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Preparation and reactions of some fluorine containing silanes

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Title:
Preparation and reactions of some fluorine containing silanes
Creator:
Oliver, Ward Hopkins, 1930-
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Gainesville
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[s.n.]
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Copyright Date:
1964
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English
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v, 61 l. : illus. ; 28 cm.

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Subjects / Keywords:
Alkenes ( jstor )
Atoms ( jstor )
Carbon ( jstor )
Ethers ( jstor )
Fluorine ( jstor )
Lithium ( jstor )
Reagents ( jstor )
Research facilities ( jstor )
Silanes ( jstor )
Silicon ( jstor )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Organofluorine compounds ( lcsh )
Silane compounds ( lcsh )
Silicon compounds ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

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Thesis:
Thesis - University of Florida.
Bibliography:
Bibliography: l. 58-60.
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Also available on World Wide Web
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Manuscript copy.
General Note:
Vita.

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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




Full Text

PAGE 1

PREPARATION AND REACTIONS OF SOME FLUORINE CONTAINING SILANES By WARD HOPKINS OLIVER A DISSERTATION PRESENTED TO THE GRADUATE COUNQL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA December, 1964

PAGE 2

ACKNOWLEDGMENTS The author wishes to express his appreciation to those whose assistance, advice and encouragement have greatly contributed to the success of this research: To Dr. Paul Tarrant, director of this research and Chairman of the Supervisory Committee, whose creative idesis, assistance, and guidance were essential factors in the undertsiking ar^ completion of this work ; to the members of the Supervisory Conmittee for donating their time, advice, and assistance; to Dr. V/allace Brey, for the interpretation of nuclear magnetic resonance spectra; and to the Anny Natick Laboratories, for financial support of this research. Special thanks are due to the author's wife, for her encouragement, understanding, and help in the preparation of this dissertation. XI

PAGE 3

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 Me SiCH2CP=CF2 1^ Preparation of Compounds of the Type RMe2SiCH2CH2CP=CF2 l6 Preparation of Compounds of the Type RMe2SiCH2CH2CH2CF=CF2 19 Reactions of Me SiCF=CF2 22 Reaction of ClMe2SiCF=CF2 with Pentafluorophenylmagnesium Bromide 26 Reactions of Me^SiCH2CH2CP=CF2 2? Thermal Dimerization of ClMe2SiCH2CH2CH2CF^F2 29 Preparation of Fluoroisopropoxysilanes 29 EXPERIMENTAL 39 General 39 Preparation of Trifluorovinylsilanes 39 Preparation of 2,3,3— Trifluoroallyltriraethylsilane kj Preparation of (3,^,V-Trifluoro— 3— butenyl)silanes ^3 Preparation of (4,5,5~Trifluoro— ^pentenyl)silanes 45 Reactions of Trifluorovinyltriraethylsilane 46 Preparation of l,2HDifluoroaiefins from the Products of the Organolithium Reactions 50 ill

PAGE 4

Reactions of (3,4,4-Trifluoro-3-butenyl)trimethylsilane 52 Thermal Dimerization of (^,5,5-Trifluoro-Vpentenyl)dimethyl— chlorosilane 53 Preparation of Halogenated Isopropoxysilanes 5^ SUMMARY 56 BIBLIOGRAPHY 58 BIOGRAPHICAL NOTE 61

PAGE 5

LIST OF TABLES Table Page 1. Olefins Prepared from Me^SiCJ^F2 via Lithium Reagents 25 2. Physical Properties of Compounds Prepared 34

PAGE 6

I. INTRODUCTION The rapid advancement of technology during and since World War II has demanded the development of many materials that were not available 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 temperatures. 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 V/ar 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 Quaterraaster General established at the University of Florida and elsewhere 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 stability and resistance to chemical attack generated great interest. Subsequent work has proven quite fruitful, and the work in these laboratories has been centered predominately around synthesis of fluorinecontaining monomers. Early interest centered around olefins and 1

PAGE 7

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 (3^) prepared new iluorotilefins by the reaction of Grignard reagents with simple fluorodlefins. Polymers containing a large percentage of fluorine tend to lack flexibility. Since heteroatonis in the backbone or side chain of polymers can add flexibility, methods of preparing the appropriate monomers were studied. O'Connor (3I) and Pisacane (15) prepared fluorine— containing nitroso compounds; Stump (32) prepared fluorine— containing unsaturated ethers; and Tomasino (36) prepared several silanes and siloxanes containing fluoroSlefin groups. Polydimethylsilicone rubber is knovm for its exceptional thermal stability and resistance to ozone. It has excellent electrical properties and very low water absorption. However, it is degraded by strong acids and bases, and is particularly prone to swelling in hydrocarbon 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 3 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 research to develop fluoro— silicone elastomers. Under this program

PAGE 8

McBee (9) prepared the first difunctional fluorine-containing silane, CH Si(OCH J^CH^CH^CF by the reaction of CF CH^CH^HgBr with CH Si(OCH-) . 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 v;as achieved using CH Cl^SiCH CH^CF , a compound reported by Tarrant, et al. (27). This rubber, called Silastic LS-53, retained all of the exceptional high and low temperature properties of silicone rubber with" the added feature of excellent fuel and oil resistance (I6). 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 compounds 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. ^V' ^ 2^ 30oS:oOo ^ (C^3^x^^^^(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

PAGE 9

Grignard and organolithium reagents react with silicon halides, alkoxides, and hydrides to form compounds with new silicon-carbon bonds. Me^SiCl + C^H^MgBr >Me.SiC.H^ Me-SiOEt + C^H,Li ^ Me^SiC^H+ LiOEt 3 05 3 o 5 (C,H^)-SiH + C^H^Li 5(C.H^),Si + LiH 053 05 55^ The chlorides are more easily replaced than the alkoxides or the hydrides : Cl2Si(0Et)2 + 2MeMgCl ^ Me2Si(0Et)2 + 2MgCl2 ClSi(Me2)H + CF2=CragBr 5^ CF2=CFSi(Me2)H + MgBrCl Because of the availability o^ organosilicon chlorides, and the great variety of organoraetallic 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 y— rays. Chloroplatinic acid appears to be the most effective of these catalysts when u.v. light is not practical. H PtCl^ Cl^SiH + CH^=CHCH„ ^-^ Cl„SiCH-CH,CH3 2 3 oi* u.v. 3223 This reaction is general and is especially valuable in that a carbon-silicon bond can be formed without disturbing the

PAGE 10

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 Compounds Complex organosilicon com.oounds 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) n CH CH2CHO + CH2=CHSiMe^ ^ s^ CK CH2CCK2CH2SiMe^ SiH^ + CH2=CHSiH "•'^' ^ H SiCK2CH2SiH The halides are also useful: CH COOH II Me SiCH2Cl + CH COOK ^ jMe SiCH20CCH^ A \e CHp,— CH^ Me SiCH2Cl '''^ > Me SiCH2MgCl ^-^ Ife^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 g.-oups in hydrocarbon molecules. All of the above methods have been used to prepare fluorine containing silanes. Haszeldine (5) was the first to report the successful

PAGE 11

preparation by the direct method. CF T + Si ^^ ^ ' (CFJ Sil,, N 3 J X CV-x; This method has been used with other perfluoroaikyl 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 + KeSi(OEt) ^ HeSi(02t)2CH,CK2CF The organometallic method has been used very extensively to prepare fluorine— containing silicon monomers. Tarrant and coworkers (2?) were able to prepare a similar monomer to McBee's in a much more convenient reaction: CF CH=CH2 + MeSiHCl^ ^^'^ > Me(Cl2)SiCH2CH2CF 60% The free-radical addition of perhaloalkanes to olefins is an important step in preparing silanes containing fluoroSlefin groups. Tarrant (23) reported the following reactions : ^^2°2 CF2BrCFClBr + CH2=CHSiMe^ ^ CF2BrCFClCH2CHBrSiMe YOU ^ CF2BrCFClCH=CHSiMe. In these laboratories Tomasino studied the free-radical addition of CF BrCFClBr to a series of alkenyl silicon compounds. These compounds were vinyldimethylethoxysilane, vinyldimethylchlorosilane,

PAGE 12

divinyldimethylsilane, allyltrimethylsilane, diallyldircethylsilane, vinylpentamethyldisiloxane, and l,3-divinyl-l,l,3,3-tetraniethyldisiloxane. The addition products obtained were further dehalogenated and/or dehydrohalogenated to form new unsaturated compounds. It was found that the normal addition products vjere obtained when CF2BrCFClBr was reacted with the vinylsilanes. However, in the dehalogenation of these products with zinc and ethanol considerable reduction of the bromine on the carbon a to the silicon took place. For instance, in the dehalogenation of CF^BrCFClCH^CHBrSiMe-, a hjp yield of the expected CF2=CFCH2CHBrSi:-:ewas 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 bromir.c; atom. Reaction of CF2BrCFClCH2CHBrSiMe^ with concentrated sulfuric acid gave [CF2BrCFClCH2CHBrSi!^e2320 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 \^rith 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 3 to the silicon atom are quite unstable to heat and form terminal olefins (22). Diallyldiraethylsilane, however, gave the desired monoaddition product, CF2BrCFClCH2CHBrCH2Si(Me2)CH2CH=CH2. The first trifluorovinylsilane derivative was prepared by Knunyants {2h) , He reacted CF2=CFMgI with SiCl^ 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=CFT^gI was

