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• • 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
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
• • 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
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
  • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
• • 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
  • C07C19/00—Acyclic saturated compounds containing halogen atoms
  • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
  • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
• • 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 hydrochlorofluorocarbon.
• Hydrochlorofluorocarbon (hereinafter, also referred to as HCFC) is used as a new cleaning agent, a refrigerant, a foaming agent and an aerosol, or a synthetic raw material thereof.
• HCFC may be used as a raw material for synthesizing hydrochlorofluoroolefins (hereinafter, also referred to as HCFO).
• HCFO hydrochlorofluoroolefins
• HCFC-244ca 3-chloro-1,1,2,2-tetrafluoropropane
• HCFC can be obtained by reacting a fluorocarbon-containing alcohol with a chlorinating agent.
• a fluorinated alcohol diadder a compound in which two molecules of fluorinated alcohol are added as a by-product together with the target HCFC (hereinafter, also referred to as a fluorinated alcohol diadder). Etc. are generated. Therefore, it is necessary to convert such by-products into HCFCs after chlorination.
• the present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing HCFC with a small amount of by-products, high yield and high purity.
• a method for producing hydrochlorofluorocarbon which comprises reacting a fluorine-containing alcohol with a chlorinating agent in the presence of a catalyst to replace the hydroxyl group of the fluorine-containing alcohol with a chlorine atom.
• the catalyst is phosphine oxide.
• a method for producing a hydrochlorofluorocarbon which comprises using at least one chlorinating agent selected from the group consisting of thionyl chloride, oxalyl chloride and phosgene as the chlorinating agent.
• X-R f -CH 2 OH (1) (In the formula, X represents a hydrogen atom or a fluorine atom, and R f represents a fluoroalkylene group having 1 or more carbon atoms.) (3)
• the fluorine-containing alcohol is 2,2,3,3-tetrafluoropropanol or 2,2,3,3,4,5,5-octafluoropentanol, (1) or.
• R 1 , R 2 , and R 3 each independently contain a monovalent hydrocarbon group which may have a substituent or a monovalent which may have a substituent. Represents a nitrogen heterocyclic group (however, the carbon atom constituting the ring is bonded to the phosphorus atom).
• R 1 to R 3 are all phenyl groups
• R 1 and R 2 are phenyl groups and R 3 is a pyridyl group
• R 1 to R 3 are all 4-fluorophenyl groups.
• the hydrochlorofluorocarbon is 3-chloro-1,1,2,2-tetrafluoropropane or 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane. , (13).
• the hydrochlorofluoroolefin is 1-chloro-2,3,3-trifluoropropene or 1-chloro-2,3,3,4,5,5-heptafluoropentene, (13). ) Or (14).
• the method for producing HCFC of the present invention uses phosphine oxide as a catalyst and reacts a fluorocarbon-containing alcohol with a specific chlorinating agent in the presence thereof. It is characterized by. By the reaction of the fluorinated alcohol with a specific chlorinating agent, the hydroxyl group of the fluorinated alcohol is replaced with a chlorine atom to generate HCFC. In the production method of the present invention, the amount of by-products produced is small, and HCFC can be produced with high yield and high purity.
• the components used in the production method of the present invention will be described in detail, and then the procedure of the production method will be described in detail.
• a fluorine-containing alcohol is used as a raw material.
• the fluorinated alcohol as a raw material may be a mixture of two or more kinds of fluorinated alcohols. That is, the production method of the present invention is industrially advantageous because it is possible to co-produce two or more types of HCFCs.
• the fluorine-containing alcohol used in the production method of the present invention is not particularly limited, and is preferably a primary alcohol, that is, a compound represented by the following formula (1) from the viewpoint of reactivity.
• X-R f -CH 2 OH (1) (In the formula, X represents a hydrogen atom or a fluorine atom, and R f represents a fluoroalkylene group having 1 or more carbon atoms.)
• the carbon number of R f is preferably 1 to 7, more preferably 1 to 5, further preferably 1 to 4, and particularly preferably 2 to 4.
