JP2006062963A - 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: Z-(R<SP>1</SP>)<SB>m</SB>-SiR<SP>2</SP>R<SP>3</SP>R<SP>4</SP>[wherein, Z is a monovalent 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; R<SP>1</SP>is a divalent organic group; (m) is 0 to 10; and R<SP>2</SP>to R<SP>4</SP>are each 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; Z-(R<SP>1</SP>)<SB>m</SB>-MgX<SP>20</SP>[wherein, R<SP>1</SP>and (m) are each the same as above; and X<SP>20</SP>is a halogen atom] with a compound of the formula: X<SP>21</SP>-SiR<SP>2</SP>R<SP>3</SP>R<SP>4</SP>[wherein, X<SP>21</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. Alternatively, a compound having one thiophene ring as a functional group at the end of the molecule and having the thiophene ring bonded to a silicon atom via a linear hydrocarbon group has been proposed (for example, Japanese Patent No. 2889768: 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 electric 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);
Z- (R ¹ ) _m -SiR ² R ³ R ⁴ (α)
(In the formula, Z is a monovalent organic group derived from a condensed polycyclic heterocyclic compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered ring; R ¹ is a divalent group; M is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms). About.

The present invention also provides a general formula (β);
Z- (R ¹ ) _m -MgX ²⁰ (β)
(In the formula, Z is a monovalent organic group derived from a condensed polycyclic heterocyclic compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered ring; R ¹ is a divalent group; An organic group; m is an integer of 0 to 10; X ²⁰ is a halogen atom; and a general formula (γ);
X ²¹ —SiR ² R ³ R ⁴ (γ)
(Wherein X ²¹ represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 4 carbon atoms; R ^{2 to} R ⁴ each independently represents 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.

  According to the present invention, there is provided a π-electron conjugated organosilane compound containing a skeleton of a condensed polycyclic heterocyclic compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered ring. Since the compound of the present invention has a self-organization ability because it has a silyl group at the terminal, a highly crystallized organic thin film having very high stability can be obtained by a solution method. Can be configured. In addition, since the organosilane compound of the present invention contains a skeleton of a condensed polycyclic heterocyclic compound, stabilization of LUMO of the compound is promoted. Therefore, use as an n-type semiconductor material can be expected. Conventionally, many developments of p-type semiconductor materials have been made. However, since development of n-type semiconductor materials as in the present invention has hardly been made, not only organic thin film transistor materials but also organic materials such as solar cells, fuel cells, sensors, etc. In devices, the organosilane compounds of the present invention are very useful.

(Organic silane compound)
The π-electron conjugated organosilane compound of the present invention has the general formula (α);
Z- (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 formula (α), Z is a monovalent organic group derived from a condensed polycyclic heterocyclic compound exhibiting π-electron conjugation, that is, one from any ring constituent atom of the condensed polycyclic heterocyclic compound. It is a monovalent residue obtained by removing the hydrogen atom. 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.

  The condensed polycyclic heterocyclic compound from which the organic group Z is derived is composed of a 5-membered ring and / or a 6-membered ring, and has at least one, preferably 1 or 2 heterocycles. As heteroatoms constituting the heterocyclic ring, silicon atoms (Si), germanium atoms (Ge), tin atoms (Sn), titanium atoms (Ti) zirconium atoms (Zr), nitrogen atoms (N), phosphorus atoms (P), Examples include an oxygen atom (O), a sulfur atom (S), a selenium atom (Se), or a tellurium atom (Te). Considering the yield in the synthesis of the condensed polycyclic heterocyclic compound, N, O and S are preferable as the hetero atom.

Examples of the 5-membered ring and 6-membered ring that can constitute the condensed polycyclic heterocyclic compound include the following rings. In addition, when the following rings constitute a condensed polycyclic heterocyclic compound by condensation, usually two carbon atoms in the ring are shared with other rings.

In the above specific examples, Y _I is commonly Si, Ge, Sn, Ti, or Zr.
Y _II is N or P in common.
Y _III is commonly O, S, Se or Te.

  The number of condensed rings constituting the condensed polycyclic heterocyclic compound is 2 to 10, and the number of condensed rings is preferably 2 to 5 from the viewpoint of yield.

  Specific examples of the organic group Z derived from such a condensed polycyclic heterocyclic compound include the following groups:

（式中、Ｘ^１はＣ、Ｎ、ＯまたはＳであり、Ｘ^２はＣまたはＮである（ただし、Ｘ^１およびＸ^２が同時にＣの場合は除く）；ｎ１は０〜８の整数である）

Wherein X ¹ is C, N, O or S, and X ² is C or N (except when X ¹ and X ² are simultaneously C); n1 is an integer of 0 to 8 is there)

（式中、Ｘ^３はＮ、ＯまたはＳである；ｎ２及びｎ３は０≦ｎ２＋ｎ３≦７を満たす整数である）

(Wherein X ³ is N, O or S; n2 and n3 are integers satisfying 0 ≦ n2 + n3 ≦ 7)

