Synthesis of compounds analogous to methyl sterculate Item Type text; Dissertation-Reproduction (electronic) Authors El Eris, Talib Mishin, 1930- 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 28/09/2021 14:26:32 Link to Item http://hdl.handle.net/10150/565208 SYNTHESIS OF COMPOUNDS ANALOGOUS TO METHYL STERCULATE v • ' • \ ¥ ■ ' TaliU Me El Eris A Dissertation Submitted to the Faculty of the “COMMITTEE ON AGRICULTURAL BIOCHEMISTRY AND NUTRITION In Partial Fulfillment of the Requirements For the Degree of DOCTOR OF PHILOSOPHY In the Graduate College THE UNIVERSITY OF ARIZONA 1970 THE UNIVERSITY OF ARIZONA GRADUATE COLLEGE I hereby recommend that this dissertation prepared under my direction by Talib M» El Eris_________________________ entitled Synthesis of Compounds Analogous to Methyl Sterculate» be accepted as fulfilling the dissertation requirement of the degree o f ____________ Doctor of Philosophy______________ Dissertation Directorirector D a t e j 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:* XL-/ 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. 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 Uni­ versity 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 repro­ duction of this manuscript in whole dr in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the pro­ posed use of the material is in the interests of scholarshipe In all other instances, however, permis­ sion must be obtained from the author. ACKNOWLEDGMENTS The author wishes to express his. sincere appre­ ciation and gratitude; To Dr. H„ W„ Kircher for his helpful counsel and guidance in directing the course of this work and prepa­ ration of this dissertation. To Drs. A. R. Kemmerer and M. G. Vavich for en­ abling me to complete my graduate studies in the Depart­ ment of Agricultural Biochemistry and Nutrition. To Dr. Eo H. Pryde of the Oilseed Crops Labora­ tory of the Northern Research Laboratory, USDA, Peoria, Illinois, for supplying EAZ and MAZ. TABLE OF (CONTENTS Page LIST OF ILLUSTRATIONS..............___ ......... vi ABSTRACT .....................................o. v113. I. INTRODUCTION. .................................. 1 II. E ill J? ■ IMENTAL................................... 16 Preparation of Oleyl Alcohol............... 16 Preparation of Oleyl Tosylate.............. i? Preparation of 9-0ctadecene................ 18 Oxidation of 9-0ctadecene.................. 19 Preparation of Potassium Tert-hutoxide...=. 20 Preparation of 1,l-Dichloro-2,3-dioctyl- cyclopropane . @ . ./. ........................ 20 Preparation of 1,l-Dihromo-2,3"dioctyl- c y c1op ropane............................. 21 Preparation of 1,l-Dichloro-2-octyl-3- (7-carhomethoxyheptyl}-cyclopropane...... 25 Preparation of 9,10-Nonadecadiene ( D roc t y 1 .Al 1 en. e 2 7 Oxidation of Dioctyl Allene................ 29 Preparation of ^-Bromo-^-hutyrolactone..... 30 ' 2-0xo-3-tetrahydrofuranyl Triphenylphos- phonium Bromide pd-Triphenylphosphonium- (^-“hutyrolactone) Bromide. ............... 33 Cyclopropyltriphenylphosphonium Bromide.... 36 Attempted Synthesis of ^/-Triphenylphos- phonium-(^-undecalactone) Bromide ........ 36 Preparation of Phenyllithium............... 37 Heptylidenecyclopropane ..... 38 Bromination of Heptylidenecyclopropane..... 39 Hydrogenation of Heptylidenecyclopropane... 39 1,2-Me thylene-2-dode c ene................... 44 Ethyl-10,ll-methylene-9-undecenoate........ 46 Methyl-10,ll-methylene-9-undecenoate....... 48 III. DISCUSSION...................................... 55 iv V TABLE OF CONTENTS— Continued Page IV. ^5 e e e c.o o oe e e o oe e fre e ep o e e e e e e-e 9 .e0 o 6:6 e e e e e'o REFERENCES o@o*oe*@o@ee@eoe»e*#*oe*eo*ooe@o@oap LIST OF ILLUSTRATION'S Figure Page 1 . I.E. spectrum of 9-oetadecene in CS^ solution.. 