JPH06116278A - Cycloalkenylalkylsilane - Google Patents

Abstract

PURPOSE:To obtain a new high-purity cycloalkenylalkylsilane. CONSTITUTION:A cycloalkenylalkylsilane expressed by the formula R1(CH2)nSi(R<2>)H2 [R<1> is 6-8C cyclic hydrocarbon group having one unsaturated double bond; R<2> is 1-4C alkyl group; (n) is integer of 0-2], e.g. 5-norbornen-2-yl- methylsilane. This compound can readily be produced by reducing a dichlorosilane expressed by the formula R1-(CH2)n-Si(R<2>)Cl2 using a reducing agent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel organosilicon compound, cycloalkenylalkylsilane.

[0002]

Conventionally, an alkenylsilane having three hydrogen atoms represented by SiH ₃ (simply referred to as alkenylsilane) has been known (JP-A 1-222138).
No. 3), a cycloalkenylalkylsilane having two bulky cyclic hydrocarbon groups having two hydrogen atoms, an alkyl group, and one double bond as represented by SiH _2. Has not been done. The alkenylsilane is generally produced by substituting a hydrogen atom of monosilane represented by SiH ₄ as a raw material with an alkyl group.

[0003] However, gaseous monosilane has a drawback that it is not safe because it is difficult to handle in production and spontaneously ignitable or explosive. Also,
Monoalkenylsilane can be easily produced by hydrosilating monosilane once. On the other hand, cycloalkenylalkylsilane is
Although it can be produced by further introducing an alkyl group into the obtained monoalkenylsilane, it is difficult to introduce only one alkyl group, so that it is difficult to produce a pure product. It was

[0004]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned drawbacks, and as a result, by reducing dichlorosilane, a novel and highly pure cyclic hydrocarbon group having a bulky structure has been obtained. The present inventors have found that a cycloalkenylalkylsilane that is easy to manufacture can be easily produced and reached the present invention. Therefore, it is an object of the present invention to provide a novel cycloalkenylalkylsilane of high purity.

[0005]

The above objects of the present invention are as follows.
Was achieved by ^{_{R 1 ─ (CH 2) n}} ─Si (R 2) cycloalkenylalkyl silane represented by H _2. However, in the above formula, R ¹ has one unsaturated double bond, a cyclic hydrocarbon group having 6 to 8 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and n is It is an integer of 0 to 2. Among these compounds, a cycloalkenylalkylsilane in which R ¹ is a group represented by Chemical Formula 3 or 4 below, R ² is a methyl group, and n is 0 or 2 is preferable.

[0006]

[Chemical 3]

[Chemical 4] In the above formula, R ¹ has one unsaturated double bond and is a cyclic hydrocarbon group having 6 to 8 carbon atoms, and R ² is 1 to 1 carbon atoms.
The alkyl group of 4 and n are integers of 0-2.

The above R ^1- (CH ₂ ) _n --Si (R ² )
The cycloalkenylalkylsilane represented by H ₂ (hereinafter referred to as the cycloalkenylalkylsilane of the present invention) is
R ^1- (CH ₂ ) _n --Si (R ² ) Cl ₂ represented by dichlorosilane (hereinafter simply referred to as dichlorosilane)
It can be easily produced by reducing with a reducing agent.

The reduction reaction is carried out in a non-solvent system or in a solvent,
It can be performed by adding a reducing agent to dichlorosilane. Examples of the solvent that can be used include aliphatic hydrocarbons and aromatic hydrocarbons, and ether solvents such as ethyl ether, butyl ether and tetrahydrofuran are particularly preferable.

The reducing agent that can be used is not particularly limited, but metal hydrogen complex salt compounds such as lithium aluminum hydride, sodium borohydride and lithium borohydride are particularly preferable. The amount of the reducing agent used is preferably in the range of 1.0 to 2.0 mol, and particularly preferably in the range of 1.1 to 1.3 mol, based on 1 mol of dichlorosilane. The excess reducing agent can be treated by adding ethyl acetate, dilute hydrochloric acid or the like to the reaction system after the reaction is completed.

The reaction temperature is preferably in the range of -60 ° C to 60 ° C, particularly preferably in the range of -20 ° C to 30 ° C. The obtained reaction product can be easily isolated by distillation or the like, and thus the cycloalkenylalkylsilane of the present invention can be obtained in high yield and high purity.

