JPH07165769A - Organic germanium compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound represented by a specific formula, having halogen, atoms, etc., on both germanium atoms, and useful for producing germanium-containing polymers useful as electronic.optical function materials. CONSTITUTION:A compound of formula I [Ar<1> is arylene; B<1>-B<3> each is a (cyclo) alkyl, an aryl, an aralkyl, a halogen], e.g. p-bis (chlorodimethylgermyl)benzene. This compound is obtained by reacting an organic halide compound of the formula: X-R<1>-X [R<1> is a (substituted)alkylene, a cycloalkylene, an alkenylene, arylene, a divalent aliphatic heterocyclic ring, a divalent aromatic heterocyclic ring, an aralkylene; X is a halogen] with a digermane compound of formula II [Z is Cl, Br, an alkoxy; A<1>, A<2> are each a (cyclo)alkyl, an aryl, an aralkyl, fluoro; (m), (n) are each 1, 2] in the presence of a palladium-containing catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing an organic germanium compound and a novel organic germanium compound. Organic germanium compounds are used as additives to catalysts and polymers, and also attract attention as bactericides, antiseptics, antitumor agents, and the like. Also,
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 Organic germanium compounds have hitherto been produced by reacting a halogermane with a carbanion reagent such as a Grignard reagent or an organolithium reagent, or by reacting a germyl anion with an organic halide. However, since these methods use highly reactive anion reagents, they are difficult to use industrially. In addition, halogermanes generate a germyl anion by a metal exchange reaction with a Grignard reagent or the like, so that side reactions also occur. Furthermore, these methods were not suitable for the production of compounds having a halogen-germanium bond, since the bond reacts with the reaction reagent under the reaction conditions.

Another method for producing an organic germanium reagent is a hydrogermylation reaction between hydrogermanes and acetylenes or olefins. A compound having a halogen-germanium bond can be produced by this method, but this method cannot be applied in principle when the organic group newly introduced on germanium is not derived from acetylenes or olefins.

[0004]

In order to overcome these problems of the prior art, it is necessary to provide a new method for binding an organic group and germanium without using an anion reagent. , A novel organogermanium compound is provided.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an alkyl, alkenyl, aryl or aralkyl halide is
The present inventors have found the novel fact that they easily react with polyhalo or polyalkoxy digermanes in the presence of a palladium-containing catalyst, and have completed the present invention based on this finding.

That is, the method for producing the compound according to the present invention is as follows. Formula ^{X-R 1 -X (V)} ( wherein R ¹ is an alkylene group which may have a substituent,
Cycloalkylene group, alkenylene group, arylene group,
A divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or
It is an aralkylene group, and X represents a halogen atom. )
An organohalogen compound represented by the formula: Z _m A ¹ _n A ² _3-mn GeGeA ¹ _n A ² _3-mn Z _m (II) in the presence of a palladium-containing catalyst (wherein Z is chlorine, bromine or alkoxy) Group, A ¹ and A ² represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or fluorine, and m and n are 1 or 2). General formula Z _m A ¹ _n A ² _3-mn GeR ¹ GeA ¹ _n A ² _3-mn Z _m (VI) (wherein R ¹ is the same as formula (V), Z, A ¹ , A ² , m and n
Is the same as formula (II). ) And / or the general formula X _m A ¹ _n A ² _3-mn GeR ¹ GeA ¹ _n A ² _3-mn Z _m (VII) (wherein R ¹ and X are of the formula (V)) And Z, A ¹ , A ² , m
And n are the same as in formula (II). ) And / or the general formula X _m A ¹ _n A ² _3-mn GeR ¹ GeA ¹ nA ² _3-mn X _m (VIII) (wherein R ¹ and X are the same as the formula (V)) , A ¹ , A ² , m and n are the same as those in the formula (II).). The compounds according to the present invention obtained by this method are as follows. (1) General formula B ¹ B ² B ³ GeCH ₂ Ar ¹ CH ₂ GeB ¹ B ² B ³ (XI) (In the formula, Ar ¹ is an arylene group, and B ¹ , B ² and B ³ may be the same or different. Represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom), and (2) the general formula B ¹ B ² B ³ GeAhGeB ¹ B ² B ³ (XII) ( In the formula, Ah is a divalent aromatic heterocyclic group, B ¹ , B ² and B
³ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different from each other. ) An organic germanium compound represented by.

The organic halogen compound represented by the general formula X-R ¹ -X (V) used in the above-mentioned synthesis of the compound according to the present invention has two organic groups R ^{1 which} are alkylene groups, cycloalkylene groups and alkenylene. A group, an arylene group, a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or an aralkylene group is used. To give an example, 1,3-dibromopropane, 1,4-dibromocyclohexane, 1,2-dichloroethylene, 1,2-dibromoethylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 2, 5-
Dibromothiophene, benzal chloride, benzal bromide,
Examples include α, α′-dichloro-p-xylene.

