AU2005227844A1 - Haloketone refrigerant compositions and uses thereof - Google Patents

Description

WO 2005/094395 PCT/US2005/001511 TITLE OF INVENTION HALOKETONE REFRIGERANT COMPOSITIONS AND USES THEREOF CROSS REFERENCE(S) TO RELATED APPLICATION(S) 5 This application claims the priority benefit of U.S. Provisional Application 60/549,978, filed March 4, 2004, and U.S. Provisional Application 60/575,037, filed May 26, 2004, and U.S. Provisional Application 60/584,785, filed June 29, 2004. 10 BACKGROUND OF THE INVENTION 1. Field of the Invention. The present invention relates to compositions for use in refrigeration and air conditioning systems comprising at least one haloketone or combinations thereof. Further, the present invention relates 15 to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising at least one haloketone or combinations thereof. The compositions of the present invention are useful in processes for producing refrigeration or heat or as heat transfer fluids. 20 2. Description of Related Art. The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being 25 phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC 134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as 30 a result of the Montreal Protocol. Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need 35 to identify new refrigerants with reduced global warming potential for the automobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for 1 WO 2005/094395 PCT/US2005/001511 refrigerants that can be used in all areas of the refrigeration and air conditioning industry. Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or 5 "natural" refrigerants such as C02 or ammonia. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought. The object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique 10 characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants. BRIEF SUMMARY OF THE INVENTION 15 The present invention relates to a haloketone refrigerant or heat transfer fluid selected from the group consisting of: 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 20 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 25 2-chloro-1 ,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;

CF

3 C(O)CBrFCF 2

CF

3 ;

CF

3

C(O)CF

2

CF

2 CBrF 2 ; CBrF 2

C(O)CF(CF

3

)

2 ;

CF

3 C(O)CBr(CF 3

)

2 ; 30 CBrF 2

CF

2

C(O)CF

2

CF

3 ;

CF

3 CBrFC(O)CF 2 CF3;

CF

3 CBrFC(O)CF 2

CF

2

CF

3 ;

CF

3

CF

2 C(O)CBrFCF 2

CF

3 ;

CF

3

CF

2

C(O)CF

2

CF

2 CBrF 2 ; 35 CF 3 C(O)CBr(CF 3

)CF

2

CF

3 ;

CF

3

C(O)CF(CF

3 )CBrFCF 3 ;

CF

3 C(O)CBrFCF 2

CF

2

CF

2

CF

3 ; 2 WO 2005/094395 PCT/US2005/001511 CF3C(O)CF 2

CF

2

CF

2

CF

2 CBrF 2 ; CF3CBrFC(O)CF 2

CF

2 CF2CF 3 ; CF3CF 2 G(O)CBrFCF 2

CF

2

CF

3 ; CF3CF 2

C(O)CF

2

CF

2

CF

2 CBrF 2 ; 5 CF3CF 2 CBrFC(O)CF 2

CF

2 0F 3 ; CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 ; CF3CBrFC(O)CF(CF 3

)CF

2

CF

3 ;

CF

3

CF

2 C(O)CBr(CF3)0F 2 0F 3 ; CF3CF2C(O)CF(CBrF 2

)CF

2

CF

3 ; 10 CBrF 2

CF

2 CF2C(O)CF(CF 3

)

2 ;

CF

3

CF

2 CBrFC(O)CF(CF 3 )2; CF3CF 2

CF

2 C(O)CBr(CF 3

)

2 ;

(CF

3

)

2 CBrC(O)CF(CF 3

)

2 ;

CF

3 CBrFCF 2

C(O)CF(CF

3

)

2 ; 15

CHF

2

CF

2 C(O)CBr(CF 3

)

2 ; (CFz 3

)

2 CHC(O)CBr(CF 3

)

2 ;

CHF

2

CF

2 C(O)CBrFCF 3 ;

(CF

3

)

2 CHC(O)CBrFCF 3 ;

(CF

3

)

2 CHC(O)CBrF 2 ; 20 CBrF 2

CF

2

C(O)CH(CF

3

)

2 ; CBrF 2

C(O)CF(CF

3

)OCF

3 ; CBrF2CF 2

C(O)CF(CF

3

)OCF

3 ; CBrF2CF 2

CF

2 C(O)CF(0F 3

)OCF

3 ; CBrF 2

C(O)CF(CF

3 )0C 2

F

5 ; 25 CBrF 2

CF

2

C(O)CF(CF

3 )0C 2

F

5 ; CBrF 2 C(O)CF(0F 3

)OCF

2

C

2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF

2

C

2

F

5 * CBrF 2

C(O)CF(CF

3

)OCF(CF

3

)

2 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF(CF

3

)

2 ; 30 CF3CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 ;

CF

3 gCBrFC(O)CF(CF 3

)OCF

3 ;

CF

3 gCBrFC(O)CF(CF 3

)OC

2

F

5 ;

CF

3 CBrFC(O)CF(CF 3 )0CF 3 ; (CF3)2CBrC(O)CF(CF 3

)OCF

3 ; 35 CF 3 CBrFC(O)CF(CF 3 )0C 2 Fg; (0F3) 2 CBrC(O)CF(CF 3

)OC

2

F

5 ; CF3CBrFC(O)CF(CF 3 )00F 2

C

2

F

5 ; 3 WO 2005/094395 PCT/US2005/001511

CF

3 CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 ; CBrF 2

C(O)CF(OCF

2

CHF

2

)CF

3 ; CBrF 2 C(O)CH (OCF 2 CH F 2

)CF

3 ; CBrF 2

C(O)CF(OCH

3

)CF

3 ; 5 CBrF 2

C(O)CF(CF

2 0CH 3

)CF

3 ;

CCIF

2 CFBrC(O)CF 2

CF

3 ; CBrF 2

CFCIC(O)CF

2

CF

3 ;

CCIF

2 CFBrC(O)CF(CF 3

)

2 ; CBrF 2

CFCIC(O)CF(CF

3

)

2 ; 10 CCIF 2 CFBrC(O)CF(CF 3

)(C

2

F

5 ); CBrF 2 CFCIC(O)CF(CF3)(C 2

F

5 );

CCIF

2 C(O)CBr(CF 3

)

2 ;

CCIF

2

CF

2 C(O)CBr(CF 3

)

2 ;

CF

3 CCIFC(O)CBr(CF 3

)

2 ; 15 CCIF 2 C(O)CBrFCF 3 ;

CCIF

2

CF

2 (O)CCBrFCF 3 ;

CF

3 CCIFC(O)CBrFCF 3 ; CBrF 2

C(O)CCI(CF

3

)

2 ; CBrF 2

CF

2

C(O)CC(CF

3

)

2 ; 20 CBrF 2

C(O)CCIFCF

3 ; CBrF 2

CF

2

C(O)CCIFCF

3 ; and combinations thereof. Disclosed herein also are the above listed compounds for use in refrigeration or air conditioning systems employing a centrifugal compressor, refrigeration or air conditioning systems employing a multi 25 stage centrifugal compressor, and/or employing a single slab/single pass heat exchanger, or refrigeration or air conditioning systems employing a 2-stage centrifugal compressor. Also disclosed herein are processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink using the 30 present inventive compositions. DETAILED DESCRIPTION OF THE INVENTION The haloketone refrigerant compositions of the present invention comprise a single compound or a combination comprising more 35 than one haloketone compound. Compositions of the present invention have no ozone depletion potential and low global warming potential . For example, haloketones, 4 WO 2005/094395 PCT/US2005/001511 alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use. The haloketones of the present invention are compounds containing fluorine, carbon, at least one ketone group oxygen, and 5 optionally hydrogen, chlorine or bromine. Haloketones may be represented by the formula R 3

COR

4 , wherein R 3 and R 4 are independently selected from straight or branched chain, saturated or unsaturated, aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine. R 3 and R 4 may be joined to form a cyclic 10 haloketone ring. The haloketones may contain from about 2 to 10 carbon atoms. Preferred haloketones contain 4 to 8 carbon atoms. The haloketones of the present invention may further contain heteroatoms, such as oxygen thus forming additional ketone groups, ether groups, aldehyde groups, or ester groups. Representative haloketones are listed 15 in Table 1. The bromofluoroketones of the present invention comprise at least one selected from the group consisting of: monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, 20 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. The following compounds are representative of the monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, 25 (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones of the present invention:

CF

3 C(O)CBrFCF 2

CF

3 , CF 3

C(O)CF

2

CF

2 CBrF 2 , CBrF 2

C(O)CF(CF

3

)

2 ,

CF

3 C(O)CBr(CF3) 2 , CBrF 2

CF

2

C(O)CF

2

CF

3 , CF 3 CBrFC(O)CF 2

CF

3 ,

CF

3 CBrFC(O)CF 2

CF

2

CF

3 , CF 3

CF

2 C(O)CBrFCF 2

CF

3 , 30 CF 3

CF

2

C(O)CF

2

CF

2 CBrF 2 , CF 3 C(O)CBr(CF 3

)CF

2

CF

3 ,

CF

3 C(O)CF(CF3)CBrFCF 3 , CF 3 C(O)CBrFCF 2

CF

2

CF

2

CF

3 ,

CF

3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 , CF 3 CBrFC(O)CF 2

CF

2

CF

2

CF

3 ,

CF

3

CF

2 C(O)CBrFCF 2

CF

2

CF

3 , CF 3

CF

2

C(O)CF

2

CF

2

CF

2 CBrF 2 ,

CF

3

CF

2 CBrFC(O)CF 2

CF

2

CF

3 , CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 , 35 CF 3 CBrFC(O)CF(CF 3

)CF

2

CF

3 , CF 3

CF

2 C(O)CBr(CF 3

)CF

2

CF

3 ,

CF

3

CF

2 C(O)CF(CBrF 2

)CF

2

CF

3 , CBrF 2

CF

2

CF

2

C(O)CF(CF

3

)

2 ,

CF

3

CF

2 CBrFC(O)CF(CF 3

)

2 , CF 3

CF

2

CF

2 C(O)CBr(CF 3

)

2 , 5 WO 2005/094395 PCT/US2005/001511 (0F 3

)

2 CBrC(O)CF(CF 3

)

2 , CF 3 CBrFCF 2

C(O)CF(CF

3

)

2 ,

OHF

2

CF

2 C(O)CBr(0F 3

)

2 , (0F 3

)

2 CHC(O)CBr(CF 3

)

2 ,

CHF

2

CF

2 C(O)CBrFCF 3 , (0F 3

)

2 CHC(O)CBrFCF 3 , (0F 3

)

2 CHC(O)CBrF 2 , CBrF 2

CF

2

C(O)CH(CF

3

)

2 , CBrF 2 C(O)CF(0F 3

)OCF

3 , 5 CBrF 2

CF

2

C(O)CF(CF

3

)OCF

3 , CBrF 2

CF

2

CF

2 C(O)CF(0F 3 )00F 3 , CBrF 2

C(O)CF(CF

3 )0C 2

F

5 , CBrF 2

CF

2

C(O)CF(CF

3 )0C 2

F

5 , CBrF 2

C(O)CF(CF

3

)OCF

2

C

2 FFs, CBrF 2

CF

2 C(O)CF(0F 3

)OCF

2

C

2

F

5 , CBrF 2 C(O)CF(0F 3

)OCF(CF

3

)

2 , CBrF 2

CF

2 C(O)CF(0F 3

)OCF(CF

3

)

2 ,

CF

3 CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 , CF 3 CBrFC(O)GF(CF 3 )00F 3 , 10 CF 3 CBrFC(O)CF(CF 3 )0C 2

F

5 , CF 3 CBrFC(O)CF(0F 3

)OCF

3 ,

(GF

3

)

2 CBrC(O)CF(0F 3

)OCF

3 , CF 3 CBrFC(O)CF(CF3)0C 2

F

5 , (0F 3

)

2 CBrC(O)CF(CF 3 )0C 2

F

5 , CF 3 CBrFC(O)CF(CF 3

)OCF

2

C

2

F

5 ,

CF

3 CBrFC(O)CF(CF3)OCF(CF 3

)

2 , CBrF 2

C(O)CF(OCF

2 CH F 2

)CF

3 , CBrF 2

C(O)CH(OCF

2 CH F 2

)CF

3 , CBrF 2

C(Q)CF(OCH

3 )0F 3 , 15 CBrF 2

C(O)CF(CF

2 00H 3

)CF

3 , CCIF 2 CFBrC(O)CF 2

CF

3 , CBrF 2

CFCIC(O)CF

2 CF3, CCI F 2 CFBrC(O)CF(CF 3

)

2 , CBrF 2

CFCIC(O)CF(CF

3

)

2 , CCIF 2 CFBrC(O)CF(CF 3

)(C

2

F

5 ), CBrF 2

CFCIC(O)CF(CF

3

)(C

2

F.

