JP2009120570A - New carbonyl-bridged athene-based compound and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new athene-based compound precursor efficiently producing a highly regular electroconductive thin film according to a simple method. <P>SOLUTION: The carbonyl-bridged athene-based compound is represented by general formula (1) äwherein, Z represents -C(=O)-; m and n represent each an integer of ≥0; and R<SB>1</SB>and R<SB>2</SB>represent each independently any of H, a 1-30C alkyl, a 1-30C halogenated alkyl, a 6-30C aryl, a 4-30C heteroaryl, a 1-30C alkoxy, a 6-30C aryloxy, a 3-30C trialkylsilyl, or a halogen}. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel carbonyl-bridged acene compound useful as a raw material for a conductive thin film constituting an organic semiconductor device or the like. The present invention also relates to an easy process for producing such a carbonyl bridged acene compound.

  In recent years, semiconductor device patterns have been miniaturized and the degree of circuit integration has been increasing, and it is now desirable to establish a technique for forming conductive thin films of several nanometers (nm) to several tens of nanometers. ing. As an example of a technique for forming such a thin conductive thin film on a semiconductor, a method for forming a self-assembled (Self Assembling) thin film (hereinafter referred to as an SA thin film) using organic molecules has been recently proposed. This technique utilizes the property that organic molecules are arranged in a regular structure, and can produce a thin film having extremely few defects and high order. The SA thin film can be formed by applying organic molecules or a precursor thereof to a substrate such as a semiconductor by a technique such as printing or ink jet.

  Various pentacene addition compounds that are precursors of pentacene, which is a kind of acene compound, have been reported as materials suitable for the formation of SA thin films (see Patent Documents 1 to 3 and Non-Patent Documents 1 and 2 below). . However, there have been many problems in efficiently producing thin films having a regular structure using these pentacene adducts with simple and inexpensive equipment. For example, in order to convert these pentacene adducts into pentacene, light irradiation with expensive equipment is required, thermal decomposition at a high temperature of 200 ° C. or higher is required, or a long time of 1 hour at 150 ° C. It required thermal decomposition.

In view of these problems, a method for directly forming a pentacene thin film by dissolving pentacene at a high temperature has recently been reported (see Patent Document 4 and Non-Patent Documents 3 and 4 below). These methods are slightly simpler than the above-mentioned method of converting the pentacene addition compound to pentacene, but in order to dissolve pentacene having a very low solubility, a complicated process, that is, a solvent having a high boiling point of 200 ° C. or higher is used as a solvent. And a step of obtaining a dispersion of pentacene fine particles by heating a mixture of pentacene and a solvent to a high temperature and quenching. Furthermore, in these methods, it is necessary to reheat the dispersion to 100 ° C. to 200 ° C. after coating the dispersion on the substrate. Therefore, these methods are still not sufficient for efficiently producing a conductive thin film.
U.S. Patent Publication No. 2003/0144562 US Patent Publication No. 2004/0119073 US Patent Publication No. 2004/0183070 JP 2005-281180 A Tetrahedoron Letters, 46, 1981 (2005) J. et al. Am. Chem. Soc. 2004, 126, 12740 (1994) Synth. Met. , 153, 1 (2005) Applied physics 75 (3), 565 (2006)

  The present invention was devised in view of the current state of the prior art, and the object thereof is a novel acene compound precursor capable of efficiently producing a highly regular conductive thin film by a simple method and a method for producing the same. Is to provide.

  In order to achieve such an object, the present inventors have conducted intensive studies on a precursor that is more easily dissolved in an organic solvent than a target acene compound and can be easily converted into an acene compound by a simple operation. The bridged acene compound has good solubility in many organic solvents, and can easily produce the target acene compound by heating at a temperature of about 100 ° C. to 150 ° C. for a short time. I found. Furthermore, the present inventors have found that this carbonyl-bridged acene-based compound has two synthetic routes utilizing the Diels-Alder reaction, that is, (A) a method in which a condensed benzyne is reacted with dimethylidene norbornenes, and (B It has been found that by using any synthetic route of the method of reacting norbornadiene with orthodihaloquinodimethane, it can be easily derived via a hydroxymethylene bridged acene compound. Based on these findings, the present inventors have completed the present invention.

（式中、Ｚは−Ｃ（＝Ｏ）−を表わす。ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるカルボニル架橋型アセン系化合物が提供される。 That is, according to the present invention, the general formula (1)

(In the formula, Z represents —C (═O) —. M and n each represents an integer of 0 or more. R ₁ and R ₂ each independently represent H, C1 to C30 alkyl, or C1 to C30. Alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen. A carbonyl bridged acene compound is provided.

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるヒドロキシメチレン架橋型アセン系化合物が提供される。 Moreover, according to the present invention, the general formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen) is provided.

（式中、ｍは０以上の整数を表わす。Ｒ_１はＨ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表されるジメチリデンノルボルネン類と
一般式（５）

（式中、ｎは０以上の整数を表わす。Ｒ_２はＨ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表される縮合ベンザイン類を反応させることにより、一般式（６）

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表される環化体もしくはそのアルカリ金属塩を得、この環化体もしくはそのアルカリ金属塩を脱水素させることにより、
一般式（３）

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表されるオキシメチレン架橋型アセン系化合物を得、このオキシメチレン架橋型アセン系化合物を分解することにより、
一般式（２）

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるヒドロキシメチレン架橋型アセン系化合物を得ることを特徴とする一般式（２）で表されるヒドロキシメチレン架橋型アセン系化合物の製造方法が提供される。 Moreover, according to the present invention,
General formula (4)

(In the formula, m represents an integer of 0 or more. R ₁ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy. , C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen R ₃ is C2-C30 acyl, C2-C30 α-alkoxyalkyl, tetrahydropyranyl, C4-C30 t -Represents an alkyl, a C3-C30 trialkylsilyl or a C8-C30 allyldialkylsilyl) and a general formula (5)

(In the formula, n represents an integer of 0 or more. R ₂ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy) , C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen) is reacted to give a general formula (6)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl), or an alkali metal salt thereof, By dehydrogenating this cyclized product or its alkali metal salt,
General formula (3)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl). By decomposing oxymethylene bridged acene compounds,
General formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen)) is obtained. A method for producing a hydroxymethylene bridged acene compound represented by the general formula (2) is provided.

（式中、ｍは０以上の整数を表わす。Ｒ_１はＨ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表されるノルボルナジエン類と
一般式（８）

（式中、ｎは０以上の整数を表わす。Ｘはハロゲンを表わす。Ｒ_２はＨ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるオルトジハロキノジメタン類を反応させることにより、一般式（９）

（式中、ｍ，ｎは０以上の整数を表わす。Ｘはハロゲンを表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表される環化体を得、この環化体を脱ハロゲン化水素させることにより、
一般式（３）

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。）で表されるオキシメチレン架橋型アセン系化合物を得、このオキシメチレン架橋型アセン系化合物を分解することにより、
一般式（２）

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるヒドロキシメチレン架橋型アセン系化合物を得ることを特徴とする一般式（２）で表されるヒドロキシメチレン架橋型アセン系化合物の製造方法が提供される。 Moreover, according to the present invention, the general formula (7)

(In the formula, m represents an integer of 0 or more. R ₁ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy. , C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen R ₃ is C2-C30 acyl, C2-C30 α-alkoxyalkyl, tetrahydropyranyl, C4-C30 t -Represents an alkyl, a C3-C30 trialkylsilyl or a C8-C30 allyldialkylsilyl.) And a norbornadiene represented by the general formula (8)

(In the formula, n represents an integer of 0 or more. X represents a halogen. R ₂ represents H, a C1-C30 alkyl, a C1-C30 halogenated alkyl, a C6-C30 aryl, or a C4-C30 heteroaryl. , C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen) is reacted with an orthodihaloquinodimethane represented by the general formula (9 )

(In the formula, m and n represent an integer of 0 or more. X represents a halogen. R ₁ and R ₂ each independently represents H, a C1-C30 alkyl, a C1-C30 halogenated alkyl, a C6- C3 aryl, C4 to C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen, R ₃ represents C2 to C30 acyl, C2 C30 α-alkoxyalkyl, tetrahydropyranyl, C4 to C30 t-alkyl, C3 to C30 trialkylsilyl, or C8 to C30 allyldialkylsilyl). By dehydrohalogenating this cyclized product,
General formula (3)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl). By decomposing oxymethylene bridged acene compounds,
General formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen)) is obtained. A method for producing a hydroxymethylene bridged acene compound represented by the general formula (2) is provided.

