JP4126542B2 - Method for producing decomposition reaction product of fluorine-containing ester compound - Google Patents

Description

  The present invention relates to a method for producing an ester bond decomposition reaction product, particularly a useful fluorine-containing compound. More specifically, the present invention relates to a method for efficiently decomposing an ester bond of a fluorinated ester compound to produce a decomposition reaction product, and further to a method for efficiently producing a fluorinated ester compound used in the method.

  Conventionally, as a method of fluorinating all C—H moieties in a C—H-containing compound to C—F, a method using cobalt trifluoride, a method of directly fluorinating using a fluorine gas, or fluorination A method of electrolyzing hydrogen to perform a fluorination reaction (electrochemical fluorination, hereinafter referred to as “ECF method”) is known. Among these methods, as a method of directly fluorinating using fluorine gas, a method performed in a gas phase and a method performed in a liquid phase are known. However, in the method performed in the gas phase, there is a problem that the C—C single bond is cleaved during the fluorination reaction, and various kinds of by-products are generated, and the method performed in the liquid phase is advantageous (WO00 / 56694). .

  Further, (1) a method of decomposing an ester bond of a perfluoroester compound at 224 to 254 ° C. (J. Am. Chem. Soc. 1998, 120, 7117), (2) a perfluoroester compound in the presence of NaF There are known a method of ester decomposition reaction at 200 ° C. (US3900372), and a method of (3) ester decomposition reaction of a perfluoroester in a batch reaction in the presence of a solvent and NaF or KF (US5466877).

  However, the document (1) does not describe or suggest that the reaction is carried out in the presence of an alkali metal fluoride. In addition, the method described in the document (1) has a problem that the reaction temperature is high and the substrate on which the reaction can be performed is limited. The methods described in the documents (2) and (3) have a problem that the yield is low and the reaction rate is low. The literature (3) describes an example in which the reaction does not proceed when the reaction is carried out without the presence of a solvent.

  The present invention has been made for the purpose of solving the above-mentioned problems, and provides a method for producing a decomposition product continuously by effectively decomposing an ester bond of a fluorine-containing ester compound. Furthermore, this invention provides the method of manufacturing efficiently the fluorine-containing ester compound used for this method.

That is, the present invention provides the following production methods and compounds.
1. -20 A method of obtaining a decomposition reaction product by an ester bond to decompose ester bonds of the fluorinated ester compound which can be decomposed, the decomposition reaction of the ester bond in the presence of KF without solvent substantially 100 A method for producing a decomposition reaction product, characterized in that the reaction is carried out at a reaction temperature of 0 ° C., the fluorine-containing ester compound is continuously supplied to the reaction zone, and the reaction is carried out while continuously taking out the decomposition reaction product from the reaction zone. .
2. 2. The production method according to 1 above, wherein the fluorine-containing ester compound is a compound having —C (O) O—CF— as a partial structure.

3. In the above 1 or 2 , the fluorine-containing ester compound is a compound represented by the formula (4), and the decomposition reaction product is a compound represented by the formula (5) and / or a compound represented by the formula (6). The manufacturing method as described .
R ^CF COOCFR ^AF R ^BF (4)
R ^AF R ^BF C = O (5)
R ^CF COF (6)
Here, R ^AF is a fluorine atom or a monovalent organic group, R ^BF is a monovalent organic group, or R ^AF and R ^BF may be bonded to each other to form a divalent organic group. ^CF is a monovalent organic group, and a fluorine atom is present in at least one group selected from R ^AF , R ^BF and R ^CF.

4). R ^AF , R ^BF And R ^CF Is a perfluoroalkyl group having 1 to 10 carbon atoms, Luo (partial chloroalkyl) group, perfluoroalkoxyalkyl group or perfluor A (partial chloro (alkoxyalkyl)) group, R ^AF Is a fluorine atom Or R ^AF And R ^BF Are jointly perfluoroalkylene groups having 1 to 10 carbon atoms, Perfluoro (partial chloroalkylene) group, perfluoroalkyleneoxyalkylene group Or a perfluoro (partial chloro (alkyleneoxyalkylene)) group, The manufacturing method described.

5. A compound represented by formula (4) is reacted with a compound represented by formula (1) and a compound represented by formula (2) to obtain a compound represented by formula (3). 4. The production method according to 3 above, which is a compound produced by reacting a compound represented by) with fluorine in a liquid phase.
HOCHR ^A R ^B (1)
R ^C COX (2)
R ^C COOCHR ^A R ^B (3)

Here, when R ^AF is a fluorine atom, R ^A is a hydrogen atom, and when R ^A and R ^AF are the same monovalent organic group, R ^A is a monovalent organic group that is not fluorinated. R ^a when the R ^a and R ^AF are different monovalent organic group is a monovalent organic group fluorinated, R ^B when there is the R ^B and R ^BF is the same monovalent organic group In the case of a monovalent organic group that is not fluorinated and R ^B and R ^BF are different monovalent organic groups, R ^B is a monovalent organic group that is fluorinated.

Further, R ^A and R ^B when R ^AF and R ^BF are bonded to form a divalent organic group with one another are combined to form a divalent organic group with one another, from R ^A and R ^B The divalent organic group formed from R ^A and R ^B when the formed divalent organic group is the same as the divalent organic group formed from R ^AF and R ^BF is a divalent organic group that is not fluorinated. There, divalent organic group formed from R ^a and R ^B when different is a divalent organic radical fluorination.
R ^C where the R ^C and R ^CF are the same monovalent organic group is a monovalent organic group which is not fluorinated, R ^C where the R ^C and R ^CF are different monovalent organic groups fluorine It is a monovalent organic group to be converted.
X is a halogen atom.

6). 6. The production method according to 5 above, wherein the compound represented by the formula (3) has a fluorine atom content of 30 to 84% by mass.

7). R ^A is a hydrogen atom, a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, an etheric oxygen atom-containing monovalent saturated hydrocarbon group, or a partial halogeno (an etheric oxygen atom-containing monovalent saturated hydrocarbon). A group in which R ^AF is a fluorine atom or a group in which substantially all of the hydrogen atoms present in R ^A are substituted with fluorine atoms,
R ^B is a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, an etheric oxygen atom-containing monovalent saturated hydrocarbon group, or a partial halogeno (etheric oxygen atom-containing monovalent saturated hydrocarbon) group. , R ^BF is a group in which substantially all of the hydrogen atoms present in R ^B are substituted with fluorine atoms,
Alternatively, R ^A and R ^B are bonded to each other to form a divalent saturated hydrocarbon group, a partial halogeno divalent saturated hydrocarbon group, an etheric oxygen atom-containing divalent saturated hydrocarbon group, or a partial halogeno (etheric oxygen atom-containing 2 Valent saturated hydrocarbon) group, and R ^AF and R ^BF are groups in which substantially all of the hydrogen atoms present in the group formed from R ^A and R ^B are substituted with fluorine atoms,
R ^C and R ^CF are the same group and are a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial halogeno (containing an etheric oxygen atom) 7. The production method according to 5 or 6 above, wherein substantially all of the hydrogen atoms present in the group selected from (monovalent saturated hydrocarbon) groups are groups substituted with fluorine atoms.