5 ), CCIF 2 C(O)CBr(CF 3

)

2 ,

CCIF

2

CF

2 C(O)CBr(CF 3

)

2 , CF 3 C0IFC(O)CBr(CF 3

)

2 , CCIF 2 C(O)CBrFCF 3 , 20 CCIF 2

CF

2 (O)CCBrFCF 3 , CF 3 00I FC(O)CBrFCF 3 , CBrF 2

C(O)CCI(CF

3

)

2 , CBrF 2

CF

2

C(O)CCI(CF

3

)

2 , CBrF 2

C(O)CCIFCF

3 and CBrF 2

CF

2 C(O)CCI FOE 3 . TABLE 1 25 Compound Chemical Formula Chemical Name GAS Rea. I INo. Haloketones PEIK CF 3

CF

2 C(O)CF(CFa) 2 1,1,1,2,2,4,5,5,5-nonafluoro-4- 756-13-8 (trifiuoromethyl)-3-pentanone (or _____________ erfluoroethylisopropyl ketone) PMIK CF 3

CCO)CF(CF

3

)

2 1 ,1,1,3,4,4,4-heptafluoro-3- 756-12-7 (trifluoromethyl)-2-butanone (or p rfluoromethylisopropyl ketone)

(CF

3

)

2 CFC(O)CF(CF3)2 1,1,1 ,2,4,5,5,5-octafluoro-2,4 bis(trifluo ro methyl)-3-penta none ______

CHF

2

CF

2

C(O)CF(CF

3

)

2 I ,11,2,4,4,5,5-octafluoro-2 ______________(trifluoromethyl)-3-pentanone

CF

3

CF

2

CF

2

COCF(CF

3

)

2 1 ,1 ,1,2,4,4,5,5,6,6, 6-undecafluoro-2 (trifluoromethyl)-3-hexanone CF3OCF 2 - 1,1,2,2,4,5,5,5-octafluoro-1

CF

2

C(O)CF(CF

3

)

2 (trifluoromethoxy)-4-(trifluoromethyl)-3 pentanone

CF

3

CF

2

C(O)CH(CF

3

)

2 I ,11,2,2,5,5,5-octafluoro-4- 61637-91-0 _____________ _________________(trifluoromethyl)-3-pentanone______

CF

3

CF

2 C(O)CCI(CF3) 2 2-chloro-1 ,1 ,1,4,4,5,5,5-octafluoro-2- 83714-48-1 6 WO 2005/094395 PCT/US2005/001511 (trifluoromethyl)-3-pentanone

CF

3 C(O)CBrFCF 2

CF

3 3-bromo-1,1,1,3,4,4,5,5,5-nonafluoro-2 perfluoropentanone

CHF

2

CF

2 C(0)CBrFCF3 2-bromo-1,1,1,2,4,4,5,5-octafluoro-3 pentanone 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone (PEIK) is commercially available from 3 MTM (St. Paul, Minnesota). 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone (PMIK); 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 5 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 pentanone; and 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone may be prepared as described in US 6,478,979 incorporated herein by 10 reference. 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone may be prepared from "HFP dimer" as described by England in Journal of Organic Chemistry, volume 49(no. 21), pages 4007 to 4008 (1984). 2 chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone may be prepared as described by Saloutina, et al. in Izvestiya Adademii Nauk 15 SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The bromofluoroketones of the present invention described previously including monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, 20 (fluoroal koxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones can be prepared as described in the following. Monobromoperfluoroketones CF 3

C(O)CF

2

CF

2 CBrF 2 ,

CF

3

CF

2

C(O)CF

2

CF

2 CBrF 2 and CF 3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 of the 25 present invention may be prepared by bromination of the corresponding monohydroperfluoroketones by the technique of Kolenko and Plashkin in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1648 to 1650 (1977), and by Zapevalov, et al. in Zhurnal Organicheskoi Khimii, Vol. 26, pages 265 to 272 (1990). CF 3

C(O)CF

2

CF

2 CBrF 2 may be 30 prepared by bromination of monohydroperfluoroketone

CF

3

C(O)CF

2

CF

2

CHF

2 , which may be prepared by isomerization of an epoxide as described by Zapelov et al. in Zhurnal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva, Vol. 18, pages 591 to 593 (1973). CF 3

CF

2

C(O)CF

2

CF

2 CBrF 2 and CF 3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 7 WO 2005/094395 PCT/US2005/001511 may be prepared by bromination of monohydroperfluoroketones

CF

3

CF

2

C(O)CF

2

CF

2

CHF

2 and CF 3

C(O)CF

2

CF

2

CF

2

CF

2

CHF

2 , respectively, by the technique of Saloutina, et al. in Zhumal Organicheskoi Khimii, Vol. 29, pages 1325 to 1336 (1993). 5 Preparation of monobromoperfluoroketones

CF

3

C(O)CF

2

CF

2 CBrF 2 , CF 3

CF

2

C(O)CF

2

CF

2 CBrF 2 and

CF

3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 of the present invention by conversion of the monohydroperfluoroketone terminal C-H bond to a terminal C-Br may be carried out using brominating agents such as elemental bromine, 10 phosphorous pentabromide, or a mixture of bromine and phosphorous tribromide. The preferred brominating agent is a mixture of bromine and phosphorous tribromide. Reaction of a monohydroperfluoroketone and a brominating agent may be carried out under substantially anhydrous conditions in the 15 vapor phase or liquid phase in a container fabricated from materials of construction suitable for contact with bromine and hydrogen bromide at temperatures of about 300 0 C to 600 0 C. Examples of such materials of construction include metallic alloys containing a nickel such as, for example, Hastelloy T M C and Hastelloy T M B. The reaction takes place 20 under the autogenous pressures of the reactants at the reaction temperature. The ratio of the brominating agent to the monohydroperfluoroketones is at least about I mole of brominating agent per mole of monohydroperfluoroketone and preferably about 1.3 moles of 25 brominating agent per mole of monohydroperfluoroketone. More than 1.7 moles of brominating agent per mole of monohydroperfluoroketone provides little benefit. Brominating the monohydroperfluoroketone may be conducted at temperatures of from about 300 0 C to about 6000C. Using the preferred 30 brominating agent, the temperature is preferably conducted from about 300 0 C to 350 0 C. Contact times between the brominating agent and the monohydroperfluoroketone may be from about one hour to about twenty hours. At the end of the contact period the reaction mixture is cooled 35 and then treated with a reagent to decompose the brominating agent such as sodium sulfite. The monobromoperfluoroketone may be isolated by collecting the organic phase followed by distillation. 8 WO 2005/094395 PCT/US2005/001511 Monobromoperfluoroketones CF 3

CF

2 C(O)CBrFCF 2 CF3,

CF

3 CF2CBrFC(O)CF(CF3)2, (CF 3

)

2 CBrC(O)CF(CF 3

)

2 ,

CF

3

CF

2 C(O)CBr(CF 3

)CF

2

CF

3 and CF3CBrFC(O)CF(CF 3 )CF2CF3, as well as mixtures of monobromoperfluoroketones of the present invention 5 CF 3 C(O)CBrFCF 2

CF

3 and CF 3 CBrFC(O)CF 2

CF

3 , or

CF

3 C(O)CBrFCF 2

CF

2

CF

2 CF3 and CF 3 CBrFC(O)CF 2

CF

2 CF2CF3, or

CF

3

CF

2 C(O)CBrFCF 2

CF

2 CF3 and CF 3

CF

2 CBrFC(O)CF 2 CF2CF3, may be prepared by contacting perfluoroolefin epoxides, such as the epoxide of perfluoro-2-pentene, perfluoro-2-heptene, or perfluoro-3-heptene, with an 10 alkali metal bromide as described by Saloutina et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The perfluoroolefin epoxides may be prepared by contacting perfluoroolefin with an alkali metal hypohalite as described by Kolenko, et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 2509-2512 (1979). 15 The contact of perfluoroolefin epoxides with alkali metal bromides may be carried out in a polar non-protic solvent such as glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl 20 sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile. Preferred solvents for contacting perfluoroolefin epoxides with alkali metal bromides are glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl 25 ether, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile. Alkali metal bromides suitable for opening the perfluoroolefin epoxide ring and formation of a C-Br bond include lithium bromide, sodium bromide, potassium bromide, and cesium bromide; sodium and lithium 30 bromide are preferred. The mole ratio of the alkali metal bromide to the perfluoroolefin epoxide is at least about 2:1, preferably about 10:1. Reaction of alkali metal bromides and perfluoolefin epoxide may be conducted in the liquid phase under substantially anhydrous 35 conditions at temperatures of from about I 00C to about 1500C, with contact times of from about 0.5 hour to about thirty-six hours. Specific pressure conditions are not critical. 9 WO 2005/094395 PCT/US2005/001511 At the end of the contact period the reaction mixture may be distilled to isolate the monobromoperfluoroketone. Monobromoperiluoroketones of the present invention CBrF 2

C(O)CF(CF

3

)

2 , CBrF 2

CF

2

C(O)CF

2

CF

3 , CF 3 CBrFCF 2

C(O)CF(CF

3

)

2 , 5 CF 3

CF

2

C(O)CF

2

CF

2

CF

2 CBrF 2 , CBrF 2

CF

2

CF

2

C(O)CF(CF

3

)

2 , and CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 may be prepared by reacting a monobromoperfluoroacyl fluoride with a perfluoroolefin. CBrF 2

C(O)CF(CF

3

)

2 may be prepared by reacting CBrF 2 C(O)F with CF 3

CF=CF

2 ; CBrF 2

CF

2

C(O)CF

2

CF

3 may be prepared by reacting 10 CBrF 2

CF

2 C(O)F with CF 2

=CF

2 ; CF 3

CF

2

C(O)CF

2

CF

2

CF

2 CBrF 2 may be prepared by reacting CBrF 2

CF

2

CF

2

CF

2 C(O)F with CF 2

=CF

2 ; CBrF 2

CF

2

CF

2

C(O)CF(CF

3

)

2 may be prepared by reacting CBrF 2

CF

2

CF

2 C(O)F with CF 3

CF=CF

2 ; CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 3

CF=CFCF

3 ; and 15 CF 3 CBrFCF 2

C(O)CF(CF

3

)

2 may be prepared by reacting

CF

3 CBrFCF 2 C(O)F with CF 3

CF=CF

2 . Monobromoperfluoroketones of the present invention

CF

3 C(O)CBr(CF 3

)

2 , CF 3 CBrFC(O)CF 2

CF

2

CF

3 , CF 3 C(O)CBr(CF 3

)CF

2

CF

3 ,

CF

3

C(O)CF(CF

3 )CBrFCF 3 , CF 3

CF

2

CF

2 C(O)CBr(CF 3

)

2 , may be prepared 20 by reacting a perfluoroacyl fluoride with a monobromoperfluoroolefin.

CF

3 C(O)CBr(CF 3

)

2 may be prepared by reacting CF 3 C(O)F with

CF

3 CBr=CF 2 ; CF 3 CBrFC(O)CF 2

CF

2

CF

3 may be prepared by reacting CBrF=CF 2 with CF 3

CF

2

CF

2 C(O)F; a mixture of CF 3 C(O)CBr(CF 3

)CF

2

CF

3 and CF 3

C(O)CF(CF

3 )CBrFCF 3 may be prepared by reacting 25 CF 3 CBr=CFCF 3 with CF 3 C(O)F; and CF 3

CF

2

CF

2 C(O)CBr(CF 3

)

2 may be prepared by reacting CF 3

CF

2

CF

2 C(O)F with CF 3 CBr=CF 2 . (Perfluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula RIC(O)CF(CF 3 )ORF, wherein R 1 is a C1 to C 3 monobromoperfluoroalkyl radical, and RF is a C 1 to C 3 perfluoroalkyl 30 radical, may be obtained by reacting monobromoperfluoroacy fluorides of the formula R 1 C(O)F with perfluorovinyl ethers of the formula

CF

2 =CFORF. Representative (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CBrF 2

C(O)CF(CF

3

)OCF

3 , CBrF 2

CF

2

C(O)CF(CF

3

)OCF

3 , 35 CBrF 2

CF

2

CF

2

C(O)CF(CF

3

)OCF

3 , CBrF 2

C(O)CF(CF

3

)OC

2

F

5 , CBrF 2

CF

2

C(O)CF(CF

3

)OC

2

F

5 , CBrF 2

C(O)CF(CF

3

)OCF

2

C

2

F

5 , 10 WO 2005/094395 PCT/US2005/001511 CBrF 2

CF

2

C(O)CF(CF

3

)OCF

2

C

2

F

5 , CBrF 2

C(O)CF(CF

3

)OCF(CF

3 )2, CBrF 2

CF

2

C(O)CF(CF

3

)OCF(CF

3

)

