WO1992010454A1

WO1992010454A1 - Partially fluorinated alkanols having a tertiary structure

Info

Publication number: WO1992010454A1
Application number: PCT/US1991/006967
Authority: WO
Inventors: Chien Chi Li; Kane David Cook; Rajat Subhra Basu
Original assignee: Allied-Signal Inc.
Priority date: 1990-12-04
Filing date: 1991-09-25
Publication date: 1992-06-25
Also published as: AU8763991A

Abstract

Novel partially fluorinated alkanes having formula (I), wherein each R is the same or different and is selected from the group consisting of CF3, CHF2, CH2F, and CH3CF2, and R' is an alkyl or fluoroalkyl group having 1 to 6 carbon atoms have utility as solvents in a variety of industrial cleaning applications including cold cleaning, dry cleaning, and defluxing of printed circuit boards.

Description

PARTIALLY FLUORINATED ALKANQLS HAVING A TERTIARY STRUCTURE FIELD OF THE INVENTION

This invention relates to novel partially

fluorinated alkanols having a tertiary structure and 4 to 9 carbon atoms. These compounds are useful in a variety of vapor degreasing, cold cleaning, and solvent cleaning applications including defluxing and dry cleaning.

BACKGROUND OF THE INVENTION Cold cleaning is an application where numerous solvents are used. In most cold cleaning applications, the soiled part is either immersed in the fluid or wiped with rags or similar objects soaked in solvents and allowed to air dry.

In cold cleaning applications, the use of the aerosol packaging concept has long been found to be a convenient and cost effective means of dispensing

solvents. Aerosol products utilize a propellant gas or mixture of propellant gases, preferably in a liquified gas rather than a compressed gas state, to generate sufficient pressure to expel the active ingredients, i.e. product concentrates such as solvents, from the container upon opening of the aerosol valve. The propellants may be in direct contact with the solvent, as in most conventional aerosol systems, or may be isolated from the solvent, as in barrier-type aerosol systems. Vapor degreasing and solvent cleaning with

fluorocarbon based solvents have found widespread use in industry for the degreasing and otherwise cleaning of solid surfaces, especially intricate parts and difficult to remove soils.

In its simplest form, vapor degreasing or solvent cleaning consists of exposing a room temperature object to be cleaned to the vapors of a boiling solvent. Vapors condensing on the object provide clean distilled solvent to wash away grease or other contamination. Final

evaporation of solvent from the object leaves behind no residue as would be the case where the object is simply washed in liquid solvent.

For soils which are difficult to remove, where elevated temperature is necessary to improve the cleaning action of the solvent, or for large volume assembly line operations where the cleaning of metal parts and

assemblies must be done efficiently and quickly, the conventional operation of a vapor degreaser consists of immersing the part to be cleaned in a sump of boiling solvent which removes the bulk of the soil, thereafter immersing the part in a sump containing freshly distilled solvent near room temperature, and finally exposing the part to solvent vapors over the boiling sump which

condense on the cleaned part. In addition, the part can also be sprayed with distilled solvent before final rinsing.

Vapor degreasers suitable in the above-described operations are well known in the art. For example,

Sherliker et al. in U.S. Patent 3,085,918 disclose such suitable vapor degreasers comprising a boiling sump, a clean sump, a water separator, and other ancillary

equipment. Chlorofluorocarbon solvents, such as

trichlorotrifluoroethane, have attained widespread use in recent years as effective, nontoxic, and nonflammable agents useful in degreasing applications and other solvent cleaning applications. One isomer of

trichlorotrifluoroethane is

1,1,2-trichloro-1,2,2-trifluoroethane (known in the art as CFC-113). CFC-113 has a boiling point of about 47°C and has been found to have satisfactory solvent power for greases, oils, waxes and the like. It has therefore found widespread use for cleaning electric motors, compressors, heavy metal parts, delicate precision metal parts, printed circuit boards, gyroscopes, guidance systems, aerospace and missile hardware, aluminum parts and the like.

Another commonly used solvent is chloroform (known in the art as HCC-20) which has a boiling point of about 63ºC. Perchloroethylene is a commonly used dry cleaning and vapor degreasing solvent which has a boiling point of about 121°C. These compounds are disadvantageous for use as solvents because they are toxic; also, chloroform causes liver damage when inhaled in excess.

Although chlorine is known to contribute to the solvency capability of a compound, fully halogenated chlorofluorocarbons and hydrochlorocarbons are suspected of causing environmental problems in connection with the earth's protective ozone layer. Thus, the art is seeking new compounds which do not contribute to environmental problems but yet provide the solvency properties of

CFC-113. From an environmental standpoint, partially fluorinated alkanols are of interest because they are considered to be stratospherically safe substitutes for the currently used fully halogenated chlorofluorocarbons. It is an object of this invention to provide novel partially fluorinated alkanols which are liquid at room temperature and which are useful as solvents for use in vapor degreasing, cold cleaning, and other solvent

cleaning applications including defluxing applications and dry cleaning.

Another object of the invention is to provide novel environmentally acceptable solvents for use in the

aforementioned applications.

Other objects and advantages of the invention will become apparent from the following description.

