JP6957084B2 - Method for producing condensed polycyclic compound - Google Patents

Description

The present invention relates to a method for producing a condensed polycyclic compound. More specifically, the present invention relates to a method for producing a condensed polycyclic compound that can be suitably used as a material for a light emitting element, an n-type organic semiconductor material, or the like.

The cross-coupling reaction represented by Suzuki-Miyaura coupling is a useful method for bonding carbon atoms of organic compounds, and in a narrow sense, it consists of benzene-benzene, which is often found in pharmaceuticals and functional materials. A method for synthesizing a skeleton called a biaryl skeleton. A carbon-carbon bond can be constructed by mixing a compound having a carbon-metal bond (organic metal compound) and a compound having a carbon-halogen bond in the presence of a catalyst (carbon-metal / carbon-halogen type). [CM / CX] type, formula (A) below). Although it was very difficult to synthesize the biaryl skeleton before 1970, various cross-coupling reactions were developed based on the research by Kumada and Tamao et al. Among them, the coupling reaction using a palladium catalyst between an organoboron compound and an aryl halide is called a Suzuki-Miyaura coupling reaction, and is most used because of the ease of handling and low toxicity of the organoboron compound. It is a method that is used. At present, this biaryl skeleton synthesis method is widely used from basic research to the production of pharmaceuticals and functional materials, and has become indispensable.
Although the cross-coupling reaction is a very useful reaction as described above, it is necessary to prepare a reaction substrate having a carbon-metal and a carbon-halogen bond, respectively. The preparation requires a plurality of steps, and in some cases, some compounds cannot be synthesized from the viewpoint of functional group tolerance. Therefore, a cross-coupling reaction that does not require a carbon-metal or carbon-halogen bond, that is, a cross-coupling reaction (carbon-hydrogen / carbon) between carbon-hydrogen and carbon-hydrogen, which are bonds contained in any aryl compound. -Hydrogen type [CH / CH] type, the following formula (B)) has been desired to be developed. To date, the synthesis of various compounds using such carbon-hydrogen and carbon-hydrogen cross-coupling reactions has been reported (see Non-Patent Documents 1 to 8).

By the way, in organic electroluminescent devices, which have been researched and developed in recent years, materials that enable the realization of high-performance devices have been studied, and compounds having a plurality of aromatic rings in the structure, aromatic rings, and other ring structures have been studied. There is a report that a compound having a specific structure having an electroluminescent structure was produced (see Patent Documents 1 to 4).

Korean Patent No. 10-142295 International Publication No. 2012/141273 International Publication No. 2015/167300 Korean Publication No. 10-2013-0070431

Hiroyuki Kaida and 3 other people "Chemistry Letters", Vol. 44, 2015, p1125-1127 One person from outside Hataaki Yoshimoto, "Bulletin of the Chemical Society of Japan," Vol. 46, 1973, p2490-2492. Bjorn Åkermark and 3 others "Journal of Organic Chemistry", Vol. 40, No. 9, 1975, pp. 1365-1367 Helena Hagelin and two others "Chemistry A European Journal", Vol. 5, No. 8, 1999, pp. 2413-2416 4 people outside Benoit Liegault "The Journal of Organic Chemistry", Vol. 73, 2008, p502-2528 4 people from outside Rui Che "Chemistry A European Journal", Vol. 20, 2014, 7258-7261 Three people from outside Kenta Saito "Chemistry A European Journal", Vol. 21, 2015, p8365-8368 One person outside Jan Bergman "Tetrahedron Letters", Vol. 34, 1978, p3143-3146

As described above, the synthesis of condensed ring compounds having various structures using the cross-coupling reaction has been reported, but the application range of the cross-coupling reaction is wide, and various compounds are further synthesized using the cross-coupling reaction. There is room to consider how to do this.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a new method for producing a condensed ring compound using a cross-coupling reaction.

The present inventor has studied various new methods for producing a condensed ring compound using a cross-coupling reaction, and found that a plurality of rings are shrunk with respect to an aromatic ring or a nitrogen-containing heteroaromatic ring using the cross-coupling reaction. We have found that a condensed polycyclic compound having a ringed structure can be produced more easily than before, and arrived at the present invention. The production method of the present invention is a useful method that can also be used for producing a compound suitable as a material for the above-mentioned organic electroluminescent device or n-type organic semiconductor.

