WO2025064346A1 - Procédés de préparation de 2-chloro-1,1,1,2-tétrafluoropropane - Google Patents

Procédés de préparation de 2-chloro-1,1,1,2-tétrafluoropropane Download PDF

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WO2025064346A1
WO2025064346A1 PCT/US2024/046884 US2024046884W WO2025064346A1 WO 2025064346 A1 WO2025064346 A1 WO 2025064346A1 US 2024046884 W US2024046884 W US 2024046884W WO 2025064346 A1 WO2025064346 A1 WO 2025064346A1
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chloro
trifluoropropene
reacting
ene
tetrafluoropropane
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Sheng Peng
Andrew Jackson
Andrey Anatolievich Filatov
Yurii Lvovich Yagupolskii
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Chemours Co FC LLC
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Chemours Co FC LLC
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Priority to CN202480057736.4A priority Critical patent/CN121816334A/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons

Definitions

  • 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.
  • HFOs Hydrofluoroolefins
  • CFCs chlorofluorocarbons
  • HCFCs hydrofluorofluorocarbons
  • 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.
  • 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.
  • 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.
  • 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.
  • boron trifluoride 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).
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • 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.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is
  • 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’.
  • C n-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.
  • C n -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.
  • the alkyl group contains from 1 to 6 carbon atoms.
  • C n-m alkenyl 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.
  • the alkenyl moiety contains 2 to 6 carbon atoms.
  • the alkenyl group is substituted by 2s F atoms, wherein “s” is the number of carbon atoms in the alkenyl group.
  • C n-m fluoroalkyl 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.
  • the fluoroalkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
  • C n-m fluoroalkoxy 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.
  • the fluoroalkoxy group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.
  • fluorinated sulfonic acid refers to a compound of group R F -SOsH, wherein variable R F is as defined herein.
  • R F is fluoro or a moiety comprising at least one F atom, as described herein.
  • halogen refers to fluoro, chloro, bromo and iodo. In some embodiments, the halo is fluoro.
  • dehydrohalogenation 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.
  • dehydrochlorination refers to a process during which hydrogen and chlorine on adjacent carbons in a molecule are removed to form the corresponding olefin.
  • the phrase “optionally substituted” means unsubstituted or substituted.
  • the substituents are independently selected, and substitution may be at any chemically accessible position.
  • 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.
  • mixing 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.
  • reactants e.g., 2-chloro-3,3,3-trifluoroprop-1-ene, hydrogen fluoride, and boron trihalide
  • the mixing 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.
  • 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
  • mixing is provided by a mechanical agitator.
  • 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.
  • 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.
  • 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.
  • about 0.1 to about 50 horsepower/1000 gallon of liquid is imparted to the agitator, making the agitator agitate the reaction mixture.
  • about 0.5 to about 40 horsepower/1000 gallon of liquid is imparted to the agitator, making the agitator agitate the reaction mixture.
  • about 1 to about 35 horsepower/1000 gallon of liquid is imparted to the agitator, causing the agitator to agitate the reaction mixture.
  • 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.
  • a process of the present application is performed in the presence of a caustic (or base) that would dissociate when placed in water.
  • 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.
  • the processes of the present application may be conducted in the presence of a catalyst (e.g., a boron trihalide catalyst).
  • a catalyst e.g., a boron trihalide catalyst.
  • HFO hydrofluoroolefin
  • HCFC-243db or 243db 1 ,1 ,1-trifluoro-2,3-dichloropropane
  • HCFC-244bb or 244bb 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane
  • HFC-245cb 1 , 1 ,1 ,2,2-pentafluoropropane
  • HCFO-1233xf or 1233xf 2-chloro-3,3,3-trifluoroprop-1-ene
  • HFO-1234yf or 1234yf 2,3,3,3-tetrafluoroprop-1-ene or 2, 3,3,3- tetrafluoropropene
  • HFO-1243zf or 1243zf 3,3,3-trifluoroprop-1-ene
  • the present application provides processes for preparing 2-chloro-1 , 1 ,1 ,2- tetrafluoropropane (244bb).
  • 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).
  • 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.
  • the boron trihalide is selected from the group consisting of boron trifluoride (BF3), boron trichloride (BCI3), and boron tribromide (BBrs).
  • the boron trihalide is boron trifluoride (BF3).
  • the process is performed in the absence of the fluorinated sulfonic acid.
  • the process is performed in the presence of the fluorinated sulfonic acid.
