JPWO2019124220A1 - Method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane and production of 1-chloro-2,3,3,4,5,5-heptafluoropentene Method - Google Patents

Abstract

Providing an efficient production method capable of producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane with high selectivity without the need for complicated post-treatment steps. 2,2,3,3,4,5,5-octa 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 first step of reacting fluoropentanol with thionyl chloride to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, and the above 2,2,3,3 A second step of obtaining 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane by thermally decomposing 4,4,5,5-octafluoropentanesulfonic acid chloride. A method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane having and.

Description

The present invention relates to a method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane and 1-chloro-2,3,3,4,5,5-hepta. The present invention relates to a method for producing fluoropentene.

1-Chloro-2,3,3,4,5,5-heptafluoro-1-pentene (CHCl = CFCF ₂ CF ₂ CF ₂ H; HCFO-1437dycc) is a new cleaning agent, refrigerant, foaming agent, It is used as a solvent, an aerosol, or a synthetic raw material thereof. For example, 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane (CF ₂ HCF ₂ CF ₂ CF ₂ CClH ₂ , HCFC-448occc) is used to produce HCFO-1437 dycc. It is used as a synthetic raw material for.

As a method for producing HCFC-448occc, Non-Patent Document 1 describes that a triethylamine complex of a polyfluorinated alcohol is reacted with thionyl chloride to obtain polyfluoroalkylchlorosulfite, and then polyfluoroalkylchlorosulfite is used as diethylene glycol. Disclosed is a method for obtaining HCFC-448occc by reacting with an alkali metal halide such as LiCl in the presence of. In this method, triethylamine hydrochloride is precipitated in the reaction for obtaining polyfluoroalkylchlorosulfite from the polyfluorinated alcohol, so that a filtration treatment for removing the precipitated salt is required. Further, in the reaction for obtaining HCFC-448occc from polyfluoroalkylchlorosulfite, since diethylene glycol is used, there is a problem that the volumetric efficiency is poor and the productivity is lowered as a result.

In addition, Non-Patent Document 2 discloses a method for obtaining HCFC-448occc by reacting 2,2,3,3,4,5,5-octafluoropentanol with phosphorus triphenylchloride. .. In the above-mentioned production method, since phosphorus triphenylchloride remains as a solid content after the reaction, there is a problem that the post-treatment step is complicated.

Further, Non-Patent Document 2 discloses a method of obtaining HCFC-448occc and then reacting HCFC-448occc with sodium methoxide to defluoride hydrogen HCFC-448occc to obtain HCFO-1437dycc. Has been done. However, in the above method, it is considered that the target product, HCFO-1437 dycc, reacts with sodium methoxide. As a result, the yield of HCFO-1437 dycc is as low as about 50%, which is an industrially useful production method. It's hard to say.

Polyfluoroalkyl Chlorosulfits as New Polyfluolinating Agents, (Russia), 2002, Vol. 75, No. 7, pp. 1162-1165 Zhurnal Organicheskoi Kimii, (Russia), 1988, Vol. 24, No. 8, pp. 1626-1633

The present invention is capable of producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane (HCFC-448occc) with high selectivity without the need for complicated post-treatment steps. The purpose is to provide an efficient manufacturing method that can be performed.
The present invention also yields 1-chloro-2,3,3,4,5,5-heptafluoropentene (HCFO-1437dycc) in an industrially advantageous manner using readily available raw materials. It is an object of the present invention to provide an efficient method for producing HCFO-1437 dycc, which can be produced with selectivity and high yield.

The present invention relates to a method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane having the constitutions described in the following [1] to [11] and [12]. Provided is a method for producing 1-chloro-2,3,3,4,5,5-heptafluoropentene having the composition described.
[1] In the presence of at least one nitrogen-containing organic compound selected from the group consisting of N, N-dimethylformamide, dimethylacetamide, pyridine and tetramethylurea, 2,2,3,3,4,5, The first step of reacting 5-octafluoropentanol with thionyl chloride to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, and the above 2,2,3 , 3,4,4,5,5-octafluoropentane Sulfonic acid chloride is thermally decomposed to obtain 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane. A method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane, which comprises two steps.
[2] The 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to claim [1], wherein the reaction temperature is 0 to 70 ° C. in the first step. Manufacturing method.
[3] In the first step, the molar ratio of thionyl chloride to 2,2,3,3,4,5,5-octafluoropentanol (thionyl chloride / 2,2,3,3,4) 4,5,5-octafluoropentanol) is 0.1 to 5, 5-chloro-1,1,2,2,3,3,4,5-octa according to [1] or [2]. Method for producing fluoropentane.
[4] In the first step, one predetermined amount of 2,2,3,3,4,5,5-octafluoropentanol and thionyl chloride is used as a to be supplied, and the other is to be supplied. 5-Chloro-1,1,2,2,3,3 according to any one of [1] to [3], which is added at a rate of 0.0015 to 5 mol / mol · min as the addition amount per unit molar amount. , 4,4-Octafluoropentane manufacturing method.

[5] In the first step, the contact time between 2,2,3,3,4,5,5-octafluoropentanol and thionyl chloride is set to 1 to 8 hours [1] to [4]. 5. The method for producing 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane according to any one of.
[6] In the first step, the mass ratio of the nitrogen-containing organic compound to 2,2,3,3,4,5,5-octafluoropentanol (nitrogen-containing organic compound / 2,2,3). 5-Chloro-1,1,2,2,3 according to any one of [1] to [5], wherein 3,4,5,4,5-octafluoropentanol) is 0.001 to 1. Method 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 of thermal decomposition is 70 to 170 ° C. in the second step. , 4,4-Octafluoropentane manufacturing method.

[8] 5-Chloro-1,1,2,2,3,3,4,4 according to any one of [1] to [7], wherein the thermal decomposition reaction is carried out in a solvent in the second step. -A method for producing octafluoropentane.
[9] Production of 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to [8], wherein the solvent is a nitrogen-containing organic compound in the second step. Method.
[10] In the second step, 5-chloro-1,1,2,2,3,3,4,4 according to [8] or [9], wherein the solvent is N, N-dimethylformamide. -A method for producing octafluoropentane.
[11] In the second step, the mass ratio of the solvent to the 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride (solvent / 2,2,3,3). 5. Chloro-1,1,2,2,3 according to any one of [8] to [10], wherein the amount of 4,4,5,5-octafluoropentanesulfonic acid chloride) is 0.01 to 1. A method for producing 3,4,4-octafluoropentane.
[12] 5-Chloro-1,1,2,2,3,3,4,4-octafluoropentane was obtained by the production method according to any one of [1] to [11], and 5 was obtained. -Chloro-1,1,2,2,3,3,4,5-octafluoropentane is reacted with hydrogen fluoride in a base aqueous solution to cause 1-chloro-2,3,3,4,4. , 5,5-Heptafluoropentene, a method for producing 1-chloro-2,3,3,4,5,5-heptafluoropentene.

In this specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, but the abbreviation is used instead of the compound name as necessary. Further, as an abbreviation, only the number after the hyphen (−) and the lowercase alphabetic part (for example, “448occc” in “HCFC-448occc” and “1437dycc” in “HCFO-1437dycc”) may be used.

Further, 1437 dycc has Z-form and E-form which are geometric isomers depending on the position of the substituent bonded to the carbon having a double bond. In the present specification, when a compound name or an abbreviation of a compound is used for a compound in which Z-form and E-form are present, an arbitrary ratio of Z-form or E-form, or Z-form and E-form is used. 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 each compound.

According to the method for producing 448 occc of the present invention, complicated post-treatment steps are not required, and 448 occc can be efficiently produced with a high selectivity.
According to the method for producing 1437 dycc of the present invention, 1437 dycc can be produced with high selectivity and high yield by an industrially advantageous method using easily available raw materials.

