PROCESS TO PRODUCE 1,1,2-TRIFLUOROPROPENE (HFO-1243yc)

Abstract

A process includes contacting a compound of formula CF2X-CFY-CH3 with an activated zinc powder, where X is selected from Cl and F and Y is selected from Cl, Br and l. The process also includes producing a product mixture including 1,1,2-trifluoropropene (HFO-1243yc). The process may be a one-step process, a two-step process, or a three-step process. A product mixture includes 1,1,2-trifluoropropene (HFO-1243yc).

Description

TS0074-W001TITLE PROCESS TO PRODUCE 1 ,1 ,2-TRIFLUOROPROPENE (HFO-1243yc) CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of U.S. Provisional Application 63 / 756,391 filed February 10, 2025, and U.S. Provisional Application 63 / 799,818 filed May 5, 2025, the disclosure of each of which is incorporated herein by reference it its entirety.FIELD

[0002] The present disclosure relates to processes of producing olefins. More specifically, the present disclosure relates to processes of producing 1,1,2-trifluoropropene (CH3-CF=CF2; HFO-1243yc).BACKGROUND

[0003] Hydrofluoroolefins (HFOs) having low ozone depletion potential (ODP) and low global warming potential (GWP) have been replacing saturated CFCs (chlorofluorocarbons), HCFCs (hydrochlorofluorocarbons), and HFCs (hydrofluorocarbons) in a variety of applications for several years, because saturated hydrohalocarbons tend to have high GWP values. For example, HFC-32 (CH2F2), HFC-125 (C2HF5), and HFC-134a (CH2FCF3) have GWPs of 675, 3500, and 1430, respectively. As a result, low ODP and low GWP materials continue to be of interest for uses, such as, for example, as next generation refrigerants (NGRs), solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids.

[0004] Although HFCs do not contribute to the destruction of stratospheric ozone, they contribute to the "greenhouse effect", i.e., global warming. As a result of their contribution to global warming, HFCs have come under scrutiny, and their widespread use may also be limited in the future.

[0005] This regulatory landscape is continuously evolving, taking into consideration properties beyond just ODP and GWP. More particularly, there is a need for refrigerant compositions that not only meet low ODP standards and haveTS0074-W001low global warming potentials, but that also exhibit low or no flammability, provide superior performance in a variety of applications and which meet the standards of evolving regulations.

[0006] There is a need in this art for new refrigerants that meet evolving regulations as well as provide heat transfer and refrigerant characteristics that meet or exceed the effectiveness of conventional refrigerants, as well as processes for making these refrigerants. One such candidate is 1,1,2-trifluoropropene (CH3-CF=CF2; HFO-1243yc), for example.SUMMARY

[0007] In an example embodiment, a process comprises contacting a compound of formula CF2X-CFY-CH3 with a zinc powder, wherein X is selected from Cl and F and Y is selected from Cl, Br and I; and producing a product mixture or composition comprising 1,1,2-trifluoropropene (HFO-1243yc).

[0008] In one embodiment, in the formula CF2X-CFY-CH3, X is F and Y is Cl. That is, in one embodiment, the compound of formula CF2X-CFY-CH3 is 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC-244bb, CF3CFCICH3). In one embodiment, in the formula CF2X-CFY-CH3, X is F and Y is Br. That is, in one embodiment, the compound of formula CF2X-CFY-CH3 is 2-bromo-1,1,1,2-tetrafluoropropane (HBFC-244bbB, CFsCFBrCHs). In one embodiment, in the formula CF2X-CFY-CH3, X is Cl and Y is Cl. That is, in one embodiment, the compound of formula CF2X-CFY-CH3 is 1,2-dichloro-1 ,1 ,2-trifluoropropane (CCIF2CCIFCH3C, HCFC-243bc).

[0009] In another example embodiment, a process comprises contacting 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB, CF3CBr=CH2) with hydrogen fluoride and producing a product mixture or composition comprising HBFC-244bbB.

[0010] In another example embodiment, a process comprises contacting 2,3-dibromo-1,1,1,2-tetrafluoropropane (CFsCFBrCF Br, HBFC-234baB) with hydrogen (H2) and producing a product mixture or composition comprising HBFC-244bbB.

[0011] In another example embodiment, a process comprises contacting 2, 3,3,3-tetrafluoropropene (HFO-1234yf, CF3CF=CH2) with bromine (B ) and producing a product mixture or composition comprising HBFC-234baB.TS0074-W001

[0012] In another example embodiment, a process comprises contacting 2,3-dichlroo-3,3-difluoropropene (CCIF2CCI=CH2, HCFO-1232xf) with hydrogen fluoride and producing a product mixture or composition comprising HCFC-243bc.

[0013] In another example embodiment, a process comprises contacting 1, 1,2,3-tetrachloropropene (CCl2=CCICH2CI, HCO-1230xa) with hydrogen fluoride and producing a product mixture or composition comprising 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf).

[0014] In another example embodiment, a product mixture or composition is formed by any of the processes disclosed herein.

[0015] Other features and advantages of the present invention will be apparent from the following more detailed description.DETAILED DESCRIPTION

[0016] In some embodiments of the invention, a process produces 1,1,2-trifluoropropene (HFO-1243yc) from a compound of formula CF2X-CFY-CH3, where X is selected from Cl and F and Y is selected from Cl, Br and I.

[0017] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having”, or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

[0018] The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consists of” appears in a clause of the body of a claim,TS0074-W001rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0019] The transitional phrase “consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.

[0020] Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising”, it should be readily understood that (unless otherwise stated) the description should be interpreted to also include such an invention using the terms “consisting essentially of” or “consisting of”.

[0021] Also, the terms “a” and “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0022] Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range. Moreover, all ranges set forth herein are intended to include not only the particular ranges specifically described, but also any combination of values therein, including the minimum and maximum values recited.

[0023] When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, theTS0074-W001range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0024] As used herein, the gas chromatography-mass spectrometry with a flame ionization detector (GC-MS-FID) peak area correlates to the amount of a compound present as a proportion of the total area of all detected peaks. FID area% can be converted to mol% using a response factor either calculated or measured.

[0025] As used herein, the term “about” in certain embodiments can be quantified to mean ± 1%, ± 2%, ± 3% and up to and including ±10% of the stated value, and all whole numbers and fractions therebetween.TABLE OF COMPOUNDS

[0026] By way of example, mention is made of the following compounds:

[0027] Some of the compounds present in the compositions of the present invention identified in the Table of Compounds may exist as different configurational isomers or stereoisomers. The present invention is intended to include all single configurational isomers, single stereoisomers, or any combination or mixture thereof. For instance, 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) exists as a Z-isomer, an E-isomer, or any combination or mixture of both isomers in any ratio. Single isomers or multiple isomers of the same compound may be used in any proportion.TS0074-W001First Embodiment

[0028] In a first embodiment, a process includes contacting a compound of formula CF2X-CFY-CH3 with a metal, where X is selected from Cl and F and Y is selected from Cl, Br and I. The process also includes producing a product mixture or composition including HFO-1243yc.

[0029] In some embodiments, the metal is a reactive metal. As used herein, reactive metal refers to reactive metals such as magnesium turnings, activated zinc powder, aluminum, and a powder of any of the following metals: magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc, indium, and combinations thereof. Magnesium turnings are pieces of magnesium which are cut to produce small pieces with higher surface areas and generally low amounts of surface oxides (which reduce reactivity). In some embodiments, the reactive metal powders of magnesium, calcium, titanium, iron, cobalt, nickel, copper, zinc and indium are Rieke metals, which are prepared by a specific procedure which produces high surface area metal powders which are very reactive in reactions such as those of the present invention. Without wishing to be bound by any particular theory, Rieke metals are thought to be highly reactive because they have high surface areas and lack passivating surface oxides.

