JPWO2018025590A1 - Process for producing nitrogen-containing heterocyclic compound and nitrogen-containing heterocyclic compound - Google Patents

Abstract

An object of the present invention is to provide a method for producing a nitrogen-containing heterocyclic compound which has high yield and high purity and is excellent in production suitability and environmental suitability. In the method for producing a nitrogen-containing heterocyclic compound of the present invention, a compound having a structure represented by the following general formula [1] is reacted with bromine in the presence of a silver salt, sulfuric acid and carboxylic acid, A compound having a structure represented by the general formula [2] is synthesized. [Chemical formula 1]

Description

  The present invention relates to a method for producing a nitrogen-containing heterocyclic compound and a nitrogen-containing heterocyclic compound. More specifically, the present invention relates to a method for producing a nitrogen-containing heterocyclic compound capable of providing a nitrogen-containing heterocyclic compound useful as a material for an organic electroluminescent device in a high yield.

  It is known that the following azadibenzofuran is reacted with bromine in the presence of sulfuric acid and water to obtain a brominated product in a yield of 33% (see, for example, Patent Document 1). Under these conditions, 35 mL of sulfuric acid and 100 mL of water are used with respect to 34 g of azadibenzofuran, but since stirring is difficult, improvement is required from the viewpoint of production suitability.

For example, although it is conceivable to increase the amount of water, it is not effective because precipitation of the reaction substrate and a marked decrease in reactivity are observed.
In addition, although increasing the amount of sulfuric acid enables stirring, the reaction system becomes very active, side reactions such as dibromination occur, and a large amount of waste liquid due to neutralization treatment is not preferable for environmental suitability, so new A method of synthesis has been sought.

JP, 2011-84531, A

  The present invention has been made in view of the above problems and circumstances, and the problem to be solved is to provide a method for producing a nitrogen-containing heterocyclic compound having high yield and high purity and excellent in production suitability and environmental suitability. It is.

As a result of examining the cause of the above problems and the like in order to solve the above problems, the present inventor has found that a high yield can be obtained by reacting a compound having a specific structure with bromine in the presence of a silver salt, sulfuric acid and carboxylic acid The present invention has also been found to provide a method for producing a nitrogen-containing heterocyclic compound having a specific structure which is high in purity and excellent in production suitability and environmental suitability.
That is, the above-mentioned subject of the present invention is solved by the following means.

（式中、Ｘは、酸素原子又は硫黄原子を表す。Ａ_１〜Ａ_４は、それぞれ窒素原子又はＣＲを表す。ただし、Ａ_１〜Ａ_４のうち少なくとも一つは窒素原子である。Ｒ及びＲ_１〜Ｒ_３は、それぞれ水素原子又は置換基を表す。）1. A compound having a structure represented by the following general formula [1] is reacted with bromine in the presence of a silver salt, sulfuric acid and a carboxylic acid to synthesize a compound having a structure represented by the following general formula [2] Method for producing a nitrogen-containing heterocyclic compound

(Wherein, X represents an oxygen atom or a sulfur atom. A _{1 to} A ₄ each represent a nitrogen atom or CR. However, at least one of A _{1 to} A ₄ is a nitrogen atom. R and R _{1 to} R ₃ each represent a hydrogen atom or a substituent.)

（式中、Ｘは、酸素原子又は硫黄原子を表す。Ｒ_１〜Ｒ_６は、それぞれ水素原子又は置換基を表す。）2. The compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [3], and the compound having a structure represented by the general formula [2] is The manufacturing method of the nitrogen-containing heterocyclic compound of 1st term which is a compound which has a structure represented by following General formula [4].

(Wherein, X represents an oxygen atom or a sulfur atom. R _{1 to} R ₆ each represent a hydrogen atom or a substituent.)

（式中、Ｘは、酸素原子又は硫黄原子を表す。Ｘ_１は、臭素原子又はヨウ素原子を表す。Ｒ_１〜Ｒ_５は、それぞれ水素原子又は置換基を表す。）3. The compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [5], and the compound having a structure represented by the general formula [2] is The manufacturing method of the nitrogen-containing heterocyclic compound of 1st term or 2nd term which is a compound which has a structure represented by following General formula [6].

(In the formula, X represents an oxygen atom or a sulfur atom. X ₁ represents a bromine atom or an iodine atom. R _{1 to} R ₅ each represent a hydrogen atom or a substituent.)

