Photochemical 1,3-cycloaddition of olefins to substituted benzenes Item Type text; Dissertation-Reproduction (electronic) Authors Linstid, Henry Clay Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 27/09/2021 09:55:08 Link to Item http://hdl.handle.net/10150/565399 PHOTOCHEMICAL 1,3-CYCLOADDITION OF OLEFINS TO SUBSTITUTED BENZENES by Henry Clay Linstid III A Dissertation Submitted to the Faculty of the DEPARTMENT OF CHEMISTRY In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 1 9 7 8 THE UHIVERSITY OF ARIZOM GRADUATE COLLEGE I hereby reeoaaend thsfc this dissertation prepared under my direction by ______Henrv Clav Linstid III____________ ' entitled PHOTOCHEMICAL 1» 3-CYCLOADDITION OF OT.EFTNS TO SUBSTITUTED BENZENES ______________________ be accepted as fulfilling the dissertation requirement for the degree of _______ DOCTOR OF PHILOSOPHY W r f Date As members of the Final Examination Committee0 we certify that we have read this dissertation and agree that it may be presented for final defense. I I O/r fh/lX Final approval and acceptance of this dissertation is contingent oh the candidate”s adequate performance and defense thereof at the final oral examination* STATEMENT BY AUTHOR This dissertation has been submitted in partial fulfillment of requirements for an advanced degree at The University of Arizona and is deposited in the University Library to be. made available to borrowers under rules of the Library. Brief quotations from this dissertation are allowable without special permission, provided-that accurate acknowledgment of source is made. Requests for permission for extended quotation form or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGNED: -/(Q For Sharon, Ben and The Little Stranger ACKNOWLEDGMENTS The author wishes to express his thanks to Dr, Lee B. Jones for his help and guidance in this research. In addition, the helpful advice of Dr. Robert Bates and Dr. Michael Barfield is sincerely appreciated. A special note of thanks is due to the highly skilled members of the Electronics Shop, Mr. John Barrowman, Mr. Ted Parker, Mr. Allen Morgan, and Mr. Steve Turner. Without their invaluable aid, the author's position as NMR research assistant would have been a much less pleasant experience. Finally, the important role of many friends and coworkers of the author cannot be forgotten. In particular, the friendship and professional association with Dr. George P. Marshall were of inestimable value in the completion of this work. TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS ................................. vii LIST OF TABLES ............... , . x ABSTRACT ............................................. ' . xii INTRODUCTION . 1 R E S U L T S .................. 13 Synthetic Procedures ... 13 The 1,3-Photocycloaddition of Cyclopentene to B e n z e n e . 14 The 1,3-Photocycloaddition of Cyclopentene to Anisole ............... 20 The Photochemical Cycloaddition of Cyclopentene to Methyl Benzoate 25 Attempted Photocycloaddition of Cyclopentene to Phenyl Acetate . 35 Attempted Photocycloaddition of Various Olefins to Methyl ortho-Anisate ........ 35 The Photochemistry of 4-Phenylbut-l-ene ..... 37 The Photochemistry of 5-Phenylpent-l-ene ......... 47 The Intramolecular 1,3-Photocycloaddition of Phenyl But-3-enyl E t h e r .................... 62 The Intramolecular 1,2-Photocycloaddition of Methyl 2-(but-3-enyl)benzoate ........ 69 The Intramolecular 1,3-Photocycloaddition of Methyl 2-Allyloxybenzoate ..... ......... 74 . The Intramolecular 1,4-Photocycloaddition of Methyl 2-(but-3-enyloxy)benzoate ........... 84 DISCUSSION ........... 94 EXPERIMENTAL .......................... 115 General ............. 115 Preparation of Methyl ortho-Anisate ....... 117 Preparation of Allyl Methyl Ether . ........ 118 Preparation of Methanol-0-d . .................... 119 Preparation of 4-Phenylbut-l-ene........... 119 Preparation of Methyl 2-(but-3-enyl)benzoate . 121 vi TABLE OF CONTENTS— Continued Page Preparation of Methyl 2-Allyloxybenzoate ......... 125 Preparation of Methyl 5-Methy1-2- ally loxybenzoate and Methyl 4-Methyl- 2-ally loxybenzoate................................... 126 General Procedure for Photolyses ........... , 127 Sensitized Irradiation of Methyl 2- (But-3-enyloxy)benzoate ...................... • 134 REFERENCES .............................................. 135 LIST.OF ILLUSTRATIONS Figure Page 1. Possible mechanistic scheme for the photocycloaddition of olefins to b e n z e n e ........................................ 