That is, the present invention is a method for producing a condensed polycyclic compound having a structure in which a plurality of rings including an aromatic ring are fused, and the production method is described in the following formula (1);

(In the formula, X ^{1 to} X ⁶ represent the same or different carbon atom or nitrogen atom. The dotted arc indicates the aromatic hydrocarbon ring or sulfur atom together with the carbon-carbon double bond portion represented by the solid line. , Indicates that an aromatic heterocyclic structure containing an oxygen atom or a nitrogen atom is formed, and when X ^{1 to} X ⁶ are all carbon atoms, the nitrogen atom of the benzene ring, fluorene ring, carbazole ring or carbazole ring Is a ring structure other than the ring substituted with a sulfur atom or an oxygen atom. M is the same or different, a methylene group optionally substituted with an oxygen atom, a sulfur atom, a carbonyl group, or a halogen atom or an organic group. or ^.R 1, ^{R 2} representing an amino group are the same or different, a hydrogen atom, the number of each ^.m 1, ^{m 2} represents an organic group which is a substituent of a halogen atom or a ring structure ^R 1, ^{R 2 M 1} is 0 to 2, and m ² is a number of 1 or more. When a ^{plurality of R 1} and R ² are bonded to an aromatic ring or a complex aromatic ring structure forming an arc portion of a dotted line. In the above, organic groups may be bonded to each other to form a ring structure. N is 2 or 3) by a reaction for forming a bond between the ring structures of the polycyclic compound. The following formula (2);

(In the equation, X ^{1 to} X ⁶ , dotted arc, M, R ¹ , R ² , m ¹ , m ² , and n are the same as in equation (1).) A method for producing a condensed polycyclic compound, which comprises a step of synthesizing the formula compound.
The present invention will be described in detail below.
A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

In the method for producing a condensed polycyclic compound of the present invention, a condensed polycyclic compound represented by the above formula (2) is produced by a reaction for forming a bond between the ring structures of the compound represented by the above formula (1). It is characterized by including a step of synthesizing. As described in Patent Documents 1 to 4 described above, the condensed polycyclic compound also includes a compound useful as a material for an organic electroluminescent device. The production method of the present invention is a production method that makes it possible to easily produce such a condensed polycyclic compound. The method for producing a condensed polycyclic compound of the present invention is characterized in that a cross-coupling reaction occurs at two or more places and two or more condensed ring structures are formed on one aromatic ring. .. When a raw material that undergoes a cross-coupling reaction at only one site is used, a side reaction of dimerization may proceed and the yield of the product may deteriorate, but as in the present invention, cross at two or more sites. When the coupling reaction is carried out, the progress of such side reactions is small and the reactivity tends to be improved. Therefore, the desired production is performed in a higher yield than when the cross-coupling reaction is carried out at only one site. You can get things.
The method for producing a condensed polycyclic compound of the present invention includes other steps as long as it includes a step of synthesizing the condensed polycyclic compound represented by the above formula (2) from the compound represented by the above formula (1). It may be included.

In the above formula (1), the dotted arc is formed with an aromatic hydrocarbon ring or an aromatic heterocyclic structure containing a sulfur atom, an oxygen atom or a nitrogen atom together with a carbon-carbon double bond portion represented by a solid line. Indicates that you are.
Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, and a pentacene ring.
Examples of the aromatic heterocycle include a sulfur atom-containing heterocycle such as a thiophene ring, a benzothiophene ring, a thiazole ring, and a ring in which the nitrogen atom of the carbazole ring is replaced with a sulfur atom; the nitrogen atom of the furan ring, the oxazole ring, and the carbazole ring is oxygen. Oxygen atom-containing heterocycles such as atomically substituted rings; pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyridazine ring, pyrazine ring, pyrimidine ring, indole ring, isoindole ring, quinoline ring, isoquinoline ring, phenanthridine Examples thereof include a nitrogen atom-containing heterocycle such as a ring and a carbazole ring.
^{However, when X 1 to} X ⁶ in the above formula (1) are all carbon atoms, in the dotted arc, the nitrogen atom of the benzene ring, fluorene ring, carbazole ring or carbazole ring is replaced with a sulfur atom or an oxygen atom. It is a ring structure other than a ring. These ring structures are structures represented by the following formulas (3-1) to (3-5), respectively.

