JP2017124976A - Method for producing 1,2-bis(silyl)ethylene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an efficient method for producing a 1,2-bis(silyl)ethylene compound, which makes it possible to obtain a 1,2-bis(silyl)ethylene compound in an excellent yield by a reaction in a non-closed system.SOLUTION: There is provided a method for producing a 1,2-bis(silyl)ethylene compound represented by the general formula (2) by reacting a vinylsilane compound represented by the general formula (1) in a solvent in the presence of a ruthenium catalyst (in the general formula (1), Rand Reach independently represent a substituted or unsubstituted C1-C20 monovalent hydrocarbon group, and n is an integer of 0, 1 or 2; and in the general formula (2), R, Rand n are the same as in the general formula (1)). The method uses, as the solvent, an organooxysilane compound (excluding the vinylsilane compound of the formula (1)).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a 1,2-bissilylethylene compound, and more specifically, an efficient 1,2-bissilylethylene compound in which a vinylsilane compound is reacted in a predetermined solvent in the presence of a catalyst. It relates to a manufacturing method.

1,2-bissilylethylene compounds are compounds useful as silane coupling agents, raw materials for organic silica hybrid materials, etc., and are known to be obtained by metathesis reaction of vinylsilane compounds in the presence of a catalyst. .
Specifically, as a process for producing 1,2-bis (triethoxysilyl) ethylene, vinyltriethoxysilane is reacted under reflux in a state of being sealed in a Schlenk tube in the presence of Grubbs first generation catalyst. A technique is known (Non-Patent Document 1).
Also known is a method of performing a disproportionation reaction of triethoxysilane using benzene or toluene as a solvent in the presence of a ruthenium catalyst and sealed in a Schlenk flask (Patent Document 1).

On the other hand, in a non-sealed production method, Ru ₃ (CO) ₁₂ is used as a catalyst in a benzene solvent, vinyltriethoxysilane is heated to about 80 ° C. in the presence of triphenylsilane, and the reaction solution is not refluxed. A method of reacting is known (Non-Patent Document 2).
Also known is a method in which an ionic liquid is used as a solvent and a RuH (CO) (PCy ₃ ) ₂ catalyst is used and the reaction solution is reacted at 130 ° C. without refluxing (Non-Patent Documents 3 and 4).

However, since each of the above-mentioned production methods is a method in which a vinylsilane compound, a catalyst, and a solvent used as necessary are charged and reacted at the same time, there may be a case where reaction is suddenly caused and reaction control becomes difficult. Industrial implementation is difficult.
In addition, in order to produce a 1,2-bissilylethylene compound industrially safely by the method of patent document 1, although adding a vinylsilane compound and making it react in the solvent containing a catalyst, it is conventional. In a system using an organic solvent such as toluene and xylene, sufficient reactivity cannot be obtained.

Further, in the production methods of Patent Document 1 and Non-Patent Document 1 performed in a sealed state, the by-produced ethylene cannot be discharged out of the system, so the pressure in the reactor rises. Therefore, in order to produce industrially by this method, it is necessary to use a pressure vessel special in pressure resistance, which is disadvantageous in terms of safety and manufacturing cost.
On the other hand, although the production method of Non-Patent Document 2 is performed in a non-sealed state, it is necessary to use harmful benzene as a solvent and the reaction system cannot be brought to reflux conditions, so when triethoxyvinylsilane is used. There is a problem that it is difficult to remove by-produced ethylene out of the system and the yield is not improved.
In addition, although the production methods of Non-Patent Documents 3 and 4 are also performed in a non-sealed state, it is necessary to use an expensive ionic liquid as a solvent, which increases the production cost and describes a method for separating the product from the ionic liquid. Therefore, it is difficult to implement industrially.

Polish Patent No. 182268

Vercaemst, Cael et al, Jornal of Materials Chemistry, 19 (46), 8839-8845, 2009 : Seki Yoshio et al, Journal of Organometallic Chemistry, 369 (1), 117-123, 1989. Rogaiski, Szymon et al, Applied Catalysi, A: General, 445-446, 2012 Rogaiski, Szymon et al, Applied Catalysi, A: General, 261-268, 2012

  The present invention has been made in view of the above circumstances, and the efficiency of a 1,2-bissilylethylene compound capable of obtaining a 1,2-bissilylethylene compound in a good yield by a reaction in an unsealed system. An object of the present invention is to provide an efficient manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have reduced the reactivity of the vinyl silane compound by using an organooxysilane compound as a solvent when the vinyl silane compound is reacted in the presence of a ruthenium catalyst. In addition, it is found that a 1,2-bissilylethylene compound can be obtained in a good yield, and the reaction time is maintained while maintaining the catalytic activity by using a phosphine compound or an antioxidant as a co-catalyst together with a ruthenium catalyst. The present invention has been completed.

