Method for producing 1,1,1-trifluoro-2,2-bisarylethane, and 1,1,1-trifluoro-2,2-bisarylethane

Abstract

According to the present invention, the following effects are achieved: by subjecting a mixture of 2,2,2-trifluoroacetaldehyde and hydrogen fluoride to a condensation reaction with an aryl compound under anhydrous conditions, 1,1,1-trifluoro-2,2-bisarylethane can be efficiently produced by a simple operation. The obtained 1,1,1-trifluoro-2,2-bisarylethane can be purified by a simple purification method such as crystallization operation and distillation to improve purity.

Description

Technical Field

[0001] The present invention relates to a method for producing 1,1,1-trifluoro-2,2-bisarylethane and 1,1,1-trifluoro-2,2-bisarylethane. Background Art

[0002] 2,2-bis(4-hydroxyphenyl)propane (common name: bisphenol A), which has a special skeleton, is a resin raw material monomer (polycarbonate, epoxy, and polyimide) mainly used in high-performance components in the field of electronic technology and mobile fields, just like 2,2-bis(4-hydroxyphenyl)propane (common name: bisphenol A), which is a general resin monomer. As disclosed in International Publication No. 2016 / 117237, it is known that the resin obtained from 2,2-bis(4-hydroxyphenyl)ethane (common name: bisphenol E), which is one of the representative compounds of 2,2-bis(4-hydroxyphenyl)ethane, generally has very unique physical properties that can take into account both flexibility and high heat resistance. On the other hand, the resin obtained from 1,1,1-trifluoro-2,2-bis(arylethane) having a trifluoromethyl group as the subject of the present invention and having a central skeleton is an excellent optical material having physical properties such as low dielectric constant, low refractive index, high transparency, and high solubility, and several manufacturing methods are known to date.

[0003] The prior art regarding the production method of 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane discloses the following methods: a method in which a hydrate, which is an equivalent of 2,2,2-trifluoroacetaldehyde (Fluoral), is treated with phenol in the presence of hydrogen fluoride to obtain 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane (Patent Document 1); a method in which a methyl hemiacetal of 2,2,2-trifluoroacetaldehyde is reacted with phenols in the presence of hydrogen chloride gas to obtain the corresponding 1,1,1 -trifluoro-2,2-bis(4-aminophenyl)ethane method (Patent Document 2); a method for synthesizing 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane by reacting the methyl hemiacetal of 2,2,2-trifluoroacetaldehyde with aromatic hydrocarbons in the presence of boron trifluoride (BF3) as a Lewis acid catalyst (Non-Patent Document 1); and a method for obtaining 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane from the ethyl hemiacetal of 2,2,2-trifluoroacetaldehyde and aniline (Non-Patent Document 2).

[0004] On the other hand, the method for producing 1,1,1-trifluoro-2,2-bisarylethane from stabilized anhydrous 2,2,2-trifluoroacetaldehyde in hydrogen fluoride as disclosed in the present invention has not been reported.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: U.S. Patent No. 3388097

[0008] Patent Document 2: Japanese Patent Publication No. 57-502055

[0009] Non-patent literature

[0010] Non-patent document 1: ORGANIC LETTERS, 2011, Vol. 13, No. 15, pp. 4128-4131

[0011] Non-patent document 2: HIGH PERFORMANCE POLYMERS, 2001, Vol. 13, No. 4, pp. 301-312 Summary of the invention

[0012] Problem that the invention aims to solve

[0013] In order to effectively obtain the target 1,1,1-trifluoro-2,2-diarylethane through the condensation reaction of an aromatic compound and 2,2,2-trifluoroacetaldehyde, it is usually preferred to add a Bronsted acid or a Lewis acid to promote the reaction. In form, the condensation reaction will produce a stoichiometric amount of water in order to obtain the target product, but considering the physical properties of the Bronsted acid and the Lewis acid added as catalysts, these additives are preferably in an anhydrous reaction state as much as possible. However, 2,2,2-trifluoroacetaldehyde usually uses relatively stable hydrates and hemiacetals as its equivalents, and these commercially available ones usually contain more than stoichiometric amounts of water and alcohol, and it is difficult to say that they are in an anhydrous reaction state. The raw material 2,2,2-trifluoroacetaldehyde is generally a highly polymerizable compound, so it is a difficult compound to handle itself, so it is extremely difficult to prepare and use anhydrous 2,2,2-trifluoroacetaldehyde for the aforementioned condensation reaction.

[0014] In the production examples of 1,1,1-trifluoro-2,2-bis(aryl)ethane (Patent Documents 1-2 and Non-Patent Documents 1-2), hydrates and hemiacetals of 2,2,2-trifluoroacetaldehyde as the raw material are used as the equivalents thereof. As the reaction proceeds, there is a concern that water and alcohol generated from the raw material 2,2,2-trifluoroacetaldehyde may hinder the reaction. Therefore, in order to smoothly proceed the reaction, it is necessary to add a large amount of Bronsted acid and Lewis acid as additives. In addition, the yield of 1,1,1-trifluoro-2,2-bis(aryl)ethane obtained in this reaction is generally moderate.

[0015] An object of the present invention is to provide a method for efficiently producing 1,1,1-trifluoro-2,2-bisarylethane from inexpensive and highly reactive anhydrous 2,2,2-trifluoroacetaldehyde by a simple operation.

[0016] Solutions for solving problems

[0017] The present inventors have conducted intensive research in view of the above-mentioned problems. As a result, they have obtained the following knowledge: by subjecting a mixture of 2,2,2-trifluoroacetaldehyde and hydrogen fluoride (in this specification, the mixture may be referred to as "a mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride") to a condensation reaction with an aryl compound represented by the general formula [1] under anhydrous conditions, 1,1,1-trifluoro-2,2-bisarylethane represented by the general formula [2] can be selectively obtained.

[0018]

[0019] [In the general formula [1], X1 each independently represents a hydroxyl group, an amino group, a carboxyl group, or a halogen group, and m represents an integer of 0 to 3. R1 each independently represents a monovalent organic group, and n represents an integer of 0 to (5-m).]

[0020]

[0021] [In the general formula [2], X1, R1, m and n are the same as X1, R1, m and n in the general formula [1]. ]

[0022] When focusing on 2,2,2-trifluoroacetaldehyde, a raw material used in the present invention, as disclosed in Japanese Patent Application Laid-Open No. 3-184933, its preparation method can be converted into 2,2,2-trifluoroacetaldehyde almost quantitatively by catalytic gas phase fluorination reaction of inexpensive chloral (2,2,2-trichloroacetaldehyde). However, due to the physical properties of this compound, it is very difficult to remove hydrogen fluoride and hydrogen chloride used in the reaction mixture obtained, and complicated purification operations are required.

[0023] However, when the reaction mixture of 2,2,2-trifluoroacetaldehyde, hydrogen fluoride and hydrogen chloride obtained by this method is treated under anhydrous conditions, it is unexpected that hydrogen chloride can be preferentially removed from the reaction mixture by refluxing hydrogen fluoride under normal pressure, and a new insight that it can be stably treated as a solution of a mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride is obtained. It should be noted that when an aryl compound is added to the mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride, the residual hydrogen fluoride has the function of an acidic substance itself, and therefore can be expected to be used as an acid catalyst and a dehydrating agent.

[0024] Furthermore, the following favorable insights were obtained: the reaction rate was significantly improved by the coexistence of Bronsted acid and Lewis acid as additives in the reaction system. It can be inferred that this is because the additive acts as a promoter of the dehydration reaction, making it easier for the condensation reaction to proceed. The obtained 1,1,1-trifluoro-2,2-bisarylethane can be purified by simple purification methods such as crystallization operation and distillation, and the usefulness and value of the present invention are extremely high. In addition, the following insights were obtained: using 1,1,1-trifluoro-2,2-bisarylethane and reacting aromatic diamines with tetracarboxylic dianhydride, it is possible to easily produce polyimides having physical properties such as high transparency and high solubility.

[0025] That is, the present invention provides: 1,1,1-trifluoro-2,2-bisarylethane described in the following [Invention 1] to [Invention 13] and a method for producing a polyimide using 1,1,1-trifluoro-2,2-bisarylethane, and 1,1,1-trifluoro-2,2-bisarylethane described in the following [Invention 14] to [Invention 37].

[0026] [Invention 1]

[0027] A production method, comprising subjecting a mixture of 2,2,2-trifluoroacetaldehyde and hydrogen fluoride to a condensation reaction with an aryl compound represented by the following general formula [1] under anhydrous conditions to obtain 1,1,1-trifluoro-2,2-bisarylethane represented by the following general formula [2],

[0028]

[0029] [In the general formula [1], X1 each independently represents a hydroxyl group, an amino group, a carboxyl group, or a halogen group, and m represents an integer of 0 to 3. R1 each independently represents a monovalent organic group, and n represents an integer of 0 to (5-m).]

[0030]

[0031] [In the general formula [2], X1, R1, m and n are the same as X1, R1, m and n in the general formula [1]. ]

[0032] [Invention 2]

[0033] The production method according to Invention 1, wherein a Lewis acid or a Bronsted acid is added as an additive in the above reaction.

[0034] [Invention 3]

[0035] The production method according to Invention 2, wherein the Lewis acid or the Bronsted acid is at least one selected from the group consisting of inorganic acids, organic acids and metal halides.

[0036] [Invention 4]

[0037] According to the production method described in Invention 3, the inorganic acid is at least one selected from the group consisting of phosphoric acid, hydrogen chloride, hydrogen bromide, concentrated nitric acid, concentrated sulfuric acid, fuming nitric acid and fuming sulfuric acid, and the organic acid is at least one selected from the group consisting of formic acid, acetic acid, oxalic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.

[0038] [Invention 5]

[0039] The production method according to Invention 2, wherein the metal halide is a metal halide comprising at least one metal selected from the group consisting of boron (III), tin (II), tin (IV), titanium (IV), zinc (II), aluminum (III), antimony (III) and antimony (V).

[0040] [Invention 6]

[0041] The production method according to Invention 2, wherein the metal halide is at least one selected from the group consisting of boron trifluoride (III), aluminum trichloride (III), zinc dichloride (II), titanium tetrachloride (IV), tin tetrachloride (IV), and antimony pentachloride (V).

