WO2004094365A1

WO2004094365A1 - Method for producing fluorine-containing sulfonyl fluoride compound

Info

Publication number: WO2004094365A1
Application number: PCT/JP2004/005874
Authority: WO
Inventors: Koichi Murata; Takashi Okazoe; Eisuke Murotani
Original assignee: Asahi Glass Company, Limited
Priority date: 2003-04-24
Filing date: 2004-04-23
Publication date: 2004-11-04
Also published as: JP2006143589A

Abstract

A method for producing a fluorine-containing sulfonyl fluoride compound which comprises oxidizing RB-E-RA-S-S-RA-E-RB to form XSO2-RA-E-RB (2), reacting the oxidation product with fluorine in a liquid phase to form FSO2-RAF-EF-RBF, and decomposing the fluorination product to prepare FSO2-RAF-COF, wherein RA represents a divalent organic group, RAF represents a divalent organic group or the like, RB represents a monovalent organic group, RBF represents a monovalent organic group or the like, E represents -COOCH2-, EF represents -COOCF2- and X represents a halogen atom. The method is almost free from major conventional difficulties associated with the production of the above sulfonyl fluoride, and also allows the production of fluorine-containing sulfonyl fluoride compounds having various molecular structures and being useful as a raw material for an ion exchange resin or the like with good efficiency at a low cost.

Description

Specification

Technical field of producing fluorine-containing sulfonyl fluoride compounds>

The present invention relates to a method for producing a fluorine-containing sulfonyl fluoride compound useful as an ion exchange resin raw material or the like.

Background technology>

Fluorine-containing sulfonyl fluoride compounds having a fluoroformyl group (for example,

The following compound (i) is a compound useful as a raw material for an ion exchange resin. Conventionally, a compound having a fluoroformyl group is tetrafluoroethylene and zirconium trioxide.

It is synthesized by a method of reacting a perfluoroalkylene oxide with a cyclic compound obtained by a reaction with (SO _s ). For example, as shown in the following formula, the following compound (i) can be obtained by reacting the above cyclic compound with hexafluoropropylene oxide (T. Hiyama (T. Hiyama)) , Organofluorin 'Compounds: Chemistry and Applications, Springer-Verlag (Springer-Verlag), Berlin (Ber 1 in), 2000, pp. 228-230). mm ", F ₂ C = CF ₂

However, conventional synthetic method was disadvantageous way to industrial implementation because it requires careful handling so _3. In addition, because of the difficulty of synthesis, price reduction could not be achieved. Furthermore, since the obtained compound (i) is limited to a compound having a side chain (one CF ₃ ), the performance and membrane of an ion exchange membrane synthesized from a derivative of the compound (i) There were also characteristics problems.

As a method for solving the above problem, a hydrocarbon-based sulfonic acid derivative having a hydroxyl group is used as a starting material to form an ester with a fluorinated carboxylic acid, which is directly fluorinated and thermally decomposed to obtain a fluorosulfonyl having a fluoroformyl group. The following method for obtaining a fluoride compound has been proposed (see International Publication No. WO 02/41438, Pamphlet 1,).

However, also in this method, since the starting material is limited to a sulfonic acid compound such as isethionic acid, the skeleton of the obtained compound is limited.

Invention disclosure>

The present invention has been made for the purpose of solving the problems of the prior art, and uses a readily available raw material, and has a structure which is difficult to obtain efficiently with the prior art. The present invention provides a method capable of producing a compound.

The present inventors have invented a method of converting a disulfide compound into a sulfonyl halide compound, reacting the compound with fluorine in a liquid phase, and then decomposing the reactant to obtain a desired fluorine-containing sulfonylfluoride. And found that the compound can be produced, thereby completing the present invention.

That is, the gist of the present invention is as follows: 1> to <8>.

<1> When a compound represented by the following formula (1) is oxidized to a compound represented by the following formula (2), and when X of the compound represented by the formula (2) is a fluorine atom, As it is, or when X is a halogen atom other than a fluorine atom, X is replaced by a fluorine atom, and then the compound represented by the formula (2) wherein X is a fluorine atom is dissolved in a liquid phase. Reacting with fluorine to form a compound represented by the following formula (3), and further represented by the formula (3) A method for producing a fluorine-containing sulfonyl fluoride compound, which comprises decomposing a compound to obtain a compound represented by the following formula (4).

^{^{^{^{R B -ER A -SSR A -ER B}}}} - - · (1)

XS0 ₂ -R ^A -ER ^B ... (2)

FS0 ₂ -R ^AF -E ^F -R ^BF

FS〇 ₂ -R ^AF — C〇F · · · (4)

(Wherein, R ^A represents a divalent organic group. R ^B represents a monovalent organic group. E represents —COO CH ₂ —, and the carbon atom forming the keto group of E is represented by R ^A. bind or binds to R ^B. X represents a halogen atom. R ^AF is a bivalent organic radical divalent organic group or R ^a the same as R ^a is fluorinated. R ^BF is . a monovalent organic group R ^B the same monovalent organic group or R ^B is fluorinated E ^F is one CO_〇_CF ₂ - represents a).

<2> The production method according to <1>, wherein the compound represented by the formula (2) has a fluorine content of 30% by mass or more.

<3> The production method according to <1> or <2>, wherein the compound represented by the formula (2) has a molecular weight of 200 to 1300.

<4> R ^AF is a perfluoro divalent saturated hydrocarbon group, a perfluoro (partially halogeno divalent saturated hydrocarbon) group, a perfluoro (divalent saturated hydrocarbon containing a hetero atom) group, and a perfluoro (partially halogeno (containing a hetero atom containing A divalent organic group selected from the group consisting of a divalent saturated hydrocarbon)) group, wherein R ^BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially halogeno monovalent saturated hydrocarbon) group, A monovalent organic group selected from the group consisting of a monovalent saturated hydrocarbon containing a hydrogen atom and a perfluoro (partially halogeno (monovalent saturated hydrocarbon containing a heteroatom)) group. The production method described in Crab.

<5> The compound represented by the formula (1) is a compound obtained by reacting a compound represented by the following formula (5) with a compound represented by the following formula (6): 1> to <4 > The production method according to any one of the above.

E ¹ — R ^A -S— S-R ^A — E ¹ · · · (5)

R ^B -E ²

(Wherein, R ^A and R ^B have the same meanings as above, and E ¹ and E ² are one COY. And the other represents one CH ₂ OH, and Y represents a halogen atom or a hydroxyl group. 6> Decompose the compound represented by the formula (3) to obtain the compound represented by the formula (4), and obtain the compound represented by the following formula (7). The production method according to any one of the above.

R ^BF -COF

(In the formula, R ^BF has the same meaning as described above.)

<7> As the compound represented by the formula (6), a compound represented by the formula (7) obtained by decomposing the compound represented by the formula (3), or a compound represented by the formula (7) <5> The production method according to <5>, wherein a compound represented by the following formula (8) obtained by reduction of

R ^BF -COF

R ^BF -CH ₂ OH (8)

(In the formula, R ^BF has the same meaning as described above.)

<8> Hexafluoropropylene oxide is added to the compound represented by the formula (4) obtained by the production method described in any of <1> to <7>, and the compound is represented by the following formula (9). A process for producing a fluorine-containing sulfonyl vinyl ether compound, comprising obtaining a compound represented by the formula (9) and subjecting the compound (9) to a thermal decomposition reaction to obtain a compound represented by the following formula (10).

FS〇 ₂ — R ^AF — COF · · · (4)

FS0 ₂ -R ^AF -CF ₂ OCF (CF ₃ ) COF

FS0 ₂ -R ^AF -CF ₂ OCF = CF ₂ · '· (10).

BEST MODE FOR CARRYING OUT THE INVENTION>

Hereinafter, the method for producing the fluorine-containing sulfonyl fluoride compound of the present invention will be described. In the present specification, the compound represented by the formula (1) is abbreviated as “compound 1”.

The same applies to compounds represented by other formulas.

First, terms used in the present specification will be described below. The following explanation applies consistently even when the compounds are different.

