Title: Coupling reactions of fluoroalkyl iodides
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 Material Information
Title: Coupling reactions of fluoroalkyl iodides
Physical Description: iv, 83 l. : illus. ; 28 cm.
Language: English
Creator: Tsoukalas, Skevos Nicholas, 1928-
Publication Date: 1966
Copyright Date: 1966
 Subjects
Subject: Fluoroalkyl iodides   ( lcsh )
Zinc   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 82.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
 Record Information
Bibliographic ID: UF00097884
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000421891
oclc - 11021109
notis - ACG9889

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COUPLING REACTIONS OF

FLUOROALKYL IODIDES






















By
SKEVOS N. TSOUKALAS











A DISSERTATION PRLSLNTLD 10 THE GRADUATE COUNCIL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DFGREE OF DOCTOR OF PHILOSOPHY









UNIVERSITY OF FLORIDA


April, 1966














ACKNOWLEDGMENTS


The author wishes to extend his thanks to his research

director, Dr. Paul Tarrant, for his thoughtful guidance

throughout this investigation. He wishes also to thank the

administration of Peninsular ChemResearch, Inc. for the use

of the equipment of the company and for the many donations

of chemicals. Special thanks are extended to all the

employees of Peninsular ChemResearch, Inc. for their aid

and encouragement.

The success of this work was in no small part due to

the patience and understanding of the author's wife, Helen.












TABLE OF CONTENTS


Page

ACKNOWLEDGMENTS 1i

LIST OF TABLES iv

INTRODUCTION 1

DISCUSSION 5

Reaction of Saturated Primary Perfluoroalkyl
Halides with Zinc 5

Reaction of Saturated Secondary Ferfluoroalkyl
Halides with Zinc 12

Reactions of Perfluorovinyl Halides with Zinc 13

Cross-Coupling Reaction of Perfluoroalkyl
Iodides with Iodetrifluoroethylene and
Bromotrifluoroethylene in the Presence of
Zinc 13

Reaction of Fluorine-Containing Alkyl Halides
with Zinc 17

Reactions of Aromatic Iodides and Bromides
Containing Fluorine with Zinc 27

Reaction of Perfluoroacyl Iodides with Zinc 29

EXPERT BRlTAL 31

SUMMARY 73

APPENDIX 76

BIBLIOGRAPHY 82

BIOGRAPHICAL SKETCH 83


iii













LIST OF TABLES


Table Page

1. Products of the Reaction of CF I and C F I
with Zinc in Acetic Anhydride 2nd Variat&on
of their Ratios with Temperature 10

2. Products of the Reaction of CF I and CF =CFI
with Line in Acetic Anhydride and Variation
of their Ratios with Temperature 16

3. Products of the Reaction of C F I and CF =CFI
with Zinc in Acetic Anhydride aZd Variation
of their Retios with Temperature 70

4. Properties of Compounds Prepared 71













I. INTRODUCTION


The coupling of alkyl iodides with the aid of various

metals is not a novel reaction. The well-known Wurtz reac-

tion is a typical example; in it organic halides are coupled

to give a hydrocarbon with twice as many carbon atoms as the

original halide. Investigators in the field of organic

fluorine chemistry have realized the importance of the

coupling reaction and some fluorine containing alkyl halides

have been coupled with zinc or mercury. In several cases,

when a fluorine containing alkyl iodide was allowed to react

with zinc, the corresponding organozinc iodide was also

formed in addition to the coupled and other products.

Earlier attempts by Emeleus and Haszeldine (1) to pre-

pare CF ZnI and C2 FZnI from zinc, CF3I and C2F I failed and
25 2 57)
no coupled product was reported. A few years later, Miller

(2) reported the preparation of CF 7nI and C F11ZnI from

the reaction of the corresponding iodides with zinc in

dioxane or ether. In addition, he obtained some C6F14 and

C10F22 resulting from coupling of the C3F 7 and C FllI.

However, when he allowed CFCl2I to react with zinc he ob-

tained mainly CFC12H resulting from reduction of the start-

ing material and some coupled product, CFC12CFC12. In this

case the organozinc compound was not formed. In 1951







Haszeldine (3) prepared CF3ZnI and C3F ZnI but made no men-
tion of the coupled product at that time. Later (4) the o5,

same author obtained a small yield of C6F14 from the reac-
tion of C3F7I and zinc in ether and a good yield of C6F14

when C3F I was passed through a tube packed with zinc at

3100 C.
Haszeldine and Steel (5) have reported the addition

of CF3I to CF2=CFC1 under ultraviolet irradiation. From

this reaction they obtained a mixture of telomers with the
general formula CF3(CF2CFC1)nI. Under certain conditions

the compound, CF CF2CFClI, is formed as a major product.

These workers treated CF3CF2CFC1I with mercury under ultra-
violet irradiation and obtained the coupled product,

CF CF2CFC1CFC1CF2CF. IMusgrave, Chambers and Savory (6)

have also coupled (CF3)2CFI using mercury and ultraviolet
irradiation. When they allowed (CF3)2CFI to react with
zinc in boiling dioxane they obtained (CF3)2CFZnI and made

no mention of the coupled product.
In an attempt to prepare perfluorobutadiene, Haszeldine

(7) first coupled the iodide, CF2ClCFC1I, with zinc in dry (tS)
dioxane, and the coupled product was in turn dehalogenated
to yield CF2 CFCFwCF2. He also coupled the compound,

CF2BrCFClI, using mercury and ultraviolet irradiation. Two

years later, Henne (8) successfully repeated the same reac-
tion with CFPClCFClI in a mixed solvent of acetic anhydride 19q

and methylene chloride. Using the same solvent system, Henne

also coupled C3F3C 1Br with zinc and obtained C6F6C1g.







Shi-Chun Hung (9) reported the preparation of the com-

pound, H(CF2)81 by coupling I(CF2)4H with zinc or mercury.

Internal coupling of fluorine-containing dibromides has also

been reported by some investigators. Tarrant, Lovelace and

Lilyquist (10) have prepared F2CH2C(CH3)2 from

CF2BrCH2CBr(CH3)2 and zinc in 1-propanol, and Harmon (11)

reported the preparation of 2CF from the reaction of

Br(CF2)3Br with zinc. Although isolated examples of the

coupling reaction of fluorine-containing iodides have been

reported for several years, no systematic study of the syn-

thetic possibilities of this reaction has been carried out.

The main purpose of this research was to examine the

factors involved in the coupling of fluorineicontaining

halides with zinc, and to try, if possible, to develop a

synthetic procedure for new and interesting fluorine

compounds.

The first aim of the project was to determine whether

or not the reaction of fluorocarbon iodides with zinc is

a general reaction. A second objective was to determine

if chlorides or bromides would participate in coupling

reaction. Another objective was to determine whether the

coupling reaction is restricted to saturated primary

fluoroalkyl iodides or whether secondary and tertiary

halides could also be coupled, as well as the unsaturated

ones. It would also be interesting to see if the aromatic

halides, containing fluorine on the ring, could be coupled.








A coupling reaction of an organic halide containing fluorine

as well as ether funetional groups would be of gret value

in synthesis, as it would create the possibility of synth*-

sizing new fluorine copeonds with functional groups which

would permit further transformations.

The cross-coupling of various iodides would also be of

great interest and if it could be carried through suoeess-

fully, a variety of fluorine compounds seuld be synthesized.












II. DISCUSSION


Reaction of Saturated Priary Perfluereolkyl
Halides with Zinc

As was mentioned in Section I, the lower fluoroalkyl

iodides react with activated zine dust or granular zinc

to yield a mixture of products resulting from coupling

of the perfluoroalkyl radical and from reduction of the

perfluoroalkyl iodide. In some instances, an olefin with

the same number of carbons is also formed. In our labora-

tory when perfluoro-n-propyl iodide, C3FI, was allowed to

react with zinc powder activated by addition of one drop

40% hydrogen bromide, in dry ethyl ether as a solvent, a

mixture of n-C6F14 and CF3CF2CHF2 was obtained in a ratio

of 2:1, as well as a small amount of CF CF=CF2. The solids

formed in this reaction also yielded on heating, CF3CF=CF2,

indicating that the organozin eesopound was probably formed

during the reaction.

In a similar way, when perfluoro-n-heptyl iodide,

C7F151, was allowed to react with activated granular zinc

in a mixture of acetic anhydride and methylene chloride,

a yield of 67% of the coupled product, C14F30, was

obtained but the reduction product was not isolated.








The CF3(CF2)12CF3, a waxy solid, was identified by its

melting point, fluorine elemental analysis, and its NMR

spectrum. The infrared spectrum was also consistent with

the above structure, being almost identical to that of

Teflon. The infrared spectra of the lower members of satu-

rated fluorocarbons differ markedly; however, as the chain

of carbon atoms increases in length, the infrared spectra

become simpler and approach the spectrum of Teflon (see

Appendix).

In studying the effect of the chain length of the

saturated perfluoroalkyl iodides on the coupling reaction

with zinc, it was found desirable to react an iodide with

as many carbon atoms as possible, in order to obtain a

clearer picture of their relative reactivity and the ease

of their coupling with zinc. The perfluoroalkyl iodides,

however, are usually prepared from the silver salts of the

perfluorocarboxylic acids by heating with iodine. The lack

of perfluorocarboxylie acids with long chain lengths was an

obstacle in obtaining the desired starting material. A long

straight chain alcohol with the formula HC10F20CH20H,

obtained from Peninsular ChemBesearch, Inc. was converted

into the acid HC10F20COOH by oxidation with KMnO4 in aeette

acid solution. Then, the silver salt of the asid,

HC10F20oCOQg, was prepared by reaction of the acid with

silver exlde in diteane.








Heating of the silver salt with exeess of iodine at

1300 C. yielded the iodide 1C10F20I in which the hydrogen

and iodine atoms are attached to the two end carbon atoms

of the chain. This iodide was a white crystalline solid

with a melting point 69-700 C. Its structure was veri-

fled by fluorine analysis and by NMR spectroscopy.

Since the hydrogen and iodine atoms are attached to

carbon atoms separated by a chain of eight carbon atoms,

it is reasonable to assume that the effect of the hydrogen

on the earbon-iodine bond would be negligible and that the

iodide will react with zinc the same way the perfluorodeeyl

iodide, C10F211, would.

When the HCo0F20I was added to a mixture of acetic

anhydride, methylene chloride and granular zinc activated

by hydrobromic acid, and the mixture was heated under con-

tinuous stirring to 55 C., a reaction took place and white

solids precipitated, showing positive I" test.

Treatment of the reaction mixture with dilute B2SO4

dissolved all the solids and a heavy organic layer was

isolated which, upon removal of the methylene chloride in

the vacuum system, yielded a yellow solid. After purifi-

cation, the material appeared to be a white crystalline

solid with a melting point of 1650 C. and a boiling point

of 2860 C. This solid was considered to be the coupling

product HC20F40H and it was obtained in a 75% yield. The








NNE spectral and anslylsis for flvertno or* In ****v@t 00S

the above, forwaula.

It Is appa~renk that th# incrage~d ohain length has a

rather benfeficil Wffebt :on the GWAPling rmeation. Ila

general, it ean be said that any n-perfluere*alkyl 194edif
w111 reeet with zinme undr proper renditions. &nd that t14#

yield of thoecoupling product will intreFSs k OSo the1so t

of the earbon ch&ain Is incevosed.:

It Is reasonabl* to expbaet two different perfluervmwjkyl

iodides when reacted togethexr witth zin to feross*Mpl.

