JP2004269507A - Method for producing fluorine-containing ester compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an ester compound (IV), capable of reducing the using amount of a hydrocarbon-based solvent used in the preparation of the ester compound (IV), and also performed in simple equipment including an apparatus for recovering the hydrocarbon-based solvent from recovered solvent. <P>SOLUTION: This method for producing the fluorine-containing ester compound (IV) expressed by formula (IV) by performing an ester interchange reaction of an ester compound (I) expressed by formula (I) with a benzyl alcohol compound (II) expressed by formula (II) in the presence of the hydrocarbon-based solvent in a reaction pot is provided by distilling off a mixture of methanol or ethanol produced as a by-product in the ester interchange reaction and the hydrocarbon-based solvent to the outside of the reaction pot, bringing the mixture in contact with water and returning the separated hydrocarbon-based solvent to the reaction pot. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

  The present invention relates to a method for producing a fluorine-containing ester compound useful as an active ingredient of a pesticidal agent.

（式中、Ｒ^１はメチル基または炭素数３〜４のアルケニル基を表し、Ｒ^２は水素原子またはメチル基を表し、Ｒ^４は、ハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基、ハロゲン原子で置換されていてもよい炭素数２〜３のアルケニル基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルコキシル基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルキルチオ基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルコキシル基が結合したメチル基、水素原子またはハロゲン原子を表す。）
で示されるシクロプロパンカルボン酸 ２，３，５，６−テトラフルオロベンジルエステル化合物が有害生物防除剤の有効成分として有用であることが知られており（例えば、特許文献１）、その製造方法としては、特許文献２において、次のエステル化合物（I）と、ベンジルアルコール化合物（II）を炭化水素系反応溶媒の存在下に、反応釜内でエステル交換反応させ、副生したメタノールもしくはエタノールと炭化水素系反応溶媒を反応釜外へ留出させ、同時に、得られた反応混合物中に新たに炭化水素系反応溶媒を加えてさらに反応させる方法が開示されている。 Formula (IV)

(Wherein, R ¹ represents a methyl group or an alkenyl group having 3 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ⁴ has 1 to 3 carbon atoms which may be substituted with a halogen atom. An alkyl group, an alkenyl group having 2 to 3 carbon atoms which may be substituted by a halogen atom, an alkoxyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom, a carbon atom which may be substituted by a halogen atom Which represents a methyl group, a hydrogen atom or a halogen atom to which an alkylthio group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom is bonded.
It is known that cyclopropanecarboxylic acid 2,3,5,6-tetrafluorobenzyl ester compound represented by the formula (1) is useful as an active ingredient of a pesticide (for example, Patent Document 1). In Patent Document 2, a transesterification reaction of the following ester compound (I) and a benzyl alcohol compound (II) in a reaction vessel in the presence of a hydrocarbon-based reaction solvent is carried out in A method is disclosed in which a hydrogen-based reaction solvent is distilled out of a reactor, and at the same time, a hydrocarbon-based reaction solvent is newly added to the obtained reaction mixture to further react.

（式中、Ｒ^１はメチル基または炭素数３〜４のアルケニル基を表し、Ｒ^２は水素原子またはメチル基を表し、Ｒ^３はメチル基またはエチル基を表す。） Formula (I)

(In the formula, R ¹ represents a methyl group or an alkenyl group having 3 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a methyl group or an ethyl group.)

（式中、Ｒ^４は、ハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基、ハロゲン原子で置換されていてもよい炭素数２〜３のアルケニル基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルコキシル基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルキルチオ基、ハロゲン原子で置換されていてもよい炭素数１〜３のアルコキシル基が結合したメチル基、水素原子またはハロゲン原子を表す。） Formula (II)

(Wherein, R ⁴ is an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 or 3 carbon atoms which may be substituted with a halogen atom, or a substituent substituted with a halogen atom. C1-C3 alkoxyl group which may be substituted by a halogen atom, C1-C3 alkylthio group optionally substituted by a halogen atom, C1-C3 alkoxyl group which may be substituted by a halogen atom Represents a methyl group, a hydrogen atom or a halogen atom.)

