JP2000191666A - Production of fluorinated aryl magnesium halide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely, efficiently and industrially obtain a fluorinated aryl magnesium halide not containing impurities such as colored component and useful as a Grignard reagent, etc., by reacting a specific hydrocarbon magnesium halide with a specific halogenated fluoroaryl in a specific solvent. SOLUTION: A hydrocarbon magnesium halide of the formula R6MgXa (R6 is a hydrocarbon; Xa is chlorine, bromine or the like) (e.g. bromopentafluorobenzene) is reacted with a halogenated fluoroaryl of formula I (R1 to R5 are each H, fluorine, a hydrocarbon or the like and three or more groups thereof are fluorine; Xb is bromine or iodine) (e.g. bromopentafluorobenzene) in a solvent containing a chain-like ether-based solvent such as diethyl ether, preferably at a lower temperature between a temp. of -10 to 100 deg.C and a reflux temperature to provide the objective compound of formula II (e.g. pentafluorophenylmagnesium bromide). The compound is useful for production of tris(fluoroaryl)boron, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fluoroarylmagnesium halide useful as a Grignard reagent used in various organic synthesis reactions. Further, the present invention relates to a method for producing a fluoroaryl boron derivative useful as, for example, a co-catalyst of a metallocene catalyst (polymerization catalyst) used for a cationic complex polymerization reaction or a catalyst for photopolymerization of silicone. .

[0002]

2. Description of the Related Art Fluorinated arylmagnesium halides are useful compounds, for example, as Grignard reagents used in various organic synthesis reactions. Further, the fluoroaryl magnesium halide is, for example,
It is useful as a cocatalyst for increasing the activity of a metallocene catalyst (polymerization catalyst) used for the cationic complex polymerization reaction, or as an intermediate for producing a fluoroaryl boron derivative which is a compound useful as a photopolymerization catalyst for silicone. Compound. Incidentally, metallocene catalysts have been particularly noted in recent years as polyolefin polymerization catalysts.

[0003] Various methods for synthesizing fluorinated aryl magnesium halides have been proposed.
hem. Soc., 166 (1959) discloses a method for synthesizing pentafluorophenyl magnesium bromide, a kind of fluoroaryl magnesium halide, by reacting bromopentafluorobenzene with magnesium using diethyl ether as a solvent. It has been disclosed.

Further, J. Organometal. Chem., 11, 619-6.
22 (1968) and J. Organometal.Chem., 26, 153-156 (1
971) discloses a method of fluorinating using a Grignard exchange reaction between halogenated aryl fluorides (chloropentafluorobenzene, bromopentafluorobenzene and iodopentafluorobenzene) and ethylmagnesium halide using tetrahydrofuran (THF) as a solvent. A method for synthesizing pentafluorophenyl magnesium halide, which is a kind of arylmagnesium halide, is disclosed. Further, US Pat. No. 5,693,261 discloses a method for synthesizing pentafluorophenyl magnesium halide by utilizing a Grignard exchange reaction between chloropentafluorobenzene and isopropylmagnesium halide.

On the other hand, Japanese Patent Application Laid-Open No. 9-295985 discloses a method for preparing an aryl magnesium fluoride halide (Grignard reagent) by reacting an aryl halide fluoride with magnesium using an alkyl halide as a catalyst. It has been disclosed.

[0006]

SUMMARY OF THE INVENTION The above J. Chem. Soc.,
In the method for synthesizing pentafluorophenyl magnesium bromide described in 166 (1959), the synthesized pentafluorophenyl magnesium bromide is markedly colored by a coloring component which is an impurity generated by a side reaction or the like. For this reason, when synthesizing a fluoroaryl boron derivative using the pentafluorophenyl magnesium bromide as a Grignard reagent, the final product fluoroaryl boron derivative may be colored unless the coloring component is removed. The problem arises.

The above-mentioned J. Organometal. Chem., 1
1, 619-622 (1968) and J. Organometal.Chem., 26, 153.
In the method for producing pentafluorophenylmagnesium halide described in -156 (1971), THF is used as a solvent. However, for example, when the obtained arylboron fluoride derivative is synthesized using a THF solution of pentafluorophenylmagnesium halide, the obtained arylboron fluoride derivative is a strong Lewis acid,
There are problems that ring-opening polymerization of the THF used as a solvent is caused, and that a large amount of by-products are generated.

In the method for producing pentafluorophenyl magnesium halide described in US Pat. No. 5,693,261, the reactivity of chloropentafluorobenzene is low. There is a problem that it is necessary to use an excessive amount of fluorobenzene, and a step of removing the excessively used chloropentafluorobenzene from a final product (final product) is required.

In the method for preparing a Grignard reagent described in Japanese Patent Application Laid-Open No. 9-295985, when diethyl ether is used as a solvent (reaction solvent), the color of the prepared Grignard reagent is reduced, but it is still black. When a color is used and another ether solvent is used as a reaction solvent, there is a problem that the reaction hardly proceeds.

Usually, in the preparation of a Grignard reagent using a halogenated aryl fluoride and magnesium, diethyl ether is used as a solvent. However, for example, in the reaction of bromopentafluorobenzene with magnesium, the heat of reaction (89 kcal / mol) is so large that it is difficult to control the reaction. In particular, diethyl ether has a low boiling point and is flammable. Therefore, there is a problem in terms of safety.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to produce a fluoroarylmagnesium halide containing no impurities such as coloring components in a milder reaction than the conventional reaction. Accordingly, it is an object of the present invention to provide a method which can be manufactured safely, efficiently and industrially. Another object of the present invention is to provide a method for efficiently and easily producing an aryl boron boron derivative having high purity, which is useful as, for example, a co-catalyst of a metallocene catalyst or a catalyst for photopolymerization of silicone. Is to provide.

[0012]

Means for Solving the Problems The inventors of the present application have intensively studied a method for producing a fluorinated arylmagnesium halide and a method for producing a fluorinated arylboron derivative. As a result, a Grignard exchange reaction between a hydrocarbon magnesium halide and a halogenated aryl fluoride is carried out in a solvent containing a chain ether-based solvent, whereby a fluorinated aryl magnesium halide containing no impurities such as coloring components can be obtained. With a mild reaction compared to safe,
It has been found that it can be manufactured efficiently and industrially. In addition, they have found that the reaction is particularly suitably performed in a solvent containing a chain ether solvent excluding diethyl ether. Then, by reacting the boron aryl compound with the aryl magnesium fluoride obtained by the above-described production method, an aryl boron derivative containing no impurities such as coloring components can be produced with high purity, efficiently and easily. They have found that they can do this and have completed the present invention.

That is, the method for producing a fluorinated aryl magnesium halide according to the first aspect of the present invention has the following general formula (1):

[0014]

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[0015] _{(wherein, R 1, R 2, R} 3, R 4, R 5 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and, of the R ₁ to R ₅ At least three of them are fluorine atoms, X _a is a chlorine atom,
(Representing a bromine atom or iodine atom) represented by the formula:
A hydrocarbon magnesium halide represented by the general formula (2): R ₆ MgX _a (2) wherein R ₆ represents a hydrocarbon group, and X _a represents _a chlorine atom, a bromine atom or an iodine atom. , General formula (3)

[0016]

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[0017] (In the formula, represents _{R 1, R 2, R 3} , R 4, R 5 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group, and an alkoxy group, of the R ₁ to R ₅ Wherein at least three of them are fluorine atoms, and X _b represents a bromine atom or an iodine atom) with a halogenated aryl fluoride in a solvent containing a chain ether solvent. I have.

Further, the method for producing tris (fluoroaryl) boron according to the second aspect of the present invention comprises the general formula (5)

[0019]

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[0020] _{(wherein, R 1, R 2, R} 3, R 4, R 5 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and, of the R ₁ to R ₅ The present invention relates to a method for producing tris (fluoroaryl) boron represented by the formula (1), wherein at least three of them are fluorine atoms. A fluorinated arylmagnesium halide, represented by the general formula (4) B (X _C ) ₃ (4) (where X _C represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an alkylalkoxy group) And reacting it with a boron compound.

