JPH04364191A - Production of organogermanium compound and new organogermanium compound - Google Patents

Abstract

PURPOSE:To readily obtain various compounds useful as raw materials for Ge-containing polymers without using an anionic reagent by reacting an organic halogen compound with a specific digermane in the presence of a Pd-containing catalyst. CONSTITUTION:An organic halogen compound shown by the formula RX (R is alkyl, aryl, etc.; X is halogen) is made to react with a digermane (e.g. 1,2- dichloro-1,2,2-tatramethyldigermane) shown by formula I (Z is Cl, Br, etc.; A<1> and A<2> are alkyl, F, etc.; (m) and (n) are 1 or 2) to give the objective compound shown by formula II and/or formula III. The reaction is carried out preferably at room temperature to 250 deg.C. Chlorodimethyl-beta-styrylgermane, etc., among the objective compounds shown by formula II are new compounds.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 catalysts and additives to polymers, and are also attracting attention as bactericidal agents, preservatives, antitumor agents, and the like. It is also in the spotlight as a monomer for producing germanium-containing polymers useful as electronic and optical functional materials.

0002

BACKGROUND OF THE INVENTION Conventionally, organic germanium compounds have been produced by reacting halogermanes with carbanion reagents such as Grignard reagents and organolithium reagents, or by reacting germyl anions with organic halides. However, since these methods use highly reactive anionic reagents, their industrial use is difficult. In addition, halogermanes generate germyl anions through metal exchange reactions with Grignard reagents, etc., and therefore cause side reactions. Furthermore, these methods were not suitable for producing compounds having a halogen-germanium bond because the bond reacts with a reaction reagent under the reaction conditions.

Another method for producing organic germanium reagents is a hydrogelmylation reaction between hydrogermanes and acetylenes or olefins. Although it is possible to produce a compound having a halogen-germanium bond using this method, this method cannot be applied in principle if the organic group newly introduced onto the germanium is not derived from acetylenes or olefins.

0004

[Problems to be Solved by the Invention] In order to overcome these problems of the prior art, it is necessary to provide a new method for bonding an organic group and germanium without using an anionic reagent. , novel organogermanium compounds are provided.

[0005]

[Means for Solving the Problems] As a result of extensive research in order to solve the above problems, the present inventors have found that alkyl, alkenyl, aryl or aralkyl halides are
We have discovered the novel fact that polyhalo or polyalkoxydigermanes easily react in the presence of a palladium-containing catalyst, and have completed the present invention based on this knowledge.

That is, according to the present invention, (1) general formula RX
(I) (wherein R is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, or an aralkyl group which may have a substituent, and represents a halogen atom. ) in the presence of a palladium-containing catalyst, an organic halogen compound represented by
-nZm (II) (wherein Z represents chlorine or bromine or an alkoxy group, A1 and A2 represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or fluorine, m and n are 1 or 2) ) characterized by reacting with a digermane represented by
General formula RGeA1nA23-m-nZm (III)
(wherein, R is the same as in formula (I), and Z, A1, A2, m and n are the same as in formula (II).) and/or the general formula RGeA1nA23-m-nXm (IV) ( In the formula, R
and X is the formula (I), A1, A2, m and n are the formula (
Same as II). ), (2) General formula X-R1-X
(V) (In the formula, R1 is an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or an aralkylene group which may have a substituent). group, and X represents a halogen atom) in the presence of a palladium-containing catalyst.
-nZm (II) (wherein Z represents chlorine, bromine or an alkoxy group, A1 and A2 represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or fluorine, m
and n is 1 or 2. ) with the general formula Zm A1nA23-m-nGeR1 GeA1n
A23-m-nZm (VI) (wherein, R1 is the same as the formula (V), and Z, A1, A2, m and n are the same as the formula (II)) and/or the general formula Xm A1nA23-m-nGeR1 GeA1n
A23-m-nZm (VII) (wherein,
R1 and X are the same as in formula (V), and Z, A1, A2, m and n are the same as in formula (II). ) and/or the general formula Xm A1nA23-m-nGeR1 GeA1n
A23-m-nXm (VIII) (wherein, R1 and X are the same as formula (V), and A1, A2, m and n are the same as formula (II)), (3 ) General formula ArMe2 GeX1
(IX) (In the formula, Ar represents an aryl group, Me represents a methyl group, and X1 represents bromine or iodine.) An organic germanium compound represented by the general formula ArCH=CHGeB1 B2 B3 (
X) (wherein Ar represents an aryl group, B1, B2
and B3 represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different. ), (5) General formula B1 B2 B3 GeCH2 Ar1 CH2
GeB1 B2 B3 (XI) (in the formula A
r1 represents an arylene group, and B1, B2 and B3 represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different. ), and (6) an organic germanium compound represented by the general formula B1 B2 B3 GeAhGeB1B2 B3
(XII) (In the formula, Ah represents a divalent aromatic heterocyclic group, and B1, B2, and B3 represent 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 is provided.

