JP7026361B2 - A novel method for producing a perfluoroalkylating agent using monohydroperfluoroalkane as a starting material, and a method for producing an aromatic perfluoroalkyl compound using them. - Google Patents

Description

The present invention is a method for producing a perfluoroalkylating agent for synthesizing an aromatic perfluoroalkyl compound which is an important intermediate for organic electronic materials, pharmaceuticals, pesticides, polymer functional materials, etc., using monohydroperfluoroalkane as a starting material. Regarding.

Organic compounds having a perfluoroalkyl group are important intermediates for organic electronic materials, pharmaceuticals, pesticides, polymer functional materials and the like. Among them, many synthetic examples of trifluoromethyl compounds have been reported.

As a method for introducing a trifluoromethyl group onto the aromatic ring, a cross-coupling reaction between the corresponding aromatic halide and the trifluoromethylating agent is effective. In the trifluoromethylation reaction of aromatic halides, trifluoromethyl copper (CF ₃ Cu) obtained by reacting a trifluoromethyl source with a copper compound as an intermediate is produced, which cross-cups with the aromatic halide. The ring reaction completes the reaction and gives an aromatic trifluoromethyl compound. As a trifluoromethyl source, a ruppato-placash reagent (trifluoromethyltrimethylsilane, CF ₃ SiMe ₃ ) (Patent Document 1) is known. However, it is undeniable that the need to use an expensive trifluoromethyl source in this method is an obstacle to mass production.

On the other hand, trifluoromethane is industrially produced in large quantities as a by-product of the Teflon (registered trademark) manufacturing process, can be obtained in large quantities at low cost, and has the potential as a trifluoromethyl source. It is an attractive material as a trifluoromethyl source for producing group trifluoromethyl compounds. So far, after allowing a base to act on trifluoromethane, trifluoromethyl copper was prepared by reacting with a copper compound, and an aromatic trifluoromethyl compound was synthesized by a cross-coupling reaction with an aromatic halide. Reports have been made (Non-Patent Documents 1 and 2). In this method, trifluoromethane, which is inexpensive and available in large quantities, can be used, but the base used as a reactant (mainly tertiary butoxypotassium, t-BuOK) is expensive, and the copper compound (mainly CuI) is stoichiometrically used. The current situation is that it is not always effective for application to industrial mass production because it requires a certain amount of theory.

As an attempt to reduce the amount of copper used, an appropriate trifluoromethylating agent is used, and the aromatic trifluoro is reacted with an aromatic halide in the presence of a catalytic amount of a copper compound and a coordination compound containing nitrogen. It has been reported that a methyl compound was obtained. In this reaction, triethyltrifluoromethylsilane (Non-Patent Document 3), which is expensive as a trifluoromethyl source, or fluoral, which is relatively inexpensive but has limited uses, cannot be easily obtained in large quantities. Induced Cylated Trifluoromethylhemiaminal (
Non-patent document 4) is used. Cyrilized trifluoromethylhemiaminal can also be synthesized from trifluomethane and morpholinocarbaldehyde, which are relatively inexpensive and industrially available in large quantities, but in this case the expensive reagents (Tris (trimethylsilyl) amine, N ( SiMe ₃ ) ₃ ) is required (Non-Patent Document 5).

As for triethyltrifluoromethylsilane and silylated trifluoromethylhemiaminal, the triethylfluorosilane by-produced after the reaction and the hemiaminoal moiety cannot be recovered and are disposed of as waste.

For the purpose of effective use of resources, if silylated trifluoromethylcarbinol is used, waste reduction can be expected by theoretically recovering and reusing the carbinol moiety as benzophenone, but silylation has been performed so far. Since trifluoromethylcarbinol has not attracted attention as a trifluoromethylating agent, there are no reports of using the compound as a trifluoromethylating agent.

For the synthesis of silylated trifluoromethylcarbinol, a reaction between CF ₃ SiMe ₃ and benzophenone (Non-Patent Document 6) or a reaction between trifluoromethane, benzophenone and N (SiMe ₃ ) ₃ (Non-Patent Document 7) has been reported. However, in the former case, expensive CF ₃ SiMe ₃ must be used, and in the latter case, an expensive reagent (N (SiMe ₃ ) ₃ ) is required, and in addition, the selectivity of the silylated product is low and the raw material is low. The problem that the carbinol of the above remains remains.

Trifluoromethyltrimethoxyborate potassium (Non-Patent Documents 8 and 9) and trifluoromethyltriolborate potassium (Non-Patent Document 10) have also been reported as compounds that can be used as aromatic trifluoromethylating agents.

However, in the conventional method, when these borate salts are used as an aromatic trifluoromethylating agent, a stoichiometric amount of a copper compound is required (Non-Patent Document 8). Further, even in the case of the catalytic reaction, a 20 mol% catalyst was used (Non-Patent Documents 9 and 10), and the catalytic efficiency could not be said to be high.

Furthermore, trifluoromethyltrimethoxyborate potassium cannot be stored for a long period of time due to its low stability and difficulty in isolation, and must be prepared for each reaction.

On the other hand, trifluoromethyltriolborate potassium obtained by the reaction of trifluoromethyltrimethylborate potassium with the corresponding triol is easy to handle because it is a stable crystal in the atmosphere, and is easier to handle as a trifluoromethylating agent than the former. It is valid.

However, in the conventional method, expensive CF ₃ SiMe ₃ is required for the synthesis of trifluoromethyltrimethoxyborate potassium and trifluoromethyltriolbolate potassium, and there remains a problem for industrial mass production (). Non-Patent Documents 9, 10, 11). Further, although an example of preparing trifluoromethyltrimethoxybolate potassium using trifluoromethane, which can be obtained in large quantities at low cost, has been reported, it is known that the borate salt does not act as an aromatic trifluoromethylating agent. Only the structure was identified by converting to the potassium trifluoromethyltrifluoroborate, and no report was made on the synthesis of potassium trifluoromethyltriolbolate (Non-Patent Document 12).

J. Am. Chem. Soc., 2011, 133, p20901-20913 J. Am. Chem. Soc., 2013, 135, p16837-16840 Chem. Commun., 2009, p1909-1911 Adv. Synth. Catal., 2011, 353, p1247-1252 Org. Lett., 2000, 2, p2101-2103 J. Am. Chem. Soc., 1989, 11, p393-395 J. Org. Chem., 2000, 65, p8848-8856 Annual Meeting of the Chemical Society of Japan (March 2011) 1C6-17 Chem. Eur. J., 2011, 17, p2689-2697 The 13th International Kyoto Conference on New Aspects of Organic Chemistry PB (C) -34 Tetrahedron Lett., 2003, 44, p8273-8277 Science 2012, 338, p1324-1327

Japanese Patent No. 5072679

The present inventors aim to solve the conventional technical problems "reduction of catalysts, use of inexpensive trifluoromethyl source and regeneration of used trifluoromethylating agents" in the catalytic aromatic trifluoromethylation reaction. As a result of a sharp study, we succeeded in developing a simple method for producing silylated trifluoromethylcarbinol and trifluoromethyltriolbolate potassium from trifluoromethane.

In addition, when a catalytic aromatic trifluoromethylation reaction was carried out using a trifluoromethylating agent synthesized by the method developed by the inventors, the amount of catalyst was smaller than that reported in the past, that is, 0.2 mol. It was found that the reaction proceeded even when the equivalent was reduced to 0.1 mol equivalent.

Furthermore, it was confirmed that when silylated trifluoromethylcarbinol was used, it could be recovered as benzophenone after the reaction.

［式中、Ｒ_Ｆは、炭素数１～２の直鎖あるいは炭素数３～１０の直鎖、分岐あるいは環状構造を有することもあるアルキル基であって炭素上の水素が全てフッ素で置換されたペルフルオロアルキル基を表し、Ｒ^１およびＲ^２は、それぞれ独立に、水素原子あるいは炭素数１～２の直鎖あるいは炭素数３～１０の直鎖、分岐あるいは環状構造を有することもある置換基を有しても良いアルキル基、アリール基、ヘテロアリール基、アラルキル基、アルケニル基、またはアルキニル基であり、Ｒ^１とＲ^２は一体となって環を形成していてもよく、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子あるいは炭素数１～２の直鎖あるいは炭素数３～１０の直鎖、分岐あるいは環状構造を有することもある置換基を有しても良いアルキル基、アリール基、ヘテロアリール基、アラルキル基、アルケニル基、またはアルキニル基を表わす］
であらわされる化合物の製造方法であって、
一般式［２］：
Ｒ_Ｆ－Ｈ ［２］
［式中、Ｒ_Ｆは前記のとおりである］
で示されるモノヒドロペルフルオロアルカン、一般式［３］：

［式中、Ｒ^１およびＲ^２は前記のとおりである］
で示されるカルボニル化合物、およびＫＯＨを有機溶媒中で反応させて、一般式［４］：

［式中、Ｒ_Ｆ、Ｒ^１およびＲ^２は前記のとおりである］
で表される化合物を得た後、一般式［４］の化合物と一般式［５］：

［式中、Ｒ^３、Ｒ^４及びＲ^５は、前記のとおりである］
で示される化合物とを有機溶媒中で反応させることを特徴とする、一般式［１］で表される化合物の製造方法。
（２）
一般式［１］：

［式中、Ｒ_Ｆ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は前記のとおりである］
であらわされる化合物の製造方法であって、
一般式［２］：
Ｒ_Ｆ－Ｈ ［２］
［式中、Ｒ_Ｆは前記のとおりである］
で示されるモノヒドロペルフルオロアルカン、一般式［３］：

［式中、Ｒ^１およびＲ^２は前記のとおりである］
で示されるカルボニル化合物、およびＮａＨを有機溶媒中で反応させた後、当該反応液と一般式［６］：
Ｒ^３Ｒ^４Ｒ^５Ｓｉ－Ｃｌ ［６］
［式中、Ｒ^３、Ｒ^４及びＲ^５は、前記のとおりである］
で示される化合物とを反応させることを特徴とする、一般式［１］で表される化合物の製造方法。
（３）
一般式［７］：

［式中、Ｒ_Ｆは前記のとおりであり、Ｒ^６は水素原子あるいは炭素数１～２の直鎖あるいは炭素数３～１０の直鎖、分岐あるいは環状構造を有することもある置換基を有しても良いアルキル基、アリール基、ヘテロアリール基、アラルキル基、アルケニル基、またはアルキニル基を表わし、Ｍは元素周期律表におけるＩ族、ＩＩ族、ＩＩＩ族、ＩＶ族、Ｖ族、ＶＩ族、ＶＩＩ族、ＶＩＩＩ族、ＩＸ族、Ｘ族、ＸＩ族、ＸＩＩ族、及びＸＩＩＩ族に属する金属あるいは無置換若しくは炭素数１から１０のアルキル基を置換基として有しても良いアンモニウムであり、それらは単独であっても、複数の物質の混合物であっても良く、ｙはＭであらわされる物質の酸化数に一致する］
であらわされる化合物の製造方法であって、
一般式［２］：
Ｒ_Ｆ－Ｈ ［２］
［式中、Ｒ_Ｆは前記のとおりである］
で示されるモノヒドロペルフルオロアルカンと、塩基およびホウ酸トリアルキルを有機溶媒中で反応させた後、当該反応液と一般式［８］：

