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WO2025115975A1 - Method for producing aromatic amino compound - Google Patents

Method for producing aromatic amino compound Download PDF

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Publication number
WO2025115975A1
WO2025115975A1 PCT/JP2024/042210 JP2024042210W WO2025115975A1 WO 2025115975 A1 WO2025115975 A1 WO 2025115975A1 JP 2024042210 W JP2024042210 W JP 2024042210W WO 2025115975 A1 WO2025115975 A1 WO 2025115975A1
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group
carbon atoms
carbon
producing
aromatic amino
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Japanese (ja)
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将人 長尾
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Nissan Chemical Corp
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Nissan Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/42—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by saturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C229/44—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton with carboxyl groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by unsaturated carbon chains
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/22—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/74—Benzo[b]pyrans, hydrogenated in the carbocyclic ring

Definitions

  • the present invention relates to a method for producing aromatic amino compounds that have at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring, and are useful as intermediates in the production of agricultural pharmaceuticals and electronic materials.
  • aromatic amino compounds can be produced by reducing aromatic nitro compounds.
  • aromatic nitro compounds that have at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a part other than the aromatic ring, the multiple bond is also reduced depending on the conditions, so it is usually difficult to reduce only the nitro group to an amino group while leaving the multiple bond intact. Therefore, methods have been sought for selectively reducing only the nitro group of an aromatic nitro compound to an amino group.
  • Patent Document 1 discloses a method for producing a substituted aromatic amino compound containing at least one carbon-carbon, carbon-nitrogen, or carbon-oxygen multiple bond in the aromatic moiety or side chain by catalytic hydrogenation of the corresponding substituted aromatic nitro compound in the presence of a modified noble metal catalyst, in which rhodium, ruthenium, iridium, platinum, or palladium having an oxidation state of less than 5 and modified with an inorganic or organic phosphorus compound is used as the noble metal catalyst.
  • Patent Document 2 proposes a method for selectively hydrogenating aromatic nitro compounds to aromatic amino compounds using a Pt/C catalyst poisoned with a trace amount of iron.
  • an object of the present invention is to provide a novel method for producing an aromatic amino compound, which is useful as a production intermediate for agricultural chemicals and electronic materials, and which can reduce an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a part other than an aromatic ring to an amino group with high selectivity and without impairing the reaction rate.
  • the present inventors have conducted intensive research and have found a method for selectively reducing only the nitro group by catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a portion other than the aromatic ring with a specific noble metal supported catalyst in the presence of a specific phosphorus compound, thereby completing the present invention. That is, the present invention has discovered that the above problems can be solved by the following configuration.
  • a method for producing an aromatic amino compound comprising catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring with a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3): P(R 1 ) 3 (1)
  • each of the multiple R 1s independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atom
  • R 4 represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 1 to 18 carbon atoms, an alkylenedioxy group having 1 to 18 carbon atoms, an arylene group having 6 to 24 carbon atoms, an arylene dioxy group having 6 to 24 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or a cycloalkylenedioxy group having 3 to 18 carbon atoms, which may have a substituent.
  • [6] The method for producing an aromatic amino compound according to any one of [1] to [5], wherein the Pt/C catalyst is an iron-poisoned Pt/C catalyst.
  • compound (DN) an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring
  • compound (DN) an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring
  • a numerical range expressed using "to” means a range including the numerical values described before and after “to” as the upper and lower limits.
  • the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages.
  • the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents a propyl group
  • Bu represents a butyl group
  • n- represents normal
  • t- represents tertiary
  • o- represents ortho
  • Cy represents a cyclohexyl group
  • Ph represents a phenyl group
  • Bn represents a benzyl group
  • Tol represents a tolyl group
  • acac represents acetylacetonate.
  • the production method of the present invention includes, for example, a method for producing an aromatic amino compound represented by the following reaction formula 1.
  • L represents a single bond or a divalent group
  • X represents CR11
  • Y represents O, NR12 or CR13R14
  • R11 , R12 , R13 and R14 each independently represent a hydrogen atom or a monovalent group, provided that R11 , R12 , R13 and R14 are not bonded to each other, and instead, X and Y may be bonded to each other as a triple bond.
  • Each of the multiple R1s is independently defined as above.
  • X and Y may combine together to form a cyclic structure such as a 5-membered or 6-membered ring.
  • cyclic structure include cyclic olefins such as cyclohexene, cyclohexadiene, pyran, dihydropyran, dihydrofuran, cyclohexen-1-one, dihydropyrrole, dihydropyridine, and tetrahydropyridine. That is, when the compound (DN) which is an aromatic nitro compound is, for example, a compound having cyclohexene as the cyclic structure, it is a compound having the following structure. (In the formula, L represents a single bond or a divalent group.)
  • Y may be bonded to a benzene ring substituted with a nitro group, and specific examples include compounds having the following structures.
  • the present invention is a method for producing an aromatic amino compound by catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring with a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3).
  • A phosphorus compound selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3).
  • the aromatic nitro compound used in the present invention is an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a portion other than the aromatic ring.
  • the aromatic nitro compound is preferably an aromatic mononitro compound or an aromatic dinitro compound.
  • an ⁇ , ⁇ -unsaturated carbonyl group is preferred.
  • Examples of aromatic nitro compounds having an ⁇ , ⁇ -unsaturated carbonyl group as a multiple bond include compounds having the following structures (I) to (III).
  • R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group
  • R 7 represents a hydrogen atom or a monovalent group
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 each independently represent a hydrogen atom or a methyl group
  • n represents an integer of 1 to 2.
  • R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group, R 7 represents a hydrogen atom or a monovalent group, and n represents an integer of 1 to 2.
  • the divalent groups in R 5 , R 6 , R 8 and R 9 include unsubstituted or fluorine-substituted alkylene groups having 1 to 20 carbon atoms.
  • alkylene groups having 1 to 20 carbon atoms -CH 2 - or -CF 2 - may be replaced with a group selected from the group consisting of -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring and a divalent heterocyclic ring (with the proviso that the groups selected from these groups are not adjacent to each other), and among these, an unsubstituted alkylene group having 1 to 6 carbon atoms (with the -CH 2 - on the side bonding to the benzene ring in the alkylene group being replaced with a group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -NH
  • the monovalent group for R 7 includes an unsubstituted or fluorine-substituted alkyl group having 1 to 20 carbon atoms.
  • -CH 2 - or -CF 2 - may be replaced with a group selected from the group consisting of -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, and a divalent heterocyclic ring (with the proviso that groups selected from these groups are not adjacent to each other), and among these, an unsubstituted alkyl group having 1 to 6 carbon atoms (with -CH 2 - in the alkyl group being replaced with a group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -NH- (with the proviso that groups selected from these groups are not adjacent to each other)) is preferred
  • the phosphorus compound used in the present invention includes at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3).
  • P(R 1 ) 3 (1) each of the multiple R 1s independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.
  • PO(R 2 ) 3 (2) In formula (2), each of the multiple R 2 's independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alken
  • R 4 represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 1 to 18 carbon atoms, an alkylenedioxy group having 1 to 18 carbon atoms, an arylene group having 6 to 24 carbon atoms, an arylene dioxy group having 6 to 24 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or a cycloalkylenedioxy group having 3 to 18 carbon atoms, which may have a substituent.
  • R 1 in the above formula (1) examples include methyl, ethyl, normal propyl (n-Pr), isopropyl (i-Pr), normal butyl (n-Bu), tertiary butyl (t-Bu), phenyl (Ph), benzyl (Bn), methoxy (OMe), ethoxy (OEt), normal propyloxy (On-Pr), normal butyloxy (On-Bu), phenoxy (OPh), and benzyloxy.
  • n-Bu, Ph , OMe, OEt, On-Bu, and OPh are preferred, and OMe and OEt are more preferred in terms of higher selectivity.
  • R2 in the above formula (2) include hydrogen, methyl, ethyl, n-Pr, i-Pr, n-Bu, t-Bu, n-octyl, cyclohexyl, Ph, p-methylphenyl, p-methoxyphenyl, benzyl, OMe, OEt, n-propyloxy, n-butyloxy, OPh, and benzyloxy. From the viewpoint of higher selectivity, hydrogen, methyl, n-Bu, n-octyl, and Ph are preferred, and hydrogen, methyl, and Ph are more preferred.
  • R3 in the above formula (3) include hydrogen, methyl, ethyl, n-Pr, i-Pr, n-Bu, t-Bu, n-octyl, cyclohexyl, Ph, p-methylphenyl, p-methoxyphenyl, benzyl, OMe, OEt, n-propyloxy, n-butyloxy, OPh, and benzyloxy. From the viewpoint of higher selectivity, methyl, ethyl, OMe, OEt, and Ph are preferred, and from the viewpoint of higher selectivity, methyl, OMe, OEt, and Ph are more preferred.
  • R 4 in the above formula (3) include methylene, ethylene, propylene, butylene, pentylene, hexylene, 1,2-phenylene, 1,3-phenylene, 2,2'-biphenylene, 2,2'-binaphthylene, 1,8-naphthylene, 1,8-(9,9-dimethyl)xanthenylene, and 1,1'-ferrocenylene.
  • methylene, ethylene, propylene, butylene, 1,2-phenylene, 2,2'-biphenylene, 2,2'-binaphthylene, 1,8-naphthylene, and 1,1'-ferrocenylene are preferred, and methylene, ethylene, propylene, butylene, and 2,2'-binaphthylene are more preferred from the viewpoint of higher selectivity.
  • R 1 , R 2 , and R 3 in the formula may have include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a phenyl group, a hydroxyl group, a methoxy group, an i-propyloxy group, a t-butyloxy group, an amino group, a dimethylamino group, a cyano group, a formyl group, a carboxy group, a sulfoxy group, a fluoro group, a chloro group, a bromo group, and an iodo group.
  • the phosphorus compound (A) include PMe3 , PEt3 , P(n-Pr) 3 , P (n-Bu) 3 , P (t-Bu) 3 , P(n- C6H13 ) 3 , P(n- C8H17 ) 3 , PCy3 , PBn3 , PPh3, P(o-Tol) 3 , P(OMe) 3 , P(OEt) 3 , P(On-Pr) 3 , P(On-Bu) 3 , P(OPh) 3 , P(OBn) 3 , P(O)(n-Bu) 3 , and P(O)Ph3 .
  • P(n-Bu) 3 , PPh 3 , P(OMe) 3 , P(OEt) 3 , P(On-Bu) 3 and P(OPh) 3 are preferred, with P(OMe) 3 and P(OEt) 3 being more preferred from the viewpoint of higher selectivity.
  • the amount of phosphorus compound (A) used is preferably 50 mol % or less, more preferably 35 mol % or less, relative to the aromatic nitro compound (DN) in terms of ease of removal after the reaction, and is preferably 5 mol % or more, more preferably 10 mol % or more in terms of excellent selectivity.
  • the amount of Pt/C catalyst used is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 20% by weight or less, more preferably 10% by weight or less, relative to the aromatic nitro compound (DN).
  • the amount of platinum supported in the Pt/C catalyst is preferably 0.5 to 5% by weight, and more preferably 1 to 5% by weight, based on the total weight of the Pt/C catalyst.
  • the Pt/C catalyst is preferably poisoned with S, Cu, V, or Fe, and more preferably poisoned with Fe.
  • the amount of Fe used for poisoning is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the Pt/C catalyst poisoned with Fe, from the viewpoint of suppressing side reactions, and is preferably 1.0% by weight or less, and more preferably 0.5% by weight or less, from the viewpoint of not reducing the catalytic activity.
  • a vanadium compound from the viewpoint of suppressing the production of azoxy compounds.
  • a vanadium compound VO(acac) 3 , VO (acac) 2 , NH4VO3 , V2O5 , VOCl3 , VCl6 , [VO(SCN) 4 ] 2- , VOSO4 , LiVO3 , NaVO3 , KVO3 , and VCl3 are preferred, and VO(acac) 2 is more preferred.
  • the amount of vanadium compound used is preferably 1.0 mol% or less relative to compound (DN), and more preferably 0.2 mol% or less.
  • the amount of vanadium compound used is 0.1 mol% or more.
  • reaction may be carried out in a solvent.
  • Any reaction solvent may be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the reaction.
  • reaction solvents that can be used include water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone)), ethers (Et 2 O, i-Pr 2 O, TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), THF (tetrahydrofuran), dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene,
  • the reaction temperature in the catalytic reduction is usually from -90°C to 200°C, preferably from 0°C to 100°C.
  • the reaction time in the catalytic reduction is usually 0.05 to 100 hours, preferably 0.5 to 20 hours, and more preferably 0.5 to 10 hours.
  • the reaction pressure during catalytic reduction is usually from normal pressure to 10 MPaG, and preferably from normal pressure to 0.8 MPaG.
  • nitro compounds used here are known compounds and can be synthesized according to known methods described in the literature.
  • 2-(3,5-dinitrobenzoyloxy)ethyl methacrylate can be reacted according to the method described in Japanese Patent No. 5560715 to obtain the compound.
  • Synthesis Examples 1-a-2 to 1-a-8 were synthesized in accordance with the method described in Synthesis Example 1-a-1, except that the type of phosphorus compound as an additive, the amount of DN-1 used, the amount of 1 wt % Pt/C catalyst poisoned with 0.2 wt % iron added, the amount of vanadium oxide bisacetylacetonate (VO(acac) 2 added, and the amount of toluene used as a solvent were changed.
  • Table 1 shows the types of additives used in Synthesis Examples 1-a-1 to 1-a-8 and Comparative Synthesis Examples, the amount of DN-1 used, the amount of 1 wt % Pt/C catalyst added, the amount of vanadium oxide bisacetylacetonate (VO(acac) 2 ) added, the amounts of toluene and ethyl acetate used as solvents, the LC relative area percentage of DA-1, the HPLC relative area percentage of the over-reduced product (DA-1'), the selectivity, and the reaction yield.
  • nitro compounds used here are known compounds and can be synthesized in accordance with known methods described in the literature.
  • (E)-4-(6-(methacryloyloxy)hexyloxy)cinnamic acid (2-(2,4-dinitrophenyl)ethyl) ester can be obtained by reacting in accordance with the method described in Japanese Patent No. 6733552.
  • (E)-4-nitrocinnamic acid ethyl ester can be a commercially available product such as that manufactured by Tokyo Chemical Industry Co., Ltd.
  • the LC relative area percentage of DA-3 was 99.5%, the reaction yield was 98%, and the over-reduced product (DA-3') was not detected.
  • the catalyst was filtered, and the residue was washed twice with THF (2.00 g). The filtrate was concentrated to 10.0 g, toluene (20.0 g) was added, and the mixture was concentrated again to 10.0 g. Heptane (10.0 g) was added, and the mixture was cooled to 0° C. The precipitated crystals were filtered, washed twice with heptane (2.00 g), and dried under reduced pressure at 40° C.
  • 4-nitrochalcone can be any commercially available product, such as that manufactured by Tokyo Chemical Industry Co., Ltd.
  • 4-Nitrobenzonitrile can be generally purchased from commercial sources (for example, from Tokyo Chemical Industry Co., Ltd.).
  • DN-6-nitro-2H-1-benzopyran used here can be reacted in accordance with the method described in Japanese Patent No. 4258658 to obtain the compound.
  • the HPLC relative area percentage of DA-6 was 99.7%, and no over-reduced product (DA-6') was detected.
  • the catalyst was filtered, and the residue was washed twice with toluene (4.00 g).
  • Acetic anhydride (2.09 g, 20.5 mmol) was added dropwise to the filtrate at 25 ° C. over 6 minutes, and then the mixture was stirred at 25 ° C. for 1 hour.
  • the compound (DN-7) used here can be obtained by reacting it according to the method described in Japanese Patent No. 5737291.
  • the HPLC relative area percentage of DA-7 was 99.9%, and the HPLC relative area percentage of the over-reduced product ((E)-DA-7', (Z)-DA-7', or DA-7") was 0.1%.
  • the catalyst was filtered, and the filter cake was washed twice with THF (3.00 g).
  • the filtrate was distilled at 50° C. to remove toluene, and 13.6 g of a solution was obtained. 12.1 g of the obtained solution was dried under reduced pressure at 100° C. to obtain a yellow glassy solid (DA-7) (yield: 2.45 g, 98.9%).

