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Studies in Catalytic Carbonylation of Amines for the Synthesis of Disubstituted Ureas and Carbamates

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Studies in Catalytic Carbonylation of Amines for the Synthesis of Disubstituted Ureas and Carbamates STUDIES IN CATALYTIC CARBONYLATION OF AMINES FOR THE SYNTHESIS OF DISUBSTITUTED UREAS AND CARBAMATES MAHESH RAJARAM DIDGIKAR UNDER THE GUIDANCE OF Dr. S. P. GUPTE CHEMICAL ENGINEERING AND PROCESS DEVELOPMENT DIVISION NATIONAL CHEMICAL LABORATORY PUNE-411 008, INDIA JUNE 2009 STUDIES IN CATALYTIC CARBONYLATION OF AMINES FOR THE SYNTHESIS OF DISUBSTITUTED UREAS AND CARBAMATES A THESIS SUBMITTED TO THE UNIVERSITY OF PUNE FOR THE DEGREE OF DOCTOR OF PHILOSOPHY IN CHEMISTRY BY MAHESH RAJARAM DIDGIKAR UNDER THE GUIDANCE OF Dr. S. P. GUPTE AT CHEMICAL ENGINEERING AND PROCESS DEVELOPMENT DIVISION NATIONAL CHEMICAL LABORATORY PUNE-411 008, INDIA JUNE 2009 CERTIFICATE This is to certify that the work incorporated in the thesis, “Studies in Catalytic Carbonylation of Amines for the Synthesis of Disubstituted Ureas and Carbamates” submitted by Mr. Mahesh R. Didgikar, for the Degree of Doctor of Philosophy, was carried out by the candidate under my supervision in the C.E. & P.D. Division, National Chemical Laboratory, Pune – 411 008, India. Such material as has been obtained from other sources has been duly acknowledged in the thesis. Dr. S. P Gupte (Research Supervisor) Declaration I hereby declare that the thesis entitled “Studies in catalytic carbonylation of amines for the synthesis of disubstituted ureas and carbamates”, submitted for the Degree of Doctor of Philosophy to the University of Pune, has been carried out by me at the National Chemical Laboratory, Pune under the supervision of Dr. S. P. Gupte. The work is original and has not been submitted in part or full by me for any other degree or diploma to this or any other University. Date: Place: (Mahesh R. Didgikar) Dedicated to My Parents ACKNOWLEDGEMENT I wish to express my sincere gratitude to my research guide, Dr. S. P. Gupte. I feel deeply indebted to his immense contribution in the making of this thesis. I wish to acknowledge his ceaseless inspiration, thoughtful guidance, constructive criticism, patience and friendship to shape up the researcher in me. I take this opportunity to salute his supporting attitude that has always led me to think and work independently. My deepest regards for the patience he has kept and given me enough time for learning. I am deeply indebted to Dr. R. V. Chaudhari, former Head, Homogeneous Catalysis Division, National Chemical Laboratory (NCL). His able guidance has always inspired me. I am grateful to Council of Scientific and Industrial Research (CSIR), India for the research fellowship. I am thankful to former Director Dr. Paul Ratnasamy and present Director Dr. S. Sivaram, NCL for allowing me to carry out research work and extending me all the possible infrastructural facilities. I take this opportunity to express my sincere gratitude to Mr. Sunil Joshi, who has been a wondeful guide, a true friend and a great moral support. Needless to say that it was his blessings and sincere good wishes, which has transformed into my thesis today. I would like to acknowledge Dr. R. Jaganathan, Dr. R. M. Deshpande, Dr. A. A. Kelkar, Dr. V. V. Ranade, Dr. V. H. Rane, Dr. C. V. Rode, Dr. S. S. Divekar, Dr, Shubhangi Umbarkar, Mr. P. B. Jadkar and Mr. Raheja, past or present staff of C.E. and P. D. Division, NCL, for their help, support and encouragement. My research journey has been pleasurable and fruitful with my friend Kalpendra. He has been the closest of my friends, a great source of encouragement, and a good critic who has given valuable suggestions, and surely will continue to do so. I sincerely acknowledge my senior colleagues and friends Dr. Shrikant kulkarni and Dr. Sunil Tonde, who have been my constant source of encouragement. I take this opportunity to thank them from the bottom of my heart. I must also mention my gratefulness for my friends and colleagues Debu, Yogesh, Tushar, Avinash M., Manisha K., Manisha T., Charu, Makarand, Anand, Nandu, Anup, Savita, Lalita, PP, Nitin, Abhishek, Bibhas, Amit Deshmukh, Amit Chaudhari, Vikas, JP, Deepak, Sangita, Samadhan, and many in NCL, who are not named in person for their valuable suggestions and helping hands. I am deeply thankful to my dear friends and labmates Nilesh Kulkarni, Archana, Charu, Swapna, Aditi, Swapnali, Ravi, Sandeep, Umesh, Satish, Sanjay and Raj. They made my stay at NCL a sweet and memorable experience. Saving the best for the last, I can never thank enough my aai, baba and tai. Their moral support and genuine blessings have shaped up the