JPS6126791B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an advantageous process for producing silicon compounds having a vinyloxy group bonded to a silicon atom.

A method for producing a silicon compound having a vinyloxy group bonded to a silicon atom is described in Japanese Patent Publication No. 42-16611.
The method described in Japanese Patent Publication No. 42-23567 is known. The method disclosed in Japanese Patent Publication No. 42-235671 involves reacting a silicon chloride compound with metallic sodium and acetone when producing an isopropenoxy silicon compound from a silicon chloride compound. This method has the major disadvantages of using metallic sodium, which is difficult to handle industrially, and of generating a large amount of hydrogen gas during the reaction, which is dangerous in factory operations. The method disclosed in Japanese Patent Publication No. 42-16611 involves reacting a silicon compound having a chlorine atom bonded to a silicon atom with an aldehyde or ketone having an enolizable carbonyl group in the presence of zinc chloride and a free hydrogen chloride binding agent. be.

In producing a silicon compound having a vinyloxy group bonded to a silicon atom by reacting a silicon chloride compound with an aldehyde or ketone having an enolizable carbonyl group in the presence of a dehydrochlorination agent, the present inventors By having one or more substances selected from metallic copper and copper compounds present in the reaction system, the reaction is completed more quickly and fewer by-products are produced than when zinc chloride is used. We have discovered that it is possible to advantageously produce products with high purity.

For example, using acetone, triethylamine and vinyltrichlorosilane in the proportions described in Example 1, adding vinyltrichlorosilane to
^The same 0.675×
When the same reaction was carried out with the addition of 10 ^-2 times the mole of cupric chloride, the composition of the reaction solution 20 hours after the start of the reaction was examined, and in both cases, the starting material vinyltrichlorosilane was almost completely removed. However, the ratio of the concentrations of vinyltriisopropenoxysilane, the target product, and vinyldiisopropenoxychlorosilane, its precursor (percentage ratio of vinyldiisopropenoxychlorosilane to vinyltriisopropenoxysilane) is 5% for zinc chloride and 0.15 for cupric chloride.
It was %. Also, using zinc chloride to achieve this ratio of 0.15% requires more than 40 hours.
In this way, when zinc chloride is used, the conversion of vinyl diisopropenoxychlorosilane to vinyl triisopropenoxysilane is slower than when copper chloride is used, and therefore, vinyl diisopropenoxychlorosilane is less likely to be mixed into the product. The amount of oxychlorosilane increases, which is disadvantageous in terms of use, as it causes a large chlorine content when vinyltriisopropenoxysilane is used as a raw material for a sealant, for example. In addition, in the above reaction, zinc chloride was used to adjust the concentration ratio of vinyltriisopropenoxysilane and vinyldiisopropenoxychlorosilane in the reaction product to 0.15 20 hours after the start of the reaction.
% or less, it is necessary to carry out the reaction in an autoclave at high temperature and pressure, but when copper or a copper compound is used as a catalyst, the reaction can be carried out for several hours under the same temperature and pressure conditions. The reaction is completed. In this way, using copper or a copper compound as a catalyst allows the reaction to proceed more quickly and easily than when using zinc chloride, and when zinc chloride is used, the reaction proceeds without using an autoclave. By using copper or copper compounds, reactions that are difficult to complete or require a very long time to complete can be easily carried out under normal pressure, and even more quickly if carried out at high temperature and pressure. The reaction can be completed. Moreover, when zinc chloride is used, the product contains many colloidal suspensions in the form of white pellets, and these suspensions are difficult to separate and remove even by filtration or rectification. Furthermore, when zinc chloride is used in a reaction using acetone as a compound having a carbonyl group, medityl oxide is produced as a by-product, which causes an off-flavor to the product. These drawbacks observed when using zinc chloride are not observed at all when using metallic copper or copper compounds, and this is likely due to the reaction proceeding by completely different reaction mechanisms in both cases. Conceivable.

Examples of the silicon chloride compound used in the present invention include, but are not limited to, the following substances. Examples of inorganic silicon chloride compounds include tetrachlorosilane and trichlorosilane. In the organosilicon chloride compound, the organic groups can be of the same type or different types when plural, such as alkyl, cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy or aralkoxy groups, They can have substituents that do not interfere with the reaction of the invention. For example, organic trichlorosilanes include methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, etc.; organic dichlorosilanes include methyldichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, etc.
Divinyldichlorosilane, methylphenyldichlorosilane, methylvinyldichlorosilane, etc.; organic monochlorosilanes such as trimethylchlorosilane, triethylchlorosilane, trivinylchlorosilane; organic silicon chloride compounds containing substituents such as chloropropyltrichlorosilane, trifluoropropyl trichlorosilane; These include chlorosilane, methyltrifluoropropyldichlorosilane, and the like. Furthermore, like the above-mentioned chloromonosilanes, chlorodisilanes, bis(chlorosilyl)alkanes, and chlorosiloxanes can also be used as raw materials in the method of the present invention.

