JP2019123694A - Method of producing nitrogen-containing heterocyclic compound - Google Patents

Abstract

To provide a method of producing a nitrogen-containing heterocyclic compound obtained in a reduced number of steps and a high yield.SOLUTION: In a method of producing a nitrogen-containing heterocyclic compound, a compound represented by the specified general formula [1] and a compound represented by the specified general formula [2] are reacted to obtain a compound represented by the specified general formula [3].SELECTED DRAWING: Figure 1

Description

  The present invention relates to a useful intermediate of an organic synthetic compound, in particular, a nitrogen-containing heterocyclic compound useful as a material for organic electroluminescence and a method for producing a nitrogen-containing heterocyclic compound derived therefrom.

As a method of synthesizing azadibenzofuran, N-oxide of the nitrogen atom of the pyridine ring as shown in the following route is followed by cyclization by C-H / C-H activation reaction and further synthesis of azadibenzofuran by reduction reaction The method is known. For example, Non-Patent Document 1 discloses a reaction formula corresponding to a part of the following route.
This method has a problem that the yield of cyclization reaction is low. Moreover, in this method, after making the nitrogen atom of a pyridine into N-oxide, it is necessary to reduce | restore and return, There existed a problem that the number of processes becomes long.

Org. Lett., 2015, 17 (3), p.

  The present invention has been made to solve the above problems, and its object is to provide a method for producing a nitrogen-containing heterocyclic compound obtained in a short number of steps and a high yield.

  The above-mentioned subject was able to be solved by the following composition.

  1. The nitrogen-containing heterocyclic compound is characterized in that a compound represented by the following general formula [1] is reacted with a compound represented by the following general formula [2] to obtain a compound represented by the following general formula [3] Production method.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 Represents an integer of

  2. A Pd catalyst and an imidazo represented by the following general formula [5] or the following general formula [6] without purifying the nitrogen-containing heterocyclic compound produced by the method for producing a nitrogen-containing heterocyclic compound according to the above 1 A method for producing a nitrogen-containing heterocyclic compound, which comprises reacting in the presence of a rhinium salt to obtain a compound represented by the following general formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent, and B represents an anion.

  3. The carbene compound represented by the following general formula [7] or the following general formula [8] coordinates without purifying the nitrogen-containing heterocyclic compound produced by the method for producing a nitrogen-containing heterocyclic compound described in 1 above. A method for producing a nitrogen-containing heterocyclic compound, which comprises reacting in the presence of the resulting Pd complex to obtain a compound represented by the following general formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent.)

  4. The nitrogen-containing heterocyclic compound produced by the method for producing a nitrogen-containing heterocyclic compound according to the above 1 is reacted in the presence of a Pd catalyst and a compound represented by the following general formula [9] without purification. A process for producing a nitrogen-containing heterocyclic compound, which comprises obtaining a compound represented by the formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{8 to} R _{11 each} represent an alkyl group, a cycloalkyl group or an aryl group.

5. A compound represented by the following general formula [3] is reacted in the presence of a Pd catalyst and an imidazolinium salt represented by the following general formula [5] or the following general formula [6] to obtain a compound represented by the following general formula [4] A method for producing a nitrogen-containing heterocyclic compound, which is characterized by obtaining a compound represented.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent, and B represents an anion.

  6. A compound represented by the following general formula [3] is reacted in the presence of a Pd complex to which a carbene compound represented by the following general formula [7] or the following general formula [8] is coordinated, by the following general formula [4] A method for producing a nitrogen-containing heterocyclic compound, which is characterized by obtaining a compound represented.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent.)

  7. A compound represented by the following general formula [3] is reacted in the presence of a Pd catalyst and a compound represented by the following general formula [9] to obtain a compound represented by the following general formula [4] Method for producing a nitrogen-containing heterocyclic compound.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{8 to} R _{11 each} represent an alkyl group, a cycloalkyl group or an aryl group.

