WO2002026679A1

WO2002026679A1 - Process for producing fluorinated alcohol

Info

Publication number: WO2002026679A1
Application number: PCT/JP2001/008432
Authority: WO
Inventors: Hidekazu Okamoto; Takashi Okazoe; Kunio Watanabe; Hirokazu Takagi
Original assignee: Asahi Glass Company, Limited
Priority date: 2000-09-27
Filing date: 2001-09-27
Publication date: 2002-04-04
Also published as: JPWO2002026679A1; AU2001290289A1

Abstract

A process for producing in high yield a fluorinated alcohol having any desired structure. The process comprises reacting RARBCHOH (1) with RCCOX (2) to form R?ARBCHOCORC¿ (3), fluorinating it in a liquid phase to form R?AFRBFCFOCORCF¿ (4), decomposing the fluorinated compound at the ester bond and obtaining RAFRBFCO (5) and RCFCOF (6) from the resultant reaction products, and then reducing the compound (5) and the compound (6) to obtain RAFRBFCHOH (7) or RAFCH2OH (7a) and RCFCH2OH (8), respectively. In the formulae, RA is a monovalent organic group; RAF is a monovalent organic group obtained through fluorination of RA, etc.; RB is hydrogen or a monovalent organic group; RBF is fluorine, a monovalent organic group obtained through fluorination of RB, etc.; R?C and RCF¿ may be the same or different and each is a monovalent organic group optionally fluorinated, etc.; and X is a halogen atom.

Description

Description Method for producing fluorinated alcohol

The present invention relates to a method for producing an industrially useful fluorinated alcohol. <Background technology>

Fluorinated alcohol compounds with a fluorocarbon alkyl group at the a-carbon have high acidity of alcohol hydrogen due to the electron-withdrawing property of the fluoroalkyl group, and have specific properties compared to the corresponding hydrocarbon alcohol. For example, it is known to be a good solvent for polyimides such as nylon which do not dissolve in ordinary organic solvents, and a good solvent for polar compounds such as ionic compounds.

Applications that take advantage of this feature include dye solvents used in the production of write-once compact discs (CD-R).

As a conventionally known method for synthesizing a fluorinated alcohol, a method of adding a fluororefin such as tetrafluoroethylene or hexafluoropropylene to methanol / ethanol (Japanese Patent Application Laid-Open No. 54-154707, Journ alof Fl uorine Chemistry, 28 (1985) 291), a method for reducing fluorine-containing carboxylic acids having a specific structure and a ride (Japanese Patent Publication No. 1-25729, Japanese Unexamined Patent Publication No. 279337), a method of hydrolyzing 2-chloro-1,1,1 trifluoroethane in the presence of a carboxylate (JP-A-58-134040, JP-A-58-140031) and the like. .

However, the structure of fluorinated alcohols that can be produced by conventional methods is limited by the method of assembling the carbon skeleton of the alcohol. Depending on the structure, it could not be synthesized or required a multi-step reaction. In the method of reducing the fluorine-containing force Rupon acid halide, the fluorine-containing carboxylic acid Hara Id electrolytic fluorination (Electrochemical Fluor inat ion ₀ hereinafter mounting serial and ECF method.) Or the like to synthesize in However, there is a problem that the yield is low, and particularly, it is difficult to produce a compound having an etheric oxygen atom by the ECF method, and it is economically disadvantageous.

'' Disclosure of the invention>

According to the present invention, as a result of examining various causes of the problems of the conventional method, first, when a substrate having a low molecular weight when performing a fluorination reaction in a liquid phase, the boiling point of the substrate decreases, We focused on the reaction between fluorine and the substrate in the gas phase, and the decomposition reaction of the compound. Therefore, a compound having a carbon skeleton corresponding to the target compound is obtained at low cost, an arbitrary compound is ester-bonded to the compound, fluorinated, and then the ester bond is decomposed and reduced to obtain alcohols as raw materials. The present inventors have found that a fluorinated alcohol having a corresponding structure can be obtained, and reached the present invention. Furthermore, they found an industrial continuous process by recycling the acylfluoride compound obtained from the decomposition reaction product of the ester bond.

That is, the present invention provides the following compound (3) by reacting the following compound (1) with the following compound (2), and fluorinating the compound (3) in a liquid phase to give the following compound (4): The following compound (5) and Z or the following compound (6) are obtained from the reaction product obtained by decomposing the ester bond of the compound (4), and then the compound (5) and / or the compound (6) is reduced. The following compound (7) is obtained from compound (5) (however, the following compound (7a) when R ^BF is a fluorine atom), and the following compound (8) is obtained from compound (6). Production of one or more fluorinated alcohols selected from compound (7), compound (7a), and compound (8) Provide a way.

R ^A R ^B CHOH (1)

R ^c COX (2)

R ^AB CHOCOR ^c (3)

RAF _R BF _CFOCOR CF ₍₄₎

R ^AF R ^BF CO (5)

R ^CF COF (6)

RAF _R BF _CHOH ( ₇ )

R ^AF CH ₂ OH (7a)

R ^CF CH ₂ OH (8)

However, R ^A and R ^AF are monovalent organic groups which may be the same or different, and when R ^A and R ^AF are different, R ^AF is a monovalent organic group in which R ^A is fluorinated .

R ^B is a hydrogen atom or a monovalent organic group, R ^BF when R ^B is a hydrogen atom is a fluorine atom, R ^BF when R ^B is a monovalent organic group, be the same as R ^B a different one optionally may monovalent organic group, R ^BF when the R ^B and R ^BF are different monovalent organic group, a monovalent organic group R ^B is fluorinated.

Or, R ^A and R ^B may be bonded to form a divalent organic group with one another, R ^AF and R ^BF of該場case forms a divalent organic radical bonded to each other, R ^A It is well, formed from R ^AF and R ^BF when varies also have been different in same divalent organic group made form from R ^B, and divalent organic group formed from R ^AF and R ^BF and The divalent organic group is a group in which the divalent organic group formed from R ^A and R ^B is fluorinated.

R ^c and R ^CF are each a monovalent organic group which may be the same or different, and when R ^c and R ^CF are different, R ^CF is a monovalent organic group in which R ^c is fluorinated; In addition, at least one of R ^A , R ^B , and R ^c is a group having a fluorine atom. X is a halogen atom. BEST MODE FOR CARRYING OUT THE INVENTION>

The organic group in the present specification refers to a group that essentially requires a carbon atom, and may be a saturated group or an unsaturated group. Examples of the atom that can be substituted with fluorine include a hydrogen atom bonded to carbon. Examples of the atomic group that can be substituted with fluorine include a carbon-carbon unsaturated double bond and a carbon-carbon unsaturated triple bond. For example, when a carbon-carbon double bond is present in an organic group, fluorine is added to the carbon-carbon double bond by fluorination in a liquid phase to form a carbon-carbon single bond. When a carbon-carbon triple bond is present in an organic group, fluorine is added to the carbon-carbon triple bond by fluorination in a liquid phase to form a carbon-carbon single bond or a carbon-carbon double bond. A bond is formed.

The monovalent organic group is preferably a monovalent hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, an octagenated monovalent hydrocarbon group, or a halogenated (heteroatom-containing monovalent hydrocarbon) group. These groups which are groups are particularly preferred. The divalent organic group is preferably a divalent hydrocarbon group, a heteroatom-containing divalent hydrocarbon group, a halogenated divalent hydrocarbon group, or a halogenated (heteroatom-containing divalent hydrocarbon) group. These groups are particularly preferred. As used herein, the term “saturated group” refers to a group in which a carbon-carbon bond in the group is composed of only a single bond. The organic group preferably has 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase used during the fluorination reaction.

The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and is preferably an aliphatic hydrocarbon group. Further, a single bond, a double bond, or a triple bond may be present as a carbon-carbon bond in the aliphatic hydrocarbon group. The aliphatic hydrocarbon group has a linear structure, a branched structure, a cyclic structure, or a partial cyclic structure. Structure.

Further, as the halogen atom in the halogenated group, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is preferable, and a fluorine atom, a chlorine atom, or a bromine atom is preferable. Or a fluorine atom and a chlorine atom are preferable, and a fluorine atom is more preferable. In the present specification, octagenation means that one or more hydrogen atoms have been replaced by halogen atoms. Partial octupenization means that a part of hydrogen atoms has been replaced by haptic atoms. That is, a hydrogen atom is present in the partially halogenated group. Perhalogenation means that all of the hydrogen atoms have been fluorinated. That is, there is no hydrogen atom in the perhalogenated group. The terms halogenation, partial halogenation, and perhalogenation have the same meaning when a halogen atom is specified. The number of halogen atoms present in the halogenated, halogenated, and bell-halogenated groups may be one or more.

Examples of the saturated monovalent hydrocarbon group include an alkyl group, and the structure may be any of a linear structure, a branched structure, a cyclic structure, and a partially cyclic structure. Examples of the saturated divalent hydrocarbon group include an alkylene group, and the structure may be any of a linear structure, a branched structure, a ring 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 having a straight-chain structure include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkyl group having a branched structure include an isopropyl group, an isobutyl group, a sec monobutyl group, a tert-butyl group, and the like. Examples of the alkyl group having a ring structure include a cycloalkyl group, a bicycloalkyl group, a group having an alicyclic spiro structure, and a 3- to 6-membered cycloalkyl group is preferable, and a cyclopentyl group or a cycloalkyl group is preferred. Xyl groups and the like.

