WO2002048085A1

WO2002048085A1 - Process for producing product of decomposition of fluorinated ester compound

Info

Publication number: WO2002048085A1
Application number: PCT/JP2001/010889
Authority: WO
Inventors: Kunio Watanabe; Yasuhiro Suzuki; Koichi Yanase; Takashi Okazoe
Original assignee: Asahi Glass Company, Limited
Priority date: 2000-12-13
Filing date: 2001-12-12
Publication date: 2002-06-20
Also published as: JPWO2002048085A1; JP4126542B2; AU2002221128A1

Abstract

A process for production with high productivity which comprises efficiently decomposing a fluorinated ester compound at a low temperature and a high reaction rate. In the process, a fluorinated ester compound having a decomposable ester bond is decomposed at the ester bond to obtain a decomposition product. The ester bond decomposition reaction is conducted in the presence of KF at a temperature of 200°C or lower substantially without using a solvent. The reaction is conducted while continuously supplying the fluorinated ester compound to the reaction zone and continuously discharging the decomposition products from the reaction zone.

Description

Specification

Method for producing a decomposition reaction product of a fluorine-containing ester compound

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 fluorine-containing ester compound to produce a decomposition reaction product, and further relates to a method for efficiently producing a fluorine-containing ester compound used in the method. Background technology>

Conventionally, as a method of fluorinating all of the C-H portion in a C-H-containing compound to C-F, a method of using cobalt trifluoride, a method of directly fluorinating using fluorine gas, or a method of fluorinating. Hydrogen chloride 方法 A method of performing a fluorination reaction by electrolysis (electrofluorination, hereinafter referred to as “ECF method”) is known. Among these methods, direct fluorination using fluorine gas is known to be performed in a gas phase or in a liquid phase. However, the method performed in the gas phase has a problem that a C—C single bond is broken during the fluorination reaction and various types of by-products are generated, and the method performed in the liquid phase is advantageous (WO 00 / 56694).

Also, (1) a method of decomposing the ester bond of the perfluoroester compound at 224 to 254 ° C aAm. Chem. Soc. 1998, 120, 7117), (2) a method of decomposing the perfluoroester compound by Na Method of performing ester decomposition reaction at 80 to 200 ° C in the presence of F (US 3900372), (3) Method of performing ester decomposition reaction of perfluoroester by batch reaction in the presence of solvent and NaF or KF (US 5466877), are known.

However, the literature in (1) requires that the reaction be carried out in the presence of alkali metal fluoride. Is neither described nor suggested. 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 references (2) and (3) have a problem that the yield is low and the reaction rate is low. Reference (3) describes an example in which the reaction does not proceed when the reaction is performed in the absence of a solvent. Invention disclosure>

The present invention has been made to solve the above problems, and provides a method for continuously decomposing a fluorine-containing ester compound by effectively decomposing an ester bond of the fluorine-containing ester compound. Further, the present invention provides a method for efficiently producing the fluorine-containing ester compound used in the method.

That is, the present invention provides the following manufacturing method.

1. A method for obtaining a decomposition reaction product by decomposing an ester bond of a fluorine-containing ester compound in which an ester bond can be decomposed, wherein the ester bond decomposition reaction is carried out in the presence of KF without substantially using a solvent. At a reaction temperature of not more than ° C, and continuously supplying the fluorinated ester compound to the reaction zone, and performing the reaction while continuously extracting the decomposition reaction product from the reaction zone. Production method.

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 a compound represented by Z or the formula (6). Production method.

R ^CF CO〇CFR ^AF R ^BF (4)

RAF _R BF _{C = 0} (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 A fluorine atom is present in at least one group selected from R ^AF , R ^BF and R ^CF which is a monovalent organic group.

3. A compound represented by the formula (4) is reacted with a compound represented by the formula (1) and a compound represented by the formula (2) to form a compound represented by the formula (3); (3) The production method described above, which is a compound produced by reacting the compound represented by (3) with fluorine in a liquid phase.

HOCHRARB (1)

R ^c COX (2)

R ^c C〇OCHR ^A R ^B (3)

Here, when R ^AF is a fluorine atom, RA is a hydrogen atom, and when R ^A and R ^AF are the same monovalent organic group, R ^A is a non-fluorinated monovalent organic group, and When R ^AF is a different monovalent organic group, R ^A is a monovalent organic group to be fluorinated, and when R ^B and R ^BF are the same monovalent organic group: ^B is not fluorinated When R ^B and R ^BF are monovalent organic groups that are different monovalent organic groups, RB is a monovalent organic group to be fluorinated.

When R ^AF and R ^BF are bonded to each other to form a divalent organic group, R ^A and R ^B are bonded to each other to form a divalent organic group, and R ^A and R ^B 2 Ataiyu machine group formed from the, R ^AF and a divalent organic group is a divalent organic not fluorinated formed from R ^a and R ^B when it is identical to the divalent organic group formed from R ^BF a group, a divalent organic group formed from R ^a and R ^B when different is a divalent organic radical fluorination.

When RC and RCF are the same monovalent organic group, _R t; is a non-fluorinated monovalent organic group, and when R ^G and R ^eF are different monovalent organic groups, R ^e is fluorinated Is a monovalent organic group.

X is a halogen atom.

4. The compound represented by the formula (3) has a fluorine atom content of 30 to 84% by mass. The above-mentioned manufacturing method.

