JP6840931B2 - Method for Producing Fused Ring Aromatic Compound - Google Patents

Description

The present invention relates to a method for producing a useful organic compound and a fused aromatic compound which is an intermediate thereof.

The basic structure of an organic electroluminescent device is that a light emitting layer containing a light emitting material is sandwiched between a hole transport layer and an electron transport layer, and an anode and a cathode are attached to the outside thereof, and the positive electroluminescence device is injected into the light emitting layer. It is an element that utilizes the emission of light (fluorescence or phosphorescence) associated with exciton deactivation caused by the recombination of holes and electrons, and is applied to displays and the like. The hole transport layer is divided into a hole transport layer and a hole injection layer, the light emitting layer is divided into an electron block layer, a light emitting layer and a hole block layer, and the electron transport layer is divided into an electron transport layer and an electron injection layer. It may be configured.

In recent years, a large number of organic electric field light emitting elements using fused aromatic compounds typified by nitrogen-substituted dibenzothiophene compounds, nitrogen-substituted dibenzofuran compounds, and nitrogen-substituted carbazole compounds for the light emitting layer and the electron transport layer have been proposed (for example, patents). (Refer to Documents 1 to 3), but few efficient methods for synthesizing them have been reported, and a simple synthesizing method is required.

International Publication No. 2004/095891 Pamphlet Japanese Unexamined Patent Publication No. 2011-84531 US 2009/0134784 Pamphlet

Simple synthesis of nitrogen-substituted dibenzothiophene compounds, nitrogen-substituted dibenzofuran compounds, and nitrogen-substituted carbazole compounds, which are useful compounds as materials for organic electroluminescent devices, is desired.

As a result of diligent studies to solve the above problems, the present inventors have the following general formula (1).

(During the ceremony,
Ring A represents an aromatic ring having an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur as a ring-constituting atom (the ring may have a substituent).
Y and Y'are independently carbon atoms which may have substituents, nitrogen atoms which may have substituents, oxygen atoms, sulfur atoms, single bonds, or 1,2-ethylene. It shows a diyl group and either Y or Y'is a single bond.
R ¹ is an aromatic group having 4 to 66 carbon atoms (the group is a fluorine atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, and the like. A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. It may have a leaving group as a substituent), a leaving group, a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms. )
Aromatic compound represented by, the following general formula (2), or (6)

(During the ceremony,
R ² is an aromatic group (in which the 4-66 carbon atoms, a fluorine atom, a methyl group, an ethyl group, a straight chain of 3 to 10 carbon atoms, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. It may have a leaving group as a substituent), represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms.
W ¹ represents a cyano group, an aminocarbonyl group, an acetyl group, or a formyl group.
Z ² represents a leaving group.
W ² represents an aminocarbonyl group or an acetyl group. )
By reacting the compound represented by ^{(3) and, when W 1} is a formyl group, an ammonium salt in combination, the general formula (3), (5), or (7)

(During the ceremony,
Rings A, Y, Y', R ¹ , and R ² are the same as described above.
X ⁵ represents a group represented by CR ^{3 or a nitrogen atom.}
R ³ is an aromatic group having 4 to 66 carbon atoms (the group is a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, or an alkoxy group having 3 to 10 carbon atoms. , An alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a desorbing group as a substituent). .. )
It has been found that a condensed aromatic compound represented by (hereinafter, also referred to as “the present compound”) can be easily and efficiently produced, and the present invention has been completed. The compound represented by the general formula (3), (5), or (7) is extremely useful as an organic electroluminescent device material or a manufacturing intermediate thereof.

Hereinafter, the present invention will be described in detail.

The present invention relates to the above-mentioned manufacturing method (hereinafter, also referred to as "the present manufacturing method").

Hereinafter, the aromatic compound represented by the general formula (1) may be abbreviated as the compound (1). Further, compound (2) and the like, which will be described later, are also used as the same abbreviations.

In compound (1), ring A represents an aromatic ring having an atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur as a ring-constituting atom (the ring may have a substituent). ..

Ring A is not particularly limited, but for example, benzene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, 1,2,4-triazine ring, naphthalene ring, quinoline ring, isoquinoline ring, quinazoline ring, and the like. Kinoxalin ring, naphthylidine ring, thiophene ring, furan ring, pyrol ring, imidazole ring, 1,2,3-triazole ring, oxazole ring, isooxazole ring, thiazole ring, isothiazole ring, benzothiophene ring, benzofuran ring, indole ring , Fluorene ring, phenanthrene ring, anthracene ring, pyrene ring, crisen ring, or pyrimidine ring (these rings may have a substituent) and the like.

The substituent that the ring A may have is not particularly limited, but for example, an aromatic group having 4 to 66 carbon atoms (the group is a fluorine atom, a methyl group, an ethyl group, or 3 carbon atoms). A linear, branched or cyclic alkyl group of 10 to 10, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, 1 to 1 carbon atoms. 3 halogenated alkoxy group, diarylamino group having 10 to 36 carbon atoms, or elimination group (for example, chlorine atom, bromine atom, iodine atom, trifurate, etc.) may be used as a substituent), elimination. Examples thereof include a group (for example, chlorine atom, bromine atom, iodine atom, trifurate, etc.), hydrogen atom, deuterium atom, methyl group, ethyl group, alkyl group having 3 to 10 carbon atoms and the like.

The aromatic group having 4 to 66 carbon atoms defines only the ring skeleton which may be condensed or linked, and the carbon number of the aromatic group does not include the carbon number of the substituent. In the aromatic group having 4 to 66 carbon atoms, the aromatic group is not particularly limited as long as it is an aromatic hydrocarbon group, a heteroaromatic group, or a fused or linked product thereof.

