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PREPARATION AND REACTIONS OF
PARTIALLY FLUORINATED DIENES









BY

JERRY RONALD PATTON


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


1980

















ACKNOWLEDGEMENTS


The author wishes to express his appreciation to Dr. Paul

Tarrant, who directed this research, for his advice and under-

standing.

The author is very grateful to Dr. Wallace Brey and his

research group for assistance in the interpretation of the NMR

spectra and also thankful to Dr. Roy King and Ms. Jackie Dugan

for their able assistance with the mass spectral data.

Thanks are due PCR, Incorporated, for the use of their

equipment and instruments. Many helpful conversations were held

with Dr. Keith Baucom, Dr. Eugene C. Stump, Jr., and Dr. Ralph

De Pasquale of that company.














TABLE OF CONTENTS


PAGE

ACKNOWLEDGEMENTS ii

ABSTRACT x

LIST OF TABLES viii

SECTION 1 INTRODUCTION 1

Preparation of Olefins 1

Reactions of Olefins 2

2 + 2 Cycloaddition Reactions 2

Nucleophilic Reactions 4

Radical Reactions 8

SECTION 2 RESULTS AND CONCLUSIONS 13

Preparation of Olefins 13

Reactions of Olefins Prepared 24

Cycloaddition Reactions 24

Radical Additions 30

Reactions with Nucleophiles 34

Conclusions 44

SECTION 3 EXPERIMENTAL 51

Preparation of Precursors 52

Addition of 1,2-Dibromo-2- 52
chlorotrifluoroethane (CF2BrCFClBr)
to Propene (CH2=CHCH3)

Attempted Reaction of 1,2-Dibromo- 54
2-chlorotrifluoroethane (CF2BrCFC1Br)
with 1,3-Butadiene (CH2=CHCH=CH2)

iii











Addition of 1,2-Dibromo-2-chlorotri- 54
fluoroethane (CF2BrCFClBr) to
Trifluoropropene (CF3CH=CH2)

Addition of 1,2-Dichloro-2-iodo- 55
trifluoroethane (CF2Cl-CFCII) to
Trifluoropropene (CH2=CHCF3)

Preparation of l-Bromo-2-iodotetra- 56
fluoroethane (CF2BrCF2I)

Addition of l-Bromo-2-iodo- 57
tetrafluoroethane (CF2BrCF2I)
to Ethylene

Preparation of Olefins 57

Attempted Dehydrohalogenation of 57
CF2BrCFClCH2CHBrCH3 with
Aqueous Sodium Hydroxide

Dehydrohalogenation of 58
CF2BrCFClCH2CHBrCH3 with
Potassium-t-Butoxide and
Dimethylsulfoxide

Dehydrohalogenation of 58
CF2BrCFClCH2CHBrCH3 with
Ethanolic Potassium Hydroxide

Dehydrohalogenation of 59
CF2BrCF2CH2CH2I with Ethanolic
Potassium Hydroxide

Dehydrohalogenation of 60
CF2BRCFC1CH2CH(CF3)CH2CHBrCF3
with Ethanolic Potassium Hydroxide

Dehydrohalogenation of 60
CF2ClCFClCH2CHICF3 with Ethanolic
Potassium Hydroxide

Decarboxylation of 61
CF2CICFBrCF2CFBrCF2COONa

The Dehalogenation of 61
CF2BrCFCCH=CHCH3 with Zinc











Dehalogenation of 62
CF2BrCFCICH2CKBrCH3 with Zinc

Dehalogenation of 63
CF2BrCFClCH2CH(CF3)CH2CHBrCF3
with Zinc

Dehalogenation of 64
CF2CICFBrCF2CF=CF2 with Zinc

Dehalogenation of 64
CF2ClCFClCH=CHCF3 with Zinc

Dehalogenation of 65
CF2ClCFClCH2CHICF3 with Zinc

Reactions of Olefins Prepared 66

2 + 2 Reactions of Chlorotrifluoro- 66
ethylene with CF2=CFCH=CHCH3

2 + 2 Cycloaddition of 2,2,-Dichloro- 67
difluoroethylene with CF2=CFCH=CHCH3

Dimerization of CF2=CFCH=CHCH3 67

Dimerization of CF2=CFCH=CF3 67

Co-dimerization of CF2=CFCH=CHCH3 68
with CF2=CFCH=CHCFs

Attempted 2 + 2 Cycloaddition of 68
Chlorotrifluoroethylene with
CF2=CFCH2CHBrCH3

Attempted Reaction of Butadiene with 69
CF2=CFCH2CHBrCHa

Attempted Reaction of Butadiene 69
with CF2=CFCH=CHCH3

Radical Addition of Bromotrichloro- 69
methane to CF2=CFCH2CHBrCH3 with
Benzoyl Peroxide

Radical Addition of CC1lBr to 70
CF2=CFCH=CHCH3 Using Benzoyl Peroxide












Radical Addition of CC13Br with 71
CF2=CFCH=CHCF3 Using Benzoyl Peroxide

2 + 2 Cycloaddition Reaction of 71
Chlorotrifluoroethylene with
CF2=CFCF2CF=CF2

The Addition of Bromine to CF2=CFCF2CF=CF2 71

The Attempted Radical Addition of 2-lodo- 72
heptafluoropropane to CF2=CFCF2CF=CF2

The Attempted Reaction of Trifluoronitro- 72
somethane with CF2=CFCF2CF=CF2

The Reaction of Ozone with CF2 CFCH=CHCH3 73
CF2 CFCH=CHCH3

The Reaction of Ethanol and Potassium 74
Hydroxide with CF2=CFCH=CHCH3

The Reaction of Ethanol and Potassium 74
Hydroxide with CF2=CFCH=CHCF3

Addition of Bromine to CF2=CFCH=CH3 75

Addition of Bromine to CF2=CFCH=CHCF3 76

The Reaction of Trifluoronitrosomethane 76
with CF2=CFCH=CHCH3 at -78C

The Reaction of Trifluoronitrosomethane 78
(CF3NO) with CF2=CFCH=CHCF3 at -78C

The Reaction of Phenylmagnesium Bromide 78
with CF2=CFCH=CHCH3

The Reaction of Phenylmagnesiun Bromide 79
with CF2=CFCH=CHCF3

Attempted Reaction of CF2=CFCH=CHCH3 80
with Diethylamine

Reaction of CF2=CFCH2CHBrCH3 with 80
Magnesium

Attempted Reaction of CF2=CFCH=CHCF3 81
with H2S04 and Water












SECTION 4 ENVIRONMENTAL IMPACT UZ

Explanation of Symbols and Abbreviations 85
for Environmental Impact

REFERENCES 189

BIOGRAPHICAL SKETCH 192

















LIST OF TABLES



NUMBER PAGE

I FLUORINATED STARTING MATERIALS 14

II FLUORINATED OLEFINS FROM 19
*
CF2BrCFClCH2CHBrCH3

III FLUORINATED OLEFINS FROM THE 25
CF2ClCFClCH2CHICF,

IV FLUORINATED OLEFINS FROM 26
CF2C1CFBrCF2CFBrCF2COONa

V 2 + 2 CYCLOADDITION REACTIONS 27

VI RADICAL ADDITION REACTIONS 35

VII NUCLEOPHILIC REACTIONS 41

VIII REACTIONS OF THE 1,1,2-TRIFLUORO- 47
PENTADIENE-1,3

IX REACTIONS OF THE 1,1,2,5,5,5- 49
HEXAFLUOROPENTADIENE-1,3

X REACTIONS OF THE PERFLUOROPENTADIENE-1,4 50

XI MASS SPECTRUM OF CF2BrCFC1CH2CHBrCH3 92
(BOTH DIASTEREOMERS)

XII MASS SPECTRUM OF CF2BrCFCICH2CHCH2CHBrCF3 97
CFs

XIII MASS SPECTRUM OF CF2BrCFClCH=CHCH3 104

XIV MASS SPECTRUM OF CF2=CFCE=CHCH3 113


viii











XV MASS SPECTRUM OF CF2=CFCH2CRBrCH3 117

XVI MASS SPECTRUM OF CF2=CFCF2CF-CF2 122

XVII MASS SPECTRUM OF CF2CFCH=CHCH3 126

CF2CFCH=CHCH3

XVIII MASS SPECTRUM OF CC3lCF2CFBrCH2CHBrCH3 131

XIX MASS SPECTRUM OF CH3CHO2CF2CFHCH=CHCH3
AND CH3CH20FCF=CHCH2CH3 MIXTURE 139

XV MASS SPECTRUM OF CF2BrCFBrCH=CHCHE 142

XXI MASS SPECTRUM OF CF2CF=CHCCH3 146
\ /
N--0
I
CF3

XXII MASS SPECTRUM OF CF2ClCFClCH2CHICF3 152

XXIII MASS SPECTRUM OF CF2CICFC1CH=CHCF3 155

XXIV MASS SPECTRUM OF CF2=CFCH=CHCFs 159

XXV MASS SPECTRUM OF CC13CF2CFBrCH=CHCH3 163

XXVI MASS SPECTRUM OF CF2CFCH=CHCF3 166
I I
CF2CFCH=CHCF3

XXVII MASS SPECTRUM OF CF2CFCH=CHCF3 169
I I
CF2CFCH=CHCH3

XXVIII MASS SPECTRUM OF CF2BrCF=CHCHBrCF3 AND 175
CF2BrCFBrCH=CHCF3

XXIX MASS SPECTRUM OF CF2CF=CHCHCF3 180
\ /
N-0
CF3

XXX MASS SPECTRUM OF C6H5CF=CFCH=CHCH3 182

XXXI MASS SPECTRUM OF C6HsCF=CFCH=CHCF2 185

XXXII MASS SPECTRUM OF CF2-C1CFC1CH2CH=CF2 189
















Abstract of Dissertation Presented to the Graduate Council
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy



PREPARATION AND REACTIONS OF
PARTIALLY FLUORINATED DIENES

By

Jerry Ronald Patton

December 1980

Chairman: Dr. Paul Tarrant
Major Department: Department of Chemistry


The preparation of three fluorine-containing dienes, 1,1,2-

trifluoropentadiene-1,3 (I), 1,1,2,5,5,5-hexafluoropentadiene-l,3

(II), and 1,4-perfluoropentadiene (III) was carried out. Two

asymmetric centers present in the precursors of I and II,

CF2BrCFC1CH2CHBrCH3 (IV) and CF2ClCFClCH2CHICF3 (V), made possible

the separation of two diastereomers for each alkane. The dehydro-

halogenation reaction of IV and V with ethanolic potassium

hydroxide gave exclusively the trans products, CF2BrCFClCH=CHCH3 (VI)

and CF2ClCFC1CH=CHCF3 (VII). The products realized by dehalogenation

of VI and VII with zinc were the respective dienes I and II. The 1,4-

perfluoropentadiene was prepared by the decarboxylation reaction

of CF2ClCFBrCFaCFBrCF2COONa to give the olefin CF2ClCFBrCF2CF=CF ,

which was dehalogenated with zinc to give the diene III.










Three types of reactions were studied with the dienes, 2 + 2

cycloaddition, nucleophilic addition, and radical addition. The

formation of a cyclobutane product from I at OC indicated the

unusual reactivity of this diene. At a temperature of 100*C, both

I and II reacted quantitatively in 20 hours to give the respective

cyclobutane products. The reaction of a mixture of I and II at

1000C gave an almost statistical distribution of the two homo-

cyclobutane products along with the mixed cyclobutane. The attempt

to form cyclobutane products from 1,4-perfluoropentadiene was

unsuccessful.

Nucleophilic addition reactions using phenylmagnesium bromide

and ethanolic potassium hydroxide with I gave the addition-

elimination product and products formed by 1,2 and 1,4 addition,

respectively. Reaction of II with phenylmagnesium bromide resulted

in the addition-elimination product. Alcohol added 1,4 to give

the ether.

Three types of radical initiated reactions were studied with

the dienes. Trifluoronitrosomethane reacted with I and II,

respectively, to give the Diels-Alder products and polymer products

which contained both 1,2 and 1,4 structural units. No reaction

took place between III and CF3NO. The addition of bromine to I

gave only the 1,2 adduct. Diene II reacted with bromine to give

both 1,2 and 1,4 addition products. 1,4-Perfluoropentadiene reacted

with bromine to give 1,2 addition product with no cyclization

products detected. Bromotrichloromethane gave the simple 1 to 1










adduct with diene I and higher telomers with no 1 to 1 adduct

structure for II. Diene III did not react with CCl3Br.

Eight new compounds were prepared and characterized by

infrared analysis, NMR, and mass spectral data.

















SECTION 1

INTRODUCTION

Preparation of Olefins



A number of reports has appeared in the literature on the

preparation and reaction of haloalkanes to give fluorine-containing

enes and dienes. Very little information, however, has been made

available on the study of the reactions of 1,1,2-trifluoro-dienes.

Hexafluorobutadiene-1,3, because of its availability, has been

historically the most studied of the fluorine-containing diene

compounds. Examples of polymerization reactions involving homo-

polymers, co-polymers, and ter-polymers of hexafluorobutadiene-1,3

are prevalent in literature reports.

The preparations of fluorine-containing dienes have been

reported by several groups.1-3 A general method for the preparation

of these compounds can be shown as follows:



1. XCF2CFYZ + CH2=CHR -> CF2XCFYCH2CHZR

X = Cl, Br; Y = Cl; Z = Br, I; R = CH,, CF,
KOH *
2. CF2XCFYCH2CHZR -_--> CF2XCFYCH=CHR


Zinc
3. CF2XCRYCH=CHR -in- > CF2=CFCH=CHR
EtOH









The free radical addition reactions, involving halogen-containing

compounds to olefins, have been used extensively to prepare fluoro-

alkanes.1'2'4-10 The dehydrohalogenation is facilitated with

potassium hydroxide and ethanol since the adjacent halogens cause the

hydrogen to be more acidic than in hydrocarbon surroundings.

Dehalogenation with zinc in ethanol is common for the preparation

of fluorinated olefins.

The usual reactions of fluoroalkenes such as halogen addition,

radical initiated additions, nucleophilic attack, and 2 + 2 cyclo-

additions, have not been thoroughly studied for 1,1,2-trifluoro-

dienes. The lack of activity in this area prompted our research.



Reactions of Olefins

2 + 2 Cycloaddition Reactions

Fluorinated olefins usually give 2 + 2 cycloaddition products

when treated thermally as shown below:



4. CF2=CFX --> CF2-CFX
I I
CF2-CFX

X = Cl, F, Br, I, OCH3, etc.



The 2 + 2 cycloaddition reaction has been mechanistically shown to

be a two-step bi-radical process.11












5. CF2=CFX --> CF2-CFX CF2-CFX

CF2-CFX CF2-CFX

X = F, Cl, Br, I, OCH3, etc.



Those olefins which are very reactive in forming 2 + 2 cyclo-

addition products usually give no 2 + 4 Diels-Alder products.

For example, tetrafluoroethylene reacts with butadiene to give only

the vinylcyclobutane.11



6. CF2=CF2 + CH2=CH-CH=CH2 -- > CH2-CH-CH=CH2
I I
CF2-CF2



Diels-Alder products are only isolated from reactions where the diene

is locked into a cisoid configuration such as cyclic dienes. Cyclo-

pentadiene is one of the few dienes which form Diels-Alder products

with fluoroolefins. A good review of Diels-Alder reactions of

organic fluorine compounds can be found in Fluorine Chemistry Reviews,

Vol. 1, No. 2.12

Hexafluorobutadiene-1,3 has been described as acting neither as

the diene nor dienophile in a Diels-Alder reaction.



7. CF2=CF-CF=CF2 --> CF2-CF-CF=CF2
I I
CF2-CF-CF=CF2










The only product isolated as the 2 + 4 Diels-Alder adduct with

this diene has been that derived from trifluoronitrosomethane.

Trifluoronitrosomethane has been reported to react with fluorinated

dienes via a radical anion mechanism, probably involving
e.
CF3N(O)N(O)-CF,.13 The reaction with hexafluorobutadiene-1,3 gives

the 2 + 4 Diels-Alder adduct along with polymeric products.


8. CF3NO + CF2=CFCF=CF2 -> CF2-CF=CF-CF2

N- 0 + 1,2 and 1,4

CF3 polymer



The study of 2 + 2 cycloaddition reactions of fluorine-containing

dienes, other than hexafluorobutadiene-1,3, has been neglected by

previous workers.


Nucleophilic Reactions

Most reactions involving fluorine-containing olefins are

nucleophilic in nature, due to the stabilization of the anion by the

halogen atoms in the a or B-position. Hydrocarbon and partially

fluorinated olefins undergo electrophilic reactions because of

stabilization of the intermediate positive charge. The higher the

degree of fluorination the more likely the nucleophilic reaction to

predominate, as the example shows.


+ _
9. CF2=CH2 + P- -> CF2-CHs -- > CF3-CH3


CF3 CF. + CF3
F C=CF2 + --> F3 ---> CH-CF
CF3 CF3 CF3










Fluorine-containing olefins are very susceptible to attack by nucleo-

philes such as Grignard reagents, alkoxides, and halide anions.14-17

Examples of these reactions are as follows:



10. RMgX + CF2=CFR' --> RCF=CFR' + MgXF



11. Rt + CFa=CF2 ROH> ROCF2CF2H + ROCF=CF2



12. MF + CF2=CFR' -> CF3-CFR' + 12 -> CF3CFIR' + MI



R = alkyl, aryl

R' = F, Cl, Rf, etc.

M = Na, K, Cs



The reactivities toward nucleophiles of dienes which contain

fluorine vary. Tarrant and Heyes15 found that Grignard reagents

such as allylmagnesium bromide did not react with fluorinated

dienes such as l,l,2-trifluoropentadiene-l,4. The usual reaction

of Grignard reagents gives the olefin by loss of fluoride ion.

The addition-elimination or SN2' type reaction of Grignard

reagents with fluorinated olefins is well documented.18 Rearrange-

ments of the intermediate anion have been reported,19 with the

conjugated olefin predominating where possible.



13. C6H!MgBr + CF2=CFCF2C1 --> C6HsCF=CF-CF2C1 predominant

and product

C6H5CF2-CF=CF2











CF2Cl ,CF2C1
14. C6sHMgBr + CH2=C CeHCH2-C
CF2Cl CF2

and

CF2C1
C6H,-CH2-CC
kCFCl



The reaction of alkyl Grignard reagents with olefins which

contain fluorine has been shown by Okukara14 to give two products.



15. CH3CH2MgX + CF2=CC12 -- > CHCH2-CF2-CC12H + CH3CH2-CFCC12

predominant product



A radical intermediate, not hydrolysis of the intermediate

CH3CH2CF2CC12MgX, was proposed to account for the formation of the

major product.

Nucleophiles such as ethoxide (CH3-CHa2-0 have been added

to hexafluorobutadiene-1,3 to give several products depending on

reaction conditions. Knunyants et al.20'21 reported the following

sequence:



16. CH3CH20H + CF2=CFCF=CF2 (C2H)3N > CF2=CFCFHCF20CH2CH3
R.T.1,2 adduct
P 1 1,2 adduct


CFa-CF=CHCF2OCH2CHa










The allylic rearrangement of the fluoroether was unexpected

for this type of unsaturated compound, but it was probably caused by

the attack of fluoride anion, obtained from the partial hydrolysis

of the ether, followed by the rearrangement and loss of fluoride.

The same group also found that at higher temperatures, 90-100C,

the 1,4 addition product was obtained.



17. CH3CH20H + CF2=CFCF=CF2 90C200N > CHCHOCF2CF=CFCF2H

1,4 adduct



Dedek and Kovac22 reported the following results from the reaction of

ethanol and sodium ethoxide with hexafluorobutadiene-1,3.



18. CH3CH20H + CH3CH2ONa + CF2=CFCF=CF2 ->

CH3CHaOCF2CF=CHCOOCH2CH3



Their product probably arose by the following reactions.



19. CFz=CFCF=CF2 + CHsCH20H CH3CH2ONa > CH3CH20CF2CFHCF=CF2



20. CH3CH2OCF2CFHCF=CF2 + CH3CH20H -> CH3CH20CF2CFHCFHCF20CH2CH3


-HF
21. CH3CH2OCFzCFHCFHCF2OCH2CH3 ---> CH3CH20CF2CF=CHCF20CH2CH3

I hydrolysis

CH3CH20CF2CF=CHCOOCH2CH3










The various results were ascribed to temperature dependence and

base strength differences. The addition of alcohols to fluorine-

containing conjugated triene systems has also been studied by Dedek

and Kovac22 and results in addition-elimination reaction to give

the a,u-triene diether.



22. CF2=CFCF=CFCF=CF2 + CH3CH20H + CH3CHO0Na --



CH3CH20CF=CFCF=CFCF=CFOCH2CH3



The study of nucleophilic attack on fluorinated 1,1,2-trifluoro-

diene systems has not been reported except for isolated cases such as

fluoride anion induced rearrangement of perfluorinated compounds.23'24



23. CF2=CFCF=CFCF3 + CsF -> CFCCCF2CF3C



Radical Reactions

Halogen atoms are added to the double bonds of fluorinated

olefins by radical means.24 Electrophilic ionic additions such as

occur in hydrocarbon olefins are rare but do occur in olefins

which contain both hydrogen and fluorine. In the fluorine-

containing 1,1,2-trifluoro-dienes we propose to study, two products

can be formed.










24. CFa=CF-CH=CHR + Br2 -> CF2Br-CFBr-CH=ChR 1,2 adduct

and

CF2Br-CF=CH-CHBrR 1,4 adduct

R = CH3, CF3



Study of halogen addition to fluorinated conjugated dienes has

been limited to selected dienes such as hexafluorobutadiene-1,3,

1,1,2-trifluorobutadiene-l,3, and 1,1,2,4-tetrafluorobutadiene-1,3.

Rondarev et al.25 proposed an ionic mechanism in the bromination

of the selected dienes. From hexafluorobutadiene-1,3, the (E)-1,4-

dibromoperfluoro-2-butene was formed exclusively.



25. CF2=CFCF=CF2 + Br2 --> F C /CF2Br
CF2Br. C F



The 1,4-addition product was also obtained in the reaction

of iodine monochloride with the butadienes and an ionic mechanism

was proposed.25



26. IC1 + CF2=CF-CH=CH2 --> CFClCF=CHCH2I



A good review of reactions between fluoroolefins and electrophiles

can be found in Fluorine Chemistry Reviews, Vol. 3.26

Other results involving hydrocarbon radical reactions with

fluorinated dienes have shown that dienes such as hexafluorobuta-

diene-1,3 are more reactive than mono-olefins. The difference in










reactivity, however, is not so great as in the corresponding

hydrocarbon systems. Sass et al.10 found the reactivity of radicals

with fluorinated olefins to decrease according to the following

substitution pattern: CF2=CF2 > CF2=CFOR > CF2=CFRf. He carried

out the addition of methane to the alkenes by the reactions shown

below:

o 0 o
II A II -CO
27. CHa-C-O-O-C-CH3 -- > 2CH3-C-0 --- > 2 -CH3



28. *CH3 + CFa=CFR -> CH1-CF2-CFR


CHs

29. CH3CF2-CFR + CHa-CH-CH2-CH2C2CH2CHs -- > CH3CF2CFHR

R = F, OR or Rf




Halogen addition reactions and polymerizations are the only

types of radical reactions which have been reported for conjugated

1,1,2-trifluoro-dienes except for the isolated case where Muramatsu

added bromotrichloromethane to CF2=CFCH=CH2.8

Muramatsu and Tarrant8 studied the radical addition of bromo-

trichloromethane to 1,1,2-trifluorobutadiene and the non-conjugated

l,l,2-trifluoropentadiene-l,4. The attack on the hydrocarbon

segment of the dienes was unexpected.



30. CClsBr + CF2=CFCH=CH2 --> CCI3CH2CH=CFCF2Br and polymer by

1,4 addition










31. CC13Br + CF2=CFCH2CH=CH2 -> CCl3CH2CHBrCH2CFCF2

and

CC13CH2CHBrCH2CFBrCF2CC13



Polymerization of conjugated dienes gives polymers of both

1,2 and 1,4 structure. The polymerizations proceed by a radical

mechanism.27'28



32. CF2=CFCF=CFCF3 --A> -fCF2CF+n
In
CF
II
CF
I
CF CF

and -jCF2CF=CFCF}-



Non-conjugated perfluorodienes are reported to give intramolecular

cyclic polymers.29-35



33. CF2=CFCF2CF=CF2 A> -JCF2CF-CF
I I
CF2CF- n



According to Muramatsu et al.4 even hindered partially fluorinated

pentadienes such as 2-methyl-3,4,5,5,5-pentafluoro-l,3-pentadiene

polymerized to give both 1,2 and 1,4 polymer structures. Muramatsu

obtained polymers which contained both vinyl side chains and double

bonds in the backbone of the polymer.












CF,
CF

CH3 CF
34. CH2=C-CF=CFCF3 ---- > CH2-C
CH3 n 1,2 polymer


CH3

and-4CH2-C=CF-CF 1,4 polymer
CF3 n



A study.of the reactions of 1,1,2-trifluoro-dienes with

radicals and nucleophiles, and in cycloaddition reactions, was

begun to extend our knowledge in this area.

The recent concern for environmental considerations prompts

the environmental impact study at the end of the Experimental

Section. Each chemical used is listed with its NIOSH registry

number and available toxicity data. Due to the small scale and

research quantities of chemicals prepared, no detrimental effect

on the environment was expected.

















SECTION 2

RESULTS AND CONCLUSIONS



A study of the reactions of three 1,1,2-trifluoropentadienes

has been carried out. The results of radical reactions, nucleophilic

reactions, and 2 + 2 cycloadditions will be presented.



Preparation of Olefins

The three systems chosen for study were 1,1,2-trifluoropentadiene-

1,3 (CF2=CFCH=CHCH3, I), l,l,2,5,5,5-hexafluoropentadiene-1,3

(CF2=CFCH=CHCF3, II), and 1,4-perfluoropentadiene (CF2=CFCF2CF=CF2,

III). Two asymmetric centers are present in both CFzBrCFClCH2CHBrCH3

and CF2ClCFClCHzCHICF3 and only the trans olefins were obtained by

dehydrohalogenation. For these reasons the preparations of the

respective olefins, CFaBrCFClCH=CHCH3 and CF2ClCFCICH=CHCF3, and

dienes CF2=CFCH=CHCHS and CF2=CFCH=CHCFa, are treated separately.

Reactions and conclusions will be discussed together to show the

similarities and differences of the various dienes. Table I contains

the fluorinated starting materials used in olefin preparation.

The first diene studied was l,l,2-trifluoropentadiene-l,3

(I), which was prepared by the method of Tarrant and Gillman.1 The

following reaction scheme shows the sequence and yields of the

various reactions:









TABLE I

FLUORINATED STARTING MATERIALS


Compound

CF2BrCFClBr

CF2BrCF2I

CF2BrCFClCH2CHBrCHsI

CFOBrCF2CH2CH2I

CF2ClCFBrCF2CFBrCF2COONa2

CF2BrCFClCH2CH(CFS)CH2CHBrCF,


CF2ClCFClI

CPaC1CFC1CH2CHIICFp3

CF0NO


Boiling
Point

91C

78-79C

177-182C

160-161C



(56-59C/
0.1 mm)

100-101"C

160-161C


Preparation Method

CF2=CFC1 + Br2

CF2CF2 + Br2 + 12

CF2BrCFClBr + CH2=CHCHs

CF2BrCF2I + CH2=CH2

CF2C1CFBrCF2CFBrCF2COF + Na2COs

CF2BrCFC1Br + CH2=CHCFs


C=CFC1 + IC1

CF2CICFC1I + CH2=CHCF3

CF3C02NO heat > CF2NO


% Yield

90%

28%

83%

58%


Infrared Figure

Figure 1

Figure 11

Figures 2 and 3

Figure 12


25% Figure 7


Figure 51


1) Two diastercomers. Precursor to CF2=CFCII=CIICI1 (I)
2) Two diastercomers. Precursor to CF2=CFCF2CF=CF2 (III)
3) Two diastereomers. Precursor to CF2=CFCH=CHCF, (II)










Reaction Scheme 1



autoclave *
. CFBrCFCBr + CH2=CHCH3 peroxide> CF2BrCFClCH2CHBrCH3
peroxide

80% yield of two diastereomers



KOH *
2. CF2BrCFClCH2CHBrCH3 --- > CF2BrCFClCH=CHCH3
EtOH

88% trans olefin only



Zinc
3. CF2BrCFClCH=CHCH3 -n> CF2=CFCH=CH3 92%
EtOH



Tarrant and Gillman1 did not report the presence of two

diastereomers in the products obtained in reaction 1. Their

yield in step 2 was 45%. The trans geometry of CF2BrCFClCH=CHCHa

obtained in step 2 was not discovered by these workers. Our

procedure gave a three-fold increase in yield for the diene (I).

The two diasteromers from Step 1 were isolated on a 40-plate

Oldershaw column. Each gave the same mass spectrum. However, NMR

analysis indicated the components to be the two diastereomeric

products.

In step 2, a reported yield of 45% was expected.1 A much higher

yield of 88% was realized from the mixed diastereomers, but the

yield decreased rapidly with other impurities present. The NMR

analysis also indicated only one isomer, the trans olefin, to be

present. Space-filling models readily explained the exclusion of

the cis olefin from the product. The presence of the chlorine and

the CF2Br group on the 0 carbon prohibits free rotation of the CHBr








moiety. Trans elimination, being favored, gives only the trans olefin

from both the R and S configuration about the asymmetric CHBr center.


H,
rotation
for trans
elimination


Preferred S

configuration


KOH
EtOH


CF2BrCFC1 H
C=C
H CH3

trans product


CF2BrCFCl


Br
J-


CFClCF2Br

Preferred R

Configuration


rotation
for trans
elimination


Br

CF2BrCFCl H


H CH3

H


k,












KOH CFBrCFCl H
EtOH H
H- CH,



The size of the CF2BrCFCl group does not allow rotation to place

this group between the bromine atom and methyl group, therefore; no

cis product was formed. Two possible olefins were expected from the
*
dehydrohalogenation of CF2BrCFClCH2CHBrCH3.


4* KOH *
4. CFaBrCFC CHBrCHC 3 EtOH> CF2BrCFClCH=CHCH3

and

CFBrCF=CHCHBrCH3




That the only product isolated was CF2BrCFClCH=CHCH3 was attributed

to the greater leaving ability of bromine compared to chlorine. In

contrast, Piccardi et al.3 reported the ethanolic potassium
*
hydroxide dehydrohalogenation of CF3CFBrCH2CHBrCH3 to give both

olefins.



KOH *
5. CF3CFBrCH2CHBrCH3 -- CF3CF=CHCHBrCH3
EtOH
and

CF3CFBrCH=CHCH3



The attempted dehydrohalogenation of CF2BrCFCICH2CHBrCH3

using aqueous (50%) sodium hydroxide was carried out at 800C. The

two materials were immiscible and no reaction was detected over a









*
one-hour period. Reaction of the alkane, CF2BrCFClCH2CHBrCH3, with

potassium t-butoxide in dimethyl sulfoxide gave the desired olefin,

CF2BrCFClCH=CHCH3, in 73% yield. Of the three reagents, ethanolic

potassium hydroxide gave the best yield and purest crude product.
*
The reaction of CF2BrCFClCH2CHBrCHs with zinc was carried out to give

CF2=CFCH2CHBrCHa as an alternate precursor to CFa=CFCH=CHCH3. The

yield in this reaction, 79%, was not as good as that from
*
CF2BrCFClCH=CHCH3.

The dehalogenation in step 3 was reported to give a 60% yield

with CF2BrCFCICH=CHCH3. A 92% yield was realized from the pure
*
trans olefin. The products prepared from CF2BrCFClCH2CHBrCH3

along with the preparation method, yield, and boiling points

are reported in Table II. Each product was completely identified

by infrared, NMR, and mass spectral analysis.

NMR and mass spectral data for each diastereomer prepared in

Step 1, and each of the olefins obtained are presented in the

Experimental Section. Infrared spectra are given for all starting

materials as well as the reaction products.

After being stored at 0C for 20 days, the diene had reacted

to give the cyclobutane derivative and a white granular polymer.



6. 2 CF2=CFCH=CHCH3 --> CF2CFCH=CHCH3 + polymer
I I
CF2CFCH=CHCH3

















Compound


CF2=CFCH2CHBrCH3



CF2BrCFClCH=CHCH3



CF2=CFCH=CHCH3



CF2CFCH=CI1CH3

CF2CFCi=CHC1l3


TABLE II

k
FLUORINATED OLEFINS FROM CF2BrCFC1CH2CHBrCH3


Boiling
Point Preparation Method


Zinc
110-111C CF2BrCFClCCHHBrCHs Z >
EtOH



133-134C CF2BrCFClC2CHHBrCH3 >O
EtOH


0* Zinc
44-45C CF2BrCFClCH=CHCHs ---

160161 DimEtrization of CFCFCHCC

160-161oC Dimnrization of CF2=CFCIL=CHCHs


% Yield


91%



88%



92%



100%


Infrared Figure


Figure 24



Figure 13



Figure 20



Figure 31










A higher reaction temperature is usually required for 2 + 2

cycloaddition reactions. Chlorotrifluoroethylene does not form

the cyclic dimer below 175C and even activated fluorocarbon olefins

require a temperature of 100C for extended periods of time. The

remaining reactions of 1,1,2-trifluoropentadiene-l,3 were carried

out on freshly prepared and distilled diene. These reactions will

be reported after procedures for the preparation of the remaining

dienes have been described.

To acquire information on fluorocarbon compounds which contain

iodine, l-bromo-2-iodotetrafluoroethane was prepared and added to

ethylene. The butane was converted to the olefin by the following

reaction scheme.



Reaction Scheme 2



1. CF2=CF2 + Br2 + I2 Autocle CF2BrCF2Br (31%) +



CF2BrCF21 (49%) + CF2ICF21 (20%)



2. CF2BrCF2I + CH2=CH2 benzoyl > CF2BrCF2CH2CH2I 68%
peroxide



KOH
3. CF2BrCF2CHCH2I OH- > CF2BrCF2CH=CH2 76%



The reaction of ethylene with the iodide, CF2BrCF2I, was

found to take place thermally at 1500C in four hours to give the

desired adduct. The discovery of this fact in the preparation of

the precursor for l,l,2,5,5,5-hexafluoropentadiene-l,3 was fortuitous.









An attempt to prepare l,l,2,5,5,5-hexafluoropentadiene-l,3 (II)

was made. The reaction of 1,2 dibromo-2-chlorotrifluoroethane

with trifluoropropene was carried out using the same procedure as

with propene. The only product isolated, however, was the adduct

containing two moieties of trifluoropropene. This result can be

attributed to the presence of the CF3 group adjacent to the carbon

containing the unpaired electron, which stabilizes this radical,
*
CFBrCFClCHzCHCF3, and makes it less reactive than

CF2BrCFCICH2HCH3. Tarrant and Lilyquist2 also noted the relative

inability of CF3CH=CH2 to form 1 to 1 adducts with CF2BrCFClBr.



CF2BrCFClBr + CF3CH=CH2 -> CF2BrCFCl CH2CH 12CHBrCF3
CFa n



n = 1, 2, 3, etc.



Higher molecular weight components were also obtained but

not isolated. The following sequence for the formation of the

2 to 1 adduct is proposed.



CF2BrCFClBr + CF3CH=CH2 benzoyl > CF2BrCFClCH2HCF
peroxide
I + CF3CH=CH2
CF2BrCFClBr C *
CF2BrCFClCHI 2 CCII2CHBrCF < CF2BrCFClHCHCH2CCF3
CF3 CF3










A diene was formed by the reaction of zinc on the octane

above. It was identified by NMR, infrared analysis, and mass

spectral data as CF2=CFCH2CHCH2CH=CF2. The formation of a CH=CF2

CF3

group with zinc was not expected since Tarrant and Keller36-showed

that coupled and reduced products predominated with fluorinated

compounds containing iodine.


