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Description  |
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FIELD OF THE INVENTION
This invention relates to novel partially fluorinated alkanes having a
tertiary structure and 4 to 9 carbon atoms. These compounds are useful in
a variety of vapor degreasing, cold cleaning, and solvent cleaning
applications including defluxing and dry cleaning.
CROSS-REFERENCE TO RELATED APPLICATION
Commonly assigned concurrently filed patent application U.S. Ser. No.
546,173 claims a method for preparing foam using a partially fluorinated
alkane having four or five carbon atoms and a tertiary structure as a
blowing agent.
BACKGROUND OF THE INVENTION
Cold cleaning is an application where numerous solvents are used. In most
cold cleaning applications, the soiled part is either immersed in the
fluid or wiped with rags or similar objects soaked in solvents and allowed
to air dry.
In cold cleaning applications, the use of the aerosol packaging concept has
long been found to be a convenient and cost effective means of dispensing
solvents. Aerosol products utilize a propellant gas or mixture of
propellant gases, preferably in a liquified gas rather than a compressed
gas state, to generate sufficient pressure to expel the active
ingredients, i.e. Product concentrates such as solvents, from the
container upon opening of the aerosol valve. The propellants may be in
direct contact with the solvent, as in most conventional aerosol systems,
or may be isolated from the solvent, as in barrier-type aerosol systems.
Vapor degreasing and solvent cleaning with fluorocarbon based solvents have
found widespread use in industry for the degreasing and otherwise cleaning
of solid surfaces, especially intricate parts and difficult to remove
soils.
In its simplest form, vapor degreasing or solvent cleaning consists of
exposing a room temperature object to be cleaned to the vapors of a
boiling solvent. Vapors condensing on the object provide clean distilled
solvent to wash away grease or other contamination. Final evaporation of
solvent from the object leaves behind no residue as would be the case
where the object is simply washed in liquid solvent.
For difficult to remove soils where elevated temperature is necessary to
improve the cleaning action of the solvent, or for large volume assembly
line operations where the cleaning of metal parts and assemblies must be
done efficiently and quickly, the conventional operation of a vapor
degreaser consists of immersing the part to be cleaned in a sump of
boiling solvent which removes the bulk of the soil, thereafter immersing
the part in a sump containing freshly distilled solvent near room
temperature, and finally exposing the part to solvent vapors over the
boiling sump which condense on the cleaned part. In addition, the part can
also be sprayed with distilled solvent before final rinsing.
Vapor degreasers suitable in the above-describe operations are well known
in the art. For example, Sherliker et al. in U.S. Pat. No. 3,085,918
disclose such suitable vapor degreasers comprising a boiling sump, a clean
sump, a water separator, and other ancillary equipment.
Chlorofluorocarbon solvents, such as trichlorotrifluoroethane, have
attained widespread use in recent years as effective, nontoxic, and
nonflammable agents useful in degreasing applications and other solvent
cleaning applications. One isomer of trichlorotrifluoroethane is
1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113).
CFC-113 has a boiling point of about 47.degree. C and has been found to
have satisfactory solvent power for greases, oils, waxes and the like. It
has therefore found widespread use for cleaning electric motors,
compressors, heavy metal parts, delicate precision metal parts, printed
circuit boards, gyroscopes, guidance systems, aerospace and missile
hardware, aluminum parts and the like.
Another commonly used solvent is chloroform (known in the art as HCC-20)
which has a boiling point of about 63.degree. C. Perchloroethylene is a
commonly used dry cleaning and vapor degreasing solvent which has a
boiling point of about 121.degree. C. These compounds are disadvantageous
for use as solvents because they are toxic; also, chloroform causes liver
damage when inhaled in excess.
Although chlorine is known to contribute to the solvency capability of a
compound, fully halogenated chlorofluorocarbons and hydrochlorocarbons are
suspected of causing environmental problems in connection with the earth's
Protective ozone layer. Thus, the art is seeking new compounds which do
not contribute to environmental problems but yet provide the solvency
properties of CFC-113. From an environmental standpoint, hydrofluorocarbon
and hydrocarbon Compounds are of interest because they are considered to
be stratospherically safe substitutes for the currently used fully
halogenated chlorofluorocarbons. Mathematical models have substantiated
that hydrofluorocarbons and hydrocarbons will not adversely affect
atmospheric chemistry as not contributing to ozone depletion and to
green-house global warming in comparison to the fully halogenated species.
The problems with hydrofluorocarbons as solvents are that known straight
chain hydrofluorocarbons such as CH.sub.3 (CF.sub.2).sub.4 H and CH.sub.3
CH.sub.2 (CF.sub.2).sub.3 H do not have the solvency power of CFC-113. A
branched hydrofluorocarbon such as CF.sub.3 CH(CF.sub.3).sub.2 is
nonflammable but has a boiling point of about 15.degree. C. and thus, is
not liquid at room temperature at atmospheric pressure and is not useful
in cold cleaning applications. The problems with hydrocarbons as solvents
are that branched hydrocarbons such as isobutane are flammable and have
such low boiling points that they are not liquid at room temperature and
are not useful in cold cleaning applications. The problem with alkanols as
solvents is that branched alkanols such as isobutanol are flammable.
It is an object of this invention to provide novel hydrofluorocarbon
compounds which are liquid at room temperature and which are useful as
solvents for use in vapor degreasing, cold cleaning, and other solvent
cleaning applications including defluxing applications and dry cleaning.
Another object of the invention is to provide novel environmentally
acceptable solvents for use in the aforementioned applications.
Other objects and advantages of the invention will become apparent from the
following description.
DETAILED DESCRIPTION OF THE INVENTION
We have found a novel class of hydrofluorocarbons which we believe have
good solvency characteristics. The present novel compounds are of the
Formula:
##STR2##
wherein each R is the same or different and is selected from the group
consisting of CF.sub.3, CHF.sub.2, CH.sub.2 F, and CH.sub.3 CF.sub.2 --,
and R' is an alkyl or fluoroalkyl group having 1 to 6 carbon atoms with
the proviso that when each R is CF.sub.3, R' is not CF.sub.3
(CF.sub.2).sub.2 --, CF.sub.2 --, or CF.sub.3.
