WO2019176592A1

WO2019176592A1 - Method for producing heteroatom-containing aromatic vinyl compound

Info

Publication number: WO2019176592A1
Application number: PCT/JP2019/008161
Authority: WO
Inventors: 健介鷲頭
Original assignee: 住友ゴム工業株式会社
Priority date: 2018-03-12
Filing date: 2019-03-01
Publication date: 2019-09-19
Also published as: JP2019156747A

Abstract

A method for producing a heteroatom-containing aromatic vinyl compound of formula (I): R¹-R²-Y [wherein: R¹ represents a specific aromatic group; R² represents Si(R¹⁰)(R¹¹) wherein R¹⁰ and R¹¹ independently represent a specific group; and Y represents a specific group], said method comprising: (A) a step for reacting a Grignard reagent-containing reaction solution, which is obtained by reacting a specific compound of formula (II): R¹-X¹ with magnesium, with a specific halogen compound of formula (III): X²-R²-X³ to give a specific halogenated aromatic vinyl intermediate of formula (IV): R¹-R²-X³ in a crudely purified state; and (B) a step for adding an organic metal nucleophilic agent containing Y to the reaction mixture containing the halogenated aromatic vinyl intermediate obtained in step (A) and thus introducing the functional group Y thereinto to give the heteroatom-containing aromatic vinyl compound represented by formula (I).

Description

Process for producing heteroatom-containing aromatic vinyl compound

The present invention relates to a method for producing an aromatic vinyl compound having a hetero atom.

An aromatic vinyl compound having a substituent containing a hetero atom is an important intermediate for pharmaceuticals and electronic materials, and is also an important monomer component of a functional polymer.

Conventionally, for example, the following methods are known as methods for producing monoalkoxydialkylsilylstyrene. A dihalogenated dialkylsilane is reacted with an alkyl alcohol in the presence of an organic solvent and a tertiary amine to produce a monoalkoxychlorosilane. Thereafter, by-product hydrochloride is removed by Celite filtration or the like, and then purified by distillation and reacted with a Grignard reagent derived from halogenated styrene. The obtained monoalkoxydialkylsilylstyrene is filtered from the magnesium halide salt and then purified by distillation.

Non-Patent Document 1 discloses that a dialkyldichlorosilane and alcohol are reacted at 0 ° C. for 5 hours in an inert gas atmosphere under a hydrocarbon solvent using amines as a deoxidizer and filtered. , A method for obtaining monoalkoxychlorosilane through solvent washing and distillation.

However, in the method described in Non-Patent Document 1, a salt of hydrogen chloride and an amine is produced. However, since this salt is soluble in a hydrocarbon solvent, it is difficult to remove it by filtration, solvent washing, and distillation alone. There exists a problem of reducing the yield and purity of the target product due to the side reaction in the next step.

In addition, monoalkoxychlorosilane is highly reactive and easily decomposes in the air, causing a decrease in purity and yield, or reacting with moisture to generate hydrogen chloride, which is a problem in handling safety. There is. Moreover, the loss of the target product at the time of filtration separation from the produced salt and distillation purification occurs, which causes a decrease in yield. Furthermore, in the reaction with the Grignard reagent, the alkoxysilyl group of the resulting monoalkoxydialkylsilylstyrene also has reactivity with the Grignard reagent, so that there is a problem that an unintended side reaction occurs.

Therefore, an object of the present invention is to provide a production method capable of obtaining a target heteroatom-containing aromatic vinyl compound with high purity and high yield.

As a result of intensive studies, the present inventor can obtain a heteroatom-containing aromatic vinyl compound with high purity and high yield safely by using a halogenated aromatic vinyl compound as a starting material and reacting in one pod. The present inventors have found that the above problems can be solved, and have further studied to complete the present invention.

That is, the present invention
[1] Formula (I): R ¹ -R ² -Y
(Wherein R ¹ is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent, R ² is Si (R ¹⁰ ) (R ¹¹ ), In the formula, R ¹⁰ and R ¹¹ are each independently a group containing at least one atom selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur and oxygen atoms, Y is carbon, A functional group containing at least one atom selected from the group consisting of silicon, nitrogen, sulfur and oxygen atoms)
A process for producing a heteroatom-containing aromatic vinyl compound represented by
(A) Formula (II): R ¹ -X ¹
(Wherein R ¹ is the same as above, and X ¹ is halogen)
A reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound represented by the formula, preferably 4-chlorostyrene, 4-bromostyrene or 2-vinyl-6-chloropyridine,
Formula (III): X ² -R ² -X ³
(Wherein X ² and X ³ are each independently halogen, and R ² is the same as above)
, Preferably dichlorodiC _1-6 alkylsilanes such as dichlorodimethylsilane, dichlorodiethylsilane and dichlorodipropylsilane, dichloroditrimethylsiloxysilane, cycloalkyloditriethylsiloxysilane, dichlorodidimethylsiloxysilane or dichloro Dichlorodialkylsiloxysilanes such as didiethylsiloxysilane, tetrahalogenated silanes such as tetrachlorosilane, dichloro (acetoxyethyl) (methyl) silane, (methyl) silane, dichloro (acetoxymethyl) dichloro (methyl) silane or dichloro (acetoxyethyl) ) Dihalogendialkoxysila such as dihalogen (acyloxyalkyl) (alkyl) silane such as (ethyl) silane, dichloroditert-butoxysilane , Dichloro (phenoxy) (methyl) silane, dichloro (phenyl) (methyl) silane, dichlorodidimethylaminosilane, dichlorocyanopropylmethylsilane, dichloro (ethoxypropyl) (methyl) silane, dichloro (ethoxypropyl) (ethyl) silane Dichloro (methoxypropyl) (methyl) silane, dichloro (methoxypropyl) (ethyl) silane, dichloro (dimethylamidomethyl) (methyl) silane, dichloro (N, N-dimethylamidomethyl) (methyl) silane, 2- ( Reacting a compound selected from dichloromethylsilyl) thiophene and [(dichloromethyl) methyl] thiobenzene,
Formula (IV): R ¹ -R ² -X ³
(Wherein R ¹ , R ² and X ³ are the same as above)
And (B) an organometallic nucleophile containing a functional group Y in the reaction mixture containing the halogenated aromatic vinyl intermediate obtained in step (A). A process for producing a heteroatom-containing aromatic vinyl compound represented by formula (I) by adding a functional group Y by adding
[2] (C) The production method according to the above [1], comprising the step of isolating the heteroatom-containing aromatic vinyl compound represented by the formula (I) obtained in the step (B) by filtration and / or vacuum distillation ,
[3] An organometallic nucleophile is
Formula (V): M ¹ -Y
(Wherein M ¹ is an alkali metal and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms)
Preferably represented by sodium methoxide, potassium methoxide, lithium methoxide, cesium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, cesium ethoxide, sodium n-butoxide, potassium n- Butoxide, lithium n-butoxide, cesium n-butoxide, sodium s-butoxide, potassium s-butoxide, lithium s-butoxide, cesium s-butoxide, sodium t-butoxide, potassium t-butoxide, lithium t-butoxide, cesium t- Butoxide, sodium n-propoxide, potassium n-propoxide, lithium n-propoxide, cesium n-propoxide, sodium isopropoxide, potassium isopropoxide, lithium iso Metal alkoxides such as lopoxide and cesium isopropoxide, metal salts of phenols such as sodium phenoxide, potassium phenoxide, lithium phenoxide and cesium phenoxide, sodium dimethylamide, potassium dimethylamide, lithium dimethylamide, cesium dimethylamide, sodium diethyl Amide, potassium diethylamide, lithium diethylamide, cesium diethylamide, sodium diisopropylamide, potassium diisopropylamide, lithium diisopropylamide, cesium diisopropylamide, sodium tris (trimethylsilyl) amide, potassium tris (trimethylsilyl) amide, lithium tris (trimethylsilyl) amide, cesium tris (Trimethylsilyl) amide etc. Select from metal amides, sodium thiolate, potassium thiolate, lithium thiolate, cesium thiolate, sodium benzene thiolate, potassium benzene thiolate, metal salts of thiols such as lithium benzene thiolate, cesium benzene thiolate, and alkyl lithium such as n-butyllithium. An organometallic compound, or formula (VI):