DETAILED DESCRIPTION OF THE INVENTION

We have found a novel class of alkanols which we believe have good solvency characteristics. The present novel compounds are of the Formula:

wherein each R is the same or different and is selected from the group consisting of CF₃, CHF₂, CH₂F, and

CH₃CF₂-, and R' is an alkyl or fluoroalkyl group

having 1 to 6 carbon atoms. Because C in the Formula above has three alkyl groups thereon, these novel compounds have a tertiary structure. We believe that this tertiary structure provides good solvency power. When the present compounds are used as solvents, the compounds have good solvency power for polar contaminants such as polyols and amines and for nonpolar contaminants including hydrocarbons such as mineral oil. We also believe that these novel

compounds have boiling points which are comparable to those of currently used solvents.

Preferably, R' in the Formula above is selected from the group consisting of CF₃, CHF₂, CH₂F, CH₃,

CF₃CF₂-, CF₃(CF₂)₂-, CF₃CF₂CHF-,

CF₃CF₂CH₂-, CF₃CHF-, CF₃(CHF)₂-,

CF₃CHFCF₂-, CF₃CHFCH₂-, CF₃CH₂-,

CF₃(CH₂)₂-, CF₃CH₂CF₂-, CF₃CH₂CHF-,

CHF₂CF₂-, CHF₂(CF₂)₂-, CHF₂CF₂CHF-,

CHF₂CF₂CH₂-, CHF₂CHF-, CHF₂(CHF)₂-,

CHF₂CHFCF₂-, CHF₂CHFCH₂-, CHF₂CH₂-,

CHF₂(CH₂)₂-, CHF₂CH₂CF₂-, CHF₂CH₂CHF-,

CH₂FCF₂-, CH₂F(CF₂)₂-, CH₂FCF₂CHF-,

CH₂FCF₂CH₂-, CH₂FCHF-, CH₂F(CHF)₂-,

CH₂FCHFCF₂-, CH₂FCHFCH₂-, CH₂FCH₂-,

CH₂F(CH₂)₂-, CH₂FCH₂CF₂-, CH₂FCH₂CHF-,

CH₃CF₂-, CH₃(CF₂)₂-, CH₃CF₂CHF-,

CH₃CF₂CH₂-, CH₃CHF-, CH₃(CHF)₂-,

CH₃CHFCF₂-, CH₃CHFCH₂-, CH₃CH₂-,

CH₃(CH₂)₂-, CH₃(CH₂)₃-, CH₃CH₂CF₂-,

CH₃(CH₂)₂CF₂-, CH₃(CH₂)₃CF₂-,

CH₃CH₂(CF₂)₂-, CH₃(CH₂)₂(CF₂)₂-, and

CH₃(CH₂)₃(CF₂)₂-.

In the Formula above, when one R is CF₃, the other R is CHF₂, and R' is CH₃, the compound is

2-methyl-1,1,1,3,3-pentafluoro-2-propanol. When one R is CF₃, the other R is CHF₂, and R' is CF₃CF₂-, the

compound is

2-difluoromethyl-1,1,1,3,3,4,4,4-octafluoro-2-butanol. When one R is CF₃, the other R is CHF₂, and R' is

CH₃CF₂-, the compound is

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-butanol. When one R is CF₃, the other R is CHF₂, and R' is

CH₃(CF₂)₂-, the compound is

2-difluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-ρentanol. When one R is CF₃, the other R is CHF₂, and R' is

CH₃CH₂CF₂-, the compound is

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol. When one R is CF₃, the other R is CHF₂, and R' is

CH₃CH₂(CF₂)₂-, the compound is

2-difluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol.

When one R is CF₃, the other R is CH₂F, and R' is CH₃, the compound is

2-methyl-1,1,1,3-tetrafluoro-2-propanol. When one R is CF₃, the other R is CH₂F, and R' is CHF₂CHF-, the

compound is

2-fluoromethyl-1,1,1,3,4,4-hexafluoro-2-butanol. When one R is CF₃, the other R is CH₂F, and R' is CH₃CF₂-,

the compound is

2-fluoromethyl-1,1,1,3,3-pentafluoro-2-butanol. When one R is CF₃, the other R is CH₂F, and R' is

CH₃(CF₂)₂-, the compound is 2-fluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-pentanol. When one R is CF₃, the other R is CH₂F, and R' is

CH₃CH₂CF₂-, the compound is

2-fluoromethyl-1, 1,1,3, 3-pentafluoro-2-pentanol. When one R is CF₃, the other R is CH₂F, and R' is

CH₃CH₂(CF₂)₂-, the compound is

2-fluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol.

When one R is CF₃, the other R is CH₃CF₂-,

and R' is CH₃, the compound is

2-methyl-1,1,1,3,3-pentafluoro-2-butanol. When one R is CHF₂, the other R is CH₂F, and R' is CH₃, the

compound is 2-methyl-1,1,3-trifluoro-2-propanol.

It is believed that the present novel compounds may be prepared by adapting known methods for preparing known alkanols coupled with the knowledge of one skilled in the art. For example,

2-methyl-1,1,1,3,3-pentafluoro-2-propanol may be prepared by reacting commercially available

1,1,1-trifluoro-2-propanone with CF₂ carbene to form

2-trifluoromethyl-1,1-difluoro-1-propene which may then be reacted with sulfuric acid and then water to form

2-methyl-1,1,1,3,3-pentafluoro-2-propanol.

