JP4857984B2 - Method for producing fluorine-containing diol and derivatives thereof - Google Patents

Description

  The present invention relates to a fluorine-containing diol represented by the formula [2], which is a compound useful as a monomer raw material corresponding to a next-generation photoresist.

It relates to the manufacturing method.

  Esters of acrylic acids such as acrylic acid and methacrylic acid in fluorine-containing diols are promising compounds as monomer raw materials for next-generation resist materials, and resists containing these esters as constituents have light transmission and surface adsorption properties. It is known that it is excellent (Patent Document 1). The fluorine-containing diol represented by the formula [2], which is the target compound of the present invention, is also derived from the fluorine-containing ester represented by the formula [4].

(In the formula, R ¹ represents any group of H, C _m H _{2m + 1} , and C _n F _{2n + 1} (m and n each represents an integer of 1 to 4).
Is also a promising compound as a monomer raw material for next-generation resist materials.

  As a production technique related to the fluorine-containing diol represented by the formula [2], which is the object of the present invention, conventionally, a fluorine-containing hydroxyketone represented by the formula [5]

(Wherein R ¹ is a hydrogen atom, or a chain or cyclic alkyl group having 1 to 7 carbon atoms. R ² is a chain or cyclic alkyl group having 1 to 7 carbon atoms, a phenyl group, or a substituted phenyl group. R ¹ and R ² may be linked to form a ring.) Is reduced with aluminum isopropoxide using isopropanol as a solvent, and fluorine-containing diols represented by the formula [6]

(Wherein R ¹ and R ² are the same as in formula [5])
There is known a method of obtaining (Patent Document 2).
JP 2003-040840 A US Pat. No. 3,660,711

  In the method of Patent Document 2, since isopropanol is used as a solvent and a large amount of aluminum isopropoxide is used as a reducing agent, there is a problem of discharging a large amount of aluminum waste, waste water from an inclusion machine, and the like on an industrial scale. When implemented, it was a burden.

  Here, in this invention, it was a subject to provide the conditions which can implement the manufacturing method of the fluorine-containing diol shown by Formula [2] on an industrial scale.

  In view of the problems of the prior art, the present inventors have intensively studied. As a result, the hydroxyketone represented by the formula [1]

Is reduced with hydrogen in the presence of a ruthenium catalyst to give a fluorine-containing diol represented by the formula [2]

Was found to be able to be produced in a good yield under mild reaction conditions with little waste (first step).

Here, the “ruthenium catalyst” refers to a ruthenium metal or ruthenium supported on a carrier (activated carbon, alumina, silica, clay, etc.) or a ruthenium salt (for example, RuCl ₃ , RuBr ₃ , Ru (NO ₃ ) _3. Etc.), ruthenium complexes (eg Ru (CO) ₅ , Ru (NO) ₅ , K ₄ [Ru (CN) ₆ ], Ru (phen) ₃ Cl ₃ (where phen represents phenanthroline)), ruthenium oxide, etc. Refers to that.

  The present inventors have prepared a fluorine-containing hydroxyketone represented by the formula [5].

Has been found to be able to produce fluorine-containing diols represented by the formula [6] by contacting them with hydrogen in the presence of a ruthenium catalyst (Japanese Patent Application No. 2005-018862).

According to this method, as a starting compound represented by the formula [5], “a compound in which R ¹ is H and R ² is a cyclohexyl group” (a compound represented by the following formula [7])

By using this, the fluorine-containing diol represented by the formula [2], which is the object of the present application, can be produced. However, the compound represented by the formula [7] is very expensive and has a problem that it is difficult to obtain a large amount.

  Here, when the present inventors continued further examination, when the hydroxyketone represented by the formula [1] was brought into contact with hydrogen in the presence of a ruthenium catalyst, the phenyl group was also hydrogenated (reduced). It was found that the fluorine-containing diol represented by [2] was produced together.

  The hydroxyketone represented by the formula [1] is a compound that can be produced at a very low cost using hexafluoroacetone and acetophenone as raw materials. That is, as a result of the present invention, the fluorine-containing diol represented by the formula [2] can be produced in a particularly advantageous manner economically compared to the case where the compound represented by the formula [7] is used as a raw material. .