As used herein, the term “organic group” refers to a group containing one or more carbon atoms. A "halogeno group" is a group in which one or more of the hydrogen atoms bonded to a carbon atom has been replaced with a halogen atom. 004/005874

Say. “Bellhalogeno group” refers to a group in which substantially all of the hydrogen atoms bonded to carbon atoms have been replaced with halogen atoms, and “partial halogeno group” refers to a group in which some of the hydrogen atoms bonded to carbon atoms have been substituted. Refers to a group substituted with a halogen atom. In this case, for example, when the octa-gen atom is a fluorine atom, it is described as “fluo port”, “perfluo port”, “partially fluoro”. As the “perfluoro group”, a group in which all of the hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms is preferable, but even when an unsubstituted hydrogen atom remains, the property as a group is “ In the present invention, when it is substantially equivalent to a "perfluoro group", it is included in the concept of "perfluoro group" .In the present invention, "fluorination" refers to introducing a fluorine atom into a compound. The fluorination is usually performed by replacing a hydrogen atom bonded to a carbon atom with a fluorine atom. As the hetero atom-containing group, a group containing an etheric oxygen atom (（-) is particularly preferable.

In the method for producing a fluorine-containing sulfonyl fluoride compound of the present invention, compound 1 is oxidized to compound 2 (hereinafter also referred to as “oxidation step”), and then compound 2 is reacted with fluorine in a liquid phase. Compound 3 (hereinafter also referred to as “fluorination step”), and further decomposing compound 3 to obtain compound 4 below (hereinafter also referred to as “decomposition step”). Compound 4 is a compound useful as an ion exchange resin raw material or the like.

R ^B -ER ^A -SSR ^A -ER ^B

XS〇 ₂ — R ^A — E-R ^B · · · (2)

FS〇 ₂ -R ^AF -E ^F — R ^BF · · · · (3)

FS〇 ₂ -R ^AF -C〇F (4)

As ^RA in compound 1, a divalent hydrocarbon group, a halogeno divalent hydrocarbon group, a heteroatom-containing divalent hydrocarbon group, or a halogeno (hetero atom-containing divalent hydrocarbon) group is preferable. Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent alicyclic hydrocarbon group, and a divalent aliphatic hydrocarbon group is preferable. In the divalent aliphatic hydrocarbon group, a single bond, a double bond, or a triple bond may exist (or coexist) as a carbon-carbon bond. The divalent aliphatic hydrocarbon group has a linear structure, a branched structure, a cyclic structure, or a structure partially having a cyclic structure. Any of these may be used.

RA is more preferably a divalent saturated hydrocarbon group, a partially octalogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group or a partially octalogeno (heteroatom-containing divalent saturated hydrocarbon) group. Those groups containing no atoms are particularly preferred, and divalent saturated hydrocarbon groups or heteroatom-containing divalent saturated hydrocarbon groups are particularly preferred.

When R ^A is a divalent saturated hydrocarbon group, examples include an alkylene group, a cycloalkylene group, and a cycloalkylalkylene group. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable. As the cycloalkylene group, a 3- to 6-membered cycloalkylene group or a group in which at least one hydrogen atom of the cycloalkylene group is substituted with an alkyl group is preferable. As the cycloalkylalkylene group, a group in which one hydrogen atom of an alkyl group having 1 to 3 carbon atoms is substituted with a 3- to 6-membered cycloalkyl group is preferable.

When R A is a partially halogeno divalent saturated hydrocarbon group, a group in which the above divalent saturated hydrocarbon group is partially halogenated can be mentioned. The partially halogeno divalent saturated hydrocarbon group may have a linear structure or a branched structure, or may have a partially cyclic structure, and may have a partially fluoroalkylene group or a partially fluoroalkyl group. A chloroalkylene) group is preferred. The partial halogeno divalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms.

When R ^A is a heteroatom-containing divalent saturated hydrocarbon group, a divalent heteroatom or a divalent heteroatom group is introduced between the carbon atoms of the divalent saturated hydrocarbon group. Or a group in which a hetero atom is bonded to a carbon atom of the above divalent saturated hydrocarbon group, or a divalent hetero atom or a divalent heteroatom group is bonded to the carbon atom at the bonding terminal of the above divalent saturated hydrocarbon group. And a group bonded thereto. As the heteroatom-containing divalent saturated hydrocarbon group, a group having 1 to 20 carbon atoms is preferable, and from the viewpoint of usefulness of the compound, an etheric oxygen atom-containing divalent saturated hydrocarbon group is preferable, and an etheric oxygen atom-containing Alkylene groups are particularly preferred.

When R ^A is a partial halogeno (hetero atom-containing divalent saturated hydrocarbon) group, a group in which the above-mentioned hetero atom-containing divalent saturated hydrocarbon group is partially halogenated can be mentioned, and a partial fluoro ( Etheric oxygen atom containing alkylene) groups are preferred. Partial halo The geno (heteroatom-containing divalent saturated hydrocarbon) group may have a straight-chain structure or a branched structure, or may have a partial ring structure. The partial halogeno (hetero atom-containing divalent saturated hydrocarbon) group preferably has 1 to 20 carbon atoms.

R ^B (monovalent organic group) in compound 1 is preferably a monovalent hydrocarbon group, a halogeno monovalent hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, or a halogeno (heteroatom-containing monovalent hydrocarbon) group. .

R ^B is preferably a group of the fluorine-containing, Furuoro monovalent saturated hydrocarbon group, or Furuoro particularly preferred (hetero atom-containing monovalent saturated hydrocarbon) group, Perufuruo port monovalent saturated hydrocarbon group or, Perfluoro (heteroatom containing monovalent saturated hydrocarbon) groups are particularly preferred.

When RB is a perfluoromonovalent saturated hydrocarbon group, it may have a linear structure, a branched structure, or may have a partial ring structure, and is preferably a perfluoroalkyl group. . The carbon number of the perfluoro monovalent saturated hydrocarbon group is preferably 1 to 20, and particularly preferably 2 to 20.

When R ^B is Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group is preferably a group having a carbon number of 1 to 20, 2 to 10 carbon atoms are particularly preferred. Further, from the viewpoint of availability, ease of production, and usefulness of the product, a group containing an etheric oxygen atom is preferable, and a perfluoro (alkoxyalkyl) group or a perfluoroalkoxyl group is particularly preferable.

E one C_〇_〇_CH ₂ - represents two E in formula (1) is, both of the two bind to R ^B by a carbon atom that form a keto group, or form two even keto group And is preferably bonded to R ^A at a carbon atom. As a result, two molecules of compound 2 generated by oxidation of compound 1 become the same molecule.

Compound 1 can be obtained by subjecting compound 5 and compound 6 to an esterification reaction (hereinafter, referred to as “esterification step”).

E ¹ -R ^A -S— S— R ^A — E ¹ · ·-(5)

R ^B -E ²

E ¹ and E ² are one — COY and the other — CH ₂ OH, especially as to which one of E ¹ and E ² is one CH ₂ OH and which is one COY There is no limitation. Y represents an octylogen atom or a hydroxyl group, and Υ is preferably a fluorine atom, a chlorine atom or a hydroxyl group.

The esterification reaction between compound 5 and compound 6 in the esterification step can be carried out under known esterification reaction conditions.

The reaction may be carried out in the presence of a solvent (hereinafter referred to as “solvent 1”), but is preferably carried out in the absence of solvent 1 from the viewpoint of volumetric efficiency (for example, edited by The Chemical Society of Japan). , "Experimental Chemistry Course", 4th edition, Vol. 22 (Organic synthesis IV-acid · amino acid-peptide), Maruzen, Tokyo, 1992, pp. 50-51). When the solvent 1 is used, dichloromethane and chloroform are preferred. The use amount of the solvent 1 is preferably 50 to 500% by mass based on the total amount of the compound 5 and the compound 6.

In the esterification reaction, when Y in E ¹ or E ² is a halogen atom, an acid represented by HY is generated. It is preferable to discharge the acid out of the reaction system together with the nitrogen stream.