• R f may contain a hydrogen atom, it is preferably a perfluoroalkylene group, and particularly preferably a linear perfluoroalkylene group.
• fluorine-containing alcohol examples include 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol (hereinafter, also referred to as TFPO), 2,2,3,3,3-pentafluoropropanol, and the like.
• fluorine-containing alcohol examples include 2,2,2-trifluoroethanol, TFPO, 2,2,3,3,3-pentafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol.
• 2,2,3,4,4,4-hexafluorobutanol, OFPO, or 3,3,4,4,5,5,6,6,6-nonafluorohexanol is preferred, TFPO, 2,2. More preferably, 3,3,3-pentafluoropropanol, 2,2,3,3,4,4,4-heptafluorobutanol, 2,2,3,4,4,4-hexafluorobutanol, or OFPO. , TFPO or OFPO are particularly preferred.
• fluorinated alcohol When fluorinated alcohol is used, it may be a mixture with other compounds. That is, the raw material of the production method of the present invention may contain fluorinated alcohol, and for example, a mixture of fluorinated alcohol and another compound may be used as the raw material.
• Examples of other compounds contained in the raw materials applied to the production method of the present invention include impurities such as raw materials for producing fluorinated alcohols and by-products produced in addition to the fluorinated alcohols when producing fluorinated alcohols.
• impurities such as raw materials for producing fluorinated alcohols and by-products produced in addition to the fluorinated alcohols when producing fluorinated alcohols.
• by-products generated from the impurities may be removed by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption.
• the impurities are preferably compounds that are inert in the production method of the present invention.
• Fluorine-containing alcohol is preferably contained as a main component in the raw material.
• the content of the fluorine-containing alcohol is preferably 50% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of the raw material.
• the upper limit is 100% by mass.
• an alcohol other than the fluorinated alcohol from the viewpoint of increasing the selectivity of HCFC in the reaction between the fluorinated alcohol and the specific chlorinating agent.
• the amount of alcohol other than the fluorinated alcohol is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, still more preferably 100 mass ppm or less, based on the total amount of the fluorinated alcohol.
• the chlorinating agent used in the production method of the present invention is at least one chlorinating agent selected from the group consisting of thionyl chloride, oxalyl chloride and phosgene from the viewpoint of reactivity with a catalyst described later.
• chlorinating agents a mixture of two or more thereof may be used.
• thionyl chloride and oxalyl chloride are preferable because HCFC can be produced more efficiently.
• the molar ratio of the chlorinating agent used to the fluorinated alcohol used is from the point that HCFC can be produced more efficiently. 0.01 to 100 is preferable, 0.05 to 50 is more preferable, 0.1 to 10 is further preferable, and 0.5 to 5 is particularly preferable. Within the above range, the formation of by-products is suppressed and the volumetric efficiency of the reactor is improved.
• R 1 , R 2 , and R 3 each independently have a monovalent hydrocarbon group which may have a substituent or a monovalent which may have a substituent. Represents a nitrogen-containing heterocyclic group (however, the carbon atom constituting the ring is bonded to the phosphorus atom).
• Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group such as an alkyl group, an alkenyl group and an alkynyl group, a monovalent alicyclic hydrocarbon group such as a cycloalkyl group and a cycloalkenyl group, and a phenyl group.
• the aryl group of, etc. may be mentioned.
• the number of carbon atoms of the monovalent hydrocarbon group is preferably 8 or less, more preferably 6 or less, excluding the substituent.
• Substituents that the monovalent aliphatic hydrocarbon group may have include a monovalent alicyclic hydrocarbon group, an aryl group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, an alkoxy group and the like. Can be mentioned.
• Substituents that the monovalent alicyclic hydrocarbon group may have include a monovalent alicyclic hydrocarbon group, an aryl group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, and an alkoxy group. And so on.
• Examples of the substituent that the aryl group may have include a monovalent alicyclic hydrocarbon group, a monovalent heterocyclic group, a halogen atom such as a fluorine atom, and an alkoxy group.