  • the fluorinated sulfonic acid is a compound of Formula I: wherein:
  • R F is selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R 1 -O-CX 1 H-C(X 1 )2-; each X 1 is independently selected from the group consisting of H and fluoro, provided that at least one X 1 is fluoro; and
  • R 1 is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted.
  • R F is selected from the group consisting of fluoro, C1-6 fluoroalkyl, and C1-6 fluoroalkoxy. In some embodiments, R F is selected from the group consisting of fluoro, C1-3 fluoroalkyl, and C1-3 fluoroalkoxy. In some embodiments, R F is selected from the group consisting of fluoro, C1-3 fluoroalkyl, and C1-3 fluoroalkoxy.
  • R F is R 1 -O-CX 1 H-C(X 1 )2-.
  • R 1 is unsubstituted C1-6 alkyl.
  • R 1 is C1-6 fluoroalkyl.
  • R 1 is unsubstituted C2-6 alkenyl.
  • R 1 is C2-6 fluoroalkenyl.
  • each X 1 is fluoro. In some embodiments, one X 1 group is H and two X 1 groups are fluoro. In some embodiments, two X 1 groups are H and one X 1 group is fluoro.
  • 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.
  • the fluorinated sulfonic acid is selected from the group consisting of fluorosulfonic acid, trifluoromethanesulfonic acid, 1 , 1 ,2,2- tetrafluoroethane-1 -sulfonic acid.
  • the fluorinated sulfonic acid is fluorosulfonic acid or trifluoromethanesulfonic acid (/.e., triflic acid).
  • the fluorinated sulfonic acid is fluorosulfonic acid.
  • the fluorinated sulfonic acid is trifluoromethanesulfonic acid.
  • 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.
  • 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 to about
  • 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.
  • a molar excess of boron trihalide is used based on 1 molar equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).
  • a catalytic amount of boron trihalide is used based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf).
  • 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.
  • 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).
  • 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.
  • 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 processes provided herein further comprise substantially isolating the 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC-244bb).
  • 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.
  • the processes provided herein further comprise substantially isolating (e.g., purifying) 2-chloro-1 ,1,1,2-tetrafluoropropane (HCFC- 244bb)via distillation.
  • 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).
  • a reaction mixture e.g., hydrogen fluoride, boron trihalide, fluorinated sulfonic acid, or any combination thereof.
  • the one or more additional components of the reaction mixture are removed via distillation.
  • 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).
  • 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).
  • 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).
  • a fluorinated sulfonic acid e.g., a fluorinated sulfonic acid of Formula I
  • the processes provided herein comprise preparing a composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane (HCFC-244bb) and one or more additional components.
  • 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).
  • the composition comprising 2-chloro-1 ,1 ,1,2-tetrafluoropropane comprises less than about 1% by weight 1 ,1,1,2,2-pentafluoropropane (HFC-245cb).
  • the composition comprising 2-chloro-1, 1 , 1 ,2- tetrafluoropropane 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).
  • 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).
  • composition comprising 2-chloro-1 ,1 ,1 ,2-tetrafluoropropane further comprises less than about 2% by weight of unreacted 2- chloro-3, 3, 3, -trifluoropropene (1233xf).
  • 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).
  • 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).
  • 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.
  • 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-
  • 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.
  • 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.
  • 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.
  • 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.
  • the second reaction zone is comprised of one or more reactors operated in series.
  • the first and the second reaction zones each comprise CSTR reactors.
  • 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.
  • carryover boron trihalide e.g., BF3
  • fluorinated sulfonic acid e.g., a compound of Formula I, as described herein
  • 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 R F -SOsH represents the optional fluorinated sulfonic acid component of the processes of the invention.
  • 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).
  • the dehydrochlorination reaction comprises reacting the 2-chloro-1,1,1,2-tetrafluoropropane (244bb) with caustic to form 2,3,3,3-tetrafluoropropene (1234yf).
  • 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.
  • 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.
  • the first adiabatic reactor is upstream of and in fluid communication with a heat exchanger.
  • the heat exchanger is in fluid communication and upstream of a subsequent adiabatic reactor.
  • the adiabatic reaction zone consists of two reactors, a first adiabatic reactor and a final adiabatic reactor.
  • a heat exchanger is downstream from the first adiabatic reactor and upstream of the final adiabatic reactor.
