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CHEMICAL CONSTITUENTS OF ARTEMISIA FILIFOLIA (TORR.) Item Type text; Dissertation-Reproduction (electronic) Authors Torrance, Sterling Jay, 1943- 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 05/10/2021 04:38:05 Link to Item http://hdl.handle.net/10150/290336 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 on 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 Road Ann Arbor, Michigan 48106 73-30,250 TORRANCE, Sterling Jay, 1943- CHEMICAL CONSTITUENTS OF ARTEMISIA FILIFOLIA TORR. The University of Arizona, Ph.D., 1973 Chemistry, organic l University Microfilms, A XEROX Company , Ann Arbor, Michigan THTS riTSSRRTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED. CHEMICAL CONSTITUENTS OF ARTEMISIA FILIFOLIA TORR. by Sterling Jay Torrance 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 19 7 3 THE UNIVERSITY OF ARIZONA. GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Sterling Jay Torrance entitled CHEMICAL CONSTITUENTS OF ARTEMISIA FILIFOLIA TORR. be accepted as fulfilling the dissertation requirement of the degree of DOCTOR OF PHILOSOPHY 7A/73 Dissertation Director Date After inspection of the final copy of the dissertation, the following members of the Final Examination Committee concur in its approval and recommend its acceptance:"" ^/•73 tHfvvC/ Urt ' This approval and acceptance is contingent on the candidate's adequate performance and defense of this dissertation at the final oral examination. The inclusion of this sheet bound into the library copy of the dissertation is evidence of satisfactory performance at the final examination. t 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 from 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: ACKNOWLEDGMENTS The author wishes to express his gratitude to Drs. C. Steelink, the director of this research, T. A. Geissman, J. Wolinsky, and R. G. Carlson for assistance during the course of this work. The author is especially grateful for financial assistance in the forms of a National Science Foundation Summer Traineeship (Summer, 1971), Atlantic Richfield Company Fellowship (I Semester, 1971-72), and a University of Arizona Predoctoral Fellowship (II Semester, 1972-73). iii TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS viii LIST OF TABLES . X ABSTRACT xi INTRODUCTION 1 { RESULTS AND DISCUSSION 4 A. filifolia Monoterpene Lactones 4 Minor Monoterpene Constituents of A. filifolia 32 Other Constituents of A.' filifolia 36 BIOSYNTHETIC IMPLICATIONS 43 EXPERIMENTAL 59 Collection of the Plant Material 60 Steam Distillation of the Plant Material 60 Fractional Distillation of the Steam Distillate 61 Hydrolysis of the A. filifolia Lactones 12 and 13; Isolation of Hydroxy-acids W and M . 61 FractionaT^Crystallization of 17 and 18 64 Regeneration of Lactone 12 from^the Hydroxy-acid 17 . 66 Regeneration oflactone 13 from the Hydroxy^HCid 13 •••••••••••••••• 66 Preparation of i^enchone Oxime (Figure 4) 67 Acid Ifydrolysis of Fenchone Oxime; oc- and P-Fencholenic Acid Nitriles (Figure 4) 68 Selective Saponification of the Mixture of a- and P-Fencholenic Acid Nitriles; 3- Fencholenic Acid and a-Fencholenic Acid Amide (Figure 4) 69 Hydrolysis of a-Fencholenic Acid Amide; a-Fencholenic Acid (Figure 4) 71 Preparation of Geranic Acid (Figure 4) 72 Preparation of (jO-Filifolone (Figure 4) 74 iv V TABLE OF CONTENTS—Continued Page Hydrolysis of Filifolone; a-Fencholenic Acid (Figure 4) 75 Iodolactone of a-Fencholenic Acid (Figure 4) . 