WO2023171325A1 - Procédé de fabrication d'alcène - Google Patents

Procédé de fabrication d'alcène Download PDF

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WO2023171325A1
WO2023171325A1 PCT/JP2023/005792 JP2023005792W WO2023171325A1 WO 2023171325 A1 WO2023171325 A1 WO 2023171325A1 JP 2023005792 W JP2023005792 W JP 2023005792W WO 2023171325 A1 WO2023171325 A1 WO 2023171325A1
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halogen atom
producing
ether
atom
alkene
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PCT/JP2023/005792
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Japanese (ja)
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賢輔 鈴木
康寛 近藤
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株式会社クレハ
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

Definitions

  • the present invention relates to a method for producing alkenes.
  • Patent Document 1 As a method for producing halogenated alkenes, a method is known in which an alkali is used in the elimination reaction of hydrogen halide from a halogenated alkane substituted with a plurality of halogen atoms.
  • Patent Document 1 R A method for producing alkenes in high yield by carrying out a de-HCl reaction of -142b is disclosed.
  • Patent Document 2 discloses a method for producing vinylidene fluoride using DMSO as a solvent.
  • Patent No. 6974221 German Patent Invention No. 01959343
  • Patent Document 1 has a problem in that the alkali metal salt as a by-product salt dissolves in the aqueous solution and accumulates, making it difficult for the inorganic alkali to dissolve in the aqueous solution, making it difficult for the reaction to proceed. .
  • the manufacturing method disclosed in Patent Document 2 it is desired to recover and recycle the solvent from the viewpoint of manufacturing costs, but since DMSO decomposes at a temperature near its boiling point, it is difficult to recover it by distillation. Further, according to studies by the present inventors, the conversion rate of the halogenated alkane, which is a raw material, is not sufficient in the conventional method for producing alkenes.
  • the present invention was made in order to solve the above problems, and its purpose is to achieve a high conversion rate of the halogenated alkane as a raw material, a small decrease in the production rate over time, and an easy to recover and recycle.
  • An object of the present invention is to provide a method for producing alkenes using a simple solvent.
  • the present inventors made an onium salt and a cation scavenger coexist in a single-phase solution containing a nonpolar solvent and a specific alkali metal hydroxide, and brought such a solution into contact with a halogenated alkane.
  • the inventors have discovered that the above-mentioned problems can be solved by producing alkenes in this manner, and have completed the present invention.
  • the method for producing an alkene according to the present invention comprises a non-polar solvent, at least one alkali metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and an onium salt. , a cation scavenger, and a one-phase solution is brought into contact with a halogenated alkane represented by general formula (1) that is soluble in a nonpolar solvent.
  • R1 and R2 are different from each other and represent a halogen atom or a hydrogen atom
  • R3 is a hydrogen atom, a halogen atom of the same type as R1 or R2, or a carbon atom whose bond dissociation energy is
  • R4 represents a halogen atom larger than the halogen atom represented by R1 or R2
  • R4 is a hydrogen atom, a halogen atom of the same type as R1 or R2, or a halogen atom with a bond dissociation energy between it and a carbon atom that is larger than the halogen atom represented by R1 or R2.
  • the onium salt is preferably a quaternary ammonium salt.
  • the quaternary ammonium salt is preferably at least one selected from the group consisting of quaternary ammonium chloride and quaternary ammonium bromide.
  • the non-polar solvent is preferably an aromatic hydrocarbon-based non-polar solvent.
  • the aromatic hydrocarbon nonpolar solvent is preferably at least one selected from the group consisting of toluene, isopropylbenzene, and o-dichlorobenzene.
  • the cation scavenger is preferably at least one selected from the group consisting of crown ethers, polyalkylene glycols, and derivatives thereof.
  • the halogenated alkane is preferably a compound in which R1 or R2 represents a chlorine atom in the general formula (1).
  • the halogenated alkane is preferably 1,1-difluoro-1-chloroethane, and the contacting step is preferably a step of producing 1,1-difluoroethylene.
  • the present inventors made an onium salt and a cation scavenger coexist in a single-phase solution containing a nonpolar solvent and a specific alkali metal hydroxide, and brought such a solution into contact with a halogenated alkane. It has been found that the alkali metal hydroxide and the halogenated alkane can be efficiently reacted by doing so. This method does not require the use of water as a co-solvent. That is, salts (alkali metal salts or alkaline earth metal salts) produced as by-products by the reaction between the alkali metal hydroxide and the halogenated alkane are difficult to dissolve in the solution.