PAGE 13

reacted with alkyl or phenyl substututed chlorosilanes. Seyferth, however, was able to prepare Et^SiCF=CF„ from the reac— tion of Et SiCl with CF2=CFI-lgBr in THF (l?) and Me SiCr^F^ from the reaction of Me„SiCl with CF =CFLi (21). He also prepared Me SiCF=CF2 from CF2=CFMgBr, but the product boils very close to THF (6?°) and had to be broitiinated before it could be recovered. Knunyants (24) found that all the Si— C bonds in Si(C?=CFp), were broken under the influence of aqueous base, yielding CF„=GFH quantita— 'tively. Seyferth (18) obtained, in reacting Et^SiCF=CF„ with EtOk'a, a 69> yield of (Et Si)20 and only 285^ of the expected Et SiCF^^JFGC^H He further found in reacting phenyllithiura with Et^SiCP^OFthat the third mole of C^H^Li cleaved the Si-C bond: C.H Li Et^SiCF=<:F„ + C.HXi ^ Et^SiCF=CFC,H^ ^-2 j^ 3 2 6 5 3 o 5 C,H Li Et^SiCF=<:(C.Hj„ or Et^SiC(C/H J=CFC.H^ ^-^ ?Et^SiC.H^ 3 o>2 3d5o$ 365 6 5 65 These reactions indicate the instability of the Si-C bond in Si— CF=CFR to basic media. Further, considering the failure to get mixed products in reacting CFp^CFMgl with SiCl, , 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— TT overlap between the unsaturated carbon atom and the silicon atom. The electron withdrawing effect of the fluorine atoms is transmitted to the silicon

PAGE 14

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 : :CF=CF„ >C'dF=CF^ ^, ^.jx -^ — w — , .oJ.CF=CF-, + CI Cl\ ^f ^ {\'F CI No compounds of the type R Si-CH^CP^^:?^ or R SiCH2CH2CH2CF=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) CF=CF^ received primary consideration, where n = 0, 1, 2, or 3 and R represents a reactive group such as ethoxide, chlorine or hydrogen.

PAGE 15

II. DISCUSSION In the course of this research, comoounds of the type K-Ie.^Si(CH^ ) CF=CF^ have been prepared, R may represent a methyl group, chlorine, ethoxide, or the syrtLTietrical disiloxane ; and n may be 0, 1, 2, or 3The compounds will be grouped for study according to the value of n, since each group required a different method of synthesis. The reactions will be considered separately. In addition, a new method of preparing fluorine— containing alk— oxides of silicon will be discussed. Preparation of Compounds of the Type RIfe^SiCF=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 organor.3tallic compounds. However, at the beginning of this research, the only trifluorovinylsilanes reported were tetra-( trifluorovinyl )silane {2^-) , trifluorovinyl triethylsilane (17), and trifluorovinyltriethoxysilane (19). These were prepared via the Grignard reagent. Later, Seyferth (21) reported the preparation of trifluorovinyltriraethylsilane from trifluorovinyllithium. He prepared the lithium reagent by the metal exchange reaction between tri— fluorovinyltin compounds and phenyllithium, a process envolving several steps and giving rise to low over-all yields. 10

PAGE 16

11 ->• SnCCF^F^)^ ^^^ > SnCl^ + kCF^=CYKgBr CF2=CFLi + Sn?h^ Me SiCl Me SiCF^F^ Tarrant, et al. , had meanwhile discovered a facile method of preparing trifluorovinyllithivuii via the halogen exchange reaction between bronotrifluoroethylene and alkyllithium compounds at -?8°, By this method, trifluorovinyltrimethylsilane [I] was prepared during this research in yields of 6^^ without the separation of intemediates. MeLi + CF2=CFBr -78' CF2=CFLi + MeBr Me SiCl Me SiCP=CF2 [I] The physical properties of this conipound were consistent with those reported by Seyferth. It should be noted that the trifluoro vinyl 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 2J\d 5.6 microns. Triphenyltrifluorovinyltin (prepared in this laboratory) absorbs at 5.88 microns, while tris— trifluorovinylboron absorbs at 5.95 microns (2). All of the metal compounds mentioned have empty p— or d— orbitals on the metal atom which are undoubtedly 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 VT'bonding.

PAGE 17

12 It was anticipated that other conpounds of this series could be prepared with R being a functional group, such as chlorine or the ethoxide. As mentioned in the Introduction, Knunyants (24) found that only the tetra— substituted product was obtained when C?2=CK'lgI was reacted with SiClji^. It was hoped that ClMe2SiC?^?„ could be prepared by reacting CF_=CFLi with MepSiCl„ in a 1 :1 ratio. However, only the di— substituted product was obtained: CF2=CFLi + Me^SiCl, ?(C?2=CF)2SiHe2 [VII] Elemental analysis, Mr^ 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 reactive toward these reagents than the alkoxysilanes. Thus, ClSiMe20C2Hc was prepared from Ke2SiCl2 and C2H^0H in triamylamine. This compound then reacted with CF2=CFLi to form C2H^0SiMe2CF=CF2 , and the chlorosilane was then prepared by reaction with PCI . NR ^f CF =CFLi KeoSiClo + Eton ^-^^ EtOSiCl 5^ 2 2 I Me Me PCI Me EtOSiCP=CF^ ^-—^ ClSiCF^F, Me Me [II] [III] The compounds were identified by elemental analysis, Mr^ data, and their infrared spectra.

PAGE 18

13 Compounds such as II and III might 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 CF-^OFSiMepOSil'fepCf^^o could undoubtedly have been prepared readily i'l'om either II or III, but was actually prepared by another method before II and III were synthesized. The compound ClSiMe^OSiMepCl was prepared by the method of Patnode and Vilcox (14). This dichlorodisiloxane was then reacted with CF2=CFLi to prepare IV: Me Me I I LSiOSiC I I Me He ZMe^SiCl^ + H„0 ^ ClSiOSiCl + 2KC1 2 2 ^ 1 I 2CF2=CFLi 'i'' I ^ CF^=CFSiOSiC?=CF„ 2 1 I 2 Me Me [IV] Eloiioi-tal analysis, i.r. spectra, and Mr-, data were consistent with the assigned sti-ucture. Another interesting compound of thj.s series was prepared where R represents hydrogen. The reactivity of the silicon-hydrogen bond was discussed in the Introduction. Trifluorovinyldim.ethiylsilane was prepared by the reaction of dimethylchlorosilane with trifluorovinylmagnesium bromide : Me Me I 1 HSiCl + CF^=CR'Ig3r ^ HSiCf^F^ Me >-e [V]

PAGE 19

14 Elemental analysis and Mr^ data vrere consistent v:ith this structure. In addition to infrared absorption at 5.83 niicrons for the C?2=CF group, a strong absorption at 4. 6y microns was present which indicates the Si— H bond. Two later attempts to prepare this corapound using CF2=CFLi failed. A brown tar was obtained in each reaction. Prepara-tion of Me ^ SiCH ^ CFM:? ^ Tarrant and Warner (34) discovered that Grignard reagents would substitute organic groups for fluorine in fluorodlefins. Dixon (3) discovered that lithium reagents would likevrise substitute, and that they gave somewhat greater yields of the new olefins than the Grignard reagents : PJ-IgX + CF^=CX2 ^ RCF=CX2 + MgFX RLi + CF2=CX2 •>• RCF=CX2 + LiF With tetrafluoroethylens, Grignard reagents give, in general, monosubstituted products. Lithium compounds, aryllithium compounds in particular, tend to give di— substituted products : PhLi + CF2=C?2 ^ PhCP=CF2 + PhCF=CF?h mostly It was hoped that 2,3,3— trifluoroallyltrimethylsilane could be prepared from the Grignard reagent of chloromethyltrimethylsilane : CF=CF Me SiCH2Cl + Mg >Me SiCHMgCl Me SiCH2CP^F2

PAGE 20

15 This reaction was run both by allowing a cold solution of Grignard reagent and CF^=C?2^ to warn to room tercperature 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 vrith bromo— methyl trimethylsilane. A cold solution of the lithium cor.pound and CF^=CFj, v/as allowed to warm to room temperature. An exotherifiic reaction took place and most of the material v:as lost. Recovered material gave a product boiling about 100° wh_Lch shov;ed no infrared absorption that would indicate a fluorodlefin. The tetrafluoroethylene was probably lost when the reaction heated. The reaction was repeated in a sealed tube. The CF2=CF2 '^'^^^ condensed 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 comoound was obtained. Me SiCH^Li + CF^=<:?^ ^ Me^SiCH2CF=<:F2 [VIII] Elemental analysis, infrared spectra, and l-.r^ 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 likely that a lithium reagent of the type Ri'Ie2SiCH2Li could be prepared where R is a functional group of interest in this series. The chemistry of VIII was not investigated at length.