Wherein M ² is an alkaline earth metal, Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and R ³ is halogen , A functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and may be the same as or different from Y)
And preferably magnesium dimethoxide, magnesium diethoxide, magnesium di n-butoxide, magnesium di s-butoxide, magnesium di tert-butoxide, magnesium di n-propoxide, magnesium diisopropoxide, etc. An organometallic compound selected from phenols such as magnesium diphenoxide, and more preferably, M ² is magnesium, R ³ is halogen, Y is C _1-10 alkyl, C _2-10 Alkenyl, C _1-6 acyloxy C _1-6 alkyl, C _6-12 aryl, cyano C _1-6 alkyl, C _1-6 alkoxy C _1-6 alkyl, C _4-10 heterocyclyl, thiobenzene C _1-6 alkyl or a Grignard reagent is an amido C _1-6 alkyl above [1] or [2] described Manufacturing method,
[4] The production method of the above-mentioned [3], wherein the organometallic nucleophile is a metal alkoxide or a Grignard reagent,
[5] R ¹⁰ and R ¹¹ are each independently halogen, C _1-10 alkyl, C _2-10 alkenyl, tri-C _1-6 alkylsiloxy, C _1-6 acyl, C _1-6 acyloxy, C _1-6 acyloxy C _1-6 alkyl, C _1-6 alkoxy, C _6-12 aryl, C _6-12 aryloxy, amino, C _1-6 alkylamino, di-C _1-6 alkylamino, cyano C _1- [1] to [4] above, which is ₆ alkyl, C _1-6 alkoxy C _1-6 alkyl, C _4-10 heterocyclyl, thiobenzene C _1-6 alkyl, C _1-6 alkylamide or amide C _1-6 alkyl The production method according to any one of
[6] Y is C _1-10 alkyl, C _2-10 alkenyl, tri-C _1-6 alkylsiloxy, silanol, C _1-6 acyl, C _1-6 acyloxy, C _1-6 acyloxy C _1-6 alkyl C _1-6 alkoxy, C _6-12 aryl, C _6-12 aryloxy, amino, C _1-6 alkylamino, di-C _1-6 alkylamino, cyano C _1-6 alkyl, C _1-6 alkoxyC The production according to any one of [1] to [5] above, which is _1-6 alkyl, C _4-10 heterocyclyl, thionyl, thiobenzene C _1-6 alkyl, C _1-6 alkylamide or amide C _1-6 alkyl. Method,
[7] The production method according to any one of [1] to [6] above, wherein the step (A) is started in the presence of an initiator, and [8] the halogen compound of the formula (III) is dichlorodi-C _1-10 The production method according to any one of [1] to [7] above, which is alkylsilane or dichlorothiophene C _1-10 alkylsilane.

Formula (I): R ¹ -R ² -Y of the present invention (wherein R ¹ is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent) , R ² is Si (R ¹⁰ ) (R ¹¹ ), wherein R ¹⁰ and R ¹¹ are each independently selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur or oxygen atoms. Y is a group containing at least one atom, and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms), Si A method for producing a heteroatom-containing aromatic vinyl compound containing at least one heteroatom selected from O, N, and S, wherein (A) Formula (II): R ¹ -X ¹ (wherein R ¹ is the same as defined above, X ¹ is a compound represented by a halogen) To the reaction solution containing the Grignard reagent obtained by reacting magnesium, formula ^{^{(III): X 2 -R 2}} -X 3 ( wherein, X ² and X ³ is a halogen independently, R ² is the And a halogen compound represented by the formula (IV): R ¹ —R ² —X ³ (wherein R ¹ , R ² and X ³ are the same as above) An organometallic nucleophile containing a functional group Y is added to the reaction mixture containing the halogenated aromatic vinyl intermediate obtained in the step (B) and the step (A). According to the method for producing a heteroatom-containing aromatic vinyl compound represented by the formula (I), including the step of introducing the functional group Y and obtaining the heteroatom-containing aromatic vinyl compound represented by the formula (I), A heteroatom-containing aromatic vinyl compound represented by the formula (I) has a high purity and a high purity. It is possible to obtain safely at a rate.

