JP2006248923A - Method for producing acenes - Google Patents

Abstract

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ａ¹及びＡ²は、それぞれ、同一又は異なって、炭化水素基等を表す。Ｐ¹及びＰ²は脱離基を示す。Ｒ⁷及びＲ⁸は、それぞれ、同一または異なって、ハロゲン原子等を示す。ｍは０以上の整数であり、ｎは１以上の整数である。］
【選択図】なし
【Task】
Providing a method for selectively removing substituents once introduced into an acene derivative, actively and efficiently without increasing the number of synthesis steps.
[Solution]
By reacting a ring compound represented by the following formula (3) with a reducing agent and then reacting with an electrophile or a nucleophile, the leaving groups P ¹ and P ² in the ring compound are eliminated. By doing so, the above-mentioned problems are solved.
[Chemical 1]

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , A ¹ and A ² are the same or different and each represents a hydrocarbon group or the like. P ¹ and P ² represent a leaving group. R ⁷ and R ⁸ are the same or different and each represents a halogen atom or the like. m is an integer of 0 or more, and n is an integer of 1 or more. ]
[Selection figure] None

Description

  The present invention relates to a method for producing acenes.

  Acenes such as anthracene, naphthacene, and pentacene are conjugated polymers, are known as substances having high carrier mobility, and are expected to be used as useful electronic materials. By making such a material easily soluble in an organic solvent, synthesis and processing are facilitated, and it becomes easy to produce a thin film, so that its usefulness is dramatically increased.

  Since acenes have solubility in organic solvents depending on the introduced substituents and their positions, in order to make acenes a more useful electronic material, they can be placed at any position on acenes and their precursors. It was necessary to develop a technique for introducing an arbitrary substituent.

So far, various acenes can be synthesized by the homologation method of diyne. However, if the substituent once introduced can be selectively removed, the synthesis method has high utility value. It is already known that the trimethylsilyl group is eliminated during the cyclization reaction depending on the conditions. Therefore, it is known that various substituted acenes can be synthesized by the homologation method. However, the yield of the silyl group elimination reaction by this method is still low, and therefore, a technique that is positively efficient and does not increase the number of synthesis steps has been demanded.
JP 2000-26339 A

  Therefore, there has been a demand for a method for selectively removing a substituent once introduced into an acene derivative, actively and efficiently without increasing the number of synthesis steps.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ、互いに独立し、同一または異なって、水素原子；ハロゲン原子；ヒドロキシ基；置換基を有していてもよいＣ₁〜Ｃ₂₀炭化水素基；置換基を有していてもよいＣ₁〜Ｃ₂₀アルコキシ基；置換基を有していてもよいＣ₆〜Ｃ₂₀アリールオキシ基；置換基を有していてもよいアミノ基；又は置換基を有していてもよいシリル基であり、Ａ¹及びＡ²は、それぞれ、互いに独立し、同一または異なって、水素原子；ハロゲン原子；置換基を有していてもよいＣ₁〜Ｃ₂₀炭化水素基；置換基を有していてもよいＣ₁〜Ｃ₂₀アルコキシ基；置換基を有していてもよいＣ₆〜Ｃ₂₀アリールオキシ基；置換基を有していてもよいＣ₇〜Ｃ₂₀アルキルアリールオキシ基；置換基を有していてもよいＣ₁〜Ｃ₂₀アルコキシカルボニル基；置換基を有していてもよいＣ₆〜Ｃ₂₀アリールオキシカルボニル基；ヒドロキシカルボニル基；イミド基；シアノ基（−ＣＮ）；カルバモイル基（−Ｃ（＝Ｏ）ＮＨ₂）；ハロホルミル基（−Ｃ（＝Ｏ）−Ｘ、式中、Ｘはハロゲン原子を示す。）；ホルミル基（−Ｃ（＝Ｏ）−Ｈ）；イソシアノ基；イソシアナト基；チオシアナト基；若しくはチオイソシアナト基であり、又はこれらの置換基を１つ以上組み合わせた基であり、但し、Ａ¹及びＡ²は、互いに架橋して、式−Ｃ（＝Ｏ）−Ｂ−Ｃ（＝Ｏ）−で示される環を形成してもよく（式中、Ｂは、酸素原子又は式−Ｎ（Ｂ¹）−で示される基（式中、Ｂ¹は、水素原子、Ｃ₁〜Ｃ₂₀炭化水素基、又は、ハロゲン原子である）である）。Ｐ¹及びＰ²は、それぞれ、互いに独立し、同一または異なって、−ＭＸ¹Ｘ²Ｘ³（式中、Ｍは周期表第１４族の金属、ケイ素、スズ、又はゲルマニウムであり、Ｘ¹、Ｘ²及びＸ³は、それぞれ、互いに独立し、同一または異なって、水素原子；又は置換基を有していてもよいＣ₁〜Ｃ₂₀炭化水素基である。）、又は、−ＳＯ₂Ｘ⁴（式中、Ｘ⁴は、水素原子；又は置換基を有していてもよいＣ₁〜Ｃ₂₀炭化水素基である。）で表される脱離基であり、ｍは０以上の整数であり、ｎは１以上の整数である。下記式に示される結合は、単結合又は二重結合を示す。

］還元剤とを反応させ、次いで、求電子剤または求核剤と反応させることにより、前記環化合物中の脱離基Ｐ¹及びＰ²を脱離する工程を含むことを特徴とする、下記式（２）で示される炭化水素縮合環の製造方法が提供される。

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｍ及びｎは、上記の意味を有する。下記式に示される結合は、単結合又は二重結合を示す。

Ｒ⁷及びＲ⁸は、それぞれ、互いに独立し、同一または異なって、ハロゲン原子；Ｃ₁〜Ｃ₂₀炭化水素基；Ｃ₁〜Ｃ₂₀アルコキシ基；又はアミノ基である。］ That is, in one aspect of the present invention, a ring compound represented by the following formula (3):

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently the same or different and have a hydrogen atom; a halogen atom; a hydroxy group; a substituent. C ₁ -C ₂₀ hydrocarbon group which may have a substituent; C ₁ -C ₂₀ alkoxy group which may have a substituent; C ₆ -C ₂₀ aryloxy group which may have a substituent; An optionally substituted amino group; or a silyl group optionally having a substituent, wherein A ¹ and A ² are each independently the same or different and are each independently a hydrogen atom; a halogen atom; C ₁ -C ₂₀ hydrocarbon group which may have; C ₁ -C ₂₀ alkoxy group which may have a substituent; C ₆ -C ₂₀ aryloxy group which may have a substituent; which may have a substituent C ₇ -C ₂₀ alkylaryl group; which may have a substituent ₁ -C ₂₀ alkoxycarbonyl group; optionally substituted C ₆ -C ₂₀ aryloxycarbonyl group; hydroxy group; imido group; a cyano group (-CN); carbamoyl group (-C (= O) NH ₂ ); haloformyl group (—C (═O) —X, wherein X represents a halogen atom); formyl group (—C (═O) —H); isocyano group; isocyanato group; thiocyanato group; Or a thioisocyanato group, or a group in which one or more of these substituents are combined, provided that A ¹ and A ² are bridged with each other to form the formula —C (═O) —B—C (═O) (Wherein B is an oxygen atom or a group represented by the formula —N (B ¹ ) — (wherein B ¹ is a hydrogen atom, C ₁ -C ₂₀ carbonization). A hydrogen group or a halogen atom). P ¹ and P ² are each independently the same or different and represent -MX ¹ X ² X ³ (wherein M is a metal of Group 14 of the periodic table, silicon, tin, or germanium; X ¹ , X ² and X ³ are each independently the same or different and are a hydrogen atom; or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent.) Or —SO ₂ X ⁴ (wherein X ⁴ is a hydrogen atom; or an optionally substituted C _{1 to} C ₂₀ hydrocarbon group), and m is 0 or more. It is an integer, and n is an integer of 1 or more. The bond represented by the following formula represents a single bond or a double bond.

