JPH02247187A - Novel organosilicon compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R<1> to R<3> represent alkyl, aryl or aralkyl). EXAMPLE:Dimethyl[2-(1-methylindolyl)]silane. USE:A raw material for producing a silicon thin film by gas-phase polymerization method and a raw material for a coloring matter for an optical disc. PREPARATION:An N-substituted indole expressed by formula II (example; N- methylindole) is reacted with an alkyllithium (preferably t-butyllithium) in an inert atmosphere to form an organolithium compound expressed (by formula III, which is then reacted with a dihalosilane expressed by formula IV (X represents halogen) (preferably dichlorodimethylsilane, etc.). In the reactions, 1-1.2 mole alkyllithium is preferably used to 1 mole compound expressed by formula II, and 0.5-0.6mol dihalosilane to 1mol compound expressed by formula II, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel organosilicon compound.
This invention relates to indolyl-substituted monosilane compounds. Such organosilicon compounds are useful, for example, as raw materials for producing silicon thin films by gas phase polymerization, or as raw materials for dye materials for optical disks.

Various organosilicon compounds have been known in the past, but compared to organic carbon compounds, their research has not yet progressed as far as they have. For example, various organosilicon compounds having substituents such as alkyl groups, phenyl groups, alkoxy groups, and halogen atoms on the silicon atom have been known, but organosilicon compounds in which the silicon atom is substituted with a heterocycle Very little is known about the compound, and, of course, no method has been established for its production.

The object of the present invention is to provide a novel organosilicon compound having a heterocycle as a substituent on a silicon atom, particularly an indolyl-substituted monosilane compound.

The organosilicon compound according to the present invention is characterized by being represented by the formula % (wherein R1, R2 and R3 each independently represent an alkyl group, an aryl group or an aralkyl group).

In the above formula (I), R1, R2 and R3 preferably each independently represent an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 13 carbon atoms. As specific examples, alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 5ec-butyl, t-butyl, amyl, hexyl groups, etc., and aryl groups include Examples of the aralkyl group include phenyl, tolyl, and methoxyphenyl groups. Examples of the aralkyl group include hensyl, phenethyl, and p-methylbenzyl groups.

Therefore, specific examples of preferred organosilicon compounds according to the invention include, for example, dimethyldi[2(1-methylindolyl)]silane, methylphenyldi[2-(1-methylindolyl)]silane, diphenyldi[2-(1-methylindolyl)]silane, and diphenyldi[2-(1-methylindolyl)]silane. -methylindolyl)]silane, and the like.

Such a novel organosilicon compound according to the present invention can be obtained by reacting an alkyllithium with an N-substituted indole represented by the general formula (wherein R1 is the same as above) under an inert atmosphere. (in which R1 is the same as above) is produced, and then,
It can be obtained by reacting this compound with a dihalosilane represented by the general formula % (wherein R2 and R3 are the same as above, and X represents a halogen atom).

In the above-mentioned formula (II), R■ is the same as above, and therefore, as the N-substituted indole, for example, N-
Methylindole, N-phenylindole, etc. are preferably used. Furthermore, the N-substituted indole may have an alkyl group, an aralkyl group, or an aralkyl group as described above on the benzene ring as a substituent.

In addition, examples of the alkyllithium include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, 5ec-butyllithium, t-butyllithium, amyllithium,
Examples include hexyllithium, but in particular, t
-Butyllithium is preferably used.

The above reaction is carried out under an inert atmosphere, usually in a solvent. The solvent is not particularly limited as long as it is inert to the alkyl lithium used, but
For example, ether solvents such as diethyl ether, dimethoxyethane, dioxane, and tetrahydrofuran, aliphatic hydrocarbons such as pentane and hexane, aromatic hydrocarbons such as benzene, toluene, and xylene, or mixed solvents thereof are preferably used. Further, the alkyl lithium is also usually prepared in the same inert solvent as these and used as such a solution. Generally, nitrogen, argon, etc. are suitable as the inert atmosphere.

The N-substituted indole is reacted with an alkyl lithium to obtain a lithiated N-substituted indole compound represented by the formula (I By adding dihalosilane represented by (IV) and reacting, the desired organosilicon compound according to the present invention can be obtained.

In the dihalosilane represented by formula (IV), R2 and R3 are the same as above, and X represents a halogen atom, such as chlorine, bromine or iodine. especially,
Dichlorosilane is preferably used. Therefore, as the dihalosilane, for example, dichlorodimethylsilane, dichlorodiphenylsilane, methylphenyldichlorosilane, dichlorodibenzylsilane, etc. are preferably used.

In the reaction between an N-substituted indole and an alkyl lithium, the alkyl lithium is generally used in an amount of 1 to 1.2 mol per 1 mol of the N-substituted indole. Further, dihalosilane is generally used in an amount of 0.5 to 0.6 mol per 1 mol of N-substituted indole.