In addition, when Y in E ¹ or E ² is a hydroxyl group, water is generated. Therefore, it is preferable to allow a dehydrating agent to be present in the reaction system to allow the reaction to proceed (for example, “The Chemical Society of Japan,” Experimental Chemistry ", 4th edition, Vol. 22 (organic synthesis IV-acid 'amino acid' peptide), Maruzen, Tokyo, 1992, pp. 45-46). As the dehydrating agent, trifluoroacetic anhydride and thionyl chloride are preferably used. The amount of the dehydrating agent is preferably 2 to 20 moles per mole of Compound 5.

The reaction temperature of the esterification reaction is preferably not less than 150 ° C., 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, hereinafter the same) is preferably normal pressure to 2 MPa.

The crude product containing compound 1 produced by the esterification reaction may be purified according to the purpose or used as it is in the next reaction, etc., since the reaction in the next step can proceed smoothly. It is desirable to carry out purification.

As a method for purifying the crude product, the method described in International Publication WO02 / 44138 can be applied.

Compound 5 is readily available or can be easily synthesized by known methods. It is a compound that can be used. Further, since the ^RA portion in Compound 5 can be easily designed, the molecular structure of Compound 1 obtained can be variously set.

Specific examples of the compound 5 include the following compounds.

H0C0C¾ C¾ SSCH ₂ CH ₂圆,

H0C0C¾ CH ₂ CH ₂ SSC¾ CH ₂ CH ₂ COOH (5-1),

C1C0C¾ C¾ SSCH ₂ C¾ COCL

C1C0CH ₂ CH ₂ C¾ SSCH ₂ CH ₂ CH ₂ C0C1,

H0C¾CH _₂ SSC¾CH ₂ 0H.

Further, specific examples of the compound 6 include, but are not limited to, the following compounds.

CF ₃ CF ₂ CH ₂ OH,

CF ₃ CF ₂ CF ₂ CH ₂ 0H,

_{_{_{_{CF 3 CF 2 CF 2 CF 2}}}} CH 2 0H,

(CF ₃ ) ₂ CFC¾ OH,

CF ₃ CF ₂ CF ₂ 0CF (CF ₃ ) CH ₂ OE

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH (6-1),

HCF ₂ CF ₂ C¾0H,

HCF ₂ CF ₂ CF ₂ CF ₂ C¾ 0H,

CF ₃ C0F,

CF ₃ CF ₂ C0F,

CF ₃ CF ₂ CF ₂ C0F,

(CF ₃ ) ₂ CFC0F,

CF ₃ CF ₂ CF ₂ CF ₂ OCF (CF ₃ ) C0F,

CF ₃ CF ₂ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C0F.

Specific examples of compound 1 include, but are not limited to, the following compounds.

CF ₃ CF ₂ C¾ 0C0C¾ C¾ SSC¾ C¾ C00C¾ CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ CH ₂ 0C0CH ₂ CH ₂ SSCH ₂ CH ₂ C00CH ₂ CF ₂ CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ CF ₂ CH ₂ 0C0CH ₂ C¾ SSC¾ CH ₂ C00CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ , 5874

Ten

(CF ₃ ) ₂ CFC¾ 0C0C¾ CH ₂ SSC¾ CH ₂ C00C¾ CF (CF ₃ ) ₂ ,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) C¾ OCOC¾ CH ₂ SSC¾ CH ₂ COOCH ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

(CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C¾ OCOC¾ CH ₂ S) ₂ ,

HCF ₂ CF ₂ CH ₂ OCOCH ₂ CH ₂ SSC¾ C¾ C00CH ₂ CF ₂ CF ₂ H,

HCF ₂ CF ₂ CH ₂ CF ₂ CH _{2 0} C0CH ₂ CH ₂ SSC¾ C¾ C00CH ₂ CF ₂ C¾ CF ₂ CF ₂ H,

CF ₃ CF ₂ C¾ 0C0CH ₂ C¾ CH ₂ SSCH ₂ CH ₂ CH ₂ C00CH ₂ CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ CH ₂ OCOC¾ CH ₂ CH ₂ SSCH ₂ CH ₂ CH ₂ COOC¾ CF ₂ CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ CF ₂ C¾ 0C0CH ₂ CH ₂ CH ₂ SSCH ₂ CH ₂ CH ₂ COOCH ₂ CF ₂ CF ₂ CF ₂ CF ₃ ,

(CF ₃ ) ₂ CFCH ₂ 0C0CH ₂ CH ₂ C¾ SSCH ₂ CH ₂ CH ₂ COOCH ₂ CF (CF ₃ ) ₂ ,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CH ₂ OCOCH ₂ CH ₂ CH ₂ SSCH ₂ C¾ CH ₂ COOCH ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ , (CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ 0C0CH ₂ CH ₂ CH ₂ S) ₂ (1-1),

_{_{_{_{HCF 2 CF 2 CH 2 0C0CH 2}}}} CH 2 CH 2 SSC¾ C¾ C¾ C00CH 2 CF 2 CF 2 H,

HCF ₂ CF ₂ CH ₂ CF ₂ CH ₂ OCOC¾ C¾ CH ₂ SSCH ₂ CH ₂ CH ₂ COOC¾ CF ₂ CH ₂ CF ₂ CF ₂ H,

CF ₃ CF ₂ C00CH ₂ C¾ SSCH ₂ CH ₂ 0C0CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ COOC¾ CH ₂ SSC¾ C¾ OCOCF ₂ CF ₂ CF ₃ ,

(CF ₃ ) ₂ CFC00CH ₂ CH ₂ SSCH ₂ C¾ OCOCF (CF ₃ ) ₂ ,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOC¾ CH ₂ SSCH ₂ CH ₂ OCOCF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOC¾ CH ₂ SSC¾ CH ₂ OCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) 0-CF ₂ CF ₂ CF ₃

In the present invention, an oxidation step of oxidizing Compound 1 to Compound 2 is performed. In compound 2, R ^A , R ^B , and E are the same as those in formula (1). X represents a halogen atom. X is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

A method for producing compound 2 in which X is a halogen atom includes a method of reacting halogen (X ₂ ) in a solvent containing water. X in halogen (X ₂ ) corresponds to X in compound 2. According to the method, compound 2 having a desired X can be produced regardless of the type of Y of compound 1. In this reaction, the compound represented by the formula HO X is produced by the reaction of halogen (X ₂ ) with water, and the compound represented by the HO X oxidizes a sulfur atom, and at the same time, a YS bond Is oxidatively cleaved. It is thought to do.

As the solvent containing water (hereinafter, referred to as “solvent 2”), water, a mixed solvent of water and acetic acid, or a mixed solvent of water and acetate nitrile is preferable. The amount of the solvent 2 is preferably at least 2 times, more preferably 5 to 50 times the mass of the compound 1. The amount of water is preferably 4 to 2000 times, more preferably 20 to 1000 times, the mole of Compound 1.

As a method of producing compound 2 in which X is a chlorine atom in the oxidation reaction of compound 1, a method of reacting compound 1 with chlorine in a solvent containing water to obtain compound 2 is preferable (for example, Japan The Chemical Society, “Experimental Chemistry Course”, Vo 1.14 (Synthesis and Reaction of Organic Compounds III), Maruzen, Tokyo, 1978, pp. 1785-178 6).

As the chlorine, chlorine gas may be used as it is, or chlorine gas diluted with an inert gas may be used. As the inert gas, nitrogen gas or helium gas is preferable, and nitrogen gas is particularly preferable for economic reasons. The amount of chlorine in the nitrogen gas is not particularly limited, and is preferably 10 V o 1% or more in view of efficiency, and particularly preferably 20 vol% or more.

Usually, the reaction temperature in the oxidation reaction is preferably not lower than 120 ° C. and not higher than the boiling point of the solvent 2, and is preferably 0 ° C. to +60 in view of the reaction yield, selectivity, and ease of industrial implementation. . The reaction pressure in the oxidation reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.

As a method of producing compound 2 in which X is a bromine atom, a method of reacting compound 1 with bromine (Br ₂ ) in a solvent containing water is preferable.

As the method for forming a compound 2 X is a fluorine atom, it may be employed a method of oxidizing a compound 1 in full Tsu acid N0 _2.