It is a figure which shows an example of the apparatus used in the manufacturing method of 448occc of embodiment. It is a figure which shows an example of another apparatus used in the manufacturing method of 448occc of embodiment. It is a figure which shows an example of the reactor used in the manufacturing method of 1437 dycc of embodiment.

<Manufacturing method of 448 occc>
Hereinafter, the method for producing 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (CF ₂ HCF ₂ CF ₂ CF ₂ CClH ₂ ) of the present embodiment will be specifically described. ..

The method for producing 448occc of the present embodiment is at least one nitrogen-containing organic compound selected from the group consisting of N, N-dimethylformamide, dimethylacetamide, pyridine and tetramethylurea (hereinafter, also simply referred to as "nitrogen-containing organic compound"). , 2,2,3,3,4,5,5-octafluoropentanol (CF ₂ HCF ₂ CF ₂ CF ₂ CH ₂ OH, hereinafter referred to as "OFPO") and chloride in the presence of. The first to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride (CF ₂ HCF ₂ CF ₂ CF ₂ CH ₂ OSOCl) by reacting with thionyl (SOCl ₂ ). And a second step of obtaining 448 occc by thermally decomposing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride.

The reaction between OFPO and thionyl chloride in the first step is represented by the following formula (1).

In the above reaction, 1-pentanol-2 represented by the following formula (2) is used as a by-product together with 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. , 2,3,3,4,5,5-octafluoro-1,1-sulfite may be produced. Therefore, the product of the above reaction has a composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride and, if a by-product is produced by the above reaction, the by-product. Obtained as a thing. Here, 1-pentanol-2,2,3,3,4,5,5-octafluoro-1,1-sulfite is 2,2,3,3,4,5,5. -One molecule of OFPO is added to octafluoropentane sulfonic acid chloride. Hereinafter, 1-pentanol-2,2,3,3,4,5,5-octafluoro-1,1-sulfite will also be 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 between OFPO and thionyl chloride. As the nitrogen-containing organic compound, N, N-dimethylformamide (DMF) is preferable from the viewpoint of obtaining a sufficient reaction rate. The nitrogen-containing organic compound may be used alone or in combination of two or more.

In the first step, the mass ratio of the nitrogen-containing organic compound to OFPO (nitrogen-containing organic compound / OFPO) is preferably 0.001 to 1. When the mass ratio (nitrogen-containing organic compound / OFPO) is within the above range, a sufficient reaction rate can be obtained. In addition, the production of OFPO diadducts, which are by-products, is suppressed, and the selectivity of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride increases. The mass ratio (nitrogen-containing organic compound / OFPO) is more preferably 0.002 or more, and further preferably 0.005 or more, from the viewpoint of further suppressing the formation of OFPO diadducts and the like. The mass ratio (nitrogen-containing organic compound / OFPO) is more preferably 0.5 or less, and even more preferably 0.1 or less.

In the first step, the molar ratio of thionyl chloride to OFPO (thionyl chloride / OFPO) is preferably 0.1 to 5. When the molar ratio (thionyl chloride / OFPO) is within the above range, the formation of OFPO diadducts, which are by-products, is suppressed, and 2,2,3,3,4,5,5-octafluoro. Increases the selectivity of pentane sulfonic acid chloride. The molar ratio (thionyl chloride / OFPO) is more preferably 0.3 or more, further preferably 0.5 or more, and particularly preferably 0.8 or more from the viewpoint of increasing the conversion rate of the raw material. The molar ratio (thionyl chloride / OFPO) is more preferably 4 or less.

In the first step, the reaction temperature is preferably 70 ° C. or lower. When the reaction temperature is 70 ° C. or lower, the conversion rate of OFPO and the selectivity of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride are improved.

Further, in the first step, it is preferable that the reaction temperature is 0 ° C. or higher. When the reaction temperature is 0 ° C. or higher, a sufficient reaction rate can be obtained. The reaction temperature in the first step is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint that the reaction can be effectively advanced and the reaction rate can be further increased.

If the reaction proceeds rapidly, a large amount of hydrogen chloride gas is generated, the pressure in the reactor rises, and the reactor may be damaged. When a large amount of hydrogen chloride gas is generated, raw materials such as OFPO and thionyl chloride, 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride are removed from the reactor together with hydrogen chloride gas. It may be discharged.

From the above, the first step is preferably carried out at a reaction temperature of 0 ° C. to 70 ° C., and more preferably 30 ° C. to 70 ° C. Within this range, the reaction can proceed effectively and 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride can be obtained with high selectivity.

The first step may be performed in a batch system or in a continuous system. The first step is carried out by accommodating a predetermined amount of OFPO and thionyl chloride as a feedstock in the reactor and gradually adding the other to the feedstock in the reactor when the batch method is performed. be able to. In the first step, for example, thionyl chloride is contained in a reactor in a predetermined amount and OFPO is gradually added to thionyl chloride, or OFPO is used as a feed and the predetermined amount is reacted. This can be done by accommodating in a vessel and gradually adding thionyl chloride to OFPO. At this time, the nitrogen-containing organic compound is preferably mixed with OFPO or thionyl chloride in advance. The entire predetermined amount of the nitrogen-containing organic compound may be mixed with either OFPO or thionyl chloride. Further, the nitrogen-containing organic compound may be mixed by dividing a predetermined amount into OFPO and thionyl chloride.

Further, when the first step is carried out in a batch manner as described above, the addition of the other compound of OFPO and thionyl chloride is added to the supplied product consisting of a predetermined amount of either OFPO or thionyl chloride. The rate is preferably 0.0015 to 5 mol / mol · min as the amount of addition per unit mole (1 mol) of the to be fed. 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 OFPO diadducts and the like which are by-products can be produced. 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.

When the first step is carried out in a continuous manner, OFPO, thionyl chloride and a nitrogen-containing organic compound are continuously supplied into the reactor at a predetermined supply rate at a predetermined molar ratio, and these are continuously supplied into the reactor in a predetermined manner. It can be done in contact for hours. In this case, it is preferable that the nitrogen-containing organic compound is mixed with OFPO or thionyl chloride in advance and supplied into the reactor from the viewpoint of operational efficiency. When the first step is carried out continuously, the supply rate of OFPO, thionyl chloride and nitrogen-containing organic compounds to the reactor is adjusted by the supply flow rate of each compound.

When the first step is carried out continuously, the supply rate of OFPO into the reactor is 0.0015 to 5 mol / mol · min with respect to the supply amount (molar amount) of thionyl chloride per minute. Or the supply rate of thionyl chloride is 0.0015 to 5 mol / mol · min with respect to the supply amount (molar amount) per minute of OFPO. Is preferable.

The reaction time in the first step is, for example, 1 to 8 hours, depending on the amount of OFPO and thionyl chloride. The reaction time in the first step is represented by the contact time between OFPO and thionyl chloride. For example, as described above, the first step is carried out in a batch manner, and a predetermined amount of one of OFPO and thionyl chloride is contained in the reactor as a feedstock, and the other is gradually charged into the feedstock in the reactor. When it is carried out by addition, it is the time from the start of supply of OFPO and thionyl chloride to the supply of the other until the generation of hydrogen chloride gas is stopped and the reaction is completed. When the first step is carried out continuously, the reaction time is the residence time of OFPO and thionyl chloride in the reactor.

When water is present in the reaction system between OFPO and thionyl chloride, thionyl chloride is decomposed into sulfur dioxide and hydrogen chloride by the reaction between thionyl chloride and water. In addition, when water is present in the reaction system, 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride decomposes into OFPO, sulfur dioxide and hydrogen chloride. Therefore, in order to suppress these decompositions, it is preferable to reduce the amount of water in the reaction system as much as possible. Examples of the method for reducing water include a method of replacing the atmosphere of the reaction system with a dry gas. The water content 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 OFPO.