（式中、Ｒ¹およびＲ²は、互いに独立して、置換または非置換の炭素数１〜２０の１価炭化水素基を表し、ｎは、０、１または２の整数を表す。）
で表されるビニルシラン化合物を、溶媒中、ルテニウム触媒存在下で反応させる、下記一般式（２）

（式中、Ｒ¹、Ｒ²およびｎは、前記と同じ。）
で表される１，２−ビスシリルエチレン化合物の製造方法であって、前記溶媒として、オルガノオキシシラン化合物（ただし、式（１）のビニルシラン化合物は除く。）を用いることを特徴とする１，２−ビスシリルエチレン化合物の製造方法、
２． 前記反応を、２００℃以下に保って還流下で行う１の１，２−ビスシリルエチレン化合物の製造方法、
３． 前記ルテニウム触媒と前記オルガノオキシシラン化合物との混合物中に、前記ビニルシラン化合物を添加しながら反応を行う、または前記ビニルシラン化合物および前記オルガノオキシシラン化合物の混合物を添加しながら反応を行う１または２の１，２−ビスシリルエチレン化合物の製造方法、
４． 前記ビニルシラン化合物および前記オルガノオキシシラン化合物として、予め還流脱気したものを用いる３の１，２−ビスシリルエチレン化合物の製造方法、
５． 前記ビニルシラン化合物が、トリメトキシビニルシランまたはトリエトキシビニルシランである１〜４のいずれかの１，２−ビスシリルエチレン化合物の製造方法、
６． 前記オルガノオキシシラン化合物が、テトラオルガノオキシシラン、トリオルガノオキシシラン、ジオルガノオキシシラン、モノオルガノオキシシラン、およびビス（オルガノオキシシリル）アルカンから選ばれる少なくとも１種である１〜５のいずれかの１，２−ビスシリルエチレン化合物の製造方法、
７． 助触媒として、ホスフィン化合物または酸化防止剤を添加する１〜６のいずれかの１，２−ビスシリルエチレン化合物の製造方法
を提供する。 That is, the present invention
1. The following general formula (1)

(In the formula, R ¹ and R ² independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0, 1 or 2.)
The following general formula (2) is reacted in the presence of a ruthenium catalyst in a solvent.

(Wherein R ¹ , R ² and n are the same as described above.)
A process for producing a 1,2-bissilylethylene compound represented by the formula 1, wherein an organooxysilane compound (excluding the vinylsilane compound of formula (1)) is used as the solvent: A method for producing a 2-bissilylethylene compound,
2. 1. The method for producing 1,2-bissilylethylene compound according to 1, wherein the reaction is carried out under reflux while maintaining at 200 ° C. or lower,
3. The reaction is carried out while adding the vinylsilane compound to the mixture of the ruthenium catalyst and the organooxysilane compound, or the reaction is carried out while adding the mixture of the vinylsilane compound and the organooxysilane compound. , 2-bissilylethylene compound production method,
4). The method for producing a 1,2-bissilylethylene compound according to 3, wherein the vinylsilane compound and the organooxysilane compound are preliminarily refluxed and degassed,
5. The method for producing a 1,2-bissilylethylene compound according to any one of 1 to 4, wherein the vinylsilane compound is trimethoxyvinylsilane or triethoxyvinylsilane,
6). Any one of 1-5, wherein the organooxysilane compound is at least one selected from tetraorganooxysilane, triorganooxysilane, diorganooxysilane, monoorganooxysilane, and bis (organooxysilyl) alkane. A method for producing a 1,2-bissilylethylene compound,
7). Provided is a method for producing a 1,2-bissilylethylene compound according to any one of 1 to 6, wherein a phosphine compound or an antioxidant is added as a co-catalyst.