  The method for producing a nitrogen-containing heterocyclic compound of the present invention can obtain a nitrogen-containing heterocyclic compound in a short number of steps and in a high yield.

It is a flowchart of the manufacturing method of the nitrogen-containing heterocyclic compound in this invention. It is a flowchart of the manufacturing method of the nitrogen-containing heterocyclic compound in this invention.

Hereinafter, the present invention will be described in more detail.
As shown in FIG. 1, the method for producing a nitrogen-containing heterocyclic compound includes Step S101 of obtaining a compound represented by General Formula [3].

In the method for producing a nitrogen-containing heterocyclic compound, a compound represented by the following general formula [1] is reacted with a compound represented by the following general formula [2] to obtain a compound represented by the following general formula [3] It is.
The nitrogen-containing heterocyclic compound represented by the general formula [3] is a useful intermediate of an organic synthetic compound, particularly a nitrogen-containing heterocyclic compound useful as a material for organic electroluminescence.

In general formulas [1] to [3], Y represents an oxygen atom or a sulfur atom. Among these, preferred is an oxygen atom.
In general formulas [1] to [3], R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Among these, preferred is an aryl group.

In the general formulas [1] to [3], R _{1 to} R ₂ each represent a substituent.
In the general formulas [1] to [3], A _{1 to} A ₇ represent N or CR ₃ , and R ₃ represents a hydrogen atom or a substituent. However, the number of N of A _{1 to} A ₄ is 1 to 2, preferably 1.
In general formulas [1] to [3], m ₁ represents an integer of 0 to ₂ , and m ₂ represents an integer of 0 to 3.

  It is preferable to use a base in combination in the reaction of reacting the compound represented by the general formula [1] with the compound represented by the general formula [2] to obtain the compound represented by the general formula [3]. Examples of the base include alkali metal salts (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, cesium fluoride, sodium t-butoxide, potassium t-butoxide and the like), amine derivatives (triethylamine and the like) and the like. Preferred among these is potassium carbonate.

  As a reaction solvent used for the reaction to obtain the compound represented by the general formula [3] by reacting the compound represented by the general formula [1] with the compound represented by the general formula [2], an aprotic solvent ( For example, DMF, DMAc, DMSO, NMP etc., aromatic hydrocarbon solvents (eg xylene, dichlorobenzene etc), ether solvents (eg ethylene glycol dimethyl ether etc) can be mentioned. Preferred among these is DMSO.

  As for the reaction temperature of reaction which obtains the compound represented by General formula [3], 100-160 degreeC is preferable normally. If the reaction temperature is 100 ° C. or more, the reaction is further promoted. On the other hand, if the reaction temperature is 160 ° C. or less, side reactions can be suppressed. The reaction temperature is more preferably 130 ° C. or more from the viewpoint of promoting the reaction. The reaction temperature is more preferably 150 ° C. or less from the viewpoint of suppressing the side reaction. That is, the reaction temperature is preferably 100 to 160 ° C., more preferably 130 to 150 ° C.

  As shown in FIG. 2, the method for producing a nitrogen-containing heterocyclic compound comprises the step of obtaining a compound represented by the general formula [3] and the step S102 of obtaining a compound represented by the general formula [4] Including.

[Method for Producing Compound Represented by General Formula [4] (1)]
The method for producing a nitrogen-containing heterocyclic compound is a compound represented by the following general formula [3] in the presence of a Pd catalyst and an imidazolinium salt represented by the following general formula [5] or the following general formula [6] To obtain a compound represented by the following general formula [4].
The nitrogen-containing heterocyclic compound represented by the general formula [4] is a nitrogen-containing heterocyclic compound derived from the compound represented by the general formula [3], and is particularly useful as a material for organic electroluminescence It is a nitrogen-containing heterocyclic compound.

In general formulas [3] to [6], Y represents an oxygen atom or a sulfur atom. Among these, preferred is an oxygen atom.
In general formulas [3] to [6], R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Among these, preferred is an aryl group.