[0030] In some embodiments, the metal is selected from zinc, magnesium, cadmium, and combinations thereof. In one embodiment, the metal is zinc. In one embodiment, the metal is zinc powder. In some embodiment, the metal is activated zinc powder.

[0031] In some embodiments, the metal is activated by an acid, and more particularly is activated by contact with an acid before used for reaction with the compound of formula CF2X-CFY-CH3. In some embodiments, the zinc is activated by an acid, such as HCI. In some embodiments, the activated zinc powder is activated by aqueous hydrochloric acid and dried. In some embodiments, the activation is carried out by washing zinc powder with aqueous hydrochloric acid having a concentration of 1 M to about 5 M. In some embodiments, the activation also includes washing the zinc powder with water and acetone prior to the drying. In some embodiments, the drying occurs under nitrogen (N2). In some embodiments, the drying includes vacuum drying. In certain embodiments disclosed herein, zincTS0074-W001powder is activated with HCI (e.g., aqueous or in an alcohol) and is then used to convert a compound of formula CF2X-CFY-CH3 to HFO-1243yc.

[0032] In some embodiments, the contacting occurs in the presence of a catalyst.

[0033] In some embodiments, the contacting occurs in the presence of a solvent.

[0034] In some embodiments, the contacting occurs in the presence of a catalyst and a solvent.

[0035] In some embodiments, the solvent is a polar protic solvent or polar aprotic solvent. In some embodiments, the solvent is selected from alcohol, amide, pyridine and ether. In certain embodiments disclosed herein, the solvent comprises an alcohol selected from methanol, ethanol, propanol, isopropanol and ethylene glycol. In some embodiments, the solvent is dried methanol. In some embodiments, the solvent comprises an amide selected from dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylacetamide (DMAC).

[0036] In some embodiments, the catalyst is selected from zinc salt, ammonium salt and phosphonium salt. In some embodiments, the catalyst comprises a zinc salt selected from zinc acetate and zinc chloride. In some embodiments, the catalyst comprises an ammonium salt, such as tetrabutylammonium bromide (TBAB). It will be understood by those skilled in the art that any suitable salt which is soluble in the solvent of the reaction may be utilized as the catalyst.

[0037] In some embodiments, the mole ratio of organic (e.g., compound of formula CF2X-CFY-CH3) to metal is from about 0.8:1 to about 1 :3, or about 1 : 1 to about 1 :3, preferably about 1 :2, or preferably about 1:1.2. In some embodiments, the mole ratio of organic (e.g., compound of formula CF2X-CFY-CH3) to catalyst is from about 0.8:1 to about 1:3, or about 1:1 to about 1:3, preferably about 1:2, or preferably about 1:1.2. In some embodiments, the mole ratio of metal to catalyst is from about 0.8:1 to about 1:3, or about 1 :1 to about 1:3, preferably about 1:2, or preferably about 1:1.2.

[0038] In some embodiments, the compound of formula CF2X-CFY-CH3, the metal, the catalyst, and the solvent are added to a reactor and the reactor is sealed. The reactor may operate in batch, semi-batch, continuous or semi-continuous modes. In some embodiments, the reactor is an autoclave.TS0074-W001

[0039] In some embodiments, the method further comprises an optional step of cooling the reactor to a reduced temperature, for example to remove the air or inert gases from the reactor without losing the solvent which has already been charged into the reactor and to facilitate the vapor transfer of CF2X-CFY-CH3 material into reactor. In some embodiments, the method further comprises removing the air or inert gases from the reactor by vacuum.

[0040] In some embodiments, an appropriate temperature for the cooling may include, but is not limited to, 0 to -60°C, alternatively -20 to -60°C, alternatively -30 to -50°C, alternatively -35 to -45°C, alternatively about -40°C, or any value, range, or sub-range therebetween.

[0041] In some embodiments, the process does not involve the optional cooling step. In such embodiments, the process may be carried out, for example, by first loading the metal and catalyst into the reactor, removing the air or inert gases from the reactor by vacuum, and then charging solvent and the CF2X-CFY-CH3 feed material into the reactor.

[0042] According to the present invention, the method further comprises heating the reaction mixture to a reaction temperature and preferably agitating the reaction mixture in the reactor for a reaction time to effect dehalogenation of the compound of formula CF2X-CFY-CH3 to HFO-1243yc.

[0043] In some embodiments, an appropriate reaction temperature may include, but is not limited to, about 60°C to about 200°C, alternatively about 70°C to about 190°C, alternatively about 80°C to about 180°C, alternatively about 90°C to about 170°C, alternatively about 100°C to about 160°C, alternatively about 110°C to about 150°C, alternatively about 120°C to about 140°C, or any value, range, or sub-range therebetween.

[0044] In some embodiments, an appropriate reaction time may include, but is not limited to, 1 to 24 hours, alternatively 5 to 15 hours, alternatively 8 to 12 hours, alternatively 9 to 11 hours, alternatively about 10 hours, or any value, range, or subrange therebetween.

[0045] In some embodiments, the reaction begins at a reaction pressure of about 0 psig, and the reaction pressure in the sealed reactor is measured to monitor theTS0074-W001progress of the reaction. In some embodiments, the pressure in the sealed reactor increases over time, which is indicative of the progress of the reaction. In some embodiments, the reaction is run until a predetermined reaction pressure is reached. An appropriate reaction pressure at which to stop the reaction may include, but is not limited to, about 80 psig to about 1500 psig, about 100 psig to about 1500 psig, about 200 psig to about 1500 psig, about 300 psig to about 1500 psig, about 400 psig to about 1500 psig, about 500 psig to about 1500 psig, at least about 80 psig, at least about 100 psig, at least about 150 psig, at least about 200 psig, at least about 250 psig, at least about 300 psig, at least about 350 psig, at least about 400 psig, at least about 450 psig, at least about 500 psig, at least about 550 psig, at least about 600 psig, at least about 650 psig, at least about 700 psig, at least about 750 psig, at least about 800 psig, at least about 850 psig, at least about 900 psig, at least about 950 psig, at least about 1000 psig, at least about 1050 psig, at least about 1100 psig, at least about 1150 psig, at least about 1200 psig, at least about 1250 psig, at least about 1300 psig, at least about 1350 psig, at least about 1400 psig, at least about 1450 psig, or any value, range, or sub-range therebetween. In some embodiments, the reaction pressure is measured during the producing to monitor progression of the dehalogenation reaction. In some embodiments, the reaction runs until the pressure increase reaches a plateau which indicates the end of the reaction.

[0046] In some embodiments, where the process is carried out continuously, the target product (e.g., HFO-1243yc) is continuously removed from the reactor, for example through an overhead condenser which keeps the CF2X-CFY-CH3 compound and solvent in the reactor, but allows the product (e.g., HFO-1243yc) to exit the reactor since the boiling point of HFO-1243yc is much lower than CF2X-CFY-CH3 and the solvent.

[0047] In some embodiments, the catalyst, the reaction temperature, the reaction pressure and / or the reaction time is selected to provide a product mixture having a high yield of HFO-1243yc.

[0048] In some embodiments, the high yield of HFO-1243yc in the product mixture is at least 40 mol%, alternatively at least 50 mol%, alternatively at least 60 mol%, alternatively at least 75 mol%, alternatively at least 80 mol%, alternatively at least 85TS0074-W001mol%, alternatively at least 90 mol%, or any value, range, or sub-range therebetween.

