Title: Preparation and reactions of some fluorine containing silanes
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Title: Preparation and reactions of some fluorine containing silanes
Physical Description: v, 61 l. : illus. ; 28 cm.
Language: English
Creator: Oliver, Ward Hopkins, 1930-
Publisher: s.n.
Place of Publication: Gainesville
Publication Date: 1964
Copyright Date: 1964
 Subjects
Subject: Silane compounds   ( lcsh )
Silicon compounds   ( lcsh )
Organofluorine compounds   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
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non-fiction   ( marcgt )
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Thesis: Thesis - University of Florida.
Bibliography: Bibliography: l. 58-60.
Additional Physical Form: Also available on World Wide Web
General Note: Manuscript copy.
General Note: Vita.
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Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
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Resource Identifier: alephbibnum - 000424024
oclc - 11069390
notis - ACH2429

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PREPARATION AND REACTIONS OF SOME

FLUORINE CONTAINING SILANES


















By
WARD HOPKINS OLIVER


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
December, 1964














ACKNOWLEDGMENTS


The author wishes to express his appreciation to those whose as-

sistance, advice and encouragement have greatly contributed to the

success of this research: To Dr. Paul Tarrant, director of this re-

search and Chairman of the Supervisory Committee, whose creative ideas,

assistance, and guidance were essential factors in the undertaking and

completion of this work; to the members of the Supervisory Committee

for donating their time, advice, and assistance; to Dr. Wallace Brey,

for the interpretation of nuclear magnetic resonance spectra; and to

the Army Natick Laboratories, for financial support of this research.

Special thanks are due to the author's wife, for her encourage-

ment, understanding, and help in the preparation of this dissertation.













TABLE OF CONTENTS


Page

ACKNOWLEDGMENTS ii

LIST OF TABLES v

INTRODUCTION 1

DISCUSSION 10

Preparation of Compounds of the Type RMe2SiCF=CF2 10

Preparation of Me3SiCH2CF=CF2 14

Preparation of Compounds of the Type RMe2SiCH2CH2CP=CF2 16

Preparation of Compounds of the Type RMe2SiCH2CH2CH2CFCF2 19

Reactions of Me SiCF=CF2 22

Reaction of ClMe2SiCF=CF2 with Pentafluorophenylmagnesium
Bromide 26

Reactions of Me SiCH2CH2CF2CF 27

Thermal Dimerization of CIMe2SiCH2CH2CH2CF=CF2 29

Preparation of Fluoroisopropoxysilanes 29

EXPERIMENTAL 39

General 39

Preparation of Trifluorovinylsilanes 39

Preparation of 2,3,3-Trifluoroallyltrimethylsilane 43

Preparation of (3,4,4-Trifluoro-3-butenyl)silanes 43

Preparation of (4,5,5-Trifluoro-4-pentenyl)silanes 45

Reactions of Trifluorovinyltrimethylsilane 46

Preparation of 1,2-Difluorodlefins from the Products of
the Organolithium Reactions 50







Reactions of (3,4,4-Trifluoro-3-butenyl)trimethylsilane 52
Thermal Dimerization of (4,5,5-Trifluoro-4-pentenyl)dimethyl-
chlorosilane 53

Preparation of Halogenated Isopropoxysilanes 54

SUMiARY 56

BIBLIOGRAPHY 58

BIOGRAPHICAL NOTE 61













LIST OF TABLES


Table Page

1. Olefins Prepared from Me SiCF=CF2 via Lithium Reagents 25

2. Physical Properties of Compounds Prepared 34














I. INTRODUCTION


The rapid advancement of technology during and since World War

II has demanded the development of many materials that were not avail-

able twenty-five years ago. High performance aircraft and rockets

require structual materials which are both light and strong; their

engines require metals that will withstand extreme heat, as do their

surfaces; they require fuels of very high energy content. Elastomeric

materials are needed in many modern applications that maintain their

properties over a wide temperature range, especially at low tempera-

tures. In addition, very often they must be resistant to hydrocarbon

solvents and harsh chemicals as well as different types of radiation.

It became evident soon after World War II that natural rubber

could not be improved to meet the needs that further progress demanded.

To meet the increasing need for new elastomers, the Office of the

Quatermaster General established at the University of Florida and else-

where in 1951 a long-range Arctic Rubber Program. Under this program,

these laboratories, under the direction of Dr. Paul Tarrant, have been

responsible for the synthesis of new monomers.

The discovery of Teflon, although not an elastomer, indicated the

possible use of fluorine-substituted polymers. Its high thermal sta-

bility and resistance to chemical attack generated great interest.

Subsequent work has proven quite fruitful, and the work in these labo-

ratories has been centered predominately around synthesis of fluorine-

containing monomers. Early interest centered around olefins and

1








dienes; thus Lovelace and Attaway (26) developed methods of preparing

fluorine-substituted butadienes; Gray (4), Lutz (8), and Taylor (33)

prepared fluorine-substituted isoprenes; Taylor (35) also prepared

several isobutylenes; and Warner (34) prepared new fluorodlefins by the

reaction of Grignard reagents with simple fluorodlefins.

Polymers containing a large percentage of fluorine tend to lack

flexibility. Since heteroatoms in the backbone or side chain of poly-

mers can add flexibility, methods of preparing the appropriate monorers

were studied. O'Connor (31) and Pisacane (15) prepared fluorine-con-

taining nitroso compounds; Stump (32) prepared fluorine-containing

unsaturated ethers; and Tomasino (36) prepared several silanes and

siloxanes containing fluoro8lefin groups.

Polydimethylsilicone rubber is known for its exceptional thermal

stability and resistance to ozone. It has excellent electrical prop-

erties and very low water absorption. However, it is degraded by

strong acids and bases, and is particularly prone to swelling in hydro-

carbon solvents.

The thermal stability and inertness of fluorocarbons to chemical

attack and to solvents recommended their incorporation into silicone

rubber to improve its properties. Studies showed that fluorine on a

carbon either a or B to the silicon atom decreased the stability of

the molecule to both heat and strong base. Fluorine atoms three or

more removed from the silicon atom, however, caused no decrease in

stability.

As part of a broad program to develop new polymers, the Materials

Laboratory of the Wright Air Development Center (WADC) undertook re-

search to develop fluoro-silicone elastomers. Under this program








McBee (9) prepared the first difunctional fluorine-containing silane,

CH Si(OCH )2CH2CH2CF3, by the reaction of CF CH2CH2MgBr with CH Si-

(OCH3) His attempts to polymerize this material and to copolymerize

it with dimethyldichlorosilane yielded only viscous oils. However,

at Dow-Corning (as part of the WADC project) an elastomeric polymer was

achieved using CH C12SiCH2CH2CF, a compound reported by Tarrant, et al.

(27). This rubber, called Silastic LS-53, retained all of the excep-

tional high and low temperature properties of silicone rubber with' the

added feature of excellent fuel and oil resistance (16).

If an elastomer is to be produced in any quantity, it is necessary

that the monomers be produced in good yield by an economical process.

The more important general syntheses of silanes will be considered

below:

1. The Direct Synthesis

The most important method of preparing organosilicon com-

pounds is the direct reaction of an organic halide with elemental

silicon. The reaction occurs when the halide vapors are passed

over silicon at high temperatures in the presence of a metal

catalyst. A mixture of products occurs.


CH C1 + Si Cu300 0 (CH
3 30O-400-3o (4-x)

but reaction conditions can be varied to favor a particular

product. Copper is the preferred catalyst with alkyl halides,

although several other metals can be used. Silver is the most

effective catalyst with aryl halides.

2. The Organometallic Method







Grignard and organolithium reagents react with silicon

halides, alkoxides, and hydrides to form compounds with new

silicon-carbon bonds.


Me SiCI + C6H5 gBr ------ Me SiC6H5


Me3SiOEt + C6H5Li Me3SiC6H5 + LiOEt


(C6H5)3SiH + C6H5Li --- (C6H5)4Si + LiH


The chlorides are more easily replaced than the alkoxides

or the hydrides:


Cl2Si(OEt)2 + 2MeMgCl ------ Me2Si(OEt)2 + 2MgC12


ClSi(Me2)H + CF2=CFMgBr --- CF2=FSi(Me2)H + MgBrCl


Because of the availability of organosilicon chlorides, and

the great variety of organometallic reagents, this is the most

versatile method of preparing organosilicon compounds.