CF3CF3
Zinc I
CF3CFICF,3 C > CF3CFHCF and CF3C-C-CF3
CF3COOEt
F F



The successful preparations of the desired 1,1,2,5,5,5-hexa-

fluoropentadiene-1,3 was carried out following the sequence described

by Tarrant and Lilyquist2 as shown in reaction scheme 3.



Reaction Scheme 3



150C *
1. CF2ClCFCII + CH=CHCF3 > CF2ClCFClCH2CHICF3 80%
4 hours



2 KOH *
2. CF2ClCFCICH2CHICF3 F---> CF2CICFCICH=CHCF3 70%
EtOll

trans only

Zinc
3. CF2ClCFClCH=CHCF3 E- n > CF2=CFCH=CHCF3 80%
-EtOH









Two diastereomers of CF2CICFCl2C2CHICF3 were obtained from

the addition reaction, step 1. Dehydrohalogenation gave only the

trans olefin, CF2C1CFC1CH=CHCF3, in step 2. Tarrant and Lilyquist2

did not report two diastereomeric products in step 1, or the

exclusive trans geometry for the olefin obtained in Step 2.

Comparable yields were obtained by our procedures. The loss of the

bulky iodine is greatly favored over the loss of chlorine and with

iodine being a better leaving group, the product was exclusively

the trans olfein. The trans geometry in the olefin has been

previously explained for CF2BrCFClCH=CHCH3 formation from
*
CF2BrCFClCH2CHBrCH3. The l,l,2,5,5,5-hexafluoropentadiene-l,3,

obtained in step 3, was purified on a 25-plate Oldershaw column

and the correct boiling point was found to be 43-440C instead of

50C as reported by Tarrant and Lilyquist.2 The sample boiling at

50C was found to contain 92% of the desired diene and 8% of

CF2C1CFClCH=CHCF3.
*
The dehalogenation of CF2C1CFClCH2CHICF3 with zinc in

ethanol gave an interesting new olefin.



Zinc
CF2C1CFC1CH2CHICF3 t-- > CF2ClCFClCH2CH=CF2




> CF-=CFCH2CHICF3



The olefin was identified by the difluorovinyl absorption in the

infrared (5.67p) and F19 NMR data. Mass spectral analysis gave the










molecular ions for the two chlorine system and a cracking pattern

identifying the olefin unequivocally. The expected product,

CF2=CFCH2CHICF3, was not found. The list of olefins prepared from

CF2C1CFClCH2CHICF, is given in Table III.

The final pentadiene prepared was 1,4-perfluoropentadiene using

the reaction sequence reported by Fearn et al.30 as shown below.



Reaction Scheme 4


A heat *
1. CF2ClCFBrCF2CFBrCF2COONa > CF2CICFBrCF2CF=CF2 70%



Zinc
2. CF2ClCFBrCF2CF=CF2 --nc-> CF2 CFCFF=CF2 75%
EtOH



Our synthesis gave comparable yields to that of Fearn et al.30

Each of the compounds was identified by infrared analysis, NMR, and

mass spectral data. Table IV gives the pertinent data concerning

the compounds involved in the preparation of 1,4-perfluoropentadiene.



Reactions of Olefins Prepared

Cycloaddition Reactions

The 2 + 2 cycloaddition reaction of the three fluorine-containing

pentadienes was studied using both fluoroolefins and fluorodienes as

well as butadiene itself. Table V shows the reactions carried out

in this study. The only 2 + 2 cycloaddition products isolated

were from the conjugated pentadienes reacting with themselves or each

other.


















Compound



CF2ClCFClCH=CHCFs



CF2ClCFClCH2CH=CF2



CF2=CFCI=CIICFs



CF2CFCll=CIICF

CF2CFC1I[CllCFP


TABLE III

FLUORINATED OLEFIN FROM THE CF2ClCFClCH2CHICFs


Boiling
Point Preparation Method



KOH
88C CF2ClCFClCH2CHICFs EtH>


S Zinc
101-103C CF2ClCFClCH2CHICF3 Et>
EtOH


Zinc
43-44C CF2ClCFaC lCI=CH=CHCFS



133-135C Dimerization of CF2=CFCII=CHCFa


% Yield



70%



72%



92%



100%


Infrared Figure



Figure 55



Figure 80



Figure 57



Figure 63



















Compound



CF2ClCFBrCF2CF=CF2



CF2=CFCF2CF=CF2


TABLE IV


FLUORINATED OLEFINS FROM CF2C1CFBrCF2CFBrCF2COONa


Boiling
Point Preparation Method % Yield



*heat
104-1060C CF2ClCFBrCF2CFBrCF2COONa > 70%



Zinc
36-38C CF2ClCFBrCF2C=CF2 > 75%
EtOH


Infrared Figure



19



29









TABLE V

2 + 2 CYCLOADDITION REACTIONS


Olefin 1

CF2=CFCH=CHCH3



CF2=CFCH=CHCH3

CF2=CFCH=CHCH3

CF2=CFCH=CHCF3



CF2=CFCII=ClHC1L


CFl--CFCIL2C11BrCII

CF=:2CFUC]2CF=Ca

CF2=CFCH=CIICH3

CFa=CFCH2CHlBrCHl

CF2=CFCF2CF=CF2


Olefin 2

CF2=CFCH=CHCH3



CF2=CCl2

CF2=CFC1

CF2=CFCH=CHCF3



CF:=CFCHI=CIiCF,


CFalCFC1

CI: -Cl]"C- CI-CFa

CH2=CHCH=C1H2



CF2=CFC1


Time


Temp.


(Hrs) (OC) Product

16 100 CF2CFCH=CHCH3
(1)
CFaCFCH=CHCH3

20 160 (1)

20 160 (1)

20 100 CF2CFCH=CHCF3
(2)
CF2CFCH=CHCF3

20 105 (1), (2) plus

CF2CFCH-CHCH1

CF2CFCH=CHCF3


No cyclo-addition

No cyclo additLon

(1)

No cyclo-addition

No cyclo-addition


Yield
%7

100



100

100

100



30 (1)

45 (3)

20 (2)


I.R.
Figure

31



31

31

63



65


products formed

products formed

100 31

products formed

products formed


NMR
Figure

32



32

32

64


Mass
Spec.
Table

XVII



XVII

XVII

XXVI
N^


76 XXVII


32 XVII


1









0O
CF2=CFCH=ClCH3 ----> CF2-CF-CH=CHCH3
I I
(I) CF2-CF-CH=CHCH3


CF2=CFCH=CHCF3

(II)


---> CF2-CF-CH=CH-CF3

CFCF =CH-CF
CFa-CF-CH=CH-CF3


CF2=CFCH=CHCF3

(II)

+ -->

CF2=CFCH=CHCH3

(I)


CF2CFCH=CHCH3
I I
CF2CFCH=CHCH3

30%


CF2CFCH=CHCF3
+ I
CF2CFCH=CHCF3

20%


+

CF2CFCH=CHCH3
I I
CF2CFCH=CHCF3

45%


The mixed cyclobutane was observed along with the two expected

homocyclobutane products when a mixture of the 1,1,2-trifluoro-

pentadiene-1,3 and 1,l,2,5,5,5-hexafluoropentadiene-l,3 was

allowed to react.

The relative amounts of the cyclobutane products are almost a

statistical distribution suggesting the two dienes have the same

order of reactivity.

The attempted reaction of other olefins, CF2=CFC1, CF2=CCI2, and

CH2=CHCH=CH2 with the 1,1,2-trifluoro-dienes resulted in cyclo-

butane products containing only the 1,1,2-trifluoro-diene molecules.










CF2=CFCH=CHCH3 + CF2=CFCl -> CF2CFCH=CHCH,


I I
(I) CFCC1


--> CF2CFCHI-CHCH3

CF2CFCH=CHCH_



We conclude that the reactivity of the 1,1,2-trifluoro-dienes in

forming 2 + 2 cyclobutane products is much greater than fluorinated

olefins such as CF2=CFC1.

Fluorocarbon dienes react to give cyclobutane products both

intra and intermolecularly. The thermal reaction of perfluoro-

hexadiene-1,5 has been reported to give the intramolecular 2 + 2

cycloaddition product.37



CF2=CFCF2CF2CF=CF2 --> CF2CFCF2

CF2CFCF2



In general the reaction conditions for 2 + 2 cycloaddition

reactions are rather harsh, i.e, temperatures exceeding 2000C for the

cycloaddition reaction to predominate. The substituent effect is

noteworthy since ethers, CF2=CFOR, react more readily than vinyl

alkanes or perfluorinated olefins in the preparation of cyclobutane

products. The formation of a cyclobutane product from

CF2=CFCH=CHCH3 (I) at 0C was totally unexpected. Literature

accounts gave no indication of any olefins undergoing a 2 + 2










cycloaddition at such mild conditions. The stabilization of the

proposed biradical intermediate coupled with the conjugated

system is credited with this result.



CF2CFCHCHCH3 CF2CF=CHCHCH,
I <-->I .
CF2CFCH=CHCH3 CF2CFCH=CHCHs



product



In none of the reactions was any cyclohexene products isolated

thus indicating that no 2 + 4 Diels-Alder addition had occurred.

The conjugated fluorinated pentadiene systems react preferentially to

give 2 + 2 cycloaddition products.

The activation of the trifluorovinyl moiety by conjugation

of a hydrocarbon olefin is very evident in the 2 + 2 cycloaddition

reactions. Note should be taken of the decreased reactivity of

CF2=CFCH2CHBrCH3 as compared to that of both CF2=CFCH=CCHC3 and

CF2=CFCH=CHCF3. 1,4-Perfluoropentadiene, moreover, showed no

activity towards this type of reaction as none of the cyclobutane

product was found.



Radical Additions

A study was made of the reaction of the three dienes with

trifluoronitrosomethane (CF3NO), with bromine (Br2), and with bromo-

trichloromethane (CCl1Br) in the presence of benzoyl peroxide.









Trifluoronitrosomethane is reported to react with fluorinated

olefins by a radical anion mechanism.22 Both partially fluorinated

dienes, l,l,2-trifluoropentadiene-l,3 (I) and 1,1,2,5,5,5-

hexafluoropentadiene-1,3 (II) gave 2 + 4 Diels-Alder type products

with CFsNO as well as polymers in which 1,2 and 1,4 addition structures

were observed. The polymer was isolated and analyzed by

infrared analysis. The spectrum showed absorptions at 5.65p

and 5.82p, indicative of both 1,2 and 1,4 structures.



CFNO + CF2=CFCH=CR ----> CF2CF=CHCIR
\ I
N-- 0
I
CF3



+ NO-CF2CF=CHC
[CF3 R n

The 1,4 polymer structure

R = CH3, CF3


+ --NOCF2CF--
1 I
CFs CH n

CH

R

The 1,2 polymer structure










The Diels-Alder products obtained from the reaction of

trifluoronitrosomethane with I and II were not unexpected

since hexafluorobutadiene-1,3 gives the 2 + 4 cycloaddition

product from the reaction with trifluoronitrosomethane.13

Stabilization of the intermediate radical anion by resonance

would explain the 2 + 4 cycloaddition result.



CFsNO + CF2=CFCH=CHR --> CF2CF=CH.--.CHR
I
N--O

CF3
I


R = CHa, CF3

CF2CF=CHCHR
\ /
N-
I
CF3



The 1,4-perfluoropentadiene did not react with CF3NO either at

-780C or room temperature.

We consider halogen addition to be a radical process for

fluorine-containing dienes. Two of the three dienes do contain

hydrocarbon segments and we would expect addition to the hydrocarbon

segment if the halogen addition were an electrophilic process.

The actual product obtained was formed by addition to the CF2=CF

moiety. The process is described by the following sequence.










CF2=CFCH=CHR + Br --> BrCF2CFCH=CHR


BrCF2CFBrCU=CHR

R = CH, CF3 1,2 addition product



CF2=CFCH=CHR + Br2 -> BrCF2CF=CHCIR

I
BrCF2CF=CHCHBrR

1,4 addition product



The 1,l,2,5,5,5-hexafluoropentadiene-l,3 gave both addition

products with bromine while 1,1,2-trifluoropentadiene-l,3 gave only

the 1,2 addition product. If the addition had been electrophilic

in nature, the 1,l,2-trifluoropentadiene-l,3 would have been

expected to yield the 1,4-addition product. These results are in

accord with the findings of Rondarev et al.25 who report the addition

of iodine monochloride to CF2=CFCH=CHCF3, a fluorine-containing

1,3-pentadiene, gave the 1,4 addition product, while P. Brown et al.33

found halogen addition to 5,5,5-trifluoropentadiene-1,3 to give both

1,2 and 1,4 addition.



CF3CH=CHCH=CH2 + Br -> CF3CHBrCH=CHCH2Br 1,4 addition

CF3CH=CHCHBrCH2Br 1,2 addition



1,4-Perfluoropentadiene gave 1,2 bromine addition with no

tetrabromo addition product or cyclization products being formed.

Bromotrichloromethane was added to l,l,2-trifluoropentadiene-1,3










(I) and 1,1,2,5,5,5-hexafluoropentadiene-l,3 (II), using benzoyl

peroxide as the initiator. The 1,l,2-trifluoropentadiene-l,3 gave

the 1,2-addition product while the 1,1,2,5,5,5-hexafluoropentadiene-

1,3 gave higher telomers but none of the one to one adduct.



CC3lBr + CF2=CFCH=CHCH3 -> CC13CF2CFBrCE=CHCHt



CC13Br + CF2=CFCH=CHCF3 -> higher teloners



The resonance stabilization of the intermediate radical and

subsequent addition of another olefinic molecule has already been

noted above. The addition of CClaBr was also carried out with

CF2=CFCH2CHBrCH3 to give two diastereomers of CC13CF2CFBrCH2CHBrCH3.

A reaction was attempted between 2-iodoheptafluoropropane and 1,4-

perfluoropentadiene at 1500C for 36 hours. No addition product

formed and the starting materials were recovered.

Table VI gives the products from the reactions of CF3NO, CClBr,

and Br2 with the dienes.



Reactions with Nucleophiles

The reaction of nucleophiles with fluorine-containing olefins

is well documented in the literature. The study of nucleophilic

attack of dienes, however, has been limited to hexafluorobutadiene-

1,3. The addition of Grignard reagents to perfluorinated olefins

normally gives substitution products by a SN2' type of reaction.







TABLE VI

RADICAL ADDITION REACTIONS


Olefin

CF2=CFCII=CIICH3


CF2=CFCH2CHBrCH3



CF2=CFCI=CHCFS

CF=CCFCF2CF=CF2

CF2=CFCF2CF=CF2



CF2=CFCH=CHCHE




CF2=CFCH=CHCFs


Radical
Source

CClsBr


Cl3Br

CClsBr

CC3 Br

CFSCFICFS

CF5NO



CF3NO




CF3NO


Time
(hr1

4


Temp
(C)

70


Products

CF2CFCH=CHCHS

CF2CFCH=CHCH3


Mass
Yield I.R. NMR Spec.
(%) Fig. Fig. Table Initiator

60 (1) Benzoyl
Peroxiide


CC13CF2CFBrCH=HCHC (2) 40 (2) 60

16 160 Two diastereomers of 65 34

CC13CF2CFBrCH2CHBrCHs

20 80 No 1/1 adduct or polymers

36 155 No 1/1 products or polymers

48 0 No 1/1 adduct or polymers
48 -78

48 -78 CF2CF=CHCHCHC 50 (3) 57
N 0

CFs (3) + 1,2 and 1,4 polymers

24 -78 CF2CF=CHCHCF3 50 (4) 72
N 0 + 1, 2 and 30
CF30 (polymer)
CFs 1,4 polymers


XXV

XVIII Benzoyl
Peroxide


Benzoyl
Peroxide
Heat


48 XXI




74 XXIX









TABLE VI (Continued)


Olefin

CF2=CFCF2CF=CF2

CF2=CFCH=CHCH3

CF2=CFCH=CHCF3


Radical
Source

Br2

Br2

Br2


Time Temp
(hr) (OC) Products

1 50 CF2BrAFBrCF2CF=CF2

1 3 CF2BrCFBrCH=CHCHs

1 0 CF2BrCFBrCH=CHCH3
(25%)


Yield
(%).

76

95

96


I.R.
Fig.

38

45

70


NMR
Fig.

39

46

71


Mass
Spec.
Table



XV

XXVIII


and

CF2BrCF=CHCHBrCF3 (75%)









RMgX + CF2=CFR' --> RCF=CFR' + MgFX



Aromatic Grignard reagents give predominant products containing

conjugated double bonds.32


C6HsMgBr + CF2=CFCF2C1 --> C6HsCF=CFCF2Cl


C6HsCF2CF=CF2


8.6%


Alkyl Grignard reagents react with fluorohaloolefins to

give an alkene in which the more easily eliminated halogen anion

is displaced.


CF2C1
RMgX + CH2=C
CF2C1


R = alkyl


CFC1
--> RCH2C
CF2

I.


predominant product


CF2C1
RCH2Cx

CFC1


A good review of the reaction of Grignard reagents, both alkyl and

aryl, can be found in Chemistry of Organic Fluorine Compounds by

M. Hudlicky.18










Alkyl Grignard reagents undergo either addition-elimination

or alkyl addition by radical means. The alkyl addition reaction

was well documented by K. Okuhara14 for fluoroolefins.



RMgX + CF2=CC2 --> RCF2CCl2H + RCF=CCl2

R = alkyl predominant product



The alkyl addition product was found to be formed by a radical

process and not hydrolysis of the magnesium complex, RCF2CC12MgBr.

The reaction of phenylmagnesium bromide with each of the

dienes gave the expected addition-elimination reaction products.

The l,l,2,5,5,5-hexafluoropentadiene-l,3 (II) was characterized by

a good yield (68%) of both cis,trans and transtrans dienes.

F F
\ /
CF2=CFCH=CHCF3 + C6HMgBr -> C =-C H
C6H, C=C
/ \
H CF3


cis,trans


H CF,
\ /CF
F C-=C
\ / \
and C=:C H
C6Hs F

trans,trans



When the reaction was run at -30C and quenched with D20 instead

of water, the only product isolated was the substituted










derived diene. This result suggests a concerted reaction since

no deuterium was incorporated into the product.

The product contained only the diene conjugated with the

benzene ring. Since the nonconjugated product was a possibility,

the stabilization of the conjugated product was the predominated

factor in determining the course of the reaction.



C6,HMgBr + CF2=CFCH=CHCF3 -- > Cs6HCF=CFCH=CHCF3



C6HsCF2CF=CHCH=CF2



The proposed mechanism for nucleophilic addition can be shown

as follows.



P + CF2=CFCH=CHR' > RCF2C H=CHR' 2, 3

RCF2CF=CHCA '

R' = CH, CF3

R = CH3CH2CP, C6H,



1. RCF=CFCH=CHR' addition-elimination or substitution

2. RCF3CFHCH=CHR' 1,2-addition

3. RCF2CF=CHCH2R' 1,4-addition










Table VII show the nucleophilic reactions with the fluorinated

1,1,2-trifluoro-diene systems. The addition of ethanolic potassium

hydroxide to 1,1,2-trifluoropentadiene-l,3 and 1,1,2,5,5,5-hexa-

fluoropentadiene-1,3 gave both 1,2 and 1,4 addition products for

the trifluoropentadiene system and only 1,4 addition product for the

more fluorinated hexafluoropentadiene system.



CF2=CFCH=CHCH3 + CH3CH20H ----> CH3CH20CF2CCFHCH=CHCH

1,2 addition product

and

CH3CH2OCF2CF=CHCH2CHH

1,4 addition product



KOH
CF2=CFCH=CHCF3 + CH3CH2OH > CH3CH2OCF2CF=CHCH2CF3

1,4 addition product only



The stabilization of the proposed anion intermediate by the

CF3 moiety of l,1,2,5,5,5-hexafluoropentadiene-l,3 (II) as compared

to the CH3 group of l,l,2-trifluoropentadiene-l,3 (I) would

explain the predominance of the 1,4 addition product in the more

fluorinated system. Each adduct was unstable in moist air and

hydrolyzed to an acid fluoride.

Since the nucleophilic attack of ethanolic potassium hydroxide

on l,l,2,5,5,5-hexafluoropentadiene-1,3 gave only the 1,4-addition









TABLE VII

NUCLEOPHILIC REACTIONS


Time T
Nucleophiles Olefin (Hrs)



CH3CH2P/CH3CH2OH CF2=CFCH=CHCH3 1


CLIIC1120 c /C. 11 C





C,1,Q MgrB


CF2 =CFCI 1= CUCFq


CF2=CFC11=C1tCll


CF2 CFCH1=CIIC V


emp.
(C)


Yield


Product


35 CHSCH20CF2CFHCH=CHCH3 65
(80%)

CHsCH20CF2CF=CHCH2CHs
(20%)

56 C11iC1120CF2CF=CllCll2CFF 67


37 C6llCF=CFCII=CllCll 15


50 Both Cis and Trans
Isomers 68
C6HsCF=CFCH=CHCF3


Ld I.R. NMR
Figure Figure



42 43


77 78










product, the possibility of an attack of the first carbon followed

by elimination of fluoride at the five carbon was possible.


O
CH3CH20a + CF2=CFCH=CHCF3 -- > CH3CH2OCF2CF=CCHCHCF





CHsCH20CF2CF=CHCHHCF3 CH3CH2OCF2CF=CHCH=CF2



None of this diene was detected. The low reactivity of

l,1,2-trifluoropentadiene-l,3 toward aryl Grignard reagents

could not readily be explained since nucleophilic attack of ethoxide

gave essentially the same yield as the more fluorinated pentadiene,

1,1,2,5,5,5-hexafluoropentadiene-l,3.

Several miscellaneous reactions were carried out on products

as well as on the pentadienes. The cyclic dimer of CF2=CFCH=CHCH3

was treated with ozone in methylene chloride until no starting

olefin remained.



CF2CFCH=CHCH3
I + Ozone -- > Ozonide
CF2CFCH=CHCH3


The viscous product showed reactivity with potassium iodide

indicating the presence of the ozonide. An attempt to decompose

the ozonide gave polymeric tars.










Since Knunyants et al.20 found reaction of diethyl amine with

hexafluorobutadiene-1,3 to give the addition product, the reaction

with l,l,2-trifluoropentadiene-l,3 was expected to give the addition

product.



(CH3CH2)2NH + CF2=CFCF=CF2 -> (CH3CH2)2NCF2CFHCF=2

H20

0
II
(CHaCH2)2NCCFHCF=CF2



Hydrolysis gave the N,N-diethylamide as shown. The attempted

reaction of diethylamine with the l,l,2-trifluoropentadiene-l,3

gave no adduct after 48 hours. The 2 + 2 cyclodimer was the only

isolated product.

No reaction was observed after six hours when 1,1,2,5,5,5-

hexafluoropentadiene-1,3 was treated with 20% sulfuric acid. The

electrophilic addition to the hydrocarbon segment of the diene

was expected.



HSO4 + CF2=CFCH=CHCF3 --> CF2=CFCH2CHCF3 or CF=CFCHCH2CF3
OH OH



Apparently, both the CF2=CF and CFs groups destabilize the carbonium

ion which would be formed in the first step of the reaction.










One of the intermediate olefins, CF2=CFCH2CHBrCH3, was treated

with magnesium in diethyl ether to give a 10% yield of the desired

coupled product along with polymeric material. The proposed scheme is

as follows.



MgBr

CFa=CFCH2CHBrCH3 + Mg iethyl > CF2=CFCHI2CP CH
ether

+

CF2=CFCH2CHBrCH3

CFa=CFCH2CHCH3 C
CF2=CECU2CHCH3 I
(-)-----
CF=CFCH2CHCHs CF2=CFCH2CHCH3
n I
CF2=CFCH2CHCH3
CF=CFCH2CHBrCH3



The polymer was not characterized fully since the yield

was low and most of the recovered material was tar.



Conclusions

The activation of the trifluorovinyl segment of the 1,1,2-

trifluoropentadiene-1,3 (I) by the hydrocarbon unsaturated segment

was immediately evident in the 2 + 2 cycloaddition reaction. There

has been no previous report of a cyclobutane formed at 0C from a

fluorinated olefin or diene. The 1,l,2-trifluoropentadiene-1,3

was so reactive that no other 2 + 2 cycloaddition products were

formed with a variety of olefins, both fluorocarbon and hydrocarbon.

Radical reactions such as bromine addition and bromotrichloromethane










addition gave the 1,2 addition product, while the trifluoronitroso-

methane gave the 2 + 4 Diels-Alder adduct along with polymer

containing 1,2 and 1,4 addition structure.

Nucleophilic additions to 1,1,2-trifluoropentadiene-1,3

gave the expected results for aryl Grignard reagents and both 1,2

and 1,4 addition for the reaction with ethoxide.

Reactions with the l,l,2,5,5,5-hexafluoropentadiene-l,3 (II)

also show the reactivity of the mixed trifluorovinyl, hydrocarbon

olefin combination. This diene readily formed the expected

cyclobutane derivative. A mixed cyclobutane was found when 1,1,2-

trifluoropentadiene-1,3 was treated with (II). Bromine added 1,2 and

1,4 to give the corresponding alkenes in 25% and 75% yields,

respectively. The reaction of bromotrichloromethane gave only

polymers with l,l,2,5,5,5-hexafluoropentadiene-l,3. Trifluoronitroso-

methane again gave the 2 + 4 Diels-Alder adduct with (II) along with

polymers with 1,2 and 1,4 structures. The expected elimination or

substitution reaction from aryl Grignard reagents was realized in

68% yield, giving both the cis,trans and trans,trans products.

Ethanol addition gave only the 1,4 addition product in 67% yield.

The 1,4-perfluoropentadiene was found to be unreactive compared

to (I) and (II). No 2 + 2 cycloaddition products were formed and no

products from radical reactions were isolated except for the 1,2

addition product with bromine. None of the tetrabromo addition

product or cyclized product was formed. Trifluoronitrosomethane

gave no adducts at -780C and at ambient temperature.






46


Tables VIII, IX and X give the reactions, products, and

yields for each system, l,1,2-trifluoropentadiene-l,3; 1,1,2,5,5,5-

hexafluoropentadiene-1,3; and 1,4-perfluoropentadiene.










TABLE VIII

REACTIONS OF THE 1,1,2-TRIFLUOROPENTADIENE-1,3


Reaction Type Reactant

2 + 2 Cycloaddition CF2=CFCl


2 + 2 Cycloaddition



2 + 2 Cycloaddition



2 + 2 Cycloaddition



2 + 2 Cycloaddition

Radical


Time
(hr)

20


Temp
(C)

160


Products

CF2CFCH=CHCH3
I I
CF2CFCH=CHCH3


Yield


100


CF2=CC12 16 160 CF2CFCH=CHCHs 100
I I
CF2CFCH=CHCH3

CF2=CFCH=CICH3 16 100 CF2CFCH=CHCHs 100
I I
CF2CFCH-CHCH3

CF2=CFCII=CIICF 20 105 CF2CFCH=CHCHI 45
I I
CF2CFCII=CIICF3

Cl2"=CIHCI1=CH2 4 120 None of the hydrocarbon product

CClsBr 4 70 CClsCF2CFBrCH=CHCHS 40

+ 2+2 Cycloaddition product 60


Comments

No adduct formed
between CTFE and
1,1,2-trifluoro-
pentadiene-1,3


The yield of homo-
dimers (cyclic)
was 55%

No reaction

Only the 1,2
addition product







TABLE VIII (Continued)


Radical


CFNO


Radical


Nucleophilic



Nucleophilic


CHsCH2aMr



C6HMgBr


48 -78 2+4 Diels-Alder Product
polymer 1,2 and 1,4



30 3 CF2BrCFBrCH=CHCH3


1 35 CHsCH20CF2CFHCH=CHCHs (80%)

CH3CH20CF2CF=CHCH2CHs (20%)

5 37 C6HsCF=CF=CHCH3


50 CF2CF=CHCHCH3
50 \ /
N- 0
CFs + polymers

95 Only the 1,2
addition product

65 Both 1,2 and 1,4
addition products
formed

15 Slow reaction,
lower yield.








TABLE IX

REACTIONS OF THE 1,1,2,5,5,5-HEXAFLUOROPENTADIENE-1,3


Reaction Type

2 + 2 Cycloaddition



2 + 2 Cycloaddition


Radical

Radical


Reactant

CF2=CFCH=CHCF3



CFz=CFCH=CHCH3


Time Temp.


2
2


CClsBr

CF3NO


Radical


Nucleophilic


Nucleophilic


CH3CH2ad


C6HsMgBr


[r) (C) Product

0 100 CF2CFCH=CHCF
I
CF2CFCH=CHCF3

t0 105 CF2CFCH=CHCHs
I I
CF2CFCH=CHCF3

20 80 Polymers

!4 -78 2 + 4 Diels-Alder
adduct and both
1,2 and 1,4 polymer


1 0 CF2BrCFBrCH=CHCF3 (25%)

CF2BrCF=CHCHBrCF3 (75%)

1 56 CH3CH20CF2CF=CHCH2CH3


1 50 C6H3CF=CFCH=CHCF3


Yield
(%1

10O


Comments

Quantitative yield
of the cyclobutane
dimer


45



No 1/1 adduct

50 CF2CF=CHCHCFs
N--0
/
CFs + polymers

Both 1,2 and 1,4
adducts formed
96

67 Only the 1,4
adduct formed

68 Both cis,trans and
trans,trans isomers
formed


Y












REACTIONS OF THE


Reaction Type



Cycloaddition

Cycloaddition

Radical

Radical


TABLE X

PERFLUOROPENTADIENE-1,4


Time Temp.
Reactants (hr) (C)


CF2=CFCF2CF=CF2

CF2=CFC1

CFsCFICF3

CFsNO


Products


No cycloaddition product

No cycloaddition product

No radical addition

No radical addition


50 CF2BrCFBrCF2CF=CF2


Yield
(%


Radical
















SECTION 3

EXPERIMENTAL



The analytical work on the compounds prepared was carried out

as follows: Gas-liquid chromatography (GLC) was accomplished on a

Hewlett Packard 5710A gas chromatograph equipped with a thermal

conductivity detector. A 20-foot QF-l column with a 10% loading

on acid washed Chromosorb W was the column of choice. A methyl

trifluoropropyl silicone oil (QF-1) proved adequate for separation of

the fluorine-containing products. Infrared analyses were performed

using a liquid smear of sample between sodium chloride crystals. A

Perkin Elmer 727B instrument was employed. Nuclear magnetic resonance

(NMR), both proton H1 and fluorine F19, were performed by Dr. Wallace

Brey using a Varian XL-100 spectrometer with external standard. Mass

spectral data were compiled on an AEI-MS-30 mass spectrometer with a

DS-30 data system with the assistance of Dr. Roy King and Ms. Jackie

Dugan. Any deviation, such as column change for GLC analysis, etc.,

will be presented in the experimental for specific reactions. All

temperatures are reported in degrees centigrade (C) with boiling

points being as observed and uncorrected.










Preparation of Precursors



Addition of 1,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFClBr) to
Propene (CH2=CHCH3)

The attempted reaction was carried out in a five-liter, three-

necked flask equipped with a gas inlet, a condenser, a thermowell,

and backed by a Dry-Ice acetone trap. The 1,2-dibromo-2-chlorotri-

fluoroethane (CTFE dibromide, 1,385 grams, 5 moles) was added and

stirred under a dry nitrogen sweep for two hours while the material

was heated to reflux. Benzoyl peroxide (10 grams) was added and the

propene (CH2=CHCH3) addition was begun. After one hour, an additional

five grams of benzoyl peroxide was added and, subsequently, five grams

every hour for three additional hours. At the end of four hours, a

sample revealed no addition product had formed even though there had

been added 170 grams (4 moles) of propene. The reaction was terminated

and the starting materials recovered (Figure 1).

A three-liter autoclave was cleaned, equipped with a 5,000 psi

rupture disc and pressure checked with dry nitrogen. The autoclave

was evacuated and cooled in liquid oxygen before a mixture of CTFE

dibromide (CF2BrCFClBr, 1,385 grams, 5 moles) and benzoyl peroxide

(20 grams) was added. The propene (CH2=CHCH3, 210 grams, 5 moles)

was condensed into the autoclave through a vacuum manifold. After

the system was warmed to ambient temperature, the autoclave was

placed in a heater/rocker and heated to 1500C with rocking for 16

hours. The autoclave was cooled to room temperature and the overgases

collected. The remaining liquid (1,505 grams) was distilled to give

880 grams of starting CF2BrCFClBr along with 485 grams of material










which had a boiling point of 176-1810C (83% yield). A GLC analysis

on an SE-30 nickel column showed two components which did not give a

base line separation. Further separation was carried out on a

40-plate Oldershaw column to give the two fractions in greater

than 90% purity. Nuclear magnetic resonance analysis confirmed
*
the structure to be two diastereomers of CF2BrCFClCH2CHBrCH3

(Figures 2 6). Figure 2 lower boiling diastereomer. IR

(liquid) maxima in microns 3.34 (C-H), 8.1, 8.18, 8.32, 8.95 (C-F),

9.6, 10.0, 10.4, 12.55. Figure 3 higher boiling diastereomer.

IR (liquid) maxima in microns 3.3 (C-H), 8.1, 8.15, 8.33 (C-F), 9.5,

12.5, 12.7. Figure 4 F19 NMR, two fluorines, doublet for CF2Br;

one fluorine, multiple for CFC1; mass spectrum m/e 320 (M ), 239,

237 (M-Br), 203, 201 (M-Br and Cl), 159, 157 (M-2Br), 121 (M-C2F3,CBr).

High resolution mass spectrum, CsF3Br2ClH6, calculated mass 315.84,

measured 315.85.

The three-liter autoclave reaction was repeated to obtain an

additional 472 grams (80% yield) of material, CF2BrCFCCH2CHBrCH3,

for further reactions.

A three-liter autoclave reaction was repeated using propene

(210 grams, 5 moles), 1,2-dibromo-2-chlorotrifluoroethane (2,806 grams,

10.2 moles) and benzoyl peroxide (30 grams). The reaction was carried

out at 150C for 24 hours and was worked up as the previous reactions.

The liquid products were distilled to give 661 grams of the two

diastereomers in 80% yield based on consumed propene.










Attempted Reaction of l,2-Dibromo-2-chlorotrifluoroethane
(CF2BrCFClBr) with 1,3-Butadiene (CH2=CHCH=CH2)

A three-liter autoclave was cleaned and equipped with a 5,000 psi

rupture disc before being pressure checked with 600 psi of dry nitrogen.

After venting the nitrogen, a full vacuum was applied and the autoclave

was cooled to -196C with liquid oxygen. Benzoyl peroxide (15 grams)

was dissolved in the 1,2-dibromo-2-chloro-trifluoroethane (1,040 grams)

and sucked into the evacuated autoclave. The 1,3-butadiene (135 grams)

was vacuum transferred into the autoclave and the system was heated to

120C for 16 hours. After the autoclave was cooled to ambient

temperature, the overgases were collected (120 grams). Distillation

gave recovered 1,2-dibromo-2-chlorotrifluoroethane (996 grams) and

-30 grams of higher molecular weight oil. The simple adduct (1 to 1)

was not present.



Addition of l,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFC1Br) to
Trifluoropropene (CF3CH=CH2)

A three-liter autoclave was equipped with a 5,000 psi rupture disc

and pressure checked to 700 psi with dry nitrogen. The nitrogen was

vented and a full vacuum applied to the system before the autoclave

was cooled to -196C with liquid oxygen. The 1,2-dibromo-2-chloro-

trifluoroethane (1,108 grams) in which benzoyl peroxide (15 grams)

was dissolved was then sucked into the evacuated autoclave. Trifluoro-

propene (266 grams) was condensed into the system before the autoclave

was heated to 120C and rocked for 20 hours. After the system was

cooled to room temperature, the overgases were collected (101 grams)

and the liquid products poured into a distillation flask. The









1,2-dibromo-2-chlorotrifluoroethane was recovered (960 grams) leaving

280 grams of higher boiling material. Distillation gave 105 grams of

material with a boiling point less than 180C which by GLC analysis

was a composite of four peaks. The higher boiling fraction (90 grams,

bp 56-59/0.1 mm) was found to be two sets of diastereoners of

CF2BrCFClCH2CH(CF3)CH2CHBrCF3 (25% yield, Figures 7 10). Figure

7 IR (liquid) maxima in microns 3.35 (C-H), 8.0, 8.4, 8.75, 8.95

(C-F), 9.6, 13.0. Figure 8 H1 NfR multiplets for CH3r, CH2, CH,

CH2. Figure 9 F19 NMR, Figure 10 F19 NMR, Table XII Mass

spectrum m/e 445 (Mi), 369, 367 (M-Br), 287 (M-2Br), 273, 271,

(M-CzF3ClBr), 259, 257 (M-C3F3ClBrH2).

