Dehydrohalogenation of hydrochlorofluorocarbons

Abstract

To solve the following problem: there is a need to conduct dehydrohalogenation reactions in the absence of phase transfer catalysts.SOLUTION: The present specification relates to a dehydrohalogenation process, comprising contacting a halofluoroalkane of formula RCXYCZQT with a caustic agent in an aqueous solvent in the absence of a catalyst, optionally in the presence of an amine, while providing mixing with power input ranging from about 0.1 to about 50 HP / 1000 gallons to produce a product comprising a fluoroolefin of formula RCX=CZQ, wherein: R is a perfluorinated alkyl group; X, Z and Q are independently H or halogen; and one of Y and T is H and the other thereof is halogen.SELECTED DRAWING: None

Description

[Technical field]

[0001] This disclosure relates generally to the dehydrohalogenation of hydrochlorofluorocarbons (HCFCs) in the liquid phase in the absence of a dehydrohalogenation catalyst (including a phase transfer catalyst) to produce hydrochlorofluoroolefins (HCFOs). [Background technology]

[0002] Hydrochlorofluoroolefins (HCFOs) have low ozone depletion potential and low global warming potential and are considered as potential replacements for saturated CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons). HCFOs can be employed in a wide range of applications, including their use as refrigerants, solvents, blowing agents, cleaning agents, aerosol propellants, dielectrics, fire extinguishing agents, and power cycle operating fluids. For example, HCFO-1233xf (CF3CCl=CH2) can be used as a blowing agent, fire extinguishing agent, refrigerant, etc. HCFO-1233xf is also an intermediate in the production of 2,3,3,3-tetrafluoropropene (HFO-1234yf), a refrigerant with zero ozone depletion potential and low global warming potential.

[0003] Traditionally, phase transfer catalysts have been used for the preparation of HCFOs. They accelerate the reaction, but they also pose environmental problems due to the need to dispose of these spent catalysts. Furthermore, the use of phase transfer catalysts increases the cost of the dehydrohalogenation reaction.

[0004] Because they are expensive, elimination of the use of phase transfer catalysts would reduce the cost of these dehydrohalogenation reactions. In addition, their elimination could make waste disposal easier and less expensive. Additionally, elimination of phase transfer catalysts could simplify the dehydrohalogenation reactions by reducing the need to recycle and recover them from the process. Finally, because catalysts reduce the activation energy of the dehydrohalogenation, they are more prone to cracking the dehydrohalogenation products and wasting starting material. Elimination of phase transfer catalysts in the dehydrohalogenation reaction could reduce this risk. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, a need exists to carry out the dehydrohalogenation reaction without the presence of a phase transfer catalyst. [Means for solving the problem]

[0006] The present disclosure provides a dehydrohalogenation process without the presence of a dehydrohalogenation catalyst, including a phase transfer catalyst. The process includes contacting a halofluoroalkane having the formula RCXYCZQT with a caustic in an aqueous solution at a temperature range of about 20° C. to about 100° C. while mixing at a power ranging from about 0.1 to about 50 horsepower per 1000 gallons (HP / 1000 gal) to produce a product including a fluoroolefin having the formula RCX=CZQ, where R is a perfluorinated alkyl group, X, Z, and Q are independently H or a halogen, and one of Y and T is H and the other is a halogen, such as chlorine, bromine, or iodine. In another embodiment, an amine or ammonia is further present. In yet another embodiment, the process includes contacting a halofluoroalkane RCXYCZQT with a caustic and an amine having the formula NR1R2R3 in an aqueous solution at a temperature range of about 0° C. to about 80° C. while mixing at a power ranging from about 0.1 to about 50 horsepower per 1000 gallons (HP / 1000 gal) to produce a product comprising a fluoroolefin having the formula RCX=CZQ, where R is a perfluorinated alkyl group, X, Z and Q are independently H or halogen, one of Y and T is H and the other is halogen, and R1, R2 and R3 are independently hydrogen, an alkyl group, an aryl, an arylalkyl group, a heterocycle, a heterocyclic alkyl group or N(R4)(R5)N(R6)(R7), where R4, R5, R6 and R7 are independently hydrogen, an alkyl group, an aryl, an arylalkyl group, a heterocycle or a heterocyclic alkyl group. In one embodiment, the molar ratio of amine to RCXYCZQT ranges from about 0.02 to about 3. In another embodiment, the molar ratio of amine to caustic ranges from about 0.02 to about 3. In yet another embodiment, the molar ratio of caustic to halofluoroalkane ranges from about 0.01 to about 0.05; in another embodiment, from about 0.02 to about 4, in another embodiment, from about 0.04 to about 2, and in yet another embodiment, from about 0.05 to about 1.5.In yet another embodiment, the molar ratio of amine to RCXYCZQT ranges from about 0.02 to about 3, the molar ratio of amine to caustic ranges from about 0.02 to about 3, and the molar ratio of halofluoroalkane to caustic ranges from about 0.01 to about 5.

[0007] Features and advantages of the present disclosure will become apparent from the following non-limiting examples of various aspects of the invention. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a graph showing temperature and pressure versus time for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 28° C. in a 200 ml shaker tube reactor in the absence of a phase transfer catalyst, as described in Example 1. [Diagram 2] FIG. 2 is a graph showing temperature and pressure versus time for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 55° C. in a 200 ml shaker tube reactor in the absence of a phase transfer catalyst, as described in Example 2. [Diagram 3] FIG. 1 is a graph showing temperature and pressure versus time for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 80° C. in a 200 ml shaker tube reactor in the absence of a phase transfer catalyst, as described in Example 3. [Figure 4] FIG. 1 is a graph showing the change in temperature and agitation speed versus time for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 55° C. in an autoclave in the absence of a phase transfer catalyst, as described in Example 5. [Diagram 5]FIG. 1 is a graph showing temperature versus time at various stirring speeds for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 80° C. in an autoclave in the absence of a phase transfer catalyst, as described in Example 7. [Figure 6] FIG. 13 is a graph showing temperature versus time at various stirring speeds for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 60° C. in an autoclave in the absence of a phase transfer catalyst, as described in Example 10. [Figure 7] FIG. 13 is a graph showing pressure versus time at various agitation speeds for the dehydrochlorination of 2,3-dichloro-1,1,1-trifluoropropane with 12 wt % NaOH at 60° C. in an autoclave in the absence of a phase transfer catalyst, as described in Example 10. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as defined in the appended claims. Additional features and advantages of one or more of the embodiments will become apparent from the following detailed description and claims.

[0010] As used herein, the terms "comprise," "comprising," "include," "including," "has," "having," or any other variations thereof, are intended to encompass non-exclusive inclusions. For example, a process, method, article, or apparatus that includes listed 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. Furthermore, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or. For example, a condition A or B is satisfied by any 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).

[0011] Additionally, the use of "a" or "an" is employed to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be interpreted to include one or at least one, and the singular also includes the plural, unless it is clear that something else is meant.

[0012] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. Similar or equivalent methods and materials to those described herein can be used in carrying out or testing embodiments of the present invention, but suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety unless specifically cited. In case of conflict, the present specification, including definitions, will take precedence. In addition, materials, methods, and examples are merely illustrative and are not intended to be limiting.

[0013] When an amount, concentration, or other value or parameter is given as a range, a preferred range, or a list of upper and / or lower preferred values, this should be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are individually disclosed. When a range of numerical values ​​is given herein, unless otherwise stated, it is intended that the range includes the endpoints thereof, and all integers and fractions within the range.

[0014] As used herein, the term "dehydrohalogenation" refers to the process of removing hydrogen and a halogen (e.g., Cl, Br, or I) on adjacent carbons in a molecule to form the corresponding olefin.