5. ^RA is a hydrogen atom, 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 (a monovalent saturated hydrocarbon group containing an etheric oxygen atom) A saturated hydrocarbon group), wherein R ^AF is a fluorine atom or a group in which substantially all of the hydrogen atoms present in R ^A have been replaced by 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 octalogeno (etheric oxygen atom-containing monovalent saturated hydrocarbon) group Wherein R ^BF is a group in which substantially all of the hydrogen atoms present in R ^B have been replaced by fluorine atoms;

Or combines R ^A and R ^B are each other bivalent saturated hydrocarbon group, partially halogeno 2 Atai飽sum hydrocarbon group, an etheric oxygen atom-containing bivalent saturated hydrocarbon group or moiety halogenoalkyl (etheric oxygen atom, A divalent saturated hydrocarbon) group, wherein R ^AF and R ^BF are groups in which substantially all of the hydrogen atoms in the group formed from R ^A and R ^B have been replaced by fluorine atoms;

R ^c and R ^{e F} 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 (etheric oxygen The above-described production method, wherein substantially all of the hydrogen atoms present in the group selected from the group consisting of an atom-containing monovalent saturated hydrocarbon group are substituted with fluorine atoms.

6. The above-mentioned production method, wherein the compound represented by the formula (3) has a molecular weight of from 200 to 100.

7. The above production method wherein the ester bond decomposition reaction is carried out by a liquid phase reaction.

8. The above production method, wherein the decomposition reaction of the ester bond is carried out by a gas phase reaction at a reaction temperature not lower than the boiling point of the decomposition reaction product and not higher than 100. BEST MODE FOR CARRYING OUT THE INVENTION>

In the following description of the present specification, a compound represented by the formula (4) is referred to as a compound (4). The same applies to compounds represented by other formulas.

In the present specification, the organic group refers to a group essentially including a carbon atom, and includes a saturated or unsaturated structure.

As the organic group, a hydrocarbon group, an octogeno hydrocarbon group, a hetero atom-containing hydrocarbon group, or a halogeno (hetero atom-containing hydrocarbon) group is preferable. From the viewpoint of solubility in the liquid phase used in the fluorination reaction, these organic groups are preferably groups having 1 to 20 carbon atoms, and particularly preferably groups having 1 to 10 carbon atoms.

The hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group. Examples of the monovalent saturated aliphatic hydrocarbon group include an alkyl group and a cycloalkyl group, and the structure of the alkyl group may be any of a straight-chain structure, a branched structure, a ring structure, and a partially ring-shaped structure. You may. 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, and a structure having a ring portion.

The alkyl group or the alkylene group preferably has 1 to 10 carbon atoms. Examples of the alkyl group include 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, and a cycloalkyl group part in which the alkyl group is an alkyl group. And a cycloalkylalkyl group.

Examples of the alkylene group include groups in which one hydrogen atom of the above-mentioned alkyl group is a bond, and a linear or branched alkylene group is preferable.

Examples of the cycloalkyl group include a 3- to 6-membered cycloalkyl group, and a cyclopentyl group and a cyclohexyl group are preferable. As a cycloalkylene group Is preferably a cyclopentylene group or a cyclohexylene group.

In the present specification, a halogeno group refers to a group in which one or more hydrogen atoms have been replaced by halogen atoms. The halogeno group may be a group having a hydrogen atom or a group not having a hydrogen atom. A partial halogeno group refers to a group in which part of a hydrogen atom has been replaced by a halogen atom. That is, the partial halogeno group is a group having a hydrogen atom. The Belha geno group is a group in which all of the hydrogen atoms are fluorinated, and is a group in which no hydrogen atoms are present. The meanings of the terms halogeno, partial halogeno, and bergha-geno have the same meaning even when the ノ and ゲン atoms are specified.

Examples of the halogen atom in the halogeno group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom, a chlorine atom, or a bromine atom is preferable.From the viewpoint of the usefulness of the compound, only a fluorine atom, or It preferably comprises a fluorine atom and a chlorine atom.

A halogeno hydrocarbon group is a group in which one or more of the hydrogen atoms present in the hydrocarbon group has been replaced by a halogen atom.

The monovalent halogeno saturated hydrocarbon group is preferably a fluoroalkyl group or a fluoro (partial cycloalkyl) group, etc., and is preferably a perfluoroalkyl group or a perfluoro (partial cycloalkyl) group (ie, a partial cycloalkyl group). In which all of the hydrogen atoms in the group are replaced by fluorine atoms). As the divalent halogeno saturated hydrocarbon group, a fluoroalkylene group or a fluoro (partial cycloalkylene) group is preferable, and a perfluoroalkylene group or a perfluoro (partial chloroalkylene) group (that is, a partial cycloalkylene group) is preferred. Wherein all of the hydrogen atoms in the group are replaced by fluorine atoms). The perfluoro (partially fluoroalkyl) group is the same as the perfluoroalkyl group, and the perfluoro (partially alkylene) group is the same as the perfluoroalkylene group.

A hetero atom-containing hydrocarbon group is a group such as an oxygen atom, a nitrogen atom, or a sulfur atom. A group consisting of a terrorist atom, a carbon atom, and a hydrogen atom. As the hetero atom, an etheric oxygen atom (o of c_o—C) is particularly preferred. The heteroatom is preferably present between the carbon-carbon atoms of the hydrocarbon group or at the bonding terminus of said 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 the usefulness of the compound, availability, ease of production, and usefulness of the product) , An alkoxyalkyl group, etc.) are preferable, and the divalent group is preferably an alkylene group containing an etheric oxygen atom (eg, a polyoxyalkylene group).

