JPH06279477A - Production of cyclopentadienyl group-containing silicon or germanium compound - Google Patents

Abstract

PURPOSE:To efficiently produce a bulky cyclopentadienyl group-containing silicon or germanium compound in good yield in a short time. CONSTITUTION:The characteristic of this method for producing a cyclopentadienyl group-containing silicon or germanium compound is reacting (i) a lithium, a sodium or a potassium salt of a cyclopentadiene derivative with (ii) a halogenated silicon compound or a halogenated germanium compound in the presence of a diamine compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a process for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound.

[0002]

BACKGROUND OF THE INVENTION In recent years, metallocene complex catalysts having a cyclopentadienyl group as a ligand have been attracting attention as new olefin polymerization catalysts. Among such cyclopentadienyl group-based ligands, the cyclopentadienyl group-containing silicon compound or germanium compound is chiral and stereorigid when coordinated with a central metal (for example, zirconium). It has attracted attention because it can form (stereorigid) metallocene complexes. In particular, a zirconocene complex having such a ligand is known to be important as a catalyst component capable of producing an olefin with high polymerization activity (European Patent Application Publication No. 12).
9,368).

The metallocene complex having such a ligand is also useful as a catalyst for Diels-Alder reaction, hydrogenation reaction and the like. The cyclopentadienyl group-containing silicon compound (or germanium compound) used as the ligand of the metallocene complex as described above is generally a lithium, sodium or potassium salt of a cyclopentadiene derivative, and a silicon halide compound (or germanium halide). (Organometallics 3 1470 (1984), Chem.B.
erichte 119 1750 (1986), J. Am. Chem. Soc. 112 9558 (1
990), JP-A-2-221258, JP-A-3-21607,
JP-A-4-268307).

Specifically, for example, in JP-A-2-221258, a solution of an indenyllithium salt prepared from indene and n-butyllithium is slowly added to a dimethyldichlorosilane solution and then Dimethyldi (1-indenyl) silane was obtained at a yield of 71% by reacting overnight, and in JP-A-4-268307, dimethyldi (2-methyl-1-indenyl) silane was obtained by the same method. The yield is 16%.

In Chem. Berichte 119 1750 (1986), a solution of 1,2,3,4-tetramethylcyclopentadienyllithium and dimethyldichlorosilane is heated for 5 days to give dimethylbis (2, 3,4,5-Tetramethylcyclopentadienyl) silane is obtained with a yield of 65%.

However, the conventional method as described above is
Both of them have to be reacted for a long time, and the yield is low, especially when trying to produce a compound in which two or more groups having large steric hindrance are bonded to silicon or germanium. However, there is a problem that the yield is further reduced.

For this reason, if a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, especially a silicon compound or germanium compound having a bulkier cyclopentadienyl group substituted with an alkyl group or the like, If a method that can be manufactured well appears, its industrial value will be extremely great.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a cyclopentadienyl group-containing silicon compound or cyclopentadienyl useful for producing a metallocene complex catalyst component and the like. Group-containing germanium compound, in particular a cyclopentadienyl-group-containing silicon capable of producing a silicon compound or a germanium compound having a more bulky cyclopentadienyl group substituted with an alkyl group or the like in a short time and in a high yield An object of the present invention is to provide a method for producing a compound or a cyclopentadienyl group-containing germanium compound.

[0009]

The method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to the present invention comprises (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative, and (i)
i) It is characterized by reacting a silicon halide compound or a germanium halide compound in the presence of a diamine compound.

In the present invention, the diamine compound as described above is preferably N, N'-tetraalkylethylenediamine. The metal salt of the cyclopentadiene derivative (i) used in the present invention is preferably a metal salt of a cyclopentadiene derivative having 2 to 4 substituents in the cyclopentadienyl skeleton, and further a lithium salt. Is preferred.

Further, (ii) the silicon halide compound is preferably dihalodialkylsilane, dihalodiarylsilane or dihaloalkylarylsilane, and the germanium halide compound is dihalodialkylgermane, dihalodiarylgermane or dihalodiarylgermane. It is preferably haloalkylarylgermane.

