Process for preparation of 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. Also provided are methods of preparing HFO-1234yf using the 2-chloro-1, 1, 1, 2-tetrafluoropropane and a composition comprising the 2-chloro-1, 1, 1, 2-tetrafluoropropane, as well as methods of preparing HFO-1234yf using the 2-chloro-1, 1, 1, 2-tetrafluoropropane and the composition comprising the 2-chloro-1, 1, 1, 2-tetrafluoropropane.

Description

Technical Field

[0001] This 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 fluorinated sulfonic acid. Background Technology

[0002] Hydrofluoroolefins (HFOs) have low ozone depletion potential and low global warming potential, and are considered candidates to replace saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HFOs can be used in a wide range of applications, including as refrigerants, solvents, foam expanders, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle working fluids. Summary of the Invention

[0003] This application particularly provides methods for preparing 2-chloro-1,1,1,2-tetrafluoropropane (244bb), which include reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide.

[0004] This application also provides compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), and BF3, which can be prepared according to one or more methods 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 pertains. Methods and materials used in this invention are described herein; alternatively, suitable methods and materials known in the art may also be used. The materials, methods, and examples described are exemplary only and are not intended to be limiting. All publications, patent applications, patents, sequences, database entries, and other references mentioned herein are incorporated herein by reference in their entirety. In case of any conflict, this specification and its included definitions shall prevail. Detailed Implementation

[0006] 2-Chloro-1,1,1,2-Tetrafluoropropane (244bb) is a key intermediate in the process for preparing HFO-1234yf. Exemplary commercial methods involve the addition of hydrogen fluoride to 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in the presence of an antimony catalyst to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb). The methods described herein offer less corrosive and cost-effective alternatives, for example, optionally using a boron trihalide catalyst instead of an antimony catalyst in the presence of fluorinated sulfonic acid, as shown in Scheme I.

[0007] Option I.

[0008]

[0009] The method of this application can provide additional options for selecting the reactor type required for HF / 1233xf chemistry. For example, unlike SbX5 catalysts (where X is a halide), boron trifluoride (BF3) is a gas and can be operated in a flow-through reactor. BF3 can be readily separated from the 244bb / HF mixture and subsequently recycled. Finally, BF3 is a milder fluorination catalyst compared to antimony fluorination catalysts and does not promote the formation of undesirable byproducts (e.g., 245cb formation).

[0010] Definitions and Abbreviations

[0011] As used herein, the terms “comprising,” “including,” “having,” or any other variations thereof are intended to cover non-exclusive inclusion. For example, a process, method, article of manufacture, or apparatus that includes a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article of manufacture, or apparatus. Furthermore, unless expressly stated otherwise, “or” refers to an inclusive or non-exclusive or. For example, conditions A or B satisfy one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); and both A and B are true (or exist).

[0012] Furthermore, the terms "an" or "a" are used to describe the elements and components described herein. This is for convenience only and to give a general meaning to the scope of the invention. The description should be understood to include one or at least one, and the singular includes the plural, unless it is obvious that it means otherwise.

[0013] When quantities, concentrations, or other values ​​or parameters are given as a list of ranges, preferred ranges, or preferred upper and / or preferred lower limits, it should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. Wherever a numerical range is given herein, the range is intended to include its endpoints, as well as all integers and fractions within that range, unless otherwise indicated.

[0014] As used herein, the term "substantially composed of" is used to define a composition or method that includes, in addition to those disclosed in the literature, materials, steps, features, components, or elements, provided that such additionally included materials, steps, features, components, or elements do not significantly affect one or more essential and novel features of the invention protected by the claims, particularly the mode of action for achieving the desired result of any of the methods of the invention. The term "substantially composed of" occupies an intermediate position between "comprising" and "composed of".

[0015] Throughout the definition, the term "C" n-m The instruction includes a range of endpoints, where n and m are integers and indicate the number of carbons. Examples include C. 1-3 C 1-6 wait.

[0016] As used in this article, the term "C" n-m "Alkyl" refers to a saturated hydrocarbon group having n to m carbon atoms, which can be straight-chain or branched. 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, etc. In some embodiments, the alkyl group contains 1 to 6 carbon atoms.

[0017] As used in this article, "C" n-m "Alkenyl" refers to an alkyl group having one or more carbon-carbon double bonds and having n to m carbon atoms. Exemplary alkenyl groups include, but are not limited to, vinyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, etc. In some embodiments, the alkenyl moiety contains 2 to 6 carbon atoms. In some embodiments, the alkenyl group is replaced by 2s F atoms, where "s" is the number of carbon atoms in the alkenyl group.

[0018] As used in this article, the term "C" n-m "Fluoroalkyl" refers to an alkyl group having one to 2s+1 F atoms, where "s" is the number of carbon atoms in the alkyl group, and 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.

[0019] As used in this article, the term "C" n-m "Fluoroalkoxy" refers to a compound of the formula -OC with one to 2s+1 F atoms. n-m The fluoroalkyl group, wherein "s" is the number of carbon atoms in the alkyl group, and 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.

[0020] As used herein, the term "fluorinated sulfonic acid" refers to the group R. F Compounds with -SO3H, where the variable R F As defined herein. In some implementations, R F It is fluorine or a portion containing at least one F atom, as described herein.

[0021] The term "halogen" or "halogenated" refers to fluorination, chlorination, bromination, and iodination. In some implementations, halogenation is fluorination.

[0022] As used herein, the term “dehydrohalogenation” refers to a process in which hydrogen and halogens (e.g., Cl, Br, or I) on adjacent carbons in a molecule are removed to form the corresponding olefin.

[0023] As used herein, the term “dehydrochlorination” refers to a process in which hydrogen and chlorine are removed from adjacent carbons in a molecule to form the corresponding olefin.

[0024] As used herein, the phrase “optionally substituted” means either unsubstituted or substituted. Substituents are chosen independently, and substitution can occur at any chemically accessible position. As used herein, the term “substituted” means that a hydrogen atom has been removed and replaced by a substituent. It should be understood that substitution at a given atom is limited by valence.

[0025] As defined herein, the term "mixing" refers to the process of stirring reactants (e.g., 2-chloro-3,3,3-trifluoroprop-1-ene, hydrogen fluoride, and boron trihalide) at a specific mixing power, for example, from about 0.1 to about 50 hp / 1000 gallons of reaction mixture. Mixing (i.e., stirring) can be achieved, for example, by mechanical means (e.g., a stirrer or in an oscillator, such that the reactants are substantially well mixed with each other under conditions sufficient to allow 2-chloro-3,3,3-trifluoroprop-1-ene to react with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane) and by other means known in the art or as described herein.

[0026] Therefore, in some embodiments, mixing is provided by a mechanical stirrer. However, the mixing power input can alternatively be provided by other methods. These methods are known in the industry and include mixing using bubbles from gas added to the container or bubbles from gas generated within the container by liquid evaporation. Mixing can also be provided by drawing liquid from the container into a pump and pumping the liquid back into the container. Static mixers, rotor-stator heads, or other devices designed to mix the contents can be present in the liquid circulation path to provide additional mixing power input. Mixing can be provided by a single method or by a combination of two or more methods.