The process for producing a tetrakis (fluoroaryl) borate / magnesium compound of the invention according to claim 3 is represented by the general formula (6):

[0022]

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[0023] _{(wherein, R 1, R 2, R} 3, R 4, R 5 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and, of the R ₁ to R ₅ At least three of which are fluorine atoms, and X _C represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an alkylalkoxy group). In order to solve the above-described problem,
Wherein the fluorinated arylmagnesium halide obtained by the production method described above is reacted with the boron compound represented by the general formula (4).

The method for producing a fluoroarylborate / magnesium halide derivative according to the invention described in claim 4 is represented by the general formula (8):

[0025]

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[0026] _{(wherein, R 1, R 2, R} 3, R 4, R 5 are each independently a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and, of the R ₁ to R ₅ At least three of which are fluorine atoms, R ₇ represents a hydrocarbon group, and X _d represents a chlorine atom, a bromine atom or an iodine atom). In order to solve the above-mentioned problems, tris (fluoroaryl) boron obtained by the production method according to claim 2 and a compound represented by the following general formula (7): R ₇ MgX _d (7) R ₇ represents a hydrocarbon group, and X _d represents a chlorine atom, a bromine atom or an iodine atom).

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (1) according to the present invention
The method for producing a fluorinated arylmagnesium halide represented by the general formula (2) includes a hydrocarbon magnesium halide represented by the general formula (2) (hereinafter, referred to as a hydrocarbon magnesium halide (2)). This is a method in which a Grignard exchange reaction is carried out with the represented halogenated aryl fluoride. The obtained fluorinated arylmagnesium halide is suitable as an intermediate for producing a fluorinated arylboron derivative.

The fluorinated arylboron derivative to be produced in the present invention is specifically defined by the general formula (5)
A tris (fluoroaryl) boron represented by the following formula, a tetrakis (fluoroaryl) borate / magnesium compound represented by the general formula (6), and the general formula (8)
And a fluoroaryl borate / magnesium halide derivative represented by the formula:

Therefore, as a method for producing the fluoroaryl boron derivative according to the present invention, a method for producing tris (fluoroaryl) boron represented by the general formula (5) and a method for producing the tris (fluoroaryl) boron represented by the general formula (6) The method for producing the tetrakis (fluoroaryl) borate / magnesium compound represented by the above method is a method of reacting the fluorinated arylmagnesium halide obtained by the above method with the boron compound represented by the general formula (4). . Further, the method for producing a fluoroaryl borate / magnesium halide derivative represented by the general formula (8) as the method for producing a fluoroaryl boron derivative according to the present invention includes the above tris (fluoroaryl) boron, This is a method of reacting a hydrocarbon magnesium halide represented by the general formula (7) (hereinafter referred to as hydrocarbon magnesium halide (7)).

The fluorinated arylmagnesium halide to be produced in the present invention is represented by the general formula (1)
Substituent represented by ₁ to R ₅ are each independently a hydrogen atom, a fluorine atom, is composed of a hydrocarbon group, and an alkoxy group, but at least three of the substituents represented by the R ₁ to R ₅ The compound is _a fluorine atom, wherein the substituent represented by Xa is a chlorine atom, a bromine atom or an iodine atom.

The fluorinated arylboron derivative to be produced in the present invention is represented by the general formula (5) or (6).
-In (8), the substituents represented by R _{1 to} R ₅ are each independently constituted by a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and the substituents represented by R _{1 to} R ₅ At least three of the groups are fluorine atoms, and in the general formula (6), the substituent represented by X _c is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an alkylalkoxy group; In the above general formula (8), the compound represented by the formula wherein the substituent represented by R ₇ is a hydrocarbon group and the substituent represented by X _d is a chlorine atom, a bromine atom or an iodine atom.

The above-mentioned hydrocarbon group includes, specifically, an aryl group, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear alkyl group having 2 to 12 carbon atoms. And a branched or cyclic alkenyl group. The above-mentioned hydrocarbon group is an atom that is inert to the reaction according to the present invention, for example, a fluorine atom, an oxygen atom,
It may further have a functional group containing a sulfur atom, a nitrogen atom and the like, that is, an inert functional group. As the functional group,
Specifically, for example, methoxy group, methylthio group, N,
N-dimethylamino group, o-anis group, p-anis group,
Examples include a trimethylsilyloxy group, a dimethyl-t-butylsilyloxy group, and a trifluoromethyl group.

The above alkoxy group is represented by the general formula (A) -OR _a (wherein _Ra represents _a hydrocarbon group).
_The hydrocarbon group represented by a is, for example, an aryl group, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and a linear chain having 2 to 12 carbon atoms. , Alkenyl, and the like. In addition, the above-mentioned hydrocarbon group may further have a functional group which is inactive to the reaction according to the present invention.

Specific examples of the alkoxy group represented by the general formula (A) include, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- Butoxy, t-butoxy, cyclohexyloxy, allyloxy, phenoxy and the like.

The above-mentioned alkylalkoxy group is
Specifically, for example, an alkoxy group containing a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms is shown. The above-mentioned alkylalkoxy group may further have a functional group which is inactive to the reaction according to the present invention.

Hereinafter, the method for producing a fluorinated arylmagnesium halide according to the present invention will be described more specifically.

Specific examples of the halogenated fluoroaryl represented by the general formula (3) include bromopentafluorobenzene, iodopentafluorobenzene, 1-bromo-2,3,4,5-tetrafluorobenzene. Benzene, 1-
Bromo-2,3,4,6-tetrafluorobenzene, 1
-Bromo-2,3,5,6-tetrafluorobenzene,
1-iodo-2,3,4,5-tetrafluorobenzene, 1-iodo-2,3,4,6-tetrafluorobenzene, 1-iodo-2,3,5,6-tetrafluorobenzene, 1- Bromo-2,3,4-trifluorobenzene, 1-bromo-2,3,5-trifluorobenzene,
1-bromo-2,4,5-trifluorobenzene, 1-
Bromo-2,4,6-trifluorobenzene, 1-bromo-3,4,5-trifluorobenzene, 1-iodo-
2,3,4-trifluorobenzene, 1-iodo-2,
3,5-trifluorobenzene, 1-iodo-2,4,
5-trifluorobenzene, 1-iodo-2,4,6-
Trifluorobenzene, 1-iodo-3,4,5-trifluorobenzene and the like.

In the above general formula (3), the halogenated fluorinated aryl in which at least three of the substituents represented by R _{1 to} R ₅ are not a fluorine atom can be substituted with the hydrocarbon magnesium halide (2). Does not cause Grignard exchange reaction.

Specific examples of the above-mentioned hydrocarbon magnesium halide (2) include phenyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium iodide, methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, Ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, n-propyl magnesium chloride, n bromide
-Propyl magnesium, n-propyl magnesium iodide, isopropyl magnesium chloride, isopropyl magnesium bromide, isopropyl magnesium iodide, n-butyl magnesium chloride, n-butyl magnesium bromide, n-butyl magnesium iodide, allyl magnesium chloride, odor Allyl magnesium iodide, allyl magnesium iodide, cyclohexyl magnesium chloride, cyclohexyl magnesium bromide, cyclohexyl magnesium iodide and the like can be mentioned.

Of the above exemplified hydrocarbon magnesium halides (2), phenyl magnesium chloride, phenyl magnesium bromide, phenyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, n-propyl magnesium chloride, N-propyl magnesium bromide, n-propyl magnesium iodide, isopropyl magnesium chloride, isopropyl magnesium bromide, isopropyl magnesium iodide, allyl magnesium chloride, allyl magnesium bromide, allyl magnesium iodide, cyclohexyl magnesium chloride, cyclohexyl magnesium bromide And cyclohexylmagnesium iodide are particularly preferred.