As the alkyl group having a ring portion, the alkyl group having the above-mentioned ring structure is substituted ( Examples include an alkyl group having a straight-chain or branched structure, or a group in which the ring group of the alkyl group is further substituted with an alkyl group having a straight-chain or branched structure. A group in which at least one is substituted with a 3- to 6-membered cycloalkyl group is preferable, and a cyclopentylmethyl group, a cyclohexylethyl group, an ethylcyclohexylmethyl group, and the like are particularly preferable. Examples of other groups include an alkyl group having an aromatic ring (eg, an aralkyl group such as a benzyl group and a phenethyl group) and an alkyl group having a heterocyclic ring (eg, a pyridylmethyl group, a furfuryl group, and the like).

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.

The saturated halogenated hydrocarbon group refers to a group in which one or more of the hydrogen atoms present in the above-mentioned saturated hydrocarbon group is replaced by a halogen atom. You don't have to. The partially halogenated saturated hydrocarbon group refers to a group in which a part of the hydrogen atoms present in the above saturated hydrocarbon group has been replaced by halogen atoms. Hydrogen atoms are present in partially halogenated saturated hydrocarbon groups. The bell-halogenated saturated hydrocarbon group refers to a group in which all of the hydrogen atoms present in the saturated hydrocarbon group have been replaced by hydrogen and hydrogen atoms. No hydrogen atom exists in the perhalogenated saturated hydrocarbon group.

The saturated halogenated hydrocarbon group may have a straight-chain structure or a branched structure, may have a ring structure or a structure having a ring portion, and preferably has 1 to 20 carbon atoms. Among the saturated halogenated hydrocarbon groups, a monovalent group includes a fluoroalkyl group or a fluoro (partial alkyl) group, and a divalent group includes a fluoroalkylene group or a fluoro (partial alkyl) group. Alkylene) group and the like. Among the saturated perhalogenated hydrocarbon groups, the monovalent group includes a perfluoroalkyl group or a perfluoro (partially alkyl) group (that is, a group in which all the hydrogen atoms in the partial chloroalkyl group are fluorinated). preferable. As a divalent group Is a perfluoroalkylene group or a perfluoro (partial cycloalkylene) group

(Ie, a group in which all of the hydrogen atoms in the partial cycloarlene group are fluorinated) are preferred. Further, a perfluoro (partial fluoroalkyl) group is the same as a perfluoroalkyl group, and a perfluoro (partial fluoroalkylene) group is the same as a perfluoroalkylene group.

A saturated heteroatom-saturated hydrocarbon group refers to a group consisting of a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom, a carbon atom, and a hydrogen atom. The carbon number of the heteroatom-containing saturated hydrocarbon group is preferably from 1 to 20. The heteroatom may be a heteroatom itself or a heteroatom formed by combining heteroatoms or heteroatoms with other atoms. It is preferable that the hetero atom and the hetero atom group are not changed by a decomposition reaction of an ester bond (for example, a thermal decomposition reaction). Examples of the hetero atom include an etheric oxygen atom (C—O of C), = 0, and ≡N. An etheric oxygen atom is particularly preferred. Examples of the heteroatom-containing saturated hydrocarbon group include a group in which a divalent heteroatom or a divalent heteroatom group is inserted between carbon and carbon atoms of the saturated hydrocarbon group, or a carbon atom in the saturated hydrocarbon group. A group in which a heteroatom is bonded to an atom or a group in which a divalent heteroatom or a divalent heteroatom group is bonded to a carbon atom at the bonding terminal of the saturated hydrocarbon group is preferable.

As the hetero atom-containing group, an etheric oxygen atom-containing group is particularly preferred from the viewpoint of the usefulness of the compound. In particular, from the viewpoints of availability, ease of production, and usefulness of the product, the monovalent group is preferably an alkyl group containing an etheric oxygen atom (for example, an alkoxyalkyl group). As the valent group, an alkylene group containing an etheric oxygen atom (for example, a polyoxyalkylene group) is preferable. Examples of the monovalent aliphatic hydrocarbon group having a ring portion in which an etheric oxygen atom is inserted between one carbon atom of carbon include, for example, an alkyl group having a dioxolane skeleton. As the alkoxyalkyl group, a group in which one of the hydrogen atoms present in the alkyl group is substituted with an alkoxy group is preferable. The alkoxy group preferably has 1 to 10 carbon atoms. Examples of the alkoxyalkyl group include an ethoxymethyl group, an 11-propoxyethyl group, a 2-propoxyethyl group, and the like.

The saturated halogenated (hetero atom-containing hydrocarbon) group is preferably a saturated fluoro (hetero atom-containing hydrocarbon) group or a saturated fluoro (partial chroma (hetero atom-containing hydrocarbon)) group. The number of carbon atoms in the halogenated (heteroatom-containing saturated hydrocarbon) group is :! ~ 20 is preferred.

A saturated perhalogenated (heteroatom-containing hydrocarbon) group may have a linear or branched structure and may be a saturated perfluorinated (heteroatom-containing hydrocarbon) group or a saturated perfluorinated (partial chloroform) group. Mouth (heteroatom containing hydrocarbon)) groups are preferred. As the monovalent group, a perfluoro (hetero atom-containing alkyl) group or a perfluoro (partial port (hetero atom-containing alkyl)) group is preferable, and a perfluoro (alkoxyl) group or a perfluoro (partial port (alkoxyl)) group is particularly preferable. The divalent group is preferably a group in which one of the halogen atoms in a perhalogenated (heteroatom-containing monovalent saturated hydrocarbon) group is a bond, and a perfluoro (polyoxyalkylene) group is preferred. preferable.

Examples of these groups are specifically shown in the specific compounds described below. In the compound (1), R ^A and R ^B are preferably a group containing a hydrogen atom from the viewpoint of availability, and a saturated group having a hydrogen atom is more preferable for the intended reaction. It can be carried out efficiently and is also preferable from the viewpoint of usefulness of the intended fluorinated alcohol. ^RG is preferably a group containing a fluorine atom, since a continuous reaction can be carried out by reusing the compound produced by the production method of the present invention. The hydrogen atom in R ^B versa preferred.

^RA is a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, — It is preferably a monovalent saturated hydrocarbon group containing a telluric oxygen atom or a partially octalogenated (monovalent saturated hydrocarbon containing a etheric oxygen atom) group, and R ^B is a hydrogen atom or a monovalent. It is preferably a saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (monovalent saturated hydrocarbon containing an etheric oxygen atom) group. In particular, R ^A is an alkyl group, a partial alkyl group, an alkoxyalkyl group, or a partial alkyl (alkoxyalkyl) group, and R ^B is a hydrogen atom, an alkyl group, a partial alkyl group, an alkoxyalkyl group, or a partial alkyl group. R ^AF is a group in which all of the hydrogen atoms present in R ^A are substituted with fluorine atoms, and R ^BF is a group in which all of the hydrogen atoms present in R ^A are a fluorine atom or RB. It is preferably a group substituted by a fluorine atom.

Also, may also be linked R ^A and R ^B each other to form a divalent organic group, in the case of that the bivalent saturated hydrocarbon group, a partially halogenated bivalent saturated hydrocarbon group, ether property An oxygen atom-containing divalent saturated hydrocarbon group or a partially halogenated (etheric oxygen atom-containing divalent saturated hydrocarbon) group is preferred. In particular, an alkylene group, a partially branched alkylene group, an alkyleneoxyalkylene group, or a partially saturated hydrocarbon group is preferred. Preferably, it is a mouth (alkyleneoxyalkylene) group.

^Re is a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partial halogenation (a monovalent saturated hydrocarbon containing an etheric oxygen atom) It is preferable that all of the hydrogen atoms present in the group selected from the groups are substituted with fluorine atoms, in which case R ^CF is the same group as R ^c .

Compound (1) is a compound that is easily available or can be easily synthesized by a known method. Specific examples of the compound (1) include the following compounds. However, in the following, Cy represents a cyclohexyl group. (CH ₃ ) ₂ CHOH,

CH ₃ CH ₂ CH (CH ₃ ) OH,

CH ₂ = CHCH (CH ₃ ) OH,

CH ₃ (CH ₂ ) ₂ CH (CH ₃ ) OH,

CH ₂ C 1 CHC 1 CH ₂ CH (CH ₃ ) OH,

CH ₂ C 1 CHC 1 (CH ₂ ) ₂ OH,

CF ₂ C 1 CFC 1 CH ₂ CH (CH ₃ ) OH,

CF ₂ C 1 CFC 1 (CH ₂ ) ₂ OH,

Cy〇H,

CH ₃ CH ₂ OH,

CH ₃ (CH ₂ ) ₂ OH,

CH ₃ (CH ₂ ) ₃ OH,

CH ₂ = CHCH ₂ OH,

In the present invention, the compound (1) is reacted with the compound (2). The compound (2) is preferably a compound in which X is a fluorine atom in that it can react in a continuous process described below. The structure of R ^e in compound (2) is preferably adjusted in relation to the structure of R ^A in compound (1) so that compound (3) is easily dissolved in the liquid phase during fluorination. Specific examples of the compound (2) include the following compounds. CF ₃ CF ₂ C〇F,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF,

CF ₃ CF ₂ CF ₂ 〇CF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF.

