JPH1129578A - Production of boron-based compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing, in a high yield, a high-purity boron-based compound useful for, e.g. a photo-polymerization initiator or the like by using a specific stock material, reaction solvent and reaction process. SOLUTION: This method comprises a series of steps, (1) reacting (A) a Li- or Mg-containing compound, a compound shown by the formula R1 -Y1 (R1 is an alkyl, alkenyl or the like; and Y1 is a halogen) and a borate ester compound shown by formula I (R3 to R5 are each an alkyl, alkenyl, aryl or the like) with each other in a solvent to produce a boronate compound shown by formula II, (2) reacting compound shown by formula II with a compound shown by formula III (R6 to R11 are each an alkyl, H or the like) to produce a boron- based compound shown by formula IV, (3) reacting the compound shown by formula IV, a compound shown by the formula R2 -Y1 (R2 is the same as R1 ) and the component A with each other in a solvent to produce a metallic salt of borate shown by formula V (M is Li or Mg; and (n) is 1 or 2), and (4) ion- exchanging reaction between the metallic salt of borate and an onium halide shown by the formula, Z<+> .X<-> (Z<+> is ammonium cation or the like; and X is a halogen) to produce the objective boron-based compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a boron-based compound, and more particularly to a method for producing a boron-based compound useful as a photopolymerization initiator or a light-absorbing decolorizer.

[0002]

2. Description of the Related Art A method for producing tetramethylammonium methyltriphenylborate, which is one of the boron-based compounds represented by the general formula (1), is based on lithium methyltriphenylborate obtained from triphenylborane and methyllithium. A method for obtaining a late by ion exchange with tetramethylammonium bromide is generally known [for example,
J. of Amer. Chem. Soc. , 107 volumes,
(1985) 6710-6711].

[0003] Further, a method for producing triphenylborane is as follows.
A method obtained by reacting magnesium metal, boron trifluoride diethyl etherate, and phenyl bromide in diethyl ether is generally known [for example, J. Am. of Organic Chem. , 51
Vol., (1986) 427-432].

Specifically, in the case of the above-mentioned tetramethylammonium methyltriphenylborate, phenyl bromide is reacted with metallic magnesium in diethyl ether to prepare a Grignard reagent, which is then reacted with boron trifluoride diethyl etherate to give diethyl ether. Add dropwise to the solution in ether. Further stirring for several hours gives triphenylborane. Without isolation, methyllithium is added to obtain lithium methyltriphenylborate, tetramethylammonium bromide is added thereto, and ion exchange is performed to obtain tetramethylammonium methyltriphenylborate.

[0005] Alkyl dialkyl boronates (or
As a method for producing an aryldialkylboronate, a method of reacting a trialkylboric acid with a Grignard reagent or organolithium in diethyl ether is generally known [for example, Organometallics (1993)].
Year), 1058-1067]

As a method for producing alkylborinane (or arylborinane), a method for producing dihydroxyalkylborane (or dihydroxyarylborane) as a raw material is generally known [for example, J. Am. of
Chem. Soc. (A), (1970), 3339
３３3345]

[0007]

In the above-mentioned conventional production method, the solvent for the Grignard reaction, triarylborane or trialkylborane reaction is limited to diethyl ether due to the side reaction problem [for example, J. .
of Organic Chem. , 51, (198
6 years) 427-432]. However, in general, the Grignard reaction is more likely to occur in tetrahydrofuran than in diethyl ether [eg, Basic Organic Chemistry (Mitsuaki Mukaiyama, edited by Maruzen), p. 79]. There is a problem that the final yield is low.

[0008] An object of the present invention is to solve such a problem in the conventional production method and to obtain a high-purity boron-based compound useful as a photopolymerization initiator or a light-absorbing decolorizer in a high yield. It is to provide a possible manufacturing method.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on such problems, and as a result, have found that the problems can be solved by using a specific starting material, a reaction solvent and a specific reaction step. It came to accomplish.

That is, claim 1 of the present invention is to react a compound containing lithium or magnesium with a compound represented by the general formula (2) and a borate compound represented by the general formula (3) in a solvent. Thereby, the first step of producing the boronate compound represented by the general formula (4) and the second step of reacting the boronate compound represented by the general formula (4) with the compound represented by the general formula (5) And a method for producing a boron compound represented by the general formula (6) (hereinafter sometimes referred to as a borinane compound).

[0011]

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(Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. Y ₁ represents a halogen atom. )

[0013]

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(Wherein R ₃ , R ₄ , and R ₅ may be the same or different and each may be an optionally substituted alkyl group, an optionally substituted alkenyl group, Represents an aryl group which may be substituted, an aralkyl group which may be substituted, and an alicyclic group which may be substituted.)

[0015]

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(Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. R ₄ and R ₅ may be the same or different, and each may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, Represents an aralkyl group which may be possessed, or an alicyclic group which may be substituted. )

[0017]

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(Wherein R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group, Represents an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alicyclic group, and a hydrogen atom.

[0019]

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(Wherein R ₁ represents an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁
May be the same or different, and may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl Represents a group, an alicyclic group which may have a substituent, or a hydrogen atom. )

A second aspect of the present invention is to react a compound containing lithium or magnesium with a compound represented by the general formula (2) and a borate compound represented by the general formula (3) in a solvent. A first step of producing a boronate compound represented by the general formula (4), and reacting the boronate compound represented by the general formula (4) with the compound represented by the general formula (5) to form a compound represented by the general formula ( A second step of producing a boron-based compound represented by the formula (6), a compound containing lithium or magnesium, a compound represented by the formula (7) and a boron-based compound represented by the formula (6) in a solvent And a third step of producing a borate metal salt represented by the general formula (8) by reacting the onium halide represented by the general formula (9) with the borate metal salt represented by the general formula (8) Ion exchange Characterized by comprising the fourth step of the response, a method for producing a boron-based compound represented by the general formula (1).

[0022]

Embedded image

(Wherein R ₁ is an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. Y ₁ represents a halogen atom. )

[0024]

Embedded image

(Wherein R ₃ , R ₄ and R ₅ may be the same or different, and each may have an alkyl group which may be substituted, an alkenyl group which may be substituted, Represents an aryl group which may be substituted, an aralkyl group which may be substituted, and an alicyclic group which may be substituted.)

[0026]

Embedded image

(Wherein R ₁ is an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. R ₄ and R ₅ may be the same or different, and each may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, Represents an aralkyl group which may be possessed, or an alicyclic group which may be substituted. )

[0028]

Embedded image

(Wherein R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group, Represents an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alicyclic group, and a hydrogen atom.

[0030]

Embedded image

(Wherein R ₁ represents an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁
May be the same or different, and may be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl Represents a group, an alicyclic group which may have a substituent, or a hydrogen atom. )

[0032]

Embedded image

(Wherein R ₂ represents an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted,
It represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group. Y ₁ represents a halogen atom. )

[0034]

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(Wherein R ₁ and R ₂ are different from each other, and R ₁ and R ₂ are each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, M represents a lithium atom or magnesium, which represents an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted heterocyclic group, or an optionally substituted alicyclic group. Represents an atom, n = 1, 2.)

[0036]

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(In the formula, Z ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a phosphonium cation, or an iodonium cation. X represents a halogen atom.)

[0038]

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(Wherein R ₁ and R ₂ are different from each other, and R ₁ and R ₂ are each independently an alkyl group which may be substituted, an alkenyl group which may be substituted, Z ⁺ represents an ammonium cation, an aryl group which may be substituted, an aralkyl group which may be substituted, a heterocyclic group which may be substituted, and an alicyclic group which may be substituted; (Representing a sulfonium cation, an oxosulfonium cation, a phosphonium cation, and an iodonium cation.)