（式中、Ｘ^４およびＸ^５はそれぞれ独立してＣまたはＮである（ただし、Ｘ^４およびＸ^５が同時にＣの場合は除く）；ｎ４は０〜８の整数である）

(In the formula, X ⁴ and X ⁵ are each independently C or N (except when X ⁴ and X ⁵ are simultaneously C); n4 is an integer of 0 to 8)

（式中、Ｘ^６およびＸ^７はそれぞれ独立してＣまたはＮである（ただし、Ｘ^６およびＸ^７が同時にＣの場合は除く）；ｎ５は０〜８の整数である）

(In the formula, X ⁶ and X ⁷ are each independently C or N (except when X ⁶ and X ⁷ are simultaneously C); n5 is an integer of 0 to 8)

（式中、Ｘ^８およびＸ^９はそれぞれ独立してＣ、Ｎ、ＯまたはＳである（ただし、Ｘ^８およびＸ^９が同時にＣの場合は除く）；ｎ６及びｎ７は０≦ｎ６＋ｎ７≦７を満たす整数である）

(Wherein X ⁸ and X ⁹ are each independently C, N, O or S (except when X ⁸ and X ⁹ are simultaneously C); n6 and n7 satisfy 0 ≦ n6 + n7 ≦ 7) Is an integer that satisfies

（式中、Ｘ^１０およびＸ^１１はそれぞれ独立してＣまたはＮである（ただし、Ｘ^１０およびＸ^１１が同時にＣの場合は除く）；ｎ８及びｎ９は０≦ｎ８＋ｎ９≦７を満たす整数である）。

(Wherein X ¹⁰ and X ¹¹ are each independently C or N (except when X ¹⁰ and X ¹¹ are simultaneously C); n8 and n9 are integers satisfying 0 ≦ n8 + n9 ≦ 7) ).

The organosilane compound (α) may have a divalent organic group between the organic group Z and a silyl group described later. That is, in the formula (α), R ¹ is a divalent organic group, and m is an integer of 0 to 10.

Specifically, the organic group R ¹ is a divalent organic group derived from a π electron conjugated molecule or a non-π electron conjugated molecule, that is, two hydrogen atoms are removed from a π electron conjugated molecule or a non-π electron conjugated molecule. It is a divalent residue or a complex group thereof.

Examples of the π-electron conjugated molecule that derives the organic group R ¹ include a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, and a condensed polycyclic aromatic hydrocarbon compound.
An example of the monocyclic aromatic hydrocarbon compound is benzene.

Examples of the hetero atom contained in the monocyclic heterocyclic compound include N, O, S, Si, Ge, Se, Te, P, Sn, Ti, and Zr atoms, and preferably from the viewpoint of synthesis cost. N, O, S.
Examples of such preferable monocyclic heterocyclic compounds include furan, pyrrole, pyridine, pyrimidine, pyrroline, imidazoline, pyrazoline, thiophene, oxazole, isoxazole, thiazole, and isothiazole.

（式中、ｎ１０は０〜８の整数である）で表される化合物、フェナレン、ペリレン、コロネン、オバレンが挙げられる。 The condensed polycyclic aromatic hydrocarbon compound is formed by condensing two or more benzene rings, and preferably has symmetry, particularly line symmetry, from the viewpoint of conductivity. Specific examples of such preferred compounds include, for example, the general formula;

(Wherein n10 is an integer of 0 to 8), phenalene, perylene, coronene and ovalene.

  Examples of the condensed polycyclic aromatic hydrocarbon compound represented by the above general formula include naphthalene, anthracene, tetracene (naphthacene), pentacene, hexacene, heptacene, and octacene.

Examples of the non-π electron conjugated molecule that induces the organic group R ¹ include a linear saturated aliphatic hydrocarbon compound). From linear saturated aliphatic hydrocarbon compound - (CH ₂₎ m _- is induced.

When m is 2 or more, the plurality of organic groups R ¹ may be the same group, or part or all of them may be different.

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.

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

で表されるπ電子共役系有機シラン化合物； (1) General formula (I);

A π-electron conjugated organosilane compound represented by:

In general formula (I), X ¹ is C, N, O or S, preferably N, O or S, more preferably N; specifically, when X ¹ is C, it is —CH ₂ —; When X ¹ is N, it is —NH—, and when X ¹ is O or S, it is —X ¹ —;
X ² is C or N, preferably N; specifically, —CH═ when X ² is C and —N═ when X ² is N;
Except when X ¹ and X ² are C at the same time;
n1 is an integer of 0-8, preferably 0-3;

（式中、ｎ１０は０〜８、好ましくは０または１の整数である）からなる群から選択される２価の有機基である。最も好ましいＲ^１は前記一般式（ｉ）〜（ｉｉｉ）の基である；後述のｍが２以上のとき、複数の有機基Ｒ^１は同一の基であってもよいし、または一部または全部が異なっていても良い；
ｍは０〜１０、好ましくは０〜７、より好ましくは０〜３の整数である；
Ｒ^２〜Ｒ^４はそれぞれ独立してハロゲン原子または炭素数１〜４のアルコキシ基、好ましくは塩素原子、メトキシ基、エトキシ基である。 In the formula (I), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably the following general formulas (i) to (iv);

(Wherein n10 is a divalent organic group selected from the group consisting of 0 to 8, preferably an integer of 0 or 1). Most preferred R ¹ is a group of the above general formulas (i) to (iii); when m described below is 2 or more, the plurality of organic groups R ¹ may be the same group, or a part or All may be different;
m is an integer of 0 to 10, preferably 0 to 7, more preferably 0 to 3;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (I).

