JP5357405B2 - Method for producing aromatic amine compound - Google Patents

Description

  The present invention relates to a method for producing an aromatic amine compound, and more particularly to a method for producing an aromatic amine compound in which an amine compound and a halide are reacted using an ionic compound as one of catalysts.

  An ionic liquid (also referred to as an ionic liquid, an ionic fluid, or a room temperature molten salt) that is one form of an ionic compound is a molten salt formed by combining a cation and an anion. A characteristic of the ionic liquid is that it is in a liquid state in a wide temperature range of −50 to 400 ° C., and many that are in a liquid state at room temperature (25 ° C.) are also known.

  Such an ionic liquid exhibits high polarity based on an aprotic ionic structure and has an excellent dissolving power with respect to organic compounds and inorganic compounds. Using this property, many attempts have been made to use ionic liquids as reaction solvents for organic synthesis. When an ionic liquid is used as a reaction solvent, the solute is solvated only with ions, and thus the reaction proceeds under a completely different environment from that when water and an organic solvent are used as the reaction solvent. Some ionic liquids have the property of being hardly soluble in water and organic solvents having low polarity, and can provide an environment for multiphase reaction. Furthermore, since it has almost no volatility, it is excellent in terms of safety, and has attracted much attention as a reaction solvent in organic synthesis.

For example, Non-Patent Document 2 to Non-Patent Document 13 report examples of synthesis methods using an ionic compound as a reaction solvent. Specifically, Friedel-Craft reaction (see Non-Patent Documents 10 and 11), Diels-Alder reaction (See Non-Patent Documents 12 and 13), Suzuki-Miyaura coupling reaction, Wittig reaction, non-utilization using metal catalyst. Known are asymmetric synthesis reaction, Sonogashira coupling reaction (see non-patent document 7), Mizorogi-Heck reaction (see non-patent document 8), carbonylation reaction (see non-patent document 9), and the like.
Great Organic Chemistry, vol. 16, 52 (1959), Asakura Shoten, Organic Chemistry Course 3, 66 (1983), Maruzen, etc.) T. T. et al. Welton, Chem. ReV. 1999, 2071 J. et al. D. Holbrey, K.M. R. Seddon, Clean Prod. Proc. , 1, 1999, 223 P. Wasserscheid, et al. , Angew. Chem. Int. Ed. 2000, 39, 3772 R. Sheldon, Chem. Commun. , 2001, 399 D. Zhao, M .; Wu, Y .; Kou, E .; Min, Catal. Today, 2002, 74, 157 T. T. et al. Fukuyama, M .; Shinmen, S .; Nishitani, M .; Sato, and I.S. Ryu, 0 rg. Lett. , 4, 1691 (2002) S. Liu, T .; Fukuyama, M .; Sato, and I.S. Ryu, Synlett. , 1814 (2004) T. T. et al. Fukuyama, R .; Yamaura, and I.I. Ryu, Can. J. et al. Chem. , 83, 711 (2005) Song, C.I. E. Shim, W .; H. Roh, E .; J. et al. Choi, J .; H. Chem. Commum. 2000, 1695 J. et al. A. Boon, J. et al. A. Levisky, J. et al. L. Pflug, J. et al. S. Wilkes. J. et al. Org. Chem. 51,480 (1986) M.M. J. et al. Earle, P.M. B. McComac ,; R. Seddon, Green Chem. 1999, 1, 23; J. et al. Howart, K.M. Hanlon, D.C. Fayne, P.M. McCormac. Tetrahedron Lett. 38, 3097 (1997)

  However, as described in Non-Patent Document 1, for the synthesis of important intermediates in the field of medicine and agrochemicals and arylamines useful as electron transport materials, copper catalysts and palladium are prepared from aryl halides and amine compounds. A synthesis method using a catalyst is known, but no example of synthesis in a reaction system containing an ionic liquid or an ionic compound has been reported.

  Being able to realize organic synthesis in a reaction system containing an ionic liquid or ionic compound, it is possible to realize a synthesis having advantages different from various conventional techniques such as enabling the reuse of reaction solvents and catalysts. It is assumed that development of a method for producing an aromatic amine compound using an ionic compound is expected.