In the general formulas [3] to [6], R _{1 to} R ₂ each represent a substituent.
In the general formulas [3] to [6], A _{1 to} A ₇ represent N or CR ₃ , and R ₃ represents a hydrogen atom or a substituent. However, the number of N of A _{1 to} A ₄ is 1 to 2, preferably 1.
In general formulas [3] to [6], m ₁ represents an integer of 0 to ₂ , and m ₂ represents an integer of 0 to 3.
In general formulas [3] to [6], R _{4 to} R ₇ each represent a hydrogen atom or a substituent.

  In general formulas [3] to [6], B represents an anion. Examples of the anion represented by B include halide, tetrafluoroborate, tetraphenylborate and acetate.

Examples of the Pd catalyst include PdCl ₂ , Pd (OAc) ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ dppf, Pd (dba) ₂ , Pd / c and the like.
It is preferable to use the usage-amount of Pd catalyst in 0.01-0.3 mol with respect to 1 mol of compounds represented by General formula [3], and it is especially preferable to use in 0.02-0.1 mol. preferable.
The imidazolinium salt represented by the general formula [5] or the general formula [6] is preferably used in the range of 0.01 to 0.3 mol with respect to 1 mol of the compound represented by the general formula [3], It is particularly preferable to use in the range of 0.02 to 0.1 mol.

As described above, the compound represented by the general formula [3] can be obtained by reacting the compound represented by the general formula [1] with the compound represented by the general formula [2]. it can. However, as the compound represented by the general formula [3], those obtained by methods other than this method can also be used.
In any of the methods, the obtained compound represented by the general formula [3] is a Pd catalyst and imidazolinium represented by the general formula [5] or the general formula [6] without purification. It can be used for the reaction in the presence of a salt. However, it may be used after purification.

[Method for Producing Compound Represented by General Formula [4] (2)]
The method for producing a nitrogen-containing heterocyclic compound is carried out in the presence of a Pd complex in which a carbene compound represented by the following general formula [7] or the following general formula [8] is coordinated with a compound represented by the following general formula [3] To obtain a compound represented by the following general formula [4].

In the general formulas [3], [4], [7] and [8], Y represents an oxygen atom or a sulfur atom. Among these, preferred is an oxygen atom.
In the general formulas [3], [4], [7] and [8], R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Among these, preferred is an aryl group.

In the general formulas [3], [4], [7] and [8], R _{1 to} R ₂ each represent a substituent.
In the general formulas [3], [4], [7] and [8], A _{1 to} A ₇ represent N or CR ₃ , and R ₃ represents a hydrogen atom or a substituent. However, the number of N of A _{1 to} A ₄ is 1 to 2, preferably 1.
In general formulas [3], [4], [7], and [8], m ₁ represents an integer of 0 to ₂ , and m ₂ represents an integer of 0 to 3.
In the general formulas [3], [4], [7] and [8], R _{4 to} R ₇ each represent a hydrogen atom or a substituent.

  The Pd complex coordinated by the carbene compound represented by the general formula [7] or the general formula [8] is used in the range of 0.01 to 0.3 mol with respect to 1 mol of the compound represented by the general formula [3] It is preferable to use in the range of 0.02 to 0.1 mol.

As described above, the compound represented by the general formula [3] can be obtained by reacting the compound represented by the general formula [1] with the compound represented by the general formula [2]. it can. However, as the compound represented by the general formula [3], those obtained by methods other than this method can also be used.
In any of the methods, the obtained compound represented by the general formula [3] is a Pd to which the carbene compound represented by the general formula [7] or the general formula [8] is coordinated without purification. It can be used for the reaction in the presence of a complex. However, it may be used after purification.

[Method for Producing Compound Represented by General Formula [4] (3)]
The method for producing a nitrogen-containing heterocyclic compound is a reaction of a compound represented by the following general formula [3] in the presence of a Pd catalyst and a compound represented by the following general formula [9], and a table of the following general formula [4] Compounds to be obtained.

