WO2013062733A1

WO2013062733A1 - Catalytic processes for making hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds

Info

Publication number: WO2013062733A1
Application number: PCT/US2012/058981
Authority: WO
Inventors: Ekaterina N. Swearingen
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2011-10-24
Filing date: 2012-10-05
Publication date: 2013-05-02
Anticipated expiration: 2014-04-24
Also published as: US20140303410A1; CN103917507A; US9212109B2

Abstract

Disclosed is a process involving contacting a hydrohalobutane selected from the group consisting of CF₂HCHClCH₂CCl₂H, CF₃CHClCH₂CCl₂H, CF₃CHClCH₂CCl₃, CF₃CClHCHFCCl₂H and CF₃CClHCHFCCl₃, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCl₅ and SbF₅ to form a first product mixture containing a hydromonochlorofluorobutane. Also disclosed is a process involving contacting a hydrohalopentane selected from the group consisting of CF₂HCHClCH₂CX₂CX₃and CF₃CHClCH₂CX₂CX₃, wherein each X is independently selected from the group consisting of F and Cl, and not all X are fluorines, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCl₅ and SbF₅ to form a first product mixture containing a hydromonochlorofluoropentane. A compound of the formula CF₃CHClCH₂CHF₂ is also disclosed.

Description

TITLE

CATALYTIC PROCESSES FOR MAKING HYDROMONOCHLOROFLUOROBUTANE AND HYDROMONOCHLOROFLUOROPENTANE COMPOUNDS

BACKGROUND

This disclosure relates in general to the catalytic fluorination processes of making hydromonochlorofluorobutane and

hydromonochlorofluoropentane compounds in the presence of antimony halide catalysts.

HCFCs (hydrochlorofluorocarbons), such as

hydromonochlorofluorobutane and hydromonochlorofluoropentane compounds, can be employed in a wide range of applications, including their use as aerosol propellants, refrigerants, cleaning agents, expansion agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents. They are also useful as intermediates to internal hydrofluorobutenes and internal hydrofluoropentenes which are potential candidates to replace HCFCs in the applications noted above. Internal hydrofluorobutenes and internal hydrofluoropentenes, such as CF₃CH=CHCHF₂ and

CF₃CH=CHCF₃, are believed to be safe for the stratospheric ozone layer and have low global warming potentials (GWPs).

SUMMARY OF THE DISCLOSURE

The present disclosure provides a process comprising contacting a hydrohalobutane selected from the group consisting of

CF₂HCHCICH₂CCI₂H, CF3CHCICH2CCI2H, CF3CHCICH2CCI3,

CF3CCIHCHFCCI2H and CF3CCIHCHFCCI3, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluorobutane.

The present disclosure also provides a process comprising contacting a hydrohalopentane selected from the group consisting of CF2HCHCICH2CX2CX3 and CF3CHCICH2CX2CX3, wherein each X is independently selected from the group consisting of F and CI, and not all X are fluorines, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluoropentane.

The present disclosure also provides a new compound of the formula CF3CHCICH2CHF2. It is particularly useful as an intermediate for producing an internal hydrofluorobutene of the formula CF₃CH=CHCHF₂. BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 - FIG. 1 is a graphical representation of the ¹ H NMR spectrum of CF3CHCICH2CHF2.

FIG. 2 - FIG. 2 is a graphical representation of the ¹⁹F NMR spectrum of CF3CHCICH2CHF2.

DETAILED DESCRIPTION

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the inventive concept(s), as defined in the appended claims. Other features and benefits of any one or more of the embodiments will be apparent from the following detailed description, and from the claims.

As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). Also, use of "a" or "an" are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

When an amount, concentration, or other value or parameter is given as either a range, preferred range or a list of upper preferable values and/or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

The term "hydromonochlorofluorobutane", as used herein, means a n-butane wherein the hydrogens are partially substituted by some fluorines and one chlorine. Hydromonochlorofluorobutanes in this disclosure are selected from the group consisting of CF2HCHCICH2CF2H,

CF3CHCICH2CHF2, CF3CHCICH2CF3, CF3CCIHCHFCF2H, and

CF3CCIHCHFCF3.

