JP5796487B2 - Heterogeneous catalyst and method for producing triarylamine compound using the same - Google Patents

Description

  The present invention relates to a heterogeneous catalyst used in a coupling reaction including a support, a palladium compound and a specific phosphine compound, and a method for producing an arylamine compound using the same.

  Generally, a triarylamine compound used for an electronic material is synthesized by a condensation reaction between a corresponding aryl halide and an arylamine compound. For example, a method of synthesizing from a corresponding iodobenzene and an arylamine compound using a copper catalyst (Ullmann reaction) is known. In these reactions, a large amount of copper catalyst and a high reaction temperature are used. In other words, for a reason such as a long reaction time, the yield of the product triarylamine compound is lowered, and at the same time, impurities and decomposition products that adversely affect the properties of the target compound are by-produced. For this reason, it has been difficult to separate and remove the catalyst and to purify the triarylamine compound, resulting in an increase in production cost. In recent years, in order to solve this problem, heterogeneous catalysts have been developed.

  As a heterogeneous catalyst containing palladium, a catalyst in which palladium hydroxide and 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (phosphine ligand) are supported on carbon is used. A production method in which an aliphatic amine compound and an aryl halide are reacted is proposed (for example, Patent Document 1).

  In addition, a method for producing a triarylamine compound using a heterogeneous catalyst in which palladium-supported carbon and a phosphine ligand (1,1′-bis (diphenylphosphino) ferrocene or dicyclohexylbiphenylphosphine) are combined has been proposed. (For example, Patent Document 2 and Non-Patent Document 1).

  However, as a result of experiments by the present inventors, it has been found that the reported heterogeneous catalyst has a low reaction activity and requires a high reaction temperature and a long reaction time.

  On the other hand, in recent years, synthesis of arylamine polymers for electronic material members has been actively studied. In the case of the arylamine polymer, it is difficult to remove the catalyst from the product as compared with the low molecular weight arylamine, and therefore, a production method capable of easily removing the catalyst is required.

  From the above, a heterogeneous catalyst for coupling reaction, particularly preferably a heterogeneous catalyst for producing an arylamine compound and / or arylamine polymer, which can be industrially used and easily removed after the reaction, and Development of the manufacturing method of the used arylamine compound and / or arylamine polymer is calculated | required.

JP 2005-336084 A JP 2006-335712 A

Advanced Synthesis & Catalysis, Volume, Issue, 153-1532 (2010)

  The present invention has been made in view of the above-mentioned background art, and the object thereof is a heterogeneous catalyst for coupling reaction, particularly preferably an arylamine compound, which can be industrially used and can be easily removed after the reaction. Another object of the present invention is to provide a heterogeneous catalyst for producing an arylamine polymer and a method for producing an arylamine compound and / or an arylamine polymer using the heterogeneous catalyst.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have achieved a coupling reaction in a high yield by using a heterogeneous catalyst containing a support, a palladium compound, and a specific phosphine compound. In addition, the inventors have found that arylamine compounds can be obtained in a high yield, and further found that triarylamine polymers that have been difficult to produce with conventional heterogeneous catalysts can be obtained, thereby completing the present invention. It was.

  That is, this invention relates to the heterogeneous catalyst as shown below, and its use.

[1]
A heterogeneous catalyst used for a coupling reaction, comprising a support, a palladium compound, and tri (tert-butyl) phosphine, and the content of the palladium compound is 0. The heterogeneity is characterized in that it is 03 to 0.2 times by weight, and the content of tri (tert-butyl) phosphine is 0.6 to 12 times moles per mole of palladium atoms in the palladium compound. catalyst.

[2]
The heterogeneous catalyst according to [1], wherein the coupling reaction is a coupling reaction of an arylamine compound and an aromatic compound having a substituent that can be easily removed.

[3]
The heterogeneous catalyst according to [1] or [2], wherein the support is carbon.