HoevYer, no refeorenee has Imee femnd in the l4teraturv oon-

corning this rvaetion. Seveal *tp*:riments with. varlows

perfluorselkyl led14es haLv* o"Ptirme this epeta*&tion; the

cross-eompled pretwets sort obtainot In yields deperA~nt

upon the t6WWmpature, as. Wotl .4 (m t~hd drys**4 of tho Sol-

vent and 6f fthe sorting mttrial8. Whonev*# the ta1*0st

and tho rvaottants @Lre not W411 dr**d., th .il j6 th

coupled Droduot Is roduced and thou* af tbo retdustLen

pradatt(s) ar* intres#et.

The #ffoet of the temperatfen ft tho 41Atrtb#*Ian 01

th# pro"**$s Is well illuxtyated by '41e rweuatin 4f tritlee-

resothyl letld# so* iubeldsethl 944 with zhee in

&**tiod *nhyt4Lr# to # &#etWat. #k# so"e q*&sk~t#t Of

reade~nV4 AMA v&t %00*fad 04610d lit 0WhW too" W&Il

*Wp*10e. 0"e of wkhen "m ket44 *e Igo* C.. tom *eee04








room temperature. The products were analysed by gas

chromatography; the results are shown in Table 1.

It is evident from the figures in Table 1 that the

cross-eoupled reaction is favored at higher temperatures.

In addition to the predvet famed from cress-eoupling of

the two iodides, the coupled produet of eaah iodide is

also formed, as in the Wurtz r4actlon.

The same reaction, when carriedd out in diozane as a

solvent yielded no coupled products, but only the reduc-

tion products of the two iodides, CF3H and C2F5H, were

obtained. Treatment of the solids produced in the reac-

tion in dioxane with water also yielded some CF H and

C2F H, probably by hydrolysis of the CF3ZnI and C2F5?nI.

After studying the coupling reaction of the

perfluoro-n-alkyl iodides with zine, the investigation of

the same reaction of perfluoro-n-alkyl bromides and chlo-

rides was Investigated. When a atture of

heptafluo.o-n-propyl bromide, zinc, acetic anhydride and

methylene chloride was sealed in a glass ampule and the

ampule was heated to 1000 C., the starting material was

recovered and only a small amount of the reduction product

C3F H was found. At higher Itmperatures the conversion is

higher, but even at 2750 C. 30% of the C3F 7r remained

unahanged and 70% wms conVerted into C3F H. No coupled

preduet or olefin, CF 3C*CF2, was detected in this reaction.




















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In another experiment, when difluorodibroaeoaethane was

allowed to react with granular zine in a mixture of acetic

anhydride and methylene chloride as solvent, the reduction

product was not formed and a 15% yield of CF2=CF2 was

obtained. The formation of the tetrafluoroethylene may be

explained if we assume that the difluoroearbene CF2 is

formed as intermediate from the CF2Dr2 and zinc, and further

that 2:CF2 diradicals combine, yielding the CF2=CF2.

Another possibility is that the coupled product CF2BrCF2Br

is first formed and dehalogenates further with zinc

yielding the CF2=CF2. A further attempt was made to cross-

couple CF2Br2 with C3F I. However, the products that were

isolated, C3F'7,H C6F14, C3F7Dr, indicated that no cross-

coupling took place. The C F 7i and the C6F14 resulted from

reduction and coupling of the CF I, respectively, and the

C3F Br was probably formed by abstraction of a bromine atom

from the CF2Ir2 by a C3F7 radical.

It is evident from the previous discussion that the

perfluoroalkyl bromides are more reluctant to react with

zinc than the perfluoroalkyl iodides, and it was expected

that the perfluoroalkyl chlorides would be even less

reactive than the bromides. Indeed when a mixture of

perfluoreethyl chloride, C2F5Cl, granular zinc and dry ethyl

ether was sealed in a glass ampule and the ampule was

heated to 1000 C. under ultraviolet irradiation, the

starting material, C2F5C1, was reeevered unchanged.







Thuat of the saturated primary p-erfluoroalkyl halides,
only the iodides couple with zinc..





Secondary perfluorealkyl halides are not as readily
available as the primary ones and tho study of their reac-
tion with zinc was limited to the reaction of heptafluoro-
isopropyl iodide with zinc.
When this iodide was added to a mixture of acetic
anhydride and activated zinc, reaction took plice at room
temperature and heat was Ovolved. The product isolated from
the above reaction was found by gas chromatography to be
composed of 25% CF3cF=cF 21P 50% CF 3 cFHF30 2% unreacted
starting material, (CF 3)2CFI, and 8% of a compound Identi-
fied by molecular weight and NMR to be the Coupled product
(CF 3)2CF-CF(CF 3)2*
Since no other secondary porfluoroealkyl iodide was
available for study, no definite conclusion. can be derived
In regard to the ralatl'tf reactivity of tha primary and
secondary p-erfluoroalkyl Iodides. It smewe, however, that
thit secondary react with comparable oaso with zinc, but
the predominant ps*4Mets are the reduetlon product and tht
corresponding olofin and the preparatory value of thia
reaction Is questionabli due to the 9mall Yiwld of th,*
cop~dpouc bsind







Reactions of Perfluorovinyl
Halides with 7.inc


In attempting the reaction of unsaturated perfluoro-

alkyl halides of the vinyl type, it was hoped that a new

route could be developed for the preparation of perfluoro-

butadiene by coupling of the halide with zinc. This would

be of great practical value because it would eliminate the

several steps involved in the preparation of perfluorobuta-

diene. The reaction with zinc was studied with the iodo-

trifluoroethylene and with the bromotrifluoroethylene in

acetic anhydride, in perfluoroacetic anhydride, and in

ethyl ether as solvents.* The reactivity of those compounds

with zinc is lower than those of the saturated perfluoro-

alkyl iodides and bromides, and no reaction takes place at

room temperature. Above 600 C., however, both the iodotri-

fluoroethylene and the bromotrifluoroethylene reacted and

they both yielded the same product, CF2=CFH, which is the

reduction product. Variation of the solvent system as well

as irradiation of the reaction mixture with an ultraviolet

lamp did not change the course of the reaction and again

the sole product was the reduction product without even a

trace of the coupled product, CF2=CF-CF=CF2.


Cross Coupling Reaction of Perfluoroalkyl Iodides
With lodotrifluoroethylene and Bromotrifluoroethylene
in the Presence of 7inc


The coupling of a perfluoroalkyl iodide with iodotri-

fluoroethylene or bromotrifluoroethylene could result in








the formation of an alpha fluoro olefin with two more

carbon atoms than the original saturated iodide. Con-

sidering the fact that olefins, whether organic or

perfluorinRted, are one of the most versatile and most

valuable group of compounds, the success of the above

coupling reaction would be of synthetic value, making

feasible the preparation of alpha olefins that perhaps

would be difficult to synthesize by other methods.

When trifluoromethyl iodide and iodotrifluoroethylene

were mixed together and were allowed tc react with zinc

in acetic anhydride at 1300 C., solids were formed that

gave a positive test for iodide ion. The volatile

products were separated by gas chromatography and a

small amount of the desired olefin, CF3CF=CF2, was

obtained in addition to the coupled and the reduction

products CF3CF3, CF i, and CF2=CFI:.

In order to improve the yield of the olefin, three

glass ampules, charged with the same quantities of CF I,

CF2=CFI, zinc and acetic anhydride, were allowed to react

at different temperatures. One ampule was left at room

temperature, and the other two were heated to 600 C. and

1200 C., respectively. Analysis of the reaction mixtures







by gas chromatography showed that the yield of the cross

-coupled product, e.g. the olefin, is greater at the lower

temperature. Complete analysis of the reaction mixtures

at the three different temperatures was made and the

results were tabulated in Table 2.

Since it was found previously that the iodotrifluoro-

ethylene would not react at room temperature, the formation

of the olefin and of the CF2=CFI must have been caused by

some intermediate species resulting from the reaction of

trifluoromethyl iodide and zinc.

Analogous results were obtained when the iodotrifluoro-

ethylene and perfluoro-n-iodopropane were allowed to react

with zinc in acetic anhydride as a solvent. The composition

of the products of this reaction at 250 C., 60 C., and

1250 C. has been tabulated in Table 3.

When perfluoroacetic anhydride was used as a solvent

in the reaction of CF3I and CF2=CFI with zinc, a yield of

7% of the coupled product was obtained at 1000 C. reaction

temperature.

While the saturated perfluoroalkyl bromides were found

incapable of coupling and also cross-coupling with other

bromides or iodides, reaction of CF2=CFBr with CF I yielded

a small amount of CF3CF=CF2, together with C2F6, CF3H and

CF,2=CFH. No attempt was made to improve the yield. A

further attempt to cross-couple CF =CFI with C F 5C was

unsuccessful. When those two compounds were treated with

























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zinc in acetic anhydride-methylene chloride as a solvent,

the C F C1 was recovered and the CF2=CFI was converted into

the reduction product, CF2=CFH.

It is apparent from the previous discussion that,

while it is possible to prepare an alpha olefin by cross

-coupling with zinc of a saturated perfluoroalkyl iodide

and CF2=CFI or CF2=CFBr, the yields are low and unless some

way is found to improve them, the practical value of this

reaction is small.

The possibility of preparing olefins of the type

CF2 CFR (where R is an aliphatic alkyl group containing

no fluorine) by cross-coupling of CF2=CFI and RI with the
2-
aid of zinc, was examined. When a mixture of CFfCFI,

C2H51, activated zinc and dimethyl sulfoxide as a solvent

was sealed in a glass tube, reaction began at room tempera-

ture and the heat of the reaction warmed the reaction tube.

Analysis of the products by gas chromatography showed that

the major product, C2H6, was formed in a 65% yield by

reduction of the C2H I but no other product was isolated.


Reaction of Fluorine-Containing Alkyl
Halides with Zinc


In this section, the coupling reaction of iodides

containing fluorine as well as other elements such as

hydrogen, chlorine and oxygen is described. The experi-

mental results indicated that it is possible for iodides

containing other elements besides fluorine to couple.







However, whenever dehalogenation is possible, it is pre-

ferred over the coupling reaction. The yields of the

coupling product varied from iodide to iodide and some-

times they were satisfactory.

When a mixture of l,1,2-trifluoro-l-chloro-2-iodoethane

CF2ClCFHI, activated zinc, and dioxane was sealed in a glass

ampule, reaction started as soon as the ampule was brought

to room temperature, and heat was evolved. The products

obtained from this reaction were CF2=CFH in 97% yield

resulting from dehalogenation of the starting material,

and CF2=CFC1 in 3% yield. Better results, however, were

obtained when this reaction was carried out in a three

-necked flask with a mixture of acetic anhydride-methylene

chloride as a solvent. As soon as the starting material

was added to the mixture of acetic anhydride-methylene

chloride and zinc, an exothermic reaction began. The

temperature of the reaction mixture was kept at 350 C.

with a water bath.

When the reaction mixture was analyzed by gas chroma-

tography the following compounds were separated and

identified:

Ratio of Products

CF2C1CFHCFHCFHCF2C1 45%

CF2ClCFHCH2CFHCF2C1 45%

CF2ClCFHI 10% Unreacted starting material


The first compound resulted from coupling of the









starting material and the second, surprisingly enough,

apparently from cross-coupling of the starting material

with the solvent CH2C1l. Those two compounds were identi-

fied by their molecular weight, and by chlorine analysis.

