JP5899010B2 - ANANTHOLENE COMPOUND AND PROCESS FOR PRODUCING THE SAME - Google Patents

Description

  The present invention relates to a novel anthanthrene compound and a method for producing the same.

  In recent years, organic semiconductors have attracted attention as materials that can replace inorganic semiconductors typified by silicon. Such organic semiconductors are used, for example, in organic electroluminescence elements (OLEDs), solar cells, transistors, and the like. In particular, they are superior in flexibility compared to inorganic semiconductors, and are controlled by controlling the molecular structure. Therefore, it is expected in the field of printed electronics formed by roll-to-roll printing.

  Among such organic semiconductors, as a low molecular organic semiconductor, it is known that a molecule having an acene skeleton typified by pentacene exhibits high semiconductor characteristics. However, since the acene skeleton has a reactive site in the molecule and is easily oxidized, there is a problem in atmospheric stability, and a more stable molecule is required.

  For the purpose of improving such a stability problem, for example, a specific antanthrene-based compound having a peri-xanthenoxanthene skeleton is being developed as an organic semiconductor [for example, Japanese Patent Application Laid-Open No. 2010-6794 Gazette (patent document 1), Japanese translations of PCT publication No. 2009-544743 (patent document 2), Chem. Mater. 2009, 21, 552-556 (Non-Patent Document 1) etc.], application to such an organic semiconductor device is expected. Although these documents disclose compounds having various anthanthrene skeletons, the compounds in which a formyl group (and further a halogen atom) is substituted at a specific substitution position of an anthanthrene (dioxaanthanthrene) skeleton are disclosed. Is not disclosed.

  Such an anthanthrene compound is synthesized, for example, by oxidative coupling of 1,1′-bi-2-naphthols as disclosed in Patent Document 2. However, in such a method, depending on the position and structure of the substituent of 1,1'-bi-2-naphthols, the oxidative coupling reaction may not proceed easily and the yield may be low.

  JP 2011-12001 (Patent Document 3) discloses a substituent such as a p-ethylphenyl group using a reaction of brominated dioxaanthanthrene (Suzuki-Miyaura coupling reaction). Techniques for introducing or oligomerizing are disclosed. However, in such a method, it is difficult to introduce a functional group with high regioselectivity, and there is a problem in molecular design.

  Under such circumstances, development of new anthanthrene compounds and synthesis methods is demanded.

JP 2010-6794 A (Claims) JP-T 2009-544743 (Claims, paragraph [0043]) JP 2011-12001 A (Claims, Examples)

Chem. Mater. 2009, 21, 552-556

  Accordingly, an object of the present invention is to provide a novel anthanthrene compound useful as an organic semiconductor or an intermediate (precursor) thereof.

  Another object of the present invention is to provide a method capable of efficiently producing the above-described anthanthrene-based compound.

  As a result of intensive studies to achieve the above object, the present inventor has a 2,2′-dihydroxy (or mercapto) -3,3′-diformyl-8,8′-dihalo-1,1′-binaphthyl skeleton. Surprisingly, a compound or the like is easily cyclized between the 1-position and the 8′-position and between the 1′-position and the 8-position with elimination of hydrogen halide or the like, and a dioxaanthanthrene skeleton, etc. In addition to being able to be used as an organic semiconductor as is, a novel antanthrene-based compound obtained by such a reaction (such as a compound having a dioxaanthanthrene skeleton) can be used as a functional group, a formyl group (further, Since it has a substituent (such as a halogen atom), it can be easily modified (substituent conversion) and is suitable as an intermediate (or precursor) for a desired organic semiconductor. And, to complete the present invention.

  That is, the compound of the present invention is represented by the following formula (1).

(In the formula, E represents an oxygen atom or a sulfur atom, R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom or a substituent, and R ¹ and R ² , R ² and R ^3, or R ³ and R ⁴ are bonded to each other. And may form a ring.)
In the above formula (1), at least one of R ^{1 to} R ⁴ may be a halogen atom (bromine atom, iodine atom, etc.), and in particular, at least one of R ^{2 to} R ⁴ is a halogen atom (particularly an iodine atom). ). Typically, in formula (1), R ¹ may be a hydrogen atom, and at least two of R ^{2 to} R ⁴ may be iodine atoms. In particular, in formula (1), E is an oxygen atom, R ¹ and R ⁴ may be a hydrogen atom, and R ² and R ³ may be an iodine atom.

