Processes and intermediates for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene and (E)-1,1,1,4,4,4-hexafluorobut-2-ene

Abstract

To provide a method for preparing 1,1,3-trichloro-4,4,4-trifluorobutane-1-en which is an intermediate product as a key of preparation of (E)-1,1,1,4,4,4-hexafluorobutane-2-en.SOLUTION: There are provided a method for preparing 1,1,3-trichloro-4,4,4-trifluorobutane-1-en in a gas phase which includes (i) a step of heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a chromium catalyst selected from a chromium oxide, a carbon supported chromium oxide, a chromium chloride and a carbon supported chromium chloride, in the absence of a hydrogen fluoride; a method for preparing 1,1,3-trichloro-4,4,4-trifluorobutane-1-en in a liquid phase which includes (ii) a step of heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of an iron chloride (III) catalyst, in the absence of a hydrogen fluoride; and a method for preparing (E)-1,1,1,4,4,4-hexafluorobutane-2-en in a gas phase which includes (iii) a step of heating 1,1,3-trichloro-4,4,4-trifluorobutane-1-en in the presence of a chromium catalyst selected from a chromium oxide, a carbon supported chromium oxide, a chromium chloride and a carbon supported chromium chloride.SELECTED DRAWING: None

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 62 / 594,383, filed December 4, 2017, the entire disclosure of which is incorporated herein by reference.

[0002] FIELD OF THE INVENTION The present invention relates to processes and intermediates for preparing (E)-1,1,1,4,4,4-hexafluoro-2-butene and compositions that may be useful in applications including refrigerants, high temperature heat pumps, organic Rankine cycles, as fire extinguishing / flame suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids. [Background technology]

[0003] Over the past several decades, many industries have been working to find alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide variety of applications, including as aerosol propellants, refrigerants, cleaning agents, blowing 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 abrasives, and displacement drying agents. In the search for alternatives to these versatile compounds, many industries have focused on the use of hydrofluorocarbons (HFCs). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Provisional Patent Application No. 62 / 594,383 Summary of the Invention [Means for solving the problem]

[0005] The present application provides, inter alia, a process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, a key intermediate in the preparation of (E)-1,1,1,4,4,4-hexafluorobut-2-ene. The process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene includes heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a transition metal catalyst to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, and substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0006] The present application further provides a process for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene using the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene described herein.

[0007] The present application further provides compositions prepared according to one or more of the processes described herein.

[0008] The present application further provides for the use of the compositions of the present invention in applications including refrigeration (e.g., as a refrigerant composition), high temperature heat pumps, organic Rankine cycles, fire extinguishing / flame suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0009] 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. Methods and materials for use in the present invention are described herein; other suitable methods and materials known in the art may also be used. The materials, methods, and examples are illustrative only and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated herein by reference in their entirety. In case of conflict, the present specification, including definitions, will control. DETAILED DESCRIPTION OF THE INVENTION

[0010] While HFCs do not contribute to stratospheric ozone depletion, they are of concern because they contribute to the "greenhouse effect," i.e., global warming. Because of their contribution to global warming, HFCs have also come under scrutiny, and their widespread use may be restricted in the future. Therefore, there is a need for compositions that do not contribute to stratospheric ozone depletion and also have a low global warming potential (GWP). Certain hydrofluoroolefins, such as 1,1,1,4,4,4-hexafluoro-2-butene (CF3CH=CHCF3, HFO-1336mzz), achieve both goals. For example, (E)-HFO-1336mzz (i.e., (E)-1,1,1,4,4,4-hexafluoro-2-butene) is useful in many applications (e.g., as a foam expansion agent or refrigerant) due to its low GWP, nonflammability, high efficiency, and thermal stability. This application describes key intermediates useful in the preparation of (E)-1,1,1,4,4,4-hexafluoro-2-butene, processes for preparing the intermediates, and an integrated process for preparing the intermediates.

[0011] definition 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 includes a list of elements is not necessarily limited to those elements and may include other elements not expressly listed or inherent in such process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive "or," not 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 absent), A is false (or absent) and B is true (or present), and both A and B are true (or present).

[0012] Additionally, the use of "a" or "an" is used 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 interpreted to include one or at least one, and the singular also includes the plural unless it is clear that a different meaning is intended.

[0013] As used herein, the term "about" is meant to account for variation due to experimental error (e.g., plus or minus about 10% of the stated value). All measurements reported herein are understood to be modified by the term "about," unless otherwise specified, regardless of whether the term "about" is explicitly used.

[0014] When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of upper and / or lower preferred values, this is to be understood as specifically disclosing all ranges formed from any pairing of any upper range value or preferred upper value and any lower range value or preferred lower value, whether or not the ranges are separately disclosed. When a range of numerical values ​​is described herein, unless otherwise indicated, the range is intended to include its endpoints, and to include all integers and fractions within the range.

[0015] Global warming potential (GWP) is an index used to estimate the relative global warming contribution resulting from the atmospheric emission of one kilogram of a particular greenhouse gas compared to the emission of one kilogram of carbon dioxide. GWP can be calculated for various time horizons and indicates the impact of a given gas over its atmospheric lifetime. GWP over a 100-year time horizon is the commonly referenced value.

[0016] Throughout the definition, the term "C n~m " indicates a range inclusive of the endpoints, and n and m are integers indicating the number of carbon atoms. Examples include C 1~4 , C 1~6 Examples include:

[0017] As used herein, the term "C n~m "Alkyl" refers to a saturated hydrocarbon group having n to m carbons, which may be straight-chained or branched. Examples of alkyl moieties include, but are not limited to, chemical groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl; and higher homologs such as 2-methyl-1-butyl, n-pentyl, 3-pentyl, n-hexyl, 1,2,2-trimethylpropyl, and the like. In some embodiments, alkyl groups have 1 to 6, 1 to 4, 1 to 3, or 1 to 2 carbon atoms.

[0018] As used herein, "halide" refers to fluoride, chloride, bromide, or iodide. In some embodiments, halo is chlorine or bromine.

[0019] As used herein, "tri(C n~m "P(O)O(C alkyl phosphate)" has the formula P(O)O(C n~m alkyl)3 (wherein each C n~m Alkyl refers to a saturated hydrocarbon group that may be linear or branched, having n to m carbon atoms, where each C n~m The alkyl groups may be the same or different. n~m Examples of alkyl) phosphates include, but are not limited to, trimethyl phosphate, triethyl phosphate, tributyl phosphate, dimethyl ethyl phosphate, dimethyl butyl phosphate, butyl ethyl methyl phosphate, and the like.

[0020] As used herein, "alkali metal hydroxide base" refers to a compound of formula MOH, where M is an alkali metal (e.g., sodium, potassium, etc.).

[0021] As used herein, the term "substantially isolated" means that a compound or composition is at least partially or substantially separated from the environment in which the compound or composition was formed or detected. Partial separation can include, for example, a composition enriched in a compound provided herein. Substantial separation can include a composition containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of a compound provided herein. Methods for isolating compounds and compositions are routine in the art.

