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LEEGWATER, Arie, 1940- STERIC EFFECTS in ORGANIC CHEMISTRY: PART I SOME CHEMISTRY of DI-T-BUTYLKETENE; PART N ALKALINE HYDROLYSIS of SUBSTITUTED METHYL BENZOATES

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LEEGWATER, Arie, 1940- STERIC EFFECTS in ORGANIC CHEMISTRY: PART I SOME CHEMISTRY of DI-T-BUTYLKETENE; PART N ALKALINE HYDROLYSIS of SUBSTITUTED METHYL BENZOATES This dissertation has been microfilmed exactly as received 68-3013 LEEGWATER, Arie, 1940- STERIC EFFECTS IN ORGANIC CHEMISTRY: PART I SOME CHEMISTRY OF DI-T-BUTYLKETENE; PART n ALKALINE HYDROLYSIS OF SUBSTITUTED METHYL BENZOATES. The Ohio State University, Ph.D., 1967 Chemistry, organic University Microfilms, Inc., Ann Arbor, Michigan STERIC EFFECTS IN ORGANIC CHEMISTRY PART I SOME CHEMISTRY OF DI-T-BUTYLKETENE PART II ALKALINE HYDROLYSIS OF SUBSTITUTED METHYL BENZOATES DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University by Arie Leegwater, B.A. The Ohio State University 1967 Approved by Adviser Department of Chemistry ACKNOWLEDGMENTS I wish to thank Dr. Melvin S, Newman for his assistance and direction in the course of this work, and for his invaluable help in the preparation of this manuscript. Thanks also are extended to fellow graduate students and professors for many helpful discussions and donations of time and materials. ii VITA October 2, 1940.................... Born, Heerhugowaard, The Netherlands I9Ô2 ............................... B.A. Calvin College Grand Rapids, Michigan 1962-196 3.......................... Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1963-196 7..........................Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio ill TABLE OF CONTENTS PART I SOME CHEMISTRY OP DI-T-BUTYLKETENE Page INTRODUCTION AND HISTORICAL........................... 2 RESULTS AND DISCUSSION................................ 9 The Preparation of Di-t-butylketene. ............ 9 The Reactions of Di-t-butylketene with Formal­ dehyde, Acetaldehyde and Acetone............... 12 Attempted Addition of Reactive Reagents to Di-t-butylketene............................... 14 Preliminary Photochemical Investigation of Di-t-butylketene............................... 18 Conclusion and Summary............... 20 EXPERIMENTAL.......................................... 21 Generalizations.................................. 21 Intermediates...... 22 Preparation of 1,1-Di-t-butylethanol. .......... 22 Preparation of 1,1-Di-t-butylethylene............ 23 Preparation of 2,2-Di-t-butylethanol, Di-t-butyl- acetic Acid and Di-t-butylacetylchloride....... 25 Preparation of Di-t-butylketene................. 25 Preparation of Phenylmercurie Bromide........... 25 Preparation of Phenyl (trichloromethyl)mercury 26 Preparation of Bromomalononitrile............... 2? Preparation of Trimethylsulfoxonium Iodide....... 28 Reactions........................................ 28 Addition of Formaldehyde to Di-t-butylketene; o(,cK -Di-t-butyl-P-propiolactone............... 28 Attempted Addition of Acetone to Di-t-butylketene. JO Attempted Addition of Acetaldehyde to Di-t-butyl- ketene......................................... 30 Attempted Addition of Diazomethane to Di-t-butyl- ketene........ 32 Attempted Addition of Simmons-Smith Reagent to Di-t-butylketene............ 32 iv Page Attempted Addition of Dlchlorocarbene to Di-t-butylketene........................... 32 Attempted Addition of Dicyanocarbene to Di-t-butylketene...... 34 Attempted Addition of Sulfene to Di-t-bmtylketene. 34 Attempted Addition of Benzyne to Di-t-butylketene, 35 Attempted Addition of Dimethylsulfoxonium Methylid to Di-t-butylketene................ J6 Lithium Aluminum Hydride Reduction of cy,« -Di-t- butyl-^-propiolactone: Methyl-di-t-butylacetic Acid........................................ 37 "Mixed" Hydride Reduction of ,c^-Di-t-butyl - -propiolactone: Methyl-di-t-butylacetic Acid. 38 Attempted Reduction ofc<,#-Di-t-butyl-P-propio- lactone with Iso-propylmagnesium Iodide.... 38 Attempted Base Hydrolysis of oc.cx-Di-t-butyl -^-propiolactone........................... 39 Attempted Alkylation of cx.ex -Di-t-butyl-P-propio- lactone by Methyl Iodide..................... 39 PART II ALKALINE HYDROLYSIS OF SUBSTITUTED METHYL BENZOATES INTRODUCTION AND HISTORICAL........................... 42 PREPARATION OF ACIDS AND ESTERS....................... 51 STRUCTURES OF ACIDS AND ESTERS........................ 56 EXPERIMENTAL.......................................... 59 Generalizations.................... 59 Preparation of Diazomethane...................... 59 Intermediates............... 59 Preparation of 3-Methyl-3-»6-endoxo-l,2,3.6-tetra- hydrophthalic Anhydride........................ 59 Preparation of 3-Methylphthalic Anhydride........ 60 Preparation of 3-Chlorophthalic Anhydride........ 6l Preparation of o-Benzoylbenzoic Acids and Esters.. 62 Preparation of Methyl p-Benzoylbenzoate......... 