As the alkoxyalkyl group, a group having 1 to 10 carbon atoms in the alkoxy group is preferable. Examples of the alkoxyalkyl group include an ethoxymethyl group, an 11-propoxyl group, and a 2-propoxyl group. As the polyoxyalkylene group, a polyoxyethylene group and a polyoxypropylene group are preferable. The halogeno (hetero atom-containing hydrocarbon) group refers to a group in which one or more of the hydrogen atoms of the hetero atom-containing hydrocarbon group has been substituted with a halogen atom. As the monovalent group, a fluoro (alkoxyalkyl) group or a fluoro (partial alkyl (alkoxyalkyl)) group is preferred, and a perfluoro (alkoxyalkyl) group or a Belfluoro (partial alkyl (alkoxyalkyl)) group is particularly preferred. . 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 which can undergo a decomposition reaction of the ester bond is decomposed. Examples of the fluorine-containing ester compound in which an ester bond can be decomposed include a compound having a partial structure (a C (0) 0-CF-) in which a fluorine atom is bonded to a carbon atom adjacent to an oxygen atom forming an ester bond. Can be The carbon atom to which the fluorine atom in this partial structure is bonded has an additional bond. A monovalent atom (a fluorine atom is preferred in terms of availability) or a monovalent organic group (a trifluoromethyl group is preferred in terms of availability) is bonded to the bond. Is also good. Alternatively, the carbon atom to which the fluorine atom is bonded may be a carbon atom forming a ring. The partial structure in the fluorinated ester compound is one or more, preferably 1 to 10, and more preferably 1 or 2 from the viewpoint of the usefulness of the compound and the ease of the reaction operation.

Hereinafter, a compound having one decomposable ester bond will be described as an example. As the fluorine-containing ester compound having one decomposable ester bond, the following compound (4) is preferable.

R ^CF CO〇CFR ^AF R ^BF (4)

Here, R ^AF , R ^BF , and R ^eF are as described above. The compound (4) is preferably a substantially perfluorinated compound. A substantially perfluorinated compound refers to a compound whose properties as a compound are equivalent to those of a perfluorinated compound, even when a non-fluorinated hydrogen atom is present. Further, R ^AF , R ^BF , and R ^GF are a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partial chromate (monovalent saturated hydrocarbon)) group, a perfluoro (a monovalent saturated hydrocarbon containing an etheric oxygen atom) group, and a perfluoro group. (Partial port (etheric oxygen atom-containing monovalent saturated hydrocarbon)) group is preferable, and in ^RAF , a fluorine atom is also preferable in addition to the above. Further, as R ^AF , R ^BF and R ^CF , a perfluoroalkyl group, a perfluoro (partially alkyl)) group, a perfluoroalkoxyalkyl group, and a perfluoro (partially alkoxyalkyl) group are particularly preferred. In addition, in ^RAF , a fluorine atom is also preferable in addition to the above.

In addition, R ^AF and R ^BF jointly form a perfluoro divalent saturated hydrocarbon group, a perfluoro (partially halogeno (divalent saturated hydrocarbon)) group, a perfluoro (a divalent saturated hydrocarbon containing an etheric oxygen atom) group, or a perfluoro group. (Partial halogeno (etheric acid Divalent saturated hydrocarbons containing carbon atoms))

And a perfluoro (partial cycloalkylene)) group, a perfluoroalkyleneoxyalkylene group, or a perfluoro (partial cycloalkylenealkylene) group.

Specific examples of the compound (4) include a compound represented by the following formula. However

In the following formulas, C y ^F is pel full O b a cyclohexyl group, R ^{1 F} and R "represents an independently, respectively It fluorine atom or Bok Rifuruoromechiru group.

CF ₃ CF ₂ CF ₂ 0CFR ^{2 F} C00CFR ^{1 F} (CF ₃ )

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCFR ^{1 F} CF ₂ CFC ¹ CF ₂ C1

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCFR ^{1 F} CF ₂ CF ₃

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCFR ^{1 F} CF ₂ CF ₂ CF ₃

CF ₃ CF ₂ CF ₂ 0CFR ^{2 F} C00Cy ^F

CF ₃ CF ₂ CF ₂ OCF ₂ COOCFR ^{1 F} CF ₂ 0CF ₂ CF ₂ CF ₃

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCFR ^{2 F} COOCFR ^{1 F} (CF ₃ )

In the present invention, the ester bond of the fluorinated ester compound is decomposed. The conditions and method of the ester bond decomposition reaction are appropriately determined depending on the type of the fluorinated ester compound and the intended fluorinated compound (whether the target compound is the compound (5) or the compound (6)). Can be changed. The decomposition reaction of the ester bond is performed while continuously supplying the fluorine-containing ester compound to the reaction zone and continuously extracting the decomposition reaction product from the reaction zone.

The reaction of the present invention is carried out substantially without using a solvent. Here, the solvent refers to a liquid mixture other than the compounds involved in the reaction (ie, the fluorine-containing ester compound and its decomposition reaction product). The supply rate of the fluorinated ester compound and the withdrawal 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 the apparatus, the reaction conditions and the like. For example, when the fluorinated ester compound is a compound having a boiling point lower than the decomposition reaction temperature of the ester bond, the decomposition reaction of the ester bond can be performed in a gas phase reaction mode.

When the reaction is carried out in a gas phase reaction mode, the gaseous fluorinated ester compound may be passed through a reactor in which KF is a fixed bed or a fluidized bed. On the other hand, when the boiling point of the fluorine-containing ester compound is equal to or higher than the decomposition reaction temperature of the ester bond, the reaction is preferably performed by a liquid phase reaction method. When the reaction is carried out in a liquid phase reaction mode, it is preferred that KF and the fluorinated ester compound are charged into the reaction vessel and stirred, and the fluorinated ester compound is supplied thereto to carry out the reaction. 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. Furthermore, in this case, it is preferable that the reaction and distillation are simultaneously performed using a reaction apparatus provided with distillation or the like, so that the reaction is performed while continuously distilling the reaction product from the reaction site. Since the decomposition reaction product of the ester bond usually has a lower boiling point than that of compound (4), it can be continuously and efficiently extracted by distillation. The decomposition reaction of the ester bond is performed in the presence of KF. KF acts as a nucleophile, and F— derived from KF nucleophilically adds to the carbonyl group present in the ester bond of compound (4), and R ^AF R ^BF CFO— (6) is generated. F— is further eliminated from R ^AF R ^BF CFO— to produce compound (5). The eliminated F— reacts in the same manner as another compound (4). 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 from 1 to 500 mol%, more preferably from 5 to 50 mol%, based on compound (4).