8). R ^A And R ^B Are each an alkyl group or a partial chloroalkyl group having 1 to 10 carbon atoms. , An alkoxyalkyl group or a partial chloroalkoxyalkyl group, and R ^A As water May be an elementary atom or R ^A And R ^B Are alkylene groups having 1 to 10 carbon atoms , A partial chloroalkylene group, an alkyleneoxyalkylene group or a partial chloro (alkylene Oxyalkylene) group,
R ^AF And R ^BF Are each a C 1-10 perfluoroalkyl group, perfluoro B (partial chloroalkyl) group, perfluoroalkoxyalkyl group or perfluoro ( A partial chloro (alkoxyalkyl)) group, and R ^AF May be a fluorine atom Or R ^AF And R ^BF Together with a C 1-10 perfluoroalkylene group, Rufluoro (partial chloroalkylene) group, perfluoroalkyleneoxyalkylene group Or a perfluoro (partial chloro (alkyleneoxyalkylene)) group,
R ^C And R ^CF Are the same group, and a perfluoroalkyl group having 1 to 10 carbon atoms, Rufluoro (partial chloroalkyl) group, perfluoroalkoxyalkyl group or perf Luo (partial chloro (alkoxyalkyl)) group,
The manufacturing method in any one of said 5-7 whose X is a fluorine atom.

9. The manufacturing method in any one of said 5-8 whose molecular weight of the compound represented by Formula (3) is 200-1000.
10. 10. The production method according to any one of 1 to 9 above, wherein the ester bond decomposition reaction is performed by a liquid phase reaction.
11. 10. The production method according to any one of 1 to 9 above, wherein the decomposition reaction of the ester bond is not less than the boiling point of the decomposition reaction product and is performed by a gas phase reaction at a reaction temperature of −20 to 100 ° C.

12 A compound represented by the following formula (A-4).

In the following description of the present specification, a compound represented by the formula (4) is described as a compound (4). The same applies to compounds represented by other formulas.
In the present specification, the organic group refers to a group in which a carbon atom is essential, and includes both saturated and unsaturated structures.
As the organic group, a hydrocarbon group, a halogeno hydrocarbon group, a hetero atom-containing hydrocarbon group, or a halogeno (hetero atom-containing hydrocarbon) group is preferable. These organic groups are preferably groups having 1 to 20 carbon atoms, particularly groups having 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase used during the fluorination reaction.

  The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, is preferably an aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group. Examples of the monovalent saturated aliphatic hydrocarbon group include an alkyl group or a cycloalkyl group, and the structure of the alkyl group is any of a linear structure, a branched structure, a ring structure, or a structure that is partially a ring. May be. Examples of the divalent saturated hydrocarbon group include an alkylene group and a cycloalkylene group, and the structure of the alkylene group may be any of a linear structure, a branched structure, or a structure having a ring portion.

As for carbon number of an alkyl group or an alkylene group, 1-10 are preferable. As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cycloalkylalkyl group, or a cycloalkyl group moiety is further substituted with an alkyl group. And cycloalkylalkyl groups.
In addition, examples of the alkylene group include groups in which one of the hydrogen atoms of the alkyl group is a bond, and a linear or branched alkylene group is preferable.
Moreover, as a cycloalkyl group, a 3-6 membered cycloalkyl group is mentioned, A cyclopentyl group and a cyclohexyl group are preferable. The cycloalkylene group is preferably a cyclopentylene group or a cyclohexylene group.

In the present specification, the halogeno group refers to a group in which one or more hydrogen atoms are substituted with a halogen atom. The halogeno group may be a group in which a hydrogen atom is present or a group in which a hydrogen atom is not present. The partial halogeno group refers to a group in which a part of hydrogen atoms is replaced with a halogen atom. That is, the partial halogeno group is a group in which a hydrogen atom exists. The perhalogeno group is a group in which all of the hydrogen atoms are substituted with halogen atoms, and is a group in which no hydrogen atoms are present. The meanings of the terms halogeno, partial halogeno and perhalogeno have the same meaning even when a halogen atom is specified.
Examples of the halogen atom in the halogeno group include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a fluorine atom, a chlorine atom, or a bromine atom is preferable. In particular, from the viewpoint of the usefulness of the compound, only the fluorine atom or fluorine It preferably consists of atoms and chlorine atoms.

The halogeno hydrocarbon group refers to a group in which one or more hydrogen atoms present in the hydrocarbon group are substituted with a halogen atom.
As the monovalent halogeno saturated hydrocarbon group, a fluoroalkyl group or a fluoro (partially chloroalkyl) group is preferable, and a perfluoroalkyl group or a perfluoro (partially chloroalkyl) group (that is, all of the hydrogen atoms in the part chloroalkyl group are A group substituted with a fluorine atom) is preferred. The divalent halogeno saturated hydrocarbon group is preferably a fluoroalkylene group or a fluoro (partially chloroalkylene) group, and a perfluoroalkylene group or a perfluoro (partially chloroalkylene) group (that is, all of the hydrogen atoms in the part chloroalkylene group are A group substituted with a fluorine atom) is preferred. The perfluoro (partial fluoroalkyl) group is the same as the perfluoroalkyl group, and the perfluoro (partial fluoroalkylene) group is the same as the perfluoroalkylene group.

The hetero atom-containing hydrocarbon group refers to a group consisting of a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, a carbon atom, and a hydrogen atom. As the hetero atom, an etheric oxygen atom (C—O—C of O) is particularly preferable. The heteroatom is preferably present between the carbon-carbon atoms of the hydrocarbon group or at the bond terminal of the hydrocarbon group.
As the heteroatom-containing hydrocarbon group, an alkyl group containing an etheric oxygen atom as a monovalent group (for example, from the viewpoint of availability of a compound, availability, ease of production, and usefulness of a product (for example, , An alkoxyalkyl group, etc.) are preferable, and the divalent group is preferably an alkylene group containing an etheric oxygen atom (for example, a polyoxyalkylene group).

