JP2006062964A - pi-ELECTRON-CONJUGATED ORGANIC SILANE COMPOUND AND METHOD FOR PRODUCING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a compound used for producing an organic thin film excellent in peeling resistance and also having a high ordering property, crystallinity and electroconductive characteristic, and a method for producing the same. <P>SOLUTION: This π-electron-conjugated organosilane compound is expressed by the formula: H-(R<SP>1</SP>)<SB>m</SB>-SiR<SP>2</SP>R<SP>3</SP>R<SP>4</SP>[wherein, R<SP>1</SP>is a divalent organic group derived from a fused polycyclic hetero ring compound having 2-10 number of the fused rings constituted by 5- or 6-membered rings; (m) is 2 to 10 integer; and R<SP>2</SP>to R<SP>4</SP>are each independently a halogen atom or a 1-4C alkoxy]. The method for producing the organosilane compound is provided by performing the Grignard reaction of a compound of the formula; H-(R<SP>1</SP>)<SB>m</SB>-MgX<SP>1</SP>[wherein, R<SP>1</SP>and (m) are each the same as above; and X<SP>1</SP>is a halogen atom] with a compound of the formula: X<SP>2</SP>-SiR<SP>2</SP>R<SP>3</SP>R<SP>4</SP>[wherein, X<SP>2</SP>is H, a halogen atom or a 1-4C alkoxy; and R<SP>2</SP>to R<SP>4</SP>are each the same as above]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a π-electron conjugated organosilane compound and a method for producing the same, and more particularly, to a π-electron conjugated organosilane compound that is a novel conductive or semiconductive substance useful as an electrical material and a method for producing the same. .

  In recent years, semiconductors using inorganic materials are easy to manufacture, easy to process, can respond to device enlargement, and can be expected to reduce costs due to mass production, and synthesize organic compounds with more functions than inorganic materials. Because of this, semiconductors using organic compounds (organic semiconductors) are attracting attention, and semiconductor materials are being developed along with device research and development. Conventionally, since semiconductor layers have been mainly formed by vapor deposition, material development has been mainly focused on π-electron conjugated skeletons, and a typical example is pentacene. On the other hand, the semiconductor layer formed by vapor deposition has problems such as complicated processes and low film strength, and thus has a strong interaction with the substrate and forms a crystalline thin film. The development of organic materials that can be used is required.

As a method for forming such an organic thin film, in recent years, a method using self-organization has attracted attention, and accordingly, a material having self-organization ability has been developed. Of these, silicon-based compound films are attracting attention because of their high durability, and typical developments include silane coupling agents having an alkyl group with a high water-repellent effect and a fluorinated alkyl group as an organic functional group. Or the compound which has one thiophen ring as a functional group at the terminal of a molecule | numerator, and couple | bonded the thiophen ring with the silicon atom via the linear hydrocarbon group is proposed (for example, patent document 1).
Japanese Patent No. 2889768

  However, with the organic compounds proposed above, it has not been possible to obtain an organic thin film having sufficient order, crystallinity, and electrical conductivity.

  The present invention has been made in view of the above problems, and can be easily crystallized by a simple manufacturing method to form an organic thin film, and the obtained organic thin film is firmly adsorbed on the substrate surface, It is an object of the present invention to provide a compound for producing an organic thin film that prevents physical peeling and has high order, crystallinity, and electrical conductivity, and a method for producing the same.

The present invention relates to a general formula (α)
H- (R ¹ ) _m -SiR ² R ³ R ⁴ (α)
(In the formula, R ¹ is a divalent organic group derived from a condensed polycyclic hydrocarbon compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered monocyclic hydrocarbon ring. M is an integer of 2 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms).

