Patent Description:
The fluorocarbon industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for many applications has been the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire extinguishing agents, blowing agents and propellants. These new compounds, such as HFC refrigerants, HFC-134a and HFC-<NUM> 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 a result of the Montreal Protocol.

In addition to ozone depleting concerns, global warming is another environmental concern in many of these applications. Thus, there is a need for compositions that meet both low ozone depletion standards as well as having low global warming potentials (GWPs). Certain hydrofluoroolefin compositions are believed to meet both goals. Thus, there is also a need for economical manufacturing processes that provide these compositions.

(Z)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-Hexafluoro-<NUM>-butene (Z-1336mzz) is a hydrofluoroolefin having use in refrigerants, heat transfer compositions, thermodynamic cycle (e.g. heating or cooling cycle) working fluids, aerosol propellants, foaming agents (blowing agents), solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, foaming agents for polyolefins and polyurethane, gaseous dielectrics, power cycle working fluids, fire extinguishing agents, and fire suppression agents in liquid or gaseous form. The GWP for cis-HFO-1336mzz has been estimated from atmospheric lifetime to be <<NUM> for the <NUM> year time horizon.

<CIT> discloses a liquid phase process for producing halogenated alkane adducts of the formula: CAR<NUM>R<NUM>CBR<NUM>R<NUM>. <CIT>discloses a preparation method of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane.

There is a need in this art for a process that can produce (Z)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-1336mzz) efficiently and economically.

The present invention relates to a process for producing a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (CCl<NUM>CH<NUM>CCl<NUM>CF<NUM>, 333jfa) as described in claim <NUM>. The present disclosure provides processes for the production of hydrofluoroolefin Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-CF<NUM>CH=CHCF<NUM>, Z-1336mzz) and intermediates useful in its production. The processes set forth herein provide cost-effective synthesis routes to Z-1336mzz starting with CF<NUM>CCl<NUM> and CH<NUM>=CCl<NUM> or CCl<NUM> and CF<NUM>Cl=CH<NUM>.

In an embodiment, a process for producing a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (CCl<NUM>CH<NUM>CCl<NUM>CF<NUM>, 333jfa), comprises contacting a halogenated alkane with an olefin in the presence of a mononitrile and a catalyst comprising copper (II) chloride, wherein the halogenated alkane is chosen from <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane (CF<NUM>CCl<NUM>, 113a) and carbon tetrachloride (CCl<NUM>), provided that when the halogenated alkane is <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane, the olefin is vinylidene chloride (CH<NUM>=CCl<NUM>, VDC) and when the halogenated alkane is carbon tetrachloride, the olefin is <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (CF<NUM>CCl=CH<NUM>, 1233xf).

In an embodiment, a process comprises contacting 333jfa, produced as set forth hereinabove, with hydrogen fluoride (HF) in the gas phase or liquid phase, in the presence of a fluorination catalyst under conditions to produce a product mixture comprising <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluorobutane (CF<NUM>CCl<NUM>CH<NUM>CF<NUM>, 336mfa).

In an embodiment, a process comprises contacting 336mfa, produced as set forth hereinabove, with base, and optionally a phase transfer catalyst, to produce a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluorobutyne.

In an embodiment, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne is reacted with hydrogen and a hydrogenation catalyst to produce a product mixture comprising Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-1336mzz).

The present disclosure provides a process for the production of Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene comprising (a) contacting a halogenated alkane with an olefin in the presence of a mononitrile and a catalyst comprising copper (II) chloride, wherein the halogenated alkane is chosen from <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane and carbon tetrachloride, provided that when the halogenated alkane is <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane, the olefin is vinylidene chloride and when the halogenated alkane is carbon tetrachloride, the olefin is <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene to produce a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane; (b) contacting <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane with hydrogen fluoride in the gas phase or liquid phase, in the presence of a fluorination catalyst under conditions to produce a product mixture comprising <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluorobutane; (c) contacting <NUM>,<NUM>-dichloro-<NUM>, <NUM>, <NUM>,<NUM>,<NUM>,<NUM>-hexafluorobutane with base and a phase transfer catalyst to produce a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne; and (d) contacting <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne with hydrogen and a hydrogenation catalyst to produce a product mixture comprising Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene.

In any of the foregoing processes, the desired product may be recovered from the product mixture comprising such desired product.

The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the present disclosure, as defined in the appended claims. Other features and advantages of the processes disclosed herein will be apparent from the following more detailed description of the preferred embodiments, taken in conjunction with the present disclosure.

The transitional phrase "consisting of' excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consists of" appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of" is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s), especially the mode of action to achieve the desired result of any of the processes disclosed herein. The term 'consisting essentially of occupies a middle ground between "comprising" and 'consisting of'.