[0012]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to the present invention will be specifically described below.

The method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to the present invention comprises (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative, and (ii)
The silicon halide compound or the germanium halide compound is reacted in the presence of a diamine compound.

(I) Metal salt of cyclopentadiene derivative (i) Lithium, sodium or potassium salt of (i) cyclopentadiene derivative used in the above reaction
(i) a cyclopentadiene derivative forming a metal salt of a cyclopentadiene derivative) includes cyclopentadiene, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group such as methoxy, ethoxy and butoxy, phenoxy, Allyloxy group such as methylphenoxy and dimethylphenoxy, nitro group, amino group such as amino, dimethylamino and diethylamino, urea, N ', N'-
Urea groups such as dimethylurea, N, N ', N'-trimethylurea, halogens of F, Cl, Br, I, organosilicons such as trimethylsilane, triethylsilane and tributylsilane, trimethylgermane, triethylgermane, tributylgermane, etc. The cyclopentadiene compound having a substituent such as organic germanium, organic tin such as trimethyltin, triethyltin, and tributyltin. These substituents may be plural, and the plural substituents may be the same or different.

Of the above-mentioned substituents, the number of carbon atoms is 1 to 3.
Specific examples of the hydrocarbon group of 0 include an alkyl group such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, decyl and dodecyl, aryl such as phenyl, methylphenyl, dimethylphenyl, octylphenyl and naphthyl. Group, and these may be combined with the adjacent carbon of cyclopentadiene to form a ring, and these include indene derivatives, 4,5,6,
Includes 7-tetrahydroindene derivatives and fluorene derivatives. Further, these substituents are methoxy, ethoxy,
Alkoxy group such as butoxy, phenoxy, methylphenoxy, allyloxy group such as dimethylphenoxy, nitro group, amino group such as amino, dimethylamino, diethylamino, urea, N ', N'-dimethylurea, N, N', N ' -Urea groups such as trimethylurea, halogens of F, Cl, Br and I, organosilicons such as trimethylsilyl, triethylsilyl and tributylsilyl, trimethylgermane,
It may be substituted with organic germanium such as triethylgermane or tributylgermane, or organic tin such as trimethyltin, triethyltin or tributyltin.

Examples of such a cyclopentadiene derivative include, but are not limited to, the followings. Cyclopentadiene, methylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,2,3- or 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, tert-butylcyclopentadiene , Ethylcyclopentadiene, phenylcyclopentadiene, trimethylsilylcyclopentadiene,
1,2-dimethyl-4-ethylcyclopentadiene, 1,2-dimethyl-4-tert-butylcyclopentadiene, 1,2-dimethyl
-4-trimethylsilylcyclopentadiene, naphthylcyclopentadiene, 1,2-dimethyl-4- (3-methoxypropyl) cyclopentadiene, indene, 1-methylindene, 2-methylindene, 2-ethylindene, 2-isopropylindene, 2-phenylindene, 2-trimethylsilylindene, 3-methylindene, 4-methylindene, 5-
Methylindene, 6-methylindene, 7-methylindene, 2-methyl-4-methoxyindene, 4,7-dimethylindene, 2,4,7-trimethylindene, 2,4-diisopropylindene, 2-methyl-4 -Isopropylindene, 4,5,6,7
-Tetrahydroindene, 2-methyl-4,5,6,7-tetrahydroindene, fluorene and the like can be mentioned.

In the present invention, having 2 to 4 substituents,
In particular, it is preferable to use cyclopentadiene, indene, fluorene or the like having 3 or 4 substituents, for example, 1,2,4-trimethylcyclopentadiene,
(1,2,3,4-tetramethylcyclopentadiene, 1,2-dimethyl-4-tert-butylcyclopentadiene, 1,2-dimethyl
-4-Trimethylsilylcyclopentadiene, 1,2-dimethyl-4-ethylcyclopentadiene, indene, 2-methylindene, 2-ethylindene, fluorene and the like are preferable.

