Processes for preparing 2-chloro-1,1,1,2-tetrafluoropropane

Abstract

The present application relates to the preparation of 2-chloro-1,1,1,2-tetrafluoropropane from 2-chloro-3,3,3-trifluoroprop-1-ene in the presence of a boron catalyst and, optionally, a fluorinated sulfonic acid. Processes of preparing HFO-1234yf using the 2-chloro-1,1,1,2-tetrafluoropropane and compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane are also provided.

Description

TITLE OF THE INVENTIONPROCESSES FOR PREPARING 2-CHLORO-1 ,1,1 ,2-TETRAFLUOROPROPANETECHNICAL FIELD

[0001] The present application relates to the preparation of 2-chloro-1 ,1,1 ,2- tetrafluoropropane from 2-chloro-3,3,3-trifluoroprop-1-ene in the presence of a boron catalyst and, optionally, a fluorinated sulfonic acid.BACKGROUND

[0002] Hydrofluoroolefins (HFOs), having low ozone depletion potential and low global warming potentials, are regarded as candidates for replacing saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HFOs can be employed in a wide range of applications, including their use as refrigerants, solvents, foam expansion agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishants, and power cycle working fluids.SUMMARY

[0003] The present application provides, inter alia, processes of preparing 2- chloro-1,1,1,2-tetrafluoropropane (244bb), comprising reacting 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide.

[0004] The present application further provides compositions comprising 2-chloro- 1 ,1 ,1 ,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), and BF3, which may be prepared according to one or more processes described herein.

[0005] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Methods and materials are described herein for use in the present invention; other, suitable methods and materials known in the art can also be used. The materials, methods, and examples are illustrative only and not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated by1INCORPORATED BY REFERENCE (RULE 20.6)reference in their entirety. In case of conflict, the present specification, including definitions, will control.DETAILED DESCRIPTION

[0006] 2-Chloro-1,1,1,2-tetrafluoropropane (244bb) is a key intermediate in processes for preparing HFO-1234yf. An exemplary commercial process involves addition of hydrogen fluoride to 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), in the presence of an antimony catalyst, to form the 2-chloro-1 ,1,1 ,2-tetrafluoropropane (244bb). The processes described herein provides a less corrosive and cost- effective alternative to replacing the antimony catalyst, for example, with a boron trihalide catalyst optionally in the presence of a fluorinated sulfonic acid as shown in Scheme I.Scheme I.BF3- ► CF3CCIFCH3 fluorinatedsulfonic acid (optional)

[0007] The processes of the present application can provide additional options for selecting the type of reactor needed for HF / 1233xf chemistry. For example, unlike an SbXs catalyst (where X is halide), boron trifluoride (BF3) is a gas and can be run in a flow-through type reactor. BF3 can be easily separated from a mixture of 244bb / HF and subsequently recycled. Finally, BF3 is a milder fluorination catalyst compared to an antimony fluorination catalyst and does not promote undesirable formation of side products (e.g., 245cb formation).Definitions and Abbreviations

[0008] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is2INCORPORATED BY REFERENCE (RULE 20.6)false (or not present) and B is true (or present), and both A and B are true (or present).

[0009] Also, use of “a” or “an” are employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

[0010] When an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and / or lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range.

[0011] As used herein, the term “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 “consists essentially of’ or “consisting essentially of” occupies a middle ground between “comprising” and “consisting of’.

[0012] Throughout the definitions, the term “Cn-m” indicates a range which includes the endpoints, wherein n and m are integers and indicate the number of carbons. Examples include C1-3, C1-6, and the like.

[0013] As used herein, the term “Cn-m alkyl” refers to a saturated hydrocarbon group that may be straight-chain or branched, having n to m carbons. Exemplary alkyl moieties include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n- butyl, tert-butyl, isobutyl, sec-butyl, 2-methyl-1-butyl, n-pentyl, 3-pentyl, n-hexyl, 1 ,2,2-trimethylpropyl, and the like. In some embodiments, the alkyl group contains from 1 to 6 carbon atoms.3INCORPORATED BY REFERENCE (RULE 20.6)

[0014] As used herein, “Cn-malkenyl” refers to an alkyl group having one or more double carbon-carbon bonds and having n to m carbons. Exemplary alkenyl groups include, but are not limited to, ethenyl, n-propenyl, isopropenyl, n-butenyl, sec- butenyl, and the like. In some embodiments, the alkenyl moiety contains 2 to 6 carbon atoms. In some embodiments, the alkenyl group is substituted by 2s F atoms, wherein “s” is the number of carbon atoms in the alkenyl group.

[0015] As used herein, the term “Cn-mfluoroalkyl” refers to an alkyl group having from one F atom to 2s+1 F atoms, where “s” is the number of carbon atoms in the alkyl group, wherein the alkyl group has n to m carbon atoms. In some embodiments, the fluoroalkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0016] As used herein, the term “Cn-mfluoroalkoxy” refers to a group of formula -O- Cn-m fluoroalkyl, having from one F atom to 2s+1 F atoms, where “s” is the number of carbon atoms in the alkyl group, wherein the alkyl group has n to m carbon atoms. In some embodiments, the fluoroalkoxy group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.

[0017] As used herein, the term “fluorinated sulfonic acid” refers to a compound of group RF-SOsH, wherein variable RFis as defined herein. In some embodiments, RFis fluoro or a moiety comprising at least one F atom, as described herein.

[0018] The term “halogen” or “halo” refers to fluoro, chloro, bromo and iodo. In some embodiments, the halo is fluoro.

[0019] The term “dehydrohalogenation”, as used herein, means a process during which hydrogen and halogen, e.g., Cl, Br or I on adjacent carbons in a molecule are removed to form the corresponding olefin.

[0020] As used herein, the term “dehydrochlorination” refers to a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed to form the corresponding olefin.

[0021] As used herein, the phrase “optionally substituted” means unsubstituted or substituted. The substituents are independently selected, and substitution may be at any chemically accessible position. As used herein, the term “substituted” means that a hydrogen atom is removed and replaced by a substituent. It is to be understood that substitution at a given atom is limited by valency.4INCORPORATED BY REFERENCE (RULE 20.6)

[0022] The term “mixing”, as defined herein, refers to the process of stirring the reactants (e.g., 2-chloro-3,3,3-trifluoroprop-1-ene, hydrogen fluoride, and boron trihalide), at a particular mixing power of, for example, about 0.1 to about 50 horsepower per 1000 gallons of the reaction mixture. The mixing ( / .e., stirring) can be effected, for example, by mechanical means (e.g., a stirrer or in a shaker so that the reactants are substantially thoroughly mixed with one another under conditions sufficient to react 2-chloro-3,3,3-trifluoroprop-1-ene with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane) and by other means known in the art or as described herein.

[0023] Accordingly, in some embodiments, mixing is provided by a mechanical agitator. However, the mixing power input can alternatively be provided by other methods. These methods are known in the industry and include using the mixing provided by gas bubbles from gas added to the vessel or generated within the vessel by vaporization of liquid. Mixing can also be provided by withdrawing the liquid from the vessel to a pump and pumping the liquid back into the vessel. A static mixer, rotor stator heads, or other device intended to mix the contents can be present in the circulation path of the liquid to provide additional mixing power input. Mixing can be provided by a single method or by a combination of two or more methods.