JP-A-2000-63329 JP-A-2002-167355 ([0019] to [0022])

In the above method, unless a large amount of a hydrocarbon-based reaction solvent is used to quickly remove by-produced alcohol from the reaction system, the purity of the obtained ester compound (IV) may be reduced. Further, the recovered hydrocarbon solvent (recovered solvent) cannot be used for the next reaction of the ester compound (IV) without separating the by-produced methanol or ethanol, and methanol or by-produced from the recovered solvent cannot be used. In order to separate ethanol, a reaction tank, a condenser for condensing the recovered solvent, a recovery tank for the recovered solvent, and a facility for recovering only the hydrocarbon reaction solvent from the recovered solvent were required. Further, since a large amount of the recovery solvent is used, a large-capacity facility group is required industrially.
An object of the present invention is to reduce the amount of a hydrocarbon solvent used in the production of an ester compound (IV), and to provide a simple facility including a facility for recovering a hydrocarbon solvent from a recovery solvent. And to provide a method for producing an ester compound (IV).

  The present invention provides a method for producing a fluorine-containing ester compound represented by the formula (IV) by subjecting an ester compound (I) and a benzyl alcohol compound (II) to a transesterification reaction in a reaction vessel in the presence of a hydrocarbon solvent. And distilling a mixture of methanol or ethanol by-produced during the transesterification reaction and the hydrocarbon solvent out of the reaction vessel, contacting the mixture with water, and separating the separated hydrocarbon solvent. A method for producing a fluorinated ester compound (IV), which comprises returning the compound to a rectification column.

Among them, the transesterification reaction is carried out according to the formula (III)
R ⁵ OLi (III)
(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms.)
The reaction is preferably performed in the presence of a lithium compound represented by

Further, the mixture is preferably brought into contact with water via a rectification column, and the contact between the mixture and water and the separation of the hydrocarbon solvent are preferably carried out at 0 to 50 ° C.
Examples of the hydrocarbon-based solvent include a linear aliphatic hydrocarbon solvent having 5 to 8 carbon atoms, a branched aliphatic hydrocarbon solvent having 5 to 8 carbon atoms, and an alicyclic hydrocarbon solvent having 5 to 8 carbon atoms. At least one hydrocarbon solvent selected from the group consisting of

  Further, the present invention provides a reaction vessel (11) for performing a transesterification reaction, a rectification column (12) provided on the upper part of the reaction vessel, and a condenser (13) connected to the top of the rectification column. ), A separator (14) connected to a lower part of the condenser, and a pipe (17) for refluxing the hydrocarbon solvent layer (15) of the separator to the reaction vessel (17). Using 10), the ester compound (I) and the benzyl alcohol compound (II) are subjected to a transesterification reaction in a reaction vessel (11) in the presence of a hydrocarbon-based solvent, and methanol or ethanol by-produced during the transesterification reaction is used. And a mixture with a hydrocarbon solvent via a rectification column (12), the mixture is condensed in a condenser (13), contacted with water in a separator (14), and the separated hydrocarbons The system solvent layer (15) is connected to the rectification column (12) via the pipe (17). A process for producing a fluorinated ester compound (IV), wherein the refluxing Te.

  According to the production method of the present invention, the purity of the obtained fluorinated ester compound (IV) is high and the fluorinated ester compound (IV) can be used for the production method of the fluorinated ester compound (IV) from the recovered solvent even when using less hydrocarbon solvent. There is no need to provide a process for recovering a suitable hydrocarbon solvent and equipment for the process.

Hereinafter, the present invention will be described in detail.
The alkenyl group having 3-4 carbon atoms represented by R ¹ in the ester compound used in the present invention (I), for example, 2-methyl-1-propenyl group, 1-propenyl and 1-butenyl groups are mentioned Can be
Examples of the ester compound (I) include compounds in which R ¹ is an alkenyl group having 3 to 4 carbon atoms and R ₂ is a hydrogen atom, and compounds in which R ¹ and R ₂ are both methyl groups. .