In the present invention, by performing the reaction using KF, other alcohols such as NaF can be used. Decomposition reaction products can be obtained more efficiently at lower temperatures than when using potassium metal fluoride. The upper limit of the reaction temperature is 200 ° C, preferably 150 ° C, particularly preferably 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 120 ° C. Since the decomposition reaction of the ester bond 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 fluorinated ester compound is in a night state under the decomposition reaction conditions, a solvent is not required since the compound itself forms a liquid phase. When it is gaseous, the reaction can be performed without using a solvent. That is, while the conventional ester-bond decomposition reaction was carried out in the liquid phase in the presence of a solvent, the method of the present invention can be carried out without using a solvent with substantially no solvent, so that the volumetric efficiency is improved. This is also advantageous from the viewpoint of controlling by-products. The reaction can be carried out at a low reaction temperature both in the case of carrying out the reaction in the gas phase and in the case of carrying out the reaction in the liquid phase.

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

In the present invention, a target compound is obtained from a reaction product of a decomposition reaction of an ester bond. Examples of the reaction product include a compound having a terminal structure of one COF and a ketone compound. For example, in the decomposition reaction of the ester bond of the compound (4), the following compounds (5) and Ζ or the compound (6) ) Can be generated.

_R AF _R BF _{C = 0} (5)

R ^CF COF (6)

Here, R ^AF , R ^BF and R ^eF are the same groups corresponding to compound (4), and the 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 mentioned as the specific examples of the compound (5). However, in the following formula, R ^1F represents a fluorine atom or a trifluoromethyl group.

CF ₃ COR ^{1 F}

CF ₃ CF ₂ COR ^{1 F}

CF, 3 CF ', 2 C ^ F, 2 COR ^{1 F}

CF ₃ CF ₂ CF ₂ 0 CF ₂ COR ^{1 F}

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COR ' ^F

Further, when R ^AF in the compound (5) is a fluorine atom, it is preferable that the compound (5) and the compound (6) formed by the decomposition reaction of the ester bond have the same structure. When the compound (5) and the compound (6) have the same structure, the purification process 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 a fluorination reaction of compound (3A) described below.

R ^BF COOCF ₂ R ^BF (4A)

However, R ^BF has the same meaning as described above, and the preferred embodiment is also the same.

Compound (4) can be obtained by reacting compound (1) with compound (2) to give compound (3), and reacting compound (3) with fluorine in a liquid phase to produce compound (3). (4) is preferred. The method can be carried out according to the method of WOOZ5 6694 by the present inventors, and a compound having an arbitrary structure can be obtained. As the compound (1), because a fluorine-free alcohol can be easily obtained, R ^A and R ^B are a hydrogen atom, a monovalent saturated hydrocarbon group, a partially saturated monovalent saturated hydrocarbon group, A monovalent saturated hydrocarbon group containing an etheric oxygen atom or a partial chloro (monovalent saturated hydrocarbon containing an etheric oxygen atom) group is preferable, and ^RA is preferably a hydrogen atom in addition to the above. Further, as R ^A and R ^B , an alkyl group, a partially substituted alkyl group, an alkoxyalkyl group, and a partially substituted alkoxyalkyl 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 compound (1) are jointly a divalent saturated hydrocarbon group,

(Divalent saturated hydrocarbon) group, etheric oxygen atom-containing divalent saturated hydrocarbon group, and partial chloro (etheric oxygen atom-containing divalent saturated hydrocarbon) group, preferably alkylene It is preferable to form a group, a partial cycloalkylene group, an alkyleneoxyalkylene group or a partial cycloalkylene (alkyleneoxyalkylene) group. As the compound (1), a compound having an arbitrary structure can be obtained by easily obtaining the compound (1) corresponding to the structure of the compound (4) because compounds having various structures can be easily obtained.

(4) can be easily manufactured.

Specific examples of the compound (1) include a compound represented by the following formula. However

In the following formula, Cy represents a cyclohexyl group, and R ¹ represents a hydrogen atom or a methyl group.

CH ₃ CHR ¹ OH

CH ₃ C¾ CHR ¹ OH

C¾ = CHCH 'OH

CH ₃ CH ₂ C¾ CHR ¹ OH

CH ₂ C1CHC1CH ₂ CHR ¹ OH

CF ₂ C1CFC1CH ₂ CHR ¹ OH

CyOH

R ^c in compound (2) is preferably a monovalent organic group having a fluorine atom, and is a monovalent saturated hydrocarbon group, a partially octalogeno monovalent saturated hydrocarbon group, or a monovalent saturated hydrocarbon group containing an etheric oxygen atom. A group in which substantially all of the hydrogen atoms present in a group selected from a hydrogen group and a partial octalogeno (monovalent saturated hydrocarbon containing an etheric oxygen atom) group are substituted with a fluorine atom is preferable, and in particular, perfluoro Monovalent saturated hydrocarbon group, perfluoro (partial chromate (monovalent saturated hydrocarbon)) group, perfluoro (etheric oxygen atom-containing monovalent saturated hydrocarbon) group, perfluoro (partial chromate (etheric oxygen atom containing) Monovalent saturated hydrocarbon)) groups are preferred, and especially perfluoroalkyl groups, perfluoro (partial cycloalkyl) groups, perfluoroalkoxyalkyl groups, Furuoro (partial black port (alkoxyalkyl)) group is preferred.