  • a one-phase solution contains a nonpolar solvent and at least one kind selected from the group consisting of an alkali metal hydroxide and an alkaline earth metal hydroxide. It includes an alkali metal hydroxide, an onium salt, and a cation scavenger.
  • the halogenated alkane is contained within the gas phase. For example, by bringing a gas phase containing a halogenated alkane into contact with the solution (liquid phase), the halogenated alkane is dissolved in the solution, and the alkali metal hydroxide and the halogenated alkane react, Alkenes are produced.
  • the nonpolar solvent is one that can sufficiently dissolve the halogenated alkane, and at least one alkali metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
  • alkali metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
  • the nonpolar solvents may be used alone or in combination of two or more. Examples of the nonpolar solvent include ether nonpolar solvents, aliphatic hydrocarbon nonpolar solvents, and aromatic hydrocarbon nonpolar solvents. Among these, aromatic hydrocarbon-based nonpolar solvents are preferred from the viewpoint of alkene production efficiency.
  • ether type nonpolar solvent examples include diethyl ether, dipropyl ether, methylpropyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl-sec-butyl ether, methyl-tert-butyl ether, methylpentyl ether, and methyl isopropyl ether.
  • aliphatic hydrocarbon nonpolar solvents examples include pentane, hexane, heptane, octane, nonane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, cyclohexane, and methyl.
  • Cyclohexane 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, propylcyclohexane, butylcyclohexane, Examples include decalin and paraffins.
  • aromatic hydrocarbon nonpolar solvents examples include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, isopropylbenzene, and 1,2,3-trimethyl.
  • paraffins As the nonpolar solvent, paraffins, toluene, isopropylbenzene, and o-dichlorobenzene are preferred, and toluene is more preferred, from the viewpoint of alkene production efficiency.
  • the one-phase solution may contain a solvent other than the non-polar solvent.
  • the solvent other than the non-polar solvent is not particularly limited as long as it is compatible with the non-polar solvent and does not inhibit the dissolution of the alkali metal hydroxide, onium salt, and cation trapping agent.
  • the solvent is a solvent that can be uniformly mixed with the above-mentioned nonpolar solvent.
  • solvents other than non-polar solvents include alcohol.
  • the alcohol may be a monohydric alcohol or a dihydric or higher alcohol.
  • Solvents other than non-polar solvents may be used alone or in combination of two or more.
  • monohydric alcohols examples include saturated aliphatic hydrocarbon alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butyl alcohol, and n-pentyl alcohol; saturated alcohols such as cyclopentanol and cyclohexanol; Alicyclic hydrocarbon alcohols include unsaturated aliphatic hydrocarbon alcohols such as allyl alcohol and 2-propyn-1-ol. Among these, saturated aliphatic hydrocarbon alcohols are preferred from the viewpoint of alkene production efficiency, and saturated aliphatic hydrocarbon alcohols having a branched chain are particularly preferred. When a monohydric alcohol has a branched chain, the molecular structure becomes bulky and the production of by-products is easily suppressed.
  • dihydric or higher alcohols examples include glycols such as ethylene glycol, trimethylene glycol, propylene glycol, and tetramethylene glycol; and triols such as glycerin and 1,2,4-butanetriol.
  • the content of solvents other than the non-polar solvents is preferably 99% by volume or less, more preferably 50% by volume or less, and even more preferably 25% by volume or less, when the content of all solvents is 100% by volume.
  • amount of the solvent other than the above-mentioned non-polar solvent is within this range, it is easier to produce the alkene more efficiently.
  • the alkali metal hydroxide contained in the one-phase solution is at least one selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.
  • the alkali metal hydroxides may be used alone or in combination of two or more.
  • Examples of the alkali metal hydroxide include potassium hydroxide (KOH), sodium hydroxide (NaOH), and lithium hydroxide (LiOH).
  • Examples of the alkaline earth metal hydroxide include magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), and the like.
  • potassium hydroxide (KOH) and sodium hydroxide (NaOH) are preferred from the viewpoint of reactivity with halogenated alkanes.