[0027] In some embodiments, the reactor agitates the reaction mixture by delivering power to the agitator on the liquid in the stirrable vessel. The power input is calculated based on a combination of parameters, including the geometry of the vessel, the design of the baffles (if present), the design of the impeller, and the impeller rotation speed. This calculation is performed by those skilled in the art. In the methods described herein, to maximize yield, in one embodiment, the bases are mixed together to produce small bubbles and a high interfacial surface area. An autoclave reactor is an example of a reactor capable of achieving the aforementioned horsepower per gallon of liquid. In some embodiments, about 0.1 to about 50 hp / 1000 gallons of liquid is applied to the agitator to agitate the reaction mixture. In some embodiments, about 0.5 to about 40 hp / 1000 gallons of liquid is applied to the agitator to agitate the reaction mixture. In some embodiments, about 1 to about 35 hp / 1000 gallons of liquid is applied to the agitator to agitate the reaction mixture.

[0028] As used herein, the term "caustic alkali" refers to an alkali that dissociates when placed in water. Examples include alkali metal oxides, hydroxides, or amides, such as sodium oxide or potassium oxide, or sodium hydroxide or potassium hydroxide, or sodium amide or potassium amide; or alkaline earth metal hydroxides, alkaline earth metal oxides or amides, alkali metal carbonates, or alkali metal phosphates or alkali metal carboxylates. In some embodiments, the method of this application is carried out in the presence of a caustic alkali (or base) that dissociates when placed in water.

[0029] As used herein, the term "boron trihalide" refers to a compound of the formula BX3, where each X is an independently chosen halide (i.e., a fluoride, chloride, bromide, or iodide). In some embodiments, each X is the same. In some embodiments, boron trihalide is BF3, BCl3, or BBr3. In some embodiments, boron trihalide is BF3.

[0030] As described herein, the methods of this application can be carried out in the presence of a catalyst (e.g., a boron trihalide catalyst). As used herein, the term "catalyst" refers to a substance that accelerates a chemical reaction but is not consumed by the reaction; therefore, it can be recovered at the end of the reaction in a form that has not undergone chemical change.

[0031] The following abbreviations may be used throughout this patent application:

[0032] CFC: Chlorofluorocarbons

[0033] HFO: Hydrofluoroolefin

[0034] HCFC: Hydrochlorofluorocarbons

[0035] HCFC-243db or 243db: 1,1,1-trifluoro-2,3-dichloropropane

[0036] HCFC-244bb or 244bb: 2-chloro-1,1,1,2-tetrafluoropropane

[0037] HF: Hydrogen fluoride

[0038] HFC-245cb: 1,1,1,2,2-pentafluoropropane

[0039] 250fb: 1,1,1,3-Tetrachloropropane

[0040] 253fb: 3-Chloro-1,1,1-trifluoropropane

[0041] HCFO-1233xf or 1233xf: 2-chloro-3,3,3-trifluoroprop-1-ene

[0042] HFO-1234yf or 1234yf: 2,3,3,3-tetrafluoropropene or 2,3,3,3-tetrafluoropropene

[0043] HFO-1243zf or 1243zf: 3,3,3-trifluoroprop-1-ene

[0044] 1230xa: 1,1,2,3-Tetrachloroprop-1-ene

[0045] Method of the Invention

[0046] This application provides a method for preparing 2-chloro-1,1,1,2-tetrafluoropropane (244bb). In some embodiments, this application provides a method comprising reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb).

[0047] In some embodiments, the preparation of 2-chloro-1,1,1,2-tetrafluoropropane (244bb) involves reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide and fluorinated sulfonic acid.

[0048] In some embodiments, boron trihalide is selected from the group consisting of boron trifluoride (BF3), boron trichloride (BCl3), and boron tribromide (BBr3). In some embodiments, boron trihalide is boron trifluoride (BF3).

[0049] In some implementations, the method is carried out in the absence of fluorinated sulfonic acid.

[0050] In some embodiments, the method is carried out in the presence of fluorinated sulfonic acid. In some embodiments, the fluorinated sulfonic acid is a compound of formula I:

[0051]

[0052] in:

[0053] R F Choose free fluorine, C 1-6 Fluoroalkyl, C 1-6 Fluoroalkoxy and R 1 -O-CX 1 HC(X 1 Groups consisting of 2-

[0054] Each X 1 The group consisting of H and fluorine is selected independently, provided that at least one X is present. 1 It is fluorine; and

[0055] R 1 It is C 1-6 Alkyl or C 2-6 Alkenes, each of which can be optionally substituted.

[0056] In some implementation schemes, R F Choose free fluorine, C 1-6 Fluorinated alkyl groups and C 1-6 The group consisting of fluoroalkoxy groups. In some embodiments, R F Choose free fluorine, C 1-3 Fluoroalkyl and C 1-3 The group consisting of fluoroalkoxy groups. In some embodiments, R F Choose free fluorine, C 1-3 Fluorinated alkyl groups and C 1-3 The group consisting of fluoroalkoxy groups.

[0057] In some implementation schemes, R F It is R 1 -O-CX 1 HC(X 1 )2-. In some implementations, R 1 It is unreplaced C 1-6 Alkyl group. In some embodiments, R 1 It is C 1-6 Fluoroalkyl. In some embodiments, R 1 It is unreplaced C 2-6 Alkenyl. In some embodiments, R 1 It is C 2-6 Fluoroalkenyl.

[0058] In some implementations, each X 1 It is fluorine. In some implementations, an X 1 The group is H, and there are two X groups. 1The group is fluorine. In some embodiments, the two X groups... 1 The group is H, and there is an X. 1 The radical is fluorine.

[0059] 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.

[0060] In some embodiments, the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, and 1,1,2,2-tetrafluoroethane-1-sulfonic acid. In some embodiments, the fluorinated sulfonic acid is fluorosulfonic acid or trifluoromethanesulfonic acid (i.e., trifluoromethylsulfonic acid). In some embodiments, the fluorinated sulfonic acid is fluorosulfonic acid. In some embodiments, the fluorinated sulfonic acid is trifluoromethanesulfonic acid.

[0061] 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-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.

[0062] Additional fluorinated sulfonic acids that can be used in the methods described herein can be found, for example, in U.S. Patent No. 2,403,207 and U.S. Patent Publication No. 20060276670, the disclosures of which are incorporated herein by reference in their entirety.

[0063] In some embodiments, the reaction is carried out at temperatures from about 0°C to about 200°C, for example, from about 0°C to about 150°C, from about 0°C to about 125°C, from about 0°C to about 100°C, from about 0°C to about 75°C, from about 0°C to about 50°C, from about 0°C to about 25°C, from about 25°C to about 200°C, from about 25°C to about 150°C, from about 25°C to about 125°C, from about 25°C to about 100°C, from about 25°C to about 75°C, from about 25°C to about 50°C, from about 50°C to about 200°C, from about The temperature is to be carried out at 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.