  In the present invention, the compound represented by the following formula (2) is reacted (cyclization reaction) (or HX is eliminated from the compound represented by the formula (2)), whereby the compound (the above formula: A method for producing a compound represented by (1) is also included.

(In the formula, X represents a leaving group that can be removed by reacting with the group -EH, and E and R ^{1 to} R ⁴ are the same as above.)
In the above formula (2), X may be a halogen atom, particularly an iodine atom.

  In the method, the compound represented by the formula (2) may be reacted in the presence of a base (for example, at least one selected from carboxylic acid metal salts and metal hydroxides).

  As described above, the compound represented by the formula (1) of the present invention (such as a dioxaanthanthrene compound) is suitable as an organic semiconductor or an intermediate thereof. Therefore, the present invention also includes an electronic device (for example, one selected from a photoelectric conversion element, a switching element, and a rectifying element) including the compound represented by the formula (1) (or a derivative thereof).

Further, the present invention includes a novel method for producing a compound that can be a precursor of the compound represented by the formula (1). That is, this method is a method for producing a compound represented by the following formula (2a-1),
A compound represented by the following formula (2b-1) and N, N-dihalo-5,5-dialkylhydantoin (for example, N, N-diiodo-5,5-dimethylhydantoin) are reacted to form the following formula ( A step of obtaining a compound represented by 2b-2);
The compound represented by (2b-2) obtained in this step is reacted with N, N-dihalo-5,5-dialkylhydantoin and trifluoromethanesulfonic acid and represented by the following formula (2c-1). Obtaining a compound;
And solvolysis of the compound represented by the following formula (2c-1) obtained in this step to obtain a compound represented by the following formula (2a-1).

(Wherein, X ¹ is a halogen atom, R ^{1a to} R ^4a are hydrogen atoms or halogen atoms, and at least one of R ^{1a to} R ^4a (for example, R ^2a and / or R ^3a ) is a halogen atom. )

  The novel compound of the present invention is a novel anthrene compound having a formyl group at a specific position, and is useful as an organic semiconductor or an intermediate (precursor) thereof. In the method of the present invention, such an anthanthrene compound can be efficiently produced by a simple or easy method of cyclization reaction (typically reaction in the presence of a base).

[Anthanthrene compounds]
The compound of the present invention (anthanthrene-based compound, compound having an anthanthrene skeleton) is represented by the following formula (1).

(In the formula, E represents an oxygen atom or a sulfur atom, R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom or a substituent, and R ¹ and R ² , R ² and R ^3, or R ³ and R ⁴ are bonded to each other. And may form a ring.)
In said formula (1), E is an oxygen atom or a sulfur atom, and two E may be the same or different. Preferred E may be an oxygen atom.

