JP2013163663A - Method for producing fused ring compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing fused ring compounds, capable of conveniently producing tetrabenzocoronene and its derivatives.SOLUTION: A method for producing fused ring compounds is provided by comprising a ring formation process for obtaining a coronene derivative fused ring compound by reacting a compound expressed by formula (1) [wherein, Rto Rare each H, alkyl which may have substituents, alkoxy which may have substituents, alkylthio which may have substituents, aryl which may have substituents, a monovalent aromatic heterocyclic group which may have substituents or a halogen atom; and ring A, ring B, ring C and ring D are each an aromatic ring which may have substituents] with an oxidizing agent.

Description

  The present invention relates to a method for producing a fused ring compound.

  It is known that a disk-shaped condensed ring compound in which an aromatic ring is condensed forms a one-dimensional column structure in which crystals have a very short interplanar spacing due to strong π-π interaction. For this reason, it is known that the charge (which means holes and electrons; the same applies hereinafter) along this column structure has a high mobility and becomes a useful organic semiconductor material. Applications to electronic devices such as the first are being studied.

  Among the above disk-shaped condensed ring compounds, coronene and derivatives thereof having the same symmetry as benzene are well known, and coronene derivatives introduced with functional groups such as long chain alkyl groups are highly ordered columns. Since a liquid crystal phase having a structure is formed, it is also useful as a liquid crystal material.

  Examples of the coronene derivative include tetrabenzo [a, d, j, m] coronene (hereinafter sometimes abbreviated as “tetrabenzocoronene”). Tetrabenzocoronene and derivatives thereof whose electronic state is changed are compounds that are expected to be applied to organic semiconductor materials and the like from the viewpoints of electron transport properties and self-integration ability.

Examples of the method for producing tetrabenzocoronene and derivatives thereof include the synthesis method disclosed in Non-Patent Document 1. In this synthesis method, benzophenone or a derivative thereof is used as a starting material, and an olefin intermediate is formed into a ring by a two-stage reaction of an oxidative photocyclization reaction and an intramolecular cyclization reaction using FeCl ₃ as a catalyst. Alternatively, a derivative thereof is synthesized.

Journal of Organic Chemistry, 2010, Vol. 75, 8069.

  However, tetrabenzocoronene and its derivatives are useful compounds as organic semiconductor materials and the like, but their production methods are complicated. For example, in the production method of Non-Patent Document 1, a number of steps are required from the starting material to the target product. As described above, the conventional method for producing tetrabenzocoronene is complicated, for example, requires a large number of steps, so that the cost of raw materials and other reagents to be used and an increase in production time have been problems.

  Then, this invention aims at providing the manufacturing method of a condensed ring compound which can manufacture tetrabenzo coronene and its derivative (s) simply.

［式中、
Ｒ^１１、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ同一又は相異なり、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよい１価の芳香族複素環基又はハロゲン原子を表す。また、Ｒ^１１とＲ^１３が互いに結合して、それらが結合しているベンゼン環と縮合する環状構造を形成してもよく、Ｒ^１２とＲ^１４が互いに結合して、それらが結合しているベンゼン環と縮合する環状構造を形成してもよい。
Ａ環、Ｂ環、Ｃ環及びＤ環は、それぞれ同一又は相異なり、置換基を有していてもよい芳香環を表す。］ In order to achieve the above object, the method for producing a fused ring compound of the present invention comprises reacting a compound represented by the formula (1) with an oxidizing agent to produce a fused ring compound represented by the formula (2). The resulting ring formation step.

[Where:
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted monovalent aromatic heterocyclic group or a halogen atom. Further, R ¹¹ and R ¹³ may be bonded to each other to form a cyclic structure that is condensed with the benzene ring to which they are bonded, and R ¹² and R ¹⁴ are bonded to each other so that they are bonded. You may form the cyclic structure condensed with a benzene ring.
A ring, B ring, C ring and D ring are the same or different and each represents an aromatic ring which may have a substituent. ]

  According to the method for producing a fused ring compound of the present invention, the fused ring compound can be produced from the compound represented by the formula (1) in one ring forming step in which a cyclization reaction is performed with an oxidizing agent. . In this case, since the reagent to be used is an oxidizing agent that is usually available at a low cost and is a one-stage ring formation step as described above, tetrabenzocoronene and its derivatives can be easily produced.

