• Abstract and Figures
• Public Full-text

University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Spring 1993 I Asymmetric photochemistry II Exploratory and mechanistic studies on the triplet sensitized vapor phase photochemistry of allenes III Developments in the synthesis of strained cyclic cumulenes William Calvin Shakespeare University of New Hampshire, Durham Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation Shakespeare, William Calvin, "I Asymmetric photochemistry II Exploratory and mechanistic studies on the triplet sensitized vapor phase photochemistry of allenes III Developments in the synthesis of strained cyclic cumulenes" (1993). Doctoral Dissertations. 1740. https://scholars.unh.edu/dissertation/1740 This Dissertation is brought to you for free and open access by the Student Scholarship at University of New Hampshire Scholars' Repository. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of University of New Hampshire Scholars' Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand corner and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Company 300 North Zeeb Road. Ann Arbor. Ml 48106-1346 USA 313/761-4700 800/521-0600 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Order Number 9400399 I. Asymmetric photochemistry, n . Exploratory and mechanistic studies on the triplet sensitized vapor phase photochemistry of allenes. III. Developments in the synthesis of strained cyclic cumulenes Shakespeare, William Calvin, Ph.D. University of New Hampshire, 1993 UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. I. ASYMMETRIC PHOTOCHEMISTRY. II. EXPLORATORY AND MECHANISTIC STUDIES ON THE TRIPLET SENSITIZED VAPOR PHASE PHOTOCHEMISTRY OF ALLENES. III. DEVELOPMENTS IN THE SYNTHESIS OF STRAINED CYCLIC CUMULENES. William C. Shakespeare B. A. Gettysburg College, 1985 DISSERTATION Submitted to the University of New Hampshire in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Chemistry May, 1993 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation has been examined and approved. (L 'J li P. --- Dissertation Director, Rfcnard P. Johnson Professor of Chemistry C Pf a ls i/ s ' ( y l- O ^ M . Paul R. Jones, Professor of Chemistry Sterling A^lTomellini, Associate Professor of Chemistry Gary R /N eisman, Associate Professor of Chemis Roy. B. orberyProfessor of Physics Date Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. DEDICATION This work is dedicated to my loving parents, William and Anne Shakespeare. Their love and support throughout my often unpredictable youth was unabating. I remember well the myriad projects that my mother assisted me with, the one involving Ham Hocks and Hush Puppies being up near the top! I remember my fathers attendance at all of my swim meets as a child (his swims in the pool at half-time perhaps being the highlight!), and how pleased it made me feel. I could want nothing more than to give to my children as much love as my parents have given to me. Thanks you two. Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGMENTS If I were to acknowledge each and every individual who in some way affected my soujourn at the University of New Hampshire, this portion of my thesis would probably be the longest. However, there are several individuals who warrant special comment. The first is my loving wife Betina. Her support and dedication to excellence has had a profound affect on my life, both as a scientist and as a husband. Indeed, I owe a great del to her. She has not, however, succeded in curbing my unquenchable desire to procrastonate, perhaps no one will. I would also like to acknowledge my advisor Dr. Richard Johnson for his guidance and support throughout the years. He was an excellent mentor with a richly diversified background who taught us all a great deal. Additionally, I would like to thank the people in the instru­ mentation center: Dee Cardin, Bill Dotchin, and Richard Sweet. A special note of thanks to Kathy Gallagher with whom I spent many hours acquiring deuterium spectra. I would also like to acknowledge the assistance of Chiefura Noda who allowed me extensive use of his printer and trouble shooting abilties. Finally, I would like to thank all of my friends at the University, both past and present, who made the experience so enjoyable! Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS DEDICATION.................................................................................................. iii ACKNOWLEDGMENTS.................................................................................. iv TABLE OF CONTENTS....................................................................................v LIST OF SCHEMES........................................................................................viii LIST OF FIGURES..........................................................................................xv LIST OF TABLES.......................................................................................... xvii ABSTRACT...................................................................................................xviii CHAPTER PAGE GENERAL INTRODUCTION............................................................................. 1 I. ASYMMETRIC ORGANIC PHOTOCHEMISTRY...................................... 2 Introduction .......................................................................................2 Asymmetric Induction by Energy Transfer .........................4 Results and Discussion .................................................................... 9 Photoresolution of 1,3-Diphenylallene ................................11 Photoresolution of 1,3-Cyclooctadiene .............................. 12 Photoresolution of trans-1,2-Diphenylcyclopropane..14 Conclusion .......................................................................................15 II. THE PHOTOCHEMISTRY OF ALLENES................................................ 17 Introduction ..................................................................................... 17 Allene Singlet Photochemistry .............................................. 18 Allene Triplet Photochemistry .............................................. 21 Triplet Vapor Phase Photochemistry of Cyclohexylallene and Vinylidenecycloheptane ..........................28 Exploratory Triplet Photochemistry .................................... 28 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. II. THE PHOTOCHEMISTRY OF ALLENES (corvt) Benzene Sensitized Vapor Phase Irradiation of Cyclohexylallene .................................................................33 Benzene Sensitized Vapor Phase Irradiation of Vinylidenecycloheptane ..................................................... 34 Benzene Sensitized Solution Phase Irradiation of Cyclohexylallene and Vinylidenecycloheptane ................ 35 Discussion of Benzene Sensitized Vapor Phase Irradiation of Cyclohexylallene ............................................. 35 Discussion of Benzene Sensitized Vapor Phase Irradiation of Vinylidenecycloheptane ................................ 42 Discussion of Benzene Sensitized Solution Phase Irradiation of Cyclohexylallene and Vinylidenecycloheptane .........................................................43 Conclusion ............................................................................. 44 Ab Initio Study of Hydrogen Abstraction by Triplet Cyclopropylidene and Planar Triplet Allene ..............................45

Load more

  223

Copy Link