• Examples of the monovalent nitrogen-containing heterocyclic group include a heterocyclic group having 1 or 2 nitrogen atoms such as a pyridyl group and an imidazolyl group.
• Examples of the substituent that the monovalent nitrogen-containing heterocyclic group may have include a monovalent alicyclic hydrocarbon group, an aryl group, a halogen atom such as a fluorine atom, and the like.
• R 1 , R 2 , and R 3 are independently phenyl group, pyridyl group, 4-fluorophenyl group, 2-tolyl group, respectively, from the viewpoint that HCFC can be produced more efficiently.
• It is preferably a methyl group, a butyl group, or a 3-methylcyclopentenyl group, more preferably a phenyl group, a pyridyl group, a 4-fluorophenyl group, or a 2-tolyl group, and a phenyl group, a pyridyl group, or a pyridyl group.
• It is more preferably a 4-fluorophenyl group, and particularly preferably a phenyl group.
• R 1 to R 3 are all phenyl groups
• R 1 and R 2 are phenyl groups and R 3 are pyridyl groups
• R 1 to R 3 are all 4-fluorophenyl groups.
• R 1 to R 3 are all 2-tolyl groups
• R 1 to R 3 are all phenyl groups
• R 1 and R 2 are phenyl groups and R 3 is. It is more preferable that it is a pyridyl group, or that all of R 1 to R 3 are 4-fluorophenyl groups, and it is particularly preferable that all of R 1 to R 3 are phenyl groups.
• the molar ratio of phosphine oxide used to the fluorinated alcohol used is 0.0001 to that for obtaining a sufficient reaction rate. 10 is preferable, 0.001 to 5 is more preferable, 0.01 to 1 is further preferable, and 0.1 to 0.5 is particularly preferable.
• the phosphine oxide is preferably used by dissolving it in a reaction component or an inert solvent. From the viewpoint of reducing waste liquid, it is preferable to dissolve it in a fluorine-containing alcohol or a chlorinating agent before use.
• a fluorinated alcohol is brought into contact with a chlorinating agent in the presence of phosphine oxide using a reactor.
• the shape and structure of the reactor are not particularly limited, and any reactor may be used as long as it can be reacted by introducing a fluorine-containing alcohol and a chlorinating agent.
• a reactor examples include a glass reactor, a SUS reactor, a glass lining reactor, a resin lining reactor and the like.
• the temperature adjusting unit may be any one capable of adjusting the reaction temperature between the fluorine-containing alcohol and the chlorinating agent. Examples of such a thing include an oil bath and the like.
• the temperature control unit may be provided integrally with the reactor.
• the production method of the present invention can be carried out by either a gas phase reaction or a liquid phase reaction, and is preferably carried out by a liquid phase reaction from the viewpoint of being more industrially advantageous.
• liquid phase reaction means that the fluorinated alcohol and the chlorinating agent are reacted in a liquid state in the presence of phosphine oxide.
• a fluorine-containing alcohol which is a raw material heated to a gas state, and a chlorinating agent are supplied into the reactor, and phosphine oxide filled in the reactor and a gas state are included.
• a procedure for contacting a fluoroalcohol with a chlorinating agent to obtain HCFC can be mentioned.
• a gas (diluted gas) inert to the above reaction may be supplied to the reactor because it is effective for adjusting the flow rate, suppressing by-products, suppressing the deactivation of the catalyst, and the like.
• the diluent gas include nitrogen, carbon dioxide, helium, and argon.
• phosphine oxide is dissolved in a fluorinated alcohol or a chlorinating agent in advance, and the fluorinated alcohol in a liquid state and the chlorinating agent in a liquid state are brought into contact with each other by means such as stirring. Then, the means for obtaining HCFC can be mentioned. It is preferable to dissolve phosphine oxide in a chlorinating agent and bring the fluorinated alcohol in a liquid state into contact with the chlorinating agent in a liquid state by means such as stirring.