63 Preparation of 2-Acetyl-6-chlorobenzoic Acid..... 63 Preparation of 2-Acetyl-6-methylbenzoic Acid 65 Preparation of Methyl o-Acetylbenzoate.......... 67 Page Preparation of 2,6-Dlmethylbromobenzene......... 68 Preparation of 2,6-Dimethylbenzolc Acid and Methyl 2,6-Dimethylbenzoate................ 69 Preparation of 7-Methylphthalide..... 69 Preparation of 7-Chlorophthalide................. 71 Preparation of 2-Formyl-6-methylbenzoic Acid...... 72 Preparation of 2-Formyl-6-chlorobenzoic Acid 72 HYDROLYSES OF ESTERS Experimental Procedure........'.................. 7^ Calculation of Rate Constants...'........... 75 Kinetic Data..................................... 77 Discussion of the Kinetic Data................... 102 Vi LIST OP TABLES (PART II) TABLE Page 1. Infrared Spectra of Some o-Acylbenzolc Acids - Potassium Bromide Wafers.............. 58 2. Kinetic Run No. 3................................ 78 3 . Kinetic Run No. 4 ............................... 79 4. Kinetic Run No. 1................................ 80 5. Kinetic Run No. 2 ............................... 81 6. Kinetic Run No. 11.............................. 83 7 . Kinetic Run No. 7................... 84 8. Kinetic Run No. 8............... 85 9. Kinetic Run No. 9......... 86 10. Kinetic Run No. 10.............................. 87 11. Kinetic Run No. 5.««............................. 88 12. Kinetic Run No. 6 ............................... 89 13. Kinetic Run No. 12.............................. 90 14. Kinetic Run No. 13................................ 91 15* Kinetic Run No. 14.............................. 92 16. Kinetic Run No. I5.................... 93 17. Kinetic Run No. I6 ............................... 94 18. Kinetic Run No. I7 ........................ 95 19. Kinetic Runs No. 18,19........ ‘........ 96 20. Kinetic Run No. 20.............................. 97 vii TABLE Page 21. Kinetic Run No. 21..................... 98 22. Kinetic Run No. 22...... 99 23. Kinetic Run No. 23. .......... 100 24. Kinetic Run No. 24............................ 101 25. SUMMARY OF KINETIC DATA....................... IO3 26. SUMMARY OF KINETIC DATA....................... 104 27. Relative Rates of Hydrolysis of Benzoyl and Acetyl Esters............. IO5 28. Relative Rates of Hydrolysis of Some n-and '/'-Methyl Q-Benzoylbenzoates................. II6 viii ILLUSTRATION Figure Page 1. Alkaline Hydrolysis Plot of Methyl a-Aoetyl- benzoate.................................... 82 ix PART I SOME CHEMISTRY OF DI-T-BUTYLKETENE INTRODUCTION AND HISTORICAL The interesting and highly reactive cumulative system of olefin and carbonyl double bond (^C=C=0) present in ketenes drew little attention after Staudinger's classic work.l Only recently, the work of Hasek and Martin with ^H. Staudinger, "Die Ketene", F. Enke, Stuttgart, 1912. dimethylketene^ and n-butylethylketene^ has aroused a new 2 R. H. Hasek, R. D. Clark, and J, H. Chaudet, J, Org. Chem., 3130 (I96I); R. H. Hasek, E. U. Elam and J. C. Martin, ibid, 43^0 (I96I); R. H, Hasek, E. U. Elam, J. C. Martin and R, D. Clark, ibid, 60 (I962) J. C. Martin, V. W. Goodlett and R. D. Burpitt, ibid, 1 0 , 4309 (1965). H. Hasek and J. C. Martin, J. Org. Chem,, 28. 1468 (1963); R. H, Hasek, P. G, Gott and J. C. Martin, ibid, 22, 1239 (1964); J. C. Martin, P. G. Gott, V. W. Goodlett and R. H. Hasek, ibid, JO, 4l?5 (I965); R. H. Hasek, P. S. Gott and J. C. Martin, ibid, Jl, 1931 (1966), interest in ketene chemistry,^ In general diphenylketene 4 For an excellent review, see R, H, Lacey, "The Chemistry of Alkenes", S, Patai, Ed,, Interscience Publishers, Inc., New York, N, Y,, 1964, Chapter 14; see also, "Organic Reactions", Vol. Ill, John Wiley and Sons, Inc,, New York, N, Y., 1946, p. 108. and diphenyleneketene are more susceptible to reactions with nucleophilic reagents and in four-center cyclic reactions with other reagents containing multiple bonds than are the dialkylketenes. For some representative ketenes the following order of reactivity in 1,2 cyclo- additions with olefins has been established.^ C. Martin, P. G. Gott, V. W. Goodlett and R. H. Hasek, J. Org. Chem., JO, 4l?5 (1965). C/Hg . CH^ . n-Bu . H N5 =0=0\ > \0 =0=0\ > \ 0=0=0\ > \0=0=0 In.i960, di-t-butylketene^ (I), the first aliphatic ^M. S. Newman, A. Arkell and T. Pukunaga, J. Am. Ohem. Soc., 82, 2498 (I96O). ketene stable as a monomer was synthesized. The absence of dimerization was attributed to the size of the two t-butyl groups. Two stable oc-carbethoxyketenes, ( ,« -dimethylbenzyl)carbethoxyketene (II) and t-butylcarbethoxyketene (III), were synthesized in I962.? S, Newman and E. A. Zuech, J. Org. Chem. 27. 1436 (1962). (CHo)oC EtO_C EtO.C^ ; j \ \ 2 \ c=c=o c=c=o c=c=o (CH^)^c/ (CH^) V ( CH ^)^ I II III Early exploratory experiments revealed that I was rather unreactive when compared to other ketenes.^ For example, the addition of water to I occurred slowly unless catalyzed by acid or base,
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