In the formula (1), the substituent represented by R ^{1 to} R ⁴ is not particularly limited, and examples thereof include hydrocarbon groups [eg, alkyl groups (eg, methyl, ethyl, propyl, isopropyl, butyl, s A linear or branched C _1-10 alkyl group such as -butyl, t-butyl, pentyl group, preferably a C _1-6 alkyl group, more preferably a C _1-4 alkyl group), a haloalkyl group (for example, Halo C _1-4 alkyl groups such as chloromethyl, trichloromethyl, trifluoromethyl, tetrafluoropropyl groups, etc.), alkenyl groups (for example, C _2-6 alkenyl groups such as vinyl, propenyl, isopropenyl, butenyl groups, preferably Is a _C2-4 alkenyl group), a cycloalkyl group (for example, a _C5-10 cycloalkyl group such as a cyclohexyl group). , Aryl groups (eg, C _6-14 aryl groups such as phenyl group, methylphenyl group (tolyl group), ethylphenyl group, dimethylphenyl group (xylyl group), naphthyl group), aralkyl groups (eg, benzyl, phenethyl group) C _6-10 aryl-C _1-4 alkyl group, etc.]], halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom etc.), hydroxyl group, mercapto group, (thio) ether group [eg, An alkoxy group (for example, a C _1-6 alkoxy group such as methoxy, ethoxy, butoxy, t-butoxy group), an alkylthio group (for example, a C _1-6 alkylthio group corresponding to the above alkoxy group such as a methylthio group), an aryloxy group _{(C 6-10} aryloxy groups such as phenoxy group), hydroxyalkyl Kill group (e.g., hydroxymethyl, hydroxy C _1-10 alkyl group such as hydroxyethyl group), mercapto group (e.g., mercaptomethyl, mercapto C _1-10 alkyl group such as mercaptoethyl group), a formyl group, an acyl group [For example, alkylcarbonyl groups (for example, C _1-6 alkyl-carbonyl groups such as acetyl and propionyl groups), aroyl groups (for example, benzoyl groups and the like)], carboxyl groups, ester groups [for example, alkoxy-carbonyl groups ( methoxycarbonyl, ethoxycarbonyl, C _1-6 alkoxy such as butoxycarbonyl group - carbonyl group), aryloxycarbonyl group (such as phenoxycarbonyl group), alkylamino such as an amino group, a substituted amino group (e.g., dimethylamino group Group), a carbamoyl group, a nitro group, C _1-10 trialkylsilyl group such as a cyano group, a silicon atom-containing group {e.g., silyl group [for example, trialkylsilyl group (e.g., trimethylsilyl group, t- butyl dimethylsilyl group A substituted silyl group such as)], a phosphorus atom-containing group {eg, a phosphino group [eg, a diarylphosphino group (eg, a C _6-10 arylphosphino group such as diphenylphosphino group)], a phosphinyl group [ For example, a diarylphosphinyl group (for example, a diC _6-10 arylphosphinyl group such as a diphenylphosphinyl group)], etc.], a substituent in which these substituents are bonded to each other [for example, an alkoxyaryl group ( For example, a C _1-4 alkoxy C _6-10 aryl group such as a methoxyphenyl group)] and the like Can be mentioned.

In Formula (1), R ¹ and R ² , R ² and R ^3, or R ³ and R ⁴ may be bonded to each other to form a ring [or R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ may be bonded to each other to form a divalent group]. Examples of such rings include hydrocarbon rings [eg, cycloalkane rings (eg, C _5-10 cycloalkane rings such as cyclopentane and cyclohexane rings), arene rings (eg, benzene rings, naphthalene rings, etc.). Cyclic or condensed polycyclic C _6-14 arene ring)], hetero ring [eg, oxacycloalkane ring (eg, oxa C _4-6 cycloalkane ring such as oxacyclopentane ring, oxacyclohexane ring), azacyclo Alkane ring, thiocycloalkane ring, etc.]. Typical rings include an arene ring, a heterocyclic ring, and the like, and in particular, a ring that forms an aromatic ring together with an anthanthrene skeleton (for example, a dioxaanthanthrene skeleton) may be used. The ring may further be a ring substituted with the above-mentioned exemplified substituents. R ² may form a ring with R ¹ and R ³ , and R ³ may form a ring with R ² and R ⁴ , respectively. For example, when R ² forms a benzene ring with both R ¹ and R ³ (or R ³ is both R ² and R ⁴ ), a naphthalene ring is formed, and all of R ^{1 to} R ⁴ are benzene. In the case of forming a ring, a phenanthrene ring is formed together with a naphthalene ring constituting an anthanthrene skeleton.

In the formula (1), R ^{1 to} R ⁴ may be the same or different from each other. Two R ^{1 s} , two R ^{2 s} , two two R ^{3 s} , and two R ^{4 s} may be the same or different, and particularly the same.

In a preferred embodiment, in formula (1), at least one of R ^{1 to} R ⁴ may be a halogen atom (bromine atom, iodine atom, etc., particularly iodine atom), and in particular, at least two of R ^{2 to} R ⁴ (In particular, R ² and R ³ ) may be a halogen atom (particularly an iodine atom). In such a preferred embodiment, when all are not halogen atoms, the rest of R ^{1 to} R ⁴ may be hydrogen atoms or substituents other than halogen atoms.

The typical combinations of R ^{1 to} R ⁴ are shown below.

[Production method]
The anthanthrene compound of the present invention is not particularly limited, but is a compound represented by the following formula (2) (2,2′-dihydroxy or dimercapto-3,3′-diformyl-8,8′-dihalo-1, The compound can be efficiently obtained by reacting (cyclizing) a compound having a 1′-binaphthyl skeleton or the like. That is, when a compound represented by the following formula (2) is reacted, in the following formula (2), HX (dehalogenation) is present between the 1-position and the 8′-position and between the 1′-position and the 8-position, respectively. A cyclization reaction (a reaction forming -E-) occurs with elimination of hydrogen and the like, and the compound of the present invention is obtained.

