JP2002226491A - Method for producing fluorinated aryl metal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fluorinated aryl metal compound, with which an impurity-free fluorinated aryl metal compound such as bis(pentafluorophenyl)dialkyltin, etc., having a slight discoloration, can be simply and inexpensively produced and purified. SOLUTION: The fluorinated aryl metal compound is obtained by reacting a hydrocarbon magnesium halide with a halogenated fluoroaryl in a solvent containing an ether-based solvent to give a fluorinated aryl magnesium halide, and reacting the fluorinated aryl magnesium halide with an organometallic compound. Tin is more preferable as a metal atom contained in the organometallic compound. A chain-type ether solvent is preferable as the ether- based solvent, more concretely, diisopropyl ether, dibutyl ether and t-butyl methyl ether are more preferable. Preferably a magnesium halide being a by- product of the fluorinated aryl metal is precipitated and removed or treated with an acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to, for example, bis (pentafluorophenyl) dimethyltin and bis (pentafluorophenyl) dimethyltin useful as intermediates for pharmaceuticals and agrochemicals, polymerization catalysts, polymerization co-catalysts, catalysts for photopolymerization of silicone, etc. The present invention relates to a method for producing a fluorinated aryl metal compound such as (pentafluorophenyl) dibutyltin.

[0002]

2. Description of the Related Art Fluorinated aryl metal compounds such as bis (pentafluorophenyl) dimethyltin and bis (pentafluorophenyl) dibutyltin are, for example, intermediates for pharmaceuticals and agricultural chemicals, polymerization catalysts, polymerization co-catalysts, and photopolymerization catalysts for silicone. And compounds useful as intermediates thereof.

For example, in J. Chem. Soc., (1964) 4782, pentafluorophenyl magnesium bromide (Grignard reagent) obtained by reacting bromopentafluorobenzene with magnesium using diethyl ether as a solvent And a method of reacting dimethyltin dibromide at reflux temperature for 2 days to synthesize bis (pentafluorophenyl) dimethyltin with a yield of 58%.

[0004] For example, see Japanese Patent Application Laid-Open No. 2000-19166.
No. 6 discloses that a Grignard exchange reaction between a hydrocarbon magnesium halide such as methylmagnesium bromide and an aryl halide fluoride such as bromopentafluorobenzene is carried out in a solvent containing a chain ether solvent. A method is disclosed for safely, efficiently and industrially producing a fluorinated arylmagnesium halide containing no impurities such as coloring components by a milder reaction than in the past.

Further, for example, Organometallics., (1998)
In 5492, bromopentafluorobenzene and butyllithium were used with -78
A method of synthesizing bis (pentafluorophenyl) dimethyltin at a yield of 95% by reacting pentafluorophenyllithium and dimethyltin dichloride obtained at a temperature of −78 ° C. at −78 ° C. is disclosed.

[0006]

However, the above-mentioned J.
In the method described in Chem. Soc., (1964) 4782, since diethyl ether which is a compound having a low boiling point is used as a solvent, it is difficult to control the temperature of the reaction system, and the flammability is high. There is a problem that special care is required for handling. In addition, a diethyl ether solution of pentafluorophenylmagnesium bromide obtained by reacting bromopentafluorobenzene with magnesium is colored black due to impurities generated by a side reaction or the like. For this reason, bis (pentafluorophenyl) dimethyltin obtained by reacting the above-mentioned pentafluorophenylmagnesium bromide with dimethyltin dibromide is colored black. ,
It is necessary to distill the reaction solution containing the compound.

Further, in the above-mentioned production method, when pentafluorophenylmagnesium bromide is reacted with dimethyltin dibromide, magnesium dibromide which is a magnesium halide is produced together with bis (pentafluorophenyl) dimethyltin which is a target substance. It is by-produced. However, since magnesium dibromide is soluble in a solvent such as diethyl ether, it is necessary to remove magnesium dibromide from the solution in order to purify bis (pentafluorophenyl) dimethyltin. J. Chem. Soc., (1964) 4782 discloses a method for removing a magnesium halide by treating a reaction solution containing the magnesium halide with aqueous ammonium chloride. However, when the reaction solution is treated with aqueous ammonium chloride, there is a problem that it is difficult to separate an organic layer and an aqueous layer. Therefore, J. Chem.
The production method described in Soc., (1964) 4782 cannot be said to be an industrially advantageous method. In addition, when a fluoroaryl metal compound containing magnesium halide as an impurity is used, for example, as a polymerization catalyst, the activity of the catalyst is significantly reduced.

The problem described in J. Chem. Soc., (1964) 4782, in which pentafluorophenylmagnesium bromide is colored by impurities generated by a side reaction or the like, is described in Japanese Patent Application Laid-Open No. 2000-191666. In the method for producing an aryl magnesium halide,
The problem can be solved by obtaining a pentafluorophenyl magnesium bromide containing no impurities such as coloring components by a Grignard exchange reaction. However, JP-A-2000-191666 discloses that further reaction of tin with a fluorinated arylmagnesium halide is disclosed.
Further, there is no description that a fluoroaryl magnesium halide can be used as a raw material as a specific intermediate of a fluoroaryl metal compound.

On the other hand, in the production method described in Organometallics., (1998) 5492, it is necessary to cool the reaction system to -78 ° C., and therefore, it is difficult to carry out the method industrially.

[0010] Therefore, a method for easily and inexpensively producing and purifying a fluorinated aryl metal compound has been desired. That is, the present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to provide a method capable of easily and inexpensively producing and purifying a less-colored arylfluorometal compound containing no impurities. Is to provide.

[0011]

According to the present invention, in order to solve the above problems, pentafluorophenylmagnesium bromide, which is an intermediate in the process of synthesizing bis (pentafluorophenyl) dialkyltin, which is the final product, is synthesized. In doing so, various synthetic routes different from the above-mentioned conventional synthetic reaction were examined. As a result, the reaction reached another synthesis route in which side reactions are less likely to occur and less coloring due to generated impurities. Another synthetic route is specifically to carry out a Grignard exchange reaction. Then, the intermediate pentafluorophenylmagnesium bromide, which has been synthesized by another synthesis route (Grignard exchange reaction), is further reacted with dialkyltin dichloride to obtain the final target bis (pentafluorophenyl) dialkyl. A new synthetic route to obtain tin efficiently and with less coloring could be devised.