[0015] As used herein, the term "dehydrochlorination" refers to the process of removing hydrogen and chlorine on adjacent carbons in a molecule to form the corresponding olefin.

[0016] As used herein, the terms "fluoroolefin" and "fluoroalkene" are synonymous and used interchangeably. They are each defined as a molecule containing hydrogen, carbon, fluorine, and a carbon-carbon double bond, and optionally containing chlorine or other halogen atoms. Examples are described throughout the specification. One example is HCFO-1233xf.

[0017] As used herein, the term "halofluoroalkane" means a saturated alkane containing carbon, hydrogen, fluorine and at least one halogen other than fluorine, such as I, Br or Cl.

[0018] As used herein, the term "chlorofluoroalkane" means a saturated alkane containing carbon, hydrogen, fluorine and chlorine, and optionally other halogens.

[0019] As used herein, the term "alkyl", alone or in compound words such as "perfluorinated alkyl group", includes cyclic or acyclic and straight or branched alkyl groups, such as, for example, methyl, ethyl, n-propyl, i-propyl, or other isomers. For example, an alkyl group may contain 1-10 carbon atoms. An alkyl group may be a lower alkyl containing 1 to 6 carbon atoms.

[0020] As used herein, the term "perfluorinated alkyl group" refers to an alkyl group in which all hydrogens on a carbon atom are replaced by fluorine. Examples of perfluorinated alkyl groups include -CF3 and -CF2CF3.

[0021] As defined herein, "aryl," used alone or in combination, means an aromatic ring containing 6, 10, 14 or 18 ring carbon atoms, including, for example, phenyl, α-naphthyl, β-naphthyl, anthracenyl, and the like.

[0022] As defined herein, use of the term "arylalkyl" means that an alkyl group is attached at one end to the backbone and at the other end to an aryl group, including, for example, benzyl, phenethyl, phenpropyl, and the like.

[0023] The term "heterocycle", when used alone or in compound terms, means an aromatic, partially aromatic, partially saturated or saturated monocyclic, bicyclic or tricyclic ring system containing 3 to 14 ring atoms, where one, two or three of the ring atoms are independently selected from nitrogen, oxygen and sulfur, and the remaining ring atoms are carbon atoms. The heterocycle may be a fused ring system containing two or three fused rings; at least one of the rings contains at least one heteroatom selected from nitrogen, oxygen or sulfur. The heteroatom ring atoms may be located on a fully saturated, partially saturated or aromatic ring. The heterocycle may be fully heteroaromatic or partially heteroaromatic, where one of the rings fused to the heterocycle is aromatic or the heteroatom is on a ring atom of an aromatic ring. As used herein, heterocyclic includes heteroaromatic. Furthermore, the heterocyclic ring may contain one or more double bonds, either between two ring carbons, between two ring nitrogen atoms, or between a ring nitrogen atom and a ring carbon atom. The designation of aza, oxa or thio as a prefix of heterocyclyl means that at least one ring nitrogen, ring oxygen or ring sulfur atom is present as a ring atom, respectively. The ring nitrogen atom of a heterocyclic compound may be a basic nitrogen atom. The ring nitrogen atom or ring sulfur atom of a heterocyclic compound may also be optionally oxidized to the corresponding N-oxide, S-oxide or S,S-dioxide. When a heteroaryl is substituted with a hydroxy group, the corresponding tautomer is also included.Exemplary heterocycles include piperidyl, pyrrolidyl, piperazinyl, morpholinyl, tetrahydrofuryl, thiomorpholinyl, thiazolidinyl, 1,3-dioxolanyl, 1,4-dioxanyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, pyrazinyl, thienyl, isothiazolyl, oxazolyl, pyrazolyl, furanyl, pyrrolyl, 1,2,4-thiadiazolyl, pyridazinyl, quinoxalinyl, phthalazinyl, imidazo[1,2-a]pyridine, imidazo[2,1-b]thiazolyl, benzofuranyl, aza. These include indolyl, benzimidazolyl, benzothienyl, thienopyridyl, thienopyrimidyl, pyrrolopyridyl, imidazopyridyl, benzoazaindolyl, 1,2,4-triazinyl, benzothiazolyl, imidazolyl, indolyl, indolizinyl, isoxazolyl, isoquinolinyl, isothiazolyl, oxadiazolyl, pyrazinyl, pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl, pyrrolyl, quinazolinyl, quinolinyl, 1,3,4-thiadiazolyl, thiazolyl, thienyl and thiazolyl.

[0024] As defined herein, the term "heterocyclic alkyl" means an alkyl group attached at one terminus to a heterocyclic ring and at the other terminus to the main chain.

[0025] The term "halogen" means fluorine, chlorine, bromine and iodine.

[0026] The term "aqueous solvent" refers to a solvent that includes water or a mixture of one or more solvents mixed with water. In one embodiment, water is the sole solvent. However, aqueous solvents may also include water mixed with other solvents that are miscible with water, such as methanol, ethanol, 1-propanol, 2-propanol, 1,3-butanediol, 1,2-butanediol, acetonitrile, acetaldehyde, acetone, ethylene glycol, propylene glycol, tetrahydrofuran, triethylene glycol, 1,3-propanediol, glycerol, 1,4-dioxane, and the like.

[0027] As described herein, in one embodiment, the halofluoroalkane is mixed with a caustic in an aqueous solvent at a mixing power in the range of about 0.1 to about 150 horsepower per 1000 gallons to produce a fluoroolefin. As defined herein, the term "mixing" refers to the process of stirring the reactants, the halofluoroalkane and the caustic at a specific mixing power of about 0.1 to about 50 horsepower per 1000 gallons of aqueous solution. Stirring, i.e., mixing, in one embodiment, can be accomplished by mechanical means, such as a stirrer or shaker, to allow the reactants to mix substantially thoroughly with each other under conditions sufficient to dehydrohalogenate the halofluoroalkane to produce a fluoroolefin.

[0028] As used herein, the terms "mixing power" and "agitating power" or similar terms are synonymous and are used interchangeably.

[0029] Some fluoroolefins in the present disclosure, such as CF3CH=CHCl (HCFO-1233zd), exist as different configurational isomers, or stereoisomers. If no particular isomer is specified, the present disclosure refers to one configurational isomer, one stereoisomer, or any combination thereof. For example, HCFO-1233zd is meant to represent the E isomer, the Z isomer, or any combination, or a mixture of both isomers in any ratio.

[0030] Disclosed in embodiments is a liquid phase dehydrohalogenation process comprising contacting a halofluoroalkane having the formula RCXYCZQT with a caustic in an aqueous solvent at a temperature range of about 20° C. to about 100° C. while providing mixing at a power input ranging from about 0.1 to about 50 HP / 1000 gallons to produce a fluoroolefin having the formula RCX=CZQ, where R is a perfluorinated alkyl group, X, Z and Q are independently H or halogen, one of Y and T is hydrogen and the other is a halogen, such as chlorine, bromine or iodine. The conditions described are effective for the dehydrohalogenation reaction to occur, and the halofluoroalkane is dehydrohalogenated by the caustic base to form the corresponding fluoroolefin.

[0031] In one embodiment, either Y or T (but not both) is chlorine, in which case the process is a dehydrochlorination reaction.

[0032] In some embodiments of the invention, R is -CF3 or -CF2CF3. In some embodiments of the invention, RCXYCQZT is CF3CHClCH2Cl (HCFC-243db) and RCX=CQZ is CF3CCl=CH2 (HCFO-1233xf). Other examples include RCXYCQZT as CF3CH2CHCl2, CF3CCl2CH3, CF3CHFCH2Cl, CF3CHClCH2F, CF2CH2CHClF, CF3CClFCH3, with the respective reaction products being CF3CH=CHCl, CF3CCl=CH2, CF3CF=CH2, CF3CH=CHF, CF3CH=CHF and CF3CF=CH2.

