WHICH DO NOT CONTRIBUTE SUBSTANTIALLY 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 2 chlorine atoms, and have OH rate constants from about 8 to about 25 cm ³ /molecule/secx10 ^" .

in response to the need for stratosphericaliy safe materials, substitutes have been developed and continue to be developed. 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 degreasing and defluxing substrates. In the EPA "Findings of the Chlorofluorocarbon Chemical Substitutes International Committee", EPA-600/9-88-009 (April 1988), it was reported that HCFC- 123 and 1 ,1-dichloro-1-f luoroethane (known in the art as HCFC- 141b) have potential as replacements for CFC-113 as cleaning agents.

The problem with these substitutes is that they have a long atmospheric lifetime as determined by their reaction with OH radicals in the troposphere. Table I below contains the OH rate constants and corresponding atmospheric lifetimes for these substitutes. In Table I, Exp K _0H stands for experimental K _0H rate constant, Est K _0H stands for estimated K _0H rate constant, Exp Life stands for experimental lifetime, and Est Life stands for estimated lifetime. The unit on the rate constant is cm ³ /molecule/ sec x 10- ¹⁴ and the unit on the lifetime is years.

TABLE I

It would be desirable to have substitutes with OH rate constants of at least about

8 cm ³ /molecule/secx10 ^"14 which equates to an atmospheric lifetime of 12 months or less.

If the OH rate constant of a compound is too high, the compound is a VOC (Volatile Organic Compound) because it is so reactive that it forms carbon dioxide which contributes to global warming. Thus, it would be desirable to have substitutes with OH rate constants of 25 crn ³ /rnolecule/secx10 ^"14 or less which equates to an atmospheric lifetime of at least 4 months.

Commonly assigned U.S. Patent 4,947,881 teaches a method of cleaning using hydrochlorofiuoropropanes having 2 chlorine atoms and a difluoromethylene group. European Publication 347,924 published December 27, 1989 teaches hydrochlorofiuoropropanes having a difluoromethylene group. International Publication Number WO 90/08814 published August 9, 1990 teaches azeotropes having at least one hydrochlorofiuoropropane having a difluoromethylene group.

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 quantities and as a result, substantial quantities of solvents are used to clean them.

Thus, substitutes having OH rate constants between about 8 and about 25 cm ³ /molecule/secx10 ^'14 and which are useful in many applications including as solvents are needed in the art.

SUMMARY OF THE INVENTION

Straight chain and branched chain hydrochlorofluorocarbons having 3 to 5 carbon atoms and 1 or 2 chlorine atoms total over 1100 compounds. Out of this over 1100 compounds, I was surprised to find a class of 88 hydrochlorofluorocarbons having OH rate constants from about 8 to about 25 cm ³ /molecule/secx10 ^"14 .

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 Compounds under Atmospheric Conditions", Chem. Rev. 86. 69

(1986) and Taylor et al., "Laser Photolysis/Laser-Induced Fluorescence Studies of Reaction Rates of OH with CH ₃ CI, CH ₂ CI ₂ , and CHCI ₃ over an Extended Temperature Range", Int. J. of Chem. Kinetics 21. 829 (1989).

The straight chain hydrochlorofluorocarbons having 3 carbon atoms of the present invention are listed in Table II below. The unit on the calculated K _0H is cm ³ /molecule/sec x 10 ^'14 and the unit on the calculated lifetime is years in Table II.

TABLE II

TABLE II (CONTINUED)

NUMBER CHEMICAL FORMULA

HCFC-253eb CCIFHCFHCFH ₂

HCFC-253ec CH ₃ CFHCF ₂ CI

HCFC-253fa CF ₂ HCH ₂ CFCIH

HCFC-253fc CFH ₂ CH ₂ CF ₂ CI

HCFC-262fa CF ₂ HCH ₂ CCIH ₂

HCFC-262fb CFH ₂ CH ₂ CFCIH

HCFC-271b CH ₃ CFCICH ₃

HCFC-271d CH ₃ CCIHCFH ₂

HCFC-271fb CH,CH,CFCIH

This present class with its OH rate constants between about 8 to about 25 cm ³ /moiecule/secx10' ¹⁴ was unexpected. I discovered this when I compared isomers having the same -CAB- group wherein -CAB- is -CCI ₂ -, -CH ₂ -, -CCIH-, -CCIF-, and -CHF- as the covered compound. I found that the isomers had OH rate constants less than 8 or greater than 25 cm ³ /molecule/sec x 10 ^"14 . For example, CFCIHCFHCFCIH and CF ₂ CICFHCCIH ₂ of the present invention have K _0H values of 19.1 and 8.4 cm ³ /molecule/sec x 10 ^'14 respectively as shown in Table II. In contrast, the isomers, CF ₂ HCFHCCI ₂ H and CCI ₂ FCFHCFH ₂ , have K _0H values of 31.3 and 30.0 cm ³ /molecule/sec x 10 ^*14 respectively as shown in Table VII, and thus, are VOCs.