[0064] In some embodiments, the reaction is carried out at a temperature of about 25°C to about 200°C. In some embodiments, the reaction is carried out at a temperature of about 25°C to about 155°C. In some embodiments, the reaction is carried out at a temperature of about 25°C to about 150°C. In some embodiments, the reaction is carried out at a temperature of about 45°C to about 150°C. In some embodiments, the reaction is carried out at a temperature of about 40°C to about 155°C. In some embodiments, the reaction is carried out at a temperature of about 45°C to about 150°C. In some embodiments, the reaction is carried out at a temperature of about 40°C to about 80°C. In some embodiments, the reaction is carried out at a temperature of about 45°C to about 75°C.

[0065] In some embodiments, a molar excess of boron trihalide is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). In some embodiments, a catalytic amount of boron trihalide is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0066] In some embodiments, based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), boron trihalide of about 0.1 equivalent to about 10 equivalents is used, for example, about 0.1 equivalent to about 5 equivalents, about 0.1 equivalent to about 1 equivalent, about 0.1 equivalent to about 0.5 equivalents, about 0.1 equivalent to about 0.25 equivalents, about 0.25 equivalent to about 10 equivalents, about 0.25 equivalent to about 5 equivalents, about 0.25 equivalent to about 1 equivalent, about 0.25 equivalent to about 0.5 equivalents, about 0.5 equivalent to about 10 equivalents, about 0.5 equivalent to about 5 equivalents, about 0.5 equivalent to about 1 equivalent, about 1 equivalent to about 10 equivalents, about 1 equivalent to about 5 equivalents, or about 5 equivalents to about 10 equivalents. In some implementations, boron trihalide is used in amounts of about 0.25 to about 1.25 equivalents, based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0067] In some implementations, a molar excess of hydrogen fluoride is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) (i.e., an amount greater than 1 molar equivalent of hydrogen fluoride based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf); for example, it should be understood that in a reactor system, hydrogen fluoride may be used as a gas to pass through the reaction mixture and thus contact the reaction mixture).

[0068] In some embodiments, based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), about 1 equivalent to about 100 equivalents of hydrogen fluoride are used, such as about 1 equivalent to about 75 equivalents, about 1 equivalent to about 50 equivalents, about 1 equivalent to about 25 equivalents, about 1 equivalent to about 10 equivalents, about 10 equivalents to about 100 equivalents, about 10 equivalents to about 75 equivalents, about 10 equivalents to about 50 equivalents, about 10 equivalents to about 25 equivalents, about 25 equivalents to about 100 equivalents, about 25 equivalents to about 75 equivalents, about 25 equivalents to about 50 equivalents, about 50 equivalents to about 100 equivalents, about 50 equivalents to about 75 equivalents, or about 75 equivalents to about 100 equivalents. In some implementations, approximately 5 to approximately 15 equivalents of hydrogen fluoride are used based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0069] In some embodiments, the methods provided herein also include substantially separating 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). "Substantially separated" means that the compound is at least partially or substantially separated from the environment in which it is formed or detected. Partial separation may include, for example, compositions rich in 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb). Substantial separation may include compositions containing at least about 50% by weight, at least about 60% by weight, at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, at least about 97% by weight, or at least about 99% by weight of the compounds or salts thereof provided herein. Methods for separating compounds are conventional in the art.

[0070] In some embodiments, the method provided herein also includes substantially separating (e.g., purifying) 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) by distillation. In some embodiments, the method includes substantially separating 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) by removing one or more additional components from the reaction mixture (e.g., hydrogen fluoride, boron trihalide, fluorinated sulfonic acid, or any combination thereof). In some embodiments, one or more additional components of the reaction mixture are removed by distillation.

[0071] The method of the present invention can be carried out, for example, in one or more reaction zones under conditions that effectively produce 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) or a composition containing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0072] Therefore, in some embodiments, the method provided herein further includes contacting 2-chloro-1,1,1,2-trifluoropropene (1233xf) with hydrogen fluoride in the presence of boron trihalide in multiple reaction zones under conditions that effectively produce 2-chloro-3,3,3-tetrafluoropropane (HCFC-244bb) or a composition containing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0073] Therefore, in some embodiments, the method provided herein further includes contacting 2-chloro-1,1,1,2-trifluoropropene (1233xf) with hydrogen fluoride in multiple reaction zones in the presence of boron trihalide and fluorinated sulfonic acid (e.g., fluorinated sulfonic acid of formula I) under conditions that effectively produce 2-chloro-3,3,3-tetrafluoropropane (HCFC-244bb) or a composition containing 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb), respectively.

[0074] In some embodiments, the methods provided herein include preparing compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and one or more additional components. In some embodiments, the compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) comprise less than about 2% by weight of 1,1,1,2,2-pentafluoropropane (HFC-245cb). In some embodiments, the compositions comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) comprise less than about 1% by weight of 1,1,1,2,2-pentafluoropropane (HFC-245cb).

[0075] 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 some 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).

[0076] In some embodiments, more than about 85% of 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 90% of 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 95% of 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 2-chloro-3,3,3-trifluoropropene (1233xf) is converted to 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb).

[0077] In some embodiments, the multiple reaction zones include multiple reactors operating in series. In some embodiments, the multiple reactors include at least a first reactor and a second reactor operating in series.

[0078] In some implementations, the method provided herein also includes:

[0079] a) In the first reaction zone, under conditions that effectively produce a first composition comprising unreacted HCFO-1233xf, a first amount of 2-chloro-3,3,3-tetrafluoropropane (HCFC-244bb), and a first amount of 1,1,1,2,2-pentafluoropropane (HFC-245cb), the feed 2-chloro-1,1,1,2-trifluoropropene (HCFO-1233xf) is contacted with hydrogen fluoride, a first boron trihalide, and optionally a first fluorinated sulfonic acid;

[0080] b) In the second reaction zone, under the conditions for producing the second composition, the first composition is contacted with boron trihalide and optionally a second fluorinated sulfonic acid, wherein the second composition comprises 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and less than about 5% by weight of 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) relative to the feed 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf), and less than about 2% by weight of 1,1,1,2,2-pentafluoropropane (HFC-245cb).

[0081] In some embodiments, the first boron trihalide and the second boron trihalide are the same. In some embodiments, the first boron trihalide and the second boron trihalide are each BF3. In some embodiments, the first boron trihalide and the second boron trihalide are different.

[0082] In some embodiments, the first fluorinated sulfonic acid and the second fluorinated sulfonic acid are the same. In some embodiments, the first fluorinated sulfonic acid and the second fluorinated sulfonic acid are different. In some embodiments, the first fluorinated sulfonic acid and the second fluorinated sulfonic acid are each independently selected from compounds of formula I as described herein.

[0083] In some embodiments, the first reaction zone does not contain the first fluorinated sulfonic acid. In some embodiments, the first reaction zone contains the first fluorinated sulfonic acid.

[0084] In some embodiments, the second reaction zone does not contain a second fluorinated sulfonic acid. In some embodiments, the second reaction zone contains a second fluorinated sulfonic acid.

[0085] In some embodiments, the second reaction zone comprises one or more reactors operating in series. In some embodiments, the first and second reaction zones each comprise a CSTR reactor. In some embodiments, the first composition further comprises residual boron trihalide (e.g., BF3) and optionally residual fluorinated sulfonic acid (e.g., a compound of formula I as described herein) removed from the first composition prior to contact in the second reaction zone.

