US 2010O217017A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0217017 A1 BOnrath et al. (43) Pub. Date: Aug. 26, 2010 (54) NOVEL REACTION WITH A GOLD (86). PCT No.: PCT/EPO8/04485 CATALYST S371 (c)(1), (2), (4) Date: May 7, 2010 (76) Inventors: WernerJocelyn Fischesser,Bonrath, Freiburg Wittenheim (DE); (30) Foreign ApplicationO O Priority Data (FR) Jun. 5, 2007 (EP) .................................. O701 1032.5 Publication Classification Correspondence Address: (51) Int. Cl. SFOSE,Sith9 floor 52) U.S.C07D Cl. 307/62 ........................................................ (2006.01) 549/315 ARLINGTON, VA 22203 (US) (52) (57) ABSTRACT (21) Appl. No.: 12/600,859 The invention relates to a process for the catalytic conversion of a carbohydrate, an alcohol, an aldehyde or a poly-hydroxy compound in the presence of a catalyst containing gold in a (22) PCT Filed: Jun. 5, 2008 solvent. US 2010/0217017 A1 Aug. 26, 2010 NOVEL REACTION WITH A GOLD Sen from the group consisting of alcohols, aldehydes and/or CATALYST polyhydroxy compounds, such as carbohydrates, carbohy drate derivatives, starch hydrolysates, in particular mono-, di or trisaccharides, in aqueous phase, where the conversion is 0001. The invention relates to a process for the catalytic carried out catalytically using a metal catalyst containing conversion of a carbohydrate, an alcohol, an aldehyde or a gold. It may be provided also to jointly convert mixtures of polyhydroxy compound in the presence of a catalyst contain said starting materials. ing gold in a solvent. 0011 Being envisaged for an industrial process, it is one 0002. In many industrial processes, the conversion, e.g. objective of the invention to increase the space time yield of the oxidation, of carbohydrates, alcohols, aldehydes or poly the conversion. hydroxy compounds in aqueous phase plays a decisive role 0012. In a preferred embodiment of the present invention, and often forms the critical stage of synthesis processes. the conversion is an oxidation of said starting materials, car 0003. Thus, for example, the D-gluconic acid required for bohydrates, for example glucose, Sorbose, diacetone Sorbose, many industrial applications is prepared by an oxidation of Sucrose, maltose, lactose, starch hydrolysates and/or isoma D-glucose, which is carried out as a microbial oxidation using litulose preferably being oxidized to the corresponding carbo Aspergillus niger: hydrate acids. Because of the very aggressive conditions dur 0004. A further important oxidation is the formation of ing oxidations, the long-term stability observed according to 2-keto-L-gulonic acid from Sorbose as intermediate step in the invention and the metal leaching which does not arise in the preparation of ascorbic acid (vitamin C). The classical this embodiment are particularly Surprising. Reichstein process here provides a 2-stage reaction in which, 0013. In a further embodiment, the conversion is a reduc in a complex manner an L-Sorbofuranose is formed, which is tion, in particular a hydrogenation, reducing Sugars, such as, then oxidized to 2-keto-L-gulonic acid, for example by an for example, glucose, fructose, Xylose, Sorbose, isomaltose, electrochemical method or catalytically using nickel oxide. isomalitulose, trehalulose, maltose and/or lactose, being 0005. The hydrogenation of reducing mono- and disac hydrogenated to give the corresponding Sugar alcohols. In charides with supported noble metal catalysts is described in this way, it is possible, for example, to obtain isomalt, 1.1- DE 19523008 A1. For industrial production, i.e. on a large GPM (1-O-alpha.-D-glucopyranosyl-D-mannitol) or scale designed for large conversions, such catalysts are, how 1,6-GPS (6-O-alpha.-D-glucopyranosyl-D-sorbitol) ever, unsuitable, meaning that Raney nickel catalysts gener enriched mixtures from isomalitulose. Such enriched mix ally have to be used on an industrial scale. tures are described in DE 19531 396 C2. 0006. It is therefore inprinciple known, e.g. from EPO 201 0014. In a further embodiment, the industrial conversion 957 A2, WO 97/34861, U.S. Pat. No. 5,643,849 or tetrahe of said starting materials can be a reductive amination, pref dron letters 38 (1997),9023-9026, to carry out such reactions, erence being given to reductively aminating reducing Sugars, in particular oxidations, catalytically, in particular using in particular glucose, fructose, Xylose, Sorbose, isomaltose, noble metal catalysts, mild reaction conditions with regard to isomalitulose, trehalulose, maltose and/or lactose. the pH and the reaction temperature being made possible. 