WO2008017342A1 - Oxydation catalytique de terpène avec des catalyseurs de métaux nobles - Google Patents

Oxydation catalytique de terpène avec des catalyseurs de métaux nobles Download PDF

Info

Publication number
WO2008017342A1
WO2008017342A1 PCT/EP2007/005231 EP2007005231W WO2008017342A1 WO 2008017342 A1 WO2008017342 A1 WO 2008017342A1 EP 2007005231 W EP2007005231 W EP 2007005231W WO 2008017342 A1 WO2008017342 A1 WO 2008017342A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxygen
terpene
catalyst
oxidation
bar
Prior art date
Application number
PCT/EP2007/005231
Other languages
German (de)
English (en)
Inventor
Thomas Gedig
Daniel Decker
Andreas Martin
Angela KÖCKRITZ
Udo Armbruster
Michael Kant
Original Assignee
Clariant Specialty Fine Chemicals (Deutschland) Gmbh
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant Specialty Fine Chemicals (Deutschland) Gmbh filed Critical Clariant Specialty Fine Chemicals (Deutschland) Gmbh
Publication of WO2008017342A1 publication Critical patent/WO2008017342A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
    • C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups

Definitions

  • the invention relates to the heterogeneous-catalytic oxidation of oxygen-containing terpenes in the liquid phase using noble metal-containing catalysts and oxygen, mixtures of oxygen and inert gases or air as an oxidant in the corresponding carboxylic acids.
  • terpenes of different oxidation states can serve as reactants, for example terpene alcohols or terpene aldehydes.
  • the use of supported noble metal catalysts is essential for achieving high product selectivities.
  • the catalysts used in the process according to the invention consist of noble metals and oxidic support materials.
  • the catalyst contains gold alone or gold in combination with one or more metal compounds from the group consisting of Rh, Ir, Pd, Pt and Ag.
  • the precious metals or precious metal combinations are present in the oxidation state 0.
  • the oxidic support materials include Al 2 O 3 , TiO 2 , SiO 2 , aluminosilicates, ZrO 2 , CeO 2 , Y 2 O 3 , Nb 2 O 3 , zeolites and mesoporous materials such as MCM-41 (Mobil OiI Corp.), SBA- 15 (SBA Materials, Inc.).
  • Carrier catalysts in the liquid phase in the corresponding aldehydes and carboxylic acids transferred (WO 2002/016 298).
  • activated alcohols such as diols, (H. Berndt, I. Pitsch, S. Evert, K. Struve, M.-M. Pohl, J. Radnik, A. Martin, Appl. Catal. A: Gen. 244 ( 2003) 169;) or triols, eg Glycerol, gold has been described as a suitable selective catalyst for the aerobic oxidation to carboxylic acids.
  • Polymer-stabilized colloidal gold nanoclusters served as catalysts for long-chain diols, they must be separated after the reaction on polymer membranes (PGN Mertens, I. FJ Vankelecom, PA Jacobs, DE De Vos, Gold Bulletin 38 (2005) 157-162) and are not particularly leaching-stable.
  • Aldehydes can react in a radical process with oxygen to form peracids in addition to a catalytic oxidation without catalyst in a radical process, they can oxidize another molecule of aldehyde to acid and even react to a molecule of acid, the best solvents are halogenated hydrocarbons. The cleavage of the peracid can be problematic, it could be achieved in JP 2001011009 by pyrolysis under inert gas in aliphatic hydrocarbons as a solvent.
  • gold on oxidic supports is a suitable catalyst system for the aerobic oxidation
  • Aldonic acids (WO 2004/099 114 A8, H. Berndt, A. Martin, I. Pitsch, U. Pruess, K.D. Vorlop, Catal. Today 91-92 (2004) 191).
  • the reaction requires an alkaline medium (pH 8-12).
  • side reactions may occur in the oxidation of CH-acidic aldehydes (e.g., aldol reaction, Cannizzaro reaction).
  • Unsaturated aliphatic aldehydes can also be oxidized with copper, silver and gold supported catalysts continuously in the gas phase at 300 to 600 0 C with oxygen to the unsaturated carboxylic acids (DE 000019 722 567). However, these reaction conditions are not suitable for terpene compounds.
  • terpene carboxylic acids such as citronellic acid
  • microbial methods S. Oda, T. Sugai, H. Ohta, Bull. Chem. Soc., Japan, 73 (2000) 2819.
  • space-time yields are not sufficient for an industrial process.
  • the object of the present invention is thus to provide a process which uses a long-term stable and easily recyclable catalyst with a very high catalyst productivity and at the same time good yields and selectivities under mild reaction conditions with reaction temperatures ⁇ 100 0 C and slightly basic pH supplies.
  • the inventive method fulfills the stated object and relates to a process for the oxidation of terpenes in the liquid phase in the presence of a gold-containing supported catalyst by an oxygen-containing gas to the corresponding terpene carboxylic acids.
  • terpene alcohols or terpene aldehydes are used according to the invention.
  • terpene alcohols are in particular primary terpene alcohols, such. Geraniol, nerol, citronellol, dihydrocitronellol, lavandulol, famesol, myrtenol, lanceol, phytol, plaunotol, betulenol, khusol, drimenol, santalol, geranylgeraniol, all-trans-retinol or 3,4-dehydroretinol in question.
  • the starting sterene of the formula (1) is preferably used in concentrations of from 0.01 mol / l to 10 mol / l, in particular from 0.1 mol / l to 2 mol / l.
  • the gold-containing catalysts used in the method according to the invention preferably contain 0.1 to 10 wt .-% Au and 0.1 to 10 wt .-% of one or more noble metals from the group: Rh, Ru, Ir, Pd, Pt and / or Ag , applied to an oxidic carrier material.
  • the precious metals or precious metal combinations are mainly present in the oxidation state 0.