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Abstract

Provided is a new method for producing an aromatic amino compound that is useful as a production intermediate for electronic materials and pharmaceutical and agricultural chemicals, and that has, at a moiety other than an aromatic ring, at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen.　This method for producing an aromatic amino compound is characterized by catalytically reducing an aromatic nitro compound having, at a moiety other than an aromatic ring, at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen, by using a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by formula (1), phosphorus compounds represented by formula (2), and phosphorus compounds represented by formula (3).　(1): P(R1)3 (2): PO(R2)3 (3): (R3)2P-R4-P(R3)2 (The meaning of each symbol in formulae (1)-(3) is as defined in the description.)

Description

芳香族アミノ化合物の製造方法Method for producing aromatic amino compounds

　本発明は、農医薬品や電子材料の製造中間体として有用な、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族アミノ化合物の製造方法に関する。 The present invention relates to a method for producing aromatic amino compounds that have at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring, and are useful as intermediates in the production of agricultural pharmaceuticals and electronic materials.

　芳香族アミノ化合物は、芳香族ニトロ化合物を還元することで製造しうることが知られている。一方、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物を還元してアミノ化合物を製造する場合、当該多重結合も、条件によっては還元を受けることから、当該多重結合を残しながらニトロ基のみをアミノ基に還元することは、通常困難であり、芳香族ニトロ化合物のニトロ基のみを選択的にアミノ基に還元する方法が模索されてきた。 　It is known that aromatic amino compounds can be produced by reducing aromatic nitro compounds. On the other hand, when producing amino compounds by reducing aromatic nitro compounds that have at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a part other than the aromatic ring, the multiple bond is also reduced depending on the conditions, so it is usually difficult to reduce only the nitro group to an amino group while leaving the multiple bond intact. Therefore, methods have been sought for selectively reducing only the nitro group of an aromatic nitro compound to an amino group.

　このような還元反応を記載した文献として、例えば、特許文献１には、芳香族部分又は側鎖に炭素－炭素、炭素－窒素、又は炭素－酸素多重結合の少なくとも１個を含む置換芳香族アミノ化合物を、改質された貴金属触媒の存在下に、相当する置換芳香族ニトロ化合物の接触水素化により製造する方法であって、貴金属触媒として、５未満の酸化状態を有する、無機又は有機リン化合物で改質された、ロジウム、ルテニウム、イリジウム、白金又はパラジウムを用いる方法が開示されている。
　また、特許文献２では、Ｐｔ／Ｃ触媒を微量の鉄で被毒した触媒を用いて芳香族ニトロ化合物を芳香族アミノ化合物に選択的に水素化する方法が提案されている。 As an example of a document describing such a reduction reaction, Patent Document 1 discloses a method for producing a substituted aromatic amino compound containing at least one carbon-carbon, carbon-nitrogen, or carbon-oxygen multiple bond in the aromatic moiety or side chain by catalytic hydrogenation of the corresponding substituted aromatic nitro compound in the presence of a modified noble metal catalyst, in which rhodium, ruthenium, iridium, platinum, or palladium having an oxidation state of less than 5 and modified with an inorganic or organic phosphorus compound is used as the noble metal catalyst.
Furthermore, Patent Document 2 proposes a method for selectively hydrogenating aromatic nitro compounds to aromatic amino compounds using a Pt/C catalyst poisoned with a trace amount of iron.

特表２００１－５０１２０１号公報Special Publication No. 2001-501201 独国特許出願公開１０２０１１００３５９０号明細書DE 10 2011 003 590 A1

　このように、芳香族ニトロ化合物のニトロ基のみを選択的にアミノ基に還元する方法が提案されているが、芳香族ニトロ化合物のニトロ基のみをより高い選択性でアミノ基に還元し、かつ、反応速度を損なうことなく還元できる方法が要望されている。
　上記の鑑み、本発明の課題は、農医薬品や電子材料の製造中間体として有用な、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物をより高い選択率で、かつ反応速度を損なうことなくアミノ基に還元することができる芳香族アミノ化合物の新規な製造方法を提供することである。 Thus, methods for selectively reducing only the nitro group of an aromatic nitro compound to an amino group have been proposed, but there is a demand for a method for reducing only the nitro group of an aromatic nitro compound to an amino group with higher selectivity and without impairing the reaction rate.
In view of the above, an object of the present invention is to provide a novel method for producing an aromatic amino compound, which is useful as a production intermediate for agricultural chemicals and electronic materials, and which can reduce an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a part other than an aromatic ring to an amino group with high selectivity and without impairing the reaction rate.

　本発明者らはこのような状況に鑑み、鋭意検討した結果、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物を、特定のリン化合物の存在下、特定の貴金属の担持触媒で接触還元することにより、ニトロ基のみを選択的に還元する方法を見出し、本発明に至った。
　すなわち、本発明は、以下の構成により上記課題が解決できることを見出した。 In view of the above circumstances, the present inventors have conducted intensive research and have found a method for selectively reducing only the nitro group by catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a portion other than the aromatic ring with a specific noble metal supported catalyst in the presence of a specific phosphorus compound, thereby completing the present invention.
That is, the present invention has discovered that the above problems can be solved by the following configuration.

［１］　芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物を、下記式（１）で表されるリン化合物、下記式（２）で表されるリン化合物、および下記式（３）で表されるリン化合物からなる群から選択される少なくとも１種のリン化合物（Ａ）の存在下、Ｐｔ／Ｃ触媒で接触還元することを特徴とする、芳香族アミノ化合物の製造方法。
　Ｐ（Ｒ１）３　　　（１）
（式（１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　ＰＯ（Ｒ２）３　　　（２）
（式（２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　（Ｒ３）２Ｐ-Ｒ４-Ｐ（Ｒ３）２　　　（３）
（式（３）中、複数のＲ３は、それぞれ独立して、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。式（３）中、Ｒ４は炭素数１～１８のアルキレン基、炭素数１～１８のアルケニレン基、炭素数１～１８のアルキレンジオキシ基、炭素数６～２４のアリーレン基、炭素数６～２４のアリーレンジオキシ基、炭素数３～１８のシクロアルキレン基、又は炭素数３～１８のシクロアルキレンジオキシ基を表し、これらは置換基を有していても良い。）
［２］　上記リン化合物（Ａ）がＰ（ＯＭｅ）３、または、Ｐ（ＯＥｔ）３である、［１］に記載の芳香族アミノ化合物の製造方法。
［３］　上記リン化合物（Ａ）の使用量が、上記芳香族アミノ化合物に対して５～５０モル％である［１］または［２］に記載の芳香族アミノ化合物の製造方法。
［４］　上記芳香族ニトロ化合物が下記式（１）～（３）のいずれかの構造で表される［１］～［３］のいずれかに記載の芳香族アミノ化合物の製造方法。

