JP6166648B2 - Method for producing amine compound - Google Patents

Description

  The present invention relates to a method for producing an amine compound.

  Amine compounds are a group of compounds useful as raw materials for medical pesticides and electronic materials, and these compound groups have long been known to be synthesized by the Ullmann reaction using a copper catalyst (copper compound). (For example, refer to Patent Document 1 and Non-Patent Document 1).

  In recent years, it has been reported that a wide range of amine compounds can be synthesized by combining a palladium catalyst with a suitable ligand and a strong base, tert-butoxy sodium (tert-BuONa). (For example, refer to Patent Document 2 and Non-Patent Documents 2 and 3).

JP-A-8-48974 JP 10-139742 A

Chem. Lett. , Pp. 1145 (1989) Angew. Chem. Int. Ed. Engl. , 34, no. 12, 1348 (1995) J. et al. Am. Chem. Soc. , 118, 7215 (1996)

  However, the Ullmann reaction requires a high temperature of 150 ° C. or more and a long reaction time, and the yield of the target amine compound is not satisfactory. In addition, in the method in which an appropriate ligand and tert-BuONa, which is a strong base, are combined with a palladium catalyst, there is a problem in that the amine compound is decomposed during the reaction to produce a by-product, resulting in a decrease in yield. .

  An object of the present invention is to provide a novel method for producing an amine compound.

〔式中、
Ｘは、脱離基を表す。
Ａｒ^１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子２個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子２個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子２個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子２個を除いた基を表す。
Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。
Ａｒ^１とＲ^１は、直接結合して又は連結基を介して環を形成してもよい。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、Ａｒ^１とＲ^１は、前述と同じ意味を表す。〕 That is, the present invention is represented by the formula (2), in which the compound represented by the formula (1) is reacted with each other in the presence of the transition metal compound and the organic solvent under the condition of the atmospheric pressure of 5.5 MPa or less. The manufacturing method of the high molecular compound containing the structural unit is provided.

[Where,
X represents a leaving group.
Ar ¹ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding two atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding two hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group obtained by removing two hydrogen atoms from
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹ and R ¹ may be bonded directly or through a linking group to form a ring.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Wherein Ar ¹ and R ¹ represent the same meaning as described above. ]

〔式中、
ｍは、１〜４の整数を表す。
Ａｒ^１１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｍ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｍ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｍ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｍ個を除いた基を表す。
Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。
Ａｒ^１１とＲ^１は、直接結合して又は連結基を介して環を形成してもよい。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、
ｎは、１〜４の整数を表す。
Ａｒ^１２は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｎ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｎ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｎ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｎ個を除いた基を表す。
Ｘは、脱離基を表す。Ｘが複数個ある場合、それらは同一でも相異なってもよい。〕

〔式中、Ａｒ^１１、Ａｒ^１２、Ｒ^１、Ｒ^ａ、Ｘ、ｍ及びｎは、前述と同じ意味を表す。〕 The present invention secondly reacts the compound represented by the formula (11) with the compound represented by the formula (12) in the presence of a transition metal compound and an organic solvent under the condition of an atmospheric pressure of 5.5 MPa or less. A method for producing an amine compound, comprising producing a compound represented by formula (13).

[Where,
m represents an integer of 1 to 4.
Ar ¹¹ is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which m atoms are removed, and an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is removed from an aromatic amine compound which may have a substituent, wherein m hydrogen atoms on the aromatic ring are removed. Represents a group in which m hydrogen atoms have been removed.
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹¹ and R ¹ may be directly bonded or form a ring via a linking group.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Where,
n represents an integer of 1 to 4.
Ar ¹² is a group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding n atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding n hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group in which n hydrogen atoms have been removed.
X represents a leaving group. When there are a plurality of X, they may be the same or different. ]

[Wherein, Ar ¹¹ , Ar ¹² , R ¹ , R ^a , X, m and n represent the same meaning as described above. ]

〔式中、
ｐは、１〜４の整数を表す。
Ａｒ^５１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｐ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｐ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｐ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｐ個を除いた基を表す。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、Ａｒ^１２、Ａｒ^５１、Ｒ^ａ、Ｘ、ｐ及びｎは、前述と同じ意味を表す。〕 In the present invention, the compound represented by the formula (51) is reacted with the compound represented by the formula (12) in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. The manufacturing method of an amine compound which manufactures the compound represented by Formula (52) is provided.

[Where,
p represents an integer of 1 to 4.
Ar ⁵¹ is a group obtained by removing p hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which p atoms are removed, an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is optionally substituted with a group in which p hydrogen atoms on the aromatic ring are removed Represents a group in which p hydrogen atoms have been removed.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Wherein, Ar ¹² , Ar ⁵¹ , R ^a , X, p and n represent the same meaning as described above. ]

  ADVANTAGE OF THE INVENTION According to this invention, the novel manufacturing method of an amine compound can be provided.

  In the method for producing an amine compound of the present invention, by using an amine compound having an N—Si structure, the target amine compound can be produced in a high yield under mild conditions.

  Hereinafter, the present invention will be described in detail.

<Explanation of terms>
In the present specification, the term “structural unit” means a unit structure present in one or more polymer compounds.

In the present specification, the term “C _p -C _q ” (p and q are positive integers satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p. It represents that it is q pieces. For example, “C ₁ -C ₁₂ alkyl group” indicates that the alkyl group has 1 to 12 carbon atoms, and “C ₁ -C ₁₂ alkylphenoxy group” indicates the carbon atom of the alkyl moiety in the group. The number is 1-12.

  In this specification, the term “which may have a substituent” attached immediately before a compound or group means that the hydrogen atom of the compound or group is not substituted with a substituent, and It means both when a part or all of the hydrogen atoms of a compound or group are substituted with a substituent.

  In this specification, the term “substituent” means a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an aryl unless otherwise specified. Alkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, heterocyclic thio group, amino group, silyl group, acyl group, acyloxy group, imine residue, amide group, acid imide group, carboxyl group, cyano Group, nitro group, hydroxy group and oxy group.

  As a halogen atom used as a substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

  The alkyl group used as a substituent may be linear, branched or cyclic. The number of carbon atoms of the linear alkyl group is usually 1-20, preferably 1-10, more preferably 1-8. The number of carbon atoms of the branched and cyclic alkyl group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 8. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isoamyl group, a hexyl group, a cyclohexyl group, and a heptyl group. Octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, and dodecyl group.

  The alkoxy group used as a substituent may be linear, branched or cyclic, and the number of carbon atoms of the linear alkoxy group is usually 1 to 20, preferably 1 to 10, more preferably. Is 1-8. The number of carbon atoms of the branched and cyclic alkoxy group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 8. Examples of the alkoxy group include a methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, Examples include heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, and dodecyloxy group.

  The alkylthio group used as a substituent may be linear, branched or cyclic, and the linear alkylthio group usually has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. . The number of carbon atoms of the branched and cyclic alkylthio group is usually 3 to 20, preferably 3 to 10, and more preferably 3 to 8. Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group. Octylthio group, nonylthio group, decylthio group, and laurylthio group.

  The aryl group used as a substituent is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon. The carbon atom number of the aryl group used as a substituent is 6-60 normally, Preferably it is 6-48, More preferably, it is 6-20, More preferably, it is 6-14. Examples of the aryl group include a phenyl group, a biphenyl group, a terphenyl group, a fluorenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a perylenyl group.

  The carbon atom number of the aryloxy group used as a substituent is 6-60 normally, Preferably it is 6-20. Examples of the aryloxy group used as a substituent include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group.

  The carbon atom number of the arylthio group used as a substituent is 6-60 normally, Preferably it is 6-30. Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, and a 2-naphthylthio group.

The carbon atom number of the arylalkyl group used as a substituent is 7-60 normally, Preferably it is 7-30. Examples of the arylalkyl group include a phenyl-C ₁ -C ₁₂ alkyl group, a naphthyl-C ₁ -C ₁₂ alkyl group, and an anthracenyl-C ₁ -C ₁₂ alkyl group.

The number of carbon atoms of the arylalkoxy group used as a substituent is usually 7 to 60, preferably 7 to 20. Examples of the arylalkoxy group include a phenyl-C ₁ -C ₁₂ alkoxy group, a 1-naphthyl-C ₁ -C ₁₂ alkoxy group, and a 2-naphthyl-C ₁ -C ₁₂ alkoxy group.

The carbon atom number of the arylalkylthio group used as a substituent is 7-60 normally, Preferably it is 7-30. Examples of the arylalkylthio group include a phenyl-C ₁ -C ₁₂ alkylthio group, a 1-naphthyl-C ₁ -C ₁₂ alkylthio group, and a 2-naphthyl-C ₁ -C ₁₂ alkylthio group.

The number of carbon atoms of the arylalkenyl group used as a substituent is usually 8 to 60, preferably 8 to 30. Examples of the arylalkenyl group include a phenyl _-C 2 _{-C 12} alkenyl group, 1-naphthyl _-C 2 _{-C 12} alkenyl group, and 2-naphthyl _-C 2 _{-C 12} alkenyl groups. _As the C 2 _{-C 12} alkenyl group include a vinyl group, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 1-pentenyl group, 2-pentenyl group, 1-hexenyl Group, 2-hexenyl group, and 1-octenyl group.

The number of carbon atoms of the arylalkynyl group used as a substituent is usually 8 to 60, preferably 8 to 30. Examples of the arylalkynyl group include a phenyl _-C 2 _{-C 12} alkynyl group, 1-naphthyl _-C 2 _{-C 12} alkynyl group, and 2-naphthyl _-C 2 _{-C 12} alkynyl groups. Examples of the C _{2 to} C ₁₂ alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group and 1-hexynyl. Group, 2-hexynyl group, and 1-octynyl group.

  The monovalent heterocyclic group used as a substituent refers to a group obtained by removing one hydrogen atom on a heterocyclic ring from a heterocyclic compound. The number of carbon atoms of the monovalent heterocyclic group is usually 3 to 60, preferably 3 to 20. The monovalent heterocyclic group includes a monovalent aromatic heterocyclic group. Examples of the monovalent heterocyclic ring include thienyl group, pyrrolyl group, furyl group, pyridyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, triazinyl group, pyrrolidyl group, piperidyl group, imidazolyl group, thiazolyl group, oxazolyl group, Examples include morpholinyl group, carbazolyl group, phenoxazinyl group, phenothiazinyl group, quinolyl group, and isoquinolyl group.

  The number of carbon atoms of the heterocyclic thio group used as a substituent is usually 3 to 60, preferably 3 to 20. Examples of the heterocyclic thio group include a thienylthio group, a pyrrolylthio group, a furylthio group, a pyridylthio group, a pyridazinylthio group, a pyrimidylthio group, a pyrazinylthio group, a triazinylthio group, a pyrrolidylthio group, a piperidylthio group, a quinolylthio group, and an isoquinolylthio group. .

  The number of carbon atoms of the acyl group used as a substituent is usually 2 to 20, preferably 2 to 18. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group.

  The number of carbon atoms of the acyloxy group used as a substituent is usually 2 to 20, preferably 2 to 18. Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group.

〔式中、Ｍｅはメチル基を表す。以下、同様である。〕 The imine residue used as a substituent is a group obtained by removing one hydrogen atom in this structure from an imine compound having a structure represented by the formula: H—N═C <or the formula: —N═CH—. means.
Examples of such imine compounds include compounds in which a hydrogen atom bonded to a nitrogen atom in aldimine, ketimine, and aldimine is substituted with an alkyl group, aryl group, arylalkyl group, arylalkenyl group, arylalkynyl group, or the like. It is done. The number of carbon atoms in the imine residue is usually 2-20, preferably 2-18. Examples of the imine residue include a general formula: —CR ^β = N—R ^γ or a general formula: —N═C (R ^γ ) ₂ (wherein R ^β is a hydrogen atom, an alkyl group, an aryl group, an aryl represents an alkyl group, an arylalkenyl group, or an arylalkynyl group, the R ^gamma alkyl group, an aryl group, an arylalkyl group, an arylalkenyl group, or an arylalkynyl group. However, if R ^gamma there are two, 2 R ^γ bonds to each other to form a ring as a divalent group (for example, an alkylene group having 2 to 18 carbon atoms such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group). May be included). Examples of the imine residue include groups represented by the following formulas.

