WO2018025554A1 - Nitrogen-containing heterocyclic compound production method - Google Patents

Nitrogen-containing heterocyclic compound production method Download PDF

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WO2018025554A1
WO2018025554A1 PCT/JP2017/024488 JP2017024488W WO2018025554A1 WO 2018025554 A1 WO2018025554 A1 WO 2018025554A1 JP 2017024488 W JP2017024488 W JP 2017024488W WO 2018025554 A1 WO2018025554 A1 WO 2018025554A1
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group
compound
general formula
structure represented
nitrogen
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杉田　修一
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コニカミノルタ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing a nitrogen-containing heterocyclic compound.
  • this invention relates to the manufacturing method of the nitrogen-containing heterocyclic compound which can provide the nitrogen-containing heterocyclic compound useful as an organic electroluminescent element material with a high yield.
  • the present invention has been made in view of the above problems and situations, and its solution is to provide a method for producing a nitrogen-containing heterocyclic compound from which a nitrogen-containing heterocyclic compound can be obtained with high yield and high purity. is there.
  • the present inventor has found that a compound having a reactive group such as dihalogen having a specific structure and an amine compound having a specific structure are present in the presence of a Pd catalyst and a phosphine ligand.
  • the inventors have found that a nitrogen-containing heterocyclic compound having a specific structure can be obtained with a high yield and a high purity by reacting under the above conditions, and the present invention has been achieved. That is, the said subject of this invention is solved by the following means.
  • a compound having a structure represented by the following general formula [1] and a compound having a structure represented by the following general formula [2] are reacted in the presence of a Pd catalyst and a phosphine ligand, and the following general formula [3]
  • combines the compound which has a structure represented by these.
  • X is a halogen atom
  • .Z 1 and Z 2 represents an alkyl sulfonate group or an aryl sulfonate group, each non-metallic atomic group necessary for forming an aromatic hydrocarbon ring or aromatic heterocyclic ring
  • Z 3 represents a simple bond or a divalent linking group
  • X 1 represents an oxygen atom or a sulfur atom
  • a 1 to A 4 each represent a nitrogen atom or CR, provided that A 1 to (At least one of A 4 is a nitrogen atom.
  • R and R 1 to R 3 each represents a hydrogen atom or a substituent.
  • the compound having a structure represented by the general formula [2] is a compound having a structure represented by the following general formula [4], and a compound having a structure represented by the general formula [3]
  • Z 1 and Z 2 each represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • Z 3 represents a simple bond or a divalent linking group.
  • X 1 represents an oxygen atom or a sulfur atom
  • R 1 to R 6 each represents a hydrogen atom or a substituent.
  • the method for producing a nitrogen-containing heterocyclic compound of the present invention comprises a compound having a structure represented by the general formula [1] and a compound having a structure represented by the general formula [2], a Pd catalyst and a phosphine ligand. And a compound having the structure represented by the general formula [3] is synthesized.
  • This feature is a technical feature common to or corresponding to the embodiments described below.
  • the compound having a structure represented by the general formula [2] is a compound having a structure represented by the general formula [4], and a compound having a structure represented by the general formula [3]
  • a compound having a structure represented by the following general formula [5] is preferable.
  • the phosphine ligand has a structure represented by the general formula [6].
  • Z 3 is preferably a simple bond.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the method for producing a nitrogen-containing heterocyclic compound of the present invention comprises a compound having a structure represented by the following general formula [1] and a compound having a structure represented by the following general formula [2], a Pd catalyst and a phosphine ligand. And a compound having a structure represented by the following general formula [3] is synthesized.
  • the compound having the structure represented by the general formula [1] two aromatic hydrocarbon rings or aromatic heterocycles are linked via Z 3 , and a halogen atom is substituted at each ortho position. It is a structural feature.
  • the same symbol represents the same atom, atomic group or substituent.
  • X represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group.
  • Z 1 and Z 2 each represents a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • Z 3 represents a simple bond or a divalent linking group.
  • X 1 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.
  • Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, particularly preferred are a chlorine atom and a bromine atom.
  • Examples of the alkyl sulfonate group represented by X include a methanesulfonyl group and an ethanesulfonyl group.
  • Examples of the aryl sulfonate group represented by X include a benzenesulfonyl group and a tosyl group.
  • Examples of the aromatic hydrocarbon ring containing Z 1 and Z 2 include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-tell Phenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyranthrene ring, anthraanthrene Ring, dibenzofuran ring, dibenzodiophene ring, carbazole ring and the like.
  • a benzene ring is particularly preferred.
  • the aromatic heterocycle containing Z 1 and Z 2 include a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, an oxadiazole ring, a triazole ring, and an imidazole.
  • Ring pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring and the like.
  • a pyridine ring particularly preferred is a pyridine ring.
  • an aromatic heterocyclic ring is particularly preferable.
  • the divalent linking group represented by Z 3 may include, for example, a hydrocarbon group such as alkylene, alkenylene, alkynylene, and arylene, a hetero atom, a thiophene-2,5-diyl group, It may be a divalent linking group derived from a compound having an aromatic heterocycle such as a pyrazine-2,3-diyl group (also referred to as a heteroaromatic compound), or a chalcogen atom such as oxygen or sulfur. There may be. Further, it may be a group linked via a hetero atom such as an alkylimino group, a dialkylsilanediyl group or a diarylgermandiyl group. A mere bond is a mere bond that directly bonds the connecting substituents together. Of these, preferred is a mere bond.
  • examples of the substituent represented by R and R 1 to R 3 include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, and a sulfonamide group.