で表されるπ電子共役系有機シラン化合物； (2) General formula (II);

A π-electron conjugated organosilane compound represented by:

In general formula (II), X ³ is N, O or S, preferably N or O; specifically, when X ³ is N, it is —NH—, and when X ³ is O or S. Is —X ³ —;
n2 and n3 are integers satisfying 0 ≦ n2 + n3 ≦ 7, preferably 0 ≦ n2 + n3 ≦ 2.

In the formula (II), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably, it is a divalent organic group selected from the group consisting of the general formulas (i) to (iv) (wherein n10 is 0 to 8, preferably 0 or 1). Most preferred R ¹ is a group of the above general formulas (i) and (iii); when m described below is 2 or more, a plurality of organic groups R ¹ may be the same group or a part or All may be different;
m is an integer of 0-10, preferably 0-2, more preferably 0 or 1;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (II).

で表されるπ電子共役系有機シラン化合物； (3) General formula (III);

A π-electron conjugated organosilane compound represented by:

In the general formula (III), X ⁴ and X ⁵ are each independently C or N, preferably X ⁴ is N, and X ⁵ is C; specifically, when X ⁴ is C— CH =, when X ⁴ is N, -N =; when X ⁵ is C, -CH =; when X ⁵ is N, -N =;
Except when X ⁴ and X ⁵ are simultaneously C;
n4 is an integer of 0-8, preferably 0-3, more preferably 0 or 1;

In the formula (III), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably, it is a divalent organic group selected from the group consisting of the general formulas (i) to (iv) (wherein n10 is 0 to 8, preferably 0 or 1). Most preferred R ¹ is a group of the above general formulas (ii) and (iii); when m described below is 2 or more, a plurality of organic groups R ¹ may be the same group or a part or All may be different;
m is an integer of 0-10, preferably 0-2, more preferably 0 or 1;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (III).

で表されるπ電子共役系有機シラン化合物； (4) General formula (IV);

A π-electron conjugated organosilane compound represented by:

In general formula (IV), X ⁶ and X ⁷ are each independently C or N, preferably X ⁶ and X ⁷ are simultaneously N; specifically, when X ⁶ is C, —CH═ Yes, when X ⁶ is N, -N =; when X ⁷ is C, -CH =; when X ⁷ is N, -N =;
Except when X ⁶ and X ⁷ are C at the same time;
n5 is an integer of 0-8, preferably 0-3, more preferably 0 or 1;

In the formula (IV), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably, it is a divalent organic group selected from the group consisting of the general formulas (i) to (iv) (wherein n10 is 0 to 8, preferably 0 to 3). Most preferred R ¹ is a group of the above general formula (i); when m described later is 2 or more, the plurality of organic groups R ¹ may be the same group, or a part or all of them are different. May be;
m is an integer from 0 to 10, preferably 0 to 3;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

  In the general formula (IV), when m is 0, the condensed benzene ring or heterocyclic ring may have a hydrophobic group such as an alkyl group having 1 to 30 carbon atoms.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (IV).

で表されるπ電子共役系有機シラン化合物； (5) General formula (V);

A π-electron conjugated organosilane compound represented by:

In the general formula (V), X ⁸ and X ⁹ are each independently C, N, O, or S, and the combination of X ⁸ -X ⁹ is N—S, N—O, S—O, N—N. And C—N are preferred, more preferably NS; specifically, —CH ₂ — when X ⁸ is C, —NH— when X ⁸ is N, and X ⁸ is O. or when the S -X ⁸ - is; also, -CH ₂ when ^{X 9} is C - is, when ^{X 9} is N is -NH-, when ^{X 9} is O or S -X ⁹ - is;
Except when X ⁸ and X ⁹ are simultaneously C;
n6 and n7 are integers satisfying 0 ≦ n6 + n7 ≦ 7, preferably 0 ≦ n6 + n7 ≦ 2.

In the formula (V), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably, it is a divalent organic group selected from the group consisting of the general formulas (i) to (iv) (wherein n10 is 0 to 8, preferably 0 to 3). Most preferred R ¹ is a group of the above general formulas (i) to (iii); when m described below is 2 or more, the plurality of organic groups R ¹ may be the same group, or a part or All may be different;
m is an integer from 0 to 10, preferably from 0 to 4;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (V).