[Wherein, Me represents a methyl group. The same applies hereinafter. ]

  The number of carbon atoms of the amide group used as a substituent is usually 1-20, preferably 2-18. Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a diformamide group, a diacetamido group, a dipropioamide group, a dibutyroamide group, and a dibenzamide group.

The acid imide group used as a substituent means a group obtained by removing one hydrogen atom bonded to the nitrogen atom from the acid imide. The acid imide group usually has 4 to 20 carbon atoms, preferably 4 to 18 carbon atoms. Examples of the acid imide group include groups represented by the following formulas.

  The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

  [Method for producing amine compound]

〔式中、
Ｘは、脱離基を表す。
Ａｒ^１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子２個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子２個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子２個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子２個を除いた基を表す。
Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。
Ａｒ^１とＲ^１は、直接結合して又は連結基を介して環を形成してもよい。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、Ａｒ^１とＲ^１は、前述と同じ意味を表す。〕 <First Embodiment>
In the first embodiment of the method for producing an amine compound of the present invention, a compound represented by the formula (1) is reacted with each other in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. It is a manufacturing method of the high molecular compound containing the structural unit represented by (2).

[Where,
X represents a leaving group.
Ar ¹ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding two atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding two hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group obtained by removing two hydrogen atoms from
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹ and R ¹ may be bonded directly or through a linking group to form a ring.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Wherein Ar ¹ and R ¹ represent the same meaning as described above. ]

In formula (1), X represents a leaving group. Examples of the leaving group include a halogen atom and a group having a sulfonate structure. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, A chlorine atom, a bromine atom, and an iodine atom are preferable. Examples of the group having a sulfonate structure include a group represented by the formula: R _s SO ₃ — (wherein R _s has an alkyl group which may have a substituent, or a substituent. A group represented by the formula: R _s ′ SO ₃ — (wherein R _s ′ is a C _{1 to} C ₁₂ alkyl group, C substituted with a halogen atom). . _{to 1} -C ₁₂ alkyl _group, C 1 _{-C 12} aryl group, or a halogen atom represents a substituted _C 1 _{-C 12} aryl group) is preferable, trifluoromethanesulfonate group _(CF 3 _SO 3 -), methanesulfonate group _(CH 3 _SO 3 -), ethanesulfonate sulfonate group _{(C 2 H 5 SO 3 -} ), benzenesulfonate group _{(C 6 H 5 SO 3 -} ), p- toluenesulfonate group _{(CH 3 C 6 H 4 SO} 3 -) Jill sulfonate group _{(C 6 H 5 CH 2 SO} 3 -) it is more preferred. Among them, as the leaving group, a chlorine atom, a bromine atom, an iodine atom, trifluoromethanesulfonate group _{(CF 3 SO 3 -),} p- toluenesulfonate group _{(CH 3 C 6 H 4 SO} 3 -) are preferred.

In the formula (1), Ar ¹ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, and a heterocyclic compound which may have a substituent. A group in which two hydrogen atoms on the heterocyclic ring are removed from, or an aromatic amine compound which may have a substituent, which may have a group or substituent in which two hydrogen atoms on the aromatic ring are removed from A group obtained by removing two hydrogen atoms from an aliphatic unsaturated hydrocarbon. Ar ¹ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent on a heterocyclic ring. Groups in which two hydrogen atoms have been removed are preferred.

In Ar ¹ , the number of carbon atoms of the aromatic hydrocarbon is usually 6 to 60, preferably 6 to 48, more preferably 6 to 20, more preferably 6 to 14, excluding the number of carbon atoms of the substituent. is there. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, biphenyl, terphenyl, indene, fluorene, fluorenone, pyrene, perylene, and phenanthrene, and benzene, naphthalene, anthracene, biphenyl, and fluorene are preferable.

In Ar ¹ , the number of carbon atoms of the heterocyclic compound is usually 2 to 60, preferably 2 to 48, more preferably 2 to 20, more preferably 2 to 14, not including the number of carbon atoms of the substituent. is there. Examples of the heterocyclic compound include pyridine, pyrazine, quinoline, isoquinoline, furan, benzofuran, thiophene, benzothiophene, pyrrole, indole, carbazole, oxadiazole, thiadiazole, thiazole, oxazole, phosphole, pyrimidine, triazine, pyridazine, Examples include dibenzosilol, dibenzophosphole, phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran.

In Ar ^1, the number of carbon atoms of an aromatic amine compound, not including the carbon atom number of substituent, typically 5 to 100, preferably 6 to 80, more preferably 10 to 60, more preferably at 12 to 40 is there. The aromatic amine compound may be any of primary amine, secondary amine and tertiary amine, but secondary amine and tertiary amine are preferred. Examples of the aromatic amine compound include an N-alkylaminoaryl compound, an N-arylaminoaryl compound, an N, N-dialkylaminoaryl compound, an N-alkyl-N-arylaminoaryl compound, and an N, N-diarylaminoaryl. Examples thereof include a transannular structure-containing aromatic amine compound represented by a compound, an N, N-diarylaminoaryl compound, carbazole and phenoxazine.

In Ar ¹ , the number of carbon atoms of the aliphatic unsaturated hydrocarbon does not include the number of carbon atoms of the substituent, and is usually 2 to 60, preferably 2 to 30, more preferably 2 to 20, and more preferably 2 to 2. 10. The aliphatic unsaturated hydrocarbon is not particularly limited as long as it is an aliphatic hydrocarbon having at least one double bond or triple bond (preferably a double bond). For example, alkene, alkyne, alkadiene, alkadiyne, Triene and alkatriin are mentioned, alkene, alkadiene and alkatriene are preferable, and alkene is more preferable. Examples of the alkene include ethylene, propylene, butene, pentene, and hexene, and ethylene, propylene, and butene are preferable.

In formula (1), R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent which remove | excluded one hydrogen atom on an aromatic ring is represented. R ¹ is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent on a heterocyclic ring. A group in which one hydrogen atom is removed is preferred.

In R ^1, number of carbon atoms in the aliphatic hydrocarbon, not including the carbon atom number of substituent, usually 1 to 60, preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 10 is there. The aliphatic hydrocarbon may be an aliphatic saturated hydrocarbon or an aliphatic unsaturated hydrocarbon. Examples of the aliphatic hydrocarbon include alkanes, alkenes, alkynes, alkadienes, alkadienes, alkatrienes, and alkatriins. Alkanes, alkenes, alkadienes, and alkatrienes are preferable, and alkanes and alkenes are more preferable. Examples of the alkane include methane, ethane, propane, butane, pentane, and hexane, and methane, ethane, propane, and butane are preferable.
Examples of the alkene include ethylene, propylene, butene, pentene, and hexene, and ethylene, propylene, and butene are preferable.

In R ¹ , examples of the aromatic hydrocarbon and the heterocyclic compound include the aromatic hydrocarbon and the heterocyclic compound exemplified for Ar ¹ .

Ar ¹ and R ¹ may be bonded directly or through a linking group to form a ring.

Examples of the linking group that links Ar ¹ and R ¹ include a divalent group represented by the following formula. Examples of the linking group also include a divalent group in which two or more divalent groups represented by the following formula are bonded.

〔式中、Ｒは置換基を表し、Ａｒは炭素原子数が６〜６０の炭化水素基を表す。〕

[Wherein, R represents a substituent, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms. ]

In the above formula, R is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. Ar is preferably an aromatic hydrocarbon or a heterocyclic compound. In R, examples of the halogen atom, alkyl group, alkoxy group, aryl group and monovalent heterocyclic group include the halogen atom, alkyl group, alkoxy group, aryl group, 1 Valent heterocyclic group. Examples of aromatic hydrocarbons and heterocyclic compounds in Ar include the aromatic hydrocarbons and heterocyclic compounds exemplified for Ar ¹ .

In formula (1), R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ^a is preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and an alkyl group or substituent which may have a substituent. An aryl group which may have is more preferable. The carbon atom number of an alkyl group is 1-60 normally without including the carbon atom number of a substituent, Preferably it is 1-30, More preferably, it is 1-20, More preferably, it is 1-12. The number of carbon atoms of the aryl group is usually 6 to 60, preferably 6 to 49, more preferably 6 to 20, and still more preferably 6 to 14, excluding the number of carbon atoms of the substituent. In R ^a , examples of the halogen atom, alkyl group, and aryl group include the halogen atom, alkyl group, and aryl group exemplified as substituents in <Glossary of Terms>. A plurality of ^Ra may be the same or different.

で表される、Ｒ^ａと結合して形成されるシリル基（以下、単に「式（３１）で表される基」ともいう。）としては、例えば、トリメチルシリル基（ＴＭＳ）、トリエチルシリル基（ＴＥＳ）、トリｎ−プロピルシリル基、トリイソプロピルシリル基（ＴＩＰＳ）、ジメチルイソプロピルシリル基、ジエチルイソプロピルシリル基、ｔｅｒｔ−ブチルジメチルシリル基（ＴＢＤＭＳ）、ｎ−ペンチルジメチルシリル基、ｎ−ヘキシルジメチルシリル基、ｎ−ヘプチルジメチルシリル基、ｎ−オクチルジメチルシリル基、２−エチルヘキシルジメチルシリル基、ｎ−ノニルジメチルシリル基、ｎ−デシルジメチルシリル基、３，７−ジメチルオクチルジメチルシリル基、ｎ−ラウリルジメチルシリル基、フェニル−Ｃ_１〜Ｃ_１２アルキルシリル基、Ｃ_１〜Ｃ_１２アルコキシフェニル−Ｃ_１〜Ｃ_１２アルキルシリル基、Ｃ_１〜Ｃ_１２アルキルフェニル−Ｃ_１〜Ｃ_１２アルキルシリル基、１−ナフチル−Ｃ_１〜Ｃ_１２アルキルシリル基、２−ナフチル−Ｃ_１〜Ｃ_１２アルキルシリル基、フェニル−Ｃ_１〜Ｃ_１２アルキルジメチルシリル基、トリフェニルシリル基、トリ−ｐ−キシリルシリル基、トリベンジルシリル基、ジフェニルメチルシリル基、ｔｅｒｔ−ブチルジフェニルシリル基、ジメチルフェニルシリル基が挙げられる。式（３１）で表される基としては、トリメチルシリル基（ＴＭＳ）、トリエチルシリル基（ＴＥＳ）、トリイソプロピルシリル基（ＴＩＰＳ）、ｔｅｒｔ−ブチルジメチルシリル基（ＴＢＤＭＳ）が好ましく、トリメチルシリル基（ＴＭＳ）、トリエチルシリル基（ＴＥＳ）がより好ましい。 In the formula (1), the following formula (31):

As the silyl group formed by bonding to R ^a (hereinafter, also simply referred to as “group represented by the formula (31)”), for example, a trimethylsilyl group (TMS), a triethylsilyl group ( TES), tri-n-propylsilyl group, triisopropylsilyl group (TIPS), dimethylisopropylsilyl group, diethylisopropylsilyl group, tert-butyldimethylsilyl group (TBDMS), n-pentyldimethylsilyl group, n-hexyldimethylsilyl Group, n-heptyldimethylsilyl group, n-octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group, n-nonyldimethylsilyl group, n-decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group, n-lauryl butyldimethylsilyl group, a phenyl _-C 1 _{-C 12} alkylsilyl _Group, C 1 _{-C 12} alkoxyphenyl _-C 1 _{-C 12} alkylsilyl _group, C 1 _{-C 12} alkylphenyl _-C 1 _{-C 12} alkylsilyl group, 1-naphthyl _-C 1 _{-C 12} alkylsilyl group, 2 - naphthyl _-C 1 _{-C 12} alkylsilyl group, a phenyl _-C 1 _{-C 12} alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, tert- butyl diphenyl Examples thereof include a silyl group and a dimethylphenylsilyl group. The group represented by the formula (31) is preferably a trimethylsilyl group (TMS), a triethylsilyl group (TES), a triisopropylsilyl group (TIPS), or a tert-butyldimethylsilyl group (TBDMS), and a trimethylsilyl group (TMS) A triethylsilyl group (TES) is more preferable.

