JPH08295695A - New organic halosilane compound - Google Patents

Abstract

PURPOSE: To obtain the subject new compound which is a specific 9,10-bis(alkylphenylhalosilyl)anthracene compound useful as a raw material, etc., for organosilicon-based polymers useful for various applications such as a luminous, a photoconductive and a resist materials. CONSTITUTION: A new 9,10-bis(alkylphenylhalosilyl)anthracene of formula I (R is a 1-3C alkyl; Ph is phenyl; X<1> and X<2> are each a halogen). This compound is useful as a raw material monomer, etc., for organosilicon-based polymers useful for various applications such as a luminous, a photoconductive and a resist materials. The organic halosilane compound is obtained by reacting 9,10- dilithioanthracene, etc., of formula II with an alkylphenyldihalosilane of formula III (X<4> is a halogen) in an inert solvent in an inert gas atmosphere. Furthermore, the compound is thermally reacted with an organic dihalosilane in the presence of an alkali metal to afford a polysilane having structural units of formulas IV and V (R<2> and R<3> are each a 1-10C alkyl or an aryl).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel organic halosilane compound. Organic halosilane compounds are used industrially or in synthetic chemistry as a raw material monomer for an organosilicon polymer, which has been attracting attention as a silicone raw material or a silylating agent, and in recent years as a light emitting material, a photoconductive material, a resist material and the like. It is an important compound. The present invention relates to a novel monomer that can be used as a raw material for producing an organosilicon polymer useful as a light emitting material, a photoconductive material, a resist material and the like.

[0002]

2. Description of the Related Art Organosilicon polymers have been attracting attention in recent years as polymers having a light emitting function and the like. For example,
It has been clarified that the organic polysilane emits light by σ-σ conjugation derived from the Si—Si bond of the main chain. For example, poly (methyl-n-propylsilane), which is a typical polysilane, exhibits an emission spectrum having a maximum wavelength of 340 nm, and poly (di-n-hexylsilane) exhibits emission having a maximum wavelength of 342 nm. . However, since the emission wavelength of the polysilane is in the ultraviolet region, it cannot be applied as a material for a display element or the like. On the other hand, in poly (diphenylsilane) in which two substituents are all aryl groups, poly (diphenylsilane) soluble in an organic solvent, in which an alkyl group is introduced into the para-position of both phenyl groups located in the side chains thereof, -P-alkylphenylsilane) is known to have an emission maximum near the visible region of 400 nm [Chemical Reviews, Vol. 89, No. 6, page 1382 (1989). ]. However, its luminous efficiency is quite low, and in order to obtain poly (di-p-alkylphenylsilane) soluble in an organic solvent,
It was necessary to introduce relatively long-chain n-butyl or n-hexyl into the alkyl group. Therefore, it becomes very difficult to synthesize the raw material monomer for obtaining the polymer, and the reactivity of the monomer is lowered, resulting in that the produced polymer can be obtained only in a yield of about several%, resulting in low emission efficiency. In addition, it is not satisfactory in practice. Further, as a document relating to an organosilicon polymer, the formula

[0003]

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(In the formula, R ^a represents a π-conjugated divalent organic group having 2 to 30 carbon atoms, R ^b represents a hydrocarbon group having 1 to 30 carbon atoms, and X ^a represents ^a halogen atom. , M is 1 ≦ m ≦
JP-A-6-9786 discloses ^a silicon-containing organic compound represented by the formula (2, n represents a number satisfying n ≧ 2) (arylene group is included in various groups listed as ^Ra ), Further, in the description of the prior art in this document, a poly (disilanylene phenylene) derivative, a poly (disilanylene naphthylene) derivative and the like are mentioned. However, this compound has a low luminous efficiency and is not sufficiently satisfactory for practical use.

Also, the formula

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[0006] (wherein, R ^c and R ^d are the same or different straight-chain alkyl group having 1 to 6 carbon atoms, and is the total number of carbon atoms of R ^c and R ^d is 8 or less, X ^b And X ^c are the same or different halogen atoms), and 9,10-bis (dialkylhalosilyl) anthracene (Japanese Patent Application No. 6-129692) and an anthrylene group in a part of the main chain using the same. A polysilane derivative (Japanese Patent Application No. 6-129693) introduced with is applied for a patent by the present applicant, but this polysilane derivative has no aromatic group in R ^c and R ^d . In the above 9,10-bis (dialkylhalosilyl) anthracene, the formula:

[0007]

[Chemical 4]

The compound represented by the formula has already been published [Proceedings of the 68th Spring Meeting of the Chemical Society of Japan, page 353 (199)
4)].

