JPS61207389A - Novel disilacyclopentane compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I [R is (un)substituted monofunctional hydrocarbon]. EXAMPLE:1,1,2,2-Tetramethyl-3-vinyldimethylsilylmethyl-5-vinyldimethyl silyl-1,2- disilacyclopentane. USE:A crosslinking agent in high polymer chemistry. PREPARATION:1,2-Divinyldisilane shown by the formula II is reacted in the presence of preferably 5-50ppm calculated as platinum of a platinum catalyst (e.g., chloroplatinic acid, etc.) in usually 2-5 times as much a solvent such as aliphatic or aromatic hydrocarbon as the compound at 80-140 deg.C usually for 2-5hr.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel disilacyclobentane compound useful as a crosslinking agent in polymer chemistry and as an intermediate in the synthesis of various compounds, and a method for producing the same.

[Conventional technology]

Conventionally, a reaction involving cleavage of the 5i-5i bond of vinyldisilane has been carried out using monovinyldisilane represented by the general formula: [wherein, Vi: vinyl group, Me: methyl group, L: ligand] and disilacyclopentane. The only known examples are the palladium-catalyzed disproportionation reaction with ethanol and the platinum-catalyzed solvolysis reaction between monovinyldisilane and ethanol represented by the following formula (Advances in Organometall).
icChemistry, 19 (1981) 213
-255).

[Purpose of the invention]

An object of the present invention is to provide a novel disilacyclopentane compound useful as a crosslinking agent in molecular synthesis and as an intermediate in the synthesis of various compounds.

Another object of the present invention is to provide a method for producing the disilacyclopentane compound by a reaction that involves cleavage of the 5i-SL bond, but is completely different from the conventional reaction. .

[Structure of the invention]

The present invention provides two new substances represented by the following general formulas (I) and (If).

[In the formula, multiple R's may be the same or different,
Each represents a substituted or unsubstituted monovalent hydrocarbon group. ] Compounds of general formulas (1) and (II) are represented by general formula (■)
: [In the formula, R is the same as general formulas (1) and (II)] By reacting 1,2-divinylsilane in the presence of a platinum-based catalyst, produced as a dimerized product of the divinylsilane. be done.

The general formula CII [
) in the 1,2-divinylsilane, specific examples of R are:
Aliphatic hydrocarbon groups such as methyl, ethyl, propyl, butyl, vinyl, allyl; alicyclic hydrocarbon groups such as cyclohexyl, methylcyclohexyl, cyclopentyl; aromatic hydrocarbon groups such as phenyl, tolyl, xylyl, benzyl, etc. These may be substituted with halogens such as fluorine, chlorine, bromine and iodine, alkoxy groups, silyl groups, siloxy groups, etc.

The platinum-based catalyst used in the above production method is not particularly limited.
Examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum vinyl siloxane, platinum black, complexes of chloroplatinic acid and olefins or aldehydes, and in particular chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum vinyl siloxane. is highly active and preferred. The appropriate amount of platinum-based catalyst used in the reaction is 5-50 parts of platinum based on the entire reaction solution.
pm range. When the amount is less than 5 ppm, the reaction is slow and inefficient, and when it is more than 50 ppm, polymerization of the compound of general formula (I) will occur, resulting in a decrease in yield.

The above production method is usually carried out in an organic solvent, and preferred organic solvents include aliphatic hydrocarbons such as n-hexane, n-hebutane, and n-octane; aromatic hydrocarbons such as benzene, toluene, and xylene; and tetrahydrofuran. , dioxane, dibutyl ether, and other ethers. The amount of the solvent to be used is not particularly limited, but it is preferably 2 to 5 times (by weight) the amount of divinyldisilane of general formula (III) as a raw material. If the amount of solvent is too small, the yield of the target compound will decrease, and if it is too large, the reaction rate will decrease, resulting in a long reaction time, and the resulting compound of general formula (1) will polymerize, resulting in a decrease in the yield. descend.

The appropriate temperature for the reaction is about 50-200°C, preferably 80-14°C.
The temperature is in the range of 0°C, and the reaction is usually completed in 2 to 5 hours.