The reaction was repeated using a higher ratio of 1,2-dibromo-

2-chlorotrifluoroethane to trifluoropropene with essentially the

same results. There was no evidence of the presence of the 1 to 1

addition product but .25% of the 1,2-dibromo-2-chlorotrifluoroethane

had added to two molecules of trifluoropropene to give

CF2BrCFClCH2CH(CF3)CCHCHBrCF (92 grams).



Addition of 1,2-Dichloro-2-iodotrifluoroethane (CF2C1-CFC1I) to
Trifluoropropene (CH2=CHCF3)

A three-liter autoclave was equipped with a 3,000 psi rupture

disc and pressure checked at 800 psi with dry nitrogen before being

evacuated to full vacuum. The autoclave was cooled in liquid oxygen

before the 1,2-dichloro-2-iodotrifluoroethane (1,000 grams, 3.58 moles)

and benzoyl peroxide (11 grams) was sucked into the evacuated

system. The trifluoropropene (170 grams, 1.77 moles) was condensed

in via a glass vacuum system. The mixture was heated at 100C for










four hours before being cooled to ambient temperature. Work-up

showed that no reaction had occurred.

The three-liter autoclave reaction was repeated and the reactants

heated to 150C with rocking for four hours. After being cooled to

room temperature and the volatiles collected, the liquid products

were distilled to give CF2ClCFC1I (685 grams, 2.16 moles), and the
*
desired CF2CICFClCH2CHICF3 (315 grams, .84 moles, bp 161-1660C) in

75% yield. The large boiling range is due to the presence of two sets

of diastereomers. (Figures 51 54). Figure 51 both diastereomers.

IR (liquid) maxima in microns 3.30 (C-H), 7.6, 7.8, 8.05, 8.15, 8.45,

8.8 (C-F), 9.2, 10.0. Figure 52 F19 N R, three fluorines,

doublet CF3; two fluorines, CF2C1 triplet; one fluorine, multiple

for CFCl; Figure 53 and C H1 NMR, complicated multiple for both

CH2 and CHI, Table XXII mass spectrum n/e 376, 374 (M+), 291, 289

(M-CF2Cl), 349, 247 (M-I), 213, 211 (M-I and Cl).

The reaction was repeated in a three-liter autoclave using the

recovered CF2ClCFClI (685 grams, 2.16 moles) and trifluoropropene

(170 grams, 1.77 moles) to give an additional 310 grams of

CF2ClCFC1CH2CHICF3 in 80% distilled yield.



Preparation of l-Bromo-2-iodotetrafluoroethane (CF2BrCF2I)

A three-liter autoclave was used to prepare the l-bromo-2-iodo-

tetrafluoroethane. After being pressure and vacuum checked and cooled

to -196'C, the autoclave was charged with bromine (480 grams) and

iodine (790 grams), and the tetrafluoroethylene was condensed in

(1,100 grams). The reaction mixture was heated to 2000C for 20 hours










with rocking before being cooled to ambient temperature. The over-

gases were vented and the liquid products distilled to give 1,2-dibromo-

tetrafluoroethane (210 grams), l-bromo-2-iodotetrafluoroethane (610

grams, bp 79-80"C, 23% distilled yield), 1,2-diiodotetrafluoroethane

(360 grams) and 560 grams of a residue which contained higher telomers

(Figure 11).



Addition of l-Bromo-2-iodotetrafluoroethane (CF2BrCFI2) to Ethylene

A three-liter autoclave was equipped as in previous reactions,

evacuated and cooled to -196C before the benzoyl peroxide (15 grams)

and l-bromo-2-iodotetrafluoroethane (610 grams) were added. Ethylene

(120 grams) was condensed into the autoclave and the system was warmed

to 120C for 16 hours with rocking. After cooling, the autoclave was

vented and the liquid products distilled to give l-bromo-2-iodotetra-

fluoroethane (151 grams), l-bromo-4-iodo-l,l,2,2-tetrafluorobutane

(286 grams, bp 160-161C, 58% distilled yield), and 210 grams of

higher boiling material (Figure 12).



Preparation of Olefins



Attempted Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with 50% Aqueous
Sodium Hydroxide

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

a reflux condenser, a thermometer, and a dropping funnel. Aqueous

sodium hydroxide (NaOH, 320 grams of 50%) was added to the flask and
*
stirred as the mixture was heated to 80'C. The CF2BrCFClCH2CHBrCH3

(169 grams, 0.53 moles) was added via the dropping funnel over a one-










hour period. The organic material immediately formed a lower layer

and did not react with the caustic solution.


*
Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with Potassium t-Butoxide
and Dimethyl Sulfoxide

A 500-ml, three-necked flask was equipped with a mechanical

stirrer, a condenser backed by a liquid oxygen cooled trap, a thermo-

meter, and a dropping funnel. The potassium-t-butoxide (41 grams,

0.37 moles) and dimethyl sulfoxide (200 ml) were added to the flask

and the mixture stirred. The fluorocarbon, CF2BrCFClCH2CHBrCH.

(95 grams, 0.3 moles) was added dropwise via the dropping funnel and

the mixture was heated to I130C before a reflux was noted. The

condenser was replaced with a distillation head and 65 grams of

material was collected. Redistillation gave 52 grams of

CFBrCFClCH=CHCH3 (bp 133-134C, 73% yield, Figures 13 15). Figure

13 IR (liquid) maxima in microns 3.36 (C-H), 6.0 (C=C), 8.25, 8.3,

8.8, (C-F) 9.9, 10.4, 10.7, 11.2, 12.5, 14.0. Figure 14 H1 N R.

Two types of vinyl protons, two hydrogens; and a doublet, three

hydrogens, for CH3. Figure 15 F19 NMR. Table XIII mass spectrum

m/e 238 (M ), 159, 157 (M-Br), 203, 201, (M-C1), 107 (M-Br, Cl and

CH3). High resolution mass spectrum, CsF3HsClBr, calculated mass

236.09, measured 235.92.



Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with Ethanolic Potassium
Hydroxide

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a condenser. Ethanol (250 ml) and

potassium hydroxide (65 grams) were stirred until the base had gone










into solution. The CF2BrCFCICHBrCH3 (320 grams, 0.95 moles) was

added dropwise and an exotherm to 600C was noted over a two-hour

period. After being stirred for an additional three hours, the

material was washed twice with one liter of ice water to give 230

grams of product. After the mixture was dried over molecular sieves,

distillation gave 217 grams of CF2BrCFCICCH=CHCH (88% yield, bp

133-134C).
*
The dehydrohalogenation of CF2BrCFCICHCBrCH3 (329 grams, 1.03

moles) was repeated using potassium hydroxide (63 grams, 1.1 moles)

in ethanol (600 ml). Distillation of the product gave

CF2BrCFClCH=CHCHa (bp 131-132'C, 181 grams, 74% yield).



Dehydrohalogenation of CFBrCF2CH2CH2I with Ethanolic Potassium
Hydroxide

The attempted reaction of CF2BrCF2CH2CHI with aqueous sodium

hydroxide gave only recovered starting material but alcoholic

potassium hydroxide gave the desired olefin. A 250-ml, three-

necked flask was equipped with a magnetic stirrer, dropping funnel,

thermowell, and a condenser before being charged with ethanol (150 ml)

and potassium hydroxide (10 grams). The CF2BrCFCH2CH2I (61 grams,

0.19 moles) was added dropwise over a two-hour period. After the

material was washed with 500 ml of ice water, the organic layer was

collected and dried over molecular sieves. Distillation of the

crude product (36 grams) gave 28 grams of 99+% pure CF2BrCF2CH=CH2

(80% distilled yield, bp 64C, Figures 16 18).










Dehydrohalogenation of CF2BrCFClCH2CH(CF3)CH2CHBrCF, with Ethanolic
Potassium Hydroxide

The dehydrohalogenation of CF2BrCFCICH2CH(CF3)CH2CHBrCF3 with

ethanolic potassium hydroxide was attempted in a 250-mi, three-necked

flask equipped with a magnetic stirrer, dropping funnel, thermometer,

and condenser. The potassium hydroxide (18 grams, 0.32 moles) and

ethanol (200 ml) were placed in the flask and stirred for 30 minutes.

The CF2BrCFCICH2CH(CF3)CH2CHBrCF3 (100 grams, 0.22 moles) was added

over a one-hour period and stirred for an additional two hours. After

the material-was washed with ice water (500 ml), the organic layer was

collected and dried over molecular sieves. The product was the

starting material which was recovered in 85% yield.



Dehydrohalogenation of CF2CICFC1CH2CHICF3 with Ethanolic Potassium
Hydroxide

A one-liter, three-necked flask was equipped with a magnetic

stirrer, dropping funnel, distillation head and thermowell. The

potassium hydroxide (76 grams, 1.25 moles), water (225 ml), and

ethanol (300 ml) were placed in the flask and stirred as the mixture

was heated to 700C. The CF3C1CFClCH2CHiCF3 (300 grams, 0.8 moles)

was added slowly via the dropping funnel as the mixture was heated

to 80C with material distilling front the reaction mixture. The

product, CF2CICFCICH=CHCF3 (131 grams, bp 880C), was washed with water

and dried over molecular sieves. Distillation gave a 70% yield

(Figures 55 58). Figure 55 IR (liquid) maxima in microns 3.18

(C-H), 5.88 (C=C), 7.61, 7.8, 8.2, 8.6 (C-F), 9.3, 9.5, 10.3, 11.0,

11.5, 12.6. Figure 56 F19 NMR, three fluorines, doublet for CF3;










two fluorines, double for CF2C1; one fluorine, multiple for CFC1.

Table XXIII mass spectrum m/e 246 (M1), 211 (M-C1), 163, 161

(M-CF2C1).
*
The reaction was repeated using CF2ClCFClCH2CHICF3 (280 grams,

0.75 moles). The product was collected in 60% yield after being
0
separated from the ethanol and dried over 4A molecular sieves.



Decarboxylation of CF2ClCFBrCF2CFBrCF2COONa

A one-liter, three-necked flask was equipped with a mechanical

stirrer, thermometer, and a distillation head. The CF2ClCFBrCF2CFBr-

CF2COONa (400 grams, 0.84 moles) was placed in the flask along with

diglyme (500 ml) and the mixture was heated to 90C slowly with the

evolution of CO2. The mixture was then heated to a flask temperature

of 1450C while the product distilled from the flask. The collected

material contained the CF2ClCFBrCF2CF=CF2 along with diglyme. The

diglyme was washed from the mixture with ice water to give 190 grans

of 98+% pure CF2ClCFBrCF2CF=CF2 (bp 104-106C, Figure 19). Figure 19 -

IR (liquid) maxima in microns 5.6 (CF2=CF), 7.4, 7.7, 8.7, 9.0 (GF),

9.6, 10.2, 11.0, 11.2, 11.6, 123, 12.7, 13.5.



The Dehalogenation of CF2BrCFClCH=CHCH3 with Zinc

A one-liter, three-necked flask was equipped with a mechanical

stirrer, a dropping funnel, a thermometer, and a Vigreux column with

a distillation head. The zinc (65 grams, 1.01 moles) and ethanol

(250 ml) were placed in the flask and stirred while being heated to

65C. The CF2BrCFC1CH=CHCH3 (210 grams, 0.88 moles) was added drop-

wise via the dropping funnel over a one-hour period with the product










distilling out as it was formed. The product, CF2=CFCH=CHCH3, was

collected (85 grams, 97% pure, bp 44-45C, 78% yield, Figures 20 23).

Figure 20 IR (liquid) maxima in microns 3.4 (C-H), 5.6 (CF2=CF), 6.05

(CH=CH), 7.8, 7.95, 8.5, 9.0 (C-F), 9.5, 10.5. Figure 22 H1 NKR,

three hydrogens, doublet (CH3); two hydrogens, multiple (CH=CH).

Figure 23 F19 NMR, three fluorines, four sets of multiplets. Table

XIV mass spectrum m/e 122 (M+), 121 ('-H), 103, (M-F), 102 (M-HF),

109 (M-H2F), 72 (M-CFa). High resolution mass spectrum, CsF3H5,

calculated mass 122.09, measured 122.03.

The reaction was repeated using CF2BrCFClCH=CHCH3 (40 grams),

zinc (40 grams), and ethanol (150 ml). The product was collected,

washed with ice water, dried over molecular sieves and distilled to

give 19 grams of CF2=CFCH=CHCHs (bp 44-45C, 92% yield).

The preparation of CF2=CFCH=CHCH3 was repeated using

CF2BrCFClCH=CHCH3 (145 grams, 0.61 moles), zinc (46 grams, 0.69 moles)

and ethanol (150 ml). The product which distilled from the reaction

mixture, washed twice with ice water and dried over molecular sieves

gave CF2=CFCH=CHCH3 (69 grams, 92% yield, bp 44-45C).



Dehalogenation of CF2BrCFClCH2CHBrCH3 with Zinc

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a Vigreux column with a distillation

head. The zinc (76 grams, 1.19 moles) and ethanol (250 ml) were placed

in the flask and heated to 45'C with stirring before the fluorocarbon

was added dropwise. An exothermic reaction ensued and the temperature

rose to 800C. After being stirred for one and one-half hours, the









liquid was decanted into one-liter of water and the organic layer was

separated and dried. Distillation gave CF2=CFCH2CHBrCHM (67 grams,

bp 110-111C, 91% yield, Figures 24 26). Figure 24 IR (liquid)

maxima in microns 3.38, 3.45 (C-H), 5.61 (CF2=CF), 7.8, 8.0, 8.2,

8.6 (C-F), 9.0, 9.4, 9.6, 9.8, 10.2. Figure 25 F19 XR2, three

fluorines, three sets of multiplets for CF2=CF, Figure 26 H1

NMR, three hydrogen, doublet for CH3; two hydrogen, two sets of

multiplets for CH2; one hydrogen, sextet for CHBr. Table XV mass

spectrum m/e 204, 202 (M ) 123 (M-Br), 109, 107 (M-C3F7H2), 103

(M-H, F, Br); 95 (M-C2H7Br). High resolution mass spectrum,

CsFH6Br, calculated mass 202.10, measured 201.96.



Dehalogenation of CF2BrCFClCH2CH(C)CHCrC3 with Zinc

A 250-mi, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a distillation head. The ethanol

(150 ml) and zinc (20 grams, 0.31 moles) were added to the flask and

stirred as a few drops of bromine were added to activate the zinc.

The mixture was heated to 50C before the CF2BrCFClCH2CH(CF3)CH2CHBrCF3

(31 grams, 0.066 moles) was added via the dropping funnel. An exotherm

was immediately noted and distillation gave ethanol and fluorocarbon

product. After being washed with ice water to remove the ethanol,

the organic layer was separated, dried over molecular sieves and

distilled to give CF2=CFCH2CH(CF3)CH2CH=CF2 (bp 134-1380C, 95% yield,

16 grams, Figures 27 and 28). Figure 27 IR (liquid) maxima in

microns 3.38 (C-H), 5.55 (CF2=CF), 5.7 (CF2=CH), 7.7, 8.0, 8.4,

8.5, 9.0 (C-F). Figure 28 F19 NMR, three fluorines, singlet CF3;

two fluorines, multiple (CF2=CH); three fluorines, multiple (CF,=CF).









Dehalogenation of CF2ClCFBrCF2=CFCF with Zinc

A one-liter, three-necked flask was equipped with a magnetic

stirrer, Vigreux column, thermometer, and dropping funnel. A distil-

lation head backed by a liquid oxygen trap was used to collect the

product. The zinc (60 grams, 0.94 moles), ethanol (500 ml), and

bromine (3 ml) were added to the flask and stirred as the mixture was

heated to 50C. The CF2ClCFBrCF2CF=CF2 (190 grams, 0.58 moles) was

added dropwise via the dropping funnel as the product was collected in

the distillation head. After the product was washed with ice water,

the organic material was dried over molecular sieves and distilled to

give CF2=CFCF2CF=CF2 (92 grams, 75% yield, bp 36-38'C, Figures 29 30).

Figure 29 IR (liquid) maxima in microns 5.6 (CF2=CF), 7.4, 7.6,

7.8, 8.35, 8.42, (C-F), 9.7, 10.8, 11.2. Figure 30 F19 NMR, eight

fluorines, six sets of multiplets for the (CF2=CF)2CFz. Table XVI -

mass spectrum m/e 212 (M+), 162 (M-CF2), 143 (M-CF3), 131 (M-C2F,),

93, (M-C2Fs). High resolution mass spectrum, CsFa, calculated mass

212.04, measured 211.99.



Dehalogenation of CF2ClCFCICH=CHCF3 with Zinc

A 250-mi, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, distillation head, and a thermometer. The zinc (40

grams) and ethanol (150 ml) were placed in the flask and stirred as

bromine (1 ml) was added to activate the zinc. The mixture was heated

to 65'C before the olefin CF2C1CFCICH=CHCF3 (90 grams, 0.36 moles) was

added dropwise. The product immediately distilled from the reaction

mixture and, after the material was washed with ice water and dried










over molecular sieves, the CF2=CFCH=CHCF3 (59 grams, bp 43-44C, 92%

yield) was distilled. (Figures 57 59). Figure 57 IR (liquid)

maxima in microns 3.35 (C-H), 5.7 (CF,=CF), 5.95 (CH=CH), 7.58, 7.7,

7.8, 8.7 (C-F), 10.3, 12.0. Figure 58 F19 NMR, three fluorines,

singlet for CF3, three fluorines, three sets of multiplets for (CF2=CF).

Figure 59 H1 NMR, two hydrogens, complex multiple for CH=CH.

Table XXIV mass spectrum m/e 176 (M ), 157 (M-F), 126 (M-CF2), 107

(MCF3). High resolution mass spectrum, CsF6sH, calculated mass 176.07

measured 176.01.

The reaction was repeated using 55 grams of CF2ClCFClCH=CHCF3

to give 31 grams of CF2=CFCH=CHCF3 for a 80% distilled yield.



Dehalogenation of CF2C1CFCICH2CHICF3 with Zinc

A 250-mi, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, short column, distillation head, and thermometer.

The flask was charged with ethanol (150 ml) and zinc (20 grams) and the

mixture stirred and one ml. of bromine was added. The mixture was

heated to 50C as the CF2ClCFClCH2CHICF3 (90 grams) was added dropwise

and an immediate exotherm to 800C was noted. After the mixture was

allowed to cool to ambient temperature, the solution was added to one

liter of ice water. The organic layer was collected and dried before

distillation. The product, CF2ClCFCICH2CH=CF2 (37 grams, 72% yield),

was distilled (bp 101-1030C) and was 99+% pure by GLC analysis (Figures

80 and 81). Figure 80 IR (liquid) maxima in microns 5.67 (CF2=CH),

7.55, 7.9, 8.15, 8.4, 8.62, 9.1, (C-F), 9.3, 9.9, 12.3. Figure 81 -

F19 NMR, two fluorines, multiple for (CF2=CH), two fluorines, double

for CF2C1, one fluorine, multiple for CFC1. Table XXXII Mass










spectrum m/e 230 (M ), 193 (M-C1), 143, (M-CF2Cl), 77 (M-C2F3C12).

High resolution mass spectrum, CF,35C12H3, calculated mass 228.07,

measured 227.95, C5sF35C137C1Ha, calculated mass 230.07, measured

229.95.



Reactions of Olefins Precared



2 + 2 Reactions of Chlorotrifluoroethylene with CF2=CFCH=CHCH3

An ampoule was charged with one gram of CF2=CFCH=CHCH3 and cooled

in liquid oxygen before a full vacuum was applied and one gram of

chlorotrifluoroethylene was condensed into the system. The ampoule

was sealed under vacuum and placed in an oil bath at 1600C for 20

hours. After it was cooled to ambient temperature, the ampoule was

frozen in liquid oxygen and opened. The overgases were vented and

1.2 grams of product was collected. Infrared analysis indicated a

R'CH=CHR absorption. A larger sample was then prepared using 6.1

grams of CF2=CFCH=CHCH3 and 5.8 grams of chlorotrifluoroethylene.

The product was completely characterized as the dimer of CFc=CFCH=CHCH3

with the following 2 + 2 structure (bp 160-161C, quantitative yield,

CF2--CFCH=CHCH3
I I
CF2--CFCH=CHCH3

Figures 31 33). Figure 31 IR (liquid) maxima in microns 3.35, 3.41

(C-H), 5.95 (CH=CH), 7.2, 7.25, 7.9, 8.4 (C-F), 10.1, 10.4, 11.2.

Figure 32 H1 NMR, three hydrogen, doublet for CH3; two hydrogens,

two sets of multiplets for (CH=CH). Figure 33 F19 NMR, two

fluorines, two sets of multiplets for CF's; four fluorines, five sets

of multiplets for both CF2's. Table XVII Mass spectrum m/e 244 (M ),

122 (M-CFF3H3).









2 + 2 Cycloaddition of 2,2-Dichlorodifluoroethylene with CF2=CFCH=CHCH3

An ampoule was charged with CF2=CFCH=CHCH3 (6.1 grams, 0.05 moles)

and frozen in liquid oxygen while being evacuated to full vacuum. The

CF2=CC12 (6.7 grams, 0.05 moles) was condensed into the ampoule and

the system sealed under vacuum. After reacting for 16 hours at 160C

in an oil bath, the tube was opened and the overgases vented. The

only product isolated was the 2 + 2 cyclic diner of CF2=CFCH=CHCH3.



Dimerization of CF2=CFCH=CHCH3

An ampoule was charged with CF2=CFCH=CHCH3 (15 grams) and

evacuated after being cooled in liquid oxygen. The system was sealed

under vacuum and heated in an oil bath at 100C for 16 hours. When

the ampoule was opened, the dimer was the only product present.

CF2- CFCH=CHCH3
I I
CF2- CFCH=CHCH3



Dimerization of CF2=CFCH=CHCF3

A 50-ml ampoule was charged with CF2=CFCH=CHCF3 (4.4 grams,

0.025 moles) sealed and heated to 80C for 20 hours. After being

cooled to ambient temperature, the ampoule was opened. Infrared

analysis indicated some unreacted diene. A GLC analysis showed the

material to be 50% unreacted diene and 50% 2 + 2 cyclic dimer.

The reaction was repeated at 100C for 20 hours to give complete

conversion of CF,=CFCH=CHCF3 to the diner CFCFCH=CHCF3 (bp 133-1350C

CF2CFCH=CHCF3

Figures 63 and 64). Figure 63 IR (liquid) maxima in microns 3.18










(C-H), 5.85 (CH=CH), 7.55, 7.8, 8.3, 8.75 (C-F), 10.4, 10.7.

Figure 64 F19 NMR, three fluorines, doublet for CF3, two

fluorines, two sets of multiplets for CF's; four fluorines, six

sets of multiplets for CF2's. Table XXVI Mass spectrum 352

(M+), 176 (M-CFs6H2), 157 (M-CsF7H2), 126 (M-CsFeHz).



Co-dimerization of CF2=CFCH=CHCH3 with CF2=CFCH=CHCF3

A 50-ml ampoule was charged with CF2=CFCH=CHCH3 (2 grams) and

CF2=CFCH=CHCF3 (3 grams) before being sealed and heated to 1050 for

20 hours. The ampoule was cooled to ambient temperature, and the

ampoule was opened. Infrared analysis showed no CF2=CF- absorption.

Distillation gave three fractions, the 2 + 2 cyclic dimer of

CF2=CFCH=CHCF3, the co-dimer of CF2=CFCH=CHCF3 and CF2=CFCH=CHCH3,

and the 2 + 2 cyclic dimer of CF2=CFCH=CCH3 (Figures 65 and 66).

Figure 65 IR (liquid) maxima in microns 3.18, 3.3, 3.35, (C-H), 5.88

(CH=CH), 7.1, 7.6, 7.8, 8.38, 8.7, (C-F), 10.3, 10.7. Figure 66 -

F19 hMR, three fluorines, doublet for CF3; four fluorines, multiplets

for CF2 in cyclobutane; two fluorines, multiplets for CF in cyclo-

butane. Table XXVII Mass spectrum m/e 298 (M+), 176 (M-C3F3H,), 122

(M-C5F7H2).



Attempted 2 + 2 Cycloaddition of Chlorotrifluoroethylene with
CF2=CFCH2CHBrCH3

An ampoule was charged with CF2=CFCH2CHBrCH3 (10.1 grams, 0.05

moles), which was frozen and evacuated, before the chlorotrifluoro-

ethylene (5.8 grams, 0.05 moles) was condensed into the system. After










the ampoule was heated for 20 hours at 1400C in an oil bath, it was

opened and the overgases vented. The only product isolated was the

starting CF2=CFCH2CHBrCH3.

SThe reaction of CF2=CFCH2CHBrCHU with chlorotrifluoroethylene

was repeated at 160C with similar results. No 2 + 2 addition was

found and the olefin, CF2=CFCH2CHBrCH3, was recovered.



Attempted Reaction of Butadiene with CF2=CFCH2CHBrCH3

An ampoule was charged with butadiene (0.84 grams) and

CF2=CFCH2CHBrCH3 (4.06 grams). The ampoule was sealed and heated to

1250C for 20 hours. After cooling to room temperature the ampoule

was opened and the CF2=CFCH2CHBrCH3 was recovered unreacted.

The reaction was repeated using a large excess of butadiene

(3.36 grams) with no reaction again after 20 hours at 120'C.



Attempted Reaction of Butadiene with CF2=CFCH=CHCH3

A 500-ml ampoule was charged with CF2=CFCH=CHCH3 (6.1 grams,

0.05 moles) and butadiene (5.4 grams, 0.1 moles) before being heated to

1200C for four hours. A fog was noted after one hour and black solids

had formed after four hours and the reaction was worked-up. After

the excess butadiene was removed, the only liquid product collected

was the 2 + 2 cyclodimer of the pentadiene.



Radical Addition of Bromotrichloromethane to CF2=CFCH2CHBrCH3
with Benzoyl Peroxide

An ampoule was charged with bromotrichloromethane (9.9 grams),

CF2=CFCH2CHBrCH3 (10.0 grams) and benzoyl peroxide (0.4 grams). After










being cooled to -196'C, the ampoule was evacuated to full vacuum and

sealed. The system was heated in an oil bath at 160C for 16 hours

before being opened and the products collected. Distillation gave

9.1 grams of material (bp 80-88'C/0.1 mm) which showed two peaks by

GLC analysis. Analysis showed the product to be two sets of diastere-

omers of CCl3CF2CFBrCH2CHBrCH, (79% yield, Figures 34 34). Figure

34 IR (liquid) maxima in microns 3.31, 3.38 (C-H), 8.3, 8.5, 8.7, 9.1,

(C-F) 9.7, 10.1, 11.7, 11.9, 12.0. Figure 36 H1 NMR, three

hydrogens, doublet for CH3; two hydrogens, multiplets for CH2; one

hydrogen, multiple for CHBr. Figure 37 F19 NTR, two fluorines,

two sets of doublets for CF2; one fluorine, two sets of multiplets

for CF. Table XVIII Mass spectrum m/e 398, 400, 402 M ), 323,

321, 319 (M-Br), 287, 285, 283 (M-Br+Cl). High resolution mass

spectrum, CeH,35C13F379Br2, calculated mass 397.10, measured mass

397.79.



Radical Addition of CCl3Br with CF2=CFCH=CHCH3 Using Benzoyl Peroxide

A 500-ml ampoule was charged with bromotrichloromethane, CCl3Br,

(197 grams, 1 mole), benzoyl peroxide (2 grams) and the pentadiene,

CF2=CFCH=CHCH3, (12.2 grams, 0.1 mole). The mixture was heated to

70C for four hours before being placed in a distillation flask and

the CCl3Br removed. The remaining material (14 grams) was further

distilled on a micro-column to give the 2 + 2 cyclodimer (7 grams)

and the desired adduct CC13CF2CFBrCH=CHCH, (6 grams, bp 225-230C

Figures 60 62). Figure 60 IR (liquid) maxima in microns 3.3

(C-H), 5.85 (CHI=CH), 7.6, 7.9, 8.7 (C-F), 9.5, 11.5, 11.8, 12.6,

13.4. Figure 61 F19, two fluorines, two multiplets for CF2; one









fluorine, two multiplets for CF. Figure 62 H1 NIR, three hydrogens,

two doublets for CHs; two hydrogens, two multiplets for vinyl

hydrogens. Table XXV Mass spectrum m/e no parent peak, 241, 239,

(M-Br), 203, 201 (M-CCI3), 151 (M-CC3lCF2-CF2), 122 (M-Br, CC13,

107 (M-Br, CCls) CH3). High resolution mass spectrum, C6HF335-

Cla79Br, calculated mass 318.10, measured 317.96.



Radical Addition of CC13Br with CF2=CFCH=CHCF Using Benzoyl Peroxide

A 100-ml ampoule was charged with CClBr (19.8 grams, 0.1 mole)

benzoyl peroxide (0.2 grams) and CF2=CFCH=CHCF, (4.4 grams, 0.025

moles) before being heated to 80C for 20 hours. The material was

then distilled on a micro column to give 3.6 grams of higher boiling

material. NMR analysis indicated higher telomers and no simple adduct.



2 + 2 Cycloaddition Reaction of Chlorotrifluoroethylene with
CFa=CFCF2CF=CF2

The attempted cycloaddition reaction of chlorotrifluoroethylene

with CF2=CFCF2CF=CF2 was carried out in an ampoule at 160C for 48

hours. The CF2=CFC1 (5.8 grams,0.05 moles) and F,l,4-pentadiene (10.6

grams, 0.05 moles) were placed in the ampoule, sealed, and heated to

1600C. After the ampoule was opened and the overgases vented, the

starting material, CF2=CFCF2CF=CF2, was recovered.



The Addition of Bromine to CF2=CFCF2CF=CF2

A 50-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a condenser. The CF2=CFCF2CF=CF2

(10.6 grams, 0.05 moles) was placed in the flask and stirred as the










bromine (8.0 g) was added dropwise via the dropping funnel. As the

reaction proceeded, the temperature rose to 50'C and the flask was

cooled in a water bath. After the bromine had been added, the mixture

was distilled to give the dibromide CF2BrCFBrCF2CF=CF2 (76% yield,

14 grams, bp 126-127C, Figures 38 and 39). Figure 38 IR (liquid)

maxima in microns 5.6 (CF2=CF), 7.4, 7.65 (CF2=CF), 8.5, 9.0 (C-F),

9.5, 10.4, 11.7. Figure 39 F19 NMR, two fluorines, triplet for

(CF2=C); one fluorine, multiple for (CF=C); two fluorines, a

doublet of doublets for center CF2; one fluorine, a multiple for

CFBr; two fluorines and two multiplets for CF2Br.



The Attempted Radical Addition of 2-IodoheDtafluoropropane with
CF2=CFCF2CF=CF2

An ampoule was loaded with 2-iodoheptafluoropropane (14.8 grams,

0.05 moles) and CF2=CFCF2CF=CF2 (10.6 grams, 0.05 moles) before being

cooled to -196C in liquid oxygen and evacuated. After being sealed,

the ampoule was warmed to 1550C for 36 hours. The pentadiene,

CF2=CFCF2CF=CF2, and CF3CFICF3 were the only products recovered.



The Attempted Reaction of Trifluoronitrosorethane with
CFZ=CFCF2CF=CF2

An ampoule was charged with CF2=CFCF2CF=CF2 (4.2 grams, 0.02

moles) before being cooled in liquid oxygen and evacuated. Trifluoro-

nitrosomethane (CF3NO, 2.0 grams, 0.02 moles) was condensed into the

ampoule and the system sealed. The ampoule was allowed to warm to

-780C in a Dry-Ice acetone bath over a 48-hour period. Since the










deep blue color of CFaNO still remained, the ampoule was warmed to 0C

for an additional 48 hours, then to ambient temperature for eight

hours. When the ampoule was opened, the only products recovered were

trifluoronitrosomethane and CF2=CFCF2CF=CF2.



The Reaction of Ozone with CF2--CFCH=CHCH3
I I
CF2 -CFCH=CHCH3

A 250-mi Erylenmeyer flask was equipped with a gas inlet tube

and a outlet which was vented to the outside. The diner,

CF23-CFC1ICR013
CF2--CFCH=CHCH3
CF2- CFCH=CHCH3

(25 grams, 0.12 moles) was dissolved in methylene chloride (150 ml)

and placed in the reactor. Ozone, from a Welback ozone generator, was

bubbled through the mixture for three hours at \2% ozone concentration

(2.5 equivalents of ozone) after the solution had been cooled to -78C

in a Dry-Ice acetone bath. After removal of the methylene chloride,

a water white semi-viscous fluid remained which contained none of

the starting material. The reactivity of this material with potassium

iodide indicated the presence of the ozonide (Figures 40 and 41).


/ \
0- 0



I0-0'
CF2 CFCH CHCH
0

Figurr 40 IR (liquid) maxima in microns 3.3, 3.38 (C-E), 7.2,

7.9, 8.3, 8.9, 9.1 (C-F), 11.2. Figure 41 HI NMR, three

hydrogens, doublet for CH3; two hydrogens, multiple for CH.









An attempt to decompose the ozonide with zinc and acetic acid

became a run-away reaction after \20 minutes and only polymeric

tars remained.



The Reaction of Ethanol and Potassium Hydroxide with CF2=CFCH=CHCH3

A 100-ml, three-necked flask was equipped with a magnetic

stirrer, thermometer, dropping funnel, and a condenser backed by a

liquid oxygen trap. The ethanol (50 ml) and potassium hydroxide (6

grams, 0.12 moles) were added to the flask and stirred as the

CF2=CFCH=CHCH3 (11.2 grams, 0.1 moles) was added dropwise. An exotherm

to 35C was noted and, after one hour, the mixture was washed with ice

water (500 ml). The lower organic layer was collected and dried over

molecular sieves and distilled to give 9.2 grams of a mixture of

CHICH20CF2CFHCH=CHCH3 (80%) and CH3CH20CF2CF=CHCH2I3 (20%) (bp 125-

1290C, Figures 42 44). Figure 42 IR (liquid) maxima in microns

3.35 (C-H), 5.8 (CF=CH), 5.92 (CH=CH), 7.7, 7.82, 8.2, 8.7 (C-F),

9.5 (C-O), 10.3. Figure 43 H1 NMR, three hydrogens, doublet

for CH3; three hydrogens, triplet for CHI; two hydrogens, multiple

for CH2; three hydrogens, three types of vinyl hydrogens. Figure 44 -

F19 NMR, one fluorine, multiple for (CF=C); one fluorine, multiple

for (CFH); two fluorines, multiple for (CF2). Table XIX Mass

spectrum m/e 168 (M+), 153 (M-CH3), 151 (X-CHs), 139 (M-C2H5),

148 (M-HF), 123 (M-C2H50).



The Reaction of Ethanol and Potassium Hydroxide with CF2=CFCH=CHCF3

A 50-ml, three-neck flask was equipped with a thermometer,

reflux condenser, dropping funnel, and magnetic stirrer. The ethanol










(20 ml) and potassium hydroxide (0.5 grams) were placed in the flask

and stirred over a 20-minute period. The CF,=CFCH=CHCF3 (8.8 grams)

was added via the dropping funnel over a 20-minute period with an

exotherm to 56C noted. After being cooled to room temperature, the

mixture was added to 100 ml of ice water and the organic layer collected

and dried over molecular sieves. Distillation gave 5.3 grams of

product, CH3CH2OCF2CF=CHCH2CF3 (bp 103-105C, Figures 67 69).