The term "hydromonochlorofluoropentane", as used herein, means a n-pentane wherein the hydrogens are partially substituted by some fluorines and one chlorine. Hydromonochlorofluoropentanes in this disclosure are selected from the group consisting of

CF2HCHCICH2CF2CF3 and CF3CHCICH2CF2CF3. The term "hydrohalobutane", as used herein, means a n-butane wherein the hydrogens are partially substituted by chlorines and fluorines. Hydrohalobutanes in this disclosure are selected from the group consisting of CF2HCHCICH2CCI2H, CF3CHCICH2CCI2H, CF₃CHCICH₂CCI₃,

CF3CCIHCHFCCI2H and CF3CCIHCHFCCI3.

The term "hydrohalopentane", as used herein, means a n-pentane wherein the hydrogens are partially substituted by chlorines and fluorines. Hydrohalopentanes in this disclosure are selected from the group consisting of CF2HCHCICH2CX2CX3 and CF3CHCICH2CX2CX3, wherein each X is independently selected from the group consisting of F and CI, and not all X are fluorines.

The term "internal hydrofluorobutene", as used herein, means a partially fluorine-substituted butene wherein the carbon-carbon double bond is not at the terminal position. Internal hydrofluorobutenes in this disclosure are selected from the group consisting of CF₂HCH=CHCF₂H, CF₃CH=CHCHF₂, CF₃CH=CHCF₃, CF₃CH=CFCF₂H, and CF₃CH=CFCF₃.

The term "internal hydrofluoropentene", as used herein, means a partially fluorine-substituted pentene wherein the carbon-carbon double bond is not at the terminal position. Internal hydrofluoropentenes in this disclosure are selected from the group consisting of CF₂HCH=CHCF₂CF3 and CF₃CH=CHCF₂CF₃.

The term "dehydrochlorinating", "dehydrochlorination" or

"dehydrochlorinated", as used herein, means a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed.

The internal hydrofluorobutenes and internal hydrofluoropentenes exist as different configurational isomers or stereoisomers. When the specific isomer is not designated, the present description is intended to include all single configurational isomers, single stereoisomers, or any combination thereof. For instance, CF₃CH=CHCHF₂ is meant to represent the E-isomer, Z-isomer, or any combination or mixture of both isomers in any ratio.

Hydrohalobutanes and hydrohalopentanes may be prepared by the processes known in the art. Hydrohalobutanes and hydrohalopentanes may also be prepared by catalytic addition reactions of CHCI₃, CCI₄ or CF3CCI3 with suitable alkenes. For example, CF₂HCHCICH₂CCI₂H can be synthesized by addition reaction of CHCI₃ with CF₂HCH=CH₂;

CF₃CHCICH₂CCI₂H can be synthesized by addition reaction of CHCI3 with CF₃CH=CH₂; CF₃CHCICH₂CCI₃ can be synthesized by addition reaction of CCI₄ with CF₃CH=CH₂; CF₃CCIHCHFCCI₂H can be synthesized by addition reaction of CHCI₃ with CF₃CH=CHF; CF3CCIHCHFCCI3 can be synthesized by addition reaction of CCI₄ with CF₃CH=CHF; and

CF₃CHCICH₂CCI₂CF₃ can be synthesized by addition reaction of CF3CCI3 with CF₃CH=CH₂. Suitable catalysts for such addition reactions include copper catalysts and iron catalysts. A copper catalyst typically comprises cupric chloride and a suitable reductant (e.g., copper powder,

phenylhydrazine), and is typically used together with a solvent (e.g., acetonitrile). An iron catalyst typically comprises iron powder and ferric chloride, and is typically used together with a co-catalyst (e.g., tributyl phosphate). Further information on the preparation of hydrohalobutanes and hydrohalopentanes is provided in Russian Patent Application

Numbers 2010147009, 2010147008 and 20100147002 [FL1564, FL1565 and FL1388].

Reactors, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the processes of embodiments of the inventive concept(s) described herein should be constructed of materials resistant to corrosion. Typical materials of construction include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.

Fluorination Processes for Making Hvdromonochlorofluorobutane or Hvdromonochlorofluoropentane Compounds

Disclosed is a process comprising contacting a hydrohalobutane selected from the group consisting of CF₂HCHCICH₂CCI₂H,

CF₃CHCICH₂CCI₂H, CF₃CHCICH₂CCI₃, CF₃CCIHCHFCCI₂H and

CF3CCIHCHFCCI3, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluorobutane. In some embodiments of this invention, the hydromonochlorofluorobutane is recovered from the first product mixture.

