JP2012140421A - Method of producing organic metal compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing organic metal compounds, especially dialkyl metallocene compounds, efficiently without using low temperatures.SOLUTION: The method of producing organic metal compounds comprises reacting a tetrahalo metal compound delivered as solution from a syringe pump S1 with an alkyllithium compound delivered as solution from a syringe pump S2 in a microreactor consisting of a T-shaped micromixer M1 and a microtube reactor R1 to form a tetraalkyl metal compound and then reacting the tetraalkyl metal compound with a compound having an active proton which is delivered as solution from a syringe pump S3 in a microreactor consisting of a T-shaped micromixer M2 and a microtube reactor R2.

Description

The present invention relates to a method for producing an organometallic compound, particularly a metallocene compound.

Organometallic compounds, particularly metallocene compounds, are widely used as olefin polymerization catalyst components. In conventionally known metallocene compounds, the ligand of the central metal atom usually includes a pi-bonded ligand such as a cyclopentadienyl group and a halogen atom which is a sigma-bonded ligand such as a chlorine atom. It is used. Further, a dimethyl metallocene compound having an alkyl group, particularly a methyl group, instead of the halogen atom has been developed and used as an olefin polymerization catalyst component.
Here, as a method for producing a dimethyl metallocene compound, a method is known in which a cyclopentadienyl ligand metal salt is reacted with a transition metal compound, and the obtained metallocene dihalide is reacted with an alkylating agent (for example, Patent Documents). 1).
As another method for producing a dimethylmetallocene compound, methyllithium and indene are reacted to obtain a mixture of lithioindene and methyllithium. By reacting the mixture with zirconium tetrachloride, bisindenylzirconium dimethyl is obtained. A manufacturing method is known (for example, Patent Document 2).

International Publication WO96 / 19488 JP-T-2001-516367

However, although the method described in Patent Document 1 requires a two-step reaction step even though the yield of the dimethylmetallocene compound is as low as 24%, the intermediate metallocene dihalide is isolated and purified. There is a problem that the process is complicated and the efficiency is low.
In addition, although the method described in Patent Document 2 has a good yield of about 80%, it requires a low temperature of −70 to −80 ° C. and is a batch reaction, so that the reaction efficiency is low. is there.

  An object of this invention is to provide the method of manufacturing an organometallic compound, especially a dialkyl metallocene compound efficiently, without using low temperature.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by performing a reaction using a microreactor, and have completed the present invention.

  That is, in the method of the present invention, a tetrahalo metal compound is reacted with an alkyl lithium compound in a microreactor to form a tetraalkyl metal compound (hereinafter referred to as a first reaction), and then the tetraalkyl metal compound is reacted in the microreactor. The present invention relates to a method for producing an organometallic compound characterized by reacting with a compound having active protons (hereinafter referred to as a second reaction).

  According to the present invention, an organometallic compound, particularly a dialkyl metallocene compound can be efficiently produced without using a low temperature, and thus has high industrial utility value.

  The method of the present invention involves reacting a tetrahalo metal compound with an alkyl lithium compound in a microreactor to form a tetraalkyl metal compound, and then reacting the tetraalkyl metal compound with a compound having an active proton in the microreactor to form an organic compound. A metal compound is produced.

The microreactor used in the present invention is a reaction apparatus using a micro space used for performing a chemical reaction as a reaction field, and the apparatus is composed of a micromixer and a microtube. Here, the micromixer has a space where two or more inflow channels, one or more outflow channels and the two or more inflow channels merge, and the diameter of the inflow channel connected to the merge space is 0.01 to It is about 1000 micrometers. There is no restriction | limiting in particular about the shape of the micromixer used by this invention, Well-known things, such as a T-shaped mixer and a Y-shaped mixer, can be used. Moreover, a microtube with a diameter of 10 to 1000 micrometers is usually used.

  First, the first reaction will be described. The first reaction comprises a step of reacting a tetrahalo metal compound with an alkyl lithium compound in a microreactor to produce a tetraalkyl metal compound.

The tetrahalo metal compound used in the first reaction is represented by the formula (1):
MX ₄ (1)
(In the formula, M represents zirconium, titanium or hafnium, and X represents a halogen atom.)
The tetrahalo metal compound represented by these is mentioned.

  In formula (1), M represents zirconium, titanium or hafnium, and zirconium is preferred. X represents a halogen atom, and specific examples include a chlorine atom, a bromine atom and an iodine atom, with a chlorine atom being preferred.

  Specific examples of the tetrahalo metal compound include zirconium tetrachloride, titanium tetrachloride, and hafnium tetrachloride.

Examples of the alkyl lithium compound include the formula (2):
LiR ¹ (2)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms.)
The alkyl lithium compound represented by these is mentioned.

In formula (2), R ¹ is an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

  Specific examples of the alkyllithium compound include methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, isobutyllithium, sec-butyllithium, and tert-butyllithium, and methyllithium is preferred.

As a solvent for producing a tetraalkyl metal compound by reacting a tetrahalo metal compound with an alkyl lithium compound in a microreactor, an ether solvent is usually used. The ether solvent used may be used individually by 1 type, and may mix and use 2 or more types. Specific examples of the ether solvent include THF, dioxane, diethyl ether, dibutyl ether and the like, and THF is preferable.