Figure 67 IR (liquid) maxima in microns 3.3 (C-H), 5.78 (CH=CH), 7.6,

7.8, 7.95, 8.2, 8.65, (C-F), 9.3, 9.6 (C-O). Figure 68 F19 NSR

three fluorines, multiple for (CF3). Figure 69 H1 NMR, three

hydrogens, triplet (CHs); two hydrogens, multiple (CH2-O); one

hydrogen, multiple (CH=C); two hydrogens, multiple (CH2).



Addition of Bromine to CF=CFCH=CHCH3

A 50-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and reflux condenser backed by a liquid

oxygen trap. The diene, CF2=CFCH=CHCH3, (2.6 grams, 0.021 moles) was

placed in the flask and cooled in an ice water bath to +3'C. The

bromine (3 grams) was added dropwise and a very vigorous reaction

observed. The exotherm reached 40C and was controlled by the rate

of addition of bromine. There was collected 5.3 grams of product,

CF2BrCFBrCH=CHCH3, which was distilled to give 4.2 grams of pure

product (bp 152-1550C, Figures 45 and 46). Figure 45 IR (liquid)

maxima in microns 3.34, 3.4 (C-H), 5.9 (CH=CH), 7.7, 8.0, 8.4, 8.8

(C-F), 9.3, 9.7, 10.0, 10.6, 11.2, 11.7, 13.0. Figure 46 H1 n R,

three hdrogens, doublet for CH3; two hydrogens, two types of vinyl

hydrogen. Table XV Mass spectrum m/e 283, 282 (H ), 203, 201

(M-Br), 153, 151 (M-CF2Br), 122 (M-Br2).










Addition of Bromine to CF2=CFCH=CHCF3

A 50-ml, three-necked flask was placed in an ice water bath and

equipped with a magnetic stirrer, condenser, thermowell, and dropping

funnel. The diene, CF2=CFCH=CHCF3 (8.8 grams, 0.05 mole) was placed

in the flask and cooled to 0C before the bromine (8 grams) was added

via the dropping funnel. The reaction was slow and, after one hour,

the color had disappeared. Infrared analysis indicated the 1,4-

addition product had been formed. NMR analysis proved the mixture to

be a 75/25 ratio of 1,4- to 1,2-addition (bp 124-126'C, Figures 70

and 71). Figure 70 IR (liquid) maxima in microns 3.15, 3.28 (C-H),

5.8 CF=CH, 5.85 (CH=CH, 7.5, 7.6, 7.95, 8.3, 8.6, 8.7 (C-F), 9.4,

10.6, 11.1, 13.5. Figure 71 F19 N2R, three fluorines, two

multiplets for (CF3); two fluorines, two multiplets for (CF=C) and

(CFBr); three fluorines, two multiplets for (CF3). Table XXVIII -

mass spectrum m/e 336 (M+), 257, 255 ('--Br), 238, 236 (M-FBr), 186

(M-Br-CFa). High resolution mass spectrum CF6H279Br2, calculated

mass 334.07, measured 333.84.



The Reaction of Trifluoronitrosomethane with CF,=CFCH=CHCH3 at -78C

An ampoule was charged with CF2=CFCH=CHCH3 (2.25 grams, 0.02

moles) before being cooled with liquid oxygen to -196C and evacuated.

The trifluoronitrosomethane (CF3NO, 2.0 grams, 0.02 moles) was

condensed into the ampoule and the system sealed. The ampoule was then

placed in a Dry-Ice acetone bath at -780C for 48 hours. A green,

thick oil was present; therefore, the anpoule was opened and the

overgases were vented. The product, a slightly yellow viscous liquid,










was recovered (3.1 gram) and placed in a 5-ml flask. A full vacuum

was applied to remove the lower boiling component which was identified

as CF2CF=CHCHCH3 (2.0 grams), the 2 + 4 cycloaddition product. The
\ /
N--0

CF,

remaining polymeric material contained two types of olefin absorptions

as characterized by infrared analysis. Both -1NOCFzC- and

CF3 CH n
I I
CH 1,2 addition

CH3 product

SNOCF2CF=CHCH -

CF3 CHa n 1,4 addition product



of the polymer were found to be present (Figures 47 49). Figure

47 IR (liquid) maxima in microns, 3.32 (C-H), 5.85 (CF=C),

7.2, 7.7, 7.93, 8.3, 8.4, 8.8 (C-F), 9.25, 9.6, 11.0, 13.6.

Figure 48 HI NMR, three hydrogens, doublet for (CH3); one

hydrogen, multiple for (CH-O); one hydrogen, vinyl hydrogen

multiple. Figure 49 F19 NMR, three fluorines, nultiplet for

(CFa-N); one fluorine, quartet for (CF=C); two fluorines,

multiple for (CF2-N). Table XXI Mass spectrum n/e 221 (M ),

122 (M-CFSNO), 121 (M-CF3NOH). Figure 53 1,2 and 1,4 polymer

with CF3NO. High resolution mass spectrum, C6sHF6NO, calculated

mass 221.11, measured 221.03.










The Reaction of Trifluoronitrosomethane (CF3NO) with CF2=CFCH=CHCF3
at -78C

A 50-ml ampoule was charged with CFSNO, trifluoronitrosomethane,

(2 grams) and CF2=CFCH=CHCFs (3.52 grams). The ampoule was sealed

and the mixture placed in a Dry-Ice acetone bath for 24 hours. The

ampoule was then opened and the products collected (5.1 gram).

Distillation gave the 2 + 4 cycloaddition product (bp 100-1020C,

2.2 gram) and polymer (1.4 grams, Figures 72 75). Figure 72 -

IR (liquid) maxima in microns 3.2 (C-H), 5.85 (CF=CH), 7.8, 8.3,

8.7, 8.8 (C-F.), 10.7, 11.1. Figure 73 IR (liquid) maxima in

microns 3.16 (C-H), 5.85, (CF=CH), 6.2 (CH=CH), 7.5, 8.0 9.0

(C-F), 8.3, 10.2, 10.7. Figure 74 HI NM, one hydrogen,

multiple for (CH-0); one hydrogen, doublet of pentets for vinyl

hydrogen. Figure 75 F19 NMR, three fluorines, multiple for

(CFa-N); one fluorine, multiple for (CF=CH); two fluorines,

multiple for (CF2-); three fluorines, multiplet for (CF3-C).

Table XXIX Mass spectrum m/e 275 (M ), 256 (M-F), 206 (M-CF3),

176 (M-CF3NO), 126 (M-CF3NO, CF2). High resolution mass spectrum,

CsH2FNO, calculated mass 275.08, measured 275.00.



The Reaction of Phenylmagnesium Bromide with CF2=CFCH=CHCH3

A 250-ml, three-necked flask was equipped with a magnetic stirrer,

thermometer, reflux condenser, and a dropping funnel. The flask was

set up in an ice water bath before the ethyl ether (150 ml) and

CF2=CFCH=CHCH3 (12.2 grams, 0.1 moles) were added. The mixture

was stirred as the phenylmagnesium bromide (0.1 mole) was added over










a 30-minute period. The temperature did not increase as had been

expected. After being stirred for five hours, the mixture was

hydrolyzed in ice water, the ether layer was collected and dried

over molecular sieves. The ethyl ether was removed to give 5 grams

of higher boiling material which was vacuum distilled to give 2.1

grams of a mixture of biphenyl, phenol, and 1.2 grams of the desired

product CsHCF=CFCH=CHCH3 (Figure 76). Figure 76 IR (liquid)

maxima in microns 3.22, 3.25, 3.32, (C-H), 5.8 CF=CF, 6.2 (C6Hs),

8.0 8.4 (C-F), 13, 14 aromatic. Table XXX Mass spectrum m/e

180 (M+), 179 (M-H), 165 (M-CHa), 154 (x-C2H2), 153 (M-C2H3), 152

(M-C2H4).



The Reaction of Phenylmagnesium Bromide with CF2=CFCH=CHCF3

A 100-ml, three-necked flask was equipped with a magnetic stirrer,

a thermometer, a reflux condenser, and a dropping funnel. The ethyl

ether (30 ml) and CF2=CFCH=CHCF3 (8.8 grams, 0.05 moles) were placed in

the flask and stirred as the phenylmagnesium bromide (0.05 moles) was

added dropwise via the dropping funnel. There was an immediate

exotherm to 50C with vigorous reflux of the ether. The addition was

carried out over a 30-minute period and, after one hour of stirring,

the solution was hydrolyzed in ice water. The ether layer was

collected, dried over molecular sieves and the ether removed. Further

vacuum distillation gave the desired C6HsCF=CFCH=CHCF3 (8 grams,

bp 60-65/0.1 mm, 68% distilled yield). A GLC indicated two isomers,

cis and trans in a 65/35 ratio (Figures 77 and 78). Figure 77 -

IR (liquid) maxima in microns. 3.18, 3.32 (C-H), 5.95 (CF=CF),









6.19 (aromatic), 7.6, 7.8, 7.9, 8.8 (C-F), 10.2, 12.9, 14.1.

Figure 78 F19 NMR, three fluorines, multiple for (CF3); two

fluorines, multiplets for (CF=CF) both cis and trans. Table XXXI -

Mass spectrum m/e 235, 234 (M ), 165 (M-CF3), 164 (M-CF,, H),

145 (M-CF, HF). High resolution mass spectrum CiiH7Fs, calculated

234.17, measured 234.05.

The reaction was repeated at -30C using the same ratio of

starting material. The hydrolysis was carried out with D20 and

the ether layer collected, dried over molecular sieves and the ether

removed to give only C6HCF=CFCH=CHCF3 and no C6HsCF2CFDCH=CHCF3

showing that the [C6HsCF2CFCH=CHCF3] is not an intermediate.



Attempted Reaction of CF2=CFCH=CHCH3 with Diethylamine

A 250-ml, three-necked flask was equipped with a magetic stirrer,

dropping funnel, reflux condenser, and thermometer. The ethyl ether

(150 ml) and diethyl amine (7.4 grams) were placed in the flask and

stirred at 50C in an ice water bath before the diene CF2=CFCH=CHCH3

(12.2 grams, 0.1 mole) was added via the dropping funnel. There was

no apparent reaction and the mixture was warmed to ambient tempera-

ture and stirred for 48 hours. The ethyl ether was then removed

under vacuum to give 6.6 grams of higher boiling material which was

distilled and determined to be the 2 + 2 cyclic diner of the

CF2=CFCH=CHCH3.










Reaction of CF2=CFCH2CHBrCH3 with Magnesium

A 50-ml flask was equipped with a magnetic stirrer and a reflux

condenser before being charged with magnesium turnings (0.1 mole,

2.4 grams) and 10 ml of ethyl ether. The CF2=CFCH2CHBrCH3 (24 grams,

0.2 mole) was added and an immediate exotherm caused the ether to

reflux. After the addition was complete, the mixture was hydrolyzed

and the ether layer collected and dried over molecular sieves. The

ether was removed to leave the starting material (13 grams) and

higher boiling material (7 grams). Further vacuum distillation gave

1.1 grams of material identified as the desired coupled product along

with polymeric material (Figure 79). Figure 79 IR (liquid)

maxima in microns 3.32 (C-H), 5.52 (CF2=CF), 7.7, 7.95, 8.7, (C-F),

9.2, 12.5.



Attempted Reaction of CF,=CFCH=CHCF3 with H2SO, and Water

A 25-mi flask was equipped with a magnetic stirrer and a reflux

condenser before being charged with water (10 ml) and H2S0O (2 ml).

The diene CF2=CFCH=CHCF3 (2 grams) was added and the mixture stirred

for six hours. A sample was then taken and infrared analysis

showed that no reaction had taken place.
















SECTION 4

ENVIRONMENTAL IMPACT



Due to the small scale usage of chemicals and proper disposal

procedures, there was no unexpected impact on the environment. A

listing of the compounds used along with the (NIOSH) National

Institute for Occupational Safety and Health Registry data are

included.



1. Acetic acid (CH3COOH) AF-1225000 TXDS oral rat

LDso: 3310 mg/kg TL 10 ppm DOT corrosive material

0 0
2. Benzoyl peroxide C-OO-0- DM-8575000 TXDS

oral-hum LDLo 500 mg/kg TL 5 g/kg DOT organic peroxide

3. Bromine (Br2) EF 9100000 TXDS inh mus LCso: 750 ppm/

9 min. TL TWA 0.1 ppm DOT corrosive material

4. Butadiene (CH2=CHCH=CH2) E1-9275000 TXDS oral rat

LDso: 5480 mg/kg TL 1000 ppm DOT flammable gas

5. 1,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFClBr)

KH-7600000 TXDS inh-rat LcLo 25,270 ppm/15 M

harmless liquid for shipping purposes

6. Dichloroiodotrifluoroethane No listing, considered

harmless










7. Diethyleneglycol dimethyl ether (CH3OCH2CHO2CH2CH20CH3) -

No listing, considered nontoxic, compared to tetraethylene-

glycol dimethyl ether.

8. Dimethyl sulfide (CHsSCH3) PV-5075000 TXDS oral rat

LDso: 535 mg/kg 'DOT flammable liquid

9. Dimethyl sulfoxide (CH3SO2CH3) PV-6210000 TXDS oral nus

LDso: 21 grams/kg DOT fla=zable

10. Ethanol (CHCCHO2H) KQ-6300000 TXDS oral rat LDo:

14 grams/kg TL 1000 ppm DOT flammable liquid.

11. Ethylene (CH2=CH2) KU-5340000 TXDS inh mus LCso: 95 ppm

TLm 96: 1000-100 ppm DOT flammable gas

12. Iodine (12) NN-1575000 TXDS oral human LDLo: 5 mg/kg

inh dog LDLo: 40 mg/kg TL 0.1 ppm

13. Methylene chloride (CH2C12) PA-8050000 TXDS oral rat

LDso: 167 mg/kg TL 2000 ppm DOT ORM A otherwise

restricted material

14. Ozone (Oz) RS-8225000 TXDS inh rat LCso: 4.8 ppm/4H

TL 0.1 ppm DOT toxic gas

15. Potassium t-butoxide (CH1C(CHa)20 K ) No listing

DOT corrosive solid.

16. Potassium hydroxide (KOH) TI-2100000 TXDS oral rat

LDso: 365 mg/kg TL 2 mg/on DOT corrosive material

17. Propene (CH2=CHCH3) UC-6740000 AQTX TLm 96: over 1000 ppm

DOT flammable gas











18. Pyridine D UR-8400000 TXDS oral rat LDso:



891 mg/kg TL 5 ppm DOT flammable liquid

19. Sodium hydroxide (NaOH) WB-4900000 TL 2 mg/m3

IRDS skin rabbit 50 mg/24 H SEV DOT corrosive material

20. Tetrafluoroethylene (CF2=CF2) KX-4000000 TXDS inh rat

LCso: 40,000 ppm/4 H DOT Flammable gas

21. Trifluoropropene (CF3CH=CH2) No listing

22. Zinc (Zn) ZG-8600000 TXDS inh human TCLo: 124 mg/m3/

50 min.

23. Zinc bromide (ZnBr2) ZN 1400000 TXDS oral rat LDso:

350 mg/kg TL 1 mg/m3 DOT corrosive solid










Explanation of Symbols and Abbreviations for Environmental Impact



TXDS Toxic dose data

inh Inhalation

rat rat

ppm Parts per million

M Minutes (min.)

LcLo Lowest lethal concentration

LDso Lethal dose calculated to cause 50%

of the experimental animal population

to die

LDLo Lowest lethal dose

TL Threshold limits

TLm 96 Concentration which will kill 50% of

the exposed organism within 96 hours

AQTX Aquatic toxicity ratings

SEV Severe irritation effects

DOT Department of Transportation







































.". ...-'. ,. J [ ,: J ,. ... 6 ,l .. ", .,,,, l.: '" I,. .
FREQUENCY (CM')



Figure 1 Infrared Spectrum of CF2BrCFC1Br







































FREQUENCY ICM -)


Figure 2 Infrared Spectrum of CFBrCFCCH L Biling Diateremer
Figure 2 Infrared Spectrum of CF2BrCFC1CI{CHBrCH3 Lower Boiling Diastereomer







































