JP2012116825A - Method for producing acene diimide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method easily producible of an acene diimide compound.SOLUTION: The method for producing an acene diimide compound comprises a step of obtaining the acene diimide compound by reacting an acene dicarboxylic acid compound or a carboxylic derivative thereof with an isocyanate compound in the presence of a catalyst. For obtaining the acene diimide compound, the method may include a step of obtaining 1,2-diol by subjecting an acene compound and vinylene carbonate to Diels-Alder reaction, and a step of obtaining the acene dicarboxylic compound by oxidative cleavage of the resulting 1,2-diol.

Description

  The present invention relates to a method for producing an acene diimide compound such as anthracene diimide or tetracene diimide.

  As represented by naphthalene diimide and perylene diimide, aromatic diimides have low LUMO and are attracting attention as n-type organic electronic materials. About these aromatic diimides, various research and development are performed aiming at the application to an organic solar cell or organic EL. Conventionally, as a method for producing aromatic diimides, there are generally known methods for synthesizing naphthalene diimide by oxidizing and decomposing pyrene or synthesizing perylene diimide by coupling naphthalene imide. The general manufacturing method of group diimides has not been established.

  As a method for producing an acene diimide compound that is an aromatic diimide, for example, Patent Document 1 discloses a method for synthesizing a tetracene diimide compound from tetracene. According to the method disclosed in Patent Document 1, tetracene is reacted with bromine to bromination at positions 5, 6, 11 and 12, and then n-BuLi and formaldehyde are sequentially reacted to replace the bromo group with a hydroxymethyl group. Furthermore, the hydroxymethyl group is oxidized to a carboxy group with potassium permanganate to obtain tetracene substituted at the 5, 6, 11 and 12 positions with the carboxy group. Then, the 5-position and 6-position carboxy groups and the 11-position and 12-position carboxy groups are dehydrated and condensed to acid anhydrides, and then reacted with an alkylamine to obtain a tetracene diimide compound.

Chinese Patent Application No. 1990488

  However, the method disclosed in Patent Document 1 is considered to be difficult to implement if judged from common sense of organic synthetic chemistry, and is not suitable for at least industrial mass synthesis. That is, in this method, by reacting 5,6,11,12-tetrabromotetracene with n-BuLi, tetracene in which lithium is bound to four positions of 5, 6, 11, 12 is theoretically obtained as an intermediate. However, such a compound is chemically very unstable and is very difficult to be subjected to the next reaction as desired, or the yield itself is considered to be very low. In the reaction of oxidizing a hydroxymethyl group to a carboxy group, the oxidation capability of potassium permanganate is so strong that the tetracene skeleton is decomposed and the desired product (5,6,11,12-tetracarboxytetracene) is obtained. Or the yield is considered to be very low. In fact, according to experimental findings by the present inventors, the target compound could not be obtained by such a reaction. Therefore, it is considered that it is actually difficult to produce an acenediimide compound by the method disclosed in Patent Document 1.

  This invention is made | formed in view of the said situation, The objective is to provide the method which can manufacture an acene diimide compound simply.

  The present inventors have intensively studied to solve the above problems. As a result, if four carboxy groups are not introduced into the acene compound as in the method described in Patent Document 1, but the number of carboxy groups to be introduced is two, the acene diimide compound is very simple and efficient. The present invention was completed by finding that the dicarboxylic acid compound itself as an intermediate compound can be easily produced.

  The acene diimide compound according to the present invention is prepared by reacting an acene dicarboxylic acid compound represented by the following formula (3) or a carboxylic acid derivative thereof with an isocyanate compound represented by the following formula (4) in the presence of a catalyst. Or an acenediimide compound represented by the following formula (2).

  In the above formulas (1) to (3), m represents an integer of 0 or more, n represents an integer of 0 or more, and in formulas (1), (2), (4), R represents 1 carbon atom. Represents an -20 alkyl group or an aryl group having 6 to 12 carbon atoms.

  As the catalyst used when the acene dicarboxylic acid compound represented by the formula (3) or the carboxylic acid derivative thereof is reacted with the isocyanate compound represented by the formula (4), a Lewis acid catalyst is preferable.

