JPS6328425B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a novel silane compound useful as an intermediate in the synthesis of various compounds, and also to a method useful as a method for crosslinking polymer compounds. [Prior Art] Conventionally, the reaction involving the cleavage of the Si-Si bond in vinyldisilane has the general formula: [In the formula, Vi: vinyl group, Me: methyl group, L: ligand] Palladium-catalyzed disproportionation reaction between monovinyldisilane and disilacyclopentane,
and the following formula: The only known platinum-catalyzed solvolysis reaction between monovinyldisilane and ethanol (Advances in Organometallic
Chemistry, 19 (1981) 213-255). The reaction used in the production method of the present invention is a reaction that involves the cleavage of vinyldisilane, but it is a reaction that is completely different from conventional reactions, and involves the addition of vinyldisilane to a vinylsilane compound. [Object of the Invention] An object of the present invention is to provide a manufacturing method capable of synthesizing a novel trisilylethane derivative compound useful as an intermediate for the synthesis of various compounds in a one-step reaction. Another object of the present invention is to provide a method for adding vinyldisilane to a vinylsilane compound, which is useful as a method for introducing a functional group into a compound and a method for crosslinking a polymer. [Structure of the Invention] The present invention is based on the general formula (): [Wherein, R may be the same or different and is a monovalent substituted or unsubstituted hydrocarbon group other than an ethynyl group, a halogen atom, a siloxy group, or a polymer residue; R′ may be the same or different It is also a lower alkyl group]. A method for producing a trisilylethane derivative compound represented by the general formula (): (R) ₃ SiCH=CH ₂ ... () [wherein R may be the same or different and defined in the general formula () above] [In the formula, R' _may be _{the same} or different. and R and R' are as defined in the general formula ()] in the presence of a platinum-based catalyst. In the present invention, the monovalent hydrocarbon group represented by the substituent R includes, for example, aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, vinyl, and allyl; alicyclic groups such as cyclohexyl group, methylcyclohexyl group, and cyclopentyl group; Formula hydrocarbon group: Aromatic hydrocarbon groups such as phenyl, tolyl, xylicyl, benzyl, etc. can be mentioned, and these can be substituted with halogens such as fluorine, chlorine, bromine, and iodine, alkoxy groups, silyl groups, siloquine groups, etc. may have been done. R further represents fluorine, chlorine, bromine,
Halogen atom of iodine; trimethylsiloxy group,
It may be a siloxy group such as a triethylsiloxy group; or a residue of various polymer compounds such as organopolysiloxane or polyether. Furthermore, examples of R' include lower alkyl groups such as methyl, ethyl, propyl, butyl, and hexyl. The platinum-based catalyst used in the above production method is not particularly limited, and examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum vinyl siloxane, platinum black, and a complex of chloroplatinic acid and olefin or aldehyde. In particular, chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum vinyl siloxane are highly active and preferred. The appropriate amount of platinum-based catalyst used in the reaction is 5 to 50 ppm of platinum based on the entire reaction solution.
is within the range of If it is less than 5 ppm, the reaction is slow and inefficient, and if it is more than 50 ppm, no further effect can be expected and it is not economical. The above production method is usually carried out in an organic solvent, and preferred organic solvents include aliphatic hydrocarbons such as n-hexane, n-heptane, and n-octane; aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran, Ethers such as dioxane and dibutyl ether can be mentioned. The amount of solvent used is not particularly limited, but the concentration of the compounds of general formulas () and () as reaction components is 5 to 80%.
% by weight is generally preferred since a good yield can be obtained. The usage ratio (mole ratio, ()/
()) is desirably selected from a range of 1 to 5. When two or more vinyl groups are bonded to the silicon atom of the general formula (), the compound of the general formula () can be obtained in good yield even if the molar ratio of ()/() is about 1, but the vinyl group When there is only one, a higher yield can be obtained by selecting a larger molar ratio of ()/(). In this way, the general formula ()
It is desirable to vary the proportions of the compounds of general formula () and general formula () depending on the number of vinyl groups bonded to the silicon atom. The appropriate temperature for the reaction is about 50-200℃, preferably 80-140℃.
℃ range, and the raw material compound usually disappears in 2 to 5 hours and the reaction is completed. If the reaction temperature is too low, the reaction will take a long time. If the reaction temperature is too high, the reaction components, compounds of general formulas () and (), are consumed in side reactions, or the generated compounds of general formula () are lost in secondary reactions, resulting in a decrease in yield. It is desirable that the reaction time be as short as possible within the above-mentioned appropriate temperature range and within a necessary and sufficient range for the reaction to be completed. A prolonged reaction causes the generated compound of general formula () to be lost through secondary reactions, resulting in a decrease in yield. Note that the reaction is preferably carried out under a dry inert atmosphere such as nitrogen or argon. If the generated compound of general formula () has a relatively low molecular weight, it can be separated from the reaction mixture obtained by the above reaction by distillation or preparative gas chromatography. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples. Parts mean parts by weight unless otherwise specified. Example 1 In a reactor purged with nitrogen gas, vinylsilane or vinylsiloxane represented by the following formula (ii) and vinyldisilane represented by the following formula (iii) were charged in the ratio shown in Table 1. , toluene was used as a solvent in an amount of 1000 g per mole of compound of formula (ii). Additionally, platinum vinyl siloxane was added as a catalyst to the reaction mixture at a concentration of 20 ppm (platinum content).
Substituents R ¹ , R ² of formula (ii) and formula (iii) in each experiment,
R ³ and R ⁴ are also shown in Table 1. The reaction was carried out at a temperature of 110°C for 2 hours. The resulting reaction mixture was subjected to flash distillation under vacuum to separate the product, which was then purified by preparative gas chromatography. The obtained product compound was subjected to NMR spectrum analysis, GC/MASS
It was subjected to analysis and elemental analysis. The analysis results revealed that a compound of the following formula (i) was produced. (ii) R ¹ R ² R ³ SiCH＝CH ₂ H ₂ C＝CHSiMe ₂ SiMe ₂ R ⁴ (i) The analysis results were as follows. (1) NMR spectrum: As shown in Table 1. (2) Elemental analysis: In each experiment, the analytical values for H, C, and Si were within the error of the theoretical values. (3) GC/MASS analysis: In each experiment, molecular ion peaks could be observed.

【table】

〔Effect of the invention〕

According to the production method of the present invention, functional groups such as vinyl groups, halogen atoms, alkoxy groups, etc. can be easily introduced into vinylsilane compounds in one step reaction, and the resulting new compounds of the present invention can be used as intermediates for the synthesis of various compounds. It is useful as This production method can also be used as a method for introducing functional groups into polymers and as a method for crosslinking polymers.

Claims (1)

[Claims] 1 General formula (): [Wherein, R may be the same or different and is a monovalent substituted or unsubstituted hydrocarbon group other than an ethynyl group, a halogen atom, a siloxy group, or a polymer residue; R' may be the same or different It is also a lower alkyl group. ] A method for producing a trisilylethane derivative compound represented by the general formula (): (R) ₃ SiCH=CH ₂ ...() [wherein R may be the same or different, and in the general formula () Vinylsilane represented by the general formula (): CH ₂ ＝CH−Si(R′) ₂ −Si(R′) ₂ (R) …() [In the formula, even if R′ is the same, and R and R' are as defined in the general formula ()] in the presence of a platinum-based catalyst. 2. The method according to claim 1, comprising:
A method in which at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, and ethers is used as a reaction catalyst. 3. The method according to claim 1, comprising:
A method in which the platinum-based catalyst is selected from chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum vinyl siloxane.