The aromatic group having 4 to 66 carbon atoms is not particularly limited, but for example, a phenyl group, a biphenylyl group, a terphenyl group, a naphthyl group, a naphthylphenyl group, a phenylnaphthyl group, a naphthylbiphenyl group, or a biphenylnaphthyl. Group, diphenylnaphthyl group, phenylnaphthylphenyl group, anthryl group, anthrylphenyl group, phenylanthryl group, phenylanthrylphenyl group, phenanthryl group, phenanthrylphenyl group, phenylphenanthryl group, pyrenyl group, phenylpyre Nyl group, pyrenylphenyl group, fluorenyl group, fluorenylphenyl group, phenylfluorenyl group, fluoranthenyl group, phenylfluoranthenyl group, fluoranthenylphenyl group, peryleneyl group, phenylperyleneyl group, peri Renylphenyl group, triphenylenyl group, phenyltriphenylenyl group, triphenylenylphenyl group, tetrasenyl group, phenyltoterasenyl group, tetrasenylphenyl group, chrysenyl group, phenylcrisenyl group, chrysenylphenyl group ( (Aromatic hydrocarbon group that may be linked or condensed), pyridyl group, phenylpyridyl group, pyridylphenyl group, bipyridyl group, biphenylpyridyl group, pyridylbiphenyl group, diphenylpyridyl group, pyrimidyl group, phenylpyrimidyl Group, pyrimidylphenyl group, pyrazil group, phenylpyrazil group, pyrazilphenyl group, triazinyl group, phenyltriazyl group, triazilphenyl group, quinolyl group, phenylquinolyl group, quinolylphenyl group, pyridylquinolyl group, Isoquinolyl group, phenylisoquinolyl group, isoquinolylphenyl group, pyridylisoquinolyl group, quinoxalinyl group, phenylquinoxalinyl group, quinoxalinylphenyl group, acridinyl group, phenylacridinyl group, acridinyl Phenyl group, phenanthridinyl group, phenylphenanthridinyl group, phenanthridinylphenyl group, phenanthrolinyl group, phenylphenanthrolinyl group, phenanthrolinylphenyl group, pyrrolyl group, phenylpyrrolill group , Pyrrolylphenyl group, pyridylpyrrrolyl group, furanyl group, phenylfuranyl group, furanylphenyl group, pyridylfuranyl group, thienyl group, phenylthienyl group, thienylphenyl group, imidazolyl group, phenylimidazolyl group, imidazolylphenyl group , Oxazolyl group, Phenyl Oxazolyl group, Oxazolyl pheni Lu group, isoxazolyl group, phenylisoxazolyl group, isoxazolylphenyl group, oxadiazolyl group, phenyloxadiazolyl group, oxadiazolylphenyl group, thiazolyl group, phenylthiazolyl group, thiazolylphenyl group, Indrill group, phenylindolyl group, indrill phenyl group, benzofuranyl group, phenylbenzofuranyl group, benzofuranylphenyl group, benzothiazolyl group, phenylbenzothiazolic group, benzothiazolylphenyl group, benzoimidazolyl group, phenylbenzoimidazolyl group Group, benzoimidazolyl phenyl group, benzoxazolyl group, phenylbenzoxazolyl group, benzoxazolylphenyl group, benzothiazolyl group, phenylbenzothiazolyl group, benzothiazolylphenyl group, dibenzofuranyl group, phenyldibenzo Furanyl group, dibenzofuranylphenyl group, dibenzothienyl group, phenyldibenzothienyl group, dibenzothienylphenyl group, carbazolyl group, phenylcarbazolyl group, carbazolylphenyl group, pyridylcarbazolyl group, pyridylphenylcarbazolyl Group, Carbolinyl Group, PhenylCarbolinyl Group, Carbolinylphenyl Group, Indolocarbazolyl Group, Phenylindrocarbazolyl Group, Phenylindrocarbazolylphenyl Group, Indolocarbazolylphenyl Group, India Examples thereof include a logibenzothienyl group, a phenylindodibenzothienyl group, and an indodibenzothienylphenyl group (these are heteroaromatic groups that may be linked or condensed).

The linear, branched, or cyclic alkyl group having 3 to 10 carbon atoms is not particularly limited, and is, for example, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or tert-butyl. Group, n-pentyl group, sec-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, benzyl group, phenethyl group, etc. Can be mentioned.

The linear, branched, or cyclic alkoxy group having 3 to 10 carbon atoms is not particularly limited, and is, for example, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, or tert-. Butoxy group, n-pentyloxy group, sec-pentyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group , Benzyloxy group, phenethyloxy group and the like.

The alkyl halide group having 1 to 3 carbon atoms is not particularly limited, but for example, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloroethyl group, or a dichloro. Examples thereof include an ethyl group, a trichloroethyl group, a pentachloroethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group, a chloropropyl group and a fluoropropyl group.

The halogenated alkoxy group having 1 to 3 carbon atoms is not particularly limited, but for example, a chloromethyloxy group, a dichloromethyloxy group, a trichloromethyloxy group, a fluoromethyloxy group, a difluoromethyloxy group, or a tri. Fluoromethyloxy group, chloroethyloxy group, dichloroethyloxy group, trichloroethyloxy group, pentachloroethyloxy group, fluoroethyloxy group, difluoroethyloxy group, trifluoroethyloxy group, pentafluoroethyloxy group, chloro Examples thereof include a propyloxy group and a fluoropropyloxy group.

The diarylamino group having 10 to 36 carbon atoms represents an amino group in which two kinds of aryl groups which may be different are bonded, and means that the total carbon number is 10 to 36.

The diarylamino group having 10 to 36 carbon atoms is not particularly limited, but for example, N, N-diphenylamino group, N-tolyl-N-phenylamino group, N, N-ditrilamino group, N, N. -Dibiphenylamino group, N, N-di (terphenyl) amino group, N-phenyl-N-naphthylamino group, N-phenyl-N-biphenylamino group, N-phenyl-N-terphenylamino group, N -Biphenyl-N-terphenylamino group and the like can be mentioned.