[0024] In some embodiments, the reactor stirs the reaction mixture by imparting to the agitator the power to stir the liquid in the tank. The power input is calculated based on the combination of several parameters, including the geometry of the vessel, design of baffles, if any, design of the impeller, and speed at which the impeller rotates. This calculation is performed by one of ordinary skill in the art. In the process described herein, to maximize the yield, in an embodiment the base are mixed together, generating small bubbles and high interphase surface area.Autoclave reactors are examples of reactors that could achieve the above-identified horsepower per gallon of liquid. In some embodiments, about 0.1 to about 50 horsepower / 1000 gallon of liquid is imparted to the agitator, making the agitator agitate the reaction mixture. In some embodiments, about 0.5 to about 40 horsepower / 1000 gallon of liquid is imparted to the agitator, making the agitator agitate the reaction mixture. In some embodiments, about 1 to about 35 horsepower / 1000 gallon of liquid is imparted to the agitator, causing the agitator to agitate the reaction mixture.5INCORPORATED BY REFERENCE (RULE 20.6)

[0025] As used herein, the term “caustic” refers to a base that would dissociate when placed in water. Examples include an alkali metal oxides, hydroxide, or amide, such as sodium or potassium oxide or sodium or potassium hydroxide or sodium or potassium amide; or alkaline earth metal hydroxide, alkaline earth metal oxide or amide, alkali metal carbonate or alkali metal phosphate or alkali metal carboxylate. In some embodiments, a process of the present application, is performed in the presence of a caustic (or base) that would dissociate when placed in water.

[0026] As used herein, the term “boron trihalide” refers to a compound of the formula BX3, wherein each X is an independently selected halide ( / .e., fluoride, chloride, bromide, iodide). In some embodiments, each X is the same. In some embodiments, the boron trihalide is BF3, BCb, or BBrs. In some embodiments, the boron trihalide is BF3.

[0027] As described herein, the processes of the present application may be conducted in the presence of a catalyst (e.g., a boron trihalide catalyst). As used herein, the term “catalyst”, refers to a substance that speeds up the chemical reaction, but is not consumed by the reaction; thus, it can be recovered chemically unchanged at the end of the reaction.

[0028] The following abbreviations may be used throughout the present application:CFC: chlorofluorocarbonHFO: hydrofluoroolefinHCFC: hydrochlorofluorocarbonHCFC-243db or 243db: 1 ,1 ,1-trifluoro-2,3-dichloropropaneHCFC-244bb or 244bb: 2-chloro-1 ,1 ,1 ,2-tetrafluoropropaneHF: hydrogen fluorideHFC-245cb: 1 , 1 ,1 ,2,2-pentafluoropropane250fb: 1 ,1 , 1 ,3-tetrachloropropane253fb: 3-chloro-1 , 1 , 1-trifluoropropaneHCFO-1233xf or 1233xf: 2-chloro-3,3,3-trifluoroprop-1-ene6INCORPORATED BY REFERENCE (RULE 20.6)HFO-1234yf or 1234yf: 2,3,3,3-tetrafluoroprop-1-ene or 2, 3,3,3- tetrafluoropropeneHFO-1243zf or 1243zf: 3,3,3-trifluoroprop-1-ene1230xa: 1 , 1 ,2,3-tetrachloroprop-1 -eneProcesses of the Invention

[0029] The present application provides processes for preparing 2-chloro-1 , 1 ,1 ,2- tetrafluoropropane (244bb). In some embodiments, the present application provides a process comprising reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form the 2-chloro-1 , 1 ,1 ,2- tetrafluoropropane (244bb).

[0030] In some embodiments, the process of preparing 2-chloro-1 , 1 ,1 ,2- tetrafluoropropane (244bb) comprises reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid.

[0031] In some embodiments, the boron trihalide is selected from the group consisting of boron trifluoride (BF3), boron trichloride (BCI3), and boron tribromide (BBrs). In some embodiments, the boron trihalide is boron trifluoride (BF3).

[0032] In some embodiments, the process is performed in the absence of the fluorinated sulfonic acid.

[0033] In some embodiments, the process is performed in the presence of the fluorinated sulfonic acid. In some embodiments, the fluorinated sulfonic acid is a compound of Formula I:wherein:RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R1-O-CX1H-C(X1)2-; each X1is independently selected from the group consisting of H and fluoro, provided that at least one X1is fluoro; andR1is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted.7INCORPORATED BY REFERENCE (RULE 20.6)

[0034] In some embodiments, RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, and C1-6 fluoroalkoxy. In some embodiments, RFis selected from the group consisting of fluoro, C1-3 fluoroalkyl, and C1-3 fluoroalkoxy. In some embodiments, RFis selected from the group consisting of fluoro, C1-3 fluoroalkyl, and C1-3 fluoroalkoxy.

[0035] In some embodiments, RFis R1-O-CX1H-C(X1)2-. In some embodiments, R1is unsubstituted C1-6 alkyl. In some embodiments, R1is C1-6 fluoroalkyl. In some embodiments, R1is unsubstituted C2-6 alkenyl. In some embodiments, R1is C2-6 fluoroalkenyl.

[0036] In some embodiments, each X1is fluoro. In some embodiments, one X1group is H and two X1groups are fluoro. In some embodiments, two X1groups are H and one X1group is fluoro.

[0037] In some embodiments, the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, 1 , 1 ,2,2- tetrafluoroethane-1 -sulfonic acid, 1 ,1 ,2-trifluoro-2-(trifluoromethoxy)ethane-1-sulfonic acid, 1 ,1 ,2-trifluoro-2-(perfluoroethoxy)ethane-1-sulfonic acid, and 1 ,1 ,2,2,4,5,5,7,8,8-decafluoro-3,6-dioxo-4-(trifluoromethyl)oct-7-ene-1-sulfonic acid.

[0038] In some embodiments, the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, 1 , 1 ,2,2- tetrafluoroethane-1 -sulfonic acid. In some embodiments, the fluorinated sulfonic acid is fluorosulfonic acid or trifluoromethanesulfonic acid ( / .e., triflic acid). In some embodiments, the fluorinated sulfonic acid is fluorosulfonic acid. In some embodiments, the fluorinated sulfonic acid is trifluoromethanesulfonic acid.

[0039] In some embodiments, the fluorinated sulfonic acid is selected from 1 ,1 ,2- trifluoro-2-(trifluoromethoxy)ethane-1-sulfonic acid, 1 ,1 ,2-trifluoro-2- (perfluoroethoxy)ethane-l-sulfonic acid, and 1 ,1 ,2,2,4,5,5,7,8,8-decafluoro-3,6- dioxo-4-(trifluoromethyl)oct-7-ene-1-sulfonic acid.

[0040] Additional fluorinated sulfonic acids useful in the processes described herein can be found, for example, in U.S. Patent No. 2,403,207 and U.S. Patent Publication No. 20060276670, the disclosure of each of which is incorporated herein by reference in its entirety.8INCORPORATED BY REFERENCE (RULE 20.6)

[0041] In some embodiments, the reacting is performed at a temperature of from about 0°C to about 200°C, for example, about 0°C to about 150°C, about 0°C to about 125°C, about 0°C to about 100°C, about 0°C to about 75°C, about 0°C to about 50°C, about 0°C to about 25°C, about 25°C to about 200°C, about 25°C to about 150°C, about 25°C to about 125°C, about 25°C to about 100°C, about 25°C to about 75°C, about 25°C to about 50°C, about 50°C to about 200°C, about 50°C to about 150°C, about 50°C to about 125°C, about 50°C to about 100°C, about 50°C to about 75°C, about 75°C to about 200°C, about 75°C to about 150°C, about 75°C to about 125°C, about 75°C to about 100°C, about 100°C to about 200°C, about 100°C to about 150°C, about 100°C to about 125°C, about 125°C to about 200°C, about 125°C to about 150°C, or about 150°C to about 200°C.

[0042] In some embodiments, the reacting is performed at a temperature of from about 25°C to about 200°C. In some embodiments, the reacting is performed at a temperature of from about 25°C to about 155°C. In some embodiments, the reacting is performed at a temperature of from about 25°C to about 150°C.ln some embodiments, the reacting is performed at a temperature of from about 45°C to about 150°C. In some embodiments, the reacting is performed at a temperature of from about 40°C to about 155°C. In some embodiments, the reacting is performed at a temperature of from about 45°C to about 150°C. In some embodiments, the reacting is performed at a temperature of from about 40°C to about 80°C. In some embodiments, the reacting is performed at a temperature of from about 45°C to about 75°C.