As an alkoxyalkyl group, the group whose carbon number of an alkoxy group part is 1-10 is preferable. Examples of the alkoxyalkyl group include an ethoxymethyl group, a 1-propoxyethyl group, and a 2-propoxyethyl group. The polyoxyalkylene group is preferably a polyoxyethylene group or a polyoxypropylene group.
The halogeno (hetero atom-containing hydrocarbon) group refers to a group in which one or more hydrogen atoms of the hetero atom-containing hydrocarbon group are substituted with a halogen atom. As the monovalent group, a fluoro (alkoxyalkyl) group or a fluoro (partial chloro (alkoxyalkyl)) group is preferable, and a perfluoro (alkoxyalkyl) group or a perfluoro (partial chloro (alkoxyalkyl)) group is particularly preferable. As the divalent group, a fluoro (polyoxyalkylene) group is preferable, and a perfluoro (polyoxyalkylene) group is particularly preferable.

  In the present invention, the ester bond of the fluorine-containing ester compound capable of decomposing the ester bond is decomposed. Examples of the fluorinated ester compound capable of decomposing an ester bond include compounds having a partial structure (—C (O) O—CF—) in which a fluorine atom is bonded to a carbon atom adjacent to an oxygen atom forming the ester bond. . The carbon atom to which the fluorine atom in this partial structure is bonded further has a bond. Even if a monovalent atom (a fluorine atom is preferable in terms of availability) or a monovalent organic group (a trifluoromethyl group is preferable in terms of availability) is bonded to the bond. Good. Alternatively, the carbon atom to which the fluorine atom is bonded may be a carbon atom that forms a ring. Further, the partial structure in the fluorine-containing ester compound is 1 or more, preferably 1 to 10, and particularly preferably 1 or 2 from the viewpoint of the usefulness of the compound and the ease of reaction operation.

Hereinafter, a compound having one ester bond that can be decomposed will be described as an example. As the fluorine-containing ester compound having one ester bond that can be decomposed, the following compound (4) is preferred.
R ^CF COOCFR ^AF R ^BF (4)

Here, R ^AF , R ^BF and R ^CF are as described above. The compound (4) is preferably a substantially perfluorinated compound. A substantially perfluorinated compound refers to a compound having the same properties as a perfluorinated compound even when a hydrogen atom that is not fluorinated is present. Further, R ^AF , R ^BF and R ^CF are a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially chloro (monovalent saturated hydrocarbon)) group, a perfluoro (etheric oxygen atom-containing monovalent saturated hydrocarbon) group, a perfluoro ( A partial chloro (etheric oxygen atom-containing monovalent saturated hydrocarbon)) group is preferred, and in R ^AF , a fluorine atom is also preferred in addition to the above.
Further R ^AF, R ^BF, as R ^CF is a perfluoroalkyl group, a perfluoro (partially chlorinated alkyl) group, perfluoroalkoxy group, a perfluoro (partially chlorinated (alkoxyalkyl)) groups are particularly preferred, in R ^AF, the In addition, a fluorine atom is also preferred.

In addition, R ^AF and R ^BF are combined with a perfluoro divalent saturated hydrocarbon group, a perfluoro (partial halogeno (divalent saturated hydrocarbon)) group, a perfluoro (etheric oxygen atom-containing divalent saturated hydrocarbon) group, or a perfluoro group. (Partial halogeno (etheric oxygen atom-containing divalent saturated hydrocarbon)) group is preferable, and in particular, a perfluoroalkylene group, a perfluoro (partial chloroalkylene ) group , a perfluoroalkyleneoxyalkylene group, or a perfluoro (partial chloro (alkyleneoxyalkylene)) Groups are preferred.

Specific examples of the compound (4) include compounds represented by the following formula. In the following formulae, Cy ^F represents a perfluorocyclohexyl group, and R ^1F and R ^2F each independently represent a fluorine atom or a trifluoromethyl group.

  In the present invention, the ester bond of the fluorine-containing ester compound is decomposed. Conditions and methods for the ester bond decomposition reaction are appropriately changed depending on the type of the fluorine-containing ester compound and the target fluorine-containing compound (whether the target compound is compound (5) or compound (6), etc.). sell. The ester bond decomposition reaction is carried out while continuously supplying the fluorine-containing ester compound to the reaction zone and continuously removing the decomposition reaction product from the reaction zone.

The reaction of the present invention is carried out without substantially using a solvent. Here, the solvent refers to a liquid mixture other than a compound involved in the reaction (that is, a fluorine-containing ester compound and a decomposition reaction product thereof).
The supply rate of the fluorinated ester compound and the extraction rate of the reaction product of the decomposition reaction can be appropriately changed depending on the reactivity of the fluorinated ester compound, the type of apparatus, the reaction conditions, and the like. For example, when the fluorine-containing ester compound is a compound having a boiling point lower than the ester bond decomposition reaction temperature, the ester bond decomposition reaction can be carried out in a gas phase reaction mode.

In the case of carrying out the reaction in a gas phase reaction, a gaseous fluorine-containing ester compound may be passed through a reaction apparatus having KF as a fixed bed or a fluidized bed. On the other hand, when the boiling point of the fluorinated ester compound is equal to or higher than the decomposition temperature of the ester bond, the reaction is preferably carried out by a liquid phase reaction method. When the reaction is carried out in a liquid phase reaction, it is preferable to carry out the reaction by charging KF and a fluorinated ester compound in a reaction tank and stirring the mixture, and then supplying the fluorinated ester compound thereto. At this time, in order to efficiently extract the decomposition reaction product, the reaction temperature is preferably set to be equal to or higher than the boiling point of the target decomposition reaction product. Further in this case, using the reaction apparatus with a distillation column, by carrying out the reaction with distillation simultaneously preferably the reaction product from the reaction field for performing continuous distillation while reacting. Since the decomposition reaction product of the ester bond usually has a lower boiling point than the compound (4), it can be extracted continuously and efficiently by distillation.

The ester bond decomposition reaction is carried out in the presence of KF. KF acts as a nucleophile, F ⁻ derived from KF is nucleophilically added to the carbonyl group present in the ester bond of compound (4), and R ^AF R ^BF CFO ⁻ is eliminated and the compound (6) is generated. Further, F ⁻ is eliminated from R ^AF R ^BF CFO ⁻ to produce the compound (5). The detached F ⁻ reacts in the same manner as another compound (4) molecule. Therefore, KF used at the beginning of the reaction may be a catalytic amount or may be used in excess. That is, the amount of KF is preferably 1 to 500 mol%, particularly preferably 5 to 50 mol%, relative to compound (4).

In the present invention, by carrying out the reaction using KF, a decomposition reaction product can be obtained efficiently at a lower temperature than when other alkali metal fluorides such as NaF are used. The upper limit of the reaction temperature is 100 ° C. The lower limit of the reaction temperature in the gas phase reaction is preferably the boiling point of the reaction product of the decomposition reaction, and particularly preferably −20 ° C. Since the ester bond decomposition reaction of the present invention can be carried out at a low reaction temperature, it is advantageous in production and is suitable as an industrial production method.