The present invention relates to the formula (I): R ¹ —R ² —Y (wherein R ¹ is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent. , R ² is Si (R ¹⁰ ) (R ¹¹ ), wherein R ¹⁰ and R ¹¹ are each independently selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur or oxygen atoms. Y is a group containing at least one atom, and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms) A method for producing a containing aromatic vinyl compound, which is represented by (A) Formula (II): R ¹ -X ¹ (wherein R ¹ is the same as above, and X ¹ is halogen) A reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound is added to the formula (III : X ^² -R ² -X ³ (wherein, X ² and X ³ is a halogen independently, R ² is as defined above) by reacting a halogen compound represented by the formula (IV) A step of producing a halogenated aromatic vinyl intermediate represented by: R ¹ -R ² -X ³ (wherein R ¹ , R ² and X ³ are the same as above), and step (B) ( Into the reaction mixture containing the halogenated aromatic vinyl intermediate obtained in A), an organometallic nucleophile containing a functional group Y is added to introduce the functional group Y, and the heteroatom-containing compound represented by the formula (I) It is a manufacturing method of the hetero atom containing aromatic vinyl compound represented by Formula (I) including the process of obtaining an aromatic vinyl compound.

By completing the reaction in one pod via the halogenated aromatic vinyl compound represented by the above formula (IV) as an intermediate, the formation of by-products is suppressed, and the above formula (I) is obtained in high purity and high yield. The heteroatom-containing aromatic vinyl compound having a substituent containing a vinyl group and a substituent containing a heteroatom can be produced safely.

In step (A), formula (II): R ¹ -X ¹ (wherein R ¹ is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent, ^In a reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound of ¹ is halogen, the compound of formula (III): X ² —R ² —X ³ (wherein X ² and X ³ are each independently R ² is Si (R ¹⁰ ) (R ¹¹ ), wherein R ¹⁰ and R ¹¹ are each independently a group consisting of halogen, carbon, silicon, nitrogen, sulfur or oxygen atoms. And a halogen compound of the formula (IV): R ¹ -R ² -X ³ (wherein R ¹ , R ² and X ³ are the above-mentioned groups). The same as that of the halogenated aromatic vinyl intermediate.

R ¹ is an aromatic group which has a vinyl group and may be substituted with a group inert to the Grignard reagent, and the vinyl group means a reactive carbon-carbon double bond. The aromatic group of the “aromatic group optionally substituted with a group inert to the Grignard reagent” constitutes a ring, for example, a 5- to 14-membered aryl group, preferably a 5- to 6-membered aryl group A 5- to 14-membered heteroaryl group, preferably a 5- to 6-membered heteroaryl group containing at least one, preferably 1 to 2, heteroatoms such as nitrogen, sulfur, oxygen, etc. as atoms, Examples include those having a bond to X ¹ at a carbon atom in the ring, such as phenyl, pyridyl, pyrimidinyl, thienyl, furanyl, naphthyl, quinolyl, benzofuranyl, anthracenyl, and the like, and phenyl is preferred. Examples of the group inert to the Grignard reagent that may be substituted with the aromatic group of the “aromatic group optionally substituted with an inert group to the Grignard reagent” include an alkyl group (for example, 1 to 5 carbon atoms). Alkyl groups, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.), ether groups, silyl ether groups, and the like. The group inert to the Grignard reagent may be substituted at any substitutable position of the aromatic group, but preferably has a bond to X ^{1 at} the para position of the substitution position by the vinyl group. It is preferable to substitute at other substitutable positions. When two or more substituents are present, the substituents may be the same or different. The number of substituents is preferably 1 to 3, more preferably 1.

X ¹ is halogen, selected from a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.

Formula (II): R ¹ -X ¹ (wherein R ¹ is an aromatic group having a vinyl group, which may be substituted with a group inert to the Grignard reagent, and X ¹ is a halogen) Specific examples of the compound include 4-chlorostyrene, 4-bromostyrene, 2-vinyl-6-chloropyridine and the like.

X ² and X ³ are each independently a halogen such as a chlorine atom, a bromine atom or an iodine atom, and a chlorine atom is preferable from the viewpoint of low cost and availability.

R ² is Si (R ¹⁰ ) (R ¹¹ ), wherein R ¹⁰ and R ¹¹ are each independently at least one selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur and oxygen atoms. A group containing more than one kind of atom. For example, R ¹⁰ and R ¹¹ each independently include a group containing halogen, linear or branched alkyl, linear or branched alkenyl, carbonyl, amide, amino, ether, phenol or phenyl, Specifically, halogen, C _1-10 alkyl, C _2-10 alkenyl, tri C _1-6 alkylsiloxy, C _1-6 acyl, C _1-6 acyloxy, C _1-6 acyloxy C _1-6 alkyl, C _1-6 alkoxy, C _6-12 aryl, C _6-12 aryloxy, amino, C _1-6 alkylamino, di-C _1-6 alkylamino, cyano C _1-6 alkyl, C _1-6 alkoxy C _{1 -6} alkyl, C _4-10 heterocyclyl, thiobenzene C _1-6 alkyl, C _1-6 alkylamide, amide C _1-6 alkyl and the like are preferable.

In R ¹⁰ or R ¹¹ , the halogen is a chlorine atom, a bromine atom or an iodine atom.

In the present specification, “C _1-10 alkyl” is a linear or branched saturated hydrocarbon group having 1 to 10 carbon atoms, and is not particularly limited, but examples thereof include methyl, ethyl, propyl, Examples thereof include isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like. R ¹⁰ or R ¹¹ is more preferably methyl, ethyl, octyl or the like.

In the present specification, “C _2-10 alkenyl” is a hydrocarbon group having 2 to 10 carbon atoms having at least one straight-chain or branched carbon-carbon double bond, and is not particularly limited. Are, for example, ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 2-pentenyl and the like.

In the present specification, examples of “tri-C _1-6 alkylsiloxy” include trimethylsiloxy, triethylsiloxy, tributylsiloxy, tri-iso-propylsiloxy, tri-tert-butylsiloxy and the like.

In the present specification, “C _1-6 acyl” means one obtained by removing an OH group from a carboxylic acid having 1 to 6 carbon atoms, and is not particularly limited. Specifically, methanoyl, Examples include ethanoyl and benzoyl.

In the present specification, “C _1-6 acyloxy” is not particularly limited, and examples thereof include acetoxy, propanoyloxy, acryloyloxy, methacryloyloxy, malonyloxy, benzoyloxy and the like.