[0043] In some embodiments, a molar excess of boron trihalide is used based on 1 molar equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). In some embodiments, a catalytic amount of boron trihalide is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0044] In some embodiments, about 0.1 to about 10 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), for example, about 0.1 to about 5, about 0.1 to about 1, about 0.1 to about 0.5, about 0.1 to about 0.25, about 0.25 to about 10, about 0.25 to about 5, about 0.25 to about 1 , about 0.25 to about 0.5, about 0.5 to about 10, about 0.5 to about 5, about 0.5 to about 1 , about 1 to about 10, about 1 to about 5, or about 5 to about 10 equivalents.9INCORPORATED BY REFERENCE (RULE 20.6)In some embodiments, about 0.25 to about 1.25 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0045] In some embodiments, a molar excess of hydrogen fluoride is used based on 1 molar equivalent of the 2-chloro-3, 3, 3-trifluoroprop-1-ene (1233xf) ( / .e., an amount greater than 1 equivalent of hydrogen fluoride based on 1 equivalent of 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf); for example, it is understood that in a reactor system, the hydrogen fluoride can be passed over the reaction mixture as a gas, thereby contacting the reaction mixture).

[0046] In some embodiments, about 1 to about 100 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), for example, about 1 to about 75, about 1 to about 50, about 1 to about 25, about 1 to about 10, about 10 to about 100, about 10 to about 75, about 10 to about 50, about 10 to about 25, about 25 to about 100, about 25 to about 75, about 25 to about 50, about 50 to about 100, about 50 to about 75, or about 75 to about 100. In some embodiments, about 5 to about 15 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0047] In some embodiments, the processes provided herein further comprise substantially isolating the 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC-244bb). By “substantially isolated” is meant that the compound is at least partially or substantially separated from the environment in which it was formed or detected. Partial separation can include, for example, a composition enriched in the 2-chloro- 1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb). Substantial separation can include compositions containing at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, at least about 97%, or at least about 99% by weight of the compounds provided herein, or salt thereof. Methods for isolating compounds are routine in the art.

[0048] In some embodiments, the processes provided herein further comprise substantially isolating (e.g., purifying) 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC- 244bb)via distillation. In some embodiments, the process comprises substantially isolating the 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC-244bb) by removing one or more additional components of a reaction mixture (e.g., hydrogen fluoride, boron trihalide, fluorinated sulfonic acid, or any combination thereof). In some10INCORPORATED BY REFERENCE (RULE 20.6)embodiments, the one or more additional components of the reaction mixture are removed via distillation.

[0049] The processes of the present invention can be performed, for example, over one or more reaction zones under conditions effective to produce the 2-chloro- 1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb), or a composition comprising 2-chloro- 1 , 1 ,1 ,2-tetrafluoropropane (HCFC-244bb).

[0050] Accordingly, in some embodiments, the processes provided herein further comprise contacting 2-chloro-3, 3, 3, -trifluoropropene (1233xf) with hydrogen fluoride in the presence of boron trihalide in multiple reaction zones under conditions effective to produce the 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb), or a composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb).

[0051] Accordingly, in some embodiments, the processes provided herein further comprise contacting 2-chloro-3, 3, 3, -trifluoropropene (1233xf) with hydrogen fluoride in the presence of boron trihalide and a fluorinated sulfonic acid (e.g., a fluorinated sulfonic acid of Formula I) in multiple reaction zones under conditions effective to produce the 2-chloro-1 ,1,1 ,2-tetrafluoropropane (HCFC-244bb), or a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0052] In some embodiments, the processes provided herein comprise preparing a composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb) and one or more additional components. In some embodiments, the composition comprising 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC-244bb) comprises less than about 2% by weight 1 ,1 ,1 ,2,2-pentafluoropropane (HFC-245cb). In some embodiments, the composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb) comprises less than about 1% by weight 1 ,1,1,2,2-pentafluoropropane (HFC-245cb).

[0053] In some embodiments, the composition comprising 2-chloro-1, 1 , 1 ,2- tetrafluoropropane (HCFC-244bb) further comprises less than about 50% by weight of unreacted 2-chloro-3, 3, 3, -trifluoropropene (1233xf). In some embodiments, the composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb) further comprises less than about 10% by weight of unreacted 2-chloro-3,3,3,- trifluoropropene (1233xf). In some embodiments, the composition comprising 2- chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) further comprises less than about 5% by weight of unreacted 2-chloro-3, 3, 3, -trifluoropropene (1233xf). In some11INCORPORATED BY REFERENCE (RULE 20.6)embodiments, the composition comprising 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb) further comprises less than about 2% by weight of unreacted 2- chloro-3, 3, 3, -trifluoropropene (1233xf).

[0054] In some embodiments, greater than about 85% of the 2-chloro-3,3,3,- trifluoropropene (1233xf) is converted to 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC- 244bb). In some embodiments, greater than about 90% of the 2-chloro-3,3,3,- trifluoropropene (1233xf) is converted to 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC- 244bb). In some embodiments, greater than about 95% of the 2-chloro-3,3,3,- trifluoropropene (1233xf) is converted to 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC- 244bb). In some embodiments, more than about 98% of the 2-chloro-3,3,3,- trifluoropropene (1233xf) is converted to 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC- 244bb).

[0055] In some embodiments, the multiple reaction zones comprise multiple reactors operated in series. In some embodiments, the multiple reactors comprise at least a first and second reactors operated in series.

[0056] In some embodiment, the processes provided herein further comprise: a) contacting, in a first reaction zone, feed 2-chloro-3, 3, 3, -trifluoropropene (HCFO-1233xf) with hydrogen fluoride, a first boron trihalide, and, optionally, a first fluorinated sulfonic acid under conditions effective to produce a first composition comprising unreacted HCFO-1233xf, a first amount of 2-chloro- 1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb), and a first amount of 1 , 1 , 1 ,2,2- pentafluoropropane (HFC-245cb); b) contacting, in a second reaction zone, the first composition with a boron trihalide, and, optionally, a second fluorinated sulfonic acid under conditions to produce a second composition, wherein the second composition comprises 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (HCFC-244bb), and less than about 5% 2- chloro-3, 3, 3, -trifluoropropene (HCFO-1233xf) by weight relative to the amount of feed 2-chloro-3, 3, 3, -trifluoropropene (HCFO-1233xf), and less than about 2% by weight 1 , 1 ,1 ,2,2-pentafluoropropane (HFC-245cb).

[0057] In some embodiments, the first and second boron trihalide are the same. In some embodiment, the first and second boron trihalide each BF3. In some embodiment, the first and second boron trihalide are different.12INCORPORATED BY REFERENCE (RULE 20.6)

[0058] In some embodiments, the first and second fluorinated sulfonic acids are the same. In some embodiments, the first and second fluorinated sulfonic acids are different. In some embodiments, the first and second fluorinated sulfonic acids are each an independently selected compound of Formula I, as described herein.

[0059] In some embodiments, the first reaction zone does not comprise the first fluorinated sulfonic acid. In some embodiments, the first reaction zone comprises the first fluorinated sulfonic acid.

[0060] In some embodiments, the second reaction zone does not comprise the second fluorinated sulfonic acid. In some embodiments, the second reaction zone comprises the second fluorinated sulfonic acid.

[0061] In some embodiments, the second reaction zone is comprised of one or more reactors operated in series. In some embodiments, the first and the second reaction zones each comprise CSTR reactors. In some embodiments, said first composition further comprises carryover boron trihalide (e.g., BF3), and, optionally carryover fluorinated sulfonic acid (e.g., a compound of Formula I, as described herein) which is removed from the first composition prior to contacting in said second reaction zone.