  In the above method for producing a condensed ring compound, the A ring, the B ring, the C ring, and the D ring are the same or different and are preferably benzene rings that may have a substituent. This is because the condensed ring compound obtained by the production method of the present invention has higher electron transport properties.

In the above method for producing a condensed ring compound, the oxidizing agent is preferably a compound represented by the formula (3).
MX _n (3)
[Wherein, M represents a group 4 to group 13 atom in the periodic table.
X is independently a halogen atom, —OSO ₂ R ^a (R ^a represents an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent). Or a group represented by —OCOR ^b (R ^b represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent). Represents. When two or more X exists, they may be the same or different.
n represents an integer of 1 to 4. ]

  More specifically, the oxidizing agent is aluminum chloride, aluminum bromide, iron (III) chloride, iron (III) bromide, copper chloride, copper bromide, copper trifluoromethanesulfonate, molybdenum chloride, titanium chloride, four It is preferable that it is at least one compound selected from the group consisting of lead acetate, thallium trifluoroacetate and boron trifluoride. Of these, the oxidizing agent is preferably aluminum chloride and / or copper trifluoromethanesulfonate. This is because the use of these compounds as the oxidizing agent facilitates the above-described cyclization reaction. Moreover, since these oxidizing agents do not require light in the cyclization reaction, it is possible to perform the ring formation step more easily.

［式（４）、（５）及び（６）中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ａ環、Ｂ環、Ｃ環及びＤ環は、それぞれ上記と同義である。］ Moreover, in the manufacturing method of said condensed ring compound, it is preferable to implement the process of synthesize | combining the compound represented by Formula (1) by a specific method before the said ring formation process. That is, before the ring formation step, the 1-position, 4-position, 5-position and 8-position of the anthraquinone derivative represented by the formula (4) are respectively substituted with the A ring, C ring, D ring and B ring, A step of obtaining intermediate 1 represented by formula (5), a step of nucleophilic addition of a methyl group to the carbonyl group in intermediate 1 to obtain intermediate 2 represented by formula (6), and The step of obtaining a compound represented by the formula (1) by intramolecular dehydration of the hydroxyl group in the intermediate 2 is preferably performed.

[In the formulas (4), (5) and (6), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , A ring, B ring, C ring and D ring have the same meanings as above. ]

  In each step performed before the above ring formation step, a commercially available anthraquinone derivative is used as a starting material, and a compound represented by the formula (1) can be synthesized in three steps therefrom. it can. Therefore, in the method for producing a condensed ring compound including these steps, it is possible to produce the condensed ring compound in a total of four steps together with the ring formation step. Each of these steps is simple and can be performed using a relatively inexpensive reagent. Therefore, according to the method for producing a fused ring compound of the present invention including these steps, the fused ring compound can be more easily produced, and the cost and time for that can be reduced. .

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of the condensed ring compound which can manufacture tetrabenzo coronene and its derivative (s) more simply than before.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

[Ring formation process]
The method for producing a fused ring compound of the present embodiment includes a ring forming step of obtaining a fused ring compound represented by the formula (2) by reacting a compound represented by the formula (1) with an oxidizing agent. . Hereinafter, such a ring formation step will be described.

<Compound represented by Formula (1)>
First, the compound represented by Formula (1) for obtaining a condensed ring compound will be described.
In the formula (1), R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different from each other, and each may have a hydrogen atom, an alkyl group which may have a substituent, or a substituent. An alkoxy group, an alkylthio group which may have a substituent, an aryl group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent or a halogen atom. Further, R ¹¹ and R ¹³ may be bonded to each other to form a cyclic structure that is condensed with the benzene ring to which they are bonded, and R ¹² and R ¹⁴ are bonded to each other so that they are bonded. You may form the cyclic structure condensed with a benzene ring. A ring, B ring, C ring and D ring are the same or different from each other, and represent an aromatic ring. The aromatic ring includes both aromatic hydrocarbon rings and aromatic heterocyclic rings.