[0049] In some embodiments, the dehalogenation reaction occurs in the liquid phase. In some embodiments, the dehalogenation reaction produces a vapor phase.

[0050] In one embodiment, the compound of formula CF2X-CFY-CH3 is selected from HCFC-244bb, HBFC-244bbB and HCFC-243bc.

[0051] In one embodiment, herein referred to as Embodiment 1A, the compound of formula CF2X-CFY-CH3 is HCFC-244bb. In one embodiment, the feed composition for reaction with the metal (e.g., zinc) comprises, consists essentially of or consists of HCFC-244bb, preferably as the main component, more preferably in amounts of about 99 wt% or greater based on the total amount of the feed composition.

[0052] According to Embodiment 1 A, a process of forming HFO-1243yc includes contacting HCFC-244bb with a metal, such as an activated or non-activated zinc powder, and producing a product mixture including HFO-1243yc, as shown below. In some embodiments, the contacting further includes contacting a catalyst, such as TBAB or ZnCl2, as described in greater detail above.HCFC-244bb + Zn HFO-1243yc + ZnFCI (Embodiment 1 A)

[0053] ZnFCI is also formed as a product of the dehalogenation reaction.

[0054] In some embodiments, according to Embodiment 1A, the present invention relates to liquid phase reaction of HCFC-244bb and zinc at a temperature between about 60°C and about 200°C, preferably from about 80°C to about 180°C, in the presence of a catalyst preferably selected from a zinc salt (e.g., ZnCl2 or zinc acetate), ammonium salt (e.g., tetrabutylammonium bromide) or phosphonium salt, and in the presence of a solvent preferably selected from alcohol, amide, pyridine and ether, and more preferably an alcohol solvent such as methanol. In some embodiments, the zinc used for this reaction has been activated by an acid, for example zinc powder which has been activated with HCI (e.g., aqueous or in an alcohol). In other embodiments, the zinc, preferably zinc powder, is non-activated. Preferably, a molar ratio of HCFC-244bb:metal for the liquid phase conversion of HCFC-244bb is in the range of about 0.8:1 to about 1 :3.TS0074-W001

[0055] In some embodiments, the present invention relates to a composition comprising HFO-1243yc and one or more additional compounds selected from tetrafluoroethylene, 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, hexafluorobutene, propane, propene, 1 ,1 ,1 ,2-tetrafluoropropane, dimethyl either, methanol, 2-chloro-1,1,1,2-tetrafluoropropane, 1 -butene, 1 -chloro-2, 3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1 -chloro-3,3,3-trifluoropropene and 3,3,4,4,4-pentafluorobutene. In some embodiments, the composition is formed by the process according to Embodiment 1A.

[0056] In some embodiments, the present invention relates to a composition comprising HFO-1243yc and one or more additional compounds selected from 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1 ,1 ,1 ,2-tetrafluoropropane, dimethyl either, 1,1,1,3,3,3-hexafluoro-2-methylpropane, 2-chloro-1, 1 ,1 ,2-tetrafluoropropane, 2-chloro-3,3,3-trifluoropropene, heptafluorohexane, hexafluorohexene and chlorohexafluorohexene. In some embodiments, the composition is formed by the process according to Embodiment 1 A.

[0057] In some embodiments, the present invention relates to a composition comprising HFO-1243yc and one or more additional compounds selected from HFO-1234yf, HFO-1243zf, HFO-1336, HFC-254eb, HFO-1345, HCFC-244bb, 2-butene, HCFO-1224yd, HCFO-1233xf, HFO-1243 isomer(s), CeHeFe, C4H3F5, HCFC-243db and CeHsCIFe. In some embodiments, the composition is formed by the process according to Embodiment 1A.

[0058] In one embodiment, referred to herein as Embodiment 1 B, the compound of formula CF2X-CFY-CH3 is HBFC-244bbB. In one embodiment, the feed composition for reaction with the metal (e.g., zinc) comprises, consists essentially of or consists of HBFC-244bbB, preferably as the main component, more preferably in amounts of about 99 wt% or greater based on the total amount of the feed composition.

[0059] According to Embodiment 1 B, a process of forming HFO-1243yc includes contacting HBFC-244bbB with a metal, such as an activated or non-activated zinc powder, and producing a product mixture including HFO-1243yc, as shown below. InTS0074-W001some embodiments, the contacting further includes contacting a catalyst, such as TBAB or ZnCl2, as described in greater detail above.CF3CFBrCH3+Zn HFO-1243yc + ZnFBr (Embodiment 1 B)

[0060] ZnFBr is also formed as a product of the dehalogenation reaction.

[0061] In some embodiments, according to Embodiment 1 B, the present invention relates to liquid phase reaction of HBFC-244bbB and zinc at a temperature between about 60°C and about 200°C, preferably from about 110°C to about 130°C, in the presence of a catalyst preferably selected from a zinc salt (e.g., ZnCh or zinc acetate), ammonium salt (e.g., tetrabutylammonium bromide) or phosphonium salt, and in the presence of a solvent preferably selected from alcohol, amide, pyridine and ether, and more preferably an alcohol solvent such as methanol. In some embodiments, the zinc used for this reaction has been activated by an acid, for example zinc powder which has been activated with HCI (e.g., aqueous or in an alcohol). In other embodiments, the zinc, preferably zinc powder, is non-activated. Preferably, a molar ratio of HBFC-244bbB:metal for the liquid phase conversion of HBFC-244bbB is in the range of about 0.8: 1 to about 1 :3.

[0062] In one embodiment, referred to herein as Embodiment 1 C, the compound of formula CF2X-CFY-CH3 is HCFC-243bc. In one embodiment, the feed composition for reaction with the metal (e.g., zinc) comprises, consists essentially of or consists of HCFC-243bc, preferably as the main component, more preferably in amounts of about 99 wt% or greater based on the total amount of the feed composition.

[0063] According to Embodiment 1 C, a process of forming HFO-1243yc includes contacting HCFC-243bc with a metal, such as an activated or non-activated zinc powder, and producing a product mixture including HFO-1243yc, as shown below. In some embodiments, the contacting further includes contacting a catalyst, such as TBAB or ZnCl2, as described in greater detail above.CCIF2CFCICH3 + Zn HFO-1243yc + ZnCl2 (Embodiment 1C)

[0064] ZnCl2 is also formed as a product of the dechlorination reaction.TS0074-W001

[0065] In some embodiments, according to Embodiment 1 C, the present invention relates to liquid phase reaction of HCFC-243bc and zinc at a temperature between about 60°C and about 200°C, in the presence of a catalyst preferably selected from a zinc salt (e.g., ZnCl2 or zinc acetate), ammonium salt (e.g., tetrabutylammonium bromide) or phosphonium salt, and in the presence of a solvent preferably selected from alcohol, amide, pyridine and ether, and more preferably an alcohol solvent such as methanol. In some embodiments, the zinc used for this reaction has been activated by an acid, for example zinc powder which has been activated with HCI (e.g., aqueous or in an alcohol). In other embodiments, the zinc is non-activated. Preferably, a molar ratio of HCFC-243bc:metal for the liquid phase conversion of HCFC-243bc is in the range of about 0.8:1 to about 1 :3.

[0066] In some embodiments, the process is a one-step reaction to form HFO-1243ycfrom a compound of formula CF2X-CFY-CH3. In some embodiments, the product mixture formed by the dehalogenation reaction of the compound of formula CF2X-CFY-CH3 comprises a composition comprising HFO-1243yc.