[0062] Once prepared according to a process of the invention, the 2-chloro- 1 ,1 ,1 ,2-tetrafluoropropane, or a composition comprising the 2-chloro-1, 1,1,2- tetrafluoropropane can then be used to prepare additional compounds, including HFO-1234yf, as shown below in Schemes Il-Ill, where X is halide and RF-SOsH represents the optional fluorinated sulfonic acid component of the processes of the invention.Scheme II.13INCORPORATED BY REFERENCE (RULE 20.6)

[0063] In some embodiments, the process provided herein further comprises dehydrochlorinating the 2-chloro-1 ,1 ,1,2-tetrafluoropropane (244bb) to form 2, 3,3,3- tetrafluoropropene (HFO-1234yf). In some embodiments, the dehydrochlorination reaction comprises reacting the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with caustic to form 2,3,3,3-tetrafluoropropene (1234yf).

[0064] Additional processes for preparing HFO-1234yf and / or 244bb can be found, for example, in U.S. Patent Application Nos: 12 / 404,130, and U.S. Patent Publication Nos. 20140350309 and 20140303409, the disclosure of each of which is incorporated herein by reference in its entirety.

[0065] For example, in some embodiments, the process of preparing HFO-1234yf and / or 244bb can be performed adiabatic reaction zone (e.g., in one or more adiabatic reactors). The adiabatic reaction zone comprises at least two serially- connected adiabatic reactors and having a heat exchanger in fluid communication disposed between each two reactors in series.

[0066] In some embodiment, the adiabatic reaction zone comprises a first adiabatic reactor and a final adiabatic reactor. The first adiabatic reactor is a preceding adiabatic reactor relative to any adiabatic reactors or heat exchangers downstream from the first adiabatic reactor in the adiabatic reaction zone. The final adiabatic reactor is a subsequent adiabatic reactor relative to any adiabatic reactors or heat exchangers upstream of the final adiabatic reactor in the adiabatic reaction zone.

[0067] In some embodiments, the first adiabatic reactor is upstream of and in fluid communication with a heat exchanger. In some embodiments, the heat exchanger is in fluid communication and upstream of a subsequent adiabatic reactor.14INCORPORATED BY REFERENCE (RULE 20.6)

[0068] In some embodiments, the adiabatic reaction zone consists of two reactors, a first adiabatic reactor and a final adiabatic reactor. In some embodiments, a heat exchanger is downstream from the first adiabatic reactor and upstream of the final adiabatic reactor.

[0069] One skilled in the art will understand the relationships between the first adiabatic reactor, which has no preceding (upstream) reactor, a subsequent adiabatic reactor, which has at least one preceding reactor and the final adiabatic reactor, which has no subsequent (downstream) reactor and is a subsequent reactor. In some embodiments, the adiabatic reactors in the adiabatic reaction zone are in fluid communication with heat exchangers, wherein a heat exchanger is disposed between two reactors.

[0070] In some embodiments, the adiabatic reaction zone consists of a first adiabatic reactor, one or more additional adiabatic reactors (e.g., a second adiabatic reactor, a third adiabatic reactor, and the like, which may also be referred to as subsequent adiabatic reactors) and a final adiabatic reactor, wherein each reactor operates adiabatically and a heat exchanger is arranged between the first adiabatic reactor and the one or more additional adiabatic reactors and a heat exchanger is arranged between each of the reactors. An upper limit of the number of adiabatic reactors and heat exchangers, wherein a heat exchanger is disposed between two reactors in the adiabatic reaction zone may be based on practical reasons such as controlling cost and complexity or based on achieving a particular goal such as conversion of starting material or a formation of a particular product. In some embodiments, two or more adiabatic reactors are used in the adiabatic reaction zone, for example two to ten reactors, two to four reactors, or two to three reactors.

[0071] The adiabatic reactors may be of any shape that is conducive to performing one or more of the processes described herein. In some embodiments, each reactor is independently a cylindrical tube or pipe, each of which may be straight or coiled. In some embodiments, the reactor is a plug flow reactor. Plug flow reactors minimize back mixing thereby resulting in lower overall conversion.

[0072] Due to the corrosive nature of one or more of the processes described herein, adiabatic reactors for use in the adiabatic reaction zone disclosed herein may be comprised of materials which are resistant to corrosion. Exemplary materials15INCORPORATED BY REFERENCE (RULE 20.6)include, but are not limited to, stainless steel, (e.g., austenitic type, copper-clad steel, nickel-based alloy, gold, gold-lined, or quartz). Nickel-based alloys are available commercially and include, for example, high nickel alloys, such as Monel™ nickelcopper alloys, Hastelloy™ nickel-based alloys, and Inconel™ nickel-chromium alloys. In some embodiments, the reactor is comprised of nickel-based alloy. In some embodiments, one or more adiabatic reactors may be lined with fluoropolymer, provided the fluoropolymer is compatible with the reaction temperature of the process. Other materials may include SiC or graphite for corrosion resistance.

[0073] In addition to the adiabatic reactors of the adiabatic reaction zone disclosed herein, heat exchangers, effluent lines, units associated with mass transfer, contacting vessels (pre-mixers), distillation columns, and feed and material transfer lines associated with reactors, heat exchangers, vessels, columns, and units that are used in the processes provided herein should be constructed of materials resistant to corrosion, such as those recited above.

[0074] In some embodiments, the present application provides an adiabatic reaction zone. In some embodiments, the adiabatic reaction zone is suitable for performing one or more of the processes described herein. In some embodiments, the adiabatic reaction zone comprises at least two adiabatic reactors. In some embodiments, a heat exchanger is arranged between each of the reactors. In some embodiments, the processes provided herein comprise providing an adiabatic reaction zone comprising at least two serially-connected adiabatic reactors and having a heat exchanger disposed in sequence and in fluid communication between each two reactors in series; introducing a starting material of a process described herein into an adiabatic reaction zone wherein a first reaction product is produced in a first adiabatic reactor; passing the first reaction product from the first adiabatic reactor to a heat exchanger to produce an intermediate product; then introducing the intermediate product from the heat exchanger to a subsequent adiabatic reactor wherein a second reaction product is produced; and optionally, passing the second reaction product from the subsequent adiabatic reactor through a heat exchanger prior to introducing the second reaction product into a third adiabatic reactor, if present, and so on.16INCORPORATED BY REFERENCE (RULE 20.6)

[0075] Notwithstanding the foregoing, other process steps may occur upstream of the adiabatic reaction zone. The upstream process steps may be performed in one or more reactors. For clarity, even if one or more reactors are present upstream, the “first adiabatic reactor” referred to herein refers to a first adiabatic reactor in a series of adiabatic reactors in which a process provided herein performed (e.g., a process of preparing 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), comprising reacting 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and optionally in the presence of a fluorinated sulfonic acid) wherein a heat exchanger is located between the first adiabatic reactor in the series and the second (subsequent) reactor in the series. Thus, any reactors in which process steps are performed upstream of the adiabatic reaction zone and thus upstream of the first adiabatic reactor as thus defined, cannot be considered the “first adiabatic reactor”.

[0076] There may be other processes which occur downstream from the processes in the adiabatic reaction zone as described herein.

[0077] In some embodiments, heat exchangers are used in the processes performed in the adiabatic reaction zones as described herein. In some embodiments, a heat exchanger is arranged between two adiabatic reactors in series. In some embodiments, the heat exchangers replace the heat used by the reactions which are endothermic processes (e.g., dehydrohalogenation reactions). In some embodiments, the heat exchangers used herein may be shell and tube heat exchangers. In some embodiments, heat exchangers may employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers, electric heaters, among others. Heat exchangers may provide heat by electric heating. In some embodiments, heat exchangers may use process streams as heat exchange fluid. Other designs may be used which are compatible with the physical and chemical requirements of the processes described herein, including the temperature and corrosive nature of the reaction components.