The present invention also provides a general formula (β);
H- (R ¹ ) _m -MgX ¹ (β)
(In the formula, R ¹ is a divalent organic group derived from a condensed polycyclic hydrocarbon compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered monocyclic hydrocarbon ring. M is an integer of 2 to 10; X ¹ is a halogen atom) and a general formula (γ);
X ² —SiR ² R ³ R ⁴ (γ)
Wherein X ² is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 4 carbon atoms; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms. The present invention relates to a method for producing the above π-electron conjugated organosilane compound, characterized by causing a Grignard reaction with the compound to be produced.

  Since the organic silane compound of the present invention has a silyl group at the terminal and thus has a self-organizing ability, the organic thin film has a very high stability and is highly crystallized by a solution method. Can be configured. Moreover, since the organosilane compound of the present invention contains a skeleton of a condensed polycyclic hydrocarbon compound, high conductivity can be imparted when an organic thin film is formed. Therefore, the organosilane compound of the present invention is very useful not only in organic thin film transistor materials but also in organic devices such as solar cells, fuel cells, and sensors.

(Organic silane compound)
The π-electron conjugated organosilane compound of the present invention has the general formula (α);
H- (R ¹ ) _m -SiR ² R ³ R ⁴ (α)
(Hereinafter, the organosilane compound represented by the general formula (α) is referred to as an organosilane compound (α)).

In the formula (α), R ¹ is a divalent organic group derived from a π-electron conjugated condensed polycyclic hydrocarbon compound composed of a 5-membered ring and / or a 6-membered monocyclic hydrocarbon ring. Yes, that is, a divalent residue obtained by removing two hydrogen atoms from any ring-constituting atom of the condensed polycyclic hydrocarbon compound. The π electron conjugation means that π electrons that control the π bond are delocalized based on the σ bond and π bond of the compound.

Examples of the 5-membered ring and 6-membered monocyclic hydrocarbon ring constituting such a condensed polycyclic hydrocarbon compound include the following rings.

  The total number of condensed rings (monocyclic hydrocarbon rings) constituting the condensed polycyclic hydrocarbon compound is 2 to 10, and 2 to 5 is preferable in consideration of the yield.

Examples of the condensed polycyclic hydrocarbon compound capable of deriving the organic group R ¹ include compounds represented by the following general formulas (I) to (IX). That is, each of the organic groups R ¹ may be independently a divalent organic group derived from a condensed polycyclic hydrocarbon compound selected from the group consisting of such compounds.

In formula (I), n1 is an integer of 0 to 8, preferably 0 to 4.
In formula (II), n2 and n3 are each an integer of 0 or more such that the sum thereof is 1 to 9, preferably 2 to 6. n2 and n3 respectively represent the number of condensed benzene rings extending in the lower left direction and the lower right direction in the above general formula.
In the formula (III), n4 and n5 are each an integer of 1 or more such that the sum thereof is 2 to 9, preferably 2 to 6. n4 and n5 respectively represent the number of condensed benzene rings extending in the lower left direction and the lower right direction in the above general formula.
In formula (IV), n6 is an integer of 0-7, preferably 2-6. n6 represents the number of condensed benzene rings extending rightward in the above general formula.

  Specific examples of the condensed polycyclic hydrocarbon compound represented by the general formula (I) include the following compounds.

  Specific examples of the condensed polycyclic hydrocarbon compound represented by the general formula (II) include the following compounds.

  Specific examples of the condensed polycyclic hydrocarbon compound represented by the general formula (III) include the following compounds.

  Specific examples of the condensed polycyclic hydrocarbon compound represented by the general formula (IV) include the following compounds.

The position of the two hydrogen atoms from which the condensed polycyclic hydrocarbon compound is removed to derive the divalent organic group R ¹ , that is, the bonding position with other groups in the organic group R ¹ is not particularly limited. However, for example, when the compound molecule is substantially linear, it is preferably at both ends of the molecule. Further, for example, when the compound molecule has line symmetry, it is preferable that the bond position is such that the line connecting the two bond positions passes through the midpoint of the center line serving as a reference for line symmetry. Further, for example, when the compound molecule has point symmetry, it is preferable that the bond position is such that a line connecting the two bond positions passes through the center point which is a reference for point symmetry.

