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Xerox University Microfilms 300 North Zeeb Rood Ann Arbor, Michigan 48106 11 INFORMATION TO USERS This material was produced from a microfilm copy of the original document. While the most advanced technological means to photograph and reproduce this document have been used, the quality is heavily dependent upon the quality of the original submitted. The following explanation of techniques is provided to help you understand markings or patterns which may appear on this reproduction. 1. The sign or "target" for pages apparently lacking from the document photographed is "Missing Page(s)". If it was possible to obtain the missing page(s) or section, they are spliced into the film along with adjacent pages. This may have necessitated cutting thru an image and duplicating adjacent pages to insure you complete continuity. 2. When an image^pn the film is obliterated with a large round black mark, it is an indication that the photographer suspected that the copy may have moved during exposure and thus cause a blurred image. You will find a good image of the page in the adjacent frame. 3. When a map, drawing or chart, etc., was part of the material being photographed the photographer followed a definite method in "sectioning" the material. It is customary to begin photoing at the upper left hand corner of a large sheet and to continue photoing from left to right in equal sections with a small overlap. If necessary, sectioning is continued again — beginning below the first row and continuing on until complete. 4. The majority of users indicate that the textual content is of greatest value, however, a somewhat higher quality reproduction could be made from "photographs" if essential to the understanding of the dissertation. Silver prints of "photographs" may be ordered at additional charge by writing the Order Department, giving the catalog number, title, author and specific pages you wish reproduced. 5. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. Xerox University Microfilms 300 North Zeeb Rood Ann Arbor, Michigan 48106 11 73-18,901 HENZEL, Kay Ann, 1946- PARTICIPATION BY NEIGHBORING CYCLOOCTATETRAENYL GROUPS IN SOLVOLYTIC DISPLACEMENT REACTIONS. The Ohio State University, Ph.D., 1973 Chemistry, organic i j University Microfilms, A XERO\Company , Ann Arbor, Michigan j PARTICIPATION BY NEIGHBORING CYCLOOCTATETRAENYL GROUPS IN SOLVOLYTIC DISPLACEMENT REACTIONS. DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By Kay Ann Henzel, B.S ***** The Ohio State University 1973 Approved by A U V X O WJL Department of Chemistry DEDICATION To my unborn child who caused this thesis to be written in great haste, and to the man who made it all possible. ii ACKNOWLEDGMENT The author would like to express her gratitude to Dr. Leo A. Paquette for his guidance, patience, and encouragement. ill VITA November 19, 19*1-6 ...... Born, Phillipsburg, New Jersey X9^^ B#S«, Bucknell Universi "by, Lewi sburg, Pennsylvania. 1968-I969 ............. Teaching Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio 1969-1973 .......... ..... Research Assistant, Department of Chemistry, The Ohio State University, Columbus, Ohio PUBLICATIONS "The Chemistry of Flavandiones. Reaction with Diazomethane, J, Org, Chem.. 3 7 , 277*1- (1972). FIELDS OF STUDY Major field: Organic Chemistry TABLE OP CONTENTS Page DEDICATION.......................... 11 ACKNOWLEDGMENT................................ ill VITA ..................................... lv LIST OF TABLES ................................ vl INTRODUCTION.................................... ll'l 1 RESULTS AND DISCUSSIONS ........ 28 EXPERIMENTAL.............................. 83 REFERENCES ............ 15^ v LIST OP TABLES Table Page I. Buffered Hydrolysis Rate Data .......... 32 II. Buffered (NaOAc) Acetolysis Rate Data ... III. Product Variation During Acetolysis of 89-OBs............................... 59 IV. Paramagnetic-Induced.Shifts for.Protons of 155-OH ........................... 63 V. Solvolysis of 92-C1 in 50# Aqueous Acetone at 30.1°.... .:...................... 139 VI. Solvolysis of 92-C1 in 50# Aqueous Acetone at 40.0° ...................... 140 VII. Solvolysis of 92-C1 in 50% Aqueous Acetone at 4-9.9° ... .77....... .............. 1^1 VIII. Solvolysis of 88-C1 in 50% Aqueous Acetone at 30.10 ....77........ ............. 1^2 IX. Solvolysis of 88-Cl in 50# Aqueous Acetone at ^o.o° ....r:....... ;............. 1^3 X. Solvolysis of 88-Cl in 50# Aqueous Acetone at 49.9° ___ r:....... ;............. l4if XI. Solvolysis of 1^0-OBs in 0.10065 N NaOAc/ HOAc at 75.00 “ ... ;................ 1^5 XII. Solvolysis of lij-O-OBs In O.IOO65 N NaOAc/ HOAc at 85.0° T T ..................... 1 k6 XIII. Solvolysis of l^J-O-OBs in O.IOO65 N NaOAc/ HOAc at 9 5 .00 lTT ............. 