The desorbing group is not particularly limited, but for example, a hydrogen atom, a chlorine atom, a bromine atom, a trifurate, a tosylate, an iodine atom, an amino group (for example, an amino group, a methylamino group, an ethylamino group, a butylamino group). Group, phenylamino group, dimethylamino group, diethylamino group,), metal-containing group (eg, Li, Na, MgCl, MgBr, MgI, CuCl, CuBr, CuI, AlCl ₂ , AlBr ₂ , Al (Me) ₂ , Al (Et) ₂ , Al ( ⁱ Bu) ₂ , Sn (Me) ₃ , Sn (Bu) ₃ , SnF ₃ , ZnR ³⁴ (R ³⁴ represents a halogen atom. ZnR ³⁴ includes ZnCl, ZnBr, ZnI, etc. (Examples include), Si (R ³¹ ) ₃ (for example, SiMe ₃ , SiPh ₃ , SiMePh ₂ , SiCl ₃ , SiF ₃ , Si (OMe) ₃ , Si (OEt) ₃ , Si (OMe) ₂ OH, etc.), BF ₃ K, B (OR ³² ) ₂ (for example, B (OH) ₂ , B (OMe) ₂ , B (O ⁱ Pr) ₂ , B (OBu) ₂ , B (OPh) _2, etc.), B (OR) ³³ ) ₃ etc.) can be exemplified.

A ligand such as an ether or an amine may be coordinated to the metal-containing group, and the type of the ligand is not limited as long as it does not inhibit the reaction formula (1).

Further, as B (OR ³² ) ₂ , those represented by the following (I) to (VII) can be exemplified, and those represented by (II) are preferable in terms of good yield.

Examples of the B (OR ³³ ) ₃ include those shown in the following (I) to (III).

Of these leaving groups, chlorine atom, bromine atom, triflate, iodine atom, B (OR ³² ) ₂ or B (OR ³³ ) ₃ are selected from the viewpoint of ease of post-reaction treatment and ease of raw material procurement. preferable.

The aromatic groups having 4 to 66 carbon atoms are each independently a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, an alkoxy group having 3 to 10 carbon atoms, and carbon. It may have a substituent selected from the group consisting of an alkyl halide group having a number of 1 to 3, an alkoxy halide group having 1 to 3 carbon atoms, and a diarylamino group having 10 to 36 carbon atoms. May be plural. When there are a plurality of substituents, each substituent may be the same or different.

As the substituent that the aromatic group having 4 to 66 carbon atoms may have, a methyl group or a diarylamino group having 10 to 36 carbon atoms is preferable in terms of excellent charge transport characteristics.

Further, as the leaving group that the aromatic group having 4 to 66 carbon atoms may have, it is useful from the fused ring aromatic compounds obtained by the production methods represented by the reaction formulas (1) to (10). Hydrogen atom, chlorine atom, bromine atom, iodine atom, trifurate, tosylate, metal-containing group (for example, Sn (Me) ₃ , Sn (Bu) ₃ , Si (R ³¹⁾ ) ₃ (for example, SiMe ₃ , SiPh ₃ , SiMePh ₂ , SiCl ₃ , SiF ₃ , Si (OMe) ₃ , Si (OEt) ₃ , Si (OMe) ₂ OH, etc.), BF ₃ K, B (OR ³² ) _{2 ^{(e.g., B (OH) 2, B}} (OMe) 2, B (O i Pr) 2, B (OBu) 2, B (OPh) 2 or the like), ^{B (OR} _{33) 3,} etc.) and the like can be mentioned ..

Ring A is an aromatic ring having an atom selected from the group consisting of carbon and nitrogen as a ring-constituting atom (the ring may have a substituent) because of its excellent production efficiency of this compound. It is preferably a benzene ring, a pyridine ring, a pyrimidine ring, or a pyrazine ring (these rings may have a substituent), preferably a benzene ring, a pyridine ring, a pyrimidine ring, or a pyrazine ring. Rings (These rings may have a elimination group, a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a phenyl group, a trill group, a naphthyl group, a biphenyl group, or a pyridyl group as substituents. Good).

In the aromatic compound represented by the general formula (1), Y and Y'are independent of each other, a carbon atom which may have a substituent, a nitrogen atom which may have a substituent, and oxygen. It represents an atom, a sulfur atom, a single bond, or a 1,2-ethylenediyl group, and either Y or Y'is a single bond.

The substituents in the carbon atom and the nitrogen atom which may have the substituents described in Y and Y'are not particularly limited, but are the same groups as the substituents which the ring A may have. Can be exemplified.

In the aromatic compound represented by the general formula (1), R ¹ is an aromatic group having 4 to 66 carbon atoms (the group is a fluorine atom, a methyl group, an ethyl group, a straight chain having 3 to 10 carbon atoms, and the like. A branched or cyclic alkyl group, a methoxy group, an ethoxy group, a linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, or a halogenated group having 1 to 3 carbon atoms. It may have an alkoxy group, a diarylamino group having 10 to 36 carbon atoms, or a desorbing group as a substituent), a desorbing group, a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, or 3 carbon atoms. Represents a linear, branched, or cyclic alkyl group of 10. )
Shown in the ^{R 1,} an aromatic group of 4-66 carbon atoms, straight-chain having 3 to 10 carbon atoms, branched, or cyclic alkyl group, straight chain having 3 to 10 carbon atoms, branched, or cyclic alkoxy group The alkyl halide group having 1 to 3 carbon atoms, the alkoxy halide group having 1 to 3 carbon atoms, the diarylamino group having 10 to 36 carbon atoms, and the leaving group are the same as the definitions in the ring A. The same applies to the preferred ones.

In addition, in terms of excellent efficiency and yield of this production method, the compounds represented by the general formula (1) are the following general formulas (1-A), (1-B), (1-C), and ( It is preferably a compound represented by 1-D).