  • the oxidic support materials include Al 2 O 3 , TiO 2 , SiO 2 , aluminosilicates, ZrO 2 , CeO 2 , Y 2 O 3 , Nb 2 O 3 , zeolites and mesoporous materials such as MCM-41, SBA-15.
  • the support of the gold particles on oxidic support materials improves the properties of the catalysts used compared with carbonaceous support materials, such as activated carbon, carbon black and organic carriers. They can be recycled several times, they are easily separable from the products and long-term stability against oxidation and leaching. This advantage is evident when compared to noble metal nanoparticles embedded in organic polymers which show strong leaching or lack of stability under reaction conditions in liquid-phase oxidations with molecular oxygen (A. Biffis, L. Minati, J. Catal., 236 (2005) 405).
  • the gold catalyst used increases the yield and the selectivity of the oxidation to the terpene carboxylic acids.
  • an oxygen-containing gas preferably pure oxygen, air or mixtures of oxygen and intergass, e.g. Nitrogen or argon used.
  • the oxygen content of the oxygen-containing gas is preferably between 5% and 99%, in particular in the range of 20% to 99%.
  • the oxygen-containing gas is introduced at pressures of from 1 bar to 20 bar into the reaction solution.
  • the process according to the invention can be carried out in the solvent which is preferable for ecological and safety reasons.
  • the process according to the invention is preferably carried out at atmospheric pressure. However, the use of higher pressure up to 10 bar is not excluded.
  • the gas stream should be added via a gassing stirrer. By the speed of the gas stream, the turnover can be controlled. Preference is given to operating at a pressure in the range from 1 bar to 5 bar, wherein the oxygen-containing gas is introduced at a rate of 10 ml / min to 5000 ml / min.
  • terpene carboxylic acids for example, in an aqueous medium in the pH range of pH 8 to pH 12, in particular in the range of pH 8 to pH 9, and at temperatures between 5 ° C and 120 0 C, in particular from 50 0 C to 9O 0 C are prepared.
  • the reaction also proceeds in the more alkaline pH range, but side reactions such as the Aldol and Cannizzaro reactions are favored, resulting in poorer product selectivity.
  • solvents for the process according to the invention for example, aliphatic alcohols having 1 to 5 carbon atoms, halogenated hydrocarbons having 1 to 10 carbon atoms or aromatic
  • Hydrocarbons having 6 to 10 carbon atoms are used.
  • water is used as the solvent.
  • the inventive method is characterized in that high catalyst productivities of 7350 mol Rea ⁇ ⁇ tand / Mol ⁇ ataiysator for a batch
  • citronellol In a 1 l glass reactor equipped with a gassing stirrer, a heater and an automatic pH control, 0.05 mol of citronellol are dispersed in 400 ml of water. The mixture is adjusted with KOH to a pH of 9 and brought to a temperature of 80 0 C. 1 g of catalyst (1% Au on Al 2 O 3 ) is added to the dispersion. With vigorous stirring, oxygen is introduced at a rate of 200 ml / min. The pH is kept constant over the entire reaction time of 5 h. Upon completion, cool to room temperature. The reaction solution is adjusted to pH 3 with dilute hydrochloric acid and extracted three times with 100 ml of dichloromethane each time. The organic solution is dried over Na 2 SO 4 and analyzed by HPLC (YMC Hydrosphere C18, 60:40 vol .-% acetonitrile / 0.1% aqueous trifluoroacetic acid).
  • HPLC YMC Hydrosphere C18, 60:40 vol .-
  • the procedure is as in Example 1, except that 0.05 mol of citronellal is used as the substrate.
  • Example 3 The procedure is as in Example 2, except that 0.15 mol of citronellal be used.
  • Example 6 The procedure is as in Example 3 except that only 0.25 g of catalyst (1% Au on Al 2 O 3 ) are used.
  • Example 7
  • Example 2 The procedure is as in Example 2, except that oxygen is passed through the reaction solution at a rate of 50 ml / min.
  • Example 9 The procedure is as in Example 2, except that air is passed through the reaction solution at a rate of 200 ml / min.
  • Example 2 The procedure is as in Example 2, except that 0.5% Au-0, 5% Pt on activated carbon is used as the catalyst.
  • Example 2 The procedure is as in Example 2, except that 0.05 mol of citral are used as the substrate.
  • Catalyst Recycling The experiment is carried out as described in Example 2. After completion of the catalyst is filtered off, washed several times with water and used in a new run. The recycling of the Catalyst was repeated over 6 reaction cycles. The conversions, yields and selectivities achieved are listed in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne l'oxydation catalytique de terpène contenant de l'oxygène en phase liquide en utilisant des catalyseurs contenant des métaux nobles et de l'oxygène, des mélanges d'oxygène et de gaz inertes ou de l'air en tant qu'oxydant. Du terpène de différents degrés d'oxydation peut ainsi servir en tant que réactif, par exemple le terpène alcool ou le terpène aldéhyde. L'utilisation de catalyseurs supportés à base de métaux nobles est essentielle à l'obtention d'une meilleure sélectivité de produits. Une meilleure sélectivité en acide carboxylique est obtenue à un pH de 8 à 12, une température de réaction de 5 à 120 °C et une pression de 1 à 10 bars, avec un rendement quantitatif.
PCT/EP2007/005231 2006-08-10 2007-06-14 Oxydation catalytique de terpène avec des catalyseurs de métaux nobles WO2008017342A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006037447.9 2006-08-10
DE200610037447 DE102006037447A1 (de) 2006-08-10 2006-08-10 Katalytische Oxidation von Terpenen mit Edelmetallkatalysatoren

