JPH09227574A - Production of fluoroarylmagnesium derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject derivative useful as e.g. a fluoroarylating reagent by reaction between a specific fluoroaryl compound, a halohydrocarbon and magnesium in an ether-based solvent or mixed solvent of an ether-based solvent with a hydrocarbon-based solvent. SOLUTION: This fluoroarylmagnesium derivative (e.g. pentafluorophenylmagnesium bromide) useful as e.g. a fluoroarylating reagent is obtained efficiently and easily at low cost by reaction between a fluoroaryl compound of formula I (R1 -R3 are each H, F, a hydrocarbon or alkoxy)(e.g. pentafluorobenzene), a halohydrocarbon of the formula R0 X (R0 is a hydrocarbon; X is Cl, Br or I) (e.g. isopropyl bromide) and magnesium in an ether-based solvent (e.g. diethyl ether) or mixed solvent of an ether-based solvent with a hydrocarbon-based solvent (e.g. toluene) at >=30 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fluorinated arylmagnesium derivative which is suitable as a reactant (organic synthesis reagent) for introducing aryl fluoride into various organic compounds.

[0002]

2. Description of the Related Art Fluorinated arylmagnesium derivatives, which are a type of Grignard reagents, are useful, for example, as reagents (organic synthesis reagents) for introducing aryl fluoride into various organic compounds. In addition, the fluorinated arylmagnesium derivative has recently attracted particular attention as a raw material for synthesizing a tris (fluoroaryl) boron compound useful as a cocatalyst for a metallocene catalyst (polymerization catalyst).

As a method for obtaining the above fluorinated arylmagnesium derivative, for example, J. Org. Chem., 29, 2385.
In (1964), an alkylmagnesium derivative such as ethylmagnesium bromide (EtMgBr) is added dropwise to a solution prepared by dissolving pentafluorobenzene in an ether solvent such as tetrahydrofuran (THF) to cause a reaction with an aryl fluoride. A method for obtaining a pentafluorophenyl magnesium derivative as a magnesium derivative is described. In addition, for example, in JP-A-6-247976, a solution prepared by mixing an alkyl magnesium derivative in an ether solvent is added dropwise to a solution prepared by dissolving pentafluorobenzene in an ether solvent to cause a reaction. , A method for obtaining pentafluorophenyl magnesium derivatives is described.

In these methods, a pentafluorophenyl magnesium derivative is obtained by performing an exchange reaction for exchanging an alkyl group in the alkyl magnesium derivative for a pentafluorophenyl group.

[0005]

However, in the above conventional method, the pentafluorophenyl magnesium derivative is obtained by once forming the alkyl magnesium derivative and then performing the above exchange reaction. That is, before obtaining the pentafluorophenyl magnesium derivative,
Since the alkyl magnesium derivative has to be prepared separately, the reaction process has two steps.

The present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to efficiently and simply and inexpensively produce a fluorinated arylmagnesium derivative by making the reaction process substantially one step. It is to provide a method that can be manufactured.

[0007]

Means for Solving the Problems The inventors of the present invention have made extensive studies as to a method for producing a fluorinated arylmagnesium derivative, and as a result, fluorinated aryl, a halogenated hydrocarbon, and magnesium, in an ether solvent, or By reacting in a mixed solvent of an ether solvent and a hydrocarbon solvent, the reaction step can be substantially performed in one step, which makes the fluorinated arylmagnesium derivative efficient and simple and inexpensive. The present invention has been completed by discovering that the present invention can be manufactured.

That is, in order to solve the above-mentioned problems, the method for producing a fluorinated arylmagnesium derivative according to the first aspect of the present invention comprises

[0009]

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(Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and X represents a chlorine atom, a bromine atom or an iodine atom). And a general formula (1).