(In the formula, X represents a leaving group that can be removed by reacting with the group -EH, and E and R ^{1 to} R ⁴ are the same as above.)
In the above formula (2), the group X is a group -EH (or a hydrogen atom constituting the group -EH), that is, HX by reaction with a hydroxyl group or a mercapto group (constituting a hydroxyl group or a mercapto group). There is no particular limitation as long as cyclization (formation of -E-) is possible with elimination of, for example, halogen atom (chlorine atom, bromine atom, iodine atom, etc.), alkanesulfonyloxy group (methanesulfonyloxy group, etc.) C _1-4 alkanesulfonyloxy group) of haloalkane sulfonyloxy group (e.g., halo C _1-4 alkanesulfonyloxy group such as trifluoromethanesulfonyloxy group), an arylsulfonyl group (e.g., such as tosyl group C _{6- 10} arylsulfonyloxy group) and the like. Among these, a halogen atom (particularly an iodine atom) is preferable. The two Xs may be the same or different groups, and may usually be the same. Moreover, in Formula (2), R < ¹ > -R < ⁴ > is the same as that of the said Formula (1) including a preferable aspect.

  The compound represented by the formula (2) is not particularly limited, and the compounds represented by the following formula (2a) are coupled using a conventional method (for example, a method described in WO2011 / 111762). It can be produced by (dehydrogenation coupling).

(In the formula, X and R ^{1 to} R ⁴ are the same as above.)
The compound represented by the formula (2a) is easily selectively dehydrogenated between the hydrogen atoms at the 1-position, but if necessary, the compound (dehydrogenated coupling between the hydrogen atoms at the 1-position ( That is, the compound represented by the formula (2) may be used separately from the reaction product. Further, the compound represented by the formula ^(2a), by using a combination of R 1 to R ⁴ are different compounds, the two ^{R 1,} R 2, ^{R 3} and / or ^{R 4} in a different formula (2) The compound represented is obtained.

(Compound represented by Formula (2a))
As the compound (2-naphthaldehydes) represented by the formula (2a), a commercially available product may be used, and a compound synthesized by a conventional method (for example, a method described in WO2011 / 111762) is used. May be.

  For example, among the compounds represented by the formula (2a), a compound in which X is a halogen atom includes a compound (2b) represented by the following formula and an N, N-dihalo-5,5-dialkylhydantoin (for example, N, N-diiodo-5,5-dimethylhydantoin and the like) and trifluoromethanesulfonic acid are reacted to produce a compound represented by the following formula (2c), and this compound (2b) is solvolyzed (hydrolyzed). , Methanol decomposition, etc.). The solvolysis may be performed in the presence of an alkali or an acid.

(In the formula, X ¹ is a halogen atom, and R ^{1 to} R ⁴ are the same as above.)
That is, in the above reaction, a trifluoromethanesulfonyloxy group is introduced at the 3-position, and the 5-position of 2-naphthaldehydes is halogenated.

In this reaction, in formula (2b), at least 8-position of 2-naphthaldehydes is halogenated, but in formula (2b), a compound in which R ^{1 to} R ⁴ are hydrogen atoms is used. In (2c), a compound in which at least one of R ^{1 to} R ⁴ and X ¹ are a halogen atom can also be obtained. For example, a compound represented by the following formula (2b-1), N, N-dihalo-5,5-dialkylhydantoin (such as N, N-diiodo-5,5-dimethylhydantoin) and trifluoromethanesulfonic acid May be reacted to produce a compound represented by the following formula (2c-1).

(Wherein, X ¹ is a halogen atom, R ^{1a to} R ^4a are hydrogen atoms or halogen atoms, and at least one of R ^{1a to} R ^4a (for example, R ^2a and / or R ^3a ) is a halogen atom. )
In such a reaction, halogenation can be carried out stepwise by utilizing the difference in halogenation rate between 5-position and 6-9 position of 2-naphthaldehyde. For example, the compound represented by the above formula (2b-1) is reacted with N, N-dihalo-5,5-dialkylhydantoin in the presence of an acid catalyst (for example, trifluoromethanesulfonic acid) to form the following formula. The compound represented by (2b-2) was produced, and the obtained compound represented by (2b-2) was reacted with N, N-dihalo-5,5-dialkylhydantoin and trifluoromethanesulfonic acid. You may manufacture the compound represented by the said Formula (2c-1).