  Specific examples of the ester compound (I) include methyl 2,2-dimethyl-3- (2-methyl-1-propenyl) cyclopropanecarboxylate and 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate Methyl 2,2-dimethyl-3- (1-butenyl) cyclopropanecarboxylate, methyl 2,2,3,3-tetramethylcyclopropanecarboxylate, 2,2-dimethyl-3- (2-methyl Ethyl-1-propenyl) cyclopropanecarboxylate, ethyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, ethyl 2,2-dimethyl-3- (1-butenyl) cyclopropanecarboxylate, and Ethyl 2,2,3,3-tetramethylcyclopropanecarboxylate.

Examples of the alkyl group having 1 to 3 carbon atoms, which may be substituted with a halogen atom, represented by R ⁴ in the benzyl alcohol compound (II) include a methyl group, an ethyl group, and a trifluoromethyl group. Examples of the alkenyl group having 2 to 3 carbon atoms, which may be substituted with a halogen atom, represented by R ⁴ include a vinyl group, an allyl group, and a 2,2-dichlorovinyl group. Examples of the alkoxyl group having 1 to 3 carbon atoms, which may be substituted with a halogen atom, represented by R ⁴ include a methoxy group and a trifluoromethoxy group. Examples of the alkylthio group having 1 to 3 carbon atoms, which may be substituted with a halogen atom, represented by R ⁴ include a methylthio group. Examples of the methyl group represented by R ^{4 to} which an alkoxyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom is bonded include a methoxymethyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Specific examples of the benzyl alcohol compound (II) include 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,4,5,6-pentafluorobenzyl alcohol, 2,3,5,6-tetrafluoro -4-chlorobenzyl alcohol, 2,3,5,6-tetrafluoro-4-bromobenzyl alcohol, 2,3,5,6-tetrafluoro-4-methylbenzyl alcohol, 2,3,5,6-tetra Fluoro-4-difluoromethylbenzyl alcohol, 2,3,5,6-tetrafluoro-4-trifluoromethylbenzyl alcohol, 2,3,5,6-tetrafluoro-4-vinylbenzyl alcohol, 2,3,5 2,6-tetrafluoro-4-allylbenzyl alcohol, 2,3,5,6-tetrafluoro-4- (2,2-dichlorovinyl ) Benzyl alcohol, 2,3,5,6-tetrafluoro-4-methoxybenzyl alcohol, 2,3,5,6-tetrafluoro-4-difluoromethoxybenzyl alcohol, 2,3,5,6-tetrafluoro- 4-trifluoromethoxybenzyl alcohol, 2,3,5,6-tetrafluoro-4-methylthiobenzyl alcohol, and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol.

Examples of the ester compound represented by the formula (IV) include a compound in which R ¹ is an alkenyl group having 3 to 4 carbon atoms and R ² is a hydrogen atom, and both R ¹ and R ² are methyl groups. Compounds.

The present invention is a method for producing a fluorine-containing ester compound (IV) by subjecting an ester compound (I) and a benzyl alcohol compound (II) to a transesterification reaction in a reaction vessel in the presence of a hydrocarbon solvent.
The amount of the ester compound (I) used is preferably in the range of 1 to 3 mol, more preferably 1 to 3 mol, more preferably 1 mol of the benzyl alcohol compound (II), in order to facilitate separation and recovery after the reaction. Ranges from 1 to 2 moles.

Examples of the hydrocarbon solvent include halogenated hydrocarbons (1,2-dichloroethane, monochlorobenzene, etc.), and linear or branched aliphatic hydrocarbons having 5 to 8 carbon atoms (pentane, hexane, heptane, Octane), alicyclic hydrocarbons having 5 to 8 carbon atoms (such as cyclohexane and cycloheptane), and aromatic hydrocarbons (such as toluene and xylene).
The amount of the hydrocarbon solvent to be used is 0.5 to 100 parts by weight, preferably 1 to 10 parts by weight, per 1 part by weight of the benzyl alcohol compound (II). When the organic solvent is used in an amount of 0.5 part by weight or more, it is preferable because side reactions other than the transesterification reaction tend to be suppressed, and when it is 100 parts by weight or less, the volume efficiency in the reaction tank tends to be improved. .

