JPS6059916B2 - Method for producing 1,2-disilylalkene compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a mono-disilyl alkene compound, that is, an alkene compound having silyl groups on both sides of a carbon-carbon double bond. The present invention relates to a method of inserting a carbon-carbon double bond between carbon-carbon double bonds.

The high-boiling fraction produced as a by-product when synthesizing methylchlorosilanes by the direct method mainly consists of methylchlorodisilanes, especially disilanes containing 3 to 4 chlorine atoms,
There were limited ways to directly utilize this effectively.

Therefore, many studies have been conducted on methods of reacting these disilanes to convert them into industrially useful organosilicon compounds. The main method is to react these disilanes with hydrogen chloride or halogenated hydrocarbons in the presence of amines, ammonium salts, phosphonium salts, or transition metal complexes to produce hydrosilanes and various hydrocarbons. A method for obtaining substituted silanes is a method for obtaining alkenylsilanes by reacting di-alkoxylated disilanes with an acetylene derivative at a high temperature of 400 to 450°C. However, for both 1 and 2, only half of the silicon atoms in disilanes can be used as the desired hydrosilane, alkenylsilane, etc., and especially when tetrafunctional disilanes are used as a starting material, industrially It has the disadvantage of producing large amounts of methyltrichlorosilane and methyltrialkoxysilane, which are of low utilization. In addition, in case 1, it is difficult to control the reaction, and most of them require a high-pressure reactor. In case 2, all reactions must be carried out in a high-pressure reactor and at high temperatures. However, there is a problem in that it is difficult to control the reaction.

On the other hand, the following method is known for synthesizing silane derivatives having a carbon-carbon aliphatic double bond other than vinylsilanes.

That is, 1 arche. Reactions between organic metal reagents and halosilanes, methods for reacting 2-acetylene and chlorosilanes in magnesium-hexamethylphosphoric triamide, methods for reacting 8-alkoxydisilanes and acetylene compounds at high temperatures, tetrachloroplatinic acid, etc. - This is a method of hydrosilylating an acetylene compound in the presence of a catalyst. However, method 1 makes it difficult to synthesize alkenyl organometallic reagents, method 2 yields only limited types of alkenylsilanes, and method 3 yields 400 to 45
There are a number of problems with method 4, such as requiring a high temperature of 100 yen (200 yen), making it difficult to control the reaction, and generally having low yields and often involving side reactions. The present invention
A method for producing 1,2-disilyl alkene compounds in good yield by reacting disilanes and acetylene compounds with tetrakis(triphenylphosphine)palladium as a catalyst under mild reaction conditions, that is, at relatively low temperatures. This is what we provide.

That is, the present invention provides the following formulas: Disilanes (4) represented by the general formula (St... R7 and R8 are selected from the group consisting of a hydrogen atom, an alkyl group, a phenyl group, a trimethylsilyl group, and an alkoxycarbonyl group; Acetylene compounds (B
) in the presence of tetrakis(triphenylphosphine)palladium at a temperature of 160°C or less, represented by the general formula (St, .Rl to R8 are as described above), 1 -Related to a method for producing a 2-disilylalkene compound.

The disilanes (4) used in the present invention have the general formula RlR
2R3SiSiR4R5R6. Here R1-
R6 is as described above and may be the same or different. Alkyl groups include methyl, ethyl, propyl, and butyl groups; alkoxy groups include methoxy, ethoxy, propoxy, and butoxy groups; acyloxy groups include acetoxy; and halogen atoms include chlorine. Illustrated. Among these, due to the ease of obtaining raw materials and ease of synthesis, they are produced as by-products during the synthesis of methylchlorosilanes by direct methods. R1~R
Those in which 6 is a methyl group and/or a chlorine atom are desirable, and in particular, from the viewpoint of availability, 1,2-dimethyl-1●1,2●2-tetrachlorodisilane and 1●1●
2-trimethyl-1●2●2-trichlorodisilane, 1,1,2,2-tetramethyl-1●2-dichlorodisilane is preferable since the product is the most useful bifunctional compound. . In addition, these disilanes can be easily obtained by alcoholysis,
Disilanes in which R1 to R6 are a methyl group and/or a methoxy group or an ethoxy group are also desirable because they are easily available and do not produce strongly acidic by-products when mixed with water. Examples of such disilanes include the following. S
tl In the above and below compositional formulas, the following abbreviations are used for simplicity. The acetylene compound (B) used in the present invention is represented by the general formula R7CmiCR8.

