JPH07628B2 - Method for producing organic bisgermylethanes - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing an organic germanium compound. Organic germanium compounds are used as additives to catalysts and polymers, and also attract attention as fungicides, preservatives, antitumor agents, and the like. It is also in the spotlight as a monomer for producing a germanium-containing polymer useful as an electronic / optical functional material.

[0002]

2. Description of the Related Art For bis (germyl) ethanes,
It was produced by a method using dangerous or expensive reagents such as a reaction between acetylenes and hydrogermanes, a method for obtaining bis (germyl) mercury, and the like. On the other hand, there are also a method of reacting a mixture of tetrahalogermane and dihalogermylene with an olefin, and a method of reacting a trihalogermane with an olefin in an ether, but these methods have three halogens substituted on a germyl group. It is applicable only to the production of 1,2-bis (germyl) ethanes. Therefore, it was not possible to produce a halogen- or alkoxy group on a germyl group useful as a monomer for producing a germanium-containing polymer and an organic group such as an alkyl group or an aryl group having both substituents. .

[0003]

An object of the present invention is to provide a method for producing 1,2-bis (germyl) ethanes having various substituents in a single step without using acetylene, alkali metal, mercury or the like. To provide.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that various olefins easily react with digermanes in the presence of a nickel group transition metal-containing catalyst. The present invention has been completed based on this finding.

That is, according to the present invention, the general formula R ¹ CH═CHR ² (I) (wherein R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an acyloxy group, Olefins represented by the general formula A ¹ A ² A ³ GeGeA ⁴ A ⁵ A ⁶ (II, which may be the same or different from each other and may be bonded to each other to form a ring). (Wherein A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, acyloxy groups, N, N-dialkylamino groups, A digermane represented by fluorine, chlorine, or bromine, which may be the same or different from each other) in the presence of a nickel group transition metal-containing catalyst. ^{1 A 2 A 3 Ge (R} 1 ^{CH-CH (R 2) GeA} 4 A 5 A 6 (III) (R 1, R 2, A 1, A 2, A 3, A 4, A 5 and A ⁶
Has the same meaning as in formula (I) and formula (II). The method for producing 1,2-bis (germyl) ethane represented by the formula (1) is provided.

As the olefins represented by the general formula (I) used in the present invention, various ones having hydrogen, an alkyl group, a cycloalkyl group, an alkoxy group or an acyloxy group as a substituent are used. For example, ethylene, propylene, cis-2-butene, cyclopentene, norbornene, methyl vinyl ether,
Vinyl acetate etc. can be mentioned.

The digermanes represented by the general formula (II), which is another raw material used in the present invention, have as their substituents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyloxy group, N. , N-dialkylamino group, various ones having fluorine, chlorine or bromine as a substituent are used. Examples of these digermanes include hexamethyldigermane, hexaethyldigermane, phenylpentamethyldigermane, 1,2-dimethoxy-1,1,2,2-tetramethyldigermane,
1,2-bis (dimethylamino) -1,1,2,2-tetramethyldigermane, 1,2-dichloro-1,1,
2,2-tetramethyldigermane, 1,2-difluoro-1,1,2,2-tetraphenyldigermane, hexafluorodigermane and the like can be mentioned.

The ratio of the olefins to the digermane compound in the present invention is not particularly limited, but considering the yield and the like, it is preferably in the range of 100 times to 1/10. When using a gaseous olefin,
It can be used at a pressure above or below normal pressure.

In the present invention, a nickel group transition metal-containing catalyst is used as the catalyst. As the nickel group transition metal-containing catalyst, various conventionally known ones containing palladium, platinum or nickel can be used, and a catalyst supported on activated carbon, a salt, a complex having a ligand, or the like can be used. . Specific examples thereof include palladium carbon, palladium acetate, palladium chloride, dichlorobis (triphenylphosphine) palladium, dichlorobis (triethylphosphine) palladium, dichlorobis (trimethylphosphine) palladium, dichlorobis (trimethoxyphosphine) palladium, tetrakis ( Triphenylphosphine) palladium, tetrakis (triethylphosphine) palladium, tris (triphenylphosphite) palladium, dichlorobis (benzonitrile) palladium, bis (dibenzylideneacetone) palladium, platinum carbon, platinum black, chloroplatinic acid and its salts, Platinum chloride, Zeise salt, tetrakis (triphenylphosphine) platinum, tetrakis (dimethylphenylphosphine) platinum, tetrakis (toluene) Phenyl phosphite) platinum, dichlorobis (triphenylphosphine)
Platinum, ethylene bis (triphenylphosphine) platinum,
Chlorohydridobis (triethylphosphine) platinum, dichloro (tetramethylethylenediamine) platinum, dibromobis (trimethylphosphite) platinum, dichlorobis (benzonitrile) platinum, bis (cyclooctadiene)
Platinum, dichloro (cyclooctadiene) platinum, bis (dibenzylideneacetone) platinum, tetrakis (triphenylphosphine) nickel, tetrakis (triethylphosphine) nickel, ethylenebis (triphenylphosphite) nickel, bis (cyclooctadiene) nickel Etc. These salts and complexes can be used alone, but phosphines such as triphenylphosphine, methyldiphenylphosphine, triethylphosphine, trimethylphosphine, etc., which are about 1 to 10 times the metal atom, trimethylphosphite, triphenyl. It may be used together with a ligand such as phosphite or phosphite such as 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane. The amount of these nickel group transition metal-containing catalysts used may be a so-called catalytic amount, and generally, in a molar ratio to digermanes,
It is used in the range of 0.00001-0.5.

