JPH0764862B2 - Process for producing organic bis-germyl butenes and novel organic bis-germyl butenes - Google Patents

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 obtained thereby. Organic germanium compounds are used as additives to catalysts and polymers, and also attract attention as bactericides, antiseptics, antitumor agents, and the like. It is also in the spotlight as a monomer for producing a germanium-containing polymer useful as an electronic and optical functional material.

[0002]

BACKGROUND OF THE INVENTION 1,4-Bis (germyl) -2-butenes are produced by reacting 1,4-dichloro-2-butene with trihalogermane in ether. However, this method is peculiar to trihalogermane, and it is 1,4 in which three halogens are substituted on germanium.
-Applicable only to the production of bis (germyl) -2-butenes.

There is also a method of obtaining 1,4-bis (trimethylgermyl) -2-butene by metathesis of allyltrimethylgermane with a rhenium-based catalyst, but this method can be applied only to those in which the substituent on germanium is methyl. Therefore, the 1,4-bis (germyl)-
The 2-butenes are limited to those in which all the substituents on the germyl group are halogen and those in which all the substituents on the germyl group are alkyl groups, and are useful as a monomer for producing a germanium-containing polymer, It has not been known that a germyl group has a halogen or alkoxy group and an organic group such as an alkyl group or an aryl group, which have both substituents.

[0004]

The object of the present invention is to provide a method for producing 1,4-bis (germyl) -2-butenes having various substituents in one step, and to obtain by this method. A halogen atom on the germyl group,
1,4-bis (germyl) -2 having both an organic group
-To provide butenes.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that various dienes react with dikermans in the presence of a palladium-containing catalyst. The facts have been found, and the present invention has been completed based on this finding.

That is, according to the present invention,(1) General formula (I) R¹CH = C (R^Two) -C (R^Three) = CHR^Four  (In the formula, R¹, R^Two, R^ThreeAnd R^FourIs a hydrogen atomOrAl
Represents a kill group, which may be the same or different from each other
Or they may be bonded to each other to form a ring. )
Represented by the general formula (II) A¹A^TwoA^ThreeGeGeA^FourA⁵A⁶  (In the formula, A¹, A^Two, A^Three, A^Four, A⁵And A⁶Is al
Kill groupOrFluorine, chlorineOrbromineatomRepresents each other
It may be the same or different. )
Reacts with digermanes in the presence of palladium-containing catalysts.
General formula (III) A¹A^TwoA^ThreeGe (R¹) CH-C (R^Two) = C
(R^Three) -CH (R^Four) GeA^FourA⁵A⁶  (R¹, R^Two, R^Three, R^Four, A¹, A^Two, A^Three, A^Four,
A⁵And A⁶Has the same meaning as in formula (I) and formula (II)
One. ) 1,4-bis(Germill)-2-bu
Manufacturing method of martens, and(2) General formula (IV) X_mR⁵ _nR⁶ _3-m-nGe (R¹) CH-C
(R^Two) = C (R^Three) -CH (R^Four) GeR⁵ _nR⁶
_3-m-nX_m  (Where X is halogenatomAnd R⁵And R⁶Is al
killBaseIt may be the same or different
M is1,n is 1 or 2 and R¹, R^Two, R^Three
And R^FourRepresents a hydrogen atom or an alkyl group and is the same as each other.
Can be different or different and are joined together to form a ring
You may have. ) 1,4-bis (germi)
Le) -2-butenes are provided.

As the dienes represented by the general formula (I) used in the method of the present invention, various ones in which the substituent is hydrogen or an alkyl group can be used. For example, butadiene, Examples include isoprene, 2,3-dimethylbutadiene, 1,3-cyclohexadiene and the like.

The general formula (II) used in the method of the present invention
In The digermane compound represented, alkyl or off <br/> Tsu element, but is used which with a substituent chlorine or bromine atom, if illustrate these digermane compounds, hexamethyldisiloxane germane, Hekisaechiruji Germa emissions, 1, 2-dichloro-1,1,2,2-tetramethyldisiloxane Germa down, can be cited f <br/> hexafluorobutene di germane like.

The ratio of the diene 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. When a gaseous diene is used, it can be used at a pressure above or below atmospheric pressure.

In the present invention, a catalyst containing vanadium is used as the 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 ( Examples thereof include triphenylphosphine) palladium, tetrakis (triethylphosphine) palladium, tris (triphenylphosphite) palladium, dichlorobis (benzonitrile) palladium, and bis (dibenzylideneacetone) valadium. These salts, complexes, etc. can be used alone, but phosphines such as triphenylphosphine, methyldiphenylphosphine, triethylphosphine, trimethylphosphine, etc., which are about 1 to 10 times the palladium atom, trimethylphosphite, triphenyl Phosphite, 1-phospha-2,
6,7-Trioxa-4-ethylbicyclo [2,2,2
2] It may be used together with a ligand such as phosphite such as octane. 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 to digermanes.

The process of the invention is carried out at reaction temperatures above 0 ° C., 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 general formula (I
As the compound represented by II), a compound having hydrogen or an alkyl group as a substituent on carbon can be obtained. For example, 1,4-bis (trimethylgermyl) -2-butene, 1 4- bis (chloro-dimethyl germyl) -2-methyl-2-butene emissions and the like.