[0067] The product mixture or composition may be treated by a purification process to remove one or more impurities. Appropriate purification processes may include, but are not limited to, a simple distillation, a fractional distillation, an extractive distillation, ora solvent scrubbing.Second Embodiment

[0068] In some embodiments, the process comprises a one-step reaction that forms the compound of formula CF2X-CFY-CH3.

[0069] In some embodiments, the compound of formula CF2X-CFY-CH3 is HBFC-244bbB, and the process comprises contacting HBFO-1233xfB with hydrogen fluoride, optionally in the presence of a catalyst such as SbCIs or SbFs, and producing a first product mixture or composition including HBFC-244bbB by a hydrofluorination reaction, as shown in Reaction (A).CF3CBr=CH2+ HF CF3CFBrCH3(A)

[0070] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HFO-1243yc, wherein the HBFC-244bbB formed byTS0074-W001Reaction (A) is utilized to form a second product mixture or composition comprising HFO-1243yc. In some embodiments, the reaction to form the HFO-1234yc from the HBFC-244bbB is as described above with respect to Embodiment 1 , and more particularly with respect to Embodiment 1 B.

[0071] In one embodiment, the series of reactions are integrated, wherein the HBFC-244bbB produced by Reaction (A) is supplied as the feed composition for the reaction of Embodiment 1B to form HFO-1243yc, as follows:CF3CBr=CH2+ HF CF3CFBrCH3CF3CFBrCH3+Zn HFO-1243yc + ZnFBrThird Embodiment

[0072] In some embodiments, the compound of formula CF2X-CFY-CH3is HBFC-244bbB, and the process comprises contacting HBFC-234baB with hydrogen (H2) and producing a product mixture or composition including HBFC-244bbB by a hydrodebromination reaction, as shown in Reaction (B).CF3CFBrCH2Br + H2CF3CFBrCH3+ HBr (B)

[0073] Hydrogen bromide is also formed as a product of the hydrodebromination reaction.

[0074] In some embodiments, reaction (B) is carried out in the vapor phase, preferably in the presence of a catalyst such as Pd / C. For the catalyst, the Pd loading may be from about 0.1 % to about 5%. The reaction may be carried out at a temperature from about 80°C to about 250°C. The ratio of H2to organic feed material (e.g., CF3CFBrCH2Br) may be from about 30:1 to about 2:1.

[0075] In some embodiments, the process comprises a reaction that forms a precursor compound of the compound of formula CF2X-CFY-CH3. In some embodiments, where the compound of formula CF2X-CFY-CH3is HBFC-244bbB, the precursor compound is HBFC-234baB.

[0076] In some embodiments, the precursor compound HBFC-234baB is formed by contacting HFO-1234yf with bromine (Br2) and producing a product mixture orTS0074-W001composition including HBFC-234baB by a bromination reaction, as shown in Reaction C.HFO-1234yf + Br2CF3CFBrCH2Br (C)

[0077] In some embodiments, reaction (C) is carried out in the vapor phase or liquid phase, for example by UV irradiation. In other embodiments, reaction (C) is carried out in the liquid phase in the presence of a catalyst, such as FeCh. The reaction may be carried out at a temperature from about 60°C to about 150°C, preferably from about 80°C to about 120°C. The ratio of Br2to organic feed material (e.g., HFO-1234yf) may be from about 0.8:1 to about 1.2:1. The reaction is preferably carried out in the absence of a solvent. The conversion rate is preferably greater than 90%. The selectivity is preferably greater than 90%. Reaction time may vary depending on temperature. For example, at a reaction temperature of 100°C, reaction time may be about 5 hours.

[0078] In some embodiments, the present invention relates to a composition comprising HBFC-234baB and one or more additional compounds selected from HFO-1234yf, CF3CFBrCH2CI and CH2Br2. In some embodiments, the composition is formed by reaction (C).

[0079] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HBFC-244bbB, wherein the HBFC-234baB formed by reaction (C) is utilized to form a product mixture or composition comprising HBFC-244bbB. In some embodiments, the reaction to form the HBFC-244bbB from HBFC-234baB is as described above with respect to reaction (B).

[0080] In one embodiment, the series of reactions are integrated, wherein the HBFC-234baB produced by reaction (C) is supplied as the feed composition for the reaction of reaction (B) to form HBFC-244bbB, as follows:HFO-1234yf + Br2CF3CFBrCH2BrCF3CFBrCH2Br + H2CF3CFBrCH3

[0081] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HFO-1243yc, wherein the HBFC-244bbB formed by reaction (B) is utilized to form a product mixture or composition comprising HFO-TS0074-W0011234yc. In some embodiments, the reaction to form the HFO-1234ycfrom the HBFC-244bbB is as described above with respect to Embodiment 1 , and more particularly with respect to Embodiment 1 B.

[0082] In one embodiment, the series of reactions are integrated, wherein the HBFC-244bbB produced by reaction (B) is supplied as the feed composition for the reaction of Embodiment 1B to form HFO-1243yc, as follows:CF3CFBrCH2Br + H2CF3CFBrCH3CF3CFBrCH3+Zn HFO-1243yc + ZnFBr

[0083] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HFO-1243yc, wherein HBFC-234baB is formed by reaction (C) and is utilized to form a product mixture or composition comprising HBFC-244bbB according to reaction (B), and the HBFC-244bbB formed by Reaction (B) is utilized to form a product mixture or composition comprising HFO-1234yc. In some embodiments, the reaction to form the HFO-1234yc from the HBFC-244bbB is as described above with respect to Embodiment 1 , and more particularly with respect to Embodiment 1 B.

[0084] In one embodiment, the series of reactions are integrated, wherein the HBFC-234baB produced by reaction (C) is supplied as the feed composition for the reaction of Reaction (B) to form HBFC-244bbB which, in turn, is supplied as the feed composition for the reaction of Embodiment 1B to form HFO-1243yc, as follows:HFO-1234yf + Br2CF3CFBrCH2BrCF3CFBrCH2Br + H2> CF3CFBrCH3CF3CFBrCH3+Zn HFO-1243yc + ZnFBrFourth Embodiment

[0085] In some embodiments, the compound of formula CF2X-CFY-CH3is HCFC-243bc, and the process comprises contacting HCFO-1232xf with hydrogen fluoride and producing a product mixture or composition including HCFC-243bc by a hydrofluorination reaction, as shown in Reaction (D).CCIF2CCI=CH2+ HF CCIF2CFCICH3(D)TS0074-W001

[0086] In some embodiments, reaction (D) is carried out in the liquid phase, preferably in the presence of a catalyst such as SbCIs or SbFs. The reaction may be carried out at a temperature from about -10°C to about 100°C. The ratio of HF to organic feed material may be from about 1 : 1 to about 10:1.

[0087] In some embodiments, the process comprises a reaction that forms a precursor compound of the compound of formula CF2X-CFY-CH3. In some embodiments, where the compound of formula CF2X-CFY-CH3 is HCFC-243bc, the precursor compound is HCFO-1232xf.

[0088] In some embodiments, the precursor compound HCFO-1232xf is formed by contacting HCO-1230xa with hydrogen fluoride and producing a product mixture or composition including HCFO-1232xf by a fluorodechlorination reaction, as shown in Reaction (E).CCl2=CCICH2CI + 2 HF CCIF2CCI=CH2 + 2 HCI (E)

[0089] HCI is also formed as a product of the fluorodechlorination reaction.