All the organic groups R ¹ may be the same or part or all may be different.

In the present invention, a preferable combination of the organic group R ¹ is a combination of groups derived from a compound selected from the following group a.
Group a: Compounds represented by general formulas (I) to (V).

In the formula (α), m represents the number of organic groups R ¹ bonded by a single bond, and is not particularly limited as long as it is an integer of 2 or more. An integer of 10, especially 2 to 5 is preferred.

In the above formula (α), R ^{2 to} R ⁴ constituting the silyl group are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms. The alkoxy group is preferably linear.
Specific examples of the alkoxy group include, for example, methoxy group, ethoxy group, n-propoxy group, 2-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like. In the alkoxy group, part of hydrogen may be further substituted with another substituent, for example, a trialkylsilyl group (the alkyl group has 1 to 4 carbon atoms), an alkoxy group (1 to 4 carbon atoms), or the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom, and a chlorine atom is preferable in consideration of reactivity.
Preferred R ^{2 to} R ⁴ are each independently a chlorine atom or an alkoxy group having 1 to 2 carbon atoms, and more preferably the same group.

Preferable specific examples of the organic silane compound (α) as described above include the following organic silane compounds.

(Production method)
The organic compound (α) of the present invention has the general formula (β);
H- (R ¹ ) _m -MgX ¹ (β)
Wherein R ¹ and m are the same as in general formula (α); X ¹ is a halogen atom, and a general formula (γ);
X ² —SiR ² R ³ R ⁴ (γ)
(Wherein X ² is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 4 carbon atoms; R ^{2 to} R ⁴ are the same as those in formula (α)) and Grignard It can be produced by reacting.

  For example, the reaction temperature is preferably −100 to 150 ° C., more preferably −20 to 100 ° C. The reaction time is, for example, about 0.1 to 48 hours. The reaction is usually carried out in an organic solvent that does not affect the reaction. Examples of the organic solvent that does not adversely influence the reaction include aliphatic or aromatic hydrocarbons such as hexane, pentane, benzene, and toluene, ether solvents such as diethyl ether, dipropyl ether, dioxane, and tetrahydrofuran (THF), and tetrachloride. Examples thereof include halogenated hydrocarbons such as carbon and methylene chloride, and these can be used alone or as a mixed solution. Of these, diethyl ether, THF and carbon tetrachloride are preferred. The reaction may optionally use a catalyst. As the catalyst, a known catalyst such as a platinum catalyst, a palladium catalyst, or a nickel catalyst can be used.

  The organosilane compound (α) thus obtained can be isolated and purified from the reaction solution by known means such as phase transfer, concentration, solvent extraction, fractional distillation, crystallization, recrystallization, chromatography and the like. it can.

The compound represented by the general formula (β) (hereinafter referred to as the compound (β); Grignard reagent) is represented by the general formula (β-1) in the same organic solvent as described above.
H- (R ¹ ) _m -X ¹ (β-1)
(Wherein R ¹ , m and X ¹ are the same as those in formula (β)) and obtained by reacting with magnesium metal (hereinafter referred to as compound (β-1)). Can do.

Compound (β-1) has the general formula (β-2);
H- (R < ¹ >) _m- H ([beta] -2)
(Wherein R ¹ and m are the same as those in formula (β)), N-chlorosuccinimide in a solvent such as carbon tetrachloride (hereinafter referred to as compound (β-2)) (NCS), N-bromosuccinimide (NBS) or the like can be used for halogenation at a predetermined position.