75 Dehydroiodination of a-Fencholenic Acid Iodolactone; Preparation of Lactone 2 (Figure 4) m 76 Hydrogenolysis of A. filifolia Lactones 12 and 13; Preparation of Carboxylic Acids' 9 ancPlO 78 Preparation of a-Cyclogeranic Acid (5) 79 Hydrogenation of the Carboxylic Acid Mixture 9+10 from A. filifolia; Preparation of 1f;he Carboxylic Acid 11 81 Preparation of 2,4-Dime^hyl-l,3-pentadiene (Figure 5) 83 Preparation of the Carboxylic Acid 9 (Figure 5) ? 84 Hydrolysis of Chrysanthenone; Preparation of Carboxylic Acid 9 (Figure 5) 85 Hydrogenation of Synthetic 9; Preparation of Carboxylic Acid 11 (Figure 5) 86 Methanolysis of the^A. filifolia Lactone (12 + 13) Mixture; Preparation of 19 88 Oxi$ationwof 19; Preparation of the Keto-acid 89 Photolysis of^Verbenone; Preparation of Chrysanthenone (Figure 8) 90 Oxidation of Chrysanthenone; Chrysanthenone Epoxide (Figure 8) 93 Solvolysis of Chrysanthenone Epoxide; Preparation of the Acid 17 (Figure 8) 95 Thermal Rearrangement of Chrysanthenone Epoxide; Preparation of Lactone 12 (Figures 8 and 9) T 96 Bromination of the Acid 9; Preparation of Lactone 12 (Figure 10 )w 96 Photolysis^of Chrysanthenone; Preparation of the Ketone 22 (Figure 11) 98 Oxidation of Preparation of Epoxide 23 (Figure ll)MMtt ^ ... 101 Thermal Rearrangement of Epoxide 23; Preparation of Lactone 13 (Figure 11) 104 Solvolysis of Epoxide 23 ^Preparation of Hydroxy-acid 18 (Figure 11) 106 Preparation of Methyl—2-butenoic Acid (Senecioic Acid, p,0-Dimethylacrylic Acid) (Figure 12) 107 vi TABLE OF CONTENTS—Continued Page Attempted Lewis Acid-catalyzed Diels-Alder Reaction of Senecioic Acid and Isoprene (Figure 12) 108 Preparation of Ethyl 3-Methyl-2-butenoic Acid (Ethyl Senecioate) 109 Attempted Lewis Acid-catalyzed Diels-Alder Reaction of Ethyl Senecioate and Isoprene (Figure 12) Ill Performic Acid Oxidation of 9; Preparation of Lactone 28 (Figure 13) . .m 112 Iodolactonization of the Carboxylic Acid 9; Preparation of Iodolactone 30 (Figure l^f) ... 113 WAAj4 Preparative GLC of the A. filifolia Steam Distillate; Isolation of the Mixture of Lactones 12+13 114 Preparative^^LC o¥ Lactone 12; Isolation of the Mixture of Lactones l^w+ 13 115 TTHeating of_ TLactone . 12T „ mm mm 115 Steam Distillation ol Lactone 12 116 Steam Distillation of 17; Isolation of the Mixture of Lactones 1'$ + 13 116 Photolysis of ( + )-Verbenone'f^Obtention of (+)-Chrysanthenone (Figure 8) 117 Oxidation of (+)-Chrysanthenone; Preparation of (-)-Chrysanthenone Epoxide (Figure 8) . 118 Thermolysis of (-)-Chrysanthenone Epoxide; Preparation of (-)-Lactone 12 (Figure 8) . 119 Hydrolysis of (-)-Chrysanthenone Epoxide; Preparation of (+)-17 (Figure 8) 119 Preparative GLC of the A. filifolia Steam Distillate; Isolation of (-)-Verbenone, Borneol Piperitenone, and the Enedione 34 (Figure 15) 120 Preparation of (+)-Verbenone 2,4- Dinitrophenylhydrazone 122 Preparation of Piperitenone 2,4- Dinitrophenylhydrazone 123 Preparation of [3-Isophorone (Figure 17) 123 Preparation of 4-Hydroxy-3,5,5-trimethylcyclohex- 2-en-l-one (Figure 17)..... 125 Oxidation of 4-Hydroxy-3,5,5-trimethylcyclohex- 2-en-l-one; Preparation of the Ene-dione 34 (Figure 17) T.