CA2115253A1

CA2115253A1 - Hydrochlorofluorocarbons having oh rate constants which do not contribute substantially to ozone depletion and global warming

Info

Publication number: CA2115253A1
Application number: CA002115253A
Authority: CA
Inventors: Chien C. Li
Original assignee: Individual
Current assignee: Honeywell International Inc
Priority date: 1991-08-16
Filing date: 1992-08-13
Publication date: 1993-03-04
Also published as: EP0641300A1; US5316690A; BR9206357A; WO1993004025A1; AU2470092A; JPH07501046A; US5705716A

Abstract

The present invention provides hydrochlorofluorocarbons having 3 to 5 carbon atoms, 1 to 2 chlorine atoms, and an OH rate constant from about 8 to about 25 cm3/molecule/sec x 10-14. The hydrochlorofluorocarbons are useful as solvents and blowing agents.

Description

WO 93/04025 PC[/US92/067g8 211S253 :

HYDROCHLOROFLUOROCARBONS HAVING OH RATE CONSTANTS
WHICH DO NOT CONTRIBUTE S~STANTIALLY TO OZONE
DEPLETION AND GLOBAL WARMING

BACKGROUND OF THE INVENTION

The present invention relates to a class of hydrochlorofluorocarbons which have 3 to 5 carbon atoms, have 1 to 10 2 chlorine atoms, and have OH rate constants from about 8 to about 25 cm3tmolecule/secx10 ~

In response to the need for stratospherically safe materials, substitutes have been developed and continue to be developed.
15 Research Disclosure 14623 (June 1978) reports that 1,1 -dichloro-2,2,2-trifluoroethane (known in the art as HCFC-123) is a useful solvent for de~reasin~ and denuxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 ~April 1988), it was reported that 20 HCFC-123 and 1,1-dichloro-1-fluoroethane (known in the art as HCF~-141 b) have potential as replacements for CFC-113 as cleaning agents.

The problem with these substitutes is ~at they have a long atmospheric lifetime as determined by their reaction with OH radicals 25 in the troposphere. Table I below contains the OH rate constants and correspondin~ atmospheric lifetimes for these sub~titutes. In Table 1, EXP KOH stands for experimental KOH rate constant, Est ICOH stands for estimated KOH rate constant, Exp Life stands for experimental lifetime, and Est Life stands for estimated lifetime. The unit on the rate 30 constant is cm3/molecule/sec x 1 ~'~ and the unit on the lifetime is years.

wo 93/04025 PCr/US92/067g8 2~'~s~S3 - 2 -TABLE I
_ _ .
Numb~r Fomlula E~ E~t Ko~ E~lp l.ifo E-t Ufo HCFC-123 C~a2CF~ 3.72.96 2.0 2.6 HCFC-l 2~ CF~CI~laF 1.0 1.00 7.5 7.5 S ~ HCFC-141b CFCI~CH~ 0.75 2.10 10.1 3.6 HCFC-142b Cf2aCH~ 0.38 2.10 19.9 6 . ¦ HCfC-22~ CF~CF~CHa~ 2.~9 3.30 2.3 2.3 ¦ HCFC~ cb CaF*F~CHaF 0.91 3.8~ 2 1.96 HCC-l~O CCI,CH, 1.21.21 ~.3 _ 6.3 It would be desirable to have substitutes with OH rate constants of at least about 8 cm3/molecule/secx101~ which equates to an atrnospheric lifetime of 15 12 months or less.

If the OH rate constant of a compound is too high, the compound is a VOC ~Volaffle Organic Compound) because it is so reactive that it forms carbon dioxide which contributes to global 20 warming. Thus, it would be desirable to have substitutes with OH
rate constants of 25 cm3/molecule/secx101~ or less which equates to an atrnospheric lifetime of at least 4 months.

Commonly assigned U.S. Patent 4,947,881 teaches a method 25 of cleaning using hydrochlorofluoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published December 27, 1g89 teaches hydrochlorofluoropropan~s having a difluoromethylene group. International Publication Number WO 90108814 published August 9, 1990 teaches azeotropes having 30 at least one hydrochlorofluoropropane having a difluoromethylene group.

WO 93/0~025 PCI`/US92/06798 2ll52~3 A wide variety of consumer parts is produced on an annual basis in the United States and abroad. Many of these parts have to be ;~
cleaned during various manufacturing stages in order to remove undesirable contaminants. These parts are produced in large 5 quantities and as a result, substantial quantitiès of so!vents are used to clean them.

Thus, substitutes having OH rate constants between about 8 and about 25 cm3/molecule/secxlO '~ and which are useful in many 10 applications including as solvents are needed in the art.

SUMMARY OFTHE INVENTION

Strai~ht chain and branched chain hydrochloro~uorocarbons havin~ 3 to 5 car~on atoms and 1 or 2 chlorine atoms total over 1100 compounds. Out of this over 1100 compounds, I was surprised to ffnd a olass of 88 hydrochlorofluorocarbons havin~ OH rate constants from about 8 to about 25 20 cm3/molecule/secx1 o~

The OH rate constant can be determined by any method known in the art. For example, see Atkinson, ~Kinetics and Mechanisms of the Gas-Phase Reactions of the Hydroxyl Radical with Organic 25 Compounds under Atmospheric Conditionsn, Chem~ Rev. ~. 69 ~1986) and Taylor et al., ~Laser Photolysis/Laser-lnduced Fluorescence Studies of Reaction Rates of OH with CH~CI, CH2CI2, and CHCI~ over an Extended Temperature Ran~e", Int. J. of Chem. Kinetics ;~, 829 (1 989).

