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Process for the Oxidation of Alcohol And/Or Aldehyde

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Process for the Oxidation of Alcohol And/Or Aldehyde (19) TZZ ¥Z¥_T (11) EP 2 307 395 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 51/285 (2006.01) C07C 57/145 (2006.01) 11.09.2013 Bulletin 2013/37 C07C 51/56 (2006.01) C07D 307/58 (2006.01) C07D 307/68 (2006.01) (21) Application number: 09780732.5 (86) International application number: (22) Date of filing: 16.07.2009 PCT/EP2009/059180 (87) International publication number: WO 2010/007139 (21.01.2010 Gazette 2010/03) (54) PROCESS FOR THE OXIDATION OF ALCOHOL AND/OR ALDEHYDE GROUPS VERFAHREN ZUR OXIDIERUNG VON ALKOHOL- UND/ODER ALDEHYD-GRUPPEN PROCÉDÉ POUR L’OXYDATION D’UN ALCOOL ET/OU DE GROUPES D’ALDÉHYDES (84) Designated Contracting States: (56) References cited: AT BE BG CH CY CZ DE DK EE ES FI FR GB GR • SALADINO R ET AL: "A new and efficient HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL synthesis of ortho- and para-benzoquinones of PT RO SE SI SK SM TR cardanol derivatives by the catalytic system MeReO3-H2O2" J.CHEM.SOC.,PERKIN TRANS. (30) Priority: 18.07.2008 EP 08160771 1, 2000, pages 581-586, XP002506581 cited in the application (43) Date of publication of application: • SALADINO R ET AL: "Selective oxidation of 13.04.2011 Bulletin 2011/15 phenol and anisole derivatives to quinones with hydrogen peroxide and polymer-supported (73) Proprietor: SOLVAY SA methylrhenium trioxide systems" 1120 Bruxelles (BE) TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 58, no. 42, (72) Inventors: 14 October 2002 (2002-10-14), pages 8493-8500, • SALADINO, Raffaele XP004388260 ISSN: 0040-4020 I-00175 Rome (IT) • CRESTINI ET AL: "Immobilized methyltrioxo • FARINA, Angela rhenium (MTO)/H2O2 systems for the oxidation I-00142 Rome (IT) of lignin and lignin model compounds" BIOORGANIC & MEDICINAL CHEMISTRY, (74) Representative: Vande Gucht, Anne et al ELSEVIER SCIENCE LTD, GB, vol. 14, no. 15, 1 Solvay S.A. August 2006 (2006-08-01), pages 5292-5302, Département de la Propriété Industrielle XP005508668 ISSN: 0968-0896 Rue de Ransbeek, 310 • HERRMANN W A ET AL: "The selective catalytic 1120 Bruxelles (BE) oxidation of terminal alcohols: a novel four- component system with MTO as catalyst" JOURNAL OF ORGANOMETALLIC CHEMISTRY, ELSEVIER-SEQUOIA S.A. LAUSANNE, CH, vol. 579, no. 1-2, 5 May 1999 (1999-05-05), pages 404-407, XP004170591 ISSN: 0022-328X Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 307 395 B1 Printed by Jouve, 75001 PARIS (FR) EP 2 307 395 B1 Description [0001] The present application claims the benefit of the European application no. 08160771.5 filed on July 18, 2009. [0002] The present invention relates to a process for the oxidation of alcohol and/or aldehyde groups. In particular, it 5 relates to an oxidizing process based on peroxo compounds, heterogeneous rhenium based catalysts and co- catalysts. [0003] The use of rhenium based catalysts to activate hydrogen peroxide for the oxidation of various functional groups, and especially alcohol and/or aldehyde groups, is known in the prior art. The catalytic cycle of methyltrioxorhenium is for example disclosed in W.A. Hermann et al., Chemische Berichte, 126, 4 (1993) and in J.H. Espenson et al., J. Am. Chem. Soc., 117, 9243 (1995). 10 [0004] Applications of rhenium based catalysts are disclosed, for example, in the international patent application WO 00/61639 which relates to oxidized starch obtained by oxidizing native starch in an acidic solvent in the presence of hydrogen peroxide, rhenium (VI) or (VII) oxide, methyltrioxorhenium (MTO) or alkyl rhenium oxide in homogeneous phase, a ditertiary alkyl nitroxyl and hydrogen halide. [0005] Another use is disclosed in the US patent application 2006/0070953 A1 which relates to the catalytic oxidation 15 of tyrosol into hydroxytyrosol in the presence of hydrogen peroxide, a protic solvent, and methyltrioxorhenium (MTO), preferably in homogeneous phase. [0006] A third example is the use of hydrogen peroxide and of methyltrioxorhenium (MTO) in homogeneous phase for the synthesis of ortho- and para-benzoquinones of cardanol derivatives, disclosed in an article from R. Saladino et al., J. Chem. Soc., Perkin Trans. 1, 581-586 (2000). The oxidation reaction of various benzoquinones of cardanol 20 derivatives was tested in various solvents selected from acetic acid, ethanol, and a mixture ethanol - tetrafluoroboric acid (HBF4) in excess. Depending on the derivatives tested, the best results were obtained using acetic acid or the mixture ethanol - HBF4. [0007] These processes have the disadvantage to be conducted in homogeneous phase, which do not allow an easy recovery of the catalyst. 