To prepare

2-difluoromethyl-1,1,1,3,3,4,4,4-octafluoro-2-butanol, caesium fluoride and perfluoro-3-methylbut-1-ene may be reacted in moist sulpholan as taught by Robert N.

Haszeldine et al., "Fluoro-olefin Chemistry. Part 11. Some Reactions of Perfluoro-3-methylbut-1-ene under Ionic and Free-radical Conditions", J. Chem. Soc. 565 (1979) to form 2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane. The 2-trifluoromethyl-1,1,1,3,3,4,4,4-octafluorobutane may then be dehydrohalogenated and then reacted with sulfuric acid and then water to form

2-difluoromethyl-1,1,1,3,3,4,4,4-octafluoro-2-butanol. As another example,

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-butanbl may be prepared by fluorinating commercially available 2-butanone to form 2,2-difluorobutane which may then be

dehydrogenated to form 3,3-difluoro-1-butene. CF₃ may then be added to the 3,3-difluoro-1-butene to form

2-trifluoromethyl-1,3,3-trifluorobutane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3-trifluoro-1-butene. The

2-trifluoromethyl-1,3,3-trifluoro-1-butene may then be reacted with hydrogen fluoride to form

2-difluoromethyl-1,1,1,3,3,3-hexafluorobutane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3-tetrafluoro-1-butene which may then be reacted with sulfuric acid and then water to form 2-difluoromethyl-1,1,1,3,3-pentafluoro-2-butanol.

As another example,

2-difluoromethyl-1,1,1,3,3,4,4-heρtafluoro-2-pentanol may be prepared by fluorinating commercially available

2,3-pentanedione to form 2,2,3,3-tetrafluoropentane which may then be dehydrogenated to form

3,3,4,4-tetrafluoro-1-pentene. CF₃ may then be added to the 3,3,4,4-tetrafluoro-1-pentene to form

2-trifluoromethyl-1,3,3,4,4-pentafluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene. The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene may then be reacted with hydrogen fluoride to form

2-trifluoromethyl-1,1,3,3,4,4-hexafluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3,4,4-hexafluoro-1-pentene which may then be reacted with sulfuric acid and then water to form 2-difluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-pentanol. As another example,

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol may be prepared by fluorinating commercially available

3-pentanone to form 3,3-difluoropentane which may then be dehydrogenated to form 3,3-difluoro-1-pentene. CF₃ may then be reacted with the 3,3-difluoro-1-ρentene to form 2-trifluoromethyl-1,3,3-trifluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3-trifluoro-1-pentene. The

2-trifluoromethyl-1,3,3-trifluoro-1-pentene may then be reacted with hydrogen fluoride to form

2-trifluoromethyl-1,1,3,3-tetrafluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3-tetrafluoro-1-pentene which may then be reacted with sulfuric acid and then water to form 2-difluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol.

As another example,

2-difluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol may be prepared by fluorinating commercially available

3,4-hexanedione to form 3,3,4,4-tetrafluorohexane which may then be dehydrogenated to form

3,3,4,4-tetrafluoro-1-hexene. CF₃ may then be added to the 3,3,4,4-tetrafluoro-1-hexene to form

2-trifluoromethyl-1,3,3,4,4-pentafluorohexane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene. The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene may then be reacted with hydrogen fluoride to form

2-trifluoromethyl-1,1,3,3,4,4-hexafluorohexane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3,4,4-hexafluoro-1-hexene which may then be reacted with sulfuric acid and then water to form 2-difluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol. As another example,

2-methyl-1,1,1,3-tetrafluoro-2-propanol may be prepared by reacting commercially available methacrylic acid with hydrogen fluoride to form 2-methyl-3-fluoropropanoic acid which may then be fluorinated to form

2-methyl-1,1,1,3-tetrafluoropropane. The

2-methyl-1,1,1,3-tetrafluoropropane may then be

dehydrogenated and reacted with sulfuric acid and then water to form 2-methyl-1,1,1,3-tetrafluoro-2-ρropanol.

As another example,

2-fluoromethyl-1,1,1,3,4,4-hexafluoro-2-butanol may be prepared by fluorinating commercially available

3-chloropropionic acid to form 1,1,1,3-tetrafluoropropane which may then be reacted with CHF₂CF carbene to form 2-fluoromethyl-1,1,1,3,4,4-hexafluorobutane. The

2-fluoromethyl-1,1,1,3,4,4-hexafluorobutane may then be dehydrogenated and reacted with sulfuric acid and then water to form

2-fluoromethyl-1,1,1,3,4,4-hexafluoro-2-butanol.

