WO2007116112A1 - Procédé de préparation d'oxymes au moyen de catalyseurs d'or - Google Patents

Procédé de préparation d'oxymes au moyen de catalyseurs d'or Download PDF

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Publication number
WO2007116112A1
WO2007116112A1 PCT/ES2007/070065 ES2007070065W WO2007116112A1 WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1 ES 2007070065 W ES2007070065 W ES 2007070065W WO 2007116112 A1 WO2007116112 A1 WO 2007116112A1
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WO
WIPO (PCT)
Prior art keywords
gold
combinations
process according
solvent
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/ES2007/070065
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English (en)
Spanish (es)
Inventor
Avelino Corma Canos
Pedro Serna Merino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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Publication of WO2007116112A1 publication Critical patent/WO2007116112A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/66—Silver or gold
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/10—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes from nitro compounds or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation

Definitions

  • the present invention deals with a new process for the production of oximes by selective hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using gold catalysts.
  • the oximes specifically, the cyclohexanone oxime is a key product as an intermediate in the production of epsilon-caprolactam, a precursor to nylon-6.
  • commercial processes for the production of cyclohexanone oxime include the reaction of cyclohexanone with hydroxylamine sulfate and ammonia. This process is far from ideal, considering the large number of steps required and the generation of sulfates as a byproduct.
  • Various processes have been proposed in order to improve the production process of cyclohexanone oxime. In most cases, the direct use of hydroxylamine or its generation in situ in the reaction medium is considered, assuming a relatively high degree of danger due to the high explosive index of the product.
  • cyclohexanone oxime Some variants of the above processes for producing cyclohexanone oxime disclose different forms for the production of hydrogen peroxide in situ, prior to its reaction with ammonia.
  • the CN- 1,472, 197 patent relates to a process of producing cyclohexanone oxime by ammoximation of cyclohexanone with ammonia and H 2 O 2 produced by the method of the anthraquinone.
  • US Patent 5,599,987 the production of cyclohexanone oxime is disclosed by a process similar, but in which hydrogen peroxide is obtained by oxidation of isopropanol with O 2 .
  • JP-2001-213,854 an alternative route for the production of cyclohexanone oxime is proposed in which benzene is used as the starting product to form cyclohexene by partial dehydrogenation with a catalyst.
  • 1-nitro-1-cyclohexene is obtained by a nitration reaction and as a last step a catalyst B is used to produce the cyclohexanone oxime through the partial hydrogenation of the nitro ⁇ - ⁇ -unsaturated compound.
  • the present invention relates to a process for the preparation of oximes characterized in that it comprises a catalytic hydrogenation of the corresponding nitro ⁇ , ⁇ -unsaturated compound using a gold catalyst.
  • the oxime is cyclohexanone oxime and the nitro compound is 1-nitro-1-cyclohexene.
  • it is a process for the preparation of the cyclohexanone oxime characterized in that it comprises a catalytic hydrogenation of 1-nitro-1-cyclohexene using gold catalysts.
  • the gold catalysts of the present invention catalyze the selective hydrogenation of nitro ⁇ , ⁇ -unsaturated groups to the corresponding oxime, avoiding the direct hydrogenation of the double bond to form the saturated nitro compound.
  • gold can be supported on an inorganic support.
  • Gold, or modified gold, as explained later in this report, can be supported in order to increase its dispersion and decrease the particle size on supports of inorganic or carbonaceous nature, as is known in the field. of metal catalysts.
  • the percentage by weight of gold with respect to the solid support on which it is supported is preferably between 0.1 and 15% gold and more preferably between 0.5 and 5% gold.
  • gold can be applied in metallic or ionic form on the support.
  • said support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica gel, silicic acid, lanthanum oxide, alumina, zinc oxide, calcium carbonate, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate, lead carbonate and combinations thereof.
  • said support is selected from iron oxide, titanium oxide, cerium oxide, silica and combinations thereof.
  • the molar ratio between gold and the nitro compound is preferably between 0.01 and 10%, more preferably between 0.05 and 3%.
  • the gold may be doped with a second metal.
  • a metal other than gold as a modifier or dopant is introduced into the catalyst of the process.
  • This metal modifier can improve the catalytic properties of the material.
  • this doped or modified gold may also be supported, as explained above.
  • the modifying metal is selected from palladium, platinum, rhodium, nickel, copper, ruthenium, lead, mercury, bismuth, germanium, cadmium, arsenic, antimony, silver, iron, manganese, cobalt, ruthenium and combinations thereof .
  • the weight ratio of gold to said modifying metal is preferably 1: 0.001 and more preferably 1: 0.5.
  • the process of the present invention further comprises a source of hydrogen that can be any hydrogen donor molecule.
  • the hydrogen source is selected from ammonium formate, formic acid, decaborane, cyclohexene, cyclohexadiene, phosphoric acid and combinations thereof.
  • the process is preferably carried out at atmospheric pressure and at a temperature between 25 0 C and
  • the source of hydrogen is molecular hydrogen. This process is preferably carried out at a pressure between 1 and 100 bar and at a temperature between 2O 0 C and 25O 0 C, and more preferably at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 15O 0 C.
  • the hydrogenation reaction can be carried out with or without solvent.
  • a particularly interesting advantage of the use of gold, according to the present invention is that the choice of the reaction solvent is not critical. It is possible to use solvents that are not normally inert in the presence of palladium and platinum catalysts.
  • solvent it is preferably selected from water, alcohols preferably selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isomeric butane, cyclohexanol and combinations thereof; ethers preferably selected from diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, dimethoxyethane and combinations thereof; esters preferably selected from ethyl acetate, butyl acetate and combinations thereof; ketones preferably selected from butyrolactone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and combinations thereof; carboxylic acids preferably selected from acetic acid, propionic acid and combinations thereof; aprotic dipole solvents preferably selected from dimethylformamide, N-methylpyrrolidine, dimethylacetamide, sulfo
  • Said solvent serves as a means of dissolution or to facilitate separation processes.
  • said solvent is selected from toluene, xylene, tetrahydrofuran, dioxane, methyl ethyl ketone, methanol, ethanol and combinations thereof.
  • the process of the present invention can also be carried out in the presence of one or more co-solvents.
  • Said co-solvent is preferably selected from ethanol, acetone, acetonitrile and combinations thereof.
  • the process is carried out in the absence of solvent.
  • the reagents that are hydrogenated during the process are preferably in the liquid, gas or coexistence phase of both.
  • the process of the present invention can be carried out in the gas-solid phase (catalyst) or in a gas-liquid-solid system (catalyst).
  • said process can be carried out in a reactor in discontinuous or continuous mode, and catalyst recovery can be enhanced by recirculation or regeneration.
  • the use of gold as a catalyst can be complemented with any promoter additive.
  • Example-1 Preparation of catalyst 1.5% A11 / TIO2
  • the gold catalyst supported on titanium oxide was prepared by deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCU (0.01M), previously adjusted to pH 7 with NaOH. To prepare 1 g of catalyst, 75 mg of HAuCU should be used. The mixture was kept stirring at 343 K under vigorous stirring for 2 hours, controlling the pH to a value of 7. The sample was then filtered, washed with deionized water until the chlorides were removed, dried under vacuum at 353 K and calcined at 673 K in air.
  • Example-2 Preparation of cyclohexanone oxime with H 2 using 1.5% Au / TiO 2 catalyst
  • Example-3 Preparation of cyclohexanone oxime with ammonium formate using catalyst 1.5% Au / Ti ⁇ 2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention se rapporte à un procédé de préparation d'oxymes qui comprend l'hydrogénation catalytique du composé nitro α, β-insaturé correspondant au moyen d'un catalyseur d'or.
PCT/ES2007/070065 2006-04-12 2007-03-28 Procédé de préparation d'oxymes au moyen de catalyseurs d'or Ceased WO2007116112A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200601117A ES2289925B2 (es) 2006-04-12 2006-04-12 Procedimiento para la preparacion de oximas utilizando catalizadores de oro.
ESP200601117 2006-04-12