A step of removing leaving groups P ¹ and P ² in the ring compound by reacting with a reducing agent and then reacting with an electrophile or a nucleophile, A method for producing a hydrocarbon condensed ring represented by the formula (2) is provided.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n have the above-mentioned meanings. The bond represented by the following formula represents a single bond or a double bond.

R ⁷ and R ⁸ are each independently the same or different and are each a halogen atom; a C ₁ -C ₂₀ hydrocarbon group; a C ₁ -C ₂₀ alkoxy group; or an amino group. ]

In one aspect of the present invention, P ¹ and P ² are each independently the same or different, and are a trimethylsilyl group, trimethylgermanium group, trimethyltin group, tributyltin group, triphenylsilyl group, triisopropylsilyl group, triethyl A silyl group, a dimethylsilyl group, or a dimethylphenylsilyl group is preferred.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、ｍ及びｎは、上記の意味を有する。下記式に示される結合は、単結合又は二重結合を示す。

］ In another aspect of the present invention, the method includes the step of aromatizing the hydrocarbon condensed ring obtained in one aspect of the present invention in the presence of a dehydrogenating reagent. A method for producing acenes represented by the formula:

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , m and n have the above-mentioned meanings] The bond represented by the following formula represents a single bond or a double bond.

]

  By the method of the present invention, a substituent once introduced into an acene derivative can be selectively removed actively and efficiently without increasing the number of synthesis steps.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ａ¹、Ａ²、Ｐ¹、Ｐ²、Ｒ⁷、Ｒ⁸、ｍ及びｎは、上記の意味を有する。］ In the present invention, a ring compound represented by the following formula (3) is reacted with a reducing agent, and then reacted with an electrophile or a nucleophile, whereby leaving groups P ¹ and P in the ring compound are reacted. characterized in that it comprises a step of desorbing ^2, a method for producing a fused-ring hydrocarbon (an aspect of the present invention) represented by the following formula (2), obtained following formula in one aspect of the present invention A process for producing an acene represented by the following formula (1), comprising the step of aromatizing the hydrocarbon condensed ring represented by (2) in the presence of a dehydrogenating reagent (other than the present invention) Side).

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , A ¹ , A ² , P ¹ , P ² , R ⁷ , R ⁸ , m and n have the above meanings] . ]

In one aspect of the present invention, a ring compound represented by the following formula (3) is used.

In the above formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently the same or different and have a hydrogen atom; halogen atom; hydroxy group; Optionally substituted C ₁ -C ₂₀ hydrocarbon group; optionally substituted C ₁ -C ₂₀ alkoxy group; optionally substituted C ₆ -C ₂₀ aryloxy group; substituted An amino group which may have a group; or a silyl group which may have a substituent.

In the present specification, the hydrocarbon group of the “C ₁ -C ₂₀ hydrocarbon group” may be a saturated or unsaturated acyclic group, or a saturated or unsaturated cyclic group. When the C ₁ -C ₂₀ hydrocarbon group is acyclic, it may be linear or branched. The “C ₁ -C ₂₀ hydrocarbon group” includes a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₄ -C ₂₀ alkyl dienyl group, a C _6- C ₁₈ aryl group, C ₇ -C ₂₀ alkylaryl group, C ₇ -C ₂₀ arylalkyl group, C ₄ -C ₂₀ cycloalkyl group, C ₄ -C ₂₀ cycloalkenyl group, (C ₃ ~C ₁₀ cycloalkyl) C ₁ -C ₁₀ alkyl groups and the like are included.

In the present specification, "C ₁ -C ₂₀ alkyl group" is preferably C ₁ -C ₁₀ alkyl group, more preferably a C ₁ -C ₆ alkyl group. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, dodecanyl and the like.

In the present specification, "C ₂ -C ₂₀ alkenyl group" is preferably C ₂ -C ₁₀ alkenyl group, more preferably a C ₂ -C ₆ alkenyl group. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methylallyl, 2-butenyl and the like.

In the present specification, "C ₂ -C ₂₀ alkynyl group" is preferably C ₂ -C ₁₀ alkynyl group, more preferably a C ₂ -C ₆ alkynyl group. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, and the like.

In the present specification, "C ₄ -C ₂₀ alkyldienyl group" is preferably C ₄ -C ₁₀ alkadienyl group, more preferably a C ₄ -C ₆ alkadienyl group. Examples of alkyldienyl groups include, but are not limited to, 1,3-butadienyl and the like.

In the present specification, the “C ₆ -C ₁₈ aryl group” is preferably a C ₆ -C ₁₂ aryl group. Examples of the aryl group include, but are not limited to, phenyl, 1-naphthyl, 2-naphthyl, indenyl, biphenylyl, anthryl, phenanthryl and the like.

In the present specification, the “C ₇ -C ₂₀ alkylaryl group” is preferably a C ₇ -C ₁₂ alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, o-cumenyl, m -Cumenyl, p-cumenyl, mesityl and the like can be mentioned.

In the present specification, the “C ₇ -C ₂₀ arylalkyl group” is preferably a C ₇ -C ₁₂ arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenyl Examples include phenylbutyl and 5-phenylpentyl.

In the present specification, the “C ₄ -C ₂₀ cycloalkyl group” is preferably a C ₄ -C ₁₀ cycloalkyl group. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

In the present specification, the “C ₄ -C ₂₀ cycloalkenyl group” is preferably a C ₄ -C ₁₀ cycloalkenyl group. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and the like.

In the present specification, the “C ₁ -C ₂₀ alkoxy group” is preferably a C ₁ -C ₁₀ alkoxy group, and more preferably a C ₁ -C ₆ alkoxy group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy and the like.

In the present specification, the “C ₆ -C ₂₀ aryloxy group” is preferably a C ₆ -C ₁₂ aryloxy group. Examples of aryloxy groups include, but are not limited to, phenyloxy, naphthyloxy, biphenyloxy, and the like.

In one aspect of the present invention, “C ₁ -C ₂₀ hydrocarbon group”, “C ₁ -C ₂₀ alkoxy group”, “C” represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ _A substituent may be introduced into the “ _6- C ₂₀ aryloxy group”, “amino group”, and “silyl group”. Examples of the substituent include a C _{1 to} C ₁₀ hydrocarbon group (for example, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C _{1 to} C ₁₀ alkoxy group (for example, , Methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ -C ₁₂ aryloxy groups (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), amino groups, hydroxyl groups, halogen atoms (eg, fluorine, chlorine, bromine, iodine) ) Or a silyl group. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

  In the present specification, examples of “optionally substituted amino group” include, but are not limited to, amino, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  In this specification, examples of “optionally substituted silyl group” include, but are not limited to, dimethylsilyl, diethylsilyl, trimethylsilyl, triethylsilyl, trimethoxysilyl, triethoxysilyl, diphenyl Examples include methylsilyl, triphenylsilyl, triphenoxysilyl, dimethylmethoxysilyl, dimethylphenoxysilyl, and methylmethoxyphenyl.

In one aspect of the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are each independently the same or different and represent a hydrogen atom; a C ₁ -C ₂₀ alkyl group; C ₆ -C ₁₈ aryl group; C ₁ -C ₂₀ alkoxy group; preferably a halogen atom, a hydrogen atom; have a substituent a silyl group C ₁ -C ₁₀ alkyl radical; C ₆ -C ₁₂ aryl group; C ₁ -C ₁₀ alkoxy group; silyl group which may have a substituent; or a halogen atom is more preferable, and a hydrogen atom or a fluorine atom is more preferable.