2 , CF 3 CBrFC(O)CF(CF 3 )OCF(CF3)2,

CF

3 CBrFC(O)CF(CF 3

)OCF

3 , and CF 3 CBrFC(O)CF(CF 3 )OC2F. CBrF 2

C(O)CF(CF

3

)OCF

3 may be prepared by reacting 5 CBrF 2 C(O)F with CF 2

=CFOCF

3 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF

3 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 2

=CFOCF

3 ; CBrF 2

CF

2

CF

2

C(O)CF(CF

3

)OCF

3 may be prepared by reacting CBrF 2

CF

2

CF

2 C(O)F with CF 2

=CFOCF

3 ; CBrF 2

C(O)CF(CF

3

)OC

2

F

5 may be prepared by reacting CBrF 2 C(O)F with CF 2

=CFOC

2

F

5 ; 10 CBrF 2

CF

2

C(O)CF(CF

3

)OC

2

F

5 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 2

=CFOC

2

F

5 ; CBrF 2

C(O)CF(CF

3

)OCF

2

C

2

F

5 may be prepared by reacting CBrF 2 C(O)F with CF 2

=CFOCF

2

C

2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3 )OCF2C2F5 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 2

=CFOCF

2

C

2

F

5 ; CBrF 2

C(O)CF(CF

3

)OCF(CF

3

)

2 15 may be prepared by reacting CBrF 2 C(O)F with CF 2

=CFOCF(CF

3

)

2 ; CBrF 2

CF

2

C(O)CF(CF

3 )OCF(CF3)2 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 2

=CFOCF(CF

3

)

2 ; CF 3 CBrFC(O)CF(CF 3

)OCF

3 may be prepared by reacting CF 3 CBrFC(O)F with CF 2

=CFOCF

3 ; and

CF

3 CBrFC(O)CF(CF 3

)OC

2 F5 may be prepared by reacting CF 3 CBrFC(O)F 20 with CF 2

=CFOC

2

F

5 . (Perfluoroalkoxy)monobromoperfluoroketones of the formula RlC(O)CF(CF 3 )ORF may also be obtained by reacting perfluoroalkoxyperfluoroacyl fluorides of the formula RFOCF(CF 3 )C(O)F with a monobromoperfluoroolefin. Representative 25 (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CF 3 CBrFC(O)CF(CF 3 )OCF3, (CF 3

)

2 CBrC(O)CF(CF 3 )OCF3,

CF

3 CBrFC(O)CF(CF 3 )OC2F5, (CF 3

)

2 CBrC(O)CF(CF 3

)OC

2 F5,

CF

3 CBrFC(O)CF(CF 3

)OCF

2

C

2 F, and CF 3 CBrFC(O)CF(CF 3 )OCF(CF3)2.

CF

3 CBrFC(O)CF(CF 3 )OCF3 may be prepared by reacting 30 CF 3 0C(CF 3 )FC(O)F with CF 2 =CBrF; (CF 3

)

2 CBrC(O)CF(CF 3 )OCF3 may be prepared by reacting CF 3 0C(CF 3 )FC(O)F with CF 3 CBr=CF 2 ;

CF

3 CBrFC(O)CF(CF 3

)OC

2

F

5 may be prepared by reacting

C

2

F

5 0C(CF 3 )FC(O)F with CF 2 =CBrF; (CF 3

)

2 CBrC(O)CF(CF 3 )OC2F5 may be prepared by reacting C 2

F

5

OC(CF

3 )FC(O)F with CF 3 CBr=CF 2 ; 35 CF3CBrFC(O)CF(CF3)OCF 2

C

2 F5 may be prepared by reacting

C

2

F

5

CF

2

OC(CF

3 )FC(O)F with CF 2 =CBrF; and 11 WO 2005/094395 PCT/US2005/001511

CF

3 CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 may be prepared by reacting

(CF

3

)

2

CFOC(CF

3 )FC(O)F with CF 2 =CBrF. (Fluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula R 1

C(O)CX(CF

3

)OR

2 , wherein X is H or F, R 1 is 5 a C1, C2, or C3 bromoperfluoroalkyl radical, and R 2 is a C1 to C3 alkyl or fluoroalkyl radical, may be prepared by reacting monobromoperfluoroacyl fluorides of the formula R 1 C(O)F with hydrofluorovinyl ethers of the formula CF 2 =CXO R 2 . Representative (fluoroalkoxy)monobromoperfluoroketones include 10 CBrF 2

C(O)CF(OCF

2

CHF

2

)CF

3 , CBrF 2

C(O)CH(OCF

2

CHF

2

)CF

3 , CBrF 2

C(O)CF(OCH

3

)CF

3 , and CBrF 2

C(O)CF(CF

2 0CH 3

)CF

3 . CBrF 2

C(O)CF(OCF

2

CHF

2

)CF

3 may be prepared by reacting CBrF 2 C(O)F with CF 2

=CFOCF

2

CHF

2 ; CBrF 2

C(O)CH(OCF

2

CHF

2

)CF

3 may be prepared by reacting CBrF 2 C(O)F with CF 2

=CHOCF

2

CHF

2 ; and 15 CBrF 2

C(O)CF(OCH

3

)CF

3 may be prepared by reacting CBrF 2 C(O)F with

CF

2

=CFOCH

3 . Another (fluoroalkoxy)monobromoperfluoroketone of the present invention includes CBrF 2

C(O)CF(CF

2 0CH 3

)CF

3 , prepared by reacting CBrF 2 C(O)F with CF 3

CF=CFOCH

3 . 20 The reaction of fluoroacyl fluorides with fluoroolefins is described by Fawcett, et al. in U. S. Patent No. 3,185,734 and Journal of the American Chemical Society, Vol. 84, pages 4285 to 4288 (1962). The teachings of these references may be applied to the aforementioned preparation of monobromoperfluoroketones by the reaction of 25 monobromoperfluoroacyl fluorides with perfluoroolefins as well as the aforementioned preparation of monobromoperfluoroketones by the reaction of perfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (perfluoroalkoxy)monobromoperfluoroketones by the reaction of 30 monobromoperfluoroacyl fluorides with perfluorovinyl ethers, or by the reaction of perfluoroalkoxyperfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (fluoroalkoxy)monobromoperfluoroketones by the reaction of monobromoperfluoroacyl fluorides with hydrofluorovinyl ethers. 35 Though not essential for preparing the ketones of the present invention, reaction of a fluoroacyl fluoride (such as a perfluoroacyl fluoride or monobromoperfluoroacyl fluoride) with a fluoroolefin (such as a 12 WO 2005/094395 PCT/US2005/001511 perfluoroolefin, monobromoperfluoroolefin, perfluorovinyl ether or hydrofluorovinyl ether) may be performed in a polar non-protic solvent such as N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and glycol ethers such 5 as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Preferred solvents for reacting fluoroacyl fluorides with fluoroolefin are glycol ethers. The reaction may be run under substantially anhydrous conditions. 10 The mole ratio of the fluoroolefin to fluoroacyl fluoride during the reaction may be at least about 1:1 to about 2:1, and preferably is about 1.1. The reaction of fluoroacyl fluoride with fluoroolefin is preferably conducted in the presence of a fluoride ion source such as an alkali metal 15 fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth metal fluoride, tetraalkylammonium fluoride, tetraalkylammonium hydrogen fluoride, trialkylammonium fluoride, or non-oxidizing transition metal fluorides. Preferred fluoride ion sources are potassium fluoride, cesium fluoride, and potassium bifluoride. The fluoride ion source may be present 20 at a level of 5 mole percent to 20 mole percent, preferably about 10 mole percent, based on the quantity of fluoroolefin present. Temperatures of from about 500C to about 2500C, preferably from about 100 C to about 1500C are effective to produce any of the fluorinated ketones of the present invention by reaction of a fluoroacy 25 fluoride with a fluoroolefin. The reaction of fluoroacyl fluoride with fluoroolefin may take place in batch mode or in semi-batch mode with the fluoroacyl fluoride added gradually to the mixture of the fluoroolefin, solvent, and fluoride ion source. Contact times suitable for the reaction may be from about 0.5 30 hour to about 24 hours. The reaction typically takes place under autogenous pressure provided by the reactants at the reaction temperature. Though not added intentionally to the reactions, hydrogen fluoride may be present in small amounts during the reactions of fluoroacyl 35 fluorides due to the presence of traces of water. Reaction of fluoroacyl fluorides with fluoroolefins may be conducted in a vessel formed of materials compatible with hydrogen fluoride at elevated temperatures and 13 WO 2005/094395 PCT/US2005/001511 pressures. Examples of such materials include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as MonelTM nickel-copper alloys, Hastelloy nickel-based alloys and, Inconel nickel-chromium alloys, and copper-clad steel. 5 The haloketone products may be isolated from the reaction mixture as a lower liquid layer or by distillation. After removing traces of fluoride salts by washing with water, such products may be purified by distillation. The present invention further includes 10 monohydromonobromoperfluoroketones in which one of the C-F bonds in a perfluoroketone has been replaced by a C-Br bond, and in addition, another of the C-F bonds in said perfluoroketone has been replaced by a C-H bond. Monohydromonobromoperfluoroketones of the present invention comprise CHF 2

CF

2 C(O)CBrFCF 3 , (CF 3

)

2 CHC(O)CBrFCF 3 , 15 CHF 2

CF

2 C(O)CBr(CF 3

)

2 , (CF 3

)

2 CHC(O)CBr(CF 3

)

2 , (CF 3

)

2 CHC(O)CBrF 2 and CBrF 2

CF

2

C(O)CH(CF

3

)

2 .

CHF

2

CF

2 C(O)CBrFCF 3 may be prepared by reacting

CHF

2

CF

2 C(O)F with CBrF=CF 2 ; (CF 3

)

2 CHC(O)CBrFCF 3 may be prepared by reacting (CF 3

)

2 CHC(O)F with CBrF=CF 2 ; CHF 2

CF

2 C(O)CBr(CF 3

)

2 may 20 be prepared by reacting CHF 2

CF

2 C(O)F with CF 3 CBr=CF 2 ;

(CF

3

)

2 CHC(O)CBr(CF3) 2 may be prepared by reacting (CF 3

)

2 CHC(O)F with CF 3 CBr=CF 2 ; and CBrF 2

CF

2

C(O)CH(CF

3

)

2 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 3

CH=CF

2 . The monohydromonobromoperfluoroketone

(CF

3

)

2 CHC(O)CBrF 2 may be 25 prepared by the reaction of the bromofluoroacyl fluoride CBrF 2 C(O)F with the monohydroperfluoroolefin CF 3

CH=CF

2 . The production of monohydromonobromoperfluoroketones by the reaction of monohyd roperfluoroacyl fluorides with monobromoperfluoroolefins, as well as by the reaction of 30 monobromoperfluoroacyl fluorides with monohydroperfluoroolefins, may use reaction conditions and procedure similar to those discussed hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin. The present invention further comprises monochloromonobromoperfluoroketones in which one of the C-F bonds in 35 a perfluoroketone has been replaced by a C-Br bond, and in addition, another one of the C-F bonds in said perfluoroketone has been replaced by a C-Cl bond. Monochloromonobromoperfluoroketones of the present 14 WO 2005/094395 PCT/US2005/001511 invention comprise compounds of the formula CXF 2

CFYC(O)CFRCF

3 , wherein X is CI and Y is Br, or wherein X is Br and Y is Cl, and wherein R is F, a CF 3 radical, or a C 2

F

5 radical. These compounds may be prepared by contacting an acid fluoride of the formula CXF 2 CFYC(O)F, prepared as 5 disclosed by Darst, et al. in U. S. Patent No. 5,557,010, with a perfluoroolefin of the formula CFR=CFR. Representative monochloromonobromoperfluoroketones include CCIF 2 CFBrC(O)CF 2

CF

3 , prepared by reacting CCIF 2 CFBrC(O)F with CF 2

=CF

2 ; CBrF 2

CCIFC(O)CF

2

CF

3 , prepared by reacting CBrF 2 CCIFC(O)F with 10 CF 2

=CF

2 ; CCiF 2 CFBrC(O)CF(CF 3

)

2 , prepared by reacting

CCIF

2 CFBrC(O)F with CF 2

=CFCF

3 ; and CBrF 2

CCIFC(O)CF(CF

3 )2, prepared by reacting CBrF 2 CCIFC(O)F with CF 2

=CFCF

3 . Monochloromonobromoperfluoroketones of the present invention further comprise CCIF 2 C(O)CBr(CF 3

)

2 , CCIF 2

CF

2 C(O)CBr(CF 3

)

2 , 15 CF 3 CCIFC(O)CBr(CF 3

)

2 , CCIF 2 C(O)CBrFCF 3 , CCIF 2

CF

2 C(O)CBrFCF 3 , and CF 3 CCIFC(O)CBrFCF 3 which may be prepared by reacting a monochloroperfluoroacyl fluoride with a monobromoperfluoroolefin.