Specific examples of the compound (2) include the same compounds as the 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). And the compound (2A) produce the following compound (3A)

R ^B CH ₂ OH (1 A)

R ^BF COF (2 A)

R ^B COOCH ₂ R ^BF (3 A)

Next, compound (4) is obtained by reacting compound (3) produced by the reaction between compound (1) and compound (2) with fluorine in a liquid phase. The reaction between compound (1) and compound (2) can be carried out by applying known ester reaction methods and conditions.

In the reaction between compound (1) and compound (2), HF is generated. For example, an alkali metal fluoride (preferably NaF or KF) or a trialkylamine may be present in the reaction system. The HF scavenger is preferably used when compound (1) or compound (2) is an acid-labile compound. When an HF scavenger is not used, it is preferable to discharge HF out of the reaction system by entraining HF in a nitrogen stream. When an alkali metal fluoride is used, it is preferably 1 to 10 moles per mole of the compound (2).

In general, the reaction temperature of the compound (1) with the compound (2) is preferably not less than 50 T :, more preferably not more than + 100 ° C or not more than the boiling point of the solvent. The reaction time of the reaction can be appropriately changed depending on the supply rate of the raw materials and the amount of the compound used in the reaction. The reaction pressure (gauge pressure, the same applies hereinafter) is preferably from 0 to 2 MPa.

The molar ratio of the compound (1) to the compound (2) is preferably such that the amount of the compound (2) was 0.5 to 5 times, more preferably 1 to 2 times, the mole of the compound (1). Better.

The crude product containing the compound (3) produced by the reaction of the compound (1) with the compound (2) may be purified according to the purpose or used as it is for the next reaction or the like. From the viewpoint of stably performing the fluorination reaction in the process, it is desirable to carry out separation and purification.

The fluorine content (the fluorine content is the ratio of the mass of fluorine atoms to the molecular weight) of compound (3) obtained by reacting compound (1) with compound (2) is preferably 30% by mass or more. The fluorine content is preferably from 30 to 84% by mass, more preferably from 30 to 76% by mass. If the fluorine content is too low, the solubility of compound (3) in the liquid phase will be extremely low, and the reaction system during the fluorination reaction will be non-uniform. Can not be fed into the reaction system. The upper limit of the fluorine content is not particularly limited, but those that are too high are difficult to obtain, are expensive, and are not economical. Further, the molecular weight of the compound (3) is preferably from 200 to 1,000 in 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 evaporate, 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, purification of compound (3) may be difficult.

Specific examples of the compound (3) include a compound represented by the following formula. However

In the following formulas, 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.

CF ₃ CF ₂ CF ₂ 0CFR ^2F C00CHR '(CH ₃ )

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCHR ¹ C¾ CHC 1CH ₂ C1

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCHR ¹ CH ₂ CH ₃

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCHR ¹ CH ₂ C¾ CH ₃

CF ₃ CF ₂ CF ₂ 0CFR ^2F C00Cy

CF ₃ CF ₂ CF ₂ OCFR ^{2 F} COOCHR ¹ C¾ CFC1 CF ₂ C1

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCFR ^{2 F} COOCHR ¹ (CH ₃ )

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

In the compound (4), R ^AF is a monovalent saturated hydrocarbon group, a partially octalogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial halogeno (a monovalent saturated hydrocarbon group containing an etheric oxygen atom). saturated hydrocarbon) is preferably substantive all of the hydrogen atoms present in radicals are radicals or fluorine atoms substituted by fluorine atoms selected from the group, all of the hydrogen atoms present in the fluorine atom or R ^a Particularly preferred are fluorinated groups. In addition, ^RBF 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 (a monovalent saturated hydrocarbon containing an etheric oxygen atom) preferably substantially all of the hydrogen atoms present in groups are substituted groups where a fluorine atom selected from group, particularly preferably all of the hydrogen atoms present in R ^B is fluorinated groups . R ^GF is a same group as R ^e, monovalent saturated hydrocarbon groups, moieties eight Rogeno monovalent saturated hydrocarbon group, ether oxygen atom-containing monovalent saturated hydrocarbon group, and partially eight Rogeno (etheric It is preferable that substantially all of the hydrogen atoms present in the group selected from the oxygen atom-containing monovalent saturated hydrocarbon groups are substituted with fluorine atoms, and particularly those groups in which all are fluorinated. It is preferred that

When fluorinating compound (3) in a liquid phase, it is preferable to introduce fluorine gas into a solvent in which compound (3) is present. The fluorine gas may be used as it is, or may be a fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic 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 that can dissolve fluorine (F,). The solution As the medium, a solvent that does not contain a C—H bond and requires a C—F bond is preferable. In addition, a perfluoroalkane or one selected from a chlorine atom, a nitrogen atom, and an oxygen atom An organic solvent obtained by perfluorinating a known organic solvent having the above atoms in the structure is preferable. Further, as the solvent, it is preferable to use a solvent having high solubility of the compound (3). Particularly, when the compound (4), the compound (5) or the compound (6) is used, the post-treatment after the reaction becomes easy. Advantageous and preferred.

The amount of the solvent to be used is preferably at least 5 times, more preferably 10 to 100 times, the mass of the compound (3).

The reaction system of the fluorination reaction is preferably a continuous system rather than a batch system. In particular, the following continuous method is preferable from the viewpoint of reaction yield and selectivity. That is, the solvent is charged into the reactor, and stirring is started. Next, a continuous method in which the compound (3) and fluorine gas are continuously and simultaneously supplied at a predetermined molar ratio to a liquid phase in a reactor at a predetermined reaction temperature and a predetermined reaction pressure. When supplying the compound (3), the compound (3) may or may not be diluted with the solvent. However, in order to improve the selectivity and suppress the amount of by-products, the compound (3) diluted with the solvent is supplied. Is preferred. When diluting the compound (3) with a solvent, the amount of the solvent with respect to the compound (3) is preferably at least 5 times, more preferably at least 10 times the mass.

