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Thermochemical Insight Into “Green Chemistry” Processes: Experiment and Ab Initio Calculations

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Thermochemical Insight Into “Green Chemistry” Processes: Experiment and Ab Initio Calculations THERMOCHEMICAL INSIGHT INTO “GREEN CHEMISTRY” PROCESSES: EXPERIMENT AND AB INITIO CALCULATIONS A THESIS submitted for the Degree of Doctor of Philosophy (Ph.D.) of the Mathematics and Nature Science Department of Rostock University by Alexey V. Toktonov, born in 25.05.1977, in Ulan-Ude (Russian Federation) from Rostock Rostock, 21.04.2009 THERMOCHEMISCHE EINSICHT IN EINIGE “GREEN CHEMISTRY” PROZESSE: EXPERIMENT UND AB INITIO BERECHNUNGEN DISSERTATION zur Erlangung des akademischen Grades Doctor rerum naturalium (Dr. rer. nat.) der Mathematisch-Naturwissenschaftlichen Fakultät der Universität Rostock vorgelegt von Alexey V. Toktonov, geb. am 25.05.1977 in Ulan-Ude (Russische Föderation) aus Rostock Rostock, 21.04.2009 1 Gutachter: Prof. Dr. Armin Börner (Institut für Chemie der Universität Rostock) 2 Gutachter: PD Dr. Sergey P. Verevkin (Institut für Chemie der Universität Rostock) Tag der mündlichen Prüfung: 07.04.2009 Tag der Verteidigung: 21.04.2009 ACKNOWLEDGEMENTS I would like to express my sincere gratitude to my scientific adviser PD Dr. Sergey P. Verevkin for his continuous and patient guidance, advice and support. He guided me all this time and in many respects his energy resulted to this thesis. I would also like to thank Dr. Vladimir N. Yemel’yanenka for his valuable and immediate assistance in computations and calorimetric experiments. Deep appreciation is due for all present and former colleagues of PD Dr. Sergey P. Verevkin‘s working group and all colleagues of Physical Chemistry Department in Rostock, and especially for head of Physical Chemistry Department in Rostock University, Prof. Dr. Andreas Heintz, for friendly and working atmosphere. Special thanks to co-workers of Leibnitz-Institute of Catalysis in Rostock, especially to Prof. Dr. Udo Kragl and Prof. Dr. Armin Börner for their valuable help in the enzyme-catalyzed polymer chemistry and hydrogenation chemical processes respectively. Author expresses sincerely thanks to researchers of laboratory of Condensation Polymers in A.N. Nesmeyanov Institute of Organoelement Compounds (Moscow, Russian Academy of Sciences), especially to Prof. Dr. Yakov S. Vygodskii for the professional advice, valuable support and help in organisation of the experiments in synthesis of polyamidines. Also, my deep appreciation is due for head of laboratory of Chemistry of Natural and Synthetic Polymers in Baikal Institute of Nature Management (Ulan-Ude, Siberian Branch of Russian Academy of Sciences), Prof. Dr. Dmitry M. Mognonov and co-workers, especially for Dr. Zhanna P. Mazurevskaya and Dr. Svetlana O. Botoeva for their support. In conclusion, I would like to thank the Research Training Group 1213 (Graduiertenkolleg) of German Science Foundation (Deutsche Forschungs- gemeinschaft) for the financial support. i ii LIST OF PAPERS This thesis is a summary of the following papers: 1. Toktonov, A. V.; Mognonov, D. M.; Mazurevskaya, Zh. P.; Botoeva, S. O. Synthesis of Polyamidines based on Aromatic Bis(imidoyl) Chlorides in Solution, Polymer Science, Ser. A 2006, 48(1), 1–10. 2. Verevkin, S.P.; Toktonov, A.V.; Chernyak, Y.; Schäffner, B.; Börner, A. Vapour pressure and enthalpy of vaporization of cyclic alkylene carbonates, Fluid Phase Equilibria 2008, 268, 1-6. 3. Verevkin, S.P.; Emel'yanenko, V.N.; Toktonov, A.V.; Chernyak, Y.; Schäffner, B.; Börner, A. Cyclic alkylene carbonates. Experiment and first principle calculations for prediction of thermochemical properties, J. of Chemical Thermodynamics 2008, 40(9), 1428-1432. 4. Emel'yanenko, V.N.; Toktonov, A.V.; Kozlova, S.A.; Verevkin, S.P.; Andrushko, V.; Andrushko, N.; A. Börner. Structure-Energy Relationships in Unsaturated Esters of Carboxylic Acids. Thermochemical Measurements and ab Initio Calculations, J. Physical Chemistry A 2008, 112(17), 4036–4045. 5. Verevkin, S.P.; Emel'yanenko, V.N.; Toktonov; A.V.; Duwensee, J.; Kragl, U.; Schick, C. Thermodynamics of Sebacic Acid and Butandiol-1,4 and their Biocatalytic Polymerisation, Industrial&Engineering Chemistry Research, 2008, in press. 6. Verevkin, S.P.; Toktonov; A.V.; Emel'yanenko, V.N.; Goodrich, P.; Hardacre, C. Thermochemistry of Ionic Liquid-Catalysed Reactions. Theoretical and Experimental Study of the Beckmann Rearrangement- Kinetic or Thermodynamic Control? Industrial&Engineering Chemistry Research 2009, submitted. 7. Verevkin, S.P.; Emel'yanenko, V.N.; Toktonov; A.V.; Börner, A.; Heller, D. Asymmetric Hydrogenation of Non Functionalized Olefins in Propylene Carbonate – Kinetic or Thermodynamic Control? Industrial&Engineering Chemistry Research 2009, submitted. 