JP3427144B2 - Method for producing 3-chloropropylsilanes - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 3-chloropropylsilanes useful as a silane coupling agent and as a raw material for producing various silicon compounds.

[0002]

2. Description of the Related Art It is known that 3-chloropropylsilanes are useful as raw materials for producing silane coupling agents and various silicon compounds. 3-Chloropropylsilanes are usually obtained by a hydrosilylation reaction represented by the following formula A.

[0003]

[Chemical 1]

Specifically, allyl chloride and hydrosilanes are reacted in the presence of various catalysts or radical initiators,
3-Chloropropylsilanes are produced. For hydrosilylation of allyl chloride, platinum catalysts such as chloroplatinic acid in isopropyl alcohol (Speier's) are commonly used.
(Catalyst) is used. However, when a platinum catalyst is used, reduction of allyl chloride as shown in the following formula B occurs at the same time and the yield of 3-chloropropylsilanes decreases.

[0005]

[Chemical 2]

Conventionally, in order to reduce the rate of the reduction reaction represented by the above formula B, a system in which an additive which becomes a ligand is added to a platinum compound, or a platinum complex catalyst in which a ligand is bound in advance is used. Is being developed. As typical examples of such a ligand, amine compounds such as tributylamine and organic phosphorus compounds such as triphenylphosphine are known.

Further, JP-A-60-52159 discloses a catalyst in which s-butylamine and platinum tetrachloride are combined. Czechoslovakian Patent No. 176909 of 1979 describes a catalyst in which tributylamine or dimethylaniline and chloroplatinic acid are combined. Further, Japanese Patent Publication No. 56-29873 discloses a combination of phenothiazine and chloroplatinic acid.

Further, Cuihua Xuebao 19
1989, Vol. 10, No. 2, p. 213, there is a report that a mixture of chloroplatinic acid and triphenylphosphine in a ratio of 1: 1 is used as a catalyst. Czechoslovak Patent 1979 1
Japanese Patent No. 76910 discloses a catalyst in which 1,2-bis (diphenylphosphino) ethane and chloroplatinic acid are combined. Polish Patent 1992 No. 1562
No. 41 discloses that bis (triphenylphosphine) (ethylene) platinum (0) is used as a platinum complex catalyst. Further, in JP-A-55-145693, dichlorobis (triphenylphosphine) is disclosed.
A synthetic method using platinum (II) is described.

[0009]

With the catalysts described in the above publications, no matter which catalyst is used, the yield of 3-chloropropylsilanes is higher than that when a platinum catalyst without an additive is used. The rate will improve somewhat. However, since the rate of reduction reaction is still large, the various catalysts described in the above publications are not satisfactory.

There is a method of adding a radical initiator as a method for carrying out hydrosilylation without using a platinum catalyst. However, in the radical reaction, various by-products are formed by an unintended chain reaction, so that the purpose is The yield of 3-chloropropylsilanes, which is a product, does not increase.

Since 3-chloropropylsilanes are very useful compounds as basic raw materials for various silane coupling agents, a slight improvement in yield is a great industrial advantage. For this reason, the development of a catalyst that can obtain 3-chloropropylsilanes in a higher yield than before has been awaited.

The present invention has been made to solve the above problems, and when hydrolyzing allyl chloride, the rate of the reduction reaction, which is a side reaction, is suppressed to a low level, and 3-chloropropylsilanes are produced in good yield. The purpose is to provide a method of doing.

[0013]

Means for Solving the Problems and Modes for Carrying Out the Invention The present inventor has conducted extensive studies to achieve the above object, and as a result, in the case of carrying out hydrosilylation reaction of allyl chloride and hydrosilanes in the presence of a platinum catalyst. , The following general formula (1) R ¹ R ² N (CH ₂ ) _n OR ³ (1) (In the formula, R ¹ and R ² represent a hydrogen atom or an alkyl group, and R 1
¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom or an acetyl group. n is an integer of 2-10. ) By adding and reacting the amino alcohol derivative, the reduction reaction of the above formula B is suppressed,
The present inventors have found that 3-chloropropylsilanes can be produced in high yield and have completed the present invention.

The present invention will be described in more detail below. In the method for producing 3-chloropropylsilanes of the present invention, allyl chloride and hydrosilanes are mixed with a mixture of an aminoalcohol derivative of the above formula (1) and a platinum catalyst. It is a reaction in the presence.

