[go: up one dir, main page]

WO2019124220A1 - Procédé de production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane et procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoropentène - Google Patents

Procédé de production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane et procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoropentène Download PDF

Info

Publication number
WO2019124220A1
WO2019124220A1 PCT/JP2018/045931 JP2018045931W WO2019124220A1 WO 2019124220 A1 WO2019124220 A1 WO 2019124220A1 JP 2018045931 W JP2018045931 W JP 2018045931W WO 2019124220 A1 WO2019124220 A1 WO 2019124220A1
Authority
WO
WIPO (PCT)
Prior art keywords
chloro
reaction
octafluoropentane
occc
ofpo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/045931
Other languages
English (en)
Japanese (ja)
Inventor
真理 市野川
厚史 藤森
卓也 岩瀬
岡本　秀一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to JP2019561024A priority Critical patent/JP7259764B2/ja
Priority to CN201880081963.5A priority patent/CN111491910B/zh
Publication of WO2019124220A1 publication Critical patent/WO2019124220A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • 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
    • 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
    • C07C301/00—Esters of sulfurous acid

Definitions

  • the present invention relates to a process for producing 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane and 1-chloro-2,3,3,4,4,5,5-hepta
  • the present invention relates to a method for producing fluoropentene.
  • CHCl CFCF 2 CF 2 CF 2 H; HCFO-1437dycc
  • 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (CF 2 HCF 2 CF 2 CF 2 CClH 2 , HCFC-448occc), for producing HCFO-1437dycc Used as a synthetic raw material for
  • Non-Patent Document 1 makes a polyfluorinated alkyl chlorosulfite by reacting a triethylamine complex of a polyfluorinated alcohol with thionyl chloride to obtain a polyfluoroalkyl chlorosulfite as a diethylene glycol
  • a process for obtaining HCFC-448occc by reaction with an alkali metal halide such as LiCl in the presence of
  • an alkali metal halide such as LiCl
  • triethylamine hydrochloride is precipitated, and therefore, a filtration process for removing the precipitated salt is required.
  • the reaction for obtaining HCFC-448occc from polyfluoroalkyl chlorosulfite there is a problem that volumetric efficiency is poor and productivity is lowered as a result of using diethylene glycol.
  • Non-Patent Document 2 discloses a method of reacting HC2, 2-3, 3, 4, 4, 5, 5-octafluoropentanol with phosphorus triphenyl chloride to obtain HCFC-448occc. .
  • triphenyl phosphorus chloride remains as a solid after the reaction, and there is a problem that the post-treatment step becomes complicated.
  • Non-Patent Document 2 discloses a method for obtaining HCFO-1437dycc by dehydrofluorination of HCFC-448occc by reacting HCFC-448occc with sodium methoxide after obtaining HCFC-448occc above. It is done. However, in the above method, it is considered that the target product HCFO-1437dycc reacts with sodium methoxide, and as a result, the yield of HCFO-1437dycc is as low as about 50%, which is an industrially useful process. It is hard to say.
  • the present invention does not require a complicated post-treatment step, and produces 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc) with high selectivity.
  • the purpose is to provide an efficient manufacturing method that can be performed.
  • the present invention is also an industrially advantageous method using readily available raw materials to increase 1-chloro-2,3,3,4,4,5,5-heptafluoropentene (HCFO-1437dycc).
  • An object of the present invention is to provide an efficient method for producing HCFO-1437 dycc which can be produced with high selectivity and high yield.
  • the present invention provides a method for producing 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane having the constitution described in the following [1] to [11] and [12] There is provided a process for the preparation of 1-chloro-2,3,3,4,4,5,5-heptafluoropentene having the described composition.
  • a predetermined amount of one of 2,2,3,3,4,4,5,5-octafluoropentanol and thionyl chloride is a feed, and the other is a feed of 5-chloro-1,1,2,2,3,3 described in any one of [1] to [3] which is added at a rate of 0.0015 to 5 mol / mol ⁇ min as an addition amount per unit molar amount , 4, 4-octafluoropentane production method.
  • the contact time of 2,2,3,3,4,4,5,5-octafluoropentanol with thionyl chloride is set to 1 to 8 hours [1] to [4]
  • the mass ratio of the nitrogen-containing organic compound to the 2,2,3,3,4,4,5,5-octafluoropentanol (nitrogen-containing organic compound / 2,2,3,3, 5-chloro-1,1,2,2,3, 3 according to any one of [1] to [5], wherein the 3,4,4,5,5-octafluoropentanol) is 0.001 to 1.
  • Process for producing 3,4,4-octafluoropentane [7]
  • 5-chloro-1,1,2,2,3,3 according to any one of [1] to [6] wherein the reaction temperature for thermal decomposition is 70 to 170 ° C. , 4, 4-octafluoropentane production method.
  • the mass ratio of the solvent to the 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride (solvent / 2,2,3,3,3, 5-chloro-1,1,2,2,3,3 according to any one of [8] to [10], wherein the 4,4,5,5-octafluoropentanesulfonic acid chloride) is 0.01 to 1.
  • 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane obtained by the method according to any of [12] [1] to [11], 5 By dehydrofluorination reaction of -chloro-1,1,2,2,3,3,4,4-octafluoropentane in aqueous base solution, 1-chloro-2,3,3,4,4 And 5,5-heptafluoropentene, which is a process for producing 1-chloro-2,3,3,4,4,5,5-heptafluoropentene.
  • 1437 dycc has geometric isomers Z form and E form depending on the position of the substituent bonded to the carbon having a double bond.
  • any ratio of the Z form or the E form, or the Z form and the E form Indicates a mixture of When (Z) or (E) is added after the compound name or the abbreviation of the compound, it indicates that it is the Z form or the E form of the respective compound.
  • 448 occc can be efficiently produced with high selectivity without the need for complicated post-treatment steps.
  • 1437 dycc production method of the present invention 1437 dy dy cc can be produced with high selectivity and high yield by an industrially advantageous method using easily available raw materials.
  • the method for producing 448 occc according to this embodiment is characterized in that at least one nitrogen-containing organic compound selected from the group consisting of N, N-dimethylformamide, dimethylacetamide, pyridine and tetramethylurea (hereinafter simply referred to as “nitrogen-containing organic compound” as well) Note) in the presence of 2,2,3,3,4,4,5,5-octafluoropentanol (CF 2 HCF 2 CF 2 CF 2 CH 2 OH, hereinafter referred to as “OFPO”) and chloride.
  • nitrogen-containing organic compound selected from the group consisting of N, N-dimethylformamide, dimethylacetamide, pyridine and tetramethylurea
  • the reaction of OFPO with thionyl chloride in the first step is represented by the following formula (1).
  • 1-pentanol-2 represented by the following formula (2) as a by-product together with 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride 2,3,3,4,4,5,5-octafluoro-1,1-sulphite may be formed. Therefore, the product of the above reaction contains 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride and, if such a by-product is produced in the above reaction, a composition containing the by-products. It is obtained as a thing.
  • 1-pentanol-2,2,3,3,4,4,5,5-octafluoro-1,1-sulfite is 2,2,3,3,4,4,5,5 -One molecule of OFPO added to octafluoropentanesulfonic acid chloride.
  • 1-pentanol-2,2,3,3,4,4,5,5-octafluoro-1,1-sulfite is also referred to as “OFPO diadduct”.
  • the first step is carried out in the presence of at least one nitrogen-containing organic compound selected from the group consisting of N, N-dimethylformamide, dimethylacetamide, pyridine and tetramethylurea.
  • the nitrogen-containing organic compound has a catalytic action in the reaction of the formula (1) and can promote the reaction of OFPO with thionyl chloride.