The ratio of the hydrocarbon magnesium halide (2) to the aryl fluoride halide is not particularly limited, but the fluoroaryl magnesium halide is produced for the purpose of selectively producing tris (fluoroaryl) boron. In this case, it is more preferably in the range of 0.8 equivalent to 2.0 equivalents, and further preferably in the range of 0.9 equivalent to 1.5 equivalents. If the above ratio is less than 0.8 equivalent, a large amount of unreacted aryl halide fluoride may remain in the final product, tris (aryl aryl) boron. It is difficult to remove the aryl halide fluoride remaining in the final product, and there is a case where the product cannot be used as a product. In addition, the above ratio is 2.0
If the amount exceeds the equivalent, a large amount of unreacted hydrocarbon magnesium halide (2) may remain.

On the other hand, in the case of producing a fluoroarylmagnesium halide for the purpose of selectively producing a tetrakis (fluoroaryl) borate / magnesium compound, the above ratio is preferably in the range of 0.8 to 2.0 equivalents. More preferably, it is even more preferably in the range of 0.9 to 1.5 equivalents. If the above ratio is less than 0.8 equivalent, the yield of the final product, tetrakis (fluoroaryl) borate / magnesium compound, may be low. If the ratio exceeds 2.0 equivalents, a large amount of unreacted hydrocarbon magnesium halide (2) may remain. Therefore, for example, it takes time to remove these unreacted compounds. Therefore, in order to leave the unreacted aryl halide fluoride unremoved and to remove the unreacted hydrocarbon magnesium halide (2) for the next step without removing the aryl halide fluoride, The ratio of the magnesium magnesium halide (2) is from 1 equivalent to 1.
The reaction may be performed within the range of 2 equivalents.

The reaction between the halogenated fluoroaryl and the hydrocarbon magnesium halide (2) is carried out in a solvent containing a chain ether solvent. The solvent containing the chain ether-based solvent is capable of dissolving or suspending the halogenated aryl halide and the hydrocarbon magnesium halide (2), and is a liquid state inert to the reaction according to the present invention. Any compound may be used as long as it is not particularly limited.

Specific examples of the chain ether solvent include, for example, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-
Butyl methyl ether, diisoamyl ether, 1,2
Aliphatic ether solvents such as -dimethoxyethane and 1,2-diethoxyethane; and the like, and these may be used alone or in combination of two or more.

Further, the linear ether solvents exemplified above include, for example, aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as cyclopentane, cyclohexane and methylcyclohexane; benzene May be used in the form of a mixed solvent mixed with a solvent other than a chain ether-based solvent such as aromatic hydrocarbon solvents such as toluene, xylene and anisole. Further, for example, a cyclic ether such as tetrahydrofuran can also be mixed to the extent that ring-opening polymerization is not caused or a by-product is not generated. As the solvent mixed with the chain ether-based solvent, only one kind may be used, or two or more kinds may be used in combination. Hereinafter, unless otherwise specified, the term “solvent” refers to a solvent containing a chain ether-based solvent.

The reaction between the halogenated aryl halide and the hydrocarbon magnesium halide (2) proceeds gently because the heat of reaction is smaller than that of the conventional reaction (for example, the reaction between bromopentafluorobenzene and magnesium). I do. Therefore, in the method for producing a fluoroarylmagnesium halide according to the present invention, it is easy to control the reaction, and the reaction can be smoothly performed in a solvent. Therefore, a mixed solvent of a chain ether-based solvent and, for example, another solvent having a higher boiling point than that of the chain ether-based solvent can be used, so that the above reaction can be performed more safely. it can.

The ratio (concentration) of the chain ether solvent in the solvent containing the chain ether solvent is not particularly limited as long as the above reaction can proceed smoothly. However, it is more preferably 1.0% by weight or more, still more preferably 5.0% by weight or more, and particularly preferably 10.0% by weight or more. If the above ratio is less than 1.0% by weight, the efficiency of the reaction is low due to the use of a large amount of solvent, and the reaction rate may be extremely low.

The amount of the solvent used is such that the halogenated fluoroaryl and the hydrocarbon magnesium halide (2) can be dissolved or suspended and the reaction can proceed smoothly. Although not particularly limited, the concentration of the synthesized fluoroaryl magnesium halide in the reaction solution is more preferably in the range of 0.1% by weight to 80% by weight,
It is more preferably in the range of 1.0% to 70% by weight, and particularly preferably in the range of 5.0% to 60% by weight. If the above concentration is less than 0.1% by weight, the amount of the solvent used is large, so that the efficiency of the reaction is poor,
In addition, the reaction rate may be extremely slow. On the other hand, when the concentration exceeds 80% by weight, handling may be difficult such as precipitation of fluorinated arylmagnesium halide.

The method for mixing the aryl fluoride halide and the hydrocarbon magnesium halide (2) is not particularly limited. For example, the method for mixing the aryl halide halide or the solution thereof with the hydrocarbon magnesium halide (2) May be added dropwise, or an aryl halide or a solution thereof may be added dropwise to a solution of the hydrocarbon magnesium halide (2). Moreover,
A method in which a halogenated fluoroaryl or a solution thereof and a solution of a hydrocarbon magnesium halide (2) are dropped into a solvent may be employed.

The reaction temperature of the above reaction is not particularly limited, but is preferably -30 ° C. or more and the reflux temperature of the above solvent, more preferably -20 ° C. or more and 200 ° C.
Alternatively, the temperature is more preferably equal to or lower than the lower temperature among the reflux temperatures, and particularly preferably equal to or higher than -10 ° C and equal to or lower than 100 ° C or the lower temperature among the reflux temperatures.

The reaction time and pressure of the above reaction are as follows:
There are no particular restrictions on the reaction temperature, the amount of the hydrocarbon magnesium halide (2), the amount of the aryl fluoride halide, the combination of both, and the composition of the solvent.
The reaction may be appropriately set according to other reaction conditions so that the reaction is completed. Therefore, the pressure may be any of normal pressure, pressurization, and pressure reduction. Further, the above reaction is desirably performed in an atmosphere of an inert gas such as a nitrogen gas.

By performing the above Grignard exchange reaction, a fluorinated arylmagnesium halide represented by the general formula (1) is produced. The fluorinated arylmagnesium halide produced by the above reaction is a compound useful as a Grignard reagent or the like used in various organic synthesis reactions, for example, for producing a fluorinated arylboron derivative described in detail below. Used as an intermediate.

At this time, when the fluoroarylmagnesium halide used as an intermediate is colored by a coloring component which is an impurity generated by a side reaction or the like, the produced fluoroarylboron derivative also It is colored by the coloring component.

However, according to the production method of the present invention, fluorinated arylmagnesium halides can be synthesized by a mild reaction with small heat of reaction, so that impurities such as coloring components are not generated. Therefore, according to the above-mentioned production method, it is possible to provide a fluorinated arylmagnesium halide useful as a Grignard reagent or the like used in various organic synthesis reactions.

In the method for producing a fluoroarylmagnesium halide according to the present invention, an alkyl halide is produced together with the target fluoroarylmagnesium halide. However, the alkyl halide does not adversely affect the performance of the fluoroaryl magnesium halide as a Grignard reagent. Therefore, when producing, for example, a fluoroaryl boron derivative using a fluoroaryl magnesium halide, it is not necessary to remove the alkyl halide prior to the production. The above-mentioned alkyl halide can be distilled off together with the solvent, for example, by heating performed when producing the fluoroaryl boron derivative.

Next, the method for producing the tris (fluoroaryl) boron and the tetrakis (fluoroaryl) borate / magnesium compound as the fluoroarylboron derivative according to the present invention will be described more specifically below.

Specific examples of the boron compound represented by the general formula (4) include boron trifluoride, boron trichloride, boron tribromide, boron triiodide, and trimethoxy boron. Can be These boron compounds may form a complex with, for example, diethyl ether or tetrahydrofuran.