Also, CFH ₂ CFCICF ₂ H of the present invention has a K _0H of 12.0 cm ³ /moiecule/sec x 10 ^"14 as shown in Table II. In contrast, the isomer, CF ₃ CFCICH ₃ , has a K _0H of 1.8 cm ³ /molecule/sec x 10 ^"14 as shown in Table VII, and thus, has a long atmospheric lifetime. The isomers, CFH ₂ CCI ₂ CFH ₂ and CH ₃ CCI ₂ CF ₂ H, have K _0H values of 49.33

and 34.14 cm ³ /molecule/secx10 ^'14 respectively as shown in Table VII and thus, are VOCs.

Additionally, CH ₃ CFHCCI ₂ F of the present invention has a K _0H of 8.6 cm ³ /molecule/sec x 10 ^'14 as shown in Table II. In contrast, the isomers, CCIH ₂ CFHCCIFH and CFH ₂ CFHCCI ₂ H, have K _0H values of 31.8 and 39.57 cm ³ /molecule/sec x 10 ^'14 respectively as shown in Table VII, and thus, are VOCs.

Additionally, CF ₂ HCH ₂ CCIH ₂ and CFH ₂ CH ₂ CFCIH of the present invention have K _0H values of 14.99 and 17.8 cm ³ /molecule/sec x 10 ^{" 1} respectively as shown in Table II. In contrast, the isomer, CF ₂ CICH ₂ CH ₃ , has a K _OH of 2.9 cm ³ /molecule/sec x 10 ^"14 as shown in Table VII, and thus, has a long atmospheric lifetime. Additionally, CH ₃ CH ₂ CFCIH of the present invention has a K _QH of 9.98 cm ³ /moiecule/sec x 10 ^"14 as shown in Table II. In contrast, the isomer, CFH ₂ CH ₂ CCIH ₂ , has a K _OH value of 35.8 cm ³ /molecule/sec x 10 ^"14 as shown in Table VII, and thus, is a VOC.

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

For example, Haszeldine, Nature 165, 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- trifluoropropyne. By using 3,3,3-trifiuoropropyne as a starting material, CF ₃ CFCICCIH ₂ (HCFC-234bb) may be prepared as follows. Commercially available trifluoromethyi iodide may be reacted with acetylene to prepare 3,3,3-trifiuoro-1-iodopropene which is then

dehydroiodinated to form 3,3,3-trifiuoropropyne. The 3,3,3- trifluoropropyne may then be reacted with commercially 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.

CF ₂ CICFHCCIH ₂ (HCFC-243ec) may be prepared as follows. , Commercially available 1 ,1 ,3-trichioropropene 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- difluoro-1-propene which may then be reacted with commercially available hydrogen fluoride to form 1 ,3-dichloro-1 ,1 , 2-trif iuoropropane.

CFH ₂ CFCICF ₂ H (HCFC-244ba) may be prepared as follows. Commercially available 1 ,3-difluoro-2-propanol may be dehydrated to 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- chioropropane.

CFH ₂ CFHCF ₂ CI (HCFC-244ec) may be prepared as follows.

Commercially available 1 ,1 ,3-trichloropropene may be fluorinated to form 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 1-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- tetraf Iuoropropane.

CFCIHCH ₂ CF ₃ (HCFC-244fa) may be prepared as follows. Commercially available 1 ,1 ,3-trichloropropene may be fluorinated to

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- tetraf iuoropropane.

CF ₂ HCH ₂ CF ₂ CI (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 dehydrohalogenated to form 1 ,3, 3-trifluoro-1 -propyne. The 1 ,3,3- trifluoro-1 -propyne may then be reacted with commercially available hydrogen chloride to form 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.

CH ₃ CFCICF ₂ H (HCFC-253bb) may be prepared as follows. Commercially available 1 ,2-dibromopropane may be dehydrohalogenated to form propyne. The propyne may then be fluorinated, chlorinated, and fluorinated to form 2-chloro-1 ,1 ,2- trifluoropropane.

