JPH0827160A - Production of metal complex ligand - Google Patents

Abstract

PURPOSE:To readily produce a metal complex ligand useful as a raw material for a Ziegler catalyst in high yield. CONSTITUTION:A substituted cyclopentadienyl anion is reacted with an aminoalkoxysilane shown by the general formula t-BuNH-Si(R<1>R<2>)(OR<3>) (R<1>, R<2> and R<3> are each an alkyl group) to give the objective metal complex ligand shown by the general formula t-BuNH-Si(R<1>R<2>)-X(R<1> and R<2> are each an alkyl group; X is a substituted cyclopentadienyl group) useful as a raw material for a Ziegler catalyst.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula t-BuNH-Si (R
The present invention relates to a method for producing a metal complex ligand represented by ¹ R ² ) -X (wherein R ¹ and R ² are alkyl groups, and X is a substituted cyclopentadienyl group). This metal complex ligand is industrially extremely useful as a raw material for a Ziegler catalyst.

[0002]

2. Description of the Related Art Conventionally, a metal complex complex represented by the general formula t-BuNH-Si (R ¹ R ² ) -X (wherein R ¹ and R ² are alkyl groups and X is a substituted cyclopentadienyl group) is used. The method for synthesizing the ligand includes (1) X-Si (R ¹ R ² ) _2- Cl (wherein R ¹ and R ² are alkyl groups,
X is a substituted cyclopentadienyl group) and t-BuNH ₂ are reacted (JP-A-3-63088). (2) X-Si (R ¹ R ² ) ₂ -Cl (wherein R ¹ and R ² are alkyl groups, X
Is a substituted cyclopentadienyl group) and t-BuNHLi (US-5057475). (3) Method of reacting (t-BuNH) Si (R ¹ R ² ) ₂ -Cl (wherein R ¹ and R ² are alkyl groups, X is a substituted cyclopentadienyl group) with a cyclopentadienyl anion (WO-938199). It has been known.

In both the production methods (1) and (2), X-Si (R ¹ R ² ) ₂ -Cl (wherein R ¹ and R ² are alkyl groups, X is a substituted cyclopentadienyl group). ) Compounds need to be used. However, since this compound is thermally unstable, it is difficult to manufacture, and handling such as storage requires caution. Furthermore, (1) X-Si (R ¹ R ² ) _2- Cl (wherein R ¹ and R ² are alkyl groups and substituted cyclopentadienyl groups) and t-BuNH ₂
The method of reacting with and has the problems that the reaction time is extremely long and the yield thereof is low. On the other hand, the method of reacting (2) X-Si (R ¹ R ² ) ₂ -Cl (wherein R ¹ and R ² are alkyl groups, X is a substituted cyclopentadienyl group) with t-BuNHLi is Although it has the advantage of a shorter reaction time than the method (1), it requires the use of expensive organolithium reagents when preparing t-BuNHLi, and its production requires special equipment. There are some problems. Further, the production method of (3) is a production method that overcomes the problems of (1) and (2), but the aminochlorosilane compound used as a raw material is a compound that easily undergoes a reaction such as hydrolysis, so it is easy to handle. In addition to the need for caution, side reactions easily occur in the reaction system, and as a result, the purity and yield of the desired product are reduced.

[0004]

As described above, the object of the present invention is to provide a compound of the general formula t-BuNH-Si (R ¹ R ² ) -X (where: R ¹ and R ² are alkyl groups, and X is a substituted cyclopentadienyl group), and to provide a method for easily and efficiently producing a metal complex ligand.

[0005]

Means for Solving the Problems As a result of intensive studies on the method for producing a metal complex ligand, the present inventors have found that a desired product can be easily prepared by reacting a substituted cyclopentadienyl anion with an aminoalkoxysilane compound. In addition, they have found that they can be produced with high yield and completed the present invention.

That is, the present invention provides a substituted cyclopentadienyl anion and the general formula t-BuNH-Si (R ¹ R ² ) (OR ³ ), where R ¹ , R ² and R ³ are alkyl groups. By reacting with an aminoalkoxysilane compound shown in the general formula t-BuNH-Si
This is a method for producing a metal complex ligand represented by (R ¹ R ² ) -X (wherein R ¹ and R ² are alkyl groups, and X is a substituted cyclopentadienyl group). In the present invention, a substituted cyclopentadienyl anion and the general formula t-BuNH-Si (R ¹ R ² ) (OR ³ )
(Wherein R ¹ , R ² and R ³ are alkyl groups) reacts rapidly with an aminoalkoxysilane compound represented by the general formula t-BuNH-Si (R ¹ R ² ) A metal complex ligand represented by -X (wherein R ¹ and R ² are alkyl groups and X is a substituted cyclopentadienyl group) can be obtained easily and in good yield.

The present invention will be described in detail below. The substituted cyclopentadienyl anion used in the present invention can be prepared by all known methods utilizing a substituted cyclopentadiene compound, an alkali metal compound and the like. Examples of the substituted cyclopentadiene compound include methylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, tert-butylcyclopentadiene, indene and fluorene.

The alkaline metal compound is lithium,
Examples include potassium, sodium, lithium hydride, potassium hydride, sodium hydride, methyllithium, n-butyllithium, t-butyllithium and the like.