The molar ratio of the fluoroarylmagnesium halide represented by the general formula (1) to the boron compound (fluoroarylmagnesium halide / boron compound) is not particularly limited. ~ 5.
More preferably, it is within the range of 0. When the tris (fluoroaryl) boron represented by the general formula (5) as the fluoroarylboron derivative is selectively produced, the above molar ratio is 2.0 to 3.4. It is more preferable to set within the range, and it is particularly preferable to set within the range of 2.5 to 3.3. On the other hand, when the tetrakis (fluoroaryl) borate / magnesium compound represented by the general formula (6) as the fluoroaryl boron derivative is selectively produced, the above molar ratio is set to 3.5 to 5 Is more preferably set within a range of 3.7 to 4.5, and particularly preferably set within a range of 3.7 to 4.5.

In the reaction between the aryl magnesium fluoride halide and the boron compound, the boron compound or a solution thereof is mixed with a solution (reaction liquid) of the aryl magnesium halide obtained by synthesizing the aryl magnesium halide. This is done by: That is, the above reaction is performed in the solvent used at the time of producing the fluorinated arylmagnesium halide. From the viewpoint of safety, the solvent is usually more preferably a solvent containing a chain ether solvent except diethyl ether. However, in the reaction between the fluoroaryl magnesium halide and the boron compound, 1) the reaction The rate may be extremely slow, or 2) a side reaction may occur, resulting in a decrease in the yield of the above-mentioned aryl boron trifluoride or tetrakis (fluoroaryl) borate / magnesium compound. In this case, about 0.5 to 3.0 equivalents of diethyl ether with respect to the fluorinated arylmagnesium halide (which may form a complex with the boron compound).
By performing the reaction in the presence of, the reaction results can be improved.

The amount of the solvent used is not particularly limited as long as it can dissolve or suspend the fluorinated arylmagnesium halide and the boron compound and can proceed the above-mentioned reaction smoothly. Not something. Further, for example, when the boron compound is mixed in the form of a solution, the solvent used for forming the solution may be the same compound as the solvent used in the production of the fluoroarylmagnesium halide, or a different compound. It may be. Further, if necessary, a solvent is added to dilute the reaction solution, or a solvent different from the solvent used during the reaction is added, and then the solvent is exchanged by distilling off the solvent used during the reaction. Can also.

The method of mixing the solution of the fluoroarylmagnesium halide and the boron compound is not particularly limited. For example, when the tris (fluoroaryl) boron is selectively produced, the boron compound Alternatively, a method of dropping a solution of a fluoroarylmagnesium halide into the solution is more preferable. On the other hand, when a tetrakis (fluoroaryl) borate / magnesium compound is selectively produced, a solution of the fluoroarylmagnesium halide is preferably added. , A boron compound or a solution thereof may be added dropwise, or a solution of a fluoroarylmagnesium halide may be added dropwise to the boron compound or a solution thereof. Further, a method of dropping a solution of a fluoroarylmagnesium halide and a boron compound or a solution thereof into a solvent may be employed.

The mixing temperature at the time of mixing the solution of the fluoroarylmagnesium halide and the boron compound is not particularly limited. For example, when the tris (fluoroaryl) boron is selectively produced, -30 ° C ~
The temperature is more preferably in the range of 50 ° C, and even more preferably in the range of -10 ° C to 40 ° C. If the mixing temperature is lower than −30 ° C., the reaction may be extremely slow, and if it exceeds 50 ° C., a tetrakis (fluoroaryl) borate / magnesium compound may be by-produced. On the other hand, when the tetrakis (fluoroaryl) borate / magnesium compound is selectively produced, the mixing temperature is more preferably −30 ° C. or higher and the reflux temperature of the solvent or lower, more preferably −20 ° C. or higher. More preferably, the temperature is not higher than 200 ° C. or the lower of the reflux temperatures.
It is particularly preferred that it is below 50 ° C. or the lower of the reflux temperatures.

Although the reaction temperature of the above reaction is not particularly limited, it is more preferably -30 ° C. or more and not more than the reflux temperature of the solvent. For example, tris (fluoroaryl) boron is selectively used. -2
It is more preferable that the temperature is 0 ° C or higher and 150 ° C or lower but not more than the lower temperature of the reflux temperature, and particularly it is higher than -10 ° C and 100 ° C or lower than the lower temperature of the reflux temperature. preferable. The reaction temperature is -30 ° C
If it is lower, the reaction may be extremely slow.
If it exceeds 50 ° C. (or the above-mentioned reflux temperature), tris (fluoroaryl) borane may be decomposed. When the tetrakis (fluoroaryl) borate / magnesium compound is selectively produced, the temperature is more preferably 0 ° C. or more, 200 ° C. or the lower temperature of the reflux temperature, and more preferably 30 ° C. or more, It is particularly preferred that the temperature is not higher than 150 ° C. or the lower of the reflux temperatures. If the reaction temperature is lower than −30 ° C., the reaction may be extremely slow. On the other hand, if it exceeds 200 ° C. (or the above-mentioned reflux temperature), the tetrakis (fluoroaryl) borate / magnesium compound may be decomposed. is there.

The reaction time and pressure of the above reaction are as follows:
The reaction is not particularly limited, and the reaction may be completed according to other reaction conditions, such as the reaction temperature, the amount of the fluoroarylmagnesium halide, the amount of the boron compound, the combination of the two, and the composition of the solvent. What is necessary is just to set suitably.
Therefore, the pressure may be any of normal pressure, pressurization, and pressure reduction. Further, the above reaction is desirably performed in an atmosphere of an inert gas such as a nitrogen gas. In addition, together with or after the reaction, if necessary, the solvent and / or the alkyl halide by-produced during the production of the fluoroarylmagnesium halide can be distilled off. Alternatively, the solvent exchange can be performed together with or after the reaction.

By performing the above Grignard reaction, tris (fluoroaryl) boron represented by the above general formula (5) and tetrakis (fluoroaryl) borate represented by the above general formula (6). One of the magnesium compounds is selectively produced. According to the production method of the present invention, a tris (fluoroaryl) boron and a tetrakis (fluoroaryl) borate / magnesium compound containing no impurities such as coloring components can be obtained.

Next, a method for producing a fluoroaryl borate / magnesium halide derivative as a fluoroaryl boron derivative according to the present invention will be described more specifically below.

As the hydrocarbon magnesium halide (7), specifically, for example, in addition to the compounds exemplified as the hydrocarbon magnesium halide (2), p-fluorophenyl magnesium bromide,
2,6-difluorophenyl magnesium bromide,
2,4,6-trifluorophenyl magnesium bromide, 2,3,5,6-tetrafluorophenyl magnesium bromide and the like can be mentioned.

The ratio of the hydrocarbon magnesium halide (7) to the tris (fluoroaryl) boron represented by the general formula (5) is not particularly limited, but
0.5 equivalent or more is more preferable, the range of 0.5 equivalent to 5.0 equivalent is more preferable, and the range of 1.0 equivalent to 3.0 equivalent is particularly preferable. If the above ratio is less than 0.5 equivalent, a large amount of unreacted tris (fluoroaryl) boron may remain. If the ratio exceeds 5.0 equivalents, a large amount of unreacted hydrocarbon magnesium halide (7) may remain. Therefore, for example, it takes time to remove these unreacted compounds.

The reaction between the tris (fluoroaryl) boron and the hydrocarbon magnesium halide (7) is carried out by reacting a solution (reaction liquid) of the tris (fluoroaryl) boron obtained by synthesizing the tris (fluoroaryl) boron. )
And a solution of a hydrocarbon magnesium halide (7). That is, the above reaction is carried out in the solvent used during the production of tris (fluoroaryl) boron. From the viewpoint of safety, the solvent is usually more preferably a solvent containing a chain ether-based solvent except diethyl ether, but is preferably a solvent containing tris (fluoroaryl) boron and a hydrocarbon magnesium halide (7). In the reaction, 1) the reaction speed is extremely slow,
2) A side reaction occurs and the above-mentioned fluorinated aryl borate
The yield of the magnesium compound may decrease. In this case, for the tris (fluoroaryl) boron,
About 0.5 to 3.0 equivalents of diethyl ether (which may form a complex with (fluoroaryl) boron)
By performing the reaction in the presence of, the reaction results can be improved.

