JPH0764861B2 - Process for producing organic bis-germyl ethylenes and novel organic bis-germyl ethylenes - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a novel method for producing an organogermanium compound and a novel organogermanium compound obtained thereby. 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 Regarding 1,2-bis (germyl) ethylenes, a method using a reagent having a high reactivity and a problem in handling, such as a conventional metal acetylide or bis (germyl) mercury, or digerman in the presence of a strong base. It has been manufactured by a method that is industrially impractical, such as a method of reacting with acetylenes in a lower carcinogenic hexamethylphosphoric triamide.

On the other hand, there are also a method of reacting a mixture of tetrahalogermane and dihalogermylene with acetylenes and a method of reacting trihalogermane in ether with acetylenes. In these methods, three halogens are present on a germyl group. It is only applicable to the production of substituted 1,2-bis (germyl) ethylenes. Therefore, the 1,2-bis (germyl) ethylenes known so far are
The substituents of the germyl group are limited to those having all alkyl groups or all halogens, and halogen or alkoxy groups and organic groups such as alkyl groups or aryl groups on the germyl group useful as a monomer for producing a germanium-containing polymer. Those having both substituents of the radical were not known.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to use 1,2-bis (1)-((bis) () having various substituents without using an alkali metal, mercury or the like, and without using a highly toxic solvent or the like. It is to provide a method for producing germyl) ethylenes in a single step, and to provide 1,2-bis (germyl) ethylenes having both a halogen or an alkoxy group and an organic group on the germyl group.

[0005]

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

That is, according to the present invention, (1) the general formula (I) R¹C≡CR^Two  (In the formula, R¹And R^TwoIs a hydrogen atom, alkyl group, aryl
LeBasis orAlkoxy carbonylBaseRepresent and be the same as each other
Or may be different. ) Acetylene
With the general formula (II) A¹A^TwoA^ThreeGeGeA^FourA⁵A⁶  (In the formula, A¹, A^Two, A^Three, A^Four, A⁵And A⁶Is al
killGroup or fluorine,chlorineOrbromineatomRepresents each other
It may be the same or different. )
Existence of digermanes and catalysts containing nickel group transition metals
General formula (III) A characterized by reacting under¹A^TwoA^ThreeGe (R¹) C = C (R^Two) GeA^FourA⁵
A⁶  (R¹, R^Two, A¹, A^Two, A^Three, A^Four, A⁵And A⁶
Has the same meaning as in formula (I) and formula (II). )
To produce 1,2-bis (germyl) ethylenes
Method, and (2) general formula (IV) X_mR^Three _nR^Four _3-m-nGeC (R¹) = C (R^Two)
GeR^Three _nR^Four _3-m-nX_m (In the formula,X isFluorine, chlorine or bromine atomRepresents,
R^ThreeAnd R^FourIs alkylBaseRepresent and be the same as each other
Or they may be different, and m is1,n is 1 or 2
R¹And R^TwoIs hydrogen atom, alkyl group, arylBasis
OrAlkoxy carbonylBaseRepresent and are the same as each other
Or they may be different. ) 1,2-bi represented by
Su (germyl) ethylenes are provided.

[0007] As acetylenes of the general formula (I) used in the present invention, the substituent is hydrogen atom, an alkyl group, an aryl group, various things can be used is a alkoxycarbonyl group, this to exemplify, it may be mentioned acetylene, propyne, 1-hexyne, 4-octyne, phenylacetylene, tigers down, a isethionate dicarboxylic acid dimethyl, propiolic acid ethyl Le like.

As the digermanes which is another raw material used in the present invention, digermanes represented by the general formula (II) in which all the hydrogens bonded to germanium atoms are replaced are used. Alkyl group, full Tsu element, various digermane to substituent chlorine or bromine is used, if illustrate these digermane compounds, hexamethyldisiloxane germane, hexaethyl di Germa emissions, 1, 2-dichloro-1,
1,2,2, - tetramethyldisiloxane Germa down, can be cited f hexafluorobutene di germane like.

The ratio of the acetylenes to the digermane compound in the method of 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. Moreover, when using gaseous acetylenes, normal pressure is sufficient.