[4]
In the presence of the heterogeneous catalyst, the solvent and the base according to any one of [1] to [3], the general formula (1)

(In the formula, Ar ¹ and Ar ² each independently represent a plurality of aryl groups having 6 to 60 carbon atoms and a plurality of substituents having 1 to 18 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. A heteroaryl group having 4 to 20 carbon atoms which may have a hydrogen atom, or Ar ¹ and Ar ² are directly or from 1 to 3 atoms selected from the group consisting of carbon, nitrogen and oxygen It may be bonded by a cross-linked structure, provided that Ar ¹ and Ar ² do not simultaneously represent a hydrogen atom.)
An arylamine compound represented by general formula (2):

(In the formula, Ar ³ may have a plurality of substituents having 1 to 18 carbon atoms and may have a plurality of aryl groups having 6 to 60 carbon atoms or a plurality of substituents having 1 to 18 carbon atoms. -Represents a heteroaryl group of -20, X represents a substituent that can be easily removed, and n represents an integer of 1-10.)
A process for producing a triarylamine compound, characterized by reacting with an aromatic compound represented by the formula:

[5]
The triarylamine compound has the general formula (3)

(In the formula, each Ar ⁴ independently has a plurality of arylene groups having 6 to 60 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms. And an optionally substituted heteroarylene group having 4 to 20 carbon atoms, each of Ar ⁵ independently represents an aryl group having 6 to 60 carbon atoms, or a carbon atom that may have a plurality of substituents having 1 to 18 carbon atoms. A heteroaryl group having 4 to 20 carbon atoms, which may have a plurality of substituents of 1 to 18. m represents an integer of 2 or more.)
The method for producing a triarylamine compound according to [4], comprising a triarylamine polymer having a skeleton represented by the formula:

[6]
The amount of the palladium compound is 0.001 to 0.2 times mol in terms of palladium atom with respect to 1 mol of the arylamine compound represented by the general formula (1), [4] or [5 ] The triarylamine compound manufacturing method of description.

[7]
[4] to [6], wherein the base is used in an amount of 1.0 to 20 moles per mole of the arylamine compound represented by the general formula (1). A method for producing a triarylamine compound.

[8]
The method for producing a triarylamine compound according to any one of [4] to [7], wherein the base is one or more bases selected from alkali metal alkoxides.

[9]
X in General formula (2) is a halogen atom or a triflate group, The manufacturing method as described in any one of [4] thru | or [8] characterized by the above-mentioned.

[10]
Reaction temperature is 60-200 degreeC, The triarylamine compound manufacturing method as described in any one of [4] thru | or [9] characterized by the above-mentioned.

  The heterogeneous catalyst of the present invention is expected to be suitable for industrial use since it exhibits higher activity than conventional heterogeneous catalysts and can significantly improve the reaction yield of triarylamine compounds.

  In addition, by using the heterogeneous catalyst of the present invention, it is possible to produce a triarylamine polymer, which has been difficult with conventional heterogeneous catalysts, and it is possible to establish a production process that is extremely simple and inexpensive to remove the catalyst. become. The triarylamine polymer is expected to be used as an organic EL device material because of its chemical structural characteristics.

  Further, according to the present invention, the catalyst can be easily removed and the catalyst can be reused, so that the manufacturing cost can be reduced. Therefore, it is possible to efficiently and inexpensively produce a triarylamine compound and / or a triarylamine polymer used for an organic electroluminescent element, an electrophotographic photosensitive member, and the like.

  The heterogeneous catalyst for coupling reaction of the present invention is a heterogeneous catalyst containing a support, a palladium compound, and tri (tert-butyl) phosphine, and the content of the palladium compound is converted to palladium atoms with respect to the weight of the support. And the content of tri (tert-butyl) phosphine is 0.6 to 12 times by mole with respect to 1 mole of palladium atom in the palladium compound. It is a heterogeneous catalyst characterized by being.

  Here, from the viewpoint of economy, the content of the palladium compound is preferably 0.05 to 0.15 times by weight in terms of palladium atom with respect to the weight of the carrier. Similarly, from the viewpoint of economic efficiency, the content of tri (tert-butyl) phosphine is preferably 0.8 to 10 times the mol of 1 mol of the palladium atom in the palladium compound.

  The heterogeneous catalyst of the present invention may include a carrier (hereinafter referred to as “palladium supported material”) on which a palladium compound is supported and tri (tert-butyl) phosphine.

  The coupling reaction using the heterogeneous catalyst of the present invention is not particularly limited. For example, a reaction in which a boron compound and an organic halide compound are cross-coupled (for example, Suzuki-Miyaura coupling reaction), organic magnesium Reaction that cross-couples the reagent and halide compound (for example, Kumada coupling reaction), reaction that cross-couples the organic zinc reagent and halide compound (for example, Negishi coupling reaction), and has an easily removable substituent Reactions for cross-coupling aryl compounds and arylamine compounds (for example, Buchwald-Hartwig reaction), reactions for aryl compounds having easily detachable substituents and alkynyl aryl compounds (for example, Sonogashira coupling) Reaction) It is possible. Among these, it is particularly preferable to use it in a reaction for cross-coupling an aryl compound having an easily detachable substituent and an arylamine compound in that the product can be obtained with high purity and high efficiency.