In addition, in the reaction between OFPO and thionyl chloride, alcohol other than OFPO should not be contained from the viewpoint of increasing the selectivity of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. preferable. The amount of alcohol other than OFPO 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 OFPO.

The OFPO and the nitrogen-containing organic compound may exist in the state of a mixture of OFPO and water or a mixture of the nitrogen-containing organic compound and water due to a mixture of water (moisture) in the atmosphere during storage, for example. Even in such a case, for the same reason as described above, the 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, and then OFPO or the nitrogen-containing organic compound is supplied to the reactor. It is preferable to do so. As a method for reducing water, for example, a mixture of OFPO and water or a mixture of a 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. Examples thereof include a method in which a mixture of an organic compound and water is mixed and then contacted with a desiccant such as zeolite or silica to remove water.

When water is removed from the mixture of OFPO and water and the mixture of nitrogen-containing organic compound and water, the water content in the mixture of OFPO and water or the mixture of nitrogen-containing organic compound and water is the amount of OFPO or nitrogen-containing organic compound, respectively. With respect to the amount (the amount of OFPO or the amount of the nitrogen-containing organic compound), it is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, still more preferably 100 mass ppm or less. When water is removed by mixing a mixture of OFPO and water or a mixture of nitrogen-containing organic compound and water, 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. With respect to (the amount of OFPO and the total amount of DMF), it is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, still more preferably 100 mass ppm or less.

In the first step, a composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is obtained. The composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride may contain, for example, a nitrogen-containing organic compound, an unreacted raw material OFPO and thionyl chloride. , OFPO diadders may be included as by-products.

When DMF is used as the nitrogen-containing organic compound in the first step, a composition containing 2,2,3,3,4,5,5-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 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride with DMF. .. Hereinafter, 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is also referred to as an “intermediate”. The compound represented by the formula (3) is also referred to as an "intermediate-DMF adduct". In the second step, it is estimated that 448 occc is produced by thermally decomposing the intermediate-DMF adduct.

In the second step, 448 occc is obtained by thermally decomposing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride.

In the second step, only 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride may be thermally decomposed, and 2,2,3 obtained in the first step may be obtained. , 3, 4,4,5,5-octafluoropentane sulfonic acid chloride may be thermally decomposed in the state of the composition.

In the second step, 448 occc is produced as shown in the following formula (4) by thermally decomposing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. Specifically, 448 occc is produced by a sulfur dioxide desulfide reaction.

The thermal decomposition temperature is preferably 70 ° C. or higher. When the temperature is 70 ° C. or higher, the thermal decomposition of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is promoted. From the viewpoint of further promoting thermal decomposition, 80 ° C. or higher is more preferable, 100 ° C. or higher is further preferable, and 110 ° C. or higher is particularly preferable, and 115 ° C. or higher is most preferable from the viewpoint of increasing the reaction rate and the conversion rate of the intermediate. .. In addition, the thermal decomposition temperature suppresses the volatilization of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride before thermal decomposition, and improves the yield of 448 occc. It is preferably 170 ° C. or lower from the viewpoint that it can be used. The temperature of thermal decomposition refers to the temperature inside the reactor that performs thermal decomposition, more specifically, the temperature of the liquid phase inside the reactor.

Furthermore, when DMF is used as the nitrogen-containing organic compound, when the reaction temperature is 170 ° C. or higher, DMF is decomposed into formic acid, and formic acid is 2,2,3,3,4,5,5-octafluoropentane. By reacting with sulfonic acid chloride, 2,2,3,3,4,5,5-octafluoropentylformamide represented by the following formula (5) is produced as a by-product. The reaction temperature is preferably 170 ° C. or lower from the viewpoint of suppressing the formation of this by-product. Hereinafter, 2,2,3,3,4,5,5-octafluoropentylformate will be referred to as "intermediate-formic acid adduct".

In the second step, the thermal decomposition is preferably carried out in the presence of a solvent. The use of a solvent can promote the production of 448 occc. The solvent is a compound capable of dissolving 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride and 448occc, which is inactive in the reaction of the above formula (4). As the solvent, the above-mentioned nitrogen-containing organic compound can be used, and specifically, DMF, tetramethylurea, dimethylacetamide, pyridine and the like can be used. Of these, DMF is particularly preferable because 448 occc can be efficiently obtained. As the solvent, it is preferable to use the same compound as the nitrogen-containing organic compound used in the first step.

In the second step, when the pyrolysis is carried out in the presence of a solvent, the mass ratio of the solvent to 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride (solvent / 2,2). , 3,3,4,5,5-octafluoropentanesulfonic acid chloride) is preferably 0.01 to 1. If the amount of the solvent is within the above range, the production of 448 occc can be further promoted, and 448 occc can be obtained in a high yield.

The thermal decomposition in the second step may be performed in a batch system or a continuous system. From the viewpoint of manufacturing efficiency, it is preferable to carry out the continuous method. The pyrolysis pressure in the second step may be normal pressure, reduced pressure or pressurized.

When the second step is carried out in a batch manner, it depends on the amount and supply rate of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride subjected to thermal decomposition. For example, it is preferable to carry out thermal decomposition in 1 to 40 hours.

In the second step, a composition containing 448 occc can be obtained. In the obtained composition containing 448 occc, in addition to the target product 448 occc, unreacted 2,2,3,3,4,5,5-octafluoropentane sulfonic acid chloride, OFPO, OFPO diaddition The body, hydrogen chloride, sulfur dioxide, etc. may be included. When DMF is used as the nitrogen-containing organic compound or solvent, the composition containing 448 occc may contain DMF, an intermediate-DMF adduct, an intermediate-formic acid adduct and the like.

In order to neutralize hydrogen chloride and sulfur dioxide in the composition containing 448 occc, it is preferable to bring the composition containing 448 occc into contact with an aqueous alkaline solution. Examples of the alkaline aqueous solution used at this time include a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution. After contact with the alkaline aqueous solution, 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.

In order to neutralize impurities, the method of bringing the composition containing 448 occc into contact with the alkaline aqueous solution as described above can be carried out in a short time in the absence of a phase transfer catalyst or a water-soluble organic solvent. preferable. As a result, 448 occc itself does not come into sufficient contact with the alkaline aqueous solution, and by contacting it with an alkaline aqueous solution as described later, the hydrogen fluoride reaction generated from 448 occc to 1437 dycc can be suppressed.

By thermally decomposing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride in the second step, 2,2,3,3,4,5,5- The conversion rate of octafluoropentane sulfonic acid chloride can be 50% or more.

Further, according to the present invention, the selectivity of 448 occc can be increased to 50% or more by going through the second step. Here, 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 produced) / (the molar amount of the consumed intermediate) × 100).

When the composition containing 448 occc is brought into contact with the alkaline aqueous solution, the selectivity of 448 occc is determined in the organic phase obtained by contacting the distillate with respect to the molar amount of the intermediate consumed in the second step to the alkaline aqueous solution. It is calculated as the ratio of the molar amount of 448 occc ((molar amount of 448 occc) / (molar amount of the consumed intermediate) × 100).

Compounds other than 448occ contained in the organic phase, for example, OFPO, OFPO diadder, nitrogen-containing organic compound, solvent, DMF, intermediate-DMF adduct, intermediate-formic acid adduct can be separated by ordinary distillation. It can, which gives a high purity of 448 occc. Distillation of the composition containing 448 occc may be carried out at normal pressure, reduced pressure, or pressurized, and is preferably carried out under reduced pressure.

