Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
  • B01J31/0235—Nitrogen containing compounds
  • B01J31/0239—Quaternary ammonium compounds
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
  • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
  • B01J2531/98—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases
  • B01J2531/985—Phase-transfer catalysis in a mixed solvent system containing at least 2 immiscible solvents or solvent phases in a water / organic solvent system
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • 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 an alkene.
• Patent Document 1 and Patent Document 2 describe a method in which a gaseous halogenated alkane is brought into contact with a catalyst under a high-temperature and high-pressure condition of 200 ° C. or higher to cause the elimination reaction of the hydrogen halide. Has been.
• the present invention has been made in view of the above problems.
• a method for producing an alkene by contacting a gaseous halogenated alkane with an alkaline aqueous solution in the presence of a phase transfer catalyst, the collection of the alkene as a reaction product is achieved. It is an object of the present invention to provide a method for producing an alkene capable of further improving the rate.
• the method for producing an alkene according to the present invention for solving the above-described problem includes a liquid phase containing an alkaline aqueous solution and a water-insoluble solvent, and a gas phase containing a halogenated alkane that is soluble in the water-insoluble solvent. Contacting in the presence of a moving catalyst.
• the yield of the alkene as a reaction product can be further improved.
• a method for producing an alkene is provided.
• the liquid phase is in a state where the alkaline aqueous solution and the water-insoluble solvent are separated, or in the state where the other liquid is dispersed in one liquid of the alkaline and water-insoluble solvents.
• the gas phase is brought into contact with such a liquid phase, the halogenated alkane is dissolved in a non-water-soluble solvent, and thus the reaction efficiency is further increased, so that the yield of the alkene as a reaction product is further improved. it is conceivable that.
• the liquid phase includes the alkaline aqueous solution and the non-aqueous solvent, and further includes a phase transfer catalyst.
• the alkaline aqueous solution may be an aqueous solution obtained by dissolving an alkaline compound such as an oxide or hydroxide of an alkali metal atom or alkaline earth metal atom in water as a solvent.
• alkaline compound include potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ). And calcium oxide (CaO).
• potassium hydroxide (KOH) and sodium hydroxide (NaOH) are preferred, and sodium hydroxide (NaOH) is more preferred.
• the content of the alkaline compound in the alkaline aqueous solution is 1% by mass with respect to the total mass of the alkaline aqueous solution. It is preferably 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and further preferably 30% by mass or more and 50% by mass or less.
• the content of the alkaline compound can be arbitrarily determined according to the type of halogenated alkane causing the elimination reaction of hydrogen halide.
• the phase transfer catalyst acts between the alkaline compound contained in the alkaline aqueous solution and a halogenated alkane that is hardly soluble in the alkaline aqueous solution, and an anion derived from the alkaline compound (for example, OH ⁇ ion).
• an anion derived from the alkaline compound for example, OH ⁇ ion.
• the phase transfer catalyst promotes the transfer of the anion acting as the base into the water-insoluble solvent. Therefore, in the present invention, the halogenated alkane dissolved from the gas phase and the anion acting as the base whose movement is promoted by the phase transfer catalyst are present in a high concentration in the water-insoluble solvent. Therefore, it is considered that the elimination reaction of hydrogen halide from the halogenated alkane proceeds more efficiently.
• the phase transfer catalyst may be a known phase transfer catalyst, for example, crown ether, onium salt, cryptate, polyalkylene glycol, and derivatives thereof.
• Examples of the crown ether include 18-crown-6, 15-crown-5 and 12-crown-4.
• Examples of the crown ether derivatives include dibenzo-18-crown-6, dicyclohexano-18-crown-6, and dibenzo-24-crown-8.
• Examples of the onium salt include quaternary phosphonium salts and quaternary ammonium salts.
• Examples of the quaternary phosphonium salts include tetra-n-butylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, triphenylmethylphosphonium bromide, triphenylmethylphosphonium chloride, bis [tris (dimethylamino) phosphine]. Examples include iminium chloride and tetratris [tris (dimethylamino) phosphinimino] phosphonium chloride.
• Examples of the quaternary ammonium salts include tetramethylammonium chloride, tetramethylammonium bromide, benzyltriethylammonium chloride, methyltrioctylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetradecyltrimethylammonium bromide, tetradecyl Examples include trimethylammonium chloride, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, and tetrabutylammonium hydrogensulfate.
• Examples of other onium salts include 4-dialkylaminopyridinium salts and tetraphenylarsonium chloride.
• polyalkylene glycol compound examples include glycols and alkyl ether compounds of the glycols.
• glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, diisopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, and tetramethylene glycol. It is.