I2UO IOUU 000 6X 400


Figure 3 Infrared Spectrum of CFaBrCFC1CIC2CIlBrClls Higher Boiling Diastereomer






















r w.
-o-
NC-I LL
00YUI-0~~ O D
U~DOC~n~O~O~ D
YYINI'PI
~~~YIT~~L
YLIU ~~ryl I~
li-I-(-l-tfFfcHft+l~-1~'-l-ltlj-f~t


KI" -;-.:,i-tt r G,,, -
^l~i^^ 4l1e^^^^^^ l


~-4 4


I~,


-I-
i I


-ll llilll


Vr 1


I-l



































A B



Figure 5 -.F19 NMR of Lower Boiling Diastereomer of CF2BrCFClCH2CHBrCH3
A B


































A B



figure 6 F1i? MR of Higher Boiling Diastereomer of CF2BrCFCICHaCHBrCHI
A B








TABLE XI

MASS SPECTRUM OF CF2BrCFCICH2CHBrCH3 (BOTH DIASTEREOMERS)

Molecular Weight 320. Listing of peaks with >1% base peak intensity
along with M peak. 79 239 121 107

Br CF2CFC1 CH2 CHBrCH3


Nominal Mass

320
318
316
241
240
239
238
237
219
217
204
203
202
201
197
195
183
181
175
173
171
160
159
158
157
155
153
147
145
142
141
140
139
138
137
131
129
127
123
122
121
120
119


% Int. Base

0.2 MP
0.4
0.2
6.5
1.5
26.4
1.3
20.6
1.2
1.1
1.4
21.1
1.5
22.0
1.4
1.0
4.0
4.1
1.4
2.0
1.3
1.1
14.9
3.1
53.6
9.1
1.3
2.3
2.0
1.0
1.1
1.0
11.0
2.4
20.2
6.2
7.5
1.5
3.8
11.1
26.5
1.3
3.4


Nominal Mass

118
116
113
111
110
109
108
107
106
105
103
102
101
96
95
94
93
91
89
87
85
83
82
81
80
79
78
77
76
75
73
72
71
70
69
68
67
66
65
64
63
62
61


% Int. Base

1.6
4.2
6.0
16.3
1.7
61.9
3.7
69.5
1.4
1.1
2.5
4.0
9.7
1.0
26.8
1.2
19.8
3.0
1.6
3.0
5.5
2.8
3.6
3.9
4.6
4.3
2.0
13.1
1.1
10.2
3.0
3.5
7.8
1.9
15.4
1.6
3.0
2.0
35.7
3.3
100.0
1.3
3.2








































40DO 3LoO 32GO 2800 2400 2000 ION 1600 400 1200 1000 600 600 400
FREQUENCY (CM'-1



Figure 7 Infrared of CF2BrCFClCI2C1I (CI%)CH2CUIr rCF3


















































AP - - - C-- --- C -- --- - --- -


CF,

Figure 8 11 NMR of CF2BrCFC1C[2CIIC1L2CII~r
C B C A


-77-





















N u *"







A


Figure 9 F19 NMR of CF2BrCFC1CH2CHCH2CHBrCF3
A
CF3











iI'Il

III


Figure 10 F19 NMR of CF2BrCFC1 2CHCH2CHHBrCF,
B C
CF,











TABLE XII
*
MASS SPECTRUM OF CF2BrCFCICH2CHCH2CHBrCF3
CF3

Molecular Wejght 445. Listing of peaks with >1% base peak intensity
along with M peak.


369
367 289 175 163
303 287 177 161
301
CF2BrCFCl CH2 CH CH2 CHBrCF3
CF3


Nominal Mass % Int. Base

305 3.3
303 5.4
301 2.9
299 1.4
297 1.0
289 9.2
288 2.5
287 26.1
285 3.3
283 1.4
273 2.3
272 3.8
271 34.8
269 5.5
268 2.3
267 5.5
265 1.5
264 1.0
263 1.3
259 3.9
258 1.5
257 11.8
255 2.4
253 6.3
252 5.2
251 37.9
249 1.7
[Peaks >5%]
237 6.0
232.5 5.1
225 9.5


Nominal Mass

445
443
391
389
388
387
383
371
370
369
368
367
354
353
351
349
347
341
339
337
334
333
330.5
327
321
319
317
313
311
309
307


% Int. Base

1.7 @
1.2
1.2
3.8
1.1
3.1
1.2
4.1
2.0
18.0
1.7
14.9
1.6
17.3
19.5
14.1
10.9
2.1
8.2
6.2
1.2
13.3
14.5
1.2
1.5
5.4
4.1
1.3
1.1
2.0
5.7











Nominal Mass % Int. Base

223 5.4
221 9.7
211 5.7
209 7.0
207 6.2
205 5.1
201 12.1
195 6.8
193 9.0
191 8.9
189 10.3
183 5.9
179 5.6
177 44.1
176 7.5
175 41.6
173 5.5
171 11.7
163 13.4
161 12.0
157 11.9
155 6.1
147 5.1
145 19.1
143 6.7


Nominal Mass


% Int. Base

5.6
9.3
23.9
22.4
25.7
5.8
5.0
8.0
8.4
42.5
33.1
14.3
7.3
6.2
5.7
100.0
7.5
8.0
23.0
6.1
7.5
72.0
11.5
67.3
12.7







































12D IwIO UDO 60O 40Q


Figure 11 Infrared Spectrum of CF2BrCF2I







































1600 3o00 OO 240 2000 10o 100 400 14 100 1000 o00o 00 400
FRLQUENCt (CMl'



Figure 12 Infrared Spectrum of CF2BrCF2CH2CH2I







































4000 3600 3200 2800 2400 2000 1800 600
FREQUENCY( CM-)



Figure 13 Infrared of CF2BrCFC1CH=CHCHs










-.. -......- . ..



ao0














A



B C









Figure 14 H1 NMR of CF2BrCFC1CH=CHCH3
C BA



















i ; I:
i i 01











Figure 15 F19 NM of CFiBrCFC1CH=CHCH,
A











TABLE XIII

MASS SPECTRUM OF CF2BrCFClCH=CHCH3

Molecular Weight 238. Listing of peaks with >1% base peak intensity
along with M1 peak.


79 157, 159
Br CFzCFClCH=CHCH3


201, 203
CF2BrCFCH=CHCH,

Cl 35


Base peak 107
79 107 15
BrfCF2CFCH=CH1 CH3
Cl 35
Cl 35


Nominal Mass %Int. Base


Nominal Mass % Int. Base


0.7
0.6
4.4
4.6
2.0
6.8
1.9
1.6
4.1
1.9
2.4
9.5
8.6
1.1
2.4
1.6
32.5
4.7
100.0
1.0
1.6
3.1
9.3
9.0
3.9


4.6
2.3
5.4
2.1
1.7
2.2
1.9
1.4
4.4
5.5
1.0
6.1
24.5
2.2
7.0
1.3
1.7
1.7
2.6
1.0
3.6
4.7
1.8
20.4























20




I 1I j
4(O 36r00 3200 9000 7400 200 00000 0 000
fWOQULNCY (CM'


1~urc ..16 in1frrrcd SpectLuil Of CF21a1CF~tc1CIIf1.


























O









SIA






Figure 17 F19 NMR of CF2BrCF2CH=CiI2
B A

















2: !:241-
Et;:F e.41~41PP4


i FFII.(,) PI 2 i'
I 5 S .B I l.![ 53
2 595.?I 3.)il 342 ,
I 5i2.27 2.921 13;
4 s at.11 2.212 7 t
S S2:,9( 5.222 Wt
1 5(t0s. 1 t.i. 1 3




1 1.6E I..l '5Z'


TMS


Figure 18 Ii1 NMR of CF2BrCF2CII=CI12









































40)0 3600 3200 2 000 400 2000 1800 100 1400 1?00 1000 800 600 400
FRLQUCNCY CM-')



Figure 19 Infrared Spectrum of CF2C1CFBrCF2CF=CFa









MICROMET1RS 1,m


4000 3600 3200 2U00 2400 2000 100 1600 1400
FtQOUENCY [VO'CM



Figure 20 Infrared Spectrum of CF2=CFCH=CIlCH3






INJECT TIME ?23 -L :12: 5

"- .-"__ .-=- ............ .. ... --- -.. .............................-...--.. ..... ......-.-..-... --.---- -- --















TGP-22-1
COLUMHN:GLRSS 2R 0QF--1
L TEMP: 730 HELD F0:: 2 MT
TEMP: 0 O

'EAK4 ARER PT RRER BC

I 0. n41 1.29 320 02
2 1.292 1. 49 101322 02
3 97. i.' 1. F.: 762267 08
4 0. .37 2. t 1075 05
5 1.15 2. 1.246 05
6 R2,9 1. 1 1951 01
7 0077 3. 92 G600 21
S 0.857 12 6719 21

TOTAL 1OP 789C42-


Figure 21 GLC Analysis of CF-CFCH=CllCIl3







1 i ,. .!. ;L I ,.. ,. i L. L .... . T L.. L A I p .L..- A L: .. l . II,.- LW-

VI




I


H




U C A
- ,, ,__-,,--._ . : _---r .- --r_-,-.T. --=-


Figure 22 H1 NMR of CF2=CFCCIICHIC
C BA












































F F
c\ 4/
Figure 23 F19 NMR of c=c

F C=CIICH9
131











TABLE XIV

MASS SPECTRUM OF CF,=CFCH=CHCH3

Molecular Weight 122. Listing of all peaks with >1% base intensity
along with M peak.



CFa=CFCH=CH CH, F CF= CFCH=CHCHJ H
107 103 72 102






Nominal Mass % Base Int. Nominal Mass % Base Int.

122 100.0 0 >5% Base Intensity
121 25.3 89 5.6
120 2.8 83 10.8
119 5.4 77 23.0
111 1.4 76 7.2
107 4.4 75 24.6
106 2.4 72 49.1
104 1.4 71 27.3
103 19.7 70 11.0
102 12.2 69 32.2
101 47.3 58 5.5
100 1.1 57 25.1
99 3.5 56 5.9
96 2.0 53 27.3
95 32.7 52 8.2
94 3.6 51 39.5
93 2.4 50 13.3





















4 i 40 i t
i0



I I i I I''1 I ^ " il l ?


4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 400
FREQUENCY (CM"I


Figure 24 Infrared Spectrum of CF2=CFCH2CHBrCH3









































L -- ---- -- --- --


F F

Figure 25 V19 NMR of CN\ :C=
F CICIflkrCI[1
13



























0a











C B A




Figure 26 H1 NMR of CF2=CFCfi2CHBrCH3
BC A











TABLE XV

MASS SPECTRUM OF CF2=CFCH2CHBrCH3

Molecular Weight 204. Listing of peaks with >1% base peak intensity
along with M peak.


95 108 123
CF2=CFCH2UC CH,
Br


% Int. Base

9.8
10.1
1.3
1.3
5.8
100.0
6.9
2.7
1.3
50.0
8.5
48.7
2.0
3.3
16.6
1.5
4.6
4.6
56.4


Nominal Mass


94
93
89
88
86.5
84
83
82
81
[Peaks
77
75
73
72
69
59
57
53
51


% Int. Base


1.2
1.5
2.4
1.5
2.6
1.1
5.6
4.5
2.8
>5% Int. base]
21.8
9.6
9.0
7.9
44.3
67.9
12.7
9.5
18.3


Nominal Mass

204
202
157
155
124
123
122
121
110
109
108
107
106
104
103
102
101
96
95
































)0 3W0 3200 2300 2400 2000 ll0 1600 1400 1200 1000 U0D 600 400
FREQUENCY I CM )

Figure 27 lufrared Spectrum of C2=2CFC112CllC1l2Cll=CF2
I F


SCF
i l 1 f! i I 'I


)0 3W0 300 2000 2800 2000 Io w 1600 1400 1200 00 O 800 OO 6 400
[QUV[NC0 CO'M

Flgure 27 Infrared Spectrun of CFa2CF112CI1a1 2CllClCl l 2
C~a












































Figure 28 F19 hIIR of


F F
-, A

F CII2MCHCI2CCC
BI
SCFRH
F









































)0 3600 3200 2000 2400 2000 1800 100 1400
FREQUENCY ICM1)




Figure 29 Infrared Spectrum of CF2=CFCF2CF=CF2














loo I















0 BC





A


F F

Figure 30 F19 NMR of C=CFCFzCF=C
I-, I--











TABLE XVI

MASS SPECTRUM OF CF2=CFCF2CF=CF2

Molecular Wejght 212. Listing of peaks with >1% base peak intensity
along with MJ peak.


131 162 50
CF2CFFCF22CF = 2CF2




Nominal Mass


213
212 >P
205
195
194
163
162
155
144
143
132
131
124
117
112
105
100
94
93
86
85
81
75
74
69
62
55
50
43
32
31
29
28


143 93 193
CF2,SCFCF2CJ=CF2
F 19


% Int. Base


2.9
52.7
1.4
1.2
16.4
1.6
36.5
1.7
4.7
84.3
3.2
100.0
12.1
1.3
9.7
3.7
1.6
3.0
87.7
1.9
1.0
5.4
2.3
13.6
57.1
3.5
6.3
5.0
1.0
9.1
54.8
1.3
29.7









' I ift*" .. : "I i TI 'i 11 I i h ''i[i;ll -- !i



S'













Figur 1 Inrard Sctru CFCFC=CICII
4-I II
SCFC FC ll=CiI CI




CFaCFCll=CllCH13

















2o. A
10











C
















Figure 32 H1 NMR of CF2CFCH=CHCH3
I I

CF2Cl'CIIH ClICIlS
C BA




























H
















1B A
Figure 33 F1o NMR of CF.2CCII=CIICI1,

CF2 CFCIt-CIICI I:
11 A












TABLE XVII


MASS SPECTRUM OF


CFCFCH=CHCH3
I I
CF2 CFCH=CHCH3


Molecular Weight 244. Listing of peak with >1% base peak intensity
along with M peak.

122
CF2CFCH=CHCH3


CF2CFCH=CHCH,
122


Nominal Mass


244
197
135
133
129
127
123
122
121
115
109
107
103
102
101
95
91
89
83
81
77
76
75


% Int. Base


0.1
2.0
2.3
1.6
3.2
2.2
5.9
100.0
10.4
1.0
1.9
1.2
4.3
6.1
6.5
4.5
5.4
1.4
1.7
1.4
3.3
1.0
2.8


Nominal Mass % Int. Base


2.3
12.9
8.0
1.5
5.1
1.8
1.0
1.2
3.7
1.2
13.9
1.0
6.0
1.2
1.4
1.2
4.2
1.8
3.0
6.5
5.4
93.5
3.8
















































3600 3200 2000 2400 2000 1U00 1600 1400 12003 00
FREQUENCY (CM-l)





Figure 34 Infrared Spectrum of CCCFCFBrCH2CHBrCH3


N
-4








'.hf .Fr rffnp i? italIe i











2. -
g 8i15
s-------. v w -

=y, "-"*


J OP-4 .l ?

14N[TTnl. TFMPI 'H1
FTNnL TEMPI 7?P

F1ilE .ETHnn

RMALVT, .TMO





14 n0. n ?


7 P. 1417




17 t, 7
5 7o

12 n.0 7


1 3 t i
11 n, 1,n

15 4l.L71 .
1; 24. 77

I 0. 71

2T 1, r 71T

TOTnL IPA.


r.Ni 'MNI o-1 0%
HFIl FnP0 7 in
PnTEr 1; d.5/atn

A, OUIM 2 TNDEX 2

TRM. I7. 19 q

PT ~EPn H C



SR 170071;, 71
1. 2 12 72 1

5. >4 t 6Gr7r t 11
75,5nr itnn 42
5.94 16671 92


?;.nr, 7105 n7

q. 19 79717 0A
A. nn 210 A7
9.00 n 7?4 A7
C). 9 F 0?
1. 5 07,1 027
tAN, 9 GrT1;f*r A2

it1. n 7t1 n n
1?.an 1 iA q2
17,7 "nimt q
It. T; 211 t n 01

1q957RO









































C B A



Figure 36 H1 NMR of CC1CF2CFBrCII2CIlBrCII
BC A




































BH





B A








*
Figure 37 p NMR of CC13CF2CF~rCICIICU~rGi12
B A











TABLE XVIII
*
MASS SPECTRUM OF CClICF2CFBrCH2CHBrCH3

Molecular Wejght 400. Listing of all peaks >1% base intensity
along with 1 peak.


321 323 Br Br
319 1 I
CJCCClaFCFCHCFCHCHCH
283, 285, 287


Nominal Base

402
400
398
323
321
319
287
285
283
243
241
239
237
235
225
223
221
219
207
206
205
204
203
201


% Int. Base

0.7
0.5
0.2
2.7
4.1
2.1
1.4
3.4
2.5
1.8
5.3
6.6
1.8
1.3
1.4
4.9
7.2
3.8
1.9
1.1
4.5
1.7
7.7
3.5


221, 223
219 239, 241, 243
CC13CF2C FCH2CIHCH3
Br Br



Nominal Base % Int. Base


195
193
191
189
187
[Peaks
177
167
153
151
145
143
132
129
127
125
123
122
121
119
117
111
109
107


1.2
1.6
1.8
3.8
3.1
>5% Base Int.]
5.4
5.3
6.8
7.1
9.6
10.1
5.1
10.9
13.4
5.1
6.8
6.1
11.6
13.2
12.7
12.6
68.5
100.0









































FREQUENCY (CM')



Figure 38 Infrared of CF2BrCFBrCF2CF=CF2

























E


B B D 5


A





Figure 39 F19 NMR of CF2BrCFBrCF2CF=CF2
E D C A B

















61












.f0) 3600 3200 200 2400 2000 1800 1600 1400 1200 1000 800 60. 0 400
FREQUENCY IGC")

Figure 40 Infrared Spectrum of CF2CFCH CHCH3 Ozonolysis Product
::1ji ii













Si I
; i i I [ i i | I! [ i l i 1 i i -i !





.10(t 3600 3200 7aoo 240o 2000 1000 60 10 1200 moo BO0 too 400

^000


CF2CFCH CHCH3
-.00 o0o'












































Figure 41 I1 NMNR of CF2CFCII-CllCll Ozonidc
CFCI;CIICIICIic






































40u0 3600 3200 2000 2400 2000 1000 1600 1400 1200 1 00) 00 600 4UO
FREQUENCY CM-')



Figure 42 Infrared Spectrum of C2HsOCF2CF=CH2CH 3 (85%) and C2HsOCF2CFHCH=CHCHs (15%)













































DC E B F
A


Figure 43 H1 NMR of CIICH20OCF2CFHCH=CHC and CH3CH20CF2CF=CHCIHCHs
F E A D C B F E G F

































Bo
00


11




























Figure 44 F19 NMR of CHsCH20CF2CFHCH=CCHCH and CH3CH20CF2CF=CHCH2CH
B A B C










TABLE XIX

MASS SPECTRUM OF CH3CH2OCF2CFHCH=CH3 and
CH3CH20CF2CF=CECH2CH3 MIXTURE


Molecular Weight 168. Listing
along with M peak.


15 153 123 H 122
CH3 CH2 O CF2CF=CHCHCH3
139


Nominal Mass

168
155
153
151
149
148
146
139
135
134
132
129
123
122
121
120
119
118
117
116
115
111
108


% Int. Base

0.5
0.8
4.8
5.6
0.5
2.9
0.9
0.5
1.6
2.7
0.6
0.6
1.1
4.8
2.2
8.8
2.2
3.0
1.2
0.8
0.6
0.6
0.5


of peaks with >0.5% base peak intensity



139 _F l48
C3 CH20J CF CCH=CECH3
45 103J-
H 1


Nominal Mass


% Int. Base


107 0.9
106 0.5
105 2.0
104 2.1
103 12.3
102 2.2
101 13.1
100 4.7
99 3.1
95 20.6
Peak intensity >1%







































0 36Co 3200 2800 2400 o2000 1)o0 0 1400
FREQUENCY CM-']




Figure 45 Infrared Spectrum of CF2BrCFBrClH=CIlCH3

























Ci






A


L'{ h '--L I ,



Figure 46 H1 NMR of CF2BrCFBrCH=CHCH3
C BA











TABLE XV

MASS SPECTRUM OF CF2BrCFBrCH=CHCH3

Molecular Weight 282. Listing of all peaks with >1% base intensity
along with MW peak.


203, 201
Br CF2CFCH=CHCH3
r 122
Br


201
203 155, 153
Br CF2 CFCH=CHCH3
Br


81
81 19 F
79 1 181, 183
Br CF2CCH=CHCHsSH
Br 102 1


Nominal Mass

283
282
281
219
217
204
203
202
201
188
186
184
183
182
181
175
173
157
155
153


% Int. Base

0.2 M
0.1
0.5
2.3
1.9
5.4
98.4
5.5
100.0
1.8
1.8
2.6
6.4
2.7
6.0
1.4
1.5
3.8
3.9
3.2


Nominal Mass

151
139
138
137
131
129
123
122
121
120
119
113
111
109
107
106
103
102
101
95


% Int. Base

3.2
5.1
1.9
5.9
3.8
3.3
7.1
77.0
30.5
1.9
5.5
1.3
1.5
1.1
3.9
1.6
7.5
14.9
28.3
25.2























I i l ,

S------- 0 4 4 I







\ /
3 00 3200 2800 2400 000 100 16 1400 1200 1000 8U00 600 400
FREQULNCY(CM"'


Figure 47 Infrared of CFCF=CHCHICFS
N-0
CFS













i I

:c-------
ii
i


.1


CBA
Figure 48 H1 NMR of CF2CF=CHCHCH3
N-0
CF
CF3











































Figure 49 F19 NMR of


B C
CF2CF=CILtll,
N-o

CF,
A


I I I 1


II IIC~(1(
't











TABLE XXI


MASS SPECTRUM OF


CF2CF=CHCHCH3
\ /
N--0

CF
CF3


Molecular Weight 221. Listing for peaks
along with M peak.


>1% base peak intensity


121
CF2CF=CHCHCH2 H
N- 0 122
CF3


Nominal Mass


221
182
156
123
122
121
118
114
109
103
102
101
96
95
94
91
89
77
76
75
73
72
71
70
69


% Int. Base


2.5 C
2.8
2.4
5.8
100.0
10.9
1.3
1.9
1.0
2.4
5.2
6.8
1.6
5.0
1.5
2.9
2.5
2.4
1.7
3.3
1.5
19.4
10.8
1.8
34.3








,~ ~ 1 , , .... ; i ,, h l '1 I, I; IJ ,,II i ,, , ,. , ,) II I I I : i I , ,
: ,' II
I 1 i i i I I "





3LCO 3700 2 7Z 2 i' 'I\ 180 1 60 100 120 0A) 00 60 0
NI i
Fiur 50 :, f R of an
,,1 l i I I '' , i I ,
i I I i / i I, ', I ', '
',,r~ ~~ j ',' I ;I i ", ',, 'i ,,,,/ (l ,-, ,="!

ii /; i/
.1 ..I I I I I
.. ,, ,, I '1 I ,I ,, ',',
I ; I ' ''
' : i ' ii ,, = ,'I' ', ,
"-' , L i I ' V
"-,, : I :, ; i i , -



''Jji" '

XIII 2IICO 3200 2000 240o0 2000 1000 1600 1400 1200 i 11i 000 000 400
FOOOOUONCf( I ")

Figure 50 -Infrared Spectrum of Polymer from Reaction of CF3NO and CF==CFCI{=CHCH3










































X 30 3 3200 2800 24 00 200 00 1600 1400 1200 1000 800 60 400
FR[QUENCY(CM-'i



Figure 51 Infrared Spectrum of CF2C1CFCICH2CHICF,

























B







al




LA




. igre 52 - 9 NMR of CF CCFC1--i- 12CHICF




Figure 52 F19 NMR of CFaC1CFCI1CIIzCHICFs






























0U,



















*r *
Figure 53 F19 NMR of CFC1CFClCI2CHIICF3
C





































A B



Figure 54 H1 NMR of CF2C1CFC1CH2CHICFs
B A










TABLE XXII

MASS SPECTRUM OF CF2ClCFClCH2CHICF3

Molecular Weight 376. Isotopes of Cl and I give parent peaks with
M/E 374, 375 376, 378. Listing of peaks with >1% base peak intensity
along with P- peak.

291 213 249
289 355 19 211 I 247
CF2C1 CFCICH2CHICFI2F ClJCF2CFClCH2CHCF3

Nominal Mass % Int. Base Nominal Mass % Int. Base

378 9.6 207 7.5
376 66.0 205 2.1
375 5.0 204 28.3
374 91.7 203 7.3
355 0.7 [>5% Base Intensity]
291 5.5 193 11.6
290 0.7 192 7.8
289 16.3 191 10.3
281 0.8 177 57.6
280 1.1 176 6.9
278 1.6 175 6.1
259 1.4 164 7.6
257 2.7 163 14.5
254 0.9 162 20.6
253 2.9 161 36.2
251 3.9 159 8.8
250 1.3 157 6.9
249 21.1 153 14.7
248 1.9 151 30.6
247 33.1 149 29.1
245 1.0 147 9.3
243 3.1 145 7.9
241 3.3 143 6.1
231 1.7 142 5.0
230 1.9 135 6.6
229 9.8 133 49.7
228 2.8 131 13.6
227 15.9 129 9.4
225 1.2 128 25.0
224 1.1 127 59.6
223 24.1 126 10.9
222 2.1 119 5.2
221 1.3 117 14.8
219 0.9 116 12.5
214 2.5 113 49.5
213 31.6 111 22.7
212 7.9 103 9.7
211 100.0 101 15.0
210 1.4 96 5.7
209 23.9 95 31.6
208 1.7







































0 3600 3 00 2o0 2400 2000 1100 1600 1400 10 0 00 0 600 400
IREQULNCY (OA'')




Figure 55 Infrared Spectrum of CFCI1CFC1CHI-ClICF













































Figure 56 F19 NMR of CF2ClCZFClCH=CHCF,
c B A


% . . . . .






155



TABLE XXIII

MASS SPECTRUM OF CF2C1CFC1CH=CHCF3

Molecular Weight 246. Listing of peaks with >1% base peak intensity
along with M peak.


229
227
ClSCF2CFC1CH=CHCFa IF


Cl
1 126
CFCI CFCH=CHCF3
161
163


Nominal Mass

246
229
227
213
212
211
209
207
193
192
191
179
177
176
175
171
164
163
162
161
157
149
147
145
144
143


% Int. Base

0.1
1.4
2.3
7.4
1.3
23.6
1.0
1.5
1.4
0.6
4.3
0.9
1.5
2.2
2.0
0.6
1.4
32.6
4.6
100.0
2.9
0.9
2.7
2.8
1.0
0.5


Nominal Mass % Int. Base

142 3.0
141 1.0
137 1.5
131 1.1
129 3.1
127 1.0
126 11.3
125 1.4
116 1.2
114 0.9
113 22.1
112 1.0
111 27.1
107 1.8
106 1.6
105 0.6
103 1.4
101 2.0
[>5% Base Int.]
95 5.8
87 7.1
85 19.6
75 6.0
70 10.4
57 8.5











MICROMETERS (pm)


Sf 1213 1410 8 0 25











0m





7- -









4- -------~- Ic-IUIC- CC--i HI IICCII I~- ~ ~ ~ ~ ~ CI~C i



------------


4000 O000 320U 2000 24X) 20U0


1U00( 16UO
FREQUENCY(CM')


Figure 57 Infrared Spuctrum of CF2-(C;FC1C11C13


--


1400 12Jx IWO UU 60) 400


~ -~ - -- -~ --


5











































F F
Figure 58 F19 NMR of D C=CB

F CII=CHCI
C A


1 _~__I___~_




































B A



Figure 59 H1 NMR of CF2=CFCH=CHCF3
B A











TABLE XXIV

MASS SPECTRUM OF CF2=CFCH=CHCF3


Molecular Weight 176. Listing of peaks with >1% base
along with M peak.


126 107
CF2=j CFCH=CHCF2 F


% Int. Base

82.7 o
2.4
1.0
2.0
30.3
1.9
1.3
22.5
4.3
100.0
2.7
2.2
2.9
13.1
10.1
1.0
1.5
3.6
3.2
6.8
2.9
1.7


peak intensity


107 151
CF2=CFCH=CH 2CFJ F


Noninal Mass

76
75
69
68
58
57
56
55
51
50
44
43
42
41
40
39
38
37
32
31
29
27


% Int. Base

3.2
21.3
35.5
1.7
1.4
48.8
13.3
2.2
5.9
1.8
2.4
7.4
3.5
7.1
1.8
1.8
4.4
3.3
24.9
10.6
3.9
2.0


Nominal Mass

176
163
161
158
157
145
138
137
127
126
125
123
113
107
106
105
100
95
93
88
87
83


















II 4

M I T If I::l 4




40W 3400 3200 2800 2400 200 0 0 160 1400 1200 1000 800 00 400
FREQUENCY (CM')


Figure 60 Infrared Spectrum of CC13CF2CFBrCH=CHCH
















































Figure 61 F19 NMR of CCl3CF2CFBrCH=CHCH3
B A


r 1













Figure 62 H1 NMR of CC13CF2CFBrCH=CHCHs
C BA


!E B


d L









TABLE XXV

MASS SPECTRUM OF CCI3CF2CFBrCH=CCHCH

Molecular Weight 319. Listing of peaks with >0.5% base peak intensity.


203
201 151
CICC12 CF2 CFCH=CHCH3
Br


167
C1
C 169 107
CI CCl CF2CFCH=CHJCH3
204 Br 239


CC1 CF CFCH=CHCH3
Br


Nominal Mass

319
285
283
245
244
243
242
241
240
239
225
223
221
219
209
207
206
205
204
203
202
201
199
193
191
189
187
185
184
183
181
179
177
175
173


Nominal Mass


% Int. Base


% Int. Base

No parent peak
0.7
0.5
0.7
0.5
6.1
1.3
16.8
1.3
17.1
0.6
0.8
0.5
0.6
0.9
1.4
1.9
2.8
3.6
16.7
1.0
15.0
1.7
0.5
1.9
2.3
1.0
1.1
0.5
2.6
2.1
0.6
0.6
0.8
1.7


172 0.5
171 2.9
170 1.2
169 6.4
168 2.2
167 2.7
166 1.7
165 1.3
164 1.3
163 1.9
161 0.8
159 0.9
158 1.3
157 2.0
156 1.4
[>5% Int. Base]
133 6.7
131 8.2
129 22.2
122 22.8
121 23.7
119 23.7
117 22.9
109 33.7
108 5.1
107 100.0
102 6.4
101 13.3
95 9.0
91 5.0
83 5.3
77 5.2
75 5.6
72 6.2
71 11.6
69 8.3












..-: . - -- - ---






Si j


000 3600 3200 2800 2400 2000 18600 1600 1400 200 1000 800 600 400
FREQUENCY | CM-'

Figure 63 Infrared Spectrum of CF2CFCH=CHCF3
I I
CF2CFCH=CHCFs

























AA
IB


B C A
Figure 64 F19 NMR of CF2CFCH=CHCF,
I I
CF2CFCH=CIICF3
BC A











TABLE XXVI


MASS SPECTRUM OF



Molecular Weight 352. Listing
along with M peak.


Nominal Mass

352
252
213
207
183
177
176
163
161
158
157
145
137
133
127
126
125
119
114
113
111
107
106
100
95
93
88
85
75
69
57
56
51
44
40
32
31


CF2CFCHCHHCF
CF2CFCH=CHCF3

of peaks with >1% base peak intensity



% Int. Base

0.1 i
1.1
1.5
2.3
5.0
5.2
100.0
8.4
3.2
1.3
24.5
8.1
2.9
1.2
2.7
61.6
1.2
2.1
1.5
3.4
1.1
3.2
1.9
1.2
5.8
1.0
2.0
1.0
6.0
16.2
8.2
1.1
4.5
1.0
1.3
22.0
2.5

































600 3200 2800 2400 00 100) 1600 1400 12~00 1000 800 c00 400
FREQUENCY (CMiI

Figure 65 Infrared Spectrum of CF2CFCII-C1 CF l
I I
Cl CFCIL=clCFs






























B





BCA
Figure 66 F19 NMR of CF2CFCH=CHCF3
I I
CCFCFCI=CHCHs
B C











TABLE XXVII

MASS SPECTRUM OF CF2CFCH=CHCF3
I I
CF2CFCH=CHCG3

Molecular Weight 298. Listing of peaks with >1% base peak intensity
along with M peak.

126 157 176
CF-CFCH=CHCF2(F
CF2-CFCH=CCHCH3
122


Nominal Mass

298
213
211
198
195
183
177
176
175
169
164
163
161
158
157
145
138
137
133
132
129
127
126
125
123
122


% Int. Base

0.1 me
2.5
3.2
1.0
1.2
5.3
4.2
59.2
1.2
1.0
1.0
11.2
13.5
1.6
23.9
7.5
1.0
3.4
1.9
1.1
4.3
4.2
31.1
1.3
6.2
100.0


Nominal Mass

121
119
114
113
111
109
107
106
103
102
101
100
95
93
91
89
87
85
83
77
76
75
72
71
69


% Int. Base

9.4
2.1
1.6
4.7
3.1
2.6
5.4
1.5
2.9
4.4
5.5
1.0
6.7
1.2
3.9
1.2
1.6
2.3
1.1
3.0
1.1
5.6
10.5
5.6
11.7










MICnoMETEnS l(m)


Figure 67 Infrared Spectrum of CF3CH20CF2CF=CHCH2CF3 and CH3CH20CF2CFHCH=CHCFs










-i-. .i.,
i

i
i, I
r
;
;;


BC A
Figure 68 F19 NMR of CH3CH20CF2CF=CHCH2CF,


~~:'L~Y"II-------___-


I iiil . -i iri:l I I . .


1000 1


-


CCLCU~LLI-I~CUI~L~


c~U_














.,D. .C... .. . .
lono





















TMS
III iilllII AiiliI- IlU V J -L J II_


A B DC
Figure 69 111 NMR of CIISClli20CF2CF=CHCI2CF










































40W2 3600 MuO ROOO 2400 2000 1U00 10M .100 1200 1000 00 000 400
WQU0NCY (CM-1)



v I guvc 70 Inofraorcd SpectrumI o[ CllIIrCF=CIIGIICIIrCl (75%) and GVU11rGVH'rCHICII1CE (25Z)






























AA' I
^ -- -~ n I"-'- ~-- -------



C C'




*
Figure 71 F19 NMR of CF2BrCF=CHCHBrCF3 and CF2BrCFBrCH=CHCF3
A C B A' C' B'











TABLE XXVIII

MASS SPECTRUM OF CF2BrCF=CHCHBrCF, and CF2BrCFBrCH=CHCF3


Molecular Weight 336. Listing
along with M .

157
176 107
Br CF2CF=CHCH CF2iF
Br 225
257


Nominal Mass

336
258
257
256
255
238
237
236
235
217
215
211
207
205
193
191
188
186
185
177
176
175
173
163


% Int. Base

0.2
6.1
96.9
6.2
100.0
7.7
2.4
7.7
2.4
0.7
0.5
1.0
8.0
7.8
2.7
3.1
2.5
2.6
0.5
3.3
60.0
4.2
1.3
1.5


of all peaks >0.5% base intensity


Brj CFCF=HCHBrJ CF2F
186


Nominal Mass % Int. Base

162 0.5
161 4.3
160 0.5
158 0.8
157 13.0
156 1.7
155 3.5
[>5% Int. Base]
137 5.9
131 6.5
129 6.7
126 64.1
113 30.1
107 10.0
106 6.5
95 5.4
88 5.5
75 14.4
69 27.5
57 26.4
56 6.8

























I1 I Ii(







4000 3O00 3200 2U00 2400 2000 10U0 1o00 1I00 1200 1000 000 G000 40
FRnQUCNCY(CM'l



Figure 72 Infrared Spectrum of CF2CF=C1lICICF3

N-0

C/
C013










MICROMETERS lmi
6


4000 3600 3200 200 2400 2000 100 1600 1400 1200 1000 800 600 400
FREQUENCY CM'I



Figure 73 Infrared Spectrum of Polymers of Reaction Between CF3NO + CF2=CFCH=CHCFs


































B A


Figure 74 H1 NMR of


BA
CF2CF=CHCHCFs
\ /
N-0
/C
CF%





































CB A
Figure 75 F19 NMR of CF2CF=CHCHCFs
\ /
N-O

CFs
D











TABLE XXIX

MASS SPECTRUM OF CF2CF=CHCHCF3
N--0
/

CFListing of peaks with base peak intensity along ith peak.
Listing of peaks with >1% base peak intensity along with > peak.

126 69
CF2 CF=CHCH I CF,


CF2
R-0

C f{F 256
176
206


Nominal Mass

275
256
206
177
176
168
158
157
156
145
140
130
127
126
125
123
118
114
113
107


% Int. Base

1.3 MP
4.6
12.4
5.4
100.0
1.0
1.2
5.9
6.0
6.9
1.1
2.9
1.8
40.2
1.1
2.2
4.4
2.7
1.3
1.7


Nominal Mass

96
95
91
75
72
70
69
57
51
50
45
44
43
32
31
30
29
28


% Int. Base

1.0
4.1
2.5
4.2
1.6
1.0
62.3
5.0
1.9
1.4
1.9
3.5
1.4
4.3
2.8
2.7
4.7
18.4











































0 36OO 3200 2000 2400 2000 1b00 1600 1400 1200 100 BO 600 400
FKLQULNCY (CM')



Figure 76 Infrared Spectrum of C6H1CF=CFCH=CHCHe











TABLE XXX

MASS SPECTRUM OF CsHsCF=CFCH=CHCH3

Molecular Weight 180. Listing of all peaks >0.5% intensity base
along with M


139 152 165 179
C6HCF=CFfCH=fCHfCH2 H


Nominal Mass % Int. Base Nominal Mass % Int. Base

181 1.0 133 1.2
180 5.6 M 129 1.4
179 3.1 128 4.0
178 2.3 127 3.2
177 0.6 126 2.1
166 0.9 122 11.4
165 6.4 121 7.6
164 1.5 119 1.1
163 0.6 118 6.7
161 0.5 117 3.4
160 1.9 115 5.6
159 0.8 109 1.2
158 0.7 107 5.2
157 0.5 105 4.3
156 1.4 104 1.1
155 13.0 103 2.7
154 100.0 102 3.4
153 40.9 101 1.9
152 27.5 95 1.2
151 7.8 94 7.0
150 2.3 91 3.3
149 0.5 89 2.4
146 1.3 87 1.3
145 5.6 79 2.9
[>1% Int. Base] 78 3.6
139 1.8 77 11.8











MICnOMCETCnS (pm)


FREQUENCY (CM')



Figure 77 Infrared Spectrum of C6HsCF=CFCH=CHCF3































10

B;n~,y?,-r---~ r -


B B C
F F1 F
\ / A /
Figure 78 F19 NMR of C6H,C=CCH=CHCF3 Cis and C6HsC=CCH=CHCF3 Trans
F A
C










TABLE XXXI

MASS SPECTRUM OF CsHsCF=CFCH=CHCF3

Molecular Weight 234. Listing of peaks with >1% base peak intensity
along with l peak.


7 69
CeHs (CF=CFCH=CH CF3
77 165


Nominal Mass

235
234
219
215
214
213
195
193
183
182
175
169
166
165
164
163
162
155
154
153


69
Cs6HCF=CCH=C CF3
145 ~L--
F H
165


% Int. Base


5.4
46.6
1.8
5.2
2.0
6.8
5.4
1.5
1.9
2.8
1.1
2.9
10.4
100.0
48.9
4.7
1.0


Nominal Mass

152
151
146
145
144
143
138
133
127
125
115
82
77


% Int. Base

3.2
5.8
7.6
25.6
2.9
2.8
2.1
4.1
3.4
3.7
9.9
5.4
3.1
3.8
3.6
3.2
7.5
5.1
5.8
29.8









MICFnOMCI Cm (prm)


) 36 3200 2800 2400 20O 150 100 1400 120 100o 8 600 400
FREQUENCYJCM')



Figure 79 Infrared of CF2=CFCH2CHCHs
ICF
CF2=CFCH2CHCiH3








































FREQUcNCY (CM-i)



Figure 80 Infrared Spectrum of CF2C1CFC1CH=CF2





































i C B A



Figure 81 F19 NMR of CF2ClCFClCH2CH=CF2
C A B












TABLE XXXII

MASS SPECTRUM OF CF2-ClCFCICH2CH=CF2

Molecular Weight 230. Listing of peaks with >1% base peak intensity
along with M peak.

193 195
ClfCF2 CF CH2CH=CF2
Cl 77


Nominal Mass

230
228
195
193
177
175
173
163
157
145
143
137
131
129
127
123
116
113
111
108
107
101


% Int. Base

2.1 MP
3.3
1.3
4.4
1.2
1.1
3.2
2.4
2.4
2.4
7.0
1.6
1.2
3.2
3.9
1.2
1.2
4.6
6.0
3.5
1.4
1.0


Nominal Mass

95
93
89
88
87
85
78
77
75
73
69
67
64
58
57
51
45
44
43


% Int. Base

16.1
5.9
1.0
1.3
4.0
10.9
3.3
100.0
4.3
1.3
5.6
2.7
1.0
1.3
5.1
14.8
1.3
1.1
3.6













REFERENCES


1.- P. Tarrant and Earl G. Gillman, J. Am. Chem. Soc., 76,
5423 (1954).

2. P. Tarrant and Marvin R. Lilyquist, J. Am. Chem. Soc., 77,
3640 (1955).

3. P. Piccardi, M. Modena and E. Santoro, J. Chem. Soc. Perkins
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4. H. Muramatsu, K. Inukai, T. Ueda, Chem. Soc. of Japan,
41, No. 9, 2129-2134 (1968).

5. K. L. Paciorek, U. S. Patent 3,067,264 (1962).

6. P. Tarrant and E. C. Stump, Jr., J. Org. Chem., 26,
4646 (1961).

7. P. Tarrant, M. R. Lilyquist, A. M. Lovelace, U. S. Patent
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10. V. P. Sass; T. A. Nadervel; D. S. Rondarev; L. S. Bresler;
and S. V. Sokolov, Zh. Org. Khim., 9(2) 225-8(1973).

11. William H. Sharkey, Fluorine Chemistry Reviews, 2,
1 (1968).

12. D. R. A. Perry, Fluorine Chemistry Reviews, 1, 2,
253 (1967).

13. M. C. Henry, C. B. Griffis, and E. C. Stump, Jr., Fluorine
Chemistry Reviews, 1, 1, 15 (1967).

14. K. Okuhara, J. Am. Chem. Soc., 102:1, 244 (1980).











15. P. Tarrant and J. Heyes, J. Org. Chem., 30, 1485 (1965).

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5095 (1979).

17. A. Fainberg and W. T. Miller, Jr., J. Am. Chem. Soc.,
79, 4170 (1957).

18. M. Hudlicky, Chemistry of Organic Fluorine Compounds,
Ellis Howard Publisher, Chichester, England, (1976).

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20. I. L. Knunyants, B. L. Dyatkin and E. P. Mochalina,
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Doklady Akad. Nauk. SSSR, 124, 1065-8 (1959).

22. V. Dedek and M. Kovac paper at the IXth International
Symposium on Fluorine Chemistry, 030 (1979).

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Chem. Soc., 83, 1767 (1961).

24. R. D. Dresdner, F. N. Tulmac, and J. A. Young, J. Chem.
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Chemistry Reviews, 3, 45 (1969).

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(1960).

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192



35. C. S. Marvel, J. Polymer Sci., 48, 101 (1960).

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BIOGRAPHICAL SKETCH


Jerry Ronald Patton was born March 16, 1946, in Comanche,

Texas. After moving to Arcadia, Florida, at the age of two, he

attended public school in Arcadia, where he graduated from DeSoto

County High School in June, 1964.

He attended the University of Florida where he received his

Bachelor of Science degree in June, 1968. Mr. Patton went to

work with PCR, Incorporated, in July, 1968, working in research

with high density damping fluids. After gaining experience in

silicone and fluorocarbon chemistry, Mr. Patton entered graduate

school at the University of Florida in 1972, while continuing to

work for PCR, Incorporated. Upon receiving his Masters of Science

degree in June, 1974, he continued his employment and started

advance studies toward a Ph.D. degree.

Mr. Patton is married to the former Jonnett Gumm of West

Virginia and has a daughter, Brandi, and a son, Brian.












I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly presentation and
is fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.




Paul Tarrant, Chairman
Professor of Chemisty









I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly presentation and
is fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.




George B. Butler
Professor of Chemisty









I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly presentation and
is fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.




W. S. Brey, Jr.
Professor of Chemist;t












I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly presentation and
is fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.




W. M. Jones
Professor of Chemisty









I certify that I have read this study and that in my opinion
it conforms to acceptable standards of scholarly presentation and
is fully adequate, in scope and quality, as a dissertation for the
degree of Doctor of Philosophy.




ohn E. Singley
Professor of Evironmental
Engineering







This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences
and to the Graduate Council, and was accepted as partial fulfillment
of the requirements for the degree of Doctor of Philosophy.



December, 1980
Dean, Graduate School




Preparation and reactions of partially fluorinated dienes
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 Material Information
Title: Preparation and reactions of partially fluorinated dienes
Physical Description: xii, 193 leaves : ill. ; 28 cm.
Language: English
Creator: Patton, Jerry Ronald, 1946- ( Dissertant )
Tarrant, Paul ( Thesis advisor )
Butler, George B. ( Reviewer )
Brey, W. S. ( Reviewer )
Jones, W. M. ( Reviewer )
Singley, John E. ( Reviewer )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 1980
Copyright Date: 1980
 Subjects
Subjects / Keywords: Diolefins   ( lcsh )
Organic compounds -- Synthesis   ( lcsh )
Addition reactions   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Abstract: The preparation of three fluorine-containing dienes, 1,1,2- trifluoropentadiene-1,3 (I), l,l,2,5,5,5-hexafluoropentadiene-l,3 (II), and 1,4-perfluoropentadiene (III) was carried out. Two asymmetric centers present in the precursors of I and II, CF 2 BrCFClCH2 CHBrCH3 (IV) and CF 2C1CFC1CH2 CHICF 3 (V) , made possible the separation of two diastereomers for each alkane. The dehydrohalogenation reaction of IV and V with ethanolic potassium hydroxide gave exclusively the trans products, CF 2 BrCFClCH=CHCH3 (VI) and CF 2 C1CFC1CH=CHCF 3 (VII) . The products realized by dehalogenation of VI and VII with zinc were the respective dienes I and II. The 1,4- perfluoropentadiene was prepared by the decarboxylation reaction of CF 2 ClCFBrCF 2 CFBrCF2 C00Na to give the olefin CF 2ClCFBrCF2CF=CF2 , which was dehalogenated with zinc to give the diene III. Three types of reactions were studied with the dienes, 2+2 cycloaddition, nucleophilic addition, and radical addition. The formation of a cyclobutane product from I at 0°C indicated the unusual reactivity of this diene. At a temperature of 100°C, both I and II reacted quantitatively in 20 hours to give the respective cyclobutane products. The reaction of a mixture of I and II at 100°C gave an almost statistical distribution of the two homocyclobutane products along with the nixed cyclobutane. The attempt to form cyclobutane products from 1,4-perfluoropentadiene was unsuccessful. Nucleophilic addition reactions using phenylmagnesium bromide and ethanolic potassium hydroxide with I gave the additionelimination product and products formed by 1,2 and 1,4 addition, respectively. Reaction of II with phenylmagnesium bromide resulted in the addition-elimination product. Alcohol added 1,4 to give the ether. Three types of radical initiated reactions were studied with the dienes. Trifluoronitrosomethane reacted with I and II, respectively, to give the Diels-Alder products and polymer products which contained both 1,2 and 1,4 structural units. No reaction took place between III and CF 3N0. The addition of bromine to I gave only the 1,2 adduct. Diene II reacted with bromine to give both 1,2 and 1,4 addition products. 1,4-Perfluoropentadiene reacted with bromine to give 1,2 addition product with no cyclization products detected. Bromotrichlorome thane gave the simple 1 to 1 adduct with diene I and higher teloniers with no 1 to 1 adduct structure for II. Diene III did not react with CCl 3 Br. Eight new compounds were prepared and characterized by infrared analysis, NMR, and mass spectral data.