[0022] As used herein, a "transition metal oxide" refers to a metal oxide having the formula MO ywhere M is a transition metal (e.g., chromium, iron, etc.) and y is the oxidation state of the transition metal. Exemplary transition metal oxides include, but are not limited to, chromium (III) oxide (Cr2O3), iron (II) oxide (FeO), iron (III) oxide (Fe2O3), and the like. The transition metal oxide may optionally be supported on a substrate such as activated carbon, alumina, and fluorinated alumina. Additional transition metal oxide catalysts and support substrates can be found, for example, in U.S. Pat. No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

[0023] As used herein, a "transition metal halide" refers to a compound of the formula MX y X refers to a compound of formula (II) where M is a transition metal (e.g., chromium, iron, etc.), X is a halide (e.g., fluoride, chloride, etc.), and y is the oxidation number of the transition metal. Exemplary transition metal halides include, but are not limited to, iron(III) chloride (FeCl), titanium(IV) chloride (TiCl), and the like. Additional transition metal halides can be found, for example, in U.S. Pat. No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

[0024] As used herein, "absence of HF" means that no flow of HF is present during the reaction, but does not exclude the use of HF to activate the catalyst prior to the reaction.

[0025] The compounds described herein can be asymmetric (e.g., having one or more stereocenters). Unless otherwise specified, all stereoisomers, such as enantiomers and diastereomers, are intended. Cis / trans and / or E / Z geometric isomers of the compounds of the invention are described and may be isolated as a mixture of isomers or as separated isomeric forms.

[0026] [Table 1]

[0027] process The present application provides a process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (e.g., a gas phase process or a liquid phase process). In some embodiments, the process includes heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a metal catalyst (e.g., a first metal catalyst) to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0028] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out in the absence of hydrogen fluoride (HF).

[0029] In some embodiments, the process further comprises substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. In some embodiments, the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is substantially isolated by distillation.

[0030] Exemplary metal catalysts useful in the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene include, but are not limited to, transition metal halides (e.g., Group IVb metal halides, Group Vb metal halides), transition metal oxides (e.g., chromium oxide), Group IIIa metal halides (e.g., aluminum halides such as aluminum chloride or aluminum fluoride), and combinations thereof. In some embodiments, the metal catalyst is selected from the group consisting of antimony halides (e.g., SbCl, SbCl, SbF), tin halides (e.g., SnCl), tantalum halides (e.g., TaCl), titanium halides (e.g., TiCl), niobium halides (e.g., NCl), molybdenum halides (e.g., MoCl), iron halides (e.g., FeCl), chromium halides (e.g., chromium chloride), chromium oxide, aluminum halides (e.g., aluminum chloride or aluminum fluoride), alumina halides (e.g., alumina fluoride), fluorinated chromium halides, fluorinated chromium oxides, fluorinated aluminum halides, fluorinated aluminum oxides, or any combination thereof. Additional metal catalysts can be found, for example, in U.S. Pat. No. 8,461,401, the disclosure of which is incorporated herein by reference in its entirety.

[0031] In some embodiments, the metal catalyst is a transition metal catalyst. In some embodiments, the transition metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst. In some embodiments, the transition metal catalyst is selected from chromium oxide, chromium chloride, and iron(III) chloride. In some embodiments, the transition metal catalyst is supported on a substrate (e.g., carbon).

[0032] In some embodiments, the transition metal oxide catalyst is a transition metal oxide catalyst. In some embodiments, the transition metal oxide catalyst is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium oxide. In some embodiments, the chromium oxide is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium(III) oxide. In some embodiments, the transition metal oxide catalyst is carbon-supported chromium(III) oxide.

[0033] In some embodiments, the transition metal catalyst is a transition metal halide catalyst. In some embodiments, the transition metal halide is supported on a substrate. In some embodiments, the metal halide catalyst is an iron halide catalyst. In some embodiments, the metal halide catalyst is a chromium halide catalyst. In some embodiments, the metal halide catalyst is iron(III) chloride. In some embodiments, the metal halide catalyst is chromium chloride. In some embodiments, the metal halide catalyst is carbon-supported chromium chloride.

[0034] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene includes contacting a metal catalyst with hydrogen fluoride to form an activated metal catalyst (e.g., a partially or fully fluorinated metal catalyst). In some embodiments, the activated metal catalyst is prepared prior to heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of the metal catalyst.

[0035] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene further comprises contacting carbon-supported chromium(III) oxide with hydrogen fluoride to form an activated carbon-supported chromium(III) oxide catalyst prior to heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of the carbon-supported chromium(III) oxide catalyst.

[0036] In some embodiments, the process for preparing the activated metal catalyst is carried out at a temperature of about 30° C. to about 350° C., e.g., about 30° C. to about 300° C., about 30° C. to about 250° C., about 30° C. to about 200° C., about 30° C. to about 100° C., about 100° C. to about 350° C., about 100° C. to about 300° C., about 100° C. to about 250° C., about 100° C. to about 200° C., about 200° C. to about 350° C., about 200° C. to about 300° C., about 200° C. to about 250° C., about 250° C. to about 350° C., about 250° C. to about 300° C., or about 300° C. to about 350° C. In some embodiments, the contacting of the metal catalyst with hydrogen fluoride is carried out at a temperature of about 280° C. to about 320° C.

[0037] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a gas phase process. In some embodiments, the gas phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out in the absence of an additional solvent component.

[0038] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a vapor phase process at a temperature of about 100° C. to about 500° C., e.g., about 100° C. to about 400° C., about 100° C. to about 300° C., about 100° C. to about 200° C., about 200° C. to about 500° C., about 200° C. to about 400° C., about 200° C. to about 300° C., about 300° C. to about 500° C., about 300° C. to about 400° C., or about 400° C. to about 500° C. In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a vapor phase process at a temperature of about 150° C. to about 200° C.

[0039] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a liquid phase process. In some embodiments, the liquid phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out in the absence of an additional solvent component.

[0040] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a liquid phase process at a temperature of about 30° C. to about 200° C., e.g., about 30° C. to about 150° C., about 30° C. to about 120° C., about 30° C. to about 75° C., about 75° C. to about 200° C., about 75° C. to about 150° C., about 75° C. to about 120° C., about 120° C. to about 200° C., about 120° C. to about 150° C., or about 150° C. to about 200° C. In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out as a liquid phase process at a temperature of about 75° C. to about 115° C.

[0041] In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out at a pressure of from about 0 psig to about 200 psig, e.g., from about 0 psig to about 150 psig, from about 0 psig to about 100 psig, from about 0 psig to about 50 psig, from about 50 psig to about 200 psig, from about 50 psig to about 150 psig, from about 50 psig to about 100 psig, from about 100 psig to about 200 psig, from about 100 psig to about 150 psig, or from about 150 psig to about 200 psig. In some embodiments, the process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is carried out at a pressure of from about 0 psig to about 150 psig.