[0042] [Invention 7]

[0043] The production method according to any one of Inventions 1 to 6, wherein the reaction is performed without using an organic solvent.

[0044] [Invention 8]

[0045] The production method according to any one of Inventions 1 to 7, wherein the reaction is carried out within a temperature range of -20°C to +200°C and a pressure range of 0.1 MPa to 4.0 MPa (absolute pressure).

[0046] [Invention 9]

[0047] A production method comprising the following steps: a step of obtaining an aromatic diamine represented by formula [2A]; and a step of polycondensing the aromatic diamine with a tetracarboxylic dianhydride represented by general formula

[17] to obtain a polyimide having a repeating unit represented by general formula

[18] .

[0048]

[0049] [In the general formula [2A], n is an integer of 0 to 4, and R1 each independently represents a monovalent organic group.]

[0050]

[0051] [In general formula

[17] , R2 It is a tetravalent organic group.]

[0052]

[0053] [In general formula

[18] , R 1 is a divalent organic group represented by the general formula [2B], R 2 is a tetravalent organic group,

[0054]

[0055] [In the general formula [2B], n is an integer of 0 to 4, and R3 has the same meaning as R1 in the general formula [2A].]].

[0056] [Invention 10]

[0057] The production method according to Invention 9, wherein R 1 It is at least one divalent organic group selected from the following.

[0058]

[0059] [Invention 11]

[0060] The production method according to Invention 9 or 10, wherein R 2 is at least one tetravalent organic group selected from the following.

[0061]

[0062] [Invention 12]

[0063] The production method according to any one of Inventions 9 to 11, wherein the weight average molecular weight of the polyimide is 1,000 to 1,000,000.

[0064] [Invention 13]

[0065] The production method according to any one of Inventions 9 to 12, wherein the step of polycondensing the aromatic diamine represented by the general formula [2A] and the tetracarboxylic dianhydride represented by the general formula

[17] to obtain the polyimide represented by the general formula

[18] comprises the following steps: reacting the aromatic diamine represented by the general formula [2A] with the tetracarboxylic dianhydride represented by the general formula

[17] to obtain a polyamic acid having a repeating unit represented by the general formula

[19] ; ​​and

[0066] A step of converting the polyamic acid represented by the general formula

[19] into a polyimide represented by the general formula

[18] by dehydration ring closure.

[0067]

[0068] [In general formula

[19] , R 1 With R in the general formula

[18] 1 Same meaning, R 2 With R in the general formula

[17] 2 The meaning is the same. ].

[0069] [Invention 14]

[0070] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula [3], wherein:

[0071]

[0072] [In formula [3], n represents an integer of 1 to 4. ]

[0073] [Invention 15]

[0074] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 14 is 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane represented by formula [3a],

[0075]

[0076] In the formula, Me represents a methyl group.

[0077] [Invention 16]

[0078] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 14 is 1,1,1-trifluoro-2,2-bis(2-methyl-4-aminophenyl)ethane represented by formula [3b],

[0079]

[0080] In the formula, Me represents a methyl group.

[0081] [Invention 17]

[0082] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 14 is 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane represented by formula [4a],

[0083]

[0084] In the formula, Me represents a methyl group.

[0085] [Invention 18]

[0086] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 14 is 1,1,1-trifluoro-2,2-bis(2,3-dimethyl-4-aminophenyl)ethane represented by formula [4b],

[0087]

[0088] In the formula, Me represents a methyl group.

[0089] [Invention 19]

[0090] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 14 is 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-aminophenyl)ethane represented by formula [4c],

[0091]

[0092] In the formula, Me represents a methyl group.

[0093] [Invention 20]

[0094] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula [5], wherein:

[0095]

[0096] [In formula [5], n represents an integer of 1 to 4.]

[0097] [Invention 21]

[0098] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 20 is 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane represented by formula [5a],

[0099]

[0100] [Invention 22]

[0101] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula [6], wherein:

[0102]

[0103] [In formula [6], n represents an integer of 1 to 5.]

[0104] The following compounds are not included:

[0105]

[0106] [Invention 23]

[0107] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 22 is 1,1,1-trifluoro-2,2-bis(3,4-dimethylphenyl)ethane represented by formula [6a],

[0108]

[0109] In the formula, Me represents a methyl group.

[0110] [Invention 24]

[0111] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula [7], wherein:

[0112]

[0113] [In formula [7], n represents an integer of 1 to 4.]

[0114] (However, the following compounds are not included).

[0115]

[0116] [Invention 25]

[0117] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 24 is 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-hydroxyphenyl)ethane represented by formula [7a],

[0118]

[0119] In the formula, Me represents a methyl group.

[0120] [Invention 26]

[0121] A 1,1,1-trifluoro-2,2-bis(3-methoxy-4-hydroxyphenyl)ethane represented by formula [8], wherein:

[0122]

[0123] In the formula, Me represents a methyl group.

[0124] [Invention 27]

[0125] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula

[11] , wherein:

[0126]

[0127] In formula

[11] , n represents an integer of 1 to 4.

[0128] [Invention 28]

[0129] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 27 is 1,1,1-trifluoro-2,2-bis(3-fluoro-4-aminophenyl)ethane represented by formula [11a],

[0130]

[0131] [Invention 29]

[0132] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 27 is 1,1,1-trifluoro-2,2-bis(2-fluoro-4-aminophenyl)ethane represented by formula [11b],

[0133]

[0134] [Invention 30]

[0135] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula

[12] , wherein:

[0136]

[0137] In formula

[12] , n represents an integer of 1 to 4.

[0138] [Invention 31]

[0139] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 30 is 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-aminophenyl)ethane represented by formula [12a],

[0140]

[0141] [Invention 32]

[0142] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula

[13] , wherein:

[0143]

[0144] In formula

[13] , n represents an integer of 1 to 4.

[0145] [Invention 33]

[0146] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 32 is 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)ethane represented by formula [13a],

[0147]

[0148] [Invention 34]

[0149] A 1,1,1-trifluoro-2,2-bis(aryl)ethane represented by formula

[14] , wherein:

[0150]

[0151] In formula

[14] , n represents an integer of 1 to 4.

[0152] [Invention 35]

[0153] The 1,1,1-trifluoro-2,2-bisarylethane according to Invention 34 is 1,1,1-trifluoro-2,2-bis(3-fluoro-4-hydroxyphenyl)ethane represented by formula [14a],

[0154]

[0155] [Invention 36]

[0156] A 1,1,1-trifluoro-2,2-bis(3-nitro-4-hydroxyphenyl)ethane represented by formula

[15] , wherein:

[0157]

[0158] [Invention 37]

[0159] A 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)ethane represented by formula

[16] , wherein:

[0160]

[0161] Effects of the Invention

[0162] According to the present invention, there is an effect that 1,1,1-trifluoro-2,2-bisarylethane can be efficiently produced by a simple operation from anhydrous 2,2,2-trifluoroacetaldehyde which is inexpensive and highly reactive. DETAILED DESCRIPTION

[0163] The present invention will be described in detail below. The present invention is not limited to the following embodiments, and can be appropriately implemented based on the general knowledge of those skilled in the art within the scope of the present invention.

[0164] As shown in the following reaction formula, the 1,1,1-trifluoro-2,2-bisarylethane of the present invention having one trifluoromethyl group can be obtained by reacting a mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride with an aryl compound represented by the general formula [1].

[0165] [Solution 1]

[0166]

[0167] The 2,2,2-trifluoroacetaldehyde used as the starting material in the present invention can be prepared by using a hydrate or hemiacetal of 2,2,2-trifluoroacetaldehyde, which is a commercially available product (product of Tokyo Chemical Industry Co., Ltd.) as its equivalent. On the other hand, the hydrate or hemiacetal of 2,2,2-trifluoroacetaldehyde can be prepared by the method described in Japanese Patent Application Laid-Open No. 5-97757.

[0168] Generally, 2,2,2-trifluoroacetaldehyde is used as a hydrate or hemiacetal in most cases. Therefore, when 2,2,2-trifluoroacetaldehyde is used under anhydrous conditions, anhydrous 2,2,2-trifluoroacetaldehyde can be prepared by dehydrating the hydrate or hemiacetal of 2,2,2-trifluoroacetaldehyde as described in the present invention. On the other hand, as described in the method described in Japanese Patent Application Laid-Open No. 3-184933, inexpensive chloral can be converted into 2,2,2-trifluoroacetaldehyde almost quantitatively by catalytic gas phase fluorination reaction, and anhydrous 2,2,2-trifluoroacetaldehyde can also be prepared by using it (Preparation Example 1).

[0169] 2,2,2-Trifluoroacetaldehyde, which is the starting material of the present invention, is a low-boiling compound and is generally a compound that is highly self-reactive and difficult to handle. However, in this process, a new finding is obtained that 2,2,2-trifluoroacetaldehyde can be handled very stably in a hydrogen fluoride solution. When 2,2,2-trifluoroacetaldehyde is treated in hydrogen fluoride, 1,2,2,2-tetrafluoroethanol, which is an adduct formed by 2,2,2-trifluoroacetaldehyde and hydrogen fluoride, is generated as shown in the following scheme (Preparation Example 1).

[0170] [Solution 2]

[0171]

[0172] Thus, it can be inferred that 1,2,2,2-tetrafluoroethanol forms an equilibrium state between the 2,2,2-trifluoroacetaldehyde and the adduct, and since there is an excess of hydrogen fluoride in the system, the equilibrium state is maintained, and as a result, the decomposition of 2,2,2-trifluoroacetaldehyde is suppressed. It was confirmed that the 2,2,2-trifluoroacetaldehyde in the aforementioned hydrogen fluoride not only improves the stability of the compound but also increases the boiling point, and 2,2,2-trifluoroacetaldehyde, which is a low-boiling compound, can be easily handled as an adduct of hydrogen fluoride even near room temperature.