In the present specification, “C _1-6 acyloxy C _1-6 alkyl” is not particularly limited, but “C _1-6 acyloxy” as defined herein such as acetoxyethyl is added. And an alkyl group having 1 to 6 carbon atoms as defined herein.

In the present specification, “C _1-6 alkoxy” means an alkyl group having 1 to 6 carbon atoms bonded to an oxygen atom, and is not particularly limited. Ethoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, propoxy, methylenedioxy and the like.

In the present specification, “C _6-12 aryl” means a group derived from an aromatic hydrocarbon having 6 to 12 carbon atoms, and is not particularly limited. Examples thereof include 3-phenylpropyl, tolyl, xylyl, cumenyl, benzyl, phenethyl, cinamyl, biphenyl and the like, and may have a substituent.

In the present specification, “C _6-12 aryloxy” is not particularly limited, and examples thereof include phenoxy and 3-phenoxypropyl, which may have a substituent.

In the present specification, “C _1-6 alkylamino” is not particularly limited, and specifically includes methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, tert-butyl. Examples include amino and sec-butylamino.

In the present specification, “di-C _1-6 alkylamino” is not particularly limited, but dimethylamino, diethylamino, ethylmethylamino, dipropylamino, diisopropylamino, dibutylamino, di-tert-butyl. Examples include amino.

In the present specification, “cyano C _1-6 alkyl” includes an alkyl group having 1 to 6 carbon atoms as defined herein, to which a “cyano” group is added.

In the present specification, “C _1-6 alkoxy C _1-6 alkyl” has 1 to 6 carbon atoms as defined in the present specification to which “C _1-6 alkoxy” as defined in the present specification is added. An alkyl group.

In the present specification, “C _4-10 heterocyclyl” is not particularly limited, but is a heterocycle having 4 to 10 carbon atoms having at least one heteroatom selected from N, O or S. A group generated by removing one hydrogen atom from a ring atom, and specific examples include thienyl, pyrrolidyl, pyrrolyl, pyridyl, furanyl and the like.

In the present specification, “thiobenzene C _1-6 alkyl” is not particularly limited, and examples thereof include an alkyl group having 1 to 6 carbon atoms as defined in the present specification to which thiobenzene is added.

“Amido C _1-6 alkyl” is not particularly limited, but is substituted with an alkyl group such as dimethylamide, diethylamide, dipropylamide, di-iso-propylamide, dibutylamide, di-tert-butylamide and the like. And an alkyl group having 1 to 6 carbon atoms, as defined herein, to which is added an amide group.

Specific examples of the halogen compound of the above formula (III) are not particularly limited, but include dichlorodiC _1-6 alkylsilanes such as dichlorodimethylsilane, dichlorodiethylsilane or dichlorodipropylsilane, dichloroditrimethyl. Siloxysilane, Cycloditriethylsiloxysilane, Dichlorodidimethylsiloxysilane or dichlorodialkylsiloxysilane such as dichlorodidiethylsiloxysilane, Tetrahalogenated silane such as tetrachlorosilane, Dichloro (acetoxyethyl) (methyl) silane, (Methyl) silane Dihalogen (acyloxyalkyl) (alkyl) silanes such as dichloro (acetoxymethyl) dichloro (methyl) silane or dichloro (acetoxyethyl) (ethyl) silane, dichloroditert-but Dihalogen dialkoxysilanes such as xysilane, dichloro (phenoxy) (methyl) silane, dichloro (phenyl) (methyl) silane, dichlorodidimethylaminosilane, dichlorocyanopropylmethylsilane, dichloro (ethoxypropyl) (methyl) silane, dichloro (ethoxy Propyl) (ethyl) silane, dichloro (methoxypropyl) (methyl) silane, dichloro (methoxypropyl) (ethyl) silane, dichloro (dimethylamidomethyl) (methyl) silane, dichloro (N, N-dimethylamidomethyl) (methyl) ) Silane, 2- (dichloromethylsilyl) thiophene, [(dichloromethyl) methyl] thiobenzene, and the like. Of these, dichloro C _1-6 alkylsilane is preferable, and dichlorodimethylsilane is particularly preferable.

In the step (A), for example, an ether solvent usually used for Grignard reaction is added to metal magnesium under an inert gas atmosphere, and a catalyst amount of an initiator usually used to produce a Grignard reagent is added and stirred. The compound of II) is preferably dropped and stirred to obtain a Grignard reagent, and the halogen compound of formula (III) is preferably dropped directly into the reaction solution containing the obtained Grignard reagent.

The inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and helium gas. Nitrogen gas is preferable from the viewpoint of low cost and availability.

The amount of metal magnesium used is preferably 1.00 to 1.20 mol, more preferably 1.05 to 1.10 mol, per 1 mol of the compound of the above formula (II).

The ether solvent is not particularly limited, and examples thereof include diethyl ether, dimethoxyethane, diethoxymethane, t-butyl methyl ether, dibutyl ether, tetrahydrofuran (THF), diglyme and the like, and tetrahydrofuran is preferable. .

The initiator is not particularly limited, and examples thereof include iodine and alkyl halides such as 1,2-dibromoethane. Of these, 1,2-dibromoethane is preferable because it is inexpensive and easily available.

The amount of the halogen compound of the formula (III) used is preferably an equimolar amount with respect to the compound of the formula (II), and used in the range of 1.01 to 1.10 mol with respect to 1 mol of the compound of the formula (II). be able to.

The reaction temperature in step (A) is preferably 0 to 80 ° C, more preferably 40 to 60 ° C. Further, in the step (A), the reaction temperature when the obtained Grignard reagent is reacted with the halogen compound of the above formula (III) is preferably 0 to 80 ° C., more preferably 10 to 50 ° C., particularly in the reaction vessel. The temperature is preferably not more than 50 ° C, more preferably not more than 30 ° C. The reaction time in step (A) is preferably 1.0 to 3.0 hours, more preferably 1.5 to 2.0 hours after the dropwise addition of the compound of formula (II) in the preparation reaction of the Grignard reagent. The reaction of the obtained Grignard reagent with the compound of the above formula (III) is carried out by adding the compound of the above formula (III) dropwise over 1 to 8 hours, preferably 2 to 5 hours, usually at 10 to 40 ° C., preferably Is preferably carried out at 20 to 40 ° C.