[0086] Once prepared according to the method of the invention, 2-chloro-1,1,1,2-tetrafluoropropane or compositions containing 2-chloro-1,1,1,2-tetrafluoropropane can be used to prepare additional compounds, including HFO-1234yf, as shown in schemes II-III below, wherein X is a halide and R F -SO3H represents the optional fluorinated sulfonic acid component in the method of the present invention.

[0087] Option II.

[0088]

[0089] Option III.

[0090]

[0091] In some embodiments, the method provided herein further includes dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (HFO-1234yf). In some embodiments, the dehydrochlorination reaction includes reacting 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

[0092] Other methods for preparing HFO-1234yf and / or 244bb can be found, for example, in U.S. Patent Application No. 12 / 404,130 and U.S. Patent Publications Nos. 20140350309 and 20140303409, the disclosures of which are incorporated herein by reference in their entirety.

[0093] For example, in some embodiments, the preparation of HFO-1234yf and / or 244bb can be carried out in an adiabatic reaction zone (e.g., in one or more adiabatic reactors). The adiabatic reaction zone includes at least two adiabatic reactors connected in series and has a heat exchanger arranged in fluid communication between each pair of reactors connected in series.

[0094] In some embodiments, the adiabatic reaction zone includes a first adiabatic reactor and a final adiabatic reactor. The first adiabatic reactor is the preceding adiabatic reactor relative to any adiabatic reactor or heat exchanger downstream of the first adiabatic reactor in the adiabatic reaction zone. The final adiabatic reactor is the subsequent adiabatic reactor relative to any adiabatic reactor or heat exchanger upstream of the final adiabatic reactor in the adiabatic reaction zone.

[0095] In some embodiments, the first adiabatic reactor is located upstream of and in fluid communication with the heat exchanger. In some embodiments, the heat exchanger is in fluid communication with and located upstream of a subsequent adiabatic reactor.

[0096] In some embodiments, the adiabatic reaction zone consists of two reactors: a first adiabatic reactor and a final adiabatic reactor. In some embodiments, the heat exchanger is located downstream of the first adiabatic reactor and upstream of the final adiabatic reactor.

[0097] Those skilled in the art will understand the relationship between a first adiabatic reactor without an upstream reactor, a subsequent adiabatic reactor with at least one upstream reactor, and a final adiabatic reactor without a downstream reactor. In some embodiments, the adiabatic reactors in the adiabatic reaction zone are in fluid communication with a heat exchanger, wherein the heat exchanger is disposed between two reactors.

[0098] In some embodiments, the adiabatic reaction zone comprises a first adiabatic reactor, one or more additional adiabatic reactors (e.g., a second adiabatic reactor, a third adiabatic reactor, etc., which may also be referred to as a subsequent adiabatic reactor), and a final adiabatic reactor, wherein each reactor operates adiabatably, and a heat exchanger is arranged between the first adiabatic reactor and one or more additional adiabatic reactors, and between each reactor. The upper limit on the number of adiabatic reactors and heat exchangers (where the heat exchanger is arranged between two reactors in the adiabatic reaction zone) can be based on practical reasons, such as controlling cost and complexity, or based on achieving specific objectives, such as feedstock conversion or the formation of specific products. In some embodiments, two or more adiabatic reactors are used in the adiabatic reaction zone, such as two to ten reactors, two to four reactors, or two to three reactors.

[0099] Adiabatic reactors can have any shape that facilitates the execution of one or more of the methods described herein. In some embodiments, each reactor is independently a cylindrical tube or pipe, each of which can be straight or coiled. In some embodiments, the reactor is a plug flow reactor. Plug flow reactors minimize backmixing, resulting in a lower overall conversion rate.

[0100] Due to the corrosive nature of one or more methods described herein, the adiabatic reactor used for the adiabatic reaction zone disclosed herein can be constructed of corrosion-resistant materials. Exemplary materials include, but are not limited to, stainless steel (e.g., austenitic, copper-clad steel, nickel-based alloys, gold, gold-plated, or quartz). Nickel-based alloys are commercially available and include, for example, high-nickel alloys such as Monel. ™ Nickel-copper alloy, Hastelloy ™ Nickel-based alloys and Inconel ™ Nickel-chromium alloy. In some embodiments, the reactor is constructed of a nickel-based alloy. In some embodiments, one or more adiabatic reactors may be lined with a fluoropolymer, provided that the fluoropolymer is compatible with the reaction temperature of the method. Other materials may include SiC or graphite for corrosion resistance.

[0101] In addition to the adiabatic reactor in the adiabatic reaction zone disclosed herein, heat exchangers, discharge pipes, units related to mass transfer, contact vessels (premixers), distillation columns, and feed and material transfer lines associated with the reactors, heat exchangers, vessels, columns, and units used in the methods provided herein should also be constructed of corrosion-resistant materials, such as those described above.

[0102] In some embodiments, this application provides an adiabatic reaction zone. In some embodiments, the adiabatic reaction zone is suitable for carrying out one or more methods described herein. In some embodiments, the adiabatic reaction zone includes at least two adiabatic reactors. In some embodiments, a heat exchanger is arranged between each reactor. In some embodiments, the method provided herein includes providing an adiabatic reaction zone comprising at least two adiabatic reactors connected in series and having a heat exchanger arranged sequentially and in fluid communication between every two reactors connected in series; introducing starting materials of the method described herein into the adiabatic reaction zone, wherein a first reaction product is generated in a first adiabatic reactor; transferring the first reaction product from the first adiabatic reactor to the heat exchanger to generate an intermediate product; then introducing the intermediate product from the heat exchanger to a subsequent adiabatic reactor, wherein a second reaction product is generated; and optionally, passing the second reaction product from the subsequent adiabatic reactor through the heat exchanger before introducing the second reaction product into a third adiabatic reactor (if present), etc.

[0103] Despite the foregoing, other process steps may occur upstream of the adiabatic reaction zone. These upstream process steps may be carried out in one or more reactors. For clarity, even if one or more reactors are present upstream, the term "first adiabatic reactor" as used herein refers to the first adiabatic reactor in a series of adiabatic reactors in which the methods provided herein (e.g., the method for preparing 2-chloro-1,1,1,2-tetrafluoropropane (244bb), including the reaction of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide and optionally in the presence of fluorinated sulfonic acid) are carried out, wherein a heat exchanger is located between the first adiabatic reactor in the series and the second (subsequent) reactor in the series. Therefore, any reactor in which process steps are carried out upstream of the adiabatic reaction zone and thus upstream of the so-called first adiabatic reactor cannot be considered a "first adiabatic reactor."

[0104] Other processes may exist downstream of the process that occur in the adiabatic reaction zone as described in this article.