Further, the second step may be carried out by reactive distillation using a reactor provided with a distillation column. By extracting high-purity 448 occc as a distillate from the top of the distillation column by reactive distillation, the load in the subsequent distillation step can be reduced. The pressure in the reactor and in the distillation column for reactive distillation is preferably 30-2000 hPa, more preferably 100-1500 hPa, more preferably 200-1100 hPa, in terms of obtaining high purity 448 occc and increasing the recovery of 448 occc. More preferred. Further, the amount of 448 occc recovered can be further increased by extracting the composition containing 448 occc remaining as the residual liquid in the kettle and distilling it.

Through the first step, the second step and the distillation, the content of OFPO diadduct in the composition containing 448 occc can be reduced to less than 10% by mass. The content of the OFPO diadduct is preferably 7% by mass or less, and more preferably 5% by mass or less.

Further, according to the present invention, the content of 448 occc in the obtained composition containing 448 occc can be increased to 80% by mass or more by going through the first step, the second step and distillation. The content of 448occc is preferably 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more.

In the first step and the second step, the same reaction device may be used, or different reaction devices may be used. Examples of the reactor that can be used in both the first step and the second step include those having a reactor, a temperature controller, and the like.

As a reactor, OFPO and thionyl chloride can be introduced and reacted, and 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride can be thermally decomposed. Anything is fine. Examples of the material of such a reactor include glass, stainless steel such as SUS, glass lining material, resin lining material and the like.

As a temperature adjusting unit, the reaction temperature between OFPO and thionyl chloride can be adjusted, and the temperature at the time of thermal decomposition of 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. Anything that can be adjusted. Examples of such a thing include an oil bath and a heater. The temperature adjusting unit may be provided integrally with the reactor.

On the other hand, when different reaction devices are used for the first step and the second step, the reaction device used in each step need only have the functions necessary for the step. By using different reaction devices for the first step and the second step, for example, an industrially used device can be used, and mass production of 448 occc can be facilitated.

FIG. 1 is an apparatus used when the first step is performed by the batch method and the second step is performed by a continuous method, and shows an example of an industrially used device.

In FIG. 1, in the first step, a predetermined amount of thionyl chloride is contained in the reactor 11 as an object to be fed, and a mixed solution of OFPO and a nitrogen-containing organic compound is continuously supplied to the reactor 11 at a predetermined supply rate. However, the present invention is not limited to this. The reactor 10 takes out the reactor 11, the raw material supply means 12 for supplying the reactor 11 with a mixed solution of OFPO and a nitrogen-containing organic compound, and the liquid phase after the reaction from the reactor 11, and performs the second step. The liquid supply means 13 for supplying to the reactor 14 is provided. The reactor 10 further includes means 15 for extracting the liquid phase after the reaction from the reactor 14.

Further, the reactor 11 and the reactor 14 are configured to regulate the temperature inside the reactor by a temperature controller (not shown). The reactor 10 has an alkaline cleaning means 16 for contacting the liquid phase after the reaction taken out from the reactor 14 with the alkaline aqueous solution and a separation means 17 for separating the liquid phase after contacting with the alkaline aqueous solution into an organic phase and an aqueous phase. It has.

In the reactor 10, while thionyl chloride is contained in the reactor 11, a mixed solution of OFPO and a nitrogen-containing organic compound is supplied into the reactor 11 from the raw material supply means 12 at a predetermined supply flow rate, and thionyl chloride is supplied. Is added to. The supply flow rate of the mixed solution of OFPO and the nitrogen-containing organic compound can be automatically controlled by installing, for example, a mass flow controller. In the reactor 11, thionyl chloride reacts with OFPO in the presence of a nitrogen-containing organic compound to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. The resulting liquid phase consisting of the composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is then supplied to the reactor 14 by the liquid feeding means 13.

In the reactor 14, the composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is heated to a predetermined temperature by a temperature controller (not shown), and 2,2. 3,3,4,5,5-octafluoropentane sulfonic acid chloride is pyrolyzed to produce 448 occc. The liquid phase composed of the produced composition containing 448 occc is taken out from the reactor 14 by the liquid feeding means 15, passed through the alkaline cleaning means 16 and brought into contact with the alkaline aqueous solution, and then the organic phase and water are brought into contact with the alkaline aqueous solution by the separating means 17. Separated into phases. The target product, 448 occc, can be obtained in the organic phase separated in this way.

FIG. 2 is an apparatus used when both the first step and the second step are continuously performed, and shows an example of an industrially used apparatus.

The reactor 20 shown in FIG. 2 comprises a reactor 21 that performs the first step, a raw material supply means 22a that supplies thionyl chloride to the reactor 21, a raw material supply means 22b that supplies OFPO, and a nitrogen-containing organic compound. It is provided with a raw material supply means 22c to be supplied. Further, the reactor 20 includes a liquid supply means 23 that takes out the liquid phase after the reaction from the reactor 21 and supplies it to the reactor 24 that performs the second step. The reactor 20 further includes means 25 for extracting the liquid phase after the reaction from the reactor 24.

Further, the reactor 21 and the reactor 24 are configured to regulate the temperature inside the reactor by a temperature controller (not shown). The reactor 20 includes an alkaline cleaning means 26 for bringing the liquid phase after the reaction taken out from the reactor 24 into contact with the alkaline aqueous solution, and a separation means 27 for separating the liquid phase after contact with the alkaline aqueous solution into an organic phase and an aqueous phase. It has.

Thionyl chloride, OFPO and nitrogen-containing organic compounds are supplied into the reactor 21 at a predetermined supply flow rate by the raw material supply means 22a to 22c. At this time, the nitrogen-containing organic compound may be mixed with any one of thionyl chloride and OFPO and supplied to the reactor 21. The flow rate of thionyl chloride, OFPO, and nitrogen-containing organic compound supplied to the reactor 21 can be automatically controlled by installing, for example, a mass flow controller. In the reactor 21, thionyl chloride reacts with OFPO in the presence of a nitrogen-containing organic compound to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride. The resulting liquid phase consisting of the composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is then supplied to the reactor 24 by the liquid feeding means 23.

In the reactor 24, the composition containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is heated to a predetermined temperature by a temperature controller (not shown), and 2,2. 3,3,4,5,5-octafluoropentane sulfonic acid chloride is pyrolyzed to produce 448 occc. The liquid phase composed of the produced composition containing 448 occc is taken out from the reactor 24 by the liquid feeding means 25, passes through the alkaline cleaning means 26 and comes into contact with the alkaline aqueous solution, and then the organic phase and the aqueous phase are brought into contact with the alkaline aqueous solution by the separating means 27. Is separated into.
The target product, 448 occc, can be obtained in the organic phase separated in this way.

<Manufacturing method of 1437 dycc>
The method for producing 1-chloro-2,3,3,4,5,5-heptafluoropentene (1437 dycc) of the present invention is the above-mentioned method of the present invention, 5-chloro-1,1,2, 2,3,3,4,5-octafluoropentane (448 occc) is obtained, and the obtained 448 occc is subjected to a hydrogen fluoride reaction in an aqueous solution of a base to obtain 1437 dycc.

The reaction according to the method for producing 1437 dycc of the present embodiment is represented by the following formula (6).

The 1437dycc obtained by the production method of the present embodiment has a high proportion of halogen that suppresses flammability and has a carbon-carbon double bond in the molecule that is easily decomposed by OH radicals in the atmosphere, and is flammable. Is low, has little impact on the ozone layer, and has little impact on global warming. Therefore, it is highly useful as a solvent and an operating medium (a heat medium used for heat exchange, etc., an operating medium used for a heat cycle system, etc.).