As the compound (2), a commercially available product may be used, or the compound (6) which is a product in the production method of the present invention, or the compound (5) when R ^BF is a fluorine atom may be used. In the present invention, R ^A as the compound (1), that the structure of the R ^B may use a variety of different structures is one of the advantages. That is, by performing the reaction of the present invention using the compound (1) having R ^A and R ^B corresponding to R ^A ^F and R ^BF of the desired fluorinated alcohol, it is difficult to obtain by the conventional method. Compound (7) can be produced. In the compound (7) which was difficult to obtain a conventional method, (R ^AF) (R ^BF) CH- moiety and R ^AF in the - structure of fluorine Kaa alcohol or a complex partial, vapor phase fluorination Low-molecular-weight fluorinated alcohols that produce various types of by-products when produced by a fluorination reaction.

In the present invention, the reaction between the compound (1) and the compound (2) may be carried out in the presence of a solvent (hereinafter, referred to as a solvent 1), but is carried out in the absence of the solvent 1. Is preferred from the viewpoint of volumetric efficiency. When the solvent 1 is used, dichloromethane, chloroform, triethylamine, or a mixed solvent of triethylamine and tetrahydrofuran is preferable. The amount of the solvent 1 used is preferably 50 to 500% by mass based on the total amount of the compound (1) and the compound (2).

Further, in the reaction between compound (1) and compound (2), an acid represented by HX is generated. When a compound in which X is a fluorine atom is used as the compound (2), HF is generated. Therefore, an alkali metal fluoride (such as sodium fluoride) or a trialkylamine is present in the reaction system as a HF scavenger. May be. HF scavengers are particularly preferred when compound (1) or compound (2) is acid labile. When no HF scavenger is used, it is preferable to discharge HF out of the reaction system by accompanying the HF with a nitrogen stream. When the alkali metal fluoride is used, the amount is preferably 1 to 10 times the mol of the compound (2).

In general, the reaction temperature of the reaction between the compound (1) and the compound (2) is preferably 15 ° τ: or higher, more preferably +100 or lower, or lower than the boiling point of the solvent. The reaction time of the reaction is appropriately determined according to the supply rate and supply amount of the compound. It can be changed as needed. The reaction pressure (gauge pressure, the same applies hereinafter) is preferably normal pressure to 2 MPa.

The reaction of compound (1) with compound (2) produces compound (3). R ^A and R ^B in the compound (3) is the same as the base in the compound (1), and R ^c in the compound (3) is a base the same group in the compound (2).

The fluorine content of the compound (3) is preferably at least 30% by mass, particularly preferably from 30 to 86% by mass, particularly preferably from 30 to 76% by mass. If the fluorine content is too low, the solubility in the liquid phase will be extremely low, and the reaction system of the fluorination reaction will be uneven, and compound (3) will not be able to be fed into the reaction system well. There's a problem. The upper limit of the fluorine content is not limited, but if it is too high, the production cost of compound (3) is high and it is 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 the following compounds.

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCH (CH ₃ ) ₂ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCH (CH ₃ ) CH ₂ CHC 1 CH ₂ C 1,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCH (CH ₃ ) CH ₂ CH ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCH (CH ₃ ) (CH ₂ ) ₂ CH ₃ , CF ₃ (CF ₂ ) ₂ 〇CF (CF ₃ ) CO〇Cy,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCH (CH ₃ ) CH ₂ CFC 1 CF ₂ C 1, CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCH (CH ₃ )

2 ゝ

CF ₃ (CF ₂ ) ₂ 〇CF (CF ₃ ) COOCH ₂ CH ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) C〇OCH ₂ CH ₂ CHC 1 CH ₂ C 1,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CH ₂ ) ₂ CH ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CH ₂ ) ₃ CH ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CH ₂ ) ₂ CFC 1 CF ₂ C 1,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCH ₂ CH ₃ .

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, and may be used in the next reaction or the like as it is in high purity. From the viewpoint of safely carrying out the fluorination reaction in the next step, it is preferable to purify the crude product, and it is particularly desirable to remove the compound (1) from the crude product. As a method for purifying the crude product containing the compound (3), a method for distilling the crude product as it is, a method for treating the crude product with diluted alkaline water or the like, and a method for separating the crude product into an appropriate organic solvent And then distillation, silica gel column chromatography, and the like.

Next, in the present invention, compound (3) is reacted with fluorine in a liquid phase to obtain compound (4). The fluorination reaction in the present invention refers to a reaction in which at least one fluorine atom is bonded in the molecule of the compound (3).

In compound (4): ^AF is a group corresponding to R ^A , R ^BF is a group corresponding to R ^B , and R ^CF is a group corresponding to R ^c . Before and after the fluorination reaction, the arrangement of the carbon atoms of these groups does not change, and a compound (4) having a carbon skeleton corresponding to the compound (3) is obtained. However, when in the compound (3) is carbon one-carbon unsaturated bond, the bonding state 1 or more to be added fluorine atoms unsaturated bonds as mentioned above may change _c In the present invention, the fluorination in the liquid phase is preferably performed by a method of introducing fluorine gas into the liquid phase containing the compound (3). 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 V o 1% or more from the viewpoint of efficiency, and particularly preferably 20 V o 1% or more.

As the liquid phase, it is preferable to use a solvent capable of dissolving fluorine (F ₂ ) (hereinafter referred to as solvent 2). The solvent 2 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 chlorine atom, a nitrogen atom, and an oxygen atom. An organic solvent obtained by perfluorinating a known organic solvent having at least one kind of atom in the structure is preferable. Further, as the solvent 2, a compound

It is preferable to use a solvent having high solubility of (3), particularly preferably a solvent capable of dissolving 1% by mass or more of compound (3), particularly preferably a solvent capable of dissolving 5% by mass or more. Examples of the solvent 2 include perfluoroalkanes (FC-72, etc.), perfluoro alcohols (FC-75, FC-77, etc.), perfluoropolyethers (trade name) : Krytox, Fonpurin, Galden, Demnum, etc.), Fluorocarbons (R-113, trade name: CFC), Fluoropolyethers, Perfluoroalkylamines (for example, Perflu And an inert fluid (trade name: Florinert).

Further, as the solvent 2, one or more of the compound (4), the compound (5) and the compound (6) having a function as a solvent can be used. In particular, when compound (4), fluorine-containing ketone (5) or compound (6) is used as a solvent, there is an advantage that post-treatment after the reaction is facilitated.

The amount of the solvent 2 is preferably at least 5 times the mass of the compound (3), particularly preferably 10 to 100 times the mass. The fluorination reaction is preferably performed in a batch system or a continuous system. In each case, it is preferable to perform the fluorination method 1 or the fluorination method 2 described below. In particular, from the viewpoint of the reaction yield and the selectivity, it is preferable to carry out the fluorination method 2. In addition, the fluorine gas may be a fluorine gas diluted with an inert gas such as a nitrogen gas, regardless of whether the method is performed in a batch mode or in a continuous mode.

[Fluorination method 1] Compound (3) and solvent 2 are charged into a reactor, and stirring is started. Next, the reaction is carried out while continuously supplying fluorine gas to the liquid phase in the reactor at a predetermined reaction temperature and reaction pressure.

[Fluorination method 2] Charge solvent 2 into a reactor and start stirring. Then, the compound (3) and fluorine gas are continuously and simultaneously supplied at a predetermined molar ratio to the liquid phase in the reactor at a predetermined reaction temperature and reaction pressure.

When supplying the compound (3) in the fluorination method 2, the compound (3) may or may not be diluted with the solvent 2, but since the selectivity is improved and the amount of by-products is suppressed, the compound diluted with the solvent 2 is used. It is preferable to supply (3). When diluting compound (3) with a solvent in fluorination method 2, the amount of solvent 2 is preferably at least 5 times, more preferably at least 10 times, the mass of compound (3). Is preferred.

Regarding the fluorination reaction, whether the reaction is carried out in a batch mode or in a continuous mode, the reaction is carried out in a state where the amount of fluorine is always in excess with respect to the hydrogen atoms in compound (3). It is preferable to use fluorine so as to be at least 1.5 times equivalent (ie, at least 1.5 times mol) from the viewpoint of selectivity. It is preferable that the amount of fluorine 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 not less than 160 and not more than the boiling point of the compound (3). From the viewpoint of reaction yield, selectivity, and ease of industrial implementation, the reaction temperature is preferably −50 to −10. 100 ° C is particularly preferred, and 120 ° C to 150 ° C is particularly preferred. Fluorine The reaction pressure of the chemical reaction is not particularly limited, and 0 to 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.

Furthermore, 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 or to perform ultraviolet irradiation. Thereby, the compound (3) present in the reaction system can be efficiently fluorinated, and the reaction rate can be drastically improved.

The C—H bond-containing compound is an organic compound other than the compound (3), particularly preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like. The amount of the C—H bond-containing compound to be added is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, based on the hydrogen atoms in compound (3).

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.

Compound (4) is produced by the fluorination reaction of compound (3).

In the compound (4), when R ^A is a group having no atom or atomic group that can be substituted by fluorine, or when R ^A is not fluorinated, R ^AF is the same group as R ^A. R ^A has an atom or an atomic group that can be substituted by fluorine, and when fluorinated, R ^AF is a different group from R ^A. The same applies to R ^B , R ^BF , R ^c , and R ^CF.