CH ₃ CFHCF ₂ CI (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 dehydrogenated to form 1-chloro-1 -propyne. The 1-chioro-1 -propyne may then be reacted with commercially available hydrogen fluoride to form 1 -chloro-1 -fiuoro-1 -propene which may then be fluorinated to form 1-chloro-1 ,1 , 2-trif iuoropropane.

The preferred straight chain hydrochlorofluorocarbons having 3 carbon atoms are CF ₂ CICFHCCIH ₂ , CFH ₂ CFCICF ₂ H, CFH ₂ CFHCF ₂ CI, CFCIHCH ₂ CF ₃ , CF ₂ HCH ₂ CF ₂ CI, CH ₃ CFCICF ₂ H, and CH ₃ CFHCF ₂ CI.

The straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table III below. The unit on the calculated K _0H is cm ³ /molecule/secx10 ^'14 and the unit on the calculated lifetime is years in Table III below.

TABLE III

TABLE III (CONTINUED)

Known methods for making fluorinated compounds can be modified in order to form the straight chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention.

For example, R. N. Haszeldine et al., "Addition of Free Radicals to Unsaturated Systems. Part XIII. Direction of Radical Addition to Chloro-1 : 1 -dif luoroethylene". J. of Amer. Chem. Soc. 2193 (1957) teach the reaction of trifluoroiodomethane with chloro-1 :1 - difiuoroethyleπe to prepare 3-chioro-1 :1 :1 :2:2-peπtafluoro-3- iodopropane which is then chlorinated to form 1 ,1-dichloro-2,2,3,3,3- pentaf Iuoropropane (known in the art as HCFC-225ca). This known method can be modified to form CF ₃ CF ₂ CH ₂ CCIH ₂ (HCFC-355mcf) as follows. Commercially available perfluoroethyl iodide can be reacted with commercially available ethylene to prepare 1,1 ,1 ,2,2-pentafluoro- 4-iodobutane which is then chlorinated to form 1 ,1 ,1 ,2,2-pentafluoro- 4-chlorobutane.

CH ₃ CF ₂ CFHCF ₂ CI (HCFC-355lec) 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 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-difiuoro-1 -propyne which may then be fluorinated to form 1-chloro-1 ,2,3,3-tetrafluoro-1-butene which may then be reacted with commercially available hydrogen fluoride to form l-chioro-1 ,1 ,2,3,3- pentafluorobutane.

CF ₃ CH ₂ CH ₂ CF ₂ CI (HCFC-355lff) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be dechlorinated to form hexafluoro-2-butyne. The hexafluoro-2-butyne may be hydrogenated to form 1 ,1 ,1 ,4,4,4-hexaf luorobutane which may be chlorinated to form 1-chloro-1 ,1 ,4,4,4-pentaf luorobutane.

CFH ₂ CH ₂ CFCICF ₃ (HCFC-355mbf) may be prepared as follows.

Commercially available 1 ,4-dichloro-2-butyne may be reacted with commercially available hydrogen fluoride to form 1 ,4-dichloro-2-fluoro- 2-butene which may be fluorinated to form 1 ,2,4-trifluoro-2-butene. The 1 ,2,4-trifluoro-2-butenβ may be reacted with commercially available hydrogen chloride to form 2-chloro-1 , 2, 4-trif luorobutane which may be dehydrohalogenated, fluorinated, dehydrohalogenated, and fluorinated to form 2-chloro-1 ,1 ,1 ,2,4-pentafluorobutane.

CH ₃ CF ₂ CCIHCF ₃ (HCFC-355mdc) may be prepared as follows. Commercially available 3,4-dichloro-1-butene may be dehydrogenated to form 3,4-dichloro-1-butyne which may be reacted with commercially available hydrogen fluoride to form 1 ,2-dichloro-3,3- dif luorobutane. The 1 ,2-dichloro-3,3-dif luorobutane may be dehydrogenated to form 1 ,2-dichloro-3,3-difluoro-1-butene which may be reacted with commercially available hydrogen fluoride to form 2-

chloro-1 ,1 ,3,3-tetrafiuorobutane. The 2-chloro-1 , 1 ,3,3- tetrafiuorobutane 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-pentaf luorobutane.

CH ₃ CFCICFHCF ₃ (HCFC-355meb) may be prepared as follows. Commercially available 1 ,3-dichloro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1 ,3-difluoro-1 -butene. The 3-chioro-1 ,3-difluoro-1- butene may be fluorinated to form 2-chloro-2,3,4,4-tetrafluorobutane which may be dehydrohalogenated to 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-2,3,4,4,4-pentafluorobutane.