(In the formula, Y'' represents an oxygen atom, a sulfur atom, a nitrogen atom which may have a substituent, or a carbon atom which may have a substituent. Rings A and R ¹ are general formulas. Represents the same definition as (1).
The substituent at the nitrogen atom which may have the above-mentioned substituent is not particularly limited, but the same substituent as the above-mentioned substituent in the substituent which may have the ring A is exemplified. be able to.

The compounds represented by the following general formula (2) or (6) are as follows.

(During the ceremony,
R ² is an aromatic group (in which the 4-66 carbon atoms, a fluorine atom, a methyl group, an ethyl group, a straight chain of 3 to 10 carbon atoms, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. It may have a leaving group as a substituent), represents a hydrogen atom, a heavy hydrogen atom, a methyl group, an ethyl group, or a linear, branched, or cyclic alkyl group having 3 to 10 carbon atoms.
W ¹ represents a cyano group, an aminocarbonyl group, an acetyl group, or a formyl group.
Z ² represents a leaving group.
W ² represents an aminocarbonyl group or acetyl. )
In R ^2, an aromatic group of 4-66 carbon atoms, straight-chain having 3 to 10 carbon atoms, branched, or cyclic alkyl group, straight chain having 3 to 10 carbon atoms, branched, or cyclic alkoxy group, the carbon number The alkyl halide groups 1 to 3, the alkoxy group halide having 1 to 3 carbon atoms, the diarylamino group having 10 to 36 carbon atoms, and the leaving group are the same as the definitions in the ring A, and are preferable. Is the same.

The ^{aminocarbonyl group in W 1} is not particularly limited, but for example, an aminocarbonyl group, a bis (trimethylsilyl) aminocarbonyl group, or the like having a substituent that is easily eliminated in the process of the cyclization reaction is used. Can be mentioned.

The acetyl group in W ¹ is not particularly limited, and examples thereof include substituted or unsubstituted ethanoyl groups, propanoyl groups, butanoyl groups, phenylethanoyl groups and the like.

The ^{leaving group shown in Z 2} is the same as the definition in the ring A, and the same applies to the preferable one.

The aminocarbonyl group and the acetyl group in ^{W 2} are not particularly limited, and examples thereof include the same ^{groups as those exemplified in W 1 above.}

Regarding the production method of the present invention, when W ¹ is a formyl group, an ammonium salt is used in combination.

The ammonium salt is not particularly limited, and examples thereof include NH ₄ F, NH ₄ Cl, NH ₄ Br, NH ₄ I, NH ₄ OAc, NH ₄ OTf, and NH ₄ OTs. ..

The amount of the ammonium salt used is not particularly limited, but is preferably 0.1 to 100 times the molar amount of 1 mol of the compound represented by the general formula (2), according to the production method of the present invention. In terms of good yield, it is preferably 1 to 20 times the molar amount.

The production method of the present invention can be carried out in the presence of a base or an acid, or can be carried out in the absence of an acid or a base.

The base that can be used in the production method of the present invention is not particularly limited, but for example, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, etc. Examples thereof include potassium acetate, sodium acetate, potassium phosphate, sodium phosphate, sodium fluoride, potassium fluoride, cesium fluoride and the like. Of these, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, potassium phosphate, and sodium phosphate are preferable, and potassium phosphate is more preferable, in terms of good yield.

In the production method of the present invention, the amount of the base used is not particularly limited, but it is preferably 0.1 to 10 times the molar amount of 1 mol of the compound (1), and the yield is good. More preferably, the molar amount is 0 to 4.0 times.

The acid that can be used in the production method of the present invention is not particularly limited, but for example, hydrochloric acid, sulfuric acid, carbonic acid, phosphoric acid, acetic acid, benzoic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p. -Toluene sulfonic acid, Eaton's reagent ( _{10: 1 mixture of methane sulfonic acid and P 2} O ₅ ), various Lewis acids and the like can be mentioned. Lewis acids include AlCl ₃ , Al (OTf) ₃ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , Zn (OTf) ₂ , FeCl ₂ , FeCl ₃ , BF ₃ , GaCl ₃ , InCl ₃ , InBr ₃ , InI ₃ , In. (OTf) ₃ , Yb (OTf) ₃ , SiMe ₃ Cl, SiMe ₃ I, SiMe ₃ OTf and the like can be mentioned. Of these, hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and Eaton's reagent are preferable, and sulfuric acid is more preferable, in terms of good yield.

The production method of the present invention is preferably carried out in a solvent. The solvent is not particularly limited, but for example, water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), tetrahydrofuran (THF), toluene, benzene, diethyl ether, 1,4-dioxane, ethanol, butanol, xylene and the like. Can be exemplified, and these may be used in combination as appropriate. Further, the substrate compound (2) or (6) may be used as a solvent. Of these, THF and DMF are preferable in terms of good yield.

In the production method of the present invention, the amount of the acid used is not particularly limited, but it is preferably 0.1 to 10 times the molar amount of 1 mol of the compound (1), and the yield is good. More preferably, the molar amount is 0 to 4.0 times. It is also possible to use an acid as a solvent.

The production method of the present invention can be expressed more concretely by the reaction formulas (1), (2) and (3) shown below.

Next, the reaction of the reaction formula (1) will be described.

The reaction formula (1) is a reaction for obtaining a condensed aromatic compound represented by the general formula (3a) by reacting the compound (1a) and the compound (2) in the presence or absence of a base or an acid. is there. The compound (1a) is a subordinate concept of the compound (1), and the compound (3a) is a subordinate concept of the compound (3).