PAGE 21

16 Preparations of Compounds of the Type Rlfe^SiCH^ CH^ Cf^F Tomasino (3o)j in his studies of some fluorine— containing organo— silicon compounds, prepared the first corcpound of this series. He added CFpBrCFClBr to CHp=C;3iMe-, and then dehalogenated 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: CF„BrC?ClBr + CH„=CHSi.Me^ ^ CF„BrCFClCH^CKBrSiMe^ CF2BrCFClCH2CHBrSiMe^"q^^ > ^ CF^^^^FCH^CHBrSiMe^ 43^ + CF2=CFCH2CH2SiMe 21^ Thus it is obvious that the a— bromine 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 : CF^BrCFClCH^CHBrSiMe ^^q^ > products "^^ > CF2=CFCH,CH2SiMe [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.

PAGE 22

17 Another compound desired in this series, the symmetrical disilox— ane, was also prepared by Tonasino. Hovrever, it was also a by-product 'obtained in lo\-i yield: M, '-e Me I I CF^BrCFClBr + (CH2=CHSi)20 ^ (CF2BrCFClCH2CHBrSi)20 16^ Me Me Me Me I I ^^^ •» (CF2=<:FCH2CHBrSi)20 + iC?^<:FC'A^C}i^Sl)^0 Me Me Since the first step in this reaction gave only a 16;^ yield of the desired intennediate, a different approach was sought to prepare the disiloxane. The reaction of silicon hydrides T'ri. th olefins, discussed in the Introduction, generally goes in very good yields : H.PtClg R.SiH + CH„=CKR' ^^— ^ R^SiCH„CH„R» 3 2 or u.v. 3 2 2 CF^BrCFClCHOH^ and ClSi?-ie2H are both coMsercially available. It was found that their reaction product gave a very desirable intermediate : f H,PtCl^ t ClSiH + CHo=CKCFClCF„Br ^—^ ClSiCH„CH»CFClCF_Br I 2 2 I ^
PAGE 23

18 Elemental analysis and Mrr^ data support this structure. This reaction gave the desired prcduct in an acceptable yield. Other products were obtained, but diraethyldichlorosilane 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. Corapound X could then give the desired disiloxane hy two possible pathways : Me I ^ ClSiCH CH2C^^^2 Me ! LSiC I Me ^Zn Me ClSiCH,CK^CFClCF„Br H3O OCSiCH^CH^CI^F^)^ ( SiCH„CH^CFClCF„Br ) „ 8Z70 CXII] Pathway A was attempted, using THF as a solvent. The dehalogenartion appeared to proceed normally. Since the cbJLorosilane was desired at this step, hydrolysis to remove the zinc 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. Pathv;ay B, however, went v;ith no difficulty. The yield in the dehalogenation step can probably be improved considerably, since no attempt was made to find optimum conditions. The properties of XIII agree vrith those reported by Toraasino.

PAGE 24

19 An attempt to prepare ClMepSiCH CH2CP=CF2 directly by adding dime thylchloros 11 ane to 1,1,2— trifluoro—l,3~t)''it'a-diene in a sealed tube with HpPtCl/ at ?0° resulted in an explosion. Irradiation of dimethyl— chlorosilane and 1,1,2— trifluoro— 1,2— butadiene in a sealed tube in sunlight gave a v:hite polyr.er characteristic of the polyner obtained by irradiation of the butadiene alone. Prepare.ion of Compounds of the Type ILMe^ SiCH^CH^Ch\C?=C?^ The preparation of a silane of the type RSiCH2CH2CH2CF=CF2 required Me some special considerations. Tomasino had attempted to prepare an analogous compound by the addition of C?2BrCFClBr to CH2=CHCH2Siyie . He obtained, however, clea\'-age products of his desired intermediate: CF^BrCFClBr + CH2=CHCH2SiMe >[CF^BrCFClCH^CKBrCH^SiMe^] ^ Me SiBr + CF2BrCFClCH2CH=CH2 It could not be determined if the addition product actually formed, or whether the intermediate radical form cleaved: CF2BrCFClCH2CHCH^ :SiMe =CF2BrCFClCH2CH=CH2 + -SiMe^ If the addition product v:ere formed, it would not be expected to be stable at the reaction temperature, because 3-halo silanes cleave at around 80-90<^ to form alkenes and the halo silane (22): Et SiCH2CH2Cl >Et^SiCl + CH2=CH2 Tomasino was successful in obtaining an addition product with diallyldimethylsilane, but HBr was lost during distillation:

PAGE 25

20 CF^BrCFClBr + CH„^=CHCH2SiCH2C}^=CK2 J Sj I Me [CF^BrCFClCH^CHBrCH^SiCH^CK^^^CH^] Me Me I CF2BrCFClCK2CK=CHSiCH2CH^H2 Me It was concluded that this method would be useless in the preparation of the desired series of compounds. A possible method that was considered, but never tried, was the use of the Grignard or lithium reagent of the appropriate silane with tetrafluoroethylene. Me^SiCH^CP'M + CK^=CF^ ^ Me^SiCH„CH„CHCF=CF„ + MF Thiis method involves the use of pressure vessels because of the boiling point of the CF^=CF^. Also, yields are often quite low in such reactions, and the incorporation of a functional group on the silicon atom would be difficult. The method finally chosen to prepare the Ri-le2SiCH2CH2CH2C?=CF2 compounds was the addition of dimethylchlorosilane to CF^=CFCH2Cn=CH2, a compound prepared in fair yields by Tarrant and Oilman (28) : CF2BrCFClBr + CH2=CHCH,^C1 >CF2BrCFClCH^CHBrCH2Cl C7^=CFC:h' CH=CK, ale. ^. 2^^ "--2""^"2 The possibility of addition to either end of the diene is obvious. At the time of this research,, no study of the relative reactivity of

PAGE 26

21 fluoroi!lefins and hydrocsjrbon olefins in such reactions had been made. Concurrently vri.th this research, in these laboratories Muramatsu arjl Tarrant (11) studied the relative reactivity of this pentadiene toward the free-radical addition of CCl Br. They found that after 6 days irradiation, attack on the hydrocarbon vinyl group was predcninant. After 11 days a fixture of the tv;o products was obtained. After 25 days, addition to both double bonds of the fluorodlefin was complete. CCl 3r + CH-:^HCH„CF=CF^ --^~ ^^ CCl,CH_CH3rCH<,C?^F„ 3 c ^. 2 b c.i::ys 3 2 2 2 "•^-;?CCl^CH^CHBrCH^CFErCF^CCl, 25 days ^^.-.^.^2^— -^-g— 2"""3 Thus, it is obvious that a free radical attack would take place preferentially at the hydrocarbon vinyl group. Vlhile the Si— H group can be readily added across an olefin by free radical initiation, addition by means of metal chloride catalysis is generally considered to be an ionic process (23). It was decided to run the reaction using HpPtCl^ as a catalyst: We Me f H PtClg f ClSiH + CH_=CHCH„CF^F, ^-^ ClSiCH„CH^CH.CF=CF„ I 2 2 2 I 2 2 2 2 Me Me 85^ [XIV] Ke LSiC I Me ClSiCF2CFKCH2CH=<;H2 The reaction was carried out in a sealed glass tube due to the lox

PAGE 27

22 boiling point of the diene (38°). The solution ^^/as heated at about 75° overnight and conversion was essentially quantitative. The distilled product showed only one infrared absorption which could be attrit to a carbon-carbon double bond. This vias at 5.52 p., which indicated a trifluorovinyl group. Thus addition ^sas to the hydrocarbon vinyl group to give XIV. Elemental analysis and Mr^^ data also support this structure. The preparation of the trimethyl derivative was accomplished by reacting XIV with the nethyl Grignard reagent. While the fluoroclefin might also be expected to react x-jith the Grignard reagent, the much greater reactivity of the silicon— chlorine bond led to the desired product in good yield: ClSiCH^CH^CH^CF^^G?^ + KsMgBr ^ •.e^S±CE^CE^CE^CF=C?^ 05/0 [XV] Structural proof was by elemental analysis, infrared spectra, and Mr^ data. The disiloxane was readily prepared by reacting XIV with water: Me Me 2ClSiCH„CH.CH„CF=CF„ ^^ >0(SiCH-CH^CH^C?=CF„)_ |/i22 2 i222 d. Z Reactions of Me .. SiCF=CF ^ Seyferth, in his studies of the vinyl derivatives of metals, has investigated the addition reactions of trifluorovinyltriethylsilane (19)