Figure JPOXMLDOC01-appb-C000002
（式中、Ｒ５、Ｒ６、Ｒ８、Ｒ９はそれぞれ独立して単結合又は２価の基を表し、Ｒ７は水素原子又は１価の基を表し、ｎは１～２の整数を表す。）
［５］　上記Ｐｔ／Ｃ触媒における白金の担持量が、Ｐｔ／Ｃ触媒全重量に対して０．５～５ｗｔ％である［１］～［４］のいずれかに記載の芳香族アミノ化合物の製造方法。
［６］　上記Ｐｔ／Ｃ触媒が鉄で被毒されたＰｔ／Ｃ触媒である［１］～［５］のいずれかに記載の芳香族アミノ化合物の製造方法。
［７］　前記Ｐｔ／Ｃ触媒の使用量が、芳香族ニトロ化合物に対して１～２０重量％である［１］～［６］のいずれかに記載の芳香族アミノ化合物の製造方法。
［８］　上記接触還元における反応温度が０～１００℃であり、反応時間が０．５時間～２０時間である［１］～［７］のいずれかに記載の芳香族アミノ化合物の製造方法。
［９］　さらに、バナジウム化合物を共存させる、［１］～［８］のいずれかに記載の芳香族アミノ化合物の製造方法。
［１０］　バナジウム化合物がＶＯ（ａｃａｃ）２である［９］に記載の芳香族アミノ化合物の製造方法。
［１１］　使用するバナジウム化合物の量が、芳香族ニトロ化合物に対して０．１～１．０ｍｏｌ％である［９］または［１０］に記載の芳香族アミノ化合物の製造方法。 [1] A method for producing an aromatic amino compound, comprising catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring with a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3):
P(R 1 ) 3 (1)
(In formula (1), each of the multiple R 1s independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
PO(R 2 ) 3 (2)
(In formula (2), each of the multiple R 2 's independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
(R 3 ) 2 P-R 4 -P(R 3 ) 2 (3)
(In formula (3), each of the multiple R 3 's independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent. In formula (3), R 4 represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 1 to 18 carbon atoms, an alkylenedioxy group having 1 to 18 carbon atoms, an arylene group having 6 to 24 carbon atoms, an arylene dioxy group having 6 to 24 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or a cycloalkylenedioxy group having 3 to 18 carbon atoms, which may have a substituent.)
[2] The method for producing an aromatic amino compound according to [1], wherein the phosphorus compound (A) is P(OMe) 3 or P(OEt) 3 .
[3] The method for producing an aromatic amino compound according to [1] or [2], wherein the amount of the phosphorus compound (A) used is 5 to 50 mol % based on the aromatic amino compound.
[4] The method for producing an aromatic amino compound according to any one of [1] to [3], wherein the aromatic nitro compound is represented by any one of the structures of the following formulas (1) to (3):
Figure JPOXMLDOC01-appb-C000002
 (In the formula, R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group, R 7 represents a hydrogen atom or a monovalent group, and n represents an integer of 1 to 2.)
[5] The method for producing an aromatic amino compound according to any one of [1] to [4], wherein the amount of platinum supported in the Pt/C catalyst is 0.5 to 5 wt % based on the total weight of the Pt/C catalyst.
[6] The method for producing an aromatic amino compound according to any one of [1] to [5], wherein the Pt/C catalyst is an iron-poisoned Pt/C catalyst.
[7] The method for producing an aromatic amino compound according to any one of [1] to [6], wherein the amount of the Pt/C catalyst used is 1 to 20% by weight based on the aromatic nitro compound.
[8] The method for producing an aromatic amino compound according to any one of [1] to [7], wherein the reaction temperature in the catalytic reduction is 0 to 100° C. and the reaction time is 0.5 to 20 hours.
[9] The method for producing an aromatic amino compound according to any one of [1] to [8], further comprising the coexistence of a vanadium compound.
[10] The method for producing an aromatic amino compound according to [9], wherein the vanadium compound is VO(acac) 2 .
[11] The method for producing an aromatic amino compound according to [9] or [10], wherein the amount of the vanadium compound used is 0.1 to 1.0 mol % based on the aromatic nitro compound.

　本発明の製造方法によれば、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物（以下、単に「化合物（ＤＮ）」ともいう）のニトロ基のみを選択的に、かつ、反応速度を損なうことなく、還元することができる。従って、農医薬品や電子材料の製造中間体として有用な、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族アミノ化合物を安価に、効率的に製造することが出来る。 　According to the manufacturing method of the present invention, only the nitro group of an aromatic nitro compound (hereinafter also referred to simply as "compound (DN)") having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring can be selectively reduced without impairing the reaction rate. Therefore, it is possible to inexpensively and efficiently manufacture aromatic amino compounds having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring, which are useful as intermediates in the manufacture of agricultural pharmaceuticals and electronic materials.

　本明細書全体を通して、以下の用語及び略号の意味は、以下のとおりである。
　「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。本明細書に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　Ｍｅはメチル基、Ｅｔはエチル基、Ｐｒはプロピル基、Ｂｕはブチル基、ｎ－はノルマル、ｔ－はターシャリー、ｏ－はオルト、Ｃｙはシクロヘキシル基、Ｐｈはフェニル基、Ｂｎはベンジル基、Ｔｏｌはトリル基、ａｃａｃはアセチルアセトナートを表す。 Throughout this specification, the following terms and abbreviations have the following meanings:
A numerical range expressed using "to" means a range including the numerical values described before and after "to" as the upper and lower limits. In the numerical ranges described in stages in this specification, the upper or lower limit described in a certain numerical range may be replaced with the upper or lower limit of another numerical range described in stages. In addition, in the numerical ranges described in this specification, the upper or lower limit described in a certain numerical range may be replaced with a value shown in the examples.
Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, n- represents normal, t- represents tertiary, o- represents ortho, Cy represents a cyclohexyl group, Ph represents a phenyl group, Bn represents a benzyl group, Tol represents a tolyl group, and acac represents acetylacetonate.

　以下、本発明の芳香族アミノ化合物の製造方法について説明する。
　本発明の芳香族アミノ化合物の製造方法の詳細を説明するにあたり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限り以下の内容に限定されるものではなく、適宜変更して実施することができる。 The process for producing an aromatic amino compound of the present invention will now be described.
In explaining the details of the method for producing an aromatic amino compound of the present invention, specific examples will be given. However, the present invention is not limited to the following content as long as it does not deviate from the spirit of the present invention, and can be appropriately modified and carried out.

　本発明の製造方法としては、例えば、下記の反応式１で表される芳香族アミノ化合物の製造方法が挙げられる。

Figure JPOXMLDOC01-appb-C000003
　式中、Ｌは単結合又は２価の基を表し、ＸはＣＲ１１を表し、ＹはＯ、ＮＲ１２またはＣＲ１３Ｒ１４を表し、Ｒ１１、Ｒ１２、Ｒ１３及びＲ１４はそれぞれ独立に水素原子または１価の基を表し、ただし、Ｒ１１、Ｒ１２、Ｒ１３及びＲ１４が結合しない代わりにＸとＹとの結合が三重結合になっていてもよい。複数のＲ１は、それぞれ独立して、上記の定義と同じである。 The production method of the present invention includes, for example, a method for producing an aromatic amino compound represented by the following reaction formula 1.
Figure JPOXMLDOC01-appb-C000003
 In the formula, L represents a single bond or a divalent group, X represents CR11 , Y represents O, NR12 or CR13R14 , and R11 , R12 , R13 and R14 each independently represent a hydrogen atom or a monovalent group, provided that R11 , R12 , R13 and R14 are not bonded to each other, and instead, X and Y may be bonded to each other as a triple bond. Each of the multiple R1s is independently defined as above.

　また、ＸとＹとの結合が二重結合である場合には、ＸとＹとが一緒になって、５員環または６員環などの環状構造を形成しても良く、上記環状構造の具体例としては、例えばシクロヘキセン、シクロヘキサジエン、ピラン、ジヒドロピラン、ジヒドロフラン、シクロヘキセン－１－オン、ジヒドロピロール、ジヒドロピリジン、テトラヒドロピリジンなどの環状オレフィンが挙げられる。
　すなわち、芳香族ニトロ化合物である化合物（ＤＮ）が、例えば、上記環状構造としてシクロヘキセンを有する化合物の場合には、以下の構造を有する化合物である。

Figure JPOXMLDOC01-appb-C000004
　（式中のＬは単結合又は２価の基を表す。） In addition, when the bond between X and Y is a double bond, X and Y may combine together to form a cyclic structure such as a 5-membered or 6-membered ring. Specific examples of the cyclic structure include cyclic olefins such as cyclohexene, cyclohexadiene, pyran, dihydropyran, dihydrofuran, cyclohexen-1-one, dihydropyrrole, dihydropyridine, and tetrahydropyridine.
That is, when the compound (DN) which is an aromatic nitro compound is, for example, a compound having cyclohexene as the cyclic structure, it is a compound having the following structure.
Figure JPOXMLDOC01-appb-C000004
 (In the formula, L represents a single bond or a divalent group.)

　また、ＸとＹとの結合が二重結合である場合には、Ｙがニトロ基の置換したベンゼン環に結合してもよく、具体例としては、以下の構造を有する化合物が挙げられる。

Figure JPOXMLDOC01-appb-C000005
Furthermore, when the bond between X and Y is a double bond, Y may be bonded to a benzene ring substituted with a nitro group, and specific examples include compounds having the following structures.
Figure JPOXMLDOC01-appb-C000005

　本発明は、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物を、下記式（１）で表されるリン化合物、下記式（２）で表されるリン化合物、および下記式（３）で表されるリン化合物からなる群から選択される少なくとも１種のリン化合物（Ａ）の存在下、Ｐｔ／Ｃ触媒で接触還元することにより芳香族アミノ化合物を製造する方法である。 The present invention is a method for producing an aromatic amino compound by catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen, and carbon-oxygen in a portion other than the aromatic ring with a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3).

　本発明において用いる芳香族ニトロ化合物は、芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物である。
　芳香族ニトロ化合物としては、芳香族モノニトロ化合物、または、芳香族ジニトロ化合物が好ましい。
　上記多重結合の中でもα、β－不飽和カルボニル基が好ましい。多重結合としてα、β－不飽和カルボニル基を有する芳香族ニトロ化合物としては、例えば以下の構造を有する化合物は（Ｉ）～（ＩＩＩ）が挙げられる。 The aromatic nitro compound used in the present invention is an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a portion other than the aromatic ring.
The aromatic nitro compound is preferably an aromatic mononitro compound or an aromatic dinitro compound.
Among the above multiple bonds, an α,β-unsaturated carbonyl group is preferred. Examples of aromatic nitro compounds having an α,β-unsaturated carbonyl group as a multiple bond include compounds having the following structures (I) to (III).

Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ５、Ｒ６、Ｒ８、Ｒ９はそれぞれ独立して単結合又は２価の基を表し、Ｒ７は水素原子又は１価の基を表し、Ｒ１０、Ｒ１１、Ｒ１２、Ｒ１３、Ｒ１４、Ｒ１５、Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９はそれぞれ独立して水素原子またはメチル基を表し、ｎは１～２の整数を表す。）
Figure JPOXMLDOC01-appb-C000006
 (In the formula, R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group, R 7 represents a hydrogen atom or a monovalent group, R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , and R 19 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 2.)

　また、上記式（Ｉ）～（ＩＩＩ）で表される化合物としては、以下の化合物（１）～（３）が好ましい。

Figure JPOXMLDOC01-appb-C000007
（上記式中、Ｒ５、Ｒ６、Ｒ８、Ｒ９は、それぞれ独立して単結合又は２価の基を表し、Ｒ７は水素原子又は１価の基を表す。ｎは１～２の整数を表す。） As the compounds represented by the above formulas (I) to (III), the following compounds (1) to (3) are preferable.
Figure JPOXMLDOC01-appb-C000007
 (In the above formula, R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group, R 7 represents a hydrogen atom or a monovalent group, and n represents an integer of 1 to 2.)