  In the above-described reaction in which an aryl compound having an easily detachable substituent and an arylamine compound are cross-coupled, the easily detachable substituent is not particularly limited, and examples thereof include a chlorine atom and a bromine atom. And halogen atoms such as iodine atom, trifluoromethanesulfonyloxy group (triflate group), alkanesulfonyloxy group such as methanesulfonyloxy group, arylsulfonyloxy group such as benzenesulfonyloxy group and p-toluenesulfonyloxy group. . Among these, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom or a triflate group is preferable. In addition, the aromatic compound having a substituent that can be easily eliminated is not particularly limited, and examples thereof include an aromatic compound represented by the general formula (2).

  Although it does not specifically limit as a support | carrier in the heterogeneous catalyst of this invention, Carbon, a silica, an alumina, a zeolite, activated clay, resin etc. are mentioned. Among these, carbon is particularly preferable in that it has a large specific surface area, high catalytic activity, and stability to a base.

  The palladium compound is not particularly limited, and palladium (II) nitrate, palladium (II) sulfate, tetraammine palladium (II) chloride, tetraammine palladium (II) bromide, tetraammine palladium (II) nitrate, tetraammine palladium ( II) Sulfate, palladium chloride (II), palladium hydroxide (II), palladium acetate (II), bis (2,4-pentanedionato) palladium (II), dichloro (1,5-cyclooctadiene) palladium (II), dichlorobis (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (0), tris (dibenzylideneacetone) dipalladium (0) and the like.

  As the palladium-supported product, a commercially available product can be used, or a product produced by a known method can be used. Moreover, although a water-containing product may be used or a dry product may be used, it is preferable to use a dry product from the viewpoint of reaction activity. Even when using water-containing products from the viewpoint of handling safety, immediately after use, wash with a hydrophilic organic solvent such as alcohol or ether in an inert gas atmosphere, and then use non-aqueous organic materials such as hexane, toluene, or xylene. By washing with a solvent and vacuum drying until there is no weight loss, the same effect as a dried product can be obtained.

  In the heterogeneous catalyst of the present invention, the content of the palladium compound is 0.03 to 0.2 times the weight of the support in terms of palladium atoms.

  In the heterogeneous catalyst of the present invention, the content of tri (tert-butyl) phosphine is 0.6 to 12 times mol for 1 mol of palladium atom in the palladium compound.

  The heterogeneous catalyst of the present invention can be separately adjusted before the reaction, or can be adjusted and used when mixing reagents in the reaction or during the reaction.

  The triarylamine production method of the present invention (hereinafter referred to as “the present production method”) is characterized by producing a triarylamine compound and / or a triarylamine polymer using the above heterogeneous catalyst.

  Specifically, by reacting the arylamine compound represented by the general formula (1) and the aromatic compound represented by the general formula (2) in the presence of the heterogeneous catalyst, the solvent, and the base, Triarylamine compounds can be produced. The triarylamine compound produced at this time may include a triarylamine polymer having a skeleton represented by the general formula (3).

  In the present production method, as the solvent, a solvent inert to the reaction can be used and is not particularly limited, and examples thereof include water, an ether organic solvent, an aromatic hydrocarbon organic solvent, and the like. . More specifically, diethyl ether, isopropyl ether, tert-butyl methyl ether, cyclopentyl methyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, benzene, toluene, xylene, mesitylene and the like or a mixture thereof can be used. Of these solvents, toluene, xylene, and mesitylene are particularly preferable. The solvent is preferably used after being deaerated.

  The base in this production method is not particularly limited, but sodium hydride, potassium hydride, lithium hydride, sodium amide, potassium amide, lithium amide, potassium carbonate, sodium carbonate, lithium carbonate, rubidium carbonate, cesium carbonate, carbonate Inorganic bases such as potassium hydrogen, sodium hydrogen carbonate, sodium metal, potassium metal, lithium metal, methoxy sodium, methoxy potassium, ethoxy sodium, ethoxy potassium, ethoxy lithium, tert-butoxy lithium, tert-butoxy sodium, tert-butoxy potassium, etc. One or more bases selected from the group consisting of alkali metal alkoxides can be used.

  The amount of the base used is not particularly limited, but it is preferably used in an amount of 1.0 to 20 times the amount of 1 mol of the aromatic compound represented by the general formula (2). If it is 1.0 times mole or more, reaction will fully advance, and if it is 20 times mole or less, it is economically preferable.