CH ₃ CFCICF ₂ CF ₂ H (HCFC-355pcb) may be prepared as follows.

Commercially available 1 ,3-dichioro-2-butene may be fluorinated to form 2-chloro-2,3,4-trifluorobutane which may be dehydrogenated to form 3-chloro-1 ,2,3-trifiuoro-1 -butene. The 3-chloro-1 ,2,3-trifluoro-1- butene may be fluorinated to form 2-chloro-2,3, 3,4,4- pentaf luorobutane.

CH ₃ CF ₂ CF ₂ CFCIH (HCFC-355rcc) may be prepared as follows. Commercially available 1 ,3-dichloro-2-butene may be fluorinated to form 1-chloro-2, 3, 3-trif luorobutane which may be dehydrogenated to form 1-chloro-2,3,3-trifluoro-1 -butene. The 1-chloro-2,3,3-trifluoro-1- butene may be fluorinated to form 1-chloro-1 ,2,2,3,3- pentafluorobutane.

CH ₃ CCIHCFHCF ₃ (HCFC-364med) may be prepared as follows. Commercially available 1 ,3-dichioro-2-butene may be reacted with

commercially available hydrogen fluoride to form 1 ,3-dichloro-2- f luorobutane which may be dehydrohalogenated to form 1 ,3-dichloro- 1 -butene. The 1 ,3-dichloro-1 -butene may be fluorinated to form 2- chloro-3,4,4-trifluorobutane which may be dehydrohalogenated to form 3-chloro-1 ,1-difluoro-1-butene. The 3-chloro- 1 , 1-dif luoro-1- butene may be fluorinated to form 2-chloro-3,4,4,4-tetrafiuorobutane.

The preferred straight chain hydrochlorofluorocarbons having 4 carbon atoms are CH ₃ CF ₂ CFHCF ₂ CI, CF ₃ CH ₂ CH ₂ CF ₂ CI, CFH ₂ CH ₂ CFCICF ₃ , CH ₃ CF ₂ CCIHCF ₃ , CH ₃ CFCICFHCF ₃ ,

CH ₃ CFCICF ₂ CF ₂ H, CH ₃ CF ₂ CF ₂ CFCIH, and CH ₃ CCIHCFHCF ₃ .

The branched chain hydrochlorofluorocarbons having 4 carbon atoms of the present invention are listed in Table IV below. The unit on the calculated K _0H is cm ³ /molecule/sec x 10 ^'14 and the unit on the calculated lifetime is years in Table IV below.

TABLE IV

Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 4 carbon atoms of the present invention.

CH ₃ C(CF ₃ )HCF ₂ CI (HCFC-355ims) may be prepared as follows.

Commercially available 1 -chloro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2-difluoro-2-methyipropane which may be dehydrohalogenated to form 1-chloro-1-fluoro-2-methylpropene. The 1-chloro-1-fluoro-2-methylpropene may be fluorinated to form 1- chloro-1 , 1 , 2-trif iuoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-3,3-difluoro-2-ππethylpropene. 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 dehydrogenated to form 3-chioro-1 ,3,3-trifluoro-2-methylpropene. The 3-chloro-1 ,3,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1 ,1 ,2,3,3-pentafluoro-2-methylpropane which may be dehydrohalogenated 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.

CH ₃ C(CF ₂ H)CICF ₃ (HCFC-355mps) may be prepared as follows. Commercially available 1 -chloro-2-methγlpropene may be fluorinated to form 1 ,1 ,2-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3,3-difluoro-2-methyipropene. The 3,3- difiuoro-2-methylpropene may be fluorinated to form 1 ,1 ,2,3- tetrafluoro-2-methytpropane which may be dehydrohalogenated to form 1 ,3,3-trifluoro-2-methylpropene. The 1 ,3,3-trifluoro-2- methylpropene may be fluorinated to form 1 ,1 ,2,3,3-pentafluoro-2- methylpropane which may be dehydrohalogenated to form 1 ,1 ,3,3-

tetraf luoro-2-methylpropene. The 1 ,1 ,3,3-tetrafluoro-2-methylpropene may be chlorinated to form 1 ,2-dichloro-1 ,1 ,4,4-tetrafluoro-2- methylpropane which may be fluorinated to form 2-chloro- 1 ,1 , 1 ,3,3- pentafluoro-2-methγlpropane.