(In the formula, R ^{1a to} R ^4a are hydrogen atoms or halogen atoms, and at least one of R ^{1a to} R ^4a (for example, R ^2a and / or R ^3a ) is a halogen atom.)
In the above reaction, the proportion of the compound represented by formula (2b-1) and N, N-dihalo-5,5-dialkylhydantoin is less likely to cause halogenation at the 8-position of 2-naphthaldehyde. From the viewpoint, 1 mol of the compound represented by the formula (2b-1) is 3 mol or less (for example, 1 to 2.8 mol) of N, N-dihalo-5,5-dialkylhydantoin, preferably 1 It may be about 2 to 2.5 mol, more preferably about 1.3 to 2.3 mol, particularly about 1.5 to 2.1 mol.

  The reaction (cyclization reaction) of the present invention may be usually performed in the presence of a base. By using a base, the naphthoxy anion is generated by hydrogen abstraction of the group -EH, the nucleophilic attack to the carbon atom substituted by the group -X of the generated naphthoxy anion, and the elimination (addition elimination) of the group X. It seems that a series of reactions easily proceed and a ring structure is easily formed. Examples of the base include, but are not limited to, carboxylic acids such as organic bases {eg, organic acid salts [eg, acetates (eg, alkali acetates or alkaline earth metal salts such as sodium acetate, potassium acetate, calcium acetate)]. Salts (such as carboxylic acid metal salts)], metal alkoxides (for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide), amines [for example, trialkylamine (such as triethylamine)) Secondary amines], inorganic bases [eg, metal hydroxides (eg, alkali hydroxides or alkaline earth metal salts such as sodium hydroxide, potassium hydroxide, calcium hydroxide), metal carbonates (eg, lithium carbonate) , Alkalis such as potassium carbonate, sodium carbonate, cesium carbonate Alkaline earth metal carbonates), the metal hydrogen carbonate (e.g., potassium hydrogen carbonate, alkali or alkaline earth metal bicarbonates, such as sodium bicarbonate), ammonia, etc.], and others. The bases may be used alone or in combination of two or more.

In the present invention, even a general base such as a carboxylate [e.g., an alkanoate such as acetate (e.g., _C1-4 alkanoate)] or a metal hydroxide is efficiently dehydrohalogenated. Reaction can be promoted. Therefore, the method of the present invention is extremely simple and excellent in versatility.

  The ratio of the base can be selected from a range of, for example, about 0.1 to 30 molar equivalents (for example, 0.5 to 25 molar equivalents) with respect to 1 mol of the compound represented by the formula (2). The molar equivalent may be 1.5 to 15 molar equivalents (for example, 1.8 to 12 moles), more preferably 2 molar equivalents or more (for example, 2 to 10 molar equivalents).

  In the reaction, a metal catalyst may be used as necessary. Examples of the metal catalyst include transition metal catalysts such as palladium catalysts [eg, palladium compounds (palladium acetate, palladium chloride, etc.), tungsten catalysts, etc.]. The metal catalysts may be used alone or in combination of two or more.

  The ratio of the metal catalyst is, for example, 0.0001 to 3 mol, preferably 0.0005 to 1 mol, and more preferably 0.001 to 0.00 mol per 1 mol of the compound represented by the formula (2). About 5 mol (for example, 0.005-0.3 mol) may be sufficient. The ratio of the metal catalyst is, for example, 0.00001 to 1 mol, preferably 0.0001 to 0.5 mol, more preferably 0.001 to 0.3 mol (for example, 0 mol) with respect to 1 mol of the base. 0.005 to 0.1 mol).

  The reaction can be performed in the presence or absence of a solvent. The solvent is not particularly limited as long as it is inert in the reaction. For example, hydrocarbons (for example, aliphatic hydrocarbons such as hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclohexane and cyclopentane) Aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (such as haloalkanes such as methylene chloride and chloroform), esters (such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether) Acetates such as monoacetate), ketones (eg, chain ketones such as acetone and ethyl methyl ketone; cyclic ketones such as cyclohexanone), ethers (eg, diethyl ether, dibutyl ether, propylene glycol monomethyl ether, Jeechile Chain ethers such as glycol dimethyl ether; cyclic ethers such as dioxane and tetrahydrofuran), alcohol solvents (eg, alkanols such as methanol, ethanol, isopropanol, and butanol), nitrile solvents (eg, acetonitrile, benzonitrile, etc.), Nitro solvents (for example, nitrobenzene and the like), amides (dimethylformamide and the like), water and the like can be mentioned. These solvents may be used alone or in combination of two or more.