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 disclosure. 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 disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present disclosure, suitable methods and materials are described below. In case of conflict with any publication, patent application, patent, and other reference mentioned herein, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

Provided are exemplary synthesis processes of preparing compositions (product mixtures) including (Z)-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-1336mzz). Embodiments of the present disclosure include synthesis routes to <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-1336mzz) starting with the readily available halogenated compounds, CCl<NUM>, CF<NUM>CCl<NUM>, CH<NUM>=CCl<NUM>, CF<NUM>CCl=CH<NUM>.

The processes disclosed herein may be conducted in a reactor suitable for reaction conditions of temperature and pressure and made of a material that is resistant to the reactants and products employed. The reactor may be constructed from materials which are resistant to the corrosive effects of hydrogen fluoride such as stainless steel, Hastelloy®, Inconel®, Monel®, gold or gold-lined or quartz. The reactions may be conducted batchwise, continuous, semi-continuous or combinations thereof. Suitable reactors include batch reactor vessels and tubular reactors.

By "recover" it is meant to sufficiently isolate the desired product to make it available for its intended use, either as a starting material for a subsequent reaction step or, in the case of recovering Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene, useful, for example, as or in a composition as a refrigerant or foam expansion agent or solvent or fire extinguishant or electronic gas or other use.

The details of the recovery step will depend on the compatibility of the product mixture with the reaction conditions of the subsequent reaction step. For example, if the product is produced in a reaction medium that is different from or incompatible with a subsequent reaction step, then the recovery step may include separation of the desired product from the product mixture including the reaction medium. This separation may occur simultaneously with the contacting step when the desired product is volatile under the reaction conditions. The volatilization of the desired product can constitute the isolation and thereby the recovery of the desired product. If the volatilized product includes undesired components, the desired product may be separated, by selective distillation, for example.

The steps for recovering the desired product from the product mixture, preferably comprise separating the desired product from catalyst or other component(s) of the product mixture used to produce the desired product or produced in the process.

The present disclosure provides, inter alia, processes to produce Z-1336mzz, and intermediates for producing Z-1336mzz. Such process uses low cost, readily available starting materials such as <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane and carbon tetrachloride.

Production of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane CCl<NUM>CH<NUM>CCl<NUM>CF<NUM> 333jfa).

In an embodiment for producing <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (CF<NUM>CCl<NUM>CH<NUM>CCl<NUM>, 333jfa), <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane (CF<NUM>CCl<NUM>, 113a) is charged to a reactor, heated, and contacted with vinylidene chloride (CH<NUM>=CCl<NUM>, VDC), in the presence of a catalyst comprising copper (II) chloride and a mononitrile, at a temperature and pressure sufficient to form <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane, as shown in Scheme (1A).

In an alternate embodiment for producing <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane, carbon tetrachloride (CCl<NUM>) is charged to a reactor, heated, and contacted with <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (CF<NUM>CCl=CH<NUM>, 1233xf), in the presence of a catalyst comprising copper (II) chloride and a mononitrile, at a temperature and pressure sufficient to form <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane, as shown in Scheme (1B).

In some embodiments, the above additions of a halogenated alkane to an olefin may be performed at a temperature of <NUM> to <NUM>. In some embodiments the temperature is <NUM> to <NUM>. In some embodiments, the reaction is performed as a batch reaction and reaction time may be up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, up to <NUM> hours, less than <NUM> hours, less than <NUM> hours, less than <NUM> hours, less than <NUM> hours, and combinations thereof.

In some embodiments, the reaction may be performed at a reactor pressure of <NUM> pound per square inch gauge (psig) to <NUM> pounds per square inch gauge (psig) (<NUM> to <NUM> kPa).

The mononitrile may be chosen from acetonitrile, propionitrile, butyronitrile. In some embodiments, the mononitrile is propionitrile. The molar ratio of mononitrile to the Cu(II) catalyst is at least <NUM> and no more than <NUM>. This ratio may be between <NUM> and <NUM> or between <NUM> and <NUM> or between <NUM> and <NUM>.

The process to produce 333jfa may further comprise recovering 333jfa from the product mixture prior to use of the recovered 333jfa as a starting material in a process to produce HCFC-336mfa, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne and HFO-Z-1336mzz, for example, as set forth herein. Processes for recovering 333jfa from the product mixture may include one or any combination of purification techniques, such as distillation, that are known in the art. By "recovering" 333jfa from the product mixture, a product comprising at least <NUM>% or at least <NUM>% or at least <NUM>% 333jfa is produced.

In an embodiment, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (333jfa) undergoes a fluorination reaction. In this embodiment, <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane is contacted with hydrogen fluoride (HF) in the presence of a fluorination catalyst at a temperature and pressure sufficient to form a product comprising <NUM>,<NUM>-dichloro-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluorobutane, as shown in Scheme (<NUM>).