  • N, N-dimethylformamide (DMF) is preferable from the viewpoint of obtaining a sufficient reaction rate.
  • the nitrogen-containing organic compounds may be used alone or in combination of two or more.
  • the mass ratio of the nitrogen-containing organic compound to the OFPO is preferably 0.001 to 1.
  • the mass ratio (nitrogen-containing organic compound / OFPO) is in the above range, a sufficient reaction rate can be obtained.
  • the formation of the by-product OFPO di-adduct is suppressed, and the selectivity of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is increased.
  • the mass ratio (nitrogen-containing organic compound / OFPO) is more preferably 0.002 or more, and still more preferably 0.005 or more, from the viewpoint of further suppressing the formation of the OFPO di-adduct.
  • the mass ratio (nitrogen-containing organic compound / OFPO) is more preferably 0.5 or less, further preferably 0.1 or less.
  • the molar ratio of thionyl chloride to OFPO is preferably 0.1 to 5.
  • the molar ratio (thionyl chloride / OFPO) is preferably 0.3 or more, more preferably 0.5 or more, and particularly preferably 0.8 or more from the viewpoint of increasing the conversion of the raw material.
  • the molar ratio (thionyl chloride / OFPO) is more preferably 4 or less.
  • the reaction temperature is preferably 70 ° C. or less.
  • the conversion of OFPO and the selectivity of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride are improved.
  • the reaction temperature is preferably 0 ° C. or higher. When the reaction temperature is 0 ° C. or more, a sufficient reaction rate can be obtained.
  • the reaction temperature in the first step is preferably 20 ° C. or higher, and more preferably 30 ° C. or higher from the viewpoint of effectively advancing the reaction and increasing the reaction rate.
  • the reaction proceeds rapidly, a large amount of hydrogen chloride gas is generated, which may increase the pressure in the reactor and damage the reactor.
  • the raw materials such as OFPO and thionyl chloride, 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride and hydrogen chloride gas may be added to the outside of the reactor. It may be discharged.
  • the first step is preferably performed at a reaction temperature of 0 ° C. to 70 ° C., and more preferably 30 ° C. to 70 ° C. Within this range, the reaction proceeds effectively, and 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is obtained with high selectivity.
  • the first step may be performed batchwise or continuously.
  • the first step is carried out batchwise, it is carried out by storing predetermined amounts of one of OFPO and thionyl chloride as a feed in the reactor and gradually adding the other to the feed in the reactor. be able to.
  • a predetermined amount of thionyl chloride is supplied as a feed into the reactor, and OFPO is gradually added to thionyl chloride, or a predetermined amount of OFPO is reacted as a feed, and then reacted.
  • the reaction can be carried out by gradually adding thionyl chloride to OFPO.
  • the nitrogen-containing organic compound may be mixed with any one of OFPO and thionyl chloride in a predetermined amount.
  • a predetermined amount of the nitrogen-containing organic compound may be divided into OFPO and thionyl chloride and mixed.
  • addition of the other compound of OFPO and thionyl chloride to be added to the supplied material comprising a predetermined amount of either OFPO or thionyl chloride is preferably 0.0015 to 5 mol / mol ⁇ min as an addition amount per unit mol (1 mol) of the feed. If the addition rate is 0.0015 mol / mol ⁇ min or more, the reaction can be sufficiently advanced, and if the addition rate is 5 mol / mol ⁇ min or less, the formation of the by-product OFPO di-adduct etc. It can be suppressed.
  • the addition rate is more preferably 0.0125 mol / mol ⁇ min or more, and more preferably 1.5 mol / mol ⁇ min or less.
  • the first step when carried out continuously, OFPO, thionyl chloride and nitrogen-containing organic compound are continuously fed into the reactor at a predetermined feed rate at a predetermined molar ratio, and these are predetermined in the reactor. It can be done in contact with time.
  • the nitrogen-containing organic compound is preferably pre-mixed with OFPO or thionyl chloride and fed into the reactor in terms of operation efficiency.
  • the feed rates of OFPO, thionyl chloride and nitrogen-containing organic compound to the reactor are controlled by the feed flow rates of the respective compounds.
  • the feed rate of OFPO into the reactor is 0.0015 to 5 mol / mol ⁇ min with respect to the feed amount (molar amount) of thionyl chloride per minute
  • the thionyl chloride feed rate is set to 0.0015 to 5 mol / mol ⁇ min with respect to the feed amount (molar amount) per minute of OFPO, or Koji is preferred.
  • the reaction time in the first step is, for example, 1 to 8 hours, depending on the amounts of OFPO and thionyl chloride.
  • the reaction time in the first step is represented by the contact time of OFPO with thionyl chloride.
  • the first step is carried out batchwise, and a predetermined amount of one of OFPO and thionyl chloride is contained as a feed in the reactor, and the other is gradually added to the feed in the reactor. In the case where the addition is carried out, it is the time from the start of supply of the other, with one of OFPO and thionyl chloride as the feed, to the end of the reaction after the generation of hydrogen chloride gas ceases.
  • the reaction time is the residence time of OFPO and thionyl chloride in the reactor.
  • thionyl chloride When water is present in the reaction system of OFPO and thionyl chloride, thionyl chloride is decomposed into sulfur dioxide and hydrogen chloride by the reaction of thionyl chloride with water. Also, when water is present in the reaction system, 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is decomposed into OFPO, sulfur dioxide and hydrogen chloride. Therefore, in order to suppress these decompositions, it is preferable to reduce water in the reaction system as much as possible. As a method of reducing water, for example, a method of replacing the atmosphere of the reaction system with a dry gas is mentioned.
  • the water content is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and still more preferably 100 mass ppm or less, with respect to the total amount of OFPO.
  • no alcohol other than OFPO should be contained.
  • the amount of alcohol other than OFPO is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and still more preferably 100 mass ppm or less based on the total amount of OFPO.
  • OFPO or nitrogen-containing organic compound may be mixed with moisture (moisture) in the air and be present in the form of a mixture of OFPO and water or a mixture of nitrogen-containing organic compound and water.
  • moisture moisture
  • water contained in the mixture of OFPO and water or the mixture of nitrogen-containing organic compound and water is reduced as much as possible for the same reason as described above, and then the OFPO or nitrogen-containing organic compound is supplied to the reactor. It is preferable to do.
  • a mixture of OFPO and water or a mixture of nitrogen-containing organic compound and water is brought into contact with a desiccant such as zeolite or silica to remove water, or a mixture of OFPO and water and nitrogen-containing
  • a desiccant such as zeolite or silica
  • the method of contacting with desiccants, such as a zeolite and a silica, and removing water is mentioned.
  • the amount of water in the mixture of OFPO and water or the mixture of nitrogen-containing organic compound and water is OFPO or nitrogen-containing organic compound respectively
  • the amount is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 100 ppm by mass or less with respect to the amount (the amount of OFPO or the amount of nitrogen-containing organic compound).
  • the water content in the mixture of OFPO, nitrogen-containing organic compound and water is the total amount of OFPO and nitrogen-containing organic compound
  • the amount is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 100 ppm by mass or less with respect to (total amount of OFPO and DMF).