  The reaction may be carried out under cooling, at room temperature or under heating, and particularly under heating. Although reaction temperature is not specifically limited, For example, 30-200 degreeC (for example, 40-180 degreeC), Preferably it is 50-160 degreeC, More preferably, it is about 60-150 degreeC (for example, 70-130 degreeC), It may be about 50-150 degreeC (for example, 60-100 degreeC) normally. In addition, reaction time can be suitably selected according to reaction temperature, and you may adjust, confirming the grade of the production | generation of the compound represented by Formula (1) using gas chromatography etc.

  The reaction may be performed under normal pressure, increased pressure, or reduced pressure, or may be performed under reflux. The reaction may be performed in an oxidizing atmosphere, but may be generally performed in a non-oxidizing atmosphere [for example, in a nitrogen gas or a rare gas (such as helium or argon)].

  After completion of the reaction, the product may be isolated using a conventional separation and purification means such as concentration, drying, crystallization, recrystallization, filtration, extraction, distillation, chromatography and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Synthesis example]
In the following two synthesis methods, 5,5 ′, 6,6 ′, 8,8′-hexaiodo-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl was synthesized as follows. Was synthesized.

[Synthesis Example 1]
(1) Preparation of 5,7,8-triiodo-3- (trifluoromethylsulfonyl) oxy-2-naphthaldehyde N, N′-diiodo-5,5-dimethylhydantoin (17.0 g, 44 under nitrogen atmosphere) 7 mmol), CH ₂ Cl ₂ (160 mL) was added, trifluoromethanesulfonic acid (7.93 mL, 89.6 mmol) was added dropwise at 60 ° C., and then 2-naphthaldehyde (2.00 g, 12. 8 mmol) was dissolved in CH ₂ Cl ₂ (40 mL) in the same manner. After stirring at 60 ° C. for 3 hours, the reaction solution was quenched by adding an aqueous sodium sulfite solution. The organic layer was washed with water and saturated brine, dried over magnesium sulfate, filtered and concentrated. Acetonitrile is added to the obtained brown viscous body and dissolved, and recrystallization is performed overnight at −20 ° C., whereby a compound represented by the following formula, that is, 5,7,8-triiodo-3- (trifluoromethylsulfonyl) ) Oxy-2-naphthaldehyde (3.36 g, 38%) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 10.35 (s, 1H), 8.89 (s, 1H), 8.65 (s, 1H), 8.13 (s, 1H)
¹³ C-NMR (CDCl ₃ ) δ: 185.90, 149.37, 147.01, 143.54, 135.78, 135.20, 129.13, 126.69, 119.21 (q, J = 319.7 Hz), 116.36, 112.56, 99.73.

(2) Preparation of 5,7,8-triiodo-3-hydroxy-2-naphthaldehyde Synthesized 5,7,8-triiodo-3- (trifluoromethylsulfonyloxy) -2-naphthaldehyde (1.00 g, 1,4-dioxane (4.70 mL) and methanol (2.20 mL) were added to 1.47 mmol), and then a 1N aqueous sodium hydroxide solution (4.40 mL, 4.40 mmol) was added dropwise thereto. Stir for hours. After completion of the reaction, the reaction solution was quenched by adding 6N hydrochloric acid aqueous solution. The suspension was subjected to filtration, and the residue was washed with water, followed by air drying, and the compound represented by the following formula, ie, 5,7,8-triiodo-3-hydroxy-2-naphthaldehyde (793 mg, 98%).

¹ H-NMR (CDCl ₃ ) δ: 10.52 (s, 1H), 10.20 (s, 1H), 8.58 (s, 1H), 8.51 (s, 1H), 7.59 ( s, 1H).