The intermediate fluorinated arylmagnesium halide, specifically pentafluorophenylmagnesium bromide, is difficult to cause a side reaction in the synthetic route employed in the present invention, so that pentafluorophenylmagnesium is obtained. Bromide is not colored. Therefore, it is not necessary to purify pentafluorophenyl magnesium bromide, and it can be used in the next step. In addition, when the organometallic compound is further reacted with the above-mentioned fluorinated arylmagnesium halide, even if a series of steps, specifically, a continuous step is performed, it is possible to obtain a fluorinated arylmetal compound which is the final target product with little coloring. This is a very useful synthesis route that can also simplify the series of steps. That is, in the production method of the present invention, without purifying the intermediate, a fluoroarylmagnesium halide, specifically, pentafluorophenylmagnesium bromide,
By further reacting the organometallic compound as a series of steps, it is possible to obtain the final desired product, that is, a fluorinated arylmetal compound, specifically, a bis (pentafluorophenyl) dialkyltin. A more specific configuration is presented below.

The general formula (5) of the present invention

[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 which are fluorine atoms, M represents a metal atom belonging to Group IV, R ⁶ represents a hydrocarbon group, and n is 1 to 3). In order to solve the above-mentioned problem, the method is based on the general formula (1) R ⁷ MgX _a (1) (wherein R ⁷ represents a hydrocarbon group, and X _a is a chlorine atom, a bromine atom or an iodine atom) A hydrocarbon magnesium halide represented by the general formula (2):

[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 At least three of which are fluorine atoms, and X _c represents a bromine atom or an iodine atom), and a halogenated aryl halide represented by the general formula: Equation (3)

[0018]

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[0019] ^{(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, Xa represents a chlorine atom, a bromine atom or an iodine atom), and a general formula (4) (R ⁶ ) _4-n M (X _b ) _n (4) (wherein, R ⁶ represents a hydrocarbon group, n is 1 to 3,
M represents a metal atom belonging to Group IV, and _Xb represents a halogen atom).

In order to solve the above-mentioned problems, the method for producing a fluoroaryl metal compound of the present invention is further characterized in that the metal atom contained in the organometallic compound is tin.

In order to solve the above-mentioned problems, the method for producing a fluoroaryl metal compound of the present invention further comprises the step of further preparing bis (pentafluorophenyl)
It is characterized by being a dialkyl tin.

In order to solve the above-mentioned problems, the process for producing a fluoroaryl metal compound of the present invention further comprises the above-mentioned fluoroaryl metal compound and MgX _a X _b as a by-product represented by the following general formula (6): MgX _a X _b. (6) wherein X _a represents a chlorine atom, a bromine atom or an iodine atom, and X _b represents a halogen atom, and a magnesium halide represented by the following formula is obtained as a solution in an ether solvent. It is characterized in that magnesium halide is precipitated and removed.

In order to solve the above-mentioned problems, the method for producing a fluoroaryl metal compound of the present invention further comprises adding an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent to the ether solvent. It is characterized in that the magnesium halide is precipitated and removed by adding one kind of solvent selected from hydrogen-based solvents.

In order to solve the above-mentioned problems, the method for producing a fluoroaryl metal compound of the present invention further comprises the general formula (6) MgX _a X _b . ... (6) wherein X _a represents a chlorine atom, a bromine atom or an iodine atom, and X _b represents a halogen atom, to obtain a magnesium halide solution represented by the following formula: It is characterized by being treated with an acid.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The process for producing a fluoroaryl metal compound according to the present invention is characterized in that hydrofluoric acid is obtained by reacting a hydrocarbon magnesium halide with a halogenated aryl fluoride in a solvent containing an ether solvent. Is a method of reacting an aryl magnesium halide with an organometallic compound.

The hydrocarbon magnesium halide used as a starting material in the present invention is represented by the following general formula (1): R ⁷ MgX _a (1) (wherein R ⁷ represents a hydrocarbon group, X _a is a chlorine atom, A bromine atom or an iodine atom). In the formula, the hydrocarbon group represented by R ⁷ specifically includes an aryl group such as a phenyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, and a cyclic group having 3 to 12 carbon atoms. An alkyl group, and a linear or branched alkenyl group having 2 to 12 carbon atoms, or 3 to 1 carbon atoms.
2 represents a cyclic alkenyl group. As the above alkyl group, specifically, a methyl group, an ethyl group, a propyl group,
Examples include isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, t-pentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As the above alkenyl group, specifically,
An allyl group is mentioned. Among the above exemplified hydrocarbon groups,
Phenyl group, ethyl group, propyl group, isopropyl group,
A cyclohexyl group and an allyl group are more preferred. The above-mentioned hydrocarbon group is a functional group containing an atom inert to the reaction and purification (treatment) according to the present invention, for example, a fluorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, and the like. It may further have a functional group. As the functional group, specifically, a methoxy group, a methylthio group, an N, N-
Examples include a dimethylamino group, an o-anis group, a p-anis group, a trimethylsilyloxy group, a dimethyl-t-butylsilyloxy group, and a trifluoromethyl group.

The above-mentioned hydrocarbon magnesium halide, which is a Grignard reagent, can be easily obtained, for example, by reacting a corresponding halogenated hydrocarbon with magnesium using a general technique. As the hydrocarbon magnesium halide, for example,
Hydrocarbon magnesium bromide such as ethyl magnesium bromide is exemplified.

The aryl halide fluoride used as a starting material in the present invention has the general formula (2)

[0029]

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(Wherein, R ^{1 to} R ⁵ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least three of the R ^{1 to} R ⁵ are fluorine atoms. _Xc represents a bromine atom or an iodine atom)
It is a compound represented by these. In the formula, the hydrocarbon group in the substituents represented by R ^{1 to} R ⁵ is specifically an aryl group such as a phenyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, A cyclic alkyl group having 3 to 12 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or a cyclic alkenyl group having 3 to 12 carbon atoms. As the above alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, t-pentyl group, hexyl group, octyl group Groups, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Specific examples of the above alkenyl group include an allyl group. In addition, the above-mentioned hydrocarbon group is a functional group containing an atom, a fluorine atom, a nitrogen atom, an oxygen atom, a sulfur atom, and the like that are inert to the reaction and purification (treatment) according to the present invention, It may further have a group. As the functional group, specifically, a methoxy group, a methylthio group,
Examples include an N, N-dimethylamino group, an o-anis group, a p-anis group, a trimethylsilyloxy group, a dimethyl-t-butylsilyloxy group, and a trifluoromethyl group.