  Moreover, according to this invention, the hydroxymethylene bridge | crosslinking type acene type compound represented by General formula (2) is oxidized, The manufacturing method of the carbonyl bridged type acene type compound represented by General formula (1) characterized by the above-mentioned. Is provided.

（式中、ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。）で表されるアセン系化合物の製造方法が提供される。 According to the present invention, the carbonyl bridged acene compound represented by the general formula (1) is decomposed by heating to its decomposition temperature.

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 trialkylsilyl, or halogen is represented.).

The carbonyl bridged acene compound of the present invention is more easily dissolved in an organic solvent than the target acene compound, and easily converted into the target acene compound by a simple operation of heating at a temperature of about 100 to 150 ° C. for a short time. Since it can be converted, it can be used to efficiently produce a highly regular conductive thin film useful in the field of organic semiconductor devices and the like by a simple method.
In addition, as an organic solvent used for dissolving acene compounds and their precursors, use of trichlorobenzene having a higher halogen number, monochlorobenzene having a lower halogen number than dichlorobenzene, or xylene containing no halogen, from the viewpoint of environmental protection. Although desirable, the carbonyl bridged acene compound of the present invention has a decomposition temperature close to the boiling point of monochlorobenzene (132 ° C.) and the boiling point of xylene (about 140 ° C.). A method for producing a gentle conductive thin film can be provided.

（スキーム中、Ｚは−Ｃ（＝Ｏ）−を表わす。ｍ，ｎは０以上の整数を表わす。Ｒ_１、Ｒ_２はそれぞれ独立して、Ｈ、Ｃ１〜Ｃ３０のアルキル、Ｃ１〜Ｃ３０のハロゲン化アルキル、Ｃ６〜Ｃ３０のアリール、Ｃ４〜Ｃ３０のヘテロアリール、Ｃ１〜Ｃ３０のアルコキシ、Ｃ６〜Ｃ３０のアリールオキシ、Ｃ３〜Ｃ３０のトリアルキルシリルまたはハロゲンのいずれかを表わす。Ｒ_３はＣ２〜Ｃ３０のアシル、Ｃ２〜Ｃ３０のα−アルコキシアルキル、テトラヒドロピラニル、Ｃ４〜Ｃ３０のｔ−アルキル、Ｃ３〜Ｃ３０のトリアルキルシリルまたはＣ８〜Ｃ３０のアリルジアルキルシリルのいずれかを表わす。） The carbonyl bridged acene compound of the general formula (1) of the present invention is a kind of precursor of an acene compound which is a material for a conductive thin film, and is a carbonyl bridge, that is, a bridge of —C (═O) —. Part of an acene compound. The outline of the production method of this compound is shown in the following reaction scheme 1. The compound of the general formula (1) can be easily obtained by decomposing the oxymethylene bridged acene compound of the general formula (3) to obtain a hydroxymethylene bridged acene compound of the general formula (2) and oxidizing it. Obtainable. The oxymethylene bridged acene compound of the general formula (3) has two synthetic routes utilizing the Diels-Alder reaction, that is, (A) the condensation of the general formula (5) to the dimethylidene norbornenes of the general formula (4). It can be induced by using any one of the synthesis routes of the method of reacting benzynes and the method of reacting the orthodihaloquinodimethanes of the general formula (8) with the norbornadienes of the general formula (7). .

(In the scheme, Z represents —C (═O) —. M and n each represents an integer of 0 or more. R ₁ and R ₂ each independently represent H, C1 to C30 alkyl, or C1 to C30. halogenated alkyl, aryl C6 to C30, heteroaryl C4 to C30, alkoxy of C1-C30, aryloxy C6 to C30, is .R ₃ representing one of trialkylsilyl or halogens C3 to C30 C2～ C30 acyl, C2 to C30 α-alkoxyalkyl, tetrahydropyranyl, C4 to C30 t-alkyl, C3 to C30 trialkylsilyl, or C8 to C30 allyldialkylsilyl)

（図中、Ｚ、ｍ、ｎ、Ｒ_１、Ｒ_２及びＲ_３は反応スキーム１について定義されるものと同じである。） Next, the method for producing the carbonyl-bridged acene compound of the present invention using the synthesis route (A) and the synthesis route (B) will be described more specifically.
Process for producing carbonyl bridged acene compound of the present invention using synthetic route (A) :
The details of the method for producing the carbonyl bridged acene compound of the present invention using the synthesis route (A) are shown in the following reaction scheme 2. In this production method, first, the cyclized product of the general formula (6) or its alkali is obtained by the Diels-Alder reaction (1) -A of the dimethylidene norbornenes of the general formula (4) and the condensed benzines of the general formula (5). A metal salt is introduced. This cyclized product or alkali metal salt thereof is then converted to an oxymethylene bridged acene compound of the general formula (3) by dehydrogenation reaction (2) -A. This oxymethylene bridged acene compound is converted to a hydroxymethylene bridged acene compound of the general formula (2) by the decomposition reaction (3) under acid, alkali or neutral conditions. This hydroxymethylene bridged acene compound is further derived into a carbonyl bridged acene compound of the general formula (1) by oxidation reaction (4).

(In the figure, Z, m, n, R ₁ , R ₂ and R ₃ are the same as defined for Reaction Scheme 1.)

Each reaction shown in the above reaction scheme 2 will be described more specifically.
Reaction (1) -A
Reaction (1) -A is a reaction for obtaining a cyclized product of general formula (6) by Diels-Alder reaction of dimethylidene norbornenes of general formula (4) and condensed benzines of general formula (5).
Examples of the dimethylidene norbornene of the general formula (4) used in the reaction (1) -A include 7-acetoxy-2,3-bismethylidene-5,6-benzonorbornene, 7- (p-chlorobenzoyloxy)- 2,3-bismethylidene-5,6-benzonorbornene, 7-benzyloxy-2,3-bismethylidene-5,6-benzonorbornene, 7-t-butoxy-2,3-bismethylidene-5,6-benzonorbornene, 7- (α-ethoxy) ethoxy-2,3-bismethylidene-5,6-benzonorbornene, 7- (α-pyranyl) oxy-2,3-bismethylidene-5,6-benzonorbornene, 7-acetoxy-2 3-bismethylidene-5,6-naphthonorbornene, 7- (p-chlorobenzoyloxy) -2,3-bismethylidene -5,6-naphthonorbornene, 7-benzyloxy-2,3-bismethylidene-5,6-naphthonorbornene, 7-t-butoxy-2,3-bismethylidene-5,6-naphthonorbornene, 7- (α- Ethoxy) ethoxy-2,3-bismethylidene-5,6-naphthnorbornene, 7- (α-pyranyl) oxy-2,3-bismethylidene-5,6-naphthnorbornene, 7-acetoxy-2,3-bismethylidene-5 , 6-anthranorbornene, 7- (p-chlorobenzoyloxy) -2,3-bismethylidene-5,6-anthranorbornene, 7-benzyloxy-2,3-bismethylidene-5,6-anthrannorbornene, 7-t -Butoxy-2,3-bismethylidene-5,6-anthranorbornene, 7- (α-ethoxy) ethoxy 2,3 Bisumechiriden 5,6 anthrahydroquinone norbornene, 7- (alpha-pyranyl) the substituent on the benzene ring of the oxy-2,3-Bisumechiriden 5,6 anthranilamide norbornene and the compounds _R 1 ( R ₁ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 tri And a compound to which alkylsilyl or halogen is bound).

The C1-30 alkyl in the substituent R ₁ is not particularly limited, and examples thereof include methyl, ethyl, propyl, n-butyl, isobutyl, neopentyl, octyl, dodecyl, etc .; the C1 to C30 halogenated alkyl group includes Although not particularly limited, for example, trifluoromethyl, trifluoroethyl, perfluorohexyl and the like can be mentioned; C6-C30 aryl is not particularly limited, and phenyl, perfluorophenyl, methylphenyl, dioctylphenyl, trifluoromethyl Phenyl, naphthyl, biphenyl and the like can be mentioned; C4-C30 heteroaryl is not particularly limited, and examples thereof include thienyl, pyrrolyl, pyridyl, hexylthienyl, benzothienyl, carbazolyl, etc .; C1-C30 alkoxy Or C6-C30 aryloxy is not particularly limited, and examples thereof include methoxy, ethoxy, octyloxy, phenoxy, naphthoxy, perfluorophenoxy, perfluoronaphthoxy and the like, and C3-C30 trialkylsilyl groups are particularly limited. Examples thereof include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tri-n-octylsilyl group. Halogen is not particularly limited, and examples thereof include fluorine, chloro, and bromo.