  • a composition comprising 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is obtained.
  • the composition containing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride may contain, for example, a nitrogen-containing organic compound, an unreacted raw material OFPO and thionyl chloride. And OFPO diadduct as a by-product.
  • a composition containing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride obtained in the first step May contain a compound represented by the following formula (3) obtained by reacting a part or all of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride with DMF .
  • 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is also referred to as "intermediate”.
  • the compound represented by the formula (3) is also referred to as “intermediate-DMF adduct”.
  • the intermediate-DMF adduct is presumed to be thermally decomposed to form 448 occc.
  • occc is obtained by pyrolyzing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride.
  • 448 occc is produced as shown in the following formula (4) by thermally decomposing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride. Specifically, 448 occc is produced by the desulfurization sulfur reaction.
  • the thermal decomposition temperature is preferably 70 ° C. or higher.
  • the thermal decomposition of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is promoted.
  • 80 ° C. or more is more preferable, 100 ° C. or more is more preferable, 110 ° C. or more is particularly preferable, and 115 ° C. or more is most preferable from the viewpoint .
  • the thermal decomposition temperature suppresses the volatilization of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride before thermal decomposition, and improves the yield of 448 occc 170 degrees C or less is preferable from the point which can be carried out.
  • the thermal decomposition temperature refers to the temperature in the reactor where the thermal decomposition is performed, more specifically, the temperature of the liquid phase in the reactor.
  • reaction temperature when DMF is used as the nitrogen-containing organic compound, when the reaction temperature is 170 ° C. or higher, DMF is decomposed to form formic acid, and formic acid is 2,2,3,3,4,4,5,5-octafluoropentane.
  • a 2,2,3,3,4,4,5,5-octafluoropentyl formate represented by the following formula (5) is by-produced.
  • the reaction temperature is preferably 170 ° C. or less from the viewpoint of suppressing the formation of this by-product.
  • 2,2,3,3,4,4,5,5-octafluoropentyl formate is referred to as "intermediate-formic acid adduct".
  • the thermal decomposition is preferably performed in the presence of a solvent.
  • the solvent can be used to promote the formation of 448 occc.
  • the solvent can dissolve 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride and 448 occc, and is a compound inactive in the reaction of the above formula (4).
  • the above-mentioned nitrogen-containing organic compounds can be used. Specifically, DMF, tetramethylurea, dimethylacetamide, pyridine and the like can be used. Among them, DMF is particularly preferable because 448 occc can be efficiently obtained.
  • the solvent it is preferable to use the same compound as the nitrogen-containing organic compound used in the first step.
  • the mass ratio of the solvent to 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride (solvent / 2,2
  • the ratio of 3,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride) is preferably 0.01 to 1. If the amount of solvent is within the above range, the formation of 448 occc can be further promoted, and 448 occc can be obtained in high yield.
  • the thermal decomposition in the second step may be carried out batchwise or continuously. From the viewpoint of production efficiency, continuous operation is preferred.
  • the pressure of the pyrolysis in the second step may be normal pressure, reduced pressure or increased pressure.
  • thermal decomposition is preferably performed in 1 to 40 hours.
  • a composition comprising 448 occc can be obtained.
  • the composition containing 448 occc obtained in addition to the target substance 448 occc, unreacted 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride, OFPO, OFPO diaddition May contain body, hydrogen chloride and sulfur dioxide.
  • the composition containing 448 occc may include DMF, an intermediate-DMF adduct, an intermediate-formic acid adduct, and the like.
  • the composition comprising 448 occc is contacted with an aqueous alkaline solution to neutralize hydrogen chloride and sulfur dioxide in the composition comprising 448 occc.
  • an aqueous alkali solution used at this time sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, etc. are mentioned.
  • the composition containing 448 occc is separated into an organic phase and an aqueous phase. Since 448 occc is contained in the organic phase, 448 occc can be obtained by separating and recovering the organic phase.
  • a method of bringing a composition containing 448 occc into contact with an alkaline aqueous solution as described above for neutralization of impurities it may be carried out in a short time in the absence of a phase transfer catalyst or a water-soluble organic solvent. preferable.
  • the 448 occc itself does not come in contact with the aqueous alkali solution sufficiently, and the dehydrofluorination reaction generated from 448 occc to 1437 dycc can be suppressed by bringing the 448 occc into contact with the aqueous alkaline solution as described later.
  • 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride By thermally decomposing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride in the second step, 2,2,3,3,4,4,5,5-
  • the conversion of octafluoropentanesulfonic acid chloride can be 50% or more.
  • the selectivity of 448 occc can be made 50% or more by going through the second step.
  • the selectivity (%) of 448 occc is the ratio of the molar amount of 448 occc in the composition containing 448 occc obtained in the second step to the molar amount of the intermediate consumed in the second step ((( The molar amount of 448 occc) / (molar amount of intermediate consumed) ⁇ 100).
  • the selectivity of 448 occc is determined by bringing the distillate to the molar amount of the intermediate consumed in the second step into contact with an aqueous alkaline solution.
  • the ratio of the molar amount of 448 occc ((molar amount of 448 occc) / (molar amount of intermediate consumed) ⁇ 100).
  • Compounds other than 448 occ contained in the organic phase for example, OFPO, OFPO diadduct, nitrogen-containing organic compound, solvent, DMF, intermediate-DMF adduct, intermediate-formic acid adduct may be separated by ordinary distillation Yes, which gives high purity 448 occc. Distillation of the composition containing 448 occc may be performed at any pressure, reduced pressure or increased pressure, and is preferably performed at reduced pressure.
  • the second step may also be carried out by reactive distillation using a reactor equipped with a distillation column.
  • the pressure in the reactor for performing reactive distillation and in the distillation column is preferably 30 to 2000 hPa, more preferably 100 to 1500 hPa, and 200 to 1100 hPa in that high purity 448 occc is obtained and the recovery amount of 448 occc is increased. More preferable.
  • the amount of 448 occc recovered can be further increased by extracting the composition containing 448 occc remaining as a bottoms and distilling it.
  • the content of the OFPO diadduct in the composition containing 448 occc can be made less than 10% by mass. 7 mass% or less is preferable, and, as for content of OFPO 2 adduct, 5 mass% or less is more preferable.
  • content of 448 occc in the composition containing 448 occc obtained can be 80 mass% or more by passing through a 1st process, a 2nd process, and distillation. 85 mass% or more is preferable, as for content of 448 occc, 90 mass% or more is more preferable, and 95 mass% or more is more preferable.
  • the same reactor may be used, or different reactors may be used.