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 (trimethylphosphite) palladium, and tetrakis (triphenyl). Phenylphosphine) palladium, tetrakis (triethylphosphine) palladium, tris (triphenylphosphite) palladium, dichlorobis (benzonitrile) valadium, bis (dibenzylideneacetone) palladium, platinum carbon, platinum black, chloroplatinic acid and its salts, chloride Platinum, Zeise salt, tetrakis (triphenylphosphine) platinum, tetrakis (dimethylphenylphosphine) platinum, tetrakis (to) Phenyl phosphite) platinum, dichlorobis (triphenylphosphine) platinum, ethylenebis (triphenylphosphine) platinum, chloro hydride bis (triethylphosphine) platinum, dichloro (tetramethylethylenediamine) platinum,
Dibromobis (trimethylphosphite) platinum, dichlorobis (benzonitrile) platinum, bis (cyclooctadiene) platinum, dichloro (cyclooctadiene) platinum, bis (dibenzylideneacetone) platinum, tetrakis (triphenylphosphine) nickel, tetrakis (triethyl) Phosphine) nickel, ethylene bis (triphenylphosphite) nickel, bis (cyclooctadiene)
Examples include nickel. These salts and complexes can be used alone, but are 1 to 10 times the metal atom.
Phosphines such as triphenylphosphine, methyldiphenylphosphine, trimethylphosphine, triethylphosphine, etc., trimethylphosphite, triphenylphosphite, 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2 , 2] Octane and other phosphites may be used together. The nickel group transition metal-containing catalyst may be used in 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 process according to the invention is carried out at reaction temperatures above 0 ° C., preferably room temperature to 250 ° C. Further, the method of the present invention can be carried out in the presence or absence of a solvent, but when a solvent is used, a commonly used solvent,
For example, various organic solvents such as benzene, toluene and hexane can be used. 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.

In the method of the present invention, the compound represented by the general formula (III) obtained when acetylene is used is hydrogen on a carbon, an alkyl group, an aryl group,
Although it obtained having various substituents such as alkoxycarbonyl group, if illustrate these, 1,2-bis (trimethylgermyl) ethylene emissions, 1, 2-bis (chloro-dimethyl germyl) ethylene 1,2-bis (trifluorogermyl) ethylene, 1,2-bis (trifluorogermyl) -1-propene, 4,5-bis (triethylgermyl) -4-octene, α, β-bis (chloro-dimethyl germyl) styrene emissions, 1, and 2-bis (chloro-dimethyl germyl) fumaric acid dimethyl, 1,2-bis (chloro-dimethyl germyl) maleate-dimethyl-like.

According to the method of the present invention, the above general formula (I
It is possible to obtain novel 1,2-bis (germyl) ethylenes represented by V). In the above formula, X represents a halogen atom , R ³ and R ⁴ represent an alkyl group, and m represents
1, n is 1 or 2, R ¹ and R ² are hydrogen atoms,
Alkyl group, Wath Table <br/> an aryl group, alkoxycarbonyl group.

[0014]

EFFECTS OF THE INVENTION According to the method of the present invention, 1,2-bis (germyl) ethylenes can be produced in a single step from readily available acetylenes under neutral conditions, and their separation and purification are easy. is there. The bis (germyl) represented by the general formulas (III) and (IV) obtained by the present invention
The compound is suitable as a raw material for producing a germanium-containing polymer.

[0015]

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 ml, phenylacetylene 5 mmol,
Heated in a 120 ° C. oil bath for 3 hours. As a result of gas chromatography analysis of the reaction solution, 0.40 mmol of (Z) -α, β-bis (chlorodimethylgermyl) styrene, (E) -α, β-
Bis (chlorodimethylgermyl) styrene 0.05mm
It was confirmed that ol was generated.

[0016] As a result of distilling the reaction solution with Kukuellohr,
0.31 mmol of (Z) -α, β-bis (chlorodimethylgermyl) styrene was obtained. This is a novel compound not yet published in the literature, and its physical properties are as follows.

Colorless liquid Bp 120 ° C./0.7 mmHg,
NMR (CDCl ₃ ) δ 0.82 (s, 6H, Ge (C
_{H 3) 2), 1.04 (} s, 6H, Ge (C
_{H 3) 2), 6.94 (} s, 1H, = CHGe), 7.
_{05-7.40 (m, 5H, C 6} H 5) ppm. MS
(M / z) 378 (1, M ⁺ ), 363 (3, MM)
e), 343 (17, M-Cl), 241 (32, M-)
ClMe ₂ Ge), 206 (6, M-ClMe ₂ Ge-
Cl), 139 (100, GeMe ₂ Cl), 109
(14, GeCl), 104 (14, Me ₂ Ge), 8
9 (22, MeGe) High resolution MS 379.9192
_{(C 12 H 18 Ge 2 Cl} 2 Calculated 379.920
9)

Example 2 A reaction was carried out in the same manner as in Example 1 except that a glass sealed tube was used instead of the autoclave and the reaction was carried out without solvent. As a result, (Z) -α, β-bis (chlorodimethyl) Germil)
0.52 mmol of styrene and 0.10 mmol of (E) -α, β-bis (chlorodimethylgermyl) styrene were produced.

Example 3 The reaction was carried out in the same manner as in Example 1 using a flask equipped with a reflux condenser instead of the autoclave, and the result was (Z).
0.55 mmol of -α, β-bis (chlorodimethylgermyl) styrene was produced.