The amounts of the solvents used are tris (fluoroaryl) boron and hydrocarbon magnesium halide (7).
Can be dissolved or suspended, and it is sufficient that the reaction can proceed smoothly.
There is no particular limitation. Further, for example, the solvent used when forming the solution of the hydrocarbon magnesium halide (7) may be the same compound as the solvent used when producing the tris (fluoroaryl) boron, or may be a different compound. . Further, if necessary, a solvent is added to dilute the reaction solution, or a solvent different from the solvent used during the reaction is added, and then the solvent is exchanged by distilling off the solvent used during the reaction. Can also.

The method for mixing the solution of tris (fluoroaryl) boron and the solution of hydrocarbon magnesium halide (7) is not particularly limited.
A solution of hydrocarbon magnesium halide (7) may be dropped into a solution of tris (fluoroaryl) boron, or a solution of hydrocarbon magnesium halide (7) may be added to a solution of hydrocarbon magnesium halide (7).
A solution of tris (fluoroaryl) boron may be added dropwise. Further, a method in which a solution of tris (fluoroaryl) boron and a solution of hydrocarbon magnesium halide (7) are dropped into the solvent may be adopted.

The mixing temperature when mixing the solution of tris (fluoroaryl) boron and the solution of hydrocarbon magnesium halide (7) is not particularly limited,
-30 ° C or higher, more preferably not higher than the reflux temperature of the solvent, more preferably -20 ° C or higher, and still more preferably 200 ° C or lower of the lower of the reflux temperatures, and -10 ° C or higher. It is particularly preferred that the temperature is not higher than 150 ° C. or the lower of the reflux temperatures.

The reaction temperature of the above reaction is not particularly limited, but it is more preferably −30 ° C. or higher but not higher than the reflux temperature of the solvent. Is more preferably 30 ° C. or higher and 150 ° C. or lower of the reflux temperature. If the reaction temperature is lower than −30 ° C., the reaction may be extremely slow. On the other hand, if it exceeds 200 ° C. (or the above-mentioned reflux temperature), the fluoroaryl borate / magnesium halide derivative may be decomposed.

The reaction time and pressure of the above reaction are as follows:
The reaction temperature is not particularly limited, and depends on other reaction conditions such as the reaction temperature, the amount of tris (fluoroaryl) boron, the amount of hydrocarbon magnesium halide (7), the combination of both, and the composition of the solvent. The reaction may be appropriately set so that the reaction is completed. Therefore, the pressure may be any of normal pressure, pressurization, and pressure reduction. Further, the above reaction is desirably performed in an atmosphere of an inert gas such as a nitrogen gas. still,
Along with or after the reaction, if necessary, the solvent and / or the alkyl halide by-produced during the production of the fluoroarylmagnesium halide can be distilled off. Alternatively, the solvent exchange can be performed together with or after the reaction.

By performing the above Grignard reaction, a fluoroaryl borate / magnesium halide derivative represented by the general formula (8) is produced. According to the production method of the present invention, a fluoroaryl borate / magnesium halide derivative containing no impurities such as coloring components can be obtained.

Since the fluorinated aryl boron derivative obtained by the above reaction does not contain impurities such as coloring components, for example, a co-catalyst of a metallocene catalyst (polymerization catalyst) provided for a cationic complex polymerization reaction, It is a compound useful as a catalyst for photopolymerization and the like.

[0077]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 After sufficiently replacing the inside of a reaction vessel equipped with a thermometer, a dropping funnel, a stirrer, a nitrogen gas introducing pipe, and a reflux condenser with nitrogen gas, the reaction vessel was charged with hydrocarbon magnesium. 300 ml of a diethyl ether (chain ether solvent) solution containing 0.765 mol of methylmagnesium bromide as halide (2) was charged.
Further, 0.729 mol of bromopentafluorobenzene as an aryl halide fluoride was charged into the dropping funnel.

Then, bromopentafluorobenzene in the dropping funnel was added dropwise at room temperature over 90 minutes, and the mixture was further stirred for 30 minutes while maintaining the temperature at room temperature. Thus, pentafluorophenyl magnesium bromide as a fluorinated aryl magnesium halide was obtained as a colorless diethyl ether solution.

The yield of pentafluorophenylmagnesium bromide produced by the above reaction was determined by ¹⁹ F-NMR.
(Nuclear magnetic resonance) determined by measuring the spectrum. That is, ¹⁹ F-NMR was measured under predetermined conditions using p-fluorotoluene as an internal standard. In the measurement, trifluoroacetic acid was used as a standard substance, and the position of the signal was 0 ppm. Then, ¹⁹ resulting F
From the NMR chart, the integral value of the fluorine atom of p-fluorotoluene and the integral value of the fluorine atom at the ortho position of the pentafluorophenyl group in pentafluorophenylmagnesium bromide were determined, and pentafluorophenylmagnesium bromide was obtained from both integral values. Was calculated. As a result, the yield of pentafluorophenyl magnesium bromide was 93.5 mol% based on bromopentafluorobenzene.

Example 2 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.729 mol of ethyl magnesium bromide as a hydrocarbon magnesium halide (2) was added to the reaction vessel. Containing diethyl ether solution 3
00 ml was charged. Further, 0.729 mol of bromopentafluorobenzene was charged into the dropping funnel.

Then, at room temperature, bromopentafluorobenzene in the dropping funnel was added dropwise over 90 minutes, and the mixture was further stirred for 30 minutes while maintaining the temperature at room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless diethyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 95.0 mol% based on bromopentafluorobenzene.

Example 3 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.197 g of n-propylmagnesium bromide as hydrocarbon magnesium halide (2) was added to the reaction vessel. 100 ml of a diethyl ether solution containing moles were charged. Further, 0.182 mol of bromopentafluorobenzene was charged into the dropping funnel.

Next, bromopentafluorobenzene in the dropping funnel was added dropwise at room temperature over 2 hours, and the mixture was further stirred for 30 minutes while maintaining the temperature at room temperature. This allows
Pentafluorophenyl magnesium bromide was obtained as a colorless diethyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 92.2 mol% based on bromopentafluorobenzene.

Example 4 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, the reaction vessel was charged with n-bromide.
T-butyl methyl ether containing 0.0214 mol of -propylmagnesium (chain ether solvent)
22 ml of the solution were charged. In addition, 0.0184 mol of bromopentafluorobenzene was charged into the dropping funnel.

Next, bromopentafluorobenzene in the dropping funnel was added dropwise at room temperature over 45 minutes, and the mixture was further stirred for 3 hours while maintaining the temperature at room temperature. This allows
Pentafluorophenyl magnesium bromide was obtained as colorless t-butyl methyl ether.

The yield of pentafluorophenyl magnesium bromide produced by the above reaction was determined by the following method. That is, iodine 0.02 was added to the obtained reaction solution.
The reaction was carried out by dropping a solution of t-butyl methyl ether containing 5 moles of pentafluorophenylmagnesium bromide into pentafluorobenzene iodide, and the amount of pentafluorobenzene iodide produced was quantified by gas chromatography. As a result, the yield of pentafluorophenyl magnesium bromide was 95.4 mol% based on bromopentafluorobenzene.

Example 5 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.198 mol of ethyl magnesium bromide as a hydrocarbon magnesium halide (2) was added to the reaction vessel. 130 ml of a t-butyl methyl ether (chain ether solvent) solution containing the suspension was charged. Further, 0.182 mol of bromopentafluorobenzene was charged into the dropping funnel. Then, bromopentafluorobenzene in the dropping funnel was added dropwise over 45 minutes at room temperature, and the mixture was further stirred for 4 hours while maintaining the temperature at room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless t-butyl methyl ether solution. As a result of analysis by the same method as in Example 1, the yield of pentafluorophenylmagnesium bromide was 98.98% based on bromopentafluorobenzene.
It was 0 mol%.