CH ₃ C(CFCIH)FCF ₃ (HCFC-355mrs) may be prepared as follows. Commercially available 1 -chioro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2-difluoro-2-methylpropane which may be dehydrohalogenated to form 3-chioro-3-fluoro-2-methylpropene. The 3-chloro-3-fluoro-2-methylpropene may be fluorinated to form 1- chloro-1 ,2,3-trifluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1 ,3-difluoro-2-methylpropene. The 3-chloro-1 ,3-difluoro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2,3,3-tetrafluoro-2-methylpropane which may be dehydrohalogenated to form 3-chloro-1 , 1 ,3-trifluoro-2-methylpropene. The 3-chloro-1 ,1,3-trifluoro-2-methylpropene may be fluorinated to form 1-chloro-1 ,2,3,3,3-pentafluoro-2-methylpropane.

The preferred branched hydrochlorofluorocarbons having 4 carbon atoms are CH ₃ C(CF ₃ )HCF ₂ CI, CH ₃ C(CF ₂ H)CICF ₃ , and CH ₃ C(CFCIH)FCF ₃ .

The branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention are listed in Table V below. The unit on the calculated K _0H is cm ³ /molecule/sec x 10 ^'14 and the unit on the calculated lifetime is years in Table V below.

Known methods for making fluorinated compounds can be modified in order to form the branched hydrochlorofluorocarbons having 5 carbon atoms of the present invention.

CFH ₂ CH ₂ C(CF ₂ CI)FCF ₃ (HCFC-356mlfq) may be prepared as follows. Commercially available 1 ,4-dichloro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 1 ,4-dichloro- 2-trifluoromethyl-3-iodobutane which may be dehydrohalogenated to form 1 ,4-dichloro-3-trif luoromethy 1-1 -butene. The 1 r-dichloro-3- trifluoromethyl- 1 -butene may be hydrogenated to form 1 ,4-dichloro-2- trifluoromethylbutane which may be fluorinated to form 1 -chloro-2- trifluoromethyl-4-fluorobutane. The 1 -chloro-2-trifluoromethyl-4- f luorobutane may be dehydrogenated to form 1 -chloro-2- trifluoromethyl-4-fluoro-1 -butene which may be fluorinated to form 1- chloro-2-trif luoromethy I- 1 ,2,4-trif luorobutane. The 1-chloro-2- trifluoromethyl-1 ,2,4-trifluorobutane may be dehydrohalogenated to form 1-chloro-2-trifluoromethyl-1 ,4-difluoro-1 -butene which may be fluorinated to form 1-chloro-2-trifluoromethyl-1 ,1 ,2,4- tetraf luorobutane.

CF ₃ CFHC(CH ₃ )FCF ₂ CI (HCFC-357lsem) may be prepared as follows. Commercially available 1 ,4-dichloro-2-butene may be reacted with commercially available iodomethane to form 1 ,4-dichloro-3-iodo- 2-methylbutane which may be dehydrohalogenated to form 1 ,4- dichloro-3-methyl-1 -butene. The 1 ,4-dichioro-3-methyl-1 -butene may be fluorinated to form 1-chloro-2-methyl-3,4,4-trif luorobutane which may be dehydrohalogenated to form 1 , 1-dif luoro-3-methyl-4-chloro-1- butene. The 1 ,1-difluoro-3-methyl-4-chloro-1 -butene may be fluorinated to form 1-chloro-2-methyl-3,4,4,4-tetraf luorobutane which may be dehydrogenated to form 1-chloro-2-methyl-3,4,4,4-tetrafluoro-

1 -buteπe. The 1-chloro-2-methyl-3,4,4,4-tetrafluoro-1 -butene may be fluorinated to form 1 -chloro-2-methyl-1 ,2,3,4,4,4-hexafluorobutane which may be dehydrohalogenated to form 1 -chloro-2-methyl- 1 , 3, 4,4,4-pentafluoro-1 -butene. The 1-chloro-2-methyl-1 , 3,4,4,4- pentafluoro-1 -butene may be fluorinated to form 1 -chioro-2-methyl- 1 ,1 ,2,3,4,4,4-heptafiuorobutane.