In the present invention, the lithium, sodium or potassium salt of such a cyclopentadiene derivative is used, and among these, the lithium salt of the cyclopentadiene derivative is preferable.

The lithium, sodium or potassium salt of the (i) cyclopentadiene derivative used in the present invention as described above is diethyl ether, tetrahydrofuran,
Synthesized by reacting the corresponding cyclopentadiene derivative with a lithium metal, sodium metal or potassium metal or their hydride, amidated, alkylated or arylated compound in an inert solvent such as hexane or benzene. can do.

(Ii) Silicon halide compound or halogen
Examples of the halogen forming the silicon halide compound or the germanium halide compound used in the present invention include fluorine, chlorine, bromine and iodine, preferably chlorine and bromine, and more preferably chlorine. The silicon halide compound or the germanium halide compound is
It has 1 to 4 halogens, and these halogens may be the same or different. Substituents other than halogen in the silicon halide compound or germanium halide compound include hydrogen, hydrocarbon groups having 1 to 30 carbon atoms, organic silyl groups such as trimethylsilyl, triethylsilyl, triphenylsilyl, and methyldiphenylsilyl, trimethylgermane. , An organic germane group such as triethylgermane, triphenylgermane and methyldiphenylgermane, an alkoxy group such as methoxy and ethoxy,
Examples include aryloxy groups such as phenoxy and methylphenoxy. When a plurality of these substituents are present, they may be the same or different.

Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl, butyl, hexyl, octyl, dodecyl and cyclohexyl, and aryl groups such as phenyl, tolyl, dimethylphenyl and naphthyl. To be In addition, these hydrocarbons include alkoxy groups such as methoxy and ethoxy, allyloxy groups such as phenoxy and methylphenoxy, nitro groups, amino,
Amino groups such as dimethylamino and diethylamino, urea groups such as urea, N ', N'-dimethylurea, N, N', N'-trimethylurea, halogens such as F, Cl, Br and I,
It may be substituted with an organic silicon such as trimethylsilyl, triethylsilyl, tributylsilyl, an organic germanium such as trimethylgermane, triethylgermane, tributylgermane, an organic tin such as trimethyltin, triethyltin, tributyltin and the like.

Examples of these include, but are not limited to, the following. Monohalogenated silicon compounds such as methylchlorosilane, dimethylchlorosilane, diphenylchlorosilane, trimethylchlorosilane, triethylchlorosilane, triphenylchlorosilane, methyldiphenylchlorosilane, methylphenylbromosilane, and methylphenyliodosilane, methyldichlorosilane, phenyldichlorosilane, dimethyldiphenylsilane. Chlorosilane, diethyldichlorosilane, di-tert-
Butyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, di (2-methylphenyl)
Dichlorosilane, di (2,6-dimethylphenyl) dichlorosilane, dicyclohexyldichlorosilane, 1,4-tetramethylenedichlorosilane, 1,5-pentamethylenedichlorosilane, di (trimethylsilyl) dichlorosilane, methyltrimethylsilyldichlorosilane, di Dihalogenated silicon compounds (dihalosilane compounds) such as naphthyldichlorosilane, methylnaphthyldichlorosilane, 1,1,2,2-tetramethyl-1,2-dichlorodisilane, dimethyldibromosilane, trichlorosilane, methyltrichlorosilane, phenyltri Examples thereof include trihalogenated silicon compounds such as chlorosilane and phenyltribromosilane, and tetrahalogenated silicon compounds such as tetrachlorosilane and tetrachlorogermane.

Examples of the germanium halide compound include the above-mentioned silicon halide compounds in which silicon is replaced by germanium. Of these, compounds having a secondary or tertiary alkyl group or an aromatic hydrocarbon group bonded are preferable, and specific examples include isopropyl group, sec-butyl group, cyclohexyl group, tert-
A compound having a butyl group, a phenyl group, a tolyl group, a dimethylphenyl group, a naphthyl group, or the like bonded thereto is preferable
Further, a dihalogenated silicon compound or a dihalogenated germanium compound having such a group is preferable, and particularly dihalodialkylsilane, dihalodiarylsilane, dihaloalkylarylsilane, dihalodialkylgermane, dihalodiarylgermane or dihaloalkylarylgermane. Is preferred.