  • the reaction apparatus that can be used for both the first step and the second step include those having a reactor, a temperature regulator, and the like.
  • OFPO and thionyl chloride can be introduced and reacted, and 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride can be pyrolyzed. What is necessary.
  • glass, stainless steel such as SUS, a glass lining material, a resin lining material, etc. may be mentioned.
  • the reaction temperature of OFPO and thionyl chloride can be adjusted, and the temperature at the thermal decomposition of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride As long as it can adjust.
  • an oil bath, a heater, etc. are mentioned.
  • the temperature control unit may be provided integrally with the reactor.
  • the reactor used in each step may have only the functions necessary for the step.
  • an apparatus used industrially can be used, and mass production and the like of 448 occc becomes easy.
  • FIG. 1 shows an example of an apparatus used when the first step is performed in the batch mode and the second step is performed in the continuous mode, and is used industrially.
  • a predetermined amount of thionyl chloride is accommodated in the reactor 11 as a feed, and a mixed solution of OFPO and a nitrogen-containing organic compound is continuously supplied thereto at a predetermined supply rate.
  • the reaction apparatus 10 performs the second step by removing the liquid phase after the reaction from the reactor 11, the raw material supply means 12 for supplying the mixed solution of OFPO and the nitrogen-containing organic compound to the reactor 11, the reactor 11.
  • a liquid supply means 13 for supplying the reactor 14 is provided.
  • the reactor 10 further includes means 15 for removing the liquid phase after reaction from the reactor 14.
  • the reactor 11 and the reactor 14 are comprised so that the temperature in a reactor may be adjusted with the temperature control apparatus which is not shown in figure.
  • the reaction apparatus 10 comprises an alkaline cleaning means 16 for bringing a liquid phase after reaction taken out of the reactor 14 into contact with an alkaline aqueous solution, and a separation means 17 for separating the liquid phase after contacting the alkaline aqueous solution into an organic phase and an aqueous phase. Is equipped.
  • a mixed solution of OFPO and nitrogen-containing organic compound is supplied from the raw material supply means 12 into the reactor 11 at a predetermined supply flow rate, and thionyl chloride Is added to
  • the supply flow rate of the mixed solution of OFPO and the nitrogen-containing organic compound can be automatically controlled, for example, by installing a mass flow controller or the like.
  • thionyl chloride and OFPO react in the presence of the nitrogen-containing organic compound to form 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride.
  • the liquid phase composed of the composition containing the 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride thus produced is then fed to the reactor 14 by the feeding means 13.
  • a composition containing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is heated to a predetermined temperature by a temperature controller not shown,
  • the 3,4,4,5,5-octafluoropentanesulfonic acid chloride is pyrolyzed to form 448 occc.
  • the liquid phase composed of the composition containing 448 occc formed is taken out of the reactor 14 by the liquid transfer means 15, passed through the alkaline cleaning means 16 and brought into contact with the alkaline aqueous solution, and thereafter the organic phase and water are separated by the separation means 17. Separated into phases.
  • the desired substance 448 occc can be obtained in the organic phase separated in this way.
  • FIG. 2 shows an example of an apparatus used when performing the first step and the second step in a continuous manner, and which is used industrially.
  • the reactor 20 shown in FIG. 2 comprises a reactor 21 for carrying out the first step, a raw material supply means 22a for supplying thionyl chloride to the reactor 21, a raw material supply means 22b for supplying OFPO, and a nitrogen-containing organic compound.
  • a raw material supply means 22c for supplying is provided.
  • the reaction apparatus 20 is provided with the liquid supply means 23 which takes out the liquid phase after reaction from the reactor 21, and supplies it to the reactor 24 which performs a 2nd process.
  • the reactor 20 further includes means 25 for removing the liquid phase after reaction from the reactor 24.
  • the reactor 21 and the reactor 24 are comprised so that the temperature in a reactor may be adjusted with the temperature control apparatus which is not shown in figure.
  • the reaction apparatus 20 comprises an alkaline cleaning means 26 for bringing a liquid phase after reaction taken out of the reactor 24 into contact with an alkaline aqueous solution, and a separation means 27 for separating the liquid phase after being contacted with an alkaline aqueous solution into an organic phase and an aqueous phase. Is equipped.
  • Thionyl chloride, OFPO and a nitrogen-containing organic compound are supplied into the reactor 21 at predetermined flow rates by the raw material supply means 22a to 22c.
  • the nitrogen-containing organic compound may be mixed with any one of thionyl chloride or OFPO and supplied to the reactor 21.
  • the supply flow rate of thionyl chloride, OFPO and nitrogen-containing organic compound to the reactor 21 can be controlled automatically, for example, by installing a mass flow controller or the like.
  • thionyl chloride and OFPO react in the presence of the nitrogen-containing organic compound to form 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride.
  • the liquid phase composed of the composition containing the 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride thus produced is then fed to the reactor 24 by the feeding means 23.
  • a composition containing 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride is heated to a predetermined temperature by a temperature controller not shown,
  • the 3,4,4,5,5-octafluoropentanesulfonic acid chloride is pyrolyzed to form 448 occc.
  • the liquid phase composed of the composition containing 448 occc formed is taken out of the reactor 24 by the liquid transfer means 25, passed through the alkaline cleaning means 26 and brought into contact with the alkaline aqueous solution, Separated into The desired substance 448 occc can be obtained in the organic phase separated in this manner.
  • the method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoropentene (1437dycc) of the present invention is 5-chloro-1,1,2,5 by the method of the present invention described above.
  • 2,3,3,4,4-octafluoropentane (448 occc) is obtained, and the obtained 448 occc is subjected to dehydrofluorination reaction in an aqueous solution of a base to obtain 1437 dycc.
  • reaction relating to the method for producing 1437 dycc of this embodiment is represented by the following formula (6).
  • the 1437 dycc obtained by the manufacturing method of the present embodiment has a high proportion of halogen which suppresses the flammability and has a carbon-carbon double bond which is easily decomposed by OH radicals in the atmosphere in the molecule, Have low impact on the ozone layer and low impact on global warming. Therefore, the usefulness as a solvent, a working medium (a heat medium used for heat exchange etc., a working medium used for a heat cycle system etc., etc.) is high.
  • the 1437 dy s cc obtained by the manufacturing method of the present embodiment may be only the Z form, the E only, or a mixture of the Z form and the E form.
  • the Z form, 1437 dycc (Z) has higher chemical stability than the E form, 1437 dycc (E), and is more preferable as a solvent or a working medium.
  • 1437 dycc containing 1437 dycc (Z) can be manufactured efficiently.
  • 1437 dycc in which the content ratio of 1437 dycc (Z) is higher than that of 1 437 dycc (E) can be obtained.
  • reaction (6) 446 occc is dehydrofluorinated in an aqueous solution of a base It is.
  • any material containing 448 occc may be used, and for example, 448 occc obtained by the method of producing 448 occc in the above embodiment can be used.
