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WO2007116111A1 - Procédé de préparation de composés amino au moyen de catalyseurs d'or - Google Patents

Procédé de préparation de composés amino au moyen de catalyseurs d'or Download PDF

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Publication number
WO2007116111A1
WO2007116111A1 PCT/ES2007/070064 ES2007070064W WO2007116111A1 WO 2007116111 A1 WO2007116111 A1 WO 2007116111A1 ES 2007070064 W ES2007070064 W ES 2007070064W WO 2007116111 A1 WO2007116111 A1 WO 2007116111A1
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Prior art keywords
groups
gold
combinations
solvent
process according
Prior art date
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Ceased
Application number
PCT/ES2007/070064
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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 WO2007116111A1 publication Critical patent/WO2007116111A1/fr
Anticipated expiration legal-status Critical
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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
    • 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
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8906—Iron and noble metals
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • 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
    • 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 relates to a process for obtaining amino compounds by selective hydrogenation of nitro compounds in the presence, or not, of other reducible functional groups, using gold catalysts.
  • Patent FR-2,792,630 discloses the preparation of group VIII catalysts for hydrogenating various functional groups in the structure of organic compounds, among which is the nitro group.
  • group VIII metals are always included in the catalyst composition.
  • the chemoselectivity of hydrogenation of nitro groups in the presence of other functional groups is not considered.
  • gold has not been used as the active phase of the catalyst, since it was generally accepted that gold alone was little or no reactive as a catalyst.
  • gold by itself, it is an active and selective catalyst for reducing nitro groups, both when the nitro group is the only reducible functional group of the molecule and when other reducible functional groups are present, using H2 or another hydrogen donor molecule as the reducing agent.
  • the present invention relates to a process for the preparation of amino compounds, characterized in that it comprises a catalytic hydrogenation of the corresponding aromatic nitro compound using a gold catalyst.
  • This process for the selective hydrogenation of aromatic nitro compounds can be carried out when the nitro group is the only reducible functional group or in the presence of other reducible functional groups, such as for example aldehydes, ketones, olefins, nitriles, esters, amides , etc., using gold catalysts.
  • the aromatic nitro compound may further comprise one or more nitro groups.
  • aromatic nitro compound and “amino compounds”, in the context of the present invention, refer to those systems that obey the Hückel electron 4n + 2 rule, for example aromatic hydrocarbons, such as benzenes, polycyclic hydrocarbons (including those partially hydrogenatable, such as tetralin); biphenyls; cyclopentadienyl anion; heteroaromatic compounds, such as pyridines, pyrrols, azoles, diazines, triazines, triazoles, furans, thiophenes and oxazoles; condensed aromatic compounds, such as ⁇ ndoles, quinolines, isoquinolines, carbazoles, purines, phthalazines, benzotriazoles, benzofurans, cinnolines, quinazoles, acridines and benzothiophenes.
  • aromatic hydrocarbons such as benzenes, polycyclic hydrocarbons (including those partially hydrogenatable, such as tetralin); biphen
  • the aromatic nitro compound has a general formula Ar-NO 2 , where Ar is an aromatic ring selected from unsubstituted aryl rings and aryl rings with one or more substitutions.
  • substitutions refer to substitutions of groups selected from Cl to C8 alkyl groups, aromatic or aliphatic vinyl groups Cl to C4, aromatic or aliphatic vinyl groups Cl to C4, alkoxy groups Cl to C8, aryloxy C6H 5 to CioH 8 , fluorine groups, chlorine groups, bromine groups, iodine groups, hydroxy groups, groups with unsaturated carbon-carbon bonds, O- (CO) -alkyl groups, 0- (CO) -aryl groups, COOH groups, OH groups, SH groups, CN groups, SO3- groups, S ⁇ 2-alkyl groups, NH 2 groups, NH-alkyl groups, NH 2 SO 2 groups, NSO 2 - (alkyl) 2 groups, SO 2 -NH-alkyl groups, aromatic or aliphatic aldehyde groups Cl to C4, aliphatic or aromatic ketone groups, imino group Cl to C6, ether groups Cl to C6, thioester, sulfides and combinations thereof.
  • unsaturated carbon-carbon bond includes alkenes, alkynes and alenes bonds.
  • Hydrogenation of nitro groups with gold catalysts according to the present invention can be carried out using molecular hydrogen at pressures between 1 and 100 bars, and at temperatures between 20 0 C and 250 ° C, preferably at a pressure between 5 and 50 bars and at temperatures between 100 0 C and 150 ° C.
  • selective hydrogenation can be achieved through supported gold or encapsulated in an inorganic support.
  • Gold, or modified gold, as explained later in this memory is 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 between gold and the inorganic support on which it is supported is present between 0.1 and 15% gold, more preferably between 0.5 and 5% gold.
  • gold can be applied in metallic or ionic form on said inorganic support.
  • said inorganic support is selected from active carbon, iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica, silicic acid, lanthanum oxide, alumina, zinc oxide, carbonate calcium, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate or lead carbonate and combinations thereof.