Specific examples of compound 2 when X is a chlorine atom include the following compounds. Specific examples of the case where X is a bromine atom or a fluorine atom include the following compounds in which C 1 is replaced by Br or F.

C1S0 ₂ C¾ CH ₂ C00CH ₂ CF ₂ CF

C1S0 ₂ C¾ CH ₂ C00CH ₂ CF ₂ CF ₂ CF ₃ , C1S0 ₂ C¾ CH ₂ C00C¾ CF ₂ CF ₂ CF ₂ CF ₃ ,

C1S0 ₂ CH ₂ C¾ C00CH ₂ CF (CF peak,

C1S0 ₂ CH ₂ CH ₂ C00CH ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ ,

C1S0 ₂ C¾ CH ₂ C00CH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ ,

C1S0 ₂ CH ₂ CH ₂ C00CH ₂ CF ₂ CF ₂ H,

C1S0 ₂ CH ₂ C¾ C00CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ H,

C1S0 ₂ CH ₂ CH ₂ CH ₂ COOCH ₂ CF ₂ CF "

C1S0 ₂ CH ₂ CH ₂ C¾ COOCH ₂ CF ₂ CF ₂ CF ₃ ,

C1S0 ₂ CH ₂ CH ₂ C¾ C00CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ ,

_{_{_{C1S0 2 C¾ CH 2 CH 2 COOCH}}} 2 CF (CF 3) have

C1S0 ₂ CH ₂ CH ₂ CH ₂ COOC¾ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ ,

C 1 S0 ₂ CH ₂ CH ₂ CH ₂ C00CH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

C1S0 ₂ CH ₂ CH ₂ CH ₂ COOCH ₂ CF ₂ CF ₂ H,

C1S0 ₂ C¾ CH ₂ CH ₂ C00CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ H,

C1S0 ₂ CH ₂ CH _{2 0} C0 CF ₂ CF ₃ ,

C1S0 ₂ CH ₂ CH ₂ OCOCF ₂ CF ₂ CF ₃ ,

C1S0 ₂ C¾ CH ₂ OCOCF (CF ₃ ) ₂ ,

_{_{_{C1S0 2 CH 2 CH 2 OCOCF (}}} CF 3) 0CF 2 CF 2 CF 3,

C1S0 ₂ C¾ CH ₂ OCOCF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ .

In the present invention, when X of the compound 2 generated in the oxidation step is a fluorine atom, the compound 2 is used as it is in the fluorination reaction. On the other hand, when X of compound 2 is a halogen atom other than a fluorine atom (hereinafter, referred to as another halogen atom), the fluorination reaction is performed after replacing the other halogen atom with a fluorine atom.

Compound 2 in which X is a fluorine atom has an advantage that the yield of the fluorination reaction is remarkably improved as compared with the case where X is another halogen atom. Therefore, in the present invention, compound 2 in which X is a fluorine atom is used for the fluorination reaction.

As a method of substituting another octogen atom with a fluorine atom, in a solvent, fluorinated lithium (Scott, R.B .; Gord Xon, M.J.J.Org.Chem. 1) 9 5 6, 21, 38 5) or potassium hydrogen fluoride (Gramsta 5874

13 d, T .; Haze 1 dine, R. N. J. Chem. Soc. 195 5, 173.) is preferred.

As a solvent (hereinafter, referred to as “solvent 3”) used for the substitution reaction, a mixed solvent of water and dioxane or a mixed solvent of water and acetate nitrile is preferable. The amount of the solvent 3 is preferably at least 2 times, more preferably 5 to 50 times, the mass of the compound 6.

The reaction temperature of the substitution reaction is usually from 120 to the boiling point of the solvent 3, and is preferably from 0 ° C to 160 ° C from the viewpoint of the reaction yield, selectivity, and the ease of industrial implementation. . The reaction pressure of the substitution reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.

Specific examples of the compound 2 in which X obtained by the substitution reaction is a fluorine atom include the compounds in which the chlorine atom in the specific examples of the compound 2 is replaced with a fluorine atom.

In the present invention, the fluorine content of compound 2 is preferably 30% by mass or more. By setting the fluorine content to 30% by mass or more, the solubility in the liquid phase during the fluorination reaction becomes good. The fluorine content of compound 2 can be appropriately adjusted according to the type of the liquid phase of the fluorination reaction, and the fluorine content is more preferably 30 to 86% by mass, and still more preferably 30 to 76% by mass. The use of compound 2 having a fluorine content of 86% by mass or less is advantageous in that it is excellent in economics and that the available compounds are not limited.

Further, the molecular weight of compound 2 is preferably from 200 to 130. By setting the molecular weight of compound 2 to 200 or more, a decrease in the boiling point of compound 2 is suppressed, and in the course of fluorination, compound 2 is volatilized, thereby reducing the yield of fluorinated products and causing a decomposition reaction. Can be prevented. On the other hand, by setting the molecular weight to 1300 or less, it is possible to prevent a decrease in solubility in a liquid phase.

Compound 2 is a divalent organic radical R ^AF is the R ^A the same divalent organic group or R ^A in formula (3) to give compound 3 performs fluorination step of reacting with fluorine in a liquid phase is fluorinated It is. R ^A is a non-fluorinated group or R ^A can be fluorinated R ^AF , if not a group, but not fluorinated, is the same group as R ^A. For example, when R ^A is a berhalogeno divalent hydrocarbon group or a berhalogeno (heteroatom-containing divalent hydrocarbon) group, the halogen atom in these groups does not change even when reacted with fluorine in the liquid phase. Therefore, R ^AF is the same group as R ^A.

R ^BF is a group the same group or R ^B and R ^B fluorinated. R ^BF is or a group R ^B is not fluorinated, when R ^B is not fluorinated even if a group which can be fluorinated is the same group as R ^B. For example, R ^B is, Beruharogeno monovalent hydrocarbon group, Beruharogeno case of (hetero atom-containing monovalent hydrocarbon) group, a halogen atom in these groups may be reacted with fluorine in a liquid phase to a change ^Therefore , R ^BF is the same group as R ^B.

R ^AF is a perfluorinated divalent saturated hydrocarbon group, a perfluorinated (partially halogenated divalent saturated hydrocarbon) group, a perfluorinated (heteroatom-containing divalent saturated hydrocarbon) group, or a perfluoro (partially halogenated (heteroatom-containing divalent saturated hydrocarbon) group) preferably that it is a hydrocarbon)) group, these groups are each a group having a carbon skeleton structure corresponding to R ^a same number of carbon atoms and R ^a.

R ^BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially halogeno monovalent saturated hydrocarbon) group, a perfluoro (monovalent saturated hydrocarbon containing a hetero atom) group, or a perfluoro (partially halogeno (heteroatom containing (Saturated hydrocarbon)). R ^B and R ^BF and easily implement fluorine Kahan response to be described later of the same group are particularly preferred in that it can implement the continuous process. That is, R ^B in the formula (2) is also a perfluoro monovalent saturated hydrocarbon group or a perfluoro group.

(Heteroatom-containing monovalent saturated hydrocarbon) group.

E ^F represents one C〇OCF ₂ —.

The orientation of the base of E ^F also corresponds to E. For example, if a carbon atom forming a keto group E is bonded to R ^A, said carbon atom of E ^F is bound to R ^AF, carbon atom to form a keto group E is bonded to R ^B If there are, the carbon atom of E ^F is bound to R ^BF.

The fluorination reaction is carried out by a liquid-phase fluorination reaction carried out in the liquid phase from the viewpoint of operability and yield of the reaction (Ok azoe T. eta 1., Adv. Synth. Cata 1., 2001 , 343, 219 ·). The fluorination reaction is performed by the ECF method, Four

15 The Baltic fluorination method or the method of reacting with fluorine in the gas phase can theoretically be performed, but the method in which fluorination in the liquid phase is particularly advantageous in terms of reaction yield, ease of reaction operation, etc. It is.

The fluorination reaction is preferably carried out by a method of reacting compound 2 with fluorine (F ₂ ) in the presence of a solvent (hereinafter referred to as “solvent 4”) to give compound 3. As fluorine, fluorine gas may be used as it is, or 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 economic reasons. The amount of fluorine in the nitrogen gas is not particularly limited, but is preferably 10 vo 1% or more from the viewpoint of efficiency, and particularly preferably 20 vol% or more.