  The alkyl group may have a substituent. The number of carbon atoms of the alkyl group excluding this substituent is preferably 1-60, and more preferably 1-20. The alkyl group may be a linear alkyl group or a branched alkyl group, and may be a cycloalkyl group.

  Specific examples of the alkyl group include linear alkyl groups such as methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, and n-octadecyl group; Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 3,7,11-trimethyldodecyl group, 2-hexyldecyl group, 2-octyldodecyl group Branched alkyl groups such as cyclopentyl group, cyclohexyl group and the like.

  Examples of the substituent that the alkyl group may have include an alkoxy group, an aryl group, and a halogen atom. Specific examples of the alkyl group having a substituent include a methoxyethyl group, a benzyl group, a trifluoromethyl group, and a perfluorohexyl group.

  The alkoxy group may have a substituent. The number of carbon atoms of the alkoxy group excluding this substituent is preferably 1-60, and more preferably 1-20. The alkoxy group may be either a linear alkoxy group or a branched alkoxy group, and may be a cycloalkoxy group.

  Specific examples of the alkoxy group include n-butyloxy group, n-hexyloxy group, 2-ethylhexyloxy group, 3,7-dimethyloctyloxy group, n-dodecyloxy group and the like. Examples of the substituent that the alkoxy group may have include an aryl group and a halogen atom.

  The alkylthio group may have a substituent. The number of carbon atoms of the alkylthio group excluding this substituent is preferably 1-60, and more preferably 1-20. The alkylthio group may be a linear alkylthio group or a branched alkylthio group, or may be a cycloalkylthio group.

  Specific examples of the alkylthio group include an n-butylthio group, an n-hexylthio group, a 2-ethylhexylthio group, a 3,7-dimethyloctylthio group, and an n-dodecylthio group. Examples of the substituent that the alkylthio group may have include an aryl group and a halogen atom.

  An aryl group is an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic ring from an aromatic hydrocarbon, a group having a benzene ring, a group having a condensed ring, an independent aromatic ring, and a condensed group It includes a group in which two or more selected from a ring are directly bonded. The aromatic hydrocarbon may have a substituent, and thus the aryl group may also have a substituent derived therefrom.

  The number of carbon atoms of the aryl group excluding the substituent is preferably 6 to 60, and more preferably 6 to 20. As the aryl group, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2- Examples include a fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 4-phenylphenyl group.

  Examples of the substituent that the aryl group may have include an alkyl group, an alkoxy group, an alkylthio group, a heteroaryl group, and a halogen atom. Examples of the aryl group having a substituent include 4-hexylphenyl group, 3,5-dimethoxyphenyl group, and pentafluorophenyl group. When the aryl group has a substituent, the substituent is preferably an alkyl group.

  A monovalent aromatic heterocyclic group is an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting an aromatic heterocyclic ring from an aromatic heterocyclic compound, a group having a condensed ring, independently And a group in which two or more selected from the aromatic heterocyclic ring and the condensed ring are directly bonded. The aromatic heterocyclic compound may have a substituent, and thus the monovalent aromatic heterocyclic group may also have a substituent derived therefrom.

  The number of carbon atoms of the monovalent aromatic heterocyclic group excluding the substituent is preferably 2 to 60, and more preferably 3 to 20. The monovalent aromatic heterocyclic group includes 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group. 2-imidazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like.

  Examples of the substituent that the monovalent aromatic heterocyclic group may have include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, and a halogen atom. Examples of the monovalent aromatic heterocyclic group having a substituent include a 5-octyl-2-thienyl group and a 5-phenyl-2-furyl group. When the monovalent aromatic heterocyclic group has a substituent, the substituent is preferably an alkyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

As described above, in the compound represented by the formula (1) may be bonded R ¹¹ and R ¹³ are each other to form a ring structure to which they are fused with a benzene ring bonded, R ¹² And R ¹⁴ may be bonded to each other to form a cyclic structure condensed with the benzene ring to which they are bonded. The formed cyclic structure may be an aliphatic ring or an aromatic ring, and may contain atoms other than carbon atoms as atoms constituting the ring. As atoms other than carbon atoms, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms and the like can be mentioned.