［式中、Ｒ^６は前記のとおりである］
で示されるトリオールを反応させることを特徴とする、一般式［７］で表される化合物の製造方法。
（４）
使用する塩基がカリウムヘキサメチルジシラジドであることを特徴とする、（３）に記載の製造方法。
（５）
使用するホウ酸トリアルキルが、ホウ酸トリメチルであることを特徴とする、（３）または（４）に記載の製造方法
（６）
使用するトリオールが、２－ヒドロキシメチル－２－メチル－１，３－プロパンジオールであることを特徴とする、（３）～（５）のいずれかに記載の製造方法。
（７）
一般式［９］：
Ｒ^７－Ｘ ［９］
［式中、Ｒ^７は置換基を有しても良いアリール基あるいはヘテロアリール基を表わし、Ｘはフッ素、塩素、臭素あるいはヨウ素を表す］
で示される化合物と、一般式［１］：

［式中、Ｒ_Ｆ、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５は前記のとおりである］
で示される化合物とを、銅触媒、窒素配位子及び金属フッ化物存在下、有機溶媒中で反応させることを特徴とする、一般式［１０］：
Ｒ_Ｆ－Ｒ^７ ［１０］
［式中、Ｒ_Ｆ、Ｒ^７は前記のとおりである］
で示される芳香族ペルフルオロアルキル化合物の製造方法。
（８）
使用する銅触媒がヨウ化銅（Ｉ）であることを特徴とする、（７）に記載の製造方法。
（９）
使用する窒素配位子が９，１０－フェナントロリンであることを特徴とする、（７）または（８）に記載の製造方法。
（１０）
使用する金属フッ化物がフッ化セシウムであることを特徴とする、（７）～（９）のいずれかに記載の製造方法。
（１１）
使用する化合物［１］の使用量が、一般式［９］で示される化合物の０．５～２当量であることを特徴とする、（７）～（１０）のいずれかに記載の製造方法。
（１２）
使用する銅触媒の使用量が、一般式［９］で示される化合物の０．０１～０．９９当量であることを特徴とする、（７）～（１１）のいずれかに記載の製造方法。
（１３）
使用する窒素配位子の使用量が、一般式［９］で示される化合物の０．０１～０．９９当量であることを特徴とする、（７）～（１２）のいずれかに記載の製造方法。
（１４）
使用する金属フッ化物の使用量が、一般式［９］で示される化合物の０．１～５．０当量であることを特徴とする、（７）～（１３）のいずれかに記載の製造方法。
（１５）
一般式［９］：
Ｒ^７－Ｘ ［９］
[式中、Ｒ^７、Ｘは前記のとおりである]
で示される化合物と、一般式 ［７］：

［式中、Ｒ_Ｆ、Ｒ^６、Ｍ^ｙ＋は前記のとおりである］
で示される化合物とを、銅触媒及び窒素配位子存在下、有機溶媒中で反応させることを特徴とする、一般式［１０］：
Ｒ_Ｆ－Ｒ^７ ［１０］
［式中、Ｒ_Ｆ、Ｒ^７は前記のとおりである］
で示される芳香族ペルフルオロアルキル化合物の製造方法。
（１６）
使用する銅触媒がヨウ化銅（Ｉ）であることを特徴とする、（１５）に記載の製造方法。
（１７）
使用する窒素配位子が９，１０－フェナントロリンであることを特徴とする、（１５）または（１６）に記載の製造方法。
（１８）
使用する化合物［７］の使用量が、一般式［９］で示される化合物の０．５～２当量であることを特徴とする、（１５）～（１７）のいずれかに記載の製造方法。
（１９）
使用する銅触媒の使用量が、一般式［９］で示される化合物の０．０１～０．９９当量であることを特徴とする、（１５）～（１８）のいずれかに記載の製造方法。
（２０）
使用する窒素配位子の使用量が、一般式［９］で示される化合物の０．０１～０．９９当量であることを特徴とする、（１５）～（１９）のいずれかに記載の製造方法。
（２１）
使用する有機溶媒がジグライム、ジメチルホルムアミド（ＤＭＦ）、テトラヒドロフラン（ＴＨＦ）およびジメチルスルホキシドからなる群から選ばれる少なくとも１種であることを特徴とする、（１）～（２０）のいずれかに記載の製造方法。 The present invention provides the following aspects.
(1)
General formula [1]:

[In the formula, RF is an alkyl group having a linear structure having 1 to 2 carbon atoms or a linear group having 3 to 10 carbon atoms, which may have a branched or cyclic structure, and all hydrogen on the carbon is substituted with _fluorine . Representing a perfluoroalkyl group, R ¹ and R ² may independently have a hydrogen atom, a linear group having 1 to 2 carbon atoms, a linear group having 3 to 10 carbon atoms, a branched group, or a cyclic structure. It is an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group, or an alkynyl group, and R ¹ and R ² may be integrated to form a ring, and R ³ ,. R ⁴ and R ⁵ are each independently an alkyl having a hydrogen atom or a linear chain having 1 to 2 carbon atoms or a linear chain having 3 to 10 carbon atoms, or a substituent which may have a branched or cyclic structure. Represents a group, aryl group, heteroaryl group, aralkyl group, alkenyl group, or alkynyl group]
It is a method for producing the compound represented by
General formula [2]:
RF- _H [2]
[In the formula, _RF is as described above]
Monohydroperfluoroalkane represented by, general formula [3]:

[In the formula, R ¹ and R ² are as described above]
The carbonyl compound represented by (1) and KOH are reacted in an organic solvent, and the general formula [4]:

[In the formula, RF, _R ¹ and R ² are as described above]
After obtaining the compound represented by, the compound of the general formula [4] and the general formula [5] :.

[In the formula, R ³ , R ⁴ and R ⁵ are as described above]
A method for producing a compound represented by the general formula [1], which comprises reacting the compound represented by (1) with the compound represented by (1) in an organic solvent.
(2)
General formula [1]:

[In the formula, R _F , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above]
It is a method for producing the compound represented by
General formula [2]:
RF- _H [2]
[In the formula, _RF is as described above]
Monohydroperfluoroalkane represented by, general formula [3]:

[In the formula, R ¹ and R ² are as described above]
After reacting the carbonyl compound represented by (1) and NaH in an organic solvent, the reaction solution and the general formula [6]:
R ³ R ⁴ R ⁵ Si-Cl [6]
[In the formula, R ³ , R ⁴ and R ⁵ are as described above]
A method for producing a compound represented by the general formula [1], which comprises reacting with the compound represented by.
(3)
General formula [7]:

[In the formula, RF is as described above, and _R ⁶ has a hydrogen atom or a linear group having 1 to 2 carbon atoms or a linear group having 3 to 10 carbon atoms, or a substituent which may have a branched or cyclic structure. May represent an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group, or an alkynyl group, and M represents a group I, a group II, a group III, a group IV, a group V, or a group VI in the Periodic Table of the Elements. , VII, VIII, IX, X, XI, XII, and XIII, or ammonium which may have an unsubstituted or alkyl group having 1 to 10 carbon atoms as a substituent. They may be alone or a mixture of multiple substances, where y corresponds to the oxidation number of the substance represented by M].
It is a method for producing the compound represented by
General formula [2]:
RF- _H [2]
[In the formula, _RF is as described above]
After reacting the monohydroperfluoroalkane represented by (1) with a base and trialkyl borate in an organic solvent, the reaction solution and the general formula [8] :.

[In the formula, R ⁶ is as described above]
A method for producing a compound represented by the general formula [7], which comprises reacting the triol represented by.
(4)
The production method according to (3), wherein the base used is potassium hexamethyldisilazide.
(5)
The production method (6) according to (3) or (4), wherein the trialkyl borate used is trimethyl borate.
The production method according to any one of (3) to (5), wherein the triol used is 2-hydroxymethyl-2-methyl-1,3-propanediol.
(7)
General formula [9]:
R ⁷ -X [9]
[In the formula, R ⁷ represents an aryl group or a heteroaryl group which may have a substituent, and X represents fluorine, chlorine, bromine or iodine].
The compound represented by the above and the general formula [1] :.

[In the formula, R _F , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above]
The compound represented by the above formula is reacted in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride, and the general formula [10]:
RF- _R ⁷ [10]
[In the formula, RF and _R ⁷ are as described above]
A method for producing an aromatic perfluoroalkyl compound represented by.
(8)
The production method according to (7), wherein the copper catalyst used is copper (I) iodide.
(9)
The production method according to (7) or (8), wherein the nitrogen ligand used is 9,10-phenanthroline.
(10)
The production method according to any one of (7) to (9), wherein the metal fluoride used is cesium fluoride.
(11)
The production method according to any one of (7) to (10), wherein the amount of the compound [1] used is 0.5 to 2 equivalents of the compound represented by the general formula [9]. ..
(12)
The production method according to any one of (7) to (11), wherein the amount of the copper catalyst used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. ..
(13)
The description according to any one of (7) to (12), wherein the amount of the nitrogen ligand used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. Production method.
(14)
The production according to any one of (7) to (13), wherein the amount of the metal fluoride used is 0.1 to 5.0 equivalent of the compound represented by the general formula [9]. Method.
(15)
General formula [9]:
R ⁷ -X [9]
[In the formula, ^R7 and X are as described above]
The compound represented by the above and the general formula [7] :.

[ ^In the formula, RF, _R6 , ^{My +} are as described above]
The compound represented by the above formula is reacted in an organic solvent in the presence of a copper catalyst and a nitrogen ligand, and the general formula [10]:
RF- _R ⁷ [10]
[In the formula, RF and _R ⁷ are as described above]
A method for producing an aromatic perfluoroalkyl compound represented by.
(16)
The production method according to (15), wherein the copper catalyst used is copper (I) iodide.
(17)
The production method according to (15) or (16), wherein the nitrogen ligand used is 9,10-phenanthroline.
(18)
The production method according to any one of (15) to (17), wherein the amount of the compound [7] used is 0.5 to 2 equivalents of the compound represented by the general formula [9]. ..
(19)
The production method according to any one of (15) to (18), wherein the amount of the copper catalyst used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. ..
(20)
The description according to any one of (15) to (19), wherein the amount of the nitrogen ligand used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. Production method.
(21)
The organic solvent used is at least one selected from the group consisting of diglyme, dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl sulfoxide, according to any one of (1) to (20). Production method.

INDUSTRIAL APPLICABILITY According to the present invention, an aromatic perfluoroalkyl compound which is an important intermediate for organic electronic materials, pharmaceuticals, pesticides, polymer functional materials, etc., using monohydroperfluoroalkanes typified by trifluoromethane and pentafluoroethane as starting materials. It has become possible to provide a simple method for producing a perfluoroalkylating agent required for synthesis. Among the monohydroperfluoroalkanes, trifluoromethane in particular is a gas that produces a large amount and has a high global warming effect, so its treatment method and disposal method have been raised as issues. In the present invention, since it is possible to provide an effective utilization method of trifluoromethane having a high global warming effect and a treatment method thereof, it is possible to make a practical contribution in terms of economy and environment.

Hereinafter, the present invention will be described in detail. Among the monohirodoperfluoroalkanes represented by the general formula [2], the present invention uses trifluoromethane, which is produced in large quantities industrially, as a starting material, and is used as an organic electronic material, a pharmaceutical, a pesticide, a polymer functional material, etc. A simple method for producing a compound represented by the general formula [1] or [7], which can be used as a perfluoroalkylating agent for synthesizing an aromatic perfluoroalkyl compound which is an important intermediate of the above, and general methods using them. It provides an aromatic perfluoroalkyl compound represented by the formula [10].

The scope of the present invention is not limited to these explanations, and other than the following notations, the present invention can be appropriately modified and implemented without departing from the spirit of the present invention.

(Action)
In the conventional method, an expensive base such as tertiary butoxypotassium (t-BuOK) was required for activation of trifluoromethane, whereas the present invention is characterized in that an inexpensive base such as potassium hydroxide can be used. be. After isolating trifluoromethylcarbinol obtained by reacting trifluoromethane with benzophenone in the presence of potassium hydroxide, a new method was developed to induce silylated trifluoromethylcarbinol by acting with a silylating agent. did.