In a third aspect of the present invention, in the method for producing a boron compound according to the first or second aspect, the first step comprises the step of combining the compound containing lithium or magnesium with the compound represented by the general formula (2). The reaction is carried out in a solvent, and the compound represented by the general formula (3) is added thereto and reacted.
The compound represented by the general formula (3) is reacted with a compound containing lithium or magnesium and the compound represented by the general formula (2) reacted in a solvent, or lithium or magnesium is reacted. The compound represented by the general formula (4) is reacted with the compound containing the compound represented by the general formula (2) in a solvent and the compound represented by the general formula (3) at the same time to react. And producing a boronate compound.

According to a fourth aspect of the present invention, in the method for producing a boron compound according to the first or second aspect, the compound containing lithium or magnesium is metallic lithium, metallic magnesium, or an organic lithium compound. And

According to a fifth aspect of the present invention, in the method for producing a boron compound according to the second aspect, the compound containing lithium or magnesium used in the third step is an organic lithium compound.

According to a sixth aspect of the present invention, in the method for producing a boron compound according to the second aspect, the solvent used in the third step is tetrahydrofuran.

[0044]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned general formula (1) representing a boron compound produced by the method for producing a boron compound of the present invention.
R ₁ and R ₂ in the formula are different from each other, and R ₁ and R ₂
Are each independently an alkyl group which may have a substituent,
Optionally substituted alkenyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted heterocyclic group, optionally substituted alicyclic group Represents a group. Z ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a phosphonium cation, and an iodonium cation.

The alkyl group which may be substituted at R ₁ and R ₂ is specifically preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms. Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl,
Hexyl, heptyl, octyl, 3-methoxypropyl, 4-chlorobutyl, 2-diethylaminoethyl and the like can be mentioned.

The alkenyl group which may be substituted at R ₁ and R ₂ is specifically a substituted or unsubstituted linear or branched alkenyl group having 2 to 12 carbon atoms.
For example, vinyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group,
Dodecinyl group, prenyl group and the like can be mentioned.

The aryl group optionally substituted by R ₁ and R ₂ is specifically a substituted or unsubstituted aryl group, for example, phenyl, tolyl, xyl, 4-ethylphenyl, 4-ethylphenyl, Butylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, 2-methylphenyl, 2-methoxyphenyl,
Examples thereof include 1-naphthyl, 2-naphthyl, 6-methoxy-2-naphthyl, and 4-methyl-naphthyl.

The aralkyl group optionally substituted with R ₁ and R ₂ is specifically a substituted or unsubstituted aralkyl group, for example, a benzyl group, a phenethyl group, a propiophenyl group, a 1- Examples thereof include a naphthylmethyl group, a 2-naphthylmethyl group, and a 4-methoxybenzyl group.

The heterocyclic group which may be substituted at R ₁ and R ₂ is specifically a substituted or unsubstituted heterocyclic group such as a pyridyl group, a quinolyl group, a methylpyridyl group, an indolyl group. And the like.

The alicyclic group which may be substituted at R ₁ and R ₂ is specifically a substituted or unsubstituted alicyclic group, for example, a cyclohexyl group, a 4-methylcyclohexyl group,
Examples thereof include a cyclopentyl group and a cycloheptyl group.

Specific examples of the ammonium cation for Z ⁺ include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetranormalbutylammonium cation, tetranormalpentylammonium cation, tetranormaloctylammonium cation, Tetrabenzylammonium cation, tetraphenylammonium cation, tetracyclohexylammonium cation, tetraphenylammonium cation, triphenylphenacylammonium cation, triphenyl (4-aminophenyl) ammonium cation, N
-Methylpyridinium cation, N-butylpyridinium cation and the like.

Examples of the sulfonium cation for Z ⁺ include, for example, dimethyl-tert-butylsulfonium cation, dimethylbenzylsulfonium cation,
Dimethyl (4-chlorobenzyl) sulfonium cation, dibutyl (4-bromobenzyl) sulfonium cation, dimethyl (4-cyanobenzyl) sulfonium cation, dimethylphenacylsulfonium cation, dibutylethoxysulfonium cation, dimethylphenoxysulfonium cation, methyl (dimethylamino) )
Examples include (4-tolyl) sulfonium cation, dimethyl (methylthio) sulfonium cation, dimethyl (phenylthio) sulfonium cation, triphenylsulfonium cation, and 4-methoxyphenyldiphenylsulfonium cation.

The oxosulfonium cation at Z ⁺ is
Specifically, for example, dimethyl-tert-butyloxosulfonium cation, dimethylbenzyloxosulfonium cation, dimethyl (4-chlorobenzyl) oxosulfonium cation, dibutyl (4-bromobenzyl) oxosulfonium cation, dimethyl (4-cyanobenzyl) ) Oxosulfonium cation, dimethylphenacyloxosulfonium cation, dibutylethoxyoxosulfonium cation, dimethylphenoxyoxosulfonium cation, methyl (dimethylamino) (4-tolyl) oxosulfonium cation, dimethyl (methylthio) oxosulfonium cation, dimethyl (phenylthio) Oxosulfonium cation, triphenyloxosulfonium cation, 4-methoxyphenyldiphenyl , And the like Kiso sulfonium cation.

Examples of the phosphonium cation for Z ⁺ include, for example, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrapropylphosphonium cation, tetranormal butyl phosphonium cation, tetranormal pentyl phosphonium cation, tetranormal octyl phosphonium cation, Examples thereof include a tetrabenzylphosphonium cation, a tetraphenylphosphonium cation, a tetracyclohexylphosphonium cation, a tetraphenylphosphonium cation, a triphenylphenacylphosphonium cation, and a triphenyl (4-aminophenyl) phosphonium cation.

Specific examples of the iodonium cation for Z ⁺ include, for example, diphenyliodonium cation,
Butoxyphenyl (4-methylphenyl) iodonium cation, bis (4-aminophenyl) iodonium cation and the like can be mentioned.

Specific examples of the boron compound represented by the general formula (1) include, for example, tetramethylammonium ethyltributylborate, tetranormalbutylammonium phenethyltrimethylborate, and tetraethylammoniumphenyltriisobutyl. Borate, tetranormal butyl ammonium phenethyl tri (4-methylphenyl) borate, tetramethyl ammonium ethyl triphenyl borate, tetra normal butyl ammonium phenethyl tri (4-methylphenyl) borate, tetraethyl ammonium normal octyl tri (4,5- (Diethylphenyl) borate, tetra-n-butylammonium-n-pentyltri (4-methoxyphenyl) borate, tetra-n-octyl-ammonium Malbutyl tri (1-naphthyl) borate, tetra-n-butyl ammonium normal butyl tri (2-naphthyl) borate, tetra-n-butyl ammonium normal butyl tri (6-methoxy-2-naphthyl) borate, tetra-n-butyl ammonium normal butyl tri (4- Methyl-naphthyl) borate, tetranormalethylammonium normal octyltri (4,5-diethylnaphthyl) borate, tetranormalbutylammoniumethyltriacenaphthylborate, N-methylpyridinium normalbutyltriphenylborate, triphenylsulfonium normalbutyl Tri (1-naphthyl) borate, triphenyloxosulfonium n-butyl tri (1-naphthyl) borate, tetra-n-butyl Suho iodonium n-butyl triphenyl borate, diphenyl iodonium n-butyl triphenyl borate and the like.

R ₁ in the general formula (2) is the same as R _{1 in the} general formula (1). Y ₁ represents a halogen atom.

Specific examples of the compound represented by the general formula (2) include, for example, methyl bromide, ethyl chloride, propyl chloride, isopropyl chloride, butyl chloride, isobutyl bromide, pentyl bromide, hexyl bromide, Octyl chloride, 3-propylmethoxy bromide, vinyl bromide, propenyl bromide, butenyl bromide,
Pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, bromobenzene, iodobenzene, bromotoluene, bromoxylene, 1-bromo-4-ethylbenzene, 1-bromo-4
-Butylbenzene, 1-bromo-4-tertbutylbenzene, 1-bromo-4-methoxybenzene, 1-bromo-4-diethylaminobenzene, 1-bromo-2-methylbenzene, 1-bromo-2-methoxybenzene, 1
-Bromo-naphthalene, 1-bromo-4-methylnaphthalene, benzyl chloride, phenethyl bromide, 1
-Bromo-3-phenylpropane, 1- (bromomethyl) naphthalene, 2- (bromomethyl) naphthalene, 2
-Bromo-6-methoxynaphthalene, 4-methoxybenzyl chloride, cyclohexyl chloride, 1-chloro-4-methylcyclohexane and the like can be mentioned.