　上記Ｒ５、Ｒ６、Ｒ８、Ｒ９における２価の基としては、非置換若しくはフッ素原子によって置換されている炭素原子数１～２０のアルキレン基が挙げられる。上記炭素原子数１～２０のアルキレン基中の－ＣＨ２－又は－ＣＦ２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＮＨ－、二価の炭素環および二価の複素環からなる群から選ばれる基（ただし、これらの群から選ばれる基は互いに隣り合わない）に置き換えられていてもよく、なかでも、非置換の炭素原子数１～６のアルキレン基（アルキレン基中のベンゼン環と結合する側の－ＣＨ２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－および－ＮＨ－から選ばれる基（ただし、これらの群から選ばれる基は互いに隣り合わない）に置き換えられていてもよい）が好ましい。 The divalent groups in R 5 , R 6 , R 8 and R 9 include unsubstituted or fluorine-substituted alkylene groups having 1 to 20 carbon atoms. In the alkylene groups having 1 to 20 carbon atoms, -CH 2 - or -CF 2 - may be replaced with a group selected from the group consisting of -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring and a divalent heterocyclic ring (with the proviso that the groups selected from these groups are not adjacent to each other), and among these, an unsubstituted alkylene group having 1 to 6 carbon atoms (with the -CH 2 - on the side bonding to the benzene ring in the alkylene group being replaced with a group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH- and -NH- (with the proviso that the groups selected from these groups are not adjacent to each other)) is preferred.

　上記Ｒ７における１価の基としては、非置換若しくはフッ素原子によって置換されている炭素原子数１～２０のアルキル基が挙げられる。上記炭素原子数１～２０のアルキル基中の－ＣＨ２－又は－ＣＦ２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＮＨ－、二価の炭素環および二価の複素環からなる群から選ばれる基（ただし、これらの群から選ばれる基は互いに隣り合わない）に置き換えられていてもよく、なかでも、非置換の炭素原子数１～６のアルキル基（アルキル基中の－ＣＨ２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨＣＯ－、－ＣＯＮＨ－および－ＮＨ－から選ばれる基（ただし、これらの群から選ばれる基は互いに隣り合わない）に置き換えられていてもよい）が好ましい。 The monovalent group for R 7 includes an unsubstituted or fluorine-substituted alkyl group having 1 to 20 carbon atoms. In the alkyl group having 1 to 20 carbon atoms, -CH 2 - or -CF 2 - may be replaced with a group selected from the group consisting of -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, and a divalent heterocyclic ring (with the proviso that groups selected from these groups are not adjacent to each other), and among these, an unsubstituted alkyl group having 1 to 6 carbon atoms (with -CH 2 - in the alkyl group being replaced with a group selected from -O-, -COO-, -OCO-, -NHCO-, -CONH-, and -NH- (with the proviso that groups selected from these groups are not adjacent to each other)) is preferred.

　本発明において用いるリン化合物としては、下記式（１）で表されるリン化合物、下記式（２）で表されるリン化合物、および下記式（３）で表されるリン化合物からなる群から選択される少なくとも１種のリン化合物（Ａ）が挙げられる。
　Ｐ（Ｒ１）３　　　（１）
（式（１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　ＰＯ（Ｒ２）３　　　（２）
（式（２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　（Ｒ３）２Ｐ-Ｒ４-Ｐ（Ｒ３）２　　　（３）
（式（３）中、複数のＲ３は、それぞれ独立して、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。式（３）中、Ｒ４は炭素数１～１８のアルキレン基、炭素数１～１８のアルケニレン基、炭素数１～１８のアルキレンジオキシ基、炭素数６～２４のアリーレン基、炭素数６～２４のアリーレンジオキシ基、炭素数３～１８のシクロアルキレン基、又は炭素数３～１８のシクロアルキレンジオキシ基を表し、これらは置換基を有していても良い。） The phosphorus compound used in the present invention includes at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2), and phosphorus compounds represented by the following formula (3).
P(R 1 ) 3 (1)
(In formula (1), each of the multiple R 1s independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
PO(R 2 ) 3 (2)
(In formula (2), each of the multiple R 2 's independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
(R 3 ) 2 P-R 4 -P(R 3 ) 2 (3)
(In formula (3), each of the multiple R 3 's independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent. In formula (3), R 4 represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 1 to 18 carbon atoms, an alkylenedioxy group having 1 to 18 carbon atoms, an arylene group having 6 to 24 carbon atoms, an arylene dioxy group having 6 to 24 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or a cycloalkylenedioxy group having 3 to 18 carbon atoms, which may have a substituent.)

　上記式（１）におけるＲ１の具体例としては、メチル、エチル、ノルマルプロピル（ｎ－Ｐｒ）、イソプロピル（ｉ－Ｐｒ）、ノルマルブチル（ｎ－Ｂｕ）、ターシャリーブチル（ｔ－Ｂｕ）、フェニル（Ｐｈ）、ベンジル（Ｂｎ）、メトキシ（ＯＭｅ）、エトキシ（ＯＥｔ）、ノルマルプロピルオキシ（Ｏｎ－Ｐｒ）、ノルマルブチルオキシ（Ｏｎ－Ｂｕ）、フェノキシ（ＯＰｈ）、ベンジルオキシなどが挙げられるが、ｎ－Ｂｕ、Ｐｈ、ＯＭｅ、ＯＥｔ、Ｏｎ－Ｂｕ、ＯＰｈが好ましく、選択率がより高い点から、ＯＭｅ、ＯＥｔがより好ましい。 Specific examples of R 1 in the above formula (1) include methyl, ethyl, normal propyl (n-Pr), isopropyl (i-Pr), normal butyl (n-Bu), tertiary butyl (t-Bu), phenyl (Ph), benzyl (Bn), methoxy (OMe), ethoxy (OEt), normal propyloxy (On-Pr), normal butyloxy (On-Bu), phenoxy (OPh), and benzyloxy. Of these, n-Bu, Ph , OMe, OEt, On-Bu, and OPh are preferred, and OMe and OEt are more preferred in terms of higher selectivity.

　上記式（２）におけるＲ２の具体例としては、水素、メチル、エチル、ｎ－Ｐｒ、ｉ－Ｐｒ、ｎ－Ｂｕ、ｔ－Ｂｕ，ｎ－オクチル、シクロヘキシル、Ｐｈ，ｐ－メチルフェニル、ｐ－メトキシフェニル、ベンジル、ＯＭｅ、ＯＥｔ、ノルマルプロピルオキシ、ノルマルブチルオキシ、ＯＰｈ、ベンジルオキシなどが挙げられるが、選択率がより高い点から、水素、メチル、ｎ－Ｂｕ、ｎ－オクチル、Ｐｈが好ましく、水素、メチル、Ｐｈがより好ましい。 Specific examples of R2 in the above formula (2) include hydrogen, methyl, ethyl, n-Pr, i-Pr, n-Bu, t-Bu, n-octyl, cyclohexyl, Ph, p-methylphenyl, p-methoxyphenyl, benzyl, OMe, OEt, n-propyloxy, n-butyloxy, OPh, and benzyloxy. From the viewpoint of higher selectivity, hydrogen, methyl, n-Bu, n-octyl, and Ph are preferred, and hydrogen, methyl, and Ph are more preferred.

　上記式（３）におけるＲ３の具体例としては、水素、メチル、エチル、ｎ－Ｐｒ、ｉ－Ｐｒ、ｎ－Ｂｕ、ｔ－Ｂｕ，ｎ－オクチル、シクロヘキシル、Ｐｈ，ｐ－メチルフェニル、ｐ－メトキシフェニル、ベンジル、ＯＭｅ、ＯＥｔ、ノルマルプロピルオキシ、ノルマルブチルオキシ、ＯＰｈ、ベンジルオキシなどが挙げられるが、選択率がより高い点から、メチル、エチル、ＯＭｅ、ＯＥｔ、Ｐｈが好ましく、選択率がより高い点から、メチル、ＯＭｅ、ＯＥｔ、Ｐｈがより好ましい。
　上記式（３）におけるＲ４の具体例としては、メチレン、エチレン、プロピレン、ブチレン、ペンチレン、ヘキシレン、１，２－フェニレン、１，３－フェニレン、２，２’－ビフェニレン、２，２’－ビナフチレン、１，８－ナフチレン、１，８－（９，９－ジメチル）キサンテニレン、１，１’－フェロセニレンが挙げられるが、なかでも、メチレン、エチレン、プロピレン、ブチレン、１，２－フェニレン、２，２’－ビフェニレン、２，２’－ビナフチレン、１，８－ナフチレン、１，１’－フェロセニレンが好ましく、選択率がより高い点から、メチレン、エチレン、プロピレン、ブチレン、２，２’－ビナフチレンがより好ましい。 Specific examples of R3 in the above formula (3) include hydrogen, methyl, ethyl, n-Pr, i-Pr, n-Bu, t-Bu, n-octyl, cyclohexyl, Ph, p-methylphenyl, p-methoxyphenyl, benzyl, OMe, OEt, n-propyloxy, n-butyloxy, OPh, and benzyloxy. From the viewpoint of higher selectivity, methyl, ethyl, OMe, OEt, and Ph are preferred, and from the viewpoint of higher selectivity, methyl, OMe, OEt, and Ph are more preferred.
Specific examples of R 4 in the above formula (3) include methylene, ethylene, propylene, butylene, pentylene, hexylene, 1,2-phenylene, 1,3-phenylene, 2,2'-biphenylene, 2,2'-binaphthylene, 1,8-naphthylene, 1,8-(9,9-dimethyl)xanthenylene, and 1,1'-ferrocenylene. Among these, methylene, ethylene, propylene, butylene, 1,2-phenylene, 2,2'-biphenylene, 2,2'-binaphthylene, 1,8-naphthylene, and 1,1'-ferrocenylene are preferred, and methylene, ethylene, propylene, butylene, and 2,2'-binaphthylene are more preferred from the viewpoint of higher selectivity.

　式中のＲ１、Ｒ２、Ｒ３が有しても良い置換基としては、例えば、メチル基、エチル基、ｉ－プロピル基、ｔ－ブチル基、フェニル基、ヒドロキシル基、メトキシ基、ｉ－プロピルオキシ基、ｔ－ブチルオキシ基、アミノ基、ジメチルアミノ基、シアノ基、ホルミル基、カルボキシ基、スルホキシ基、フルオロ基、クロロ基、ブロモ基、ヨード基が挙げられる。 Examples of the substituent that R 1 , R 2 , and R 3 in the formula may have include a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a phenyl group, a hydroxyl group, a methoxy group, an i-propyloxy group, a t-butyloxy group, an amino group, a dimethylamino group, a cyano group, a formyl group, a carboxy group, a sulfoxy group, a fluoro group, a chloro group, a bromo group, and an iodo group.

　リン化合物（Ａ）の具体例としては、ＰＭｅ３、ＰＥｔ３、Ｐ（ｎ－Ｐｒ）３、Ｐ（ｎ－Ｂｕ）３、Ｐ（ｔ－Ｂｕ）３、Ｐ（ｎ－Ｃ６Ｈ１３）３、Ｐ（ｎ－Ｃ８Ｈ１７）３、ＰＣｙ３、ＰＢｎ３、ＰＰｈ３、Ｐ（ｏ－Ｔｏｌ）３、Ｐ（ＯＭｅ）３、Ｐ（ＯＥｔ）３、Ｐ（Ｏｎ－Ｐｒ）３、Ｐ（Ｏｎ－Ｂｕ）３、Ｐ（ＯＰｈ）３、Ｐ（ＯＢｎ）３、Ｐ（Ｏ）（ｎ－Ｂｕ）３、Ｐ（Ｏ）Ｐｈ３、（±）－ＢＩＮＡＰ（２，２’-ビス(ジフェニルホスフィノ)-１，１-ビナフチル）、（＋）－ＢＩＮＡＰ、（－）－ＢＩＮＡＰ，ｄｅｐｅ（１，２-ビス(ジエチルホスフィノ)エタン）,ｄｐｐｍ（１，１－ビス(ジフェニルホスフィノ)メタン）、ｄｐｐｅ（１，２－ビス(ジフェニルホスフィノ)エタン）、ｄｐｐｐ（１，３－ビス(ジフェニルホスフィノ)プロパン）、ｄｐｐｂ（１，４－ビス(ジフェニルホスフィノ)ブタン）、ｄｐｐｂｚ（１,２-ビス(ジフェニルホスフィノ)ベンゼン）、ｄｐｐｆ（１,１'-ビス(ジフェニルホスフィノ)フェロセン）、Ｘａｎｔｐｈｏｓ、などが挙げられる。 Specific examples of the phosphorus compound (A) include PMe3 , PEt3 , P(n-Pr) 3 , P (n-Bu) 3 , P (t-Bu) 3 , P(n- C6H13 ) 3 , P(n- C8H17 ) 3 , PCy3 , PBn3 , PPh3, P(o-Tol) 3 , P(OMe) 3 , P(OEt) 3 , P(On-Pr) 3 , P(On-Bu) 3 , P(OPh) 3 , P(OBn) 3 , P(O)(n-Bu) 3 , and P(O)Ph3 . , (±)-BINAP (2,2'-bis(diphenylphosphino)-1,1-binaphthyl), (+)-BINAP, (-)-BINAP, depe (1,2-bis(diethylphosphino)ethane), dppm (1,1-bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), dppb (1,4-bis(diphenylphosphino)butane), dppbz (1,2-bis(diphenylphosphino)benzene), dppf (1,1'-bis(diphenylphosphino)ferrocene), Xantphos, and the like.