The micromixer is used for mixing the tetrahalo metal compound and the alkyl lithium compound. It is preferable to use the micromixer because the mixing efficiency is improved and the progress of the reaction is accelerated.

  The use ratio of the tetrahalo metal compound and the alkyl lithium compound is not particularly limited, and an alkyl lithium compound may be used in such an amount that a desired tetraalkyl metal compound is obtained. Specifically, the amount is usually 4 to 8 mol, preferably 4 to 6 mol, relative to 1 mol of the tetrahalo metal compound.

  In the first reaction, a tetrahalo metal compound and an alkyl lithium compound are reacted in a microreactor to produce a tetraalkyl metal compound. The reaction temperature is not particularly limited, but is usually about −10 to 100 ° C., preferably about 0 to 50 ° C., more preferably 0 to 35 ° C. When heating or cooling the reaction system, for example, a method of immersing the microreactor in a heat medium set to a predetermined temperature can be employed.

  Further, the liquid feeding method for supplying the tetrahalo metal compound and the alkyl lithium compound to the microreactor is not particularly limited, and a known method can be adopted. Specifically, for example, a liquid feeding pump for liquid chromatography, a syringe pump, or the like that can send liquid at a constant flow rate may be used.

  There is no particular limitation on the liquid feeding speed when the mixture of the tetrahalo metal compound and the alkyl lithium compound is supplied to the microreactor. Specifically, for example, in the case of a reactor having an inner diameter of 1000 micrometers and a length of about 200 centimeters. The flow rate may be adjusted so that the residence time is about 12.4 to 94.2 seconds, preferably about 12.4 to 47.1 seconds.

  The tetraalkyl metal compound thus obtained is usually used as it is in the second reaction. Specific examples of the resulting tetraalkyl metal compound include tetramethylzirconium, tetraethylzirconium, tetrapropylzirconium, tetraisopropylzirconium, tetrabutylzirconium, tetraisobutylzirconium, tetrasec-butylzirconium, tetratert-butylzirconium, Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetraisopropyltitanium, tetrabutyltitanium, tetraisobutyltitanium, tetrasec-butyltitanium, tetratert-butyltitanium, tetramethylhafnium, tetraethylhafnium, tetrapropylhafnium, tetraisopropylhafnium, Tetrabutyl hafnium, tetraisobutyl ha Bromide, tetra-sec- butyl hafnium, tetra tert- butyl hafnium, and the like.

  Next, the second reaction will be described. The second reaction comprises a step of reacting the tetraalkyl metal compound obtained in the first reaction with a compound having active protons in a microreactor to produce an organometallic compound.

  As a compound which has an active proton, the compound represented by either of Formula (3)-Formula (5) is mentioned, for example.

Formula (3):
HNR ² R ³ (3)
(Wherein R ² and R ³ are the same as or different from each other, and represent an alkyl group having 1 to 8 carbon atoms),

Formula (4):

（式中、Ｒ^４及びＲ^５は互いに同一又は異なって、水素原子、ハロゲン原子、アルキル基、アリール基又はエステル基を示すか、或いはＲ^４及びＲ^５が末端で互いに結合してアリール基、エステル基、ハロゲン原子で置換されていてもよいＣ５〜Ｃ６の環を形成する。）、

(Wherein R ⁴ and R ⁵ are the same as or different from each other and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an ester group, or R ⁴ and R ⁵ are bonded to each other at the end to form an aryl group; An ester group, a C5-C6 ring optionally substituted with a halogen atom is formed).

Formula (5):

（式中、Ｒ^６及びＲ^７は互いに同一又は異なって、水素原子、ハロゲン原子、アルキル基、アリール基又はエステル基を示すか、或いはＲ^６及びＲ^７が末端で互いに結合してアリール基、エステル基、ハロゲン原子で置換されていてもよいＣ５〜Ｃ６の環を形成する。Ｂは炭素原子または珪素原子を有する架橋基を示す。）

(Wherein R ⁶ and R ⁷ are the same as or different from each other and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an ester group, or R ⁶ and R ⁷ are bonded to each other at the terminal to form an aryl group; An ester group forms a C5 to C6 ring optionally substituted with a halogen atom, and B represents a bridging group having a carbon atom or a silicon atom.

In Formula (3), R ² and R ³ are the same as or different from each other, and represent an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 3 carbon atoms. More preferred. Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group and the like.

  Specific examples of the compound having an active proton represented by the formula (3) include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, disec-butylamine, ditert-butylamine, dipentylamine. , Dihexylamine, diheptylamine, dioctylamine, ethylmethylamine, methylpropylamine, methylisopropylamine, ethylpropylamine, ethylisopropylamine and the like.

In the formula (4), R ⁴ and R ⁵ are the same or different from each other and represent a hydrogen atom, an alkyl group, an aryl group, an ester group or a halogen atom, or R ⁴ and R ⁵ are bonded to each other at the terminal to form an aryl. A C5-C6 ring optionally substituted with a group, an ester group or a halogen atom is formed. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Specific examples of the aryl group include a phenyl group and a 4-methylphenyl group. Specific examples of the ester group include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, and tert-butyl ester. Specific examples of the halogen atom include chlorine, bromine, iodine and the like.