R ₃ , R ₄ and R in the general formula (3)
₅ may be the same or different, and each may have an optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted aralkyl group, optionally substituted Represents a good alicyclic group.

The optionally substituted alkyl group at R ₃ , R ₄ and R ₅ is preferably a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl, octyl, 3-methoxypropyl, 4-chlorobutyl, and 2-diethylaminoethyl.

The alkenyl group optionally substituted with R ₃ , R ₄ and R ₅ is specifically defined as having 2 to 12 carbon atoms.
And a substituted or unsubstituted linear or branched alkenyl group is preferred, and examples thereof include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a dodecynyl group, and a prenyl group.

The aryl group optionally substituted with R ₃ , R ₄ and R ₅ is specifically a substituted or unsubstituted aryl group, for example, phenyl, tolyl, xyl,
4-ethylphenyl, 4-butylphenyl, 4-ter
Examples thereof include t-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, 2-methylphenyl, 2-methoxyphenyl, 1-naphthyl, 2-naphthyl, and 4-methyl-naphthyl.

The aralkyl group which may be substituted at R ₃ , R ₄ and R ₅ is specifically a substituted or unsubstituted aralkyl group, for example, benzyl group, phenethyl group, propiophenyl Group, 1-naphthylmethyl group, 2-
Examples include a naphthylmethyl group and a p-methoxybenzyl group.

The alicyclic group which may be substituted at R ₃ , R ₄ and R ₅ is specifically a substituted or unsubstituted alicyclic group, for example, a cyclohexyl group, 4-methylcyclohexyl Group, cyclopentyl group, cycloheptyl group and the like.

Specific examples of the compound represented by the general formula (3) include, for example, trimethyl boric acid, triethyl boric acid, trinormal propyl boric acid, triisopropyl boric acid, and trinormal butyl boric acid. , Triisobutyl boric acid, trinormal octyl boric acid, butyl diethyl boric acid, ethyl di (2-phenethyl) boric acid, triphenyl boric acid, diethyl-4-methoxyphenyl boric acid, diethyl cyclohexyl boric acid, and the like. .

R ₁ in the general formula (4) is the same as R _{1 in the} general formula (1). R ₄ and R ₅ are respectively the same as R ₄ and R _{5 in} the general formula (3).

Specific examples of the boronate compound represented by the general formula (4) include, for example, dimethylethyl boronate, diethyl normal propyl boronate,
Diisopropyl normal butyl boronate, diisobutyl methyl boronate, di normal octyl benzyl boronate, di (2-phenethyl) normal butyl boronate, diphenyl normal propyl boronate, diisopropyl phenyl boronate, diethyl (4-methoxyphenyl) boronate, dicyclohexyl Normal octyl boronate and the like can be mentioned.

In the general formula (5), R ₆ , R ₇ , R ₈ ,
R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group, an optionally substituted alkenyl group, and an optionally substituted aryl group. ,
Represents an aralkyl group which may be substituted, an alicyclic group which may be substituted, and a hydrogen atom.

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R
_The alkyl group which may have a substituent at ₁₁ , specifically,
A substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms is preferable.
Ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, hexyl, heptyl,
Octyl, 3-methoxypropyl, 4-chlorobutyl,
2-diethylaminoethyl and the like can be mentioned.

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R
_The alkenyl group optionally having a substituent at ₁₁ is specifically preferably a substituted or unsubstituted linear or branched alkenyl group having 2 to 12 carbon atoms, for example, a vinyl group,
Examples include a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a dodecynyl group, and a prenyl group.

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R
_The aryl group which may have a substituent at ₁₁ , specifically,
A substituted or unsubstituted aryl group such as phenyl, tolyl, xyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 4-diethylaminophenyl, 2-methylphenyl, -Methoxyphenyl, 1-naphthyl, 2-
Examples include naphthyl and 4-methyl-naphthyl.

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R
_The aralkyl group optionally having a substituent at ₁₁ is specifically a substituted or unsubstituted aralkyl group, for example, a benzyl group, a phenethyl group, a propiophenyl group, a 1-naphthylmethyl group, a 2-naphthyl Examples include a methyl group and a p-methoxybenzyl group.

R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R
_The alicyclic group which may have a substituent at ₁₁ is specifically a substituted or unsubstituted alicyclic group, for example, a cyclohexyl group,
Examples thereof include a 4-methylcyclohexyl group, a cyclopentyl group, and a cycloheptyl group.

Specific examples of the compound represented by the general formula (5) include, for example, 1,3-propanediol, 1,3-butanediol, 1,3-hexanediol, 2,4 -Pentanediol, 3-methyl-1,3-
Butanediol, 2-phenyl-1,3-propanediol, 2-benzyl-1,3-propanediol, 2-
Cyclohexyl-1,3-propanediol and the like can be mentioned.

R ₁ in the general formula (6) is the same as R _{1 in the} general formula (1). R ₆ , R ₇ , R ₈ , R ₉ ,
R ₁₀ and R ₁₁ are respectively R ₆ , R ₇ and R in the general formula (5).
₈ , R ₉ , R ₁₀ and R ₁₁ are the same.

As an example of the boron compound represented by the general formula (6), specifically, for example, 2-methyl-
1,3,2-dioxaborinane, 2-ethyl-1,3,3
2-dioxaborinane, 2-normalpropyl-1,
3,2-dioxaborinane, 2-normalbutyl-1,
3,2-dioxaborinane, 2-phenyl-1,3,2
-Dioxaborinane, 2-naphthyl-1,3,2-dioxaborinane, 2-normalbutyl-4-methyl-1,
3,2-dioxaborinane, 2-normalbutyl-5-
Phenyl-1,3,2-dioxaborinane, 2-normalbutyl-4-methyl-1,3,2-dioxaborinane, and the like can be given.

R ₂ in the general formula (7) is the same as R _{2 in the} general formula (1). Y ₁ represents a halogen atom.

Specific examples of the compound represented by the general formula (7) include, for example, methyl bromide, ethyl chloride, propyl chloride, isopropyl chloride, butyl chloride, isobutyl bromide, pentyl bromide, hexyl bromide, Octyl chloride, 3-propylmethoxy bromide, vinyl bromide, propenyl bromide, butenyl bromide,
Pentenyl bromide, hexenyl bromide, heptenyl bromide, octenyl bromide, bromobenzene, iodobenzene, bromotoluene, bromoxylene, 1-bromo-4-ethylbenzene, 1-bromo-4
-Butylbenzene, 1-bromo-4-tertbutylbenzene, 1-bromo-4-methoxybenzene, 1-bromo-4-diethylaminobenzene, 1-bromo-2-methylbenzene, 1-bromo-2-methoxybenzene, 1
-Bromo-naphthalene, 1-bromo-4-methylnaphthalene, benzyl chloride, phenethyl bromide, 1
-Bromo-3-phenylpropane, 1- (bromomethyl) naphthalene, 2- (bromomethyl) naphthalene, 2
-Bromo-6-methoxynaphthalene, 4-methoxybenzyl chloride, cyclohexyl chloride, 1-chloro-4-methylcyclohexane and the like can be mentioned.

[0079] R ₁ and R ₂ in the general formula (8) is identical to R ₁ and R ₂ in the general formula (1). M represents a lithium atom or a magnesium atom.