  Further, when the fluorine-containing ester compound is in a liquid state under the decomposition reaction conditions, since the compound itself forms a liquid phase, no solvent is required. Moreover, when it is gaseous, it can react without using a solvent. That is, while the conventional ester bond decomposition reaction was performed in the liquid phase in the presence of a solvent, the method of the present invention can be carried out in the absence of a solvent without substantially using a solvent, so that the volumetric efficiency is improved. And advantageous from the viewpoint of suppression of by-products. In addition, the reaction can be carried out at a low reaction temperature both in the case of the gas phase reaction and the liquid phase reaction.

  Furthermore, according to the method of the present invention, the reaction rate of the ester bond decomposition reaction is significantly improved by carrying out the reaction in the presence of KF. Therefore, the production amount of the target compound per unit time when the decomposition reaction is continuously performed is greatly improved, which is extremely advantageous in terms of production efficiency.

In the present invention, the desired compound is obtained from the reaction product of the ester bond decomposition reaction. Examples of the reaction product include a compound having a terminal structure of —COF and a ketone compound. For example, in the decomposition reaction of the ester bond of compound (4), the following compound (5) and / or compound (6) Can be generated.
R ^AF R ^BF C = O (5)
R ^CF COF (6)
Here, R ^AF , R ^BF and R ^CF are the same group corresponding to the compound (4), and preferred embodiments are also the same.

Specific examples of the compound (5) include the following compounds. Specific examples of the compound (6) include compounds in which R ^1F is a fluorine atom among the compounds listed as specific examples of the compound (5). However, in the following formula, R ^1F represents a fluorine atom or a trifluoromethyl group.

Furthermore, when R ^AF in the compound (5) is a fluorine atom, it is preferable that the compound (5) and compound (6) produced by the ester bond decomposition reaction have the same structure. When compound (5) and compound (6) have the same structure, the purification step of the decomposition reaction product can be greatly simplified, and an efficient production method can be achieved.

As such a compound (4), the following compound (4A) is preferable. Compound (4A) can be obtained by fluorination reaction of compound (3A) described later.
R ^BF COOCF ₂ R ^BF (4A)
However, R ^BF has the same meaning as described above, and preferred embodiments are also the same.

  The compound (4) can be obtained by reacting the compound (1) with the compound (2) to give a compound (3), and the compound (3) produced by reacting the compound (3) with fluorine in the liquid phase. (4) is preferred. The method can be carried out according to the method of the present inventors by WO 00/56694, and a compound having an arbitrary structure can be obtained.

As compound (1), since alcohols containing no fluorine are readily available, as R ^A and R ^B , hydrogen atom, monovalent saturated hydrocarbon group, partially chloro monovalent saturated hydrocarbon group, etheric property An oxygen atom-containing monovalent saturated hydrocarbon group or a partial chloro (etheric oxygen atom-containing monovalent saturated hydrocarbon) group is preferred, and as R ^A , a hydrogen atom is also preferred in addition to the above. Furthermore, as R ^A and R ^B , an alkyl group, a partial chloroalkyl group, an alkoxyalkyl group, and a partial chloroalkoxyalkyl group are particularly preferable, and as R ^A , a hydrogen atom is also preferable in addition to the above.

Or, R ^A and R ^B of the compound (1) are a divalent saturated hydrocarbon group, a partial chloro (divalent saturated hydrocarbon) group, an etheric oxygen atom-containing divalent saturated hydrocarbon group, or a partial chloro (ether). A divalent saturated hydrocarbon containing a reactive oxygen atom) group is preferable, and an alkylene group, a partial chloroalkylene group, an alkyleneoxyalkylene group, or a partial chloro (alkyleneoxyalkylene) group is particularly preferable. . Since compound (1) can easily obtain compounds having various structures, compound (1) corresponding to the structure of compound (4) can be easily obtained and compound (4) having an arbitrary structure can be easily obtained. Can be manufactured.

Specific examples of the compound (1) include compounds represented by the following formula. In the following formulae, Cy represents a cyclohexyl group, and R ¹ represents a hydrogen atom or a methyl group.

Further, R ^C in the compound (2) is preferably a monovalent organic group having a fluorine atom, a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon containing an etheric oxygen atom. And a group in which substantially all of the hydrogen atoms present in a group selected from a group and a partial halogeno (etheric oxygen atom-containing monovalent saturated hydrocarbon) group are substituted with fluorine atoms, particularly perfluoromonovalent saturated hydrocarbons. Group, perfluoro (partial chloro (monovalent saturated hydrocarbon)) group, perfluoro (etheric oxygen atom-containing monovalent saturated hydrocarbon) group, perfluoro (partial chloro (etheric oxygen atom-containing monovalent saturated hydrocarbon)) group Among them, a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoroalkoxyalkyl group, a perfluoro (part Chloro (alkoxyalkyl)) group is preferred.

Specific examples of compound (2) include the same compounds as compound (6). In the case of obtaining the compound (5) in which R ^AF is a fluorine atom, the following compound (1A) is preferable as the compound (1), and the following compound (2A) is preferable as the compound (2). In the reaction (2A), the following compound (3A) is produced.
R ^B CH ₂ OH (1A)
R ^BF COF (2A)
R ^B COOCH ₂ R ^BF (3A)

Next, the compound (3) produced by the reaction between the compound (1) and the compound (2) is reacted with fluorine in the liquid phase to obtain the compound (4). The reaction between the compound (1) and the compound (2) can be carried out by applying known ester reaction methods and conditions.
Since HF is generated in the reaction between the compound (1) and the compound (2), an alkali metal fluoride (NaF or KF is preferable) or a trialkylamine may be present in the reaction system as an HF scavenger. The HF scavenger is preferably used when the compound (1) or the compound (2) is an acid labile compound. Further, when no HF scavenger is used, it is preferable to discharge HF outside the reaction system with a nitrogen stream. When using an alkali metal fluoride, it is preferable to set it as 1-10 times mole with respect to a compound (2).

In general, the reaction temperature between the compound (1) and the compound (2) is preferably −50 ° C. or higher, and preferably + 100 ° C. or lower or the boiling point temperature of the solvent or lower. The reaction time of the reaction can be appropriately changed according to the feed rate of the raw material and the amount of compound used in the reaction. The reaction pressure (gauge pressure, hereinafter the same) is preferably 0 to 2 MPa.
The amount ratio of the compound (1) to the compound (2) is preferably 0.5 to 5 times mol, particularly preferably 1 to 2 times mol, of the compound (2) with respect to the compound (1). .
The crude product containing the compound (3) produced by the reaction between the compound (1) and the compound (2) may be purified according to the purpose or used as it is in the next reaction. Separation and purification are desirable from the viewpoint of stably performing the fluorination reaction in the process.