In the formula, the alkoxy group in the substituents represented by R ^{1 to} R ⁵ is represented by the following general formula (A) —OR _a (where R _a represents _a hydrocarbon group). Where R _a
Are specifically an aryl group such as a phenyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, and A linear or branched alkenyl group having 2 to 12 carbon atoms, or a cyclic alkenyl group having 3 to 12 carbon atoms. In addition, the above-mentioned hydrocarbon group may further have a functional group which is inert to the reaction and the purification (treatment) according to the present invention. Specific examples of the alkoxy group represented by the general formula (A) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a t-butoxy group. Group, cyclohexyloxy group, allyloxy group,
And phenoxy groups.

Accordingly, as the halogenated aryl fluoride, specifically, bromopentafluorobenzene, iodopentafluorobenzene, 1-bromo-2,3,4,
5-tetrafluorobenzene, 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, and 1-iodo -3,4,5-trifluorobenzene.

The ether solvent contained in the solvent used for reacting the hydrocarbon magnesium halide with the halogenated aryl fluoride is, specifically, dimethyl ether, diethyl ether, dipropyl ether,
Diisopropyl ether, dibutyl ether, diisobutyl ether, di-t-butyl ether, dipentyl ether, dihexyl ether, dioctyl ether, t
-Butyl methyl ether, dimethoxymethane, diethoxymethane, 1,2-dimethoxyethane, and 1,2-
A chain ether solvent of diethoxyethane; tetrahydrofuran, tetrahydropyran, 1,4-dioxane,
And a cyclic ether solvent of 1,3-dioxolane;
Aromatic ether solvents of anisole and phenetole; and the like. One of these ether solvents may be used alone, or two or more thereof may be used in combination. Among the ether solvents exemplified above, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, di-t-butyl ether are useful in terms of convenience of the solvent, ease of reaction, yield, separation of the target product, and the like. , T-butyl methyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, anisole and phenetole are more preferred.

Examples of other solvents that can be used in combination with the ether-based solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane; cyclopentane, cyclohexane, cycloheptane, and An alicyclic hydrocarbon solvent of methylcyclohexane; an aromatic hydrocarbon solvent of benzene, toluene, and xylene; and the like, but any compound that does not inhibit the reaction according to the present invention can be used. Expar, a commercially available hydrocarbon solvent, Isopar
Hydrocarbon solvents such as C, IsoparE, and IsoparG (all are registered trademarks) may be used. Further, as a solvent containing an ether-based solvent, a solvent used when a halogenated hydrocarbon is reacted with magnesium to form the above-mentioned hydrocarbon magnesium halide can also be used.

In general, when a fluoroarylmagnesium halide is prepared by reacting a halogenated arylfluoride with magnesium, the reaction does not proceed (reactivity decreases) in a solvent such as diisopropyl ether or dibutyl ether. Usually, diethyl ether or tetrahydrofuran is used as a solvent. However, the Grignard exchange reaction between the hydrocarbon magnesium halide and the halogenated aryl fluoride in the production method according to the present invention proceeds even in a solvent such as diisopropyl ether or dibutyl ether. Therefore, it is not necessary to use a low-boiling point compound such as diethyl ether or ring-opening polymerizable tetrahydrofuran as a solvent. Further, by performing the Grignard exchange reaction, a less colored arylmagnesium halide can be prepared. As a result, a less colored arylfluorometal compound can be obtained.

As a method of mixing the above-mentioned hydrocarbon magnesium halide with the aryl halide fluoride, for example, a method of dropping a solution of the hydrocarbon magnesium halide into the aryl halide halide or a solution thereof; , And a method of dropping an aryl halide or a solution thereof and a solution of a hydrocarbon magnesium halide into a solvent. be able to.

The reaction conditions for the above reaction are more preferably such that the molar ratio between the hydrocarbon magnesium halide and the halogenated aryl halide is in the range of 0.8: 1 to 2.0: 1, and 0.9 : 1 to 1.5: 1. Further, the amount of the solvent used is more preferably such that the concentration of the obtained fluoroarylmagnesium halide is in the range of 0.1% by weight to 80% by weight, and more preferably 1.0% to 70% by weight. More preferably, the amount falls within the range. The lower limit of the reaction temperature is -30.
C. or higher, more preferably -20.degree. C. or higher. The upper limit of the reaction temperature is more preferably equal to or lower than the reflux temperature of the above-mentioned solvent, and when the reflux temperature exceeds 200 ° C, further preferably equal to or lower than 200 ° C. The reaction time may be set as appropriate according to the combination of the hydrocarbon magnesium halide and the halogenated aryl fluoride, the reaction temperature, and the like. further,
The above reaction is desirably performed in an atmosphere of an inert gas such as nitrogen gas. The fluorinated arylmagnesium halide is obtained in the form of a reaction solution (solution or suspension) dissolved or suspended in the above solvent. The halogenated hydrocarbon (R ⁷ X _c ) by-produced together with the fluoroarylmagnesium halide can be used in the next reaction without removing it from the reaction system. May be removed.

The organometallic compound used as a raw material in the present invention is represented by the general formula (4) (R ⁶ ) _4-n M (X _b ) _n (4) (wherein R ⁶ represents a hydrocarbon group) , N is 1-3,
M represents a metal atom belonging to Group IV, and _Xb represents a halogen atom). In the formula, examples of the hydrocarbon group represented by R ⁶ include the same substituents as the hydrocarbon group represented by R ⁷ . Among the substituents, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group are more preferred. In the formula, tin is particularly preferable as a metal atom belonging to Group IV (short-period type; Group 4 and Group 14 in long-period type) represented by M. Further, X _b in the organometallic compound is more preferably a chlorine atom or a bromine atom. Further, n in the formula is more preferably 2. Examples of the organometallic compound include dimethyltin dichloride, diethyltin dichloride, dibutyltin dichloride, dimethyltin dibromide, diethyltin dibromide, and organometallic chlorides of dibutyltin dibromide.

