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Microwave Assisted Synthesis of Dehydrated Sugar Derivatives Hydroxymethylfurfural, Levulinic Acid, Anhydrosugar Alcohols, and E

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Microwave Assisted Synthesis of Dehydrated Sugar Derivatives Hydroxymethylfurfural, Levulinic Acid, Anhydrosugar Alcohols, and E (19) TZZ _T (11) EP 2 598 466 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 51/00 (2006.01) C07D 307/02 (2006.01) 28.09.2016 Bulletin 2016/39 C07C 67/00 (2006.01) C07D 307/93 (2006.01) C07D 493/04 (2006.01) C07D 307/46 (2006.01) (2006.01) (2006.01) (21) Application number: 11812946.9 C07D 307/48 C07D 307/50 C07C 59/185 (2006.01) (22) Date of filing: 18.07.2011 (86) International application number: PCT/US2011/044324 (87) International publication number: WO 2012/015616 (02.02.2012 Gazette 2012/05) (54) MICROWAVE ASSISTED SYNTHESIS OF DEHYDRATED SUGAR DERIVATIVES HYDROXYMETHYLFURFURAL, LEVULINICACID, ANHYDROSUGAR ALCOHOLS, AND ETHERS THEREOF MIKROWELLENUNTERSTÜTZTE SYNTHESE VON DEHYDRIERTEN ZUCKERDERIVATEN, HYDROXYMETHYLFURFURAL, LÄVULINSÄURE, ANHYDROZUCKERALKOHOLEN SOWIE DEREN ETHERN SYNTHÈSE ASSISTÉE PAR RAYONNEMENT MICROONDES DES DÉRIVÉS DE SUCRES DÉSHYDRATÉS HYDROXYMÉTHYLFURFURAL, ACIDE LÉVULINIQUE, ALCOOLS DE SUCRE ANHYDRES ET LEURS ÉTHERS (84) Designated Contracting States: (74) Representative: dompatent von Kreisler Selting AL AT BE BG CH CY CZ DE DK EE ES FI FR GB Werner - GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO Partnerschaft von Patent- und Rechtsanwälten PL PT RO RS SE SI SK SM TR mbB Deichmannhaus am Dom (30) Priority: 30.07.2010 US 369350 P Bahnhofsvorplatz 1 50667 Köln (DE) (43) Date of publication of application: 05.06.2013 Bulletin 2013/23 (56) References cited: WO-A2-2009/155020 US-A- 5 558 899 (73) Proprietor: Archer-Daniels-Midland Company US-A1- 2007 213 544 US-A1- 2007 213 544 Decatur, IL 62526 (US) US-A1- 2009 156 841 US-A1- 2009 156 841 US-A1- 2009 253 920 US-A1- 2009 281 338 (72) Inventors: • HOWARD, Stephen J. • QI X ET AL: "Catalytical conversion of fructose Sherman and glucose into 5-hydroxymethylfurfural in hot Illinois 62684 (US) compressed water by microwave heating", • SANBORN, Alexandra J. CATALYSIS COMMUNICATIONS, ELSEVIER Lincoln SCIENCE,AMSTERDAM, NL, vol. 9, no. 13, 20 July Illinois 62656 (US) 2008 (2008-07-20), pages 2244-2249, XP022824415, ISSN: 1566-7367, DOI: 10.1016/J.CATCOM.2008.04.025 [retrieved on 2008-05-13] 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 2 598 466 B1 Printed by Jouve, 75001 PARIS (FR) (Cont. next page) EP 2 598 466 B1 • XINHUA QI ET AL: "Catalytic dehydration of • THOMAS S. HANSEN ET AL: "Efficient fructose into 5-hydroxymethylfurfural by microwave-assisted synthesis of ion-exchange resin in mixed-aqueous system by 5-hydroxymethylfurfural from concentrated microwave heating", GREEN CHEMISTRY, vol. aqueous fructose", CARBOHYDRATE 10, no. 7, 1 January 2008 (2008-01-01), page 799, RESEARCH, vol. 344, no. 18, 1 December 2009 XP055043574, ISSN: 1463-9262, DOI: (2009-12-01), pages 2568-2572, XP055097102, 10.1039/b801641k ISSN: 0008-6215, DOI: 10.1016/j.carres.2009.09.036 2 EP 2 598 466 B1 Description TECHNICAL FIELD 5 [0001] The present disclosure relates to improved methods of producing the dehydrated sugar derivatives such as 2,5-(hydroxymethyl)furfural ether and ester derivatives, levulinate esters, anhydrosugar alcohols ether and ester deriv- atives using microwave radiation to catalyze the reactions. BACKGROUND 10 [0002] The principle sugars from plant materials, glucose and fructose, have been shown to be useful renewable starting materials for the production of a variety of organic compounds that may substitute for petroleum based com- pounds. For example, the furan compound, 2,5-(hydroxymethyl)furaldehyde, also known as 2,5-(hydroxymethyl)furfural (HMF) a five membered heterocycle obtained by dehydration of a hexose, most efficiently from fructose. 15 [0003] HMF has strong potential in industrial and commercial applications especially for polymer applications due to its multi-functionality which allows for use as a monomer in polymerization reactions. 