3. Addition of Olefins to Silicon Hydrides

Olefins (and alkynes) can be added to silicon hydrides in

the presence of a catalyst such as peroxides, acids, metals,

metal salts, ultraviolet light, or %7-rays. Chloroplatinic acid

appears to be the most effective of these catalysts when u.v.

light is not practical.

H2PtCl6
Cl SiH + CH2=CHCH3 or u.v. C3lSiCH2CH2CH3


This reaction is general and is especially valuable in that

a carbon-silicon bond can be formed without disturbing the








silicon-chlorine bond, as would be the case with organometallic

reagents. This method has become a very important laboratory

and industrial process.

4. Preparations from Carbon-Functional Or-anosilicon Comnounds

Complex organosilicon compounds may be prepared by further

reaction with a functional group already present in an organic

substituent attached to a silicon atom. Many carbon-functional

organosilicon compounds are readily prepared and are available

commercially.

Silanes containing olefinic groups, such as vinyl and allyl

groups, are perhaps the most important of these.


(CH COO)2
CH CH2CHO + CH2=CHSiMe3 CH CH2CCH2CH2SiMe


SiH4 + CH2=CHSiH3 u.v.. H SiCH2CH2SiH3


The halides are also useful:

0
CH COOH II
Me3SiCH2C1 + CH COOK Me SiCH2OCCH

/0
CH2-CH2
Me SiCH2Cl -- Me SiCH2MgC1 CH2-CH2 Me SiCH2CH2CH20H


These are very general examples. The reactions under this heading

are very extensive, and with some notable exceptions, are the same

as would be expected of the functional groups in hydrocarbon mole-

cules.

All of the above methods have been used to prepare fluorine con-

taining silanes. Haszeldine (5) was the first to report the successful








preparation by the direct method.


CF I + Si (CF )xSi(4-x)


This method has been used with other perfluoroalkyl halides, but poor

yields are generally obtained and thus the method is not of importance

in monomer synthesis.

McBee's synthesis of the first difunctional fluorine-containing

silane has already been referred to (9):


CF CH2CH2MgBr + MeSi(OEt) -- > MeSi(0Et)2CH2CH2CF3


The organometallic method has been used very extensively to prepare

fluorine-containing silicon monomers.

Tarrant and coworkers (27) were able to prepare a similar monomer

to McSee's in a much more convenient reaction:


CF CCHCH2 MeSiHC12 P -->- Me(C12)SiCH2CH2CF 60%


The free-radical addition of perhaloalkanes to olefins is an important

step in preparing silanes containing fluorodlefin groups. Tarrant (23)

reported the following reactions:

Bz C
CF2BrCFClBr + CH2=CHSiMe3 Bz CF2BrCFClCH2CHBrSiMe

SCF2BrCFClCH=CHSiMe3


In these laboratories Tomasino studied the free-radical addition

of CF2BrCFClBr to a series of alkenyl silicon compounds. These com-

pounds were vinyldimethylethoxysilane, vinyldimethylchlorosilane,








divinyldimethylsilane, allyltrinethylsilane, diallyldimethylsilane,

vinylpentamethyldisiloxane, and 1,3-divinyl-1,1,3,3-tetramethyldi-

siloxane. The addition products obtained were further dehalogenated

and/or dehydrohalogenated to form new unsaturated compounds.

It was found that the normal addition products were obtained when

CF2BrCFClBr was reacted with the vinylsilanes. However, in the dehalo-

genation of these products with zinc and ethanol considerable reduction

of the bromine on the carbon c to the silicon took place. For instance,

in the dehalogenation of CF2BrCFC1CH2CHBrSiMe a 43% yield of the ex-

pected CF2=CFCH2CHBrSiMe3 was obtained, as well as an additional 21%

of the reduced product, CF2=CFCH2CH2SiMe This phenomenon was noted

in each of the compounds containing a a bromi.. atom.

Reaction of CF2BrCFClCH2CHBrSiMe3 with concentrated sulfuric acid

gave [CF2BrCFClCH2CHBrSiMe2]20 in 16% yield. This compound was then

dehalogenated to give a mixture of unsaturated disiloxanes, including

[CF2=CFCH2CH2SiMe2]20 in a 5% yield.

Reaction of CF2BrCFClBr with allyltrimethylsilane did not give the

expected CF2BrCFClCH2CHBrCH2SiMe but instead CF2BrCFClCH2CH=CH2 was

obtained in a 30% yield. This was undoubtedly formed from the expected

addition product, since it is known that silanes containing a halogen

S to the silicon atom are quite unstable to heat and form terminal

olefins (22). Diallyldinethylsilane, however, gave the desired mono-

addition product, CF2BrCFClCH2CHBrCH2Si(Me2)CH2CH=CH2.

The first trifluorovinylsilane derivative was prepared by

Knunyants (24). He reacted CF2=CFMgI with SiC14 and obtained Si(CF=CF2

as the only product. It is interesting to note that no mixed products

were obtained. Knunyants failed to obtain products when CF2=CFMgI was








reacted with alkyl or phenyl substututed chlorosilanes.

Seyferth, however, was able to prepare Et3SiC=CFF2 from the reac-
2
tion of Et SiC1 with CF2=CFMgBr in THE (17) and Me SiCF=CF2 from the

reaction of Me SiC1 with CF2 FLi (21). He also prepared Me SiCF=F2

from CF2 CFgBr, but the product boils very close to TSF (670) and had

to be brominated before it could be recovered.

Knunyants (24) found that all the Si-C bonds in Si(C-=CF2) were

broken under the influence of aqueous base, yielding CF =CFH quantita--

*tively. Seyferth (18) obtained, in reacting Et SiCF=CF with Et0;:a,

a 69% yield of (Et Si)20 and only 28% of the expected Et SiCF=CFOC2 "
3 2 3 2-5-
He further found in reacting phenyllithiun with Et SiCF=CF2 that the

third mole of C6H5Li cleaved the Si-C bond:


CG6H5Li
Et SiCFCF2 + C H5Li -- Et SiC-=CFC6H5 5

CjH Li
Et3SiCFC(C6H5)2 or Et3SiC(C6HS)=CFC6H Et SiCH


655
+ C 6H5C=CC6 5


These reactions indicate the instability of the Si-C bond in

Si-CF=FR to basic media. Further, considering the failure to get

mixed products in reacting CF2=CFMgI with SiC14, it is obvious that the

presence of a fluorinated olefinic linkage a to a silicon atom renders

the silicon atom more susceptable to nucleophilic attack. This can be

explained quite readily, realizing that there is p- 77 d- 77- overlap

between the unsaturated carbon atom and the silicon atom. The electron

withdrawing effect of the fluorine atoms is transmitted to the silicon







atom through the empty d-orbitals, leaving it effectively electron

deficient. An electron-rich group could then readily attack the

silicon atom, displacing the trifluorovinyl group or other group with

its pair of electrons:



X:-- XSi + :C=CF2 CHF=CF2



or



C 9/ Cl
-CI UI/\ 0\ CI i
X.--- :Si-C C --- iCF=CF + Cl
CCF Cl" 2

No compounds of the type R Si-CH2C=CF2 or R 3SiCH2CH2CH2CF=CF2

have been reported.

On the basis of the previous work discussed here, it was proposed

to prepare new organosilicon monomers containing fluorine and to study

some of their reactions. The preparation of a series of silanes of the

general formula R-Si(Me2)(CH2)nCF-=F2 received primary consideration,

where n = 0, 1, 2, or 3 and R represents a reactive group such as

ethoxide, chlorine or hydrogen.













II. DISCUSSION


In the course of this research, compounds of the type R!e2Si(C92)n

CF=CF, have been prepared. R may represent a methyl group, chlorine,

ethoxide, or the symmetrical disiloxane; and n may be 0, 1, 2, or 3.

The compounds will be grouped for study according to the value of n,

since each group required a different method of synthesis. The reac-

tions will be considered separately.

In addition, a new method of preparing fluorine-containing alk-

oxides of silicon will be discussed.


Preparation of Conmounds of the Tpe RXeSiCF=CF,

The preparation of trifluorovinyl-Grignard (6,7,13) and -lithium

(20,30) reagents made possible the incorporation of the trifluorovinyl

group into many organic and organomrtallic compounds. However, at the

beginning of this research, the only trifluorovinylsilanes reported

were tetra-(trifluorovinyl)silane (24), trifluorovinyltriethylsilane

(17), and trifluorovinyltriethoxysilane (19). These were prepared via

the Grignard reagent. Later, Seyferth (21) reported the preparation

of trifluorovinyltrimethylsilane from trifluorovinyllithium. He pre-

pared the lithium reagent by the metal exchange reaction between tri-

fluorovinyltin compounds and phenyllithium, a process involving several

steps and giving rise to low over-all yields.