  • the crude solution containing 448 occc obtained by the 448 occc production method of the above embodiment may be used as it is, or the crude solution may be used after being purified by a known method.
  • the starting material for the reaction (6) may contain impurities such as byproducts other than 448 occc and unreacted raw materials in the production method of 448 occc from the viewpoint of economy, but those containing no other impurities besides 448 occc Conceptually preferred.
  • the impurity is preferably a compound that does not inhibit 448 occc's dehydrofluorination reaction.
  • 1437 dycc, OFPO, DMF etc. can be illustrated.
  • the ratio of 448 occc to the total amount of impurities and 448 occc is preferably 85% by mass to less than 100% by mass, and more preferably 90% by mass to 99% by mass.
  • the ratio of the total amount of 1437 dycc, OFPO and DMF is to efficiently produce 1437 dycc. More than 0 mass% and 15 mass% or less are preferable with respect to the total amount, and 0.1 mass% or more and 7 mass% or less are more preferable.
  • the content ratio of OFPO is preferably more than 0% by mass and 3% by mass or less relative to the total amount of the starting materials, 0.1% by mass or more and 1% by mass or less More preferable. If the content of OFPO is within the above range, the manufacturing cost can be suppressed and the selectivity of 1437 dycc is further improved.
  • the base in the reaction (6) is not particularly limited as long as it is a base that can carry out the dehydrofluorination reaction of the reaction (6).
  • the base is preferably at least one selected from the group consisting of metal hydroxides, metal oxides and metal carbonates.
  • Examples of the metal hydroxide include alkaline earth metal hydroxides and alkali metal hydroxides.
  • As the alkaline earth metal hydroxide magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide are preferable, and as the alkali metal hydroxide, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable.
  • the metal hydroxide may be one type, or two or more types.
  • the metal oxide examples include alkali metal oxides and alkaline earth metal oxides.
  • alkali metal oxide sodium oxide is preferable, and as the alkaline earth metal oxide, calcium oxide is preferable.
  • the metal oxide may be of one type, two or more types, or a complex oxide of two or more types of metals.
  • metal carbonates include alkali metal carbonates and alkaline earth metal carbonates.
  • the alkali metal carbonates include carbonates of lithium, sodium, potassium, rubidium, cesium or francium.
  • the alkaline earth metal carbonates include carbonates of beryllium, magnesium, calcium, strontium, barium or radium.
  • the metal carbonate may be one type, or two or more types.
  • the metal hydroxide is preferably at least one selected from potassium hydroxide and sodium hydroxide. Potassium hydroxide or sodium hydroxide may be used alone, or potassium hydroxide and sodium hydroxide may be used in combination.
  • the amount of the base relative to 448 occc is preferably 0.5 to 10 mol, more preferably 0.5 to 5.0 mol per mol of 448 occc, 0.5 to 2.5 mol is more preferable, and 0.5 to 2.0 mol is most preferable.
  • a base is used as an aqueous solution of a base.
  • an aqueous alkali metal hydroxide solution is preferable, and an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is more preferable.
  • the amount of the base relative to the total amount of the aqueous solution of the base is preferably 0.5 to 40% by mass, and more preferably 10 to 40% by mass. If the amount of the base relative to the total amount of the aqueous solution of the base is equal to or more than the above lower limit value, a sufficient reaction rate is easily obtained, and the separation of the desired product by two-layer separation is easily performed. If it is below the said upper limit, since a base will be easy to melt
  • FIG. 3 shows an example (reactor 30) of an apparatus used industrially for the 1437 dycc manufacturing method of the present embodiment.
  • 448 occc is accommodated in advance for the compound involved in the base aqueous solution stored in the raw material tank (denoted by the reference numeral 32) and other reactions used as needed. It supplies to the reactor 31 which carried out, and makes it react.
  • the composition containing the produced 1437 dycc is recovered from the reactor 31, but is cooled via the cooler 33 as necessary. Furthermore, it is preferable to collect the product from which the water has been removed by passing it through the dewatering tower 34 from the recovery tank 35 containing the product if necessary.
  • the well-known reactor used for the dehydrofluorination reaction in liquid phase reaction is preferable.
  • the material of the reactor 31 include iron, nickel, an alloy containing these as a main component, and glass. If necessary, lining treatment such as resin lining or glass lining may be performed on the reactor 31.
  • the reaction temperature in the reaction (6) is preferably 0 to 80 ° C., more preferably 0 to 60 ° C., still more preferably 10 to 50 ° C., and particularly preferably 20 to 40 ° C.
  • the reaction temperature is the temperature in the reactor, more specifically, the temperature of the liquid phase in the reactor. In the apparatus shown in FIG. 3, the temperature in the reactor 31 is the reaction temperature.
  • the pressure in the reactor during the reaction is not particularly limited, but is preferably ⁇ 0.1 to 10 MPa, more preferably 0 to 5 MPa, and still more preferably 0 to 1 MPa.
  • the pressure in the reactor is preferably at least 448 occc vapor pressure at the reaction temperature.
  • reaction (6) can be carried out either semi-continuously, batchwise or continuously.
  • reaction time can be suitably adjusted with a general method by each system.
  • the reaction time is preferably 1 to 50 hours in the case of a batch system, and is preferably 1 to 20 hours in the case of a continuous system, since the conversion of 448 occc and the selectivity of 1437 dycc which are raw materials can be easily controlled.
  • the residence time of the raw material in the reactor is regarded as the reaction time.
  • the reaction (6) is preferably carried out in the presence of a phase transfer catalyst so that the raw material 448 occc and the aqueous solution of the base can be efficiently contacted. Moreover, you may carry out in presence of water-soluble organic solvents, such as a tetraglyme, in the range which does not affect reaction. In order to speed up the reaction, it is preferred to use a phase transfer catalyst.
  • phase transfer catalysts include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers and the like, and quaternary ammonium salts, quaternary phosphonium salts and quaternary arsonium Salts and sulfonium salts are preferred, and quaternary ammonium salts are more preferred.
  • R 11 ⁇ R 14 each independently represents a monovalent hydrocarbon group, or a monovalent hydrocarbon group inert functional group bonded to the reaction, Y 1 - represents a monovalent anion).
  • R 11 to R 14 are a hydrocarbon group, examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group, with an alkyl group and an aryl group being preferable.
  • the number of carbon atoms in each of R 11 to R 14 is preferably 1 to 100, and more preferably 4 to 30.
  • R 11 to R 14 may be the same or different from each other.
  • R 11 to R 14 are a monovalent hydrocarbon group to which a functional group inert to the reaction is bonded is appropriately selected depending on the reaction conditions, but a halogen atom, an alkoxycarbonyl group, an acyloxy Groups, nitrile groups, acyl groups, carboxyl groups, alkoxyl groups and the like.
  • the compound represented by the above formula (i) is preferably a combination of the following quaternary ammonium (R 11 R 12 R 13 R 14 N + ) and the following Y 1- .
  • Y 1 ⁇ fluorine ion, chloride ion, bromine ion, iodine ion, hydroxide ion.
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC chlorides
