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WO2025115975A1 - Procédé de production d'un composé amino aromatique - Google Patents

Procédé de production d'un composé amino aromatique 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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carbon atoms
carbon
producing
aromatic amino
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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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    • 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
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    • 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
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    • 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
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    • 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

L'invention concerne un nouveau procédé de production d'un composé amino aromatique qui est utile en tant qu'intermédiaire de production pour des matériaux électroniques et des produits chimiques pharmaceutiques et agricoles, et qui a, au niveau d'une fraction autre qu'un cycle aromatique, au moins une liaison multiple choisie parmi le carbone-carbone, le carbone-azote et le carbone-oxygène.　Ce procédé de production d'un composé amino aromatique est caractérisé par la réduction catalytique d'un composé nitro aromatique ayant, au niveau d'une fraction autre qu'un cycle aromatique, au moins une liaison multiple choisie parmi le carbone-carbone, le carbone-azote et le carbone-oxygène, à l'aide d'un catalyseur Pt/C en présence d'au moins un composé de phosphore (A) choisi dans le groupe constitué par les composés de phosphore représentés par la formule (1), les composés de phosphore représentés par la formule (2), et les composés de phosphore représentés par la formule (3).　(1) : P(R1)3 (2) : PO(R2)3 (3) : (R3)2P-R4-P(R3)2 (la signification de chaque symbole dans les formules (1)-(3) est telle que définie dans la description.)
PCT/JP2024/042210 2023-11-30 2024-11-28 Procédé de production d'un composé amino aromatique Pending WO2025115975A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001501201A (ja) * 1996-09-23 2001-01-30 ノバルティス アクチエンゲゼルシャフト 置換芳香族アミノ化合物の製造方法
JP2017523195A (ja) * 2014-07-31 2017-08-17 エグゼリクシス， インコーポレイテッド フッ素１８標識化カボザンチニブ及びその類似体の調製方法
JP2021001207A (ja) * 2013-10-23 2021-01-07 日産化学株式会社 新規なジアミン、ポリアミック酸、及びポリイミド
JP2023156374A (ja) * 2018-06-19 2023-10-24 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子並びに該液晶表示素子の製造方法

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JP2001501201A (ja) * 1996-09-23 2001-01-30 ノバルティス アクチエンゲゼルシャフト 置換芳香族アミノ化合物の製造方法
JP2021001207A (ja) * 2013-10-23 2021-01-07 日産化学株式会社 新規なジアミン、ポリアミック酸、及びポリイミド
JP2022103258A (ja) * 2013-10-23 2022-07-07 日産化学株式会社 新規なジアミン、ポリアミック酸、及びポリイミド
JP2017523195A (ja) * 2014-07-31 2017-08-17 エグゼリクシス， インコーポレイテッド フッ素１８標識化カボザンチニブ及びその類似体の調製方法
JP2023156374A (ja) * 2018-06-19 2023-10-24 日産化学株式会社 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子並びに該液晶表示素子の製造方法

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