  Examples of such a cyclic structure include the following structures.

In the formulas representing the above cyclic structures, R ² is the same or different and represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or a halogen atom. The definition and specific examples of the alkyl group, aryl group, monovalent aromatic heterocyclic group or halogen atom represented by R ² are as follows: alkyl group, aryl group, monovalent group represented by the aforementioned R ^{11 to} R ¹⁴ . The definition and specific examples of the aromatic heterocyclic group or halogen atom are the same.

In the formula (1), A ring, B ring, C ring and D ring are the same or different and each represents an aromatic ring. The aromatic ring may have a substituent. The number of carbon atoms in the aromatic ring is preferably 2 to 60, more preferably 2 to 22, and further preferably 3 to 14. The number of carbon atoms does not include the number of carbon atoms of the substituent that the aromatic ring has.
As the aromatic ring, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, perylene ring, fluorene ring, oxazole ring, thiazole ring, furan ring, thiophene ring, pyrrole ring, pyridine ring, pyrazine ring, Pyrimidine ring, benzofuran ring, benzothiophene ring, benzopyrrole ring, quinoline ring, isoquinoline ring, thieno [3,2-b] thiophene ring, thieno [2,3-b] thiophene ring, dithieno [3,2-b: 2 ′, 3′-d] thiophene ring and the like.

At least one of the A ring, the B ring, the C ring, and the D ring is preferably a benzene ring that may have a substituent, and two may be benzene rings that may have a substituent. More preferably, three are benzene rings which may have a substituent, and more preferably all are benzene rings which may have a substituent. Incidentally, A ring, as the ring B, C and D rings have substituent which may have, the same thing can be exemplified as the substituents exemplified as the R ¹¹ to R ^14.

  When at least one of the A ring, the B ring, the C ring, and the D ring is a benzene ring having a substituent, the substituent bonded to the benzene ring is in the ortho position with respect to the bond to the condensed ring. It is preferably located in the para position, and more preferably located in the para position. This is because when the A ring, the B ring, the C ring, or the D ring is a benzene ring having a substituent at such a position, the electron transport property of the obtained condensed ring compound becomes higher.

  As a compound represented by Formula (1), the compound represented by the following formula | equation (1-1)-Formula (1-9) is mentioned, for example, Formula (1-1)-Formula (1-5) The compound represented by Formula (1-1), the compound represented by Formula (1-2), and the compound represented by Formula (1-4) are preferable.

<Oxidizing agent>
An oxidizing agent is a compound that can extract electrons from the compound represented by the above formula (1). The oxidizing agent does not react with other reagents such as a solvent or other than the intended portion (specifically, A ring, B ring, C ring and D ring) in the compound represented by formula (1). It is preferable that it is. Further, it is more preferable that the oxidant is a compound that can smoothly react without irradiation with light and can obtain the compound represented by the formula (2) with a sufficient yield.

Examples of the oxidizing agent include compounds represented by the following formula (3).
MX _n (3)
[Wherein, M represents a group 4 to group 13 atom in the periodic table.
X represents a halogen atom, —OSO ₂ R ^a (R ^a represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent). Or a group represented by —OCOR ^b (R ^b represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent). When two or more X exists, they may be the same or different.
n represents an integer of 1 to 4. ]

  In the formula (3), M is a group 4 to group 13 atom in the periodic table, preferably a group 4 to group 13 metal atom in the periodic table, an aluminum atom, an iron atom, a copper atom, a molybdenum atom, Titanium atoms, lead atoms, and thallium atoms are more preferable.

  In the formula (3), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom and a chlorine atom are preferable.

In Formula (3), R ^a represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. The definition and specific examples of the alkyl group, aryl group or monovalent aromatic heterocyclic group represented by R ^a are the alkyl group, aryl group or monovalent aromatic represented by the aforementioned R ^{11 to} R ^14. The definition and specific examples of the heterocyclic group are the same.