[0078] In some embodiments, each heat exchanger may be operated independently of the other heat exchangers in the adiabatic reaction zone. In some embodiments, each heat exchanger may be operated to provide an intermediate product having the same temperature as the intermediate product exiting another17INCORPORATED BY REFERENCE (RULE 20.6)heat exchanger in the adiabatic reaction zone. In some embodiments, each heat exchanger may be operated to provide an intermediate product having a different temperature relative to intermediate products exiting other heat exchangers in the adiabatic reaction zone.

[0079] In some embodiments, each heat exchanger may be independently disposed in a vessel with the preceding or subsequent adiabatic reactor. In some embodiments, each heat exchanger may be independently disposed in a separate vessel from the preceding or subsequent adiabatic reactor. In some embodiments, fluid communication is maintained between subsequent adiabatic reactors through heat exchangers as set forth previously.

[0080] In some embodiments, a heat exchanger as described herein may also be used to heat starting material to desired reaction temperature upstream of the first adiabatic reactor either in the adiabatic reaction zone or external to the adiabatic reaction zone.

[0081] In some embodiments, the processes provides here further comprise: (a) removing impurities from a reactor (e.g., an adiabatic reactor as described herein) such that the reactor is substantially free of impurities; (b) providing a starting composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb), which has been prepared according to a process provided herein, in the reactor under conditions effective to produce a final composition comprising 2, 3,3,3- tetrafluoropropene (HFO-1234yf).

[0082] In some embodiments, the impurities in the reactor are selected from the group consisting of metal halides, metal oxides, and carbonaceous materials. In some embodiments, the metal halides comprise halides of Ni, Cr, Fe, Mo, Nb, Cu, and Co.

[0083] In some embodiments, the step of removing impurities from the reactor comprises introducing a reducing agent into the reactor under conditions effective to convert any metal halides or metal oxides into metallic metals.

[0084] In some embodiments, the reducing agent is selected from the group consisting of H2, NH3, CO, C1-C12 hydrocarbons, and combinations of these.18INCORPORATED BY REFERENCE (RULE 20.6)

[0085] In some embodiments, the step of removing impurities from the reactor comprises introducing an oxidizing agent into the reactor under conditions effective to burn off the carbonaceous materials in the reactor.

[0086] In some embodiments, the oxidizing agent is selected from the group consisting of H2O, CO2, O2, air, O3, CI2, N2O, and combinations of these. In some embodiments, the oxidizing agent comprises oxygen.

[0087] In some embodiments, the step of removing impurities from the reactor comprises physically removing carbonaceous materials, metal oxides, and metal halides from the reactor. In some embodiments, the step of physically removing the carbonaceous materials, metal oxides, and metal halides from the reactor is selected from the group consisting of electrical polishing, mechanical polishing, hydraulic methods, and combinations of these.

[0088] In some embodiments, the selectivity of preparing the 2, 3,3,3- tetrafluoropropene (1234yf) is at least 90% or higher.

[0089] In some embodiments, the process provided here further comprises: (a) providing a starting composition comprising 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), prepared according to a process provided herein, in a reactor that is substantially free from impurities; and (b) contacting the starting composition in the reactor under conditions effective to produce a final composition comprising 2, 3,3,3- tetrafluoropropene (1234yf).

[0090] In some embodiments, the selectivity of preparing the 2, 3,3,3- tetrafluoropropene is at least 90% or higher.

[0091] In some embodiments, the present application provides a process comprising: (i) providing a composition comprising 2-chloro-1 ,1 , 1 ,2- tetrafluoropropane (244bb), which has been prepared according to a process provided herein; (ii) reducing the level of hydrogen fluoride within the composition such that it is substantially free of hydrogen fluoride; and (iii) contacting said starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (1234yf).

[0092] In some embodiments, the level of hydrogen fluoride is reduced within the composition such that hydrogen fluoride is present in the composition in an amount19INCORPORATED BY REFERENCE (RULE 20.6)less than about 500 ppm. In some embodiments, the level of hydrogen fluoride is reduced within the composition such that hydrogen fluoride is present in the composition in an amount less than about 50 ppm. In some embodiments, reducing the hydrogen fluoride level of the composition comprises the distilling of the hydrogen fluoride, passing the composition through a scrubber, or passing the composition over a solid sorbent.

[0093] In some embodiments, the solid sorbent is selected from the group consisting of alumina, calcium carbonate, sodium carbonate, and sodium aluminate.

[0094] The present application further provides a process, comprising (i) providing a starting composition comprising 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) that has been prepared according to a process provided herein, that is substantially free of HF; and (ii) contacting said starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (1234yf).

[0095] In some embodiments, the hydrogen fluoride is present in the composition in an amount less than about 500 ppm. In some embodiments, the hydrogen fluoride is present in the composition in an amount less than about 50 ppm.

[0096] In some embodiments, the contacting of said starting composition with a dehydrochlorination catalyst occurs in the vapor phase. In some embodiments, the contacting of said starting composition with a dehydrochlorination catalyst occurs in the liquid phase.

[0097] In some embodiments, the catalyst is selected from the group consisting of (i) one or more metal halides, (ii) one or more halogenated metal oxides, (iii) one or more zero-valent metals / metal alloys, and (iv) a combination of two or more of these.

[0098] In some embodiments, the dehydrochlorinating occurs in the vapor phase.

[0099] In some embodiments, the intermediate products made in each step are purified before reacting in the next step so that impurities in the 2,3,3,3- tetrafluoropropene (1234yf) made in the final step can be removed to achieve the desired purity, for example >99.5% by weight. Purification techniques known in the art such as distillation, extraction, decantation, and adsorption can be used. One skilled in the art will recognize that impurities that are advantageous to remove20INCORPORATED BY REFERENCE (RULE 20.6)before the final reaction step to make 2,3,3,3-tetrafluoropropene (1234yf) are those that have, or react to form those that have, similar boiling points to 2,3,3,3- tetrafluoropropene (1234yf).

[0100] In some embodiments, the 2-chloro-3, 3, 3, -trifluoropropene (1233xf) described herein can be prepared according to a process comprising dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (243db) to form the 2-chloro-3,3,3-trifluoropropene (1233xf). In some embodiments, the dehydrochlorinating comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with caustic to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

[0101] In some embodiments, the step of preparing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) is performed according to the process disclosed in U.S. Patent No.: 8,884,083, the disclosure of which is incorporated herein by reference in its entirety.

[0102] Accordingly, in some embodiments, the process of preparing 2-chloro-3,3,3-trifluoropropene (1233xf) comprises contacting 1 , 1 , 1-trifluoro-2,3- dichloropropane (243db) with a catalyst in a reaction zone to produce a product mixture comprising 2-chloro-3,3,3-trifluoropropene (1233xf), wherein said catalyst comprises MY supported-on carbon, and M is K, Na or Cs, and Y is F, Cl or Br. In some embodiments, the carbon is an activated carbon. In some embodiments, the carbon is an acid washed activated carbon. In some embodiments, M is K and Y is F or Cl.

[0103] In some embodiments, the temperature in the reaction zone is from about 140°C to about 400°C. In some embodiments, the temperature in the reaction zone is from about 150°C to about 250°C. In some embodiments, the temperature in the reaction zone is from about 175°C to about 225°C.

[0104] In some embodiments, the product selectivity for preparing the 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 90 mole %. In some embodiments, the product selectivity for preparing the 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 95 mole %. In some embodiments, the dehydrochlorination selectivity for preparing the 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 90 mole %.21INCORPORATED BY REFERENCE (RULE 20.6)

[0105] In some embodiments, the process of preparing 2-chloro-3,3,3- trifluoropropene (1233xf) comprises dehydrochlorinating 1,1 ,1 ,3-tetrachloropropane (250fb) to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

[0106] In some embodiments, the process of preparing 2-chloro-3,3,3- trifluoropropene (1233xf) is a process disclosed in US 20120215035, the disclosure of which is incorporated herein by reference in its entirety.