Example 6 After the inside of the same reaction vessel as in Example 1 was sufficiently replaced with nitrogen gas, 0.088 mol of ethylmagnesium bromide was suspended and contained in the reaction vessel.
-Dimethoxyethane (chain ether solvent) solution 60
ml. Further, 0.081 mol of bromopentafluorobenzene was charged into the dropping funnel. Further, after 0.5 g of methyl iodide was charged using a micro syringe, the mixture was stirred at room temperature for 10 minutes. Next, bromopentafluorobenzene in the dropping funnel was added dropwise over 45 minutes, and the mixture was further stirred at room temperature for 4 hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless 1,2-dimethoxyethane solution. As a result of analysis by the same method as in Example 1, the yield of pentafluorophenylmagnesium bromide was 98.5 mol% based on bromopentafluorobenzene.

Example 7 After the inside of the same reaction vessel as in Example 1 was sufficiently replaced with nitrogen gas, n-bromide was added to the reaction vessel.
100 ml of a diisopropyl ether (chain ether solvent) solution containing 0.197 mol of -propylmagnesium suspended therein was charged. Further, 0.182 mol of bromopentafluorobenzene was charged into the dropping funnel.

Then, at room temperature, bromopentafluorobenzene in the dropping funnel was added dropwise over 10 minutes.
Stirred at 0 ° C. for a further 5 hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless diisopropyl ether solution. As a result of analysis by the same method as in Example 4, the yield of pentafluorophenylmagnesium bromide was 90.9 mol% based on bromopentafluorobenzene.

Example 8 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, diisopropyl ether (chain-like) containing 0.066 mol of ethylmagnesium bromide suspended in the reaction vessel was used. Ether solvent) solution 70m
l was charged. Further, 0.060 mol of bromopentafluorobenzene and 20 ml of diisopropyl ether (chain ether solvent) were charged into the dropping funnel. Next, a diisopropyl ether solution of bromopentafluorobenzene in the dropping funnel was dropped over 2 hours,
The mixture was further stirred for 12 hours while maintaining the room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless diisopropyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 94.3 mol% based on bromopentafluorobenzene.

Example 9 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, dipropyl ether (chain) containing 0.065 mol of ethylmagnesium bromide suspended in the reaction vessel was used. 50 ml of an ethereal solvent) solution. Further, 0.060 mol of bromopentafluorobenzene and 20 ml of dipropyl ether (chain ether solvent) were charged into the dropping funnel. Next, a dipropyl ether solution of bromopentafluorobenzene in the dropping funnel was added dropwise over 1 hour, and the mixture was further stirred for 2 hours while maintaining the room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless dipropyl ether solution. As a result of analysis by the same method as in Example 1, the yield of pentafluorophenylmagnesium bromide was 94.6 mol% based on bromopentafluorobenzene.

Example 10 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.188 mol of isopropylmagnesium bromide as a hydrocarbon magnesium halide (2) was added to the reaction vessel. 90 ml of a dibutyl ether (chain ether solvent) solution containing the suspension was charged. Further, 0.182 mol of bromopentafluorobenzene and 50 ml of dibutyl ether (chain ether solvent) were charged into the dropping funnel. Next, a dibutyl ether solution of bromopentafluorobenzene in the dropping funnel was added dropwise at room temperature over 2 hours, and the mixture was further stirred at 35 ° C for 2 hours. Thus, pentafluorophenyl magnesium bromide was obtained as a pale yellow dibutyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 9 based on bromopentafluorobenzene.
It was 7.5 mol%.

Example 11 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.0195 mol of phenylmagnesium bromide as a hydrocarbon magnesium halide (2) was added to the reaction vessel. 9 ml of a diethyl ether solution was charged. In addition, 0.0184 mol of bromopentafluorobenzene was charged into the dropping funnel.

Then, bromopentafluorobenzene in the dropping funnel was added dropwise at room temperature over 5 minutes, and the mixture was further stirred for 2.5 hours while maintaining the temperature at room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless diethyl ether solution. As a result of analysis in the same manner as in Example 4, the yield of pentafluorophenylmagnesium bromide was 78.0 mol% based on bromopentafluorobenzene.

Example 12 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.0188 mol of cyclohexylmagnesium bromide as hydrocarbon magnesium halide (2) was added to the reaction vessel. 20 ml of a diethyl ether solution was charged. In addition, 0.0186 mol of bromopentafluorobenzene was charged into the dropping funnel.

Next, bromopentafluorobenzene in the dropping funnel was added dropwise over 5 minutes at room temperature, and the mixture was further stirred for 2 hours while maintaining the temperature at room temperature. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless diethyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 88.5 mol% based on bromopentafluorobenzene.

Example 13 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 20 ml of a diethyl ether solution containing 0.0180 mol of ethylmagnesium bromide was charged into the reaction vessel. Also, in the dripping funnel,
0.017 mol of iodopentafluorobenzene as a halogenated aryl fluoride was charged.

Then, at room temperature, iodopentafluorobenzene in the dropping funnel was added dropwise over 30 minutes, and the mixture was further stirred at room temperature for 2 hours. This allows
Pentafluorophenyl magnesium bromide was obtained as a colorless diethyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 92.1 mol% based on iodopentafluorobenzene.

Example 14 After the inside of the same reaction vessel as in Example 1 was sufficiently substituted with nitrogen gas, 30 ml of a toluene solution containing 0.016 mol of bromopentafluorobenzene was charged into the reaction vessel. Further, 10 ml of a diethyl ether solution containing 0.0180 mol of ethylmagnesium bromide was charged into the dropping funnel.

Then, at room temperature, ethylmagnesium bromide in the dropping funnel was added dropwise over 30 minutes, and the mixture was further stirred at room temperature for 2 hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a colorless toluene-diethyl ether mixed solution. Example 1
As a result of analysis by the same method as in the above, the yield of pentafluorophenylmagnesium bromide was 91.9 mol% based on bromopentafluorobenzene.

Example 15 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, t-butyl containing 0.0199 mol of n-propylmagnesium bromide suspended in the reaction vessel was used. 20 ml of a methyl ether solution were charged. Further, 0.0183 mol of 1-bromo-2,3,5,6-tetrafluorobenzene as aryl halide fluoride was charged into the dropping funnel.

Then, at room temperature, 1-bromo-2,3,5,6-tetrafluorobenzene in the dropping funnel was added dropwise over 20 minutes, and the mixture was further stirred at room temperature for 4 hours. Thus, 2,3,5,6-tetrafluorophenyl magnesium bromide as a fluorinated aryl magnesium halide was obtained as a colorless t-butyl methyl ether solution. As a result of analysis in the same manner as in Example 1, the yield of 2,3,5,6-tetrafluorophenyl magnesium bromide was 1-bromo-2,3,3.
85.2 based on 5,6-tetrafluorobenzene
Mole%.

Example 16 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 9 ml of a diethyl ether solution containing 0.020 mol of n-propylmagnesium bromide was charged into the reaction vessel. It is. Also, 1-bromo- as halogenated aryl fluoride was added to the dropping funnel.
0.020 mol of 2,4,6-trifluorobenzene was charged.

Then, at room temperature, 1-bromo-2,4,6-trifluorobenzene in the dropping funnel was added dropwise over 15 minutes, and the mixture was further stirred at room temperature for 2 hours. Thus, 2,4,6-trifluorophenyl magnesium bromide as a fluorinated aryl magnesium halide was obtained as a colorless diethyl ether solution. As a result of analysis by the same method as in Example 1, 2, 4, 6
The yield of -trifluorophenylmagnesium bromide was 55.5 mol% based on 1-bromo-2,4,6-trifluorobenzene.

Comparative Example 1 After the inside of the same reaction vessel as in Example 1 was sufficiently replaced with nitrogen gas, 30 ml of a diethyl ether solution containing 0.066 mol of ethylmagnesium bromide was charged into the reaction vessel. Further, 0.060 mol of chloropentafluorobenzene was charged into the dropping funnel.

Next, chloropentafluorobenzene in the dropping funnel was added dropwise at room temperature over 15 minutes, and the reaction was continued for 8 hours while maintaining the reflux temperature (37 ° C.).
Stirred at room temperature for 10 hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a diethyl ether solution. As a result of analysis in the same manner as in Example 1,
The yield of pentafluorophenylmagnesium bromide was 21.21 based on chloropentafluorobenzene.
It was 6 mol%.