[0033] The chlorofluoroalkanes, i.e., RCXYCZQT, used in the dehydrohalogenation process of this disclosure can be synthesized by methods known in the art. For example, HCFC-243db can be prepared by chlorinating CF3CH=CH2 or by the addition reaction of CFClH2 with CF2=CHCl.

[0034] The reaction process is carried out in the presence of a caustic agent, which in one embodiment includes a base that dissociates when placed in water. Examples include alkali metal oxides, hydroxides or amides, such as sodium or potassium oxide, sodium or potassium hydroxide, or sodium 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.

[0035] However, as defined, the term "caustic" excludes amines, including ammonia. Unless specifically indicated to the contrary, the term "amine" includes ammonia.

[0036] Unless otherwise specified, as used herein, the term "alkali metal hydroxide" means a compound or mixture of compounds selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

[0037] Similarly, the term "alkali metal amide" means a compound selected from lithium amide, sodium amide, potassium amide, rubidium amide and cesium amide, or a mixture of compounds thereof.

[0038] Unless otherwise specified, as used herein, the term "alkaline earth metal hydroxide" means a compound selected from beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and mixtures of such compounds.

[0039] Similarly, the term "alkaline earth metal amide" means a compound selected from beryllium amide, magnesium amide, calcium amide, strontium amide and barium amide, or a mixture of such compounds.

[0040] The caustic may include NaOH, KOH, LiOH, CsOH, Ca(OH)2, Zn(OH)2, Na2CO3, K2CO3, K3PO4, Na3PO4, KF or CsF, etc., and may be dissolved in the aqueous solution or in aqueous suspension. The caustic in the aqueous phase is present in an amount effective for dehydrohalogenation.

[0041] In one embodiment, the molar ratio of caustic to halofluoroalkane having the formula RCXYCZQT ranges from about 0.01 to about 5. In one embodiment, the molar ratio ranges from about 0.02 to about 4, in another embodiment from about 0.04 to about 2, and in yet another embodiment from about 0.05 to about 1.5. Thus, for example, the molar ratios are 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.40, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, 0.50, 0.51, 0.52, 0.53, 0.54, 0.55, 0.56, 0.57, 0.58, 0.59, 0.60, 0.61, 0.62, 0.63, 0.64, 0.65, 0.66, 0.67, 0.68, 0.69, 0.70, 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.90, 0.81, 0.82, 0.83 ,0.84,0.85,0.86,0.87,0.88,0.89,0.90,0.91,0.92,0.93,0.94,0.95,0.96,0.97,0.98,0.99,1.00,1.01,1.02,1.03,1.04,1.05,1.06,1.07,1.08,1.09,1.10,1.11,1.12,1.13,1.14,1.15,1.16,1.17,1.18,1.19,1.20,1.21,1.22,1.23,1.24,1.25,1.26,1.27,1.28,1.29,1.30,1.31,1.32,1.33,1.34,1.35,1.36,1.37,1.38,1.39,1.40,1.41,1.42,1.43,1.44,1.45,1.46,1.47,1.48,1.49,1.50,1.51,1.52,1.53,1.54,1.55,1.56,1.57,1.58,1.59,1.60,1.61,1.62,1.63,1.64,1.65,1.66,1.67,1.68,1.69,1.70,1.71,1.72,1.73,1.74,1.75,1.76,1.77,1.78,1.79,1.80,1.81,1.82,1.83,1.84,1.85 6, 1.27, 1.28, 1.29, 1.30, 1.31, 1.32, 1.33, 1.34, 1.35, 1.36, 1.37, 1.38, 1.39, 1.40, 1.41, 1.42, 1.43, 1.44, 1.45, 1.46, 1.47, 1.48, 1.49, 1.50, 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, 1.57, 1.58, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69、1.70、1.71、1.72、1.73、1.74、1.75、1.76、1.77、1.78、1.79、1.80、1.81、1.82、1.83、1.84、1.85、1.86、1.87、1.88、1.89、1.90、1.91、1.92、1.93、1.94、1.95、1.96、1.97、1.98、1.99、2.00、2.01、2.02、2.03、2.04、2.05、2.06、2.07、2.08、2.09、2.10、2.11、2.12、2.13、2.14、2.15、2.16、2.17、2.18、2.19、2.20、2.21、2.22、2.23、2.24、2.25、2.26、2.27、2.28、2.29、2.30、2.31、2.32、2.33、2.34、2.35、2.36、2.37、2.38、2.39、2.40、2.41、2.42、2.43、2.44、2.45、2.46、2.47、2.48、2.49、2.50、2.51、2.52、2.53、2.54、2.55、2.56、2.57、2.58、2.59、2.60、2.61、2.62、2.63、2.64、2.65、2.66、2.67、2.68、2.69、2.70、2.71、2.72、2.73、2.74、2.75、2.76、2.77、2.78、2.79、2.80、2.81、2.82、2.83、2.84、2.85、2.86、2.87、2.88、2.89、2.90、2.91、2.92、2.93、2.94、2.95、2.96、2.97、2.98、2.99、3.00、3.01、3.02、3.03、3.04、3.05、3.06、3.07、3.08、3.09、3.10、3.11、3.12、3.13、3.14、3.15、3.16、3.17、3.18、3.19、3.20、3.21、3.22、3.23、3.24、3.25、3.26、3.27、3.28、3.29、3.30、3.31、3.32、3.33、3.34、3.35、3.36、3.37、3.38、3.39、3.40、3.41、3.42、3.43、3.44、3.45、3.46、3.47、3.48、3.49、3.50、3.51、3.52、3.53、3.54、3.55、3.56、3.57、3.58、3.59、3.60、3.61、3.62、3.63、3.64、3.65、3.66、3.67、3.68、3.69, 3.70, 3.71, 3.72, 3.73, 3.74, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, 3.81, 3.82, 3.83, 3.84, 3.85, 3.86, 3.87, 3.88, 3.89, 3.90, 3.91, 3.92, 3.93, 3.94, 3.95, 3.96, 3.97, 3.98, 3.99, 4.00, 4.01, 4.0 2, 4.03, 4.04, 4.05, 4.06, 4.07, 4.08, 4.09, 4.10, 4.11, 4.12, 4.13, 4.14, 4.15, 4.16, 4.17, 4.18, 4.19, 4.20, 4.21, 4.22, 4.23, 4.24, 4.25, 4.26, 4.27, 4.28, 4.29, 4.30, 4.31, 4.32, 4.33, 4.34, 4.35 ,4.36,4.37,4.38,4.39,4.40,4.41,4.42,4.43,4.44,4.45,4.46,4.47,4.48,4.49,4.50,4.51,4.52,4.53,4.54,4.55,4.56,4.57,4.58,4.59,4.60,4.61,4.62,4.63,4.64,4.65,4.66,4.67,4.68, It may be 4.69, 4.70, 4.71, 4.72, 4.73, 4.74, 4.75, 4.76, 4.77, 4.78, 4.79, 4.80, 4.81, 4.82, 4.83, 4.84, 4.85, 4.86, 4.87, 4.88, 4.89, 4.90, 4.91, 4.92, 4.93, 4.94, 4.95, 4.96, 4.97, 4.98, 4.99, 5.00.