The NMR spectrum also was in agreement with the above

formulas of the products.

Repetition of this reaction under a variety of condi-

tions indicated that the best yields of coupled product

were obtained when the temperature was controlled around

30-350 C. and when the starting material was added in large

portions and not dropwise. An increase in temperature as

well as dropwise addition of the starting material favored

the dehalogenation reaction.

Following the successful coupling of CF2C1CFI-I, the

reaction of the l,l,l-trifluoro-2-iodoethane, CF CH2I, with

zinc was attempted in the same solvent system and at 350 C.

When the starting material, CF3CH2I, was added in one por-

tion to the mixture of solvent and zinc, exothermic reac-

tion began immediately and the temperature was kept at

35e C. with the aid of a water bath. When the reaction
mixture was analyzed by gas chromatography, the following

eempounds were separated:







Ratio of Products

CF2=CH2 48% Identified by its IR spectrum

CH CF3 40% Identified by its IR spectrum

CF CH2CH2CF 12% Identified by molecular weight
determination, fluorine analysis
and by its NMR spectrum.


Originally the methylene chloride was added to the

solvent, acetic anhydride, in order to keep the boiling

point low and prevent overheating. It seems, however, that

the CH2C12 plays also a part in determining the course of

the reaction. Thus when the previous reaction of CF3CH21

with zinc was carried out in acetic anhydride as a solvent

and without the presence of CH2C12, the coupled product,

CF3CH2CH2CF3, was formed only in traces. The importance

of the solvent in the course of this reaction has been

demonstrated several times. While, for example,

1,1,2-trifluoro-1,2-dichloro-2-iodoethane, CF2CICFC1I, has

been found to react with zinc in acetic anhydride-methylene

chloride as a solvent, producing a high yield of the coup-

led product, CF2C1CFCCFCCFC2C1, when the reaction was

carried out in dimethyl sulfoxide, only the dehalogenation

product was formed.

A further attempt was made to cross couple iodides

containing other elements besides fluorine with iodides

of the same type or with perfluoro iodides and also with

hydrocarbon iodides.







When a mixture of l,ll-trifluoro-2-iodoethane and

trifluoromethyl iodide was added to a dispersion of acti-

vated zinc in perfluoroacetic anhydride, reaction took

place. Analysis of the reaction mixture gave the following

products:

Ratio of Products

C2F6 12% Resulting from coupling of CF I

CF H 12% Resulting from reduction of CF3I

CF3I 50% Unreacted

CF CH3 10% Resulting from reduction of CF CH2I

(CF CO)2 11% Solvent


No cross-coupled product was isolated. Similarly, reaction

of CF3CH2I and C2F5I with activated zinc in acetic anhy-

dride yielded only the dehalogenation product of CF3CIH2I,

CF2=CH12 in 20% yield and the reduction product of C2F5I,

CF5H.

Despite the fact that CF2C1CFClI and CF CH2I react

individually with zinc giving, among other products, the

coupled product, when their cross-coupling was attempted

in dioxane, the only products separated from the reaction

mixture were the reduction and the dehalogenation products

of CF3CH21, CJ 3C 3 (5%) and CP2=CH2 (70%), as well as the

de alegenation product of CFClCFClI, CF2=CFC1 (15%). A

small yield of CF2=CF-CF=CF2 (2%) was also obtained from

this reaction, being formed probably by first coupling








' --C'^ IC,- 1.nd 7ub reonuemnt C e-.lo-


vc, el


inc



it

the


t i f ct

le fluori]

ucc eed

of 1,

ter of -


S-c


o t


th t 1, 1 -o ed to

i t' 1 sulfo eld

1 product. ow ever,

I zcine in di. et 1 sul-

1 eti rion ct, -

So f the rtteots

.inn ii ith other

oroe encour re ult C


3 WL A 2' 2 3
o -:-. uoroaroQionic 1o ,

from 7luorosuccinic

?"luoro succinic i e


ouIt


t ol~il

1~r


tl"I et


I-,


I oV24


It,

Sof


Ler ent t 1 .


I to

of thi


re ct i
1 ,,
I .


:ro: -i



c to ie:


net' rl


-ei "ti


S',


e


Mtifi







It was highly desirable to couple this compound with

zinc because perfluoreadipic acid would have resulted from

sush a coupling. Shortly after this iodide was added to a

dispersion of activated zinc in dioxane, heat was liberated

indicating that reaction was taking place. When the reac-

tion mixture was analyzed, both the reduction product,

CF2 G2COOH,0 9 as well as the coupled product,
CH OCO(CF2)4COOCH3, were obtained in a ratio of coupling:

reduction of 1.85.

After the successful coupling of ICF2CF2COOCH3 in

dioxane, the same reaction was carried out in dry ethyl

ether as a solvent and at room temperature. Again a mix-

ture of the reduction and of the coupled product was ob-

tained which was found by gas chromatography to consist

of 45% coupled and 19.5% reduction product.

Beginning with perfluoroglutaric anhydride and by

steps analogous those used in the preparation of the

ICP2C?2COOCH3, the preparation of the methyl ester of the

Y-iodoperfluorobutyric acid was accomplished. Thus the

anhydride was first treated with an equivalent amount of

/COOCH3
dry methyl alcohol yielding the half ester, (CF2)3CH ,
2 N^COOH

which in turn was treated with silver oxide to yield the

,COOCH3
silver salt of the half ester, (CFF2) g When the
silver salt was heated with excess of odine, a yield of
silver salt was heated with excess of iodine, a yield of







80% of the iodide, ICF2P2C2CF2COOCH3 was Obtabind. The

structure of this compennd was vipT.rfLed by IKR and by

elemental analysis. Addition of ICC F CF2 20CH be a

dispersion of activated zins in dry etktl 1ther was

follewd by heat evolution. Whei th- rem.tion matrixt

was analyzed by gas chreoatmogXphy a 45% yield of the

coupled product, (F2)6 3, and an 18% yield f the
')COOCH3

reduction product, CF2HCF2CF2COOCH3, was obtained. The

structures of both products were verified by NMIR spectEa,

by elemental analysis and saponification equilvlents. The

ratio of seapling:reAoction equals 2.5.

The coupling of the prtfluei e iode-eater s:auli be

developed into a very nletfl creation for the preparation

of perfluorodisarbEtlie acids. The fact, hwtrf, hatac%

those iodeesters are prepared ftre the pe rfluera sucAinic

and perflaoregmlbtarie anhy1rid*s whiah anv net roedily

available materials, ru ma@es th4 useftlnes of this o-lth*

until some any Uan be found to prepare the above esnhdfiles

mere reeta.ly An altriatt* route was atteaWt d $or t-h

preparation of p~if lntrire~ji f ioe aejid by S rtle.n 0r

chleraperl toiiea arl .cids with zinc. When, Y tflieiY

a quentp' -ip WutP im &feituifMeiMh llinLtqIf aId dli O a
spepai et mr in in ae s MaLU&d6- -a-WSflat
chlaforilem, Mir oA-:rr acud eM I'aM

....e. a.. an







Another interesting series of reactions was carried

out with fluoroiodides containing one or mere ether

oxygen. These iodides were prepared from the correspond-

ing fluoro acids, which were obtained free E. I. duPont de

Nemours and Company under the following names:

CF
1 3
Diser Acid: C3F OCFCOOIJ

CF CF

Trimer Acid: C3F OCFCF2OCFOGH

CF CF CF
I 3 I 3 i 3
Tetramer Acid: C3F OCFCF2OCFCF2OCFCOOH


Reaction with silver oxide in dry ethyl ether con-

verted the above acids into their silver salts. The silver

salts in turn, when heated with excess of iodine, were con-

CF CF CF
1 3 1 3 1 3
verted into the iodides C3F OCF-I, C3F70CPCF2OCFI, and

CF CF CF

C3F OCF-CF2OCFCF2OCFI in yields from 60-70%.

It was mentioned in Seetion II that the secondary

perfluoroalkyl iodides couple only into a small extent with

zinc and that the maIn products are the reduction and the

dehalogenation preduets. Analogous results were obtained

CF
en C added o a ure of activated zinc and3
wKen C F OCFI was added to a mixture of activated zinc and
3?f







dry ethyl ether. Analysis of the product mixture gave 94%
of the reduction preduet, C3F7OCFHCF3, and 6% of the

CF3 f3
coupled product C F OCF-CFOC F Both compounds were

identified by eleamntal analysis. meleaular weight detop-
mination and NMR spectrum. The reaslts obtained when the
trimer and tetramer iodides were reacted with zinc in ether
were similar to those in the rea:timn of the dimer iodide
with zine. The reduction and eewpled preduets of the above

iodides were obtained as shown below.
CF CF CF CF
I 3 3 -3 1 3
C3F OCFCF200FH, (C3F7OCFCF2OCF-) 2

CF CgF C CF CF WF
I 3 3 3 3 3 I3
C3 FOCFCF200FCF2OCFH, (C3F0OCFCP 2002CF2OCF-) 2

The silver salt of t thtedramer aeid was treated with
bromine at room tel*pftture and a elear liquid was obtain.M

in a yield of 81%. This liquid was ftnd to be shremato-

graphically puwn and gave a boiling peint of 159e C. It
was beLiLef that this liquid was the bramids,
OF CF! CF
1i3 3 3
C F OCF-ir2 Q^Ci OFBr. NLMg SiR spcitrus awd sletBMal
analysis whifled theh aover fnumwta. W Men bthis bmai&e

was adatd to a, nupmasti of attt4ket ztna Jn ab*SiS:

.andxd w.a chlwt*h Yl chl ana t mi turf elg n fd
e fl"' a. *h4 .: I.l.s .e..t l e. a..t, p i S .I ...







the reaction flask. From the reaction mixture, a high

boiling liquid was separated in a yield of approximately

30% and gave the same boiling point (2250 C.) and the same

infrared spectrum as the coupled product,

CF CF CF3

(C3FOCFCF2OCFCF2OCF-)2, obtained from the reaction of

CF CF3 CF

C 3FOCFCF OCFCF2OCFI with zinc.

This is the first bromide containing fluorine which

was successfully coupled with zinc, and it is also a sec-

dary bromide. A primary bromide, SF OCHFCF2Br, containing

also oxygen, was prepared by addition of SF OF to the olefin

CFH=CFBr. This bromide was allowed to react in dry ethyl

ether with activated zinc under ultraviolet irradiation,

at room temperature. From the reaction mixture there was

separated a small amount of liquid boiling higher than

ether. It was separated by gas chromatography and found

to be a mixture of SFO5CHFCF2H and (SFsOCHFCF2-)2, result-

ing from reduction and coupling of the SF OCHFCF2Br,

respectively. The NMR spectra verified both structures.


Reactions of Aromatic Iodi4ds and Bromides
Containin Fluorine with Zinc


The study of the reaetien of the fluorine-containing

aromatic iodides and bromides with zinc was restricted to

the investigation of the reactions of pentafluorolodoben-

zene, C6F51; p-iodobenazetriflaeride and E-bremobenotri-
fluoride. Because of the expense of these three cmpouinds,







small quantities were used in each reaction and the isola-

tion of the products was therefore difficult. When a few

grams of pentafluorolodobenzene was added to a mixture of

granular zinc, acetic anhydride and methylene chloride,

reaction began at room temperature and solid products

separated. These solids gave a positive test for fluoride

ion and were soluble in dilute acid. It is believed that

the solid was zinc fluoride. The expected coupled product,

C6F5-C6F5, is a solid melting at 650 C., but it is not

soluble in water. No other product was isolated from this

reaction except a few drops of oily, tarry material in

insufficient quantity for any further work. Nield,

Stephens and Tatlow (12) reported the preparation of

C6F5-C6F5 by heating C6F5Br with copper at 2500 C.