Compound (3) from the R ^A and R ^B are obtained compounds are hydrogen containing group Yasuiko, R ^AF and R ^BF in the compound (4) is a hydrogen atom in R ^A and R ^B is its Each is preferably a fluorinated group. Further, the compound (4) compound (3) from that preferably a compound which is Perufuruoro of compound (4) in each R ^AF and R ^BF of hydrogen atoms contained in R ^A and R ^B of It is particularly preferred that all are fluorinated groups. That is, R ^AF and R ^BF are a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (etheric oxygen atom, respectively). (Contained monovalent saturated hydrocarbon) It is preferable that all hydrogen atoms present in the group are substituted with fluorine atoms (however, in ^RBF , a fluorine atom is also preferable), an alkyl group, alkyl group, § Turkey alkoxyalkyl group or a partially halogenated (alkoxyalkyl) all of the hydrogen atoms present in the group are substituted by fluorine atoms are particularly preferable (provided that, in the R ^B ^F, especially also fluorine atom Preferred).

Alternatively, R ^AF and R ^BF are bonded to each other to form a divalent saturated hydrocarbon group, a partially halogenated divalent saturated hydrocarbon group, a divalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (etheric (Oxygen atom-containing divalent saturated hydrocarbon) It is preferable to form a group in which all of the hydrogen atoms in the group are substituted with fluorine atoms, and particularly, an alkylene group, a partial cycloalkylene group, an alkyleneoxyalkylene group, or It is preferable that all the hydrogen atoms present in the partially halogenated (alkyleneoxyalkylene) group are substituted with fluorine atoms.

R ^eF is a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, and a partially halogenated (monovalent saturated hydrocarbon group containing an etheric oxygen atom). It is preferable that all of the hydrogen atoms present in the group selected from the group consisting of hydrogen) are substituted with fluorine atoms.

Specific examples of the compound (4) include the following compounds. Here, Cy ^F in the following formula represents a perfluorocyclohexyl group.

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCF (CF ₃ ) ₂ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCF (CF ₃ ) CF ₂ CFC 1 CF ₂ C 1,

CF ₃ (CF ₂ ) ₂ 〇CF (CF ₃ ) COOCF (CF ₃ ) CF ₂ CF ₃ , CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCF (CF ₃ ) (CF ₂ ) ₂ CF ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COOCy ^F

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCF (CF ₃ )

2 ゝ

CF ₃ (CF ₂ ) ₂ 〇CF (CF ₃ ) COOCF ₂ CF ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CF ₂ ) ₂ CFC 1 CF ₂ C 1,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CF ₂ ) ₂ CF ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) COO (CF ₂ ) ₃ CF ₃ ,

CF ₃ (CF ₂ ) ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COOCF ₂ CF ₃ ,

In the case of a reaction in which a hydrogen atom is replaced with a fluorine atom in a fluorination reaction, HF is by-produced. To remove by-product HF, it is preferable to coexist with an HF scavenger in the reaction system or to contact the HF scavenger with the outlet gas at the reactor gas outlet. As the HF scavenger, the same one as described above is used, and NaF is preferable.

The amount of the HF scavenger coexisting in the reaction system is preferably 1 to 20 times, and more preferably 1 to 5 times the molar amount of the total 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 to room temperature, particularly preferably maintained at about 20 ° C.) (b) NaF Pellet packed bed, and (c) cooler (preferably maintained between 78 ° C and 10 ° C, preferably — maintained between 30 ° C and 0 ° C) with (a) — ( b) It is preferable to install them in series in the order of (c). In addition, a liquid return line for returning the aggregated liquid from the cooler in (c) to the reactor may be provided. 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.

In the present invention, the ester bond of the compound (4) is further decomposed.

The reaction for decomposing the ester bond of compound (4) is preferably carried out by decomposing the ester bond by heating, or by decomposing the ester bond in the presence of a nucleophile or an electrophile. preferable.

When the ester bond is decomposed by heating (hereinafter referred to as thermal decomposition), it is preferable to select the type of reaction depending on the boiling point of the compound (4) and its stability. For example, in the case of thermally decomposing the easily vaporizable compound (4), a vapor phase pyrolysis method of continuously decomposing in the gas phase and condensing and recovering the outlet gas containing the product may be employed.

The reaction temperature of the gas phase pyrolysis method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, particularly preferably from 150 to 250 ° C. In addition, an inert gas not directly involved in the reaction may be allowed to coexist in the reaction system. Examples of the inert gas include nitrogen gas and carbon dioxide gas. The inert gas is preferably added in an amount of about 0.1 to 50 V o 1% based on the compound (4). If the amount of inert gas added is large, the amount of product recovered may decrease.

In the gas phase pyrolysis method, it is preferable to use a tubular reactor. When a tubular reactor is used, the residence time is preferably about 0.1 second to 10 minutes on an empty tower basis. The reaction pressure is not particularly limited. When the compound (4) is a high boiling point compound, the reaction is preferably performed under reduced pressure. In particular, when the compound (4) is a low-boiling compound, it is preferable to carry out the reaction under pressure because decomposition of the product is suppressed and the reaction rate is increased.

When performing a gas phase reaction using a tubular reactor, fill the reaction tube with glass, an alkali metal salt, or an alkaline earth metal salt to promote the reaction and fix it. The reaction is preferably carried out in a bed or in a fluidized bed.

As the alkali metal salt or alkaline earth metal salt, carbonate or fluoride is preferable. Examples of the glass include common soda glass, and glass beads having a fluidity in the form of beads are particularly preferable. Alkali metal salts include sodium carbonate, sodium fluoride, potassium fluoride, potassium carbonate, or lithium carbonate. Examples of the alkaline earth metal salt include calcium carbonate, calcium fluoride, magnesium carbonate and the like.

Of these, alkali metal salts are preferable, alkali metal fluorides are particularly preferable, and potassium fluoride is particularly preferable. The use of potassium fluoride is particularly preferred in that the yield of the decomposition reaction is high, the reaction can be carried out even at a low reaction temperature, and the reaction can be carried out efficiently even with a small amount of potassium fluoride. The alkali metal salt may be supported on a carrier or used. Carriers include activated carbon, activated alumina, zirconia, or salts of different types of alkali metals. Further, when the reaction tube is filled with glass, an alkali metal salt, or an alkaline earth metal salt and reacted in a fluidized bed, glass beads or light ash of sodium carbonate is used. It is particularly preferable to use one having a particle size of about 100 to 250 m.

The gas phase reaction is preferably carried out in the presence of an inert gas which is not directly involved in the thermal decomposition reaction for the purpose of promoting the vaporization of the compound (4). Examples of the inert gas include nitrogen gas, carbon dioxide gas, helium gas, and argon gas. The amount of the inert gas is preferably about 0.01 to 50 vo 1% based on the compound (4). If the amount of the inert gas is too large, the amount of the recovered product may be low, which is not preferable. On the other hand, when compound (4) is a compound that is difficult to vaporize, it is preferable to employ a liquid phase pyrolysis method in which the liquid (4) is heated in a liquid state in the reactor. The reaction pressure in this case is not limited. In general, the product of the ester bond decomposition reaction has a lower boiling point than compound (4). From this point, it is preferable to carry out the reaction while distilling using a reactor equipped with a distillation column, and to carry out the reaction by vaporizing and continuously extracting the product. Alternatively, a method may be used in which the products are collectively extracted from the reactor after the completion of the heating. The reaction temperature in this liquid phase pyrolysis method is preferably from 50 to 300, particularly preferably from 100 to 250.

When 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 a solvent 3). It is preferable from the viewpoint of suppressing by-products. Solvent 3 is not particularly limited as long as it does not react with compound (4) and is compatible with compound (4) and does not react with compound (5) and compound (6) to be formed. . As the solvent 3, it is preferable to select a solvent that is easily separated at the time of purifying the compound (5) or at the time of purifying the compound (6) described later. Specific examples of the solvent 3 include an inert solvent such as perfluorotrialkylamine, and a chlorotrifluoroethylene oligomer (for example, trade name: CFC) having a high boiling point among the fluorocarbons such as chlorofluorocarbons. I like it. The amount of the solvent 3 is preferably from 10 to 1000% by mass based on the compound (4). When the ester bond of the compound (4) is decomposed by a method of reacting with a nucleophile or an electrophile in a liquid phase, the reaction can be carried out without a solvent, even in the absence of a solvent. ) May be performed, and it is preferable to perform without solvent from the viewpoint of volumetric efficiency and suppression of by-products. The solvent 4 is preferably the same as the solvent 3. As the nucleophile, F— is preferable, and F— derived from alkali metal fluoride is particularly preferable. As alkali metal fluorides, NaF, NaHF ₂ , KF, and CsF are preferred. Of these, NaF is preferred in terms of economy, and KF is particularly preferred in terms of reactivity. When using a nucleophile (eg, F-I), F— nucleophilically adds to the carbonyl group present in the ester bond of compound (4), and R ^AF R ^BF CF 0_ is eliminated. As a result, acid fluoride [compound (6)] is generated. R ^AF R ^BF CFO Then, F_ is eliminated to form a ketone [compound (5)]. However, depending on the conditions of the thermal decomposition reaction, compound (6) may be further decomposed to produce another compound (for example, an unsaturated compound described later). The eliminated F— reacts in the same way as another compound (4) molecule. Therefore, the nucleophile used at the beginning of the reaction may be a catalytic amount or may be used in excess. That is, the amount of the nucleophile such as F_ is preferably from 1 to 500 mol%, particularly preferably from 10 to 100 mol%, particularly preferably from 5 to 50 mol%, based on the compound (4). The reaction temperature is preferably from -30 to the boiling point of the solvent or the compound (4), and particularly preferably from 20 ° C to 250 ° C. This method is also preferably carried out in a reactive distillation mode.