  Specific examples of the compound represented by the formula (4) include cyclopentadiene, mono-, di-, tri-, tetra- and pentamethylcyclopentadiene, chlorocyclopentadiene, bromocyclopentadiene, iodocyclopentadiene, and cyclopentadiene carboxylic acid. Methyl, indene, 2-methylindene, 2-methyl-4-phenylindene, 2-ethyl-4-phenylindene, 2-isopropyl-4-phenylindene, 4-chloroindene, 4-bromoindene, 4-iodoindene 2-methyl-4-chloroindene, 2-methyl-4-bromoindene, 2-methyl-4-iodoindene, methyl 2-methylindene-4-carboxylate and the like.

In the formula (5), R ⁶ and R ⁷ are the same or different from each other and represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an ester group, or R ⁶ and R ⁷ are bonded to each other at the terminal to form an aryl. A C5-C6 ring optionally substituted with a group, an ester group or a halogen atom is formed. B represents a bridging group having a carbon atom or a silicon atom. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Specific examples of the aryl group include a phenyl group and a 4-methylphenyl group. Specific examples of the ester group include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, and tert-butyl ester. Specific examples of the halogen atom include chlorine, bromine, iodine and the like. Specific examples of B include dimethylsilanediyl, methylphenylsilanediyl, diphenylsilanediyl, methylcyclohexylsilanediyl, ethylene, and the like, with dimethylsilanediyl and ethylene being preferred.

  Specific examples of the compound having an active proton represented by the formula (5) include dimethylsilanediylbiscyclopentadiene, dimethylsilanediylbis (methylcyclopentadiene), dimethylsilanediylbis (dimethylcyclopentadiene), and dimethylsilanediyl. Bis (trimethylcyclopentadiene), dimethylsilanediylbis (tetramethylcyclopentadiene), dimethylsilanediylbis (pentamethylcyclopentadiene), dimethylsilanediylbis (chlorocyclopentadiene), dimethylsilanediylbis (bromocyclopentadiene), dimethyl Silanediylbis (iodocyclopentadiene), dimethylsilanediylbis (methyl cyclopentadienecarboxylate), dimethylsilanediylbisindene, dimethylsilane Didiylbis (2-methylindene), dimethylsilanediylbis (2-methyl-4-phenylindene), dimethylsilanediylbis (2-ethyl-4-phenylindene), dimethylsilanediylbis (2-isopropyl-4-phenyl) Indene), dimethylsilanediylbis (4-chloroindene), dimethylsilanediylbis (4-bromoindene), dimethylsilanediylbis (4-iodoindene), dimethylsilanediylbis (indene-4-carboxylate methyl), Dimethylsilanediylbis (2-methyl-4-chloroindene), dimethylsilanediylbis (2-methyl-4-bromoindene), dimethylsilanediylbis (2-methyl-4-iodoindene), dimethylsilanediylbis ( 2-methylindene-4-ca Methyl borate) ethylenebis (cyclopentadiene), ethylenebis (methylcyclopentadienyl), ethylenebis (dimethylcyclopentadiene), ethylenebis (trimethylcyclopentadiene), ethylenebis (tetramethylcyclopentadiene), ethylenebis (penta Methylcyclopentadiene), ethylene bis (chlorocyclopentadiene), ethylene bis (bromocyclopentadiene), ethylene bis (iodocyclopentadiene), ethylene bis (methyl cyclopentadienecarboxylate), ethylene bisindenylzirconium dimethyl, ethylene bis (2 -Methylindene), ethylenebis (2-methyl-4-phenylindenyl), ethylenebis (2-ethyl-4-phenylindene), ethylenebis (2-isopropyl Pyr-4-phenylindene), ethylene bis (4-chloroindene), ethylene bis (4-bromoindene), ethylene bis (4-iodoindene), ethylene bis (indene-4-carboxylate methyl), ethylene bis ( 2-methyl-4-chloroindene), ethylenebis (2-methyl-4-bromoindene), ethylenebis (2-methyl-4-iodoindene), ethylenebis (methyl 2-methylindene-4-carboxylate) Etc.

As the solvent for producing an organometallic compound by reacting a tetraalkyl metal compound with a compound having an active proton in a microreactor, an ether solvent is usually used. The ether solvent used may be used individually by 1 type, and may mix and use 2 or more types. Specific examples of the ether solvent include THF, dioxane, diethyl ether, dibutyl ether and the like, and THF is preferable.

The mixing of the tetraalkyl metal compound and the compound having an active proton can be performed in the same apparatus as in the first reaction.

  The ratio of the tetraalkyl metal compound and the compound having active protons is not particularly limited, and a compound having active protons in such an amount that a desired organometallic compound can be obtained may be used. Specifically, it is 2 to 10 mol, preferably 2 to 5 mol, per 1 mol of the tetraalkyl metal compound.

  In the second reaction, a tetraalkyl metal compound is reacted with a compound having an active proton in a microreactor to produce an organometallic compound. The reaction temperature is not particularly limited, but is usually about −10 to 100 ° C., preferably about 0 to 50 ° C., more preferably about 0 to 35 ° C. When heating or cooling the reaction system, for example, a method of immersing the microreactor body in a heat medium set at a predetermined temperature can be employed.