From the one reaction run it appears that both the

iodine and the fluorine atoms react with the zinc. The

path of the reaction of 2-iodotrifluoromethylbenzene,

CF3 I, with activated zinc in the same solvent mixture

was not very different. This compound does react under

these conditions but the reaction product is a tarry mass

which could not be purified; no useful product could be

isolated. Whereas the CF3c I reacted with zinc at room

temperature, the corresponding bromide CF 3 Br was found

to be completely inert even at the reflux temperature of

the acetic anhydride.







An attempt to cross-couple CF 3 \ Br with C F I or

CF3Q I with CF3I In acetic anhydride and in dimethyl

sulfoxide resulted in the coupling and reduction of C F7I

and CF3I. No product was isolated arising from the

aromatic halides. Reaction of CF3Q Br and CF2=CFI with

activated zinc in acetic anhydride at room temperature and

at 1000 C., resulted in reduction of the CF2=CFI. The

CF30 Br was recovered unchanged in both cases.

Reactions of Perfluoroacyl Iodides with Zinc

From this class of compounds the reaction of trifluo-

roacetyl iodide CF COI, and pentafluoropropionyl iodide

was studied. Both substances were prepared by heating the

corresponding chlorides with HI under pressure.

Addition of trifluoroacetyl iodide to a dispersion of

granular zinc in dry ethyl ether resulted in a fast exo-

thermic reaction. Analysis of the reaction mixture showed

it to contain 95% CF311, 2% C2F6 and 3% CF3I. The first two

products were probably formed by initial formation of the
11
radical CF C- which, after elimination of CO, would yield

the radical CF3 The CF radical in turn could abstract

a hydrogen atom from the solvent forming CF3H, or could

couple to give the C2F6. In addition to these products,

a small amount of a tarry material was isolated by

evaporation of the ebQter. This tarry material showed




30


carbonyl absorptions in the infrared. Analogous results

were obtained when pentafluoropropionyl iodide was allowed

to react in ether with zinc. The products isolated were

C2F5H 78% and C4F10 22%.














III. EXPERIMENTAL


Two general methods were employed in carrying out

the coupling reactions.

Method 1

When the reactants were volatile compounds, the

coupling reaction was carried out in a heavy wall glass

ampule which had been dried by heating under vacuum. The

zinc was added first to the ampule and then the volatile

reactants were transferred under vacuum. The reaction

mixture was cooled to liquid-oxygen temperature and, after

the air was completely removed by pumping, the ampule was

sealed and allowed to warm up to room temperature. In

same instances the reaction was allowed to go to comple-

tion at room temperature and other times the temperature

was raised to the desired degree.

Upon completion of the reaction, the ampule was opened

under vacuum, and the volatile products were transferred

to a metal cylinder. The separation of the products was

a6eamplished by gas chromatography.

Mfthed 2

When the reactants were high boiling substances, the

reaction was carried out in a Pyrex flask equipped with







reflux condenser, magnetic stirrer and an outlet tube

connected to a trap cooled in liquid-oxygen, for the

collection of any volatile product that would be formed

during the reaction. After completion of the reaction,

the mixture was filtered to remove the unreacted zinc and

the zinc halides formed during the reaction, and, depending

on the amount of product, gas chromatography or distilla-

tion was used to separate the various components of the

reaction mixture. All the glassware and the starting

materials were dried before use. The zinc was activated

by treatment with 5% hydrochloric acid and dried under

vacuum or by addition of one drop of 40% HBr in water.

Reaction of CF CF2COI with zinc in ethyl ether at 0 C.
--3--2
Method 2 was employed.

Amount of reactants:

CF3CF2CO: 10 g. (0.036 mole)

Granular zinc: 5 g. (0.073 gram-atom)

Solvent: Ethyl ether: 50 ml.

Reaction temperature: 12 hours

Three minutes after the reactants were mixed, reaction

started as indicated by the refluxing of ether and by the

liberation of iodine. Distillation of the reaction mixture

yielded 4 g. of product which was separated by gas chreoa-

tography into two compounds. These compounds were

identified by their infrared spectra as C2F5H. 78%, and

C4F10, 22%.







Reaction of CP COI with zinc in ether
-- 3
Method 2 was employed.

Amount of reactants:

CF COI: 6 g. (0.027 mole)

Granular zinc: 5 g. (0.073 gram-atom)

Solvent: Ethyl ether: 10 al.

Reaction temperature: 250 C.

Reaction time: 12 hours

Distillation of the reaction mixture yielded 3 g. of pro-

duct. Separation of the product by gas chromatography gave

the following compounds, identified by their infrared

spectra in the ratio: C2F6 2%, CF3H 95%. and CF3I 3%.

Reaction of CF CFPC1 with zinc in ether under ultraviolet
irradiation '

Method 1 was employed.

Amount of reactants:

CCFCF21: 10 g. (0.065 mole)

Granular zinc: 3 g. (0.044 gram-atom)

Reaction temperature: 1000 C.

Reaction time: 12 hours

The starting material was recovered unreacted.

HIggtion of CF2,CCFCII with zinc in ether

Method 2 was employed.

Amount of reactants:

CF2CICFC1I: 5.5 g. (0.02 mole)

Granular zinc: 3 g. (0.044 gram-atom)

Solvent: Ethyl ether 50 ml.







Reaction temperature: 250 C.

Reaction time: 12 hours

In 30 seconds after the reactants were mixed, liberation

of iodine began and the relation mixture beeane dark bruow.

During the liberation of iodine, heat was evolved and the

ether refluxed. Separation of the reaction mixture by gas

chromatography yielded 1 g. of a compound identified by its

infrared spectrum as CF2=CFC1. No other product was iden-

fled.

Reaction of C F, 1 with zinc in acetic anhyg ldg-iethyleoe
chloride '

Method 2 was employed.

Amount of reactants:

C F151: 4 g. (0.008 mole)

Granular zinc: 3 g. (0.054 gran-atem)

Solvent:

Acetic anhydride: 20 al.

Ethylene chloride: 25 El.

Reaction temperature: 550 c.

Reaction time: 48 hours

The reselimn mixture was treated with cold 10% sulfajic

acid in order to hydrelyze t.he see*le an.hydride, wkln a

waxy solid (2 g,) prelipitated. The solid ras washed

several tdiPs with distilled water, aad wkia dried under

vaeUtm, aave a mlt ing poeit of 80e C. It is. essetad to

be the as.M prfetait, C14,7 The luA1ffttM Sf*P4iW of







the solid is very similar to that of Teflon. The IJMR

spectrum is in accord with the above formula. The yield

was 67%. Elemental analysis for F was:

Calculated: 77.3% Observed: 76.2%

Reretion of C3F I with zinc in ethyl ether

Method 2 was employed.

Amount of reactants:

C3F I: 8 g. (0.027 mole)

Granular zinc: 3 g. (0.044 gram-atom)

Solvent: Ethyl ether: 50 ml.

Reaction temperature; 250 C.

Reaction time: 12 hours

Chromategraphic separation of the reaction mixture gave

two products identified by their infrared spectra as

C6F14 and CF7 H in the ratio of 2:1. The solids remaining

after removal of the volatile material yielded some

CF CF=CF2 on pyrolysis, suggesting that C3F TnI was also

formed.

Rseltion of HIC F I with zinc in acetic anhydride
-methylene chi 1ta

Method 2 was employed.

Amount of reactants:

HC10F20I: 12 g. (0.02 mole)

Granular zinc: 1.5 g. (0.02 gram-atom)

Solvent: Acetic anhydride: 20 ml.

Methylene chloride 25 ml.







Reaction temperature: 55 C.

Reaction time: 6 hao.s

Within 6 heors the mixture became thiek from the feorn tten

of white solids and the renetion was stopped. The rhi-ntr4

was shaken with ice-eold 10% sulfuric acid to hydrelyi.

the acetic anhydride. The organic layer was separate@ and

after evaporation of the solvents, a yellow solid was ob-

tained. The solid was purified by washing with ethor and

the yellow color was removed. The washed product was a

white cryetalline solid, m.p. 1650 C. and b.p, 2860 C.

which appeared to be H(CF 20)H. The F analysis was:

Calculated: 76% Observed: 75.2%

Yield: 75%.

Reaction of CF I and F3 CF2I..th zAs ,An eetic anh aridh

Method I was employed. This reaetion was run in

triplicate.
Amount of reastants:

CFP I 2 g. (0.01 mole)

CFPg721: 2.5 g. (0O.01 mole)

Zine peter: 5 gs (0.07 gras-aftem)

Solveit: AcAtic anhydride 10 i3.

Ractien tlm*~eratre: t 250 C., t2 60e C.,
t l2a0 C.

rasetrin tLn: 12 bese

The products te tihe three tta;ttens enre flt aIM by
gas chrOftwrmaey and %ItN gitl of th" %mrlMONas t s

was shou Tat 1.O







Reaction of CFPI knd CF CF.I with zine in dioanne

Method 1 was employed.

Amount of resetants:

CF3I: 2 g, (0.01 mole)

CF3CF2I: 2.5 g. (0.01 mole)

Zinc dust: 10 g. (0.145 gram-atom)

Reaction temperature: 250 C.

Reaction time: 48 hours

The product (2.1 g.) was separated by gas chromatography

into two components identified by their infrared spectra

as CF H and C2F H. The solids obtained from this reaction

gave some C 3H and C7 FH on treatment with water, probably

coming from hydrolysis of CF ZnI and C2FSAnI.

Reaction of C FnBr with zinc in acetic anhydrie-metkllene
chloride f

Method 1 was employed.

Amount of reaetants:

CF 7Br: 4 g. (0.016 mole)

Granular zinc: 3 g. (0.045 gram-atom)

Solvent: Acetic anhydride: 3 ml.

Nethylene chloride: 4 ml.

Reaction temperature: 2750 C.

Reaction time: 4 hours

The mixture was separated by gas chromatography into two

compounds identified by their infrared spectra as C3F H

and C3 .Br, in the ratio of 30:70.







Reaction of CF2Br2 with zinc in acetic anhydride-methylene
Chloride

Method 2 was employed.

Amount of reactants:

CF2Br2: 9 g. (0.04 mole)

Granular zinc: 3.4 g. (0.08 gram-atom)

Solvent: Acetic anhydride: 21 g.

Methylene chloride: 24 g.

Reaction temperature: 25-330 C.

Reaction time: 12 hours

Chromatographic separation of the volatile products gave

the following compounds:

CF 2CF2 CF2Br2 C2C12

in the ratio: 15:5:40.

Reaction of CF^BrCFeBr with zinc in acetic anhydride
-methylene chl-bride

Method 2 was employed.

Amount of reactants:

CF2BrCF2Br: 13 g. (0.05 mole)

Granular zinc: 3.4 g. (0.08 gram-atom)

Solvent: Acetic anhydride: 21 g.

Methylene chloride: 24 g.

Reaction temperature 12 hours

Chromatographic separation of the volatile showed the

main product to be CF2=CF2, 35%, along with CH2C12, 60%,

and an unknown material, 15%.