General formula RX used in the present invention
Examples of R in the organic halogen compound represented by (I) include those with various structures such as an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, or an aralkyl group. is used. Specific examples of this compound include methyl bromide, methyl iodide, ethyl bromide, 1-iodohexane, cyclohexyl bromide, vinyl bromide, β-bromostyrene, β-iodostyrene, α-bromostyrene, and bromobenzene. , o-iodotoluene, α-bromonaphthalene, 2-iodothiophene, 3-bromofuran, benzyl chloride, α-phenethyl bromide, and the like.

General formula X-R1-X used in the present invention

In the organic halogen compound represented by (V), the two organic groups R1 are an alkylene group, a cycloalkylene group,
Various alkenylene groups, arylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, and aralkylene groups are used. Examples include 1,3-dibromopropane, 1,4-dibromocyclohexane, 1
, 2-dichloroethylene, 1,2-dibromoethylene,
Examples include 1,4-dibromobenzene, 1,4-diiodobenzene, 2,5-dibromothiophene, benzal chloride, benzal bromide, α,α'-dichloro-p-xylene, and the like.

Another raw material used in the present invention, which has the general formula Zm A1nA23-m-nGeGeA1nA23
Digermanes represented by -m-nZm (II) include various ones having chlorine, bromine or an alkoxy group as the substituent Z, and an alkyl group, cycloalkyl group, aryl group, aralkyl group or fluorine as A1 and A2. However, to give an example, 1, 2
-dichloro-1,1,2,2-tetramethyldigermane, 1,2-dichloro-1,1,2,2-tetraethyldigermane, 1,1,2,2-tetrachloro-1,2-diphenyl Digermane, 1,2-dimethoxy-1,1,2
, 2-tetramethyl digermane, 1,2-dibromo-1
, 2-dimethyl-1,2-dicyclohexyldigermane, and the like.

[0010] There is no particular restriction on the ratio of the organic halide to the digermane compound used in the present invention, but
Considering the yield and the like, a range of about 100 times to 1/10 is preferable.

In the present invention, a palladium-containing catalyst is used as the catalyst. As the palladium-containing catalyst, various conventionally known catalysts can be used, and catalysts supported on activated carbon, salts, complexes having ligands, etc. can be used. Specific examples of these include palladium carbon, palladium acetate, palladium chloride, dichlorobis(
triphenylphosphine) palladium, dichlorobis(
triethylphosphine)palladium, dichlorobis(trimethylphosphine)palladium, dichlorobis(trimethylphosphine)palladium, tetrakis(triphenylphosphine)palladium, tetrakis(triethylphosphine)palladium, tris(triphenylphosphine)palladium, dichlorobis(benzonitrile)palladium , bis(dibenzylideneacetone)palladium, and the like. These supported catalysts, salts,
Complexes etc. can be used alone, but phosphines such as triphenylphosphine, methyldiphenylphosphine, trimethylphosphine, triethylphosphine, trimethylphosphite, triphenylphosphite, etc. can be used in an amount of about 1 to 10 times the palladium atom. , 1-phospha-2,6,7-trioxa-4-ethylbicyclo[
It may be used in coexistence with phosphites such as 2,2,2]octane, or ligands such as isonitriles.