11 2. 60 MHz NMR spectrum Of the 1,3- photocycloadduct of cyclopentene and benzene . ................................. 16 13 3. Reconstructed C NMR spectrum of the 1,3- photocycloadduct of cyclopentene and b e n z e n e ........... .... ....................... 17 4. 60 MHz "*"H NMR spectrum of the 1,3- photocycloadduct of cyclopentene to anisole ............. 22 13 5. Reconstructed C NMR spectrum of the 1,3- photocycloadduct of cyclopentene and anisole ........... 23 1 6. 60 MHz H NMR spectrum of the 1,3- photocycloadducts of cyclopentene and methyl benzoate formed in cyclohexane .... 28 7. 60 MHz "bl NMR spectrum of the 1,2- photocycloadduct of cyclopentene and methyl benzoate formed in methanol ............ 31 8. 60 MHz "*"H NMR spectrum of the 1,3- photocycloadduct of cyclopentene and methyl benzoate formed in methanol ...... 34 9. 60 MHz "*"H NMR spectrum of product _14 of the photolysis of 4-phenylbut-3-ene in methanol ............................. 41 10. 60 MHz ^H NMR spectrum of product 15 of the photolysis of 4-phenylbut-3-ene in methanol ............... 42 vii viii LIST OF ILLUSTRATIONS— Continued Figure Page 1 ■ 11. 60 MHz H NMR spectrum of product lj5 of the photolysis of 4-phenylbut-3-ene in methanol ............................. 43 12. 60 MHz ^"H NMR spectrum of the intramolecular 1.3-photocycloadduct of 5-phenylpent-l-ene , . 51 13 . 13. Reconstructed C NMR spectrum of the intramolecular 1,3-photocycloadduct of 5-phenylpent-l-ene ........ 52 • i 14. 60 MHz H NMR spectrum of the major product of the irradiation of 5-phenylpent-l-ene in methanol, ]_8 56 1 15. 60 MHz H NMR spectrum of the minor product of the irradiation of 5-phenylpent-l-ene in methanol, l j ) ............... * . 57 1 16. 60 MHz H NMR spectrum of the intramolecular 1.3-photocycloadduct of phenyl but-3-enyl e t h e r .......................................... 65 17. Results of homonuclear decoupling on the 60 MHz H NMR spectrum of the major product of the photolysis of phenyl but-3-enyl ether . 68 13 18. Reconstructed C NMR spectrum of the intramolecular 1,3-photocycloadduct of phenyl but-3-eriyi ether ..... .'......... 71 1 19. 60 MHz H NMR spectrum of the intramolecular 1.2-photocycloadduct of methyl 2-(but-3- enyl) benzoate ................. 73 20. 60 MHz H NMR spectrum of the intramolecular 1.3-photocycloadduct of methyl 2- allyloxybenzoate ......... 77 13 21. Reconstructed C NMR spectrum of the intramolecular 1,3-photocycloadduct of methyl 2-allyloxybenzoate .......... 82 *i 22. 60 MHz H NMR spectrum of the intramolecular 1.4-photocycloadduct of methyl 2-(but-3- enyloxy)benzoate ............... 87 i ix LIST OF ILLUSTRATIONS— Continued Figure Page 13 • 23. Reconstructed C NMR spectrum of the intramolecular 1,4-photocycloadduct of methyl 2-(but-3-enyloxy)benzoate....... 89 24. Isomerism in the formation of 1,3- photocycloadducts ............................. 104 25. Mechanism proposed by Sullivan (1973) for the formation of the major product of photolysis of methyl 2-allyloxybenzoate in methanol . 108 26. Proposed mechanism for the formation of the major product of photolysis of methyl 2-allyloxybenzoate in methanol .... 110 21. Two dimensional schematic representation of the reaction topology for the cyclo- addition of olefins to benzenes . 113 LIST OF TABLES Table - Page 1. Ionization potentials and quantum yields ($) of adduct for mono-olefins that form 1.3-photocycloadducts with benzene (IP = 9.24 eV) .................. 4 1 2. UV, IR, H NMR and mass spectral data for the 1,3-photocycloadduct of cyclopentene and benzene ............................. 15 13 3. C NMR chemical shifts and line assign­ ments for the 1,3-photocycloadduct of cyclopentene and benzene . 18 4. IR, NMR and mass spectral data for the 1.3-photocycloadduct of cyclopentene and anisqle ............................... 21 5. "^C NMR chemical shifts and line assignments for the 1,3-photocycloadduct of cyclo­ pentene and anisqle ........ ......... 24 6. IR, NMR and mass spectral data for the 1.3-photocycldadducts of cyclopentene and methyl benzoate formed in cyclohexane .... 26 1 7. IR, H NMR and mass spectral data for the 1,2-photocycloadduct and the 1,3- photocycloadduct of cyclopentene and methyl benzoate formed in methanol ........... 3 0 8. IR, "*"H NMR and mass spectral data for the photoproducts resulting from the irradiation of 4-phenylbut-l-ene in methanol ................................. 38 1 9. IR, H NMR