In the general formulas [3], [4] and [9], Y represents an oxygen atom or a sulfur atom. Among these, preferred is an oxygen atom.
In general formulas [3], [4] and [9], R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Among these, preferred is an aryl group.

In the general formulas [3], [4] and [9], R _{1 to} R ₂ each represent a substituent.
In the general formulas [3], [4] and [9], A _{1 to} A ₇ represent N or CR ₃ , and R ₃ represents a hydrogen atom or a substituent. However, the number of N of A _{1 to} A ₄ is 1 to 2, preferably 1.
In general formulas [3], [4] and [9], m ₁ represents an integer of 0 to ₂ , and m ₂ represents an integer of 0 to 3.
General formula [3], [4], in _[9], R 8 _{to R 11} represents an alkyl group, a cycloalkyl group, an aryl group.
R ₈ and R ₉ are preferably an aryl group.
R ₁₀ and R ₁₁ are preferably a cycloalkyl group or an alkyl group, and particularly preferably a t-butyl group.

Examples of the Pd catalyst include PdCl ₂ , Pd (OAc) ₂ , Pd (PPh ₃ ) ₄ , PdCl ₂ dppf, Pd (dba) ₂ , Pd / c and the like.
It is preferable to use the usage-amount of Pd catalyst in 0.01-0.3 mol with respect to 1 mol of compounds represented by General formula [3], and it is especially preferable to use in 0.02-0.1 mol. preferable.

The compound represented by the general formula "9" is preferably used in a range of 0.01 to 0.3 mol, more preferably a range of 0.02 to 0.1 mol, per 1 mol of the compound represented by the general formula [3]. It is particularly preferred to use
The compound represented by the general formula "9" is preferably used in combination with an aliphatic carboxylic acid, and particularly preferably used in combination with pivalic acid.

As described above, the compound represented by the general formula [3] can be obtained by reacting the compound represented by the general formula [1] with the compound represented by the general formula [2]. it can. However, as the compound represented by the general formula [3], those obtained by methods other than this method can also be used.
In any of the methods, the obtained compound represented by the general formula [3] is used for the reaction in the presence of a Pd catalyst and the compound represented by the general formula [9] without purification. Can. However, it may be used after purification.

  In the methods (1) to (3) for producing the compound represented by the general formula [4], it is preferable to use a base in combination in the reaction to obtain the compound represented by the general formula [4]. Examples of the base include alkali metal salts (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, cesium fluoride, sodium t-butoxide, potassium t-butoxide and the like), amine derivatives (triethylamine and the like) and the like. Among these, potassium carbonate, sodium t-butoxide and potassium t-butoxide are preferred.

  In the production methods (1) to (3) of the compound represented by the general formula [4], the reaction temperature for the reaction to obtain the compound represented by the general formula [4] is preferably 100 to 160 ° C. in general. If the reaction temperature is 100 ° C. or more, the reaction is further promoted. On the other hand, if the reaction temperature is 160 ° C. or less, side reactions can be suppressed. The reaction temperature is more preferably 130 ° C. or more from the viewpoint of promoting the reaction. The reaction temperature is more preferably 150 ° C. or less from the viewpoint of suppressing the side reaction. That is, the reaction temperature is preferably 100 to 160 ° C., more preferably 130 to 150 ° C.

As the substituent represented by R _{1 to} R ₇ in the general formulas [1] to [8], for example, alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, heterocycle (eg, dibenzofuran) Ring, azadibenzofuran ring, dibenzodiophen ring, carbazole ring etc.) sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino , Imide, ureido, sulfamoylamino, alkoxycarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, carboxyl, 2- (2- (2- Lysyl) include the groups such as phenyl. Among these, preferred is an aryl group.

Among the substituents represented by R ₄ and R ₅ , preferred is an aryl group, more preferred is a branched alkyl group at two ortho positions, and a 2,6-diisopropylphenyl group is particularly preferred.