The compound (β-2) can be obtained by linking a condensed polycyclic hydrocarbon compound that derives R ¹ by a Grignard reaction. For example, the general formula (β-3);
HR ^1a -R ^1b -H (β-3)
(Wherein R ^1a and R ^1b are the same as R ¹ in formula (β) and may be the same or different) (hereinafter referred to as compound (β-3)). Prepared a Grignard reagent using one of the compound represented by the general formula (β-4) or the compound represented by the general formula (β-5), and the Grignard reagent and the other compound It can obtain by making it react with the halide of this.
HR ^la- H (β-4)
(Wherein R ^1a is the same as in general formula (β-3))
HR ^1b -H (β-5)
(Wherein R ^1b is the same as in general formula (β-3))

  For example, when preparing a Grignard using the compound (β-4), generally, a predetermined site of the compound is halogenated, and a metal such as magnesium is allowed to act on the halogen atom to prepare a Grignard reagent. Next, the Grignard reagent may be reacted with a halide of the compound (β-5). In this case, in particular, when both ends of the compound (β-4) are dihalogenated and a Grignard reagent prepared by allowing a metal such as magnesium to act on both halogen atoms is reacted with the monohalide of the compound (β-5). A compound corresponding to the compound (β) can be obtained.

  A compound (β-2) in which m is 3 or more can be obtained by newly repeating a Grignard reaction as described above using a desired condensed polycyclic hydrocarbon compound.

The condensed polycyclic hydrocarbon compound and the halide thereof corresponding to the compound (β-4) and the compound (β-5) can be obtained as a commercial product, or can be synthesized.
For example, 2-bromonaphthalene is a CAS. No. It is a known substance registered as 90-11-9, and is available as a commercial product.
Also, for example, 2,7-dibromofluorene is obtained from CAS. No. It is a known substance registered as 16433-88-8, and is available as a commercial product.
Also, for example, 2-bromofluorene is a CAS. No. It is a known substance registered as 1133-80-8, and is available as a commercial product.
Also, for example, benzo [k] fluoranthene is available from CAS. No. It is a known substance registered as 207-08-9, and is available as a commercial product.
Also, for example, 1-bromopyrene is a CAS. No. It is a known substance registered as 1714-29-0 and is available as a commercial product.
Also, for example, perylene is available from CAS. No. It is a known substance registered as 198-55-0, and is available as a commercial product.
Also, for example, 1-benzoanthracene is available from CAS. No. It is a known substance registered as 56-55-3, and is available as a commercial product.
Also, for example, phenanthrene is CAS. No. It is a known substance registered as 85-01-8, and is commercially available.

For example, the acene skeleton-containing molecule represented by the general formula (I) can be synthesized by the following method.
Examples of the method for synthesizing the acene skeleton-containing molecule include a method in which a hydrogen atom bonded to a carbon atom at a predetermined position of a raw material compound is substituted with a triflate group, reacted with furan or a derivative thereof, and subsequently oxidized. Can be mentioned. An example of a method for synthesizing an acene skeleton using this method is shown below. In addition, substituents such as a cyano group and a trimethylsilyl group can be removed by a known method.

(Organic thin film and method for forming the same)
An organic thin film (particularly, a monomolecular film) can be formed using the organosilane compound (α) of the present invention. Preferably, the monomolecular film is formed on a substrate.

The organosilane compound (α) can be adsorbed (bonded) to the substrate through a chemical bond (particularly silanol bond (—Si—O—)) by a silyl group. Therefore, in the monomolecular film made of the organosilane compound (α), the organosilane compound (α) molecules are arranged so that the silyl group is located on the substrate side and the R ¹ group is located on the film surface side. As a result, such a monomolecular film has high orderness (crystallinity) of the compound molecule and excellent peeling resistance. Moreover, since the organosilane compound (α) contains an R ¹ group exhibiting π-electron conjugation, the resulting monomolecular film is an organic layer (thin film) in organic devices such as organic thin film transistors, organic photoelectric conversion elements, and organic electroluminescence elements. ) Is excellent in electrical characteristics such as carrier movement characteristics.