  Moreover, about the liquid feeding method at the time of supplying the compound which has a tetraalkyl metal compound and an active proton to a microreactor, it can carry out by the method similar to a 1st reaction.

  There is no particular limitation on the liquid feeding speed when a mixture of a tetraalkyl metal compound and a compound having an active proton is supplied to the microreactor. Specifically, for example, a reactor having an inner diameter of 1000 micrometers and a length of about 200 centimeters. In this case, the flow rate may be adjusted so that the residence time is about 12.4 to 94.2 seconds, preferably about 12.4 to 47.1 seconds.

  When the compound having an active proton to be used is a compound represented by any one of the formulas (3) to (5), the organometallic compound thus obtained has the formula (6) to formula ( 8).

Formula (6):
M (NR ² R ³ ) ₄ (6)
(Wherein M, R ² and R ³ are the same as above),

Formula (7):

（式中、Ｍ、Ｒ^１、Ｒ^４及びＲ^５は前記と同じ。）、

(Wherein, M, R ¹ , R ⁴ and R ⁵ are the same as above),

Formula (8):

（式中、Ｍ、Ｒ^１、Ｂ、Ｒ^６及びＲ^７は前記と同じ。）

(In the formula, M, R ¹ , B, R ⁶ and R ⁷ are the same as above.)

  Specific examples of the compound represented by the formula (6) include tetrakisdimethylamidozirconium, tetrakisdiethylamidozirconium, tetrakisdipropylamidozirconium, tetrakisdiisopropylamidozirconium, tetrakisdibutylamidozirconium, tetrakisdiisobutyramidezirconium, tetrakisdisec- Butyramide zirconium, tetrakisdi tert-butylamide zirconium, tetrakisdipentylamide zirconium, tetrakisdihexylamide zirconium, tetrakisdiheptylamide zirconium, tetrakis dioctylamide zirconium, tetrakisethylmethylamide zirconium, tetrakismethylpropylamide zirconium, tetrakismethylisopropylamide zirconium , Tetrakisethylpropylamide zirconium, tetrakisethylisopropylamide zirconium, tetrakisdimethylamido titanium, tetrakisdiethylamido titanium, tetrakisdipropylamido titanium, tetrakisdiisopropylamido titanium, tetrakisdibutylamido titanium, tetrakisdiisobutylamido titanium, tetrakisdi sec-butylamido titanium , Tetrakisdi tert-butylamido titanium, tetrakisdipentylamido titanium, tetrakisdihexylamido titanium, tetrakisdiheptylamido titanium, tetrakis dioctylamido titanium, tetrakisethylmethylamido titanium, tetrakismethylpropylamido titanium, tetrakismethi Isopropylamido titanium, tetrakisethylpropylamido titanium, tetrakisethylisopropylamido titanium, tetrakisdimethylamido hafnium, tetrakisdiethylamidohafnium, tetrakisdipropylamidohafnium, tetrakisdiisopropylamidohafnium, tetrakisdibutylamidohafnium, tetrakisdiisobutylamidohafnium, tetrakisdisec-butyl Amido hafnium, tetrakisdi tert-butylamide hafnium, tetrakisdipentylamide hafnium, tetrakisdihexylamide hafnium, tetrakisdiheptylamide hafnium, tetrakisdioctylamide hafnium, tetrakisethylmethylamide hafnium, tetrakismethylpropylamide hafnium And tetrakismethylisopropylamide hafnium, tetrakisethylpropylamide hafnium, tetrakisethylisopropylamide hafnium, and the like.

