JP3408601B2 - Synthetic method of alkenylsilane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] This invention relates to the synthesis of alkenylsilanes.
About the law. [0002] BACKGROUND OF THE INVENTION Alkenylsilane polymers or
Copolymers such as pyrene exhibit various useful properties
Is expected to be a new monomer for functional materials
It is. Various synthetic routes for the synthesis of alkenylsilane
Alkenylchlorosilane as a raw material
And dispersing a reducing agent such as metal hydride in a solvent.
The method of synthesis is one of the most effective synthesis methods because it is simple.
is there. Reduction of alkenylchlorosilane to alkenyl
When synthesizing a run, lithium aluminum high
Dried (LiAlH₄) As a reducing agent
Are known, and the alkenyl sila
Is obtained. [0003] SUMMARY OF THE INVENTION Alkenylchlorosila
In the synthesis of alkenylsilane by reducing
LiAlH₄Is usually dispersed in a solvent.
Was. However, LiAlH₄Although expensive
Even if the yield is good, 70%
The reaction temperature is as high as 50 ° C to 80 ° C, and this reaction is exothermic
Because it is a reaction, it is difficult to control the reaction.
You. [0004] [MEANS FOR SOLVING THE PROBLEMS] Sodium aluminum
Hydride (NaAlH₄) Is LiAlH₄Similar to
Synthesis of alkenylsilane as a reducing agent but according to the present invention
Is low in reactivity and inexpensive, but
Use was difficult. In view of such a situation, the present inventor
And others worked diligently to find that alkenylchlorosilane
NaAlH, which is inexpensive but has low reducing power,₄
Is dissolved in a specific solvent to obtain LiAlH₄To
85% or more compared to the case of dispersing in solvent
Found that it can be reduced to alkenylsilane with high yield
Thus, the present invention has been achieved. That is, the present invention provides a compound represented by the general formula C_m H_2m-1SiH_n
Cl_3-n(M is an integer of 2 to 5 and n is an integer of 0 to 2)
From the alkenylchlorosilane and hydride, the general formula C
_m H_2m-1SiH_ThreeSynthesizes the alkenylsilane represented by
In the, sodium aluminum high as hydride
Using dry, tetrahydrofuran, ethylene glycol
Chole dimethyl ether or diethyl ether
React in the presence of one or more combinations of solvents
The synthesis of alkenyl silanes
You. The present invention will be described in more detail. Implementation method
Is LiAlH_FourCustomary methods of using as a reducing agent and
Almost the same. Therefore, the customary details are
For the sake of simplicity, focus on the features that
A detailed embodiment will be described. The solvent used in the present invention is tet
Lahydrofuran, ethylene glycol dimethyl ether
Or a combination of one or more of diethyl ether
And a suitable solvent is tetrahydro
Furan, ethylene glycol dimethyl ether or di
Ethyl ether is mentioned. The method for synthesizing alkenylsilane is not a simple one.
Although not particularly limited, for example, the following
The synthesis method will be described. As a preparation for synthesis,
Dissolve the reducing agent in a SUS reaction vessel
Start by adjusting the solvent. Na used in this reaction
AlH₄Is LiAlH₄Reacts violently with moisture as does
Therefore, use it in an atmosphere where moisture is eliminated as much as possible. That
NaAlH₄When charging in a reaction vessel, the method is
There are various possibilities, but anyway, it can be done at the time of preparation
Only need to be careful not to contact the moisture in the air
It is. For example, dry box for small amount synthesis
Contact with air or, if large quantities, contact with air
Use a pre-dissolved one in a solvent to reduce
Conceivable. When the reaction is ready as described above,
Subsequently, alkenylchlorosilane is supplied to the reaction vessel.
I do. If the reaction temperature at this time is too high, the control of the reaction is
Becomes difficult and the solvent is the same as the alkenylsilane formed.
0-50 ° C.
Is more preferable, more preferably 5 to 40C, most preferably.
Is preferably from 10 to 30C. If performed at the reaction temperature,
Easy reaction control just by passing warm water through the jacket
This is preferable because the entrainment of the solvent can be prevented. What is the required amount of alkenylchlorosilane?
Can be selected, but 10 equivalents of reducing agent
7-14 equivalents of kenylchlorosilane are common. What
The effect obtained by the present invention is the same as that described above.
Not only in touch operation, but also in synthesis in continuous operation
It is not something to be done. The reduction reaction of alkenylchlorosilane is rapid.
And the formation of alkenylsilane is almost instantaneous after the start of the reaction.
Starts at time. When the alkenylsilane produced is in a gaseous
The carrier gas together with the carrier gas
And collect the gas generated using a suitable refrigerant.