In the above formula (1), M represents the same or different methylene group or amino group which may be substituted with an oxygen atom, a sulfur atom, a carbonyl group, or a halogen atom or an organic group. The methylene group and amino group which may be substituted with a halogen atom or an organic group are represented by the following formulas (4) and (5), respectively;

(In the formula, R ^{3 to} R ⁵ represent the same or different hydrogen atom, halogen atom or organic group).
When M is a methylene group or an amino group which may be substituted with a halogen atom or an organic group, examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the organic group to be substituted include the same groups as the following organic groups of R ¹ and R ² , but when the organic group to be substituted with the methylene group or the amino group is a hydrocarbon group, the hydrocarbon group may be a hydrocarbon group. An alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group and a propyl group is preferable.
Among these, M is preferably a methylene group or an amino group which may be substituted with an oxygen atom, a sulfur atom or a hydrocarbon group. More preferably, it is an oxygen atom or a sulfur atom.

In the above formula (1), R ¹ and R ² represent the same or different organic groups which are hydrogen atoms, halogen atoms or ring structure substituents. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the organic group include a haloalkyl group having 1 to 20 carbon atoms such as a methyl chloride group, a methyl bromide group, a methyl iodide group, a fluoromethyl group, a difluoromethyl group and a trifluoromethyl group; a methyl group, an ethyl group and a propyl group. , A linear or branched alkyl group having 1 to 20 carbon atoms such as an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, Cyclic alkyl group having 3 to 20 carbon atoms such as cycloheptyl group; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group , Octyloxy group, etc., linear or branched alkoxy group having 1 to 20 carbon atoms; hydroxyl group; thiol group; epoxy group; nitro group; azo group; allyl group; cyano group; amino group; methylamino group, Mono or dialkylamino group having an alkyl group having 1 to 20 carbon atoms such as ethylamino group, dimethylamino group and diethylamino group; amino group such as diphenylamino group and carbazolyl group; acyl such as acetyl group, propionyl group and butyryl group Group: Alkenyl group having 2 to 20 carbon atoms such as vinyl group, 1-propenyl group, allyl group, butenyl group and styryl group; 2 to 20 carbon atoms such as ethynyl group, 1-propynyl group, propargyl group and phenylacetylyl group. Alkinyl group of 2 to 20 carbon atoms such as vinyloxy group and allyloxy group; alkynyloxy group having 2 to 20 carbon atoms such as ethynyloxy group and phenylacetyloxy group; phenoxy group, naphthoxy group and biphenyloxy group , Pyrenyloxy group and other aryloxy groups having 6 to 20 carbon atoms; trifluoromethyl group, trifluoromethoxy group, pentafluoroethoxy group and other perfluoro groups having 1 to 20 carbon atoms and longer chain perfluoro groups; diphenyl Boryl group having 1 to 20 carbon atoms such as boryl group, dimesitylboryl group, bis (perfluorophenyl) bolyl group and diboronic acid ester group; carbonyl group having 1 to 20 carbon atoms such as acetyl group and benzoyl group; acetoxy group and benzoyl group. A carbonyloxy group having 1 to 20 carbon atoms such as an oxy group; an alkoxycarbonyl group having 2 to 20 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group and a phenoxycarbonyl group; 20 sul Finyl group; silyl group having 1 to 20 carbon atoms such as trimethylsilyl group, triisopropylsilyl group, dimethyl-tert-butylsilyl group, trimethoxysilyl group, triphenylsilyl group; halogen atom, alkyl group, alkoxy group, alkyl halide A phenyl group, a 2,6-xylyl group, a mesityl group, a duryl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a toluyl group, anisyl group, a fluorophenyl group which may be substituted with a group or the like. , Diphenylaminophenyl group, dimethylaminophenyl group, diethylaminophenyl group, phenanthrenyl group and other aryl groups having 6 to 20 carbon atoms; oligoaryl groups having 12 to 20 carbon atoms; thienyl group, frill group, silacyclopentadienyl group. , Oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, acridinyl group, quinolyl group, quinoxaloyl group, phenanthloryl group, benzothienyl group, benzothiazolyl group, indolyl group, carbazolyl group, pyridyl group, pyrrolyl group, benzoxazolyl group, Heterocyclic groups having 1 to 20 carbon atoms such as pyrimidyl group and imidazolyl group; oligo heterocyclic groups having 2 to 20 carbon atoms; carboxyl groups; carboxylic acid esters having 2 to 20 carbon atoms; epoxy groups; isocyano groups; cyanate groups; isocyanates Group; thiocyanate group; isothiocyanate group; carbamoyl group; N, N-dialkylcarbamoyl group having 2 to 20 carbon atoms such as N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group; formyl group; nitroso group; formyl Oxy group; stannyl group; phosphino group; silyloxy group; arylsulfonyloxy group having 6 to 20 carbon atoms; alkylsulfonyloxy group having 1 to 20 carbon atoms; alkylthio group having 1 to 20 carbon atoms; arylthio group having 6 to 20 carbon atoms Group; arylalkyl group with 7 to 20 carbon atoms; arylalkenyl group with 8 to 20 carbon atoms; arylalkynyl group with 8 to 20 carbon atoms; arylalkoxy group with 7 to 20 carbon atoms; arylalkylthio with 7 to 20 carbon atoms Group; monovalent heterocyclic group having 1 to 20 carbon atoms; monovalent heterocyclic group having 1 to 20 carbon atoms substituted with a halogen atom, haloalkyl group or the reactive group; monovalent group having 2 to 20 carbon atoms. Oligo heterocyclic group; examples thereof include a halogen atom, a haloalkyl group, or a monovalent oligo heterocyclic group having 2 to 20 carbon atoms substituted with the reactive group.
Further, as a ring structure formed by bonding organic groups to each other, a structure in which carbon atoms constituting the organic group form a bond can be mentioned.