  • the adiabatic reactors in the adiabatic reaction zone are in fluid communication with heat exchangers, wherein a heat exchanger is disposed between two reactors.
  • 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.
  • 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
  • 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.
  • 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.
  • the adiabatic reactors may be of any shape that is conducive to performing one or more of the processes described herein.
  • each reactor is independently a cylindrical tube or pipe, each of which may be straight or coiled.
  • the reactor is a plug flow reactor. Plug flow reactors minimize back mixing thereby resulting in lower overall conversion.
  • adiabatic reactors for use in the adiabatic reaction zone disclosed herein may be comprised of materials which are resistant to corrosion. Exemplary materials
  • INCORPORATED BY REFERENCE 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 MonelTM nickelcopper alloys, HastelloyTM nickel-based alloys, and InconelTM nickel-chromium alloys.
  • the reactor is comprised of nickel-based alloy.
  • 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.
  • 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.
  • the present application provides an adiabatic reaction zone.
  • the adiabatic reaction zone is suitable for performing one or more of the processes described herein.
  • the adiabatic reaction zone comprises at least two adiabatic reactors.
  • a heat exchanger is arranged between each of the reactors.
  • 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.
  • 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
  • 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 (1233x
  • heat exchangers are used in the processes performed in the adiabatic reaction zones as described herein.
  • a heat exchanger is arranged between two adiabatic reactors in series.
  • the heat exchangers replace the heat used by the reactions which are endothermic processes (e.g., dehydrohalogenation reactions).
  • the heat exchangers used herein may be shell and tube heat exchangers.
  • 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.
  • 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.
  • 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 another
  • 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.
  • 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.
  • 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.
  • the processes 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).
  • a reactor e.g., an adiabatic reactor as described herein
  • HCFC-244bb 2-chloro-1 ,1 ,1,2-tetrafluoropropane
  • the impurities in the reactor are selected from the group consisting of metal halides, metal oxides, and carbonaceous materials.
  • the metal halides comprise halides of Ni, Cr, Fe, Mo, Nb, Cu, and Co.
  • 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.
  • the reducing agent is selected from the group consisting of H2, NH3, CO, C1-C12 hydrocarbons, and combinations of these.
  • 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.
  • the step of removing impurities from the reactor comprises physically removing carbonaceous materials, metal oxides, and metal halides from the reactor.
  • 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.
  • the selectivity of preparing the 2, 3,3,3- tetrafluoropropene is at least 90% or higher.
  • 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).
  • 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.
  • 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.
  • the solid sorbent is selected from the group consisting of alumina, calcium carbonate, sodium carbonate, and sodium aluminate.
  • 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).
  • 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.
  • 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.
  • 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.
  • the dehydrochlorinating occurs in the vapor phase.
  • 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.
  • impurities that are advantageous to remove
  • INCORPORATED 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).
  • 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-
  • 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 step of preparing 2-chloro-3,3,3-trifluoropropene 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.
  • 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.
  • the carbon is an activated carbon.
  • the carbon is an acid washed activated carbon.
  • M is K and Y is F or Cl.
  • 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.
  • 3,3,3-trifluoropropene (1233xf) is at least 90 mole %.
  • the product selectivity for preparing the 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 95 mole %.
  • the dehydrochlorination selectivity for preparing the 2-chloro-3,3,3-trifluoropropene (1233xf) is at least 90 mole %.
  • 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).
  • 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.
  • 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).
  • 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).
  • the process is conducted in the presence of hydrogen fluoride (HF).
  • HF hydrogen fluoride
  • the mole ratio of HF to 2-chloro- 3,3,3-trifluoropropene in the reaction zone is no more than 0.9.
  • 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.
  • 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 %.
  • 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).