However, since potassium hydroxide is used as a base in this reaction, chlorotrimethylsilane, which is a highly versatile silylating agent, cannot be used, and the reaction cannot be completed in one step. The cause is that chlorotrimethylsilane is immediately decomposed in the presence of potassium hydroxide.

Therefore, we have also newly developed a process for performing the above reaction in one step. That is, by changing the base to sodium hydride that does not react with chlorotrimethylsilane, allowing benzophenone to act in the presence of trifluoromethane, and then reacting with chlorotrimethylsilane in one pot without isolating trifluoromethylcarbinol. In addition to the availability of highly versatile chlorotrimethylsilane, we have succeeded in synthesizing silylated trifluoromethylcarbinol in one step.

It was confirmed that the silylated trifluoromethylcarbinol obtained in the present invention can be obtained as an aromatic trifluoromethyl compound in high yield by a catalytic aromatic trifluoromethylation reaction. Furthermore, it was confirmed that the by-produced benzophenone can be recovered and used again for the synthesis of trifluoromethylating agent.

In the conventional synthesis method of trifluoromethyltriolborate potassium, no report has been made on a one-step synthesis method from inexpensive trifluoromethane.

Since the yield of the intermediate trifluoromethyltrimethoxyborate salt decreases when n-butyllithium is used as the base, potassium hexamethyldisilazide, which has high selectivity for proton extraction, is used and trimethyl borate is allowed to act. Trifluoromethyltrimethylborate potassium could be obtained efficiently. However, the trifluoromethyltrimethoxyborate salt is unstable and cannot be isolated. Therefore, the present inventor has succeeded in developing a process for obtaining trifluoromethyltriolbolate potassium in one step by reacting with triol in one pot without isolating the trifluoromethyltrimethoxyborate salt. Specifically, by reacting trifluoromethane with potassium hexamethyldisilazide and trimethyl borate, and then adding triol to the reaction mixture, we are developing a new process to obtain the desired trifluoromethyltriolbolate potassium in one pot. Successful.

It was confirmed that an aromatic trifluoromethyl compound can be obtained in high yield in a catalytic aromatic trifluoromethylation reaction using trifluoromethyltriolbolate potassium obtained by the synthetic route of the present invention. Furthermore, in the present invention, it has been newly found that the amount of the catalyst can be reduced as compared with the conventional method, that is, the amount can be reduced from 0.2 molar equivalent to 0.1 molar equivalent.

(Explanation of reaction material)
The specific reaction will be described below.
[Cyrilized perfluoroalkylcarbinol represented by the general formula [1]]
The silylated _{perfluoroalkylcarbinol} represented by the general formula [1] of the present invention is not particularly limited, and the substituent represented by RF is a linear group having 1 to 2 carbon atoms or a linear group having 3 to 26 carbon atoms, particularly a carbon number of carbon atoms. It is an alkyl group having 3 to 10 linear, branched or cyclic structures, and represents a perfluoroalkyl group in which all hydrogen on the carbon is substituted with fluorine, specifically, a trifluoromethyl group and a pentafluoroethyl group. Group, heptafluoropropyl group, heptafluoroisopropyl group, pentafluorocyclopropyl group, nonafluorobutyl group, nonafluoroisobutyl group, nonafluoroterriary butyl group, heptafluorocyclobutyl group, undecafluoropentyl group, nonafluorocyclopentyl Group, tridecafluorohexyl group, undecafluorocyclohexyl group, pentadecafluoroheptyl group, tridecafluorocycloheptyl group, heptadecafluorooctyl group, pentadecacyclooctyl group, nonadecafluorononyl group, heptadecafluorocyclononyl Represents a group, a henicosafluorodecenyl group, a nonadecafluorocyclodecenyl group, and the like.
As the substituent represented by R ¹ and R ² , in addition to the hydrogen atom, a linear group having 1 to 2 carbon atoms or a linear group having 3 to 26 carbon atoms, particularly a linear group having 3 to 10 carbon atoms, a branched or cyclic structure is used. Represents an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group or an alkynyl group which may have, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tertiary. Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, phenyl group. , Naftyl group, anthranyl group, naphthalsenyl group, pentasenyl group, hexasenyl group, coronyl group, pyrrolyl group, frill group, thienyl group, pyridyl group, pyrimidyl group, pyrazil group, pyridadyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl Group, indrill group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalyl group, phthalazyl group, quinazolyl group, naphthylylyl group, cinnolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzyl group, phenethyl group. , Vinyl group, allyl group, prenyl group, propagyl group, etc., and atoms other than hydrogen atom, such as nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine, etc., are substituted on these carbon atoms. It may be in the state of being done.

Further, R ¹ and R ² may be integrated to form an aliphatic ring or a heterocycle having 3 to 26 carbon atoms, particularly 3 to 10 carbon atoms, specifically, cyclopropanone, cyclobutanone, and cyclo. Pentanone, Cyclohexanone, Cycloheptanone, Cyclooctanone, Cyclononanone, Cyclodecanone, 3-Pyrrolidinone, N-Methyl-3-pyrrolidinone, N-Ethyl-3-pyrrolidinone, N-propyl-3-pyrrolidinone, N-isopropyl-3 -Pyrrolidinone, N-butyl-3-pyrrolidinone, N-isobutyl-3-pyrrolidinone, N-tertiarybutyl-3-pyrrolidinone, N-pentyl-3-pyrrolidinone, N-hexyl-3-pyrrolidinone, N-heptyl-3 -Pyrrolidinone, N-octyl-3-pyrrolidinone, N-nonyl-3-pyrrolidinone, N-decyl-3-pyrrolidinone, N-cyclopropyl-3-pyrrolidinone, N-cyclobutyl-3-pyrrolidinone, N-cyclopentyl-3- Pyrrolidinone, N-cyclohexyl-3-pyrrolidinone, N-cycloheptyl-3-pyrrolidinone, N-cyclooctyl-3-pyrrolidinone, N-cyclononyl-3-pyrrolidinone, N-cyclodecyl-3-pyrrolidinone, N-phenyl-3- Pyrrolidinone, N-naphthyl-3-pyrrolidinone, N-anthranyl-3-pyrrolidinone, N-naphthacenyl-3-pyrrolidinone, N-pentasenyl-3-pyrrolidinone, N-hexacenyl-3-pyrrolidinone, N-coronyl-3-pyrrolidinone, N-pyrrolill-3-pyrrolidinone, N-frill-3-pyrrolidinone, N-thienyl-3-pyrrolidinone, N-pyridyl-3-pyrrolidinone, N-pyrimidyl-3-pyrrolidinone, N-pyrazyl-3-pyrrolidinone, N- Pyridadyl-3-pyrrolidinone, N-pyrazolyl-3-pyrrolidinone, N-imidazolyl-3-pyrrolidinone, N-oxazolyl-3-pyrrolidinone, N-thiazolyl-3-pyrrolidinone, N-indrill-3-pyrrolidinone, N-benzofuryl- 3-Pyrrolidinone, N-benzothienyl-3-pyrrolidinone, N-quinolyl-3-pyrrolidinone, N-isoquinolyl-3-pyrrolidinone, N-quinoxalyl-3-pyrrolidinone, N-phthalazyl-3-pyrrolidinone, N-quinazolyl-3 -Pyrrolidinone, N-naphthylidyl-3-pyrrolidinone, N-synnolyl-3-pyrrolidinone, N-benzoimidazolyl-3-pyrrolidinone, N-ben Zoxazolyl-3-pyrrolidinone, N-benzothiazolyl-3-pyrrolidinone, N-benzyl-3-pyrrolidinone, N-phenethyl-3-pyrrolidinone, N-vinyl-3-pyrrolidinone, N-allyl-3-pyrrolidinone, N-prenyl- 3-Pyrrolidinone, N-propagyl-3-pyrrolidinone, 4,5-dihydro-3 (2H) -furanone, 4,5-dihydro-3 (2H) -thiophenone, 3-piperidinone, N-methyl-3-piperidinone, N-Ethyl-3-piperidinone, N-propyl-3-piperidinone, N-isopropyl-3-piperidinone, N-butyl-3-piperidinone, N-isobutyl-3-piperidinone, N
-Tershary Butyl-3-piperidinone, N-pentyl-3-piperidinone, N-hexyl-3-piperidinone, N-heptyl-3-piperidinone, N-octyl-3-piperidinone, N-nonyl-3-piperidinone, N -Decil-3-piperidinone, N-cyclopropyl-3-piperidinone, N-cyclobutyl-3-piperidinone, N-cyclopentyl-3-piperidinone, N-cyclohexyl-3-piperidinone, N-cycloheptyl-3-piperidinone, N -Cyclooctyl-3-piperidinone, N-cyclononyl-3-piperidinone, N-cyclodecyl-3-piperidinone, N-phenyl-3-piperidinone, N-naphthyl-3-piperidinone, N-anthranyl-3-piperidinone, N- Naphthenyl-3-piperidinone, N-pentasenyl-3-piperidinone, N-hexacenyl-3-piperidinone, N-coronyl-3-piperidinone, N-pyrrolill-3-piperidinone, N-furyl-3-piperidinone, N-thienyl- 3-Piperidinone, N-pyridyl-3-piperidinone, N-pyrimidyl-3-piperidinone, N-pyrazyl-3-piperidinone, N-pyridazyl-3-piperidinone, N-pyrazolyl-3-piperidinone, N-imidazolyl-3- Piperidinone, N-oxazolyl-3-piperidinone, N-thiazolyl-3-piperidinone, N-indrill-3-piperidinone, N-benzofuryl-3-piperidinone, N-benzothienyl-3-piperidinone, N-quinolyl-3-piperidinone , N-isoquinolyl-3-piperidinone, N-quinoxalyl-3-piperidinone, N-phthalazyl-3-piperidinone, N-quinazolyl-3-piperidinone, N-naphthylidyl-3-piperidinone, N-cinnolyl-3-piperidinone, N -Benzoimidazolyl-3-piperidinone, N-benzoxazolyl-3-piperidinone, N-benzothiazolyl-3-piperidinone, N-vinyl-3-piperidinone, N-allyl-3-piperidinone, N-prenyl-3-piperidinone, N-propagil-3-piperidinone, dihydro-2H-pyran-3 (4H) -one, dihydro-2H-thiopyran-3 (4H) -on, 4-piperidinone, N-methyl-4-piperidinone, N-ethyl- 4-piperidinone, N-propyl-4-piperidinone, N-isopropyl-4-piperidinone, N-butyl-4-piperidinone, N- Isobutyl-4-piperidinone, N-tershalybutyl-4-piperidinone, N-pentyl-4-piperidinone, N-hexyl-4-piperidinone, N-heptyl-4-piperidinone, N-octyl-4-piperidinone, N- Nonyl-4-piperidinone, N-decyl-4-piperidinone, N-cyclopropyl-4-piperidinone, N-cyclobutyl-4-piperidinone, N-cyclopentyl-4-piperidinone, N-cyclohexyl-4-piperidinone, N-cyclo Heptyl-4-piperidinone, N-cyclooctyl-4-piperidinone, N-cyclononyl-4-piperidinone, N-cyclodecyl-4-piperidinone, N-phenyl-4-piperidinone, N-naphthyl-4-piperidinone, N-anthranyl -4-piperidinone, N-naphthacenyl-4-piperidinone, N-pentasenyl-4-piperidinone, N-hexacenyl-4-piperidinone, N-coronyl-4-piperidinone, N-pyrrolill-4-piperidinone, N-frill-4 -Piperidinone, N-thienyl-4-piperidinone, N-pyridyl-4-piperidinone, N-pyrimidyl-4-piperidinone, N-pyrazyl-4-piperidinone, N-pyridadyl-4-piperidinone, N-pyrazolyl-4-piperidinone , N-imidazolyl-4-piperidinone, N-oxazolyl-4-piperidinone, N-thiazolyl-4-piperidinone, N-indrill-4-piperidinone, N-benzofuryl-4-piperidinone, N-benzothienyl-4-piperidinone, N-quinolyl-4-piperidinone, N-isoquinolyl-4-piperidinone, N-quinoxalyl-4-piperidinone, N-phthalazyl-4-piperidinone, N-quinazolyl-4-piperidinone, N-naphthylyl-4-piperidinone, N- Synnolyl-4-piperidinone, N-benzoimidazolyl-4-piperidinone N-benzoxazolyl-4-piperidinone, N-benzothiazolyl-4-piperidinone N-benzyl-4-piperidinone, N-phenethyl-4-piperidinone, N-vinyl -4-piperidinone, N-allyl-4-piperidinone, N-prenyl-4-piperidinone, N-propagil-4-piperidinone, tetrahydro-4H-pyran-4-one, tetrahydro-4H-thiopyran-4-one, etc. Can be mentioned.