SnCI4 + 4CF2=CMgBr --- Sn(CF=CF2)4 PhLi

CF2=CFLi + SnPh4

IMe SiCI

Me SiC=CF2


Tarrant, et al., had meanwhile discovered a facile method of preparing

trifluorovinyllithiumr via the halogen exchange reaction between bromo-

trifluoroethylene and alkyllithium compounds at -780. By this method,

trifluorovinyltrimethylsilane [I] was prepared during this research in

yields of 65% without the separation of intermediates.


MeLi + CF2=CFBr 7 CF 2=Ci + MeBr

Me SiC1

Me SiCF=CF2

[I]

The physical properties of this compound were consistent with those re-

ported by Seyferth. It should be noted that the trifluorovinyl group

in this compound shows absorption in the infrared at 5.83 microns,

while the same group attached to carbon, hydrogen, bromine, or chlorine

absorbs between 5.5 and 5.6 microns. Triphenyltriflucrovinyltin (pre-

pared in this laboratory) absorbs at 5.88 microns, while tris-trifluoro-

vinylboron absorbs at 5.95 microns (2). All of the metal compounds

mentioned have empty p- or d-orbitals on the metal atom which are un-

doubtedly responsible for the large shift from the usual absorption

frequency. As a matter of fact, the authors in the above reference use

this shift as evidence for carbon-boron 177- bonding.







It was anticipated that other compounds of this series could be

prepared with R being a functional group, such as chlorine or the eth-

oxide. As mentioned in the Introduction, Knunyants (24) found that

only the tetra-substituted product was obtained when CF2=C~ gI was re-

acted with SiCl4. It was hoped that ClMe2SiC?=CF2 could be prepared

by reacting CF2=CFLi with Me2SiCI2 in a 1:1 ratio. However, only the

di-substituted product was obtained:


CF =CFLi + Me2SiC12 --- (CF2=CF)2SiMe [VII]


Elemental analysis, MrD data, and infrared data were consistent with

this structure.

The alkoxysilanes undergo approximately the same reactions as the

chlorosilanes. Both, for instance, can be displaced by a Grignard or

or lithium reagent. However, the chlorosilanes are somewhat more reac-

tive toward these reagents than the alkoxysilanes. Thus, CiSiMe20C2H5

was prepared from Me2SiC12 and C2H OH in triamylacine. This compound

then reacted with CF2-CFLi to form C2HO5SiMe2CF=CF2, and the chloro-

silane was then prepared by reaction with PC13.


NH ie CF =CnLi
Me2SiC12 + EtOH -3 EtOSiC1
Me


Me Me
Iee PC1 Me
EtOSiCF=CF2 > ClSiCF=CF2
Me Me


[II] [III]


The compounds were identified by elemental analysis, YrD data, and their

infrared spectra.








Compounds such as II and III night be of interest as crosslinking

agents in polymers or intermediates in preparing other trifluorovinyl-

silicon derivatives.

The symmetrical disiloxane is another di-functional compound in

the series under consideration. The compound CF2OCFSi:e20SiMe2CF=CF

could undoubtedly have been prepared readily f-om either II or III, but

was actually prepared by another method before II and III were synthe-

sized. The compound ClSiMe20SiiMe2C was prepared by the method of

Patnode and Wilcox (14). This dichlorodisiloxane was then reacted with

CF2-=CLi to prepare IV:


Me Me
I I
2Me2SiC2 + H20 ---s ClSiOSiC1 + 2HC1
2 2 2 I I
Me Me

:*e '-e
2CF2=CFLi i
SCF 2=CFiOSiC'=CF2
Me i'e

[IV]


-c:-..Lal analysis, i.r. spectra, and MrD data were consistent with the

assigned structure.

Another interesting compound of this series was prepared where R

represents hydrogen. The reactivity of the silicon-hydrogen bond was

discussed in the Introduction. Trifluorovinyldimethylsilane was pre-

pared by the reaction of dimethylchlorosilane with trifluorovinylmag-

nesium bromide:


Me Me
HSiCl + CF2gFMgBr ---- HSiCF=CF2
Me Me

[v]








Elemental analysis and MrD data were consistent with this structure.

In addition to infrared absorption at 5.83 microns for the CF2CF group,

a strong absorption at 4.65 microns was pre-snt which indicates the

Si-H bond. Two later attempts to prepare this compound using CF2=CFLi

failed. A brown tar was obtained in each reaction.


P-e -"on of Y-'S7C __C__

Tarrant and Warner (34) discovered that Grignard reagents would

substitute organic groups for fluorine in fluoro8lefins. Dixon (3)

discovered that lithium reagents would likewi-se substitute, and that

they gave somewhat greater yields of the new olefins than tne Grignard

reagents:


RgX + CF2=CX2 RC?=CX2 + MgFX


RLi + CF2=CX2 RCF=CX2 + LiF


With tetrafluoroeth-ylene, Grignard reagents give, in general, mono-

substituted products. Lithium compounds, aryllithium compounds in par-

ticular, tend to give di-substituted products:


PhLi + CF2 CF2 PhCF=CF + PhCF=CFPh

mostly


It was hoped that 2,3,3-trifluoroallyltrimethylsilane could be prepared

from the Grignard reagent of chloromethyltrimethylsilane:


CF2=CF2
Me SiCH C1 + Mg Me SiCHMgCl "
3 2 3


Me SiCH2CF=CF2
*3 2- 2








This reaction was run both by allowing a cold solution of Grignard rea-

gent and CF2=CF2 to warm to room temperature and by shaking the mixture

in a sealed tube for several days. In neither case was any reaction

observed.

The lithium~ reagent was prepared by reacting lithium with brono-

methyltrimethylsilane. A cold solution of the lithium ccopound and

CF2=CF2 was allowed to warm to room temperature. An exother.ic reac-

tion took place and most of the material was lost. Recovered material

gave a product boiling about 1000 which showed no infrared absorption

that would indicate a fluorodlefin. The tetrafluoroethylene was proba-

bly lost when the reaction heated.

The reaction was repeated in a sealed tube. The CF2CF2 was con-

densed into the tube at liquid nitrogen temperature, and the tube

placed in an ice bath. After two days, the tube was opened and the

desired compound was obtained.


:e SiCH2Li + CF2=CF2 --- eSiCH2CF=CF2

[VIII]


Elemental analysis, infrared spectra, and MrD data all support the

structure as shown. It should be noted that the i.r. absorption due

to the double bond is at 5.83 microns. There is no shift observed due

to the silicon atom in the allylic position.

Other compounds of this series were not prepared. It is not like-

ly that a lithium reagent of the type PRe2SiCH2Li could be prepared

where R is a functional group of interest in this series. The chemis-

try of VIII was not investigated at length.








Prer.rat4ionr of Cc- :yrona. of the '-* Kie __2_C.-:2 _CF,
---__-- 2 2

Tonasino (36), in his studies of some fluorine-conta ninng organo-

silicon compounds, prepared the first co-.pound of this series. He

added CF2BrCFClBr to CH2-C..Lie,, and then dehacogcnated the product

with zinc to obtain the olefin. He found that a considerable amount of

the bromine on the carbon atom adjacent to the silicon atom was reduced:


CF23rCFClBr + CH2=CMSike ---- CF2BrCFClCH2CZBrSiMe3


CF2BrCFClCH2CH3rSiXeOe CF2=CFC" -. :.-: 1.

4 3

+ CF2=CFCH2CISi-e3

21%


Thus it is obvious that the a-bronine atom is readily reduced. Since

this reduced product was desired in this research, it was anticipated

that the yield could be increased by the addition of concentrated

hydrochloric acid to the reaction mixture, containing excess zinc, when

the dehalogenation was complete:


CF2BrCFC1CH CHBrSiMe Et H > products H- C


CF2=CFCH2CH2SiMe3

65%

[IX]


This compound had the same properties as reported by Tomasino. It

should be noted that the yield is almost exactly the same as Tomanino's

total for the two compounds, indicating that reduction of the bromide


is quantitative.








Another compound desired in this series, the syrmetrical disilox-

ane, was also prepared by Tomasino. However, it was also a by-product

obtained in low yield:


!:o i:e
CF2BrCFClBr + (CH2-=HSi)20 ---- (CF2BrCFClCH2CHSrSi)20
h2 e Me
16%


n:e ::e
Zn I
t (CF,=CFCH2CHr Si),0 + (CF2=CFCH CH Si)0
Me .e

20o 5%


Since the first step in this reaction gave only a 16' yield of the

desired intermediate, a different approach was sought to prepare the

disiloxane.