In Formula (3), ^Rb represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups may have a substituent. The definition and specific examples of the alkyl group, aryl group or monovalent aromatic heterocyclic group represented by R ^b are as follows: the alkyl group, aryl group or monovalent aromatic represented by the aforementioned R ^{11 to} R ^14. The definition and specific examples of the heterocyclic group are the same.

  Preferred examples of the oxidizing agent include aluminum chloride, aluminum bromide, iron (III) chloride, iron (III) bromide, copper chloride, copper bromide, copper trifluoromethanesulfonate, molybdenum chloride, titanium chloride, and lead tetraacetate. , Thallium trifluoroacetate and boron trifluoride.

  Among these, from the viewpoint of increasing the yield of the reaction, it is preferable to use aluminum chloride and / or copper trifluoromethanesulfonate as the oxidizing agent, and it is more preferable to use a combination of aluminum chloride and copper trifluoromethanesulfonate.

  In the ring formation step, the amount of the oxidizing agent used is preferably 4 to 1000 mol, more preferably 8 to 500 mol, relative to 1 mol of the compound represented by formula (1). It becomes possible to make a ring formation process advance favorably by making an oxidizing agent into a suitable usage-amount.

<Fused Ring Compound Represented by Formula (2)>
The condensed ring compound represented by Formula (2) is obtained by the ring formation step described above. In addition, R < ¹¹ >, R <^12> , R <^13> and R < ¹⁴ > in Formula (2), and A ring, B ring, C ring, and D ring are synonymous with the case of said Formula (1), respectively.

  Examples of such fused ring compounds include the following compounds.

＜反応条件＞
上述した環形成工程における反応温度は、−２０〜２００℃であることが好ましい。反応を効率的に進行させる観点からは、０℃以上がより好ましく、２０℃以上がさらに好ましい。また、副反応を抑える観点からは、１５０℃以下がより好ましく、１００℃以下がさらに好ましい。

<Reaction conditions>
The reaction temperature in the ring formation step described above is preferably -20 to 200 ° C. From the viewpoint of allowing the reaction to proceed efficiently, 0 ° C. or higher is more preferable, and 20 ° C. or higher is more preferable. Moreover, from a viewpoint of suppressing a side reaction, 150 degrees C or less is more preferable, and 100 degrees C or less is further more preferable.

  The reaction time is preferably 1 minute to 200 hours. From the viewpoint of sufficiently allowing the reaction to proceed, one hour or more is more preferable.

  The reaction in the ring formation step may be performed in the absence of a solvent or in the presence of a solvent, but is preferably performed in the presence of a solvent. When using a solvent, the solvent used should just be an inert solvent with respect to a cyclization reaction, may be used individually by 1 type, and is good also as a mixed solvent which mixed several solvent. Examples of the solvent include aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane; aromatic hydrocarbon solvents such as nitrobenzene; ether solvents such as tetrahydrofuran and anisole; aprotic polar solvents such as nitromethane; carbon disulfide and the like. Can be mentioned. Carbon disulfide is preferred because of the high solubility of the compound represented by formula (1).

  The reaction may be carried out in air or in an inert gas atmosphere, but it is preferably carried out in an inert gas atmosphere such as nitrogen or argon from the viewpoint of suppressing side reactions.

<Reaction in ring formation step>
In the ring formation step, as described above, the compound represented by the formula (1) is reacted with the oxidizing agent to obtain the condensed ring compound represented by the formula (2). The reaction in such a ring formation step is formally made up of two methylidene groups present in the compound represented by the formula (1) and the A ring, B ring, C ring and D ring adjacent thereto. This is a reaction in which four covalent bonds are formed between them to form a ring structure. These covalent bonds are not formed simultaneously, but sequentially in random order.

For example, in the ring formation step, a sequential reaction proceeds as shown in the following formula.