Remotion of C F3I and CF.2By2 with zinc in acetic anhydride
Method 1 was employed.

Amount of reactants:
C3F I: 3 g. (0.01 mole)

CF2Br2: 3 g. (0.015 mole)

Zinc powder: 2 g. (0.03 gram-atom)

Solvent: Acetic anhydride: 3 ml.

Reaction temperature: 1000 C.

Reaction time: 12 hours

Analysis of the volatile product (2.5 g.) by gas chroma-
tography gave the following components, identified by

their infrared spectra, in the ratio:

C3F' 7, 40% C3FBr, 5% C6F14, 5%
CF2Br2, 15% unknown material, 35%.

Reaction of (CF )2CFI with zinc in acetic anhydride
Method 1 was employed.

Amount of reactants:

(CF3)2CFI: 2 g. (0.007 mole)
Zinc powder: 1 g. (0.015 gram-atom)

Solvent: Acetic anhydride: 2 ml.
Reaction temperature: 250 C.
Reaction time: 12 hours

Chromatographic separation of the product, gave the

following compounds identified by their infrared spectra:

CCFFCF2CF. 25% CF3CFHCF3, 50% (CF3)2CFI, 9%

CF )2CF1 2 8% unknowns, 8%.
OCF3)2CF 2 was identified by NMR and molecular weight.







Analysis for F:

Calculated: 73.6%, Observed: 72.4%

Molecular weight:

Calculated: 338 Observed: 335

Reaction of CF2=CFI with zinc in acetic anhydride

Method 1 was employed.

Amount of reactants:

CF2=CFI: 4 g. (0.02 mole)

Zinc dust: 7 g. (0.1 gram-atom)

Solvent: Acetic anhydride: 10 ml.

Reaction temperature: 1300 C.

Reaction time: 12 hours

Analysis of the volatile product (1.5 g.) showed the

presence of one major component identified by its infrared

spectrum as CF =CFH. Ilo coupled product was formed.

Reaction of CF,=CFI with zinc in ethyl ether and under
ultraviolet irradiation

Method 2 was employed.

Amount of reactants:

CF2=CFI: 5 g. (0.024 mole)

Granular zinc: 3 g. (0.044 gram-atom)

Solvent: Ethyl ether: 50 ml.

Reaction time: 12 hours

Analysis of the product by gas chromatography gave only

one component which was identified by its infrared spectrum

as the reduction product, CF2=CFH.








Reaction of OF2=CFBr with zinc in perfluoroaottic anhydride

Method 1 was employed.

Amount of reactants:

CF2=CFBr: 3.5 g. (0.028 mole)
Zinc dust: 7 g. (0.1 gram-atom)

Solvent: Perfluoroacetic anhydride: 8 ml.

Reaction temperature: 600 C.

Reaction time: 12 hours

The only product isolated was the CF2=CFH and no coupled

product was detected.

Reaction of CF2CCIOFI with zinc in diox~ne

Method 1 was employed.

Amount of reactants:

CF2ClCFHI: 5 g. (0.02 mole)

Zinc dust: 3 g. (0.045 gram-atom)

Solvent: Dioxane: 3 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours

The volatile product (2 g.) was analyzed by gas chroma-

tegraphy and infrared spectroscepy and was fund to

consist of:

CF2-CFH, 97% CF2-CFCl, 3%

A small amount of starting material was also recovered.

Reacsti. of CF CICFHI with zine in aegtie anhydride


Method 2 was employed.







Amount of reactants:

CF C1CFHI: 12.2 g. (0.05 mole)

:ranular zinc: 3.4 g. (0.05 gram-atem)

Solvent: Acetic anhydride: 21 g.

Methylene chloride 24 g.

Reaction temperature: 350 C.

Reaction time: 6 hours

The reaction mixture was treated with cold 10% H2SO4 to

hydrolyze the anhydride, and the organic layer was sepa-

rated, washed with aqueous sodium bicarbonate, distilled

water, and then dried with calcium chloride. The product

(7 g.) was analyzed by gas chromatography and two compounds

were isolated and identified by molecular weight, NMR and

elemental analysis.

CF2C1CFHCFHCF2C1. 45% CF2CCFHCCFHH2CF 2C1, 45%

Analysis for F:

Calculated: 48.5% 47.7%

Observed: 47.6% 46.2%

In addition, 10% of the starting material, CF2ClCFHI, was

recovered.

Reictin of CF,21,I with zjqnc in acetic anhydride-muetylene
chloride '

Nethod 2 was employed.

Amount of reactants:

or3 Ci i: 10,5 ~, (0.05 molp)

Granular z2ine: 3.4 g. (0.05 aam-ea.Ie)







Solvent: Aeetic anhydride: 21 g.

Methylene chloride: 24 g.

Reaction temperature: 350 C.

Reaction time: 12 hours

The volatile product was analyzed by gas chromatography

and the following compounds were identified in the ratio

CF2=CH2, 48% CF3CH 40% and 12% of an

unknown with m.w. 164. The NMR spectrum of the unknown

is in accord with the formula CF CH2CH2CF3 which also has

a theoretical m.w. of 166.

Analysis for F:

Calculated for C4H4F6, 68.8% Observed: 67.9%

Reaction of CF CH2I with zinc in acetic anhydride

Method 2 was employed.

Amount of reactants:

CF3CH2I: 6 g. (0.03 mole)

Granular zinc: 1.7 g. (0.04 gram-atom)

Solvent: Acetic anhydride: 30 ml.

Reaction temperature: 30-35 C.

Reaction time: 12 hours

Analysis of the volatiles by gas chromatography showed that

the coupled product, (CF3CH2)2, was formed only in traces.

Bemttjon of F QcZCIC with zinc in dliethYl sulfoxide
Method 1 was employed.

Amount of reaetants:
CF2CICFClI: 5 g. (0.018 mole)

Activated zine powder: 5 g. (0.07 gram-atom)







Solvwnt: Diaethyl sulfoxide: 5 ml.

Reaction teprature: 25 C.
Reaction time: 12 hours

Only two compounds were present and they were identified
by their infrared spectra ass

CF2-Cf., 5% cyF=2 cl., 95%
Reaction of CF QdI and OF I with zinc dust in peflMP-
aceti- andride
Method 1 was employed.

Amount of reactants:
CF 1: 2.1 g. (0.01 hele)

CF CH2II 2.1 g. (0.01 *ole)

Activated zinc dust: 7 g. (0.1 gram-aem)

Solvent: Perfluoroaeetic anhydride: 8 a1.

Reaction temperature: 1000 C.

Reaction time: 12 heors

The volatile product (4 g.) was analyzed by gas chrein-

tography and five compeunds were idtntiftld by their Infra-

red spectra and in the rates

C2F, 12% CFr,. 12% CF3I, 1p5 CF CH3, 10
(CF300)20, 11% and small amount of unkatens.
!iEL of CB anA cJrI wijh z-tI xest IK *gaWi


Me *kod 1 wns employed.

Amemunt Of inrefats.:

a3F Q I 2.5 (0..1 y)

C Ins US 7 g (0.1 L S&*mA)
5aE iaie 7 .0 ( -01 -gas)









Solvents Acetic anhydride: 8 ml.

Reaction temperature: 250 C.

Reaction times 12 hours

Analysis of the product showed the presence of the follow-

ing compounds:

CF2=CH2, 20% C2F5H Unknowns, 10%

No coupled product was found.

Reaction of CF2CICFCII and CF CH2I with zinc in dioxane

Method 1 was employed.

Amount of reactants:

CF2CICFClI: 3 g. (0.01 mole)

CF Ch2I: 3 g. (0.014 mole)

Solvents Dioxane: 8 ml.

Reaction temperature: 800 C.

Reaction time: 8 hours

The following compounds were identified in the reaction

product:

CF2=CH'2, 70% CF3CHJ. 5% CF2=CF2, 15%

CF 2CFCF=CF2, 2%
The last compound was obviously formed by coupling of the

CF2CICFC1I to give CF ClCFClCFPCCF2C1, and subsequent de-

chlorination of the latter by zinc.

Resacion of CF CICHFI and CF ClCFClI with zinc in acetic
anhy ariae- htie i2ne chloride

Method 2 was employed.








Amount of reactants:

CF2C1CFHI: 6 g. (0.025 mole)
CF2CICFC1II 7 g. (0.025 mole)

Granular zinc: 6.8 g. (0.1 gram-atom)

Solvent: Acetic anhydride: 21 g.

Methylene chloride: 24 g.

Reaction temperature: 350 C.

Reaction times 12 hours

The reaction mixture was treated with 10% sulfuric acid

to hydrolyze the acetic anhydride. The organic layer was

separated and washed several times with distilled water.

Chromatographic analysis of the organic layer gave the

following products:

Unreacted starting materials, 65%

CF2C1CFCHCFCF2Cl, 10%

CF2ClCFHCH2CFHCF2C1, 10%

Unidentified substances, 15%

Reaction of CF2CICFIII and CH31 with zinc in dimethyl
sulfoxide

Method 1 was employed.

Amount of reactants:

CF2 CCPHI: 5 g. (0.02 mole)

CH 3I: 4.5 g. (0.032 mole)

Activated zinc; 3 g. (0.05 gram-atom)

Solvent: Dimethyl sulfoxide: 3 ml.

Resetion temperature: 250 C.

Reaction time: 12 hours








Analysis of the product (5 g.) by gas chromatography showed

that it consisted of the following compounds, identified

by their infrared spectra:

CF2-CFH, 90% CF2=CFC1. 2% CF3I, 8%

Reaction of ICF2CF2COOCHJ with zinc in dioxane

Method 2 was employed.

Amount of reactants:

ICF2CF2COOCH3: 9 g. (0.03 mole)
Granular zinc: 8 g. (0.112 gram-atom)

Solvent: Diozane: 50 ml.

Reaction temperature: 550 C.

Reaction times 3 hours

Extraction of the reaction mixture with petroleum ether

and removal of the petroleum ether yielded 3.5 g. of

liquid product. This product was found by gas chromatog-

/COOCH-
raphy to be a mixture of 65% (CF2)9 3 and 35%
'C00ooCH3

HCF2CF2COOCH3. The structures of the above compounds were

verified by NMR spectra.

,COOCH
Yield of (CF2)4 OOC 3

Analysis for F:

Theoretical: 47.8% Observed: 47%

Yield of HCF2CFPCOOCH3: 20%








Analysis for r:

Theoretical: 47.8% Observed: 48.1%
Ratio of coupled product 185.
reduction product
Reaction of ICCF2FCOOCH3 with zinc in diethyl other

Method 2 was employed.

Amount of reactants:

ICF2CF2COOCH3,: 9 g. (0.03 mole)

Granular zinc: 8 g. (0.112 gram-atom)

Solvent: Ethyl ether: 100 ml.

Reaction temperature: 350 C.

Reaction time: 12 hours

A high boiling liquid (4 g.) was separated from the reac-

tion mixture after the evaporation of the solvent. This

-COOCH
liquid was found to be comprised of (CF2)4 CO 70%
'COOCH 3
and HCF2CF2COOCH3, 30%.

Yield:

Coupled product, 45% Reduction product, 19.5%
Ratio of coupled product 2-
reduction product 2
The saponification equivalent of the coupled product,

/COOCH
(CF2,)" was found to be 163; theoretical, 159.
2 COOCH3

Reaction of ICF CF CF COOCH with zinc in ethyl ether
with and without ultrviolet irradiation

In a 50 ml. round bottom flask were placed 2 g.

