Method for preparing HFO-1252ZC from HCFO-1233XF and HBFO-1233XFB

Abstract

Provided herein is a process for the preparation of 1, 1-difluoropropene (HFO-1252zc, CF2 = CHCH3) by means of at least one intermediate selected from the group consisting of 2-chloro-1, 1, 1-trifluoropropane (HCFC-253db), 2-bromo-3, 3, 3-trifluoropropene (HBFO-1233xfB), and 2-bromo-1, 1, 1-trifluoropropane (HBFC-253dbB).

Description

Cross-references to related applications

[0001] This patent application claims the benefit of priority to U.S. Provisional Application 63 / 527,160, filed July 17, 2023, and U.S. Provisional Application 63 / 565,029, filed March 14, 2024, the disclosure of each of which is incorporated herein by reference in its entirety. Technical Field

[0002] This invention relates to methods, compositions, and uses for preparing difluoroolefins. Background Technology

[0003] For decades, numerous industries have been searching for alternatives to ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). CFCs and HCFCs have been used in a wide range of applications, including as aerosol propellants, refrigerants, cleaning agents, expanders for thermoplastic and thermosetting foams, heat transfer media, gaseous dielectrics, fire extinguishing and flame retardants, power circulation working fluids, polymerization media, particulate removal fluids, carrier fluids, polishing abrasives, and displacement desiccants. In the search for replacements for these versatile compounds, many industries have shifted to hydrofluorocarbons (HFCs).

[0004] Although HFCs do not cause stratospheric ozone depletion, they contribute to the "greenhouse effect," or global warming. Because of this contribution to global warming, HFCs have received close attention, and their widespread use may be limited in the future.

[0005] The regulatory environment is constantly evolving, and the characteristics taken into consideration are no longer limited to ozone depletion potential (ODP) and global warming potential (GWP). More specifically, there is a need for refrigerant compositions that not only meet low ODP standards and have low GWP, but also exhibit low or no flammability, provide excellent performance in a wide range of applications, and meet the standards of evolving regulations.

[0006] There is a need in the art for novel refrigerants that meet evolving regulations and provide heat transfer and refrigerant properties that meet or exceed the efficiency of conventional refrigerants.

[0007] Some fluoropropylenes (such as 1,1-difluoropropylene (HFO-1252zc)) are potential new refrigerants. Effective and efficient methods for preparing 1,1-difluoropropylene (HFO-1252zc) and its intermediates and compositions are still needed. Summary of the Invention

[0008] In some embodiments, the present invention relates to a method for preparing 1,1-difluoropropene (HFO-1252zc, CF2=CHCH3) from at least one intermediate selected from: 2-chloro-1,1,1-trifluoropropane (HCFC-253db, CF3CHClCH3); 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB, CF3CHBrCH3); 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf, CF3CCl=CH2) or 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB, CF3CBr=CH2).

[0009] In some embodiments, the present invention relates to providing fluoroolefins, converting fluoroolefins into haloalkanes having halogens on adjacent carbon atoms, and dehalogenating adjacent carbon atoms to form HFO-1252zc.

[0010] In some embodiments, the present invention relates to a method for preparing HFO-1252zc from a precursor of the formula CF3CX=CH2, wherein X is selected from Cl, Br or I.

[0011] In some embodiments, the present invention relates to a method for preparing a compound of the formula CF3CHXCH3 by contacting a compound of the formula CF3CX=CH2 with hydrogen in the presence of a catalyst, wherein X is selected from Cl, Br or I.

[0012] In some embodiments, the present invention relates to a method for preparing HFO-1252zc by reacting a compound of the formula CF3CHXCH3 with a metal (such as Zn or Mg), or by reacting a compound of the formula CF3CHXCH3 with hydrogen in the presence of a catalyst, wherein X is selected from Cl, Br or I.

[0013] In some embodiments, the method includes two steps to convert a precursor or starting material into HFO-1252zc. In some embodiments, the first step includes converting the precursor CF3CX=CH2 into an intermediate compound of the formula CF3CHXCH3 by reacting it with H2 in the presence of a catalyst, wherein X is selected from Cl, Br, or I. In some embodiments, the second step includes converting the intermediate CF3CHXCH3 into HFO-1252zc by reacting it with a metal (such as Zn or Mg) or by reacting it with H2 in the presence of a catalyst.

[0014] In some embodiments, the CF3CX=CH2 compound is HCFO-1233xf, and the CF3CHXCH3 compound is HCFC-253db, as shown in the following reaction:

[0015] In some embodiments, the present invention relates to a method and composition for preparing HCFC-253db from HCFO-1233xf.

[0016] In some embodiments, the CF3CX=CH2 compound is HBFO-1233xfB, and the CF3CHXCH3 compound is HBFC-253dbB, as shown in the following reaction:

[0017] In some embodiments, the present invention relates to a method and composition for preparing HBFC-253dbB from HBFO-1233xfB.

[0018] In some embodiments, the CF3CHXCH3 compound converted from HFO-1252zc using hydrogen is HCFC-253db, as shown in the following reaction:

[0019] In some embodiments, the CF3CHXCH3 compound converted by metal to HFO-1252zc is HCFC-253db, as shown in the following reaction (where M represents a metal preferably selected from Zn, Mg, or combinations thereof):

[0020] In some embodiments, the present invention relates to a method for preparing HFO-1252zc from HCFC-253db and compositions thereof.

[0021] In some embodiments, the CF3CHXCH3 compound converted from HFO-1252zc using hydrogen is HBFC-253dbB, as shown in the following reaction:

[0022] In some embodiments, the CF3CHXCH3 compound converted by metal to HFO-1252zc is HBFC-253db, as shown in the following reaction (where M represents a metal preferably selected from Zn, Mg, or combinations thereof):

[0023] In some embodiments, the present invention relates to a method for preparing HFO-1252zc from HBFC-253dbB and a composition thereof.

[0024] In some embodiments, the present invention relates to a method and compositions thereof for preparing HFO-1252zc from HCFO-1233xf or HBFO-1233xfB.

[0025] In some embodiments, the present invention relates to a method and compositions thereof for preparing HFO-1252zc from HCFO-1233xf or HBFO-1233xfB and HCFC-253db or HBFC-253dbB.

[0026] One embodiment of the present invention disclosed herein relates to a method for converting HCFO-1233xf via the intermediate HCFC-253db to form HFO-1252zc.

[0027] One embodiment of the present invention disclosed herein relates to a method for converting HBFO-1233xfB via intermediate HBFC-253dbB to form HFO-1252zc.

[0028] In some embodiments disclosed herein, HFO-1252zc is prepared according to any of the following two-step reaction schemes:

[0029] Where M is a metal, and more specifically a reactive metal, such as zinc, magnesium, or a combination thereof.

[0030] Some embodiments involve compositions comprising HCFO-1233xf, HBFO-1233xfB, 1,1,1-trifluoropropane (HFC-263fb, CF3CH2CH3), HCFC-253db, and HBFC-253dbB.

[0031] Some embodiments involve compositions comprising up to about 10 mol% of HFC-263fb and up to about 99.5 mol% of HCFC-253db based on 100% of the total composition.

[0032] Some embodiments involve compositions comprising HCFO-1233xf, up to about 10 mol% of HFC-263fb and up to about 99.5 mol% of HCFC-253db based on a total composition of 100 mol%, wherein the term “about” is defined as 10 mol% of an indicated value selected from one of the following: ±1%, ±2%, ±3%, ±4%, ±5%, ±6%, ±7%, ±8%, ±9%, or ±10%.

[0033] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of, one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), and 1-fluoropropylene (HFO-1261ze). Pentafluorobutene isomers (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0034] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO). -1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc is present in the composition.

[0035] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-13). 45) 2-Butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HFC-252dc), wherein at least HFO-1252zc and HFO-1243zf are present.

[0036] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of at least two or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-1 345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc and HFO-1261ze are present.

[0037] Some embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of at least two or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO- 1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc and HFC-263fb are present.

[0038] Some embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of the following: HCFC-253db, HFC-263fb, HCFO-1233xf, and HFO-1252zc.

[0039] Some embodiments disclosed herein relate to compositions comprising, substantially comprising, or consisting of the following: HCFC-253db, HFC-263fb, HFO-1243zf, HCFO-1233xf, HFO-1252zc, HFO-1261ze, HBFC-253dbB, and HBFO-1233xfB.

[0040] Some embodiments disclosed herein relate to compositions containing, substantially consisting of, or composed of, greater than 0% and at most about 10%, about 20%, about 30%, or about 40% or higher of HFO-1252zc based on the total amount of the composition, wherein the term “about” is defined as an indicated value and ±1%, ±2%, ±3, ±4%, ±5%, ±6, ±7%, ±8%, ±9, or ±10%.

[0041] Some embodiments disclosed herein relate to compositions comprising or consisting substantially of HFO-1252zc, based on the total amount of the composition, comprising or consisting of about 10 mol% to about 50 mol%, about 10 mol% to about 40 mol%, about 10 mol% to about 30 mol%, or about 10 mol% to about 20 mol%, wherein the term “about” is defined as an indicated value and ±1%, ±2%, ±3, ±4%, ±5%, ±6, ±7%, ±8%, ±9, or ±10%.

[0042] One embodiment disclosed herein relates to a system comprising a first reactor and an optional second reactor, which are configured independently. The first reactor and / or the second reactor can operate in a gas phase and / or a liquid phase consistent with the reactions disclosed herein.

[0043] 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 pertains. In case of any conflict, this specification and the definitions included herein shall prevail. Although methods and materials similar to or equivalent to those described herein may be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. Furthermore, materials, methods, and examples are illustrative only and are not intended to be limiting. Attached Figure Description

[0044] Figure 1 A first reactor and an optional second reactor arranged in series are depicted.

[0045] Figure 2 The NMR analysis during the reaction at 60 °C is shown. Detailed Implementation

[0046] The foregoing overview and the following detailed description are exemplary and illustrative only, and do not constitute a limitation on the invention as defined in the appended claims. Further features and benefits of any one or more embodiments will become apparent from the following detailed description and claims.

[0047] Before addressing the details of the implementation schemes described herein, certain terms are defined or clarified as follows.

[0048] As used herein, the term “about” means indicated values ​​and ±1%, ±2%, ±3%, ±4%, ±5%, ±6%, ±7%, ±8%, ±9%, or ±10%.

[0049] As used herein, the term "hydrogen (halogenated) alkane" means a molecule containing hydrogen, carbon, and optionally fluorine and / or chlorine and / or bromine and / or iodine, and without a carbon-carbon double bond (halogenated fluorine, chlorine, bromine, iodine). Examples are described throughout this specification. The term hydrogen (halogenated) alkane includes alkanes and halogenated alkanes.

[0050] As used herein, the term “dehydrohalogenation” means the loss of HX from a hydrohalogenated alkane, where X = F, Cl, Br, I, and H and X are located on adjacent carbons in the hydrohalogenated alkane. For example, as used herein, the term “dehydrofluorination” (“dehydrofluorinating” or “dehydrofluorinated”) means the process during which hydrogen and fluorine are removed from adjacent carbons in the molecule; and as used herein, the term “dehydrochlorination” (“dehydrochlorinating” or “dehydrochlorinated”) means the process during which hydrogen and chlorine are removed from adjacent carbons in the molecule.

[0051] As used in this article, the term "dehalogenation" refers to the loss of halogen without the loss of hydrogen, such as the loss of halogen on adjacent carbon atoms.

[0052] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, condition A or B satisfies either of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0053] The transitional phrase "consistently composed of..." is used to define compositions or methods that include materials, steps, features, components, or elements in addition to those disclosed in the literature, provided that these additionally included materials, steps, features, components, or elements do not significantly affect the essential and novel features of the invention protected by the claims, particularly the mode of action of any process in carrying out the invention to achieve the desired result. The term "consistently composed of..." occupies an intermediate position between "comprising" and "composed of...".