The reaction with HF may be carried out in the gas phase or the liquid phase. A liquid medium may be added to the liquid phase reaction. An example of a liquid medium is the 333jfa reactant itself. The gas phase or liquid phase reaction includes a fluorination catalyst.

The fluorination reaction may be conducted in a reaction zone comprising any reaction vessel of appropriate size for the scale for the reaction. In some embodiments, the reaction zone comprises a reaction vessel comprised of materials which are resistant to corrosion. In some embodiments, these materials comprise alloys, such as nickel-based alloys such as Hastelloy®, nickel-chromium alloys commercially available from Special Metals Corp. under the trademark Inconel® (hereinafter "Inconel®") or nickel-copper alloys commercially available from Special Metals Corp. (New Hartford, New York) under the trademark Monel®, or vessels having fluoropolymers linings. In other embodiments, the reaction vessel may be made of other materials of construction including stainless steels, in particular of the austenitic type, and copper-clad steel.

In a catalyzed gas phase fluorination process, the fluorination catalyst may be chosen from carbon; graphite; alumina; fluorinated alumina; aluminum fluoride; alumina supported on carbon; aluminum fluoride supported on carbon; fluorinated alumina supported on carbon; magnesium fluoride supported on aluminum fluoride; metals (including elemental metals, metal oxides, metal halides, and/or other metal salts); metals supported on aluminum fluoride; metals supported on fluorinated alumina; metals supported on alumina; and metals supported on carbon; mixtures of metals.

Suitable metals for use in gas phase fluorination catalysts (optionally supported on alumina, aluminum fluoride, fluorinated alumina, or carbon) include chromium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, manganese, rhenium, scandium, yttrium, lanthanum, titanium, zirconium, and hafnium, copper, silver, gold, zinc, and/or metals having an atomic number of <NUM> through <NUM> (i.e., the lanthanide metals). Preferably when used on a support, the total metal content of the catalyst will be from <NUM> to <NUM> percent by weight based on the total weight of the catalyst; typically from <NUM> to <NUM> percent by weight based on the total weight of the catalyst.

Useful fluorination catalysts for the gas phase process include chromium-based catalysts, such as chromium oxyfluoride or chromium oxide, which catalyst may either be unsupported, or supported on a support such as activated carbon, graphite, fluorinated graphite, or fluorinated alumina. The chromium catalyst may either be used alone, or in the presence of a co-catalyst selected from nickel, cobalt, manganese or zinc salt. In some embodiments, a chromium catalyst is high surface area chromium oxide, or chromium/nickel on fluoride alumina (Cr/Ni/AlF<NUM>), the production of which is reported in European Patent <CIT>.

Chromium oxyfluoride catalysts may be made by processes known to those skilled in the art, such as, for example by treating Cr<NUM>O<NUM> (chromium oxide) with HF, CCl<NUM>F or hydrofluorocarbons, as disclosed in <CIT>.

Chromium catalysts are preferably activated before use, for example, as disclosed in <CIT>.

In a gas phase fluorination process, the molar ratio of HF to 333jfa in some embodiments may be from <NUM> to <NUM>. In other embodiments, the molar ratio of HF to 333jfa is from <NUM> to <NUM>. HF may be added in an amount of <NUM> to <NUM> moles per mole of 333jfa.

In some embodiments, the gas phase fluorination process is performed at an elevated temperature, for example at a temperature in the range of <NUM> to <NUM> or from <NUM> to <NUM>. In some embodiments, the temperature is in the range of <NUM> to <NUM>.

In some embodiments, the gas phase fluorination process is performed at a pressure in the range of <NUM> to <NUM> psi (<NUM> to <NUM> MPa). In some embodiments, the reaction is performed at substantially atmospheric pressure.

In some embodiments, contact time for the gas phase fluorination process may be from <NUM> second to <NUM> seconds. In some embodiments, contact time for the gas phase fluorination process may be from <NUM> to <NUM> seconds or <NUM> seconds to <NUM> seconds. In other embodiments, contact time for the gas phase fluorination process may be from <NUM> to <NUM> seconds.

The gas phase fluorination reaction may further comprise recovering 336mfa from the product mixture to reduce the other components of the product mixture. Processes for recovering 336mfa may include one or any combination of purification techniques, such as distillation, that are known in the art. By "recovering" 336mfa from the product mixture, a product comprising at least <NUM>% or at least <NUM> or at least <NUM>% 336mfa is produced.

In a catalyzed liquid phase fluorination process, the fluorination catalyst may include Lewis acid catalyst such as metal halides. The halide may be chosen from fluoride, chloride, bromide. The metal halide may be a transition metal halide or other metal halide. Transition metal chlorides include halides of titanium, tantalum, niobium, tin, tungsten and antimony. Other suitable metal halide catalysts include boron trifluoride.