  This invention is made | formed in view of the said objective, The objective is to provide the manufacturing method of the aromatic amine compound which can be synthesize | combined with a sufficient yield using an ionic compound.

  The present inventors diligently studied a method for producing an aromatic amine compound. As a result, the inventors have found a novel method for producing an aromatic amine compound capable of synthesizing an aromatic amine compound with high yield by reacting an amine compound with a halide using a specific ionic compound and a metal compound as a catalyst.

The method for producing an aromatic amine compound according to the present invention includes a step of reacting an amine compound and a halide using a metal compound as a catalyst in the presence of a base and an ionic compound,
At least one of the amine compound and the halide contains an aryl group, and the ionic compound is a compound composed of a cation moiety containing a phosphorus atom and an anion moiety.

  In the method for producing an aromatic amine compound according to the present invention, the ionic compound is represented by the following general formula (1).

(In the formula (1), R ¹ is an aryl group or an alkyl group, A is a halogen atom or an anionic molecule, the aryl group and the alkyl group may have a substituent, and The alkyl group may have a branched chain, and a plurality of R ¹ may be the same as or different from each other.

In the method for producing an aromatic amine compound according to the present invention, the amine compound has the following general formula (2):
NH _n- (R ⁴ ) _3-n (2)
(In the formula (2), R ⁴ is an aryl group or an alkyl group, and the aryl group or the alkyl group may have a substituent, and the alkyl group has a branched chain. N is an integer of 1 or 2. A plurality of R ⁴ may be the same or different from each other.

In the method for producing an aromatic amine compound according to the present invention, the aryl halide or the alkyl halide is represented by the following general formula (3).
R ⁵ -X (3)
(In Formula (3), R ⁵ is an aryl group or an alkyl group having 1 to 8 carbon atoms, X is a halogen atom, and the aryl group and the alkyl group may have a substituent.) It is preferable that it is a compound shown by these.

  In the method for producing an aromatic amine compound according to the present invention, the ionic compound is preferably an ionic liquid. In the present invention, the ionic liquid is sometimes referred to as an ionic liquid, an ionic fluid, or a room temperature molten salt, and is a molten salt formed by combining a cation moiety and an anion moiety. That is, it is a liquid (molten) compound in a wide temperature range of −50 to 400 ° C.

  In the method for producing an aromatic amine compound according to the present invention, the metal compound is preferably a compound having a transition metal element.

  In the method for producing an aromatic amine compound according to the present invention, the base is preferably a metal alkoxide.

  The method for producing an aromatic amine compound according to the present invention includes a step of reacting an amine compound containing an aryl group with a halide using an ionic compound and a metal compound as a catalyst in the presence of a base, and the ionic compound comprises: It is a compound comprising a cation moiety containing a phosphorus atom and an anion moiety.

  The method for producing an aromatic amine compound according to the present invention includes a step of reacting an amine compound and an aryl halide using a ionic compound and a metal compound as a catalyst in the presence of a base, the ionic compound comprising a phosphorus atom. It is a compound consisting of a cation moiety and an anion moiety.

  According to the present invention, an aromatic amine compound is synthesized in a high yield by reacting an amine compound and a halide using a cation compound containing a phosphorus atom and an anion site as a catalyst and a metal compound as a catalyst. A novel method for producing an aromatic amine compound can be realized.

  According to the present invention, a novel method for producing an aromatic amine compound capable of synthesizing an aromatic amine compound in a high yield is realized by reacting an amine compound with a halide using a specific ionic compound and a metal compound as a catalyst. can do.

  Hereinafter, the present invention will be described in more detail.

  The method for producing an aromatic amine compound according to the present invention includes a step of reacting an amine compound and a halide using a metal compound as a catalyst in the presence of a base and a specific ionic compound. At this time, at least one of the amine compound and the halide is a compound containing an aryl group.