Incidentally, it tetrabenzoporphyrins coronene, which is an example of possible compounds produced by the production method of a fused ring compound of the present embodiment, when having a substituent at the position of R ³ and R ⁴ represented by the following formula (9), Since it exhibits higher electron transport properties than those having a substituent at the position of R ⁵ represented by formula (10), it can be an organic semiconductor with higher properties. In addition, as R < ³ > and R < ⁴ >, the same thing as the substituent which said A ring-D ring may have can be illustrated. Especially, it is preferable to have an alkyl group, an alkoxy group, or an alkylthio group as a substituent represented by R ³ and R ⁴ because higher electron transport properties are exhibited.

In particular, according to the ring formation step of this embodiment, it is easy to introduce a substituent at the positions of R ³ and R ⁴ represented by the formula (9). On the other hand, in the conventional method for producing tetrabenzocoronene, a substituent is easily introduced at the position of R ⁵ represented by the formula (10) due to steric hindrance during the reaction, and the positions of R ³ and R ⁴ described above. It was difficult to introduce a substituent into. Therefore, the method for producing a condensed ring compound of the present embodiment also has an effect that tetrabenzocoronene having higher characteristics as an organic semiconductor can be produced.

[Production Method of Compound Represented by Formula (1)]
In the method for producing a fused ring compound of the present embodiment, the compound represented by formula (1), which is a starting material for the ring formation step, is produced by the following method prior to the ring formation step described above. It is preferable to carry out the process. That is, the compound represented by the formula (1) can be produced by a simple method using a commercially available anthraquinone derivative as a starting material.

  As a method for producing the compound represented by the formula (1), first, an aromatic ring corresponding to the A ring, the C ring, the D ring and the B ring at the 1-position, 4-position, 5-position and 8-position of the anthraquinone derivative, respectively. And then a nucleophilic addition of a methyl group to the 9 and 10 position carbonyl groups. By this nucleophilic addition, the 9th and 10th carbon atoms have a hydroxyl group and a methyl group derived from a carbonyl group. And the compound represented by Formula (1) which has a methylidene group in carbon of 9th-position and 10th-position can be obtained by carrying out intramolecular dehydration of the hydroxyl group produced in this way.

The anthraquinone derivative as a starting material, represented by the above formula (4), those having an ^R 11 ^{to R 14} in a position corresponding to the ^R 11 ^{to R 14} of the compound represented by the formula (1) for the purpose Use. Specific examples of such anthraquinone derivatives include the following.

Next, the 1st, 4th, 5th and 8th positions of the anthraquinone derivative are respectively substituted with the A ring, the C ring, the D ring and the B ring to produce the intermediate 1 represented by the formula (5). . Intermediate 1 can be obtained, for example, by reacting a boronic acid ester represented by the following formula (8-1) to formula (8-3) with an anthraquinone derivative. X in the formula (8-1) to the formula (8-3) represents any of the A ring to the D ring and can be appropriately selected.

In this reaction, by using a complex such as RuH ₂ (CO) (PPh ₃ ) ₃ as a catalyst, each aromatic ring is selectively introduced into the 1st, 4th, 5th and 8th positions of the anthraquinone derivative. be able to. In particular, by using such a catalyst, an aryl group can be introduced in the ortho position with respect to those functional groups in a benzene ring having a functional group composed of an acyl group or a derivative thereof. Furthermore, by using a solvent such as pinacolone, the introduction reaction of the A-ring to the D-ring can be advanced while suppressing the reduction reaction that is a competitive reaction of the reaction.

  Next, a reaction for nucleophilic addition of a methyl group to the 9th and 10th carbonyl groups of intermediate 1 is performed to obtain intermediate 2 represented by formula (6). As the methylating agent used for this nucleophilic addition, a methyl group can be introduced nucleophilically into the 9th and 10th carbonyl carbons of Intermediate 1 and does not react with other parts of the anthraquinone derivative. Those are preferred. Specific examples of the methylating agent include methyl lithium and Grignard reagent.

  The intermediate 2 obtained in the methylation reaction is obtained as a mixture of diastereomers having different steric configurations of two methyl groups introduced into the molecule, but the compounds obtained after the dehydration reaction described later are the same. Therefore, it can be used without distinction in the next step.