[0011]

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## STR1 ## wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and a general formula (2) R ₀ X (2) (in the formula, R ₀ represents a hydrocarbon group, and X represents a chlorine atom, a bromine atom, or an iodine atom), and magnesium, and an ether solvent. It is characterized in that the reaction is carried out in a medium or in a mixed solvent of an ether solvent and a hydrocarbon solvent.

According to the method of the first aspect, the reaction process can be substantially one step. As a result, the fluorinated arylmagnesium derivative can be efficiently and easily manufactured at low cost.

Further, in order to solve the above-mentioned problems, the method for producing a fluorinated arylmagnesium derivative according to a second aspect of the present invention is the method for producing a fluorinated arylmagnesium derivative according to the first aspect, wherein an ether solvent, Alternatively, in a mixed solvent of an ether solvent and a hydrocarbon solvent,
It is characterized in that after mixing the aryl fluoride and magnesium, the halogenated hydrocarbon is mixed.

In order to solve the above-mentioned problems, the method for producing a fluorinated arylmagnesium derivative according to a third aspect of the present invention is the method for producing a fluorinated arylmagnesium derivative according to the first or second aspect, wherein an ether solvent, Alternatively, in a mixed solvent of an ether solvent and a hydrocarbon solvent,
It is characterized in that the mixing temperature for mixing the halogenated hydrocarbon is not less than -20 ° C and not more than the reflux temperature of the solvent.

In order to solve the above problems, the method for producing a fluorinated arylmagnesium derivative according to the invention of claim 4 is the method for producing a fluorinated arylmagnesium derivative according to claim 1, 2 or 3, wherein the reaction temperature is But 30
It is characterized in that the temperature is not lower than 0 ° C and not higher than the reflux temperature of the solvent.

In order to solve the above-mentioned problems, the method for producing a fluorinated arylmagnesium derivative according to the fifth aspect of the present invention is the method for producing a fluorinated arylmagnesium derivative according to the first, second, third, or fourth aspect. It is characterized in that the ratio of halogenated hydrocarbon to aryl fluoride is 0.5 equivalent or more and the ratio of magnesium to aryl fluoride is 0.5 equivalent or more.

According to the above method, the fluorinated arylmagnesium derivative can be produced more efficiently and easily.

A method for producing a fluorinated arylmagnesium derivative according to a sixth aspect of the present invention is, in order to solve the above-mentioned problems, a method for producing a fluorinated arylmagnesium derivative according to the first, second, third, fourth or fifth aspect. In the above, the aryl fluoride is pentafluorobenzene.

According to the above method, the pentafluorophenylmagnesium derivative can be produced efficiently, easily and inexpensively.

The present invention will be described in detail below. The method for producing a fluorinated arylmagnesium derivative represented by the general formula (3) according to the present invention includes an aryl fluoride represented by the general formula (1) and a halogen represented by the general formula (2). It is a method of reacting a modified hydrocarbon with magnesium in an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent.

The aryl fluoride represented by the general formula (1) used as a starting material in the present invention is represented by the following formula:
A compound in which the substituents represented by R ₁ , R ₂ and R ₃ are each independently composed of a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group.

The above-mentioned hydrocarbon group is specifically 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. , A branched or cyclic alkenyl group 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 functional group include a methoxy group, a methylthio group, an N, N-dimethylamino group, an o-anis group, and a p-type group.
—Anis group, trimethylsilyl group, dimethyl-t-butylsilyloxy group, trifluoromethyl group and the like.

The above alkoxy group is represented by the general formula (4) --OR ₄ (4) (wherein R ₄ represents a hydrocarbon group), and in the formula, R
_The hydrocarbon group represented by 4 specifically includes, 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. Group, branched chain, or cyclic alkenyl group. 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 (4) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec- Examples thereof include butoxy group, t-butoxy group, cyclohexyloxy group, allyloxy group and phenoxy group.