WO 93/04025 PC1`/US92/06798 211S~5~

The s~raight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention are listed in Table ll below. The unit on the calculated KOH jS cm3/molecule/sec x 1014 and the unit on the calculated life~me is years in Table ll.
s TABLE ll Number Chemical Formula ~OH Lifetime HCFC-234aa CF2HCCI2CF2H 24.5 0.30 HCFC-234ab CFH2CCI2CF3 11.9 0.64 HCFC-234ba CF2HCFCICFCIH 22.9 0.33 HCFC-234bb CF3CFCICclH2 9 5 0.80 HCFC-234bc CFH2CFCICF2CI 13.1 0.58 HCFC-234fa CF2CICH2CF2CI 8.2 0.92 HCFC-234fb CF3CH2CFcl2 8.2 0.92 HCFC-243ea CFCIHCFHCFCIH 19.1 0.40 HCFC-243ec CF2CICFHCClH2 8.~ 0.90 HCFC-244Sa CFH2CFCICF2H 12.0 0.63 HCFC-244da CF2HCCIHCF2H 11.85 0.64 HCFC-244db CF3CCIHCFH2 9.3 ~ 0.81 HCFC-244ea CF2HCFHCFCIH 11.9 0.64 HCFC-244eb CF3CFHCClH2 10.5 0.72 HCFC-244ec CFH2CFHCF2CI 10.1 0.75 HCFC-244fa CFCIHCH2CFI 8.5 0.89 HCFC-244fb CF2HCH2CF2CI 9.15 0.83 HCFC-252dc CH~CCIHCF2CI 15.3 0.49 HCFC-252ec CH~CFHCCI2F 8.6 0.88 HCFC-253ba CFH2CFCICFH2 17.7 0.43 HCFC-253bb CH3CFCICF2H 13.8 0-55 HCFC-253ea CF2HCFHCclH2 14.5 0.52 WO 93/04025 PCr/US92/06798 ~¢52S3 :.
TABLE ll ~CONTINUED) NUMBER CHEMICAL FORMULA ~OH LIFETIME

HCFC-253eb CCIFHCFHCFH2 16.5 0.46 HCFC-253ec CH3CFHCF2CI 8.0 0.95 HCFC-253fa CF2HCH2CFCIH 14.5 0.52 HCFC-253fc CFH2CH2CF2cl 11.5 0.66 HCFC-262fa CF2HCH2CClH2 14.99 0.50 HCFC-262fb CFH2CH2CFCIH 17.8 0.43 HCFC-271 b CH3CFCICH3 9.95 0.76 HCFC-271d CH3CCIHCFH2 19.44 0.39 HCFC-271fb CH3CH2CFCIH 9.98 0.76 This present class with its OH rate constants between about 8 15 to about 25 cm3/molecule/secxlO '~ was unexpected. I discovered this when I compared isomers havin~ the same -CA~ group wherein -CAB- is -CCI2-, -CH2-, -CCIH-, -CCIF-, and -CHF- as the covered compound. I found that the isomers had OH rate constants less than 8 or ~reater than 25 cm3/molecule/sec x 101~. For example, 20 CFCIHCFHCFCIH and CF2CICFHCCIH2 of the present invenffon have KOH values of 19.1 and 8.4 cm3/molecule/sec x 1~'~ respectively as shown in Table ll. In contrast, the isomers, CF2HCFHCCI2H and CCI2FCFHCFH2, have KOH values of 31.3 and 30.0 cm3/molecule/sec x 10 '~ respectively as shown in Table Vll, and ~us, are VOCs.
Also, CFH2CFCICF2H of the present invention has a KOH of 12.0 cm3/molecule/sec x 10~'~ as shown in Table ll. In contrast, the isomer, CF3CFCICH3, has a l(OH Of 1.8 cm3/molecule/sec x 10 '~ as shown in Table Vll, and thus, has a long atrnospheric lifetime. The 30 isomers, CFH2Ca2CFH2 and CH~CCI2CF2H, have Ko~ values of 49.33 WO g3/04025 ' PCr/USg2/067g8 2115253 .....

and 34.14 cm3/molecule/secx10 1~ respectively as shown in Table Vll and thus, are VOCs.

Additionally, CH3CFHCCI2F of the present invention has a KOH of 5 8.6 cm3/molecule/sec x 10l~ as shown in Table ll. In contrast, the isomers, CCIH2CFHCCIFH and CFH2CFHCCI2H, have KOH values of 31.8 and 39.57 cm3/molecule/sec x 10'~ respeetively as shown in Table Vll, and thus, are VOCs.

Additionally, CF2HCH2CCIH2 and CFH2CH2CFCIH of the present invention have KOH values of 14.99 and 17.8 cm3/molecule/sec x 10 14 respectively as shown in Table 11. In contrast, the isomer, CF2CICH2CH " has a KOH O~ 2.9 cm3/molecule/sec x 10 1~ as shown in Tabb Vll, and thus, has a long atmospheric lifetime. Additionally, .CH~CH2CFCIH of the present invention has a KOH of 9.98 cm3/molecule/sec x 10 l~ as shown in Table ll. In contrast, the isomer, CFH2CH2CCIH2, has a ICOH value of 35.8 cm3/molecule/sec x 10 l4 as shown in Table Vll, and thus, is a VOC.

Known methods for making fluorinated compounds can be `
modffled in order to form the straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention.

For example, Haszeldine, Nature ~, 152 (1950) teaches the reaction of trifluoroiodomethane and acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then dehydroiodinated to form 3,3,3-trffluoropropyne. By usin~ 3,3,3-trifluoropropyne as a starting material, CF,CFCICCIH2 (HCFC-234bb) may be prepared as follows.
Commercially available trifluoromethyl iodide may be reacted with acetylene to prepare 3,3,3-trifluoro-1-iodopropene which is then .

~ .

WO g3/04025 PCr/USg2/06798 :

211~253 dehydroiodinatsd to form 3,3,3-trifluoropropyne. The 3,3,3-trifluoropropyne may then be reacted with commerciallv available hydrogen fluoride to form 2,3,3,3-tetrafluoro-1-propene which is then chlorinated to form 1,2-dichloro-2,3,3,3-tetrafluoropropane.
CF2CICFHCCIH2 (HCFC-243ec) may be prepared as follows.
Commercially available 1,1,3-trichloropropene may be dehydrohalogenated to form 1,3-dichloro-1- propyne. The 1,3-dichloro-1-propyne may then be fluorinated to form 1 ,3-dichloro-1,2-10 dffluoro-1-propene which may then be reacted wim commercially available hydrogen fluoride to form 1,3-dichloro-1,1,2-trifluoropropane.

CFH2CFCICF2H (HCFC-244ba) may be prepared as follows.
Commercially available 1 ,3-dmuoro-2-propanol may be dehydrated to 15 form 1 ,3-difluoro-1 -propene which may then be dehydrohalogenated to form 3-fluoro-1-propyne. The 3-fluoro-1-propyne may then be fluorinated, chlorinated, and fluorinated to form 1,1,2,3-tetrafluoro-2-chloropropane.

CFH2CFHCF2CI (HCFC-244ec) may be preparcd as fo700ws.
Commercially available 1,1,3-trichloropropene may be fluorinated to foml 1,1-dichloro-3-fluoro-1-propene which may then be dehydrohalogenated to form 1-chloro-3-fluoro-1-propyne. The 1-chloro-3-fluoro-1-propyne may then be fluorinated to form l-chloro-1,2,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,2,3-telrafluoropropane.