Although the reaction temperature and reaction time are not particularly limited, for example, in the reaction between an N-substituted indole and an alkyl lithium, the alkyl lithium solution is added to the N-substituted indole solution at a temperature ranging from -100°C to 25°C. ℃, preferably in the range of -80°C to 30°C, and then at a temperature in the range of -30°C to 80°C, preferably 0 to 40°C, usually for several minutes to about 10 minutes. time, preferably 3
Stir for 0 minutes to 2 hours, thus forming the lithiated N-substituted indole.

Then, in the reaction of this lithiated N-substituted indole with a dihalosilane, the dihalosilane is added to the reaction mixture containing the lithiated N-substituted indole at a temperature usually from -100°C to 80°C, preferably from -80°C to 30°C. After addition at a temperature of -30°C to 80°C, preferably
At a temperature in the range of 0 to 50°C, usually for 30 minutes to about 4
The reaction is allowed to proceed with stirring for 0 hours, preferably from 1 hour to 20 hours.

After the reaction is completed, the solvent is distilled off from the reaction mixture under reduced pressure, and the resulting residue is recrystallized from an appropriate solvent or distilled under reduced pressure to obtain the desired indolyl-substituted monosilane compound. As the recrystallization solvent, aromatic hydrocarbons, aliphatic hydrocarbons, or mixed solvents thereof are suitable, for example.

According to the present invention, an indolyl-substituted monosilane compound, which is a novel organosilicon compound, is provided.

Such an organosilicon compound can be obtained by reacting an N-substituted indole with an alkyllithium and then reacting it with a dihalosilane.

Implementation (2) The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 (Synthesis of dimethyldi[2-(1-methylindolyl)]silane) 7 ml of a solution of 1.31 g (10 mmol) of 1-methylindole in tetrahydrofuran was cooled to -78°C, and a solution of 1.7 molar concentration was added to the solution. 7.1 ml of a hexane solution of t-butyllithium/l was added. The temperature was raised to 25° C. and stirred at this temperature for 1.5 hours. After this, the reaction mixture was again cooled to -78°C and dichlorodimethylsilane was added to 0.6°C.
5 g (5.0 mmol) was added, then warmed to room temperature and stirred for 2 hours.

After the reaction, the solvent was distilled off from the reaction mixture under reduced pressure, and the resulting residue was recrystallized from a mixed solvent of toluene/hexane (volume ratio 1/1) to give dimethyldi(1-(1-methylindolyl)). ] 0.80 g of silane was obtained as colorless needle crystals. Yield: 50%.

Melting point 107-108°C Infrared absorption spectrum (KBrBr method, cm') 149
0, 1462.1350.1298.1070.895
．． 820875, 734.677°1■-Nuclear magnetic resonance absorption spectrum (CDCI3 solution, δ
(ppm)) 0.76 (68,s, 5iCH3), 3.
60 (6H,s, NCH3)6.84 (2
H,s, olefinic H), 6.9-7
．． 3 (6H, maromatic H)+7.
5-7.7 (21+, m, aromati
c11).

Mass spectrum (m/e) 318 (M”), 303.187.144゜Example 2 (methylphenyldiC2-(1-methylindolyl))
Synthesis of silane) In Example 1, instead of dichlorodimethylsilane,
Methylphenyldi(2-(1-methylindolyl))silane was obtained in the same manner as in Example 1, except that methylphenyldichlorosilane was used. Yield: 40%.

Melting point: 151-153°C Infrared absorption spectrum (KBrBr method, cm-') 1
490, 1460. 1420.1350. 132
0. 1296. 1100°1065, 802.79
0.739.720.623°+1-nuclear magnetic resonance absorption spectrum (CDCI3 solution, δ (ppm)) 1.00 (3H,s, 5iCHs), 3.66 (
6H,s, NCF13) 6.70 (2H,S,
olefinic H) + 6.9-7.7 (
13H+ maromatic H).

Mass spectrum (m/e) 380 (M+).

Example 3 (Synthesis of diphenyldi[2-(1-methylindolyl)]silane) In Example 1, instead of dichlorodimethylsilane,
Diphenyldi[2(1-methylindolyl)]silane was obtained as needle-shaped crystals in the same manner as in Example 1 except that dichlorodiphenylsilane was used. Yield 60%.

Melting point: 206-207°C Infrared absorption spectrum (KBrBr method, cm-') 14
90, 1460.1422.1352.1300.11
03.1070790, 740.698.630.50
0゜1H-nuclear magnetic resonance absorption spectrum (CDC13 solution, δ (ppm)) 3.57 (6H,s, NCt(+), 6.73
(2)1. s, olefinicH) + 7.0-
7.8 (18H, m, aromatic H).

Mass spectrum (m/e) 442 (M”).

Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent Patent attorney Itsube Makino

Claims (4)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R^1, R^2, and R^3 each independently represent an alkyl group, an aryl group, or an aralkyl group.) An organosilicon compound characterized by the following: (2) Dimethyldi[2-(1-methylindolyl)]silane. (3) Methylphenyldi[2-(1-methylindolyl)]silane. (4) Diphenyldi[2-(1-methylindolyl)]
Silane.