Because C in the Formula above has three alkyl groups thereon, these novel
compounds have a tertiary structure. We believe that this tertiary
structure provides good solvency power. The R component of the Formula
above helps to make the hydrogen of the Formula above more acidic and
therefore, more polar; thus, when the present compounds are used as
solvents, the compounds have good solvency power for polar contaminants
such as polyols and amines. The R' component of the Formula above helps to
make the compounds nonpolar; thus, when the present compounds are used as
solvents, the compounds also have good solvency power for nonpolar
contaminants including hydrocarbons such as mineral oil. We also believe
that these novel compounds have boiling points in the range of about 35 to
about 80.degree. C. which are comparable to those of CFC-113 and
chloroform.
Preferably, R' in the Formula above is selected from the group consisting
of CF.sub.3, CHF.sub.2, CH.sub.2 F, CH.sub.3, CF.sub.3 (CF.sub.2)n--,
CF.sub.3 CF.sub.2 CHF--, CF.sub.3 CF.sub.2 CH.sub.2 --, CF.sub.3 (CHF)n--,
CF.sub.3 CHFCF.sub.2 --, CF.sub.3 CHFCH.sub.2 --, CF.sub.3
(CH.sub.2).sub.n --, CF.sub.3 CH.sub.2 CF.sub.2 --, CF.sub.3 CH.sub.2
CHF--, CHF.sub.2 (CF.sub.2).sub.n --, CHF.sub.2 CHFCF.sub.2 --, CHF.sub.2
CHFCH.sub.2 --, CHF.sub.2 (CHF).sub.n --, CHG.sub.2 CHFCF.sub.2 --,
CHG.sub.2 CHFCH.sub.2 --, CHF.sub.2 (CH.sub.2).sub.n --, CHF.sub.2
CH.sub.2 CF.sub.2 --, CHF.sub.2 CH.sub.2 CHF--, CH.sub.2 F(CF.sub.2).sub.n
--, CH.sub.2 FCF.sub.2 CHF--, CH.sub.2 FCF.sub.2 CH.sub.2 --, CH.sub.2
F(CHF).sub.n --, CH.sub.2 FCHFCF.sub.2 --, CH.sub.2 FCHFCH.sub.2 --,
CH.sub.2 F(CH.sub.2).sub.n --, CH.sub.2 FCH.sub.2 CF.sub.2 --, CH.sub.2
FCH.sub.2 CHF--, CH.sub.3 (CF.sub.2).sub.n --, CH.sub.3 CF.sub.2 CHF--,
CH.sub.3 CF.sub.2 CH.sub.2 --, CH.sub.3 (CHF).sub.n --, CH.sub.3
CHFCF.sub.2 --, CH.sub.3 CHFCH.sub.2 --, and CH.sub.3 (CH.sub.2).sub.m
(CF.sub.2).sub.n, and m is 1 to 3, and n is 1 or 2 with the proviso that
when each R is CF.sub.3, R' is not CF.sub.3, CF.sub.3 CF.sub.2 --, or
CF.sub.3 (CF.sub.2).sub.2 --.
In the Formula above, when one R is CF.sub.3, the other R is CHG.sub.2, and
R' is CH.sub.3, the compound is 2-methyl-1,1,1,3,3-pentafluoropropane.
When one R is CF.sub.3, the other R is CH.sub.2 F, and R' is CH.sub.3, the
compound is 2-methyl-1,1,1,3-tetrafluoropropane. When one R is CF.sub.3,
the other R is CH.sub.2 F, and R' is CHG.sub.2 CHF--, the compound is
2-fluoromethyl-1,1,1,3,4,4-hexafluorobutane. When one R is CF.sub.3, the
other R is CH.sub.3 CF.sub.2 --, and R' is CH.sub.3, the compound is
2-methyl-1,1,1,3,3-pentafluorobutane. When one R is CHG.sub.2, the other R
is CH.sub.2 F, and R' is CH.sub.3, the compound is
2-methyl-1,1,3-trifluoropropane. When one R is CHG.sub.2, the other R is
CH.sub.2 F, and R' is CHF.sub.2 CH.sub.2 --, the compound is
2-fluoromethyl-1,1,4,4-tetrafluorobutane.
The present novel compounds may be prepared by adapting known methods for
preparing hydrofluorocarbons. For example,
2-methyl-1,1,1,3,3-pentafluoropropane may be prepared by reacting
commercially available 1,1,1-trifluoro-2-propanone with CF.sub.2 carbane
to form 2-trifluoromethyl-1,1-difluoro-1-propene which may then be
hydrogenated to form 2-methyl-1,1,1,3,3-pentafluoropropane.
As another example, 2-methyl-1,1,1,3-tetrafluoropropane may be prepared by
reacting commercially available methacrylic acid with hydrogen fluoride to
form 2-methyl-3-fluoropropanoic acid which may then be fluorinated to form
2-methyl-1,1,1,3-tetrafluoropropane.
As another example, 2-fluoromethyl-1,1,1,3,4,4-hexafluorobutane may be
prepared by fluorinating commercially available 3-chloropropionic acid to
form 1,1,1,3-tetrafluoropropane which may then be reacted with CHG.sub.2
CF carbene to form 2-fluoromethyl-1,1,1,3,4,4-hexafluorobutane.