[0042] In one embodiment, an amine or ammonia is further present. In one embodiment, the dehydrohalogenation reaction is carried out in the presence of the caustic agent described above and an amine having the formula R1R2R3N, where R1, R2 and R3 are as defined above. The alkyl, heterocyclic, aryl, aralkyl and heterocyclic alkyl groups of R1, R2 and R3 can be substituted or unsubstituted. Substituted alkyl, heterocyclic, aryl, aralkyl or heterocyclic alkyl groups herein means that one or more hydrogens on a carbon atom are replaced by a functional group such as a hydroxyl group, an alkoxy group, a halogen, an amino group, etc. As defined herein, the amine can be an aliphatic amine, an aromatic amine, a heterocyclic amine or a mixture thereof. In some embodiments of the present invention, the amine is an aliphatic amine.

[0043] In some embodiments of the invention, when present, the amine can be a primary amine, a secondary amine, a tertiary amine, or a mixture thereof. In some embodiments of the invention, the amine is a primary unsubstituted alkylamine having the formula RNH2, where R is a C1-C 16 In some embodiments of the present invention, the amine is a primary unsubstituted alkylamine having the formula RNH, where R is a C-C unsubstituted alkyl group. Examples of primary unsubstituted alkylamines include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, amylamine, isoamylamine, tert-amylamine, hexylamine, and mixtures thereof.

[0044] In some embodiments of the present invention, the amine, when present, is a secondary unsubstituted alkylamine having the formula R1R2NH, where each of R1 and R2 is independently a C1-C6 unsubstituted alkyl group. In some embodiments of the present invention, the amine is a secondary unsubstituted alkylamine having the formula R1R2NH, where each of R is independently a C1-C3 unsubstituted alkyl group. Examples of secondary unsubstituted alkylamines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-sec-butylamine, diamylamine, dihexylamine, and mixtures thereof.

[0045] In some embodiments of the present invention, the amine is a tertiary unsubstituted alkylamine having the formula R1R2R3N, where each of R1, R2 and R3 is independently a C1-C6 unsubstituted alkyl group. In some embodiments of the present invention, when present, the amine is a tertiary unsubstituted alkylamine having the formula R1R2R3N, where each of R1, R2 and R3 is independently a C1-C3 unsubstituted alkyl group. Examples of tertiary unsubstituted alkylamines include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof.

[0046] In other embodiments of the invention, the amine, if present, is selected from the group consisting of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, isopropylamine, dipropylamine, diisopropylamine, tripropylamine, butylamine, sec-butylamine, tert-butylamine, dibutylamine, tributylamine, di-sec-butylamine, amylamine, isoamylamine, tert-amylamine, diamylamine, triamylamine, hexylamine, dihexylamine, trihexylamine, 1,1,3,3-tetramethylbutylamine, N,N-dimethylethylamine, N,N-dimethylpropylamine, N,N-dimethylbutylamine, and mixtures thereof.

[0047] In other embodiments of the invention, the amine has one, two or three substituted alkyl groups, which may be the same or different, in which one or more hydrogens on the carbon atoms are replaced with hydroxyl groups. Examples of such amines are ethanolamine (H2NCH2CH2OH), diethanolamine, triethanolamine, tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), 2-(methylamino)ethanol (CH3NHCH2CH2OH), 2-(ethylamino)ethanol (CH3CH2NHCH2CH2OH), 2-(propylamino)ethanol (CH3CH2CH2NHCH2CH2OH), 2-(isopropylamino)ethanol ((CH3)2CHNHCH2CH2OH), 2-(butylamino)ethanol (CH3(C H2)3NHCH2CH2OH), 2-(tert-butylamino)ethanol ((CH3)3CNHCH2CH2OH), triisopropanolamine ([CH3CH(OH)CH2]3N), N,N-dimethylethanolamine (HOCH2CH2N(CH3)2), 1-dimethylamino-2-propanol ((CH3)2NCH2CH(OH)CH3), 3-dimethylamino-1-propanol ((CH3)2N(CH2)3OH), 2-amino-2-methyl-1-propanol ((CH3)2C(NH2)CH2OH), and mixtures thereof.

[0048] In yet another embodiment of the invention, one of R1, R2 and R3 of the amine has a C1-C6 substituted alkyl group in which one or more hydrogens on a carbon atom are replaced by a hydroxy group, and the remaining groups are independently selected from hydrogen and C1-C6 16 Examples of such amines are selected from the group consisting of unsubstituted alkyl groups. Examples of such amines are ethanolamine (H2NCH2CH2OH), tris(hydroxymethyl)aminomethane ((HOCH2)3CNH2), 2-(methylamino)ethanol (CH3NHCH2CH2OH), 2-(ethylamino)ethanol (CH3CH2NHCH2CH2OH), 2-(propylamino)ethanol (CH3CH2CH2NHCH2CH2OH), 2-(isopropylamino)ethanol ((CH3)2CHNHCH2CH2OH), 2-(butylamino)ethanol (CH3(CH2)3NHCH2CH2OH), 2-(tert-butylamino)ethanol ((CH3)3CNHCH2CH2OH), N,N-dimethylethanolamine (HOCH2CH2N(CH3)2), 1-dimethylamino-2-propanol ((CH3)2NCH2CH(OH)CH3), 3-dimethylamino-1-propanol ((CH3)2N(CH2)3OH), 2-amino-2-methyl-1-propanol ((CH3)2C(NH2)CH2OH), and mixtures thereof. In some embodiments of the invention, at least one of R1, R2, and R3 of the amine is a C1-C6 substituted alkyl group in which one or more hydrogens on a carbon atom are replaced with an amino group, and the remaining groups are independently selected from hydrogen and C1-C6 substituted alkyl groups. 16 Unsubstituted alkyl groups are selected from the group consisting of. Examples of such amines include 3-(dimethylamino)propylamine ((CH3)2N(CH2)3NH2), 3-(diethylamino)propylamine ((C2H5)2N(CH2)3NH2), and mixtures thereof.

[0049] In some embodiments of the present invention, the amine, when present, is a polyamine. Examples of polyamines include ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4-diaminobutane, 1,3-diaminopentane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-pentanediamine, spermidine (N-(3-aminopropyl)butane-1,4-diamine), spermine (N,N'-bis(3-aminopropyl)butane-1,4-diamine), diethylenetriamine, triethylenetetramine, and mixtures thereof.

[0050] In some embodiments of the present invention, the amine, when present, is a heterocyclic amine. Examples of heterocyclic amines include pyrrolidine, pyrroline (including 1-pyrroline, 2-pyrroline and 3-pyrroline), piperidine, piperazine, morpholine, imidazole, pyrazole, pyridine, pyrimidine, pyridazine, pyrazine, pyridine, bipyridine (including 2,2'-bipyridine, 4,4'-bipyridine, 2,3'-bipyridine and 3,4'-bipyridine, etc.), and mixtures thereof.

[0051] In another embodiment of the invention, the amine, when present, is hydrazine (NH2NH2), a hydrazine derivative such as an alkyl hydrazine, an aryl hydrazine, or an aralkyl hydrazine, and mixtures thereof. Examples of hydrazine derivatives include methyl hydrazine (CH3NHNH2), 1,1-dimethyl hydrazine ((CH3)2NNH2), 1,2-dimethyl hydrazine (CH3NHNHCH3), phenyl hydrazine, 2,4-dinitrophenyl hydrazine, and mixtures thereof.

[0052] In some embodiments of the present invention, the amine, when present, is an aromatic amine. Examples of aromatic amines include aniline, o-toluidine, m-toluidine, p-toluidine, xylidine, 2,4,6-trimethylaniline, o-anisidine, m-anisidine, p-anisidine, N-methylaniline, N,N-dimethylaniline, N-ethylaniline, N,N-diethylaniline, and mixtures thereof.

[0053] In one embodiment, mixtures of any of the above-mentioned amines may also be used in the present disclosure.