Specific examples of the above aryl fluorides include pentafluorobenzene, 1,2,3,5.
-Tetrafluorobenzene, 1,2,4,5-tetrafluorobenzene, 1,2,4-trifluorobenzene,
1,3,5-trifluorobenzene, 1,3-difluorobenzene, 2,3,5,6-tetrafluorotoluene, 2,3,4,6-tetrafluorotoluene, 2,
3,5-trifluorotoluene, 2,4,6-trifluorotoluene, 2,4-difluorotoluene, 2,3
5,6-tetrafluoroanisole, 2,3,4,6-
Tetrafluoroanisole, 2,4,5-trifluoroanisole, 2,4,6-trifluoroanisole,
Examples thereof include 2,4-difluoroanisole and 3,5-difluoroanisole.

In the halogenated hydrocarbon represented by the general formula (2), in the formula, X is a chlorine atom, a bromine atom or an iodine atom, and the substituent represented by R ₀ is a hydrocarbon group. It is a compound. The above hydrocarbon group is specifically, for example, an aryl group, a straight chain having 1 to 12 carbon atoms, a branched chain, or a cyclic alkyl group, and a straight chain having 2 to 12 carbon atoms, A branched chain or cyclic alkenyl group and the like are shown. 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 functional group include methoxy group, methylthio group, N, N-dimethylamino group, o-
Examples thereof include anis group, p-anis group, trimethylsilyl group, dimethyl-t-butylsilyloxy group and trifluoromethyl group.

Specific examples of the above-mentioned halogenated hydrocarbon include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide and n-chloride.
Propyl, n-propyl bromide, n-propyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, n-butyl chloride, n-butyl bromide, n-butyl iodide, isobutyl chloride, isobutyl bromide, iodine Isobutyl iodide, sec-butyl chloride, sec-butyl bromide, iodide sec
-Butyl, t-butyl chloride, t-butyl bromide, t-iodide
-Butyl, hexyl chloride, hexyl bromide, hexyl iodide, cyclohexyl chloride, cyclohexyl bromide, cyclohexyl iodide, allyl chloride, allyl bromide, allyl iodide, benzene chloride, benzene bromide, benzene iodide, etc. . Of the above exemplified halogenated hydrocarbons, ethyl chloride, ethyl bromide, ethyl iodide, isopropyl chloride, isopropyl bromide, isopropyl iodide, allyl chloride, allyl bromide and allyl iodide are particularly preferred. Also,
Two or more kinds of halogenated hydrocarbons may be appropriately mixed and used, if necessary.

The ratio of the halogenated hydrocarbon to the fluorinated aryl is not particularly limited, but is preferably 0.5 equivalent or more, more preferably within the range of 0.5 equivalent to 3.0 equivalent, and 0. The range of 0.8 equivalent to 1.5 equivalents is particularly preferable. When the proportion of the halogenated hydrocarbon is less than 0.5 equivalent, unreacted aryl fluoride increases,
It may not be possible to efficiently produce the arylmagnesium fluoride derivative.

The above magnesium is preferably in a shape having a relatively large surface area such as powder, granules, flakes (ribbon shape) or the like so that the reaction can proceed more easily. The ratio of magnesium to aryl fluoride is not particularly limited, but is preferably 0.5 equivalent or more, more preferably 0.5 equivalent to 3.0 equivalent, and more preferably 0.8 equivalent to 1 equivalent. Particularly preferred is a range of 5 equivalents. If the proportion of magnesium is less than 0.5 equivalents, the amount of unreacted aryl fluoride increases, and the fluorinated aryl magnesium derivative may not be efficiently produced.

The above ether solvent dissolves the fluorinated aryl, the halogenated hydrocarbon, and the target fluorinated arylmagnesium derivative, and is a liquid compound inert to the reaction according to the present invention. However, it is not particularly limited. Specific examples of the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, di-2-methoxy. Chain ethers such as ethyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane; and the like. These compounds may be used alone or in combination of two or more. Of the compounds exemplified above, diethyl ether and tetrahydrofuran are more preferred because the reaction proceeds more easily.