As another example,

2-fluoromethyl-1,1,1,3,3-pentafluoro-2-butanol may be prepared by fluorinating commercially available 2-butanone to form 2,2-difluorobutane which may then be

2-trifluoromethyl-1,3,3-trifluoro-1-butene. The

2-trifluoromethyl-1,3,3-trifluoro-1-butene may then be reacted wtih sulfuric acid and then water to form

2-fluoromethyl-1,1,1,3,3-pentafluoro-2-butanol. As another example,

2-fluoromethyl-1,1,1,3,3,4,4-heρtafluoro-2-pentanol may be prepared by fluorinating commercially available

2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene. The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-pentene may then be reacted with sulfuric acid and then water to form

2-fluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-pentanol.

As another example,

2-fluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol may be prepared by fluorinating 3-pentanone to form

3,3-difluoropentane which may then be dehydrogenated to form 3,3-difluoro-1-pentene. CF₃ may then be reacted with the 3,3-difluoro-1-pentene to form

2-trifluoromethyl-1,3,3-trifluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3-trifluoro-1-pentene. The

2-trifluoromethyl-1,3,3-trifluoro-1-pentene may then be reacted with sulfuric acid and then water to form

2-fluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol.

As another example,

2-fluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol may be prepared by fluorinating commercially available

3,3,4,4-tetrafluoro-1-hexene. CF₃ may then be added to the 3,3,4,4-tetrafluoro-l-hexene to form

2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene. The 2-trifluoromethyl-1,3,3,4,4-pentafluoro-1-hexene may then be reacted with sulfuric acid and then water to form 2-fluoromethyl-1,1,1,3,3,4,4-heptafluoro-2-hexanol.

As another example,

2-methyl-1,1,1,3,3-pentafluoro-2-butanol may be prepared by fluorinating commercially available

2-methyl-1-buten-3-yne to form

3-methyl-1,2,3,4-tetrafluoro-1-butene which may then be reacted with hydrogen fluoride to form

2-methyl-1,2,3,3,4-pentafluorobutane. The

2-methyl-1,2,3,3,4-pentafluorobutane may then be

dehalogenated to form 3-methyl-2,3,4-trifluoro-1-butene which may then be reacted with hydrogen fluoride to form 2-methyl-1,2,3,3-tetrafluorobutane. The

2-methyl-1,2,3,3-tetrafluorobutane may then be

dehalogenated to form 2-methyl-1,3,3-trifluoro-1-butene which may then be fluorinated to form

2-methyl-1,1,2,3,3-pentafluorobutane. The

2-methyl-1,1,2,3,3-pentafluorobutane may then be

dehydrohalogenated to form

2-methyl-1,1,3,3-tetrafluoro-1-butene which may then be reacted with hydrogen fluoride to form

2-methyl-1,1,1,3,3-pentafluorobutane. The

2-methyl-1,1,1,3,3-ρentafluorobutane may then be

dehydrogenated and then reacted with sulfuric acid and water to form 2-methyl-1,1,1,3,3-pentafluoro-2-butanol. As another example,

2-methyl-1,1,3-trifluoro-2-propanol may be prepared by reacting commercially available fluoroacetone with a CF₂ carbene to form 2-methyl-1,1,3-trifluoro-1-propene which may then be reacted with sulfuric acid and then water to form 2-methyl-1,1,3-trifluoro-2-propanol.

Preferably, each R in the Formula above is the same. When each R is CHF₂ and R' is CF₃, the compound is 2-difluoromethyl-1,1,1,3,3-pentafluoro-2-propanol.

When each R is CHF₂ and R' is CHF₂, the compound is

2-difluoromethyl-1,1,3,3-tetrafluoro-2-propanol. When each R is CHF₂ and R' is CH₂F, the compound is

2-fluoromethyl-1,1,3,3-tetrafluoro-2-propanol. When each R is CHF₂ and R' is CH₃, the compound is

2-methyl-1,1,3,3-tetrafluoro-2-propanol. When each R is CH₂F and R' is CHF₂, the compound is

2-fluoromethyl-1,1,3-trifluoro-2-propanol. When each R is

CH₂F and R' is CH₂F, the compound is

2-fluoromethyl-1,3-difluoro-2-propanol.

As another preparation example,

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-propanol may be prepared by fluorinating commercially available

1,1,1,3,3-pentachloro-2-propanone to form

1,1,1,3,3-pentafluoro-2-propanone which may then be reacted with CF₂ carbene to form

2-difluoromethyl-1,1,3,3,3-tetrafluoro-1-propene. The

2-difluoromethyl-1,1,3,3,3-tetrafluoro-1-propene may then be reacted with sulfuric acid and then water to form

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-propanol. As another example, the

2-difluoromethyl-1,1,3,3-tetrafluoro-2-propanol may be prepared by fluorinating commercially available

1,1,3-trichloro-2-propanone to form

1,1,3-trifluoro-2-propanone which may then be reacted with

CF₂ carbene to form

2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene. The

2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene may then be hydrogenated to form

2-fluoromethyl-1,1,3,3-tetrafluoropropane. The

2-fluoromethyl-1,1,3,3-tetrafluoropropane may then be dehydrogenated to form

2-difluoromethyl-1,3,3-trifluoro-1-propene which may then be reacted with hydrogen fluoride to form

2-difluoromethyl-1,1,3,3-tetrafluoropropane. The

2-difluoromethyl-1,1,3,3-tetrafluoropropane may then be dehydrogenated and then reacted with sulfuric acid and then water to form

2-difluoromethyl-1,1,3,3-tetrafluoro-2-propanol.