Thesis: Thesis (Ph. D.)--University of Florida, 1980.
Bibliography: Includes bibliographic references (leaves 190-192).
General Note: Typescript.
General Note: Vita.
Statement of Responsibility: by Jerry Ronald Patton.
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Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000100421
oclc - 07421346
notis - AAL5882
sobekcm - UF00099246_00001
System ID: UF00099246:00001

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PREPARATION AND REACTIONS OF
PARTIALLY FLUORINATED DIENES









BY

JERRY RONALD PATTON


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


1980

















ACKNOWLEDGEMENTS


The author wishes to express his appreciation to Dr. Paul

Tarrant, who directed this research, for his advice and under-

standing.

The author is very grateful to Dr. Wallace Brey and his

research group for assistance in the interpretation of the NMR

spectra and also thankful to Dr. Roy King and Ms. Jackie Dugan

for their able assistance with the mass spectral data.

Thanks are due PCR, Incorporated, for the use of their

equipment and instruments. Many helpful conversations were held

with Dr. Keith Baucom, Dr. Eugene C. Stump, Jr., and Dr. Ralph

De Pasquale of that company.














TABLE OF CONTENTS


ACKNOWLEDGEMENTS

ABSTRACT

LIST OF TABLES

SECTION 1 INTRODUCTION

Preparation of Olefins

Reactions of Olefins

2 + 2 Cycloaddition Reactions

Nucleophilic Reactions

Radical Reactions

SECTION 2 RESULTS AND CONCLUSIONS

Preparation of Olefins

Reactions of Olefins Prepared

Cycloaddition Reactions

Radical Additions

Reactions with Nucleophiles

Conclusions

SECTION 3 EXPERIMENTAL

Preparation of Precursors

Addition of 1,2-Dibromno-2-
chlorotrifluoroethane (CF2BrCFClBr)
to Propene (CH2=CHCH3)

Attempted Reaction of 1,2-Dibromo-
2-chlorotrifluoroethane (CF2BrCFClBr)
with 1,3-Butadiene (CH2=CHCH=CH2)


PAGE

ii

x

viii

1

1

2

2

4

8

13

13

24

24

30

34

44

51

52

52



54










Addition of 1,2-Dibromo-2-chlorotri- 54
fluoroethane (CF2BrCFClBr) to
Trifluoropropene (CF3CH=CH2)

Addition of l,2-Dichloro-2-iodo- 55
trifluoroethane (CF2Cl-CFCII) to
Trifluoropropene (CH2=CHCF3)

Preparation of l-Bromo-2-iodotetra- 56
fluoroethane (CF2BrCF2I)

Addition of l-Bromo-2-iodo- 57
tetrafluoroethane (CF2BrCF2I)
to Ethylene

Preparation of Olefins 57

Attempted Dehydrohalogenation of 57
CF2BrCFClCH2CHBrCH3 with
Aqueous Sodium Hydroxide

Dehydrohalogenation of 58
CF2BrCFClCH2CHBrCH3 with
Potassium-t-Butoxide and
Dimethylsulfoxide

Dehydrohalogenation of 58
CF2BrCFClCH2CHBrCH3 with
Ethanolic Potassium Hydroxide

Dehydrohalogenation of 59
CF2BrCF2CH2CH2I with Ethanolic
Potassium Hydroxide

Dehydrohalogenation of 60
CF2BRCFClCH2CH(CF3)CH2CHBrCF3
with Ethanolic Potassium Hydroxide

Dehydrohalogenation of 60
CF2ClCFClCH2CHICF3 with Ethanolic
Potassium Hydroxide

Decarboxylation of 61
CF2ClCFBrCF2CFBrCF2C00ONa

The Dehalogenation of 61
CF2BrCFClCH=CHCH3 with Zinc











Dehalogenation of 62

CF2BrCFClCH2CHBrCH3 with Zinc

Dehalogenation of 63
CF2BrCFClCH2CH(CF3)CH2CHBrCF3
with Zinc

Dehalogenation of 64
,
CF2ClCFBrCF2CF=CF2 with Zinc

Dehalogenation of 64
CF2ClCFClCH=CHCF3 with Zinc

Dehalogenation of 65
CF2ClCFClCH2CHICF3 with Zinc

Reactions of Olefins Prepared 66

2 + 2 Reactions of Chlorotrifluoro- 66
ethylene with CF2=CFCH=CHCH3

2 + 2 Cycloaddition of 2,2,-Dichloro- 67
difluoroethylene with CF2=CFCH=CHCH3

Dimerization of CF2=CFCH=CHCH3 67

Dimerization of CF2=CFCH=CF3 67

Co-dimerization of CF2=CFCH=CHCH3 68
with CF2=CFCH=CHCF3

Attempted 2 + 2 Cycloaddition of 68
Chlorotrifluoroethylene with
CF2=CFCH2CHBrCH3

Attempted Reaction of Butadiene with 69
CF2=CFCH2CHBrCH3

Attempted Reaction of Butadiene 69
with CF2=CFCH=CHCH3

Radical Addition of Bromotrichloro- 69
methane to CF2=CFCH2CHBrCH3 with
Benzoyl Peroxide

Radical Addition of CCl3Br to 70
CF2=CFCH=CHCH3 Using Benzoyl Peroxide












Radical Addition of CCl3Br with 71
CF2=CFCH=CHCF3 Using Benzoyl Peroxide

2 + 2 Cycloaddition Reaction of 71
Chlorotrifluoroethylene with
CF2=CFCF2CF=CF2

The Addition of Bromine to CF2=CFCF2CF=CF2 71

The Attempted Radical Addition of 2-Iodo- 72
heptafluoropropane to CF2=CFCF2CF=CF2

The Attempted Reaction of Trifluoronitro- 72
somethane with CF2=CFCF2CF=CF2

The Reaction of Ozone with CF2 CFCH=CHCH3 73
CF2 CFCH=CHCH3

The Reaction of Ethanol and Potassium 74
Hydroxide with CF2=CFCH=CHCH3

The Reaction of Ethanol and Potassium 74
Hydroxide with CF2=CFCH=CHCF3

Addition of Bromine to CF2=CFCH=CHCH3 75

Addition of Bromine to CF2=CFCH=CHCF3 76

The Reaction of Trifluoronitrosomethane 76
with CF2=CFCH=CHCH3 at -78C

The Reaction of Trifluoronitrosomethane 78
(CF3NO) with CF2=CFCH=CHCF3 at -78C

The Reaction of Phenylmagnesium Bromide 78
with CF2=CFCH=CHCH3

The Reaction of Phenylmagnesium Bromide 79
with CF2=CFCH=CHCF3

Attempted Reaction of CF2=CFCH=CHCH3 80
with Diethylamine

Reaction of CF2=CFCH2CHBrCH3 with 80
Magnesium

Attempted Reaction of CF2=CFCH=CHCF3 81
with H2SO4 and Water












SECTION 4 ENVIRONMENTAL IMPACT


Explanation of Symbols and Abbreviations 85
for Environmental Impact

REFERENCES 189

BIOGRAPHICAL SKETCH 192

















LIST OF TABLES


NUMBER PAGE

I FLUORINATED STARTING MATERIALS 14

II FLUORINATED OLEFINS FROM 19
CF2BrCFClCH2CHBrCH3

III FLUORINATED OLEFINS FROM THE 25
CF2ClCFClCH2CHICF3

IV FLUORINATED OLEFINS FROM 26
CF2CICFBrCF2CFBrCF2COONa

V 2 + 2 CYCLOADDITION REACTIONS 27

VI RADICAL ADDITION REACTIONS 35

VII NUCLEOPHILIC REACTIONS 41

VIII REACTIONS OF THE 1,1,2-TRIFLUORO- 47
PENTADIENE-1,3

IX REACTIONS OF THE 1,1,2,5,5,5- 49
HEXAFLUOROPENTADIENE-1,3

X REACTIONS OF THE PERFLUOROPENTADIENE-1,4 50
*
XI MASS SPECTRUM OF CF2BrCFClCH2CHBrCH3 92
(BOTH DIASTEREOMERS)

XII MASS SPECTRUM OF CF2BrCFC1CH2CHCH2CHBrCF3 97
CF3

XIII MASS SPECTRUM OF CF2BrCFClCH=CHCH3 104

XIV MASS SPECTRUM OF CF2=CFCH=CHCH3 113


viii











xv

xvi:

xvi:'



XVIII

XIX


Xv

xxi:




Xx"i

xxiii:

XXIV

xxv

xxv'



Xxvi:'



xxviii


XXIX




Xxxx

Xxxi:

xxxi:i:


MASS SPECTRUM OF CF2=CFCH2CHBrCH3

MASS SPECTRUM OF CF2=CFCF2CF-CF2

MASS SPECTRUM OF CF2CFCH=CHCH3
I I
CF2CFCH=CHCH3

MASS SPECTRUM OF CC*,CF2CFBrCH2CHBrCH3

MASS SPECTRUM OF CH3CH2OCF2CFHCH=CHCH3
AND CH3CH2OCF2CF=CHCH2CH3 MIXTURE

MASS SPECTRUM OF CF2BrCFBrCH=CHCH3

MASS SPECTRUM OF CF2CF=CHCHCH3
\ /
N-0
I
CF3

MASS SPECTRUM OF CF2ClCFClCH2CHICF3

MASS SPECTRUM OF CF2ClCFClCH=CHCF3

MASS SPECTRUM OF CF2=CFCH=CHCF3

MASS SPECTRUM OF CC13CF2CFBrCH=CHCH3

MASS SPECTRUM OF CF2CFCH=CHCF3
I I
CF2CFCH=CHCF3

MASS SPECTRUM OF CF2CFCH=CHCF3
I I
CF2CFCH=CHCH3

MASS SPECTRUM OF CF2BrCF=CHCHBrCF3 AND
CF2BrCFBrCH=CHCF3

MASS SPECTRUM OF CF2CF=CHCHCF3
\ /
N--0
I
CF3

MASS SPECTRUM OF C6H5CF=CFCH=CHCH3

MASS SPECTRUM OF C6HsCF=CFCH=CHCF3

MASS SPECTRUM OF CF2-ClCFClCH2CH=CF2


152

155

159

163

166


117

122

126



131


139

142

146
















Abstract of Dissertation Presented to the Graduate Council
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy



PREPARATION AND REACTIONS OF
PARTIALLY FLUORINATED DIENES

By

Jerry Ronald Patton

December 1980

Chairman: Dr. Paul Tarrant
Major Department: Department of Chemistry



The preparation of three fluorine-containing dienes, 1,1,2-

trifluoropentadiene-l,3 (I), 1,1,2,5,5,5-hexafluoropentadiene-l,3

(II), and 1,4-perfluoropentadiene (III) was carried out. Two

asymmetric centers present in the precursors of I and II,

CF2BrCFClCH2CHBrCH3 (IV) and CF2ClCFClCH2CHICF3 (V), made possible

the separation of two diastereomers for each alkane. The dehydro-

halogenation reaction of IV and V with ethanolic potassium

hydroxide gave exclusively the trans products, CF2BrCFClCH=CHCH3 (VI)

and CF2ClCFClCH=CHCF3 (VII). The products realized by dehalogenation

of VI and VII with zinc were the respective dienes I and II. The 1,4-

perfluoropentadiene was prepared by the decarboxylation reaction

of CF2ClCFBrCF2CFBrCF2COONa to give the olefin CF2ClCFBrCF2CF=CF2,

which was dehalogenated with zinc to give the diene III.










Three types of reactions were studied with the dienes, 2 + 2

cycloaddition, nucleophilic addition, and radical addition. The

formation of a cyclobutane product from I at 0C indicated the

unusual reactivity of this diene. At a temperature of 100C, both

I and II reacted quantitatively in 20 hours to give the respective

cyclobutane products. The reaction of a mixture of I and II at

100C gave an almost statistical distribution of the two homo-

cyclobutane products along with the mixed cyclobutane. The attempt

to form cyclobutane products from 1,4-perfluoropentadiene was

unsuccessful.

Nucleophilic addition reactions using phenylmagnesium bromide

and ethanolic potassium hydroxide with I gave the addition-

elimination product and products formed by 1,2 and 1,4 addition,

respectively. Reaction of II with phenylniagnesium bromide resulted

in the addition-elimination product. Alcohol added 1,4 to give

the ether.

Three types of radical initiated reactions were studied with

the dienes. Trifluoronitrosomethane reacted with I and II,

respectively, to give the Diels-Alder products and polymer products

which contained both 1,2 and 1,4 structural units. No reaction

took place between III and CF3NO. The addition of bromine to I

gave only the 1,2 adduct. Diene II reacted with bromine to give

both 1,2 and 1,4 addition products. 1,4-Perfluoropentadiene reacted

with bromine to give 1,2 addition product with no cyclization

products detected. Bromotrichloromethane gave the simple 1 to 1










adduct with diene I and higher telomers with no 1 to 1 adduct

structure for II. Diene III did not react with CC13Br.

Eight new compounds were prepared and characterized by

infrared analysis, NMR, and mass spectral data.

















SECTION 1

INTRODUCTION

Preparation of Olefins



A number of reports has appeared in the literature on the

preparation and reaction of haloalkanes to give fluorine-containing

enes and dienes. Very little information, however, has been made

available on the study of the reactions of 1,1,2-trifluoro-dienes.

Hexafluorobutadiene-l,3, because of its availability, has been

historically the most studied of the fluorine-containing diene

compounds. Examples of polymerization reactions involving homo-

polymers, co-polymers, and ter-polymers of hexafluorobutadiene-l,3

are prevalent in literature reports.

The preparations of fluorine-containing dienes have been

reported by several groups.1-3 A general method for the preparation

of these compounds can be shown as follows:



1. XCF2CFYZ + CH2=CHR --> CF2XCFYCH2CHZR

X = Cl, Br; Y = Cl; Z = Br, I; R = CH3, CF3
KOH *
2. CF2XCFYCHCHZR EtOH > CF2XCFYCH=CHR


CZinc
3. CFXCRYCH=CHR > CF2=CFCH=CHR
CF2XRYCHGHR EtOH









The free radical addition reactions, involving halogen-containing

compounds to olefins, have been used extensively to prepare fluoro-

alkanes.1'2'4-10 The dehydrohalogenation is facilitated with

potassium hydroxide and ethanol since the adjacent halogens cause the

hydrogen to be more acidic than in hydrocarbon surroundings.

Dehalogenation with zinc in ethanol is common for the preparation

of fluorinated olefins.

The usual reactions of fluoroalkenes such as halogen addition,

radical initiated additions, nucleophilic attack, and 2 + 2 cyclo-

additions, have not been thoroughly studied for 1,1,2-trifluoro-

dienes. The lack of activity in this area prompted our research.



Reactions of Olefins

2 + 2 Cycloaddition Reactions

Fluorinated olefins usually give 2 + 2 cycloaddition products

when treated thermally as shown below:


A
4. CF2=CFX > CF2-CFX
I I
CF2-CFX

X = Cl, F, Br, I, OCH3, etc.



The 2 + 2 cycloaddition reaction has been mechanistically shown to

be a two-step bi-radical process.11











5. CF2=CFX -> CF2-CFX CF2-CFX
I > __
CF2-CFX CF2-CFX

X = F, Cl, Br, I, OCH3, etc.



Those olefins which are very reactive in forming 2 + 2 cyclo-

addition products usually give no 2 + 4 Diels-Alder products.

For example, tetrafluoroethylene reacts with butadiene to give only

the vinylcyclobutane.11



6. CF2=CF2 + CH2=CH-CH=CH2 > CH2-CH-CH=CHz
I I
CF2-CF2



Diels-Alder products are only isolated from reactions where the diene

is locked into a cisoid configuration such as cyclic dienes. Cyclo-

pentadiene is one of the few dienes which form Diels-Alder products

with fluoroolefins. A good review of Diels-Alder reactions of

organic fluorine compounds can be found in Fluorine Chemistry Reviews,
!
Vol. 1, No. 2.12

Hexafluorobutadiene-l,3 has been described as acting neither as

the diene nor dienophile in a Diels-Alder reaction.



7. CF2=CF-CF=CF2 -> CF2-CF-CF=CF2
I I
CF2-CF-CF=CF2










The only product isolated as the 2 + 4 Diets-Alder adduct with

this diene has been that derived from trifluoronitrosomethane.

Trifluoronitrosomethane has been reported to react with fluorinated

dienes via a radical anion mechanism, probably involving
0.
CF3N(0)N(0)-CF3.13 The reaction with hexafluorobutadiene-l,3 gives

the 2 + 4 Diels-Alder adduct along with polymeric products.


8. CF3NO + CF2=CFCF=CF2 -> CF2-CF=CF-CF2

N--O0 + 1,2 and 1,4

CF3 polymer



The study of 2 + 2 cycloaddition reactions of fluorine-containing

dienes, other than hexafluorobutadiene-l,3, has been neglected by

previous workers.


Nucleophilic Reactions

Most reactions involving fluorine-containing olefins are

nucleophilic in nature, due to the stabilization of the anion by the

halogen atoms in the a or R-position. Hydrocarbon and partially

fluorinated olefins undergo electrophilic reactions because of

stabilization of the intermediate positive charge. The higher the

degree of fluorination the more likely the nucleophilic reaction to

predominate, as the example shows.


E) 10
9. CF2=CH2 + IP -> CF2-CH3 > CF3-CH3


CF3 CF3 CF3
C=CF2 + F-' -> CF3 --> CH-CF3

CF, CF3 CF3










Fluorine-containing olefins are very susceptible to attack by nucleo-

philes such as Grignard reagents, alkoxides, and halide anions.14-17

Examples of these reactions are as follows:



10. RMgX + CF2-CFR' -> RCF=CFR' + MgXF



11. R(P + CF2=CF2 ROH > ROCF2CF2H + ROCF=CF2



12. MF + CF2=CFR' -> CF3-CFR' + 12 -> CF3CFIR' + MI

IP

R = alkyl, aryl

R' = F, Cl, Rf, etc.

M = Na, K, Cs



The reactivities toward nucleophiles of dienes which contain

fluorine vary. Tarrant and Heyes15 found that Grignard reagents

such as allylmagnesium bromide did not react with fluorinated

dienes such as l,l,2-trifluoropentadiene-l,4. The usual reaction

of Grignard reagents gives the olefin by loss of fluoride ion.

The addition-elimination or SN2' type reaction of Grignard

reagents with fluorinated olefins is well documented.18 Rearrange-

ments of the intermediate anion have been reported,19 with the

conjugated olefin predominating where possible.



13. C6HsMgBr + CF2=CFCF2CI --> C6H5CF=CF-CF2CI predominant

and product

C6HsCF2-CF=CF2










CF2CI
14. C6HsMgBr + CH2=C F2Cl
ICF2Cl


,CF2CI
_____ C6HCH2-C0
-> CF2


and

CF2CI
CH4-CH2-C0
kCFC1


The reaction of alkyl Grignard reagents with olefins which

contain fluorine has been shown by Okukara14 to give two products.


15. CH3CH2MgX + CF2=CC12


-- > CH3CH2-CF2-CCl2H + CH3CH2-CF=CCI2

predominant product


A radical intermediate, not hydrolysis of the intermediate

CH3CH2CF2CCI2MgX, was proposed to account for the formation of the

major product.

Nucleophiles such as ethoxide (CH3-CH2-CA have been added

to hexafluorobutadiene-l,3 to give several products depending on

reaction conditions. Knunyants et al.20'21 reported the following

sequence:



16. CH3CH2OH + CF2=CFCF=CF2 (C2H5)3N > CF2=CFCFHCF2OCH2CH3
R.T.

P 1 1,2 adduct


CF3-CF=CHCF2OCH2CH3









The allylic rearrangement of the fluoroether was unexpected

for this type of unsaturated compound, but it was probably caused by

the attack of fluoride anion, obtained from the partial hydrolysis

of the ether, followed by the rearrangement and loss of fluoride.

The same group also found that at higher temperatures, 90-100C,

the 1,4 addition product was obtained.


17. CHCHH + CF2=CFCF=C (C2Hs)3N > CH3CH2OCF2CF=CFCF2H
17. CH3CH20H + CF2=CFCF=CF2 90-1000C

1,4 adduct



Dedek and Kovac22 reported the following results from the reaction of

ethanol and sodium ethoxide with hexafluorobutadiene-l,3.



18. CHCH20H + CH3CH2ONa + CF2=CFCF=CF2 ->

CH3CH2OCF2CF=CHCOOCH2CH3



Their product probably arose by the following reactions.



19. CF2=CFCF=CF2 + CH3CH20H CH3CH2ONa > CH3CH2OCF2CFHCF=CF2



20. CHCH2OCF2CFHCF=CF2 + CH3CH20H -> CH3CH2OCF2CFHCFHCF2OCH2CH3

-HF
21. CH3CH2OCF2CFHCFHCF2OCH2CH3 -HF> CH3CH2OCF2CF=CHCF2OCH2CH3

I hydrolysis

CH3CH2OCF2CF=CHCOOCH2CH3










The various results were ascribed to temperature dependence and

base strength differences. The addition of alcohols to fluorine-

containing conjugated triene systems has also been studied by Dedek

and Kovac22 and results in addition-elimination reaction to give

the a,o-triene diether.



22. CF2=CFCF=CFCF=CF2 + CH3CH20H + CH3CH20Na ->



CH3CH20CF=CFCF=CFCF=CFOCH2CH3



The study of nucleophilic attack on fluorinated 1,1,2-trifluoro-

diene systems has not been reported except for isolated cases such as

fluoride anion induced rearrangement of perfluorinated compounds.23'24



23. CF2=CFCF=CFCF3 + CsF --> CF3C CCF2CF3



Radical Reactions

Halogen atoms are added to the double bonds of fluorinated

olefins by radical means.24 Electrophilic ionic additions such as

occur in hydrocarbon olefins are rare but do occur in olefins

which contain both hydrogen and fluorine. In the fluorine-

containing 1,1,2-trifluoro-dienes we propose to study, two products

can be formed.










24. CF2=CF-CH=CHR + Br2 -> CF2Br-CFBr-CH=CHR 1,2 adduct

and

CF2Br-CF=CH-CHBrR 1,4 adduct

R = CH3, CF,



Study of halogen addition to fluorinated conjugated dienes has

been limited to selected dienes such as hexafluorobutadiene-l,3,

1,l,2-trifluorobutadiene-l,3, and 1,1,2,4-tetrafluorobutadiene-l,3.

Rondarev et al.25 proposed an ionic mechanism in the bromination

of the selected dienes. From hexafluorobutadiene-l,3, the (E)-l,4-

dibromoperfluoro-2-butene was formed exclusively.



25. CF2=CFCF=CF2 + Br2 -> FC CCF2Br
CF2Br- V F



The 1,4-addition product was also obtained in the reaction

of iodine monochloride with the butadienes and an ionic mechanism

was proposed.25



26. IC1 + CF2=CF-CH=CH2 -> CF2ClCF=CHCH2I



A good review of reactions between fluoroolefins and electrophiles

can be found in Fluorine Chemistry Reviews, Vol. 3.26

Other results involving hydrocarbon radical reactions with

fluorinated dienes have shown that dienes such as hexafluorobuta-

diene-l,3 are more reactive than mono-olefins. The difference in










reactivity, however, is not so great as in the corresponding

hydrocarbon systems. Sass et al.10 found the reactivity of radicals

with fluorinated olefins to decrease according to the following

substitution pattern: CF2=CF2 > CF2=CFOR > CF2=CFR. He carried
f.

out the addition of methane to the alkenes by the reactions shown

below:

0 0 0
II P, A II -C02
27. CH3-C-0-0-C-CH3 > 2CH3-C-0 > 2 *CH3



28. *CH3 + CF2=CFR -> CH%-CF2-CFR


CH3
29. CH3CF2-CFR + CH3-CH-CH2-CH2CH2CH2CH3 -- > CH3CF2CFHR

R = F, OR or Rf




Halogen addition reactions and polymerizations are the only

types of radical reactions which have been reported for conjugated

1,1,2-trifluoro-dienes except for the isolated case where Muramatsu

added bromotrichloromethane to CF2=CFCH=CH2.8

Muramatsu.and Tarrant8 studied the radical addition of bromo-

trichloromethane to 1,1,2-trifluorobutadiene and the non-conjugated

l,l,2-trifluoropentadiene-l,4. The attack on the hydrocarbon

segment of the dienes was unexpected.



30. CCl3Br + CF2=CFCH=CH2 -> CCI3CH2CH=CFCF2Br and polymer by

1,4 addition










31. CCl3Br + CF2=CFCH2CH=CH2 --> CC13CH2CHBrCH2CF=CF2

and

CCl3CH2CHBrCH2CFBrCF2CC13



Polymerization of conjugated dienes gives polymers of both

1,2 and 1,4 structure. The polymerizations proceed by a radical

mechanism.27'28




32. CF2=CFCF=CFCF3 --> -fCF2CF*
I n
CF
II
CF
I
CF3 CF3

and -fCF2CF=CFCF]-



Non-conjugated perfluorodienes are reported to give intramolecular

cyclic polymers.29-35



33. CF2=CFCF2CF=CF2 -A> -CF2CF-CF2
I I
CF2CFI n




According to Muramatsu et al.4 even hindered partially fluorinated

pentadienes such as 2-methyl-3,4,5,5,5-pentafluoro-l,3-pentadiene

polymerized to give both 1,2 and 1,4 polymer structures. Muramatsu

obtained polymers which contained both vinyl side chains and double

bonds in the backbone of the polymer.











CF3
CF
I I
CH3 CF
34. CH2=C-CF=CFCF3 --> CH2C --
CHu n 1,2 polymer

CH3

and H2-C=CF-CF 1,4 polymer
CF3 n




A study.of the reactions of 1,1,2-trifluoro-dienes with

radicals and nucleophiles, and in cycloaddition reactions, was

begun to extend our knowledge in this area.

The recent concern for environmental considerations prompts

the environmental impact study at the end of the Experimental

Section. Each chemical used is listed with its NIOSH registry

number and available toxicity data. Due to the small scale and

research quantities of chemicals prepared, no detrimental effect

on the environment was expected.

















SECTION 2

RESULTS AND CONCLUSIONS



A study of the reactions of three 1,1,2-trifluoropentadienes

has been carried out. The results of radical reactions, nucleophilic

reactions, and 2 + 2 cycloadditions will be presented.



Preparation of Olefins

The three systems chosen for study were 1,1,2-trifluoropentadiene-

1,3 (CF2=CFCH=CHCH3, I), l,l,2,5,5,5-hexafluoropentadiene-l,3

(CF2=CFCH=CHCF3, II), and 1,4-perfluoropentadiene (CF2=CFCF2CF=CF2,
*
III). Two asymmetric centers are present in both CF2BrCFClCH2CHBrCH3

and CF2C1CFClCH2CHICF3 and only the trans olefins were obtained by

dehydrohalogenation. For these reasons the preparations of the

respective olefins, CF2BrCFClCH=CHCH3 and CF2ClCFClCH=CHCF3, and

dienes CF2=CFCH=CHCH3 and CF2=CFCH=CHCF3, are treated separately.

Reactions and conclusions will be discussed together to show the

similarities and differences of the various dienes. Table I contains

the fluorinated starting materials used in olefin preparation.

The first diene studied was l,l,2-trifluoropentadiene-l,3

(I), which was prepared by the method of Tarrant and Gillman.1 The

following reaction scheme shows the sequence and yields of the

various reactions:















"Eli




30 -4 H ::

C11 w Q Q


'o
Cq
a) C







H 0 0 0 0) 0 60



1-4
H- 0 cC Cfl c0c-
!> m C4 00 LfO 0M
bl^


1-1







NO
jfl


L 0










In oC
r- ON


+ Cn 0





,--I ~ ~ r r=4. z ,-
0 U 0Q U a u
r a u u V)
) u C i ) 9
+II II I I II .
N U 0 N A
N 4 r-q
$-I N C 0 C.) 0) 41J
pq H X F4C
W + + + C
+ C4
+ r4 t4 $ +
+ m c m w H
H H $4 -4 z
HX C N U u H r C) 0
C) N p.Li F14 r-i p. 0 t- Z
~~p $4 C) C) C C C
pq mi U pq U
M CA ( $4 Hi N 0 -4 0
II II M P~ U) C II U) C
N N N N N4 N N N nI
rX4 44r4 4Z4 44 44 r=4 ;:4 r4
) u U u L) C) u u U


U u
C) 0 0
0o cc1 i'


oo r C. o
r r- o
-4 r-


r-1
U


*1CU
N

'ci N a
0 4


N NN
r0 1 M rX1
0 pl p p
a, m pq Mq

u 0- C-) u-


u

o D-
\o ,'i


'-'0o


m
rZ4

Cd


N N
o a
u 0




r$40
H ^s
N l U


r-i pq ^-
a L) -KU



C) N N
U U C

N pq U


rX 4 rZ4


C) Cu U)


I I
o o



-1 -1


C-) L
P.
N







C-) K
ri



.-4 -4
O I0
N U
*uL
'-
a- C


HA z
H








z
MH





0


r,-1 ( o
-H -H H
0 0 O0
PQ P4|


-- /-4





41 1 41'
p. w $
-4 I-
SJ U L)










C)UL
II II II
N N N










"a Q
000
0 0 0
P 14 _



00 0








.L~i Li 4
$-1 -I 4-)
^ -1~. )-1
00 0








c a) En
p-i -i co
3J 3


0 0 0











:r-4 :
C1 l) a










Reaction Scheme 1



autoclave *
1. CF2BrCFClBr + CH2=CHCH3 peroxide > CF2BrCFClCH2CHBrCH3
peroxide

80% yield of two diastereomers



KOH *
2. CF2BrCFClCH2CHBrCH3 EtOH > CF2BrCFClCH=CHCH3

88% trans olefin only


Zinc
3. CF2BrCFClCH=CHCH3 Znc> CF2=CFCH=CH3 92%
EtOH



Tarrant and Gillman1 did not report the presence of two

diastereomers in the products obtained in reaction 1. Their
,
yield in step 2 was 45%. The trans geometry of CF2BrCFClCH=CHCH3

obtained in step 2 was not discovered by these workers. Our

procedure gave a three-fold increase in yield for the diene (I).

The two diasteromers from Step 1 were isolated on a 40-plate

Oldershaw column. Each gave the same mass spectrum. However, NMR

analysis indicated the components to be the two diastereomeric

products.

In step 2, a reported yield of 45% was expected.1 A much higher

yield of 88% was realized from the mixed diastereomers, but the

yield decreased rapidly with other impurities present. The NMR

analysis also indicated only one isomer, the trans olefin, to be

present. Space-filling models readily explained the exclusion of

the cis olefin from the product. The presence of the chlorine and

the CF2Br group on the 0 carbon prohibits free rotation of the CHBr









moiety. Trans elimination, being favored, gives only the trans olefin

from both the R and S configuration about the asymmetric CHBr center.


CFClCF2Br


1 rotation
for trans CH
CH 3 H elimination C3

CFClCF2Br

Preferred S

configuration









CF2BrCFCl


Preferred R

Configuration


rotation
for trans
elimination


KOH
EtOH


CF2BrCFCl .H
C=C
H CH3

trans product


Br

H



H
H











Br

CF2BrCFCl H


H CH3

H












KOH CF2BrCFClI H
EtOH H CH3




The size of the CF2BrCFCl group does not allow rotation to place

this group between the bromine atom and methyl group, therefore; no

cis product was formed. Two possible olefins were expected from the

dehydrohalogenation of CF2BrCFClCH2CHBrCH3.


KOH *
4. CF2BrCFClCH2CHBrCH3 EtOH> CF2BrCFClCHCHCH3

and

CF2BrCF=CHCHBrCH3




That the only product isolated was CF2BrCFClCH=CHCH3 was attributed

to the greater leaving ability of bromine compared to chlorine. In

contrast, Piccardi et al.3 reported the ethanolic potassium
*
hydroxide dehydrohalogenation of CF3CFBrCH2CHBrCH3 to give both

olefins.



KOH *
5. CF3CFBrCH2CHBrCH3 -EtOH> CF3CF=CHCHBrCH3

and

CF3CFBrCH=CHCH3


*k *k
The attempted dehydrohalogenation of CF2BrCFClCH2CHBrCH3
using aqueous (50%) sodium hydroxide was carried out at 80C. The

two materials were immiscible and no reaction was detected over a









JL *
one-hour period. Reaction of the alkane, CF2BrCFClCH2CHBrCH3, with

potassium t-butoxide in dimethyl sulfoxide gave the desired olefin,

CF2BrCFClCH=CHCH3, in 73% yield. Of the three reagents, ethanolic

potassium hydroxide gave the best yield and purest crude product.

The reaction of CF2BrCFClCH2CHBrCH3 with zinc was carried out to give

CF2=CFCH2CHBrCH3 as an alternate precursor to CF2=CFCH=CHCH3. The

yield in this reaction, 79%, was not as good as that from

CF2BrCFClCH=CHCH3.

The dehalogenation in step 3 was reported to give a 60% yield
*
with CF2BrCFClCH=CHCH3. A 92% yield was realized from the pure
*
trans olefin. The products prepared from CF2BrCFClCH2CHBrCH3

along with the preparation method, yield, and boiling points

are reported in Table II. Each product was completely identified

by infrared, NMR, and mass spectral analysis.

NMR and mass spectral data for each diastereomer prepared in

Step 1, and each of the olefins obtained are presented in the

Experimental Section. Infrared spectra are given for all starting

materials as well as the reaction products.

After being stored at 0C for 20 days, the diene had reacted

to give the cyclobutane derivative and a white granular polymer.



6. 2 CF2=CFCH=CHCH3 --> CF2CFCH=CHCH3 + polymer
I I
CF2CFCH=CHCH3








19






0n



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S$4 $4 4 1-i


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rx-P-


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u Uu










A higher reaction temperature is usually required for 2 + 2

cycloaddition reactions. Chlorotrifluoroethylene does not form

the cyclic dimer below 175C and even activated fluorocarbon olefins

require a temperature of 100C for extended periods of time. The

remaining reactions of l,l,2-trifluoropentadiene-l,3 were carried

out on freshly prepared and distilled diene. These reactions will

be reported after procedures for the preparation of the remaining

dienes have been described.

To acquire information on fluorocarbon compounds which contain

iodine, l-bromo-2-iodotetrafluoroethane was prepared and added to

ethylene. The butane was converted to the olefin by the following

reaction scheme.



Reaction Scheme 2



1. CF2=CF2 + Br2 + 12 Autoclave> CF2BrCF2Br (31%) +



CF2BrCF2I (49%) + CF21CF2I (20%)


benzoyl>CFrCCHC1 68
2. CF2BrCF2I + CH2=CH2 benzoyl > CF2BrCF2CH2CH2I 68%



KOH
peroxide



3. CF2BrCF2CH2CH21 EtOH > CF2BrCF2CH=CH2 76%



The reaction of ethylene with the iodide, CF2BrCF2I, was

found to take place thermally at 150C in four hours to give the

desired adduct. The discovery of this fact in the preparation of

the precursor for l,l,2,5,5,5-hexafluoropentadiene-l,3 was fortuitous.









An attempt to prepare l,l,2,5,5,5-hexafluoropentadiene-l,3 (II)

was made. The reaction of 1,2 dibromo-2-chlorotrifluoroethane

with trifluoropropene was carried out using the same procedure as

with propene. The only product isolated, however, was the adduct

containing two moieties of trifluoropropene. This result can be

attributed to the presence of the CF3 group adjacent to the carbon

containing the unpaired electron, which stabilizes this radical,

CF2BrCFClCH2CHCF3, and makes it less reactive than
0
CF2BrCFClCH2CHCH3. Tarrant and Lilyquist2 also noted the relative

inability of CF3CH=CH2 to form 1 to 1 adducts with CF2BrCFClBr.



CF2BrCFClBr + CF3CH=CH2--> CF2BrCFCl CH2CH --CH2CHBrCF3
I
CF3 n



n = 1, 2, 3, etc.



Higher molecular weight components were also obtained but

not isolated. The following sequence for the formation of the

2 to 1 adduct is proposed.



CF2BrCFClBr + CF3CH=CH2 benzoyl *
peroxide CF2BrCFClCH2HCF3

I + CF3CH=CH2

CF2BrCFClBr F CH
CF2BrCFClCH2CHCH2CHBrCF3 CF2BrCFClCH2CHCH2CHCF,
3 3
CF3 CF3










A diene was formed by the reaction of zinc on the octane

above. It was identified by NMR, infrared analysis, and mass

spectral data as CF2=CFCH2CHCH2CH=CF2. The formation of a CH=CF2

CF3

group with zinc was not expected since Tarrant and Keller36-showed

that coupled and reduced products predominated with fluorinated

compounds containing iodine.


CF3CF3
Zinc I I
CF3CFICF3 C >CO CF3CFHCF3 and CF3C-C-CF3
CF3COOEt I I
F F




The successful preparations of the desired 1,1,2,5,5,5-hexa-

fluoropentadiene-l,3 was carried out following the sequence described

by Tarrant and Lilyquist2 as shown in reaction scheme 3.



Reaction Scheme 3


150C *
1. CFClCFClI + CH2=CHCF3 4hor> CF2ClCFClCH2CHICF3 80%
4 hours


KOH *
2. CF2ClCFClCH2CHICF3 EtOH > CF2ClCFClCH=CHCF3 70%


trans only


Zinc
3. CF2ClCFClCH=CHCF3 EtOH > CF2=CFCH=CHCF3 80%









Two diastereomers of CF2ClCFClCH2CHICF3 were obtained from

the addition reaction, step 1. Dehydrohalogenation gave only the
*2
trans olefin, CF2ClCFCICH=CHCF3, in step 2. Tarrant and Lilyquist2

did not report two diastereomeric products in step 1, or the

exclusive trans geometry for the olefin obtained in Step 2.

Comparable yields were obtained by our procedures. The loss of the

bulky iodine is greatly favored over the loss of chlorine and with

iodine being a better leaving group, the product was exclusively

the trans olfein. The trans geometry in the olefin has been
*
previously explained for CF2BrCFClCH=CHCH3 formation from

CF2BrCFClCH2CHBrCH3. The l,l,2,5,5,5-hexafluoropentadiene-l,3,

obtained in step 3, was purified on a 25-plate Oldershaw column

and the correct boiling point was found to be 43-44C instead of

50C as reported by Tarrant and Lilyquist.2 The sample boiling at

50C was found to contain 92% of the desired diene and 8% of

CF2ClCFClCH=CHCF3.

The dehalogenation of CF2ClCFClCH2CHICF3 with zinc in

ethanol gave an interesting new olefin.


Zinc *
CF2ClCFClCH2CHICF3 EtOH > CF2ClCFClCH2CH=CF2




> CF2=CFCH2CHICF3



The olefin was identified by the difluorovinyl absorption in the