Comparative Example 2 After the inside of the same reaction vessel as in Example 1 was sufficiently replaced with nitrogen gas, n-bromide was added to the reaction vessel.
20 ml of a t-butyl methyl ether solution containing 0.0201 mol of -propylmagnesium suspended therein was charged.
In addition, 0.0182 mol of 1-bromo-4-fluorobenzene was charged into the dropping funnel.

Next, at room temperature, 1-bromo-4-fluorobenzene in the dropping funnel was added dropwise over 10 minutes, and then the reaction solution was heated to 56 ° C. and further stirred for 2 hours. The obtained reaction solution was analyzed in the same manner as in Example 1. However, the reaction solution did not contain 4-fluorophenylmagnesium bromide. That is, n-propylmagnesium bromide and 1-bromo-4-
It did not react with fluorobenzene.

Comparative Example 3 After the inside of the same reaction vessel as in Example 1 was sufficiently purged with nitrogen gas, n bromide was added to the reaction vessel.
20 ml of a diethyl ether solution containing 0.0201 mol of propylmagnesium were charged. Also, 1-bromo-2,6-difluorobenzene 0.018 was added to the dropping funnel.
2 moles were charged.

Next, 1-bromo-2,6-difluorobenzene in the dropping funnel was added dropwise over 10 minutes at room temperature, and the reaction solution was heated to 40 ° C. and stirred for another 2 hours. The obtained reaction solution was analyzed in the same manner as in Example 1. However, the reaction solution did not contain 2,6-difluorophenylmagnesium bromide. That is, n-propylmagnesium bromide and 1-bromo-2,6-difluorobenzene did not react.

Comparative Example 4 After the inside of the same reaction vessel as in Example 1 was sufficiently replaced with nitrogen gas, 0.051 mol of magnesium and 65 ml of dibutyl ether were charged into the reaction vessel and cooled to 5 ° C. . Further, 0.050 mol of bromopentafluorobenzene was charged into the dropping funnel. Further, 0.33 g (0.03 g) of ethyl bromide was placed in the reaction vessel.
03 mol: 6.1 based on bromopentafluorobenzene
Mol%) and stirred at room temperature for 1 hour. Then 4
After the bromopentafluorobenzene in the dropping funnel was added dropwise at 0 ° C over 1 hour, the reaction was further performed for 1 hour while maintaining the reaction solution at 40 ° C. Thereafter, the reaction solution was cooled to room temperature, and the obtained reaction solution was analyzed in the same manner as in Example 1. As a result, the yield of pentafluorophenyl magnesium bromide was 5.6 mol% based on bromopentafluorobenzene.

Example 17 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, the reaction vessel was charged with diethyl ether containing 0.056 mol of boron trifluoride-diethyl ether complex as a boron compound. 70 ml of an ether solution were charged. In addition, 120 ml of a diethyl ether solution containing 0.168 mol of pentafluorophenylmagnesium bromide as a fluoroarylmagnesium halide obtained in Example 3 was charged into the dropping funnel.

Next, the diethyl ether solution in the dropping funnel was added dropwise over 1 hour while stirring the diethyl ether solution in the reaction vessel at room temperature, and the reaction solution was heated and refluxed for 4 hours. Thereafter, the reaction solution was cooled to room temperature. Thus, tris (pentafluorophenyl) boron as tris (fluoroaryl) boron was obtained as a colorless diethyl ether solution.

As a result of analysis in the same manner as in Example 1, the yield of tris (pentafluorophenyl) boron was 93.6 mol% based on pentafluorophenylmagnesium bromide.

Example 18 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, the reaction vessel was charged with diisopropyl containing 0.017 mol of boron trifluoride-diethyl ether complex as a boron compound. Ether solution 20
ml. Further, 0.05 g of pentafluorophenyl magnesium bromide as a fluorinated aryl magnesium halide obtained in Example 6 was added to the dropping funnel.
Diisopropyl ether solution containing 7 mol suspended 10
0 ml was charged. Next, the diisopropyl ether solution in the dropping funnel was added dropwise over 1 hour while stirring the diisopropyl ether solution in the reaction vessel at room temperature, and the mixture was further reacted (aged) at 35 ° C. for 2 hours. afterwards,
The reaction was cooled to room temperature. Thus, a colorless diisopropyl ether solution of tris (pentafluorophenyl) boron was obtained.

As a result of analysis in the same manner as in Example 1, the yield of tris (pentafluorophenyl) boron was 57.1 mol% based on pentafluorophenylmagnesium bromide.

Example 19 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, the reaction vessel was charged with diisopropyl containing 0.019 mol of boron trifluoride-diethyl ether complex as a boron compound. Ether solution 20
ml, and 0.060 mol of diethyl ether. Further, a dropping funnel was charged with 100 ml of a diisopropyl ether solution containing 0.057 mol of pentafluorophenylmagnesium bromide as a fluoroarylmagnesium halide obtained in Example 8 suspended therein. Next, the diisopropyl ether solution in the dropping funnel was added dropwise over 1 hour while stirring the diisopropyl ether solution in the reaction vessel at room temperature, and the mixture was further reacted (aged) at 35 ° C. for 2 hours. Thereafter, the reaction solution was cooled to room temperature. Thus, tris (pentafluorophenyl) boron was obtained as a colorless diisopropyl ether solution.

As a result of analysis in the same manner as in Example 1, the yield of tris (pentafluorophenyl) boron was 93.3 mol% based on pentafluorophenylmagnesium bromide.

Example 20 After obtaining pentafluorophenylmagnesium bromide in Example 2, the following reaction was carried out (at 1 pot). That is, the inside of the reaction vessel used in Example 2 was sufficiently replaced with nitrogen gas.
The reaction vessel contained 400 ml of a diethyl ether solution containing 0.692 mol of pentafluorophenyl magnesium bromide. Also, 0.173 mol of boron trifluoride diethyl ether complex was charged into the dropping funnel.

Then, at room temperature, the boron trifluoride diethyl ether complex in the dropping funnel was added dropwise over 1.5 hours, and then dibutyl ether (chain ether solvent) was added.
0 ml was added to the reaction via the dropping funnel. Then, after adding dibutyl ether, the reaction solution was heated to 130 ° C.
The mixture was allowed to react (age) at elevated temperature, and diethyl ether and ethyl bromide by-produced during the synthesis of pentafluorophenyl magnesium bromide were distilled off at normal pressure. Thereafter, the reaction solution was cooled to room temperature. This allows
Tetrakis (pentafluorophenyl) as a tetrakis (fluoroaryl) borate / magnesium compound
Borate magnesium bromide was obtained as a colorless dibutyl ether solution.

As a result of analysis in the same manner as in Example 1, the yield of tetrakis (pentafluorophenyl) borate / magnesium bromide was 91.5 mol% based on pentafluorophenyl magnesium bromide.

Example 21 After obtaining pentafluorophenylmagnesium bromide in Example 10, the following reaction was carried out (at 1 pot). That is, the reaction vessel used in Example 10 contained 170 ml of a dibutyl ether solution containing 0.177 mol of pentafluorophenyl magnesium bromide. In addition, a boron trifluoride diethyl ether complex 0.04
5 moles were charged. Further, the reflux condenser was replaced with a distillation apparatus.

Next, while stirring the dibutyl ether solution in the reaction vessel at room temperature, the boron trifluoride diethyl ether complex in the dropping funnel was added dropwise over 1 hour.
The isopropyl bromide by-produced during the synthesis of pentafluorophenylmagnesium bromide was distilled off while reacting (aging) at 00 ° C. for another 2 hours. Thereafter, the reaction solution was cooled to room temperature. Thus, tetrakis (pentafluorophenyl) borate / magnesium bromide was obtained as a colorless dibutyl ether solution. Example 1
As a result of analysis in the same manner as in the above, the yield of tetrakis (pentafluorophenyl) borate / magnesium bromide was 90.2 mol% based on pentafluorophenylmagnesium bromide.