  According to the method for producing a 1,2-bissilylethylene compound of the present invention, a 1,2-bissilylethylene compound can be industrially and safely used in an unsealed manner without using a special and expensive high pressure resistant production apparatus. Can be manufactured.

Hereinafter, the present invention will be specifically described.
In the process for producing a 1,2-bissilylethylene compound according to the present invention, a vinylsilane compound represented by the general formula (1) is reacted in a solvent in the presence of a ruthenium catalyst, and the general formula (2)
In the production of a 1,2-bissilylethylene compound represented by the formula, an organooxysilane compound is used as a solvent.

Here, R ¹ and R ² each independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, but is substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms. Group is preferable, and an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms is more preferable. N represents an integer of 0, 1 or 2.
The monovalent hydrocarbon group is not particularly limited, but specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Linear alkyl groups such as octyl, n-decyl and n-octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, t-butyl and 2-ethylhexyl groups; cyclic alkyl groups such as cyclopentyl and cyclohexyl groups; vinyl, Examples thereof include alkenyl groups such as propenyl group; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl group and the like. In particular, from the viewpoint of availability of raw materials, R ¹ is preferably a methyl group and R ² is preferably a methyl group or an ethyl group.
Each monovalent hydrocarbon group may have at least one hydrogen atom substituted with a halogen atom (fluorine, chlorine, bromine, iodine atom), a cyano group, a nitro group, an amino group, or the like. .

  Specific examples of the vinylsilane compound represented by the general formula (1) include trimethoxyvinylsilane, triethoxyvinylsilane, tri-n-propoxyvinylsilane, triisopropoxyvinylsilane, tri-n-butoxyvinylsilane, and triphenoxyvinylsilane. Triorganooxysilane; methyldimethoxyvinylsilane, methyldiethoxyvinylsilane, ethyldimethoxyvinylsilane, ethyldiethoxyvinylsilane, methyldiphenoxyvinylsilane, ethyldiphenoxyvinylsilane, and the like; dimethylmethoxyvinylsilane, dimethylethoxyvinylsilane, diethylmethoxyvinylsilane , Diethylethoxyvinylsilane, dimethylphenoxyvinylsilane, diethylphenoxyvinylsilane, etc. Although such organooxysilane are mentioned, in the present invention, in particular, trimethoxyvinylsilane or triethoxy vinyl silane is preferred.

  Specific examples of the 1,2-bissilylethylene compound represented by the general formula (2) obtained by the reaction of the vinylsilane compound represented by the general formula (1) include 1,2-bis (tri Methoxysilyl) ethylene, 1,2-bis (triethoxysilyl) ethylene, 1,2-bis (tri-n-propylsilyl) ethylene, 1,2-bis (triisopropylsilyl) ethylene, 1,2-bis ( Tri-n-butoxysilyl) ethylene, 1,2-bis (triphenoxysilyl) ethylene, 1,2-bis (methyldimethoxysilyl) ethylene, 1,2-bis (methyldiethoxysilyl) ethylene, 1,2- Bis (ethyldimethoxysilyl) ethylene, 1,2-bis (methyldiphenoxysilyl) ethylene, 1,2-bis (ethyldiphenoxysilyl) ethylene, , 2-bis (dimethylmethoxysilyl) ethylene, 1,2-bis (dimethylethoxysilyl) ethylene, 1,2-bis (diethylmethoxysilyl) ethylene, 1,2-bis (diethylethoxysilyl) ethylene, 1,2 -Bis (dimethylphenoxysilyl) ethylene, 1,2-bis (diethylphenoxysilyl) ethylene and the like.