In the above formula (3), A ¹ and A ² are each independently the same or different and are each a hydrogen atom; a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; good C ₁ -C ₂₀ alkoxy group which may have a group, which may have a substituent group C ₆ -C ₂₀ aryloxy group; which may have a substituent C ₇ -C ₂₀ alkylaryl An oxy group; an optionally substituted C ₁ -C ₂₀ alkoxycarbonyl group; an optionally substituted C ₆ -C ₂₀ aryloxycarbonyl group; a hydroxycarbonyl group; an imide group; a cyano group ( -CN); carbamoyl group (-C (= O) NH _2); haloformyl group (-C (= O) -X, wherein, X is a halogen atom);. a formyl group (-C (= O) -H); isocyanato group; isocyanato group; thiocyanato group; Or a thioisocyanato group, or a group obtained by combining one or more of these substituents.

In the present specification, the “C ₇ -C ₂₀ alkylaryloxy group” is preferably a C ₇ -C ₁₂ alkylaryloxy group. Examples of alkylaryloxy groups include, but are not limited to, methylphenyloxy, ethylphenyloxy, propylphenyloxy, butylphenyloxy, dimethylphenyloxy, diethylphenyloxy, dipropylphenyloxy, dibutylphenyloxy, methyl Examples thereof include ethylphenyloxy, methylpropylphenyloxy, ethylpropylphenyloxy and the like.

In the present specification, the “C ₁ -C ₂₀ alkoxycarbonyl group” is preferably a C ₁ -C ₁₀ alkoxycarbonyl group. Examples of alkoxycarbonyl groups include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, 2-methoxyethoxycarbonyl, t-butoxycarbonyl, and the like.

In the present specification, the “C ₆ -C ₂₀ aryloxycarbonyl group” is preferably a C ₆ -C ₁₂ aryloxycarbonyl group. Examples of the aryloxycarbonyl group include, but are not limited to, phenoxycarbonyl, naphthoxycarbonyl, phenylphenoxycarbonyl, and the like.

In one aspect of the present invention, “C ₁ -C ₂₀ hydrocarbon group”, “C ₁ -C ₂₀ alkoxy group”, “C ₆ -C ₂₀ aryloxy group”, “amino group” represented by A ¹ and A ² ”,“ Silyl group ”,“ C ₇ -C ₂₀ alkylaryloxy group ”,“ C ₁ -C ₂₀ alkoxycarbonyl group ”,“ C ₆ -C ₂₀ aryloxycarbonyl group ”have a substituent introduced. May be. Examples of the substituent include a C _{1 to} C ₁₀ hydrocarbon group (for example, methyl, ethyl, propyl, butyl, phenyl, naphthyl, indenyl, tolyl, xylyl, benzyl, etc.), C _{1 to} C ₁₀ alkoxy group (for example, , Methoxy, ethoxy, propoxy, butoxy, etc.), C ₆ -C ₁₂ aryloxy groups (eg, phenyloxy, naphthyloxy, biphenyloxy, etc.), amino groups, hydroxyl groups, halogen atoms (eg, fluorine, chlorine, bromine, iodine) ) Or a silyl group. In this case, one or more substituents may be introduced at substitutable positions, and preferably 1 to 4 substituents may be introduced. When the number of substituents is 2 or more, each substituent may be the same or different.

In one aspect of the present invention, A ¹ and A ² may be bridged with each other to form a ring represented by the formula —C (═O) —B—C (═O) —. In the above formula, B is an oxygen atom or a group represented by the formula —N (B ¹ ) — (wherein B ¹ is a hydrogen atom, a C _{1 to} C ₂₀ hydrocarbon group, or a halogen atom. ).

In one aspect of the present invention, A ¹ and A ² are each independently the same or different and are a hydrogen atom; a C ₁ -C ₂₀ alkyl group; a C ₆ -C ₁₈ aryl group; a C ₁ -C ₂₀ alkoxy group. ; C ₁ -C ₂₀ alkoxycarbonyl group; a hydroxycarbonyl group; a carbamoyl group; imido group; a hydroxymethyl group; formyl group:; is preferably a halogen atom halomethyl group.

In the above formula (3), P ¹ and P ² are each independently the same or different and are a leaving group represented by —MX ¹ X ² X ³ or —SO ₂ X ⁴ .

  In the above formula, M is a metal belonging to Group 14 of the periodic table, silicon, tin, or germanium, preferably silicon, tin, or germanium, and more preferably silicon or tin.

In the above formula, X ¹ , X ² and X ³ are each independently the same or different and are a hydrogen atom; or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, hydrogen atom; C ₁ -C ₂₀ alkyl group; preferably a or C ₆ -C ₁₈ aryl group, a hydrogen atom, methyl, ethyl, propyl, isopropyl, n- butyl, sec- butyl, tert- butyl, or phenyl More preferably.

In the above formula, X ⁴ is a hydrogen atom; or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent, and a C _{1 to} C ₂₀ alkyl group; or may have a substituent. A C ₆ -C ₁₈ aryl group is preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, or tolyl is more preferable.

In one aspect of the present invention, P ¹ and P ² are preferably -MX ¹ X ² X ³ (wherein M, X ¹ , X ² and X ³ have the above-mentioned meanings), and trimethylsilyl More preferably a group, a trimethylgermanium group, a trimethyltin group, a tributyltin group, a triphenylsilyl group, a triisopropylsilyl group, a triethylsilyl group, a dimethylsilyl group, or a dimethylphenylsilyl group.

  1 aspect of this invention WHEREIN: m is an integer greater than or equal to 0, Preferably it is an integer of 0-10, it is preferable that it is 0-7, and it is preferable that it is 0-4.

  1 aspect of this invention WHEREIN: n is an integer greater than or equal to 1, Preferably it is an integer of 1-10, it is preferable that it is 1-6, and it is preferable that it is 1-3.

単結合の場合には、Ｒ³及びＲ⁴に直接結合している炭素原子には、さらに水素原子が直接結合している。 In one aspect of the present invention, the bond represented by the following formula represents a single bond or a double bond.

In the case of a single bond, a hydrogen atom is further directly bonded to the carbon atom directly bonded to R ³ and R ⁴ .

  In one aspect of the present invention, the ring compound represented by the above formula (3) is reacted with a reducing agent. Examples of the reducing agent used include metal hydrides, and lithium aluminum hydride is preferable.

  In one aspect of the present invention, the amount of the reducing agent is 1 mol to 10 mol, preferably 2 mol to 5 mol, more preferably 2 mol, relative to 1 mol of the ring compound represented by the above formula (3). Mol to 4 mol.

In one aspect of the invention, it is then reacted with an electrophile or nucleophile. This adds the substituents R ⁷ and R ⁸ in the reaction product.
In one aspect of the present invention, the substituents R ⁷ and R ⁸ vary depending on the electrophile or nucleophile used, but are halogen atoms; C ₁ -C ₂₀ hydrocarbon groups; C ₁ -C ₂₀ alkoxy groups; or an amino group and a halogen atom such as bromine; methyl, C ₁ -C ₁₀ alkyl groups such as ethyl group, a methoxy group, C ₁ -C ₁₀ alkoxy groups such as ethoxy group; preferably a or amino group .
In one aspect of the invention, the electrophile or nucleophile used can include an electrophile or nucleophile containing substituents R ⁷ and R ⁸ , for example, substituents R ⁷ and R A halogenating agent containing ⁸ , an alkylating agent, an aminating agent, a reaction reagent for ether production, and the like. More specifically, a halogenating agent or an alkylating agent is preferable, and examples of the halogenating agent include phosphorus tribromide and bromine.

  In one aspect of the present invention, the amount of the electrophile or nucleophile is 0.1 mol to 10 mol, preferably 0.3 mol to 1 mol of the ring compound represented by the above formula (3). 3 moles, more preferably 0.5 moles to 2 moles.