The amount of these palladium-containing catalysts used may be a so-called catalytic amount, and is generally used in a molar ratio of 0.00001 to 0.5 with respect to the digermanes. The reaction of the present invention is carried out at 0°C or higher, preferably from room temperature to 250°C.
The reaction temperature is . Furthermore, the reaction of the present invention can be carried out in the presence or absence of a solvent, but when a solvent is used, commonly used solvents such as 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 generally be easily achieved by means commonly used in organic chemistry, such as distillation and chromatography.

General formula RGeA1nA23-m-nZm (III) obtained in the present invention
In the organogermanium compound represented by, the substituent R is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, or an aralkyl group, and the substituents A1 and A2 are Various compounds having an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a fluorine group and a chlorine, bromine or alkoxy group as the substituent Z can be obtained. Examples of these organic germanium compounds include chlorotrimethylgermane, chloroethyldimethylgermane, chlorodimethylhexylgermane, chlorocyclohexyldimethylgermane, bromodimethylvinylgermane, chlorodimethyl-1-propenylgermane, and chlorodimethyl-β.
-Styrylgermane, bromodimethyl-β-styrylgermane, iododimethyl-β-styrylgermane, bromodimethyl-α-styrylgermane, chlorodimethylphenylgermane, chlorodiethylphenylgermane, chlorodimethyltolylgermane, chlorodiethylanisylgermane, bromo Dimethylphenylgermane, iododimethylphenylgermane, iododimethyltolylgermane, chlorodimethyl-α-naphthylgermane, iododimethyl-2-thienylgermane, bromodimethyl-3-
Frill germane, chlorobenzyldimethylgermane, bromobenzyldimethylgermane, chlorodimethyl-α-
Examples include phenethylgermane.

General formula obtained by the present invention Zm A1nA23-m-nGeR1 GeA1n
A23-m-nZm (VI) Xm A1nA23
-m-nGeR1 GeA1nA23-m-nZm (
VII) Xm A1nA23-m-nGeR1 G
eA1nA23-m-nXm (VIII) As the substituent R1, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, etc. A cyclic group or an aralkylene group, substituents A1 and A2 are alkyl, cycloalkyl, aryl, aralkyl, or fluorine, substituent Z is chlorine, bromine, or alkoxy, and substituent X is a halogen atom. Various products having the following properties can be obtained. Examples of these organic germanium compounds include 1,3-bis(
chlorodimethylgermyl)bropane, 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(bromodimethylgel) mil)thiophene, α,α-bis(chlorodimethylgermyl)toluene, α,α'-bis(chlorodimethylgermyl)-p-xylene, and the like.

The present invention also provides general formula ArMe2 GeX1
A novel organogermanium compound represented by (IX) (wherein Ar represents an aryl group, Me represents a methyl group, and X1 represents bromine or iodine) is provided. Examples of these compounds include bromodimethylphenylgermane, iododimethylphenylgermane, bromodimethyltolylgermane, anisylbromodimethylgermane, and the like.

The present invention is based on the general formula ArCH=CHGeB1 B2 B3 (X)
(In the formula, Ar represents an aryl group, and B1, B2, and B3 represent 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.) I will provide a. Examples of these compounds are:
Examples include chlorodimethyl-β-styrylgermane, bromodimethyl-β-styrylgermane, bromodiethyl-β-styrylgermane, bromomethylphenyl-β-styrylgermane, trimethyl-β-styrylgermane, and the like.