ICF2CF2CF2COOCH3 dissolved in ether, and the solution

stirred under an ultraviolet lamp. Yellow color appeared








in the solution and had deepened to orange at the end of

30 minutes; it was unchanged after an additional hour.

Then a few granules of zinc were added and after 5 minutes,

iodine was liberated. The purple color of the solution

persisted since the amount of zinc added was not enough

to remove all the iodine liberated. When the reaction

mixture was treated with aqueous sodium thiosulfate the

iodine color was dispelled.

In a similar experiment with exactly the same amounts

of reactants and solvent, but without ultraviolet irradia-

tion, the addition of a few granules of zinc did not initi-

ate the reaction, and the color was yellow at the end of

30 minutes. It was necessary to add 0.15 g. of zinc to

initiate the reaction and to liberate iodine in 3 minutes.

This experiment indicated that the reaction has an induc-

tion period and that ultraviolet irradiation initiates the

reaction.

Reaction of ICF CFpCF2COOCI with zine in ethyl ether

NMthod 2 was employed.

Amount of reactants:

ICF2CF2CF2COOCH 3 9 g. (0.026 mole)
Granular zinc: 8 g. (0.113 gram-atom)

Solvent: Ethyl ether: 100 ml.

Reaction temperature: 250 C.

Reaction time: 24 hours








A high boiling liquid (3.5 g.) was isolated which was shown

COOCH
by gas chromatography to be a mixture of 72% (CF2 )C 3

and 28% H(CF,)3CCOCH3.

Yield of coupled product: 45%

Fluorine analysis for C8H6F8C4:

Calculated: 54.5% Observed: 53.2%

Yield of reduction product: 18%

Fluorine analysis for C6H6F602:

Calculated: 54.3% Observed: 53.4%
Ratio of coupled product 2.5.
reduction product
The structures of the coupled and of the redmetion product

were in accord with NMR. Molecular weight determination

-COOCH1
of the (CF2)6 from the saponification equivalent
COOCH,,

gave the value, 416; theoretical molecular weight, 418.

Reaction of (CfH3)2SHCl and CF 3C2I with zinc in dioxane

Method 2 was employed.

Amount of reactants:

CF CH 2I 20 g. (0.095 mole)

(CH3)2SIHC1: 10 g. (0.036 mole)

Granular zinc: 10 g. (0.145 gras-mole)

Solvent: DiewEne: 30 ml.

Reaction tmpevature: 250 C.

Reaetiwio ti-se: 12 hewrs








Chromategraphic analysis of the reaction mixture gave the

following components:

CF2sCI2, 14% CF3 ClH 6% (CH3)2SIHF, 65%

CF CH2CH2CF3, 5% Unknown, 10%
CF
S3
R..etion of dimer acid silver salt C F OCF-COOAg with
iodine

In a round bottom flask were placed 15 g. (0.02 mole)

of powdered iodine, and the flask was heated with a low gas

flame until the reactants were melted and the iodine began

to boil. Then the flask was evacuated and a liquid product

was collected in a liquid oxygen trap. The product was

treated with sodium thiosulfate to remove the iodine and

dried with calcium chloride. The product was found by

molecular weight, NMR and elemental analysis to be pure
CF
3
C3F OCFI.

Yield: 8 g. (57%) Boiling point: 840 C.

Molecular weight:

Theoretioal: 412 Observed: 416

n0 = 1.3148

Fluorine analysis for C5F110:

Calculated: 50.08% Obherved: 51.3%
CF
S3
Reaction of CF CF2CF gff.S with zinc in ethyl ether

Method 2 was employed.






Amount of reactantwt:
CF
I I

CF CP2-0-CFI:2:5 s.(00
Gftymslar zine: 1 9. (0.015 9tapa"
solvvft:o Ethyl ether:5 l
Rmeation twwo"*ture: 25 C
Re&Ction times 12 hW
Distillation *I the volatiles afforded 1.5 *. of Yoeta
boiling higher than other which wag analxtod bW gans ho
tography and shown to consist of the followhag pefos
I

c 3 F70cracOF3: 94% (C) 3 7ocF-) 2
Kalweular w*Uhnt
Theoret Ical: 2 &6 shoeel 57.0
Observe9d: 24B5 ob.re 63
Analysis few flolurine.
Theeratil:"1 77,5% ?hrst : 7#6
Observed: 76.6% obsevrted 75-20
NMR:
In agrement witiq Uhore

S3 3 3
W~b Zn g #0



Xe*"d2 it







Amount of reactants:
CF CF CF
1 .3 3
C3F7CCFCF2OCFCF2OCFI: 10 g. (0.013 mole)

Granular zinc: 5 g. (0.073 gram-atom)

Solvent: Acetic anhydrides 20 ml.

Pethylene chloride: 20 ml.

Reaction temperature: 450 C.

Reaction times 12 hours

A liquid product (5 g.) was obtained from the reaction
CF CF CF
1 3 s 3 1 3
mixture and identified as (C3F OCCF2OCFCF2CFOF-)2;

b.p., 255 C.; nO = 1.2903; NRR consistent with above

structure.

Fluorine analysis for C22F4606a

Calculated: 70.8% Observed: 71.5%
CF CF CF
1 3 1 3 5 3
Reaction of C F OGPCF OOFCF OCFI with zinc in ether

Method 2 was employed.

Amount of material:
CF CF CF
1 3 1 3 i 3
C3F OCFCF2OCFCF2OCFI: 8 g. (0.011 mole)

Granular zinc: 5 g. (0.073 gram-atom)

Solvent: Ethyl ether: 50 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours

The reaction mixture was filtered to remove unreacted zinc;

the filtrate was washed with water to remove ZnI2, and then

dried with calcium chloride. Upon evaporation of the ether,








4 g. of high boiling liquid was obtained which was found

to be the coupled product.
CF CF CF
1 3 1 3 1F3
Reaction of C F OCFCF OCFCFOCFCOOAg with bromine
3-L7- 2-2
Method 1 was employed.

Amount of reactants:
CF CF CF
F,3 F.3 F3
C3F OCFCF2OCFCFCFCCFCOOAg: 13 g. (0.017 mole)

Promine: 20 g. (0.125 mole)

Reaction temperature: 250 C.

Reaction time: 12 hours

A liquid product (9 g.) was obtained. Chromatographic

analysis of the product gave only one peak. It is expected
CF CF CF
S3 1 3 iF3
to be the C F OCFCF OCFCF2OCFBr.

Yield: 81%; b.p.: 1590 C.; NMR: consistent with above

structure.

Fluorine analysis for C11F23Br03:

Calculated: 64.0% Observed: 64.8%.

Reaction of SFOCHFCF Br with zinc in ethyl ether under
ultraviolet irradiation

Method 2 was employed.

Amount of reactants:

SFSOCFHCF2Dr: 2 g.

Granular zinc: 3 g. (0.044 gram-atom)

Solvent: Ethyl ether: 25 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours








Distillation of the reaction mixture yielded 0.8 g. of a

liquid product. The NhM spectrum of this liquid suggests

that it is a mixture of 85% coupled product, (SF OCHICF2-)2,

and 15% of the reduction product, SFPOCIFCF2H. No starting

material was available to produce larger quantities of the

product and isolate the two compounds.

RCiLon of CF I and C2F I with zinc in acetic anhtlrile
- roThfi.ne tehoride

Method 1 was employed.

Amount of reactants:

CF 3I 2 g. (0.01 mole)

C2 F5: 2.5 g. (0.01 mole)
Zinc dust: 10 g. (0.145 gram-atom)

Solvent: Acetic anhydride: 5 al.

Methylene chloride: 5 ml.

Reaction temperature: 1300 C.

Reaction time: 12 hours

Analysis of the volatile product (2 g.) gave four compounds,

identified by their infrared spectra as:

C2F C3F8 CSFO C2FsH
26 38 510 25
Beaetion of CF3I and. 0F CFI with zinc in Loetic anhydride
Method 1 was employed.

Amount of reactants:

CF I: 2.0 g. (0.01 mole)

CFP2CFI: 2.2 g. (0.01 mole)
Zinc powders 7 g. (0.1 gra9.lato )








Solvent: Acetic anhydride:

Reaction temperature: 1300 C.

Reaction time: 12 hours

The product (2 g.) analyzed by gas chromatography was found

to contain five main components identified by their infra-

red spectra as:

CF3I CF2=CFH C2F CF3CF=CF2
2 2 2 6 2 2
Reaction of CP I and CF2=CFI with zinc in acetic anhydride

This reaction was run in triplicate. Method 1 was

employed.

Amount of reactants:

CF Is 2 g. (0.01 mole)

C2F5I: 2.2 g. (0.01 mole)

Zinc powder: 5 g. (0.07 gram-atom)

Reaction temperatures: 600, 250. 1200 C.

Reaction time: 12 hours

The products were analyzed by gas chromatography and the

ratio of the various components at different temperatures

were calculated. The results are tabulated in Table 2.

Reaction of CF I and CF =CFI with zinc in perfluoroacetic
anhydride

Method 1 was employed.

Amount of reactants:

CF I: 2 g. (0.01 mole)

CF2=CFI: 2 g. (0.01 mole)

Zinc dust: 7 g. (0.1 gram-atom)








Solvent: Perfluoroacetic anhydrides

Resetion temperature: 1000 C.

Reaction time: 12 hours

The volatile product (2.2 g.) was analyzed by gas chroma-

tography and the following fractions were identified:

CF I, 15% CF2=CFH, 25% CF CF-CF2, 7%

CF3I, 50% Untlowns, 3%

Reaction of CF I and CF2=CFBr with zinc in acetic anhydride

Method 1 was employed.

Amount of reactants:

CF I: 2 g. (0.01 mole)

CF2=CFBr: 1.6 g. (0.01 mole)

Zinc powder: 2.5 g. (0.035 gram-atom)

Solvent: Acetic anhydride: 5 ml.

Reaction temperature: 1200 C.

Reaction time: 12 hours

Analysis of the product (1 g.) gave the following compounds

identified by their infrared spectra:

C2F6 CF3H CF Br
CF CF=CF2 CF I CF2=CFBr
aftl on of CJFQl and CF2=CFI with zinc in acetic anhydride
- Mwehrla cn iIe
Method 1 was employed.

Amount of reactants:
C2F Cl: 5 g. (0.032 mole)

CF2=CFIi 3.5 g. (0.017 mole)
Line powder: 5 g. (0.073 gram-atom)







Aolvdct: NActic ndrie3al
MehleecholoridR 3 *l.
Reaet ion temperatiwore 100 C*
Reafteion t iner 12 hwars
Th* s'tarting Swterial, C2 p5C., and .h ... ..tion pout
CF~~~ V.F. heeioaedi eai e s ~atmet 1, 653.rdnt
2~ 25


Xethod 1 was employee.
Amount of r~etwtantl
CF *-CI: 3 e.(0,015 Sol*)

C 2 H5 1 5 g,(0.03 *ole)
Gr~anslr z ime 3 9# (0405 mata
Solvent: Dieshy slfxie
Resetion tempeaT~fuIr: C.0
Rmact lon t tw.41 heaoe
Analysis of the poredast (3 x# ) by gas c~hvagtegvaplgy g*ave
two compwnntns Lfwtitfted. bf thoir intftaged speetra sts:
CH 03 , 63% Unpeo"*4OF c2wCI 5
F



li*thd 2 *a* empj#pA.
Aaentof rAw#A*Atee64


DrI 5 4# (06 tf-O )

C4040e v #em W 4 ( 00' 000sa WOmtO-








Solvent: Acetic anhydride: 20 ml.