  Specific examples of the compound represented by the formula (7) include biscyclopentadienylzirconium dimethyl, bismethylcyclopentadienylzirconium dimethyl, bisdimethylcyclopentadienylzirconium dimethyl, and bistrimethylcyclopentadienylzirconium. Dimethyl, bistetramethylcyclopentadienylzirconium dimethyl, bispentamethylcyclopentadienylzirconium dimethyl, bis (chlorocyclopentadienyl) zirconium dimethyl, bis (bromocyclopentadienyl) zirconium dimethyl, bis (iodocyclopentadi) Enyl) zirconium dimethyl, bis (cyclopentadienecarboxylate) zirconium dimethyl, bisindenylzirconium dimethyl, bis (2-indenyl) zirco Um dimethyl, bis (2-methyl-4-phenylindenyl) zirconium dimethyl, bis (2-ethyl-4-phenylindenyl) zirconium dimethyl, bis (2-isopropyl-4-phenylindenyl) zirconium dimethyl, bis (4 -Chloroindenyl) zirconium dimethyl, bis (4-bromoindenyl) zirconium dimethyl, bis (4-iodoindenyl) zirconium dimethyl, bis (2-methyl-4-chloroindenyl) zirconium dimethyl, bis (2-methyl) -4-bromoindenyl) zirconium dimethyl, bis (2-methyl-4-iodoindenyl) zirconium dimethyl, bis (2-methylindene-4-carboxylate methyl) zirconium dimethyl, biscyclopentadienyltitanium dimethyl, bi Methylcyclopentadienyltitanium dimethyl, bisdimethylcyclopentadienyltitanium dimethyl, bistrimethylcyclopentadienyltitanium dimethyl, bistetramethylcyclopentadienyltitanium dimethyl, bispentamethylcyclopentadienyltitanium dimethyl, bis (chlorocyclo Pentadienyl) titanium dimethyl, bis (bromocyclopentadienyl) titanium dimethyl, bis (iodocyclopentadienyl) titanium dimethyl, bis (cyclopentadienecarboxylate methyl) titanium dimethyl, bisindenyltitanium dimethyl, bis (2- Indenyl) titanium dimethyl, bis (2-methyl-4-phenylindenyl) titanium dimethyl, bis (2-ethyl-4-phenylindenyl) ) Titanium dimethyl, bis (2-isopropyl-4-phenylindenyl) titanium dimethyl, bis (4-chloroindenyl) titanium dimethyl, bis (4-bromoindenyl) titanium dimethyl, bis (4-iodoindenyl) titanium Dimethyl, bis (2-methyl-4-chloroindenyl) titanium dimethyl, bis (2-methyl-4-bromoindenyl) titanium dimethyl, bis (2-methyl-4-iodoindenyl) titanium dimethyl, bis (2 -Methyl indene-4-carboxylate) titanium dimethyl, biscyclopentadienyl hafnium dimethyl, bismethylcyclopentadienyl hafnium dimethyl, bisdimethylcyclopentadienyl hafnium dimethyl, bistrimethylcyclopentadienyl huff Um dimethyl, bistetramethylcyclopentadienyl hafnium dimethyl, bispentamethylcyclopentadienyl hafnium dimethyl, bis (chlorocyclopentadienyl) hafnium dimethyl, bis (bromocyclopentadienyl) hafnium dimethyl, bis (iodocyclopentadi) Enyl) hafnium dimethyl, bis (methyl cyclopentadienecarboxylate) hafnium dimethyl, bisindenyl hafnium dimethyl, bis (2-indenyl) hafnium dimethyl, bis (2-methyl-4-phenylindenyl) hafnium dimethyl, bis (2- Ethyl-4-phenylindenyl) hafnium dimethyl, bis (2-isopropyl-4-phenylindenyl) hafnium dimethyl, bis (4-chloroindenyl) hafnium dimethyl Bis (4-bromoindenyl) hafnium dimethyl, bis (4-iodoindenyl) hafnium dimethyl, bis (2-methyl-4-chloroindenyl) hafnium dimethyl, bis (2-methyl-4-bromoindenyl) hafnium And dimethyl, bis (2-methyl-4-iodoindenyl) hafnium dimethyl, bis (2-methylindene-4-carboxylate methyl) hafnium dimethyl, and the like.