(Amine compound)
As an amine compound used with the manufacturing method in this invention, a primary amine compound and a secondary amine compound can be illustrated. As the amine compound, an aliphatic amine compound or an aromatic amine compound can be used.

  Aliphatic amines are primary amines such as aliphatic primary amines such as ethylamine, propylamine, butylamine, isobutylamine, tert-butylamine, pentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine and the like. Can be exemplified.

As aromatic amines, the following general formula (2)
NH _n- (R ⁴ ) _3-n (2)
(In Formula (2), R ⁴ is an aryl group or an alkyl group, and the aryl group or alkyl group may have a substituent. N is an integer of 1 or 2. R ⁴ with each other, the compound represented by each other may be the same or different.) are preferred.

  Specifically, aniline, o-fluoroaniline, m-fluoroaniline, p-fluoroaniline, o-anisidine, m-anisidine, p-anisidine, o-toluidine, m-toluidine, p-toluidine, 2-naphthylamine, Aromatic primary amines such as 2-aminobiphenyl and 4-aminobiphenyl are listed. The secondary amines are not particularly limited, and examples thereof include piperazine, 2-methylpiperazine, homopiperazine, N-methylhomopiperazine, 2,6-dimethylpiperazine, N-methylpiperazine, and N-ethyl. Piperazine, N-ethoxycarbonylpiperazine, N-benzylpiperazine, morpholine, 2,6-dimethylmorpholine, piperidine, 2,6-dimethylpiperidine, 3,3-dimethylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, 4-piperidone cyclic secondary amines such as ethylene ketal, pyrrolidine, 2,5-dimethylpyrrolidine, dimethylamine, diethylamine, N-methylaniline optionally having a substituent on the aromatic ring, N-ethylaniline, N- Methylbenzylamine, N-methylphenethyl Non-cyclic secondary amines such as amines and diphenylamine derivatives are listed.

  In the present invention, the amine compound is 0.2 mol or more and 2.0 mol or less with respect to 1 mol of aryl halide or alkyl halide, or 0.2 mol or more with respect to 1 mol of halogen atom on the ring of aryl halide, It may be present in the reaction system in a range of 2.0 mol or less. Considering that the recovery of the unreacted amine compound becomes complicated, the range is 0.4 mol or more and 1.2 mol or less with respect to 1 mol of aryl halide, or with respect to 1 mol of halogen atom on the ring of aryl halide. It is preferably present in the reaction system in the range of 0.4 mol or more and 1.2 mol or less.

