JPH0641474B2 - Method for producing disilanes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to dehydrogenative condensation of monohydrosilanes in the presence of a specific catalyst containing platinum and a 2 or 4 electron donating ligand as a constituent component. The present invention relates to a characteristic method for producing disilanes.

[Prior Art] Disilanes are useful as photoresist materials having resistance to oxygen plasma etching.

Conventionally, disilanes, except by-products in the production of halosilane, or those having a structure obtained as a derivative thereof, are subjected to polycondensation of halosilanes in the presence of alkali metals such as lithium and sodium, or with halosilanes. A general method is to manufacture by reacting an alkali metal silicide such as silyllithium. However, this method is dangerous because it uses an alkali metal, and disilanes having a substituent capable of reacting with the alkali metal cannot be produced in principle.

On the other hand, hydrosilanes are subjected to dehydrogenative condensation using a transition metal catalyst, and the method for producing disilanes is attracting attention because it does not require the use of a dangerous alkali metal as compared with the method using halosilanes described above. , Already using a rhodium catalyst (J. Organomet. Che.
m. , 55 , C7 (1974), Organometa.
Llics, 2 , 740 (1983), Organom
et al., 6 , 1595 (1987)), a method using a titanium catalyst (J. Organomet. Che.
m. , 279 , C11 (1985)) and a method using a platinum catalyst (Organometallics, 6 , 1).
590 (1987)) is known.

[Problems to be Solved by the Invention and Object of the Invention] However, any of these methods using dehydrogenative condensation is a method using dihydrosilane or trihydrosilane as a starting material.
It was necessary to use silane having at least one hydrogen atom as a raw material. In the case of silane having one hydrogen atom on one silicon atom, that is, monohydrosilane, dehydrogenative condensation cannot be carried out by the above-mentioned conventional technique, and a small amount of disilane is produced (Organome).
tallics, 2 , 740 (1983), Organ.
Ometallics, 6 , 1590 (1987)) did not exceed the amount of noble metal used as a catalyst, and could not be said to be an economically excellent method. (J. Organome
t. Chem. , 55 , C7 (1974)), it is argued that this fact requires the existence of two or more hydrogen atoms on one silicon atom in order for the dehydrogenative condensation to proceed. .

The present invention intends to solve the above problems associated with the dehydrogenative condensation of monohydrosilanes and to provide a novel method for producing disilanes.

[Means for Solving the Problems] The present invention comprises monohydrosilanes (1) platinum and at least one equivalent or more of organic nitrogen and organic phosphorus having at least one alkyl group as an organic group. In the presence of a complex catalyst containing 2 or 4 electron-donating ligands selected from the group, or (2) platinum metal or a compound thereof, and at least 1 equivalent or more of organic nitrogen with respect to platinum and an alkyl group as an organic group In the presence of a catalytic amount of both 2 or 4 electron-donating ligands selected from the group consisting of organic phosphorus having at least one of, or (3) the complex catalyst and at least one alkyl group as organic nitrogen and an organic group. 2 or 4 selected from the group consisting of organic phosphorus
A method for producing disilanes, which comprises reacting at 50 ° C. or higher in the presence of both electron donating ligands.

Substituents other than hydrogen on the silicon of the monohydrosilane used in the method of the present invention are halogen, alkyl group, cycloalkyl group, aryl group, heterocyclic group, aralkyl group, alkoxy group, aryloxy group, secondary amino group. , An acyloxy group, etc., and these groups are substituted with an inert substituent excluding a substituent that undergoes hydrosilylation such as an alkenyl group, an alkynyl group, a formyl group, and an acyl group, and a substituent having an active hydrogen. Good. Examples of these groups include chlorine, methyl group, ethyl group, isopropyl group, t-butyl group, cyclohexyl group, phenyl group, p
-Methoxyphenyl group, o-tolyl group, m-chlorophenyl group, α- or β-naphthyl group, benzyl group, ethoxy group, dimethylamino group, phenoxy group, 2-cyanoethyl group, piperidino group, acetoxy group and the like. .

The catalyst used in the present invention is an organic phosphorus ligand having at least one alkyl group as an organic nitrogen or an organic group in which nitrogen or phosphorus acts as a 2 or 4 electron donating ligand, at least with respect to platinum. It is a platinum complex contained in one equivalent molecule. However, even if these ligands are not complexed with platinum in advance, the platinum component and the ligand component are added to the reaction system so that the ligand component is at least 1 equivalent to platinum. The coexistence method can effectively act as a catalyst.