8. Verevkin, S.P.; Emel'yanenko, V.N.; Toktonov; A.V.; Leol’ko, A.; Duwensee, J.; Kragl, U.; Sarge, S. Thermochemical and Ab Initio Studies of Biodiesel Fuel Surrogates: 1,2,3-Propanetriol Triacetate, 1,2-Ethanediol Diacetate, and 1,2- Ethanediol Monoacetate. Industrial&Engineering Chemistry Research 2009, accepted. iii ii CONTENTS Acknowledgements .......................................................................................................................................... i List of Papers ................................................................................................................................................. iii 1. Preface ....................................................................................................................................... 1 2. Cyclic Carbonates: Experiment and Ab Initio Calculation for Prediction of Their Thermochemical Properties. 2.1. Introduction ...................................................................................................................................... 5 2.2. Vapour Pressures, Enthalpies of Sublimation and Vaporization .................................................. 6 2.2.1. Ethylene Carbonate ........................................................................................................................ 7 2.2.2. Propylene Carbonate ...................................................................................................................... 8 2.2.3. Butylene Carbonate ........................................................................................................................ 8 2.2.4. Glycerine Carbonate ....................................................................................................................... 8 2.3. Correlations of Vapour Pressures .................................................................................................. 8 2.4. Enthalpies of Formation of Cyclic Alkylene Carbonates ............................................................... 9 2.5. Ab Initio Calculations for Cyclic Alkylene Carbonates .................................................................10 2.6. Structure-Energy Relationships. Strain Enthalpies (HS) of Cyclic Alkylene Carbonates ...........11 3. Reactions in Cyclic Carbonates: Asymmetric Hydrogenation in Propylene Carbonate. 3.1. Introduction ....................................................................................................................................15 3.2. Asymmetric Hydrogenation of 1-Methylene-1,2,3,4-tetrahydronaphtalene ................................16 3.2.1. Computational and Thermochemical Study of Isomers, 1-Methylene-1,2,3,4-tetrahydro- naphthalene and 4-Methyl-1,2-dihydronaphthalene....................................................................17 3.3. Hydrogen Solubility in Various Solvents ......................................................................................18 4. Thermochemistry of Ionic Liquid-Catalyzed Reactions: Experimental and Theoretical Study of Beckmann Rearrangement of Cyclohexanone Oxime and 2-Butanone Oxime. 4.1. Introduction ....................................................................................................................................21 4.2. Vapour Pressures, Enthalpies of Vaporization ............................................................................22 4.2.1. N-Methylpropanamide ..................................................................................................................22 4.3. Enthalpies of Formation (Combustion Calorimetry) ................................................................... 24 4.4. Ab Initio Calculations ..................................................................................................................... 24 4.4.1. Thermodynamic Analysis of Beckmann Rearrangement: Kinetic or Thermodynamic Control? .........................................................................................................................................25 4.4.2. G3MP2-Enthalpies of Formation of Amides and Oximes ...........................................................27 4.5. Experimental Study of Beckmann Rearrangement in the Liquid Phase ....................................27 5. Thermochemical Study of Enzymatic Polymerization Based on Reaction of 1,4-Butanediol with Sebacic Acid. 5.1.1. Introduction ....................................................................................................................................31 5.2. Vapour Pressures, Enthalpies of Sublimation and Vaporization of Monomers .........................32 5.2.1. Butanediol-1,4 ...............................................................................................................................32 5.2.2. Decandioic Acid (Sebacic Acid) ...................................................................................................32 5.2.3. Dodecandioic Acid ........................................................................................................................32
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