Publications (1)

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WO2007116112A1 true WO2007116112A1 (fr) 2007-10-18

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PCT/ES2007/070065 Ceased WO2007116112A1 (fr) 2006-04-12 2007-03-28 Procédé de préparation d'oxymes au moyen de catalyseurs d'or

Country Status (2)

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ES (1) ES2289925B2 (fr)
WO (1) WO2007116112A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2337004A1 (es) * 2008-10-16 2010-04-19 Universidad Politecnica De Valencia Procedimiento de hidrogeneracion selectiva de nitrocicloalcanos para obtener oximas ciclicas.
WO2014191589A1 (fr) * 2013-05-27 2014-12-04 Consejo Superior De Investigaciones Científicas (Csic) Procédé d'obtention directe d'oxime de cyclohexanone à partir de nitrodérivés

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346674A1 (fr) * 1988-06-13 1989-12-20 Mitsubishi Kasei Corporation Procédé pour la synthèse d'oximes
JP2001213854A (ja) * 2000-02-02 2001-08-07 Asahi Kasei Corp シクロヘキサノンオキシムの製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346674A1 (fr) * 1988-06-13 1989-12-20 Mitsubishi Kasei Corporation Procédé pour la synthèse d'oximes
JP2001213854A (ja) * 2000-02-02 2001-08-07 Asahi Kasei Corp シクロヘキサノンオキシムの製造方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200175, Derwent World Patents Index; AN 2001-650716 *
KABALKA ET AL.: "The palladium assisted transfer reduction of a,b-unsaturated nitroalkenes to oximes using ammonium formate", SYNTHETIC COMMUNICATIONS, vol. 20, no. 16, 1990, pages 2453 - 2458 *
SEUNG HWANG LEE ET AL.: "Catalytic transfer hydrogenation of conjugated nitroalkenes using decarborane: synthesis of oximes", ORGANIC AND BIOMOLECULAR CHEMISTRY, vol. 1, no. 7, 2003, pages 1099 - 1100 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2337004A1 (es) * 2008-10-16 2010-04-19 Universidad Politecnica De Valencia Procedimiento de hidrogeneracion selectiva de nitrocicloalcanos para obtener oximas ciclicas.
WO2010043738A1 (fr) * 2008-10-16 2010-04-22 Universidad Politécnica De Valencia (Upv) Procédé d'hydrogénation sélective de nitrocycloalcanes pour obtenir des oximes cycliques
ES2337004B1 (es) * 2008-10-16 2011-02-15 Universidad Politecnica De Valencia Procedimiento de hidrogenacion selectiva de nitrocicloalcanos para obtener oximas ciclicas.
WO2014191589A1 (fr) * 2013-05-27 2014-12-04 Consejo Superior De Investigaciones Científicas (Csic) Procédé d'obtention directe d'oxime de cyclohexanone à partir de nitrodérivés

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Publication number Publication date
ES2289925A1 (es) 2008-02-01
ES2289925B2 (es) 2008-08-16

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