[0009]

DISCLOSURE OF THE INVENTION The present inventors have aimed to efficiently obtain a high molecular weight organosilicon polymer which emits light in the visible region and is soluble in ordinary organic solvents.
As a result of intensive research on the organic halosilane which is the monomer, an alkylphenylhalosilyl group has been introduced at the 9- and 10-positions of anthracene, which is easy to synthesize as a monomer, and when made into a polymer, it is visible in the visible region. The present invention has been completed by discovering a novel organic halosilane compound which emits light, is excellent in mechanical strength, and is capable of obtaining a soluble high molecular weight polymer in high yield.

[0010]

The present invention is based on the formula [1]

[0011]

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(Wherein R is a linear alkyl group having 1 to 3 carbon atoms, Ph is a phenyl group, and X ¹ and X ² are the same or different halogen atoms) , 1
0-bis (alkylphenylhalosilyl) anthracene (hereinafter referred to as bissilylanthracene compound [1])
Is provided.

R in the bissilylanthracene compound [1] of the present invention is a linear alkyl group having 1 to 3 carbon atoms, preferably a methyl group. Whether R is branched,
When the carbon number exceeds 3, the steric hindrance thereof lowers the reactivity as a monomer, resulting in a decrease in polymer yield, which is industrially disadvantageous. Specific examples of R include a methyl group, an ethyl group and an n-propyl group. The halogen atom represented by X ¹ or X ² in the bissilylanthracene compound [1] is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

Specific examples of the bissilylanthracene compound [1] according to the present invention include 9,10-bis (methylphenylchlorosilyl) anthracene, 9,10-bis (ethylphenylchlorosilyl) anthracene, 9,10-
Bis (n-propylphenylchlorosilyl) anthracene, 9,10-bis (methylphenylbromosilyl) anthracene, 9,10-bis (ethylphenylbromosilyl) anthracene, 9,10-bis (n-propylphenylbromosilyl) Anthracene, 9-methylphenylchlorosilyl-10-methylphenylbromosilyl anthracene, 9-ethylphenylchlorosilyl-10-
Examples thereof include ethylphenyl bromosilyl anthracene and 9-n-propylphenylchlorosilyl-10-n-propylphenyl bromo silyl anthracene, and preferred examples include 9,10-bis (methylphenylchlorosilyl) anthracene and 9,10-bis. (Methylphenyl bromosilyl) anthracene is mentioned, and a particularly preferable example is 9,10-bis (methylphenylchlorosilyl) anthracene. The bissilylanthracene compound [1] has, for example, the formula [2]

[0015]

[Chemical 6]

9,10-dilithioanthracene represented by the formula or the formula [3]

[0017]

[Chemical 7]

A Grignard reagent represented by the formula (wherein X ³ is a halogen atom), that is, 9,10-dimagnesium halogenoanthracene, and a compound of the formula [4]

[0019]

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(Wherein R is a linear alkyl group having 1 to 3 carbon atoms, Ph is a phenyl group, and X ⁴ is a halogen atom), and an alkylphenyldihalosilane represented by the following formula: By reacting in an inert solvent in an inert gas atmosphere, it can be easily obtained in high yield. The halogen atom represented by X ⁴ is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

Specific examples of the alkylphenyldihalosilane [4] include methylphenyldichlorosilane, ethylphenyldichlorosilane, n-propylphenyldichlorosilane, methylphenyldibromosilane, ethylphenyldibromosilane and n-propylphenyldibromosilane. Among them, preferred examples include methylphenyldichlorosilane and methylphenyldibromosilane, and particularly preferred examples include methylphenyldichlorosilane.

An aprotic organic solvent is preferable as the inert solvent, and specific examples thereof include diethyl ether, tetrahydrofuran, n-hexane, n-octane, n-pentane, benzene, toluene, xylene and the like. Examples of the inert gas include argon and nitrogen. The inert solvent is preferably used in such an amount that the concentration of 9,10-dilithioanthracene [2] or 9,10-dimagnesium halogenoanthracene [3] is 100 mmol / L to 2 mol / L. Alkylphenyldihalosilane [4] and 9,10-dilithioanthracene [2] or 9,10-dimagnesium halogenoanthracene [3]
The reaction ratio with is preferably 2 to 10 equivalents of alkylphenyldihalosilane [4] with respect to 9,10-dilithioanthracene [2] or 9,10-dimagnesium halogenoanthracene [3], More preferably, it is 2 to 6 equivalents. If it is less than 2 equivalents, the yield of the reaction product may decrease, and if it exceeds 10 equivalents, the yield of the target product is not adversely affected, and the alkylphenyldihalosilane [4] is wasted. It is industrially disadvantageous. The reaction temperature is preferably -30 to 70 ° C, more preferably 0 to 50 ° C, most preferably 10 to 50 ° C. If it is lower than -30 ° C, the reaction rate may not be sufficient, and if it exceeds 70 ° C, the selectivity of the reaction may decrease. The reaction time varies depending on the reaction temperature, the reaction solvent and the like, but the reaction is usually completed within 24 hours.