  • Pd catalyst examples include PdCl 2 , Pd (OAc) 2 , Pd (pph 3 ) 4 , PdCl 2 (dppf), Pd (dba) 2 , Pd / C, and the like.
  • the amount of the Pd catalyst used is preferably in the range of 0.01 to 0.3 mol, preferably in the range of 0.02 to 0.2 mol, relative to 1 mol of the compound having the structure represented by the general formula [2]. It is particularly preferred to use in
  • phosphine ligands for palladium include trialkylphosphines (eg, tributylphosphine, tri-t-butylphosphine, tricyclohexylphosphine), phosphines having at least one aryl group (eg, triphenylphosphine, SPhos (2-Dicyclohexylphosphino-2 ′). , 6'-dimethylbiphenyl), XPhos (2-Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl) and the like.
  • trialkylphosphines eg, tributylphosphine, tri-t-butylphosphine, tricyclohexylphosphine
  • phosphines having at least one aryl group eg, triphenylphosphine, SPhos (2-Dicyclohexylpho
  • phosphine having one aryl group is preferable, and SPhos is particularly preferable.
  • the phosphine ligand is preferably used in the range of 0.3 to 3 mol, particularly preferably in the range of 0.5 to 2 mol, relative to 1 mol of the Pd catalyst.
  • the phosphine ligand is preferably used in the range of 0.02 to 0.5 mol with respect to 1 mol of the compound having the structure represented by the general formula [1], but is used in the range of 0.03 to 0.1 mol. It is particularly preferred. It is preferable to use a base in the above reaction.
  • Examples of the base include alkali metal salts (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, cesium fluoride, sodium t-butoxide, etc.), amine derivatives (triethylamine, etc.) and the like.
  • reaction solvent examples include xylene, toluene, THF, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1,4-dioxane, and the like. Of these, xylene is preferred.
  • the reaction temperature is usually preferably in the range of 50 to 140 ° C., particularly preferably in the range of 60 to 100 ° C.
  • the compound having the structure represented by the general formula [2] is a compound having a structure represented by the following general formula [4], and a compound having a structure represented by the general formula [3] Is preferably a compound having a structure represented by the following general formula [5].
  • Z 1 and Z 2 each represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring.
  • Z 3 represents a simple bond or a divalent linking group.
  • X 1 represents an oxygen atom or a sulfur atom.
  • R 1 to R 6 each represent a hydrogen atom or a substituent.
  • Z 1 and Z 2 represent non-metallic atomic group represented by the general formula [1] and can use the Z 1 and Z 2 same of [2], also a divalent linking group represented by Z 3 use the same be able to.
  • the substituent represented by R 1 ⁇ R 6 has the general formula [1] and can use the same as the substituent represented by R 1 ⁇ R 6 of [2], further substituted with a substituent The point which may be done is also the same.
  • the phosphine ligand preferably has a structure represented by the following general formula [6].
  • R 7 to R 9 each represents an alkyl group, a cycloalkyl group, or an aryl group. Of the groups represented by R 7 , particularly preferred is a cycloalkyl group. Of the groups represented by R 8 and R 9 , an alkyl group is particularly preferable. Examples of the cycloalkyl group represented by R 7 to R 9 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.
  • the alkyl group R 7 ⁇ R 9 represent, for example, methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl group, a pentyl group, an octyl group.
  • Examples of the aryl group represented by R 7 to R 9 include a phenyl group, a biphenyl group, and a terphenyl group.
  • Synthesis example 1 (comparative example) ⁇ Synthesis of Exemplified Compound 3-6 >> 7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.3 g of Ligand A were added and heated at 120 ° C. for 5 hours. After concentration under reduced pressure, the obtained solid was washed with water and dried. 5 L of a 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 7.0 g of brown crystals (yield 50%, purity 87.5%).
  • Synthesis Example 2 (present invention) ⁇ Synthesis of Exemplified Compound 3-6 >> 7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. The mixture was stirred for 3 hours under water cooling, and the precipitated crystals were filtered, washed with water and dried.
  • Synthesis Example 3 (present invention) ⁇ Synthesis of Exemplified Compound 3-6 >> 7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 0.96 g of Exemplified Compound 6-2 were added and heated at 120 ° C. for 4 hours. The mixture was stirred for 3 hours under water cooling, and the precipitated crystals were filtered, washed with water and dried.
  • Synthesis example 4 (comparative example) ⁇ Synthesis of Exemplified Compound 3-12 >> 7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.3 g of Ligand A were added and heated at 120 ° C. for 5 hours. After concentration under reduced pressure, the obtained solid was washed with water and dried. 5 L of a 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized from toluene / acetonitrile to obtain 6.5 g of brown crystals (yield 45%, purity 86.5%).
  • Synthesis Example 5 (present invention) ⁇ Synthesis of Exemplified Compound 3-12 >> 7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. The mixture was stirred for 3 hours under water cooling, and the precipitated crystals were filtered, washed with water and dried.
  • Synthesis Example 6 (present invention) ⁇ Synthesis of Exemplified Compound 3-12 >> 7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 0.62 g of Pd (OAc) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. The mixture was stirred for 3 hours under water cooling, and the precipitated crystals were filtered, washed with water and dried.
  • the method for producing a nitrogen-containing heterocyclic compound of the present invention can be suitably used for producing, for example, a nitrogen-containing heterocyclic compound used as a material for an organic electroluminescence device.