  • active carbon iron oxide, titanium oxide, cerium oxide, magnesium oxide, zirconium oxide, silica, silicic acid, lanthanum oxide, alumina, zinc oxide, carbonate calcium, calcium phosphate, calcium sulfate, barium sulfate, lead oxide, lead sulfate or lead carbonate and combinations thereof.
  • the inorganic 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%, and more preferably between 0.05 and 3%.
  • the gold may be doped with a second metal.
  • a metal other than gold is introduced as a gold modifier in the process catalyst. This metal can modify the activity / selectivity ratio of catalyst depending on the reaction to be performed.
  • this doped or modified gold may also be supported, as explained above.
  • the modifying metal, or dopant 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 between gold and the modifying metal is preferably 1: 0.001 and more preferably 1: 0.5.
  • the hydrogenation reaction is carried out by means of a hydrogen source 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 a temperature between 25 ° C and 120 0 C.
  • the source of hydrogen is molecular hydrogen. This procedure is preferably carried out at a pressure between 1 and 100 bar and at a temperature between 20 0 C and 250 0 C, and more preferably at a pressure between 5 and 50 bar and at a temperature between 100 0 C and 150 0 C.
  • the hydrogenation reaction can be carried out in the presence or absence of 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 hydrogenation reaction 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 the recovery of the catalyst can be carried out by recirculation or regeneration.
  • the use of gold as a catalyst can be complemented with any promoter additive.
  • the process of the present invention is described below using examples, which are illustrative only and should not limit the scope of the present invention:
  • 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 HAuCl 4 (0.01M), previously adjusted to pH 7 with NaOH. To prepare 1 g of catalyst, 75 mg of HAuCl 4 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 3-amino styrene with H 2 using catalyst 5, 5% Au / TiO 2
  • Example-3 Preparation of 4-aminobenzonitrile with H 2 using catalyst 5, 5% Au / TiO 2
  • Example-5 Preparation of catalyst 4.5% Au / Fe 2 O 3
  • the gold catalyst supported on iron oxide was prepared by the deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCl 4
  • Example-6 Preparation of 3-amino styrene with H 2 using the catalyst 4.5% Au / Fe 2 O 3
  • Example-7 Preparation of 4-aminobenzonitrile with H 2 using the catalyst 4.5% Au / Fe 2 O 3
  • the contents of the autoclave are heated to 140 ° C and pressurized with 25 bars of hydrogen, setting a stirring level of 1000 rpm.
  • the evolution of the reaction was followed in relation to gas consumption (pressure inside the reactor) and by analysis of the liquid phase by gas chromatography and mass spectrometry.
  • Example-8 Preparation of 4-aminobenzamide with H 2 using the catalyst 4.5% Au / Fe 2 O 3
  • Example-9 Preparation of catalyst 2.1% Au / Ce ⁇ 2
  • the gold catalyst supported on high surface cerium oxide (180 m 2 / g) was prepared by deposition-precipitation technique. Deposition-precipitation of gold was carried out by adding the support to an aqueous solution of HAuCl 4 (0.01M), previously adjusted to pH 10 with NaOH. To prepare 1 g of catalyst, 105 mg of HAuCl 4 should be used. The mixture was kept stirring at room temperature under vigorous stirring for 12 hours, controlling the pH to a value of 10. The sample was then filtered, washed with deionized water until the chlorides were removed and dried at 373 K.
  • Example-10 Preparation of 4-aminobenzamide with H 2 using 2.1% Au / Ce ⁇ 2 catalyst
  • 1.6 g of catalyst, prepared according to Example 9 are added to a solution of 3.3 g of 4-nitrobenzamide in 100 mL of a 4/1 tetrahydrofuran / ethanol mixture by weight, and 1.1 g of o-xylene is used as the internal standard of the reaction.
  • the autoclave content is heated to 120 ° C and pressurized with 15 bars of hydrogen, setting a stirring level of 1000 rpm.
  • the evolution of the reaction was followed in relation to the consumption of gas (pressure inside the reactor) and by analysis of the liquid phase by chromatography of gases and mass spectrometry.
  • 4-aminobenzamide was produced with a yield of 79% and a selectivity greater than 99%.
  • the gold catalyst on mesoporous silica material type MCM-41 was prepared from an aqueous solution of HAuCl 4 and dodecacyltrimethylammonium bromide (CTMABr) to which a suitable amount of an aqueous solution of aqueous solution was slowly added at 40 ° C. NaBH 4 , such that the final molar composition was: 1 CTMABr: 0.043 Au: 0.069 NaBH 4 : 600 H 2 O. Next, an adequate amount of sodium silicate was added to the solution of HAuCl 4 , the pH of the solution at a value of 10 with H 2 SO 4 1.2 M.
  • CTMABr dodecacyltrimethylammonium bromide
  • each reagent should be such that the molar composition of the final gel is: 1 CTMABr: 1.4 SiO 2 : 2800 H 2 O.
  • the hydrothermal synthesis of MCM material -41 with gold particles supported on its surface should be carried out at 100 ° C for 12 hours.
  • the gel obtained is filtered, washed with deionized water, dried at 60 ° C and finally calcined at 560 ° C.
  • Example-12 Preparation of 4-amino styrene with H 2 using the 2% Au / MCM-41 catalyst
  • Example-13 Preparation of 4-amino styrene with ammonium formate using catalyst 2. l% Au / Ti ⁇ 2
  • Example-14 Preparation of 4-amino styrene with H 2 in the absence of solvent using the catalyst 1.5% Au / TiO 2