[0054] In some embodiments of the present invention, the amine, when present, is selected from the group consisting of heterocyclic amines, hydrazines, derivatives thereof, and mixtures thereof. In some embodiments of the present invention, the amine is a heterocyclic amine and mixtures thereof.

[0055] In one embodiment, one of R1, R2, and R3 is hydrogen, and the others of R1, R2, and R3 are independently lower alkyl. In one embodiment, R2 and R3 can be the same or different. In yet another embodiment, R1, R2, and R3 are the same or different and are other than hydrogen. For example, R1, R2, and R3 are independently lower alkyl. In yet another embodiment, R1 is phenyl, alkyl, pyridine, alkyl-substituted pyridine, and R2 and R3 are as defined above. In another embodiment, the amine is hydrazine.

[0056] In one embodiment, the amines, when present, are trialkyl or dialkyl amines, with preferred amines being trialkyl amines.

[0057] It should be noted that all combinations and permutations of R1, R2 and R3 are contemplated.

[0058] In one embodiment, when present, the molar ratio of amine to halofluoroalkane ranges from about 0.02 to about 3. In one embodiment, the molar ratio ranges from about 0.05 to about 0.5, and in another embodiment, the molar ratio ranges from about 0.05 to about 0.25.

[0059] Additionally, in one embodiment, when present, the molar ratio of amine to caustic agent ranges from about 0.05 to about 3, in another embodiment from about 0.05 to about 1, and in yet another embodiment from about 0.05 to about 0.5.

[0060] The reaction is carried out in the absence of a catalyst, in the presence or absence of an amine. By "catalyst" is meant a substance that speeds up a chemical reaction but is not consumed by the reaction; therefore, at the end of the reaction, it can be recovered without chemical change. A phase transfer catalyst is a heterogeneous catalyst that promotes the transfer of reactants from one phase to the other phase in which the reaction occurs. For example, a phase transfer catalyst is a catalyst that promotes the transfer of ionic compounds, for example, from an aqueous phase to an organic phase. When water is used as the solvent, an aqueous or inorganic phase exists as a result of the alkali metal hydroxide, and an organic phase exists as a result of the fluorocarbon. The phase transfer catalyst promotes the reaction of these different components. Various phase transfer catalysts may function in different ways, but their mechanism of action does not define their usefulness in the present invention, provided that they promote the dehydrohalogenation reaction. The phase transfer catalyst may be ionic or neutral, and is typically selected from the group consisting of crown ethers, onium salts, cryptands, polyalkylene glycols, and their derivatives (e.g., their fluorinated derivatives).

[0061] Crown ethers are cyclic molecules in which ether groups are linked by dimethylene bonds. Crown ethers form molecular structures that are believed to be capable of accepting or retaining alkali metal hydroxide ions. Examples include 18-crown-6 (especially in combination with potassium hydroxide), 15-crown-5 (especially in combination with sodium hydroxide), and 12-crown-4 (especially in combination with lithium hydroxide).

[0062] Derivatives of the above crown ethers, such as dibenzyl-18-crown-6, dicyclohexanyl-18-crown-6, dibenzyl-24-crown-8 and dibenzyl-12-crown-4, are considered to be phase transfer catalysts and are excluded.Other compounds similar to crown ethers that differ by the replacement of one or more oxygen atoms with other types of donor atoms, especially N or S, are also excluded.Furthermore, fluorinated derivatives, such as compounds in which one or more hydrogen atoms are replaced by fluorine, are also excluded.

[0063] Cryptands are another class of compounds that are excluded. These are three-dimensional polymacrocyclic chelators formed by linking bridgehead structures with chains containing appropriately spaced donor atoms. The donor atoms of the bridge may all be O, N, or S, or the compound may be a mixed donor macrocycle in which the bridge chain contains a combination of such donor atoms. Cryptands that contain bicyclic molecules that are the result of linking a nitrogen bridgehead with a chain of (-OCH2CH2-) groups, as in, for example, [2.2.2] cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, available under the brand names Kryptand 222 and Kryptofix 222), are excluded.

[0064] Any kind of onium salt that is useful as a catalyst is excluded, including quaternary phosphonium salts and quaternary ammonium salts.Specific examples of such phosphonium salts and quaternary ammonium salts that are excluded include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride (commercially available under the trade names Aliquat™ 336 and Adogen™ 464), tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, tetra-n-butylammonium hydrogen sulfate, tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride and benzyltriethylammonium chloride are excluded.

[0065] Other onium salts that exhibit high temperature stability (e.g., up to about 200° C.), such as 4-dialkylaminopyridinium salts, tetraphenylarsonium chloride, bis[tris(dimethylamino)phosphine]iminium chloride, and tetrakis[tris(dimethylamino)phosphineimino]phosphonium chloride, are also excluded.

[0066] Polyalkylene glycol compounds useful as phase transfer catalysts are also excluded. For example, those of formula R 6 O(R 5 O) m R 7 Also excluded are polyalkylene glycol compounds represented by the formula: 5 is C 1-10 R is an alkylene group of the formula 6 and R 7 Each of these is independently H, C 1-10 an alkyl group, an aryl group (i.e. an aromatic group containing 6, 10, 14 ring carbon atoms, or a heteroaryl group containing 5 to 14 ring atoms and having 1 to 3 heteroatoms selected from N, O and S and the remaining ring atoms being carbon atoms, e.g., phenyl, naphthyl or pyridinyl) or an arylalkyl group (e.g., benzyl or C 1-10and m is an integer of at least 2. Also excluded are the aforementioned polyalkylene glycols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and tetramethylene glycol, monoalkyl glycol ethers, such as the monomethyl, monoethyl, monopropyl, and monobutyl ethers, of the aforementioned glycols, dialkyl ethers, such as tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether, phenyl ethers, benzyl ethers, and polyalkylene glycols, such as polyethylene glycol (average molecular weight about 300) and polyethylene glycol (average molecular weight about 400), and dialkyl (e.g., dimethyl, dipropyl, dibutyl) ethers of the aforementioned polyalkylene glycols.

[0067] Because the dehydrohalogenation reactions described herein are carried out in the liquid phase, vapor phase catalysts which catalyze the dehydrohalogenation reaction in the vapor phase are also excluded.

[0068] Dehydrohalogenation catalysts, such as dehydrochlorination catalysts, are not used in the reactions described herein, thus minimizing the cost of the reaction. This is because these catalysts are expensive. But more importantly, due to environmental concerns, these catalysts are difficult to dispose of, adding additional cost to the catalyst system. The present process is carried out in the absence of catalysts and does not include this additional cost. Furthermore, the elimination of phase transfer catalysts simplifies the dehydrohalogenation reaction by reducing the need for recycling and recovery of these catalysts from the process. Finally, since these catalysts lower the activation energy of the dehydrohalogenation reaction and are more prone to decompose the dehydrohalogenation products to form starting materials, the elimination of phase transfer catalysts in the dehydrohalogenation reaction reduces this risk.

[0069] The dehydrohalogenation reaction is carried out in an aqueous solvent with or without the presence of an amine. For example, in one embodiment, the dehydrohalogenation reaction is carried out in water. However, a co-solvent or diluent may be present to change the viscosity of the system, to act as a more favorable phase for the reaction with the product, or to increase the thermal mass. Useful co-solvents or diluents include those that do not react with the process or negatively affect the equilibrium or reaction kinetics of the process, such as alcohols such as methanol and ethanol; diols such as ethylene glycol; ethers such as diethyl ether, dibutyl ether, THF, dioxane; esters such as methyl acetate, ethyl acetate; linear, branched and cyclic alkanes such as cyclohexane, methylcyclohexane; fluorinated diluents such as hexafluoroisopropanol, perfluorotetrahydrofuran; fluorinated diluents such as hexafluoroisopropanol, perfluorotetrahydrofuran and perfluorodecalin.