  • the content of the alkali metal hydroxide is appropriately selected depending on the type of the alkali metal hydroxide. From the viewpoint of increasing the production efficiency of alkenes and making it difficult to cause deterioration of the reaction vessel, piping, etc., the content of the alkali metal hydroxide in the solution is determined by controlling the content of halogenated alkanes (for example, the general formula ( It is preferably 0.5 to 5 mol, more preferably 0.5 to 2.5 mol, and even more preferably 1 to 2 mol, per 1 mol of the compound represented by 1).
  • the one-phase solution includes an onium salt and a cation scavenger.
  • the alkali metal hydroxide is promoted to dissolve in the nonpolar solvent, and the desired reaction is likely to occur in the solution.
  • onium salts include quaternary phosphonium salts and quaternary ammonium salts.
  • Onium salts may be used alone or in combination of two or more.
  • the quaternary phosphonium salt include tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, bis[tris(dimethylamino)phosphine]
  • Examples include iminium chloride, tetratris[tris(dimethylamino)phosphinimino]phosphonium chloride, and the like.
  • quaternary ammonium salts examples include quaternary ammonium chloride, quaternary ammonium bromide, etc. Specific examples include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, and methyltrioctyl.
  • Examples include ammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and tetrabutylammonium hydrogen sulfate.
  • Examples of other onium salts include 4-dialkylaminopyridinium salts and tetraphenylarsonium chloride.
  • the content of onium salt in the solution (liquid phase) is set to 0.
  • the amount is preferably from 0.01 to 5 mol, more preferably from 0.02 to 1 mol, and even more preferably from 0.05 to 0.5 mol.
  • the cation scavenger may be any known cation scavenger, such as crown ether, cryptate, polyalkylene glycol, and derivatives thereof.From the viewpoint of production efficiency of alkenes, crown ether, polyalkylene glycol, and at least one selected from the group consisting of derivatives thereof.
  • the cation scavengers may be used alone or in combination of two or more.
  • crown ether examples include 18-crown 6-ether, 15-crown 5-ether, and 12-crown 4-ether.
  • examples of crown ether derivatives include dibenzo-18-crown 6-ether, dicyclohexano-18-crown 6-ether, dibenzo-24-crown 8-ether, and the like.
  • polyalkylene glycols examples include glycols.
  • polyalkylene glycol derivatives include alkyl ether compounds of the above-mentioned glycols.
  • the glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, tetramethylene glycol, and the like. .
  • alkyl ether compounds of the above glycols include monoalkyl ethers of the above glycols (e.g., monomethyl ether compound, monoethyl ether compound, monopropyl ether compound, monobutyl ether compound, etc.), dialkyl ethers of the above glycols, etc.
  • tetraethylene glycol dimethyl ether tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, etc.
  • phenyl ethers of the above glycols phenyl ethers of the above glycols
  • benzyl ethers of the above glycols dialkyl ethers of polyalkylene glycols (specifically, polyethylene glycol dimethyl ether, etc.) (average molecular weight: about 240), polyethylene glycol dimethyl ether (average molecular weight: about 300), polyethylene glycol dibutyl ether (average molecular weight: about 300), polyethylene glycol dimethyl ether (average molecular weight: about 400), etc.
  • Cryptates are three-dimensional polymacrocyclic chelators formed by linking bridgehead structures with chains containing appropriately spaced donor atoms.
  • Examples of cryptates include nitrogen bridgeheads (-OCH Examples include bicyclic molecules obtained by bonding with 2 CH 2 -) chains.
  • the content of the cation scavenger in the solution (liquid phase) is determined based on 1 mole of halogenated alkane (for example, a compound represented by general formula (1) described below).
  • the amount is preferably 0.01 to 5 mol, more preferably 0.02 to 1 mol, and even more preferably 0.05 to 0.5 mol.
  • the solution does not substantially contain water.
  • substantially free of water means that the amount of water in the solution is 1% by mass or less.
  • the gas phase during alkene production contains a halogenated alkane as a raw material, and after the reaction has proceeded, it further contains an alkene as a reaction product.
  • the halogenated alkane is a halogenated alkane represented by general formula (1) that is soluble in a nonpolar solvent.