• alkyl ether compounds of the glycols include monoalkyl ethers of these glycols (for example, monomethyl ether compounds, monoethyl ether compounds, monopropyl ether compounds, and monobutyl ether compounds), dialkyl ethers (specific examples) Specifically, tetraethylene glycol dimethyl ether and pentaethylene glycol dimethyl ether), phenyl ethers, benzyl ethers, and polyalkylene glycols (specifically, polyethylene glycol (average molecular weight: about 300) dimethyl ether, polyethylene glycol ( Average molecular weight: about 300) dibutyl ether, polyethylene glycol (average molecular weight: about 400) dimethyl ether, and the like.
• monoalkyl ethers of these glycols for example, monomethyl ether compounds, monoethyl ether compounds, monopropyl ether compounds, and monobutyl ether compounds
• dialkyl ethers specifically, tetraethylene glycol dimethyl
• the cryptate is a three-dimensional polymacrocyclic chelator formed by joining bridgehead structures with chains containing appropriately spaced donor atoms.
• Examples of the cryptate include nitrogen bridge heads such as 2.2.2 cryptate-4,7,13,16,21,24-hexaoxa-1,10-diasabicyclo [8.8.8] hexacosane (- Bicyclic molecules obtained by bonding with OCH 2 CH 2 —) chains are included.
• the content of the phase transfer catalyst in the reaction system is preferably 0.01% by mass or more and 3% by mass or less, and 0.05% by mass or more with respect to the total mass of the alkaline compound contained in the alkaline aqueous solution. It is more preferably 1% by mass or less, and further preferably 0.1% by mass or more and 0.5% by mass or less.
• the water-insoluble solvent is an organic solvent that is incompatible with the alkaline aqueous solution and forms a phase different from the alkaline aqueous solution in the liquid phase, and is capable of sufficiently dissolving the halogenated alkane. That's fine.
• the water-insoluble solvent means an organic solvent having a water solubility of 10% or less. Examples of these water-insoluble solvents include alcohol-based water-insoluble solvents, ether-based water-insoluble solvents, aliphatic hydrocarbon-based water-insoluble solvents, and aromatic hydrocarbon-based water-insoluble solvents. included. Of these, ether-based water-insoluble solvents, aliphatic hydrocarbon-based water-insoluble solvents, and aromatic hydrocarbon-based water-insoluble solvents are preferable, and aromatic hydrocarbon-based water-insoluble solvents are more preferable.
• alcohol-based water-insoluble solvent examples include octanol and the like.
• ether-based water-insoluble solvents examples include diethyl ether, dipropyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl-sec-butyl ether, methyl tert-butyl ether, methyl pentyl ether.
• Examples of the aliphatic hydrocarbon-based water-insoluble solvents include pentane, hexane, heptane, octane, nonane, decane, dodecane, undecane, tridecane, decalin, 2,2,4,6,6-pentamethylheptane, Cyclohexane, methylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, ethylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, propylcyclohexane, Examples include butylcyclohexane, decalin, and paraffins.
• aromatic hydrocarbon-based water-insoluble solvents examples include benzene, toluene, o-xylene, m-xylene, p-xylene, ethylbenzene, trimethylbenzene, ethyltoluene, propylbenzene, isopropylbenzene, 1, 2, 3-trimethylbenzene, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 2-ethyltoluene, 3-ethyltoluene, 4-ethyltoluene, cymene, chlorobenzene, o-dichlorobenzene, m-di Examples include chlorobenzene, p-dichlorobenzene, tetralin, and anisole.
• the water-insoluble solvent may be vegetable oil such as soybean oil, sesame oil, olive oil, and cottonseed oil.
• water-insoluble solvents are preferably paraffins, toluene, isopropylbenzene and o-dichlorobenzene, more preferably toluene, isopropylbenzene and o-dichlorobenzene, and even more preferably o-dichlorobenzene.
• the content of the water-insoluble solvent in the reaction system is preferably 0.01 to 10 times, and preferably 0.1 to 5 times the total mass of the halogenated alkane. More preferably, it is 0.5 times or more and 2 times or less.
• the water-insoluble solvent is preferably a solvent having a specific gravity lower than that of the alkaline aqueous solution from the viewpoint of facilitating contact with the gas phase.
• a solvent having a specific gravity heavier than that of the alkaline aqueous solution may be used.
• the gas phase contains the halogenated alkane and, after the reaction proceeds, further contains an alkene that is a reaction product.
• the halogenated alkane is a molecule that has at least one halogen atom and at least one hydrogen atom in the molecule, and becomes a gas at room temperature.
• the halogenated alkane is desorbed as hydrogen halide together with hydrogen bonded to the adjacent carbon atom by contact with the liquid phase in the presence of a phase transfer catalyst to produce an alkene.
• the halogenated alkane may be a molecule that has at least two halogen atoms and at least one hydrogen atom in the molecule and becomes a gas at room temperature.