で表されるπ電子共役系有機シラン化合物； (6) General formula (VI);

A π-electron conjugated organosilane compound represented by:

In general formula (VI), X ¹⁰ and X ¹¹ are each independently C or N, preferably N at the same time; specifically, when X ¹⁰ is C, —CH═ and X ¹¹ is N -N = when X ¹¹ is C; -CH = when X ¹¹ is C; and -N = when X ¹¹ is N;
Except when X ¹⁰ and X ¹¹ are simultaneously C;
n8 and n9 are integers satisfying 0 ≦ n8 + n9 ≦ 7, preferably 0 ≦ n8 + n9 ≦ 2.

In the formula (VI), R ^{1 to} R ⁴ and m are the same as those in the formula (α).
Specifically, R ¹ is a divalent organic group, that is, a monocyclic aromatic hydrocarbon compound, a monocyclic heterocyclic compound, a condensed polycyclic aromatic hydrocarbon compound described above in the description of the general formula (α), Alternatively, it is a divalent residue obtained by removing two hydrogen atoms from a saturated aliphatic hydrocarbon compound or a composite group thereof. Preferably, it is a divalent organic group selected from the group consisting of the general formulas (i) to (iv) (wherein n10 is 0 to 8, preferably 0 to 3). Most preferred R ¹ is a group of the above general formula (iii); when m described later is 2 or more, the plurality of organic groups R ¹ may be the same group, or part or all of them are different. May be;
m is an integer of 0-10, preferably 0-2;
R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms, preferably a chlorine atom, a methoxy group, or an ethoxy group.

  In the general formula (VI), when m is 0, the condensed benzene ring or heterocyclic ring may have a hydrophobic group such as an alkyl group having 1 to 30 carbon atoms.

The following compounds are mentioned as a further specific example of such an organosilane compound of general formula (VI).

(Production method)
The organic compound (α) of the present invention has the general formula (β);
Z- (R ¹ ) _m -MgX ²⁰ (β)
Wherein Z, R ¹ and m are the same as in general formula (α); X ²⁰ is a halogen atom, and general formula (γ);
X ²¹ —SiR ² R ³ R ⁴ (γ)
(Wherein X ²¹ represents a hydrogen atom, a halogen atom or an alkoxy group having 1 to 4 carbon atoms; R ^{2 to} R ⁴ each independently represents a halogen atom or an alkoxy group having 1 to 4 carbon atoms) The compound can be produced by a Grignard reaction. In addition, the organosilane compound of the said general formula (I)-(VI) can also be manufactured according to the said method.

  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, and ether solvents such as diethyl ether, dipropyl ether, dioxane, and tetrahydrofuran (THF). These can be used alone or as a mixture. Of these, diethyl ether and THF are preferable. 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.
Z- (R ¹ ) _m -X ²⁰ (β-1)
(Wherein, Z, R ¹ , m and X ²⁰ are the same as those in the general formula (β)) by reacting with metal magnesium (hereinafter referred to as compound (β-1)). Obtainable.

The compound (β-1) when m is 0 is represented by the general formula (β-2) or (β-3);
Z-H (β-2)
Z-OH (β-3)
(Commonly, in the formula, Z is the same as in the general formula (β)) (hereinafter referred to as the compound (β-2) or (β-3), respectively) such as carbon tetrachloride. It can be obtained by halogenation at a predetermined position using N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) or the like in a solvent.

The compound (β-1) when m is 0 can also be obtained as a commercial product.
For example, 2-chlorobenzimidazole (CAS.NO7228-38-8), 2-chlorophenothiazine (CAS.NO92-39-7) and 2-chloroquinoline (CAS.NO612-62-4) are each, for example, Sigma-Aldrich shares. It is available as a commercial product from the company.

Compounds (β-2) and (β-3) are generally available as commercial products.
For example, 4,7-dimethyl-1,10-phenanthroline (CAS.NO3248-05-3), 2-hydroxydibenzofuran (CAS.NO86-77-1), 2-hydroxycarbazole (CAS.NO86-79-3) 2,3-dimethylquinoxaline (CAS.NO2379-55-7) is commercially available, for example, from Sigma-Aldrich Corporation.

The compound (β-1) when m is 1 or more is the compound (β-2) or the general formula (β-4);
_{^{H- (R 1) m -H (}} β-4)
(Wherein R ¹ and m are the same as those in the general formula (β)), a Grignard reagent using one compound of the compound (hereinafter referred to as the compound (β-4)) is prepared, It can be obtained by reacting the Grignard reagent with the halide of the other compound.

  In particular, when preparing a Grignard using the compound (β-4), generally, both ends of the compound are dihalogenated, and a metal such as magnesium is allowed to act on only one halogen atom to prepare a Grignard reagent. Next, the Grignard reagent may be reacted with a halide of the compound (β-2).