(Halide)
As the halide used in the production method according to the present invention, an aryl halide or an alkyl halide can be used. Specific examples include compounds represented by the following general formula (Y).
R ⁵ -X (3)
(In Formula (3), R ⁵ is an aryl group or an alkyl group having 1 to 8 carbon atoms, X is a halogen atom, and the aryl group and alkyl group may have a substituent.)
Examples of the aryl halide in which R ⁵ is an aryl group include the following compounds. Bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole, o-bromotoluene, m-bromotoluene, p-bromotoluene, o-bromophenol, m-bromophenol, p-bromophenol, 2- Bromobenzotrifluoride, 3-bromobenzotrifluoride, 4-bromobenzotrifluoride, 1-bromo-2,4-dimethoxybenzene, 1-bromo-2,5-dimethoxybenzene, 2-bromophenethyl alcohol, 3-bromophenethyl alcohol, 4-bromophenethyl alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene, 2-bromo-p-xylene, 3-bromo-o-xylene, 4 -Bromo-o-xylene, 4-bromo-m-xylene, 5-bromo-m-xyl Len, 1-bromo-3- (trifluoromethoxy) benzene, 1-bromo-4- (trifluoromethoxy) benzene, 2-bromobiphenyl, 3-bromobiphenyl, 4-bromobiphenyl, 4-bromo-1,2 Aryl bromides such as-(methylenedioxy) benzene, 1-bromonaphthalene, 2-bromonaphthalene, 1-bromo-2-methylnaphthalene, 1-bromo-4-methylnaphthalene;
Chlorobenzene, o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2-chloro Benzotrifluoride, 3-chlorobenzotrifluoride, 4-chlorobenzotrifluoride, 1-chloro-2,4-dimethoxybenzene, 1-chloro-2,5-dimethoxybenzene, 2-chlorophenethyl alcohol, 3 -Chlorophenethyl alcohol, 4-chlorophenethyl alcohol, 5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene, 2-chloro-p-xylene, 3-chloro-o-xylene, 4- Chloro-o-xylene, 4-chloro-m-xylene, 5-chloro-m-xyl 1-chloro-3- (trifluoromethoxy) benzene, 1-chloro-4- (trifluoromethoxy) benzene, 2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene, 2- Aryl chlorides such as chloronaphthalene, 1-chloro-2-methylnaphthalene, 1-chloro-4-methylnaphthalene;
Iodobenzene, o-iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol, p-iodophenol, 2- Iodobenzotrifluoride, 3-iodobenzotrifluoride, 4-iodobenzotrifluoride, 1-iodo-2,4-dimethoxybenzene, 1-iodo-2,5-dimethoxybenzene, 2-iodophenethyl alcohol, 3-iodophenethyl alcohol, 4-iodophenethyl alcohol, 5-iodo-1,2,4-trimethylbenzene, 2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4 -Iodo-o-xylene, 4-iodo-m-xylene, 5-iodo-m-ki Lene, 1-iodo-3- (trifluoromethoxy) benzene, 1-iodo-4- (trifluoromethoxy) benzene, 2-iodobiphenyl, 3-iodobiphenyl, 4-iodobiphenyl, 1-iodonaphthalene, 2- Aryl iodides such as iodonaphthalene, 1-iodo-2-methylnaphthalene, 1-iodo-4-methylnaphthalene;
Fluorobenzene, o-fluoroanisole, m-fluoroanisole, p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene, o-fluorophenol, m-fluorophenol, p-fluorophenol, 2- Fluorobenzotrifluoride, 3-fluorobenzotrifluoride, 4-fluorobenzotrifluoride, 1-fluoro-2,4-dimethoxybenzene, 1-fluoro-2,5-dimethoxybenzene, 2-fluorophenethyl alcohol, 3-fluorophenethyl alcohol, 4-fluorophenethyl alcohol, 5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene, 2-fluoro-p-xylene, 3-fluoro-o-xylene, 4 -Fluoro-o-xylene 4-fluoro-m-xylene, 5-fluoro-m-xylene, 1-fluoro-3- (trifluoromethoxy) benzene, 1-fluoro-4- (trifluoromethoxy) benzene, 2-fluorobiphenyl, 3-fluoro Biphenyl, 4-fluorobiphenyl, 4-fluoro-1,2- (methylenedioxy) benzene, 1-fluoronaphthalene, 2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene, 1-fluoro-4-methylnaphthalene, etc. Aryl fluorides and the like are exemplified.

  Also, 1,2-dibromobenzene, 1,3-dibromobenzene, 1,4-dibromobenzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 4,4′-dibromobiphenyl, 4,4′- Dichlorobiphenyl, 4,4′-iodobiphenyl, 1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene, 1-bromo-4-fluorobenzene, 2-bromochlorobenzene, 3-bromochlorobenzene, 4- Bromochlorobenzene, 2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride, 5-bromo-2-chlorobenzotrifluoride, 1-bromo-2,3-dichlorobenzene, 1-bromo -2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene, 2-bromo-4-fur Aryl halides having two or more halogen atoms such as rotoluene, 2-bromo-5-fluorotoluene, 3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene, 4-bromo-3-fluorotoluene are also present. It can be illustrated as an aryl halide used in the invention.