PAGE 28

and the reaction of nucleophilic reagents vath trifluorovinyltriethyl— silane (18). The reactions of trifluorovinyltrimethylsilane would be expected to be similar to those of the triethyl cor.pound, and for this reason the addition reactions vjere not studied. In his studies of nucleophilic reactions the trifluorovinyl group underwent, in general, the normal reactions of fluorodllefins. An exception was the reaction of the silane with sodiuni ethoxide in ethanol, where the n:ajor product was triethylethoxysilane, and in a lesser yield the displacement (or addition-^linination) product, Et_SiC?=C?CEt. This is consistent with the instability of the trifluorovinyl— silicon bond in base. He found, however, that organor.etallie compounds, and r.etal alkoxides in nonprotonic solvents, gave good yields of the displacement products. Thus, reaction with various Grignard and lithium reagents, as v/ell as sodium alkoxides, phenolates, and tnercaptides gave products of the t;>-pe St^SiC?^?R. He also studied the reaction of the silane v.'ith excess phenyllithiuin, and found that the third mole of phenyllithium broke the carbon— silicon bond : Et SiCF=CF2 + PhLi ^ Et SiCF=C??h ^^'^' ^ Et SiCF=CPh2 or Et SiCPh=CFPh PhLi Et„SiPh + LiCPh=CFPh PhC^CPh + Li The instability of (CF2=CF),Si to base, already discussed, and the Instability of Seyferth's compound to a third mole of phenyllithium,

PAGE 29

24 prompted a further study of the nuclcophilic reactions or As anticipated, it was found that lithium reagents would reac ly to form compounds of the type MeSiCP=CFR, if no excess lithiv were used. Of the lithium reagents used, only ferrocenyl— and &-lithium failed to give adducts. In both cases it is very doubtful that the desired lithium compound was actually formed. Adducts were formed where R represents methyl, n— butyl, phenyl, m-trifluoromethylphenyl, 1— napthyl, 2— thiophenyl , allyl, and vinyl. The yields in the cases of the methyl, allyl, and vinyl products were poor. It is obvious that, if the silicon— carbon bond is as subject to basic hydrolysis in compounds of the type SiCI'^FR as in the trifluoro— vinylsilanes, this would represent a general method of pr^o.-.--i.-.r 1,2— difluoro<31efins. Each of the Me^SiCF=CFR adducts i-ias reacted in alcoholic KOH solution. Good yields of the desired olefins, CHP=CFR, was obtained in the cases of the nr-butyl, phenyl, m— trifluoromethylphenyl, and 1— napthyl adducts. In the cases of the methj'-l, allyl, and vinyl adducts, insufficient starting m.aterial (Me„SiCF^FR) was available. In each case a small amount of olefin was obtained, but not enough for positive identification. In the case of the 2— thiophenyl compound, the product obtained decomposed into a black tar in about 48 hours. Vfnile the infrared spectra was consistent for SC, H CF=CKF, the elemental analysis was somewhat off from the calculated values. Since the compound had appeared pure by vapor phase chromatography, the compound had probably decomposed too much by the tim.e the elemental analysis was run. The olefins prepared by this method and the intennediates are listed in Table 1.

PAGE 30

25 TABLE 1 Olefins Prepared from Me_SiCF=CF, via Lithium Reagents Lithium Reacrent Method of PreDar:ition Intermediate Product Final Olefin CHjLl Me SiCF=CFCH n-C^H^Li Me^SiCP=CFC^H^ CHF^FC.H^ C.H.Li & Me^SiCP=<:FC.H^ 3 o 5 Me-SiCF=CFf^ CF. Me SiCF^:F Me SiCF=C? CH2=CHCH2Li Me SiCIM:FCH2CH=CH2 CH^=CHLi Me,,SiC?=CFCK=CH^ ->FuLi + LiEr a. Prepared directly: RBR + 2Li b.. Prepared by halogen— lithium exchange : PcBr + BuLi RLi + BuBr c. Prepared by tin— lithium exchange : R,.Sn + 4PhLi RLi + Ph, Sn ^ d. The desired olefin was not positively identified.

PAGE 31

26 Another common reaction of fluoroSlefins 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 : 2Me^SiCf^F_ ~^^ =Me,SiCF-^F^ 3 2 3 I I 2 Me SiCF-CF^ 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 product and a thick oil were formed. No volatile products were obtained. Reaction of ClMe p SiCF=CFp with Pentafluorophenylmaffliesium Bromide As an example of the use of ClMepSiCF^F[III] as an intermediate in the synthesis of other silanes, III was reacted with pentafluoro— phenylmagnesium bromide : Me + ClSiCF=CF„ sI 2 Me [VI] Having noted the instability of the silicon— carbon bond to base in the fluoroSlefin derivatives previously discussed, it was desired to find if the pentafluorophenyl group would be stable under similar

PAGE 32

27 conditions. The above compound [VIl was reacted in alcoholic KOH. A gas, presumably CHF^F^, was evolved. If the carbon— silicon bend vcre stable to base, one would expect to find l,3-di(pentafluo. .',— l»l»3>3~tetraineth3''ldisiloxane anong the products aftsr adding water. If the bond were not stable to base, pentafluorol , mid be expected. ExaTiination of the products actually forr.ed found none of the disiloxane, but pentafluorobenzene (identified by comparison of infrared spectra and v.p. c. retention tir.e v.-ith those of an authentic sample) was present. CF=CF. r' + CF2=CHF + cyclic siloxanes Reactions of Me SiCH ^CH^CF=CF^ Treatnent of (CH ) SiCH^CH^CFM^F^ [Villi for two days at 200° in a sealed tube gave the diner in 33/^ yield: 203 2Me SiCH2CH2CF=CF2 ^ Me^SiCH„CH,CF-CF, J 2 2| I 2 Me SiCH2CH^CF-<:F2 [XXIX] . i_-.a_y3is, infrared and n.m. r. spectra, and l-ir-r. data are con— z-3\.3nz vdth this structure. Unreacted starting material was recovered, which indicates the stability of both the olefin and the product at this temoerature. Soxe discoloration vras apparent.

PAGE 33

o reactbelieved to be either CH^=CHCH-C.% . ^ -^ xjas obtained. Elemental analysis was correct for either corr.pound and infrared spectra indicated the presence of a vinyl group. The sample was lost, hovrever, before analysis was complete. Another interesting compound was prepared from VIII by the addition of NOCl: Me SiCH^CK^CFM:?^ ^"^^ > Me^SiCH^CH^CFCF^Cl NO Elemental analysis and n.m. r. data indicated that this product was formed. The deep blue color characteristic of aliphatic nitroso cor;rpounds was present. (CH ) SiCH^CH CF=CF2 was found to be quite resistant to nucleop'rJ-lic reagents. Refluxing sodium ethoxide in ethanol failed to attack the olefin in a period of 20 hours. The same reaction wcs run in a sealed tube at 150° for 12 hours xvithout success. Tarrant and Heyes (29) found that BrCH2CH2CF=CF2 wo-uld not react with CH^^CHCH^HgX, whereas perhalo fluoroSlefins gave fair to good yields in all cases. This would indicate that hydrocarbon substituents on fluorocJlefins decrease their activity tovrard nuclecphilic compounds. Phenyllithiu-Ti, on the other hand, reacted vjith VIII to give the substitution product in good yield:

PAGE 34

29 PhLi + CF^=CFCH^C.%SiMe^ ^ PhCF=CFCH,CH_SiMe„ Elemental analysis and infi-ared spectra agree with this structure. Therr^al Dimorization o f ClMe„SiCH„CH„C!LC7<;y, — ii C C iL ^ The only reaction attempted \n.Vn. the pentenyl derivatives was thermal dimerization of XIII : 2ClSiCH„Cr' CH„CF=C?„ ^^ Cl:iCH_CH^CH„CF-<:?, \ C C C C \ C ii £. cisiCh' ch.ch„cf-k:f„ I 2 c iC iL [XXXI] Elemental analysis is consistent with this formula. The conipound, a solid, was obtained in k-2% yield. It is interesting to note the possibility of foi-n^iing a polyrier \\'hich would contain the cyclobutyl group in the backbone of the chain. No further reactions were attenpted with the FJ-!e2SiCr:2CH2CH2CF=CF2 compounds. There is no reason to expect ther:i to differ from the reactions of the next lovrer members of the homologous series. Preparation of Flv.oroisopropoxysilanes Galas and Duff ant (1) found that trichlorosilane and triphenylsilane added to aliphatic ketones to form the corresponding alkoxides when irradiated with ultra violet light. Having tx\'o fluorinated ace— tones (CF^CCF^ and CF„C1CCF^C1) available, it was decided to attempt 3 J) ^ ^