CFCIHCH2CF3 (HCFC-244fa) may be prepared as follows.
Commercially available 1,1,3-trichloropropene may be fluorinated to .

WO 93/04025 PCI`/US92/06798 2l~52~3 form 1,1,1,2,3-pentafluoropropane. The 1,1,1,2,3-pentafluoropropane may then be dehydrohalogenated to form 1,3,3,3-tetrafluoro-1-propene which may then be reacted with commercially available hydrogen chloride to form 1-chloro-1,3,3,3-5 tetrafluoropropane.

CF2HCH2CF2CI ~HCFC-244fb) may be prepared as follows.
Commercially available 2,2,3,3-tetrafluoro-1-propanol may be fluorinated to form 1,1,1,2,2,3-hexafluoropropane which may then be 10 dehydrohalogenatedtoforrn 1,3,3-tritluoro-1-propyne. The 1,3,3-trifluoro-1-propyne may then be reacted with commercially available hydro~en chloride to forrn 1-chloro-1,3,3-trifluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1-chloro-1,1,3,3-tetrafluoropropane.
CH3CFCICF2H (HCFC-253bb) may be prepared as follows.
Commercially available 1 ,2-dibromopropane may be dehydrohalo~enated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1,1,2-20 trffluoropropane.

CH3CFHCF2CI ~HCFC-253ec) may be prepared as follows.
Commercially available 1 ,2-dichloropropane may be dehydrohalogenated to form 1-chloro-1-propene which may then be 25 dehydrogenated to form 1-chloro-1-propyne. The 1-chloro-1-propyne may then be reacted with commercially available hydrogen fluoride to form l-chloro-l-fluoro-1-propene which may then be fluorinated to form 1-chloro-1,1,2-trifluoropropane.

wO 93/0402s Pcr/usg2/067s8 .

21152.~3 The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF2CICFHCCIH2, CFH2CFCICF2H, CFH2CFHCF2CI, CFCIHCH2CF3, CF2HCH2CF2CI, CHICFClCFzH, and CH3CFHCF2CI.

The s~ai~ht chain hydrochlorofluorocarbons having 4 carbon atoms of ~e present inven~on are listed in Table lll below. The unit on the cslculated Ko,1 is cm3/molecule/secx10 l~ and the unit on the calculated lifetime is years in Table lll below.
TABLE lll Number Chemical Formula ~ Lifetime HCFC-3541cd CHJCCIHCF2CF2CI 12.8 0.59 HCFC-354mbd CH3CCIHCFCICF, 11.9 0.63 HCFC-3551cf CFH2CH2CF2CF2CI 12.0 0.63 HCFC-355bc CH3CF2CFHCF2CI 12.8 0.59 HCFC-3S51ef CF2HCH2CFHCF2CI 15.6 0.48 HCFC-355ffl CF3CH2CH2CF2CI 10.4 0.73 HCFC-355mbf CFH2CH2CFCICF3 11.5 0.66 HCFC-355mcf CF~CF2CH2CCIH2 8.93 0.85 HCFC-355mdc CH3CF2CCIHCF3 12.0 0.63' HCFC-355mdf CF2HCH2CaHCF3 14.3 -- 0.53 HCFC-355meb CH3CFCICFHCF3 11.8 0.64 HCFC-355med CFH2CCIHCFHCF3 14.1 0.54 HCFC-355mfb CFH2CFCICH2CF3 15.9 0.48 HCFC-355mfc CF3CH2CF2CclH2 13.2 0.57 HCFC-355mfd CF2HCCIHCH2CF3 14.9 0.51 HCFC-355mfe CFCIHCFHCH2CF3 15.1 0.50 HCFC-355pcb CHJCFCICF2CF2H 15.7 0.48 HCFC-355rcc CH,CF2CF2CFCIH 15.2 0.50 HCFC-3631bfs CH~CH2CCIFCF2CI 13.4 0.56 HCFC-364med CH3CCIHCFHCF3 15.0 0.50 wo g3/0402s Pcr/uss2/067ss .

2115~S3 TABLE lll ~CONTINUED) NUMBER CHEMICAL FORMULA ~OHLIFETIME

HCFC-364rnff CFCIHCH2CH2CF3 15.50.49 HCFC-3731ef CH3CH2CFHCF2CI 9.11 0.83 HCFC-373mfd CH3CCIHCH2CF3 14.3 0.53 HCFC-373mff CF3CH2CH2CclH2 13.2 0.57 HCFC-391 rff CH3CH2CH2CFCIH 10.3 0.73 HCFC-391 sbf CH3CH2CFCICH3 14.2 0.53 Known methods for making fluorinated eompounds ean be modffied in order to form the strai~ht ehain hydroehlorofluorocarbons havin~ 4 carbon atoms of the present invention.

For example, R. N. Haszeldine et ~I., "Addition of Free Radicals to Unsaturated Systems. PartXIII. Direction of Radieal Additionto Chloro-1:1-difluoroethylene", J. of Amer. Chem. Soe., 2193 (1957) teach the reaction of trifluoroiodomethane with ehloro~
difluoroethylene to prepare 3-chloro-1 :1 :1 :2:2-pentafluoro-3-20 iodopropane which is then chlorinated to form 1,1-dichloro-2,2,3,3,3-pentafluoropropane (known in the art as HCFC-225ca). This known method can be modified to form CF3CF2CH2CCIH2 (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1,1,2,2-pentafluoro-25 4iodobutane which is then chlorinat~d to form 1,1,1,2,2-pentafluoro-4chlorobutane.

CH3CF2CFHCF2CI (HCFC-3551ec) may be prepared as follows.
Commereially available 1,3-diehloro-2-butene may be fluorinated to WO 93/04025 PCl'~USg2/06798 21152.53 form 1-chloro-2,3,3-trifluorobutane which may then be dehydrohalogenated to form 1-chloro-3,3-difluoro-1-butene. The 1-chloro-3,3-difluoro-1-butene may then be dehydrogenated to form 1-chloro-3,3-difluoro-1-propyne which may then be fluorinated to form 5 1-chloro-1,2,3,3-tetrafh~oro-1-butene which n~ay then be reacted with commerciallv available hydrogen fluoride to form 1-chloro-1,1,2,3,3-pentafluorobutane.

CF~CH2CH2CF2Cl IHCFC-3551ff) may be prepared as follows.
10 Commercially available 2,3-dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butvne. The hexafluoro-2-butyne may be hydro~enated to form 1,1,1,4,4,4hexafluorobutane which may be chlorinated to form 1-chloro-1,1,4,4,4pen~afluorobutane.