(In the general formula,
The same definitions as above are given for ^{R 1} , R ² , W ¹ , Y, and X ^5.
X ^{1 to} X ⁴ independently ^{represent CR 3} or a nitrogen atom.
R ³ is an aromatic group having 4 to 66 carbon atoms (independently, a fluorine atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 10 carbon atoms, a methoxy group and an ethoxy group. , A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, Alternatively, it may have a leaving group as a substituent), a hydrogen atom, a heavy hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 10 carbon atoms, methoxy. Group, ethoxy group, linear, branched or cyclic alkoxy group with 3 to 10 carbon atoms, methylthio group, ethylthio group, linear, branched or cyclic sulfide group with 3 to 10 carbon atoms, 0 to 12 carbon atoms Represents an alkylamino group or a diarylamino group having 10 to 36 carbon atoms. )
In R ^3, aromatic group 4-66 carbon atoms, straight-chain having 3 to 10 carbon atoms, branched, or cyclic alkyl group, straight chain having 3 to 10 carbon atoms, branched, or cyclic alkoxy group, the carbon number The alkyl halide groups 1 to 3, the alkoxy group halide having 1 to 3 carbon atoms, the diarylamino group having 10 to 36 carbon atoms, or the leaving group are the same as the definitions in the ring A, and are preferable. Is the same.

The linear, branched, or cyclic sulfide group having 3 to 10 carbon atoms in R ³ is not particularly limited, and is, for example, an n-propyl sulfide group, an isopropyl sulfide group, an n-butyl sulfide group, sec. -Butyl sulfide group, tert-butyl sulfide group, n-pentyl sulfide group, sec-pentyl sulfide group, cyclopentyl sulfide group, n-hexyl sulfide group, cyclohexyl sulfide group, n-heptyl sulfide group, n-octyl sulfide group, n -Nonyl sulfide group, n-decyl sulfide group, benzyl sulfide group, phenethyl sulfide group and the like can be mentioned.

In R ^3, the alkyl amino group having 0 to 12 carbon atoms is not particularly limited, for example, dimethylamino group, diethylamino group, diisopropylamino group, diallylamino group, tert- butyl group, cyclohexylamino group Etc. can be exemplified.

The compound (1a) and the compound (2) used in the reaction of the reaction formula (1) can be produced by using a known production method, or a commercially available product can be used.

The compound (1a) is not particularly limited, and for example, the following compounds represented by 1-1 to 1-150 can be exemplified.

The compound (2) is not particularly limited, and for example, the following compounds represented by 2-1 to 2-200 can be exemplified. However, Ac of 2-101 to 2-150 represents an acetyl group, and 2-151 to 2-200 is used in combination with an ammonium salt.

The molar ratio of the compound (1a) to the compound (2) used in the reaction formula (1) is not particularly limited, but the molar ratio of the compound (2) is 0.1 to 10 times the molar ratio of 1 mol of the compound (1a). In terms of good yield of compound (3), it is preferably 1.0 to 2.0 times the molar amount. It is also possible to use compound (2) as a substrate and a solvent.

Next, the reaction of the reaction formula (2) will be described.

The reaction formula (2) is a reaction for obtaining a condensed aromatic compound represented by the general formula (5a) by reacting the compound (4a) and the compound (2) in the presence or absence of a base or an acid. is there. The compound (4a) is a subordinate concept of the compound (1), and the compound (5a) is a subordinate concept of the compound (5).

(In the general formula, R ² , X ^{1 to} X ⁴ , W ¹ , Y, and X ⁵ have the same definitions as described above ^{. Z 1} represents a leaving group.)
The ^{leaving group represented by Z 1} is not particularly limited, but the same leaving group as illustrated in Ring A can be exemplified.

The compound (4a) and the like used in the reaction of the reaction formula (2) can be produced by a known production method, or a commercially available product can be used.

The compound (4a) is not particularly limited, and for example, the following compounds represented by 4-1 to 4-150 can be exemplified.

As the compound (2), the compound represented by the above-mentioned 2-1 to 2-200 can be exemplified.

Next, the reaction of the reaction formula (3) will be described.

The reaction formula (3) is a reaction for obtaining a condensed aromatic compound represented by the general formula (7a) by reacting the compound (1a) and the compound (6) in the presence or absence of a base or an acid. Is. The compound (7a) is a subordinate concept of the compound (7).

(In the general formula, R ¹ , R ² , X ^{1 to} X ⁵ , W ² , Z ² , and Y have the same definitions as described above.)
The compound (1a) used in the reaction of the reaction formula (3) can be exemplified by the compound represented by the above-mentioned 1-1 to 1-150.

The compound (6) is not particularly limited, and for example, the following compounds represented by 6-1 to 6-20 can be exemplified.

The purity of the compounds (3), (5), and (7) obtained by the production method of the present invention can be increased by performing treatments such as reprecipitation, concentration, filtration, and purification after completion of each reaction. .. In order to further purify the product, it may be purified by recrystallization, silica gel column chromatography, sublimation or the like, if necessary.

With respect to the compounds (5) and (7), the compound (3) can be produced by using a generally known raw material and a generally known method.

For example, the following compounds (8) or (9) can be produced by reacting the compounds (5a) and (7a) with a conventionally known halogenating agent or sulfonylating agent.

(In the general formula, R ¹ , R ² , X ^{1 to} X ⁵ , and Y have the same definitions as described above ^{. Z 3} represents a leaving group.)
The ^{leaving group represented by Z 3} is not particularly limited, but the same leaving group as described above can be exemplified.

For the above compounds (8) and (9), the compound (3a) can be easily synthesized by using a conventionally known coupling reaction.

(In the general formula, R ¹ , R ² , X ^{1 to} X ⁵ , Y, and Z ³ have the same definitions as described above ^{. Z 4} represents a leaving group.)
The ^{leaving group represented by Z 4} is not particularly limited, but the same leaving group as described above can be exemplified.

The compounds (10) and (11) used in the reaction formula (5) can be produced by using a known production method, or commercially available products can also be used.

The compounds (10) and (11) are not particularly limited, and for example, the compounds represented by the following 10-1 to 10-63 can be exemplified.

(Wherein, ^{Z 4} is the same definition as ^{Z 4} in the above reaction formula (5).)
The fused ring aromatic compound represented by the general formula (3) of the present application can be preferably used in an organic electroluminescent device, and the fused ring aromatic compound can be preferably used in an electron transport layer, an electron injection layer, or a light emitting layer.

