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  • A QUANTUM THEORETICAL

    STUDY OF THE 1,3-DIPOLAR

    CYCLOADDITION REACTIONS

    THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE

    REQUIREMENT OF THE DEGREE OF

    DOCTOR OF PHILOSOPHY (SCIENCE)

    IN CHEMISTRY

    OF

    THE UNIVERSITY OF BURDWAN

    TAPAS KUMAR DAS, M.Sc.

    DEPARTMENT OF CHEMISTRY

    THE UNIVERSITY OF BURDWAN

    BURDWAN-713104

    WEST BENGAL, INDIA

    MAY-2012

    TA

    PA

    S K

    UM

    AR

    D

    AS

    2

    01

    2

  • A QUANTUM THEORETICAL STUDY OF

    THE 1,3-DIPOLAR

    CYCLOADDITION REACTIONS

    Submitted by

    Tapas Kumar Das

    DEPARTMENT OF CHEMISTRY

    UNIVERSITY OF BURDWAN

    A THESIS

    SUBMITTED IN PARTIAL FULFILMENT OF

    THE REQUIREMENT FOR THE DEGREE OF

    DOCTOR OF PHILOSOPHY

    IN CHEMISTRY

    TO

    THE UNIVERSITY OF BURDWAN BURDWAN-713104

    INDIA MAY-2012

  • Dedicated to.

    My parents.

    .for their untiring love and blessings

  • The University of Burdwan

    Dr. Manas Banerjee

    Professor

    Department of Chemistry Golapbag,

    Burdwan 713104, India.

    Tel: +91-342-2533913 (O)

    +91-33-26845255 (R)

    Fax: +91-342-2530452 (O)

    E-mail: manasban@rediffmail.com

    Dated, 04.05.2012

    TO WHOM IT MAY CONCERN

    This is to certify that the thesis entitled A QUANTUM THEORETICAL STUDY

    OF THE 1,3-DIPOLAR CYCLOADDITION REACTIONS is the result of

    work done by Mr. Tapas Kumar Das, M.Sc., who has been registered to The

    University of Burdwan on 15.05.2006 for the award of Doctor of Philosophy

    (Science) under my supervision. This work, neither in part nor whole, has been

    submitted for fetching any degree by Mr. Das or others, to the best of my

    knowledge.

    This is also to certify that he has fulfilled all the requirements under the regulation

    relating to the nature of work, qualifying course work, period of research satisfying

    residential requirement and presentation of seminar talks etc. in the due time.

    (Manas Banerjee)

    [Supervisor]

  • Acknowledgements

    I take this golden opportunity to express my deepest sense of gratitude to my

    Supervisor Prof. Manas Banerjee for his guidance, encouragement, support and help

    rendered to me during my research tenure here without which my Thesis would have

    not been completed.

    I would like to thank the Head of the Department of Chemistry, University of

    Burdwan, for providing the facilities for necessary items. I would also like to extend

    my sincere thanks to the teachers of our Chemistry Department for their kind

    assistance whenever I felt the need for anything necessary for the completion of my

    Ph. D program.

    I sincerely thank all my friends and colleagues of my school, Ramnagar Atul

    Vidyalaya, Head Master: Mr. Prasanta Kumar Chakraborty, and Assistant Teachers:

    Anirban Seth, Abhijit Ray, Susanta Maity, Amit Adhya, Ujjwal Bhar and specially

    my research colleagues Mr. Kalyan Ghosh, Ms. Tandrima Chaudhuri, Mrs. Sneha

    Salampuria for all their encouragement, help and support.

    I would also like to thank all the research scholars and non-teaching staff of the

    chemistry department for their help and support rendered to me in the course of my

    research.

    Without the encouragement, inspiration, blessings and support of my Parents Mr.

    Nirapada Das and Smt. Susama Das, I would not have reached this stage. Here I

    would like to mention specially my wife Smt. Sampa Das and sons Subhadeep Das

    and Arghadeep Das without whose inspiration and moral support I would have never

    reached this far.

    Above all, I thank to the almighty God for His blessing and providing me so much.

    Burdwan

    May, 2012 Mr. Tapas Kumar Das

  • Contents

    Contents

    Dedication

    Letter of supervisor

    Acknowledgements

    PAGE

    Chapter 1 1-18

    General Introduction

    1.1. Cycloaddition Reaction 2

    1.2. Classification of Cycloaddition Reactions 8

    1.3. Need for a Quantum-Theoretical Study 10

    1.4. The Major Objectives of Study 11

    1.5. Previous Works of Different Research Groups 11

    1.6. General Scope of the Present Work 13

    References 17-18

    Chapter 2 19-48

    General methodology and theoretical approach towards chemical reactions 2.1 . Theoretical Chemistry and Chemical Reactions 20

    2.2 . Geometry Optimization 20

    2.3 . Test for a True Minimum 21

    2.4 . Transition State Optimization and its Location 22

    2.5 . Test for True Transition State 23

    2.6 . Quantum Chemical Tools for Electronic Energy Calculation 23

    2.6.1. The Hartree-Fock Self-Consistent Field Method 23

    2.6.2. Moller-Plesset Perturbation Theory 27

    2.6.3. Density Functional Theory 29

    2.7. Natural Bond Orbital (NBO) Analysis 33

    2.7.1. Wiberg Bond Index 35

    2.8. Chemical Reactivity Indexes 35

  • Contents

    2.8.a) Chemical Hardness 35

    2.8.b) Electronic Chemical Potential 37

    2.8.c) The Global Electrophilicity Index 37

    2.8.d) The Fukui Function 38

    2.8.e) The Local Electrophilicity Index 39

    2.8.f) The Global Nucleophilicity Index 39

    2.8.g) The Local Nucleophilicity Index 40

    2.8.h) Global and Local Softness 40

    2.8.i) Enthalpy or Heat of the Reaction 41

    2.8.j) Enthalpy of Activation 41

    2.8.k) Free Energy of the Reaction 42

    2.8.l) Free Energy of Activation 42

    2.8.m) Activation Energy 43

    2.8.n) Rate Constant 43

    2.8.o) Paulings Partial Bond Order (PBO) 46

    2.8.p) Charge Transfer at Transition State (CT) 46

    References 47-48

    Chapter 3 49-70

    Studies on cyclization of azomethine ylides with substituted alkenes

    3.1. Introduction 50

    3.2. Computational Method 52

    3.3. Results and Discussion 53

    3.3.1. Reaction of Acyclic Azomethine Ylides with Alkenes 57

    3.3.2. Reactions of Cyclic Azomethine Ylides with Alkenes

    Bearing Electron Withdrawing Substituents 60

    3.4. Nature of the Transition State 65

    3.5. Conclusion

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