CFH2CH2CFClCF3 (HCFC-355mbf) may be prepared as follows.
; Commercially avaibble 1 ,4dichloro-2~butyne may be reacted withcommercially available hydrogen fluoride to form 1 ,4~`dichloro-2-fluoro-2-butene which may be fluorinated to form 1,2,4trifluoro-2-butene.
The 1,2,4trifluoro-2-butene may be reacted with commercially 20 available hydrogen chloride to form 2-chloro-1 ,2,4trifluorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, - and fluorinated to form 2-chloro-1,1,1,2,4pentafluorobutane.

CH3CF2CClHCF3 ~HCFC-355mdc) may be prepared as follows.
25 Commercially available 3,4dichloro-1-butene may be dehydrogenated to form 3,'1 dichloro-1-butyne which maV be reacted with commercially available hydrogen fluoride to form 1,2-dichloro-3,3-difluorobutane. The 1 ,2-dichloro-3,3-difluorobutane may be dehydrogenated to form 1,2-dichloro-3,3-dmuoro-1-butene which may 30 be reacted with commercially available hydrogen fluoride to form 2-wo g3/04025 rcr/uss2/067ss 21152~3 chloro-1,1 ,3,3-tetrafluorobutane. The 2-chloro-1,1,3,3-tetrafluorobutane may be dehydrogenated to form 2-chloro-1,1,3,3-tetrafluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-chloro-1,1,1,3,3-pentafluorobutane.
CH3CFCICFHCF3 (HCFC-355meb) may be prepared as follows.
Commercially available 1 ,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4trinuorobutane which may be dehydrohalogenated to form 3-chloro-1 ,3-di~uoro-1-butene. The 3-chloro-1 ,3-difluoro-1-10 butene may be fluorinated to form 2-chloro-2,3,4,4-tetrafluorobutane which may be dehydrohalo~enatedto form 3-chloro-1,1,3-trifluoro-1 butene. The 3-chloro-1,1,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,4,4,4pentafluorobutane.

CH3CFClCF2Cf2H (HCFC-355pcb) may be prepared as follows.
Commercially available 1 ,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4 trinuorobutane whkh may be déhydrogenated to form 3-chloro-1,2,3-trffluoro-1-butene. The 3-chloro-1,2,3-trifluoro-1-butene may be fluorinated to form 2-chloro-2,3,3,4,4 20 pentafluorobutane.

CH3CF2CF2CFCIH (HCFC-355rcc) may be prepared as follows.
Commercially available 1 ,3-dichloro-2-butene may be fluorinated to form 1-chloro-2,3,3-trifluorobutane which may be dehydrogenated to 25 form 1-chloro-2,3,3-trffluoro-1-butene. The 1-chloro-2,3,3-trifluoro-1-butene ma~/ be fluorinated to form 1-chloro-1,2,2,3,3-pentanuorobutane.

CH3CCIHCFHCF3 (HCFC-364med) may be prepared as follows.
30 Commercially available 1,3-dichloro-2-butene may be reacted wim WO 93/04025 PCI`/US92/06798 211S25~3 commercially avaiiable hydrogen fluoride to form 1 ,3-dichloro-2-fluorobutane which may bé dehydrohalogenated to form 1 ,3-dichloro-1-butene. The 1,3-dichloro-1-butene may be fluorinated to form 2-chloro-3,4,4trifiuorobutane which may be dehydrohalogenated to 5 form 3-chloro-1,1-dffluoro-1-butene. The 3-chloro-1,1-difluoro-1-butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafluorobutane.

The preferred s~ai~ht chain hydrochlorofluorocarbons having 4 carbon atoms are CH3CF2CFHCF2CI, CF3CH2CH2CF2CI, CFH2CH2CFCICF3, CH3CF2CCIHCF3, CH3CFCICFHCF3, CH3CFCICF2CF2H, CH3CF2CF2CFCIH, and CH3CCIHCFHCF3.

The branched chain hydrochlorofluorocarbons having 4 carbon atoms of the present inven~on are listed in Table IV below. The unit 15 on ~e calculated Ko~ is cm3/molecule/sec x 10 1~ and the unit on the calculated life~me is years in Tablo IV below.

TABLE IV
Number Çhemical Formula ~OH Lifetime HCFC^345icms CH3c~cF3)FcFcl2 9 11 0.83 HCFC-34511s CH3C(CF2CI~FCF2CI 9. 11 0.83 HCFC-355ims CH3C(CF3)HCF2CI 8.3 0.91 HCFC-355mop CF2HC(CCIH2)HCF3 14.5 0.52 HCFC-355mps CH3C~CF2H)CICF3 15.3 0.50 HCFC-355mrs CH3C~CFCIH)FCF3 15.1 0.50 HCFC-373mss CH3C(CH3)CICF3 13.4 0.56 .

W093/0402~i PCI/US92/067g8 211S2~3 Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.

CH3C(CF3)HCF2CI (HCFC-3551ms) may be prepared as follows.
Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2-difluoro-2-methylpropane which may be dehydrohalogenatedtoform1-chloro-1-fluoro-2-methylpropene. The 1-chloro-1-fluoro-2-methylpropene may be nuorinated to form 1-chloro-1,1,2-trffluoro-2-methylpropanewhich may be dehydrohalogenated to form 3-chloro-3,3-dmuoro-2-methylpropene.
The 3-chloro-3,3-difluoro-2-methylpropene may be fluorinated to form - 1-chloro-1,1,2,3-tetrafluoro-2-methylpropane which may be dèhydro~enated to form 3-chloro-1 ,3,3-trifluoro-2-methylpropene.
The 3-chloro-1 ,3,3-trifluoro-2-methylpropene may be ~uorinated to form 1-chlor~1,1 ,2,3,3-pentafluoro-2-methylpropane which may be ~; dehydrohalo~enated to form 3-chloro-1,1,3,3-tetrafluoro-2-methylpropene. The 3-chloro-1,1 ,3,3-tetrafluoro-2-methylpropene may be fluorinated to form 1-chloro-1,1,3,3,3-pentafluoro-2-methylpropane.