[0054] The transitional phrase "composed of..." does not include any unspecified elements, steps, or components. If included in the claims, protection will not be provided for materials other than those stated, except for impurities typically associated with them. When the phrase "composed of..." appears in a clause of the body of a claim, rather than immediately following the preamble, it only limits the elements set forth in that clause; other elements as a whole are not excluded from the claims.

[0055] Where the applicant has defined the invention or a part thereof using open-ended terms such as “comprising”, it should be readily understood (unless otherwise stated) that the description should be interpreted as also including inventions using terms such as “substantially composed of” or “composed of”.

[0056] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0057] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0058] As used in this paper, the GC / FID peak area is related to the amount of compound present as a proportion of the total area of ​​all detected peaks. The FID area % can be converted to mol% using a calculated or measured response factor.

[0059] As used herein, the term “about” is intended to account for variations due to experimental error (e.g., adding or subtracting approximately 10% ± 1%, ± 2%, ± 3, ... ± 10% of the indicated value). Unless otherwise expressly stated, all measurements reported herein should be understood to be modified by the term “about”, whether or not the term is explicitly used.

[0060] The compounds mentioned in this disclosure may be represented by codes, chemical structures, and / or chemical names based on the naming conventions for fluorine-containing compounds. For convenience and reference, selected compounds with codes, structures, and chemical names are provided in Table 1.

[0061]

[0062] method

[0063] In some embodiments, the present invention relates to a method for preparing HFO-1252zc from a precursor of the formula CF3CX=CH2, wherein X is selected from Cl, Br or I.

[0064] In some embodiments, the present invention relates to a method for preparing a compound of the formula CF3CHXCH3 by contacting a compound of the formula CF3CX=CH2 with hydrogen in the presence of a catalyst, wherein X is selected from Cl, Br or I.

[0065] In some embodiments, the present invention relates to a method for preparing HFO-1252zc by reacting a compound of the formula CF3CHXCH3 with a metal (such as Zn or Mg), or by reacting a compound of the formula CF3CHXCH3 with hydrogen in the presence of a catalyst, wherein X is selected from Cl, Br or I.

[0066] In some embodiments, the method includes two steps to convert a precursor or starting material into HFO-1252zc. In some embodiments, the first step includes converting the precursor CF3CX=CH2 into an intermediate compound of the formula CF3CHXCH3 by reacting it with H2 in the presence of a catalyst, wherein X is selected from Cl, Br, or I. In some embodiments, the second step includes converting the intermediate CF3CHXCH3 into HFO-1252zc by reacting it with a metal (such as Zn or Mg) or by reacting it with H2 in the presence of a catalyst.

[0067] In other embodiments disclosed herein, the CF3CHXCH3 compound is prepared according to step (1) and / or HFO-1252zc is prepared in a two-step manner according to the following two-step reaction scheme:

[0068] Where X is selected from Cl, Br or I, and M is selected from Zn or Mg or a combination thereof.

[0069] In the implementation of the two-step method, the CF3CX=CH2 compound is the precursor and the CF3CHXCH3 compound is the intermediate.

[0070] In some embodiments, the conversion of the CF3CX=CH2 compound to the CF3CHXCH3 compound takes place in the gas phase or liquid phase.

[0071] In some embodiments, the conversion of the CF3CX=CH2 compound to the CF3CHXCH3 compound is carried out with or without a support selected from carbon, Al2O3, or SiC in the presence of a catalyst selected from Pd, Pt, Ni, Cu, Au, or combinations thereof.

[0072] In some embodiments, the conversion of CF3CHXCH3 compound to HFO-1252zc is carried out in the gas phase using hydrogen in the presence of a catalyst selected from Cu, Ni, Au, or combinations thereof, with or without a support selected from carbon, Al2O3, or SiC.

[0073] In some embodiments, the conversion of CF3CHXCH3 compounds to HFO-1252zc is carried out in the liquid phase by reaction with a metal (such as Zn or Mg), optionally in the presence of a catalyst and / or optionally in the presence of a solvent.

[0074] In some embodiments, the CF3CX=CH2 compound is HCFO-1233xf, and the CF3CHXCH3 compound is HCFC-253db.

[0075] In some embodiments disclosed herein, the present invention relates to a method and compositions thereof for preparing HCFC-253db using HCFO-1233xf as a starting material according to the following reaction:

[0076] In some embodiments disclosed herein, the present invention relates to a method and composition thereof for converting HCFC-253dbc to HFO-1252zc according to any of the following reactions:

[0077] In certain embodiments disclosed herein, the present invention relates to a two-step method and compositions thereof for preparing HFO-1252zc using HCFO-1233xf as a starting material according to any of the following two-step reaction schemes:

[0078] One embodiment of the present invention disclosed herein relates to a method for converting HCFO-1233xf via the intermediate HCFC-253db to form HFO-1252zc.

[0079] The hydrogenation of HCFO-1233xf to HCFC-253db can be carried out in the gas or liquid phase. The reaction of HCFO-1233xf with hydrogen is also called hydrogenation or hydrogenolysis.

[0080] The hydrogenation reaction of HCFO-1233xf with HCFC-253db is carried out in the gas phase at temperatures ranging from about 20°C to about 80°C, preferably about 20°C and about 60°C. In some embodiments disclosed herein, HCFO-1233xf is converted to HCFC-253db at temperatures of about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, or about 80°C, and all values ​​and ranges therebetween.

[0081] The hydrogenation reaction of HCFO-1233xf with HCFC-253db is carried out in the liquid phase at temperatures ranging from about 20°C to about 120°C, preferably about 30°C and about 110°C. In some embodiments disclosed herein, HCFO-1233xf is converted to HCFC-253db at temperatures ranging from about 20°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, or about 120°C, and all values ​​and ranges therebetween.

[0082] In some implementations, the reaction between HCFO-1233xf and hydrogen is carried out in the gas phase at a pressure of 0 psig to approximately 250 psig (inclusive of all values ​​and ranges therebetween).

[0083] In some embodiments, the molar ratio of hydrogen to HCFO-1233xf used for the gas-phase conversion of HCFO-1233xf to HCFC-235db is in the range of about 0.5:1 to about 3:1, preferably about 1:1 to about 2:1.

[0084] In some embodiments, the molar ratio of hydrogen to HCFO-1233xf used for the liquid-phase conversion of HCFO-1233xf to HCFC-235db is in the range of about 0.5:1 to about 2:1, preferably about 0.8:1 to about 1.2:1.

[0085] In some embodiments disclosed herein, the reaction between HCFO-1233xf and hydrogen is optionally carried out in the presence of a diluent, such as nitrogen.

[0086] In some embodiments disclosed herein, HCFO-1233xf is converted to HCFC-253db in the gas or liquid phase in the presence of a catalyst, and more specifically a hydrogenation catalyst.

[0087] In some embodiments, the hydrogenation catalyst for converting HCFO-1233xf to HCFC-253db by reaction with hydrogen comprises a metal catalyst. In some embodiments, the catalyst comprises a metal selected from Pd, Pt, Ni, Cu, Au, or combinations thereof, with or without a support selected from carbon, graphite (e.g., SiC), or metal oxides (e.g., Al2O3). In some embodiments, the catalyst has been treated with hydrogen. In some embodiments, the catalyst is Pd / Al2O3 or Pd / C.

[0088] Based on the total weight of the support and catalyst, the amount of catalyst (e.g., palladium) on the support can range from 0.01 wt% to 10 wt%. In some embodiments disclosed herein, based on the total weight of the support and catalyst, the amount of catalyst (e.g., palladium) on the support is at most and includes 0.005 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%. %, 1.5 wt% or 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10 wt%, and all values ​​and ranges therein, including but not limited to 0.005 wt% to 0.05 wt%, 0.01 wt% to 0.1 wt%, 0.01 wt% to 0.5 wt%, 0.01 wt% to 1.0 wt%, or 0.01 wt% to 2.0 wt%, 0.02 wt% to 5.0 wt%, and 0.02 wt% to 10.0 wt%.

[0089] In some embodiments, in order to convert HCFO-1233xf to HCFC-253db in the gas phase, the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably from about 0.02 wt% to about 0.05 wt%, including all values ​​and ranges therein, based on the total weight of the support and catalyst.

[0090] In some embodiments, the catalyst used for the vapor hydrogenation reaction of HCFO-1233xf is a Pd / Al2O3 catalyst, wherein the Pd loading is in the range of 0.01 wt% to 0.05 wt%.

[0091] In some embodiments, in order to convert HCFO-1233xf to HCFC-253db in the liquid phase, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%, based on the total weight of the support and the catalyst, including all values ​​and ranges therein.

[0092] In some embodiments, the catalyst used for the liquid-phase hydrogenation reaction of HCFO-1233xf is a Pd / C catalyst, wherein the Pd loading ranges from 0.1 wt% to 10 wt%.

[0093] Hydrogenation catalysts supported on low-ash carbon are described in U.S. Patent No. 5,136,113, the entire disclosure of which is incorporated herein by reference, and can also be used for the conversion of HCFO-1233xf to HCFC-253db.

[0094] In some embodiments disclosed herein, the reaction of HCFO-1233xf with hydrogen to form HCFC-253db is carried out in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably a metal contained on a support, and optionally in the presence of nitrogen. The amount of catalyst on the support ranges from about 0.01 wt% to about 10 wt% for liquid-phase methods and from about 0.01 wt% to about 0.1 wt% for gas-phase methods.

[0095] In some embodiments disclosed herein, the reaction of HCFO-1233xf with hydrogen to form HCFC-253db is carried out in the liquid phase at a temperature of about 20°C to about 120°C, preferably about 30°C to about 110°C, in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably contained on a support, and preferably wherein the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably about 0.4 wt% to about 6 wt%, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HCFO-1233xf for the liquid-phase conversion of HCFO-1233xf to HCFC-235db is in the range of about 0.5:1 to about 2:1, more preferably about 0.8:1 to about 1.2:1.

[0096] In some embodiments disclosed herein, the reaction of HCFO-1233xf with hydrogen to form HCFC-253db is carried out in the gas phase at a temperature of about 20°C to about 120°C, preferably about 30°C to about 110°C, in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably contained on a support, and preferably wherein the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably about 0.02 wt% to about 0.05 wt%, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HCFO-1233xf for the gas-phase conversion of HCFO-1233xf to HCFC-235db is in the range of about 0.5:1 to about 3:1, more preferably about 1:1 to about 2:1.

[0097] In some embodiments, the present invention relates to the conversion of HCFC-253db to HFO-1252zc by contacting HCFC-253db with hydrogen. More specifically, HCFC-253db is converted to HFO-1252zc by hydrogenation to remove halogens from adjacent carbons to form double bonds. The removal of adjacent halogens is considered as hydrodehalogenation.

[0098] In some implementations, HCFC-253db is an intermediate formed by step (1) of the above reaction scheme of converting HCFO-1233xf into HCFC-253db, thereby providing the present invention with a multi-step integration method for forming HFO-1252zc from HCFO-1233xf.

[0099] In some implementations, the conversion of HCFC-253db to HFO-1252zc is carried out in the gas phase using hydrogen.

[0100] In some embodiments disclosed herein, HCFC-253db is converted to HFO-1252zc in the gas phase using H2 at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C.

[0101] In some embodiments disclosed herein, at approximately 200°C, approximately 205°C, approximately 210°C, approximately 215°C, approximately 220°C, approximately 225°C, approximately 230°C, approximately 235°C, approximately 240°C, approximately 245°C, approximately 250°C, approximately 255°C, approximately 260°C, approximately 265°C, approximately 270°C, approximately 275°C, approximately 280°C, approximately 285°C, approximately 290°C, approximately 295°C, approximately 300°C, approximately 305°C, approximately 310°C, approximately 315°C, approximately 320°C, approximately 325°C, approximately 330°C, approximately 335°C, approximately 340°C, approximately 345°C, approximately 350°C, approximately 355°C, approximately 360°C, approximately... At temperatures of 365°C, approximately 370°C, approximately 375°C, approximately 380°C, approximately 385°C, approximately 390°C, approximately 395°C, approximately 400°C, approximately 405°C, approximately 410°C, approximately 415°C, approximately 420°C, approximately 425°C, approximately 430°C, approximately 435°C, approximately 440°C, approximately 445°C, approximately 450°C, approximately 455°C, approximately 460°C, approximately 465°C, approximately 470°C, approximately 475°C, approximately 480°C, approximately 485°C, approximately 490°C, approximately 495°C, or approximately 500°C and all values ​​and ranges therebetween, HCFC-253db is converted to HFO-1252zc in the gas phase using H2.