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  • Organic Chemistry (AREA)
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Abstract

The present invention addresses the problem of providing a nitrogen-containing heterocyclic compound production method by which a nitrogen-containing heterocyclic compound having a high purity can be obtained with a high yield. The nitrogen-containing heterocyclic compound production method according to the present invention comprises synthesizing a compound having a structure represented by general formula [3], by causing a reaction of a compound having a structure represented by general formula [1] with a compound having a structure represented by general formula [2] in the presence of a Pd catalyst and a phosphine ligand.

Description

含窒素複素環化合物の製造方法Method for producing nitrogen-containing heterocyclic compound
　本発明は、含窒素複素環化合物の製造方法に関する。より詳しくは、本発明は、有機エレクトロルミネッセンス素子用材料として有用な含窒素複素環化合物を高収率で提供することができる含窒素複素環化合物の製造方法に関する。 The present invention relates to a method for producing a nitrogen-containing heterocyclic compound. In more detail, this invention relates to the manufacturing method of the nitrogen-containing heterocyclic compound which can provide the nitrogen-containing heterocyclic compound useful as an organic electroluminescent element material with a high yield.
　ビピリジルジハライドとアミン化合物からジアザカルバゾールを形成する合成法として、Ｐｄ触媒存在下でイミダゾリニウム塩を用いる方法が知られている（例えば、特許文献１参照。）。 As a synthesis method for forming diazacarbazole from bipyridyl dihalide and an amine compound, a method using an imidazolinium salt in the presence of a Pd catalyst is known (for example, see Patent Document 1).
　しかしながら、この合成法を、含窒素複素環化合物に使用すると、反応が途中でとまり、触媒を追加しても反応が進行しない場合があることがわかった。 However, it has been found that when this synthesis method is used for a nitrogen-containing heterocyclic compound, the reaction stops in the middle and the reaction may not proceed even if a catalyst is added.
特開２０１０－２６０８１５号公報JP 2010-260815 A
　本発明は、上記問題・状況に鑑みてなされたものであり、その解決課題は、高収率かつ高純度で含窒素複素環化合物が得られる含窒素複素環化合物の製造方法を提供することである。 The present invention has been made in view of the above problems and situations, and its solution is to provide a method for producing a nitrogen-containing heterocyclic compound from which a nitrogen-containing heterocyclic compound can be obtained with high yield and high purity. is there.
　本発明者は、上記課題を解決すべく上記問題の原因等について検討した結果、特定構造を有するジハロゲン等の反応基を有する化合物と特定構造を有するアミン化合物とを、Ｐｄ触媒及びホスフィンリガンドの存在下で反応させることにより、高収率かつ高純度で特定構造の含窒素複素環化合物が得られることを見いだし、本発明に至った。
　すなわち、本発明の上記課題は、下記の手段により解決される。 As a result of studying the cause of the above-mentioned problem in order to solve the above-mentioned problems, the present inventor has found that a compound having a reactive group such as dihalogen having a specific structure and an amine compound having a specific structure are present in the presence of a Pd catalyst and a phosphine ligand. The inventors have found that a nitrogen-containing heterocyclic compound having a specific structure can be obtained with a high yield and a high purity by reacting under the above conditions, and the present invention has been achieved.
That is, the said subject of this invention is solved by the following means.
　１．下記一般式［１］で表される構造を有する化合物と下記一般式［２］で表される構造を有する化合物とを、Ｐｄ触媒及びホスフィンリガンドの存在下で反応させ、下記一般式［３］で表される構造を有する化合物を合成する含窒素複素環化合物の製造方法。
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｘは、ハロゲン原子、アルキルスルホネート基又はアリールスルホネート基を表す。Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ａ１～Ａ４は、それぞれ窒素原子又はＣＲを表す。ただし、Ａ１～Ａ４のうち少なくとも一つは窒素原子である。Ｒ及びＲ１～Ｒ３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] and a compound having a structure represented by the following general formula [2] are reacted in the presence of a Pd catalyst and a phosphine ligand, and the following general formula [3] The manufacturing method of the nitrogen-containing heterocyclic compound which synthesize | combines the compound which has a structure represented by these.
Figure JPOXMLDOC01-appb-C000004
 (Wherein, X is a halogen atom, .Z 1 and Z 2 represents an alkyl sulfonate group or an aryl sulfonate group, each non-metallic atomic group necessary for forming an aromatic hydrocarbon ring or aromatic heterocyclic ring Z 3 represents a simple bond or a divalent linking group, X 1 represents an oxygen atom or a sulfur atom, and A 1 to A 4 each represent a nitrogen atom or CR, provided that A 1 to (At least one of A 4 is a nitrogen atom. R and R 1 to R 3 each represents a hydrogen atom or a substituent.)
　２．前記一般式［２］で表される構造を有する化合物が、下記一般式［４］で表される構造を有する化合物であり、かつ
　前記一般式［３］で表される構造を有する化合物が、下記一般式［５］で表される構造を有する化合物である第１項に記載の含窒素複素環化合物の製造方法。
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ｒ１～Ｒ６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 [2] is a compound having a structure represented by the following general formula [4], and a compound having a structure represented by the general formula [3] The method for producing a nitrogen-containing heterocyclic compound according to Item 1, which is a compound having a structure represented by the following general formula [5].
Figure JPOXMLDOC01-appb-C000005
 (In the formula, Z 1 and Z 2 each represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Z 3 represents a simple bond or a divalent linking group. X 1 represents an oxygen atom or a sulfur atom, and R 1 to R 6 each represents a hydrogen atom or a substituent.)
　３．前記ホスフィンリガンドが、下記一般式［６］で表される構造を有する第１項又は第２項に記載の含窒素複素環化合物の製造方法。
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ７～Ｒ９は、それぞれアルキル基、シクロアルキル基又はアリール基を表す。） 3. The method for producing a nitrogen-containing heterocyclic compound according to item 1 or 2, wherein the phosphine ligand has a structure represented by the following general formula [6].