The halogenated aromatic vinyl intermediate of the above formula (IV) obtained in the step (A) is used in the next step (B) as it is without purification or isolation.

In the step (B), an organometallic nucleophile containing a functional group Y is added to the reaction mixture containing the halogenated aromatic vinyl intermediate of the above formula (IV) obtained in the step (A) to convert the functional group Y. Introducing a heteroatom-containing aromatic vinyl compound represented by the formula (I).

The organometallic nucleophile is not particularly limited as long as it contains a functional group Y and the functional group Y can be introduced into the halogenated aromatic vinyl intermediate of the above formula (IV). (V): M ¹ -Y (wherein M ¹ is an alkali metal and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms) Or an organometallic compound represented by formula (VI):

Wherein M ² is an alkaline earth metal, Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and R ³ is halogen , A functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and may be the same as or different from Y). It is done.

M ¹ is an alkali metal, and specific examples include lithium, sodium, potassium, cesium and the like.

Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, specifically, halogen, C _1-10 alkyl, C _2-10 Alkenyl, Tri C _1-6 alkylsiloxy, Silanol, C _1-6 acyl, C _1-6 acyloxy, C _1-6 acyloxy C _1-6 alkyl, C _1-6 alkoxy, C _6-12 aryl, C _{6- 12} aryloxy, amino, C _1-6 alkylamino, diC _1-6 alkylamino, cyano C _1-6 alkyl, C _1-6 alkoxy C _1-6 alkyl, C _4-10 heterocyclyl, thionyl, thiobenzene C _{1 -6} alkyl, C _1-6 alkylamide, amide C _1-6 alkyl and the like are preferable. In the compound of the formula (V), Y may be any functional group that forms a salt with an alkali metal, and is preferably C _1-10 alkyl, C _1-6 alkoxy, di-C _1-6 alkylamino, or the like. In the compound of the formula (VI), Y may be a functional group that forms a salt with an alkaline earth metal or a group that can take a Grignard reagent with M ² and R ³ .

The organometallic compound of the formula (V) is not particularly limited, and examples thereof include sodium methoxide, potassium methoxide, lithium methoxide, cesium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, Cesium ethoxide, sodium n-butoxide, potassium n-butoxide, lithium n-butoxide, cesium n-butoxide, sodium s-butoxide, potassium s-butoxide, lithium s-butoxide, cesium s-butoxide, sodium t-butoxide, potassium t-butoxide, lithium t-butoxide, cesium t-butoxide, sodium n-propoxide, potassium n-propoxide, lithium n-propoxide, cesium n-propoxide, sodium isopropoxide, potassium Metal alkoxides such as um isopropoxide, lithium isopropoxide, cesium isopropoxide, metal salts of phenols such as sodium phenoxide, potassium phenoxide, lithium phenoxide, cesium phenoxide, sodium dimethylamide, potassium dimethylamide, lithium dimethylamide , Cesium dimethylamide, sodium diethylamide, potassium diethylamide, lithium diethylamide, cesium diethylamide, sodium diisopropylamide, potassium diisopropylamide, lithium diisopropylamide, cesium diisopropylamide, sodium tris (trimethylsilyl) amide, potassium tris (trimethylsilyl) amide, lithium Tris (trimethylsilyl) amide, cesium Metal amides such as tris (trimethylsilyl) amide, sodium thiolate, potassium thiolate, lithium thiolate, cesium thiolate, sodium benzene thiolate, potassium benzene thiolate, lithium benzene thiolate, metal salts of thiols such as cesium benzene thiolate, n-butyl lithium, etc. And alkyl lithium.

M ² is an alkaline earth metal, and specific examples thereof include magnesium and calcium.

R ³ may be any functional group that forms a salt with halogen or an alkaline earth metal, and includes at least one atom selected from the group consisting of halogen, silicon, nitrogen, sulfur, and oxygen atoms. Etc. R ³ is, for example, halogen such as chlorine, bromine or iodine, or C _1-10 alkyl, C _2-10 alkenyl, tri-C _1-6 alkylsiloxy, silanol, C _1-6 acyl, C _1-6 acyloxy, C _1-6 acyloxy C _1-6 alkyl, C _1-6 alkoxy, C _6-12 aryl, C _6-12 aryloxy, amino, C _1-6 alkylamino, di-C _1-6 alkylamino, cyano C _1- Preferred are ₆ alkyl, C _1-6 alkoxy C _1-6 alkyl, C _4-10 heterocyclyl, thionyl, thiobenzene C _1-6 alkyl, C _1-6 alkylamide, amide C _1-6 alkyl and the like.

The organometallic compound of the above formula (VI) is not particularly limited. For example, magnesium dimethoxide, magnesium diethoxide, magnesium di n-butoxide, magnesium di s-butoxide, magnesium di tert-butoxide, magnesium Examples thereof include metal alkoxides such as di-n-propoxide and magnesium diisopropoxide, and metal salts of phenols such as magnesium diphenoxide. In the organometallic compound of the above formula (VI), M ² is magnesium, R ³ is halogen, Y is C _1-10 alkyl, C _2-10 alkenyl, C _1-6 acyloxy C _1-6. Grignard reagents which are alkyl, C _6-12 aryl, cyano C _1-6 alkyl, C _1-6 alkoxy C _1-6 alkyl, C _4-10 heterocyclyl, thiobenzene C _1-6 alkyl or amide C _1-6 alkyl; You can also

In the step (B), for example, the vinyl aromatic peak derived from the Grignard reagent in the reaction mixture is directly applied to the reaction mixture obtained in the step (A) by gas chromatography-mass spectrometry (GC-MS) or the like. After confirming the disappearance of the above, by adding dropwise an organometallic compound of the above formula (V) or (VI) dissolved in an ether solvent similar to that used in the step (A) under an inert gas atmosphere, for example. Preferably it is done.

As the inert gas and the ether solvent, those described for the step (A) can be used similarly, and those used in the step (A) are preferably used.

The amount of the organometallic compound of the formula (V) or (VI) used is preferably an equimolar amount with respect to the compound of the formula (II), and 1.0 to 3.0 with respect to 1 mol of the compound of the formula (II). It can be used in a molar range.