  Specific examples of the compound represented by the formula (8) include dimethylsilanediylbiscyclopentadienylzirconium dimethyl, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (dimethylcyclopenta). Dienyl) zirconium dimethyl, dimethylsilanediylbis (trimethylcyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (tetramethylcyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (pentamethylcyclopentadienyl) zirconium dimethyl, Dimethylsilanediylbis (chlorocyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (bromocyclopentadienyl) zirconium dimethyl, dimethyl Rusilanediylbis (iodocyclopentadienyl) zirconium dimethyl, dimethylsilanediylbis (methyl cyclopentadienecarboxylate) zirconium dimethyl, dimethylsilanediylbisindenylzirconium dimethyl, dimethylsilanediylbis (2-methylindenyl) zirconium dimethyl Dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dimethyl, dimethylsilanediylbis (2-ethyl-4-phenylindenyl) zirconium dimethyl, dimethylsilanediylbis (2-isopropyl-4-phenylindene) Nyl) zirconium dimethyl, dimethylsilanediylbis (4-chloroindenyl) zirconiumdimethyl, dimethylsilanediylbis (4-bromoindenyl) zirconi Dimethylsilane, dimethylsilanediylbis (4-iodoindenyl) zirconium dimethyl, dimethylsilanediylbis (methyl indene-4-carboxylate) zirconium dimethyl, dimethylsilanediylbis (2-methyl-4-chloroindenyl) zirconium dimethyl, Dimethylsilanediylbis (2-methyl-4-bromoindenyl) zirconium dimethyl, dimethylsilanediylbis (2-methyl-4-iodoindenyl) zirconium dimethyl, dimethylsilanediylbis (2-methylindene-4-carboxylic acid) Methyl) zirconium dimethyl, ethylenebis (cyclopentadienyl) zirconium dimethyl, ethylenebis (methylcyclopentadienyl) zirconium dimethyl, ethylenebis (dimethylcyclopentadienyl) di Luconium dimethyl, ethylene bis (trimethylcyclopentadienyl) zirconium dimethyl, ethylene bis (tetramethylcyclopentadienyl) zirconium dimethyl, ethylene bis (pentamethylcyclopentadienyl) zirconium dimethyl, ethylene bis (chlorocyclopentadienyl) ) Zirconium dimethyl, ethylene bis (bromocyclopentadienyl) zirconium dimethyl, ethylene bis (iodocyclopentadienyl) zirconium dimethyl, ethylene bis (methyl cyclopentadienecarboxylate) zirconium dimethyl, ethylene bisindenyl zirconium dimethyl, ethylene bis ( 2-methylindenyl) zirconium dimethyl, ethylenebis (2-methyl-4-phenylindenyl) zirconium dimethyl, Tylene bis (2-ethyl-4-phenylindenyl) zirconium dimethyl, ethylenebis (2-isopropyl-4-phenylindenyl) zirconium dimethyl, ethylenebis (4-chloroindenyl) zirconium dimethyl, ethylenebis (4-bromoindene) Nyl) zirconium dimethyl, ethylene bis (4-iodoindenyl) zirconium dimethyl, ethylene bis (indene-4-carboxylate methyl) zirconium dimethyl, ethylene bis (2-methyl-4-chloroindenyl) zirconium dimethyl, ethylene bis ( 2-methyl-4-bromoindenyl) zirconium dimethyl, ethylenebis (2-methyl-4-iodoindenyl) zirconium dimethyl, ethylenebis (2-methylindene-4-carboxylate methyl) zirconi Dimethylsilane, dimethylsilanediylbiscyclopentadienyl titanium dimethyl, dimethylsilanediylbis (methylcyclopentadienyl) titanium dimethyl, dimethylsilanediylbis (dimethylcyclopentadienyl) titanium dimethyl, dimethylsilanediylbis (trimethylcyclopentadiene) Enyl) titanium dimethyl, dimethylsilanediylbis (tetramethylcyclopentadienyl) titanium dimethyl, dimethylsilanediylbis (pentamethylcyclopentadienyl) titanium dimethyl, dimethylsilanediylbis (chlorocyclopentadienyl) titanium dimethyl, dimethyl Silanediylbis (bromocyclopentadienyl) titanium dimethyl, dimethylsilanediylbis (iodocyclopentadienyl) Titanium dimethyl, dimethylsilanediylbis (methyl cyclopentadienecarboxylate) titanium dimethyl, dimethylsilanediylbisindenyltitanium dimethyl, dimethylsilanediylbis (2-methylindenyl) titaniumdimethyl, dimethylsilanediylbis (2-methyl-4) -Phenylindenyl) titanium dimethyl, dimethylsilanediylbis (2-ethyl-4-phenylindenyl) titanium dimethyl, dimethylsilanediylbis (2-isopropyl-4-phenylindenyl) titanium dimethyl, dimethylsilanediylbis (4 -Chloroindenyl) titanium dimethyl, dimethylsilanediylbis (4-bromoindenyl) titaniumdimethyl, dimethylsilanediylbis (4-iodoindenyl) titanium Dimethylsilane, dimethylsilanediylbis (methyl indene-4-carboxylate) titanium dimethyl, dimethylsilanediylbis (2-methyl-4-chloroindenyl) titanium dimethyl, dimethylsilanediylbis (2-methyl-4-bromoindenyl) ) Titanium dimethyl, dimethylsilanediylbis (2-methyl-4-iodoindenyl) titanium dimethyl, dimethylsilanediylbis (methyl 2-methylindene-4-carboxylate) titanium dimethyl, ethylenebis (cyclopentadienyl) titanium Dimethyl, ethylenebis (methylcyclopentadienyl) titanium dimethyl, ethylenebis (dimethylcyclopentadienyl) titanium dimethyl, ethylenebis (trimethylcyclopentadienyl) titanium dimethyl Ethylene bis (tetramethylcyclopentadienyl) titanium dimethyl, ethylene bis (pentamethylcyclopentadienyl) titanium dimethyl, ethylene bis (chlorocyclopentadienyl) titanium dimethyl, ethylene bis (bromocyclopentadienyl) titanium dimethyl, Ethylene bis (iodocyclopentadienyl) titanium dimethyl, ethylene bis (methyl cyclopentadienecarboxylate) titanium dimethyl, ethylene bisindenyltitanium dimethyl, ethylene bis (2-methylindenyl) titanium dimethyl, ethylene bis (2-methyl- 4-phenylindenyl) titanium dimethyl, ethylenebis (2-ethyl-4-phenylindenyl) titanium dimethyl, ethylenebis (2-isopropyl-4-) Phenylindenyl) titanium dimethyl, ethylenebis (4-chloroindenyl) zirconium dimethyl, ethylenebis (4-bromoindenyl) titanium dimethyl, ethylenebis (4-iodoindenyl) titanium dimethyl, ethylenebis (indene-4- Carboxylic acid methyl) titanium dimethyl, ethylene bis (2-methyl-4-chloroindenyl) titanium dimethyl, ethylene bis (2-methyl-4-bromoindenyl) titanium dimethyl, ethylene bis (2-methyl-4-iodoindene Nyl) titanium dimethyl, ethylenebis (2-methylindene-4-carboxylate methyl) titanium dimethyl, dimethylsilanediylbiscyclopentadienylhafniumdimethyl, dimethylsilanediylbis (methylcyclopentadi) Nyl) hafnium dimethyl, dimethylsilanediylbis (dimethylcyclopentadienyl) hafnium dimethyl, dimethylsilanediylbis (trimethylcyclopentadienyl) hafnium dimethyl, dimethylsilanediylbis (tetramethylcyclopentadienyl) hafnium dimethyl, dimethylsilane Diylbis (pentamethylcyclopentadienyl) hafnium dimethyl, dimethylsilanediylbis (chlorocyclopentadienyl) hafnium dimethyl, dimethylsilanediylbis (bromocyclopentadienyl) hafnium dimethyl, dimethylsilanediylbis (iodocyclopentadi) Enyl) hafnium dimethyl, dimethylsilanediylbis (methyl cyclopentadienecarboxylate) hafnium dimethyl, dimethylsilanediyl Sudenylhafnium dimethyl, dimethylsilanediylbis (2-methylindenyl) hafniumdimethyl, dimethylsilanediylbis (2-methyl-4-phenylindenyl) hafniumdimethyl, dimethylsilanediylbis (2-ethyl-4-phenyl) Indenyl) hafnium dimethyl, dimethylsilanediylbis (2-isopropyl-4-phenylindenyl) hafniumdimethyl, dimethylsilanediylbis (4-chloroindenyl) hafniumdimethyl, dimethylsilanediylbis (4-bromoindenyl) hafnium Dimethyl, dimethylsilanediylbis (4-iodoindenyl) hafnium dimethyl, dimethylsilanediylbis (methyl indene-4-carboxylate) hafnium dimethyl, dimethylsilanediylbis (2-methyl) Til-4-chloroindenyl) hafnium dimethyl, dimethylsilanediylbis (2-methyl-4-bromoindenyl) hafniumdimethyl, dimethylsilanediylbis (2-methyl-4-iodoindenyl) hafniumdimethyl, dimethylsilanediyl Bis (2-methylindene-4-carboxylate) hafnium dimethyl, ethylene bis (cyclopentadienyl) hafnium dimethyl, ethylene bis (methylcyclopentadienyl) hafnium dimethyl, ethylene bis (dimethylcyclopentadienyl) hafnium dimethyl , Ethylenebis (trimethylcyclopentadienyl) hafnium dimethyl, ethylenebis (tetramethylcyclopentadienyl) hafnium dimethyl, ethylenebis (pentamethylcyclopentadienyl) hafni Dimethyl, ethylenebis (chlorocyclopentadienyl) hafnium dimethyl, ethylene bis (bromocyclopentadienyl) hafnium dimethyl, ethylene bis (iodocyclopentadienyl) hafnium dimethyl, ethylene bis (methyl cyclopentadienecarboxylate) hafnium dimethyl, Ethylene bis (indenyl) hafnium dimethyl, ethylene bis (2-methylindenyl) hafnium dimethyl, ethylene bis (2-methyl-4-phenylindenyl) hafnium dimethyl, ethylene bis (2-ethyl-4-phenylindenyl) hafnium dimethyl , Ethylenebis (2-isopropyl-4-phenylindenyl) hafnium dimethyl, ethylenebis (4-chloroindenyl) hafnium dimethyl, ethylenebis (4-bromoi Denyl) hafnium dimethyl, ethylene bis (4-iodoindenyl) hafnium dimethyl, ethylene bis (indene-4-carboxylate methyl) hafnium dimethyl, ethylene bis (2-methyl-4-chloroindenyl) hafnium dimethyl, ethylene bis ( 2-methyl-4-bromoindenyl) hafnium dimethyl, ethylene bis (2-methyl-4-iodoindenyl) hafnium dimethyl, ethylene bis (2-methylindene-4-carboxylate methyl) hafnium dimethyl, and the like.