As another example,

2-fluoromethyl-1,1,3,3-tetrafluoro-2-propanol may be prepared by fluorinating commercially available

1,1,3-trichloro-2-proρanone to form

1,1,3-trifluoro-2-propanone which may then be reacted with CF₂ carbene to form

2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene. The

2-fluoromethyl-1,1,3,3-tetrafluoro-1-propene may then be reacted with sulfuric acid and then water to form

2-fluoromethyl-1,1,3,3-tetrafluoro-2-ρropanol.

As another example,

2-methyl-1,1,3,3-tetrafluoro-2-ρropanol may be prepared by fluorinating commercially available

1,1-dichloro-2-propanone to form 1,1-difluoro-2-propanone which may then be reacted with CF₂ carbene to form 2-methyl-1,1,3,3-tetrafluoro-1-propene. The

2-methyl-1,1,3,3-tetrafluoro-1-propene may then be reacted with sulfuric acid and then water to form

2-methyl-1,1,3,3-tetrafluoro-2-propanol.

As another example, the

2-fluoromethyl-1,1,3-trifluoro-2-propanol may be prepared by oxidizing commercially available

1,3-difluoro-2-propanol to 1,3-difluoro-2-propanone which may then be reacted with a CF₂ carbene to form

2-fluoromethyl-1,1,3-trifluoro-1-propene. The

2-fluoromethyl-1,1,3-trifluoro-1-propene may then be reacted with sulfuric acid and then water to form

2-fluoromethyl-1,1,3-trifluoro-2-propanol.

As another example, the

2-fluoromethyl-1,3-difluoro-2-propanol may be prepared by oxidizing commercially available 1,3-difluoro-2-proρanol to 1,3-difluoro-2-propanone which may then be reacted with a CF₂ carbene to form

2-fluoromethyl-1,1,3-trifluoro-1-propene. The

2-fluoromethyl-1,1,3-trifluoro-1-ρropene may then be hydrogenated to form

2-fluoromethyl-1,1,3-trifluoropropane. The

2-fluoromethyl-1,1, 3-trifluoropropane may then be

dehydrohalogenated to form

2-fluoromethyl-1,3-difluoro-1-propene which may then be reacted with sulfuric acid and then water to form

2-fluoromethyl-1,3-difluoro-2-propanol. More preferably, each R in the Formula above is CF₃. When R' is CF₃CF₂CHF-, the compound is

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentanol. To prepare

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentanol, commercially available hexafluoropropene may be

oligomerized with commercially available trimethylamine in a dipolar aprotic solvent such as commercially available tetrahydrofuran to provide (CF₃)₂C:CFCF₂CF₃ as

taught by W. Brunskill et al., "Anionic Oligomerisation of Hexafluoropropene: Fission of a Carbon-Carbon Bond by Fluoride Ion", Chemical Communications. 1444 (1970); the (CF₃)₂C:CFCF₂CF₃ may then be reacted with sulfuric

acid and then water to form

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentanol.

Most preferably, each R is CF₃ and R' is selected from the group consisting of CHF₂, CH₃,

CF₃CF₂CHF-, CF₃CHF-, CF₃CH₂-, CHF₂CH₂-,

CH₃CF₂-, CH₃CH₂CF₂-, CH₃ (CH₂)₂CF₂-,

CH₃CH₂-, and CH₃(CH₂)₂-. The names of the

preceding preferred hydrofluorocarbons are

2-difluoromethyl-1,1,1,3,3,3-hexafluoro-2-proρanol;

2-methyl-1,1,1,3,3,3-hexafluoro-2-propanol;

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentanol; 2-trifluoromethyl-1,1,1,3,4,4,4-heptafluoro-2-butano1;

2-trifluoromethyl-1,1,1,4,4,4-hexafluoro-2-butanol;

2-trifluoromethyl-1,1,1,4,4-pentafluoro-2-butanol;

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-butanol;

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol;

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-hexanol;

2-trifluoromethyl-1,1,1-trifluoro-2-butanol; and

2-trifluoromethyl-1,1,1-trifluoro-2-pentanol. As another example,

2-difluoromethyl-1,1,1,3,3,3-hexafluoro-2-propanol may be prepared by treating commercially available

hexafluoropropene with hydrogen fluoride as taught by commonly assigned U.K. Patent 902,590 to form

1,1,1,2,3,3,3-heptafluoropropane. The

1,1,1,2,3,3,3-heptafluoropropane may then be heated at 475-700°C in the presence of activated carbon as taught by commonly assigned U.S. Patent 2,981,763 which is

incorporated herein by reference to form

2-trifluoromethyl-1,1,1,3,3,3-hexafluoropropane or

nonafluoroisobutane. The nonafluoroisobutane may then be treated with commercially available benzoyl chloride in the presence of commercially available triethylamine as taught by B. L. Dyatkin et al., "The Perfluoro-t-butyl Anion in the Synthesis of Organofluorine Compounds", Russian Chemical Reviews 45(7). 607 (1976) to form

perfluoroisobutene. The perfluoroisobutene may then be reacted with sulfuric acid and then water to form

2-difluoromethyl-1,1,1,3,3,3-hexafluoro-2-propanol.