CF ₃ CFCIC(CH ₃ )FCF ₂ H (HCFC-357mbsp) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-2-methyl-1 ,1 ,1 ,4,4 _l 4-hexafluoropropane which may be fluorinated to form 2-methyl-3-chioro- 1 ,1 , 1 ,2,3,4,4- heptafluorobutane. The 2-methyl-3-chloro-1 , 1 ,1 , 2,3,4,4- heptafluorobutane may be dehalogenated to form 3-chloro-2-methyl- 1 ,1 ,3,4,4,4-hexafluoro-1 -butene which may be reacted with commercially available hydrogen fluoride to form 3-chloro-2-methyl- 1 ,1 ,2,3, 4,4,4-heptaf luorobutane.

CF ₃ CF ₂ C(CH ₃ )CICF ₂ H (HCFC-357mcsp) may be prepared as follows. Commercially available 2,3-dichlorohexafiuoro-2-buteπe may be reacted with iodomethane to form 2-methyl-2,3-dichloro-3-iodo- 1 ,1 ,1 ,4,4,4-hexafluorobutane which may be fluorinated to form 2- methyl-1 ,1 ,1 ,2,3,3,4,4,4-nonafluorobutane. The 2-methyl- 1 ,1,1 , 2,3, 3,4,4,4-πonafluorobutane may be dehalogenated to form 2- methyl-1 ,1 ,3,3,4,4,4-heptafluoro-1 -butene which may be reacted with commercially available hydrogen chloride to form 2-chloro-2-methyl- 1 ,1 ,3,3,4,4,4-heptaf luorobutane.

CH ₃ CF ₂ C(CF ₂ CI)HCF ₃ (HCFC-357mlcs) may be prepared as follows. Commercially available 1 ,3-dichloro-2-butene may be reacted

with commercially available trifluoromethyl iodide to form 1 ,3-dichioro- 2-trifluoromethyl-3-iodobutane which may be fluorinated to form 1 ,3,3-trifluoro-2-trifluoromethyibutane. The 1 ,3,3-trifluoro-2- trifiuoromethylbutane may be dehydrogenated to form 1 ,3,3-trifluoro- 2-trif luoromethyl-1 -butene which may be fluorinated to form 1 , 1 ,2,3,3-pentafluoro-2-trifluoromethylbutane. The 1 , 1 ,2,3,3- pentafluoro-2-trifluoromethylbutane may be dehydrohalogenated to form 1 ,1 , 3, 3-tetrafluoro-2-trif luoromethy 1-1 -butene which may be reacted with commercially available hydrogen chloride to form 1 - chloro-1 , 1 ,3,3-tetrafluoro-2-trifluoromethylbutane.

CH ₃ CFCIC(CF ₃ )HCF ₃ (HCFC-357mmbs) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2, 3-dichloro-3-iodo-2-trif luoromethy 1-1 ,1 ,1 ,4,4,4-hexafluorobutane which may be fluorinated to form 2-trif luoromethy 1-1 , 1 ,1 , 2,3,3,4,4,4- nonafluorobutane. The 2-trif luoromethy 1-1 , 1 ,1 , 2,3, 3,4,4,4- nonafluorobutane may be dehalogenated to form 3-trifluoromethyl- 1 ,1 ,2,3,4,4,4-heptafluoro-1 -butene which may be hydrogenated to form 2-trif luoromethyl-1 , 1 ,1 , 2,3,4,4-heptaf luorobutane. The 2- trifluoromethyl-1 ,1 ,1 ,2,3,4,4-heptafluorobutane may be dehydrohalogenated to form 3-trifiuoromethyl-1 ,2,3,4,4,4-hexafiuoro- 1 -butene which may be hydrogenated to form 3-trif luoromethyi- 1 ,2,3,4,4,4-hexafluorobutane. The 3-trif luoromethy 1-1 , 2,3,4,4,4- hexafluorobutane may be dehydrohalogenated to form 3- trifluoromethyl-2, 3, 4,4,4-pentafluoro-1 -butene which may be reacted with commercially available hydrogen chloride to form 3-chloro-2- trif luoromethy 1-1 ,1 ,1 ,2,3-pentafluorobutane. The 3-chloro-2- trifluoromethyl-1 ,1 ,1 ,2,3-pentaf luorobutane may be dehalogenated to form 3-chloro-2-trif luoromethy 1-1 , 1 , 3-trif luoro-1 -butene which may be

reacted with commercially available hydrogen fluoride to form 3- chloro-2-trif luoromethy 1-1 ,1 , 1 ,3-tetrafluorobutane.