The solvent 4 is preferably a solvent that does not contain a C—H bond and essentially has a C—F bond, and is further selected from perfluoroalkanes or a group consisting of a chlorine atom, a nitrogen atom, and an oxygen atom. An organic solvent obtained by perfluorinating a known organic solvent having at least one atom in its structure is preferable. Further, as the solvent 4, a solvent having high solubility for the compound 2 is preferably used, and a solvent capable of dissolving the compound 2 in an amount of 1% by mass or more, particularly preferably a solvent capable of dissolving the compound 2 in an amount of 5% by mass or more is preferable.

As an example of the solvent 4, the same solvent as the solvent used in the fluorination step described in WO 02/41438 can be used. The amount of the solvent 4 is preferably at least 5 times the mass of the compound 2, and particularly preferably 10 to 100 times the mass of the compound 2.

The reaction system of the fluorination reaction may be a batch system or a continuous system, and for each method, the method described in WO 02/41438 can be applied. It is preferable to use a fluorine gas diluted with an inert gas such as nitrogen gas, regardless of whether the fluorine gas is used in the patch system or in the continuous system. The amount of fluorine used in the fluorination reaction should be such that the amount of fluorine is always an excess equivalent to the hydrogen atoms that can be fluorinated, whether the reaction is carried out in a batch mode or in a continuous mode. It is preferable to use fluorine gas, and it is particularly preferable to use fluorine gas in an amount of 1.5 times equivalent or more (that is, 1.5 times mole or more) from the viewpoint of selectivity. It is preferable that the amount of fluorine gas is always maintained in an excessive amount from the start to the end of the reaction. The reaction temperature of the fluorination reaction is usually preferably from 160 to the boiling point of compound 2, and from the viewpoint of the reaction yield, selectivity, and the ease of industrial implementation, it is -50 to +10. 0 ° C is particularly preferable, and 120 to 150 is particularly preferable. The reaction pressure of the fluorination reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoints of reaction yield, selectivity, and the ease of industrial implementation.

Further, in order to allow the fluorination reaction to proceed efficiently, it is preferable to add a C—H bond-containing compound to the reaction system in the latter stage of the reaction or to perform ultraviolet irradiation. As the method of addition, the amount of addition, and specific compounds, the specific examples described in the fluorination step described in WO 02/41438 can be applied.

The fluorination reaction in the present invention is preferably a reaction for perfluorinating Compound 2. That is, the compound 3 is preferably a compound in which the compound 2 is perfluorinated.

Specific examples of compound 3 obtained in the fluorination step include the following compounds.

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF (CF mountain,

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ C00CF ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF (CF peak,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ CF ₂ C00CF ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ (3-1),

FS0 ₂ CF ₂ CF ₂ 0C0CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ 0C0CF ₂ CF ₂ CF

FS0 ₂ CF ₂ CF ₂ 0C0CF (CF ₃ ) FS0 ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ,

FS0 ₂ CF ₂ CF ₂ OCOCF (CF ₃ ) 0CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ .

Next, in the present invention, a decomposition step of decomposing the ester bond of compound 3 to obtain compound 4 is performed.

The decomposition step is preferably carried out by a thermal decomposition reaction or a decomposition reaction carried out in the presence of a nucleophile or an electrophile (Okazoe T. eta 1., A dv. Synth. Cata 1., 201, 334, 219.).

The thermal decomposition reaction can be performed by heating compound 3. The reaction type of the thermal decomposition reaction is preferably selected depending on the boiling point of Compound 3 and its stability. For example, in the case of thermally decomposing compound 3 which is easily vaporized, adopt a gas phase pyrolysis method in which the exit gas containing the obtained compound 4 is condensed and recovered by continuously decomposing it in the gas phase. You.

The reaction temperature of the gas phase pyrolysis method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, and particularly preferably from 150 to 250 ° C. Further, the reaction may be carried out in the presence of an inert gas not directly involved in the reaction in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas. It is preferable to add about 0.01 to 50 vol% of the inert gas to the compound 3. Large amounts of inert gas may reduce the amount of product recovered.

On the other hand, when compound 3 is a compound that is difficult to vaporize, it is preferable to employ a liquid phase pyrolysis method in which the liquid is heated in a liquid state in the reactor. The reaction pressure in this case is not limited. Normally, the reaction is carried out in a reactor equipped with a distillation column, and the product containing compound 4 has a lower boiling point than compound 3, so the reaction distillation method is used to vaporize the product and continuously withdraw it. It is preferably obtained by a method. Alternatively, a method may be employed in which the products are collectively extracted from the reactor after the completion of the heating. The reaction temperature of this liquid phase pyrolysis method is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.

In the case of performing the thermal decomposition by the liquid phase pyrolysis method, the thermal decomposition may be performed without a solvent or in the presence of a solvent (hereinafter, referred to as “solvent 5 J.”) The solvent 5 is not particularly limited as long as it does not react with the compound 3 and does not react with the compound 4. The solvent 5 is easily separated during the purification of the compound 4. It is preferable to select one. As a specific example of the solvent 5, an inert solvent such as perfluorotrialkylamine and perfluoronaphthylene, and a trifluoromethyl ethylene oligomer having a high boiling point among chlorofluorocarbons are preferred. The amount of the solvent 5 is preferably from 10 to 100% by mass based on the compound 3. In the case where compound 3 is decomposed by reacting it with a nucleophile or an electrophile in a liquid phase, the reaction can be carried out without solvent even in the presence of a solvent (hereinafter referred to as “solvent 6”). You may go. The solvent 6 is preferably the same as the solvent 5. As the nucleophile, F— is preferable, and F— derived from alkali metal fluoride is particularly preferable. The fluoride of an alkali metal, N a F, N a HF 2, KF, C s F C., these N a F and KF terms of economy Contact and reactivity of particularly preferred.

When a nucleophile (eg, F—) is used, the nucleophile used at the beginning of the reaction may be a catalytic amount or an excess amount. The amount of the nucleophile such as F— is preferably from 1 to 500 mol%, more preferably from 1 to 100 mol%, particularly preferably from 5 to 50 mol%, based on compound 3. The reaction temperature is preferably from −30 ° C. to (a temperature between the boiling point of the solvent 6 and the compound 3), and particularly preferably from 120 ° C. to 120 ° C. This method is also preferably carried out by a reactive distillation method in a reactor equipped with a distillation column. The decomposition process occurs decomposition of E ^F, 2 two - COF group is formed. Specific examples of the compound 4 obtained in the decomposition step include the following compounds.

FS0 ₂ CF ₂ CF ₂ COF,

FS0 ₂ CF ₂ CF ₂ CF ₂ COF (4-1)>

Compound 4 obtained by the production method of the present invention is a compound useful as a monomer raw material for ion-exchange resins because it has an FS〇 ₂ — group at a terminal. For the derivation to the monomer, various methods utilizing the reactivity of one C 0 F group present at the other end can be applied. Further, according to the present invention, since various compounds having an ^RA group can be obtained as the compound represented by the formula (1), it is possible to obtain a chemical prosthesis 4 having an ^RAF group corresponding to the ^RA .

The production process of the present invention can be improved to a more efficient process by producing the compounds in the process and recycling the products. For example, compound 5 Examples of the compound 6 to be reacted include a method using the following compound 7 or the following compound 8.

The concept of this process can be expressed as: However, the symbols in the following formula have the same meanings as described above, and X ¹ represents a halogen atom other than a fluorine atom.

(4) Compound 7 can be obtained together with compound 4 from the reaction product of the decomposition step of compound 3. Compound 8 can be obtained by reduction reaction of compound 7.

R ^BF -COF

R ^BF -CH ₂ OH (8)

(Wherein, it has the same meaning as R ^BF in equation (3).)

When compound 7 is obtained by reducing compound 7, a method in which compound 7 is replaced with a suitable ester and then reacted with a metal hydride in the liquid phase (for example, Niederpruem H., Voss, P Ger. 1, 300, 539, p. 3-4.) Or by contacting compound 7 with hydrogen gas in the presence of a suitable catalyst (Novo tny M "US 4, 273, 947, p. 7− 10.)