  In this production method, the arylamine compound represented by the general formula (1) is represented as follows.

Ar ¹ and Ar ² may each independently have a plurality of substituents having 1 to 18 carbon atoms and may have a plurality of aryl groups having 6 to 60 carbon atoms and a plurality of substituents having 1 to 18 carbon atoms. A good C 4-20 heteroaryl group or hydrogen atom is shown.

  Although it does not specifically limit as a C1-C18 substituent, For example, a propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl Group, stearyl group, cyclopropyl group, cyclohexyl group and other alkyl groups, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, stearyloxy group, etc. Alkoxy groups, such as halogenated alkyl groups such as trifluoromethyl group, trichloromethyl group and 2-fluoroethyl group, halogenated alkoxy groups such as trifluoromethoxy group, trichloromethoxy group and 2-fluoroethoxy group, phenyl group, 2 -Methylphenyl group, 3-methylphenyl group, 4-methyl Phenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group Aryl groups such as phenanthryl group and benzofluorenyl group, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxy Phenoxy group, 2-cyanophenoxy group, 3-cyanophenoxy group, 4-cyanophenoxy group, 4-methylphenyloxy group, 3-methylphenyloxy group, 4-biphenyloxy group, 3-biphenyloxy group, 1-naphthyl Aryloxy such as oxy group and 2-naphthyloxy group Group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, 2-methylpyridyl group, 3-methylpyridyl group, 4-methylpyridyl group, 2-methoxypyridyl group, 3-methoxy Pyridyl group, 4-methoxypyridyl group, 2-cyanopyridyl group, 3-cyanopyridyl group, 4-cyanopyridyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, benzoimidazolyl group, indazolyl group, benzothiazolyl group , Benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-benzooxadiazolyl group, quinolyl group, isoquinolyl group, Quinoxalyl group, quinazolyl group, acridinyl group, 1,10-phenane Heteroaryl group such as trolyl group, pyrrolyl group, furyl group, thienyl group, indolyl group, benzothienyl group, 4-carbazolyl group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group, diphenylamino group, phenylbiphenylamino Groups and the like.

  Here, a plurality of substituents having 1 to 18 carbon atoms may be bonded to an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms. When multiple bonds are used, the types of the substituent having 1 to 18 carbon atoms may be different or the same.

  The aryl group having 6 to 60 carbon atoms is not particularly limited, and examples thereof include a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3- Methoxyphenyl group, 4-methoxyphenyl group, 2-cyanophenyl group, 3-cyanophenyl group, 4-cyanophenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, phenanthryl group, benzofluorenyl group, pyrenyl Group, spirobifluorenyl group, stilbenyl group and the like.

  The heteroaryl group having 4 to 20 carbon atoms is not particularly limited, but is imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, 2-methylpyridyl group, 3-methyl Pyridyl group, 4-methylpyridyl group, 2-methoxypyridyl group, 3-methoxypyridyl group, 4-methoxypyridyl group, 2-cyanopyridyl group, 3-cyanopyridyl group, 4-cyanopyridyl group, pyrimidyl group, pyrazyl group 1,3,5-triazyl group, benzoimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group, benzoisoxazolyl group, 2,1,3-Benzoxadiazolyl group, quinolyl group, isoquinolyl group Quinoxalyl group, quinazolyl group, acridinyl group, 1,10-phenanthroyl group, pyrrolyl group, furyl group, thienyl group, indolyl group, benzothienyl group, 4-carbazolyl group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group Etc.

Ar ¹ and Ar ² may be the same or different, but Ar ¹ and Ar ² do not represent a hydrogen atom at the same time. That is, it is not ammonia.

Ar ¹ and Ar ² may be bonded directly or by a crosslinked structure composed of 1 to 3 atoms selected from the group consisting of carbon, nitrogen, and oxygen.

  Although it does not specifically limit as said bridge | crosslinking structure, For example, a methylene group, ethylene group, n-propylene group, an ether bond, an ester bond, an amide bond, an oxybismethylene group etc. are mentioned.

In this case, the above-mentioned crosslinked structure and a cyclic skeleton having Ar ¹ , Ar ² and a nitrogen atom in the general formula (1) as constituent elements are formed. The cyclic skeleton is not particularly limited, and examples thereof include a carbazole skeleton, a phenoxazine skeleton, a phenothiazine skeleton, a dithienopyrrole skeleton, and a diflopyrrole skeleton.