  The organometallic compound thus obtained is isolated by a known method such as extraction or crystallization, and can be further purified by a known purification method such as recrystallization.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples. In addition, the Example and the comparative example were implemented using the microreactor apparatus shown in FIG.

Example 1
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (35 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 100 cm), zirconium tetrachloride in THF / toluene (11/1) mixed solution prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 9.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and analyzed by NMR internal standard. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 76%.

Example 2
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (30 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 100 cm), zirconium tetrachloride in THF / toluene (11/1) mixed solution prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 9.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and analyzed by NMR internal standard. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 68%.

Example 3
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (35 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and subjected to NMR internal standard analysis. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 61%.

Example 4
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (30 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and subjected to NMR internal standard analysis. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 57%.

Example 5
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (25 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and subjected to NMR internal standard analysis. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 70%.

Example 6
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (0 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 100 cm), zirconium tetrachloride in THF / toluene (11/1) mixed solution prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, a 0.35M ethylmethylamine THF solution is sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 2.4 mL / min. At the same time, the reaction solution discharged from R1 was fed to produce tetrakis (N-ethyl-N-methylamido) zirconium. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 12.4 seconds. The obtained reaction solution was sampled for 1 minute and subjected to NMR internal standard analysis. As a result, tetrakis (N-ethyl-N-methylamido) zirconium was obtained in a yield of 58%.

Example 7
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (35 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 100 cm), zirconium tetrachloride in THF / toluene (11/1) mixed solution prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, 0.9M indene in THF was sent to R2 (inner diameter: 1000 μm, length: 200 cm) via R2 (inner diameter: 500 μm) with a syringe pump S3 at a flow rate of 1.1 mL / min. The reaction solution discharged from R1 was fed to produce bisindenylzirconium dimethyl. The residence time in R1 was 9.1 seconds, and the residence time in R2 was 15.0 seconds. The obtained reaction solution was sampled for 1 minute and analyzed by NMR internal standard. As a result, bisindenylzirconium dimethyl was obtained in a yield of 55%.