On the carbon atom constituting the aliphatic ring or heterocyclic ring, there is a group containing atoms other than hydrogen atom as a substituent, for example, nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine and the like. Specifically, 4-aminocyclohexanone, 4- (methylamino) cyclohexanone, 4- (ethylamino) cyclohexanone, 4- (propylamino) cyclohexanone, 4- (isopropylamino) cyclohexanone, 4- (butyl) may be used. Amino) cyclohexanone, 4- (isobutylamino) cyclohexanone, 4- (territory butylamino) cyclohexanone, 4- (pentylamino) cyclohexanone, 4- (hexylamino) cyclohexanone, 4- (heptylamino) cyclohexanone, 4- (octyl) Amino) cyclohexanone, 4- (nonylamino) cyclohexanone, 4- (decylamino) cyclohexanone, 4- (cyclopropylamino) cyclohexanone, 4- (cyclobutylamino) cyclohexanone, 4- (cyclopentylamino) cyclohexanone, 4- (cyclohexylamino) Cyclohexanone, 4- (cyclohexylamino) cyclohexanone, 4- (cyclooctylamino) cyclohexanone, 4- (cyclononylamino) cyclohexanone, 4- (cyclodecylamino) cyclohexanone, 4- (phenylamino) cyclohexanone, 4- (naphthyl) Amino) cyclohexanone, 4- (anthranylamino) cyclohexanone, 4- (naphthacenylamino) cyclohexanone, 4- (pentasenylamino) cyclohexanone, 4- (hexacenylamino) cyclohexanone, 4- (coronylamino) cyclohexanone, 4- (Pyrrolylamino) cyclohexanone, 4- (frillamino) cyclohexanone, 4- (thienylamino) cyclohexanone, 4- (pyridylamino) cyclohexanone, 4- (pyrimidylamino) cyclohexanone, 4- (pyrazylamino) cyclohexanone, 4- (pyridadylamino) cyclohexanone , 4- (Pyrazolylamino) Cyclohexanone, 4- (Imidazolylamino) Cyclohexanone, 4- (Oxazolylamino) Cyclohexanone, 4- (Thiazolylaminoamino) Cyclohexanone, 4- (Indrillamino) Cyclohexanone, 4- ( Benzofurylamino) cyclohexanone, 4- (benzothienylamino) cyclohexanone, 4- (kinori) Luamino) cyclohexanone, 4- (isoquinolylamino) cyclohexanone, 4- (quinoxalylamino) cyclohexanone, 4- (phthalazylamino) cyclohexanone, 4- (quinazolylamino) cyclohexanone, 4- (naphthylylamino) cyclohexanone, 4 -(Synnolylamino) cyclohexanone, 4- (benzoimidazolylamino) cyclohexanone, 4- (benzoxazolylamino) cyclohexanone, 4- (benzothiazolylamino) cyclohexanone, 4- (benzylamino) cyclohexanone, 4- (phenethyl) Amino) cyclohexanone, 4- (vinylamino) cyclohexanone, 4- (allylamino) cyclohexanone, 4- (prenylamino) cyclohexanone, 4- (propagilamino) cyclohexanone, 4- (dimethylamino) cyclohexanone, 4- (diethylamino) cyclohexanone , 4- (dipropylamino) cyclohexanone, 4- (diisopropylamino) cyclohexanone, 4- (dibutylamino) cyclohexanone, 4- (diisobutylamino) cyclohexanone, 4- (territory butylamino) cyclohexanone, 4- (dipentylamino) Cyclohexanone, 4- (dihexylamino) cyclohexanone, 4- (diheptylamino) cyclohexanone, 4- (dioctylamino) cyclohexanone, 4- (dynonylamino) cyclohexanone, 4- (didecylamino) cyclohexanone, 4- (dicyclopropylamino) cyclohexanone , 4- (Dicyclobutylamino) cyclohexanone, 4- (dicyclopentylamino) cyclohexanone, 4- (dicyclohexylamino) cyclohexanone, 4- (dicycloheptylamino) cyclohexanone, 4- (dicyclooctylamino) cyclohexanone, 4- (Dicyclononylamino) cyclohexanone, 4- (cyclodecylamino) cyclohexanone, 4- (diphenylamino) cyclohexanone, 4- (dinaphthylamino) cyclohexanone, 4- (dianthranylamino) cyclohexanone, 4- (dinaphthacenyl) Amino) cyclohexanone, 4- (dipentacenylamino) cyclohexanone, 4- (dihexacenylamino) cyclohexanone, 4- (dicoronylamino) cyclohexanone, 4- (dipyrrolillamino) cyclohexanone, 4- (difurylamino) cyclohexanone, 4 -(Ji Thienylamino) cyclohexanone, 4- (dipyridylamino) cyclohexanone, 4- (dipyrimidylamino) cyclohexanone, 4- (dipyrazylamino) cyclohexanone, 4- (dipyridadylamino) cyclohexanone, 4- (dipyrazolylamino) cyclohexanone , 4- (diimidazolylamino) cyclohexanone, 4- (dioxazolylamino) cyclohexanone, 4- (dithiazolylamino) cyclohexanone, 4- (diindrillamino) cyclohexanone, 4- (dibenzofurylamino) cyclohexanone, 4 -(Dibenzothienylamino) cyclohexanone, 4- (diquinolylamino) cyclohexanone, 4- (diisoquinolylamino) cyclohexanone, 4- (diquinoxalylamino) cyclohexanone, 4- (diphthalazylamino) cyclohexanone, 4- (diki) Nazolylamino) cyclohexanone, 4- (dinaphthylylamino) cyclohexanone, 4- (dicinnolylamino) cyclohexanone, 4- (dibenzoimidazolylamino) cyclohexanone, 4- (dibenzoxazolylamino) cyclohexanone, 4- (dibenzothia) Zorylamino) cyclohexanone, 4- (dibenzylamino) cyclohexanone, 4- (diphenylamino) cyclohexanone, 4- (divinylamino) cyclohexanone, 4- (diallylamino) cyclohexanone, 4- (diprenylamino) cyclohexanone, 4 -(Dipropagilamino) cyclohexanone, 4-hydroxycyclohexanone, 4- (methoxy) cyclohexanone, 4- (ethoxy) cyclohexanone, 4- (propoxy) cyclohexanone, 4- (isopropoxy) cyclohexanone, 4- (butoxy) cyclohexanone, 4- (isobutoxy) cyclohexanone, 4- (territory butoxy) cyclohexanone, 4- (pentyloxy) cyclohexanone, 4- (hexyloxy) cyclohexanone, 4- (heptyloxy) cyclohexanone, 4- (octyloxy) cyclohexanone, 4- (Nonyloxy) cyclohexanone, 4- (decyloxy) cyclohexanone, 4- (cyclopropoxy) cyclohexanone, 4- (cyclobutoxy) cyclohexanone, 4- (cyclopentyloxy) cyclohexanone, 4- (cyclohexyloxy) cyclohexanone, 4- (cycloheptyloxy) ) Cyclohexanone, 4- Clooctyloxy) cyclohexanone, 4- (cyclononyloxy) cyclohexanone, 4- (cyclodecyloxy) cyclohexanone, 4- (phenoxy) cyclohexanone, 4- (naphthoxy) cyclohexanone, 4- (anthrasenyloxy) cyclohexanone, 4- (Naphthalsenyloxy) cyclohexanone, 4- (pentasenyloxy) cyclohexanone, 4- (hexacenyloxy) cyclohexanone, 4- (coronyloxy) cyclohexanone, 4- (pyrrolilloxy) cyclohexanone, 4- (furyloxy) cyclohexanone , 4- (thienyloxy) cyclohexanone, 4- (pyridyloxy) cyclohexanone, 4- (pyrimidyloxy) cyclohexanone, 4- (pyrazyloxy) cyclohexanone, 4- (pyridazyloxy) cyclohexanone, 4- (pyrazolyloxy) cyclohexanone, 4- (imidazolyloxy) ) Cyclohexanone, 4- (oxazolyloxy) cyclohexanone, 4- (thiazolyloxy) cyclohexanone, 4- (indrilloxy) cyclohexanone, 4- (benzofuryloxy) cyclohexanone, 4- (benzothienyloxy) cyclohexanone, 4- ( Kinoryloxy) cyclohexanone, 4- (isoquinolyloxy) cyclohexanone, 4- (quinoxalyloxy) cyclohexanone, 4- (phthalazyloxy) cyclohexanone, 4- (quinazolyloxy) cyclohexanone, 4- (naphthylyloxy) cyclohexanone, 4 -(Synnolyloxy) cyclohexanone, 4- (benzoimidazolyloxy) cyclohexanone, 4- (benzoxazolyloxy) cyclohexanone, 4- (benzothiazolyloxy) cyclohexanone, 4- (benzyloxy) cyclohexanone, 4- (phenethyl) Oxy) cyclohexanone, 4- (vinyloxy) cyclohexanone, 4- (allyloxy) cyclohexanone, 4- (prenyloxy) cyclohexanone, 4- (propagyloxy) cyclohexanone, 4-mercaptocyclohexanone, 4- (methylthio) cyclohexanone, 4- ( Ethylthio) cyclohexanone, 4- (propylthio) cyclohexanone, 4- (isopropylthio) cyclohexanone, 4- (butylthio) cyclohexanone, 4- (isobutylthio) cyclohexanone, 4- (territory butylthio) cyclohexanone, 4- (Pentilthio) cyclohexanone, 4- (hexylthio) cyclohexanone, 4- (heptylthio) cyclohexanone, 4- (octylthio) cyclohexanone, 4- (nonylthio) cyclohexanone, 4- (decylthio) cyclohexanone, 4- (cyclopropylthio) cyclohexanone, 4 -(Cyclobutylthio) cyclohexanone, 4- (cyclopentylthio) cyclohexanone, 4- (cyclohexylthio) cyclohexanone, 4- (cycloheptylthio) cyclohexanone, 4- (cyclooctylthio) cyclohexanone, 4- (cyclononylthio) cyclohexanone , 4- (cyclodecylthio) cyclohexanone, 4- (phenylthio) cyclohexanone, 4- (naphthylthio) cyclohexanone, 4- (anthranylthio) cyclohexanone, 4- (naphthacenylthio) cyclohexanone, 4- (pentasenylthio) cyclohexanone, 4- (hexacenylthio) ) Cyclohexanone, 4- (coronylthio) cyclohexanone, 4- (pyrrylthio) cyclohexanone, 4- (furylthio) cyclohexanone, 4- (thienylthio) cyclohexanone, 4- (pyridylthio) cyclohexanone, 4- (pyrimidylthio) cyclohexanone, 4- (pyramidylthio) Cyclohexanone, 4- (pyridazilthio) cyclohexanone, 4- (pyrazolylthio) cyclohexanone, 4- (imidazolylthio) cyclohexanone, 4- (oxazolylthio) cyclohexanone, 4- (thiazolylthio) cyclohexanone, 4- (indrillthio) cyclohexanone, 4-( Benzofurylthio) cyclohexanone, 4- (benzothienylthio) cyclohexanone, 4- (quinolylthio) cyclohexanone, 4- (isoquinolylthio) cyclohexanone, 4- (quinoxalylthio) cyclohexanone, 4- (phthalazylthio) cyclohexanone, 4- (quinazolylthio) cyclohexanone, 4- (naphthylylthio) cyclohexanone, 4- (cinnolylthio) cyclohexanone, 4- (benzoimidazolylthio) cyclohexanone, 4- (benzoxazolylthio) cyclohexanone, 4- (benzothiazolylthio) cyclohexanone, 4- (benzylthio) cyclohexanone, 4 -(Phenetylthio) cyclohexanone, 4- (vinylthio) cyclohexanone, 4- (allylthio) cyclohexanone, 4- (prenylthio) ) Cyclohexanone, 4- (propagilthio) cyclohexanone, 4-fluorocyclohexanone, 4-chlorocyclohexanone, 4-bromocyclohexanone, 4-iodocyclohexanone, and the like.