（式中、Ｘは、酸素原子又は硫黄原子を表す。Ａ_１〜Ａ_４は、窒素原子又はＣＲを表す。ただし、Ａ_１〜Ａ_４のうち少なくとも一つは窒素原子である。Ｒ及びＲ_１〜Ｒ_３は、水素原子又は置換基を表す。Ｒ_７は、アルキル基又はアリール基を表す。）4. A compound having a structure represented by the following general formula [2] is reacted with a compound having a structure represented by the following general formula [7], and further reacted with an acid to be represented by the following general formula [8] The method for producing a nitrogen-containing heterocyclic compound according to any one of the items 1 to 3, wherein a compound having a structure is produced.

(In the formula, X, _.A 1 to A ₄ representing an oxygen atom or a sulfur atom represents a nitrogen atom or a CR. _However, at least one of A 1 to A ₄ is a nitrogen atom .R and R _{1 to} R _{3 each} represent a hydrogen atom or a substituent R ₇ represents an alkyl group or an aryl group)

（式中、Ｘは、酸素原子又は硫黄原子を表す。Ｘ_１は、臭素原子又はヨウ素原子を表す。Ｒ_１〜Ｒ_５は、それぞれ水素原子又は置換基を表す。）5. The nitrogen-containing heterocyclic compound which is a compound which has a structure represented by following General formula [6].

(In the formula, X represents an oxygen atom or a sulfur atom. X ₁ represents a bromine atom or an iodine atom. R _{1 to} R ₅ each represent a hydrogen atom or a substituent.)

  According to the above means of the present invention, it is possible to provide a method for producing a nitrogen-containing heterocyclic compound which is high in yield and high in purity and excellent in production suitability and environmental suitability.

  Although the mechanism for expressing the effect of the present invention or the mechanism of action is not clear, using acetic acid instead of increasing water and sulfuric acid moderates the reaction and suppresses the formation of by-products I guess it can be done.

The method for producing a nitrogen-containing heterocyclic compound of the present invention comprises reacting a compound having a structure represented by the above general formula [1] with bromine in the presence of a silver salt, sulfuric acid and a carboxylic acid, A compound having a structure represented by [2] is synthesized.
The nitrogen-containing heterocyclic compound of the present invention is a compound having a structure represented by the above general formula [6].
These features are technical features that are common to or correspond to the following embodiments.

  In addition, a compound having a structure represented by the general formula [1] is a compound having a structure represented by the general formula [3], and a compound having a structure represented by the general formula [2] It is preferable that it is a compound which has a structure represented by the said General formula [4].

  Further, a compound having a structure represented by the general formula [1] is a compound having a structure represented by the general formula [5] and a compound having a structure represented by the general formula [2] It is preferable that it is a compound which has a structure represented by said general formula [6].

  Further, a compound having a structure represented by the general formula [2] and a compound having a structure represented by the general formula [7] are reacted with each other to further react with an acid to give a table of the general formula [8]. It is preferable to produce a compound having the following structure.

  BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in the following description uses the numerical value described before and after that in the meaning included as a lower limit and an upper limit.

<< Summary of Production Method of Nitrogen-Containing Heterocyclic Compound >>
The method for producing a nitrogen-containing heterocyclic compound of the present invention comprises reacting a compound having a structure represented by the following general formula [1] with bromine in the presence of a silver salt, sulfuric acid and a carboxylic acid to obtain the following general formula It is characterized in that a compound having a structure represented by [2] is synthesized.

In the formula, X represents an oxygen atom or a sulfur atom. A _{1 to} A ₄ each represent a nitrogen atom or CR. However, at least one of A _{1 to} A ₄ is a nitrogen atom. R and R _{1 to} R ₃ each represent a hydrogen atom or a substituent.

X represents an oxygen atom or a sulfur atom, and a particularly preferred one of the groups represented by X is an oxygen atom.
A _{1 to} A ₄ represent a nitrogen atom or CR. However, it is preferable that at least one of A _{1 to} A ₄ is a nitrogen atom, preferably one is a nitrogen atom, and particularly, A ₁ is a nitrogen atom.
Examples of the substituent represented by R and R _{1 to} R ₃ include, for example, alkyl group, cycloalkyl group, alkenyl group, aryl group, acylamino group, sulfonamide group, alkylthio group, arylthio group, halogen atom, heterocycle ( For example, dibenzofuran ring, azadibenzofuran ring etc.) group, sulfonyl group, sulfinyl group, phosphonyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, Carbamoyloxy group, amino group, alkylamino group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, ca. Bokishi each group such group.