By reacting the fluoroarylmagnesium halide obtained by the above method with an organometallic compound in a solvent, the compound represented by the general formula (5)

[0040]

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(Wherein, R ^{1 to} R ⁵ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and at least three of the R ^{1 to} R ⁵ are fluorine atoms. And M represents a metal atom belonging to Group IV; R ⁶ represents a hydrocarbon group; and n is 1 to 3).

The method of mixing the fluorinated arylmagnesium halide and the organometallic compound is a method of adding the organometallic compound to a solution of the fluorinated arylmagnesium halide, ie, the reaction solution obtained by the above reaction; And a method of adding the reaction solution obtained by the above reaction to the above. The organometallic compound may be in the form of a solution diluted with a solvent or a suspended suspension.

The reaction conditions for the above reaction are such that the molar ratio of the fluoroaryl magnesium halide to the organometallic compound is
It is more preferably in the range of 0.1: 1 to 10: 1, and even more preferably in the range of 0.5: 1 to 5: 1. Further, the amount of the solvent used is more preferably such that the concentration of the target fluoroaryl metal compound is in the range of 0.1% by weight to 80% by weight, and more preferably 1.0% by weight to 70% by weight. % Is more preferable. The lower limit of the reaction temperature is more preferably -30 ° C or higher, and further preferably -20 ° C or higher. The upper limit of the reaction temperature is more preferably equal to or lower than the reflux temperature of the above-mentioned solvent, and when the reflux temperature exceeds 200 ° C, further preferably equal to or lower than 200 ° C. The reaction time may be appropriately set according to the combination of the fluoroarylmagnesium halide and the organometallic compound, the reaction temperature, and the like. The fluorinated aryl metal compound is
It is obtained in the state of a reaction solution dissolved in the above solvent. The above reaction is desirably performed in an atmosphere of an inert gas such as nitrogen gas.

The fluorinated aryl metal compound obtained by the above method is a metal compound having at least one fluorinated aryl group in which at least three of the hydrogen atoms in the aryl group are substituted with fluorine atoms. As the fluorinated aryl group, a pentafluorophenyl group is more preferred. Further, n in the above formula is more preferably 2. Therefore, the fluoroaryl metal compound is
Bis (pentafluorophenyl) dialkyltin such as bis (pentafluorophenyl) dimethyltin and bis (pentafluorophenyl) dibutyltin is particularly preferred.

In the above method, together with the target fluoroaryl metal compound, a general formula (6) MgX _a X _b (6) (wherein X _a represents a chlorine atom, a bromine atom or an iodine atom) , X _b represents a halogen atom) as a by-product, a solution of a fluoroaryl metal compound and a magnesium halide in an ether-based solvent, or a suspension in which a magnesium halide is precipitated. Obtained as a suspension.

Specific examples of the magnesium halide include magnesium fluoride chloride, magnesium fluoride bromide, magnesium fluoride iodide, magnesium dichloride, magnesium chloride bromide, magnesium chloride iodide,
It is at least one compound selected from magnesium dibromide, magnesium bromide, and magnesium diiodide. The production method of the present invention is applicable to a reaction system in which these are mixed.

As the ether solvent contained in the solution containing the aryl metal fluoride compound and the magnesium halide, specifically, the hydrocarbon magnesium halide is reacted with the halogenated aryl fluoride. An ether-based solvent contained in the solvent used at that time is exemplified.

To remove the magnesium halide from this solution, when obtained as a solution,
In a preferred embodiment, (A) the magnesium halide is precipitated and precipitated as a solid to remove it, or (B) it is purified by treatment with an acid. Further, when obtained as a suspension, (C) filtration or (B)
A preferred form is purification by treatment with an acid. Only one of these processes may be performed, or two or more of these processes may be performed in combination.

(A) Specific methods for depositing and precipitating magnesium halide as a solid include, for example,
A method of mixing a solvent that does not dissolve magnesium halide (hereinafter, referred to as solvent A) with the above-mentioned solvent; a residue obtained by distilling an ether-based solvent from the above-mentioned solution (concentrated liquid)
And a solvent A; a solvent having a boiling point higher than the boiling point of the ether solvent contained in the solution and not dissolving the magnesium halide (hereinafter referred to as a solvent B); After mixing, the ether solvent is distilled off from the mixture, and if necessary, the concentrated solution is cooled;
After heating the solvent B to a temperature higher than the boiling point of the ether solvent contained in the solution, the solvent B is heated to a temperature higher than the boiling point of the ether solvent contained in the solution. A method in which the ether solvent is distilled off while adding the solution, and the concentrated solution is cooled if necessary.

Examples of the solvent A and the solvent B include aliphatic hydrocarbon solvents such as pentane, hexane, heptane and octane; and alicyclic solvents such as cyclopentane, cyclohexane, cycloheptane and methylcyclohexane. Hydrocarbon solvents; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; ether solvents such as diisopropyl ether and dibutyl ether; One of these solvents A and B may be used alone, or two or more thereof may be used in combination. The amount of the solvent A or the solvent B to be used with respect to the solvent may be an amount that enables efficient purification. When two or more solvents A and B are used in combination, the proportion of each solvent can be appropriately set. Examples of the solvent A and the solvent B include commercially available hydrocarbon solvents such as IsoparC and IsoparC.
A hydrocarbon-based mixed solvent such as parE and IsoparG may be used.

In the above method, the solution and the solvent A
May be added to the solution, or the solution may be added to the solvent A. The temperature at which the solution and the solvent A are mixed is, specifically, −100 ° C.
~ 200 ° C, more preferably -50 ° C.
More preferably, it is in the range of from 150C to 150C. More preferably, it is in the range of −20 ° C. to 120 ° C.

In the above method, as a method of mixing the solution and the solvent B, the solvent B may be added to the solution, or the solution may be added to the solvent B. Moreover, the temperature at the time of mixing the solution and the solvent B is, specifically, −100 ° C.
More preferably within the range of 200C, -50C
More preferably, it is in the range of 150 to 150 ° C.

In the above methods (1) to (4), as a method of distilling off the ether solvent, a method of heating a solution or a mixed solution under normal pressure (atmospheric pressure) may be employed. A method of heating the solution or mixture under pressure or under pressure may be employed. When the ether-based solvent is distilled off under normal pressure, the heating temperature may be at least the boiling point of the ether-based solvent. Further, in the above method, the cooling temperature in the case of cooling the concentrated solution obtained by distilling the ether-based solvent may be set so that the magnesium halide is sufficiently precipitated.