  In addition, as an arylamine compound shown by General formula (1), a commercial item may be used and what was manufactured by the well-known method may be used.

  In the production method, the aromatic compound represented by the general formula (2) is represented as follows.

Ar ³ is an aryl group having 6 to 60 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms or a heterogeneity having 4 to 20 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. An aryl group is shown.

Substituent having 1 to 18 carbon atoms, a carbon aryl group having 6 to 60 carbon atoms, and a heteroaryl group having 4 to 20 carbon atoms is not particularly limited, for example, exemplified by Ar ¹ and Ar ² Examples thereof include the same substituents having 1 to 18 carbon atoms, aryl groups having 6 to 60 carbon atoms, and heteroaryl groups having 4 to 20 carbon atoms.

In Ar ³ , a plurality of substituents having 1 to 18 carbon atoms may be bonded to an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms. When multiple bonds are used, the types of the substituent having 1 to 18 carbon atoms may be different or the same.

  X represents a substituent that can be easily removed.

  The substituent that can be easily removed is not particularly limited, and examples thereof include halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom, an alkane such as a trifluoromethanesulfonyloxy group (a triflate group), and a methanesulfonyloxy group. Examples thereof include arylsulfonyloxy groups such as a sulfonyloxy group, a benzenesulfonyloxy group, and a p-toluenesulfonyloxy group. Among these, a halogen atom such as a chlorine atom, a bromine atom or an iodine atom or a triflate group is preferable.

  In the aromatic compound represented by the general formula (2), n represents an integer of 1 to 10. Among these, the integer of 1-5 is preferable at the point of raw material availability.

  As an aromatic compound shown by General formula (2), a commercial item may be used and what was manufactured by the well-known method may be used.

  In this production method, the arylamine polymer having a skeleton represented by the general formula (3) is shown as follows.

Each of Ar ⁴ independently represents an arylene group having 6 to 60 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a carbon which may have a plurality of substituents having 1 to 18 carbon atoms. A heteroarylene group of formula 4 to 20 is shown.

The substituent having 1 to 18 carbon atoms is not particularly limited, for example, can be exemplified the same substituents as substituents of 1 to 18 carbon atoms shown by Ar ^1, and Ar ^2.

  Here, a plurality of substituents having 1 to 18 carbon atoms may be bonded to an arylene group having 6 to 60 carbon atoms or a heteroarylene group having 4 to 20 carbon atoms. When a plurality of bonds are present, the substituents may be different or the same.

  The arylene group having 6 to 60 carbon atoms is not particularly limited. For example, a phenylene group, a tolylene group, a methoxyphenylene group, a cyanophenylene group, a biphenylylene group, a terphenylylene group, a naphthylene group, a fluorenylene group, a phenanthrylene group, A benzofluorenylene group, a pyrenylene group, a spirobifluorenylene group, a stilbenylene group, etc. can be mentioned.

  The heteroarylene group having 4 to 20 carbon atoms is not particularly limited, but imidazole diyl group, pyrazole diyl group, thiazole diyl group, isothiazole diyl group, oxazole diyl group, isoxazole diyl group, pyridine diyl group, Methoxypyridinediyl group, cyanopyridinediyl group, pyrimidinediyl group, pyrazinediyl group, 1,3,5-triazinediyl group, benzimidazolediyl group, indazolediyl group, benzothiazolediyl group, benzoisothiazolediyl group, 2,1 , 3-Benzothiadiazolediyl group, benzoxazolediyl group, benzisoxazolediyl group, 2,1,3-benzooxadiazolediyl group, quinolinediyl group, isoquinolinediyl group, quinoxalinediyl group, quinazoly Diyl group, acridinine diyl group, 1,10-phenanthroline diyl group, pyrroline diyl group, frangyl group, thiophene diyl group, indole diyl group, benzothiophene diyl group, 4-carbazolediyl group, 9-carbazole diyl group, dibenzo A thiophenediyl group, a dibenzofurandiyl group, etc. can be mentioned.

Ar ⁵ is each independently an aryl group having 6 to 60 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms, or a carbon which may have a plurality of substituents having 1 to 18 carbon atoms. The heteroaryl group of several 4-20 is shown.

Substituent having 1 to 18 carbon atoms, a carbon aryl group having 6 to 60 carbon atoms, and a heteroaryl group having 4 to 20 carbon atoms is not particularly limited, for example, exemplified by Ar ¹ and Ar ² Examples thereof include the same substituents having 1 to 18 carbon atoms, aryl groups having 6 to 60 carbon atoms, and heteroaryl groups having 4 to 20 carbon atoms.