[0070] The dehydrohalogenation reactions described herein, in the presence or absence of an amine, are carried out at a temperature range of about 20° C. to 100° C., and in another embodiment, from about 30° C. to about 90° C. Thus, the dehydrohalogenation reaction of the present process can be carried out at temperatures ranging from 20° C., 21° C., 22° C., 23° C., 24° C., 25° C., 26° C., 27° C., 28° C., 29° C., 30° C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39° C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48° C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C., 57° C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., 66° C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C., 75° C., 76° C., 77° C., 78° C., 79° C., 80° C , 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C.

[0071] However, when an amine is present, the reaction may be carried out at lower temperatures, i.e., the dehydrohalogenation reaction is carried out in the presence of an amine at a temperature range of from about 0° C. to about 100° C., and in another embodiment, from about 15° C. to about 90° C. Therefore, the dehydrohalogenation reaction of this process is performed at 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 8 It may be performed at 0°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, or 100°C.

[0072] The dehydrohalogenation process can be carried out at superatmospheric, atmospheric, or subatmospheric pressures with or without the presence of an amine. In one embodiment, the pressure of the dehydrohalogenation reaction is carried out at a pressure range of about -10 psig to about 150 psig, in another embodiment from about 0 psig to about 100 psig, and in yet another embodiment from about 5 psig to about 100 psig. Thus, for example, the pressure can be -10 psig, -9 psig, -8 psig, -7 psig, -6 psig, -5 psig, -4 psig, -3 psig, -2 psig, -1 psig, 0 psig, 1 psig, 2 psig, 3 psig, 4 psig, 5 psig, 6 psig, 7 psig, 8 psig, 9 psig, 10 psig, 11 psig, 12 psig, 13 psig, 14 psig, 15 psig, 16 psig, 17 psig, 18 psig, 19 psig, 20 psig, 21 psig, 22 psig, 23 psig, 24 psig, 25 psig, 26 psig, 27 psig, 28 psig, 29 psig, 30 psig, 31 psig, 32 psig, 33 psig, 34 psig, 35 psig, 36 psig, 37 psig, 38 psig, 39 psig, 40 psig, 41 psig, 42 psig, 43 psig, 44 psig, 45 psig, 46 psig, 47 8psig, 19psig, 20psig, 21psig, 22psig, 23psig, 24psig, 25psig, 26psig, 27psig, 28psig, 29psig, 30psig, 31psig, 32ps ig, 33psig, 34psig, 35psig, 36psig, 37psig, 38psig, 39psig, 40psig, 41psig, 42psig, 43psig, 44psig, 45psig, 46psig, 47psig, 48psig, 49psig, 50psig, 51psig, 52psig, 53psig, 54psig, 55psig, 56psig, 57psig, 58psig, 59psig, 60psig, 61 psig, 62psig, 63psig, 64psig, 65psig, 66psig, 67psig, 68psig, 69psig, 70psig, 71psig, 72psig, 73psig, 74psig, 75psi g, 76psig, 77psig, 78psig, 79psig, 80psig, 81psig, 82psig, 83psig, 84psig, 85psig, 86psig, 87psig, 88psig, 89psig, 9 0psig, 91psig, 92psig, 93psig, 94psig, 95psig, 96psig, 97psig, 98psig, 99psig, 100psig, 101psig, 102psig, 103psig,104psig, 105psig, 106psig, 107psig, 108psig, 109psig, 110psig, 111psig, 112psig, 113psig, 114psig, 115psig , 116psig, 117psig, 118psig, 119psig, 120psig, 121psig, 122psig, 123psig, 124psig, 125psig, 126psig, 127psig , 128 psig, 129 psig, 130 psig, 131 psig, 132 psig, 133 psig, 134 psig, 135 psig, 136 psig, 137 psig, 138 psig, 139 psig, 140 psig, 141 psig, 142 psig, 143 psig, 144 psig, 145 psig, 146 psig, 147 psig, 148 psig, 149 psig, or 150 psig. In one embodiment, the pressure may be a value between any of the psig integers listed above.

[0073] The dehydrohalogenation reaction is carried out in a reactor constructed of materials that are resistant to the corrosive effects of halide salts, such as chlorides and caustic, with or without the presence of an amine. The reactor may be optionally lined with TFE or PFA. The reactor may have a reflux column and a condenser at the top to keep the less volatile starting materials in the reactor while allowing the more volatile products to exit as vapors. In one embodiment, the reactor is a tank capable of holding liquid and includes an agitator and an integrated heating / cooling system. The agitator is a stirrer that agitates, i.e., mixes, the liquid in the reactor. The reactor further includes a controller in communication with the agitator, the controller designed to control the rotation of the agitator. The agitator in one embodiment is powered by an electric motor to control the rotation speed of the agitator to agitate, i.e., mix, the liquid. In another embodiment, the reactor has a centrally mounted drive shaft connected to a drive unit. In one embodiment, impellers are attached to the drive shaft. In one embodiment, the impellers cover about one-half to about two-thirds of the diameter of the reactor. The reactor may also use baffles, i.e., fixed impellers that break the flow caused by the rotating agitator. These may be fixed to the lid of the vessel or attached to the inside of the side wall. These vessels may be of different sizes, from less than 1 liter to over 40,000 liters. Liquids and solids are usually admitted through a connection on the top lid of the reactor. Vapors and gases are also discharged through a connection at the top. Liquids are usually discharged from the bottom or through a dip tube attached to the top.

[0074] The reactor mixes the reaction mixture consisting of RCXYCZQT and caustic, and if present, amine, by providing power to an agitator to mix the liquid in the tank. The power input is calculated based on a combination of several parameters including the shape of the vessel, the configuration of the baffles, the configuration of the impeller, if present, and the rotational speed of the impeller. This calculation can be performed by one skilled in the art. In the process described herein, in one embodiment, to maximize the yield, the caustic, RCXYCZQT, and if present, amine or ammonia are mixed together to generate small bubbles and high interphase surface area. An autoclave reactor is an example of a reactor that can achieve the horsepower per gallon of liquid defined above. In one embodiment, about 0.1 to about 50 horsepower per 1000 gallons of liquid is delivered to the agitator which agitates the reaction mixture, while in another embodiment, about 0.5 to about 40 horsepower per 1000 gallons of liquid is delivered to the agitator which agitates the reaction mixture, and in another embodiment, about 1 to about 35 horsepower per 1000 gallons of liquid is delivered to the agitator which mixes the reaction mixture.

[0075] While the examples described below use mixing provided by a mechanical agitator, the mixing power input can be provided by other methods. These methods are known in the art and include using mixing provided by gas bubbles from a gas added to the container or by vaporization of a liquid within the container. 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 stationary heads, or other devices 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 a combination of two or more methods.

[0076] The dehydrohalogenation process may be carried out in the presence of an inert gas, such as He, Ar or N2, in the presence or absence of an amine. In some embodiments of the invention, an inert gas is fed to the reactor along with the starting materials.

[0077] In one embodiment, the dehydrohalogenation process described herein is carried out in a liquid phase, aqueous solvent, in the presence or absence of an amine, using well-known chemical engineering practices, such as continuous, batch, semi-continuous processes, or combinations thereof.

[0078] Under the conditions described, and in all cases of continuous, batch or semi-continuous processes, the reaction is completed in a relatively short time after initiation. In one embodiment, a reaction time of up to about 4 hours is sufficient. For example, in one embodiment, the reaction time ranges from about 1 to about 120 minutes, while in another embodiment, the reaction time ranges from about 3 to about 60 minutes, and in another embodiment, from about 5 to about 30 minutes.