Example 22 After sufficiently replacing the inside of the same reaction vessel with nitrogen gas as in Example 1, the reaction vessel was charged with 0.010 g of p-fluorophenylmagnesium bromide as hydrocarbon magnesium halide (7). 20 ml of a diethyl ether solution containing moles were charged. Further, a dropping funnel was charged with 16 ml of a diethyl ether solution containing 0.010 mol of tris (pentafluorophenyl) boron as tris (fluoroaryl) boron obtained in Example 17.

Next, the diethyl ether solution in the dropping funnel was added dropwise over 5 minutes while stirring the diethyl ether solution in the reaction vessel at room temperature.
And stirred for an additional 3 hours. Thereafter, the reaction solution was cooled to room temperature. As a result, p-fluorophenyl-tris (pentafluorophenyl) borate / magnesium bromide as a fluoroaryl borate / magnesium halide derivative was obtained as a colorless diethyl ether solution.

As a result of analysis in the same manner as in Example 1, p
The yield of -fluorophenyl-tris (pentafluorophenyl) borate magnesium bromide is p-
86.3 mol% based on fluorophenylmagnesium bromide.

Comparative Example 5 After the inside of the same reaction vessel as in Example 1 was sufficiently substituted with nitrogen gas, 0.188 mol of magnesium and 65 g of diethyl ether were charged into the reaction vessel. Further, 0.182 mol of bromopentafluorobenzene was charged into the dropping funnel. Next, bromopentafluorobenzene in the dropping funnel was added dropwise over 3 hours at room temperature while stirring the diethyl ether in the reaction vessel, and the mixture was reacted (aged) at reflux temperature (39 ° C.) for 2 hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a black diethyl ether solution.
As a result of analysis in the same manner as in Example 1, the yield of pentafluorophenylmagnesium bromide was 97.5 mol% based on bromopentafluorobenzene.

After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.060 mol of a boron trifluoride-diethyl ether complex and diethyl ether 48
g. In addition, the above-mentioned diethyl ether solution of pentafluorophenyl magnesium bromide was charged into the dropping funnel. Next, a diethyl ether solution of pentafluorophenylmagnesium bromide in the dropping funnel was added dropwise over 1 hour at room temperature while stirring the diethyl ether in the reaction vessel, followed by reaction (aging) at 35 ° C. for 2 hours. Thereafter, the reaction solution was cooled to room temperature.
As a result of analysis by the same method as in Example 1, the yield of tris (pentafluorophenyl) boron was 87.6 mol% based on bromopentafluorobenzene,
The obtained diethyl ether solution of tris (pentafluorophenyl) boron was colored black.

Comparative Example 6 After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 50 ml of a tetrahydrofuran solution containing 0.018 mol of ethylmagnesium bromide was charged into the reaction vessel. Further, 0.018 mol of bromopentafluorobenzene was charged into the dropping funnel. Next, while stirring the tetrahydrofuran solution in the reaction vessel at room temperature, bromopentafluorobenzene in the dropping funnel was added dropwise over 10 minutes.
Reacted for hours. Thereby, pentafluorophenyl magnesium bromide was obtained as a pale yellow solution of tetrahydrofuran. As a result of analysis in the same manner as in Example 1,
The yield of pentafluorophenylmagnesium bromide was 93.% based on bromopentafluorobenzene.
9 mol%.

After sufficiently replacing the inside of the same reaction vessel as in Example 1 with nitrogen gas, 0.0056 mol of boron trifluoride tetrahydrofuran complex and 50 ml of tetrahydrofuran were charged into the reaction vessel. Further, the above-mentioned tetrahydrofuran solution of pentafluorophenyl magnesium bromide was charged into the dropping funnel. Then, a tetrahydrofuran solution of pentafluorophenyl magnesium bromide in the dropping funnel in the dropping funnel was added dropwise over 1 hour while stirring the tetrahydrofuran in the reaction vessel at room temperature.
The reaction (aging) was performed at 5 ° C. for 2 hours. Thereafter, the reaction solution was cooled to room temperature. As a result of analysis in the same manner as in Example 1,
The yield of tris (pentafluorophenyl) boron was 35.4 mol% based on bromopentafluorobenzene. Further, the obtained mixed solution of tris (pentafluorophenyl) boron in tetrahydrofuran-diethyl ether was pale yellow, but contained many by-products.

[0133]

By employing the method for producing a fluoroarylmagnesium halide according to the present invention, a fluoroarylmagnesium halide containing no impurities such as coloring components can be safely produced by a milder reaction than the conventional method. To
There is an effect that it can be manufactured efficiently and industrially. Since the production method according to the present invention reacts a hydrocarbon magnesium halide with a halogenated aryl fluoride in a solvent containing a chain ether solvent, for example, a conventional production method in which bromopentafluorobenzene is reacted with magnesium. The reaction heat is lower than the method. Therefore, the reaction proceeds gently, and it is easy to control the reaction. The fluorinated arylmagnesium halide obtained by the above production method is a compound useful as a Grignard reagent used in various organic synthesis reactions.

Further, a method for producing a fluoroaryl boron derivative according to the present invention, that is, using a fluoroarylmagnesium halide obtained by the above production method,
By employing a method for producing tris (fluoroaryl) borane, tetrakis (fluoroaryl) borate / magnesium compound, and a fluoroarylborate / magnesium halide derivative, arylboron fluoride containing no impurities such as coloring components This has the effect that the derivative can be produced efficiently and easily with high purity. The fluoroaryl boron derivative obtained by the above-mentioned production method is a compound useful as, for example, a co-catalyst of a metallocene catalyst used for a cationic complex polymerization reaction, a catalyst for photopolymerization of silicone, and the like.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ikuno Ikuyo 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Naoko Hirano 5-8 Nishi-Mabori-cho, Suita-shi, Osaka Within Nippon Shokubai (72) Inventor Yukiko Ariyoshi 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the R _{1 to} R ₅ 3
One is a fluorine atom, and X _a represents a chlorine atom, a bromine atom or an iodine atom), and is a method for producing a fluorinated arylmagnesium halide represented by the following general formula (2): R ₆ MgX _a. 2) wherein R ₆ represents a hydrocarbon group, X _a represents _a chlorine atom, a bromine atom or an iodine atom, and a hydrocarbon magnesium halide represented by the general formula (3): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the R _{1 to} R ₅ 3
Is a fluorine atom, and X _b represents a bromine atom or an iodine atom), and reacted with a halogenated aryl fluoride in a solvent containing a chain ether solvent. A method for producing magnesium halide. 2. A fluorinated aryl magnesium halide obtained by the production method according to claim 1, and B (X _C ) ₃ (4) wherein X _C is a fluorine atom or chlorine. (Representing an atom, a bromine atom, an iodine atom or an alkylalkoxy group) with a boron compound represented by the general formula (5): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the R _{1 to} R ₅ 3
Is a fluorine atom). 3. A fluorinated aryl magnesium halide obtained by the production method according to claim 1, and B (X _C ) ₃ (4) wherein X _C is a fluorine atom, chlorine (Representing an atom, a bromine atom, an iodine atom or an alkylalkoxy group) with a boron compound represented by the general formula (6): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the R _{1 to} R ₅ 3
One is a fluorine atom, X _C is a fluorine atom, a chlorine atom,
A tetrakis (fluoroaryl) borate / magnesium compound represented by a bromine atom, an iodine atom or an alkylalkoxy group). 4. Tris (fluoroaryl) boron obtained by the production method according to claim 2, and R ₇ MgX _d ... (7) wherein R ₇ represents a hydrocarbon group. , X _d represents a chlorine atom, a bromine atom or an iodine atom), and is reacted with a hydrocarbon magnesium halide represented by the following general formula (8): (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least one of the R _{1 to} R ₅ 3
One is a fluorine atom, R ₇ represents a hydrocarbon group, and X _d
Represents a chlorine atom, a bromine atom or an iodine atom).