infrared (5.670) and F19 NMR data. Mass spectral analysis gave the










molecular ions for the two chlorine system and a cracking pattern

identifying the olefin unequivocally. The expected product,

CF2=CFCH2CHICF3, was not found. The list of olefins prepared from

CF2ClCFClCH2CHICF3 is given in Table III.

The final pentadiene prepared was 1,4-perfluoropentadiene using

the reaction sequence reported by Fearn et al.30 as shown below.



Reaction Scheme 4


heat *
1. CF2ClCFBrCF2CFBrCF2COONa > CF2ClCFBrCF2CF=CF2 70%


2. Zinc > CF2=CFCF2CF=CF2 75%
2. CF2ClCFBrCF2CF=CF2 EtOH



Our synthesis gave comparable yields to that of Fearn et al.30

Each of the compounds was identified by infrared analysis, NMR, and

mass spectral data. Table IV gives the pertinent data concerning

the compounds involved in the preparation of 1,4-perfluoropentadiene.



Reactions of Olefins Prepared

Cycloaddition Reactions

The 2 + 2 cycloaddition reaction of the three fluorine-containing

pentadienes was studied using both fluoroolefins and fluorodienes as

well as butadiene itself. Table V shows the reactions carried out

in this study. The only 2 + 2 cycloaddition products isolated

were from the conjugated pentadienes reacting with themselves or each

other.























































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00
CF2=CFCH=CHCH3 --> CF2-CF-CH=CHCH3
I I
(I) CF2-CF-CH=CHCH3


CF2=CFCH=CHCF3 A- > CF2-CF-CH=CH-CF3

(II) CF2-CF-CH=CH-CF3



CF2=CFCH=CHCF3 CF2CFCH=CHCH3 CF2CFCH=CHCF3
I I + I I
(II) CF2CFCH=CHCH3 CF2CFCH=CHCF3
A
+ --> 30% 20%

CF2=CFCH=CHCH3 +

(I) CF2CFCH=CHCH3
I I
CF2CFCH=CHCF3

45%



The mixed cyclobutane was observed along with the two expected

homocyclobutane products when a mixture of the 1,1,2-trifluoro-

pentadiene-l,3 and l,1,2,5,5,5-hexafluoropentadiene-l,3 was

allowed to react.

The relative amounts of the cyclobutane products are almost a

statistical distribution suggesting the two dienes have the same

order of reactivity.

The attempted reaction of other olefins, CF2=CFCl, CF2=CCl2, and

CH2=CHCH=CH2 with the 1,1,2-trifluoro-dienes resulted in cyclo-

butane products containing only the 1,1,2-trifluoro-diene molecules.









CF2=CFCH=CHCH3 + CF2=CFC1 7/-> CF2CFCH=CHCH3
I I
(I) CF2CCI


-> CF2CFCH=CHCH3
I I
CF2CFCH=CHCH3



We conclude that the reactivity of the 1,1,2-trifluoro-dienes in

forming 2 + 2 cyclobutane products is much greater than fluorinated

olefins such as CF2=CFCl.

Fluorocarbon dienes react to give cyclobutane products both

intra and intermolecularly. The thermal reaction of perfluoro-

hexadiene-1,5 has been reported to give the intramolecular 2 + 2

cycloaddition product.37

A
CF2=CFCF2CF2CF=CF2 > CF2CFCF2
I I I
CF2CFCF2



In general the reaction conditions for 2 + 2 cycloaddition

reactions are rather harsh, i.e, temperatures exceeding 200C for the

cycloaddition reaction to predominate. The substituent effect is

noteworthy since ethers, CF2=CFOR, react more readily than vinyl

alkanes or perfluorinated olefins in the preparation of cyclobutane

products. The formation of a cyclobutane product from

CF2=CFCH=CHCH3 (I) at 0C was totally unexpected. Literature

accounts gave no indication of any olefins undergoing a 2 + 2










cycloaddition at such mild conditions. The stabilization of the

proposed biradical intermediate coupled with the conjugated

system is credited with this result.



CF2CFCH=CHCH3 < CF2CF=CHCHCH3
I <-->I .
CF2CFCH=CHCH3 CF2CFCH=CHCH3

4'I

product



In none of the reactions was any cyclohexene products isolated

thus indicating that no 2 + 4 Diels-Alder addition had occurred.

The conjugated fluorinated pentadiene systems react preferentially to

give 2 + 2 cycloaddition products.

The activation of the trifluorovinyl moiety by conjugation

of a hydrocarbon olefin is very evident in the 2 + 2 cycloaddition

reactions. Note should be taken of the decreased reactivity of
,
CF2=CFCH2CHBrCH3 as compared to that of both CF2=CFCH=CHCH3 and

CF2=CFCH=CHCF3. 1,4-Perfluoropentadiene, moreover, showed no

activity towards this type of reaction as none of the cyclobutane

product was found.



Radical Additions

A study was made of the reaction of the three dienes with

trifluoronitrosomethane (CF3NO), with bromine (Br2), and with bromo-

trichloromethane (CCl3Br) in the presence of benzoyl peroxide.










Trifluoronitrosomethane is reported to react with fluorinated

olefins by a radical anion mechanism.22 Both partially fluorinated

dienes, l,l,2-trifluoropentadiene-l,3 (I) and 1,1,2,5,5,5-

hexafluoropentadiene-l,3 (II) gave 2 + 4 Diels-Alder type products

with CF3NO as well as polymers in which 1,2 and 1,4 addition structures

were observed. The polymer was isolated and analyzed by

infrared analysis. The spectrum showed absorptions at 5.65p

and 5.82p, indicative of both 1,2 and 1,4 structures.


CF3NO + CF2=CFCH=CHR -- > CF2CF=CHCHR
\ I
N-- 0
I
CF3



{ --NO-CF2CF=CHCH--
I I
CF3 R n

The 1,4 polymer structure

R = CH3, CF3



+ --NOCF2CF--
I I
CF3 CH n

CH

R
The 1,2 polymer structure










The Diels-Alder products obtained from the reaction of

trifluoronitrosomethane with I and II were not unexpected

since hexafluorobutadiene-l,3 gives the 2 + 4 cycloaddition

product from the reaction with trifluoronitrosomethane.13

Stabilization of the intermediate radical anion by resonance

would explain the 2 + 4 cycloaddition result.

0
CF3NO + CF2=CFCH=CHR > CF2CF=CH.--CHR
I
N-O*
iCF3
I

R = CH3, CF3 *

CF2CF=CHCHR
\ /
N- 0
I
CF3



The 1,4-perfluoropentadiene did not react with CF3NO either at

-78C or room temperature.

We consider halogen addition to be a radical process for

fluorine-containing dienes. Two of the three dienes do contain

hydrocarbon segments and we would expect addition to the hydrocarbon

segment if the halogen addition were an electrophilic process.

The actual product obtained was formed by addition to the CF2=CF

moiety. The process is described by the following sequence.









CF2=CFCH=CHR + Br2 -> BrCF2FCH=CHR

'I
BrCF2CFBrCH=CHR

R = CH3, CF3 1,2 addition product



CF2=CFCH=CHR + Br2 -> BrCF2CF=CHCHR

1I
BrCF2CF=CHCHBrR

1,4 addition product



The l,l,2,5,5,5-hexafluoropentadiene-l,3 gave both addition

products with bromine while l,l,2-trifluoropentadiene-l,3 gave only

the 1,2 addition product. If the addition had been electrophilic

in nature, the l,l,2-trifluoropentadiene-l,3 would have been

expected to yield the 1,4-addition product. These results are in

accord with the findings of Rondarev et al.25 who report the addition

of iodine monochloride to CF2=CFCH=CHCF3, a fluorine-containing

1,3-pentadiene, gave the 1,4 addition product, while P. Brown et al.33

found halogen addition to 5,5,5-trifluoropentadiene-l,3 to give both

1,2 and 1,4 addition.



CF3CH=CHCH=CH2 + Br2 -> CF3CHBrCH=CHCH2Br 1,4 addition

CF3CH=CHCHBrCH2Br 1,2 addition



1,4-Perfluoropentadiene gave 1,2 bromine addition with no

tetrabromo addition product or cyclization products being formed.

Bromotrichloromethane was added to l,l,2-trifluoropentadiene-l,3










(I) and l,l,2,5,5,5-hexafluoropentadiene-l,3 (II), using benzoyl

peroxide as the initiator. The l,l,2-trifluoropentadiene-l,3 gave

the 1,2-addition product while the 1,1,2,5,5,5-hexafluoropentadiene-

1,3 gave higher telomers but none of the one to one adduct.



CC13Br + CF2=CFCH=CHCH3 -> CC13CF2CFBrCH=CHCH3



CCl3Br + CF2=CFCH=CHCF3 -> higher telomers



The resonance stabilization of the intermediate radical and

subsequent addition of another olefinic molecule has already been

noted above. The addition of CCl3Br was also carried out with

CF2=CFCH2CHBrCH3 to give two diastereomers of CC13CF2CFBrCH2CHBrCH3.

A reaction was attempted between 2-iodoheptafluoropropane and 1,4-

perfluoropentadiene at 150C for 36 hours. No addition product

formed and the starting materials were recovered.

Table VI gives the products from the reactions of CF3NO, CCl3Br,

and Br2 with the dienes.



Reactions with Nucleophiles

The reaction of nucleophiles with fluorine-containing olefins

is well documented in the literature. The study of nucleophilic

attack of dienes, however, has been limited to hexafluorobutadiene-

1,3. The addition of Grignard reagents to perfluorinated olefins

normally gives substitution products by a SN2' type of reaction.
















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RMgX + CF2=CFR' -> RCF=CFR' + MgFX



Aromatic Grignard reagents give predominant products containing

conjugated double bonds.32


C6H5MgBr + CF2=CFCF2C1 -> C6H5CF=CFCF2Cl


C6HsCF2CF=CF2


32%


8.6%


Alkyl Grignard reagents react with fluorohaloolefins to

give an alkene in which the more easily eliminated halogen anion

is displaced.


.CF2CI
RMgX + CH2=C
CF2CI


R = alkyl


.1~


RCH2C CFC1
CF2


predominant product


RCH2CCF2C
CFCl



A good review of the reaction of Grignard reagents, both alkyl and

aryl, can be found in Chemistry of Organic Fluorine Compounds by

M. Hudlicky.18










Alkyl Grignard reagents undergo either addition-elimination

or alkyl addition by radical means. The alkyl addition reaction

was well documented by K. OkuharaI4 for fluoroolefins.



RMgX + CF2=CC12 -> RCF2CCl2H + RCF=CCl2

R = alkyl predominant product



The alkyl addition product was found to be formed by a radical

process and not hydrolysis of the magnesium complex, RCF2CCI2MgBr.

The reaction of phenylmagnesium bromide with each of the

dienes gave the expected addition-elimination reaction products.

The l,l,2,5,5,5-hexafluoropentadiene-l,3 (II) was characterized by

a good yield (68%) of both cistrans and trans,trans dienes.

F F

CF2=CFCH=CHCF3 + CaHsMgBr -> C =C H
7 \ /
CsH5 C=C
-, \
H CF3


cis,trans


H CF3
\ /
F C-=C
\ / \
and C C H
C6H5 F

trans,trans



When the reaction was run at -30C and quenched with DO20 instead

of water, the only product isolated was the substituted










derived diene. This result suggests a concerted reaction since

no deuterium was incorporated into the product.

The product contained only the diene conjugated with the

benzene ring. Since the nonconjugated product was a possibility,

the stabilization of the conjugated product was the predominated

factor in determining the course of the reaction.



C6HsMgBr + CF2=CFCH=CHCF3 -- > C6H5CF=CFCH=CHCF3



C6H5CF2CF=CHCH=CF2



The proposed mechanism for nucleophilic addition can be shown

as follows.


iP + CF2=CFCH=CHR' > RCF2C-H=CHR'

RCF2CF=CHC1H'


- > 1, 2, 3


R'= CH3, CF3

R = CH3CH2CP, C6HS0


RCF=CFCH=CHR'

RCF2CFHCH=CHR'

RCF2CF=CHCH2R'


addition-elimination or substitution

1,2-addition

1,4-addition










Table VII show the nucleophilic reactions with the fluorinated

1,1,2-trifluoro-diene systems. The addition of ethanolic potassium

hydroxide to l,l,2-trifluoropentadiene-l,3 and 1,1,2,5,5,5-hexa-

fluoropentadiene-l,3 gave both 1,2 and 1,4 addition products for

the trifluoropentadiene system and only 1,4 addition product for the

more fluorinated hexafluoropentadiene system.


KOH
CF2=CFCH=CHCH3 + CH3CH20H >KOH CH3CH20CF2CFHCH=CHCH3

1,2 addition product

and

CH3CH20CF2CF=CHCH2CH3

1,4 addition product



CF2=CFCH=CHCF3 + CH3CH2OH KOH > CH3CH20CF2CF=CHCH2CF3

1,4 addition product only



The stabilization of the proposed anion intermediate by the

CF3 moiety of l,l,2,5,5,5-hexafluoropentadiene-l,3 (II) as compared

to the CH3 group of l,l,2-trifluoropentadiene-l,3 (I) would

explain the predominance of the 1,4 addition product in the more

fluorinated system. Each adduct was unstable in moist air and

hydrolyzed to an acid fluoride.

Since the nucleophilic attack of ethanolic potassium hydroxide

on l,l,2,5,5,5-hexafluoropentadiene-l,3 gave only the 1,4-addition





























g -4


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42


product, the possibility of an attack of the first carbon followed

by elimination of fluoride at the five carbon was possible.

0
CHCH2CH + CF2=CFCH=CHCF3 -- > CH3CH20CF2CF=CHCHCF3





CH3CH20CFaCF=CHCH2CF3 CH3CH20CF2CF=CHCH=CF2



None of this diene was detected. The low reactivity of

l,l,2-trifluoropentadiene-l,3 toward aryl Grignard reagents

could not readily be explained since nucleophilic attack of ethoxide

gave essentially the same yield as the more fluorinated pentadiene,

l,l,2,5,5,5-hexafluoropentadiene-l,3.

Several miscellaneous reactions were carried out on products

as well as on the pentadienes. The cyclic dimer of CF2=CFCH=CHCH3

was treated with ozone in methylene chloride until no starting

olefin remained.



CF2CFCH=CHCH3
I I + Ozone --> Ozonide
CF2CFCH=CHCH3


The viscous product showed reactivity with potassium iodide

indicating the presence of the ozonide. An attempt to decompose

the ozonide gave polymeric tars.









Since Knunyants et al.20 found reaction of diethyl amine with

hexafluorobutadiene-l,3 to give the addition product, the reaction

with l,l,2-trifluoropentadiene-l,3 was expected to give the addition

product.



(CH3CH2)2NH + CF2=CFCF=CF2 -> (CH3CH2)2NCF2CFHCF=CF2

H20

0
II
(CH3CH2)2NCCFHCF=CF2



Hydrolysis gave the N,N-diethylamide as shown. The attempted

reaction of diethylamine with the l,l,2-trifluoropentadiene-l,3

gave no adduct after 48 hours. The 2 + 2 cyclodimer was the only

isolated product.

No reaction was observed after six hours when 1,1,2,5,5,5-

hexafluoropentadiene-l,3 was treated with 20% sulfuric acid. The

electrophilic addition to the hydrocarbon segment of the diene

was expected.



H2SO4 + CF2=CFCH=CHCF3 --> CF2=CFCH2CHCF3 or CF2=CFCHCH2CF3
OH OH



Apparently, both the CF2=CF and CF3 groups destabilize the carbonium

ion which would be formed in the first step of the reaction.








*
One of the intermediate olefins, CF2=CFCH2CHBrCH3, was treated

with magnesium in diethyl ether to give a 10% yield of the desired

coupled product along with polymeric material. The proposed scheme is

as follows.



MgBrP

CF2=CFCH2CHBrCH3 + Mg Death l er CF2CFCH2CIP CH3
ether+


CF2=CFCH2CHBrCH3



CF=CFCH2CHCH3 CF2=CFCH2CHCH3
| I n I
CF2=CFCH2CHCH3
CF=CFCH2CHBrCH3



The polymer was not characterized fully since the yield

was low and most of the recovered material was tar.



Conclusions

The activation of the trifluorovinyl segment of the 1,1,2-

trifluoropentadiene-l,3 (I) by the hydrocarbon unsaturated segment

was immediately evident in the 2 + 2 cycloaddition reaction. There

has been no previous report of a cyclobutane formed at 0C from a

fluorinated olefin or diene. The l,l,2-trifluoropentadiene-1,3

was so reactive that no other 2 + 2 cycloaddition products were

formed with a variety of olefins, both fluorocarbon and hydrocarbon.

Radical reactions such as bromine addition and bromotrichloromethane










addition gave the 1,2 addition product, while the trifluoronitroso-

methane gave the 2 + 4 Diels-Alder adduct along with polymer

containing 1,2 and 1,4 addition structure.

Nucleophilic additions to l,l,2-trifluoropentadiene-l,3

gave the expected results for aryl Grignard reagents and both 1,2

and 1,4 addition for the reaction with ethoxide.

Reactions with the l,l,2,5,5,5-hexafluoropentadiene-l,3 (II)

also show the reactivity of the mixed trifluorovinyl, hydrocarbon

olefin combination. This diene readily formed the expected

cyclobutane derivative. A mixed cyclobutane was found when 1,1,2-

trifluoropentadiene-l,3 was treated with (II). Bromine added 1,2 and

1,4 to give the corresponding alkenes in 25% and 75% yields,

respectively. The reaction of bromotrichloromethane gave only

polymers with l,l,2,5,5,5-hexafluoropentadiene-l,3. Trifluoronitroso-

methane again gave the 2 + 4 Diels-Alder adduct with (II) along with

polymers with 1,2 and 1,4 structures. The expected elimination or

substitution reaction from aryl Grignard reagents was realized in

68% yield, giving both the cis,trans and trans,trans products.

Ethanol addition gave only the 1,4 addition product in 67% yield.

The 1,4-perfluoropentadiene was found to be unreactive compared

to (I) and (II). No 2 + 2 cycloaddition products were formed and no

products from radical reactions were isolated except for the 1,2

addition product with bromine. None of the tetrabromo addition

product or cyclized product was formed. Trifluoronitrosomethane

gave no adducts at -78C and at ambient temperature.






46


Tables VIII, IX and X give the reactions, products, and

yields for each system, l,l,2-trifluoropentadiene-l,3; 1,1,2,5,5,5-

hexafluoropentadiene-l,3; and 1,4-perfluoropentadiene.







47



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SECTION 3

EXPERIMENTAL



The analytical work on the compounds prepared was carried out

as follows: Gas-liquid chromatography (GLC) was accomplished on a

Hewlett Packard 5710A gas chromatograph equipped with a thermal

conductivity detector. A 20-foot QF-1 column with a 10% loading

on acid washed Chromosorb W was the column of choice. A methyl

trifluoropropyl silicone oil (QF-1) proved adequate for separation of

the fluorine-containing products. Infrared analyses were performed

using a liquid smear of sample between sodium chloride crystals. A

Perkin Elmer 727B instrument was employed. Nuclear magnetic resonance

(NMR), both proton H1 and fluorine F19, were performed by Dr. Wallace

Brey using a Varian XL-100 spectrometer with external standard. Mass

spectral data were compiled on an AEI-MS-30 mass spectrometer with a

DS-30 data system with the assistance of Dr. Roy King and Ms. Jackie

Dugan. Any deviation, such as column change for GLC analysis, etc.,

will be presented in the experimental for specific reactions. All

temperatures are reported in degrees centigrade (C) with boiling

points being as observed and uncorrected.










Preparation of Precursors



Addition of 1,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFClBr) to
Propene (CH2=CHCH3)

The attempted reaction was carried out in a five-liter, three-

necked flask equipped with a gas inlet, a condenser, a thermowell,

and backed by a Dry-Ice acetone trap. The l,2-dibromo-2-chlorotri-

fluoroethane (CTFE dibromide, 1,385 grams, 5 moles) was added and

stirred under a dry nitrogen sweep for two hours while the material

was heated to- reflux. Benzoyl peroxide (10 grams) was added and the

propene (CH2=CHCH3) addition was begun. After one hour, an additional

five grams of benzoyl peroxide was added and, subsequently, five grams

every hour for three additional hours. At the end of four hours, a

sample revealed no addition product had formed even though there had

been added 170 grams (4 moles) of propene. The reaction was terminated

and the starting materials recovered (Figure 1).

A three-liter autoclave was cleaned, equipped with a 5,000 psi

rupture disc and pressure checked with dry nitrogen. The autoclave

was evacuated and cooled in liquid oxygen before a mixture of CTFE

dibromide (CF2BrCFClBr, 1,385 grams, 5 moles) and benzoyl peroxide

(20 grams) was added. The propene (CH2=CHCH3, 210 grams, 5 moles)

was condensed into the autoclave through a vacuum manifold. After

the system was warmed to ambient temperature, the autoclave was

placed in a heater/rocker and heated to 150C with rocking for 16

hours. The autoclave was cooled to room temperature and the overgases

collected. The remaining liquid (1,505 grams) was distilled to give

880 grams of starting CF2BrCFClBr along with 485 grams of material










which had a boiling point of 176-181C (83% yield). A GLC analysis

on an SE-30 nickel column showed two components which did not give a

base line separation. Further separation was carried out on a

40-plate Oldershaw column to give the two fractions in greater

than 90% purity. Nuclear magnetic resonance analysis confirmed
*
the structure to be two diastereomers of CF2BrCFClCH2CHBrCH3

(Figures 2 6). Figure 2 lower boiling diastereomer. IR

(liquid) maxima in microns 3.34 (C-H), 8.1, 8.18, 8.32, 8.95 (C-F),

9.6, 10.0, 10.4, 12.55. Figure 3 higher boiling diastereomer.

IR (liquid) maxima in microns 3.3 (C-H), 8.1, 8.15, 8.33 (C-F), 9.5,

12.5, 12.7. Figure 4 F19 NMR, two fluorines, doublet for CF2Br;

one fluorine, multiple for CFC1; mass spectrum m/e 320 (M ), 239,

237 (M-Br), 203, 201 (M-Br and Cl), 159, 157 (M-2Br), 121 (M-C2F3CIBr).

High resolution mass spectrum, C5F3Br2ClH6, calculated mass 315.84,

measured 315.85.

The three-liter autoclave reaction was repeated to obtain an
*
additional 472 grams (80% yield) of material, CF2BrCFClCH2CHBrCH3,

for further reactions.

A three-liter autoclave reaction was repeated using propene

(210 grams, 5 moles), l,2-dibromo-2-chlorotrifluoroethane (2,806 grams,

10.2 moles) and benzoyl peroxide (30 grams). The reaction was carried

out at 150C for 24 hours and was worked up as the previous reactions.

The liquid products were distilled to give 661 grams of the two

diastereomers in 80% yield based on consumed propene.










Attempted Reaction of l,2-Dibromo-2-chlorotrifluoroethane
(CF2BrCFClBr) with 1,3-Butadiene (CH2=CHCH=CH2)

A three-liter autoclave was cleaned and equipped with a 5,000 psi

rupture disc before being pressure checked with 600 psi of dry nitrogen.

After venting the nitrogen, a full vacuum was applied and the autoclave

was cooled to -196C with liquid oxygen. Benzoyl peroxide (15 grams)

was dissolved in the l,2-dibromo-2-chloro-trifluoroethane (1,040 grams)

and sucked into the evacuated autoclave. The 1,3-butadiene (135 grams)

was vacuum transferred into the autoclave and the system was heated to

120%C for 16 hours. After the autoclave was cooled to ambient

temperature, the overgases were collected (120 grams). Distillation

gave recovered l,2-dibromo-2-chlorotrifluoroethane (996 grams) and

'-30 grams of higher molecular weight oil. The simple adduct (1 to 1)

was not present.



Addition of l,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFCIBr) to
Trifluoropropene (CF3CH=CH2)

A three-liter autoclave was equipped with a 5,000 psi rupture disc

and pressure checked to 700 psi with dry nitrogen. The nitrogen was

vented and a full vacuum applied to the system before the autoclave

was cooled to -196C with liquid oxygen. The l,2-dibromo-2-chloro-

trifluoroethane (1,108 grams) in which benzoyl peroxide (15 grams)

was dissolved was then sucked into the evacuated autoclave. Trifluoro-

propene (266 grams) was condensed into the system before the autoclave

was heated to 1200C and rocked for 20 hours. After the system was

cooled to room temperature, the overgases were collected (101 grams)

and the liquid products poured into a distillation flask. The









l,2-dibromo-2-chlorotrifluoroethane was recovered (960 grams) leaving

280 grams of higher boiling material. Distillation gave 105 grams of

material with a boiling point less than 180C which by GLC analysis

was a composite of four peaks. The higher boiling fraction (90 grams,

bp 56-59/O.l mm) was found to be two sets of diastereomers of

CF2BrCFClCH2CH(CF3)CH2CHBrCF3 (25% yield, Figures 7 10). Figure

7 IR (liquid) maxima in microns 3.35 (C-H), 8.0, 8.4, 8.75, 8.95

(C-F), 9.6, 13.0. Figure 8 H1 NMR multiplets for CHBr, CH2, CH,

CH2. Figure 9 F19 NMR, Figure 10 F19 NMR, Table XII Mass

spectrum m/e 445 (M +), 369, 367 (M-Br), 287 (M-2Br), 273, 271,

(M-C2F3ClBr), 259, 257 (M-C3F3ClBrH2).

The reaction was repeated using a higher ratio of 1,2-dibromo-

2-chlorotrifluoroethane to trifluoropropene with essentially the

same results. There was no evidence of the presence of the 1 to 1

addition product but n25% of the 1,2-dibromo-2-chlorotrifluoroethane

had added to two molecules of trifluoropropene to give

CF2BrCFClCH2CH(CF3)CH2CHBrCF3 (92 grams).



Addition of l,2-Dichloro-2-iodotrifluoroethane (CF2Cl-CFClI) to
Trifluoropropene (CH2=CHCF3)

A three-liter autoclave was equipped with a 3,000 psi rupture

disc and pressure checked at 800 psi with dry nitrogen before being

evacuated to full vacuum. The autoclave was cooled in liquid oxygen

before the l,2-dichloro-2-iodotrifluoroethane (1,000 grams, 3.58 moles)

and benzoyl peroxide (11 grams) was sucked into the evacuated

system. The trifluoropropene (170 grams, 1.77 moles) was condensed

in via a glass vacuum system. The mixture was heated at 100C for










four hours before being cooled to ambient temperature. Work-up

showed that no reaction had occurred.

The three-liter autoclave reaction was repeated and the reactants

heated to 150C with rocking for four hours. After being cooled to

room temperature and the volatiles collected, the liquid products

were distilled to give CF2ClCFClI (685 grams, 2.16 moles), and the

desired CF2ClCFClCH2CHICF3 (315 grams, .84 moles, bp 161-166C) in

75% yield. The large boiling range is due to the presence of two sets

of diastereomers. (Figures 51 54). Figure 51 both diastereomers.

IR (liquid) maxima in microns 3.30 (C-H), 7.6, 7.8, 8.05, 8.15, 8.45,

8.8 (C-F), 9.2, 10.0. Figure 52 F19 N2 R, three fluorines,

doublet CF3; two fluorines, CF2CI triplet; one fluorine, multiple

for CFC1; Figure 53 and C H1 NMR, coi-plicated multiple for both

CH2 and CHI, Table XXII mass spectrum n/e 376, 374 (M +), 291, 289

(M-CF2Cl), 349, 247 (M-I), 213, 211 (M-I and Cl).

The reaction was repeated in a three-liter autoclave using the

recovered CF2ClCFClI (685 grams, 2.16 moles) and trifluoropropene

(170 grams, 1.77 moles) to give an additional 310 grams of

CF2C1CFC1CH2CHICF3 in 80% distilled yield.



Preparation of l-Bromo-2-iodotetrafluoroethane (CF2BrCF2I)

A three-liter autoclave was used to prepare the l-bromo-2-iodo-

tetrafluoroethane. After being pressure and vacuum checked and cooled

to -196C, the autoclave was charged with bromine (480 grams) and

iodine (790 grams), and the tetrafluoroethylene was condensed in

(1,100 grams). The reaction mixture was heated to 200C for 20 hours










with rocking before being cooled to ambient temperature. The over-

gases were vented and the liquid products distilled to give 1,2-dibromo-

tetrafluoroethane (210 grams), l-bromo-2-iodotetrafluoroethane (610

grams, bp 79-80C, 23% distilled yield), 1,2-diiodotetrafluoroethane

(360 grams) and 560 grams of a residue which contained higher telomers

(Figure 11).



Addition of l-Bromo-2-iodotetrafluoroethane (CF2BrCF2I) to Ethylene

A three-liter autoclave was equipped as in previous reactions,

evacuated and cooled to -196C before the benzoyl peroxide (15 grams)

and l-bromo-2-iodotetrafluoroethane (610 grams) were added. Ethylene

(120 grams) was condensed into the autoclave and the system was warmed

to 120C for 16 hours with rocking. After cooling, the autoclave was

vented and the liquid products distilled to give l-bromo-2-iodotetra-

fluoroethane (151 grams), l-bromo-4-iodo-l,l,2,2-tetrafluorobutane

(286 grams, bp 160-161C, 58% distilled yield), and 210 grams of

higher boiling material (Figure 12).



Preparation of Olefins



Attempted Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with 50% Aqueous
Sodium Hydroxide

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

a reflux condenser, a thermometer, and a dropping funnel. Aqueous

sodium hydroxide (NaOH, 320 grams of 50%) was added to the flask and
*^ *
stirred as the mixture was heated to 80C. The CF2BrCFClCH2CHBrCH3

(169 grams, 0.53 moles) was added via the dropping funnel over a one-










hour period. The organic material immediately formed a lower layer

and did not react with the caustic solution.


*
Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with Potassium t-Butoxide
and Dimethyl Sulfoxide

A 500-ml, three-necked flask was equipped with a mechanical

stirrer, a condenser backed by a liquid oxygen cooled trap, a thermo-

meter, and a dropping funnel. The potassium-t-butoxide (41 grams,

0.37 moles) and dimethyl sulfoxide (200 ml) were added to the flask
*
and the mixture stirred. The fluorocarbon, CF2BrCFClCH2CHBrCH3

(95 grams, 0.3 moles) was added dropwise via the dropping funnel and

the mixture was heated to 1l30C before a reflux was noted. The

condenser was replaced with a distillation head and 65 grams of

material was collected. Redistillation gave 52 grams of

CF2BrCFClCH=CHCH3 (bp 133-1340C, 73% yield, Figures 13 15). Figure

13 IR (liquid) maxima in microns 3.36 (C-H), 6.0 (C=C), 8.25, 8.3,

8.8, (C-F) 9.9, 10.4, 10.7, 11.2, 12.5, 14.0. Figure 14 H1 \1KR.

Two types of vinyl protons, two hydrogens; and a doublet, three

hydrogens, for CH3. Figure 15 F19 NMR. Table XIII mass spectrum

m/e 238 (M +), 159, 157 (M-Br), 203, 201, (M-C1), 107 (M-Br, Cl and

CH3). High resolution mass spectrum, C5F3H5ClBr, calculated mass

236.09, measured 235.92.



Dehydrohalogenation of CF2BrCFClCH2CHBrCH3 with Ethanolic Potassium
Hydroxide

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a condenser. Ethanol (250 ml) and

potassium hydroxide (65 grams) were stirred until the base had gone









*
into solution. The CF2BrCFClCH2CHBrCH3 (320 grams, 0.95 moles) was

added dropwise and an exotherm to 60C was noted over a two-hour

period. After being stirred for an additional three hours, the

material was washed twice with one liter of ice water to give 230

grams of product. After the mixture was dried over molecular sieves,

distillation gave 217 grams of CF2BrCFClCH=CHCH3 (88% yield, bp

133-134C).
*
The dehydrohalogenation of CF2BrCFClCH2CHBrCH3 (329 grams, 1.03

moles) was repeated using potassium hydroxide (63 grams, 1.1 moles)

in ethanol (600 ml). Distillation of the product gave

CF2BrCFClCH=CHCH3 (bp 131-132C, 181 grams, 74% yield).



Dehydrohalogenation of CF2BrCF2CH2CH2I with Ethanolic Potassium
Hydroxide

The attempted reaction of CF2BrCF2CH2CHI with aqueous sodium

hydroxide gave only recovered starting material but alcoholic

potassium hydroxide gave the desired olefin. A 250-ml, three-

necked flask was equipped with a magnetic stirrer, dropping funnel,

thermowell, and a condenser before being charged with ethanol (150 ml)

and potassium hydroxide (10 grams). The CF2BrCF2CH2CH2I (61 grams,

0.19 moles) was added dropwise over a two-hour period. After the

material was washed with 500 ml of ice water, the organic layer was

collected and dried over molecular sieves. Distillation of the

crude product (36 grams) gave 28 grams of 99+% pure CF2BrCF2CH=CH2

(80% distilled yield, bp 64C, Figures 16 18).










Dehydrohalogenation of CF2BrCFClCH2CH(CF3)CH2CHBrCF3 with Ethanolic
Potassium Hydroxide

The dehydrohalogenation of CF2BrCFClCH2CH(CF3)CH2CHBrCF3 with

ethanolic potassium hydroxide was attempted in a 250-mi, three-necked

flask equipped with a magnetic stirrer, dropping funnel, thermometer,

and condenser. The potassium hydroxide (18 grams, 0.32 moles) and

ethanol (200 ml) were placed in the flask and stirred for 30 minutes.
*
The CF2BrCFClCH2CH(CF3)CH2CHBrCF3 (100 grams, 0.22 moles) was added

over a one-hour period and stirred for an additional two hours. After

the material-was washed with ice water (500 ml), the organic layer was

collected and dried over molecular sieves. The product was the

starting material which was recovered in 85% yield.


*
Dehydrohalogenation of CF2ClCFClCH2CHICF3 with Ethanolic Potassium
Hydroxide

A one-liter, three-necked flask was equipped with a magnetic

stirrer, dropping funnel, distillation head and thermowell. The

potassium hydroxide (76 grams, 1.25 moles), water (225 ml), and

ethanol (300 ml) were placed in the flask and stirred as the mixture

was heated to 70C. The CF3CICFClCH2CHICF3 (300 grams, 0.8 moles)

was added slowly via the dropping funnel as the mixture was heated

to 80C with material distilling from the reaction mixture. The

product, CF2ClCFClCH=CHCF3 (131 grams, bp 88C), was washed with water

and dried over molecular sieves. Distillation gave a 70% yield

(Figures 55 58). Figure 55 IR (liquid) maxima in microns 3.18

(C-H), 5.88 (C=C), 7.61, 7.8, 8.2, 8.6 (C-F), 9.3, 9.5, 10.3, 11.0,

11.5, 12.6. Figure 56 F19 NMR, three fluorines, doublet for CF3;










two fluorines, doublet for CF2CI; one fluorine, multiple for CFC1.

Table XXIII mass spectrum m/e 246 (M+ ), 211 (M-CI), 163, 161

(M-CF2CI2).
*
The reaction was repeated using CF2ClCFClCH2CHICF3 (280 grams,

0.75 moles). The product was collected in 60% yield after being
0
separated from the ethanol and dried over 4A molecular sieves.



Decarboxylation of CF2ClCFBrCF2CFBrCF2COONa

A one-liter, three-necked flask was equipped with a mechanical

stirrer, thermometer, and a distillation head. The CF2ClCFBrCF2CFBr-

CF2COONa (400 grams, 0.84 moles) was placed in the flask along with

diglyme (500 ml) and the mixture was heated to 90C slowly with the

evolution of CO2. The mixture was then heated to a flask temperature

of 145C while the product distilled from the flask. The collected

material contained the CF2ClCFBrCF2CF=CF2 along with diglyme. The

diglyme was washed from the mixture with ice water to give 190 grams

of 98+% pure CF2ClCFBrCF2CF=CF2 (bp 104-106C, Figure 19). Figure 19 -

IR (liquid) maxima in microns 5.6 (CF2=CF), 7.4, 7.7, 8.7, 9.0 (GF),

9.6, 10.2, 11.0, 11.2, 11.6, 123, 12.7, 13.5.


*
The Dehalogenation of CF2BrCFClCH=CHCH3 with Zinc

A one-liter, three-necked flask was equipped with a mechanical

stirrer, a dropping funnel, a thermometer, and a Vigreux column with

a distillation head. The zinc (65 grams, 1.01 moles) and ethanol

(250 ml) were placed in the flask and stirred while being heated to