• Fluorine-containing alcohol in a liquid state, a catalyst and a chlorinating agent may be added to the reactor at the same time, and the temperature of the reactor may be raised after the addition. , Fluorine-containing alcohol may be added.
• Fluorine-containing alcohol may be added.
• the latter liquid phase reaction is preferable from the viewpoint of reaction temperature, reaction time, reaction yield and HCFC selectivity. Further, when the production method of the present invention is carried out by a liquid phase reaction, it is preferable from the viewpoint that a reactor having a smaller size than the gas phase reaction can be adopted.
• the reaction temperature (temperature in the reactor) in the production method of the present invention is preferably 0 to 150 ° C., more preferably 10 to 125 ° C., still more preferably 20 to 100 ° C. from the viewpoint of more efficiently producing HCFC. .. If the reaction temperature does not reach the above range, the reaction rate and the reaction yield may decrease, unreacted fluorine-containing alcohol remains excessively, and the conversion rate of the fluorine-containing alcohol tends to decrease. Further, when the reaction temperature exceeds the above range, a fluorocarbon-containing alcohol diadduct is excessively generated, and the selectivity of HCFC tends to decrease.
• the temperature inside the reactor can be controlled by adjusting the temperature and pressure of the raw materials supplied to the reactor. If necessary, the inside of the reactor can be supplementarily heated by an electric heater, a microwave generator, or the like.
• the manufacturing method of the present invention may be carried out in a batch manner or in a continuous manner.
• it can be carried out by accommodating a predetermined amount of one of the fluoroalcohol-containing alcohol and the chlorinating agent as a feedstock in the reactor and gradually adding the other to the feedstock in the reactor. ..
• the chlorinating agent is contained in the reactor as a feedstock and a predetermined amount thereof is contained in the reactor, and the fluorinated alcohol is gradually added to the chlorinating agent, or the fluorinated alcohol is used as a feedstock and the predetermined amount is reacted. It can be carried out by accommodating it in a vessel and gradually adding a chlorinating agent to a fluorinated alcohol.
• the phosphine oxide is preferably mixed in advance with a fluorine-containing alcohol or a chlorinating agent.
• the entire predetermined amount of phosphine oxide may be mixed with either a fluorinated alcohol or a chlorinating agent. Further, the phosphine oxide may be divided into a fluorine-containing alcohol and a chlorinating agent in a predetermined amount and mixed.
• the fluoroalcohol-containing alcohol, the chlorinating agent and the phosphine oxide are continuously supplied into the reactor at a predetermined supply rate at a predetermined molar ratio, and these are brought into contact with each other in the reactor for a predetermined time. It can be carried out.
• the phosphine oxide is mixed with a fluorine-containing alcohol or a chlorinating agent in advance and supplied into the reactor from the viewpoint of operational efficiency.
• the supply rate of the fluoroalcohol-containing alcohol, the chlorinating agent and the phosphine oxide to the reactor is adjusted by the supply flow rate of each compound and the sulfur dioxide gas or hydrogen chloride gas generated during the reaction. Will be done.
• the reaction time in the production method of the present invention is, for example, 2 to 8 hours, although it depends on the amounts of phosphine oxide, fluorine-containing alcohol and chlorinating agent.
• the reaction time in the production method of the present invention is represented by the contact time between the fluorinated alcohol and the chlorinating agent. For example, as described above, it is carried out in a batch manner, and a predetermined amount of one of the fluorine-containing alcohol and the chlorinating agent is contained in the reactor as a feedstock, and the other is gradually added to the feedstock in the reactor. This is the time from the start of supply of the other to the end of the reaction after the generation of hydrogen chloride gas has subsided, with one of the fluorine-containing alcohol and the chlorinating agent as the target. When the production method of the present invention is carried out continuously, the reaction time is the residence time of the fluorinated alcohol and the chlorinating agent in the reactor.
• the reaction product mixture containing HCFC When the production method of the present invention is carried out by a liquid phase reaction, it is preferable to bring the reaction product mixture containing HCFC into contact with an alkaline aqueous solution in order to neutralize hydrogen chloride and sulfur dioxide in the reaction product mixture containing HCFC.
