TW201223925A - Process for production of aromatic amine compound - Google Patents

Abstract

A process for producing an aromatic amine compound, which comprises reacting an aromatic halide, an amine compound and an alkali metal alkoxide with one another in the presence of a compound having a trivalent phosphorous atom and a nickel halide.

Description

201223925 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a process for producing an aromatic amine compound. [Prior Art] The aromatic amine compound can be used as a compound of a pharmaceutical, a pesticide, a liquid crystal material, an organic electroluminescence (Organic Electro-Luminescence) material, and the like as a synthetic intermediate. In Adv. Synth. Catal. 2006, 348, 21 97-2202 Table 2. Entry 6 is described in the presence of piperidinecarboxylic acid and copper iodide, with bromobenzene and 2,6-dimethylaniline and potassium carbonate. Carry out a reaction to produce the following formula

A method of expressing an aromatic amine compound. SUMMARY OF THE INVENTION The present invention provides a method for producing an aromatic amine compound which reacts an aromatic halide, an amine compound and an alkali metal alkoxide in the presence of a compound having a trivalent phosphorus atom and a nickel halide. &lt;2&gt; The manufacturing method described in <1> by mixing a compound having a trivalent phosphorus atom, a nickel halide, an aromatic halide, an amine compound, and an alkali metal alkoxide; -5- 201223925 &lt;3&gt;&lt;1&gt; by reacting a compound having a trivalent phosphorus atom with a nickel halide, and mixing the obtained mixture with an aromatic halide, an amine compound, and an alkali metal alkoxide to carry out a reaction &lt;2&gt; The production method described; <4> An aromatic halide is a formula (1) RHx)n (1) (wherein R1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or may have The aromatic heterocyclic group of 5 to 30 membered rings of the substituent, each independently of X, is a chlorine atom, a bromine atom or an iodine atom, and η is 1, 2 or 3). The amine compound is a compound of the formula (2) (R 2 ^ N ^ H) m (2) (wherein R 2 is each independently, a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or a 5 to 30 member ring which may have a substituent The heterocyclic group, m is an integer of 1 to 3. When m is 1, two R2 groups may bond to each other to form a nitrogen-containing ring together with a nitrogen atom, and the aromatic amine compound is a formula (3) (1)q. ——R1 -N—(R2) 3-m (8)m-l (3) η—q (wherein X, R1, R2, m and η have the same meaning as above. q is x bonded to R1

The substitution number of S -6 - 201223925, n-q is an integer of 1 to 3). The production method according to any one of <1> to <3>, wherein the compound halide is a formula (1-1) R1 - X (1-1) (wherein R1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or an aromatic heterocyclic group of 5 to 30 membered rings which may have a substituent. X is a chlorine atom, a bromine atom or an iodine atom. (2) (R2tN+H)ra (2) (wherein R2 is each independently a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or a heterocyclic group of a 5 to 3 member ring which may have a substituent. m An integer of 1 to 3 'm is 1'. 2 R2 may mutually bond with a nitrogen atom to form a nitrogen-containing ring. The compound represented by 〇, the aromatic amine compound is of the formula (3-1) (Rl) pT (R2)- (3-1)

(8) OTP (wherein, R1, R2 and m have the same meanings as described above. p is the substitution number of R1 bonded to the nitrogen atom, and m-p is an integer of 0 to 2). The production method according to any one of <1> to &lt;3&gt;; -7- 3 201223925 &lt;6&gt; aromatic halide is of the formula (ll) R1 - X d-ι) In the formula, R1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or an aromatic heterocyclic group having 5 to 30 member rings which may have a substituent. X is a chlorine atom, a bromine atom or a bowl atom). The amine compound is a compound of the formula (2-1) (R2-)^-NH (2-1) (wherein R2 is each independently, and is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or a 5~ which may have a substituent a 30-membered ring heterocyclic group. m is an integer of 1 to 3, and 2 R2 may be bonded to each other to form a nitrogen-containing ring together with a nitrogen atom). The compound represented by the aromatic amine compound is of the formula (3-2)

Rl N—(r2) 2 (3_2) (wherein R1 and R2 have the same meaning as described above). The production method according to any one of <1> to <3>, wherein the compound having a trivalent phosphorus atom is a trialkylphosphine, a 1,1'-double (two) At least selected from the group consisting of phenylphosphino)ferrocene, 1,1'-bis(dicyclohexylphosphino)ferrocene and 1,1'-bis(diisopropylphosphino)ferrocene A production method according to any one of <1> to <6>, or the like.

S-8 - 201223925 BEST MODE FOR CARRYING OUT THE INVENTION The present invention is an aromatic amine compound which reacts an aromatic halide, an amine compound and an alkali metal alkoxide in the presence of a compound having a trivalent phosphorus atom and a nickel halide. Manufacturing method. The aromatic halide may, for example, be a compound in which one or more hydrogen atoms of an aromatic group having an aromatic hydrocarbon having 6 to 30 carbon atoms which may have a substituent are substituted by a halogen atom, and 5 to which a substituent may be substituted. A compound in which one or more hydrogen atoms contained in an aromatic group of an aromatic heterocyclic compound of a 30-membered ring is substituted with a halogen atom. Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom. Specific examples of the aromatic halide include, for example, the formula (1) ΚΗΧ) π (1) (wherein R1 is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or 5 to 30 members which may have a substituent The aromatic heterocyclic group of the ring, each independently of X, is a chlorine atom, a bromine atom or an iodine atom, and η is 1, 2 or 3). The compound represented by the formula (1) wherein η is 1 or 2 is preferred. The aromatic hydrocarbon group means a part of a hydrogen atom contained in the aromatic hydrocarbon which becomes a bond. The aromatic hydrocarbon group may have a condensed ring structure. It is preferred to use an aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon constituting the aromatic hydrocarbon group include benzene, biphenyl, naphthalene, anthracene, anthracene and phenanthrene. In terms of aromatic hydrocarbon group, -9 - 201223925 can be exemplified by phenyl, biphenyl, naphthyl, anthracenyl, fluorenyl, phenanthryl, phenylenediyl, naphthyldiyl, anthracenyl, fluorenyl, phenanthrenyl , benzotriyl, naphthyltriyl, ruthenium, decyl and phenanthrenyl. The aromatic heterocyclic group is a group in which a part of a hydrogen atom contained in the aromatic heterocyclic compound becomes a bond. The hetero atom contained in the aromatic heterocyclic group may, for example, be an oxygen atom, a sulfur atom or a nitrogen atom. The aromatic heterocyclic group may have a condensed ring structure. It is preferred to use an aromatic heterocyclic group of 5 to 6 membered rings. Examples of the aromatic heterocyclic compound constituting the aromatic heterocyclic group include furan, thiophene, pyrrole, pyridine, pyrimidine, quinoline, isoquinoline and quinoxaline. Examples of the aromatic heterocyclic group include a furyl group, a thienyl group, a pyrrolyl group, a pyridyl group, a pyrimidinyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a furanyl group, a thiophenediyl group, and a pyrrole group. Base, pyridyldiyl, pyrimidinediyl, quinolinediyl, isopiperinediyl, salvian quinonediyl, furantriyl, thiophenetriyl, pyrrolidinyl, pyridyltriyl, pyrimidinetriyl, quinoline III Base, isoquinoxatriyl and quinoxaline triyl. The aromatic hydrocarbon group or the aromatic heterocyclic group may have a substituent which is not related to the reaction. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, a trifluoromethyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. An aryloxy group having 6 to 20 carbon atoms, a mercapto group having 2 to 20 carbon atoms, an amine group substituted with 2 hydrocarbon groups having 1 to 20 carbon atoms, and a cyano group. Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert. butyl group, pentyl group, and 2,2- Dimethylpropyl, cyclopentyl 'hexyl, cyclohexyl, heptyl, 2-methylpentyl, octyl, 2-ethylhexyl, anthracenyl, fluorenyl, undecyl, dodecyl