20 25 [0004] Generation of HMF by dehydration of fructose produces three equivalents of water as by products, and the 30 formation of 3 double bonds (two alkenes and one aldehyde). In order to compete as substitutes or replacements in the chemicals market, HMF must be produced at relatively low cost. The production of HMF has been studied for years, but an efficient and cost-effective method of producing HMF has yet to be found. Extended reaction times, high temperatures and pressures cause complications to arise from the rehydration of HMF after the dehydration occurs, which often yields the byproducts of levulinic acid and formic acid. Another competing side reaction is the polymerization of HMF and/or 35 fructose to form humin. [0005] A low yield of HMF is typically obtained when the synthesis is performed in aqueous conditions because of the low selectivity of the dehydration reaction. Low selectivity simultaneously leads to increased polymerization reactions and humin formation, which also interfere with the synthesis of HMF. Where attempts have been made to solve problems associated with aqueous systems, the HMF reaction product is generally sequestered by organic solvent extraction or 40 adsorption onto a resin as soon as it is formed. These systems fail to directly address the issue of low selectivity for HMF. In addition, these systems generally suffer from high dilution or partially irreversible adsorption of HMF and increase cost due to handling and use of the organic solvents or resins. Thus, a selective aqueous reaction system wherein HMF is the predominant product formed at would be desirable. [0006] Levulinic acid is made by dehydration of hexose, which generates HMF as an intermediate, followed by de- 45 formylation resulting in the loss of formic acid. Levulinic acid and levulinate esters have been used as important inter- mediates in pharmaceutical and fine chemical processes. 50 55 [0007] Anhydrosugar alcohols, such as sorbitan and isosorbide derived from glucose, are mono cyclic and bi-cyclic 3 EP 2 598 466 B1 ring compounds that are made by the dehydration of 1 or 4 water molecules, respectfully, from a hexitol, which is typically made by hydrogenation of a hexose. 5 10 15 [0008] Of all the known isohexides, isosorbide is considered to be one of high importance because of its use in the formation of pharmaceutical compounds, in food production, cosmetic production, plastic and polymer production, and in other potential industrial uses such as in the production of polyurethane, polycarbonate, polyesters, and polyamides (Stoss and Hemmer, 1991). 20 [0009] Several processes for the production of anhydrosugar alcohols (including isohexides such as isosorbide) have been reported. For example, PCT application number PCT/US99/00537 (WO 00/14081), discloses collecting methods and a continuous production method with recycling of organic solvent. Most methods involve the use of concentrated acids and organic solvents. Goodwin et al., Carbohydrate Res. 79:133-141 (1980) have disclosed a method involving the use of acidic-cation-exchange resin in place of concentrated, corrosive acids, but with low yield of isosorbide product. 25 An alternative is the supersaturation-based method, as disclosed in U.S. Pat. No. 4,564,692 (Feldmann, et al., Jan. 14, 1986). However, a need continues for a process for production of very pure dianhydrosugaralcohols, at reasonable yields. [0010] These dehydrated ring derivatives of hexoses, may further be used for making several other compounds, for example, by making ether derivatives of the free alcohol groups as illustrated below: 30 35 Where R can be alkyl, allyl,, or aryl 40 [0011] For example, the anhydrosugar alcohol, isosorbide, can be used as a starting material in the formation of isosorbide dimethyl ether and isosorbide dinitrate or as an intermediate in various organic synthesis reactions. Isosorbide dimethyl ether is useful as an industrial solvent, a pharmaceutical additive, and in personal care products, while isosorbide dinitrate is useful as a medication to relieve the pain of angina attacks or reduce the number of such attacks by improving 45 blood flow to the heart. Similar processes are also described in WO 2009/155020 A2; US 2007/0213544 A1; US 2009/0156841 A1; US 2009/0253920 A1; QI X et al., "Catalytical conversion of fructose and glucose into 5-hydroxymethylfurfural in hot com- pressed water by microwave heating", Catalysis Communications, Elsevier Science, Amsterdam, NL, Vol. 9, No 13, (2008-07-20), pages 2244-2249; Xinhua Qi et al., "Catalytic dehydration of fructose into 5-hydroxymethylfurfural by 50 ionexchange resin in mixed-aqueous system by microwave heating", Green Chemistry, Vol. 10, No. 7, (2008-01-01), page 799 and Thomas S. Hansen et al., "Efficient microwave-assisted synthesis of 5-hydroxymethylfurfural from con- centrated aqueous fructose", Carbohydrate Research, Vol. 344. No. 18, (2009-12-01), pages 2568-2572. [0012] Accordingly, there is a need in the art to find methods of making a variety dehydrated sugar compounds and derivatives thereof that is cost effective and efficient. 55 BRIEF SUMMARY [0013] Methods of producing a variety of dehydrated sugar derivatives are provided. Commonly, for any of the dehy- 4 EP 2 598 466 B1 drated sugar derivatives the methods include forming a reaction mixture comprising
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