In some embodiments, the fluorination catalyst is chosen from SbF<NUM>, SbCl<NUM>, SbCl<NUM>, SnCl<NUM>, TaCl<NUM>, TiCl<NUM>, NbCls, MoCl<NUM>, WCl<NUM>, antimony (V) chlorofluorides, and combinations thereof. In some embodiments, the metal halide is SbF<NUM>. In some embodiments, the metal halide is TaCl<NUM>. In some embodiments, the metal halide is antimony (V) chlorofluorides. In one embodiment, the catalyst includes tantalum pentachloride, antimony pentachloride, or antimony pentafluoride.

In a liquid phase fluorination process, the hydrogen fluoride is present at a molar ratio of HF to 333jfa of between <NUM>:<NUM> to <NUM>:<NUM>. In one embodiment, the hydrogen fluoride is present at a molar ratio of HF to 333jfa of about <NUM>:<NUM>.

In some embodiments, the liquid phase fluorination process is performed at a temperature of between <NUM> and <NUM>. In some embodiments, the temperature may be greater than <NUM>. In other embodiments, the temperature may be less than <NUM>.

In some embodiments, the liquid phase fluorination reaction is performed at a pressure in the range of <NUM> to <NUM> psi (<NUM> to <NUM> MPa). In some embodiments, the reaction is performed at substantially atmospheric pressure.

In some embodiments, the contact time of a liquid phase fluorination reaction is from <NUM> minute to <NUM> hours or from <NUM> minutes to <NUM> hours or from <NUM> hour to <NUM> hours.

The desired product HCFC-336mfa may be recovered from the reactor when the process is carried out in a liquid medium by purging unreacted chlorine, distilling off unreacted 333jfa, and filtering off the catalyst. When performed in the liquid phase, the catalyst may be filtered off if present in sufficiently high concentration that catalyst precipitates from product mixture prior to or during or after distillation. Alternatively, the catalyst may remain in the distillation heel. In some embodiments, the product mixture from the fluorination reaction may undergo recovery and purification steps. Such steps may include washing with water, drying, and distillation.

The product produced in a gas phase or liquid phase fluorination process may comprise CF<NUM>CCl<NUM>CH<NUM>CF<NUM> (336mfa) and additional compounds chosen from CF<NUM>CCl<NUM>CH<NUM>CFCl<NUM>, CHF<NUM>CH<NUM>CCl<NUM>CF<NUM> and mixtures thereof.

The present disclosure further provides a process comprising contacting HCFC-336mfa with base to produce a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne (CF<NUM>C≡CCF<NUM>) in a dehydrochlorination reaction, as shown in Scheme (<NUM>). The base is preferably a basic aqueous medium. This reaction step is preferably performed in the presence of a phase transfer catalyst.

The base is a basic aqueous medium comprising a solution of an alkali metal hydroxide or alkali metal halide salt or other base in water. The base may be chosen from hydroxide, oxide, carbonate, or phosphate salts of alkali, alkaline earth metals and mixtures thereof. In some embodiments, the base is chosen from lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate, sodium phosphate, potassium phosphate, and mixtures thereof.

In some embodiments the basic aqueous solution has a pH of over <NUM>. In some embodiments, the basic aqueous solution has a pH of over <NUM>. In some embodiments, the basic aqueous solution has a pH of <NUM>-<NUM>. In some embodiments, the basic aqueous solution contains small amounts of organic liquids which may be miscible or immiscible with water. In some embodiments, the liquid in the basic aqueous solution is at least <NUM>% water. In some embodiments the water is tap water; in other embodiments the water is deionized or distilled.

This reaction step is preferably performed in the presence of a phase transfer catalyst. As used herein, phase transfer catalyst is intended to mean a substance that facilitates the transfer of ionic compounds into an organic phase from an aqueous phase. In this step, the organic phase comprises the HCFC-336mfa reactant, and the aqueous phase comprises the basic aqueous medium. The phase transfer catalyst facilitates the reaction of these dissimilar and incompatible components. While various phase transfer catalysts may function in different ways, their mechanism of action is not determinative of their utility in processes of the present disclosure provided, that the phase transfer catalyst facilitates the dehydrochlorination reaction.

Suitable phase transfer catalysts include quaternary alkylammonium salts. In some embodiments, the catalyst includes tetrabutylammonium bromide or N-methyl-N,N,N-trioctylammonium chloride. In some embodiments, at least one alkyl group of the quaternary alkylammonium salt contains at least <NUM> carbons. An example of quaternary alkylammonium salt wherein three alkyl groups contain at least <NUM> carbon atoms is N-methyl-N,N,N-trioctylammonium chloride, sold under the tradename ALIQUAT® <NUM>, by Alfa Aesar - Fisher Scientific. An example of quaternary alkylammonium salt wherein four alkyl groups contain at least <NUM> carbon atoms includes tetraoctylammonium salt.