  In the production method of the present invention, the acene dicarboxylic acid compound represented by the formula (3) is subjected to Diels-Alder reaction between the acene compound represented by the following formula (5) and vinylene carbonate to obtain 1,2-diol. The obtained 1,2-diol is preferably obtained by oxidative cleavage. That is, the method for producing an acene diimide compound of the present invention includes a step of obtaining 1,2-diol by Diels-Alder reaction of an acene compound represented by the following formula (5) and vinylene carbonate, and the obtained 1,2- It is preferable to further include a step of oxidative cleavage of the diol to obtain the acene dicarboxylic acid compound represented by the formula (3).

[In Formula (5), m and n are the same as said Formula (1)-Formula (3). ]

  Through the above steps, the acene dicarboxylic acid compound represented by the formula (3) can be obtained very easily from the acene compound represented by the formula (5). Therefore, the acene diimide compound can be more easily produced using the acene compound as a starting material.

  In the above reaction, the oxidative cleavage of 1,2-diol is preferably performed in the presence of periodic acid, sodium periodate, 2-iodoxybenzoic acid, Dess-Martin periodinane, or lead tetraacetate.

  Conventionally, silicon or the like has been used as a semiconductor material, but in Japan where resources are scarce, a cheaper organic semiconductor material is eagerly desired. According to the production method of the present invention, an acenediimide compound that can be an organic semiconductor material can be easily produced. Therefore, the present invention contributes to the development and practical application of organic solar cells, organic EL, organic transistors, and the like. It is very useful in industry.

  Hereinafter, the present invention will be described in detail including the production of the acene dicarboxylic acid compound (3) which is an intermediate compound.

1. Diels-Alder reaction step As the starting material compound of the present invention, it is preferable to use an acene compound (5) and vinylene carbonate (6) which are relatively easily available. From these compounds, 1,2-diol is obtained by Diels-Alder reaction and alkaline hydrolysis reaction.

  In formula (5), m represents an integer of 0 or more, and n represents an integer of 0 or more. Therefore, m + n may be 0 or more. The upper limits of m and n are not particularly limited, but m + n is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less, from the viewpoint of ease of production and availability of the acene compound represented by formula (5). .

  The Diels-Alder reaction is performed by heating a solution containing the acene compound (5) and vinylene carbonate (6). In the Diels-Alder reaction, in order to increase the reaction yield based on the acene compound (5), vinylene carbonate (6) is more than equimolar amount of the acene compound (5) (more preferably more than 1.5 times molar amount). It is preferable to use it. The Diels-Alder reaction may be performed for 6 hours to 5 days in a temperature range of 100 ° C. to 260 ° C., for example, in an inert gas atmosphere such as nitrogen gas or argon gas. What is necessary is just to adjust reaction temperature and reaction time suitably according to the thermal stability of a starting material or a reaction product, and the progress of reaction.

  In the Diels-Alder reaction, vinylene carbonate (6) is predominantly reacted with the benzene ring skeleton close to the center of the acene compound (5). In the acene compound (5), the benzene ring skeleton closer to the center is more likely to have an electron density, and the vinylene carbonate (6) is likely to be selectively added to a site having a higher electron density.

  By reacting the acene compound (5) with the vinylene carbonate (6), a 1,2-diol compound represented by the following formula (7) is obtained. In the following formula (7), m and n are the same as in the above formula (5). Since vinylene carbonate (6) has a predominant reaction with the benzene ring skeleton close to the center of the acene compound (5), a 1,2-diol compound of the following formula (7) can be obtained in a higher yield. Mn is preferably −2 or more and 4 or less, more preferably −1 or more and 3 or less, and further preferably 0 or more and 2 or less.

2. Oxidative cleavage step Next, the 1,2-diol obtained is oxidatively cleaved to obtain an acenedialdehyde compound (8). In the following formula (8), m and n are the same as in the above formula (5).