Specific examples of the borate metal salt represented by the general formula (8) include, for example, lithium ethyl tributyl borate, lithium phenethyl trimethyl borate, lithium phenyl triisobutyl borate, and lithium phenethyl tributyl borate. (4-methylphenyl) borate, lithium ethyltriphenylborate, magnesium bis (phenethyltri (4-methylphenyl) borate), magnesium bis (normal octyltri (4,
5-diethylphenyl) borate), magnesium bis (normalpentyltri (4-methoxyphenyl) borate), lithium normalbutyltri (1-naphthyl)
Borate, magnesium bis (normal butyl tri (2
-Naphthyl) borate), magnesium bis (normal butyltri (4-methylnaphthyl) borate), lithium normal octyltri (4,5-diethylnaphthyl)
And borate, magnesium bis (ethyltriacenaphthyl borate) and the like.

Z ⁺ in the general formula (9) is the same as Z ^{+ in the} general formula (1). X represents a halogen atom.

Specific examples of the onium halide represented by the general formula (9) include, for example, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium iodide, tetranormal butylammonium bromide, tetranormal Pentyl ammonium chloride, tetra normal octyl ammonium bromide, tetrabenzyl ammonium bromide, tetraphenyl ammonium bromide, tetracyclohexyl ammonium bromide, N-methyl pyridinium chloride, N-butyl pyridinium bromide, dimethyl-tert-butyl sulfonium bromide, dimethyl benzyl sulfonium bromide, Dimethyl (4-chlorobenzyl) sulfonium bromide, di Chill (4-bromobenzyl) sulfonium chloride, dimethyl (4-cyanobenzyl)
Sulfonium bromide, dimethylphenacylsulfonium chloride, dibutylethoxysulfonium chloride, dimethylphenoxysulfonium bromide, methyl (dimethylamino) (4-tolyl) sulfonium bromide, dimethyl (methylthio) sulfonium bromide, dimethyl (phenylthio) sulfonium bromide, triphenylsulfonium chloride , 4-methoxyphenyldiphenylsulfonium bromide, dimethyl-tert-butyloxosulfonium bromide,
Dimethylbenzyloxosulfonium bromide, dimethyl (4-chlorobenzyl) oxosulfonium chloride, dibutyl (4-bromobenzyl) oxosulfonium chloride, dimethyl (4-cyanobenzyl) oxosulfonium chloride, dimethylphenacyloxosulfonium chloride, dibutylethoxyoxosulfonium chloride Bromide, dimethylphenoxyoxosulfonium chloride, methyl (dimethylamino) (4-tolyl) oxosulfonium chloride, dimethyl (methylthio) oxosulfonium bromide, dimethyl (phenylthio) oxosulfonium bromide, triphenyloxosulfonium chloride, 4-methoxyphenyldiphenyloxo Sulfonium iodide, tetramethylphosphonium Chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetranormalbutylbutylphosphonium bromide, tetranormalpentylphosphonium bromide, tetranormaloctylphosphonium chloride, tetrabenzylphosphonium chloride, tetraphenylphosphonium iodide, tetracyclohexylphosphonium bromide, tetraphenylphosphonium bromide, Triphenylphenacylphosphonium chloride, triphenyl (4-aminophenyl) phosphonium bromide,
Diphenyliodonium chloride, 4-butoxyphenyl (4-methylphenyl) iodonium chloride,
Bis (4-aminophenyl) iodonium chloride and the like can be mentioned.

As the compound containing lithium or magnesium used in the present invention, specifically, for example, metal lithium, metal magnesium, methyl lithium, ethyl lithium, normal butyl lithium and the like can be mentioned.

As the solvent used in the present invention, specifically, for example, diethyl ether, normal butyl ethyl ether, dinormal propyl ether, diisopropyl ether, dinormal butyl ether, 1,2-dimethoxyethane, tetrahydrofuran, Ether solvents such as 4-dioxane, and hydrocarbon solvents such as hexane and cyclohexane, benzene, toluene, and aromatic solvents such as xylene, among these,
Diethyl ether, tetrahydrofuran, hexane and toluene can be preferably used.

In the present invention, the boron compound represented by the general formula (6) is produced in the following first step and second step. (First step) A compound containing lithium or magnesium is reacted with a compound represented by the general formula (2) in a solvent, and a compound represented by the general formula (3) is added thereto and reacted. A compound obtained by reacting a compound containing lithium or magnesium with a compound represented by the general formula (2) in a solvent to the compound represented by (3), or reacting the compound; or a compound containing lithium or magnesium And a compound represented by the general formula (2) reacted in a solvent;
The boronate compound represented by the general formula (4) is produced by simultaneously adding and reacting the compound represented by the general formula (3), and (second step) the boronate compound represented by the general formula (4) And the compound represented by the general formula (5) to produce a boron-based compound represented by the general formula (6).

In the present invention, the boron compound represented by the general formula (1) is produced in the following first to fourth steps. (First and second steps) Subsequent to the first and second steps, (third step) A compound containing lithium or magnesium is reacted with a compound represented by the general formula (7) in a solvent. A boron-based compound represented by the general formula (6) is added and reacted, or a compound containing lithium or magnesium and a compound represented by the general formula (7) are added to the boron-based compound represented by the general formula (6). Is reacted in a solvent, or a compound containing lithium or magnesium is reacted with a compound represented by the general formula (7) in a solvent;
A boron-based compound represented by the general formula (6) is simultaneously added and reacted, or a compound containing lithium or magnesium and a compound containing the general formula (7) in the presence of the boron-based compound represented by the general formula (6)
Is reacted in a solvent to produce a borate metal salt represented by the general formula (8) (fourth step). The boron-based compound represented by the general formula (1) is produced by adding an onium halide represented by the formula (9) and conducting an ion exchange reaction.

Specifically, for example, in the first step,
Using metal magnesium as the compound containing lithium or magnesium, and using a halide as the compound represented by the general formula (2), the compound represented by the general formula (4) is obtained by using any one of the above methods. Can be produced.

In the first step, any one of the above-mentioned methods may be used, using metal lithium as a compound containing lithium or magnesium, and using a halide as a compound represented by the general formula (2). Can be used to produce the boronate compound represented by the general formula (4).

In the first step, an organic lithium compound is used as a compound containing lithium or magnesium, and a halide is used as a compound represented by the general formula (2). The boronate compound represented by the general formula (4) can be produced by the method.

In the third step, metal magnesium is used as the compound containing lithium or magnesium, and a halide is used as the compound represented by the general formula (7). Can be used to produce the above borate metal salt.

In the third step, any one of the above-mentioned methods may be used, using metal lithium as the compound containing lithium or magnesium, and using a halide as the compound represented by the general formula (VII). Can be used to produce the above borate metal salt.

Further, in the third step, an organic lithium compound is used as a compound containing lithium or magnesium, and a halide is used as a compound represented by the above general formula (7). The borate metal salt can be produced using a method.

The first step in the present invention can be specifically carried out, for example, as follows. In the first step, an example of a reaction for producing a boronate compound represented by the general formula (4) using metal magnesium as a lithium compound or a magnesium compound will be specifically described. In this case, the above reaction is a reaction for preparing a Grignard reagent.

When a small amount of an ether solution of a halide represented by the general formula (2) is added to metallic magnesium and the mixture is stirred, the reaction temperature eventually rises, and the reaction (a Grignard reaction) starts. When the reaction hardly occurs, iodine, methyl iodide and the like may be added as an initiator. The reaction temperature is preferably near the boiling point of the solvent used, and an ether-based solution of a halide represented by the general formula (2) is added so as to maintain this temperature.

For example, in tetrahydrofuran,
It is desirable to add a halide solution in tetrahydrofuran so as to react at around 72 ° C. After adding the ether solution of the halide represented by the general formula (2), the mixture is further stirred at room temperature to around the boiling point of the solvent for about 30 minutes to 20 hours to complete the reaction. The compound prepared here is the Grignard reagent.

In the case of the above reaction, a solution of the compound represented by the general formula (3) in the Grignard reagent (preferably a solution using the same solvent as the Grignard reaction solvent)
Is added so that the reaction temperature becomes about -100 ° C to around the boiling point of the solvent.