The R ¹ and R ² are preferably halogen atoms such as hydrogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom; methyl chloride group, methyl bromide group, methyl iodide group and fluoro. Haloalkyl groups such as methyl group, difluoromethyl group, trifluoromethyl group; carboxyl group, hydroxyl group, thiol group, epoxy group, isocyanate group, amino group, azo group, acyl group, allyl group, nitro group, alkoxycarbonyl group, Reactive groups such as formyl group, cyano group, silyl group, stannyl group, boryl group, phosphino group, silyloxy group, arylsulfonyloxy group, alkylsulfonyloxy group; linear or branched alkyl having 1 to 4 carbon atoms. Group; linear or branched alkyl group having 1 to 4 carbon atoms substituted with a halogen atom, haloalkyl group or the reactive group; linear or branched alkoxy group having 1 to 8 carbon atoms; halogen atom , Haloalkyl group or linear or branched alkoxy group having 1 to 8 carbon atoms substituted with the reactive group; aryl group; halogen atom, haloalkyl group or aryl group substituted with the reactive group; oligoaryl; Group; oligoaryl group substituted with halogen atom, haloalkyl group or reactive group; monovalent heterocyclic group; monovalent heterocyclic group substituted with halogen atom, haloalkyl group or reactive group; monovalent Oligo heterocyclic group; monovalent oligo heterocyclic group substituted with halogen atom, haloalkyl group or reactive group; alkylthio group; aryloxy group; arylthio group; arylalkyl group; arylalkoxy group; arylalkylthio group; alkenyl Group; alkenyl group substituted with halogen atom, haloalkyl group or reactive group; alkynyl group; alkynyl group substituted with halogen atom, haloalkyl group or reactive group is preferred. More preferably, a hydrogen atom, a bromine atom, an iodine atom, a boryl group, an alkynyl group, an alkenyl group, a formyl group, a stenyl group, a phosphino group; a halogen atom, a haloalkyl group, an aryl group substituted with the reactive group; a halogen atom. , Haloalkyl group or oligoaryl group substituted with the reactive group; monovalent heterocyclic group substituted with halogen atom, haloalkyl group or the reactive group; substituted with halogen atom, haloalkyl group or the reactive group A monovalent oligo heterocyclic group; an alkenyl group; an alkenyl group substituted with a halogen atom, a haloalkyl group or the reactive group; an alkynyl group; an alkynyl group substituted with a halogen atom, a haloalkyl group or the reactive group. ..