　中でも、Ｐ（ｎ－Ｂｕ）３、ＰＰｈ３、Ｐ（ＯＭｅ）３、Ｐ（ＯＥｔ）３、Ｐ（Ｏｎ－Ｂｕ）３、Ｐ（ＯＰｈ）３が好ましく、選択率がより高い点から、Ｐ（ＯＭｅ）３、Ｐ（ＯＥｔ）３、がより好ましい。 Among these, P(n-Bu) 3 , PPh 3 , P(OMe) 3 , P(OEt) 3 , P(On-Bu) 3 and P(OPh) 3 are preferred, with P(OMe) 3 and P(OEt) 3 being more preferred from the viewpoint of higher selectivity.

　本発明における、リン化合物（Ａ）の使用量は、反応後に除去しやすいという点から、芳香族ニトロ化合物である化合物（ＤＮ）に対して５０モル％以下であることが好ましく、３５モル％以下であることが更に好ましく、選択率が優れる点から、５モル％以上であることが好ましく、１０モル％以上であることが更に好ましい。 In the present invention, the amount of phosphorus compound (A) used is preferably 50 mol % or less, more preferably 35 mol % or less, relative to the aromatic nitro compound (DN) in terms of ease of removal after the reaction, and is preferably 5 mol % or more, more preferably 10 mol % or more in terms of excellent selectivity.

　本反応において、Ｐｔ／Ｃ触媒の使用量は、芳香族ニトロ化合物である化合物（ＤＮ）に対して、１重量％以上であることが好ましく、３重量％以上であることがより好ましく、２０重量％以下であることが好ましく、１０重量％以下であることがより好ましい。 In this reaction, the amount of Pt/C catalyst used is preferably 1% by weight or more, more preferably 3% by weight or more, and preferably 20% by weight or less, more preferably 10% by weight or less, relative to the aromatic nitro compound (DN).

　Ｐｔ／Ｃ触媒における白金の担持量は、Ｐｔ／Ｃ触媒全重量に対して、０．５～５重量％であることが好ましく、１～５重量％であることがより好ましい。 The amount of platinum supported in the Pt/C catalyst is preferably 0.5 to 5% by weight, and more preferably 1 to 5% by weight, based on the total weight of the Pt/C catalyst.

　本反応において、Ｐｔ／Ｃ触媒としては、Ｓ、Ｃｕ、Ｖ、または、Ｆｅで被毒されたものを用いることが好ましく、Ｆｅで被毒されたものがより好ましい。被毒に使用されるＦｅのドープ量は、Ｆｅで被毒されたＰｔ／Ｃ触媒の全重量を基準として、副反応を抑えるという観点から、０．０５重量％以上であることが好ましく、０．１重量％以上であることがより好ましく、触媒活性を低下させないという観点から、１．０重量％以下であることが好ましく、０．５重量％以下であることがより好ましい。 In this reaction, the Pt/C catalyst is preferably poisoned with S, Cu, V, or Fe, and more preferably poisoned with Fe. The amount of Fe used for poisoning is preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the total weight of the Pt/C catalyst poisoned with Fe, from the viewpoint of suppressing side reactions, and is preferably 1.0% by weight or less, and more preferably 0.5% by weight or less, from the viewpoint of not reducing the catalytic activity.

　本反応において、バナジウム化合物をさらに共存させることが、アゾキシ化合物の生成を抑制するという観点から好ましい。このようなバナジウム化合物としては、ＶＯ（ａｃａｃ）３、ＶＯ（ａｃａｃ）２、ＮＨ４ＶＯ３、Ｖ２Ｏ５、ＶＯＣｌ３、ＶＣｌ６、［ＶＯ（ＳＣＮ）４］２－、ＶＯＳＯ４、ＬｉＶＯ３、ＮａＶＯ３、ＫＶＯ３、ＶＣｌ３が好ましく、ＶＯ（ａｃａｃ）２がより好ましい。 In this reaction, it is preferable to further coexist a vanadium compound from the viewpoint of suppressing the production of azoxy compounds. As such a vanadium compound, VO(acac) 3 , VO (acac) 2 , NH4VO3 , V2O5 , VOCl3 , VCl6 , [VO(SCN) 4 ] 2- , VOSO4 , LiVO3 , NaVO3 , KVO3 , and VCl3 are preferred, and VO(acac) 2 is more preferred.

　本反応において、バナジウム化合物の使用量は、多過ぎると生成物中に残存する可能性が高くなるため、好ましくは、化合物（ＤＮ）に対して１．０モル％以下であり、さらに好ましくは０．２モル％以下である。また、バナジウム化合物の使用量は、アゾキシ化合物の生成を十分に抑制するという観点から、０．１モル％以上であることが好ましい。 In this reaction, if the amount of vanadium compound used is too large, there is a high possibility that it will remain in the product, so it is preferably 1.0 mol% or less relative to compound (DN), and more preferably 0.2 mol% or less. In addition, from the viewpoint of sufficiently suppressing the production of azoxy compounds, it is preferable that the amount of vanadium compound used is 0.1 mol% or more.

　本反応は、溶媒中で行ってもよい。反応溶媒としては、当該反応条件下において安定であって、不活性で、反応を妨げないものであればいずれも使用できる。反応溶媒として、水、アルコール類、アミン類、非プロトン性極性有機溶媒（ＤＭＦ（ジメチルホルムアミド）、ＤＭＳＯ（ジメチルスルホキシド）、ＤＭＡｃ（ジメチルアセトアミド）、ＮＭＰ（Ｎ－メチルピロリドン）など）、エーテル類（Ｅｔ２Ｏ、ｉ－Ｐｒ２Ｏ、ＴＢＭＥ（ｔｅｒｔ－ブチルメチルエーテル）、ＣＰＭＥ（シクロペンチルメチルエーテル）、ＴＨＦ（テトラヒドロフラン）、ジオキサンなど）、脂肪族炭化水素類（ペンタン、へキサン、ヘプタン、石油エーテルなど）、芳香族炭化水素類（ベンゼン、トルエン、キシレン、メシチレン、クロロベンゼン、ジクロロベンゼン、ニトロベンゼン、テトラリンなど）、ハロゲン系炭化水素類（クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタンなど）、低級脂肪酸エステル類（酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチルなど）、ニトリル類（アセトニトリル、プロピオニトリル、ブチロニトリルなど）などが使用できる。これらの溶媒は、反応の起こり易さなどを考慮して適宜選択することができ、1種単独で又は2種以上混合して用いることができる。また場合によっては、上記溶媒は、適当な脱水剤や乾燥剤を用いて水を含有しない溶媒として用いることもできる。 The reaction may be carried out in a solvent. Any reaction solvent may be used as long as it is stable under the reaction conditions, is inert, and does not interfere with the reaction. Examples of reaction solvents that can be used include water, alcohols, amines, aprotic polar organic solvents (DMF (dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (dimethylacetamide), NMP (N-methylpyrrolidone)), ethers (Et 2 O, i-Pr 2 O, TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), THF (tetrahydrofuran), dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogenated hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), and nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected in consideration of the ease of reaction, etc., and can be used alone or in combination of two or more. In some cases, the above solvents can be used as water-free solvents by using an appropriate dehydrating agent or drying agent.

　接触還元の際の反応温度は、通常－９０℃～２００℃であり、好ましくは０℃～１００℃である。
　接触還元の際の反応時間は、通常０．０５時間～１００時間であり、好ましくは０．５時間～２０時間であり、より好ましくは０．５時間～１０時間である。
　接触還元の際の反応圧力は、通常常圧～１０ＭＰａＧであり、好ましくは常圧～０．８ＭＰａＧである。 The reaction temperature in the catalytic reduction is usually from -90°C to 200°C, preferably from 0°C to 100°C.
The reaction time in the catalytic reduction is usually 0.05 to 100 hours, preferably 0.5 to 20 hours, and more preferably 0.5 to 10 hours.
The reaction pressure during catalytic reduction is usually from normal pressure to 10 MPaG, and preferably from normal pressure to 0.8 MPaG.

　以下、本発明を実施例によりさらに具体的に説明するが、これらの実施例によって本発明の解釈が限定されるものではない。なお、実施例にて採用した分析装置及び分析条件は、下記のとおりである。 The present invention will be explained in more detail below with reference to examples, but the interpretation of the present invention is not limited to these examples. The analytical equipment and analytical conditions used in the examples are as follows.

１Ｈ－ＮＭＲ；
　装置：　日本電子株式会社製　ＥＣＺ（４００　ＭＨｚ）
　測定溶媒：　ＣＤＣｌ３
　基準物質：　テトラメチルシラン（ＴＭＳ）　（ＴＭＳの１Ｈのδ値を０．０　ｐｐｍ　とする。） 1 H-NMR;
Equipment: ECZ (400 MHz) manufactured by JEOL Ltd.
Measurement solvent: CDCl3
Reference substance: Tetramethylsilane (TMS) (The δ value of 1 H of TMS is set to 0.0 ppm.)

ＨＰＬＣ；
　装置：ＨＰＬＣ、株式会社島津製作所製　ＬＣ－２０ＡＤ
　カラム：Ｉｎｅｒｔｓｉｌ　ＯＤＳ－３　（ＧＬ　Ｓｃｉｅｎｃｅ），　５μｍ　Φ４．６×２５０　ｍｍ
　カラム温度：４０　℃
　溶離液：（Ａ）アセトニトリル／（Ｂ）５０　ｍＭ　リン酸カリウム緩衝液（ｐＨ＝７）
Ａ／Ｂ　＝　３５／６５　（０～１０ｍｉｎ．）－６０／４０（１３－３０ｍｉｎ．）（ｖ／ｖ）
　流速：１．０　ｍＬ／ｍｉｎ
　検出法：ＵＶ（２５４　ｎｍ）
　データ採取時間：３０　ｍｉｎ． HPLC;
Apparatus: HPLC, Shimadzu Corporation LC-20AD
Column: Inertsil ODS-3 (GL Science), 5 μm Φ4.6 × 250 mm
Column temperature: 40 ° C.
Eluent: (A) acetonitrile/(B) 50 mM potassium phosphate buffer (pH = 7)
A/B = 35/65 (0-10min.) - 60/40 (13-30min.) (v/v)
Flow rate: 1.0 mL/min
Detection method: UV (254 nm)
Data collection time: 30 min.

［芳香族アミノ化合物の合成例］
＜合成例１＞　２－（３，５－ジアミノベンゾイルオキシ）エチルメタクリレートの製造（化合物ＤＡ－１） [Synthesis Example of Aromatic Amino Compound]
Synthesis Example 1: Production of 2-(3,5-diaminobenzoyloxy)ethyl methacrylate (Compound DA-1)

Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008

　ここで用いられるニトロ化合物は公知化合物であり、文献記載の公知の方法に準じて合成できる。例えば２－（３，５－ジニトロベンゾイルオキシ）エチルメタクリレートは、特許第５５６０７１５号に記載の方法に準じて反応させることにより、化合物を得ることができる。 The nitro compounds used here are known compounds and can be synthesized according to known methods described in the literature. For example, 2-(3,5-dinitrobenzoyloxy)ethyl methacrylate can be reacted according to the method described in Japanese Patent No. 5560715 to obtain the compound.