R ⁵ may be an alkyl group having 1 to 8 carbon atoms. Such alkyl halides include chloromethane, bromomethane, iodomethane, chloroethane, bromoethane, iodoethane, 1-chloropropane, 1-bromopropane, 1-iodopropane, 2-chloropropane, 2-bromopropane, 2-iodopropane, 1 -Chloro-2-methylpropane, 1-bromo-2-methylpropane, 1-iodo-2-methylpropane, 2-chloro-2-methylpropane, 2-bromo-2-methylpropane, 2-iodo-2- Methylpropane, 1-chlorobutane, 1-bromobutane, 1-iodobutane, 2-chlorobutane, 2-bromobutane, 2-iodobutane, 1-chloropentane, 1-bromopentane, 1-iodopentane, 2-chloropentane, 2-bromo Pentane, 2-iodopentane, 1- Rohekisan, 1-bromo-hexane, 1-iodo-hexane, 1-chloro-heptane, 1-bromo-heptane, 1-iodo-heptane, 1-chloro octane, 1-bromo-octane, can be exemplified 1-iodo-octane.

(Ionic compounds)
The ionic compound according to the present invention is a compound comprising a cation moiety containing a phosphorus atom and an anion moiety. Specifically, it is a compound represented by the following general formula (1).

(In the formula (1), R ¹ is an aryl group or an alkyl group, A is a halogen atom or an anionic molecule, the aryl group and the alkyl group may have a substituent, and The alkyl group may have a branched chain, and a plurality of R ¹ may be the same as or different from each other.)

When R ¹ is an alkyl group, R ¹ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, s-butyl group, n-pentyl group, n-hexyl group, n -An octyl group can be mentioned, but it is not necessarily limited to this.

When R ¹ is an aryl group, examples thereof include, but are not limited to, a phenyl group, a tolyl group, and a naphthyl group.

As the compound represented by the general formula (1), specifically, the cation moiety is a kind of triphenyl n-hexylphosphonium cation, triphenyl n-octylphosphonium cation, triphenylmethylphosphonium cation, and the anion moiety is halide ion, triflate anion, tetrafluoroborate anion, hexafluoro borate anion, nitrate ion, sulfate ^{_{ion, N (CF 3 SO 2)}} 2 -, N (CN) 2 -, C (CN) 2 -, CH An ionic compound which is ^a kind of ₃ OSO ₃ ⁻ or (C ₂ H ₅ ) ₂ PO ₄ ^— can be exemplified.

  In the production method according to the present invention, the ionic compound is preferably 0.00001 mol or more, more preferably 0.0001 mol or more and 10 mol or less, relative to the halide (or amine compound), More preferably, it is 0.0001 mol or more and 0.2 mol or less.

  The ionic compound is preferably an ionic liquid. In this case, an ionic compound can be used as a solvent. Here, the ionic liquid may be referred to as an ionic liquid, an ionic fluid, or a room temperature molten salt, and is a molten salt formed by combining a cation moiety and an anion moiety. That is, it is liquid (melted) in a wide temperature range of −50 to 400 ° C.

  The ionic compound preferably used in the present invention is triphenyl n-octylphosphonium-tetrafluoroborate, triphenyl n-octylphosphonium-hexafluorophosphate, triphenyl n-octylphosphonium-bis (trifluoromethylsulfonyl) imide, Triphenyl n-octylphosphonium-dicyanamide, triphenyl n-hexylphosphonium-tetrafluoroborate, triphenyl n-hexylphosphonium-hexafluorophosphate, triphenyl n-hexylphosphonium-bis (trifluoromethylsulfonyl) imide, triphenyl n -Hexylphosphonium-dicyanamide, tri-t-butyl-n-octylphosphonium-tetrafluoroborate, tri-t-butyl-n-octylphospho Um-hexafluorophosphate, tri-t-butyl-n-octylphosphonium-bis (trifluoromethylsulfonyl) imide, tri-t-butyl-n-octylphosphonium-dicyanamide, tri-t-butyl-n-hexylphosphonium-tetrafluoroborate , Tri-t-butyl-n-hexafluphosphonium-hexylorophosphate, tri-t-butyl-n-hexylphosphonium-bis (trifluoromethylsulfonyl) imide, tri-t-butyl-n-hexylphosphonium-dicyanamide, etc. be able to.