  As the substrate, for example, an elemental semiconductor such as silicon or germanium, a compound semiconductor material such as gallium arsenide or selenium gallium, or a polymer material such as quartz glass, polyethylene, polyethylene terephthalate, or polytetrafluoroethylene can be used. The substrate may be made of an inorganic material used as an electrode of a semiconductor device, and a film made of an organic material may be formed on the surface of the substrate. In the present invention, the substrate surface has a hydrophilic group such as a hydroxyl group or a carboxyl group, in particular, a hydroxyl group. When the hydroxyl group does not have a hydroxyl group, the substrate surface may be subjected to a hydrophilic treatment to impart the hydrophilic group to the substrate surface. The hydrophilic treatment of the substrate can be performed by immersion in a hydrogen peroxide solution-sulfuric acid mixed solution, irradiation with ultraviolet light, or the like.

Hereinafter, a method for forming an organic thin film using the organosilane compound (α) will be described.
In forming the organic thin film, first, the silyl group of the organosilane compound (α) is hydrolyzed and reacted with the substrate surface to form a monomolecular film that is directly adsorbed (bonded) to the substrate. Specifically, for example, a so-called LB method (Langmuir Blodget method), a dipping method, a coating method, or the like can be employed.

Specifically, for example, in the LB method, the organic silane compound (α) is dissolved in a non-aqueous organic solvent, and the obtained solution is dropped on the water surface whose pH is adjusted to form a thin film on the water surface. At this time, R ^{2 to} R ⁴ groups in the silyl group of the organosilane compound (α) are converted to hydroxyl groups by hydrolysis. Next, pressure is applied to the water surface in this state, and the substrate having a hydrophilic group (especially a hydroxyl group) is pulled up, whereby the silyl group in the organosilane compound (α) reacts with the substrate to form a chemical bond (especially a silanol bond). ) To form a monomolecular film. The pH of the water into which the solution is dropped may be adjusted as appropriate so that the R ^{2 to} R ⁴ groups are hydrolyzed.

Further, for example, in the dipping method and the coating method, the organic silane compound (α) is dissolved in a non-aqueous organic solvent, and a substrate having a hydrophilic group (particularly a hydroxyl group) on the surface is immersed in the obtained solution and pulled up. Alternatively, the resulting solution is coated on the substrate surface. At this time, the R ^{2 to} R ⁴ groups in the silyl group of the organosilane compound (α) are hydrolyzed by a trace amount of water in the non-aqueous organic solvent and converted into a hydroxyl group. Next, by holding for a predetermined time, the silyl group in the organosilane compound (α) reacts with the substrate to form a chemical bond (particularly a silanol bond) to obtain a monomolecular film. When the R ^{2 to} R ⁴ groups are not hydrolyzed, a small amount of water adjusted in pH may be mixed in the solution.

  The non-aqueous organic solvent is not particularly limited as long as it is incompatible with water and can dissolve the organic silane compound (α), and for example, hexane, chloroform, carbon tetrachloride and the like can be used.

  After forming the monomolecular film, the non-reacted organosilane compound is usually washed away from the monomolecular film using a non-aqueous organic solvent. Further, it is washed with water and left to stand or dried by heating.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example.
Example 1; Synthesis of organosilane compound represented by general formula (A) First, 100 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM 2-bromonaphthalene (CASno. 90-11-9). 2,6-dibromonaphthalene was synthesized by reacting at 60 ° C. for 2 hours in an N ₂ atmosphere. Subsequently, after synthesizing Grignard reagent by dissolving 2-bromonaphthalene 40 mM in THF, adding metal magnesium and reacting at 60 ° C. for 1 hour in an N 2 atmosphere, the THF solution containing 2,6-dibromonaphthalene 20 mM is added to the THF solution. Grignard reagent was added and reacted at 20 ° C. for 9 hours to synthesize [2,2 ′; 6 ′, 2 ″] Ternephthalene. Thereafter, 20 mM NBS and AIBN were added to a carbon tetrachloride solution containing 10 mM of the [2,2 ′; 6 ′, 2 ″] ternaphthalene, and reacted at 60 ° C. for 2 hours in an N ₂ atmosphere. Bromo- [2,2 ′; 6 ′, 2 ″] ternaphthalene was formed, then magnesium metal was added and reacted at 60 ° C. for 1 hour in an N 2 atmosphere to synthesize a Grignard reagent. Further, chlorotriethoxysilane 10 mM Was added and reacted at 60 ° C. for 2 hours to obtain the title compound in a yield of 40%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1090 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
7.9 ppm (m) (4H aromatic)
7.6 ppm (m) (8H aromatic)
7.5ppm (m) (4H aromatic)
7.3 ppm (m) (3H aromatic)
3.6 ppm (m) (6H ethoxy group methylene group)
1.5 ppm (m) (9H ethoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (A).