The reaction product of the ester decomposition reaction of compound (4) contains compound (6) together with compound (5) under ordinary conditions.

Specific examples of the compound (5) include the following compounds.

(CF ₃ ) ₂ CO,

CF ₃ CF ₂ COCF ₃ ,

CF ₃ (CF ₂ ) ₂ COCF ₃ ,

CF ₂ C 1 CFC 1 CF ₂ COCF ₃ ,

CF ₃ C〇F,

CF ₃ CF ₂ C〇F,

CF ₃ (CF ₂ ) ₂ COF,

CF ₂ C 1 CFC 1 CF ₂ COF,

On the other hand, compound (6) is a compound in which R ^c in compound (2) is R ^GF and X is a fluorine atom. Specific examples of the compound (6) include the compounds exemplified in the compound (2).

The compound (6) is preferably reused as the compound (2) to be reacted with the compound (1), and the compound (5) can be continuously produced by reusing the compound (2). That is, the compound (1) is reacted with the compound (2) to give a compound (3), the compound (3) is fluorinated in a liquid phase to give a compound (4), and then an ester bond of the compound (4) The compound (6) is obtained from the reaction product obtained by decomposing the compound (6), and a part or all of the compound (6) is used again as the compound (2) to react with the compound (1), whereby the compound (5) can be continuously obtained. Can be manufactured.

In the present invention, the compound (6) and Z or the compound (5) are obtained from the product of the ester decomposition reaction, and are reduced. Compound (6) alone, compound (5) alone, or a mixture of compound (6) and compound (5) may be isolated from the product of the esterification reaction. These can be appropriately changed depending on the desired form of the fluorinated alcohol. Here, R ^BF is a fluorine atom, and RA _F and RC; if _F is the same structure, since it becomes the same compound as the compound ₍₅₎ with the compound (6), the product compound ( Only 5) (or only compound (6)), which has the advantage of eliminating the need for product separation. In the reduction reaction, compound (7) is formed from compound (5). However, compound (7a) is formed from compound (5) in which R ^BF is a fluorine atom. Compound (8) is formed from compound (6). R ^AF and R ^{BF in} compound (7) and compound (7a) have the same meanings as those in compound (5), and R ^GF in compound (8) has the same meaning as in compound (6). Show. The fluorinated alcohol in the present invention refers to one or more compounds selected from compound (7), compound (7a), and compound (8).

The reduction reaction is preferably performed by ordinary hydrogen reduction, and particularly preferably performed using hydrogen in the presence of a metal-supported catalyst. Preferably, 0.5 to 5% by weight of the metal in the catalyst is supported on the support, particularly preferably 1 to 3% by weight. The amount of hydrogen relative to the compound to be reduced is preferably not less than the stoichiometric amount, more preferably 1.2 to 10 times, particularly preferably 1.5 to 5 times, the reaction activity and catalyst. It is preferable in terms of durability and product recovery.

Further, the metal-supported catalyst is preferably a catalyst in which palladium or a group 8-10 element containing palladium as a main component is supported on a carrier. Group 8 to 10 elements other than palladium include iron, cobalt, nickel, Ru, Rh, Ir, and Pt, and these are preferably added alone or in combination of two or more. 8 to: The addition amount of the group I0 element is preferably 0.01 to 50 parts by weight based on 100 parts by weight of palladium.

Further, in order to improve the activity and durability of the catalyst, a metal component other than the group 8 to 10 element can be further used. The metal-supported catalyst is preferably a metal catalyst (hereinafter, referred to as a specific metal catalyst) essentially including an element selected from Groups 8 to 10 and a Group 11 element. Examples of Group 8 to 10 elements include the same elements as described above, and Pd, Rh, Ir, and Pt are particularly preferable. The Group 11 element is selected from Cu, Ag and Au, with Au being particularly preferred. Group 11 elements are 8-1 It has the effect of highly dispersing and stabilizing the element component selected from Group 0 in the catalyst. When the element components selected from the group 8 to 10 are highly dispersed and stabilized, (d) the number of active sites and the activity are increased, and the reducing ability of the catalyst is improved. The reduction reaction proceeds even at low reaction temperatures, and halogenated alcohols can be obtained with high yield and long catalyst life. (E) Since the aggregation (synthesis ring) of the metal fine particles is suppressed, the heat resistance is improved, and the catalyst is hardly deactivated even when the temperature of the catalyst layer increases. (Ii) Since the catalyst surface is always kept in a highly reduced state, it prevents acidic compounds such as hydrogen chloride and hydrogen fluoride, which are poisonous substances, from adsorbing on the catalyst surface, thereby achieving high yield. The reduction reaction can be performed with a long catalyst life. In addition, there is an advantage that a complicated process for purifying the substrate before reduction is not required.

The amount of the group 11 element contained in the specific metal catalyst with respect to the group 8 to 10 element is preferably 0.01 to 90% by mass from the viewpoint of the effect of increasing the dispersion and stabilization of the group 11 element. More preferably, it is from 0.1 to 50% by mass, particularly preferably from 0.1 to 30% by mass.

Further, the metal catalyst is preferably a catalyst in which the above-mentioned metal component is supported on activated carbon. For example, in a specific metal catalyst, a group 8-10 element and a group 11 element are supported on the support. Preferably, the catalyst is a modified catalyst. As the carrier, for example, activated carbon, aluminum, zirconia, and the like are suitable, and activated carbon is particularly preferable. As the activated carbon, those prepared from raw materials such as wood, charcoal, fruit ash, coconut husk, peat, lignite, or coal can be used. Vegetable raw materials are preferable to mineral raw materials, and coconut husk activated carbon is particularly suitable. Yashigara activated carbon is considered to be superior in activity and durability because it has a larger surface area, less impurities such as silica, and higher acid resistance than other activated carbons. The ash content of the activated carbon is preferably from 0.01 to 20% by mass. The amount of the group 8 to 10 element to be supported on the carrier is preferably from 0.01 to 5% by mass, more preferably from 0.01 to 10% by mass, in view of the reduction ability and economy of the catalyst. Particularly preferably, 0.5 to 5% by mass It is.

Also, the shape of the carrier is preferably formed from about 2 to 5 mm in length of molded coal, about 4 to 50 mesh of crushed coal, granular coal, or the like. Molded coal is particularly preferred. The method for supporting the metal on the activated carbon is not particularly limited, and a conventional method, for example, supporting palladium chloride alone or together with a metal chloride of another group 8 to 10 element on a carrier, drying, and further drying this with hydrogen For example, a reduction method is used. Activated carbon catalysts supporting Group 8 metals are durable and do not require long-term activation, but if activated, hydrogen reduction is carried out at 100-300 ° C, preferably 200-300 ° C. Is preferred.

Specific examples of the metal catalyst in the present invention include, in addition to the catalysts described in Examples described later, Rh—Co—CuZ activated carbon (C) (a catalyst in which Rh, Co, and Cu are supported on activated carbon; ), Rh-Co-AgZC, Rh-Co-Au / C, Pt_AuZC, Pd-Ni-CuZC, Pd-Ni-Ag / C, Pd-Ni-AuZC, Ru-Au / C, P d-Cu / A 1 2 0 3, P d-Ag / A 1 2 0 3, P d-Au / A 1 2 0 3, P d_P t- AuZA 1 2 〇 _3, P d-Rh _{_{-Au / A 1 2 0 3,}} Pd- I r one _{_{Au / A 1 2 0 3,}} Rh-Ag / A 1 2 0 3, Rh-Au / A 1 2 〇 _{3, Rh-C o-Cu} / A 1 ₂ 0 _3, Rh one C o one _{_{Ag / A 1 2 0 3,}} Rh- Co one _{_{Au / Al 2 0 3, P}} t -Au / A 1 2 0 3, P dN i -Cu / A 1 2 0 _3> Pd-N i one _{_{Ag / Al 2 0 3, Pd}} -N i -Au / A 1 2 0 3, Ru-Au / A 1 2 0 3, Pd - Cu / Z R_〇 _2, Pd-Ag / Z r0 _2, Pd- AuZZ R_〇 _{2, Pd- P t- A uZZ r0} 2, P d-Rh-Au / Z r 0 2, P d- I r- AuZZ r 0 2, Rh- Ag / Z r0 _{2, Rh-Au / Z r} 0 2, R h- C o- C uZZ r 0 2, Rh- Co one _{Ag / Z r0 2, Rh- C} o- Au / Z R_〇 _2, P t Au / Z R_〇 _2, Pd-N i one _{Cu / Z r0 2, Pd_N i-} AgZZ r 0 2, P d- N Bok _{Au / Z r 0 2, Ru} -Au / Z r0 2 , and the like. Certain metal catalysts are highly durable catalysts that can be used repeatedly with little deactivation even after a long reduction reaction. Further, by using a specific catalyst, excellent reaction results can be maintained without using an acid acceptor or the like.