[0173] When the prepared 2,2,2-trifluoroacetaldehyde is treated as a mixture with hydrogen fluoride, the amount of hydrogen fluoride used is usually 0.1 to 100 moles, preferably 1 to 75 moles, and more preferably 2 to 50 moles relative to 1 mole of the prepared 2,2,2-trifluoroacetaldehyde. When the amount of hydrogen fluoride added is less than 0.1 mole, a sufficient stabilization effect cannot be obtained, so it is not preferred. In addition, even if more than 100 moles of hydrogen fluoride are added, the same stabilization effect can be expected, but it is not preferred from the perspective of productivity and economy. In addition, the mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride used in this process sometimes contains excessive hydrogen fluoride, but because it has the function of an acidic substance possessed by hydrogen fluoride itself, it effectively acts as an acid catalyst and a dehydrating agent, and can also be used as an additive to promote the reaction, so it can be said that the mixture of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride as a raw material has advantages in handling.

[0174] X1 in the aryl compound represented by the general formula [1] is not limited as long as it is a substituent that can be induced to become a functional monomer, and each independently represents a hydroxyl group, an amino group, a carboxyl group, and a halogen atom. Among them, a hydroxyl group and an amino group are preferred. The number (m) of X1 bonded to the aryl compound is an integer of 0 to 3, preferably an integer of 1 to 2.

[0175] In the aryl compound represented by the general formula [1], R1 each independently represents a monovalent organic group. The monovalent organic group is not limited, and preferably includes alkyl, alkoxy, cycloalkyl, aryl, alkenyl, alkynyl, aryloxy, amino, alkylamino, arylamino, cyano, nitro, silyl, and halo (e.g., fluoro) groups, which may optionally have substituents such as fluorine atoms and carboxyl groups, and more preferably alkyl, alkoxy, fluorinated alkyl (e.g., trifluoromethyl), halo (e.g., fluoro), and nitro. The alkyl group as R1 is not limited, and preferably is a linear or branched alkyl group having 1 to 6 carbon atoms, and preferably n-butyl, sec-butyl, isobutyl, tert-butyl, n-propyl, isopropyl, ethyl, and methyl groups, and particularly preferably ethyl and methyl groups. On the other hand, the alkoxy group as R1 is not limited, and is preferably a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, among which n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-propoxy, isopropoxy, ethoxy and methoxy are preferred, and ethoxy and methoxy are particularly preferred. In addition, the alkyl group and alkoxy group may be substituted with, for example, a halogen atom, alkoxy group and halogenated alkoxy group in any number and in any combination on any carbon thereof. Furthermore, when the number of R1 in the aromatic compound is 2 or more, these two or more R1s may be connected to form a saturated or unsaturated, monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms. The number (n) of bonded R1 in the aromatic compound is an integer from 0 to (5-m), preferably an integer from 0 to 2.

[0176] The amount of the aryl compound used may be 1 mol or more per mol of 2,2,2-trifluoroacetaldehyde, and is preferably 2 to 10 mol because the reaction proceeds smoothly. Furthermore, in consideration of post-treatment operations, 2 to 5 mol is particularly preferred.

[0177] The present invention can be carried out in the presence of a reaction solvent. The reaction solvent can include aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers, esters, amides, nitrile, sulfoxides, etc. As specific examples, n-hexane, cyclohexane, n-heptane, benzene, toluene, ethylbenzene, xylene, mesitylene, dichloromethane, chloroform, 1,2-dichloroethane, diethyl ether, tetrahydrofuran, diisopropyl ether, tert-butyl methyl ether, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, propionitrile, dimethyl sulfoxide, etc. can be listed. These reaction solvents can be used alone or in combination.

[0178] It should be noted that the present invention can also be reacted without using a solvent. As disclosed in the examples described later, when reacting without a solvent, there is an advantage that the purification operation after the reaction is simple and convenient, and the target product of high purity is obtained only by a simple purification operation, and it is more preferred.

[0179] In this step, when a Lewis acid or a Bronsted acid is added to the reaction system together with the 2,2,2-trifluoroacetaldehyde / hydrogen fluoride mixture and the aryl compound, the conversion rate of the condensation reaction in the present invention can be improved, and thus it is listed as one of the preferred embodiments of the present invention.

[0180] The Lewis acid used in this step is a metal halide containing at least one metal selected from the group consisting of boron (III: referred to as oxidation number. The same applies to the following description), tin (II), tin (IV), titanium (IV), zinc (II), aluminum (III), antimony (III) and antimony (V). It should be noted that the metal halide used is generally preferably a halide of a metal that can obtain the maximum atomic valence.

[0181] Among the metal halides using these metals, boron trifluoride (III), aluminum trichloride (III), zinc dichloride (II), titanium tetrachloride (IV), tin tetrachloride (IV), and antimony pentachloride (V) are particularly preferred.

[0182] In order for the Lewis acid to function as an additive, the amount used is preferably 0.001 mol or more, usually 0.01 to 2.0 mol, per 1 mol of 2,2,2-trifluoroacetaldehyde. However, using the Lewis acid in an amount exceeding 2.0 equivalents is not economically preferable.

[0183] The Bronsted acid used in this process is an inorganic acid or an organic acid. Specific examples of the inorganic acid include phosphoric acid, hydrogen chloride, hydrogen bromide, concentrated nitric acid, concentrated sulfuric acid, fuming nitric acid and fuming sulfuric acid. Specific examples of the organic acid include formic acid, acetic acid, oxalic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and the like.

[0184] In order for the Bronsted acid to function as an additive, the amount used is 0.001 mol or more, and usually 0.01 to 2.0 mol is preferred relative to 1 mol of 2,2,2-trifluoroacetaldehyde. However, using Bronsted acid in an amount exceeding 2.0 equivalents is not economically preferred.

[0185] The temperature condition may be in the range of -20 to +200°C, preferably -10 to +180°C, and particularly preferably 0 to +160°C.

[0186] The pressure condition can be carried out in the range of atmospheric pressure to 4.0 MPa (absolute pressure, the same below), usually preferably from atmospheric pressure to 2.0 MPa, particularly preferably from atmospheric pressure to 1.5 MPa. As the reaction vessel used in the present invention, stainless steel, monel alloy, etc. can be used. TM , Hastelloy TM A reactor capable of carrying out sufficient reaction under normal pressure or under pressure, such as a metal container such as a nickel container, a container lined with tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, propylene resin, and polyethylene resin, etc.

[0187] The reaction time is usually within 24 hours, but varies according to the combination of the 2,2,2-trifluoroacetaldehyde / hydrogen fluoride mixture and the aromatic compound, and the reaction conditions caused by the amount of Lewis acid or Bronsted acid used as an additive. Preferably, the progress of the reaction is tracked by analytical means such as gas chromatography, thin layer chromatography, liquid chromatography, nuclear magnetic resonance, etc., and the time when the starting substrate almost disappears is taken as the end point of the reaction.

[0188] In the post-treatment after the reaction, the reaction termination liquid is subjected to a common purification operation, for example, the reaction termination liquid is injected into an aqueous solution of water or an alkali metal inorganic base (for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate or potassium carbonate, etc.), and extracted with an organic solvent (for example, ethyl acetate, toluene, mesitylene, dichloromethane, etc.), so that the target 1,1,1-trifluoro-2,2-bisarylethane monomer represented by the general formula [2] can be easily obtained. The target product can be purified to a higher chemical purity by activated carbon treatment, distillation, recrystallization, column chromatography, etc. as needed.

[0189] The production method of this embodiment can produce 1,1,1-trifluoro-2,2-bisarylethane represented by formula [1] with high isomer selectivity. Among the compounds represented by formula [1], for example, the compound represented by formula [3], the compound represented by formula [5], the compound represented by formula [6], the compound represented by formula [7], the compound represented by formula [8], the compound represented by formula

[11] , the compound represented by formula

[12] , the compound represented by formula

[13] , the compound represented by formula

[14] , the compound represented by formula

[15] and the compound represented by formula

[16] can be produced with particularly high isomer selectivity and high yield using the method of this embodiment. It should be noted that in the following formulas, "n" represents an integer of 1 to 5, and "Me" represents a methyl group.

[0190]

[0191] (However, the compounds of formula [6] do not include the following compounds:)

[0192]

[0193] (However, the compounds of formula [7] do not include the following compounds:)

[0194]

[0195] In the formula, Me represents a methyl group.

[0196]

[0197]

[0198] Among the compounds represented by formula [3], 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane represented by formula [3a], 1,1,1-trifluoro-2,2-bis(2-methyl-4-aminophenyl)ethane represented by formula [3b], 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane represented by formula [4a], 1,1,1-trifluoro-2,2-bis(2,3-dimethyl-4-aminophenyl)ethane represented by formula [4b], and 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-aminophenyl)ethane represented by formula [4c] can be produced in high yield by the method of this embodiment. In the following formulas, "Me" represents a methyl group.

[0199]

[0200] Among the compounds represented by formula [5], 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane represented by formula [5a] can be produced in high yield by the method of this embodiment.

[0201]

[0202] Among the compounds represented by formula [6], 1,1,1-trifluoro-2,2-bis(3,4-dimethylphenyl)ethane represented by formula [6a] can be produced at a high yield by the method of this embodiment. In the following formulae, "Me" represents a methyl group.

[0203]

[0204] Among the compounds represented by formula [7], 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-hydroxyphenyl)ethane represented by formula [7a] can be produced at a high yield by the method of this embodiment. In the following formulae, "Me" represents a methyl group.

[0205]

[0206] Among the compounds represented by formula

[11] , 1,1,1-trifluoro-2,2-bis(3-fluoro-4-aminophenyl)ethane represented by formula [11a] and 1,1,1-trifluoro-2,2-bis(2-fluoro-4-aminophenyl)ethane represented by formula [11b] can be produced in high yield by the method of this embodiment.

[0207]

[0208] Among the compounds represented by formula

[12] , 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-aminophenyl)ethane represented by formula [12a] can be produced in high yield by the method of this embodiment.

[0209]

[0210] Among the compounds represented by formula

[13] , 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)ethane represented by formula [13a] can be produced in high yield by the method of this embodiment.