Preparation Example 1; Synthesis of 2-bromopentacene 2-Bromopentacene used in Example 2 was synthesized by the following method. First, 100 mM pentacene dissolved in 50 mL carbon tetrachloride and NBS were added to a 100 ml eggplant flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, and reacted in the presence of AIBN for 1.5 hours. After removing unreacted substances and HBr by filtration, the stored 2-bromopentacene was obtained by using a column chromatograph to take out a reservoir brominated at only one position.

Example 2; Synthesis of organosilane compound represented by general formula (B) First, 50 mM of 2,7-dibromofluorene (CASNO. 16433-88-8) was dissolved in a THF solution, and magnesium metal was added. By reacting at 60 ° C. for 8 hours, Grignard reagent 1 represented by the formula (1) was formed.

Subsequently, the Grignard reagent 2 represented by the following formula (2) is obtained by adding the Grignard reagent 1 to the THF solution containing 25 mM 2-bromopentacene formed in Preparation Example 1 and reacting at 20 ° C. for 2 hours. Formed.

Furthermore, 25 mM 2-bromofluorene (CASNO. 1133-80-8) was added and reacted at 20 ° C. for 3 hours, whereby 7-pentacene-2-yl-9H, 9′H- [2,2 ′] bifluorenyl was converted. Synthesized. Thereafter, magnesium metal is added and reacted at 60 ° C. for 1 hour in an N ₂ atmosphere to synthesize a Grignard reagent represented by the following formula (3). Further, 10 mM of chlorotrimethoxysilane is added and reacted at 60 ° C. for 2 hours. This gave the title compound in 25% yield.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1080 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.2 ppm (m) (2H pentacene)
8.0 ppm (m) (2H pentacene)
7.9 ppm (m) (9H pentacene and fluorene)
7.8 ppm (m) (4H pentacene and fluorene)
7.6 ppm (m) (5H pentacene and fluorene)
7.4 ppm (m) (3H pentacene and fluorene)
3.9 ppm (m) (4H fluorene)
3.6 ppm (m) (9H methoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (B).

Example 3; Synthesis of Organosilane Compound Represented by General Formula (C) First, 50 mM of 2,6-dibromonaphthalene, which is an intermediate of Example 1, was dissolved in a THF solution, and magnesium metal was added. By reacting at 8 ° C. for 8 hours, Grignard reagent 1 represented by the formula (4) was formed.

On the other hand, 100 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM of benzo [k] fluoranthene (CASNO.207-08-9), reacted at 60 ° C. for 2 hours in an N ₂ atmosphere, and unreacted matter was filtered. Then, 2-bromo-benzo [k] fluoranthene was synthesized by taking out a reservoir brominated at only one position using a column chromatograph. Subsequently, 2- (6-bromo-naphthalen-2-yl)-is added by adding 20 mM 2-Bromo-benzo [k] fluoranthene to a THF solution containing 20 mM Grignard reagent and reacting at 20 ° C. for 4 hours. Benzo [k] fluoranthene was synthesized. Furthermore, magnesium metal is added to a carbon tetrachloride solution containing 10 mM of 2- (6-bromo-naphthalen-2-yl) -benzo [k] fluoranthene and reacted at 60 ° C. for 1 hour to synthesize Grignard reagent 2. Then, in the same manner as in Example 2, 10 mM chlorotrimethoxysilane was added and reacted at 60 ° C. for 2 hours to obtain the title compound in a yield of 30%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1080 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.1 ppm (m) (1H benzofluoranthene)
8.0 ppm (m) (1H benzofluoranthene)
7.9 ppm (m) (2H benzofluoranthene and naphthalene)
7.8 ppm (m) (1H benzofluoranthene)
7.7 ppm (m) (7H benzofluoranthene and naphthalene)
7.6 ppm (m) (1H benzofluoranthene)
7.5ppm (m) (1H naphthalene)
7.3 ppm (m) (3H benzofluoranthene and naphthalene)
3.6 ppm (m) (9H methoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (C).