The 1437dycc obtained by the production method of the present embodiment may be Z-form only, E-form only, or a mixture of Z-form and E-form. The Z-form 1437dycc (Z) has higher chemical stability than the E-form 1437dycc (E), and is more preferable as a solvent or an operating medium. Then, according to the production method of the present embodiment, 1437 dycc including 1437 dycc (Z) can be efficiently produced. Further, according to the production method of the present embodiment, 1437 dycc having a higher content ratio of 1437 dycc (Z) than 1437 dycc (E) can be obtained.

The method for producing 1437 dycc of the present embodiment is to defluoride 448 occc in an aqueous solution of a base according to the reaction represented by the formula (6) (hereinafter referred to as reaction (6)) as described above. Is.

As the starting material for the reaction (6), any one containing 448 occc may be used. For example, 448 occc obtained by the method for producing 448 occc of the above embodiment can be used. The crude liquid containing 448 occc obtained by the method for producing 448 occc of the above embodiment may be used as it is, or the crude liquid may be purified by a known method before use. From the viewpoint of economy, the starting material for the reaction (6) may contain impurities such as by-products other than 448 occc and unreacted raw materials in the method for producing 448 occc, but those containing no impurities other than 448 occc are used. Conceptually preferable. The impurity is preferably a compound that does not inhibit the defluorinated hydrogen reaction of 448 occc. Examples of impurities include 1437 dycc, OFPO, DMF and the like.

When the starting material contains impurities, the ratio of 448 occc to the total amount of impurities and 448 occc is preferably 85% by mass or more and less than 100% by mass, and more preferably 90% by mass or more and 99% by mass or less.

Further, when the starting material of the reaction (6) contains at least one compound selected from 1437 dycc, OFPO and DMF, the ratio of the total amount of 1437 dycc, OFPO and DMF is the starting material in order to efficiently produce 1437 dycc. It is preferably more than 0% by mass and 15% by mass or less, and more preferably 0.1% by mass or more and 7% by mass or less with respect to the total amount.

When the starting material of the reaction (6) contains OFPO, the content ratio of OFPO is preferably more than 0% by mass and 3% by mass or less, preferably 0.1% by mass or more and 1% by mass or less, based on the total amount of the starting materials. More preferred. When the content of OFPO is within the above range, the production 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 capable of carrying out the defluorination hydrogen reaction in 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 kind or two or more kinds.

Examples of the metal oxide include alkali metal oxides and alkaline earth metal oxides. Sodium oxide is preferable as the alkali metal oxide, and calcium oxide is preferable as the alkaline earth metal oxide. Further, the metal oxide may be one kind, two or more kinds, and further may be a composite oxide of two or more kinds of metals.

Examples of the metal carbonate include alkali metal carbonates and alkaline earth metal carbonates. Alkali metal carbonates include lithium, sodium, potassium, rubidium, cesium or francium carbonates. Alkaline earth metal carbonates include beryllium, magnesium, calcium, strontium, barium or radium carbonates. The metal carbonate may be one kind or two or more kinds.

Of the above bases, it is preferable to use a metal hydroxide. As the metal hydroxide, at least one selected from potassium hydroxide and sodium hydroxide is preferable. Potassium hydroxide or sodium hydroxide may be used alone, or potassium hydroxide and sodium hydroxide may be used in combination.

The amount of base with respect to 448 occc is preferably 0.5 to 10 mol, more preferably 0.5 to 5.0 mol, based on 1 mol of 448 occc, from the viewpoint of improving the conversion rate of 448 occc and the selectivity of 1437 dycc. More preferably 0.5 to 2.5 mol, most preferably 0.5 to 2.0 mol.

In reaction (6), the base is used as an aqueous solution of the base. As the aqueous solution of the base, an aqueous alkali metal hydroxide solution is preferable, and an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is more preferable.

The amount of the base with respect to the total amount of the aqueous solution of the base is preferably 0.5 to 40% by mass, more preferably 10 to 40% by mass. When the amount of the base with respect 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 can be easily obtained, and the target product can be easily separated by the two-layer separation. If it is not more than the above upper limit value, the base is easily sufficiently dissolved and the metal salt is less likely to be precipitated, which is likely to be advantageous in an industrial process. Further, the amount of the base with respect to the total amount of the aqueous solution of the base is more preferably 20 to 38% by mass, and most preferably 20 to 35% by mass. When the amount of base is 20% by mass or more based on the total amount of the aqueous solution of base, the conversion rate of 448 occc becomes higher and the reaction rate becomes faster.

FIG. 3 shows an example (reaction device 30) of an apparatus industrially used in the 1437 dycc manufacturing method of the present embodiment.

In the production method of the present embodiment, as shown in FIG. 3, 448 occc is previously contained in the base aqueous solution contained in the raw material tank (indicated by reference numeral 32) and other compounds involved in the reaction used as necessary. It is supplied to the reactor 31 and reacted. The resulting composition containing 1437 dycc is recovered from the reactor 31 and, if necessary, cooled via the condenser 33. Further, it is preferable to recover the product from the recovery tank 35 containing the product from which the water has been removed by passing it through the dehydration tower 34 as needed.

As the reactor 31, a known reactor used for the defluorinated hydrogen reaction in the liquid phase reaction is preferable. Examples of the material of the reactor 31 include iron, nickel, alloys containing these as main components, glass and the like. If necessary, the reactor 31 may be subjected to lining treatment such as resin lining and glass lining. Further, it is preferable to provide a stirring means in the reactor 31 and carry out the reaction while stirring so that the reaction is carried out in a state where the raw materials, products, bases, solvents and the like are uniformly distributed in the reaction system.

Here, the reaction temperature in the reaction (6) is preferably 0 to 80 ° C, more preferably 0 to 60 ° C, further preferably 10 to 50 ° C, and particularly preferably 20 to 40 ° C. By setting the reaction temperature within the above range, the formation of by-products can be suppressed, the conversion rate of 448 occc can be improved, and the yield and selectivity of 1437 dycc can be improved. Furthermore, among the 1437 dycc isomers, the Z isomer can be selectively obtained. Here, the reaction temperature is the temperature inside the reactor, and more specifically, the temperature of the liquid phase inside the reactor. In the apparatus shown in FIG. 3, the temperature inside 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 even more preferably 0 to 1 MPa. The pressure in the reactor is preferably greater than or equal to the vapor pressure of 448 occc at the reaction temperature.

The reaction (6) can be carried out by any of a semi-continuous method, a batch method, and a continuous method. The reaction time can be appropriately adjusted by a general method according to each method. The reaction time is preferably 1 to 50 hours for the batch type and 1 to 20 hours for the continuous type because it is easy to control the conversion rate of 448 occc as a raw material and the selectivity of 1437 dycc. In the case of the continuous type, 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 448оccc and the aqueous solution of the base can be efficiently contacted. Further, it may be carried out in the presence of a water-soluble organic solvent such as tetraglime as long as it does not affect the reaction. It is preferable to use a phase transfer catalyst in order to increase the reaction rate.

Examples of the phase transfer catalyst include a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary ammonium salt, a sulfonium salt, and a crown ether, and examples thereof include a quaternary ammonium salt, a quaternary phosphonium salt, and a quaternary ammonium salt. Salts and sulfonium salts are preferable, and quaternary ammonium salts are more preferable.

Examples of the quaternary ammonium salt include compounds represented by the following formula (i).

（ただし、式（ｉ）中、Ｒ^１１〜Ｒ^１４は、それぞれ独立して、１価の炭化水素基、又は反応に不活性な官能基が結合した１価の炭化水素基を表し、Ｙ^１−は、１価の陰イオンを表す。）

(However, in formula (i), R ^{11 to} R ¹⁴ each independently represent a monovalent hydrocarbon group or a monovalent hydrocarbon group to which a functional group inert to the reaction is bonded, and Y ^{1 -} represents a monovalent anion).