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

Abstract

L'invention se rapporte à un procédé de préparation de composés amino qui comprend l'hydrogénation catalytique du composé nitroaromatique correspondant au moyen d'un catalyseur d'or.
PCT/ES2007/070064 2006-04-10 2007-03-28 Procédé de préparation de composés amino au moyen de catalyseurs d'or Ceased WO2007116111A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ES200601011A ES2285934B1 (es) 2006-04-10 2006-04-10 Procedimiento para preparar compuestos amino utilizando catalizadores de oro.
ESP200601011 2006-04-10

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WO2007116111A1 true WO2007116111A1 (fr) 2007-10-18

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071727A1 (fr) * 2007-12-05 2009-06-11 Consejo Superior De Investigaciones Cientificas Procédé d'hydrogénation sélective de composés nitroaromatiques substitués
ES2345028A1 (es) * 2009-03-10 2010-09-13 Universidad Politecnica De Valencia Preparacion de carbamatos en "one pot" con catalizadores solidos.
CN102285891A (zh) * 2011-06-30 2011-12-21 浙江工业大学 一种由芳香硝基化合物催化加氢制备芳胺的方法
US20150031901A1 (en) * 2011-11-29 2015-01-29 Sanofi Method for preparing 5-amino-benzofuran derivatives
CN104974047B (zh) * 2014-04-03 2017-02-15 长春工业大学 硝基苯乙烯催化加氢制备氨基苯乙烯的方法
US9611242B2 (en) 2011-03-29 2017-04-04 Sanofi Process for preparation of dronedarone by N-butylation
US9701654B2 (en) 2012-02-13 2017-07-11 Sanofi Process for preparation of dronedarone by removal of hydroxyl group
US9708281B2 (en) 2012-01-20 2017-07-18 Sanofi Process for preparation of dronedarone by the use of dibutylaminopropanol reagent
CN107417568A (zh) * 2017-05-26 2017-12-01 长春工业大学 硝基芳香化合物催化加氢制备氨基芳香化合物的方法
CN109070062A (zh) * 2016-03-23 2018-12-21 恩亿凯嘉股份有限公司 催化剂混合物
US11452992B2 (en) 2019-03-20 2022-09-27 King Fahd University Of Petroleum And Minerals Iron oxide supported rhodium catalyst for nitroarene reduction
CN115445626A (zh) * 2022-09-26 2022-12-09 长春工业大学 一种硝基苯乙炔加氢制备氨基苯乙炔的催化剂