The reaction of the present invention is carried out at a reaction temperature of 0 ° C or higher, preferably room temperature to 250 ° C. Further, the reaction of the present invention can be carried out in the presence or absence of a solvent. When a solvent is used, a commonly used solvent, for example, various organic solvents such as benzene, toluene and hexane are used. be able to. Separation and purification of the desired product from the reaction mixture can be generally easily achieved by means commonly used in organic chemistry such as distillation and chromatography.

The present invention provides 1,2-bis (germyl) ethanes represented by the general formula (III). As an example of these 1,2-bis (germyl) ethanes,
1,2-bis (chlorodimethylgermyl) ethane, 1,
2-bis (trimethylgermyl) propane, 2,3-bis (triethylgermyl) butane, 1,2-bis (chloromethylphenylgermyl) ethane, 1,2-bis (trimethylgermyl) cyclopentane, 2 , 3-Bis (chlorodimethylgermyl) norbornane, 1,2-bis (trimethylgermyl) -1-methoxyethane, 1,2
-Bis (trimethylgermyl) -1-acetoxyethane and the like.

[0012]

INDUSTRIAL APPLICABILITY According to the present invention, various 1,2-bis (germyl) ethanes can be produced from readily available olefins under neutral conditions, and their separation and purification are easy. The bis (germyl) compound represented by the general formula (III) obtained by the present invention is suitable as a raw material for producing a germanium-containing polymer.

[0013]

EXAMPLES Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Example 1 1,2-dichloro-1,1,2,2-in an autoclave
Tetramethyldigermane 1 mmol, tetrakis (triphenylphosphine) palladium 0.05 mmol, toluene 2
Then, 50 ml of ethylene was introduced under pressure, and the mixture was heated and stirred in a 120 ° C. oil bath for 162 hours. After autoclave cooling,
As a result of gas chromatography analysis, 0.32 mmol of 1,2-bis (chlorodimethylgermyl) ethane was obtained.

Example 2 As a result of carrying out the reaction in the same manner as in Example 1 except that 0.05 mmol of dichlorobis (trimethylphosphine) palladium was used in place of tetrakis (triphenylphosphine) palladium and the reaction time was 45 hours, 0.77 mmol of 1,2-bis (chlorodimethylgermyl) ethane was obtained.

Example 3 Instead of dichlorobis (trimethylphosphine) palladium, bis (dibenzylideneacetone) palladium.
05 mmol and 1-phospha-2,6,7-trioxa-
4-Ethylbicyclo [2,2,2] octane 0.10mm
The reaction was performed in the same manner as in Example 2 except that ol was added, and as a result, 1.00 mmol of 1,2-bis (chlorodimethylgermyl) ethane was obtained.

Example 4 In place of dichlorobis (trimethylphosphine) palladium, tetrakis (triphenylphosphine) platinum.
The reaction was performed in the same manner as in Example 2 except that 05 mmol was used and the reaction temperature was 150 ° C., to obtain 0.02 mmol of 1,2-bis (chlorodimethylgermyl) ethane.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07B 61/00 300

Claims (1)

[Claims] 1. A general formula R ¹ CH═CHR ² (I) (wherein R ¹ and R ² represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or an acyloxy group, and even if they are the same as each other. Olefins represented by the general formula A ¹ A ² A ³ GeGeA ⁴ A ⁵ A ⁶ (II) (in the formula, A may be different from each other and may be bonded to each other to form a ring). ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyloxy group, an N, N-dialkylamino group, fluorine, chlorine or bromine. Of the general formula A ¹ A ² A ³ Ge, characterized in that they are reacted with each other in the presence of a nickel group transition metal-containing catalyst. ^{(R 1) CH-CH (} R 2) G ^{A 4 A 5 A 6 (III} ) (R 1, R 2, A 1, A 2, A 3, A 4, A 5 and A ⁶
Has the same meaning as in formula (I) and formula (II). ) The method for producing 1,2-bis (germyl) ethane represented by