When R ^{11 to} R ¹⁴ are hydrocarbon groups, examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group and an aryl group, and an alkyl group and an aryl group are preferable. The number of carbon atoms of each of R ^{11 to} R ¹⁴ is preferably 1 to 100, more preferably 4 to 30. R ^{11 to} R ¹⁴ may be the same group or different groups, respectively.

When R ^{11 to} R ¹⁴ are monovalent hydrocarbon groups to which a functional group inert to the reaction is bonded, the functional group is appropriately selected depending on the reaction conditions, but is a halogen atom, an alkoxycarbonyl group, and an acyloxy. Examples thereof include a group, a nitrile group, an acyl group, a carboxyl group and an alkoxyl group.

The quaternary ammonium (R ¹¹ R ¹² R ¹³ R ¹⁴ N ⁺ ) in the above formula (i) includes tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, and methyltri-n-. Octylammonium, cetyltrimethylammonium, benzyltrimethylammonium, benzyltriethylammonium, cetylbenzyldimethylammonium, cetylpyridinium, n-dodecylpyridinium, phenyltrimethylammonium, phenyltriethylammonium, N-benzylpicolinium, pentamethonium, hexamethonium, etc. Can be mentioned.

As Y ^1-in the above formula (i) is fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion, hydroxide ion, acetate ion , Saprophytic acid ion, benzenesulfonic acid ion, p-toluenesulfonic acid ion and the like, preferably fluorine ion, chlorine ion, bromine ion, iodine ion, hydrogen sulfate ion, hydroxide ion, fluorine ion, chlorine ion, etc. Bromine ions, iodine ions and hydroxide ions are more preferable, and chlorine ions or bromine ions are even more preferable.

As the compound represented by the above formula (i), a combination of the following quaternary ammonium (R ¹¹ R ¹² R ¹³ R ¹⁴ N ⁺ ) and the following Y ^1- is preferable from the viewpoint of versatility and reactivity. ..
Quaternary ammonium (R ¹¹ R ¹² R ¹³ R ¹⁴ N ⁺ ): tetramethylammonium, tetraethylammonium, tetra-n-propylammonium, tetra-n-butylammonium, methyltri-n-octylammonium.
Y ^1- : Fluorine ion, chlorine ion, bromine ion, iodine ion, hydroxide ion.

The quaternary ammonium salts include tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), and methyltri-n-octylammonium from the viewpoint of industrial availability, price, and ease of handling. It is preferably at least one selected from the group consisting of chloride (TOMAC).

Examples of the quaternary phosphonium salt include compounds represented by the following formula (ii).

（ただし、式（ii）中、Ｒ^２１〜Ｒ^２４は、それぞれ独立して、１価の炭化水素基を表し、Ｙ^２−は、１価の陰イオンを表す。Ｒ^２１〜Ｒ^２４は、それぞれ同じ基であってもよいし、異なる基であってもよい。）

(However, in formula (ii), R ^{21 to} R ²⁴ each independently represent a monovalent hydrocarbon group, Y ^2- represents a monovalent anion, and R ^{21 to} R ²⁴ represent monovalent anions. They may be the same group or different groups.)

Examples of the hydrocarbon group in R ^{21 to} R ²⁴ include 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.

The quaternary phosphonium (R ²¹ R ²² R ²³ R ²⁴ P ⁺ ) in the above formula (ii) includes tetraethylphosphonium, tetra-n-butylphosphonium, ethyltri-n-octylphosphonium, cetiltriethylphosphonium, and cetiltri-n-. Examples thereof include butylphosphonium, n-butyltriphenylphosphonium, n-amyltriphenylphosphonium, methyltriphenylphosphonium, benzyltriphenylphosphonium, tetraphenylphosphonium and the like.

Y as ^2-, chlorine ion, fluorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydrogen sulfate ion, hydroxide ion, acetate ion, benzoate ion, benzene Examples thereof include sulfonic acid ion and p-toluene sulfonic acid ion, and fluorine ion, chlorine ion and bromine ion are preferable.
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.

Examples of the quaternary arsonium salt include compounds represented by the following formula (iii).

ただし、式（iii）中、Ｒ^３１〜Ｒ^３４は、式（ii）におけるＲ^２１〜Ｒ^２４と同様であり、好ましい態様も同様である。Ｙ^３−は１価の陰イオンを表す。Ｙ^３−としては、ハロゲンイオンが好ましく、フッ素イオン、塩素イオン、臭素イオンがより好ましい。

However, in the formula (iii), R ^{31 to} R ³⁴ are the same as those of R ^{21 to} R ²⁴ in the formula (ii), and the preferred embodiment is also the same. Y ^3- represents a monovalent anion. Y as ³ is preferably a halogen ion, fluorine ion, chlorine ion, bromine ion and more preferable.

Examples of the quaternary arsonium salt represented by the above formula (iii) include triphenylmethylarsonium fluoride, tetraphenylarsonium flolide, triphenylmethylarsonium chloride, tetraphenylarsonium chloride, tetraphenylarsonium bromide and the like. Can be mentioned.
As the quaternary arsonium salt, triphenylmethylarsonium chloride is preferable.

Examples of the sulfonium salt include compounds represented by the following formula (iv).

（ただし、式（iv）中、Ｒ^４１〜Ｒ^４３及びＹ^４−は、式（iii）におけるＲ^３１〜Ｒ^３４及びＹ^３−と同様であり、好ましい態様も同様である。）

(However, in formula (iv), R ^{41 to} R ⁴³ and Y ^4- are the same as R ^{31 to} R ³⁴ and Y ^3- in formula (iii), and the preferred embodiments are also the same.)

Examples of the sulfonium salt represented by the above formula (iv) include di-n-butylmethylsulfonium iodide, tri-n-butylsulfonium tetrafluoroborate, dihexylmethylsulfonium iodide, dicyclohexylmethylsulfonium iodide, and dodecylmethylethylsulfonium. Examples thereof include chloride and tris (diethylamino) sulfonium difluorotrimethyl silicate.
As the sulfonium salt, dodecylmethylethyl sulfonium chloride is preferable.

Examples of the crown ether include 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6 and the like.
Among the above-mentioned phase transfer catalysts, TBAC, TBAB, and TOMAC are preferable from the viewpoint of industrial availability, price, and ease of handling.

The amount of the phase transfer catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5.0 parts by mass, and further preferably 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. When the amount of the phase transfer catalyst is within the above range, a sufficient reaction rate can be easily obtained. If it is out of the above range, it is difficult to obtain the reaction promoting effect, and it tends to be disadvantageous in terms of cost. When a phase transfer catalyst is used, it is preferable that the phase transfer catalyst is mixed with 448 occc in advance and supplied to the reactor in the state of a mixed solution with 448 occc. Further, when the amount of the phase transfer catalyst is 0.1 to 1.0 part by mass with respect to 100 parts by mass of 448 occc, the selectivity and yield of 1437 dycc are high, which is most preferable.

When a phase transfer catalyst is used, the material of the reaction process, the reactor, and the reactor may be the same as when the phase transfer catalyst is not used. Further, the reaction conditions such as the concentration of the base, the amount used, and the reaction temperature may be the same as when the phase transfer catalyst is not used.

In reaction (6), compounds involved in the reaction such as, for example, 448 occc, an aqueous solution of base, a water-soluble organic solvent and / or a phase transfer catalyst, if necessary, are supplied to the reactor, and the mixture is stirred so as to be uniform. However, it can be advanced by setting desired temperature conditions and pressure conditions.