The reaction temperature in step (B) is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. In particular, the temperature in the reaction vessel is preferably not more than 40 ° C, more preferably not more than 35 ° C. Usually, the progress of the reaction in the step (B), that is, the production of the heteroatom-containing aromatic vinyl compound of the formula (I) is fast, and the reaction is completed almost simultaneously with the completion of the dropping.

It is preferable to perform the step (C) of isolating the heteroatom-containing aromatic vinyl compound of the formula (I) obtained in the step (B) by filtration and / or vacuum distillation.

Filtration is performed by, for example, filtering the reaction solution obtained using a filter such as a cellulose filter and collecting the filtrate. The obtained filtrate is preferably concentrated under reduced pressure, the solvent is distilled off, and further distilled under reduced pressure.

The filter used for filtration is not particularly limited, but a cellulose filter having a mesh of 70 mm is preferably used. PTFE may be used as the material of the filter, and silica gel, alumina, celite, or the like may be used as the filter medium.

The vacuum concentration is preferably performed at an external temperature of 30 ° C./0.2 kPa to 60 ° C./0.2 kPa, and the vacuum distillation is preferably performed at 30 ° C./0.1 kPa to 120 ° C./0.1 kPa. It is possible to carry out by collecting the main distillation according to the boiling point of the heteroatom-containing aromatic vinyl compound.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

Hereinafter, various chemicals used in Examples and Comparative Examples are shown together. Each chemical was purified.
(Compound of formula (II))
4-Bromostyrene: Wako Pure Chemical Industries, Ltd. 4-Bromothiophene: Tokyo Chemical Industry Co., Ltd. (halogen compound of formula (III))
Dichlorodimethylsilane: Tokyo Chemical Industry Co., Ltd. Trichloromethylsilane: Tokyo Chemical Industry Co., Ltd. (organometallic compound of formula (V))
Ethoxy potassium: Wako Pure Chemical Industries, Ltd. Isopropoxy potassium: Wako Pure Chemical Industries, Ltd.
tert-Butoxy potassium: lithium diisopropylamide manufactured by Wako Pure Chemical Industries, Ltd .: 1.5 mol / L solution (organometallic compound of formula (VI)) manufactured by Tokyo Chemical Industry Co., Ltd.
n-octylmagnesium bromide: manufactured by Tokyo Chemical Industry Co., Ltd., about 22% THF solution, about 1 mol / L
Ethanol: Wako Pure Chemical Industries, Ltd. Isopropanol: Wako Pure Chemical Industries, Ltd.
tert-butanol: Wako Pure Chemical Industries, Ltd. Triethylamine: Wako Pure Chemical Industries, Ltd. Hexane: Wako Pure Chemical Industries, Ltd. Magnesium: Wako Pure Chemical Industries, Ltd. Dibromoethane: Wako Pure Chemical Industries, Ltd. ( Manufactured by THF (tetrahydrofuran): manufactured by Wako Pure Chemical Industries, Ltd.

Example 1: Synthesis of ethoxydimethyl (4-vinylphenyl) silane

Under a nitrogen gas atmosphere, 13.15 g (0.54 mol) of magnesium, 33.9 g of THF, and 1.87 g (0.01 mol) of 1,2-dibromoethane were placed in a 500 mL glass four-necked flask. Stir at 26 ° C. for 30 minutes. Next, 92.00 g (0.50 mol) of 4-bromostyrene was added dropwise so that the internal temperature did not exceed 60 ° C., and the mixture was stirred at 24 to 26 ° C. for 3 hours to react with (4-vinylphenyl) magnesium bromide. 45.9 g of liquid was prepared. A solution of 127.96 g (0.50 mol) of dichlorodimethylsilane and 30.3 g of THF was added dropwise to the obtained reaction solution over 3 hours so that the internal temperature did not exceed 30 ° C. After confirming disappearance of the styrene peak derived from (4-vinylphenyl) magnesium bromide by GC-MS, the inner temperature of a solution of 42.08 g (0.50 mol) of ethoxypotassium and 40.2 g of THF does not exceed 35 ° C. The filtrate was collected by filtration with a cellulose filter (mesh 70 mm), and the filtrate was collected and concentrated under reduced pressure at an external temperature of 40 ° C./0.2 kPa to distill off the solvent. Then, it distilled under reduced pressure at 70 degreeC / 0.1kPa, and collect | recovered the fraction whose boiling point is 45 degreeC / 0.1kPa as a main distillation. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 70.4%. As a result of analysis by GC-MS, dimethylbis (4-vinylphenyl) silane was not detected, and the purity of ethoxydimethyl (4-vinylphenyl) silane was 99.9%.

Example 2: Synthesis of iso-propoxydimethyl (4-vinylphenyl) silane

Other than using 49.06 g (0.50 mol) of iso-propoxy potassium in place of ethoxy potassium and distilling under reduced pressure at 75 ° C./0.1 kPa to collect a fraction having a boiling point of 70 ° C./0.1 kPa as the main distillation Obtained iso-propoxydimethyl (4-biphenyl) silane in the same manner as in Example 1. The total yield calculated from the molar ratio of the starting 4-bromostyrene was 72.4%. As a result of GC-MS analysis, no dimethylbis (4-vinylphenyl) silane was detected, and the purity of iso-propoxydimethyl (4-vinylphenyl) silane was 99.9%.

Example 3: Synthesis of tert-butoxydimethyl (4-vinylphenyl) silane

Except that 56.10 g (0.50 mol) of tert-butoxy potassium was used instead of ethoxy potassium, distilled under reduced pressure at 80 ° C./0.1 kPa, and the fraction having a boiling point of 73 ° C./0.1 kPa was recovered as the main distillation Produced tert-butoxydimethyl (4-vinylphenyl) silane in the same manner as in Example 1. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 74.1%. As a result of GC-MS analysis, no dimethylbis (4-vinylphenyl) silane was detected, and the purity of tert-butoxydimethyl (4-vinylphenyl) silane was 99.9%.

Example 4: Synthesis of diisopropylaminodimethyl (4-vinylphenyl) silane

Implemented except that lithium diisopropylamide (0.50 mol) was used instead of ethoxypotassium and distilled under reduced pressure at 130 ° C / 0.1 kPa and the fraction having a boiling point of 96 ° C / 0.1 kPa was recovered as the main distillation. In the same manner as in Example 1, diisopropylamino (4-vinylphenyl) silane was obtained. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 74.1%. As a result of GC-MS analysis, the purity of diisopropylamino (4-vinylphenyl) silane was 99.9%.