[0090] In some embodiments, reaction (E) is carried out as described in International Application No. PCT / US2024 / 042003, the entire disclosure of which is herein incorporated by reference in its entirety.

[0091] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HCFC-243bc, wherein the HCFO-1232xf formed by Reaction (E) is utilized to form a product mixture or composition comprising HCFC-243bc. In some embodiments, the reaction to form the HCFC-243bc from HCFO-1232xf is as described above with respect to Reaction (D).

[0092] In one embodiment, the series of reactions are integrated, wherein the HCFO-1232xf produced by Reaction (E) is supplied as the feed composition for the reaction of Reaction (D) to form HCFC-243bc, as follows:CCI2=CCICH2CI + 2 HF CCIF2CCI=CH2+ 2 HCI CCIF2CCI=CH2+ HF — > CCIF2CFCICH3

[0093] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HFO-1243yc, wherein the HCFC-243bc formed by Reaction (D) is utilized to form a product mixture or composition comprising HFO-TS0074-W0011234yc. In some embodiments, the reaction to form the HFO-1234ycfrom the HCFC-243bc is as described above with respect to Embodiment 1, and more particularly with respect to Embodiment 1C.

[0094] In one embodiment, the series of reactions are integrated, wherein the HCFC-243bc produced by Reaction (D) is supplied as the feed composition for the reaction of Embodiment 1C to form HFO-1243yc, as follows:CCIF2CCI=CH2+ HF CCIF2CFCICH3 CCIF2CFCICH3+Zn HFO-1243yc + ZnCI2

[0095] In some embodiments, the process comprises a multi-step reaction or series of reactions to form HFO-1243yc, wherein HCFO-1232xf is formed by Reaction (E) and is utilized to form a product mixture or composition comprising HCFC-243bc according to Reaction (D), and the HCFC-243bc formed by Reaction (D) is utilized to form a product mixture or composition comprising HFO-1234yc. In some embodiments, the reaction to form the HFO-1234yc from the HBFC-244bbB is as described above with respect to Embodiment 1 , and more particularly with respect to Embodiment 1C.

[0096] In one embodiment, the series of reactions are integrated, wherein the HCFO-1232xf produced by Reaction (E) is supplied as the feed composition for the reaction of Reaction (D) to form HCFC-243bc which, in turn, is supplied as the feed composition for the reaction of Embodiment 1C to form HFO-1243yc, as follows:CCI2=CCICH2CI + 2 HF CCIF2CCI=CH2+ 2 HCI CCIF2COCH2 + HF > CCIF2CFCICH3 CCIF2CFCICH3+Zn HFO-1243yc + ZnCI2

[0097] In multi-step embodiments, the intermediate product mixture or mixtures of any of the above-described multi-step processes may be treated by a purification process to remove one or more impurities. Appropriate purification processes may include, but are not limited to, a simple distillation, a fractional distillation, an extractive distillation, or a solvent scrubbing. In some embodiments, any of the integrated processes disclosed herein further comprises separation and / orTS0074-W001purification steps to recover the desired intermediate and / or the desired reaction product (e.g., HFO-1243yc).

[0098] In one embodiment, the total amount of the additional compounds is between greater than 0.001 wt.% and less than 2 wt.%, preferably less than 1 wt.%, 0.9 wt.%, 0.8 wt.%, 0.7 wt.%, 0.6 wt.%, 0.5 wt.%, 0.4 wt.%, 0.3 wt.%, 0.2 wt.%, 0.1 wt.%, 0.09 wt.%, 0.08 wt.%, 0.07 wt.%, 0.06 wt.%, 0.05 wt.%, 0.04 wt.%, 0.03 wt.%, 0.02 wt.%, or 0.01 wt.%, and all values and ranges therebetween provided the total amount of the composition is 100 wt.%.

[0099] The invention will be described in greater detail by way of specific examples. The following examples are offered for illustrative purposes and are not intended to limit the invention in any manner. Those of skill in the art will readily recognize a variety of non-critical parameters which can be changed or modified to yield essentially the same results.EXAMPLESExample 1 : Formation of HFO-1243yc starting from HCFC-244bb

[0100] A product mixture including HFO-1243yc was formed in a one-step process by dehalogenation of HCFC-244bb.

[0101] 8 g Zn powder, previously activated by aqueous HCI and dried under N2, was added into an autoclave together with 23 g 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), 2 g tetrabutylammonium bromide (TBAB), and 40 g dried methanol. After the autoclave was sealed, it was chilled to -40°C, and then a full vacuum was pulled to remove air. The reaction mixture was then heated to 180°C with agitation and agitated at 180°C for 10 hours. After the reaction mixture was cooled to room temperature, the vapor phase of the reactor was blown into a 75-mL cylinder and was analyzed by GC-MS-FID. The GC-MS-FID analyses of the vapor phase and liquid phase of the reaction product are provided in Tables 1 and 2. The major detected product in the vapor phase was 67.0% (FID area%) HFO-1243yc. After adjusting for detected methanol (i.e., exclusion of the methanol solvent in integration), the yield of HFO-1243yc was about 69.5% (FID area%).TS0074-W001Table 1 : GC analysis of vapor phase of reaction productTable 2: GC analysis of liquid phase of reaction product*Methanol is present but is subtracted from GC quantitationExample 2: Formation of HFO-1243yc starting from HCFC-244bb

[0102] A product mixture including HFO-1243yc was formed in a one-step process by dehalogenation of HCFC-244bb.

[0103] 65 g Zn powder (non-activated) was added into an autoclave together with 110 g HCFC-244bb, 10 g ZnCI2 and 180 g dried methanol. After the autoclave is sealed, it was chilled to -40°C and then full vacuum was pulled to remove air. Then,TS0074-W001the reaction mixture was heated to 160°C with agitation and agitated at 160°C for 18 hours. Afterwards, the reaction mixture was cooled to room temperature. Vapor phase of reactor was blown into a 250ml cylinder and liquid phase of product was analyzed by GC-MS-FID. The GC-MS-FID analysis of the liquid phase of the reaction product is provided in Table 3. After adjusting for detected methanol (i.e., exclusion of the methanol solvent in integration), the yield of HFO-1243yc, which was the major detected non-methanol product in the liquid phase, was 61.5% (FID area%).Table 3: GC analysis of liquid phase of reaction product*Methanol is present but is subtracted from GC quantitationExample 3: Formation of HFO-1243yc starting from HCFC-244bbB

[0104] A product mixture including HFO-1243yc was formed in a one-step process by dehalogenation of HCFC-244bb.

[0105] 65.7 g Zn powder (non-activated) was added into an autoclave together with 110 g HCFC-244bb, 10 g TBAB and 178.8 g dried DMF. After the autoclave was sealed, it was chilled to -40°C and then full vacuum was pulled to remove air. Then, the reaction mixture was heated to 100°C with agitation and agitated at 100°C for 20 hours. Afterwards, the reaction mixture was cooled to 60°C. Vapor phase of reactor was blown into a 250ml cylinder and liquid phase of product was analyzed by GC-TS0074-W001MS-FID. The GC-MS-FID analysis is provided in Table 4. The major detected product in the liquid phase was 86% (FID area%) HFO-1243yc.Table 4: GC analysis of liquid phase of reaction productExample 4: Formation of HFO-1243yc starting from CF3CBr=CH2

[0106] A product mixture including HFO-1243yc is formed from CF3CBr=CH2 in a two-step process by a hydrofluorination followed by a dehalogenation.