  In one aspect of the present invention, typically, a reducing agent suspension is dropped into a solution of the ring compound represented by the above formula (3) and stirred, and an acid is added to the reaction solution to extract a product. To do. Subsequently, the hydrocarbon condensed ring shown by said Formula (2) can be obtained by adding an electrophile or a nucleophile to the solution of an extract, and stirring.

In one aspect of the present invention, the reaction is preferably performed in a temperature range of 0 ° C to 100 ° C, more preferably in a temperature range of 10 ° C to 50 ° C, and further preferably in a temperature range of 20 ° C to 30 ° C. .
In one aspect of the present invention, the pressure is preferably atmospheric pressure.
In one aspect of the present invention, the reaction time is preferably 1 hour to 48 hours and more preferably 3 hours to 24 hours in the reaction of the ring compound represented by the above formula (3) with the reducing agent. Preferably, it is 5 hours-7 hours, and it is especially preferable.
In the reaction with the electrophile or nucleophile, the reaction time is preferably 1 hour to 24 hours, more preferably 1 hour to 6 hours, and particularly preferably about 1 hour.

  In one aspect of the present invention, the solvent used in the reaction of the ring compound represented by the above formula (3) and the reducing agent is preferably a solvent capable of dissolving the ring compound represented by the above formula (3). As the solvent, an aliphatic or aromatic organic solvent is used. For example, ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; N Amides such as N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; aromatic hydrocarbons such as benzene and toluene are used.

  In one aspect of the present invention, the solvent used in the reaction with the electrophile or nucleophile is a solvent that can dissolve the reaction product of the ring compound represented by the above formula (3) and the reducing agent. preferable. As the solvent, an aliphatic or aromatic organic solvent is used. For example, ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; N Amides such as N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; aromatic hydrocarbons such as benzene and toluene are used.

［式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｍ及びｎは、上記の意味を有する。Ｒ⁷及びＲ⁸は、それぞれ、互いに独立し、同一または異なって、ハロゲン原子；Ｃ₁〜Ｃ₂₀炭化水素基；Ｃ₁〜Ｃ₂₀アルコキシ基；又はアミノ基である。］ In another aspect of the present invention, the method includes the step of aromatizing the hydrocarbon condensed ring obtained in one aspect of the present invention in the presence of a dehydrogenating reagent. A method for producing acenes represented by the formula:

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n have the above-mentioned meanings. R ⁷ and R ⁸ are each independently the same or different and are each a halogen atom; a C ₁ -C ₂₀ hydrocarbon group; a C ₁ -C ₂₀ alkoxy group; or an amino group. ]

［式中、Ｙ¹、Ｙ²、Ｙ³、及び、Ｙ⁴は、それぞれ、互いに独立し、同一または異なって、ハロゲン原子又はシアノ基である。］ In another aspect of the present invention, the hydrocarbon condensed ring represented by the above formula (2) obtained in one aspect of the present invention is reacted with a dehydrogenation reagent. Preferred examples of the dehydrogenation reagent to be used include compounds represented by the following formula (4).

[Wherein Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently the same or different and are a halogen atom or a cyano group. ]

In the above formula (4), when Y ¹ , Y ² , Y ³ and Y ⁴ are halogen atoms, a chlorine atom, bromine atom or iodine atom is preferred, a chlorine atom or bromine atom is more preferred, and chlorine Atoms are more preferred.
For example, Y ¹ , Y ² , Y ³ , and Y ⁴ may all be chlorine atoms. That is, chloranil may be used. Alternatively, Y ¹ and Y ² may be a cyano group, and Y ³ and Y ⁴ may be a chlorine atom. That is, 2,3-dichloro-5,6-dicyanoquinone (DDQ) may be used. Y ¹ , Y ² , Y ³ , and Y ⁴ may all be cyano groups. That is, 2,3,5,6-tetracyanoquinone may be used.

  In another aspect of the present invention, typically, an acene represented by the above formula (1) is added to a hydrocarbon condensed ring solution represented by the above formula (2) by adding a dehydrogenating reagent and heating. Can be obtained.

  In another aspect of the present invention, the amount of the dehydrogenation reagent to be used is 0.1 mol to 10 mol, preferably 0.5 mol, relative to 1 mol of the hydrocarbon condensed ring represented by the above formula (2). It is -6 mol, More preferably, it is 0.8 mol-4 mol.

  In another aspect of the present invention, when a quinone represented by the above formula (4) is used as a dehydrogenation reagent, the quinone represented by the above formula (4) further undergoes a Diels-Alder reaction with the product acenes. As a result, a by-product may be formed. If desired, by-products are removed by column chromatography or the like.

  In another aspect of the present invention, when the quinone represented by the above formula (4) is used as a dehydrogenation reagent, the carbonization represented by the above formula (2) is used to prevent the formation of such a by-product. It is preferable to use 0.9 mol to 1.2 mol, more preferably 0.9 mol to 1.15 mol, and more preferably 0.95 mol to 1.10 mol per one saturated bond of the hydrogen condensed ring. It is more preferable to use the molar amount.

In another aspect of the present invention, the reaction is preferably performed in a temperature range of 50 ° C to 200 ° C, more preferably in a temperature range of 60 ° C to 150 ° C, and even more preferably in a temperature range of 80 ° C to 120 ° C. Is called.
In another aspect of the present invention, the pressure is preferably normal pressure.
In another aspect of the present invention, the reaction time is preferably 1 hour to 24 hours, more preferably 1 hour to 12 hours, and particularly preferably 1 hour to 3 hours.

  In another aspect of the present invention, the solvent used is preferably a solvent that can dissolve the hydrocarbon condensed ring represented by the above formula (2). As the solvent, an aliphatic or aromatic organic solvent is used. For example, ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as methylene chloride; halogenated aromatic hydrocarbons such as o-dichlorobenzene; N Amides such as N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; aromatic hydrocarbons such as benzene and toluene are used.

  Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the following examples.

All reactions were carried out using an anhydrous solvent under a nitrogen atmosphere unless otherwise specified.
THF was dehydrated using sodium / benzophenone system.
Unless otherwise specified, commercially available products were used as they were without purification.

  The following models were used for NMR. NMR-JEOL JNM-AL300, Bruker ARX-400

トリメチルシリルアセチレン（13.6 mL, 96 mmol）のTHF（100 mL）溶液に、臭化エチルマグネシウムのTHF溶液（0.96 M, 100 mL, 96 mmol）を加え、40℃で1時間かくはんする。この溶液に塩化銅(I)（1.19 g, 12 mmol）と1,2-ビス（ヨードメチル）ベンゼン（8.59 g, 24 mmol）を加え、2時間加熱還流する。反応液を氷冷し、塩化アンモニウム水溶液を加え、ヘキサンで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を淡黄色油状物として得る（6.55 g, 91%）。 Reference example 1
Synthesis of 1,2-bis (3-trimethylsilyl-2-propynyl) benzene

To a solution of trimethylsilylacetylene (13.6 mL, 96 mmol) in THF (100 mL) is added ethylmagnesium bromide in THF (0.96 M, 100 mL, 96 mmol), and the mixture is stirred at 40 ° C. for 1 hour. To this solution, copper (I) chloride (1.19 g, 12 mmol) and 1,2-bis (iodomethyl) benzene (8.59 g, 24 mmol) are added and heated under reflux for 2 hours. The reaction mixture is ice-cooled, aqueous ammonium chloride solution is added, and the mixture is extracted with hexane. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a pale yellow oil (6.55 g, 91%).

¹ H NMR (CDCl ₃ , δ) 0.19 (s, 18 H), 3.65 (s, 4 H), 7.25-7.28 (m, 2 H), 7.45-7.48 (m, 2 H); ¹³ C NMR (CDCl ₃ , δ) 0.06, 23.89, 87.40, 103.42, 127.18, 128.63, 134.17.