-10- S 201223925, thirteen base, fourteen base, fifteen base, sixteen base, seventeen base, eighteen base, nineteen base and twenty base. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group. , 2,2-dimethylpropoxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, decyloxy 'fluorenyloxy, -yloxy, twelve Alkoxy, thirteenoxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonanoyloxy and octayloxy The base is preferably an alkoxy group having 1 to 6 carbon atoms. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 4-methylphenyl group, a 2-methylphenyl group, a 1-naphthyl group, a 2-naphthyl '3-phenanthryl group, and a 2-fluorenyl group. Examples of the aryloxy group having 6 to 20 carbon atoms include a phenoxy group, a 4-methylphenoxy group, a 2-methylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and 3 An aryl group having 6 to 20 carbon atoms and an oxygen atom, such as a phenanthryloxy group or a 2-fluorenyloxy group. Examples of the fluorenyl group having 2 to 20 carbon atoms include a carbon number of 2, for example, an ethylene group, a propyl group, a butyl group, an isobutyl group, a benzamidine group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, and the like. 20 aliphatic or aromatic sulfhydryl groups. The amine group substituted with two hydrocarbon groups having 1 to 20 carbon atoms may, for example, be a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group or a dibutylamino group. Di-sec-butylamino, di-tert-butylamino, 2,2-dimethylpropylamino, 1-pyrrolyl, 1-pyrrolidinyl, 1-piperidinyl and 9-fluorene Azolyl. The aromatic hydrocarbon group which may have a substituent may, for example, be a monocyclic aromatic hydrocarbon group having 6 to 20 carbon atoms and a condensed aromatic hydrocarbon group which may have a substituent of -11 - 201223925. Specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, a 3-biphenyl group, and 4 -biphenyl, anthracenyl, 2-indenyl, 2-indenyl, 1,3-phenylene, 1,4-phenylene, 4,4,-biphenyl-1,1'-diyl , naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-2, 6-diyl, naphthalene-2,7-diyl, 9H-indole-2,7-diyl, phenanthrene-2,7-diyl, 蒽-1,4-diyl, 蒽_ 9,10-di Base, benzene-1,3,5-triyl, benzene-1,2,5-triyl, benzene-1,2,3-triyl and naphthalene-1,3,5-diyl. The aromatic heterocyclic group which may have a substituent may, for example, be a 2-furyl group, a 3-furyl group, a 2-thienyl group, a 3-thienyl group, a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. , 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-quinolinyl, 3-quinolinyl, 5-quinolinyl, 8-quinolinyl, 3-isoquinolinyl, 4-iso Quinolinyl, 5-isoquinolyl, 8-isoquinolinyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, pyridine-2,5-diyl, pyridine- 2,6-diyl, pyridine-3,5-diyl, quinoxaline-2,5-diyl, furan-2,5-diyl, thiophene-2,5-diyl, 2,2 '- Bithiophene-5,5 '-diyl, pyridine-2,6-diyl, pyridine-2,5-diyl, pyridine-3,5-diyl, pyridine-2,3-diyl, 2,2 '-bipyridyl 5,5'-diyl, pyrimidine-2,5-diyl, quinoline-2,5-diyl, sormine-5,8-diyl, quinoline-2,6-di Base, isoquinoxaline-1,4-diyl, isoquinoline-5,8-diyl, 2,1,3-benzothiadiazole-4,7-diyl'quinoxaline-5,8 - Diyl and quinoxaline _ 2,6-diyl. The aromatic halide may, for example, be a compound represented by the formula (1) of n = 1, that is, the formula (1 -1)

S -12- 201223925 R1—x (l-i) (wherein R1 and X have the same meaning as above). The compound represented. The aromatic halide may, for example, be a compound represented by the formula (1) wherein n = 2, that is, a formula (1 - 2 ) R4X) 2 (1-2) (wherein R1 and X have the same meanings as defined above. ). The compound represented. Examples of the aromatic halide include bromobenzene, hydrazine-bromoanisole, m-bromoanisole, P-bromoanisole, 0-bromotoluene, m-bromotoluene, p-bromotoluene, and 2- Bromobenzotrifluoride, 3-bromobenzotrifluoride, 4-bromobenzotrifluoride, 1-bromo-2,4-dimethoxybenzene, 5-bromo-1,2,4-tri Methylbenzene, 2-bromo-m-xylene, 2-bromo-P-xylene, 3-di-indole-xylene, 4-di-indole-xylene, 4-di-m-xylene, 5 - desert-m-xylene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromo-2-methylnaphthalene, bromo-4 -methylnaphthalene, 2-bromophenanthrene, 3-bromophenanthrene, 1-bromoindole, 2-bromoindole, 9-bromoindole, 1-bromoindole, 2-bromoindole, 2-bromoindole, 2-bromo-9 , 9-dihexyl-911-oxime, 2-bromo-9,9-dioctyl-91^芴, 4461^-butyl-2,6-dimethylbromobenzene, 2, bromoethylbenzene, 3 '-Bromoethyl benzene, 4'-bromoethyl benzene, 2'-bromobenzophenone, 3 bromobenzophenone, 4'-bromobenzophenone, Ι α- 201223925 bromo-2-phenoxy Benzobenzene, 1-bromo-3-phenoxybenzene, 1-bromo-4-phenoxybenzene, 2-bromo-indole, hydrazine-dimethylaniline, 3-bromo-indole, hydrazine-dimethylaniline 4-bromo-N,N-dimethylaniline, 3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene, 4-bromo-3-fluorotoluene, 2-bromofuran, 3-bromofuran, 2-bromothiophene, 3-bromothiophene, 2-bromo Pyridine, 3-bromopyridine, 4-bromopyridine, 2-bromoquinoline, 3-bromoquinoline, 5-bromohydrin, 8-bromoquinoline, 2-bromoquinoxaline, 5-bromoquinoxaline, Aromatic monobromide such as 6-bromohydrazone; chlorobenzene, hydrazine-chloroanisole, m-chloroanisole, p-chloroanisole, hydrazine-chlorotoluene, m-chlorotoluene, p- Chlorotoluene, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene, 5-chloro-1, 2,4-trimethylbenzene, 2-chloro-111-xylene, 2-chloro-1-xylene, 3-chloro-indole-xylene, 4-chloro-indole-xylene, 4-chloro-m- Xylene, 5-chloro-m-xylene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene, 2-chloronaphthalene, 1-chloro-2-methylnaphthalene, 1-Chloro-4-methylnaphthalene, 2-chlorophenanthrene, 3-chlorophenanthrene, 1-chloroindole, 2-chloroindole, 9-chloroindole, 1-chloroindole, 2-chloroindole, 2-chloroindole, 2,6-Dimethylchlorobenzene, 2'-chloroethylbenzene, 3'-chloroethylbenzene, 4'-chloroethylbenzene, 2'-chlorobenzophenone, 3'-chlorobenzophenone ketone , 4'-chlorobenzophenone' 1-chloro-2-phenoxybenzene, 1-chloro-3-phenoxybenzene, 1-chloro-4-phenoxybenzene, 2-chloro-indole, hydrazine - dimethylaniline, 3-chloro-indole, hydrazine-dimethylaniline, 4-chloro-indole, hydrazine-dimethylaniline, 3-chloro-4-fluorotoluene, 4-chloro-2-fluorotoluene, 4-chloro-3-fluorotoluene, 2-chlorofuran, 3-chlorofuran, 2-chlorospirol, 3-chlorothiophene, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-chloroquinoline, An aromatic monochloride such as 3-chlorosalphline, 5-chlorosporin, 8-chloroquinoline, 2-chlorosalopline, 5-chlorosalin or 6-chloroquinoxaline;