The organooxysilane compound used as the solvent of the present invention is not particularly limited as long as it is a silane compound containing an organooxy group (however, the vinylsilane compound of the formula (1) is excluded). Compounds that do not contain sulfur or nitrogen atoms that reduce activity are preferred.
Specific examples thereof include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane and tetraisobutoxysilane; tetraaryloxysilanes such as tetraphenoxysilane; Methoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane , Ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyl Limethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n -Hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-undecyltrimethoxysilane, n -Undecyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-tetradecyltrimethoxysilane, n-tetradecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-he Trialkoxysilanes such as sadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane; triaryloxysilanes such as methyltriphenoxysilane, ethyltriphenoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, Dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane , Diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, diisobutyldimethoxysilane, di- Dialkoxysilanes such as isobutyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, dimethyldiphenoxysilane, diethyl Diaryloxysilanes such as diphenoxysilane; trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propoxysilane, trimethylisopropoxysilane, trimethyl-n-butoxysilane, trimethylphenoxysilane, triethylmethoxysilane, triethylethoxysilane, triethyl- n-propoxysilane, triethylisopropoxysilane, triethyl-n-butoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri Isopropylmethoxysilane, triisopropylethoxysilane, ethyldimethylmethoxysilane, ethyldimethylethoxysilane, n-propyldimethylmethoxysilane, n-propyldimethylethoxysilane, isopropyldimethylmethoxysilane, isopropyldimethylethoxysilane, n-butyldimethylmethoxysilane, n-butyldimethylethoxysilane, isobutyldimethylmethoxysilane, isobutyldimethylethoxysilane, s-butyldimethylmethoxysilane, s-butyldimethylethoxysilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, n-pentyldimethylmethoxy Silane, n-pentyldimethylethoxysilane, n-hexyldimethylmethoxysilane, n-hexyldimethyl Toxisilane, n-heptyldimethylmethoxysilane, n-heptyldimethylethoxysilane, n-octyldimethylmethoxysilane, n-octyldimethylethoxysilane, n-decyldimethylmethoxysilane, n-decyldimethylethoxysilane, n-undecyldimethylmethoxy Silane, n-undecyldimethylethoxysilane, n-dodecyldimethylmethoxysilane, n-dodecyldimethylethoxysilane, n-tetradecyldimethylmethoxysilane, n-tetradecyldimethylethoxysilane, n-hexadecyldimethylmethoxysilane, n- Monoalkoxysilanes such as hexadecyldimethylethoxysilane, n-octadecyldimethylmethoxysilane, n-octadecyldimethylethoxysilane; trimethylphenoxysilane; Monoaryloxysilanes such as triethylphenoxysilane; 1,2-bis (trimethoxysilyl) ethane, 1,1-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1,1- Bis (triethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,4-bis ( Triethoxysilyl) butane, 1,2-bis (trimethoxysilyl) ethylene, 1,1-bis (trimethoxysilyl) ethylene, 1,2-bis (triethoxysilyl) ethylene, 1,1-bis (triethoxy Silyl) ethylene, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethyllsilyl) ethane, , 2-bis (dimethoxymethylsilyl) ethylene, 1,2-bis (diethoxymethylsilyl) ethylene, 1,2-bis (methoxydimethylsilyl) ethane, 1,2-bis (ethoxydimethylsilyl) ethane, 1, Examples thereof include bis (alkoxysilyl) alkanes such as 2-bis (methoxydimethylsilyl) ethylene and 1,2-bis (ethoxydimethylsilyl) ethylene.

These organooxysilane compounds may be used alone or in combination of two or more. When two or more types of organooxysilane are used, the mixing ratio is arbitrary, and the mixing ratio may be determined in consideration of the boiling point of the mixed solution.
Further, the organooxysilane compound (mixture thereof) preferably has a boiling point difference capable of being separated by distillation from the 1,2-bissilylethylene compound produced by the reaction. From such a viewpoint, tetramethoxysilane, methyltrimethoxy Silane, dimethyldimethoxysilane, 1,2-bis (trimethoxysilyl) ethylene, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, bis (triethoxysilyl) ethylene, and mixtures thereof are preferred.
In addition, in the production method of the present invention, various solvents conventionally used in this type of reaction can be added in addition to the above-mentioned organooxysilane compound as long as the reaction efficiency is not hindered. Is preferably used in a proportion of 70% by mass or more, more preferably in a proportion of 80% by mass or more, still more preferably in a proportion of 90% by mass or more, and further preferably a reaction with a single solvent. .

  The amount of the organooxysilane compound used in the present invention is not particularly limited, but since it is used as a solvent in the reactor, at least the equipment such as a stirrer and thermometer installed in the reactor can be used. It is preferable to use a limited amount. In particular, when the reaction is carried out under reflux with only the vinylsilane compound added, the internal temperature may increase depending on the boiling point of the bissilylethylene compound to be produced. It is preferable to adjust the amount so that the reaction temperature can be kept within the temperature range described below.