This is the simplest collection method. Also, the alkenyl formed
When the silane is liquid, after the reaction is completed,
It is a general method to carry out separation from a solvent. In addition, obtained
Alkenylsilane yield
It is calculated on a molar basis relative to the amount of silane used. [0011] The following examples further illustrate the present invention.
explain in detail. Example 1 In a dry box, add 445 g of tetrahydrofuran to Na
AlH_FourDissolve 40 g (0.74 mol) and add 1 liter
Stir in a SUS reaction vessel with a jacket
Was. Room temperature water was passed through the reaction vessel jacket. Next
In addition, vinyl dichlorosilane (C₂H₃SiCl₂) 22
5g (1.77mol) with some amount of nitrogen gas
While gradually supplying the reaction vessel. The generated gas is
86 g as a result of collection using liquid nitrogen as a refrigerant
(1.48 mol) of vinylsilane was obtained. The yield is about
It was 83 mol%. Embodiment 2 As in Example 1, NaA was added to 270 g of diethyl ether.
1H₄50 g (0.86 mol) was dissolved, and the same as in Example 1 was dissolved.
And stirred. The reaction vessel jacket
Was passed through water at room temperature. Next, vinyl trichlorosila
(C₂H₃SiCl₃) 240 g (1.49 mol)
While slowly entraining a small amount of nitrogen gas.
Was supplied to the vessel. The generated gas uses liquid nitrogen as a refrigerant.
As a result of using and collecting, 76 g (1.31 mol) of vinyl
The silane was obtained. The yield was about 88 mol%. Embodiment 3 As in Example 1, ethylene glycol dimethyl ether
473 g of NaAlH₄40 g (0.74 mol)
The mixture was dissolved, charged in the same reaction vessel as in Example 1, and stirred. The
Room temperature water was passed through the reaction vessel jacket. Next,
Nyltrichlorosilane (C₂H₃SiCl₃) 310 g
(1.92 mol) with some amount of nitrogen gas
And gradually supplied to the reaction vessel. The generated gas is a liquid
As a result of collecting using body nitrogen as a refrigerant, 100 g
(1.74 mol) of vinylsilane was obtained. The yield is about
It was 91 mol%. Embodiment 4 As in Example 1, 445 g of tetrahydrofuran was added to Na
AlH₄After dissolving 40 g (0.74 mol) of Example 1,
The same reaction vessel was charged and stirred. The reaction vessel jacket
Room temperature water was passed through the unit. Next, allyltrichloro
Silane (C₃H ₅SiCl₃) 200g (1.14mo
1) while gradually entraining a small amount of nitrogen gas.
It was supplied to the reaction vessel. The generated gas uses liquid nitrogen as a refrigerant.
As a result of use and collection, 72 g (1.0 mol)
Lusilane was obtained. The yield was about 88 mol%. Comparative Example 1 In the same manner as in Example 1, 385 g of dibutyl ether was added.
NaAlH₄Disperse 40 g (0.74 mol)
The same reaction vessel as in Example 1 was charged and stirred. The reaction vessel
Room temperature water was passed through the jacket. Next, vinyl jig
Lorosilane (C ₂H₃SiCl₂) 225 g (1.77)
mol) with a slight amount of nitrogen gas.
It was supplied to the reaction vessel. As a result, you can check the yield
Not enough vinylsilane was formed. Comparative Example 2 In the same procedure as in Example 1, 525 g of dioxane was added to NaA.
1H₄Example 1 58 g (1.07 mol) was dispersed.
The same reaction vessel was charged and stirred. The reaction vessel jacket
Room temperature water was passed through the unit. Next, allyltrichloro
Silane (C₃H ₅SiCl₃) 275g (1.57mo)
1) while gradually entraining a small amount of nitrogen gas.
It was supplied to the reaction vessel. As a result, enough to confirm the yield
No significant amount of allylsilane was formed. [0017] [0018] As described in detail above, NaAl
H₄Is inexpensive but has a weak reducing ability,
Is limited under selected conditions. Subject of the present invention
When used for the reduction of alkenylchlorosilanes
It is the same as above. However, certain solvents such as the present invention
By using, NaAlH₄The return capacity of
LiAlH expensive as a reducing agent₄Equivalent or better effect
NaAlH₄Becomes practical. as a result,
Inexpensive NaAlH₄And a high yield is obtained.
The economic effect is great.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-230392 (JP, A) JP-A-7-173173 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB name) C07F 7/08

Claims (1)

(57) [Claims 1] The general formula C _m H _2m-1 SiH _n Cl _3-n (m = 2
-5, n = 0 to 2) alkenyl silane represented by the general formula C _m H _{2m -1} SiH ₃ from alkenyl chlorosilane represented by the formula and hydrogenated sodium aluminum hydride. A method for synthesizing an alkenylsilane, wherein the reaction is performed in the presence of a solvent of one or more of tetrahydrofuran, ethylene glycol dimethyl ether and diethyl ether.