  Any of the above substituents may be further substituted by a substituent, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonamide group, an alkylthio group, an arylthio group, a halogen atom, Heterocyclic group, sulfonyl group, sulfinyl group, phosphonyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, Each group such as alkylamino group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carboxy group and the like can be mentioned. .

<bromine>
The amount of bromine used in the present invention is preferably in the range of 0.8 to 1.3 times the molar ratio of the compound having the structure represented by the general formula [1], particularly preferably 0.9. It is within the range of 1.2 times.

Silver salt
Examples of the silver salt used in the present invention include silver acetate, silver sulfate, silver carbonate, silver nitrate, silver phosphate, silver oxide, silver halide and the like. Among these, silver sulfate is preferred.
The amount of the silver salt used in the present invention is preferably in the range of 0.3 to 3 mol, particularly preferably 0.5 to 1.5 mol, per 1 mol of the compound having the structure represented by the general formula [1]. It is in the range.

Sulfuric acid
The amount of sulfuric acid used in the present invention is preferably in the range of 1 to 5 mL, particularly preferably 1 to 3 mL, per 1 g of the compound having the structure represented by the general formula [1].

<carboxylic acid>
Examples of the carboxylic acid used in the present invention include acetic acid, propionic acid, butyric acid, pivalic acid, benzoic acid and the like, with preference given to acetic acid.
Advantages of using a carboxylic acid are that the reaction becomes mild and the formation of by-products can be suppressed, the stirring is good and the production suitability is excellent, and the carboxylic acid is a weak acid and there is no need to neutralize it. And the like.
The amount of the carboxylic acid used in the present invention is preferably in the range of 5 to 50 mL, particularly preferably 10 to 30 mL, per 1 g of the compound having the structure represented by the general formula [1].

  In the present invention, since the generation of by-products can be suppressed, the reaction rate (measured by HPLC) can be improved, and the yield can be improved. The yield is preferably 75% or more, particularly preferably 80% or more.

  The amount of water used in the present invention is preferably in the range of 1 to 5 mL, particularly preferably in the range of 1 to 3 mL, per 1 g of the compound having the structure represented by the general formula [1].

  Furthermore, a compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [3], and a compound having a structure represented by the general formula [2] It is preferable that it is a compound which has a structure represented by following General formula [4].

In the formula, X represents an oxygen atom or a sulfur atom. R _{1 to} R ₆ each represent a hydrogen atom or a substituent.
Substituents represented by R ₁ to R ₆ in general formula [1] and can use the same as the substituent represented by R ₁ to R ₆ in [2], further be substituted with a substituent The same is true for the points that may be used.

The compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [5], and the compound having a structure represented by the general formula [2] is It is preferable that it is a compound which has a structure represented by following General formula [6].
The nitrogen-containing heterocyclic compound of the present invention is a compound having a structure represented by the following general formula [6].

The substituent represented by R _{1 to} R ₅ can be the same as the substituent represented by R _{1 to} R ₆ in the general formulas [1] and [2], and is further substituted by a substituent The same is true for the points that may be used.
X ₁ represents a bromine atom or an iodine atom, and a preferable one of the groups represented by X ₁ is an iodine atom.

  Further, a compound having a structure represented by the general formula [2] is reacted with a compound having a structure represented by the following general formula [7], and further reacted with an acid to give a table of the following general formula [8] It is preferable to produce a compound having the following structure.

In the formula, X represents an oxygen atom or a sulfur atom. A _{1 to} A ₄ represent a nitrogen atom or CR. However, at least one of A _{1 to} A ₄ is a nitrogen atom. R and R _{1 to} R _{3 each} represent a hydrogen atom or a substituent. R ₇ represents an alkyl group or an aryl group.
The substituents represented by R, R _{1 to} R ₃ and R ₇ may be the same as the substituents represented by R _{1 to} R ₆ in the general formulas [1] and [2], and further substituted The same applies in that it may be substituted by a group.

The alkyl group represented by R _7, for example a methyl group, an ethyl group, n- propyl group, iso- propyl, n- butyl group, a pentyl group, an octyl group.
Moreover, as an aryl group represented by R ₇ , for example, a phenyl group, a biphenyl group, a terphenyl group and the like can be mentioned.