  The oxidative cleavage reaction of the 1,2-diol structural moiety is preferably performed in the presence of an oxidizing agent. As the oxidizing agent, a known oxidizing agent can be used. Preferably, for example, periodic acid, sodium periodate, 2-iodoxybenzoic acid, Dess-Martin Periodinane (DMP), or Use lead tetraacetate. Dess-Martin periodinane is a common name for 1,1,1-triacetoxy-1,1-dihydro-1,2-benziodoxol-3 (1H) -one. If such an oxidizing agent is used, the oxidative cleavage reaction of the 1,2-diol structure can be efficiently advanced under relatively mild conditions. These oxidizing agents are preferably used in a molar amount of 1.0 times or more of the oxidation equivalent necessary for oxidative cleavage of the 1,2-diol structural portion, and in a molar amount of 1.2 times or more. More preferably, a molar amount of 5.0 times or less is preferably used, and a molar amount of 3.0 times or less is more preferably used.

  A reaction that oxidatively cleaves 1,2-diol using periodic acid or sodium periodate is generally known as a Malaprade reaction. The reaction of oxidative cleavage of 1,2-diol using lead tetraacetate is generally known as the Criegee reaction. The reaction of oxidative cleavage of 1,2-diol using 2-iodoxybenzoic acid can be referred to documents such as Org. Biomol. Chem., 5, 767-771 (2007).

  In the oxidative cleavage reaction, 2-iodoxybenzoic acid is preferably used because the reaction can proceed under relatively mild conditions. In this case, it is preferable to use dimethyl sulfoxide (DMSO) as a solvent from the viewpoint of increasing the solubility of 2-iodoxybenzoic acid. The oxidative cleavage reaction using 2-iodoxybenzoic acid may be performed at a temperature range of 20 ° C. to 200 ° C. for 5 minutes to 24 hours, for example. What is necessary is just to adjust reaction temperature and reaction time suitably according to the thermal stability of a starting material or a reaction product, and the progress of reaction.

3. Oxidation step Next, the aldehyde group of the obtained acene dialdehyde compound (8) is oxidized to form a carboxy group, thereby obtaining an acene dicarboxylic acid compound (3).

  A known oxidation reaction may be used as a method for oxidizing an aldehyde group to form a carboxy group, and it is preferable to use sodium chlorite that can be oxidized under relatively mild conditions as an oxidizing agent. In particular, as a method capable of oxidizing an aldehyde group to a carboxy group under relatively mild conditions, it is preferable to use a Pinnick (Kraus) oxidation reaction using sodium chlorite. The Pinnick (Kraus) oxidation reaction is described with reference to documents such as J. Org. Chem., 45, 4825 (1980), J. Org. Chem., 45, 1175 (1980), Tetrahedron, 37, 2091 (1981). it can.

  When an aldehyde group is oxidized to a carboxy group using a Pinnick (Kraus) oxidation reaction, for example, the acenedialdehyde compound (8) is dissolved in a suitable solvent, and then 2-methyl-2-butene is added. By adding sodium chlorite and sodium dihydrogen phosphate dissolved in water, the oxidation reaction of the acenedialdehyde compound (8) proceeds.

  As a solvent for dissolving the acenedialdehyde compound (8), a solvent capable of dissolving the acenedialdehyde compound (8) and having compatibility with water may be appropriately selected. For example, dimethyl ether, diethyl ether, methyl ethyl Ethers such as ether and tetrahydrofuran: Ketones such as acetone and methyl ethyl ketone may be used.

  Sodium chlorite and sodium dihydrogen phosphate are preferably used in equimolar amounts, and sodium chlorite and sodium dihydrogen phosphate are used in an equimolar amount or more of the aldehyde group of the acenedialdehyde compound (8) (more The molar amount is preferably 1.2 times or more. The Pinnick (Kraus) oxidation reaction may be performed, for example, in a temperature range of −20 ° C. to 60 ° C. for 10 minutes to 48 hours in an inert gas atmosphere such as nitrogen gas or argon gas. What is necessary is just to adjust reaction temperature and reaction time suitably according to the thermal stability of a starting material or a reaction product, and the progress of reaction.

  Alternatively, when a corresponding dihalogen compound such as a dibromo compound is readily available or can be synthesized, it can be lithiated with butyllithium or the like, or a Grignard reagent to be reacted with carbon dioxide, whereby an acene dicarboxylic acid compound ( 3).