[0102] In some embodiments disclosed herein, HCFC-253db is converted to HFO-1252zc in the gas phase using H2 at pressures from 0 psig to approximately 250 psig (inclusive of all values ​​and ranges therebetween).

[0103] In some embodiments, the molar ratio of hydrogen to HCFC-253db used for gas-phase conversion of HCFC-235db is in the range of about 5:1 to about 40:1, preferably about 10:1 to about 30:1.

[0104] In some embodiments disclosed herein, the reaction between HCFC-253db and hydrogen is optionally carried out in the presence of a diluent, such as nitrogen.

[0105] In some embodiments disclosed herein, HCFC-253db is converted to HFO-1252zc in the gas phase using H2, in the presence of a catalyst. In some embodiments, the catalyst for the conversion of HCFC-253db to HFO-1252zc comprises a metal selected from Ni, Cu, Au, or combinations thereof, with or without a support (such as carbon, graphite (e.g., SiC), or metal oxides (e.g., Al2O3)). In some embodiments, the catalyst has been treated with hydrogen. In some embodiments, the catalyst is Au / C or Cu / C.

[0106] Based on the total weight of the support and catalyst, the amount of catalyst on the support can range from about 2% by weight to about 10% by weight. In some embodiments disclosed herein, based on the total weight of the support and catalyst, the amount of catalyst on the support is at most and includes 2.0% by weight, 3.0% by weight, 4.0% by weight, 5.0% by weight, 6.0% by weight, 7.0% by weight, 8.0% by weight, 9.0% by weight, 10% by weight, and all values ​​and ranges therebetween.

[0107] In some embodiments, the catalyst used for the gas-phase conversion of HCFC-253db to HFO-1252zc is an Au / C catalyst, wherein the Au loading is in the range of about 2% to about 10% by weight.

[0108] Hydrogenation catalysts supported on low-ash carbon are described in U.S. Patent No. 5,136,113, the entire disclosure of which is incorporated herein by reference, and can be used for the conversion of HCFC-253db to HFO-1252zc.

[0109] In some embodiments disclosed herein, HCFC-253db reacts with reactive hydrogen to form HFO-1252zc in the gas phase at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C, in the presence of a catalyst, preferably contained on a support of a metal (such as Au or Cu on the support), and preferably wherein the amount of catalyst on the support ranges from 2% by weight to 10% by weight, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HCFC-253db for the gas-phase conversion of HCFC-235db is in the range of about 5:1 to about 40:1, more preferably from about 10:1 to about 30:1.

[0110] In some embodiments, the present invention relates to the conversion of HCFC-253db to HFO-1252zc by contacting HCFC-253db with a metal (such as Zn, Mg, or a combination thereof). More specifically, the conversion of HCFC-253db to HFO-1252zc with a metal is achieved by removing halogens from adjacent carbons to form double bonds. The removal of adjacent halogens is considered as dehalogenation.

[0111] In some implementations, HCFC-253db is an intermediate formed by step (1) of the above reaction scheme of converting HCFO-1233xf into HCFC-253db, thereby providing the present invention with a multi-step integration method for forming HFO-1252zc from HCFO-1233xf.

[0112] In some embodiments, the conversion of HCFC-253db to HFO-1252zc occurs in the liquid phase via a metal (such as Zn or Mg or a combination thereof). In some embodiments, the metal is a reactive metal.

[0113] In some embodiments, the reaction of HCFC-253db with a metal (e.g., zinc) occurs in the liquid phase at a temperature of about 50°C to about 180°C, preferably about 80°C to about 150°C.

[0114] In some embodiments, the reaction of HCFC-253db with a metal (e.g., zinc) occurs in the liquid phase at temperatures of about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 110°C, about 115°C, about 120°C, about 125°C, about 130°C, about 135°C, about 140°C, about 145°C, about 150°C, about 155°C, about 160°C, about 165°C, about 170°C, about 175°C, or about 180°C, and all values ​​and ranges therebetween.

[0115] In some implementations, the reaction of HCFC-253db with a metal (e.g., zinc) occurs under autogenous pressure.

[0116] In some embodiments, the molar ratio of metal to HCFC-235db used for liquid-phase conversion of HCFC-253db is in the range of about 1:1 to about 5:1, preferably about 1.05:1 to about 3:1.

[0117] In some implementations, the metal is activated by acid, and more specifically by contact with acid prior to reaction with HCFC-253db.

[0118] In some embodiments, the metal is zinc, and more specifically, zinc powder. In some embodiments, the zinc is activated with an acid (e.g., HCl). In some embodiments disclosed herein, the zinc powder is activated with HCl (e.g., aqueous or alcoholic) and then used to convert HCFC-253db to HFO-1252zc.

[0119] In some implementations, the reaction of HCFC-253db with a metal (e.g., zinc) is carried out in the absence of a catalyst.

[0120] In some embodiments, the reaction of HCFC-253db with a metal (e.g., zinc) is carried out in the presence of a catalyst. In some embodiments, the catalyst is selected from zinc salts, ammonium salts, and phosphonium salts. In some embodiments, the catalyst comprises a zinc salt selected from zinc acetate and ZnCl2. In some embodiments, the catalyst comprises an ammonium salt, such as tetrabutylammonium bromide.

[0121] In some embodiments, the reaction of HCFC-253db with a metal (e.g., zinc) is carried out in the presence of a solvent. In some embodiments, the solvent is selected from alcohols, amides, pyridines, and ethers. In some embodiments disclosed herein, the solvent comprises an alcohol selected from methanol, ethanol, propanol, isopropanol, and ethylene glycol.

[0122] In some implementations, the reaction of HCFC-253db with a metal (e.g., zinc) is carried out in the liquid phase in the presence of a catalyst and a solvent.

[0123] In other embodiments, the present invention relates to a liquid-phase reaction of HCFC-253db with zinc at a temperature of about 50°C to about 180°C, preferably about 80°C to about 150°C, in the presence of a catalyst preferably selected from zinc salts (e.g., ZnCl2 or zinc acetate), ammonium salts (e.g., tetrabutylammonium bromide), or phosphonium salts, and in the presence of a solvent preferably selected from alcohols, amides, pyridines, and ethers, and more preferably from methanol, ethanol, propanol, isopropanol, and ethylene glycol. In some embodiments, the zinc used for the reaction has been acid-activated, for example, zinc powder activated with HCl (e.g., aqueous or in an alcohol). Preferably, the molar ratio of metal to HCFC-253db for the liquid-phase conversion of HCFC-235db is in the range of about 1:1 to about 5:1, more preferably about 1.05:1 to about 3:1.

[0124] In some embodiments, the CF3CX=CH2 compound is HBFO-1233xfB, and the CF3CHXCH3 compound is HBFC-253dbB.

[0125] In some embodiments disclosed herein, the present invention relates to a method and compositions thereof for preparing HBFC-253dbB using HBFO-1233xfB as a starting material according to the following reaction:

[0126] In some embodiments disclosed herein, the present invention relates to a method and compositions thereof for converting HBFC-253dbB to HFO-1252zc according to any of the following reactions:

[0127] In certain embodiments disclosed herein, the present invention relates to a two-step method and compositions thereof for preparing HFO-1252zc using HBFO-1233xfB as a starting material according to any of the following two-step reaction schemes:

[0128] One embodiment of the present invention disclosed herein relates to a method for converting HBFO-1233xfB via intermediate HBFC-253dbB to form HFO-1252zc.

[0129]

[0130] The hydrogenation of HBFO-1233xfB to HBFC-253dbB can be carried out in the gas or liquid phase. The reaction of HBFO-1233xfB with hydrogen is also called hydrogenation or hydrogenolysis.

[0131] The hydrogenation reaction of HBFO-1233xfB and HBFC-253dbB is carried out in the gas phase at temperatures ranging from about 30°C to about 130°C, preferably about 60°C and about 110°C. In some embodiments disclosed herein, HCFO-1233xf is converted to HCFC-253dbB or HBFO-1233xfB is converted to HBFC-253dbB at temperatures ranging from about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, about 120°C, or about 130°C, and all values ​​and ranges therebetween.

[0132] The hydrogenation reaction of HBFO-1233xfB with HBFC-253dbB is carried out in the liquid phase at temperatures ranging from about 40°C to about 120°C, preferably about 60°C and about 100°C. In some embodiments disclosed herein, HBFO-1233xfB is converted to HBFC-253dbB at temperatures ranging from about 40°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C, about 110°C, or about 120°C, and all values ​​and ranges therebetween.

[0133] In some implementations, the reaction between HBFO-1233xfB and hydrogen is carried out in the gas phase at a pressure of 0 psig to approximately 250 psig (inclusive of all values ​​and ranges therebetween).

[0134] In some embodiments, the molar ratio of hydrogen to HBFO-1233xfB used for the gas-phase conversion of HBFO-1233xfB to HBFC-253dbB is in the range of about 1:1 to about 10:1, preferably about 2:1 to about 8:1.

[0135] In some embodiments, the molar ratio of hydrogen to HBFO-1233xfB used for the liquid-phase conversion of HBFO-1233xfB to HBFC-253dbB is in the range of about 0.5:1 to about 3:1, preferably about 0.8:1 to about 2:1.

[0136] In some embodiments disclosed herein, the reaction between HBFO-1233xfB and hydrogen is optionally carried out in the presence of a diluent, such as nitrogen.

[0137] In some embodiments disclosed herein, HBFO-1233xfB is converted to HBFC-253dbB in the gas or liquid phase in the presence of a catalyst, and more specifically a hydrogenation catalyst.

[0138] In some embodiments, the hydrogenation catalyst for converting HBFO-1233xfB to HBFC-253dbB by reaction with hydrogen comprises a metal catalyst. In some embodiments, the catalyst, with or without a support selected from carbon, graphite (e.g., SiC), or metal oxides (e.g., Al₂O₃), comprises a metal selected from Pd, Pt, Ni, Cu, Au, or combinations thereof. In some embodiments, the catalyst has been treated with hydrogen. In some embodiments, the catalyst is Pd / Al₂O₃ or Pd / C.

[0139] The amount of catalyst (e.g., palladium) on the support can range from 0.1 wt% to 10 wt% based on the total weight of the support and catalyst (e.g., palladium). In some embodiments disclosed herein, the amount of catalyst on the support, based on the total weight of the support and catalyst (e.g., palladium), is at most and includes 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1.0 wt%, 1.5 wt%, or 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10 wt%, and all values ​​and ranges therebetween.

[0140] In some embodiments, in order to convert HBFO-1233xfB to HBFC-253dbB in the gas phase, the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, more preferably from about 0.2 wt% to about 0.8 wt%, based on the total weight of the support and the catalyst, including all values ​​and ranges therein.

[0141] In some embodiments, the catalyst used for the vapor hydrogenation reaction of HBFO-1233xfB is a Pd / Al2O3 catalyst, wherein the Pd loading is in the range of 0.1 wt% to 1.0 wt%.

[0142] In some embodiments, in order to convert HBFO-1233xfB to HBFC-253dbB in the liquid phase, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%, based on the total weight of the support and the catalyst, including all values ​​and ranges therein.

[0143] In some embodiments, the catalyst used for the liquid-phase hydrogenation reaction of HBFO-1233xfB is a Pd / C catalyst, wherein the Pd loading ranges from 0.1 wt% to 10 wt%.

[0144] Hydrogenation catalysts supported on low-ash carbon are described in U.S. Patent No. 5,136,113, the entire disclosure of which is incorporated herein by reference, and can also be used for the conversion of HBFO-1233xfB to HBFC-253dbB.