〔式中、Ｘ、Ｒ^ａ及びＲは、前述と同じ意味を表す。ＹはＣ−Ｒまたは窒素原子を表す。
〕 As a compound represented by Formula (1), the compound represented by a following formula is mentioned, for example.

[Wherein, X, R ^a and R represent the same meaning as described above. Y represents C—R or a nitrogen atom.
]

In the above formula, “(R) ₅ ” represents that 5 hydrogen atoms on the aromatic ring are each substituted with R. Similarly, “(R) ₄ ” represents that four hydrogen atoms on the aromatic ring are each substituted with R, and “(R) ₃ ” represents three hydrogen atoms on the aromatic ring. It represents that each is substituted with R.

  In the manufacturing method of 1st Embodiment, the compound represented by Formula (1) is made to react in presence of a transition metal compound and an organic solvent on the conditions of the atmospheric pressure of 5.5 Mpa or less.

  The pressure during the reaction is not particularly limited as long as it is 5.5 MPa or less, but is preferably 3.0 MPa or less, more preferably 1.0 MPa or less, still more preferably 0.5 MPa or less, even more preferably 0.3 MPa or less, Particularly preferably, it is 0.2 MPa or less. Although the minimum of the atmospheric | air pressure at the time of reaction is not specifically limited, Usually, it is 0.1 MPa. In a preferred embodiment, the atmospheric pressure during the reaction is atmospheric pressure (atmospheric pressure). Even when the reaction is carried out under such mild atmospheric pressure conditions, the production method of the present invention can produce the target amine compound with high yield.

  Examples of the transition metal compound include palladium compounds, ruthenium compounds, rhodium compounds, nickel compounds, iron compounds, and copper compounds. Palladium compounds, rhodium compounds, or nickel compounds are preferable, and palladium compounds or nickel compounds are more preferable. . Transition metal compounds are generally used as catalysts.

  The amount of the transition metal compound used is preferably 0.00001 to 0.1 molar equivalents, more preferably 0.0001 to 0.1 molar equivalents, more preferably the number of moles of the compound represented by formula (1). Preferably it is 0.0005-0.07 molar equivalent, More preferably, it is 0.001-0.05 molar equivalent, Especially preferably, it is 0.005-0.01 molar equivalent.

  Examples of the palladium compound include a compound (complex compound) containing tetravalent, divalent, or zerovalent palladium. Specific examples of the palladium compound include, but are not limited to, sodium hexachloropalladium (IV) tetrahydrate, potassium hexachloropalladium (IV), palladium (II) chloride, palladium (II) bromide, palladium acetate (II ), Palladium (II) acetylacetonate, dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro (cycloocta -1,5-diene) palladium (II), palladium (II) trifluoroacetate, bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), tri (Dibenzylideneacetone) dipalladium (0) chloroform complex, tetrakis (triphenylphosphine) palladium (0), tetrakis (methyldiphenylphosphine) palladium (0), bis [1,2-bis (diphenylphosphino) ethane] palladium (0), bis (acetate) bis (triphenylphosphine) palladium (II), [1,2-bis (diphenylphosphino) ethane] dichloropalladium (II), trans-dibromobis (triphenylphosphine) palladium (II) Cis-dichlorobis (dimethylphenylphosphine) palladium (II), dichlorobis (methyldiphenylphosphine) palladium (II), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (tri Tilphosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (tri-o-tolylphosphine) palladium (II), and dichlorobis (tri-o-methoxyphosphine) palladium (II). . Among them, tetrakis (methyldiphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0), dichlorobis (tricyclohexylphosphine) palladium (II), dichlorobis (triethyl) Phosphine) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorobis (tri-o-tolylphosphine) palladium (II), or dichlorobis (tri-o-methoxyphosphine) palladium (II) is preferred.

  As a nickel compound, the compound (complex compound) containing bivalent, monovalent, or zerovalent nickel is mentioned, for example. Specific examples of the nickel compound are not particularly limited. For example, bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel (0), tetrakis (triphenylphosphine) Nickel (0), dichlorobis (triphenylphosphine) nickel (II), [1,2-bis (diphenylphosphino) ethane] dichloronickel (II), dichlorobis (tricyclohexylphosphine) nickel (II), dichlorobis (trimethylphosphine) ) Nickel (II), dichlorobis (tributylphosphine) nickel (II), [1,3-bis (diphenylphosphino) propane] dichloronickel (II), [1,1′-bis (diphenylphosphino) ferrocene] dichloro Nickel (II , Chloro (cyclopentadienyl) (triphenylphosphine) nickel (II), dichloronickel (II) ethylene glycol dimethyl ether complex, dichloronickel (II) hexaammonate, nickel (II) chloride, nickel (II) chloride hydrate , Nickel (II) chloride hexahydrate, bis (ethylenediamine) nickel (II) chloride hydrate, tris (ethylenediamine) nickel (II) chloride hydrate, nickel (II) bromide, dibromobis (triphenylphosphine) nickel (II) , Dibromobis (tributylphosphine) nickel (II), dibromonickel (II) ethylene glycol dimethyl ether complex, dibromonickel (II) hexaammonate Nickel (II) bromide hydrate, nickel (II) bromide trihydrate, [2,3-bis (2,6-diisopropylphenylphosphino) butane] dibromonickel (II), and diiodonickel (II) It is done. Among them, from the viewpoint of versatility and price, bis (1,5-cyclooctadiene) nickel (0), tetrakis (triphenylphosphine) nickel (0), dichlorobis (triphenylphosphine) nickel (II), dibromobis (tri Phenylphosphine) nickel (II), bis [1,2-bis (diphenylphosphino) ethane] dichloronickel (II), bis [1,3-bis (diphenylphosphino) propane] dichloronickel (II), nickel ( II) Chloride or nickel (II) bromide is preferred.

  When the transition metal compound does not contain a ligand such as phosphine, it is preferable to add a compound that acts as a ligand.

  Examples of the compound that acts as a ligand include a phosphine compound having an alkyl group, a phosphine compound having an aryl group, or a phosphine compound having both an alkyl group and an aryl group. Compounds that act as ligands include triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, and tris (p-fluorophenyl). Phosphine, tris (o-methoxyphenyl) phosphine, tris (m-methoxyphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri (m-chlorophenyl) phosphine , Tri (p-chlorophenyl) phosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-n-butylphosphine, tri-2-furylphosphine, 2- (dicyclohexylphosphino) biphenyl (Cy-Johnp) hos), 2- (di-tert-butylphosphino) biphenyl (Johnphos), 2- (di-tert-butylphosphino) -2'-methylbiphenyl, 2- (dicyclohexylphosphino) -2 ', 6' -Dimethoxy-1,1'-biphenyl (Sphos), 2- (dicyclohexylphosphino) -2 ', 6'-diisopropoxy-1,1'-biphenyl (Rufos), 2- (dicyclohexylphosphino) -3 , 6-dimethoxy-2 ′, 4 ′, 6′-triisopropyl-1,1′-biphenyl (Bretphos), 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl (Davephos) 2-dicyclohexylphosphino-2′-methyl-biphenyl (Mephos), 2- (dicyclo (Hexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl (Xphos), 2- (dicyclohexylphosphino) -1,1-diphenyl-1-propene (Cy-vBRIDP) 2- (di-tert-butylphosphino) -1,1-diphenyl-1-propene (vBRIDP), 1- (dicyclohexylphosphino) -2,2-diphenyl-1-cyclopropane (Cy-cBRIDP), 1,2,3,4,5-pentaphenyl-1 ′-(di-tert-butylphosphino) ferrocene (Qphos), 1,3-bis (2,6-diisopropylphenyl) imidazolinium chloride (SIPr. HCl), preferably 2- (dicyclohexylphosphino) biphenyl (Cy-Johnphos), 2- (di-ter -Butylphosphino) biphenyl (Johnphos), 2- (dicyclohexylphosphino) -2 ', 6'-dimethoxy-1,1'-biphenyl (Sphos), 2- (dicyclohexylphosphino) -2', 6'- Diisopropoxy-1,1′-biphenyl (Ruphos), 2- (dicyclohexylphosphino) -3,6-dimethoxy-2 ′, 4 ′, 6′-triisopropyl-1,1′-biphenyl (Brettphos), 2- (dicyclohexylphosphino) -2 ′-(N, N-dimethylamino) biphenyl (Davephos), 2-dicyclohexylphosphino-2′-methyl-biphenyl (Mephos), 2- (dicyclohexylphosphino) -2 ′ , 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (Xpho s), 2- (dicyclohexylphosphino) -1,1-diphenyl-1-propene (Cy-vBRIDP), 2- (di-tert-butylphosphino) -1,1-diphenyl-1-propene (vBRIDP) 1- (dicyclohexylphosphino) -2,2-diphenyl-1-cyclopropane (Cy-cBRIDP), 1,2,3,4,5-pentaphenyl-1 ′-(di-tert-butylphosphino) Ferrocene (Qphos) and 1,3-bis (2,6-diisopropylphenyl) imidazolinium chloride (SIPr · HCl) are more preferable.

  When a compound acting as a ligand is added, the addition amount is not particularly limited, but is 0.001 to 0.5 molar equivalents relative to the number of moles of the compound represented by formula (1). Is preferred.

  Even when the transition metal compound contains a ligand such as phosphine, a compound acting as the above-mentioned ligand may be added.

In the production method of the first embodiment, the reaction may be performed in the presence of a base. Examples of the base include inorganic bases, organic bases, and inorganic salts. Specific examples of the base include, but are not limited to, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate, potassium phosphate, magnesium carbonate, calcium carbonate, water Sodium oxide, potassium hydroxide, potassium phosphate, tert-butoxy lithium (LiO ^t Bu), tert-butoxy sodium (NaO ^t Bu), tert-butoxy potassium (KO ^t Bu), lithium fluoride, sodium fluoride, fluorine And potassium acetate, cesium fluoride, sodium acetate, and potassium acetate. Among these, from the viewpoint of reactivity and ^{economy, NaO t Bu, KO t Bu} , sodium fluoride, potassium fluoride, cesium fluoride, potassium sodium acetate and acetic acid are preferred, ^KO t Bu, potassium fluoride and acetic acid Sodium is more preferred.

  The base is used by dissolving or dispersing in an organic solvent as necessary. When using a base, the usage-amount is preferably 0.1-50 molar equivalent with respect to the number-of-moles of the compound represented by Formula (1), More preferably, it is 1-20 molar equivalent.

  In the production method of the first embodiment, the reaction may be performed in the presence of a phase transfer catalyst. Among these, when the solubility of the base used for the reaction in the organic solvent is low, it is preferable to use a phase transfer catalyst.

  Examples of the phase transfer catalyst include tetraalkylammonium halide, tetraalkylammonium hexahalophosphate, and tetraalkylammonium tetrahaloborate. The type and amount of the phase transfer catalyst may be appropriately selected according to the type of compound represented by formula (1), the type of organic solvent, and the amount of organic solvent. A phase transfer catalyst may be used individually by 1 type, and may use 2 or more types together.

  In the tetraalkylammonium halide, tetraalkylammonium hexahalophosphate, and tetraalkylammonium tetrahaloborate, examples of the alkyl group include methyl, ethyl, isopropyl, n-propyl, tert-butyl, and n-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group and n-octyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  Specific examples of tetraalkylammonium halides include tetramethylammonium fluoride, tetraethylammonium fluoride, tetra-n-butylammonium fluoride, tetra-tert-butylammonium fluoride, tetramethylammonium chloride, tetraethylammonium chloride, and chloride. Tetra-n-butylammonium chloride, tetra-tert-butylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetra-tert-butylammonium bromide, tetramethylammonium iodide, Tetraethylammonium iodide, tetra-n-butylammonium iodide, tetra-tert-butylammonium iodide, tetra-n-pentylammonium fluoride, salt Tetra-n-pentylammonium, tetra-n-pentylammonium bromide, tetra-n-pentylammonium iodide, tetra-n-hexylammonium fluoride, tetra-n-hexylammonium chloride, tetra-n-hexylammonium bromide Tetra-n-hexylammonium iodide, tetra-n-heptylammonium fluoride, tetra-n-heptylammonium chloride, tetra-n-heptylammonium bromide, tetra-n-heptylammonium iodide, tetra-n fluoride -Octylammonium fluoride, tetra-n-octylammonium chloride, tetra-n-octylammonium bromide, tetra-n-octylammonium iodide, and tri-n-octylmethylammonium chloride.