65C. The CF2BrCFClCH=CHCH3 (210 grams, 0.88 moles) was added drop-

wise via the dropping funnel over a one-hour period with the product










distilling out as it was formed. The product, CF2=CFCH=CHCH3, was

collected (85 grams, 97% pure, bp 44-45C, 78% yield, Figures 20 23).

Figure 20 IR (liquid) maxima in microns 3.4 (C-H), 5.6 (CF2=CF), 6.05

(CH=CH), 7.8, 7.95, 8.5, 9.0 (C-F), 9.5, 10.5. Figure 22 H1 nMR,

three hydrogens, doublet (CH3); two hydrogens, multiple (CH=CH).

Figure 23 F19 NMR, three fluorines, four sets of multiplets. Table

XIV mass spectrum m/e 122 (M+), 121 (M-H), 103, (M-F), 102 (M-HF),

109 (M-H2F), 72 (M-CF2). High resolution mass spectrum, CsF3Hs,

calculated mass 122.09, measured 122.03.

The reaction was repeated using CF2BrCFCICH=CHCH3 (40 grams),

zinc (40 grams), and ethanol (150 ml). The product was collected,

washed with ice water, dried over molecular sieves and distilled to

give 19 grams of CF2=CFCH=CHCH3 (bp 44-45C, 92% yield).

The preparation of CF2=CFCH=CHCH3 was repeated using

CF2BrCFClCH=CHCH3 (145 grams, 0.61 moles), zinc (46 grams, 0.69 moles)

and ethanol (150 ml). The product which distilled from the reaction

mixture, washed twice with ice water and dried over molecular sieves

gave CF2=CFCH=CHCH3 (69 grams, 92% yield, bp 44-45C).


*
Dehalogenation of CF2BrCFClCH2CHBrCH3 with Zinc

A 500-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a Vigreux column with a distillation

head. The zinc (76 grams, 1.19 moles) and ethanol (250 ml) were placed

in the flask and heated to 450C with stirring before the fluorocarbon

was added dropwise. An exothermic reaction ensued and the temperature

rose to 80C. After being stirred for one and one-half hours, the









liquid was decanted into one-liter of water and the organic layer was

separated and dried. Distillation gave CF2=CFCH2CHBrCH3 (67 grams,

bp 110-111C, 91% yield, Figures 24 26). Figure 24 IR (liquid)

maxima in microns 3.38, 3.45 (C-H), 5.61 (CF2=CF), 7.8, 8.0, 8.2,

8.6 (C-F), 9.0, 9.4, 9.6, 9.8, 10.2. Figure 25 F19 NR, three

fluorines, three sets of multiplets for CF2=CF, Figure 26 H1

NMR, three hydrogens, doublet for CH3; two hydrogens, two sets of

multiplets for CH2; one hydrogen, sextet for CHBr. Table XV mass

spectrum m/e 204, 202 (M +) 123 (M-Br), 109, 107 (M-C3F7H2), 103

(M-H, F, Br); 95 (M-C2H7Br). High resolution mass spectrum,

C3F3H6Br, calculated mass 202.10, measured 201.96.



Dehalogenation of CF2BrCFClCH2CH(CF3)CH2CHBrCF3 with Zinc

A 250-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a distillation head. The ethanol

(150 ml) and zinc (20 grams, 0.31 moles) were added to the flask and

stirred as a few drops of bromine were added to activate the zinc.
*L *
The mixture was heated to 50C before the CF2BrCFClCH2CH(CF3)CH2CHBrCF3

(31 grams, 0.066 moles) was added via the dropping funnel. An exotherm

was immediately noted and distillation gave ethanol and fluorocarbon

product. After being washed with ice water to remove the ethanol,

the organic layer was separated, dried over molecular sieves and

distilled to give CF2=CFCH2CH(CF3)CH2CH=CF2 (bp 134-138C, 95% yield,

16 grams, Figures 27 and 28). Figure 27 IR (liquid) maxima in

microns 3.38 (C-H), 5.55 (CF2=CF), 5.7 (CF2=CH), 7.7, 8.0, 8.4,

8.5, 9.0 (C-F). Figure 28 F19 NMR, three fluorines, singlet CF3;

two fluorines, multiple (CF2=CH); three fluorines, multiple (CF2=CF).









Dehalogenation of CF2ClCFBrCF2CF=CF2 with Zinc

A one-liter, three-necked flask was equipped with a magnetic

stirrer, Vigreux column, thermometer, and dropping funnel. A distil-

lation head backed by a liquid oxygen trap was used to collect the

product. The zinc (60 grams, 0.94 moles), ethanol (500 ml), and

bromine (3 ml) were added to the flask and stirred as the mixture was

heated to 50C. The CF2ClCFBrCF2CF=CF2 (190 grams, 0.58 moles) was

added dropwise via the dropping funnel as the product was collected in

the distillation head. After the product was washed with ice water,

the organic material was dried over molecular sieves and distilled to

give CF2=CFCF2CF=CF2 (92 grams, 75% yield, bp 36-38C, Figures 29 30).

Figure 29 IR (liquid) maxima in microns 5.6 (CF2=CF), 7.4, 7.6,

7.8, 8.35, 8.42, (C-F), 9.7, 10.8, 11.2. Figure 30 F19 NMR, eight

fluorines, six sets of multiplets for the (CF2=CF)2CF2. Table XVI -

mass spectrum m/e 212 (M +), 162 (M-CF2), 143 (M-CF3), 131 (M-C2F3),

93, (M-C2F5). High resolution mass spectrum, C5F8, calculated mass

212.04, measured 211.99.



Dehalogenation of CF2ClCFClCH=CHCF3 with Zinc

A 250-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, distillation head, and a thermometer. The zinc (40

grams) and ethanol (150 ml) were placed in the flask and stirred as

bromine (1 ml) was added to activate the zinc. The mixture was heated

to 65C before the olefin CF2ClCFClCH=CHCF3 (90 grams, 0.36 moles) was

added dropwise. The product immediately distilled from the reaction

mixture and, after the material was washed with ice water and dried










over molecular sieves, the CF2=CFCH=CHCF3 (59 grams, bp 43-44C, 92%

yield) was distilled. (Figures 57 59). Figure 57 IR (liquid)

maxima in microns 3.35 (C-H), 5.7 (CF2=CF), 5.95 (CH=CH), 7.58, 7.7,

7.8, 8.7 (C-F), 10.3, 12.0. Figure 58 F19 NMR, three fluorines,

singlet for CF3, three fluorines, three sets of multiplets for (CF2=CF).

Figure 59 H1 NMR, two hydrogens, complex multiple for CH=CH.

Table XXIV mass spectrum m/e 176 (M+ ), 157 (M-F), 126 (M-CF2), 107

(MCF3). High resolution mass spectrum, C5F6H2, calculated mass 176.07

measured 176.01.

The reaction was repeated using 55 grams of CF2ClCFClCH=CHCF3

to give 31 grams of CF2=CFCH=CHCF3 for a 80% distilled yield.


*
Dehalogenation of CF2CICFClCH2CHICF3 with Zinc

A 250-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, short column, distillation head, and thermometer.

The flask was charged with ethanol (150 ml) and zinc (20 grams) and the

mixture stirred and one ml. of bromine was added. The mixture was

heated to 50C as the CF2ClCFClCH2CHICF3 (90 grams) was added dropwise

and an immediate exotherm to 80C was noted. After the mixture was

allowed to cool to ambient temperature, the solution was added to one

liter of ice water. The organic layer was collected and dried before

distillation. The product, CF2ClCFClCH2CH=CF2 (37 grams, 72% yield),

was distilled (bp 101-103C) and was 99+% pure by GLC analysis (Figures

80 and 81). Figure 80 IR (liquid) maxima in microns 5.67 (CF2=CH),

7.55, 7.9, 8.15, 8.4, 8.62, 9.1, (C-F), 9.3, 9.9, 12.3. Figure 81 -

F19 NMR, two fluorines, multiple for (CF2=CH), two fluorines, doublet

for CF2Cl, one fluorine, multiple for CFC1. Table XXXII Mass










spectrum m/e 230 (M4 ), 193 (M-C1), 143, (M-CF2Cl), 77 (M-C2F3C12).

High resolution mass spectrum, CsF535C12H3, calculated mass 228.07,

measured 227.95, CsF535C137C1H3, calculated mass 230.07, measured

229,95.



Reactions of Olefins Prepared



2 + 2 Reactions of Chlorotrifluoroethylene with CF2=CFCH=CHCH3

An ampoule was charged with one grand of CF2=CFCH=CHCH3 and cooled

in liquid oxygen before a full vacuum was applied and one gram of

chlorotrifluoroethylene was condensed into the system. The ampoule

was sealed under vacuum and placed in an oil bath at 160C for 20

hours. After it was cooled to ambient temperature, the ampoule was

frozen in liquid oxygen and opened. The overgases were vented and

1.2 grams of product was collected. Infrared analysis indicated a

R'CH=CHR absorption. A larger sample was then prepared using 6.1

grams of CF2=CFCH=CHCH3 and 5.8 grams of chlorotrifluoroethylene.

The product was completely characterized as the dimer of CF2=CFCH=CHCH3

with the following 2 + 2 structure (bp 160-161C, quantitative yield,

CF2-CFCH=CHCH3
I I
CF2- CFCH=CHCH3

Figures 31 33). Figure 31 IR (liquid) maxima in microns 3.35, 3.41

(C-H), 5.95 (CH=CH), 7.2, 7.25, 7.9, 8.4 (C-F), 10.1, 10.4, 11.2.

Figure 32 H1 NMR, three hydrogens, doublet for CH3; two hydrogens,

two sets of multiplets for (CH=CH). Figure 33 F19 NMR, two

fluorines, two sets of multiplets for CF's; four fluorines, five sets

of multiplets for both CF2's. Table XVII Mass spectrum m/e 244 (M ),

122 (M-C5F3H3).









2 + 2 Cycloaddition of 2,2-Dichlorodifluoroethylene with CF2=CFCH=CHCH3

An ampoule was charged with CF2=CFCH=CHCH3 (6.1 grams, 0.05 moles)

and frozen in liquid oxygen while being evacuated to full vacuum. The

CF2=CCl2 (6.7 grams, 0.05 moles) was condensed into the ampoule and

the system sealed under vacuum. After reacting for 16 hours at 160C

in an oil bath, the tube was opened and the overgases vented. The

only product isolated was the 2 + 2 cyclic dimer of CF2=CFCH=CHCH3.


Dimerization of CF2=CFCH=CHCH3

An ampoule was charged with CF2=CFCH=CHCH3 (15 grams) and

evacuated after being cooled in liquid oxygen. The system was sealed

under vacuum and heated in an oil bath at 100C for 16 hours. When

the ampoule was opened, the dimer was the only product present.

CF2- CFCH=CHCH3
CF-I I = 3
CF2 --CFCH=CHCHI3


Dimerization of CF2=CFCH=CHCF3

A 50-ml ampoule was charged with CF2=CFCH=CHCF3 (4.4 grams,

0.025 moles) sealed and heated to 800C for 20 hours. After being

cooled to ambient temperature, the ampoule was opened. Infrared

analysis indicated some unreacted diene. A GLC analysis showed the

material to be 50% unreacted diene and 50% 2 + 2 cyclic dimer.

The reaction was repeated at 100C for 20 hours to give complete

conversion of CF2=CFCH=CHCF3 to the dimer CF2CFCH=CHCF3 (bp 133-135C
I 1
CF2CFCH=CHCF3

Figures 63 and 64). Figure 63 IR (liquid) maxima in microns 3.18









(C-H), 5.85 (CH=CH), 7.55, 7.8, 8.3, 8.75 (C-F), 10.4, 10.7.

Figure 64 F19 NMR, three fluorines, doublet for CF3, two

fluorines, two sets of multiplets for CF's; four fluorines, six

sets of multiplets for CF2's. Table XXVI Mass spectrum 352

(M +), 176 (M-CFH2), 157 (M-CF7H2), 126 (M-C6FH2).



Co-dimerization of CF2=CFCH=CHCH3 with CF2=CFCH=CHCF3

A 50-ml ampoule was charged with CF2=CFCH=CHCH3 (2 grams) and

CF2=CFCH=CHCF3 (3 grams) before being sealed and heated to 105C for

20 hours. The ampoule was cooled to ambient temperature, and the

ampoule was opened. Infrared analysis showed no CF2=CF- absorption.

Distillation gave three fractions, the 2 + 2 cyclic dimer of

CF2=CFCH=CHCF3, the co-dimer of CF2=CFCH=CHCF3 and CF2=CFCH=CHIICH3,

and the 2 + 2 cyclic dimer of CF2=CFCH=CHCH3 (Figures 65 and 66).

Figure 65 IR (liquid) maxima in microns 3.18, 3.3, 3.35, (C-H), 5.88

(CH=CH), 7.1, 7.6, 7.8, 8.38, 8.7, (C-F), 10.3, 10.7. Figure 66 -

F19 NMR, three fluorines, doublet for CF3; four fluorines, multiplets

for CF2 in cyclobutane; two fluorines, multiplets for CF in cyclo-

butane. Table XXVII Mass spectrum m/e 298 (M+ ), 176 (M-C5F3H3), 122

(M-CsF7H2).



Attempted 2 + 2 Cycloaddition of Chlorotrifluoroethylene with
CF2=CFCH2CHBrCH3

An ampoule was charged with CF2=CFCH2CHBrCH3 (10.1 grams, 0.05

moles), which was frozen and evacuated, before the chlorotrifluoro-

ethylene (5.8 grams, 0.05 moles) was condensed into the system. After










the ampoule was heated for 20 hours at 140C in an oil bath, it was

opened and the overgases vented. The only product isolated was the

starting CF2=CFCH2CHBrCH3.

The reaction of CF2=CFCH2CHBrCH3 with chlorotrifluoroethylene

was repeated at 160C with similar results. No 2 + 2 addition was

found and the olefin, CF2=CFCH2CHBrCH3, was recovered.



Attempted Reaction of Butadiene with CF2=CFCH2CHBrCH3

An ampoule was charged with butadiene (0.84 grams) and

CF2=CFCH2CHBrCH3 (4.06 grams). The ampoule was sealed and heated to

125C for 20 hours. After cooling to room temperature the ampoule

was opened and the CF2=CFCH2CHBrCH3 was recovered unreacted.

The reaction was repeated using a large excess of butadiene

(3.36 grams) with no reaction again after 20 hours at 120C.



Attempted Reaction of Butadiene with CF2=CFCH=CHCH3

A 500-ml ampoule was charged with CF2=CFCH=CHCH3 (6.1 grams,

0.05 moles) and butadiene (5.4 grams, 0.1 moles) before being heated to

120C for four hours. A fog was noted after one hour and black solids

had formed after four hours and the reaction was worked-up. After

the excess butadiene was removed, the only liquid product collected

was the 2 + 2 cyclodimer of the pentadiene.



Radical Addition of Bromotrichloromethane to CF2=CFCH2CF3rCH3
with Benzoyl Peroxide

An ampoule was charged with bromotrichloromethane (9.9 grams),

CF2=CFCH2CHBrCH3 (10.0 grams) and benzoyl peroxide (0.4 grams). After









being cooled to -196C, the ampoule was evacuated to full vacuum and

sealed. The system was heated in an oil bath at 160C for 16 hours

before being opened and the products collected. Distillation gave

9.1 grams of material (bp 80-88C/0.1 mm) which showed two peaks by

GLC analysis. Analysis showed the product to be two sets of diastere-

omers of CCl3CF2CFBrCH2CHBrCH3 (79% yield, Figures 34 34). Figure

34 IR (liquid) maxima in microns 3.31, 3.38 (C-H), 8.3, 8.5, 8.7, 9.1,

(C-F) 9.7, 10.1, 11.7, 11.9, 12.0. Figure 36 H1 NMR, three

hydrogens, doublet for CH3; two hydrogens, multiplets for CH2; one

hydrogen, multiple for CHBr. Figure 37 F19 NMR, two fluorines,

two sets of doublets for CF2; one fluorine, two sets of multiplets

for CF. Table XVIII Mass spectrum m/e 398, 400, 402 M ), 323,

321, 319 (M-Br), 287, 285, 283 (M-Br+Cl). High resolution mass

spectrum, C6H535C13F379Br2, calculated mass 397.10, measured mass

397.79.



Radical Addition of CCl3Br with CF2=CFCH=CHCH3 Using Benzoyl Peroxide

A 500-ml ampoule was charged with bromotrichloromethane, CCl3Br,

(197 grams, 1 mole), benzoyl peroxide (2 grams) and the pentadiene,

CF2=CFCH=CHCH3, (12.2 grams, 0.1 mole). The mixture was heated to

70C for four hours before being placed in a distillation flask and

the CCl3Br removed. The remaining material (14 grams) was further

distilled on a micro-column to give the 2 + 2 cyclodimer (7 gra=s)

and the desired adduct CC13CF2CFBrCH=CHCH3 (6 grams, bp 225-230C

Figures 60 62). Figure 60 IR (liquid) maxima in microns 3.3

(C-H), 5.85 (CH=CH), 7.6, 7.9, 8.7 (C-F), 9.5, 11.5, 11.8, 12.6,

13.4. Figure 61 F19, two fluorines, two multiplets for CF2; one









fluorine, two multiplets for CF. Figure 62 H1 NMiR, three hydrogens,

two doublets for CH3; two hydrogens, two multiplets for vinyl

hydrogens. Table XXV Mass spectrum m/e no parent peak, 241, 239,

(M-Br), 203, 201 (M-CCI), 151 (M-CCI3CF2-CF2), 122 (M-Br, CC13,

107 (M-Br, CC13) CH3). High resolution mass spectrum, C6H5F335-

C3l79Br, calculated mass 318.10, measured 317.96.



Radical Addition of CCl3Br with CF2=CFCH=CHCF3 Using Benzoyl Peroxide

A 100-ml ampoule was charged with CC13Br (19.8 grams, 0.1 mole)

benzoyl peroxide (0.2 grams) and CF2=CFCH=CHCF3 (4.4 grams, 0.025

moles) before being heated to 80C for 20 hours. The material was

then distilled on a micro column to give 3.6 grams of higher boiling

material. NMR analysis indicated higher telomers and no simple adduct.



2 + 2 Cycloaddition Reaction of Chlorotrifluoroethylene with
CF2=CFCF2CF=CF2

The attempted cycloaddition reaction of chlorotrifluoroethylene

with CF2=CFCF2CF=CF2 was carried out in an ampoule at 160C for 48

hours. The CF2=CFCl (5.8 grams,0.05 moles) and F,l,4-pentadiene (10.6

grams, 0.05 moles) were placed in the ampoule, sealed, and heated to

160C. After the ampoule was opened and the overgases vented, the

starting material, CF2=CFCF2CF=CF2, was recovered.



The Addition of Bromine to CF2=CFCF2CF=CF2

A 50-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and a condenser. The CF2=CFCF2CF=CF2

(10.6 grams, 0.05 moles) was placed in the flask and stirred as the


I










bromine (8.0 g) was added dropwise via the dropping funnel. As the

reaction proceeded, the temperature rose to 50C and the flask was

cooled in a water bath. After the bromine had been added, the mixture

was distilled to give the dibromide CF2BrCFBrCF2CF=CF2 (76% yield,

14 grams, bp 126-127C, Figures 38 and 39). Figure 38 IR (liquid)

maxima in microns 5.6 (CF2=CF), 7.4, 7.65 (CF2=CF), 8.5, 9.0 (C-F),

9.5, 10.4, 11.7. Figure 39 F19 NMR, two fluorines, triplet for

(CF2=C); one fluorine, multiple for (CF=C); two fluorines, a

doublet of doublets for center CF2; one fluorine, a multiple for

CFBr; two fluorines and two multiplets for CF2Br.



The Attempted Radical Addition of 2-IodoheDtafluoropropane with
CF2=CFCF2CF=CF2

An ampoule was loaded with 2-iodoheptafluoropropane (14.8 grams,

0.05 moles) and CF2=CFCF2CF=CF2 (10.6 grams, 0.05 moles) before being

cooled to -196C in liquid oxygen and evacuated. After being sealed,

the ampoule was warmed to 155C for 36 hours. The pentadiene,

CF2=CFCF2CF=CF2, and CF3CFICF3 were the only products recovered.



The Attempted Reaction of Trifluoronitrosomethane with
CF2=CFCF2CF=CF2

An ampoule was charged with CF2=CFCF2CF=CF2 (4.2 grams, 0.02

moles) before being cooled in liquid oxygen and evacuated. Trifluoro-

nitrosomethane (CF3NO, 2.0 grams, 0.02 moles) was condensed into the

ampoule and the system sealed. The ampoule was allowed to warm to

-78C in a Dry-Ice acetone bath over a 48-hour period. Since the









deep blue color of CF3NO still remained, the ampoule was warmed to 0C

for an additional 48 hours, then to ambient temperature for eight

hours. When the ampoule was opened, the only products recovered were

trifluoronitrosomethane and CF2=CFCF2CF=CF2.



The Reaction of Ozone with CF2-CFCH=CHCH3
I I
CF2 --CFCH=CHCH3

A 250-ml Erylenmeyer flask was equipped with a gas inlet tube

and a outlet which was vented to the outside. The diner,

CF2-CFCH=CHCH3
I I
CF2- CFCH=CHCH3

(25 grams, 0.12 moles) was dissolved in methylene chloride (150 ml)

and placed in the reactor. Ozone, from a Welback ozone generator, was

bubbled through the mixture for three hours at n2% ozone concentration

(2.5 equivalents of ozone) after the solution had been cooled to -78C

in a Dry-Ice acetone bath. After removal of the methylene chloride,

a water white semi-viscous fluid remained which contained none of

the starting material. The reactivity of this material with potassium

iodide indicated the presence of the ozonide (Figures 40 and 41).

0-0
/ \
CF2-CFCH CHCH3
I I 010
^0
CF2- CFCH CHCH3


Figure 40 IR (liquid) maxima in microns 3.3, 3.38 (C-E), 7.2,

7.9, 8.3, 8.9, 9.1 (C-F), 11.2. Figure 41 H1 NMR, three

hydrogens, doublet for CH3; two hydrogens, multiple for CH.









An attempt to decompose the ozonide with zinc and acetic acid

became a run-away reaction after ,20 minutes and only polymeric

tars remained.



The Reaction of Ethanol and Potassium Hydroxide with CF2=CFCH=CHCH3

A 100-ml, three-necked flask was equipped with a magnetic

stirrer, thermometer, dropping funnel, and a condenser backed by a

liquid oxygen trap. The ethanol (50 ml) and potassium hydroxide (6

grams, 0.12 moles) were added to the flask and stirred as the

CF2=CFCH=CHCH3 (11.2 grams, 0.1 moles) was added dropwise. An exotherm

to 35C was noted and, after one hour, the mixture was washed with ice

water (500 ml). The lower organic layer was collected and dried over

molecular sieves and distilled to give 9.2 grams of a mixture of

CH3CH20CF2CFHCH=CHCH3 (80%) and CH3CH2OCF2CF=CHCH2CH3 (20%) (bp 125-

129C, Figures 42 44). Figure 42 IR (liquid) maxima in microns

3.35 (C-H), 5.8 (CF=CH), 5.92 (CH=CH), 7.7, 7.82, 8.2, 8.7 (C-F),

9.5 (C-0), 10.3. Figure 43 H1 NMR, three hydrogens, doublet

for CH3; three hydrogens, triplet for CH3; two hydrogens, multiple

for CH2; three hydrogens, three types of vinyl hydrogens. Figure 44 -

F19 NMR, one fluorine, multiple for (CF=C); one fluorine, multiple

for (CFH); two fluorines, multiple for (CF2). Table XIX Mass

spectrum m/e 168 (M1 ), 153 (M-CH3), 151 (M-CHs), 139 (M-C2Hs),

148 (M-HF), 123 (M-C2H5O).



The Reaction of Ethanol and Potassium Hydroxide with CF2=CFCH=CHCF3

A 50-ml, three-neck flask was equipped with a thermometer,

reflux condenser, dropping funnel, and magnetic stirrer. The ethanol










(20 ml) and potassium hydroxide (0.5 grams) were placed in the flask

and stirred over a 20-minute period. The CF2=CFCH=CHCF3 (8.8 grams)

was added via the dropping funnel over a 20-minute period with an

exotherm to 56C noted. After being cooled to room temperature, the

mixture was added to 100 ml of ice water and the organic layer collected

and dried over molecular sieves. Distillation gave 5.3 grams of

product, CH3CH2OCF2CF=CHCH2CF3 (bp 103-105C, Figures 67 69).

Figure 67 IR (liquid) maxima in microns 3.3 (C-H), 5.78 (CH=CH), 7.6,

7.8, 7.95, 8.2, 8.65, (C-F), 9.3, 9.6 (C-0). Figure 68 F19 NMR
4
three fluorines, multiple for (CF3). Figure 69 H1 NMR, three

hydrogens, triplet (CH3); two hydrogens, multiple (CH2-0); one

hydrogen, multiple (CH=C); two hydrogens, multiple (CH2).



Addition of Bromine to CF2=CFCH=CHCH3

A 50-ml, three-necked flask was equipped with a magnetic stirrer,

dropping funnel, thermometer, and reflux condenser backed by a liquid

oxygen trap. The diene, CF2=CFCH=CHCH3, (2.6 grams, 0.021 moles) was

placed in the flask and cooled in an ice water bath to +3C. The

bromine (3 grams) was added dropwise and a very vigorous reaction

observed. The exotherm reached 40C and was controlled by the rate

of addition of bromine. There was collected 5.3 grams of product,

CF2BrCFBrCH=CHCH3, which was distilled to give 4.2 grams of pure

product (bp 152-155C, Figures 45 and 46). Figure 45 IR (liquid)

maxima in microns 3.34, 3.4 (C-H), 5.9 (CH=CH), 7.7, 8.0, 8.4, 8.8

(C-F), 9.3, 9.7, 10.0, 10.6, 11.2, 11.7, 13.0. Figure 46 H1 NMR,

three hdrogens, doublet for CH3; two hydrogens, two types of vinyl

hydrogen. Table XV Mass spectrum m/e 283, 282 (1 ), 203, 201

(M-Br), 153, 151 (M-CF2Br), 122 (M-Br2).










Addition of Bromine to CF2=CFCH=CHCF3

A 50-mi, three-necked flask was placed in an ice water bath and

equipped with a magnetic stirrer, condenser, thermowell, and dropping

funnel. The diene, CF2=CFCH=CHCF3 (8.8 grams, 0.05 mole) was placed

in the flask and cooled to 0C before the bromine (8 grams) was added

via the dropping funnel. The reaction was slow and, after one hour,

the color had disappeared. Infrared analysis indicated the 1,4-

addition product had been formed. NMR analysis proved the mixture to

be a 75/25 ratio of 1,4- to 1,2-addition (bp 124-126C, Figures 70

and 71). Figure 70 IR (liquid) maxima in microns 3.15, 3.28 (C-H),

5.8 CF=CH, 5.85 (CH=CH, 7.5, 7.6, 7.95, 8.3, 8.6, 8.7 (C-F), 9.4,

10.6, 11.1, 13.5. Figure 71 F19 NR, three fluorines, two

multiplets for (CF3); two fluorines, two multiplets for (CF=C) and

(CFBr); three fluorines, two multiplets for (CF3). Table XXVIII -

mass spectrum m/e 336 (M+ ), 257, 255 (M-Br), 238, 236 (M-FBr), 186

(M-Br-CF3). High resolution mass spectrum CsF6H279Br2, calculated

mass 334.07, measured 333.84.



The Reaction of Trifluoronitrosomethane with CF2=CFCH=CHCH3 at -78C

An ampoule was charged with CF2=CFCH=CHCH3 (2.25 grams, 0.02

moles) before being cooled with liquid oxygen to -196C and evacuated.

The trifluoronitrosomethane (CF3NO, 2.0 grams, 0.02 moles) was

condensed into the ampoule and the system sealed. The ampoule was then

placed in a Dry-Ice acetone bath at -780C for 48 hours. A green,

thick oil was present; therefore, the ampoule was opened and the

overgases were vented. The product, a slightly yellow viscous liquid,










was recovered (3.1 gram) and placed in a 5-ml flask. A full vacuum

was applied to remove the lower boiling component which was identified

as CF2CF=CHCHCH3 (2.0 grams), the 2 + 4 cycloaddition product. The
\ /
N-0


/
CF3

remaining polymeric material contained two types of olefin

as characterized by infrared analysis. Both -NOCF2CF--

j CF3 CH n

CH
I
CH,

-{NOCF2CF=CHCH--

CF3 CHa n 1,4 addition product


absorptions

and



1,2 addition

product


of the polymer were found to be present (Figures 47 49). Figure

47 IR (liquid) maxima in microns, 3.32 (C-H), 5.85 (CF=C),

7.2, 7.7, 7.93, 8.3, 8.4, 8.8 (C-F), 9.25, 9.6, 11.0, 13.6.

Figure 48 H1 NMR, three hydrogens, doublet for (CH3); one

hydrogen, multiple for (CH-O); one hydrogen, vinyl hydrogen

multiple. Figure 49 F19 NMR, three fluorines, multiplet for

(CF3-N); one fluorine, quartet for (CF=C); two fluorines,

multiple for (CF2-N). Table XXI Mass spectrum m/e 221 (M +),

122 (M-CF3NO), 121 (M-CF3NOH). Figure 53 1,2 and 1,4 polymer

with CF3NO. High resolution mass spectrum, C6HsF6NO, calculated

mass 221.11, measured 221.03.










The Reaction of Trifluoronitrosomethane (CF3NO) with CF2=CFCH=CHCF3
at -78C

A 50-ml ampoule was charged with CF3NO, trifluoronitrosomethane,

(2 grams) and CF2=CFCH=CHCF3 (3.52 grams). The ampoule was sealed

and the mixture placed in a Dry-Ice acetone bath for 24 hours. The

ampoule was then opened and the products collected (5.1 gram).

Distillation gave the 2 + 4 cycloaddition product (bp 100-102C,

2.2 gram) and polymer (1.4 grams, Figures 72 75). Figure 72 -

IR (liquid) maxima in microns 3.2 (C-H), 5.85 (CF=CH), 7.8, 8.3,

8.7, 8.8 (C-F.), 10.7, 11.1. Figure 73 IR (liquid) maxima in

microns 3.16 (C-H), 5.85, (CF=CH), 6.2 (CH=CH), 7.5, 8.0 9.0

(C-F), 8.3, 10.2, 10.7. Figure 74 H1 NMR, one hydrogen,

multiple for (CH-0); one hydrogen, doublet of pentets for vinyl

hydrogen. Figure 75 F19 NMR, three fluorines, multiple for

(CF3-N); one fluorine, multiple for (CF=CH); two fluorines,

multiple for (CF2-); three fluorines, multiplet for (CF3-C).

Table XXIX Mass spectrum m/e 275 (M+ ), 256 (M-F), 206 (M-CF3),

176 (M-CF3NO), 126 (M-CF3NO, CF2). High resolution mass spectrum,

C6H2F9NO, calculated mass 275.08, measured 275.00.



The Reaction of Phenylmagnesium Bromide with CF2=CFCH=CHCH3

A 250-ml, three-necked flask was equipped with a magnetic stirrer,

thermometer, reflux condenser, and a dropping funnel. The flask was

set up in an ice water bath before the ethyl ether (150 ml) and

CF2=CFCH=CHCH3 (12.2 grams, 0.1 moles) were added. The mixture

was stirred as the phenylmagnesium bromide (0.1 mole) was added over










a 30-minute period. The temperature did not increase as had been

expected. After being stirred for five hours, the mixture was

hydrolyzed in ice water, the ether layer was collected and dried

over molecular sieves. The ethyl ether was removed to give 5 grams

of higher boiling material which was vacuum distilled to give 2.1

grams of a mixture of biphenyl, phenol, and 1.2 grams of the desired

product C6HsCF=CFCH=CHCH3 (Figure 76). Figure 76 IR (liquid)

maxima in microns 3.22, 3.25, 3.32, (C-H), 5.8 CF=CF, 6.2 (C6H5),

8.0 8.4 (C-F), 13, 14 aromatic. Table XXX Mass spectrum m/e

180 (M+), 179 (M-H), 165 (M-CH3), 154 (M-C2H2), 153 (M-C2H3), 152

(M-C2H4).



The Reaction of Phenylmagnesium Bromide with CF2=CFCH=CHCF3

A 100-ml, three-necked flask was equipped with a magnetic stirrer,

a thermometer, a reflux condenser, and a dropping funnel. The ethyl

ether (30 ml) and CF2=CFCH=CHCF3 (8.8 grams, 0.05 moles) were placed in

the flask and stirred as the phenylmagnesium bromide (0.05 moles) was

added dropwise via the dropping funnel. There was an immediate

exotherm to 50C with vigorous reflux of the ether. The addition was

carried out over a 30-minute period and, after one hour of stirring,

the solution was hydrolyzed in ice water. The ether layer was

collected, dried over molecular sieves and the ether removed. Further

vacuum distillation gave the desired C6H5CF=CFCH=CHCF3 (8 grams,

bp 60-65/0.1 mm, 68% distilled yield). A GLC indicated two isomers,

cis and trans in a 65/35 ratio (Figures 77 and 78). Figure 77 -

IR (liquid) maxima in microns. 3.18, 3.32 (C-H), 5.95 (CF=CF),









6.19 (aromatic), 7.6, 7.8, 7.9, 8.8 (C-F), 10.2, 12.9, 14.1.

Figure 78 F19 NMR, three fluorines, multiple for (CF3); two

fluorines, multiplets for (CF=CF) both cis and trans. Table XXXI -

Mass spectrum m/e 235, 234 (MW), 165 (M-CF_), 164 (M-CF3, H),

145 (M-CF3, HF). High resolution mass spectrum CnIH7Fs, calculated

234.17, measured 234.05.

The reaction was repeated at -30C using the same ratio of

starting material. The hydrolysis was carried out with D20 and

the ether layer collected, dried over molecular sieves and the ether

removed to give only C6H5CF=CFCH=CHCF3 and no C6HsCF2CFDCH=CHCF3

showing that the [C6HsCF2CFCH=CHCF3] is not an intermediate.



Attempted Reaction of CF2=CFCH=CHCH3 with Diethylamine

A 250-ml, three-necked flask was equipped with a magetic stirrer,

dropping funnel, reflux condenser, and thermometer. The ethyl ether

(150 ml) and diethyl amine (7.4 grams) were placed in the flask and

stirred at 5C in an ice water bath before the diene CF2=CFCH=CHCH3

(12.2 grams, 0.1 mole) was added via the dropping funnel. There was

no apparent reaction and the mixture was warmed to ambient tempera-

ture and stirred for 48 hours. The ethyl ether was then removed

under vacuum to give 6.6 grams of higher boiling material which was

distilled and determined to be the 2 + 2 cyclic dimner of the

CF2=CFCH=CHCH3.









Reaction of CF2=CFCH2CHBrCH3 with Magnesium

A 50-ml flask was equipped with a magnetic stirrer and a reflux

condenser before being charged with magnesium turnings (0.1 mole,

2.4 grams) and 10 ml of ethyl ether. The CF2=CFCH2CHBrCH3 (24 grams,

0.2 mole) was added and an immediate exotherm caused the ether to

reflux. After the addition was complete, the mixture was hydrolyzed

and the ether layer collected and dried over molecular sieves. The

ether was removed to leave the starting material (13 grams) and

higher boiling material (7 grams). Further vacuum distillation gave

1.1 grams of material identified as the desired coupled product along

with polymeric material (Figure 79). Figure 79 IR (liquid)

maxima in microns 3.32 (C-H), 5.52 (CF2=CF), 7.7, 7.95, 8.7, (C-F),

9.2, 12.5.



Attempted Reaction of CF2=CFCH=CHCF3 with H2SO. and Water

A 25-mi flask was equipped with a =agnetic stirrer and a reflux

condenser before being charged with water (10 ml) and H2S04 (2 ml).

The diene CF2=CFCH=CHCF3 (2 grams) was added and the mixture stirred

for six hours. A sample was then taken and infrared analysis

showed that no reaction had taken place.
















SECTION 4

ENVIRONMENTAL IMPACT



Due to the small scale usage of chemicals and proper disposal

procedures, there was no unexpected iLpact on the environment. A

listing of the compounds used along with the (NIOSH) National

Institute for Occupational Safety and Health Registry data are

included.



1. Acetic acid (CH3COOH) AF-1225000 TXDS oral rat

LD50: 3310 mg/kg TL 10 ppm DOT corrosive material

0 0
2. Benzoyl peroxide O)-C-OO-C- ?j DM-8575000 TXDS

oral-hum LDLo 500 mg/kg TIL 5 g/kg DOT organic peroxide

3. Bromine (Br2) EF 9100000 TXDS inh mus LCso: 750 ppm/

9 min. TL TWA 0.1 ppm DOT corrosive material

4. Butadiene (CH2=CHCH=CH2) EI-9275000 TXDS oral rat

LDso: 5480 mg/kg TL 1000 ppm DOT flammable gas

5. 1,2-Dibromo-2-chlorotrifluoroethane (CF2BrCFClBr)

KH-7600000 TXDS inh-rat LcLo 25,270 ppm/15 M

harmless liquid for shipping purposes

6. Dichloroiodotrifluoroethane No listing, considered

harmless










7. Diethyleneglycol dimethyl ether (CH3OCH2CH2OCH2CH2OCH3) -

No listing, considered nontoxic, compared to tetraethylene-

glycol dimethyl ether.

8. Dimethyl sulfide (CH3SCH3) PV-5075000 TXDS oral rat

LD5o: 535 mg/kg DOT flammable liquid

9. Dimethyl sulfoxide (CH3SO2CH3) PV-6210000 TXDS oral =us

LD5o: 21 grams/kg DOT flanmnable

10. Ethanol (CHsCH2OH) KQ-6300000 TXDS oral rat LD50o:

14 grams/kg TL 1000 ppm DOT flammable liquid.

11. Ethylene (CH2=CH2) KU-5340000 TXDS inh mus LCso: 95 ppm

TLm 96: 1000-100 ppm DOT flammable gas

12. Iodine (12) NN-1575000 TXDS oral human LDLo: 5 mg/kg

inh dog LDLo: 40 mg/kg TL 0.1 ppm

13. Methylene chloride (CH2C12) PA-8050000 TXDS oral rat

LD5o: 167 mg/kg TL 2000 ppi DOT ORM A otherwise

restricted material

14. Ozone (Oz) RS-8225000 TXDS inh rat LCso50: 4.8 ppm/4H

TL 0.1 ppm DOT toxic gas

15. Potassium t-butoxide (CH3C(CH3)20-K) No listing

DOT corrosive solid.

16. Potassium hydroxide (KOH) TT-2100000 TXDS oral rat

LD5o: 365 mg/kg TL 2 mg/m' DOT corrosive material

17. Propene (CH2=CHCH3) UC-6740000 AQTX TLm 96: over 1000 ppm

DOT flammable gas










18. Pyridine (Do UR-8400000 TXDS oral rat LD0o:


891 mg/kg TL 5 ppm DOT flammable liquid

19. Sodium hydroxide (NaOH) WB-4900000 TL 2 mg/m3

IRDS skin rabbit 50 mg/24 H SEV DOT corrosive material

20. Tetrafluoroethylene (CF2=CF2) KX-4000000 TXDS inh rat

LCso: 40,000 ppm/4 H DOT Flammable gas

21. Trifluoropropene (CF3CH=CH2) No listing

22. Zinc (Zn) ZG-8600000 TXDS inh human TCLo: 124 mg/m3/

50 min.

23. Zinc bromide (ZnBr2) ZN 1400000 TXDS oral rat LDo50:

350 mg/kg TL 1 mg/m3 DOT corrosive solid










Explanation of Symbols and Abbreviations for Environmental Impact



TXDS Toxic dose data

inh Inhalation

rat rat

ppm Parts per million

M Minutes (nin.)

LcLo Lowest lethal concentration

LDso Lethal dose calculated to cause 50%

of the experimental animal population

to die

LDLo Lowest lethal dose

TL Threshold limits

TLm 96 Concentration which will kill 50% of

the exposed organism within 96 hours

AQTX Aquatic toxicity ratings

SEV Severe irritation effects

DOT Department of Transportation

























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