[0107] Accordingly, in some embodiments, the process provided herein further comprises contacting 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) with a catalyst in a reaction zone to produce a product mixture comprising 2-chloro-3,3,3- trifluoropropene (1233xf).

[0108] In some embodiments, the process further comprises contacting 1,1,1- trifluoro-2,3-dichloropropane (243db) with a chromium oxyfluoride catalyst in a reaction zone to produce a product mixture comprising 2-chloro-3,3,3- trifluoropropene (1233xf).

[0109] In some embodiments, the process is conducted in the presence of hydrogen fluoride (HF). In some embodiments, the mole ratio of HF to 2-chloro- 3,3,3-trifluoropropene in the reaction zone is no more than 0.9.

[0110] In some embodiments, the temperature in the reaction zone is from about 200°C. to about 500°C. In some embodiments, the temperature in the reaction zone is from about 275°C. to about 450°C.

[0111] In some embodiments, the product selectivity to form 2-chloro-3,3,3- trifluoropropene is at least 90 mole %. In some embodiments, the dehydrochlorination selectivity to 2-chloro-3,3,3-trifluoropropene is at least 95 mole %.

[0112] In some embodiments, the 1,1,1-trifluoro-2,3-dichloropropane (243db) is prepared according to a process comprising chlorinating 3,3,3-trifluoropropene (1243zf) to form the 1,1 ,1-trifluoro-2,3-dichloropropane (243db). In some embodiments, said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with the chlorine or HCI / oxygen to form the 1 , 1 , 1 -trifluoro-2,3- dichloropropane (243db). In some embodiments, said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with chlorine to form the 1 , 1 , 1-trifluoro-22INCORPORATED BY REFERENCE (RULE 20.6)2,3-dichloropropane (243db). In some embodiments, said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with HCI / oxygen to form the 1,1,1- trifluoro-2,3-dichloropropane (243db).

[0113] In some embodiments, the process of preparing 1 , 1 , 1-trifluoro-2,3- dichloropropane (243db) is a process disclosed in U.S. Patent No. 9,938,208, the disclosure of which is incorporated herein by reference in its entirety.

[0114] Accordingly, in some embodiments, the process of preparing 1 , 1 , 1-trifluoro- 2,3-dichloropropane (243db) comprises contacting 3,3,3-trifluoropropene (1243zf) with chlorine in the liquid phase, in the absence or presence of a chlorination catalyst and with or without exposure to UV light, to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0115] In some embodiments, the chlorination catalyst comprises at least one metal halide, wherein the metal is a metal from Group 13, 14 or 15 of the periodic table or a transition metal or combination thereof. In some embodiments, the metal halide is supported on activated carbon. In some embodiments, the activated carbon is acid washed or caustic washed. In some embodiments, the metal is nickel, chromium, iron, scandium, yttrium, lanthanum, titanium, zirconium, hafnium, vanadium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, palladium, copper, zinc, tantalum, aluminum, tin, or lead. In some embodiments, the metal halide is nickel halide, iron halide or chromium halide. In some embodiments, the halide is a chloride. In some embodiments, the metal halide is nickel chloride, iron halide or chromium halide.

[0116] In some embodiments, the chlorination occurs in the vapor phase with or without a chlorination catalyst. In some embodiments, the chlorination is conducted at a temperature ranging from about 80°C to about 200°C and a pressure ranging from about 10 psig to about 100 psig, with the mole ratio of 3,3,3-trifluoropropene (1243zf) to chlorine gas ranging from about 1:0.02 to about 1: 1.

[0117] In some embodiments, the 3,3,3-trifluoropropene (1243zf) is prepared according to a process comprising reacting 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form the 3,3,3-trifluoropropene (1243zf). In some embodiments, the catalyst is selected from a chrome catalyst or an alumina catalyst.23INCORPORATED BY REFERENCE (RULE 20.6)

[0118] In some embodiments, the 3,3,3-trifluoropropene (1243zf) is prepared according to a process disclosed in U.S. Patent Application No. 15 / 917,376, the disclosure of which is incorporated herein by reference in its entirety.

[0119] Accordingly, in some embodiments the 3,3,3-trifluoropropene (1243zf) is prepared according to a process comprising reacting 3-chloro-1 ,1,1-trifluoropropane (253fb) with a base, wherein the reacting is conducted in the absence of a phase transfer catalyst. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst. In some embodiments, the reacting is conducted in an aqueous solvent component. In some embodiments, the reacting is conducted in an aqueous solvent component and in the absence of a phase transfer catalyst. In some embodiments, the reacting is conducted in water and in the absence of a phase transfer catalyst.

[0120] In some embodiments, the 3,3,3-trifluoropropene (1243zf) is prepared in the absence of a phase transfer catalyst and the aqueous solvent component comprises 0 to 40% w / w of an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and the aqueous solvent component comprises 0 to 30% w / w of an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and the aqueous solvent component comprises 0 to 20% w / w of an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and the aqueous solvent component comprises 0 to 10% w / w of an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and the aqueous solvent component does not comprise an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and an organic solvent. In some embodiments, the reacting is conducted in the absence of a phase transfer catalyst and an organic solvent component selected from an aliphatic alcohol, such as methanol, ethanol, n-propanol, isopropanol, butanol, and the like. In some embodiments, the reacting is conducted as a liquid phase reaction. In some embodiments, the reacting is performed in the presence of water.24INCORPORATED BY REFERENCE (RULE 20.6)

[0121] The present application further provides a process, comprising: i) reacting 1,1,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) chlorinating the 3,3,3-trifluoropropene (1243zf) to form 1 , 1 , 1-trifluoro-2,3- dichloropropane (243db); iii) dehydrochlorinating the 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) to form 2- chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1 , 1,1,2- tetrafluoropropane (244bb); and v) dehydrochlorinating the 2-chloro-1 ,1,1 ,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

[0122] The present application further provides a process, comprising: i) reacting 1,1,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) reacting the 3,3,3-trifluoropropene (1243zf) with chlorine or HCI / oxygen to form 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db); iii) reacting 1 ,1,1-trifluoro-2,3-dichloropropane (243db) with a first caustic to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1 , 1 , 1 ,2- tetrafluoropropane (244bb); and v) reacting the 2-chloro-1 ,1,1 ,2-tetrafluoropropane (244bb) with a second caustic to form 2,3,3,3-tetrafluoropropene (1234yf).

[0123] The present application provides a process, comprising: i) reacting 3-chloro-1,1 ,1 -trifluoropropane (253fb) with a base to form 3,3,3- trifluoroprop-1-ene (1243zf), wherein the reacting is conducted in the absence of a phase transfer catalyst; ii) reacting the 3,3,3-trifluoropropene (1243zf) with chlorine or HCI / oxygen to form 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db);25INCORPORATED BY REFERENCE (RULE 20.6)iii) reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a first caustic provided herein to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3, 3, 3, -trifluoropropene (1233xf) with hydrogen fluoride form 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb); and v) reacting the 2-chloro-1 ,1,1 ,2-tetrafluoropropane (244bb) with a second caustic provided herein to form 2,3,3,3-tetrafluoropropene (1234yf).

[0124] In some embodiments, step iv) comprises reacting the 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide (e.g., BF3) and a fluorinated sulfonic acid provided herein {e.g. a compound of Formula I).

[0125] In some embodiments, step iv) is performed at a temperature of from about 25°C to about 200°C, as described herein. In some embodiments, step iv) is performed at a temperature of from about 45°C to about 150°C. In some embodiments, step iv) is performed at a temperature of from about 40°C to about 155°C. In some embodiments, step iv) is performed at a temperature of from about 45°C to about 150°C. In some embodiments, step iv) is performed at a temperature of from about 40°C to about 80°C. In some embodiments, step iv) is performed at a temperature of from about 45°C to about 75°C.