In the reaction (6), the reaction (6) may be carried out by compatibilizing the aqueous phase and the organic phase with a water-soluble organic solvent instead of the phase transfer catalyst. When a water-soluble organic solvent is used, it is preferable to sufficiently stir the compounds involved in the reaction in the reaction system in order to make them uniform. Examples of the water-soluble organic solvent include dimethyl sulfoxide, tetraglime, acetonitrile and the like. Of these, dimethyl sulfoxide and tetraglime are preferable because they have a boiling point suitable for the reaction (6). Further, in the reaction (6), the phase transfer catalyst and the water-soluble organic solvent may be used in combination.

When the reaction solution is allowed to stand after the reaction is completed, it separates into an organic phase and an aqueous phase. In addition to the unreacted 448 occc and the target product 1437 dycc, the organic phase may contain by-products. By-products include 1-chloro-3,3,4,5,5-hexafluoropentene and 5-chloro-1,1,2,3,3,4,5-heptafluoropentene (HCFO). -1437cycc, hereinafter also referred to as "1437cycc"). When a composition containing 448 occc and impurities is used as a raw material, 2,3,3,4,5,5-heptafluoro-1- (5-heptafluoro-1-) represented by the following chemical formula (v) is used as a by-product. 2,2,3,3,4,5,5-octafluoropentoxy) Pentene and the like may be included.

Except for the target product, 1437 dycc, it can be easily removed from the reaction product of the reaction (6) by a known method such as separation by distillation. The unreacted 448 occc can be reused as a starting material for the reaction (6). At that time, the crude solution after separating 1437 dycc from the reaction product may be used as it is, or unreacted 448 occc may be purified from the crude solution and used.

As described above, 1437 cycc is mentioned as a by-product, but in the defluorinated hydrogen reaction in this reaction (6), the by-product of 1437 cycl is sufficiently suppressed, and for example, it is contained in the reaction product. The amount of 1437 cycl can be 100 ppm or less. Therefore, the production method of the present embodiment is an excellent method capable of selectively producing 1437 dycc, which is the target compound.

According to the production method of the present embodiment, 1437 dycc, which is useful as a solvent having a low global warming potential and a working medium, can be obtained from 448 occc by an economically advantageous method that can be industrially implemented, with a high selectivity and a high yield. Obtained at.

Hereinafter, the present invention will be specifically described with reference to Examples. The present invention is not limited to these examples.

<Manufacturing method of 448 occc>
(First step; intermediate manufacturing step)
[Example 1-1]
A four-necked flask (reactor) equipped with a stirrer and a Dimroth condenser was immersed in an oil bath to prepare a reactor. Then, after accommodating thionyl chloride in 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 was adjusted so that the reaction temperature 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 an intermediate crude solution containing 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride is added. Obtained. Then, the composition of the intermediate crude liquid was analyzed by 1H-NMR and 19F-NMR (JNM-ECP400, manufactured by JEOL Ltd.). Table 1 summarizes the reaction conditions and the composition of the crude intermediate solution.

In the table, the OFPO conversion rate (%) is the ratio of the molar amount of OFPO consumed in the first step to the molar amount of OFPO charged in the first step ((molar amount of OFPO consumed). / (Molar amount of OFPO charged) × 100).

Further, in the table, the intermediate selectivity (%) is the intermediate (2,2,3,3,4,5,4) 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 the produced intermediate) / (molar amount of OFPO consumed) × 100).
The selectivity of other compounds is calculated in the same manner for each compound.
The "active ingredient" represents an intermediate and an intermediate-DMF adduct, and the "active ingredient selectivity" was calculated by the total molar amount of the active ingredients.

The intermediate yield (%) is the ratio of the molar amount of the intermediate produced in the first step to the molar amount of OFPO charged in the first step ((molar amount of the produced intermediate) /. (Molar amount of OFPO charged) × 100). The reaction time is the elapsed time from the start of dropping OFPO to the end of stirring, that is, the elapsed time from the end of the generation of hydrogen chloride gas to the end of the reaction.

[Example 1-2-1-7]
The reactor and procedure were the same as in Example 1 except that the reaction conditions were changed as shown in Table 1. Table 1 summarizes the reaction conditions, the composition of the crude intermediate solution, and the analysis results.

(Second step; 448 occc manufacturing process)
[Example 2-1]
In a four-necked flask equipped with a stirrer and a distillation column, in the presence of DMF, OFPO and thionyl chloride were reacted at a reaction temperature of 30 to 70 ° C., and DMF was added as an intermediate crude liquid and a solvent to 130 ° C. Along with heating, the distillation line (Dimroth condenser) was cooled to −20 ° C. As a result, 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride was thermally decomposed. Table 2 shows the composition of the intermediate crude liquid used and the amount of the intermediate crude liquid. The molar amount of the intermediate crude liquid was represented by the total molar amount of the compounds contained in the intermediate crude liquid.

Then, the fraction was neutralized by contacting it with a 20 mass% potassium hydroxide aqueous solution, and the organic phase portion was recovered from the neutralized fraction and its composition was analyzed. The analysis was performed using gas chromatography (GC). As the column, DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies Co., Ltd.) was used. Table 2 shows the amount of 448 occc obtained in the fraction.

Further, the composition of the residual liquid in the kettle remaining in the four-necked flask was analyzed by 1H-NMR and 19F-NMR (JNM-ECP400, manufactured by JEOL Ltd.). Further, the amount of each compound recovered in the second step was calculated from the amount of 448 occc in the distillate and the composition of the residual liquid in the kettle. The results are shown in Table 2.

In Table 2, the intermediate conversion rate (%) is the intermediate consumed in the second step with respect to the molar amount of the intermediate used in the second step (the molar amount of the intermediate in the crude intermediate liquid). The ratio of the molar amount of the body ((molar amount of the consumed intermediate) / (molar amount of the charged intermediate) × 100).

Further, in Table 2, the OFPO diadduct selectivity (%) is the ratio of the molar amount of the OFPO diadduct produced in the second step to the molar amount of the intermediate consumed in the second step (((). The molar amount of the OFPO diadduct produced) / (the molar amount of the consumed intermediate) × 100). The selectivity of other compounds is calculated in the same manner for each compound.

Further, 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). The molar amount of the intermediate obtained) × 100).

[Example 2-2]
The second step was carried out using 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, reaction results, and the like.

[Example 2-3]
In a four-necked flask equipped with a stirrer and a distillation column, in the presence of DMF, OFPO and thionyl chloride were reacted at a reaction temperature of 30 to 70 ° C., and DMF was added as an intermediate crude liquid and a solvent to 110 ° C. Along with heating, the distillation line (Dimroth condenser) was cooled to −20 ° C. As a result, 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride was thermally decomposed. Table 2 shows the composition of the intermediate crude liquid used and the amount of the intermediate crude liquid. The molar amount of the intermediate crude liquid was represented by the total molar amount of the compounds contained in the intermediate crude liquid.

The composition of the residual liquid in the kettle remaining in the four-necked flask was analyzed by 1H-NMR and 19F-NMR (JNM-ECP400, manufactured by JEOL Ltd.). Further, the amount of each compound recovered in the second step was calculated from the composition of the residual liquid in the kettle. The results are shown in Table 2.

[Example 2-4]
The second step was carried out using 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, reaction results, and the like.

[Example 2-5]
The second step was carried out using 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, reaction results, and the like.

As shown in the above examples, after reacting OFPO with thionyl chloride in the presence of DMF to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, By thermally decomposing this 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride to obtain a reaction solution containing 448 occc, a complicated post-treatment step is not required and high selection is required. It becomes possible to produce 448 chloride at a rate, and 448 chloride can be efficiently produced.