In the case of the above reaction, a Grignard reagent is added to a solution of the compound represented by the general formula (3) (preferably a solution using the same solvent as the Grignard reaction solvent) at a reaction temperature of -100 ° C to a solvent. -100 ° C. after addition, and 30 minutes at around the boiling point of the solvent.
Let react for about 2 hours.

In the case of the above reaction, a solution of the Grignard reagent and the compound represented by the general formula (3) (preferably, a solution using the same solvent as the Grignard reaction solvent)
Is added simultaneously so that the reaction temperature becomes about -100 ° C to around the boiling point of the solvent, and after the addition, the reaction is carried out at about -100 ° C to around the boiling point of the solvent for about 30 minutes to 2 hours.

After completion of the reaction, the reaction solution is heated to distill off the solvent, and further heated to distill the boronate compound represented by the general formula (4). The first step is completed by adding an organic solvent (preferably ethyl acetate or diethyl ether) and, if necessary, adding water and / or an acid to separate only the organic phase and, if necessary, purifying by distillation. I do.

In the first step, an example of the reaction for producing the boronate compound represented by the general formula (4) using lithium metal as the compound containing lithium or magnesium will be specifically described.

As described above, metal lithium is used as the compound containing lithium or magnesium, and the halide represented by the general formula (2) is used.
In this case, the solvent may be an ether-based solvent such as diethyl ether or tetrahydrofuran, or a solvent such as hexane or cyclohexane. In this case, the reaction is generally carried out at -100 ° C to around room temperature under an inert gas.

Specifically, the above-mentioned solvent is added to lithium metal, and a halide solution is added thereto. The reaction temperature varies depending on the halide and solvent used. For example, in the reaction between lithium metal and bromobenzene in diethyl ether, it is desirable to add a diethyl ether solution of bromobenzene so that the reaction temperature becomes -78 to -70 ° C. After adding the halide solution, the mixture is further stirred at -100 ° C to around room temperature for about 30 minutes to 2 hours to prepare an organolithium compound.

In the case of the above reaction, a solution obtained by dissolving the compound represented by the general formula (3) in the above-mentioned solvent (preferably an ether-based solvent) in this organolithium compound has a reaction temperature of -100. The reaction is carried out at -100 ° C to room temperature for about 30 minutes to 2 hours.

In the case of the above reaction, an organic lithium compound is added to a solution obtained by dissolving the compound represented by the general formula (3) in the above-mentioned solvent (preferably an ether solvent) at a reaction temperature of -100 ° C. to room temperature. The reaction is carried out for about 30 minutes to 2 hours.

In the case of the above reaction, a solution of an organic lithium compound and a compound represented by the general formula (3) (preferably an ether solvent) is adjusted so that the reaction temperature is from -100 ° C. to around the boiling point of the solvent. Add at the same time.
The reaction is carried out at about the boiling point of the solvent for about 30 minutes to 2 hours.

After the reaction is completed, the reaction solution is heated to remove the solvent, and further heated to distill the boronate compound represented by the above general formula (IV). The first step is completed by adding an organic solvent (preferably ethyl acetate or diethyl ether) and, if necessary, adding water and / or an acid to separate only the organic phase and, if necessary, purifying by distillation. I do.

Next, an example of the reaction for producing the above-mentioned borate metal salt in the first step using an organic lithium compound as a compound containing lithium or magnesium will be specifically described.

As described above, an organic lithium compound is used as a compound containing lithium or magnesium, and an aromatic halide represented by the general formula (2) is used.
It can also be manufactured using any of the above methods.

Some of the organic lithium compounds are commercially available in the form of a solution such as a hexane solution, a cyclohexane solution, and a diethyl ether solution, and can be easily obtained. In this case, a solvent for the reaction may be an ether solvent such as diethyl ether or tetrahydrofuran, or a solvent such as hexane or cyclohexane.

In general, the reaction is carried out at -100 ° C. under an inert gas.
Performed at around room temperature. An organic lithium compound is prepared by adding a halide solution to the organic lithium compound solution so that the reaction temperature is in the range of −100 ° C. to room temperature. The reaction temperature varies depending on the halide and solvent used. For example, normal butyl lithium in diethyl ether and 1
The reaction with -bromo-2,5-dimethylbenzene gives -78
It is preferable to add a diethyl ether solution of 1-bromo 2,5-dimethylbenzene so that the reaction is carried out at -10C. After the addition of the halide solution,
Stir at about 100 ° C. to room temperature for about 30 minutes to 2 hours to prepare an organic lithium compound. Alternatively, the organolithium compound can be prepared by adding the organolithium compound to the halide solution under the same conditions.

In the case of the above reaction, a solution obtained by dissolving the compound represented by the general formula (3) in this organic lithium compound in the above-mentioned solvent (preferably an ether solvent) has a reaction temperature of-. The reaction mixture is added at about 100 ° C. to room temperature, and after the addition, the reaction is carried out at −100 ° C. to room temperature for about 30 minutes to 2 hours.

In the case of the above reaction, an organic lithium compound is added to a solution of the compound represented by the general formula (3) in a solvent as described above (preferably an ether solvent) at a reaction temperature of -100 ° C. After the addition, the reaction is carried out at -100 ° C to around room temperature for about 30 minutes to 2 hours.

In the case of the above reaction, a solution (preferably an ether solvent) of the organolithium compound and the compound represented by the general formula (3) is adjusted so that the reaction temperature becomes -100 ° C. to around the boiling point of the solvent. Add at the same time.
The reaction is carried out at about the boiling point of the solvent for about 30 minutes to 2 hours.

After the reaction is completed, the reaction solution is heated to distill off the solvent, and further heated to distill the boronate compound represented by the general formula (4). The first step is completed by adding an organic solvent (preferably ethyl acetate or diethyl ether) and, if necessary, adding water and / or an acid to separate only the organic phase and, if necessary, purifying by distillation. I do.

The second step in the present invention can be specifically carried out, for example, as follows. To the boronate compound or the boronate compound solution obtained in the first step, the compound represented by the general formula (5) and, if necessary, an appropriate organic solvent (preferably hexane or toluene) are added. The mixture is stirred at room temperature to around the boiling point of the solvent to carry out transesterification. At this time, if necessary, water and / or
Alternatively, an acid may be added to accelerate the reaction. The transesterification reaction may be performed while distilling off water. The reaction solution after the transesterification reaction is distilled to obtain the boron compound represented by the general formula (6).

The third step in the present invention can be carried out following the second step, specifically, for example, as follows. In the third step, an example of a reaction for producing a borate metal salt represented by the general formula (8) using metal magnesium as a lithium compound or a magnesium compound will be specifically described. In this case,
Is a reaction for preparing a Grignard reagent.

When a small amount of an ether solution of a halide represented by the general formula (7) is added to magnesium metal, and the mixture is agitated, the reaction temperature rises soon and the reaction (a Grignard reaction) starts. When the reaction hardly occurs, iodine, methyl iodide and the like may be added as an initiator. The reaction temperature is preferably around the boiling point of the solvent used, and an ether solution of a halide represented by the general formula (7) is added so as to maintain this temperature.

For example, in tetrahydrofuran,
It is desirable to add a halide solution in tetrahydrofuran so as to react at around 72 ° C. After adding the ether solution of the halide, the reaction is further completed by stirring at room temperature to near the boiling point of the solvent for about 30 minutes to 20 hours. The compound prepared here is the Grignard reagent.

In the case of the above reaction, a solution of the boron compound represented by the general formula (6) (preferably a solution using the same solvent as the solvent for the Grignard reaction) is added to this Grignard reagent at a reaction temperature of room temperature to room temperature. The solvent is added so as to be in the vicinity of the boiling point of the solvent.
The reaction is completed for about 2 hours to complete the third step.