[0042] The present application further provides a process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a base to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. In some embodiments, the process of heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a base is carried out as a liquid phase process. In some embodiments, the process of heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a base is carried out in an aqueous solvent.

[0043] In some embodiments, the process further comprises substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. In some embodiments, the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is substantially isolated by distillation.

[0044] Exemplary bases include, but are not limited to, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, and sodium bicarbonate, each of which may optionally be prepared in water to form an aqueous base mixture or solution. In some embodiments, the base is an aqueous base.

[0045] In some embodiments, the aqueous base is an aqueous alkali metal hydroxide base.

[0046] In some embodiments, the aqueous base is aqueous sodium hydroxide or aqueous potassium hydroxide.

[0047] In some embodiments, the present application provides a vapor phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) contacting carbon-supported chromium(III) oxide with hydrogen fluoride at a temperature of about 280°C to about 320°C to form an activated carbon-supported chromium(III) oxide catalyst; ii) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of an activated carbon supported chromium (III) oxide catalyst at a temperature of about 150°C to about 200°C and a pressure of about 0 psig to 150 psig to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0048] In some embodiments, the vapor phase process further comprises substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0049] In some embodiments, the heating in step ii) of the gas phase process is carried out in the absence of hydrogen fluoride.

[0050] In some embodiments, the present application provides a liquid phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of iron(III) chloride at a temperature of about 75°C to about 115°C to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0051] In some embodiments, the liquid phase process further comprises substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene.

[0052] In some embodiments, the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene prepared according to the processes described herein is substantially isolated in greater than about 75% yield, greater than about 85% yield, greater than about 90% yield, greater than about 95% yield, greater than about 97% yield, greater than about 99% yield, or greater than about 99.5% yield.

[0053] In some embodiments, 1,1,3-trichloro-4,4,4-trifluorobut-1-ene prepared according to the processes described herein is substantially isolated to greater than about 75% purity, greater than about 85% purity, greater than about 90% purity, greater than about 95% purity, greater than about 97% purity, greater than about 99% purity, or greater than about 99.5% purity.

[0054] The present application further provides a process that includes heating 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (e.g., substantially isolated 1,1,3-trichloro-4,4,4-trifluorobut-1-ene prepared according to the processes described herein) in the presence of a metal catalyst (e.g., a second metal catalyst) to form (E)-1,1,1,4,4,4-hexafluorobut-2-ene.

[0055] Exemplary metal catalysts useful in the process for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene include, but are not limited to, metal halides, halide metal oxides, neutral (or zero oxidation state) metals or metal alloys, or bulk or supported activated carbon. Additional exemplary metal catalysts useful for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene can be found, for example, in U.S. Pat. No. 8,461,401 and U.S. Patent Application No. 15 / 124,738, the disclosures of each of which are incorporated herein by reference in their entirety.

[0056] In some embodiments, the metal catalyst (e.g., second metal catalyst) useful in the process for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene is a transition metal catalyst (e.g., second transition metal catalyst). In some embodiments, the transition metal catalyst is a transition metal oxide catalyst. In some embodiments, the transition metal oxide catalyst is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium oxide. In some embodiments, the chromium oxide is supported on a substrate. In some embodiments, the transition metal oxide catalyst is chromium(III) oxide. In some embodiments, the transition metal oxide catalyst is carbon-supported chromium(III) oxide.

[0057] In some embodiments, the 2,4,4,4-tetrachloro-1,1,1-trifluorobutane described herein can be prepared by the addition of a metal catalyst (e.g., a third transition metal catalyst) and a tri(C 1~6It is prepared by a process comprising reacting 3,3,3-trifluoroprop-1-ene with carbon tetrachloride in the presence of a (alkyl) phosphate.

[0058] In some embodiments, the transition metal catalyst useful in the preparation of 2,4,4,4-tetrachloro-1,1,1-trifluorobutane is iron powder.

[0059] In some embodiments, tri(C 1~6 The alkyl phosphate is tributyl phosphate.

[0060] Additional processes and conditions for preparing 2,4,4,4-tetrachloro-1,1,1-trifluorobutane can be found, for example, in U.S. Pat. No. 8,461,401 and U.S. patent application Ser. No. 15 / 124,738, the disclosures of each of which are incorporated herein by reference in their entirety.

[0061] The processes and chemical reactions described herein can be monitored according to any suitable method known in the art. For example, product formation can be monitored by nuclear magnetic resonance spectroscopy (e.g., 1 H or 13 C), infrared spectroscopy, mass spectrometry, or by chromatographic methods such as high performance liquid chromatography (HPLC) or liquid chromatography mass spectrometry (LCMS). One skilled in the art can purify compounds by a variety of methods, including, but not limited to, high performance liquid chromatography (HPLC) or distillation.

[0062] composition The present application further provides compositions prepared according to one or more of the processes described herein. In some embodiments, the compositions of the present invention are substantially isolated.

[0063] In some embodiments, the compositions of the present invention comprise a major component (e.g., (E)-1,1,1,4,4,4-hexafluorobut-2-ene or 2,4,4,4-tetrachloro-1,1,1-trifluorobutane) in combination with one or more minor components (i.e., additional compounds or adjunct components). In some embodiments, the compositions of the present invention are prepared according to one or more of the processes described herein. In some embodiments, the major component of the composition comprises greater than about 50 mole percent, greater than about 75 mole percent, greater than about 85 mole percent, greater than about 90 mole percent, greater than about 95 mole percent, greater than about 97 mole percent, greater than about 99 mole percent, or greater than about 99.5 mole percent of the composition.

[0064] The minor components of the compositions described herein can, for example, improve the solubility of the active ingredient (e.g., the major component of the composition) in the polymer component of the aerosol or foam. Additionally, in refrigerant applications such as use in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), the minor components of the compositions can also improve the solubility of refrigeration lubricants such as mineral oil, alkylbenzenes, synthetic paraffins, synthetic naphthenes, poly(alpha)olefins, polyol esters (POE), polyalkylene glycols (PAG), polyvinyl ethers (PVE), or perfluoropolyethers (PFPE), or mixtures thereof.

[0065] Additionally, the presence of trace compounds in samples of the compositions of the present invention can be used to identify the process by which the compound was manufactured.

[0066] In some embodiments, the present application provides: (E)-1,1,1,4,4,4-hexafluorobut-2-ene, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene A composition comprising:

[0067] In some embodiments, the composition comprises a major component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene in combination with one or more of the following minor components: (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-Chloro-1,1,4,4,4-pentafluorobut-2-ene.

[0068] In some embodiments, the composition comprises a major component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene in combination with the following minor components: (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-Chloro-1,1,4,4,4-pentafluorobut-2-ene.

[0069] In some embodiments, the composition comprises greater than about 90 mole percent (E)-1,1,1,4,4,4-hexafluorobut-2-ene.

[0070] In some embodiments, the composition comprises greater than about 97 mole percent (E)-1,1,1,4,4,4-hexafluorobut-2-ene.