[0105] In some embodiments, a heat exchanger is used in the process carried out in an adiabatic reaction zone as described herein. In some embodiments, the heat exchanger is arranged between two adiabatic reactors in series. In some embodiments, the heat exchanger replaces the heat used in the endothermic reaction (e.g., dehydrohalogenation reaction). In some embodiments, the heat exchanger used herein may be a shell-and-tube heat exchanger. In some embodiments, the heat exchanger may be a finned tube heat exchanger, a microchannel heat exchanger, and vertical or horizontal single-pass tube or plate heat exchangers, an electric heater, etc. The heat exchanger may provide heat by electric heating. In some embodiments, the heat exchanger may use the process feed stream as the heat exchange fluid. Other designs compatible with the physical and chemical requirements of the methods described herein may be used, including temperature and the corrosive properties of the reactants.

[0106] In some embodiments, each heat exchanger may operate 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 leaving another heat exchanger in the adiabatic reaction zone. In some embodiments, each heat exchanger may be operated to provide an intermediate product with a different temperature relative to the intermediate products leaving other heat exchangers in the adiabatic reaction zone.

[0107] In some embodiments, each heat exchanger may be arranged independently in the vessel along with an preceding or subsequent adiabatic reactor. In some embodiments, each heat exchanger may be arranged independently in a vessel separate from an preceding or subsequent adiabatic reactor. In some embodiments, fluid communication is maintained between subsequent adiabatic reactors via heat exchangers as previously described.

[0108] In some implementations, the heat exchanger described herein may also be used to heat the starting material to the desired reaction temperature, either within or upstream of the first adiabatic reactor outside the adiabatic reaction zone.

[0109] In some embodiments, the method provided herein further includes: (a) removing impurities from the reactor (e.g., an adiabatic reactor as described herein) such that the reactor is substantially free of impurities; and (b) in the reactor, providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) prepared according to the method provided herein, under conditions that effectively produce a final composition comprising 2,3,3,3-tetrafluoropropene (HFO-1234yf).

[0110] In some embodiments, the impurities in the reactor are selected from the group consisting of metal halides, metal oxides, and carbon-containing materials. In some embodiments, the metal halides include halides of Ni, Cr, Fe, Mo, Nb, Cu, and Co.

[0111] In some embodiments, the step of removing impurities from the reactor includes introducing a reducing agent into the reactor under conditions that effectively convert any metal halide or metal oxide into a metallic metal.

[0112] In some implementation schemes, the reducing agent is selected from H2, NH3, CO, Cl-C. 12 Hydrocarbons and combinations thereof form a group.

[0113] In some implementations, the step of removing impurities from the reactor includes introducing an oxidant into the reactor while effectively burning off the carbonaceous material in the reactor.

[0114] In some embodiments, the oxidant is selected from the group consisting of H2O, CO2, O2, air, O3, Cl2, N2O, and combinations thereof. In some embodiments, the oxidant contains oxygen.

[0115] In some embodiments, the step of removing impurities from the reactor includes physically removing carbonaceous materials, metal oxides, and metal halides from the reactor. In some embodiments, the step of physically removing carbonaceous materials, metal oxides, and metal halides from the reactor is selected from the group consisting of electropolishing, mechanical polishing, hydraulic methods, and combinations thereof.

[0116] In some embodiments, the selectivity for preparing 2,3,3,3-tetrafluoropropylene (1234yf) is at least 90% or higher.

[0117] In some embodiments, the method provided herein further includes: (a) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb) prepared according to the method provided herein in a substantially impurity-free reactor; and (b) contacting the starting composition in the reactor under conditions that effectively produce a final composition comprising 2,3,3,3-tetrafluoropropene (1234yf).

[0118] In some implementations, the selectivity for preparing 2,3,3,3-tetrafluoropropylene is at least 90% or higher.

[0119] In some embodiments, this application provides a method comprising: (i) providing a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb) prepared according to the method provided herein; (ii) reducing the level of hydrogen fluoride in the composition such that it is substantially free of hydrogen fluoride; and (iii) contacting the starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (1234yf).

[0120] In some embodiments, the level of hydrogen fluoride in the composition is reduced such that the amount of hydrogen fluoride present in the composition is less than about 500 ppm. In some embodiments, the level of hydrogen fluoride in the composition is reduced such that the amount of hydrogen fluoride present in the composition is less than about 50 ppm. In some embodiments, reducing the hydrogen fluoride level in the composition includes distilling the hydrogen fluoride, passing the composition through a scrubber, or passing the composition through a solid adsorbent.

[0121] In some implementations, the solid adsorbent is selected from the group consisting of alumina, calcium carbonate, sodium carbonate, and sodium aluminate.

[0122] This application also provides a method comprising (i) providing a starting composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb) prepared according to the method provided herein, the starting composition being substantially free of HF; and (ii) contacting the starting composition with a dehydrochlorination catalyst to produce a final composition comprising 2,3,3,3-tetrafluoropropene (1234yf).

[0123] In some embodiments, the amount of hydrogen fluoride present in the composition is less than about 500 ppm. In some embodiments, the amount of hydrogen fluoride present in the composition is less than about 50 ppm.

[0124] In some embodiments, the contact between the starting composition and the dehydrochlorination catalyst is carried out in the vapor phase. In some embodiments, the contact between the starting composition and the dehydrochlorination catalyst is carried out in the liquid phase.

[0125] In some embodiments, the catalyst is selected from the group consisting of: (i) one or more metal halides, (ii) one or more halide metal oxides, (iii) one or more zero-valent metals / metal alloys, and (iv) combinations of two or more of these.

[0126] In some implementations, dechlorination is carried out in the vapor phase.

[0127] In some embodiments, the intermediates prepared in each step are purified prior to the reaction in the next step to remove impurities from the 2,3,3,3-tetrafluoropropylene (1234yf) prepared in the final step, achieving a desired purity, such as >99.5% by weight. Purification techniques known in the art, such as distillation, extraction, decantation, and adsorption, can be used. Those skilled in the art will recognize that impurities advantageously removed prior to the final reaction step in the preparation of 2,3,3,3-tetrafluoropropylene (1234yf) are those with similar boiling points to 2,3,3,3-tetrafluoropropylene (1234yf), or those that react to form substances with similar boiling points.

[0128] In some embodiments, the 2-chloro-3,3,3-trifluoropropene (1233xf) described herein can be prepared by a method comprising dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (243db) to form 2-chloro-3,3,3-trifluoropropene (1233xf). In some embodiments, dehydrochlorination comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a caustic base to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0129] In some embodiments, the steps for preparing 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) are performed according to the method disclosed in U.S. Patent No. 8,884,083, the disclosure of which is incorporated herein by reference in its entirety.

[0130] Therefore, in some embodiments, a method for 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 activated carbon. In some embodiments, the carbon is acid-washed activated carbon. In some embodiments, M is K, and Y is F or Cl.

[0131] 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.

[0132] In some embodiments, the product selectivity for preparing 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 90 mol%. In some embodiments, the product selectivity for preparing 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 95 mol%. In some embodiments, the dehydrochlorination selectivity for preparing 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 90 mol%.

[0133] In some embodiments, the method for preparing 2-chloro-3,3,3-trifluoropropene (1233xf) includes dehydrochlorinating 1,1,1,3-tetrachloropropane (250fb) to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0134] In some embodiments, the method for preparing 2-chloro-3,3,3-trifluoropropene (1233xf) is disclosed in US20120215035, the disclosure of which is incorporated herein by reference in its entirety.

