Synthesis, Structural Evaluation and Studies of Reactivity of Heteroperoxovanadates (V) And Development of Solid acid Catalysts for Organic Transformations Saitanya Kumar Bharadwaj Department of Chemistry A Thesis Submitted in Fulfillment of the Degree of Doctor of Philosophy To Indian Institute of Technology Guwahati Guwahati-781039, ASSAM, INDIA June, 2009 TH-779_05612207 Dedicated to my Father TH-779_05612207 Statement INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Guwahati 781 039, India Department of Chemistry STATEMENT I do hereby declare that the matter embodied in this thesis is the result of investigations carried out by me in the Department of Chemistry, Indian Institute of Technology Guwahati, India under the guidance of Professor Mihir K, Chaudhuri, FASc., FNA and co-guidance of Dr. Gopal Das, Associate Professor. In keeping with the general practice of reporting scientific observations, due acknowledgements have been made wherever the work described is based on the findings of other investigators. June, 2009 Saitanya K Bharadwaj IIT Guwahati -i- TH-779_05612207 Certificate INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Guwahati 781 039, India Department of Chemistry CERTIFICATE It is certified that the work contained in the thesis entitled “ Synthesis, Structural Evaluation and Studies of Reactivity of Heteroperoxovanadates (V) And Development of Solid acid Catalysts for Organic Transformations” by Saitanya K Bharadwaj, a student in the Department of Chemistry, Indian Institute of Technology, Guwahati for the award of degree of Doctor of Philosophy has been carried out under my supervision/ co-supervision and that this work has not been submitted elsewhere for a degree. Mihir K. Chaudhuri, FASc., FNA Dr. Gopal Das Co- Supervisor Supervisor Associate Professor, Department of Chemistry Professor, Department of Chemistry IITGuwahati, Guwahati-781039, India IITGuwahati, Guwahati-781039, India Phone: +91-361-2582302 Phone: +91-361-2582314 E-mail: [email protected] Fax: +91-361-2582349 Or E-mail: [email protected] Vice Chancellor, Tezpur University Tezpur-784 028, India Phone: +91-3712-267003, Fax: +91-3712-267006 E-mail: [email protected] June 2009 -ii- TH-779_05612207 Ph D Grade card INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Guwahati 781 039, India Department of Chemistry CERTIFICATE OF COURSE WORK This is to certify that Saitanya K Bharadwaj has satisfactorily completed all the courses required for the Ph. D degree program. These courses include 1) CH 605 : Applied crystallography 2) CH 627 : New Reagents in Organic Chemistry 3) CH 611 : Bioinorganic Chemistry 4) CH 630 : A Fundamental Approach to Physical Chemistry Professor A. Chattopadhyay Professor T. Punniyamurthy Head Secretary Department of Chemistry Departmental Post Graduate Committee IIT Guwahati IIT Guwahati -iii - TH-779_05612207 Ph D Grade card INDIAN INSTITUTE OF TECHNOLOGY GUWAHATI Guwahati 781 039, India Ph.D. GRADE CARD Roll No.: 05612207 Department: Chemistry Name: Saitanya K Bharadwaj Semester: July 2005-June 2006 Course Course Name Credit Grade CH 605 Applied crystallography 6 AB CH 627 New Reagents in Organic Synthesis 6 AB CH 611 Bioinorganic Chemistry 6 AA CH 630 A Fundamental Approach to Physical Chemistry 6 BB Semester Performance Index: (S. P. I): 9.00 Cumulative Performance Index: (C. P. I): 9.00 June, 2009 Assistant Registrar (Academic) -iv- TH-779_05612207 Acknowledgment ACKNOWLEDGMENT It is my immense pleasure to express my sincere gratitude to my guide, Professor Mihir K. Chaudhuri, FASc., FNA for his precious suggestion, incisive guidance and decisive insights during the entire course of Ph.D. research. I would like to thank my co-guide Dr. Gopal Das for his help and support. I remain obliged to Dr. R. C. Deka of Tezpur University, who has introduced me to a new field of Chemistry. I am also thankful to Professor Samir Bhatacharya, FASc., FNA of Visva Bharati, Shantineketan, West Bengal for his kind advice and help. I would like to thank all faculty members of Department of Chemistry of IIT Guwahati for their invaluable suggestions. I wish to acknowledge my sincere gratitude to the Council of Scientific and Industrial Research (CSIR), India for financial support and IIT Guwahati for all the facilities that were made available to me. I am thankful to Dr. Mamoranjan Kar of Center for Nanotechnology, Mr. Babulal Das of Department of Chemistry, Mr. Chandan Borgohain and Mr. Kulakamal Senapati of Central Instruments Facility for their help in all characterizations (Powder XRD, Single Crystal XRD, SEM, NMR etc.) required during my research work. I also thank Lipikaba, Abhilashaba, Parikshitda, Digantada, Mondolda, Nylotpalda, and Santanu for helping me selflessly. It is my pleasant duty to acknowledge with thanks the