When it is desired to obtain a bissilylanthracene compound [1] in which X ¹ and X ² are different from each other, for example, an alkylphenyldihalosilane [4] in which X ⁴ is X ¹ is used.
And a mixture of alkylphenyldihalosilanes [4] in which X ⁴ is X ² or both compounds are staggered for 9,1
Means such as sequential reaction with 0-dilithioanthracene [2] or 9,10-dimagnesium halogenoanthracene [3] can be used. To obtain the produced bissilylanthracene compound [1] from the reaction solution obtained by the above reaction, the by-produced lithium halide or magnesium halide precipitate is removed from the reaction solution by filtration, decantation or the like, and then the reaction solvent is used. May be distilled off under reduced pressure, and the residue may be purified by a method such as recrystallization from an inert solvent such as pentane. The obtained bissilylanthracene compound [1] is a yellow solid.

[0024]

EXAMPLES The present invention will be specifically described below based on Examples and Reference Examples. In Reference Examples, the weight average molecular weight and the number average molecular weight were determined by the GPC method (in terms of polystyrene), and the molar ratio (%) of structural units and the emission efficiency were determined by the methods described below. (1) Molar ratio (%) of structural units It is calculated by the following procedure. The standard absorbance for anthracene is determined as follows.
A standard solution in which a predetermined molar amount of anthracene is dissolved in a chloroform solvent is prepared, and the molar absorbance at λmax of UV absorption is measured, and this is used as the standard absorbance. The number of moles of the structural unit A during the purpose formation is determined as follows.
A solution of the target product (polymer) having the same solvent as the standard solution and the same molar concentration (converted from the number average molecular weight of the entire polymer) was prepared, and the molar absorbance of λmax attributed to anthracene in UV absorption was measured. The standard absorbance is divided to obtain the number of moles of the anthrylene group in the target production. This is equal to the number of moles of structural unit A. The weight of the structural unit A during the objective production is calculated by the following formula. Weight of structural unit A = (molecular weight of structural unit A obtained by subtracting halogen atoms X ¹ and X ² from bissilylanthracene compound [1] used as a raw material) × (mol number of structural unit A) Structural unit in the objective formation The number of moles of B is calculated by the following formula. Number of moles of structural unit B = (weight of target product used for measurement of molar absorbance−weight of structural unit A) / (structure obtained by subtracting halogen atoms X ⁵ and X ⁶ from silane compound [5] used as a raw material Molecular Weight of Unit B) Structural Unit A / Structural Unit B Molar Ratio (%) During Target Generation
Is calculated by the following formula. Structural unit A / structural unit B [molar ratio (%)] = (number of moles of structural unit A determined by) × 100 / (number of moles of structural unit B determined by) (2) Luminous efficiency Standard substance in chloroform As the formula

[Chemical 9] Was measured using Alq ₃ (emission efficiency 10.1%).

EXAMPLE A reactor equipped with a stirrer and an external cooling jacket is
21.5 g (64 mmol) of dibromoanthracene was added, the system was degassed in vacuum, and the atmosphere was made dry argon. Add 260 ml of dehydrated and purified diethyl ether, and add n-butyllithium (1
A solution of 0.2 g of hexane (100 ml) was gradually fed to the reactor and stirred under an argon atmosphere at 10 to 30 ° C. for 3 hours to produce 9,10-dilithioanthracene. In a separate reactor equipped with stirrer and external cooling jacket, 100 ml of diethyl ether and 66.9 of methylphenyldichlorosilane are placed.
g (350 mmol), and under argon atmosphere at room temperature,
The 9,10-dilithioanthracene obtained above was added dropwise to the contents, and the mixture was stirred at 10 to 30 ° C. for 20 hours for reaction. By-produced lithium chloride was filtered off, the reaction solvent was distilled off under reduced pressure, and then recrystallized from n-pentane.
Obtained 9,10-bis (methylphenylchlorosilyl) anthracene as a yellow solid. The yield was 42%.

As a result of analyzing the chlorine content of this compound,
The chlorine content was 14.41% by weight, which was in good agreement with the calculated value of 14.54% by weight. The 1H nuclear magnetic resonance spectrum [measured using deuterated chloroform (7.25 ppm) as a standard] is shown in FIG. From Figure 1, the chemical shift δ (ppm) is 8.4 to 7.3.
(9,10-substituted anthracene), 7.7 ~7.4 (Si-C 6
H ₅ ), 1.3 (Si—CH ₃ ), and the result measured by MS spectrum was m / z 488 (M ⁺ ), and the obtained compound was 9,10-bis (methylphenylchlorosilyl). It was confirmed to be anthracene.