4). Next, the acene dicarboxylic acid compound (3) or a carboxylic acid derivative thereof is reacted with an isocyanate compound represented by the following formula (4) in the presence of a catalyst to obtain an acene diimide compound.

  In formula (3), m represents an integer of 0 or more, and n represents an integer of 0 or more. Therefore, m + n may be 0 or more. The upper limits of m and n are not particularly limited, but m + n is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less, from the viewpoint of ease of production and availability of the acene dicarboxylic acid represented by formula (3). preferable.

  In formula (4), R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

The alkyl group may be linear, branched, or have an alicyclic structure. The alkyl group may have a substituent. The substituent that the alkyl group has is preferably at least one selected from the group consisting of a halogen group and a C _6-12 aryl group. Any isocyanate compound having such an alkyl group can be obtained or produced relatively easily. As carbon number of an alkyl group, 1-12 are preferable and 1-8 are more preferable. The carbon number of the alkyl group includes the carbon number of the substituent bonded to the alkyl group. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, i-butyl group, tert-butyl group, and pentyl. Group, hexyl group, heptyl group, octyl group, dodecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, benzyl group, 2-phenylethyl group, trifluoromethyl group and the like.

The aryl group may be monocyclic, polycyclic (including fused cyclic), or a plurality of aromatic rings connected by a single bond. The aryl group may have a substituent. The substituent that the aryl group has is preferably at least one selected from the group consisting of a halogen group, a C _1-6 alkyl group, a C _1-6 halogenated alkyl group, and a C _1-6 alkoxy group. Any isocyanate compound having such an aryl group can be obtained or produced relatively easily. As carbon number of an aryl group, 6-10 are more preferable. The carbon number of the aryl group includes the carbon number of the substituent bonded to the aryl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group.

  The acene dicarboxylic acid compound (3) may be used in the form of a free carboxylic acid, or may be used as a carboxylic acid derivative such as an acid anhydride or an acid halide. The carboxylic acid derivative includes an acyl derivative. What is necessary is just to convert a free carboxylic acid and a carboxylic acid derivative into arbitrary forms mutually by a well-known method.

  The acene dicarboxylic acid compound (3) is preferably used as a carboxylic acid halide (acid halide) in order to increase the reactivity between the carboxylic acid and the isocyanate. Examples of carboxylic acid halides include carboxylic acid fluorides, carboxylic acid chlorides, carboxylic acid bromides, carboxylic acid iodides, and the like, which are obtained easily and from the point of reactivity of the obtained carboxylic acid halides. As the carboxylic acid halide, a carboxylic acid chloride is preferably used. In order to make the acene dicarboxylic acid compound (3) into a carboxylic acid halide, the acene dicarboxylic acid compound may be reacted with a halogenating agent such as thionyl chloride, oxalyl chloride, sulfuryl chloride, or phosphorus trichloride. That is, the acene dicarboxylic acid halide (3) may be obtained by reacting the acene dicarboxylic acid compound (3) with the halogenating agent.

  By reacting an acene dicarboxylic acid compound represented by the formula (3) or a carboxylic acid derivative thereof with an isocyanate compound represented by the formula (4) in the presence of a catalyst, it is represented by the following formula (1) or the following formula (2). An acenediimide compound is produced.

  In the above formulas (1) and (2), m, n, and R represent the same meaning as in the above formulas (3) and (4). That is, m represents an integer of 0 or more, n also represents an integer of 0 or more, and R represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms. In addition, when obtaining the acene diimide compound shown by Formula (2), n needs to be 1 or more. That is, when n is 0, the acene diimide compound represented by the formula (2) cannot be obtained.

  As the catalyst used when the acene dicarboxylic acid compound (3) or a carboxylic acid derivative thereof and the isocyanate compound (4) are reacted (hereinafter, sometimes referred to as “imidation catalyst”), a Lewis acid catalyst may be used. preferable. By using a Lewis acid catalyst as an imidation catalyst, an imidization reaction with an isocyanate compound can proceed efficiently.