The anions of such salts may be halides such as chloride or bromide, hydrogen sulfate, or any other commonly used anion.

Specific quaternary alkylammonium salts include tetraoctylammonium chloride, tetraoctylammonium hydrogen sulfate, tetraoctylammonium bromide, methytrioctylammonium chloride, methyltrioctylammonium bromide, tetradecylammonium chloride, tetradecylammonium bromide, and tetradodecylammonium chloride.

According to one embodiment, a process to produce a product mixture comprising CF<NUM>C≡CCF<NUM> comprises contacting 336mfa with base and a phase transfer catalyst under reaction conditions effective to achieve conversion of 336mfa of at least <NUM>% per hour.

In other embodiments, the alkyl groups of the quaternary alkylammonium salt contain from <NUM> to <NUM> carbon atoms and a non-ionic surfactant is present in the aqueous basic medium. According to such embodiments, the phase transfer catalyst and reaction conditions are effective to achieve conversion of HCFC-336mfa preferably at least <NUM>% per hour. The anions of quaternary alkylammonium salt wherein the alkyl group contains <NUM> to <NUM> carbon atoms may be halides such as chloride or bromide, hydrogen sulfate, or any other commonly used anion. Quaternary alkylammonium salts mentioned above may be used in this embodiment provided their alkyl groups contain <NUM> to <NUM> carbon atoms. Specific additional salts include tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium hydrogen sulfate.

Preferred non-ionic surfactants include ethoxylated nonylphenol or an ethoxylated C12-C15 linear aliphatic alcohol. Useful non-ionic surfactants include Bio-soft® N25-<NUM> and Makon® <NUM>, which are obtainable from Stepan Company, Northfield, IL.

In some embodiments, the quaternary alkylammonium salt is added in an amount of from <NUM> mole percent to <NUM> mole percent of the HCFC-336mfa. In other embodiments, the quaternary alkylammonium salt is added in an amount of from <NUM> mole percent to <NUM> mole percent of the HCFC-336mfa. In yet other embodiments, the quaternary alkylammonium salts is added in an amount of from <NUM> mole percent to <NUM> mole percent of the HCFC-336mfa. In some embodiments, the quaternary alkylammonium salt is added in an amount of from <NUM> mole percent to <NUM> mole percent of the HCFC-336mfa and the weight of non-ionic surfactant added is from <NUM> to <NUM> times the weight of the quaternary alkylammonium salt. These amounts apply to each of the above- mentioned embodiments of the quaternary alkylammonium salt used.

In some embodiments, the reaction mixture is heated to a temperature of <NUM> to <NUM>, preferably conducted at a temperature of from <NUM> to <NUM>, most preferably at <NUM>.

In some embodiments, the reaction is heated for <NUM> hour to <NUM> hours, <NUM> hours to <NUM> hours, <NUM> hours to <NUM> hours, and combinations thereof.

In some embodiments, the reaction is performed at substantially atmospheric pressure.

In some embodiments, the base includes a strong base. In some embodiments, the base includes sodium hydroxide or potassium hydroxide.

In some embodiments, the dehydrochlorination reaction of 336mfa to <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne is performed in the presence of an alkali metal halide salt. The alkali metal may be sodium or potassium. The halide may be chloride or bromide. A preferred alkali metal halide salt is sodium chloride. Without wishing to be bound by any particular theory, it is believed that the alkali metal halide salt stabilizes the phase transfer catalyst. Although the dehydrochlorination reaction itself produces alkali metal chloride, and in particular sodium chloride if sodium hydroxide is used as the base, addition of extra sodium chloride provides a further effect of increasing the yield of <NUM>, <NUM>, <NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne. In some embodiments, the alkali metal halide is added at from <NUM> to <NUM> equivalents per mole of phase transfer catalyst. In other embodiments, the alkali metal halide is added at from <NUM> to <NUM> equivalents per mole of phase transfer catalyst. In yet other embodiments, the alkali metal halide is added at from <NUM> to <NUM> equivalents per mole of phase transfer catalyst. These amounts apply to each of the quaternary alkylammonium salts mentioned above.

The product <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,-hexafluoro-<NUM>-butyne (boiling point -<NUM>) may be recovered from the product mixture by distillation, wherein the butyne vaporizes from the aqueous medium and can then be condensed.

The present disclosure further provides a hydrogenation process comprising contacting <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne with hydrogen at a temperature and pressure sufficient to produce a product mixture comprising Z-<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene (Z-1336mzz), as shown in Scheme (<NUM>). This process is preferably performed in the presence of a hydrogenation catalyst, which is an alkyne-to-alkene catalyst. <CHM>
<CHM>.