二塩化ジルコノセン（3.51 g, 12 mmol）のTHF（30 mL）溶液を-78℃に冷却し、n-ブチルリチウムのヘキサン溶液（1.54 M, 15.6 mL, 24 mmol）をゆっくり加える。10分後反応液を-40℃に昇温し、30分後再び-78℃に冷却して10分かくはんする。この溶液に、参考例１で得られた1,2-ビス(3-トリメチルシリル-2-プロピニル)ベンゼン（2.99 g, 10 mmol）のTHF（10 mL）溶液を加えて、室温でかくはんする。3時間後、0℃に冷却して、塩化銅(I)（1.98 g, 20 mmol）とアセチレンジカルボン酸ジメチル（3.7 mL, 30 mmol）を加えて再び室温に戻して、6時間かくはんする。反応液に3M塩酸を加えて、酢酸エチルで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製した後、得られた固体をメタノールで洗浄する。得られた無色粉末を真空乾燥して、表題化合物を得る（1.73 g, 39%）。 Reference example 2
Synthesis of 1,4-bis (trimethylsilyl) -2,3-bis (methoxycarbonyl) -9,10-dihydroanthracene

A solution of zirconocene dichloride (3.51 g, 12 mmol) in THF (30 mL) is cooled to −78 ° C., and n-butyllithium in hexane (1.54 M, 15.6 mL, 24 mmol) is slowly added. After 10 minutes, the temperature of the reaction solution is raised to -40 ° C, and after 30 minutes, it is cooled to -78 ° C again and stirred for 10 minutes. To this solution is added a solution of 1,2-bis (3-trimethylsilyl-2-propynyl) benzene (2.99 g, 10 mmol) obtained in Reference Example 1 in THF (10 mL), and the mixture is stirred at room temperature. After 3 hours, cool to 0 ° C., add copper (I) chloride (1.98 g, 20 mmol) and dimethyl acetylenedicarboxylate (3.7 mL, 30 mmol), return to room temperature, and stir for 6 hours. Add 3M hydrochloric acid to the reaction mixture and extract with ethyl acetate. The residue obtained by distilling off the solvent is purified by silica gel column chromatography, and the resulting solid is washed with methanol. The resulting colorless powder is dried in vacuo to give the title compound (1.73 g, 39%).

¹ H NMR (CDCl ₃ , δ) 0.46 (s, 18 H), 3.85 (s, 6 H), 4.04 (s, 4 H), 7.23-7.27 (m, 2 H), 7.32-7.35 (m, 2 H); ¹³ C NMR (CDCl ₃ , δ) 1.73, 38.41, 52.29, 126.17, 126.41, 135.58, 135.90, 137.22, 145.85, 170.50.

参考例２で得られた1,4-ビス(トリメチルシリル)-2,3-ビス(メトキシカルボニル)-9,10-ジヒドロアントラセン（4.50 g, 10.2 mmol）のTHF溶液を0℃に冷却して、水素化リチウムアルミニウム（1.16 g, 30.6 mmol）のTHF（70 mL）懸濁液をゆっくり滴下する。室温で6時間攪拌した後、反応液に水および3M塩酸を静かに加える。有機物をクロロホルムで抽出して減圧下溶媒を留去する。得られた無色固体を1,2-ジクロロエタンに溶解し、三臭化リン（0.96 mL, 10 mmol）を加え室温で1時間かくはんする。反応液に水を加え、有機層をクロロホルムで抽出する。溶媒を留去して得られる固体をメタノールで洗浄することで、表題化合物を無色粉末として得る（2.18 g, 58%）。 Synthesis of 2,3-bis (bromomethyl) -9,10-dihydroanthracene

The THF solution of 1,4-bis (trimethylsilyl) -2,3-bis (methoxycarbonyl) -9,10-dihydroanthracene (4.50 g, 10.2 mmol) obtained in Reference Example 2 was cooled to 0 ° C., A suspension of lithium aluminum hydride (1.16 g, 30.6 mmol) in THF (70 mL) is slowly added dropwise. After stirring at room temperature for 6 hours, water and 3M hydrochloric acid are gently added to the reaction mixture. The organic substance is extracted with chloroform, and the solvent is distilled off under reduced pressure. The obtained colorless solid is dissolved in 1,2-dichloroethane, phosphorus tribromide (0.96 mL, 10 mmol) is added, and the mixture is stirred at room temperature for 1 hour. Water is added to the reaction mixture, and the organic layer is extracted with chloroform. The solid obtained by distilling off the solvent is washed with methanol to give the title compound as a colorless powder (2.18 g, 58%).

¹ H NMR (CDCl ₃ , δ) 3.93 (s, 4 H), 4.68 (s, 4 H), 7.19-7.31 (m, 6 H); ¹³ C NMR (CDCl ₃ , δ) 30.24, 35.59, 126.29, 127.37, 130.05, 134.20, 135.66, 138.21.

実施例１で得られた2,3-ビス(ブロモメチル)-9,10-ジヒドロアントラセン（366 mg, 1.0 mmol）のアセトン(20 mL)溶液に、ヨウ化ナトリウム（749 mg, 5.0 mmol）を加え室温で一晩かくはんした。反応液から、減圧下にアセトンを留去し、残留物を水およびメタノールで洗浄する。得られた固体を減圧乾燥して、表題化合物を得る（414 mg, 90%）。 Reference example 3
Synthesis of 2,3-bis (iodomethyl) -9,10-dihydroanthracene

To a solution of 2,3-bis (bromomethyl) -9,10-dihydroanthracene (366 mg, 1.0 mmol) obtained in Example 1 in acetone (20 mL), sodium iodide (749 mg, 5.0 mmol) was added. Stir overnight at room temperature. Acetone is distilled off from the reaction solution under reduced pressure, and the residue is washed with water and methanol. The resulting solid is dried under reduced pressure to give the title compound (414 mg, 90%).

¹ H NMR (CDCl ₃ , δ) 3.87 (s, 4H), 4.58 (s, 4H), 7.18-7.28 (m, 6H); ¹³ C NMR (CDCl ₃ , δ) 2.17, 35.72, 126.34, 127.41, 129.69 , 135.10, 135.85, 137.90.

トリメチルシリルアセチレン（0.57 mL, 4.0 mmol）のTHF（10 mL）溶液に、臭化エチルマグネシウムのTHF溶液（0.96 M, 4.2 mL, 4.0 mmol）を加え、40℃で1時間かくはんする。この溶液に塩化銅(I)（50 mg, 0.50 mmol）と、参考例３で得られた2,3-ビス(ヨードメチル)-9,10-ジヒドロアントラセン（460 mg, 1.0 mmol）を加え、2時間加熱還流する。反応液を氷冷し、塩化アンモニウム水溶液を加え、ヘキサンで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を淡黄色油状物として得る（280 mg, 70%）。 Reference example 4
Synthesis of 2,3-bis (3-trimethylsilyl-2-propynyl) -9,10-dihydroanthracene

To a solution of trimethylsilylacetylene (0.57 mL, 4.0 mmol) in THF (10 mL) is added ethylmagnesium bromide in THF (0.96 M, 4.2 mL, 4.0 mmol), and the mixture is stirred at 40 ° C. for 1 hour. To this solution, copper (I) chloride (50 mg, 0.50 mmol) and 2,3-bis (iodomethyl) -9,10-dihydroanthracene (460 mg, 1.0 mmol) obtained in Reference Example 3 were added, and 2 Heat at reflux for hours. The reaction mixture is ice-cooled, aqueous ammonium chloride solution is added, and the mixture is extracted with hexane. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a pale yellow oil (280 mg, 70%).

¹ H NMR (CDCl ₃ , δ) 0.24 (s, 18 H), 3.65 (s, 4 H), 3.92 (s, 4 H), 7.17-7.24 (m, 2 H), 7.26-7.31 (m, 2 H), 7.36 (s, 2 H); ¹³ C NMR (CDCl ₃ , δ) 0.10, 23.58, 35.58, 87.05, 103.88, 126.03, 127.38, 127.88, 131.84, 135.33, 136.42.