• one of the at least two halogen atoms (one having a small bond dissociation energy with a carbon atom) is brought into contact with the liquid phase in the presence of a phase transfer catalyst. It desorbs as hydrogen halide together with hydrogen bonded to adjacent carbon atoms to produce a halogenated alkene.
• halogen atom examples include a fluorine (F) atom, a chlorine (Cl) atom, a bromine (Br) atom, and an iodine (I) atom.
• halogenated alkane examples include fluoroethane, 1,1-difluoroethane, 1,1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoro.
• 1,1-difluoro-1-chloroethane, 1,1,1,2-tetrafluoro-2-chloropropane, 1,1,1,2-tetrafluoro-3-chloropropane, 1,1,1, 2,2-pentafluoropropane and 1,1,1,2,2-pentafluoro-3,3-dichloropropane are preferred.
• the halogenated alkane is preferably a halogenated alkane represented by the general formula (1).
• R1 represents a halogen atom
• R2 represents a hydrogen atom, a halogen atom of the same type as R1, or a halogen atom having a bond dissociation energy between R1 and a carbon atom larger than the atom represented by R1.
• R3 represents a halogen atom of the same kind as R1, a halogen atom whose bond dissociation energy between R1 is larger than the atom represented by R1, or an optionally substituted halogen atom having 1 or more carbon atoms
• the following alkyl groups are shown.
• the halogenated alkene represented by the general formula (2) is generated by elimination of the hydrogen halide (R1-H).
• R2 is the same as R2 in the general formula (1) and represents a hydrogen atom or a halogen atom
• R3 is the same as R3 in the general formula (1), a halogen atom, or An alkyl group having 1 to 3 carbon atoms that may be substituted with any halogen atom.
• a halogen atom represented by R1 a halogen atom that can be represented by R2 and R3, or a halogen atom that substitutes an alkyl group that can be represented by R3; May be the same kind of atoms or different kinds of atoms.
• R3 when R3 is an alkyl group substituted with a halogen atom, the alkyl group may be substituted with a plurality of halogen atoms, or all hydrogens may be substituted with halogen atoms. May be. At this time, the plurality of halogen atoms to be substituted may all be the same type of atom or a combination of different types of halogen atoms.
• R1 is preferably a fluorine (F) atom, a chlorine (Cl) atom or a bromine (Br) atom, and a chlorine (Cl) atom or a bromine (Br) atom. More preferably, it is a chlorine (Cl) atom.
• R2 or R3 is preferably a fluorine (F) atom, and R2 and R3 Are more preferably fluorine (F) atoms.
• the halogenated alkane can be 1,1-difluoro-1-chloroethane, and the halogenated alkene that is a reaction product at this time is 1,1-difluoroethylene (vinylidene fluoride). Can do.
• the content of the halogenated alkane in the reaction system is preferably 0.03% by mass or more and 6% by mass or less, based on the total mass of the reaction solution containing the phase transfer catalyst in the reaction system. % To 5% by mass, more preferably 1% to 4% by mass.
• the gas phase may contain an inert gas such as nitrogen (N 2 ) gas and argon (Ar) gas.
• an inert gas such as nitrogen (N 2 ) gas and argon (Ar) gas.
• N 2 nitrogen
• Ar argon
• the halogenated alkane and the reaction product are substantially used. It is preferable to contain only. “Substantially” means that 99% by volume or more of the gas phase is the halogenated alkane and the reaction product.
• the above-described alkene production method may include a step of bringing the liquid phase and the gas phase into contact with each other. At this time, stirring the liquid phase includes the non-water-soluble solvent finely dispersed in the alkaline aqueous solution and the alkaline aqueous solution containing more base that causes elimination reaction of hydrogen halide. This is preferable from the viewpoint of increasing the contact area and further improving the yield of the alkene as the reaction product.
• the above-described alkene production method may further include a step of separating and recovering the alkene as a reaction product from the gas phase after the contact.
• the separation and recovery can be performed by a known method.
• the alkaline aqueous solution, the phase transfer catalyst and the water-insoluble solvent are added to a reaction vessel having a sufficient capacity to form the liquid phase, and then the gaseous halogen is used. This can be achieved by introducing the alkane fluoride into the reaction vessel.
• the liquid phase may be prepared in the reaction vessel by introducing the alkaline aqueous solution, the phase transfer catalyst and the water-insoluble solvent into the reaction vessel, or prepared by mixing them in advance. You may throw into the said reaction container.
• the order of these inputs or mixing is not particularly limited.
• an inert gas may be introduced into the reaction vessel before introducing the halogenated alkane.
