (0.50 mole) of

allene and 41 g. (0.35 mole) of chlorotrifluoroethylene. The autoclave

was then sealed and heated for twelve hours at 125-150*. Fractional










distillation of the resulting liquid material gave 4 g. (7.3%

conversion) of material. XV. b.p. 96-98. n22 1.3853 d22 1.2950.

and 9 g. (19% conversion) of material. XVI, b.p. 150-152." n2 1.4030,

d22 1.6675. Al. Called. for C?4F3l: .RD. 27.97. Found: RD. 28.97.

Called. for CH q6C12: MRD, 40.82. Found: M,. 39.97.



Proposed Structure of XV

CH2-C=CH2
CF2-CFC1

Evidence supporting proposed structure:

(1) Mode of formation and molar refraction.

(2) Infrared absorption.

(a) No band in the region of 5.64' CF2=CF- group

absent.

(b) Band at 5.90 ; CH2= attached to a four-membered

ring.

(c) No band in the region of 131; it has been

reported that methylene eyolobutane does not

absorb in this region either.

(3) Because of its similarity to XVII, XV is also believed
to have only the 1,2-type structure.










Proposed Structure of XVI

CFC1-CF

CkZ-C--CHZ

CF2-CFCl

Evidence supporting proposed structure:

(1) Mode of formation and molar refraction.

(2) Infrared absorptions.

(a) No band in the region of 5.6p; CF,=CF- group

absent.

(b) Band at 11.13p; cyclobutane structure present.

(c) Weak band 5.96p; probably due to impurity from XV.

(3) Because of its similarity to XV, XVI is also believed to

have only the 1,2-type structure.



16. 1,1.3-Trifluoro-. 3-butadiene

A mixture of 11 g. (0.10 mole) of 1,l,2-trifluoro-l,3-

butadiene, 12 g. (0.10 mole) of chlorotrifluoroethylene and 2 g. of

inhibitor was heated in a sealed tube for twelve hours at 100.

Distillation of the resulting liquid material gave 10 g. of material

b.p. 90-120o. A gas chromatogram of this material showed four major

peaks, three of which were due to the dimer of the diene as was shown

from an independent experiment. No further attempt was made to

identify the separate components of the mixture.










17. 2.3-Dichlorohexafluoro-2-butene

A mixture of 20 g. (0.086 mole) of 2,3-dichlorohexa-

fluoro-2-butene and 20 g. (0.17 mole) of chlorotrifluoroethylene was

heated in a sealed tube for sixteen hours at 225*. Upon distillation

no material boiling higher than 2,3-dichlorohexafluoro-2-butene was

obtained.



18. Cyclohexeae

The autoclave was charged with 41 g. (0.50 mole) of

cyclohexene and 60 g. (0.52 mole) of chlorotrifluoroethylene. The

autoclave was then sealed and heated while rocking for sixteen hours

at 1750. Upon distillation no material boiling higher than cyclohexene

was obtained.





D. Miscellaneous Addition Reactions

1. l.l-Dichloro-2.2-difluoroethylene with Propene

The autoclave was charged with 21 g. (0.50 mole) of

propene, 70 g. (0.53 mole) of l,l-dichloro-2.2-difluoroethylene and

2 g. of inhibitor. The autoclave was then sealed and heated while

rocking for sixteen hours at 2250. The resulting liquid was reacted

with 63.5 g. (1 g. atom) of zinc dust in 200 ml. of dioxane in order

to remove 1,1.2,2-tetrachlorotetrafluorocyclobutane from the reaction

mixture. This material and the desired product have similar boiling

points. The mixture was then filtered to remove the solid material,

the remaining liquid washed several times with water to remove the









dioxane and dried over calcium chloride. Fractional distillation gave

14.5 g. (17% conversion) of material, XVIII, b.p. 131*, 21 1.4170,

d41 1.3175. Ana. Calod. for CH6F2C12: MR. 33.30; fC. 34.31;

%H, 3.46. Found: MRp 33.41; %C. 34.53; tH, 3.68.



Proposed Structure of XVIII

CH -CHCH,
1 2-1 3
CF2-CC12

Evidence supporting proposed structure:

(1) Mode of formation and elemental analyses.