person in me, and has instilled in me a sense of belongingness, responsibility and ability. Their constant encouragement has made me succeed through this journey. No thanks can be enough to acknowledge the encouragement and support of my wife, Sheetal. She has been my constant source of strength. I am also thankful to Sonal, Shardul and Kunal for their support and encouragement. June 2009 Mahesh R. Didgikar List of Contents Description Page Number Chapter Index i List of Tables vi List of Figures vii List of Schemes xi Abstract of the Thesis xiv Appendix I - List of abbreviations xxiii List of Publication /Conferences / Symposia xxiv Chapter 1 Introduction and literature survey 1.1 Introduction 1 1.2 Catalysis and fine chemical industry 3 1.3 Carbonylation using phosgene 7 1.3.1 Synthesis of substituted ureas and carbamates using phosgene 8 1.3.2 Synthesis of polycarbonates using phosgene 9 1.3.3 Synthesis of polyurethanes using phosgene 10 1.3.4 Environmental concerns 11 1.4 Synthesis and applications of substituted ureas 12 1.4.1 Applications of substituted ureas in fine and specialty chemicals 12 1.4.2 Non-phosgene, reagent-based methods of synthesis 13 1.4.3 Green methods of synthesis of substituted ureas 22 1.5 Synthesis and applications of carbamates 28 1.5.1 Non-phosgene, reagent based methods for carbamate synthesis 29 1.5.2 Eco-friendly methods for carbamate synthesis 32 1.6 Oxidative carbonyaltion of amines 41 1.6.1 General features of oxidative carbonylation reaction 41 1.6.2 Mechanism of oxidative carbonylation of amines 52 1.6.3 Safety Aspects in Oxidative Carbonylation 56 1.7 Scope and objective of the thesis 58 References 59 i Chapter II. Aqueous-Biphasic Oxidative Carbonylation of Amines Using Water- soluble Transition Metal Catalysts 2.1 Introduction 69 2.2 Experimental section 71 2.2.1. Materials 71 2.2.1.1. Chemicals 71 2.2.1.2.. Synthesis of N-ligands 72 2.2.1.3. Synthesis of Pd(OAc)2(bipy) 78 2.2.1.4. Synthesis of water-soluble transition metal catalysts 79 2.2.2. General procedure for oxidative carbonylation of amines 80 2.2.2.1. Experimental set-up 80 2.2.2.2 Typical procedure for oxidative carbonylation of amines 81 2.2.3. Analytical methods 81 2.3. Results and discussion 84 2.3.1. Preliminary experiments to establish the activity of water-soluble 84 catalyst 2.3.2. Effect of agitation speed 86 2.2.3. Typical oxidative carbonylation reaction and concentration-time 86 profile 2.3.4. Screening of water-soluble transition metal complexes 88 2.3.5. Effect of solvents 89 2.3.6. Effect of iodide promoters 90 2.3.7. Effect of iodide concentration 91 2.3.8. Recycle studies 92 2.3.8.1. Catalyst recycle 92 2.3.8.2. Promoter recycle 93 2.3.8.3. Catalyst recycle: Oxidation state of Pd 94 2.3.9. Screening of water-soluble N-ligands 97 2.3.10. Effect of reaction parameters on the reaction 99 2.3.10.1. Effect of reaction temperature 99 2.3.10.2. Effect of aniline concentration 100 ii 2.3.10.3. Effect of variation in PCO 101 2.3.10.4. Effect of variation in PO2 102 2.3.11. Proposed mechanism 103 2.3.12. Screening of amine substrates 104 2.3.12.1. Primary monoamines as substrates 105 2.3.12.2. Primary diamines as substrates 106 2.3.12.3. Secondary amines as substrates 107 2.4. Conclusions 109 References 111 Chapter III. Lead Oxide Catalyzed Methoxycarbonylation of Amines with Dimethylcarbonate 3.1 Introduction 122 3.2 Experimental section 124 3.2.1. Materials 124 3.2.2. Experimental set-up 124 3.2.3. Typical Experimental Procedure for Methoxycarbonylation of 125 Amines 3.2.4. Typical Experimental Procedure for Kinetic Studies 126 3.2.5. Catalyst recycle experiment procedure 126 3.2.6. Experimental Procedure for Catalyst Pretreatment Investigation 126 3.2.7. Reaction Work-Up And Isolation of Carbamates 127 3.3. Analytical Methods 128 3.4. Results and Discussion 130 3.4.1. Preliminary catalyst screening 130 3.4.2. Standard Concentration-Time (C-T) Profile and Mass Balance 132 3.4.3. Induction period 133 3.4.3.1. Effect of Pb3O4 Concentration on Induction Period 133 3.4.3.2. Effect of Aniline Concentration on Induction Period 134 iii 3.4.3.3. Effect of Reaction Temperature on Induction Period 134 3.4.4. Inhibition of Reaction Progress by Products 135 3.4.4.1. Effect of Methyl-N-Phenyl Carbamate 135 3.4.4.2. Effect of Methanol concentration 136 3.4.5. Catalyst recycle 137 3.4.6. Effect of Catalyst Pre-Treatment 138 3.4.6.1. Effect of Catalyst Pre-Treatment With Aniline 138 3.4.6.2. Effect of Catalyst Pre-Treatment with Dimethyl Carbonate 139 3.4.7. Screening of Amine Substrates 140 3.4.8. Kinetic study 144 3.4.8.1. Preliminary experiments 144 3.4.8.2. Effect of Catalyst (Pb3O4) Concentration 144 3.4.8.3. Effect of Temperature 145 3.4.8.4.
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