A known catalyst may be used as the Lewis acid catalyst. For example, Ag (I), B (III), Al (III), Sn (IV), Bi (III), Yb (III), Sc (III), A complex such as V (IV) or Ti (IV) may be used. Especially, it is preferable to use a bismuth catalyst from the point which an imidation reaction advances efficiently. Known ligands may be used as the ligand of the complex, and examples thereof include halogen such as chlorine, bromine and iodine; bistrifluoromethanesulfonylimide (NTf ₂ ); trifluoromethanesulfonyl (OTf) and the like.

  By reacting the acene dicarboxylic acid compound (3) or its carboxylic acid derivative with the isocyanate compound (4) under a catalyst, the isocyanate group of the isocyanate compound (4) reacts with the carboxy group of the acene dicarboxylic acid compound (3). Then, the isocyanate compound (4) is introduced into the acene dicarboxylic acid compound (3), and then the structural portion derived from the isocyanate group forms a ring in cooperation with a part of the aromatic ring of the acene dicarboxylic acid compound (3), It is considered that an acenediimide compound represented by 1) or formula (2) is obtained. Therefore, the acene diimide compound represented by the formula (1) or the formula (2) can be obtained efficiently.

  The acene dicarboxylic acid compound (3) or a carboxylic acid derivative thereof and the isocyanate compound (4) are preferably used in the following ratio range. That is, the molar ratio defined by [molar amount of isocyanate compound (4)] / [molar amount of acene dicarboxylic acid compound (3) or its carboxylic acid derivative] is preferably 1.5 or more. More preferably, it is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

  The reaction of the acene dicarboxylic acid compound (3) or its carboxylic acid derivative and the isocyanate compound (4) represented by the formula (4) (hereinafter sometimes referred to as “imidation reaction”) may be carried out in a solvent. preferable. Examples of the solvent include hydrocarbons such as benzene, toluene, p-xylene, m-xylene, octane and decane; halogen-containing hydrocarbons such as chlorobenzene, dichlorobenzene and dichloroethane. Furthermore, the reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.

  The imidization reaction may be performed, for example, in a temperature range of 20 ° C. to 200 ° C. for 10 minutes to 24 hours. What is necessary is just to adjust suitably the reaction temperature and reaction time of imidation reaction according to the thermal stability of a starting material or a reaction product, and the progress of reaction.

  In the imidization reaction, which of the compound represented by formula (1) and the compound represented by formula (2) is dominant in the resulting acenediimide compound depends on the number of rings of the acenedicarboxylic acid (3) (that is, m + n Value). Moreover, it is thought that the kind of acene diimide compound obtained preferentially changes also with the kind of imidation catalyst and reaction conditions (temperature, solvent, etc.) of imidation reaction.

  After the imidation reaction, the reaction product and the solvent may be separated by an appropriate separation means such as distillation. Further, the reaction product may be purified using an appropriate purification means such as column chromatography or recrystallization to obtain an acene diimide compound represented by formula (1) or formula (2).

  According to the production method of the present invention, as described above, by reacting the acene dicarboxylic acid compound (3) or its carboxylic acid derivative with the isocyanate compound (4) in the presence of a catalyst, the formula (1) or An acene diimide compound represented by the formula (2) can be obtained. The acene diimide compound is useful as an organic semiconductor material, for example.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the scope of the present invention is not limited thereto.

Example 1
(1) Production of 1,2-diol compound 4000 mg (17.2 mmol) of tetracene (naphthacene) was dissolved in 80 mL of xylene, 4100 mg (47.4 mmol) of vinylene carbonate was added thereto, and the mixture was stirred at 180 ° C. for 3 days under an argon atmosphere. The Diels-Alder reaction was allowed to proceed. Then, 44 mL of 4 mol / L KOH was added and hydrolyzed to obtain 4340 mg (15.1 mmol) of a 1,2-diol compound. The yield in the Diels-Alder reaction was 88%.