In the above formula (1), m ¹ and m ² represent the numbers of ^{R 1} and R ² , respectively ^{, m 1} is 0 to 2, and m ² is a number of 1 or more.
m ¹ is preferably 1 or 2.
m ² is preferably 1 to 10. More preferably, it is 1 to 6, and even more preferably, it is 1 to 4.

In the above formula (1), ^{the position where R 1} other than M or hydrogen atom is bonded to the ^{ring structure formed by X 1 to} X ⁶ is not particularly limited, but the nitrogen atom is contained in ^{X 1 to} X ^6. In this case, it is preferable that ^{R 1} other than M or a hydrogen atom is bonded to the atom next to the nitrogen atom. When a nitrogen atom is contained in the ring structure, it is assumed that the nitrogen atom causes a decrease in reactivity, but when a compound having a structure in which a substituent is introduced in the vicinity of the nitrogen atom is used, the reaction by the nitrogen atom The effect of sexual deterioration is small. In this way, it is considered that the introduction of the substituent in the vicinity of the nitrogen atom, which is presumed to be the cause of the decrease in reactivity, contributes to the improvement in yield.

Specific examples of the compound represented by the above formula (1) include compounds represented by the following formulas (6-1) to (6-24) and substituents (the above formula) in the ring structure of these compounds. (1) structure of substituent groups) are bonded, represented by R ² are exemplified in. Examples of R in the formulas (6-5), (6-6), (6-17), and (6-18) include groups similar to the organic groups of ^{R 1} and R ^{2 described above.}

The step of synthesizing the compound represented by the formula (2) from the compound represented by the above formula (1) is preferably carried out in the presence of a palladium catalyst. By using a palladium catalyst, the yield of the compound represented by the formula (2) can be increased.
Examples of the palladium catalyst include palladium trifluoroacetate (Pd (TFA) ₂ ), palladium acetate (Pd (OAc) ₂ ), tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ ), and dichlorobis (triphenylphosphine) palladium. _{(PdCl 2 (PPh 3) 2} ), bis (tri -tert- butylphosphine) palladium ^{_{(Pd (P t Bu 3)}} 2), tris (dibenzylideneacetone) dipalladium _{(Pd 2 dba 3), [} PdCl 2 ( Palladium compounds such as PhCN) ₂ ] and [Pd (BF ₄ ) ₂ (MeCN) ₄ ], metallic palladium, and the like can be mentioned, and one or more of these can be used.
Among these, any of Pd (TFA) ₂ is preferable. More preferably, it is Pd (TFA) ₂ . By using Pd (TFA) ₂ , the compound represented by the formula (2) can be obtained in a higher yield.

When the palladium catalyst is used, the amount used is preferably 0.1 to 100 mol% with respect to 100 mol% of the compound represented by the formula (1). It is more preferably 1 to 50 mol%, and even more preferably 2 to 30 mol%.

The above synthesis step may be carried out using a base. As the base, one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide and the like can be used.

When the above base is used, the amount used is preferably 100 to 600 mol% with respect to 100 mol% of the compound represented by the formula (1). It is more preferably 100 to 400 mol%, and even more preferably 200 to 300 mol%.

The above synthesis step may be carried out using an oxidizing agent. As the oxidizing agent, one or more kinds such as silver acetate, copper acetate, silver nitrate and silver trifluoroacetic acid (Ag (TFA)) can be used.
Among these, either silver acetate or silver trifluoroacetic acid (Ag (TFA)) is preferable. More preferably, it is silver acetate. By using silver acetate, the compound represented by the formula (2) can be obtained in a higher yield.

When the above oxidizing agent is used, the amount used is preferably 400 to 2000 mol% with respect to 100 mol% of the compound represented by the formula (1). It is more preferably 400 to 1600 mol%, and even more preferably 400 to 1200 mol%.

The above synthesis step can be carried out using a solvent. As the solvent to be used, one or 2 of acetic acid, propionic acid, pivalic acid, benzoic acid, benzene chloride, toluene, xylene, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran, diethyl ether, dioxane and the like. More than a seed can be used.
Among these, either pivalic acid or propionic acid is preferable. More preferably, it is pivalic acid. By using pivalic acid, the compound represented by the formula (2) can be obtained in a higher yield.

