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Catalytic Applications of Solid Acid/Base Catalyst for the Benign Synthesis of Fine Chemicals

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Catalytic Applications of Solid Acid/Base Catalyst for the Benign Synthesis of Fine Chemicals CATALYTIC APPLICATIONS OF SOLID ACID/BASE CATALYST FOR THE BENIGN SYNTHESIS OF FINE CHEMICALS A THESIS SUBMITTED TO THE UNIVERSITY OF PUNE FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY BY LALITA B. KUNDE UNDER THE GUIDANCE OF Dr. S. P. GUPTE AT CHEMICAL ENGINEERING AND PROCESS DEVELOPMENT DIVISION NATIONAL CHEMICAL LABORATORY PUNE-411 008, INDIA SEPTEMBER 2011 CERTIFICATE This is to certify that, the work incorporated in the thesis entitled “CATALYTIC APPLICATIONS OF SOLID ACID/BASE CATALYST FOR THE BENIGN SYNTHESIS OF FINE CHEMICALS” submitted by Ms. Lalita B. Kunde, for the degree of Doctor of Philosophy, was carried out by the candidate under my supervision, in the Chemical Engineering and Process Development Division, National Chemical Laboratory, Pune-411008, India. Such material as has been obtained from other sources has been duly acknowledged in the thesis. Dr. S.P.Gupte September 2011 (Research Guide) Pune Declaration by the candidate I hereby declare that the thesis entitled “Catalytic Applications of Solid Acid/Base Catalyst for the Benign Synthesis of Fine Chemicals’’ submitted by me for the degree of Doctor of Philosophy, to the University of Pune, is the record of work carried out by me under the guidance of Dr. S. P. Gupte and has not formed the basis for the award of any degree, diploma, associateship, fellowship, titles in this or any other University or other institution of higher learning. I further declare that the material obtained from other sources has been duly acknowledged in this thesis. Lalita B. Kunde September 2011 (Candidate) Pune Dedicated to My Parents Acknowledgement There are many people who have actively helped me during the tenure of my Ph.D. and I would like to thank all of them for their time, support, efforts, and friendship. There are, however, several people that I would like to acknowledge in particular. I wish to express my sincere gratitude to my research guide, Dr. S. P. Gupte for his constant support and encouragement during the course of this work. It has been an intellectually stimulating and rewarding experience to work with him. His innovative ideas and scientific knowledge have inspired me profoundly. My special thanks to Dr. R.V. Chaudhari, former Head, Homogeneous Catalysis Division, National Chemical Laboratory (NCL) for his constant support, valuable help, suggestions and guidance during my research work. His enthusiastic attitude and great understanding of the subject have inspired me profoundly. I truly feel privileged to have joined his research group. I would like to express my sincere gratitude and respect to Dr. B. D. Kulkarni, Deputy Director and Head, CEPD, NCL. I am thankful to former Director Dr. Sivaram, and present Director Dr. S. Pal, NCL for allowing me to carry out research work and extending me all the possible infrastructural facilities. I would like to gratefully acknowledge Dr. A. A. Kelkar, Dr. R. M. Deshpande, Dr. V. H. Rane, Dr. R. Jaganathan, Dr. V. V. Ranade, Dr. C. V. Rode, Dr. Shubhangi Umbarkar, and Mr. H. M. Raheja for their valuable