Some compounds (β-4) can be obtained as commercially available products, while others can be synthesized by known methods.
For example, benzene, biphenyl, terphenyl, thiophene, bithiophene, terthiophene, quarterthiophene, naphthalene, and mono- or dihalides thereof are easily available as commercial products.

For example, a benzene skeleton-containing molecule can be synthesized by the following method. However, if a method similar to that for a benzene skeleton-containing molecule is used, a heterocyclic skeleton-containing molecule containing N, Si, Ge, P, Sn, Ti, or Zr can also be synthesized.
As a method for synthesizing a benzene skeleton-containing molecule, it is effective to first use a Grignard reaction after halogenating the reaction site of benzene. If this method is used, the number of benzene rings can be controlled. In addition to the method of applying the Grignard reagent, it can be synthesized by coupling using an appropriate metal catalyst (Cu, Al, Zn, Zr, Sn, etc.).

  As an example, a method for synthesizing a benzene skeleton-containing molecule is shown below. In the following synthesis examples, only the reaction from a benzene trimer to a (3 + m) mer was shown. However, if starting materials having different numbers of units are reacted, a benzene skeleton-containing molecule other than the tetramer to 7mer can be formed.

For example, a thiophene skeleton-containing molecule can be synthesized by the following method. However, if a method similar to that for a thiophene skeleton-containing molecule is used, a heterocyclic skeleton-containing molecule containing O and N can also be synthesized.
As a method for synthesizing a thiophene skeleton-containing molecule, it is effective to first use a Grignard reaction after halogenating the reaction site of thiophene. If this method is used, the number of thiophene rings can be controlled. In addition to the method of applying the Grignard reagent, it can be synthesized by coupling using an appropriate metal catalyst (Cu, Al, Zn, Zr, Sn, etc.).

Furthermore, for the thiophene skeleton-containing molecule, the following synthesis method can be used in addition to the method using the Grignard reagent.
That is, first, the 2′-position or 5′-position of thiophene is halogenated (eg, chlorinated). Examples of the halogenating method include treatment with 1 equivalent of N-chlorosuccinimide and phosphorous oxychloride (POCl ₃ ). As the solvent at this time, for example, a chloroform / acetic acid (AcOH) mixed solution or DMF can be used. Further, the halogenated thiophene is reacted with each other in a DMF solvent using tris (triphenylphosphine) nickel ((PPh ₃ ) ₃ Ni) as a catalyst, resulting in a halogenated portion. Can directly bond thiophenes together.

Furthermore, divinyl sulfone is added to the halogenated thiophene and coupled to form a 1,4-diketone body. Subsequently, Lawesson's agent (Lawesson Regent: LR) or P ₄ S ₁₀ is added in the dry toluene solution, and the mixture is refluxed overnight for about 3 hours in the latter case, thereby causing a ring-closing reaction. As a result, a thiophene skeleton-containing molecule having one thiophene more than the total number of coupled thiophenes can be synthesized.
Using the above reaction of thiophene, the number of thiophene rings can be increased.

  As an example, a method for synthesizing a thiophene skeleton-containing molecule is shown below. In the following synthesis examples, only a reaction from a dimer to a tetramer of thiophene and a reaction from a trimer of thiophene to a hexamer or a hexamer are shown. However, by reacting with thiophene having a different number of units, a thiophene skeleton-containing molecule other than the 4, 6 or 7-mer can be formed. For example, a thiophene pentamer can be formed by reacting 2-chlorobithiophene, which is chlorolated with NCS after coupling 2-chlorothiophene, with a 2-chloro thiophene trimer. Furthermore, if thiophene tetramer is chlorinated with NCS, thiophene 8 or 9-mer can be further formed.

  Further, for example, a molecule containing a benzene skeleton and a thiophene skeleton can be synthesized by combining the synthesis methods of the benzene skeleton-containing molecule and the thiophene skeleton-containing molecule.

For example, an acene skeleton-containing molecule 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.

(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 composed 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 Z 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 a Z 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. As a result, it has excellent 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 (I-1) The title compound was synthesized by the following method. First, in a 500 ml glass flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel in a nitrogen atmosphere, 0.5 mol of metal magnesium and 300 ml of THF (tetrahydrofuran) were charged, and 0.5 mol of 2-chlorobenzimidazole was added. It dropped over 2 hours from the dropping funnel at 50 to 60 ° C., and after completion of dropping, the mixture was matured at 65 ° C. for 2 hours to prepare a Grignard reagent. Subsequently, 1.0 mol of SiCl ₄ (tetrachlorosilane) and 300 ml of toluene were charged into a 1 liter glass flask, cooled on ice, and a Grignard reagent was added over 2 hours at an internal temperature of 20 ° C. or less. Maturation was performed at 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted tetrachlorosilane were removed from the filtrate to obtain the title compound in a yield of 50%.

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. 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.
7.7 ppm (m) (2H aromatic)
7.2 ppm (m) (2H aromatic)
5.2 ppm (m) (1H hydrogen having a direct bond with a nitrogen atom)
3.8 ppm (m) (6H ethoxy group methylene group)
1.4 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (I-1).