In the case of the above reaction, a Grignard reagent is added to a solution of the boron compound represented by the general formula (6) (preferably a solution using the same solvent as the Grignard reaction solvent) at a reaction temperature of room temperature to the solvent. And the reaction is carried out at room temperature to near the boiling point of the solvent for about 30 minutes to 2 hours after the addition to complete the third step.

In the case of the above reaction, a Grignard reagent and a solution of the boron compound represented by the general formula (6) (preferably a solution using the same solvent as the Grignard reaction solvent) are reacted at a temperature of −100. C. to the boiling point of the solvent at the same time, and after the addition, the reaction is allowed to proceed at −100 ° C. to about the boiling point of the solvent for about 30 minutes to 2 hours, thereby completing the third step.

In the case of the above reaction, for example, a small amount of an ether-based solution of a halide represented by the general formula (7) is added to metallic magnesium and a boron-based compound represented by the general formula (6), followed by stirring. Eventually, the reaction temperature rises and the reaction starts. When the reaction hardly occurs, iodine, methyl iodide and the like may be added as an initiator. The reaction temperature is preferably around the boiling point of the solvent used, and an ether solution of a halide represented by the general formula (7) is added so as to maintain this temperature. For example, it is desirable to add a halide solution of tetrahydrofuran so as to cause the reaction in tetrahydrofuran at around 67 to 72 ° C. After adding the ether solution of the halide, the third step is completed by further reacting the mixture at room temperature to near the boiling point of the solvent for about 30 minutes to 20 hours.

In the third step, an example of the reaction for producing the above borate metal salt by using lithium metal as a compound containing lithium or magnesium will be specifically described.

As described above, using lithium metal as a compound containing lithium or magnesium, and using a halide represented by the general formula (7),
In this case, an ether solvent such as diethyl ether or tetrahydrofuran, or a solvent of hexane or cyclohexane can be used. In this case, the reaction is generally carried out under an inert gas,
It is performed at about 100 ° C. to about room temperature.

More specifically, the above-mentioned solvent is added to lithium metal, and a halide solution is added thereto. The reaction temperature varies depending on the halide and solvent used. For example, in the reaction between lithium metal and bromobenzene in diethyl ether, it is desirable to add a diethyl ether solution of bromobenzene so that the reaction temperature becomes -78 to -70 ° C. After adding the halide solution, the mixture is further stirred at -100 ° C to around room temperature for about 30 minutes to 2 hours to prepare an organolithium compound.

In the case of the above reaction, a solution obtained by dissolving the boron-based compound represented by the general formula (6) in the above-mentioned solvent (preferably an ether-based solvent) in this organolithium compound has a reaction temperature. -100 ° C. to room temperature, and after the addition, at −100 ° C. to room temperature, 30
The third step is completed by allowing the reaction to proceed for about 1 minute to 2 hours.

In the case of the above reaction, an organic lithium compound is added to a solution of the boron compound represented by the general formula (6) in the above-mentioned solvent (preferably an ether solvent) at a reaction temperature of -100 ° C. The reaction is completed for about 30 minutes to 2 hours at about room temperature to complete the third step.

In the case of the above reaction, a solution (preferably an ether solvent) of an organolithium compound and a boron compound represented by the general formula (6) is reacted at a temperature of -100 ° C.
To about the boiling point of the solvent at the same time. After the addition, the reaction is carried out at -100 ° C to about the boiling point of the solvent for about 30 minutes to 2 hours, thereby completing the third step.

Next, an example of the reaction for producing the above-mentioned borate metal salt in the third step by using an organic lithium compound as the compound containing lithium or magnesium will be specifically described. Using an organolithium compound as the compound containing lithium or magnesium as described above, and using an aromatic halide represented by the general formula (7),
It can also be manufactured using any of the above methods.

Some of the organic lithium compounds are commercially available in the form of a solution such as a hexane solution, a cyclohexane solution, and a diethyl ether solution, and can be easily obtained. In this case, a solvent for the reaction may be an ether solvent such as diethyl ether or tetrahydrofuran, or a solvent such as hexane or cyclohexane.

In general, the reaction is carried out at -100 ° C. under an inert gas.
Performed at around room temperature. An organic lithium compound is prepared by adding a halide solution to the organic lithium compound solution so that the reaction temperature is in the range of −100 ° C. to room temperature. The reaction temperature varies depending on the halide and solvent used. For example, the reaction of normal butyl lithium and 1-bromo 2,5-dimethylbenzene in diethyl ether is -7
It is preferable to add a diethyl ether solution of 1-bromo 2,5-dimethylbenzene so that the reaction is carried out at 8 to -10 ° C. After adding the halide solution, the mixture is further stirred at -100 ° C to around room temperature for about 30 minutes to 2 hours to prepare an organolithium compound. Alternatively, the organolithium compound can be prepared by adding the organolithium compound to the halide solution under the same conditions.

In the case of the above reaction, the organolithium compound is combined with a boron compound represented by the general formula (6) as described above in a solvent (preferably an ether solvent).
Is added so that the reaction temperature becomes about -100 ° C. to room temperature.
The third step is completed by allowing the reaction to proceed for about 1 minute to 2 hours.

In the case of the above reaction, an organic lithium compound is added to a solution of the boron compound represented by the general formula (6) in the above-mentioned solvent (preferably an ether solvent) at a reaction temperature of -100. The third step is completed by adding the mixture so that the temperature becomes about 0 ° C. to room temperature, and allowing the mixture to react at about −100 ° C. to about room temperature for about 30 minutes to 2 hours.

In the case of the above reaction, a solution (preferably an ether solvent) of an organolithium compound and a boron compound represented by the general formula (6) is reacted at a temperature of -100 ° C.
To about the boiling point of the solvent at the same time. After the addition, the reaction is carried out at -100 ° C to about the boiling point of the solvent for about 30 minutes to 2 hours, thereby completing the third step.

The fourth step in the present invention is, specifically,
For example, it can proceed as follows. After the completion of the third step, the reaction solution is partitioned between water and an appropriate organic solvent (preferably, ethyl acetate or diethyl ether), and the onium halide represented by the general formula (9) is added to the aqueous phase in an amount of 1.2 to 5 or the like. Then, the mixture is vigorously stirred to ion-exchange the metal cation portion of the borate. After washing with water one or two more times, only the organic phase is distilled off under reduced pressure. A solvent such as diethyl ether, hexane, or methanol is added to the residue, and the precipitate is collected by filtration and washed well with a solvent such as diethyl ether or hexane to remove the boron compound represented by the general formula (1). Obtainable.

According to the conventional production method, for example, when the compound represented by the general formula (1) is tetramethylammonium methyl (4-methylphenyl) borate, tri (4
When producing (-methylphenyl) borane, tetra (4-methylphenyl) borate may be by-produced as a side reaction to lower the purity, but according to the present invention, there is no possibility of this side reaction, A high-purity boron compound can be obtained.

[0137]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples unless departing from the gist of the present invention.

Example 1 An example of the production of 2-methyl-1,3,2-dioxaborinane will be described. (First step) 1.00 g (41.1 m) of metallic magnesium
mol) with 10 mg of iodine and 10 m of diethyl ether
15.0 ml of a 2.0 M solution of methyl bromide in diethyl ether (30.
0 mmol) is added dropwise so that the reaction temperature becomes -20 to -10 ° C, and the mixture is further stirred at -10 to 0 ° C for 2 hours. To this, 4.38 g (30.0 mmol) of triethyl boric acid
At −78 to −70 ° C., and further stirred at room temperature for 2 hours. After the completion of the reaction, 200 ml of diethyl ether was added to the reaction solution.
10 ml of concentrated hydrochloric acid, little by little,
Add 0 ml little by little. The reaction solution is transferred to a separating funnel, washed with 80 ml of water and concentrated.

(Second Step) To the solution after the first step was added 10 ml of toluene and 2.28 g of 1,3-propanediol.
And refluxed at 80 ° C. for 30 minutes. This reaction solution was distilled under reduced pressure to obtain 2.48 g of 2-methyl-1,3,2-dioxaborinane.