• reaction temperature The temperature inside the reaction vessel (reaction temperature) at this time can be 20 ° C. or higher and lower than 200 ° C., but is preferably 20 ° C. or higher and 140 ° C. or lower, and preferably 40 ° C. or higher and 100 ° C. or lower. More preferably, it is 40 degreeC or more and 80 degrees C or less.
• the pressure inside the reaction vessel after the introduction of the halogenated alkane can be from atmospheric pressure to 5.0 MPa, preferably from atmospheric pressure to 2.0 MPa, preferably from atmospheric pressure to 0.2 MPa.
• the pressure is more preferably 8 MPa or less, further preferably 0.1 MPa or more and 0.5 MPa or less, and particularly preferably 0.1 MPa or more and 0.3 MPa or less.
• reaction time after the introduction of the halogenated alkane may be about 0.5 hours or more and 8 hours or less.
• Example 1 To a 1 L pressure-resistant reaction vessel with a stirrer (hereinafter also simply referred to as “reaction vessel”), 409.7 g of a 50 mass% NaOH aqueous solution was added. Next, the entire amount of the aqueous solution obtained by completely dissolving 0.5013 g of tetrabutylammonium bromide in 106.5 g of water was charged into the reaction vessel. Thereafter, 5.7 g of liquid paraffin was charged into the reaction vessel, the reaction vessel was completely sealed, and the inside of the reaction vessel was depressurized with a vacuum pump, and 9.2 g of 1,1-difluoro-1-chloroethane (R— 142b) was charged.
• reaction vessel 1 L pressure-resistant reaction vessel with a stirrer
• Example 2 To the reaction vessel, 409.7 g of a 50 mass% NaOH aqueous solution was added. Next, the entire amount of the aqueous solution obtained by completely dissolving 0.5011 g of tetrabutylammonium bromide in 96.5 g of water was charged into the reaction vessel. Thereafter, 10.0 g of toluene was charged into the reaction vessel, the reaction vessel was completely sealed, and the inside of the reaction vessel was depressurized with a vacuum pump, and 14.9 g of 1,1-difluoro-1-chloroethane (R-142b ). After the above preparation was completed, stirring was started and the temperature was raised to 80 ° C.
• R-142b 1,1-difluoro-1-chloroethane
• Example 3 To the reaction vessel, 410.5 g of 50 mass% NaOH aqueous solution was added. Next, the entire amount of the aqueous solution obtained by completely dissolving 0.5013 g of tetrabutylammonium bromide in 95.7 g of water was charged into the reaction vessel. Thereafter, 8.6 g of isopropylbenzene was charged into the reaction vessel, the reaction vessel was completely sealed, and the inside of the reaction vessel was depressurized with a vacuum pump, and 11.9 g of 1,1-difluoro-1-chloroethane (R— 142b) was charged. After the above preparation was completed, stirring was started and the temperature was raised to 80 ° C.
• R— 142b 1,1-difluoro-1-chloroethane
• Example 4 To the reaction vessel, 410.5 g of 50 mass% NaOH aqueous solution was added. Next, the entire amount of an aqueous solution obtained by completely dissolving 0.5016 g of tetrabutylammonium bromide in 95.7 g of water was charged into the reaction vessel. Thereafter, 13.0 g of orthodichlorobenzene was charged into the reaction vessel, the reaction vessel was completely sealed, and the inside of the reaction vessel was depressurized with a vacuum pump, and 8.7 g of 1,1-difluoro-1-chloroethane (R -142b) was charged. After the above preparation was completed, stirring was started and the temperature was raised to 80 ° C.
• Example 5 To the reaction vessel, 410.5 g of 50 mass% NaOH aqueous solution was added. Next, the entire amount of the aqueous solution obtained by completely dissolving 0.5013 g of tetrabutylammonium bromide in 95.7 g of water was charged into the reaction vessel. Thereafter, 13.0 g of orthodichlorobenzene was charged into the reaction vessel, the reaction vessel was completely sealed, and the inside of the reaction vessel was depressurized with a vacuum pump, and 8.7 g of 1,1-difluoro-1-chloroethane (R -142b) was charged. After the above preparation was completed, stirring was started and the temperature was raised to 80 ° C.
• the pressure in the reaction vessel during the temperature holding was set to 0.25 MPa to 0.26 MPa. After 3 hours, heating was stopped and the reaction solution was cooled to 40 ° C. or lower, and a gas phase sample was collected in a gas collection bag. The collected gas phase sample was analyzed by gas chromatography in the same manner as in Example 1. The analytical results showed 25.5 GC area% 1,1-difluoroethylene (VDF), 74.5 GC area% 1,1-difluoro-1-chloroethane (R-142b).
• alkenes such as halogenated alkenes can be produced more efficiently. Therefore, according to the present invention, it is expected to contribute to the advancement and spread of technology in fields such as synthesis using alkenes such as halogenated alkenes.

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• 2018
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