It is preferable to carry out the transesterification reaction in the presence of the following lithium compound (III) because the conversion of the reaction tends to be improved.
R ⁵ OLi (III)
In the formula, examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a t-butyl group.
Specific examples of the lithium compound (III) include lithium methoxide, lithium ethoxide, lithium propoxide, lithium isopropoxide, and lithium-t-butoxide.
The amount of the lithium compound (III) to be used is generally 0.0001 to 0.5 mol, preferably 0.001 to 0.1 mol, per 1 mol of the benzyl alcohol compound (II).

In the transesterification reaction, the mixture of the by-product alcohol and the hydrocarbon-based solvent is heated at a temperature equal to or higher than the boiling point of methanol or ethanol (hereinafter, collectively referred to as a by-product alcohol) derived from R ³ , usually at 70 to 200 ° C. To the outside of the reaction system.
Specifically, the reaction apparatus will be described with reference to the apparatus diagram of FIG. 1, which is an embodiment. The reaction apparatus includes a reaction vessel (11) for performing a transesterification reaction and a rectification column ( 12), a condenser (13) connected to the top of the rectification column, a separator (14) connected to a lower part of the condenser, and a layer (15) of a hydrocarbon solvent of the separator. ) To the rectification column (12).
Then, the ester compound (I) and the benzyl alcohol compound (II) are transesterified in the reaction vessel (11) in the presence of a hydrocarbon solvent, and the by-product alcohol produced by the transesterification reaction is converted into a hydrocarbon solvent. In the form of a mixture with the rectification column (12). The mixture is condensed in a condenser (13). A water layer (16) is prepared in advance in the separator (14), and after the condensed mixture is brought into contact with water, the hydrocarbon solvent becomes the layer (15). The hydrocarbon solvent layer (15) is returned to the rectification column (12) via the pipe (17).

Here, the number of theoretical plates of the rectification column (12) may be one or more, but is usually about 1 to 10 steps, and preferably about 3 to 8 steps. The rectification tower (12) may be, for example, a rectification tower of a tray type, a packed type, or the like. Among them, a packed type is preferable because the efficiency of removing low boiling components (product alcohol) is higher.
As the packing used in the packed rectification column, a commercially available packing may be used.For example, Raschig ring, Berl saddle, Paul ring, Interlock saddle, Lessing ring, Terralet, McMahon packing, Canon packing, Dickson packing And irregularly packed materials such as Sulzer BX, Melapack, Flexipack and Gempack.

  As the condenser, a surface heat exchanger such as a multi-tube cylindrical heat exchanger, a double-tube heat exchanger, or a plate heat exchanger is generally used. Examples include a regenerative heat exchanger such as a valve switching type regenerative heat exchanger, a liquid-connected indirect heat exchanger, and a direct contact heat exchanger.

In the separator (14), the by-product alcohol in the mixed solution is absorbed by the aqueous layer, and the hydrocarbon solvent is separated to form a hydrocarbon solvent layer. Since the hydrocarbon-based solvent layer is usually located above the aqueous layer, a pipe (17) for refluxing the hydrocarbon-based solvent to the rectification column (12) is provided above the separator (14).
Further, the inside of the separator (14) is preferably maintained at about 0 to 50 ° C. When the temperature is 0 ° C or higher, the freezing of the aqueous layer tends to be suppressed, and when the temperature is 50 ° C or lower, the proportion of by-product alcohol contained in the hydrocarbon solvent layer is low, and as a result, the transesterification reaction This is preferable because the reaction rate tends to increase.
The separator (14) may be provided with a cooler to control the temperature in such a range, but usually, the mixture may be cooled to about 0 to 50 ° C by the condenser (13).

  Hereinafter, the present invention will be described in detail with reference to Production Examples, but the present invention is not limited to these Examples. The numbers of the reactors correspond to those in FIG.