S -14- 201223925 Iodobenzene, anthraquinone-iodoanisole, m-iodoanisole, p-iodophenylmethylmethyltoluene, m-beitoluene, p-iodotoluene, .2-cup benzotrifluoride, And trifluoride, 4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxy-5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2 -Iodine-P-dimethylhydrazine-indole-xylene, 4-ya-indole-xylene, 4-iodo-m-xylene, 5-] toluene, 2-iodobiphenyl, 3-iodobiphenyl, 4 -Iodobiphenyl, 1-iodophthalene, 1-iodo-2-methylnaphthalene, 1-iodo-4-methylnaphthalene, 2-iodophenanthrene, 3-iodophenanthrenequinone, 2-iodopyrene, 9-iodine蒽, 1-iodo oxime, 2-iodo oxime, 2-iodo oxime, 2-iodo iodine, 2'-iodoethyl benzene, 3'-iodoethyl benzene, 4'-iodoethyl benzophenone, 3'-iodobenzophenone, 4'-iodobenzophenone, 1-iodobenzene, 1-moth-3-phenoxybenzene, 1-indol-4-phenoxybenzene, 2-iodine· Methylaniline, 3-iodo-N,N-dimethylaniline, 4-iodo-N,N-dimethyl, 2-iodofuran, 3-iodofuran, 2-iodothiophene, 3-iodothiophene, 2- , 3-iodopyridine, 4-iodopyridine, 2-iodoporphyrin, 3-iodoquinoline, 5-, 8-cycloproplinine, 2-iodo; quinoxaline, 5-quinoxalinoline, 6-iodine Quinoa aromatic And 1-chloro-4-iodobenzene, 1-chloro-3-iodobenzene, 1-chloro-2-iodobenzene, 1·benzene, 1-bromo-3-ylidene, 1-bromo-2-ene Benzene, 3-oxo-4-fluorotoluene, fluorotoluene, 4-iodo-3-fluorotoluene, 1-bromo-4-iodophthalene, 9-bromo-10-iodobromo-1 oxime-iodonium, 4-bromo -4 '-iodo-1,1 '-biphenyl, 4-chloro-4 '-iodo-1, 2,7-diiodo-9H-indole, 2-bromo-7-iodine-9H-indole, 2 -Bromo-9,9-diiodo-911-oxime, 2-bromo-9,9-dioctyl-7-iodo-911-oxime, 1,4-di1,4-dibromobenzene, 1,4 - two bowls of benzene, 1,3-two bowls of benzene, 1,2 - di Yao thin diiodonaphthalene, 1,4-diiodonaphthalene, 9,10-diiodofluorene, 9-bromo-10-iodoquinone; 〇-iodo 3-iodophenylbenzene, I benzene, 3-nod-m-di-2-iodonaphthalene: 1, 1-spiral, 6-dimethyl, 2,-iodo-2-phenoxy-N,N-di Alkyl aniline • Provocation is more than bromo-4-column 4-iodo-2-: -2-, -2-phenylene-7-chlorobenzene, £ ' 1,3-, 4, 4,- -15- 201223925 Dichloro-1,1'-biphenyl, 4,4'-dibromo-1,1'-biphenyl, 4,4'-diiodo-1,1'-biphenyl, 2,7-diiodo-9,9-dihexyl-9H-indole, 2,7-diiodo-9,9·dioctyl-91^-indole, 2,7-diiodo-9,9-di (12) Base-911-芴, 2-bromo-5-iodine Furan, 2-bromo-5-iodothiophene, 2,5-diiodofuran, 2,5-diiodothiophene, 2,3-diiodothiophene, 3,4-diiodothiophene, 5,5'-diiodo -2,2'-bithiophene, 2-bromo-5-iodofuran, 2-bromo-5-iodothiophene, 2,6-diiodopyridine, 2,5-diiodopyridine, 3,5-diiodopyridine , 2,3-diiodopyridine, 5,5'-diiodo-2,2'-bipyridine, 2,5-diiodopyrimidine, 6-bromo-iodoquinoline, 2,5-diiodoquinoline, 2,6-diiodoquinoline, 5,8-diiodoquinoline, 1,4-diiodoisoquinoline, 5,8-diiodoisoquinoline, 4,7-diiodo-2,1,3 An aromatic dihalide such as benzothiadiazole, 2,5-diiodoporphyrin, 2,6-diiodoquinoxaline or 5,8-diiodoquinoxaline. In the present specification, the amine compound contains ammonia. As the amine compound, for example, ammonia, a primary amine, a secondary amine, and the above-mentioned primary amine and secondary amine do not contain a halogen atom. The amine compound may, for example, be a compound of the formula (2) (R2-)^-N-(-H)ra (2) (wherein R 2 is each independently, and may be a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or may be a heterocyclic group of 5 to 30 membered rings having a substituent. m is an integer of 1 to 3, and when 111 is 1, two R 2 groups may bond each other with a nitrogen atom to form a compound represented by a nitrogen-containing ring. R2 is an aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent, and may have