[0145] In some embodiments disclosed herein, the reaction of HBFO-1233xfB with hydrogen to form HBFC-253dbB is carried out in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably a metal contained on a support, and optionally in the presence of nitrogen. The amount of catalyst on the support ranges from 0.1 wt% to 10 wt% for liquid-phase methods and from about 0.1 wt% to about 1 wt% for gas-phase methods.

[0146] In some embodiments disclosed herein, the reaction of HBFO-1233xfB with hydrogen to form HBFC-253dbB is carried out in the liquid phase at a temperature of about 40°C to about 120°C, preferably about 60°C to about 100°C, in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably containing a metal on a support, and preferably wherein the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably about 0.4 wt% to about 6 wt%, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HBFO-1233xfB for the liquid-phase conversion of HBFO-1233xfB to HBFC-253dbB is in the range of about 0.5:1 to about 3:1, more preferably about 0.8:1 to about 2:1.

[0147] In some embodiments disclosed herein, the reaction of HBFO-1233xfB with hydrogen to form HBFC-253dbB is carried out in the gas phase at a temperature of about 30°C to about 130°C, preferably about 60°C to about 110°C, in the presence of a catalyst, preferably Pd / Al2O3 or Pd / C, preferably containing a metal (such as Pd on a support), and preferably wherein the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, more preferably from about 0.2 wt% to about 0.8 wt%, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HBFO-1233xfB for the gas-phase conversion of HBFO-1233xfB to HBFC-253dbB is in the range of about 1:1 to about 10:1, more preferably from about 2:1 to about 8:1.

[0148] In some embodiments, the present invention relates to the conversion of HBFC-253dbB to HFO-1252zc by contacting HBFC-253dbB with hydrogen. More specifically, HBFC-253dbB is converted to HFO-1252zc by hydrogenation to remove halogens from adjacent carbons to form double bonds. The removal of adjacent halogens is considered as hydrodehalogenation.

[0149] In some implementations, HBFC-253dbB is an intermediate formed by step (1) of the above reaction scheme of converting HBFO-1233xfB into HBFC-253dbB, thereby providing the present invention with a multi-step integration method for forming HFO-1252zc from HBFO-1233xfB.

[0150] In some implementations, the conversion of HBFC-253dbB to HFO-1252zc is carried out in the gas phase using hydrogen.

[0151] In some embodiments disclosed herein, HBFC-253dbB is converted to HFO-1252zc in the gas phase using H2 at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C.

[0152] In some embodiments disclosed herein, at approximately 200°C, approximately 205°C, approximately 210°C, approximately 215°C, approximately 220°C, approximately 225°C, approximately 230°C, approximately 235°C, approximately 240°C, approximately 245°C, approximately 250°C, approximately 255°C, approximately 260°C, approximately 265°C, approximately 270°C, approximately 275°C, approximately 280°C, approximately 285°C, approximately 290°C, approximately 295°C, approximately 300°C, approximately 305°C, approximately 310°C, approximately 315°C, approximately 320°C, approximately 325°C, approximately 330°C, approximately 335°C, approximately 340°C, approximately 345°C, approximately 350°C, approximately 355°C, approximately 360°C, approximately... At temperatures of 365°C, approximately 370°C, approximately 375°C, approximately 380°C, approximately 385°C, approximately 390°C, approximately 395°C, approximately 400°C, approximately 405°C, approximately 410°C, approximately 415°C, approximately 420°C, approximately 425°C, approximately 430°C, approximately 435°C, approximately 440°C, approximately 445°C, approximately 450°C, approximately 455°C, approximately 460°C, approximately 465°C, approximately 470°C, approximately 475°C, approximately 480°C, approximately 485°C, approximately 490°C, approximately 495°C, or approximately 500°C and all values ​​and ranges therebetween, HBFC-253dbB is converted to HFO-1252zc in the gas phase using H2.

[0153] In some embodiments disclosed herein, HBFC-253dbB is converted to HFO-1252zc in the gas phase using H2 at pressures from 0 psig to approximately 250 psig (inclusive of all values ​​and ranges therebetween).

[0154] In some embodiments, the molar ratio of hydrogen to HBFC-253dbB used for gas-phase conversion of HBFC-235dbB is in the range of about 5:1 to about 40:1, preferably from about 10:1 to about 30:1.

[0155] In some embodiments disclosed herein, the reaction between HBFC-253dbB and hydrogen is optionally carried out in the presence of a diluent, such as nitrogen.

[0156] In some embodiments disclosed herein, HBFC-253dbB is converted to HFO-1252zc in the gas phase using H2, in the presence of a catalyst. In some embodiments, the catalyst for the conversion of HBFC-253dbB to HFO-1252zc comprises a metal selected from Ni, Cu, Au, or combinations thereof, with or without a support (such as carbon, graphite (e.g., SiC), or metal oxides (e.g., Al2O3)). In some embodiments, the catalyst has been treated with hydrogen. In some embodiments, the catalyst is Au / C or Cu / C.

[0157] Based on the total weight of the support and catalyst, the amount of catalyst on the support can range from about 2% by weight to about 10% by weight. In some embodiments disclosed herein, based on the total weight of the support and catalyst, the amount of catalyst on the support is at most and includes 2.0% by weight, 3.0% by weight, 4.0% by weight, 5.0% by weight, 6.0% by weight, 7.0% by weight, 8.0% by weight, 9.0% by weight, 10% by weight, and all values ​​and ranges therebetween.

[0158] In some embodiments, the catalyst used for the gas-phase conversion of HBFC-253dbB to HFO-1252zc is an Au / C catalyst, wherein the Au loading is in the range of about 2% to about 10% by weight.

[0159] Hydrogenation catalysts supported on low-ash carbon are described in U.S. Patent No. 5,136,113, the entire disclosure of which is incorporated herein by reference, and can be used for the conversion of HBFC-253dbB to HFO-1252zc.

[0160] In some embodiments disclosed herein, HBFC-253dbB reacts with reactive hydrogen to form HFO-1252zc at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C, in the presence of a catalyst, preferably contained in a metal (such as Au or Cu on a support), and preferably wherein the amount of catalyst on the support ranges from about 2% by weight to about 10% by weight, and optionally in the presence of nitrogen. Preferably, the molar ratio of hydrogen to HCFC-253db for the gas-phase conversion of HCFC-235db is in the range of about 5:1 to about 40:1, more preferably from about 10:1 to about 30:1.

[0161] In some embodiments, the present invention relates to the conversion of HBFC-253dbB to HFO-1252zc by contacting HCFC-253dbB with a metal (such as Zn, Mg, or a combination thereof). More specifically, HBFC-253dbB is converted to HFO-1252zc by removing halogens from adjacent carbons to form double bonds. The removal of adjacent halogens is considered as dehalogenation.

[0162] In some implementations, HBFC-253dbB is an intermediate formed by step (1) of the above reaction scheme of converting HBFO-1233xfB into HBFC-253dbB, thereby providing the present invention with a multi-step integration method for forming HFO-1252zc from HBFO-1233xfB.

[0163] In some embodiments, the conversion of HBFC-253dbB to HFO-1252zc occurs in the liquid phase via a metal (such as Zn or Mg, or a combination thereof). In some embodiments, the metal is a reactive metal.

[0164] In some embodiments, the reaction of HBFC-253dbB with a metal (e.g., zinc) occurs at a temperature of about 40°C to about 120°C, preferably about 50°C to 100°C.

[0165] In some embodiments, the reaction of HBFC-253dbB with a metal (e.g., zinc) occurs at temperatures of about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, about 110°C, about 115°C, or about 120°C, and all values ​​and ranges therebetween.

[0166] In some implementations, the reaction of HBFC-253dbB with a metal (e.g., zinc) occurs under autogenous pressure.

[0167] In some embodiments, the molar ratio of metal to HBFC-235dbB used for the liquid phase conversion of HBFC-253dbB is in the range of about 1:1 to about 5:1, preferably from about 1.05:1 to about 3:1.

[0168] In some implementations, the metal is activated by acid, and more specifically by contact with acid prior to reaction with HBFC-253dbB.

[0169] In some embodiments, the metal is zinc, and more specifically, zinc powder. In some embodiments, the zinc is activated with an acid (e.g., HCl). In some embodiments disclosed herein, the zinc powder is activated with HCl (e.g., aqueous or in an alcohol) and then used to convert HBFC-253dbB to HFO-1252zc.

[0170] In some implementations, the reaction of HBFC-253dbB with a metal (e.g., zinc) is carried out in the absence of a catalyst.

[0171] In some embodiments, the reaction of HBFC-253dbB with a metal (e.g., zinc) is carried out in the presence of a catalyst. In some embodiments, the catalyst is selected from zinc salts, ammonium salts, and phosphonium salts. In some embodiments, the catalyst comprises a zinc salt selected from zinc acetate and ZnCl2. In some embodiments, the catalyst comprises an ammonium salt, such as tetrabutylammonium bromide.

[0172] In some embodiments, the reaction of HBFC-253dbB with a metal (e.g., zinc) is carried out in the presence of a solvent. In some embodiments, the solvent is selected from alcohols, amides, pyridines, and ethers. In some embodiments disclosed herein, the solvent comprises an alcohol selected from methanol, ethanol, propanol, isopropanol, and ethylene glycol.

[0173] In some implementations, the reaction of HBFC-253dbB with a metal (e.g., zinc) is carried out in the liquid phase in the presence of a catalyst and a solvent.

[0174] In other embodiments, the present invention relates to a liquid-phase reaction of HBFC-253dbB with zinc at a temperature of about 40°C to about 120°C, preferably about 50°C to about 100°C, in the presence of a catalyst preferably selected from zinc salts (e.g., ZnCl2 or zinc acetate), ammonium salts (e.g., tetrabutylammonium bromide), or phosphonium salts, and in the presence of a solvent preferably selected from alcohols, amides, pyridines, and ethers, and more preferably from alcohol solvents selected from methanol, ethanol, propanol, isopropanol, and ethylene glycol. In some embodiments, the zinc used for the reaction has been acid-activated, for example, zinc powder activated with HCl (e.g., aqueous or in an alcohol). Preferably, the molar ratio of metal to HBFC-253dbB for the liquid-phase conversion of HBFC-235dbB is in the range of about 1:1 to about 5:1, more preferably about 1.05:1 to about 3:1.

[0175] In one embodiment, HBFO-1233xfB used in any of the above methods is formed from HFO-1243zf. More specifically, in some embodiments, HFO-1243zf is converted to dibromotrifluoropropane in the presence of Br2, and dibromotrifluoropropane is converted to HBFO-1233xfB in the presence of a caustic agent.

[0176] In some embodiments, the present invention relates to a method for preparing HFO-1252zc from at least one compound selected from HCFC-253db, HBFC-253dbB, HCFO-1233xf and HBFO-1233xfB in one or more reactors.

[0177] In some embodiments, the present invention relates to a system for performing a multi-step method, such as Figure 1 As shown, the first feed 10 is converted into an intermediate in reactor 20 and discharged as a first product stream 30. The first product stream is transferred to reactor 40 for further reaction, which may include one or more reactors. The final product mixture is discharged through line 50. Reactor 20 and one or more reactors 30 can be configured for liquid-phase or gas-phase conversion. Intermediate product streams, such as the first product stream 30, can be processed, and the intermediates / products can be recovered prior to downstream processing.

[0178] Composition

[0179] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of, one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), and 1-fluoropropylene (HFO-1261ze). Pentafluorobutene isomers (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0180] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (H The following substances are present: 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc is present.

[0181] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-13). 45) 2-Butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc and HFO-1243zf are present.

[0182] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-13). 45) 2-Butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc and HFO-1261ze are present.

[0183] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-13). 45) 2-Butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc), wherein at least HFO-1252zc and HFC-263fb are present.