CH3C~CF2H)CICF3 ~HCFC-355mps) may be prepared as follows.
Commercially available 1-chloro-2-methylpropene may be fluorinated to forrn 1,1,2-trifluoro-2-methylpropane which may be dehydrohalo~enated to form 3,3-difluoro-2-methylpropene. The 3,3-difluoro-2-methylpropene may be fluorinated to forrn 1,1,2,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 1,3,3-trffluoro-2-mothylpropene. The 1,3,3-trffluoro-2-n~lpropene may bo fluorinated to form 1,1 ,2,3,3-pentafluoro-2-methvlpropane which may be dehydrohalogenated to fonn 1,1,3,3-' ~

WO g3/04025 PCr/USg2/06798 2 5 ~

tetrafluoro-2-methylpropene. The 1,1,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1,2-dichloro-1,1,4,4tetrafluoro-2-methylpropane which may be fluorinated to form 2-chloro-1,1,1,3,3-pentafluoro-2-methylpropane.
CH~C~CFCIH)FCF3 ~HCFC-3S5mrs) may be prepared as follows.
Commercially available 1-chloro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2-dîfluoro-2-methylpropane which may be dehydrohalo~onated to form 3-chloro-3-fluoro-2-methylpropene. The 10 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2,3-trffluoro-2-methylpropane which may be dehydrohalo~enated to form 3-chloro-1 ,3-difluoro-2-methylpropene.
The 3-chlor~1 ,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2,3,3-tetrafluoro-2-methylpropane which may be 15 dehydrohalo~enated to form ~-chloro-1,1 ,3-trifluoro-2-methylpropene.
The 3~hlor~1,1 ,3-tri~uoro-2-methylpropene may be fluorinated to form 1~hloro-1 ,2,3,3,3-pentafluoro-2-methylpropane.

The preferred branched hydrochlorofluorocarbons having 4 20 carbon atoms are CH3C(CF3)HCF2CI, CH3C(CF2H)CICF3, and CH3C:~CFCIH)FCF3.

The branched hydrochlorofluorocarbons having S carbon atoms of the present invention are listed in Table V below. The unit on the 25 calculated Ko~ is cm3/molecule/sec x 10 '~ and the unit on the calculated lifetime is years in Table V below.

TABLE V
Number Chemical Formula ~OH Lifetime HCFC-356mlfq CFH2CH2C~CF2CI)FCF3 12.0 0.63 HCFC-3571csp CF2CICF2C(CH3)FCF2H 15.1 0.50 HCFC-3571sem CF3CFHC(CH~)FCF2CI 14.6 0.52 HCFC-357mbsp CF3CFCIC(CH3)FCF2H 15.C 0.50 HCFC-357mcpo CF3CF2C~CF2H)HCCIH2 14.7 0.51 HCFC-357mcsp CF~CF2C~CH3)CICF2H 13.7 0-55 HCFC-357mcsr CF~CF2C~CH~)FCFCIH 15.1 0.50 HCFC-357mlcs CH~CF2C~CF2CI)HCF3 10.7 û.71 HCFC-357mmbs CHJCFCIC~CF3)HCF3 9.5 0.80 HCFC-357mmel` CF2CICHFC(CH3)FCF3 14.3 0.53 HCFC-357mmfo CH2CICH2C(CF~)FCF3 8.8 0.86 HCFC-357mmfq CFH,CH2C(CF3)CICF3 11.5 0.66 HCFC-357mmfr CFCIHCH2C(CFJ)HCF3 14.0 0.54 HCFC-357mofm CFJCH2C(CCIH2)FCF3 14.1 0.54 HCFC-357msem CFJCFHC(CH3)CICF3 13.0 0.57 HCFC-358mcsr CFJCF2C(CH3)FCCIFH 13.8 0.55 HCFC-366mmds CH3CCIHC(CF3)HCF3 12.8 ~ 0.59 HCFC-366mmfo CCIH2CH2C(CF3)HCF3 13.2 0.57 HCFC-3751css CF2CICF2C(CH3)FCH3 10.7 0.71 HCFC^375mbss CF3CFCIC(CH3)FCH3 10.7 0.71 HCFC-3931ess CF2CICFHC(CH3)HCH3 12.1 0.62 HCFC-393mdss CF3CCIHC(CH3)HCH3 10.0 0.76 HCFC-393sfms CH3CH2C(CF3)CICH3 13.0 0.58 HCFC-3-11-1rfss CFCIHCH2C(CH3)HCH3 13.4 0.56 21152~3 Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention.

CFH2CH2C(CFzCl)FCFa ~HCFC-356mlfq) may be prepared as follows. Commercially available 1,4dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1,~dichloro-2-trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form 1,Wichloro-3-triflyoromethyl-1-butene. The 1 ~dichloro-3-trifluoromethyl-1-butene may be hydrogenated to form 1,4dichloro-2-trifluoromethylbutane which may be fluorinated to form 1-chloro-2-trffluoromethyl 4 fluorobutane. The 1-chloro-2-trifluoromethyl-4-fluorobutane may be dehydrogenated to form 1-chloro-2-trinuoromethyl-4fluoro-1-butene which may ~e fluorinated to form 1-chloro-2-trifluoromethyl-1,2,4-trifluorobutane. The 1-chloro-2-trifluoromethyl-1 ,2,4trifluorobutane may be dehydrohalogenated to form 1-chloro-2-trifluoromethyl-1 ,4-dffluoro-1-butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1,1,2,~
tetrafluorobutane.
CF3CFHC(CH3)FCF2CI (HCFC-3571sem) may be prepared as follows. Comrnercially available 1,4 dichloro-2-butene may be reacted with commercially available iodomethane to form 1,1 dichloro-3-iodo-2-methylbutane which may be dehydrohalogenated to form 1,4 dichloro-3-methyl-1-butene. The 1,1 dichloro-3-methyl-1-butene may be fluorinated to form 1-chloro-2-methyl-3,4,~trifluorobutane which may be dehydrohalo~enated to form 1 ,1-difluoro-3-methyl-4chloro-1-butene. The 1,1-difluoro-3-methyl-4chlor~1-butene may be tluorinated to form l-chloro-2-methyl-3,4,4,4tetrafluorobutane which may be dehydrogenated to form 1-chloro-2-methyl-3,4,4,4-tetrafluoro-WO 93/04025 PCI`/US92/067g8 21152~3 l-butene. The 1-chloro-2-methyl-3,4,4,~tetrafluoro-1-butene may be fluorinated to form 1-chloro-2-methyl-1,2,3,4,4,4hexafluorobutane which may be dehydrohalogenated to form l-chloro-2-methyl-1 ,3,4,4,4pentafluoro-1-butene. The 1-chloro-2-methyl-1,3,4,4,~
5 pentafluoro-1 butene may be fluorinated to forrn 1-chloro-2-methyl-1 ,1 ,2,3,4,4,4-heptafluorobutane.