The digermanes represented by the general formula Z _m A ¹ _n A ² _3-mn GeGeA ¹ _n A ² _3-mn Z _m (II), which is another raw material used in the above synthesis of the compound according to the present invention, As the substituent Z, various ones having chlorine, bromine or alkoxy group, and A ¹ and A ² having an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or fluorine are used. , 2-Dichloro-1,1,2,2-tetramethyldigermane, 1,2-dichloro-1,1,2,2-
Tetraethyldigermane, 1,1,2,2-tetrachloro-1,2-diphenyldigermane, 1,2-dimethoxy-1,1,2,2-tetramethyldigermane, 1,2
-Dibromo-1,2-dimethyl-1,2-dicyclohexyl digermane and the like can be mentioned.

The ratio of the organic halide used in the above-mentioned synthesis of the compound according to the present invention to the digermane compound is not particularly limited, but in view of yield and the like, it is in the range of 100 times to 1/10. preferable.

In the above synthesis of the compound according to the present invention, a palladium-containing catalyst is used as a catalyst. As the palladium-containing catalyst, various conventionally known ones 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 (trimethylphosphite) palladium, tetrakis (triphenyl). Phenylphosphine) palladium, tetrakis (triethylphosphine) palladium,
Examples thereof include tris (triphenylphosphite) palladium, dichlorobis (benzonitrile) palladium, bis (dibenzylideneacetone) palladium and the like. These supported catalysts, salts, complexes and the like can be used alone, but phosphines such as triphenylphosphine, methyldiphenylphosphine, trimethylphosphine, triethylphosphine and the like, which are about 1 to 10 times the palladium atom, trimethyl Coexisting with phosphite, triphenylphosphite, phosphite such as 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane, or ligand such as isonitrile You may use.

The amount of the palladium-containing catalyst used may be a so-called catalytic amount, and is generally used in the range of 0.00001 to 0.5 in terms of molar ratio with respect to the digermanes.
The above synthetic reaction is carried out at 0 ° C. or higher, preferably at room temperature to 250.
It is carried out at a reaction temperature of ° C. Further, this reaction can be carried out in the presence or absence of a solvent, and when a solvent is used, a commonly used solvent, for example, various organic solvents such as benzene, toluene, hexane and the like can be used. it can. 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 general formula Z _m A ¹ _n A ² _3-mn GeR ¹ GeA ¹ _n A ² _3-mn Z _m (VI) X _m A ¹ _n A ² _3-mn GeR ¹ GeA obtained by the above synthetic reaction ¹ _n A ² _3-mn Z _m (VII) X _m A ¹ _n A ² _3-mn GeR ¹ GeA ¹ _n A ² _3-mn X _m (VII
As the organic germanium compound represented by I), as the substituent R ¹ , an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, a divalent aliphatic heterocyclic group, 2
A valent aromatic heterocyclic group or an aralkylene group with a substituent A
¹ and A ² may be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or fluorine, a substituent Z may be chlorine, bromine or an alkoxy group, and a substituent X may be a halogen atom. . Examples of these organic germanium compounds are 1,3-bis (chlorodimethylgermyl) bropan, 1,4-bis (chlorodimethylgermyl) cyclohexane, 1,2-
Bis (chlorodimethylgermyl) ethylene, 1,2-bis (bromodimethylgermyl) ethylene, 1,4-bis (chlorodimethylgermyl) benzene, 1,4-bis (bromodimethylgermyl) benzene, 1- Bromodimethylgermyl-2-chlorodimethylgermylbenzene,
1-iododimethylgermyl-2-chlorodimethylgermylbenzene, 2,5-bis (chlorodimethylgermyl) thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, 2,5-bis (bromo Examples include dimethylgermyl) thiophene, α, α-bis (chlorodimethylgermyl) toluene, α, α'-bis (chlorodimethylgermyl) -p-xylene.

The present invention has the general formula B ¹ B ² B ³ GeCH ₂ Ar ¹ CH ₂ GeB ¹ B ² B ³ (XI) (wherein Ar ¹ is an arylene group and B ¹ , B ² and B ³ are the same as each other). A novel organic germanium compound represented by an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a halogen atom, which may be different, is provided. Examples of these compounds include α, α′-bis (chlorodimethylgermyl) -p-xylene, α,
α'-bis (trimethylgermyl) -p-xylene,
α, α'-bis (chlorodimethylgermyl) -2,6-
Examples thereof include dimethylnaphthalene, α, α-bis (chloromethylphenylgermyl) -p-xylene and the like.

The present invention has the general formula B ¹ B ² B ³ GeAhGeB ¹ B ² B ³ (XII) (wherein Ah is a divalent aromatic heterocyclic group, B ¹ , B ² and B).
³ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different from each other, and provides a novel organic germanium compound. Examples of these compounds are 2,5-
Bis (chlorodimethylgermyl) thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, 2,5-bis (bromodimethylgermyl) thiophene, 2,5-bis (trimethylgermyl) thiophene, 2 , 5-bis (chlorodimethylgermyl) furan,
2,5-bis (triethylgermyl) pyridine and the like can be mentioned.