[0184] Certain embodiments disclosed herein relate to compositions comprising, substantially consisting of, or consisting of one or more compounds selected from the following: propane, 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1-trifluoropropane (HFC-263fb), dichloromethane (HCC-30), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), tetrafluorobutane (HFC-374), chlorofluoropropene (HCFO-1251), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3-difluoropropene (HBFO-1242xfB), dichlorotrifluoropropane isomer (HCFC-243), and dibromotrifluoropropane (C3H3Br2F3), wherein at least HBFO-1233xfB is present.

[0185] In some embodiments, the present invention relates to compositions comprising HFC-263fb and HCFC-253db.

[0186] In some embodiments, the present invention relates to compositions comprising HFC-263fb, HCFO-1233xf, and HCFC-253db.

[0187] In some embodiments, the present invention relates to compositions comprising HFO-1252zc, HFC-263fb, HCFO-1233xf, and HCFC-253db.

[0188] In some embodiments, the present invention relates to compositions comprising up to 50 mol% of HFC-263fb and up to about 99 mol% of HCFC-253db based on a total composition of 100 mol%.

[0189] In some embodiments, the present invention relates to compositions comprising HFC-263fb and HCFC-253dbB.

[0190] In some embodiments, the present invention relates to compositions comprising HFC-263fb, HCFO-1233xfB and HCFC-253dbB.

[0191] In some embodiments, the present invention relates to compositions comprising HFO-1252zc, HFC-263fb, HCFO-1233xfB and HCFC-253dbB.

[0192] For all compositions disclosed herein, except for HFO-1252zc, the total amount of other compounds may be about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, about 1% by weight or less, about 0.9% by weight or less, about 0.8% by weight or less, about 0.7% by weight or less, about 0.6% by weight or less, about 0.5% by weight or less, about 0.4% by weight or less, about 0.3% by weight or less, about 0.2% by weight or less, about 0.1% by weight or less, about 0.09% by weight or less, about 0.08% by weight or less, about 0.07% by weight or less, about 0.06% by weight or less, about 0.05% by weight or less, about 0.04% by weight or less, about 0.03% by weight or less, about 0.02% by weight or less, or about 0.01% by weight or less, or about 10 ppm or less, or about 1 ppm or less.

[0193] Certain embodiments of the invention disclosed herein relate to any of the aforementioned compositions that are free of or substantially free of Group A fluorinated substances. In one embodiment, as used herein, “Group A fluorinated substance” includes any substance that satisfies the following condition: (i) contains at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached thereto); as well as(ii) It complies with the persistence criteria in soil / sediments and water as set out in Annex XIII (Section 1.1.1) of the EU REACH Regulation (https: / / reachonline.eu / reach / en / annex-xiii-1-1.1-1.1.1.html, accessed 2 May 2023), and the publication of that criterion is cited in Annex XV Restriction Report of 22 March 2023, the publication of which is incorporated herein by reference (https: / / echa.europa.eu / documents / 10162 / f605d4b5-7c17-7414-8823-b49b9fd43aea, accessed 2 May 2023).

[0194] In another implementation, as used herein, “Group A fluorinated substances” include those with a Henry's Law constant ≤ 250 Pa*m 3 / mol and Any substance containing at least one fully fluorinated methyl (-CF3) or methylene (-CF2-) carbon atom (without any H / Cl / Br / I attached to it).

[0195] In the implementation plan, Group A fluorinated substances include, but are not limited to, TFA.

[0196] As used herein, the phrase "free of" relating to the presence of Group A fluorinated substances in the compositions of the present invention means that the amount of such substances in the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by gas chromatography with a flame ionization detector, gas chromatography with a mass detector (by analyzing a gas or liquid sample), and / or ion chromatography (by analyzing a water sample after bubbling a hot fluid through water). Such methods are well known to those skilled in the art. As used herein, the phrase "substantially free" regarding the presence of Group A fluorinated substances in the compositions of the present invention means, when measured by gas chromatography (GC), such as gas chromatography (GC) with a flame ionization or electron capture detector, or GC coupled with a mass detector (GC / MS method), by ion chromatography (IC) or ion chromatography-mass spectrometry (IC-MS), or by high performance liquid chromatography (HPLC) or high performance liquid chromatography-mass spectrometry (HPLC-MS), the amount of such substances in the composition is >0 wt% and ≤ 5 wt%, or >0 wt% and ≤ 4 wt%, or >0 wt% and ≤ 3 wt%, or >0 wt% and ≤ 2 wt%, or >0 wt% and ≤ 1 wt%, and all values ​​and ranges therein. TFA analytical standards can be used with gas chromatography or ion chromatography and are available from, for example, Sigma Aldrich.

[0197] In a preferred embodiment, the degradation products of the compositions according to the invention are free of or substantially free of Group A fluorinated substances. As used herein, the phrase "free of" in relation to the formation of Group A fluorinated substances as degradation products of the compositions of the invention means that the theoretical molar yield of such substances in the environmental compartments of air, soil / sediment, and water generated during the tropospheric degradation of the composition is sufficiently low to be undetectable, including but not limited to 0%, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques. As used herein, the phrase “substantially free” regarding the formation of Group A fluorinated substances from the compositions of the present invention means, when measured by GC techniques (e.g., GC or GC / MS methods with flame ionization or electron capture detectors), by IC or IC-MS techniques, or by HPLC or HPLC-MS techniques, all values ​​and ranges in between, of such substances generated in the environmental compartments of air, soil / sediment, and water during the tropospheric degradation of the composition.

[0198] In this invention, the reactor, distillation column, and related feed lines, effluent lines, and related units used for applying the method of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical construction materials well-known in the field of fluorination include stainless steel (especially austenitic stainless steel) and well-known high-nickel alloys (such as Monel). ™ Nickel-copper alloy, Hastelloy ™ Nickel-based alloys and Inconel ™ Nickel-chromium alloys and copper-clad steel.

[0199] In this invention, a series of reaction steps for preparing HFO-1252zc are carried out in one or more gas-phase reactors, one or more liquid-phase reactors, and combinations thereof.

[0200] In this invention, a series of reaction steps for preparing HFO-1252zc are carried out in one or more gas-phase reactors, one or more liquid-phase reactors, and combinations thereof, and the effluent from the reactors is optionally separated to recycle unreacted feed material and to purify / concentrate intermediates for downstream conversion.

[0201] Example

[0202] Example 1: Hydrogenation of HCFO-1233xf to HCFC-253db in the gas phase using 0.02% Pd / Al2O3.

[0203] In a 12-inch ½" OD Monel reactor, 4 ml of 0.02% Pd / Al₂O₃ was loaded. The catalyst was treated with H₂ at 120°C for 1 hour. The reactor was then cooled to 30°C. H₂ and N₂ feeds were controlled by mass flow controllers, and HCFO-1233xf was fed by a pump. The reaction test conditions are listed in Table 2 below. The reactor effluent was analyzed by online GC-MS-FID. The analytical results are listed in Table 2 below, showing complete high conversion of HCFO-1233xf and good selectivity for HCFC-253dB.

[0204]

[0205] Example 2: Using 0.04% Pd / A in the gas phase l2 O3 hydrogenates HCFO-1233xf to HCFC-253db.

[0206] In a 12-inch ½" OD Monel reactor, 4 ml of 0.04% Pd / Al₂O₃ was loaded. The catalyst was treated with H₂ at 120°C for 1 hour. The reactor was then cooled to 30°C. H₂ and N₂ feeds were controlled by mass flow controllers, and HCFO-1233xf was pumped in. The reaction test conditions are listed in Table 3 below. The reactor effluent was analyzed by online GC-MS-FID. The analytical results, listed in Table 3 below, show complete high conversion of HCFO-1233xf and good selectivity for HCFC-253dB.

[0207]

[0208]

[0209] Example 3: Hydrogenation of HCFO-1233xf to HCFC-253db in the liquid phase using 0.5% Pd / C

[0210] 8 g of 0.5% Pd / C was loaded into a 400 ml Hastelloy C shaking tube. The tube was then cooled to -30°C and evacuated. 200 g of HCFO-1233xf was added to the shaker, and the tube was heated back to 100°C. At 100°C, H2 was slowly added to a pressure of 250 psig. A rapid pressure drop indicated that the reaction was occurring under these conditions. H2 was added further until the pressure in the reactor no longer decreased. Approximately 3 g of H2 was added at the end of the test. The products of the reaction were analyzed by GC-MS-FID and are shown in Table 4 below.

[0211]

[0212] Example 4: Hydrogenation of HCFO-1233xf to HCFC-253db in the liquid phase using 5% Pd / C

[0213] 8 g of 5% Pd / C was loaded into a 400 mL Hastelloy C shaking tube. The tube was purged three times with H2 pressure, then pressurized to 250 psig with H2 and heated to 60 °C for 3 hours. Afterward, the H2 was purged, and the shaking tube was cooled to -30 °C and evacuated. 200 g of HCFO-1233xf was added to the shaker, and the tube was heated back to 40 °C. At 40 °C, H2 was slowly added to a pressure of 250 psig. A rapid pressure drop indicated that the reaction was occurring under these conditions. Further H2 was added until the reactor pressure no longer decreased. Approximately 3 g of H2 was added at the end of the test. The products of the reaction were analyzed by GC-MS-FID and are shown in Table 5 below.

[0214]

[0215] Example 5: Hydrogenation of HCFC-253db to HFO-1252zc in the gas phase using 4% Au / carbon

[0216] In a 12-inch ½" OD Monel reactor, 4 ml of 4% Au / C was loaded. The catalyst was treated with H2 flow for 1 hour at 200°C. The reactor was then heated to 260°C. 10 sccm of H2 was fed and controlled via a mass flow controller, and HCFC-253db was fed via a pump at a rate of 0.5 ml / h. The reactor effluent was analyzed by online GC-MS-FID. The analysis results showed that approximately 20 mol% of HFO-1252zc was formed in the reaction mixture, and the major byproduct was HFC-263fb.

[0217] Example 6: Conversion of HCFC-253db to HFO-1252zc in the liquid phase using zinc powder

[0218] 20 g of pre-activated zinc powder (activated with 2% HCl) and 50 g of ethanol were added to a 400 ml Hastelloy C autoclave. After heating to 70 °C, 20 g of HCFC-253db was added to the reactor. The increase in reactor pressure indicated that the reaction had occurred. After stirring at 70 °C for 30 minutes, the reactor temperature was further increased to 90 °C, and the contents were stirred at 90 °C for 2 hours. After cooling the reactor to room temperature, the products from the reactor were analyzed by GC-MS-FID, which showed the formation of approximately 30% HFO-1252zc. The main byproduct was HFC-263fb.

[0219] Example 7: Conversion of HCFC-253db to HFO-1252zc in the liquid phase by reacting zinc powder with TBAB at 140°C .

[0220] 0.8 g of pre-activated zinc powder (activated with 2% HCl), 0.13 g of TBAB, 1.25 g of 253 dB, and 4 g of methanol were added to a 10 ml Hastelloy C autoclave. The autoclave was then cooled to -40 °C and evacuated. It was subsequently heated to 140 °C and maintained at 140 °C with stirring for 16 hours. The reactor pressure was increased to approximately 820 psig. The reactor was then cooled to room temperature. The vapor fraction of the products from the reactor was analyzed by GC-MS-FID, and the results are listed in Table 6 below.

[0221]

[0222] Example 8: Conversion of HCFC-253db to HFO-1252zc in the liquid phase by reacting zinc powder with TBAB at 120°C .

[0223] 1 g of pre-activated zinc powder (activated with 2% HCl), 0.25 g of TBAB, 1 g of 253 dB, and 4 g of methanol were added to a 10 ml Hastelloy C autoclave. The autoclave was then cooled to -40 °C and evacuated. It was then heated to 120 °C and maintained at 120 °C with stirring for 16 hours. The reactor pressure was increased to approximately 1040 psig. The reactor was then cooled to room temperature. The vapor fraction of the products from the reactor was analyzed by GC-MS-FID, and the results are listed in Table 7 below.

[0224]

[0225] Example 9: Conversion of HCFC-253db to HFO-1252zc in the liquid phase by reacting zinc powder with ZnCl2 at 120°C .