(2) Infrared absorptions.

(a) No band in the region of 5.801; CF2=CC1- group

absent.

(b) No band in the region of 6.10y; C=C absent.

(c) Band at 11.024; cyclobutane structure present.

(3) MR results show the presence of only one kind of four-
membered ring structure. Because of its similarity to

XIX, XVIII is also believed to have the 1,2-type structure

(-CCI2- group adjacent to the -CHCH3- group).



2. Chlorotrifluoroethylene dith Hitrosobenzene

The autoclave was charged with 40 g. (0.37 mole) of

nitrosobenzene, 55 g. (0.47 mole) of chlorotrifluoroethylene and 2 g.

of inhibitor. The autoclave was sealed and at about room temperature

a violent reaction occurred blowing the rupture disc. The remaining









material in the autoclave was carbon.



3. Chlorotrifluoroethylene with Benzonitrile

The autoclave was charged with 53 g. (0.52 mole) of

benronitrile and 50 g. (0.43 mole) of chlorotrifluoroethylene. The

autoclave was then sealed and heated while rocking for eighteen hours

at 1800. Forty-eight grare of unreacted chlorotrifluoroethylene and

53 g. of benzonitrile i.are recovered. Thus, chlorotrifluoroethylena

failed to react with benzonitrile under the above conditions.



4. Perfluoroacrylonitrile Diaer (16)

Eleven grams (0.10 mole) of perfluoroacrylonitrile

was heated in a sealed tube for eight hours at 2250. A considerable

amount of carbonized material was noted inside the tube. Fractional

distillation of the resulting liquid material gave 7 g. (64 conversion)

of material. XXIV. b.p. 75-780, n0 1.3328, d20 1.4809. MRD, called. for

C6F6N2: 27.69. Found: 28.88.



Proposed Structure of XXIV

CF2-CFCN
I I
CF2-CFON

Evidence supporting proposed structure:

(1) Mode of formation and molar refraction.

(2) Infrared absorption.

(a) No band in the region of 5.604; CF2=CF- group

absent.









(b) Band at 4.44J,; -CN group present.

(3) NM results show the presence of two kinds of four-
membered ring structures which are probably cia-trans

isomers of the above 1,2-type structure.



5. 1,1,2-Trifluoro-l, 3-butadiene Dimer

A mixture of 15 g. (0.14 mole) of 1,1,2-trifluoro-

1,3-butadiene and 2 g. of inhibitor was heated in a sealed tube for

twelve hours at 1000. Eleven grams of a rubbery polymer and 4 g. of

material, b.p. 100-130, were obtained. A gas chromatogram of this

material gave three major peaks, all of which were assumed to be due

to various isomers of the dimer. No further attempt was made to

identify the separate components of the mixture.



6. Thermal Reaction of 2-Chloropentafluoropropene

The autoclave was charged with 65 g. (0.39 mole) of

2-chloropentafluoopropene. The autoclave was then sealed and heated

while rooking for eighteen hours at 350. Upon distillation of the

resulting liquid material 8.5 g. of material, b.p. 54-78, was

obtained. A gas chromatogram of this material showed six major peaks.

No further attempt was made to identify the separate components of the

mixture.



7. Thermal Reaction of 2-Chloro-1.2-difluorovinyl Pethyl Ither

The autoclave was charged with 30 g. (0.23 mole) of

2-chloro-l,2-difluorovinyl methyl ether and 2 g. of inhibitor. The









autoclave was then sealed and heated while rocking for twelve hours

at 190*. Fractional distillation of the resulting liquid material

gave 5 g. of material, b.p. 110-117o. This material upon standing

produced a white solid which was not identified.





E. Reactions of Addition Products

1. I with Bromine

A solution of I (10 g., 0.058 mole) in carbon tetra-

chloride (10 ml.) was placed in a 100 Al., three-necked flask fitted

with a reflux condenser, a stirrer and a dropping funnel. The flask

was cooled in a Dry Ice-acetone bath maintained at -200 to -10e. A

solution of 9.6 g. (0.06 mole) of bromine in 10 ml. of carbon tetra-

chloride was added slowly. After addition was complete, the reaction

mixture was brought to roon temperature and stirred for one hour.