As another example, 2-methyl-1,1,1,3,3-pentafluorobutane may be prepared by
fluorinating commercially available 2-methyl-1-buten-3-yne to form
3-methyl-1,2,3,4-tetrafluoro-1-butene which may then be reacted with
hydrogen fluoride to form 2-methyl-1,2,3,3,4-pentafluorobutane. The
2-methyl-1,2,3,3,4-pentafluorobutane may then be dehalogenated to form
3-methyl-2,3,4-trifluoro-1-butene which may then be reacted with hydrogen
fluoride to form 2-methyl-1,2,3,3-tetrafluorobutane. The
2-methyl-1,2,3,3-tetrafluorobutane may then be dehalogenated to form
2-methyl-1,3,3-trifluoro-1-butene which may then be fluorinated to form
2-methyl-1,1,2,3,3-pentafluorobutane. The
2-methyl-1,1,2,3,3-pentafluorobutane may then be dehydrohalogenated to
form 2-methyl-1,1,3,3-tetrafluoro-1-butene which may then be reacted with
hydrogen fluoride to form 2-methyl-1,1,1,3,3-pentafluorobutane. The
boiling point of 2-methyl-1,1,1,3,3-pentafluorobutane is calculated to be
about 60.degree. C. Because of its boiling point,
2-methyl-1,1,1,3,3-pentafluorobutane would be particularly useful as a
solvent substitute for chloroform.
For example, 2-methyl-1,1,3-trifluoropropane may be prepared by reacting
commercially available fluoroacetone with a CF.sub.2 carbene to form
2-fluoromethyl-1,1,3-trifluoro-1-propene which may then be hydrogenated to
form 2-methyl-1,1,3-trifluoropropane.
As another example, 2-fluoromethyl-1,1,4,4-tetrafluorobutane may be
prepared by oxidizing commercially available 3-fluoro-1,2-propanediol to
form a product which may then be reacted with CF.sub.2 carbene to form
2-fluoromethyl-1,1,4,4-tetrafluoro-1,3-butadiene which may then be
hydrogenated to form 2-fluoromethyl-1,1,4,4-tetrafluorobutane.
Preferably, each R in the formula above is the same. When each R is
CHG.sub.2 and R' is CF.sub.3, the compound is
2-difluoromethyl-1,1,1,3,3-pentafluoropropane. When each R is CHG.sub.2
and R' is CHG.sub.2, the compound is
2-difluoromethyl-1,1,3,3-tetrafluoropropane. When each R is CHG.sub.2 and
R' is CH.sub.2 F, the compound is
2-fluoromethyl-1,1,3,3-tetrafluoropropane. When each R is CHF.sub.2 and R'
is CH.sub.3, the compound is 2-methyl-1,1,3,3-tetrafluoropropane. When
each R is CH.sub.2 F and R' is CHF.sub.2, the compound is
2-fluoromethyl-1,1,3-trifluoropropane. When each R is CH.sub.2 F and R' is
CH.sub.2 F, the compound is 2-fluoromethyl-1,3-difluoropropane. When each
R is CH.sub.3 CF.sub.2 -- and R' is CF.sub.3, the compound is
3-trifluoromethyl-2,2,4,4-tetrafluoropentane.
As another preparation example,
2-difluoromethyl-1,1,1,3,3-pentafluoropropane may be prepared by
fluorinating commercially available 1,1,1,3,3-pentachloro-2-propanone to
form 1,1,1,3,3-pentafluoro-2-propanone which may then be reacted with
CF.sub.2 carbene to form 2-difluoromethyl-1,1,3,3,3-tetrafluoro-1-propene.
The 2-difluoromethyl-1,1,3,3,3-tetrafluoro-1-propene may then be
hydrogenated to form 2-difluoromethyl-1,1,1,3,3-pentafluoropropane.
As another example, the 2-difluoromethyl-1,1,3,3-tetrafluoropropane may be
prepared by fluorinating commercially available
1,1,3-trichloro-2-propanone to form 1,1,3-trifluoro-2-propanone which may
then be reacted with CF.sub.2 carbene to form
2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene. The
2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene may then be hydrogenated to
form 2-fluoromethyl-1,1,3,3-tetrafluoropropane. The
2-fluoromethyl-1,1,3,3-tetrafluoropropane may then be dehydrogenated to
form 2-difluoromethyl-1,3,3-trifluoro-1-propene which may then be reacted
with hydrogen fluoride to form
2-difluoromethyl-1,1,3,3-tetrafluoropropane.
As another example, 2-fluoromethyl-1,1,3,3-tetrafluoropropane may be
prepared by fluorinating commercially available
1,1,3-trichloro-2-propanone to form 1,1,3-trifluoro-2-Propanone which may
then be reacted with CF.sub.2 carbene to form
2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene. The
2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene may then be hydrogenated to
form 2-fluoromethyl-1,1,3,3-tetrafluoropropane.
As another example, 2-methyl-1,1,3,3-tetrafluoropropane may be prepared by
fluorinating commercially available 1,1-dichloro-2-propanone to form
1,1-difluoro-2-propanone which may then be reacted with CF.sub.2 carbene
to form 2-methyl-1,1,3,3-tetrafluoro-1-propene. The
2-methyl-1,1,3,3-tetrafluoro-1-propene may then be hydrogenated to form
2-methyl-1,1,3,3-tetrafluoropropane.
As another example, the 2-fluoromethyl-1,1,3-trifluoropropane may be
prepared by oxidizing commercially available 1,3-difluoro-2-propanol to
1,3-difluoro-2-propanone which may then be reacted with a CF.sub.2 carbene
to form 2-fluoromethyl-1,1,3-trifluoro-1-propene. The
2-fluoromethyl-1,1,3-trifluoro-1-propene may then be hydrogenated to form
2-fluoromethyl-1,1,3-trifluoropropane.
As another example, the 2-fluoromethyl-1,3-difluoropropane may be prepared
by oxidizing commercially available 1,3-difluoro-2-propanol to
1,3-difluoro-2-propanone which may then be reacted with a CF.sub.2 carbene
to form 2-fluoromethyl-1,1,3-trifluoro-1-propene. The
2-fluoromethyl-1,1,3-trifluoro-1-propene may then be hydrogenated to form
2-fluoromethyl-1,1,3-trifluoropropane. The
2-fluoromethyl-1,1,3-trifluoropropane may then be dehydrohalogenated to
form 2-fluoromethyl-1,3-difluoro-1-propene which may then be hydrogenated
to form 2-fluoromethyl-1,3-difluoropropane.