In some embodiments, the hydrogenation catalyst is a palladium catalyst, such as a catalyst comprising palladium dispersed on aluminum oxide or titanium silicate, doped with silver and/or a lanthanide. The loading of palladium dispersed on the aluminum oxide or titanium silicate is relatively low. In some embodiments, the palladium loading is from <NUM> ppm to <NUM> ppm. In other embodiments, the palladium loading is from <NUM> ppm to <NUM> ppm. In some embodiments, the palladium catalyst is doped with at least one of silver, cerium or lanthanum. In some embodiments, the mole ratio of cerium or lanthanum to palladium is from <NUM>:<NUM> to <NUM>:<NUM>. In some embodiments the mole ratio of silver to palladium is about <NUM>:<NUM>.

In some embodiments, the hydrogenation catalyst includes Lindlar (<NUM>% Pd on CaCO<NUM> poisoned with lead). The lead compound may be lead acetate, lead oxide, or any other suitable lead compound.

The Lindlar catalyst may be further deactivated or conditioned with quinoline. The amount of palladium on the support is typically about <NUM>% by weight but may be any catalytically effective amount. In some embodiments, the amount of palladium on the support in the Lindlar catalyst is greater than <NUM>% by weight. In yet other embodiments, the amount of palladium on the support may be from <NUM>% by weight to <NUM>% by weight.

In some embodiments, the amount of the catalyst used is from <NUM>% by weight to <NUM>% by weight of the amount of the <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne. In other embodiments, the amount of the catalyst used is from <NUM>% by weight to <NUM>% by weight of the amount of the butyne. In yet other embodiments, the amount of the catalyst used is from <NUM>% to <NUM>% by weight of the amount of the butyne.

In some embodiments, this reaction step is performed in the presence of a solvent. In one such embodiment, the solvent is an alcohol. Typical alcohol solvents include ethanol, i-propanol and n-propanol. In other embodiments, the solvent is a fluorocarbon or hydrofluorocarbon. Typical fluorocarbons or hydrofluorocarbons include <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-decafluoropentane and <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-heptafluorocyclopentane.

In some embodiments, reaction of the <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne with hydrogen is preferably performed with addition of hydrogen in portions, with increases in the pressure of the vessel of no more than about <NUM> psi (<NUM> MPa) with each addition. In other embodiments, the addition of hydrogen is controlled so that the pressure in the vessel increases no more than about <NUM> psi (<NUM> MPa) with each addition. In some embodiments, after enough hydrogen has been consumed in the hydrogenation reaction to convert at least <NUM>% of the butyne to Z-1336mzz, hydrogen may be added in larger increments for the remainder of the reaction. In other embodiments, after enough hydrogen has been consumed in the hydrogenation reaction to convert at least <NUM>% of the butyne to the desired butene, hydrogen may be added in larger increments for the remainder of the reaction. In yet other embodiments, after enough hydrogen has been consumed in the hydrogenation reaction to convert at least <NUM>% of the butyne to desired butene, hydrogen may be added in larger increments for the remainder of the reaction. In some embodiments, the larger increments of hydrogen addition may be <NUM> psi (<NUM> MPa). In other embodiments, the larger increments of hydrogen addition may be <NUM> psi (<NUM> MPa).

In some embodiments, the molar ratio is <NUM> mole of hydrogen to <NUM> mole of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne. In other embodiments, the molar ratio is from <NUM> mole to <NUM> mole, hydrogen to butyne. In yet other embodiments, the amount of hydrogen added is from <NUM> mole of hydrogen to <NUM> moles of butyne. In yet other embodiments, the amount of hydrogen added is from <NUM> moles of hydrogen to <NUM> moles of butyne.

In some embodiments, the hydrogenation is performed at ambient temperature (<NUM> to <NUM>). In other embodiments, the hydrogenation is performed at above ambient temperature. In yet other embodiments, the hydrogenation is performed at below ambient temperature. In yet other embodiments, the hydrogenation is performed at a temperature of below about <NUM>.

In some embodiments, a reaction vessel containing hexafluoro-<NUM>-butyne and catalyst is cooled to about -<NUM> under reduced pressure. The temperature of the reactor may then be allowed to warm to room temperature. Hydrogen gas may then be slowly added to the reaction vessel. In some embodiments, the rate of addition of hydrogen gas is regulated to result in a pressure change within the reaction vessel of less than <NUM> MPa (<NUM> psi), less than <NUM> MPa (<NUM> psi), and/or less than <NUM> MPa (<NUM> psi). The addition of hydrogen may be continued until a slight excess of hydrogen is provided to the reaction vessel.

In an embodiment of a continuous process, a mixture of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne and hydrogen is passed through a reaction zone containing the catalyst. A reaction vessel, e.g., a metal tube, may be used, packed with the catalyst to form the reaction zone. In some embodiments, the molar ratio of hydrogen to the butyne is about <NUM>: <NUM>. In other embodiments of a continuous process, the molar ratio of hydrogen to the butyne is less than <NUM>:<NUM>. In yet other embodiments, the molar ratio of hydrogen to the butyne is about <NUM>: <NUM>.