The amount of the ether solvent used is not particularly limited, but for example, the concentration of the obtained fluorinated arylmagnesium derivative is 0.1% by weight to 80% by weight.
Is preferred.

The above hydrocarbon solvent is not particularly limited as long as it is a liquid compound inert to the reaction of the present invention. As hydrocarbon solvents,
Specifically, for example, pentane, isopentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, paraffin, aliphatic hydrocarbons such as petroleum ether; benzene, toluene, o-
Xylene, m-xylene, p-xylene, 1,2,3-
Aromatic hydrocarbons such as trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,5-trimethylbenzene, 1,3,5-trimethylbenzene, ethylbenzene, propylbenzene and butylbenzene; These compounds may be used alone or in combination of two or more.

The mixing ratio of the ether-based solvent and the hydrocarbon-based solvent is not particularly limited as long as they are uniformly mixed to form a mixed solvent, but the volume ratio is 1 It is preferably in the range of 0 to 1:10. Also,
The amount of the mixed solvent used is not particularly limited,
For example, the amount of the obtained fluorinated arylmagnesium derivative is preferably about 0.1% by weight to 80% by weight.

A mixture in which an aryl fluoride, a halogenated hydrocarbon, and magnesium are mixed with an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent (hereinafter, both are simply referred to as a solvent). The order is not particularly limited. As the mixing order, specifically, for example, aryl fluoride, halogenated hydrocarbon,
And magnesium are mixed with the solvent substantially simultaneously;
After mixing the aryl fluoride and magnesium into the solvent, mix the halogenated hydrocarbon; after mixing the aryl fluoride into the solvent, mix the halogenated hydrocarbon and magnesium substantially simultaneously; mixing the magnesium into the solvent Mixing the fluoroaryl and the halogenated hydrocarbon substantially simultaneously; mixing the magnesium in the solvent, mixing the arylfluoride, and then mixing the halogenated hydrocarbon; the fluoroaryl and the halogenated hydrocarbon After mixing hydrogen with the solvent, magnesium is mixed; and the like. Of the above exemplified methods, after mixing the aryl fluoride and magnesium in a solvent,
The mixing order in which the halogenated hydrocarbons are mixed is particularly preferred.

The mixing method of mixing the fluorinated aryl and / or the halogenated hydrocarbon with the above-mentioned solvent is not particularly limited, but continuous or sequential dropping is preferred. The reaction can be more easily controlled by dropping an aryl fluoride or a halogenated hydrocarbon. In addition, the dropping method is not particularly limited. The aryl fluoride and the halogenated hydrocarbon may be added dropwise as they are, or may be added in a diluted state by adding a solvent.

The mixing temperature for mixing the fluorinated aryl and / or the halogenated hydrocarbon with the above solvent is not particularly limited, but when mixing the halogenated hydrocarbon with the solvent, the mixing temperature is not limited. Is -20 ° C or higher and not higher than the reflux temperature of the solvent, more preferably -20 ° C to 100 ° C.
, More preferably within the range of 20 ° C to 70 ° C. By mixing the halogenated hydrocarbon with the solvent within the above temperature range, the reaction can be more easily controlled. Even if the mixing temperature is adjusted to be lower than −20 ° C., compared with the case where mixing is performed within the above temperature range,
It is industrially disadvantageous because a remarkable effect cannot be obtained. When the mixing temperature exceeds the reflux temperature of the solvent, it becomes difficult to control the reaction. In addition, the mixing temperature is -20 ° C.
As mentioned above, it is industrially easy to adjust the temperature within the reflux temperature of the solvent.