The ruthenium catalyst can be appropriately selected from the catalysts conventionally used for this type of reaction, but is particularly preferably a ruthenium complex catalyst, more preferably a ruthenium carbene complex catalyst.
Specific examples of the ruthenium catalyst include (3-phenyl-1H-indene-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride, bis (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (triphenylphosphine) -3,3. -Diphenylpropenylidene ruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylidene ruthenium dichloride, bis (1,3-diisopropylimidazoline-2-ylidene) benzylidene ruthenium dichloride, bis (1,3-dicyclohexylimidazolin-2-ylidene ) Benzylidene ruthenium dichloride, (1,3-dimesityrylimidazoline-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, 1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (Tricyclohexylphosphine) ethoxymethylidene ruthenium dichloride and the like.
Among these catalysts, (3-phenyl-1H-indene-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride and bis (tricyclohexylphosphine) benzylideneruthenium dichloride are preferable because of good reaction selectivity. In particular, (3-phenyl-1H-indene-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride is more preferable from the viewpoint of reaction selectivity, reactivity, availability of catalyst, and the like.

  In the production method of the present invention, the amount of the ruthenium catalyst used is not particularly limited, but considering that an efficient reaction is carried out while maintaining a moderate reaction rate, the amount of the ruthenium catalyst is 0.1% relative to 1 mol of the vinylsilane compound. 0001 mmol to 0.1 mol, preferably 0.001 mmol to 0.01 mol is preferred.

In the production method of the present invention, a phosphine compound or an antioxidant may be added as a co-catalyst for the purpose of reducing the reaction time by improving the activity of the ruthenium catalyst or suppressing its deactivation.
Specific examples of the phosphine compound include triphenylphosphine, diphenylcyclohexylphosphine, phenyldicyclohexylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-o-tolylphosphine, tri -M-tolylphosphine, tri-p-tolylphosphine and the like can be mentioned, and tricyclohexylphosphine is particularly preferable.
Antioxidants include phenol compounds such as 2,6-di-t-butyl-4-methylphenol and 2,2'-methylenebis (6-t-butyl-4-methylphenol); L-ascorbic acid, Examples include α-tocopherol, and L-ascorbic acid is particularly preferable.
The amount of these cocatalysts added is not particularly limited as long as the desired effect is exhibited, but is preferably 0.1 to 10 mol, more preferably 0.5 to 4 mol, relative to 1 mol of the ruthenium catalyst. preferable.

The method for producing a bissilylethylene compound of the present invention can be carried out by mixing a raw material vinylsilane compound, a solvent organooxirane compound, a ruthenium catalyst, and a co-catalyst used as necessary in any order. In particular, it is preferable to carry out the reaction by adding a vinylsilane compound to a mixture of a ruthenium catalyst and an organooxysilane compound as a solvent.
At this time, the vinylsilane compound may be added alone, or in order to keep the reaction temperature within a certain range, it may be added as a mixture of the vinylsilane compound and the organooxysilane compound as a solvent.
Furthermore, it is preferable that the vinylsilane compound to be added and the organooxysilane compound used therewith are refluxed and deaerated in advance before the reaction. This reflux deaeration can prevent a decrease in the activity of the catalyst, reduce the amount of catalyst used, and shorten the reaction time.

The production method of the present invention is preferably carried out under reflux in order to remove by-produced ethylene out of the system.
The reaction temperature at the time of reflux varies depending on the kind of the vinylsilane compound as a raw material. However, if the reaction temperature exceeds 200 ° C, the activity of the catalyst may be lowered. In particular, it is preferable to reflux at 140 to 180 ° C.
As described above, an organooxysilane compound that is a solvent may be added together with the vinylsilane compound so that the reaction temperature falls within a certain range. The activity can be effectively prevented from decreasing, and the work of adjusting the heating to maintain the reflux can be reduced.

For example, in the reaction of vinyltriethoxysilane, the reaction temperature is preferably maintained at 150 to 180 ° C., and the reaction is performed under reflux. As a method of maintaining this reaction temperature, tetraethoxysilane is used as a solvent. And a method of adding vinyltriethoxysilane in such an amount that the temperature at the end of the reaction is 180 ° C.
Further, as a method of maintaining the reaction temperature at 150 to 165 ° C., a mixed liquid of methyltriethoxysilane and bis (triethoxysilyl) ethylene or a mixed liquid of methyltriethoxysilane and tetraethoxysilane is used as a solvent. A method in which triethoxysilane and methyltriethoxysilane are added and reacted, or a mixed liquid of methyltrimethoxysilane and bis (trimethoxysilyl) ethylene is used as a solvent, and vinyltrimethoxysilane and methyltrimethoxysilane are mixed. The method of adding and reacting is mentioned.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In addition, the following reaction rates are the values measured using gas chromatography (GC-2014, Shimadzu Corporation Corp.).

