JP6424840B2 - Process for producing 1,2-bissilylethylene compound - Google Patents

Description

  The present invention relates to a process for the preparation of 1,2-bissilylethylene compounds and, more particularly, of 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 the manufacturing method.

A 1,2-bissilylethylene compound is a compound useful as a silane coupling agent, a raw material of an organic silica hybrid material, etc., and is known to be obtained by metathesis reaction of a vinylsilane compound in the presence of a catalyst .
Specifically, as a process for producing 1,2-bis (triethoxysilyl) ethylene, it is produced by reacting vinyltriethoxysilane under reflux in the presence of Grubbs 1st generation catalyst in a sealed state in a Schlenk tube A method is known (Non-Patent Document 1).
There is also known a method of performing disproportionation reaction of triethoxysilane in the presence of a ruthenium catalyst and using benzene or toluene as a solvent in a closed state in a Schlenk flask (Patent Document 1).

On the other hand, as a method of manufacturing under closed condition, vinyl triethoxysilane is heated to about 80 ° C. in benzene solvent using Ru ₃ (CO) ₁₂ as catalyst, in the presence of triphenylsilane, and the reaction liquid is not refluxed. The method to make it react is known (nonpatent literature 2).
There is also known a method in which an ionic liquid is used as a solvent, and a reaction solution is reacted without reflux at 130 ° C. using a RuH (CO) (PCy ₃ ) ₂ catalyst (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 needed are charged at a time and reacted, there is a possibility that reaction may occur rapidly and reaction control may become difficult. , Industrial implementation is difficult.
In addition, in the method of Patent Document 1, in order to safely produce the 1,2-bissilylethylene compound industrially, it is conceivable to add a vinylsilane compound to a solvent containing a catalyst and make it react. In the system using an organic solvent such as toluene or xylene used, sufficient reactivity can not be obtained.

Further, in the processes of Patent Document 1 and Non-patent Document 1 which are carried out in a closed state, ethylene by-produced can not be discharged out of the system, so the pressure in the reactor rises. Therefore, in order to industrially produce by this method, it is necessary to use a special pressure vessel, which is disadvantageous in terms of safety and manufacturing cost.
On the other hand, although the production method of Non-Patent Document 2 is carried out in a non-sealed manner, it is necessary to use harmful benzene as a solvent, and since the reaction system can not be set to reflux conditions, when using triethoxyvinylsilane. It is difficult to remove by-produced ethylene out of the system and there is a problem that 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 manner, it is necessary to use an expensive ionic liquid as a solvent, which increases the production cost and describes a method of separating the product from the ionic liquid It is difficult to implement industrially because it is not

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 a non-closed system. Purpose is to provide a practical manufacturing method.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that when using a vinylsilane compound in the presence of a ruthenium catalyst, the reactivity of the vinylsilane compound is reduced by using an organooxysilane compound as a solvent. It is found that a 1,2-bissilylethylene compound can be obtained in 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 the ruthenium catalyst. It has been found that the present invention can be shortened.

（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)

(Wherein, R ¹ and R ² each 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 vinylsilane compound represented by the formula is reacted in the presence of a ruthenium catalyst in a solvent:

(Wherein, R ¹ , R ² and n are as defined above)
A process for producing a 1,2-bissilylethylene compound represented by the formula 1, wherein an organooxysilane compound (but excluding the vinylsilane compound of the formula (1)) is used as the solvent 1, Method for producing 2-bissilylethylene compound,
2. A method for producing a 1,2-bissilylethylene compound according to 1, wherein the reaction is carried out under reflux while keeping the temperature at 200 ° C. or lower,
3. The reaction is performed while adding the vinylsilane compound to a mixture of the ruthenium catalyst and the organooxysilane compound, or the reaction is performed while adding a mixture of the vinylsilane compound and the organooxysilane compound 1 or 2 1 , A method of producing a 2-bissilylethylene compound,
4. 3. The method for producing a 1,2-bissilylethylene compound according to 3, wherein the vinylsilane compound and the organooxysilane compound are previously degassed by reflux degassing,
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 to 5, wherein the organooxysilane compound is at least one selected from tetraorganooxysilane, triorganooxysilane, diorganooxysilane, monoorganooxysilane, and bis (organooxysilyl) alkanes. A process for producing a 1,2-bissilylethylene compound,
7. Provided is a method for producing any one of 1,2-bissilylethylene compounds, wherein a phosphine compound or an antioxidant is added as a cocatalyst.