Regarding the amount of fluorine used in the fluorination reaction, whether the reaction is carried out in a batch mode or in a continuous mode, the amount of fluorine is always an excess equivalent to the hydrogen atom in compound (3). It is preferable to use fluorine as described above, and it is particularly preferable to use fluorine so as to be 1.5 times equivalent or more (that is, 1.5 times mole or more) in terms of selectivity. The upper limit of the amount of fluorine is preferably 3.0 times or less.

The reaction temperature of the fluorination reaction is usually preferably 160 ° C. or higher and the boiling point of the compound (3) or lower, and is preferably 150 ° C. in view of the reaction yield, selectivity, and industrial easiness. To + 100 ° C is particularly preferable, and −20 ° C to 150 ° C is particularly preferable. Fluorination The reaction pressure of the 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 industrial easiness.

Further, in order to efficiently advance the fluorination, it is preferable to add a CH 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 at a later stage of the fluorination reaction, or to perform ultraviolet irradiation at a later stage of the reaction. As a result, 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 is 0.1 to 10 mol% based on the hydrogen atoms in the compound (3). And preferably 0.1 to 5 mol%.

The C-H bond-containing compound is preferably added in a state where fluorine gas is present in the reaction system. Further, 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, HF is produced as a by-product, so it is preferable to coexist an HF scavenger in the reaction system for the purpose of removing HF, or to contact the HF scavenger with the outlet gas at the reactor gas outlet. As the HF scavenger, NaF is preferable. When the HF scavenger is present in the reaction system, the amount 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 an HF scavenger is placed at the reactor gas outlet, (a) a cooler (preferably maintained at 10 ° C to room temperature, particularly preferably maintained at about 20) (Port) NaF pellets (A) The cooling layer (preferably maintained at a temperature of 78 ° C to + 10 ° C, more preferably maintained at a temperature of 30 ° C to 0 ° C) -It is preferable to install them in series in the order of (c). In addition, a liquid return line for returning the condensed liquid from the cooler in (c) to the reactor may be provided.

The fluorination of this compound (3) results in the compound (3) being substantially perfluorinated. It is preferable to carry out until the reaction is completed, especially until the perfluorination is effected.

The crude product containing the compound (4) obtained by the fluorination reaction may be used as it is in the next step, or may be purified to 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 compounds (5) and Z or compound (6) by the production method of the present invention is as follows.

That is, the compound (1A) is reacted with the compound (2A) to give a compound (3A), and the compound (3A) is reacted with fluorine in a liquid phase to give a compound (4A). In the compound (4A), This is a method for obtaining a compound (2A) from a reaction product obtained by performing the above-described ester bond decomposition reaction. Further, by reacting compound (2A) with compound (1A) again, compound (2A) can be continuously and efficiently produced. Examples>

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

[Example 1 (Example)]

2 L capacity equipped with a stirrer made of stainless steel autoclave in 97% purity _{_{_{of? 3 (CF 2) 2 OCF}}} (CF 3) COOCF 2 CF (CF 3) O (CF 2) 2 CF 3 crude liquid (hereinafter "Perufuru 1800 g) and KF powder (30 g) produced by the spray drying method were charged, and the temperature was raised to 70 ° C with stirring. When the specified temperature was reached, the crude perfluoroester solution was continuously fed at a rate of 115 gZh. Generated gas is continuously extracted through a stainless steel jacketed column heated at 60 provided at the top of the reactor, Trapped in the pump. From the weight of the captured product and the analysis by GC, CF ₃ (CF ₂ ) ₂₀ CF (CF ₃ ) COF (hereinafter abbreviated as “(HFPO) ₂ ”) is generated at a rate of 110 g / h. It was confirmed. 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 crude perfluoroester solution was 215 gZh. The weight of the product captured by the dry ice trap and analysis by GC confirmed that (HFPO) ₂ was produced 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 crude perfluoroester and 55 g of NaF powder (manufactured by Morita Chemical Industry Co., Ltd.) were charged into the reactor, and the temperature was raised to 140 ° C. with stirring. The NaF powder was heat-treated at 120 ° C for 2 hours before use. When the temperature reached a predetermined temperature, the crude perfluoroester solution was continuously fed at a rate of 60 gZh. From the weight of the product captured by the dry ice trap and the analysis by GC, it was confirmed that (H FPO) ₂ was produced at a rate of 57 gZh. The yield of (HFPO) ₂ was 99%.

[Example 4 (Example)] Production example of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃

(Example 4-1) CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) C〇OCH ₂ CH (CH ₃ ) OCH ₂ CH ₂ CH ₃ Production Example

CH ₃ CH ₂ CH ₂ OCH (CH ₃ ) CH ₂ OH (620 g) was charged into the flask and stirred while bubbling nitrogen gas through. CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CO F (3604 g) was added dropwise over 8 hours while maintaining the internal temperature at 25 to 35. After the 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 continuing to bubble nitrogen gas. The resulting reaction mixture was used for the reaction of Example 4-2.

(Example 4-1-2) CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) C〇OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃

The CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF (2340 g) obtained in Example 4-11 was added to a 300 OmL nickel autoclave, and the mixture was stirred and kept at 25 ° C. At the autoclave gas outlet, a cooler kept at 2 Ot, a packed bed of NaF pellets, and a cooler kept at 10 ° C were installed in series. In addition, a liquid return line was installed to return the coagulated liquid from the cooler kept at 10 一 to the autoclave. After nitrogen gas was blown in for 1.5 hours, fluorine gas diluted to 20% by volume with nitrogen gas (hereinafter abbreviated as diluted fluorine gas) was blown in at a flow rate of 8.91 L / h for 3 hours.