Publications (1)

Publication Number Publication Date
WO2008017342A1 true WO2008017342A1 (fr) 2008-02-14

Family

ID=38561941

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/005231 WO2008017342A1 (fr) 2006-08-10 2007-06-14 Oxydation catalytique de terpène avec des catalyseurs de métaux nobles

Country Status (2)

Country Link
DE (1) DE102006037447A1 (fr)
WO (1) WO2008017342A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011006183A1 (fr) * 2009-07-16 2011-01-20 Commonwealth Scientific And Industrial Research Organisation Cinéol
WO2011020878A2 (fr) 2009-08-21 2011-02-24 Basf Se Procédé de production d'acide pentène-4-oïque

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342862A (en) * 1971-03-22 1974-01-03 Givaudan & Cie Sa Process for preparing hydroxycitronellal
WO2002016298A1 (fr) * 2000-08-18 2002-02-28 E.I. Du Pont De Nemours And Company Catalyseur a base d'or destine a l'oxydation selective

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342862A (en) * 1971-03-22 1974-01-03 Givaudan & Cie Sa Process for preparing hydroxycitronellal
WO2002016298A1 (fr) * 2000-08-18 2002-02-28 E.I. Du Pont De Nemours And Company Catalyseur a base d'or destine a l'oxydation selective