If the reaction temperature is too low, the reaction will take a long time, and moreover, the polymerization of the produced compound of general formula (T) will proceed, resulting in a decrease in yield. Even if the reaction temperature is too high, the produced compound of general formula (1) will polymerize, resulting in a decrease in yield. It is desirable that the reaction time be as short as possible within the necessary and sufficient range for one reaction to be completed within the above-mentioned appropriate temperature range.

Note that the reaction is preferably carried out under a dry inert atmosphere such as nitrogen or argon.

General formula (1
), (II) can be separated, for example, by flash distillation under vacuum, and according to this method, the compounds of general formulas (I) and (11) are separated as a mixture. For example, by subjecting the resulting mixture to preparative gas chromatography.

Each compound of general formula (1) and (II) can be isolated.

〔Example〕

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.

11L 1.2-divinyltetramethyldisilane 5 parts, toluene 20 parts, platinum-vinylsiloxane (platinum content 1%) 0.0
Charge 25 parts to a reactor purged with nitrogen gas.

A homogeneous solution was formed and the mixture was heated at 110° C. for 5 hours. Analysis of the reaction mixture obtained by gas chromatography revealed that the raw material, 1,2-divinyltetramethyldisilane, had completely disappeared and two types of compounds had been produced in equal amounts. The reaction mixture was subjected to flash distillation under vacuum to separate the product compounds as a mixture (total yield 9
0%). Next, this mixture of produced compounds was isolated into each peak component by preparative gas chromatography, and each compound was analyzed by NMR spectroscopy, gas chromatography-mass spectrometry (GC/
MASS) and elemental analysis. From the data obtained.

The product compound is 1,1,2,2-tetramethyl-3-
Vinyldimethylsilylmethyl-5-vinyldimethylsilyl-1,2-disilacyclopentane (hereinafter referred to as "compound (
i)” (yield 45%) and --61
, 1,3,3-tetramethyl-2-vinyldimethylsilylmethyl-4-vinyldimethylsilyl-1,3-disilacyclopentane (hereinafter abbreviated as compound (ii)) and (yield 45%). Ta. The analysis results are shown below.

NMR (CCI4) δppm Knee 0.42 to -0.04 (m, LH), 0.01 (
s, 12H).

0.20.0.16(d, 6H), 0.18(s,
6H), 0.40-1.38(m, 5t(), 5
．． 56-6.68 (m, 6H); GC/MASS
: 340 (M") ; Analysis elemental value: CHSi Measured value: 56.52 10.55 33.01 Theoretical value: 56.39 10.65 32.96 parts MR (
CC14) δppm Knee 0.04 to -0.42 (m, 2) 1), 0.02
(s, 24H).

0.40-1.16 (m, 4H), 5.56-6.
68 (m, 6H); GC/MASS: 340 (M
”) ; Element content value: CHSi Measured value: 56.29 10.64 32.67 Theoretical value: 56.39 10.65 32.96
The reaction was carried out in the same manner as in Example 1, except that a solution of 1a.6H20) in 2-ethylhexanol and a platinum content of 1% was used as a catalyst. The same two compounds obtained in Example 1 were obtained in the same yield as in Example 1.

Chisumu ■l The reaction was carried out in the same manner as in Example 1, except that xylene was used instead of toluene. The same results as in Example 1 were obtained. Furthermore, similar results were obtained when dioxane was used as the solvent.

The reaction was carried out in the same manner as in Example 1 except that the reaction temperature was changed to 60°C. The reaction hardly proceeded, with only a slight decrease in the starting compound disilazane.

Example 1 Using xylene as a solvent, the reaction temperature was set to 140°C (ii
) yield was 30%.

J [fresh] - The reaction was carried out in the same manner as in Example 1, except that the reaction time was changed to 48 hours. Compound (i) is not obtained, compound (ii)
The yield was about 45%.

The amount of platinum vinyl siloxane used as a catalyst was reduced to 0.
．． Two experiments were conducted in the same manner as in Example 1 except that the amounts were changed to 0.05 parts and 0.1 parts.

When the amount of catalyst was 0.005 parts, the amount of divinyldisilane as a raw material was reduced by only 5%.

When the catalyst amount is 0.1 part, the raw material divinyldisilane disappears, compound (i) is not obtained, and compound (it)
The yield was 20%.