Example 4; Synthesis of organosilane compound represented by general formula (D) First, 50 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM 1-bromopyrene (CASNO.1714-29-0), 1,6-Dibromopyrene was synthesized by reacting at 60 ° C. for 2 hours under N ₂ atmosphere. Subsequently, a Grignard reagent was formed by adding metal magnesium to a THF solution containing 100 mM 1-bromonaphthalene and reacting at 60 ° C. for 2 hours. Furthermore, 1,6-di-naphthalen-2-yl-pyrene was synthesized by adding 25 mM of 1,6-dibromopyrene to a THF solution containing 50 mM of Grignard reagent and reacting at 20 ° C. for 4 hours. Thereafter, bromation was performed by adding 50 mM NBS and AIBN to a carbon tetrachloride solution containing 20 mM of 1,6-di-naphthalen-2-yl-pyrene and reacting at 60 ° C. for 2 hours in an N ₂ atmosphere. Thereafter, magnesium metal was added to a carbon tetrachloride solution containing 10 mM of the bromide and reacted at 60 ° C. for 1 hour to synthesize a Grignard reagent. Thereafter, 10 mM chlorotriethoxysilane was added and reacted at 60 ° C. for 2 hours in the same manner as in Example 1 to obtain the title compound in a yield of 25%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1080 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.2 ppm (m) (1H pyrene)
8.0 ppm (m) (2H pyrene)
7.9 ppm (m) (3H pyrene and naphthalene)
7.7 ppm (m) (10H pyrene and naphthalene)
7.5ppm (m) (2H naphthalene)
7.3 ppm (m) (3H naphthalene)
3.6 ppm (m) (6H ethoxy group methylene group)
1.5 ppm (m) (9H ethoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (D).

Example 5: Synthesis of organosilane compound represented by formula (E) First, 6-bromo- [2,2 ′; 6 ′, 2 ″] ternaphthalene, which is an intermediate of Example 1, was prepared. A Grignard reagent was formed by adding metallic magnesium to a THF solution containing 20 mM and reacting at 60 ° C. for 1 hour in an N ₂ atmosphere. Subsequently, 20 mM of the Grignard reagent was added to a THF solution containing 6 mM of 6-bromo- [2,2 ′; 6 ′, 2 ″] ternaphthalene, and the mixture was reacted at 20 ° C. for 3 hours. The indicated intermediate was synthesized.

Furthermore, after adding 20 mM NBS and AIBN in a carbon tetrachloride solution containing 10 mM of the intermediate and reacting at 60 ° C. for 2 hours in an N ₂ atmosphere, a compound having a terminal brominated compound was synthesized, and then metal magnesium Was added and reacted at 60 ° C. for 1 hour to synthesize a Grignard reagent, and 10 mM tetrachlorosilane was added and reacted at 60 ° C. for 2 hours to obtain the title compound in a yield of 25%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1095 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed. Direct NMR measurement of the resulting compound is impossible due to the high reactivity of the compound, so the compound was reacted with ethanol (hydrogen chloride generation was confirmed), and the terminal chlorine was converted to an ethoxy group. Then, measurement was performed.
7.9 ppm (m) (10H aromatic)
7.7 ppm (m) (14H aromatic)
7.5ppm (m) (10H aromatic)
7.3 ppm (m) (3H aromatic)
3.7 ppm (m) (6H ethoxy group methylene group)
1.4 ppm (m) (9H ethoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (E).