The present invention is based on the general formula B1 B2 B3 GeCH2 Ar1 CH2
GeB1 B2 B3 (XI) (wherein Ar1 is an arylene group, B1, B2 and B3 are an alkyl group, a cycloalkyl group, which may be the same or different from each other,
The present invention provides a novel organogermanium compound represented by an aryl group, an aralkyl group, or a halogen atom. Examples of these compounds include α,α'-bis(chlorodimethylgermyl)-p-xylene, α,α'-bis(trimethylgermyl)-p-xylene, and α,α'-bis(chlorodimethylgermyl)-p-xylene. Examples include mil)-2,6-dimethylnaphthalene, α,α-bis(chloromethylphenylgermyl)-p-xylene, and the like.

The present invention is based on the general formula B1 B2 B3 GeAhGeB1B2 B3
(XII) (wherein Ah is a divalent aromatic heterocyclic group, B
1 , B2 and B3 each represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different. Examples of these compounds include 2,5-bis(chlorodimethylgermyl)
Thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, 2,5-bis(bromodimethylgermyl)thiophene, 2,5-bis(trimethylgermyl)thiophene, 2,5-bis(chlorodimethyl) (germyl)furan, 2,5-bis(triethylgermyl)pyridine, and the like.

[0019]

According to the present invention, various organic germanium compounds can be obtained from various organic halogen compounds without using an anionic reagent. In particular, even when the organic group newly introduced onto germanium is not derived from acetylene or olefin, an organic germanium compound having a halogen-germanium bond can be easily produced, and its industrial value is great.

[0020]

EXAMPLES Next, the present invention will be explained in more detail with reference to 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, t
rans-1,2-dichloroethylene 0.5 mmol
, 2 ml of toluene was added, and the mixture was heated and stirred in an oil solution at 180° C. for 15 hours. After cooling the autoclave, gas chromatography analysis revealed that 0.30 mmol of trans-1,2-bis(chlorodimethylgermyl)ethylene was produced.

Example 2 c instead of trans-1,2-dichloroethylene
The reaction was carried out in the same manner as in Example 1 except that is -1,2-dichloroethylene was used. As a result, trans -1,
2-bis(chlorodimethylgermyl)ethylene 0.08
mmol was produced.

Example 3 p instead of trans-1,2-dichloroethylene
The reaction was carried out in the same manner as in Example 1, except that dibromobenzene was used and the reaction was carried out at 150°C for 20 hours. As a result, p-
Bis(chlorodimethylgermyl)benzene 0.06mm
I got ol.

Example 4 1 mmol of benzyl chloride was used instead of trans-1,2-dichloroethylene, and 2 mmol of benzene was used instead of toluene.
The reaction was carried out in the same manner as in Example 1, except that 0.93 mmol of benzylchlorodimethylgermane was obtained, except that the reaction was carried out at 120° C. for 10 hours. By subjecting the reaction solution to Kugelrohr distillation, 0.80 mmol of benzylchlorodimethylgermane was isolated.

Example 5 The reaction was carried out in the same manner as in Example 4, except that 1 mmol of benzyl bromide was used instead of benzyl chloride and the reaction was carried out at 120°C for 5 hours. As a result, 0.21 mmol of benzyl chlorodimethyl germane, 0.19 mmol of bromodimethylgermane was obtained.

Example 6 The reaction was carried out in the same manner as in Example 5 except that the reaction time was changed to 10 hours.
24 mmol, benzyl bromodimethyl germane 0.2
1 mmol was obtained.

Example 7 The reaction was carried out in the same manner as in Example 1, except that 1 mmol of methyl iodide was used instead of trans-1,2-dichloroethylene and the reaction was carried out at 120°C for 15 hours.
0.18 mmol of chlorotrimethylgermane was obtained.

Example 8 The reaction was carried out in the same manner as in Example 7 except that the reaction was carried out at 80°C for 16 hours. As a result, chlorotrimethylgermane was 0.13
mmol was obtained.