[0071] In some embodiments, the composition comprises greater than about 99 mole percent (E)-1,1,1,4,4,4-hexafluorobut-2-ene.

[0072] In some embodiments, a composition comprising a primary component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene is prepared according to one or more of the processes described herein.

[0073] In some embodiments, the present application provides a composition comprising: (E)-1,1,1,4,4,4-hexafluorobut-2-ene, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene Including, Provided is a composition prepared according to a process comprising heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a metal catalyst to form the composition, wherein the metal catalyst is defined according to the definition provided herein for the process of the invention.

[0074] In some embodiments, the composition comprises a major component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene in combination with one or more of the following minor components: (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene; The composition comprises: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a first metal catalyst to form a first mixture comprising 1,1,3-trichloro-4,4,4-trifluorobut-1-ene; ii) heating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the presence of a second metal catalyst to form the composition; and prepared according to a process comprising: The metal catalyst is defined according to the definition provided herein for the process of the present invention.

[0075] In some embodiments, the composition comprises a major component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene in combination with the following minor components: (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene; The composition comprises: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a first metal catalyst to form a first mixture comprising 1,1,3-trichloro-4,4,4-trifluorobut-1-ene; ii) heating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the presence of a second metal catalyst to form the composition; and prepared according to a process comprising: The metal catalyst is defined according to the definition provided herein for the process of the present invention.

[0076] In some embodiments, the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is substantially isolated prior to the heating in step ii).

[0077] In some embodiments, the composition comprising a major component that is (E)-1,1,1,4,4,4-hexafluorobut-2-ene is substantially isolated.

[0078] In some embodiments, the present application provides: 2,4,4,4-tetrachloro-1,1,1-trifluorobutane, 1,1,1-trichloro-4,4,4-trifluorobutane, and A composition comprising 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane is provided.

[0079] In some embodiments, the composition comprises a major component that is 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in combination with one or more of the following minor components: 1,1,1-trichloro-4,4,4-trifluorobutane, and 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane.

[0080] In some embodiments, the composition comprises a major component that is 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in combination with the following minor components: 1,1,1-trichloro-4,4,4-trifluorobutane, and 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane.

[0081] In some embodiments, the composition comprises greater than about 90 mole percent 2,4,4,4-tetrachloro-1,1,1-trifluorobutane.

[0082] In some embodiments, the composition comprises greater than about 97 mole percent 2,4,4,4-tetrachloro-1,1,1-trifluorobutane.

[0083] In some embodiments, the composition comprises greater than about 99 mole percent 2,4,4,4-tetrachloro-1,1,1-trifluorobutane.

[0084] In some embodiments, a composition comprising a primary component that is 2,4,4,4-tetrachloro-1,1,1-trifluorobutane is prepared according to one or more of the processes described herein.

[0085] In some embodiments, the composition comprises a major component that is 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in combination with the following minor components: 1,1,1-trichloro-4,4,4-trifluorobutane, and 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane; The composition comprises: i) Metal catalysts and tri(C 1~6 reacting 3,3,3-trifluoroprop-1-ene with carbon tetrachloride in the presence of a transition metal catalyst in the presence of a (alkyl) phosphate to form the composition; The metal catalyst and tri(C 1~6 (Alkyl)phosphate is defined according to the definition provided herein for the process of the present invention.

[0086] In some embodiments, the composition comprising a major component that is 2,4,4,4-tetrachloro-1,1,1-trifluorobutane is substantially isolated.

[0087] How to use The compositions provided herein (i.e., compositions of the present invention) may be useful in a wide range of applications, including, for example, use as refrigerants, high temperature heat pumps, use in organic Rankine cycles, fire extinguishing / flame suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.

[0088] In some embodiments, a minor component of the composition containing at least one chlorine atom can improve the solubility of the major component of the composition (e.g., (E)-1,1,1,4,4,4-hexafluorobut-2-ene or 2,4,4,4-tetrachloro-1,1,1-trifluorobutane) in the polymeric component of the aerosol or foam.

[0089] For example, unsaturated fluorocarbons such as (E)-1,1,1,4,4,4-hexafluoro-2-butene exhibit different solubility than other fluorocarbon propellants. This low solubility can make the preparation of single-phase aqueous homogeneous aerosol formulations difficult. The presence of low levels of chlorinated impurities can improve mixing and facilitate the use of the formulation and aerosol product.

[0090] Unsaturated fluorocarbons such as (E)-1,1,1,4,4,4-hexafluorobut-2-ene exhibit different solubility characteristics than other common blowing agents. This low solubility can aid in seeding the growth of small bubbles during the foaming reaction, but can also make compound mixing difficult. The presence of low levels of chlorine-based impurities can improve mixing and foam processing performance without negating the benefits of low HFO solubility. Additionally, chlorine compounds generally have low vapor thermal conductivity, thus providing improved thermal insulation performance for foam insulation products.

[0091] Additionally, for refrigerant applications such as use in air conditioning, heat pumps, refrigeration, and power cycles (e.g., organic Rankine cycles), the minor components of the compositions of the present invention containing at least one chlorine atom may also improve solubility in refrigeration lubricants such as mineral oil, alkyl benzenes, synthetic paraffins, synthetic naphthenes, poly(alpha)olefins, polyol esters (POEs), polyalkylene glycols (PAGs), polyvinyl ethers (PVEs), or perfluoropolyethers (PFPEs), or mixtures thereof.

[0092] Furthermore, the trace components of the composition of the present invention can help improve leak detection. Refrigerant leakage can lead to the loss of refrigerant from the system, which increases operating costs due to the need to replenish the refrigerant, and even a small loss of refrigerant from the system can affect proper operation. Ultimately, refrigerant leakage can lead to excessive environmental pollution. In particular, even low levels of chlorine compounds can improve the detectability of refrigerant at the leak site. Therefore, the system can be repaired or redesigned to prevent refrigerant leakage.

[0093] The concentration of minor components in a composition (e.g., minor components that are chlorinated compounds) must be kept low because higher concentrations of minor components can cause compatibility issues with materials of construction. In aerosols, these compatibility issues can occur with the aerosol container (e.g., can) or with plastic valve components. In foams, these compatibility issues can occur with equipment seals and gaskets. Furthermore, in aerosol products, interactions of higher concentrations of minor components (e.g., minor components that are chlorinated compounds) can cause formulation instability. For example, in foam products, high concentrations of chlorinated compounds can soften the foam, resulting in dimensional instability and poor foam strength.

[0094] The compositions described herein may also be useful as low global warming potential (GWP) heat transfer compositions, refrigerants, power cycle working fluids, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, dispersion media, displacement drying agents, buffing agents, polymerization media, blowing agents for polyolefins and polyurethanes, gas dielectrics, fire extinguishing agents, and fire suppression agents, in liquid or gas form. In some embodiments, the compositions provided herein may be useful as working fluids used to transport heat from a heat source to a heat sink. Such heat transfer compositions may also be useful as refrigerants in cycles where the fluid undergoes a phase change (e.g., changing from liquid to gas and vice versa).