-16- S 201223925 Aromatic heterocyclic group of a 5- to 30-membered ring having a substituent, an alkyl group having 1 to 30 carbon atoms which may have a substituent, or a non-aromatic group of 5 to 30 membered rings which may have a substituent The heterocyclic group is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and a carbon number of 6 to 20 which may have a substituent. Aromatic hydrocarbon groups are particularly preferred. The aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent and the aromatic heterocyclic group having 5 to 30 member rings which may have a substituent may, for example, be the same as the above R1. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, an eleven group, a dodecyl group, a thirteen group, or a fourteenth Linear, alkyl, hexadecanyl, hexadecanyl, hexadecanyl, hexyl, hexyl, etc.; isopropyl, isobutyl, sec-butyl, tert-butyl a branched alkyl group such as 2,2-dimethylpropyl, 2-methylpentyl or 2-ethylhexyl; and a cyclic alkyl group such as a cyclopentyl group or a cyclohexyl group. Examples of the non-aromatic heterocyclic group include 2-tetrahydrofuranyl, 2-tetrahydrothiophenyl, 1,4-diox-2-yl, 1,4-thiaxan-2-yl, and 1, 4-Dithiaalkyl-2-yl, 2-morpholinyl, 2-pyrrolidinyl, 2-piperidinyl, 3-pyrrolidinyl, 3-piperidinyl and 2-piperazinyl. The substituent which the alkyl group and the non-aromatic heterocyclic group may have is the same as the substituent which the aromatic hydrocarbon group and the aromatic heterocyclic group may have. In the case of R2, for example, the same as the above R1 can be mentioned. The amine compound is represented by the formula (2 -1 ) -17- 201223925 (R2 士-NH (2-1) (wherein R2 has the same meaning as described above). The compound represented is preferred, and the two R2 are the same formula (2- 1) The compound is more preferable. The amine compound is represented by the formula (2-2) R2-NH2 (2-2) (wherein R2 has the same meaning as defined above). The compound represented by 'is also preferred. For the amine compound, for example, Amine, propylamine, butyl isobutylamine, tert-butylamine, amylamine, cyclohexylamine, hexylamine, octylamine, aniline, guanidine-fluoroaniline, Hi-fluoroaniline, p-fluorine 〇-methoxyaniline, m-methoxyaniline, p-methoxyaniline, 2-amine, 3-methylaniline, 4-methylaniline, 1-naphthylaniline, 2-naphthalene, 2-amine Biphenyl, 1-aminoindole, 2-aminobiphenyl, 4-aminodiaminophenanthrene, 2-aminobenzotrifluoride, 4-aminobenzotrifluorinated benzonitrile , 4-aminobenzonitrile, 4-tert-butylaniline, 4-yl-2,6-dimethylaniline, 4'-aminoethylbenzene, 4-aminodiphenyl 3'-amine Acetylbenzene, 3-aminobenzophenone, 2'-aminoethyl phenyl benzophenone, 2-phenoxyaniline, 3-phenoxyaniline, 4-benzene , N,N-dimethyl-1,3-phenylenediamine, hydrazine, hydrazine-dimethyl-1,4-benzenediazine, 2-methylpiperazine, homopiperazine, N-methylhomopel Amine, 2,6-di-formylamine, amine, heptaniline, methylphenylaniline benzene, 9-, 2-tert-butanone, 2-aminooxyaniline, piperidine

S -18- 201223925 嚷, N-ethyl piperazine, N-ethoxycarbonyl piperazine, ... benzyl piperazine, morpholine, 2,6-dimethylmorpholine, piperidine, 2,6 _ Methylpiperidine, 3,3 dimethylpiperazine, 3,5-dimethylpiperidine '2-ethylpiperidine, pyrrolidine, 2,5-dimethyl laloryl, dimethylamine' Diethylamine, N-methylaniline, N-ethylaniline, N-methylbenzylamine, diphenylamine 'bis(4-methylphenyl)amine, N_phenyl_ 2,6- Dimethylaniline, N-phenyl_4-tert-butyl-2,6-dimethylaniline and N_phenyl-1-calylamine. The amount of the compound to be used may be adjusted depending on the number of halogen atoms contained in the aromatic halide and the number of hydrogen atoms bonded to the nitrogen atom contained in the amine compound. Specifically, the amine compound is used in an amount in which the hydrogen atom bonded to the nitrogen atom contained in the amine compound is usually in the range of 0.01 to 100 moles, relative to the halogen atom associated with the reaction of the aromatic halide. The amine compound is preferably used in an amount ranging from 0.1 to 10 moles. When the number of hydrogen atoms bonded to the nitrogen atom contained in the amine compound is 2 or more, the primary amine, the secondary amine, and the tertiary can be selectively produced by adjusting the amounts of the amine compound and the aromatic halide. amine. For example, when ammonia is used as the amine compound, one of the grades represented by Ι^-ΝΗζ can be selectively produced by using an aromatic halide represented by the formula (1-1) of 0.9 to 1.1 mol with respect to the ammonia 1 molar. The amine, which is capable of selectively producing a secondary amine represented by R^z-NH, relative to ammonia, using an aromatic halide represented by 1.8 to 2.2 moles (1-1) with respect to ammonia 1 mole. 1 mole, using the aromatic halide represented by 2.7 to 3.3 moles (1-1), can selectively produce a tertiary amine represented by &quot;hN. For nickel halide, for example, nickel fluoride (II), nickel (II) chloride -19 - 201223925 'Nickel bromide (Π) and nickel (II) iodide. Nickel halide can be anhydrate or hydrate. 2-methoxyethyl ether can also be used. Or a coordinating compound such as ethylene glycol dimethyl acid or the like is added to the nickel halide. The amount of the nickel halide used is usually in the range of 0.001 to 0.8 mol, preferably in the range of 0.001 to 0.8 mol. 〇.〇1~〇·4 mole range. When the amount of nickel halide used is 0.001 mol or more, the yield of the aromatic amine compound tends to be high, preferably 0.8 mol. In the following, a nickel halide and a compound having a trivalent phosphorus atom are easily removed, and a compound having a trivalent phosphorus atom means a compound having a trivalent phosphorus atom in the molecule (hereinafter, also referred to as "phosphorus compound". ”), preferably a compound in which a nickel atom can coordinate a phosphorus atom is more preferably a compound having one phosphorus atom in a molecule of a nickel atom-coordinated phosphorus compound, that is, a single-seat compound which can be a nickel atom. a phosphorus compound of a seat or a compound of two phosphorus atoms in a molecule of a phosphorus compound I in a nickel atom, that is, a phosphorus compound which can serve as a two-position ligand of a nickel atom. Examples of the phosphorus compound include triphenylphosphine, tri-indolyl-tolylphosphine, tri-m-tolylphosphine, tris-fluorenyltolylphosphine, stilbene (1-naphthyl)phosphine, and ginseng (P-). Methoxyphenyl)phosphine, ginseng-methoxyphenyl)phosphine, cis(pentafluorophenyl)phosphine, ginseng (P-trifluoromethylphenyl)phosphine, ginseng (4-fluorophenyl) Triarylphosphine such as phosphine, tris-2-furylphosphine; triterp-butylphosphine, tri-tert-butyl scale tetrafluoroborate, tributyl a trialkylphosphine such as a phosphine, a triethylphosphine, a tricyclohexylphosphine or a tricyclohexylamine tetrafluoroborate. A phosphorus compound which can be a single-site ligand is preferably a trialkylphosphine, and a tricyclohexylphosphine is preferred. .