These compounds of the general formula (4) can be synthesized with reference to the following publicly known documents 1 to 3.
Known Document 1: Org. Biomol. Chem. , 3 , 448 (2005)
Known Document 2: Helvetica Chimca Acta, 68, 236 (1985)
Known Document 3: J. Org. Amer. Chem. Soc. , 98 , 1810 (1976)

The condensed benzynes of the general formula (5) used in the reaction (1) -A are usually obtained as reactive species in the reaction system by allowing a 2,3-dihalogenated acene compound to act on a dehalogenating agent. be able to. Examples of 2,3-dihalogenated acene compounds include 1-fluoro-2-iodobenzene, 1-fluoro-2-bromobenzene, 1,2-dibromobenzene, 1,2-diiodobenzene, 2-fluoro-3- Iodonaphthalene, 2-bromo-3-fluorobenzene, 2-fluoro-3-bromonaphthalene, 2-chloro-3-iodonaphthalene, 2-chloro-3-bromonaphthalene, 2,3-diiodonaphthalene, 2,3 -Dibromonaphthalene, 2,3-diiodoanthracene, 2,3-dibromoanthracene, 2,3-diiodotetracene, 2,3-dibromotetracene, and the above substituent R ₂ on the benzene ring of these compounds ( R ₂ is H, alkyl of C1-C30, a halogenated alkyl C1-C30, a C6~C30 aryl, C4～C3 Heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, may be mentioned compounds.) Bound to represent one of trialkylsilyl or halogen C3 to C30.

The C1-30 alkyl in the substituent R ₂ is not particularly limited, and examples thereof include methyl, ethyl, propyl, n-butyl, isobutyl, neopentyl, octyl, dodecyl and the like; the C1 to C30 halogenated alkyl group includes Although not particularly limited, for example, trifluoromethyl, trifluoroethyl, perfluorohexyl and the like can be mentioned; C6-C30 aryl is not particularly limited, and phenyl, perfluorophenyl, methylphenyl, dioctylphenyl, trifluoromethyl Phenyl, naphthyl, biphenyl and the like can be mentioned; C4-C30 heteroaryl is not particularly limited, and examples thereof include thienyl, pyrrolyl, pyridyl, hexylthienyl, benzothienyl, carbazolyl, etc .; C1-C30 alkoxy Or C6-C30 aryloxy is not particularly limited, and examples thereof include methoxy, ethoxy, octyloxy, phenoxy, naphthoxy, perfluorophenoxy, perfluoronaphthoxy and the like, and C3-C30 trialkylsilyl groups are particularly limited. Examples thereof include a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, and a tri-n-octylsilyl group. Halogen is not particularly limited, and examples thereof include fluorine, chloro, and bromo.

  As a dehalogenating agent, alkali metals such as Li, Na, K, or alkali organic metals such as methyllithium, n-butyllithium, t-butyllithium, N, N-diisopropyllithium amide, and phenyllithium should be used. Can do.

Preparation of the condensed benzines of the general formula (5) can be carried out with reference to the following known documents 4 to 6.
Known Document 4: J. Org. Chem. Soc. (C), 2162 (1970)
Known Document 5: European Polym. J. et al. , 27, 27-33 (1991)
Known document 6: J. Org. Amer. Chem. Soc. , 128 , 9612 (2006)

  In the reaction (1) -A, the amount of the 2,3-dihalogenated acene compound used as a raw material for the condensed benzynes of the general formula (5) is 1 part by weight of the dimethylidene norbornenes of the general formula (4). It is preferable that it is 1-10 weight part, More preferably, it is 1-4 weight part. Moreover, it is preferable that the usage-amount of a dehalogenating agent is 1-6 weight part with respect to 1 weight of 2, 3- dihalogenated acene type compounds, More preferably, it is 1-4 weight part.

  This reaction is carried out substantially under the conditions for preparing the condensed benzynes of the general formula (5) using a 2,3-dihalogenated acene-based compound, and the reaction vessel is used in an inert gas atmosphere such as argon or nitrogen. 2,3-dihalogenated acene-based compound, dimethylidene norbornene of general formula (4) and a dehalogenating agent are charged, and the temperature is -90 to 120 ° C, preferably -70 to 80 ° C for 1 to 60 hours. Preferably it can carry out by making it react for 1 to 30 hours. The reaction reagent is preferably added all at once or sequentially, and a method of adjusting the concentration of the reaction reagent such as dropwise addition can also be applied. In addition, this reaction is usually carried out in a normal pressure open system, but it can also be carried out under normal pressure to pressure using a sealed container.

  In this reaction, a solvent is used as necessary. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and diethylbenzene; halogenated aromatic hydrocarbon solvents such as chlorobenzene, fluorobenzene, α, α, and α-trifluorotoluene; diethyl ether , Ether solvents such as tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and the like can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 500 parts by weight, more preferably 5 to 250 parts by weight, based on 1 part by weight of the dimethylidene norbornenes of the general formula (4).

  As a method for isolating the cyclized product of the general formula (6), which is the product of this reaction, extraction, crystallization, column chromatography or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product. Further, the isolation of the product is not necessarily required for this reaction step, and the product can be isolated after the next reaction (2) -A or the subsequent reaction (3).

Reaction (2) -A
Reaction (2) -A is a reaction in which the cyclized product of general formula (6) obtained by reaction (1) -A is dehydrogenated to obtain an oxymethylene bridged acene compound of general formula (3). . Dehydrogenation reagents used in this reaction include benzoquinones such as 2,3,5,6-tetrachloro-p-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 2, 2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, 1-azobis-1-cyclohexanecarbonitrile, dimethyl- Low temperature decomposable azo compounds such as 2,2′-azobisisobutyrate, alkali metals such as Li, Na and K, or methyl lithium, n-butyl lithium, t-butyl lithium, N, N-diisopropyl lithium amide And alkali organic metals such as phenyl lithium. In addition, when performing this reaction following said reaction (1) -A, since the dehalogenation reaction reagent used in reaction (1) -A acts also as a dehydrogenation reaction reagent of this reaction, reaction ( 1) A dehydrogenation reaction reagent is substantially renewed by adjusting the amount of the dehalogenation reaction reagent so that the dehalogenation reaction reagent used in -A remains in the reaction system after the reaction. It is also possible to carry out the reaction (2) -A without adding to.

  It is preferable that the usage-amount of the said dehydrogenation reaction reagent is 1-10 weight part with respect to 1 weight part of cyclization bodies of General formula (6), More preferably, it is 1-5 weight part.

  This reaction can be generally carried out under normal pressure conditions at 0 to 200 ° C., preferably 0 to 150 ° C., for 1 to 50 hours, preferably 1 to 30 hours.

  In this reaction, a solvent is used as necessary. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and diethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene. Halogenated aromatic hydrocarbon solvents such as dichloromethylene, chloroform, dichloroethane and the like, ether ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Solvent: Amide-based solution such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone , It is possible to use acetonitrile, and the like nitrile solvents butyronitrile. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 500 parts by weight, more preferably 5 to 250 parts by weight, based on 1 part by weight of the compound of the general formula (6) of the raw material.

  As an isolation method of the oxymethylene bridged acene compound of the general formula (3), which is a product of this reaction, extraction, crystallization, column chromatography, or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product. Further, the isolation of the product is not necessarily required for this reaction step, and the product can be isolated after the next reaction (3) is carried out.

Reaction (3)
Reaction (3) is a reaction for decomposing the oxymethylene bridged acene compound of general formula (3) obtained by reaction (2) -A to obtain a hydroxymethylene bridged acene compound of general formula (2). is there. The reaction reagent used in this reaction is a catalytic hydrogenation catalyst or ester which is reacted under acid, base or neutral conditions depending on the structure of the substituent R ₃ of the oxymethylene bridged acene compound of general formula (3) A hydrolase is used. Acids for making the acidic conditions include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfone Inorganic and organic acids such as acid, acetic acid, chloroacetic acid, fluoroacetic acid, trifluoroacetic acid, and aqueous solutions thereof can be used. In addition, bases for basic conditions include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, lithium methoxide, potassium methoxide, ammonia, methylamine, dimethylamine, propylamine, Inorganic and organic bases such as hydrazine and methyl hydrazine and aqueous solutions thereof can be used.