[Example 1]
A 1 L four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Among them, 1.84 g (2 mmol) of (3-phenyl-1H-indene-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride (manufactured by Umicore, hereinafter referred to as “Umicore M1 catalyst”) and tetraethoxysilane 528 .9 g was charged and 380.6 g (2.0 mol) of vinyltriethoxysilane was added dropwise over 15 hours at a reaction temperature of 162 to 178 ° C. and refluxing (0.92 g (1 mmol) of Umicore M1 catalyst was added on the way). ), And further aged for 8 hours under reflux.
The reaction rate of vinyltriethoxysilane was 95% or more, and the resulting reaction solution was distilled under reduced pressure to obtain 305.9 g (0.868 mol) of 1,2-bis (triethoxysilyl) ethylene (yield: (86.8%).

[Example 2]
A 2 L four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Among them, 1.11 g (1.2 mmol) of Umicore M1 catalyst and 63.7 mg (2.4 mmol) of tricyclohexylphosphine, and 242.4 g of methyltriethoxysilane and 202.0 g of 1,2-bis (triethoxysilyl) ethylene. And a mixture of 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane was added dropwise over 14 hours at a reaction temperature of 155 to 160 ° C. and under reflux (on the way, Umicore M1 catalyst 0.56 g (0.6 mmol) was added), and further aged for 8 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction solution was distilled under reduced pressure to obtain 664.4 g of 1,2-bis (triethoxysilyl) ethylene. In consideration of 1,2-bis (triethoxysilyl) ethylene used as a solvent, 1,2-bis (triethoxysilyl) ethylene obtained by the reaction was 462.4 g (1.31 mol) (yield) : 87.4%).

[Example 3]
A 2 L four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. It was charged with 1.11 g (1.2 mmol) of Umicore M1 catalyst and 63.7 mg (2.4 mmol) of tricyclohexylphosphine, 141.5 g of methyltriethoxysilane and 297.8 g of tetraethoxysilane, Under a reaction temperature and under reflux, a mixed liquid of 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane was dropped over 18 hours (on the way, 0.56 g (0.6 mmol of Umicore M1 catalyst) ) Was added) and further aged for 12 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the resulting reaction solution was distilled under reduced pressure to obtain 457.7 g (1.30 mol) of 1,2-bis (triethoxysilyl) ethylene (yield: 86.5%).

[Example 4]
A 2 L four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Among them, 692.3 mg (0.75 mmol) of Umicore M1 catalyst and 264.2 mg (1.5 mmol) of L-ascorbic acid, and 242.4 g of methyltriethoxysilane and 1,2-bis (triethoxysilyl) ethylene 202. 0 g was charged, and a mixture of 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane was added dropwise over a period of 16 hours at a reaction temperature of 155 to 160 ° C. and refluxing. Aged for hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction solution was distilled under reduced pressure to obtain 664.4 g of 1,2-bis (triethoxysilyl) ethylene. Considering 1,2-bis (triethoxysilyl) ethylene used as a solvent, the amount of 1,2-bis (triethoxysilyl) ethylene obtained by the reaction was 460.1 g (1.30 mol) (yield) : 87.0%).

[Example 5]
A 2 L four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Among them, 692.3 mg (0.75 mmol) of Umicore M1 catalyst and 264.2 mg (1.5 mmol) of L-ascorbic acid, and 242.4 g of methyltriethoxysilane and 1,2-bis (triethoxysilyl) ethylene 202. 00.9 g, 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane which were degassed by refluxing for 1 hour before dropping at a reaction temperature of 155 to 160 ° C. and under reflux. Was added dropwise over 14 hours and aged for another 10 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction solution was distilled under reduced pressure to obtain 667.4 g of 1,2-bis (triethoxysilyl) ethylene. In consideration of 1,2-bis (triethoxysilyl) ethylene used as a solvent, 1,2-bis (triethoxysilyl) ethylene obtained by the reaction was 465.4 g (1.30 mol) (yield) : 88.0%).