Since the cycloalkenylalkylsilane of the present invention has a double bond excellent in reactivity and also has a SiH group having an addition reactivity, it is copolymerized with olefins such as ethylene and propylene through the double bond. In addition to being capable of effecting the crosslinking reaction of SiH groups in the presence of water using light or a metal catalyst, a silylating agent or a silane coupling agent for imparting various functions to an olefin polymer. Is useful as

[0012]

INDUSTRIAL APPLICABILITY The cycloalkenylalkylsilane of the present invention is a cycloalkenylalkylsilane of extremely high purity because it is produced by reducing dichlorosilane. Further, the cycloalkenylalkylsilane of the present invention uses liquid dichlorosilane as a raw material, which is easy to handle, has no explosive properties, and is excellent in safety, and therefore has a high yield and is extremely easy to produce. Alkenyl silane.

[0013]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Example 1. A 500 ml flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 11.0 g of lithium aluminum hydride (LiAlH ₄ ) and 150 ml of dry tetrahydrofuran, and -20 to 3
After cooling to 0 ° C, dry tetrahydrofuran 50m
A solution in which 100 g of 5-norbornen-2-yl-methyldichlorosilane was dissolved was added dropwise to 1 liter, and the reaction was carried out at a temperature condition of 20 to 25 ° C. for 2 to 3 hours.

To the obtained reaction solution, 150 ml of a 10 wt% HCl aqueous solution was added dropwise over 1 hour to obtain an excess of LiAL.
H ₄ was treated. Next, the reaction solution was washed several times with water, tetrahydrofuran was transferred to the aqueous phase, and then the organic phase was separated.
The obtained organic phase was distilled to obtain 53 g of a colorless transparent liquid having a boiling point of 65 ° C. under a pressure of 41 mmHg. When the obtained liquid was analyzed by gas chromatography, it was confirmed that the liquid was a single component.

The obtained liquid has a molecular ion peak (M / Z = 13) by gas chromatography mass spectrometry.
8), ¹ H-NMR spectrum (Table 1), infrared absorption spectrum (FIG. 1), refractive index at 25 ° C. (1.4764) and specific gravity at 25 ° C. (0.885) are represented by the following chemical formula 5. It was confirmed to be 5-norbornen-2-yl-methylsilane. The isolated yield was 79%.

[Chemical 5]

[0017]

[Table 1]

Example 2. Instead of the 5-norbornene-2-yl-methyldichlorosilane used in Example 1, 1
-(3-hexen-1-yl) -2-methyldichlorosilylethane was used in the same manner as in Example 1 except that 4
55.6 g of a colorless transparent liquid having a boiling point of 42 ° C. under a pressure of mmHg was obtained.

When the obtained liquid was analyzed by gas chromatography, it was confirmed that the liquid was a single component. The obtained liquid has a molecular ion peak (M / Z = 15) by gas chromatography mass spectrometry.
4), ¹ H-NMR spectrum (Table 2), infrared absorption spectrum (FIG. 1), refractive index at 25 ° C. (1.4666) and specific gravity at 25 ° C. (0.838). It was confirmed to be 1- (3-hexen-1-yl) -2-methylsilylethane. The isolation yield is 80%
Met.

[Chemical 6]

[0020]

[Table 2]

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the liquid obtained in Example 1.

FIG. 2 is an infrared absorption spectrum diagram of the liquid obtained in Example 2.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuyuki Matsumura 1 Hitomi, Osamu, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (3)

[Claims] ^1. A cycloalkenylalkylsilane represented by R 1-(CH ₂ ) _n --Si (R ² ) H ₂ ; wherein R ¹
Is a cyclic hydrocarbon group having one unsaturated double bond and having 6 to 8 carbon atoms, R ² is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 2. . 2. The cycloalkenylalkylsilane according to claim 1, wherein R ¹ is a group represented by the following chemical formula 1, R ² is a methyl group and n is 0. [Chemical 1] 3. The cycloalkenylalkylsilane according to claim 2, wherein R ¹ is a group represented by the following chemical formula 2, R ² is a methyl group and n is 2. [Chemical 2]