The fluorinated aryl, the halogenated hydrocarbon, and magnesium are mixed with the above-mentioned solvent which is a non-aqueous solvent and then stirred, whereby the three reactions proceed in the solvent. Then, magnesium gradually dissolves as the reaction proceeds. During the reaction, if water is present in the reaction system, the generated aryl magnesium magnesium derivative reacts with water and is decomposed. Therefore, the above reaction is desirably performed in an atmosphere of an inert gas such as nitrogen gas. Further, even during the above mixing, it is desirable that the reaction system, that is, the inside of the reaction vessel is replaced with an inert gas such as nitrogen gas. Further, it is desirable that the above-mentioned solvent, aryl fluoride, and halogenated hydrocarbon do not contain moisture. The method for dehydrating the aryl fluoride, the halogenated hydrocarbon, and the solvent is not particularly limited.

The reaction temperature is not lower than 30 ° C and not higher than the reflux temperature of the solvent, more preferably in the range of 30 ° C to 200 ° C.
More preferably, it is adjusted within the range of 30 ° C to 70 ° C.
When the reaction temperature is lower than 30 ° C., the progress of the reaction is delayed and the fluorinated arylmagnesium derivative cannot be efficiently produced, which is not preferable. Further, when the reaction temperature exceeds the reflux temperature of the solvent, it becomes difficult to control the reaction.

The reaction time is such that the above reaction is completed.
What is necessary is just to set suitably according to reaction temperature, the combination of the aryl fluoride and the halogenated hydrocarbon, and the usage amount.
The reaction pressure is not particularly limited, and may be any of normal pressure (atmospheric pressure), reduced pressure, and increased pressure.

The fluorinated arylmagnesium derivative represented by the general formula (3) is produced by the above method.
Further, a hydrocarbon represented by the general formula (5) R ₀ H (5) (wherein R ₀ represents a hydrocarbon group) is by-produced. The hydrocarbon may be separated from the fluoroarylmagnesium derivative as necessary. The separation method is not particularly limited.

According to the above-mentioned method, the reaction process can be substantially carried out in one step. Also, by the above method,
The fluorinated aryl magnesium derivative can be obtained in high yield and high selectivity. As a result, the fluorinated arylmagnesium derivative can be efficiently and easily manufactured at low cost. The aryl magnesium fluoride derivative is
For example, as a reactant (organic synthesis reagent) for introducing aryl fluoride into various organic compounds, and as a raw material for synthesizing tris (fluoroaryl) boron compound useful as a co-catalyst for metallocene catalyst (polymerization catalyst), It is useful.
Furthermore, when the aryl fluoride is pentafluorobenzene, the pentafluorophenylmagnesium derivative can be efficiently and easily produced at low cost.
The obtained fluorinated arylmagnesium derivative is preferably handled in an atmosphere of an inert gas such as nitrogen gas so as not to react with water.

[0043]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 The inside of a reaction vessel equipped with a thermometer, a dropping funnel, a stirrer, a nitrogen gas introduction tube, and a reflux condenser was sufficiently replaced with nitrogen gas. 2.187 g (0.090 mol) of magnesium and 15.131 g of pentafluorobenzene as aryl fluoride in the reaction vessel.
(0.090 mol) and 15 ml of diethyl ether as a solvent (ether solvent) were charged. In addition, isopropyl bromide 11.62 as halogenated hydrocarbon
A dropping funnel was charged with a mixed solution prepared by mixing 4 g (0.095 mol) with 10 ml of diethyl ether. The ratio of isopropyl bromide to pentafluorobenzene and the ratio of magnesium to pentafluorobenzene were each about 1.06 equivalent.

Then, under a nitrogen stream, the above mixed solution was added dropwise over 0.5 hours while stirring the above contents. The temperature of the contents at the start of dropping was 25 ° C, and the temperature (mixing temperature) of the contents during dropping reached 57.5 ° C.

After the completion of dropping, the reaction solution was added to 57.
The mixture was stirred at 5 ° C. (reaction temperature) for 3 hours to be reacted (aged). As a result, pentafluorophenyl magnesium bromide as a fluorinated aryl magnesium derivative was obtained in a diethyl ether solution.