CCIF

2 C(O)CBr(CF 3

)

2 may be prepared by reacting CCIF 2 C(O)F with

CF

3 CBr=CF 2 ; CCIF 2

CF

2 C(O)CBr(CF 3 )2 may be prepared by reacting 20 CCIF 2

CF

2 C(O)F with CF 3 CBr=CF 2 ; CF 3 CCIFC(O)CBr(CF 3

)

2 may be prepared by reacting CF 3 CCIFC(O)F with CF 3 CBr=CF 2 ;

CCIF

2 C(O)CBrFCF 3 may be prepared by reacting CCIF 2 C(O)F with

CF

2 =CBrF; CCIF 2

CF

2 C(O)CBrFCF 3 may be prepared by reacting

CCIF

2

CF

2 (O)F with CF 2 =CBrF; CF 3 CCIFC(O)CBrFCF 3 may be prepared 25 by reacting CF 3 CCIFC(O)F with CF 2 =CBrF. Monochloromonobromoperfluoroketones of the present invention further include CBrF 2

C(O)CCI(CF

3

)

2 , CBrF 2

CF

2 C(O)CCI(CF3)2, CBrF 2

C(O)CCIFCF

3 , and CBrF 2

CF

2

C(O)CCIFCF

3 which may be prepared by reacting a monobromoperfluoroacyl fluoride with a 30 monochloroperfluoroolefin. CBrF 2

C(O)CCI(CF

3

)

2 may be prepared by reacting CBrF 2 C(O)F with CF 3

CCI=CF

2 ; CBrF 2

CF

2

C(O)CC(CF

3

)

2 may be prepared by reacting CBrF 2

CF

2 C(O)F with CF 3

CCI=CF

2 ; CBrF 2

C(O)CCIFCF

3 may be prepared by reacting CBrF 2 C(O)F with CF 2 =CCIF; and CBrF 2

CF

2

C(O)CCIFCF

3 may 35 be prepared by reacting CBrF 2

CF

2 C(O)F with CF 2 =CCIF. The formation of monohydromonobromoperfluoroketones by the reaction of fluoroacyl fluorides of the formula CXF 2 CFYC(O)F with 15 WO 2005/094395 PCT/US2005/001511 perfluoroolefins, or by the reaction of monochloroperfluoroacyl fluorides with monobromoperfluoroolefins, or by the reaction of monobromoperfluoroacyl fluorides with monochloroperfluoroolefins, may use reaction conditions and procedure similar to those discussed 5 hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin. The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be 10 used, if desired. The refrigerant or heat transfer compositions of the present invention include: 1,1, 1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 15 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 pentanone; 20 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone;

CF

3 C(O)CBrFCF 2

CF

3 ;

CF

3

C(O)CF

2

CF

2 CBrF 2 ; CBrF 2

C(O)CF(CF

3

)

2 ; 25 CF 3 C(O)CBr(CF 3

)

2 ; CBrF 2

CF

2

C(O)CF

2 CF3;

CF

3 CBrFC(O)CF 2

CF

3 ;

CF

3 CBrFC(O)CF 2

CF

2

CF

3 ;

CF

3

CF

2 C(O)CBrFCF 2

CF

3 ; 30 CF 3

CF

2

C(O)CF

2

CF

2 CBrF 2 ;

CF

3 C(O)CBr(CF 3

)CF

2

CF

3 ;

CF

3

C(O)CF(CF

3 )CBrFCF 3 ;

CF

3 C(O)CBrFCF 2

CF

2

CF

2

CF

3 ;

CF

3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 ; 35 CF 3 CBrFC(O)CF 2

CF

2

CF

2

CF

3 ;

CF

3

CF

2 C(O)CBrFCF 2

CF

2

CF

3 ;

CF

3

CF

2

C(O)CF

2

CF

2

CF

2 CBrF 2 ; 16 WO 2005/094395 PCT/US2005/001511

CF

3

CF

2 CBrFC(O)CF 2 CF2CF3; CBrF 2

CF

2 C(O)CF(0F 3 )CF2CF 3 ;

CF

3 CBrFC(O)CF(CF 3 9)CF 2

CF

3 ;

CF

3

CF

2 C(O)CBr(0F 3

)CF

2

CF

3 ; 5 CF 3

CF

2 C(O)CF(CBrF 2

)CF

2

CF

3 ; CBrF 2

CF

2

CF

2 C(O)CF(CF3)2;

CF

3

CF

2 CBrFC(O)CF(CF3)2;

CF

3

CF

2

CF

2 C(O)CBr(CF 3

)

2 ;

(CF

3

)

2 CBrC(O)CF(0F 3

)

2 ; 10 CF 3 CBrFCF 2 C(O)CF(0F3)2;

CHF

2

CF

2 C(O)CBr(CF 3

)

2 ;

(CF

3

)

2 CHC(O)CBr(CF 3

)

2 ;

CHF

2

CF

2 C(O)CBrFCF 3 ;

(CF

3

)

2 CHC(O)CBrFCF3; 15 (0F 3

)

2 CHC(O)CBrF 2 ; CBrF 2

CF

2 C(O)CH(CF3)2; CBrF 2 C(O)CF(0F 3

)OCF

3 ; CBrF 2

CF

2 C(O)CF(CF3)OCF 3 ; CBrF 2

CF

2

CF

2

C(O)CF(CF

3 )OCF3; 20 CBrF 2

C(O)CF(CF

3 )0C 2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3 )0C2F5; CBrF 2 C(O)CF(0F 3

)OCF

2 C2F5; CBrF 2

CF

2 C(O)CF(CF3)00F 2

C

2

F

5 ; CBrF 2

C(O)CF(CF

3 )OCF(CF3)2; 25 CBrF 2

CF

2

C(O)CF(CF

3 )OCF(CF3)2;

CF

3 CBrFC(O)CF(CF 3 )OCF(CF3)2;

CF

3 CBrFC(O)CF(CF 3

)OCF

3 ;

CF

3 CBrFC(O)CF(0F 3 )0C 2

F

5 ;

CF

3 CBrFC(O)CF(CF 3

)OCF

3 : 30 (CF 3

)

2 CBrC(O)CF(CF 3 )00F 3 ;

CF

3 CBrFG(O)CF(CF 3 )0C2F5;

(CF

3

)

2 CBrC(O)CF(0F 3 )0C 2

F

5 ;

CF

3 CBrFC(O)CF(CF 3

)OCF

2

C

2

F

5 ;

CF

3 CBrFC(O)CF(CF 3 )OGF(CF3)2; 35 CBrF 2

C(O)CF(OCF

2

CHF

2 )0F3; CBrF 2 C(O)CH (OCF 2

CHF

2 )0F 3 ; CBrF 2

C(O)CF(OCH

3 )0F 3 ; 17 WO 2005/094395 PCT/US2005/001511 CBrF 2

C(O)CF(CF

2 0CH 3

)CF

3 ;

CCIF

2 CFBrC(O)CF 2

CF

3 ; CBrF 2

CFCIC(O)CF

2

CF

3 ;

CCIF

2 CFBrC(O)CF(CF 3

)

2 ; 5 CBrF 2

CFCIC(O)CF(CF

3

)

2 ;

CCIF

2 CFBrC(O)CF(CF 3

)(C

2

F

5 ); CBrF 2

CFCIC(O)CF(CF

3

)(C

2

F

5 );

CCIF

2 C(O)CBr(CF 3

)

2 ;

CCIF

2

CF

2 C(O)CBr(CF 3

)

2 ; 10 CF 3 CCIFC(O)CBr(CF 3

)

2 ;

CCIF

2 C(O)CBrFCF 3 ;

CCIF

2

CF

2 (O)CCBrFCF 3 ;

CF

3 CCIFC(O)CBrFCF 3 ; CBrF 2

C(O)CCI(CF

3

)

2 ; 15 CBrF 2

CF

2

C(O)CCI(CF

3

)

2 ; CBrF 2

C(O)CCIFCF

3 ; CBrF 2

CF

2

C(O)CCIFCF

3 ; and combinations thereof. The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal 20 stabilizer such as nitromethane. The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant composition by permitting one to observe the fluorescence of the dye 25 under an ultra-violet light at the point of a leak within a refrigeration or air conditioning system. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants. By "ultra-violet" dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or "near" ultra-violet region of the 30 electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning apparatus, 35 the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, 18 WO 2005/094395 PCT/US2005/001511 naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof. Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, 5 ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes. Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only 10 hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon. 15 Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME). Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R4[(OR 2 )xOR 3 ]y, wherein: x is an 20 integer from 1-3; y is an integer from 1-4; R 1 is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least 25 one of R 1 and R 3 is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. In the present polyoxyalkylene glycol ether solubilizing agents represented by R 1

[(OR

2 )xOR 3 ]y: x is preferably 1 2; y is preferably 1; R 1 and R 3 are preferably independently selected from 30 hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms;

R

2 is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 35 250 atomic mass units. The R 1 and R 3 hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R' and

R

3 hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, 19 WO 2005/094395 PCT/US2005/001511 isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. 5 Mylar@), R' and R 3 are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R 2 aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals - (OR 2 ). - that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical 10 comprising R2 in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R 2 oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R 1 is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms 15 and y bonding sites, the radical may be linear, branched or cyclic. Representative R' aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R 1 aliphatic hydrocarbon 20 radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3 trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals. Representative polyoxyalkylene glycol ether solubilizing agents 25 include but are not limited to: CH 3 0CH 2

CH(CH

3 )O(H or CH 3 ) (propylene glycol methyl (or dimethyl) ether), CH 3 0[CH 2

CH(CH

3

)O]

2 (H or CH 3 ) (dipropylene glycol methyl (or dimethyl) ether), CH 3

O[CH

2

CH(CH

3

)O]

3 (H or CH 3 ) (tripropylene glycol methyl (or dimethyl) ether),

C

2

H

5 0CH 2

CH(CH

3 )O(H or C 2

H

5 ) (propylene glycol ethyl (or diethyl) ether), 30 C 2

H

5

O[CH

2

CH(CH

3

)O]

2 (H or C 2

H

5 ) (dipropylene glycol ethyl (or diethyl) ether), C 2

H

5

O[CH

2

CH(CH

3 )O]3(H or C 2

H

5 ) (tripropylene glycol ethyl (or diethyl) ether), C 3

H

7 0CH 2

CH(CH

3 )O(H or C 3

H

7 ) (propylene glycol n-propyl (or di-n-propyl) ether), C 3

H

7 0[CH 2 CH(CH3)O]2(H or C 3

H

7 ) (dipropylene glycol n-propyl (or di-n-propyl) ether), C 3

H

7 0[CH 2

CH(CH

3

)O]

3 (H or C 3

H

7 ) 35 (tripropylene glycol n-propyl (or di-n-propyl) ether), C 4

H

9

OCH

2

CH(CH

3 )OH (propylene glycol n-butyl ether), C 4 H9O[CH 2 CH(CH3)O]2(H or C 4 Hg) (dipropylene glycol n-butyl (or di-n-butyl) ether), C 4

H

9

O[CH

2

CH(CH

3 )01 3 (H 20 WO 2005/094395 PCT/US2005/001511 or C 4

H

9 ) (tripropylene glycol n-butyl (or di-n-butyl) ether),

(CH

3

)

3

COCH

2

CH(CH

3 )OH (propylene glycol t-butyl ether),

(CH

3

)

3

CO[CH

2

CH(CH

3 )O]2(H or (CH 3

)

3 ) (dipropylene glycol t-butyl (or di-t butyl) ether), (CH 3

)

3

CO[CH

2

CH(CH

3 )01 3 (H or (CH 3

)

3 ) (tripropylene glycol t 5 butyl (or di-t-butyl) ether), C 5

H

11 0CH 2

CH(CH

3 )OH (propylene glycol n pentyl ether), C 4

H

9

OCH

2

CH(C

2

H

5 )OH (butylene glycol n-butyl ether),

C

4

H

9

O[CH

2

CH(C

2

H

5

)O]

2 H (dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C 2

H

5

C(CH

2

O(CH

2

)

3

CH

3

)

3 ) and trimethyloipropane di-n-butyl ether (C 2

H

5

C(CH

2 0C(CH 2

)

3

CH

3

)

2

CH

2 OH). 10 Amide solubilizing agents of the present invention comprise those represented by the formulae RCONR 2

R

3 and cyclo-[R4CON(R 5 )-], wherein R1, R 2 , R 3 and R5 are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon 15 atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R 1 , R 2 , R 3 and R 5 may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens 20 (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R 1 , R 2 , R 3 and R 5 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and 25 heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 13 , and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative 30 R 1 , R 2 , R 3 and R 5 aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents are those wherein R 4 35 in the aforementioned formula cyclo-[R 4