(Metal compound)
The metal compound used in the production method according to the present invention is a compound that can react with the ionic compound described above and exhibit a catalytic action. Specifically, a compound containing a transition metal element is preferable. As such a metal compound, Fe, Co, Ni, Cu, Zn, Ga, Ge, Ru, Rh, Pd, Ag, Cd, In, Sn, Os, Ir, Pt, Au, Hg, and Tl. Mention may be made of compounds containing at least one selected metal element. Among these, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt are preferable, Ni, Pd, and Pt are more preferable, and Pd is more preferable.

  Of the above metal elements, a palladium compound can be suitably used as the metal compound. Although it does not specifically limit as a palladium compound, For example, tetravalent palladium compounds, such as sodium hexachloropalladium (IV) acid tetrahydrate and hexachloropalladium (IV) potassium, palladium (II) chloride, bromide Palladium (II), palladium acetate (II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichloro Bivalent palladium compounds such as tetraamminepalladium (II), dichloro (cycloocta-1,5-diene) palladium (II), palladium trifluoroacetate (II), tris (dibenzylideneacetone) dipalladium 0), tris (dibenzylideneacetone) dipalladium chloroform complex (0), tetrakis (triphenylphosphine) palladium (0) 0-valent palladium compounds such as and the like.

  In the present invention, the amount of the metal compound used is not particularly limited, but is preferably 0.00001 mol (0.001 mol%) or more in terms of metal element with respect to 1 mol of aryl halide or alkyl halide. . If a palladium compound is in the said range, an aromatic amine compound can be manufactured with high conversion. Furthermore, in order to improve activity, the more preferable usage-amount of a palladium compound is 0.00025 mol (0.025 mol%) or more in conversion of palladium with respect to 1 mol of aryl halides or alkyl halides. In addition, this range is a range which can fully exhibit an effect, when economical efficiency is considered.

(reaction)
In the production method according to the present invention, the amine compound and halide are reacted in the presence of a base using an ionic compound and a metal compound as a catalyst. Specifically, an aromatic amine compound is produced according to the following reaction formula (1). In addition, although the following reaction formula (1) shows an example in which one halogen atom is substituted with an amine compound among the halogen atoms in the halide, it is not limited thereto. For example, when a halide containing two or more halogen atoms is used, an aromatic amine compound in which two or more halogen atoms in the halide are substituted with an amine compound can be produced.

(In the above reaction formula (1), R ¹ represents an aryl group or an alkyl group, R ⁴ represents an aryl group or an alkyl group, and R ⁵ represents an aryl group or an alkyl group having 1 to 8 carbon atoms. In the reaction formula (1), the aryl group or the alkyl group may have a substituent, n is 1 or 2. X + Y = n, X is 0 or 1, and Y is 1 or Note that at least one of R ⁴ and R ⁵ is an aryl group, and a plurality of R ¹ groups and R ⁴ groups may be the same as or different from each other.

  In the present invention, the base used is not particularly limited as long as it is at least one selected from inorganic bases and organic bases. As the base, a metal alkoxide is preferable. Among them, sodium methoxide, lithium methoxide, potassium methoxide, sodium ethoxide, lithium ethoxide, potassium ethoxide, sodium isopropoxide, lithium isopropoxide, potassium isopropoxide, sodium t-butoxide, lithium t-butoxide Alkali metal alkoxides such as potassium t-butoxide are more preferable, and sodium t-butoxide, lithium t-butoxide, and potassium t-butoxide are more preferable. These bases may be added to the reaction system as they are, or may be prepared in situ from an alkali metal, an alkali metal hydride, an alkali metal hydroxide and an alcohol and added to the reaction system.

  The amount of the base used is preferably 1.0 mol or more per 1.0 mol of aryl halide or alkyl halide. If the amount of the base is less than 1.0 mol, the yield of arylamines may be low. Even if the base is added in a large excess, the yield of arylamines is not changed, but the post-treatment operation after the completion of the reaction becomes complicated, so that the more preferable amount of the base is 1.0 mol or more, 3.0 The range is less than the mole.