The excess bromine was then removed by shaking with sodium thiosulfate

solution. The organic layer was separated, washed with water, dried

over calcium chloride and distilled under reduced pressure to give

14 g. (72.24 conversion) of material, XXV. b.p. 96-980/8 ma.,
22 22
n2 1.4898, d2 1.9836. Aaj. Called. for CgH6F C1Br2: MR,. '8.59;

%C. 21.81; %H. 1.83. Found: MRD. 48.25; fC. 22.28; *-H. 1.94.



2. III with Bromine

In the manner described above 6.0 g. (0.038 mole) of

bromine in 5 ml. of carbon tetrachloride was added to a solution of III








(4.0 g., 0.015 mole) in 5 ml. of carbon tetrachloride. Distillation
gave 4.5 g. (70.0% conversion) of material, XXVI, b.p. 84-850/1.5 mm.,
3 1.5503. d 2.3748. Anal. Called. for C6F3IBr: MRD. 56.51;

%C, 17.08; %H, 1.43. Found: MRD, 56.74; C. 17.62; %H, 1.53.



3. IV with Bromine
In the manner previously described 7.0 g. (0.044 mole)
of bromine in 5 ml. of carbon tetrachloride was added to a solution

of IV (8.0 g., 0.043 mole) in 5 ml. of carbon tetrachloride.
Distillation gave 9.5 g. (64.1% conversion) of material, XXVII,
b.p. 830/3 mm., n 1.5198; d42 1.9897. Anal. Called. for C66F2Cl2Br2:

MRD. 52.97; %c. 20.78; %H, 1.74. Found: MRD, 53.01; %C, 20.80;
%H, 2.03.


4. V with Bromine
In the manner previously described 12.0 g. (0.075 mole)
of bromine in 10 ml. of carbon tetrachloride was added to a solution
of V (12.5 g., 0.061 mole) in 10 ml. of carbon tetrachloride.
Distillation gave 14.5 g. (65.0% conversion) of material, XXVIII,

b.p. 75-79o/7 ia.. nD 1.4351, d4 1.9715. The physical constants

agree with those reported by McBee (19).


5. VIII with Bromine
In the manner previously described 18.0 g. (0.113 mole)
of bromine in 15 ml. of carbon tetrachloride was added to a solution
of VIII (9.0 g., 0.066 mole) in 10 ml. of carbon tetrachloride.









Distillation gave 5.5 g. (28.7% conversion) of material, XXIX,
2222
b.p. 96-98/10 m., n22 1.4874. d22 1.9690. Anal. Calad. for

C6H F3Br2: HD. 43.24; %C, 24.35; %H, 2.38. Found: RD'. 43.25;

C. 24.48; %H, 2.74.


6. I with Methanolic Potassium Hydroxide

To a 100 ml. three-necked flask fitted with a reflux

condenser, a stirrer and a dropping funnel was added 30 g. (0.176 mole)

of I. Potassium hydroxide (10 g.. 0.175 mole) dissolved in 60 ml.

of methyl alcohol was added dropwise while the reaction flask was

eooled in an ice bath. After addition was complete, the reaction

mixture was poured into 500 ml. of cold water. The organic layer was

separated, washed with water, dried over calcium chloride and distilled

to give 14 g. (62.24 conversion) of material. XXI. b.p. 84-110. Anal.

Calcd. for C6gHF,: %C. 53.75; %H. 3.73. Found: C. 51.86; MU. 3.43.

This material polymerized upon standing and the monmer has been

assigned the structure CH2-CC=CH2 for reasons discussed previously.
1 11
CF2-CF


7. VII with Methanolic Potassium Hydroxide

To a 100 al. three-necked flask fitted with a reflux

condenser, a stirrer and a dropping funnel was added 25 g. (0.103 mole)

of VII. Potassium hydroxide (7.0 g., 0.125 mole) dissolved in 50 al.

of methyl alcohol was added dropwise while the reaction flask was

heated to 70-80. After addition was complete, the reaction mixture








was poured into 500 ml. of cold water. The organic layer was separated,
washed with water, dried over calcium chloride and distilled to give
7 g. (41.9% conversion) of material, XXXI, b.p. 132-134, nj 1.4048.

d1 1.0912. Anal. Cald. for CH9F3: RD. 36.48; %c, 59.25; %H, 5.59.