PAGE 35

the addition of raethyldichlor. ossible pathways were invisioncd. First, no reaction might take place, the silane might add as in acetone: CI CF^ MeSiH + C=0 CI CF^ 01 CF^ :> 3 Third, a competing reaction might go faster, as the perhaloacetones are kncivn to be cleaved by ultraviolet light (3?) = u, V. CF CO? — ' ^CF^^G+ OF • — -1^-1-5:2CF • + 0=0 Other products Various products would be expected, as the free radicals so formed would be able to abstract a hydrogen from the silane as well as to cobine to form hexafluoroe thane. Fourth, addition across the carbon— G::y gen bond might go in the opposite direction from the product obtained with acetone. Du Pont chemists, working with perfluorothioke tones, found addition reactions to go differently from the hydrocarbon analogs (10) : CF^ i ^3 _ ^ C=S + Me, NKSO^^ KCSSO„ "^Kfe, I ^3 I 3 ^ V/hile

PAGE 36

C=S + Me. NKSO„ ^>IISCSO_ ^WAe, I ^3 1 3 ^ This can readily be explained by the greater electror.ej:ativity of the fluorine atoiri: Oxygen, however, is much more electronegative than sulfur. The effect of the trifluoronethyl groups would not be as great in the ketone as in the thioketone. But, if inverse addition should take place, it would be a new method of forming a carbon-silicon bond : ?f3 c;t rnr? CI

PAGE 37

CI 1

PAGE 38

:^±ij.. indicated loss of most of +'' "logcr.. The isopropoxy groups probably cleaved slowly to give e>.>.. ...,-. ._ cross— linking to £orm the hard, brittle solid which resulted on standing.

PAGE 39

o o -a c o Ge. o o i

PAGE 40

o o C\.' CM 73 . e J=i CJ n O O t-,

PAGE 41

i Q JO o 11 3 '! -H •T3 C O a e o u

PAGE 42

37 o o Cv) CM n ON a. s ^S. 0) ;3 . o o as e CO ON o 00 o o o\

PAGE 43

o c 'aR. a; (i^ 3: h o— rj>-^o o s n

PAGE 44

III. EXPERIMENTAL General All temperatures reported are uncorrected and are given in degrees Centigrade. Molar refraction (Mr^) data were calcxilated from bond refraction values reported by Warrick (38). It was found that the experimental Mr J. 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 detennined with an Abbe refractometer at 20 degrees Centigrade, densities were determined at 20 degrees Centigrade 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 dimethyltrifluorovinylsilane, were prepared by adding the appropriate chlorosilane to a solution of trifluorovinyllithium at -78°. The trifluorovinyllithium was generally prepared as follows : 39

PAGE 45

acetone bath and condeniid in a cold .. turned dark blue aftor abo-.t 30 about two hcv.rc Trims thylchlorc..-. ^ stirred solution of trifluoroviiv at — 7B^. The reaction raixture was allci^^d to cc slov;ly. The mixture was then hydrol;. separated and dried over CaClp. Distiilatic. Of) 67°, n^ I.358O, i.r. Aon at 5.83 ^i. '. 65°, r^^ 1.3569, i.r. absorption at 5.83 tx, ) Tri f 1 uoro vinyldime t hyle ' Dinethylchlv niole of absolute ethanol to ^ t.--i— amylaaiine with stir. -ve yields ox" about ^O'fo of the desired p. Ah small aiiiounts of the dichloro and diethoxy compounds as i. -.5. Dirr.sthylchloroethoxysilane (3O g. , 0.22 mole) was slowly added to a stirred solution of trifluorovinyllithium (0.22 mole) at -73°. Tr.j mixture was allowed to come to room temperature slowly. The lithium chloride was filtered out and the remaining solution was distilled to

PAGE 46

yield 20 g. II (50vi), b.p. 103-'^°, nj^ 1.36'r2, d ° 1.028, Hr^ calcd. 39.9, found '1^0.3. Aral. Calcd. for C^H^^F 03i : C, 39.12; H, 6.02; F, 30.9^. Found: C, 38.90; H, 6.26; F, 3I.O5. TrifliTt>rovin.yldin;ethylchloror,ilvn.nG [HI] Trifliiorovinyldiinethylethoxysilone [II] (I5 g. , O.O85 mole) vras slowly added to PCI (6.1 c, 0.0^5 riole) at 0° with stirring. Stirring was continued for 5 hours and the solution distilled, yielding S.l g. Ill (55:-), b.p. 87", r.^° 1.3?6^, d~° 1.15^, ^--rry calcd. y'r.2, found 34.7. Anal. Calcd. for C^H.CIF Si : C, 27.51; H, 3.^6; F, 32.64. Found: C, 27.74; H, 3.68; F, 32.81. l,"-Bij:-trinuorovir!:-l-] ,1,3.3-^ .'ill l,3~01chloro— 1,1,3,3— tetrair.ethyldisiloxane was y by adding water in dioxir.e slovrly to a solution of dichlorodimethylsilane in ethar in the marjier described by Patnode and V/ilcox (14). This compound (11.5 g. , 0.056 Kole) was then added to a stirred solution of trifluorovinyllithiu;ii (0.12 nole) at -73°. The mixture was allovrcd to come to room temperature, water was added, and the organic layer separated and dried. Distillation yielded 8.3 g. IV (50^), b.p. 53-54'*/20jm, OA pA n^ 1.3691, d 1.136, Krp calcd. 57.^, found 58.3. Anal. Calcd. for C^H^^^^GSig : C, 32. 60; K, 4.11; F, 38.72. Found: C, 32.54; H, 4.23; F, 38.46. TrJ fluorovinyldiTnethylsilsne [V] Bromotrifluoroethylene was bubbled into a 3OO r.l. 3-nscked flask containing 120 nl. THF and 5 g. (0.2 niole) magnesium. Vrnen the reaction

PAGE 47

iai'ted, the mix'. collectc .: i over CaCl^. ,.?-50« •f 1.3513, d^°^. C, 3-!^. 55; H, 5.28; F, ^1-0.29. Pentaflr 0_0'i [HI] ('^ ^-v" yielded 7.2 g. (57^) v., . Anal . Calcd for C .; .;, i,.v,-; j , •:;/.;-,. rcu;... ; C, 38.45; H, 2.18; F., Bis-trif] • ' One ffiole of trifluo: .t — 78° vras added to dichloro:: ilane {6y g. , O.5 inole) at —75°. The mixtur: allowed to cor;cto roon; temperature. The lithium halide v:as : out and the filt. The only product, in addition to re— 2C covered dichlorodiinethyl silane, was 30«5 g. ^^^^ (56fo), b.p. 98°, n~ Of) 1.3633, d 1,272, Mr^ c.j, found 38.5. An?l. forC-32.73; H, 2.7^; F, 51.77. Found: C, 32.43; H, 2.97; F, 51.48.

PAGE 48

^3 Preparation of 2,3,3-Trifluoroallyltrimeth.ylsilane [Villi Bromoraethyltrimethylsilane (8.^ g. , O.O5 mole) was reacted with an excess of dispersed lithium in 50 ml. ether. The lithiiim reagent formed was filtered to remove the remaining lithium and added to a 100 ml. thick-walled glass tube. Tetrafluoroethylene (6 g. , O.O6 mole) v/as condensed into the tube at liquid nitrogen temperature. The tube was evacuated and sealed and left in aJi ice bath overnight, and at room temperature for 12 hours. The tube was opened and all volatile materials 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. (42^) VIII, b.p. 89*', n^° 1.37^5, d^° 0.949, Mr^^ calcd. 39.2, found 40.4. Anal . Calcd. for C^xH^^F Si : 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 [IX] 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 (I30 g. , 2 moles) was heated to reflux. ( 1 , 4-Dibromo-3chloro-3,4,4-trifluorobutyl)trimethylsilane (188 g. , O.5O mole) was added at a rate to maintain reflux ;ri.thout 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^ HCl 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 water layer was discarded; the ether layer was

PAGE 49

hMwashed twice more with water and dried over CaCl„. Distillation yielded 68.5 g. (75^) [IX], b.p. 112-114°, n^ I.38O8. Tomasino reported b.p. llif", n^^ 1.3790. (3,4,A^Trifluoro— 3— chloro— 4H3romobut.vl)dimeth,ylchlorosilane [X] A solution of dimethylchlorosilane (25 g. , O.37 mole), 3,4,^tri— fluoro— 3— chloro-4-bromo-l— butene (57 g. , 0.26 mole) and 1/2 ml. 1 M solution of H-PtCl^ in isopropyl alcohol was refluxed in a 200 ml. flask for 24 hours. Distillation of the products gave 11 g. dimethyldichloro— silane and 35.8 g. X (445^), b.p. 205°, n^ 1.4400, d 1.513, Mr^ calcd. 56.4, found, 56.0. Anal . Calcd. for C^H^QBrCl^F Si : C, 22.65; H, 3.I6; F, 17.91. Found: C, 22.69; H, 3.57; F, 18.97. (3,4,V-Trifluoro— 3— chloro— 4-^romobutyl)meth,yldichlorosilane [XI] A solution of methyldichlorosilane (23 g. , 0.020 mole), 3,4,4— tri— fluoro— 3-chloro— '+— bromo— 1— butene (40 g. , 0.18 mole), and I/2 ml. 1 M H-PtCl/solution in isopropyl alcohol was refluxed 24 hours. Distilla— 20 20 tion gave 45 g. (71^) XI, b.p. 220°, n^^ 1.4451, d I.6076, Mr^ calcd. 56.1, found 56.0. Anal . Calcd. for C H BrCl F Si : 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 THF was removed and the flask temperature increased, the residue quickly