Also disclosed is a process comprising contacting a

hydrohalopentane selected from the group consisting of

CF2HCHCICH2CX2CX3 and CF3CHCICH2CX2CX3, wherein each X is independently selected from the group consisting of F and CI, and not all X are fluorines, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluoropentane. In some embodiments of this invention, the hydromonochlorofluoropentane is recovered from the first product mixture.

The processes above are fluorination processes for making hydromonochlorofluorobutane or hydromonochlorofluoropentane compounds. During the processes, the hydrohalobutane starting materials are selectively fluorinated to form hydromonochlorofluorobutane products, and the hydrohalopentane starting materials are selectively fluorinated to form hydromonochlorofluoropentane products.

In some embodiments of this invention, the hydrohalobutane starting material is CF2HCHCICH2CCI2H, and the corresponding

hydromonochlorofluorobutane product is CF2HCHCICH2CF2H.

In some embodiments of this invention, the hydrohalobutane starting material is CF3CHCICH2CCI2H, and the corresponding

hydromonochlorofluorobutane product is CF3CHCICH2CHF2.

In some embodiments of this invention, the hydrohalobutane starting material is CF₃CHCICH₂CCI₃, and the corresponding

hydromonochlorofluorobutane product is CF3CHCICH2CF3.

In some embodiments of this invention, the hydrohalobutane starting material is CF3CCIHCHFCCI2H, and the corresponding

hydromonochlorofluorobutane product is CF₃CCIHCHFCF₂H.

In some embodiments of this invention, the hydrohalobutane starting material is CF3CCIHCHFCCI3, and the corresponding

hydromonochlorofluorobutane product is CF3CCIHCHFCF3. In some embodiments of this invention, the hydrohalopentane starting material is CF2HCHCICH2CX2CX3, and the corresponding hydromonochlorofluoropentane product is CF2HCHCICH2CF2CF3.

In some embodiments of this invention, the hydrohalopentane of the formula CF2HCHCICH2CX2CX3 is selected from the group consisting of CF2HCHCICH2CCI2CCI3, CF2HCHCICH2CCIFCCI3,

CF2HCHCICH2CCI2CF3, CF2HCHCICH2CCIFCF3 and

CF2HCHCICH2CCI2CCIF2.

In some embodiments of this invention, the hydrohalopentane starting material is CF3CHCICH2CX2CX3, and the corresponding

hydromonochlorofluoropentane product is CF3CHCICH2CF2CF3.

In some embodiments of this invention, the hydrohalopentane of the formula CF3CHCICH2CX2CX3 is selected from the group consisting of CF3CHCICH2CCI2CCI3, CF3CHCICH2CCIFCCI3, CF3CHCICH2CCI2CF3, CF3CHCICH2CCIFCF3 and CF3CHCICH2CCI2CCIF2.

The term "antimony halide catalyst", as used herein, means SbCI₅ or SbF₅. SbCI₅ and SbF₅ are commercially available.

The fluorination process of this disclosure is typically carried out in anhydrous or substantially anhydrous conditions, which means that water, which is detrimental to the reaction, should be excluded as much as possible from the reaction zone.

Typically, the fluorination process of this disclosure is carried out in a liquid phase. It can be carried out in batch reactors, continuous reactors or any combination of such reactors by methods known in the art. In some embodiments of this invention, HF and antimony halide catalyst are pre- mixed before contacting or reacting with hydrohalobutane or

hydrohalopentane. In some embodiments of this invention,

hydrohalobutane or hydrohalopentane is fed to a reaction zone containing the mixture of HF and antimony halide catalyst. In some embodiments of this invention, hydrohalobutane or hydrohalopentane is co-fed with HF to a reaction zone containing the antimony halide catalyst.

The temperature employed in the reaction zone for the fluorination process of this disclosure typically ranges from about 60° C to about 160° C. In some embodiments of this invention, the temperature employed in the reaction zone for the fluorination process of this disclosure ranges from about 80° C to about 140° C. In some embodiments of this invention, the temperature employed in the reaction zone for the fluorination process of this disclosure ranges from about 100° C to about 140° C.

The pressure in the reaction zone for the fluorination process of this disclosure can be subatmospheric, atmospheric or superatmospheric. In some embodiments of this invention, the fluorination process of this disclosure is conducted under autogenous pressure.

The fluorination process of this disclosure uses a molar ratio of HF to the hydrohalobutane or hydrohalopentane starting material that is at least stoichiometric. The stoichiometric amount is the total number of CI substituents on the hydrohalobutane or hydrohalopentane starting materials minus one. For example, the stoichiometric ratio of HF to CF₃CHCICH₂CCI₂H is 2:1 .