Example 6: Synthesis of organosilane compound represented by formula (F) First, 100 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM 1-benzoanthracene (CASNO.56-55-3). Then, 3-bromo-benzo [a] anthracene was synthesized by reacting at 60 ° C. for 2 hours in an N ₂ atmosphere. Subsequently, magnesium metal was added to a THF solution containing 20 mM of 3-bromo-benzo [a] anthracene and reacted at 65 ° C. for 2 hours to synthesize a Grignard reagent. In addition, 100 mM NBS and AIBN were added to a carbon tetrachloride solution containing 50 mM phenanthrene (CASNO.85-01-8), and reacted at 60 ° C. for 3 hours in an N ₂ atmosphere, whereby 2,7-dibromo-phenanthrene was obtained. Synthesized. Subsequently, by adding 5 mM of the Grignard reagent to a THF solution containing 5 mM of the 2,7-dibromo-phenanthrene and reacting at 60 ° C. for 2 hours, 3- (7-bromo-phenanthren-2-yl) -Benzo [a] anthracene was synthesized. Furthermore, 10 mM NBS and AIBN were added to a carbon tetrachloride solution containing 1 mM of 3- (7-bromo-phenanthren-2-yl) -benzo [a] anthracene, and the mixture was reacted at 60 ° C. for 2 hours in an N ₂ atmosphere. Metallic magnesium was added and reacted at 60 ° C. for 1 hour to synthesize a Grignard reagent. 2 mM chlorotrimethoxysilane was added and reacted at 60 ° C. for 2 hours to obtain the title compound in a yield of 10%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1075 cm ⁻¹ , and it was confirmed that the compound had a SiC bond.
Furthermore, the nuclear magnetic resonance (NMR) measurement of the compound was performed.
8.5 ppm (m) (3H aromatic)
8.3 ppm (m) (4H aromatic)
8.1 ppm (m) (3H aromatic)
7.9 ppm (m) (4H aromatic)
7.7 ppm (m) (2H aromatic)
7.4 ppm (m) (3H aromatic)
3.7 ppm (m) (9H methoxy group methyl group)
From this result, it was confirmed that the obtained compound was a compound represented by the general formula (F).

  The organosilane compound of the present invention is very useful as a semiconductor material not only for organic thin film transistors but also for organic devices such as solar cells, fuel cells and sensors.

Claims (3)

Formula (α);
H- (R ¹ ) _m -SiR ² R ³ R ⁴ (α)
(In the formula, R ¹ is a divalent organic group derived from a condensed polycyclic hydrocarbon compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered monocyclic hydrocarbon ring. M is an integer of 2 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms). The R ¹ is each independently a divalent organic group derived from a condensed polycyclic hydrocarbon compound selected from the group consisting of compounds represented by formulas (I) to (IX). The π-electron conjugated organosilane compounds described;

(In Formula (I), n1 is an integer of 0 to 8; In Formula (II), n2 and n3 are each an integer of 0 or more such that their sum is 1 to 9; Formula (III ), N4 and n5 are each an integer of 1 or more such that the sum thereof is 2 to 9; in formula (IV), n6 is an integer of 0 to 7). Formula (β);
H- (R ¹ ) _m -MgX ¹ (β)
(In the formula, R ¹ is a divalent organic group derived from a condensed polycyclic hydrocarbon compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered monocyclic hydrocarbon ring. M is an integer of 2 to 10; X ¹ is a halogen atom) and a general formula (γ);
X ² —SiR ² R ³ R ⁴ (γ)
Wherein X ² is a hydrogen atom, a halogen atom or an alkoxy group having 1 to 4 carbon atoms; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms. The method for producing a π-electron conjugated organosilane compound according to claim 1, wherein the compound is subjected to Grignard reaction.