  • R 21 to R 24 each independently represent a monovalent hydrocarbon group, and Y 2- represents a monovalent anion.
  • R 21 to R 24 represent Each may be the same group or may be different groups.
  • the hydrocarbon group in R 21 to R 24 includes an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and the like, and an alkyl group and an aryl group are preferable.
  • tetraethyl phosphonium, tetra-n-butyl phosphonium, ethyl tri-n-octyl phosphonium, cetyl triethyl phosphonium, cetyl tri-n- Examples include butyl phosphonium, n-butyl triphenyl phosphonium, n-amyl triphenyl phosphonium, methyl triphenyl phosphonium, benzyl triphenyl phosphonium, tetraphenyl phosphonium and the like.
  • the quaternary phosphonium salt is preferably at least one selected from the group consisting of tetra-n-butylphosphonium chloride and tetra-n-butylphosphonium fluoride from the viewpoint of industrial availability.
  • R 31 to R 34 are the same as R 21 to R 24 in the formula (ii), and preferred embodiments are also the same.
  • Y 3- represents a monovalent anion. As Y 3 ⁇ , a halogen ion is preferable, and a fluorine ion, a chlorine ion, and a bromine ion are more preferable.
  • Examples of the quaternary arsonium salt represented by the above formula (iii) include triphenylmethylarsonium fluoride, tetraphenylarsonium fluoride, triphenylmethylarsonium chloride, tetraphenylarsonium chloride, tetraphenylarsonium bromide and the like. Can be mentioned. As the quaternary arsonium salt, triphenylmethylarsonium chloride is preferred.
  • R 41 to R 43 and Y 4- are the same as R 31 to R 34 and Y 3- in the formula (iii), and preferred embodiments are also the same.
  • di-n-butylmethylsulfonium iodide tri-n-butylsulfonium tetrafluoroborate, dihexylmethylsulfonium iodide, dicyclohexylmethylsulfonium iodide, dodecylmethylethylsulfonium Chloride, tris (diethylamino) sulfonium difluorotrimethyl silicate and the like can be mentioned.
  • the sulfonium salt dodecyl methyl ethyl sulfonium chloride is preferred.
  • crown ethers examples include 18-crown-6, dibenzo-18-crown-6, and dicyclohexyl-18-crown-6.
  • phase transfer catalysts TBAC, TBAB, and TOMAC are preferable in terms of industrial availability, price, and ease of handling.
  • the amount of phase transfer catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5.0 parts by mass, and further 0.1 to 2.0 parts by mass with respect to 100 parts by mass of 448 occc. Preferably, 0.1 to 1.5 parts by mass is particularly preferable.
  • the amount of phase transfer catalyst is most preferably 0.1 to 1.0 parts by mass with respect to 100 parts by mass of 448 occc, because the selectivity and the yield of 1437 dycc are high.
  • the reaction step, the reactor, and the materials of the reactor may be the same as in the case of not using a phase transfer catalyst.
  • the reaction conditions such as the concentration of the base, the amount used, and the reaction temperature may also be the same as in the case where the phase transfer catalyst is not used.
  • reaction (6) for example, 448 occc, an aqueous solution of a base, optionally a water-soluble organic solvent and / or a compound involved in a reaction such as a phase transfer catalyst are supplied to the reactor and stirred so as to be uniform. It is possible to proceed by setting the desired temperature condition and pressure condition.
  • the reaction (6) may be carried out by compatibilizing the aqueous phase and the organic phase using a water-soluble organic solvent instead of the phase transfer catalyst.
  • a water-soluble organic solvent it is preferable to carry out sufficient stirring in order to make the compound involved in the reaction in the reaction system homogeneous.
  • the water-soluble organic solvent include dimethyl sulfoxide, tetraglyme, and acetonitrile. Among these, dimethylsulfoxide and tetraglyme are preferable in that they have a boiling point suitable for the reaction (6).
  • a phase transfer catalyst and a water-soluble organic solvent may be used in combination.
  • the reaction solution after completion of the reaction When the reaction solution after completion of the reaction is allowed to stand, it separates into an organic phase and an aqueous phase.
  • the organic phase may contain by-products in addition to unreacted 448 occc and 1437 dycc of the target product.
  • 1-chloro-3,3,4,4,5,5-hexafluoropentine, 5-chloro-1,1,2,3,3,4,4-heptafluoropentene HCFO -1437 cycc, hereinafter referred to as "1437 cycc").
  • 2,3,3,4,4,5,5-heptafluoro-1- (1-2) represented by the following chemical formula (v) as a by-product 2,2,3,3,4,4,5,5-octafluoropentoxy) pentene etc. may be contained.
  • the production method of the present embodiment is an excellent method capable of selectively producing the target compound 1437dycc.
  • Example 1-1 A four-necked flask (reactor) equipped with a stirrer and a Dimroth condenser was immersed in an oil bath to make a reactor. Then, after thionyl chloride was placed in a four-necked flask, a mixed solution of OFPO and DMF was dropped into the four-necked flask. The temperature of the oil bath was adjusted so that the reaction temperature was 50 ° C. during the dropwise addition of the mixed solution.
  • the OFPO conversion ratio (%) is the ratio of the molar amount of OFPO consumed in the first step to the molar amount of OFPO input in the first step ((molar amount of OFPO consumed) / (Molar amount of OFPO charged) ⁇ 100).
  • the intermediate selectivity (%) means the intermediate (2, 2, 3, 3, 4, 4, 4, which was produced in the first step with respect to the molar amount of OFPO consumed in the first step).
  • the ratio of the molar amount of 5,5-octafluoropentanesulfonic acid chloride) ((molar amount of produced intermediate) / (molar amount of consumed OFPO) ⁇ 100).
  • the selectivity of other compounds is calculated similarly for each compound.
  • an active ingredient represents an intermediate and an intermediate-DMF adduct, and "an active ingredient selectivity" was computed by the molar quantity of the sum total of an active ingredient.
  • the intermediate yield (%) means the ratio of the molar amount of the intermediate formed in the first step to the molar amount of OFPO introduced in the first step ((molar amount of the generated intermediate) / (Molar amount of OFPO added) ⁇ 100).
  • the reaction time is the time from the start of the dropwise addition of OFPO to the end of stirring, that is, the time elapsed from the end of the reaction to the end of the evolution of hydrogen chloride gas.
  • Example 1-2 to 1-7 The same reactor and procedure as in Example 1 were carried out except that the reaction conditions were changed as shown in Table 1. Table 1 summarizes the reaction conditions, the composition of the intermediate crude solution and the analysis results.
  • the fraction was brought into contact with a 20% by mass aqueous potassium hydroxide solution for neutralization, and a portion of the organic phase was recovered from the neutralized fraction and analyzed for its composition.
  • the analysis was performed using gas chromatography (GC).
  • GC gas chromatography
  • DB-1301 60 m in length ⁇ 250 ⁇ m in inner diameter ⁇ 1 ⁇ m in thickness, manufactured by Agilent Technologies, Inc.
  • Table 2 shows the amount of 448 occc obtained in the fraction.
  • intermediate conversion (%) means intermediate consumed in the second step with respect to the molar amount of the intermediate used in the second step (molar amount of the intermediate in the intermediate crude liquid).
  • the ratio of the molar amount of the body ((molar amount of intermediate consumed) / (molar amount of intermediate charged) ⁇ 100).
  • OFPO di-adduct selectivity (%) is the ratio of the molar amount of OFPO di-adduct generated in the second step to the molar amount of the intermediate consumed in the second step (( The molar amount of OFPO diadduct formed / (molar amount of consumed intermediate) ⁇ 100).
  • the selectivity of other compounds is calculated similarly for each compound.
  • the 448 occc selectivity (%) is the ratio of the molar amount of 448 occc produced in the second step to the molar amount of the intermediate consumed in the second step ((molar amount of 448 occc produced) / (consumption) Molar amount of the intermediate prepared) ⁇ 100).