[0135] Therefore, in some embodiments, the method provided herein also includes contacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a catalyst in a reaction zone to produce a product mixture containing 2-chloro-3,3,3-trifluoropropene (1233xf).

[0136] In some embodiments, the method further includes contacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a chromium oxyfluoride catalyst in a reaction zone to produce a product mixture containing 2-chloro-3,3,3-trifluoropropene (1233xf).

[0137] In some embodiments, the method is carried out in the presence of hydrogen fluoride (HF). In some embodiments, the molar ratio of HF to 2-chloro-3,3,3-trifluoropropene in the reaction zone is not greater than 0.9.

[0138] 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.

[0139] In some embodiments, the product selectivity for forming 2-chloro-3,3,3-trifluoropropene is at least 90 mol%. In some embodiments, the dehydrochlorination selectivity for 2-chloro-3,3,3-trifluoropropene is at least 95 mol%.

[0140] In some embodiments, 1,1,1-trifluoro-2,3-dichloropropane (243db) is prepared according to a method comprising chlorinating 3,3,3-trifluoropropene (1243zf) to form 1,1,1-trifluoro-2,3-dichloropropane (243db). In some embodiments, the chlorination comprises reacting 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db). In some embodiments, the chlorination comprises reacting 3,3,3-trifluoropropene (1243zf) with chlorine to form 1,1,1-trifluoro-2,3-dichloropropane (243db). In some embodiments, the chlorination comprises reacting 3,3,3-trifluoropropene (1243zf) with HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0141] In some embodiments, the method for preparing 1,1,1-trifluoro-2,3-dichloropropane (243dB) is disclosed in U.S. Patent No. 9,938,208, the disclosure of which is incorporated herein by reference in its entirety.

[0142] Therefore, in some embodiments, the method for preparing 1,1,1-trifluoro-2,3-dichloropropane (243db) includes contacting 3,3,3-trifluoropropene (1243zf) with chlorine in the liquid phase to form 1,1,1-trifluoro-2,3-dichloropropane (243db) in the absence or presence of a chlorination catalyst and with or without exposure to UV light.

[0143] In some embodiments, the chlorination catalyst comprises at least one metal halide, wherein the metal is a metal or transition metal from Group 13, 14, or 15 of the periodic table, or a combination thereof. In some embodiments, the metal halide is supported on activated carbon. In some embodiments, the activated carbon is acid-washed or alkali-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.

[0144] In some embodiments, chlorination is carried out in the vapor phase with or without a chlorination catalyst. In some embodiments, chlorination is carried out at a temperature ranging from about 80°C to about 200°C and a pressure ranging from about 10 psig to about 100 psig, wherein the molar ratio of 3,3,3-trifluoropropylene (1243zf) to chlorine is in the range of about 1:0.02 to about 1:1.

[0145] In some embodiments, 3,3,3-trifluoropropylene (1243zf) is prepared according to a method comprising reacting 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropylene (1243zf). In some embodiments, the catalyst is selected from chromium catalysts or alumina catalysts.

[0146] In some embodiments, 3,3,3-trifluoropropylene (1243zf) is prepared according to the method disclosed in U.S. Patent Application No. 15 / 917,376, the disclosure of which is incorporated herein by reference in its entirety.

[0147] Therefore, in some embodiments, 3,3,3-trifluoropropene (1243zf) is prepared according to a method comprising reacting 3-chloro-1,1,1-trifluoropropane (253fb) with a base, wherein the reaction is carried out in the absence of a phase transfer catalyst. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst. In some embodiments, the reaction is carried out in an aqueous solvent component. In some embodiments, the reaction is carried out in an aqueous solvent component and in the absence of a phase transfer catalyst. In some embodiments, the reaction is carried out in water and in the absence of a phase transfer catalyst.

[0148] In some embodiments, 3,3,3-trifluoropropylene (1243zf) is prepared in the absence of a phase transfer catalyst, and the aqueous solvent component contains 0 to 40% w / w of an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component contains 0 to 30% w / w of an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component contains 0 to 20% w / w of an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component contains 0 to 10% w / w of an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst, and the aqueous solvent component does not contain an organic solvent. In some embodiments, the reaction is carried out in the absence of both a phase transfer catalyst and an organic solvent. In some embodiments, the reaction is carried out in the absence of a phase transfer catalyst and an organic solvent component selected from aliphatic alcohols such as methanol, ethanol, n-propanol, isopropanol, butanol, etc. In some embodiments, the reaction is carried out as a liquid-phase reaction. In some embodiments, the reaction is carried out in the presence of water.

[0149] This application also provides a method comprising:

[0150] i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf).

[0151] ii) Chloride 3,3,3-trifluoropropene (1243zf) to form 1,1,1-trifluoro-2,3-dichloropropane (243db);

[0152] iii) Dehydrochlorinate 1,1,1-trifluoro-2,3-dichloropropane (243db) to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0153] iv) Reaction of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and

[0154] v) Dehydrochlorinate 2-chloro-1,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

[0155] This application also provides a method comprising:

[0156] i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf).

[0157] ii) React 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0158] iii) React 1,1,1-trifluoro-2,3-dichloropropane (243db) with a first caustic base to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0159] iv) Reaction of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and

[0160] v) React 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a second caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

[0161] This application provides a method comprising:

[0162] i) Reacting 3-chloro-1,1,1-trifluoropropane (253fb) with a base to form 3,3,3-trifluoroprop-1-ene (1243zf), wherein the reaction is carried out in the absence of a phase transfer catalyst;

[0163] ii) React 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0164] iii) React 1,1,1-trifluoro-2,3-dichloropropane (243db) with the first caustic base provided herein to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0165] iv) Reaction of 2-chloro-3,3,3-trifluoropropene (1233xf) with hydrogen fluoride to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and

[0166] v) React 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with the second caustic base provided herein to form 2,3,3,3-tetrafluoropropene (1234yf).

[0167] In some embodiments, step iv) includes reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide (e.g., BF3) and fluorinated sulfonic acids provided herein (e.g., compounds of formula I).

[0168] In some embodiments, step iv) is performed at a temperature of about 25°C to about 200°C, as described herein. In some embodiments, step iv) is performed at a temperature of about 45°C to about 150°C. In some embodiments, step iv) is performed at a temperature of about 40°C to about 155°C. In some embodiments, step iv) is performed at a temperature of about 45°C to about 150°C. In some embodiments, step iv) is performed at a temperature of about 40°C to about 80°C. In some embodiments, step iv) is performed at a temperature of about 45°C to about 75°C.