The reaction yield of pentafluorophenyl magnesium bromide was determined by measuring ¹⁹ F-NMR. That is, the measurement sample was prepared by extracting a part of the reaction solution after the completion of the reaction and mixing the reaction solution with deuterated benzene under a nitrogen atmosphere. In addition, ¹⁹ F-NM
R was measured under predetermined conditions. Then, ¹⁹ resulting F
From the NMR chart, the integral value of the fluorine atom at the meta position of pentafluorobenzene and the integral value of the fluorine atom at the meta position of the pentafluorophenyl group in pentafluorophenyl magnesium bromide were obtained, and pentafluorophenyl was calculated from both integrated values. The amount of magnesium bromide was calculated.

As a result, the reaction yield of pentafluorophenyl magnesium bromide was 83.1 mol%.

Example 2 The inside of the reaction vessel similar to that in Example 1 was thoroughly replaced with nitrogen gas. 2.183 g (0.090 mol) of magnesium, 15.126 g (0.090 mol) of pentafluorobenzene, and tetrahydrofuran 15 as a solvent (ether solvent) were placed in the reaction vessel.
ml. Also, isopropyl bromide 11.646
The dropping funnel was charged with a mixed solution prepared by mixing 10 g of tetrahydrofuran (10 g) (0.095 mol). The ratio of isopropyl bromide to pentafluorobenzene and the ratio of magnesium to pentafluorobenzene were each about 1.06 equivalent.

Then, under a nitrogen stream, the above mixed solution was added dropwise over 50 minutes while stirring the above contents.
The temperature of the contents at the start of dropping was 25 ° C, and the temperature (mixing temperature) of the contents during dropping reached 50.0 ° C.

After completion of dropping, the reaction liquid was adjusted to 50.
The mixture was stirred at 0 ° C. (reaction temperature) for 3 hours to be reacted (aged). As a result, pentafluorophenyl magnesium bromide was obtained in the state of a tetrahydrofuran solution.

The reaction yield of pentafluorophenyl magnesium bromide was determined by the same method as in Example 1. As a result, the reaction yield of pentafluorophenyl magnesium bromide was 90.1 mol%.

Example 3 The inside of the reaction vessel similar to that in Example 1 was sufficiently replaced with nitrogen gas. 2.217 g (0.091 mol) of magnesium, 15.318 g (0.091 mol) of pentafluorobenzene, 15 ml of diethyl ether as an ether solvent, and 5 ml of toluene as a hydrocarbon solvent were charged into the reaction vessel. . Also,
A mixed solution prepared by mixing 12.364 g (0.101 mol) of isopropyl bromide with 10 ml of diethyl ether was placed in a dropping funnel. The ratio of isopropyl bromide to pentafluorobenzene is about 1.11 equivalents, and the ratio of magnesium to pentafluorobenzene is
It was 1.00 equivalent.

Then, under a nitrogen stream, the above mixed solution was added dropwise over 0.5 hours while stirring the above contents. The temperature of the contents at the start of dropping was 25 ° C, and the temperature of the contents during dropping (mixing temperature) reached 61.0 ° C.
The mixing ratio of diethyl ether and toluene was 5: 1 by volume.

After completion of the dropping, the reaction solution was charged with 61.
The mixture was stirred at 0 ° C. (reaction temperature) for 3 hours to be reacted (aged). As a result, pentafluorophenyl magnesium bromide was obtained in the state of a mixed solution of diethyl ether and toluene.

The reaction yield of pentafluorophenyl magnesium bromide was determined by the same method as in Example 1. As a result, the reaction yield of pentafluorophenyl magnesium bromide was 80.0 mol%.

Example 4 The same operation, reaction and measurement as in Example 3 were carried out except that the reaction time (aging time) in Example 3 was changed from 3 hours to 5 hours. As a result, the reaction yield of pentafluorophenyl magnesium bromide was 82.2 mol%.

