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The Photochemistry of Some Acyclic Ketones Containing a Silicon Or a Tin Atom

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The Photochemistry of Some Acyclic Ketones Containing a Silicon Or a Tin Atom University of New Hampshire University of New Hampshire Scholars' Repository Doctoral Dissertations Student Scholarship Summer 1965 THE PHOTOCHEMISTRY OF SOME ACYCLIC KETONES CONTAINING A SILICON OR A TIN ATOM PERRY LESTER MAXFIELD Follow this and additional works at: https://scholars.unh.edu/dissertation Recommended Citation MAXFIELD, PERRY LESTER, "THE PHOTOCHEMISTRY OF SOME ACYCLIC KETONES CONTAINING A SILICON OR A TIN ATOM" (1965). Doctoral Dissertations. 816. https://scholars.unh.edu/dissertation/816 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]. This dissertation has been microfilmed exactly as received 6 6-5974 MAXFIELD, Perry Lester, 1933- THE PHOTOCHEMISTRY OF SOME ACYCLIC KETONES CONTAINING A SILICON OR A TIN ATOM. University of New Hampshire, Ph.D., 1965 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan THE PHOTOCHEMISTRY OF SOME ACYCLIC KETONES CONTAINING A SILICON OR A TIN ATOM BY PERRY LESTER MAXFIELD B. S., Brigham Young University, 1961 A THESIS Submitted to the University of New Hampshire In Partial Fulfillment of The Requirements for the Degree of Doctor of Philosophy Graduate School Department of Chemistry August, 1964 This thesis has been examined and approved. Date ACKNOWLEDGMENT I wish to express my gratitude to the Department of Chemistry of the University of New Hampshire for the help and guidance which I have received during my stay here. Acknowledg ment is also due the United States Department of Health, Edu­ cation, and Welfare for a National Defense Education Fellow­ ship which has been so helpful in financing the three years of study. I especially want to thank Dr. Henry G. Kuivila, my advisor, for the assistance, encouragement, and guidance which he has freely given while I was performing the experimental work and preparing this manuscript. I also want to thank my family for the patience they have shown and the encouragement they have given to me during these years of school. TABLE OF CONTENTS Page LIST OF TABLES ........................................ vii LIST OF FIGURES ....................................... viii I. INTRODUCTION ........................................... 1 II. STATEMENT OF PROBLEM ................................. 6 III. RESULTS AND DISCUSSION .............................. 10 A. 2-Sila-2,2-dimethyl-7-phenylheptan-7-one(III) 10 B. 2-Sila-2,2-dimethy1-6-phenylhexan-6 -one(IV).. 13 C. 2-Sila-2,2-dimethylheptan-6 -one(V) 15 D. l-Sila-l-phenyl-4-butanal(XVII) ............... 18 E. 2-Sila-2,2-dimethyl-5-phenylpentan-5-one(VI) 21 F. 2-Sila-2,2-dimethylhexan-5-one(VII) .......... 24 G. Trimethylsilylacetophenone(VIII)............... 27 H. Trimethylsilylacetone(IX) ....................... 30 I. Benzoyltrimethylsilane(X) 32 J. 4-(1-Phenyl-l-oxobutyl)trimethyIsilane(XI) .. 37 K. 5 -(2-Oxopentyl)trimethyltin(XII) .............. 41 L. 3-(1-Phenyl-l-oxopropy1)trimethyltin(XIII) .. 43 M. 4-(2-0xobutyl)trimethyltin(XIV) ............... 45 N. Mechanisms for the Tin compounds .............. 46 0. Benzoyltrimethylgermane(XV) .................... 53 P. 3 -(TrimethyIsilyl)acrolein(XVI) ............... 54 IV. EXPERIMENTAL ........................................... 56 A. Photolysis Procedures ............................ 57 B. Isolation of Photolysis Products .............. 62 C. Preparation of Silanes .......................... 62 1. 2-Sila-2,2-dimethylhexan-5-one(VII) ...... 62 2. 5-Sila-5,5-dichlorohexanonitrile ........ 64 3. 2-Sila-2,2-dimethylheptan-6-one(V) ....... 64 4. Vinyltrimethylsilane ........................ 64 5. 2-Sila-2,2-dimethyl-5-phenylpentan- 5-one(VI) ................................... 65 6 . 2-Sila-2,2-dimethylpentyl-5-nitrile ...... 65 7. 2-Sila-2,2-dimethyl-6-phenylhexan-6- one(IV) ...................................... 66 8 . 2,3-Diphenylbutan-2,3-diol ................. 67 9. Chloromethyltrimethylsilane ................ 67 iv page 10. Addition of methyldichlorosilane to methyl vinyl ketone ..................... 68 11. Iodotrimethylsilane ........................ 68 1 2 . 2 -Sila-2 ,2 -dimethy1-5-eyelohexy1-5-phenyl- pentan-5-ol ............................... 68 13. Trimethylsilylacetone(IX) ................ 69 14. Pentylsilane ................................ 69 15. Cyclohexylcarbinol ......................... 69 16. Cyclohexylchloromethane ................... 70 17. 2-Sila-2,2-dimethyl-4-cyclohexylbutane . 70 18. Benzoic anhydride .......................... 71 19. Trimethylsilylacetophenone(VIII) ........ 71 20. Addition of methylchlorosilane to allyl chloride ................................. 