[0126] In some embodiments, a molar excess of boron trihalide is used based on 1 molar equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above. In some embodiments, a catalytic amount of boron trihalide is used based on 1 equivalent of the 2-chloro-3, 3, 3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above.

[0127] In some embodiments, about 0.1 to about 10 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above. In some embodiments, about 0.25 to about 1.25 equivalents of boron trihalide are used based on 1 equivalent of the 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above.26INCORPORATED BY REFERENCE (RULE 20.6)

[0128] In some embodiments, a molar excess of hydrogen fluoride is used based on 1 molar equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above.

[0129] In some embodiments, about 1 to about 100 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above. In some embodiments, about 5 to about 15 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above.Uses

[0130] The processes provided herein are useful for preparing 2-chloro-1, 1 ,1,2- tetrafluoropropane (244bb), a compound which may be useful as an intermediate for producing 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf). HFO-1234yf is useful for a variety of applications, such as refrigerants, uses in high-temperature heat pumps, organic Rankine cycles, as fire extinguishing / fire suppression agents, propellants, foam blowing agents, solvents, and / or cleaning fluids.Compositions of the Invention

[0131] The present application further provides compositions comprising one or more major components (e.g., 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb), 2-chloro- 3,3,3-trifluoroprop-1-ene (1233xf), hydrogen fluoride, boron trihalide, fluorinated sulfonic acid, or any mixture thereof) in combination with one or more additional compounds (e.g., minor components). In some embodiments, the compositions are prepared according to one or more of the processes described herein. The presence of the additional compounds in a sample of 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), or a mixture thereof, may be used to identify the process by which one or more of the major components was manufactured.

[0132] Accordingly, the present application provides a composition, comprising 2- chloro-1 ,1,1 ,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1 -ene (1233xf), and BF3.27INCORPORATED BY REFERENCE (RULE 20.6)

[0133] In some embodiments, the composition comprises about 50 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.

[0134] In some embodiments, the composition comprises about 85 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.

[0135] In some embodiments, the composition comprises about 90 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.

[0136] In some embodiments, the composition comprises about 95 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.

[0137] In some embodiments, the composition comprises about 1 to about 45 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.

[0138] In some embodiments, the composition comprises about 1 to about 15 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.

[0139] In some embodiments, the composition comprises about 1 to about 12 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.

[0140] In some embodiments, the composition comprises about 1 to about 5 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.

[0141] In some embodiments, the composition comprises about 1 to about 3 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.

[0142] In some embodiments, the composition further comprises 1, 1,1, 2,2- pentafluoropropane (245cb).

[0143] In some embodiments, the composition comprises about 0.01 to about 1 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.

[0144] In some embodiments, the composition comprises about 0.01 to about 0.5 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.

[0145] In some embodiments, the composition comprises about 0.01 to about 0.2 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.

[0146] In some embodiments, the composition comprises about 0.01 to about 0.1 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.28INCORPORATED BY REFERENCE (RULE 20.6)

[0147] In some embodiments, the composition further comprises hydrogen fluoride.

[0148] In some embodiments, the composition further comprises a fluorinated sulfonic acid provided herein (e.g., a compound of Formula I, as described herein).EXAMPLES

[0149] 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.Example 1 - Fluorination of 2-Chloro-3,3,3-Trifluoropropene (1233xf) in the Presence of BF3

[0150] Into a 400 mL pressure reactor was added 2-chloro-3,3,3-trifluoropropene (1233xf), hydrogen fluoride, BF3. In Run 5, fluorosulfonic acid was also added to the reactor. The reactor was sealed and heated while shaking for 24 hours. After 24 hours, the reactor was cooled to room temperature and 200 ml of water was added. The organics in the reactor were vapor transferred at 70°C into a chilled, evacuated cylinder. The organics were analyzed by GC-MS. The conditions and results are shown in the following table.TABLE 1*GC area % estimated based on trends observed in Runs 1-5.INCORPORATED BY REFERENCE (RULE 20.6)OTHER EMBODIMENTS In some embodiments, the present application provides a process of preparing 2-chloro-1,1,1,2-tetrafluoropropane (244bb), comprising reacting 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide. The process of embodiment 1 , wherein the process comprises reacting the 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid. The process of embodiment 1 or 2, wherein the boron trihalide is BF3. The process of embodiment 2 or 3, wherein the fluorinated sulfonic acid is a compound of Formula I:wherein:RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R1-0-CX1H-C(X1)2-; each X1is independently selected from H and fluoro, provided that at least one X1is fluoro; andR1is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted. The process of embodiments 4, wherein RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, and C1-6 fluoroalkoxy. The process of embodiment 4, wherein RFis R1-0-CX1H-C(X1)2-. The process of any one of embodiments 2 to 4, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, 1 ,1,2,2-tetrafluoroethane-1 -sulfonic acid, 1,1,2- trifluoro-2-(trifluoromethoxy)ethane-1-sulfonic acid, 1 , 1 , 2-trifl uoro-2- (perfluoroethoxy)ethane-l -sulfonic acid, and 1,1,2,2,4,5,5,7,8,8-decafluoro-3,6- dioxo-4-(trifluoromethyl)oct-7-ene-1-sulfonic acid.INCORPORATED BY REFERENCE (RULE 20.6)The process of any one of embodiments 2 to 4, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid and trifluoromethanesulfonic acid. The process of any one of embodiments 1 to 8, wherein the reacting is performed at a temperature of from about 0°C to about 200°C. The process of any one of embodiments 1 to 8, wherein the reacting is performed at a temperature of from about 40°C to about 155°C. The process of any one of embodiments 1 to 10, wherein about 0.1 to about 10 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). The process of any one of embodiments 1 to 10, wherein about 0.25 to about 1 .25 equivalents of boron trihalide are used based on 1 equivalent of the 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf). The process of any one of embodiments 1 to 12, wherein a molar excess of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf). The process of any one of embodiments 1 to 12, wherein about 1.1 to about 100 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf). The process of any one of embodiments 1 to 12, wherein about 5 to about 15 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3.3.3-trifluoroprop-1-ene (1233xf). The process of any one of embodiments 1 to 15, further comprising dehydrochlorinating the 2-chloro-1 ,1 ,1,2-tetrafluoropropane (244bb) to form2.3.3.3-tetrafluoropropene (1234yf). The process of embodiment 16, wherein the dehydrochlorinating comprises reacting the 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb) with caustic to form2,3,3,3-tetrafluoropropene (1234yf). The process of any one of embodiments 1 to 17, wherein the 2-chloro-3,3,3,- trifluoropropene (1233xf) is prepared according to a process comprising31INCORPORATED BY REFERENCE (RULE 20.6)dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (243db) to form the 2- chloro-3,3,3-trifluoropropene (1233xf). The process of embodiment 18, wherein the dehydrochlorinating comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with caustic to form the 2- chloro-3,3,3-trifluoropropene (1233xf). The process of embodiment 18 or 19, wherein the 1 , 1 , 1-trifluoro-2,3- dichloropropane (243db) is prepared according to a process comprising chlorinating 3,3,3-trifluoropropene (1243zf) to form the 1 ,1 , 1-trifluoro-2,3- dichloropropane (243db). The process of embodiment 20, wherein said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with the chlorine or HCI / oxygen to form the 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db). The process of embodiment 20 or 21 , wherein the 3,3,3-trifluoropropene (1243zf) is prepared according to a process comprising reacting 1, 1,1,3- tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form the 3,3,3-trifluoropropene (1243zf). The process of embodiment 22, wherein the catalyst is selected from a chrome catalyst or an alumina catalyst. In some embodiments, the present application provides a process, comprising: i) reacting 1 ,1 ,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) chlorinating the 3,3,3-trifluoropropene (1243zf) to form 1 ,1 , 1 -trifluoro-2,3- dichloropropane (243db); iii) dehydrochlorinating the 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1, 1,1 ,2- tetrafluoropropane (244bb); and v) dehydrochlorinating the 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).32INCORPORATED BY REFERENCE (RULE 20.6)In some embodiments, the present application provides a process, comprising: i) reacting 1 ,1 ,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) reacting the 3,3,3-trifluoropropene (1243zf) with chlorine or HCI / oxygen to form 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db); iii) reacting 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) with a first caustic to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1 , 1 ,1 ,2- tetrafluoropropane (244bb); and v) reacting the 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb) with a second caustic to form 2,3,3,3-tetrafluoropropene (1234yf). The process of embodiment 24 or 25, wherein step iv) comprises reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid. The process of any one of embodiments 24 to 26, wherein the boron trihalide is BF3. The process of any one of embodiments 24 to 27, wherein the fluorinated sulfonic acid is a compound of Formula I:wherein:RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R1-O-CX1H-C(X1)2-; each X1is independently selected from H and fluoro, provided that at least one X1is fluoro; andR1is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted. In some embodiments, the present application provides a composition, comprising 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf), and BF3.33INCORPORATED BY REFERENCE (RULE 20.6)The composition of embodiment 29, further comprising 1,1 ,1 ,2,2- pentafluoropropane (245cb). The composition of embodiment 29 or 30, further comprising hydrogen fluoride. The composition of any one of embodiments 29 to 31 , which is prepared according to the process of any one of embodiments 1 to 28. The composition of any one of embodiments 29 to 31 , further comprising a fluorinated sulfonic acid. The composition of any one of embodiments 29 to 33, further comprising 1 ,1 ,1 ,2,2-pentafluoropropane (245cb). The composition of embodiment 33 or 34, which is prepared according to the process of any one of embodiments 2 to 28. It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims. It should be appreciated by those persons having ordinary skill in the art(s) to which the present invention relates that any of the features described herein in respect of any particular aspect and / or embodiment of the present invention can be combined with one or more of any of the other features of any other aspects and / or embodiments of the present invention described herein, with modifications as appropriate to ensure compatibility of the combinations. Such combinations are considered to be part of the present invention contemplated by this disclosure.INCORPORATED BY REFERENCE (RULE 20.6)