  • Example 2-2 The second step was performed in the same reactor and procedure as in Example 2-1 except that the reaction conditions were changed as shown in Table 2.
  • Table 2 summarizes the reaction conditions, the reaction results and the like.
  • Example 2-3 In a four-necked flask equipped with a stirrer and a distillation column, an intermediate crude solution obtained by reacting OFPO with thionyl chloride in the presence of DMF at a reaction temperature of 30 to 70 ° C. and DMF as a solvent are placed at 110 ° C. While heating, the distillation line (Dimroth condenser) was cooled to -20 ° C. Thus, thermal decomposition of 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride was performed. The composition of the intermediate crude solution used and the amount of the intermediate crude solution are shown in Table 2. The molar amount of the intermediate crude solution was represented by the sum of the molar amounts of the compounds contained in the intermediate crude solution.
  • the composition of the residue remaining in the four-necked flask was analyzed by 1 H-NMR and 19 F-NMR (JNM-ECP400, manufactured by Nippon Denshi Co., Ltd.). Furthermore, the amount of each compound recovered in the second step was calculated from the composition of the bottoms. The results are shown in Table 2.
  • Example 2-4 The second step was performed in the same reactor and procedure as in Example 2-1 except that the reaction conditions were changed as shown in Table 2.
  • Table 2 summarizes the reaction conditions, the reaction results and the like.
  • Example 2-5 The second step was carried out in the same reactor and procedure as in Example 2-3, except that the reaction conditions were changed as shown in Table 2.
  • Table 2 summarizes the reaction conditions, the reaction results and the like.
  • OFPO and thionyl chloride are reacted in the presence of DMF to produce 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride,
  • thermal decomposition of this 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride to obtain a reaction solution containing 448 occc, complicated post-treatment steps are unnecessary, and high selection is achieved. It is possible to produce 448 occc at a rate, and 448 occc can be efficiently produced.
  • Example 2-6 The second step was performed in the same reactor and procedure as in Example 2-1 except that the reaction conditions were changed as shown in Table 3. However, in Example 2-6, a distillation line was not used. The composition of the residue remaining in the four-necked flask was analyzed by 1 H-NMR and 19 F-NMR (JNM-ECP400, manufactured by Nippon Denshi Co., Ltd.). Furthermore, the amount of each compound recovered in the second step was calculated from the composition of the bottoms. Table 3 summarizes the reaction conditions, the results of the reaction, and the like.
  • Examples 2-7 to 2-8 Perform the second step in the same reactor and procedure as in Example 2-1 except that the reaction conditions are changed as shown in Table 3 (Table 2), and the amount of each compound recovered in the second step is Calculated.
  • Table 3 summarizes the reaction conditions, the results of the reaction, and the like.
  • the 448 occc used above is obtained by reacting OFPO with thionyl chloride in the presence of DMF to produce 2,2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride, and It was prepared by thermal decomposition of 2,3,3,4,4,5,5-octafluoropentanesulfonic acid chloride.
  • the recovered organic layer is washed with water and analyzed by gas chromatography.
  • the results are shown in Table 4.
  • the conversion rate of 448 occc is a ratio (mol%) of the amount of 448 occc consumed in the reaction to the total amount of 448 occc fed to the reactor.
  • the selectivity of each compound is the ratio (mol%) of each component generated to 448 occc converted, and was calculated from the result of GC analysis.
  • Table 4 also shows the actual preparation amount and the reaction conditions.
  • "TBAB / 448occc” represents the preparation amount (parts by mass) of TBAB with respect to 100 parts by mass of 448occc.
  • Example 3-2 to 3-4 As shown in Table 4, the reaction was carried out in the same manner as in Example 3-1 except that the actual preparation amount and the reaction temperature were changed, respectively, to obtain a composition containing 1437 dycc. In Examples 3-3 and 3-4, the operation was terminated when there was a large amount of solid precipitation and no change in the conversion of 448 occc due to the reaction start time was observed. Incidentally, the reaction end point was the point at which the conversion rate of 448 occc was 99% or more.
  • Example 3-5 As shown in Table 5, the reaction was carried out in the same manner as in Example 3-1 except that the preparation amount and the preparation amount of TBAB were changed, respectively, to obtain a composition containing 1437 dycc. In Example 3-5, the operation was finished when no change in the conversion of 448 occc due to the reaction start time was observed. Incidentally, the reaction end point was the point at which the conversion of 448 occc was 97% or more. Table 5 also shows Examples 3-3 having the same reaction temperature for reference.
  • Example 3-6, 3-7 As shown in Table 5, the reaction was carried out in the same manner as in Example 3-1 except that the preparation amount and the preparation amount of KOH were changed, respectively, to obtain a composition containing 1437 dycc.
  • the reaction end point was the point at which the conversion of 448 occc was 99% or more.
  • Example 3-8 As shown in Table 5, the reaction was carried out in the same manner as in Example 3-1 except that the actual preparation amount and the concentration of KOH were changed, respectively, to obtain a composition containing 1437 dycc. The operation was terminated when no change in the conversion of 448 occc due to the reaction start time was observed.
  • Example 3-5 in Table 5 it can be seen that the reaction time can be shortened as the amount of TBAB charged increases. It was also found that 1437 dycc can be produced without any change in 1437 dycc selectivity and yield by securing a sufficient reaction time even when the amount of TBAB charged is small.
  • the target amount of KOH can be reduced to produce the desired 1437 dycc with high selectivity and high yield while suppressing the amount of solid content generated.
  • the volumetric efficiency also improves, and as a result, the productivity improves.
  • the manufacturing method of 1437 dycc in a present Example can manufacture 1437 dycc efficiently.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production efficace permettant la production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane avec une sélectivité élevée sans avoir besoin d'un procédé de post-traitement compliqué. Le procédé de production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane, selon l'invention comprend une première étape consistant à faire réagir du 2,2,3,3,4,4,5,5-octafluoropentanol avec du chlorure de thionyle en présence d'au moins un composé organique contenant de l'azote choisi dans le groupe constitué par N, N-diméthyl formamide, diméthyl acétamide, pyridine et tétraméthyle urée pour produire du chlorure d'acide sulfonique 2,2,3,3,4,4,5,5-octafluoropentane, et une seconde étape consistant à dégrader thermiquement le chlorure d'acide sulfonique 2,2,3,3,4,4,5,5-octafluoropentane pour obtenir du 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane.
PCT/JP2018/045931 2017-12-19 2018-12-13 Procédé de production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane et procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoropentène Ceased WO2019124220A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2019561024A JP7259764B2 (ja) 2017-12-19 2018-12-13 ５－クロロ－１，１，２，２，３，３，４，４－オクタフルオロペンタンの製造方法及び１－クロロ－２，３，３，４，４，５，５－ヘプタフルオロペンテンの製造方法
CN201880081963.5A CN111491910B (zh) 2017-12-19 2018-12-13 5-氯-1,1,2,2,3,3,4,4-八氟戊烷的制造方法及1-氯-2,3,3,4,4,5,5-七氟戊烯的制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2017242572 2017-12-19
JP2017-242572 2017-12-19