CON(R

5 )-] may be represented by the hydrocarbylene radical (CR 6

R

7 )n, in other words, the formula: cyclo

[(CR

6

R

7 )oCON(R 5 )-] wherein: the previously-stated values for molecular 21 WO 2005/094395 PCT/US2005/001511 weight apply; n is an integer from 3 to 5; R 5 is a saturated hydrocarbon radical containing I to 12 carbon atoms; R 6 and R 7 are independently selected (for each n) by the rules previously offered defining R 1 . In the lactams represented by the formula: cyclo-[(CR 6

R

7 )nCON(R 5 )-], all R 6 and 5 R 7 are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R 5 is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones. Representative amide solubilizing agents include but are not 10 limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5 methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1 hexylcaprolactam, 1 -hexyl-5-methylpyrrolidin-2-one, 5-methyl-1 pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1 15 butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5 methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide. Ketone solubilizing agents of the present invention comprise ketones represented by the formula RCOR 2 , wherein R 1 and R 2 are 20 independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R' and R 2 in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. 25 The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R 1 and R 2 may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R 1 and R 2 may optionally include substituted hydrocarbon radicals, that is, 30 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R' and R 2 may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In 35 general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R 1 and R 2 , and the presence of any such non 22 WO 2005/094395 PCT/US2005/001511 hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R, and

R

2 aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula

R

1

COR

2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, 5 tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative ketone solubilizing agents include but are not 10 limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3 heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4 decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl 15 ketone. Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 20 to about 200 atomic mass units. R 1 in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units. R 1 may optionally include substituted hydrocarbon radicals, that is, 25 radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R' may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, 30 no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in

R

1 , and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R' aliphatic, alicyclic and aryl 35 hydrocarbon radicals in the general formula R'CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, 23 WO 2005/094395 PCT/US2005/001511 nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizing agents include but are not limited to: 1 cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1 5 cyanoheptane, I-cyanooctane, 2-cyanooctane, 1-cyanononane, 1 cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane. Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RClx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic 10 hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the 15 general formula RCIx include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. Representative chlorocarbon solubilizing agents include but are 20 not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1 chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, I-chlorooctane, 1 chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane. Ester solubilizing agents of the present invention comprise esters represented by the general formula R'C0 2

R

2 , wherein R 1 and R 2 25 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and 0, have a molecular weight of from about 80 to about 550 atomic mass units. Representative esters include but are not limited to: 30 (CH 3

)

2

CHCH

2

OOC(CH

2

)

2 -40COCH 2

CH(CH

3

)

2 (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, "Exxate 700" (a commercial C7 alkyl acetate), "Exxate 800" (a commercial C8 alkyl acetate), dibutyl phthalate, and tert-butyl 35 acetate. Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [CI: 24 WO 2005/094395 PCT/US2005/001511

R

2 0 R, 0 R 2 00 0 O'JIR R1 R2 R7 R R 5

R

3 R 5 R3 R5R6R R 4 R6~ R3 R6Ne [A] [B] [C] 5 These lactones contain the functional group -C0 2 - in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R 1 through R 8 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R 1 though 10 R 5 may be connected forming a ring with another R 1 through R 8 . The lactone may have an exocyclic alkylidene group as in structure [C], wherein R 1 through R 6 are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R, though R 6 may be connected forming a ring with another R 1 15 through R 6 . The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units. Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 2. 20 TABLE 2 Additive Molecular Structure Molecular Molecular Formula Weight (amu) (EZ)-3-ethylidene-5-methy- O 126 dihydro-furan-2-one (E,Z)-3-propylidene-5-methy- 0 O dihydro-furan-2-one CaH1202 140 (E,Z)-3-butylidene-5-methyl- 0 1 dihydro-furan-2-one CqH1O2 154 (E,Z)-3-pentylidene-5-methyl- 0 dihydro-furan-2-one C1oH16O2 168 (E,Z)-3-Hexylidene-5-methyl- C 11

HSO

2 182 dihydro-furan-2-one 25 WO 2005/094395 PCT/US2005/001511 (E,Z)-3-Heptylidene-5-methyl- 0 0 dihydro-furan-2-one 0-: ' 12

H

20 0 2 196 (E,Z)-3-octylidene-5-methyl- 0 0 dihydro-furan-2-one C 13

H

22 0 2 210 (E,Z)-3-nonylidene-5-methyl- 0 0 dihydro-furan-2-onle C 14

H

24 0 2 224 (E,Z)-3-decyiidene-5-methy- 0 0 dihydro-furan-2-one C 15

H

2 o0 2 238 (E,Z)-3-(3,5,5-trimethylhexylidene)- 0 5-methyl-dihydrofuran-2-one C 14

H

24 0 2 224 (E,Z)-3-cyclohexylmethylidene-5- 0 0 methyi-dihydrofuran-2-one 00C 12

HI

8 0 2 194 gamma-octalactone 0 0

C

8

H

14 0 2 142 gamma-nonalactone 0 0

C

9

H

16 0 2 156 gamma-decalactone 0 0

C

10

H

18 0 2 170 gamma-undecalactone 0 0 C,,Hzo~z184 gamma-dodecalactone 0 0

C

12

H

22 0 2 198 3-hexyidihydro-furan-2-one 0CjoHI80 2 170 3-heptyldihydro-furan-2-one 0 0 0 1

H

2 o0 2 184 cis-3-ethyl-5-methyl-di hydro-fu ran- 0 2-one C 7 H 1 2 0 2 128 cis-(3-propyl-5-methyi)-dihydro- 0 furan-2-one CsH 14 0 2 142 0 cis-(3-butyl-5-methyl)-dihydro-0 furan-2-one CgH 16 0 2 156 0 furan-2-one C 10

H

18 0 2 170 0 cis-3-hexyl-5-methyl-dihydro-furan- 0 2-one C 11

H

20 0O 2 184 0 26 WO 2005/094395 PCT/US2005/001511 cis-3-heptyl-5-methyl-dihydro- 0 furan-2-one C 1 2 H220 2 198 cis-3-octyl-5-methyl-dihydro-furan- 0 2-one C 1 3

H

24 0 2 212 cis-3-(3,5,5-trimethylhexyl)-5methyl-dihydro-furan-2-one C14H26O2 226 cis-3-cyclohexylmethyl-5-methyl- 0 dihydro-furan-2-one C 1 2

H

20 0 2 196 5-methyl-5-hexyl-dihydro-furan-2- 0 one C11H2002 184 0 5-methyl-5-octyl-dihydro-furan-2- 0 one C1 3

H

24 0 2 212 0 Hexahydro-isobenzofuran-1-one H C3H 12

O

2 140 0 H delta-decalactone

C

1 eH 1

O

2 170 o o de/ta-undecalactone ClIH 20 0 2 184 0 0 delta-dodecalactone

C

12

H

22 0 2 198 mixture of 4-hexyl-dihydrofuran-2- o one and 3-hexyl-dihydro-furan-2- C 10

H

18 0 2 170 one0 Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40 0 C. For instance, gamma undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl 5 5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40 0 C. Lactone solubilizing agents may be available commercially or prepared by methods as described in U. S. patent application 10/910,495 (inventors being P. J. Fagan and C. J. Brandenburg), filed August 3, 2004, incorporated herein by reference. 27 WO 2005/094395 PCT/US2005/001511 Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R 1 0R 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms;

R

2 is selected from aliphatic hydrocarbon radicals having from I to 4 5 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R' aryl radicals in the general formula R 1 0R 2 include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R 2 aliphatic hydrocarbon radicals in the general formula R 1 0R 2 include methyl, ethyl, 10 propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether. Fluoroether solubilizing agents of the present invention 15 comprise those represented by the general formula R 1

OCF

2

CF

2 H, wherein

R

1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C 8

H

1 7 0CF 2

CF

2 H and C 6

H

1 3 0CF 2

CF

2 H. It should be 20 noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether. 1,1,1-Trifluoroalkane solubilizing agents of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF 3

R

1 , wherein R 1 is selected from aliphatic and alicyclic 25 hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1 trifluoroalkane solubilizing agents include but are not limited to: 1,1,1 trifluorohexane and 1,1,1-trifluorododecane. Solubilizing agents of the present invention may be present as 30 a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether. 35 In the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight 28 WO 2005/094395 PCT/US2005/001511 percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. Solubility of these UV fluorescent dyes in refrigerants may be poor,. Therefore, methods for introducing these dyes into the refrigeration 5 or air conditioning apparatus have been awkward, costly and time consuming. US patent no. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or 10 dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature. Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for 15 introduction to the refrigeration or air conditioning apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing refrigerant even at low temperatures while maintaining the dye in solution. 20 In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about I to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant. In the compositions of 25 the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent. 30 Optionally, commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability. These additives are known within the field of refrigeration, and include, but are not limited to, anti wear agents, extreme pressure lubricants, corrosion and oxidation 35 inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,. In general, these additives are present in the inventive compositions in small amounts relative to the overall composition. 29 WO 2005/094395 PCT/US2005/001511 Typically concentrations of from less than about 0.1 weight percent to as much as about 3 weight percent of each additive are used. These additives are selected on the basis of the individual system requirements. These additives include members of the triaryl phosphate family of EP 5 (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn 0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of 10 this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. 15 Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides. Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may 20 include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing 25 agent. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus. The method comprises introducing the refrigerant 30 or heat transfer fluid composition into the refrigeration or air conditioning apparatus. This may be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and and 35 UV fluorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. 30 WO 2005/094395 PCT/US2005/001511 The resulting composition is may be used in the refrigeration or air conditioning apparatus. The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet 5 fluorescent dye to detect leaks. The presence of the dye in the compostions allows for detection of leaking refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the 10 operation of the apparatus. The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a sutiable means for detecting the 15 UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as a "black light" or "blue light". Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. Once the ultra-violet fluorescent dye containing composition has been 20 introduced to the refrigeration or air conditioning apparatus and has been allowed to circulate throughout the system, a leak can be found by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point. The present invention further relates to a method of using the 25 compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter 30 evaporating said composition. Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector, 35 and air. Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A 31 WO 2005/094395 PCT/US2005/001511 vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in 5 the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant 10 returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle. There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified as 15 reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed. 20 Either positive displacement or dynamic compressors may be used in the present inventive process. A centrifugal type compressor is the preferred equipment for the present refrigerant compositions. A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser 25 housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is 30 a stage of the compressor. Centrifugal compressors are built with from I to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled. The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure. 35 Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities. 32 WO 2005/094395 PCT/US2005/001511 Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero. A positive displacement 5 compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure. Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed 10 impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression. The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its 15 revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity. Because of its high-speed operation, a centrifugal compressor 20 is fundamentally a high volume, low-pressure machine. A centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-1 1) or 1,2,2-trichlorotrifluoroethane

(CFC

113). Large centrifugal compressors typically operate at 3000 to 25 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters. A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a 30 two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a compression ratio of about 4 to 1; that is, the absolute discharge pressure can be four times the absolute suction pressure. An example of a two 35 stage centrifugal compressor system, in this case for automotive applications, is described in US 5,065,990, incorporated herein by reference. 33 WO 2005/094395 PCT/US2005/001511 The compositions of the present invention suitable for use in a refrigeration or air conditioning systems employing a centrifugal compressor comprise at least one of: 1,1,1 ,2 ,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanole; 5 1, 1, 1, 3,4,4,4-h eptafluoro-3-(triflu oromethyl)-2-buta none; 1,1,1,2 ,4,5,5,5-octafluoro-2,4-bis(trifluoromethy)-3 pentanone; 1,1,1 ,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2 ,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethy)-3-hexalone; 1,1 ,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 10 pentanone; 1,1, 1, 2,2,5,5,5-octaflu oro-4-(trifl uoromethyl)-3-pe nta none; 2-ch lo ro- 1 , 1, 1,4,4,5,5,5-octafl uoro-2-(trifl uo romethyl)-3-penta none;

CF

3 C(O)CBrFCF 2

CF

3 ;

CF

3

C(O)CF

2

CF

2 CBrF 2 ; 15 CBrF 2

C(O)CF(CF

3

)

2 ;

CF

3 C(O)CBr(CF 3

)

2 ; CBrF 2

CF

2

C(O)CF

2

CF

3 ;

CF

3 CBrFC(O)CF 2

CF

3 ;

CF

3 CBrFC(O)CF 2

GF

2

CF

3 ; 20 CF 3

CF

2 C(O)CBrFCF 2

CF

3 ;

CF

3

CF

2

C(O)CF

2

CF

2 CBrF 2 ;

CF

3 C(O)CBr(0F 3

)CF

2

CF

3 ;

CF

3

C(O)CF(CF

3 )CBrFCF 3 ;