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

Hereinafter, the present invention will be specifically described.
The method for producing a 1,2-bissilylethylene compound according to the present invention comprises reacting a vinylsilane compound represented by the general formula (1) in the presence of a ruthenium catalyst in a solvent to obtain a compound of the general formula (2)
When manufacturing the 1, 2- bis silyl ethylene compound represented by these, it is characterized by using an organo oxysilane compound as a solvent.

Here, R ¹ and R ² independently represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, but a substituted or unsubstituted monovalent hydrocarbon having 1 to 10 carbon atoms Group is preferable, and unsubstituted C1-C10 monovalent hydrocarbon group is more preferable. Also, n represents an integer of 0, 1 or 2.
The monovalent hydrocarbon group is not particularly limited, and specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n- Linear alkyl groups such as octyl, n-decyl and n-octadecyl; Branched alkyl groups such as isopropyl, isobutyl, t-butyl and 2-ethylhexyl; Cyclic alkyl such as cyclopentyl and cyclohexyl; Vinyl Alkenyl groups such as propenyl group; Aryl groups such as phenyl and tolyl group; Aralkyl groups such as benzyl group and the like. In particular, in view of the availability of raw materials, R ¹ is preferably a methyl group, and R ² is preferably a methyl group or an ethyl group.
In each of the above monovalent hydrocarbon groups, at least one hydrogen atom therein may be substituted by a halogen atom (fluorine, chlorine, bromine, iodine atom), a cyano group, a nitro group, an amino group, etc. .

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

  In addition, 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 above 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 (dimethyl phenoxy silyl) ethylene, 1, 2- bis (diethyl phenoxy silyl) ethylene, etc. are mentioned.

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) is a catalyst. Compounds which do not contain sulfur atoms or nitrogen atoms which reduce the 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-hexane 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- Isobutyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, dialkoxysilanes such as 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, 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-pentyldimethylmethoxysilane 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 (diethoxymethylsilyl) ethane, , 2-bis (dimethoxymethylsilyl) ethylene, 1,2-bis (diethoxymethylsilyl) ethylene, 1,2-bis (methoxydimethylsilyl) ethane, 1,2-bis (ethoxydimethylsilyl) ethane, 1, And 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. The mixing ratio in the case of using two or more types of organooxysilanes is arbitrary, and the mixing ratio may be determined in consideration of the boiling point of the mixed solution.
In addition, (or a mixture of) the organooxysilane compound preferably has a difference in boiling point capable of being separated by distillation from the 1,2-bissilylethylene compound produced in the reaction, and from such a viewpoint, tetramethoxysilane, methyltrimethoxy Silanes, dimethyldimethoxysilane, 1,2-bis (trimethoxysilyl) ethylene, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, bis (triethoxysilyl) ethylene, and mixtures thereof are preferred.
In the production method of the present invention, various solvents conventionally used for this type of reaction can be added in addition to the above-mentioned organooxysilane compound, as long as the reaction efficiency is not impaired. Even in this case, the organooxysilane compound It is preferable to use at a rate of 70% by mass or more, more preferably at a rate of 80% by mass or more, still more preferably at a rate of 90% by mass or more, and still more preferably performing the reaction with a single solvent .

  The use amount of the organooxysilane compound used in the present invention is not particularly limited, but it is at least used as a solvent in the reactor, and thus at least the equipment such as a stirrer or thermometer installed in the reactor can be used. It is preferred to use in limited amounts. In particular, when the reaction is carried out under reflux by adding only a vinylsilane compound, the internal temperature may increase depending on the boiling point of the bissilylethylene compound to be produced, so a solvent for the bissilylethylene compound to be produced may be generated. Preferably, the amount is adjusted so that the reaction temperature can be maintained in the temperature range described later.