Example 2 Synthesis of Organosilane Compound Represented by General Formula (V-1) The title compound was synthesized by the following method. As in Example 1, first, 0.5 mol of magnesium metal and 30 ml of THF were charged in a nitrogen atmosphere, 0.5 mol of 2-chlorophenothiazine was added, and a Grignard reagent was prepared by reacting at 60 ° C. for 2 hours. . Subsequently, the Grignard reagent was added to a toluene solution containing 1.0 mol of chlorotrimethoxysilane and allowed to react at 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then toluene and unreacted chlorotrimethoxysilane were removed from the filtrate to obtain the title compound in a yield of 55%.

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.
7.0 ppm to 6.1 ppm (m) (7H aromatic)
5.3 ppm (1H Hydrogen having a direct bond with a nitrogen atom)
3.7 ppm (m) (9H methoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (V-1).

Example 3 Synthesis of Organosilane Compound Represented by General Formula (III-1) The title compound was synthesized by the following method. As in Example 1, first, 0.3 mol of metal magnesium and 30 ml of THF were charged in a nitrogen atmosphere, 0.3 mol of 2-chloroquinoline was added, and the mixture was reacted at 60 ° C. for 1.5 hours to obtain a Grignard reagent. It was adjusted. Subsequently, the Grignard reagent was added to a THF solution containing 0.5 mol of tetrachlorosilane and reacted at 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted tetrachlorosilane were removed from the filtrate to obtain the title compound in a yield of 55%.

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. 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.
7.8 ppm to 7.2 ppm (m) (6H aromatic)
3.7 ppm (m) (6H ethoxy group methylene group)
1.6 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (III-1).

Example 4 Synthesis of Organosilane Compound Represented by General Formula (VI-1) The title compound was synthesized by the following method. First, 1M NBS was added to a carbon tetrachloride solution containing 0.5 mM of 4,7-dimethyl-1,10-phenanthroline, stirred for 2 hours, and then filtered under reduced pressure to give 3-bromo-4,7- Dimethyl-1,10-phenanthroline was obtained. Subsequently, in the same manner as in Example 1, 0.3 mol of metal magnesium and 30 ml of THF were charged in a nitrogen atmosphere, and the 3-bromo-4,7-dimethyl-1,10-phenanthroline was added, and 1.5 ° C. at 60 ° C. Grignard reagent was prepared by reacting for a period of time. Subsequently, the Grignard reagent was added to a THF solution containing 0.5 mol of chlorotrimethoxysilane and reacted at 30 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted substances were removed from the filtrate to obtain the title compound in a yield of 50%.

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.
8.6 ppm (m) (2H aromatic)
7.7 ppm (m) (1H aromatic)
7.5ppm (m) (2H aromatic)
3.6 ppm (m) (9H methoxy group methyl group)
2.4 ppm (m) (6H methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (VI-1).

Example 5: Synthesis of organosilane compound represented by formula (II-1) The title compound was synthesized by the following method. First, in the same manner as in Example 4, 1M NBS and AIBN were added to a carbon tetrachloride solution containing 0.5 mM of 2-hydroxydibenzofuran, stirred for 2 hours, and then filtered under reduced pressure to obtain 2-bromodibenzofuran. It was. Subsequently, in the same manner as in Example 1, 0.3 mol of metallic magnesium and 30 ml of THF were charged in a nitrogen atmosphere, the 2-bromodibenzofuran was added, and the reaction was carried out at 55 ° C. for 2 hours to prepare a Grignard reagent. Subsequently, the Grignard reagent was added to a THF solution containing 0.5 mol of chlorotriethoxysilane and reacted at 20 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted substances were removed from the filtrate to obtain the title compound in a yield of 60%.

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.
7.5ppm (m) (4H aromatic)
7.2 ppm (m) (3H aromatic)
3.5 ppm (m) (6H ethoxy group methylene group)
1.6 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (II-1).

Example 6: Synthesis of organosilane compound represented by formula (II-3) The title compound was synthesized by the following method. First, similarly to Example 4, 1M NBS and AIBN were added to a carbon tetrachloride solution containing 0.5 mM of 2-hydroxycarbazole, stirred for 2 hours, and then filtered under reduced pressure to obtain 2-bromocarbazole. It was. Subsequently, in the same manner as in Example 1, 0.3 mol of metallic magnesium and 30 ml of THF were charged in a nitrogen atmosphere, the 2-bromocarbazole was added, and the mixture was reacted at 60 ° C. for 2 hours to prepare a Grignard reagent. Subsequently, the Grignard reagent was added to a THF solution containing 0.5 mol of tetrachlorosilane and reacted at 20 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted substances were removed from the filtrate to obtain the title compound in a yield of 60%.

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. 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.
8.5 ppm (m) (1H Hydrogen having a direct bond with a nitrogen atom)
7.6 ppm to 7.5 ppm (m) (4H aromatic)
7.2 ppm (m) (3H aromatic)
3.5 ppm (m) (6H ethoxy group methylene group)
1.4 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (II-3).