  Specific examples of tetraalkylammonium hexahalophosphates include tetramethylammonium hexafluorophosphate, tetramethylammonium hexachlorophosphate, tetramethylammonium hexabromophosphate, and tetramethylammonium hexaiodophosphate. Specific examples of the tetraalkylammonium tetrahaloborate include tetramethylammonium tetrafluoroborate, tetramethylammonium tetrachloroborate, tetramethylammonium tetrabromoborate, and tetramethylammonium tetraiodoborate.

  When a phase transfer catalyst is used, the amount used is preferably 0.01 to 20 molar equivalents relative to the number of moles of the compound represented by formula (1).

  Examples of the organic solvent used in the reaction include a nonpolar aromatic solvent, a polar oxygen-containing solvent, a polar nitrogen-containing solvent, and a polar sulfur-containing solvent. Specific examples of the organic solvent include benzene, toluene, xylene, mesitylene, 1,4-dioxane, tetrahydrofuran (THF), ethylene glycol dimethyl ether, cyclopentyl methyl ether (CPME), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolidione (DMI), hexamethylphosphoric triamide (HMPA), N, N′-dimethylpropylene urea (DMPU), and tetramethyl urea (TMU) may be mentioned. Preferably, toluene, cyclopentyl methyl ether (CPME), N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolidione (DMI), hexamethylphosphoric triamide ( HMPA), N, N′-dimethylpropyleneurea (DMPU), tetramethylurea (TMU), and dimethylsulfoxide (DMSO). An organic solvent may be used individually by 1 type, and may use 2 or more types together.

  The amount of the organic solvent used is preferably 1 to 1000 times the weight of the compound represented by formula (1).

  The organic solvent varies depending on the type of the organic solvent to be used, but in general, it is preferable to sufficiently perform deoxygenation before use in the reaction in order to suppress side reactions.

  The reaction of the compound represented by the formula (1) is preferably performed in an inert gas atmosphere such as argon gas or nitrogen gas.

As a method of adding a transition metal compound (and a ligand, a base and a phase transfer catalyst used as necessary) to the reaction system, a solution obtained by dissolving the compound represented by the formula (1) in an organic solvent is used. An example is a method in which a solution in which a transition metal compound (and a ligand, a base and a phase transfer catalyst used as necessary) are dissolved in an organic solvent is added while stirring in an inert gas atmosphere.
As another method, a solution in which a transition metal compound (and a ligand, a base, and a phase transfer catalyst used as necessary) are dissolved in an organic solvent is stirred in an inert gas atmosphere. The method of adding the solution which melt | dissolved the represented compound in the organic solvent is illustrated.

  The reaction can be carried out at a temperature not lower than the melting point of the organic solvent used and not higher than the boiling point. The reaction temperature is usually room temperature (25 ° C.) to 250 ° C., preferably 30 to 200 ° C., more preferably 40 to 150 ° C., further preferably 40 to 130 ° C., and still more preferably 40 to 120 ° C. Even when the reaction is carried out under such mild temperature conditions, the target amine compound can be produced with high yield according to the production method of the present invention.

  The reaction time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, still more preferably 2 to 25 hours.

  The polymer compound containing the structural unit represented by the formula (2) manufactured in the manufacturing method of the first embodiment has a polystyrene-equivalent number average molecular weight (Mn), preferably 1,000 or more, more preferably 2,000 or more, more preferably 3,000 or more. The upper limit of Mn in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less. The weight average molecular weight (Mw) in terms of polystyrene is preferably 1,000 or more, more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit of Mw in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less. The polystyrene-converted Mn and Mw can be measured by, for example, a gel permeation chromatography (GPC) method.

  The polymer compound containing the structural unit represented by the formula (2) manufactured in the manufacturing method of the first embodiment may be a homopolymer or a copolymer. When the polymer compound is a copolymer, it may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer, or a polymer having an intermediate structure thereof, For example, it may be a random copolymer having block properties. The polymer compound produced by the production method of the first embodiment includes a branch polymer (including a dendrimer) having a branched main chain and three or more terminal portions.

〔式中、
ｍは、１〜４の整数を表す。
Ａｒ^１１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｍ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｍ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｍ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｍ個を除いた基を表す。
Ｒ^１は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。
Ａｒ^１１とＲ^１は、直接結合して又は連結基を介して環を形成してもよい。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、
ｎは、１〜４の整数を表す。
Ａｒ^１２は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｎ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｎ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｎ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｎ個を除いた基を表す。
Ｘは、脱離基を表す。Ｘが複数個ある場合、それらは同一でも相異なってもよい。〕

〔式中、Ａｒ^１１、Ａｒ^１２、Ｒ^１、Ｒ^ａ、Ｘ、ｍ及びｎは、前述と同じ意味を表す。〕 Second Embodiment
In the second embodiment of the method for producing an amine compound of the present invention, a compound represented by the formula (11) and a formula (12) in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. A compound represented by formula (13) is reacted with a compound represented by the formula (13) to produce an amine compound.

[Where,
m represents an integer of 1 to 4.
Ar ¹¹ is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which m atoms are removed, and an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is removed from an aromatic amine compound which may have a substituent, wherein m hydrogen atoms on the aromatic ring are removed. Represents a group in which m hydrogen atoms have been removed.
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹¹ and R ¹ may be directly bonded or form a ring via a linking group.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Where,
n represents an integer of 1 to 4.
Ar ¹² is a group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding n atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding n hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group in which n hydrogen atoms have been removed.
X represents a leaving group. When there are a plurality of X, they may be the same or different. ]

[Wherein, Ar ¹¹ , Ar ¹² , R ¹ , R ^a , X, m and n represent the same meaning as described above. ]

In the formula (11), Ar ¹¹ is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, and a heterocyclic compound which may have a substituent. A group obtained by removing m hydrogen atoms on a heterocyclic ring from the aromatic amine compound which may have a substituent or a group obtained by removing m hydrogen atoms on an aromatic ring or a substituent A group obtained by removing m hydrogen atoms from an aliphatic unsaturated hydrocarbon. Ar ¹¹ is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent on a heterocyclic ring. A group in which m hydrogen atoms are removed is preferred.
In Ar ¹¹ , the aromatic hydrocarbon, heterocyclic compound, aromatic amine compound, and aliphatic unsaturated hydrocarbon are the same as those described for Ar ¹ .

In the formula (11), R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent which remove | excluded one hydrogen atom on an aromatic ring is represented. R ¹ is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent on a heterocyclic ring. A group in which one hydrogen atom is removed is preferred.
The aliphatic hydrocarbon, aromatic hydrocarbon and heterocyclic compound are the same as those described for R ¹ in formula (1).

In formula (11), Ar ¹¹ and R ¹ may be directly bonded or form a ring via a linking group. The linking group that connects Ar ¹¹ and R ¹ is the same as the linking group that connects Ar ¹ and R ^{1 in} Formula (1).

In formula (11), R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. The halogen atom, the alkyl group which may have a substituent, and the aryl group which may have a substituent are the same as those described for ^Ra in the formula (1).

In the formula (11), examples of the silyl group formed by bonding to R ^a are the same as those described for the group represented by the formula (31) in the formula (1).

〔式中、Ｒ^ａ及びＲは、前述と同じ意味を表す。ＹはＣ−Ｒまたは窒素原子を表す。〕 As a compound represented by Formula (11), the compound which has the following structure is mentioned, for example.

[Wherein, R ^a and R represent the same meaning as described above. Y represents C—R or a nitrogen atom. ]

In formula (12), Ar ¹² is a group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, and a heterocyclic compound which may have a substituent. A group obtained by removing n hydrogen atoms on a heterocyclic ring from the aromatic amine compound which may have a substituent or a group obtained by removing n hydrogen atoms on an aromatic ring or a substituent A group obtained by removing n hydrogen atoms from an aliphatic unsaturated hydrocarbon. Ar ¹² is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent on a heterocyclic ring. A group from which n hydrogen atoms have been removed is preferred.
In Ar ¹² , the aromatic hydrocarbon, heterocyclic compound, aromatic amine compound, and aliphatic unsaturated hydrocarbon are the same as those described for Ar ¹ .

  In formula (12), X represents a leaving group. The leaving group is the same as that described for X in formula (1). When there are a plurality of X, they may be the same or different.

〔式中、Ｒ及びＸは、前述と同じ意味を表す。〕 As a compound represented by Formula (12), the compound which has the following structure is mentioned, for example.

[Wherein R and X represent the same meaning as described above. ]

In the above formula, “(R) ₅ ” represents that 5 hydrogen atoms on the aromatic ring are each substituted with R, and “(X) ₄ ” represents 4 hydrogen atoms on the aromatic ring. Are each substituted with X. The same applies to “(R) ₄ ”, “(R) ₃ ”, “(R) ₂ ”, “(X) ₃ ”, and “(X) ₂ ”.

  In the production method of the second embodiment, the compound represented by the formula (11) and the compound represented by the formula (12) in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. And react.

  In the manufacturing method of the second embodiment, the atmospheric pressure during the reaction, the reaction temperature, the reaction time, the transition metal compound, and the organic solvent are the same as those described for the manufacturing method of the first embodiment. Also in the manufacturing method of 2nd Embodiment, you may use 1 or more types selected from the group which consists of a ligand, a base, and a phase transfer catalyst as needed. The ligand, base, and phase transfer catalyst are the same as those described for the production method of the first embodiment. According to the production method of the second embodiment, the target amine compound can be produced in good yield under mild conditions.

  The amount of the transition metal compound used is preferably 0.00001 to 0.1 molar equivalent, more preferably the total number of moles of the compound represented by formula (11) and the compound represented by formula (12). Is 0.0001 to 0.1 molar equivalent, more preferably 0.001 to 0.05 molar equivalent, still more preferably 0.005 to 0.01 molar equivalent.

  Although the usage-amount of the compound represented by Formula (11) and the compound represented by Formula (12) is not specifically limited, Of the group represented by Formula (31) in the compound represented by Formula (11) It is preferable that the leaving group in the compound represented by Formula (12) is in the range of 0.5 to 8 molar equivalents relative to the number of moles. The compound represented by the formula (12) with respect to the number of moles of the group represented by the formula (31) in the compound represented by the formula (11) from the viewpoint of economy and the ease of purification after the reaction. The leaving group therein is more preferably in the range of 0.6 to 4 molar equivalents, and still more preferably in the range of 0.8 to 2 molar equivalents.

  In the manufacturing method of 2nd Embodiment, m in Formula (11) represents the integer of 1-4, n in Formula (12) represents the integer of 1-4.

〔式中、Ａｒ^１１、Ａｒ^１２、Ｒ^１、ｎは、前述と同じ意味を表す。〕 When m = 1, the compound represented by the formula (13-1) can be produced from the compound represented by the formula (11) and the compound represented by the formula (12). When n ≧ 2, the compound represented by formula (13-1) is a compound finally obtained.

[Wherein, Ar ¹¹ , Ar ¹² , R ¹ , n represent the same meaning as described above. ]

〔式中、Ａｒ^１１、Ａｒ^１２、Ｒ^１、ｍは、前述と同じ意味を表す。〕 When n = 1, the compound represented by the formula (13-2) can be produced from the compound represented by the formula (11) and the compound represented by the formula (12). In addition, when m ≧ 2, the compound represented by the formula (13-2) is a compound finally obtained.

[Wherein, Ar ¹¹ , Ar ¹² , R ¹ , m represent the same meaning as described above. ]

  When m ≧ 2 and n ≧ 2, the compound represented by the formula (13) can be produced from the compound represented by the formula (11) and the compound represented by the formula (12). A compound (may be a polymer compound) produced by further reacting the compound represented by formula (11) and / or the compound represented by formula (12) with respect to the compound represented by (13). can do.