By carrying out the above-mentioned methods and the like, the magnesium halide can be precipitated and precipitated as a solid. The magnesium halide can be separated and removed by filtering a solution (concentrated liquid) containing the fluoroaryl metal compound and the solvent A or the solvent B. Thereby, a fluoroaryl metal compound can be easily and inexpensively produced. That is, a high-purity aryl metal compound containing no impurities can be obtained easily and at low cost.

(B) As a specific method of treating with an acid, the above solution or suspension and an aqueous solution containing an acid are mixed and stirred, and then the mixture is allowed to stand. And an aqueous layer containing a magnesium halide and an acid, and removing the solution. The magnesium halide dissolves in an aqueous solution containing an acid, but the aryl metal fluoride compound does not dissolve in the aqueous solution.

As the above-mentioned acids, inorganic acids and / or organic acids can be used. Specifically, hydrochloric acid, sulfuric acid, nitric acid,
Inorganic acids such as phosphoric acid and carbonic acid; and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, malonic acid, and succinic acid. One of these acids may be used alone, or two or more of them may be used in combination, for example, by combining an inorganic acid and an organic acid. Acids that can be used in the present invention include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, formic acid, acetic acid, propionic acid, oxalic acid, malonic acid,
And at least one acid selected from succinic acid. Further, among the acids exemplified above, at least one acid selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, malonic acid, and succinic acid is more preferable. The amount of the acid to be used is preferably 0.01 equivalent or more, more preferably 0.1 equivalent or more, with respect to the magnesium halide contained in the solution so that the purification can be performed efficiently. The concentration of the acid in the aqueous solution and the method for adjusting the aqueous solution containing the acid can be set as appropriate. In addition, when two or more kinds of acids are used in combination, the ratio of each acid can be appropriately set.

In the above method, as a method of mixing the solution with an aqueous solution containing an acid, the aqueous solution may be added to the solution, or the solution may be added to the aqueous solution. Also,
The temperature at which the solution and the aqueous solution containing the acid are mixed and stirred,
It is preferable that the temperature is higher than the temperature at which the aryl fluoride metal compound is precipitated from the solution and lower than the temperature at which the aryl fluoride metal compound decomposes. Specifically, -100C to 20C
The range of 0 ° C is preferred, the range of -50 ° C to 150 ° C is more preferred, and the range of -20 ° C to 100 ° C is even more preferred. The time for mixing the solution with the aqueous solution containing an acid can be set as appropriate.

When the organic layer and the aqueous layer are separated, a simple operation such as a liquid separation (oil / water separation) operation may be performed. The method for removing, that is, the method for removing the magnesium halide and the acid is not limited to the above method. When an acid is contained in the organic layer, if necessary, the organic layer can be easily washed with water, for example, using an aqueous solution of sodium carbonate, an aqueous solution of sodium hydrogen carbonate, or an aqueous solution of sodium hydroxide. You just need to do the operation. When the aqueous layer contains a fluoroaryl metal compound, a simple operation such as extraction (recovery) from the aqueous layer using an appropriate solvent may be performed as necessary. Furthermore, when water is contained in the organic layer, a desiccant such as anhydrous magnesium sulfate may be added to the organic layer to remove (dry) as necessary. Incidentally, the method of treating the solution with an acid, such as the above method, may be repeated as necessary so that the magnesium halide contained in the solution is sufficiently removed.

By carrying out the above-mentioned methods and the like, the magnesium halide can be separated and removed.
Thereby, a fluoroaryl metal compound can be easily and inexpensively produced. That is, a high-purity aryl metal compound containing no impurities can be obtained easily and at low cost.

[0060]

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. In addition, NMR (nuclear magnetic resonance) spectrum data in the examples uses tetramethylsilane (TMS) as a standard substance in the case of ¹ H-NMR spectrum data and trifluoroacetic acid in the case of ¹⁹ F-NMR spectrum data. It was measured as a standard. And
The signal of the standard substance was set to 0 ppm.

Example 1 A reaction process via a fluoroarylmagnesium halide obtained by a Grignard exchange reaction will be described.

A reactor equipped with a reflux condenser, a thermometer, a dropping funnel, a nitrogen gas inlet tube and a stirrer was charged with 3.23 g (0.133 mol) of magnesium, and the inside was sufficiently purged with nitrogen gas. Next, 150 ml of diisopropyl ether as a solvent was charged into the reactor, and 13.43 g (0.123 mol) of ethyl bromide was charged into the dropping funnel. Ethyl bromide was added dropwise from the dropping funnel over 2 hours while stirring the contents of the reactor at room temperature under a nitrogen gas atmosphere. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes to be aged. On the other hand, 29.99 g of bromopentafluorobenzene as a halogenated aryl fluoride was added to the dropping funnel.
(0.121 mol).

Next, bromopentafluorobenzene was added dropwise from the dropping funnel over 2 hours while stirring the contents of the reactor at room temperature under a nitrogen gas atmosphere. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes to be aged. This gave pentafluorophenyl magnesium bromide as a suspension in isopropyl ether. The reaction was not colored. After aging, 17.54 g of dibutyltin dichloride as an organometallic compound was added to the reactor.
(058 mol) and stirred at room temperature for 3 hours.

After completion of the reaction, the deposited precipitate (magnesium chlorobromide) was removed by filtration. Next, 100 ml of hexane was added to the residue obtained by concentrating the filtrate to precipitate impurities contained in the residue, followed by filtration to remove the impurities. Then, the filtrate was concentrated to obtain 31.24 g of bis (pentafluorophenyl) dibutyltin as a fluoroaryl metal compound as a colorless liquid.

As a result of analysis with a ¹⁹ F-NMR apparatus, the yield of bis (pentafluorophenyl) dibutyltin was 95.4% based on dibutyltin dichloride, and the purity was 99.5%.
2%. The NMR spectrum data of the obtained bis (pentafluorophenyl) dibutyltin is ¹ H-NMR (benzene-d ₆ , δ): 0.84 (6
H, t, J = 7.2 Hz), 1.26 (4H, m),
1.50 (8H, m) ¹⁹ F-NMR (benzene-d ₆ , δ): −45.7,
-74.4, -83.6.

Example 2 A reaction step via a fluoroarylmagnesium halide obtained by a Grignard exchange reaction will be described.