Example 4 As a result of carrying out the reaction in the same manner as in Example 1 except that acetyl acetylene of latm was used instead of phenylacetylene, and the mixture was heated in a glass Schlenk tube at 100 ° C. for 12 hours,
0.55 mmol of (E) -1,2-bis (chlorodimethylgermyl) ethylene was obtained. This is a novel compound not yet published in the literature, and its physical properties are as follows.

Colorless liquid, Bp, 80-90 ° C / 8mmH
g, IR 965 cm ⁻¹ (δ CH), NMR (CD
Cl ₃ ) δ 0.80 (s, 12H, (CH ₃ ) ₂ G
e), 6.90 (5,2H, GeHC =), MS (20
eV, m / z) 302 (2, M ⁺ ), 287 (100,
_{M-Me), 276 (16} , ClMe 2 GeGeMe 2
Cl), 267 (18, M-Cl), 165 (2, M-
ClMe ₂ Ge), 139 (55, ClMe ₂ Ge),
119 (13, Me ₃ Ge), 104 (49, Me ₂ Ge)
e), 89 (3, MeGe), high resolution MS 303.
8904 _(calculated 30 as C ₆ H 14 _{Ge 2} Cl 2
3.8896)

Example 5 The reaction was carried out in the same manner as in Example 3 except that hexamethyldigermane was used in place of 1,2-dichloro-1,1,2,2-tetramethyldigermane, resulting in (Z)- 0.01 mmol of α, β-bis (trimethylgermyl) styrene was produced. 48 while adding more phenylacetylene
As a result of heating for 0.2 hours, 0.24 mmol of (Z) -α, β
-Bis (trimethylgermyl) styrene was produced. This is a novel compound not yet published in the literature, and its physical properties are as follows.

Colorless liquid, Bp, 60-70 ° C./1 mmH
g, NMR (CDCl ₃ ) 0.29 (s, 9H, Ge
_{(CH 3) 3), 0.34} (s, 9H, Ge (CH 3)
₃ ), 6.51 (s, 1H, = CHGe), 6.9-
_{7.4 (m, 5H, C 6} H 5), MS (m / z) 323
(18, M-me), 221 (10, M-GeM
e ₃ ), 205 (8) 181 (10, PhMe ₂ G
e), 119 (100, Me ₃ Ge), 104 (10,
Me ₂ Ge), 89 (19, MeGe).

Example 6 Tetrakis (triphenylphosphine) palladium was used in place of tetrakis (triphenylphosphine) palladium, and the reaction was carried out in the same manner as in Example 4 to carry out Kugelrohr distillation. As a result, (Z) -1,2-bis 0.19 mmol of (chlorodimethylgermyl) ethylene was obtained. This is a novel compound not yet published in the literature, and its physical properties are as follows.

Colorless liquid, Bp, 70-80 ° C / 9mmH
g, NMR (CDCl ₂ ) 0.90 (s, 12H, Ge
(CH ₃ ) ₂ ), 7.03 ppm (s, 2H, = CHG
e), MS (20 eV, m / z) 287 (100, M-
Me), 276 (17), 267 (22, M-Cl),
139 (57, ClMe ₂ Ge), 129 (16), 1
19 (22, Me ₃ Ge), 104 (64, Me ₄ Ge)
e), 89 (8, MeGe).

Example 7 The reaction was carried out in the same manner as in Example 6 except that the reaction time was 48 hours. As a result, 0.29 mmol of (Z) -1,2-bis (chlorodimethylgermyl) ethylene was produced.

Example 8 The reaction was carried out in the same manner as in Example 3 except that dimethyl acetylenedicarboxylate was used instead of phenylene acetylene, and as a result, 1,2-bis (chlorodimethylgermyl) ethylenedicarboxylate dimethyl was found to be 0. 59 mmol was produced. This is a novel compound that has not been published in the literature, and its mass spectrum is as follows.

MS (m / z) 403 (17, MM
e), 383 (33, M-Cl), 281 (18, M-)
ClMe ₂ Ge), 250 (22, M-ClMe ₂ Ge)
-MeO), 187 (23), 139 (100, ClM
e ₂ Ge).

Example 9 The same reaction as in Example 1 was carried out except that the amount of phenylacetylene was 2 mmol and the reaction was carried out in a glass Schlenk tube. As a result, (Z) -α, β-bis (chloro) was obtained. (Dimethylgermyl) styrene 0.81 mmol, (E)-
α, β-bis (chlorodimethylgermyl) styrene 0.
07 mmol was produced.