PAGE 50

^5 turned black and a two— phase mixture was distilled. The products v:ere not separated and identified, but no olefinic group showed in the i.r. spectra. 1 , 3-3is( 3 ,4, V-trif luoro-3— chloro-^bromobutyl )— 1 ,1 « 3 > 3-tetramethyldi— siloxane LXIIl (3,3,^Trifluoro— 3— chloro--V-bromobutyl)diinethylchlorosilane (36 g. , 0.11 mole) was heated with stirring overnight in 25 ml. water. The organic layer was separated and dried over CaCl^. Distillation yielded on 20 23 g. (82^) XII, b.p. 125<'/mra, n^ 1.^3^5, d 1.4712, Mr^^ calcd. 101.9, found 102.7. Anal . Calcd. for C^2^20^r2Cl2F£OSi2 : C, 24.78; H, 3.47; F, 19.62. •Found: C, 24.93; H, 3.52; F, 19.74. 1 . 3-Bi s ( 3 , 4 , 4-trif luoro-3-trif luoro-3-butenyl )-l . 1 , 3 , 3-te trame thyldisiloxane 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 i
PAGE 51

for C^H^^2^1F^Si : C, 33.79; H, 5.58; F, (^^.5.5-^"; ".oles of C!L :(V, b.p. d"*^ 0.959, Hr^j calcd. Anal . Calcd. foiC ':. ?..Si : C, 45.9^; H7.73; ^^ 29.04. C, ^.71; .. 1,3-Bip(4,5,:, XIV (16 s. , 0.07^ nole) . ~j ml. water. The organic 1-i^ii etu&r a...d driod over CaCl Illation yie.": . .117°/l0rva, n^ 1.4016, d~" ... -cd. for C, ii-';-. 42; H, 6.40; F, 30.12. Found; C, 44.60; h, 6.43; F, 30.31. I with Sodiun Ethoxide if A 100 ml. 3— necked flask was equipped with a dropping funnel, stirrer, and reflux condenser. )1 (60 ml.) xras added and allowed to react with sodium (1.2 g. , O.O5 mole). I (15.^ g. , 0.10 mole) was slowly added to the stirred solution. A gas, probably trifluoroethyl— one, v/as evol jn the addition was : r-lution was diluted vdth water and extracted with eth .tion yielded 5 g-

PAGE 52

47 20 hexaraethyldisiloxane (60^), b.p. 97-99", n^^ 1.3777 (Lit. b.p. 100.4, n^° 1.3772). Attempted Dimerization of I I (7.0 g. , 0.45 mole) was sealed in a glass tube and heated at 200<* for two days. Distillation gave some starting material and 0.25 g. (3.8^) o^ material boiling 96**/24fflm, Considerable decomposition was evident. Anal . Calcd. for C-LQ%3F^Si2 : 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. , O.09O mole) was sesiled xinder N_ in a glass tube and heated at 200° for 24 hours. A black solid was obtained, but no volatile products were present. Reaction of Lithiuri Reagents with I In general, the lithium reagent was prepared either directly or by the halogen exchange reaction vrith butyllithium. The lithium reagent was then slowly added to an ether solution of I in a 3~^ecked flask equipped with a stirrer and reflux condenser. The reaction mixture was then hydrolyzed, the ether layer separated and dried, and the product obtained by distillation. Reaction of methyllithium with I . Methyllithium (O.O5 mole) was added to I (7.7 g. , O.O5 mole) in ether. A gas was evolved. A sample was collected, and the i.r. spectra indicated that it was probably CILCP=CHF. The reaction mixture was worked up as described and

PAGE 53

hS distillatir. ; l,kg. (19^) l-triinethylsilyl-l,2-difluoro-l-propene 20 20 ^^ 1.3921, d 0.917, Mr^ [XVII], b.p. Sb'^, n;:° 1.3921, d^° 0.917, Mr^ calcd. 39.1, found 39.1. Anal. Calcd. for C^H^^F^Si : C, 47.97; H, 9.06; F, 25. 50. Found: C, i^7.7S; H, 9.07; F, 25. l'^. Reaction of butyllithiura Kith I . Butyllithiuni (C.IO itioIg) v^as slowly added to I (15-4 g. , 0.1 mole) in ether. V/ork-up of the reaction !Tiixture gave 13.4 g. (705^) 1— trinethylsilyl— 1,2— difluoro— 1— he>;ene [.Will], b.D. 76°/40niin, n^° , , , , ^ ,20 . .^^ ,, , , ^„ „ , ' • ' ' D 1.4112, d 0.087, -'^rj-j calcd. 5j.0, founa 53.9. Anal . Calcd. for CoH^gF^Si : C, 56.21; H, 9.44; F, 19.76. Found: C, 56.39; H, 9.48; F, 19.53. Reaction of phenyllithium with I . Phenyllithium (O.IO rcole) was slov;ly added to I (15.4 g. , C.IO mole) in ether. Work— up of the reaction fixture gave 15. 1 g. (72/3) .8— triinethylsilyl-a,p-difluorostyrene [XIX], b.p. 70-74°/2iTm, n^° I.5062, d^° I.O3O4. Anal . Calcd. for C H,|,F Si: C, 62.22; H, 6.64; F, 17.90. Found: C, 62. 51; H, 6.53; H, 17.75. Reaction of rr^— trifluoroinethylphenyllithiuni with I . in— Bromobenzo— trifluoride (22.5 g. , 0.10 mole) was reacted with butyllithiun (0.10 mole). The reagent was then slowly added to I (15.4 g. , 0.10 mole) in ether. VJork— up of the reaction mixture gave 14.0 g, {^C%) of m— trifluoromethyl— 3— trimethylsilyl-a,3-difluorostyrene [XX] , b.p. 101-104°/6mm, r^^ 1.4640, d^° 1.181. Anal . Calcd. for C^.^H-^ F Si : C, 51.42; H, 4.68; F, 33.89. Found: C, 52.3I; K, 4.57; ?, 33.22. Reaction of 1— naphthyllithium with I . 1— Bromonaphthalene (20.7 g. , 0.10 mole) was reacted with butyllithium (O.IO mole). (It was later

PAGE 54

49 found that less than 0.10 mole of 3uLi was used, but the correct aT:ount is unkno^m. ) The 1-naphthyllithiura was slowly added to I (15.4 g., 0.10 mole) in ether. Itork-up oi the mixture gave 10 g. (3-'^^) of 1(l,2-difluoro-2-trimethylsilyl vinyl) naphthalene [XXI], b.p. 100°/l.:_:-.. n^^ 1.5588, d~^ 1.116. Anal. Calcd. for C^^H^^F^Si : C, 68.69; H, 6.I5. Found: C, 63.43; H, 6.35. Reaction of 2-thiophenyllithiurn vn.th I . 2-3romothiophene (I5.O g. , 0.09 mole) was reacted ^•ri.th butyllithium (0.09 mole). The 2-thiGr;henyllithium was slowly added to I (14 g. , 0.09 mole) in ether. V/ork-up gave 10 g. (50>o) 2-(l,2-difluoro-2-trimethylsilyl vinyl )-thiophene [XXII], b.p. 60°/2™, n^° 1.5201, d^*^ 1.135. Anal. Calcd. for C^E.^^F^S2i: C, 49.50; H, 5-54; F, 17.35. Found: C, 49.62; H, 5.52; F, I7.I7. Reaction of allvllithiura with I . Tetraallyltin (7.1 g. , 0.025 mole) was slowly added to an ether solution containing phenyllithium (0.10 mole). A precipitate of tetraphenyltin xiras formed. 1(15.4 g. , 0.10 mole) was added slov/ly to this mixture. The mixture v/as stirred for tv70 hours and filtered. Distillation of the filtrate yielded 3.5 g. (20;o) of l-trimethylsilyl-l,2-
PAGE 55

for two hours and steam distilled to remove the product I'ron the tetra— pheriyltin. The ether layer was separated, dried, and distilled. The product was found to polymerize when heated, but 2.3 g(iv/ij of 1— triinethylsilyl— 1,2-difluoro— 1,3— Dutadione [XXIV] was obtained, b.p. 45°A0Km, n^*^ 1.4400, d~° 0.944. Anal. Calcd. for C H^2^2Si = C, 51-74; H, 7.45; F, 23.41. Found: C, 52.14; H, 7,30; F, 21.36. Preparation of l,2-^ifluoro6'lefins from the Products of the Organolithium Reactions In general, the compound forr.ed in the reaction of the lithiu-n reagents on I was refluxed for about two hours in a KOH-ethanol solution. Excess water was then added and the products extracted in ether. The ether layer was then dried and the product obtained by distillation. Preparation of l,2-C)ifluoro— 1— hexene [XXV] I-Triinethylsilyl-l,2-^ifluoro-l-hexene [XVIII] (I3 g, , 0.047 mole) was reacted as above wdth 20 ml. KOI-f-ethanol solution. Work— up yielded 5 g. (6256) XXV, b.p. 73°, n~ I.368O, d 0.885, i-'r^ calcd. 29.5, foujnd 30.4. Anal. Calcd. for C^K^ qF2 : C, 6O.OO; H, 8.34; F, 3I.6I. Found: C, 59. S9; H, 8.21; F, 3I.3O. Preparation of G-,6-Difluorostyrene [XXVI] 3-Trimethylsilyl-a,3-difluorostyrene [XIX] (11,8 g. , 0.056mole) was reacted as above with 20 ml. KOK-^-thanol solution. Worl-^-up yielded 5.5 g. (61^) XXVI, b.p. 84/60, n^° 1.5056, d~° 1.155. Nad (12) reports b.p. 88-90o/6Cmm, n^ I.5C6O. Preparation of m-TrifluoroiP.ethyl-a,S-difluorostyrene [XXVII"]