[0226] 1 g of pre-activated zinc powder (activated with 2% HCl), 0.25 g of ZnCl2, 1 g of 253 dB, and 4 g of methanol were added to a 10 ml Hastelloy C autoclave. The autoclave was then cooled to -40 °C and evacuated. It was then heated to 120 °C and maintained at 120 °C with stirring for 16 hours. The reactor pressure was increased to approximately 1040 psig. The reactor was then cooled to room temperature. The vapor fraction of the products from the reactor was analyzed by GC-MS-FID, and the results are listed in Table 8 below.

[0227]

[0228] Example 10: Hydrogenation of HBFO-1233xfB to HBFC-253dbB in the gas phase using 0.5% Pd / Al2O3.

[0229] In a 12-inch ½" OD Monel reactor, 8 ml of 0.5% Pd / Al₂O₃ was loaded. The catalyst was treated with H₂ at 120°C for 1 hour. The reactor was then cooled to 30°C. H₂ and N₂ feeds were controlled by a mass flow controller, and HBFO-1233xfB was fed via a pump. The reaction test conditions are listed in Table 9 below. The reactor effluent was analyzed by online GC-MS-FID at the time points shown in Table 10 below. The analytical results, listed in Table 10 below, show complete high conversion of HBFO-1233xfB and good selectivity for HBFC-253dbB.

[0230]

[0231]

[0232]

[0233] Example 11: Conversion of HBFC-253dbB to HFO-1252zc in the liquid phase by reacting zinc powder with TBAB at 60°C .

[0234] 73 μL of CF3CHBrCH3 was mixed with 50 mg Zn and 40 mg TBAB in 2.5 mL of MeOH in an NMR tube. The mixture was allowed to stand at ambient temperature for several hours, during which time approximately half of the reaction occurred. The second half of the test was performed at 60 °C and recorded by NMR. The results of the NMR analysis during the reaction at 60 °C are shown below. Figure 2 The reaction was clean and produced only about 0.5% byproducts.

[0235] Other implementation plans

[0236] Implementation Scheme 1. A method for preparing a compound of formula (II), the method comprising contacting a compound of formula (I) with hydrogen in the presence of a catalyst, CF3CX=CH2 (I); CF3CHXCH3 (II), wherein X is selected from the group consisting of Cl, Br and I.

[0237] Implementation Scheme 2. A method for preparing HFO-1252zc (CF2=CHCH3), the method comprising contacting a compound of formula (II) with a metal or with hydrogen gas, CF3CHXCH3 (II), wherein X is selected from Cl, Br and I.

[0238] Implementation Scheme 3. A method for preparing HFO-1252zc (CF2=CHCH3), the method comprising: (i) reacting a precursor compound of formula (I) with hydrogen in the presence of a catalyst to convert the precursor compound into an intermediate compound of formula (II), and (ii) reacting the intermediate compound with a metal or with hydrogen to convert the intermediate compound of formula (II) into HFO-1252zc, CF3CX=CH2 (I); CF3CHXCH3 (II), wherein X is selected from the group consisting of Cl, Br and I.

[0239] Implementation Scheme 4. The method according to any one of Implementation Scheme 1 or 3, wherein the compound of Formula (I) is 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf, CF3CCl=CH2), and the compound of Formula (II) is 2-chloro-1,1,1-trifluoropropane (HCFC-253db, CF3CHClCH3).

[0240] Implementation Scheme 5. The method according to any one of Implementation Schemes 1 or 3 to 4, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase or liquid phase.

[0241] Implementation Scheme 6. The method according to any one of Implementation Schemes 1 or 3 to 5, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the presence of a metal-containing catalyst.

[0242] Implementation Scheme 7. The method according to Implementation Scheme 6, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and may or may not have a support.

[0243] Implementation Scheme 8. The method according to Implementation Scheme 7, wherein the carrier is selected from the group consisting of carbon, graphite and metal oxides.

[0244] Implementation Scheme 9. The method according to any one of Implementation Schemes 6 to 8, wherein the catalyst is Pd / Al2O3 or Pd / C.

[0245] Implementation Scheme 10. The method according to any one of Implementation Schemes 1 or 3 to 9, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably from about 0.02 wt% to about 0.05 wt%.

[0246] Implementation Scheme 11. The method according to Implementation Scheme 10, wherein the catalyst is a Pd / Al2O3 catalyst, and wherein preferably, the Pd loading is in the range of 0.01 wt% to 0.05 wt%.

[0247] Implementation Scheme 12. The method according to any one of Implementation Schemes 1 or 3 to 11, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase at a temperature of about 20°C to about 80°C, preferably about 20°C to about 60°C.

[0248] Implementation Scheme 13. The method according to any one of Implementation Schemes 1 or 3 to 12, wherein the molar ratio of hydrogen used for the gas-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 3:1, preferably about 1:1 to about 2:1.

[0249] Implementation Scheme 14. The method according to any one of Implementation Schemes 1 or 3 to 9, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

[0250] Implementation Scheme 15. The method according to Implementation Scheme 14, wherein the catalyst is a Pd / C catalyst, and wherein preferably, the Pd loading is in the range of 0.1 wt% to 10 wt%.

[0251] Implementation Scheme 16. The method according to any one of Implementation Schemes 1, 3 to 9 or 14 to 15, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase at a temperature of about 20°C to about 120°C, preferably about 30°C to about 110°C.

[0252] Implementation Scheme 17. The method according to any one of Implementation Schemes 1, 3 to 9 or 14 to 16, wherein the molar ratio of hydrogen used for the liquid-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 2:1, preferably about 0.8:1 to about 1.2:1.

[0253] Implementation Scheme 18. The method according to any one of Implementation Scheme 1 or 3, wherein the compound of Formula (I) is 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB, CF3CBr=CH2) and the compound of Formula (II) is 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB, CF3CHBrCH3).

[0254] Implementation Scheme 19. The method according to any one of Implementation Schemes 1, 3 or 18, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase or liquid phase.

[0255] Implementation Scheme 20. The method according to any one of Implementation Schemes 1, 3 or 18 to 19, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the presence of a metal-containing catalyst.

[0256] Implementation Scheme 21. The method according to any one of Implementation Schemes 1, 3, or 18 to 20, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, wherein the support is preferably selected from the group consisting of carbon, graphite, and metal oxides.

[0257] Implementation Scheme 22. The method according to Implementation Scheme 21, wherein the catalyst is Pd / Al2O3 or Pd / C.

[0258] Implementation Scheme 23. The method according to any one of Implementation Schemes 1, 3, or 18 to 22, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, preferably from about 0.2 wt% to about 0.8 wt%.

[0259] Implementation Scheme 24. The method according to Implementation Scheme 23, wherein the catalyst is a Pd / Al2O3 catalyst, and wherein preferably, the Pd loading is in the range of 0.1 wt% to 1.0 wt%.

[0260] Implementation Scheme 25. The method according to any one of Implementation Schemes 1, 3 or 18 to 24, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase at a temperature of about 30°C to about 130°C, preferably about 60°C to about 110°C.

[0261] Implementation Scheme 26. The method according to any one of Implementation Schemes 1, 3 or 18 to 25, wherein the molar ratio of hydrogen used for the gas-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 1:1 to about 10:1, preferably about 2:1 to about 8:1.

[0262] Implementation Scheme 27. The method according to any one of Implementation Schemes 1, 3, or 18 to 22, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

[0263] Implementation Scheme 28. The method according to Implementation Scheme 27, wherein the catalyst is a Pd / C catalyst, and wherein preferably, the Pd loading is in the range of 0.1 wt% to 10 wt%.

[0264] Implementation Scheme 29. The method according to any one of Implementation Schemes 1, 3, 18 to 22 or 27 to 28, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase at a temperature of about 40°C to about 120°C, preferably about 60°C to about 100°C.

[0265] Implementation Scheme 30. The method according to any one of Implementation Schemes 1, 3, 18 to 22 or 27 to 29, wherein the molar ratio of hydrogen used for the liquid-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 3:1, preferably about 0.8:1 to about 2:1.

[0266] Implementation Scheme 31. The method according to any one of Implementation Scheme 2 or 3, wherein the compound of Formula (II) is 2-chloro-1,1,1-trifluoropropane (HCFC-253db, CF3CHClCH3) or 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB, CF3CHBrCH3).

[0267] Implementation Scheme 32. The method according to any one of Implementation Schemes 2, 3 or 31, wherein the compound of Formula (II) is contacted with hydrogen in the presence of a catalyst, preferably in the gas phase.

[0268] Implementation Scheme 33. The method according to Implementation Scheme 32, wherein the catalyst comprises a metal catalyst, preferably the catalyst comprises a metal selected from the group consisting of Ni, Cu, Au and combinations thereof and has or does not have a support, wherein preferably the support is selected from the group consisting of carbon, graphite and metal oxides.

[0269] Implementation Scheme 34. The method according to any one of Implementation Schemes 32 to 33, wherein the catalyst is Au / C or Cu / C.

[0270] Implementation Scheme 35. The method according to any one of Implementation Schemes 32 to 34, wherein the amount of catalyst on the support ranges from about 2% by weight to about 10% by weight based on the total weight of the support and the catalyst.

[0271] Implementation Scheme 36. The method according to any one of Implementation Schemes 2, 3 or 31 to 35, wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the gas phase at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C.

[0272] Implementation Scheme 37. The method according to any one of Implementation Schemes 2, 3 or 31 to 36, wherein the molar ratio of hydrogen to the compound of Formula (II) is in the range of about 5:1 to about 40:1, preferably about 10:1 to about 30:1.

[0273] Implementation Scheme 38. The method according to any one of Implementation Schemes 2, 3 or 31, wherein the compound of Formula (II) is contacted with the metal in the absence or presence of a catalyst, preferably in the liquid phase.

[0274] Implementation Scheme 39. The method according to any one of Implementation Schemes 2, 3, 31 or 38, wherein the metal is selected from the group consisting of zinc, magnesium and combinations thereof.

[0275] Implementation Scheme 40. The method according to any one of Implementation Schemes 38 to 39, wherein the metal is acid-activated before contacting the compound of Formula (II).

[0276] Implementation Scheme 41. The method according to any one of Implementation Schemes 38 to 40, wherein the metal comprises zinc that has been activated by HCl.

[0277] Implementation Scheme 42. The method according to any one of Implementation Schemes 2, 3, 31 or 38 to 41, wherein the reaction is carried out in the presence of a catalyst, preferably the catalyst being selected from the group consisting of zinc salts, ammonium salts and phosphonium salts.

[0278] Implementation Scheme 43. The method according to Implementation Scheme 42, wherein the catalyst is selected from the group consisting of zinc acetate, ZnCl2 and tetrabutylammonium bromide.

[0279] Implementation Scheme 44. The method according to any one of Implementation Schemes 2, 3, 31 or 38 to 43, wherein the reaction is carried out in the presence of a solvent, preferably a solvent selected from the group consisting of alcohols, amides, pyridines and ethers, more preferably a solvent containing alcohols selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol.

[0280] Implementation Scheme 45. The method according to any one of Implementation Schemes 2, 3, 31 or 38 to 44, wherein the compound of formula (II) is HCFC-253db, and wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the liquid phase at a temperature of about 50°C to about 180°C, preferably about 80°C to about 150°C.

[0281] Implementation Scheme 46. The method according to any one of Implementation Schemes 2, 3, 31 or 38 to 45, wherein the compound of formula (II) is HBFC-253dbB, and wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the liquid phase at a temperature of about 40°C to about 120°C, preferably about 50°C to about 100°C.

[0282] Implementation Scheme 47. The method according to any one of Implementation Schemes 2, 3, 31 or 38 to 46, wherein the molar ratio of the metal to the compound of Formula (II) is in the range of about 1:1 to about 5:1, preferably about 1.05:1 to about 3:1.

[0283] Implementation Scheme 48. A method for preparing HCFC-253db, the method comprising contacting HCFO-1233xf with hydrogen in the presence of a catalyst.