The ruthenium catalyst can be appropriately selected from catalysts conventionally used for this type of reaction, but a ruthenium complex catalyst is particularly preferable, and a ruthenium carbene complex catalyst is more preferable.
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. -Diphenylpropenylideneruthenium dichloride, bis (tricyclohexylphosphine) t-butylvinylideneruthenium dichloride, bis (1,3-diisopropylimidazolin-2-ylidene) benzylideneruthenium dichloride, bis (1,3-dicyclohexylimidazolin-2-ylidene) ) Benzylidene ruthenium dichloride, (1,3-dimesitylimidazolin-2-ylidene) (tricyclohexylphosphine) benzylidene ruthenium dichloride, 1,3-Dimesitylimidazolidin-2-ylidene) (tricyclohexylphosphine) benzylideneruthenium dichloride, bis (tricyclohexylphosphine) ethoxymethylideneruthenium dichloride, (1,3-dimesitylimidazolidin-2-ylidene) Examples include (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 their good reaction selectivity. In particular, (3-phenyl-1H-indene-1-ylidene) bis (tricyclohexylphosphine) ruthenium dichloride is more preferable in terms of reaction selectivity, reactivity, and availability of a catalyst.

  In the production method of the present invention, the amount of the ruthenium catalyst used is not particularly limited, but in view of efficient reaction while maintaining an appropriate reaction rate, 0. 0 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 improving the activity of the ruthenium catalyst or suppressing its deactivation to shorten the reaction time.
Specific examples of phosphine compounds include triphenyl phosphine, diphenylcyclohexyl phosphine, phenyl dicyclohexyl phosphine, tricyclohexyl phosphine, tricyclopentyl phosphine, tri-n-butyl phosphine, tri-t-butyl phosphine, tri-o-tolyl phosphine, tri -M-tolyl phosphine, tri-p-tolyl phosphine and the like can be mentioned, and in particular, tricyclohexyl phosphine is preferable.
Phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and 2,2'-methylenebis (6-t-butyl-4-methylphenol) as antioxidants; L-ascorbic acid, α-tocopherol and the like can be mentioned, and in particular, L-ascorbic acid is preferable.
The addition amount of these co-catalysts is not particularly limited as long as the desired effect is exhibited, but 0.1 to 10 mol is preferable to 1 mol of the ruthenium catalyst, and 0.5 to 4 mol is more preferable. preferable.

The process for producing the bissilylethylene compound of the present invention can be carried out by mixing the vinylsilane compound as the raw material, the organooxirane compound as the solvent, the ruthenium catalyst, and the cocatalyst used as needed 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 which is 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 a vinylsilane compound and an organooxysilane compound which is a solvent.
Furthermore, it is preferable that the vinylsilane compound to be added and the organooxysilane compound to be used with this be previously subjected to reflux degassing before the reaction. This reflux degassing can prevent a decrease in the activity of the catalyst, and can reduce the amount of catalyst used or shorten the reaction time.

Further, 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 reflux varies depending on the type of the vinylsilane compound as the raw material, but if the reaction temperature exceeds 200 ° C., the activity of the catalyst may decrease, so it is preferable to keep the temperature at 200 ° C. or less to reflux. In particular, it is preferable to keep the temperature at 140 to 180 ° C. to reflux.
As described above, the reaction temperature may be in a certain range by adding an organooxysilane compound which is a solvent together with the vinylsilane compound, and in this way, the catalyst due to the increase of the reaction temperature It is possible to prevent the decrease in activity efficiently and to reduce the work of adjusting the heating to keep reflux.

As an example, in the reaction of vinyltriethoxysilane, it is preferable to keep the reaction temperature at 150 to 180 ° C. and make the reaction under reflux. As a method of keeping this reaction temperature, tetraethoxysilane is used as a solvent And a method of adding vinyltriethoxysilane in an amount such that the temperature at the end of the reaction becomes 180.degree.
Furthermore, as a method of keeping the above reaction temperature at 150 to 165 ° C., a mixed solution of methyltriethoxysilane and bis (triethoxysilyl) ethylene or a mixed solution of methyltriethoxysilane and tetraethoxysilane is used as a solvent, and vinyl is used. A method of reacting by adding triethoxysilane and methyltriethoxysilane, or using a mixed solution of methyltrimethoxysilane and bis (trimethoxysilyl) ethylene as a solvent, vinyltrimethoxysilane and methyltrimethoxysilane The method of adding and reacting is mentioned.

EXAMPLES The present invention will be more specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples.
In addition, the following reaction rates are the values measured using gas chromatography (GC-2014, Shimadzu Corp. make).