The following compounds can be used as aldehydes and ketones that can be enolized, but are not limited to these. Linear aliphatic aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, enantylaldehyde, etc. Branched aliphatic aldehydes include isobutyraldehyde, isovaleraldehyde, etc. Cyclic aldehydes include hexahydrobenzaldehyde, methylhexahydrobenzaldehyde, and saturated aliphatic monoketones As acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl nonyl ketone, etc., acetylacetone as aliphatic polyketone,
Ketones with aromatic groups such as acetonyl acetone include acetophenone, propiophenone, benzylacetone, etc.; cyclonones include cyclopentanone, methylcyclopentanone, cyclohexanone, and methylcyclohexanone; ketone esters include ethyl acetoacetate, α-ethylene; As the aldehyde, crotonaldehyde, β-ethyl acrolein, β・β-dimethylacrolein, β-propyl acrolein, β-butyl acrolein, dihydro-6,7-citral, tigrinaldehyde, α・β-dimethylacrolein, citral, vinyl Crotonaldehyde, falnesal, sorbital, etc., α-ethylenic ketones such as ethylidene acetone, propylidene acetone, butylidene acetone, isobutylidene acetone, medityl oxide, holon, cyclobent-1-en-3-one, cyclohex-1-
These include en-3-one, isophorone, carvone, carbonene, and α-ionone.

As the dehydrochlorination agent used in the present invention, organic bases such as tertiary amines are used. In particular, triethylamine is widely available due to its ease of availability. The amount of neutralizing agent used is the amount necessary for neutralization or
A small excess may be sufficient, but a large amount may also be used.
When using more than the amount necessary for neutralization, it is desirable to use a dialkylaniline having a higher boiling point than in the case of a low-boiling point target product, for example, in order to widen the boiling point of the target product and the boiling point of the neutralizing agent. It is also possible to use heterocyclic tertiary amines such as pyridine, quinoline or derivatives thereof.

When these dehydrochlorination agents are used, the reaction system becomes thick and gruely due to the precipitation of a large amount of hydrochloride produced by the reaction. Therefore, in order to facilitate the dispersion, an inert solvent (eg benzene, toluene, etc.) may be added to the reaction system as a diluent. The purpose of dilution can also be achieved by using an excess of aldehydes or ketones as raw materials or amines as dehydrochlorination agent.

The metallic copper used in the present invention is preferably used in the form of a large surface area, such as copper powder. Copper in the copper compound may be monovalent or divalent. . Copper compounds include copper oxides such as cuprous oxide,
Contains copper hydroxide and copper salts. Examples of copper compounds include copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate, copper carbonate, basic copper carbonate, copper formate, copper acetate,
Examples include, but are not limited to, copper butyrate. These salts may contain water of crystallization and may be double salts or chain salts.
The amount of these metallic copper or copper compound salts used is not particularly limited. As the amount of these compounds used increases, the reaction speeds up, so the amounts used can be appropriately selected depending on the difficulty in proceeding with the reaction due to the combination of the silicon chloride compound and the aldehydes or ketones.

As is clear to those skilled in the art from the examples of the present invention and the known art, the vinyloxy group as used herein refers to an etheric vinyl bond-containing group, that is, one of the valences of its oxygen atom is a substituted or unsubstituted vinyl group. It refers to the attached ether functionality.

Next, examples of the present invention will be shown.

Example 1 The flask from 1 is equipped with a stirrer, a reflux condenser (with drying tube), a thermometer, and a dropping funnel.
207 g of acetone, 222 g of triethylamine, and 1 g of cuprous chloride are placed in a flask, and 89 g of vinyltrichlorosilane is added from the dropping funnel. Reflux for 20 hours while stirring (reflux temperature 60-63°C). The reaction mixture is filtered, washed with acetone to remove triethylamine hydrochloride, and filtered. After the combined liquid is distilled to remove the solvent, the remaining liquid is subjected to vacuum distillation. 87 g of vinyltriisopropenoxysilane are obtained as a colorless and transparent liquid. bp70~72℃/10mm
Hg.

Example 2 Except for replacing cuprous chloride with 1 g of cupric chloride,
The same operations as in Example 1 are performed to obtain similar results. Chlorine content of the distillate is 0.019%.