As another example,

2-methyl-1,1,1,3,3,3-hexafluoro-2-propanol may be prepared by reacting commercially available hexafluoropropene with elemental sulfur and commercially available potassium fluoride in commercially available dimethylformamide under substantially atmospheric pressure and at temperatures between 25-100°C as taught by commonly assigned U.S.

Patent 4,326,068 which is incorporated herein by reference to form hexafluorothioacetone dimer. The

hexafluorothioacetone dimer may then be reacted with commercially available formaldehyde as taught by commonly assigned U.S. Patent 4,367,349 which is incorporated herein by reference to form hexafluoroisobutylene. The hexafluoroisobutylene may then be reacted with sulfuric acid and then water to form

2-methyl-1,1,1,3,3,3-hexafluoro-2-propanol. To prepare

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluorό-2-pentano1, commercially available hexafluoropropene may be

oligomerized with commercially available trimethylamine in a dipolar aprotic solvent such as commercially available tetrahydrofuran to provide (CF₃)₂C:CFCF₂CF₃ which

is then reacted with commercially available hydrogen fluoride to yield

2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane as taught by W. Brunskill et al., "Anionic Oligomerisation of Hexafluoropropene: Fission of a Carbon-Carbon Bond by Fluoride Ion", Chemical Communications. 1444 (1970). The 2-trifluoromethyl-1,1,1,3,3,4,4,5,5,5-decafluoropentane may then be dehydrohalogenated and then reacted with sulfuric acid and then water to form

2-trifluoromethyl-1,1,1,3,4,4,5,5,5-nonafluoro-2-pentanol.

As another example,

2-trifluoromethyl-1,1,1,3,4,4,4-heptafluoro-2-butanol may be prepared by reacting commercially available

1,1-difluoroethylene according to the procedure of George L. Fleming et al., "Addition of Free Radicals to

Unsaturated Systems. Part XX. The Direction of Radical Addition of Heptafluoro-2-iodopropane to Vinyl Fluoride, Trifluoroethylene, and Hexafluoropropene", J.C.S. Perkin X, 574 (1973) to form a product which may then be

fluorinated to form

2-trifluoromethyl-1,1,1,2,3,4,4,4-octafluorobutane. The 2-trifluoromethyl-1,1,1,2,3,4,4,4-octafluorobutane may then be dehydrohalogenated and then reacted with sulfuric acid and then water to form

2-trifluoromethyl-1,1,1,3,4,4,4-heptafluoro-2-butanol .

As another example,

2-trifluoromethyl-1,1,1,4,4,4-hexafluoro-2-butanol may be prepared by reacting commercially available

1,1-difluoroethylene according to the procedure of George L. Fleming et al., supra, to form a product which may then be reacted with hydrogen fluoride to form

2-trifluoromethyl-1,1,1,2,4,4,4-hexafluorobutane which may then be dehydrohalogenated and then reacted with sulfuric acid and then water to form

2-trifluoromethyl-1,1,1,4,4,4-hexafluoro-2-butanol.

As another example,

2-trifluoromethyl-1,1,1,4,4-pentafluoro-2-butanol may be prepared by reacting commercially available

1,1-difluoroethylene according to the procedure of George L. Fleming et al., supra, to form a product which may then be hydrogenated to form

2-trifluoromethyl-1,1,1,2,4,4-hexafluorobutane which may then be dehydrohalogenated and then reacted with sulfuric acid and then water to form

2-trifluoromethyl-1,1,1,4,4-pentafluoro-2-butanol.

As another example,

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-butanol may be prepared by fluorinating commercially available 2-butanone to form 2,2-difluorobutane which may then be

2-trifluoromethyl-1,3,3-trifluoro-1-butene. The

2-difluoromethyl-1,1,1,3,3-pentafluorobutane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3-tetrafluoro-1-butene which may then be fluorinated to form

2-trifluoromethyl-1,1,1,2,3,3-hexafluorobutane. The

2-trifluoromethyl-1,1,1,2,3,3-hexafluorobutane is then hydrolyzed to form

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-butanol. As another example,

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol may be prepared by fluorinating commercially available

3-pentanone to form 3,3-difluoropentane which may then be dehydrogenated to form 3,3-difluoro-1-pentene. CF₃ may then be reacted with the 3,3-difluoro-1-pentene to form 2-trifluoromethyl-1,3,3-trifluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,3,3-trifluoro-1-pentene. The

2-trifluoromethyl-1,1,3,3-tetrafluoro-1-pentene which may then be fluorinated to form

2-trifluoromethyl-1,1,1,2,3,3-hexafluoropentane. The 2-trifluoromethyl-1,1,1,2,3,3-hexafluoropentane is then hydrolyzed to form

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-pentanol.