CF

3 C(O)CBrFCF 2

CF

2

CF

2

CF

3 ; 25 CF 3

C(O)CF

2

CF

2

CF

2

CF

2 CBrF 2 ;

CF

3 CBrFC(O)C F 2

CF

2

CF

2

CF

3 ;

CF

3

CF

2 G(O)CBrFCF 2

CF

2

CF

3 ;

CF

3

CF

2

C(O)CF

2

CF

2

CF

2 CBrF 2 ;

CF

3

CF

2 CBrFC(O)CF 2

CF

2

CF

3 ; 30 CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 ;

CF

3 CBrFC(O)GF(CF 3

)CF

2

CF

3 ;

CF

3

CF

2 C(O)CBr(CF 3

)CF

2

CF

3 ;

CF

3

CF

2 C(O)CF(CBrF 2

)CF

2

CF

3 ; CBrF 2 C F 2

CF

2

C(O)CF(CF

3

)

2 ; 35 CF 3

CF

2 CBrFC(O)CF(CF 3

)

2 ;

CF

3

CF

2

CF

2 C(O)CBr(CF 3 )2; (0F 3

)

2 CBrC(O)CF(CF 3

)

2 ; 34 WO 2005/094395 PCT/US2005/001511

CF

3 CBrFCF 2

C(O)CF(CF

3

)

2 ;

CHF

2

CF

2 C(O)CBr(CF 3

)

2 ; (0F 3

)

2 CHC(O)CBr(CF 3

)

2 ; CH F 2

CF

2 C(O)CBrFCF 3 ; 5 (CF 3

)

2 CHC(O)CBrFCF 3 ; (0F 3

)

2 CHC(O)CBrF 2 ; CBrF 2

CF

2

C(O)CH(CF

3

)

2 ; CBrF 2 C(O)CF(0F 3

)OCF

3 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF

3 ; 10 CBrF 2

CF

2

CF

2 C(O)CF(0F 3

)OCF

3 ; CBrF 2

C(O)CF(CF

3 )0C 2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3 )0C 2

F

5 ; CBrF 2 C(O)CF(0F 3

)OCF

2

C

2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3 )0CF 2 02F5; 15 CBrF 2

C(O)CF(CF

3

)OCF(CF

3

)

2 ; CBrF 2

CF

2 C(O)CF(0F 3

)OCF(CF

3

)

2 ;

CF

3 CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 ;

CF

3 CBrFC(O)CF(CF 3

)OCF

3 ;

CF

3 CBrFC(O)CF(0F 3 )00 2

F

5 ; 20 CF 3 CBrFC(O)CF(CF 3

)OCF

3 ; (0F 3

)

2 CBrC(O)CF(CF 3 )OCF3;

CF

3 CBrFC(O)CF(CF 3 )0C 2

F

5 ; (0F 3

)

2 CBrC(O)CF(CF 3 )0C2F5;

CF

3 CBrFC(O)CF(CF 3 )00F 2

C

2

F

5 ; 25 CF 3 CBrFC(O)CF(CF 3

)OCF(CF

3 )2; CBrF 2

C(O)CF(OOF

2

CHF

2

)CF

3 ; CBrF 2 C(O)CH (OCF 2 CH F 2

)CF

3 ; CB rF 2 C (0CF (0 CH 3 )C F 3 CBrF 2

C(O)CF(CF

2 00H 3 )CF3; 30 CCIF 2 CFBrC(O)CF 2

CF

3 ; CBrF 2 CFCIC(0)CF 2

CF

3 ;

CCIF

2 CFBrC(O)CF(CF 3

)

2 ; CBrF 2 CFCIC(0)CF(CF 3

)

2 ;

CCIF

2 CFBrC(O)CF(CF 3

)(C

2

F

5 ); 35 CBrF 2

CFCIC(O)CF(CF

3

)(C

2

F

5 );

CCIF

2 C(0)CBr(CF 3

)

2 ;

CCIF

2

CF

2 C(O)CBr(CF 3

)

2 ; 35 WO 2005/094395 PCT/US2005/001511 CF3CCIFC(O)CBr(CF 3

)

2 ;

CCIF

2 C(O)CBrFCF 3 ;

CCIF

2

CF

2 (O)CCBrFCF 3 ;

CF

3 CCIFC(O)CBrFCF 3 ; 5 CBrF 2

C(O)CCI(CF

3

)

2 ; CBrF 2

CF

2

C(O)CC(CF

3

)

2 ; CBrF 2

C(O)CCIFCF

3 ; CBrF 2

CF

2

C(O)CCIFCF

3 ; or combinations thereof. 10 These above-listed compositions are also suitable for use in two stage centrifugal compressor systems. The compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air conditioning and heat pump 15 applications include window, ductless, ducted, packaged terminal, chillers and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems. 20 The compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers. Conventional microchannel heat exchangers may not be ideal 25 for the low pressure refrigerant compositions of the present invention. The low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat 30 exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger. The following compositions of the present invention are suitable for use in refrigeration or air conditioning systems employing a single 35 slab/single pass heat exchanger: 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone 36 WO 2005/094395 PCT/US2005/001511 1,1,1 ,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1, 1, 1 ,2,4,4,5,5-octafl uoro-2-(trifl u orom ethyl)-3-pe ntanonle; 1, ,,I,2 ,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexalofe; 1 , I ,2,2 ,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 5 pentanone; 1, 1, 1,2 ,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-peltalofe; 2-chloro-1, 1, 1,4,4,5,5,5-octafl uo ro-2-(trifl uo romethyl)-3-peltanonle;

CF

3 C(O)CBrFCF 2

CF

3 ;

CF

3

C(O)CF

2

CF

2 CBrF 2 ; 10 CBrF 2

C(O)CF(CF

3

)

2 ;

CF

3 C(O)CBr(CF 3

)

2 ; CBrF 2

CF

2

C(O)CF

2

CF

3 ;

CF

3 CBrFC(O)CF 2

CF

3 g;

CF

3 CB rFC(O)CF 2

CF

2

CF

3 ; 15 CF 3

CF

2 C(O)CBrFCF 2

CF

3 ;

CF

3

CF

2

C(O)CF

2

CF

2 CBrF 2 ;

CF

3 C(O)CBr(CF 3

)CF

2

CF

3 ;

CF

3

C(O)CF(CF

3 )CBrFCF 3 ;

CF

3 C(O)CBrFCF 2

CF

2

CF

2 CF3; 20 CF 3

C(O)CF

2

CF

2

CF

2

CF

2 OBrF 2 ;

CF

3 CBrFC(O)CF 2

CF

2

CF

2

CF

3 ;

CF

3

CF

2 C(O)CBrFCF 2

CF

2

CF

3 ;

CF

3

CF

2 C(O)C F 2

CF

2 C F 2 CBrF 2 ;

CF

3

CF

2 CBrFC(O)CF 2

CF

2 CF3; 25 CBrF 2

CF

2

C(O)CF(CF

3

)CF

2

CF

3 ;

CF

3 CBrFC(O)CF(CF 3

)CF

2

CF

3 ;

CF

3

CF

2 C(O)CBr(CF 3

)CF

2

CF

3 ;

CF

3

CF

2 C(O)CF(CBrF 2

)CF

2

CF

3 ; CBrF 2

CF

2

CF

2

C(O)CF(CF

3 )2; 30 CF 3

CF

2 CBrFC(O)CF(0F 3

)

2 ;

CF

3

CF

2

CF

2 C(O)CBr(CF 3

)

2 ;

(CF

3

)

2 CBrC(O)CF(CF3) 2 ;

CF

3 CBrFCF 2

C(O)CF(CF

3

)

2 ;

GHF

2

CF

2 C(O)CBr(CF 3

)

2 ; 35 (CF 3

)

2 CHC(O)CBr(CF 3

)

2 ;

CHF

2

CF

2 C(O)CBrFCF 3 ;

(CF

3

)

2 CHC(O)CBrFCF 3 ; 37 WO 2005/094395 PCT/US2005/001511

(CF

3

)

2 CHC(Q)CBrF 2 ; CBrF 2

CF

2

C(O)CH(CF

3

)

2 ; CBrF 2

C(O)CF(CF

3

)OCF

3 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF

3 ; 5 CBrF 2

CF

2

CF

2

C(O)CF(CF

3 )OCF3; CBrF 2

C(O)GF(CF

3 )00 2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3 )00 2

F

5 g; CBrF 2

C(O)CF(CF

3

)OCF

2

C

2

F

5 ; CBrF 2

CF

2

C(O)CF(CF

3

)OCF

2 C2F5; 10 CBrF 2

C(O)CF(CF

3

)OCF(CF

3

)

2 ; CBrF 2

CF

2

C(O)CF(CF

3 )OCF(0F3)2;

CF

3 CBrFC(O)CF(CF 3

)OCF(CF

3

)

2 ;

CF

3 CBrFC(O)CF(CF 3

)OCF

3 ;

CF

3 CBrFC(O)CF(CF 3

)OC

2 F5; 15 CF 3 CBrFC(O)CF(CF 3

)OCF

3 ; (0F 3

)

2 CBrC(O)CF(CF 3

)OCF

3 ;

CF

3 CBrFC(O)CF(CF 3 )0C 2

F

5 ;

(CF

3

)

2 CBrC(O)CF(CF 3 )0C 2

F

5 ;

CF

3 CBrFC(O)CF(CF 3

)OCF

2

C

2

F

5 ; 20 CF 3 CBrFC(O)CF(0F 3

)OCF(CF

3

)

2 ; CBrF 2

C(O)CF(OCF

2 CH F 2

)CF

3 ; CBrF 2

C(O)CH(OCF

2

CHF

2 )0F 3 ; CBrF 2

C(O)CF(OCH

3

)CF

3 ; CBrF 2 C(O)CF(0F 2 00H 3

)CF

3 ; 25 CCIF 2 CFBrC(O)CF 2

CF

3 ; CBrF 2

CFCIC(O)CF

2

CF

3 ;

CCIF

2 CFBrC(O)CF(GF) 2 ; CBrF 2

CFCIC(O)CF(CF

3

)

2 ;

CCIF

2 CFBrC(O)CF(CF3)(C 2 F5); 30 CBrF 2

CFCIC(O)CF(CF

3

)(C

2

F

5 );

CCIF

2 C(O)CBr(CF 3

)

2 ;

CCIF

2

CF

2 C(O)CBr(CF 3

)

2 ;

CF

3 00I FC(O)CBr(CF 3

)

2 ;

CCIF

2 C(O)CBrFCF 3 ; 35 CCIF 2

CF

2 (O)CCBrFCF 3 ;

CF

3 CCI FC(O)CBrFCF 3 ; CBrF 2

C(O)CCI(CF

3

)

2 ; 38 WO 2005/094395 PCT/US2005/001511 CBrF 2

CF

2 C(O)CCI(CF3)2; CBrF 2

C(O)CCIFCF

3 ; CBrF2CF 2

C(O)CCIFCF

3 ; or combinations thereof. 5 The compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pumps as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the 10 engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high 15 driving speeds is taken into account, the advantage of these low pressure systems becomes even greater. Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-1 13 in existing centrifugal equipment. 20 The present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions. The present invention further relates to a process for producing 25 heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions. The present invention further relates to a process for transfer of heat from a heat source to a heat sink via a heat transfer fluid, wherein the 30 compositions of the present invention serve as heat transfer fluids. Said process for heat transfer comprises transferring the compositions of the present invention from a heat source to a heat sink. Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, 35 object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In 39 WO 2005/094395 PCT/US2005/001511 some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well. 5 A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, or the passenger 10 compartment of an automobile requiring air conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink. 15 EXAMPLES EXAMPLE I Tip Speed to Develop Pressure Tip speed can be estimated by making some fundamental 20 relationships for refrigeration equipment that use centrifugal compressors. The torque an impeller ideally imparts to a gas is defined as T = m*(v 2 *r 2 -v1*rl) Equation 1 where 25 T = torque, N*m m = mass rate of flow, kg/s v2= tangential velocity of refrigerant leaving impeller (tip speed), m/s r2= radius of exit impeller, m 30 vi = tangential velocity of refrigerant entering impeller, m/s ri = radius of inlet of impeller, m Assuming the refrigerant enters the impeller in an essentially radial direction, the tangential component of the velocity v1 = 0, therefore 35 T = m*v2*r2 Equation 2 40 WO 2005/094395 PCT/US2005/001511 The power required at the shaft is the product of the torque and the rotative speed P = T*w Equation 3 where 5 P = power, W w = rotative speed, rez/s therefore, P = T*w = m*v 2 *r2*w Equation 4 10 At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore r2*w = v2 Equation 5 and 15 P = m*v 2 *v2 Equation 6 Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression, 20 P = m*Hi*(1000J/kJ) Equation 7 where Hi = Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg. 25 Combining the two expressions Equation 6 and 7 produces, v2*v2 = 1000*Hi Equation 8 Although Equation 8 is based on some fundamental 30 assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants. Table 3 below shows theoretical tip speeds that are calculated for 1,2,2-trichlorotrifluoroethane (CFC-1 13) and compositions of the present invention. The conditions assumed for this comparison are: 35 Evaporator temperature 40.0*F (4.4*C) Condenser temperature 11 0.0-F (43.3-C) 41 WO 2005/094395 PCT/US2005/001511 Liquid subcool temperature 10.0'F (5.5*C) Return gas temperature 75.0*F (23.8*C) Compressor efficiency is 70% 5 These are typical conditions under which small turbine centrifugal compressors perform. TABLE 3 Hi Hi*0.7 Hi*0.7 V2 V2 rel Refrigerant (Btullb) (Btulb) (KJ/Kg) (m/s) to CFC-1 13 CFC-113 10.92 7.6 17.8 133.3 n/a PEIK 11.55 8.1 18.8 137.1 103% PMIK 10.94 7.7 17.8 133.5 100%