Pethylene chloride 20 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours

The reaction mixture was treated with 10% sulfuric acid to

hydrolyze the anhydride and a heavy layer separated. How-

ever, no solids were left behind when the solvent was re-

moved. The melting point of the expected coupled product,

decafluorobiphenyl, is 650 C.

Preparation of the monomethyl ester of perfluoroglutaric
acid from the anhydride

In a three necked flask equipped with condenser,

stirrer and addition funnel were placed 30 g. (0.135 mole)

of perfluoroglutaric anhydride and the flask was cooled

with ice-water bath. Then 5 g. (0.156 mole) of methyl

alcohol were added dropwise under continuous stirring.

After the addition of the alcohol the mixture was brought

to room temperature and was left there for 2 hours to com-

plete the reaction. Then the excess of methyl alcohol was

removed by pumping in the vacuum system. The yield was

nearly quantitative.


fRes tion of CF Bar and C3F I with zinc in dimethyl
salfoxide 3 a e-

Method 1 was employed.








Amount of reactants:

CF 3 Br 3 g. (0.013 mole)

C3F 7I 3 g. (0.01 mole)

Granular zinc: 3 g. (0.05 gram-atom)

Solvent: Dimethyl sulfoxide: 3 ml.

Reaction temperature: 250 C.

Reaction time: 48 hours

Analysis of the volatile product (1.5 g.) by gas chroma-

tography gave three components, two of which were identi-

fied by their infrared spectra;

CF3CF=CF2, 2% C3F H, 96% Unknowm. 2%

Reaction of CF 3 Br and CF3I with zinc in acetic
anhydride

Method 1 was employed.

Amount of reactants:


CF3 a Br: 3 g. (0.013 mole)

CF3I: 3 g. (0.015 mole)

Granular zinc: 6 g. (0.09 gram-atom)

Solvent: Acetic anhydride

Reaction temperature: 1000 C.

Reaction time: 12 hours

The volatile product (2 g.) was analyzed by gas chromato-

graphy and was found to be composed of: CF3H, 30%

C2F6. 20% CF I, 30% and traces of CF Br.
3 .3









A small amount of high boiling material was also obtained.

The infrared spectrum showed that it was unreacted p-bromo

-trifluoromethyl benzene.


Reaction of CF3 Br and CF2=CFI with zinc in acetic
anhydride

Method 1 was employed.

Amount of reactants:


CF3 Br: 3 g. (0.013 mole)


CF2=CFI: 2.5 g. (0.01 mole)

Granular zinc: 2 g. (0.03 mole)

Solvent: Acetic anhydride: 3 ml.

Reaction temperature: 250 C.

Reaction time: 5 days

The volatile product was analyzed by gas chromatography and

found to consist of CF2=CFH and unreacted CF2=CFI. Approx-

imately 2 g. of p-bromo-trifluoromethyl benzene were also

removed.

Preparation of C F5I from the CF COOAg and iodine

In a 100 ml. round bottom flask 24 g. (0.046 mole) of

C F15COOAg, and 40 g. (0.156 mole) of iodine were mixed well

and heated with a low gas flame until the solids melted

and the iodine refluxed. Then vacuum was applied to the

reaction flask and a liquid product was collected in a

liquid-oxygen trap. Treatment of the product with sodium

thiosulfate, followed washing with water and drying with

16 g. of CFP151.








Reaction of C 7F5I with zinc in ether

Method 2 was employed.

Amount of reactants:

C7F151: 7.5 g. (0.015 mole)

Granular zinc: 8 g. (0.112 gram-atom)

Solvent: Ethyl ether: 100 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours

The solids obtained were treated with dilute hydrochloric

acid to dissolve the unreacted zinc and the zinc iodide,

and 2.3 g. of a waxy solid remained, which was identified

by its infrared spectrum as the coupled product, C14F30.

The NMR spectrum also is in accord with the above formula.

Melting point: 800 C.

Analysis for F:

Theoretical: 77.3% Observed: 76.2%

Preparation of 1CF CF2COOCH3

A 100 ml. round bottom flask containing 18 g. (0.055

mole) powdered AgOOC-CF2CF2COOCH3 and 40 g. (0.16 mole) of

powdered iodine was heated with a low gas flame until the

reaction mixture melted and the iodine started to boil.

Then a vacuum was applied to the flask and a volatile li-

quid was distilled into a liquid-air trap. The liquid was

treated with aqueous sodium thiosulfate, to free it from

the iodine, was washed with water, and dried with calcium









chloride. The amount of product was 11 g. which consti-

tutes a yield of 67%. The DNMR apestrum is in accord with

the formula, ICF2CF2COOCH .

Fluorine analysis for CkH3F4102:

Theoretical: 26.6% Observed: 27.3%

Preparation of ICF2CF2CF2COQCH3

A mixture of 10 g. (0.027 mole) of AgOOC(CF2 3CCOCII3

and 20 g. (0.08 mole) iodine was placed in a 100 ml. round

bottom flask heated with a low gas flame until the whole

reaction mixture melted and the iodine started to boil.

Then the mixture was cooled and reheated with the flame.

This cycle was repeated three times. A liquid product

appeared in the flask at room temperature which was

pumped out and collected in a liquid-oxygen trap. This

liquid was treated with aqueous sodium thiosulfate to re-

move the iodine, washed several times with water, and dried

with calcium chloride. Purified by gas chromatography, it

gave the following constants:

b.p.: 1500 C. n20: 1.4091 d201 2.1 g./cm.3

Fluorine analysis for C5 3F6102:

Theoretical: 31.8% Observed: 30.4%

The IMR is in accord with the formula, I(CF2)3C000f.

Yield: 80%

r pratxion of the silver sa t poerflerogl uci.. acid
Fmhe peruorogut and sUwas in etr

The perfluoroglutarie acid was dissolved in ether and




64


with continuous stirring the equilvaleftt &mount of silver
oxidA was added in small posrtlans. Beaetion 'took place

immediately and the hest Ovolted, bdielico. f some 61 tn*

ethor. After the addition of all the silver oxide., the:
mixtuar# Vws stirred overnight, Bfiltered under vacuyz, and
the wther removed. Since tht salt Is soluble in ether it


to the theoretical valmo.

1 3
Prke2aration of the wilver Salts of CF POOF-GOOH,
-=-3-7
CF CF CF CF 3 C'F
1 3 1 3 1 3 1
C FOCFCF CCFCOqOH and ICC CUPGF ? 0 CP qM00

The silver salts of. the xbove asids could be prepared

from the free acids 404 s:Ilter exi~to IM sther:, The weld
was dissolved In other and the oquivalent awoqat of silver

o*."* was 94ded slowly With 40entinmes sttiprro. Tk$ mix-

turet war, filtterd to *wbMov any *ftreasted silver ert&*,

and the filtxvat "mae"#ted to voeodft the either.

Aelt~ing point Of trio"r aeld silver salt.: 1320 C.
KMitIng "oAnt of **-tr**r sacid silver: $*It: 170 C.

,COOOK


in a 250 *1. rovAt bettea flask es 1a 30 g

(0.12 46le) of the Aem"NueTFy bate*ro pefltorlie *4t~

acJA d1i;sot1rd $A 1010 va*Uf"* &&ps an 16 st (0.Ot "K4)

of Silvt*w OSIA*k IV** ****AW* M* Xabined pngh 4

anA *han fila*nd fto remartl *0#986401 Al**r Ahm








dioxane was removed in vacuum and the silver salt precipi-

tated. It was reerystallized from methyl alcohol.

Yield: 73A

Kelting point: 1200 C.

Reaction of CTI I and (Ci3)21SIC with zinc in dioxane

Method 2 was employed.

Amount of reactants:

C.3 1: 14 g. (0.1 mole)

(Cli )2SIC12: 10 g. (0.08 mole)

Granular zinc: 10 g. (0.145 gram-atom)

Solvent: Dioxane: 50 ml.

Reaction temperature: 1100 C.

Reaction time: 24 hours

Analysis of the volatiles by gas ohromatography showed that

(CH3)4Si was formed in a 40% yield, together with other

unidentified products.

action of (C[I3)3SiCl with zinc in diozane

Method 1 was employed.

Amount of reaebants:

(CH3)3SiCl: 4 g. (0.037 mole)

Granular zinc: 5 g. (0.07 gram-atom)

Solvents Dioxane: 3 ml.

Reaetion temperature: 1000 C.

Reaction time 12 heurs

The starting mate-ial was recovered unchanged, indicating

*tht no reaction had taken pla*e.







Raoiction of (C1icL MEd. 3 a P :- ,I iilth sinn in dt omne
Method 1 was employed.
Amount of reactants:
(CH3)3SC101 4 g. (0.037 mole)
CF31 3 E. (0.013 .le.)
Granular zine: 5 g. (0.07 gra-matla)
Solvent: Dioxane: 3 i1,
Heaction temperature: 10 C.
Reaction times 12 hoew
Analysis of the product by gas chr i .maft@eihy showed the
following oompounds:

CF. 1, 40% CF I, 40% Me SiP, 10% UnknMa, 10%

P ?.01741 __ re 4 125 C, eta: hue dust peattna in a

A nickel tube (20 in. long and 1 in. in diametr) was
filled with activated sine and heabot to 3750 C. under a
heliau purge. Thm the heli~t flew was steppi andl tri-
fluorobrommfilthaiaen was peOi-ed through at the MAt& 6t 30
ee./min. The and of the tubr was eonnWed~ wrth a glass
tmp iamersxed in liquid-eaxygnt., tei the priieduest wsfas
eelleete'. Tih reetion was ceantint for 30 ti.ime.
Thg product oeqfloted in the Ia;p -as irud ti .g a
stemagq plit"er ad analyeed by 3as shtrmbegnef Ma
the feleiit ItoStSe, i AIf iAM & irtin trnitem



rI-F : ...... .. ... ..
c C u$a 2-60.
V.








Preparation of HC o201

In a 250 ml. flask were mixed 20 g, (0.03 mole) of

powdered HC10F20COOAg and 120 g. (0.5 mole) of iodine.

The flask was heated with a mantle to 1300 C. until the

mixture melted and it was kept at this temperature for

five hours. Carbon dioxide was eliminated during the

reaction. Then the reaction mixture was dissolved in

aqueous sodium thiosulfate giving a yellow solution. This

solution, on dilution with approximately four volumes of

distilled water, precipitated a yellowish solid which was

filtered and washed several times with water. Then it was

dried under vacuum, and extracted with ether. After removal

of the ether, a light yellow solid remained, melting at

69-70 C. It was shown to be HC10F201.

Fluorine analysis,

Theoretical: 60.06% Observed: 59.23%

Yield: 80%

MMR spectrum is in agreement with the above formula of

the product.

Reaction of C F I and CHU=CHCH2Br with zinc in acetic
anhdride 3-7

Method 1 was employed:

Amount of reactants:

CF 71: 3 g. (0.01 mole)

CH2=CCH2HBr: 3 g. (0.02 mole)

Granular zinc: 2 g. (0.03 gram-atom)







Solvent: Acetic anhydride: 3 ml.

Reaction temperature: 25 C.