  The reaction of the present invention is usually carried out in the presence of an organic solvent. The organic solvent used is not particularly limited as long as it does not inhibit the reaction. For example, aromatic organic solvents such as benzene, toluene and xylene, ether organic solvents such as diethyl ether, tetrahydrofuran and dioxane, acetonitrile, dimethylformamide, dimethyl sulfoxide, hexamethylphosphotriamide and the like can be mentioned. . Of these, aromatic organic solvents such as benzene, toluene and xylene are more preferable.

  Moreover, the manufacturing method concerning this invention can be performed under normal gas, inert gas atmosphere, such as nitrogen and argon, and you may carry out under pressure. In particular, it is preferably performed in an inert gas atmosphere.

  The present invention is preferably carried out at a reaction temperature in the range of 50 ° C. or higher and 200 ° C. or lower, more preferably in the range of 120 ° C. or higher and 180 ° C. or lower.

  In the present invention, the reaction time is not constant depending on the amount of aryl halide, amine compound, base, metal compound and ionic compound and the reaction temperature, but may be selected from a range of several minutes to 72 hours.

  After completion of the reaction, the desired compound can be obtained by treatment by a general method.

  According to the method for producing an aromatic amine compound according to the present invention, an amine compound and a halide are reacted with a specific ionic compound and a metal compound including a cation moiety containing a phosphorus element and an anion moiety as a catalyst. An aromatic amine compound can be produced with good yield.

  Hereinafter, the manufacturing method of the aromatic amine compound of this invention is demonstrated, referring an Example. Needless to say, the present invention is not limited to the following examples.

  In the following Examples 1 to 4, an aromatic amine compound (triaryl compound) was obtained according to the following reaction formula (2).

(In the reaction formula (2), R is an aryl group or an alkyl group, the aryl group and the alkyl group may have a substituent, and the alkyl group may have a branched chain. Good).

[Example 1]
In a 100 ml eggplant flask, 4.22 g (0.0249 mol) of diphenylamine, 4.50 g (0.0263 mol) of p-bromotoluene, 16.05 g of xylene, 4.80 g (0.0499 mol) of sodium tert-butoxide, triphenyl n -Hexylphosphonium tetrafluoroborate (TPPH-BF ₄ ) 1.03 g and palladium (II) acetate 5.6 mg (0.0249 mmol) were charged and refluxed (about 150 ° C.) under N ₂ atmosphere for 8.5 hours. Stir. At that time, tert-butyl alcohol was produced as a reaction by-product, and this alcohol was also refluxed. After the reaction, it was cooled to 70 ° C. by air cooling. Thereafter, 10.00 g of ultrapure water was charged, and further cooled to room temperature by air cooling. The reaction conversion rate at this point was 98.0% based on diphenylamine. In addition, the reaction conversion rate was performed using HPLC method (single surface) (reaction conversion rate was measured by the same method also about the following Examples and Comparative Examples).

[Example 2]
In a 100 ml eggplant flask, 4.24 g (0.0251 mol) of diphenylamine, 4.54 g (0.0265 mol) of p-bromotoluene, 15.96 g of xylene, 4.80 g (0.0499 mol) of sodium tert-butoxide, triphenyl n -Octylphosphonium tetrafluoroborate (TPPO-BF ₄ ) 1.02 g and palladium (II) acetate 6.4 mg (0.0285 mmol) were charged and refluxed (approximately 150 ° C.) under N ₂ atmosphere for 10.5 hours. Stir. At that time, tert-butyl alcohol was produced as a reaction by-product, and this alcohol was also refluxed. After the reaction, it was cooled to 70 ° C. by air cooling. Here, 10.00 g of ultrapure water was added, and further cooled to room temperature by air cooling. The reaction conversion rate at this point was 95.9% based on diphenylamine.