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 7 to R 9 each represents an alkyl group, a cycloalkyl group or an aryl group)
　４．前記Ｚ３が、単なる結合手である第１項から第３項までのいずれか一項に記載の含窒素複素環化合物の製造方法。 4). The method for producing a nitrogen-containing heterocyclic compound according to any one of Items 1 to 3 , wherein Z 3 is a mere bond.
　本発明の上記手段により、高収率かつ高純度で含窒素複素環化合物を得られる含窒素複素環化合物の製造方法を提供することができる。 By the above means of the present invention, it is possible to provide a method for producing a nitrogen-containing heterocyclic compound capable of obtaining a nitrogen-containing heterocyclic compound with high yield and high purity.
　本発明の含窒素複素環化合物の製造方法は、前記一般式［１］で表される構造を有する化合物と前記一般式［２］で表される構造を有する化合物とを、Ｐｄ触媒及びホスフィンリガンドの存在下で反応させ、前記一般式［３］で表される構造を有する化合物を合成することを特徴とする。この特徴は、下記実施態様に共通する又は対応する技術的特徴である。 The method for producing a nitrogen-containing heterocyclic compound of the present invention comprises a compound having a structure represented by the general formula [1] and a compound having a structure represented by the general formula [2], a Pd catalyst and a phosphine ligand. And a compound having the structure represented by the general formula [3] is synthesized. This feature is a technical feature common to or corresponding to the embodiments described below.
　前記一般式［２］で表される構造を有する化合物が、前記一般式［４］で表される構造を有する化合物であり、かつ前記一般式［３］で表される構造を有する化合物が、下記一般式［５］で表される構造を有する化合物であることが好ましい。 The compound having a structure represented by the general formula [2] is a compound having a structure represented by the general formula [4], and a compound having a structure represented by the general formula [3] A compound having a structure represented by the following general formula [5] is preferable.
　前記ホスフィンリガンドが、前記一般式［６］で表される構造を有することが、収率及び純度の観点から好ましい。 It is preferable from the viewpoint of yield and purity that the phosphine ligand has a structure represented by the general formula [6].
　前記Ｚ３が、単なる結合手であることが好ましい。 Z 3 is preferably a simple bond.
　以下、本発明とその構成要素及び本発明を実施するための形態・態様について詳細な説明をする。なお、以下の説明において示す「～」は、その前後に記載される数値を下限値及び上限値として含む意味で使用する。 Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the following description, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
《含窒素複素環化合物の製造方法の概要》
　本発明の含窒素複素環化合物の製造方法は、下記一般式［１］で表される構造を有する化合物と下記一般式［２］で表される構造を有する化合物とを、Ｐｄ触媒及びホスフィンリガンドの存在下で反応させ、下記一般式［３］で表される構造を有する化合物を合成することを特徴とする。
　一般式［１］で表される構造を有する化合物において、二つの芳香族炭化水素環又は芳香族複素環がＺ３を介して連結し、それぞれのオルト位にハロゲン原子が置換していることが構造的な特徴である。
　なお、一般式［１］～［３］で使用される記号のうち、同じ記号は同じ原子、原子団又は置換基等を表す。 << Outline of production method of nitrogen-containing heterocyclic compound >>
The method for producing a nitrogen-containing heterocyclic compound of the present invention comprises a compound having a structure represented by the following general formula [1] and a compound having a structure represented by the following general formula [2], a Pd catalyst and a phosphine ligand. And a compound having a structure represented by the following general formula [3] is synthesized.
In the compound having the structure represented by the general formula [1], two aromatic hydrocarbon rings or aromatic heterocycles are linked via Z 3 , and a halogen atom is substituted at each ortho position. It is a structural feature.
Of the symbols used in the general formulas [1] to [3], the same symbol represents the same atom, atomic group or substituent.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式中、Ｘは、ハロゲン原子、アルキルスルホネート基又はアリールスルホネート基を表す。Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ａ１～Ａ４は、それぞれ窒素原子又はＣＲを表す。ただし、Ａ１～Ａ４のうち少なくとも一つは窒素原子である。Ｒ及びＲ１～Ｒ３は、それぞれ水素原子又は置換基を表す。 In the formula, X represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group. Z 1 and Z 2 each represents a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Z 3 represents a simple bond or a divalent linking group. X 1 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が表すハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子があげられる。これらのうち特に好ましいものは、塩素原子及び臭素原子である。
　また、Ｘが表すアルキルスルホネート基としては、例えば、メタンスルホニル基、エタンスルホニル基等が挙げられる。
　また、Ｘが表すアリールスルホネート基としては、例えば、ベンゼンスルホニル基、トシル基等が挙げられる。 Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, particularly preferred are a chlorine atom and a bromine atom.
Examples of the alkyl sulfonate group represented by X include a methanesulfonyl group and an ethanesulfonyl group.
Examples of the aryl sulfonate group represented by X include a benzenesulfonyl group and a tosyl group.