The molar ratio of HF to the hydrohalobutane or hydrohalopentane starting material is typically from about the stoichiometric amount to about 50:1 . In some embodiments of this invention, the molar ratio of HF to the hydrohalobutane or hydrohalopentane starting material is from about twice the stoichiometric amount to about 30:1 . In some embodiments of this invention, the molar ratio of HF to the hydrohalobutane or

hydrohalopentane starting material is from about twice the stoichiometric amount to about 20:1 .

The hydromonochlorofluorobutane or

hydromonochlorofluoropentane product can be recovered from its reaction product mixture by well-known techniques, such as fractional distillation. At the end of the fluorination reaction, the reaction may be quenched with water or a buffer solution, such as a phosphate solution. The organic phase can be separated, dried and distilled to recover the

hydromonochlorofluorobutane or hydromonochlorofluoropentane product. In some embodiments of this invention, the recovered

hydromonochlorofluorobutane or hydromonochlorofluoropentane is at least 95 mole % pure. In some embodiments of this invention, the recovered hydromonochlorofluorobutane or

hydromonochlorofluoropentane is at least 98 mole % pure. Also disclosed is a new compound of the formula

CF₃CHCICH₂CHF₂. This is a novel hydromonochlorofluorobutane compound which may be made by reacting CF3CHCICH2CCI2H with HF in the presence of an antimony halide catalyst as demonstrated by Examples

Dehvdrochlorination Processes for Making Internal Hvdrofluorobutenes and Internal Hvdrofluoropentenes

The hydromonochlorofluorobutane formed in the fluorination process above can be further dehydrochlorinated to form a second product mixture comprising an internal hydrofluorobutene. In some embodiments of this invention, the hydromonochlorofluorobutane is CF3CHCICH2CHF2, and the corresponding internal hydrofluorobutene product is CF₃CH=CHCHF₂. In some embodiments of this invention, the hydromonochlorofluorobutane is CF3CHCICH2CF3, and the corresponding internal hydrofluorobutene product is CF₃CH=CHCF₃.

The hydromonochlorofluoropentane formed in the fluorination process above can also be further dehydrochlorinated to form a second product mixture comprising an internal hydrofluoropentene. In some embodiments of this invention, the hydromonochlorofluoropentane is

CF3CHCICH2CF2CF3, and the corresponding internal hydrofluoropentene product is CF₃CH=CHCF₂CF₃.

In some embodiments of this invention, the dehydrochlorination process is carried out by pyrolyzing hydromonochlorofluorobutane to form a second product mixture comprising an internal hydrofluorobutene. In some embodiments of this invention, the dehydrochlorination process is carried out by pyrolyzing hydromonochlorofluoropentane to form a second product mixture comprising an internal hydrofluoropentene. The term "pyrolyzing" or "pyrolysis", as used herein, means chemical change produced by heating in the absence of catalyst. Suitable reactors for pyrolysis may be of any shape consistent with the process. In some embodiments of this invention, the reactor is a cylindrical tube, either straight or coiled. Heat is applied to the outside of the tube, with the chemical reaction taking place on the inside of the tube. Of note are pyrolysis reactors wherein the flow of gases through the reactor is partially obstructed to cause back-mixing, i.e. turbulence, and thereby promote mixing of gases and good heat transfer. This partial obstruction can be conveniently obtained by placing packing within the interior of the reactor, filling its cross-section or by using perforated baffles. The reactor packing can be particulate or fibrillar, has an open structure like that of Raschig Rings or other packings with a high free volume to avoid the accumulation of coke and to minimize pressure drop, and permits a generally free flow of gas. In some embodiments of this invention, the reactor packing is in cartridge disposition for ease of insertion and removal. In some

embodiments of this invention, the pyrolysis temperature ranges from about 500° C to about 700° C. Pyrolysis processes have also been disclosed in U.S. Patent Publication No. 2010-0105967, which is

incorporated herein by reference.