（合成例１－ａ－１）
　２００ｍＬの圧力容器に２－（３，５－ジニトロベンゾイルオキシ）エチルメタクリレート（５．００ｇ、１５．４ｍｍｏｌ）、トルエン（５０．０ｇ）、亜リン酸トリエチル（０．５１２ｇ、３．０８ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ触媒（５５．０重量％含水型、０．５５６ｇ）、酸化バナジウムビスアセチルアセトナート（８．９４ｍｇ、３０．８μｍｍｏｌ）を添加し、ゲージ圧０．６０ＭＰａの水素雰囲気下、４０℃で４時間撹拌した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－１のＨＰＬＣ相対面積百分率は９８．８％、反応収率は１００％で過還元体（ＤＡ－１’）は未検出であった。
　反応終了後、酢酸エチル（２０．０ｇ）を加え、触媒をろ過した後、ろ物を酢酸エチル（５．００ｇ）で２回洗浄した。ろ液に水（２０．０ｇ）を加え、撹拌後、水層を除く操作を２回繰り返した後、有機層を４１．２ｇになるまで濃縮し、トルエン（５０．０ｇ）を加え、再度、４１．２ｇになるまで濃縮した後、０℃に冷却し、析出した結晶をろ過し、結晶をトルエン（１５．０ｇ）で２回洗浄した後、水（５．０ｇ）で２回洗浄し、４０℃で減圧乾燥し、粉末結晶（ＤＡ－１）を得た（収量３．４４ｇ、収率８６．５％）
　得られた結晶のＨＰＬＣを測定した結果、ＤＡ－１のＨＰＬＣ相対面積百分率は１００．０％で過還元体（ＤＡ－１’）は未検出であった。 (Synthesis example 1-a-1)
2-(3,5-Dinitrobenzoyloxy)ethyl methacrylate (5.00 g, 15.4 mmol), toluene (50.0 g), triethyl phosphite (0.512 g, 3.08 mmol), 1 wt % Pt/C catalyst poisoned with 0.2 wt % iron (55.0 wt % water-containing type, 0.556 g), and vanadium oxide bisacetylacetonate (8.94 mg, 30.8 μmmol) were added to a 200 mL pressure vessel, and the mixture was stirred at 40° C. for 4 hours under a hydrogen atmosphere with a gauge pressure of 0.60 MPa.
As a result of measuring the reaction solution by HPLC, the HPLC relative area percentage of DA-1 was 98.8%, the reaction yield was 100%, and no over-reduced product (DA-1') was detected.
After the reaction was completed, ethyl acetate (20.0 g) was added, the catalyst was filtered, and the residue was washed twice with ethyl acetate (5.00 g). Water (20.0 g) was added to the filtrate, and after stirring, the operation of removing the water layer was repeated twice, and the organic layer was concentrated to 41.2 g, toluene (50.0 g) was added, and the mixture was concentrated again to 41.2 g, and then cooled to 0 ° C., and the precipitated crystals were filtered, washed twice with toluene (15.0 g), washed twice with water (5.0 g), and dried under reduced pressure at 40 ° C. to obtain powder crystals (DA-1) (yield 3.44 g, yield 86.5%).
HPLC of the obtained crystals was measured, and as a result, the HPLC relative area percentage of DA-1 was 100.0%, and no over-reduced product (DA-1') was detected.

１Ｈ－ＮＭＲ（ＣＤＣｌ３）：δ　６．７７（ｄ、Ｊ＝２．４Ｈｚ，２Ｈ、Ａｒ），６．１９（ｄｄ，Ｊ＝２.４Ｈｚ，２，２Ｈｚ，１Ｈ、＝ＣＨ），６．１４（ｂｒ，１Ｈ，Ａｒ），５．５９（ｄｄ，Ｊ＝２.４Ｈｚ，２，２Ｈｚ，１Ｈ、＝ＣＨ），４．４８（ｍ，４Ｈ，ＣＨ２ＣＨ２），３．５９（ｂｒ，４Ｈ，ＮＨ２），１．９５（ｓ，３Ｈ，Ｍｅ）． 1 H-NMR (CDCl 3 ): δ 6.77 (d, J=2.4Hz, 2H, Ar), 6.19 (dd, J=2.4Hz, 2.2Hz, 1H, =CH), 6. 14 (br, 1H, Ar), 5.59 (dd, J=2.4Hz, 2,2Hz, 1H, =CH), 4.48 (m, 4H, CH 2 CH 2 ), 3.59 (br, 4H, NH 2 ), 1.95 (s, 3H, Me).

（比較合成例）
　２００ｍＬの圧力容器に、２－（３，５－ジニトロベンゾイルオキシ）エチルメタクリレート（２．００ｇ、６．１７ｍｍｏｌ）、トルエン（２０．０ｇ）、５０重量％次亜リン酸水溶液（０．１６３ｇ、１．２３ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ（５５．０重量％含水型、０．４４４ｇ）を添加し、ゲージ圧０．６０ＭＰａの水素雰囲気下、４０℃で撹拌した。撹拌開始６時間後の反応液のＨＰＬＣを測定した結果、反応は完結しておらず、ＤＡ－１のＬＣ相対面積百分率は４２．３％、過還元体（ＤＡ－１’）のＬＣ相対面積百分率は０．３％であった。さらに撹拌を行い、合計２４時間後の反応液のＨＰＬＣを測定した結果、ＤＡ－１のＨＰＬＣ相対面積百分率は９６．５％、収率は７２％で過還元体（ＤＡ－１’）のＨＰＬＣ相対面積百分率は１．０％であった。 (Comparative synthesis example)
2-(3,5-dinitrobenzoyloxy)ethyl methacrylate (2.00 g, 6.17 mmol), toluene (20.0 g), 50 wt% aqueous hypophosphorous acid solution (0.163 g, 1.23 mmol), and 1 wt% Pt/C (55.0 wt% water-containing type, 0.444 g) poisoned with 0.2 wt% iron were added to a 200 mL pressure vessel, and the mixture was stirred at 40° C. under a hydrogen atmosphere with a gauge pressure of 0.60 MPa. HPLC of the reaction solution 6 hours after the start of stirring showed that the reaction was not complete, the LC relative area percentage of DA-1 was 42.3%, and the LC relative area percentage of the over-reduced product (DA-1′) was 0.3%. Stirring was continued and the reaction solution was subjected to HPLC measurement after a total of 24 hours. As a result, the HPLC relative area percentage of DA-1 was 96.5%, the yield was 72%, and the HPLC relative area percentage of the over-reduced product (DA-1') was 1.0%.

　添加剤であるリン化合物の種類、ＤＮ－１の使用量、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ触媒の添加量、酸化バナジウムビスアセチルアセトナート（ＶＯ（ａｃａｃ）２の添加量、溶媒であるトルエンの使用量を変更した以外は、合成例１－ａ－１に記載の方法に準じて合成例１－ａ－２～合成例１－ａ－８の合成を実施した。 Synthesis Examples 1-a-2 to 1-a-8 were synthesized in accordance with the method described in Synthesis Example 1-a-1, except that the type of phosphorus compound as an additive, the amount of DN-1 used, the amount of 1 wt % Pt/C catalyst poisoned with 0.2 wt % iron added, the amount of vanadium oxide bisacetylacetonate (VO(acac) 2 added, and the amount of toluene used as a solvent were changed.

　合成例１－ａ－１～合成例１－ａ－８および比較合成例に用いた添加剤の種類、ＤＮ－１の使用量、１重量％Ｐｔ／Ｃ触媒の添加量、酸化バナジウムビスアセチルアセトナート（ＶＯ（ａｃａｃ）２）の添加量、溶媒であるトルエン、および、酢酸エチルの使用量、ＤＡ－１のＬＣ相対面積百分率、過還元体（ＤＡ－１’）のＨＰＬＣ相対面積百分率、選択率、反応収率を表１に記載する。
　なお、表中の選択率の測定方法は以下のとおりである。
　選択率（％）＝ＤＡ－１／（ＤＡ－１＋ＤＡ－１’）×１００ Table 1 shows the types of additives used in Synthesis Examples 1-a-1 to 1-a-8 and Comparative Synthesis Examples, the amount of DN-1 used, the amount of 1 wt % Pt/C catalyst added, the amount of vanadium oxide bisacetylacetonate (VO(acac) 2 ) added, the amounts of toluene and ethyl acetate used as solvents, the LC relative area percentage of DA-1, the HPLC relative area percentage of the over-reduced product (DA-1'), the selectivity, and the reaction yield.
The selectivity in the table was measured by the following method.
Selectivity (%) = DA-1/(DA-1+DA-1') x 100

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009


　表１に示されるように、合成例１－ａ－１～合成例１－ａ－８では、リン化合物（Ａ）の存在下、Ｐｔ／Ｃ触媒で接触還元することにより、芳香族ニトロ化合物のニトロ基のみを高い選択率で、かつ短い反応時間、すなわち反応速度を損なうことなく、アミノ基に還元できることがわかった。 As shown in Table 1, in Synthesis Examples 1-a-1 to 1-a-8, it was found that catalytic reduction using a Pt/C catalyst in the presence of phosphorus compound (A) reduced only the nitro groups of aromatic nitro compounds to amino groups with high selectivity and in a short reaction time, i.e., without impairing the reaction rate.

＜合成例２＞　（Ｅ）－４－（６―（メタクリロイルオキシ）ヘキシルオキシ）桂皮酸（２－（２，４－ジアミノフェニル）エチル）エステルの製造（化合物ＤＡ－２） <Synthesis Example 2> (E)-4-(6-(methacryloyloxy)hexyloxy)cinnamic acid (2-(2,4-diaminophenyl)ethyl) ester (Compound DA-2)

Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010

　ここで用いられるニトロ化合物は公知化合物であり、文献記載の公知の方法に準じて合成できる。例えば（Ｅ）－４－（６―（メタクリロイルオキシ）ヘキシルオキシ）桂皮酸（２－（２，４－ジニトロフェニル）エチル）エステルは、特許第６７３３５５２号に記載の方法に準じて反応させることにより、化合物を得ることができる。 The nitro compounds used here are known compounds and can be synthesized in accordance with known methods described in the literature. For example, (E)-4-(6-(methacryloyloxy)hexyloxy)cinnamic acid (2-(2,4-dinitrophenyl)ethyl) ester can be obtained by reacting in accordance with the method described in Japanese Patent No. 6733552.