Examples of the aminoalkoxysilane compound used in the present invention include (t-butylamino) dimethylmethoxysilane, (t-butylamino) diethylmethoxysilane, (t-butylamino) methylbutylethoxysilane and the like. You can

The production method of the present invention comprises adding a separately synthesized aminomethoxysilane compound to a substituted cyclopentadienyl anion solution generated in the presence of a solvent, or a substituted cyclopentadienyl compound solution containing a substituted cyclopentadienyl anion solution. In this method, a solution of pentadienyl anion is added. As the solvent, an ether-based single solvent such as tetrahydrofuran or diethyl ether, or a mixed solvent of an ether-based solvent and another hydrocarbon-based inert solvent such as benzene or toluene can be used.

The reaction temperature in the present invention is -100 ° C to 1
Although it can be applied in the range of 50 ° C, it is usually -78 ° C to 50 ° C in view of reaction rate and operability. The reaction time in the present invention varies depending on the raw materials used, but is generally in the range of 1 minute to 48 hours, but is usually 5 minutes to 12 hours, and actually 5 minutes to 3 hours is sufficient. . The molar ratio of the reaction between the substituted cyclopentadienyl anion compound and the aminomethoxysilane compound in the present invention can be carried out in the range of 1: 0.1 to 1:10, but is usually stoichiometrically equal to 1 Approximately 1 is preferable. The substituted cyclopentadienyl anion compound and the aminomethoxysilane compound used in the present invention easily react with oxygen, water and the like, and therefore it is preferable to carry out the reaction in the presence of an inert gas such as nitrogen and argon.

[0012]

EXAMPLES Next, the present invention will be specifically described by way of examples. Example 1 5 equipped with a stirrer, a cooler and a dropping funnel under a nitrogen stream.
Tetramethylcyclopentadiene 8 in an L 3-neck flask
A sodium tetramethylcyclopentadienyl anion solution was prepared by charging 8.6 g, tetrahydrofuran 1000 ml and sodium hydride 18.3 g and heating under reflux for 24 hours. Then, while stirring at 20 ° C., 116 g of tertiary-butylaminodimethylmethoxysilane (purity of 97% by gas chromatography analysis) and 200 ml of tetrahydrofuran synthesized by a separately known method were added dropwise from a dropping funnel over 2 hours. . Then, stirring was continued for 12 hours. Next, the contents of the flask were charged into a rotary evaporator, and the solvent used for the reaction was distilled off. The obtained white solid substance was dehydrated with hexane 300
Extract 3 times with ml. All hexane solutions obtained by extraction were charged into a rotary evaporator, and hexane was distilled off to obtain an oily substance. Subsequently, this oily substance was distilled under reduced pressure to obtain 139 g of (tetramethylcyclopentadienyl) (tertiarybutylamino) dimethylsilane. The purity of the final product was 98% by gas chromatography analysis. The yield of the final product was 76% based on the tetramethylcyclopentadienyl anion used as a raw material.

Comparative Example 1 1 equipped with a stirrer, a cooler and a dropping funnel under a nitrogen stream.
Tetramethylcyclopentadiene 1 in a 3-neck L flask
A sodium tetramethylcyclopentadienyl anion solution was prepared by charging 7.7 g, 200 ml of tetrahydrofuran and 3.66 g of sodium hydride and heating under reflux for 16 hours. Then, while stirring at 20 ° C., 22 g of tertiary butylaminodimethylchlorosilane (purity of 97% by gas chromatography analysis) and tetrahydrofuran 50 synthesized separately by a known method.
ml was added dropwise from the dropping funnel over 2 hours. Then one
Stirring was continued for 2 hours. Next, the contents of the flask were charged into a rotary evaporator, and the solvent used for the reaction was distilled off. 100 ml of dehydrated hexane was added to the obtained white solid substance.
It was extracted 3 times with. All hexane solutions obtained by extraction were charged into a rotary evaporator, and hexane was distilled off to obtain an oily substance. Subsequently, this oily substance was distilled under reduced pressure to obtain 18.6 g of (tetramethylcyclopentadienyl) (tert-butylamino) dimethylsilane. The purity of the final product was 94% by gas chromatography analysis. The yield of the final product was 51% based on the tetramethylcyclopentadienyl anion used as a raw material.

[0014]

According to the present invention, the general formula t-BuNH-Si (R
The metal complex ligand represented by ¹ R ² ) -X (wherein R ¹ and R ² are alkyl groups and X is a substituted cyclopentadienyl group) can be produced by an industrially advantageous method. The compound of the general formula t-BuNH-Si (R ¹ R ² ) -X (wherein R ¹ ,
The metal complex ligand represented by R ² is an alkyl group and X is a substituted cyclopentadienyl group) is industrially extremely useful as a raw material for a Ziegler catalyst.

Front page continuation (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2, Nakanosu, Showa Denko K.K.

Claims (4)

[Claims] 1. A substituted cyclopentadienyl anion,
A compound represented by the general formula t-BuNH-Si (R ¹ R ² ) (OR ³ ) (wherein R ¹ , R ² and R ³ are alkyl groups) is reacted to give a compound represented by the general formula t- BuNH-Si (R ¹ R ² ) -X (where
R ¹ and R ² are alkyl groups, and X is a substituted cyclopentadienyl group). 2. The method for producing a metal complex ligand according to claim 1, wherein the substituted cyclopentadienyl anion is a tetramethylcyclopentadienyl anion. 3. The aminoalkoxysilane compound is t-BuNH.
It is -Si (Me) ₂ (OMe), The manufacturing method of the metal complex ligand of Claim 1 or 2 characterized by the above-mentioned. 4. The metal complex ligand is t-BuNH-Si (Me) _2- (Cp *).
(Wherein Cp * is a tetramethylcyclopentadienyl group), The method for producing a metal complex ligand according to any one of claims 1 to 3, wherein