  The amount of the acid used is preferably 0.0001 to 10 parts by weight, more preferably 0.001 to 1 part by weight with respect to 1 part by weight of the compound of the general formula (3). Moreover, it is preferable that the usage-amount of a base is 0.1-20 weight part with respect to 1 weight part of compounds of General formula (3), More preferably, it is 1-10 weight part.

  This reaction can be generally carried out under normal pressure conditions at 0 to 200 ° C., preferably 0 to 150 ° C., for 1 to 50 hours, preferably 1 to 30 hours.

  In this reaction, a solvent is used as necessary. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol and butanol; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene and diethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, Halogenated aromatic hydrocarbon solvents such as hexafluorobenzene, α, α, α-trifluorotoluene; ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Solvent: Amide-based solution such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone Acetonitrile, nitrile solvents butyronitrile; can be used acetone, and the like ketone solvents or water such as methyl ethyl ketone. These solvents may be used alone or in combination of two or more. It is preferable that the usage-amount of a solvent is 5-500 weight part with respect to 1 weight part of compounds of General formula (3), More preferably, it is 5-250 weight part.

  As a method for isolating the hydroxymethylene bridged acene compound of the general formula (2), which is the product of this reaction, extraction, crystallization, column chromatography or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product. Further, the isolation of the product is not necessarily required for this reaction step, and the product can be isolated after the next reaction (4) is carried out.

  In order to carry out this reaction more efficiently, it is desirable to accelerate the reaction using a phase transfer catalyst when either acid or base is used. Quaternary ammonium such as tetra-N-ethylammonium bromide, tetra-N-butylammonium bromide, N-benzyltrimethylammonium chloride, N-benzyltriethylammonium bromide, triethyloctylammonium iodide as the phase transfer catalyst when using acid Examples of the phase transfer catalyst in the case of using a base include the quaternary amine salt, 18-crown-5, 18-crown-6, benzo-15-crown-5, benzo-18-crown- 6, crown ethers such as dibenzo-18-crown-6,5,6-benzo-4,7,13,16,21,24-hexoxa-1,10-diazabicyclo [8,8,8] hexacosane be able to. The amount of the phase transfer catalyst used is preferably 0.0001 to 0.1 parts by weight, more preferably 0.0005 to 0.05 parts by weight, per 1 part by weight of the compound of the general formula (3).

This reaction can be carried out with reference to the following publicly known documents 7 and 8 relating to decomposition of alcohol protecting groups and hydrolysis of esters. This reaction can be carried out in a reaction under neutral conditions using an ester hydrolase in addition to the above reaction using an acid or a base.
Known Document 7: Protective Groups In Organic Synthesis-PP, PP 10-142 (1990: John Wily & Sons)
Known Document 8: 5th Edition Experimental Chemistry Course, No. 16, 10 (2005: The Chemical Society of Japan)

Reaction (4)
Reaction (4) is a reaction in which the hydroxymethylene bridged acene compound of general formula (2) obtained by reaction (3) is oxidized to obtain a carbonyl bridged acene compound of general formula (1). This reaction is an oxidation reaction for converting a hydroxymethylene bridged acene compound of the general formula (2), which is a secondary alcohol, into a ketone. As reported in the following publicly known literature, Jones reagent, Saratt reagent, Collins reagent , Oxidation reaction using chromium oxide such as PCC, PDC, etc. (known documents 9 and 10), oxidation reaction using hypervalent iodine compound agent (known document 11), swallow acidification using dimethyl sulfoxide as an oxidizing agent (Known Document 12), oxidation reaction using sulfinimidoyl chlorides (Known Document 13), and the like can be used. From the viewpoint of safety, a method that does not use harmful chromium oxide (Known Documents 12 and 13) is desirable, and a method that does not generate odor (Known Document 13) can be used more easily.
Known Document 9: Tetrahedron Letters. 1975, 2647
Known Document 10: Tetrahedron Letters. , 1979, 399
Known Document 11: J. Org. Org. Chem. , 48, 4156 (1983)
Known Document 12: Tetrahedron, 34, 1651 (1978)
Known Document 13: Bull. Chem. Soc. Jpn. , 75, 223 (2002)

  When this reaction is carried out using the above sulfinimidoyl chloride, N-tert-butylphenylsulfinimidoyl chloride is suitable as the sulfinimidoyl chloride, and 1,8-diazabicyclo [5,4 as the base used in combination. , 0] undec-7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,4-diazabicyclo [2,2,2] octane, triethylamine, diisopropylethylamine and the like. It is preferable that the usage-amount of sulfinimidoyl chlorides is 1-10 weight part with respect to 1 weight part of compounds of General formula (2), More preferably, it is 1-3 weight part. The amount of the base used in combination is preferably 1 to 15 parts by weight, more preferably 1 to 5 parts by weight with respect to 1 part by weight of the compound of the general formula (2).

  When the above swarnidation is used in this reaction, the active oxidant is prepared from dimethyl sulfoxide and oxalyl chloride. The amount of dimethyl sulfoxide used is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 1 part by weight of the compound of the general formula (2), and the amount of oxalyl chloride used is the general formula ( It is preferable that it is 1-10 weight part with respect to 1 weight part of compounds of 2), More preferably, it is 1.2-5 weight part. As the base to be used in combination, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,4-diazabicyclo [2,2 , 2] Tertiary amines such as octane, triethylamine, diisopropylethylamine can be used. The amount of the tertiary amine used is preferably 1 to 15 parts by weight, more preferably 1.5 to 10 parts by weight with respect to 1 part by weight of the compound of the general formula (2).

  This reaction can be generally carried out under normal pressure conditions at −80 to 150 ° C., preferably −80 to 100 ° C., for 1 to 50 hours, preferably 1 to 30 hours.

  In this reaction, a solvent is used as necessary. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and diethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene. Halogenated aromatic hydrocarbon solvents such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; N, N-dimethylformamide, N, N- Use amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone, and nitrile solvents such as acetonitrile and butyronitrile. It can be. These solvents may be used alone or in combination of two or more. It is preferable that the usage-amount of a solvent is 5-500 weight part with respect to 1 weight part of the compound of General formula (2), More preferably, it is 5-250 weight part.

  As a method for isolating the carbonyl bridged acene compound of the general formula (1), which is the product of this reaction, extraction, crystallization, column chromatography or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product.

（図中、Ｚ、ｍ、ｎ、Ｒ_１、Ｒ_２及びＲ_３は反応スキーム１について定義されるものと同じである。） Method for producing carbonyl bridged acene compound of the present invention using synthetic route (B) :
The details of the method for producing a carbonyl bridged acene compound of the present invention using the synthetic route (B) are shown in the following reaction scheme 3. In this production method, first, the cyclized product of the general formula (9) is derived by the Diels-Alder reaction (1) -B of the norbornadiene of the general formula (7) and the orthodihaloquinodimethane of the general formula (8). It is burned. This cyclized product is then converted to an oxymethylene bridged acene compound of general formula (3) by dehydrohalogenation reaction (2) -B. This oxymethylene bridged acene compound is converted to a hydroxymethylene bridged acene compound of the general formula (2) by the decomposition reaction (3) under acid, alkali or neutral conditions. This hydroxymethylene bridged acene compound is further derived into a carbonyl bridged acene compound of the general formula (1) by oxidation reaction (4).

(In the figure, Z, m, n, R ₁ , R ₂ and R ₃ are the same as defined for Reaction Scheme 1.)