  The fluorine content of the compound (3) obtained by reacting the compound (1) and the compound (2) (the fluorine content is the ratio of the mass of fluorine atoms to the molecular weight) is preferably 30% by mass or more. The fluorine content is preferably 30 to 84% by mass, and particularly preferably 30 to 76% by mass. If the fluorine content is too low, the solubility of the compound (3) in the liquid phase becomes extremely low, the reaction system during the fluorination reaction becomes non-uniform, and the compound (3) is used when carried out in a continuous reaction. This causes a problem that cannot be fed successfully into the reaction system. Further, the upper limit of the fluorine content is not particularly limited, but those that are too high are difficult to obtain, expensive and not economical.

  Moreover, it is preferable that the molecular weight of the compound (3) is 200 to 1000 from the viewpoint that an undesirable fluorination reaction in the gas phase can be prevented and the fluorination reaction in the liquid phase can be carried out smoothly. If the molecular weight is too small, the compound (3) is likely to be vaporized, so that a decomposition reaction may occur in the gas phase during the fluorination reaction in the liquid phase. On the other hand, if the molecular weight is too large, it may be difficult to purify the compound (3).

Specific examples of the compound (3) include compounds represented by the following formula. In the following formulae, Cy represents a cycloalkyl group, R ¹ represents a hydrogen atom or a methyl group, and R ^2F represents a fluorine atom or a trifluoromethyl group.

The compound (3) is then fluorinated to obtain the compound (4). This fluorination is performed by a fluorination reaction in which the compound (3) is reacted with fluorine in the liquid phase. Here, the fluorination reaction is a reaction in which at least one fluorine atom is bonded to the molecule of the compound (3). R ^AF , R ^BF , and R ^CF in the compound (4) are groups corresponding to the substituents R ^A , R ^B , and R ^C in the compound (3), respectively. In these groups, carbon is added before and after the fluorination reaction. There is no change in the arrangement of atoms. In addition, the divalent organic group formed from R ^AF , R ^BF , or R ^AF and R ^{BF of} the compound (4) is the divalent organic group formed from R ^A , R ^B , or R ^A and R ^B , respectively. Are preferably different groups, and these groups are preferably fluorinated groups. In the fluorination reaction, hydrogen atoms bonded to carbon atoms are replaced with fluorine. A fluorine atom is added to the carbon-carbon unsaturated bond. The fluorination reaction may be performed on a part or all of the structure that can be fluorinated, and is preferably performed on the whole.

In compound (4), R ^AF is a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial halogeno (monovalent saturated carbon containing an etheric oxygen atom) It is preferred that substantially all of the hydrogen atoms present in the group selected from the group (hydrogen) are substituted with fluorine atoms or fluorine atoms, and all of the hydrogen atoms present in fluorine atoms or R ^A are fluorinated. It is particularly preferred that In addition, R ^BF is a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, an etheric oxygen atom-containing monovalent saturated hydrocarbon group, and a partial halogeno (etheric oxygen atom-containing monovalent saturated hydrocarbon) group. preferably substantially all of the hydrogen atoms are radicals which substituted by fluorine atoms present in a group selected, all of the hydrogen atoms present in R ^B is fluorinated groups are particularly preferred. R ^CF is the same group as R ^C and is a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partial halogeno (containing an etheric oxygen atom) It is preferred that substantially all of the hydrogen atoms present in the group selected from (monovalent saturated hydrocarbon) groups are substituted with fluorine atoms, and particularly preferred are those groups in which all are fluorinated. .

  When the compound (3) is fluorinated in the liquid phase, it is preferably carried out by introducing fluorine gas into the solvent in which the compound (3) is present. The fluorine gas may be used as it is, or a fluorine gas diluted with an inert gas may be used. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economical reasons. The amount of fluorine gas in the nitrogen gas is not particularly limited, and is preferably 10% by volume or more from the viewpoint of efficiency, and particularly preferably 20% by volume or more.

As the liquid phase, it is preferable to use a solvent capable of dissolving fluorine (F ₂ ). As the solvent, a solvent which does not contain a C—H bond and essentially requires a C—F bond is preferable, and further, a perfluoroalkane or one or more atoms selected from a chlorine atom, a nitrogen atom and an oxygen atom are contained. An organic solvent obtained by perfluorinating a known organic solvent in the structure is preferable. Further, as the solvent, it is preferable to use a solvent in which the compound (3) is highly soluble. Particularly, when the compound (4), the compound (5) or the compound (6) is used, the post-reaction after reaction is easy. Is preferable.
The amount of the solvent used is preferably 5 times or more, and particularly preferably 10 to 100 times, the amount of the compound (3).

  The reaction mode of the fluorination reaction is preferably a continuous method rather than a batch method, and the following continuous method is particularly preferable from the viewpoint of reaction yield and selectivity. That is, the solvent is charged into the reactor, and stirring is started. Next, it is a continuous method in which the compound (3) and fluorine gas are continuously and simultaneously supplied at a predetermined molar ratio to the liquid phase in the reactor under a predetermined reaction temperature and reaction pressure. When supplying the compound (3), it may or may not be diluted with a solvent, but in order to improve selectivity and suppress the amount of by-products, the compound (3) diluted with a solvent is supplied. It is preferable. Moreover, when diluting the compound (3) with a solvent, the amount of the solvent relative to the compound (3) is preferably 5 times or more, and particularly preferably 10 times or more.

  The amount of fluorine used in the fluorination reaction is such that the amount of fluorine is always an excess equivalent to the hydrogen atom in the compound (3), both when the reaction is carried out in a batch manner and in a continuous manner. It is preferable to use fluorine, and it is particularly preferable from the viewpoint of selectivity to use fluorine so that the amount is 1.5 times equivalent or more (that is, 1.5 times mole or more). The upper limit of the fluorine amount is preferably 3.0 times mol or less.

  The reaction temperature of the fluorination reaction is usually preferably −60 ° C. or higher and not higher than the boiling point of the compound (3), and is −50 ° C. to + 100 ° C. from the viewpoint of reaction yield, selectivity, and ease of industrial implementation. Particularly preferred is −20 ° C. to + 50 ° C. The reaction pressure of the fluorination reaction is not particularly limited, and 0 to 2 MPa (cage pressure; the same applies hereinafter) is particularly preferable from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.

  Furthermore, in order to advance fluorination efficiently, it is preferable to add a C—H bond-containing compound to the reaction system or to perform ultraviolet irradiation. That is, it is preferable to add a C—H bond-containing compound to the reaction system in the latter stage of the fluorination reaction, or to perform ultraviolet irradiation in the latter stage of the reaction. Thereby, the compound (3) present in the reaction system can be efficiently fluorinated, and the reaction rate can be dramatically improved.