0015. In a preferred embodiment, the metal catalyst can be Particularly suitable catalyst metals here are platinum, but combined with other known catalysts that are known in the also palladium and possibly rhodium, all noble metals in art. These catalysts comprise essentially all noble metal, for principle being Suitable, taking into consideration their activ example, platinum, palladium, rhodium and/or ruthenium. ity and their oxygen tolerance. However, the metal catalyst can also be a catalyst which 0007 U.S. Pat. No. 4,599,446 describes a process for the essentially consists of a base metal or comprises the latter, preparation of 2-keto-L-gulonic acid by oxidizing L-Sorbose where the base metal can, for example, be copper and/or with an oxygen-containing gas in water used as the Solvent nickel. and in the presence of a carrier Supported catalyst containing, 0016. In connection with the present invention, the con based on the weight of the carrier, 1-10% of platinum and/or version takes place in an aqueous solvent, preferably water. palladium and 0.5-8% of lead or bismuth, the reaction being 0017. The conversion is preferably taking place at a tem carried out with the pH of the reaction fluid kept within the perature of from 30-150° C. range of 6 to 8 0018. The reaction is advantageously performed at pH of 0008 U.S. Pat. No. 6,894,160 describes a process for the from 5 to 14. catalytic conversion of carbohydrates, alcohols, aldehydes or 0019. In connection with the present invention, a polymer polyhydroxy compounds in aqueous phase, which comprises coated particle is understood as meaning a metal particle carrying out the conversion using polymer-coated metal par around which a polymer sheath is formed, where the total ticles with a total diameter in a range from 3-200 nm as a diameter of the polymer-coated metal particle, as metal par metal-catalyst wherein the conversion is an oxidation, ticle core plus sheath, is preferably in a range from 3 to 200 wherein said process comprises the steps of mixing the com nanometerS. pound to be oxidized with the nanoparticles in an aqueous 0020. The invention provides in a particularly preferred Solution, introducing oxygen, conducting the oxidation, and manner that the alcohols, aldehydes or polyhydroxy com separating off the oxidation products obtained. pounds to be reacted, in particular carbohydrates, carbohy 0009. To ensure uniform distribution of supported cata drate derivatives or the like are converted in aqueous solution. lytic particles, it has also been proposed to Surround the The concentration can vary, but in a preferred embodiment of particles with Surfactants in order to achieve a uniform dis the invention concentrations of from 1 to 15% are used. But tribution upon application to a Support. In this technology, Glucose may also be used at higher concentrations up to 60%, however, the surfactant sheath is dissolved following uniform particularly in the form of glucose syrup. distribution of the particles in order to achieve the catalyst 0021. In particular, in a further preferred embodiment, it effect, meaning that the Sole function of the Surfactant is to may be provided to pass the products mentioned above con achieve uniform distribution. Verted according to the invention during the oxidation follow 0010. The present invention relates in particular to pro ing their conversion to a product solution to an electrodialy cesses for the industrial conversion of starting materials, cho sis, and in so doing to remove and obtain the products from US 2010/0217017 A1 Aug. 26, 2010 the resulting product solution. A particularly preferred pro (vinylphosphonic acid), polydiallyldimethylammonium cedure of this type is suitable, for example, for the preparation chloride (PDADMAC), polymethacrylamidopropyltri of monooxidized carbohydrates or carbohydrate derivatives methylammonium chloride, poly(3-chlorohydroxypropyl-2- and primary alcohols. Separating off the oxidation products methacryloxyethyldimethylammonium chloride). by means of electrodialysis, for example as described in EP 0 0031. The catalysts according to the invention can be used, 651 734 B1, leads to virtually pure products being obtained. in a preferred embodiment, also as colloids/clusters, the active component being in the form of free, i.e. not immobi 0022. The process according to the invention can thus be lized, colloids or clusters. The largest arrangement of these coupled in a preferred manner with a process and the apper colloids/clusters is, according to the invention, in the nanom taining equipment according to EP 0 651 734 B1 in order to eter range, i.e. in a range from 1 nm to 20 nm. It is only obtain the desired products in a particularly pure form by essential that the colloid particles and clusters are Surrounded means of electrodialysis. The teaching of EPO 651 734B1 is by a protecting polymer sheath. incorporated in its entirety into the disclosure content of the 0032. The catalysts can be designed according to the type present teaching with regard to the electrodialysis separation of catalyst and the reactor in question, for example as spheres, described therein, and protection is also sought therefore. beads, cylinders, hollow cylinders, meshes, powders, pressed 0023. If the catalyst particles according to the invention articles, granules, hollow spheres, fibers and films. The pro are continually used repeatedly, it must be taken into consid cess itself can be used in plants which operate continuously, eration that the polymer sheath around the nanoparticles is semicontinuously or else batchwise.