Found: MRD. 36.55; %C. 59.03; %H. 5.92.

This material has been assigned the structures

SCH2\
CH2-CHCH=CI2 and CH CFCH=CH2 for reasons discussed previously.
I I II I
CF,-CFCH=CH2 CH CPF
F2CH 2
2

8. IX with Ethanolic Potasoium Hydroxide
A solution of IX (18 g., 0.063 mole) in 95% ethyl
alcohol (20 ml.) was placed in a 100 ml., three-necked flask fitted
with a reflux condenser, a stirrer and a dropping funnel. The mixture
was heated to reflux and a solution of potassium hydroxide (15 g..
0.268 mole) dissolved in 50 ml. of 95% ethyl alcohol was added slowly.
After addition was complete, the reaction mixture was poured into
500 ml. of cold water. The organic layer was separated, washed with
water, dried over calcium chloride and distilled to give 5.5 g.
(39.8% conversion) of material, XXXII. b.p. 141 n1 1.3938, d2 1.4225.

Anal. Calcd. for C814F: MRD. 35.54; %C. 44.87; A. 1.88. Found:

M~D. 35.90; C, 44.80; %H. 2.16.
This material is the known (5) 1,2-bis(trifluoromethyl)-
benzene. CF3
Q0 CF









9. XXI with Methanolic Potasstuw Hydroxide

To a 250 ml., three-necked flask fitted with a reflux

oondenser, a stirrer and a dropping funnel was added 30 g. (0.148 mole)

of XXI. Potassium hydroxide (17 g., 0.30 mole) dissolved in 100 al.

of methyl alcohol was added dropwise while the reaction flask was

maintained at 30-40. After addition was complete, the reaction

mixture was poured into 500 ml. of cold water. The organic layer was

separated, washed with water, dried over calcium chloride and distilled

to give 8 g. (30.2% conversion) of material. XXXIII. b.p. 1810,
19 1.4290., d9 1.2654. Anal. Called. for C7HgF0: MR%. 35.63;


%C, 47.19; H. 4.53; %F. 21.33. Found: NRp, 36.44; %C. 47.18;

.H. 4.68; %F. 21.12.

This material has been assigned the structure

CH,-CCO2CH3 on the basis of its composition, mode of formation and

CF2-COCr 5

infrared spectrum.










VI SUMMARY


A study has been made of the reactions of chloretrifluoro-

ethylene, bromotrifluoroethylene. iodotrifluoroethylene, 1.1-dichloro-

difluoroethylene, perfluoropropene, perfluoroacrylonitrile, 4-bromo-

1.1.2-trifluoro-l-butene and 2,3-disehl xaorhealuoro-2-butee with

butadiene. Chlorotrifluoroethylene, bromotrifluoroethylene, iodotri-

fluoroethylene and 1,1-dichlorodifluoroethylene reacted with butadiene

to give only compounds containing the cyclobutane ring. However,

perfluoropropene, perfluoroacrylonitrile and 4-bromo-l,l,2-trifluoro-l-

butene reacted with butadiern to give in each ease both the cyclobutane

ring and the cyclohexene ring. 2,3-Dichlorohexafluoro-2-butene reacted

with butadiene to give only the cyclohexene ring.

Chlorotrifluoroethylene and a number of other fluoro6lefins

were added to various hydrocarbon olefins and dienee and a study was

made of their mode of formation.

Evidence was presented for a diradical transition state for

most of these cycloalkylation reactions.

Structures have been assigned for meat of the products and

were based on both cheical and physical evidence. Several of the

assigned structures have been definitely established by means of NMR

spectroscopy.









VII BIBLIOCRAPHY


1. Anderson, U.S. Patent 2,754.322 (1956).

2. Barney and Cairns. J. Am. Chem. Soc. 22, 3193 (1950).

3. Barriek, U.S. Patent 2,462.345 (1949).
4. Blosquist and Meinwald. J. Am. Chem. Soc. 22, 5316 (1957).

5. Brown and De Vriee. J. Am. Chei. Soc. 22, 1811 (1951).

6. Cairns, at al., J. Am. Chem. Soc. 80. 2775 (1958).

7. Coffman, Barrick, Cramer and Raaseh, J. Am. Cham. Soc. 71, 490

(1949).
8. Coyner and Hillman, J. An. Chem. Soc. 71, 324 (1949).