Example 8
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (35 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 100 cm), zirconium tetrachloride in THF / toluene (11/1) mixed solution prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, 0.9M indene in THF was sent to R2 (inner diameter: 1000 μm, length: 400 cm) via R2 (inner diameter: 250 μm) with a syringe pump S3 at a flow rate of 1.1 mL / min. The reaction solution discharged from R1 was fed to produce bisindenylzirconium dimethyl. The residence time in R1 was 9.1 seconds, and the residence time in R2 was 29.9 seconds. The obtained reaction solution was sampled for 1 minute and analyzed by NMR internal standard. As a result, bisindenylzirconium dimethyl was obtained in a yield of 56%.

Example 9
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (25 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, 0.9M indene in THF was sent to R2 (inner diameter: 1000 μm, length: 400 cm) via R2 (inner diameter: 250 μm) with a syringe pump S3 at a flow rate of 1.1 mL / min. The reaction solution discharged from R1 was fed to produce bisindenylzirconium dimethyl. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 29.9 seconds. The obtained reaction solution was sampled for 1 minute and analyzed by NMR internal standard. As a result, bisindenylzirconium dimethyl was obtained in a yield of 61%.

Example 10
A microreactor composed of two T-shaped micromixers (M1, M2) and two microtube reactors (R1, R2) was immersed in a water bath (25 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. Next, 0.9M cyclopentadiene in THF was sent at a flow rate of 1.1 mL / min to R2 (inner diameter: 1000 μm, length: 400 cm) via M2 (inner diameter: 1000 μm, length: 400 cm) with a syringe pump S3. At the same time, the reaction solution discharged from R1 was sent to produce biscyclopentadienylzirconium dimethyl. The residence time in R1 was 18.1 seconds, and the residence time in R2 was 29.9 seconds. The obtained reaction solution was sampled for 5 minutes, concentrated and dried, and the residue was suspended and washed with hexane. When the obtained hexane solution was concentrated and dried, biscyclopentadienylzirconium dimethyl was obtained in a yield of 66%.

Comparative Example 1
A microreactor composed of a T-shaped micromixer (M1) and a microtube reactor (R1) was immersed in a water bath (25 ° C.).
Via M1 (inner diameter 500 μm) to R1 (inner diameter 1000 μm, length 200 cm), a solution of zirconium tetrachloride in THF / toluene (11/1) prepared to 0.1 M and 0.25 M MeLi in THF / diethyl The ether (3/1) mixed solution was fed by syringe pumps S1 and S2 at a flow rate of 2.0 mL / min and 3.2 mL / min, respectively. The residence time in R1 was 18.1 seconds. The mixed reaction solution was added dropwise to 1.1 mL of 0.9 M indene in THF for 1 minute and reacted at 25 ° C. for 1 hour. When the obtained reaction liquid was subjected to NMR internal standard analysis, bisindenylzirconium dimethyl was obtained in a yield of 18%.

It is the schematic of the reaction apparatus used for the Example.

S1: Syringe pump 1
S2: Syringe pump 2
S3: Syringe pump 3
M1: Micromixer 1
M2: Micromixer 2
R1: Microreactor 1
R2: Microreactor 2

Claims (6)

  An organometallic compound characterized by reacting a tetrahalo metal compound with an alkyllithium compound in a microreactor to form a tetraalkyl metal compound, and then reacting the tetraalkyl metal compound with a compound having an active proton in the microreactor Manufacturing method.   The method for producing an organometallic compound according to claim 1, which is carried out in the presence of a solvent. The method for producing an organometallic compound according to claim 1 or 2, wherein the tetrahalo metal compound is represented by the formula (1).
Formula (1):
MX ₄ (1)
(In the formula, M represents zirconium, titanium or hafnium, and X represents a halogen atom.) The method for producing an organometallic compound according to any one of claims 1 to 3, wherein the alkyllithium compound is represented by the formula (2).
Formula (2):
LiR ¹ (2)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms.) The method for producing an organometallic compound according to any one of claims 1 to 4, wherein the compound having an active proton is represented by any one of the following formulas (3) to (5).
Formula (3):
HNR ² R ³ (3)
(Wherein R ² and R ³ are the same as or different from each other and represent an alkyl group having 1 to 8 carbon atoms),
Formula (4):

(Wherein R ⁴ and R ⁵ are the same as or different from each other and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an ester group, or R ⁴ and R ⁵ are bonded to each other at the end to form an aryl group; An ester group, a C5-C6 ring optionally substituted with a halogen atom is formed).
Formula (5):

(Wherein R ⁶ and R ⁷ are the same as or different from each other and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or an ester group, or R ⁶ and R ⁷ are bonded to each other at the terminal to form an aryl group; An ester group forms a C5 to C6 ring optionally substituted with a halogen atom, and B represents a bridging group having a carbon atom or a silicon atom.) The method for producing an organometallic compound according to claim 5, wherein the organometallic compound is represented by any one of the following formulas (6) to (8).
Formula (6):
M (NR ² R ³ ) ₄ (6)
(Wherein M, R ² and R ³ are the same as above),
Formula (7):

(Wherein, M, R ¹ , R ⁴ and R ⁵ are the same as above),
Formula (8):

(In the formula, M, R ¹ , B, R ⁶ and R ⁷ are the same as above.)

Images