CF

3 C(O)CBrFCF 2

CF

3 9.9 6.9 16.1 127.0 95% 10 The data shows that compounds of the present invention have tip speeds within about +/- 5 percent of CFC-1 13 and would be effective replacements for CFC-1 13 with minimal compressor design changes. EXAMPLE 2 15 Performance Data Table 4 shows the performance of various refrigerants compared to CFC-1 13. The data are based on the following conditions. Evaporator temperature 40.0-F (4.4-C) 20 Condenser temperature 110.0*F (43.30C) Subcool temperature 10.0 0 F (5.5-C) Return gas temperature 75.0-F (23.8*C) Compressor efficiency is 70% 25 TABLE 4 Evap Evap Cond P Cond P Compr Compr Capacity Capacity Refrigerant Press Press Press Press Disch T Disch T COP (Btu/min) (kw) (Psia) kPa) (Psia) (kPa) L(F LGC CFC-113 2.7 19 12.8 88 156.3 69.1 4.18 14.8 0.26 PEIK 2.2 15 12.5 86 124.6 51.4 3.73 13.4 0.24 PMIK 7.3 50 33.0 227 127.9 53.3 | 3.68 | 37.6 0.66 42 WO 2005/094395 PCT/US2005/001511

CF

3 C(O)CBrFCF 2 0.6 4 4.9 33 142.3 61.3 4.08 4.9 0.09

-CF

3 Data show the compositions of the present invention have evaporator and condenser pressures similar to CFC-I 13. Some compositions also have higher capacity or energy efficiency (COP) than CFC-1 13. 5 43

Claims (20)

1. A haloketone refrigerant or heat transfer fluid composition said composition selected from the group consisting of: 5 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3 10 pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone;

2-chloro-1 1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF 3 C(O)CBrFCF 2 CF 3 ; 15 CF 3 C(O)CF 2 CF 2 CBrF 2 ; CBrF 2 C(O)CF(CF 3 ) 2 ; CF 3 C(O)CBr(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 3 ; 20 CF 3 CBrFC(O)CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CBrF 2 ; CF 3 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 C(O)CF(CF 3 )CBrFCF3; 25 CF 3 C(O)CBrFCF 2 CF 2 CF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CBrFC(O)CF 2 CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CF 2 CBrF 2 ; 30 CF 3 CF 2 CBrFC(O)CF 2 CF 2 CF 3 ; CBrF 2 CF 2 C(O)CF(CF 3 )CF 2 CF 3 ; CF 3 CBrFC(O)CF(CF 3 )CF 2 CF3; CF 3 CF 2 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 CF 2 C(O)CF(CBrF 2 )CF 2 CF3; 35 CBrF 2 CF 2 CF 2 C(O)CF(CF 3 ) 2 ; CF 3 CF 2 CBrFC(O)CF(CF3)2; CF 3 CF 2 CF 2 C(O)CBr(CF 3 ) 2 ; 44 WO 2005/094395 PCT/US2005/001511 (CF 3 ) 2 CBrC(O)CF(CF 3 ) 2 ; CF 3 CBrFCF 2 C(O)CF(CF 3 ) 2 ; CH F 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 CHC(O)CBr(CF 3 ) 2 ; 5 CHF 2 CF 2 C(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrF 2 ; CBrF 2 CF 2 C(O)CH(CF 3 ) 2 ; CBrF 2 C(O)CF(CF 3 )OCF 3 ; 10 CBrF 2 CF 2 C(O)CF(CFa)OCF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(0F 3 )OCF3; CBrF 2 C(O)CF(CF 3 )0C 2 F 5 ; CBrF 2 CF 2 C(O)CF(CF 3 )0C2FF5; CBrF 2 C(O)CF(CF 3 )QCF 2 C2F5; 15 CBrF 2 OF 2 C(O)CF(CF 3 )OCF 2 C 2 F 5 ; CBrF 2 C(O)CF(CF 3 )OCF(0F 3 )2; CBrF 2 CF 2 C(O)CF(GF 3 )OCF(CF3)2; CF, 3 CBrFC(O)CF(0F 3 )OCF(CF 3 )2; CF 3 CBrFC(O)CF(CF3)00F3; 20 CF 3 CBrFC(O)CF(CF 3 )0C 2 F6; CF 3 CBrFC(O)CF(CF 3 )OCF 3 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)CF(CF 3 )0C 2 F 5 ; (CF 3 ) 2 CBrC(O)CF(0F 3 )0C 2 F 5 ; 25 CF 3 CBrFC(O)CF(0F 3 )OCF 2 C 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF(CF 3 ) 2 ; CBrF 2 C(O)CF(OCF 2 CH F 2 )CF 3 ; CBrF 2 C(O)CH(OCF 2 CH F 2 )CF 3 ; CBrF 2 C(O)CF(OCH 3 )CF 3 ; 30 CBrF 2 C(O)CF(CF 2 OCH 3 )CF 3 ; CCIF 2 C FBrC(O)CF 2 CFs; CBrF 2 CFCIC(O)CF 2 CF 3 ; CCIF 2 CFBrC(O)CF(CF 3 ) 2 ; CBrF 2 CFOIC(O)CF(CF3)2; 35 CCIF 2 CFBrC(O)CF(CF 3 )(C 2 F 5 ); CBrF 2 CFCIC(O)CF(CF 3 )(C 2 F 5 ,); CCIF 2 C(O)CBr(CF 3 ) 2 ; 45 WO 2005/094395 PCT/US2005/001511 CCIF 2 CF 2 C(O)CBr(CF 3 ) 2 ; CF 3 CCIFC(O)CBr(CF 3 ) 2 ; CCIF 2 C(O)CBrFCF 3 ; CCIF 2 CF 2 (O)CCBrFCF3; 5 CF 3 CCIFC(O)CBrFCF 3 ; CBrF 2 C(O)CCI(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CCI(CF 3 ) 2 ; CBrF 2 C(O)CCIFCF 3 ; CBrF 2 CF 2 C(O)CCIFCF 3 ; and combinations thereof. 10 2. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor, said composition selected from the group consisting of: 15 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 20 pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1 1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF 3 C(O)CBrFCF 2 CF 3 ; 25 CF 3 C(O)CF 2 CF 2 CBrF 2 ; CBrF 2 C(O)CF(CF3) 2 ; CF 3 C(O)CBr(CF3) 2 ; CBrF 2 CF 2 C(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 3 ; 30 CF 3 CBrFC(O)CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CBrF 2 ; CF 3 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 C(O)CF(CF 3 )CBrFCF 3 ; 35 CF 3 C(O)CBrFCF 2 CF 2 CF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CBrFC(O)CF 2 CF 2 CF 2 CF 3 ; 46 WO 2005/094395 PCT/US2005/001511 CF 3 CF 2 C(O)CBrFCF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CF 2 CBrFC(O)CF 2 CF 2 CF 3 ; CBrF 2 CF 2 C(O)CF(CF 3 )CF 2 CF 3 ; 5 CF 3 CBrFC(O)CF(0F 3 )CF 2 CF 3 ; CF: 3 CF 2 C(O)CBr(0F 3 )CF 2 CF 3 ; CF 3 CF 2 C(O)CF(CBrF 2 )CF 2 CF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(CF 3 ) 2 ; CF 3 CF 2 CBrFC(O)CF(CF 3 ) 2 ; 10 CF 3 CF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 CBrC(O)CF(CF 3 ) 2 ; CF 3 CBrFCF 2 C(O)CF(CF 3 ) 2 ; OH F 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 0H0(O)CBr(CF 3 ) 2 ; 15 CHF 2 CF 2 C(O)CBrFCF 3 ; (0F 3 ) 2 CHC(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)GBrF 2 ; CBrF 2 CF 2 C(O)CH(CF 3 )2; CBrF 2 C(O)CF(CF 3 )00F 3 ; 20 OBrF 2 CF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(CF 3 )OCF3; CBrF 2 C(O)CF(CF 3 )0C 2 F 5 ; CBrF 2 CF 2 C(O)CF(CF 3 )00 2 F 5 ; CBrF 2 C(O)CF(CF 3 )00F2C2F5; 25 CBrF 2 CF 2 C(O)CF(CF 3 )00F 2 C 2 F 5 ; CBrF 2 C(O)CF(CF 3 )OCF(CF 3 )2; CBrF 2 CF 2 C(O)CF(CF 3 )OCF(0F3)2; CF 3 CBrFC(O)CF(CF 3 )OCF(0F 3 )2; CF 3 CBrFC(O)CF(CF 3 )QCF 3 ; 30 CF 3 CBrFC(O)CF(CF 3 )0C 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF 3 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)OF(CF 3 )0C 2 F 5 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )002F5; 35 CF 3 CBrFC(O)CF(0F 3 )OCF 2 C 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF(CF 3 )2; CBrF 2 C(O)CF(OCF 2 CHF 2 )0F 3 ; 47 WO 2005/094395 PCT/US2005/001511 CBrF 2 C(O)CH(OCF 2 CHF 2 )CF 3 ; CBrF 2 C(O)CF(OCH 3 )CF 3 ; CBrF 2 C(O)CF(CF 2 0CH 3 )CF 3 ; CCIF 2 CFBrC(O)CF 2 CF 3 ; 5 CBrF 2 CFCIC(O)CF 2 CF 3 ; CCIF 2 CFBrC(O)CF(CF 3 ) 2 ; CBrF 2 CFCIC(O)CF(CF 3 ) 2 ; CCIF 2 CFBrC(O)CF(CF 3 )(C 2 F 5 ); CBrF 2 CFCIC(O)CF(CF 3 )(C 2 F 5 ); 10 CCIF 2 C(O)CBr(CF 3 ) 2 ; CCIF 2 CF 2 C(O)CBr(CF 3 )2; CF 3 CCIFC(O)CBr(CF 3 ) 2 ; CCIF 2 C(O)CBrFCF 3 ; CCIF 2 CF 2 (O)CCBrFCF 3 ; 15 CF 3 CCIFC(O)CBrFCF 3 ; CBrF 2 C(O)CCI(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CCI(CF 3 ) 2 ; CBrF 2 C(O)CCIFCF 3 ; CBrF 2 CF 2 C(O)CCIFCF 3 ; and combinations thereof. 20

3. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a multi stage or centrifugal compressor or a single slab/single pass heat exchanger, said composition selected from the group consisting of: 25 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1, 1, 1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1 ,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1 -(trifluoromethoxy)-4-(trifluoromethyl)-3 30 pentanone; 1, 1, 1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1 1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF 3 C(O)CBrFCF 2 CF 3 ; 35 CF 3 C(O)CF 2 CF 2 CBrF 2 ; CBrF 2 C(O)CF(CF 3 )2; CF 3 C(O)CBr(CF 3 ) 2 ; 48 WO 2005/094395 PCT/US2005/001511 CBrF 2 CF 2 C(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 3 ; 5 CF 3 CF 2 C(O)CF 2 CF 2 CBrF 2 ; CF 3 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 C(O)CF(CF 3 )CBrFCF 3 ; CF 3 C(O)CBrFCF 2 CF 2 CF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CF 2 CF 2 CBrF2; 10 CF 3 CBrFC(O)CF 2 CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CF 2 CBrFC(O)CF 2 CF 2 CF 3 ; CBrF 2 CF 2 G(O)CF(0F 3 )CF 2 CF3; 15 CF 3 CBrFC(O)CF(CF 3 )CF 2 CF3; CF 3 CF 2 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 OF 2 C(O)CF(CBrF 2 )CF 2 CF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(0F3)2; CF 3 CF 2 CBrFC(O)CF(CF 3 )2; 20 CF 3 OF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (0F 3 ) 2 CBrC(O)CF(0F 3 ) 2 ; CF 3 CBrFCF 2 C(O)CF(CF 3 ) 2 ; CHF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 C HC(O)CBr(CF 3 ) 2 ; 25 CHF 2 CF 2 C(O)CBrFCF 3 ; (CF 3 ) 2 C HC(Q)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrF 2 ; CBrF 2 CF 2 C(O)CH(CF 3 ) 2 ; CBrF 2 C(O)CF(CF 3 )OCF3; 30 CBrF 2 CF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 GF 2 CF 2 C(O)CF(CF 3 )OCF 3 ; CBrF 2 C(O)CF(0F 3 )0C 2 F 5 ; CBrF 2 CF 2 C(O)CF(CF 3 )0C 2 F5; CBrF 2 C(O)CF(CF 3 )OCF 2 C 2 F 5 ; 35 CBrF 2 CF 2 C(O)CF(CF 3 )OCF 2 C 2 F 5 ; CBrF 2 C(O)CF(0F 3 )OCF(CF3)2; CBrF 2 CF 2 C(O)CF(CF 3 )OCF(CF 3 )2; 49 WO 2005/094395 PCT/US2005/001511 CF 3 CBrFC(O)CF(CF 3 )OCF(CF3)2; CF 3 CBrFC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)CF(CF 3 )OC 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF3; 5 (CF 3 ) 2 CBrC(O)CF(CF 3 )OCF 3 ; CF 3 CBrFC(O)CF(CF 3 )OC 2 F 5 ; (CF 3 ) 2 CBrC(O)CF(CF 3 )OC 2 F 5 ; CF 3 CBrFC(O)CF(CF 3 )OCF 2 C 2 F5; CF 3 CBrFC(O)CF(CF 3 )OCF(CF3)2; 10 CBrF 2 C(O)CF(OCF 2 CHF 2 )CF3; CBrF 2 C(O)CH(OCF 2 CHF 2 )CF3; CBrF 2 C(O)CF(OCH 3 )CF 3 ; CBrF 2 C(O)CF(CF 2 OCH 3 )CF 3 ; CCIF 2 CFBrC(O)CF 2 CF 3 ; 15 CBrF 2 CFCIC(O)CF 2 CF 3 ; CCIF 2 CFBrC(O)CF(CF 3 )2; CBrF 2 CFCIC(O)CF(CF 3 ) 2 ; CCIF 2 CFBrC(O)CF(CF 3 )(C 2 F); CBrF 2 CFCIC(O)CF(CF 3 )(C2F5); 20 CCIF 2 C(O)CBr(CF 3 ) 2 ; CCIF 2 CF 2 C(O)CBr(CF 3 ) 2 ; CF 3 CCIFC(O)CBr(CF 3 ) 2 ; CCIF 2 C(O)CBrFCF 3 ; CCIF 2 CF 2 (O)CCBrFCF 3 ; 25 CF 3 CCIFC(O)CBrFCF 3 ; CBrF 2 C(O)CCI(CF3)2; CBrF 2 CF 2 C(O)CCI(CF 3 )2; CBrF 2 C(O)CCIFCF 3 ; CBrF 2 CF 2 C(O)CCIFCF3; and combinations thereof. 30

4. The composition of claim 3, wherein said composition is suitable for use in refrigeration or air conditioning apparatus employing a two-stage centrifugal compressor. 35 5. A haloketone refrigerant or heat transfer fluid composition represented by the formula R 3 COR 4 , wherein R 3 and R 4 are independently selected from straight or branched chain, saturated or unsaturated, 50 WO 2005/094395 PCT/US2005/001511 aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine, and wherein R 3 and R 4 may optionally be joined to form a cyclic haloketone ring, and combinations of said haloketones represented by said formula.

5

6. A composition according to claim 5, said composition selected from the group consisting of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 10 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3 pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 15 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; and 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone.

7. The composition of claim 5, said composition comprising at least one brominated haloketone selected from the group consisting of 20 monobromoperfluoroketones, monohydromonobromoperluoroketones, perfluoroalkoxy)monobromoperfluoroketones, fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. 25

8. The composition of claim 7, said composition comprising at least one selected from the group consisting of: CF 3 C(O)CBrFCF 2 CF 3 ; CF 3 C(O)CF 2 CF 2 CBrF 2 ; CBrF 2 C(O)CF(CF 3 ) 2 ; 30 CF 3 C(O)CBr(CF 3 ) 2 ; CBrF 2 CF 2 C(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 3 ; CF 3 CBrFC(O)CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 3 ; 35 CF 3 CF 2 C(O)CF 2 CF 2 CBrF 2 ; CF 3 C(O)CBr(CF 3 )CF 2 CF 3 ; CF 3 C(O)CF(CF 3 )CBrFCF 3 ; 51 WO 2005/094395 PCT/US2005/001511 CF 3 C(O)CBrFCF 2 CF 2 CF 2 CF 3 ; C F 3 0(O)C F 2 CF 2 CF 2 CF 2 CB rF 2 ; CF 3 CBrFC(O)CF 2 CF 2 CF 2 CF 3 ; CF 3 CF 2 C(O)CBrFCF 2 CF 2 CF 3 ; 5 CF 3 CF 2 C(O)CF 2 CF 2 CF 2 CBrF 2 ; CF 3 CF 2 CBrFC(O)CF 2 CF 2 CF 3 ; CBrF 2 CF 2 C(O)CF(CF 3 )0F 2 0F 3 ; CF 3 CBrFC(O)OF(CF3)CF 2 CF 3 ; CF 3 CF 2 C(O)CBr(CF 3 )CF 2 CF 3 ; 10 CF 3 CF 2 C(O)CF(CBrF 2 )CF 2 CF 3 ; CBrF 2 CF 2 CF 2 C(O)CF(CF3)2; CF 3 CF 2 CBrFC(O)CF(CF3)2; CF 3 CF 2 CF 2 C(O)CBr(CF 3 ) 2 ; (CF 3 ) 2 CBrC(O)CF(CF 3 ) 2 ; 15 CF 3 CBrFCF 2 C(O)CF(CF3)2; CH F 2 CF 2 C(O)CBr(CF 3 )2; (CF 3 ) 2 CHC(O)CBr(CF 3 ) 2 ; CH F 2 CF 2 C(O)CBrFCF 3 ; (CF 3 ) 2 CHC(O)CBrFCF 3 ; 20 (CF. 3 ) 2 CHC(O)CBrF 2 ; CBrF 2 CF 2 C(O)CH (CF3) 2 ; CBrF 2 C(O)CF(CF 3 )OCF3; CBrF 2 CF 2 C(O)CF(CF 3 )OCF3; CBrF 2 CF 2 CF 2 C(O)CF(CF 3 )0CF3; 25 CBrF 2 C(O)CF(CF 3 )0C2F5; CBrF 2 CF 2 C(O)CF(CF 3 )0C2F5; CBFF 2 C(O)CF(CF 3 )OCF 2 C2F5; CBrF 2 OF 2 C(O)CF(CF 3 )0CF 2 C2F5g CBrF 2 C(O)CF(CF 3 )OCF(CF3)2; 30 CBrF 2 CF 2 C(O)CF(CF 3 )OCF(CF3)2; GF 3 GBrFC(O)CF(CF 3 )OCF(CF3)2; CF 3 CBrFC(O)CF(CF 3 )OCF3; CF 3 CBrFC(O)CF(CF 3 )0C 2 F5g; CF 3 CBrFC(O)CF(CF 3 )OCF3; 35 (CF 3 ) 2 CBrC(O)CF(CF 3 )OCF3; CF 3 CBrFC(O)CF(CF 3 )0C2F5; (CF 3 ) 2 CBrC(O)CF(CF 3 )0C 2 F 5 ; 52 WO 2005/094395 PCT/US2005/001511 CF 3 CBrFC(O)CF(CF 3 )OCF2C2F5; CF 3 CBrFC(O)CF(CF 3 )OCF(CF3)2; CBrF 2 C(O)CF(OCF 2 CHF 2 )CF3; CBrF 2 C(O)CH(OCF 2 CHF 2 )CF 3 ; 5 CBrF 2 C(O)CF(OCH 3 )CF3; CBrF 2 C(O)CF(CF 2 OCH3)CF3; CCIF 2 CFBrC(O)CF 2 CF 3 ; CBrF 2 CFCIC(O)CF2CF3; CCIF 2 CFBrC(O)CF(CF 3 ) 2 ; 10 CBrF 2 CFCIC(O)CF(CF3)2; CCIF 2 CFBrC(O)CF(CF 3 )(C2F5); CBrF 2 CFCIC(O)CF(CF3)(C2F5); CCIF 2 C(O)CBr(CF 3 )2; CCIF 2 CF 2 C(O)CBr(CF 3 ) 2 ; 15 CF 3 CCIFC(O)CBr(CF 3 )2; CCIF 2 C(O)CBrFCF 3 ; CCIF 2 CF 2 (O)CCBrFCF3; CF 3 CCIFC(O)CBrFCF 3 ; CBrF 2 C(O)CC(CF 3 ) 2 ; 20 CBrF 2 CF 2 C(O)CCI(CF3)2; CBrF 2 C(O)CCIFCF 3 ; and CBrF 2 CF 2 C(O)CCIFCF3.

9. A process for producing refrigeration, said process 25 comprising evaporating the composition of claim 1, 2, 3, 4, or 5 in the vicinity of a body to be cooled, and thereafter condensing said composition.

10. A process for producing heat, said process comprising 30 condensing the composition of claim 1, 2, 3, 4, or 5 in the vicinity of a body to be heated, and thereafter evaporating said composition.

11. A method of using the compositions of claim 1, 2, 3, 4, or 5 for heat transfer, said method comprising transferring said composition 35 from a heat source to a heat sink. 53 WO 2005/094395 PCT/US2005/001511

12. The composition of claim 1, further comprising ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye 5 and combinations thereof.

13. The composition of claim 2, 3, 4, or 5, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, 10 xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.

14. The composition of claim 12, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, 15 dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1 trifluoroalkanes.

15. The composition of claim 14, wherein said solubilizing agent is 20 selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R 1 [(OR 2 )xOR 3 ]y, wherein: x is an integer from I to 3; y is an integer from 1 to 4; R' is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y 25 bonding sites; R 2 is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R 3 is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from I to 6 carbon atoms; at least one of R 1 and R 3 is selected from said hydrocarbon radicals; and wherein said 30 polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R 1 CONR 2 R 3 and cyclo [R 4 CON(R 5 )-], wherein R', R 2 , R 3 and R 5 are independently selected from aliphatic and alicyclic hydrocarbon radicals 35 having from I to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R 4 is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon 54 WO 2005/094395 PCT/US2005/001511 atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula RCOR 2 , wherein R 1 and R2 are independently selected from aliphatic, alicyclic and aryl 5 hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R 1 CN, wherein R 1 is selected from aliphatic, alicyclic or aryl hydrocarbon radicals 10 having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCIx, wherein; x is selected from the integers 1 or 2; R is selected from aliphatic 15 and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R 1 0R 2 , wherein: R 1 is selected from aryl hydrocarbon radicals having from 6 to 12 20 carbon atoms; R 2 is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanes represented by the formula CF 3 R 1 , 25 wherein R' is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; i) fluoroethers represented by the formula R 1 0CF 2 CF 2 H, wherein R 1 is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; and 30 j) lactones represented by structures [B], [C], and [D]: 00 0 0 0 RRs5 RR R 3 R 5 R 6 R 3 R 6R R 3 R 4 [B] [C] [D] 55 WO 2005/094395 PCT/US2005/001511 wherein, R 1 through R 8 are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is 5 from about 100 to about 300 atomic mass units; and k) esters represented by the general formula R 1 C0 2 R 2 , wherein R 1 and R 2 are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 10 550 atomic mass units.

16. A method for using the composition of claim 12 or 14, said method comprising, (a) introducing the composition into a compression refrigeration or air conditioning apparatus by (i) dissolving the ultraviolet 15 fluorescent dye in the refrigerant composition of heat transfer fluid in the presence of the solubilizing agent, and introducing the combination into said compression refrigeration or air conditioning apparatus or (ii), combining solubilizing agent and and UV flurorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing 20 refrigerant andlor heat transfer fluid.

17. A method for using the composition of claim 12 or 14 in compression refrigeration ot air conditioning apparatus, said method comprising providing said composition to said apparatus, and providing a 25 suitable means for detecting saif composition in the vicinity of said apparatus.

18. A method of using the composition of claim 12 or 14, said method comprising: 30 (i) producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or (ii) producing heat by condensing said composition in the vicinity of the body to be heated and thereafter 35 evaporation said composition. 56 WO 2005/094395 PCT/US2005/001511

19. The composition of claim 11, further comprising an odor masking agent, fragrance, or thermal stabilizer.

20. The composition of claim 18, wherein the thermal stabilizer is 5 nitromethane. 57