Note that in Ar ⁵ , a plurality of substituents having 1 to 18 carbon atoms may be bonded to an aryl group having 6 to 60 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms. When multiple bonds are used, the types of the substituent having 1 to 18 carbon atoms may be different or the same.

  m represents an integer of 2 or more.

  The amount of the heterogeneous catalyst used in this production method is such that the amount of the palladium compound is 0.001 to 0.20 times mol in terms of palladium atom with respect to 1 mol of the arylamine compound represented by the general formula (1). Preferably, the amount is 0.005 to 0.15 times mol, and more preferably 0.001 to 0.10 times mol. If it is 0.001 times mol or more, reaction will fully advance, and if it is 0.2 times mol or less, it is economically preferable, and also the point which the leakage to the reaction liquid of a palladium compound is suppressed is also preferable.

  The use amount (for example, molar ratio) of the arylamine compound represented by the general formula (1) and the aromatic compound represented by the general formula (2) in this production method is not particularly limited, and is arbitrarily set. can do. Among these, it is preferable that the usage-amount of the arylamine compound shown by General formula (1) is 0.10-20 times mole with respect to 1 mol of aromatic compounds shown by General formula (2), More preferably Is 0.25-15 moles.

  The molar ratio of the raw materials described above is usually the amine series of the arylamine compound represented by the general formula (1), the value of n in the aromatic compound represented by the general formula (2), and the target triarylamine compound. It is decided after considering the structure.

  The reaction conditions of this production method are not particularly limited, but under an inert gas atmosphere and / or a hydrogen atmosphere, a pressure of 0.1 to 3.0 MPa, a temperature range of 60 to 200 ° C., preferably Can be carried out in the temperature range of 80-180 ° C.

  Since the reaction time of this production method varies depending on the reaction conditions, it is not particularly limited. For example, the reaction time can be arbitrarily selected from 0.5 to 72 hours.

  Examples of the present invention are shown below, but the present invention is not limited to these Examples. In addition, the following apparatus was used for the analysis of a product.

  Gas chromatograph: Using Shimadzu GC-17A equipped with a capillary column (trade name “DB-5” manufactured by J & W Science), the temperature was raised from 100 ° C. to 300 ° C. at 10 ° C./min, and FID (hydrogen flame ion) Detector).

Further, as the palladium support, the amount of the palladium compound supported on the support is 0.05 times the amount of Pd / C (E101 O / W 5% Pd, manufactured by Evonik Degussa, “palladium support A” in terms of palladium atoms. And 0.1 times the amount of Pd / C (CGS-10DR, manufactured by NE CHEMCAT, referred to as “palladium supported product B”).
(Effect of tri (tert-butyl) phosphine)

Example 1
In a 50 mL round bottom flask equipped with a condenser and a thermometer, 1.4 g (9.0 mmol) of bromobenzene, 1.1 g (6.0 mmol) of 3-methyldiphenylamine, and palladium support B 0 in a nitrogen atmosphere at room temperature. .13 g (palladium atom 0.12 mmol), sodium-tert-butoxide 0.86 g (9.0 mmol) and o-xylene 6.0 g were mixed. After flowing nitrogen for about 20 minutes, o-xylene (36.4 mg (0.18 mmol) dissolved in tri (tert-butyl) phosphine (hereinafter sometimes referred to as “P- (tBu) ₃ ”) ( 150 μL) solution was added, heated to 110 ° C. under normal pressure, and stirred for 2 hours. The yield was calculated by an internal standard method using n-eicosane as an internal standard substance using gas chromatography. The results are shown in Table 1.

Example 2
Except that the palladium support B was changed to 64 mg (palladium atom 0.060 mmol) and an o-xylene (75 μL) solution in which 18.2 mg (0.090 mmol) of tri (tert-butyl) phosphine was dissolved was used. The same operation as in 1 was performed. The results are shown in Table 1.

Comparative Examples 1-4
Instead of 36.4 mg (0.18 mmol) of tri (tert-butyl) phosphine, 100 mg (0.18 mmol) of 1,1′-bis (diphenylphosphino) ferrocene (dppf), tricyclohexylphosphine (P (Cy) ₃ ) 50.5 mg (0.18 mmol), 2,2′-bis (diphenylphosphino) -1,1′-binaphthyl (BINAP) 112 mg (0.18 mmol), or tri-o-tolylphosphine (P (o- Tol) ₃ ) The same operation as in Example 1 was carried out except that 55 mg (0.18 mmol) was used. The results are shown in Table 1.