Each reaction shown in the above reaction scheme 3 will be described more specifically.
Reaction (1) -B
Reaction (1) -B is a reaction for obtaining a cyclized product of general formula (9) by Diels-Alder reaction of norbornadienes of general formula (7) and orthodihaloquinodimethanes of general formula (8).
Examples of the norbornadiene of the general formula (7) used in the reaction (1) -B include 7-acetoxy-5,6-benzonorbornadiene, 7- (p-chlorobenzoyloxy) -5,6-benzonorbornadiene, 7 -Benzyloxy-5,6-benzonorbornadiene, 7-t-butoxy-5,6-benzonorbornadiene, 7- (α-ethoxy) ethoxy-5,6-benzonorbornadiene, 7- (α-pyranyl) oxy-5 , 6-Benzonorbornadiene, 7-acetoxy-5,6-naphthonorbornadiene, 7- (p-chlorobenzoyloxy) -5,6-naphthonorbornadiene, 7-benzyloxy-5,6-naphthonorbornadiene, 7-t- Butoxy-5,6-naphthonorbornadiene, 7- (α-ethoxy) ethoxy-5,6 Naphthonorbornadiene, 7- (α-pyranyl) oxy-5,6-naphthonorbornadiene, 7-acetoxy-5,6-anthranorbornadiene, 7- (p-chlorobenzoyloxy) -5,6-anthrannorbornadiene, 7-benzyl Oxy-5,6-anthranorbornadiene, 7-t-butoxy-5,6-anthranorbornadiene, 7- (α-ethoxy) ethoxy-5,6-anthranorbornadiene, 7- (α-pyranyl) oxy-5,6 On the benzene rings of the anthornorbornadiene and these compounds R ₁ (R ₁ is H, C1-C30 alkyl, C1-C30 halogenated alkyl, C6-C30 aryl, C4-C30 heteroaryl , C1-C30 alkoxy, C6-C30 aryloxy Represents one of trialkylsilyl or halogens C3 to C30.) Can be exemplified compounds bound.

The contents of the substituents R ₁ are substantially similar to the substituent R ₁ of dimethylol isopropylidene norbornene reaction synthesis route (A) (1) General formula for use in -A (4).

These compounds of the general formula (7) can be synthesized with reference to the following publicly known documents 14 to 16.
Known Document 14: J. Org. Org. Chem. , 33 , 324 (1968)
Known Document 15: Tetrahedron, 59, 6609-6614 (2003)
Known Document 16: Synthesis, 326 (1986)

Examples of the orthodihaloquinodimethanes of the general formula (8) used in the reaction (1) -B include 1,2- (α, α′-dichloro) quinodimethane, 1,2- (α, α′-dibromo. ) Quinodimethane, 2,3- (α, α'-dichloro) naphthoquinodimethane, 2,3- (α, α'-dibromo) naphthoquinodimethane, 2,3- (α, α'-dichloro) anthra Quinodimethane, 2,3- (α, α′-dibromo) anthraquinodimethane and the above substituents R ₂ (R ₂ is H, C 1 -C 30 alkyl, C 1 -C 30 on the benzene ring of these compounds. Or a C6 to C30 aryl, a C4 to C30 heteroaryl, a C1 to C30 alkoxy, a C6 to C30 aryloxy, a C3 to C30 trialkylsilyl, or a halogen). Mention may be made of the compound.

The contents of the substituents R ₂ is substantially similar to the substituent R ₂ of the benzyne such reactions (1) General formula for use in -A synthetic routes (A) (5).

These general formula (8) orthodihaloquinodimethanes react with 2,3-bis (α, α-dihalogenated methyl) acene compounds by reacting with a dehalogenating agent in the reaction system. Can be generated as The 2,3-bis (α, α-dihalogenated methyl) acene compound can be easily obtained as a commercially available reagent, or can be synthesized with reference to the following publicly known documents 17-19.
Known Document 17: Synthesis, 328 (1986)
Known Document 18: Synthesis, 416 (1973)
Known Document 19: Chem. Ber. , 89 , 708 (1956)

  The production of orthodihaloquinodimethanes of the general formula (8) from 2,3-bis (dihalogenated methyl) acene compounds can be carried out with reference to the above-mentioned known documents 17-19.

  In the reaction (1) -B, the amount of 2,3-bis (α, α-dihalogenated methyl) acene compound used as a raw material for the orthodihaloquinodimethanes of the general formula (8) is the general formula (7). It is preferable that it is 1-10 weight part with respect to 1 weight part of norbornadiene of this, More preferably, it is 1-4 weight part. The amount of the dehalogenating agent used is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight based on 1 part by weight of the 2,3-bis (α, α-dihalogenated methyl) acene compound. Part.

  The conditions for this reaction depend on the type of dehalogenating agent used. When alkali metal iodides are used as the dehalogenating agent, this reaction is carried out in a reaction vessel with norbornadiene of general formula (7), 2,3-bis (α, α-dihalogenated methyl) acene compound, The reaction can be carried out by charging a halogenating agent and a solvent and reacting at 5 to 150 ° C., preferably 10 to 100 ° C. for 1 to 60 hours, preferably 1 to 30 hours. The reaction reagent is preferably added all at once or sequentially, and a method of adjusting the concentration of the reaction reagent such as dropwise addition can also be applied. The reaction is usually carried out in a normal pressure open system, but it can also be carried out under normal pressure to pressure using a sealed container.

  Examples of the solvent include amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N′-dimethylpyrrolidinone, N, N, N ′, N′-tetramethylurea and the like. Solvents: Nitrile solvents such as acetonitrile and butyronitrile; Halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene, etc. Can be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 500 parts by weight, more preferably 5 to 250 parts by weight, based on 1 part by weight of the norbornadiene of the general formula (7).

  On the other hand, when an alkali metal other than an alkali metal iodide or an alkali organic metal is used as a dehalogenating agent for this reaction, this reaction is carried out in a reaction vessel in an inert gas atmosphere such as argon or nitrogen. ) Norbornadiene, 2,3-bis (α, α-dihalogenated methyl) acene compound and dehalogenating agent are charged, and the temperature is -90 to 120 ° C, preferably -70 to 80 ° C for 1 to 60 hours. The reaction can be preferably carried out by reacting for 1 to 30 hours. The reaction reagent is preferably added all at once or sequentially, and a method of adjusting the concentration of the reaction reagent such as dropwise addition can also be applied. The reaction is usually carried out in a normal pressure open system, but it can also be carried out under normal pressure to pressure using a sealed container.

  In this reaction, a solvent is used as necessary. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and diethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene. And halogenated aromatic hydrocarbon solvents such as diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 500 parts by weight, more preferably 5 to 250 parts by weight, based on 1 part by weight of the norbornadiene of the general formula (7).

  As a method for isolating the cyclized product of the general formula (9), which is a product of this reaction, extraction, crystallization, column chromatography or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product. Further, the isolation of the product is not necessarily required for this reaction step, and the product can be isolated after carrying out the next reaction (2) -B.

Reaction (2) -B
In reaction (2) -B, the cyclized product of general formula (9) obtained by reaction (1) -B is dehydrohalogenated to obtain an oxymethylene bridged acene compound of general formula (3). It is a reaction. This reaction can be carried out using a dehydrohalogenation reagent. As the dehydrohalogenation reagent, organic amines can be used. For example, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine; pyridine, 2-methylpicoline, 2,4,6- Aromatic amines such as trimethylpicoline can be used. In addition, when performing this reaction following said reaction (1) -B, since the dehalogenation reaction reagent used in reaction (1) -B acts also as a dehydrohalogenation reaction reagent of this reaction, By adjusting the addition amount of the dehalogenation reagent so that the dehalogenation reagent used in the reaction (1) -B remains in the reaction system after the reaction, the dehydrohalogenation agent is substantially reduced. It is also possible to perform the reaction (2) -B without newly adding a reaction reagent.

  The amount of the organic amine-based dehydrohalogenation reagent used is preferably 2 to 20 parts by weight, more preferably 2 to 10 parts by weight with respect to 1 part by weight of the cyclized product of the general formula (9). It is.

  In this reaction, a cyclization product of the general formula (9) and a solvent are charged in a reaction vessel, and −70 to 150 ° C., preferably −40 to 100 ° C., without newly adding or adding a dehydrohalogenation reagent. The reaction can be carried out by reacting for 1 to 60 hours, preferably 1 to 30 hours. The reaction reagent is preferably added all at once or sequentially, and a method of adjusting the concentration of the reaction reagent such as dropwise addition can also be applied. The reaction is usually carried out in a normal pressure open system, but can also be carried out under normal pressure to pressure using a sealed container.