[0095] Examples of heat transfer systems include, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporative coolers, direct expansion coolers, walk-in coolers, heat pumps, mobile refrigerators, mobile air conditioning units, and combinations thereof.

[0096] In some embodiments, the compositions provided herein may be useful in mobile heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices. In some embodiments, the compositions may be useful in stationary heat transfer systems, including refrigeration, air conditioning, or heat pump systems or devices.

[0097] As used herein, a mobile heat transfer system refers to any refrigeration, air conditioning, or heating device incorporated into a transportation unit for road, rail, sea, or air. Additionally, a mobile refrigeration or air conditioning unit includes devices that are independent of any moving carrier and are known as "intermodal" systems. Such intermodal systems include "containers" (multimodal sea / land transport) and "swap bodies" (multimodal road / rail transport).

[0098] As used herein, a stationary heat transfer system is a system that is fixed in place during operation. Stationary heat transfer systems may be associated with or attached to any of a variety of buildings, or may be standalone devices located outdoors, such as soft drink vending machines. These stationary applications may be stationary air conditioning and heat pumps (including, but not limited to, chillers, high temperature heat pumps including transcritical heat pumps (e.g., condenser temperatures above 50°C, above 70°C, above 80°C, above 100°C, above 120°C, above 140°C, above 160°C, above 180°C, or above 200°C), residential, commercial, or industrial air conditioning systems including window, ductless, ducted, and packaged terminals, chillers, and exteriors connected to buildings such as rooftop systems). In stationary cooling applications, the compositions provided herein may be useful in high-, medium-, and / or low-temperature cooling appliances, including commercial, industrial, or residential refrigerators and freezers, ice makers, built-in coolers and freezers, flooded evaporative coolers, direct expansion coolers, walk-in and reach-in coolers and freezers, and combination systems. In some embodiments, the disclosed compositions may be used in supermarket refrigeration systems.

[0099] Thus, in accordance with the present invention, the compositions provided herein may be useful in methods of producing cooling, methods of producing heating, and methods of transferring heat.

[0100] In some embodiments, the present application provides a method of producing cooling, the method comprising evaporating a composition provided herein in the vicinity of an object to be cooled, and then condensing the composition.

[0101] In some embodiments, the present application provides a method of producing heat, the method comprising condensing a composition provided herein in the vicinity of an object to be heated, and then evaporating the composition.

[0102] In some embodiments, the present application provides methods of using the compositions provided herein as heat transfer fluid compositions, hi some embodiments, the methods include conveying the composition from a heat source to a heat sink.

[0103] The compositions provided herein also include, among others, R-123 (i.e., HFC-123, 2,2-dichloro-1,1,1-trifluoroethane), R-11 (i.e., CFC-11, trichlorofluoromethane), R-245fa (i.e., HFC-245fa, 1,1,1,3,3-pentafluoropropane), R-114 (i.e., CFC-114, 1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236f ... They may also be useful as low global warming potential (GWP) replacements for currently used refrigerants, including, but not limited to, R-236a (i.e., HFC-236a, 1,1,1,3,3,3-hexafluoropropane), R-236ea (i.e., HFC-236ea, 1,1,1,2,3,3-hexafluoropropane), and R-124 (i.e., HCFC-124, 2-chloro-1,1,1,2-tetrafluoroethane).

[0104] In some embodiments, the compositions provided herein may be useful as refrigerants, providing cooling performance (i.e., cooling capacity and energy efficiency) at least equivalent to the refrigerant they are seeking to replace. Additionally, the compositions of the present invention may provide heating performance (i.e., heating capacity and energy efficiency) equivalent to the refrigerant they replace.

[0105] In some embodiments, the present application provides a method of recharging a heat transfer system containing a refrigerant and lubricant to be replaced, comprising removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant within the system, and introducing one of the compositions of the present invention into the heat transfer system. In some embodiments, the lubricant in the system is partially replaced (e.g., replacing a portion of a mineral oil lubricant used with HCFC-123 with a POE lubricant).

[0106] In some embodiments, the compositions of the present invention may be used to replenish the refrigerant in a chiller. For example, if the performance of a chiller that uses HCFC-123 is reduced due to a refrigerant leak, the compositions provided herein may be added to restore performance to original specifications.

[0107] The present application further provides a heat exchange system containing any of the compositions provided herein, the system being selected from the group consisting of systems having an air conditioner, a freezer, a refrigerator, a heat pump, a water chiller, a flooded evaporative chiller, a direct expansion chiller, a walk-in cooler, a heat pump, a mobile refrigerator, a mobile air conditioning unit, and combinations thereof. Additionally, the compositions of the present invention may be useful in secondary loop systems in which the compositions function as a primary refrigerant to cool a secondary heat transfer fluid, which in turn cools a remote location.

[0108] A vapor compression refrigeration, air conditioning, or heat pump system includes an evaporator, a compressor, a condenser, and an expansion device. The vapor compression cycle reuses refrigerant in multiple steps, producing a cooling effect in some steps and a heating effect in others. The cycle can be simply described as follows: Liquid refrigerant passes through an expansion device and enters an evaporator, where it boils and removes heat from the environment, forming a vapor at a lower temperature and producing cooling. The low-pressure vapor enters the compressor, where the vapor is compressed, increasing its pressure and temperature. The high-pressure (compressed) vapor refrigerant then enters the condenser, where it condenses and releases its heat to the environment. The refrigerant returns to the expansion device, through which the liquid expands from the higher-pressure level in the condenser to the lower-pressure level in the evaporator, thus repeating the cycle.

[0109] The present application further provides foam expansion agent compositions comprising the compositions of the present invention for use in preparing foams. In some embodiments, the present application provides foamable compositions, including, but not limited to, thermoset (e.g., polyurethane, polyisocyanurate, or phenolic) foam compositions, thermoplastic (e.g., polystyrene, polyethylene, or polypropylene) foam compositions, and methods for preparing foams. In some embodiments, one or more of the present compositions can be included as a foam expansion agent in a foamable composition, which can include one or more additional components that can react and / or mix and expand under conditions suitable to form a foam or cellular structure.

[0110] The present application further provides a method of forming a foam, comprising the steps of: (a) adding a composition of the present invention to a foamable composition; and (b) processing the foamable composition under conditions effective to form a foam.

[0111] The present application further provides the use of the compositions of the present invention as a propellant in a sprayable composition. The present application also provides the sprayable composition of the present invention. The active ingredient to be sprayed along with inert ingredients, solvents, and other materials may be present in the sprayable composition. In some embodiments, the sprayable composition is an aerosol. The compositions of the present invention can be used to formulate various industrial aerosols or other sprayable compositions, such as contact cleaners, dusters, lubricant sprays, mold release sprays, insecticides, and consumer aerosols, such as personal care products (e.g., hairsprays, deodorants, and perfumes), household products (e.g., waxes, polishes, pan sprays, room fresheners, and household insecticides), and automotive products (e.g., cleaners and polishers), as well as pharmaceutical substances, such as antiasthma medications and breath fresheners. Examples include, but are not limited to, metered-dose inhalers (MDIs) for the treatment of asthma and other chronic obstructive pulmonary diseases and for delivery of medications to accessible mucous membranes or intranasal passages.