　Ｚ１及びＺ２を含む芳香族炭化水素環としては、例えば、ベンゼン環、ビフェニル環、ナフタレン環、アズレン環、アントラセン環、フェナントレン環、ピレン環、クリセン環、ナフタセン環、トリフェニレン環、ｏ－テルフェニル環、ｍ－テルフェニル環、ｐ－テルフェニル環、アセナフテン環、コロネン環、フルオレン環、フルオラントレン環、ナフタセン環、ペンタセン環、ペリレン環、ペンタフェン環、ピセン環、ピラントレン環、アンスラアントレン環、ジベンゾフラン環、ジベンゾジオフェン環、カルバゾール環等が挙げられる。これらのうちで特に好ましいものはベンゼン環である。
　Ｚ１及びＺ２を含む芳香族複素環としては、例えば、フラン環、チオフェン環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、トリアジン環、ベンゾイミダゾール環、オキサジアゾール環、トリアゾール環、イミダゾール環、ピラゾール環、チアゾール環、インドール環、ベンゾイミダゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、キノキサリン環、キナゾリン環、フタラジン環等が挙げられる。これらのうちで特に好ましいものはピリジン環である。
　Ｚ１及びＺ２を含む環として、特に好ましいものは芳香族複素環である。 Examples of the aromatic hydrocarbon ring containing Z 1 and Z 2 include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, naphthacene ring, triphenylene ring, o-tell Phenyl ring, m-terphenyl ring, p-terphenyl ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring, perylene ring, pentaphen ring, picene ring, pyranthrene ring, anthraanthrene Ring, dibenzofuran ring, dibenzodiophene ring, carbazole ring and the like. Of these, a benzene ring is particularly preferred.
Examples of the aromatic heterocycle containing Z 1 and Z 2 include a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a benzimidazole ring, an oxadiazole ring, a triazole ring, and an imidazole. Ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring and the like. Of these, particularly preferred is a pyridine ring.
As the ring containing Z 1 and Z 2 , an aromatic heterocyclic ring is particularly preferable.
　Ｚ３が表す２価の連結基としては、例えば、アルキレン、アルケニレン、アルキニレン、アリーレンなどの炭化水素基の他、ヘテロ原子を含むものであってもよく、またチオフェン－２，５－ジイル基やピラジン－２，３－ジイル基のような芳香族複素環を有する化合物（ヘテロ芳香族化合物ともいう。）に由来する２価の連結基であってもよいし、酸素や硫黄などのカルコゲン原子であってもよい。
　また、アルキルイミノ基、ジアルキルシランジイル基やジアリールゲルマンジイル基のようなヘテロ原子を介して連結する基でもよい。単なる結合手とは、連結する置換基同士を直接結合する単なる結合手である。これらのうちで好ましいものは単なる結合手である。 The divalent linking group represented by Z 3 may include, for example, a hydrocarbon group such as alkylene, alkenylene, alkynylene, and arylene, a hetero atom, a thiophene-2,5-diyl group, It may be a divalent linking group derived from a compound having an aromatic heterocycle such as a pyrazine-2,3-diyl group (also referred to as a heteroaromatic compound), or a chalcogen atom such as oxygen or sulfur. There may be.
Further, it may be a group linked via a hetero atom such as an alkylimino group, a dialkylsilanediyl group or a diarylgermandiyl group. A mere bond is a mere bond that directly bonds the connecting substituents together. Of these, preferred is a mere bond.
　一般式［２］及び一般式［３］において、Ｒ及びＲ１～Ｒ３で表される置換基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アリール基、アシルアミノ基、スルホンアミド基、アルキルチオ基、アリールチオ基、ハロゲン原子、複素環（例えば、ジベンゾフラン環、アザジベンゾフラン環、ジベンゾジオフェン環、カルバゾール環等）基、スルホニル基、スルフィニル基、ホスホニル基、アシル基、カルバモイル基、スルファモイル基、シアノ基、アルコキシ基、アリールオキシ基、複素環オキシ基、シロキシ基、アシルオキシ基、カルバモイルオキシ基、アミノ基、アルキルアミノ基、イミド基、ウレイド基、スルファモイルアミノ基、アルコキシカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、アルコキシカルボニル基、アリールオキシカルボニル基、カルボキシ基等が挙げられる。
　これらの内で好ましいものはアザジベンゾフラン環基である。
　Ｘ１は、酸素原子又は硫黄原子を表し、Ｘ１で表される基のうち特に好ましいものは、酸素原子である。 In the general formula [2] and the general formula [3], examples of the substituent represented by R and R 1 to R 3 include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acylamino group, and a sulfonamide group. , Alkylthio group, arylthio group, halogen atom, heterocyclic ring (eg, dibenzofuran ring, azadibenzofuran ring, dibenzodiophene ring, carbazole ring) 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, arylo Aryloxycarbonyl amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, and the like.
Among these, an azadibenzofuran ring group is preferable.
X 1 represents an oxygen atom or a sulfur atom, particularly preferred among the groups represented by X 1 is an oxygen atom.
〈パラジウム（Ｐｄ）触媒〉
　Ｐｄ触媒としては、例えばＰｄＣｌ２、Ｐｄ（ＯＡｃ）２、Ｐｄ（ｐｐｈ３）４、ＰｄＣｌ２（ｄｐｐｆ）、Ｐｄ（ｄｂａ）２、Ｐｄ／Ｃ等が挙げられる。
　Ｐｄ触媒の使用量は、一般式［２］で表される構造を有する化合物１ｍｏｌに対して０．０１～０．３ｍｏｌの範囲内で用いることが好ましく、０．０２～０．２ｍｏｌの範囲内で用いることが特に好ましい。 <Palladium (Pd) catalyst>
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.