Next, the reaction mixture (106 g) obtained in Example 4-11 was injected over 45.6 hours while blowing the diluted fluorine gas at the same flow rate.

Next, while blowing the diluted fluorine gas at the same flow rate, the CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF solution (18 mL) with a benzene concentration of 0.01 gZmL was heated from 25 ^ to 40. The autoclave's benzene inlet valve was closed, the autoclave's outlet valve was closed, and when the pressure reached 0.2 MPa, the autoclave's fluorine gas inlet valve was closed and stirring continued for 1 hour. I did. Next, the pressure was adjusted to normal pressure, the benzene solution (6 mL) was injected while maintaining the temperature in the reactor at 40 ° C, the benzene inlet valve of the autoclave was closed, and the outlet valve of the autoclave was closed. When the pressure reached 0.2 MPa, the fluorine gas inlet valve of the autoclave was closed, and stirring was continued for 1 hour. Further The operation of benzene injection was repeated once.

The total amount of benzene injected was 0.309 g, the total amount of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF injected was 3 OmL, and 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

Tetrahydrid furfuryl alcohol (20 g) and triethylamine (21.8 g) were placed in a flask and stirred in an ice bath. FCOCF (CF ₃ ) 0CF 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 the dropwise addition, the mixture was stirred at room temperature for 2 hours, and 5 OmL 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 5 OmL of water, dried over magnesium sulfate, and then filtered to obtain a crude liquid. The desired ester compound (66.3 g) was obtained by distillation under reduced pressure as a fraction at 88 to 89 ° CZ 2.7 kPa. GC purity was 98%.

(Example 5-2) Production example of the following compound

R-113 (1614 g) was added to a 300 OmL nickel autoclave, stirred, and kept at 25 保. At the autoclave gas outlet, a cooler maintained at 20 ° C, a packed bed of NaF pellets, and a cooler maintained at 110 ° C are installed in series. did. In addition, a liquid return line was installed to return the condensed liquid from the cooler kept at 110 ° C to the autoclave. 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 at a flow rate of 17.04 L / hl for 1 hour.

Next, a solution obtained by dissolving the crude reaction solution (54 g) obtained in Example 5-1 in R-113 (510 g) was injected over 14.7 hours while blowing the diluted fluorine gas at the same flow rate.

Next, while blowing the diluted fluorine gas at the same flow rate, and while increasing the reactor pressure,

While maintaining the pressure at 0.15 MPa, the benzene concentration was 0.05 g / mL: — 113 solution was injected while increasing the temperature from 25 ° C to 40 ° C, and the benzene inlet of the autoclave was closed. Stirring was continued for 0.3 hours. Next, while injecting the diluted fluorine gas at the same flow rate, maintaining the reactor pressure at 0.15 MPa and maintaining the reactor temperature at 40 ° C, inject 2 OmL of the above benzene solution, and stir for 0.3 hours. Continued

. The same operation was repeated three times, and the stirring was further continued for 2.0 hours. The total amount of benzene injected was 5.0 Og, and the total amount of R-113 injected was 11 mL. ¹⁹ objects

Quantification by F-NMR (internal standard: C ₆ F ₆ ) gave a yield of the title compound of 75.

%Met.

(Example 5-3) Production example of the following compound

56.5 of the crude reaction solution 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 adjusted to a temperature of 5 was installed at the top of the flask, and a liquid sample was collected with a dry ice ethanol trap at the exit of the reflux condenser. 44.0 g after cooling Of the liquid sample was collected. As a result of analysis by GC-MS, CF ₃ CF (ΔCF ₂ CF ₂ CF ₃ ) COF and the title compound were confirmed as main products. The yield of the title compound determined by NMR was 87%.

¹⁹ F- NMR (282. 7MHz, solvent CDC 1 _3, _{reference: CFC 1 3) δ (p} pm):. 26. 3 (IF), - 82. 8 (IF), -83 6 (IF), one 1 18.1 (IF), -125. 9 (IF), -126. 8 (IF), -19.3 (IF),-134.8 (1 F)

[Example 6]

(Example 6

Compound A— 2 Compound B— 2

1 Compound B—1 A mixture of compound A—1 and compound B—1: 59:41 (molar ratio) (100.0 g) and triethylamine (10.7 g) are placed in a flask, and the internal temperature is 10 ° C. Stirred below. 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 dropwise addition, the mixture was stirred at room temperature for 1 hour, and water (50 OmL) was added while keeping the internal temperature not exceeding 15 ° C. To the obtained crude liquid was added dichloropentylfluoropropane (1000 mL, trade name: AK225, manufactured by Asahi Glass Co., Ltd.), and the mixture was separated to give a lower layer. The lower layer was further washed twice with water (50 OmL), dried over magnesium sulfate, and filtered to obtain a crude liquid. Remove the crude liquid Concentration was performed overnight in a vapore, followed by distillation under reduced pressure to obtain a fraction (328.0 g) of 5962 ° C, 0.4 kPa. GC purity was 99.6%.