[0169] In some embodiments, in step iv) of the above method, a molar excess of boron trihalide is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). In some embodiments, in step iv) of the above method, a catalytic amount of boron trihalide is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0170] In some embodiments, in step iv) of the above method, about 0.1 equivalents to about 10 equivalents of boron trihalide are used based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). In some embodiments, in step iv) of the above method, about 0.25 equivalents to about 1.25 equivalents of boron trihalide are used based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0171] In some embodiments, in step iv) of the above method, an excess of hydrogen fluoride is used based on 1 molar equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0172] In some embodiments, in step iv) of the above method, about 1 equivalent to about 100 equivalents of hydrogen fluoride are used based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf). In some embodiments, in step iv) of the above method, about 5 equivalents to about 15 equivalents of hydrogen fluoride are used based on 1 equivalent of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0173] Use

[0174] The method described herein can be used to prepare 2-chloro-1,1,1,2-tetrafluoropropane (244bb), which can be used as an intermediate in the preparation of 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf). HFO-1234yf can be used in a variety of applications, such as a refrigerant for high-temperature heat pumps, organic Rankine cycles, and as a fire extinguishing / flame suppressant, propellant, foaming agent, solvent, and / or cleaning fluid.

[0175] Composition of the Invention

[0176] This application also 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) and one or more additional compounds (e.g., minor components). In some embodiments, the compositions are prepared according to one or more of the methods described herein. The presence of 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 can be used to identify the method for producing one or more major components.

[0177] Therefore, this application provides a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) and BF3.

[0178] In some embodiments, the composition comprises about 50% to about 99% of 2-chloro-1,1,1,2-tetrafluoropropane (244bb), as measured by GC-MS.

[0179] In some embodiments, the composition comprises about 85% to about 99% of 2-chloro-1,1,1,2-tetrafluoropropane (244bb), as measured by GC-MS.

[0180] In some embodiments, the composition comprises about 90% to about 99% of 2-chloro-1,1,1,2-tetrafluoropropane (244bb), as measured by GC-MS.

[0181] In some embodiments, the composition comprises about 95% to about 99% of 2-chloro-1,1,1,2-tetrafluoropropane (244bb), as measured by GC-MS.

[0182] In some embodiments, the composition comprises about 1% to about 45% of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), as measured by GC-MS.

[0183] In some embodiments, the composition comprises about 1% to about 15% of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), as measured by GC-MS.

[0184] In some embodiments, the composition comprises about 1% to about 12% of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), as measured by GC-MS.

[0185] In some embodiments, the composition comprises about 1% to about 5% of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), as measured by GC-MS.

[0186] In some embodiments, the composition comprises about 1% to about 3% of 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), as measured by GC-MS.

[0187] In some embodiments, the composition further comprises 1,1,1,2,2-pentafluoropropane (245cb).

[0188] In some embodiments, the composition comprises about 0.01% to about 1% of 1,1,1,2,2-pentafluoropropane (245cb), as measured by GC-MS.

[0189] In some embodiments, the composition comprises about 0.01% to about 0.5% of 1,1,1,2,2-pentafluoropropane (245cb), as measured by GC-MS.

[0190] In some embodiments, the composition comprises about 0.01% to about 0.2% of 1,1,1,2,2-pentafluoropropane (245cb), as measured by GC-MS.

[0191] In some embodiments, the composition comprises about 0.01% to about 0.1% of 1,1,1,2,2-pentafluoropropane (245cb), as measured by GC-MS.

[0192] In some embodiments, the composition also contains hydrogen fluoride.

[0193] In some embodiments, the composition also comprises fluorinated sulfonic acids provided herein (e.g., compounds of formula I as described herein).

[0194] Examples

[0195] The invention will be described in more detail through specific embodiments. The following embodiments are provided for illustrative purposes and are not intended to limit the invention in any way.

[0196] Example 1 - Fluorination of 2-chloro-3,3,3-trifluoropropene (1233xf) in the presence of BF3

[0197] 2-Chloro-3,3,3-trifluoropropene (1233xf), hydrogen fluoride, and BF3 were added to a 400 mL pressure reactor. In Run 5, fluorosulfonic acid was also added to the reactor. The reactor was sealed and heated for 24 hours with shaking. After 24 hours, the reactor was cooled to room temperature, and 200 mL of water was added. The organic vapors in the reactor were transferred to a cooled, evacuated cylinder at 70 °C. The organic matter was analyzed by GC-MS. The conditions and results are shown in the table below.

[0198] Table 1

[0199]

[0200] * GC area estimated based on trends observed in runs 1-5.

[0201] Other Embodiments

[0202] 1. In some embodiments, this application provides a method for preparing 2-chloro-1,1,1,2-tetrafluoropropane (244bb), the method comprising reacting 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide.

[0203] 2. The method according to embodiment 1, wherein the method comprises reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide and fluorinated sulfonic acid.

[0204] 3. The method according to embodiment 1 or 2, wherein the boron trihalide is BF3.

[0205] 4. The method according to embodiment 2 or 3, wherein the fluorinated sulfonic acid is a compound of formula I:

[0206]

[0207] in:

[0208] R F Choose free fluorine, C 1-6 Fluoroalkyl, C 1-6 Fluoroalkoxy and R 1 -O-CX 1 HC(X 1 Groups consisting of 2-

[0209] Each X 1 Independently selected from H and fluorine, provided that at least one X 1 It is fluorine; and

[0210] R 1 It is C 1-6 Alkyl or C 2-6 Alkenes, each of which can be optionally substituted.

[0211] 5. The method according to implementation scheme 4, wherein R F Choose free fluorine, C 1-6 Fluorinated alkyl groups and C 1-6 The group consisting of fluoroalkoxy groups.

[0212] 6. The method according to implementation scheme 4, wherein R F It is R 1 -O-CX 1 HC(X 1 )2-.

[0213] 7. The method according to any one of embodiments 2 to 4, wherein the fluorinated sulfonic acid is selected from the group consisting of free 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.

[0214] 8. The method according to any one of embodiments 2 to 4, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid and trifluoromethanesulfonic acid.

[0215] 9. The method according to any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of about 0°C to about 200°C.

[0216] 10. The method according to any one of embodiments 1 to 8, wherein the reaction is carried out at a temperature of about 40°C to about 155°C.

[0217] 11. The method according to any one of embodiments 1 to 10, wherein about 0.1 equivalents to about 10 equivalents of boron trihalide are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0218] 12. The method according to any one of embodiments 1 to 10, wherein about 0.25 equivalents 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).

[0219] 13. The method according to 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).

[0220] 14. The method according to any one of embodiments 1 to 12, wherein about 1.1 equivalents to about 100 equivalents of hydrogen fluoride are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0221] 15. The method according to any one of embodiments 1 to 12, wherein about 5 to about 15 equivalents of hydrogen fluoride are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

[0222] 16. The method according to any one of embodiments 1 to 15 further includes dehydrochlorinating 2-chloro-1,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

[0223] 17. The method according to embodiment 16, wherein the dehydrochlorination comprises reacting 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

[0224] 18. The method according to any one of embodiments 1 to 17, wherein the 2-chloro-3,3,3-trifluoropropene (1233xf) is prepared according to a method comprising dehydrochlorinating 1,1,1-trifluoro-2,3-dichloropropane (243db) to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

[0225] 19. The method according to embodiment 18, wherein the dehydrochlorination comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a caustic base to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

[0226] 20. The method according to embodiment 18 or 19, wherein the 1,1,1-trifluoro-2,3-dichloropropane (243db) is prepared by a method comprising chlorinating 3,3,3-trifluoropropene (1243zf) to form the 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0227] 21. The method according to embodiment 20, wherein the chlorination comprises reacting the 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form the 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0228] 22. The method according to embodiment 20 or 21, wherein the 3,3,3-trifluoropropylene (1243zf) is prepared by a method comprising reacting 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form the 3,3,3-trifluoropropylene (1243zf).