Example 10 The reaction was carried out in the same manner as in Example 9 except that the amount of phenylacetylene was 1 mmol, the reaction temperature was 100 ° C., and the reaction time was 1 hour. As a result, (Z) -α, β- 0.68 mmol of bis (chlorodimethylgermyl) styrene,
0.04 mmol of (E) -α, β-bis (chlorodimethylgermyl) styrene was produced.

Example 11 The amount of phenylacetylene was adjusted to 5 mmol, 0.40 mmol of triphenylphosphine was added, and the reaction temperature was adjusted to 1
The reaction was performed in the same manner as in Example 9 except that the reaction time was set to 00 ° C and the reaction time was set to 1 hour. As a result, 0.20 mmol of (Z) -α, β-bis (chlorodimethylgermyl) styrene, (E)
0.01 mmol of -α, β-bis (chlorodimethylgermyl) styrene was produced.

Example 12 The amount of phenylacetylene was set to 1 mmol, and dichlorobis (trimethylphosphine) palladium 0.05 was used instead of tetrakis (triphenylphosphine) palladium.
As a result of carrying out the reaction in the same manner as in Example 9 except that mmol was used, (Z) -α, β-bis (chlorodimethylgermyl) styrene 0.81 mmol, (E) -α, β-bis (chloro) Dimethylgermyl) styrene 0.07 mmol
Was generated.

Example 13 The amount of phenylacetylene was 2 mmol, and bis (dibenzylideneacetone) palladium 0.05 mmo was used instead of tetrakis (triphenylphosphine) palladium.
1 and 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane 0.10 mmol
Was added, and the reaction temperature was 100 ° C. and the reaction time was 1 hour.
0.33 mmol of -α, β-bis (chlorodimethylgermyl) styrene was produced.

Example 14 As a result of carrying out the reaction in the same manner as in Example 4 except that 0.05 mmol of dichlorobis (trimethylphosphine) palladium was used in place of tetrakis (triphenylphosphine) palladium, (E) -1,2 -0.30 mmol of bis (chlorodimethylgermyl) ethylene was produced.

Example 15 In place of tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) valadium.
05 mmol and trimethylphosphine 0.10 mmo
As a result of carrying out the reaction in the same manner as in Example 4 except that 1 was used, (E) -1,2-bis (chlorodimethylgermyl)
0.33 mmol of ethylene was produced.

Example 16 Bis (dibenzylideneacetone) palladium in place of tetrakis (triphenylphosphine) palladium
05 mmol and 1-phospha-2,6,7-trioxa-4-ethylbicyclo [2,2,2] octane 0.1
As a result of carrying out the reaction in the same manner as in Example 4 except that 0 mmol was used, 0.83 mmol of (E) -1,2-bis (chlorodimethylgermyl) ethylene was produced.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI Technical location B01J 31/28 C07B 61/00 300 (56) Reference JP-A-54-88224 (JP, A) JP-A-56-122390 (JP, A) JP-A-48-67223 (JP, A) JP-A-52-83334 (JP, A) J. ORGANO METAL. CHE M. , 117-3! (1976), C55-D57. ORGANO METALLICS, 6-5! (1987), 974-979. CHEMICAL ABSTRACT S, 60-13! (1964), 15899F-H. CHEMICAL ABSTRACT S, 65-11! (1966), 16997 EG.

Claims (2)

[Claims] 1. The general formula (I) R¹C = CR^Two (In the formula, R¹And R^TwoIs a hydrogen atom, alkyl group, aryl
LeBasis orAlkoxy carbonylBaseRepresent and be the same as each other
Or may be different. ) Acetylene
With the general formula (II) A¹A^TwoA^ThreeGeGeA^FourA⁵A⁶ (In the formula, A¹, A^Two, A^Three, A^Four, A⁵And A⁶Is al
killGroup or fluorine,chlorineOrbromineatomRepresents each other
It may be the same or different. )
Existence of digermanes and catalysts containing nickel group transition metals
General formula (III) A characterized by reacting under¹A^TwoA^ThreeGe (R¹) C = C (R^Two) GeA^FourA⁵
A⁶  (R¹, R^Two, A¹, A^Two, A^Three, A^Four, A⁵And A⁶
Has the same meaning as in formula (I) and formula (II). )
To produce 1,2-bis (germyl) ethylenes
Law. 2. The general formula (IV) XmR^Three _nR^Four _3-m-nGeC (R¹) = C (R^Two)
GeR^Three _nR^Four _3-m-nX_m  (In the formula,X isFluorine, chlorine or bromine atomRepresents,
R^ThreeAnd R^FourIs alkylBaseRepresent and be the same as each other
Or they may be different, and m is1,n is 1 or 2
R¹And R^TwoIs hydrogen atom, alkyl group, arylBasis
OrAlkoxy carbonylBaseRepresent and are the same as each other
Or they may be different. ) 1,2-bi represented by
Su (germyl) ethylenes.