  And the methylidene group is formed in the said part by carrying out the intramolecular dehydration of the hydroxyl group produced by methylation with respect to the intermediate body 2 obtained as mentioned above. Thereby, the compound represented by Formula (1) is obtained. This dehydration reaction can be performed by a known method.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Synthesis Example 1: Synthesis of 1,4,5,8-tetraphenylanthraquinone)

A magnetic stir bar was placed in a well-dried flask, a reflux condenser and a blow tube were attached, and the blow tube was connected to a vacuum / nitrogen line. To this flask was added anthraquinone (52.2 mg, 0.25 mmol), phenylboronic acid ester (476.1 mg, 2.5 mmol) and RuH ₂ (CO) (PPh ₃ ) ₃ complex (46.1 mg, 0.05 mmol). added. Next, after replacing the inside of the flask with nitrogen gas, 0.5 mL of pinacolone was added. These mixtures were reacted under reflux conditions for 24 hours. Then, the resulting precipitate was filtered and washed with chloroform to obtain 1,4,5,8-tetraphenylanthraquinone which is the target product in a yield of 28% (36.4 mg, 0.071 mmol). It was. The analysis results of the obtained product are as follows.
HRMS (ESI) calcd for [M + K] ⁺ (C ₃₈ H ₂₄ KO ₂ ) m / z 551.1413. Found 551.1406.

(Synthesis Example 2: Synthesis of 9,10-dimethyl-1,4,5,8-tetraphenyl-9,10-dihydroanthracene-9,10-diol)

  A magnetic stir bar was placed in a well-dried flask, a reflux condenser and a blower tube were attached, and the blower tube was connected to a vacuum / nitrogen line. To this flask, 10 mL of dehydrated THF and a diethyl ether solution of methyllithium (1.03 M, 9.7 mL, 10 mmol) were added. After the flask was cooled to −78 ° C., 1,4,5,8-tetraphenylanthraquinone obtained in Synthesis Example 1 was added. The reaction solution was warmed to room temperature and reacted overnight. Thereafter, dilute hydrochloric acid was added to the reaction solution at 0 ° C. to make the solution acidic. The resulting solution was extracted with dichloromethane.

The product was isolated by silica gel column chromatography (inner diameter = 30 mm, column length = 140 mm, eluent hexane: dichloromethane = 5: 1). Thus, the diastereomer (cis isomer, trans isomer) of the desired product 9,10-dimethyl-1,4,5,8-tetraphenyl-9,10-dihydroanthracene-9,10-diol A mixture of was obtained. The yield was 58% (315.6 mg, 0.58 mmol). The analysis results of the obtained product are as follows.
Diastereomer A (167.3 mg, 31%)
¹ H-NMR (CDCl ₃ ): δ (ppm) = 1.86 (s, 6H, CH ₃ ), 6.90 (s, 4H, ArH), 7.10-7.40 (m, 20H, ArH) ).
Diastereomer B (148.3 mg, 27%)
¹ H-NMR (CDCl ₃ ): δ (ppm) = 1.86 (s, 6H, CH ₃ ), 6.90 (s, 4H, ArH), 7.10-7.40 (m, 20H, ArH) ).

(Synthesis Example 3: Synthesis of 9,10-dimethylene-1,4,5,8-tetraphenyl-9,10-dihydroanthracene)

  A mixture of diastereomers of 9,10-dimethyl-1,4,5,8-tetraphenyl-9,10-dihydroanthracene-9,10-diol obtained in Synthesis Example 2 (247.5 mg, 0 .454 mmol), sodium iodide (680.4 mg, 4.54 mmol), sodium phosphinate monohydrate (481.3 mg, 4.54 mmol) and 12 mL of acetic acid were added. This mixture was reacted for 2 hours under reflux conditions. After the reaction solution was cooled to room temperature, water was added. The resulting solution was extracted with dichloromethane.