[0015]

The compound of the present invention is a completely novel digermane compound having a halogen atom or the like on both germanium atoms. This digermane compound has an excellent effect that it is used as a monomer for producing a germanium-containing polymer useful as an electronic / optical functional material by polymerizing, for example, halogen atoms at both ends as reaction sites.

[0016]

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. Reference Example 1 1,2-dichloro-1,1,2,2-in an autoclave
Tetramethyldigermane 1 mmol, tetrakis (triphenylphosphine) palladium 0.05 mmol, trans-
1,2-Dichloroethylene (0.5 mmol) and toluene (2 ml) were added, and the mixture was heated and stirred in an oil solution at 180 ° C. for 15 hours. After cooling in an autoclave, gas chromatographic analysis revealed that trans -1,
2-bis (chlorodimethylgermyl) ethylene 0.30
mmol produced.

Example 1 As a result of carrying out the reaction in the same manner as in Reference Example 1 except that p-dibromobenzene was used instead of trans-1,2-dichloroethylene and the reaction was carried out at 150 ° C. for 20 hours, p-bis ( 0.06 mmol of chlorodimethylgermyl) benzene was obtained.

Example 2 Instead of trans-1,2-dichloroethylene, α, α '
-Dichloro-p-xylene 0.50 mmol, 2 ml of benzene instead of toluene, and the reaction was carried out in the same manner as in Reference Example 1 except that the reaction was carried out at 120 ° C for 10 hours.
0.30 mmol of α, α′-bis (chlorodimethylgermyl) -p-xylene was obtained. 0.24 mmol was isolated by subjecting the reaction solution to Kugelrohr distillation. This is a new compound not listed in the literature, and its spectroscopic data is as follows.

Α, α'-bis (chlorodimethylgermyl) -p-xylene: bp 125 ° C / 6mmHg (Kugellohr)
mp 80-82 ° C; ¹ HNMR (CDCl ₃ ) δ 0.61 (s, 12H, GeCH ₃ ), 2.
63 (s, 4H, ArCH ₂ Ge), 6.99 (s, 4H, C ₆ H ₄ ); MS (EI) m / s
(Relative intensity) 380 (M ⁺ , 12), 243 (M ⁺ -GeMe ₂ Cl, 54), 13
9 (GeMe ₂ Cl, 100); Elemental analysis Found: C, 37.22; H, 5.0
4, calculated as C ₁₂ H ₂₀ Cl ₂ Ge ₂ : C, 37.89, H, 5.29
.

Example 3 2,5-instead of trans-1,2-dichloroethylene
Using 1.00 mmol of dibromothiophene, the amount of 1,2-dichloro-1,1,2,2-tetramethyldigermane was 4.00 mmol, and 2 ml of benzene was used instead of toluene, and the reaction was carried out at 150 ° C. for 12 hours. Other than that, Reference Example 1
As a result of the same reaction as described above, 2,5-bis (chlorodimethylgermyl) thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, 2,5
A mixture of -bis (bromodimethylgermyl) thiophene was obtained. The reaction solution was treated with methyllithium and then subjected to Kugelrohr distillation to obtain 0.56 mmol of 2,5-bis (trimethylgermyl) thiophene. Each product is a new compound not listed in the literature, and its spectroscopic data etc. are as follows.

2,5-bis (chlorodimethylgermyl)
Thiophene; MS (E / I) m / s (relative intensity) 358 (M ⁺ , 21), 34
^{3 (M + -Me, 100)} , 139 (GeMe 2 Cl, 39). 2,5-bis (trimethylgermyl) thiophene: bp 100 ° C / 6mmHg (Kugellohr); ¹ HNMR (acetone-d ₆ ) δ0.33 (s, 18H, GeC
H ₃ ), 7.17 (s, 2H, = CHCH =): MS (EI) m / z (relative intensity) 31
8 (M ⁺ , 9), 303 (M ⁺ -Me, 100), 119 (Me ₃ Ge, 17); High resolution
MS 319.9666, calculated for _{C 10 H 20 Ge 2 S;} 319.9705.

Example 4 The reaction was performed in the same manner as in Example 3 except that 1 mmol of 1,4-diiodobenzene was used instead of 2,5-dibromothiophene, the reaction temperature was 120 ° C., and the reaction time was 10 hours. , Methylated. By Kugelrohr distillation, 1,4-
0.51 mmol of bis (trimethylgermyl) benzene was obtained.

Claims (2)

[Claims] 1. The general formula B ¹ B ² B ³ GeCH ₂ Ar ¹ CH ₂ GeB ¹ B ² B ³ (XI) (wherein Ar ¹ is an arylene group and B ¹ , B ² and B ³ are the same or different from each other. Which represents an optionally substituted alkyl group, cycloalkyl group, aryl group, aralkyl group, or halogen atom). 2. A compound represented by the general formula B ¹ B ² B ³ GeAhGeB ¹ B ² B ³ (XII) (wherein Ah is a divalent aromatic heterocyclic group, B ¹ , B ² and B).
³ represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a halogen atom, which may be the same or different from each other. ) An organic germanium compound represented by.