Production Method In the present invention, the above-mentioned (i) metal salt of a cyclopentadiene derivative and (ii) a silicon halide compound or a germanium halide compound are reacted in the presence of a diamine compound.

Specific examples of the diamine compound used in the present invention include ethylenediamine, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N'-tetramethylethylenediamine, N, N'-tetraethylethylenediamine and N. , N'-tetrapropylethylenediamine,
N, N'-tetrabutylethylenediamine, N, N'-tetrahexylethylenediamine, N, N'-tetracyclohexylethylenediamine and other N, N'-tetraalkylethylenediamine, N, N'-tetraphenylethylenediamine, 1,2-
Diaminopropane, 1,2-di (dimethylamino) propane, 2,3-diamino-n-butane, 2,3-di (dimethylamino) -n-butane, 1,2-di (dimethylamino) cyclohexane, etc. Propylenediamine derivatives such as ethylenediamine derivatives, 1,3-di (dimethylamino) propane, 1,3-di (diethylamino) propane, 1,3-diaminopropane, o-diaminobenzene, o-di (dimethylamino) benzene, etc. Aromatic diamine derivatives of

Of these, N, N'-tetraalkylethylenediamine is preferred in the present invention. In such a production method according to the present invention, for example, (i) a lithium salt of a cyclopentadiene derivative and (ii) an organic silicon halide compound are reacted in the presence of N, N'-tetramethylethylenediamine to give bis ( The case of producing a cyclopentadienyl) -silicon compound is shown below.

[0027]

[Chemical 1]

In such a reaction, (i) the metal salt of the cyclopentadiene derivative and (ii) the silicon halide compound or the germanium halide compound are usually mixed at a molar ratio [(i) / (ii)] of 1: 1. : 20 to 20: 1, preferably 1: 5 to 5: 1.

The diamine compound has a molar ratio of 1:10 to 1 to the metal salt of the (i) cyclopentadiene derivative.
It is used in an amount of 0: 1, preferably 1: 2 to 2: 1, more preferably 1: 1.2 to 1.2: 1.

The reaction is usually carried out in the presence of a solvent. Specific examples of the reaction solvent include pentane, hexane, heptane, octane, cyclohexane, petroleum ether, benzene, hydrocarbons such as toluene, diethyl ether, dimethoxyethane, tetraglyme, diisopropyl ether, tetrahydrofuran, diphenyl ether, tert.
-Ethyl compounds such as butyl methyl ether, dioxane and anisole, amide compounds such as 1-methyl-2-pyrrolidone, urea compounds such as tetramethylurea and 1,3-dimethyl-2-imidazolidone, sulfone compounds such as sulfolane Can be mentioned.

Of these, ether compounds are preferred.
The reaction may be carried out batchwise or continuously. At this time, the diamine compound was added in advance to (i) a solution of a metal salt of a cyclopentadiene derivative, or (ii) a silicon halide compound or a germanium halide compound or a solution thereof, or a mixture of both. It may be added later.

The reaction of (i) a metal salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound is carried out at -80 ° C to 200 ° C, preferably -50 ° C to 100 ° C, more preferably -30 ° C
It is carried out at a temperature of ~ 80 ° C.

The reaction time is usually 1 minute to 2 weeks, preferably 10 minutes to 1 week, more preferably 30 minutes to 4 days. In the present invention, a cyan compound such as copper cyanide or a thiocyanic acid compound, a phosphoric amide compound such as hexamethylphosphoric triamide, and the like may be allowed to coexist in the reaction system as described above.