CF3CFCIC~CH3)FCF2H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may 10 be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-2-methyl-1, 1,1 ,4,4,4hexafluoropropane which maV be fluorinated to form 2-methyl-3-chloro-1,1,1,2,3,4,4 heptaffuorobutane. The 2-methyl-3-chloro-1,1,1,2,3,4,4 hepta~uorobutane may be dehalogenated to form 3-chloro-2-methyl-15 1,1,3,4,4,4hexafluoro-1-butene which may be reacted with commercially available hydrogon fluoride to form 3-chloro-2-methyl-1 ,1 ,2,3,4,4,4heptafluorobutane.

CF~CF2C(CH~)CICF2H ~HCFC-357mcsp) may be prepared as 20 follows. Commercially avaDable 2,3-dichlorohexsfluoro-2-6utenemay be reacted wi~ iodomethane to form 2-methyl-2,3-dichloro-3-iodo-1,1,1,4,4,4hexafluorobutane which may be fluorinated to form 2-methyl-1 ,1 ,1 ,2,3,3,4,4,4nonafluorobutane. The 2-methyl-1,1,1,2,3,3,4,4,4nonafluorobutane may be dehalogenated to form 2-25 methyl-1,1,3,3,4,4,~heptafluoro-1-butene which may be react~d with commercially available hydrogen chloride to form 2-chloro-2-memyl-1, 1 ,3,3,4,4,4heptafluorobutane.

CH,CF2C(CF2CI)HCF~ (HCFC-357mlcs) may be prepared as 30 follows. Commercially available 1 ,3-dichloro-2-butene may be reacted wo s3/0402s Pcl~/uss2/06798 211~25~

with commercially available trifluoromethyl iodide to form 1,3-dichloro-2-trifluoromethyl-3-iodobutane which may be fluorinated to form 1,3,3-trif!uoro-2-trifluoromethylbutane. The 1,3,3-trifluoro-2-trifluoromethylbutane may be dehydrogenated to form 1,3,3-trifluoro-5 2-trifluoromethyl-1-butene which may be fluorinated to form 1,1 ,2,3,3-pentafluoro-2-trifluoromethylbutane. The 1,1,2,3,3-pentafluoro-2-tri~uoromethylbutane may be dehydrohalogenated to form 1,1,3,3-tetrafluoro-2-trifluoromethyl-1-butene which may be reacted with commercially available hydrogen chloride to form 1-10 chloro-1,1,3,3-tetrafluoro-2-trifluoromethylbutane.

CH~CFCIC(CF~)HCF~ IHCFC-357mmbs) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1 5 2,3-dichloro-3-iodo-2-trffluoromethyl-1 ,1 ,1 ,4,4,4hexafluorobutane which may be fluorinated to form 2-trifluoromethyl-1,1,1,2,3,3,4,4,4 nona~uorobutane. The 2-trifluorome~yl-1, 1, 1,2,3,3,4,4,4 nonafluorobutane may be dehalogenated to form 3-trifluoromethyl-1,1,2,3,4,4,4heptafluoro-1-butene which may be hydrogenatedto 20 form 2-trifluoromethyl-1,1,1,2,3,4,4heptafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,4,4heptafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-1,2,3,4,4,4-hexafluoro-1-butene which may be hydrogenated to form 3-trifluoromethyl-1,2,3,4,4,4hexafluorobutane. The 3-trifluoromethyl-1,2,3,4,4,4-25 hexafluorobutane may be dehydrohalogenated to form 3-trifluoromethyl-2,3,4,4,4pentafluoro-1-butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2-trifluoromethyl-1,1,1 ,2,3-pentafluorobutane. The 3-chloro-2-trifluoromethyl-1,1,1,2,3-pentafluorobutane may be dehalogenated to 30 form 3-chloro-2-trifluoromethyl-1,1,3-trifluoro-1-butene which may be Wo 93/04025 PCI`/USg2/06798 reacted with commercially available hydrogen fluoride to form 3-chloro-2-trifluoromethyl- 1 ,1 ,1, 3-tetrafluorobutane.

CF2CICHFC~CHl)FCF3 ~H~:FC-357mmel) may be prepared as 5 follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1 ,4,4,4hexafluoro-2-methylbutane which may be fluorinated to form 2-methvlperfluorobutane. The 2-methylperfluorobutane may be dehalo~enated to form 1,1,2,3,4,4,4 10 heptafluoro-3-methyl-1-butene which may be reacted with commercially available hydroQen chloride to form 4-chloro-1,1 ,1 ,2,3,4,4heptafluoro-2-methylbutane.

Th- method of R.N. Haszeldine et al., supra, can be modified to 15 form CH2CICH2C(CF3)FCF, ~HCFC-357 mmfo~ as follows.
Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trffluoromethyl-1,1,1,2-tetrafluoro~iodobutane which may then be chlorinated to form 2-trifluoromethyl-l ,1,1 ,2-tetrafluoro-4chlorobutane.
CFH2CH2C~CF3)CICF3 (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethvl iodide to form 2,3-dichloro-3-iodo-1,1,1 ,4,4,4hexafluoro-2-trifluoromethylbutane 25 which may be fluorinated to form 2-chloro-2-trifluoromethyl-perfluorobutane. The 2-chloro~2-trifluoromethyl-perfluorobutane may be dehaloQenated to form 3-chloro-3-trifluoromethyl-1,1,2,4,4,1 hexanuoro-1-butene which may be hydro~enatcd to form 2-chloro-2-- trifluoromethyl-1,1,1,3,4,4hexafluorobutane. The 2-chloro-2-30 trifluoromethyl-1,1,1 ,3,4,~hexafluorobutane may be fluorinated to wo s3/0402s Pcr~uss2/067ss 21152~3 form 3-chloro-3-trifluoromethyl- 1 ,4,4,4-tetrafluoro- 1 -butene which may then be hydrogenated to form 2-chioro-2-trifluoromethyl-1,1,1,4- :
tetraflùorobutane .

CF3CFHC~CH~CîCF3 (HCFC-357msem~ may.be prepared as follows. Commerciallv available 2,3-dichlorohexafluoro-2-butene may :-be reacted with commercially available iodomethane to form 2,3-dichloro-3-iodo-1,1,1,4,4,4hexafluoro-2-methylbutane which may be chlorinated to forrn 2,3,3-trichloro-1, 1,1 ,4,4,4hexafluoro-2-memylbutane. The 2,3,3-trichloro-1,1,1 ,4,4,4hexafluoro-2-methylbutane may be dehalogenated to form 3-chloro-1,1,1,4,4,4 hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-: 1,1,1,3,4,4,4heptafluoro-2-methylbutane. The 3-chloro-1,1,1,3,4,4,4heptafluoro-2-methylbutane may be dehydrohalogenated to form 1,1,1,4,4,4hex~uoro-2-methyl-2-butene which may be reacted wi* commercially available hydrogen chloride to form 2-chloro-1, 1 ,1 ,3,4,4,4heptafluoro-2-methylbutane.