Publications (1)

Publication Number Publication Date
WO2019124220A1 true WO2019124220A1 (fr) 2019-06-27

Family

ID=66993479

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2018/045931 Ceased WO2019124220A1 (fr) 2017-12-19 2018-12-13 Procédé de production de 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane et procédé de production de 1-chloro-2,3,3,4,4,5,5-heptafluoropentène

Country Status (3)

Country Link
JP (1) JP7259764B2 (fr)
CN (1) CN111491910B (fr)
WO (1) WO2019124220A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1283897A (fr) * 1960-12-23 1962-02-09 Bayer Ag Procédé de préparation de composés organiques fluorés
RU2247110C1 (ru) * 2003-09-24 2005-02-27 Волгоградский государственный технический университет (ВолгГТУ) Способ получения полифторированных алкилхлорсульфитов
WO2016136744A1 (fr) * 2015-02-27 2016-09-01 ダイキン工業株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
WO2018131394A1 (fr) * 2017-01-10 2018-07-19 旭硝子株式会社 Procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1283897A (fr) * 1960-12-23 1962-02-09 Bayer Ag Procédé de préparation de composés organiques fluorés
RU2247110C1 (ru) * 2003-09-24 2005-02-27 Волгоградский государственный технический университет (ВолгГТУ) Способ получения полифторированных алкилхлорсульфитов
WO2016136744A1 (fr) * 2015-02-27 2016-09-01 ダイキン工業株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène
WO2018131394A1 (fr) * 2017-01-10 2018-07-19 旭硝子株式会社 Procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
RAKHIMOV, A. I. ET AL.: "New Catalytic Synthesis of Polyfluoroalkyl Chlorosulfites", RUSSIAN JOURNAL OF GENERAL CHEMISTRY, vol. 74, no. 5, 2004, pages 799 - 800, XP055620553, ISSN: 1070-3632 *
RAKHIMOV, A. I. ET AL.: "Polyfluoroalkyl Chlorosulfites as New Polyfluorinating Agents", RUSSIAN JOURNAL OF APPLIED CHEMISTRY, vol. 75, no. 7, 2002, pages 1162 - 1165, XP003006748, ISSN: 1070-4272, doi:10.1023/A:1020788902312 *
ZAPEVALOV, A. YA. ET AL.: "a, a-Disubstituted polyfluoroalkenes", ZHURNAL ORGANICHESKOI KHIMII, vol. 24, no. 8, 1988, pages 1626 - 1633, XP008110423, ISSN: 0514-7492 *

Also Published As

Publication number Publication date
CN111491910A (zh) 2020-08-04
CN111491910B (zh) 2024-07-16
JP7259764B2 (ja) 2023-04-18
JPWO2019124220A1 (ja) 2020-12-03

Similar Documents

Publication Publication Date Title
JP6860057B2 (ja) １−クロロ−２，３，３−トリフルオロプロペンの製造方法
US10399915B2 (en) Manufacturing method of 1-chloro-2,3,3,3-tetrafluoropropene
JP2015120670A (ja) １−クロロ−１，２−ジフルオロエチレンの製造方法
JP2017001990A (ja) １，２−ジクロロ−３，３，３−トリフルオロプロペンの製造方法
CN111479793B (zh) 1-氯-2,3,3,4,4,5,5-七氟戊烯的制造方法
JP7088025B2 (ja) ３－クロロ－１，１，２，２－テトラフルオロプロパンの製造方法
JP7259764B2 (ja) ５－クロロ－１，１，２，２，３，３，４，４－オクタフルオロペンタンの製造方法及び１－クロロ－２，３，３，４，４，５，５－ヘプタフルオロペンテンの製造方法
JP7488472B2 (ja) Ｚ－１，２－ジクロロ－３，３，３－トリフルオロプロペンを製造する方法
JP7647581B2 (ja) １－クロロ－２，３，３－トリフルオロプロペンの製造方法
JP7722382B2 (ja) ハイドロクロロフルオロカーボンの製造方法
JP2016222548A (ja) ヨウ化アルキル化合物の製造方法
WO2019168115A1 (fr) Procédé de production de 1,2-dichloro-2,3,3,3-tétrafluoropropane et procédé de production de 1-chloro-2,3,3,3-tétrafluoropropène
JP2013018722A (ja) １−クロロ−３，３，３−トリフルオロプロピンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18892753

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2019561024

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18892753

Country of ref document: EP

Kind code of ref document: A1