S -20- 201223925 For the phosphorus compound which can be a two-position ligand, for example, the compounds represented by the following groups (A) to (E) are grouped by (a) group, (B) group, and (C) group. The compound represented is preferably a compound represented by the group (A). (A): 1,1'-bis(diphenylphosphino)ferrocene, ruthenium, bis(dicyclohexylphosphino)ferrocene, 1,1'-bis(diisopropylphosphino) Ferrocene (B): bis(dicyclohexylphosphino)methane, bis (dicyclohexyl)yl, 1,3-bis(dicyclohexylphosphino) propyl, 丨, 4_double (Dicyclohexylphosphino)butane (C): bis(diphenylphosphino)methane, iota, 2_bis(diphenylphosphino)-benzine, 1,3-bis(diphenylphosphino) Propane, hydrazine, 4_bis(diphenylphosphino)butane (D): bis(2-diphenylphosphinophenyl)ether, 9,9-dimethyl-4,5-bis(diphenyl , phosphinyl) xanthene, 4,6-bis(diphenylphosphino) phenoxazine, (E) _ 2,2'-bis(monophenyl-t-yl)-1,1'-bincayl, The amount of 2,2,-bis(-nonylphosphino)-1,1'-biphenyl, 4,12-bis(diphenylphosphino)-[2.2]-p-cyclophenone compound is relative to halogenation In the case of nickel 1 mole, it is usually in the range of 2 2 to 20 moles, preferably in the range of 丨 4 4 moles. The alkali metal of the alkali metal alkoxide may, for example, be lithium, sodium, cesium or sodium, preferably sodium. Examples of the alkoxide of the alkali metal alkoxide include methoxide, ethoxylate, propoxide, isopropoxide, butoxide, sec-butoxide, tert-butoxide, and pentyl oxidation.物,丨卜-21 - 201223925 Dimethylpropoxide, 2,2-dimethylpropane oxide, hexyl oxide, cyclohexyl oxide, heptyl oxide, octyl oxide, sulfhydryl oxide, An alkoxide having a carbon number of 1 to 12, such as a fluorenyl oxide, is preferably a tert-butoxide. The alkali metal alkoxide may, for example, be lithium methoxide, sodium methoxide, potassium methoxide, lithium tert-butoxide, sodium tert-butoxide or potassium tert-butoxide, preferably sodium. Tert-butyl oxide. The alkali metal alkoxide may be prepared using a pre-modulated alkali metal alkoxide or in a reaction system. The amount of the alkali metal alkoxide used is usually in the range of 0.5 to 10 moles, preferably 1 to 5 moles, relative to the amine compound 1 mole. When the amount of the alkali metal alkoxide used is 0. 5 or more, the yield of the aromatic amine compound tends to be high, and if it is less than 10 m, the unreacted alkali metal alkoxide after the reaction is reacted. It is preferable that it is easy to remove. The reaction of the aromatic halide, the amine compound, and the alkali metal alkoxide can be carried out, for example, by mixing an alkali metal alkoxide, a nickel halide, a phosphorus compound, an aromatic halide, an amine compound, and a solvent necessary in any order. It is preferred to carry out the reaction by mixing a compound having a trivalent phosphorus atom with a nickel halide, and then mixing the obtained mixture with an aromatic halide, an amine compound and an alkali metal alkoxide. By mixing a compound having a trivalent phosphorus atom with a nickel halide, a nickel complex is formed and the resulting nickel complex is taken out, and the extracted nickel complex is oxidized with an aromatic halide, an amine compound, and an alkali metal alkane. The mixture is mixed to make the reaction proceed well. The mixing of the compound having a trivalent phosphorus atom and the nickel halide is carried out usually at a temperature ranging from -22 to 201223925 7 8 ° C to 250 ° C for 1 minute to 2 hours. A nickel complex is usually precipitated in the mixture obtained by the mixing, for example, a nickel complex can be taken out through a furnace. The removed nickel complex can be used as it is, or washed or dried. The mixing temperature of the obtained mixture or nickel complex compound mixed with the aromatic halide, the amine compound and the alkali metal alkoxide is usually in the range of 50 t to 250 ° C, preferably 80 ° C to 200 ° C. range. The reaction is preferably carried out in an inert gas such as nitrogen or argon. The reaction can be carried out under atmospheric pressure or under reduced pressure or under pressure. Preferably at atmospheric pressure (

The reaction can be carried out under the pressure of OkPa (counting pressure) to 10 kPa (counting pressure). The reaction can be confirmed by general analysis methods such as liquid chromatography or gas chromatography, for example, an aromatic halide or When the amine compound disappears, or when it is impossible to confirm the decrease of the aromatic halide or the amine compound, the end point of the reaction is obtained. Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethylbenzene, and isopropyltoluene; ether solvents such as tetrahydrofuran and 1,4-dioxane; and dimethyl hydrazine and N-methyl. Aprotic polar solvent such as phenyl-2-pyrrolidone, N,N-dimethylformamide, hydrazine, hydrazine-dimethylacetamide, hexamethylphosphoric acid triamide; dichloromethane, dichloroethane A halogenated aliphatic hydrocarbon solvent such as an alkane or the like. These solvents may be used singly or in combination of two or more. The aromatic hydrocarbon solvent is preferred, and xylene, trimethylbenzene or isopropyltoluene is more preferred. The amount of the solvent to be used is usually in the range of 1 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 1 part by weight of the aromatic halide. -23-201223925 When the amount of the solvent used is 1 part by weight or more, the yield of the aromatic amine compound tends to be improved, and when it is 200 parts by weight or less, the aromatic amine compound after completion of the reaction tends to be easily taken out. good. When the compound represented by the formula (1) and the amine compound are used as the aromatic halide, the compound represented by the formula (2) can be used to obtain the formula (3) (X) q-R1 -N-(R2) 3-in (3) (wherein, X, R1, R2, 〇1 and 11 are synonymous with the above, q is a substitution number bonded to R^x, and nq is an integer of 1 to 2). The aromatic amine compound represented. When the compound represented by the above formula (1-1) is used as the aromatic halide, and the compound represented by the formula (2) is used as the amine compound, the formula (3 - 1 ) (R1) p - N - (R2)3-m I (3-1) (8) m-p (wherein R1, R2 and m have the same meaning as defined above. p is the substitution number of R' bonded to the nitrogen atom, and mp is an integer of 0 to 2. ) ^ The aromatic amine compound represented. The aromatic halide is a compound represented by the above formula (1-1), and the amine compound is a formula (2 -1)

S -24- 201223925 (R2士一NH (2-1) (wherein R2 has the same meaning as described above). When the compound is represented, the formula (3-2) R1 - N- (R2) 2 (3- 2) (wherein R1 and R2 have the same meanings as defined above.) The aromatic amine compound is represented by an aromatic halide which is a compound represented by the formula (1-1), and the amine compound is a formula (2-2) R2-NH2. (2-2) (wherein R2 has the same meaning as defined above). When the compound is represented, the formula (3-3) Η R1 - N - R2 (3-3) can be obtained (wherein R1 and R2 have the same meanings as described above). The aromatic amine compound represented by the formula. The aromatic halide is a compound represented by the formula (1-2), and the amine compound is a formula (2-2) -25-201223925 R2-NH2 (2-2) , R2 has the same meaning as described above. When the compound is represented, the formula (3-4) R!-fN-R2)2 (3-4) can be obtained (wherein R1 and R2 have the same meanings as defined above). The aromatic amine compound represented. The aromatic amine compound represented by the formula (3-1) wherein p is 1 and m is 2, and examples thereof include 2-methoxy-N-methylaniline and 3-methoxy-N-methylaniline. 4-methoxy-N-methylaniline, N-methyl-2-(trifluoromethyl)aniline, N-methyl-3-(trifluoromethyl)aniline, N-methyl-4-( Trifluoromethyl) aniline, 2-ethylindenyl-N-methylaniline, 3-ethylindenyl-N-methylaniline, 4-ethylindenyl-N-methylaniline, 2-(methylamino group Benzophenone, 3-(methylamino)benzophenone, 4-(methylamino)benzophenone, N-methyl-N-(2-phenoxyphenyl)amine, N-methyl-N-(3-phenoxyphenyl)amine, N-methyl-N-(4-phenoxyphenyl)amine, N-methyl-2-methylphenylamine, N_ Methyl-3-methylphenylamine, N-methyl-4-methylphenylamine, N-methyl-1-naphthylamine, N-methyl-2-naphthylamine, N-methyl 3-naphthylamine, 1-(methylamino)phosphonium, 9-(methylamino)phosphonium, 9-(methylamino)phenanthrene, 2-(methylamino)-9H-indole, Diphenylamine, N-(2-methylphenyl)aniline, N-(3-methylphenyl)aniline, N-(4-methylphenyl)aniline, N-(2-three