  Examples of the solvent include amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N′-dimethylpyrrolidinone, N, N, N ′, N′-tetramethylurea and the like. Nitrile solvents such as acetonitrile and butyronitrile; halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, diethylbenzene; chlorobenzene, dichlorobenzene, trichlorobenzene, fluorobenzene, difluorobenzene, hexafluorobenzene, α, α, α-trifluorotoluene It diethyl ether, tetrahydrofuran, dioxane, diglyme, anisole, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the use of such ether solvents such as diethylene glycol methyl ethyl ether; halogenated aromatic hydrocarbon solvents. These solvents may be used alone or in combination of two or more. The amount of the solvent used is preferably 5 to 500 parts by weight, more preferably 5 to 250 parts by weight, based on 1 part by weight of the cyclized product of the general formula (9).

  This reaction is simpler to carry out in one pot with or without the addition of a new dehydrohalogenation reagent following the previous reaction (1) -B, and substantially the reaction conditions of reaction (1) -B It can carry out according to.

  As an isolation method of the oxymethylene bridged acene compound of the general formula (3), which is a product of this reaction, extraction, crystallization, column chromatography, or a combination of these can be used. In some cases, it is appropriate to perform these operations after concentration or solvent replacement. In addition, when it is necessary to obtain a higher-purity target product, purification operations such as extraction, crystallization, and column chromatography can be further performed on the isolated product. Further, the isolation of the product is not necessarily required for this reaction step, and the product can be isolated after the next reaction (3) is carried out.

Reaction (3)
This reaction is a reaction for decomposing the oxymethylene bridged acene compound of the general formula (3) to obtain a hydroxymethylene bridged acene compound of the general formula (2) in the production method using the synthesis route (A). This is the same as (3) and can be performed in the same manner.

Reaction (4)
This reaction is a reaction in which a hydroxymethylene bridged acene compound of the general formula (2) is oxidized to obtain a carbonyl bridged acene compound of the general formula (1) in the production method using the synthesis route (A) ( It is the same as 4) and can be performed similarly.

Production method of target acene compound of general formula (10) from carbonyl bridged acene compound of general formula (1) :
The acene compound of the general formula (10) which is the final object of the production method of the present invention is decomposed by heating the carbonyl bridged acene compound of the general formula (1) produced as described above to its decomposition temperature. By doing so, it can be easily manufactured. The decomposition temperature of the carbonyl bridged acene compound of the general formula (1) varies depending on the molecular structure of each compound, but is generally about 100 to 150 ° C. The heating time may be short, and it is generally sufficient to heat for 5 minutes. The carbonyl-bridged acene compound of the general formula (1) is usually white to slightly yellow, but when decomposed by heating and converted to the target acene compound of the general formula (10), orange (in the case of tetracene) Or blue-violet (in the case of pentacene), the end of the decomposition reaction can be confirmed using this color change as an index.

  When actually creating a conductive thin film on a substrate by applying this reaction, a solution is prepared by dissolving the carbonyl bridged acene compound of general formula (1) in a suitable solvent such as monochlorobenzene or xylene. The solution is applied to a substrate (generally ceramics such as glass, sapphire, zirconia, inorganic materials such as silicon and aluminum, or organic materials such as plastic) on which a conductive thin film is to be formed. What is necessary is just to heat about 5 minutes at the temperature of degreeC. By heating, the carbonyl bridged acene compound of the general formula (1) in the solution is decomposed into a bridged portion and converted to an acene compound of the general formula (10). Then, the acene compound is self-assembled on the substrate. A conductive thin film is formed.

  As described above, according to the method of the present invention, a conductive thin film can be formed on a substrate by heating at a temperature of 100 to 150 ° C. for about 5 minutes. In the method of the present invention, an environmentally friendly solvent such as monochlorobenzene having a small number of halogens or xylene containing no halogen can be used as the solvent. Therefore, according to the method of the present invention, a highly regular conductive thin film can be efficiently produced by a simple and environmentally friendly method.

The contents of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
Raw material compounds (4-a), (4-b), (5-a), (5-b), intermediate compounds (2-i), (2-ii), (2-iii) related to this Example ) And target compounds (1-i), (1-ii), and (1-iii) are shown below.

Example 1 : Synthesis of intermediate compound (2-i) by reaction (1) -A, reaction (2) -A, and reaction (3) Under an Ar atmosphere, 1.00 g of raw material compound (4-a) and 1, 2 -N-BuLi (15% hexane solution: 7.4 ml) was added dropwise to 10 ml of a toluene solution of 1.10 g of dibromobenzene under cooling at -60 ° C, and reacted for 4 hours. After confirming the disappearance of the raw materials, the reaction solution was concentrated, and the required product was separated from the obtained crude product by silica gel chromatography (developing solvent system: ethyl acetate / hexane). The separated acquired product is a cyclized product, and includes a product in which a part of the α-ethoxyethyl group derived from the raw material compound is eliminated.
The cyclized product obtained by the above operation was dissolved in 10 ml of MeOH, a catalytic amount of p-toluenesulfonic acid was added, and then reacted at room temperature for 1 hr. Water was added after reaction and chloroform extraction was performed. The yellow oil obtained by concentrating the extract was purified by silica gel chromatography (developing solvent system: ethyl acetate / hexane) to obtain 380 mg (38% yield) of slightly yellow powdery crystals. ¹ H-NMR of the obtained crystal was measured and confirmed to be compound (2-i). The NMR data is shown below.
[< ¹ > H-NMR] (DMSO-d: [delta]) 4.29 (d, 2H), 4.33 (ddd, H), 5.70 (d, H), 6.99-7.01 (m, 2H), 7.31-7.38 (m, 4H), 7.72-7.75 (m, 4H)

Example 2 : Synthesis of intermediate compound (2-i) by reaction (1) -B, reaction (2) -B, and reaction (3) Raw material compound (5-a) 1.0 g (4.67 mmol), α, α, α ′, α′-Tetrabromo-o-xylene (4.92 g, 11.7 mmol), NaI (4.2 g, 28.0 mmol) and DMF (50 ml) were charged into a flask and reacted at 65 ° C. for 20 hours in a nitrogen atmosphere. Water was added after reaction and toluene extraction was performed. The extract was then washed with sodium thiosulfate and concentrated under reduced pressure. The obtained yellow oil was dissolved in 40 ml of MeOH, and a catalytic amount of 50% sulfuric acid was added, followed by a reaction at 60 ° C. for 1 hr at room temperature. Water was added after reaction and chloroform extraction was performed. The yellow oil obtained by concentrating the extract was purified by silica gel chromatography (developing solvent system: ethyl acetate / hexane) to obtain 570 mg (47% yield) of slightly yellow powdery crystals. ¹ H-NMR was measured for the obtained crystals, and the same NMR data as in Example 1 was obtained. Thus, it was confirmed to be the compound (2-i).

Example 3 Synthesis of Compound (1-i) by Reaction (4) Under Ar atmosphere, N-tert- was added to 20 ml of THF solution of 374 mg of the intermediate compound (2-i) obtained in Example 1 or 2 and 293 mg of triethylamine. 5 ml of a dichloromethane solution of 470 mg of butylbenzenesulfinimidoyl chloride was added dropwise at -60 ° C. or lower and reacted for 3 hours. After the reaction, water was added and extraction operation was performed with ethyl acetate. The extract was concentrated under reduced pressure and cooled to precipitate a slightly yellow powdery crystal. The precipitate was filtered and dried to isolate 130 mg (yield 36%) of powdery crystals. This ¹ H-NMR was measured and confirmed to be compound (1-i). The analysis data is shown below.
Decomposition temperature: 112-115 ° C (changes orange when decomposed)
FT-IR (KBr: cm ⁻¹ ) 1784 (C═O)
[< ¹ > H-NMR] (CDCl3: [delta]) 4.88 (s, 2H), 7.18-7.20 (m, 2H), 7.44-7.51 (m, 4H), 7.78- 7.82 (m, 2H), 7.90 (s, 2H)
[EI-Mass] (m / z (%)) = 228 (100, M ⁺ -CO)

Example 4 Production of Tetracene (1) When 10 mg of the compound (1-i) powder obtained in Example 3 was placed in a flask and heated in an Ar atmosphere, it changed to 9 mg of an orange powder at 112 to 115 ° C. This product was hardly soluble in THF, and was confirmed to be tetracene from TOFF-Mass spectrum: M ⁺ 228.
(2) Under an Ar atmosphere, 10 mg of the compound (1-i) obtained in Example 3 was dissolved in 1 ml of THF and applied on a glass substrate. When the coating film was dried and heated to 115 ° C., it turned orange. The TOFF-Mass spectrum of this thin film was the same as the above spectrum. As a result of thermal analysis, the weight change due to the conversion of compound (1-i) to tetracene was 90% or more after 5 minutes.