[0284] Implementation Scheme 49. The method according to Implementation Scheme 48, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably from about 0.02 wt% to about 0.05 wt%.

[0285] Implementation Scheme 50. The method according to Implementation Scheme 48, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

[0286] Implementation Scheme 51. A method for preparing HBFC-253dbB, the method comprising contacting HBFO-1233xfB with hydrogen in the presence of a catalyst.

[0287] Implementation Scheme 52. The method according to Implementation Scheme 51, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, preferably from about 0.2 wt% to about 0.8 wt%.

[0288] Implementation Scheme 53. The method according to Implementation Scheme 51, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

[0289] Implementation Scheme 54. A method for preparing HFO-1252zc, the method comprising contacting HCFC-253db or HBFC-253dbB with a metal in the absence or presence of a catalyst and / or solvent, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

[0290] Implementation Scheme 55. The method according to Implementation Scheme 54, wherein the metal is acid-activated before contacting the compound of Formula (II).

[0291] Implementation Scheme 56. The method according to any one of Implementation Schemes 54 to 55, wherein the metal comprises zinc that has been activated by HCl.

[0292] Implementation Scheme 57. The method according to any one of Implementation Schemes 54 to 56, wherein the reaction is carried out in the presence of a catalyst, preferably selected from the group consisting of zinc salts, ammonium salts and phosphonium salts, and more preferably selected from the group consisting of zinc acetate, ZnCl2 and tetrabutylammonium bromide.

[0293] Implementation Scheme 58. The method according to any one of Implementation Schemes 54 to 57, wherein the reaction is carried out in the presence of a solvent, preferably a solvent selected from the group consisting of alcohols, amides, pyridines and ethers, more preferably a solvent containing alcohols selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol.

[0294] Implementation Scheme 59. A method for preparing HFO-1252zc, the method comprising contacting HCFC-253db or HBFC-253dbB with hydrogen in the presence of a catalyst.

[0295] Implementation Scheme 60. The method according to Implementation Scheme 59, wherein the catalyst comprises a metal catalyst, preferably the catalyst comprises a metal selected from the group consisting of Ni, Cu, Au and combinations thereof and has or does not have a support, wherein preferably the support is selected from the group consisting of carbon, graphite and metal oxides.

[0296] Implementation Scheme 61. The method according to any one of Implementation Schemes 59 to 60, wherein the catalyst is Au / C or Cu / C.

[0297] Implementation Scheme 62. The method according to any one of Implementation Schemes 59 to 61, wherein the amount of catalyst on the support ranges from about 2% by weight to about 10% by weight based on the total weight of the support and the catalyst.

[0298] Implementation Scheme 63. A method for preparing HFO-1252zc, the method comprising: (i) converting HCFO-1233xf to HCFC-253db by reacting HCFO-1233xf with hydrogen in the presence of a catalyst, and (ii) converting HCFC-253db to HFO-1252zc by reacting HCFC-253db with a metal in the absence of a catalyst or in the presence of a solvent, or with hydrogen in the presence of a catalyst, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

[0299] Implementation Scheme 64. A method for preparing HFO-1252zc, the method comprising: (i) converting HBFO-1233xfB to HBFC-253dbB by reacting HBFO-1233xfB with hydrogen in the presence of a catalyst, and (ii) converting HBFC-253dbB to HFO-1252zc by reacting HBFC-253dbB with a metal in the absence of a catalyst and / or in the presence of a solvent, or by reacting HBFC-253dbB with hydrogen in the presence of a catalyst, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

[0300] Implementation Scheme 65. A system comprising a source of HCFO-1233xf and hydrogen or a source of HBFO-1233xfB and hydrogen, a first reactor and a second reactor for carrying out different reactions, optionally at least one mixer connected to the first reactor for premixing reactants comprising hydrogen and HCFO-1233xf or hydrogen and HBFO-1233xfB, the second reactor being disposed downstream of the first reactor, wherein the first reactor produces a first intermediate product mixture, and the second reactor converts the intermediate product produced in the first reactor, wherein the first reactor is configured to operate in a gas phase or a liquid phase, and the second reactor is configured to operate in a gas phase or a liquid phase.

[0301] Implementation Scheme 66. The system according to Implementation Scheme 65, wherein unreacted HCFO-1233xf or HBFO-1233xfB from the first reactor is recycled.

[0302] Implementation Scheme 67. A method for converting HCFO-1233xf or HBFO-1233xfB into HFO-1252zc using a system according to any one of Implementation Schemes 65 to 66.

[0303] Implementation Scheme 68. A composition comprising, substantially comprising, or comprising of the following compounds selected from the group consisting of: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261zc). e) Pentafluorobutene isomers (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0304] Implementation Scheme 69. The composition according to Implementation Scheme 68, wherein the composition comprises HFC-263fb and HCFC-253db.

[0305] Implementation Scheme 70. The composition according to Implementation Scheme 68, wherein the composition comprises HCFO-1233xf, HFC-263fb and HCFC-253db.

[0306] Implementation Scheme 71. The composition according to Implementation Scheme 68, wherein the composition comprises HFC-263fb, HCFO-1233xf and HCFC-253db.

[0307] Implementation Scheme 72. The composition according to Implementation Scheme 68, wherein the composition comprises HFO-1252zc, HFC-263fb, HCFO-1233xf and HCFC-253db.

[0308] Implementation Scheme 73. The composition according to Implementation Scheme 68, wherein the composition comprises HFC-263fb and HBFC-253dbB.

[0309] Implementation Scheme 74. The composition according to Implementation Scheme 68, wherein the composition comprises HFC-263fb, HBFO-1233xfB and HBFC-253dbB.

[0310] Implementation Scheme 75. The composition according to Implementation Scheme 68, wherein the composition comprises HFO-1252zc, HFC-263fb, HBFO-1233xfB and HBFC-253dbB.

[0311] Implementation Scheme 76. The composition according to Implementation Scheme 68, wherein the composition comprises HCFO-1233xf, HFC-263fb, HFC-244bb and HFC-253db.

[0312] Implementation Scheme 77. A composition comprising HFO-1252zc and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc and one or more compounds selected from the group consisting of: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HF O-1252), 1-fluoropropene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0313] Implementation Scheme 78. A composition comprising HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), difluoropropylene isomer The following are listed: 1-fluoropropene (HFO-1252), 1-fluoropropene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0314] Implementation Scheme 79. A composition comprising HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoro Propylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropylene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropylene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropylene (HBFO-1242xfB), 3-chloro-3,3-difluoropropylene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropylene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0315] Implementation Scheme 80. A composition comprising HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of: propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer The following compounds are listed: 1-fluoropropene (HFO-1252), 1-fluoropropene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

[0316] Implementation Scheme 81. A composition comprising HBFO-1233xfB and one or more compounds selected from the group consisting of, substantially consisting of HBFO-1233xfB and one or more compounds selected from the group consisting of, or consisting of HBFO-1233xfB and one or more compounds selected from the group consisting of: propane, 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1-trifluoropropane (HFC-263fb), dichloromethane (HCC-3 0), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), tetrafluorobutane (HFC-374), chlorofluoropropene (HCFO-1251), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3-difluoropropene (HBFO-1242xfB), dichlorotrifluoropropane isomer (HCFC-243), and dibromotrifluoropropane (C3H3Br2F3).

[0317] While certain aspects, embodiments, and principles have been described above, it should be understood that this description is exemplary only and not intended to limit the invention or the appended claims. The various aspects, embodiments, and principles described above can be used individually or in combination with each other.

Claims

1. A method for preparing a compound of formula (II), the method comprising contacting a compound of formula (I) with hydrogen gas in the presence of a catalyst, CF3CX=CH2 (I) CF3CHXCH3 (II) X is selected from the group consisting of Cl, Br, and I.

2. A method for preparing HFO-1252zc (CF2=CHCH3), said method comprising contacting a compound of formula (II) with a metal or with hydrogen gas, CF3CHXCH3 (II) X is selected from the group consisting of Cl, Br, and I.

3. A method for preparing HFO-1252zc (CF2=CHCH3), the method comprising: (i) The precursor compound of formula (I) is converted into the intermediate compound of formula (II) by reacting the precursor compound with hydrogen in the presence of a catalyst, and (ii) The intermediate compound of formula (II) is converted into HFO-1252zc by reacting the intermediate compound with a metal or with hydrogen. CF3CX=CH2 (I) CF3CHXCH3 (II) X is selected from the group consisting of Cl, Br, and I.

4. The method according to any one of claims 1 or 3, wherein the compound of formula (I) is 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf, CF3CCl=CH2), and the compound of formula (II) is 2-chloro-1,1,1-trifluoropropane (HCFC-253db, CF3CHClCH3).

5. The method according to any one of claims 1 or 3 to 4, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase or liquid phase.

6. The method according to any one of claims 1 to 5, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the presence of a metal-containing catalyst.

7. The method of claim 6, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof, and may or may not have a support.

8. The method according to claim 7, wherein the support is selected from the group consisting of carbon, graphite and metal oxides.

9. The method according to any one of claims 6 to 8, wherein the catalyst is Pd / Al2O3 or Pd / C.

10. The method according to any one of claims 1 to 9, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably from about 0.02 wt% to about 0.05 wt%.

11. The method of claim 10, wherein the catalyst is a Pd / Al2O3 catalyst, and wherein preferably, the Pd loading is in the range of 0.01 wt% to 0.05 wt%.

12. The method according to any one of claims 1 or 3 to 11, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase at a temperature of about 20°C to about 80°C, preferably about 20°C to about 60°C.

13. The method according to any one of claims 1 or 3 to 12, wherein the molar ratio of hydrogen used for the gas-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 3:1, preferably about 1:1 to about 2:

1.

14. The method according to any one of claims 1 to 9, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

15. The method of claim 14, wherein the catalyst is a Pd / C catalyst, and wherein preferably, the Pd loading is in the range of 0.1% by weight to 10% by weight.

16. The method according to any one of claims 1, 3 to 9 or 14 to 15, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase at a temperature of about 20°C to about 120°C, preferably about 30°C to about 110°C.

17. The method according to any one of claims 1, 3 to 9 or 14 to 16, wherein the molar ratio of hydrogen used for the liquid-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 2:1, preferably about 0.8:1 to about 1.2:

1.

18. The method according to any one of claims 1 or 3, wherein the compound of formula (I) is 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB, CF3CBr=CH2), and the compound of formula (II) is 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB, CF3CHBrCH3).

19. The method according to any one of claims 1, 3 or 18, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase or liquid phase.

20. The method according to any one of claims 1, 3 or 18 to 19, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the presence of a metal-containing catalyst.

21. The method according to any one of claims 1, 3, or 18 to 20, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, wherein the support is preferably selected from the group consisting of carbon, graphite, and metal oxides.

22. The method according to claim 21, wherein the catalyst is Pd / Al2O3 or Pd / C.

23. The method according to any one of claims 1, 3, or 18 to 22, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, preferably from about 0.2 wt% to about 0.8 wt%.

24. The method of claim 23, wherein the catalyst is a Pd / Al2O3 catalyst, and wherein preferably, the Pd loading is in the range of 0.1 wt% to 1.0 wt%.

25. The method according to any one of claims 1, 3 or 18 to 24, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the gas phase at a temperature of about 30°C to about 130°C, preferably about 60°C to about 110°C.

26. The method according to any one of claims 1, 3 or 18 to 25, wherein the molar ratio of hydrogen used for the gas-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 1:1 to about 10:1, preferably about 2:1 to about 8:

1.

27. The method according to any one of claims 1, 3, or 18 to 22, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase in the presence of a catalyst, wherein preferably the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au, and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

28. The method of claim 27, wherein the catalyst is a Pd / C catalyst, and wherein preferably, the Pd loading is in the range of 0.1% by weight to 10% by weight.

29. The method according to any one of claims 1, 3, 18 to 22 or 27 to 28, wherein the conversion of the compound of formula (I) to the compound of formula (II) is carried out in the liquid phase at a temperature of about 40°C to about 120°C, preferably about 60°C to about 100°C.