co-operation and support extended to me by the authority of Tezpur University and its staff. I extend my sincere gratitude to Dr. Alak K. Buragohain, Registrar, Tezpur University for his constant encouragement and convey my thanks to Mr. Arun Sarma, Mr. Kumarjit Dutta, Dibakarda and Chetryda of office of the Vice-chancellor, Tezpur University for their kind support. I thank Dr. Sahid Hussain, my senior and Dr. Papori Goswami for their invaluable suggestions. I wish to thank my friends Susanda, Nirmal, Neraaj, Ramesh, Ballav, Amardeep, Rajeeb, Jeshmini, Shahzad, Jagannath, Debajyoti, Sonit, Prasanta, Bolinda, Jayashreeba, Musaweer, Mohan, Ziyauddin, Rajen and all other research scholars for the joyful moments shared with them at IITG and their support. My special thanks go to Siva, Subhash, Jitu, Gunin, Gopal and Rajendra, for their help and support in academic and non-academic affairs all throughout. I extend my sincerest thanks to my ‘TEZU’ friends - Digantada, Harekrishna, Sivaprasad, Amar, Kalyanda, Subrata, Lakshi, Dhruba, Surajit and others. -v- TH-779_05612207 Acknowledgment Finally, I owe heartfelt gratitude to my mother for her blessings and support, and my sisters- Dharitriba, Queenba and Maina for constantly inspiring me to carry out my research work to completion. I am thankful to all my relatives and well-wishers for their encouragement. Unique thoughts of gratitude go to my wonderful father whom I have lost just a month ago. I wish I would had the opportunity to share all this achievements with you. I miss you and I wish you were still here with me. (Saitanya K Bharadwaj) -vi - TH-779_05612207 Content CONTENTS Chapter 1: Introduction Introduction ............................................................................................................ 1 Scope of work....................................................................................................... 21 References …………………………..………………………………………… 22 Chapter 2: Materials and Methods Preparation of starting materials …………..…………………………………… 33 Elemental analysis …………………………..…………………………………. 35 Instrumental details ………………………..…………………………………….39 Computational details ……………………..……………………………………. 41 References ……………………………….……………………………………. 42 Chapter 3: Newer Heteroperoxovanadates (V): Synthesis, Structure and Reactivity Introduction ………………………………..…………………………………… 43 3.1 Synthesis, structural delineation and DFT investigation of Oxo-peroxo- dimethylpyrazole-vanadate (V) 3.1.1 Experimental …………………………………………………………. 46 3.1.2 Results and Discussion ……………………………...……………….. 48 Density Functional Theory based study …………………………….. 60 Insulinomimetic Study of Compound (1), DmpzH[VO(O 2)2dmpz]…..62 3.1.3 Conclusion …………………………………………………………… 64 3.2 Synthesis and structural delineation of Oxo-peroxo-citrato-vanadate (V) 3.2.1 Experimental …………………………………………………………. 65 3.2.2 Results and Discussion ………………………………………………. 69 3.2.3 Conclusion …………………………………………………………….74 3.3 Synthesis and structural investigation of Oxo-peroxo- µ-hydroxo and µ- fluoro-vanadates (V) 3.3.1 Experimental …………………………………………………………. 75 3.3.2 Results and Discussion ………………………………………………. 76 3.3.3 Conclusion …………………………………………………………… 82 3.4 Studies of Reactivity of Newer Peroxovanadates (V) 3.4.1 Experimental …………………………………………………………. 83 3.4.2 Results and Discussion ………………………………………………. 85 -vii - TH-779_05612207 Content 3.4.3 Conclusion …………………………………………………………...… 88 References……………………………………………………………………....... 89 Selected Spectra…………………………………………………………………... 93 Chapter 4: Oxidative Extraction of Bromide from Sea Bittern and Bromination of phenol directly with sea bittern by bio-mimicking catalysis Introduction ……………………………………………………………………… 95 4.1 Extraction of Bromide from Sea Bittern: An Eco-friendly Bio-mimetic Process 4.1.1 Experimental ………………………………………………………...…. 97 4.1.2 Results and Discussion ………………………………………..……….. 98 4.1.3 Conclusion ……………………………………………………………. 106 4.2 Direct Bromination of Phenol with Sea Bittern 4.2.1 Experimental ……………………………………………………….…. 107 4.2.2 Results and Discussion ……………………………………………. ….107 4.2.3 Conclusion …………………………………………………………….. 109 References ………………………………………………………………………. 110 Selected Spectra ………………………………………………………………… 111 Chapter 5: Development of sewer solid acid catalysts for organic transformations Introduction …………………………………………………………………….. 113 5.1 Experimental ……………………………………………………………. 117 5.2 Results and Discussion …………………………………………………..117 5.2.1 Preparation and characterization of catalysts a) Catalyst – A, Al(H 2PO 4)3................................................................ 117 (b) Catalyst-T, (TiO 2)5.45 [Ti 4H11 (PO 4)9].4 H 2O.................................. 119 5.2.2 Nitration of organic compounds with nitric acid …………………. 122 5.2.3 Phosphate impregnated titania catalyzed chemoselective sulfoxidation