Here, hydrosilanes are used as reaction substrates, and specifically, HSiX such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and the like.
₃ , HSiRX ₂ , HSiR ₂ X, HSiR _{3 and the} like can be mentioned. In addition, X is a halogen atom such as a chlorine atom, R is a monovalent carbon atom such as an alkyl group, an alkenyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms, particularly 1 to 6 unsubstituted or substituted (halogen substitution). Hydrogen radicals can be used.

The amount of the above-mentioned hydrosilanes used is preferably 0.9 to 1.4 equivalents, particularly equimolar to allyl chloride.

Examples of platinum catalysts include platinum compounds, platinum complex compounds, platinum-supported catalysts and the like.
Specifically, the platinum compound is chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, etc., the platinum complex compound is dichloro (1,5-cyclooctadiene) platinum, etc., and the platinum-supported catalyst is activated carbon or It is supported on silica gel, alumina or the like. The amount of platinum catalyst added is a catalytic amount, and is usually 1 × 10 6 with respect to allyl chloride as platinum atoms.
^-6 to 1 x 10 ^-2 equivalent.

In the present invention, the following general formula (1) R ¹ R ² N (CH ₂ ) _n OR ³ (1) (wherein R ¹ and R ² represent a hydrogen atom or an alkyl group, R 1
¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom or an acetyl group. n is an integer of 2-10. ) Used as a mixture with the amino alcohol derivative represented by

Here, the alkyl group has 1 to 1 carbon atoms.
10, especially 1 to 6, are preferable, and a primary alkyl group (straight chain alkyl group) is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group and an n-butyl group.

Examples of amino alcohol derivatives include 2-dimethylaminoethyl acetate, 2-diethylaminoethyl acetate, 3-dimethylaminopropyl acetate, 3-diethylaminopropyl acetate, 4
-Dimethylaminobutyl acetate, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylaminopropanol. Among these, 2-dimethylaminoethyl acetate, 3-dimethylaminopropyl acetate and dimethylaminoethanol are preferable, and 2-dimethylaminoethyl acetate and 3-dimethylaminopropyl acetate are particularly preferable.

The above amino alcohol derivative, when mixed with a platinum catalyst, coordinates with a platinum atom to form a complex catalyst. The amount of the amino alcohol derivative added is usually 0.1 to 10 equivalents, and particularly 0.3 to 10 equivalents, relative to the platinum atoms of the platinum catalyst.
When the platinum catalyst is chloroplatinic acid, for example, 0.1 equivalent to the number of moles of platinum atom contained.
5 equivalents, particularly 0.3 to 2 equivalents are preferred. As the amino alcohol derivative, one prepared by mixing with a platinum catalyst in advance is used, or preferably mixed in a reaction vessel before use.

The 3-chloropropylsilanes are obtained by reacting allyl chloride with hydrosilanes in the presence of a mixture of an aminoalcohol derivative and a platinum catalyst. Specifically, it is preferable to obtain the 3-chloropropylsilanes by adding an aminoalcohol derivative and a platinum catalyst to allyl chloride and then dropping hydrosilanes in a normal pressure system or a pressurized system. Alternatively, allyl chloride and hydrosilanes may be charged all at once, and then the mixture of the amino alcohol derivative and the platinum catalyst may be added and stirred. At the time of this reaction, a solvent inert to hydrosilylation, such as toluene, xylene, or tetrahydrofuran, can be used, but it is preferably carried out without a solvent in consideration of productivity.

Reacting allyl chloride with hydrosilanes
The temperature is 30 to 200 ° C, especially 40 to 150 ° C.
Is preferred. If the temperature is out of the above range, the reaction rate will increase.
It may slow down or the side reaction rate may increase.
It Reaction mixture from room temperature (allyl chloride and hydrosilanes
It is preferable to carry out in the range of the reflux temperature of (mixture with). Anti
Response pressure is 10kg / cm from atmospheric pressure² (Gauge pressure)
It is preferable to carry out.

[0024]

EFFECTS OF THE INVENTION According to the present invention, the rate of reduction reaction of allyl chloride, which is a side reaction, becomes low, which is industrially advantageous.
-Chloropropylsilanes can be produced in good yield.