The form of the platinum component used in this reaction at the time of addition is not particularly limited, and various types of organic or inorganic salts or complexes may be charged. Further, the 2 or 4 electron donating ligand composed of an organic nitrogen or an organic phosphorus having an alkyl group, which is suitable for the reaction of the present invention, includes a tertiary amine, a phosphine and a phosphite, and a particularly preferable compound. As the ligand, pyridine, 2,2'-bipyridyl, tetramethylethylenediamine, triethylamine, trimethylphosphine, dimethylphenylphosphine, methyldiphenylphosphine, 1,4-bis (diphenylphosphino)
Examples include butane, trimethylphosphite, tributylphosphine, and the like. Therefore, as the complex catalyst suitable for the reaction of the present invention, dichlorobis (trimethylphosphine) platinum, dichlorobis (triethylphosphine) platinum, tetrakis (dimethylphenylphosphine) platinum,
Diethylbis (trimethylphosphine) platinum, ethylenebis (trimethylphosphine) platinum, chlorohydridobis (triethylphosphine) platinum, dichlorobis (pyridine) platinum, dichloro (tetramethylethylenediamine) platinum, dichloro [1,4-bis (diphenylphosphino)] Butane] platinum, dichloro (2,2′-bipyridyl) platinum, dibromobis (trimethylphosphite) platinum, di-μ-chlorodichlorobis (trimethylphosphine) diplatinum, dichloro (methylisonitrile) (triethylphosphine) platinum, etc. It is illustrated.

In addition, these complex catalysts may be used together with the 2- or 4-electron donating ligand composed of the organic nitrogen or organic phosphorus. On the other hand, as the platinum component used in the coexistence with the tertiary amines, phosphines, and phosphites,
Examples include platinum black, platinum chloride, dichlorobis (benzonitrile) platinum, dichloro (cyclooctadiene) platinum, di-μ-chlorobis (π-allyl) diplatinum, and bis (dibenzylideneacetone) platinum. The amount of these catalysts used may be a so-called catalytic amount, and is generally selected in the range of 0.5 to 0.00001 in terms of molar ratio to the organosilicon compound.

The present invention is carried out at a reaction temperature of 50 ° C or higher, preferably 50 ° C to 30 ° C.

Although the present invention can be carried out without a solvent, when a solvent is used, a solvent that is usually used, that is, benzene, except for those that undergo hydrosilylation such as ketones and those that contain active hydrogen such as alcohols, It is selected from among toluene, xylene, hexane, ether and the like.

In addition, the separation and purification of the product from the reaction mixture can be generally easily achieved by means commonly used in organic chemistry such as distillation and chromatography.

[Effect of the Invention] By the method of the present invention, disilanes can be industrially advantageously obtained by catalytically dehydrocondensing a wide range of monohydrosilanes.

[Examples] Aspects of the present invention will be described in more detail based on examples.

Example 1 A glass tube was charged with 3.26 mmol of dimethylphenylsilane, 0.02 mmol of diethylbis (trimethylphosphine) platinum, and 0.16 mmol of trimethylphosphine, and the mixture was sealed and stirred in an oil bath at 150 ° C. for 12 hours. As a result of analysis by GC, the conversion rate of dimethylphenylsilane was 2
3.5%, the yield of 1,1,2,2-tetramethyl-1,2-diphenyldisilane is 10.2% based on the charged raw materials.
Met.

Examples 2 to 13 and Comparative Examples 1 to 5 The reaction of Example 1 was carried out at various temperatures and times by changing the platinum component or the ligand, and the results shown in Table 1 were obtained.

Example 14 Methyldiphenylsilane was used as the silane, dichlorobis (dimethylphenylphosphine) platinum was used as the catalyst, and the reaction of Example 1 was carried out without adding a ligand.
1,2-Dimethyl-1,1,2,2-tetraphenyldisilane was obtained with a yield of 7%.

Claims (4)

[Claims] 1. A 2- or 4-electron donating coordination selected from the group consisting of platinum and at least 1 equivalent or more of organic nitrogen and organophosphorus having at least one alkyl group as an organic group. A method for producing disilanes, which comprises reacting at 50 ° C. or higher in the presence of a complex catalyst containing a child. 2. A monohydrosilane selected from the group consisting of platinum or a compound thereof and 2 or 4 selected from the group consisting of at least one equivalent of organic nitrogen with respect to platinum and an organic phosphorus having at least one alkyl group as an organic group. A method for producing disilanes, which comprises reacting both electron donating ligands in a catalytic amount at 50 ° C. or higher. 3. A 2- or 4-electron donating coordination selected from the group consisting of platinum and at least one equivalent or more of organic nitrogen and organophosphorus having at least one alkyl group as an organic group. 2 or 4 selected from the group consisting of a catalyst containing a child and organic nitrogen and organic phosphorus having at least one alkyl group as an organic group.
A method for producing disilanes, which comprises reacting at 50 ° C. or higher in the presence of an electron donating ligand. 4. The substituents other than hydrogen on monohydrosilanes other than hydrogen are an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
Item or the method according to Item 3.