As another example, the 3-trifluoromethyl-2,2,4,4-tetrafluoropentane may be
prepared by fluorinating commercially available 2,4-pentanedione to form
2,2,4,4-tetrafluoropentane which may then be dehydrohalogenated to form
2,4,4-trifluoro-2-pentene. The 2,4,4-trifluoro-2-pentene may then be
reacted with CF.sub.3 to form
3-trifluoromethyl-2,2,4,4-tetrafluoropentane.
The boiling point of 2-difluoromethyl-1,1,3,3-tetrafluoropropane is
calculated to be about 61.degree. C. while the boiling point of
2-fluoromethyl-1,3-difluoropropane is calculated to be about 51.degree. C.
The boiling point of 3-trifluoromethyl-2,2,4,4-tetrafluoropentane is
calculated to be about 52.degree. C.
Because of its boiling point, 2-difluoromethyl-1,1,3,3-tetrafluoropropane
would be particularly useful as a solvent substitute for chloroform.
Because of their boiling points, 2-fluoromethyl-1,3-difluoropropane and
3-trifluoromethyl-2,2,4,4-tetrafluoropentane would be particularly useful
as solvent substitutes for CFC-113.
More preferably, each R in the Formula above is CF.sub.3. When R' is
CF.sub.3 CF.sub.2 CHF--, the compound is
2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoropentane. To prepare
2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoropentane, commercially
available hexafluoropropene may be oligomerized with commercially
available trimethylamine in a dipolar aprotic solvent such as commercially
available tetrahydrofuran to provide (CF.sub.3).sub.2 C:CFCF.sub.2
CF.sub.3 as taught by W. Brunskill et al., "Anionic Oligomerisation of
Hexafluoropropene: Fission of a Carbon-Carbon Bond by Fluoride Ion",
Chemical Communications, 1444 (1970); the (CF.sub.3).sub.2 C:CFCF.sub.2
CF.sub.3 may then be hydrogenated to form
2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoropentane.
Most preferably, each R is CF.sub.3 and R' is selected from the group
consisting of CHF.sub.2, CH.sub.3, CF.sub.3 CHF--, CF.sub.3 CH.sub.2 --,
CHF.sub.2 CH.sub.2 --CH.sub.3 CF.sub.2 --, CH.sub.3 (CF.sub.2).sub.2 --,
CH.sub.3 CH.sub.2 CF.sub.2 --, and CH.sub.3 CH.sub.2 CF.sub.2 CF.sub.2 --.
The names of the preceding preferred hydrofluorocarbons are
2-difluoromethyl-1,1,1,3,3,3-hexafluoropropane;
2-methyl-1,1,1,3,3,3-hexafluoropropane;
2-trifluoromethyl-1,1,1,3,4,4,4-heptafluorobutane;
2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane;
2-trifluoromethyl-1,1,1,4,4-pentafluorobutane;
2-trifluoromethyl-1,1,1,3,3-pentafluorobutane;
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluoropentane:
2-trifluoromethyl-1,1,1,3,3-pentafluoropentane; and
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluorohexane.
The present novel compounds may be prepared by adapting known methods for
preparing hydrofluorocarbons. For example,
2-difluoromethyl-1,1,1,3,3,3-hexafluoropropane may be prepared by treating
commercially available hexafluoropropene with hydrogen fluoride as taught
by commonly assigned U.K. Patent 902,590 to form
1,1,1,2,3,3,3-hexafluoropropane. The 1,1,1,2,3,3,3-hexafluoropropane may
then be heated at 475-700.degree. C. in the presence of activated carbon
as taught by commonly assigned U.S. Pat. No. 2,981,763 which is
incorporated herein by reference to form
2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane or nonafluoroisobutane.
The nonafluoroisobutane may then be treated with commercially available
benzoyl chloride in the presence of commercially available triethylamine
as taught by B. L. Dyatkin et al., "The Perfluoro-t-butyl Anion in the
Synthesis of Organofluorine Compounds", Russian Chemical Reviews 45(7),
607 (1976) to form perfluoroisobutene. The perfluoroisobutene may then by
hydrogenated to form 2-difluoromethyl-1,1,1,3,3,3-hexafluoropropane.
As another example, 2-methyl-1,1,1,3,3,3-hexafluoropropane may be prepared
by reacting commercially available hexafluoropropene with elemental sulfur
and commercially available potassium fluoride in commercially available
dimethylformamide under substantially atmospheric pressure and at
temperatures between 25-100.degree. C. as taught by commonly assigned U.S.
Pat. No. 4,326,068 which is incorporated herein by reference to form
hexafluorothioacetone dimer. The hexafluorothioacetone dimer may then be
reacted with commercially available formaldehyde as taught by commonly
assigned U.S. Pat. No. 4,367,349 which is incorporated herein by reference
to form hexafluoroisobutylene. The hexafluoroisobutylene may then be
hydrogenated to form 2-methyl-1,1,1,3,3,3-hexafluoropropane.
As another example, 2-trifluoromethyl-1,1,1,3,4,4,4-heptafluorobutane may
be prepared by reacting commercially available 1,1-difluoroethylene
according to the procedure of George L. Fleming et al., "Addition of Free
Radicals to Unsaturated Systems. Part XX. The Direction of Radical
Addition of Heptafluoro-2-iodopropane to Vinyl Fluoride,
Trifluoroethylene, and Hexafluoropropene", J. C. S. Perkin I, 574 (1973)
to form a product which may then be fluorinated to form
2-trifluoromethyl-1,1,1,2,3,4,4,4-octafluorobutane. The
2-trifluoromethyl-1,1,1,2,3,4,4,4-octafluorobutane may then be
dehydrohalogenated and then hydrogenated to form
2-trifluoromethyl-1,1,1,3,4,4,4-heptafluorobutane.
As another example, 2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane may be
prepared by reacting commercially available 1,1-difluoroethylene according
to the procedure of George L. Fleming et al., supra, to form a product
which may then be reacted with hydrogen fluoride to form
2-trifluoromethyl-1,1,1,2,4,4,4-hexafluorobutane which may then be
dehydrohalogenated and then hydrogenated to form
2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane.