The reaction temperature in the above synthesis step is not particularly limited as long as the reaction proceeds, but is preferably 0 to 200 ° C. It is more preferably 20 to 200 ° C, still more preferably 40 to 180 ° C, and particularly preferably 100 to 160 ° C.
The reaction pressure may be pressurized, normal pressure, or reduced pressure, but is preferably normal pressure. The reaction time is preferably 2 hours or more. More preferably, it is 4 to 24 hours.
The atmosphere in which the above synthesis step is performed is not particularly limited, and may be carried out in the air, or in an atmosphere of an inert gas such as nitrogen or argon, but the synthesis step can be carried out more easily by carrying out the synthesis step in the air. Can be done.

The method for producing a condensed polycyclic compound of the present invention may include a step of purifying the obtained condensed polycyclic compound represented by the above formula (2) after the above synthesis step. The purification method is not particularly limited, and a suitable method can be appropriately selected and used from methods such as extraction, filtration, silica gel chromatography, column chromatography, recycled preparative gel permeation chromatography, recrystallization, and sublimation. can. Moreover, any one of these purification methods may be used, or two or more may be used.

The condensed polycyclic compound represented by the above formula (2) obtained by the method for producing a condensed polycyclic compound of the present invention is a material for an electric light emitting element, particularly light emission, host, electron transport, and electron injection of an electric light emitting element. , the dopant is a compound useful as a hole blocking material, also used as a compound n-type semiconductor material is a heterocyclic ring X ring such as a nitrogen atom-containing ring consists of ¹ to X ⁶ in the formula (2) You can also do it. Such a condensed polycyclic compound that can be used for various purposes, that is, the following formula (2);

(In the formula, X ^{1 to} X ⁶ represent the same or different carbon atom or nitrogen atom. The dotted arc indicates the aromatic hydrocarbon ring or sulfur atom together with the carbon-carbon double bond portion represented by the solid line. , Indicates that an aromatic heterocyclic structure containing an oxygen atom or a nitrogen atom is formed, and when X ^{1 to} X ⁶ are all carbon atoms, the nitrogen atom of the benzene ring, fluorene ring, carbazole ring or carbazole ring Is a ring structure other than the ring substituted with a sulfur atom or an oxygen atom. M is the same or different, a methylene group optionally substituted with an oxygen atom, a sulfur atom, a carbonyl group, or a halogen atom or an organic group. or ^.R 1, ^{R 2} representing an amino group are the same or different, a hydrogen atom, the number of each ^.m 1, ^{m 2} represents an organic group which is a substituent of a halogen atom or a ring structure ^R 1, ^{R 2 M 1} is 0 to 2, and m ² is a number of 1 or more. When a ^{plurality of R 1} and R ² are bonded to an aromatic ring or a complex aromatic ring structure forming an arc portion of a dotted line. , The organic groups may be bonded to each other to form a ring structure. N is 2 or 3), and the condensed polycyclic compound is also the present invention. There is one.

The method for producing a condensed polycyclic compound of the present invention has the above-mentioned configuration, and is a method capable of easily producing a condensed polycyclic compound useful as a material for an organic electric field light emitting device, an n-type organic semiconductor, or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".

^{1 1} H-NMR measurement was carried out as follows.
< ^{1 1} H-NMR>
The obtained condensed polycyclic compound was used as a solution of deuterated chloroform and measured using a high-resolution nuclear magnetic resonance apparatus (product name "Gemini 2000"; 300 MHz, manufactured by Varian, Inc.). ¹ The chemical shift in 1 H-NMR was recorded as one millionth (ppm; δ scale) from tetramethylsilane on the low magnetic field side, and the hydrogen nucleus (δ0.00) of tetramethylsilane was referred to.

