PREPARATION AND REACTIONS OF SOME
FLUORINE CONTAINING SILANES
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
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
LIST OF TABLES v
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
Reactions of Me SiCH2CH2CF2CF 27
Thermal Dimerization of CIMe2SiCH2CH2CH2CF=CF2 29
Preparation of Fluoroisopropoxysilanes 29
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-
Preparation of Halogenated Isopropoxysilanes 54
BIOGRAPHICAL NOTE 61
LIST OF TABLES
1. Olefins Prepared from Me SiCF=CF2 via Lithium Reagents 25
2. Physical Properties of Compounds Prepared 34
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
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-
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
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
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
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.
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
Silanes containing olefinic groups, such as vinyl and allyl
groups, are perhaps the most important of these.
CH CH2CHO + CH2=CHSiMe3 CH CH2CCH2CH2SiMe
SiH4 + CH2=CHSiH3 u.v.. H SiCH2CH2SiH3
The halides are also useful:
CH COOH II
Me3SiCH2C1 + CH COOK Me SiCH2OCCH
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-
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:
CF2BrCFClBr + CH2=CHSiMe3 Bz CF2BrCFClCH2CHBrSiMe
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-
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:
Et SiCFCF2 + C H5Li -- Et SiC-=CFC6H5 5
Et3SiCFC(C6H5)2 or Et3SiC(C6HS)=CFC6H Et SiCH
+ 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
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.
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
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
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
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
Iee PC1 Me
EtOSiCF=CF2 > ClSiCF=CF2
The compounds were identified by elemental analysis, YrD data, and their
Compounds such as II and III night be of interest as crosslinking
agents in polymers or intermediates in preparing other trifluorovinyl-
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:
2Me2SiC2 + H20 ---s ClSiOSiC1 + 2HC1
2 2 2 I I
-c:-..Lal analysis, i.r. spectra, and MrD data were consistent with the
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-
HSiCl + CF2gFMgBr ---- HSiCF=CF2
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
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
It was hoped that 2,3,3-trifluoroallyltrimethylsilane could be prepared
from the Grignard reagent of chloromethyltrimethylsilane:
Me SiCH C1 + Mg Me SiCHMgCl "
3 2 3
*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
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
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.
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
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
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:
CF2BrCFClBr + (CH2-=HSi)20 ---- (CF2BrCFClCH2CHSrSi)20
h2 e Me
t (CF,=CFCH2CHr Si),0 + (CF2=CFCH CH Si)0
Since the first step in this reaction gave only a 16' yield of the
desired intermediate, a different approach was sought to prepare the
The reaction of silicon hydrides with olefins, discussed in the
Introduction, generally goes in very good yields:
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-
ClSiH + CH2 =CHFC1CF2Br CISiCH2CH2CFC1CF23r
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
S/Zn ey Me
CISiCH CH CFClCF2Dr 0(. .-.. ?2 2
H0 le n 42
2 -0(.:_ J:: 2.h1CF Br)
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
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
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
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:
ClSiH + CH2=-HCE2CF=CF2F CISiCH2CH2CH CFCF2
I 1 2 2 2
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-
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:
. -. r
)nd led to
Cl iC' CH2C-'C-2^ +
1 __ -
Structural proof was by elental anlysis, infrared spectra, and rD
The disiloxae was readily prepared by reacting XIV with water:
2C1SiCH22C HII2CF=CF2 O( ::c- Fc .=C F2 2
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-
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:?
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
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
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:
2Me Si=C=CF --20 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 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-
4gBr me/ \
I F< SiCF=CF
+ ClSiCF=CF -----2 i 2
:[ FJ Me e
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 ,
-isiorna "ct p.. aL ..
spect:- a.nd v.p.c. _-tention ti:.
r C -=c
+ 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 -
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) .
JL- ._ i
their ;C.Uvi-L y Lo rard a
s-s...l .on .=c in
.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
to -- -
wo.-,d ..ci o
would 1, acx 0.
_11 + -
5-ctra shows n.o azorption due to an i C r:p, a.; idata a;rco iril
cen.. tL : i
were cl..'ned i,
nl .._.. --
00 0' a C
CD O O
0 = =H cH
cO N CI M N0
o co N N
a 2-1 0 x
ii 3;C M C
0 M C
U )- 51
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,
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:
.:.-.~.. .. I .. u.
I-,i -, -~
,'5 -,- -
-u.~-.- -~ U,
- - 5 2 -
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,
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
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
68.5 g. (75%) [IX], b.p. 112-114, nD 1.3808. Tomasino reported b.p.
114, nD3 1.3790.
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-
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.
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-
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.
1,3-Bis(3 4, 4-trifluoro-3-chloro-4-bromobutyl)-1,1,3,3-tetramethyldi-
(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,
Anal. Calcd. for C12H20Br2C12F60Si2: C, 24.78; H, 3.47; F, 19.62.
-Found: C, 24.93; H, 3.52; F, 19.74.
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
CaC12. Distillation yielded 6.8 g. (42%) XIII, b.p. 950/6nm, n0 1.3932.
Tomasino (34) reported b.p. 950/6mm, n0 1.3975.
Preparation of (4,5,5-Trifluoro-4-pentenyl)silanes
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.
hexamethyldisiloxane (60%), b.p. 97-990, n0 1.3777 (Lit. b.p. 100.4,
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
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--
:XVniiI, b.p. 76/40:L, nn0
EX:VI1, b.p. 760/4C0mm, fD 1.4112, c20 0.887, MrD ca-cd. 5-.
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 .
: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.
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
nD 1.5538, d 1.110.
nl. Cald. for CHF2Si: C, 68.69; H, 6.15. .....: .
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!,
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.
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.:
/ '-,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........
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
-. ..... -. 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.
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. 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.
al-.d V. a; C;-l=..-
Tho th~ird c~i-ocrccncnt at3ilr.) rs n-ct icc~;_-,
:: 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
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.
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_ .-
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-
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;
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
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 --.. ...- ..
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.
14. W. I. Patnode and D. F. \Wlcc;:, J. An. Chn. Soc. _, j
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
20. D. Seyferth, T. Wada, and G. Raab, Tetrahedron Letters 22, 20
21. D. Seyferth, D. E. Welch, and G. Rabb, J. Am. Chem. Soc. 84, 4266
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,
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
31. P. Tarrant and D. E. O'Connor, J. Org. Chem. 29, 2012 (1964).
-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
]Docc.bor 19, 1964
2432 4 'S