[0107] A freshly prepared SbCIs (350g), anhydrous hydrogen fluoride (400g) and HBFO-1233xfB (100 g) are charged in a 2 lit Hastelloy reactor and slowly heated and maintained at 85°C for 4 hours. After 4 hours, the hot reaction mixture is slowly vented off into ice water. After completion of venting, the aqueous layer is separated. The bottom layer comprises crude organic of about 108 g with the area composition of 85% of HBFC-244bbB and 13% of HBFO-1233xfB by GC. The crude organic is further distilled to obtain pure HBFC-244bbB (e.g., at least 98% purity).

[0108] Zn powder, previously activated by aqueous HCI and dried under N2, is added into an autoclave together with the HBFC-244bbB, catalyst, and driedTS0074-W001methanol. After the autoclave is sealed, it is chilled to -40°C, and then a full vacuum is pulled to remove air. The reaction mixture is then heated to 120°C with agitation and agitated at 120°C for 10 hours. The reaction mixture is cooled to room temperature and analyzed by GC-MS-FID to confirm HFO-1243yc as the main product.Example 5: Formation of HFO-1243yc starting from HFO-1234yf

[0109] A product mixture including HFO-1243yc is formed from HFO-1234yf in a three-step process by a bromination followed by a hydrodebromination followed by a dehalogenation.

[0110] 0.62g anhydrous FeChwas loaded into a dried 400ml shaker tube. The reactor was evacuated and chilled to -30°C, and then 40g of HFO-1234yf and 55g of Br? was charged into the reactor. The mixture was agitated and heated to 100°C and agitated at 100°C for 4.5 hours and then cooled to room temperature. The pressure drop started at60°C which is indicative of the reaction having already happened at 60°C. The product was analyzed by GC-MS-FID. This analysis is provided in Table 5. The major detected product was 95.5% (FID area%) HBFC-234baB. The GC of product analysis showed 98.9% conversion and selectivity to HBFC-234baB was about 96.5%.Table 5: GC analysis of reaction product

[0111] Next, the HBFC-234baB is contacted with hydrogen (H2) in the vapor phase, in the presence of a Pd / C catalyst having a Pd loading of from about 0.1% to about 5%. The reaction is carried out at a temperature from about 80°C to about 250°C. The ratio of H2 to organic feed material is from about 30:1 to about 2:1. The reaction produces a product mixture comprising HBFC-244bbB as the major detected product by GC analysis.TS0074-W001

[0112] Next, Zn powder, previously activated by aqueous HCI and dried under N2, is added into an autoclave together with the HBFC-244bbB, catalyst, and dried methanol. After the autoclave is sealed, it is chilled to -40°C, and then a full vacuum is pulled to remove air. The reaction mixture is then heated to 120°C with agitation and agitated at 120°C for 10 hours. The reaction mixture is cooled to room temperature and analyzed by GC-MS-FID to confirm HFO-1243yc as the main product.Example 6: Formation of HFO-1243yc starting from HCQ-1230xa

[0113] A product mixture including HFO-1243yc is formed from HCO-1230xa in a three-step process by a fluorodechlorination followed by a hydrofluorination followed by a dechlorination.

[0114] HCFO-1232xf is formed by contacting HCO-1230xa with hydrogen fluoride and producing a product mixture or composition including HCFO-1232xf by a fluorodechlorination reaction, as described in International Application No.PCT / US2024 / 042003. Next, the HCFO-1232xf is contacted with hydrogen fluoride to produce a product mixture or composition including HCFC-243bc by a hydrofluorination reaction. More particularly, HCFO-1232xf and HF are contacted in the liquid phase, in the presence of a SbCIs or SbFs catalyst, at a temperature from about -10°C to about 100°C, with an HF:HCFO-1232xf ratio of from about 1:1 to about 10:1 , to produce a mixture comprising HCFC-243bc.

[0115] Zn powder, previously activated by aqueous HCI and dried under N2, is added into an autoclave together with the HCFC-243bc, catalyst, and dried methanol. After the autoclave is sealed, it is chilled to -40°C, and then a full vacuum is pulled to remove air. The reaction mixture is then heated to 120°C with agitation and agitated at 120°C for 10 hours. The reaction mixture is cooled to room temperature and analyzed by GC-MS-FID to confirm HFO-1243yc as the main product.OTHER EMBODIMENTS

[0116] Embodiment 1. A process comprising contacting a compound of formula CF2X-CFY-CH3 with a metal, wherein X is selected from Cl and F and Y is selectedTS0074-W001from Cl, Brand I; and producing a first product mixture comprising 1,1,2-trifluoropropene (HFO-1243yc).

[0117] Embodiment 2. The process of Embodiment 1 , wherein the metal is a reactive metal.

[0118] Embodiment 3. The process of Embodiment 1 or Embodiment 2, wherein the metal is selected from the group consisting of zinc, magnesium, cadmium, and combinations thereof.

[0119] Embodiment 4. The process of any of Embodiments 1 to 3, wherein the metal is zinc.

[0120] Embodiment 5. The process of any of Embodiments 1 to 4, wherein the metal is zinc powder.

[0121] Embodiment 6. The process of any of Embodiments 1 to 5, wherein the metal is activated zinc powder.

[0122] Embodiment 7. The process of any of Embodiments 1 to 6, wherein the contacting occurs in the presence of a catalyst.

[0123] Embodiment 8. The process of Embodiment 7, wherein the catalyst is selected from the group consisting of zinc salt, ammonium salt and phosphonium salt.

[0124] Embodiment 9. The process of Embodiment 8, wherein the catalyst comprises a zinc salt selected from the group consisting of zinc acetate and zinc chloride.

[0125] Embodiment 10. The process of Embodiment 8, wherein the catalyst comprises an ammonium salt, preferably tetrabutylammonium bromide

[0126] Embodiment 11. The process of any of Embodiments 1 to 10, wherein the contacting occurs in the presence of a solvent.

[0127] Embodiment 12. The process of Embodiment 11 , wherein the solvent is a polar protic solvent or polar aprotic solvent.

[0128] Embodiment 13. The process of Embodiment 11, wherein the solvent is selected from the group consisting of alcohol, amide, pyridine and ether.TS0074-W001

[0129] Embodiment 14. The process of Embodiment 13, wherein the solvent comprises an alcohol selected from the group consisting of methanol (e.g., dried methanol), ethanol, propanol, isopropanol and ethylene glycol.

[0130] Embodiment 15. The process of Embodiment 13, wherein the solvent comprises an amide selected from the group consisting of dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylacetamide (DMAC).

[0131] Embodiment 16. The process of any of Embodiments 1 to 15, wherein a mole ratio of the compound of formula CF2X-CFY-CH3 to the metal is from about 0.8:1 to about 1:3.

[0132] Embodiment 17. The process of any of Embodiments 7 to 16, wherein a mole ratio of the compound of formula CF2X-CFY-CH3 to the catalyst is from about 0.8:1 to about 1:3.

[0133] Embodiment 18. The process of any of Embodiments 7 to 16, wherein a mole ratio of the metal to the catalyst is from about 0.8:1 to about 1 :3.

[0134] Embodiment 19. The process of any of Embodiments 1 to 18, wherein the producing occurs at a temperature in the range of about 60°C to about 200°C.

[0135] Embodiment 20. The process of any of Embodiments 1 to 19, wherein the producing occurs at a pressure of about 500 psig to about 1500 psig.

[0136] Embodiment 21. The process of any of Embodiments 1 to 20, wherein the compound of formula CF2X-CFY-CH3 is selected from the group consisting of 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb), 2-bromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-244bbB) and 1,2-dichloro-1,1,2-trifluoropropane (HCFC-243bc).