  • R1 and R2 are different from each other and represent a halogen atom or a hydrogen atom
  • R3 is a hydrogen atom, a halogen atom of the same type as R1 or R2, or a carbon atom whose bond dissociation energy is
  • R4 represents a halogen atom larger than the halogen atom represented by R1 or R2
  • R4 is a hydrogen atom, a halogen atom of the same type as R1 or R2, or a halogen atom with a bond dissociation energy between it and a carbon atom that is larger than the halogen atom represented by R1 or R2.
  • the above-mentioned halogenated alkane is a molecule that has at least one halogen atom and at least three hydrogen atoms in the molecule and becomes a gas at room temperature.
  • the halogenated alkane comes into contact with the alkali metal hydroxide in the liquid phase, the halogen atom is eliminated as hydrogen halide together with the hydrogen bonded to the adjacent carbon atom, thereby producing an alkene.
  • the halogenated alkane may be a molecule that has at least two halogen atoms and at least three hydrogen atoms in the molecule and becomes a gas at room temperature.
  • a halogenated alkane comes into contact with the alkali metal hydroxide in the liquid phase, one of the at least two halogen atoms (the one with a small bond dissociation energy with a carbon atom) is separated from its neighbor. It is eliminated as a hydrogen halide along with the hydrogen bonded to the matching carbon atom, producing a halogenated alkene.
  • halogen atom contained in the halogenated alkane examples include a fluorine (F) atom, a chlorine (Cl) atom, a bromine (Br) atom, and an iodine (I) atom.
  • halogenated alkanes include fluoroethane, 1,1-difluoroethane, 1,2-difluoroethane, 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1,1, 2-tetrafluoroethane, chloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1 -dichloro-1-fluoroethane, 1,1-difluoro-1-chloroethane, 1,1-difluoro-2-chloroethane, 1,3-dichloropropane, 1,1,3-trichloro-1-fluoropropane, 1, 1,1,3,3-pentafluoropropane, 1,1,1-trifluoro-3,3-dichloroprop, 1,
  • 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, 1,1-difluoro-1-chloroethane, and 1,1-difluoro-2-chloroethane are preferred.
  • R3 is the same as R3 in general formula (1) and represents a hydrogen atom or a halogen atom
  • R4 is the same as R4 in general formula (1) and is a hydrogen atom or a halogen atom. , or an alkyl group having 1 or more and 3 or less carbon atoms which may be substituted with any halogen atom.
  • the halogen atom substituting the alkyl group may be the same type of halogen atom, or may be a different type of halogen atom.
  • R4 when R4 is an alkyl group having 1 to 3 carbon atoms substituted with any halogen atom, the alkyl group may be substituted with a plurality of halogen atoms. , all hydrogen atoms may be substituted with halogen atoms. At this time, the plurality of halogen atoms to be substituted may all be of the same type, or may be a combination of a plurality of halogen atoms of different types.
  • R1 or R2 is preferably a fluorine (F) atom, a chlorine (Cl) atom, or a bromine (Br) atom, and is preferably a chlorine (Cl) atom or a bromine (Br) atom. is more preferable, and even more preferably a chlorine (Cl) atom.
  • R3 or R4 is a fluorine (F) atom, and R3 and R4 are More preferably, both are fluorine (F) atoms.
  • the halogenated alkane may be 1,1-difluoro-1-chloroethane, and the halogenated alkene that is the reaction product in this case may be 1,1-difluoroethylene (i.e., vinylidene fluoride).
  • 1,1-difluoroethylene i.e., vinylidene fluoride
  • the content of the halogenated alkane in the reaction system is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the total solvent content, from the viewpoint of alkene production efficiency. , 10 to 25 parts by mass is more preferable.
  • the gas phase may contain an inert gas such as nitrogen (N 2 ) gas and argon (Ar) gas, but from the viewpoint of further increasing the reaction efficiency, substantially the above halogenated alkane and reaction product It is preferable to include only “Substantially” means that the total amount of the halogenated alkane and reaction product is greater than or equal to 99% by volume of the gas phase.
  • an inert gas such as nitrogen (N 2 ) gas and argon (Ar) gas
  • the method for producing an alkene described above may include a step of bringing the liquid phase and the gas phase into contact.
  • the above-described method for producing an alkene may further include a step of separating and recovering the alkene, which is a reaction product, from the liquid phase and gas phase after the contact.