(3) Preparation of 5,5 ′, 6,6 ′, 8,8′-hexaiodo-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl Iron chloride hexahydrate (1 .97 g, 7.29 mmol) and 5,7,8-triiodo-3-hydroxy-2-naphthaldehyde synthesized (200 mg, 364 μmol) were ground in a mortar and mixed. The resulting mixture was placed in a 50 mL sample tube, 0.2 mL of H ₂ O was added and slowly stirred for 1 minute. It was stirred with heating at 210 w for 780 seconds using a μ reactor (Shikoku Keiki Kogyo Co., Ltd.). After the reaction, 30 mL of 6N HCl was added and stirred for 15 hours, followed by filtration with water and drying to obtain a tan crude product. This was dissolved in bromobenzene and purified by flash column chromatography (chloroform) to obtain an orange solid. By repeating this operation once more, a compound represented by the following formula, that is, 5,5 ′, 6,6 ′, 8,8′-hexaiodo-3,3′-diformyl-2,2′-dihydroxy-1, 1'-binaphthyl was obtained.

_{^{1 H-NMR (CDCl 3)}} δ11.07 (s, 2H), 10.13 (s, 2H), 8.82 (s, 2H), 8.67 (s, 2H).

[Synthesis Example 2]
(1) Preparation of 7,8-diiodo-2-naphthaldehyde N 2 N′-Diiodo-5,5-dimethylhydantoin (4.88 g, 12.8 mmol) was added CH ₂ Cl ₂ (50 mL) under a nitrogen atmosphere. A solution of 2-naphthaldehyde (1.00 g, 6.40 mmol) dissolved in CH ₂ Cl ₂ (10 mL) after dropwise addition of trifluoromethanesulfonic acid (1.13 mL, 12.8 mmol) to the added suspension solution. Was also dropped in the same manner. After stirring at room temperature for 30 minutes, the reaction solution was quenched by adding an aqueous sodium sulfite solution. The organic layer was washed with water and saturated brine, dried over magnesium sulfate, filtered and concentrated to give a crude product (2.46 g) as a yellow solid. The crude product was purified by silica gel column chromatography (chloroform) to obtain a compound represented by the following formula, that is, 7,8-diiodo-2-naphthaldehyde (2.26 g, 87%).

¹ H-NMR (CDCl ₃ ) δ: 10.27 (s, 1H), 8.52 (d, J = 1.6 Hz, 1H), 8.16 (d, J = 8.8 Hz, IH), 8 .03 (dd, J = 8.6, 1.4 Hz, 1H), 7.90 (d, J = 7.6 Hz, 1H), 7.85 (d, J = 7.6 Hz, 1H).
¹³ C-NMR (CDCl ₃ ) δ: 191.29, 140.79, 139.22, 138.89, 137.65, 135, 83, 134.35, 134.31, 125.21, 102.08, 100.36.

(2) Preparation of 5,7,8-triiodo-3- (trifluoromethylsulfonyloxy) -2-naphthaldehyde To N, N′-diiodo-5,5-dimethylhydantoin (186 mg, 490 μmol) under nitrogen atmosphere After trifluoromethanesulfonic acid (174 μL, 1.97 mmol) was added dropwise to the suspension solution to which CH ₂ Cl ₂ (2.0 mL) was added, the resulting 7,8-diiodo-2-naphthaldehyde (100 mg, 245 μmol) was obtained. A solution in which CH ₂ Cl ₂ (3.0 mL) was dissolved was also added dropwise. After stirring for 30 minutes at room temperature, an aqueous sodium sulfite solution was added to the reaction solution to quench it. The organic layer is washed with water and saturated brine, dried over magnesium sulfate, filtered and concentrated, and a compound represented by the following formula, ie, 5,7,8-triiodo-3- (trifluoromethylsulfonyloxy) 2-Naphthaldehyde (134 mg, 80%) was obtained.

¹ H-NMR (CDCl ₃ ) δ 10.35 (s, 1H), 8.89 (s, 1H), 8.65 (s, 1H), 8.13 (s, 1H)
¹³ C-NMR (CDCl ₃ ) δ 185.90, 149.37, 147.01, 143.54, 135.78, 135.20, 129.13, 126.69, 119.21 (q, J = 319. 7 Hz), 116.36, 112.56, 99.73.

[Example 1]
Under a nitrogen atmosphere, the compound (5,5 ′, 6,6 ′, 8,8′-hexaiodo-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl obtained in Synthesis Example 1 was used. ) 0.100 g, (0.091 mmol), potassium acetate (AcOK) 75.5 mg (0.547 mmol), palladium acetate (Pd (Oac) ₂ ) 1.15 mg (5.1 μmol) with a Dimroth flask Then, 2.5 ml of ethyl methyl ketone (MeCOEt) was added and stirred at 120 ° C. for 3 hours. After the reaction, the solvent was concentrated, and the product (purity 98% or more) was obtained by washing with chloroform and water on the filter paper. The product was analyzed by NMR and high resolution mass spectrometry (HMRS) and confirmed to be the following compound.