9. Derfer, Pickett and Boord, J. Am. Chem. Soc. 71, 2482 (1949).

10. Haszeldine and Osborne, J. Chem. Soc. f19, 3880.

11. Hasseldine and Steele, J. Chem. Soc. 1957, 2800.

12. Hauptsehein, Fainberg and Braid, J. Am. Chem. Soc. 80. 842 (1958).

13. Henne and Rub, J. Am. Chem. Soc. 62, 279 (1947).
14. Hine, Physical Organic Chemistry, McOraw-Hill Book Company, Inc.,

New York, N. Y. (1956), p. 462.

15. Johbel and Buts, J. Am. Chem. Soc. 6,. 3350 (19'1).

16. La Zerte, et al., J. An. Chen. Soc. 78. 5639 (1956).

17. Lovelace, Rausch and Postelnek, Aliohatic Fluorine Cenmounds.

Reinhold Publishing Corporation, New York, rl. Y. (1958), p. 38.

18. Marrison, J. Chem. Soc. 1951, 1614.

19. McBee, lisu, Pierce and Roberts, J. Am. Chem. Soc. 27, 915 (1955).

20. Middleton, at al., J. Am. Chem. Soc. 80. 2783 (1958).
64









21. Miller, U.S. Patent 2,691,036 (1954).

22. Piston and Plieninger, Ann. 562, 239 (1949).
23. Reid and Sack, J. Am. Chem. Soc. 22, 1985 (1951).

24. Roberts and Chambers, J. Am. Chem. Soc. Z2, 5030 (1951).

25. Silversmith, Kitahara, Caserio and Roberts, J. Am. Chem. Soc.

80, 5840 (1958).
26. Smith and Shriver, The Examination of llT Organic Conpound.s

John Wiley and Sons, Inc., New York, N. Y. (1956). p. 119.

27. Tallent and Siewers, Anal. Chem. 28. 955 (1956).
28. Walling, Free Radicals in Solution. John Wiley and Sons, Inc.,

New York, N. Y. (1957), p. 187.

29. Wilson, J. Chne. Phys. 11, 369 (1943).










BIOGRAPHICAL DATA


Robert William Johnson, Jr. was born on October 9. 1927, in

Jacksonville. Florida where he attended local schools and was

graduated from Andrew Jackson High School in June, 1945.

He enlisted in the U.S. Navy in September, 1945, and served

in both the Atlantic and Pacific Areas until his discharge in

October. 1948. He entered the University of Florida in February. 1949

and received the B.S. in Chemistry in June. 1953. The author began

graduate study at Purdue University in September. 1953. and was

awarded the M.S. degree in January. 1956. The author re-entered the

University of Florida in February. 1956 and undertook the program

leading to the Ph.D. degree in Fluorine Chemistry. He held a

teaching assistantship at Purdue University, and at the University of

Florida he held a research assistantship sponsored by the Office of

the Quartermaster General. U.S. Ary.

The author is a member of Alpha Chi Sigma, Gamma Sioma Epsilon,

Sigma Xi, American Chemical Society and the American Association for

the Advaneement of Science. He is married and has one child.









This dissertation was prepared under the direction of the

chairman of the candidate's supervisory committee and has been
approved by all members of that committee. It was submitted to the
Dean of the College of Arts and Sciences and to the Graduate Council,

and was approved as partial fulfillment of the requirements for
the degree of Doctor of Philosophy.


June 8, 1959




Dean, College of Arts WdSciences




Dean, Graduate School


SUPERVISORY COMMITTEE:




Chairman


614/ /


CAS j>j- T t
OA l^^/Nhe~rtjAn'


---




University of Florida Home Page
© 2004 - 2010 University of Florida George A. Smathers Libraries.
All rights reserved.

Acceptable Use, Copyright, and Disclaimer Statement
Last updated October 10, 2010 - - mvs