二塩化ジルコノセン（351 mg, 1.2 mmol）のTHF（10 mL）溶液を-78℃に冷却し、n-ブチルリチウムのヘキサン溶液（1.54 M, 1.56 mL, 2.4 mmol）をゆっくり加える。10分後反応液を-40℃に昇温し、30分後再び-78℃に冷却して10分かくはんする。この溶液に、参考例４で得られた2,3-ビス(3-トリメチルシリル-2-プロピニル)-9,10-ジヒドロアントラセン（401 mg, 1.0 mmol）のTHF（3 mL）溶液を加えて、室温でかくはんする。3時間後、0℃に冷却して、塩化銅(I)（198 mg, 2.0 mmol）とアセチレンジカルボン酸ジメチル（0.37 mL, 3.0 mmol）を加えて再び室温に戻して、6時間かくはんする。反応液に3M塩酸を加えて、酢酸エチルで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を無色固体として得る（207 mg, 38%）。 Reference Example 5
Synthesis of 1,4-bis (3-trimethylsilyl-2-propynyl) -2,3-bis (methoxycarbonyl) -5,7,12,14-tetrahydropentacene

A solution of zirconocene dichloride (351 mg, 1.2 mmol) in THF (10 mL) is cooled to −78 ° C., and n-butyllithium in hexane (1.54 M, 1.56 mL, 2.4 mmol) is slowly added. After 10 minutes, the temperature of the reaction solution is raised to -40 ° C, and after 30 minutes, it is cooled to -78 ° C again and stirred for 10 minutes. To this solution was added a THF (3 mL) solution of 2,3-bis (3-trimethylsilyl-2-propynyl) -9,10-dihydroanthracene (401 mg, 1.0 mmol) obtained in Reference Example 4, Stir at room temperature. After 3 hours, cool to 0 ° C., add copper (I) chloride (198 mg, 2.0 mmol) and dimethyl acetylenedicarboxylate (0.37 mL, 3.0 mmol), return to room temperature, and stir for 6 hours. Add 3M hydrochloric acid to the reaction mixture and extract with ethyl acetate. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a colorless solid (207 mg, 38%).

¹ H NMR (CDCl ₃ , δ) 0.31 (s, 18 H), 3.69 (s, 6 H), 3.82 (s, 4 H), 3.87 (s, 4 H), 7.03-7.21 (m, 6 H) ; ¹³ C NMR (CDCl ₃ , δ) 1.76, 35.85, 38.06, 52.27, 125.21, 126.03, 127.34, 134.82, 135.03, 135.52, 135.81, 136.67, 146.01, 170.52.

参考例５で得られた1,4-ビス(3-トリメチルシリル-2-プロピニル)-2,3-ビス(メトキシカルボニル)-5,7,12,14-テトラヒドロペンタセン（271 mg, 0.5 mmol）のTHF（5 mL）溶液を0℃に冷却して、水素化リチウムアルミニウム（57 mg, 1.5 mmol）のTHF（5 mL）懸濁液をゆっくり滴下する。室温で6時間攪拌した後、反応液に水および3M塩酸を静かに加える。有機物をクロロホルムで抽出して減圧下溶媒を留去する。得られた無色固体を1,2-ジクロロエタンに溶解し、三臭化リン（0.05 mL, 0.5 mmol）を加え室温で1時間かくはんする。反応液に水を加え、有機層をクロロホルムで抽出する。溶媒を留去して得られる固体をメタノールで洗浄することで、表題化合物を無色粉末として得る（98 mg, 42%）。 Synthesis of 2,3-bis (bromomethyl) -5,7,12,14-tetrahydropentacene

Of 1,4-bis (3-trimethylsilyl-2-propynyl) -2,3-bis (methoxycarbonyl) -5,7,12,14-tetrahydropentacene (271 mg, 0.5 mmol) obtained in Reference Example 5 The THF (5 mL) solution is cooled to 0 ° C. and a suspension of lithium aluminum hydride (57 mg, 1.5 mmol) in THF (5 mL) is slowly added dropwise. After stirring at room temperature for 6 hours, water and 3M hydrochloric acid are gently added to the reaction mixture. The organic substance is extracted with chloroform, and the solvent is distilled off under reduced pressure. The obtained colorless solid is dissolved in 1,2-dichloroethane, phosphorus tribromide (0.05 mL, 0.5 mmol) is added, and the mixture is stirred at room temperature for 1 hour. Water is added to the reaction mixture, and the organic layer is extracted with chloroform. The solid obtained by distilling off the solvent is washed with methanol to give the title compound as a colorless powder (98 mg, 42%).

¹ H NMR (CDCl ₃ , δ) 3.79 (s, 4 H), 3.81 (s, 4 H), 4.56 (s, 4 H), 7.04-7.21 (m, 8 H); ¹³ C NMR (CDCl ₃ , (δ) 30.28, 35.33, 35.76, 126.04, 126.38, 127.37, 130.12, 133.46, 134.21, 134.77, 136.69, 138.50.

実施例２で得られた2,3-ビス(ブロモメチル)-5,7,12,14-テトラヒドロペンタセン（0.20 mmol）のトルエン（2 mL）溶液にDDQ（50 mg, 0.22 mmol）を加え100℃に加熱し、1時間撹拌したのち、室温に冷却すると、青色の目的化合物が４０％の収率で得られた。 Synthesis of 2,3-bis (bromomethyl) pentacene

DDQ (50 mg, 0.22 mmol) was added to a toluene (2 mL) solution of 2,3-bis (bromomethyl) -5,7,12,14-tetrahydropentacene (0.20 mmol) obtained in Example 2 at 100 ° C. After stirring for 1 hour and cooling to room temperature, the blue target compound was obtained in 40% yield.

実施例１で得られた2,3-ビス(ブロモメチル)-9,10-ジヒドロアントラセン（1.70 g, 4.6 mmol）とDDQ（1.16 g, 5.1 mmol）をトルエンに溶解し、90℃で3時間加熱する。室温に冷却後、反応液をメタノール中に注ぎ、生じた沈殿を濾取する。その固体を減圧乾燥することで、表題化合物を得る（1.24 g, 73%）。 Synthesis of 2,3-bis (bromomethyl) anthracene

2,3-bis (bromomethyl) -9,10-dihydroanthracene (1.70 g, 4.6 mmol) and DDQ (1.16 g, 5.1 mmol) obtained in Example 1 were dissolved in toluene and heated at 90 ° C. for 3 hours. To do. After cooling to room temperature, the reaction solution is poured into methanol, and the resulting precipitate is collected by filtration. The solid is dried in vacuo to give the title compound (1.24 g, 73%).

¹ H NMR (CDCl ₃ , δ) 4.94 (s, 4H), 7.48-7.51 (m, 2H), 7.98-8.04 (m, 4H), 8.38 (s, 2H); ¹³ C NMR (CDCl ₃ , δ) 31.64, 126.03, 126.30, 128.24, 130.41, 131.03, 132.38, 134.26.

実施例４で得られた2,3-ビス(ブロモメチル)アントラセン（1.09 g, 3.0 mmol）のアセトン溶液に、ヨウ化ナトリウム（2.25 g, 15 mmol）を加え室温で一晩かくはんした。反応液から、減圧下にアセトンを留去し、残留物を水およびメタノールで洗浄する。得られた固体を減圧乾燥して、表題化合物を得る（1.26 g, 92%）。 Reference Example 6
Synthesis of 2,3-bis (iodomethyl) anthracene

To the acetone solution of 2,3-bis (bromomethyl) anthracene (1.09 g, 3.0 mmol) obtained in Example 4, sodium iodide (2.25 g, 15 mmol) was added and stirred overnight at room temperature. Acetone is distilled off from the reaction solution under reduced pressure, and the residue is washed with water and methanol. The resulting solid is dried under reduced pressure to give the title compound (1.26 g, 92%).