〔Effect of the invention〕

Since the disilacyglopentane compound of the present invention has two vinyl groups in its molecule, it is useful as a crosslinking agent in polymer chemistry and as an intermediate raw material for producing various polymer compounds.

According to the production method of the present invention, a reversed disilacyclopentane compound can be produced easily and in high yield.

Patent Applicant: Shin-Etsu Chemical Co., Ltd. National Procedural Amendment (Koji) June 1986 φ Date Commissioner of the Patent Office Mr. Michibe Uga ■, Indication of Case: 1985 Patent Application No. 047098 2o Name of Invention: New Disilance Cyclopentane compound and its manufacturing method 3, relationship with asexuality of the person making the amendment Patent applicant address 2-6-1 Otemachi, Chiyoda-ku, Tokyo
Name Name (20B) Shin-Etsu Chemical Co., Ltd. Representative Yutabe Koita 4, Agent address 10th floor, Kojimachi Garden Building, 2-3 Kojimachi, Chiyoda-ku, Tokyo 102 (03) 237-19176
, Number of inventions increased by the amendment None 8. Contents of the amendment ■ The claims column is amended as per the attached sheet.

+1. The Detailed Description of the Invention column is amended as follows.

(1) Specification cylinder 3 Sadamigyo's following reaction equation shall be corrected as follows.

(2) "Molecular synthesis" on page 4, line 12 of the same book is corrected to "ζ polymer synthesis."

(3) In the same book, page 6, lines 2, 3 to 4, and line 6, "Divinylsilane J is corrected to rdivinyldisilane."

(4) The statement ``Moreover, it has been generated...(omitted)...decreases.'' from the bottom line of page 7 to the second line of page 8 of the same book is not practical. ” he corrected.

(5) "Even if it's too expensive" on page 8, line 2 of the same book.

ζIt's too expensive,'' he corrected.

(6) Add the following sentence next to "desirable" on page 8, line 6 of the same book.

1. This is because the polymerization of the compound of general formula (I) produced by long-term heating progresses and the yield decreases. ” (7) Same book, page 10, line 8 and second line from the bottom (7)
rNMR (CCl2) δppIIJ, 1'NMR (
CCIl, TMS external reference) (S, corrected to ppm month.

(8) "Disilazane" at the end of page 11 of the same book is corrected to "Disilane J."

(9) "ro, os section" on page 12, line 13 of the same book, [
), 005 copies.”

Claims rl) General formula (I) R II [In the formula, the R's present may be the same or different, and each represents a substituted or unsubstituted monovalent hydrocarbon group. ] A disilacyclobentane compound represented by:

. 2) A compound according to claim 1, wherein R
A compound where is a methyl group.

3) A disilacyclopentane compound represented by the general formula (II): H [wherein R is as defined in the general formula (1) above].

4) A compound according to claim 3, wherein R
A compound where is a methyl group.

5) General formula (■): [In the formula, R is as defined in the above general formula (1)] Consisting of reacting 1,2-divinyl disilane represented by the following in the presence of a platinum-based catalyst A method for producing a disilacyclopentane compound.

6) The method according to claim 5, wherein at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, and ethers is used as the reaction solvent.

7) The method according to claim 5, wherein the platinum-based catalyst is selected from chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum vinyl siloxane.

Claims (1)

[Claims] 1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (I) [In the formula, R present may be the same or different, and each R may be substituted or unsubstituted. represents a monovalent hydrocarbon group. ] A disilacyclopentane compound represented by 2) A compound according to claim 1, wherein R is a methyl group. 3) General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (II) [In the formula, R is as defined in the above general formula (I)] Disilacyclo represented by pentane compound. 4) A compound according to claim 3, wherein R is a methyl group. 5) General formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) [In the formula, R is as defined in the above general formula (I)] 1,2- A method for producing a disilacyclopentane compound, which comprises reacting divinylsilane in the presence of a platinum-based catalyst. 6) The method according to claim 5, wherein at least one organic solvent selected from aliphatic hydrocarbons, aromatic hydrocarbons, and ethers is used as the reaction solvent. 7) The method according to claim 5, wherein the platinum-based catalyst is selected from chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum vinyl siloxane.