The amount of the Pd catalyst used is preferably in the range of 0.01 to 0.3 mol, preferably in the range of 0.02 to 0.2 mol, relative to 1 mol of the compound having the structure represented by the general formula [2]. It is particularly preferred to use in
〈ホスフィンリガンド〉
　パラジウムに対するホスフィンリガンドとしては、トリアルキルホスフィン（例えば、トリブチルホスフィン、トリｔ－ブチルホスフィン、トリシクロヘキシルホスフィン）、アリール基を少なくとも一つ有するホスフィン（例えば、トリフェニルホスフィン、ＳＰｈｏｓ（２－Ｄｉｃｙｃｌｏｈｅｘｙｌｐｈｏｓｐｈｉｎｏ－２′，６′－ｄｉｍｅｔｈｏｘｙｂｉｐｈｅｎｙｌ）、ＸＰｈｏｓ（２－Ｄｉｃｙｃｌｏｈｅｘｙｌｐｈｏｓｐｈｉｎｏ－２′，４′，６′－ｔｒｉｉｓｏｐｒｏｐｙｌｂｉｐｈｅｎｙｌ）等）が挙げられる。これらの内好ましいものはアリール基を一つ有するホスフィンであり、特に好ましくはＳＰｈｏｓである。
　ホスフィンリガンドは、Ｐｄ触媒ｌｍｏｌに対して０．３～３ｍｏｌの範囲内で用いることが好ましく、０．５～２ｍｏｌの範囲内で用いることが特に好ましい。
　ホスフィンリガンドは、一般式［１］で表される構造を有する化合物１ｍｏｌに対して０．０２～０．５ｍｏｌの範囲内で用いることが好ましいが、０．０３～０．１ｍｏｌの範囲内で用いることが特に好ましい。
　上記反応には塩基を併用するのが好ましい。塩基としては、例えば、アルカリ金属塩（炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸セシウム、フッ化セシウム、ナトリウムｔ－ブトキサイド等）、アミン誘導体（トリエチルアミン等）等が挙げられる。 <Phosphine ligand>
Examples of phosphine ligands for palladium include trialkylphosphines (eg, tributylphosphine, tri-t-butylphosphine, tricyclohexylphosphine), phosphines having at least one aryl group (eg, triphenylphosphine, SPhos (2-Dicyclohexylphosphino-2 ′). , 6'-dimethylbiphenyl), XPhos (2-Dicyclohexylphosphino-2 ', 4', 6'-triisopropylbiphenyl) and the like. Of these, phosphine having one aryl group is preferable, and SPhos is particularly preferable.
The phosphine ligand is preferably used in the range of 0.3 to 3 mol, particularly preferably in the range of 0.5 to 2 mol, relative to 1 mol of the Pd catalyst.
The phosphine ligand is preferably used in the range of 0.02 to 0.5 mol with respect to 1 mol of the compound having the structure represented by the general formula [1], but is used in the range of 0.03 to 0.1 mol. It is particularly preferred.
It is preferable to use a base in the above reaction. Examples of the base include alkali metal salts (sodium carbonate, potassium carbonate, sodium hydrogen carbonate, cesium carbonate, cesium fluoride, sodium t-butoxide, etc.), amine derivatives (triethylamine, etc.) and the like.
〈反応溶媒等〉
　反応溶媒は、例えばキシレン、トルエン、ＴＨＦ、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、１，４－ジオキサン等が挙げられる。これらのうち好ましいものはキシレンである。
　反応温度は通常５０～１４０℃の範囲内で行われるのが好ましく、６０～１００℃の範囲内で行われるのが特に好ましい。 <Reaction solvent, etc.>
Examples of the reaction solvent include xylene, toluene, THF, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1,4-dioxane, and the like. Of these, xylene is preferred.
The reaction temperature is usually preferably in the range of 50 to 140 ° C., particularly preferably in the range of 60 to 100 ° C.
　また、前記一般式［２］で表される構造を有する化合物が、下記一般式［４］で表される構造を有する化合物であり、かつ前記一般式［３］で表される構造を有する化合物が、下記一般式［５］で表される構造を有する化合物であることが好ましい。 Further, the compound having the structure represented by the general formula [2] is a compound having a structure represented by the following general formula [4], and a compound having a structure represented by the general formula [3] Is preferably a compound having a structure represented by the following general formula [5].
Figure JPOXMLDOC01-appb-C000008
 　式中、Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ｒ１～Ｒ６は、それぞれ水素原子又は置換基を表す。
Figure JPOXMLDOC01-appb-C000008
 In the formula, Z 1 and Z 2 each represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Z 3 represents a simple bond or a divalent linking group. X 1 represents an oxygen atom or a sulfur atom. R 1 to R 6 each represent a hydrogen atom or a substituent.
　Ｚ１及びＺ２が表す非金属原子群は、一般式［１］及び［２］のＺ１及びＺ２同じものを使うことができ、Ｚ３が表す２価の連結基も同じものを使うことができる。
　また、Ｒ１～Ｒ６で表される置換基は、一般式［１］及び［２］のＲ１～Ｒ６で表される置換基と同じものを使うことができ、さらに置換基で置換されていてもよい点も同様である。 Z 1 and Z 2 represent non-metallic atomic group represented by the general formula [1] and can use the Z 1 and Z 2 same of [2], also a divalent linking group represented by Z 3 use the same be able to.
Further, the substituent represented by R 1 ~ R 6 has the general formula [1] and can use the same as the substituent represented by R 1 ~ R 6 of [2], further substituted with a substituent The point which may be done is also the same.
　また、前記ホスフィンリガンドが、下記一般式［６］で表される構造を有することが好ましい。 The phosphine ligand preferably has a structure represented by the following general formula [6].