As another example, 2-trifluoromethyl-1,1,1,4,4-pentafluorobutane may be
prepared by reacting commercially available 1,1-difluoroethylene according
to the procedure of George L. Fleming et al., supra, to form a product
which may then be hydrogenated to form
2-trifluoromethyl-1,1,1,2,4,4-hexafluorobutane which may then be
dehydrohalogenated and then hydrogenated to form
2-trifluoromethyl-1,1,1,4,4-pentafluorobutane.
As another example, 2-trifluoromethyl-1,1,1,3,3-pentafluorobutane may be
prepared by fluorinating commercially available 2-butanone to form
2,2-difluorobutane which may then be dehydrogenated to form
3,3-difluoro-1-butene. CF.sub.3 may then be added to the
3,3-difluoro-1-butene to form 2-trifluoromethyl-1,3,3-trifluorobutane
which may then be dehydrogenated to form
2-trifluoromethyl-1,3,3-trifluoro-1-butene. The
2-trifluoromethyl-1,3,3-trifluoro-1-butene may then be reacted with
hydrogen fluoride to form 2-difluoromethyl-1,1,1,3,3,3-hexafluorobutane
which may then be dehydrogenated to form
2-trifluoromethyl-1,1,3,3-tetrafluoro-1-butene which may then be reacted
with hydrogen fluoride to form
2-trifluoromethyl-1,1,1,3,3-pentafluorobutane.
As another example, 2-trifluoromethyl-1,1,1,3,3,4,4-heptafluoropentane may
be prepared by fluorinating commercially available 2,3-pentanedione to
form 2,2,3,3-tetrafluoropentane which may then be dehydrogenated to form
3,3,4,4-tetrafluoro-1-pentene. CF.sub.3 may then be added to the
3,3,4,4-tetrafluoro-1-pentene to form
2-trifluoromethyl-1,3,3,4,4-pentafluoropentane which may then be
dehydrogenated to form 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene.
The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene may then be reacted
with hydrogen fluoride to form
2-trifluoromethyl-1,1,3,3,4,4-hexafluoropentane which may then be
dehydrogenated to form 2-trifluoromethyl-1,1,3,3,4,4-hexafluoro-1-pentene
which may then be reacted with hydrogen fluoride to form
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluoropentane.
As another example, 2-trifluoromethyl-1,1,1,3,3-pentafluoropentane may be
prepared by fluorinating 3-pentanone to form 3,3-difluoropentane which may
then be dehydrogenated to form 3,3-difluoro-1-pentene. CF.sub.3 may then
be reacted with the 3,3-difluoro-1-pentene to form
2-trifluoromethyl-1,3,3-trifluoropentane which may then be dehydrogenated
to form 2-trifluoromethyl-1,3,3-trifluoro-1-pentene. The
2-trifluoromethyl-1,3,3-trifluoro-1-pentene may then be reacted with
hydrogen fluoride to form 2-trifluoromethyl-1,1,3,3-tetrafluoropentane
which may then be dehydrogenated to form
2-trifluoromethyl-1,1,3,3-tetrafluoro-1-pentene which may then be reacted
with hydrogen fluoride to form
2-trifluoromethyl-1,1,1,3,3-pentafluoropentane.
As another example, 2-trifluoromethyl-1,1,1,3,3,4,4-heptafluorohexane may
be prepared by fluorinating commercially available 3,4-hexanedione to form
3,3,4,4-tetrafluorohexane which may then be dehydrogenated to form
3,3,4,4-tetrafluoro-1-hexene. CF.sub.3 may then be added to the
3,3,4,4-tetrafluoro-1-hexene to form
2-trifluoromethyl-1,3,3,4,4-pentafluorohexane which may then be
dehydrogenated to form 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene.
The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene may then be reacted
with hydrogen fluoride to form
2-trifluoromethyl-1,1,3,3,4,4-hexafluorohexane which may then be
dehydrogenated to form 2-trifluoromethyl-1,1,3,3,4,4-hexafluoro-1-hexene
which may then be reacted with hydrogen fluoride to form
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluorohexane.
The boiling point of 2-difluoromethyl-1,1,1,3,3,3-hexafluoropropane is
calculated to be about 38.degree. C while the boiling point of
2-methyl-1,1,1,3,3,3-hexafluoropropane is calculated to be about
30.degree. C. The boiling point of
2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane is calculated to be about
75.degree. C. The boiling point of
2-trifluoromethyl-1,1,1,3,3-pentafluoropentane is calculated to be about
38.degree. C. while the boiling point of
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluorohexane is calculated to be
about 55.degree. C.
The present novel compounds are useful as solvents in a variety of vapor
degreasing, cold cleaning, and solvent cleaning applications including
defluxing and dry cleaning. Because of their boiling points,
2-difluoromethyl-1,1,1,3,3,3-hexafluoropropane,
2-methyl-1,1,1,3,3,3-hexafluoropropane,
2-trifluoromethyl-1,1,1,3,3-pentafluoropentane, and
2-trifluoromethyl-1,1,1,3,3,4,4-heptafluorohexane would be useful as
solvent substitutes for CFC-113. Because of its boiling point,
2-trifluoromethyl-1,1,1,4,4,4-hexafluorobutane would be particularly
useful as a solvent substitute for chloroform and perchloroethylene.
The present invention also provides a method of cleaning a solid surface
which comprises treating the surface with a compound having the Formula:
##STR3##
wherein each R is the same or different and is selected from the group
consisting of CF.sub.3, CHF.sub.2, CH.sub.2 F, and CH.sub.3 CF.sub.2, and
R' is an alkyl or fluoroalkyl group having 1 to 6 carbon atoms.