[0229] 23. The method according to embodiment 22, wherein the catalyst is selected from chromium catalysts or alumina catalysts.

[0230] 24. In some embodiments, this application provides a method comprising:

[0231] i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf).

[0232] ii) Chloride the 3,3,3-trifluoropropene (1243zf) to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0233] iii) Dehydrochlorinate the 1,1,1-trifluoro-2,3-dichloropropane (243db) to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0234] iv) Reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and

[0235] v) Dehydrochlorinate the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

[0236] 25. In some embodiments, this application provides a method comprising:

[0237] i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf).

[0238] ii) React 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db).

[0239] iii) React 1,1,1-trifluoro-2,3-dichloropropane (243db) with a first caustic base to form 2-chloro-3,3,3-trifluoropropene (1233xf).

[0240] iv) Reacting the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) with hydrogen fluoride in the presence of boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and

[0241] v) React the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a second caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

[0242] 26. The method according to 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 boron trihalide and fluorinated sulfonic acid.

[0243] 27. The method according to any one of embodiments 24 to 26, wherein the boron trihalide is BF3.

[0244] 28. The method according to any one of embodiments 24 to 27, wherein the fluorinated sulfonic acid is a compound of formula I:

[0245]

[0246] in:

[0247] R F Choose free fluorine, C 1-6 Fluoroalkyl, C 1-6 Fluoroalkoxy and R 1 -O-CX 1 HC(X 1 Groups consisting of 2-

[0248] Each X 1 Independently selected from H and fluorine, provided that at least one X 1 It is fluorine; and

[0249] R 1 It is C 1-6 Alkyl or C 2-6 Alkenes, each of which can be optionally substituted.

[0250] 29. In some embodiments, this application provides a composition comprising 2-chloro-1,1,1,2-tetrafluoropropane (244bb), 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf), and BF3.

[0251] 30. The composition according to embodiment 29, wherein the composition further comprises 1,1,1,2,2-pentafluoropropane (245cb).

[0252] 31. The composition according to embodiment 29 or 30, wherein the composition further comprises hydrogen fluoride.

[0253] 32. The composition according to any one of embodiments 29 to 31, wherein the composition is prepared according to the method of any one of embodiments 1 to 28.

[0254] 33. The composition according to any one of embodiments 29 to 31, wherein the composition further comprises fluorinated sulfonic acid.

[0255] 34. The composition according to any one of embodiments 29 to 33, wherein the composition further comprises 1,1,1,2,2-pentafluoropropane (245cb).

[0256] 35. The composition according to embodiment 33 or 34, wherein the composition is prepared according to the method of any one of embodiments 2 to 28.

[0257] 36. It should be understood that although the invention has been described in conjunction with a detailed description, 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. Those skilled in the art to which this invention pertains will understand that any feature of any particular aspect and / or embodiment of the invention described herein may be combined with one or more features of any other aspect and / or embodiment of the invention described herein, modified where appropriate to ensure compatibility of the combination. Such combinations are considered part of the invention contemplated by this disclosure.

Claims

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

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

3. The method according to claim 1, wherein the boron trihalide is BF3.

4. The method according to claim 2, wherein the fluorinated sulfonic acid is a compound of formula I: in: R F Choose free fluorine, C 1-6 Fluoroalkyl, C 1-6 Fluoroalkoxy and R 1 -O-CX 1 HC(X 1 Groups consisting of 2- Each X 1 Independently selected from H and fluorine, provided that at least one X 1 It is fluorine; and R 1 It is C 1-6 Alkyl or C 2-6 Alkenes, each of which can be optionally substituted.

5. The method according to claim 4, wherein R F Choose free fluorine, C 1-6 Fluorinated alkyl groups and C 1-6 The group consisting of fluoroalkoxy groups.

6. The method of claim 4, wherein R F It is R 1 -O-CX 1 HC(X 1 )2-.

7. The method according to claim 2, wherein the fluorinated sulfonic acid is selected from the group consisting of free 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.

8. The method according to claim 2, wherein the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid and trifluoromethanesulfonic acid.

9. The method according to claim 1, wherein the reaction is carried out at a temperature of about 0°C to about 200°C.

10. The method of claim 1, wherein the reaction is carried out at a temperature of about 40°C to about 155°C.

11. The method of claim 1, wherein about 0.1 equivalents 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 method of claim 1, wherein about 0.25 equivalents 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 method 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 method of claim 1, wherein about 1.1 equivalents to about 100 equivalents of hydrogen fluoride are used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).

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

16. The method 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 method of claim 16, wherein the dehydrochlorination comprises reacting the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

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

19. The method of claim 18, wherein the dehydrochlorination comprises reacting 1,1,1-trifluoro-2,3-dichloropropane (243db) with a caustic base to form the 2-chloro-3,3,3-trifluoropropene (1233xf).

20. The method of claim 18, wherein the 1,1,1-trifluoro-2,3-dichloropropane (243db) is prepared according to a method comprising chlorinating 3,3,3-trifluoropropene (1243zf) to form the 1,1,1-trifluoro-2,3-dichloropropane (243db).

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

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

23. The method according to claim 22, wherein the catalyst is selected from chromium catalysts or alumina catalysts.

24. A method, the method comprising: i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf). ii) Chloride the 3,3,3-trifluoropropene (1243zf) to form 1,1,1-trifluoro-2,3-dichloropropane (243db). iii) Dehydrochlorinate 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 boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and v) Dehydrochlorinate the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) to form 2,3,3,3-tetrafluoropropene (1234yf).

25. The method 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 boron trihalide and fluorinated sulfonic acid.

26. A method, the method comprising: i) React 1,1,1,3-tetrachloropropane (250fb) with hydrogen fluoride in the presence of a catalyst to form 3,3,3-trifluoropropene (1243zf). ii) React the 3,3,3-trifluoropropene (1243zf) with chlorine or HCl / oxygen to form 1,1,1-trifluoro-2,3-dichloropropane (243db). iii) React 1,1,1-trifluoro-2,3-dichloropropane (243db) with a first caustic base 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 boron trihalide to form 2-chloro-1,1,1,2-tetrafluoropropane (244bb); and v) React the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with a second caustic base to form 2,3,3,3-tetrafluoropropene (1234yf).

27. The method 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 boron trihalide and 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 according to claim 28, wherein the composition further comprises 1,1,1,2,2-pentafluoropropane (245cb).

30. The composition of claim 29, wherein the composition further comprises hydrogen fluoride.

31. The composition according to claim 30, wherein the composition is prepared by the method according to claim 1.

32. The composition according to claim 28, wherein the composition further comprises fluorinated sulfonic acid.

33. The composition according to claim 32, wherein the composition further comprises 1,1,1,2,2-pentafluoropropane (245cb).

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

35. The composition according to claim 34, wherein the composition is prepared by the method according to claim 2.

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