In addition, the catalyst amount in Table 1 was determined by the following formula.
Amount of catalyst = amount of palladium atom in heterogeneous catalyst (mol) / amount of bromobenzene (mol)

(Effect of reaction temperature)
Examples 3-5
The same operation as in Example 1 was performed except that the reaction temperature was changed to the temperature shown in Table 2. The results are shown in Table 2.

(Applicable range of easily removable substituents and aryl groups)
Examples 6-13
The same operation as in Example 1 was conducted except that bromobenzene was changed to the compounds shown in Table 3. In addition, all the addition amount of the compound shown in Table 3 is 9.0 mmol. Therefore, the amount of catalyst (= amount of palladium atom in heterogeneous catalyst (mol) / amount of bromobenzene (mol)) is all 0.02.

  However, only in Example 9, the reaction time was 20 hours. The results are shown in Table 3.

Example 14
The same operation as in Example 1 was conducted except that bromobenzene was changed to 1.8 g (4.5 mmol) of diiodobiphenyl. As a result, bis (3-methyldiphenylamino) biphenyl was obtained with a yield of 82%.

Examples 15-16
To the reaction solution obtained in Example 1, 5.0 g of water degassed under a nitrogen atmosphere and 4.0 g of o-xylene were added, and a reaction mixture containing palladium-supported substance B and tri (tert-butyl) phosphine was added. The homogeneous catalyst was filtered. The filtered heterogeneous catalyst was washed with 10 g of o-xylene three times and then recovered. The same operation as in Example 1 was performed using all of the recovered heterogeneous catalyst (Example 15). Further, the same operation as in Example 1 was performed using all of the heterogeneous catalyst recovered again in the same manner (Example 16). The above results are shown in Table 4.

  As a result, it was found that the heterogeneous catalyst of the present invention can be used repeatedly.

(Production of arylamine polymer)
Example 17
In a 100 mL eggplant-shaped flask equipped with a condenser and a thermometer, 2.4 g (6.0 mmol) of diiodobiphenyl, 0.94 g (6.3 mmol) of p-butylaniline in a nitrogen atmosphere at room temperature, palladium support A 1 .3 g (palladium atom 0.60 mmol), sodium-tert-butoxide 1.4 g (14 mmol) and mesitylene 15 g were mixed. After flowing nitrogen for about 20 minutes, a solution of o-xylene (1.9 mL) in which 0.49 g (2.4 mmol) of tri (tert-butyl) phosphine was dissolved was added and stirred at 165 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, toluene and water were added, and the heterogeneous catalyst was removed by filtration. The aqueous layer part of the filtrate was separated and removed, and then the reaction concentrate obtained by concentrating the organic layer was slowly added to acetone with stirring. Solid precipitation was confirmed in acetone. The solid was collected by filtration, washed with acetone, and then dried under reduced pressure to obtain 0.1 g of a pale yellow powder. The obtained pale yellow powder was analyzed by THF-based GPC (manufactured by Tosoh: HLC-8220; column: TSKgel SuperH3000, TSKgel SuperH2000, TSKgel SuperH1000 (all manufactured by Tosoh Corp.)), and was analyzed by weight in terms of polystyrene. It was found to be a triarylamine polymer having an average molecular weight of 2,700 and a number average molecular weight of 2,300.

Example 18 (Application to Suzuki-Miyaura coupling / synthesis of 4-methyl-1,1′-biphenyl)
In a 100 mL eggplant-shaped flask equipped with a condenser and a thermometer, 1.00 g (6.37 mmol) of bromobenzene, 0.91 g (6.69 mmol) of 4-tolylboronic acid, palladium support A at room temperature in a nitrogen atmosphere 34. 1 mg (palladium atom 0.032 mmol), dimethoxyethane 20 mL, and 20 wt% aqueous sodium carbonate solution 10.1 g (19.1 mmol as sodium carbonate) were added. After circulating nitrogen for about 20 minutes, an o-xylene (41 μL) solution in which 9.7 mg (0.048 mmol) of tri (tert-butyl) phosphine was dissolved was added, and the mixture was heated and stirred for 6 hours under reflux. After cooling to room temperature, the heterogeneous catalyst was collected by filtration, and the organic layer was separated. As a result of analyzing the organic layer by gas chromatography, 4-methyl-1,1′-biphenyl was obtained in a yield of 92%.