Preferably, R' in the Formula above is selected from the group consisting
of CF.sub.3, CHF.sub.2, CH.sub.2 F, CH.sub.3, CF.sub.3 (CF.sub.2).sub.n
--, CF.sub.3 CF.sub.3 CF.sub.2 CHF--, CF.sub.3 CF.sub.2 CH.sub.2 --,
CF.sub.3 (CHF).sub.n --, CF.sub.3 CHFCF.sub.2 --, CF.sub.3 CHFCH.sub.2 --,
CF.sub.3 (CH.sub.2).sub.n --, CF.sub.3 CH.sub.2 CF.sub.2 --, CF.sub.3
CH.sub.2 CHF--, CHF.sub.2 (CF.sub.2).sub.n --, CHF.sub.2 CF.sub.2 CHF--,
CHF.sub.2 CF.sub.2 CH.sub.2 --, CHF.sub.2 (CHF).sub.n --, CHF.sub.2
CHFCF.sub.2 --, CHF.sub.2 CHFCH.sub.2 --, CHF.sub.2 (CH.sub.2).sub.n --,
CHF.sub.2 CH.sub.2 CF.sub.2 --, CHF.sub.2 CH.sub.2 CHF--, CH.sub.2
F(CF.sub.2).sub.n --, CH.sub.2 FCF.sub.2 CHF--, CH.sub.2 FCF.sub.2
CH.sub.2 --, CH.sub.2 F(CHF).sub.n --, CH.sub.2 FCHFCF.sub.2 --, CH.sub.2
FCHFCH.sub.2 --, CH.sub.2 F(CH.sub.2).sub.n -- , CH.sub.2 FCH.sub.2
CF.sub.2 --, CH.sub.2 FCH.sub.2 CHF--, CH.sub.3 (CF.sub.2).sub.n --,
CH.sub.3 CF.sub.2 CHF--, CH.sub.3 CF.sub.2 CH.sub.2 --, CH.sub.3
(CHF).sub.n --, CH.sub.3 CHFCF.sub.2 --, CH.sub.3 CHFCH.sub.2 --, and
CH.sub.3 (CF.sub.2).sub.m (CF.sub.2).sub.n, and m is 1 to 3, and n is 1 or
2.
Preferably, each R in the Formula above is the same and more preferably,
each R in the Formula above is CF.sub.3
When R' is CF.sub.3 CF.sub.2 CF.sub.2 --, the compound is
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane. To prepare
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane, any method known
in the art may be used. For example, commercially available
hexafluoropropene may be oligomerized with commercially available
trimethylamine in a dipolar aprotic solvent such as commercially available
tetrahydrofuran to provide (CF.sub.3).sub.2 C:CFCF.sub.2 CF.sub.3 which is
then reacted with commercially available hydrogen fluoride to yield
2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane as taught by W.
Brunskill et al., "Anionic Oligomerisation of Hexafluoropropene: Fission
of a Carbon-Carbon Bond by Fluoride Ion", Chemical Communications, 1444
(1970).
When R' is CF.sub.3 CF.sub.2 --, the compound is 2-trifluoromethyl-
1,1,1,3,3,4,4,4-octafluorobutane. To prepare
2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane, any method known in
the art may be used. For example,
2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane may be prepared by
reacting caesium fluoride and perfluoro-3-methylbutlene in moist sulpholan
as taught by Robert N. Haszeldine et al., "Fluoro-olefin Chemistry. Part
11. Some Reactions of Perfluoro-3-methylbut-1-ene under Ionic and
Free-radical Conditions", J. Chem. Soc. 565 (1979).
When R' is CF.sub.3, the compound is
2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane To prepare
2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane, any method known in the
art may be used. For example, commercially available hexafluoropropene may
be reacted with hydrogen fluoride to form 1,1,1,2,3,3,3-heptafluoropropane
which may then be heated at about 475-700.degree. C. in the presence of
activated carbon to form 2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane
as taught by commonly assigned U.S. Pat. No. 2,981,763 which is
incorporated herein by reference.
The boiling point of 2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane is
calculated to be about 47.degree. C. Because of its boiling Point,
2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane would be particularly
useful as a solvent substitute for CFC-113.
In the process embodiment of the invention, the compositions may be used to
clean solid surfaces by treating the surfaces with the compounds in any
manner well known to the art such as by dipping or spraying or use of
conventional degreasing apparatus.
When the novel compounds are used to clean solid surfaces by spraying the
surfaces with the compounds, preferably, the novel compounds are sprayed
onto the surfaces by using a propellant. Preferably, the propellant is
selected from the group consisting of hydrochlorofluorocarbon,
hydrofluorocarbon, and mixtures thereof. Useful hydrochlorofluorocarbon
propellants include dichlorofluoromethane (known in the art as HCFC-21),
chlorodifluoromethane (known in the art as HCFC-22),
1,1-dichloro-2,2-difluoroethane (known in the art as HCFC-132a),
1-chloro-2,2,2-trifluoroethane (known in the art as HCFC-133), and
1-chloro-1,1-difluoroethane (known in the art as HCFC-142b); commercially
available HCFC-21, HCFC-22, and HCFC-142b may be used in the present
invention. Useful hydrofluorocarbon propellants include trifluoromethane
(known in the art as HFC-23), 1,1,1,2-tetrafluoroethane (known in the art
as HFC-134a), and 1,1-difluoroethane (known in the art as HFC-152a);
commercially available HFC-23 and HFC-152a may be used in the present
invention. Until HFC-134a becomes available in commercial quantities,
HFC-134a may be made by a known method such as that disclosed by U.S. Pat.
No. 4,851,595. Preferred propellants include chlorodifluoromethane and
1,1,1,2-tetrafluoroethane.
The present partially fluorinated alkanes may also be used as blowing
agents for preparing foam as disclosed in commonly assigned concurrently
filed patent application U.S. Ser. No. 546,173, which is incorporated
herein by reference.
The present invention is more fully illustrated by the following
non-limiting Examples.
EXAMPLES 1-540
For each example, the novel compound of the Formula above having the R and
R' groups as indicated in Table I below is made.