（合成例２）
　２００ｍＬの圧力容器に（Ｅ）－４－（６―（メタクリロイルオキシ）ヘキシルオキシ）桂皮酸（２－（２，４－ジニトロフェニル）エチル）エステル（２．００ｇ、３．８０ｍｍｏｌ）、トルエン（１０．０ｇ）、ＴＨＦ（１０．０ｇ）、亜リン酸トリエチル（０．２００ｇ、１．２０ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ（５５．０重量％含水型、０．４４４ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で２時間撹拌した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－２のＨＰＬＣ相対面積百分率は９７．８％、反応収率は９６％で過還元体（ＤＡ－２’）は未検出であった。
　反応終了後、触媒をろ過した後、ろ物をＴＨＦ（２．００ｇ）で２回洗浄した。ろ液に水（２０．０ｇ）を加え、撹拌後、水層を除く操作を２回繰り返した後、有機層を１０．０ｇになるまで濃縮し、トルエン（２０．０ｇ）を加え、再度、１０．０ｇになるまで濃縮した後、０℃に冷却し、析出した結晶をろ過し、結晶をトルエン（２．００ｇ）で２回洗浄した後、水（２．００ｇ）で２回洗浄し、４０℃で減圧乾燥し、粉末結晶（ＤＡ－２）を得た（収量１．４０ｇ、収率７８．８％）
　得られた結晶のＨＰＬＣを測定した結果、ＤＡ－２のＨＰＬＣ相対面積百分率は９８．２％で過還元体（ＤＡ－２’）は未検出であった。 (Synthesis Example 2)
To a 200 mL pressure vessel were added (E)-4-(6-(methacryloyloxy)hexyloxy)cinnamic acid (2-(2,4-dinitrophenyl)ethyl) ester (2.00 g, 3.80 mmol), toluene (10.0 g), THF (10.0 g), triethyl phosphite (0.200 g, 1.20 mmol), and 1 wt % Pt/C poisoned with 0.2 wt % iron (55.0 wt % hydrous type, 0.444 g), and the mixture was stirred at 40° C. for 2 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
As a result of measuring the reaction solution by HPLC, the HPLC relative area percentage of DA-2 was 97.8%, the reaction yield was 96%, and no over-reduced product (DA-2') was detected.
After the reaction was completed, the catalyst was filtered, and the residue was washed twice with THF (2.00 g). Water (20.0 g) was added to the filtrate, and after stirring, the operation of removing the water layer was repeated twice, and then the organic layer was concentrated to 10.0 g, toluene (20.0 g) was added, and the mixture was concentrated again to 10.0 g, and then cooled to 0 ° C., and the precipitated crystals were filtered, washed twice with toluene (2.00 g), washed twice with water (2.00 g), and dried under reduced pressure at 40 ° C. to obtain powder crystals (DA-2) (yield 1.40 g, yield 78.8%).
HPLC analysis of the resulting crystals revealed that the HPLC relative area percentage of DA-2 was 98.2%, and no over-reduced product (DA-2') was detected.

＜合成例３＞　（Ｅ）－４－アミノ桂皮酸エチルエステルの製造（化合物ＤＡ－３）

Figure JPOXMLDOC01-appb-C000011
Synthesis Example 3: (E)-Preparation of 4-aminocinnamic acid ethyl ester (Compound DA-3)
Figure JPOXMLDOC01-appb-C000011

　（Ｅ）－４－ニトロ桂皮酸エチルエステルは、東京化成工業株式会社製など、一般的に市販されているものが使用できる。 (E)-4-nitrocinnamic acid ethyl ester can be a commercially available product such as that manufactured by Tokyo Chemical Industry Co., Ltd.

（合成例３）
　２００ｍＬの圧力容器に（Ｅ）－４－ニトロ桂皮酸エチルエステル（２．００ｇ、９．０４ｍｍｏｌ）、ＴＨＦ（２０．０ｇ）、亜リン酸トリエチル（０．２００ｇ、１．２０ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ触媒（５５．０重量％含水型、０．４４４ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で３時間撹拌した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－３のＬＣ相対面積百分率は９９．５％、反応収率は９８％で過還元体（ＤＡ－３’）は未検出であった。
　反応終了後、触媒をろ過した後、ろ物をＴＨＦ（２．００ｇ）で２回洗浄した。ろ液を１０．０ｇになるまで濃縮し、トルエン（２０．０ｇ）を加え、再度、１０．０ｇになるまで濃縮した後、ヘプタン（１０．０ｇ）を加え、０℃に冷却し、析出した結晶をろ過し、結晶をヘプタン（２．００ｇ）で２回洗浄し、４０℃で減圧乾燥し、粉末結晶（ＤＡ－３）を得た（収量１．４８ｇ、収率８５．７％）
　得られた結晶のＨＰＬＣを測定した結果、ＤＡ－３のＨＰＬＣ相対面積百分率は９９．０％で過還元体（ＤＡ－３’）は未検出であった。 (Synthesis Example 3)
To a 200 mL pressure vessel were added (E)-4-nitrocinnamic acid ethyl ester (2.00 g, 9.04 mmol), THF (20.0 g), triethyl phosphite (0.200 g, 1.20 mmol), and 1 wt % Pt/C catalyst poisoned with 0.2 wt % iron (55.0 wt % water-containing type, 0.444 g), and the mixture was stirred at 40° C. for 3 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
As a result of measuring the reaction solution by HPLC, the LC relative area percentage of DA-3 was 99.5%, the reaction yield was 98%, and the over-reduced product (DA-3') was not detected.
After the reaction was completed, the catalyst was filtered, and the residue was washed twice with THF (2.00 g). The filtrate was concentrated to 10.0 g, toluene (20.0 g) was added, and the mixture was concentrated again to 10.0 g. Heptane (10.0 g) was added, and the mixture was cooled to 0° C. The precipitated crystals were filtered, washed twice with heptane (2.00 g), and dried under reduced pressure at 40° C. to obtain powder crystals (DA-3) (yield: 1.48 g, yield: 85.7%).
HPLC of the obtained crystals was measured, and as a result, the HPLC relative area percentage of DA-3 was 99.0%, and no over-reduced product (DA-3') was detected.

＜合成例４＞　（Ｅ）－４－アミノカルコンの製造（化合物ＤＡ－４）

Figure JPOXMLDOC01-appb-C000012
Synthesis Example 4: Preparation of (E)-4-aminochalcone (Compound DA-4)
Figure JPOXMLDOC01-appb-C000012

　４－ニトロカルコンは、東京化成工業株式会社製など、一般的に市販されているものが使用できる。 4-nitrochalcone can be any commercially available product, such as that manufactured by Tokyo Chemical Industry Co., Ltd.

（合成例４）
　２００ｍＬの圧力容器に４－ニトロカルコン（２．００ｇ、７．９０ｍｍｏｌ）、ＴＨＦ（２０．０ｇ）、亜リン酸トリエチル（０．２００ｇ、１．２０ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ触媒（５５．０重量％含水型、０．４４４ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で３時間撹拌した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－４のＨＰＬＣ相対面積百分率は９９．７％、反応収率は１００％で過還元体（ＤＡ－４’）は未検出であった。
　反応終了後、触媒をろ過した後、ろ物をＴＨＦ（２．００ｇ）で２回洗浄した。その後、ろ液を濃縮乾固し、得られた結晶にトルエン（１０．０ｇ）を加え、２０℃で１時間撹拌後、結晶をろ過し、トルエン（２．００ｇ）で２回洗浄し、４０℃で減圧乾燥し、粉末結晶（ＤＡ－４）を得た（収量１．４８ｇ、収率８４．２％）
　得られた結晶のＨＰＬＣを測定した結果、ＤＡ－４のＨＰＬＣ相対面積百分率は９７．３％で過還元体（ＤＡ－４’）は未検出であった。 (Synthesis Example 4)
4-Nitrochalcone (2.00 g, 7.90 mmol), THF (20.0 g), triethyl phosphite (0.200 g, 1.20 mmol), and 1 wt % Pt/C catalyst poisoned with 0.2 wt % iron (55.0 wt % water-containing type, 0.444 g) were added to a 200 mL pressure vessel, and the mixture was stirred at 40° C. for 3 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
As a result of measuring the reaction solution by HPLC, the HPLC relative area percentage of DA-4 was 99.7%, the reaction yield was 100%, and no over-reduced product (DA-4') was detected.
After the reaction was completed, the catalyst was filtered, and the residue was washed twice with THF (2.00 g). The filtrate was then concentrated to dryness, and toluene (10.0 g) was added to the obtained crystals. After stirring at 20° C. for 1 hour, the crystals were filtered, washed twice with toluene (2.00 g), and dried under reduced pressure at 40° C. to obtain powder crystals (DA-4) (yield: 1.48 g, yield: 84.2%).
HPLC analysis of the resulting crystals revealed that the HPLC relative area percentage of DA-4 was 97.3%, and no over-reduced product (DA-4') was detected.

合成例５　（Ｅ）－４－アミノベンゾニトリルの製造（化合物ＤＡ－５） Synthesis Example 5: (E)-4-aminobenzonitrile (Compound DA-5)

Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013

　４－ニトロベンゾニトリルは一般的に市販されているものが使用できる（例えば、東京化成工業株式会社製など）。 4-Nitrobenzonitrile can be generally purchased from commercial sources (for example, from Tokyo Chemical Industry Co., Ltd.).

（合成例５）
　２００ｍＬの圧力容器に４－ニトロベンゾニトリル（２．００ｇ、１３．５ｍｍoｌ）、ＴＨＦ（２０．０ｇ）、亜リン酸トリエチル（０．２００ｇ、１．２０ｍｍoｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ触媒（５５．０重量％含水型、０．４４４ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で１２時間撹拌した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－５のＨＰＬＣ相対面積百分率は９９．５％、反応収率は９６％で過還元体（ＤＡ－５’）は未検出であった。 (Synthesis Example 5)
4-Nitrobenzonitrile (2.00 g, 13.5 mmol), THF (20.0 g), triethyl phosphite (0.200 g, 1.20 mmol), and 1 wt % Pt/C catalyst (55.0 wt % water-containing type, 0.444 g) poisoned with 0.2 wt % iron were placed in a 200 mL pressure vessel, and the mixture was stirred at 40° C. for 12 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
As a result of measuring the reaction solution by HPLC, the HPLC relative area percentage of DA-5 was 99.5%, the reaction yield was 96%, and no over-reduced product (DA-5') was detected.

（合成例６）　２，２－ジメチル－６－アセチルアミノ－２Ｈ－１－ベンゾピランの製造（化合物ＤＡ－６－Ａｃ）

Figure JPOXMLDOC01-appb-C000014
(Synthesis Example 6) Preparation of 2,2-dimethyl-6-acetylamino-2H-1-benzopyran (Compound DA-6-Ac)
Figure JPOXMLDOC01-appb-C000014

　ここで用いられる２，２－ジメチル－６－ニトロ－２Ｈ－１－ベンゾピラン（ＤＮ－６）は、特許第４２５８６５８号に記載の方法に準じて反応させることにより、化合物を得ることができる。 The 2,2-dimethyl-6-nitro-2H-1-benzopyran (DN-6) used here can be reacted in accordance with the method described in Japanese Patent No. 4258658 to obtain the compound.

　２００ｍＬの圧力容器に２，２－ジメチル－６－ニトロ－２Ｈ－１－ベンゾピラン（４．００ｇ、１９．５ｍｍｏｌ）、トルエン（４０．０ｇ）、亜リン酸トリエチル（０７９１ｇ、４．７６ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ（５５．０重量％含水型、０．８８９ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で３時間撹拌した。
　ＨＰＬＣの測定は溶離液を（Ａ）アセトニトリル／（Ｂ）１０　ｍＭ　酢酸アンモニウム　Ａ／Ｂ　＝　５０／５０　（０～３０ｍｉｎ．）に変更した以外は、合成例１と同様の方法で実施した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－６のＨＰＬＣ相対面積百分率は９９．７％、過還元体（ＤＡ－６’）は未検出であった。
　反応終了後、触媒をろ過した後、ろ物をトルエン（４．００ｇ）で２回洗浄した。ろ液に２５℃で無水酢酸（２．０９ｇ、２０．５ｍｍｏｌ）を６分かけて滴下し、その後、２５℃で１時間撹拌した。続いて、４％の炭酸水素ナトリウム水溶液（４０ｇ）を加えて撹拌後、水層を除いた後、水（２０ｇ）を加えて撹拌後、水層を除いた。操作を２回繰り返した後、有機層を１６．８ｇになるまで濃縮し、０℃に冷却し、析出した結晶をろ過し、結晶をトルエン（４．００ｇ）で２回洗浄し、４０℃で減圧乾燥し、粉末結晶（ＤＡ－６－Ａｃ）を得た（収量３．２１ｇ、収率７５．８％）
　得られた結晶のＨＰＬＣを測定した結果、ＤＡ－６－ＡｃのＨＰＬＣ相対面積百分率は９９．６％で過還元体（ＤＡ－６’－Ａｃ）は未検出であった。 2,2-Dimethyl-6-nitro-2H-1-benzopyran (4.00 g, 19.5 mmol), toluene (40.0 g), triethyl phosphite (0,791 g, 4.76 mmol), and 1 wt % Pt/C (55.0 wt % hydrous type, 0.889 g) poisoned with 0.2 wt % iron were added to a 200 mL pressure vessel, and the mixture was stirred at 40° C. for 3 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
The HPLC measurement was carried out in the same manner as in Synthesis Example 1, except that the eluent was changed to (A) acetonitrile/(B) 10 mM ammonium acetate A/B = 50/50 (0 to 30 min.).
As a result of measuring the reaction solution by HPLC, the HPLC relative area percentage of DA-6 was 99.7%, and no over-reduced product (DA-6') was detected.
After the reaction was completed, the catalyst was filtered, and the residue was washed twice with toluene (4.00 g). Acetic anhydride (2.09 g, 20.5 mmol) was added dropwise to the filtrate at 25 ° C. over 6 minutes, and then the mixture was stirred at 25 ° C. for 1 hour. Subsequently, a 4% aqueous solution of sodium hydrogen carbonate (40 g) was added and stirred, and then the aqueous layer was removed. Water (20 g) was added and stirred, and then the aqueous layer was removed. After repeating the operation twice, the organic layer was concentrated to 16.8 g, cooled to 0 ° C., and the precipitated crystals were filtered, washed twice with toluene (4.00 g), and dried under reduced pressure at 40 ° C. to obtain powder crystals (DA-6-Ac) (yield 3.21 g, yield 75.8%).
HPLC analysis of the resulting crystals revealed that the HPLC relative area percentage of DA-6-Ac was 99.6%, and no over-reduced product (DA-6'-Ac) was detected.