• the alkaline aqueous solution used at this time include a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.
• the reaction product mixture containing HCFC After contact with the alkaline aqueous solution, the reaction product mixture containing HCFC is allowed to stand to separate into an organic phase and an aqueous phase. Since HCFC is contained in the organic phase, HCFC can be obtained by separating and recovering the organic phase.
• the obtained liquid of the organic layer may contain, for example, phosphine oxide, a fluorine-containing alcohol which is an unreacted raw material, or a chlorinating agent, and as by-products, a fluorine-containing alcohol diadder or a fluorine-containing liquid may be contained.
• a fluorine-containing alcohol diadder or a fluorine-containing liquid may be contained.
• By-products derived from fluorine-containing alcohols other than the alcohol diadder may also be contained.
• the production method of the present invention usually does not contain a fluorine-containing alcohol diadduct.
• the liquid of the organic layer containing the unreacted raw materials and by-products is preferably separated and purified by general distillation or the like to obtain HCFC having less unreacted raw materials or by-products.
• HCFC is contained as a main component in the reaction solution obtained by purifying if necessary.
• the content of HCFC is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass, based on the total mass of the reaction solution.
• the upper limit is 100% by mass.
• HCFC obtained by the production method of the present invention may be subjected to a hydrogen fluoride reaction to produce HCFO.
• HCFC obtained by the production method of the present invention is subjected to a defluorination hydrogen reaction in the presence of a base and / or a catalyst to produce HCFO.
• the fluorinated alcohol diaddant is contained in the raw material for producing HCFO, the fluorinated alcohol diaddant decomposes into fluorinated alcohol in the reactor and reacts with the product HCFO, so that the selectivity of HCFO decreases. there's a possibility that.
• the content of the fluorocarbon diadduct contained in the reaction solution containing HCFC obtained by the reaction between the fluorocarbon-containing alcohol and the chlorinating agent is preferably 10% by mass or less with respect to the total amount of the reaction solution containing HCFC. 5% by mass or less is more preferable, and 1% by mass or less is particularly preferable. Most preferably, it does not contain a fluorine-containing alcohol diadder.
• the production method of the present invention is preferably applied to the production of HCFO because it can suppress the production of by-products.
• 244ca is obtained.
• the reaction solution contains 244ca as a main component.
• the components other than 244ca can be removed to a desired extent by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, double layer separation and adsorption.
• the obtained 244ca may be subjected to a hydrogen fluoride reaction to produce 1233yd.
• Examples of the procedure for the defluorinated hydrogen reaction include known methods such as International Publication No. 2016/136744.
• the 244ca defluorinated hydrogen reaction may be either a liquid phase reaction or a gas phase reaction.
• the liquid phase reaction means that 244ca dissolved in a liquid state or a liquid is subjected to a hydrogen fluoride reaction.
• the gas phase reaction means that 244ca in a gaseous state is reacted with hydrogen fluoride.
• the fluorine-containing alcohol is OFPO
• 448 occc is obtained.
• the reaction solution contains 448occc as a main component.
• the components other than 448occc can be removed to the desired extent by known means such as distillation, extraction distillation, azeotropic distillation, membrane separation, two-layer separation and adsorption.
• the obtained 448 occc may be subjected to a hydrogen fluoride reaction to produce 1437 dycc.
• a hydrogen fluoride reaction to produce 1437 dycc.
• 1437 dycc Z
• Examples of the procedure for the defluorination hydrogen reaction include known methods such as Zhurnal Organicheskoi Kimii, ( Russian), 1988, Vol. 24, No. 8, pp. 1626-1633.
• the 448occc defluorinated hydrogen reaction may be either a liquid phase reaction or a gas phase reaction.
• the liquid phase reaction means that 448occc in a liquid state or dissolved in a liquid is subjected to a hydrogen fluoride reaction.
• the gas phase reaction means that 448occc in a gaseous state is subjected to a hydrogen fluoride reaction.