As the C—H bond-containing compound, benzene, toluene and the like are particularly preferable. The amount of the C—H bond-containing compound added is preferably 0.1 to 10 mol%, particularly preferably 0.1 to 5 mol%, relative to the hydrogen atom in the compound (3).
The C—H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Furthermore, when a C—H bond-containing compound is added, it is preferable to pressurize the reaction system. The pressure at the time of pressurization is preferably 0.01 to 5 MPa.

  In the fluorination reaction, since HF is by-produced, it is preferable to allow the HF scavenger to coexist in the reaction system for the purpose of removing HF, or to contact the HF scavenger and the outlet gas at the reactor gas outlet. As the HF scavenger, NaF is preferable. The amount of the HF scavenger in the reaction system is preferably 1 to 20 moles, more preferably 1 to 5 moles, based on the total amount of hydrogen atoms present in the compound (3). When placing an HF scavenger at the reactor gas outlet, (a) a cooler (preferably kept at 10 ° C. to room temperature, particularly preferably around 20 ° C.) (b) filling with NaF pellets And (c) a cooler (preferably held at −78 ° C. to + 10 ° C., more preferably held at −30 ° C. to 0 ° C.) in the order of (a)-(b)-(c) It is preferable to install them in series. In addition, you may install the liquid return line for returning the condensed liquid from the cooler of (c) to a reactor.

The fluorination of the compound (3) is preferably carried out until the compound (3) is substantially perfluorinated, particularly until it is perfluorinated.
Moreover, the crude product containing the compound (4) obtained by the fluorination reaction may be used in the next step as it is, or may be purified to have a high purity. Examples of the purification method include a method of distilling the crude product as it is under normal pressure or reduced pressure.

The best method as an industrial process for obtaining the compound (5) and / or the compound (6) by the production method of the present invention is the following method.
That is, the compound (1A) and the compound (2A) are reacted to obtain a compound (3A), and the compound (3A) is reacted with fluorine in a liquid phase to obtain a compound (4A). In this method, the compound (2A) is obtained from a reaction product obtained by decomposing an ester bond. Furthermore, if the compound (2A) is reacted again with the compound (1A), the compound (2A) can be produced continuously and efficiently.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following, 1,1,2-trichlorotrifluoroethane is referred to as R-113, and gas chromatography is referred to as GC.

[Example 1 (Example)]
A stainless steel autoclave with a 2 L capacity stirrer was added to a 97% pure CF ₃ (C
F ₂ ) ₂ OCF (CF ₃ ) COOCF ₂ CF (CF ₃ ) O (CF ₂ ) ₂ CF ₃ crude liquid (hereinafter abbreviated as “perfluoroester crude liquid”, 1800 g), and KF powder produced by spray drying ( 30 g) and charged to 70 ° C. with stirring. When the predetermined temperature was reached, the perfluoroester crude liquid was continuously fed at a rate of 115 g / h. Gas generated through a stainless steel jacketed column heated at 60 ° C. provided at the top of the reactor was continuously withdrawn and captured by a dry ice strap. From the weight of the trapped product and analysis by GC, it was confirmed that CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COF (hereinafter abbreviated as “(HFPO) ₂ ”) was generated at a rate of 110 g / h. did. The yield of (HFPO) ₂ was 99%.

[Example 2 (Example)]
The same operation as in Example 1 was performed except that the reaction temperature was 73 ° C. and the feed amount of the perfluoroester crude liquid was 215 g / h. From the weight of the product trapped by the dry eye strap and analysis by GC, it was confirmed that (HFPO) ₂ was formed at a rate of 260 g / h. The yield of (HFPO) ₂ was 99%.

[Example 3 (comparative example)]
Using the same apparatus as in Example 1, 1700 g of perfluoroester crude liquid and 55 g of NaF powder (Morita Chemical Co., Ltd.) were charged into the reactor, and the temperature was raised to 140 ° C. while stirring. The NaF powder was heat-treated at 120 ° C. for 2 hours before use. When the predetermined temperature was reached, the perfluoroester crude liquid was continuously fed at a rate of 60 g / h. From the weight of the product captured by the dry eye strap and analysis by GC, it was confirmed that (HFPO) ₂ was produced at a rate of 57 g / h. The yield of (HFPO) ₂ was 99%.

[Example 4 _{(Example)] CF 3 CF 2 CF 2} OCF (CF 3) COOCF 2 CF (CF 3) Preparation of OCF ₂ CF ₂ CF ₃ (Example _{4-1) CF 3 CF 2 CF 2} OCF (CF ₃ ) Production Example of COOCH ₂ CH (CH ₃ ) OCH ₂ CH ₂ CH ₃ CH ₃ CH ₂ CH ₂ OCH (CH ₃ ) CH ₂ OH (620 g) was placed in a flask and stirred while bubbling nitrogen gas. CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF (3604 g) was added dropwise over 8 hours while maintaining the internal temperature at 25 to 35 ° C. After completion of the dropwise addition, the reaction mixture containing the title compound and CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF was stirred at room temperature for 2 hours while nitrogen gas was continuously bubbled. The resulting reaction mixture was used for the reaction of Example 4-2.

Example 4-2 Production Example of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ CF ₃ CF obtained in Example 4-1 was added to a 3000 mL nickel autoclave. ₂ CF ₂ OCF (CF ₃ ) COF (2340 g) was added and stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a packed bed of NaF pellets, and a cooler maintained at −10 ° C. were installed in series. In addition, the liquid return line for returning the condensed liquid to the autoclave was installed from the cooler kept at -10 ° C. After blowing nitrogen gas for 1.5 hours, fluorine gas diluted to 20 volume% with nitrogen gas (hereinafter abbreviated as diluted fluorine gas) was blown for 3 hours at a flow rate of 8.91 L / h.
Next, the reaction mixture (106 g) obtained in Example 4-1 was injected over 45.6 hours while diluting fluorine gas at the same flow rate.

Next, the CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF solution (18 mL) having a benzene concentration of 0.01 g / mL is heated from 25 ° C. to 40 ° C. while diluting fluorine gas at the same flow rate. The autoclave benzene inlet valve was closed, the autoclave outlet valve was closed, and when the pressure reached 0.2 MPa, the autoclave fluorine gas inlet valve was closed and stirring was continued for 1 hour. Next, while maintaining the reactor temperature at 40 ° C., the above benzene solution (6 mL) was injected, the benzene inlet valve of the autoclave was closed, the autoclave outlet valve was closed, and the pressure was zero. When the pressure reached 2 MPa, the fluorine gas inlet valve of the autoclave was closed and stirring was continued for 1 hour. Further, the benzene injection operation was repeated once in the same manner.
The total amount of benzene injected was 0.309 g, and the total amount of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF injected was 30 mL. Further, nitrogen gas was blown for 2.0 hours. After the reaction, the product was purified by distillation to obtain a product containing the title compound (85.3 g) and CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF.