<acid>
The acid used after reacting the compound having the structure represented by the general formula [2] with the compound having the structure represented by the general formula [7] is not particularly limited, but sulfuric acid, concentrated hydrochloric acid, phosphoric acid And acetic acid, tosyl acid or methanesulfonic acid.
The reaction temperature is usually preferably in the range of 0 to 40 ° C, particularly preferably in the range of 10 to 30 ° C.

<Palladium (Pd) catalyst>
When the compound having the structure represented by the general formula [2] is reacted with the compound having the structure represented by the general formula [7], it is preferable to use a Pd catalyst or a Cu catalyst, particularly preferably a Pd catalyst .
There is no particular limitation on those usable as the Pd catalyst, but PdCl ₂ , Pd (OAc) ₂ , Pd (pph ₃ ) ₄ , PdCl ₂ (dppf), Pd (dba) ₂ , Pd / C and the like can be mentioned.
A ligand may be used in combination with a Pd catalyst, for example, trialkyl phosphines (eg, tributyl phosphine, tri t-butyl phosphine, tricyclohexyl phosphine), phosphines having at least one aryl group (eg, triphenyl phosphine, SPhos, XPhos , T-BuXPhos, etc.). Among these, phosphine having one aryl group is preferable, and particularly preferably t-BuXPhos.

<Copper (Cu) catalyst>
There is no particular limitation on the Cu catalyst, but CuCl, CuCl ₂ , CuBr, CuBr ₂ , CuI, CuI ₂ , CuO, Cu ₂ O, CuSO ₄ , Cu ₂ SO ₄ , CuOCOCH ₃ , Cu (OCOCH _{3) 2} ) etc. Of these, particularly preferred are CuI and Cu ₂ O.
A ligand may be used in combination with a Cu catalyst, for example, quaternary ammonium salts (tetra-n-butylammonium fluoride (TBAF), tetraethylammonium iodide), 2,2'-bipyridine, tri (t-butyl) phosphine, 1,2-bis (diphenylphosphino) ethane (DPPE), 1,3-bis (diphenylphosphino) propane (DPPP), 1,4-bis (diphenylphosphino) butane (DPPB), 1,1′- Bis (diphenylphosphino) ferrocene (DPPF), tricyclohexylphosphine (PCy ₃ ), aryl alcohols (eg 2-phenylphenol, 1-naphthol, 2,6-dimethylphenol, salicylaldoxime, N, N-diethyl salicylate Amide, 8-hydroxyquinoline etc., alkyl Mins (eg, 2- (dimethylamino) ethanol, 2- (dimethylamino) glycine etc.), alicyclic amines (eg, L-proline, DBU etc.), diamines (eg, 1,2-cyclohexanediamine) N, N'-dimethylethylenediamine, N, N, N ', N'- tetramethylethylenediamine etc., glycols (eg ethylene glycol, ethylene glycol dimethyl ether etc.), imidazolium carbenes (eg 1,3-) Bis (2,6-diisopropylphenyl) -4,5-dihydroimidazolium telora fluoroborate, 1,3-bis (2,6-dimethylphenyl) -4,5-dihydroimidazolium telora fluoroborate etc.), pyridines (For example, picolinic acid, 3-methylpicolinic acid, 3-hydroxypyridine Choline amide, 6-methylpicolinic acid, 2-aminomethylpyridine, 4- (dimethylamino) pyridine etc., β-diketones (eg dipivaloylmethane) or phenanthrolines (eg 1,10-phenanthroline, 4, At least one selected from 7-diphenyl-1,10-phenanthroline, 4,7-dimethyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, etc.).

<Specific examples of compounds used in the present invention>
Although the specific example of a compound which has a structure represented by General formula [1], General formula [3], or General formula [5] of this invention below is shown, this invention is not limited to these.

  Although the specific example of a compound which has a structure represented by General formula [2], General formula [4], or General formula [6] of this invention below is shown, this invention is not limited to these.

  Although the specific example of a compound which has a structure represented by General formula [7] of this invention below is shown, this invention is not limited to these.

  Although the specific example of a compound which has a structure represented by General formula [8] of this invention below is shown, this invention is not limited to these.

  EXAMPLES The present invention will be specifically described by way of examples, but the embodiments of the present invention are not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, it represents "mass part" or "mass%."