  • the above separation and recovery can be performed by known methods.
  • the above-mentioned method for producing an alkene includes, for example, charging the above-mentioned non-polar solvent, an alkali metal hydroxide, an onium salt, a cation scavenger, and other solvents as necessary into a reaction vessel having sufficient capacity. This can be carried out by preparing a one-phase solution (liquid phase), and then introducing the gaseous halogenated alkane into the reaction vessel. Note that the treatment may be performed in a batch manner or in a continuous manner.
  • Preparation of the liquid phase may be carried out within the reaction vessel by introducing a nonpolar solvent, an alkali metal hydroxide, an onium salt, and a cation scavenger into the reaction vessel, or it may be carried out before the reaction vessel is charged. .
  • the order of adding or mixing these ingredients is not particularly limited.
  • an inert gas may be introduced into the reaction vessel.
  • reaction temperature can be, for example, 20°C or higher and lower than 200°C, preferably 20°C or higher and 140°C or lower, more preferably 40°C or higher and 100°C or lower, and 40°C or higher and 80°C or higher. C. or less is more preferable.
  • the pressure inside the reaction vessel after the introduction of the halogenated alkane may be at least atmospheric pressure and at most 5.0 MPa.G, but preferably at least atmospheric pressure and at most 2.0 MPa.G. It is more preferably .0 MPa.G or less, even more preferably 0.1 MPa.G or more and 0.7 MPa.G or less, and particularly preferably 0.1 MPa.G or more and 0.5 MPa.G or less.
  • reaction time after the introduction of the halogenated alkane changes depending on the reaction conditions, but may be about 0.1 hour or more and 8 hours or less.
  • the liquid phase may be recovered and reused as is for the next reaction, or a step of recovering a solvent such as a nonpolar solvent from the liquid phase may be further performed.
  • the recovery method is not particularly limited, and may be, for example, a distillation method.
  • reaction vessel a pressure-resistant reaction vessel containing a stirring bar
  • reaction vessel a stirring bar
  • 6.8 mL of toluene, 0.7146 g of KOH, 0.2923 g of 18-crown 6-ether, and 0.3530 g of tetra Butylammonium bromide (hereinafter also referred to as "TBAB”) was added and mixed uniformly.
  • TBAB tetra Butylammonium bromide
  • R-142b 1,1-difluoro-1-chloroethane
  • Example 2 (synthesis) In the aforementioned reaction vessel, 5.8 mL of toluene, 1.0 mL of t-butyl alcohol (hereinafter also referred to as "t-BuOH"), 0.7133 g of KOH, 0.2947 g of 18-crown 6-ether, 0.3529g of TBAB was added and mixed uniformly. After the reaction container was completely sealed and the pressure inside the reaction container was reduced using a vacuum pump, 1.1 g of R-142b was charged. The contents were heated to 40°C while stirring. After confirming that the internal temperature had reached 40°C, that temperature was maintained for 0.5 hour. The internal pressure of the reaction vessel while maintaining the above temperature was 0.12 to 0.24 MPa ⁇ G. Heating was stopped after 0.5 hours, and a gas phase sample was collected into a gas collection bag while the internal temperature was 40°C.
  • t-BuOH t-butyl alcohol
  • Example 3 (synthesis) 6.8 mL of toluene, 0.4407 g of NaOH, 0.2488 g of 15-crown 5-ether, and 0.3532 g of TBAB were charged into the reaction vessel and uniformly mixed. After the reaction container was completely sealed and the pressure inside the reaction container was reduced using a vacuum pump, 1.1 g of R-142b was charged. The contents were heated to 80°C while stirring. After confirming that the internal temperature had reached 80°C, that temperature was maintained for 3 hours. The internal pressure of the reaction vessel while maintaining the above temperature was 0.35 to 0.44 MPa ⁇ G. Heating was stopped after 3 hours, and after cooling to an internal temperature of 40° C., a gas phase sample was collected in a gas collection bag.