The fused aromatic compound represented by the general formula (3) of the present application is not particularly limited, and examples thereof include the compounds represented by the following 3 to 1-3-46.

The fused ring aromatic compound represented by the general formula (3) can be preferably used as an electron transporting material (electron transporting material, electron injecting material, etc.) of the organic electroluminescent device. At this time, for the anode, hole injection layer, hole transport layer, electron blocking layer, light emitting layer, light emitting layer dopant, light emitting layer host, cathode and the like used in combination, generally known materials can be selected by those skilled in the art. Can be used in.

The configuration of the organic electroluminescent device may be any conventionally known one, and is not particularly limited.

The method for producing a thin film for an organic electroluminescent device containing the compound (3) produced by the present invention is not particularly limited, and a preferable example thereof is film formation by a vacuum vapor deposition method. The film formation by the vacuum vapor deposition method can be performed by using a general-purpose vacuum vapor deposition apparatus. The degree of vacuum in the vacuum chamber when forming a film by the vacuum vapor deposition method is that the manufacturing tact time for manufacturing organic electric field light emitting elements is short and the manufacturing cost is superior, so that commonly used diffusion pumps, turbo molecular pumps, and cryopumps are used. ^{It is preferably about 1 × 10 −2} to 1 × 10 ⁻⁶ Pa that can be reached by a pump or the like, and the vapor deposition rate is preferably 0.005 to 10 nm / sec depending on the thickness of the film to be formed. A thin film for an organic electroluminescent device made of compound (3) can also be produced by a solution coating method. For example, the compound (3) is dissolved in an organic solvent such as chloroform, dichloromethane, 1,2-dichloroethane, chlorobenzene, toluene, ethyl acetate or tetrahydrofuran, and a spin coating method, an inkjet method, a casting method or a general-purpose device is used. It is also possible to form a film by the dip method or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not construed as being limited thereto.

Example-1

Methyl 3-aminobenzothiophene-2-carboxylate (1.21 g) was dissolved in formamide (20 mL) under an argon stream, concentrated sulfuric acid (0.5 mL) was added dropwise thereto, and the mixture was then stirred at 180 ° C. for 17 hours. .. The reaction mixture was allowed to cool to 90 ° C. and then added dropwise to cold water. The precipitated solid was washed with water and then with hexane. By recrystallizing the sample with toluene (20 mL), the desired white powder of 7-chloro-benzothieno [3,2-d] pyrimidin-4-one (yield 1.0 g, yield 85%) was obtained. It was.

^{1 1} H-NMR (DMSO-d ₆ ), δ (ppm): 7.65 (d, J = 7.5Hz, 1H), 8.24 (d, J = 8.5Hz, 1H), 8.37 ( s, 1H), 8.38 (s, 1H), 12.92 (s, 1H).
DMF (21 mL) was added to 7-chloro- [1] benzothieno [3,2-d] pyrimidine-4-one (1.0 g) under an argon stream and dissolved at room temperature. Then thionyl chloride (2.5 mL) was added and stirred at 80 ° C. for 20 hours. The reaction mixture was cooled in an ice bath and water was added. Then, a 4N-sodium hydroxide aqueous solution (30 mL) and a saturated sodium hydrogen carbonate aqueous solution (3.0 mL) were added for neutralization. After cooling the mixture in an ice bath, the precipitated solid was collected by filtration, washed with water, and then washed with hexane to obtain the desired white color of 4,7-dichloro- [1] benzothieno [3,2-d] pyrimidine. A powder (yield 524 mg, yield 49%) was obtained.

^{1 1} H-NMR (DMSO-d ₆ ), δ (ppm): 7.48 (d, J = 8.4 Hz, 1H), 8.11 (d, J = 8.4 Hz, 1H), 8.13 ( s, 1H), 8.21 (s, 1H).
Example-2

Under an argon stream, 3-amino-2-benzoyl-5-bromobenzothiophene (1.29 g) was dissolved in formamide (16 mL), concentrated sulfuric acid (0.5 mL) was added dropwise thereto, and then at 180 ° C. for 22 hours. Stirred. The reaction mixture was allowed to cool to 90 ° C. and then added dropwise to cold water. The precipitated solid was washed with water and then with hexane to obtain a white powder of the desired 8-bromo-4-phenyl [1] benzothieno [3,2-d] pyrimidine (yield 1.16 g, yield 85). %) Was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.60-7.67 (m, 3H), 7.79-7.84 (m, 2H), 8.24 (d, J = 7.6Hz) , 2H), 8.76 (s, 1H), 9.42 (s, 1H).
Example-3

Under an argon stream, 3-amino-2-benzoyl-6-chlorobenzothiophene (500 mg) was dissolved in formamide (7.0 mL), concentrated sulfuric acid (0.5 mL) was added dropwise thereto, and then at 180 ° C. for 18 hours. Stirred. The reaction mixture was allowed to cool to 80 ° C. and then added dropwise to cold water. The precipitated solid was washed with water and then with hexane to obtain the desired white powder of 7-chloro-4-phenyl [1] benzothieno [3,2-d] pyrimidine (yield 478 mg, 93%). Got

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.59-7.67 (m, 4H), 7.94 (s, 1H), 8.22-8.5 (m, 2H), 8. 54 (d, J = 8.4 Hz, 1H), 9.41 (s, 1H).
Example-4