Example 1
4. Reaction substrate (690 mg, 1.0 mmol) represented by the following formula (7-1), palladium trifluoroacetate (79 mg, 0.2 mmol), silver acetate (670 mg, 4.0 mmol), pivalic acid in a Schlenk tube. 5 g was added and replaced with nitrogen. This was heated to 160 ° C. and heated and stirred for 48 hours. After completion of the reaction, the mixture was filtered through Celite using ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and water, respectively, dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel chromatography (mobile phase: ethyl acetate / hexane) to obtain the target product represented by the following formula (7-2). The yield was 65%.
The physical property values of the target object are as follows.
^{1 1} H-NMR (CDCl ₃ ): δ7.80-7.82 (m, 4H), 7.92 (s, 2H), 8.12 (s, 4H), 8.26 (d, 2H), 9 .02 (s, 1H)

Example 2
A reaction substrate (3.2 g, 10 mmol) represented by the following formula (8-1), palladium trifluoroacetate (1.6 g, 4.0 mmol), silver acetate (13 g, 80 mmol), and pivalic acid 45 g are placed in a Schlenk tube. In addition, nitrogen substitution was performed. This was heated to 160 ° C. and heated and stirred for 48 hours. After completion of the reaction, the mixture was filtered through Celite using ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and water, respectively, dried over magnesium sulfate, filtered, and then the solvent was distilled off. The obtained crude product was purified by silica gel chromatography (mobile phase: ethyl acetate / hexane) to obtain the target product represented by the following formula (8-2). The yield was 31%.
The physical property values of the target object are as follows.
^{1 1} H-NMR (CDCl ₃ ): δ7.09-7.11 (m, 2H), 7.48 (d, 2H), 7.57 (d, 2H), 8.74 (s, 1H)

Examples 3-28
By the reaction of the following reaction formula (9), compounds in which the structural portions of ^{M and R 2 were variously changed were synthesized.} The structure and yield of the synthesized compound are shown in Tables 1 to 4.

Comparative Examples 1 and 2
When a compound that undergoes a cross-coupling reaction at only one site was used as the reaction substrate as in the following reaction formulas (10) and (11), the yields were low in both cases. From this result, the technical significance of the production method of the present invention, in which a product can be obtained in a high yield by performing a cross-coupling reaction at two or more sites, was confirmed.

Claims (5)

A method for producing a condensed polycyclic compound having a structure in which a plurality of rings including an aromatic ring are fused, and the production method uses palladium trifluoroacetate as a catalyst and has the following formula (1);

(Wherein, X ⁴ is a carbon atom or a nitrogen atom table to dashed arc, carbon represented by the solid line -. An aromatic hydrocarbon ring or a sulfur atom together with the carbon-carbon double bond moiety, an oxygen atom or a nitrogen atom Indicates that an aromatic heterocyclic structure containing is formed. M is the same or different, a methylene group or a methylene group which may be substituted with an oxygen atom, a sulfur atom, a carbonyl group, or a halogen atom or an organic group. represents an amino group. R ¹ are the same or different, hydrogen atoms Komata is. R ² represents an organic group which is a substituent of the ring structure are the same or different, the replacement of a hydrogen atom, a halogen atom or a ring structure It represents an organic group comprising a group. the organic group represented by M and ^R 1, ^{R 2} is a haloalkyl group having 1 to 20 carbon atoms, a linear or branched alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms Cyclic alkyl group, linear or branched alkoxy group having 1 to 20 carbon atoms, mono or dialkylamino group having an alkyl group having 1 to 20 carbon atoms, diphenylamino group, carbazolyl group, acyl group, 2 carbon atoms. ~ 20 alkenyl groups, 2 to 20 carbon atoms alkynyl groups, 2 to 20 carbon atoms alkenyloxy groups, 2 to 20 carbon atoms alkynyloxy groups, 6 to 20 carbon atoms aryloxy groups, 1 to 20 carbon atoms Perfluoro group, boryl group having 1 to 20 carbon atoms, carbonyl group having 1 to 20 carbon atoms, carbonyloxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, sulfinyl having 1 to 20 carbon atoms. group, a silyl group having 1 to 20 carbon atoms, a halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl phenyl group optionally substituted with a group, an aryl group having 6 to 20 carbon atoms, mosquitoes carboxyl group, the number of carbon atoms 2 to 20 carboxylic acid ester groups, epoxy groups, isocyano groups, cyanate groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, carbamoyl groups, N, N-dialkylcarbamoyl groups with 2 to 20 carbon atoms, formyl groups, formyloxy Group, stannyl group, arylsulfonyloxy group having 6 to 20 carbon atoms, alkylsulfonyloxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, 7 to 20 carbon atoms Aromatic alkyl group, arylalkenyl group having 8 to 20 carbon atoms, arylalkynyl group having 8 to 20 carbon atoms, arylalkoxy group having 7 to 20 carbon atoms, arylalkylthio group having 7 to 20 carbon atoms, and 1 to 20 carbon atoms. Monovalent heterocycle, halogen atom or haloal It is one of a monovalent heterocyclic group having 1 to 20 carbon atoms substituted with a kill group. m ¹ and m ² represent the numbers of R ¹ and R ^{2 , respectively, m 1} is 0 to 2, and m ² is a number of 1 or more. If the R ² are a plurality bonded to an aromatic ring or a heteroaromatic ring structure to form an arc portion of the dotted lines, they may form a ring structure by bonding with each other an organic group. ) By the reaction of forming a bond between the ring structures of the polycyclic compound represented by the following formula (2);