[0058]

As described above, the method for producing a fluorinated arylmagnesium derivative of the present invention has the general formula (3):

[0059]

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(Wherein R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and X represents a chlorine atom, a bromine atom or an iodine atom). And a general formula (1).

[0061]

[Chemical 6]

(Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group), and an aryl fluoride represented by the general formula (2) ₀ X (2) (in the formula, R ₀ represents a hydrocarbon group, and X represents a chlorine atom, a bromine atom, or an iodine atom), and magnesium, and an ether solvent. It is a method of reacting in a medium or a mixed solvent of an ether solvent and a hydrocarbon solvent.

As a result, since the reaction process can be substantially performed in one step, there is an effect that the fluorinated arylmagnesium derivative can be efficiently and simply produced at low cost.

Further, in the method for producing a fluorinated arylmagnesium derivative of the present invention, as described above, the fluorinated aryl and magnesium are added to the ether solvent or the mixed solvent of the ether solvent and the hydrocarbon solvent. This is a method of mixing halogenated hydrocarbons after mixing.

As described above, the method for producing a fluorinated arylmagnesium derivative of the present invention can be carried out in an ether solvent or a mixed solvent of an ether solvent and a hydrocarbon solvent,
In this method, the mixing temperature for mixing the halogenated hydrocarbon is -20 ° C or higher and the reflux temperature of the solvent or lower.

As described above, the method for producing a fluorinated arylmagnesium derivative of the present invention is a method in which the reaction temperature is 30 ° C. or higher and the reflux temperature of the solvent or lower.

In the method for producing a fluorinated arylmagnesium derivative of the present invention, as described above, the ratio of the halogenated hydrocarbon to the fluorinated aryl is 0.5 equivalent or more,
In addition, the ratio of magnesium to aryl fluoride is 0.5 equivalent or more.

As a result, the fluorinated arylmagnesium derivative can be produced more efficiently and easily.

Furthermore, as described above, the method for producing a fluorinated arylmagnesium derivative of the present invention is a method in which the fluorinated aryl is pentafluorobenzene.

As a result, the pentafluorophenyl magnesium derivative can be produced efficiently, easily and inexpensively.

Claims (6)

[Claims] 1. A compound of the general formula (1) (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group), and a general formula (2) R ₀ X ... (2) (wherein, R ₀ represents a hydrocarbon group, and X represents a chlorine atom, a bromine atom, or an iodine atom), and magnesium were mixed in an ether solvent, or magnesium. , A general formula (3) characterized by reacting in a mixed solvent of an ether solvent and a hydrocarbon solvent. (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, a fluorine atom, a hydrocarbon group or an alkoxy group, and X represents a chlorine atom, a bromine atom or an iodine atom.)
The manufacturing method of the fluorinated aryl magnesium derivative represented by. 2. A mixed solvent of an ether solvent or an ether solvent and a hydrocarbon solvent, wherein aryl fluoride and magnesium are mixed and then a halogenated hydrocarbon is mixed. 1. The method for producing a fluorinated arylmagnesium derivative according to 1. 3. The mixing temperature at which the halogenated hydrocarbon is mixed with the ether solvent or the mixed solvent of the ether solvent and the hydrocarbon solvent is −20 ° C. or higher and the reflux temperature of the solvent or lower. 3. The method for producing a fluorinated arylmagnesium derivative according to claim 1 or 2. 4. The reaction temperature is 30 ° C. or higher and not higher than the reflux temperature of the solvent, wherein the reaction temperature is 30 ° C. or higher.
A method for producing the fluorinated arylmagnesium derivative described. 5. The ratio of halogenated hydrocarbon to fluorinated aryl is 0.5 equivalent or more, and the ratio of magnesium to fluorinated aryl is 0.5 equivalent or more. The method for producing a fluorinated arylmagnesium derivative according to 2, 3, or 4. 6. A fluorinated aryl is pentafluorobenzene, 1, 2, 3, 4 or 5.
A method for producing the fluorinated arylmagnesium derivative described.