[0211]

[0212] Among the compounds represented by formula

[14] , 1,1,1-trifluoro-2,2-bis(3-fluoro-4-hydroxyphenyl)ethane represented by formula [14a] can be produced in high yield by the method of this embodiment.

[0213] [Polyimide and Polyamic Acid Production Method]

[0214] In the 1,1,1-trifluoro-2,2-bisarylethane represented by the general formula [2] obtained by the method of this embodiment, an aromatic diamine represented by the following general formula [2A] is reacted with a tetracarboxylic dianhydride represented by the following general formula

[17] , thereby obtaining a polyimide having a repeating unit represented by the general formula

[18] having excellent transparency and heat resistance and excellent film-forming processability.

[0215]

[0216] [In the general formula [2A], n is an integer of 0 to 4, and R1 each independently represents a monovalent organic group.]

[0217]

[0218] [In general formula

[17] , R 2 It is a tetravalent organic group.]

[0219]

[0220] [In general formula

[18] , R 1 is a divalent organic group represented by the general formula [2B], R 2 is a tetravalent organic group,

[0221]

[0222] [In the general formula [2B], n is an integer of 0 to 4, and R3 has the same meaning as R1 in the general formula [2A]. ]

[0223] As an example of the method for producing the polyimide, there is a method of melting the above-mentioned aromatic diamine and tetracarboxylic dianhydride at 150° C. or higher.

[0224] Furthermore, as another production example, there can be cited a method of preparing the polyimide of the present embodiment by polycondensing the above aromatic diamine and tetracarboxylic dianhydride in an organic solvent and dehydrating and ring-closing the obtained polyamic acid represented by the following general formula

[19] ,

[0225]

[0226] [In general formula

[19] , R 1 With R in the general formula

[18] 1 Same meaning, R 2 With R in the general formula

[17] 2 Same meaning.]

[0227] The polycondensation reaction is preferably carried out at -20 to 80°C, and the diamine and the tetracarboxylic dianhydride are reacted at a molar ratio of 1:1.

[0228] In the diamine represented by the general formula [2A], R1 is the same as R1 in the aryl compound represented by the general formula [1]. The type of R1 is not limited. For example, when R1 is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, among which n-butyl, sec-butyl, isobutyl, tert-butyl, n-propyl, isopropyl, ethyl and methyl are preferred, and ethyl and methyl are particularly preferred.

[0229] Here, as examples when R1 is a methyl group, aromatic diamines having the following structures can be cited.

[0230]

[0231] R of the tetracarboxylic dianhydride represented by the general formula

[17] 2 The tetravalent organic group includes the following organic groups.

[0232]

[0233] Moreover, as a specific compound of tetracarboxylic dianhydride, the compound of the following structure can be illustrated.

[0234]

[0235] Examples of the polyimide of the present embodiment having a repeating unit represented by the general formula

[18] include polyimides having a structural unit represented by any of the following formulae.

[0236]

[0237]

[0238]

[0239] In the polyimide of the present embodiment, the weight average molecular weight is not particularly limited, and the weight average molecular weight of the polyimide is usually 1000 or more and 1000000 or less, preferably 30000 or more and 200000 or less. When it is less than 1000 or greater than 1000000, the performance of the polyimide as a substrate and the film-forming condition on the substrate may be affected. It should be noted that in this specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter sometimes referred to as "GPC") and converted to polystyrene using a standard polystyrene standard curve.

[0240] When other diamine compounds that can be used in combination are exemplified, from the viewpoint of easy availability, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 4-diamino-m-xylene, 2,4-diaminoxylene, 2,2-bis(4-(4-aminophenyl)hexafluoropropane, or 2,2'-bis(trifluoromethyl)benzidine can be mentioned. 2,2-bis(4-(4-aminophenyl)hexafluoropropane, which has less reduction in transparency, is particularly preferred. These can be used alone or in combination of two or more.

[0241] The organic solvent that can be used for the polycondensation reaction is not particularly limited as long as it dissolves the raw material compound, and examples thereof include amide solvents, ether solvents, aromatic hydrocarbon solvents, halogen solvents, lactone solvents, etc. Specifically, examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide (DMAc), N-methylformamide, hexamethylphosphoric acid triamide, N-methyl-2-pyrrolidone, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, diphenyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, dioxane, trioxane, benzene, anisole, nitrobenzene, benzonitrile, chloroform, dichloromethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, γ-butyrolactone, γ-valerolactone, ε-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, etc. These organic solvents may be used alone or in combination of two or more.

[0242] The polyimide (general formula

[18] ) of the present embodiment can be obtained by further dehydrating and ring-closing the polyamic acid (general formula

[19] ) obtained in the polycondensation reaction and imidizing it. The dehydrating and ring-closing reaction is carried out under conditions that promote cyclization, heating method, chemical method, etc. In the heating method, the polyamic acid just after polymerization is imidized by high temperature heating at 150 to 350° C. In the chemical method, a base such as pyridine or triethylamine and acetic anhydride are added at room temperature (0 to 50° C.) with respect to the diamine of the raw material in an amount of 0.1 molar equivalent or more and less than 10 equivalents to carry out imidization, and a solution of the polyimide of the present embodiment can be obtained. The concentration of the polyimide in the solution is preferably 5% by mass or more and 50% by mass or less. When it is less than 5% by mass, it sometimes affects practicality and efficiency. In addition, when it exceeds 50% by mass, it sometimes affects solubility. Furthermore, it is preferably 10% by mass or more and 40% by mass or less.

[0243] In addition, the polyamic acid of this embodiment which has a repeating unit represented by general formula

[19] can be exemplified by polyamic acids having a structural unit represented by any of the following formulae.

[0244]

[0245]

[0246]

[0247] The weight average molecular weight of the polyamic acid of the present embodiment is the same as that of the polyimide described above, so repeated description is omitted here. In addition, the polyimide and polyamic acid of the present embodiment may be used alone, or the polyimide and the polyamic acid may be mixed.

[0248] The polyimide of embodiment and the solution of polyamic acid can be used as raw material when manufacturing film, film.For example, in order to remove the residual monomers, low molecular weight bodies contained in the solution of the polyimide of present embodiment and polyamic acid, the solution of polyimide of present embodiment and polyamic acid is added in poor solvents such as water or alcohol, so that the polyimide and polyamic acid are precipitated, separated and purified.Then, once again, in the mode of becoming aforementioned concentration (more than 5 mass % and less than 50 mass %), it is dissolved in an organic solvent and adjusted, the solution adjusted to the concentration is coated on the parts requiring high refractive and high transparency of electronic components and optical components, thus, it is possible to form a film with excellent smoothness.

[0249] The organic solvent used here is not particularly limited as long as the polyimide and polyamic acid of the present embodiment are dissolved. For example, the same type of organic solvent as that listed in the organic solvent that can be used for the above-mentioned polycondensation reaction can be listed. It can be used alone or in a mixed solvent of two or more.

[0250] Example

[0251] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these embodiments. Here, the "%" of the composition analysis value represents the "area %" of the composition obtained by measuring the raw material or product by gas chromatography (hereinafter referred to as GC. When not specifically stated, the detector is FID).

[0252] [Catalyst Preparation Example]

[0253] 896g of special reagent CrCl3·6H2O was dissolved in pure water to make 3.0L. 400g of granular alumina was immersed in the solution and left for a day and night. Then the alumina was filtered and taken out, kept at 100°C in a hot air circulation dryer, and dried for a day and night. The obtained chromium-loaded alumina was filled in a cylindrical SUS316L reaction tube with a diameter of 4.2cm and a length of 60cm equipped with an electric furnace, and the temperature was raised to 300°C while nitrogen was passed at a flow rate of about 20mL / min. At the moment when water outflow was no longer observed, hydrogen fluoride was accompanied by nitrogen, and its concentration gradually increased. When the hot spot generated by the fluorination of the filled chromium-loaded alumina reached the outlet of the reaction tube, the reactor temperature was raised to 350°C, and this state was maintained for 5 hours to prepare the catalyst.

[0254] [Preparation Example 1]

[0255] [Solution 3]

[0256]

[0257] A gas phase reaction device (SUS316L, diameter 2.5 cm, length 40 cm) consisting of a cylindrical reaction tube equipped with an electric furnace was filled with 125 mL of the catalyst prepared in the above-mentioned catalyst preparation example as a catalyst. Air was introduced at a flow rate of about 100 mL / min, while the temperature of the reaction tube was raised to 280°C, and hydrogen fluoride was introduced at a rate of about 0.32 g / min for 1 hour. Then, chloral of formula [1] as a raw material was supplied to the reaction tube at a rate of about 0.38 g / min (contact time 15 seconds). The reaction reached stability 1 hour after the reaction started, so the gas flowing out of the reactor was captured in a SUS304 barrel with a blowing tube cooled by a refrigerant at -15°C for 18 hours.

[0258] When the hydrogen fluoride content, hydrogen chloride content, and organic matter content of 484.8 g of the collected liquid containing 2,2,2-trifluoroacetaldehyde were calculated by titration, the hydrogen fluoride content was 40% by weight, the hydrogen chloride content was 11% by weight, and the organic matter content was 49% by weight, and the recovery rate of the organic matter was 88% (based on the molar number of the raw material chloral). In addition, a portion of the recovered organic matter was collected in a resin NMR tube and 19 The degree of fluorination was confirmed by F-NMR. As a result, almost no low-valent fluoride was detected, confirming that fluorination had occurred quantitatively.

[0259] Next, a portion of the captured mixture containing 2,2,2-trifluoroacetaldehyde, 150 g (hydrogen fluoride: 40 wt%, hydrogen chloride: 11 wt%, organic matter: 49 wt%), was placed in a 500 ml SUS reactor equipped with a cooling tube through which a -15°C refrigerant was passed, a thermometer, and a stirrer, and the reactor was heated to 25°C. Under normal pressure, hydrogen fluoride was refluxed through the cooling tube while hydrogen chloride leaking from the top tower of the cooling tube was absorbed by water and removed. After 5 hours of reflux, a sample was taken from the reactor, and the hydrogen fluoride content, hydrogen chloride content, and organic matter content of the mixture were calculated by titration. The results were: hydrogen fluoride: 44 wt%, hydrogen chloride: 1 wt%, and organic matter: 55 wt%. In addition, a portion of the mixture was collected in a resin NMR tube and filtered. 19 The integral ratio of F-NMR confirmed that 2,2,2-trifluoroacetaldehyde in anhydrous hydrogen fluoride was converted into 1,2,2,2-tetrafluoroethanol, which is a composition of 2,2,2-trifluoroacetaldehyde / hydrogen fluoride. On the other hand, when water used to absorb hydrogen chloride was titrated, although some hydrogen fluoride was observed to be contained due to accompanying droplets, almost no organic matter was contained.