  Hereinafter, representative specific examples of the compound represented by the general formula [1] of the present invention will be shown, but the present invention is not limited thereto.

  Hereinafter, representative specific examples of the compound represented by the general formula [2] of the present invention will be shown, but the present invention is not limited thereto.

  Hereinafter, representative specific examples of the compound represented by the general formula [3] of the present invention will be shown, but the present invention is not limited thereto.

  Hereinafter, representative specific examples of the compound represented by the general formula [4] of the present invention will be shown, but the present invention is not limited thereto.

  Hereinafter, representative specific examples of the compound represented by the general formula [5] of the present invention will be shown, but the present invention is not limited thereto.

  Hereinafter, representative specific examples of the compound represented by the general formula [6] of the present invention will be shown, but the present invention is not limited thereto.

  Although the typical specific example of the Pd complex which the carbene compound represented by General formula [7] or General formula [8] of this invention coordinated below is shown, this invention is not limited to these.

  Hereinafter, representative specific examples of the compound represented by the general formula [9] of the present invention will be shown, but the present invention is not limited thereto.

  EXAMPLES The present invention will be specifically described by way of examples, but the embodiments of the present invention are not limited thereto.

Example 1 (comparative example)
Synthesis of Exemplified Compound 4-4

In a stream of nitrogen, 11.4 g (× 1.1 mol) of compound E, 10 g (58.8 mmol) of the exemplified compound 2-5, 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, and 135 to 140 ° C. Stir for 7 hours. Ethyl acetate was added, washed with water, and the solvent was removed by distillation under reduced pressure to obtain Compound F. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 3.4 g (× 0.1 mol) of Pd (dba) _2, 1.6 g (× 0.1 mol) of the exemplified compound 9-1, 1.8 g (× 0.3 mol) of pivalic acid, 12.2 g (××) of potassium carbonate 1.5 mol) was added and stirring was performed at 150 ° C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (silica gel, ethyl acetate / toluene) to obtain 3.7 g of a white crystal (yield 25.5%, purity 99.1%).
The structure of the exemplary compound 4-4 was confirmed by ¹ H NMR.

Exemplary Compound 4-4 ¹ H NMR (400 MHz, CDCl 3): 8.70 (d, 1 H), 7. 92 (m, 3 H), 7.74 (d, 1 H), 7.57 (m, 3 H), 7. 47 (dd, 1 H), 7.41 (dd, 1H)

Example 2 (invention)
Synthesis of Exemplified Compound 4-4

  In a nitrogen stream, 8.5 g (× 1.1 mol) of Exemplified Compound 1-1, 10 g (58.8 mmol) of Exemplified Compound 2-5, and 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, It stirred at 135-140 degreeC for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-4. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 0.76 g (x 0.02 mol) of exemplary compounds 7-2 and 16.2 g (x 2 mol) of potassium carbonate were added, and the mixture was stirred at 140 ° C for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. To this suspension was added 43 ml of acetic acid, and the mixture was stirred overnight under ice-water cooling. The precipitated crystals were filtered and dried to obtain 8.2 g of white crystals (yield 56.9%, purity 99.8%).

Example 3 (Invention)
Synthesis of Exemplified Compound 4-4

In a stream of nitrogen, 8.5 g (× 1.1 mol) of Exemplified Compound 1-1, 10 g (58.8 mmol) of Exemplified Compound 2-5, and 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, Stir at ~ 140 ° C for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-4. Next, 50 ml of DMF was added to another container, and nitrogen bubbling was performed for 20 minutes. 3.4 g (x 0.1 mol) of Pd (dba) ₂ , 2.8 g (x 0.1 mol) of the exemplified compound 6-1, and 0.79 g (x 0.12 mol) of KOBu-t were added, and the mixture was stirred for 10 minutes. The residue, 12.2 g (× 1.5 mol) of potassium carbonate was added, and the mixture was stirred at 140 ° C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (silica gel, ethyl acetate / toluene) to obtain 10.1 g of white crystals (yield 70.0%, purity 99.1%).

