Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

NANOSTRUCTURED POLYMERIC METAL-CONTAININGNANOCOMPOSITES AS EFFECTIVE NANOCATALYSTS INREACTIONS OF FINE ORGANIC SYNTHESISPP-III-16E. Sulman 1 , V. Matveeva 1 , G. Demidenko 1 , A. Bykov 1 , V. Doluda 1 , N. Lakina 1 ,L. Nikoshvili 1 , M. Sulman 1 , I. Tyamina 1 , P. Valetsky 2 , I. Tsvetkova 2 , L. Bronstein 31 Dept. of Biotechnology and Chemistry, Tver Technical University, A. Nikitin str., 22, Tver,170026, Russia, fax: +7 (4822) 449317, E-mail: sulman@online.tver.ru2 A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Science,Vavilov str., 28, Moscow, 119991, Russia3 Indiana University, Department of Chemistry, Bloomington, IN 47405, USAIntroduction. Industrial processes of fine organic synthesis using catalytic technologiescontinue to receive significant attention due to the importance of pure and cheap intermediatesin the manufacture of vitamins, pharmaceuticals and medicines. One of the most complicatedproblems is the achieving of high affectivity and stability and at the same time the use of mildconditions of catalytic stage conduction.Earlier the nanostructured polymers containing noble metal nanoparticles (MNPs) wereshown to have increased activity, selectivity and stability of active phase in various organicreactions in comparison to traditional catalysts [1, 2]. Thus, in this study several types ofpolymers were investigated: (i) amphiphilic block-copolymers; (ii) polyelectrolytes (PE); (iii)polymeric matrices. Catalytic properties of the synthesized nanocomposites were studied inselective hydrogenation of triple bond, enantioselective hydrogenation, direct selectiveoxidation of monosaccharides and full oxidation of phenols.Experimental. Homo- and heterogeneous mono- (Pd and Pt) and bimetallic (Pd-Au-, Pd-Pt- and Pd-Zn) catalysts of (i) type were prepared using poly (ethylene oxide)-blockpolyvinylpyridine(PEO-b-P2VP) and polystyrene-block-poly-4-vinylpyridine (PS-b-P4VP).In case of (ii) type catalysts, PEs (polydiallyldimethyl ammonium chloride (PDADMAC),chitosan (CS) and poly(sodium 4-styrenesulfonate) (PSS)) were deposited on alumina usingtwo methods: monolayered and “layer-by-layer” deposition. Thus Pd-PDADMAC and Pd-PSC (multilayered) were synthesized. Hypercrosslinked polystyrene (HPS) was used to obtainthe (iii) type catalysts: Pd-, Pt-, Ru-, Pd-Zn- and Pd-Pt-HPS.The oxidation reactions were conducted batchwise in PARR 4890 apparatus. The analysisof reaction mixture was performed by SpectraPhysics HPLC chromatograph. All theoxidation reactions were performed in an aqueous reaction medium. Enantioselectivehydrogenation of activated ketones was conducted also batchwise in PARR 4307 apparatus.333