(2) Production of tetracenedialdehyde 50.0 mg (0.173 mmol) of the obtained 1,2-diol compound was dissolved in 3.0 mL of dehydrated DMSO and heated to 80 ° C., and then 2-iodoxybenzoic acid was added thereto. 72.5 mg (0.259 mmol) of (IBX) was added and held at 80 ° C. for 2 hours to proceed the oxidative cleavage reaction of the 1,2-diol structure portion. Thereafter, the solvent was removed and the residue was washed with methanol to obtain 35.7 mg (0.126 mmol) of tetracenedialdehyde. The yield in the oxidative cleavage reaction was 72%.

(3) Production of tetracenedicarboxylic acid 1.176 g (4.136 mmol) of the obtained tetracenedialdehyde was suspended in 250 mL of tetrahydrofuran (THF) under argon gas atmosphere together with 10.0 mL of 2-methyl-2-butene. And cooled to 0 ° C. A solution prepared by dissolving 1.190 g (13.16 mmol) of NaClO _{2 and} 1.579 g (13.16 mmol) of NaH ₂ PO ₄ in 40 mL of water was added thereto to obtain a mixed solution. The resulting mixed solution was allowed to warm to room temperature and stirred at room temperature for 16 hours to advance the aldehyde oxidation reaction. Thereafter, THF was removed, 1M HCl was added, and the precipitated solid was separated by filtration, washed with water, and further washed with CHCl ₃ to obtain 1.00 g (3.16 mmol) of tetracene dicarboxylic acid represented by the following formula (11). Got. The yield in the aldehyde oxidation reaction was 76%.

(4) Production of tetracenediimide 30.0 mg (0.0945 mmol) of the obtained tetracenedicarboxylic acid was suspended in 2.0 mL of CH ₂ Cl _{2 in} an argon gas atmosphere together with 0.3 mL of SOCl ₂ , and the mixture was brought to 0 ° C. Cooled down. Three drops of N, N-dimethylformamide (DMF) was added thereto and stirred at 0 ° C. for 60 minutes, and then the solvent was removed to obtain a tetracene dicarboxylic acid chloride. The obtained tetracene dicarboxylic acid chloride (0.0945 mmol) was dissolved in 2 mL of o-dichlorobenzene in an argon gas atmosphere together with 0.5 mL of isopropyl isocyanate, heated to 80 ° C., and further Bi (OTf). ₃ ) 0.125 g was added and held at 120 ° C. for 2 hours to advance the imidization reaction. Thereafter, the solvent was removed, the residue was purified by column chromatography, and the purified product thus obtained was washed with methanol to obtain 19.9 mg (0.0442 mmol) of a tetracene diimide compound represented by the following formula (12). It was. The yield in the imidization reaction was 47%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 9.72 (m, 4H), 7.78 (m, 4H), 5.59-5.52 (m, 2H), 1.76 (d, J = 6 .9Hz, 12H)

Example 2
In Example 1 above, 21.0 mg of a tetracene diimide compound represented by the following formula (13) was similarly used except that 0.5 mL of n-hexyl isocyanate was used instead of isopropyl isocyanate as an isocyanate compound used in the imidization reaction. 0.0392 mmol) was obtained. The yield in the imidization reaction was 42%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 9.82 (m, 4H), 7.81 (m, 4H), 4.36 (t, J = 7.7 Hz, 4H), 1.92-1.84 (M, 4H), 1.46-1.34 (m, 12H), 0.92 (t, J = 7.0 Hz, 6H)

Example 3
In Example 1 above, as the isocyanate compound used in the imidization reaction, 0.3 mL of cyclohexyl isocyanate was used instead of isopropyl isocyanate, and 0.290 mg of Bi (OTf) ₃ was used. 14.4 mg (0.0271 mmol) of the tetracenediimide compound shown were obtained. The yield in the imidization reaction was 29%.