72 21. 1-(Trimethylsily1)-3-chloropropane ..... 72 22. 1-(Trimethylsilyl)-3-iodopropane ........ 72 23. 2-Sila-2,2-dimethyl-7-phenylheptan- 7 -one (III) ............................... 72 24. Benzyltrimethylsilane ..................... 73 25. a,o-Dibromobenzyltrimethylsilane ........ 73 26. Benzoyltrimethylsilane .................... 74 27. Phenylsilane ................................ 74 28. 1-Sila-l-phenyl-4,4-dimethoxybutane .... 74 29. 4-Sila-4-phenylbutanal .................... 75 30. 1,2-Dibenzoylethane ........................ 75 31. 1,4-bis(Trimethylsilyl)butane ............ 76 32. Ethoxytrimethylsilane ..................... 76 33. 2-Sila-2,2,6 ,7-tetramethyldecan-6 -ol ... 76 34. 1-Methyl-2-trimethylsilylcyclobutanol .. 77 D. Degradation of l-methyl-2-trimethylsilylcyclo- butanol ........................................ 78 E. Preparation of Organotin Compounds .......... 78 1. Tributyltin hydride .................... 78 2. Vinyltrimethyltin .......................... 79 3. Trimethyltin chloride ..................... 79 4. Trimethyltin hydride ....................... 79 5. Trimethyl-2-cyanoethyltin ................. 79 6 . 5 -(2 -0xopenty1)trimethyltin .............. 80 7 . 4 -(2 -0xobutyl)trimethyltin ............... 80 8 . 4-(1-Phenyl-l-oxobutyl)trimethyltin .... 81 9. 3-(1-Phenyl-l-oxopropyl)trimethyltin ... 81 v page F. Preparation of Germanes ....................... 82 1. Phenyltrichlorogermane ................... 82 2. Phenyltrimethylgermane ................... 82 3 . Bromotrimethylgermane .................... 83 4. Benzyltrimethylgermane ................... 83 5. a ,a-Dibromobenzyltrimethylgermane ..... 83 6 . Benzoyltrimethylgermane .................. 84 V. SUMMARY ............................................... 85 VI. BIBLIOGRAPHY ......................................... 91 vi LIST OF TABLES Number Page I Cyclobutanol Formation in Photolysis ........... 4 II Energies of Pertinent Bonds ...................... 7 III Photolysis of 2-sila-2,2-dimethyl-7-phenyl- heptan-7-one .................................... 12 IV Photolysis of 2-sila-2,2-dimethyl-6-phenyl- hexan-6 -one ............................. 14 V Photolysis of 2-sila-2,2-dimethylheptan-6-one 16 VI Photolysis of 2-sila-2,2-dimethyl-5-phenyl- pentan-5-one .................................... 23 VII Photolysis of 2-sila-2,2-dimethylhexan-5-one . 25 VIII Photolysis of trimethylsilylacetophenone ..... 28 IX Photolysis of benzoyltrimethylsilane .......... 34 X Photolysis of 4-(1-phenyl-l-oxobutyl)- trimethyltin .................................... 39 XI Photolysis of 5-(2-oxopentyl)trimethyltin .... 42 XII Photolysis of 3-(1-phenyl-l-oxopropyl)- trimethyltin .............. 44 XIII Photolysis of 4-(2-oxobutyl)trimethyltin ...... 47 XIV Characteristics of Hanovia Lamp 679A ........... 61 vii LIST OF FIGURES Number Page I Apparatus for Procedure (a) ........................ 58 II Apparatus for Procedure (b) ........................ 59 III Apparatus for Procedure (c) ............... 60 IV Percent Transmittance of Filters ................. 63 INTRODUCTION The photolysis of ketones in the gaseous phase has been widely studied. Acetone is an example of a ketone which has been investigated considerably. Noyes and Dorfmann^ pro­ posed the following generally accepted free radical mechanism for the photolysis of acetone. ch3coch3 hv — ^ CH3CO -p CHq - (1 ) c h 3co — ^ CH3 * + CO (2 ) 2 CH3 . --------------- — > C2H6 (3) 2 CHt CO — ^ (CH3CO)2 (4) CH3 - + CH3COCH3 CH. + CH„COCHa (5) — ^ 4 3 2 CH3 * -T- CH3COCH2 — > ch3coc2h5 (6 ) 2 CH3COCHj — ^ (ch3coch2 )2 (7) CH3COCH2 — > ch3 -i- ch2co . (3) (only at higher temperatures) All of the products shown have been isolated from the reaction 2 mixture. Dorfmann and Sheldon have shown that diethyl ketone also gives similar results. However, when a chain of three or more carbons compose one of the groups on the ketone, a different mechanism appears. 3 This was first shown by Bloch and Norrish when they photolysed 2-hexanone and found acetone and propylene to be the major products. ch3co(ch2 )3ch3 hv ^ ch3coch3 + c3h6 (9 ) -1- Similar results have been obtained for di-n-propyl ketone, methyl n-propyl ketone, methyl n-amyl ketone and methyl sec- 6 7 butyl ketone. Davis and Noyes suggested a mechanism which has been widely accepted. It involves the cleavage of the carbon-carbon bond once removed from the carbonyl with the migration of a hydrogen on the 7 -carbon atom to the carbonyl oxygen, and is often referred to as the Norrish Type II mecha­ nism. * 0 „ OH - /CH2^?H2 i R—CCHt 0CH0CH0R ' -----> R-C 1 I > R-C-CHn + R'-CH=--CH0 2 2 2 3 ... h - T r ' 2 2 H (W) Several pieces of evidence have been reported to substantiate £ this mechanism : (a) the olefin
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