The substituent represented by R ³ , R ⁴ , and R ⁵ may have a linear group having 1 to 2 carbon atoms or a linear group having 3 to 26 carbon atoms, particularly a linear group having 3 to 10 carbon atoms, a branched or cyclic structure. Represents a certain alkyl group, aryl group, heteroaryl group, aralkyl group, alkenyl group or alkynyl group, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, Pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, phenyl group, naphthyl group. , Anthranyl group, naphthacenyl group, pentasenyl group, hexasenyl group, coronyl group, pyrrolyl group, frill group, thienyl group, pyridyl group, pyrimidyl group, pyragil group, pyridadyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, indrill Group, benzofuryl group, benzothienyl group, quinolyl group, isoquinolyl group, quinoxalyl group, phthalazyl group, quinazolyl group, naphthylyl group, cinnolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzyl group, phenethyl group, vinyl group. , Allyl group, prenyl group, propagyl group, etc., and atoms other than hydrogen atom, such as nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine, etc., are substituted on these carbon atoms. But it's okay.

[Monohydroperfluoroalkane represented by the general formula [2]]
The monohydroperfluoroalkane represented by the general formula [2] in the present invention is not particularly limited, and is a corresponding _{monohydroperfluoroalkane} having the same substituent _RF as the RF of the general formula [1]. For example, trifluoromethane, pentafluoroethane, 1H-heptafluoropropane, 2H-heptafluoropropane, and the like can be mentioned.

[Carbonyl compound represented by the general formula [3]]
The carbonyl represented by the general formula [3] in the present invention is a corresponding carbonyl compound having the same substituents ^R1 and ^R2 as ^R1 and ^R2 of the general formula [1], respectively. For example, benzophenone, acetophenone, undecane-2-one, 4'-methoxyacetophenone, 3'-methoxyacetophenone, 2'-methoxyacetophenone, 4'-dimethylaminoacetophenone, 4'-acetoamide acetophenone, 4'-fluoroacetophenone, 4'. '-Chloroacetophenone, 3'-bromoacetophenone and the like can be mentioned.

[Perfluoroalkylcarbinol represented by the general formula [4]]
The perfluoroalkyl carbinol represented by the general formula [4] in the present invention has the same substituents _RF , _R ¹ , and R ² as those of the general formula [1] RF, R ¹ , and R ² , respectively. Alkyl carbinol.

[Cyrilimidazole compound represented by the general formula [5]]
The silylimidazole compound represented by the general formula [5] in the present invention is not particularly limited and has the same substituents R ³ , R ⁴ , and R ⁵ as those of the general formula [1] R ³ , R ⁴ , and R ⁵ . The corresponding silyl imidazole compound. For example, trimethylsilylimidazole, triethylsilyl imidazole, tripropylsilyl imidazole and the like can be mentioned.

[Chlorosilane compound represented by the general formula [6]]
The chlorosilane compound represented by the general formula [6] in the present invention is not particularly limited and has the same substituents R ³ , R ⁴ , and R ⁵ as those of the general formula [1] R ³ , R ⁴ , and R ⁵ . It is a chlorosilane compound. For example, trimethylsilylchlorosilane, triethylsilylchlorosilane, tertiary butyldimethylchlorosilane and the like can be mentioned.

[Perfluoroalkyltriolborate potassium represented by the general formula [7]]
The perfluoroalkyltriolbolate potassium represented by the general formula [7] of the present invention is not particularly limited and represents the same substituent _RF as the RF of the general formula [1], and the substituent represented by _R ⁶ is used. , A linear group having 1 to 2 carbon atoms or a linear group having 3 to 26 carbon atoms, particularly a linear group having 3 to 10 carbon atoms, an alkyl group which may have a branched or cyclic structure, an aryl group, or a heteroaryl group. , Aralkyl group, alkenyl group or alkynyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, hexyl group, heptyl group, octyl. Group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, phenyl group, naphthyl group, anthranyl group, naphthalsenyl group, pentasenyl group, Hexasenyl group, coronyl group, pyrrolyl group, frill group, thienyl group, pyridyl group, pyrimidyl group, pyrazil group, pyridadyl group, pyrazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, indolyl group, benzofuryl group, benzothienyl group, quinolyl Group, isoquinolyl group, quinoxalyl group, phthalazyl group, quinazolyl group, naphthylyl group, cinnolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, benzyl group, phenethyl group, vinyl group, allyl group, prenyl group, propagil group, etc. An atom other than the hydrogen atom, for example, nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine or the like may be substituted on the carbon atom.

M is a metal belonging to Group I, Group II, Group III, Group IV, Group V, Group VI, Group VII, Group VIII, Group IX, Group X, Group XI, Group XII, and Group XIII in the Periodic Table of the Elements. It is ammonium which is unsubstituted or may have an alkyl group having 1 to 10 carbon atoms as a substituent, and they may be alone or a mixture of a plurality of substances, and y is a substance represented by M. Consistent with the oxidation number of.

[Triol compound represented by the general formula [8]]
The triol compound represented by the general formula [8] in the present invention is not particularly limited, and is a corresponding triol compound having the ^same substituent R6 as R6 of the general formula [ ⁷ ]. For example, 2-hydroxymethyl-2-methyl-1,3-propanediol and the like can be mentioned.

[Aromatic halide represented by the general formula [9]]
The aromatic halide represented by the general formula [9] in the present invention is not particularly limited, and specific examples of the substituent represented by ^R7 include a phenyl group, a naphthyl group, an anthranyl group and a naphthacenyl group. It is a pentasenyl group, a hexasenyl group, a coronyl group, etc., and even when atoms other than hydrogen atoms such as nitrogen, oxygen, silicon, phosphorus, sulfur, fluorine, chlorine, bromine, iodine, etc. are substituted on these carbon atoms. Represents a good aromatic group. Alternatively, a pyrrolyl group, a furyl group, a thienyl group, a pyridyl group, a pyrimidyl group, a pyrazil group, a pyridadyl group, a pyrazolyl group, an imidazolyl group, an oxazolyl group, a thiazolyl group, an indolyl group, a benzofuryl group, a benzothienyl group, a quinolyl group and an isoquinolyl group. , Kinoxalyl group, phthalazyl group, quinazolyl group, naphthylyl group, cinnolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiazolyl group, etc., and atoms other than hydrogen atom such as nitrogen, oxygen, silicon are on their carbon atoms. , Phosyl, sulfur, fluorine, chlorine, bromine, iodine and the like may be substituted with a heterocyclic ring, and X represents fluorine, chlorine, bromine or iodine. For example, 4-nitroiodobenzene, 4-methoxyiodobenzene and the like can be mentioned.

[Aromatic perfluoroalkyl compound represented by the general formula [10]]
The aromatic perfluoroalkyl compound represented by the general formula [10] in the present invention is not particularly limited, and is the same substituent _RF as the RF of the general formula [1] and the same substitution as the _R ⁷ of the general formula [9]. Represents the group R ⁷ . For example, 4-nitro (trifluoromethyl) benzene, 4-nitro (pentafluoroethyl) benzene, 4-methoxy (trifluoromethyl) benzene and the like can be mentioned.

(Reaction condition)
Next, the reaction method in the present invention will be described in detail.
First, a method for synthesizing the silylated perfluoroalkylcarbinol of the general formula [1] will be described.

The synthesis method is divided into a two-step method and a one-step method.
The two-step method is achieved by isolating perfluoroalkylcarbinol obtained by reacting a monohydroperfluoroalkane with a carbonyl compound in the presence of potassium hydroxide and then silylating it with a silylating agent. To. On the other hand, the one-step method is achieved by reacting a monohydroperfluoroalkane with a carbonyl compound in the presence of sodium hydride and then allowing chlorosilane to act in the state of the reaction mixture without isolating the intermediate.

The details of the two-step method are as follows.
As the material of the reaction vessel used in the present invention, glass, plastics such as polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), and metals such as stainless steel, Hastelloy, and Inconel can be used, among which glass can be used. Is preferable.

When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.

The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. to 60 ° C. The reaction time can be between 1 and 100 hours, preferably 6 to 24 hours.

The amount of monohydroperfluoroalkane used is about 0.1 to 100 molar equivalents, preferably 1 to 10 molar equivalents, relative to the carbonyl compound.

The reaction pressure should be in the range of atmospheric pressure or less (1.0 × ^10-7 MPa to 0.09 MPa), normal pressure (about 0.1 MPa) or pressurized state (0.11 to 4.87 MPa). However, when the reaction is carried out using a glass reactor, it is preferably 1.0 × ^10-7 MPa to 0.11 MPa, more preferably 0.01 MPa to 0.11 MPa. On the other hand, when the reaction is carried out using a metal reactor such as an autoclave, it is preferably 0.09 × ^10-7 MPa to 4.87 MPa, more preferably 0.2 MPa to 1 MPa.

The method for introducing the monohydroperfluoroalkane will be described when the monohydroperfluoroalkane is trifluoromethane, but other monohydroperfluoroalkanes which are in the gas state in the standard state are also used in the reaction using the same method. can do. The inside of the reaction vessel may be depressurized before use for the reaction, and then trifluoromethane may be introduced to keep the inside of the reaction vessel in a trifluoromethane atmosphere, but the inside of the reaction vessel is replaced with an inert gas such as nitrogen, helium or argon. After that, trifluoromethane may be introduced and the reaction may be carried out in the state of a trifluoromethane mixed gas with the inert gas. At this time, trifluoromethane may be introduced into the reactor directly from a cylinder or cylinder equipped with a pressure reducing valve through a pipe, a sampling bag pre-filled with trifluoromethane, or a method of introducing into the reactor from a rubber balloon. On a small scale, the method of introducing from a rubber balloon into the reactor is preferable, but industrially, it is more preferable to introduce trifluoromethane into the reactor by using a pipe. Examples of the contact method between trifluoromethane and the reaction solution include a method of contact mixing at the gas-liquid interface and a method of liquefying trifluoromethane using a capacitor and mixing it with the reaction solution. The method of causing is preferable.