Here, R7 and R8 are as described above, and may be the same or different. Examples of the alkyl group include a methyl group, ethyl group, propyl group, and butyl group, and examples of the alkoxycarbonyl group include a methoxycarbonyl group. Because of its ease of synthesis and handling, R7
and at least one of R8 is a phenyl group, n-
Preferably, it is a butyl group, a trimethylsilyl group, or a methoxycarbonyl group. Such acetylene compounds include PhCmiCH, . PhC=CMesn-
Pressure °C=CHsn-BuC=CMe,. Me3SiC=C
H. An example is sMeOCOC=CCOOMe.
The amount of the acetylene compound (B) to be used relative to the disilanes (4) may be arbitrary, but considering the reactivity of the acetylene compound, it is preferably between 0.4 and 1.5 equivalents relative to the disilanes. Desirably, 0.7 to 1. It is more desirable that the temperature be between the amount of σ. Tetrakis(triphenylphosphine)palladium used in the present invention is a catalyst for the reaction between disilane (4) and acetylene compound (B).

This reaction proceeds in the presence of a metal such as nickel, palladium, or platinum, or a (0) or divalent phosphine complex of these metals, but palladium complexes, especially tetrakis (triphenylphosphine) is selected. The amount of tetrakis(triphenylphosphine)palladium used in the present invention is not particularly limited, but a very small amount is effective;
0.5 to 5 mol% or less based on the acetylene compound (B) is sufficient. The reaction of the present invention is carried out at a temperature range from room temperature to the reflux temperature of the reactants, that is, about 160 DEG C., but generally a temperature between 80 DEG and 150 DEG C. is preferred because it provides the best yield.

This reaction can be carried out at atmospheric pressure, sub-atmospheric pressure or above-atmospheric pressure, but the reaction at atmospheric pressure is advantageous as it requires less consideration regarding equipment. A solvent may be used as necessary when the reaction is vigorous or to facilitate uniform mixing of each component. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, and aliphatic hydrocarbons such as hexane. According to the present invention, it is possible to obtain a 1,2-disilylalkene compound under relatively mild conditions using disilanes, which are inevitably produced as a by-product during the synthesis of methylchlorosilanes by a direct method, as a starting material. can.

Furthermore, by cleaving this with hydrogen halides, alkali metal salts, or alkali metal alcoholates, a wide range of alkenylsilanes can be obtained much more easily than with conventional methods, and without using high temperatures or pressures. be able to. The 1,2-disilylalkene compound obtained by the present invention is itself useful as an adhesion aid or a curing agent for polyorganosiloxane.

In addition, alkenylsilanes obtained by cleavage reactions are also used as components of adhesion aids, etc., and as intermediates for introducing alkenyl groups into various polyorganosiloxanes. Organosiloxane gives a rubber-like elastic body or a resin-like substance by curing at room temperature or by heat curing, and is widely used as a heat-resistant and cold-resistant material. should not be limited by the examples. In the examples, all parts represent parts by weight. Example 1 102 parts of phenylacetylene, 1●2-dimethyl-1.
1●A mixture of 24 parts of 2,2-tetrachlorodisilane and 0.5 m of tetrakis(triphenylphosphine)palladium was heated to 140°C in a nitrogen stream at atmospheric pressure.

After 5 hours of heating, the phenylacetylene was completely consumed and 20 m of cis-1,2-bis(dichloromethylsilyl)styrene was obtained by distillation.