[0137] Embodiment 22. The process of Embodiment 21 , wherein the compound is of formula CF2X-CFY-CH3 is HBFC-244bbB, and wherein the process further comprises:(i) contacting 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB) with hydrogen fluoride and producing a second product mixture comprising the HBFC- 244bbB; orTS0074-W001(ii) contacting 2,3-dibromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-234baB) with hydrogen (H2) and producing a second product mixture comprising the HBFC- 244bbB.

[0138] Embodiment 23. The process of Embodiment 22, wherein (ii) further comprises contacting 2,3,3,3-tetrafluoropropene (HFO-1234yf) with bromine (Br2) and producing a third product mixture comprising the HBFC-234baB.

[0139] Embodiment 24. The process of Embodiment 23, wherein the HFO-1234yf and Br2 are contacted in the liquid phase in the presence of a catalyst, preferably FeCI3.

[0140] Embodiment 25. The process of Embodiment 23 or 24, wherein the HFO-1234yf and Br2 are contacted at a temperature from about 60°C to about 150°C, preferably from about 80°C to about 120°C.

[0141] Embodiment 26. The process of any of Embodiments 23 to 25, wherein a ratio of Br2 to HFO-1234yf is from about 0.8:1 to about 1.2:1.

[0142] Embodiment 27. The process of Embodiment 21 , wherein the compound is of formula CF2X-CFY-CH3 is HCFC-243bc, and wherein the process further comprises contacting 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) with hydrogen fluoride and producing a second product mixture comprising the HCFC-243bc.

[0143] Embodiment 28. The process of Embodiment 27, wherein contacting the HCFO-1232xf and HF is carried out in the liquid phase in the presence of a catalyst, preferably SbCIs or SbFs.

[0144] Embodiment 29. The process of Embodiment 27 or 28, wherein the HCFO-1232xf and HF are contacted at a temperature from about -10°C to about 100°C.

[0145] Embodiment 30. The process of any of Embodiments 27 to 29, wherein a ratio of HF to HCFO-1232xf is from about 1:1 to about 10:1.

[0146] Embodiment 31. The process of any of Embodiments 27 to 30, further comprising contacting 1 ,1 ,2,3-tetrachloropropene (HCO-1230xa) with hydrogen fluoride and producing a third product mixture comprising the HCFO-1232xf.TS0074-W001

[0147] Embodiment 32. A process comprising:contacting 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB) with hydrogen fluoride; andproducing a first product mixture comprising 2-bromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-244bbB).

[0148] Embodiment 33. A process comprising:contacting 2, 3-dibromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-234baB) with hydrogen (H2); andproducing a first product mixture comprising 2-bromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-244bbB).

[0149] Embodiment 34. The process of Embodiment 32 or 33, further comprising contacting the HBFC-244bbB with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1,2-trifluoropropene (HFO-1243yc).

[0150] Embodiment 35. The process of Embodiment 33 or 34, further comprising:contacting 2,3,3,3-tetrafluoropropene (HFO-1234yf) with bromine (B ); and producing a product mixture comprising the HBFC-234baB.

[0151] Embodiment 36. A process comprising:contacting 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) with hydrogen fluoride; andproducing a first product mixture comprising 1 ,2-dichloro-1 ,1 ,2-trifluoropropane (HCFC-243bc).

[0152] Embodiment 37. The process of Embodiment 36, further comprising contacting the HCFC-243bc with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1,2-trifluoropropene (HFO-1243yc).TS0074-W001

[0153] Embodiment 38. The process of Embodiment 36 or 37, further comprising:contacting 1,1,2,3-tetrachloropropene (HCO-1230xa) with hydrogen fluoride; andproducing a product mixture comprising the HCFO-1232xf.

[0154] Embodiment 39. A process comprising contacting 2-chloro-1, 1,1,2-tetrafluoropropane (HCFC-244bb) with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1 ,2-trifluoropropene (HFO-1243yc).

[0155] Embodiment 40. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of tetrafluoroethylene, 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, hexafluorobutene, propane, propene, 1,1,1,2-tetrafluoropropane, dimethyl either, methanol, 2-chloro-1, 1,1,2-tetrafluoropropane, 1 -butene, 1-chloro-2,3,3,3-tetrafluoropropene, 2-chloro-3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and 3,3,4,4,4-pentafluorobutene.

[0156] Embodiment 41. The composition of Embodiment 40, wherein the composition is formed according to the process of Embodiments 6, 10 and 14.

[0157] Embodiment 42. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, 1,1,1 ,2-tetrafluoropropane, dimethyl either, 1,1,1 ,3,3,3-hexafluoro-2-methylpropane, 2-chloro-1 ,1,1 ,2-tetrafluoropropane, 2-chloro-3,3,3-trifluoropropene, heptafluorohexane, hexafluorohexene and chlorohexafluorohexene.

[0158] Embodiment 43. The composition of Embodiment 42, wherein the composition is formed according to the process of Embodiments 5, 9 and 14.

[0159] Embodiment 44. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of HFO-1234yf, HFO-1243zf, HFO-1336, HFC-254eb, HFO-1345, HCFC-244bb, 2-butene, HCFO-1224yd, HCFO-1233xf, HFO-1243 isomer(s), CeHeFe, C4H3F5, HCFC-243db and CeHsCIFe.

[0160] Embodiment 45. The composition of Embodiment 44, wherein the composition is formed according to the process of Embodiments 5, 10 and 15.TS0074-W001

[0161] Embodiment 46. A composition comprising HBFC-234baB and one or more additional compounds selected from the group consisting of HFO-1234yf, CF3CFBrCH2CI and CH2Br2.

[0162] Embodiment 47. The composition of Embodiment 46, wherein the composition is formed according to the process of Embodiment 35.

[0163] While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any inventions or of what may be claimed, but rather as descriptions of features specific to particular implementations of particular inventions. Certain features that are described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub-combination or variation of a sub-combination.

[0164] Similarly, while operations are depicted in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In certain circumstances, multitasking and parallel processing may be advantageous. Moreover, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.

[0165] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which example embodiments belong. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the contextTS0074-W001of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

[0166] While the disclosure has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made, and equivalents may be substituted for elements thereof without departing from the scope of the disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the disclosure without departing from the essential scope thereof. While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

Claims

TS0074-W001CLAIMSWhat is claimed is:

1. A process comprising:contacting a compound of formula CF2X-CFY-CH3 with a metal, wherein X is selected from Cl and F and Y is selected from Cl, Br and I; andproducing a first product mixture comprising 1,1,2-trifluoropropene (HFO- 1243yc).

2. The process of claim 1 , wherein the metal is a reactive metal.

3. The process of claim 1 or claim 2, wherein the metal is selected from the group consisting of zinc, magnesium, cadmium, and combinations thereof.

4. The process of any of claims 1 to 3, wherein the metal is zinc.

5. The process of any of claims 1 to 4, wherein the metal is zinc powder.

6. The process of any of claims 1 to 5, wherein the metal is activated zinc powder.

7. The process of any of claims 1 to 6, wherein the contacting occurs in the presence of a catalyst.

8. The process of claim 7, wherein the catalyst is selected from the group consisting of zinc salt, ammonium salt and phosphonium salt.

9. The process of claim 8, wherein the catalyst comprises a zinc salt selected from the group consisting of zinc acetate and zinc chloride.