Monohydroperfluoroalkanes, which are liquid or solid at room temperature, can be used in the reaction in the same manner as ordinary liquid or solid raw materials.

Impurities may be removed from the carbonyl compound by performing a purification operation such as distillation before it is used in the reaction, but impurities to the extent that they are mixed in an industrially available state are used in the implementation of this production method. It does not cause any problems and can be used as it is.

The amount of potassium hydroxide used as a base is about 0.1 molar equivalent to 100 molar equivalents, preferably 1 molar equivalent to 20 molar equivalents, relative to monohydroperfluoroalkane. When hydrate is used or even if it is anhydrous, it is assumed that water is adsorbed, either by drying it before using it for the reaction to remove the water, or by dehydrating it in the reaction system. It is preferable to add an agent such as molecular sieves, but it is not always necessary to completely remove it. A hydrate having a hydration number of 5 or less, or an anhydrate of which is mixed in an industrially available state, that is, 5% by weight or less with respect to a hydroxide, preferably 1. Moisture content of% by weight or less, more preferably 0.1% by weight or less, does not cause any particular problem in the implementation of this production method and can be used as it is. The hydroxide can be used in the form of flakes, granules, or powder, but is preferably in the form of powder, and a method of crushing the granules before use in the reaction is more preferable.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-Dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary butylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1,2-Epoxyethane, jigglime, triglime, tetraglyme, dimethyl sulfoxide, sulforane and the like can be used, but dimethylformamide is preferable, and these can also be used in combination. Further, the above-mentioned aprotic polar solvent can be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the carbonyl compound. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After the reaction, perfluoroalkylcarbinol can be obtained by performing a purification treatment based on a usual organic chemical treatment.

Subsequently, the silylation of the isolated carbinol will be described.

As the material of the reaction vessel used for the silylation reaction, plastics such as glass, polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), stainless steel, Hastelloy, and metals such as Inconel can be used. Among them, glass is preferable.

When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.
The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. The reaction time can be between 1 and 100 hours, preferably 3 to 6 hours.

React silylimidazole as a silylating agent. The amount of silylimidazole is about 1 to 100 equivalents, preferably 1 to 10 equivalents, relative to perfluoroalkylcarbinol.

Impurities may be removed from silylimidazole by performing a purification operation such as distillation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state are used in the implementation of this production method. It does not cause any problems and can be used as it is.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-Dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary butylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1,2-Epoxyethane, jigglime, triglime, tetraglyme, dimethyl sulfoxide, sulfolane and the like can be used, but tetrahydrofuran is preferable, and these can also be used in combination. Further, the above-mentioned aprotic polar solvent can be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of perfluoroalkylcarbinol. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After the reaction, a silylated perfluoroalkylcarbinol can be obtained by performing a purification treatment based on a usual organic chemical treatment.

The details of the one-step method are as follows.
As the material of the reaction vessel used in the present invention, glass, plastics such as polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), and metals such as stainless steel, Hastelloy, and Inconel can be used, among which glass can be used. Is preferable.

When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.

The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. to 60 ° C. The reaction time can be between 1 and 100 hours, preferably 6 to 24 hours.

The amount of monohydroperfluoroalkane used is about 0.1 to 100 molar equivalents, preferably 1 to 10 molar equivalents, relative to the carbonyl compound.

The reaction pressure should be in the range of atmospheric pressure or less (1.0 × ^10-7 MPa to 0.09 MPa), normal pressure (about 0.1 MPa) or pressurized state (0.11 to 4.87 MPa). However, when the reaction is carried out using a glass reactor, it is preferably 1.0 × ^10-7 MPa to 0.11 MPa, more preferably 0.01 MPa to 0.11 MPa. On the other hand, when the reaction is carried out using a metal reactor such as an autoclave, it is preferably 0.09 × ^10-7 MPa to 4.87 MPa, more preferably 0.2 MPa to 1 MPa.

The method for introducing the monohydroperfluoroalkane will be described when the monohydroperfluoroalkane is trifluoromethane, but other monohydroperfluoroalkanes which are in the gas state in the standard state are also used in the reaction using the same method. can do. The inside of the reaction vessel may be depressurized before use for the reaction, and then trifluoromethane may be introduced to keep the inside of the reaction vessel in a trifluoromethane atmosphere, but the inside of the reaction vessel is replaced with an inert gas such as nitrogen, helium or argon. After that, trifluoromethane may be introduced and the reaction may be carried out in the state of a trifluoromethane mixed gas with the inert gas. At this time, trifluoromethane may be introduced into the reactor directly from a cylinder or cylinder equipped with a pressure reducing valve through a pipe, a sampling bag pre-filled with trifluoromethane, or a method of introducing into the reactor from a rubber balloon. On a small scale, the method of introducing from a rubber balloon into the reactor is preferable, but industrially, it is more preferable to introduce trifluoromethane into the reactor by using a pipe. Examples of the contact method between trifluoromethane and the reaction solution include a method of contact mixing at the gas-liquid interface and a method of liquefying trifluoromethane using a capacitor and mixing it with the reaction solution. The method of causing is preferable.

Monohydroperfluoroalkanes, which are liquid or solid at room temperature, can be used in the reaction in the same manner as ordinary liquid or solid raw materials.

Impurities may be removed from the carbonyl compound by performing a purification operation such as distillation before it is used in the reaction, but impurities to the extent that they are mixed in an industrially available state are used in the implementation of this production method. It does not cause any problems and can be used as it is.

The amount of sodium hydride used as a base is about 0.1 molar equivalent to 100 molar equivalents, preferably 1 molar equivalent to 20 molar equivalents, relative to monohydroperfluoroalkane. As the sodium hydride, the one containing oil and stabilized can be used as it is.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-Dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary butylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1,2-Epoxyethane, jigglime, triglime, tetraglyme, dimethyl sulfoxide, sulforane and the like can be used, but dimethylformamide is preferable, and these can also be used in combination. Further, the above-mentioned aprotic polar solvent can be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the carbonyl compound. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After reacting for a predetermined time, chlorosilane is added. The amount of chlorosilane is about 1 to 100 molar equivalents, preferably 1 to 10 equivalents, relative to the carbonyl compound.

Chlorosilane may be purified by performing a purification operation such as distillation before being used in the reaction, but impurities to the extent that they are mixed in an industrially available state are particularly present in the implementation of this production method. It doesn't matter and can be used as it is.

After the reaction, a silylated perfluoroalkylcarbinol can be obtained by performing a purification treatment based on a usual organic chemical treatment.

Next, the synthesis of perfluoroalkyltriol borate potassium will be described.
As the material of the reaction vessel used in the present invention, glass, plastics such as polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), and metals such as stainless steel, Hastelloy, and Inconel can be used, among which glass can be used. Is preferable.

When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.

The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. to 60 ° C. The reaction time can be between 1 and 100 hours, preferably 6 to 24 hours.

The amount of monohydroperfluoroalkane used is about 0.1 to 100 molar equivalents, preferably 1 to 10 molar equivalents, relative to trimethyl borate.

The reaction pressure should be in the range of atmospheric pressure or less (1.0 × ^10-7 MPa to 0.09 MPa), normal pressure (about 0.1 MPa) or pressurized state (0.11 to 4.87 MPa). However, when the reaction is carried out using a glass reactor, it is preferably 1.0 × ^10-7 MPa to 0.11 MPa, more preferably 0.01 MPa to 0.11 MPa. On the other hand, when the reaction is carried out using a metal reactor such as an autoclave, it is preferably 0.09 × ^10-7 MPa to 4.87 MPa, more preferably 0.2 MPa to 1 MPa.

The method for introducing the monohydroperfluoroalkane will be described when the monohydroperfluoroalkane is trifluoromethane, but other monohydroperfluoroalkanes which are in the gas state in the standard state are also used in the reaction using the same method. can do. The inside of the reaction vessel may be depressurized before use for the reaction, and then trifluoromethane may be introduced to keep the inside of the reaction vessel in a trifluoromethane atmosphere, but the inside of the reaction vessel is replaced with an inert gas such as nitrogen, helium or argon. After that, trifluoromethane may be introduced and the reaction may be carried out in the state of a trifluoromethane mixed gas with the inert gas. At this time, trifluoromethane may be introduced into the reactor directly from a cylinder or cylinder equipped with a pressure reducing valve through a pipe, a sampling bag pre-filled with trifluoromethane, or a method of introducing into the reactor from a rubber balloon. On a small scale, the method of introducing from a rubber balloon into the reactor is preferable, but industrially, it is more preferable to introduce trifluoromethane into the reactor by using a pipe. Examples of the contact method between trifluoromethane and the reaction solution include a method of contact mixing at the gas-liquid interface and a method of liquefying trifluoromethane using a capacitor and mixing it with the reaction solution. The method of causing is preferable.

Monohydroperfluoroalkanes, which are liquid or solid at room temperature, can be used in the reaction in the same manner as ordinary liquid or solid raw materials.

The trimethyl borate used in the reaction may be subjected to a predetermined purification operation before being used in the reaction to remove impurities, but impurities to the extent that they are mixed in an industrially available state are present. There is no particular problem in implementing the manufacturing method, and it can be used as it is.

The base used in the reaction, potassium hexamethyldisilazide, is about 0.1 to 100 molar equivalents, preferably 0.1 to 2 molar equivalents, relative to trimethyl borate. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

The triol used in the reaction is about 0.1 to 100 molar equivalents, preferably 0.1 to 2 molar equivalents, relative to trimethyl borate. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-Dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary butylmethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1,2-Epoxyethane, jigglime, triglime, tetraglyme, dimethyl sulfoxide, sulfolane and the like can be used, but tetrahydrofuran is preferable, and these can also be used in combination. Further, the above-mentioned aprotic polar solvent can be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of trimethyl borate. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After the reaction, perfluoroalkyltriolborate potassium can be obtained by performing a purification treatment based on a usual organic chemical treatment.

Although trimethyl borate and potassium hexamethyldisilazide have been described as specific examples as reaction materials, other trialkyl borate and metallic hexamethyldisilazide available in the art are used in the same manner as above. be able to. Examples of the trialkyl borate include trimethyl borate, triethyl borate, tripropyl borate, triisopropyl borate, tributyl borate, trihexyl borate, and trioctyl borate. Examples of the metal hexamethyldisilazide include lithium hexamethyldisilazide, sodium hexamethyldisilazide, and potassium hexamethyldisilazide. Of these, trimethyl borate and potassium hexamethyldisilazide are the most preferable.

Next, a case where the silylated perfluoroalkyl carbinol is used as a perfluoroalkylating agent and reacted with an aromatic halide will be described.

As the material of the reaction vessel used in the present invention, glass, plastics such as polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), and metals such as stainless steel, Hastelloy, and Inconel can be used, among which glass can be used. Is preferable.

It is preferable to use a reaction vessel that has been sufficiently dried to remove water before the reaction.
When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.

The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. to 90 ° C. The reaction time can be between 1 and 100 hours, preferably 6 to 24 hours.

The aromatic halogen compound used in the reaction may be subjected to a predetermined purification operation before being used in the reaction to remove impurities, but impurities to the extent that they are mixed in an industrially available state may be removed. There is no particular problem in implementing this manufacturing method, and it can be used as it is.

The silylated perfluoroalkyl carbinol used in the reaction is about 0.01 to 10 molar equivalents, preferably 1.2 molar equivalents to 2 molar equivalents, relative to the aromatic halogen compound. After the reaction in the previous step, the product that has undergone a normal purification operation can be used as it is.