7 ...... 1^7 vi LIST OP TABLES (Continued) Table Page XXV. Solvolysis of 139-OBs in 0.10065 N NaOAc/ HOAc at 45.0° '"77............ ......... 148 XV. Solvolysis of 139-OBs in 0.10065 N NaOAc/ HOAc at 55.0° '"TV...................... 149 XVI. Solvolysis of 139-OBs in O.IOO65 N NaOAc/ HOAc at 65.OO .............. 7 ...... 150 XVII. Solvolysis of 89-OBs in 0.10065 N NaOAc/ HOAc at 55.00 ^7............. 7 ........ 151 XVIII. Solvolysis of 89-OBs in O.IOO65 N NaOAc/ HOAc at 6 5 .0 0 ^ ...................... 152 XIX. Solvolysis of 89-OBs in O.IOO65 N NaOAc/ HOAc at 7 5 .0 0 153 vii INTRODUCTION A large part of the current chemical literature Is con­ cerned with substituents which are capable of Influencing a reaction by becoming bonded or partially bonded with the reaction center In order to stabilize the transition state.’1' This phenomenon is commonly called neighboring group par­ ticipation and frequently results in an increase in reaction rate due to the enhanced stability of the reaction inter­ mediate. This type of anchimeric assistance has been recog­ nized for heteroatom-containing groups such as methoxyl, 2 hydroxyl,^ carbonyl,** amino,thioether,^ imidazole,? etc. Although direct nucleophilic participation by hydrogen in a Q rate-determining step occurs in very few reactions, an­ chimeric assistance by carbon is well known. A vast amount of literature is devoted to aryl participation in which the aryl group bridges In the ionization step,7*Q 10 while contra­ dictory theories have also been presented.1-1' In addition, evidence has appeared to support the theory that neighboring small rings are capable of having a significant influence on *i p reaction rates. c Finally, extensive investigation has shown that neighboring olefinic bonds can function as nucleophilic neighboring groups in intramolecular displacement reactions. This category can be further subdivided into allylic and homo- allylic participation. The solvolysis reactions of a vast number of allylic compounds have been studied.^ • Winstein, Grunwald, and JonesA have suggested that the mechanism of these reactions is best described by a single mechanism which is intermediate between Snl and Sn2, rather than by competing unimolecular and bimolecular processes. Support for this hypothesis is found in the effect of solvent properties on rates of solvolysis reactions, which shows a linear relationship between solvolysis rate and solvent ionizing power. If two mechanisms were com­ peting, the reaction should change from a purely Sn2 process in solvents of very low ionizing power and high nucleophilicity to a purely Snl process in solvents of similar nucleophilicity but much higher ionizing power. A plot of solvolysis rate versus solvent ionizing power would then show a distinct curvature or even a break, designating a region of transition between mechanisms. Much can be learned about the mechanisms of allylic solvolysis reactions by studying the products formed. The solvolysis of most allylic halides yields mixtures of the i "normal" (unrearranged) and "abnormal" (rearranged) subs­ titution products and this suggests the operation of an Snl mechanism. It is not uncommon to find both members of a pair of isomeric halides giving an Identical mixture of products which is an indication not only that unimolecular substitution is Involved, but that both isomers are reacting via a common intermediate. This could be either an ion pair or a classical, mesomeric carbonium ion. 3 Isomeric allylic derivatives have also been found to give different mixtures of products under identical reaction conditions. The "product spread" simply means that one isomer may favor an Snl or Sn2 mechanism to a greater degree than its counterpart. Solvolysis of crotyl chloride (1) and methy1- vinylcarblnyl chloride (2 ) have been used as models to test the postulate that solvolysis occurs with preliminary ion­ ization, and each halide was predicted to give the same product mixture. This system was somewhat unsatisfactory as a model CH3CH=CHCH2C1 CH3CHCHSCH2 Cl 2 ROH, -H+ CH3CHCH3CH2 + CH3CH=CHCH2 0R OR since the solvolysis rates were somewhat dependent on lyate-Ion concentration. However, solvolysis In each case gave a mixture of isomeric products and although the proportions of product isomers were not exactly the same for each halide, the differ­ ences were In the direction consistent with the postulate that the mechanism is not entirely unimolecular. Many additional examples of allylic rearrangements In simple, straight-chained systems are available in a comprehensive review. ^ Allylic participation has been observed in several simple alicyclic systems. The solvolysis rates of methylcyclobut-2- enyl (3 )* cyclopent-2 -enyl (jO, and cyclohex-2 -enyl
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