  Furthermore, the present inventors have found that the above reaction proceeds at a high selectivity under specific reaction conditions. That is, the reaction for producing the fluorine-containing diol represented by the formula [2] by bringing the hydroxyketone represented by the formula [1] into contact with hydrogen in the presence of a ruthenium catalyst is performed at a relatively low temperature of 70 ° C. or less. It was found that the process proceeds with a particularly high selectivity.

  The reaction in which an aromatic compound is brought into contact with hydrogen in the presence of a transition metal catalyst and the aromatic ring of the compound is reduced to a cyclohexyl ring is a generally known reaction. However, this reaction generally requires high temperature and reaction pressure. For example, the following reaction

Therefore, the conditions of a temperature of 150 to 190 ° C. and a pressure of 6.9 MPa are required (Source: SJ Lappporte, WR Schütt, Journal of Organic Chemistry, 28, 1947-1948, 1963 ( USA)). Under such harsh conditions, the performance required for the reactor is high, the operation becomes complicated in the synthesis in a large amount, and there is a concern about the decomposition of the trifluoromethyl group or the like in the substrate targeted by the present invention. .

  However, when the present inventors examined the substrate of the present invention, the reaction proceeded at a sufficient speed even at the above-mentioned relatively low temperature, and the target product was obtained with a particularly high selectivity under such conditions. (Example 1). As a result, the production of the target fluorinated diol represented by the formula [2] on a large scale has been remarkably facilitated.

  Further, the thus obtained fluorine-containing diol represented by the formula [2] is converted into an acrylic acid derivative represented by the formula [3].

(In the formula, R ¹ represents any ^one of H, C _m H _{2m + 1} , and C _n F _{2n + 1} (m and n each represents an integer of 1 to 4), X represents F, Cl, Or a group represented by the following formula [3a]

Represents one of the following. The meaning of R ¹ in formula [3a] is the same as in formula [3]. The fluorine-containing ester represented by the formula [4], which is promising as a monomer raw material for next-generation resist materials

(In the formula, the meaning of R ¹ is the same as in formula [3].)
Can be easily manufactured (second step).

  That is, the present invention provides a method for producing a fluorine-containing diol represented by the formula [2], wherein the hydroxyketone represented by the formula [1] is reduced with hydrogen in the presence of a ruthenium catalyst. Further, the fluorine-containing diol represented by the formula [2] obtained by the above method is reacted with an acrylic acid derivative represented by the formula [3]. A method for producing a fluorine ester is also provided.

  According to the present invention, the desired 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3 is obtained by a simple operation of reduction with hydrogen in the presence of a ruthenium catalyst. -Diols can be produced.

  Hereinafter, the present invention will be described in more detail. The process of the present invention can be carried out in a batch reactor. The reaction conditions will be described below, but this does not prevent changes in the reaction conditions that can be easily adjusted by those skilled in the art in each reaction apparatus.

  In the present invention, the first step (the step of obtaining the fluorine-containing diol represented by the formula [2] by reducing the hydroxyketone represented by the formula [1] with hydrogen in the presence of a ruthenium catalyst) is essential. As an element, if necessary, the second step (the fluorine-containing diol represented by the formula [2] obtained in the first step is reacted with the acrylic acid derivative represented by the formula [3], Step of obtaining a fluorine-containing ester represented by the formula [4]) (see scheme 1 below).

  First, the first step will be described. The first step is a step of obtaining the fluorine-containing diol represented by the formula [2] by reducing the hydroxyketone represented by the formula [1] with hydrogen in the presence of a ruthenium catalyst.

  The method for synthesizing the hydroxyketone represented by the formula [1] can be produced by a known method disclosed in Patent Document 2.

  Here, the reaction temperature and reaction pressure when the hydroxyketone represented by the formula [1] is reduced with hydrogen in the presence of a ruthenium catalyst will be described in detail below.

  First, the reaction temperature for carrying out this reaction will be described in detail later, but it is 0 ° C to 150 ° C, preferably 10 ° C to 120 ° C, and particularly preferably 30 ° C to 70 ° C. If it is less than 0 degreeC, reaction rate will be very slow and will not become a practical manufacturing method.