[Example 3]
In a 100 ml eggplant flask, 4.22 g (0.0249 mol) of diphenylamine, 5.01 g (0.0293 mol) of p-bromotoluene, 16.90 g of xylene, 4.80 g (0.0499 mol) of sodium tert-butoxide, triphenylmethyl 1.00 g of phosphonium tetrafluoroborate (TPPM-BF ₄ ) and 6.4 mg (0.0285 mmol) of palladium (II) acetate were charged, refluxed (about 150 ° C.) in an N ₂ atmosphere, and stirred for 25 hours. At that time, tert-butyl alcohol is generated as a reaction by-product, and this alcohol is also refluxed. Cooled to room temperature with air cooling. The reaction conversion rate at this point was 77.8% based on diphenylamine.

[Example 4]
In a 100 ml eggplant flask, 4.23 g (0.0250 mol) of diphenylamine, 4.86 g (0.0284 mol) of p-bromotoluene, 16.10 g of xylene, 4.80 g (0.0499 mol) of sodium tert-butoxide, triphenyl n -1.25 g of octylphosphonium bromide (TPPO-Br) and 6.2 mg (0.0276 mmol) of palladium (II) acetate were charged, refluxed (about 150 ° C) in an N ₂ atmosphere, and stirred for 9 hours. At that time, tert-butyl alcohol is generated as a reaction by-product, and this alcohol is also refluxed. After the reaction, it was cooled to 70 ° C. by air cooling. Here, 10.00 g of ultrapure water was added, and further cooled to room temperature by air cooling. The reaction conversion rate at this point was 97.0% based on diphenylamine.

  After cooling, the lower aqueous layer was removed by liquid separation, and the upper xylene layer was distilled off with an evaporator at 60 ° C. and 10 mmHg. After distilling off, 8.50 g of isopropyl alcohol was added and the refrigerator was kept for 3 days. And cooled at 0 to 5 ° C. After cooling, the precipitated black crystals were filtered and washed with 10.0 g of isopropyl alcohol.

[Comparative Example 1]
In a 100 ml eggplant flask, 4.23 g (0.0250 mol) of diphenylamine, 4.52 g (0.0264 mol) of p-bromotoluene, 15.93 g of xylene, 4.80 g (0.0499 mol) of sodium-tert-butoxide, the following general formula (4) an ionic compound having an anion portion and a cation portion indicated by (BMIm-DCA) 1.01 g, were charged palladium acetate (II) 6.6 mg (0.0294 mmol), reflux under _{N 2} atmosphere (about 150 ° C.) and stirred for 7.5 hours. Then, it cooled to room temperature by air cooling. The reaction conversion rate at this point was 0% based on diphenylamine.

  As described above, in Examples 1 to 4, the amine compound and the halide could be reacted at a high conversion rate. On the other hand, in Comparative Example 1, the conversion rate was 0%, indicating that the reaction was not good.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  Aromatic amine compounds useful as intermediates or electronic materials in the field of medicine and agrochemicals can be produced.

Claims (2)

Comprising reacting an amine compound with a halide using a metal compound as a catalyst in the presence of a base and an ionic compound,
At least one of the amine compound and the halide has an aryl group, and the ionic compound is a compound composed of a cation moiety containing a phosphorus atom and an anion moiety,
The ionic compound is an ionic liquid,
The ionic liquid is triphenyl n-hexylphosphonium tetrafluoroborate (TPPH-BF ₄ ), triphenyl n-octylphosphonium tetrafluoroborate (TPPO-BF ₄ ), triphenylmethylphosphonium tetrafluoroborate (TPPM-BF ₄ ). And selected from the group consisting of triphenyl n-octylphosphonium bromide (TPPO-Br),
The metal compound, Ri palladium compound der,
The amine compound has the following general formula (2)
NH _n- (R ⁴ ) _3-n (2)
(In Formula (2), R ⁴ is an aryl group or an alkyl group, and the aryl group or the alkyl group may have a substituent, and the alkyl group may have a branched chain. N is an integer of 1 or 2, and a plurality of R ⁴ may be the same or different from each other.
The halide is represented by the following general formula (3)
R ⁵ -X (3)
(In Formula (3), R ⁵ is an aryl group and X is a halogen atom. The aryl group may have a substituent.)
The process for producing an aromatic amine compound, comprising compounds der Rukoto shown in. The production method according to claim 1 , wherein the base is a metal alkoxide.