<Transesterification reaction>
(Example 1)
2,2-dimethyl-3- (1-propenyl) was placed in a 200 L reactor (11) having a rectification tower (12) having a diameter of 80A and filled with a packing material (Macmahon packing) having a size of 6 mm and having a height of 900 mm. ) 21.6 kg of methyl cyclopropanecarboxylate, 106 kg of n-heptane and 0.11 kg of lithium methoxide, and 27 kg of molten 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol were charged. While maintaining the temperature at 103 ° C., a vapor as a mixture of methanol and n-heptane was cooled to about 30 ° C. by a condenser (13) from the top of the rectification column and condensed. The condensed mixture flows into the separator (14) in which the aqueous layer (16) has been formed in advance, is separated into two phases in the separator (14), and the upper layer (hydrocarbon solvent layer, 15) is connected to the pipe ( The mixture was refluxed to the top of the rectification column (17) via 17), while the lower aqueous layer (16) containing methanol was kept in the separator (14). The reflux was performed for 21 hours. Thereafter, the transesterification mass was cooled and washed with 48 kg of 5% sodium hydroxide and then with 400 kg of water. Thereafter, steam was continuously introduced into the reactor, and impurities were distilled off by steam distillation. The liquid in the obtained reaction vessel was dehydrated to obtain 38 kg of an organic layer. The organic layer was analyzed by gas chromatography (internal standard method) to find that 2,2,3-dimethyl-3- (1-propenyl) cyclopropanecarboxylic acid 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl [ Hereinafter, referred to as the target compound] was 96.7%. In this example, the total amount of n-heptane used for washing and the like to obtain 36.7 kg of the target compound was 114 kg in total, and the amount of the hydrocarbon solvent used was only about 3 times the weight of 37 kg of the target compound. Met.

(Example 2)
In the same reactor (10) as in Example 1, 6.72 kg of methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 25.7 kg of n-heptane, and melted 2,3,5 8 kg of 6-tetrafluoro-4-methylbenzyl alcohol and 0.04 kg of lithium methoxide were charged, and while keeping the temperature at 95 to 105 ° C. distilled from the top of the rectification column, methanol and n were fed from the top of the rectification column. -The vapor, which was a mixture with heptane, was condensed by cooling to about 30 ° C. with a condenser (13). The condensed mixture flows into the separator (14) in which the aqueous layer (16) has been formed in advance, separates into two phases in the separator (14), and connects the upper layer (hydrocarbon solvent layer, 15) to the pipe ( The mixture was refluxed to the top of the rectification column (17) via 17), while the lower aqueous layer (16) containing methanol was kept in the separator (14). The reflux was refluxed for about 9 hours. Thereafter, the transesterification reaction mass was cooled and then washed with 48 kg of water, followed by steam distillation to remove impurities. Next, the liquid in the reaction vessel was dehydrated to obtain 12.8 kg of an organic layer. The content of the target compound in the organic layer was 96.4%.
In this example, in order to obtain 12.3 kg of the target compound, the total amount of n-heptane used for washing and the like was about 35 kg, which was only about 3 times the weight of the target compound.

(Comparative Example 1)
In a 500 L reactor, 35.78 kg of methyl 2,2-dimethyl-3- (1-propenyl) cyclopropanecarboxylate, 143.8 kg of n-heptane, and 0.15 kg of lithium methoxide were charged and melted. 35.94 kg of 5,6-tetrafluoro-4-methoxymethylbenzyl alcohol was added dropwise over about 5 hours. During this time, the reaction was carried out while distilling off the methanol produced by the reaction together with n-heptane out of the system and pouring n-heptane into the reactor so that the amount of n-heptane in the kettle was almost the same as the initial charge. Was done. The amount of n-heptane added during the 5 hours was 68.6 kg. In order to further promote the reaction, n-heptane was introduced into the kettle at a temperature of 100 to 103 ° C. while distilling off methanol together with n-heptane so that the amount of n-heptane in the kettle was substantially constant. The reaction was performed while pouring over time. The amount of n-heptane used during the heat retention was 466.6 kg.
After cooling, the reaction solution was washed with 108 kg of a 5% aqueous sodium hydroxide solution, washed with 324 kg of water, further washed with 36 kg of 1% hydrochloric acid, and further washed with 72 kg of water. The organic layer after the washing was subjected to steam distillation to remove impurities. Next, the liquid in the reaction vessel was dehydrated to obtain 52.8 kg of an organic layer. When the organic layer was analyzed by gas chromatography (internal standard method), the content of the target compound was 96%.
In this example, the amount of n-heptane used for washing, etc. was about 680 kg with respect to 50.7 kg of the target compound, which was about 13 times the weight of the target compound.
Note that methanol was detected in n-heptane recovered during the reaction.