The reaction of silicon hydrides with olefins, discussed in the

Introduction, generally goes in very good yields:


H2PtCl
R SiH + CH,=CR' oru.v. R SiCH2CH2R'
3 2or u.v. 3 2 2

CF2BrCFCCCH=CH2 and ClSi'- 2H are both commercially available. It

was found that their reaction product gave a very desirable intermedi-

ate:


Me Me
Ie H2PtC16
ClSiH + CH2 =CHFC1CF2Br CISiCH2CH2CFC1CF23r
Me Me

44%

Ix]








Elemental analysis and MrD data support this structure. This reaction

gave the desired product in an acceptable yield. Other products were

obtained, but dir.etryldichlorosilano was the only one identified.

Another product, which appeared to have no hydrogen but considerable

carbon and fluorine, was obtained, but could not be separated from the

reaction mixture in sufficient purity to be identified.

Compound X could then give the desired disiloxane by two possible

pathways:




A ClSiCHCHCFCF2

S/Zn ey Me
CISiCH CH CFClCF2Dr 0(. .-.. ?2 2
Me
H0 le n 42
2 -0(.:_ J:: 2.h1CF Br)

Me [X:I]

[XII]



Pathway A was att.npted, using TTF as a solvent. The dehalogenr--

tion appeared to proceed normally. Since the chlorosila.ne was desired

at this stop, hydrolysis to remove the zine halides could not be used.

Upon distillation a reaction took place in the distilling flask and a

two phase product was obtained, which proved to be a complex mixture

that could not be separated. The contents of the distilling flask

became very black.

Pathway B, however, went with no difficulty. The yield in the de-

halogenation step can probably be improved considerably, since no at-

termt was made to find optimum conditions. The properties of XIII agree

with those reported by Tomasino.








An attempt to prepare C1Me2SiCH2CH2CF=C_2 d-reccly by adding di-

methylchlorosilane to l,l,2-trifluoro-l,3-batadicre in a sealed tuce

with H2PtC6 at 7?0 resulted in an explosion. Irradiation of dimrt:.l-

chlorosilano and l,1,2-Lrifluoro-l,2-outadier.e in a scaled tube in sun-

light gave a white polymer characteristic of the polymer obtained by

irradiation of the butadicr. a-one.


PreaTr-- ; of C?.--.. n- of th : C ,C-"-

The preparation of a silane of the type F. C"-C" ?=CF2 required

some special consideratic.s. Tomasino .hd att., acted to ore-are an

analogous compound by the addition of C 2ErCFClBr to CH2=CHCH2Si'e .

He obtained, however, cleavage products of his desired intermediate:


CF2BrCFClBr + CH2=CHCH2SiMe --- [CF2BrCFClCH2C irCH2Si:';]


---- Me SiBr + CF2 BrCFCICH2C=CH2


It could not be detcn..Lned if the addition product actually formed, or

whether the intermediate radical form cleaved:


CF2BrCFClCH2C-CH,:SiNMe --- CF BrCFC1CH I2CH2 + -SiMe


If the addition product were formed, it would not be expected to be

stable at the reaction temperature, because B-halo silanes cleave at

around 80-900 to form alkenes and the halo silane (22):


Et3SiCH2CH2C! Et 3SiCI + CH2=CH2


Tomasino was successful in obtaining an addition product with

diallyldimethylsilane, but HBr was lost during distillation:










CF? BrB-CFC 7 r + C:.


C3,r: t I C:


CF 3rC'FC C2CH C:=.


It was conc-lded i:sat this c .e, --ould be *us_-eo

tion of the dCesired series of cm-pous. possi

consider-d, but never tried, :as the use of the Gri.nar:

reagent of the appropriate silane wiitn tetrafluoroet.yl.


+ C2 2
-2 -


.-


This method in-clves the use of pressure vessels because of the boii

point of the CF2 :--so, yields are often quite lo' in such reac-

tions, and the incorp-cion of a functional group on the silicon atom

would be difficult.

The r.ethod finally chosen to prcpa-e the :-_1 -. .:=F2

conmounds was the addition of direth'ylch.lorcsilano to CF 2=7-CHCE=CH 2

a compound prepoaed in fair yields by Tarrsan-c a Gnd Gilr:an (28):


CF2BrCFCrl: + Ci2'. : 3 --- CF,ErCFCICH0CHrCH2C1

7?



The possibility of additio.. to either Ad of t'e- diene is obvious.

At the time of this resea ch no s'cud of h r-l-ive reactivity of


Ior a-th w-as

l r l4thium


S H2C -.2








fluorodlefins and hydrocarbon olefins in such reacticns had been made.

Concurrently with this research, in these laboratories ::ur:a.atsu and

Tarrant (11) studied the relative reactivity cf Lhic rpnaa-~ne toward

the free-radic-al addition of CC1 r. T'3,- fou-.d that aft-r 6 days
-3
irradiation, attack on th, hydrocar-r. vinyl grcu? w-_ pT.dcninant.

After 11 days a mixturee of the two pr -A^ts .ac obtain.. After 25

days, addition to both double bonds -f -cte Zluorocolefin was complete.


CCl r + CH2=: CC'2C -- CCl C2C-i; CH2 CF2


CCl CH CM01
25 U-aS 3 >IC.2.-2 2- --C3


Thus, it is obvious that a free radical attack would t-.e place

preferentially at the hydrocarbon vinyl group. h'":ile the S:-H Croup

can be readily added across an olefin by free radical initiation, ad-

dition by means of metal chloride catalysis is generally considered to

be an ionic process (23). It was decided to run the reaction using

H2PtCl6 as a catalyst:


'-e 2H2PtCl
ClSiH + CH2=-HCE2CF=CF2F CISiCH2CH2CH CFCF2
I 1 2 2 2
.e He

855

[xlv]

or

y.e
ClSiCa2CFHCH2CH=CH2
Me


The reaction was carried out in a sealed glass tube due to the low








`,)i _ng poin.L of t.e a uen ( ).. _e tolusio, -

oternight and conversion was es sntbll qu_ U titati. .... cu at-

product sho.-ed only cns inf.rard .b ci-ptio-n which could 't dt11

to a carbccn-carbon double ba-nd. This ,as at 5.52 -ich i-- dca: a

trifluorovinvl grour. Tus -tin a- t-o the -1(crn

to give LIV. El=mcntal analyti r _nd ar D cata is. o ..;t l=is str-

tore.


The preparation cf the t-i..;t:rl cariva:

reacting XIV wit the O-ri-. rd r..a-:.t

might also be expected to react ,it the Cri

greater reactivity of the silicon-chlorine b(

duct in good yield:


v .


. -. r

gnard reae

)nd led to


sired prz-


Cl iC' CH2C-'C-2^ +
1 __ -


- 5-


Structural proof was by elental anlysis, infrared spectra, and rD

data.

The disiloxae was readily prepared by reacting XIV with water:



'e Ho
2C1SiCH22C HII2CF=CF2 O( ::c- Fc .=C F2 2


2e 2.e
Re-tzoncs co :i- ..-.. *,


Seyferth, in his studies of the vinyl derivatives of metals, has

investigated the addition reactions of trifluorovinyltriethylsilan (19)








and tL..z rz.tion of nuc-, .. r. 1-

silane (18). Tre reactions ,, trif..a .trl.. -ii ; would be

expected to be similar to t:.3se of t:-.- t_- t:.l c-. .-u., r.l for t:.,

reason the addition raactio:.i; : e .ct .

In his studies of -uclco, lic i.. t- t- .. r.

underwent, in general t:..J r.. r :- _...s -i -.. ..n

exception .1as the rcact-on of t:.e sil wi .. ...- in

ethanol, where the :fo2ur I n wa- ....s :,, l ....... ..._i i...

lesser yield the dsp-c- n t or i....li....t.o ,- .t,

Et 'Si?~= 0t. This is a .. at .. t intllty of L trt-
-31

fluorcov.nyl-silicon bond in u . _., h ....o vcr, tl or .o.. -

lic co.pounis, and :..tJ al s roonc olvl-,.

yields of t>- displace..nr. proa.ct.. r-atio with vr_-

Grignard and lithium rea-r.ts, as .. 1 ud. al:.x- .

and mercaptides gv roucs ga of t.. .. o ..f. : .- st: ..

the reaction of the silsa._ u:Lth exc.-s ph.yllithiu ., a.L. found th-

the third mole of phnyllithiu... broke the caroon-silicon bt.nd:



EtSiCFC Phi tSiC-Fh


Et3SiCF=C:h, or Et SiCSLh~C:?