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995032941A1 (fr) * 1994-05-27 1995-12-07 Ciba-Geigy Ag Procede de preparation de composes amines insatures
WO1996036588A1 (fr) * 1995-05-18 1996-11-21 Novartis Ag Procede de preparation de composes amino aromatiques substitues
FR2792630A1 (fr) * 1999-04-26 2000-10-27 Inst Francais Du Petrole Procede d'hydrogenation de fonctions organiques en presence d'un catalyseur comprenant un metal du groupe viii et un element additionel introduit sous forme de compose organometallique hydrosoluble

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995032941A1 (fr) * 1994-05-27 1995-12-07 Ciba-Geigy Ag Procede de preparation de composes amines insatures
WO1996036588A1 (fr) * 1995-05-18 1996-11-21 Novartis Ag Procede de preparation de composes amino aromatiques substitues
FR2792630A1 (fr) * 1999-04-26 2000-10-27 Inst Francais Du Petrole Procede d'hydrogenation de fonctions organiques en presence d'un catalyseur comprenant un metal du groupe viii et un element additionel introduit sous forme de compose organometallique hydrosoluble

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009071727A1 (fr) * 2007-12-05 2009-06-11 Consejo Superior De Investigaciones Cientificas Procédé d'hydrogénation sélective de composés nitroaromatiques substitués
ES2322221A1 (es) * 2007-12-05 2009-06-17 Universidad Politecnica De Valencia Procedimiento de hidrogenacion selectiva de compuestos nitroaromaticos sustituidos.
CN102369183A (zh) * 2009-03-10 2012-03-07 康斯乔最高科学研究公司 利用固体催化剂一锅法制备氨基甲酸酯
WO2010103155A1 (fr) * 2009-03-10 2010-09-16 Consejo Superior De Investigaciones Científicas (Csic) (50%) Préparation de carbamates en monotope avec des catalyseurs solides
ES2345028B2 (es) * 2009-03-10 2011-06-06 Universidad Politecnica De Valencia Preparacion de carbamatos en "one pot" con catalizadores solidos.
US8765993B2 (en) 2009-03-10 2014-07-01 Consejo Superior De Investigaciones Cientificas One-pot production of carbamates using solid catalysts
ES2345028A1 (es) * 2009-03-10 2010-09-13 Universidad Politecnica De Valencia Preparacion de carbamatos en "one pot" con catalizadores solidos.
US9611242B2 (en) 2011-03-29 2017-04-04 Sanofi Process for preparation of dronedarone by N-butylation
CN102285891A (zh) * 2011-06-30 2011-12-21 浙江工业大学 一种由芳香硝基化合物催化加氢制备芳胺的方法
US20150031901A1 (en) * 2011-11-29 2015-01-29 Sanofi Method for preparing 5-amino-benzofuran derivatives
US9499507B2 (en) * 2011-11-29 2016-11-22 Sanofi Method for preparing 5-amino-benzoyl-benzofuran derivatives
US9708281B2 (en) 2012-01-20 2017-07-18 Sanofi Process for preparation of dronedarone by the use of dibutylaminopropanol reagent
US9701654B2 (en) 2012-02-13 2017-07-11 Sanofi Process for preparation of dronedarone by removal of hydroxyl group
CN104974047B (zh) * 2014-04-03 2017-02-15 长春工业大学 硝基苯乙烯催化加氢制备氨基苯乙烯的方法
CN109070062A (zh) * 2016-03-23 2018-12-21 恩亿凯嘉股份有限公司 催化剂混合物
CN107417568A (zh) * 2017-05-26 2017-12-01 长春工业大学 硝基芳香化合物催化加氢制备氨基芳香化合物的方法
CN107417568B (zh) * 2017-05-26 2021-10-15 长春工业大学 硝基芳香化合物催化加氢制备氨基芳香化合物的方法
US11452992B2 (en) 2019-03-20 2022-09-27 King Fahd University Of Petroleum And Minerals Iron oxide supported rhodium catalyst for nitroarene reduction
US11712680B2 (en) 2019-03-20 2023-08-01 King Fahd University Of Petroleum And Minerals Process for reducing aromatic nitro compounds with supported catalyst
CN115445626A (zh) * 2022-09-26 2022-12-09 长春工业大学 一种硝基苯乙炔加氢制备氨基苯乙炔的催化剂

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ES2285934B1 (es) 2008-12-16
ES2285934A1 (es) 2007-11-16

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