As another example,

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-hexanol may be prepared by fluorinating commercially available 3-hexanone to form 3,3-difluorohexane which may then be

dehydrogenated to form 3,3-difluoro-2-hexene. CF₃ may then be reacted with the 3,3-difluoro-2-hexene to form 2-trifluoromethyl-1,3,3-trifluorohexane which may then be dehydrogenated to form

2-trifluoromethyl-1,3, 3-trifluoro-1-hexene. The

2-trifluoromethyl-1,3,3-trifluoro-1-hexene may then be reacted with hydrogen fluoride to form

2-trifluoromethyl-1,1,3,3-tetrafluorohexane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,3,3-tetrafluoro-1-hexene which may then be fluorinated to form

2-trifluoromethyl-1,1,1,2,3,3-hexafluorohexane. The

2-trifluoromethyl-1,1,1,2,3,3-hexafluorohexane may then be hydrolyzed to form

2-trifluoromethyl-1,1,1,3,3-pentafluoro-2-hexanol.

As another example,

2-trifluoromethyl-1,1,1-trifluoro-2-butanol may be

prepared by fluorinating commercially available

butyraldehyde to form 1,1-difluorobutane which may then be dehydrogenated to form 1,1-difluoro-1-butene. CF₃ may then be reacted with the 1,1-difluoro-1-butene to form 2-trifluoromethyl-1,1,1-trifluorobutane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,1-trifluoro-2-butene. The

2-trifluoromethyl-1,1,1-trifluoro-2-butene may then be reacted with water to form

2-trifluoromethyl-1,1,1-trifluoro-2-butanol.

As another example,

2-trifluoromethyl-1,1,1-trifluoro-2-pentanol may be prepared by fluorinating commercially available 2-pentenal to form 1,1,2,3-tetrafluoropentane which may then be dehydrogenated to form 1,1-difluoro-1-pentene. CF₃ may then be reacted with the 1,1-difluoro-1-pentene to form 2-trifluoromethyl-1,1,1-trifluoropentane which may then be dehydrogenated to form

2-trifluoromethyl-1,1,1-trifluoro-2-pentene. The

2-trifluoromethyl-1,1,1-trifluoro-2-pentene may then be reacted with water to form

2-trifluoromethyl-1,1,1-trifluoro-2-pentanol. The present compounds are useful as solvents for use in vapor degreasing and other solvent cleaning

applications including defluxing, cold cleaning, dry cleaning, dewatering, decontamination, spot cleaning, aerosol propelled rework, extraction, particle remova1, and surfactant cleaning applications. These compounds are also useful as blowing agents, Rankine cycle and

absorption refrigerants, and power fluids and especially as refrigerants for centrifugal refrigeration chillers. The present invention also provides a method of cleaning a solid surface which comprises treating the surface with a compound having the Formula:

CH₃CF₂, and R' is an alkyl or fluoroalkyl group having

1 to 6 carbon atoms.

Preferably, R' in the Formula above is selected from the group consisting of CF₃, CHF₂, CH₂F, CH₃, CF₃CF₂-, CF₃(CF₂)₂-, CF₃CF₂CHF-,

CF₃CF₂CH₂-, CF₃CHF-, CF₃(CHF)₂-,

CF₃CHFCF₂-, CF₃CHFCH₂-, CF₃CH₂-,

CF₃(CH₂)₂-, CF₃CH₂CF₂-, CF₃CH₂CHF-,

CHF₂CF₂-, CHF₂(CF₂)₂-, CHF₂CF₂CHF-,

CHF₂CF₂CH₂-, CHF₂CHF-, CHF₂(CHF)₂-,

CHF₂CHFCF₂-, CHF₂CHFCH₂-, CHF₂CH₂-,

CHF₂(CH₂)₂-, CHF₂CH₂CF₂-, CHF₂CH₂CHF-,

CH₂FCF₂-, CH₂F(CF₂)₂-, CH₂FCF₂CHF-,

CH₂FCF₂CH₂-, CH₂FCHF-, CH₂F(CHF)₂-,

CH₂FCHFCF₂-, CH₂FCHFCH₂-, CH₂FCH₂-,

CH₂F(CH₂)₂-, CH₂FCH₂CF₂-, CH₂FCH₂CHF-,

CH₃CF₂-, CH₃(CF₂)₂-, CH₃CF₂CHF-,

CH₃CF₂CH₂-, CH₃CHF-, CH₃(CHF)₂-,

CH₃CHFCF₂-, CH₃CHFCH₂-, CH₃CH₂-,

CH₃(CH₂)₂-, CH₃(CH₂)₃-, CH₃CH₂CF₂-,

CH₃(CH₂)₂CF₂-, CH₃(CH₂)₃CF₂-,

CH₃CH₂(CF₂)₂-, CH₃(CH₂)₂(CF₂)₂-, and

CH₃(CH₂)₃(CF₂)₂-. In the process embodiment of the invention, the compositions may be used to clean solid surfaces by treating the surfaces with the compounds in any manner well known to the art such as by dipping or spraying or use of conventional degreasing apparatus.