[Example 5]
Example 5-1 Production Example of the following Compound

Tetrahydrofurfuryl alcohol (20 g) and triethylamine (21.8 g) were placed in a flask and stirred in an ice bath. FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (71.5 g) was added dropwise over 1 hour while maintaining the internal temperature at 10 ° C. or lower. After completion of dropping, the mixture was stirred at room temperature for 2 hours, and 50 mL of water was added at an internal temperature of 15 ° C. or lower.
The obtained crude liquid was separated, and the lower layer was washed twice with 50 mL of water, dried over magnesium sulfate, and then filtered to obtain a crude liquid. The target ester compound (66.3 g) was obtained by distillation under reduced pressure as a fraction of 88 to 89 ° C./2.7 kPa. The GC purity was 98%.

Example 5-2 Production example of the following compound

R-113 (1614 g) was added to a 3000 mL nickel autoclave, stirred, and kept at 25 ° C. At the autoclave gas outlet, a cooler maintained at 20 ° C., a packed bed of NaF pellets, and a cooler maintained at −10 ° C. were installed in series. In addition, the liquid return line for returning the condensed liquid to the autoclave was installed from the cooler kept at -10 ° C. After blowing nitrogen gas for 1.0 hour, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter abbreviated as diluted fluorine gas) was blown for 1 hour at a flow rate of 17.04 L / h.
Next, while dilute fluorine gas was blown at the same flow rate, a solution obtained by dissolving the reaction crude liquid (54 g) obtained in Example 5-1 in R-113 (510 g) was injected over 14.7 hours.

Next, while blowing the diluted fluorine gas at the same flow rate and maintaining the reactor pressure at 0.15 MPa, the temperature of the R-113 solution having a benzene concentration of 0.05 g / mL is increased from 25 ° C. to 40 ° C. 30 mL was injected, the benzene inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Next, 20 mL of the above benzene solution was injected while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C. while blowing diluted fluorine gas at the same flow rate, and stirring was continued for 0.3 hours. . The same operation was repeated three times, and stirring was continued for another 2.0 hours. The total amount of benzene injected was 5.00 g, and the total amount of R-113 injected was 111 mL. The target product was quantified by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ), and the yield of the title compound was 75%.

Example 5-3 Production Example of the following Compound

56.5 g of the reaction crude liquid obtained in Example 5-2 was charged into a flask together with 0.95 g of KF powder, and heated at 90 to 110 ° C. for 4 hours in an oil bath with vigorous stirring. A reflux condenser whose temperature was adjusted to 5 ° C. was installed at the top of the flask, and a liquid sample was collected with a dry ice / ethanol trap at the reflux outlet. After cooling, 44.0 g of a liquid sample was recovered. As a result of analysis by GC-MS, CF ₃ CF (OCF ₂ CF ₂ CF ₃ ) COF and the title compound were confirmed as main products. The yield of the title compound was determined by NMR and found to be 87%.
¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ ) δ (ppm): 26.3 (1F), −82.8 (1F), −83.6 (1F), −118.1 (1F), -125.9 (1F), -126.8 (1F), -129.3 (1F), -134.8 (1F).

[Example 6]
Example 6-1 Production Example of Compound A-2 and Compound B-2

A 59:41 (molar ratio) mixture (100.0 g) of compound A-1 and compound B-1 and triethylamine (10.7 g) were placed in a flask and stirred at an internal temperature of 10 ° C. or lower. FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (351.0 g) was added dropwise over 400 minutes while maintaining the internal temperature at 10 ° C. or lower. After completion of the dropping, the mixture was stirred at room temperature for 1 hour, and water (500 mL) was added so that the internal temperature did not exceed 15 ° C. To the obtained crude liquid, dichloropentafluoropropane (1000 mL, trade name: AK225, manufactured by Asahi Glass Co., Ltd.) was added and separated to obtain a lower layer. Further, the lower layer was washed twice with water (500 mL), dried over magnesium sulfate, and then filtered to obtain a crude liquid. The crude liquid was concentrated with an evaporator and then distilled under reduced pressure to obtain a fraction (328.0 g) of 59 to 62 ° C./0.4 kPa. The GC purity was 99.6%.

Example 6-2 Production Example of Compound A-3 and Compound B-3

Using the same reactor as in Example 5-2, R-113 (1701 g) was added and stirred and kept at 25 ° C. Diluted fluorine gas was blown in at a flow rate of 17.04 L / h for 1 hour.
Next, while diluting fluorine gas at the same flow rate, a solution obtained by dissolving the reaction crude liquid (115 g) obtained in Example 6-1 in R-113 (863 g) was injected over 24.8 hours.

Next, while blowing the diluted fluorine gas at the same flow rate and maintaining the reactor pressure at 0.15 MPa, the temperature of the R-113 solution having a benzene concentration of 0.04 g / mL is increased from 25 ° C. to 40 ° C. 30 mL was injected, the benzene inlet of the autoclave was closed, and stirring was continued for 0.3 hours. Next, 20 mL of the above benzene solution was injected while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C. while blowing diluted fluorine gas at the same flow rate, and stirring was continued for 0.3 hours. . The same operation was repeated once, and stirring was further continued for 1.0 hour. The total amount of benzene injected was 3.14 g, and the total amount of R-113 injected was 70 mL. When the target product was quantified by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ), the yield of Compound A-3 was 68%, and the yield of Compound B-3 was 93%.

[Example 6-3] Production examples of the following compounds A-4 and B-4

The reaction was carried out using the same reaction apparatus as in Example 5-3. 135.1 g of the reaction crude liquid obtained in Example 6-2 was charged into a flask together with 2.98 g of KF powder, and heated at 91 ° C. for 5 hours in an oil bath with vigorous stirring. 118.8 g of liquid sample was recovered at the reflux outlet. As a result of analysis by GC-MS, CF ₃ CF (OCF ₂ CF ₂ CF ₃ ) COF and the title compound were confirmed as main products. When the yield of the title compound was determined by NMR, the yield of the title compound A-4 was 62%, and the yield of the compound B-4 was 83%.

¹⁹ F-NMR (282.7 MHz, solvent CDCl ₃ , standard: CFCl ₃ , internal standard: C ₆ F ₆ ) δ (ppm)
Compound A-4: -51.2 (2F), -79.9 (4F).
Compound B-4: 26.2 (1F), -53.0 (1F), -57.6 (1F), -76.8 (1F), -87.7 (1F), -117.8 (1F) ).

Industrial applicability

According to the method of the present invention, the ester bond of the fluorine-containing ester compound can be decomposed at a low reaction temperature. Moreover, according to the method of the present invention, the reaction can be carried out efficiently at an unexpectedly high reaction rate without decreasing the reaction rate even when the reaction temperature is low. That is, the method of the present invention is a very advantageous method in industrial implementation.
Furthermore, according to the present invention, an ester bond decomposition reaction can be carried out while producing an arbitrary fluorine-containing ester compound by an advantageous method.