Example 5 : Synthesis of intermediate compound (2-ii) by reaction (1) -A, reaction (2) -A and reaction (3) In an Ar atmosphere, 7.5 g and 2,3 of raw material compound (4-a) -PhLi (19% butyl ether solution: 39.6 g) was added dropwise to 300 ml of a toluene solution of 8.37 g of dibromonaphthalene under cooling at -60 ° C, and reacted for 22 hours. After the reaction, the reaction solution was concentrated, and the resulting residue was subjected to silica gel chromatography (developing solvent system: ethyl acetate / hexane) to obtain 2.57 g (yield 23%) of a slightly yellow solid. This ¹ H-NMR was measured and confirmed to be a precursor of compound (2-ii). The NMR data is shown below.
[< ¹ > H-NMR] (CDCl3: [delta]) 1.17 (t, 3H), 1.26 (d, 3H), 3.33 (dq, H), 3.52 (dq, H), 4.46 (T, H), 4.47 (d, 2H), 4.82 (q, H), 7.06 to 7.09 (m, 2H), 7.33 to 7.42 (m, 4H), 7.83 (d, 2H), 7.92-7.95 (m, 2H), 8.24 (s, 2H)
2.06 g of the precursor of the obtained compound (2-ii) was suspended in methanol (300 ml), 1.03 g of p-toluenesulfonic acid monohydrate was added, and the mixture was reacted at room temperature for 1 hr. Water was added after reaction and extraction operation was performed with chloroform. The extract was washed with 10% aqueous sodium bicarbonate and concentrated to give a slightly yellow residue. When this residue was treated with an ethyl acetate / n-hexane mixture, 1.46 g (88% yield) of a slightly orange powder was obtained. This ¹ H-NMR was measured and confirmed to be compound (2-ii). The NMR data is shown below.
[< ¹ > H-NMR] (DMSO-d: [delta]) 4.33 (s, 3H), 5.78 (d, H), 7.01 to 7.04 (m, 2H), 7.33 to 7. 36 (m, 2H), 7.42-7.45 (m, 2H), 7.86 (s, 2H), 7.98-8.01 (m, 2H), 8.35 (s, 2H)

Example 6 : Synthesis of intermediate compound (2-ii) by reaction (1) -B, reaction (2) -B and reaction (3) 1.0 g of raw material compound (5-a), 2,3-bis (dibromo) Methyl) naphthalene (5.52 g), NaI (4.2 g) and DMF (60 ml) were charged into a flask and reacted at 65 ° C. for 20 hours in a nitrogen atmosphere. Water was added after reaction and toluene extraction was performed. The extract was then washed with sodium thiosulfate and concentrated under reduced pressure. The concentrate was subjected to silica gel chromatography (developing solvent system: ethyl acetate / hexane) to obtain a yellow solid. This was further dissolved in 40 ml of THF, a catalytic amount of 50% sulfuric acid was added, and then reacted at 50 ° C. for 1 hr. After the reaction, water was added, followed by extraction with chloroform, and the yellow solid obtained by concentrating the extract was suspended in MeOH to obtain 560 mg (yield 39%) of white powdery crystals. ¹ H-NMR of this crystal was measured, and the same NMR data as in Example 5 was obtained, so that it was confirmed to be the compound (2-ii).

Example 7 : Synthesis of Compound (1-ii) by Reaction (4) 1.0 g (3.24 mmol) of Intermediate Compound (2-ii) obtained in Example 5 or 6 and 2.46 g of triethylamine under Ar atmosphere 15 ml of a dichloromethane solution of 3.5 g of N-tert-butylbenzenesulfinimidoyl chloride was added dropwise to 80 ml of a tetrahydrofuran solution at −10 ° C. and reacted for 2.5 hours. The reaction precipitate was then filtered and washed with hydrous methanol to obtain a white powder. This powder was further purified by suspension with hydrous tetrahydrofuran to obtain 880 mg (yield 89%) of white powder. This ¹ H-NMR was measured and confirmed to be compound (1-ii). The analysis data is shown below.
Decomposition temperature: 120-123 ° C (changes to blue-violet by decomposition)
FT-IR (KBr: cm ⁻¹ ) 1782 (C═O)
[ ¹ H-NMR] (THF-d: δ) 4.92 (s, 2H), 7.19 to 7.22 (m, 2H), 7.41 to 7.44 (m, 2H), 7. 53 to 7.56 (m, 2H), 7.97 to 8.01 (m, 2H), 8.07 (s, 2H), 8.42 (s, 2H)
[EI-Mass] (m / z (%)) = 278 (100, M ⁺ -CO)

Example 8 : Production of pentacene (I)
When 10 mg of the powder of the compound (1-ii) obtained in Example 7 was put in a flask and heated in an Ar atmosphere, it changed to 9 mg of a blue-violet powder at 120 to 123 ° C. This product was hardly soluble in THF and was confirmed to be pentacene from TOFF-Mass spectrum: M + 278. As a result of thermal analysis, the weight change due to conversion of compound (1-ii) to pentacene was 90% or more after 5 minutes.

Example 9 Synthesis of Intermediate Compound (2-iii) by Reaction (1) -A, Reaction (2) -A and Reaction (3) Under N ₂ atmosphere, 610 mg of raw material compound (4-b) and 1,2- N-BuLi (15% hexane solution: 4 ml) was added dropwise to 20 ml of a toluene solution containing 1.04 g of dibromobenzene under cooling at −60 ° C., reacted at −60 ° C. or lower for 2 hours, and then warmed to room temperature. After the reaction, toluene extraction was performed, and then the residue obtained by concentrating the extract was purified by silica gel column chromatography to obtain 660 mg (yield 87%) of slightly yellow crystals.
Next, 660 mg of the above-mentioned slightly yellow crystals, 930 mg of 1,2,4,5-tetrachloro-p-quinone, and 30 ml of toluene were placed in the flask, and the reaction was carried out with heating under reflux for 1 hour. After the reaction, the reaction mixture was cooled to room temperature, saturated sodium bicarbonate water was added, and the precipitated salt was removed by filtration, followed by extraction with toluene. Subsequently, the toluene extract was concentrated under reduced pressure to obtain brown crystals. This product was dissolved in 30 ml of methanol, a catalytic amount of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 1 hour. Next, the reaction solution was neutralized with potassium carbonate and concentrated under reduced pressure. This concentrate was extracted with ethyl acetate, and the extract was concentrated under reduced pressure. The obtained residue was heated and dissolved in methanol, and cooled to obtain 260 mg of a fine brown powder (total yield 42%). The following analysis was performed on the obtained crystal to confirm that it was the compound (2-iii). The analysis data is shown below.
Melting point: 268-270 ° C
[< ¹ > H-NMR] (CDCl3: [delta]) 3.02 (s, 3H), 3.24 (s, 3H), 3.74 (s, 4H), 4.02 to 4.06 (m, 2H) 6.66 to 6.70 (m, 2H), 7.35 to 7.40 (m, 2H), 7.66 to 7.72 (m, 2H)
[EI-Mass] (m / z (%)) = 308 (6, M ⁺ ), 291 (5, M ⁺ —OH), 279 (100, M ⁺ —CHO)

Example 10 : Synthesis of intermediate compound (2-iii) by reaction (1) -B, reaction (2) -B, and reaction (3) 1.0 g of raw material compound (5-b), α, α, α ′, α'-Tetrabromo-o-xylene (4.00 g), NaI (3.41 g) and DMF (60 ml) were charged into a flask and reacted at 65 ° C. for 20 hours in a nitrogen atmosphere. Water was added after reaction and toluene extraction was performed. The extract was then washed with sodium thiosulfate and concentrated under reduced pressure. The concentrate was subjected to silica gel chromatography (developing solvent system: ethyl acetate / hexane) to obtain a yellow solid. This was further dissolved in 40 ml of THF, a catalytic amount of 50% sulfuric acid was added, and then reacted at 50 ° C. for 1 hr. After the reaction, water was added, followed by extraction with chloroform, and the yellow solid obtained by concentrating the extract was suspended in MeOH to obtain 640 mg (yield 55%) of white powdery crystals. ¹ H-NMR of this crystal was measured, and the same NMR data as in Example 9 was obtained. Thus, it was confirmed to be the compound (2-iii).