[0260] [Physical properties]

[0261] 1,2,2,2-Tetrafluoroethanol:

[0262] 19 F-NMR (400MHz, CFCl3) δ (ppm): -85.82 (3F, s), -137.95 (1F, d, J=54.9Hz)

[0263] Hydrogen fluoride:

[0264] 19 F-NMR (400MHz, CFCl3) δ (ppm): -193.37 (1F, s)

[0265] (Example 1)

[0266] [Solution 4]

[0267]

[0268] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44% by weight, hydrogen chloride: 1% by weight, organic matter: 55% by weight) and hydrogen fluoride 9.6g (0.48mol), benzene 4.7g (60mmol) were measured and reacted at 25°C and an absolute pressure of 0.2MPa for 24 hours. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of benzene was 98%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-diphenylethane at a yield of 97%.

[0269] [Physical properties]

[0270] 1,1,1-Trifluoro-2,2-diphenylethane,

[0271] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.68 (1H, q, J = 10.0Hz), 7.30-7.40 (10H, m)

[0272] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -65.7 (3F, d, J=8.7Hz)

[0273] (Example 2)

[0274] [Solution 5]

[0275]

[0276] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 5.7g (60mmol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and the mixture was reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice, and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of toluene was 97%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(4-methylphenyl)ethane with a yield of 97% and an isomer ratio of 56 / 32 / 3 / 3 / 2 (2,2-bis(4-methylphenyl) / 2-(4-methylphenyl)-2-(2-methylphenyl) / unidentified / unidentified / unidentified).

[0277] [Physical properties]

[0278] 1,1,1-Trifluoro-2,2-bis(4-methylphenyl)ethane,

[0279] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.31 (6H, s), 4.60 (1H, q, J = 10.0Hz), 7.14 (4H, q, J = 8.4Hz), 7.25 (4H, q, J = 7.9Hz)

[0280] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.5 (3F, d, J=8.7Hz)

[0281] (Example 3)

[0282] [Solution 6]

[0283]

[0284] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 6.4g (60mmol) of 2-xylene containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and the mixture was reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice, and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-xylene was 97%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3,4-dimethylphenyl)ethane of formula [6a], with a yield of 98% and an isomer ratio of 76 / 24 (2,2-bis(3,4-dimethylphenyl) isomer / 2-(3,4-dimethylphenyl)-2-(2,3-dimethylphenyl) isomer).

[0285] [Physical properties]

[0286] 1,1,1-Trifluoro-2,2-bis(3,4-dimethylphenyl)ethane,

[0287] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.31 (12H, s), 4.53 (1H, q, J=10.2Hz), 7.03-7.15 (6H, m)

[0288] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.4 (3F, d, J=11.5Hz)

[0289] (Example 4)

[0290] [Solution 7]

[0291]

[0292] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44% by weight, hydrogen chloride: 1% by weight, organic matter: 55% by weight) and 9.6g (0.48mol) of hydrogen fluoride and 7.7g (60mmol) of naphthalene were measured and reacted at 25°C and an absolute pressure of 0.2MPa for 24 hours. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of naphthalene was 53%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator and the recovered material was analyzed by gas chromatography. The results showed that naphthalene was 47%, 1,1,1-trifluoro-2,2-bis(naphthalene-1-yl)ethane was 53%, and the isomer ratio was 57 / 37 / 6 (2,2-bis(naphthalene-1-yl) / 2-(naphthalene-1-yl)-2-(naphthalene-2-yl) / unidentified).

[0293] [Physical properties]

[0294] 1,1,1-Trifluoro-2,2-bis(naphthalen-1-yl)ethane,

[0295] 1 H-NMR (400MHz, DMSO-d6) δ (ppm): 6.29 (1H, q, J = 10.1Hz), 7.40-8.00 (14H, m)

[0296] 19 F-NMR (400MHz, DMSO-d6, CFCl3) δ (ppm): -63.0 (3F, d, J=8.6Hz)

[0297] (Example 5)

[0298] [Scheme 8]

[0299]

[0300] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 5.7g (60mmol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and the mixture was reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice, and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of phenol was 96%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane with a yield of 94% and an isomer ratio of 78 / 22 (2,2-bis(4-hydroxyphenyl) isomer / 2-(4-hydroxyphenyl)-2-(2-hydroxyphenyl) isomer).

[0301] [Physical properties]

[0302] 1,1,1-Trifluoro-2,2-bis(4-hydroxyphenyl)ethane,

[0303] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.55 (1H, q, J = 9.9Hz), 5.10 (2H, s), 6.80 (4H, d, J = 8.6Hz), 7.22 (4H, d, J = 8.83Hz)

[0304] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.9 (3F, d, J=8.6Hz)

[0305] (Example 6)

[0306] [Solution 9]

[0307]

[0308] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 6.5g (60mmol) of 2-cresol containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured and reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-cresol was 93%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by the extraction operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(3-methyl-4-hydroxyphenyl)ethane with a yield of 93% and an isomer ratio of 96 / 4 (2,2-bis(3-methyl-4-hydroxyphenyl) isomer / unidentified).

[0309] [Physical properties]

[0310] 1,1,1-Trifluoro-2,2-bis(3-methyl-4-hydroxyphenyl)ethane,

[0311] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.21 (6H, s), 4.47 (1H, q, J = 10.1Hz), 6.76 (2H, d, J = 8.3Hz), 7.05 (2H, d, J = 8.3Hz), 7.08 (2H, s)

[0312] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.7 (3F, d, J=11.5Hz)

[0313] (Example 7)

[0314] [Scheme 10]

[0315]

[0316] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 and 9.6g (0.48mol) of hydrogen fluoride and 7.4g (60mmol) of 2,6-xylenol were weighed and reacted at 25°C and an absolute pressure of 0.2MPa for 24 hours. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2,6-xylenol was 99%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-hydroxyphenyl)ethane with a yield of 96% and an isomer ratio of 96 / 4 (2,2-bis(3,5-dimethyl-4-hydroxyphenyl) isomer / unidentified).

[0317] [Physical properties]

[0318] 1,1,1-Trifluoro-2,2-bis(3,5-dimethyl-4-hydroxyphenyl)ethane,

[0319] 1 H-NMR (400MHz, CD 3CN) δ (ppm): 2.18 (12H, s), 4.53 (1H, q, J = 10.6Hz), 6.13 (2H, s), 7.00 (4H, s)

[0320] 19 F-NMR (400MHz, CD 3CN, CFCl3) δ (ppm): -66.5 (3F, d, J=11.5Hz)

[0321] (Example 8)

[0322] [Scheme 11]

[0323]

[0324] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 and 9.6g (0.48mol) of hydrogen fluoride and 7.4g (60mmol) of 2,5-xylenol were weighed and reacted at 25°C and an absolute pressure of 0.2MPa for 24 hours. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2,5-xylenol was 93%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-hydroxyphenyl)ethane of formula [7a], with a yield of 92% and an isomer ratio of 98 / 2 (2,2-bis(2,5-dimethyl-4-hydroxyphenyl) isomer / unidentified).

[0325] [Physical properties]

[0326] 1,1,1-Trifluoro-2,2-bis(2,5-dimethyl-4-hydroxyphenyl)ethane:

[0327] 1 H-NMR (400MHz, CD 3CN) δ (ppm): 2.08 (6H, s), 2.16 (6H, s), 4.93 (1H, q, J = 10.0Hz), 6.58 (2H, s), 6.71 (2H, s), 7.05 (2H, s)

[0328] 19 F-NMR (400MHz, CD 3CN, CFCl3) δ (ppm): -65.5 (3F, d, J=8.7Hz)

[0329] (Example 9)

[0330] [Scheme 12]

[0331]

[0332] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3 g (2,2,2-trifluoroacetaldehyde: 30 mmol, hydrogen fluoride: 0.12 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1, 9.6 g (0.48 mol) of hydrogen fluoride, 5.6 g (60 mmol) of aniline, and 2.3 g (15 mmol) of trifluoromethanesulfonic acid were weighed, heated in an oil bath at 150° C., and reacted at an absolute pressure of 1.3 MPa for 5 hours. The reaction solution was poured into 100 g of ice, 70 g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted with 100 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of aniline was 96%. The organic layer recovered by the extraction operation was washed with 50 g of water, and then washed with 50 g of saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(4-aminophenyl)ethane with a yield of 93% and an isomer ratio of 92 / 8 (2,2-bis(4-aminophenyl) isomer / unidentified).

[0333] [Physical properties]

[0334] 1,1,1-Trifluoro-2,2-bis(4-aminophenyl)ethane,

[0335] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.42 (4H, s), 4.45 (1H, q, J = 10.1Hz), 6.62 (4H, d, J = 8.3Hz), 7.12 (4H, d, J = 8.3Hz)

[0336] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.9 (3F, d, J=11.5Hz)

[0337] (Example 10)

[0338] [Scheme 13]

[0339]

[0340] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 15.9 g (2,2,2-trifluoroacetaldehyde: 90 mmol, hydrogen fluoride: 0.36 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1, 28.8 g (1.44 mol) of hydrogen fluoride, 19.5 g (0.18 mol) of 2-toluidine, and 3.0 g (45 mmol) of boron trifluoride were weighed, heated in an oil bath at 150° C., and reacted at an absolute pressure of 1.3 MPa for 5 hours. The reaction solution was poured into 300 g of ice, 210 g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted with 300 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-toluidine was 98%. The organic layer recovered by the extraction operation was washed with 150 g of water, and then washed with 150 g of saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane of formula [3] as the target product with a yield of 96% and an isomer ratio of 96 / 4. In a 200 mL glass reactor equipped with a thermometer protection tube and a stirrer, 25 g of the obtained crude crystals and 75 g of toluene were added and heated to 90°C to completely dissolve them, and 50 g of heptane was added dropwise over 1 hour to precipitate crystals. After cooling to 30°C, the crystals recovered by filtration were dried using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane of formula [3a], with a yield of 87%, a purity of 99.8%, and an isomer ratio of 99% or more (2,2-bis(3-methyl-4-aminophenyl) isoform).