PhLi PhLi

Et SiPh + LiCF=CPh, EtSii'h + LiCh=CFPh



PhC=CPh + Li?


The instability of (C 2=CF)4Si to base, already ciscussed, and the

instability of Seyferth's co.mound to a third mole of phenyllithium,









M a f A r 2

afllcica L t




w UA f ot n.




AC -&I nl-






biOc ie. in the c; of the mconyl, ai i,









It is -hIU 4i h
C iIU 1"-,- Ii- -~IJ
basic hy y ; in c inothcr' t crYe .. wtl c .,n Q

,.*:si .rcIwhas would r Vpr 1Lcn a gonemi ci of
















Minorco sa aruhb L.. c.2 -
Each ofl ther prenzCd- by lai r :=c ut. V.. icY. t.Arcs ar

Con. 2=d ygil a of the dabl a ola>- VL"Z s
case ofthe--ozy!,phoy!,Vatrj


adduct" inr the casos 02 tni Ljl,~~i,~~. -il L-l J 1




s-,all _---ount of olefin was ohtainO-;C, buc CIC~, for po,..i,.v3ideti

fication, in the. case of the Z-thlqA -1.,y cayaund:l, too predust oL=

tafned~ decompo~sedi into a black tar j3 3 hours. '.'-h_ tlo infrz_~

red zpeCtra wks con~sisten~t fror SC 4H 3 :4. the el~.manta' analysis was iI~i




aj:searud pure .y vapor31 pharse tho co:;,rc:osun d: -::?ojrs hu probably

decompzyosed too much by th-e time the clensnai Ln~ralrstl j was ran..

Th-e olefins prepared by this r-.othkod and the intenmrcdlatcs are


listed in Table 1.











jifis ~~-.. JAf



rr,. ___c


CHQLi












CF
9























nC2 2Li
3




CH=C:::L


9..1u


ci


-, 2-


a. + i + L
b.. Pr:_ d h-c -ern-lithiur ex ... : ; + EjLi--

c. .--pared by Lin-lithium xcr.n e: R Sn + 4?hLi --
F.Li + Ph Sn
d. The desired olefin was not positively idcntificd.







Another common reaction of fluorodlefins is the thermal dimeriza-

tion reaction to give cyclobutanes. Trifluorovinyltrimethylsilane was

heated for two days at 200 in a sealed tube to give a very small yield

of a product tentatively identified as the dimer:


200O
2Me Si=C=CF --20 Me SiCF-CF
Me SiCF-CF2


While the amount obtained was insufficient for complete analysis, the

elemental analysis and infrared analysis was consistent for the dimer.

The remaining black, viscous liquid indicated that much decomposition

had taken place.

An attempt to prepare either the Diels-Alder product or the vinyl-

cyclobutane with 1,3-butadiene failed. Only a hard, black solid pro-

duct and a thick oil were formed. No volatile products were obtained.


Reaction of C1Me2SiCF=CF, with Pentafluoroohenylmagnesiun Bromide

As an example of the use of ClMe2SiCF=CF2 [III] as an intermediate

in the synthesis of other silanes, III was reacted with pentafluoro-

phenylmagnesium bromide:


4gBr me/ \
F Me
I F< SiCF=CF
+ ClSiCF=CF -----2 i 2
:[ FJ Me e
F
[VI]


Having noted the instability of the silicon-carbon bond to base in

the fluoro8lefin derivatives previously discussed, it was desired to

find if the pentafluorophenyl group would be stable under similar















S-,fu LO ...J .t -- .o ,






pet
-isiorna "ct p.. aL ..


spect:- a.nd v.p.c. _-tention ti:.

present.


r C -=c


N


+ CF,=C:F + c clic --1ox .


Treatr-., of (C..') CF--. ,2 ,1- for t.o

a sealed tube 0ave the dir.cr i 33' yield:


days. at -O -


^??o
:::eSiC::.?iC C


[XS .:::]



i-..-. ... ta a.-d n.m.r. spectra, and M:rD daaL are con-

sis..t i.ith this struuctc. Unreacted s~a-rting material was recovered,

which indicates the stability of both thU olo-in and the product at this

tenmer-a-r,. So.o discoloration was apparent.


of "rc) .
oi `


JL- ._ i


..

. L..a


.2







































































their ;C.Uvi-L y Lo rard a


cryllthic, onr

s-s...l .on .=c in


oi Vn


























.thermal . 1



















o 1-- -r -
K 1- .-- ......





b *il2, of fr-.ing a 13 r .ch ,, c n th-



in t.:e backbone of t:. cin.

o furtr r tic.: a t. .e ...

cc::Cuas. Ti.r. is ..o s to if r o..ne r

tions of the tr.,xt ue rs .-f t -~' as .cries.





Galas afd -fn- (1) fou..L th~i uitCko roi.2 _,n- .-.- triphc:-. -

5aana added L'to olipic kotont s to foran he corr-cpcrdi:,n kSkoxid-

when irr~ at-d with ult:- violet light. H.vang tvo flucrin.ted ac-

tones (C/F L and CFCiC!CI) available, it was decid-d to attc::.t
''3" 3


E-6..rental anc:,.'



























'7





































to -- -


7--e
























1Uc~rl


wo.-,d ..ci o






would 1, acx 0.


cl

_11 + -

1 I

L Lu









5-ctra shows n.o azorption due to an i C r:p, a.; idata a;rco iril


-0 bonr.d.


-e

-
i~,


"


,i




r.. i-


cen.. tL : i
were cl..'ned i,


nl .._.. --



















































































Ci










V"







































































i-4


























'-.4































-7-



























































-r I


C-


i-




0: 0







N:


I 0


Th






















































i



o




;"




ii


i!
















00 0' a C







O0

ON
CD O O

























0 N



0-0

0 = =H cH









NN N
0-CO


0 (
cO N CI M N0
o co N N





























a 2-1 0 x






0
O
0 uu
ii 3;C M C
0 M C
Ci -~







































































ii
















































U )- 51
ii










U

















i














III. EXPERIMENTAL


General

All temperatures reported are uncorrected and are given in degrees

Centigrade. Molar refraction (MrD) data were calculated from bond re-

fraction values reported by Warrick (38). It was found that the experi-

mental MrD values were always somewhat higher than the calculated

values when a fluorine atom was on an aromatic ring or on an olefin

conjugated with an aromatic ring. The experimental value was also high

in the butadiene, Me SiCF=CFCH=CH2. No general correction could be

calculated, so these values are not reported.

Refractive indices were determined with an Abbe refractometer at

20 degrees Centigrade, densities were determined at 20 degrees Centi-

grade using either a 5 milliliter or 1 milliliter pycnometer.

Infrared spectra were obtained using a Perkin-Elmer Infracord.

Only absorption peaks indicative of the structure are reported.

Analyses were performed by Galbraith Laboratories, Knoxville,

Tennessee.


Preparation of Trifluorovinylsilanes

The trifluorovinylsilanes, with the exception of dimethyltrifluoro-

vinylsilane, were prepared by adding the appropriate chlorosilane to a

solution of trifluorovinyllithium at -78. The trifluorovinyllithium

was generally prepared as follows:























































































































































j












































i







i-I-















.:.-.~.. .. I .. u.















i



































-t












T -


it -



_
















I-,i -, -~








,'5 -,- -



-u.~-.- -~ U,


- - 5 2 -










































































































































1-- .







Preparation of 2,3,3-Trifluoroallyltrimethylsilane [VIII1


Bromomethyltrimethylsilane (8.4 g., 0.05 mole) was reacted with an

excess of dispersed lithium in 50 ml. ether. The lithium reagent formed

was filtered to remove the remaining lithium and added to a 100 ml.

thick-walled glass tube. Tetrafluoroethylene (6 g., 0.06 mole) was

condensed into the tube at liquid nitrogen temperature. The tube was

evacuated and sealed and left in an ice bath overnight, and at room

temperature for 12 hours. The tube was opened and all volatile mate-

rials were transferred into a cold trap via an aspirator to separate

them from the solid residue. Distillation of the ether solution gave

3.6 g. (425) VIII, b.p. 890, n0 1.3745, d20 0.949, MrD calcd. 39.2,

found 40.4.

Anal. Calcd. for C 61F3Si: C, 42.84; H, 6.59; F, 33.89. Found:

C, 43.16; H, 6.61; F, 33.49.