Example 11 : Synthesis of compound (1-iii) by reaction (4) In a nitrogen atmosphere, 45 mg of oxalyl chloride and 2 ml of methylene chloride were placed in a flask, cooled to -50 ° C or lower, and 61 mg of DMSO was added, and then Example 2 ml of a methylene chloride solution of 50 mg of the intermediate compound (2-iii) obtained in 9 or 10 and 820 mg of triethylamine were added, and the temperature was gradually raised from −50 ° C. to room temperature. After the reaction, the precipitate was filtered and washed to obtain 28 mg (yield 56%) of white powder crystals. The following analysis was performed on the obtained crystal to confirm that it was the compound (1-iii). The analysis data is shown below.
Decomposition temperature: 145-147 ° C (changes to blue-violet)
FT-IR (KBr: cm ⁻¹ ) 1774 (C═O)
[ ¹ H-NMR] (THF-d: δ) 5.02 (s, 2H), 7.40-7.47 (m, 4H), 7.78-7.85 (m, 2H), 7. 94-8.00 (m, 4H)
[EI-Mass] (m / z (%)) = 278 (100, M ⁺ -CO)

Example 12 : Production of pentacene (II)
When 10 mg of the powder of the compound (1-iii) obtained in Example 11 was put in a flask and heated in an Ar atmosphere, it changed to 9 mg of blue-violet crystals at 145 to 147 ° C. This crystal was confirmed to be pentacene by the following mass analysis. As a result of thermal analysis, the weight change due to the conversion of compound (1-iii) to pentacene was 90% or more after 5 minutes.
[Toff-Mass] (m / z (%)) = 278 (100, M ⁺ )

Solubility test Compound (1-i) synthesized in Examples 3, 7 and 11 to confirm that the carbonyl bridged acene compound of general formula (1) of the present invention has higher solubility than the target acene compound. , (1-ii) and (1-iii) were measured at 30 ° C. The results are shown in the table below.

  As is apparent from the table, the carbonyl bridged acene compound of the present invention has higher solubility than the target acene compound. Therefore, when the carbonyl-bridged acene compound of the present invention is used as a raw material, it is not necessary to make fine particles or heat it many times as in the conventional method using the target acene compound as a raw material. Can be formed. Specifically, for example, the carbonyl bridged acene compound of the present invention can be dissolved in a solvent at room temperature or low temperature and applied onto a substrate, and the acene compound can be liberated in a short time by a simple heat treatment. Therefore, a conductive thin film having a high-quality alignment structure can be efficiently formed by a simple method.

  In addition, as shown in Examples 4, 8 and 12, the carbonyl bridged acene compound of the present invention can be easily converted into the target acene compound simply by heating at a temperature of 150 ° C. or lower for a single time. Therefore, when the carbonyl bridged acene compound of the present invention is used, it is possible to easily form a conductive thin film with facilities that are simpler and less expensive than conventional methods that require light irradiation, high-temperature heating, or long-time heating at low temperatures. it can.

  The carbonyl bridged acene compound of the present invention has a low decomposition temperature as shown in Examples 3, 7 and 11, and is close to the boiling point of monochlorobenzene (132 ° C.) and the boiling point of xylene (about 140 ° C.). These can be used as solvents. These solvents have a low halogen number (monochlorobenzene) or do not contain halogen (xylene), and are environmentally friendly solvents. Therefore, according to the present invention, the conductive thin film can be formed while minimizing the load applied to the environment.

In the above-mentioned examples, only one example is synthesized among many compounds included in the scope of the present invention. However, it will be understood by those skilled in the art that other compounds can be synthesized in the same manner with reference to the above-mentioned examples. Is clear. For example, the intermediate compounds (2-iv) to (2-ix) and the target compounds (1-iv) to (1-ix) as shown below have bromo substitution on the intermediate compounds and target compounds synthesized in the examples. Introduced, intermediate compound synthesized in the example or the target compound with an increased number of benzene rings, or intermediate compound synthesized in the example or the target compound with an increased number of benzene rings and introduction of bromo substitution Therefore, these compounds can be easily synthesized by appropriately changing the raw material compounds used in the examples.

  The carbonyl-bridged acene-based compound of the present invention is very useful in a wide range of fields such as organic semiconductor devices and organic transistors because it can efficiently produce a highly regular conductive thin film by a simple method.

Claims (6)

General formula (1)

(In the formula, Z represents —C (═O) —. M and n each represents an integer of 0 or more. R ₁ and R ₂ each independently represent H, C1 to C30 alkyl, or C1 to C30. Alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen. Carbonyl-bridged acene compound. General formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen.). General formula (4)

(In the formula, m represents an integer of 0 or more. R ₁ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy. , C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen R ₃ is C2-C30 acyl, C2-C30 α-alkoxyalkyl, tetrahydropyranyl, C4-C30 t -Represents an alkyl, a C3-C30 trialkylsilyl or a C8-C30 allyldialkylsilyl) and a general formula (5)

(In the formula, n represents an integer of 0 or more. R ₂ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy) , C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen).
General formula (6)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl), or an alkali metal salt thereof, By dehydrogenating this cyclized product or its alkali metal salt,
General formula (3)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl). By decomposing oxymethylene bridged acene compounds,
General formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen)) is obtained. The method for producing a hydroxymethylene bridged acene compound according to claim 2. General formula (7)

(In the formula, m represents an integer of 0 or more. R ₁ is H, C1-C30 alkyl, C1-C30 alkyl halide, C6-C30 aryl, C4-C30 heteroaryl, C1-C30 alkoxy. , C6-C30 aryloxy, C3-C30 trialkylsilyl or halogen R ₃ is C2-C30 acyl, C2-C30 α-alkoxyalkyl, tetrahydropyranyl, C4-C30 t -Represents an alkyl, a C3-C30 trialkylsilyl or a C8-C30 allyldialkylsilyl.) And a norbornadiene represented by the general formula (8)

(In the formula, n represents an integer of 0 or more. X represents a halogen. R ₂ represents H, a C1-C30 alkyl, a C1-C30 halogenated alkyl, a C6-C30 aryl, or a C4-C30 heteroaryl. , C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen) is reacted with an orthodihaloquinodimethane represented by the general formula (9 )

(In the formula, m and n represent an integer of 0 or more. X represents a halogen. R ₁ and R ₂ each independently represents H, a C1-C30 alkyl, a C1-C30 halogenated alkyl, a C6- C3 aryl, C4 to C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen, R ₃ represents C2 to C30 acyl, C2 C30 α-alkoxyalkyl, tetrahydropyranyl, C4 to C30 t-alkyl, C3 to C30 trialkylsilyl, or C8 to C30 allyldialkylsilyl). By dehydrohalogenating this cyclized product,
General formula (3)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, alkoxy of C1-C30, aryloxy C6 to C30, acyl .R ₃ is C2 to C30, which represent one of trialkylsilyl or halogens C3 to C30, C2 to C30 of α- alkoxyalkyl , Tetrahydropyranyl, C4-C30 t-alkyl, C3-C30 trialkylsilyl, or C8-C30 allyldialkylsilyl). By decomposing oxymethylene bridged acene compounds,
General formula (2)

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) C30 heteroaryl, C1 to C30 alkoxy, C6 to C30 aryloxy, C3 to C30 trialkylsilyl, or halogen)) is obtained. The method for producing a hydroxymethylene bridged acene compound according to claim 2.   The method for producing a carbonyl bridged acene compound according to claim 1, wherein the hydroxymethylene bridged acene compound according to claim 2 is oxidized. The carbonyl bridged acene compound according to claim 1 is decomposed by heating to its decomposition temperature.

(In the formula, m and n each represents an integer of 0 or more. R ₁ and R ₂ are each independently H, C1 to C30 alkyl, C1 to C30 alkyl halide, C6 to C30 aryl, C4 to C4) A C30 heteroaryl, a C1-C30 alkoxy, a C6-C30 aryloxy, a C3-C30 trialkylsilyl, or a halogen.