[Example 6-1-2] Example of production of compound A-3 and compound B-3

Compound A—3

Using the same reactor as in Example 5-2, R-113 (1701 g) was added, stirred, and kept at 25 ° C. Diluted fluorine gas was blown at a flow rate of 17.04 L_ / h for 1 hour. Next, while diluting fluorine gas was blown in at the same flow rate, a solution obtained by dissolving the reaction crude solution (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 R-113 solution with a benzene concentration of 0.04 gZmL was raised from 25 ° C to 40 ° C. While heating, 3 OmL was injected, the benzene inlet of the autoclave was closed, and stirring was continued for 0.3 hour. Next, while injecting the diluted fluorine gas at the same flow rate, while maintaining the reactor pressure at 0.15 MPa and the reactor temperature at 40 ° C, 2 OmL of the above benzene solution was injected, and the mixture was stirred for 0.3 hours. Continued. The same operation was repeated once, and the stirring was further continued for 1.0 hour. The total injection amount of benzene was 3.14 g R-113 was 7 OmL. The desired product was quantified by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ). As a result, the yield of compound A-3 was 68%, and the yield of compound B-3 was 93%.

[Example 6-3] Production example of the following compound B_4 F ₂ C-CF.

0 .0

c Compound B-4 The reaction was carried out using the same reactor as in Example 5-3. 13 5. Ig of the crude reaction solution 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. At the outlet of the reflux condenser, 118. 8 g of a liquid sample was collected. As a result of analysis by GC-MS, CF ₃ CF (ΔCF 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. The yield of the title compound A-4 was 62%, and the yield of the compound B-14 was 83%.

¹⁹ F-NMR (282. 7MHz, solvent CDC 1 _3, reference: CFC 1 _3, internal _{_{standard: C 6 F 6) δ (}} p pm)

Compound A—4: -51.2 (2 F), -79. 9. (4 F).

Compound B—4: 26.2 (IF), -53.0 (IF), -57.6 (IF)

, -76.8 (I F), —87.7 (I F), 1 17.8 (1 F). Industrial potential>

According to the method of the present invention, the ester bond of the fluorinated ester compound can be separated at a low reaction temperature. Can be done. Moreover, according to the method of the present invention, the reaction can be efficiently performed at an unexpectedly high reaction rate without lowering the reaction rate even when the reaction temperature is lowered. That is, the method of the present invention is a very advantageous method in industrial practice.

Further, according to the present invention, the decomposition reaction of the ester bond can be carried out while producing an arbitrary fluorine-containing ester compound by an advantageous method.

Claims

The scope of the claims

1. A method for obtaining a decomposition reaction product by decomposing an ester bond of a fluorinated ester compound in which an ester bond can be decomposed, wherein the ester bond decomposition reaction is performed at 200 ° C in the presence of KF without substantially using a solvent. C. and a reaction temperature of not more than C, and continuously supplying the fluorinated ester compound to the reaction zone, and performing the reaction while continuously extracting the decomposition reaction product from the reaction zone. Production method.

2. The fluorinated ester compound is a compound represented by the formula (4), and the decomposition reaction product is a compound represented by the formula (5) and a compound represented by Z or the formula (6). The production method described in 1.

R ^CF COOCFR ^{AF BF} (4)

RA F _R BF _{C = 0} (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, ^eF tt is a monovalent organic group, and a fluorine atom is present in at least one group selected from R ^AF , R ^BF , and

3. A compound represented by the formula (4) is reacted with a compound represented by the formula (1) and a compound represented by the formula (2) to form a compound represented by the formula (3); 3. The production method according to claim 2, which is a compound produced by reacting the compound represented by (3) with fluorine in a liquid phase.

HOCHRARB (1) R ^c COX (2)

R ^c C〇OCHR ^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 non-fluorinated monovalent organic group, When R ^A and R ^AF are different monovalent organic groups, R ^A is a monovalent organic group to be fluorinated, and when R ^B and R ^BF are the same monovalent organic group, R ^B is R ^B is a monovalent organic group that is not fluorinated, and when R ^B and R ^BF are different monovalent organic groups, R ^B is a monovalent organic group that is fluorinated.

When R ^AF and R ^8F are bonded to each other to form a divalent organic group, R ^A and R ^B are bonded to each other to form a divalent organic group, and R ^A and R ^B When the divalent organic group formed is the same as the divalent organic group formed from R ^AF and R ^{BF, the} divalent organic group formed from R ^A is a non-fluorinated divalent organic group. divalent organic group formed from R ^a and R ^B when different is a divalent organic radical fluorination.

When R ^c and R ^eF are the same monovalent organic group, R ^e is a non-fluorinated monovalent organic group, and when R ^c and R ^GF are different monovalent organic groups, 1 ^ is fluorine Is a monovalent organic group.

X is a halogen atom.

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

5. ^RA is a hydrogen atom, 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 (monovalent saturated hydrocarbon containing an etheric oxygen atom) group, wherein R ^AF is substantially a fluorine atom or a hydrogen atom present in ^RA. All are groups substituted by 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 have been replaced by fluorine atoms,

Or combines R ^A and R ^B are each other bivalent saturated hydrocarbon group, partially halogeno 2 Atai飽sum hydrocarbon group, an etheric oxygen atom-containing bivalent saturated hydrocarbon group or moiety halogenoalkyl (etheric oxygen atom, A divalent saturated hydrocarbon) group, wherein 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 have been replaced by fluorine atoms;

R ^G and R ^{e F} are the same group, and are a monovalent saturated hydrocarbon group, a partially halogeno monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial octaenogeno (etheric 5. The production method according to claim 3, wherein substantially all of the hydrogen atoms present in the group selected from the group consisting of an oxygen atom-containing monovalent saturated hydrocarbon) group are substituted with fluorine atoms.

6. The production method according to claim 3, 4, or 5, wherein the compound represented by the formula (3) has a molecular weight of from 200 to 100.

7. The method according to any one of claims 1 to 6, wherein the decomposition reaction of the ester bond is performed by a liquid phase reaction.

8. The production method according to any one of claims 1 to 6, wherein the decomposition reaction of the ester bond is carried out by a gas phase reaction at a reaction temperature not lower than the boiling point of the decomposition reaction product and not higher than 100 ° C.