  In addition, the by-product represented by the formula [8] at 100 ° C. or higher, for example, 110 ° C.

Begins to increase and the selectivity of the target compound decreases (see Example 2). In particular, heating to a temperature exceeding 150 ° C. causes a further decrease in the selectivity of the target compound, which is economically undesirable from the viewpoint of energy efficiency.

  In this reaction, setting the reaction temperature to 30 to 70 ° C., particularly 40 ° C. to 60 ° C. (for example, 50 ° C.) is the target product without generating the by-product represented by the formula [8]. Since the fluorine-containing diol represented by the formula [2] can be obtained with very high selectivity, it is one of the particularly preferred embodiments (see Example 1).

  The reaction pressure (referred to as hydrogen pressure; hereinafter the same) in the first step is usually 0.1 to 6 MPa (absolute pressure; hereinafter the same in this specification), preferably 0.15 to 4.0 MPa, 0.2 to 4.0 MPa is particularly preferable. However, the preferred reaction pressure has temperature dependence. That is, when the reaction is performed at a relatively high temperature (80 ° C. or higher), the reaction proceeds at a sufficient rate even at a reaction pressure of 1.0 MPa or lower, which is often preferable, but it is preferable that the reaction is performed at a low temperature (80 ° C.). A lower reaction pressure (eg, 1.6 MPa or more) is often preferred. For example, when the reaction is performed at 30 to 70 ° C., a reaction pressure of 1.6 to 4.0 MPa is particularly preferable. It is desirable to optimize the reaction pressure in accordance with various conditions such as the reaction temperature and the type and amount of the catalyst described later.

  The reaction proceeds even at a reaction pressure of less than 0.1 MPa, but in order to obtain a sufficient reaction rate, a temperature higher than 150 ° C. may be required, resulting in a side reaction being promoted. It is not preferable. On the other hand, when the pressure exceeds 6 MPa, a reaction vessel that can withstand a high pressure is required, which is not preferable because it becomes complicated.

Examples of the ruthenium catalyst used in the first step include ruthenium metal or ruthenium supported on a support (activated carbon, alumina, silica, clay, etc.), or a ruthenium salt (for example, RuCl ₃ , RuBr ₃ , Ru (NO _{3)). 3} ), ruthenium complexes (eg Ru (CO) ₅ , Ru (NO) ₅ , K ₄ [Ru (CN) ₆ ], Ru (phen) ₃ Cl ₃ (where phen represents phenanthroline)), ruthenium oxide Etc. are used.

Among these, a solid-phase catalyst in which ruthenium is supported on a carrier is particularly preferable from the viewpoint of easy availability and handling. These solid-phase catalysts can be prepared, for example, by dissolving a ruthenium salt in a solution, impregnating the solution with a support, and then reducing with H ₂ gas while heating. In particular, Ru / C (ruthenium-carbon catalyst), ruthenium-alumina catalyst, and ruthenium-silica catalyst are preferred because they are readily available commercially and have high activity. These are particularly easy to handle when using water-containing products (for example, products containing 50% by weight of water in the total weight of the catalyst). In addition, there is no particular restriction on the Ru content in the solid components (components other than water) of these catalysts, but those with about 2 to 10% by weight (for example, 5% by weight) are easily available and stable. It is preferably used because of its high properties and easy handling.

  The reaction can be carried out in the presence of a plurality of these ruthenium catalysts, but usually there is no special merit.

  The amount of the ruthenium catalyst is usually 0.0002 mol to 0.04 mol, preferably 0.0004 mol to 0.02 mol, in terms of Ru atom, per mol of the hydroxyketone represented by the formula [1]. 0.001 mol to 0.01 mol is more preferable. When the ruthenium catalyst is less than the above lower limit, the reaction rate decreases, and when it is more than the upper limit, it is not economically preferable.

  A solvent can be used in this reaction. There are no particular limitations on the type of solvent that can be used, but ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methanol, ethanol, propanol, 2-propanol, trifluoroethanol, 1,1 , 1,3,3,3-hexafluoro-2-propanol and the like are preferable, and these may be used alone or in combination with a plurality of solvents. The amount of the solvent used in this reaction is 0.005 to 100 g, preferably 0.01 to 20 g, more preferably 0.1 to 10 g, based on 1 g of hydroxyketone represented by the formula [1]. If it exceeds 100 g, it is not economically preferable from the viewpoint of productivity.