[0341] [Physical properties]

[0342] 1,1,1-Trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane, 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.13 (6H, s), 3.14 (4H, s), 4.41 (1H, q, J = 10.4Hz), 6.62 (2H, d, J = 10.4Hz), 7.01 (2H, s), 7.02 (2H, d, J = 8.3Hz)

[0343] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.7 (3F, d, J=11.5Hz)

[0344] (Example 11)

[0345] [Scheme 14]

[0346]

[0347] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3 g (2,2,2-trifluoroacetaldehyde: 30 mmol, hydrogen fluoride: 0.12 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44 wt%, hydrogen chloride: 1 wt%, organic matter: 55 wt%) and 9.6 g (0.48 mol) of hydrogen fluoride and 7.3 g (60 mmol) of 2,6-dimethylaniline were weighed, heated in an oil bath at 150°C, and reacted at an absolute pressure of 1.3 MPa for 5 hours. The reaction solution was poured into 100 g of ice, 70 g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted with 100 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2,6-dimethylaniline was 99%. The organic layer recovered by the extraction operation was washed with 50 g of water, and then washed with 50 g of a saturated sodium bicarbonate aqueous solution, and then recovered by a liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane of formula [4a], with a yield of 95% and an isomer ratio of 97 / 3 (2,2-bis(3,5-dimethyl-4-aminophenyl) isomer / unidentified).

[0348] [Physical properties]

[0349] 1,1,1-Trifluoro-2,2-bis(3,5-dimethyl-4-aminophenyl)ethane,

[0350] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.15 (12H, s), 3.55 (4H, s), 4.36 (1H, q, J = 10.4Hz), 6.62 (2H, d, J = 10.4Hz), 6.93 (4H, s)

[0351] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.6 (3F, d, J=8.6Hz)

[0352] (Example 12)

[0353] [Scheme 15]

[0354]

[0355] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44% by weight, hydrogen chloride: 1% by weight, organic matter: 55% by weight) and 9.6g (0.48mol) of hydrogen fluoride and 6.5g (60mmol) of 3-toluidine were weighed, heated in an oil bath at 150°C, and reacted at an absolute pressure of 1.3MPa for 5 hours. The reaction solution was poured into 100g of ice, 70g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted by 100g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 3-toluidine was 83%. The organic layer recovered by the extraction operation was washed with 50 g of water, and then washed with 50 g of a saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by a liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain the target product 1,1,1-trifluoro-2,2-bis(2-methyl-4-aminophenyl)ethane of formula [3b] with a yield of 71% and an isomer ratio of 97 / 2 / 1 (2,2-bis(2-methyl-4-aminophenyl) isomer / unidentified / unidentified).

[0356] [Physical properties]

[0357] 1,1,1-Trifluoro-2,2-bis(2-methyl-4-aminophenyl)ethane, 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.21 (6H, s), 3.58 (4H, bs), 4.83 (1H, q, J = 9.6Hz), 6.48 (2H, s), 6.50 (2H, d, J = 9.4Hz), 7.17 (2H, d, J = 8.7Hz)

[0358] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -65.6 (3F, d, J=11.6Hz)

[0359] (Example 13)

[0360] [Scheme 16]

[0361]

[0362] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3 g (2,2,2-trifluoroacetaldehyde: 30 mmol, hydrogen fluoride: 0.12 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44 wt%, hydrogen chloride: 1 wt%, organic matter: 55 wt%) and 9.6 g (0.48 mol) of hydrogen fluoride and 7.3 g (60 mmol) of 2,5-dimethylaniline were weighed, heated in an oil bath at 150°C, and reacted at an absolute pressure of 1.3 MPa for 5 hours. The reaction solution was poured into 100 g of ice, 70 g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted with 100 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2,5-dimethylaniline was 98%. The organic layer recovered by the extraction operation was washed with 50 g of water, and then washed with 50 g of a saturated sodium bicarbonate aqueous solution, and then recovered by a liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(2,5-dimethyl-4-aminophenyl)ethane of formula [4c], with a yield of 94% and an isomer ratio of 99 / 1 (2,2-bis(2,5-dimethyl-4-aminophenyl) isomer / unidentified).

[0363] [Physical properties]

[0364] 1,1,1-Trifluoro-2,2-bis(2,5-dimethyl-4-aminophenyl)ethane,

[0365] 1 H-NMR (400MHz, CDCl3) δ (ppm): 2.12 (6H, s), 2.19 (6H, s), 3.53 (4H, bs), 4.80 (1H, q, J = 9.6Hz), 6.45 (2H, s), 7.04 (2H, s)

[0366] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -65.5 (3F, d, J=8.7Hz)

[0367] (Example 14)

[0368] [Scheme 17]

[0369]

[0370] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3 g (2,2,2-trifluoroacetaldehyde: 30 mmol, hydrogen fluoride: 0.12 mol) of the mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44 wt%, hydrogen chloride: 1 wt%, organic matter: 55 wt%), 9.6 g (0.48 mol) of hydrogen fluoride, and 6.6 g (60 mmol) of 2-aminophenol were weighed and heated in an oil bath at 150° C. and reacted at an absolute pressure of 1.3 MPa for 5 hours. The reaction was continued for 1 h. The solution was poured into 100 g of ice, and 70 g of 48% potassium hydroxide aqueous solution was added for neutralization. The precipitated solid was recovered by suction filtration and analyzed by liquid chromatography. As a result, the conversion rate of 2-aminophenol was 97%. The obtained solid was dried by a rotary evaporator to obtain 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane of formula [5a] as the target product with a yield of 95% and an isomer ratio of 88 / 12 (2,2-bis(3-amino-4-hydroxyphenyl) / 2-(3-amino-4-hydroxyphenyl)-2-(3-hydroxy-4-aminophenyl)).

[0371] [Physical properties]

[0372] 1,1,1-Trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane,

[0373] 1 H-NMR (400MHz, CD 3OD) δ (ppm): 4.41 (1H, q, J = 10.42Hz), 4.88 (6H, s), 6.60-6.80 (6H, m)

[0374] 19 F-NMR (400MHz, CD 3OD, CFCl3) δ (ppm): -66.8 (3F, d, J=11.6Hz)

[0375] (Example 15)

[0376] [Scheme 18]

[0377]

[0378] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 5.8g (60mmol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and the mixture was reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of fluorobenzene was 99%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target 1,1,1-trifluoro-2,2-bis(4-fluorophenyl)ethane with a yield of 93% and an isomer ratio of 84 / 16 (2,2-bis(4-fluorophenyl) isomer / 2-(4-fluorophenyl)-2-(2-fluorophenyl) isomer).

[0379] [Physical properties]

[0380] 1,1,1-Trifluoro-2,2-bis(4-fluorophenyl)ethane,

[0381] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.66 (1H, q, J = 9.7Hz), 7.02-7.06 (4H, m), 7.30 (2H, d, J = 8.8Hz), 7.32 (2H, d, J = 8.8Hz)

[0382] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.3 (3F, d, J=8.7Hz), -113.8 (2F, s)

[0383] (Example 16)

[0384] [Scheme 19]

[0385]

[0386] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) of a mixture containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 (hydrogen fluoride: 44% by weight, hydrogen chloride: 1% by weight, organic matter: 55% by weight) and 9.6g (0.48mol) of hydrogen fluoride and 9.8g (60mmol) of trifluoromethoxybenzene were measured and reacted at 25°C and an absolute pressure of 0.2MPa for 24 hours. The reaction solution was injected into 50g of ice and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of trifluoromethoxybenzene was 96%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and then the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target product 1,1,1-trifluoro-2,2-bis(4-trifluoromethoxyphenyl)ethane at a yield of 94% and an isomer ratio of 91 / 9 (2,2-bis(4-trifluoromethoxyphenyl) isomer / unidentified).

[0387] [Physical properties]

[0388] 1,1,1-Trifluoro-2,2-bis(4-trifluoromethoxyphenyl)ethane,

[0389] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.72 (1H, q, J = 9.7Hz), 7.21 (4H, d, J = 8.6Hz), 7.38 (4H, d, J = 8.6Hz)

[0390] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -57.3 (6F, s), -66.1 (3F, d, J=8.7Hz)

[0391] (Example 17)

[0392] [Scheme 20]

[0393]

[0394] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.3g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 0.12mol) and 9.6g (0.48mol) of hydrogen fluoride and 7.5g (60mmol) of guaiacol containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and the mixture was reacted for 24 hours at 25°C and an absolute pressure of 0.2MPa. The reaction solution was injected into 50g of ice, and the organic matter was extracted with 50g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of guaiacol was 96%. The organic layer recovered by the extraction operation was washed with 50g of water, and then washed with 50g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3-methoxy-4-hydroxyphenyl)ethane of formula [8], with a yield of 85% and an isomer ratio of 49 / 30 / 13 (2,2-bis(3-methoxy-4-hydroxyphenyl) / 2-(3-methoxy-4-hydroxyphenyl)-2-(3-hydroxy-4-methoxyphenyl) / 2,2-bis(3-hydroxy-4-methoxyphenyl)).