Example 5: Synthesis of (2-thienyl) dimethyl (4-vinylphenyl) silane

A solution reacted with 2-thienylmagnesium bromide (0.50 mol) produced in Production Example 1 described later instead of ethoxypotassium was filtered through silica gel, and then the solvent was distilled off under reduced pressure. In the same manner as in 1, (2-thienyl) dimethyl (4-vinylphenyl) silane was obtained. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 80.6%. As a result of GC-MS analysis, the purity of (2-thienyl) dimethyl (4-vinylphenyl) silane was 99.7%.

Example 6: Synthesis of dimethyloctyl (4-vinylphenyl) silane

A crude reaction solution was obtained in the same manner as in Example 1 except that n-octylmagnesium bromide (0.50 mol) was used in place of ethoxypotassium, and then obtained by filtration through silica gel instead of the cellulose filter. The solvent was distilled off to obtain dimethyl-n-octyl (4-vinylphenyl) silane. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 84%. As a result of GC-MS analysis, the purity of dimethyloctyl (4-vinylphenyl) silane was 99.0%.

Example 7: Synthesis of methyloctyl (2-thienyl) (4-vinylphenyl) silane

Instead of dichlorodimethylsilane (0.50 mol), dichloro (2-thienyl) methylsilane (0.50 mol) was used, and n-octylmagnesium bromide (0.50 mol) was used instead of ethoxypotassium. Except for the above, a crude reaction solution was obtained in the same manner as in Example 1, and the filtrate obtained by filtration through silica gel instead of the cellulose filter was evaporated to remove methyloctyl (2-thienyl) (4-vinylphenyl). Silane was obtained. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 86%. As a result of GC-MS analysis, the purity of methyloctyl (2-thienyl) (4-vinylphenyl) silane was 99.0%.

Example 8: Synthesis of methyl (2-thienyl) ethoxy (4-vinylphenyl) silane

The crude reaction solution was used in the same manner as in Example 1 except that dichloro (2-thienyl) methylsilane (0.50 mol) produced in Production Example 2 described later was used instead of dichlorodimethylsilane (0.50 mol). After that, the filtrate obtained by filtering with silica gel instead of the cellulose filter was evaporated to obtain methyl (2-thienyl) ethoxy (4-vinylphenyl) silane. The overall yield calculated from the molar ratio of the starting 4-bromostyrene was 86%. As a result of GC-MS analysis, the purity of methyl (2-thienyl) ethoxy (4-vinylphenyl) silane was 99.0%.

Production Example 1: Production of organometallic compound of formula (VI), 2-thienylmagnesium bromide In the preparation of (4-vinylphenyl) magnesium bromide of Example 1, 4-bromothiophene (0. 50 mol) was used to produce 2-thienylmagnesium bromide.

Production Example 2: Production of Halogen Compound of Formula (III), Dichloro (2-thienyl) methylsilane In the preparation of (4-vinylphenyl) magnesium bromide of Example 1, 2-bromothiophene (0 Trichloromethylsilane was added dropwise to the solution of 2-thienylmagnesium bromide prepared using .50 mol) so that the internal temperature did not exceed 60 ° C. to prepare a THF solution of dichloro (2-thienyl) methylsilane.

Comparative Example 1: Synthesis of ethoxydimethyl (4-vinylphenyl) silane Synthesis Example 1: Synthesis of (4-biphenyl) magnesium bromide In a nitrogen gas atmosphere, 13.15 g (0. 54 mol), 33.9 g of THF, and 1.87 g (0.01 mol) of 1,2-dibromoethane were added and stirred at 24-26 ° C. for 30 minutes. Next, 92.00 g (0.50 mol) of 4-bromostyrene was added dropwise so that the internal temperature did not exceed 60 ° C., and the mixture was stirred at 24 to 26 ° C. for 3 hours to react with (4-vinylphenyl) magnesium bromide. 45.9 g of liquid was prepared.

Synthesis Example 2: Synthesis of chloroethoxydimethylsilane In a nitrogen gas atmosphere, 49.4 g (0.39 mol) of dimethyldichlorosilane and 194 g of hexane were added to a 1 L glass four-necked flask at room temperature, followed by salt / ice. While cooling to 0 ° C. in a bath, a mixed solution of 17.90 g (0.39 mol) of ethanol, 38.5 g (0.38 mol) of triethylamine, and 194 g of hexane was added for 90 minutes so that the internal temperature was 15 ° C. or less. And then stirred at 24 to 26 ° C. for 1 hour to prepare a reaction solution of chloroethoxydimethylsilane. The chloroethoxydimethylsilane reaction solution is filtered through celite, concentrated at 80 ° C under atmospheric pressure to distill off the solvent, and then distilled under reduced pressure at 80 ° C / 15 kPa, with the fraction having a boiling point of 65 ° C / 15 kPa as the main fraction. Collected to obtain purified chloroethoxydimethylsilane.

Synthesis Example 3: Synthesis of ethoxydimethyl (4-vinylphenyl) silane Chloroethoxydimethylsilane (0.39 mol) prepared in Synthesis Example 2 was placed in a nitrogen-substituted 500 mL glass four-necked flask under an ice bath. The mixture was stirred while cooling until the internal temperature became 3-10 ° C. or lower. Thereafter, the reaction solution (0.39 mol) of (4-vinylphenyl) magnesium bromide prepared in Synthesis Example 1 was added dropwise so that the internal temperature was 15 ° C. or lower, and the mixture was stirred at 24 to 26 ° C. for 20 hours. Completion of the reaction was confirmed by a constant relative peak intensity of styrene derived from (4-vinylphenyl) magnesium bromide by gas chromatography (GC). 78.2 g of the reaction solution of ethoxydimethyl (4-vinylphenyl) silane was centrifuged at 8000 rpm / 15 minutes, and 62.95 g of the supernatant was recovered and concentrated under reduced pressure at an external temperature of 40 ° C./0.2 kPa. After distilling off, it was distilled under reduced pressure at 70 ° C./0.1 kPa, and a fraction having a boiling point of 45 ° C./0.1 kPa was recovered as the main distillation. The overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 7.4%. As a result of analysis by GC-MS, 5.0% of dimethylbis (4-vinylphenyl) silane (molecular weight: 264.13) was contained as an impurity, and the purity of ethoxydimethyl (4-vinylphenyl) silane was 95. 0.0%.