In the reduction reaction using a metal hydride, the metal hydride is preferably sodium borohydride or lithium aluminum hydride. In the reaction, tetrahydrofuran, dioxane, and tetrahydrogen are used as solvents (hereinafter, referred to as “solvent 7”). It is preferred to use mouth furan. When sodium borohydride is used as the metal hydride, methanol, ethanol, or 2-propanol can be used as the solvent 7. The amount of the solvent 7 is preferably at least 2 times, more preferably 5 to 50 times the mass of the compound 7.

The reaction temperature of the reduction reaction using a metal hydride is usually preferably 150 ° C. or higher and not higher than the boiling point of the solvent 7, in view of the reaction yield, selectivity, and low industrial practice. To 0 ° C. or higher and not higher than the boiling point of the solvent. The reaction pressure is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.

In the method of contacting with hydrogen gas in the presence of a catalyst, the catalyst is preferably a palladium-based, rhodium-based, or iridium-based catalyst. The reaction may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent from the viewpoint of volumetric efficiency. The reaction temperature is usually preferably from 0 to 200. The reaction pressure is not particularly limited, and normal pressure to 10 MPa (gauge pressure) is particularly preferable from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.

Specific examples of the above process include the following examples.

The following compound 5-1 and the following compound VIII-1 are subjected to an esterification reaction to give the following compound 111, and then compound 111 is oxidized in a solvent containing water in the presence of chlorine, and further chlorine The atom is replaced with a fluorine atom to give the following compound 2_1. Next, the compound 2_1 is reacted with fluorine in a liquid phase to give the following compound 3-1. The following compound 4-1 is obtained and the compound 7-1 is obtained. Next, the compound 7-1 is reduced to compound 8-1, and the compound 8-1 reacts with the compound 5-1 again. However, R ^{B 1}

Shows a _{_{-CF (CF 3) 0CF 2 CF}} (CF 3) 0CF 2 CF 2 CF 3. Four

twenty one

S

S ¹

One

CJSOaiCHsJsCOOCHsR ¹ B1

CF ₃ CF ₂ CF ₂ OCF (C CF ₂ OCF (CF ₃ ) CH ₂ OH

(8-1)

FS0 ₂ (CH2) ₃ COOCH ₂ R ^B1

CF ₃ CF ₂ CF ₂ OCF (CF3) CF ₂ OCF (CF ₃ ) COF] (2-1) CF ₂ R ^B

(4-1)

Compound 4 produced by the above-mentioned process can be led to various useful compounds by utilizing the reactivity of one terminal C の一 F group. For example, when the terminal of compound 4 is a CF ₂ CF ₂ C ◦ F group or a CF ₂ CF (CF ₃ ) COF group, a thermal decomposition reaction (for example, Method sof Organic Chemistry ( H oub en—We y 1), the d., Ba as ne r B., Hagemann H., Ta t 1 ow J. C., Ed s., Ge org Thierne, S tutt ga rt, 1999, Vo l. E 10 b, ( Or gano-F l uo rine C omp ound s), P t. 1,. fluororesin by converting into ₂ groups one CF = CF by the method) as described in 703. etc. To produce monomer raw materials. The塲合to the ion exchange membrane, One S_〇 ₂ F groups derived from the monomers one is preferably converted to an ion-exchange group such as a subsequent step in one SO ₃ H group.

Hexafluoropropylene oxide (HFPO) is reacted with the terminal of compound 4 to obtain the following compound 9, and then the terminal group is thermally decomposed by the same method as above to obtain the following compound 10. (However, ^RAF has the same meaning as above.)

FSO. One R ^AF — CF ₂ OCF (CF ₃ ) COF · · · (9)

FSO, — R AF CF ₉ OCF = CF (10),

Compound 10 is a compound useful as a monomer for synthesizing an ion exchange membrane. Compound 1 As an example of a method for obtaining 0, the following compound (4-1) is reacted with HFPO to obtain the following compound (9-1), and the terminal group of the compound (9-1) is subjected to thermal decomposition reaction to obtain one. There is a method in which CF is converted into CF ₂ groups to lead to the following compound (10-1).

HFPO

FSO. CF ₂ GF ₂ CF ₂ COF FS0 ₂ (CF ₂ ) ₄ CF (CF ₃ ) COF → ^ FS0 ₂ (CF ₂ ) ₄ GF = CF ₂

F

Examples of the thermal decomposition reaction of the compound 9 such as the compound 911 include a gas phase thermal decomposition reaction and a thermal decomposition reaction carried out after reacting alkali hydroxide with alkali hydroxide.

The reaction temperature in the gas phase thermal decomposition reaction is preferably from 250 to 400, more preferably from 250 to 35 O :. The reaction temperature in the thermal decomposition reaction of the alkali carboxylate is preferably from 150 to 350, more preferably from 200 to 280 ° C. When the reaction temperature in the gas phase thermal decomposition reaction is 250 ° C. or higher, or when the reaction temperature in the thermal decomposition reaction of the alkali carboxylate is 150 or higher, there is an advantage that the conversion is excellent. Also, the reaction temperature in the gas phase pyrolysis reaction

When the reaction temperature is less than 400 ° C or in the thermal decomposition

When the temperature is 50 ° C or lower, generation of undesired thermal decomposition products can be suppressed.

The method described in WO02 / 44138 or the like can be applied to these techniques of the gas phase thermal decomposition reaction.

As described above, according to the production method of the present invention, sulfonyl fluoride compounds having various structures can be produced at low cost from easily available raw materials. Furthermore, in the present invention, by-products in the product can be reused as raw materials and reaction solvents. Therefore, it is an economical way to reduce raw material usage and waste. Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the following, gas chromatography is referred to as GC, and gas chromatography mass spectrometry is referred to as GC-MS. Also, TMS, tetramethylsilane CC 1 ₂ FCC 1 F _{2 is referred} to as R-113, and tetrahydrofuran is referred to as THF. The NMR spectrum data is shown as an apparent chemical shift range. ^{In the} quantification by ¹⁹ FN MR, C ₆ F ₆ was used as an internal standard.

(Example 1) FS0 ₂ (CF ₂ ) ₃ COF production example

(Example 11) Production of (S (CH ₂ ) 3 C00CH ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ) ₂ (esterification step)

Room temperature under nitrogen flow, the mixture of anhydrous Torifuruoro acetic (1 9. 3 g) (01 2) 3 (00 Ox) ₂ (10.5 g) was stirred for 1 hour. To this, F (CF ₂ ) ₃ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) CH ₂ OH (39.7 g) was added over 60 minutes while cooling with water to keep the internal temperature at 13 ° C or less. It was dropped. 2.5 hours later, the contents were added to water (120 mL), extracted four times with t-butyl methyl ether (40 mL), the organic layer was dried over magnesium sulfate, filtered, concentrated, and treated with (S (CH ₂ ) ₃ C00CH ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ) ₂ was obtained. 79% yield. The product was subjected to the oxidation step of Example 1-2 without purification.

_{NMR (300. 4MHz; CDC 1 3} , TMS) <5 2. 05 (qu i, J = 7. 1Hz, 2H), 2. 54 (. Tm, J = 7 3Hz, 2 H), 2. 7 1 (t, J = 7.1 Hz, 2H), 4.46 to 4.74 (m, 2H);

^{19 FNMR. (282. 7MHz; CDC} 1 3, CFC 1 3) δ one 78.6-1 84. 5 (4F), one 80. 0 (3 F), -81 3 (3 F), one 82. 8 (3 F), 1 129.2 (2 F), 1 133.7 (1 F),-144.6 (1 F);

IR (neat) 1762.8, 1333.4, 1236.5, 1159.3, 993.4 cm- ¹ .