10. The process of claim 8, wherein the catalyst comprises an ammonium salt, preferably tetrabutylammonium bromide11. The process of any of claims 1 to 10, wherein the contacting occurs in the presence of a solvent.

12. The process of claim 11 , wherein the solvent is a polar protic solvent or polar aprotic solvent.

13. The process of claim 11 , wherein the solvent is selected from the group consisting of alcohol, amide, pyridine and ether.TS0074-W00114. The process of claim 13, wherein the solvent comprises an alcohol selected from the group consisting of methanol (e.g., dried methanol), ethanol, propanol, isopropanol and ethylene glycol.

15. The process of claim 13, wherein the solvent comprises an amide selected from the group consisting of dimethylformamide (DMF), N-methylpyrrolidone (NMP), and dimethylacetamide (DMAC).

16. The process of any of claims 1 to 15, wherein a mole ratio of the compound of formula CF2X-CFY-CH3 to the metal is from about 0.8:1 to about 1:3.

17. The process of any of claims 7 to 16, wherein a mole ratio of the compound of formula CF2X-CFY-CH3 to the catalyst is from about 0.8:1 to about 1:3.

18. The process of any of claims 7 to 16, wherein a mole ratio of the metal to the catalyst is from about 0.8:1 to about 1 :3.

19. The process of any of claims 1 to 18, wherein the producing occurs at a temperature in the range of about 60°C to about 200°C.

20. The process of any of claims 1 to 19, wherein the producing occurs at a pressure of about 500 psig to about 1500 psig.

21. The process of any of claims 1 to 20, wherein the compound of formula CF2X- CFY-CH3 is selected from the group consisting of 2-chloro-1 ,1 ,1 ,2- tetrafluoropropane (HCFC-244bb), 2-bromo-1,1,1,2-tetrafluoropropane (HBFC- 244bbB) and 1 ,2-dichloro-1 ,1 ,2-trifluoropropane (HCFC-243bc).

22. The process of claim 21 , wherein the compound is of formula CF2X-CFY-CH3 is HBFC-244bbB, and wherein the process further comprises:(i) contacting 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB) with hydrogen fluoride and producing a second product mixture comprising the HBFC-244bbB; or(ii) contacting 2,3-dibromo-1,1,1,2-tetrafluoropropane (HBFC-234baB) with hydrogen (H2) and producing a second product mixture comprising the HBFC-244bbB.TS0074-W00123. The process of claim 22, wherein (ii) further comprises contacting 2, 3,3,3- tetrafluoropropene (HFO-1234yf) with bromine (B ) and producing a third product mixture comprising the HBFC-234baB.

24. The process of claim 23, wherein the HFO-1234yf and Brs are contacted in the liquid phase in the presence of a catalyst, preferably FeC .

25. The process of claim 23 or 24, wherein the HFO-1234yf and Br2 are contacted at a temperature from about 60°C to about 150°C, preferably from about 80°C to about 120°C.

26. The process of any of claims 23 to 25, wherein a ratio of B to HFO-1234yf is from about 0.8:1 to about 1.2:1.

27. The process of claim 21 , wherein the compound is of formula CF2X-CFY-CH3 is HCFC-243bc, and wherein the process further comprises contacting 2,3- dichloro-3,3-difluoropropene (HCFO-1232xf) with hydrogen fluoride and producing a second product mixture comprising the HCFC-243bc.

28. The process of claim 27, wherein contacting the HCFO-1232xf and HF is carried out in the liquid phase in the presence of a catalyst, preferably SbCIs or SbFs.

29. The process of claim 27 or 28, wherein the HCFO-1232xf and HF are contacted at a temperature from about -10°C to about 100°C.

30. The process of any of claims 27 to 29, wherein a ratio of HF to HCFO-1232xf is from about 1 : 1 to about 10:1.

31. The process of any of claims 27 to 30, further comprising contacting 1, 1,2,3- tetrachloropropene (HCO-1230xa) with hydrogen fluoride and producing a third product mixture comprising the HCFO-1232xf.

32. A process comprising:contacting 2-bromo-3,3,3-trifluoropropene (HBFO-1233xfB) with hydrogen fluoride; andproducing a first product mixture comprising 2-bromo-1 ,1 ,1 ,2- tetrafluoropropane (HBFC-244bbB).TS0074-W00133. A process comprising:contacting 2,3-dibromo-1 ,1 ,1 ,2-tetrafluoropropane (HBFC-234baB) with hydrogen (H2); andproducing a first product mixture comprising 2-bromo-1 ,1 ,1 ,2- tetrafluoropropane (HBFC-244bbB).

34. The process of claim 32 or 33, further comprising contacting the HBFC-244bbB with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1,2-trifluoropropene (HFO- 1243yc).

35. The process of claim 33 or 34, further comprising:contacting 2,3,3,3-tetrafluoropropene (HFO-1234yf) with bromine (B ); and producing a product mixture comprising the HBFC-234baB.

36. A process comprising:contacting 2,3-dichloro-3,3-difluoropropene (HCFO-1232xf) with hydrogen fluoride; andproducing a first product mixture comprising 1 ,2-dichloro-1 , 1 ,2- trifluoropropane (HCFC-243bc).

37. The process of claim 36, further comprising contacting the HCFC-243bc with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1,2-trifluoropropene (HFO-1243yc).

38. The process of claim 36 or 37, further comprising:contacting 1,1,2,3-tetrachloropropene (HCO-1230xa) with hydrogen fluoride; andproducing a product mixture comprising the HCFO-1232xf.

39. A process comprising contacting 2-chloro-1 ,1,1 ,2-tetrafluoropropane (HCFC- 244bb) with zinc powder, in the presence of a catalyst and a solvent, to produce a reaction mixture or composition comprising 1,1,2-trifluoropropene (HFO- 1243yc).TS0074-W00140. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of tetrafluoroethylene, 2,3, 3, 3- tetrafluoropropene, 3,3,3-trifluoropropene, hexafluorobutene, propane, propene, 1,1,1,2-tetrafluoropropane, dimethyl either, methanol, 2-chloro-1, 1,1,2- tetrafluoropropane, 1 -butene, 1-chloro-2,3,3,3-tetrafluoropropene, 2-chloro- 3,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoropropene and 3, 3, 4,4,4- pentafluorobutene.

41. The composition of claim 40, wherein the composition is formed according to the process of claims 6, 10 and 14.

42. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of 2,3,3, 3-tetrafluoropropene, 3,3,3- trifluoropropene, 1 ,1,1,2-tetrafluoropropane, dimethyl either, 1, 1,1, 3,3,3- hexafluoro-2-methylpropane, 2-chloro-1 ,1,1 ,2-tetrafluoropropane, 2-chloro- 3,3,3-trifluoropropene, heptafluorohexane, hexafluorohexene and chlorohexafluorohexene.

43. The composition of claim 42, wherein the composition is formed according to the process of claims 5, 9 and 14.

44. A composition comprising HFO-1243yc and one or more additional compounds selected from the group consisting of HFO-1234yf, HFO-1243zf, HFO-1336, HFC-254eb, HFO-1345, HCFC-244bb, 2-butene, HCFO-1224yd, HCFO- 1233xf, HFO-1243 isomer(s), C6H6F6, C4H3F5, HCFC-243db and C6H5CIF6.

45. The composition of claim 44, wherein the composition is formed according to the process of claims 5, 10 and 15.

46. A composition comprising HBFC-234baB and one or more additional compounds selected from the group consisting of HFO-1234yf, CF3CFBrCH2CI and CH2Br2.

47. The composition of claim 46, wherein the composition is formed according to the process of claim 35.

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