In some embodiments of a continuous process, the reaction zone is maintained at ambient temperature. In other embodiments of a continuous process, the reaction zone is maintained at a temperature of <NUM>. In yet other embodiments of a continuous process, the reaction zone is maintained at a temperature of about <NUM>.

In some embodiments of a continuous process, the flow rate of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne and hydrogen is maintained so as to provide a residence time in the reaction zone of about <NUM> seconds. In other embodiments of a continuous process, the flow rate of the butyne and hydrogen is maintained so as to provide a residence time in the reaction zone of about <NUM> seconds. In yet other embodiments of a continuous process, the flow rate of butyne and hydrogen is maintained so as to provide a residence time in the reaction zone of about <NUM> seconds.

It will be understood, that contact time in the reaction zone is reduced by increasing the flow rate of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butyne and hydrogen into the reaction zone. As the flow rate is increased this will increase the amount of butyne being hydrogenated per unit time. Since the hydrogenation is exothermic, depending on the length and diameter of the reaction zone, and its ability to dissipate heat, at higher flow rates it may be desirable to provide a source of external cooling to the reaction zone to maintain a desired temperature.

In some embodiments, upon completion of a batch-wise or continuous hydrogenation process, the Z-1336mzz may be recovered through any conventional process, including for example, fractional distillation. In other embodiments, upon completion of a batch-wise or continuous hydrogenation process, the Z-1336mzz is of sufficient purity to not require further purification steps.

The <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-hexafluoro-<NUM>-butene reaction product may be recovered in high yield and high purity by distillation of the reaction mixture. In some embodiments, the yield of the reaction of Scheme <NUM> is greater than <NUM> percent, greater than <NUM> percent, greater than <NUM> percent, and/or greater than <NUM> percent.

The concepts described herein will be further described in the following examples, which do not limit the scope of the present disclosure as described in the claims.

Iron powder, vinylidene chloride, Aliquat® <NUM> and sodium hydroxide are available from Sigma Aldrich, St.

113a <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane (CF<NUM>CCl<NUM>), <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (CF<NUM>CCl=CH<NUM>), hydrogen fluoride and SbCl<NUM> are purchased from Synquest Labs, Inc.

Vinylidene chloride (<NUM>, <NUM> mol) was added to the mixture of 113a (<NUM>, <NUM> mol), Fe powder (<NUM>, <NUM> mol) and triphenyl phosphine (<NUM>, <NUM> mol) in a <NUM> Hastelloy reactor. The reactor was heated up to <NUM> for <NUM> hours. The mixture was transferred to a container and analyzed by GC: <NUM>% GC yield (conversion <NUM>% and selectivity to product <NUM>%).

The mixture of Vinylidene chloride (<NUM>, <NUM> mol) and 113a (<NUM>, <NUM> mol) was heated up to <NUM> for <NUM> hours in the presence of anhydrous copper (II) chloride (<NUM>, <NUM> mol) along with <NUM> of propionitrile in a <NUM> stainless autoclave. The mixture was transferred to a container and analyzed by GC: <NUM>% GC yield (conversion <NUM>%, selectivity to product <NUM>%).

The mixture of <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (<NUM>, <NUM> mol) and CCl4 (<NUM>, <NUM> mol) was heated up to <NUM> for <NUM> hours in the presence of Fe powder (<NUM>, <NUM> mol) and triphenyl phosphine (<NUM>, <NUM> mol) in a <NUM> Hastelloy reactor. The mixture was transferred to a container and analyzed by GC: conversion <NUM>% and selectivity to product is <NUM>%.

The mixture of <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (<NUM>, <NUM> mol) and CCl4 (<NUM>, <NUM> mol) was heated up to 100oC for <NUM> hours in the presence of anhydrous copper (II) chloride (<NUM>, <NUM> mol) in <NUM> of propionitrile in a <NUM> stainless autoclave. The mixture was purified by fractionation and the distilled yield to the product is <NUM>%.

The product CF<NUM>CCl<NUM>CH<NUM>CCl<NUM> was recovered from the product mixtures of Examples <NUM>-<NUM> and has the following properties: boiling point of <NUM>-58oC (<NUM> Pa (<NUM> Hg)); <NUM> NMR (CDCl3): δ ppm <NUM> (CH2, s); 19F NMR (CDCl3): δ ppm -<NUM> (CF3, s); MS (m/z): <NUM> (M + -Cl), <NUM> (M + -Cl -<NUM>).