  In this reaction, a tetrafluoroethylene resin, a chlorotrifluoroethylene resin, a vinylidene fluoride resin, a PFA resin, a glass lined inside, a glass vessel, or a reactor made of stainless steel can be used.

  Although the method for carrying out the present invention is not limited, details will be described with respect to an example of a desirable embodiment.

A hydroxyketone represented by the formula [1], a solvent, and a catalyst are added to a reactor that can withstand reaction conditions, and hydrogen is supplied from the outside while heating to advance the reaction. The time required for the reaction depends on the reaction temperature, the type and amount of the catalyst. It is preferable to observe the state of consumption of H ₂ as needed from the pressure in the reactor, etc., and terminate the reaction when the consumption of H ₂ is virtually completed.

  The consumption of the raw material is monitored by sampling or the like, it is confirmed that the reaction is completed, and the reaction liquid is cooled. The produced fluorinated diol represented by the formula [2] is purified by applying a known method. For example, after filtering the catalyst from the obtained reaction solution, the filtrate is distilled or the filtrate is used. By crystallization, it is possible to easily obtain the fluorinated diol represented by the formula [2].

  Next, the second step will be described. In the second step, the fluorine-containing diol represented by the formula [2] obtained in the first step is replaced with the acrylic acid derivative represented by the formula [3].

(In the formula, R ¹ represents any ^one of H, C _m H _{2m + 1} , and C _n F _{2n + 1} (m and n each represents an integer of 1 to 4), X represents F, Cl, Or a group represented by the following formula [3a]

Represents one of the following. The meaning of R ¹ in formula [3a] is the same as in formula [3]. ) -Containing fluorine ester represented by the formula [4]

(In the formula, the meaning of R ¹ is the same as in formula [3].)
It is the process of obtaining.

As the substituent R ¹ of the acrylic acid derivative represented by the formula [3], H, methyl and trifluoromethyl are particularly preferred from the usefulness of the product represented by the formula [4].

  This step may be performed by a general means of esterification, but preferable methods, conditions and the like are described below.

  First, the case where the acrylic acid derivative represented by the formula [3] is an α-substituted acrylic acid halide will be described. This step is preferably performed in the presence of a base. As the base, at least one selected from the group consisting of trimethylamine, triethylamine, pyridine, 2,6-dimethylpyridine, dimethylaminopyridine, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide is preferably used. . Of these, pyridine and 2,6-dimethylpyridine are particularly preferred.

  The amount of the base used in this step is 0.2 to 2 mol, preferably 0.5 to 1.5, and preferably 0.9 to 1. mol per mol of the fluorinated diol represented by the formula [2]. Two moles are more preferred. When the amount of the base is less than 0.2 mol relative to 1 mol of the fluorine-containing diol represented by the formula [2], both the selectivity of the reaction and the yield of the target product are lowered. When the amount exceeds 2 mol, the reaction is involved. This is economically unfavorable because the amount of base to be used increases.

  The amount of the α-substituted acrylic acid halide used in this step is 0.2 to 2 mol, preferably 0.5 to 1.5 mol, relative to 1 mol of the fluorinated diol represented by the formula [2]. 0.9 to 1.2 mol is more preferable. When the amount of the α-substituted acrylate halide is less than 0.2 mol relative to 1 mol of the fluorine-containing diol represented by the formula [2], both the selectivity of the reaction and the yield of the target product are lowered, and the amount exceeds 2 mol. And α-substituted acrylate halides which are not involved in the reaction increase, which is economically undesirable from the time of disposal.

  In this step, a base hydrohalide (hydrofluoride, hydrochloride) is precipitated as a by-product. It is necessary to use a solvent to improve operability. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds such as benzene, toluene, xylene, and mesitylene, ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methylene chloride, and chloroform And halogen-based solvents such as carbon tetrachloride are preferable, and these may be used alone or in combination with a plurality of solvents.