Example 4
(1) Production of anthracene dicarboxylic acid In a reaction vessel, 25 g (74.4 mmol) of 9,10-dibromoanthracene (purchased from Tokyo Chemical Industry Co., Ltd.) was suspended in 150 mL of diethyl ether under an argon gas atmosphere. Cooled to ° C. Thereto was added dropwise 0.24 mol of n-butyllithium, and the mixture was warmed to room temperature and stirred for 1 hour. Carbon dioxide gas was blown into the reaction vessel at room temperature for 15 minutes, and then diethyl ether and water were added to the reaction solution to separate the aqueous layer. 6M HCl was added to the separated aqueous layer to precipitate the anthracene dicarboxylic acid represented by the following formula (15), which was further purified by washing with water and ethanol. 9.1 g (34.7 mmol) of anthracene dicarboxylic acid was obtained, and the yield was 46%.

(2) Production of anthracene diimide 3000 mg (1.126 mmol) of the obtained anthracene dicarboxylic acid was suspended in 15 mL of CH ₂ Cl ₂ together with 3.5 mL of SOCl _{2 in} a nitrogen gas atmosphere and cooled to 0 ° C. Three drops of DMF were added thereto, and the mixture was stirred for 60 minutes while maintaining at 0 ° C., and then the anthracene dicarboxylic acid chloride was obtained by removing the solvent. The obtained anthracene dicarboxylic acid chloride (1.126 mmol) was dissolved in 15 mL of o-dichlorobenzene together with 5 mL of isopropyl isocyanate in a nitrogen gas atmosphere, heated to 80 ° C., and further Bi (OTf) _{3 there.} 1.7g was added and it hold | maintained at 120 degreeC for 2 hours, and imidation reaction was advanced. Thereafter, the solvent was removed, the residue was purified by column chromatography, and the obtained purified product was washed with methanol to obtain 83.3 mg (0.208 mmol) of an anthracene diimide compound represented by the following formula (16). It was. The yield in the imidization reaction was 18%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 10.21 (m, J = 9.1, 1.2 Hz, 2H), 8.81 (m, J = 7.0, 1.2 Hz, 2H), 7. 99 (m, J = 9.1, 7.0 Hz, 2H), 5.49 (quintet, J = 6.9 Hz, 2H), 1.68 (d, J = 7.0 Hz, 12H)

Example 5
In Example 4 above, 100 mg of the anthracene diimide compound represented by the following formula (17) was obtained in the same manner as in Example 4 except that 2 mL of n-hexyl isocyanate was used instead of isopropyl isocyanate as the isocyanate compound used in the imidization reaction. 0.2 mmol) was obtained. The yield in the imidization reaction was 18%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 10.23 (m, 2H), 8.77-8.75 (m, 2H), 7.94 (m, J = 1.6 Hz, 2H), 4.24 (T, J = 7.7 Hz, 4H), 1.84-1.76 (m, 4H), 1.51-1.30 (m, 12H), 0.92 (t, J = 7.1 Hz, 6H)

Example 6
In Example 4, 30 mg of anthracene diimide compound represented by the following formula (18) was used in the same manner as in Example 4 except that 5 mL of cyclohexyl isocyanate was used instead of isopropyl isocyanate as the isocyanate compound used in the imidization reaction. 062 mmol) was obtained. The yield in the imidization reaction was 6%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 10.18 (m, 2H), 8.80 (m, 2H), 7.98 (m, 2H), 5.07 (m, 2H), 2.66- 2.56 (m, 4H), 1.96-1.74 (m, 10H), 1.49-1.32 (m, 6H)

Example 7
(1) Production of 1,2-diol compound 6070 mg (21.8 mmol) of pentacene was dissolved in 150 mL of xylene, 4743 mg (55.1 mmol) of vinylene carbonate was added thereto, and kept at 180 ° C. for 3 days under an argon atmosphere. The Diels-Alder reaction was allowed to proceed. Thereafter, 60 mL of 4 mol / L KOH was added and subjected to a hydrolysis treatment to obtain 3000 mg (8.88 mmol) of a 1,2-diol compound. The yield in the Diels-Alder reaction was 41%.

(2) Production of pentacenedialdehyde 130 mg (0.385 mmol) of the obtained 1,2-diol compound was dissolved in 4.0 mL of dehydrated DMSO and heated to 160 ° C., and then 2-iodoxybenzoic acid (IBX) was added thereto. ) 102 mg (0.365 mmol) was added and held at 160 ° C. for 10 minutes to allow the oxidative cleavage reaction of the 1,2-diol structure portion to proceed. Then, 80 mg (0.240 mmol) of pentacenedialdehyde was obtained by removing the solvent and washing the residue with methanol. The yield in the oxidative cleavage reaction was 62%.