PAGE 56

m-Triiluorornethyl— 3— trir.ethylsilyl-a, S-difluorostyrer.e [XX] (I3 g. , O.Oif? mole) v/as reacted as above v/ith 20 ml. KOH-ethanol solution. V/ork-up yielded 7.3 g. (755^) XXVII, b.p. 75°A0inm, n^° 1.^467, q^° 1.353. Anal. Galea, for C.H F : C, 51.94; H, 2.42; F, 45.65. Found: y z> D C, 51.79; H, 2. 50; F, 45.28. This compound formed a clear glass i-rith a M.V/. of 66,300 '.irhen heated at 90° overnight with benzoyl peroxide. Prer;£.ration of l-(l,2-ginuorovinvl)nar^hthcnlene [XXVIII" l-(l,2-Diriuoro-2-trimethylsilylvinyl) naphthalene [XXI] 9.3 g. , 0.039 mole) was reacted as above with 20 ml, KOH— ethancl solution. Work-up yielded 5-5 g(83)-^) XJiVIII, b.p. 70='/lram, n^° 1.5975, d^° 1.224. Anal. Calcd. for C^.^PLF^: C, 75.77; H, 4.24; F, 19.97. Found: C, 75.23; H, 4.10; F, 19.14. Attempted Preriaration of 2— (l,2-^ifluorovinyl)thiophens 2-(l,2-Difluoro-2-trir.ethylsilyl vinyl )-thiophene [XXIV] (8 g. , 0.04 mole) v^as reacted as above with KOH-ethanol solution. Work-*ap /I '^0 yielded ^-5 g. product, b.p. 65°/4Cmm, n~ 1.5272. The compound quickly discolored, and the next day was a black tar. Anal . Calcd. for C^H^F^Si : C, 49.30; H, 2.76; F, 25.98. Found: C, 45.41; H, 2.69; F, 27.43. Attermoted Preparation of 1,2-^ifluoro— l,^pentadiene 1— Trimethylsilyl— 1,2-diiiuorc— 1,4— pentadiene [XXIII] (3 g. , 0.017 mole) v;as reacted as above v.'ith KOH-ethanol solution. Work— up yielded a small amount of low boiling product, but not pure enough for analysis.

PAGE 57

Attempted Preparation of 1,2— Difluoro— l,3~t>''^"'^a-dienn The steam distillate from the preparation of _—^_...-. — diiluoro— l5 3~"^tadiene [XXIV] was stripped of ether by an The concentrated solution was then slowly added to a hot i.^^.. .->... •_ solution. The gases evolved were caught in a Dry Ice— acetone trap. Separation by v. p,c. gave three fractions. One was identific.: 'r' -. and H.W. as CFp,=CFIi. Another was probably IjZ-difluorobutadier.j, o„:there was not enough for elemental analysis, i.r. Data were consistent. The third component (highest boiling) vras not identified. Reactions of (3.^*-,^Trifluoro— 3— butenyl)tri!nethylsilane [iXl Thermal Dir.erization of iX IX (25 g. , 0.14 mole) was sealed in a thick— walled glass tube containing a pinch of hydroquinone. The tube was heated at 210° for •t-? hours. Distillation of the reaction mixture yielded 3 g. dimer [XXIX] Of) pn (33^), b.p. 70°/0.8, n^ 1.4059, d 1.C69, Kr^. calcd. 84.3, ^oxi-z. Anal . Calcd. for C, , H^^F.Si : C, 46.12; H, 7.19; F, 3I.26. Found: C, 46.31; H, 7.19; F, 3I.52. Reaction of Phenyllithium with IX IX (9.1 g. , 0.05 mole) was slowly added to a solution containing phenyllithium (O.O5 mole) in ether. The mixture \
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XIV (25 Z' , 0.12 nole) was heated in a sealed tube at 200^ for ^A hours. Distillation yielded 10 g. (42^) XXI, b.p. l^yj y.-^-^, -i.p. 53-5o<=. Anal. Calcd. for C^^'^pi+^lpF^Si, : C, 33. ?9; H, 5.58; F, 26. 3C. Found: C, 39.65; H, 5.5S; F, 27. 07. Prop5.ration of Kalogenated iGooropoxysilanc^.q Preparation of (1,1,1,3,3, 3-Hexaf luoroigopropo>:v)mGthvldir.hlnro,'-o 1 r, r... i vyyvi ^ -^ ' ' " Hexafiuoroacetone (I6. 6 g. , 0.10 r.ole) and nethjldichlorosilane (15,0 g. , 0.10 rr.ole) v;ere sealed in a thick-'vjalled glass tubo and irradiated in sunlight for about two weeks. Distillation gave 20 g. (63,^) ?0 20 XXXxi, b.p. 9^°, n~ 1.3333, d 1.439, Kr^ calcd. 39.7, found 40.1. Anal. Calcd. for C^K^Cl2F^0Si : C, 17.09; H, 1.^3; ?, 40.55. Found: C, 17.15; H, 1.45; F, 40. 3I. reparation of ( 1,1,3, 3-Tetrafluoro-l,?-dichloroisoproooy^v)rriethyldihlorosilane LXXX7I] ' ' l»l>3,3~^etrafluoro— 1,3-dichlorcacetone (80 g. , 0.40 r..2ls) zr.z. raethyldichlorooilane (46 g. , 0.40 r.ole) were sealed in a thick-v/alled glass tube and irradiated for about two weeks. Distillation yielded 89 g. (79^^) XXXIII, b.p. 153°, n^° 1.3930, d^° 1.524, Xr^ calcd. 49.4, found 49.3. , Anal. Calcd. for C^H^Cl^F^OSi : C, 15.25; H, 1.29; F, 24.20. Found: C, 15-85; H, I.33; F, 24.33. Preparation of (l,l,l,3,3.3-hexafluoroisopropoxy)trii^3thylsilane [XXXIVl XXXII (17 g. , 0.06 mole) was reacted ;>rith CHJ^Br (0.12 mole) in ether. The mixture vxas hydrolyzed and the organic layer dried. Distil— "d ?n ^0 lation gave 5 g. (35^^) XXXIV, b.p. 80°, n^ 1.3196, d" 1.177, "r, calcd. 40.5, found 40.3,

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53 Reaction of IX ;jith l,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 200° for 2k hours. Distillation of the liquid residue gave J, 6 g. (33. 6/o) of a compound tentatively identified as either ( CH^ ) ^SiCH„CH„CF-CF„ ( CH_ ) _SiCH„CH„CF— CF_ 33 22i|2 or 33 22| \ 2 CH2=CHCH-CH CH2-CHCH=CH2 Infrared analysis showed a vinyl group to be present. Anal . Calcd. for C^^H^qF Si : C, 55.88; H, 8.11. Found: C, 56.8?; H, 8.11. Reaction of IX with NOCl A 3— necked, 3OO ml. round— bottomed flask was fitted with a stirrer, reflux condenser, and inlet tube. DMF (I60 ml,), AlCl (11 g. , 0,082 mole), and IX (11 g. , O.O6 mole) was added to the flask. NOCl 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-) SiCH-CH_CFCFCl was obtained, n.m. r. Spectrum indicated the structure was possible, although not definite. Anal . Calcd. for C H^ GIF NO : C, 33.89; H, 5.29. Found: C, 33.76; F, 5.43. Thermal Dimerization of (4,5, 5~Trif luoro— 4-pentenyl )dimethylchlorosilane [ XIY]