Reference Example 1 Synthesis of anthrylene group-containing methylphenylpolysilane 4.6 g of sodium in a 300 ml container in an argon atmosphere.
And 140 ml of toluene were charged. Next, the system is heated to the boiling point of toluene to melt sodium in a reflux atmosphere,
The sodium was finely dispersed by vigorous stirring. After that, the content temperature was kept near the boiling point of the solvent while stirring, and 2.5 mmol (1.22 g) of toluene (10,9-bis (methylphenylchlorosilyl) anthracene obtained in the example (10
solution) and a 24-fold molar amount of methylphenyldichlorosilane (a compound of R ² = methyl group, R ³ = phenyl group, X ⁵ = X ⁶ = chlorine in the following chemical formula 10) (11.33 g). It was dripped slowly. After completion of the dropping, the reaction was carried out for about 2 hours near the boiling point of the solvent. After the completion of the polymerization reaction, the mixture was cooled to room temperature, sodium chloride produced as a by-product and excess sodium metal were separated by filtration, and the filtrate was concentrated and added dropwise to a large amount of methanol to precipitate the polymer. The precipitated polymer is separated and dried to obtain a target polymer composed of a structural unit A in which R = methyl group in Postscript 11 and a structural unit B in which R ² = methyl group and R ³ = phenyl group in Postscript 12. 3.42 g
(Yield 55.0%) was obtained as a yellow solid. This polymer showed a bimodal molecular weight distribution consisting of components having a weight average molecular weight (Mw) of 406,000 and 7,200 (Fig. 2). The number average molecular weight (Mn) of the entire polymer is 5,800, and the molar ratio (%) of structural unit A / structural unit B of the present polymer is 2.
It was 8%. The polymer also emitted light at 480 nm according to the emission spectrum. Furthermore, the luminous efficiency of this polymer was 85%.

Reference Example 2 Synthesis of anthrylene group-containing dimethylpolysilane 4.6 g of sodium and 5.0 mmol of 9,10-bis (methylphenylchlorosilyl) anthracene obtained in the example.
A solution of (2.44 g) in toluene (10 ml) and a 12-fold molar amount of dimethyldichlorosilane [in the following chemical formula 10, R ² = R ³ = methyl group, X ⁵ = X ⁶ = chlorine compound] (7.78 g) Using the same conditions and procedures as in Reference Example 1, a yellow color consisting of a structural unit A in which R = methyl group in postscript 11 and a structural unit B in which R ² = R ³ = methyl group in postscript 12 is used. Was synthesized. Polymer yield 0.94g (yield 16.9
%)Met. This polymer showed a monomodal molecular weight distribution with Mw of 1,200 (Fig. 3). Mn of this polymer is 600
And the molar ratio (%) of structural unit A / structural unit B of the present polymer was 6.5%. In addition, the emission spectrum of this polymer showed emission at 450 nm.

[0029]

INDUSTRIAL APPLICABILITY The 9,10-bis (alkylphenylhalosilyl) anthracene [1] of the present invention is an organosilicon having excellent emission characteristics, photoconductivity and resist characteristics in which the maximum emission wavelength is shifted to the visible region. It is a compound which is useful as a raw material for a polymer or as a silicone raw material and a silylating agent. The bissilylanthracene compound [1] of the present invention and the formula [5]

[0030]

[Chemical 10]

(Wherein R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, aryl groups or aralkyl groups, and X ⁵ and X ⁶ are the same or different halogen atoms). It is also possible to react with a silane compound represented by the formula A obtained by reacting these in an inert solvent in the presence of an alkali metal or an alkaline earth metal.

[0032]

[Chemical 11]

(Wherein R is a straight-chain alkyl group having 1 to 3 carbon atoms and Ph is a phenyl group) and a structural unit A and a formula B

[0034]

[Chemical 12]

(Wherein R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, aryl groups or aralkyl groups), and the structural unit A / A polysilane derivative having an anthrylene group in a part of its main chain (see Reference Example) having a molar ratio (%) of structural unit B of 0.5 to 10% and a weight average molecular weight of 1,000 to 1,000,000 emits light in the visible region. It is a high molecular weight organosilicon polymer which is excellent in light emission efficiency and soluble in ordinary organic solvents, and is useful as a light emitting material, a photoconductive material, a resist material and the like.

[Brief description of drawings]

FIG. 1 shows the 1H nuclear magnetic resonance spectrum of 9,10-bis (methylphenylchlorosilyl) anthracene of Example.

FIG. 2 shows a molecular weight distribution of the polymer obtained in Reference Example 1.

FIG. 3 shows a molecular weight distribution of the polymer obtained in Reference Example 2.

Claims (1)

[Claims] 1. A formula [1]: (In the formula, R is a linear alkyl group having 1 to 3 carbon atoms,
Ph is a phenyl group, and X ¹ and X ² are the same or different halogen atoms) 9,10-bis (alkylphenylhalosilyl) anthracene.