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011006183A1 (fr) * 2009-07-16 2011-01-20 Commonwealth Scientific And Industrial Research Organisation Cinéol
CN102482178A (zh) * 2009-07-16 2012-05-30 联邦科学和工业研究组织 桉叶素
US8710287B2 (en) 2009-07-16 2014-04-29 Commonwealth Scientific And Industrial Research Organisation Cineole
CN102482178B (zh) * 2009-07-16 2014-07-30 联邦科学和工业研究组织 桉叶素
EA020285B1 (ru) * 2009-07-16 2014-10-30 Коммонвелт Сайентифик Энд Индастриал Рисерч Организейшн Способ получения соединений - с10-монотерпеноидов из 1,8-цинеола
WO2011020878A2 (fr) 2009-08-21 2011-02-24 Basf Se Procédé de production d'acide pentène-4-oïque
US8362296B2 (en) 2009-08-21 2013-01-29 Basf Se Process for preparing 4-pentenoic acid

Also Published As

Publication number Publication date
DE102006037447A1 (de) 2008-02-14

Similar Documents

Publication Publication Date Title
DE60217548T2 (de) Organische chemische oxidation während der herstellung von wasserstoffperoxid
EP1854778B1 (fr) Procédé catalytique destiné à la fabrication d'acides de carbone aliphatiques, à chaînes droites et ramifiés en béta alkyles
EP3209650B1 (fr) Procede de preparation de carbonate de l'acide glycerique
WO2001074767A1 (fr) Procede pour la production d'alcools aromatiques, notamment de phenol
DE10009207A1 (de) Verbessertes Verfahren zur Hydroformylierung von Olefinen durch Reduzierung der Ameisensäurekonzentration
EP2244996B2 (fr) Procede de production d'esters d'acide 6-hydroxycapronique
EP2493837B1 (fr) Oxidation selective d'hydrocarbures avec des catalyseurs hétérogènes à base d'or
US20140179950A1 (en) Method of making adipic acid using nano catalyst
EP1401797B1 (fr) Procede de production d'alcools, de cetones, d'aldehydes et d'acides carboxyliques satures
DE3728222A1 (de) Verfahren zur herstellung von ethercarbonsaeuren
WO2020053035A1 (fr) Procédé de transformation chimique de sucres ou d'alcools de sucre en glycols
AT501685A1 (de) Verfahren zur oxidation von organischen substraten mittels singulett sauerstoff unter verwendung eines molybdän-ldh-katalysators
WO2008017342A1 (fr) Oxydation catalytique de terpène avec des catalyseurs de métaux nobles
DE102007005528A1 (de) Kohlenstoff-geträgerter Goldkatalysator
TW200948768A (en) Method for producing carbonyl compound
EP3672932B1 (fr) Procédé de préparation d'aldéhydes et de cétones terpéniques
WO2005066107A1 (fr) Catalyseur a phase solide, son procede de fabrication et son utilisation pour la fabrication d'arylesters
KR101515677B1 (ko) 균일한 팔라듐 나노 입자-탄소 복합체를 촉매로 한 수소와 산소를 이용한 과산화수소 직접 생산
DE10252280A1 (de) Verbesserter Katalysator und Verfahren zur Herstellung von Alkoholen durch Hydrierung an diesem Katalysator
AT502537B1 (de) Verfahren zur oxidation von organischen substraten mittels singlet sauerstoff bei hohen reaktionstemperaturen
EP0268826B1 (fr) Procédé de traitement de mélanges de réaction contenant du cyclohexylhydroperoxyde
CN109092375B (zh) 环己烷直接氧化制己二酸的自由基稳定剂
EP0993866A1 (fr) Préparation des catalyseurs de metal noble sur supports de carbone
DE102004002262A1 (de) Festphasenkatalysator, Verfahren zu seiner Herstellung und seine Verwendung zur Herstellung von Arylestern
DE1518991A1 (de) Verfahren zur Herstellung von Carbonylverbindungen

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07764647

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: RU

122 Ep: pct application non-entry in european phase

Ref document number: 07764647

Country of ref document: EP

Kind code of ref document: A1