  Here, when m = 2 and n = 2, a polymer compound or a cyclic compound can be produced from the compound represented by the formula (11) and the compound represented by the formula (12).

〔式中、Ａｒ^１１、Ａｒ^１２及びＲ^１は、前述と同じ意味を表す。〕 In a preferred embodiment, a compound represented by the formula (11) (wherein m = 2) and a compound represented by the formula (12) (wherein n = 2) are reacted to form a compound represented by the formula: A polymer compound containing the structural unit represented by (14) can be produced.

[In formula, Ar < ¹¹ >, Ar < ¹² > and R < ¹ > represent the same meaning as the above-mentioned. ]

〔式中、Ａｒ^１１、Ａｒ^１２及びＲ^１は、前述と同じ意味を表す。ｆは、１〜３０の整数を表す。〕 In another preferred embodiment, a compound represented by formula (11) (wherein m = 2) and a compound represented by formula (12) (wherein n = 2) are reacted. The cyclic compound represented by Formula (15) can be produced.

[In formula, Ar < ¹¹ >, Ar < ¹² > and R < ¹ > represent the same meaning as the above-mentioned. f represents an integer of 1 to 30. ]

When the compound represented by formula (13) further reacts with the compound represented by formula (11) and / or the compound represented by formula (12) to form a polymer compound, polystyrene of the polymer compound The converted Mn is preferably 500 or more, more preferably 1,000 or more, and still more preferably 3,000 or more. The upper limit of Mn in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less. Further, the Mw in terms of polystyrene is preferably 500 or more, more preferably 1,000 or more, and still more preferably 3,000 or more. The upper limit of Mw in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less.
The polymer compound may be a homopolymer or a copolymer. When the polymer compound is a copolymer, it may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer, or a polymer having an intermediate structure thereof, For example, it may be a random copolymer having block properties. The polymer compound produced by the production method of the second embodiment includes a branch polymer (including a dendrimer) having a branched main chain and three or more terminal portions.

<Third Embodiment>
The third embodiment of the method for producing an amine compound of the present invention is a cyclic reaction in which the compound represented by the above formula (1) is reacted in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. It is a manufacturing method of a compound.

  In the compound represented by the formula (1), a reaction between the leaving group in the same molecule and the group represented by the formula (31) causes intramolecular cyclization, or a plurality of molecules are linked to form a molecule. A cyclic compound represented by the formula (41) can be produced by intercyclization.

〔式中、Ａｒ^１とＲ^１は、前述と同じ意味を表す。ｇは、１〜３０の整数を表す。〕

[Wherein Ar ¹ and R ¹ represent the same meaning as described above. g represents an integer of 1 to 30. ]

  In the manufacturing method of the third embodiment, the atmospheric pressure during the reaction, the reaction temperature, the reaction time, the transition metal compound, and the organic solvent are the same as those described for the manufacturing method of the first embodiment. Also in the manufacturing method of 3rd Embodiment, you may use 1 or more types selected from the group which consists of a ligand, a base, and a phase transfer catalyst as needed. The ligand, base, and phase transfer catalyst are the same as those described for the production method of the first embodiment.

〔式中、
ｐは、１〜４の整数を表す。
Ａｒ^５１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｐ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｐ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｐ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｐ個を除いた基を表す。
Ｒ^ａは、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａは、同一でも相異なってもよい。〕

〔式中、Ａｒ^１２、Ａｒ^５１、Ｒ^ａ、Ｘ、ｐ及びｎは、前述と同じ意味を表す。〕 <Fourth embodiment>
In the fourth embodiment of the method for producing an amine compound of the present invention, the compound represented by the formula (51) and the formula (12) in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. A compound represented by formula (52) is reacted with the compound represented by formula (52) to produce an amine compound.

[Where,
p represents an integer of 1 to 4.
Ar ⁵¹ is a group obtained by removing p hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which p atoms are removed, an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is optionally substituted with a group in which p hydrogen atoms on the aromatic ring are removed Represents a group in which p hydrogen atoms have been removed.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Wherein, Ar ¹² , Ar ⁵¹ , R ^a , X, p and n represent the same meaning as described above. ]

In formula (51), Ar ⁵¹ is a group obtained by removing p hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a heterocyclic compound which may have a substituent. A group obtained by removing p hydrogen atoms on a heterocyclic ring from the aromatic amine compound which may have a substituent, or a group obtained by removing p hydrogen atoms on an aromatic ring or a substituent A group obtained by removing p hydrogen atoms from an aliphatic unsaturated hydrocarbon. Ar ⁵¹ is a group obtained by removing p hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent from the viewpoint of the reactivity of the compound represented by formula (51). Is preferred.
In Ar ⁵¹ , the aromatic hydrocarbon, heterocyclic compound, aromatic amine compound, and aliphatic unsaturated hydrocarbon are the same as those described for Ar ¹ .

In formula (51), R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. The halogen atom, the alkyl group which may have a substituent, and the aryl group which may have a substituent are the same as those described for ^Ra in the formula (1).

In the formula (51), examples of the silyl group formed by bonding to R ^a are the same as those described for the group represented by the formula (31) in the formula (1).

〔式中、Ｒ^ａ及びＲは、前述と同じ意味を表す。〕 Examples of the compound represented by the formula (51) include compounds having the following structure.

[Wherein, R ^a and R represent the same meaning as described above. ]

  In the manufacturing method of the fourth embodiment, the atmospheric pressure during the reaction, the reaction temperature, the reaction time, the transition metal compound, and the organic solvent are the same as those described for the manufacturing method of the first embodiment. Also in the manufacturing method of 4th Embodiment, you may use 1 or more types selected from the group which consists of a ligand, a base, and a phase transfer catalyst as needed. The ligand, base, and phase transfer catalyst are the same as those described for the production method of the first embodiment. According to the manufacturing method of 4th Embodiment, the target amine compound can be manufactured with sufficient yield on mild conditions.

  The amount of the transition metal compound used is preferably 0.00001 to 0.1 molar equivalent, more preferably the total number of moles of the compound represented by formula (51) and the compound represented by formula (12). Is 0.0001 to 0.1 molar equivalent, more preferably 0.001 to 0.05 molar equivalent, still more preferably 0.005 to 0.01 molar equivalent.

  Although the usage-amount of the compound represented by Formula (51) and the compound represented by Formula (12) is not specifically limited, Of the group represented by Formula (31) in the compound represented by Formula (51) It is preferable that the leaving group in the compound represented by Formula (12) is in the range of 0.5 to 8 molar equivalents relative to the number of moles. The compound represented by the formula (12) with respect to the number of moles of the group represented by the formula (31) in the compound represented by the formula (51) from the viewpoint of economy and the ease of purification after the reaction. The leaving group therein is more preferably in the range of 0.6 to 4 molar equivalents, and still more preferably in the range of 0.8 to 2 molar equivalents.

  In the manufacturing method of 4th Embodiment, p in Formula (51) represents the integer of 1-4, n in Formula (12) represents the integer of 1-4.

〔式中、Ａｒ^１２、Ａｒ^５１、Ｒ^ａ、Ｘ、ｐ及びｎは、前述と同じ意味を表す。〕 In the production method of the fourth embodiment, the compound represented by the formula (52) can be produced from the compound represented by the formula (51) and the compound represented by the formula (12). The compound represented by Formula (54) can be manufactured by making the compound represented by Formula (52) and the compound represented by Formula (12) react.

[Wherein, Ar ¹² , Ar ⁵¹ , R ^a , X, p and n represent the same meaning as described above. ]

〔式中、Ａｒ^１２、Ａｒ^５１、Ｒ^ａ、Ｘ、ｐ及びｎは、前述と同じ意味を表す。〕 When p ≧ 2, the compound represented by the formula (55) can be produced by reacting the compound represented by the formula (52) with the compound represented by the formula (12). it can.

[Wherein, Ar ¹² , Ar ⁵¹ , R ^a , X, p and n represent the same meaning as described above. ]

  When n ≧ 2, the compound represented by the formula (52) is reacted with the compound represented by the formula (51) and / or the compound represented by the formula (12) to obtain a polymer. Compounds or cyclic compounds can be produced.

  Here, when p = 1 and n = 2, the compound represented by the formula (51) and the compound represented by the formula (12) are reacted to produce a polymer compound or a cyclic compound. it can.

〔式中、Ａｒ^５１及びＡｒ^１２は、前述と同じ意味を表す。〕 In a preferred embodiment, a compound represented by the formula (51) (wherein p = 1) and a compound represented by the formula (12) (wherein n = 2) are reacted to form a compound represented by the formula: A polymer compound containing the structural unit represented by (53) can be produced.

[Wherein, Ar ⁵¹ and Ar ¹² represent the same meaning as described above. ]

〔式中、Ａｒ^５１及びＡｒ^１２は、前述と同じ意味を表す。ｈは、１〜３０の整数を表す。〕 In another preferred embodiment, the compound represented by formula (51) (wherein p = 1) is reacted with the compound represented by formula (12) (wherein n = 2). The cyclic compound represented by Formula (56) can be produced.

[Wherein, Ar ⁵¹ and Ar ¹² represent the same meaning as described above. h represents an integer of 1 to 30. ]

In the case of producing a polymer compound by reacting the compound represented by formula (52) with the compound represented by formula (51) and / or the compound represented by formula (12), the polymer compound The Mn in terms of polystyrene is preferably 500 or more, more preferably 1,000 or more, and still more preferably 3,000 or more. The upper limit of Mn in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less. Further, the Mw in terms of polystyrene is preferably 500 or more, more preferably 1,000 or more, and still more preferably 3,000 or more. The upper limit of Mw in terms of polystyrene is not particularly limited, but is preferably 1,000,000 or less.
The polymer compound may be a homopolymer or a copolymer. When the polymer compound is a copolymer, it may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer, or a polymer having an intermediate structure thereof, For example, it may be a random copolymer having block properties. The polymer compound produced by the production method of the second embodiment includes a branch polymer (including a dendrimer) having a branched main chain and three or more terminal portions.

[Compound]
In a preferred embodiment, the compound represented by formula (1) is a compound represented by the following formula (21-1) or formula (21-2).

〔式中、
ｋは、０又は１を表す。
Ｘ^２１は、脱離基を表す。
Ａｒ^２１は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子３個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子３個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子３個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子３個を除いた基を表す。
Ｙは、連結基を表す。
Ａｒ^２２は、置換基を有していてもよい脂肪族炭化水素から水素原子２個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子２個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子２個を除いた基を表す。
Ｒ^ａ２１は、水素原子、ハロゲン原子、置換基を有していてもよいアルキル基又は置換基を有していてもよいアリール基を表す。複数個あるＲ^ａ２１は、同一でも相異なってもよい。〕

[Where,
k represents 0 or 1.
X ²¹ represents a leaving group.
Ar ²¹ is a group obtained by removing three hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which 3 atoms are removed, an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which 3 hydrogen atoms on an aromatic ring are removed from an aromatic amine compound which may have a substituent Represents a group obtained by removing three hydrogen atoms from
Y represents a linking group.
Ar ²² represents a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon which may have a substituent, and two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded two hydrogen atoms on a heterocyclic ring from the heterocyclic compound which may have the excluded group or substituent is represented.
R ^a21 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of R ^a21 may be the same or different. ]

〔式中、
Ｘ^２１とＲ^ａ２１は、前述と同じ意味を表す。
Ａｒ^２３は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子２個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子２個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子２個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子２個を除いた基を表す。
Ａｒ^２４は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。〕

[Where,
X ²¹ and R ^a21 represent the same meaning as described above.
Ar ²³ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding two atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding two hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group obtained by removing two hydrogen atoms from
Ar ²⁴ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented. ]

In formulas (21-1) and (21-2), X ²¹ represents a leaving group. The leaving group is the same as that described for X in formula (1).

In formulas (21-1) and (21-2), R ^a21 represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. R ^a21 is the same as that described for R ^a in formula (1). A plurality of R ^a21 may be the same or different.