（合成例７）

Figure JPOXMLDOC01-appb-C000015
(Synthesis Example 7)
Figure JPOXMLDOC01-appb-C000015

　ここで用いられる（ＤＮ－７）は、特許第５７３７２９１号に記載の方法に準じて反応させることにより、化合物を得ることができる。 The compound (DN-7) used here can be obtained by reacting it according to the method described in Japanese Patent No. 5737291.

　２００ｍＬの圧力容器にＤＮ－７（３．００ｇ、７．４０ｍｍｏｌ）、ＴＨＦ（３０．０ｇ）、亜リン酸トリエチル（０．６００ｇ、３．６１ｍｍｏｌ）、０．２重量％の鉄で被毒された１重量％Ｐｔ／Ｃ（５５．０重量％含水型、０．６６７ｇ）を添加し、ゲージ圧０．３０ＭＰａの水素雰囲気下、４０℃で６時間撹拌した。
　ＨＰＬＣの測定は溶離液を（Ａ）アセトニトリル／（Ｂ）１０　ｍＭ　酢酸アンモニウム　Ａ／Ｂ　＝　６０／４０　（０～３０ｍｉｎ．）に変更した以外は、合成例１と同様の方法で実施した。
　反応液のＨＰＬＣを測定した結果、ＤＡ－７のＨＰＬＣ相対面積百分率は９９．９％、過還元体（（Ｅ）－ＤＡ－７’、または、（Ｚ）－ＤＡ－７’、または、ＤＡ－７”）のＨＰＬＣ相対面積百分率は０．１％であった。
　反応終了後、触媒をろ過した後、ろ物をＴＨＦ（３．００ｇ）で２回洗浄した。ろ液を５０℃でトルエンを留去し、１３．６ｇの溶液を得た。得られた溶液のうち１２．１ｇを１００℃で減圧乾燥し、黄色ガラス状固体（ＤＡ－７）を得た（収量２．４５ｇ、収率９８.９％）
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）：δ　６．６６（ｓ、１Ｈ、Ａｒ），６．５７（ｓ，２Ｈ、Ａｒ），４．４５－４．３７（ｍ，２Ｈ，ＣＨ２），４．０６－３．９７（ｍ，２Ｈ、ＣＨ２），３．４０（ｂｒ，４Ｈ，２ＮＨ２），３．５９（ｂｒ，４Ｈ，ＮＨ２），１．５０－１．３９（ｍ，１８Ｈ，２ｔ－Ｂｕ）． DN-7 (3.00 g, 7.40 mmol), THF (30.0 g), triethyl phosphite (0.600 g, 3.61 mmol), and 1 wt % Pt/C (55.0 wt % hydrous, 0.667 g) poisoned with 0.2 wt % iron were added to a 200 mL pressure vessel, and the mixture was stirred at 40° C. for 6 hours under a hydrogen atmosphere with a gauge pressure of 0.30 MPa.
The HPLC measurement was carried out in the same manner as in Synthesis Example 1, except that the eluent was changed to (A) acetonitrile/(B) 10 mM ammonium acetate A/B = 60/40 (0 to 30 min.).
As a result of measuring the HPLC of the reaction solution, the HPLC relative area percentage of DA-7 was 99.9%, and the HPLC relative area percentage of the over-reduced product ((E)-DA-7', (Z)-DA-7', or DA-7") was 0.1%.
After the reaction was completed, the catalyst was filtered, and the filter cake was washed twice with THF (3.00 g). The filtrate was distilled at 50° C. to remove toluene, and 13.6 g of a solution was obtained. 12.1 g of the obtained solution was dried under reduced pressure at 100° C. to obtain a yellow glassy solid (DA-7) (yield: 2.45 g, 98.9%).
1 H-NMR (CDCl 3 ): δ 6.66 (s, 1H, Ar), 6.57 (s, 2H, Ar), 4.45-4.37 (m, 2H, CH 2 ), 4.06-3.97 (m, 2H, CH 2 ), 3.40 (br, 4H, 2NH 2 ), 3.59 (br, 4H, NH 2 ), 1.50-1.39 (m, 18H, 2t-Bu).

　なお、２０２３年１１月３０日に出願された日本特許出願２０２３－２０２６７８号の明細書、特許請求の範囲及び要約書の全内容および２０２４年２月２９日に出願された日本特許出願２０２４－０２９９１９号の明細書、特許請求の範囲及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2023-202678 filed on November 30, 2023, and the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2024-029919 filed on February 29, 2024 are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (11)

　芳香族環以外の部分に炭素－炭素、炭素－窒素および炭素－酸素から選ばれる多重結合を少なくとも１つ有する芳香族ニトロ化合物を、下記式（１）で表されるリン化合物、下記式（２）で表されるリン化合物、および下記式（３）で表されるリン化合物からなる群から選択される少なくとも１種のリン化合物（Ａ）の存在下、Ｐｔ／Ｃ触媒で接触還元することを特徴とする、芳香族アミノ化合物の製造方法。
　Ｐ（Ｒ１）３　　　（１）
（式（１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　ＰＯ（Ｒ２）３　　　（２）
（式（２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。）
　（Ｒ３）２Ｐ-Ｒ４-Ｐ（Ｒ３）２　　　（３）
（式（３）中、複数のＲ３は、それぞれ独立して、炭素数１～１８のアルキル基、炭素数１～１８のアルケニル基、炭素数１～１８のアルコキシ基、炭素数６～２４のアリール基、炭素数６～２４のアリールオキシ基、炭素数３～１８のシクロアルキル基、又は炭素数３～１８のシクロアルコキシ基を表し、これらは置換基を有していても良い。式（３）中、Ｒ４は炭素数１～１８のアルキレン基、炭素数１～１８のアルケニレン基、炭素数１～１８のアルキレンジオキシ基、炭素数６～２４のアリーレン基、炭素数６～２４のアリーレンジオキシ基、炭素数３～１８のシクロアルキレン基、又は炭素数３～１８のシクロアルキレンジオキシ基を表し、これらは置換基を有していても良い。） A method for producing an aromatic amino compound, comprising catalytically reducing an aromatic nitro compound having at least one multiple bond selected from carbon-carbon, carbon-nitrogen and carbon-oxygen in a portion other than the aromatic ring with a Pt/C catalyst in the presence of at least one phosphorus compound (A) selected from the group consisting of phosphorus compounds represented by the following formula (1), phosphorus compounds represented by the following formula (2) and phosphorus compounds represented by the following formula (3):
P(R 1 ) 3 (1)
(In formula (1), each of the multiple R 1s independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
PO(R 2 ) 3 (2)
(In formula (2), each of the multiple R 2 's independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent.)
(R 3 ) 2 P-R 4 -P(R 3 ) 2 (3)
(In formula (3), each of the multiple R 3 's independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 24 carbon atoms, an aryloxy group having 6 to 24 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or a cycloalkoxy group having 3 to 18 carbon atoms, which may have a substituent. In formula (3), R 4 represents an alkylene group having 1 to 18 carbon atoms, an alkenylene group having 1 to 18 carbon atoms, an alkylenedioxy group having 1 to 18 carbon atoms, an arylene group having 6 to 24 carbon atoms, an arylene dioxy group having 6 to 24 carbon atoms, a cycloalkylene group having 3 to 18 carbon atoms, or a cycloalkylenedioxy group having 3 to 18 carbon atoms, which may have a substituent.) 　前記リン化合物（Ａ）がＰ（ＯＭｅ）３またはＰ（ＯＥｔ）３である、請求項１に記載の芳香族アミノ化合物の製造方法。 2. The method for producing an aromatic amino compound according to claim 1, wherein the phosphorus compound (A) is P(OMe) 3 or P(OEt) 3 . 　前記リン化合物（Ａ）の使用量が、前記芳香族ニトロ化合物に対して５～５０モル％である請求項１に記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to claim 1, wherein the amount of the phosphorus compound (A) used is 5 to 50 mol % relative to the aromatic nitro compound. 　前記芳香族ニトロ化合物が下記式（１）～（３）のいずれかの構造で表わされる請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。
Figure JPOXMLDOC01-appb-C000001
 （式中、Ｒ５、Ｒ６、Ｒ８、Ｒ９はそれぞれ独立して単結合又は２価の基を表し、Ｒ７は水素原子又は１価の基を表し、ｎは１～２の整数を表す。） The method for producing an aromatic amino compound according to any one of claims 1 to 3, wherein the aromatic nitro compound is represented by any one of the structures of the following formulas (1) to (3):
Figure JPOXMLDOC01-appb-C000001
 (In the formula, R 5 , R 6 , R 8 , and R 9 each independently represent a single bond or a divalent group, R 7 represents a hydrogen atom or a monovalent group, and n represents an integer of 1 to 2.) 　前記Ｐｔ／Ｃ触媒における白金の担持量が、Ｐｔ／Ｃ触媒全重量に対して０．５～５ｗｔ％である請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to any one of claims 1 to 3, wherein the amount of platinum supported in the Pt/C catalyst is 0.5 to 5 wt % based on the total weight of the Pt/C catalyst. 　前記Ｐｔ／Ｃ触媒が鉄で被毒されたＰｔ／Ｃ触媒である請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to any one of claims 1 to 3, wherein the Pt/C catalyst is an iron-poisoned Pt/C catalyst. 　前記Ｐｔ／Ｃ触媒の使用量が、前記芳香族ニトロ化合物に対して１～２０重量％である請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to any one of claims 1 to 3, wherein the amount of the Pt/C catalyst used is 1 to 20% by weight relative to the aromatic nitro compound. 　前記接触還元における反応温度が０～１００℃であり、反応時間が０．５時間～２０時間である請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to any one of claims 1 to 3, wherein the reaction temperature in the catalytic reduction is 0 to 100°C and the reaction time is 0.5 to 20 hours. 　さらに、バナジウム化合物を共存させる、請求項１～３のいずれかに記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to any one of claims 1 to 3, further comprising allowing a vanadium compound to coexist. 　前記バナジウム化合物がＶＯ（ａｃａｃ）２である請求項９に記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to claim 9, wherein the vanadium compound is VO(acac) 2 . 　使用する前記バナジウム化合物の使用量が、前記芳香族ニトロ化合物に対して０．１～１．０モル％である請求項９に記載の芳香族アミノ化合物の製造方法。 The method for producing an aromatic amino compound according to claim 9, wherein the amount of the vanadium compound used is 0.1 to 1.0 mol % relative to the aromatic nitro compound.
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