  The amount of the solvent used in this step is 0.5 to 100 g, preferably 1 to 20 g, and more preferably 2 to 10 g based on 1 g of the fluorinated diol represented by the formula [2]. If the amount of the solvent is less than 0.5 g relative to 1 g of the fluorinated diol represented by the formula [2], the slurry concentration of the hydrofluoric acid salt and hydrochloride of the base precipitated during the reaction is too high, so that the operability is lowered. To do. If it exceeds 100 g, it is not economically preferable from the viewpoint of productivity.

  The reaction temperature for carrying out this step is −50 to 200 ° C., preferably −20 to 150 ° C., and more preferably 0 ° C. to 120 ° C. If it is less than -50 degreeC, reaction rate will be very slow and it will not become a practical manufacturing method. On the other hand, if it exceeds 200 ° C., the raw material α-substituted acrylate halide or the fluorine-containing ester represented by the formula [4] is polymerized.

  In the reaction of this step, the polymerization may be carried out in the presence of a polymerization inhibitor for the purpose of preventing the raw material α-substituted acrylate halide or the product fluorine-containing ester compound from being polymerized. Polymerization inhibitors used are hydroquinone, methoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, nonflex F, nonflex H , Non-flex DCD, non-flex MBP, ozonone 35, phenothiazine, 2-methoxyphenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2-picrylhydrazine, Q- 1300 or at least one compound selected from Q-1301. The above polymerization inhibitors are commercially available products and can be easily obtained.

  The amount of the polymerization inhibitor used in this step is 0 to 0.1 mol, preferably 0.00001 to 0.05 mol, based on 1 mol of the fluorine-containing diol represented by the raw material formula [2]. 0.0001 to 0.01 mol is more preferable. Even if the amount of the polymerization inhibitor exceeds 0.1 mol with respect to 1 mol of the fluorine-containing diol represented by the formula [2] of the raw material, there is no significant difference in the ability to prevent the polymerization, and this is economically undesirable. .

  The reactor for carrying out the reaction in this step is preferably a tetrafluoroethylene resin, a chlorotrifluoroethylene resin, a vinylidene fluoride resin, a PFA resin, a glass lined inside, a glass vessel, or a stainless steel. .

  Next, the reaction in this step when the acrylic acid derivative represented by the formula [3] is an α-substituted acrylic acid anhydride will be described.

  The amount of the α-substituted acrylic anhydride to be used is usually 0.5 to 5 mol, preferably 0.7 to 3 mol, based on 1 mol of the fluorinated diol represented by the formula [2]. Two moles are more preferred. If the amount of α-substituted acrylic acid anhydride is less than 0.5 mol relative to 1 mol of the fluorine-containing diol represented by the formula [2], the conversion rate of the reaction and the yield of the target product are not sufficient, and 5 mol If it exceeds 1, α-substituted acrylic anhydride that does not participate in the reaction increases, which is economically undesirable from the time of disposal.

  Additives can be added to promote the reaction. As the additive used, at least one acid selected from the group of organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid and Lewis acids is preferably used. It is done. The amount of the additive used for this reaction is 0.01 to 2 mol, preferably 0.02 to 1.8, preferably 0.05 to 1.8 mol per mol of the fluorine-containing diol represented by the formula [2] of the substrate. 1.5 moles is more preferred. If the amount of the additive is less than 0.01 mol with respect to 1 mol of the fluorine-containing diol represented by the formula [2] of the substrate, both the conversion rate of the reaction and the yield of the target product are reduced. This is economically undesirable because the amount of additive not involved increases.

  When this reaction is carried out, the reaction temperature is usually from 80 to 200 ° C, preferably from 100 to 180 ° C, more preferably from 120 to 160 ° C when no additive is added. In this case, the reaction rate is very slow at less than 80 ° C., and if it exceeds 200 ° C., the raw α-substituted acrylic acid anhydride or the fluorine-containing ester represented by the formula [4] may be polymerized, which is not preferable. . When adding an additive, it is 0-80 degreeC, Preferably it is 10-70 degreeC, More preferably, it is 20-60 degreeC. In this case, if it is less than 0 ° C., the reaction rate is slow and it is not a practical production method. Moreover, when it exceeds 80 degreeC, a side reaction will advance easily and it is unpreferable since the selectivity of the target fluorine-containing ester compound may fall. In the present invention, it is preferable to add an additive because sufficient reactivity is obtained at a low temperature and the selectivity is improved. That is, it is possible to carry out the reaction in the temperature range of 20 to 60 ° C. by coexisting additives such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid in the system. This is one of the particularly preferred embodiments of this step.