In the same first reactor as in Example 1, 10.00 g (0.411 mol) of magnesium was charged, and the inside of the reactor was sufficiently purged with nitrogen gas. Next, 300 ml of dibutyl ether as a solvent was charged into the first reactor, and 39.70 g (0.364 mol) of ethyl bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and while maintaining the internal temperature at 30 ° C to 40 ° C, ethyl bromide was added dropwise from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 30 minutes to be aged. On the other hand, 90.00 g of bromopentafluorobenzene was added to the dropping funnel.
(0.364 mol).

Next, the contents of the first reactor were stirred under a nitrogen gas atmosphere, and the internal temperature was maintained at 30 ° C. to 40 ° C.
Bromopentafluorobenzene was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour and aged. As a result, a dibutyl ether solution of pentafluorophenyl magnesium bromide was obtained.

Subsequently, 38.60 g of dimethyltin dichloride as an organometallic compound was placed in the same second reactor as in Example 1.
(0.176 mol), and the inside was sufficiently purged with nitrogen gas. Next, 100 ml of dibutyl ether was added to the second reactor.
And the dibutyl ether solution of pentafluorophenylmagnesium bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the second reactor were stirred, and the dibutyl ether solution was added dropwise from the dropping funnel over 2 hours while maintaining the internal temperature at 30 ° C to 40 ° C. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour.

After completion of the reaction, the precipitated precipitate (magnesium chlorobromide) was removed by filtration to obtain bis (pentafluorophenyl) dimethyltin as a colorless dibutyl ether solution as a fluoroaryl metal compound. The reaction yield was analyzed with a ¹⁹ F-NMR device. That is, using the p- fluorotoluene as an internal standard, ¹⁹
F-NMR was measured under predetermined conditions. And got
^{From the 19} F-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 bis (pentafluorophenyl) dimethyltin were determined. The amount of (pentafluorophenyl) dimethyltin was calculated. As a result, the yield of bis (pentafluorophenyl) dimethyltin was 9% based on dimethyltin dichloride.
The purity was 7.5% and the purity was 99.0%.

Example 3 A reaction step via a fluorinated arylmagnesium halide obtained by Grignard exchange reaction is described.

In the same first reactor as in Example 1, 5.00 g (0.206 mol) of magnesium was charged, and the inside of the reactor was sufficiently purged with nitrogen gas. Next, 150 ml of dibutyl ether was charged into the first reactor, and 19.81 g (0.182 mol) of ethyl bromide was charged into the dropping funnel. In a nitrogen gas atmosphere, the contents of the first reactor were stirred, and the internal temperature was 30 ° C.
Ethyl bromide was added from the dropping funnel while maintaining
It was dropped over time. After the completion of dropping, the same temperature is added for another 30 minutes.
Stir for minutes and ripen. On the other hand, 45.00 g (0.182 mol) of bromopentafluorobenzene was added to the dropping funnel.
Was charged.

Next, the contents of the first reactor were stirred under a nitrogen gas atmosphere, and the internal temperature was maintained at 30 ° C. to 40 ° C.
Bromopentafluorobenzene was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour and aged. As a result, a dibutyl ether solution of pentafluorophenyl magnesium bromide was obtained.

Subsequently, 19.30 g (0.088 mol) of dimethyltin dichloride was charged into the same second reactor as in Example 1, and the inside of the reactor was sufficiently purged with nitrogen gas. Next, 100 ml of hexane as a solvent was charged into the second reactor, and the above dibutyl ether solution of pentafluorophenylmagnesium bromide was charged into the dropping funnel. In a nitrogen gas atmosphere, the contents of the second reactor were stirred, and the internal temperature was reduced to 30 ° C.
While maintaining the temperature at 滴下 40 ° C., the dibutyl ether solution was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour.

After the completion of the reaction, the deposited precipitate (magnesium chlorobromide) was removed by filtration. Next, 100 ml of hexane was added to the residue obtained by distilling off the solvent in the filtrate under reduced pressure to precipitate impurities contained in the residue, and the impurities were removed by filtration. Then, the filtrate is concentrated to obtain bis (pentafluorophenyl) dimethyltin 3
9.5 g were obtained as a colorless liquid. As a result of analysis with a ¹⁹ F-NMR apparatus, the yield of bis (pentafluorophenyl) dimethyltin was found to be 93.0% based on dimethyltin dichloride.
0% and purity was 98.5%.

Example 4 A reaction step via a fluoroarylmagnesium halide obtained by a Grignard exchange reaction is described.

The same first reactor as in Example 1 was charged with 5.00 g (0.206 mol) of magnesium, and the inside was sufficiently purged with nitrogen gas. Next, 88 g of t-butyl methyl ether was charged into the first reactor, and 21.47 g (0.197 mol) of ethyl bromide was charged into the dropping funnel.
Under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and while maintaining the internal temperature at 30 ° C to 40 ° C, ethyl bromide was added dropwise from the dropping funnel over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the above temperature for 2 hours and aged. Meanwhile, 45.0 g (0.18 g) of bromopentafluorobenzene was added to the dropping funnel.
2 mol).

Next, the contents of the first reactor were stirred under a nitrogen gas atmosphere, and the internal temperature was maintained at 30 ° C. to 40 ° C.
Bromopentafluorobenzene was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 2 hours to be aged. Thereby, pentafluorophenyl magnesium bromide was obtained as a suspension of t-butyl methyl ether. The reaction was not colored.

The reactor was charged with t-butyl methyl ether 80.
g, and 19.30 g (0.088 mol) of dimethyltin dichloride as an organometallic compound was added thereto, followed by stirring at room temperature for 3 hours.

After completion of the reaction, the precipitated precipitate (magnesium chlorobromide) was removed by filtration to obtain bis (pentafluorophenyl) dimethyltin as a fluorinated aryl metal compound as a t-butyl methyl ether solution. . As a result of analysis in the same manner as in Example 2, the yield of bis (pentafluorophenyl) dimethyltin was 96.3% based on dimethyltin dichloride, and the purity was 99.9%.
It was 0%.

Example 5 A reaction step via a fluorinated arylmagnesium halide obtained by Grignard exchange reaction is described.