Example 9 Bis(dibenzylideneacetone)palladium was used instead of tetrakis(triphenylphosphine)palladium.
05 mmol and 1-phospha-2,6,7-trioxa-4-ethylbicyclo[2,2,2]octane 0.20
The reaction was carried out in the same manner as in Example 7 except that 0.43 mmol of chlorotrimethylgermane was used.
I got it.

Example 10 1 mmol of β-bromostyrene instead of benzyl chloride
The reaction was carried out in the same manner as in Example 4, except that chlorodimethyl-tran was used and the reaction time was changed to 12 hours.
s -β-styryl germane 0.32 mmol, bromodimethyl-trans -β-styryl germane 0.5
6 mmol, chlorodimethyl-cis-β-styrylgermane 0.012 mmol, bromodimethyl-cis
-0.009 mmol of β-styryl germane was obtained.

[0030] These compounds are new compounds that have not been described in any literature, and their spectral data etc. are as follows. Chlorodimethyl-trans-β-styryl germane: bp150°C/8mmHg (Kugerrohr); 1HN
MR(CDCl3)δ0.86(s, 6H, GeC
H3), 6.67 (d, J=18Hz, 1H, C
=CHGe), 7.03(d, J=18Hz, 1
H, PhCH=C), 7.26-7.48(m,
5H, C6H5); MS (EI) m/z (relative intensity) 242 (M+, 24), 227 (M+-Me,
76), 191 (M+-Cl-Me-H, 100),
103 (M+-GeMe2Cl, 23); Elemental analysis value Actual value: C, 49.71, H, 5.37 C10
Calculated value as H13GeCl: C, 49.78, H,
5.43.

Bromodimethyl-trans-β-styryl germane: bp 150°C/8 mmHg (Kugerrohr); 1HNMR (CDCl3) δ0.98 (s, 6
H, GeCH3), 6.69 (d, J=18Hz,
1H, C=CHGe), 6.99(d, J=1
8Hz, 1H, PhCH=C), 7.29-7.
43(m, 5H, C6H5); MS(EI) m
/z (relative intensity) 286 (M+, 26), 271 (M
+-Me, 90), 191(M+-Br-Me-H,
100), 103(M+-GeMe2Br, 27)
;High resolution MS 285.9413 C10H13G
Calculated value as eBr: 285.941.

Chlorodimethyl-cis-β-styrylgermane: MS (EI) m/z (relative intensity) 227 (
M+-Me, 100), 191(M+-Cl-Me-
H, 36), 109(GeCl, 53)bromodimethyl-cis-β-styrylgermane: MS (EI)
m/z (relative intensity) 271 (M+-Me, 60),
207 (M+-Br, 100), 191 (M+-Br-
Me-H, 66), 103(M+-GeMe2Br,
19)

Example 11 The reaction was carried out in the same manner as in Example 10 except that the reaction time was changed to 15 hours, and the reaction solution was distilled using a Kugelrohr. As a result, chlorodimethyl-trans-β-styrylgermane was obtained.
．． 35 mmol, bromodimethyl-trans-β-
0.46 mmol of styryl germane was obtained.

Example 12 The reaction was carried out in the same manner as in Example 11, except that bromobenzene was used instead of β-bromostyrene, and 0.39 mmol of chlorodimethylphenylgermane and 0.31 mmol of bromodimethylphenylgermane were obtained. The latter compound is a new compound that has not been described in any literature, and its spectral data etc. are as follows.

Bromodimethylphenylgermane: bp
100℃/8mmHg (Kugerrohr); 1HNMR (
CDCl3) δ1.06 (s, 6H, GeCH3)
, 7.37-7.58 (m, 5H, C6H5); MS
(EI) m/z (relative intensity) 260 (M+, 11)
, 245(M+-Me, 100) , 181(M+-
Br, 22), 151(M+-Br-2Me, 27
); High resolution MS 259.9227, C8H11G
Calculated value as eBr: 259.9254.