A mixture of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (<NUM>, <NUM> mol), anhydrous HF (<NUM>, <NUM> mol) and antimony pentachloride (<NUM>, <NUM> mol) was stirred in a PTFE-lined vessel at <NUM>. The reaction mixture was poured into crushed ice. The organic layer was washed with water (two times), dried with MgSO4. Distillation at <NUM>-<NUM> gave <NUM> product (<NUM>% yield). The product was recovered having the following properties: <NUM> NMR (CDCl3): δ ppm <NUM> (q, JHF = <NUM>, CH2); 19F NMR (CDCl3): δ ppm: -<NUM> (t, JFH = <NUM>, 2F, CH2CF3), -<NUM> (s, 3F, CF3).

The mixture of <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (<NUM>, <NUM> mol), anhydrous HF (<NUM>, <NUM> mol) and tantalum pentachloride (<NUM>, <NUM> mol) is stirred at in a PTFE-lined vessel at <NUM>. The reaction mixture is poured into crushed ice. The organic layer is washed with water (two times), dried with MgSO4. Distillation at <NUM>-68oC gives <NUM> product (<NUM>% yield).

An Inconel® pipe (<NUM> (<NUM> inch) OD, <NUM> (<NUM> inch) length, <NUM> (<NUM> inch) wall thickness) is filled with <NUM> cc Newport chrome catalyst. The reactor is heated to the target temperature. CF<NUM>CCl<NUM>CH<NUM>CCl<NUM> is fed via an ISCO pump (<NUM>/hr) and a vaporizer controlled at 170oC. HF/CF3CCl2CH2CCl3 mole ratio is <NUM> and contact time is <NUM> seconds. The reaction is run at about <NUM> MPa (<NUM> psig). The reactor effluent is analyzed online using an Agilent® <NUM> GC/<NUM> to show <NUM>% conversion of the starting material, <NUM>% selectivity to 336mfa and <NUM>% selectivity to 1326mxz (CF3CCl=CHCF3).

NaOH aqueous solution (<NUM>, <NUM> mol) is added to CF<NUM>CCl<NUM>CH<NUM>CF<NUM> (<NUM>, <NUM> mol) and water (<NUM>) in the presence of Aliquat® <NUM> quaternary ammonium salt (<NUM>, <NUM> mol) at room temperature. The reaction temperature is raised to 70oC after the addition, and gas chromatography is used to monitor the reaction. The reaction is completed after <NUM> hours and the hexafluorobutyne is collected in a dry ice trap in greater than <NUM>% yield.

NaOH aqueous solution (<NUM>, <NUM> mol) is added to the 336mfa (<NUM>, <NUM> mol) and water (<NUM>) in the presence of tetrabutylammonium bromide (<NUM>, <NUM> mol) and Makon® <NUM> surfactant (<NUM>) at room temperature. The reaction temperature is raised to 70oC after the addition, and gas chromatography is used to monitor the reaction. The reaction is completed after <NUM> hours and the hexafluorobutyne is collected in a dry ice trap in greater than <NUM>% yield.

<NUM> of Lindlar (<NUM>% Pd on CaCO3 poisoned with lead) catalyst was charged in a <NUM> rocker bomb. <NUM> (<NUM> mol) of hexafluoro-<NUM>-butyne was charged in the rocker. The reactor was cooled to -78oC and evacuated. After the bomb was warmed to room temperature, H2 was added slowly, by increments which did not exceed ΔP=<NUM> psi (<NUM> MPa). A total of <NUM> moles H2 were added to the reactor. A gas chromatographic analysis of the crude product indicated the mixture consisted of CF3C≡CCF3 (<NUM>%), trans-isomer (E)-CF3CH=CHCF3 (boiling point <NUM>. 3oC, MS: <NUM> [MI], <NUM> [M-<NUM>], <NUM> [CF3CH=CH], <NUM> [CF3]; <NUM> NMR: <NUM> ppm (multiplet), 19F NMR: -<NUM> ppm (triplet J=<NUM>). The selectivity of this reaction to the formation of the Z-isomer was <NUM>%. The Z-isomer was recovered by distillation.

Claim 1:
A process for producing a product mixture comprising <NUM>,<NUM>,<NUM>,<NUM>,<NUM>-pentachloro-<NUM>,<NUM>,<NUM>-trifluorobutane (CCl<NUM>CH<NUM>CCl<NUM>CF<NUM>, 333jfa), comprises contacting a halogenated alkane with an olefin in the presence of a mononitrile and a catalyst comprising copper (II) chloride, wherein the halogenated alkane is chosen from <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane (CF<NUM>CCl<NUM>, 113a) and carbon tetrachloride (CCl<NUM>), provided that when the halogenated alkane is <NUM>,<NUM>,<NUM>-trichloro-<NUM>,<NUM>,<NUM>-trifluoroethane, the olefin is vinylidene chloride (CH<NUM>=CCl<NUM>, VDC) and when the halogenated alkane is carbon tetrachloride, the olefin is <NUM>-chloro-<NUM>,<NUM>,<NUM>-trifluoropropene (CF<NUM>CCl=CH<NUM>, 1233xf).