Example 7: Synthesis of organosilane compound represented by formula (IV-1) The title compound was synthesized by the following method. First, as in Example 4, 1M NBS and AIBN were added to a carbon tetrachloride solution containing 0.4 mM of 2,3-dimethylquinoxaline, and the mixture was stirred for 1.5 hours and then filtered under reduced pressure. 3-Dimethyl-7-bromoquinoxaline was obtained. Subsequently, in the same manner as in Example 1, 0.2 mol of metal magnesium and 30 ml of THF were charged in a nitrogen atmosphere, the 2,3-dimethyl-7-bromoquinoxaline was added, and the mixture was reacted at 50 ° C. for 4 hours, thereby causing a Grignard reagent. Adjusted. Subsequently, the Grignard reagent was added to a THF solution containing 0.3 mol of chlorotriethoxysilane and reacted at 20 ° C. for 1.5 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure to remove magnesium chloride, and then THF and unreacted substances were removed from the filtrate to obtain the title compound in a yield of 55%.

When infrared absorption spectrum measurement was performed on the obtained compound, absorption derived from SiC was observed at 1085 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.
8.0 ppm (m) (2H aromatic)
7.6 ppm (m) (1H aromatic)
3.5 ppm (m) (6H ethoxy group methylene group)
2.4 ppm (m) (6H methyl group)
1.4 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (IV-1).

を形成させたのち、前記グリニヤール試薬のＴＨＦ溶液中に２−クロロベンズイミダゾールを０．２Ｍを加え２０℃で１時間反応させることによって中間体（Ｂ）を形成させた。

Example 8: Synthesis of organosilane compound represented by formula (I-2) The title compound was synthesized by the following method. First, 1M NBS and AIBN were charged in a carbon tetrachloride solution containing 0.5M terphenyl, stirred for 8 hours, and then filtered under reduced pressure to obtain dibromoterphenyl. Subsequently, 0.2 mol of metallic magnesium was added in a THF atmosphere containing 0.2M of the dibromoterphenyl in a nitrogen atmosphere, and the mixture was reacted at 50 ° C. for 2 hours, whereby Grignard reagent (A).

Then, 0.2M of 2-chlorobenzimidazole was added to a THF solution of the Grignard reagent and reacted at 20 ° C. for 1 hour to form an intermediate (B).

  Further, the intermediate (B) is dissolved in THF and reacted with metallic magnesium at 55 ° C. for 2 hours to synthesize a Grignard reagent, and then added with chlorotriethoxysilane 0.1 M and reacted at 25 ° C. for 2 hours. The title compound was synthesized in 40% yield.

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.
7.7 ppm (m) (2H aromatic; derived from benzimidazole)
7.6 ppm to 7.5 ppm (m) (10H aromatic; derived from terphenyl)
7.4 ppm (m) (2H aromatic; derived from terphenyl)
7.3 ppm (m) (2H aromatic; derived from benzimidazole)
3.5 ppm (m) (6H ethoxy group methylene group)
1.4 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (I-2).
In addition, the organosilane compound from which the group derived from the organosilane compound from which the number of phenylene groups differs, and the terminal condensed polycyclic compound differs can be synthesize | combined by the same method.

Example 9: Synthesis of organosilane compound represented by general formula (V-2) The title compound was synthesized by the following method. First, 1M NBS and AIBN were charged in a carbon tetrachloride solution containing 0.5M quarterthiophene, stirred for 6 hours, and then filtered under reduced pressure to obtain dibromoquaterthiophene. Subsequently, 0.2 mol of metallic magnesium was added in a THF solution containing 0.2 M of dibromoquaterthiophene in a nitrogen atmosphere and reacted at 60 ° C. for 3 hours, so that one side of the bromo group was the same as in Example 8. A Grignard reagent containing only magnesium was formed, and 2-chlorophenothiazine was added to a THF solution containing 0.2 M, followed by reaction at 20 ° C. for 1 hour to form an intermediate (C).

  Further, the intermediate (C) was dissolved in THF, and after adding magnesium metal, the mixture was reacted at 55 ° C. for 2 hours to form a Grignard reagent, and then 0.1 M of chlorotrimethoxysilane was added at 25 ° C. for 2 hours. By reacting, the title compound was synthesized in 40% yield.

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.
8.5 ppm (m) (1H Hydrogen having a direct bond with a nitrogen atom)
7.1 ppm (m) (8H thiophene ring)
6.9 ppm (m) (5H aromatic)
6.8 ppm (m) (2H aromatic)
3.5 ppm (m) (9H methoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (V-2).
In addition, the organosilane compound from which the group derived from the organosilane compound from which the number of thiophene groups differs, and the terminal condensed polycyclic compound differs can be synthesize | combined by the same method.