Example 4 (invention)
Synthesis of Exemplified Compound 4-4

In a stream of nitrogen, 8.5 g (× 1.1 mol) of Exemplified Compound 1-1, 10 g (58.8 mmol) of Exemplified Compound 2-5, and 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, Stir at ~ 140 ° C for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-4. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 3.4 g (× 0.1 mol) of Pd (dba) ₂ , 1.6 g (× 0.1 mol) of the exemplified compound 9-1, 1.8 g (× 0.3 mol) of pivalic acid, 12.2 g (× 1 of potassium carbonate .5 mol) was added and stirring was carried out at 150.degree. C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (silica gel, ethyl acetate / toluene) to obtain 9.4 g of a white crystal (yield 65.0%, purity 99.1%).

Example 5 (Invention)
Synthesis of Exemplified Compound 4-2

  Dissolve 8.5 g (× 1.1 mol) of Exemplified Compound 1-2, 8.8 g (58.8 mmol) of Exemplified Compound 2-3, and 20.3 g (× 2.5 mol) of potassium carbonate in 80 ml of DMSO in a nitrogen stream. The mixture was stirred at 135 to 140 ° C. for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-2. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 0.67 g (x 0.02 mol) of exemplary compounds 7-1 and 16.2 g (x 2 mol) of potassium carbonate were added, and the mixture was stirred at 140 ° C for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (silica gel, ethyl acetate / toluene) to obtain 8.5 g of a white crystal (yield 64.0%, purity 99.0%).

Example 6 (invention)
Synthesis of Exemplified Compound 4-3

In a stream of nitrogen, 8.5 g (× 1.1 mol) of Exemplified Compound 1-3, 10.4 g (58.8 mmol) of Exemplified Compound 2-4, and 20.3 g (× 2.5 mol) of potassium carbonate were dissolved in 80 ml of DMSO. The mixture was stirred at 135 to 140 ° C. for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-3. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 3.4 g (× 0.1 mol) of Pd (dba) ₂ , 1.9 g (× 0.1 mol) of the exemplified compound 9-3, 1.8 g (× 0.3 mol) of pivalic acid, 12.2 g (× 1) of potassium carbonate .5 mol) was added and stirring was carried out at 150.degree. C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. Purification by column chromatography (silica gel, ethyl acetate / toluene) gave 9.2 g of white crystals (yield 62.0%, purity 99.1%).

Example 7 (Invention)
Synthesis of Exemplified Compound 4-12

In a stream of nitrogen, 8.5 g (× 1.1 mol) of Exemplified Compound 1-1, 11 g (58.8 mmol) of Exemplified Compound 2-10, and 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, Stir at ~ 140 ° C for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-12. Next, 50 ml of DMF was added to another container, and nitrogen bubbling was performed for 20 minutes. 3.4 g (x 0.1 mol) of Pd (dba) ₂ , 2.8 g (x 0.1 mol) of the exemplary compound 5-1, and 0.79 g (x 0.12 mol) of KOBu-t were added, and the mixture was stirred for 10 minutes. The residue, 12.2 g (× 1.5 mol) of potassium carbonate was added, and the mixture was stirred at 140 ° C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. The residue was purified by column chromatography (silica gel, ethyl acetate / toluene) to obtain 9.4 g of a white crystal (yield 61.1%, purity 99.0%).