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式中、Ｒ７～Ｒ９は、それぞれアルキル基、シクロアルキル基又はアリール基を表す。
　Ｒ７で表される基のうち、特に好ましいものはシクロアルキル基である。
　Ｒ８及びＲ９で表される基のうち、特に好ましいものはアルキル基である。
　Ｒ７～Ｒ９が表すシクロアルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、アダマンチル基などが挙げられる。
　Ｒ７～Ｒ９が表すアルキル基としては、例えばメチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ペンチル基、オクチル基等が挙げられる。
　Ｒ７～Ｒ９が表すアリール基としては、例えばフェニル基、ビフェニル基、ターフェニル基等が挙げられる。 In the formula, R 7 to R 9 each represents an alkyl group, a cycloalkyl group, or an aryl group.
Of the groups represented by R 7 , particularly preferred is a cycloalkyl group.
Of the groups represented by R 8 and R 9 , an alkyl group is particularly preferable.
Examples of the cycloalkyl group represented by R 7 to R 9 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and an adamantyl group.
The alkyl group R 7 ~ R 9 represent, for example, methyl group, ethyl group, n- propyl group, iso- propyl, n- butyl group, a pentyl group, an octyl group.
Examples of the aryl group represented by R 7 to R 9 include a phenyl group, a biphenyl group, and a terphenyl group.
〈本発明に用いられる化合物の具体例〉
　以下に、本発明の一般式［１］で表される構造を有する化合物の具体例を示すが、本発明はこれらに限定されるものではない。 <Specific Examples of Compounds Used in the Present Invention>
Specific examples of the compound having the structure represented by the general formula [1] of the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　以下に、本発明の一般式［２］又は一般式［４］で表される構造を有する化合物の具体例を示すが、本発明はこれらに限定されるものではない。 Specific examples of the compound having the structure represented by the general formula [2] or the general formula [4] of the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　以下に、本発明の一般式［３］又は一般式［５］で表される構造を有する化合物の具体例を示すが、本発明はこれらに限定されるものではない。 Specific examples of the compound having the structure represented by the general formula [3] or the general formula [5] of the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　以下に、本発明の一般式［６］で表される構造を有する化合物の具体例を示すが、本発明はこれらに限定されるものではない。 Specific examples of the compound having the structure represented by the general formula [6] of the present invention are shown below, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　以下に実施例を挙げて本発明を具体的に説明するが、本発明の実施態様はこれらに限定されるものではない。なお、実施例において「部」又は「％」の表示を用いるが、特に断りがない限り「質量部」又は「質量％」を表す。 Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited to these examples. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.
　合成例１（比較例）
　《例示化合物３－６の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－６を１０ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ｄｂａ）２を１．７ｇ、Ｌｉｇａｎｄ　Ａを１．３ｇ投入し１２０℃で５時間加熱した。
　減圧濃縮し、得られた固体を水洗、乾燥した。トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶７．０ｇを得た（収率５０％、純度８７．５％）。 Synthesis example 1 (comparative example)
<< Synthesis of Exemplified Compound 3-6 >>
7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.3 g of Ligand A were added and heated at 120 ° C. for 5 hours.
After concentration under reduced pressure, the obtained solid was washed with water and dried. 5 L of a 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 7.0 g of brown crystals (yield 50%, purity 87.5%).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　合成例２（本発明）
　《例示化合物３－６の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－６を１０ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ｄｂａ）２を１．７ｇ、例示化合物６－１を１．１ｇ投入し４時間１２０℃で加熱した。水冷下３時間撹拌し、析出した結晶を濾過、水洗、乾燥した。トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶１２．６ｇを得た（収率９１％、純度９８．０％）。 Synthesis Example 2 (present invention)
<< Synthesis of Exemplified Compound 3-6 >>
7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. 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 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 12.6 g of brown crystals (yield 91%, purity 98.0%).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　合成例３（本発明）
　《例示化合物３－６の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－６を１０ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ｄｂａ）２を１．７ｇ、例示化合物６－２を０．９６ｇ投入し、４時間１２０℃で加熱した。水冷下３時間撹拌し、析出した結晶を濾過、水洗、乾燥した。トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶１２．６ｇを得た（収率８８％、純度９７．０％）。 Synthesis Example 3 (present invention)
<< Synthesis of Exemplified Compound 3-6 >>
7.6 g of Exemplified Compound 1-1, 10 g of Exemplified Compound 2-6, 11 g of tC 4 H 9 ONa and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 0.96 g of Exemplified Compound 6-2 were added and heated at 120 ° C. for 4 hours. 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 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 12.6 g of brown crystals (yield 88%, purity 97.0%).
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　合成例４（比較例）
　《例示化合物３－１２の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－１２を１０．４ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ｄｂａ）２を１．７ｇ、Ｌｉｇａｎｄ　Ａを１．３ｇ投入し１２０℃で５時間加熱した。減圧濃縮し、得られた固体を水洗、乾燥した。トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶６．５ｇを得た（収率４５％、純度８６．５％）。 Synthesis example 4 (comparative example)
<< Synthesis of Exemplified Compound 3-12 >>
7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.3 g of Ligand A were added and heated at 120 ° C. for 5 hours. After concentration under reduced pressure, the obtained solid was washed with water and dried. 5 L of a 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized from toluene / acetonitrile to obtain 6.5 g of brown crystals (yield 45%, purity 86.5%).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　合成例５（本発明）
　《例示化合物３－１２の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－１２を１０．４ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ｄｂａ）２を１．７ｇ、例示化合物６－１を１．１ｇ投入し４時間１２０℃で加熱した。水冷下３時間撹拌し、析出した結晶を濾過、水洗、乾燥した。
　トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶１２．７ｇを得た（収率８８％、純度９７．５％）。 Synthesis Example 5 (present invention)
<< Synthesis of Exemplified Compound 3-12 >>
7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 1.7 g of Pd (dba) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. 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 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 12.7 g of brown crystals (yield 88%, purity 97.5%).