TABLE I
______________________________________
Example R R'
______________________________________
1 CF.sub.3, CHF.sub.2
CF.sub.3
2 CF.sub.3, CHF.sub.2
CHF.sub.2
3 CF.sub.3, CHF.sub.2
CH.sub.2 F
4 CF.sub.3, CHF.sub.2
CH.sub.3
5 CF.sub.3, CHF.sub.2
CF.sub.3 CF.sub.2
6 CF.sub.3, CHF.sub.2
CF.sub.3 (CF.sub.2).sub.2
7 CF.sub.3, CHF.sub.2
CF.sub.3 CF.sub.2 CHF
8 CF.sub.3, CHF.sub.2
CF.sub.3 CF.sub.2 CH.sub.2
9 CF.sub.3, CHF.sub.2
CF.sub.3 CHF
10 CF.sub.3, CHF.sub.2
CF.sub.3 (CHF).sub.2
11 CF.sub.3, CHF.sub.2
CF.sub.3 CHFCF.sub.2
12 CF.sub.3, CHF.sub.2
CF.sub.3 CHFCH.sub.2
13 CF.sub.3, CHF.sub.2
CF.sub.3 CH.sub.2
14 CF.sub.3, CHF.sub.2
CF.sub.3 (CH.sub.2).sub.2
15 CF.sub.3, CHF.sub.2
CF.sub.3 CH.sub.2 CF.sub.2
16 CF.sub.3, CHF.sub.2
CF.sub.3 CH.sub.2 CHF
17 CF.sub.3, CHF.sub.2
CHF.sub. 2 CF.sub.2
18 CF.sub.3, CHF.sub.2
CHF.sub.2 (CF.sub.2).sub.2
19 CF.sub.3, CHF.sub.2
CHF.sub.2 CF.sub.2 CHF
20 CF.sub.3, CHF.sub.2
CHF.sub.2 CF.sub.2 CH.sub.2
21 CF.sub.3, CHF.sub.2
CHF.sub.2 CHF
22 CF.sub.3, CHF.sub.2
CHF.sub.2 (CHF).sub.2
23 CF.sub.3, CHF.sub.2
CHF.sub.2 CHFCF.sub.2
24 CF.sub.3, CHF.sub.2
CHF.sub.2 CHFCH.sub.2
25 CF.sub.3, CHF.sub.2
CHF.sub.2 CH.sub.2
26 CF.sub.3, CHF.sub.2
CHF.sub.2 (CH.sub.2).sub.2
27 CF.sub.3, CHF.sub.2
CHF.sub.2 CH.sub.2 CF.sub.2
28 CF.sub.3, CHF.sub.2
CHF.sub.2 CH.sub.2 CHF
29 CF.sub.3, CHF.sub.2
CH.sub.2 FCF.sub.2
30 CF.sub.3, CHF.sub.2
CH.sub.2 F(CF.sub.2).sub.2
31 CF.sub.3, CHF.sub.2
CH.sub.2 FCF.sub.2 CHF
32 CF.sub.3, CHF.sub.2
CH.sub.2 FCF.sub.2 CH.sub.2
33 CF.sub.3, CHF.sub.2
CH.sub.2 FCHF
34 CF.sub.3, CHF.sub.2
CH.sub. 2 F(CHF).sub.2
35 CF.sub.3, CHF.sub.2
CH.sub.2 FCHFCF.sub.2
36 CF.sub.3, CHF.sub.2
CH.sub.2 FCHFCH.sub.2
37 CF.sub.3, CHF.sub.2
CH.sub.2 FCH.sub.2
38 CF.sub.3, CHF.sub.2
CH.sub.2 F(CH.sub.2).sub.2
39 CF.sub.3, CHF.sub.2
CH.sub.2 FCH.sub.2 CF.sub.2
40 CF.sub.3, CHF.sub.2
CH.sub.2 FCH.sub.2 CHF
41 CF.sub.3, CHF.sub.2
CH.sub.3 CF.sub.2
42 CF.sub.3, CHF.sub.2
CH.sub.3 (CF.sub.2).sub.2
43 CF.sub.3, CHF.sub.2
CH.sub.3 CF.sub.2 CHF
44 CF.sub.3, CHF.sub.2
CH.sub.3 CF.sub.2 CH.sub.2
45 CF.sub.3, CHF.sub.2
CH.sub.3 CHF
46 CF.sub.3, CHF.sub.2
CH.sub.3 (CHF).sub.2
47 CF.sub.3, CHF.sub.2
CH.sub.3 CHFCF.sub.2
48 CF.sub.3, CHF.sub.2
CH.sub.3 CHFCH.sub.2
49 CF.sub.3, CHF.sub.2
CH.sub.3 CH.sub.2 CF.sub.2
50 CF.sub.3, CHF.sub.2
CH.sub.3 CH.sub.2 (CF.sub.2).sub.2
51 CF.sub.3, CHF.sub. 2
CH.sub.3 (CH.sub.2).sub.2 CF.sub.2
52 CF.sub.3, CHF.sub.2
CH.sub.3 (CH.sub.2).sub.2 (CF.sub.2).sub.2
53 CF.sub.3, CHF.sub.2
CH.sub.3 (CH.sub.2).sub.3 CF.sub.2
54 CF.sub.3, CHF.sub.2
CH.sub.3 (CH.sub.2).sub.3 (CF.sub.2).sub.2
55 CF.sub.3, CH.sub.2 F
CF.sub.3
56 CF.sub.3, CH.sub.2 F
CHF.sub.2
57 CF.sub.3, CH.sub.2 F
CH.sub.2 F
58 CF.sub.3, CH.sub.2 F
CH.sub.3
59 CF.sub.3, CH.sub.2 F
CF.sub.3 CF.sub.2
60 CF.sub.3, CH.sub.2 F
CF.sub.3 (CF.sub.2).sub.2
61 CF.sub.3, CH.sub.2 F
CF.sub.3 CF.sub.2 CHF
62 CF.sub.3, CH.sub.2 F
CF.sub.3 CF.sub.2 CH.sub.2
63 CF.sub.3, CH.sub.2 F
CF.sub.3 CHF
64 CF.sub.3, CH.sub.2 F
CF.sub.3 (CHF).sub.2
65 CF.sub.3, CH.sub.2 F
CF.sub.3 CHFCF.sub.2
66 CF.sub.3, CH.sub.2 F
CF.sub.3 CHFCH.sub.2
67 CF.sub.3, CH.sub.2 F
CF.sub.3 CH.sub.2
68 CF.sub.3, CH.sub.2 F
CF.sub.3 (CH.sub.2).sub.2
69 CF.sub.3, CH.sub.2 F
CF.sub.3 CH.sub.2 CF.sub.2
70 CF.sub.3, CH.sub.2 F
CF.sub.3 CH.sub.2 CHF
71 CF.sub.3, CH.sub.2 F
CHF.sub.2 CF.sub.2
72 CF.sub.3, CH.sub.2 F
CHF.sub.2 (CF.sub.2).sub.2
73 CF.sub.3, CH.sub.2 F
CHF.sub.2 CF.sub.2 CHF
74 CF.sub.3, CH.sub.2 F
CHF.sub.2 CF.sub.2 CH.sub.2
75 CF.sub.3, CH.sub.2 F
CHF.sub.2 CHF
76 CF.sub.3, CH.sub.2 F
CHF.sub.2 (CHF).sub.2
77 CF.sub.3, CH.sub.2 F
CHF.sub.2 CHFCF.sub.2
78 CF.sub.3, CH.sub.2 F
CHF.sub.2 CHFCH.sub.2
79 CF.sub.3, CH.sub.2 F
CHF.sub.2 CH.sub.2
80 CF.sub.3, CH.sub.2 F
CHF.sub.2 (CH.sub.2).sub.2
81 CF.sub.3, CH.sub.2 F
CHF.sub.2 CH.sub.2 CF.sub.2
82 CF.sub.3, CH.sub.2 F
CHF.sub.2 CH.sub.2 CHF
83 CF.sub.3, CH.sub.2 F