In formulas (21-1) and (21-2), examples of the silyl group formed by bonding to R ^a21 are the same as those described for the group represented by formula (31) in formula (1). It is.

In Ar ²¹ and Ar ²³ , the aromatic hydrocarbon, the heterocyclic compound, the aromatic amine compound, and the aliphatic unsaturated hydrocarbon are the same as those described for Ar ¹ in the formula (1).

In Ar ²² and Ar ²⁴ , the aliphatic hydrocarbon, aromatic hydrocarbon, and heterocyclic compound are the same as those described for R ¹ in formula (1).

In formula (21-1), k represents 0 or 1. When k = 0, Ar ²¹ and Ar ²² are directly bonded to form a ring. When k = 1, Ar ²¹ and Ar ²² form a ring through Y. Y represents a linking group. The linking group is the same as the linking group that links Ar ¹ and R ^{1 in} Formula (1).

  Examples of the compound represented by the formula (21-1) include the formulas Carb-1 to Carb-4, the formulas POZ-1 to POZ-4, and the formula PTZ- exemplified as the compounds represented by the formula (1). 1 to PTZ-4, Formulas Phena-1 to Phena-4, Formulas DBAZE-1 to DBAZE-4, Formulas DHDBAZE-1 to DHDBASE-4, Formulas BCarb-1 to BCarb-6, Formulas DBCarb-1 to DBCarb-2 , Formulas HeCarb-1 to HeCarb-4, and compounds represented by formulas Am-5 to Am-6.

  Examples of the compound represented by the formula (21-2) include those represented by the formula Am-1 to Am-4 and the formula Am-7 to Am-12 exemplified as the compound represented by the formula (1). Compounds.

〔式中、
ｊは、２〜４の整数を表す。
Ｒ^ａ２１は、前述と同じ意味を表す。
Ａｒ^２５は、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子ｊ個を除いた基、置換基を有していてもよい複素環式化合物から複素環上の水素原子ｊ個を除いた基、置換基を有していてもよい芳香族アミン化合物から芳香環上の水素原子ｊ個を除いた基又は置換基を有していてもよい脂肪族不飽和炭化水素から水素原子ｊ個を除いた基を表す。
Ａｒ^２６は、水素原子、置換基を有していてもよい脂肪族炭化水素から水素原子１個を除いた基、置換基を有していてもよい芳香族炭化水素から芳香環上の水素原子１個を除いた基又は置換基を有していてもよい複素環式化合物から複素環上の水素原子１個を除いた基を表す。〕 In a preferred embodiment, the compound represented by the formula (11) is a compound represented by the following formula (21-3).

[Where,
j represents an integer of 2 to 4.
R ^a21 represents the same meaning as described above.
Ar ²⁵ is a group obtained by removing j hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding j atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding j hydrogen atoms on an aromatic ring from an aromatic amine compound which may have a substituent Represents a group in which j hydrogen atoms have been removed.
Ar ²⁶ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented. ]

  In formula (21-3), j represents an integer of 2 to 4. When manufacturing a high molecular compound using the compound represented by Formula (21-3), it is preferable that j is 2.

In Ar ²⁵ , the aromatic hydrocarbon, the heterocyclic compound, the aromatic amine compound, and the aliphatic unsaturated hydrocarbon are the same as those described for Ar ¹ in the formula (1).

In Ar ²⁶ , the aliphatic hydrocarbon, the aromatic hydrocarbon, and the heterocyclic compound are the same as those described for R ¹ in the formula (1).

  Examples of the compound represented by the formula (21-3) include compounds represented by the formulas Am11-16 to Am11-20 exemplified as the compound represented by the formula (11).

  Hereinafter, examples and comparative examples will be shown to describe the present invention in more detail, but the present invention is not limited to these examples.

  NMR analysis of amine compounds produced in the following Examples and Comparative Examples was performed using “Varian Mercury 400” manufactured by Agilent Technologies.

  IR analysis of the amine compound manufactured by the following example and the comparative example was performed using JASCO Corporation "FT / IR-4200".

  Molecular weight analysis by MALDI-TOF-MASS of the polymer compounds produced in the following Examples and Comparative Examples was performed using “AXIMA-CFR” manufactured by Shimadzu Corporation.

The number average molecular weight (Mn) in terms of polystyrene and the weight average molecular weight (Mw) in terms of polystyrene of the polymer compounds produced in the following Examples and Comparative Examples were measured using the following gel permeation chromatography (GPC) apparatus. .
Column: “PLgel MIXED-B” manufactured by Polymer Laboratories
Detector: UV-VIS detector “SPD-10Avp” manufactured by Shimadzu Corporation
Mobile phase: THF

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、化合物Ｓ１（９Ｈ−カルバゾール、５．０１ｇ、３０．０ｍｍｏｌ）及びＴＨＦ（３５ｍＬ）を加え、−７８℃に冷却した。その後、そこにｎ−ブチルリチウム（ｎ−ＢｕＬｉ、２．６５Ｍ、１３．６ｍＬ、３６ｍｍｏｌ）を滴下し、２時間攪拌した。得られた反応溶液にクロロトリメチルシラン（ＴＭＳＣｌ、５．２０ｍＬ、６０．０ｍｍｏｌ）を滴下した後、徐々に昇温し、室温で１８時間攪拌した。得られた反応溶液を減圧留去し、熱ヘキサンで溶解させた後、濾過により沈殿物を取り除いた。得られた濾液を減圧留去し、化合物ＣＭ１（７．０４ｇ、２９．４ｍｍｏｌ、収率９８％）を得た。
−方法２−
下記スキームに従って、化合物ＣＭ１を合成した。

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、水素化ナトリウム（ＮａＨ、４８０ｍｇ、１２．０ｍｍｏｌ）及びヘキサン（２５ｍＬ）を加えて攪拌した後、デカンテーションでヘキサンを取り除いた。その後、同様のデカンテーション操作を３回繰り返した。その後、ＮａＨを真空乾燥させ、次いで、ＴＨＦ（１０ｍＬ）を加え、０℃に冷却した。その後、そこにＴＨＦ（１５ｍＬ）に溶解させた化合物Ｓ１（９Ｈ−カルバゾール、１．６７ｇ、１０．０ｍｍｏｌ）を滴下し、室温で２時間攪拌した。得られた反応溶液にＴＭＳＣｌ（１．７３ｍＬ、２０．０ｍｍｏｌ）を滴下し、さらに室温で１８時間攪拌した。得られた反応溶液を減圧留去し、熱ヘキサンで溶解させた後、濾過により沈殿物を取り除いた。得られた濾液を減圧留去し、化合物ＣＭ１（２．０４ｇ、８．５２ｍｍｏｌ、収率９８％）を得た。 Compound CM1 was synthesized by the following two production methods.
[Synthesis Example 1] (Synthesis of Compound CM1)
-Method 1
Compound CM1 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and the compound S1 (9H-carbazole, 5.01 g, 30.0 mmol) and THF (35 mL) were added to the heat-dried reaction vessel and cooled to -78 ° C. Thereafter, n-butyllithium (n-BuLi, 2.65M, 13.6 mL, 36 mmol) was added dropwise thereto and stirred for 2 hours. Chlorotrimethylsilane (TMSCl, 5.20 mL, 60.0 mmol) was added dropwise to the resulting reaction solution, and then the temperature was gradually raised and stirred at room temperature for 18 hours. The obtained reaction solution was distilled off under reduced pressure, dissolved in hot hexane, and then the precipitate was removed by filtration. The obtained filtrate was distilled off under reduced pressure to obtain Compound CM1 (7.04 g, 29.4 mmol, yield 98%).
-Method 2-
Compound CM1 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, sodium hydride (NaH, 480 mg, 12.0 mmol) and hexane (25 mL) were added to the reaction vessel heated and dried, and the mixture was stirred and then hexane was removed by decantation. . Thereafter, the same decantation operation was repeated three times. Then NaH was vacuum dried, then THF (10 mL) was added and cooled to 0 ° C. Thereafter, compound S1 (9H-carbazole, 1.67 g, 10.0 mmol) dissolved in THF (15 mL) was added dropwise thereto and stirred at room temperature for 2 hours. TMSCl (1.73 mL, 20.0 mmol) was added dropwise to the obtained reaction solution, and the mixture was further stirred at room temperature for 18 hours. The obtained reaction solution was distilled off under reduced pressure, dissolved in hot hexane, and then the precipitate was removed by filtration. The obtained filtrate was distilled off under reduced pressure to obtain Compound CM1 (2.04 g, 8.52 mmol, yield 98%).

化合物Ｓ１に代えて化合物Ｓ２（３．５８ｍｇ、１０．０ｍｍｏｌ）を使用した以外は、上記方法２と同様にして反応を行った。ＴＭＳＣｌとの反応終了後、得られた反応溶液を減圧留去し、シリカゲルクロマトグラフィー（酢酸エチル：ヘキサン＝１：１０）で精製し、化合物ＣＭ２（２．８０ｇ、６．５１ｍｍｏｌ、収率６５％）を得た。 [Example 1] (Synthesis of Compound CM2)
Compound CM2 was synthesized according to the following scheme.

The reaction was performed in the same manner as in Method 2 above, except that compound S2 (3.58 mg, 10.0 mmol) was used instead of compound S1. After completion of the reaction with TMSCl, the obtained reaction solution was distilled off under reduced pressure and purified by silica gel chromatography (ethyl acetate: hexane = 1: 10) to obtain compound CM2 (2.80 g, 6.51 mmol, yield 65%). )

¹ H NMR (400 MHz, CDCl ₃ ) δ 8.15 (s, 1H), 7.80 (s, 1H), 7.50 (d, J = 8.4 Hz, 1H), 7.38-7 .45 (m, 2H), 7.22 (d, J = 8.4 Hz, 1H), 2.75 (t, J = 7.6 Hz, 2H), 1.65-1.72 (m, 2H), 1.20-1.42 (m, 10H), 0.88 (t, J = 7.0 Hz, 3H), 0.67 (s, 9H);
¹³ C NMR (100 MHz, CDCl ₃ ) δ 143.2, 143.0, 134.7, 128.2, 127.9, 127.1, 125.3, 122.8, 119.6, 114.5 113.0, 112.4, 35.9, 32.3, 32.1, 29.7, 29.52, 29.45, 22.85, 14.3, 1.7;
IR (neat) 2954, 2925, 2853, 1482, 1467, 1467, 1440, 1274, 1257, 1218, 1138, 1063, 1024, 971, 843, 802, 763, 699, 634 cm ⁻¹