Synthesis example 1 (comparative example)
Synthesis of Exemplified Compound B-1
34 g (0.2 mol) of Exemplified Compound A-1, 35 mL of sulfuric acid and 100 mL of water were mixed, and further 65 g of silver sulfate and 48 g (0.3 mol) of bromine were added. At room temperature, heating and refluxing were performed for 5 hours because the reaction did not proceed, but stirring was insufficient. 80 mL of water was added and 84 g of sodium carbonate was added over 10 minutes. Extract with 5000 mL of a 1: 1 mixture of toluene / tetrahydrofuran (THF) and remove the solvent. After heating to reflux with methanol, the crystals were filtered and dried to obtain 14.9 g of Exemplary Compound B-1 (yield 30%, purity 90.5%).

Synthesis Example 2 (Invention)
Synthesis of Exemplified Compound B-1
34 g (0.2 mol) of Exemplified Compound A-1, 35 mL of sulfuric acid, 10 mL of water and 340 mL of acetic acid were mixed, and further 65 g of silver sulfate and 35 g (0.22 mol) of bromine were added. The reaction proceeded at room temperature and stirring was sufficient. Stirring was performed for 3 hours. 300 mL of water was added and 84 g of sodium carbonate was added in 10 minutes. Extract with 800 mL THF and remove the solvent. After heating to reflux with methanol, the crystals were filtered and dried to obtain 40.1 g of Exemplary Compound B-1 (yield 81%, purity 98.4%).

Synthesis example 3 (comparative example)
Synthesis of Exemplified Compound B-1
When the acetic acid of Synthesis Example 2 was replaced with the same amount of water, stirring was sufficient but the reaction did not proceed.

Synthesis example 4 (comparative example)
Synthesis of Exemplified Compound B-1
34 g (0.2 mol) of Exemplified Compound A-1, 375 mL of sulfuric acid and 10 mL of water were mixed, and further 65 g of silver sulfate and 35 g (0.22 mol) of bromine were added. The reaction proceeded at room temperature and the stirring was insufficient, but stirring was performed for 3 hours. 3000 mL of water was added, and sodium carbonate was added in 895 g for 1 hour. Extract with THF 5000 mL and remove the solvent. After heating to reflux with methanol, the crystals were filtered and dried to obtain 32 g of Exemplary Compound B-1 (yield 65%, purity 90.1%).

Synthesis Example 5 (Invention)
Synthesis of Exemplified Compound B-4
50 g (0.169 mol) of Exemplified Compound A-4, 100 mL of sulfuric acid, 50 mL of water, and 1.2 L of acetic acid were mixed, and 52 g of silver sulfate was further added. Bromine was added dropwise over 10 minutes in 29.7 g (0.186 mol) and stirred for another 3 hours. 500 mL of water was added, and 240 g of sodium carbonate was added in 1 hour. The crystals were collected by filtration and dried. It was dissolved in 5 L of THF to remove insolubles. After concentration under reduced pressure, the solution is heated under reflux with methanol, and the crystals are collected by filtration and dried to obtain 53.7 g of an exemplary compound B-4 (yield 85%, purity 97.0%).

Synthesis Example 6 (Invention)
Synthesis of Exemplified Compound B-4
50 g (0.169 mol) of Exemplified Compound A-4, 100 mL of sulfuric acid, 50 mL of water, and 1.2 L of propionic acid were mixed, and 52 g of silver sulfate was further added. Bromine was added dropwise over 10 minutes in 29.7 g (0.186 mol) and stirred for another 3 hours. 500 mL of water was added and 240 g of sodium carbonate was added in 1 hour. The crystals were collected by filtration and dried. It was dissolved in 5 L of THF to remove insolubles. After concentration under reduced pressure, the solution is heated under reflux with methanol, and the crystals are collected by filtration and dried to obtain 51.2 g of an exemplary compound B-4 (yield 81%, purity 96.7%).

Synthesis Example 7 (Invention)
Synthesis of Exemplified Compound B-4
50 g (0.169 mol) of Exemplified Compound A-4, 100 mL of sulfuric acid, 50 mL of water, and 1.2 L of acetic acid were mixed, and 28 g of silver acetate was further added. Bromine was added dropwise over 10 minutes in 29.7 g (0.186 mol) and stirred for another 3 hours. 500 mL of water was added, and 240 g of sodium carbonate was added in 1 hour. The crystals were collected by filtration and dried. It was dissolved in 5 L of THF to remove insolubles. After concentration under reduced pressure, the solution is heated under reflux with methanol, and the crystals are collected by filtration and dried to obtain 51.2 g of the exemplary compound B-4 (yield 81%, purity 96.0%).