[0079] The fluoroalkane having the formula RCX=CZQ is isolated using separation techniques known in the art, such as distillation, chromatography, extraction, and the like.

[0080] The following non-limiting examples further illustrate the invention, in which 1233xf is 2-chloro-3,3,3-trifluoropropene, 1233zd is trans-1-chloro-3,3,3-trifluoropropene, 1243zf is 3,3,3-trifluoropropene, 243fa is 3,3-dichloro-1,1,1-trifluoropropene, 243db is 2,3-dichloro-1,1,1-trifluoropropane, and 233ab is 1,2,2-trichloro-3,3,3-trifluoropropane. EXAMPLES

[0081] Example 1: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 200ml shaker tube reactor at 28°C

[0082] 87.4g of 12wt% NaOH solution and 33.2g of 243db were placed in a shaker tube reactor. The reactor was shaken for 30 minutes at room temperature (28°C). The estimated mixing power was 30 to 40HP / 1000 gal. The pressure increased continuously from 1.8psig to 20.2psig as shown in Figure 1, which shows the progress of the reaction. The products were analyzed by GC-MS (Table 1), and the analysis results showed that .about.80% of the 243db was converted in 30 minutes without the use of a phase transfer catalyst. The reactants described in this example were shaken more vigorously than the reactants of Comparative Example 1, as shown by the following data, compared to the data generated in Comparative Example 1.

[0083] [Table 1]

[0084] Example 2: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 200ml shaker tube reactor at 55°C

[0085] 86g of 12wt% NaOH solution and 36.5g of 243db were placed in a shaker tube reactor. The reactor was cooled to -10°C and briefly evacuated. It was then heated to 55°C without stirring. When the temperature reached 47°C, it was shaken and heated to 55°C. It was then maintained at ~55°C for 60 minutes. The estimated mixing power was 30-40HP / 1000 gal. During the reaction, the pressure increased continuously from -6.34psig to ~47psig as shown in Figure 2, which shows the progress of the reaction. Based on the temperature and pressure profile, it was estimated that the reaction reached 98% conversion around 25 minutes. The products were analyzed by GC-MS (Table 2), and the analysis results in Table 2 indicate that ~98% of the 243db was converted.

[0086] [Table 2]

[0087] Example 3: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 200ml shaker tube reactor at 80°C

[0088] 87g of 12wt% NaOH solution and 36.1g of 243db were placed in a shaker tube reactor. The reactor was cooled to -10°C and briefly evacuated. It was then heated to 67°C without stirring. Once 67°C was reached, it was shaken and heated to 80°C. ~80°C was then maintained for 60 minutes. The estimated mixing power was 30 to 40HP / 1000 gal. During the reaction, the pressure increased continuously from 3.8psig to ~105psig as shown in Figure 3, which shows the progress of the reaction. Based on the temperature and pressure profile, it was estimated that the reaction reached 98% conversion around the 10 minute mark. The products were analyzed by GC-MS (Table 3), and the analysis results in Table 3 indicate that ~98.4% of the 243db was converted.

[0089] [Table 3]

[0090] Comparative Example 1: Dehydrochlorination at 243db with NaOH in 250ml glassware without solvent or phase transfer catalyst

[0091] A 250 ml three-neck flask was fitted with a mechanical stirrer, thermocouple and tubing leading to a bubbler. 30 g of 243db was then added to the flask and heated to 30° C. 7.2 g of 30 wt% NaOH, pre-warmed to 30° C, was then added to the 243db. After mixing at 30° C and 515 rpm for 1 hour, the mixture in the glass flask was observed to be swirling between the two liquid phases. The organic phase in the reaction vessel was analysed by GC-MS (Table 4) which indicates that 2.78% of the 243db was converted to 1233xf.

[0092] [Table 4]

[0093] Example 4: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 400ml stirred autoclave reactor at 50°C and 500 rpm

[0094] 150g of 12wt% NaOH solution was placed in a 400mL autoclave and heated to 50°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 500rpm at 50°C. The estimated mixing power was 1.2HP / 1000 gal. The pressure increased continuously from 5psig to 46psig as shown in Figure 4 which shows the progress of the reaction. After the reactor pressure stabilized, it was stirred for another 20 minutes. The products were analyzed by GC-MS (Table 5) and the analysis results show that ~99.4% of 243db was converted in 45 minutes without the use of a phase transfer catalyst.

[0095] [Table 5]

[0096] Example 5: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 400ml stirred autoclave reactor at 50°C and 1000 rpm

[0097] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 50°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 1000rpm at 50°C. The estimated mixing power was 10.1HP / 1000 gal. The pressure increased continuously from 5psig to 50psig, as shown in Figure 4, which shows the progress of the reaction. Both the temperature and pressure of the run at 1000rpm peaked sooner than at 500rpm, indicating a much faster reaction rate at 1000rpm mixing speed. After the reactor pressure stabilized, the reaction mixture was stirred for an additional 20 minutes. The products were analyzed by GC-MS (Table 6), and the analytical results indicate that ∼99.5% of 243db was converted in 30 minutes without the use of a phase transfer catalyst.

[0098] [Table 6]

[0099] Example 6: Dehydrochlorination at 243db with NaOH without phase transfer catalyst in a 400ml stirred autoclave reactor at 80°C and 500 rpm mixing speed

[0100] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 80°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 500rpm at 80°C. The estimated mixing power was 1.2HP / 1000 gal. The pressure increased continuously from 22.5psig to 100psig as shown in Figure 5 which shows the progress of the reaction. After the reactor pressure stabilized, it was stirred for another 20 minutes. The products were analyzed by GC-MS (Table 7) and the analysis results show that ~99.9% of 243db was converted in 44 minutes without the use of a phase transfer catalyst.

[0101] [Table 7]

[0102] Example 7: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 400ml stirred autoclave reactor at 80°C with mixing at 1000 rpm

[0103] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 80°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 80°C and 1000rpm. The estimated mixing power was 10.1HP / 1000gal. The pressure increased continuously from 25psig to 117psig, as shown in Figure 5, which shows the progress of the reaction. Both the temperature and pressure of the run at 1000rpm peaked sooner than at 500rpm, indicating a much faster reaction rate at 1000rpm mixing speed. After the reactor pressure stabilized, it was stirred for an additional 20 minutes. The products were analyzed by GC-MS (Table 8), and the analytical results indicate that ∼99.9% of 243db was converted in 34 minutes without the use of a phase transfer catalyst.

[0104] [Table 8]

[0105] Example 8: 243db Dehydrochlorination with NaOH without Phase Transfer Catalyst in a 400ml Stirred Autoclave Reactor at 60°C with Mixing at 500 rpm

[0106] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 60°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 60°C and 500rpm. The estimated mixing power was 1.2HP / 1000gal. The pressure increased continuously from 6psig to 62.5psig as shown in Figure 7 which shows the progress of the reaction. After the reactor pressure stabilized, it was stirred for another 20 minutes. The products were analyzed by GC-MS (Table 9) and the analysis results show that ~99.3% of 243db was converted in 35 minutes without the use of a phase transfer catalyst.

[0107] [Table 9]

[0108] Example 9: Dehydrochlorination at 243db with NaOH without phase transfer catalyst in a 400ml stirred autoclave reactor at 60°C and 1000 rpm

[0109] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 60°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 60°C and 1000rpm. The estimated mixing power was 10.1HP / 1000gal. The pressure increased continuously from 6psig to 65psig, as shown in Figures 6 and 7, which show the progress of the reaction. In the 1000rpm run, both the temperature and pressure peaked out sooner than at 500rpm, indicating a much faster reaction rate at 1000rpm mixing speed. After the reactor pressure stabilized, the reaction mixture was stirred for an additional 20 minutes. The products were analyzed by GC-MS (Table 10), and the analysis results show that ∼99.2% of 243db was converted in 30 minutes without the use of a phase transfer catalyst.