Example 3 The same procedure as in Example 1 is carried out except that 1.2 g of copper sulfate is used instead of cuprous chloride. 85 g of vinyltriisopropenoxysilane are obtained.

Example 4 The same procedure as in Example 1 is carried out except that 1.35 g of copper acetate is used instead of cuprous chloride. Colorless and transparent vinyltriisopropenoxysilane is obtained.

Example 5 Example 1 except that cuprous chloride was replaced with 1 g of copper powder
Perform the same operation as . 89 g of vinyltriisopropenoxysilane are obtained.

Example 6 50 g of trimethylchlorosilane is added to a mixture of 50 g of cyclohexanone, 0.3 g of cupric chloride, and 68 g of triethylamine, and the mixture is refluxed. Benzene is added to the gruel-like reaction mixture, removed from the flask and filtered. Furthermore, the hydrochloride was washed with benzene, and the solvent was distilled off from the combined solution to obtain 45 g of 1-cyclohexenyloxy-trimethylsilane. bp29-30℃/1mmHg.

Example 7 207 g of acetone, 222 g of triethylamine and 3 g of cupric chloride are placed in flask 1, and 71 g of dimethyldichlorosilane is added from a dropping funnel.
Reflux for 13 hours. Obtain 52 g of colorless and transparent dimethyldiisopropenoxysilane. bp58℃/6mm
Hg.

Example 8 The procedure of Example 7 was repeated except that 71 g of dimethyldichlorosilane was replaced with 82 g of methyltrichlorosilane and the mixture was refluxed for 20 hours. 72 g of methyltriisopropenoxysilane are obtained as a clear colorless liquid.
bp83-84℃/21mmHg. Chlorine content 0.020%.

Example 9 116.6 g of phenyltrichlorosilane is added from a dropping funnel to a mixed solution of 207 g of acetone, 222 g of triethylamine, and 3 g of cupric chloride. Reflux for 40 hours with stirring. After work-up, 92 g of phenyltriisopropenoxysilane are obtained. bp97~98
℃/2mmHg.

Example 10 Acetophenone 132g, triethylamine 74.5g
Add 35.6 g of dimethyldichlorosilane to a mixture of g and 0.5 g of cuprous chloride. Reflux for 2.5 hours (reflux temperature 66-68°C). The reaction mixture is filtered, washing the hydrochloride with benzene, and the liquid is evaporated. The residual liquid was distilled under reduced pressure to obtain transparent dimethyl-bis(1-phenyl-1-ethenyloxy).
Obtain 60 g of silane. bp148-152℃/2mmHg.

Example 11 Add tetrachlorosilane to a mixed solution of 276 g of acetone, 296 g of triethylamine, and 3 g of cupric chloride.
Drop 93.6g over 1 hour. After the dropwise addition is completed, the temperature is slowly raised and refluxed for 25 hours. The reaction mixture is filtered and the hydrochloride is washed with acetone and the solvent is removed from the solution. The residual liquid was subjected to vacuum distillation to obtain 70 g of transparent tetraisopropenoxysilane. b.
p.59-60℃/2mmHg.

Example 12 116.8 g of chloropropyltrichlorosilane [Cl(CH ₂ ) ₃ SiCl ₃ ] is added to a mixed solution of 207 g of acetone, 222 g of triethylamine, and 2 g of cuprous chloride. Reflux for 28 hours. After the post-treatment, 95 g of transparent and colorless chloropropyltriisopropenoxysilane are obtained. bp110-113℃/5mmHg.

Example 13 256 g of isobutyraldehyde, 1 g of cuprous chloride
82 g of methyltrichlorosilane was added dropwise to a mixed solution of 200 g of triethylamine over 1 hour.
After refluxing, toluene is added to the gruel-like reaction mixture and taken out. After overwashing and distilling off the solvent from the liquid, it is subjected to vacuum distillation. Tris-(2-methyl-1
107 g of -propenyloxy)methylsilane are obtained. bp100-105℃/9mmHg.

Example 14 The autoclave of 1 was charged in the same manner as in Example 2, and reacted at 110 to 120°C for 4 hours. 82 g of colorless and transparent vinyltriisopropenoxysilane was obtained.

Claims (1)

[Claims] 1. In producing a silicon compound having a vinyloxy group bonded to a silicon atom by reacting a silicon chloride compound with an aldehyde or ketone having an enolizable carbonyl group in the presence of a dehydrochlorinating agent, metallic copper and 1. A method for producing a silicon compound having a vinyloxy group bonded to a silicon atom, which comprises causing one or more substances selected from copper compounds to be present in the reaction system.