Under an argon stream, 3-amino-2-benzoylthioeno [2,3-b] pyridine (2.54 g) and 3,5-dichloroacetophenone (3.12 g) were added to acetic acid (20 mL), and concentrated sulfuric acid (20 mL) was added. 2.6 mL) was added, and then the mixture was heated and stirred at 120 ° C. for 65 hours. After allowing the reaction mixture to cool to room temperature, water was added. The precipitated solid was washed with water, suspended in methanol, and then saturated aqueous sodium hydrogen carbonate solution was added. The mixture was heated and stirred at 60 ° C., and the insoluble matter was filtered off. By purifying the sample by column chromatography (developing solvent: chloroform), the desired 2- (3,5-dichlorophenyl) -4-phenylthieno [3,2-b: 5,3-b'] dipyridine White powder (yield 1.54 g, yield 38%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.48 (s, 1H), 7.55 (dd, J = 7.9, 4.7Hz, 1H), 7.57-7.66 (m) , 3H), 7.85 (d, J = 8.2Hz, 2H), 7.88 (s, 1H), 8.15 (s, 2H), 8.80 (d, J = 4.7Hz, 1H) ), 8.89 (d, J = 7.9Hz, 1H).
Example-5

Under an argon stream, 3-amino-2-benzoylindole (850 mg), 3-bromo-5-chlorobenzonitrile (1.17 g), and potassium phosphate (1.53 g) were added to DMF (7.2 mL). The mixture was heated and stirred at 80 ° C. for 12 hours. After allowing the reaction mixture to cool to room temperature, water was added. The mixture is separated and extracted with chloroform and then purified by column chromatography (developing solvent: chloroform) to obtain the desired 2- (3-bromo-5-chlorophenyl) -4-phenyl-indro [3,2-d]. ] A white powder of pyrimidine (yield 347 mg, yield 22%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.44 (dd, J = 7.8, 7.2 Hz, 1H), 7.57 (d, J = 8.3 Hz, 1H), 7.61 (S, 1H), 7.64 (d, J = 7.3Hz, 1H), 7.70-7.72 (m, 3H), 8.18 (d, J = 8.2Hz, 2H), 8 .51-8.53 (m, 2H), 8.68 (s, 1H), 8.79 (s, 1H).
Example-6

3-Amino-2-benzoyl-benzothiophene (1.05 g) is dissolved in formamide (17.0 mL) under an argon stream, concentrated sulfuric acid (1.0 mL) is added dropwise thereto, and then the mixture is stirred at 180 ° C. for 15 hours. did. The reaction mixture was allowed to cool to room temperature and then added dropwise to cold water. The precipitated solid was washed with water and then with methanol to obtain the desired white powder of 4-phenyl [1] benzothieno [3,2-d] pyrimidine (yield 1.00 g, yield 92%). It was.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.58-7.66 (m, 4H), 7.72 (dd, J = 8.0, 7.2Hz, 1H), 7.96 (d) , J = 8.0Hz, 1H), 8.25 (d, J = 8.0Hz, 2H), 8.61 (d, J = 7.9Hz, 1H), 9.41 (s, 1H).
Example-7

3-Amino-2-benzoyl-benzothiophene (253 mg) and 4-bromobenzamide (240 mg) were added to Eaton's reagent (2.0 mL) under an argon stream, and the mixture was heated and stirred at 150 ° C. for 20 hours. The reaction mixture was allowed to cool to room temperature and then added dropwise to cold water. The mixture was separated and extracted with chloroform and then purified by column chromatography (developing solvent: chloroform) to allow the reaction mixture to cool to room temperature and then added dropwise to cold water. By washing the precipitated solid with water and then with methanol, a black powder of the desired 2- (4-bromophenyl) -4-phenyl [1] benzothieno [3,2-d] pyrimidine (yield 197 mg, Yield 47%) was obtained.

Reference example-1

8-Bromo-4-phenyl-benzothieno [3,2-d] pyrimidin (1.10 g), 5'-m-terphenylboronic acid (972 mg), palladium acetate (14.5 mg), and 2 under an argon stream. -Dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (92.1 mg) was suspended in THF (32 mL), 3M-potassium carbonate aqueous solution (2.4 mL) was added, and the mixture was heated and refluxed for 66 hours. did. After allowing the reaction mixture to cool, water was added and the precipitated solid was collected by filtration. The obtained solid was washed with water, methanol and hexane to obtain the desired 8- [1,1': 3', 1 "-terphenyl-5'-yl] -4-phenyl- [1] benzothieno [3]. , 2-d] A gray powder of pyrimidine (yield 1.54 g, yield 98%) was obtained.

^{1 1} H-NMR (CDCl ₃ ) δ (ppm): 7.44 (t, J = 7.3Hz, 2H), 7.53 (dd, J = 7.8, 7.3Hz, 4H), 7.60 -7.67 (m, 3H), 7.77 (d, J = 7.8Hz, 4H), 7.87 (s, 1H), 7.97 (s, 2H), 8.04 (d, J) = 8.4Hz, 1H), 8.08 (d, J = 8.4Hz, 1H), 8.28 (d, J = 7.9Hz, 2H), 8.95 (s, 1H), 9.45 (S, 1H).
Reference example-2

2- (3,5-dichlorophenyl) -4-phenylthieno [3,2-b: 5,4-b'] (1.00 g), phenylboronic acid (718 mg), palladium acetate (27. 6 mg) and 2-ditert-butylphosphino-2', 4', 6'-triisopropylbiphenyl (173 mg) were suspended in 1,4-dioxane (12 mL), and a 3M-potassium carbonate aqueous solution (4.0 mL) was added. ) Was added, and the mixture was heated under reflux for 15 hours. After allowing the reaction mixture to cool, water was added and the aqueous layer was removed by decantation. By purifying the obtained solid by column chromatography (developing solvent: chloroform), the desired 2- [1,1': 3', 1''-terphenyl-5'-yl] -4-phenyl- A gray powder (yield 417 mg, yield 35%) of thieno [3,2-b: 5,4-b'] dipyrimidine (ETL-4) was obtained.