CF~CF2C(CHI)FCCIFH (HCFC-358mcsr) may be prepared as follows. Commerciallv available 2,3-dichlorohexafluoro-2-butenemay be reacted with commercially available trifluoromethyl iodide to form 2,3-dichtoro-3-iodo-1,1,1,4,4,4hexafluoro-2-methylbutane which may be fluorinated to form 2-methyl-perfluorobutane. The 2-methyl-perfluorobutane may be dehalogenated to form 2-methyl-perfluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 1,1,2,3,3,4,4,40ctafluoro-2-methvlbutane. The 1,1,2,3,3,4,4,4Octafluoro-2-methvlbutane may be dehalogenated to forrn 1,3,3,4,4,4hexafluoro-2-methyl-1-butene which may be chlorinat~d to form 1 ,2-dichloro-1 ,3,3,4,4,4hexafluoro-2-WO g3/04025 PCI /US92/06798 211~2~3 methylbutane. The 1,2-dichloro-1,3,3,4,4,4-hexafluoro-2-methylbutane may be dehydrohalogenated to form 1-chloro-1,3,3,4,4,~hexafluoro-2-methyl-1-butene which may be reacted with commercially available hydrogen fluoride to form 1-chloro-5 1,2,3,3,4,4,4 heptafluoro-2-methylbutane.

CH3CCIHC(CF3)HCF3 (HCFC-366mmds) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichlwo-3-iodo-10 1,1,1 ,4,4,4hexafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-1,1,1,4,4,4hexafluoro-2-methyl-2-butene.
The 3-iodo-1,1,1 ,4,4,4hexafluoro-2-trifluoromethyl-2-butene may be - hydro~enated to form 3-iodo-1, 1,1 ,4,4,4hexafluoro-2-trffluoromethylbutane which may be dehydrohalogenated to form 2-15 iodo-1,1,4,4,4pentafluoro-3-trifluoromethyl-1-butene. The 2-iodo-1,1,4,4,4pentafluoro-3-trifluoromethyl-1-butene may be hydrogenated to form 3-iodo-1,1,1,4,4pentafluoro-2-trifluoromethylbutane which may be chlorinated to form 3-chloro-1,1,1,4,4pentafluoro-2-trifluoromethylbutane. The 3-chloro-1,1,1,4,4pentafluoro-2-20 trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-1,4,4,4tetrafluoro-3-trifluoromethyl-1-butene which may be hydrogenated to form 3-chloro-1,1, 1 ,4-tetrafluoro-2-trifluoromethylbutane. The 3-chloro-1, 1,1 ,4tetrafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 2-chloro-25 4,4,4trifluoro-3-trifluoromethyl-1~butene which may be hydrogenated to form 3-chloro-1,1,1-trifluoro-2-trifluoromethylbutane.

The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH2CH2C(CF2CI)FCF3, CF,CFHC(CH3)FCF2CI, 30 CF3CFCIC(CH3)FCF2H, CF3CF2C~CH3)CICF2H, CH3CF2C~CF2CI)HCF3, WO 93/04025 PCl`/US92/06798 21152S~

CH3CFCIC~CF3)HCF3, CF2CICHFC(CH3)FCF3, CH2CICH2C~CF3)FCF3, CFH2CH2C(CF3)CICF3, CF3CFHC(CH3)CICF3, CF3CF2C(CH3)FCCIFH, and ~n3~ n~ ,r31r~-r3 Other advantages of the invention will become apparent from the following description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

.
Known solvents may be blended with the hydrochlorofluorocarbons of the present invention. Examples of useful known solvents are listed in Table Vl below.

Ie~BLE Vl Number Ch~micaLE~mula HCFC-234cc CF2CICF2CclH2 HCFC-234cd CH2FCF2CFcl2 HCFC-24~ca CF2HCF2CClH2 HCFC-244cb CFH2CF2CFCIH
HCFC-253ca CFH2CF2CclH2 - 25 HCFC-253cb CH ,CF2CFCIH

HCFC-234cc may be formed by any known method such as the reaction of 1,1,1,2,2,3-hexachloropropane with antimony pentachloride and hydrogen fluoride at 100C. HCFC-234cd may be 30 formed by any known method such as the reaction of 1,1,1-trichloro-.

WO g3/04025 PCI`/US92/06798.
21~52~3 2,2,3-trifluoropropane with antimony pentachloride and hydrogen fluoride at 1 20C.

HCFC-244ca may be formed by any known method such as the 5 reaction of 1,1,2,2,3-pentachloropropane with antimony pentachloride and hydrogen fluoride at 100C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1,1,2,2-tetraHuoropropane with cesium fluoride and tetrabutylammonium bromide at 1 50C.
HCFC-253ca may be formed by any known method such as the reaction of 1 ,2,3-trichloro-2-fluoropropane with niobium pentachloride and hydrogen fluoride at 100C. HCFC-253cb may be formed by any known method such as the reaction of 1,1,2,2-tetrachloropropane 15 with tantalum pentafluoride and hydrogen fluoride at 130C.

The present hydrochlorofluorocarbons may be used as solvents in vapor de~reasing, solvent cleaning, cold cleaning, dewatering, dry cleanin~, defluxing, decontamination, spot cleaning, aerosol propelled 20 rework, extraction, particle removal, and surfactant cleaning applications. In these uses, the object to be cleaned is immersed in one or more stages in the liquid and/or vaporized solvent or is sprayed with the liquid solvent. Elevated temperatures, ultrasonic energy, and/or agitation may be used to intensify the cleaning effect.
The present hydrochlorofluorocarbons are also useful as blowing agents, RanWne cycle and absorption remgerants, and power fluids and especially as remgerants for centrifugal remgeration chillers.

~113253 The present invention is more fully illustrated by the following non-limiting Examples.

COMPARATIVES
The hydrochlorofluorocarbons having 3 carbon atoms and 1 or 2 chlorine atoms in Table Vll below are isomers of the compounds of ~e present invention. As discussed above, these compounds have OH rate constants which are less than 8 cm3/molecule/secx10 l4 or 10 gr~ater than 2S cm3/molecule/secx10 t~. The unit on the KOH jS
cm3/molecule/secx1~l4 and ~e unit on the lifetime is years in Table Vll below.