  This reaction proceeds even without solvent, but it is desirable to use a solvent in consideration of the uniformity of the reaction and the operability after the reaction. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds such as benzene, toluene, xylene, and mesitylene, ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methylene chloride, and chloroform And halogen-based solvents such as carbon tetrachloride are preferable, and these may be used alone or in combination with a plurality of solvents.

  The amount of the solvent used in this reaction is usually 0.1 to 100 g, preferably 0.5 to 50 g, more preferably 1 to 20 g based on 1 g of the fluorinated diol represented by the formula [2]. If the amount of the solvent is less than 0.1 g with respect to 1 g of the fluorine-containing diol represented by the formula [2], the merit of using the solvent cannot be sufficiently extracted. If it exceeds 100 g, it is not economically preferable from the viewpoint of productivity.

  In order to prevent the polymerization of α-substituted acrylic anhydride or product (fluorinated ester compound) in this reaction, it may be carried out in the presence of a polymerization inhibitor, and usually a polymerization inhibitor is used. It is desirable to do. Polymerization inhibitors used are hydroquinone, methoquinone, 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, nonflex F, nonflex H , Non-flex DCD, non-flex MBP, ozonone 35, phenothiazine, 2-methoxyphenothiazine, tetraethylthiuram disulfide, 1,1-diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2-picrylhydrazine, Q- 1300 or at least one compound selected from Q-1301. The above polymerization inhibitors are commercially available products and can be easily obtained.

  The amount of the polymerization inhibitor used in the present invention is usually 0.00001 to 0.1 mol, and 0.0001 to 0.05 mol per mol of the fluorine-containing diol represented by the raw material formula [2]. Preferably, 0.001 to 0.01 mol is more preferable. Even if the amount of the polymerization inhibitor exceeds 0.1 mol with respect to 1 mol of the fluorine-containing diol represented by the formula [2] of the raw material, there is no significant difference in the ability to prevent the polymerization, and this is economically undesirable. .

  The reactor used in this reaction is made of tetrafluoroethylene resin, chloro-trifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, glass container, or stainless steel. preferable.

  Although the method of performing the second step is not limited, the details of an example of a desirable mode will be described.

(A) When the acrylic acid derivative represented by the formula [3] is an α-substituted acrylic halide, a fluorine-containing diol represented by the formula [2] of a base, a solvent and a raw material in a reactor that can withstand the reaction conditions An α-substituted acrylate halide and a polymerization inhibitor are added, and the reaction is allowed to proceed by heating from outside while stirring. It is preferable to monitor the consumption of the raw material by sampling or the like, confirm that the reaction is completed, and cool the reaction solution.

  The fluorine-containing ester represented by the formula [4] produced by the method of the present invention is purified by applying a known method. For example, after removing the base hydrochloride contained in the reaction solution by filtration, The filtrate is treated with an aqueous hydrochloric acid solution, an aqueous sodium carbonate solution and an aqueous sodium chloride solution in this order, and the solvent is distilled off to obtain a crude organic material. The obtained crude organic matter can be purified by column chromatography, distillation or the like to obtain a high purity fluorine-containing ester represented by the formula [4].

(A) When the acrylic acid derivative represented by the formula [3] is an α-substituted acrylic anhydride, a reactor that can withstand the reaction conditions, a solvent, a raw material fluorine-containing diol represented by the formula [2], α- A substituted acrylic anhydride, a polymerization inhibitor and an additive are added, and the reaction is allowed to proceed by heating from outside while stirring. It is preferable to monitor the consumption of the raw material by sampling or the like, confirm that the reaction is completed, and cool the reaction solution. The fluorine-containing ester represented by the formula [4] produced by the method of the present invention is purified by applying a known method. For example, the reaction solution is treated in the order of water, an aqueous sodium bicarbonate solution, and brine. Further, the organic solvent can be obtained by distilling off the solvent. The obtained crude organic matter can be purified by column chromatography, distillation or the like to obtain a high purity fluorine-containing ester represented by the formula [4].