(In the formula, X ⁴ , the dotted arc, M, R ¹ , R ² , m ¹ , and m ² are the same as in formula (1).) The step of synthesizing the condensed polycyclic compound represented by the formula (1). A method for producing a condensed polycyclic compound, which comprises. The method for producing a condensed polycyclic compound according to claim 1, wherein the synthesis step is carried out using an oxidizing agent. The method for producing a condensed polycyclic compound according to claim 1 or 2, wherein the synthesis step is carried out using a solvent. The method for producing a condensed polycyclic compound according to any one of claims 1 to 3, wherein the synthesis step is carried out at 0 to 200 ° C. The following formula (2);

(Wherein, X ⁴ is a carbon atom or a nitrogen atom table to dashed arc, carbon represented by the solid line -. Aromatic heterocycle containing an aromatic hydrocarbon ring or a nitrogen atom together with a carbon double bond moiety .M indicating that a structure is formed, which may be the same or different, an oxygen atom, a sulfur atom, a carbonyl group, or. R ¹ a methylene group which may be substituted by a halogen atom or an organic group, The same or different represents an organic group which is a substituent of a hydrogen atom, a halogen atom or a ring structure. R ² represents the same or different organic group which is a substituent of a hydrogen atom or a ring structure. ^{The organic groups in 1} and R ² are haloalkyl groups having 1 to 20 carbon atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, cyclic alkyl groups having 3 to 20 carbon atoms, and 1 to 20 carbon atoms. Linear or branched alkoxy group, mono or dialkylamino group having an alkyl group having 1 to 20 carbon atoms, diphenylamino group, carbazolyl group, acyl group, alkenyl group having 2 to 20 carbon atoms, 2 to 20 carbon atoms Alkinyl group, alkenyloxy group having 2 to 20 carbon atoms, alkynyloxy group having 2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, perfluoro group having 1 to 20 carbon atoms, carbon number 1 to 20 Boryl group, carbonyl group having 1 to 20 carbon atoms, carbonyloxy group having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbon atoms, sulfinyl group having 1 to 20 carbon atoms, silyl group having 1 to 20 carbon atoms, halogen atom, an alkyl group, an alkoxy group, or a halogenated alkyl phenyl group optionally substituted with a group, an aryl group having 6 to 20 carbon atoms, mosquitoes carboxyl group, a carboxylic acid ester group having 2 to 20 carbon atoms, an epoxy group , Isocyano group, cyanate group, isocyanate group, thiocianate group, isothiocyanate group, carbamoyl group, N, N-dialkylcarbamoyl group having 2 to 20 carbon atoms, formyl group, formyloxy group, stanyl group, carbon number 6 to 20 Arylsulfonyloxy group, alkylsulfonyloxy group having 1 to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms, arylthio group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, 8 to 20 carbon atoms. Arylalkenyl group, arylalkynyl group having 8 to 20 carbon atoms, arylalkenyl group having 7 to 20 carbon atoms, arylalkylthio group having 7 to 20 carbon atoms, monovalent heterocycle having 1 to 20 carbon atoms, halogen atom or haloalkyl A monovalent compound with 1 to 20 carbon atoms substituted with a group It is one of the prime ring groups. m ¹ and m ² represent the numbers of R ¹ and R ^{2 , respectively, m 1} is 0 to 2, and m ² is a number of 1 or more. If the R ² are a plurality bonded to an aromatic ring or a heteroaromatic ring structure to form an arc portion of the dotted lines, they may form a ring structure by bonding with each other an organic group. ) , A condensed polycyclic compound.