^{1 1} H-NMR (CDCl ₃ ): δ7.45 (t, J = 7.4Hz, 2H), 7.51 (dd, J = 7.9, 4.7Hz, 1H), 7.52-7.65 (M, 7H), 7.79 (d, J = 8.2Hz, 4H), 7.87 (d, J = 8.2Hz, 2H), 7.93 (s, 1H), 8.02 (s) , 1H), 8.42 (s, 2H), 8.78 (d, J = 4.7Hz, 1H), 8.89 (d, J = 7.9Hz, 1H).

Nitrogen-substituted dibenzothiophene compounds, nitrogen-substituted dibenzofuran compounds, and nitrogen-substituted carbazole compounds, which are useful compounds as materials for organic electroluminescent devices, can be produced efficiently and at low cost.

An organic electroluminescent device using a fused ring aromatic compound produced by the production method of the present invention can be driven for a longer time than an organic electroluminescent device using an existing material. Further, the fused ring aromatic compound produced by the production method of the present invention can be applied not only to the electron transport layer but also to a light emitting host layer and the like. Further, it can be applied not only to an element using a fluorescent light emitting material but also to various organic electroluminescent devices using a phosphorescent light emitting material. Further, the fused ring aromatic compound produced by the production method of the present invention has high solubility, and it is possible to produce an element using not only a vacuum vapor deposition method but also a coating method. Further, it is useful not only for applications such as flat panel displays, but also for lighting applications that require low power consumption.

Claims (2)

The following general formula (1-A) or (1-B)

(During the ceremony,
Ring A represents a benzene ring or a pyridine ring (these rings may have a substituent).
Y ″ represents an oxygen atom, a sulfur atom, a nitrogen atom which may have a substituent, or a carbon atom which may have a substituent.
R ¹ is an aromatic group having 4 to 66 carbon atoms (the group is a fluorine atom, a methyl group, an ethyl group, a linear, branched or cyclic alkyl group having 3 to 10 carbon atoms, a methoxy group, an ethoxy group, and the like. A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. It may have a leaving group as a substituent). )
Aromatic compounds represented by, and the following general formula (2)

(During the ceremony,
R ² is an aromatic group (in which the 4-66 carbon atoms, a fluorine atom, a methyl group, an ethyl group, a straight chain of 3 to 10 carbon atoms, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. It may have a leaving group as a substituent), represents a methyl group, an ethyl group, or an alkyl group having 3 to 10 carbon atoms.
W ¹ represents a cyano group, an aminocarbonyl group, or an acetyl group. )
The general formula (3-A) or (3-B) , which comprises reacting a compound represented by.

(During the ceremony,
Rings A, Y'' , R ¹ , and R ² are the same as described above.
X ⁵ represents a group represented by CR ^{3 or a nitrogen atom.}
R ³ represents a hydrogen atom. )
A method for producing a material for an organic electroluminescent device represented by (however, the following general formulas (14), (23), and (24)).

(During the ceremony,
Y ² represents a sulfur atom or an oxygen atom.
R ^{3 to} R ⁶ are independently aromatic groups having 4 to 66 carbon atoms (independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, and an ethoxy group. , An alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms as a substituent. (May be good), hydrogen atom, heavy hydrogen atom, fluorine atom, methyl group, ethyl group, alkyl group with 3 to 10 carbon atoms, methoxy group, ethoxy group, alkoxy group with 3 to 10 carbon atoms, methylthio group, ethylthio group, It represents a sulfide group having 3 to 10 carbon atoms or a diarylamino group having 10 to 36 carbon atoms.
Ar ¹ and Ar ² are independently aromatic groups having 4 to 66 carbon atoms (independently, a fluorine atom, a methyl group, an ethyl group, an alkyl group having 3 to 10 carbon atoms, a methoxy group, and an ethoxy group. , An alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, a halogenated alkoxy group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a desorbing group as substituents. May have). )

(During the ceremony,
Ar ¹¹ independently represents an aromatic hydrocarbon group having 12 or less carbon atoms (which may be formed by linkage, condensed ring, or both). These groups may be substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group, an ester alkyl group, a nitrogen-containing heteroaromatic group having 6 or less carbon atoms, or a fluorine atom.
X ¹¹ independently represents a divalent aromatic hydrocarbon having 10 or less carbon atoms. These groups may be substituted with an alkyl group, an alkoxy group, or a fluorine atom.
Ar ¹² and Ar ¹³ are independently each of a nitrogen-containing heteroaromatic group having 25 or less carbon atoms (linkage, condensed ring, or ring) formed of an aromatic hydrocarbon group having 18 or less carbon atoms and at least one pyridyl group. It may be formed of both), or represents a pyrimidyl group. These groups may be substituted with an alkyl group, an alkoxy group, an alkoxyalkyl group, an ester group, an ester alkyl group, an aromatic hydrocarbon group having 18 or less carbon atoms, or a fluorine atom.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , and R ²⁶ each independently have a hydrogen atom or 1 to 6 carbon atoms. Represents a substituent of.
n ¹ , n ² , m ¹ and m ² each independently represent an integer of 0, 1 or 2.
The aromatic hydrocarbon groups or nitrogen-containing heteroaromatic groups described in Ar ¹¹ , Ar ¹² , Ar ¹³ , and X ¹¹ all have a structure in which a six-membered ring or a plurality of six-membered rings are condensed.
Moreover, each hydrogen atom in the formula may be a deuterium atom independently. )
Excludes the method for producing the compound represented by. ). R ² is an aromatic group (in which the 4-66 carbon atoms, a fluorine atom, a methyl group, an ethyl group, a straight chain of 3 to 10 carbon atoms, branched, or cyclic alkyl group, a methoxy group, an ethoxy group, A linear, branched or cyclic alkoxy group having 3 to 10 carbon atoms, an alkyl halide group having 1 to 3 carbon atoms, an alkoxy halide group having 1 to 3 carbon atoms, a diarylamino group having 10 to 36 carbon atoms, or a diarylamino group having 10 to 36 carbon atoms. The method for producing a material for an organic electric field light emitting element according to claim 1 , wherein the leaving group may be used as a substituent).