[Example 2-6]
The second step was carried out using 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, the distillate line was not used. The composition of the residual liquid in the kettle remaining in the four-necked flask was analyzed by 1H-NMR and 19F-NMR (JNM-ECP400, manufactured by JEOL Ltd.). Further, the amount of each compound recovered in the second step was calculated from the composition of the residual liquid in the kettle. Table 3 summarizes the reaction conditions, reaction results, and the like.

[Examples 2-7 to 2-8]
The second step was carried out in the same reactor and procedure as in Example 2-1 except that the reaction conditions were changed as shown in Table 3 (Table 2), and the amount of each compound recovered in the second step was measured. Calculated. Table 3 summarizes the reaction conditions, reaction results, and the like.

<Manufacturing method of 1437 dycc>
[Example 3-1]
100.7 g of 448 occc and 1.0 g of tetra-n-butylammonium bromide (TBAB) were placed in a 0.2 liter four-necked flask equipped with a stirrer and a Dimroth condenser, and the flask was cooled to 10 ° C. The reaction temperature was maintained at 10 ° C., and 153.9 g of a 34 mass% potassium hydroxide (KOH) aqueous solution was added dropwise over 30 minutes. Then, stirring was continued for 38 hours, and the organic layer was recovered. The 448occc used above is obtained by reacting OFPO with thionyl chloride in the presence of DMF to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, and then this 2 , 2,3,3,4,5,5-octafluoropentanesulfonic acid chloride was thermally decomposed to produce.

Table 4 shows the results of analysis using gas chromatography after washing the recovered organic layer with water. In the table, the conversion rate of 448 occc is the ratio (mol%) of the amount of 448 occc consumed in the reaction to the total amount of 448 occc supplied to the reactor. The selectivity of each compound was the ratio (mol%) of each component produced to the converted 448 occc, and was calculated from the GC analysis results. Table 4 also shows the actual amount charged and the reaction conditions. In Table 4, "TBAB / 448occc" represents the amount of TBAB charged (parts by mass) with respect to 100 parts by mass of 448occc.

[Example 3-2-3-4]
As shown in Table 4, the reaction was carried out in the same manner as in Example 3-1 except that the actual charge 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 the amount of solid precipitate was large and the conversion rate of 448 occc did not change depending on the reaction start time. By the way, the end point of the reaction was where the conversion rate of 448 occc was 99% or more.

As can be seen from Table 4, according to Examples 3-1 to 3-4, the desired 1437 dycc could be produced with high selectivity and high yield while suppressing the amount of solid content produced. It was also found that the lower the reaction temperature, the smaller the amount of solid content produced, and the higher the selectivity and yield of 1437 dycc.

[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 actual charge amount and the TBAB charge amount were changed, respectively, to obtain a composition containing 1437 dycc.
In Example 3-5, the operation was terminated when no change in the conversion rate of 448 occc due to the reaction start time was observed. By the way, the end point of the reaction was where the conversion rate of 448 occc was 97% or more. In addition, Table 5 also shows Examples 3-3 having the same reaction temperature for reference.

[Examples 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 actual charge amount and the KOH charge amount were changed, respectively, to obtain a composition containing 1437 dycc. The end point of the reaction was where the conversion rate 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 charge amount and the KOH concentration were changed, respectively, to obtain a composition containing 1437 dycc. The operation was terminated when no change in the conversion rate of 448 occc due to the reaction start time was observed.

As can be seen from Example 3-5 in Table 5, the reaction time can be shortened as the amount of TBAB charged is larger. It was also found that 1437 dycc can be produced without changing the selectivity and yield of 1437 dycc by ensuring a sufficient reaction time even when the amount of TBAB charged is small.

As can be seen from Examples 3-6 to 3-7 in Table 5, by reducing the amount of KOH charged, the target 1437 dycc can be produced with high selectivity and high yield while suppressing the amount of solids produced. It was. Further, it can be seen that the volumetric efficiency is also improved by reducing the amount of KOH charged, and as a result, the productivity is improved.

As can be seen from Example 3-7 in Table 5, the higher the KOH concentration, the higher the conversion rate of 448оcccc and the faster the reaction rate.

From the above, the method for producing 1437 dycc in this example can efficiently produce 1437 dycc.

10, 20, 30 ... Reactor, 11,21 ... Reactor, 12, 22a, 22b, 22c ... Raw material supply means, 13, 23 ... Liquid supply means, 14, 24 ... Reactor, 15, 25 ... Liquid delivery means , 16, 26 ... Alkaline cleaning means, 17, 27 ... Separation means, 31 ... Reactor, 32 ... Raw material tank, 33 ... Cooler, 34 ... Dehydration tower, 35 ... Recovery tank.

Claims (12)

2,2,3,3,4,5,5-octa 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 first step of reacting fluoropentanol with thionyl chloride to produce 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, and
By thermally decomposing the 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride, 5-chloro-1,1,2,2,3,3,4,5- The second step of obtaining octafluoropentane and
A method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane, which comprises. The method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to claim 1, wherein the reaction temperature is 0 to 70 ° C. in the first step. In the first step, the molar ratio of thionyl chloride to 2,2,3,3,4,5,5-octafluoropentanol (thionyl chloride / 2,2,3,3,4,4,5) , 5-Octafluoropentanol) is 0.1 to 5, according to claim 1 or 2, the method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane. .. In the first step, one of 2,2,3,3,4,5,5-octafluoropentanol and thionyl chloride is used as a feed, and the other is added per unit molar amount of the feed. 5-Chloro-1,1,2,2,3,3,4,5-octa according to any one of claims 1 to 3, which are added at a rate of 0.0015 to 5 mol / mol · min as an amount. Method for producing fluoropentane. Any one of claims 1 to 4 in which the contact time between 2,2,3,3,4,5,5-octafluoropentanol and thionyl chloride in the first step is 1 to 8 hours. 5. The method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to. In the first step, the mass ratio of the nitrogen-containing organic compound to 2,2,3,3,4,5,5-octafluoropentanol (nitrogen-containing organic compound / 2,2,3,3,4) , 4,5,5-octafluoropentanol) is 0.001 to 1, 5-chloro-1,1,2,2,3,3,4 according to any one of claims 1 to 5. , 4-Octafluoropentane manufacturing method. 5-Chloro-1,1,2,2,3,3,4 according to any one of claims 1 to 6, wherein in the second step, the reaction temperature of thermal decomposition is 70 to 170 ° C. Method for producing 4-octafluoropentane. 5-Chloro-1,1,2,2,3,3,4,4-octafluoro according to any one of claims 1 to 7, wherein the thermal decomposition reaction is carried out in a solvent in the second step. How to make pentane. The method for producing 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to claim 8, wherein in the second step, the solvent is a nitrogen-containing organic compound. The 5-chloro-1,1,2,2,3,3,4,5-octafluoropentane according to claim 8 or 9, wherein in the second step, the solvent is N, N-dimethylformamide. Production method. In the second step, the mass ratio of the solvent to the 2,2,3,3,4,5,5-octafluoropentanesulfonic acid chloride (solvent / 2,2,3,3,4,4). , 5,5-octafluoropentanesulfonic acid chloride) is 0.01 to 1, 5-chloro-1,1,2,2,3,3,4 according to any one of claims 8 to 10. , 4-Octafluoropentane manufacturing method. 5-Chloro-1,1,2,2,3,3,4,5-octafluoropentane was obtained by the production method according to any one of claims 1 to 11, and the obtained 5-chloro- 1,1,2,2,3,3,4,5-octafluoropentane is reacted with hydrogen fluoride in a base aqueous solution to cause 1-chloro-2,3,3,4,5, A method for producing 1-chloro-2,3,3,4,5,5-heptafluoropentene, which comprises obtaining 5-heptafluoropentene.

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