CF ₂ CICHFC(CH ₃ )FCF ₃ (HCFC-357mmel) may be prepared as follows. Commercially available 2,3-dichlororiexafluoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1 _f 1 ,l ,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methylperfluorobutane. The 2- methylperfiuorobutane may be dehalogenated to form 1 ,1 ,2,3,4,4,4- heptafiuoro-3-methyl-1 -butene which may be reacted with commercially available hydrogen chloride to form 4-chloro- 1 ,1 ,1 ,2,3,4,4-heptafluoro-2-methylbutane.

The method of R.N. Haszeldine et al., supra, can be modified to form CH ₂ CICH ₂ C(CF ₃ )FCF ₃ (HCFC-357 mmfo) as follows.

Commercially available perfluoroisopropyl iodide may be reacted with commercially available ethylene to prepare 2-trif luoromethy I- 1 ,1, 1 ,2- tetraf luoro-4-iodobutane which may then be chlorinated to form 2- trifluoromethyl-1 ,1 , 1 ,2-tetrafluoro-4-chlorobutane.

CFH ₂ CH ₂ C(CF ₃ )ClCF ₃ (HCFC-357mmfq) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1 ,1 ,1 ,4,4,4-hexafiuoro-2-trifluoromethylbutane which may be fluorinated to form 2-chloro-2-trifluoromethyl- perf luorobutane. The 2-chioro-2-trifluoromethyl-perfluorobutane may be dehalogenated to form 3-chloro-3-trifluoromethyl-1 , 1 ,2,4,4,4- hexafluoro-1 -butene which may be hydrogenated to form 2-chioro-2- trif luoromethy 1-1 ,1 ,1 ,3,4,4-hexafiuorobutane. The 2-chloro-2- trifluoromethyl- 1 ,1 ,1 ,3,4,4-hexafluorobutane may be fluorinated to

form 3-chioro-3-trifluoromethyl-1 ,4,4,4-tetrafluoro-1 -butene which may then be hydrogenated to form 2-chloro-2-trifluoromethyl-1 , 1 ,1 ,4- tetrafluorobutane.

CF ₃ CFHC(CH ₃ )CICF ₃ (HCFC-357msem) may be prepared as follows. Commercially available 2,3-dichlorohexafiuoro-2-butene may be reacted with commercially available iodomethane to form 2,3- dichloro-3-iodo-1 ,1 ,1 ,4,4,4-hexafiuoro-2-methylbutane which may be chlorinated to form 2,3,3-trichloro-1 ,1 ,1 ,4,4,4-hexafluoro-2- methylbutane. The 2,3,3-trichloro-1 ,1 ,1 ,4,4,4-hexafluoro-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 ,3,4,4,4-heptafluoro-2-methylbutane. The 3-chloro- 1 ,1 ,1 ,3,4,4,4-heptaf luoro-2-methylbutane may be dehydrohalogenated to form 1 ,1 ,1 ,4,4,4-hexafluoro-2-methyl-2-butene which may be reacted with commercially available hydrogen chloride to form 2- chloro-1 ,1 ,1 ,3,4,4,4-heptafluoro-2-methylbutane.

CF ₃ CF ₂ C(CH ₃ )FCCIFH (HCFC-358mcsr) may be prepared as follows. Commercially available 2,3-dichlorohexafiuoro-2-butene may be reacted with commercially available trifluoromethyl iodide to form 2,3-dichloro-3-iodo-1 ,1 ,1 ,4,4,4-hexafluoro-2-methylbutane which may be fluorinated to form 2-methyl-perf luorobutane. The 2-methyl- perf luorobutane may be dehalogenated to form 2-methyl-perfluoro-1- butene which may be reacted with commercially available hydrogen fluoride to form 1 ,1 ,2,3,3,4,4,4-octafluoro-2-methylbutane. The 1 ,1 ,2,3,3,4,4,4-octafluoro-2-methylbutane may be dehalogenated to form 1 , 3, 3,4,4,4-hexafluoro-2-methyl-1 -butene which may be chlorinated to form 1 ,2-dichloro-1 ,3,3,4,4,4-hexafluoro-2-

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- 1 ,2,3,3,4,4,4-heptafiuoro-2-methylbutane.