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、ビス（１，５−シクロオクタジエン）ニッケル（０）（Ｎｉ（ｃｏｄ）_２、６．９ｍｇ、２５μｍｏｌ、５ｍｏｌ％）、１，３−ビス（２，６−ジイソプロピルフェニル）イミダゾリニウムクロリド（ＳＩＰｒ・ＨＣｌ、１０．７ｍｇ、２５μｍｏｌ、５ｍｏｌ％）、ｔｅｒｔ−ブトキシカリウム（ＫＯ^ｔＢｕ、２．８ｍｇ、２５μｍｏｌ、５ｍｏｌ％）及びシクロペンチルメチルエーテル（ＣＰＭＥ、０．３０ｍＬ）を加え、１００℃で１時間攪拌した。得られた溶液を室温まで冷却した後、上記方法２で合成した化合物ＣＭ１（１５０．７ｍｇ、０．６３ｍｍｏｌ）、化合物Ｓ３（６１．５μＬ、０．５０ｍｍｏｌ）、酢酸ナトリウム（ＮａＯＡｃ、６９．７ｍｇ、０．８５ｍｍｏｌ）およびＣＰＭＥ（０．２ｍＬ）を加え、１００℃で２４時間攪拌した。得られた反応溶液をジクロロメタンで希釈し、フロリジルを用いて濾過した。得られた濾液を減圧留去し、室温で真空乾燥することにより粗生成物を得た。この粗生成物をカラムクロマトグラフィー（酢酸エチル：ヘキサン＝５：１）で精製し、化合物ＣＭ３（１２３．４ｍｇ、収率９６％）を得た。 [Example 2] (Synthesis of Compound CM3)
Compound CM3 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and the heat-dried reaction vessel was charged with bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ 6.9 mg, 25 μmol, 5 mol%), 1,3-bis (2,6-diisopropylphenyl) imidazolinium chloride (SIPr · HCl, 10.7 mg, 25 μmol, 5 mol%), tert-butoxy potassium (KO ^t Bu, 2.8 mg, 25 μmol, 5 mol%) And cyclopentyl methyl ether (CPME, 0.30 mL) was added, and the mixture was stirred at 100 ° C. for 1 hour. After cooling the resulting solution to room temperature, Compound CM1 (150.7 mg, 0.63 mmol), Compound S3 (61.5 μL, 0.50 mmol), Sodium Acetate (NaOAc, 69.7 mg) synthesized by Method 2 above. 0.85 mmol) and CPME (0.2 mL) were added, and the mixture was stirred at 100 ° C. for 24 hours. The resulting reaction solution was diluted with dichloromethane and filtered using florisil. The obtained filtrate was distilled off under reduced pressure, and the crude product was obtained by vacuum drying at room temperature. The crude product was purified by column chromatography (ethyl acetate: hexane = 5: 1) to obtain Compound CM3 (123.4 mg, yield 96%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、ビス（ジベンジリデンアセトン）パラジウム（０）（Ｐｄ（ｄｂａ）_２、５．８ｍｇ、１０μｍｏｌ、２ｍｏｌ％）、２−（ジシクロヘキシルホスフィノ）−２’，４’，６’−トリ−イソプロピル−１，１’−ビフェニル（Ｘｐｈｏｓ、９．５ｍｇ、２０μｍｏｌ、４ｍｏｌ％）及び１，３−ジメチル−２−イミダゾリジオン（ＤＭＩ、０．３０ｍＬ）を加え、１時間攪拌した。その後、そこに上記方法２で合成した化合物ＣＭ１（１３１．７ｍｇ、０．５５ｍｍｏｌ）、化合物Ｓ４（７０．０μＬ、０．５０ｍｍｏｌ）、フッ化カリウム（ＫＦ、１４５．３ｍｇ、２．５０ｍｍｏｌ）及びＤＭＩ（０．２ｍＬ）を加え、１００℃で１８時間加熱攪拌した。得られた反応溶液をジクロロメタンで希釈し、フロリジルを用いて濾過した。得られた濾液を減圧留去し、室温で真空乾燥することにより粗生成物を得た。この粗生成物をクロロホルムで再結晶を行い、得られた結晶を濾過により分離し、化合物ＣＭ４（８９．０ｍｇ）を得た。別途、得られた濾液を薄層カラムクロマトグラフィー（酢酸エチル：ヘキサン＝５：１）で精製し、化合物ＣＭ４（６５．７ｍｇ）を得た。得られたサンプル２点を合わせ、化合物ＣＭ４（１５４．７ｍｇ、合計収率９９％）を得た。 [Example 3] (Synthesis of Compound CM4)
Compound CM4 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and bis (dibenzylideneacetone) palladium (0) (Pd (dba) ₂ 5.8 mg, 10 μmol, 2 mol%), 2- (dicyclohexyl) was added to the reaction vessel heated and dried. Phosphino) -2 ′, 4 ′, 6′-tri-isopropyl-1,1′-biphenyl (Xphos, 9.5 mg, 20 μmol, 4 mol%) and 1,3-dimethyl-2-imidazolidione (DMI, 0.30 mL) was added and stirred for 1 hour. Thereafter, there was compound CM1 (131.7 mg, 0.55 mmol), compound S4 (70.0 μL, 0.50 mmol), potassium fluoride (KF, 145.3 mg, 2.50 mmol) and DMI synthesized by the above-mentioned method 2. (0.2 mL) was added, and the mixture was stirred with heating at 100 ° C. for 18 hours. The resulting reaction solution was diluted with dichloromethane and filtered using florisil. The obtained filtrate was distilled off under reduced pressure, and the crude product was obtained by vacuum drying at room temperature. This crude product was recrystallized from chloroform, and the obtained crystals were separated by filtration to obtain Compound CM4 (89.0 mg). Separately, the obtained filtrate was purified by thin layer column chromatography (ethyl acetate: hexane = 5: 1) to obtain Compound CM4 (65.7 mg). The obtained two samples were combined to obtain Compound CM4 (154.7 mg, total yield 99%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、ビス（１，５−シクロオクタジエン）ニッケル（０）（Ｎｉ（ｃｏｄ）_２、６．９ｍｇ、２５μｍｏｌ、５ｍｏｌ％）、１，３−ビス（２，６−ジイソプロピルフェニル）イミダゾリニウムクロリド（ＳＩＰｒ・ＨＣｌ、１０．７ｍｇ、２５μｍｏｌ、５ｍｏｌ％）、ｔｅｒｔ−ブトキシカリウム（ＫＯ^ｔＢｕ、２．８ｍｇ、２５μｍｏｌ、５ｍｏｌ％）及びシクロペンチルメチルエーテル（ＣＰＭＥ、０．３０ｍＬ）を加え、１００℃で１時間攪拌した。得られた溶液を室温まで冷却した後、化合物ＣＭ２（２１５．３ｍｇ、０．５０ｍｍｏｌ）、酢酸ナトリウム（ＮａＯＡｃ、６９．７ｍｇ、０．８５ｍｍｏｌ）及びＣＰＭＥ（０．２ｍＬ）を加え、１００℃で４６時間攪拌した。得られた反応溶液に水を加え反応停止させた。その後、ジクロロメタン（２０ｍＬ）を用いて水層を３回抽出し、有機層を飽和塩化ナトリウム水溶液で洗浄した。得られた有機層を無水硫酸マグネシウム（ＭｇＳＯ_４）で脱水後、濾過した。得られた濾液を減圧留去し、室温で真空乾燥することで、粗生成物（１５８．５ｍｇ）を得た。この粗生成物をジエチルエーテル（Ｅｔ_２Ｏ、１ｍＬ）に溶解させ、メタノール（ＭｅＯＨ）に滴下し固体を沈殿させた。得られた固体を濾取し、高分子化合物Ｐ１（７８．０ｍｇ）を得た。高分子化合物Ｐ１は、ＭＡＬＤＩ ＴＯＦ−ＭＡＳＳ測定により、１０量体（ｎ＝１０）までの成分を確認した。得られた高分子化合物Ｐ１のＧＰＣ装置で測定されたポリスチレン換算のＭｎは２，３００、Ｍｗは３，８５０であった。 [Example 4] (Synthesis of polymer compound P1)
Polymer compound P1 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and the heat-dried reaction vessel was charged with bis (1,5-cyclooctadiene) nickel (0) (Ni (cod) ₂ 6.9 mg, 25 μmol, 5 mol%), 1,3-bis (2,6-diisopropylphenyl) imidazolinium chloride (SIPr · HCl, 10.7 mg, 25 μmol, 5 mol%), tert-butoxy potassium (KO ^t Bu, 2.8 mg, 25 μmol, 5 mol%) And cyclopentyl methyl ether (CPME, 0.30 mL) was added, and the mixture was stirred at 100 ° C. for 1 hour. After cooling the resulting solution to room temperature, compound CM2 (215.3 mg, 0.50 mmol), sodium acetate (NaOAc, 69.7 mg, 0.85 mmol) and CPME (0.2 mL) were added and Stir for hours. Water was added to the obtained reaction solution to stop the reaction. Thereafter, the aqueous layer was extracted three times using dichloromethane (20 mL), and the organic layer was washed with a saturated aqueous sodium chloride solution. The obtained organic layer was dehydrated over anhydrous magnesium sulfate (MgSO ₄ ) and then filtered. The obtained filtrate was distilled off under reduced pressure and vacuum dried at room temperature to obtain a crude product (158.5 mg). This crude product was dissolved in diethyl ether (Et ₂ O, 1 mL) and added dropwise to methanol (MeOH) to precipitate a solid. The obtained solid was collected by filtration to obtain polymer compound P1 (78.0 mg). The high molecular compound P1 confirmed the component to a 10-mer (n = 10) by the MALDI TOF-MASS measurement. Polystyrene conversion Mn measured by the GPC apparatus of the obtained high molecular compound P1 was 2,300, and Mw was 3,850.

化合物ＣＭ１に代えて化合物Ｓ１を使用した以外は、実施例２と同様にして反応を行った。化合物ＣＭ３のＮＭＲ収率は４％だった。 [Comparative Example 1] (Synthesis of Compound CM3)
Compound CM3 was synthesized according to the following scheme.

The reaction was performed in the same manner as in Example 2 except that the compound S1 was used instead of the compound CM1. The NMR yield of compound CM3 was 4%.

化合物ＣＭ２に代えて化合物Ｓ２（１７９．６ｍｇ、０．５０ｍｍｏｌ）を使用した以外は、実施例４と同様にして反応を行った。得られた生成物を^１Ｈ ＮＭＲで測定したところ、実施例４で合成した高分子化合物Ｐ１で検出されたピークは確認されなかった。 [Comparative Example 2] (Synthesis of polymer compound P1)
Polymer compound P1 was synthesized according to the following scheme.

The reaction was performed in the same manner as in Example 4 except that the compound S2 (179.6 mg, 0.50 mmol) was used instead of the compound CM2. When the obtained product was measured by ¹ H NMR, the peak detected in the polymer compound P1 synthesized in Example 4 was not confirmed.

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、化合物Ｓ５（Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン、７．８１ｇ、３０．０ｍｍｏｌ）及びＴＨＦ（８０ｍＬ）を加え、−７８℃に冷却した。その後、そこにｎ−ＢｕＬｉ（２．６５Ｍ、２６．８ｍＬ、７２．０ｍｍｏｌ）を滴下し、５時間攪拌した。得られた反応溶液にＴＭＳＣｌ（１０．４ｍＬ、１２０ｍｍｏｌ）を滴下した後、徐々に昇温し、室温で１４時間攪拌した。得られた反応溶液を減圧留去し、熱ヘキサンで溶解させた後、濾過により沈殿物を取り除いた。得られた濾液を減圧留去し、化合物ＣＭ５（８．６４ｇ、２１．０ｍｍｏｌ、収率７０％）を得た。 [Example 5] (Synthesis of Compound CM5)
Compound CM5 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and the reaction vessel dried by heating was charged with compound S5 (N, N′-diphenyl-1,4-phenylenediamine, 7.81 g, 30.0 mmol) and THF (80 mL). In addition, it was cooled to -78 ° C. Thereafter, n-BuLi (2.65 M, 26.8 mL, 72.0 mmol) was added dropwise thereto and stirred for 5 hours. After TMSCl (10.4 mL, 120 mmol) was added dropwise to the obtained reaction solution, the temperature was gradually raised and the mixture was stirred at room temperature for 14 hours. The obtained reaction solution was distilled off under reduced pressure, dissolved in hot hexane, and then the precipitate was removed by filtration. The obtained filtrate was distilled off under reduced pressure to obtain Compound CM5 (8.64 g, 21.0 mmol, yield 70%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、Ｐｄ（ｄｂａ）_２（２．９ｍｇ、５．０μｍｏｌ、１ｍｏｌ％）、Ｘｐｈｏｓ（４．８ｍｇ、１０μｍｏｌ、２ｍｏｌ％）、ＤＭＩ（０．５０ｍＬ）、化合物ＣＭ５（２０１．４ｍｇ、０．５０ｍｍｏｌ）、化合物Ｓ６（２３５．５ｍｇ、１．５０ｍｍｏｌ）、フッ化セシウム（ＣｓＦ、２２７．９ｍｇ、１．５０ｍｍｏｌ）及びＤＭＩ（０．５０ｍＬ）を加え、１００℃で１４時間加熱攪拌した。得られた反応溶液をジクロロメタンで希釈し、フロリジルを用いて濾過した。得られた濾液を減圧留去し、室温で真空乾燥することにより粗生成物を得た。この粗生成物をクロロホルムで再結晶を行い、得られた結晶を濾過により分離し、化合物ＣＭ６（２０１．６ｍｇ、収率９８％）を得た。 [Example 6] (Synthesis of Compound CM6)
Compound CM6 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and Pd (dba) ₂ (2.9 mg, 5.0 μmol, 1 mol%), Xphos (4.8 mg, 10 μmol, 2 mol%), DMI was added to the heat-dried reaction vessel. (0.50 mL), compound CM5 (201.4 mg, 0.50 mmol), compound S6 (235.5 mg, 1.50 mmol), cesium fluoride (CsF, 227.9 mg, 1.50 mmol) and DMI (0.50 mL) ) And heated and stirred at 100 ° C. for 14 hours. The resulting reaction solution was diluted with dichloromethane and filtered using florisil. The obtained filtrate was distilled off under reduced pressure, and the crude product was obtained by vacuum drying at room temperature. The crude product was recrystallized from chloroform, and the obtained crystals were separated by filtration to obtain Compound CM6 (201.6 mg, yield 98%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、Ｐｄ（ｄｂａ）_２（２．９ｍｇ、５．０μｍｏｌ、１ｍｏｌ％）、Ｘｐｈｏｓ（４．８ｍｇ、１０μｍｏｌ、２ｍｏｌ％）、ＣｓＦ（２２７．９ｍｇ、３．０ｅｑ、１．５０ｍｍｏｌ）、ＤＭＩ（０．５０ｍＬ）、Ｓ７（２７７．５ｍｇ、０．５０６０ｍｍｏｌ）及びＣＭ５（２０３．８ｍｇ、０．５０６０ｍｍｏｌ）を加え、１００℃で２２時間攪拌した。反応溶液をクロロホルムで希釈し、メタノール（ＭｅＯＨ）に滴下し沈殿物をろ過し、高分子化合物Ｐ２（２９６．０ｍｇ）を得た。得られた高分子化合物Ｐ２のＧＰＣ装置で測定されたポリスチレン換算のＭｎは５，９５０、Ｍｗは１２，０００であった。 [Example 7] (Synthesis of polymer compound P2)
Polymer compound P2 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and Pd (dba) ₂ (2.9 mg, 5.0 μmol, 1 mol%), Xphos (4.8 mg, 10 μmol, 2 mol%), CsF (227.9 mg, 3.0 eq, 1.50 mmol), DMI (0.50 mL), S7 (277.5 mg, 0.5060 mmol) and CM5 (203.8 mg, 0.5060 mmol) were added and at 100 ° C. for 22 hours Stir. The reaction solution was diluted with chloroform, added dropwise to methanol (MeOH), and the precipitate was filtered to obtain polymer compound P2 (296.0 mg). Polystyrene conversion Mn measured by the GPC apparatus of the obtained high molecular compound P2 was 5,950, and Mw was 12,000.