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y:> Ana. Calcd. for C^Ii, qF^OSI : C, 29.93; H, 4.19: F, i.-?.^:: C, 30.10; H, 4.13; F, 47.66. Preparation of (1.1,3, 3— Te trafluoro— 1 , 3-<^.J chloroi . , , , ^_^ si lane LXXXVI XXXIII (31 £. , 0.1 mole) was reacted with CH.MgBr (0.2 ir.ole) in j ether. Ths ndxture was hydrolyzed, and the organic lo.yer dried. Distillation yielded I5 g. (50;^) XXT/, b.p. 138°, n^° 1.3515, d^° 1.2c3, Mtq calcd. 50.1, found 50.I. Anal . Calcd. for C^I-^ ^Cl^F^OSi : C, 26. 34; H, 3.69; F, 28. S2. Found: C, 26.39; H, 3. 81; F, 27.93. Polymerization of XXXII and X-XXIII Twenty graiTi saznples of XXXII and XXXIII were rapidly added to separate beakers containing 50 ml. water. The rdxtures were stirred rapidly. Each formed an elastoiueric gu.T. in about 10 to I5 minutes. The gu.T.3 were resilent but not strong. The gums were put on vratch— glasses to dry overnight. They hardened overnight to for.n brittle polymers. Elemental analysis of the polymer from XXXII showed only 4.41^ fluorine: analysis of the polyir.er from XXXIII showed only 7.60% chlorine. (Calcd. : 50.4% and 27.4;'-i respectively, if no hydrolysis of the iscprcpoxy groups took place. )

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IV. SUii:-i"-RY A series of silanes of the general fc been prepared, where n is 0, 1, 2, or 3f^ <-or soae functionsuL group. The first of the series, RMegSiCF^F^, was prepared by the reaction of C?2^^i X'j'ith the appropriate silane, where R is CK^, EtO, or OS±yie^CF=Cr^. V.^here R is CF^^^F, the starting silane -..-g '/a.SiCl^, and where R is H, CF„=CE-ig3r was reacted with ClMe2SiH. The conipound Me^^SiCH-CI'M^F was prepared by the reaction of Me^SiCK.Li vath CF„=CF„. ;> ^ 2 2 The conipcund Me SiCH2CH2CF=CF2 was prepared by the fr;---: addition of CF^BrCFClBr to CH2=CHSil-ie and subsequent ::::; . and reduction of the addition product. Other derivative's '.;„.c cc-cc:.-.:. .: fror. the addition product of CF^BrCFClCIW^H^ and ClMe2SiH. Derivatives of RI'le2SiCH2CH2CH2CP=CF2 were obtained froni the addition product of ClMe2SiH and CH2=CHCH CF=CF,. The chlorine, triraethyl, and disiloxane derivatives v.'ere prepared. Me_SiCF=CFp was found to give substitution products with several lithAurc compounds : RLi + Me SiC?^F2 ^ Me^SiCF=CFR Lithium compounds used were methyl, n-butyl, phenyl, r.^-trifluoromethylphenyl, 1— naphthyl, 2— thiophenyl, allyl, and vinyl. These substitutior 56

PAGE 62

pi'oducts x^'cre further reacted in alcoholic base to give 1,2-diflucrc— (Olefins with tho r^-butyl, phenyl, rr-triflucrorcethylphei-yl. and 1— naphthyl adducts. The compound Me-SiCK-CH-CF^Fwas found to resi:: . .by codiura ethoxide, but reacted with phenyllithiuir. to give Me^SiCH CH CF^FC.I',. Me_SiCH2CH^CF=CF also formed the cyclobutyl dinier upon prolonged heating, as did ClMe^SiCH CH CH,CF=CF Tito ketones, CF lJcF and CF2ClbcF2Cl, were found to react with methyldichlorosilane to give the isopropoxides, CI CF^ CI CF^Cl I I 3 I 1 2 MeSiOCH and MeSiOCH ' ' II CI CF CI CFgCl Both of these polymerized by reaction in water. Much of the alkoxido was lost, giving hard, brittle polyr.crs instead of the desired elas— tor.ers. The trinethyl derivatives '.•rere also prepared from the tv.'o alkoxides.

PAGE 63

V. BIBLIOGRA??IY 1. R. Galas £.id N. Duffant, C.R. Acad. S.i. _ _, , . Quoted in C. Eaborn, "Organosilicon '.. •, " Ac'rI:,.;.io Prdss Inc. , New York, N. Y. (1960) p. 2I3. 2. T. D. Coyle, S. L. Stafford and F. G. A. Stona, J. C;. ^.„. 1961, 3103. 3. S. Dixon, J. Org. Chani. 21, 400 (1956). k, B. E. Gray, M.S. Thesis, University of Florida, 1955. 5. R. N. Kaszeldine, l^ature l63, 1028 (1951). 6. H. D. Kaess, S. L. Stafford, aiid F. G. A. Stone, J. :..-.. u.v:.r.. 81, 6336 (1959). 7. I. L. Knunyants, R. N. Stsrlin, R. D. Yatsenko, : Izv. Akad. Nauk S.S.S.R. Otd. Khira. Nauk. 13^5 (l95oj. 8. R. P. Lutz, M.S. Thesis, University of Florida, 19559. E. T. McBee, C. VJ. Roberts, G. F. Judd, and T. S. Chao, J, Am. Chen. Soc. 77, 1292 (1955). 10. •. J. Middleton, E. C. Howard, and VJ. H. Sharkey, J. Pjn.. Chem. Soc. 8^, 2589 (1961). 11. H. Muramatsu and P. Tarrant, J. Org. Chera. 29, 1796 (I9c4). 12. M. M. Nad, T. V. Talalaeva, G. V. Kazennikova, and K. A. Kocheshkov, Izvest. Akad. Nauk S.S.S.R. Otd. Khim. Nauk. 272 (1959). 13. J. D. Park, R. J. Seffl, and J. R. Lacher, J. Am. Chea. Soc. 73, 59 (1956). Ik. W. I. Patnode and D. F. Wilcox, J. Ara. Chen. Soc. 6S, 358 (19^6). 58

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59 15. F. J. Pisacane, Ph.D. Dissertation, University of Florida, I963. 16. W. Postelnek, Ind. Eng. Chem. 50, 1602 (1958). 17. D. Seyferth, K. A. Brandle, and G. Raab, Angew. Chem. 72, 77 (i960). 18. D. Seyferth and T. Wada, J. Inorg. Chem. 1, 78 (I962). 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 (i960). 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. Khira. 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, 23^3 (195^). 27. P. Tarrant, G. W. Dyckes, R. Dunmire, and G. B. Butler, J. Am. Chem. Soc. 22, 6536 (1957). 28. P. Tarrant and E. G. Gilraan, J. Am. Chem. Soc. 76, 5^23 (195^). 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).

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32. p. Tarrant and E. C. Stump, J. 0_ 33. P. Tarrant and R. E. Taylor, J. Org. Ch<:;to. 2_ }k. P. Tarrant and D. A. Warner, J. iin. Chen. Soc. ;^ 35. R. E. Taylor, M.S. Thesis, University of 36. C. Tomasino, Ph.D. Dissertation, 37. 3. G. Tucker and E. VMttle, Proc. Chen. Soc. I963 , 9338. E. L. VJarrick, J. An. Chen. Soc. 68, 2^55 (1946).

PAGE 66

BICGRAPHIC.4L NOTE V/ard H. Oliver xvas born April 20, 1930, in Mobile, Alaba-. . attended public schools in Baldvdn County, Alabama, and graduated from Baldwin County High School in Kay, 19^. He entered the U. S. Navy the month of his graduation and served on active duty fcr a period of 10 years, 11 months and 19 dsys. Frdle in the service he attended Bel I'lar Junior College in Corpus Christi, Texas, for a period of three years. Upon being discharged, he enter.d Southern Ilissionary College, Collegedale, Tennessee, and graduated v.dth a B.S. in Cheisistry in June, 1961. He entered the University of Florida as a graduate assistant in September, 1961. He later received a fellov;ship supported by the U. S. Anny Natick Laboratories, Natick, Massachusetts. The author is r^arried to the forrcer Miss Lyda Little of Bay i-linette, Alabama, and has three children. He is a member of the American Chemical Society. 61

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This dissertation was prepared under the direction of the ch:. of the candidate's supervisory committee and has been approve...--.smbers of that coininittee. It was submitted to the Dean of the Cc of Arts and Sciences and to the Graduate Council, and ^^ras approved as partial fulfillment of the requirements for the degree of Doctor of Philosophy. December 19, 19^4 Dean, Graduate School Supervisory Corriraittee ^j:^,-^-V^

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METS:behaviorSec VIEWS Options available to the user for viewing this item
METS:behavior VIEW1 STRUCTID Default View
METS:mechanism Viewer JPEGs Procedure xlink:type simple xlink:title JPEG_Viewer()
VIEW2 Alternate
zoomable JPEG2000s JP2_Viewer()
VIEW3
Related image viewer shows thumbnails each Related_Image_Viewer()
INTERFACES Banners or interfaces which resource can appear under
INT1 Interface
UFDC_Interface_Loader