(Example 1 one _{_{2) C1S0 2 (CH 2)}} 3 COOC¾CF (CF 3) preparation of _{_{OCF 2 CF (CF 3) OCF}} 2 CF 2 CF 3 ( oxidation step

)

In a flask equipped with a dry ice condenser one obtained in Example 1-1

(S (C¾) 3 C00C¾ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ) ₂ (9.5 g), water (9 mL), and acetonitrile (8 mL) Chlorine gas was bubbled while stirring. In this state, the mixture was stirred at room temperature for 6 hours. After purging the system with nitrogen, the content was added to water (150 mL), extracted with t-butyl methyl ether (40 mL) three times, and the organic layer was dried over magnesium sulfate, filtered and concentrated. C 1 S0 ₂ (C¾) 3 C00CH ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ (9.0 g) was obtained. Yield 84

%. The product was directly used for the next fluorine substitution reaction without purification.

(Example 13) FS0 ₂ (CH ₂ ) 3 C00CH ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ Production (Fluorine substitution step)

C 1 S0 ₂ (C¾) 3 C00C¾ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ (6.9 g) obtained in Example 1-2, potassium hydrogen fluoride (1.6 g), water (2 OmL) and acetonitrile (20 mL) were placed in a flask and stirred at room temperature for 22 hours. The contents were added to water (4 OmL), extracted four times with t-butyl methyl ether (25 mL), and the organic layer was dried over magnesium sulfate, filtered and concentrated to obtain a crude liquid. The crude mixture was purified by silica gel column black Ma Bok photography (developing solvent: hexane (10): acetic acid Echiru (1) mixed solvent) to obtain _{_{FS0 2 (C) 3 COOC¾CF (}} CF 3) OCF 2 CF (CF 3) OCF ₂ CF ₂ CF ₃ (4.9 g) was obtained. 80% yield, 98% purity.

^{! H NMR (300. 4 MHz;} CDC 1 3, TMS) δ 2. 29 (qu i, J = 7. 4 Hz, 2H), 2. 67 (. T, J = 7 1 Hz, 2 H), 3.50 (dt, J = 4.7, 7.3 Hz, 2H), 4.51 to 4.78 (m, 2H);

^{19 FNMR... (282. 7MHz} ; CDC ", CFC 1 3) δ 53. 5 (IF), -78 5~- 84. 4 (4 F), -79 8 (3 F), -81 1 ( 3F), 1 82.7 (3 F), 1 129.1 (2F), 133.3 (IF), 144.5 (IF);

I R (ne at) 1761.8, 1418.7, 1306.3, 1237.2, 1200.4, 1146.0, 992.8 cm-].

(Example _{_{1- 4) FS0 2 (CF 2}} ) 3 C00CF 2 CF (CF 3) 0CF 2 CF (CF 3) preparation of 0CF _₂ CF ₂ CF ₃ (fluorination step)

R-113 (312 g) was added to a 50 OmL nickel autoclave and stirred at 25. At the autoclave gas outlet, a cooler maintained at 20 ° C, a packed bed of NaF pellets, and a cooler maintained at 1 10 were installed in series. In addition, a liquid return line was installed to return the condensed liquid from the cooler kept at -1 o ° c to the autoclave. After injecting nitrogen gas into the autoclave at room temperature for 1 hour, fluorine gas diluted to 20% with nitrogen gas (hereinafter referred to as 20% diluted fluorine) It is referred to as gas. ) Was blown at room temperature at a flow rate of 12.86 L / h for 30 minutes, and then the pressure inside the autoclave was increased to 0.15 MPa and then further blown for 30 minutes. Next, while blowing the 20% diluted fluorine gas at the same flow rate while maintaining the pressure in the reactor at 0.1 MPa, the product (5 g) obtained in Example 3 was added to R-113 (100 g). The solution dissolved in was injected over 2.8 hours.

Next, while maintaining the pressure inside the reactor at 0.15 MPa, while blowing 20% diluted fluorine gas at the same flow rate, the R-113 solution with a benzene concentration of 0-01 g / mL was raised from 25 to 40 ° C. 9 mL was injected while the temperature was raised to, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hour. The total amount of benzene injected was 0.09 g, and the total amount of R-113 injected was 9 mL.

Further, stirring was continued for 1 hour while blowing a 20% diluted fluorine gas at the same flow rate. Next, the pressure in the reactor was adjusted to normal pressure, and nitrogen gas was blown for one hour. The product was analyzed by ¹⁹ F-NMR, and it was confirmed that the title compound was contained in a yield of 60%.

^{19 F NMR (282. 7 MH z} ; CDC ", CFC 1 3) δ 46. 3 (IF), one 79.0-1 8 1. 5 (7 F), - 81. 9~- 82. 3 ( 5F), -82 .5 to 1 88.5 (3 F), — 108.4 (2 F),-1 18.3 (2 F),-121.1 (2 F),-130. 2 (2 F), -145.6 (2 F).

(Example 1-5) Production of FS0 ₂ (CF ₂ ) ₃ C0F

(Disassembly process)

Example 1 FS0 ₂ (CF ₂ ) 3 C00CF ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ (4.2 g) obtained in 1-4 together with NaF powder (0.03 g) The flask was charged and heated at .140 ° C. for 10 hours in an oil bath with vigorous stirring. A reflux condenser whose temperature was adjusted to 20 was installed at the top of the flask. After cooling, a liquid sample (4.0 g) was recovered. GC-MS analysis showed that CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF

FS0 _₂ (CF ₂₎ ₃ COF was confirmed as the main product, the yield of the title compound were filed at 73.7%. In addition, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF was obtained with a yield of 74.6%.

(Example 1-6) CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF reuse

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) obtained in Example 1-5 CF ₂ OCF (CF ₃ ) COF and an equimolar amount of methanol, The reaction was carried out in the presence of sodium fluoride to obtain CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C00CH ₃ . The obtained CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C00C¾ is reacted with sodium borohydride in 2-propanol to obtain CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF was obtained (CF ₃₎ C¾ OH. The obtained CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) C¾OH is reacted with (SC¾CH ₂ CH ₂ COOH) ₂ under the same conditions as in the above esterification step,

Was obtained _{(S (C¾) 3 C00CH 2} CF (CF 3) 0CF 2 CF (CF 3) 0CF 2 CF 2 CF 3) 2.

The obtained (S (CH ₂ ) 3 C00C¾CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ ) ₂ is reacted under the same conditions as the above oxidation step, and fluorine substitution reaction. ,

_{_{FS0 2 (CH 2) 3 C00CH}} 2 CF (CF 3) 0CF 2 CF (CF 3) to give the 0CF _₂ CF ₂ CF _3. Got

The _{_{FS0 2 (CH 2) 3 C00CH}} 2 CF (CF 3) 0CF 2 CF (CF 3) 0CF 2 CF 2 CF 3, are reacted under the same conditions as above fluorination _{_{_{step, FS0 2 (CF 2) 3}}} COOCF 2 CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ was obtained. The obtained FS0 ₂ (CF ₂ ) 3 C00CF ₂ CF (CF ₃ ) 0CF ₂ CF (CF ₃ ) 0CF ₂ CF ₂ CF ₃ is decomposed under the same conditions as in the above decomposition step to obtain FS0 ₂ (CF ₂ ) ₃ C0F and CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF were obtained.

(Example 2) FS0 ₂ (CF ₂ ) ₄ 0CF = CF ₂ production example

(Example 2-1) FS0 ₂ (CH ₂ ) ₃ COOCH ₂ CF ₂ CF ₂ CF ₂ Production of CHF ₂

Except that (S (CH ₂ ) ₃ COOH) ₂ (300 g) and H0CH ₂ CF ₂ CF ₂ CF ₂ CHF ₂ (292 g) were used, esterification step, an oxidation step according to example 1 one 2, the fluorine substitution process described in example 1 one 3 go in _{_{_{order, FS0 2 (CH 2) 3}}} COOC¾CF 2 CF 2 CF 2 CHF 2 and (3 80 g) Obtained.

^] H NMR (30.4 MHz; CDC ", TMS) δ 2.30 (m, 2H), 2.70 (t, J = 7. lHz, 2H), 3.52 (m, 2 H), 4.63 (t, J = 13.7 Hz, 2H), 6.05 (tt, J = 5.1, 51.8 Hz, 1H);

^{19 F NMR (2 8 2. 7} MHz; CDC 1 3, CFC 1 3) δ 53. 2 (1 F), - 1 1 9. 3 (2 F), - 1 24. 8 (2 F), one 1 29.4 (2 F),-1 36.6 (2 F).