Copper (I) iodide, which is a copper catalyst used in the reaction, has an equivalent amount of about 0.01 to 0.99 molars, preferably 0.01 to 0.5 molars, relative to the aromatic halogen compound. More preferably, it is 0.1 molar equivalent. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

The 9,10-phenanthroline used in the reaction is about 0.01 to 0.99 molar equivalents, preferably 0.01 molar equivalents to 0.5 molar equivalents, more preferably 0, with respect to the aromatic halogen compound. 1 molar equivalent. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

The cesium fluoride used in the reaction is about 0.1 to 100 molar equivalents, preferably 0.1 molar equivalent to 10 molar equivalents, more preferably 1 molar equivalent to 2 molar equivalents, relative to the aromatic halogen compound. be. Cesium fluoride is preferably activated by a predetermined method before use. Specifically, for this activation, it is preferable to charge the reaction vessel with cesium fluoride and then frame-dry the reaction vessel while evacuating.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary methyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1 , 2-Epoxyethane, jigglime, triglime, tetraglyme, dimethylsulfoxide, sulfolane and the like can be used, but it is preferably diglyme or dimethylformamide, and more preferably a mixture of diglyme and dimethylformamide. The above-mentioned aprotic polar solvent can also be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the aromatic halide. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After the reaction, an aromatic perfluoroalkyl compound can be obtained by subjecting it to a purification treatment based on an ordinary organic chemical treatment.

Next, a case where perfluoroalkyltrierborate potassium is used as a perfluoroalkylating agent and reacted with an aromatic halide will be described.

As the material of the reaction vessel used in the present invention, glass, plastics such as polyethylene and polypropylene, fluororesins such as Teflon and perfluoroalkoxy alkane (PFA), and metals such as stainless steel, Hastelloy, and Inconel can be used, among which glass can be used. Is preferable.

It is preferable to use a reaction vessel that has been sufficiently dried to remove water before the reaction.

When the reaction is carried out, it is preferable to carry out the reaction under an inert gas stream. Examples of the inert gas include dry air, helium, argon, nitrogen and the like, but nitrogen is preferable.

The reaction temperature can be in the range of −40 ° C. to 200 ° C., but is preferably 0 ° C. to 60 ° C. The reaction time can be between 1 and 100 hours, preferably 6 to 24 hours.

The aromatic halide used in the reaction may be subjected to a predetermined purification operation before being used in the reaction to remove impurities, but impurities to the extent that they are mixed in an industrially available state may be removed. There is no particular problem in implementing this manufacturing method, and it can be used as it is.

The perfluoroalkyltriolborate potassium used in the reaction is about 0.01 to 10 molar equivalents, preferably 1.5 to 2 molar equivalents, relative to the aromatic halide. After the reaction in the previous step, the product that has undergone a normal purification operation can be used as it is.

Copper (I) iodide, which is a copper catalyst used in the reaction, has an equivalent amount of about 0.01 to 0.99 molars, preferably 0.01 to 0.5 molars, relative to the aromatic halide. More preferably, it is 0.1 molar equivalent. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

The 9,10-phenanthroline used in the reaction is about 0.01 to 0.99 molar equivalents, preferably 0.01 to 0.5 molar equivalents, more preferably 0. to the aromatic halide. 1 molar equivalent. Impurities may be removed by performing a predetermined purification operation before use in the reaction, but impurities to the extent that they are mixed in an industrially available state do not cause any particular problem in the implementation of this production method. It can be used as it is.

An aprotonic polar solvent can be used as the solvent, and specifically, acetonitrile, propionitrile, phenyl acetonitrile, isobutyronitrile, benzonitrile, dimethylformamide, dimethylacetamide, methylformamide, formamide, N-methylpyrrolidone, N. , N-Dimethylimidazolidinone, hexamethylphosphate triamide, diethyl ether, diisopropyl ether, dibutyl ether, tertiary methyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,3-dioxane, 1,4-dioxane, 1 , 2-Epoxyethane, jigglime, triglime, tetraglyme, dimethyl sulfoxide, sulforane and the like can be used, but dimethyl sulfoxide is preferable. The above-mentioned aprotic polar solvent can also be used in combination with a non-polar solvent such as pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, ethylbenzene and the like.

The amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight, based on 1 part by weight of the aromatic halide. The solvent used may be such that the water is removed before use in the reaction, or a dehydrating agent such as molecular sieves may be added during the reaction, but the water does not necessarily have to be completely removed. The amount of water that is normally mixed in an industrially available state, that is, 5% by weight or less, preferably less than 1% by weight, and more preferably 0.1% by weight or less with respect to the solvent is carried out in this production method. It does not cause any particular problem and can be used as it is.

After the reaction, an aromatic perfluoroalkyl compound can be obtained by subjecting it to a purification treatment based on an ordinary organic chemical treatment.

Hereinafter, the present invention will be specifically described with reference to Examples, but the method for synthesizing a compound in the present invention is not limited to these Examples.
^The compounds were identified by 1H nuclear magnetic resonance spectrum analysis (NMR), ¹³ C NMR, ¹⁹ F NMR, and mass spectrum analysis (EI-MS).

（式中、Ｐｈはフェニル基、ＤＭＳＯはジメチルスルホキシド、ＴＨＦはテトラヒドロフラン、ｒ．ｔ．は室温、３０ｍｉｎは３０分の反応時間、６ｈは６時間の反応時間を示す。） [Example 1]

(In the formula, Ph is a phenyl group, DMSO is dimethyl sulfoxide, THF is tetrahydrofuran, rt is room temperature, 30 min is a reaction time of 30 minutes, and 6 h is a reaction time of 6 hours.)

Benzophenone (1.12 g, 20 mmol) containing potassium hydroxide (ground in an argon glove box in a mortar, 1.12 g, 20 mmol) and dimethyl sulfoxide (undried product, 5 mL) in a 20 mL two-necked flask under an argon atmosphere. After adding 182 mg, 1 mmol), a balloon containing an excess amount of trifluoromethane was attached. After stirring at room temperature for 6 hours, the reaction was stopped by neutralizing potassium hydroxide with 4N hydrochloric acid under an ice bath. The organic layer was extracted with diethyl ether (20 mL × 3 times), washed with water (30 mL × 3 times), washed with saturated aqueous sodium chloride solution (50 mL × 1 time), and dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration, the solvent was removed by a rotary evaporator, and trifluoromethylcarbinol 1 was obtained as a white solid in a yield of 95% (based on the raw material ketone).

The stir bar was placed in a 100 mL three-necked eggplant flask and frame-dried under reduced pressure conditions. The container was cooled to room temperature and then replaced with nitrogen. A solution prepared by adding tetrahydrofuran (pre-dried with Na and then distilled, 3.2 mL) to trifluoromethylcarbinol 1 was placed in a container with a syringe needle and stirred at 0 ° C. for 30 minutes. N-trimethylsilylimidazole (0.7 mL, 673 mg, 4.8 mmol) was slowly added at 0 ° C., and the mixture was stirred at 0 ° C. for 30 minutes. It was removed from the ice bath and stirred at 20 ° C. for 6 hours. After the reaction, the reaction was stopped by neutralizing with an aqueous sodium hydrogen carbonate solution (5 mL). It was extracted with hexane (3 x 20 mL) and washed with saturated aqueous sodium chloride solution (1 x 20 mL). Anhydrous sodium sulfate was added to the organic layer and dried, and the sodium sulfate was removed by filtration. Hexane was removed by a rotary evaporator and purified by silica gel column chromatography (hexane) to obtain silylated trifluoromethylcarbinol 2 as a colorless transparent liquid in a yield of 98% (based on compound 1).

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 0.06 (s, 9H),
7.27-7.46 (m, 10H).
¹³ C NMR (68 MHz, CDCl ₃ ) δ: 1.4, 81.9 (q,
J = 29 Hz), 125.1 (q, J = 286 Hz), 128.
1 (q, J = 2 Hz), 140.8.
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: 89.1 (s, 3F).
EI-MS m / z (%): 255 (36), 213 (16), 184 (48), 165 (96), 105 (32), 77 (100), 73 (56).

実施例１におけるトリフルオロメタンをペンタフルオロエタンに変え、実施例１と同条件で反応を行ったところ、ペンタフルオロエチルカルビノール３を無色透明液体として５１％の収率（^１９Ｆ ＮＭＲ収率、原料ケトン基準）で得た。 [Example 2]

When trifluoromethane in Example 1 was changed to pentafluoroethane and the reaction was carried out under the same conditions as in Example 1, the yield of pentafluoroethyl carbinol 3 as a colorless transparent liquid was 51% ( ¹⁹ F NMR yield, raw material). Obtained by the ketone standard).

Subsequently, trifluoromethylcarbinol 1 was changed to pentafluoroethylcarbinol 3 and the reaction was carried out under the same conditions as in Example 1. As a result, the silylated pentafluoroethylcarbinol 4 was used as a colorless transparent liquid in a yield of 92% (). (Compound 3 standard) was obtained.

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: -0.16 (s, 9H), 7.30-7.33 (m, 6H), 7.40-7.42 (m, 4H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: 45.6 (s, 2F), 84.3 (s, 3F).
EI-MS m / z (%): 255 (71), 194 (16), 165 (50), 105 (41), 77 (76), 73 (100).

（式中、Ｐｈはフェニル基、ＤＭＦはジメチルホルムアミド、ｒ．ｔ．は室温、１２ｈは１２時間の反応時間を示す。） [Example 3]

(In the formula, Ph is a phenyl group, DMF is dimethylformamide, rt is room temperature, and 12h is a reaction time of 12 hours.)

Benzophenone (182 mg, 1 mmol) was added to a 20 mL two-necked flask containing sodium hydride (purity: 50-72%, 96 mg, about 2 mmol) and dimethylformamide (dehydrated product, 1 mL) under an argon atmosphere, and then excess. A balloon containing an amount of trifluoromethane was attached and stirred at room temperature for 12 hours. Then, under an ice bath, chlorotrimethylsilane (0.63 mL, 435 mg, 4 mmol) was added, the temperature was raised to room temperature, and the mixture was stirred for 12 hours. Under an ice bath, water was added to stop the reaction. It was extracted with hexane (20 mL x 3 times), washed with water (30 mL x 1 time), washed with saturated aqueous sodium chloride solution (40 mL x 1 time), and dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration and the solvent was removed with a rotary evaporator to obtain silylated trifluoromethylcarbinol 2 as a colorless transparent liquid in a yield of 62% ( ¹⁹ F NMR yield, based on the raw material ketone).

実施例３におけるトリフルオロメタンをペンタフルオロエタンに変え、実施例３と同条件で反応を行ったところ、シリル化ペンタフルオロエチルカルビノール４を無色透明液体として８８％の収率（^１９Ｆ ＮＭＲ収率、原料ケトン基準）で得た。 [Example 4]

When trifluoromethane in Example 3 was changed to pentafluoroethane and the reaction was carried out under the same conditions as in Example 3, the yield of silylated pentafluoroethyl carbinol 4 as a colorless transparent liquid was 88% ( ¹⁹ F NMR yield). , Raw material ketone standard).

（式中、ＫＨＭＤＳはカリウムヘキサメチルジシラジド、ＴＨＦはテトラヒドロフラン、ｒ．ｔ．は室温、１ｈは１時間の反応時間、５ｈは５時間の反応時間を示す。） [Example 5]

(In the formula, KHMDS is potassium hexmethyldisilazide, THF is tetrahydrofuran, rt is room temperature, 1h is 1 hour reaction time, and 5h is 5 hours reaction time.)