[0112] The present application further provides a process for producing an aerosol product, comprising adding a composition of the present invention to a formulation in an aerosol container, wherein the composition of the present invention functions as a propellant. The present application also provides a process for producing an aerosol product, comprising adding a composition of the present invention to a barrier aerosol package (e.g., a bag-in-can or piston can), wherein the composition of the present invention is maintained separate from other formulation components in the aerosol container, and wherein the composition of the present invention functions as a propellant. The present application also provides a process for producing an aerosol product, comprising adding only a composition of the present invention to an aerosol package, wherein the composition functions as an active ingredient (e.g., a duster, or a cooling or freezing spray).

[0113] The present application further provides a process for converting heat from a heat source into mechanical energy, comprising heating a working fluid comprising the composition of the present invention and then expanding the heated working fluid, the process comprising heating the working fluid using heat provided from the heat source, and expanding the heated working fluid to generate mechanical energy when the pressure of the working fluid is reduced.

[0114] The processes for converting heat described above may be subcritical, transcritical, or supercritical cycles. In a transcritical cycle, the working fluid is compressed above its critical pressure before heating, and during subsequent expansion, the working fluid pressure is reduced below its critical pressure. In a supercritical cycle, the working fluid is maintained at a pressure above its critical pressure throughout the complete cycle (e.g., compression, heating, expansion, and cooling).

[0115] Heat sources can include, for example, low-pressure steam, industrial waste heat, solar energy, geothermal hot water, low-pressure geothermal steam (primary or secondary configuration), or distributed power generation facilities utilizing fuel cells or prime movers such as turbines, microturbines, or internal combustion engines. One source of low-pressure steam can be a process known as the two-fluid geothermal Rankine cycle. Large amounts of low-pressure steam can be found in many places, such as fossil fuel-powered power plants. Other heat sources include waste heat recovered from the exhaust gases of mobile internal combustion engines (e.g., truck or rail diesel engines or ships), waste heat from the exhaust gases of stationary internal combustion engines (e.g., stationary diesel engine generators), waste heat from fuel cells, heat available in combined heating, cooling, and power generation or district heating and cooling plants, waste heat from biomass-fueled engines, heat from natural gas or methane gas burners or methane-fired boilers or methane fuel cells (e.g., distributed power generation facilities) running on methane from a variety of sources including biogas, landfill gas, and coalbed methane, heat from the burning of bark and lignin in paper / pulp mills, heat from incinerators, heat from low-pressure steam in conventional steam power plants (to drive a "bottoming" Rankine cycle), and geothermal heat.

[0116] In some embodiments, the heat conversion process is carried out using an organic Rankine power cycle. Heat available at relatively low temperatures compared to steam (inorganic) power cycles can be used to generate mechanical power through a Rankine cycle using the working fluids described herein. In some embodiments, the working fluid is compressed before being heated. Compression can be provided by a pump that injects the working fluid into a heat transfer unit (e.g., a heat exchanger or evaporator) that heats the working fluid using heat from a heat source. The heated working fluid is then expanded to reduce its pressure. Mechanical energy is generated during the expansion of the working fluid using an expander. Examples of expanders include, but are not limited to, turbo or dynamic expanders (e.g., turbines) and positive displacement expanders (e.g., screw expanders, scroll expanders, and piston expanders). Examples of expanders also include rotary vane expanders.

[0117] The mechanical power may be used directly (e.g., to drive a compressor) or may be converted to electrical power through the use of a generator. In power cycles that reuse the working fluid, the expanded working fluid is cooled. Cooling may occur in a working fluid cooling unit (e.g., a heat exchanger or a condenser). The cooled working fluid can then be used in repeated cycles (i.e., compression, heating, expansion, etc.). The same pump used for compression may be used to transfer the working fluid from the cooling stage.

[0118] The present application further provides a method for detecting a leak from a container, the method comprising sampling air in the vicinity of the container and detecting at least one additional compound of the compositions provided herein using a means for detecting a leak, wherein the composition of the present invention is contained within the container. The term "in the vicinity of" means within 12 inches of the outer surface of the container. Alternatively, the vicinity may be within 6 inches, within 3 inches, or within 1 inch of the outer surface of the container.

[0119] The container may be any known container or system or device filled with the inventor's composition, including, but not limited to, storage containers, transport containers, aerosol cans, fire suppression systems, refrigeration devices, heat pump devices, heat transfer vessels, and power cycle devices (e.g., organic Rankine cycle systems).

[0120] The means for detecting leaks may be implemented using any known sensor designed to detect leaks, including, but not limited to, electrochemical leak detectors, corona discharge leak detectors, and mass spectrometry leak detectors. [Example]

[0121] The present invention will now be described in more detail by way of specific examples. The following examples are provided for illustrative purposes and are not intended to limit the present invention in any way.

[0122] Example 1. Vapor-phase synthesis of a composition containing E-1336mzz and 1333azd

[0123] [ka]

[0124] Step 1. 1,1,3-Trichloro-4,4,4-trifluorobut-1-ene (343jfd)

[0125] [ka]

[0126] 3,3,3-Trifluoropropene (66 g, 0.68 mol) was added to a mixture of carbon tetrachloride (158 g, 1.0 mol), Fe powder (1.12 g, 0.02 mol), and tributyl phosphate (2.66 g, 0.01 mol) in a 400 mL Hastelloy reactor. The reactor was heated to 110 °C for 3 hours. 217 g of the mixture was transferred to a container and analyzed by GC (100% TFP conversion, selectivity to 343 jfd: 88%). The same reaction was repeated twice, and all three batches of material were combined. Subsequent fractionation yielded 299 g of 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343 jfd) with a purity of 98.5%. Boiling point: 92-94 °C / 140 Torr; 1 H NMR(CDCl3,400MHz)δ 4.52(1H,qdd,J1=J2=6.9Hz,J3=1.8Hz),3.44( 1 H,dd,J1=16.0Hz,J2=1.9Hz),3.26(1H,dd,J1=16.0Hz,J2=7.6Hz). 19 F NMR(CDCl3,376MHz)δ-74.85(3F,d,J=6.9Hz). MS(EI):213(M + -Cl)

[0127] Step 2. (E)-1,1,1,4,4,4-hexafluorobut-2-ene (E-1336mzz) and 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (1333azd)

[0128] [ka]

[0129] An Inconel® pipe (0.5 inch outer diameter, 10 inch length, 0.35 inch wall thickness) was packed with 6 cc of Cr2O3 catalyst (Newport Cr). The catalyst was activated with HF at 300 °C, and the reaction was carried out in the vapor phase at 300 °C. 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (343 jfd) was fed to the reactor at 0.15 mL / h or 0.3 mL / h via a vaporizer controlled at 180 °C, and the HF feed was 8.14 sccm or 17.23 sccm. The contact time was 18 seconds or 9 seconds. The reaction pressure was 0-150 psig (0-1.03 MPa). The reactor effluent was analyzed using an Agilent® 7890GC / 5971MS, showing greater than 85 mole % E-1336mzz selectivity, with a mixture containing 1333azd, 1336mt, 346mdf, 1335lzz, Z-1336mzz, 356mff, and 1326mxz.