help and co-operation during my research stay in NCL. I would like to thank supporting staff of Homogeneous Catalysis Division, Mr. Patne, Mr. Kedari, Mr. Kamble and Mr. Durai for their help. My sincere acknowledgement to my friends Pippalad, Mrs. Savita Singote , Dr. Anand Shivarkar and Makarand Divakar, for their timely help during my difficult times. I would like to express my deepfelt gratitude to my colleagues and friends Dr.Yogesh B., Dr. Sunil T., Mahesh, Kalpendra, Nitin, Sunil Shinde, Sangeeta, Abhishek, Nandu, Deepak N., Bibhas, Debdut, Shashi, Jaypraksh, Vikas, Sunil Tekale, Vishwanath Kalyani, Chandan, Swapna, Munshi, Ajit, Amit Chaudhari, Amit Deshmukh, Himadri, Ankush B., Aniruddha, Aarti madam and many in NCL who are not named in person, for their friendship and for keeping a healthy working atmosphere and have been my extended family throughout the tenure of my work in NCL. I wish to thank CMC and Central NMR facility NCL, for characterization. I would like to gratefully acknowledge Subbu, Radha, Ravi, Shekhar, Dure, Narawde, Wanjale, Shinde and Murkute for their help in reactor and vacuum pump maintenance. Additionally I would like to acknowledge store–purchase, work shop, civil, electrical, administration sections and other supporting staff of NCL for their cooperation. No thanks can be enough to acknowledge for the encouragement and support of my mother, father, brother and Shri. Pratap Borde. They have been my constant source of strength. I thank my family and daughter Pratyusha, for making my life complete and being constant source of inspiration during my research career. Needless to say it was because of the efforts of my family, friends and relatives today I stand where I am. September, 2011 Lalita B. Kunde List of Contents Chapter index i List of tables x List of figures xii Abbreviation xv Abstract of thesis xvi Section No. Page No. Chapter I : General Introduction 1.1 Introduction 2 1.2 Fine chemicals 9 1.2.1 Solid acid/base catalysts in fine chemical synthesis 10 1.2.2 Solid acid catalysis 11 1.2.3 Solid base catalysis 11 1.3 Green Chemistry 18 1.3.1 Goal of green chemistry 20 1.3.2 Catalysis and green chemistry 21 1.3.3 E factor and green chemistry 21 Organic Inorganic Hybrid Catalysts for Sustainable 1.4 23 chemistry 1.4.1 Immobilized Ionic Liquids 24 1.5 CO2 and global warming 26 1.5.1 Carbon Dioxide as an alternative C1 Synthetic unit 27 1.5.2 Thermodynamics of CO2 conversion and utilization 29 1.5.3 Challenges for CO2 utilization 30 1.5.4 Strategies for CO2 conversion and utilization 30 1.5.5 Application of CO2 for synthesis of organic carbonate 31 1.5.6 Methods for preparation of organic carbonates 32 1.5.6.1 Phosgenation method 32 1.5.6.2 Oxidative Carbonylation of Alcohols/Phenols 34 i 1.5.6.3 Reaction of urea with alcohols/phenols 36 1.5.6.4 Preparation of organic carbonates from CO2 37 Cycloaddition of CO to Epoxides 1.6 2 39 Efficient synthesis of chalcone and flavanone catalysed by 1.7 40 immobilized IL DBTO catalyzed synthesis of 1,3,5 imidazolidine trione, 1.8 44 carbamates and oxamates. Alkylation of phenol by Dimethyl carbonates using organic 1.9 47 inorganic hybrid catalyst/ immobilized IL 1.10 Scope and objective of thesis 49 References 53 Chapter 2. Synthesis and Characterization of Immobilized Catalyst 2.1 Introduction 59 2.1.1 Support Materials 61 2.1.2 Advantages and