Example 13 The reaction was carried out in the same manner as in Example 12, except that 1 mmol of iodobenzene was used instead of bromobenzene and the reaction time was changed to 5 hours. 0.68 mmol of germane was obtained. The latter compound is a new compound that has not been described in any literature, and its spectral data etc. are as follows.

Iododimethylphenylgermane: bp
120℃/8mmHg (Kugerrohr); 1HNMR (
CDCl3) δ1.24 (s, 6H, GeCH3)
, 7.39-7.60 (m, 5H, C6H5)
;MS (EI) m/z (relative intensity) 308 (M+, 1
), 293(M+-Me, 8), 181(M+-I
, 100), 151 (M+-I-2Me, 21);
Elemental analysis value Actual value: C, 31.16, H, 3
．． 60, calculated value as C8H11GeI: C, 3
1.33, H, 3.61.

Example 14 The reaction time was 10 hours, and triphenylphosphine was 0.5 hours.
The reaction was carried out in the same manner as in Example 13 except that 10 mmol was added, and 0.29 m of chlorodimethylphenylgermane was added.
mol, iododimethylphenylgermane 0.51mm
I got ol.

Example 15 The reaction was carried out in the same manner as in Example 13 except that 0.50 mmol of iodobenzene and 0.50 mmol of benzyl chloride were added and the reaction time was changed to 10 hours. .49 mmol was obtained. The formation of benzylchlorodimethylgermane was in trace amounts.

Example 16 The reaction was carried out in the same manner as in Example 13 except that the reaction temperature was 150°C.
mmol, iododimethylphenylgermane 0.61m
Obtained mol.

Example 17 The reaction was carried out in the same manner as in Example 13, except that 0.05 mmol of dichlorobis(triphenylphosphine)palladium was used instead of tetrakis(triphenylphosphine)palladium. 24 mmol and 0.53 mmol of iododimethylphenylgermane were obtained.

Example 18 Dichlorobis(trimethylphosphine)palladium 0.05 mmol and trimethylphosphine 0.10 instead of tetrakis(triphenylphosphine)palladium
The reaction was carried out in the same manner as in Example 13 except that mmol was used. As a result, chlorodimethylphenylgermane was 0.08
mmol was obtained.

Example 19 α instead of trans-1,2-dichloroethylene
, α'-dichloro-p-xylene 0.50 mmol, benzene 2 ml instead of toluene, 120°C
The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out for 0 hours. As a result, α,α'-bis(chlorodimethylgermyl)
-p-xylene 0.30 mmol was obtained. 0.24 mmol was isolated by Kugelrohr distillation of the reaction solution. This is a new compound that has not been described in any literature, and its spectroscopic data are as follows.

α,α'-bis(chlorodimethylgermyl)-p-xylene: bp 125°C/6mmHg (Kugerrohr) mp 80-82°C; 1HNMR (CDCl
3) δ0.61 (s, 12H, GeCH3), 2
．． 63 (s, 4H, ArCH2Ge), 6.99 (s
, 4H, C6H4); MS (EI) m/s (relative intensity) 380 (M+, 12), 243 (M+-Ge
Me2Cl, 54), 139(GeMe2Cl,
100); Actual elemental analysis value: C, 37.22; H,
5.04, calculated value as C12H20Cl2Ge2:
C, 37.89, H, 5.29.