(Example 2 _ 2) FS0 ₂ (CF,) ₃ C00CF ₂ CF ₂ CF ₂ CF ₂ CF ₃

But using Example 2 1 obtained in _{_{_{FS0 2 (CH 2) 3 C00CH}}} 2 CF 2 CF 2 CF 2 CHF 2 (3 8 0 g) is the same as the method, the fluorination described in Example 1 one 4 Perform the process, FS0 ₂ (CF ₂ ) C00CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ Was obtained. Yield 55%.

^{19 F NMR. (282. 7 MH} z; CDC 1 3, CFC 1 3) 6 46. 3 (1 F), -8 1. 2 (3 F), -86 5 (2 F), - 108. 3 (2 F), 1 1 18.1 (2 F),-120.8 (2 F),-1 23.6 (2 F),-125.8 (2 F),-1 26.7 (2 F).

(Example 2 _ 3) FS0 ₂ (CF ₂ ) 3 Production of C0F (Part 2)

Example 2-2 obtained in FS0 ₂ (CF ₂₎ ₃ g of _{_{_{_{C00CF 2 CF 2 CF 2 CF 2}}}} CF 3 a 280 g containing crude liquid to the flask KF powder (3. 2 g), an oil while vigorously stirring Heated at 85-90 ° C for 2 hours in an oil bath at 85-90 ° C in a bath. At the top of the flask, a reflux condenser adjusted to 20 ° C was installed. After cooling, FS0 distilling the recovered liquid sample _₂ (CF ₂₎ 3 to obtain a COF (150 g). 95% yield.

(Example _{_{2- 4) FS0 2 (CF 2}} ) 4 OCF (CF 3) COF in Production Example (Part 2)

Examples 2-3 obtained in _{_{_{FS0 2 (CF 2) 3 COF}}} (1 50 g), C s F powder (6. 5 g), was charged to the O one Tokurebu (inner volume 250 mL) with di glyme (32 g) HFPO (93 g) was introduced over 3 hours while stirring under ice cooling. After stirring for 1 hour followed by the autoclave contents were vacuum distilled _{_{_{FS0 2 (CF 2) 4 0CF}}} (CF 3) to give the COF (21 5 g). 90% yield.

(Example 2-5) FS0 ₂ (CF ₂ ) 4 OCF (CF ₃ ) COOK production

It viewed charged potassium bicarbonate and (48 g) monoglyme the (240 mL) in a flask, under ice-cooling, FS0 obtained in Example 2 4 while stirring _{_{_{2 (CF 2) 4 0CF (}}} CF 3) COF (21 5 g ) Was added dropwise. Obtained after completion of the dropwise addition, stirred for a further 30 minutes, after which the solvent was distilled off, 9 5 ° C for 8 days, and then vacuum dried FS0 ₂ a _{_{(CF 2) 4 0CF (CF}} 3) COOK (184 g) Was. Yield 80%.

(Example 2-6) FS0 ₂ (CF ₂ )

Obtained in Examples 2-5 in flasks with traps cooled with liquid nitrogen

_{_{_{FS0 2 (CF 2) 4 0CF}}} (CF 3) were charged C00K (1 84 g), vacuum flask (400 P a, but absolute pressure) when to heating to 1 80~210 ° C, the liquid in the trap (140 g) distilled out. As a result of analyzing the liquid by ¹⁹ F NMR, formation of FSO ₂ (CF ₂ ) ₄₀ CF = CF ₂ was confirmed. Yield 95%. 1 9 F NMR.. (282. 7MHz; CDC ", CFC 1 3) δ 46. 1 (1 F), -85 1 (3 F), - 108. 1 (2 F), -113 9 (1 F ), — 12 0.6 (2 F), -122. 0 (1 F),-125.2 (2 F),-136.0 (1 F).

ADVANTAGE OF THE INVENTION According to this invention, the difficulty of manufacture which the conventional method has is solved, and fluorine-containing sulfonyl fluoride compounds having various molecular structures can be efficiently manufactured from inexpensive and easily available raw materials.

Claims

The scope of the claims

1. The compound represented by the following formula (1) is oxidized to a compound represented by the following formula (2), and when X of the compound represented by the formula (2) is a fluorine atom, Alternatively, when X is an octa-gen atom other than a fluorine atom, X is substituted with a fluorine atom, and then the compound represented by the formula (2) wherein X is a fluorine atom is treated in a liquid phase with fluorine. To give a compound represented by the following formula (3), and further decompose the compound represented by the formula (3) to obtain a compound represented by the following formula (4). For producing a fluorinated sulfonyl fluoride compound according to claim 1.

^{^{R B - E- R A - S}} - S - R A - E- R B - - · (1)

XS0 ₂ -R ^A -ER ^B

FS0 ₂ -R ^AF -E ^F _R ^BF

FS0 ₂ -R ^AF -COF (4)

(In the formula, ^RA represents a divalent organic group.

R ^B is a monovalent organic group.

E is one COOCH ₂ - represents a carbon atom to form a keto group E is attached to or R ^B binds to R ^A.

X represents a halogen atom.

R ^AF is R ^A R ^BF indicating the same divalent organic group or a divalent organic group R ^A is fluorinated and is monovalent for R ^B and the same monovalent organic group or R ^B is fluorinated E ^F which represents an organic group may include one C_〇_OCF ₂ - represents a. )

2. The method according to claim 1, wherein the compound represented by the formula (2) has a fluorine content of 30% by mass or more.

3. The method according to claim 1, wherein the compound represented by the formula (2) has a molecular weight of 200 to 1300.

4. R ^AF is perfluoro divalent saturated hydrocarbon group, perfluoro (partial halogeno A divalent organic group selected from the group consisting of a divalent saturated hydrocarbon) group, a perfluoro (divalent saturated hydrocarbon containing a hetero atom) group, and a perfluoro (partially octogeno (a divalent saturated hydrocarbon containing a hetero atom)) group Yes, R ^BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially octogeno monovalent saturated hydrocarbon) group, a perfluoro (heteroatom-containing monovalent saturated hydrocarbon) group, and a perfluoro (partially halogeno (heteroatom containing The method according to any one of claims 1 to 3, which is a monovalent organic group selected from the group consisting of a monovalent saturated hydrocarbon)) group.

5. The compound according to any one of claims 1 to 4, wherein the compound represented by the formula (1) is a compound obtained by reacting a compound represented by the following formula (5) with a compound represented by the following formula (6). The production method according to any one of the above.

E ¹ — R ^A — S— S— R ^A- ; E〗 · ·-(5)

R ^B -E ²

(Wherein, R ^A and R ^B have the same meaning as described above, ^one of E ¹ and E ² is —COY, the other is —CH ₂ OH, and Y is a halogen atom or a hydroxyl group.)

6. The compound according to any one of claims 1 to 5, wherein the compound represented by the formula (3) is decomposed to obtain the compound represented by the formula (4) and the compound represented by the following formula (7) is obtained. Manufacturing method described.

R ^BF -COF

(In the formula, R ^BF has the same meaning as described above.)

7. As the compound represented by the formula (6), a compound represented by the formula (7) obtained by decomposing the compound represented by the formula (3) or a compound represented by the formula (7) is used. The production method according to claim 5, wherein a compound represented by the following formula (8) obtained by reduction is used.

R ^BF — COF · · · (7)

R ^BF -CH ₂ OH (8)

(In the formula, R ^BF has the same meaning as described above.)

8. Hexafluoropropylene oxide is added to the compound represented by the following formula (4) obtained by the production method according to any one of claims 1 to 7, and the compound is represented by the following formula (9). A method for producing a fluorine-containing sulfonyl vinyl ether compound, characterized in that a compound represented by the following formula (10) is obtained by obtaining a compound to be obtained and subjecting the compound (9) to a thermal decomposition reaction.

'(0 T)

(6) ^z OS d () 'd OJ- y CL' ^z OSd

L8S00 / 00ZdT / 13d S9 £ t60 contract OAV