The dehydrochlorination process can also be carried out in the presence of a dehydrochlorination catalyst. In some embodiments of this invention, hydromonochlorofluorobutane is dehydrochlorinated in the presence of a dehydrochlorination catalyst to form a second product mixture comprising an internal hydrofluorobutene. In some embodiments of this invention, hydromonochlorofluoropentane is dehydrochlorinated in the presence of a dehydrochlorination catalyst to form a second product mixture comprising an internal hydrofluoropentene. Suitable

dehydrochlorination catalysts include carbon, metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); alumina; fluorided alumina; aluminum fluoride; aluminum chlorofluoride; metals supported on alumina; metals supported on aluminum fluoride or chlorofluoride; magnesium fluoride supported on aluminum fluoride;

metals supported on fluorided alumina; alumina supported on carbon; aluminum fluoride or chlorofluoride supported on carbon; fluorided alumina supported on carbon; metals supported on carbon; and mixtures of metals, aluminum fluoride or chlorofluoride, and graphite. Suitable metals for use on dehydrochlorination catalysts (optionally on alumina, aluminum fluoride, aluminum chlorofluoride, fluorided alumina, or carbon) include chromium, iron, and lanthanum. Typically, when used on a support, the total metal content of the dehydrochlorination catalyst will be from about 0.1 to 20 percent by weight; and in some embodiments from about 0.1 to 10 percent by weight. In some embodiments of this invention, dehydrochlorination catalysts include carbon, alumina, and fluorided alumina. In some embodiments of this invention, carbon includes acid-washed carbon, activated carbon and three dimensional matrix carbonaceous materials. The catalytic dehydrochlorination processes have also been disclosed in U.S. Patent No. 7,943,015, which is incorporated herein by reference.

In some embodiments of this invention, the dehydrochlorination process is carried out by contacting hydromonochlorofluorobutane with a basic aqueous solution to form a second product mixture comprising an internal hydrofluorobutene. In some embodiments of this invention, the dehydrochlorination process is carried out by contacting

hydromonochlorofluoropentane with a basic aqueous solution to form a second product mixture comprising an internal hydrofluoropentene. As used herein, the basic aqueous solution is a liquid that is primarily an aqueous liquid having a pH of over 7; and the liquid may be a solution, dispersion, emulsion, suspension or the like. In some embodiments of this invention, the basic aqueous solution has a pH of 8 or higher. In some embodiments of this invention, the basic aqueous solution has a pH of 10 or higher. In some embodiments of this invention, an inorganic base is used to form the basic aqueous solution. Such inorganic bases can be selected from the group consisting of hydroxide, oxide, carbonate, and phosphate salts of alkali, alkaline earth metals and mixtures thereof. In some embodiments, such inorganic base is sodium hydroxide, potassium hydroxide, or mixtures thereof. In some embodiments of this invention, the basic aqueous solution is an aqueous solution of a quaternary ammonium hydroxide of the formula NR OH wherein each R is independently hydrogen, a Ci to Ci₆ alkyl group, aralkyl group, or substituted alkyl group, provided that not all R are hydrogens. Examples of NR OH compounds useful in this invention are tetra-n-butylammonium hydroxide, tetra-n- propylammonium hydroxide, tetraethylammonium hydroxide,

tetramethylammonium hydroxide, benzyltrimethylammonium hydroxide, hexadecyltrimethyammonium hydroxide, and choline hydroxide.

Optionally, hydromonochlorofluorobutane or

hydromonochlorofluoropentane is contacted with the basic aqueous solution in the presence of an organic solvent. In some embodiments of this invention, the organic solvent is selected from the group consisting of benzene and its derivatives, alcohols (e.g., methanol, ethanol, propanol, isopropanol, et al.), alkyl and aryl halides, alkyl and aryl nitriles, alkyl, alkoxy and aryl ethers, amides, ketones, sulfoxides, phosphate esters and mixtures thereof. Optionally, hydromonochlorofluorobutane or

hydromonochlorofluoropentane is contacted with the basic aqueous solution in the presence of a phase transfer catalyst. As used herein, the term "phase transfer catalyst" is intended to mean a substance that facilitates the transfer of ionic compounds into an organic phase from an aqueous phase or from a solid phase. A phase transfer catalyst facilitates the reaction between water-soluble and water-insoluble reaction

components. In some embodiments of this invention, the phase transfer catalyst is selected from the group consisting of crown ethers, onium salts, cryptands, polyalkylene glycols, and mixtures and derivatives thereof. The phase transfer catalyst can be ionic or neutral. In some embodiments of this invention, onium salts include quaternary phosphonium salts and quaternary ammonium salts. Examples of quaternary ammonium salts include tetra-n-butylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltri-n-octylammonium chloride (also known as Aliquat™ 336), dodecyltrimethylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide and triphenylmethylphosphonium chloride.