[0025]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1 A 200 ml four-neck glass flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the inside of the flask was replaced with nitrogen. Allyl chloride 38.3g
(0.5 mol), dimethylaminoethyl acetate 0.7 μl (0.01 mmol), 2-ethylhexanol solution of chloroplatinic acid (platinum content 2% by weight) 0.098
g (platinum amount 0.01 mmol) was charged into the flask. The reflux condenser was flushed with brine at -15 ° C before heating the flask. After raising the temperature in the flask to 45 to 46 ° C., trichlorosilane 6 was added from the dropping funnel.
7.7 g (0.5 mol) was dropped into the flask over 6 hours. The dropping was completed while heating the reaction mixture so that it gently refluxed, and the mixture was aged for 1 hour while maintaining gentle reflux. After cooling the mixture in the flask to room temperature,
Toluene 10.0g was added and the obtained reaction product was analyzed by gas chromatography. In addition, all the reaction operations were performed under a nitrogen atmosphere.

The yield of 3-chloropropyltrichlorosilane determined using toluene as an internal standard was 72.8%.

Comparative Example 1 Tributylamine 9.3 mg (0.05 mmo) instead of dimethylaminoacetate
After carrying out other operations using l) under the same conditions as in Example 1, the reaction product finally obtained was analyzed by gas chromatography. The yield of 3-chloropropyltrichlorosilane was found to be It was 67.6%.

[Comparative Example 2] The reaction was carried out without adding dimethylaminoethyl acetate, and the reaction was not completed. Therefore, the aging time was set to 3 hours, and the other operations were carried out under the same conditions as in Example 1. After that, when the reaction product was analyzed by gas chromatography, the yield of 3-chloropropyltrichlorosilane was 65.3%.

Example 2 A 200 ml four-neck glass flask was equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the inside of the flask was replaced with nitrogen. Allyl chloride 38.3g
(0.5 mol), dimethylaminoethyl acetate 1.4 μl (0.02 mmol), 2-ethylhexanol solution of chloroplatinic acid (platinum content 2% by weight) 0.098
g (platinum amount 0.01 mmol) was charged into the flask. The reflux condenser was flushed with brine at -15 ° C before heating the flask. After raising the temperature in the flask to 45 to 46 ° C., 57.5 g (0.5 mol) of methyldichlorosilane was dropped into the flask from the dropping funnel over 6 hours. The dropping was completed while heating the reaction mixture so that it gently refluxed, and the mixture was aged for 1 hour while maintaining gentle reflux. After cooling the mixture in the flask to room temperature, 10.0 g of toluene was added, and the obtained reaction product was analyzed by gas chromatography. In addition, all the reaction operations were performed under a nitrogen atmosphere.

The yield of 3-chloropropylmethyldichlorosilane determined using toluene as an internal standard was 70.6%.

[Comparative Example 3] 9.3 mg (0.05 mmo) of tributylamine instead of dimethylaminoacetate
After carrying out the other operations under the same conditions as in Example 2 using l), the finally obtained reaction product was analyzed by gas chromatography to find that the yield of 3-chloropropylmethyldichlorosilane was Was 62.3%.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toru Kubota Toru Kubota 28-1 Nishi-Fukushima, Nishikufukushima, Nakakubiki-gun, Niigata Pref. 28-1 Nishi-Fukushima 28-1 Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Center (72) Inventor Ayumu Kiyomori 28-1 Nishi-Fukushima, Fukushima, Nakakubiki-gun, Niigata Shin-Etsu Chemical Co., Ltd. Synthetic Technology Research Center (56) References JP-A-51-95023 (JP, A) JP-A-55-145693 (JP, A) JP-A-56-103187 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07F 7/12 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. Allyl chloride and hydrosilanes are represented by the following general formula (1) R ¹ R ² N (CH ₂ ) _n OR ³ (1) (wherein R ¹ and R ² are hydrogen atoms or alkyl groups). Show, R
¹ and R ² may be the same or different from each other. R ³ represents a hydrogen atom or an acetyl group. n is an integer of 2-10. ) A method for producing 3-chloropropylsilanes, which comprises reacting in the presence of a mixture of an aminoalcohol derivative represented by the formula 4) and a platinum catalyst. 2. The method according to claim 1, wherein the amino alcohol derivative is dimethylaminoethyl acetate or dimethylaminopropyl acetate.
Method for producing chloropropylsilanes.