According to the method of the present invention, novel 1,4-bis (germyl) -2-butenes represented by the following general formula can be obtained. ^{_{X m R 5 n R 6 3}} -m-n GeC (R 1) CH-C (R
^{2) = C (R 3)} -CH (R 4) GeR 5 n R 6
_3-m-n X _m ... (IV) In the above formula, X represents a halogen atom , R ⁶ and R ⁵ represent an alkyl group , which may be the same or different, and m is 1, n. Is 1 or 2 and R ¹ , R ² , R
³ and R ⁴ represent a hydrogen atom or an alkyl group, which may be the same as or different from each other, and may be bonded to each other to form a ring.

[0014]

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, isoprene 5 mmol, and 120 ° C.
As a result of heating for 3 hours in an oil bath, 1,4-bis (chlorodimergermyl) -2-methyl-2-butene 0.19 mm
ol generated. This is a novel compound not yet published in the literature, and its physical properties are as follows.

Colorless liquid, NMR (CDCl ₃ ) δ 0.6
_{9 (s, 6H, Ge (} CH 3) 2), 0.73 (s, 6
_{H, Ge (CH 3) 2} ), 1.77 (s, 3H, CCH
₃ ), 2.01 (d, J = 8.5 Hz, 2H, GeCH
₂ CH =), 2.14 (s, 2H, GeCH ₂ C (M
e) =), MS (m / z), 344 (3, M ⁺ ), 30
9 (2, M-Cl), 207 (19, M-ClMe ₂ G
_{e), 172 (14, M} -ClMe 2 Ge-Cl), 1
_{57 (20, M-ClMe 2} Ge-ClMe), 13
9 (100, ClMe ₂ Ge), 104 (14, Me ₂
Ge), 89 (13, MeGe), high resolution MS 34
5.9345 _(calculated 345.9365 as _{C 9 H 20 Ge 2 Cl 2} ).

Examples 2 to 4 Table 1 shows the results of repeating Example 1 with the catalyst being replaced.

Example 5 Teslakis (triphenylphosphine) palladium
Using 20 mmol, the reaction temperature is 100 ° C. and the time is 20
As a result of carrying out the reaction in the same manner as in Example 1,
4-bis (chlorodimethylgermyl) -2-methyl-2
-0.4 mmol of butene was obtained.

EXAMPLE 6 Bis (dibenzylideneacetone) palladium in place of tetrakis (triphenylphosphine) palladium.
05 mmol and trimethylphosphine 0.10 mmo
As a result of performing the reaction in the same manner as in Example 1 except that 1 was added, 0.44 mmol of 1,4-bis (chlorodimethylgermyl) -2-methyl-2-butene was obtained.

Example 7 Bis (dibenzylideneacetone) palladium was used 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 1 except that 0 mmol was added, 1,4-bis (chlorodimethylgermyl) was obtained.
0.77 mmol of 2-methyl-2-butene was obtained.

[0020]

EFFECTS OF THE INVENTION According to the method of the present invention, various 1,4-bis (germyl) s from easily available dienes under neutral conditions are selected.
The 2-butenes can be produced in a single step, and their separation and purification are easy. Further, according to the present invention, a bis (germyl) compound suitable as a raw material for producing a germanium-containing polymer can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-56-122387 (JP, A) J. ORGANO METAL. CHE M. , 199 (1980), 185-193. ORGANO METAL. CHE M. , 117-3! (1976), C55-C57. ORGANO METALLICS, 6-5! (1987), 974-979. CHEMICAL ABSTRACT S, 62-12! (1965), 14064G.

Claims (2)

[Claims] 1. The general formula (I) R¹CH = C (R^Two) -C (R^Three) = CHR^Four  (In the formula, R¹, R^Two, R^ThreeAnd R^FourIs a hydrogen atomOrAl
Represents a kill group, which may be the same or different from each other
Or they may be bonded to each other to form a ring. )
Represented by the general formula (II) A¹A^TwoA^ThreeGeGeA^FourA⁵A⁶  (In the formula, A¹, A^Two, A^Three, A^Four, A⁵And A⁶Is al
Kill groupOrFluorine, chlorineOrbromineatomRepresents each other
It may be the same or different. )
Reacts with digermanes in the presence of palladium-containing catalysts.
General formula (III) A¹A^TwoA^ThreeGe (R¹) CH-C (R^Two) = C
(R^Three) -CH (R^Four) GeA^FourA⁵A⁶  (R¹, R^Two, R^Three, R^Four, A¹, A^Two, A^Three, A^Four,
A⁵And A⁶Has the same meaning as in formula (I) and formula (II)
One. ) 1,4-bis(Germill)-2-bu
Manufacturing method of martens. 2. The general formula (IV) X_mR⁵ _nR⁶ _3-m-nGe (R¹) CH-C
(R^Two) = C (R^Three) -CH (R^Four) GeR⁵ _nR⁶
_3-m-nX_m  (Where X is halogenatomAnd R⁵And R⁶Is al
killBaseIt may be the same or different
M is1,n is 1 or 2 and R¹, R^Two, R^Three
And R^FourRepresents a hydrogen atom or an alkyl group and is the same as each other.
Can be different or different and are joined together to form a ring
You may have. ) 1,4-bis (germi)
Le) -2-butenes.