In the method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to the present invention, (ii) the polyhalogenated silicon compound is used as the silicon halide compound (or the germanium halide compound). Cyclopentadienyl group-containing silicon compound in which all halogens in the polyhalogenated silicon compound (or polyhalogenated germanium compound) are substituted with cyclopentadienyl groups using the compound (or polyhalogenated germanium compound) (Or a germanium compound), or a cyclopentadienyl group-containing silicon compound (or a germanium compound) in which a part of halogen is substituted with a cyclopentadienyl group can be obtained.

Like the latter, (ii) a cyclopentadienyl group-containing silicon compound (or germanium compound) in which a part of the halogens of the polyhalogenated compound (or polyhalogenated germanium compound) is substituted with a cyclopentadienyl group. ) Is produced, (ii) the polyhalogenated silicon compound (or the polyhalogenated germanium compound) is converted into the metal salt of the (i) cyclopentadiene derivative at a molar ratio of one halogen atom to be substituted. On the other hand, 1: 2 to 2: 1, preferably 1: 1.2 to 1.
Used in an amount of 2: 1.

In this reaction, among the above addition methods, (i) a metal salt of a cyclopentadiene derivative or a solution thereof is added dropwise to a polyhalogenated silicon compound or a polyhalogenated germanium compound or a solution thereof. Is preferred.

According to the present invention as described above, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound can be produced in a short time and with a high yield.

In particular, even when a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound having a functional group with a large steric hindrance is to be obtained, the compound is produced in a good yield in a short time. be able to. More specifically, in the case where the metal salt of the (i) cyclopentadiene derivative is a metal salt of a cyclopentadienyl group having 2 to 4, especially 3 or 4 substituents as described in each raw material. And / or (ii) when the silicon halide compound (or germanium compound) has secondary or tertiary carbon or aromatic carbon, the effect of coexisting the diamine compound is increased.

Silicon compound containing cyclopentadienyl group
Alternatively, the cyclopentadienyl group-containing germanium compound as the cyclopentadienyl group-containing silicon compound produced by the present invention as described above includes monocyclopentadienyl derivative-substituted silane, dicyclopentadienyl derivative-substituted silane, and tricyclopentadienyl derivative-substituted silane. Examples thereof include pentadienyl derivative-substituted silanes, tetracyclopentadienyl derivative-substituted silanes, and compounds in which these silicons are substituted with germanium.

The cyclopentadienyl derivative is a cyclopentadiene, a cycloalkyl group having a substituent group such as a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, an allyloxy group, an amino group, a halogen, an organic silicon, an organic germanium and an organic tin. Examples include pentadiene compounds. These substituents may be plural, and the plural substituents may be the same or different.

Of the above-mentioned substituents, the number of carbon atoms is 1 to 3.
Specific examples of the hydrocarbon group of 0 include an alkyl group, an aryl group, and an alkylaryl group, which may be bonded to adjacent carbons of cyclopentadiene to form a ring, and further, these substituents May be substituted with an alkoxy group, an aryloxy group, a nitro group, an amino group, a urea group, a halogen, an organosilicon, an organogermanium or an organotin.

Among the substituents of the cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound, the substituents other than the cyclopentadienyl derivative are hydrogen, hydrocarbon groups having 1 to 30 carbon atoms, Alkoxy group, allyloxy group, halogen group, organosilicon,
Substituents such as organic germanium may be mentioned. These substituents may be the same or different. Examples of the hydrocarbon group having 1 to 30 carbon atoms among the above substituents include an alkyl group and an aryl group, and these substituents are an alkoxy group, an aryloxy group, a nitro group, an amino group,
Urea group, halogen, organosilicon, organogermanium,
It may be substituted with organic tin, organic phosphorus, or organic aluminum.