Disadvantages of immobilized catalyst 63 2.1.3 Immobilization techniques 64 2.1.3.1 Liquid-Liquid phase differentiation 64 2.1.3.1.1 Biphasic catalysis 64 2.1.3.1.2 Phase transfer catalysis 65 2.1.3.1.3 Supported liquid phase catalysis 65 2.1.3.1.4 Supported aqueous phase catalysis 65 2.1.3.2 Solid – liquid phase differentiation 65 2.1.3.2.1 Impregnation 65 2.1.3.2.2 Encapsulation 66 2.1.3.2.3 Anchoring 67 2.1.4 Immobilization on siliceous support 70 2.1.4.1 Grafting method 72 2.1.4.1.1 Post synthesis grafting method 72 2.1.4.1.2 Grafting with passive surface groups 73 2.1.4.1.3 Grafting with Reactive Surface Groups 73 ii 2.1.4.1.4 Site selective grafting 74 2.1.4.2 Coating Method 75 2.1.4.3 Co-condensation method 75 2.1.5 Ionic liquid 76 2.1.5.1 Constitution of ionic liquids 77 2.1.5.2 History of IL 79 2.1.5.3 Properties of IL 79 2.1.5.4 ILs are liquid at room temperature 81 2.1.5.5 Synthesis of IL 81 2.1.5.6 Commercial availability 81 2.1.5.7 Immobilized IL 82 2.2 Hydrotalcite 83 2.3 Clay Minerals 86 2.4 Synthesis and characterization of Immobilized IL catalysts 89 2.4.1 Experimental 89 2.4.1.1 Materials 89 2.4.2. Analytical 89 2.4.2.3 Theory and experimental procedures 91 2.4.2.3.1 X-ray diffraction (XRD) 91 2.4.2.3.2 Vibrational spectroscopy 92 2 .4.2.3.3 Transmission electron spectroscopy 93 2.4.2.3.4 Scanning Electron Microscopy 94 2.4.2.3.5 Nuclear Magnetic Resonance spectroscopy 94 2.4.2.3.6 Surface area measurement by BET Method 97 2.4.2.4 Preparation of Catalysts 98 2.4.2.4.1 Synthesis of Ionic liquids 98 2.4.2.4.1.1 Synthesis of (1-butyl-3-methyl imidazolium) chloride 98 2.4.2.4.1.2 Synthesis of (1-hexyl-3-methyl imidazolium) chloride 98 2.4.2.4.1.3 Synthesis of (1-octyl-3-methyl imidazolium) chloride 99 iii Synthesis of Immobilized IL catalyst by various methods of 2.4.2.4.2 99 immobilization Synthesis of immobilized catalyst by diffusional 2.4.2.4.2.1 99 Impregnation method Synthesis of immobilized catalyst by capillary impregnation 2.4.2.4.2.2 99 method 2.4.2.4.2.3. Grafting method 99 2.4.2.4.2.3.1 Synthesis of 1-(tri-ethoxy-silyl-propyl)-3-methyl- 99 imidazolium chloride 2.4.2.4.2.3.2 Immobilization of CAT 3 on various supports 100 2.4.2.4.2.3.2.1 Immobilization of 1-(tri-ethoxy-silyl-propyl)-3-methyl- 100 imidazolium chloride on silica support 2.4.2.4.2.3.2.2 Synthesis of MCM-41 101 2.4.2.4.2.3.2.3 Immobilization of 1-(tri-ethoxy-silyl-propyl)-3-methyl- 102 imidazolium chloride on MCM-41 support 2.4.2.4.2.3.2.4 Immobilization of 1-(tri-ethoxy-silyl-propyl)-3-methyl- 102 imidazolium chloride on montmorillonite clay support 2.4.2.4.2.3.2.5 Preparation of Zn-Al hydrotalcite 102 Immobilization of 1-(tri-ethoxy-silyl-propyl)-3-methyl- 2.4.2.4.2.3.2.6 103 imidazolium chloride on Zn/Al Hydrotalcite 2.4.2.4.2.3.2.7 Synthesis of 1-(tri-ethoxy-silyl-propyl)-pyridinium chloride 104 Immobilization of 1-(tri-ethoxy-silyl-propyl)-pyridinium 2.4.2.4.2.3.2.8 104 chloride on silica Quaternization of 3-(1-Imidazol-1-yl) propyl-functionalised 2.4.2.4.2.3.2.9 silica gel with n-butyl chloride 105 2.4.2.4.2.4 BSTFA treatment of CAT 3 immobilised on silica 105 2.4.2.5 Physicochemical characterization of catalysts 106 2.4.2.5.1 Characterization of (1-butyl-3-methyl imidazolium) chloride 106 2.4.2.5.2 Characterization of(1-hexyl-3-methyl imidazolium) chloride 106 2.4.2.5.3.
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