When the novel compounds are used to clean solid surfaces by spraying the surfaces with the compounds, preferably, the novel compounds are sprayed onto the surfaces by using a propellant. Preferably, the

propellant is selected from the group consisting of hydrochlorofluorocarbon, hydrofluorocarbon, and mixtures thereof. Useful hydrochlorofluorocarbon propellents include dichlorofluoromethane (known in the art as

HCFC-21), chlorodifluoromethane (known in the art as

HCFC-22), 1,1-dichloro-2,2-difluoroethane (known in the art as HCFC-132a), 1-chloro-2,2,2-trifluoroethane (known in the art as HCFC-133), and 1-chloro-1,1-difluoroethane (known in the art as HCFC-142b); commercially available HCFC-21, HCFC-22, and HCFC-142b may be used in the present invention. Useful hydrofluorocarbon propellants include trifluoromethane (known in the art as HFC-23),

1,1,1,2-tetrafluoroethane (known in the art as HFC-134a), and 1,1-difluoroethane (known in the art as HFC-152a); commercially available HFC-23 and HFC-152a may be used in the present invention. Until HFC-134a becomes available in commercial quantities, HFC-134a may be made by a known method such as that disclosed by U.S. Patent 4,851,595. Preferred propellants include chlorodifluoromethane and 1,1,1,2-tetrafluoroethane. The present invention is more fully illustrated by the following non-limiting Examples.

EXAMPLES 1-573 For each example, the novel compound of the Formula above having the R and R' groups as indicated in Table I below is made.

EXAMPLES 574-1,146

Metal coupons are soiled with various types of oil. The soiled metal coupons are immersed in the novel solvents of Table I above for a period of 15 seconds to 2 minutes, removed, and allowed to air dry. Upon visual inspection, the soil appears to be substantially removed.

EXAMPLES 1,147-1,719 Metal coupons are soiled with various types of oil. The soiled metal coupons are wiped with the novel solvents of Table I above and allowed to air dry. Upon visual inspection, the soil appears to be substantially removed.

Having described the invention in detail and by reference to preferred embodiments thereof, it will be apparent that modifications and variations are possible without departing from the scope of the invention defined in the appended claims.

Claims

What is claimed is;

1. A compound having the formula

wherein each R is the same or different and is selected from the group consisting of CF₃, CHF_2, CH₂F, and CH₃CF_2, and R' is an alkyl or fluoroalkyl group having 1 to 6 carbon atoms wherein said compound is not

(CF₃)₂(CH₃)COH.

2. The compound of claim 1 wherein said R' is selected from the group consisting of CF₃, CHF₂, CH₂F, CH₃, CF₃CF₂-, CF₃(CF₂)₂-, CF₃CF₂CHF-, CF₃CF₂CH₂-, CF₃CHF-, CF₃(CHF)₂-, CF₃CHFCF₂-, CF₃CHFCH₂-, CF₃CH₂-, CF₃(CH₂)₂-, CF₃CH₂CF₂-, CF3CH₂CHF-, CHF₂CF₂-, CHF₂(CF₂)₂-, CHF₂CF₂CHF-, CHF₂CF₂CH₂-, CHF₂CHF-_, CHF₂(CHF)₂-, CHF₂CHFCF₂-,

CHF₂CHFCH₂-, CHF₂CH₂-, CHF₂(CH₂)₂-, CHF₂CH₂CF₂-,

CHF₂CH₂CHF-, CH₂FCF₂-, CH₂F(CF₂)₂-, CH₂FCF₂CHF-,

CH₂FCF₂CH₂-, CH₂FCHF-, CH₂F(CHF)₂-, CH₂FCHFCF₂-,

CH₂FCHFCH₂-, CH₂FCH₂-, CH₂F(CH₂)2-, CH₂FCH₂CF₂-,

CH₂FCH₂CHF-, CH₃CF₂-, CH₃(CF₂)₂-, CH₃CF₂CHF-, CH₃CF₂CH₂-, CH₃CHF-, CH₃(CHF)₂-, CH₃CHFCF₂-, CH₃CHFCH₂-, CH₃CH₂-,

CH₃(CH₂)₂-. CH₃(CH_Z)₃-, CH₃CH₂CF₂-, CH₃(CH₂)₂CF₂-,

CH₃(CH₂)₃CF₂-_, CH₃CH₂(CF₂)₂-, CH₃(CH₂)₂(CF₂)₂-, and

CH₃ (CH₂) ₃ (CF₂)₂- .

3. The compound of claim 2 wherein each of said R is the same.

4. The compound of claim 1 wherein said compound is selected from the group consisting of

2-difluoromethyl-1,1,1,3,3-pentafluoro-2-propanol;

2-difluoromethyl-1,1,3,3-tetrafluoro-2-propanol; 2-f luoromethyl-1,1,3,3-tetraf luoro-2-propanol;

2-methyl-1,1,3,3-tetrafluoro-2-propanol;

2-f luoromethyl-1,1,3-trifluoro-2-propanol; and

2-fluoromethyl-1,3-difluoro-2-propanol .

5. The compound of claim 3 wherein each of said R is CF₃.

6. The compound of claim 5 wherein said R' is selected from the group consisting of CHF₂, CF₃CH₂-,

CF₃CHF-, CHF₂CH₂-, and CF₃CF₂CHF-.

7. The compound of claim 5 wherein said R' is

CHF₂.

8. The compound of claim 5 wherein said R' is CF₃CH₂- .

9. The compound of claim 5 wherein said R* is CF₃CHF-.

10. A method of cleaning a solid surface which comprises treating said surface with said compound of claim 1.