  Example 19 (Application to Suzuki-Miyaura Coupling / Synthesis of Triarylamine Derivative) Similar to Reference Example 1 except that 2.07 g (6.37 mmol) of 4-bromotriphenylamine was used instead of bromobenzene As a result, the yield of 4′-methyl-N, N-diphenylbiphenyl-4-amine was 84%.

Example 20 (Application to Sonogashira Coupling)
4-chloroiodobenzene 2.38 g (0.010 mol), phenylacetylene 1.13 g (0.011 mol), triethylamine 4.06 g (0.040 mol), palladium supported on a 100 mL eggplant type flask equipped with a condenser and a thermometer Product B 0.21 g (palladium atom 0.20 mmol), N, N-dimethylformamide 20 mL, deionized water 20 mL was added at room temperature in a nitrogen atmosphere, and nitrogen was passed for about 20 minutes, and then tri (tert-butyl). An o-xylene (71 μL) solution in which 61 mg (0.30 mmol) of phosphine was dissolved was added, and the mixture was heated to reflux at 100 ° C. for 24 hours.

  After completion of the reaction, 100 mL of toluene and 50 mL of 5 wt% NaCl aqueous solution were added, and then the heterogeneous catalyst was recovered by filtration, and the organic layer was separated. The organic layer was washed with 50 mL of deionized water and further dried over sodium sulfate. As a result of analysis by gas chromatography, 1-chloro-4- (phenylethynyl) benzene was obtained with a yield of 85%.

Claims (7)

Responsible body, palladium compound, and comprises a tri (tert- butyl) phosphine, the content of the palladium compound is, relative to the support weight terms of the palladium atom is 0.03 to 0.2 times by weight, and In the presence of a heterogeneous catalyst , a solvent and a base for a coupling reaction in which the content of tri (tert-butyl) phosphine is 0.6 to 12 moles per mole of palladium atom in the palladium compound, (1)

(In the formula, Ar ¹ and Ar ² each independently represent a plurality of aryl groups having 6 to 60 carbon atoms and a plurality of substituents having 1 to 18 carbon atoms which may have a plurality of substituents having 1 to 18 carbon atoms. A heteroaryl group having 4 to 20 carbon atoms which may have a hydrogen atom, or Ar ¹ and Ar ² are directly or from 1 to 3 atoms selected from the group consisting of carbon, nitrogen and oxygen It may be bonded by a cross-linked structure, provided that Ar ¹ and Ar ² do not simultaneously represent a hydrogen atom.)
An arylamine compound represented by general formula (2):

(In the formula, Ar ³ may have a plurality of substituents having 1 to 18 carbon atoms and may have a plurality of aryl groups having 6 to 60 carbon atoms or a plurality of substituents having 1 to 18 carbon atoms. -Represents a heteroaryl group of -20, X represents a substituent that can be easily removed, and n represents an integer of 1-10.)
Is reacted with an aromatic compound represented by the general formula (3)

(In the formula , each Ar ⁴ independently has a plurality of arylene groups having 6 to 60 carbon atoms, or a plurality of substituents having 1 to 18 carbon atoms, which may have a plurality of substituents having 1 to 18 carbon atoms. And an optionally substituted heteroarylene group having 4 to 20 carbon atoms , each of Ar ⁵ independently represents an aryl group having 6 to 60 carbon atoms, or a carbon atom that may have a plurality of substituents having 1 to 18 carbon atoms. A heteroaryl group having 4 to 20 carbon atoms, which may have a plurality of substituents of 1 to 18. m represents an integer of 2 or more.)
A method for producing a triarylamine compound, comprising obtaining a triarylamine polymer having a skeleton represented by the formula: The method for producing a triarylamine compound according to claim 1 , wherein the carrier is carbon . The amount of the palladium compound is, relative to the arylamine 1 mole of the compound represented by the general formula (1), characterized in that it is a 0.001 to 0.2 fold molar terms of the palladium atom, as claimed in claim 1 A method for producing a triarylamine compound. The method for producing a triarylamine compound according to claim 1, wherein the base is used in an amount of 1.0 to 20 times by mole based on 1 mole of the arylamine compound represented by the general formula (1). The method for producing a triarylamine compound according to claim 1, wherein the base is one or more bases selected from alkali metal alkoxides. The method for producing a triarylamine compound according to claim 1, wherein X in the general formula (2) is a halogen atom or a triflate group. The method for producing a triarylamine compound according to claim 1, wherein the reaction temperature is 60 to 200 ° C.