[0395] [Physical properties]

[0396] 1,1,1-Trifluoro-2,2-bis(3-methoxy-4-hydroxyphenyl)ethane,

[0397] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.81-3.84 (6H, s), 4.47-4.57 (1H, m), 6.78-6.96 (6H, m)

[0398] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.1 (3F, d, J=8.7)

[0399] (Example 18)

[0400] [Scheme 21]

[0401]

[0402] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 6.0 g (2,2,2-trifluoroacetaldehyde: 30 mmol, hydrogen fluoride: 0.12 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde captured in Preparation Example 1 (hydrogen fluoride: 40 wt%, hydrogen chloride: 11 wt%, organic matter: 49 wt%) and 9.6 g (0.48 mol) of hydrogen fluoride and 4.7 g (60 mmol) of benzene were weighed and reacted at 25°C and an absolute pressure of 0.1 MPa for 24 hours. The reaction solution was poured into 50 g of ice and the organic matter was extracted with 50 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of benzene was 99%, and that of 1,1,1-trifluoro-2,2-diphenylethane was 79%.

[0403] (Example 19)

[0404] [Scheme 25]

[0405]

[0406] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 15.5 g (2,2,2-trifluoroacetaldehyde: 82 mmol, hydrogen fluoride: 0.37 mol) of a mixture containing 2,2,2-trifluoroacetaldehyde prepared in the same manner as in Preparation Example 1 and 12.4 g (0.62 mol) of hydrogen fluoride and 20 g (165 mmol) of 2,3-dimethylaniline were weighed, heated in an oil bath at 150°C, and reacted at an absolute pressure of 0.55 MPa for 18 hours. The reaction solution was poured into 100 g of ice, 116 g of a 48% potassium hydroxide aqueous solution was added for neutralization, and the organic matter was extracted with 100 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2,3-dimethylaniline was 90%. The organic layer recovered by the extraction operation was washed with 50 g of water, and then washed with 50 g of a saturated sodium bicarbonate aqueous solution, and then recovered by a liquid separation operation. The organic layer was concentrated by a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(2,3-dimethyl-4-aminophenyl)ethane (Formula [4b]) of Formula [4b], with a yield of 77% and an isomer ratio of 99 / 1 (2,2-bis(2,3-dimethyl-4-aminophenyl) isomer / unidentified).

[0407] [Physical properties]

[0408] 1,1,1-Trifluoro-2,2-bis(2,3-dimethyl-4-aminophenyl)ethane,

[0409] 1H-NMR (400MHz, CDCl3) δ (ppm): 2.10 (6H, s), 2.18 (6H, s), 4.19 (4H, bs), 5.01 (1H, q, J = 9.6Hz), 6.59 (2H, d, J = 8.4Hz), 7.07 (2H, d, J = 8.4Hz)

[0410] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -64.6 (3F, d, J=9.2Hz)

[0411] (Example 20)

[0412] [Scheme 26]

[0413]

[0414] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48% by weight, hydrogen chloride: less than 0.1% by weight, organic matter: 52% by weight) 5.6g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 134mmol) and hydrogen fluoride 4.5g (226mmol), 2-fluoroaniline 6.7g (60mmol) were measured and heated in an oil bath at 150°C and reacted at an absolute pressure of 0.8MPa for 20 hours. The reaction solution was injected into a mixture of 50g of ice water and 50mL of ethyl acetate. After 42g of 48% potassium hydroxide aqueous solution was added for neutralization, the organic layer was washed with 50g of water and the organic layer was recovered by liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-fluoroaniline was 99%. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3-fluoro-4-aminophenyl)ethane of formula [11a], with a yield of 93% and an isomer ratio of 50 / 1 (2,2-bis(3-fluoro-4-aminophenyl) isomer / unidentified).

[0415] [Physical properties] 1,1,1-Trifluoro-2,2-bis(3-fluoro-4-aminophenyl)ethane

[0416] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.71 (4H, br-s), 4.43 (1H, q, J = 9.6Hz), 6.71 (2H, dd, J = 12.0, 8.0Hz), 6.90 (2H, d, J = 8.0Hz), 6.97 (2H, d, J = 12.0Hz)

[0417] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -134.3 (2F, br-s), -66.4 (3F, d, J=8.7Hz)

[0418] (Example 21)

[0419] [Scheme 27]

[0420]

[0421] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48% by weight, hydrogen chloride: less than 0.1% by weight, organic matter: 52% by weight) 5.6g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 134mmol) and hydrogen fluoride 9.3g (465mmol), 3-fluoroaniline 6.7g (60mmol) were weighed and heated in an oil bath at 150°C, and reacted at an absolute pressure of 1.0MPa for 16 hours. The reaction solution was injected into a mixture of 200g of ice water and 100mL of ethyl acetate. After 70g of 48% potassium hydroxide aqueous solution was added for neutralization, the organic layer was washed with 50g of water and the organic layer was recovered by liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-fluoroaniline was 94%. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(2-fluoro-4-aminophenyl)ethane of formula [11b], with a yield of 80% and an isomer ratio of 69 / 1 (2,2-bis(2-fluoro-4-aminophenyl) isomer / unidentified).

[0422] [Physical properties] 1,1,1-Trifluoro-2,2-bis(2-fluoro-4-aminophenyl)ethane

[0423] 1 H-NMR (400MHz, CDCl3) δ (ppm): 3.70 (4H, br-s), 5.20 (1H, q, J = 9.6Hz), 6.34 (2H, d, J = 11.6Hz), 6.39 (2H, d, J = 8.4Hz), 7.20 (2H, dd, J = 11.6, 8.4Hz)

[0424] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -1116.5 (2F, br-s), -66.5 (3F, d, J=8.7Hz)

[0425] (Example 22)

[0426] [Scheme 28]

[0427]

[0428] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48 wt%, hydrogen chloride: less than 0.1 wt%, organic matter: 52 wt%) 9.4 g (2,2,2-trifluoroacetaldehyde: 50 mmol, hydrogen fluoride: 226 mmol) and hydrogen fluoride 15.5 g (774 mmol), 2-isopropylaniline 13.5 g (100 mmol) were weighed and heated in an oil bath at 150°C and reacted at an absolute pressure of 0.9 MPa for 24 hours. The reaction solution was injected into a mixture of 72 g of ice water and 50 mL of ethyl acetate. After 170 g of 48% potassium hydroxide aqueous solution was added for neutralization, the organic layer was washed with 50 g of water and recovered by liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-isopropylaniline was 60%. The organic layer was concentrated using a rotary evaporator to obtain the target compound 1,1,1-trifluoro-2,2-bis(3-isopropyl-4-aminophenyl)ethane of formula

[16] with a yield of 57% and an isomer ratio of 24 / 1 (2,2-bis(3-isopropyl-4-aminophenyl) isomer / unidentified).

[0429] [Physical properties] 1,1,1-Trifluoro-2,2-bis(3-isopropyl-4-aminophenyl)ethane

[0430] 1 H-NMR (400MHz, CDCl3) δ (ppm): 1.23 (12H, d, J = 6.8Hz) 2.87 (2H, qq, J = 6.8, 6.8Hz), 3.64 (4 H, br-s), 4.44 (1H, q, J=10.0Hz), 6.61 (2H, d, J=8.4Hz), 7.02 (2H, d, J=8.4Hz), 7.14 (2H, s)

[0431] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.3 (3F, d, J=8.7Hz)

[0432] (Example 29)

[0433] [Scheme 29]

[0434]

[0435] In a 50mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48% by weight, hydrogen chloride: less than 0.1% by weight, organic matter: 52% by weight) 5.6g (2,2,2-trifluoroacetaldehyde: 30mmol, hydrogen fluoride: 135mmol) and hydrogen fluoride 9.3g (465mmol), 2-aminotrifluorotoluene 9.7g (60mmol) were weighed and heated in an oil bath at 150°C and reacted at an absolute pressure of 1.1MPa for 18 hours. The reaction solution was injected into a mixture of 50g of ice water and 50mL of ethyl acetate. After 70g of 48% potassium hydroxide aqueous solution was added for neutralization, the organic layer was washed with 50g of water and the organic layer was recovered by liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-aminotrifluorotoluene was 85%. The organic layer was concentrated using a rotary evaporator to obtain the target compound 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-aminophenyl)ethane of formula [12a] with a yield of 62% and an isomer ratio of 8 / 1 (2,2-bis(3-trifluoromethyl-4-aminophenyl) isomer / unidentified).

[0436] [Physical properties] 1,1,1-Trifluoro-2,2-bis(3-trifluoromethyl-4-aminophenyl)ethane

[0437] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.20 (4H, br-s) 4.47 (1H, q, J = 9.5Hz), 6.71 (2H, d, J = 8.9Hz), 7.25 (2H, d, J = 8.9Hz), 7.35 (2H, s)

[0438] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.6 (3F, d, J=8.7Hz), -62.8 (6F, s)

[0439] (Example 24)

[0440] [Scheme 30]

[0441]

[0442] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48% by weight, hydrogen chloride: less than 0.1% by weight, organic matter: 52% by weight) 21.1g (2,2,2-trifluoroacetaldehyde: 111mmol, hydrogen fluoride: 506mmol) and hydrogen fluoride 33.4g (1.67mol), 2-nitrophenol 30g (215mmol) were weighed and heated in an oil bath at 140°C and reacted at an absolute pressure of 1.6MPa for 24 hours. The reaction solution was injected into a mixture of 120g of ice water and 120mL of ethyl acetate. The separated organic layer was washed with 240g of a saturated sodium bicarbonate aqueous solution, and then washed with 120g of water, and the organic layer was recovered by a liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-nitrophenol was 99%. The organic layer was concentrated by rotary evaporator to obtain the target product 1,1,1-trifluoro-2,2-bis(3-nitro-4-hydroxyphenyl)ethane of formula

[15] with a yield of 95% and an isomer ratio of 3 / 1 (2,2-bis(3-nitro-4-hydroxyphenyl) / 2-(3-nitro-4-hydroxyphenyl)-2-(2-hydroxy-3-nitrophenyl)).