[0130] Example 2. Vapor phase synthesis of 1333azd

[0131] [ka]

[0132] An Inconel® pipe (0.5 inch outer diameter, 10 inch length, 0.35 inch wall thickness) was packed with 2 cc of Cr2O3 catalyst (Newport Cr). The catalyst was activated with HF at 300 °C, and the reaction was carried out in the vapor phase at 175 °C. 2,4,4,4-tetrachloro-1,1,1-trifluorobutane (343jfd; Example 1, Step 1) was fed to the reactor at 0.25 mL / h via a vaporizer controlled at 180 °C, with a contact time of 18 seconds. The reaction pressure ranged from 0 to 150 psig (0 to 1.03 MPa). The resulting product was collected in a cylinder, and NMR analysis indicated 100% conversion of 343jfd with a selectivity to 1333azd of greater than 95%. 19 F NMR (470MHz, CDCl3): δ-74.05 (3F,d,3JF-H=6.2Hz). 1 H NMR (500MHz, CDCl3): δ6.06 (1H, CHCl, d, 3JH-H = 9.9Hz), 4.99 (1H, CHCl, dq, 3JH-H = 9.9Hz, 3JH-F = 6.2Hz). MS(EI):212(M + ), 214(M + ).

[0133] Example 2. Solution phase synthesis of 1333azd

[0134] [ka]

[0135] A 250 mL three-neck round-bottom flask was charged with 6 g (0.036 mol) of FeCl3. The flask was placed in a fume hood and equipped with a thermocouple well, a dry ice condenser connected to a water scrubber, and a magnetic stir bar, and 100 mL (155 g, 0.62 mol) of 343 jfd was added to the flask. The reaction mixture was heated to approximately 80°C, at which point visible evolution of HCl was observed. The reaction temperature was slowly increased from 80°C to 110°C over a period of approximately 10 hours. The reaction progress was monitored by GC, and upon reaching >98% conversion of the starting material, the reaction mixture was poured into 500 mL of water, the organic layer separated, washed with water (300 mL), separated, dried over MgSO, filtered, and the crude material (135 g) was distilled to give 105 g (79.5%) of 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (1333azd; boiling point 115.2-115.6 °C) and 5.6 g of a residue containing residual HCFO-1333azd and starting material (major component). The purity of the isolated 1333azd was >99% (NMR and GC).

[0136] Example 3. Synthesis of E-1336mzz

[0137] [ka]

[0138] An Inconel® pipe (0.5 inch outer diameter, 10 inch length, 0.35 inch wall thickness) is packed with 6 cc of Cr2O3 catalyst (Newport Cr). The catalyst is activated with HF at 300°C, and the reaction is carried out in the vapor phase at 275°C. 1,1,3-trichloro-4,4,4-trifluorobut-1-ene (1333azd) is fed to the reactor at 0.14 mL / h or 0.29 mL / h via a vaporizer controlled at 150°C, with an HF feed of 8.14 sccm or 17.23 sccm. The contact time is 18 seconds or 9 seconds. The reaction pressure is 0-150 psig (0-1.03 MPa). The reactor effluent was analyzed online using an Agilent® 7890GC / 5971MS, showing greater than 90 mole % E-1336mzz selectivity, with the remainder of the mixture containing 1333azd, 1336mt, 346mdf, 1335lzz, Z-1336mzz, 356mff, and 1326mxz.