Claims

CLAIMSWhat is claimed is:

1. A process of preparing 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), comprising reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide.

2. The process of claim 1 , wherein the process comprises reacting the 2-chloro- 3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid.

3. The process of claim 1 , wherein the boron trihalide is BF3.

4. The process of claim 2, wherein the fluorinated sulfonic acid is a compound of Formula I:wherein:RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R1-0-CX1H-C(X1)2-; each X1is independently selected from H and fluoro, provided that at least one X1is fluoro; andR1is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted.

5. The process of claim 4, wherein RFis selected from the group consisting of fluoro, C1-6 fluoroalkyl, and C1-6 fluoroalkoxy.

6. The process of claim 4, wherein RFis R1-0-CX1H-C(X1)2-.

7. The process of claim 2, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, 1 ,1 , 2, 2-tetrafluoroethane-1 -sulfonic acid, 1 , 1 ,2-trifluoro-2- (trifluoromethoxy)ethane-l-sulfonic acid, 1 , 1 ,2-trifluoro-2- (perfluoroethoxy)ethane-l -sulfonic acid, and 1,1 ,2,2,4,5,5,7,8,8-decafluoro-3,6- dioxo-4-(trifluoromethyl)oct-7-ene-1-sulfonic acid.

8. The process of claim 2, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid and trifluoromethanesulfonic acid.35INCORPORATED BY REFERENCE (RULE 20.6)9. The process of claim 1, wherein the reacting is performed at a temperature of from about 0°C to about 200°C.

10. The process of claim 1, wherein the reacting is performed at a temperature of from about 40°C to about 155°C.

11. The process of claim 1, wherein about 0.1 to about 10 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1- ene (1233xf).

12. The process of claim 1, wherein about 0.25 to about 1 .25 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1- ene (1233xf).

13. The process of claim 1, wherein a molar excess of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

14. The process of claim 1, wherein about 1.1 to about 100 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

15. The process of claim 1, wherein about 5 to about 15 equivalents of hydrogen fluoride is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

16. The process of claim 15, further comprising dehydrochlorinating the 2-chloro- 1 ,1 ,1 ,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

17. The process of claim 16, wherein the dehydrochlorinating comprises reacting the 2-chloro-1,1,1 ,2-tetrafluoropropane (244bb) with caustic to form 2,3,3,3- tetrafluoropropene (1234yf).

18. The process of claim 1, wherein the 2-chloro-3, 3, 3, -trifluoropropene (1233xf) is prepared according to a process comprising dehydrochlorinating 1 , 1 , 1-trifluoro-2.3-dichloropropane (243db) to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

19. The process of claim 18, wherein the dehydrochlorinating comprises reacting 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) with caustic to form the 2-chloro-3.3.3-trifluoropropene (1233xf).36INCORPORATED BY REFERENCE (RULE 20.6)20. The process of claim 18, wherein the 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) is prepared according to a process comprising chlorinating 3,3,3- trifluoropropene (1243zf) to form the 1,1 ,1-trifluoro-2,3-dichloropropane (243db).

21. The process of claim 20, wherein said chlorinating comprises reacting the 3,3,3- trifluoropropene (1243zf) with the chlorine or HCI / oxygen to form the 1 ,1 ,1- trifluoro-2,3-dichloropropane (243db).

22. The process of claim 21 , wherein the 3,3,3-trifluoropropene (1243zf) is prepared according to a process comprising reacting 1 , 1 ,1 ,3- tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form the 3,3,3-trifluoropropene (1243zf).

23. The process of claim 22, wherein the catalyst is selected from a chrome catalyst or an alumina catalyst.

24. A process, comprising: i) reacting 1 ,1 ,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) chlorinating the 3,3,3-trifluoropropene (1243zf) to form 1 ,1 , 1 -trifluoro-2,3- dichloropropane (243db); iii) dehydrochlorinating the 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1, 1,1 ,2- tetrafluoropropane (244bb); and v) dehydrochlorinating the 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

25. The process of claim 24, wherein step iv) comprises reacting the 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid.INCORPORATED BY REFERENCE (RULE 20.6)26. A process, comprising: i) reacting 1 ,1 ,1 ,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf); ii) reacting the 3,3,3-trifluoropropene (1243zf) with chlorine or HCI / oxygen to form 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db); iii) reacting 1 ,1 ,1-trifluoro-2,3-dichloropropane (243db) with a first caustic to form 2-chloro-3,3,3-trifluoropropene (1233xf); iv) reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide to form 2-chloro-1, 1,1 ,2- tetrafluoropropane (244bb); and v) reacting the 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb) with a second caustic to form 2,3,3,3-tetrafluoropropene (1234yf).

27. The process of claim 26, wherein step iv) comprises reacting the 2-chloro-3,3,3- trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of a boron trihalide and a fluorinated sulfonic acid.

28. A composition, comprising 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane (244bb), 2- chloro-3,3,3-trifluoroprop-1-ene (1233xf), and BF3.

29. The composition of claim 28, further comprising 1 ,1,1 ,2,2-pentafluoropropane (245cb).

30. The composition of claim 29, further comprising hydrogen fluoride.

31. The composition of claim 30, which is prepared according to the process of claim 1.

32. The composition of claim 28, further comprising a fluorinated sulfonic acid.

33. The composition of claim 32, further comprising 1 ,1,1 ,2,2-pentafluoropropane(245cb).

34. The composition of claim 33, further comprising hydrogen fluoride.

35. The composition of claim 34, which is prepared according to the process of claim 2.38INCORPORATED BY REFERENCE (RULE 20.6)

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