S -26- 201223925 fluoromethylphenyl) aniline, N-(3-trifluoromethylphenyl)aniline, N-(4-trifluoromethylphenyl)aniline, N-(2-phenoxybenzene Aniline, N-(3-phenoxyphenyl)aniline, N-(4-phenoxyphenyl)aniline, 2-phenylaminobenzophenone, 3-phenylaminodiphenyl Methyl ketone, 4-phenylaminobenzophenone, 2-(phenylamino)biphenyl, 3-(phenylamino)biphenyl, 4-(phenylamino)biphenyl, 1-( Phenylamino)naphthalene, 2-phenylaminonaphthalene, 3-(phenylamino)naphthalene, 9-(phenylamino)anthracene, 9-(phenylamino)phenanthrene, 2-(phenyl Amino)-9H-indole, 2-(methylamino)furan, 3-(methylamino)furan, 2-(methylamino)thiophene, 3-(methylamino).thiophene, 2 -(methylamino)pyridine, 3-(methylamino)pyridine, 4-(methylamino)pyridine, 2-(methylamino)pyrimidine, 2-(methylamino)quinoline, 3-(Methylamino)isoquinoline, 2-(methylamino)quinoxaline, 2-(phenylamino)furan, 3-(phenylamino)furan, 2-(phenylamine Thiophene, 3-(phenylamino)thiophene, 2-(phenylamino)pyridine, 3-(phenylamino) Pyridine, 4-(phenylamino)pyridine, 2-(phenylamino)pyrimidine, 4-(phenylamino)pyrimidine, 2-(phenylamino)quinoline, 3-(phenylamino) Isoquinoline, 2-(phenylamino)quinoxaline, 2-bromo-N-phenylaniline, 3-bromo-N-phenylaniline, 4-bromo-N-phenylaniline, 2-chloro- N-phenylaniline, 3-chloro-N-phenylaniline, 4-chloro-N-phenylaniline, 5-bromo-2-(phenylamino)pyridine 5-chloro-2-(phenylamine Pyridine, 4-bromo-2-(phenylamino)pyridine and N-(4-bromophenyl)-2-pyridinamine-27- 201223925 η is represented by formula (3) wherein η is 2 and m is 2 The aromatic amine compound may, for example, be N,N,N'-trimethyl-1,4-phenylenediamine, N,N'-dimethyl-1,2-phenylenediamine, hydrazine, hydrazine. - dimethyl-1,3-phenylenediamine, N,N'-dimethyl-1,4-phenylenediamine, N,N'-dimethyl-1,6-phenylenediamine, hydrazine, hydrazine '-Diphenyl-1,3-phenylenediamine, 叱^^'-diphenyl-1,4-phenylenediamine, :^,&gt;^-bis(4-161^-butyl-2, 6-Dimethylphenyl)-1,4-phenylenediamine, anthracene, Ν'-bis(1-naphthyl)-1,4-phenylenediamine, anthracene, Ν'-bis(2-naphthyl) -1,4-phenylenediamine, 1,4-bis(phenylamino)naphthalene, 9, 10-bis(phenylamino)anthracene, 2,7-di(phenylamino)phenanthrene, 2,7-di(phenylamino)-9Η-oxime, 2,7-di(phenylamino) )-9,9-dioctylhydrazine, 1^,:^'-dimethyl-;^&gt;^'-diphenyl-1,4-phenylenediamine, :^\'-diphenyl- 1,3-phenylenediamine, hydrazine, Ν'-diphenyl-1,4-phenylenediamine, hydrazine, hydrazine, Ν', Ν'-tetraphenyl-1,4-phenylenediamine, hydrazine, hydrazine ,Ν',Ν'-tetraphenyl- 9Η-芴- 2,7-diamine, 9,9-dioctyl-\min, chemistry, \'-tetraphenyl-911-芴-2,7- Diamine, 2-(1-pyrrolidinyl)-pyridine, 3-(1-pyrrolidinyl)-pyridine, 4-(1-pyrrolidinyl)-pyridine, hexahydro-1-(2-pyridyl) -1,4-diazepine, hexahydro-1-(3-pyridyl)-1,4-diazepine, hexahydro-1-(4-pyridyl)-1,4-diazepine, 2 -(1-piperazinyl)-pyrimidine, 4-(2-pyrimidinyl)-morpholine, 2-(4-morpholinyl)-quinoline, 3-(4-morpholinyl)-isoquinoline and 2,5-bis(methylamino)thiophene. Examples of the aromatic amine compound represented by the formula (3) other than the above include 1-(2-furyl)-piperazine, 1-(2-thienyl)-piperazine, and 4-(2-thienyl). )-morpholine, 1-(2-pyridyl)-piperazine, 1-(3-pyridyl)-piperazine, 1-(4-pyridyl)-piperazine, 4-(2-pyridyl)- Morpholine, 4 - (