4.78 g (0.197 mol) of magnesium was charged into the same first reactor as in Example 1, and the inside of the reactor was sufficiently purged with nitrogen gas. Next, 70 g of diethyl ether was charged into the first reactor, and 21.47 g (0.197 mol) of ethyl bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and while maintaining the internal temperature at the reflux temperature of ether, ethyl bromide was added dropwise from the dropping funnel over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the above temperature for 2 hours and aged. Meanwhile, 45.0 g (0.182 mol) of bromopentafluorobenzene was charged into the dropping funnel.

Then, under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and while maintaining the internal temperature at the reflux temperature of ether, 3 parts of bromopentafluorobenzene was added from the dropping funnel.
It was added dropwise over 0 minutes. After completion of the dropping, the temperature is further increased by 2
Stirred for hours and aged. As a result, a diethyl ether solution of pentafluorophenyl magnesium bromide was obtained. The reaction was not colored.

Subsequently, 19.24 g of dimethyltin dichloride as an organometallic compound was placed in the same second reactor as in Example 1.
(0.088 mol), and the inside was sufficiently purged with nitrogen gas. Next, 70 g of diethyl ether was charged into the second reactor, and the diethyl ether solution of pentafluorophenylmagnesium bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the second reactor were stirred, and while maintaining the internal temperature at the reflux temperature of ether, a diethyl ether solution was added dropwise from the dropping funnel over 2 hours.
After completion of the dropwise addition, the mixture was further stirred at the above temperature for 1 hour. In this way, bis (pentafluorophenyl) dimethyltin as a fluoroaryl metal compound was obtained as a colorless diethyl ether solution containing magnesium chlorobromide in a dissolved state. As a result of analysis in the same manner as in Example 2,
The yield of bis (pentafluorophenyl) dimethyltin was 92.8% based on dimethyltin dichloride, and the purity was 9%.
It was 8.4%.

Example 6 A reaction step via a fluoroarylmagnesium halide obtained by Grignard exchange reaction is described.

In the same first reactor as in Example 1, 4.78 g (0.197 mol) of magnesium was charged, and the inside was sufficiently purged with nitrogen gas. Next, 70 g of diethyl ether was charged into the first reactor, and 24.23 g (0.197 mol) of n-propyl bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and while maintaining the internal temperature at the reflux temperature of ether, bromide was added from the dropping funnel.
-Propyl was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the above temperature for 2 hours and aged. On the other hand, 45.0 g of bromopentafluorobenzene (0.
182 mol).

Then, the contents of the first reactor were stirred under a nitrogen gas atmosphere, and bromopentafluorobenzene was added through a dropping funnel while maintaining the internal temperature at the reflux temperature of ether.
It was added dropwise over 0 minutes. After completion of the dropping, the temperature is further increased by 2
Stirred for hours and aged. As a result, a diethyl ether solution of pentafluorophenyl magnesium bromide was obtained.

Subsequently, 19.26 g of dimethyltin dichloride as an organometallic compound was placed in the same second reactor as in Example 1.
(0.088 mol), and the inside was sufficiently purged with nitrogen gas. Next, 70 g of diethyl ether was charged into the second reactor, and the diethyl ether solution of pentafluorophenylmagnesium bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the second reactor were stirred, and while maintaining the internal temperature at the reflux temperature of ether, a diethyl ether solution was added dropwise from the dropping funnel over 2 hours.
After completion of the dropwise addition, the mixture was further stirred at the above temperature for 1 hour. In this way, bis (pentafluorophenyl) dimethyltin as a fluoroaryl metal compound was obtained as a colorless diethyl ether solution containing magnesium chlorobromide in a dissolved state. As a result of analysis in the same manner as in Example 2,
The yield of bis (pentafluorophenyl) dimethyltin was 93.2% based on dimethyltin dichloride, and the purity was 9%.
It was 8.6%.

Example 7 A reaction step via a fluoroarylmagnesium halide obtained by Grignard exchange reaction is described.

In the same first reactor as in Example 1, 5.00 g (0.206 mol) of magnesium was charged, and the inside was sufficiently purged with nitrogen gas. Next, 150 ml of dibutyl ether was charged into the first reactor, and 21.22 g (0.195 mol) of ethyl bromide was charged into the dropping funnel. In a nitrogen gas atmosphere, the contents of the first reactor were stirred, and the internal temperature was 30 ° C.
While maintaining the temperature at -40 ° C, 3 mL of ethyl bromide was
It was added dropwise over 0 minutes. After completion of the dropwise addition, the mixture was further stirred at the above temperature for 2 hours and aged. Meanwhile, 45.0 g (0.182 mol) of bromopentafluorobenzene was added to the dropping funnel.
Was charged.

Next, the contents of the first reactor were stirred under a nitrogen gas atmosphere, and the internal temperature was maintained at 30 ° C. to 40 ° C.
Bromopentafluorobenzene was dropped from the dropping funnel over 30 minutes. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 2 hours to be aged. Thus, pentafluoromagnesium bromide was obtained as a solution of dibutyl ether.
The reaction was not colored.

Subsequently, 19.12 g (0.087 mol) of dimethyltin dichloride was charged into the same second reactor as in Example 1, and the inside thereof was sufficiently purged with nitrogen gas. Next, 100 ml of dibutyl ether as a solvent was charged into the second reactor, and the above dibutyl ether solution of pentafluorophenyl magnesium halide was charged into a dropping funnel. Under a nitrogen gas atmosphere, the contents of the second reactor were stirred, and the dibutyl ether solution was added dropwise from the dropping funnel over 2 hours while maintaining the internal temperature at 30 ° C to 40 ° C. After completion of the dropwise addition, the mixture was further stirred at the same temperature for 1 hour.

Next, 250 g of a 1M aqueous hydrochloric acid solution was charged into the dropping funnel as an aqueous solution containing an acid. While stirring the contents of the reactor, the aqueous solution in the dropping funnel was added dropwise over 1 hour while maintaining the temperature at 40 ° C. or lower. After dropping,
The contents of the reactor were transferred to a separating funnel, allowed to stand, separated into an organic layer and an aqueous layer, and the aqueous layer was extracted. Thus, bis (pentafluorophenyl) dimethyltin as a fluoroaryl metal compound was obtained as a dibutyl ether solution. As a result of analysis in the same manner as in Example 2, the yield of bis (pentafluorophenyl) dimethyltin was 95.3% based on dimethyltin dichloride, and the purity was 9%.
It was 8.8%.