[0139] Other embodiments 1. In some embodiments, the present application provides a process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a metal catalyst to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 2. The process of embodiment 1, wherein the heating is carried out in the absence of HF. 3.(ii) The process of embodiment 1 or 2, comprising the further step of substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 4. The process of any one of embodiments 1 to 3, wherein the metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst. 5. The process of embodiment 4, wherein the transition metal oxide catalyst is selected from chromium oxide, carbon-supported chromium oxide, chromium chloride, and carbon-supported chromium chloride. 6. The process of embodiment 4, wherein the transition metal oxide catalyst is chromium oxide. 7. The process of embodiment 4, wherein the transition metal oxide catalyst is carbon-supported chromium oxide. 8. The process of embodiment 7, further comprising the step of: a) contacting the carbon-supported chromium oxide with hydrogen fluoride to form an activated chromium catalyst prior to reacting in step i). 9. The process of embodiment 8, wherein the contacting in step a) is carried out at a temperature of from about 280°C to about 320°C. 10. The process of any one of embodiments 1 to 9, wherein the reaction of step i) is carried out at a temperature of about 150°C to about 200°C. 11. The process of any one of embodiments 1 to 10, wherein the reaction is carried out at a pressure of from about 0 psig to about 150 psig. 12. The process of any one of embodiments 1 to 11, wherein the process is a gas phase process. 13. The process of embodiment 4, wherein the metal halide catalyst is an iron halide catalyst. 14. The process of embodiment 13, wherein the metal halide catalyst is iron(III) chloride. 15. The process of any one of embodiments 1 to 4, 13, and 14, wherein the reaction of step i) is carried out at a temperature of from about 75°C to about 115°C. 16. The process of any one of embodiments 1-4 and 13-15, wherein the process is a liquid phase process. 17. The process of any one of embodiments 1-16, wherein the process is carried out in the absence of an additional solvent component. 18. The process of any one of embodiments 1-17, wherein the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is substantially isolated by distillation. 19. The process of any one of embodiments 1-18, wherein the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is isolated in greater than about 75% purity. 20. The process of any one of embodiments 1-19, wherein the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene is isolated in greater than about 99% purity. 21. The process according to any one of embodiments 1 to 20, wherein iii) heating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the presence of a second transition metal catalyst to form (E)-1,1,1,4,4,4-hexafluorobut-2-ene. 22. The process of embodiment 21, wherein the second transition metal oxide catalyst is chromium(III) oxide. 23. The 2,4,4,4-tetrachloro-1,1,1-trifluorobutane is reacted with a third transition metal catalyst and tri(C 1~6 23. The process of any one of embodiments 1 to 22, wherein the compound is prepared by a process comprising reacting 3,3,3-trifluoroprop-1-ene with carbon tetrachloride in the presence of a (alkyl)phosphate. 24. The process of embodiment 23, wherein the third transition metal catalyst is iron powder. 25. The bird in question (C 1~6 25. The process of embodiment 23 or 24, wherein the alkyl)phosphate is tributyl phosphate. 26. In some embodiments, the present application further describes a liquid phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of an aqueous base to form 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 27. The process of embodiment 26, further comprising the step of (ii) substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 28. The process of embodiment 26 or 27, wherein the aqueous base is an aqueous hydroxide base. 29. The process of embodiment 26 or 27, wherein the aqueous base is aqueous sodium hydroxide or aqueous potassium hydroxide. 30. The process according to any one of embodiments 26 to 29, wherein iii) heating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the presence of a transition metal catalyst to form (E)-1,1,1,4,4,4-hexafluorobut-2-ene. 31. The process of embodiment 30, wherein the transition metal catalyst is a chromium oxide catalyst. 32. The process of embodiment 30, wherein the transition metal catalyst is chromium(III) oxide. 33. The process of embodiment 30, wherein the transition metal catalyst is carbon-supported chromium(III) oxide. 34. The process of embodiment 33, further comprising, prior to the heating of step iii), contacting the carbon-supported chromium(III) oxide with hydrogen fluoride to form activated carbon-supported chromium(III) oxide. 35. In some embodiments, the present application further describes a vapor phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) contacting chromium(III) oxide with hydrogen fluoride at a temperature of about 280°C to about 320°C to form an activated chromium(III) catalyst; ii) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of an activated chromium (III) oxide catalyst at a temperature of about 150°C to about 200°C and a pressure of about 0 psig to 150 psig to form the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 36. The process of embodiment 35, further comprising substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 37. In some embodiments, the present application further describes a liquid phase process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene, comprising: i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of iron(III) chloride at a temperature of about 75°C to about 115°C to form the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 38. The process of embodiment 37, further comprising substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene. 39. The process of any one of embodiments 35-38, wherein the heating in step ii) is carried out in the absence of hydrogen fluoride. 40. In some embodiments, the present application further provides a composition comprising: (E)-1,1,1,4,4,4-hexafluorobut-2-ene, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene Including, A composition is provided that is prepared according to a process that includes heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a metal catalyst to form the composition. 41. The composition of embodiment 40, wherein the heating is carried out in the presence of hydrogen fluoride. 42. The composition of embodiment 40 or 41, wherein the metal catalyst is a transition metal oxide catalyst or a transition metal halide catalyst. 43. The composition of embodiment 40 or 41, wherein the metal catalyst is carbon-supported chromium oxide. 44. The composition of any one of embodiments 41-43, wherein the process further comprises contacting the carbon-supported chromium oxide with hydrogen fluoride to form an activated chromium catalyst before heating the 2,4,4,4-tetrachloro-1,1,1-trifluorobutane. 45. The composition of any one of embodiments 40-44, wherein the process is a gas phase process. 46. ​​In some embodiments, the present application further provides a composition comprising: (E)-1,1,1,4,4,4-hexafluorobut-2-ene, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene Including, i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a first metal catalyst to form a first mixture comprising 1,1,3-trichloro-4,4,4-trifluorobut-1-ene; ii) heating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the presence of a transition metal catalyst to form the composition; The present invention provides a composition prepared according to a process comprising: 47. The process of embodiment 46, wherein step i) is carried out in the presence of hydrogen fluoride. 48. The process of embodiment 46 or 47, wherein step ii) is carried out in the presence of hydrogen fluoride. 49. The process of embodiment 46, wherein step i) is carried out in the absence of hydrogen fluoride. 50. The process of embodiment 49, wherein step ii) is carried out in the presence of hydrogen fluoride. 51. The composition of any one of embodiments 46-50, wherein the process for preparing the composition further comprises substantially isolating the 1,1,3-trichloro-4,4,4-trifluorobut-1-ene prior to the heating of step ii). 52. The composition of any one of embodiments 46-51, wherein the process for preparing the composition further comprises substantially isolating the composition. 53. The composition of any one of embodiments 46-52, wherein the composition comprises greater than about 99 mole percent (E)-1,1,1,4,4,4-hexafluorobut-2-ene. 54. In some embodiments, the present application further provides a composition comprising: 2,4,4,4-tetrachloro-1,1,1-trifluorobutane, 1,1,1-trichloro-4,4,4-trifluorobutane, and 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane, i) Transition metal catalysts and tri(C 1~6 reacting 3,3,3-trifluoroprop-1-ene with carbon tetrachloride in the presence of a transition metal catalyst in the presence of a (alkyl) phosphate to form the composition; ii) substantially isolating the composition; The present invention provides a composition prepared according to a process comprising: 55. The composition of embodiment 54, wherein the composition comprises greater than about 99 mole percent 2,4,4,4-tetrachloro-1,1,1-trifluorobutane. 56. In some embodiments, the present application further provides a composition comprising: (E)-1,1,1,4,4,4-hexafluorobut-2-ene, (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene, 2-chloro-1,1,1,4,4,4-hexafluorobut-2-ene, 1,1,1,4,4,4-hexafluorobutane, and 1-chloro-1,1,4,4,4-pentafluorobut-2-ene Including, A composition is provided, wherein the composition is prepared according to the processes described herein. 57. In some embodiments, the present application further provides a composition comprising: 2,4,4,4-tetrachloro-1,1,1-trifluorobutane, 1,1,1-trichloro-4,4,4-trifluorobutane, and 1,1,1-trichloro-2-(chloromethyl)-3,3,3-trifluoropropane, A composition is provided, wherein the composition is prepared according to the processes described herein. 58. The composition of any one of embodiments 40-57, wherein the process for preparing the composition further comprises substantially isolating the composition.

[0140] While the present invention has been described in conjunction with its detailed description, it should be understood that the foregoing description is intended to illustrate, but not limit, the scope of the invention, which is defined by the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be understood by those skilled in the art that the present invention may be combined with any one or more of the features described herein with respect to any particular aspect and / or embodiment of the invention, with any other feature of any other aspect and / or embodiment of the invention described herein, modified appropriately to ensure compatibility of the combination. Such combinations are considered to be part of the invention contemplated by this disclosure.

Claims

1. 1. A process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in the vapor phase, comprising: (i) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of a chromium catalyst selected from chromium oxide, chromium oxide on carbon, chromium chloride, and chromium chloride on carbon, in the absence of hydrogen fluoride.

2. 1. A process for preparing 1,1,3-trichloro-4,4,4-trifluorobut-1-ene in a liquid phase, comprising: (ii) heating 2,4,4,4-tetrachloro-1,1,1-trifluorobutane in the presence of an iron(III) chloride catalyst and in the absence of hydrogen fluoride.

3. the chromium catalyst is carbon-supported chromium oxide; and The method comprises:

10. The method of claim 1, further comprising the step of: (a) contacting the carbon-supported chromium oxide with hydrogen fluoride prior to reacting in step (i).

4. 4. The method of claim 3, wherein the contacting of step (a) is carried out at a temperature of from 280°C to 320°C.

5. The method of claim 1, wherein the reaction of step (i) is carried out at a temperature of 150°C to 200°C.

6. 10. The method of claim 1, wherein the reaction of step (i) is carried out at a pressure of from 0 MPa to 1.03 MPa (0 psig to 150 psig).

7. 3. The process of claim 2, wherein the reaction of step (ii) is carried out at a temperature of from 75°C to 115°C.

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