This corresponded to 60% of the theoretical yield. Generated Sisu 1
- The physical properties and elemental analysis results of 2-bis(dichloromethylsilyl)styrene were as follows. Physical properties Boiling point 114-115°C/2wtHg Elemental analysis Actual value C43.62%H4.3O% Theoretical value C43.8O%H4.38% Example 2 The same reaction as in Example 1 was carried out with 102 parts of phenylacetylene and various I went among the Jishirans.

Disilane is 120 to 20 compared to phenylacetylene.
Tetrakis(triphenylphosphine)palladium was used as a catalyst at 0% by mole for phenylacetylene.
．． It was used in an amount of 1 to 0.5 mol%. The reaction formula is as follows. The disilanes used and reaction conditions are shown in Table 1, and the products, their yields, physical properties, and analysis results are shown in Table 2.

Example 3 Reactions similar to those in Example 1 were conducted between various disilanes and acetylene compounds.

As a catalyst, tetrakis(triphenylphosphine)palladium was used in an amount of 0.1 mol % based on the acetylene compound. Table 3 shows the acetylene compound, disilane, and reaction conditions used in the reaction, and Table 4 shows the product, its yield, physical properties, and elemental analysis results. Example 4 Using 102 parts of phenylacetylene, 21.5 parts of 1,1,2,2-tetramethyl-1●2-dimethoxydisilane, and various catalysts shown in Table 5, under the reaction conditions shown in Table 5. When the reaction was carried out in a nitrogen stream at atmospheric pressure, cis-1●2-bis(dimethylmethoxysilyl)styrene was obtained in the yield shown in Table 5.

Stl experiment 41 is according to the present invention, experiment 42
-47 are comparative examples. Example 5 A reaction similar to that of Example 1 was carried out between 102 parts of phenylacetylene and various disilanes, and the results shown in Table 6 were obtained.

Claims (1)

[Claims] 1 General formula R^1R^2R^3SiSiR^4R^5R^6 (where R^1 to R^6 are an alkyl group, an alkoxy group, a phenoxy group, an acyloxy group, and a halogen Disilanes (A) represented by (representing mutually identical or different monovalent groups selected from the group consisting of atoms) and the general formula R^7C
≡CR^8 (However, R^7 and R^8 are selected from the group consisting of a hydrogen atom, an alkyl group, a phenyl group, a trimethylsilyl group, and an alkoxycarbonyl group, and at least one of them is an alkyl group, and an acetylene compound (B) represented by a phenyl group, a trimethylsilyl group, or an alkoxycarbonyl group, which are the same or different monovalent groups, in the presence of tetrakis(triphenylphosphine)palladium at 160°C. The general formula (R^1R^2R^3S
i) (R^7)C=C(R^8)(SiR^4R^5R
^6) A method for producing a 1,2-disilylalkene compound represented by (R^1 to R^8 are as described above). 2. The manufacturing method according to claim 1, wherein R^1 to R^6 of the disilanes (A) are monovalent groups selected from a methyl group and a chlorine atom. 3 Disilane (A) is 1,2-dimethyl-1,1,2
- The manufacturing method according to claim 1, which is 2-tetrachlorodisilane. 4 Disilanes (A) are 1,1,2-trimethyl-1,
The manufacturing method according to claim 1, which is 2,2-trichlorodisilane. 5. The manufacturing method according to claim 1, wherein the disilane (A) is 1,1,2,2-tetramethyl-1,2-dichlorodisilane. 6 R^1 to R^6 of disilane (A) are methyl groups,
The manufacturing method according to claim 1, wherein the monovalent group is selected from methoxy and ethoxy groups. 7. The manufacturing method according to claim 1, wherein at least one of R^7 and R^8 of the acetylene compound (B) is a phenyl group. 8. The manufacturing method according to claim 1, wherein at least one of R^7 and R^8 of the acetylene compound (B) is an n-butyl group. 9. The manufacturing method according to claim 1, wherein at least one of R^7 and R^8 of the acetylene compound (B) is a trimethylsilyl group. 10. The manufacturing method according to claim 1, wherein at least one of R^7 and R^8 of the acetylene compound (B) is a methoxycarbonyl group. 11. The manufacturing method according to claim 1, wherein the reaction is carried out at a temperature of 80 to 150°C.