A two-necked 30 mL eggplant flask containing a stir bar was frame-dried under reduced pressure. After allowing to cool, the mixture was prepared under a nitrogen atmosphere with tetrahydrofuran (pre-dried with Na and then distilled, 8 mL) and a trifluoromethane atmosphere, and stirred at −78 ° C. for 1 hour. Then trimethyl borate (4)
15.6 mg / 446.9 μL, 4 mmol) was added, and a THF solution of potassium hexmethyldisilazide (798.0 mg / 4 mL THF, 4 mmol) was added dropwise at a rate of 1 drop per second. After completion of the dropping, the mixture was stirred at −78 ° C. for 1 hour. After completion of the reaction, the temperature was raised to room temperature, the reaction solution was sampled, and ¹⁹ F NMR was measured to obtain a trifluoromethyltrimethoxybolate salt in a yield of 88%. Subsequently, 2-hydroxymethyl-2-methyl-1,3-propanediol (420.5 mg, 3.5 mmol) and tetrahydrofuran (distilled after pre-drying with Na, 2 mL) were added to the reaction solution, and the temperature was 5 at room temperature. Stir for hours. After completion of the reaction, the mixture was filtered, washed with hexane and diethyl ether, and the solvent was distilled off to turn trifluoromethyltriolbolate potassium 5 into a light brown solid in a yield of 42% ( ¹⁹ F).
Obtained by NMR yield (based on trimethyl borate).

¹ HNMR (400 MHz, D ₂ O) δ: 0.84 (s, 3H), 3.47
(S, 6H).
¹⁹ F NMR (376 MHz, D ₂ O, C ₆ F ₆ ) δ: 88.4 (q, ² J _BF = 29.0 Hz, 3 F).

（式中、Ｐｈはフェニル基、ｐｈｅｎは９，１０－フェナントロリン、ｄｉｇｌｙｍｅはジグライム、ＤＭＦはジメチルホルムアミド、２４ｈは２４時間の反応時間を示す。） [Example 6]

(In the formula, Ph is a phenyl group, phen is 9,10-phenanthroline, diglyme is diglyme, DMF is dimethylformamide, and 24h is a reaction time of 24 hours.)

Activated cesium fluoride (91 mg, 0.6 mmol), copper (I) iodide (5.7 mg, 0.03 mmol, 10 mol%), 1,10 in a frame-dried Schlenk tube under reduced pressure under a nitrogen atmosphere. -Add phenanthroline (5.4 mg, 0.03 mmol, 10 mol%), 4-nitroiodobenzene (75 mg, 0.3 mmol), diglime (dehydrated product, 0.3 mL), dimethylformamide (dehydrated product, 0.3 mL). rice field. Cylated trifluoromethylcarbinol 2 (195 mg, 0.6 mmol) was added to the mixed solution, and the mixture was sealed under a nitrogen atmosphere and stirred at 90 ° C. for 24 hours. After completion of the reaction, the temperature was returned to room temperature, water was added, and the organic layer extracted with diethyl ether was washed with water. After drying the organic layer with anhydrous sodium sulfate and concentrating the filtrate under reduced pressure, silica gel column chromatography (hexane: ethyl acetate)
By purification at = 30: 1), 4-nitro (trifluoromethyl) benzene 6 was obtained as pale yellow crystals in a yield of 74% ( ¹⁹ F NMR yield, based on 4-nitroiodobenzene).

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.85 (d, J = 9 Hz, 2H), 8.37 (d, J = 8.8 Hz, 2H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: 98.6 (s, 3F).
EI-MS m / z (%) 192 (31), 145 (100), 125 (29), 95 (40), 75 (39).

（式中、Ｐｈはフェニル基、ｐｈｅｎは９，１０－フェナントロリン、ｄｉｇｌｙｍｅはジグライム、２４ｈは２４時間の反応時間を示す。） [Example 7]

(In the formula, Ph is a phenyl group, phen is 9,10-phenanthroline, diglyme is diglyme, and 24h is a reaction time of 24 hours.)

Activated cesium fluoride (91 mg, 0.6 mmol) and copper (I) iodide (5.7 mg, 0.03 mmol) in an argon atmosphere in a frame-dried Schlenk tube under reduced pressure.
10 mol%), 1,10-phenanthroline (5.4 mg, 0.03 mmol, 10 mol%), 4-nitroiodobenzene (75 mg, 0.3 mmol), followed by silylated pentafluoroethyl carbinol 4 (224). A solution of 0.7 mg (0.6 mmol) of jiglime (0.6 mL) was added dropwise, and the mixture was sealed under an argon atmosphere and stirred at 80 ° C. for 24 hours. After completion of the reaction, the temperature was returned to room temperature, water was added, and the organic layer extracted with diethyl ether was washed with water. After drying the organic layer with anhydrous sodium sulfate, the filtrate is concentrated under reduced pressure, and purified by silica gel column chromatography (hexane: ethyl acetate = 100: 1) to make 4-nitro (pentafluoroethyl) benzene 7 pale yellow. The crystals were obtained in a yield of 93% ( ¹⁹ F NMR yield, based on 4-nitroiodobenzene).

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 7.83 (d, J = 8.8 Hz, 2H), 8.38 (d, J = 8.8 Hz, 2H).
¹⁹ F NMR (376 MHz, CDCl ₃ ) δ: 46.4 (s, 2F), 77.3 (s, 3F).
EI-MS m / z (%): 241 (13), 172 (33), 145 (100), 125 (21), 114 (18), 75 (16).

（式中、ｐｈｅｎは９，１０－フェナントロリン、ＤＭＳＯはジメチルスルホキシド、２４ｈは２４時間の反応時間を示す。） [Example 8]
When the reaction was carried out under the same conditions as in Example 7 except that the amount of the silylated pentafluoroethyl carbinol 4 used in Example 7 was changed from 0.6 mmol to 0.36 mmol, 4-nitro (pentafluoroethyl) benzene was carried out. 7 was obtained as pale yellow crystals in a yield of 64% ( ¹⁹ F NMR yield, based on 4-nitroiodobenzene).
[Example 9]

(In the formula, phen indicates 9,10-phenanthroline, DMSO indicates dimethyl sulfoxide, and 24h indicates a reaction time of 24 hours.)

Copper (I) iodide in a Schlenk tube containing a stirrer frame-dried under reduced pressure under a nitrogen atmosphere.
(5.7 mg, 0.03 mmol), 1,10-phenanthroline (5.4 mg, 5.4 mg,)
0.03 mmol), trifluoromethyltriolbolate potassium 5 (142 mg, 0.6 mmol), 4-iodonitrobenzene (75 mg, 0.3 mmol), dimethyl sulfoxide (dehydrated product, 0.6 mL) were added. After sealing, the mixture was stirred at 60 ° C. for 24 hours. After completion of the reaction, the mixture was allowed to cool, diluted with diethyl ether, and washed with saturated aqueous ammonium chloride solution (3 times). The organic layer is dried and filtered through anhydrous sodium sulfate, the filtrate is concentrated, and crude 4-nitro (trifluoromethyl) benzene 6 is added in a yield of 95% ( ¹⁹ F NMR yield, based on 4-nitroiodobenzene). Obtained.

[Example 10]
The reaction was carried out under the same conditions as in Example 7 except that the amounts of copper (I) iodide and 9,10-phenanthroline used in Example 7 were changed from 0.03 mmol to 0.015 mmol, respectively. Pentafluoroethyl) benzene 7 was obtained as pale yellow crystals in a yield of 82% ( ¹⁹ F NMR yield, based on 4-nitroiodobenzene).

実施例９における4－ニトロヨードベンゼンを4－メトキシヨードベンゼンに変え、実施例９と同条件で反応を行ったところ、4－メトキシ（トリフルオロメチル）ベンゼン８を無
色透明液体として６５％の収率（^１９Ｆ ＮＭＲ収率、４－メトキシヨードベンゼン基準）で得た。 [Example 11]

When 4-nitroiodobenzene in Example 9 was changed to 4-methoxyiodobenzene and the reaction was carried out under the same conditions as in Example 9, 4-methoxy (trifluoromethyl) benzene 8 was converted into a colorless transparent liquid with a yield of 65%. It was obtained by the rate ( ¹⁹ F NMR yield, based on 4-methoxyiodobenzene).

^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 3.85 (s, 3H), 6.96 (d, J = 8.8 Hz, 2H), 7.55 (d, J = 8.8 Hz, 2H).
¹⁹ F NMR (376 MHz, CDCl ₃ , C6 F ₆ ) δ: _100.3 (s, 3F).
EI-MS m / z (%): 176 (100), 145 (31).

[Example 12]
When the reaction was carried out under the same conditions as in Example 11 except that the potassium trifluoromethyltriolbolate 5 in Example 11 was changed from 0.6 mmol to 0.45 mmol, 4-methoxy (trifluoromethyl) benzene 8 was colorless and transparent. 32% yield as liquid ( ¹⁹ F)
It was obtained by NMR yield (based on 4-methoxyiodobenzene).

Claims (9)

General formula [2]:
RF - _H [2]
[In the formula, RF is an alkyl group having a linear structure having 1 to 2 carbon atoms or a linear chain having 3 to 10 carbon atoms, which may have a branched or cyclic structure, and all hydrogen on the carbon is substituted with fluorine _. Perfluoroalkyl group]
Monohydroperfluoroalkane represented by, general formula [3]:

[In the formula, R ¹ and R ² each independently have a hydrogen atom or a linear group having 1 to 2 carbon atoms or a linear group having 3 to 10 carbon atoms, or a substituent which may have a branched or cyclic structure. It may be an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group, or an alkynyl group, and R ¹ and R ² may be integrated to form a ring].
The carbonyl compound represented by (1) and KOH are reacted in an organic solvent, and the general formula [4]:

[In the formula, RF , R ₁ ^and R ² are as described above]
After obtaining the compound represented by, the compound of the general formula [4] and the general formula [5] :.

[In the formula, R ³ , R ⁴ and R ⁵ are independent substituents which may have a hydrogen atom or a linear chain having 1 to 2 carbon atoms or a linear chain having 3 to 10 carbon atoms, a branched or cyclic structure. Represents an alkyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkenyl group, or an alkynyl group which may have.]
By reacting with the compound represented by the above in an organic solvent, the general formula [1]:

[In the formula, R _F , R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above]
The compound represented by is obtained, and the general formula [9] :.
R ⁷ -X [9]
[In the formula, R ⁷ represents an aryl group or a heteroaryl group which may have a substituent, and X represents fluorine, chlorine, bromine or iodine].
The compound represented by the general formula [10]: is characterized by reacting the compound represented by the formula [1] with the compound represented by the general formula [1] in an organic solvent in the presence of a copper catalyst, a nitrogen ligand and a metal fluoride.
RF- _R ⁷ [10]
[In the formula, RF and _R ⁷ are as described above]
A method for producing an aromatic perfluoroalkyl compound represented by. The production method according to claim 1, wherein the copper catalyst used is copper (I) iodide. The production method according to claim 1 or 2, wherein the nitrogen ligand used is 9,10-phenanthroline. The production method according to any one of claims 1 to 3, wherein the metal fluoride used is cesium fluoride. The production method according to any one of claims 1 to 4, wherein the amount of the compound [1] used is 0.5 to 2 equivalents of the compound represented by the general formula [9]. The production method according to any one of claims 1 to 5, wherein the amount of the copper catalyst used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. The production method according to any one of claims 1 to 6, wherein the amount of the nitrogen ligand used is 0.01 to 0.99 equivalents of the compound represented by the general formula [9]. .. The production method according to any one of claims 1 to 7, wherein the amount of the metal fluoride used is 0.1 to 5.0 equivalents of the compound represented by the general formula [9]. The production method according to any one of claims 1 to 8, wherein the organic solvent used is at least one selected from the group consisting of diglyme, dimethylformamide (DMF), tetrahydrofuran (THF) and dimethyl sulfoxide. ..