Synthesis example 8 (comparative example)
Synthesis of Exemplified Compound B-4
The acetic acid in Synthesis Example 5 was replaced with the same amount of water, but the reaction did not proceed.

Synthesis Example 9 (Invention)
Synthesis of Exemplified Compound D-2
8.9 g (0.0214 mol) of Exemplified Compound B-2, 5.0 g (0.0427 mol) of Exemplified Compound C-5, 4.1 g of tC ₄ H ₉ ONa, and 160 mL of THF are charged under a nitrogen stream The mixture was stirred for 20 minutes. To this suspension, 1.3 g of Pd (dba) ₂ and 0.7 g of t-BuXPhos were charged and refluxed for 2 hours. After THF 600 mL was charged, insolubles were removed, and the solution was concentrated under reduced pressure. The mixture was stirred for 3 hours under water cooling, and the precipitated crystals were filtered, washed with water and dried. 5 L of a mixed solution of toluene and methanol was added, and after removing insolubles, the solution was concentrated under reduced pressure. The resulting crude product was heated and suspended in acetonitrile and then filtered to obtain 12.7 g of brown crystals. Subsequently, 100 mL of ethanol and 10 mL of concentrated hydrochloric acid were added, and the mixture was refluxed for 1 hour. After stirring at room temperature for 1 hour, it was filtered. To the obtained crude product, 80 mL of ethyl acetate and 50 mL of a 10% aqueous solution of sodium carbonate were added, stirred for 1 hour, filtered, and dried to obtain 6.9 g of Exemplified Compound D-2 (yield 89%, purity 95) .2%).

  Identification of each compound in the examples was performed by MASS and NMR spectra, and it was confirmed that each was the target compound. Other exemplified compounds can also be synthesized according to the above method.

  The method for producing a nitrogen-containing heterocyclic compound of the present invention can be suitably used, for example, for producing a nitrogen-containing heterocyclic compound used as a material for an organic electroluminescent device. Moreover, the nitrogen-containing heterocyclic compound manufactured by the manufacturing method of the nitrogen-containing heterocyclic compound of this invention and the nitrogen-containing heterocyclic compound of this invention can be used suitably, for example as a material for organic electroluminescent elements.

Claims (5)

A compound having a structure represented by the following general formula [1] is reacted with bromine in the presence of a silver salt, sulfuric acid and a carboxylic acid to synthesize a compound having a structure represented by the following general formula [2] Method for producing a nitrogen-containing heterocyclic compound

(Wherein, X represents an oxygen atom or a sulfur atom. A _{1 to} A ₄ each represent a nitrogen atom or CR. However, at least one of A _{1 to} A ₄ is a nitrogen atom. R and R _{1 to} R ₃ each represent a hydrogen atom or a substituent.) The compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [3], and the compound having a structure represented by the general formula [2] is The method for producing a nitrogen-containing heterocyclic compound according to claim 1, which is a compound having a structure represented by the following general formula [4].

(Wherein, X represents an oxygen atom or a sulfur atom. R _{1 to} R ₆ each represent a hydrogen atom or a substituent.) The compound having a structure represented by the general formula [1] is a compound having a structure represented by the following general formula [5], and the compound having a structure represented by the general formula [2] is It is a compound which has a structure represented by following General formula [6], The manufacturing method of the nitrogen-containing heterocyclic compound of Claim 1 or Claim 2.

(In the formula, X represents an oxygen atom or a sulfur atom. X ₁ represents a bromine atom or an iodine atom. R _{1 to} R ₅ each represent a hydrogen atom or a substituent.) A compound having a structure represented by the following general formula [2] is reacted with a compound having a structure represented by the following general formula [7], and further reacted with an acid to be represented by the following general formula [8] The method for producing a nitrogen-containing heterocyclic compound according to any one of claims 1 to 3, wherein a compound having a structure is produced.

(In the formula, X, _.A 1 to A ₄ representing an oxygen atom or a sulfur atom represents a nitrogen atom or a CR. _However, at least one of A 1 to A ₄ is a nitrogen atom .R and R _{1 to} R _{3 each} represent a hydrogen atom or a substituent R ₇ represents an alkyl group or an aryl group) The nitrogen-containing heterocyclic compound which is a compound which has a structure represented by following General formula [6].

(In the formula, X represents an oxygen atom or a sulfur atom. X ₁ represents a bromine atom or an iodine atom. R _{1 to} R ₅ each represent a hydrogen atom or a substituent.)