S -28- 201223925 3 -pyridyl)-morpholine, 4-(4-pyridyl)-morpholine, 1-(2-pyridyl)-piperidine, 1-(3-pyridyl)piperidine and 1 - (4-pyridyl) piperidine. Examples of the compound represented by the formula (3-2) include triphenylamine, 2-diphenylaminotoluene, 3-diphenylaminotoluene, 4-diphenylaminotoluene, and tri-P. -Tolylamine, 2-methoxy-N,N-diphenyl-phenylamine, 3-methoxy-indole, fluorene-diphenyl-phenylamine, 4-methoxy-N,N-diphenyl -aniline, 2-phenoxy-N,N-diphenyl-phenylamine, 3-phenoxy-indole, fluorene-diphenyl-aniline, 4-phenoxy-indole, fluorene-diphenyl-aniline , 2-(diphenylamino)benzophenone, 3-(diphenylamino)benzophenone, 4-(diphenylamino)benzophenone, anthracene, fluorene-diphenyl -2-(trifluoromethyl)aniline, anthracene, fluorene-diphenyl-3-(trifluoromethyl)aniline, anthracene, fluorene-diphenyl-4-(trifluoromethyl)aniline, diphenyl Amino naphthalene, 9-diphenylaminopurine, 9-diphenylaminophenanthrene, 9-diphenylamino-9Η-芴, Ν,Ν-diphenyl-[1,1'-linked Phenyl]-2-amine, anthracene, fluorene-diphenyl-[1,1'-biphenyl]-3-amine, anthracene, fluorenyl-diphenyl-[1,1'-biphenyl]- 4-amine, 2-bis(phenylamino)furan, 2-di(phenylamino)thiophene, 2-di(phenylamino)pyridine, 3-di(phenylamino)pyridine 4-bis(phenylamino)pyridine, 2-bromo-indole, fluorene-diphenylaniline, 3-bromo-indole, fluorene-diphenylaniline, 4-bromo-indole, fluorene-diphenylaniline, 2-Chloro-indole, indole-diphenylaniline, 3-chloro-indole, indole-diphenylaniline, 4-chloro-indole, indole-diphenylaniline, 4'-chloro-indole, anthracene-diphenyl -[1,1'-biphenyl]-4-amine ' 4'-bromo-indole, fluorenyl-diphenyl-[1,1'-biphenyl]-4-amine, 5-bromo-indole , Ν-diphenyl-2-pyridinamine and 5-bromo-indole, fluorene-diphenyl-2-thienylamine. Among them, 4-diphenylaminotoluene, tris-tolyl-tolylamine, 2-methoxy-oxime, Ν--29- 201223925 diphenylaniline, 3-methoxy-N,N-diphenyl Aniline, 4-methoxy-N,N-diphenylaniline, 2-phenoxy-N,N-diphenylaniline, 3-phenoxy-N,N-diphenylaniline, 2-three Fluoromethyl-N,N-diphenylaniline, 3-trifluoromethyl-N,N-diphenylaniline, 4-trifluoromethyl-N,N-diphenylaniline, oxime, Ν'- Dimethyl-indole, Ν'-diphenyl-1,4-phenylenediamine, 1·diphenylaminonaphthalene, 9-diphenylaminopurine, 9-diphenylaminophenanthrene, diphenyl Amino group-9Η-芴, Ν, Ν-diphenyl-2-phenylaniline, ν, Ν-diphenyl-3-phenylaniline, anthracene, fluorene-diphenyl-4-phenylaniline, Ν,Ν'-diphenyl-1,3-phenylenediamine, anthracene, Ν'-diphenyl-1,4-phenylenediamine, anthracene, Ν'-bis(4-tert-butyl-2, 6-Dimethylphenyl)-1,4-phenylenediamine, hydrazine, hydrazine, hydrazine, Ν'-tetraphenyl-1,4-phenylenediamine, hydrazine, hydrazine, hydrazine, Ν'-four Phenyl- 9Η-芴-2,7-diamine, 9,9-dioctyl-^[小川,"'-tetraphenyl-91芴-2,7-diamine, 2-bromo-indole, Ν -diphenylaniline, 3-bromo-anthracene Ν-diphenylaniline, 4-bromo-indole, fluorene-diphenylaniline, 2-chloro-indole, fluorene-diphenylaniline, 3-chloro-indole, fluorene-diphenylaniline, 4-chloro- Ν, Ν-diphenylaniline, 4'-chloro-indole, fluorene-diphenyl-[1,1,-biphenyl]-4-amine and 4'-bromo-indole, fluorene-diphenyl- [1,1,-biphenyl]-4-amine is a solid form of the unreacted alkali metal alkoxide, nickel halide 'phosphorus compound, etc. after completion of the reaction, for example, by filtering the reaction mixture. After removing it, if necessary, after washing with water, a saturated aqueous solution of ammonium chloride or saturated brine, the aromatic amine compound can be taken out by distilling off the solvent as necessary. The extracted aromatic amine compound can also be recrystallized. Purification by general purification means such as chromatography or distillation.

S -30-201223925 [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples. The yield of the aromatic amine compound was determined by gas chromatography (GC)' by an internal standard method (internal standard material: octylbenzene). The measurement conditions are as follows. GC measuring device: manufactured by Shimadzu Corporation GC-2010 Pipe column: DB-1 manufactured by J&amp;W Company (film thickness 0.25 μηι, length 30 m, inner diameter 0.2 mm) Injection mode: split (split ratio 63)

Gasification chamber temperature: 2 50 °C Detector (FID) Temperature: 250 °C Measure the column temperature: after 10 minutes at 7 ° C, heat up to 260 ° C at 10 ° C / min, then Maintained at 260 ° C for 10 minutes [Example 1] In a reaction vessel under a nitrogen atmosphere, 1,1'-bis(diphenylphosphino)ferrocene and barium bromide in ethanol at room temperature (about Mix at 23 °c). The precipitate was filtered and dried to give dibromo[1,1'-bis(diphenylphosphino)ferrocene]nickel(II). In a glass reactor equipped with a cooling device, dibromobis(diphenylphosphino)ferrocene]nickel(II) 93 mg (0.12 mmol) and tert-butoxy sodium I73 mg were added at room temperature under argon atmosphere. (l.80 mmol), chlorobenzene 135 mg (1.20 mmol), 2,6-monomethylaniline 145 mg (1.20 mmol) 201223925 and hydrazine-xylene 3 ml. The resulting mixture was stirred under reflux for 4 hours. The reaction mixture obtained was analyzed by GC to find that N-phenyl 2,6-dimethylaniline 199 mg (yield: 84%).

Nh2 Cl - HC1 [Example 2] In a glass reactor equipped with a cooling device, dibromo[1,1,-bis(diphenyl) was added under an argon atmosphere at room temperature (about 23 ° C). Phosphinyl)ferrocene]nickel(II) 93mg (〇.12mmol), tert-butoxy sodium 173mg (1.80 mm ο 1 ), 4-bromotoluene 205mg (1.20mmol), di-p- Tolylamine 23 7 mg (1.20 mmol) and o-xylene 3 ml. The resulting mixture was stirred under reflux for 4 hours. The reaction mixture obtained was analyzed by GC, and it was found that 293 mg of tris-p-tolylamine was obtained (yield: 85%).

[Example 3] In Example 1, except that the substituted 1,1'-bis(diphenylphosphino)ferrocene was used in the same manner as in Example 1 except that tricyclohexylphosphine was used, dibromobis(tricyclic) was obtained. Hexylphosphine) Nickel (II).

S -32- 201223925 In Example 2, 'substituted dibromo^,〗, -bis(diphenylphosphino)ferrocene] Nickel (iridium) using dibromobis(tricyclohexylphosphine)nickel (Π) 94 mg The reaction was carried out in the same manner as in Example 2 except for (0.12 mmol). The obtained reaction mixture was analyzed by GC' to obtain 26 mg of tri-p-tolylamine (yield 78%). [Example 4] In a glass reactor equipped with a cooling device, 30 mg of nickel(II) bromide 2-methoxyethyl ether complex was added in an argon atmosphere at room temperature (about 23 t). 0.12 mmol, manufactured by Aldrich Co., Ltd., 1,1'-bis(diphenylphosphino)ferrocene 67 mg (0.12 mmol, manufactured by Aldrich) tert-butoxy sodium 173 mg (1.80 mmol) '4-bromo Toluene 205 mg (1.20 mmol), bis-p-tolylamine 237 mg (1.20 mmol) and o-xylene 3 ml. The resulting mixture was stirred under reflux for 4 hours. The obtained reaction mixture was analyzed by GC to give a yield of 25 mg (yield: 74%) of tris-p-tolylamine. [Example 5] The reaction was carried out in the same manner as in Example 2 except that the substituted 4-bromotoluene was used in Example 2 except that 262 mg (1.20 mmol) of 4-iodotoluene was used. The reaction mixture obtained was analyzed by G C to find that tris-P-tolylamine 2 5 6 m g (yield 74%). [Embodiment 6] -33- 201223925 In Example 4, except for the replacement,! '_Bis(diphenylphosphino)ferrocene was reacted in the same manner as in Example 4 except that tricyclohexylphosphine (〇 · 1 2 m m ο 1 ) was used. The reaction mixture obtained was analyzed by G C to give a crude product (yield: 82%) of tris-p-methylphenylamine. [Example 7] In a glass reactor equipped with a cooling device, dibromo[1,1,-bis(diphenyl) obtained in Example 1 was added under an argon atmosphere at room temperature (about 23 ° C). Radium] ferrocene] ruthenium (II) 93 mg (.0.12 mmol), tert-butoxy sodium 173 mg (1.80 mmol), 4-chlorotoluene 152 mg (1.20 mmol), di-p-tolylamine 237 mg (1.20) Methyl) and 〇-xylene 3 ml. The resulting mixture was stirred under reflux for 4 hours. The obtained reaction mixture was analyzed by GC' to obtain a tris-p-tolylamine 201 mg (yield 58%). [Example 8] In Example 1, except that 1,1'-bis(dicyclohexylphosphino)ethane was used as the substituted 1,1'-bis(diphenylphosphino)ferrocene, the same as in Example 1. This was carried out to obtain dibromo[1,2-bis(dicyclohexylphosphino)ethane]nickel (ruthenium). In a glass reactor equipped with a cooling device, dibromo[1,2-bis(dicyclohexylphosphino)ethane]nickel(II) 77 mg was added under argon at room temperature (about 23 ° C). (0·1 2mmol), tert-butoxy sodium 1 7 3 mg (

