JPS58152893A - Novel ethynylenepolysilane compound and its preparation - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI(R is alkyl; n is >=1). EXAMPLE:7,7,8,8,9,9-Hexamethyl-7,8,9-trisilacyclo-1,5-nonadiyne. USE:Agent for generating organic silylene. PROCESS:The objective compound can be prepared e.g. by reacting the compound of formula III (X is Cl or Br) (e.g. 1,3-dichlorohexamethyltrisilane) with the di-Grignard reagent of formula II derived from 1,6-hexadiyne and phenylmagnesium bromide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ethynyleneborisilane compound and a method for producing the same.

Silylene, a divalent reactive intermediate, is highly reactive and is widely studied as it is expected to be used as a cross-linking agent for polymers and in new organic synthesis reactions. Various methods are known for generating organic silylene (:SiR,), such as a method of photolyzing borine diphosphones. This method has a wide range of applications because it is easy to operate.One of the methods mentioned above is known to photodecompose dehydrated phenyldisilanes, but this method results in 1,3-silicon rearrangement. Silaethene is mainly produced, and the production yield of organic silylene is low. Moreover, its sensitivity wavelength is limited to the ultraviolet region.

An object of the present invention is to provide a novel ethynylene polysilane compound that generates organic silylene in high yield through photolysis, and a method for producing the same.

For the above purpose, we synthesized various polyethyndidine polysilane compounds and investigated the yield of organic silylene.
It has been found that the novel ethenylene bolysine compounds shown below are useful.

The novel ethynylene borisilane compound of the present invention is as follows:
It is represented by general formula (1).

(However, R in general formula (1) represents an alkyl group.)
The novel ethynylene polysilane compound of the present invention includes:
For example, 7,7,8,8,9.9-hexamethyl-7,
Examples include 8,9-)risilacyclo1,5-nonadiyne.

The novel polyethynylene polysilane compound according to the present invention can be synthesized, for example, by the following reaction.

7.7,8,8,9,9-hexamethyl-7,8,? −
Trisilacyclo 1,5-nonadiyne (a compound in which R = methyl group and R = 1 in general formula (1)) is -c
-f in a digrignard reagent derived from 1t'-hexadiyne and phenylmagnesium bromide in a solution of 1. Add S-dichlorohexamethyltrisilane,
It can be synthesized by reacting at room temperature and further refluxing.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example t 200 mg After purging a 5-bottle flask with nitrogen, 2t (10256 mol) of 1,5-hexadiyne and 30sd of diethyl ether were placed therein, and the flask was cooled with ice. To this solution, add about 1 mol of phenylmagnesium bromide in 2N THF @25.6-(110512 mol as phenylmagnesium bromide) while stirring.
The mixture was added dropwise over 0 minutes, and further stirred at room temperature for 30 minutes. Add 1,3-dichlorohexamethyltrisilane &28 to this solution.
Mixture of f (α0256 mol) and diethyl ether AOsg #! After adding the bamboo shoots at once and stirring at room temperature for 1 hour,
It was refluxed for 1 hour. After conventional treatment, the crude product was distilled under reduced pressure to obtain 7.7, 8, 8. ? ,? -hexamethyl-7,8,9-)lysilacyclo1,5-nonadi 47 was obtained f. Yield 4ss bp, 1!16-138
The structure of this compound was confirmed from the following results in nuclear magnetic resonance spectrum (CM-NMR') and high resolution mass spectrum.

11+'H-NMR (δpp wind/CDC1,) Q,
22. (6B, singlet, methyl group) α27 (
12B, singlet, methyl group) 2.47 (4H,
singlet, t, methylene group) (2) Calculated value of high-resolution mass spectrum C□HIS- = 251566 Actual value = 251564 Example 2゜ 7, 7, 8, 8, 9. synthesized by the method of Example 1. 9
-hexamethyl-7,8,9-)lysilacyclo-1゜5
-Nonadiyne 2F was dissolved in benzene 50-, and 2.9 t of diethylmethylsilane was added as a silylene scavenger, and the mixture was irradiated with a 500W low-pressure mercury lamp for 10 minutes. The reaction mixture was separated by gas chromatography and analyzed by comparison with standard samples and mass spectroscopy. As a result, 1,1-diethyl-
1 g of 2°2-trimethyldisilane (80% yield, based on silylene scavenger) was obtained.

As described above, the novel ethynylenepolysilane compound of the present invention has strong absorption in the ultraviolet region based on σ(Si-5i)-π conjugation, so it has a high efficiency of generating organic silylene through photolysis, and is a new type of silylene. Useful as a generator.

Furthermore, it can be used to form a photoelectric conversion film as follows. For example, 7,7,8,8,9.9-hexamethyl''''-7°8
．． 9-) If a toluene solution (5 to 10 g) of lysinecyclo-1,5-nonadiyne is applied on a conductive substrate, and after drying and film formation, the entire surface is irradiated with low pressure mercury, an insoluble photoelectric conversion thin film can be formed. can be formed.

Furthermore, it can be used as a photoreceptor in a laser beam patterning system in a similar manner. That is, a photoconductive insoluble thin film pattern can be formed by laser beam irradiation on a thin film of the novel substance produced by the same method as above.

Claims (1)

[Scope of Claims] t A novel ethynylenebolysilane compound proboscis, characterized by being composed of a compound represented by the general formula 0) (wherein R in the general formula (1) represents an alkyl group). 2, 7, 7, 8, 8, 9. ? -hexamethyl-7,8
，? -) The novel ethynyleneborisilane compound according to claim 1, which is 2cyclo-1,5-nonadiyne. (5) A compound represented by general formula (2) and general formula (3)
1. A method for producing a novel ethynyleneborisilane compound, which comprises reacting a compound represented by the formula ill to obtain a compound represented by the general formula ill. However, in the general formulas (1) to (3), λ is an alkyl group, and in the general formulas (2) to (4, X is CI or By, and in the general formula +13, (21, 1 or more) The sl number of the compound represented by the general formula (1) is 7.7, 8, 8
,1゜9-hexamethyl-7,8,? -) Lisilathicou-1,5-nonadiyne, and the compound represented by the general formula (sl) is ClSi (CHs)* Si CC
Ha) House 5i (CHs)m Cj or Brag
(CHs) Snow S number (C7/s) tSL (CE a)
*The method for producing a novel ethenyleneborisilane compound according to claim 5, wherein the compound is Br.