Preparation of (3,4,4-Trifluoro-3-butenyl)silanes

(3,4,4-Trifluoro-3-butenyl)trimethylsilane [IXI

A 500 ml. 3-necked flask was fitted with a stirrer, condenser, and

dropping funnel. A stirred mixture of isopropyl alcohol (200 ml.) and

zinc dust (130 g., 2 moles) was heated to reflux. (1,4-Dibromo-3-

chloro-3,4,4-trifluorobutyl)trimethylsilane (188 g., 0.50 mole) was

added at a rate to maintain reflux without added heat. After the last

of the silane was added the mixture was refluxed for an additional hour.

.The heat was then removed and 100 ml. of 38% HC1 was slowly added. Upon

completion of the reaction, the mixture was filtered to remove the zinc.

The two liquid phases were added to a 1 1. separatory funnel and water

and ether added. The -it.r layer wa discarded the ether layer -wN







washed twice more with water and dried over CaCl2. Distillation yielded
20
68.5 g. (75%) [IX], b.p. 112-114, nD 1.3808. Tomasino reported b.p.
114, nD3 1.3790.

(3,4,4-Trifluoro-3-chloro-4-bromobutyl)dimethylchlorosilane [X]

A solution of dimethylchlorosilane (25 g., 0.37 mole), 3,4,4-tri-

fluoro-3-chloro-4-bromo-l-butene (57 g., 0.26 mole) and 1/2 ml. 1 M

solution of H2PtC16 in isopropyl alcohol was refluxed in a 200 _l. flask

for 24 hours. Distillation of the products gave 11 g. dimethyldichloro-
20 20
silane and 35.8 g. X (44%), b.p. 2050, nD 1.4400, d 1.513, MrD calcd.

56.4, found, 56.0.

Anal. Calcd. for C6H10BrC12F3Si: C, 22.65; H; 3.16; F, 17.91.

Found: C, 22.69; H, 3.57; F, 18.97.

(3,4,4-Trifluoro-3-chloro-4-bromobutyl)methyldichlorosilane [XI]

A solution of methyldichlorosilane (23 g., 0.020 mole), 3,4,4-tri-

fluoro-3-chloro-4-bromo-l-butene (40 g., 0.18 mole), and 1/2 ml. 1 M

H2PtCl6 solution in isopropyl alcohol was refluxed 24 hours. Distilla-
20 d20
tion gave 45 g. (71%) XI, b.p. 2200, n 1.4451, d20 1.6076, MrD calcd.

56.1, found 56.0.

Anal. Calcd. for C5H7BrCl F 3Si: C, 17.74; H, 2.08; F, 16.84.

Found: C, 17.92; H, 2.23; F, 17.07.

Attempted Dehalogenation of X

X (7 g., 0.03 mole) was slowly added to a refluxing mixture of

zinc (5 g.) and THF. The reaction appeared to proceed smoothly with

evolution of heat. The mixture was then distilled without further

treatment, due to the reactivity of the silicon chloride. As the THI

was removed and the flask temperature increased, the residue quickly







turned black and a two-phase mixture was distilled. The products were

not separated and identified, but no olefinic group showed in the i.r.

spectra.

1,3-Bis(3 4, 4-trifluoro-3-chloro-4-bromobutyl)-1,1,3,3-tetramethyldi-
siloxane LXIII

(3,3,4-Trifluoro-3-chloro-4-bromobutyl)dimethylchlorosilane (36 g.,

0.11 mole) was heated with stirring overnight in 25 ml. water. The

organic layer was separated and dried over CaC12. Distillation yielded

23 g. (82%) XII, b.p. 1250/mm, n20 1.4345, d20 1.4712, MrD calcd. 101.9,

found 102.7.

Anal. Calcd. for C12H20Br2C12F60Si2: C, 24.78; H, 3.47; F, 19.62.

-Found: C, 24.93; H, 3.52; F, 19.74.

1,3-Bis(3,4,4-trifluoro-3-trifluoro-3-butenyl)-1,1,3,3-tetramethyldi-
siloxane XIII]

XII (22 g., 0.045 mole) slowly added to a refluxing mixture of

10 g. zinc in isopropyl alcohol. Water was added and the product

extracted with ether. The ether layer was washed twice and dried over
20
CaC12. Distillation yielded 6.8 g. (42%) XIII, b.p. 950/6nm, n0 1.3932.
20
Tomasino (34) reported b.p. 950/6mm, n0 1.3975.


Preparation of (4,5,5-Trifluoro-4-pentenyl)silanes

(4,5,5-Trifluoro-4-pentenyl)dimethylchlorosilane [XIV]

1,1,2-Trifluoro-l,4-pentadiene (50 g., 0.41 mole), prepared by the

method of Tarrant and Gilman (26), was sealed in a'thick-walled glass

tube with dimethylchlorosilane (40 g., 0.42 mole) and 1/2 ml. 1 M

H2PtC16 solution in isopropyl alcohol. The tube was heated overnight

at 750. Distillation of products yielded 75 g. (85%) XIV, b.p. 1630,

n20 1.4046, d20 1.116, MrD calcd. 48.0, found 47.6.


































































































;il










.i:





L,


































_ir_.







hexamethyldisiloxane (60%), b.p. 97-990, n0 1.3777 (Lit. b.p. 100.4,
20
nD 1.3772).

AttemDted Dimerization of I

I (7.0 g., 0.45 mole) was sealed in a glass tube and heated at 2000

for two days. Distillation-gave some starting material and 0.25 g.

(3.8%) of material boiling 960/24mm. Considerable decomposition was

evident.

Anal. Calcd. for C10H18F4Si2: C, 38.94; H, 5.88; F, 36.96.

Found: C, 39.19; H, 6.07; F, 37.22.

i.r. Data, while not conclusive, are in agreement with that expected

of the dimer.

Attempted Reaction of 1,3-Butadiene with I

I (6.7 g., 0.044 mole) and butadiene (4.75 g., 0.090 mole) was

sealed under N2 in a glass tube and heated at 2000 for 24 hours. A

black solid was obtained, but no volatile products were present.

Reaction of Lithium Reagents with I

In general, the lithium reagent was prepared either directly or by

the halogen exchange reaction with butyllithium. The lithium reagent

was then slowly added to an ether solution of I in a 3-necked flask

equipped with a stirrer and reflux condenser. The reaction mixture

was then hydrolyzed, the ether layer separated and dried, and the pro-

duct obtained by distillation.

Reaction of methyllithium with I. Methyllithium (0.05 mole) was

added to I (7.7 g., 0.05 mole) in ether. A gas was evolved. A sample

was collected, and the i.r. spectra indicated that it was probably

CH3CF=CHF. The reaction mixture was worked up as described and







s il. .4 g. (19) l-trimethylsiyl-l,2Z-ifjluro---,

.XVII, b.p. o, I.3921, d20 0.917, Hri cald. 39., ud

Anl. Calcd. for C S2Si: C, 47.97; -, 9.Co; -, 2 i

C, 47.7 ; 9.07; 25.1 .

:ct~ion of bt v! "u with I. uty thi .1 o)

lo-,ly added to I (15.4 g., 0.1 mole) in ether. ':or- of : r- .

mixture gave 13.4 g. (70 ) l-trimethylsilyl-l,2- uorc--
20
:XVniiI, b.p. 76/40:L, nn0
EX:VI1, b.p. 760/4C0mm, fD 1.4112, c20 0.887, MrD ca-cd. 5-.

53.9.

An-i. Calcd. for C 9'F Si: C, 56.21; H, 9.44; F, 19.76.

C, 56.39; K, 9.48; 7, 19.53.

Reaction of rhcn:.llithium with I. Ph..yc.ihiu ; .;o :

slowly added to I (15.4 g., 0.10 mole) in et.sr. .ork-up of :he rC -

ticn mixture gave 15.1 g. (72;,) -3--rimr thy1silyl-a, -di luorcs irs .
20 90
:XI], b.p. 7C-7 0/2, r 1.5062, d 1.0304.

al. Calcd. for C I H4F2Si: C, 62.22; H, 6.6t; 17.9. You

C, 62.51; H, 6.53; H, 17.75.

ReacLion of r,-trifluoromthvqlphrYllithiu> .i'" _. m-ro-.;.c-

trifluoride (22.5 g., 0.10 mole) was reacted with buty'lihi 'iu (0.1C

mole). The reagent was then slowly added to I (15.4 0., 0.10 Y.ole)

in ether. Work-up of the reaction mixture gave 14.0 g. (C50) of

m-trifluoromethyl-3-trimethylsilyl-a, B-difluorostyrcne [ 7X, b.p.
20 20
101-1040/6m,- nD 1.4640, d 1.181.