In addition, when hydrogen is used for the reduction of compound (5) and Z or compound (6), the amount of hydrogen is represented by the number of reaction moles for compound (5) and / or compound (6) to be reduced. It is preferably at least twice the molar amount of the above, and more preferably at least 3 to 8 times, in that the desired fluorinated alcohol can be obtained in a high yield.

The reaction pressure for the reduction reaction is preferably normal pressure or increased pressure, but may be reduced pressure. If the reaction temperature is too low, the reaction rate will be slow, and the product yield will be low.If the reaction temperature is too high, the deterioration of the catalyst will occur due to the formation of acidic compounds and an increase in the temperature of the catalyst layer. Is from 130 to 250 ° C, preferably from 150 to 200 ° C, at normal pressure. Furthermore, when a specific catalyst is used, the reaction can be carried out at a lower temperature, and the reaction temperature is preferably 30 to 450 ° C, more preferably 50 to 200 ° C, particularly preferably 70 to 150 ° C. is there.

When the reaction is performed by a gas phase method, it is preferable to use a reaction temperature and a pressure in which the raw material and the product continue to be gas in the reactor. Further, the contact time with the catalyst in the gas phase method is preferably 0.1 to 1000 seconds, particularly preferably 1 to 100 seconds, particularly preferably 4 to 60 seconds, and further preferably 5 to 20 seconds. The reaction may be carried out while diluting with an inert gas such as nitrogen to control the excessive temperature rise. According to the production method of the present invention, a desired fluorinated alcohol can be produced using the raw material compound (1) which can be obtained at low cost. Among the fluorinated alcohols obtained by the production method of the present invention, specific examples of compound (7) include the following compounds.

(CF ₃ ) ₂ CHOH, CF ₃ CF (CF ₃ ) CH〇H,

CF ₃ CF ₂ CF (CF ₃ ) CHOH,

CF C 1 CFC 1 CF (CF ₃ ) CHOH,

Particularly, specific examples of the compound (7a) include the following compounds.

CF ₃ CH ₂ OH,

CF ₃ CF ₂ CH ₂ OH,

CF ₃ CF ₂ CF ₂ CH ₂ OH,

CF ₂ C 1 CFC 1 CF ₂ CH ₂ OH.

Specific examples of the compound (8) include the following compounds.

CF ₃ CF ₂ CH ₂ OH,

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CH ₂ OH,

CF ₃ CF ₂ CF ₂ 〇CF (CF ₃ ) CF ₂ OCF (CF ₃ ) C'H ₂ 〇H.

The fluorinated alcohol obtained by the production method of the present invention has high acidity of alcoholic hydrogen due to the electron-withdrawing property of the fluorine-containing group, and has specific characteristics as compared with the corresponding hydrocarbon alcohol. For example, it is a good solvent for polyimides such as nylon which do not dissolve in ordinary organic solvents, and a good solvent for polar compounds such as ionic compounds. <Example>

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. In the following, the yield was determined from the peak area ratio of gas chromatography (GC) and NMR spectrum. Further, tetramethylsilane noted TM S, the CC 1 _₂ FCC 1 ₂ and scale one 113. The NMR spectrum data is shown as an apparent chemical shift range.

[Example 1]

Example 1 _1: Esterification process>

A 2-liter Hastelloy-C22 autoclave equipped with a reflux condenser cooled to 25 ^nC was charged with isopropanol (240 g, 4 mol), and after heating the reactor to 40 ° C, CF ₃ CF ₂ Reaction was performed by continuously introducing CF ₂ 〇CF (CF ₃ ) COF (1328 g, 4 mol) into the reactor so that the temperature rise due to the heat of reaction was 10 ° C or less. After all the CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF was added, the temperature was raised to 50 ° C. and the reaction was performed for 2 hours. After the completion of the reaction, the mixture was cooled to room temperature, and HF by-produced by the reaction was purged by introducing nitrogen gas to obtain a crude liquid (1480 g). As a result of GC, the yield of CF ₃ CF ₂ CF ₂ 〇CF (CF ₃ ) COOCH (CH ₃ ) _{2 was} 99.5%. Example 11: Fluorination process>

R-113 (312 g) was added to a 50 OmL nickel autoclave, stirred, and kept at 25 ° C. A cooler kept at 15 ° C was installed at the autoclave gas outlet. 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% with nitrogen gas is blown at a flow rate of 6.17 LZh for 1 hour The pressure inside the reactor was kept at 0.15 MPa. Next, while blowing the fluorine gas at the same flow rate and maintaining the pressure in the reactor at 0.1 MPa, the CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCH (CH ₃ ) obtained in Example 11 was obtained. After injecting a solution of ₂ (4.99 g) in R_113 (100 g) over 5.3 hours, fluorine gas was blown in at the same flow rate and the pressure inside the reactor was maintained at 0.15 MPa. 9 mL of the R_113 solution with a benzene concentration of 0.01 gZmL while increasing the temperature from 25 ^ to 40 ° C, closed the benzene inlet of the autoclave, and continued stirring for 0.5 hours. . Next, while injecting fluorine gas at the same flow rate, maintain the pressure inside the reactor at 0.15 MPa, the temperature inside the reactor at 40 ° C, and inject 6 mL of the above benzene solution into the autoclave. Was closed and stirring was continued for 0.5 hour.

The same operation was repeated once. The total amount of benzene injected was 0.219 g, and the total amount of R-113 injected was 21 mL. Furthermore, nitrogen gas was blown in for 1.5 hours to obtain the target substance from the reactor.

Was quantified the desired product ^{_{_{19 F- NMR, CF 3 CF 2}}} CF 2 OCF (CF 3) COOCF (CF 3) 2 and _{_{_{CF 3 CF 2 CF 2 OCF (}}} CF 3) COOCH (CF 3) 2 yield Were 48.1% and 19.1%, respectively.

CF ₃ CF _₂ CF ₂ 〇_CF _{_{(CF 3) COOCF (CF 3}} ) 2: 19 F - NMR (3 76. 0MHz, solvent: CDC 1 _3, _{reference: CFC I 3) δ (p} pm): -79. 4 (3F), -79.6 (3F), -79.9 (IF), -82.1 (3F), -82.2 (3F), 1 87.7 (IF), 1 130.4 (2F), — 132.1 (1F), one 143.4 (1F).

_{_{_{CF 3 CF 2 CF 2 OCF (}}} CF 3) COOCH (CF 3) 2: 19 F-NMR (3 76. 0 MHz, solvent · · CDC 1 _3, _{reference: CFC 1 3) δ (pm} ): -74. 0 (3 F), -74. 1 (3 F), -79. 9 (IF), -82. 3 (3 F), -82. 5 (3 F), -87. 7 (IF), — 130. 4 (2 F), one 132. 6 (1F :). - NMR (399. 0 MH z, solvent: CD C 1 _3, reference: TM S) δ (ppm) : 5. 80 (m, 1 H) ingredients Example 1 one 3: ester bonds minute angular Army reaction step>

Example 1 CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCF (CF ₃ ) ₂ (5 g) obtained in 1-2 was charged into a 30-OmL flask equipped with a reflux condenser at 80 ° C. (0.06 g) was added thereto, and the generated gas was heated and stirred at 150 and collected in a glass trap cooled to 178 ° C. When the reaction proceeded and all the liquid in the flask disappeared, the reaction was terminated. The collected product (4.8 g) was obtained in a glass trap.

As a result of GC, it can be seen that (CF ₃ ) ₂ CO (hereinafter, referred to as HFA) and CF ₃ CF ₂ CF ₂₀ CF (CF ₃ ) COF were formed at a molar ratio of 1: 1. I got it.

<Examples 1-4 A-D: reduction process)

The following reaction was carried out using (CF ₃ ) ₂ CO obtained by repeating the above reaction.

A catalyst (10 OmL) supporting 2 parts by weight of the metal components described in Examples 14A to 14D in Table 1 per 100 parts by weight of crushed coconut husk was added to Inconel 600, 1Z2 inches and 1 m long, respectively. The reactor was filled with the reactor and heated from the outside and kept at 170. Into this, HFA was introduced at a flow rate of 0.2 mol / h, and simultaneously, hydrogen was introduced at a flow rate of 1.6 mol / h to carry out the reaction. As a result of analyzing the outlet gas of the reactor by GC, (CF ₃ ) ₂ CHOH (hereinafter referred to as HF IP) was produced with the results shown in Table 1, respectively. (table 1)

[Example 2]

Example 11 The same reaction was carried out except that the isopropanol of Example 11 was changed to 240 g (4 mol) of propanol to obtain 1480 g of a crude liquid. As a result of GC, the yield of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCH ₂ CH ₂ CH ₃ was 99.5%.

Example 1 CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCH (CH ₃ ) ₂ obtained in Example 2 CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCH ₂ CH ₂ CH ₃ (4. The reaction was performed in the same manner except that the amount was changed to 99 g). When the product was quantified by ¹⁹ F-NMR, the yield of CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COO CF ₂ CF ₂ CF ₃ was 91%.

CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCF (CF ₃ ) ₂ obtained in Example _1-3 CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COOCF ₂ CF ₂ CF ₃ (5 g) obtained in Example 2-2 ) And the same reaction was carried out. GC results, CF ₃ CF ₂ COF and CF ₃ CF _{It was found that 2} CF ₂ OCF (CF ₃ ) C〇F was formed at a molar ratio of 1 respectively.

The following reaction was carried out using CF ₃ CF ₂ COF obtained by repeating the above reaction. A catalyst (100 mL) supporting 2 parts by mass of the metal component described in Example 2-4A to Example 2-4C in Table 2 per 100 parts by mass of coconut husk pulverized coal was 1Z2 inches long. Into a reaction tube made of Inconel 600, and heating it from the outside to keep it at 170 ° C, introducing CF ₃ CF ₂ COF at a flow rate of 0.2 molnoh, The reaction was carried out by introducing at a flow rate of 6 mol. As a result of analyzing the outlet gas of the reactor by GC, CF ₃ CF ₂ CH ₂ OH was obtained with the results shown in Table 2, respectively.

(Table 2)

[Example 3]

<Example 3-1> Esterification step

(CH ₃ ) ₂ CHOH (7.0 g) was charged into the flask, and the mixture was stirred while bubbling nitrogen gas through. FCOCF (CF ₃ ) 〇CF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (61.0 g) was added dropwise over 30 minutes while maintaining the internal temperature at 25 to 30. After the addition, the mixture was stirred at room temperature for 1 hour, and saturated aqueous sodium hydrogen carbonate (50 mL) was added. The temperature was below 15 ° C.

The obtained crude liquid was separated to obtain a lower layer. The lower layer was further washed twice with water (50 mL), dried over magnesium sulfate, and filtered to obtain a crude liquid. The crude solution was washed twice with water (5 OmL), dried over magnesium sulfate, filtered, and filtered (CH ₃ ) ₂ CHOCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) 〇CF ₂ CF ₂ CF ₃ ( 64.0 g, GC purity 98%.) Was obtained.

To a 300 OmL nickel autoclave having an external circulation tube reactor, CF ₃ CF ₂ CF ₂ 〇CF (CF ₃ ) CF ₂ 〇CF (CF ₃ ) COF (2534 g) was added, circulated and stirred, Kept at 25. At the outlet of the autoclave gas, a cooler maintained at 110 ° C was installed. After blowing nitrogen gas for 2.0 hours, 50% diluted fluorine gas was blown at a flow rate of 41.97 LZh for 2 hours. Next, while blowing 50% diluted fluorine gas at the same flow rate, (CH ₃ ) ₂ CHO C〇CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (obtained in Example 3-1) 1440 g) was injected over 24.0 hours. 1700 g of the reaction crude liquid was extracted.

Then, while blowing 50% diluted fluorine gas at the same flow rate, (CH ₃ ) ₂ C HOCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (1440 g) was added over 24.0 hours. Injected. The reaction crude liquid (1700 g) was extracted. The same operation was repeated five times, and nitrogen gas was blown for 2 hours. The reaction crude liquid (2850 g) was obtained from the autoclave.

Next, the reaction crude liquid (2500 g) was added to the autoclave, circulated and stirred, and kept at 25 ° C. After blowing nitrogen gas for 2.0 hours, 50% diluted fluorine gas was blown at a flow rate of 41.97 L / h for 2 hours. Next, while injecting 50% diluted fluorine gas at the same flow rate, (CH ₃ ) ₂ CHOCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (1440 g) was injected over 24.0 hours, and nitrogen gas was blown for 2 hours. 4190 g of a crude reaction solution was obtained.

The target product was quantified by ¹⁹ F-NMR (internal standard: C ₆ F ₆ ). The yield of (CF ₃ ) ₂ C FOCOCF (CF ₃ ) CFCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ was 94 %Met.

¹⁹ F- NMR (376. 0MHz, solvent CDC 1 _3, _{reference: CFC 1 3) <5 (} ppm):.. -78 5~- 80. 0 (7 F), -80 7 (3 F), - 81.9 to 82.8 (8 F), 18.4 to 86.3 (IF), --130.2 (2 F), -132.2 (IF), -143.1 (IF) , One 145.4 (1 F). Example 3—3 A: Ester Bond Decomposition Step>

(CF ₃ ) ₂ CFOCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) 〇CF ₂ CF ₂ CF ₃ and (CF ₃ ) ₂ CH〇COCF (CF ₃ ) OCF ₂ CF (CF ₃ ) 〇CF ₂ CF ₂ CF A mixture of ₃ and 8: 2 (mass ratio) (hereinafter, this mixture is referred to as a fluorinated ester mixture, 10.0 g.) Was charged into a flask together with 0.03 g of KF powder, and the mixture was vigorously stirred. While heating in an oil path at 120 ° C for 10 hours. At the top of the flask, a reflux condenser controlled at 20 ° C and a fluororesin collecting container were installed in series.

After cooling, a liquid sample (7.9 g) and a gaseous sample (1.9 g) were recovered. The analysis by GC-MS revealed that the gaseous sample was mainly HFA and the liquid sample was FCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF _3. confirmed. : The yield of was 95.2%. Further, FCOCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (5.9 g) was obtained from the liquid sample. <Example 3 3B>

An Inconel column (inner diameter 14 mm, length lm) was filled with a catalyst (10 to 20 mesh, 50 g) in which 10% by mass of KF was supported on NaF, and placed in a salt bath. Adjusted to 200 ° C. The fluorinated ester mixture was fed to the reactor using a metering pump at 60 gZ hours for 2 hours. At the reactor outlet, a reflux condenser adjusted to a temperature of 20 ° C was installed to separate the gaseous sample and liquid sample, and the gaseous sample (23.2 g) was placed in a fluoroplastic collection container. A liquid sample (96.5 g) was collected in a glass trap. Result of both samples were analyzed respectively by GC-MS, gas sample is HF A main product, the liquid sample F CO CF (CF ₃₎ 〇_CF _{_{_{2 CF (CF 3) OCF 2}}} CF 2 CF 3 Was confirmed to be the main product. The yield of 118 was 97.1%. In addition, FC OCF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (69.8 g) was obtained from the liquid sample. Example 3-4: Reduction process>

Coconut shell activated carbon was immersed in pure water to impregnate the water into the pores. An aqueous solution in which palladium chloride and copper sulfate were dissolved at a ratio of 9: 1 in terms of the mass ratio of Pd and CU was added dropwise little by little until the total mass of the metal component with respect to the mass of activated carbon became 0.5%. The ionic components were adsorbed on activated carbon. After further washing with pure water, it was dried at 150 ° C for 5 hours. Next, after drying at 550 in nitrogen for 4 hours, hydrogen was introduced, and reduced at 25 O for 5 hours to obtain a catalyst (Pd-CuZC catalyst).

<Catalyst Preparation Example 2> ''

The procedure was the same as in Preparation Example 1, except that palladium chloride and copper sulfate in Preparation Example 1 were changed, and that palladium sulfate and silver sulfate were changed to Pd: Ag = 9: 1 (converted mass ratio). A medium (Pd—AgZC catalyst) was obtained.

Change the palladium chloride and copper sulfate in Preparation Example 1 to Pd: Au-9: 1 (converted mass ratio) for palladium chloride and chloroauric acid, and change the drying temperature 550 ° C in Preparation Example 1 to 500. A catalyst (Pd—Au / C catalyst) was obtained in the same manner as in Preparation Example 1 except for the above.

The palladium chloride and copper sulfate in Preparation Example 1 were changed to Pd: Pt: Au = 90: 2: 8 (converted mass ratio) for palladium chloride, chloroplatinic acid, and chloroauric acid, and dried in Preparation Example 1. A catalyst (Pd-Pt-AuZC catalyst) was obtained in the same manner as in Preparation Example 1, except that the temperature was changed from 550 ° C to 500 ° C.

The palladium chloride and copper sulfate in Preparation Example 1 were changed to palladium chloride, rhodium chloride, and chloroauric acid to Pd: Rh: Au = 90: 1: 9 (converted mass ratio), and the drying temperature in Preparation Example 1 was changed. A catalyst (Pd—Rh—AuZC catalyst) was obtained in the same manner as in Preparation Example 1 except that 550 was changed to 500.

Palladium chloride, iridium chloride, and chloroauric acid were changed to Pd: Ir: Au-90: 1: 9 (converted mass ratio) in Preparation Example 1 for palladium chloride and copper sulfate. Catalyst (Pd—Ir-Au / C catalyst) was obtained in the same manner as in Preparation Example 1 except that the drying temperature (55 (TC)) was changed to 500 ° C and the reduction temperature (250) was changed to 300. .

The palladium chloride and copper sulfate in Preparation Example 1 were changed to rhodium sulfate and silver sulfate to Rh: Ag = 9: 1 (converted mass ratio), and the reduction temperature in Preparation Example 1 (250 ° C) The catalyst (Rh-Ag / C catalyst) was obtained in the same manner as in Preparation Example 1 except that the temperature was changed to 300 ° C.

Preparation Example 8

The palladium chloride and copper sulfate in Preparation Example 1 were changed to rhodium chloride and chloroauric acid with Rh: Au = 9: 1 (converted mass ratio), and the reduction temperature (250 ° C) in Preparation Example 1 was changed to 300 ° C. A catalyst (Rh—AuZC catalyst) was obtained in the same manner as in Preparation Example 1 except for the change.