(3) Production of pentacenedicarboxylic acid 80 mg (0.240 mmol) of the obtained pentacenedialdehyde was suspended in 15 mL of tetrahydrofuran (THF) in an argon gas atmosphere together with 0.37 mL of 2-methyl-2-butene. Cooled to ° C. A solution prepared by dissolving 44 mg (0.486 mmol) of NaClO ₂ and 87.5 mg (0.729 mmol) of NaH ₂ PO ₄ in 5.0 mL of water was added thereto to obtain a mixed solution. The resulting mixed solution was allowed to warm to room temperature and stirred at room temperature for 11 hours to advance the aldehyde oxidation reaction. Thereafter, THF was removed, 1M HCl was added, and the precipitated solid was separated by filtration, washed with water, and further washed with CHCl ₃ , whereby 30.4 mg (0.083 mmol) of pentacenedicarboxylic acid represented by the following formula (19) was obtained. Got. The yield in the aldehyde oxidation reaction was 34%.

(4) Production of pentacenediimide 30.0 mg (0.0893 mmol) of the obtained pentacenedicarboxylic acid was suspended in 2.0 mL of CH ₂ Cl _{2 in} an argon gas atmosphere together with 0.3 mL of SOCl _{2, and the} temperature was adjusted to 0 ° C. Cooled down. Three drops of N, N-dimethylformamide (DMF) were added thereto, and the mixture was stirred at 0 ° C. for 10 minutes, and then the solvent was removed to obtain pentacene dicarboxylic acid chloride. The obtained pentacene dicarboxylic acid chloride (0.0893 mmol) was dissolved in 3 mL of o-dichlorobenzene in an argon gas atmosphere together with 0.5 mL of isopropyl isocyanate, heated to 80 ° C., and further Bi (OTf). ₃ ) 0.125 g was added and held at 120 ° C. for 1 hour to advance the imidization reaction. Thereafter, the solvent was removed, the residue was purified by column chromatography, and the purified product obtained was further recrystallized from CHCl ₃ to give 5.0 mg (0.01 mmol) of a pentacene diimide compound represented by the following formula (20). Got. The yield in the imidization reaction was 11%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 10.90 (s, 2H), 9.82 (m, 2H), 8.23 (m, 2H), 7.83-7.80 (m, 2H), 7.63-7.60 (m, 2H), 5.68-5.64 (m, 2H), 1.80 (d, 12H)

  According to the present invention, various acene diimide compounds can be easily obtained. The obtained acenediimide compound is expected to be applied to organic solar cells, organic EL, and the like.

Claims (4)

An acene dicarboxylic acid compound represented by the following formula (3) or a carboxylic acid derivative thereof is reacted with an isocyanate compound represented by the following formula (4) in the presence of a catalyst, and the following formula (1) or the following formula (2): A method for producing an acenediimide compound, comprising a step of obtaining the acenediimide compound shown.




[In Formula (1)-(3), m represents an integer greater than or equal to 0, n represents an integer greater than or equal to 0, and in Formula (1), (2), (4), R is C1-C20. Or an aryl group having 6 to 12 carbon atoms. ]   The method for producing an acenediimide compound according to claim 1, wherein a Lewis acid catalyst is used as the catalyst. Furthermore, a process of obtaining 1,2-diol by Diels-Alder reaction of an acene compound represented by the following formula (5) and vinylene carbonate;
The method for producing an acene diimide compound according to claim 1 or 2, further comprising a step of oxidative cleavage of the obtained 1,2-diol to obtain an acene dicarboxylic acid compound represented by the formula (3).

[In Formula (5), m and n are the same as said Formula (1)-Formula (3). ]   The method for producing an acenediimide compound according to claim 3, wherein the oxidative cleavage is performed in the presence of periodic acid, sodium periodate, 2-iodoxybenzoic acid, Dess-Martin periodinane, or lead tetraacetate.