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 under reflux at a reaction temperature of 162 to 178 ° C. (0.92 g (1 mmol) of Umicore M1 catalyst was added in the middle) ), And aged for 8 hours under reflux.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction liquid 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 fitted 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 A mixed solution 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. under reflux (in the middle, An additional 0.56 g (0.6 mmol) of Umicore M1 catalyst was added and aged for 8 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction liquid 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, the amount of 1,2-bis (triethoxysilyl) ethylene obtained in the reaction was 462.4 g (1.31 mol) (yield 87.4%).

[Example 3]
A 2 L four-necked glass flask was fitted with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Into it, 1.11 g (1.2 mmol) of Umicore M1 catalyst and 63.7 mg (2.4 mmol) of tricyclohexylphosphine and 141.5 g of methyltriethoxysilane and 297.8 g of tetraethoxysilane are charged, and the temperature is 155 to 160 ° C. A mixture of 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane was added dropwise over 18 hours at a reaction temperature and under reflux (in the middle, 0.56 g (0.6 mmol of Umicore M1 catalyst) ) Added), and then aged for 12 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction liquid 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 fitted 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 is charged, and a mixed solution of 570.9 g (3.0 mol) of vinyltriethoxysilane and 634.8 g of methyltriethoxysilane is added dropwise over 16 hours at a reaction temperature of 155 to 160 ° C. under reflux, and further 12 Aged over time.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction liquid 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, the amount of 1,2-bis (triethoxysilyl) ethylene obtained in the reaction was 460.1 g (1.30 mol) (yield : 87.0%).

[Example 5]
A 2 L four-necked glass flask was fitted 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. Charge 0g, 570.9g (3.0 mol) of vinyltriethoxysilane and 634.8g of methyltriethoxysilane, which were degassed by refluxing for 1 hour before dropping under reaction temperature and reflux temperature of 155 to 160 ° C. The mixture was added dropwise over 14 hours and then aged for 10 hours.
The reaction rate of vinyltriethoxysilane was 95% or more, and the obtained reaction liquid 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, 465.4 g (1.30 mol) of 1,2-bis (triethoxysilyl) ethylene obtained in the reaction was obtained (yield : 88.0%).

[Example 6]
A 500 ml four-necked glass flask was fitted with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Among them, 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 are charged, and the reaction temperature is 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 conversion of vinyltriethoxysilane was 94%.

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

[Example 7]
A 500 ml four-necked glass flask was fitted with a reflux condenser, a thermometer and a stirrer, and the interior was purged with nitrogen. Into it, 0.46 g (0.5 mmol) of Umicore M1 catalyst and 100 g of octyltrimethoxysilane are charged, and 116.2 g (1.0 mol) of vinyldimethylmethoxysilane for 5 hours at a reaction temperature of 138 to 220 ° C. under reflux. The solution was added dropwise and aged for further 5 hours.
The reaction rate of vinyldimethylmethoxysilane was 96% or more, and the obtained reaction liquid 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. Into it, 923.1 mg (1 mmol) of Umicore M1 catalyst, 13.8 g of methyltrimethoxysilane, and 110.6 g of 1,2-bis (trimethoxysilyl) ethylene are charged, and the reaction temperature is 170 to 180 ° C. under reflux. A mixture of 296.4 g (2.0 mol) of vinyltrimethoxysilane and 70.4 g of methyltrimethoxysilane was added dropwise over 36 hours, and aging was further performed for 10 hours.
The reaction rate of vinyltrimethoxysilane was 95% or more, and the obtained reaction liquid 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)

(Wherein, R ¹ and R ² each 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 vinylsilane compound represented by the formula is reacted in the presence of a ruthenium catalyst in a solvent:

(Wherein, R ¹ , R ² and n are as defined 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 (with the exception of the vinylsilane compound of the 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 the temperature at 200 ° C or less.   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. The manufacturing method of the 1, 2- bis silyl ethylene compound as described.   The method for producing a 1,2-bissilylethylene compound according to claim 3, wherein the vinyl silane compound and the organooxysilane compound are previously degassed by reflux degassing.   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.   The said organo oxysilane compound is at least 1 sort (s) chosen from tetraorgano oxysilane, triorgano oxysilane, diorgano oxysilane, monoorgano oxysilane, and bis (organo oxy silyl) alkane. A method for producing a 1,2-bissilylethylene compound according to any one of the items 1 to 4.   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.