Comparative Example 1 9.73 g (0.400 mol) of magnesium was charged into the same first reactor as in Example 1, and
The inside was sufficiently purged with nitrogen gas. Next, 300 ml of diethyl ether as a solvent was charged into the first reactor, and 90.00 g (0.364 g) of bromopentafluorobenzene as a halogenated fluoroaryl was added to the dropping funnel.
Mol). Under a nitrogen gas atmosphere, the contents of the first reactor were stirred, and the internal temperature was adjusted to the reflux temperature of diethyl ether (3.
(5 ° C.), bromopentafluorobenzene was added dropwise from the dropping funnel over 2 hours. After the completion of the dropwise addition, the mixture was further stirred at the same temperature for 3 hours and aged. This allows
A solution of pentafluorophenyl magnesium bromide in diethyl ether was obtained.

Subsequently, 38.60 g (0.176 mol) of dimethyltin dichloride was charged into the same second reactor as in Example 1, and the inside was sufficiently purged with nitrogen gas. Next, 100 ml of diethyl ether was charged into the second reactor, and the above-mentioned diethyl ether solution of pentafluorophenylmagnesium bromide was charged into the dropping funnel. Under a nitrogen gas atmosphere, the contents of the second reactor were stirred, and a diethyl ether solution was added dropwise from the dropping funnel over 2 hours while maintaining the internal temperature at the reflux temperature of diethyl ether. After dropping,
The mixture was further stirred at the same temperature for 1 hour.

Thus, the bis (pentafluorophenyl)
G) Dimethyltin dissolved in magnesium chlorobromide
Obtained as a diethyl ether solution containing in a state. But
However, the diethyl ether solution has a
Therefore, it was colored black. ¹⁹Analyze with F-NMR equipment
Results in bis (pentafluorophenyl) dimethyltin
Is 87.9% based on dimethyltin dichloride.
there were.

[0097]

As described above, the process for producing a fluoroaryl metal compound of the present invention is obtained by reacting a hydrocarbon magnesium halide with a halogenated aryl fluoride in a solvent containing an ether solvent. And a reaction between the fluorinated aryl magnesium halide and the organometallic compound.

As described above, the method for producing a fluorinated aryl metal compound of the present invention has a configuration in which the metal atom contained in the organometallic compound is tin. As described above, the method for producing a fluoroaryl metal compound of the present invention includes:
Furthermore, the structure is such that the fluoroaryl metal compound is bis (pentafluorophenyl) dialkyltin.

Therefore, a Grignard exchange reaction is performed to prepare a fluorinated arylmagnesium halide.
A less colored fluoroaryl metal compound can be obtained. Thereby, it is possible to easily and inexpensively produce a less-colored fluoroaryl metal compound, and it is possible to easily and inexpensively isolate and purify the compound.

As described above, the process for producing a fluorinated aryl metal compound of the present invention further comprises obtaining the fluorinated aryl metal compound and a magnesium halide obtained as a by-product as a solution in an ether-based solvent. This is a configuration in which the magnesium halide is precipitated from the liquid and removed. As described above, the method for producing a fluorinated aryl metal compound of the present invention is further selected from an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent, and an aromatic hydrocarbon solvent as the ether solvent. By adding one kind of solvent, the above-mentioned magnesium halide is precipitated and removed.

As described above, the process for producing a fluorinated aryl metal compound of the present invention further comprises obtaining the fluorinated aryl metal compound and a magnesium halide obtained as a by-product as a solution in an ether-based solvent. The reaction liquid is treated with an acid.

Therefore, the fluoroaryl metal compound as a target and the magnesium halide as a by-product can be easily separated, so that impurities can be easily removed. Thereby, it is possible to easily and inexpensively produce a less-colored fluorinated aryl metal compound containing no impurities, and to easily and inexpensively isolate and purify.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshiya Iida 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Toshimitsu Moriguchi 5-8 Nishi-Maburi-cho, Suita-shi, Osaka F-term in Nippon Shokubai (reference) 4H049 VN03 VP01 VQ11 VR24 VS09 VU36 VV01 VV06 VW02 VW07 VW38

Claims (6)

[Claims] 1. A compound represented by the general formula (1): R ⁷ MgX _a (1) wherein R ⁷ represents a hydrocarbon group and X _a represents _a chlorine atom, a bromine atom or an iodine atom. A hydrocarbon magnesium halide, and a compound represented by the general formula (2): (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 Three are fluorine atoms, and X _c represents a bromine atom or an iodine atom) and a halogenated aryl fluoride 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 Three are fluorine atoms, Xa represents _a chlorine atom, a bromine atom or an iodine atom), and a general formula (4) (R ⁶ ) _4-n M (X _b ) _n (4) (wherein, R ⁶ represents a hydrocarbon group, n is 1 to 3,
M represents a metal atom belonging to Group IV, and X _b represents a halogen atom), and is reacted with an organometallic compound represented by the following 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 Three are fluorine atoms, M represents a metal atom belonging to Group IV, R ⁶ represents a hydrocarbon group, and n is 1 to 3). 2. The method according to claim 1, wherein the metal atom contained in the organometallic compound is tin. 3. The method for producing a fluoroaryl metal compound according to claim 1, wherein the fluoroaryl metal compound is bis (pentafluorophenyl) dialkyltin. 4. The above-mentioned fluorinated aryl metal compound and, as a by-product, a compound represented by the following general formula (6): MgX _a X _b (6) wherein X _a represents a chlorine atom, a bromine atom or an iodine atom; _{2. The} aryl fluoride according to claim 1, wherein a magnesium halide represented by the following formula ( _b is a halogen atom) is obtained as a solution in an ether solvent, and the magnesium halide is precipitated and removed from the reaction solution. A method for producing a metal compound. 5. The magnesium halide by adding one kind of solvent selected from an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent to the ether solvent. 5. The method for producing a fluoroaryl metal compound according to claim 4, wherein is precipitated and removed. 6. The fluorinated aryl metal compound and a by-product represented by the following general formula (6): MgX _a X _b (6) wherein X _a represents a chlorine atom, a bromine atom or an iodine atom; _The method for producing a fluoroaryl metal compound according to claim 1, wherein a magnesium halide represented by the formula ( _b is a halogen atom) is obtained as a solution in an ether solvent, and the reaction solution is treated with an acid.