Example 2 2-N-Butyl-1,
The production example of 3,2-dioxaborinane is shown. (First step) 4.38 g of triethyl boric acid (30.0 m
mol) was dissolved in 20 ml of tetrahydrofuran, and 18.8 ml (30.0 mmol) of a 1.59 M solution of normal butyl lithium in hexane was added at -78 to -70 ° C.
And further stirred at room temperature for 2 hours. After the reaction,
200 ml of diethyl ether was added to the reaction solution, and concentrated hydrochloric acid 1 was added.
0 ml is added little by little, then 50 ml of water is added little by little. The reaction solution is transferred to a separating funnel, washed with 80 ml of water and concentrated. (Second step) To the solution after the first step, 10 m
l and 2.28 g of 1,3-propanediol were added.
Reflux at C for 30 minutes. The reaction solution was distilled under reduced pressure to give 2-
2. normal butyl-1,3,2-dioxaborinane;
65 g were obtained.

Example 3 2-Phenyl-1,3,2-
The production example of dioxaborinane is shown. (First step) 1.00 g (41.1 m) of metallic magnesium
mol) and 10 mg of iodine and 10
Then, a solution of 4.71 g (30.0 mmol) of phenyl bromide in 20 ml of tetrahydrofuran was added dropwise thereto under a nitrogen atmosphere so that the reaction temperature would be 68 to 72 ° C, and further at 30 to 50 ° C for 2 hours. Stir to prepare the Grignard reagent. This Grignard reagent was added to 4.38 g (30.0 mmol) of triethyl boric acid.
l) in a solution of 20 ml of tetrahydrofuran
It is added at 78 to -70 ° C, and further stirred at room temperature for 2 hours. After completion of the reaction, diethyl ether was added to the reaction solution for 200 m.
10 ml of concentrated hydrochloric acid, and then add 50 ml of water.
Add ml little by little. The reaction solution is transferred to a separating funnel, washed with 80 ml of water and concentrated. (Second step) To the solution after the first step, 10 m
l and 2.28 g of 1,3-propanediol were added.
Reflux at C for 30 minutes. The reaction solution was distilled under reduced pressure to give 2-
3.94 g of phenyl-1,3,2-dioxaborinane
Obtained.

Example 4 2-isopropyl-1,3,3
The production example of 2-dioxaborinane is shown. (First step) 1.00 g (41.1 m) of metallic magnesium
mol) with 10 mg of iodine and 10 m of diethyl ether
Then, a solution of 3.69 g (30.0 mmol) of isopropyl bromide in 20 ml of diethyl ether was added dropwise thereto under a nitrogen atmosphere so that the reaction temperature would be 36 to 40 ° C. Stir for hours to prepare the Grignard reagent. 4.38 g (30.0 mmol) of triethyl boric acid was added to the Grignard reagent.
l) in 20 ml of tetrahydrofuran is
It is added at 78 to -70 ° C, and further stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution is heated and the solvent is distilled off, whereby a colorless solid precipitates. When this solid is further heated under reduced pressure, a colorless liquid evaporates. (Second step) 10 ml of toluene, 2.28 g of 1,3-propanediol and 0.1 ml of concentrated hydrochloric acid are added to the colorless liquid after the first step, and the mixture is refluxed at 80 ° C for 30 minutes. The reaction solution was distilled under reduced pressure to give 2-isopropyl-1,3,2-
3.14 g of dioxaborinane was obtained.

Example 5 An example of the production of tetra-n-butylammonium methyl tri (4-methylphenyl) borate will be described. (Third step) 1.00 g (41.1 m) of metallic magnesium
mol) and 10 mg of iodine and 10
Then, a solution of 5.64 g (33.0 mmol) of 4-bromotoluene dissolved in 20 ml of tetrahydrofuran was added dropwise thereto under a nitrogen atmosphere so that the reaction temperature became 67 to 72 ° C, and further at 30 to 50 ° C. Stir for 2 hours. The 2-methyl-1,3,2 produced in Example 1
-1.00 g (10.0 mmol) of dioxaborinane are added at the same temperature, and the mixture is further stirred at 30 to 50 ° C for 2 hours. (Fourth step) When the reaction solution has dropped to room temperature, 200 ml of diethyl ether is added, and then 50 ml of water is added little by little. The reaction solution was transferred to a separating funnel,
l, wash in the order of 60 ml of a 0.2 M aqueous solution of tetra-n-butylammonium bromide and 80 ml of water, and then concentrate. 200 ml of diethyl ether was added to the residue, and the precipitated solid was collected by filtration, and 5.00 g of the desired product as a white solid (9.2 g).
3 mmol) in 92% yield. When the mass spectrum of this white solid was measured, the anion part was 299 and the cation part was 242, which were in agreement with the theoretical values. The structure of the target product was confirmed by elemental analysis. The results are shown in Table 1.

Example 6 An example of the production of tetramethylammonium normal butyl trinormal octyl borate will be described. (Third step) 1.00 g (41.1 m) of metallic magnesium
mol) in a nitrogen atmosphere, 1-chlorooctane 4.91
g (33.0 mmol) in 20 ml of diethyl ether is added dropwise to prepare a Grignard reagent.
This Grignard reagent was treated with 1.42 g of 2-normalbutyl-1,3,2-dioxaborinane prepared in Example 2.
(10.0 mmol) is added dropwise to a solution of 10 ml of tetrahydrofuran so that the reaction temperature does not exceed 50 ° C. Further, the reaction is completed by stirring at 30 to 50 ° C. for 2 hours. (Fourth step) When the reaction solution has dropped to room temperature, 200 ml of diethyl ether is added, and then 50 ml of water is added little by little. The reaction solution was transferred to a separating funnel,
l, wash in the order of 0.2 M tetramethylammonium bromide aqueous solution 60 ml and water 80 ml, and concentrate. 200 ml of diethyl ether was added to the residue, and the precipitated solid was collected by filtration, and 4.39 g (9.11 mmol) of the target substance as a white solid was collected.
l) was obtained in 91% yield. When the mass spectrum of this white solid was measured, the anion part was 407 and the cation part was 74, which were in agreement with the theoretical values. The structure of the target product was confirmed by elemental analysis. The results are shown in Table 1.

Example 7 An example of the production of tetra-n-butylammonium-n-butyltri (4-tert-butylphenyl) borate is shown. (Third step) 1.00 g (41.1 m) of metallic magnesium
mol) and 10 mg of iodine,
Normal butyl-1,3,2-dioxaborinane 1.4
2 g (10.0 mmol) and 10 m of tetrahydrofuran
and 1-bromo-4-te under nitrogen atmosphere.
7.03 g (33.0 mmol) of rt-butylbenzene
In 20 ml of tetrahydrofuran was added dropwise so that the reaction temperature became 67 to 72 ° C., and 30 to 5
The reaction is completed by stirring at 0 ° C. for 2 hours. (Fourth step) When the reaction solution has dropped to room temperature, 200 ml of diethyl ether is added, and then 50 ml of water is added little by little. The reaction solution was transferred to a separating funnel,
l, wash in the order of 60 ml of a 0.2 M aqueous solution of tetra-n-butylammonium bromide and 80 ml of water, and then concentrate. 200 ml of diethyl ether was added to the residue, and the precipitated solid was collected by filtration, and 6.80 g of the desired product as a white solid (9.5).
7 mmol) in 95% yield. When the mass spectrum of this white solid was measured, the anion part was 467 and the cation part was 242, which were in agreement with the theoretical values. The structure of the target product was confirmed by elemental analysis. The results are shown in Table 1.