[0110] [Table 10]

[0111] Example 10: Dehydrochlorination with NaOH at 243db without phase transfer catalyst in a 400ml stirred autoclave reactor at 60°C and 1500 rpm

[0112] 150g of 12wt% NaOH solution was placed in a 400ml autoclave and heated to 60°C, then 68g of 243db was pumped in. The reaction mixture was mixed at 60°C and 1500rpm. The estimated mixing power was 34.1HP / 1000gal. The pressure increased continuously from 6psig to 72.5psig, as shown in Figures 6 and 7, which show the progress of the reaction. In the 1500rpm run, both the temperature and pressure peaked out sooner than at 1000rpm, indicating a much faster reaction rate at 1500rpm mixing speed. After the reactor pressure stabilized, the reaction mixture was stirred for an additional 20 minutes. The products were analyzed by GC-MS (Table 11), and the analysis results show that ∼99.2% of 243db was converted in 30 minutes without the use of a phase transfer catalyst.

[0113] [Table 11]

[0114] Example 11: Dehydrochlorination of 243db with NaOH using triethylamine

[0115] A 250 ml three-neck flask was fitted with a mechanical stirrer, thermocouple, and tubing leading to a bubbler. Then, 30 g of 243db and 10 g of triethylamine were added to the flask and heated to 30°C. Next, 7.2 g of 30 wt% NaOH, pre-warmed to 30°C, was added to the 243db and triethylamine mixture. It was allowed to mix for 1 hour. Analysis of the organic compounds in the reaction vessel by GC / MS showed a 27% conversion of 243db to 1233xf.

[0116] [Table 12]

[0117] Comparative Example 2: Dehydrochlorination at 243db with NaOH without the use of a solvent or phase transfer catalyst

[0118] A 250 ml three-neck flask was fitted with a mechanical stirrer, thermocouple, and tubing leading to a bubbler. 30 g of 243db was then added to the flask and heated to 30° C. 7.2 g of 30 wt% NaOH, pre-warmed to 30° C., was then added to the 243db. The contents of the flask were mixed at 515 rpm at 30° C. for 1 hour. Analysis of the organic compounds in the reaction vessel by GC / MS indicated a 2.78% conversion of 243db to 1233xf.

[0119] [Table 13]

[0120] Comparative Example 3: Dehydrochlorination at 243db with NaOH using toluene

[0121] A 250 ml three-neck flask was fitted with a mechanical stirrer, thermocouple, and tubing leading to a bubbler. 30 g of 243db and 10 g of toluene were then added to the flask and heated to 30° C. 7.2 g of 30 wt% NaOH, pre-warmed to 30° C., was then added to the 243db and toluene mixture. The contents of the flask were mixed at 515 rpm at 30° C. for 1 hour. Analysis of the organic compounds in the reaction vessel by GC / MS indicated a 0.87% conversion of 243db to 1233zf.

[0122] [Table 14]

[0123] It should be understood by those of ordinary skill in the art to which this invention pertains that any of the features described herein with respect to any particular aspect and / or embodiment of the invention may be combined with any one or more of the other features of any other aspect and / or embodiment of the invention described herein, with appropriate modifications to ensure compatibility of the combination, and such combinations are considered to be part of the invention contemplated by this disclosure.

[0124] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention as claimed. Other embodiments will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein.

Claims

1. 1. A dehydrohalogenation process comprising contacting a halofluoroalkane having the formula RCXYCZQT with a caustic in an aqueous solvent in the absence of a catalyst with stirring to produce a product comprising a fluoroolefin having the formula RCX=CZQ, wherein R is a perfluorinated alkyl group, X, Z and Q are independently H or a halogen, one of Y and T is H and the other is Cl, Br or I; The halofluoroalkane is CF 3 CHClCH 2 Cl, and the fluoroolefin is CF 3 CCl=CH 2 or The halofluoroalkane is CF 3 CCl 2 CH 3 and the fluoroolefin is CF 3 CCl=CH 2 and The caustic agent is NaOH, KOH, LiOH, CsOH, Zn(OH) 2 , Na 2 CO 3 , K 2 CO 3 , K 3 P.O. 4 , Na 3 P.O. 4 , KF or CsF; Further amines are present, the molar ratio of the amine to the caustic ranges from 0.02 to 3; Dehydrohalogenation process.

2. 2. The dehydrohalogenation process of claim 1, wherein the temperature ranges from 20° C. to 100° C.

3. 2. The dehydrohalogenation process of claim 1, wherein the molar ratio of said caustic to said halofluoroalkane ranges from 0.01 to 5.

4. 4. The dehydrohalogenation process of claim 3, wherein said molar ratio is from 0.02 to 4.

5. 5. The dehydrohalogenation process of claim 4, wherein said molar ratio is from 0.04 to 2.

6. 6. The dehydrohalogenation process of claim 5, wherein said molar ratio is from 0.05 to 1.

5.

7. 2. The dehydrohalogenation process of claim 1 , wherein the aqueous solvent is water.

8. 2. The dehydrohalogenation process of claim 1, wherein the amine has the formula NR1R2R3, where R1, R2 and R3 are independently hydrogen, an alkyl group, an aryl, an arylalkyl group, a heterocycle, a heterocyclic alkyl, or the formula N(R4)(R5)N(R6)(R7), where R4, R5, R6 and R7 are independently hydrogen, an alkyl group, an aryl, an arylalkyl group, a heterocycle, or a heterocyclic alkyl.

9. 2. The dehydrohalogenation process of claim 1, wherein the molar ratio of said amine to said halofluoroalkane ranges from 0.02 to 3.

10. 2. The dehydrohalogenation process of claim 1, wherein the molar ratio of said caustic to said halofluoroalkane ranges from 0.01 to 5.

11. 11. The dehydrohalogenation process of claim 10, wherein the molar ratio of the amine to the halofluoroalkane is in the range of 0.02 to 3, the molar ratio of the amine to the caustic is in the range of 0.02 to 3, and the molar ratio of the caustic to the halofluoroalkane is in the range of 0.01 to 5.

12. 2. The dehydrohalogenation process of claim 1, wherein the amine is triethylamine.

13. 10. The dehydrohalogenation process of claim 1 carried out at a pressure of from -10 psig to 150 psig.

14. 2. The dehydrohalogenation process of claim 1 , wherein the aqueous solvent is water.

15. 10. The dehydrohalogenation process of claim 1, wherein the agitation is performed with a mixing power in the range of 0.1 to 50 horsepower / 1000 gallons of liquid.

16. 16. The dehydrohalogenation process of claim 15, wherein the agitation is performed with a mixing power in the range of 0.5 to 40 horsepower / 1000 gallons of liquid.

17. 17. The dehydrohalogenation process of claim 16, wherein the agitation is performed with a mixing power in the range of 1 to 35 horsepower / 1000 gallons of liquid.

18. 10. The dehydrochlorination process of claim 1 carried out at a pressure in the range of 0 psig to 100 psig.

19. 20. The dehydrochlorination process of claim 18 carried out at a pressure in the range of from 5 psig to 100 psig.

20. 2. The dehydrochlorination process of claim 1, wherein said dehydrohalogenation process converts at least 79.7% of said halofluoroalkane to said fluoroolefin.

21. The dehydrochlorination process of any one of claims 1 to 20, further comprising a step of converting the fluoroolefins produced to 2,3,3,3-tetrafluoropropene.

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