CH ₃ CCIHC(CF ₃ )HCF ₃ (HCFC-366mmds) may be prepared as follows. Commercially available 2,3-dichlorohexafluoro-2-butene may be reacted with trifluoromethyl iodide to form 2,3-dichloro-3-iodo- 1 ,1 ,1 ,4,4,4-hexafiuoro-2-trifluoromethylbutane which may be chlorinated to form 3-iodo-1 ,1 ,1 ,4,4,4-hexafluoro-2-methyl-2-butene. The 3-iodo-1 ,1 ,1 ,4,4,4-hexafluoro-2-trifluoromethyl-2-butene may be hydrogenated to form 3-iodo- 1 ,1 ,1 , 4,4,4-hexafluoro-2- trifiuoromethylbutane which may be dehydrohalogenated to form 2- iodo- 1 ,1 , 4,4, 4-pentafluoro-3-trifluoromethyl-1 -butene. The 2-iodo-

1 ,1 , 4,4, 4-pentafluoro-3-trifluoromethyl-1 -butene may be hydrogenated to form 3-iodo-1 ,1 ,1 ,4,4-pentafluoro-2-trifiuoromethylbutane which may be chlorinated to form 3-chloro- 1 ,1 ,1 , 4,4-pentafluoro-2- trifluoromethylbutaπe. The 3-chloro-1 ,1 ,1 ,4,4-pentafiuoro-2- trifluoromethylbutane may be dehydrohalogenated to form 2-chloro- 1 ,4,4,4-tetrafluoro-3-trifiuoromethyl-1 -butene which may be hydrogenated to form 3-chloro-1 ,1 ,1 ,4-tetrafluoro-2- trifiuoromethylbutane. The 3-chloro-1 ,1 ,1 ,4-tetrafluoro-2- trifluoromethylbutane may be dehydrohalogenated to form 2-chloro- 4,4,4-trifluoro-3-trif luoromethy 1-1 -butene which may be hydrogenated to form 3-chloro-1 ,1 ,1-trifluoro-2-trifluoromethylbutane.

The preferred branched hydrochlorofluorocarbons having 5 carbon atoms are CFH ₂ CH ₂ C(CF ₂ CI)FCF ₃ , CF ₃ CFHC(CH ₃ )FCF ₂ CI, CF ₃ CFCIC(CH ₃ )FCF ₂ H, CF ₃ CF ₂ C(CH ₃ )CICF ₂ H, CH ₃ CF ₂ C(CF ₂ CI)HCF ₃ ,

CH ₃ CFCIC(CF ₃ )HCF ₃ , CF ₂ CICHFC(CH ₃ )FCF ₃ , CH ₂ CICH ₂ C(CF ₃ )FCF ₃ , CFH ₂ CH ₂ C(CF ₃ )CICF ₃ , CF ₃ CFHC(CH ₃ )CICF ₃ , CF ₃ CF ₂ C(CH ₃ )FCCIFH, and CH ₃ CCIHC(CF ₃ )HCF ₃ .

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 VI below.

TABLE VI

Number Chemical Formula

HCFC-234cc CF ₂ CICF ₂ CCIH ₂ HCFC-234cd CH ₂ FCF ₂ CFCI ₂ HCFC-244ca CF ₂ HCF ₂ CCIH ₂ HCFC-244cb CFH ₂ CF ₂ CFCIH HCFC-253ca CFH ₂ CF ₂ CCIH ₂ HCFC-253cb CH ₃ CF ₂ CFCIH

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

2,2,3-trifluoropropane with antimony pentachioride and hydrogen fluoride at 120°C.

HCFC-244ca may be formed by any known method such as the reaction of 1 ,1 ,2,2,3-pentachloropropane with antimony pentachioride and hydrogen fluoride at 100°C. HCFC-244cb may be formed by any known method such as the reaction of 1-chloro-1 , 1 ,2,2- tetrafluoropropane with cesium fluoride and tetrabutylammonium bromide at 150°C.

HCFC-253ca may be formed by any known method such as the reaction of 1 ,2,3-trichloro-2-fiuoropropane with niobium pentachioride and hydrogen fluoride at 100°C. HCFC-253cb may be formed by any known method such as the reaction of 1 ,1 ,2,2-tetrachioropropaπe with tantalum pentafluoride and hydrogen fluoride at 130°C.

The present hydrochlorofluorocarbons may be used as solvents in vapor degreasing, solvent cleaning, cold cleaning, dewatering, dry cleaning, defiuxing, decontamination, spot cleaning, aerosol propelled 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, Rankine cycle and absorption refrigerants, and power fluids and especially as refrigerants for centrifugal refrigeration chillers.

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 VII below are isomers of the compounds of the present invention. As discussed above, these compounds have OH rate constants which are less than 8 cm ³ /molecule/secx10 ^"14 or greater than 25 cm ³ /molecule/secx10 ^"14 . The unit on the K _0H is cm ³ /molecule/secx10 ^"14 and the unit on the lifetime is years in Table VII below.

TABLE VII