  • Example 4 (synthesis) Into the reaction vessel described above, 5.8 mL of toluene, 1.0 mL of t-BuOH, 0.4411 g of NaOH, 0.2604 g of polyethylene glycol dimethyl ether (average molecular weight approximately 240), and 0.3531 g of TBAB were charged. mixed in a similar manner. After the reaction container was completely sealed and the pressure inside the reaction container was reduced using a vacuum pump, 1.1 g of R-142b was charged. The contents were heated to 40°C while stirring. After confirming that the internal temperature had reached 40°C, that temperature was maintained for 0.5 hour. The internal pressure of the reaction vessel while maintaining the above temperature was 0.12 to 0.20 MPa ⁇ G. Heating was stopped after 0.5 hours, and a gas phase sample was collected into a gas collection bag while the internal temperature was 40°C.
  • Amount of water in solvent The amount of water in the solvent used in the Examples or Comparative Examples was measured using a Karl Fischer moisture meter (manufactured by Mitsubishi Chemical Analytech). Specifically, about 1 mL of the solvent used in the Examples or Comparative Examples was weighed out with a syringe, introduced directly into the electrolytic cell of the measuring device, and the amount of water in the solvent was determined by coulometric titration. The results are as follows. Amount of water in solvent 1: 77 ppm Amount of water in solvent 2: 198 ppm (Solvent composition) Solvent 1: 6.8 mL toluene Solvent 2: Combination of 5.8 mL toluene and 1.0 mL t-BuOH
  • a non-polar solvent at least one alkali metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, an onium salt, and a cation.
  • the conversion rate of R-142b showed a high value of 50% or more (Examples 1 to 4). It can be said that the combined use of an onium salt and a cation scavenger promoted the dissolution of the alkali metal hydroxide in the nonpolar solvent, and that the desired reaction occurred in the solution.

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Abstract

L'invention fournit un procédé de fabrication d'alcène qui présente un rapport de conversion élevé d'alcane halogéné constituant une matière de départ, dans lequel la chute de vitesse de production au cours du temps est faible, et qui met en œuvre un solvant facile à récupérer et à recycler.　Le procédé de fabrication d'alcène de l'invention inclut une étape au cours de laquelle sont mis en contact d'une part une solution monophasique qui contient un solvant non polaire, un hydroxyde métallique à base d'alcalis constitué d'au moins un élément parmi un hydroxyde de métal alcalin et un hydroxyde de métal alcalinoterreux, un sel d'onium et un piégeur de cations, et d'autre part un alcane halogéné représenté par la formule (1) soluble dans un solvant non polaire. Dans la formule (1), Ｒ１ et Ｒ２ sont différents l'un de l'autre, et représentent un atome d'halogène et un atome d'hydrogène, R3 représente un atome d'hydrogène, un atome d'halogène de même type que celui de R1 ou R2, ou un atome d'halogène présentant une énergie de dissociation de liaison vis-à-vis d'un atome de carbone supérieure à celle de l'atome d'halogène représenté par R1 ou R2, et R4 est identique à R3, ou représente un groupe alkyle de 1 à 3 atomes de carbone pouvant être substitué par un atome d'halogène arbitraire.
PCT/JP2023/005792 2022-03-09 2023-02-17 Procédé de fabrication d'alcène WO2023171325A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012233001A (ja) * 2001-09-25 2012-11-29 Honeywell Internatl Inc フルオロオレフィンの製造方法
JP2013018723A (ja) * 2011-07-08 2013-01-31 Central Glass Co Ltd １−クロロ−３，３，３−トリフルオロプロピンの製造方法
WO2019176151A1 (fr) * 2018-03-14 2019-09-19 株式会社クレハ Procédé de production d'alcène
JP2020023587A (ja) * 2015-07-27 2020-02-13 Ａｇｃ株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
WO2021131143A1 (fr) * 2019-12-27 2021-07-01 株式会社クレハ Procédé de fabrication d'alcène

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012233001A (ja) * 2001-09-25 2012-11-29 Honeywell Internatl Inc フルオロオレフィンの製造方法
JP2013018723A (ja) * 2011-07-08 2013-01-31 Central Glass Co Ltd １−クロロ−３，３，３−トリフルオロプロピンの製造方法
JP2020023587A (ja) * 2015-07-27 2020-02-13 Ａｇｃ株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
WO2019176151A1 (fr) * 2018-03-14 2019-09-19 株式会社クレハ Procédé de production d'alcène
WO2021131143A1 (fr) * 2019-12-27 2021-07-01 株式会社クレハ Procédé de fabrication d'alcène

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