  INDUSTRIAL APPLICABILITY The present invention is used in a method for producing a fluorinated cyclopropanecarboxylic acid benzyl ester compound (fluorinated compound (IV)) to be used for pesticides such as pest control agents, medicines such as medicines, industrial chemicals, etc. It is suitable as a general manufacturing method.

1 is an embodiment of a reaction device used for a transesterification reaction.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 10 Reaction tank 11 Rectification tower 12 Condenser 13 Separation tank 14 Separator 15 Hydrocarbon solvent layer 16 Water layer 17 Pipe for refluxing hydrocarbon solvent from separator

Claims (6)

Formula (I)

(In the formula, R ¹ represents a methyl group or an alkenyl group having 3 to 4 carbon atoms, R ² represents a hydrogen atom or a methyl group, and R ³ represents a methyl group or an ethyl group.)
An ester compound (I) represented by the formula (II)

(Wherein, R ⁴ is an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, an alkenyl group having 2 or 3 carbon atoms which may be substituted with a halogen atom, or a substituent substituted with a halogen atom. C1-C3 alkoxyl group which may be substituted by a halogen atom, C1-C3 alkylthio group optionally substituted by a halogen atom, C1-C3 alkoxyl group which may be substituted by a halogen atom Represents a methyl group, a hydrogen atom or a halogen atom.)
Of the benzyl alcohol compound (II) represented by the formula (IV) in the presence of a hydrocarbon solvent in a reaction vessel

(In the formula, R ¹ , R ² and R ⁴ represent the same meaning as described above.)
Wherein a mixture of methanol or ethanol by-produced during the transesterification reaction and a hydrocarbon-based solvent is distilled out of the reaction vessel to produce a fluorine-containing ester compound (IV) represented by the formula: A method for producing a fluorinated ester compound (IV), comprising bringing the mixture into contact with water and returning the separated hydrocarbon solvent into the reactor. The transesterification reaction is carried out according to the formula (III)
R ⁵ OLi (III)
(In the formula, R ⁵ represents an alkyl group having 1 to 4 carbon atoms.)
The method according to claim 1, wherein the reaction is performed in the presence of a lithium compound represented by the formula:   The method according to claim 1, wherein the mixture is brought into contact with water via a rectification column.   The method according to any one of claims 1 to 3, wherein the contact between the mixture and water and the separation of the hydrocarbon solvent are performed at 0 to 50 ° C.   The hydrocarbon solvent includes a linear aliphatic hydrocarbon solvent having 5 to 8 carbon atoms, a branched aliphatic hydrocarbon solvent having 5 to 8 carbon atoms, and an alicyclic hydrocarbon solvent having 5 to 8 carbon atoms. The method according to any one of claims 1 to 4, wherein at least one hydrocarbon solvent selected from the group is used.   A reaction vessel (11) for performing a transesterification reaction, a rectification tower (12) provided at the top of the reaction vessel, a condenser (13) connected to the top of the rectification tower, and the condenser Using a reactor (10) having a separator (14) connected to the lower part of the reactor and a pipe (17) for refluxing the hydrocarbon solvent layer (15) of the separator to the reaction vessel. The compound (I) and the benzyl alcohol compound (II) are subjected to transesterification in a reaction vessel (11) in the presence of a hydrocarbon solvent, and methanol or ethanol by-produced during the transesterification reaction is added to the hydrocarbon solvent. Is passed through a rectification column (12), the mixture is condensed in a condenser (13), brought into contact with water in a separator (14), and the separated hydrocarbon solvent layer (15) ) Is returned to the rectification tower (12) via the pipe (17). Process for producing a fluorinated ester compound (IV) to.

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