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, it is not restricted to these embodiments. Here, “%” of the composition analysis value represents “area%” obtained by collecting a part of the reaction mixture and measuring it by gas chromatography.
[Example 1]
Production of 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3-diol (first step)
355 g of diisopropyl ether, 4,4,4-trifluoro-3-hydroxy-1-phenyl-3- (trifluoromethyl) butane in a 1 L stainless steel pressure-resistant reactor equipped with a pressure gauge, a thermometer and a stirrer 1-one 350 g (1.22 mol), 55.0 Ru / C (50% water-containing product, manufactured by N.I. Catcat) 35.0 g was added, the inside of the reactor was replaced with hydrogen, and then heated in an oil bath. The reaction was carried out at an internal temperature of 50 ° C. and a reaction pressure of 2.6 MPa (absolute pressure). After 16 hours, the reaction was terminated by cooling to room temperature. The reaction solution was sampled and the composition was measured by gas chromatography. The target 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) was obtained except for diisopropyl ether used as a solvent. Butane-1,3-diol was 96.0% and the others were 4.0%. 5% Ru / C of the catalyst was filtered off, the solvent was distilled off from the filtrate, and then recrystallized from hexane to obtain the desired 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane- 318.2 g of 1,3-diol was obtained with a purity of 97.5%. The yield was 91%.
¹ H NMR (solvent: CDCl ₃ , reference material: TMS); δ 4.01 (s, 1H), 6.31 (s, 1H), 2.2 (m, 2H), 2.06 (m, 3H) , 1.60 (m, 6H), 1.21 (m, 3H).
¹⁹ F NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-75.9 (d, J = 10.7 Hz, 3F), −72.9 (d, J = 9.16 Hz, 3F).
CI MS m / z (relative intensity): 277 (100.0), 211 (26.3), 83 (55.8).
[Example 2]
Production of 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3-diol (first step)
A stirrer coated with tetrafluoroethylene resin in a 10 MPa pressure resistant 100 mL stainless steel reactor equipped with a thermometer and a pressure gauge, 4,4,4-trifluoro-3-hydroxy-1-phenyl-3- (tri Fluoromethyl) butan-1-one (3.0 g, 0.010 mol), 5% Ru / C catalyst (0.3 g, 10 wt%), and diisopropyl ether (10 mL) were added, and the reactor was purged with hydrogen. Then, hydrogen was continuously introduced at 0.6 (absolute pressure) MPa while heating at 110 ° C. with an oil bath. After 4 hours, it was confirmed that the decrease in internal pressure had stopped, and the reaction solution was cooled to room temperature. The reaction solution was measured by gas chromatography, and the target 1-cyclohexyl-4,4 was obtained except for diisopropyl ether used as a solvent. , 4-trifluoro-3- (trifluoromethyl) butane-1,3-diol is 69.0%, 4-cyclohexyl-1,1,1-trifluoro-2- (trifluoromethyl) butane-2- All was 29.9% and others were 1.1%.
[Example 3]
Production of 1-cyclohexyl-4,4,4-trifluoro-3-hydroxy-3- (trifluoromethyl) butyl 2-methyl acrylate (second step)
296.5 g of 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3-diol was added to a glass 1 L three-necked flask equipped with a stirrer, a thermometer, and a reflux condenser ( 1 mol), 170.8 g (1.1 mol) of methacrylic anhydride, 1.0 g of trifluoromethanesulfonic acid, and 0.1 g of 2-methoxyphenothiazine as a polymerization inhibitor were added and stirred at 130 ° C. with heating. After 3 hours, the reaction was terminated when the conversion rate of the starting material 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3-diol reached 99% or more. After cooling to room temperature, the reaction mixture was distilled under reduced pressure to collect a fraction of 112-115 ° C./0.09 kPa, and the desired 1-cyclohexyl-4,4,4-trifluoro-3-hydroxy was collected. 312.8 g of -3- (trifluoromethyl) butyl 2-methyl acrylate was obtained with a purity of 96%. The yield was 90%. ¹ H NMR (solvent: CDCl ₃ , reference material: TMS); δ 6.19 (d, J = 1.2, 1H), 5.68 (d, J = 1.2, 1H), 4.89 (dt , J = 3.9, 4.1, 1H), 2.41 (dd, J = 3.4, 3.7, 1H), 2.11 (dd, 1.2, 2.2, 1H), 1.96 (s, 3H), 1.76 (m, 6H), 1.20 (m, 6H).