The product was isolated by silica gel column chromatography (inner diameter = 15 mm, column length = 150 mm, eluent hexane: dichloromethane = 10: 1). In this way, 9,10-dimethylene-1,4,5,8-tetraphenyl-9,10-dihydroanthracene, which is the target product, was obtained. The yield was 84% (193.5 mg, 0.380 mmol). The analysis results of the obtained product are as follows.
¹ H-NMR (CDCl ₃ ): δ (ppm) = 4.85 (s, 4H, CH ₂ ), 7.26-7.41 (m, 16H, ArH), 7.42-7.50 (m , 8H, ArH).

(Example 1: Synthesis of tetrabenzo [a, d, j, m] coronene)

A magnetic stir bar was placed in a fully dried Schlenk tube, a reflux condenser and a blow tube were attached, and the blow tube was connected to a vacuum / nitrogen line. To this Schlenk tube, 9,10-dimethylene-1,4,5,8-tetraphenyl-9,10-dihydroanthracene (25.5 mg, 0.05 mmol) obtained in Synthesis Example 3 and copper trifluoromethanesulfonate ( II) (1.8082 grams, 5.0 mmol) and aluminum (III) chloride (673.5 mg, 5.1 mmol) were added. After replacing the Schlenk tube with nitrogen gas, 10 mL of carbon disulfide was added. The reaction solution was stirred at room temperature for 12 hours, and then poured into a diluted hydrochloric acid solution to stop the reaction. The solid produced by this reaction was filtered and washed with chloroform, aqueous sodium hydrogen carbonate solution, water and chloroform, and the target product tetrabenzo [a was obtained in a yield of 55% (13.9 mg, 0.028 mmol). , D, j, m] coronene was obtained. The analysis results of the obtained product are as follows.
MS (MALDI) m / z 500 [M] ⁺

Claims (6)

Reacting the compound represented by the formula (1) with an oxidizing agent,
The manufacturing method of a condensed ring compound including the ring formation process of obtaining the condensed ring compound represented by Formula (2).

[Where:
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are the same or different and each has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted monovalent aromatic heterocyclic group or a halogen atom. Further, R ¹¹ and R ¹³ may be bonded to each other to form a cyclic structure that is condensed with the benzene ring to which they are bonded, and R ¹² and R ¹⁴ are bonded to each other so that they are bonded. You may form the cyclic structure condensed with a benzene ring.
A ring, B ring, C ring and D ring are the same or different and each represents an aromatic ring which may have a substituent. ]   The method for producing a condensed ring compound according to claim 1, wherein the A ring, the B ring, the C ring, and the D ring are the same or different and are benzene rings that may have a substituent. The manufacturing method of the condensed ring compound of Claim 1 or 2 whose said oxidizing agent is a compound represented by Formula (3).
MX _n (3)
[Wherein, M represents a group 4 to group 13 atom in the periodic table.
X represents a halogen atom, —OSO ₂ R ^a (R ^a represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent). Or a group represented by —OCOR ^b (R ^b represents an alkyl group, an aryl group or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent). When two or more X exists, they may be the same or different.
n represents an integer of 1 to 4. ] The oxidizing agent is
Aluminum chloride, aluminum bromide, iron (III) chloride, iron (III) bromide, copper chloride, copper bromide, copper trifluoromethanesulfonate, molybdenum chloride, titanium chloride, lead tetraacetate, thallium trifluoroacetate and trifluoride The method for producing a fused ring compound according to claim 3, which is at least one compound selected from the group consisting of boron halides.   The method for producing a condensed ring compound according to claim 4, wherein the oxidizing agent is aluminum chloride and / or copper trifluoromethanesulfonate. Before the ring formation step,
In the formula (5), the 1-position, 4-position, 5-position and 8-position of the anthraquinone derivative represented by the formula (4) are respectively substituted with the A ring, the C ring, the D ring and the B ring. Obtaining intermediate 1 represented,
A step of nucleophilic addition of a methyl group to the carbonyl group in intermediate 1 to obtain intermediate 2 represented by formula (6);
The condensed ring compound according to any one of claims 1 to 5, wherein a step of obtaining a compound represented by the formula (1) by dehydrating a hydroxyl group in the intermediate 2 in a molecule is performed. Manufacturing method.

[In the formulas (4), (5) and (6), R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , A ring, B ring, C ring and D ring have the same meanings as above. ]