In some embodiments of this invention, the internal fluorobutene or internal fluoropentene product may be recovered from the product mixture by fractional distillation. Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

EXAMPLES

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention

described in the claims.

Example 1

Example 1 demonstrates that contacting CF3CHCICH2CCI2H with HF in the presence of SbCI₅ catalyst forms CF₃CHCICH₂CF₂H.

A 400ml Hastelloy™ shaker tube was loaded with 42.8g of

CF3CHCICH2CCI2H, 6g of SbCIs and 50g of HF. The shaker tube was heated to 80°C and kept at this temperature for 8 hrs. Then the mixture was quenched with a phosphate buffer solution. The lower layer was separated and analyzed by GC/MS. The analysis indicated the formation of the desired novel hydromonochlorofluorbutane compound

CF3CHCICH2CF2H with 31 % conversion and 61 mole % selectivity. The separated lower layers from several batchs of the reactions were combined and distilled to give pure CF3CHCICH2CF2H with boiling point of 54-56°C.

CF3CHCICH2CF2H was further characterized by mass and NMRs. NMR spectrums are also shown in FIG. 1 and FIG. 2:

MS: 181 , 162, 146, 127, 1 13, 95, 77, 69, 51 .

¹ H NMR (CDCI3): 6.07 ppm 1 H (J^F = 55.6 Hz triplet, J^H = 6.8 Hz, doublet, J^H= 2.5 Hz, doublet); 4.3 ppm 1 H, multiplet; 2.5 ppm 1 H, multiplet; 2.4 ppm 1 H, multiplet.

¹⁹F NMR (CDCI3): -76 ppm 3F (J^H = 6.8 Hz, doublet); -1 19.26 ppm 2F, multiplet.

Example 2

Example 2 demonstrates that contacting CF3CHCICH2CCI2H with HF in the presence of SbCI₅ catalyst forms CF₃CHCICH₂CF₂H. A 240 ml Hastelloy™ shaker tube was loaded with 21 .4g (0.1 mole) of CF3CHCICH2CCI2H, 6g (0.02 mole) of SbCI₅ and 24g (1 .2 mole) of HF. The shaker tube was heated to 120°C and kept at this temperature for 5 hrs. Then the mixture was quenched with a phosphate buffer solution. The lower layer was separated and analyzed by GC/MS. The analysis indicated the formation of the desired novel hydromonochlorofluorbutane compound CF₃CHCICH₂CF₂H with 65 % conversion and 81 mole % selectivity. Example 3

Example 3 demonstrates that contacting CF3CHCICH2CCI2H with HF in the presence of SbF₅ catalyst forms CF₃CHCICH₂CF₂H.

A 400ml Hastelloy™ shaker tube was loaded with 21 .4g of

CF3CHCICH2CCI2H, 2.2g of SbF₅ and 24g of HF. The shaker tube was heated to 80°C and kept at this temperature for 8 hrs. Then the mixture was quenched with a phosphate buffer solution. The lower layer was separated and analyzed by GC/MS. The analysis indicated the formation of the desired novel hydromonochlorofluorbutane compound

CF3CHCICH2CF2H with 10 % conversion and 20 mole % selectivity.

Example 4

Example 4 demonstrates that contacting CF₃CHCICH₂CF₂H with a KOH solution in the presence of Aliquat™ 336 forms CF₃CH=CHCF₂H.

A 250ml three-neck flask was equipped with thermocouple well, addition funnel, and short path distillation. The flask was charged with 30 ml of H₂O, 30 ml of isopropanol, 1 .6g of Aliquat™ 336, and 36.4g (0.2 mole) of CF3CCIHCH2CHF2. The flask was heated to 40-45°C. The receiver for the short path distillation was cooled with dry-ice. A KOH solution (21 g (0.35 mole) of KOH dissolved in 40g of water) was added dropwise to the flask. 28.9g of the product mixture contaning 38.9 % of CF₃CH=CHCF₂H, 42.2 % of CF₃CHCICH₂CF₂H and 15 % of isopropanol was collected in the receiver. The product mixture was distilled to give 7.5g (0.05 mole) of CF₃CH=CHCF₂H with boiling point of 31 .1 -34.6°C, and 13.4g of CF3CHCICH2CF2H. The conversion of the CF₃CHCICH₂CF₂H starting material was 63 %. The yield of the CF₃CH=CHCF₂H product was 40 mole %. CF₃CH=CHCF₂H above with boiling point of 31 .1 -34.6°C was distilled again to give CF₃CH=CHCF₂H with boiling point of 32.6-34.6°C. Analysis indicated that it contained both trans and cis isomers at the ratio of 6.8:1 .