¹⁹ F NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-77.07 (q, J = 9.1 Hz, 3F), −79.39 (q, J = 9.1 Hz, 3F).
CI MS m / z (relative intensity): 69 (100), 276 (24), 362 (M ⁺ , 0.6).
[Comparative Example 1]
A glass 100 mL pressure-resistant reactor equipped with a pressure gauge, a thermometer and a stirrer was charged with 10.4 g of 4,4,4-trifluoro-3-hydroxy-1-phenyl-3- (trifluoromethyl) butan-1-one ( 0.04 mol) 10 g Pd / C (50% water-containing product, manufactured by N-Chemcat) 1.0 g and diisopropyl ether 20 mL were added, and the inside of the reactor was replaced with hydrogen, followed by heating at 40 ° C. Hydrogen was continuously introduced at 1.0 MPa (absolute pressure). After 12 hours, the mixture was cooled to room temperature to obtain 24.5 g of a reaction mixture. The reaction solution was sampled and the composition was measured by gas chromatography. As a result, 4,4,4-trifluoro-1-phenyl-3- (trifluoromethyl) butane-1,3 was obtained except for diisopropyl ether used as a solvent. -Diol was 97.1% and the others were 2.9%. The reaction mixture was filtered to remove 10% Pd / C of the catalyst, the solvent was distilled off from the filtrate, and then distilled under reduced pressure to collect a fraction of 140 ° C to 143 ° C / 2.0 kPa. , 4,4-trifluoro-1-phenyl-3- (trifluoromethyl) butane-1,3-diol was obtained with a purity of 98.6%, 7.97 g. The yield was 76.1%.
¹ H NMR (solvent: CDCl ₃ , reference material: TMS); δ 7.24-7.34 (m, 5H),
6.41 (s, 1H), 5.24 (d, J = 11.7 Hz, 1H), 2.91 (s, 1H), 2.18-2.40 (m, 2H).
¹⁹ F NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-75.8 (q, J = 9.92 Hz, 3F), −79.7 (q, J = 9.92 Hz, 3F).
EI-MS m / z (relative intensity): 288 (M ⁺ , 0.8), 201 (3.5), 109 (3.4), 107 (100), 79 (63), 77 (35), 69 (8.8), 51 (12).
Thus, in Comparative Example 1, 1-cyclohexyl-4,4,4-trifluoro-3- (trifluoromethyl) butane-1,3-diol, which is an object of the present invention, cannot be obtained. It was.

Claims (5)

Hydroxyketone represented by the formula [1]

Is reduced with hydrogen in the presence of a ruthenium catalyst, and the fluorine-containing diol represented by the formula [2]

Manufacturing method. The method according to claim 1, wherein the reaction temperature is 10 to 120 ° C. The method according to claim 1 or 2, wherein the reaction temperature is 30 to 70 ° C. 4. The method according to claim 1, wherein the ruthenium catalyst is a solid phase catalyst in which ruthenium is supported on activated carbon, alumina, or silica. An acrylic acid derivative represented by the formula [3] produced from the fluorine-containing diol represented by the formula [2] produced by the method according to claim 1.

(In the formula, R ¹ represents any ^one of H, C _m H _{2m + 1} , and C _n F _{2n + 1} (m and n each represents an integer of 1 to 4), X represents F, Cl, Or a group represented by the following formula [3a]

Represents one of the following. The meaning of R ¹ in formula [3a] is the same as in formula [3]. And a fluorine-containing ester represented by the formula [4]

(In the formula, the meaning of R ¹ is the same as in formula [3].)
Manufacturing method.