[0443] [Physical properties] 1,1,1-trifluoro-2,2-bis(3-nitro-4-hydroxyphenyl)ethane,

[0444] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.69 (1H, q, J = 9.4Hz), 7.20 (2H, d, J = 8.9Hz), 7.55 (2H, dd, J = 8.7, 2.3Hz), 8.09 (2H, d, J = 2.3Hz), 10.57 (2H, s)

[0445] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -66.9 (3F, d, J=8.7Hz)

[0446] (Example 25)

[0447] [Scheme 31]

[0448]

[0449] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 32.5g (2,2,2-trifluoroacetaldehyde: 182mmol, hydrogen fluoride: 715mmol) and 29.6g (1.48mol) of hydrogen fluoride containing 2,2,2-trifluoroacetaldehyde obtained in Preparation Example 1 were measured, and 39.9g (0.365mmol) of 2-fluorophenol were reacted at 60°C and an absolute pressure of 1.0MPa for 4 hours. The reaction solution was injected into 400g of ice, and the organic matter was extracted with 400g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-fluorophenol was 99%. The organic layer recovered by the extraction operation was washed with 100g of water, and then washed with 100g of saturated sodium bicarbonate aqueous solution, and the organic layer was recovered by liquid separation operation. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3-fluoro-4-hydroxyphenyl)ethane of formula [14a], with a yield of 85% and an isomer ratio of 94 / 6 (2,2-bis(3-fluoro-4-hydroxyphenyl) isomer / unidentified).

[0450] [Physical properties] 1,1,1-trifluoro-2,2-bis(3-fluoro-4-hydroxyphenyl)ethane,

[0451] 1 H-NMR (400MHz, CDCl3) δ (ppm): 4.74 (1H, q), 6.93 (2H, t, J = 8.7Hz), 7.03 (2H, d, J = 8.5Hz), 7.12 (2H, d, J = 12.1Hz), 7.22 (2H, br-s)

[0452] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -136.3 (2F, t, J = 11.5Hz), -66.0 (3F, d, J = 8.7Hz)

[0453] (Example 26)

[0454] [Scheme 32]

[0455]

[0456] In a 100mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, a mixture containing 2,2,2-trifluoroacetaldehyde (hydrogen fluoride: 48% by weight, hydrogen chloride: less than 0.1% by weight, organic matter: 52% by weight) 9.41g (2,2,2-trifluoroacetaldehyde: 50mmol, hydrogen fluoride: 226mmol) and hydrogen fluoride 15.5g (774mmol), 2-trifluoromethylphenol 16.2g (100mmol) were measured and reacted at room temperature and an absolute pressure of 0.15MPa for 24 hours. The reaction solution was injected into a mixture of 100g of ice water and 140mL of ethyl acetate. The separated organic layer was neutralized with 100g of a saturated sodium bicarbonate aqueous solution of 240g, and then washed with 40g of water, and the organic layer was recovered by a liquid separation operation. The extracted organic layer was analyzed by gas chromatography, and the conversion rate of 2-trifluoromethylphenol was 96%. The organic layer was concentrated using a rotary evaporator to obtain the target product, 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)ethane of formula [13a], with a yield of 67% and an isomer ratio of 25 / 1 (2,2-bis(3-trifluoromethyl-4-hydroxyphenyl) isomer / unidentified).

[0457] [Physical properties] 1,1,1-trifluoro-2,2-bis(3-trifluoromethyl-4-hydroxyphenyl)ethane,

[0458] 19 F-NMR (400MHz, CDCl3, CFCl3) δ (ppm): -67.1 (3F, d, J=8.7Hz), -62.7 (6F, s)

[0459] [Comparative Example 1]

[0460] [Scheme 22]

[0461]

[0462] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.4 g (30 mmol) of 35% water-containing 2,2,2-trifluoroacetaldehyde hydrate, 12 g (0.60 mol) of hydrogen fluoride, and 4.7 g (60 mmol) of benzene were weighed and reacted at 25°C and an absolute pressure of 0.2 MPa for 24 hours. The reaction solution was poured into 50 g of ice, and the organic matter was extracted with 50 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the results showed that benzene was 19%, 1,1,1-trifluoro-2-phenyl-2-hydroxyethane was 73%, the target 1,1,1-trifluoro-2,2-diphenylethane was 7%, and the others were 1%.

[0463] [Comparative Example 2]

[0464] [Scheme 23]

[0465]

[0466] In a 100 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirrer, 5.4 g (30 mmol) of 35% water-containing 2,2,2-trifluoroacetaldehyde hydrate, 3 g (0.15 mol) of hydrogen fluoride, and 5.7 g (60 mmol) of phenol were weighed and reacted at room temperature for 15 hours. The reaction solution was poured into 50 g of ice, and the organic matter was extracted with 50 g of ethyl acetate. The extracted organic layer was analyzed by gas chromatography, and the results showed that phenol was 60%, 1,1,1-trifluoro-2-(4-hydroxyphenyl)-2-hydroxyethane was 11%, the target 1,1,1-trifluoro-2,2-bis(4-hydroxyphenyl)ethane was 24%, and others were 5%.

[0467] [Example 27]

[0468] [Scheme 24]

[0469]

[0470] Under nitrogen flow, in a 500 mL glass four-necked flask reactor equipped with a mechanical stirrer and a thermometer, 15 g (51 mmol) of 1,1,1-trifluoro-2,2-bis(3-methyl-4-aminophenyl)ethane of formula [3] obtained in Example 10, 15 g (51 mmol) of 3,3',4,4'-biphenyltetracarboxylic anhydride, and 120 g of dimethylacetamide (super dehydrated product) were weighed and dissolved. The solution was reacted in a thermostatic bath at 20 degrees for 24 hours to synthesize polyamic acid (Polyamic acid), and then 8.5 g (0.11 mmol) of pyridine and 10.9 g (0.11 mmol) of acetic anhydride were added and stirred for 2 hours to perform chemical imidization. The chemical imidization solution is a uniform high-viscosity liquid and is not gelled, so the synthesized polyimide shows high solvent solubility. The molecular weight of the obtained polyimide was measured by gel permeation chromatography (GPC), and the result was 750,000. The polyimide solution was applied to a glass plate by spin coating and fired in an inert oven under a nitrogen gas flow to produce a self-supporting film. The 5% weight loss temperature of the self-supporting film produced under a nitrogen gas flow was measured by a thermogravimetric differential thermal analyzer (TGDTA) and the result was 474 degrees, indicating that the film has the same or higher heat resistance as existing polyimides.

[0471] Industrial Applicability

[0472] The 1,1,1-trifluoro-2,2-bisarylethane used as the subject of the present invention can be used as an excellent optical material having physical properties characterized by low dielectric constant, low refractive index, high transparency, and high solubility.

[0473] This application claims priority based on Japanese patent application No. 2019-019823, filed on February 6, 2019, the disclosure of which is incorporated herein in its entirety.

Claims

1. A production method comprising subjecting a mixture of 2,2,2-trifluoroacetaldehyde and hydrogen fluoride to a condensation reaction with an aryl compound represented by the following general formula [1] under anhydrous conditions to obtain 1,1,1-trifluoro-2,2-bisarylethane represented by the following general formula [2], In the general formula [1], X1 each independently represents a hydroxyl group, an amino group, a carboxyl group, or a halogen group, m represents an integer of 0 to 3, R1 each independently represents a monovalent organic group, and n represents an integer of 0 to (5-m), In the general formula [2], X1, R1, m and n are the same as X1, R1, m and n in the general formula [1].

2. The manufacturing method according to claim 1, wherein: A Lewis acid or a Bronsted acid is added as an additive in the reaction.

3. The manufacturing method according to claim 2, wherein: The Lewis acid or the Bronsted acid is at least one selected from the group consisting of an inorganic acid, an organic acid, and a metal halide.

4. The manufacturing method according to claim 3, wherein: The inorganic acid is at least one selected from the group consisting of phosphoric acid, hydrogen chloride, hydrogen bromide, concentrated nitric acid, concentrated sulfuric acid, fuming nitric acid and fuming sulfuric acid, and the organic acid is at least one selected from the group consisting of formic acid, acetic acid, oxalic acid, benzoic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.

5. The manufacturing method according to claim 3, wherein: The metal halide is a metal halide containing at least one metal selected from the group consisting of boron (III), tin (II), tin (IV), titanium (IV), zinc (II), aluminum (III), antimony (III) and antimony (V).

6. The manufacturing method according to claim 5, wherein: The metal halide is at least one selected from the group consisting of boron trifluoride (III), aluminum trichloride (III), zinc dichloride (II), titanium tetrachloride (IV), tin tetrachloride (IV), and antimony pentachloride (V).

7. The manufacturing method according to any one of claims 1 to 6, wherein: The reaction is carried out without using an organic solvent.

8. The manufacturing method according to claim 1, wherein: The reaction is carried out in a temperature range of -20°C to +200°C and in a pressure range of 0.1 MPa to 4.0 MPa absolute pressure.

9. A production method comprising the following steps: a step of obtaining an aromatic diamine represented by the general formula [2A] by the method of any one of claims 1 to 8; and a step of polycondensing the aromatic diamine with a tetracarboxylic dianhydride represented by the general formula [17] to obtain a polyimide having a repeating unit represented by the general formula [18]. In the general formula [2A], n is an integer of 0 to 4, and R1 each independently represents a monovalent organic group. In the general formula [17], R 2 is a tetravalent organic group, In the general formula [18], R 1 is a divalent organic group represented by the general formula [2B], R 2 is a tetravalent organic group, In the general formula [2B], n is an integer of 0 to 4, and R3 has the same meaning as R1 in the general formula [2A].

10. The manufacturing method according to claim 9, wherein: R 1 is at least one divalent organic group selected from the following, 11. The manufacturing method according to claim 9 or 10, wherein: R 2 is at least one tetravalent organic group selected from the following, 12. The manufacturing method according to claim 9, wherein: The weight average molecular weight of the polyimide is 1,000 or more and 1,000,000 or less.

13. The manufacturing method according to claim 9, wherein: The step of polycondensing the aromatic diamine represented by the general formula [2A] and the tetracarboxylic dianhydride represented by the general formula [17] to obtain the polyimide represented by the general formula [18] comprises the following steps: reacting the aromatic diamine represented by the general formula [2A] with the tetracarboxylic dianhydride represented by the general formula [17] to obtain a polyamic acid having a repeating unit represented by the general formula [19]; ​​and The step of converting the polyamic acid represented by the general formula [19] into a polyimide represented by the general formula [18] by dehydration ring closure. In the general formula [19], R 1 With R in the general formula [18] 1 Same meaning, R 2 With R in the general formula [17] 2 Same meaning.

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