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、化合物Ｓ８（アニリン、２．７９ｇ、３０．０ｍｍｏｌ）及びＴＨＦ（３０ｍＬ）を加え、−７８℃に冷却した。
その後、そこにｎ−ＢｕＬｉ（２．５６Ｍ、２５．０ｍＬ、６６.０ｍｍｏｌ）を滴下し、２時間攪拌した。得られた反応溶液にＴＭＳＣｌ（１０．４ｍＬ、１２０．０ｍｍｏｌ）を滴下した後、徐々に昇温し、室温で１４時間攪拌した。得られた反応溶液を減圧留去し、熱ヘキサンで溶解させた後、濾過により沈殿物を取り除いた。得られた濾液を減圧留去し、化合物ＣＭ７（７．０４ｇ、２９．６ｍｍｏｌ、収率９９％）を得た。 [Reaction Example 5] (Synthesis of Compound CM7)
Compound CM7 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and compound S8 (aniline, 2.79 g, 30.0 mmol) and THF (30 mL) were added to the heat-dried reaction vessel and cooled to -78 ° C.
Then, n-BuLi (2.56M, 25.0 mL, 66.0 mmol) was dripped there, and it stirred for 2 hours. TMSCl (10.4 mL, 120.0 mmol) was added dropwise to the obtained reaction solution, the temperature was gradually raised, and the mixture was stirred at room temperature for 14 hours. The obtained reaction solution was distilled off under reduced pressure, dissolved in hot hexane, and then the precipitate was removed by filtration. The obtained filtrate was distilled off under reduced pressure to obtain Compound CM7 (7.04 g, 29.6 mmol, yield 99%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、Ｐｄ（ｄｂａ）_２（２．９ｍｇ、５．０μｍｏｌ、１ｍｏｌ％）、Ｘｐｈｏｓ（４．８ｍｇ、１０μｍｏｌ、２ｍｏｌ％）、ＤＭＩ（０．５０ｍＬ）、化合物ＣＭ７（１３６．７ｍｇ、０．５８ｍｍｏｌ）、化合物Ｓ３（２５６．５ｍｇ、１．５０ｍｍｏｌ）、ＣｓＦ（２２７．９ｍｇ、１．５０ｍｍｏｌ）及びＤＭＩ（０．５０ｍＬ）を加え、１００℃で１４時間加熱攪拌した。得られた反応溶液をジクロロメタンで希釈し、フロリジルを用いて濾過した。得られた濾液を減圧留去し、室温で真空乾燥することにより粗生成物を得た。この粗生成物をクロロホルムで再結晶を行い、得られた結晶を濾過により分離し、化合物ＣＭ８（１４５．１ｍｇ、収率９８％）を得た。 [Example 8] (Synthesis of Compound CM8)
Compound CM8 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and Pd (dba) ₂ (2.9 mg, 5.0 μmol, 1 mol%), Xphos (4.8 mg, 10 μmol, 2 mol%), DMI was added to the heat-dried reaction vessel. (0.50 mL), Compound CM7 (136.7 mg, 0.58 mmol), Compound S3 (256.5 mg, 1.50 mmol), CsF (227.9 mg, 1.50 mmol) and DMI (0.50 mL) were added, The mixture was heated and stirred at 100 ° C. for 14 hours. The resulting reaction solution was diluted with dichloromethane and filtered using florisil. The obtained filtrate was distilled off under reduced pressure, and the crude product was obtained by vacuum drying at room temperature. The crude product was recrystallized from chloroform, and the obtained crystals were separated by filtration to obtain Compound CM8 (145.1 mg, yield 98%).

反応容器内の気体をアルゴンガスで置換し、加熱乾燥した反応容器に、Ｐｄ（ｄｂａ）_２（２．９ｍｇ、５．０μｍｏｌ、１ｍｏｌ％）、Ｘｐｈｏｓ（４．８ｍｇ、１０μｍｏｌ、２ｍｏｌ％）、ＣｓＦ（２２７．９ｍｇ、３．０ｅｑ、１．５０ｍｍｏｌ）、ＤＭＩ（０．５０ｍＬ）、Ｓ７（２７４．５ｍｇ、０．５００５ｍｍｏｌ）及びＣＭ７（１１８．８ｍｇ、０．５００４ｍｍｏｌ）を加え、１００℃で２２時間攪拌した。反応溶液をクロロホルムで希釈し、メタノール（ＭｅＯＨ）に滴下し沈殿物をろ過し、高分子化合物Ｐ３（２０２．９ｍｇ）を得た。得られた高分子化合物Ｐ３のＧＰＣ装置で測定されたポリスチレン換算のＭｎは４，４００、Ｍｗは９，９００であった。 [Example 9] (Synthesis of polymer compound P3)
Polymer compound P3 was synthesized according to the following scheme.

The gas in the reaction vessel was replaced with argon gas, and Pd (dba) ₂ (2.9 mg, 5.0 μmol, 1 mol%), Xphos (4.8 mg, 10 μmol, 2 mol%), CsF (227.9 mg, 3.0 eq, 1.50 mmol), DMI (0.50 mL), S7 (274.5 mg, 0.5005 mmol) and CM7 (118.8 mg, 0.5004 mmol) were added and at 100 ° C. for 22 hours Stir. The reaction solution was diluted with chloroform, added dropwise to methanol (MeOH), and the precipitate was filtered to obtain polymer compound P3 (202.9 mg). The obtained polymer compound P3 had a polystyrene-converted Mn of 4,400 and Mw of 9,900 as measured by a GPC apparatus.

Claims (8)

A polymer compound containing a structural unit represented by the formula (2), which reacts the compounds represented by the formula (1) with each other in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. Production method.

[Where,
X represents a halogen atom or a group having a sulfonate structure .
Ar ¹ is a group obtained by removing two hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding two atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding two hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group obtained by removing two hydrogen atoms from
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹ and R ¹ may be bonded directly or through a linking group to form a ring.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Wherein Ar ¹ and R ¹ represent the same meaning as described above. ] A compound represented by the formula (11) and a compound represented by the formula (12) are reacted in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less. The manufacturing method of an amine compound including manufacturing the compound represented by these.

[Where,
m represents an integer of 1 to 4.
Ar ¹¹ is a group obtained by removing m hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which m atoms are removed, and an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is removed from an aromatic amine compound which may have a substituent, wherein m hydrogen atoms on the aromatic ring are removed. Represents a group in which m hydrogen atoms have been removed.
R ¹ is a hydrogen atom, a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon which may have a substituent, or a hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent. The group which remove | excluded one hydrogen atom on a heterocyclic ring from the heterocyclic compound which may have the group or substituent except one was represented.
Ar ¹¹ and R ¹ may be directly bonded or form a ring via a linking group.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Where,
n represents an integer of 1 to 4.
Ar ¹² is a group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding n atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding n hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group in which n hydrogen atoms have been removed.
X represents a halogen atom or a group having a sulfonate structure . When there are a plurality of X, they may be the same or different. ]

[Wherein, Ar ¹¹ , Ar ¹² , R ¹ , R ^a , X, m and n represent the same meaning as described above. ] A compound represented by the formula (11) (where m = 2) and a compound represented by the formula (12) (where n = 2) are reacted to represent the formula (14). The method according to claim 2, wherein a polymer compound containing a structural unit is produced.

[In formula, Ar < ¹¹ >, Ar < ¹² > and R < ¹ > represent the same meaning as the above-mentioned. ] A compound represented by the formula (51) and a compound represented by the formula (12) are reacted in the presence of a transition metal compound and an organic solvent under a pressure of 5.5 MPa or less to formula (52) The manufacturing method of an amine compound including manufacturing the compound represented by these.

[Where,
p represents an integer of 1 to 4.
Ar ⁵¹ is a group obtained by removing p hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group in which p atoms are removed, an aliphatic unsaturated hydrocarbon which may have a substituent or a group in which an aromatic ring is optionally substituted with a group in which p hydrogen atoms on the aromatic ring are removed Represents a group in which p hydrogen atoms have been removed.
R ^a represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. A plurality of ^Ra may be the same or different. ]

[Where,
n represents an integer of 1 to 4.
Ar ¹² is a group obtained by removing n hydrogen atoms on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. A group excluding n atoms, an aliphatic amine hydrocarbon optionally having a substituent or a group excluding n hydrogen atoms on the aromatic ring from an aromatic amine compound which may have a substituent Represents a group in which n hydrogen atoms have been removed.
X represents a halogen atom or a group having a sulfonate structure . When there are a plurality of X, they may be the same or different. ]

[Wherein, Ar ¹² , Ar ⁵¹ , R ^a , X, p and n represent the same meaning as described above. ] A compound represented by the formula (51) (wherein p = 1) and a compound represented by the formula (12) (where n = 2) are reacted to represent the compound represented by the formula (53). The method of Claim 4 which manufactures the high molecular compound containing a structural unit.

[Wherein, Ar ⁵¹ and Ar ¹² represent the same meaning as described above. ] R ¹ is a group obtained by removing one hydrogen atom on an aromatic ring from an aromatic hydrocarbon which may have a substituent, or a hydrogen on a heterocyclic ring from a heterocyclic compound which may have a substituent. The method according to any one of claims 1 to 3, which is a group excluding one atom.   The method according to any one of claims 1 to 6, wherein the transition metal compound is a palladium compound or a nickel compound. The amount of transition metal compound is
With respect to the number of moles of the compound represented by formula (1), with respect to the sum of the number of moles of the compound represented by formula (11) and the compound represented by formula (12), or formula (51) And the total number of moles of the compound represented by formula (12):
The method according to any one of claims 1 to 7, which is 0.0001 to 0.1 molar equivalent.