30. The method according to any one of claims 1, 3, 18 to 22 or 27 to 29, wherein the molar ratio of hydrogen used for the liquid-phase conversion of the compound of formula (I) to the compound of formula (II) is in the range of about 0.5:1 to about 3:1, preferably about 0.8:1 to about 2:

1.

31. The method according to any one of claims 2 or 3, wherein the compound of formula (II) is 2-chloro-1,1,1-trifluoropropane (HCFC-253db, CF3CHClCH3) or 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB, CF3CHBrCH3).

32. The method according to any one of claims 2, 3 or 31, wherein the compound of formula (II) is contacted with hydrogen in the presence of a catalyst, preferably in the gas phase.

33. The method of claim 32, wherein the catalyst comprises a metal catalyst, preferably the catalyst comprises a metal selected from the group consisting of Ni, Cu, Au and combinations thereof and has or does not have a support, wherein preferably the support is selected from the group consisting of carbon, graphite and metal oxides.

34. The method according to any one of claims 32 to 33, wherein the catalyst is Au / C or Cu / C.

35. The method according to any one of claims 32 to 34, wherein the amount of catalyst on the support ranges from about 2% by weight to about 10% by weight, based on the total weight of the support and the catalyst.

36. The method according to any one of claims 2, 3 or 31 to 35, wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the gas phase at a temperature of about 200°C to about 500°C, preferably about 300°C to about 450°C.

37. The method according to any one of claims 2, 3 or 31 to 36, wherein the molar ratio of hydrogen to the compound of formula (II) is in the range of about 5:1 to about 40:1, preferably about 10:1 to about 30:

1.

38. The method according to any one of claims 2, 3 or 31, wherein the compound of formula (II) is contacted with the metal in the absence or presence of a catalyst, preferably in the liquid phase.

39. The method according to any one of claims 2, 3, 31 or 38, wherein the metal is selected from the group consisting of zinc, magnesium and combinations thereof.

40. The method according to any one of claims 38 to 39, wherein the metal is acid-activated prior to contact with the compound of formula (II).

41. The method according to any one of claims 38 to 40, wherein the metal comprises zinc that has been activated by HCl.

42. The method according to any one of claims 2, 3, 31 or 38 to 41, wherein the reaction is carried out in the presence of a catalyst, preferably the catalyst being selected from the group consisting of zinc salts, ammonium salts and phosphonium salts.

43. The method according to claim 42, wherein the catalyst is selected from the group consisting of zinc acetate, ZnCl2 and tetrabutylammonium bromide.

44. The method according to any one of claims 2, 3, 31 or 38 to 43, wherein the reaction is carried out in the presence of a solvent, preferably a solvent selected from the group consisting of alcohols, amides, pyridines and ethers, more preferably a solvent containing alcohols selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol.

45. The method according to any one of claims 2, 3, 31 or 38 to 44, wherein the compound of formula (II) is HCFC-253db, and wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the liquid phase at a temperature of about 50°C to about 180°C, preferably about 80°C to about 150°C.

46. ​​The method according to any one of claims 2, 3, 31 or 38 to 45, wherein the compound of formula (II) is HBFC-253dbB, and wherein the conversion of the compound of formula (II) to HFO-1252zc is carried out in the liquid phase at a temperature of about 40°C to about 120°C, preferably about 50°C to about 100°C.

47. The method according to any one of claims 2, 3, 31 or 38 to 46, wherein the molar ratio of the metal to the compound of formula (II) is in the range of about 1:1 to about 5:1, preferably about 1.05:1 to about 3:

1.

48. A method for preparing HCFC-253db, the method comprising contacting HCFO-1233xf with hydrogen in the presence of a catalyst.

49. The method of claim 48, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 0.1 wt%, preferably from about 0.02 wt% to about 0.05 wt%.

50. The method of claim 48, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.01 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

51. A method for preparing HBFC-253dbB, the method comprising contacting HBFO-1233xfB with hydrogen in the presence of a catalyst.

52. The method of claim 51, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 1.0 wt%, preferably from about 0.2 wt% to about 0.8 wt%.

53. The method of claim 51, wherein the catalyst comprises a metal selected from the group consisting of Pd, Pt, Ni, Cu, Au and combinations thereof and has or does not have a support, and wherein preferably, based on the total weight of the support and the catalyst, the amount of catalyst on the support ranges from about 0.1 wt% to about 10 wt%, preferably from about 0.4 wt% to about 6 wt%.

54. A method for preparing HFO-1252zc, the method comprising contacting HCFC-253db or HBFC-253dbB with a metal in the absence or presence of a catalyst and / or solvent, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

55. The method of claim 54, wherein the metal is acid-activated prior to contact with the compound of formula (II).

56. The method according to any one of claims 54 to 55, wherein the metal comprises zinc that has been activated by HCl.

57. The method according to any one of claims 54 to 56, wherein the reaction is carried out in the presence of a catalyst, preferably selected from the group consisting of zinc salts, ammonium salts and phosphonium salts, and more preferably selected from the group consisting of zinc acetate, ZnCl2 and tetrabutylammonium bromide.

58. The method according to any one of claims 54 to 57, wherein the reaction is carried out in the presence of a solvent, preferably a solvent selected from the group consisting of alcohols, amides, pyridines and ethers, more preferably a solvent containing alcohols selected from the group consisting of methanol, ethanol, propanol, isopropanol and ethylene glycol.

59. A method for preparing HFO-1252zc, the method comprising contacting HCFC-253db or HBFC-253dbB with hydrogen in the presence of a catalyst.

60. The method of claim 59, wherein the catalyst comprises a metal catalyst, preferably the catalyst comprises a metal selected from the group consisting of Ni, Cu, Au and combinations thereof and has or does not have a support, wherein preferably the support is selected from the group consisting of carbon, graphite and metal oxides.

61. The method according to any one of claims 59 to 60, wherein the catalyst is Au / C or Cu / C.

62. The method according to any one of claims 59 to 61, wherein the amount of catalyst on the support ranges from about 2% by weight to about 10% by weight, based on the total weight of the support and the catalyst.

63. A method for preparing HFO-1252zc, the method comprising: (i) Converting HCFO-1233xf to HCFC-253db by reacting HCFO-1233xf with hydrogen in the presence of a catalyst, and (ii) The HCFC-253db is converted into HFO-1252zc by reacting the HCFC-253db with a metal in the absence or presence of a catalyst and / or solvent, or by reacting the HCFC-253db with hydrogen in the presence of a catalyst, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

64. A method for preparing HFO-1252zc, the method comprising: (i) Converting HBFO-1233xfB to HBFC-253dbB by reacting HBFO-1233xfB with hydrogen in the presence of a catalyst, and (ii) The HBFC-253dbB is converted into HFO-1252zc by reacting the HBFC-253dbB with a metal in the absence or presence of a catalyst and / or solvent, or by reacting the HBFC-253dbB with hydrogen in the presence of a catalyst, wherein the metal is selected from the group consisting of zinc, magnesium, and combinations thereof.

65. A system comprising a source of HCFO-1233xf and hydrogen or a source of HBFO-1233xfB and hydrogen, a first reactor and a second reactor for carrying out different reactions, optionally at least one mixer connected to the first reactor for premixing reactants comprising hydrogen and HCFO-1233xf or hydrogen and HBFO-1233xfB, the second reactor being disposed downstream of the first reactor, wherein the first reactor produces a first intermediate product mixture, and the second reactor converts the intermediate product produced in the first reactor, wherein the first reactor is configured to operate in a gas phase or a liquid phase, and the second reactor is configured to operate in a gas phase or a liquid phase.

66. The system of claim 65, wherein unreacted HCFO-1233xf or HBFO-1233xfB from the first reactor is recycled.

67. A method for converting HCFO-1233xf or HBFO-1233xfB into HFO-1252zc using the system according to any one of claims 65 to 66.

68. A composition comprising, substantially comprising, or comprising of one or more compounds selected from the group consisting of: Propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1,1-difluoropropylene (HFO-1252zc), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, Butane, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

69. The composition of claim 68, wherein the composition comprises HFC-263fb and HCFC-253db.

70. The composition of claim 68, wherein the composition comprises HCFO-1233xf, HFC-263fb and HCFC-253db.

71. The composition of claim 68, wherein the composition comprises HFC-263fb, HCFO-1233xf, and HCFC-253db.

72. The composition of claim 68, wherein the composition comprises HFO-1252zc, HFC-263fb, HCFO-1233xf, and HCFC-253db.

73. The composition of claim 68, wherein the composition comprises HFC-263fb and HBFC-253dbB.

74. The composition of claim 68, wherein the composition comprises HFC-263fb, HBFO-1233xfB and HBFC-253dbB.

75. The composition of claim 68, wherein the composition comprises HFO-1252zc, HFC-263fb, HBFO-1233xfB and HBFC-253dbB.

76. The composition of claim 68, wherein the composition comprises HCFO-1233xf, HFC-263fb, HFC-244bb and HFC-253db.

77. A composition comprising HFO-1252zc and one or more compounds selected from the group consisting of, substantially consisting of HFO-1252zc and one or more compounds selected from the group consisting of, or consisting of HFO-1252zc and one or more compounds selected from the group consisting of: Propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3, 3-Trifluoropropene (HCFO-1233xf), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

78. A composition comprising HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFO-1243zf and one or more compounds selected from the group consisting of: Propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), difluoropropylene isomer (HFO-1252), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropylene (HCFO) 1,2-dichloro-1,1,1-difluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

79. A composition comprising HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFO-1261ze and one or more compounds selected from the group consisting of: Propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), 1,1,1-trifluoropropane (HFC-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropene (HFO-1243zf), difluoropropene isomer (HFO-1252), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFC-243), difluoropropene isomer (HCFC-243), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFC-253db), 1,1,1-trifluoropropane (HFO-263fb), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropene (HFO-1243zf), difluoropropene isomer (HFO-1252), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropene (HCFC-243), dichlorotrifluoropropene (HCFC-253db), 1,1,1-trifluoropropene (HCFC-253db), 1,1,1-trifluoropropene (HFO-263fb), dichlorotrifluoroethylene (E-HFO-243 ... 2-Bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-Bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

80. A composition comprising HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of, substantially consisting of, HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of, or consisting of, HFO-1252zc, HFC-263fb and one or more compounds selected from the group consisting of: Propylene, propane, dichlorotrifluoropropane isomer (HCFC-243), 2-chloro-1,1,1-trifluoropropane (HCFC-253db), E-1,2-difluoroethylene (E-HFO-1132), Z-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropylene (HFO-1243zf), difluoropropylene isomer (HFO-1252), 1-fluoropropylene (HFO-1261ze), pentafluorobutene isomer (HFO-1345), 2-butene, butane, 2-chloro-3,3,3-trifluoropropylene (HCFO) 1,2-dichloro-1,1,1-difluoropropane (HBFC-253dbB), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), methanol, acetone, propane, propylene, 2-methoxy-propane, 2-chloropropane, 2-bromo-1,1-difluoropropene (HBFO-1242xfB), 3-chloro-3,3-difluoropropene (HCFO-1242zf), 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf), and 1,2-dichloro-1,1-difluoropropane (HCFC-252dc).

81. A composition comprising HBFO-1233xfB and one or more compounds selected from the group consisting of, substantially consisting of HBFO-1233xfB and one or more compounds selected from the group consisting of, or consisting of HBFO-1233xfB and one or more compounds selected from the group consisting of: Propane, 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1-trifluoropropane (HFC-263fb), dichloromethane (HCC-30), 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), tetrafluorobutane (HFC-374), chlorofluoropropene (HCFO-1251), 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB), 2-bromo-1,1,1-trifluoropropane (HBFC-253dbB), 2-bromo-3,3-difluoropropene (HBFO-1242xfB), dichlorotrifluoropropane isomer (HCFC-243), and dibromotrifluoropropane (C3H3Br2F3).

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