100 ml of the catalyst prepared in Preparation Examples 1 to 8 was filled into a reaction tube made of Inconel 600 having an inner diameter of 16 mm and a length of lm, heated in an oil bath, and hydrogen and HFA were introduced therein. The reduction reaction was performed under the reaction conditions shown in The results after the reaction for 100 hours are shown in the table below.

(Table 3)

[Example 3—4—9 to Example 3—4—11]

100 ml of the catalyst prepared in Preparation Examples 1 to 3 was charged into an Inconel 600 reaction tube having an inner diameter of 16 mm and a length of lm, and heated with an oil path, and hydrogen and 1,3-dichloro-1,1 were added thereto. The reduction reaction was carried out under the reaction conditions shown in the table below by introducing 3,3,3-tetrafluoro Q acetone. The results after 100 hours of reaction are shown in the table below. (Table 4)

[Example 3—4-1 1 2 to Example 3—4 1 1 4]

100 ml of the catalyst prepared in Preparation Examples 1 to 3 was filled into a reaction tube made of Inconel 600 having an inner diameter of 16 mm and a length of lm, and heated in an oil bath. In the evening, fluoroacetone was introduced to carry out a reduction reaction under the reaction conditions shown in the table below. The results after the reaction for 100 hours are shown in the table below.

41

(Table 5)

[Example 3—4—i 5 to Example 3—4—17]

CF ₃ COCF ₃ was absorbed in water three times or more in mole and distilled to obtain an azeotropic mixture of CF ₃ C (OH) ₂ CF ₃ -2H ₂₀ (boiling point: 105 106 ° C.). Next, the catalyst prepared in Preparation Example 13 (10 g, Example 15 17) or 2% Pd Z activated carbon catalyst (Nippon Engelpachi) was placed in a pressure-stirred autoclave made of Hastelloy having a capacity of 2 L. (10 g, Comparative Example 5) and the above-prepared CF ₃ C (OH) ₂ CF ₃ -2H ₂₀ (1000 g) were charged, and the vessel was replaced with hydrogen. The reaction was carried out at a reaction temperature shown in Table 4 by pressurizing to 5 MPa (gauge pressure). After reacting for 5 hours, the catalyst was separated from the reaction product by a filter, and the same reaction was repeated 10 times. The results after the tenth reaction are shown in the table below. (Table 6)

Industrial potential>

According to the present invention, a fluorinated alcohol, which has been difficult to produce for structural or reaction reasons, can be produced. In addition, starting from an inexpensive raw material that can take any structure, various fluorinated alcohols having various structures and meeting various needs can be produced in high yield. Further, by selecting the structure of the raw material, two kinds of fluorinated alcohols having different structures or a fluorinated alcohol having a single structure can be obtained. Further, by selecting the structure of the raw material, the fluorinated alcohol can be continuously produced.

Furthermore, when a specific catalyst is used for the reduction reaction, a stable long-term reduction reaction can be performed with a high yield without using an acid acceptor.

Claims

The scope of the claims

1. The following compound (1) is reacted with the following compound (2) to give the following compound (3). The compound (3) is fluorinated in a liquid phase to give the following compound (4). )), The following compound (5) and / or the following compound (6) is obtained from the reaction product obtained by decomposing the ester bond, and then the compound (5) and Z or the compound (6) are reduced to obtain the compound ( The following compound (7) is obtained from 5) (however, the following compound (7a) when R ^BF is a fluorine atom), and the following compound (8) is obtained from compound (6). A method for producing one or more fluorinated alcohols selected from the group consisting of: compound (7), compound (7a), and compound (8).

R ^A R ^B CHOH (1)

R ^c COX (2)

R ^A R ^B CHOCOR ^c (3)

_R AF _R BF _{C FOC} Q _R CF (4)

RAF _R BF _C Q ₍₅₎

R ^CF COF (6)

R ^AF R ^BF CH〇H (7)

R ^AF CH ₂ OH (7a)

R ^CF CH ₂ OH (8)

Alternatively, R ^A and R ^B may be bonded to each other to form a divalent organic group. R ^AF and R ^BF combine with each other to form a divalent organic group, and a divalent organic group formed from R ^A and R ^B and a divalent organic group formed from R ^AF and R ^BF The divalent organic group formed from R ^AF and R ^{BF in the} different case may be the same as or different from the divalent organic group formed from R ^A and R ^B. is there.

R ^G and R ^GF are each a monovalent organic group which may be the same or different, and when R ^c and R ^CF are different, R ^CF is a monovalent organic group in which R ^G is fluorinated; In addition, at least one of R ^A , R ^B , and R ^c is a group having a fluorine atom.

X is a halogen atom.

2. ^RA is a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (monovalent saturated hydrocarbon containing an etheric oxygen atom) R ^AF is a group in which all of the hydrogen atoms present in R ^A are substituted with fluorine atoms, and R ^B is a hydrogen atom, a monovalent saturated hydrocarbon group, or a partially halogenated monovalent saturated hydrocarbon group. , an ether oxygen atom-containing monovalent saturated hydrocarbon group or a partially halogenated (etheric oxygen atom-containing monovalent saturated hydrocarbon) group, all of the hydrogen atoms R ^BF is present in a fluorine atom or R ^B, is It is a group substituted by a fluorine atom, or R ^A and R ^B are bonded to each other to form a divalent saturated hydrocarbon group, a partially vaccinated divalent saturated hydrocarbon group, and a divalent saturated containing an etheric oxygen atom. Hydrocarbon group or partially halogenated (d To form a ether oxygen atom-containing bivalent saturated hydrocarbon) group, a R ^AF and R ^BF are all hydrogen atoms in the group formed by R ^A and R ^B is substitution by a fluorine atom group, R ^c and R ^eF are the same and a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, containing an etheric oxygen atom, a monovalent saturated hydrocarbon group, and a partially halogenated (containing an etheric oxygen atom) A monovalent saturated hydrocarbon) wherein all of the hydrogen atoms present in the group selected from the group are substituted with fluorine atoms. Item 1. The production method according to Item 1.

3. R ^A is an alkyl group, a partial alkyl group, an alkoxyalkyl group, or a partial alkyl group (alkoxyalkyl) group, and R ^AF is such that all of the hydrogen atoms present in R ^A have been replaced with fluorine atoms. Group,

R ^B is a hydrogen atom, an alkyl group, a partial alkyl group, an alkoxyalkyl group, or a partial alkyl (alkoxyalkyl) group, and R ^BF is a fluorine atom, or all of the hydrogen atoms present in R ^B are fluorine. A group substituted by an atom,

Or, R ^A and R ^B combine with each other to form an alkylene group, a partially cycloalkylene group, an alkyleneoxyalkylene group, or a partially cycloalkylene (alkyleneoxyalkylene) group, and R ^AF and R ^BF are All hydrogen atoms in the group formed from R ^A and R ^B which are bonded to each other are substituted with fluorine atoms,

R ^c and R ^GF are the same, and all of the hydrogen atoms present in the group selected from the group consisting of an alkyl group, a partial alkyl group, an alkoxyalkyl group and a partial alkyl group (alkoxyalkyl) are fluorine atoms. 2. The production method according to claim 1, which is a group substituted with:

4. The production method according to any one of claims 1 to 3, wherein the fluorine content in the compound (3) is 30% by mass or more.

5. The production method according to claim 1, wherein the fluorine content in the compound (3) is 30% by mass to 70% by mass.

6. The production method according to any one of claims 1 to 5, wherein the molecular weight of the compound (3) is from 200 to 1,000.

7. The production method according to claim 1, wherein R ^BF is a fluorine atom, and R ^AF and R ^CF have the same structure.

8. The production method according to any one of claims 1 to 7, wherein the produced compound (6) is used as the compound (2).

9. The production method according to any one of claims 1 to 8, wherein X is a fluorine atom.

10. The production method according to any one of claims 1 to 9, wherein the fluorination in the liquid phase is performed by introducing fluorine gas into the liquid phase containing the compound (3).

11. The production method according to claim 1, wherein the reduction is carried out by reacting with hydrogen in the presence of a metal-supported catalyst.

12. The production method according to claim 11, wherein the metal-supported catalyst is a catalyst which essentially requires at least one element selected from Group 8 to Group 10 elements and at least one Group 11 element.

13. Reduction of compound (5) and / or compound (6) in the presence of at least one element selected from the group 8 to 10 elements and at least one group 11 element catalyst From compound (5), the following compound (7) (provided that

When R ^BF is a fluorine atom, the following compound (7a)) is obtained, and from compound (6), the following compound (8) is obtained. Compound (7), compound (7a), and A method for producing one or more fluorinated alcohols selected from compound (8).

RAF _R BF _{CO (5)} R ^CF COF (6)

RAF _R BF _{CH OH} (?)

R ^AF CH ₂ OH (7a)

R ^CF CH ₂ OH (8)

However, R ^AF is a monovalent organic group, R ^BF is a fluorine atom or a monovalent organic group, or R ^AF and R ^BF may combine with each other to form a divalent organic group. R ^CF is a monovalent organic group. However, at least one of R ^AF , R ^BF , and R ^CF is a group having a fluorine atom.

14. The production method according to claim 13, wherein the reaction is performed without using an acid acceptor.

15. The production method according to any one of claims 1 to 14, wherein the hydrogen used for the reduction is at least twice the stoichiometric mole.