Example 8 An example of the production of tetra-n-butylammonium-n-butyltri (4-methyl-naphthyl) borate will be described. (Third step) 1.00 g (41.1 m) of metallic magnesium
mol) and 10 mg of iodine,
Normal butyl-1,3,2-dioxaborinane 1.4
2 g (10.0 mmol) and 10 m of tetrahydrofuran
Under a nitrogen atmosphere, a solution of 7.30 g (33.0 mmol) of 1-bromo-4-methylnaphthalene in 20 ml of tetrahydrofuran was added at a reaction temperature of 67 ml.
To 72 ° C, and further at 30 to 50 ° C for 2 hours.
The reaction is completed by stirring for an hour. (Fourth step) When the reaction solution has dropped to room temperature, 200 ml of diethyl ether is added, and then 50 ml of water is added little by little. The reaction solution was transferred to a separating funnel,
l, wash in the order of 60 ml of a 0.2 M aqueous solution of tetra-n-butylammonium bromide and 80 ml of water, and then concentrate. 200 ml of diethyl ether was added to the residue, and the precipitated solid was collected by filtration, and 6.75 g (9.1 g) of the target product as a white solid was collected.
9 mmol) in 91% yield. When the mass spectrum of this compound was measured, the anion part was 491 and the cation part was 242, which were in agreement with the theoretical values. The structure of the target product was confirmed by elemental analysis. The results are shown in Table 1.

Example 9 An example of the production of tetraethylammonium phenyl tri (2,5-dimethylphenyl) borate will be described. (Third step) Metal lithium 0.3 g (43.2 mmol)
10 ml of diethyl ether was added to 1), and 1-bromo-2,5-dimethylbenzene 6.1 was added thereto under a nitrogen atmosphere.
1 g (33.0 mmol) of diethyl ether 20 ml
Is added dropwise so that the reaction temperature becomes -75 to -65 ° C, and the mixture is further stirred at the same temperature for 2 hours. This is added dropwise to a solution prepared by dissolving 1.62 g (1.0 mmol) of 2-phenyl-1,3,2-dioxaborinane prepared in Example 3 in 10 ml of tetrahydrofuran so that the reaction temperature does not exceed 5 ° C. The reaction is completed by further stirring at 0-5 ° C for 2 hours. (Fourth step) When the temperature of the reaction solution reaches room temperature, 200 ml of diethyl ether is added, and then 50 ml of water is added little by little. The reaction solution was transferred to a separating funnel,
l, wash with 0.2 M tetraethylammonium bromide aqueous solution 60 ml and water 80 ml in this order, and concentrate. 200 ml of diethyl ether was added to the residue, and the precipitated solid was collected by filtration, and 3.80 g (7.10 mmol) of the target substance as a white solid was collected.
l) was obtained with a yield of 71%. When the mass spectrum of this product was measured, the anion part was 403 and the cation part was 1
At 30, it was in agreement with the theoretical value. The structure of the target product was confirmed by elemental analysis. The results are shown in Table 1.

[0148]

[Table 1]

[0149]

According to the method for producing a boron-based compound of the present invention, a high-purity boron-based compound useful as a photoinitiator or a light-absorbing decolorizer can be obtained in a high yield, as compared with the conventional method. Obtainable.

Claims (6)

[Claims] 1. A compound containing lithium or magnesium, a compound represented by the general formula (2) and a borate compound represented by the general formula (3) are reacted in a solvent to obtain a compound represented by the general formula (4): And a second step of reacting the boronate compound represented by the general formula (4) with the compound represented by the general formula (5). A method for producing a boron-based compound represented by the formula (6). Embedded image (Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, Y represents a heterocyclic group which may be substituted, or an alicyclic group which may be substituted.
₁ represents a halogen atom. ) (Wherein R ₃ , R ₄ , and R ₅ may be the same or different, and each represents an optionally substituted alkyl group, an optionally substituted alkenyl group, Represents an aryl group which may be substituted, an aralkyl group which may be substituted, and an alicyclic group which may be substituted.) (Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, Represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group.
₄ and R ₅ may be the same or different, and each have an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, Represents an aralkyl group which may be substituted and an alicyclic group which may be substituted. ) (Wherein R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group or may have a substitution. An alkenyl group, an aryl group which may be substituted, an aralkyl group which may be substituted, an alicyclic group which may be substituted, and a hydrogen atom. (Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, Represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group.
₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group, an optionally substituted alkenyl group, Represents an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alicyclic group, or a hydrogen atom. ) 2. A compound containing lithium or magnesium, a compound represented by the general formula (2) and a borate compound represented by the general formula (3) are reacted in a solvent to obtain a compound represented by the general formula (4): Reacting a boronate compound represented by the general formula (4) with a compound represented by the general formula (5),
A second step of producing a boron-based compound represented by the general formula (6), a compound containing lithium or magnesium, a compound represented by the general formula (7), and a boron-based compound represented by the general formula (6) Is reacted in a solvent to produce a borate metal salt represented by the general formula (8), and a borate metal salt represented by the general formula (8) is represented by the general formula (9). A method for producing a boron-based compound represented by the general formula (1), comprising a fourth step of adding an onium halide to cause an ion exchange reaction. Embedded image (Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, Y represents a heterocyclic group which may be substituted, or an alicyclic group which may be substituted.
₁ represents a halogen atom. ) (Wherein R ₃ , R ₄ , and R ₅ may be the same or different, and each represents an optionally substituted alkyl group, an optionally substituted alkenyl group, Represents an aryl group which may be substituted, an aralkyl group which may be substituted, and an alicyclic group which may be substituted.) (Wherein R ₁ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, an optionally substituted aralkyl group, Represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group.
₄ and R ₅ may be the same or different, and each have an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, Represents an aralkyl group which may be substituted and an alicyclic group which may be substituted. ) (Wherein R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group or may have a substitution. An alkenyl group, an aryl group which may be substituted, an aralkyl group which may be substituted, an alicyclic group which may be substituted, and a hydrogen atom. (In the formula, R ₁ represents an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, Represents an optionally substituted heterocyclic group or an optionally substituted alicyclic group.
₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and may have an optionally substituted alkyl group, an optionally substituted alkenyl group, Represents an optionally substituted aryl group, an optionally substituted aralkyl group, an optionally substituted alicyclic group, or a hydrogen atom. ) (In the formula, R ₂ represents an alkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an aralkyl group which may be substituted, Y represents a heterocyclic group which may be substituted, or an alicyclic group which may be substituted.
₁ represents a halogen atom. ) (Wherein R ₁ and R ₂ are different, and R ₁ , R ₂
Are each independently an alkyl group which may have a substituent,
Optionally substituted alkenyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted heterocyclic group, optionally substituted alicyclic group Represents a group. M represents a lithium atom or a magnesium atom.
n = 1,2. ) (In the formula, Z ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a phosphonium cation, and an iodonium cation. X represents a halogen atom.) (Wherein R ₁ and R ₂ are different, and R ₁ , R ₂
Are each independently an alkyl group which may have a substituent,
Optionally substituted alkenyl group, optionally substituted aryl group, optionally substituted aralkyl group, optionally substituted heterocyclic group, optionally substituted alicyclic group Represents a group. Z ⁺ represents an ammonium cation, a sulfonium cation, an oxosulfonium cation, a phosphonium cation, and an iodonium cation. ) 3. In the first step, a compound containing lithium or magnesium is reacted with a compound represented by the general formula (2) in a solvent, and a compound represented by the general formula (3) is added thereto and reacted. Or a compound represented by the general formula (3):
A compound obtained by reacting a compound containing lithium or magnesium with a compound represented by the general formula (2) in a solvent is added and reacted, or a compound containing lithium or magnesium and a compound represented by the general formula (2) are added. A compound obtained by reacting a compound in a solvent and a compound represented by the general formula (3) are simultaneously added and reacted to obtain a compound represented by the general formula (4):
The method for producing a boron-based compound according to claim 1, wherein the boronate compound represented by the following formula is produced. 4. The method for producing a boron compound according to claim 1, wherein the compound containing lithium or magnesium is a metal lithium, a metal magnesium, or an organic lithium compound. 5. The method for producing a boron-based compound according to claim 2, wherein the compound containing lithium or magnesium used in the third step is an organic lithium compound. 6. The method according to claim 2, wherein the solvent used in the third step is tetrahydrofuran.