¹ H NMR (CDCl ₃ , δ) 4.88 (s, 4H), 7.46-7.49 (m, 2H), 7.96-8.02 (m, 4H), 8.34 (s, 2H); ¹³ C NMR (CDCl ₃ , δ) 3.62, 126.03, 126.29, 128.24, 130.41, 131.03, 132.38, 134.26.

トリメチルシリルアセチレン（0.57 mL, 4.0 mmol）のTHF（10 mL）溶液に、臭化エチルマグネシウムのTHF溶液（0.96 M, 4.2 mL, 4.0 mmol）を加え、40℃で1時間かくはんする。この溶液に塩化銅(I)（50 mg, 0.50 mmol）と、参考例６で得られた2,3-ビス(ヨードメチル)アントラセン（458 mg, 1.0 mmol）を加え、2時間加熱還流する。反応液を氷冷し、塩化アンモニウム水溶液を加え、ヘキサンで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を淡黄色油状物として得る（299 mg, 75%）。 Reference Example 7
Synthesis of 2,3-bis (3-trimethylsilyl-2-propynyl) anthracene

To a solution of trimethylsilylacetylene (0.57 mL, 4.0 mmol) in THF (10 mL) is added ethylmagnesium bromide in THF (0.96 M, 4.2 mL, 4.0 mmol), and the mixture is stirred at 40 ° C. for 1 hour. Copper (I) chloride (50 mg, 0.50 mmol) and 2,3-bis (iodomethyl) anthracene (458 mg, 1.0 mmol) obtained in Reference Example 6 are added to this solution, and the mixture is heated to reflux for 2 hours. The reaction mixture is ice-cooled, aqueous ammonium chloride solution is added, and the mixture is extracted with hexane. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a pale yellow oil (299 mg, 75%).

¹ H NMR (CDCl ₃ , δ) 0.38 (s, 18H), 3.85 (s, 4H), 7.49-7.52 (m, 2H), 7.99-8.05 (m, 4H), 8.33 (s, 2H); ¹³ C NMR (CDCl ₃ , δ) 0.16, 24.25, 88.13, 103.56, 125.13, 125.48, 127.25, 128.07, 130.82, 131.67, 132.05.

二塩化ジルコノセン（351 mg, 1.2 mmol）のTHF溶液（10 mL）を-78℃に冷却し、n-ブチルリチウムのヘキサン溶液（1.54 M, 1.56 mL, 2.4 mmol）をゆっくり加える。10分後反応液を-40℃に昇温し、30分後再び-78℃に冷却して10分かくはんする。この溶液に、参考例７で得られた2,3-ビス(3-トリメチルシリル-2-プロピニル)アントラセン（399 mg, 1.0 mmol）のTHF（5 mL）溶液を加えて、室温でかくはんする。3時間後、0℃に冷却して、塩化銅(I)（238 mg, 2.4 mmol）とアセチレンジカルボン酸ジメチル（0.37 mL, 3.0 mmol）を加えて再び室温に戻して、6時間かくはんする。反応液に3M塩酸を加えて、酢酸エチルで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を無色固体として得る（205 mg, 38%）。 Reference Example 8
Synthesis of 1,4-bis (trimethylsilyl) -2,3-bis (methoxycarbonyl) -5,14-dihydropentacene

A THF solution (10 mL) of zirconocene dichloride (351 mg, 1.2 mmol) is cooled to −78 ° C., and a hexane solution of n-butyllithium (1.54 M, 1.56 mL, 2.4 mmol) is slowly added. After 10 minutes, the reaction solution is heated to -40 ° C, and after 30 minutes, it is cooled again to -78 ° C and stirred for 10 minutes. To this solution, a solution of 2,3-bis (3-trimethylsilyl-2-propynyl) anthracene (399 mg, 1.0 mmol) obtained in Reference Example 7 in THF (5 mL) is added and stirred at room temperature. After 3 hours, cool to 0 ° C., add copper (I) chloride (238 mg, 2.4 mmol) and dimethyl acetylenedicarboxylate (0.37 mL, 3.0 mmol), return to room temperature, and stir for 6 hours. Add 3M hydrochloric acid to the reaction mixture and extract with ethyl acetate. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a colorless solid (205 mg, 38%).

¹ H NMR (CDCl ₃ , δ) 0.50 (s, 18H), 3.84 (s, 6H), 4.23 (s, 4H), 7.43-7.46 (m, 2H), 7.89 (s, 2H), 7.97-8.00 ( m, 2H), 8.39 (s, 2H); ¹³ C-NMR (CDCl ₃ , δ) 1.77, 38.64, 52.29, 123.92, 125.07, 125.48, 127.99, 130.94, 131.49, 135.26, 135.78, 136.01, 145.60, 170.42.

1-ヘキシン（1.71 mL, 15 mmol）のTHF（30 mL）溶液を-78℃に冷却し、n-ブチルリチウムのヘキサン溶液（1.54 M, 8.85 mL, 13.6 mmol）を加える。その後室温で、1時間かくはんする。この溶液に、実施例４で得られた2,3-ビス(ブロモメチル)アントラセン（1.24 g, 3.4 mmol）とトルエン（20 mL）を加え、50℃で3時間加熱かくはんする。室温に冷却後、3M塩酸を加え、有機層をヘキサンで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製することで、表題化合物を無色固体として得る（1.01 g, 81%）。 Reference Example 9
Synthesis of 2,3-di-2-heptynylanthracene

A solution of 1-hexyne (1.71 mL, 15 mmol) in THF (30 mL) is cooled to −78 ° C., and a hexane solution of n-butyllithium (1.54 M, 8.85 mL, 13.6 mmol) is added. Then stir at room temperature for 1 hour. To this solution, 2,3-bis (bromomethyl) anthracene (1.24 g, 3.4 mmol) obtained in Example 4 and toluene (20 mL) are added, and the mixture is stirred with heating at 50 ° C. for 3 hours. After cooling to room temperature, 3M hydrochloric acid is added, and the organic layer is extracted with hexane. The title compound is obtained as a colorless solid by purifying the residue obtained by distilling off the solvent by silica gel column chromatography (1.01 g, 81%).

¹ H NMR (CDCl ₃ , δ) 0.95 (t, 6 H, J = 7 Hz), 1.38-1.63 (m, 8 H), 2.23-2.33 (m, 4 H), 3.76 (s, 4 H), 7.39-7.47 (m, 2 H), 7.94-8.02 (m, 2 H), 8.07 (s, 2 H), 8.36 (s, 2 H); ¹³ C NMR (CDCl ₃ , δ) 13.65, 18.63, 22.05 , 23.25, 31.12, 76.78, 83.87, 125.08, 125.49, 126.94, 128.13, 131.04, 131.66, 133.57.