CH.sub.2 FCF.sub.2
84 CF.sub.3, CH.sub.2 F
CH.sub.2 F(CF.sub.2).sub.2
85 CF.sub.3, CH.sub.2 F
CH.sub.2 FCF.sub.2 CHF
86 CF.sub.3, CH.sub.2 F
CH.sub.2 FCF.sub.2 CH.sub.2
87 CF.sub.3, CH.sub.2 F
CH.sub.2 FCHF
88 CF.sub.3, CH.sub.2 F
CH.sub.2 F(CHF).sub.2
89 CF.sub.3, CH.sub.2 F
CH.sub.2 FCHFCF.sub.2
90 CF.sub.3, CH.sub.2 F
CH.sub.2 FCHFCH.sub.2
91 CF.sub.3, CH.sub.2 F
CH.sub.2 FCH.sub.2
92 CF.sub.3, CH.sub.2 F
CH.sub.2 F(CH.sub.2).sub.2
93 CF.sub.3, CH.sub.2 F
CH.sub.2 FCH.sub.2 CF.sub.2
94 CF.sub.3, CH.sub.2 F
CH.sub.2 FCH.sub.2 CHF
95 CF.sub.3, CH.sub.2 F
CH.sub.3 CF.sub.2
96 CF.sub.3, CH.sub.2 F
CH.sub.3 (CF.sub.2).sub.2
97 CF.sub.3, CH.sub.2 F
CH.sub.3 CF.sub.2 CHF
98 CF.sub.3, CH.sub.2 F
CH.sub.3 CF.sub.2 CH.sub.2
99 CF.sub.3, CH.sub.2 F
CH.sub.3 CHF
100 CF.sub.3, CH.sub.2 F
CH.sub.3 (CHF).sub.2
101 CF.sub.3, CH.sub.2 F
CH.sub.3 CHFCF.sub.2
102 CF.sub.3, CH.sub.2 F
CH.sub.3 CHFCH.sub.2
103 CF.sub.3, CH.sub.2 F
CH.sub.3 CH.sub.2 CF.sub.2
104 CF.sub.3, CH.sub.2 F
CH.sub.3 CH.sub.2 (CF.sub.2).sub.2
105 CF.sub.3, CH.sub.2 F
CH.sub.3 (CH.sub.2).sub.2 CF.sub.2
106 CF.sub.3, CH.sub.2 F
CH.sub.3 (CH.sub.2).sub.2 (CF.sub.2).sub.2
107 CF.sub.3, CH.sub.2 F
CH.sub.3 (CH.sub.2).sub.3 CF.sub.2
108 CF.sub.3, CH.sub.2 F
CH.sub.3 (CH.sub.2).sub.3 (CF.sub.2).sub.2
109 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3
110 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2
111 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 F
112 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.3
113 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CF.sub.2
114 CF.sub. 3, CH.sub.3 CF.sub.2
CF.sub.3 (CF.sub.2).sub.2
115 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CF.sub.2 CHF
116 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CF.sub.2 CH.sub.2
117 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CHF
118 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 (CHF).sub.2
119 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CHFCF.sub.2
120 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CHFCH.sub.2
121 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CH.sub.2
122 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 (CH.sub.2).sub.2
123 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CH.sub.2 CF.sub.2
124 CF.sub.3, CH.sub.3 CF.sub.2
CF.sub.3 CH.sub.2 CHF
125 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CF.sub.2
126 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 (CF.sub.2).sub.2
127 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CF.sub.2 CHF
128 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CF.sub.2 CH.sub.2
129 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CHF
130 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 (CHF).sub.2
131 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CHFCF.sub.2
132 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CHFCH.sub.2
133 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CH.sub.2
134 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 (CH.sub.2).sub.2
135 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CH.sub.2 CF.sub.2
136 CF.sub.3, CH.sub.3 CF.sub.2
CHF.sub.2 CH.sub.2 CHF
137 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCF.sub.2
138 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 F(CF.sub.2).sub.2
139 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCF.sub.2 CHF
140 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCF.sub.2 CH.sub.2
141 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCHF
142 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 F(CHF).sub.2
143 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCHFCF.sub.2
144 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCHFCH.sub.2
145 CF.sub.3, CH.sub.3 CF.sub.2
CH.sub.2 FCH.sub.2
146 CF.sub.3, CH.sub.3 CF.sub.2
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