Example 8 (Invention)
Synthesis of Exemplified Compound 4-4

  In a stream of nitrogen, 8.5 g (× 1.1 mol) of Exemplified Compound 1-1, 10 g (58.8 mmol) of Exemplified Compound 2-5, and 20.3 g (× 2.5 mol) of potassium carbonate are dissolved in 80 ml of DMSO, Stir at ~ 140 ° C for 7 hours. Ethyl acetate was added, the mixture was washed with water, and the solvent was removed by distillation under reduced pressure to obtain Exemplified Compound 3-4. Next, 50 ml of DMF was added and nitrogen bubbling was performed for 20 minutes. 0.76 g (× 0.02 mol) of the exemplified compound 8-2 and 16.2 g (× 2 mol) of potassium carbonate were added, and the mixture was stirred at 140 ° C. for 7 hours. Ethyl acetate was added, washed with water and the solvent was removed by distillation under reduced pressure. To this suspension was added 43 ml of acetic acid, and the mixture was stirred overnight under ice-water cooling. The precipitated crystals were filtered and dried to obtain 8.1 g of white crystals (yield 56.2%, purity 99.8%).

  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.

  As described above, according to the production method of the present invention, a nitrogen-containing heterocyclic compound which is a useful intermediate of an organic synthetic compound and a nitrogen-containing heterocyclic compound derived therefrom can be obtained with a short number of steps and a high yield. Further, the nitrogen-containing heterocyclic compound obtained by the production method of the present invention is particularly useful as a material for organic electroluminescence, and has an excellent effect.

Claims (7)

The nitrogen-containing heterocyclic compound is characterized in that a compound represented by the following general formula [1] is reacted with a compound represented by the following general formula [2] to obtain a compound represented by the following general formula [3] Production method.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 Represents an integer of It is represented by Pd catalyst and following General formula [5] or following General formula [6], without refine | purifying the nitrogen-containing heterocyclic compound manufactured by the manufacturing method of the nitrogen-containing heterocyclic compound of Claim 1 A method for producing a nitrogen-containing heterocyclic compound, which comprises reacting in the presence of an imidazolinium salt to obtain a compound represented by the following general formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent, and B represents an anion. A carbene compound represented by the following general formula [7] or the following general formula [8] without purifying the nitrogen-containing heterocyclic compound produced by the method for producing a nitrogen-containing heterocyclic compound according to claim 1 A method for producing a nitrogen-containing heterocyclic compound, which comprises reacting in the presence of a coordinated Pd complex to obtain a compound represented by the following general formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent.) A nitrogen-containing heterocyclic compound produced by the method for producing a nitrogen-containing heterocyclic compound according to claim 1 is reacted in the presence of a Pd catalyst and a compound represented by the following general formula [9] without purification. A process for producing a nitrogen-containing heterocyclic compound, which comprises obtaining a compound represented by the general formula [4].

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{8 to} R _{11 each} represent an alkyl group, a cycloalkyl group or an aryl group. A compound represented by the following general formula [3] is reacted in the presence of a Pd catalyst and an imidazolinium salt represented by the following general formula [5] or the following general formula [6] to obtain a compound represented by the following general formula [4] A method for producing a nitrogen-containing heterocyclic compound, which is characterized by obtaining a compound represented.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent, and B represents an anion. A compound represented by the following general formula [3] is reacted in the presence of a Pd complex to which a carbene compound represented by the following general formula [7] or the following general formula [8] is coordinated, by the following general formula [4] A method for producing a nitrogen-containing heterocyclic compound, which is characterized by obtaining a compound represented.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{4 to} R _{7 each} represent a hydrogen atom or a substituent.) A compound represented by the following general formula [3] is reacted in the presence of a Pd catalyst and a compound represented by the following general formula [9] to obtain a compound represented by the following general formula [4] Method for producing a nitrogen-containing heterocyclic compound.

Wherein Y represents an oxygen atom or a sulfur atom, R represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, R _{1 to} R ₂ each represents a substituent, and A _{1 to} A ₇ each represent N. or represents CR _{3, R 3} represents a hydrogen atom or a substituent. _However, the number of N of a 1 to a ₄ is 1 to 2 .m ₁ is an integer of 0 to 2, _{m 2} is 0 to 3 R _{8 to} R _{11 each} represent an alkyl group, a cycloalkyl group or an aryl group.

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