Example 20 2 instead of trans-1,2-dichloroethylene
, 1.00 mmol of 5-dibromothiophene was used.
The same procedure as in Example 1 was carried out, except that the amount of 2-dichloro-1,1,2,2-tetramethyldigermane was 4.00 mmol, 2 ml of benzene was used instead of toluene, and the reaction was carried out at 150°C for 12 hours. As a result of the reaction, 2,5-
A mixture of bis(chlorodimethylgermyl)thiophene, 2-bromodimethylgermyl-5-chlorodimethylgermylthiophene, and 2,5-bis(bromodimethylgermyl)thiophene was obtained. After treating the reaction solution with methyllithium, 0.56 mmol of 2,5-bis(trimethylgermyl)thiophene was obtained by Kugelrohr distillation.
I got it. Each product is a new compound that has not been described in any literature, and its spectroscopic data are as follows.

2,5-bis(chlorodimethylgermyl)
Thiophene; MS (E/I) m/s (relative intensity) 35
8(M+, 21), 343(M+-Me, 100
), 139 (GeMe2Cl, 39). 2,5-bis(trimethylgermyl)thiophene: bp
100℃/6mmHg (Kugerrohr); 1HNMR
(acetone-d6) δ0.33(s, 18H, G
eCH3), 7.17(s, 2H, =CHCH=
): MS (EI) m/z (relative intensity) 318 (M+,
9), 303 (M+-Me, 100), 119 (Me3
Ge, 17); High resolution MS 319.9666
, Calculated value as C10H20Ge2S; 319.97
05.

Example 21 The reaction was carried out in the same manner as in Example 20, 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-bis(trimethylgermyl)benzene 0.51m
Obtained mol.

Claims (6)

[Claims] [Claim 1] General formula RX
(I) (wherein R is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aliphatic heterocyclic group, an aromatic heterocyclic group, or an aralkyl group which may have a substituent, and represents a halogen atom. ) in the presence of a palladium-containing catalyst, an organic halogen compound represented by
-nZm (II) (wherein Z represents chlorine, bromine or an alkoxy group, A1 and A2 represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or fluorine, m
and n is 1 or 2. ) with the general formula RGeA1nA23-m-nZm (III)
(wherein R, Z, A1, A2, m and n have the same meanings as above) and/or an organic germanium compound represented by the general formula RGeA1nA23-m-nXm (IV) (wherein R
, X, A1, A2, m and n have the same meanings as above. ) A method for producing an organic germanium compound represented by [Claim 2] General formula X-R1-X
(V) (In the formula, R1 is an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or an aralkylene group which may have a substituent). group, and X represents a halogen atom) in the presence of a palladium-containing catalyst.
-nZm (II) (wherein Z represents chlorine, bromine or an alkoxy group, A1 and A2 represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or fluorine, m
and n is 1 or 2. ) with the general formula Zm A1nA23-m-nGeR1 GeA1n
An organic germanium compound represented by A23-m-nZm (VI) (wherein R1, Z, A1, A2, m and n have the same meanings as above) and/or the general formula Xm A1nA23-m-nGeR1 GeA1n
A23-m-nZm (VII) (wherein,
R1, X, Z, A1, A2, m and n have the same meanings as above. ) and/or the general formula Xm A1nA23-m-nGeR1 GeA1n
A method for producing an organic germanium compound represented by A23-m-nXm (VIII) (wherein R1, X, A1, A2, m and n have the same meanings as above). [Claim 3] General formula ArMe2 GeX1
An organic germanium compound represented by (IX) (wherein Ar represents an aryl group, Me represents a methyl group, and X1 represents bromine or iodine). Claim 4: General formula ArCH=CHGeB1 B2 B3 (
X) (wherein Ar represents an aryl group, B1, B2
and B3 represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different. ) is an organic germanium compound represented by [Claim 5] General formula B1 B2 B3 GeCH2 Ar1 CH2
GeB1 B2 B3 (XI) (in the formula A
r1 represents an arylene group, and B1, B2 and B3 represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a halogen atom, which may be the same or different. ) is an organic germanium compound represented by [Claim 6] General formula B1 B2 B3 GeAhGeB1B2 B3
(XII) (In the formula, Ah represents a divalent aromatic heterocyclic group, and B1, B2, and B3 represent 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