Anal. Calld. for C12I13 F Si: C, 51.42; H, 4.68; F, 33.89. Fou

C, 52.31; H, 4.57; F, 33.22.

Reaction of -raohthyllithiun with I. l-Brcmonrap.hth l.ce 2-.7 2.,

0.10 mole) was reacted with butyllithium (0.10 mole). (It was late








found that less than 0.10 mole of BuLi was used, but thu corruc _..o

is unknown. ) The l-naphthyllithium was slowly added to I (19.4 .,

0.10 mole) in ether. ':ork-up of the mixture g:vco 10 ( ,) of 1-

(I,2-diflucro-2--ri.. thylsilylvinyl)".aphthalor.c+ L:..... b. j. 1cu/"o
20 10
nD 1.5538, d 1.110.

nl. Cald. for CHF2Si: C, 68.69; H, 6.15. .....: .

,6.35.

Reaction "-' 2-7-c --Lli-h.. vth 2- .....i

0.09 .cle) was --acted with butyllithi-.r (30.9 mole). 'h 2-..i- -

lithium was slowly ad>ed to I (14 g., 0.09 .ole) ir. u...r. i.r.-. e

10 g. (50,)) 2-(1,2-difluoro-2-trinmthylsilylvinyl)-th-L.c::..e [a:rI!,
2O2
b.p. 6ou/2m, n20 1.5>01, d2 1.135.

..nl. Calcd. for C9 F1F2SSi: C, 49.50; 3, 5.54; -'.3o. >--

C, 49.62; H, 5.52; F, 17.17.

R -- ior of i -hT iur .'ith T. Tetraallyltin (7.1 .. -.0

mole) was slowly added to an ether solution corn-ain.rng phr li-_.

(0.10 mole). A precipitate of tetraphcnyltin was for.-... 1(15.

0.10 mole) was added slowly to this mixture. The mixtu .:_. -i'_.

for two hours and filtered. Distillation of the filtrate yicc-ad 3.

g. (20o) of l-trirethylsilyl-l,2-difluoro--l,4-pentadiene [':III], b.p.
20 20
50/30=_, n' 1.4130, d0 0.924, MrD calcd. 47.9, found -8.0.

An?- Called. for CgH1F2Si: C, 54.32; H, 7.97; F, 21.58. Four.:

C, 54.33; H, 7.81; F, 21.76.

Reaction of vir.llithium with I. Tetravinyltin (5.7 g., 0.025

mole) was slowly added to an ether solution containing phenyllitium.

(0.10 mole). precipitate of tetraphenyltin was for.-.d. I (15.4 g.,

0.10 mcle) wa. slowly added to this mixture. The mixture was stirred









for tw-:;hoors aa, steam d-_is-l,L, to *:...ove nc 'rccl '2. fX

o.y nyl 2 n. .o va- ws scparatUd, dr ,,d, L. i
r. ocu,, t T,; lhon h.1 Da-Ln `, 2.:


2

/ '-,03, a i.%A.
0.acd. 2r C 2 xL: C,c-.72', C -

C, 52.14; H, 7.30; F, 1 3 6






_n .eneral, t- c C=,ratu focrr.2d in tb reaction a --

rc,,ii!ants on 1 w cas relu dcfr abocat t~zo h3>.x in. a

Exce_-s ,_-r le a a'c cand the lcroa a-c 7ac

a-i was h r the prod-ct onb a






vas rcactcd as abcve i-tt-. 20 ml. 0 anc- c solua........
20 20
5 g. (62) XXV, b.p. 730 1n3680, d 0.885, -



An;'. Calcd. for 0%F2: C, 60.00; H, 8.-,; F, 1.

c, 59.E52; H, 8.21; F, 31.30.

*~ lo ci~-


5-Tri_.othylsily1--_, -dSifluorost yrcne EXIX] 11.

was reacted as above wiith 20 rd. KOH-othancl solution. .Xrr,:-a
5.5 g. (61K; XXJiI, bsp 84160, 0~ '20 _
n. 1.5056, d 1.155. ( (12)
b.p. 82O-9Q0/, n 20
-.D -''- '-Vir ica.' _V,
-iu VY.- D












7.3


-. ..... -. o -: C, 5- 4 ; l -, 2. ; ,.; u.'.. :


C, 51-79; H, 2.50; F, 4j.2E.

Thi-s compound 'orxd a clear .:-a_ a 2:... ..

heated at 900 cvarnight with Ln-.-n o -ro:ide.

Pr
1-(1,2-Difluoro-2-trimethylsilylvinyl )ra:. l.- -. .

0.039 mole) was reacted as above -with 20 rl. KO.-at: lu

Work-up yielded 5.5 g. (83.) .VTTI, L.. 700/lrm, n- -.7;, 2

1.224.

'--1. Calcd. for C,2, F2: C, 75.77; H, 4.24; F, 15.97. Fou:._:

C, 75.23; H, 4.10; F, 19.14.

Aate-r.te.j PraraatLin of 2-(C12-,if:. i-l)thir. i

2-(1,2-Diflucro-2-tri-ethylsill vinyl )-thioenr.e [-CxV] r.

0.04 mole) was reacted as above with K0H-a-thar.ol solution. ir--_-

yielded 5.5 g. product, b.p. 650/4C0=, n0 1.5272. The compound quic.:-

discolored, and the next day was a black tar.

Aral. Calcd. for C6P FSi: C, 49.30; H, 2.76; F, 25.98. Found:

C, 45.41; H, 2.69; F, 27.43.

Att nr-ted Pre-.rattion of ~ 2--Difluoro-I ,4--"ent diere

l-Tri:methylsilyl-1,2-difluoro-1,4-pentadiene [XXIII] (3 g., 0.017

mole) w:as reacted as above with KOH-ethenol solution. .ork-up yielded

a small amount of low: boiling product, but not pure enough for analysis.















or1





al-.d V. a; C;-l=..-



Tho th~ird c~i-ocrccncnt at3ilr.) rs n-ct icc~;_-,
---sn Of2







:: c25 g. 0 14 rcicl) w 0 c i a c
_-n--n;~ a plncnc- nd ocinon. T t uj, _- i as alC


hour,. Distillation of the a. n 7 Y
20 22
3 70o/0-u, 1. _-, c).

___ CaeCd. La: C1 I C ii: C, 46.12; H, 7.19; 3, 1-.L .6

Hr.;; i, 7.19; F, 31-52.




I( (9.1 9. 0.05 monle) was slo-vly a 0i to an olut-lo. co..

nho2nollithium (0D.0 mole) in ethcr. niixtura ; was ::

hours, hydrllyzed and the organic laycr dried. Distillaticn Zv S.c .
(4) (43-p.en~y1-3 ,..-difluoro-4-butonylil )tr1.nl yls;an [CX,
-;--th~s-1~ [. 19X], b.p.

9o0/2=-n, n30 1.4990, d2o 1.00?.

r-'. C& cC. Lor C1 .0F2Si: C, 64.93; E, 7.36; `, 15.-.

0, 65.01; H, 7.67; F, 15.82.













d: 5; 5- 3; .C









He 1. s f_ ro cer-.on.e ( 0.06 j., 0.i6 :..G-t,) c_., :_-,.:..7_ ".



-iatd ian zznli.ht 'or Lbouo .L.O ; -.. Distill4 -^,m.
20 20
XXXII, b.p. 9.o, 1.i3;3, a 1. 3,, : calc. 3. -

CaLcd. 2or C C1203: C, 17.09; 1.3;

Found: C, 17.15; :, 1.45; F, 4.31.





,,3,3-?etra'lO-l, 3-c' hlcr-ace.cC (80 ., C.- ....
. othyldichlor3oilne (46 g., 0.40 :i) :ere sealea In -..

glass tube and irradiated for about two weeks. Distill .
8 (20 0
89 g. (79:T) XXXIII, b.p. 153', n3 1.3930, d2 1.524, r c_ .-

found 49.3.

nal. Cal;d. for C CL i: C, 15.25; 1.29; 2-. .

:ound: C, 15.85; H, 1.33; F, 24.33.

Fro-aration of (1,1. ,1 0'.-.-:: orisoprooyv). ~1 ..

XXXII (1? g., 0.06 mole) was reacted with CHQSDr (0.12 mole) in

ether. The mixture was hydrolyzed and the organic laysr dried. Distil-
20 20
laion gave 5 g. (35) XXX:V, .. 1.3196, d 1.77, 'rD

calcd. 40.5, found 40.3.