Example 10: Synthesis of organosilane compound represented by formula (II-2) The title compound was synthesized by the following procedure. First, 0.5 mol of metallic magnesium was added in a THF solution containing 0.5M of 2-bromodibenzofuran, which is an intermediate of Example 5, and reacted at 50 ° C. for 3 hours to form a Grignard reagent. Subsequently, 0.5M of 1-bromonaphthalene was added and then reacted at 20 ° C. for 1 hour to form 3-naphthalen-2-yl-dibenzofuran.

を形成させた後に、クロロトリエトキシシラン０．５Ｍを加え２０℃で２時間反応させることによって、表題の化合物を３０％の収率で合成した。 Furthermore, 0.5M of the 3-naphthalen-2-yl-dibenzofuran was added to a carbon tetrachloride solution containing 1MNBS and AIBN, and reacted at 55 ° C. for 2 hours, whereby intermediate (D)

The title compound was synthesized in 30% yield by adding 0.5 M chlorotriethoxysilane and reacting at 20 ° C. for 2 hours.

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.
7.8 ppm (m) (4H aromatic)
7.5ppm (m) (5H aromatic)
7.3 ppm (m) (2H aromatic)
7.2 ppm (m) (2H aromatic)
3.6 ppm (m) (6H ethoxy group methylene group)
1.5 ppm (m) (9H ethoxy group methyl group)
From these results, it was confirmed that the obtained compound was a compound represented by the general formula (II-2).
In addition, the organosilane compound from which the group derived from the organosilane compound from which the number of acene skeleton differs, and the terminal condensed polycyclic compound differs can be synthesize | combined by the same method.

  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 (9)

Formula (α);
Z- (R ¹ ) _m -SiR ² R ³ R ⁴ (α)
(In the formula, Z is a monovalent organic group derived from a condensed polycyclic heterocyclic compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered ring; R ¹ is a divalent group; M is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms). . General formula (I);

(Wherein X ¹ is a carbon atom, nitrogen atom, oxygen atom or sulfur atom, and X ² is a carbon atom or nitrogen atom (except when X ¹ and X ² are simultaneously carbon atoms); n1 Is an integer of 0 to 8; R ¹ is a divalent organic group; m is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy having 1 to 4 carbon atoms. A π-electron conjugated organosilane compound represented by: General formula (II);

(Wherein, ^{X 3} is a nitrogen atom, a certain oxygen atom or sulfur atom; is n2 and n3 is an integer satisfying 0 ≦ n2 + n3 ≦ 7; R 1 is a divalent organic group; m is 0 A π-electron conjugated organosilane compound represented by an integer of 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms. General formula (III);

(Wherein, X ⁴ and X ⁵ are each independently a carbon atom or a nitrogen atom (except when X ⁴ and X ⁵ are simultaneously carbon atoms); n4 is an integer of 0 to 8; R ¹ is a divalent organic group; m is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms). Conjugated organosilane compounds. General formula (IV);

(Wherein, X ⁶ and X ⁷ are each independently a carbon atom or a nitrogen atom (except when X ⁶ and X ⁷ are simultaneously carbon atoms); n5 is an integer of 0 to 8; R ¹ is a divalent organic group; m is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms). Conjugated organosilane compounds. Formula (V);

(Wherein X ⁸ and X ⁹ are each independently a carbon atom, nitrogen atom, oxygen atom or sulfur atom (except when X ⁸ and X ⁹ are simultaneously carbon atoms); n6 and n7 are 0) ≦ n6 + n7 ≦ 7; R ¹ is a divalent organic group; m is an integer of 0 to 10; R ^{2 to} R ⁴ each independently represent a halogen atom or a carbon number of 1 to A π-electron conjugated organosilane compound represented by (4) an alkoxy group. Formula (VI);

(Wherein X ¹⁰ and X ¹¹ are each independently a carbon atom or a nitrogen atom (except when X ¹⁰ and X ¹¹ are simultaneously carbon atoms); n8 and n9 are 0 ≦ n8 + n9 ≦ 7) R ¹ is a divalent organic group; m is an integer of 0 to 10; R ^{2 to} R ⁴ are each independently a halogen atom or an alkoxy group having 1 to 4 carbon atoms. A π-electron conjugated organosilane compound represented by R ¹ is a general formula (i) to (iv);

The π-electron conjugated organosilane compound according to any one of claims 1 to 7, which is a divalent organic group selected from the group consisting of (wherein n10 is an integer of 0 to 8). Formula (β);
Z- (R ¹ ) _m -MgX ²⁰ (β)
(In the formula, Z is a monovalent organic group derived from a condensed polycyclic heterocyclic compound having 2 to 10 condensed rings composed of a 5-membered ring and / or a 6-membered ring; R ¹ is a divalent group; An organic group; m is an integer of 0 to 10; X ²⁰ is a halogen atom; and a general formula (γ);
X ²¹ —SiR ² R ³ R ⁴ (γ)
Wherein X ²¹ 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. A π-electron conjugated organosilane compound, characterized by subjecting the compound to a Grignard reaction.