The following are examples of these, but the invention is not limited thereto. Cyclopentadienyltrimethylsilane, cyclopentadienyltriphenylsilane, cyclopentadienyltriisopropylsilane, cyclopentadienylmethyldiphenylsilane,
2-methylcyclopentadienyltriphenylsilane, 2,
3,4-trimethylcyclopentadienyltrimethylsilane, 2,3,4,5-tetramethylcyclopentadienyltrimethylsilane, 2,3,4,5-tetramethylcyclopentadienyldimethylchlorosilane, 2,3, 4,5-tetramethylcyclopentadienyldiphenylchlorosilane, 2,3,4,5-tetramethylcyclopentadienylmethyldichlorosilane,
1-indenyltrimethylsilane, 1-indenyltriphenylsilane, 2-methyl-1-indenyltriphenylsilane, 2-methyl-1-indenyldiphenylchlorosilane, 2
-Methyl-1-indenylphenyldichlorosilane, 2-methyl-4-isopropyl-1-indenyldiphenylchlorosilane and other monocyclopentadienyl silicon compounds, di (cyclopentadienyl) dimethylsilane, di (cyclopentadiene) (Enyl) phenylmethylsilane, di (cyclopentadienyl) diphenylsilane, di (2,3,5-trimethylcyclopentadienyl) dimethylsilane, di (2,3,5-
Trimethylcyclopentadienyl) phenylmethylsilane, di (2,3,5-trimethylcyclopentadienyl) diphenylsilane, di (2,3,5-trimethylcyclopentadienyl) diisopropylsilane, di (2,3, 5-trimethylcyclopentadienyl) t-butylmethylsilane, di (1-indenyl) dimethylsilane, di (1-indenyl) phenylmethylsilane, di (1-indenyl) diphenylsilane, di (1-indenyl) ditolylsilane, Di (1-indenyl) dinaphthylsilane, di (1-indenyl) di (2,6-
Dimethylphenyl) silane, di (1-indenyl) phenylchlorosilane, di (1-indenyl) dichlorosilane,
Di (2-methyl-1-indenyl) dimethylsilane, di (2-
Methyl-1-indenyl) diphenylsilane, di (2-methyl-1-indenyl) dichlorosilane, di (2-phenyl-1-)
Indenyl) dimethylsilane Di (2-methyl-4-trimethylsilyl-1-indenyl) dimethylsilane, di (2-methyl-4-phenyl-1-indenyl)
Di (cyclopentadienyl) silicon compounds such as dimethylsilane, 2-methyl-1-indenyl-cyclopentadienyldimethylsilane, 1-fluorenyl-cyclopentadienyldimethylsilane, tri (cyclopentadienyl)
Silane, tri (cyclopentadienyl) methylsilane,
Tri (cyclopentadienyl) phenylsilane, tri (cyclopentadienyl) isopropylsilane, tri (cyclopentadienyl) -t-butylsilane, tri (cyclopentadienyl) chlorosilane, tri (1-indenyl) silane, tri Such as (1-indenyl) chlorosilane, tri (1-indenyl) phenylsilane, tri (cyclopentadienyl) silicon compounds, tetra (cyclopentadienyl) silane, tetra (3-methylcyclopentadienyl) silane, etc. A tetra (cyclopentadienyl) silicon compound is mentioned.

Further, as the cyclopentadienyl group-containing germanium compound produced by the present invention, in the above-mentioned examples of the cyclopentadienyl group-containing silicon compound, compounds in which silicon is replaced by germanium can be exemplified. .

A metallocene complex obtained by reacting the above-mentioned cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound obtained in the present invention with a transition metal compound such as zirconium as described above. Is used as a highly active olefin polymerization catalyst component. When a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound is used in forming a ligand of such a metallocene complex, specifically, 2 to 4 substituents are included. Compounds having a cyclopentadiene derivative group such as a cyclopentadienyl group, an indenyl group, or a fluorenyl group group having a are preferred. Furthermore, a cyclopentadienyl group having 3 or 4 substituents, 1-position-substituted,
Compounds having cyclopentadiene derivative groups such as 2-position-substituted, 3-position-substituted, 1-position and 2-position-substituted, 1-position and 3-position-substituted or 2-position and 3-position-substituted indenyl groups or fluorenyl groups are preferred. .

[0046]

EFFECTS OF THE INVENTION According to the present invention, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound can be produced in a short time and with a good yield.

In particular, when an attempt is made to obtain a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound in which two or more groups having large steric hindrance are bonded to silicon or germanium, The compound can be produced in good yield in a short time.