二塩化ジルコノセン（901 mg, 3.07 mmol）のTHF（30 mL）溶液を-78℃に冷却し、n-ブチルリチウムのヘキサン溶液（1.54 M, 3.98 mL, 6.13 mmol）をゆっくり加える。10分後反応液を-40℃に昇温し、30分後再び-78℃に冷却して10分かくはんする。この溶液に、参考例９で得られた2,3-ジ-2-ヘプチニルアントラセン（1.02 g, 2.79 mmol）のTHF（10 mL）溶液を加えて、室温でかくはんする。3時間後、0℃に冷却して、塩化銅(I)（552 mg, 5.57 mmol）とアセチレンジカルボン酸ジメチル（1.0 mL, 8.4 mmol）を加えて再び室温に戻して、6時間かくはんする。反応液に3M塩酸を加えて、酢酸エチルで抽出する。溶媒を留去して得られる残留物をシリカゲルカラムクロマトグラフィーで精製して、表題化合物を無色固体として得る（565 mg, 40%）。 Reference Example 10
Synthesis of 1,4-dibutyl-2,3-bis (methoxycarbonyl) -5,14-dihydropentacene

A solution of zirconocene dichloride (901 mg, 3.07 mmol) in THF (30 mL) is cooled to −78 ° C., and n-butyllithium in hexane (1.54 M, 3.98 mL, 6.13 mmol) is slowly added. After 10 minutes, the temperature of the reaction solution is raised to -40 ° C, and after 30 minutes, it is cooled to -78 ° C again and stirred for 10 minutes. To this solution, a solution of 2,3-di-2-heptynylanthracene (1.02 g, 2.79 mmol) obtained in Reference Example 9 in THF (10 mL) is added and stirred at room temperature. After 3 hours, cool to 0 ° C., add copper (I) chloride (552 mg, 5.57 mmol) and dimethyl acetylenedicarboxylate (1.0 mL, 8.4 mmol), return to room temperature, and stir for 6 hours. Add 3M hydrochloric acid to the reaction mixture and extract with ethyl acetate. The residue obtained by distilling off the solvent is purified by silica gel column chromatography to obtain the title compound as a colorless solid (565 mg, 40%).

¹ H NMR (CDCl ₃ , δ) 1.02 (t, 6 H, J = 7 Hz), 1.44-1.66 (m, 8 H), 2.80-2.87 (m, 4H), 3.85 (s, 6 H), 4.11 (s, 4 H), 7.41-7.46 (m, 2 H), 7.92 (s, 2 H), 7.96-8.01 (m, 2 H), 8.38 (s, 2 H); ¹³ C NMR (CDCl ₃ , δ) 13.94, 22.99, 30.30, 33.11, 33.61, 52.22, 124.39, 125.06, 125.40, 128.04, 130.38, 131.00, 131.52, 135.10, 135.44, 138.94, 169.43.

参考例１０で得られた1,4-ジブチル-2,3-ビス(メトキシカルボニル)-5,14-ジヒドロペンタセン（102 mg, 0.20 mmol）のトルエン（2 mL）溶液を100℃に加熱しながら、DDQ（50 mg, 0.22 mmol）のトルエン（3 mL）溶液を3時間かけて滴下する。さらに2時間加熱した後室温に冷却する。反応液にメタノール（30 mL）を加え、生じた沈殿を濾取し、ヘキサンから再結晶することで、表題化合物を得る（11 mg, 11%）。 Reference Example 11
Synthesis of 1,4-dibutyl-2,3-bis (methoxycarbonyl) pentacene

While the toluene (2 mL) solution of 1,4-dibutyl-2,3-bis (methoxycarbonyl) -5,14-dihydropentacene (102 mg, 0.20 mmol) obtained in Reference Example 10 was heated to 100 ° C. , DDQ (50 mg, 0.22 mmol) in toluene (3 mL) is added dropwise over 3 hours. Heat for another 2 hours and then cool to room temperature. Methanol (30 mL) is added to the reaction mixture, and the resulting precipitate is collected by filtration and recrystallized from hexane to give the title compound (11 mg, 11%).

¹ H NMR (CDCl ₃ , δ) 1.06 (t, 6 H, J = 7 Hz), 1.54-1.65 (m, 4 H), 1.80-1.91 (m, 4 H), 3.18-3.27 (m, 4 H ), 3.93 (s, 6 H), 7.31-7.38 (m, 2 H), 7.90-7.97 (m, 2 H), 8.65 (s, 2 H), 8.88 (s, 2 H), 8.95 (s, 2 H); ¹³ C NMR (CDCl ₃ , δ) 13.99, 23.31, 30.12, 33.30, 52.28, 125.44, 125.66, 126.45, 127.03, 128.40, 129.03, 129.58, 129.89, 130.56, 131.85, 138.00, 169.55.

Claims (3)

A ring compound represented by the following formula (3);

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently the same or different and have a hydrogen atom; a halogen atom; a hydroxy group; a substituent. C ₁ -C ₂₀ hydrocarbon group which may have a substituent; C ₁ -C ₂₀ alkoxy group which may have a substituent; C ₆ -C ₂₀ aryloxy group which may have a substituent; An optionally substituted amino group; or a silyl group optionally having a substituent,
A ¹ and A ² are each independently the same or different and are each a hydrogen atom; a halogen atom; an optionally substituted C ₁ -C ₂₀ hydrocarbon group; Good C ₁ -C ₂₀ alkoxy group; optionally substituted C ₆ -C ₂₀ aryloxy group; optionally substituted C ₇ -C ₂₀ alkylaryloxy group; and C ₁ -C ₂₀ optionally alkoxycarbonyl group; optionally substituted C ₆ -C ₂₀ aryloxycarbonyl group; hydroxy group; imido group; a cyano group (-CN); carbamoyl group ( _{-C (= O) NH 2)} ; haloformyl (-C (= O) -X, wherein, X is a halogen atom);. a formyl group (-C (= O) -H) ; isocyano group; Isocyanato group; thiocyanato group; or thioisocyanate It is a nato group or a group in which one or more of these substituents are combined, provided that A ¹ and A ² are cross-linked to form the formula —C (═O) —B—C (═O) —. (Wherein B is an oxygen atom or a group represented by the formula —N (B ¹ ) — (wherein B ¹ is a hydrogen atom, a C ₁ -C ₂₀ hydrocarbon). A group or a halogen atom).
P ¹ and P ² are each independently the same or different and represent -MX ¹ X ² X ³ (wherein M is a metal of Group 14 of the periodic table, silicon, tin, or germanium; X ¹ , X ² and X ³ are each independently the same or different and are a hydrogen atom; or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent.) Or —SO ₂ A leaving group represented by X ⁴ (wherein X ⁴ is a hydrogen atom; or a C _{1 to} C ₂₀ hydrocarbon group which may have a substituent);
m is an integer greater than or equal to 0,
n is an integer of 1 or more.
The bond represented by the following formula represents a single bond or a double bond.

]
The method comprises the steps of removing a leaving group P ¹ and P ² in the ring compound by reacting with a reducing agent and then reacting with an electrophile or a nucleophile. (2) The manufacturing method of the hydrocarbon condensed ring shown.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n have the above-mentioned meanings.
The bond represented by the following formula represents a single bond or a double bond.

R ⁷ and R ⁸ are each independently the same or different and are each a halogen atom; a C ₁ -C ₂₀ hydrocarbon group; a C ₁ -C ₂₀ alkoxy group; or an amino group. ] P ¹ and P ² are each independently the same or different, and are a trimethylsilyl group, trimethylgermanium group, trimethyltin group, tributyltin group, triphenylsilyl group, triisopropylsilyl group, triethylsilyl group, dimethylsilyl group, Or the manufacturing method of the hydrocarbon condensed ring of Claim 1 which is a dimethylphenylsilyl group. A method for producing an acene represented by the following formula (1), comprising a step of aromatizing the hydrocarbon condensed ring obtained in claim 1 or 2 in the presence of a dehydrogenating reagent.

[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently the same or different and have a hydrogen atom; a halogen atom; a hydroxy group; a substituent. C ₁ -C ₂₀ hydrocarbon group which may have a substituent; C ₁ -C ₂₀ alkoxy group which may have a substituent; C ₆ -C ₂₀ aryloxy group which may have a substituent; An optionally substituted amino group; or a silyl group optionally having a substituent,
R ⁷ and R ⁸ are each independently the same or different and are a halogen atom; a C ₁ -C ₂₀ hydrocarbon group; a C ₁ -C ₂₀ alkoxy group; or an amino group,
m is an integer greater than or equal to 0,
n is an integer of 1 or more.
The bond represented by the following formula represents a single bond or a double bond.

]