Reaction of IX with 1,3-Butadiene

IX (8.2 g., 0.045 mole) and 1,3-butadiene (4.8 g., 0.09 mole) were

sealed in a thick-walled glass tube and heated at 2000 for 24 hours.

Distillation of the liquid residue gave 3.6 g. (33.6%) of a compound

tentatively identified as either


(CH ) SiCHCH2CF-CF (CH ) SiCH2CH CF-CF
3 3 2 2or 33 2 21 2
CH2=CH -CH2 CH2-CHCH=CH2


Infrared analysis showed a vinyl group to be present.

Anal. Calcd. for C1119F3Si: C, 55.88; H, 8.11. Found: C, 56.87;

H, 8.11.

Reaction of IX with NOC1

A 3-necked, 300 ml. round-bottomed flask was fitted with a stirrer,

reflux condenser, and inlet tube. DMF (160 ml.), A1C1 (11 g., 0.082

mole), and IX (11 g., 0.06 mole) was added to the flask. NOC1 was

bubbled in until no further reaction was obvious. (The reaction was

quite exothermic.) The solution was extracted with pentane, and the

pentane layer, containing the blue product, was passed through an

alumina (acid) column. The blue material was collected and the pentane

evaporated under vacuum. A deep blue product, tentatively identified

as (CH ) SiCH2CH9CFCFC1 was obtained. n.m.r. Spectrum indicated the
3 -' -NO
structure was possible, although not definite.

Anal. Calcd. for C 7H3C1F3NO: C, 33.89; H, 5.29. Found: C,

33.76; F, 5.43.


Thermal Dimerization of
(4,5,5-Trifluoro-4-pentenyl)dimethylchlorosilane [XIV]




















-- -
20' r
tillanion yi.idsd 15 Z. )., b. 1 .


AnL' .. r C -6 6 M2F3: C, 26.3; 3--
....... '-" f.- .6-.-.--.

Found: C, 2o.39; H, 3.81; F, 27.93.


Pel-".:rization of - ',:"iII


STunty gram scnpl0o of X:XII a.d 1.i e.

separate bal:crs containinZ 50 r:. -azer. Th .nn.cr, -

rapidly. Each for:.. an claoctomric -;. in a.ouL 0 LO

The gums were silent but :.ot strong. 1. .s c.. .. c-

glassd to dry- cvur.izht. --nay ha:den.d ovright o .. :

polymr.s. Eleamntal analysis of th-. pol..yir from.::: l ho' onl-

4.l', fl-uorine : analysis of th' polyr.-.n r f-'o:. sho:-d n-y

chlorine. (Cald. : 50.4 anrd 27.4; respectively, if no hy_.clysis of

the iscpropcxy groups took place.)





















or so:,:a fun:lo_-1 ,rou".0

:e first of e. ..
OSin G 2 ,

tir. of C Ii i- i J



and where 3 is C L..

The coL pound C C w-

., JSiC Li wi-ih C- SCF27?

ah ccpourc s.e. o -. -

rardi4ion. olf C 22tr l- -2l

z,: reduction of te 'd itionr -ducs. C _r L r_

tfrom o the ad_diion irc of C 2' -, od -: c "









iitaium cocpounds :


RLi + Ye SiCF2 -- e SiC=Ft
o3 o c2 "o4








penyl, l-aChthyl, 2-thi alyl, d vinyl. The sus




















in., as did : C:C C::/ r=F.

T-o :cto,.-ecs, CFPGC, a.d CFCJC.'.l, :o G.-- .

.athykljliroil;.e to give th- i ;_ -


C C C
I I |
Cl CF3 C ".I-


Both of these polyrmarized r_-ctic n

was lost, giving hard, brittle pl... i' .

toners. The trieathyl derivatives -: Lso pp-rc --.. ...- ..

alkoxides.



















Ot d in C. Eabo:n i



2. T, D. Coylc, S. L. Stag a c, Soon_ .

6 A6, 30 3.

3. ... J. C )

-. . ~J, A.S. Th.sis, C.iv;

5. R, 2. ...oldino, 2atu-u 1- . 'l" 9 )



g, 6336 (1959).

7 1. L Krunyants, R. :' St""^lin D. I- : -.

I v. Aki. }auk S.S.S... Ojd. i .. 1 ko 1 -5 (1,

8. R. P. L t..... S. Thesis Ui:,:-sit of F oride, 19r

9. -. -. :-FBEe, C. U. Ro bc', T. F. Judd, and T. S. C:..., J.

Cher. Soc. 2, 1292 (1955).

_0. :W,. J. .i`ddl on, E. C. *Hward, _Lnd. H. Shar. y ~ .

Soc. -, 259 (1961).

H1. H. t an-d P. jTarr 2, J. Cr Co.

-12, !. %M. ad, T. V. Talalaeva, ko K. .V. .

Xochoshkov, Izvest. Ak'ad. Mauk S.S.S. Otd. K-i::. nu. 272

13. J. D. Park, R. J. Seffl, c-d J. R. Lachsr, J. Am. C-. So.

59 (1956).

14. W. I. Patnode and D. F. \Wlcc;:, J. An. Chn. Soc. _, j

53








15. F. J. Pisacane, Ph.D. Dissertation, University of Florida, 1963.

16. W. Postelnek, Ind. Eng. Chem. 50, 1602 (1958).

17. D. Seyferth, K. A. Brandle, and G. Raab, Angew. Chem. 72, 77 (1960).

18. D. Seyferth and T. Wada, J. Inorg. Chem. 1, 78 (1962).

19. D. Seyferth, T. Wada, and G. E. Maciel, J. Inorg. Chem. 1, 232

(1962).

20. D. Seyferth, T. Wada, and G. Raab, Tetrahedron Letters 22, 20

(1960).

21. D. Seyferth, D. E. Welch, and G. Rabb, J. Am. Chem. Soc. 84, 4266

(1962).

22. L. H. Sommer, D. L. Bailey, W. A. Strong, and F. C. Whitmore, J.

Am. Chem. Soc. 70, 2869 (1948).

23. J. L. Speier, J. A. Webster, and G. H. Barnes, J. Am. Chem. Soc.

29, 974 (1957).
24. R. N. Sterlin, I. L. Knunyants, L. N. Pinkina, and R. D. Yatsenko,

Izv. Akad. Nauk S.S.S.R., Otd. Khim. Nauk. 1492 (1959).

25. P. Tarrant, Wright Air Development Center Technical Report 55-220,

August, 1955, p. 25.

26. P. Tarrant, J. Attaway, and A. M. Lovelace, J. Am. Chem. Soc., 76,

2343 (1954).

27. P. Tarrant, G. W. Dyckes, R. Dunmire, and G. B. Butler, J. Am.

Chem. Soc. 79, 6536 (1957).

28. P. Tarrant and E. G. Gilman, J. Am. Chem. Soc. 76, 5423 (1954).

29. P. Tarrant and J. Heyes, J. Org. Chem. (In Press).

30. P. Tarrant, P. Johncock, and J. Savory, J. Org. Chem. 28, 839

(1963).

31. P. Tarrant and D. E. O'Connor, J. Org. Chem. 29, 2012 (1964).
















i, S.



-i ~ D.A




















at4-end-d public schools in Eal4in C-.. -..o ..

Jaldwin County Hig. -chool in .:-ay, 9-c.

Ho cnltred the U. S. .'.-y the .....- c" '.is ;'.-. ... .-i -

cn active d --c a period of 10 year, 11 ror'. .. 1

in the service f.3 attw-nrd Del .ar Juni.-- C l _. C- -

Texas, for a period of throe ya-rs. .Upr. in cir. :

Southern .jaiona-y Coll., Coll C, t'.-.....es.t, .... .

'.ith a 3.3. in Ch:=-istry in Jun,, 1961.

He entered th.. Unicrosily of 7loridz a. a -

eptc=.ber, 1961. He lat-r rcei'mi a fcllo:s.-.io .. .

Army Natick Laboratories, Natik, a sahutts.

The author is married to the former ..iss Lyda Lit i- -_

r.nette, Alabama, and has three children. sH is a :;r

American Chemical Society.




















c, and; zc Sciences 40. t r-S

r~ ~ fulfllmknt of thV. raqu-lrrc.nii- ntz -d-r f

Thlossy.


]Docc.bor 19, 1964






'4. -






2-oervioory Cor-iitt~e:








___...7t






































2432 4 'S




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