• Examples 1 to 3, 6, 8 and 9 are examples of the present invention, and Examples 4, 5 and 7 are comparative examples.
• Example 1 A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor. There, triphenylphosphine oxide (in the above formula (2), R 1 to R 3 are all phenyl groups) (hereinafter, also referred to as Ph 3 PO) (5.27 g), thionyl chloride (49.5 g). ), TFPO (50.0 g) was added, and the temperature of the oil bath was adjusted so that the reaction temperature became 80 ° C.
• triphenylphosphine oxide in the above formula (2), R 1 to R 3 are all phenyl groups
• Example 2 A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor.
• Table 1 shows the results of the reaction in the same procedure as in Example 1 except that the raw material was OFPO instead of TFPO.
• Example 3 A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor.
• Table 1 shows the results of the reaction in the same procedure as in Example 1 except that the chlorinating agent was oxalyl chloride instead of thionyl chloride.
• Example 4 (First step) A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor. Then, after putting thionyl chloride into the four-necked flask, a mixed solution consisting of TFPO and N, N-dimethylformamide (hereinafter, also referred to as DMF) was dropped into the four-necked flask. The temperature of the oil bath and the dropping rate of the mixed solution were adjusted so that the reaction temperature (the temperature of the liquid phase in the four-necked flask) became 0 ° C. during the dropping of the mixed solution. After the dropping of the mixed solution was completed, stirring was continued until the generation of hydrogen chloride gas subsided, and the reaction product mixture containing 2,2,3,3-tetrafluoropropanesulfonic acid chloride was recovered.
• DMF mixed solution
• Example 5 (First step) A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor. Then, after putting thionyl chloride into the four-necked flask, a mixed solution consisting of OFPO and DMF was dropped into the four-necked flask. The temperature of the oil bath and the dropping rate of the mixed solution were adjusted so that the reaction temperature (the temperature of the liquid phase in the four-necked flask) was 50 ° C. during the dropping of the mixed solution. After the dropping of the mixed solution is completed, stirring is continued until the generation of hydrogen chloride gas subsides, and the reaction product mixture containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is recovered. did.
• the conversion rate in Tables 1 and 2 represents the ratio (%) of the molar amount consumed in the reaction to the charged amount (molar amount), and the selectivity is the production of each compound with respect to the molar amount of the consumed raw material. Represents the amount of molars consumed.
• the amount of chlorinating agent (mol / mol) represents the molar ratio of the chlorinating agent to the fluorine-containing alcohol.
• the amount of catalyst (mol / mol) represents the molar ratio of the catalyst to the fluorine-containing alcohol.
• Example 6 A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor.
• Table 2 shows the results of the reaction carried out in the same procedure as in Example 1 except that the raw material was a mixture of TFPO and OFPO instead of TFPO.
• Example 7 A four-necked flask (reactor) equipped with a stirrer, a glass distillation column filled with Raschig rings (measured number of stages 5), and a Dimroth condenser was immersed in an oil bath to form a reactor.
• Table 2 shows the results of the reaction carried out in the same procedure as in Example 4 except that the raw material was a mixture of TFPO and OFPO instead of TFPO.
• the meanings of the words in Table 2 are the same as those in Table 1.
• Example 8 The reaction was carried out in the same procedure as in Example 1 except that the catalyst was 2-diphenylphosphorylpyridine instead of Ph 3 PO (in (2) above, R 1 and R 2 are phenyl groups and R 3 is a pyridyl group). The results of the above are shown in Table 3.
• Example 9 Same as Example 1 except that the catalyst is tris (4-fluorophenyl) phosphine oxide instead of Ph 3 PO (in (2) above, R 1 to R 3 are all 4-fluorophenyl groups). Table 3 shows the results of the reaction in the procedure. The meanings of the words in Table 3 are the same as those in Table 1.
• HCFC is produced in high yield and high purity by carrying out the reaction of a fluorine-containing alcohol and a chlorinating agent in the presence of phosphine oxide without using a special operation or a reaction device. It has become possible to apply industrial-scale mass production.

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