[Example 6]
A 500 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. It was charged with 166.2 mg (0.18 mmol) of Umicore M1 catalyst, 50.5 g of methyltriethoxysilane and 60.6 g of 1,2-bis (triethoxysilyl) ethylene, at a reaction temperature of 156 to 160 ° C. under reflux. Then, a mixed solution of 34.5 g (0.18 mol) of vinyltriethoxysilane and 38.4 g of methyltriethoxysilane was added dropwise over 2.5 hours. The reaction rate of vinyltriethoxysilane was 94%.

[Comparative Example 1]
A 200 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Into this, 332.4 mg (0.36 mmol) of Umicore M1 catalyst and 34.3 g of o-xylene were charged, and 68.5 g (0.36 mol) of vinyltriethoxysilane was added at a reaction temperature of 144 to 160 ° C. under reflux. It was added dropwise over time. The reaction rate of vinyltriethoxysilane was 10%.

[Example 7]
A 500 ml four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Into this, 0.46 g (0.5 mmol) of Umicore M1 catalyst and 100 g of octyltrimethoxysilane were charged, and 116.2 g (1.0 mol) of vinyldimethylmethoxysilane was added for 5 hours at a reaction temperature of 138 to 220 ° C. under reflux. Over the course of 5 hours.
The reaction rate of vinyldimethylmethoxysilane was 96% or more, and the obtained reaction solution was distilled under reduced pressure to obtain 84.8 g (0.83 mol) of 1,2-bis (dimethylmethoxysilyl) ethylene (yield: 83.0%).

[Example 8]
A 500 mL four-necked glass flask was equipped with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. In the mixture, 923.1 mg (1 mmol) of Umicore M1 catalyst, 13.8 g of methyltrimethoxysilane, and 110.6 g of 1,2-bis (trimethoxysilyl) ethylene were charged at a reaction temperature of 170 to 180 ° C. and under reflux. Then, a mixed solution of 296.4 g (2.0 mol) of vinyltrimethoxysilane and 70.4 g of methyltrimethoxysilane was added dropwise over 36 hours, followed by aging for 10 hours.
The reaction rate of vinyltrimethoxysilane was 95% or more, and the obtained reaction solution was distilled under reduced pressure to obtain 330.7 g of 1,2-bis (trimethoxysilyl) ethylene. Considering 1,2-bis (trimethoxysilyl) ethylene used as a solvent, the amount of 1,2-bis (triethoxysilyl) ethylene obtained by the reaction was 220.1 g (0.82 mol) (yield) : 82.0%).

Claims (7)

The following general formula (1)

(In the formula, R ¹ and R ² independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0, 1 or 2.)
The following general formula (2) is reacted in the presence of a ruthenium catalyst in a solvent.

(Wherein R ¹ , R ² and n are the same as described above.)
A process for producing a 1,2-bissilylethylene compound represented by:
A method for producing a 1,2-bissilylethylene compound, wherein an organooxysilane compound (excluding the vinylsilane compound of formula (1)) is used as the solvent.   The method for producing a 1,2-bissilylethylene compound according to claim 1, wherein the reaction is carried out under reflux while maintaining at 200 ° C or lower.   The reaction is performed while adding the vinylsilane compound to the mixture of the ruthenium catalyst and the organooxysilane compound, or the reaction is performed while adding the mixture of the vinylsilane compound and the organooxysilane compound. A process for producing the 1,2-bissilylethylene compound as described.   4. The method for producing a 1,2-bissilylethylene compound according to claim 3, wherein the vinylsilane compound and the organooxysilane compound are preliminarily refluxed and degassed.   The method for producing a 1,2-bissilylethylene compound according to any one of claims 1 to 4, wherein the vinylsilane compound is trimethoxyvinylsilane or triethoxyvinylsilane.   6. The method according to claim 1, wherein the organooxysilane compound is at least one selected from tetraorganooxysilane, triorganooxysilane, diorganooxysilane, monoorganooxysilane, and bis (organooxysilyl) alkane. A process for producing a 1,2-bissilylethylene compound according to claim 1.   The method for producing a 1,2-bissilylethylene compound according to any one of claims 1 to 6, wherein a phosphine compound or an antioxidant is added as a cocatalyst.