I~BLE Vll Dl~m~ Chemical Formula .~OH Lifetime HCFC-243eb CF21 ICFHCCI2tl 31.3 0.24 HCFC-243ed CCI2FCFHCFH2 30 0 0.25 HCFC-244bb CF3t:FCICH3 1.8 -- 4.20 HCFC-252aa CFH2C:CI2CFH2 49'33 0.15 HCFC-2~2ab CH3CCI2CF2H 34.14 0.22 HCFC-252ea CCIH2CFHCCIFH 31.8 0.24 HCFC-252eb CFH2CFHCCI2H 39.57 0.19 HCFC-262fc CF2CICH2CH3 2.9 2.61 HCFC-271fa CFH2CH2CclH2 35.8 0.21 ` ' t ~ ", ~

Claims

AMENDED CLAIMS
[received by the International Bureau on 19 January 1993 (19.01.93);
original claims 1-4 replaced by amended claims 1-4; other claims unchanged (2 pages)]

1. A class of hydrochlorofluorocarbons having 3 to 5 carbon atoms. 1 to 2 chlorine atoms, and OH rate constants between about 8 and about 25 cm3/molecule/secx10-14 wherein said hydrochlorofluorocarbons are CF3HCCl2CF2H, CFH2CCl2CF3, CF2HCFClCFClH, CF3CFClCClH2, CFH2CFClCF2Cl, CF2ClCH2CF2Cl, CF3CH2CFCl2, CFClHCFHCFClH, CF2ClCFHCClH2, CFH2CFClCF2H, CF2HCClHCF2H, CF3CClHCFH2, CF2HCFHCFClH, CF3CFHCClH2, CFH2CFHCF2Cl, CFClHCH2CF3, CF2HCH2CF2Cl, CH3CClHCF2Cl, CH3CFHCCl2F, CFH2CFClCFH2, CH3CFClCF2H, CF2HCFHCClH2, CClFHCFHCFH2, CH3CFHCF2Cl, CF2HCH2CFClH, CFH2CH2CF2Cl, CF2HCH2CClH2, CFH2CHlCFClH, CH3CFClCH3, CH3CClHCFH2, CH3CH2CFClH, CH3CH2CClFCF2Cl, CH3CClHCF2CF2Cl, CH3CClHCFClCF3, CFH2CH2CF2CF2Cl, CH3CF2CFHCF2Cl, CF2HCH2CFHCF2Cl, CF3CH2CH2CF2Cl, CFH2CH2CFClCF3, CF3CF2CH2CClH2, CH3CF2CClHCF3, CF2HCH2CClHCF3, CH3CFClCFHCF3, CFH2CClHCFHCF3, CFH2CFClCH2CF3, CF3CH2CF2CClH2, CF2HCClHCH2CF3, CFClHCFHCH2CF3, CH3CFClCF2CF2H, CH3CF2CF2CFClH, CH3CClHCFHCF3, CFClHCH2CH2CF3, CH3CH2CFHCF2Cl, CH3CClHCH2CF3, CF3CH2CH2CClH2, CH3CH2CH2CFClH, CH3CH2CFClCH3, CH3C(CF3)FCFCl2, CH3C(CF2Cl)FCF2Cl, CH3C(CF3)HCF2Cl, CF2HC(CClH2)HCF3, CH3C(CF2H)ClCF3, CH3C(CFClH)FCF3, CH3C(CH3)ClCF3, CFH2CH2C(CF2Cl)FCF3, CF2ClCF2C(CH3)FCF2H, CF3CFHC(CH3)FCF2Cl, CF3CFClC(CH3)FCP2H, CF3CF2C(CF2H)HCClH2, CF3CF2C(CH3)ClCF2H, CF3CF2C(CH3)FCFClH, CH3CF2C(CF2Cl)HCF3, CH3CFClC(CF3)HCF3, CF2ClCHFC(CH3)FCF3, CH2ClCH2C(CF3)FCF3, CFH2CH2C(CF3)ClCF3, CFClHCH2C(CF3)HCF3, CF3CH2C(CClH2)FCF3, CF3CFHC(CH3)ClCF3, CF3CF2C(CH3)FCClFH, CH3CClHC(CF3)HCF3, CClH2CH2C(CF3)HCF3, CF2ClCF2C(CH3)FCH3, CF3CFClC(CH3)FCH3, CF2ClCFHC(CH3)HCH3, CF3CClHC(CH3)HCH3, CH3CH2C(CF3)ClCH3, and CFClHCH2C(CH3)HCH3.

2. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CF2HCCl2CF2H, CFH2CCl2CF3, CF2HCFClCFClH, CF3CFClCClH2, CFH2CFClCF2Cl, CF2ClCH2CF2Cl, CF3CH2CFCl2, CFClHCFHCFClH, CF2ClCFHCClH2, CFH2CFClCF2H, CF2HCClHCF2H, CF3CClHCFH2, CF2HCFHCFClH, CF3CFHCClH2, CFH2CFHCF2Cl, CFClHCH2CF3, CF2HCH2CF2Cl, CH3CClHCF2Cl, CH3CFHCCl2F, CFH2CFClCFH2, CH3CFClCF2H, CF2HCFHCClH2, CClFHCFHCFH2, CH3CFHCF2Cl, CF2HCH2CFClH, CFH2CH2CF2Cl, CF2HCH2CClH2, CFH2CH2CFClH, CH3CFClCH3, CH3CClHCFH2, and CH3CH2CFClH.

3. The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CF2ClCFHCClH2, CFH2CFClCF2H, CFH2CFHCF2Cl, CFClHCH2CF3, CF2HCH2CF2Cl, CH3CFClCF2H, and CH3CFHCF2Cl.

4 The hydrochlorofluorocarbons of claim 1 wherein said hydrochlorofluorocarbons are CH3CH2CClFCF2Cl, CH3CClHCF2CF2Cl, CH3CClHCFClCF3, CFH2CH2CF2CF2Cl, CH3CF2CFHCF2Cl, CF2HCH2CFHCF2Cl, CF3CH2CH2CF2Cl, CFH2CH2CFClCF3, CF3CF2CH2CClH2, CH3CF2CClHCF3, CF2HCH2CClHCF3, CH3CFClCFHCF3, CFH2CClHCFHCF3, CFH2CFClCH2CF3, CF3CH2CF2CClH2, CF2HCClHCH2CF3, CFClHCFHCH2CF3, CH3CFClCF2CF2H, CH3CF2CF2CFClH, CH3CClHCFHCF3, CFClHCH2CH2CF3, CH3CH2CFHCF2Cl, CF3CH2CH2CClH2, CH3CH2CH2CFClH, and CH3CH2CFClCH3.