  • 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).
  • said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with chlorine to form the 1 , 1 , 1-trifluoro-
  • said chlorinating comprises reacting the 3,3,3-trifluoropropene (1243zf) with HCI/oxygen to form the 1,1,1- trifluoro-2,3-dichloropropane (243db).
  • 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.
  • 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).
  • 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.
  • the metal halide is supported on activated carbon.
  • the activated carbon is acid washed or caustic washed.
  • 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.
  • 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.
  • the chlorination occurs in the vapor phase with or without a chlorination catalyst.
  • 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.
  • 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 catalyst is selected from a chrome catalyst or an alumina catalyst.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • 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 ,
  • 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);
  • 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).
  • a boron trihalide e.g., BF3
  • a fluorinated sulfonic acid provided herein ⁇ e.g. a compound of Formula I).
  • 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.
  • 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.
  • 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.
  • boron trihalide based on 1 equivalent of the 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) in step iv) of the processes described above.
  • 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.
  • 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.
  • 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.
  • 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.
  • HFO-1234yf 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 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).
  • 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
  • additional compounds e.g., minor components
  • the composition comprises about 50 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.
  • the composition comprises about 85 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.
  • the composition comprises about 90 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.
  • the composition comprises about 95 to about 99 percent 2-chloro-1 ,1,1,2-tetrafluoropropane (244bb) as measured by GC-MS.
  • the composition comprises about 1 to about 45 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.
  • the composition comprises about 1 to about 15 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.
  • the composition comprises about 1 to about 12 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.
  • the composition comprises about 1 to about 5 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.
  • the composition comprises about 1 to about 3 percent 2-chloro-3,3,3-trifluoroprop-1-ene (1233xf) as measured by GC-MS.
  • the composition further comprises 1, 1,1, 2,2- pentafluoropropane (245cb).
  • the composition comprises about 0.01 to about 1 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.
  • the composition comprises about 0.01 to about 0.5 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.
  • the composition comprises about 0.01 to about 0.2 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.
  • the composition comprises about 0.01 to about 0.1 percent 1 ,1 ,1 ,2,2-pentafluoropropane (245cb) as measured by GC-MS.
  • the composition further comprises hydrogen fluoride.
  • the composition further comprises a fluorinated sulfonic acid provided herein (e.g., a compound of Formula I, as described herein).
  • 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:
  • R F is selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R 1 -0-CX 1 H-C(X 1 )2-; each X 1 is independently selected from H and fluoro, provided that at least one X 1 is fluoro; and
  • R 1 is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted.
  • R F is selected from the group consisting of fluoro, C1-6 fluoroalkyl, and C1-6 fluoroalkoxy.
  • R F is R 1 -0-CX 1 H-C(X 1 )2-.
  • 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.
  • 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- t
  • 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
  • R F is selected from the group consisting of fluoro, C1-6 fluoroalkyl, C1-6 fluoroalkoxy, and R 1 -O-CX 1 H-C(X 1 )2-; each X 1 is independently selected from H and fluoro, provided that at least one X 1 is fluoro; and
  • R 1 is C1-6 alkyl or C2-6 alkenyl, each of which may be optionally substituted.
  • 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.

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Abstract

La présente demande concerne la préparation de 2-chloro-1,1,1,2-tétrafluoropropane à partir de 2-chloro-3,3,3-trifluoroprop-1-ène en présence d'un catalyseur au bore et, éventuellement, d'un acide sulfonique fluoré. L'invention concerne également des procédés de préparation de HFO-1234yf à l'aide du 2-chloro-1,1,1,2-tétrafluoropropane ainsi que des compositions contenant du 2-chloro-1,1,1,2-tétrafluoropropane.
PCT/US2024/046884 2023-09-18 2024-09-16 Procédés de préparation de 2-chloro-1,1,1,2-tétrafluoropropane Pending WO2025064346A1 (fr)

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Citations (10)

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