Reaction time: 12 hours

The volatiles (1.2 g.) when analyzed by gas chromatography

gave the following products:

CHI3CH=CH2, 80% C3F7H, 6% C6F14W 5%

C3F71, 5% Small amount of unknown

Reaction of C F I and (CH 3)C-Br with zinc in acetic
anhydride- 7
Method 1 was employed.

Amount of reactants:

C3F 1: 3 g. (0.01 mole)

(CH3)3C-Br: 3 g. (0.02 mole)

Granular zinc: 2 g. (0.03 gram-atom)

Solvent: Acetic anhydride: 3 ml.

Reaction temperature: 1000 C.

Reaction time: 12 hours

Analysis of the product (2 g.) gave the following compound

identified by their infrared spectra:

C3F7H, 85% C6F14, 10% Small amount of hydro-

carbon.

Re motion of C2F5I and CH3I with zinc dust in dimethyl
sulfoxide

Method 1 was employed.

Amount of reaetants:
C2F51: 2.5 g. (0.01 mole)

CH3I: 2 g. (0.014 sole)

Zine dust: 5 g. (0.07 gram-atem)








Solvent: Dimethyl sulfoxide: 5 ml.

Reaetion temperature: 250 C.

Reaction time: 12 hours

The volatile product (3 g.) analyzed by gas chromatography,

gave the following fractions which were identified by their

infrared spectra:

C2gF5, 95% Cr3CF2CHI. 5%

Thus, only a small amount of the coupled product was

formed.

Reaction of CF I and C H I with zinc dust in acetic
anhydride 2 -5

Method 1 was employed.

Amount of reactants:

C2F5I: 2.5 g. (0.01 mole)

C2H51: 2.5 g. (0.016 mole)

Zinc dust: 7 g. (0.1 gram-atom)

Solvent: Acetic anhydride: 8 ml.

Reaction temperature: 250 C.

Reaction time: 12 hours

The volatile portion of the reaction mixture (3 g.) was

transferred to a small cylinder and analyzed by gas chroma-

tography giving the following fractions, which were identi-

fied by their infrared spectra:

o CH 3C 60% C2F 5, 10% C 4F0, 30%





70














0-4


Pi,
09






0




4<0


F CC


8 0 r ff 4
m c

ml















E-s



,-i .-
O
< .0




0 a
,i


o o
0

t-






0
Q,

C



0

0




*













,O


0- N










C'.- 120
V' C-


'.0
a' Q 0

f-sl r


CO V





S r-q





.-O


Iq 01 rD.n
D4 L0-0 0-0
U-0 0 0 C
0 CM C. C\?
5 E r^ rz' I

0 rrJ ri. tz. jz. C4 Ci U-0-'
C^ 0 OH [ (4 & U-U U-U U-U O0
0 C C C C 0-. 0-0 0-0 0
0 0 U-0 -0 O O O N(
U 0 0 0 N CN N'
0 mcr ;X. E ow0 ( 0 0 L r.)
-) O a U = f rm. U- r
M (" CU u U-- U _0 C\ 0,
CL- 0 O O U0 -
U U O U 4 O- (" EL
0.1 C%! tL D4 U U
N --E N U u
0-I 0-H 0 0 0 0-


D 03 O








00
0 {C- CO
* .,
f n> NO


ci:



u
iJL.




o












'4
Li


















O 4 1




SH ,




r-i ) 4
1s- 4j m


0 4-.
r--1





C. 0
C >
L--



O 0

H >
0I.

Pr





0




0


N


cvI


U-0
0
(\



N -U 0 O

0 0\ 0 \ 0 o
C-0 0r 0< ,

0 NQ u EE l 0 0
UO zO




S 0\ 0 '-
". -l .) -


0 0 VV -

\n0 C- --







S10 N

C0 X C' 10
1 CN 4 4
C-















'0
C.
,0




00




0 V%
o Lo
C- rE-













IV. SUMMARY


The reaction of fluorine-containing alkyl halides

with zinc was studied in various solvents. The perfluoro-

alkyl iodides are the only perfluoroalkyl halides that

were found to couple with zinc; it was discovered that

the yield of the coupled product increases with increase

of the number of carbon atoms of the iodide. The reduc-

tion product of the iodide is almost invariably formed

during the coupling reaction. Secondary perfluoroalkyl

iodides were also found to couple with zinc; however, the

yield of the coupled product is low and often the olefin

resulting from dehalogenation of starting material is

formed. It was found that the saturated perfluoroalkyl

iodides cross-couple with other saturated iodides as well

as with trifluorolodoethylene and trifluorobromoethylene.

The yields of the olefin produced by the cross-coupling

with the last two compounds increases as the reaction

temperature decreases. It was also possible to cross

-couple a perfluoroalkyl iodide with an organic iodide

but the yield was low.

Fluoroalkyl iodides containing other elements such

as H, Cl, 0, and S were also coupled with zinc. Quite

often dehalegenation eeourred yielding an olefin. While




74:


the saturated perfluoroalkyl bromides vvre found to be

resistant to coupling, two flueroalkyl bvomides,
CF CF CF
1 3 1 3 1 3
5"" "2 3 3 7 ~2 2 '
and oxygen, vespectively, wvre eeupled sueesswoully.

Aromatic fluorine-eontaining iodideos wore found wither

to be Inert toward zinc or to yield tarry products.

The methyl stars of V,.iodoperfluoropropjonic acid

and -Iodoperfluorobutyric &aid were prepared and vwee

successfully coupled with zinc to form (CF2 ) and


(CF 2)6 ,COH3resp~etively.2 ,OK3
-COOCH3



































SPPENIDIX





-" 7 -f-"i.I"'" "' ~ ... ~ *"-r- '- ' -I- . t'0 . "~. '+"- t" T '.n- r -T'"-






I -
S- - + --- --








Infrared Spectrum of H(CF2)20H.












.C I.I) -.---0. . (-.- --




-- .1- .. I- -.- = : ... L. i =_-- - : -- -


Infrared Spectrum of C14F30.


Infrared Spectrum of "Teflon."


ft<


U i sk


I


I I.. I




**-"-*-77
Il .u )u .. .. m, .
. ... .. .... ...... .. .... ... ... .. .... .. 7


l1 7 M i T r ri' i '1 ; 1 1 i TI Q i l i[ ii




r "l.......
. . I .... .j t-. ....."
I IT




At i t- I i






Infrared Spectrum of ICF2CF2COOCH .










t4 -t'+. : ..r"1 0 . J"
I ..: . . .
... .. .. .....

















Infrared Spectrum of ICF2F2CF2C00CHR.
-T, -








U TU

V.1
3: '04

.ij 41 i


{1'~~tL4 -ML I<'


A4rT; r ztit-F


"I


-i.t Hfi


Infrared Spectrum of BrCF2CF2CF2COOCH .


F wt *4'


* **jmmH-'r *
vsa-}- i.in


f.t.I ef- H













ILI i-_I


"" n. Ir ,rr


--- IK


1 -. L-+-4-- I-


Infrared Spectrum of C F OCFHCF.


F I p T t





-. -- ..









Infrared Spectrum of CF7OCFCF2OCFCFPOCFBr.


cF3 cF3 cF3
O f











- t ,. _
-i :. -
4-t'



















'*t~j ni TH i z3 ?! P r' 'rR" -- ~ *-* -. -*_ *^


^T^ =I:- T i;-* i^..- ri | TI .i y a= i--- -!, -aiq S '


1 I
r a-


'i- i '_-"-


Infrared Spectrum of CF3CCH2CF3.


I-Th~


ri--,Z 3=IF"


1. 1 1 1
F-1


I


.. .


rga5i


4- U IL Iq U- : .:-:LJ* am. --.FW aw-' t. ',


.f"4: Q':'? ~F r~-


_ +--


SEL -M.


i'*' iMC tuuK


,LW, NG i*-


tluriibk.-L. L-L lim-h


---- 9 -F -























Infrared Spectrum of C F OCF CFOC F.

CF3 CF3


1 -44--i ii ii
Ti j 7

-LI-Li r




91 M
7-T Pi


Infrared Spectrum of (C F OCFCF20CF-)2
3 F3 7 F3
CF3 CF3


Infrared Spectrum of (CF7OCFCF2OCFCF2OCF-)2.

CF3 CF3 CF3


...~.....~. ~.
v. s lul rul s


Iw. l- I-


,5
























Infrared Spectrum of C F OCFI.

CF3


7:11

... .. . . .
.




o: W- -7-
'2i- T
az 1-
: i !_:fY~~.' t~~!~ _~Lf ~ YT t ~ ?(IC~Yifr~j~lI~t~-TI~ ~~?- LF-i


Infrared Spectrum of C F OFCFCFOCFI.

CF3 CF3


Infrared Spectrum of C F OCFCFOCFCFOCFI.
C3 7 2CF3 F CF
CF3 CF3 CF3


O orIn


un >uuu IJIK JM l









t1T-T


Infrared Spectrum of HC10F201.













V. BIBLIOGRAPHY

1. H. J. Emeleus, R. N. Iaszeldlne, J. Chem. Soc.

2948-2953 (1949).

2. W. T. Miller, E. Bergman, A. H. Fainberg, J. Am. Chem.

Soc. Z9, 4159 (1957).

3. R. N. llaszeldine, Nature 168, 1028 (1951).
4. R. ri. Haszeldine, E. G. Walaschewski, J. Chem. Soc.

3606 (1953).

5. R. N. Haszeldine and Steel, J. Chem. Soc. 1592 (1953).

6. W. K. R. Musgrave, R. D. Chambers, J. Savory, J. Chem.

Soc. 1995 (1962).

7. R. N. Haszeldine, J. Chem. Soc. 4423 (1952).
8. A. L. Henne, J. Am. Chem. Soc. 77, 2334 (1955).

9. Wei-Yuan, 3hi-Chun Hung, Tren-Fei Hsu, and Da-Nan Nee,

Hua Ilsueh Hsueh Pao 30 (1), 6972 (1964).

10. P. Tarrant, A. h. Lovelace, h. R. Lilyquist, J. Am.

Chem. Soc. 77, 2783 (1955).

11. J. Harmon, U. S. Patent 2,404,374 (1946).

12. E. Nield, R. Stephens, J. C. Tatlow, J. Chem. Soc.

166 (1959).













BIOGRAPHICAL SKETCH


Skevos N. Tsoukalas was born April 23, 1928, at

Kalymnos, Greece. In June, 1946, he was graduated from

Sixth Athens High School. Following high school he at-

tended the University of Athens, Greece, and in November,

1952, received a B. S. in Chemistry. From his graduation

until September, 1954, he was employed as analytical chem-

ist by Pireas State Hospital in Greece. In September,

1955, he came to the United States, and attended the
University of Florida from 1956 1958 when he received

a M. S. with major in Chemistry. He was employed from

1958 1959 by Harris Standard Paint Company in Tampa,

Florida, and in August, 1959, he joined the research

staff of Peninsular ChemResearch, Inc. in Gainesville,

Florida. While working at Peninsular ChemResearch, Inc.

he resumed his graduate study at the University of Florida

toward the degree of Doctor of Philosophy.

Skevos M. Tsoukalas is married to the former Helen

Samarkos and is the father of four daughters.









This dissertation was prepared under the direction

of the chairman of the candidate's supervisory committee

and has been approved by all members of the committee.

It was submitted to the Dean of the College of Arts and

Sciences and to the Graduate Council, and was approved

as partial fulfillment of the requirements for the degree

of Doctor of Philosophy.


April 23, 1966


Uean, Colige''o Arts and Sciences


Dean, Graduate School


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