Note that not all of the activities described above in the general description or the examples are required, that a portion of a specific activity may not be required, and that one or more further activities may be performed in addition to those described. Still further, the order in which activities are listed are not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the inventive concept(s) as set forth in the claims below. Accordingly, the specification is to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any feature(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature of any or all the claims.

It is to be appreciated that certain features are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination.

Claims

What is claimed is:

A process comprising contacting a hydrohalobutane selected from the group consisting of CF2HCHCICH2CCI2H, CF3CHCICH2CCI2H, CF₃CHCICH₂CCI₃, CF₃CCIHCHFCCI₂H and CF3CCIHCHFCCI3, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluorobutane.

The process of Claim 1 , further comprising recovering the hydromonochlorofluorobutane from the first product mixture.

The process of Claim 1 wherein the hydrohalobutane is

CF2HCHCICH2CCI2H, and the hydromonochlorofluorobutane is CF2HCHCICH2CF2H.

The process of Claim 1 wherein the hydrohalobutane is

CF3CHCICH2CCI2H, and the hydromonochlorofluorobutane is CF3CHCICH2CHF2.

The process of Claim 1 wherein the hydrohalobutane is

CF3CHCICH2CCI3, and the hydromonochlorofluorobutane is CF3CHCICH2CF3.

The process of Claim 1 wherein the hydrohalobutane is

CF3CCIHCHFCCI₂H, and the hydromonochlorofluorobutane is CF₃CCIHCHFCF₂H.

The process of Claim 1 wherein the hydrohalobutane is

CF3CCIHCHFCCI3, and the hydromonochlorofluorobutane is CF₃CCIHCHFCF₃.

A process comprising contacting a hydrohalopentane selected from the group consisting of CF2HCHCICH2CX2CX3 and

CF3CHCICH2CX2CX3, wherein each X is independently selected from the group consisting of F and CI, and not all X are fluorines, with HF in a reaction zone in the presence of an antimony halide catalyst selected from SbCI₅ and SbF₅ to form a first product mixture comprising a hydromonochlorofluoropentane.

The process of Claim 8, further comprising recovering the hydromonochlorofluoropentane from the first product mixture.

10. The process of Clainn 8 wherein the hydrohalopentane is

CF2HCHCICH2CX2CX3, and the hydromonochlorofluoropentane is CF2HCHCICH2CF2CF3.

1 1 . The process of Clainn 10 wherein the hydrohalopentane is selected from the group consisting of CF2HCHCICH2CCI2CCI3,

CF2HCHCICH2CCIFCCI3, CF2HCHCICH2CCI2CF3,

CF2HCHCICH2CCIFCF3 and CF2HCHCICH2CCI2CCIF2.

12. The process of Claim 8 wherein the hydrohalopentane is

CF3CHCICH2CX2CX3, and the hydromonochlorofluoropentane is CF3CHCICH2CF2CF3.

13. The process of Claim 12 wherein the hydrohalopentane is selected from the group consisting of CF3CHCICH2CCI2CCI3,

CF₃CHCICH₂CCIFCCI₃, CF3CHCICH2CCI2CF3,

CF3CHCICH2CCIFCF3 and CF3CHCICH2CCI2CCIF2.

14. The process of Claim 1 , further comprising dehydrochlorinating the hydromonochlorofluorobutane to form a second product mixture comprising an internal hydrofluorobutene.

15. The process of Claim 14 wherein the hydromonochlorofluorobutane is CF3CHCICH2CHF2, and the internal hydrofluorobutene is

CF₃CH=CHCHF₂.

16. The process of Claim 14 wherein the hydromonochlorofluorobutane is CF3CHCICH2CF3, and the internal hydrofluorobutene is

CF₃CH=CHCF₃.

17. The process of Claim 8, further comprising dehydrochlorinating the hydromonochlorofluoropentane to form a second product mixture comprising an internal hydrofluoropentene.

18. The process of Claim 17 wherein the

hydromonochlorofluoropentane is CF3CHCICH2CF2CF3, and the internal hydrofluoropentene is CF₃CH=CHCF₂CF3.

19. A compound of the formula CF3CHCICH2CHF2.