¹ H-NMR (DMSO-D ₆ ): δ 10.43 (s, 2H), 8.17 (s, 2H), 8.16 (s, 2H)
_{^{HRMS (FAB +) M + calcd}} for C 22 H 6 I 4 O 4 841.6445, found 841.6456.

[Example 2]
Under a nitrogen atmosphere, the compound (5,5 ′, 6,6 ′, 8,8′-hexaiodo-3,3′-diformyl-2,2′-dihydroxy-1,1′-binaphthyl obtained in Synthesis Example 2 was used. ) 0.050 g (0.0456 mmol) and potassium hydroxide (KOH) 5.62 g (0.100 mmol) were placed in a two-necked flask equipped with a Dimroth, and 3.0 ml of tetrahydrofuran (THF) was added thereto at 80 ° C. for 5 hours. Stir for hours. After the reaction, the product was cooled to room temperature and washed with THF and ethyl acetate (AcOEt) on a filter paper to obtain a product (purity 98% or more). The product was analyzed by NMR and HMRS, and confirmed to be the following compound (that is, the same compound obtained in Example 1).

¹ H-NMR (DMSO-D ₆ ): δ 10.43 (s, 2H), 8.17 (s, 2H), 8.16 (s, 2H)
_{^{HRMS (FAB +) M + calcd}} for C 22 H 6 I 4 O 4 841.6445, found 841.6456

  The novel ananthrene compound of the present invention can be used as an organic semiconductor, and can also be used as an intermediate (or precursor) of an organic semiconductor because it has a formyl group (and a halogen atom as a substituent). . Moreover, in the method of the present invention, the above-described anthanthrene compounds can be easily and efficiently obtained by a cyclization reaction involving dehydrohalogenation.

  Examples of the organic semiconductor include various devices such as photoelectric conversion elements (solar cell elements, organic electroluminescence elements, etc.), rectifying elements (diodes), transistors, and the like.

Claims (7)

A compound represented by the following formula (1).

(Wherein E is an oxygen atom or sulfur atom, R ^{1 to} R ⁴ are the same or different and are a hydrogen atom , hydrocarbon group, halogen atom, hydroxyl group, mercapto group, (thio) ether group, hydroxyalkyl group, mercaptoalkyl) Group, formyl group, acyl group, carboxyl group, ester group, amino group, substituted amino group, carbamoyl group, nitro group, cyano group, silicon atom-containing group or phosphorus atom-containing group , at least one of R ^{2 to} R ⁴ One is an iodine atom, and R ¹ and R ² , R ² and R ^3, or R ³ and R ⁴ may be bonded to each other to form a ring.) In the formula (1), ^{R 1} is hydrogen ^atom, at least two of claims 1 Symbol placement compound is an iodine atom R 2 to R ^4. The compound according to claim 1 or 2 , wherein in formula (1), E is an oxygen atom, R ¹ and R ⁴ are hydrogen atoms, and R ² and R ³ are iodine atoms. The method to manufacture the compound in any one of Claims 1-3 by making the compound represented by following formula (2) cyclize.

(In the formula, X represents a leaving group which can be removed by reacting with the group -EH, E is an oxygen atom or a sulfur atom , and R ^{1 to} R ⁴ are the same or different and represent a hydrogen atom, a hydrocarbon group, a halogen atom. , Hydroxyl group, mercapto group, (thio) ether group, hydroxyalkyl group, mercaptoalkyl group, formyl group, acyl group, carboxyl group, ester group, amino group, substituted amino group, carbamoyl group, nitro group, cyano group, silicon An atom-containing group or a phosphorus atom-containing group, wherein at least one of R ^{2 to} R ⁴ is an iodine atom, R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ are bonded to each other to form a ring You may do it .) The production method according to claim 4 , wherein in formula (2), X is an iodine atom. The production method according to claim 4 or 5 , wherein the compound represented by the formula (2) is reacted in the presence of a base. The production method according to claim 6 , wherein the base is at least one selected from a carboxylic acid metal salt and a metal hydroxide.