[0048]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[0049]

Example 1 All reactions were carried out under a nitrogen atmosphere. 1,
2,4-trimethylcyclopentadiene (9 mmol), N,
N'-tetramethylethylenediamine (9.9 mmol)
And 14 ml of tetrahydrofuran were cooled to −10 ° C., 6 ml of a hexane solution prepared by dissolving n-butyllithium (9.9 mmol) in 6 ml of hexane was added dropwise, and the mixture was reacted at −10 ° C. for 1 hour while stirring. It was

5 ml of a tetrahydrofuran solution prepared by dissolving dimethyldichlorosilane (5 mmol) in 5 ml of tetrahydrofuran was added dropwise to the obtained reaction solution at -10 ° C over 15 minutes, and then the reaction was carried out at room temperature for 24 hours while stirring. Let

The reaction solution was neutralized with aqueous ammonium chloride, and the organic layer was extracted with diethyl ether. By the above reaction, di (2,3,5-trimethylcyclopentadienyl)
Dimethylsilane was obtained. As a result of analysis by gas chromatography, the yield was 54%. Also unreacted 1,2,
4-Trimethylcyclopentadiene was 12%.

[0052]

Comparative Example 1 The reaction was performed in the same manner as in Example 1 except that N, N'-tetramethylethylenediamine was not used.

Di (2,3,5-trimethylcyclopentadienyl) dimethylsilane was obtained with a yield of 5%. Unreacted
The content of 1,2,4-trimethylcyclopentadiene was 31%.

[0054]

Example 2 Indene (8.4 mmol), N, N′-tetramethylethylenediamine (9.2 mmol) and 14 ml of tetrahydrofuran were cooled to −10 ° C., and n-butyllithium ( 6 (9.2 mmol)
A solution prepared by dissolving it in ml of hexane was added dropwise, and -1
The reaction was allowed to proceed for 1 hour with stirring at 0 ° C.

Then, the reaction solution obtained was brought to room temperature, to which phenylmethyldichlorosilane (4.6 mmol) was added.
5 ml of tetrahydrofuran was added at -10 ° C over 15 minutes, and the mixture was reacted at room temperature for 1 hour with stirring.

The obtained reaction liquid was treated in the same manner as in Example 1 to obtain di (1-indenyl) phenylmethylsilane.
The results of analysis by gas chromatography are shown in Table 1.

[0057]

Examples 3 to 6 In Example 2, the solvent, reaction temperature,
The reaction was performed in the same manner as in Example 2 except that the reaction time was changed as shown in Table 1. The results are shown in Table 1.

[0058]

Comparative Examples 2 and 3 The reaction was carried out in the same manner as in Example 2 except that N, N'-tetramethylethylenediamine was not used and the solvent was changed to that shown in Table 1.

The results are shown in Table 1.

[0060]

[Table 1]

Claims (5)

[Claims] 1. A method of reacting (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound in the presence of a diamine compound. A method for producing a pentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound. 2. The method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to claim 1, wherein the diamine compound is N, N′-tetraalkylethylenediamine. . 3. A lithium, sodium or potassium salt of (i) a cyclopentadiene derivative is a lithium, sodium or potassium salt of a cyclopentadiene derivative containing 2 to 4 substituents in the cyclopentadienyl skeleton. The method for producing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound according to claim 1. 4. The lithium salt of (i) a cyclopentadiene derivative, a sodium salt or a potassium salt is a lithium salt of a cyclopentadiene derivative.
Alternatively, the method for producing the cyclopentadienyl group-containing silicon compound or the cyclopentadienyl group-containing germanium compound described in 3). 5. (ii) The silicon halide compound or germanium halide compound is a dihalodialkylsilane,
2. A cyclopentadienyl group-containing silicon compound or cyclopentadiene according to claim 1, which is dihalodiarylsilane or dihaloalkylarylsilane, or dihalodialkylgermane, dihalodiarylgermane or dihaloalkylarylgermane. A method for producing an enyl group-containing germanium compound.