Comparative Example 2: Synthesis of iso-propoxydimethyl (4-vinylphenyl) silane Using 23.40 g (0.39 mol) of isopropanol instead of ethanol, distilled under reduced pressure at 85 ° C / 15 kPa, and having a boiling point of 70 ° C / 15 kPa Purified chloroisopropoxydimethylsilane was obtained in the same manner as in Synthesis Example 2 of Comparative Example 1 except that the fraction was collected as the main distillate. Iso-propoxydimethyl (4-biphenyl) silane was obtained in the same manner as in Synthesis Example 3 of Comparative Example 1 except that the chloroisopropoxydimethylsilane obtained above was used instead of chloroethoxydimethylsilane. The overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 8.2%. As a result of analysis by GC-MS, 6.2% dimethylbis (4-vinylphenyl) silane was contained as an impurity, and the purity of isopropoxydimethyl (4-vinylphenyl) silane was 93.8%. .

Comparative Example 3: Synthesis of tert-butoxydimethyl (4-vinylphenyl) silane 28.91 g (0.39 mol) of tert-butanol was used instead of ethanol and distilled under reduced pressure at 88 ° C / 15 kPa, and the boiling point was 75 ° C / Purified chloro-tert-butoxydimethylsilane was obtained in the same manner as in Synthesis Example 2 of Comparative Example 1 except that the 15 kPa fraction was collected as the main distillation.
Tert-butoxydimethyl (4-vinylphenyl) silane was obtained in the same manner as in Synthesis Example 3 of Comparative Example 1 except that the chloro-tert-butoxydimethylsilane obtained above was used instead of chloroethoxydimethylsilane. The overall yield calculated from the molar ratio of the starting dichlorodimethylsilane was 9.1%. As a result of analysis by GC-MS, 5.4% dimethylbis (4-vinylphenyl) silane was contained as an impurity, and the purity of tert-butoxydimethyl (4-vinylphenyl) silane was 94.6%. It was.

From the above results, the production methods of Examples 1 to 8 via chloro (vinylphenyl) silane as an intermediate are more than the conventional methods for producing heteroatom-containing aromatic vinyl compounds via chloroalkoxysilane as an intermediate. The target product can be obtained with high purity and high yield. Further, in the comparative example, since the hydrogen chloride triethylamine salt is generated, the operation is dangerous, whereas in the example, the target product can be safely taken out in one pot.

Claims

Formula (I): R 1 -R 2 -Y
(Wherein R 1 is an aromatic group having a vinyl group and optionally substituted with a group inert to the Grignard reagent, R 2 is Si (R 10 ) (R 11 ), In the formula, R 10 and R 11 are each independently a group containing at least one atom selected from the group consisting of halogen, carbon, silicon, nitrogen, sulfur and oxygen atoms, Y is carbon, A functional group containing at least one atom selected from the group consisting of silicon, nitrogen, sulfur and oxygen atoms)
A process for producing a heteroatom-containing aromatic vinyl compound represented by
(A) Formula (II): R 1 -X 1
(Wherein R 1 is the same as above, and X 1 is halogen)
In a reaction solution containing a Grignard reagent obtained by reacting magnesium with a compound represented by
Formula (III): X 2 -R 2 -X 3
(Wherein X 2 and X 3 are each independently halogen, and R 2 is the same as above)
A halogen compound represented by
Formula (IV): R 1 -R 2 -X 3
(Wherein R 1 , R 2 and X 3 are the same as above)
And (B) an organometallic nucleophile containing a functional group Y in the reaction mixture containing the halogenated aromatic vinyl intermediate obtained in step (A). Is added to the functional group Y to obtain a heteroatom-containing aromatic vinyl compound represented by the formula (I).
(C) The manufacturing method of Claim 1 including the process of isolating the heteroatom containing aromatic vinyl compound represented by Formula (I) obtained by process (B) by filtration and / or vacuum distillation.
Organometallic nucleophiles
Formula (V): M 1 -Y
(Wherein M 1 is an alkali metal and Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms)
Or an organic metal compound represented by formula (VI):

Wherein M 2 is an alkaline earth metal, Y is a functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and R 3 is halogen , A functional group containing at least one atom selected from the group consisting of carbon, silicon, nitrogen, sulfur and oxygen atoms, and may be the same as or different from Y)
The manufacturing method of Claim 1 or 2 which is an organometallic compound represented by these.
The process according to claim 3, wherein the organometallic nucleophile is a metal alkoxide or a Grignard reagent.
R 10 and R 11 are each independently halogen, C 1-10 alkyl, C 2-10 alkenyl, tri C 1-6 alkylsiloxy, C 1-6 acyl, C 1-6 acyloxy, C 1-6 Acyloxy C 1-6 alkyl, C 1-6 alkoxy, C 6-12 aryl, C 6-12 aryloxy, amino, C 1-6 alkylamino, di-C 1-6 alkylamino, cyano C 1-6 alkyl, C 1-6 alkoxy C 1-6 alkyl, C 4-10 heterocyclyl, thiobenzene C 1-6 alkyl, C 1-6 alkylamide or amide C 1-6 alkyl. The manufacturing method as described.
Y is C 1-10 alkyl, C 2-10 alkenyl, tri-C 1-6 alkylsiloxy, silanol, C 1-6 acyl, C 1-6 acyloxy, C 1-6 acyloxy C 1-6 alkyl, C 1 -6 alkoxy, C 6-12 aryl, C 6-12 aryloxy, amino, C 1-6 alkylamino, di-C 1-6 alkylamino, cyano C 1-6 alkyl, C 1-6 alkoxy C 1-6 The production method according to any one of claims 1 to 5, which is alkyl, C 4-10 heterocyclyl, thionyl, thiobenzene C 1-6 alkyl, C 1-6 alkylamide or amide C 1-6 alkyl.
The production method according to any one of claims 1 to 6, wherein the step (A) is started in the presence of an initiator.
The production method according to any one of claims 1 to 7, wherein the halogen compound of the formula (III) is dichlorodiC 1-10 alkylsilane or dichlorothiophene C 1-10 alkylsilane.