1.80 m m ο 1 ), chlorobenzene 135 mg (1.20 mmol), aniline 112 mg (1 ·20ιηηιο1) and p-isopropyltoluene 3 ml. The resulting mixture was at 1 40 ° C

S -34- 201223925 Stir for 4 hours. The reaction mixture obtained was analyzed by G C to give 176 mg (yield: 87%) of diphenylamine. [Example 9] In a glass reactor equipped with a cooling device, dibromo[l,i,-bis(diphenyl) obtained in Example 1 was added under an argon atmosphere at room temperature (about 23 ° C). Phosphino)ferrocene]nickel(II) 93mg (0.12mmol), tert-butoxy sodium 173mg (1.80mmol), 3-bromopyridine 190mg (1.2 0mm ο 1 ), xiaoxiao 620mg (7.20mmol) ) and o-xylene 3 ml. The resulting mixture was stirred under reflux for 4 hours. The obtained reaction mixture was analyzed by G C and it was found that 丨_( 3 _ pyridine) hydrazide 7 〇 mg (yield 8 7%) was obtained.

In Example 1, except for the substituted chlorobenzene 135 mg (1.20 mmol), dibromide 1.20 mmol, substituted 2,6 dimethylaniline 145 mg (12 〇mm〇1) was used to make [Example 10] 4-tert- In the same manner as in Example 1, except that butyl-2,6-dimethylaniline 2 4 〇mm〇1 was reacted, N,N,-bis(4-tert-butyl-2,6- was obtained. Dimethylphenyl)-1,4-phenylenediamine.

-35 201223925 Industrial Applicability According to the production method of the present invention, an aromatic amine compound which is industrially sufficiently yielded can be produced in a shorter period of time.

S -36-

Claims (1)

201223925 VII. Patent application scope: 1. A method for producing an aromatic amine compound, characterized in that an aromatic halide, an amine compound and an alkali metal alkoxide are present in the presence of a compound having a trivalent phosphorus atom and a nickel halide. Carry out the reaction. 2. The production method according to claim 1, wherein the reaction is carried out by mixing a compound having a trivalent phosphorus atom, a nickel halide, an aromatic halide, an amine compound, and an alkali metal alkoxide. 3. The production method according to claim 1 or 2, wherein the mixture obtained is mixed with an aromatic halide, an amine compound and an alkali metal alkoxide by mixing a compound having a trivalent phosphorus atom with a nickel halide. To carry out the reaction. 4. The production method according to any one of claims 1 to 3, wherein the aromatic halide is of the formula (1) Rl-fx)n (1) (wherein R is a carbon number which may have a substituent 6 ～3〇 of the aromatic hydrocarbon group or the aromatic heterocyclic ring of the 5~3〇 member ring which may have a substituent, the oxime is independent, and is a chlorine atom, a bromine atom (tetra) atom, η is a b 2 or 3), an amine compound (2) (R2^TN-^H)m (2) (wherein R2 is each independently a hydrocarbon having a carbon number of 1 to 30 which may have a substituent -37-201223925 or a substituent which may have a substituent a 30-membered ring heterocyclic group, m is an integer of 1 to 3, when 111 is 1, two R2 groups may be bonded to each other to form a nitrogen-containing ring together with a nitrogen atom, and the aromatic amine compound is a formula (3) (X) q-R1 -N-(R2)3-m (8)m-l (3) n_q (wherein, X, R1, R2, m and η have the same meaning as defined above, and q is the substitution number of X bonded to R1, Nq is a compound represented by an integer of 1 to 3. 5. The production method according to any one of claims 1 to 3, wherein the aromatic halide is a formula (1-1) R1 - X (1-1) (wherein R1 is a carbon which may have a substituent 6 to 30 of an aromatic hydrocarbon group or a 5- to 30-membered aromatic heterocyclic group which may have a substituent, X is a chlorine atom, a bromine atom or a selected atom), and the amine compound is a formula (2) (R2^N -{-H)m (2) (wherein R2 is each independently, and is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or a heterocyclic group of 5 to 30 member rings which may have a substituent, „! is 1 ～3的 integer S -38- 201223925 , when m is 1 'two R 2 can be bonded to each other to form a nitrogen-containing ring with a nitrogen atom), the aromatic amine compound is of the formula (3^) (R1) p ~N—(R2)3-m I (3-1) (9)nrp (wherein, R1, R2 and m have the same meanings as described above, and p is a substitution number of R1 bonded to a nitrogen atom mp is an integer of 0 to 2 6. The method according to any one of claims 1 to 3, wherein the aromatic halide is of the formula (1-1) R1 - X (1-D (wherein R1 is An aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent or may have a substituent An aromatic heterocyclic group of 5 to 30 membered rings, a chlorine atom, a bromine atom or an iodine atom), and an amine compound of the formula (2-1) (R2, a NH (2-1) (wherein, R2 each Independently, it may be a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent or a heterocyclic group of 5 to 30 member rings which may have a substituent, and m is an integer of 1 to 3 '2 R 2 may be bonded to each other with a nitrogen atom A compound represented by a nitrogen-containing ring is formed, and the aromatic amine compound is represented by the formula (3-2) -39-201223925 R1-N-(R2)2 (3-2) (wherein R1 and R2 have the same meanings as defined above) The production method according to any one of claims 1 to 6, wherein the compound having a trivalent phosphorus atom is a trialkylphosphine, a 1,1'-bis(diphenylphosphino) group. At least one compound S selected from the group consisting of ferrocene, 1,1'-bis(dicyclohexyl- ortho)ferrocene and 1,1'-bis(diisopropylphosphino)ferrocene 40- 201223925 Four designated representatives: (1) The representative representative of the case is: No (2) The representative symbol of the representative figure is a simple description: No 201223925 If the case has a chemical formula, please reveal the most obvious Feature of the present invention of the formula: S -4- None