25 [0008] It is also known to proceed to the oxidation of olefins into epoxides in heterogeneous phase, using polymer- supported rhenium based catalysts. Such polymer-supported catalysts are disclosed, for example, in an article from R. Saladino et al., J. Org. Chem., 67, 1323-1332 (2002). The heterogeneization of rhenium based catalysts by using a polymeric support allows an easier recovery of the catalyst and, sometimes, may improve the reactivity. [0009] Nevertheless, there is still a need for improved processes for the oxidation of alcohol and/or aldehyde groups, 30 leading to high yields, an easy recovery of the catalyst, and a good stability and reuse of the catalyst. [0010] The purpose of the present invention is to provide a new process for the oxidation of alcohol and/or aldehyde groups having improved properties compared to the processes of the prior art. [0011] The present invention therefore relates to a process for the oxidation of alcohol and/or aldehyde groups com- prising the treatment of said alcohol and/or aldehyde groups with at least one oxidizing agent chosen from peroxo 35 compounds in the presence of at least one solvent, of at least one heterogeneous rhenium based catalyst, and of a co- catalyst selected from the group consisting of HBF 4 and salts thereof. [0012] According to the present invention, it has been surprisingly found that, when alcohol and/or aldehyde groups are oxidized with a peroxo compound in the presence of a heterogeneous rhenium based catalyst and a co-catalyst such as HBF4 or a salt thereof, the stability and reuse of the catalyst is improved. Furthermore, according to the process 40 of the invention, it is easier to recover the catalyst from the reaction mixture compared to reactions conducted in homo- geneous phase, the selectivity of the reaction can be modified, and the amount of active rhenium compound added to the reaction mixture can be drastically reduced. This process is thus especially advantageous compared to the processes of the prior art. [0013] By alcohol and aldehyde groups, it is intended primary and secondary alcohol and aldehyde groups. According 45 to the present invention, such groups may be present on any substrates. For example, the compounds may be linear, branched or cyclic alkyl alcohols or aldehydes, as well as high and low molecular weight carbohydrates and carbohydrate derivatives. In a preferred embodiment, the oxidation process of the present invention is applied to at least one compound selected from the group consisting of linear, branched or cyclic alkyl alcohols and linear, branched or cyclic alkyl alde- hydes, especially to carbohydrates and carbohydrate derivatives, for example to high and low molecular weight carbo- 50 hydrates and carbohydrate derivatives, advantageously to low molecular weight carbohydrates and low molecular weight carbohydrate derivatives. High molecular weight carbohydrates, also called polysaccharides, are composed of mon- osaccharide units, usually in an amount of more than 10 to 10000 units, preferably from 25 to 5000 units, for example from 50 to 500 units, a few of them being made up of considerably more units. High molecular weight carbohydrates include, for example, starch, cellulose, hemicellulose and chitin. Cellulose has an average molecular mass equivalent 55 to about 5000 units. Low molecular weight carbohydrates include mono and oligosaccharides, composed of 1 to 10 monosaccharide residues, preferably mono- and disaccharides. The term "monosaccharide" denotes a single sugar unit without glycosidic connection to other such units. Chemically, monosaccharides are either polyhydroxyaldehydes or aldoses, such as glucose, or polyhydroxyketones or ketoses, such as fructose. Depending on their number of carbon 2 EP 2 307 395 B1 atoms, monosaccharides are classified in hexoses (6C) and pentoses (5C). Monosaccharides with fewer (trioses, tet- roses) or more carbon atoms (heptoses, octoses) are rare. Preferred low molecular weight carbohydrates according to the present invention are monosaccharides, especially pentoses and hexoses. Carbohydrate derivatives may be glyco- sides, alditols, furan derivatives, such as furfural and 5-hydroxymethylfurfural (HMF), etc. Some general information 5 about carbohydrates and carbohydrate derivatives may for example be found in online Ullmann’s Encyclopedia of In- dustrial Chemistry, DOI 10.100214356007.a05_079, "Carbohydrates" (2003). [0014] One of the essential features of the present invention resides in the nature of the heterogeneous catalyst. The term "homogeneous catalyst" means that the catalyst and reactants or their solution form a common physical phase, then the reaction is called homogeneously catalyzed. The term "heterogeneous catalyst" is used when the system is 10 such that catalyst and reactants form separate physical states. The heterogeneous catalysts may be unsupported (bulk) catalysts insoluble in the reactant mixture, or supported catalysts. [0015] The heterogeneous catalyst of the invention may be chosen from insoluble unsupported rhenium based catalysts and supported rhenium based catalysts, preferably from supported rhenium based catalysts.
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