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　合成例６（本発明）
　《例示化合物３－１２の合成》
　例示化合物１－１を７．６ｇ、例示化合物２－１２を１０．４ｇ、ｔ－Ｃ４Ｈ９ＯＮａを１１ｇ、キシレンを３００ｍＬ投入し、窒素気流下で２０分間撹拌を行った。この懸濁液にＰｄ（ＯＡｃ）２を０．６２ｇ、例示化合物６－１を１．１ｇ投入し４時間１２０℃で加熱した。水冷下３時間撹拌し、析出した結晶を濾過、水洗、乾燥した。トルエン及びメタノールの１：１混合液５Ｌを投入し、不溶分を除去後、減圧濃縮した。得られた粗製物をトルエン／アセトニトリルで再結晶し、褐色結晶１１．７ｇを得た（収率８１％、純度９６．５％）。 Synthesis Example 6 (present invention)
<< Synthesis of Exemplified Compound 3-12 >>
7.6 g of Exemplified Compound 1-1, 10.4 g of Exemplified Compound 2-12, 11 g of tC 4 H 9 ONa, and 300 mL of xylene were added and stirred for 20 minutes under a nitrogen stream. To this suspension, 0.62 g of Pd (OAc) 2 and 1.1 g of Exemplified Compound 6-1 were added and heated at 120 ° C. for 4 hours. 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 1: 1 mixture of toluene and methanol was added to remove insoluble matters, followed by concentration under reduced pressure. The obtained crude product was recrystallized with toluene / acetonitrile to obtain 11.7 g of brown crystals (yield 81%, purity 96.5%).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　実施例中の各化合物の同定はＭＡＳＳ及びＮＭＲスペクトルで行い、それぞれ目的化合物であることを確認した。その他の例示化合物も上記の方法に準じて合成することができる。 Each compound in the examples was identified by MASS and NMR spectra and confirmed to be the target compound. Other exemplary compounds can also be synthesized according to the above method.
　本発明の含窒素複素環化合物の製造方法は、例えば、有機エレクトロルミネッセンス素子用材料として用いられる含窒素複素環化合物を製造するために好適に用いることができる。 The method for producing a nitrogen-containing heterocyclic compound of the present invention can be suitably used for producing, for example, a nitrogen-containing heterocyclic compound used as a material for an organic electroluminescence device.

Claims (4)

  1. 　下記一般式［１］で表される構造を有する化合物と下記一般式［２］で表される構造を有する化合物とを、Ｐｄ触媒及びホスフィンリガンドの存在下で反応させ、下記一般式［３］で表される構造を有する化合物を合成する含窒素複素環化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘは、ハロゲン原子、アルキルスルホネート基又はアリールスルホネート基を表す。Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ａ１～Ａ４は、それぞれ窒素原子又はＣＲを表す。ただし、Ａ１～Ａ４のうち少なくとも一つは窒素原子である。Ｒ及びＲ１～Ｒ３は、それぞれ水素原子又は置換基を表す。）     A compound having a structure represented by the following general formula [1] and a compound having a structure represented by the following general formula [2] are reacted in the presence of a Pd catalyst and a phosphine ligand, and the following general formula [3] The manufacturing method of the nitrogen-containing heterocyclic compound which synthesize | combines the compound which has a structure represented by these.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, X represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group. Z 1 and Z 2 represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring, respectively. Z 3 represents a simple bond or a divalent linking group, X 1 represents an oxygen atom or a sulfur atom, and A 1 to A 4 each represent a nitrogen atom or CR, provided that A 1 to (At least one of A 4 is a nitrogen atom. R and R 1 to R 3 each represents a hydrogen atom or a substituent.)
  2. 　前記一般式［２］で表される構造を有する化合物が、下記一般式［４］で表される構造を有する化合物であり、かつ
    　前記一般式［３］で表される構造を有する化合物が、下記一般式［５］で表される構造を有する化合物である請求項１に記載の含窒素複素環化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｚ１及びＺ２は、それぞれ芳香族炭化水素環又は芳香族複素環を形成するのに必要な非金属原子群を表す。Ｚ３は、単なる結合手又は２価の連結基を表す。Ｘ１は、酸素原子又は硫黄原子を表す。Ｒ１～Ｒ６は、それぞれ水素原子又は置換基を表す。）     The compound having a structure represented by the general formula [2] is a compound having a structure represented by the following general formula [4], and a compound having a structure represented by the general formula [3] 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 [5].
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, Z 1 and Z 2 each represent a nonmetallic atom group necessary for forming an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Z 3 represents a simple bond or a divalent linking group. X 1 represents an oxygen atom or a sulfur atom, and R 1 to R 6 each represents a hydrogen atom or a substituent.)
  3. 　前記ホスフィンリガンドが、下記一般式［６］で表される構造を有する請求項１又は請求項２に記載の含窒素複素環化合物の製造方法。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ７～Ｒ９は、それぞれアルキル基、シクロアルキル基又はアリール基を表す。）     The method for producing a nitrogen-containing heterocyclic compound according to claim 1 or 2, wherein the phosphine ligand has a structure represented by the following general formula [6].
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 7 to R 9 each represents an alkyl group, a cycloalkyl group or an aryl group)
  4. 　前記Ｚ３が、単なる結合手である請求項１から請求項３までのいずれか一項に記載の含窒素複素環化合物の製造方法。 The method for producing a nitrogen-containing heterocyclic compound according to any one of claims 1 to 3 , wherein Z 3 is a mere bond.
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