Claims (12)

-20 A method of obtaining a decomposition reaction product by an ester bond to decompose ester bonds of the fluorinated ester compound which can be decomposed, the decomposition reaction of the ester bond in the presence of KF without solvent substantially 100 A method for producing a decomposition reaction product, characterized in that the reaction is carried out at a reaction temperature of 0 ° C., the fluorine-containing ester compound is continuously supplied to the reaction zone, and the reaction is carried out while continuously taking out the decomposition reaction product from the reaction zone. .   The production method according to claim 1, wherein the fluorinated ester compound is a compound having —C (O) O—CF— as a partial structure. 3. The fluorine-containing ester compound is a compound represented by the formula (4), and the decomposition reaction product is a compound represented by the formula (5) and / or a compound represented by the formula (6). The manufacturing method as described in.
R ^CF COOCFR ^AF R ^BF (4)
R ^AF R ^BF C = O (5)
R ^CF COF (6)
Here, R ^AF is a fluorine atom or a monovalent organic group, R ^BF is a monovalent organic group, or R ^AF and R ^BF may be bonded to each other to form a divalent organic group. ^CF is a monovalent organic group, and a fluorine atom is present in at least one group selected from R ^AF , R ^BF and R ^CF. R ^AF, R ^BF, and R ^CF is 1 to 10 carbon atoms, a perfluoroalkyl group, a perfluoro (partially chlorinated alkyl) group, perfluoroalkoxy group or a perfluoro (partially chlorinated (alkoxyalkyl)) group, R ^AF May be a fluorine atom, or R ^AF and R ^BF may be a C 1-10 perfluoroalkylene group, perfluoro (partial chloroalkylene) group, perfluoroalkyleneoxyalkylene group or perfluoro (partial chloro ( The production method according to claim 3, which is an alkyleneoxyalkylene) group. A compound represented by formula (4) is reacted with a compound represented by formula (1) and a compound represented by formula (2) to obtain a compound represented by formula (3). The production method according to claim 3, which is a compound produced by reacting a compound represented by) with fluorine in a liquid phase.
HOCHR ^A R ^B (1)
R ^C COX (2)
R ^C COOCHR ^A R ^B (3)
Here, when R ^AF is a fluorine atom, R ^A is a hydrogen atom, and when R ^A and R ^AF are the same monovalent organic group, R ^A is a monovalent organic group that is not fluorinated. R ^a when the R ^a and R ^AF are different monovalent organic group is a monovalent organic group fluorinated, R ^B when there is the R ^B and R ^BF is the same monovalent organic group In the case of a monovalent organic group that is not fluorinated and R ^B and R ^BF are different monovalent organic groups, R ^B is a monovalent organic group that is fluorinated.
Further, R ^A and R ^B when R ^AF and R ^BF are bonded to form a divalent organic group with one another are combined to form a divalent organic group with one another, from R ^A and R ^B The divalent organic group formed from R ^A and R ^B when the formed divalent organic group is the same as the divalent organic group formed from R ^AF and R ^BF is a divalent organic group that is not fluorinated. There, divalent organic group formed from R ^a and R ^B when different is a divalent organic radical fluorination.
R ^C where the R ^C and R ^CF are the same monovalent organic group is a monovalent organic group which is not fluorinated, R ^C where the R ^C and R ^CF are different monovalent organic groups fluorine It is a monovalent organic group to be converted.
X is a halogen atom.   The production method according to claim 5, wherein the compound represented by formula (3) has a fluorine atom content of 30 to 84 mass%. R ^A is a hydrogen atom, a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, an etheric oxygen atom-containing monovalent saturated hydrocarbon group, or a partial halogeno (an etheric oxygen atom-containing monovalent saturated hydrocarbon). A group in which R ^AF is a fluorine atom or a group in which substantially all of the hydrogen atoms present in R ^A are substituted with fluorine atoms,
R ^B is a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, an etheric oxygen atom-containing monovalent saturated hydrocarbon group, or a partial halogeno (etheric oxygen atom-containing monovalent saturated hydrocarbon) group. , R ^BF is a group in which substantially all of the hydrogen atoms present in R ^B are substituted with fluorine atoms,
Alternatively, R ^A and R ^B are bonded to each other to form a divalent saturated hydrocarbon group, a partial halogeno divalent saturated hydrocarbon group, an etheric oxygen atom-containing divalent saturated hydrocarbon group, or a partial halogeno (etheric oxygen atom-containing 2 Valent saturated hydrocarbon) group, and R ^AF and R ^BF are groups in which substantially all of the hydrogen atoms present in the group formed from R ^A and R ^B are substituted with fluorine atoms,
R ^C and R ^CF are the same group and are a monovalent saturated hydrocarbon group, a partial halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial halogeno (containing an etheric oxygen atom) The process according to claim 5 or 6, wherein substantially all of the hydrogen atoms present in the group selected from (monovalent saturated hydrocarbon) groups are groups substituted by fluorine atoms. R ^A and R ^B are each an alkyl group, a partial chloroalkyl group, an alkoxyalkyl group or a partial chloroalkoxyalkyl group having 1 to 10 carbon atoms, and R ^A may be a hydrogen atom, or R ^A and R ^B are a C 1-10 alkylene group, partial chloroalkylene group, alkyleneoxyalkylene group or partial chloro (alkyleneoxyalkylene) group,
Each R ^AF and R ^BF, of 1 to 10 carbon atoms, a perfluoroalkyl group, a perfluoro (partially chlorinated alkyl) group, perfluoroalkoxy group or a perfluoro (partially chlorinated (alkoxyalkyl)) group, in R ^AF is a fluorine R ^AF and R ^BF may together be a C 1-10 perfluoroalkylene group, perfluoro (partial chloroalkylene) group, perfluoroalkyleneoxyalkylene group or perfluoro (partial chloro (alkyleneoxy). Alkylene)) group,
R ^C and R ^CF are the same group and are a ^C 1-10 perfluoroalkyl group, perfluoro (partial chloroalkyl) group, perfluoroalkoxyalkyl group or perfluoro (partial chloro (alkoxyalkyl)) group,
X is a fluorine atom, The manufacturing method in any one of Claims 5-7.   The manufacturing method according to any one of claims 5 to 8, wherein the compound represented by the formula (3) has a molecular weight of 200 to 1,000.   The production method according to claim 1, wherein the ester bond decomposition reaction is performed by a liquid phase reaction.   The production method according to any one of claims 1 to 9, wherein the decomposition reaction of the ester bond is carried out by a gas phase reaction at a reaction temperature of -20 to 100 ° C which is not lower than the boiling point of the decomposition reaction product. A compound represented by the following formula (A-4).