22 2. GLC diagram comparing retention time of (a) 9-octadecene, (lo) dioctyl allene, and (c) 1 ,l-dichloro-2 ,3-dioctylcyclopropane, 175°, 18 It) He pressure....... 22 3. I.E. spectrum of 1,l-dichloro-2 ,3-dioctylcy­ clopropane in CS^ solution................. 23 4. I.R. spectrum of 1,l-dibromo-2 ,3-dioctylcy­ clopropane in CSg solution................. 23 5. I.R. spectrum of l,l-dichloro-2-octyl-3- (7-carbomethoxyheptyl)-cyclopropane in CS^ solution..................................... 26 6 . GLC diagram comparing retention time of (a) methyl oleate and (h) 1,l-dichloro-2- octyl-3-(7-carbomethoxyheptyl)-cyclo­ propane, 205P , 25 lb He pressure........... 26 7. I.R. spectrum of dioctyl allene in CS^ solution..................................... 31 8 . GLC diagram comparing retention time of (a) -bu tyro 1 act one and (b) tX-bromo-()-buty- rolactone, 175°, 18 lb He pressure......... 31 9. I.R. spectrum of ^-bromo-^-butyrolactone in CCl^ solution............................... 35 10. I.R. spectrum of 2-oxo-3-tetrahydrofuranyl triphenylphosphonium bromide in CHC1- solution.............................. 35 11. I.R. spectrum of cyclopropyltriphenylphos- phonium bromide in CHC1„ solution.......... 40 vi VII LIST OF ILLUSTRATIONS— Continued Figu re Page 12. GLC diagram comparing retention time of (a) hcptylidenecyclopropane and (t>) heptalde- hyde, 85°, 5 lb lie pressure................ 40 13. I.R. spectrum of heptylidenecyclopropane in CCl^ solution............................... 41 14. I.R. spectrum of brominated heptylidenecyclo­ propane in CCl^ solution................... 41 15. nmr spectrum of heptylidenecyclopropane....... 42 16. GLC diagram comparing retention time of (a) 1,2-methylene-2-dodecene and (b) decyl- aldehyde, 110° , 12 lb He pressure.......... 45 17. I.R. spectrum of 1,2-methylene-2-dodecene in CCl^ solution....................... 45 18. I.R. spectrum of brominated 1,2-methylene-2- dodecene in CCl^ solution.................. 47 19. GLC diagram comparing retention time of (a) ethyl-10, 11-methylene-9~undecenoate and (b) EAZ, 180°, 18 lb He pressure....... 47 20. I.R. spectrum of ethyl-10, 1l-methylene-9-un- decenoate in CCl^ solution................. 49 21. I.R. spectrum of hydrogenated ethyl-10,11- methylene-9-undecenoate in CCl^ solution... 49 22. I.R. spectrum of brominated ethyl-10, 11-methy­ lene-9-unde ceno ate in CCl^ solution....... 50 23. nmr spectrum of ethyl-10,ll-methylene-9- undecenoate.................................. 51 24. I.R. spectrum of methyl-10,ll-methylene-9- undecenoate in CCl^ solution............... 52 25. I.R. spectrum of hydrogenated methyl-10,11- methylene-9-undecenoate in CCl^ solution... 52 26 . nmr spectrum of methyl-10, 11-methylene-9- undecenoate.................................. 53 ABSTRACT gem-Dihalocyclopropane derivatives of 9-octa-* decene have been prepared by the Doering-Ho£fman and by the Seyferth methods and were reacted with alkyl- lithium reagents and sodium metal to produce dioctyl alienee The structure of dioctyl allene was verified by its infrared spectrum, gas chromatographic time as compared with that of 9-octadecene, and oxidation to pelargonic acid followed by GLC analysis of the meth­ ylated producte In one trial, the dioctyl allene could not be converted to the desired methyleneCyclo- propane, 9510-methylene-10-nonadecene, by reaction with zinc-copper couple and methylene iodide. A modified method for the £s£~bromination of ' y-butyrolactone is described. It does not require the use of large amount of catalyst (phosphorous tri­ bromide) and it gives higher yields than several of the methods found in the literature for bromination of carbonyl compounds in the alpha position. The methylenecyclopropanes, heptylidenecyclo- propane, 1,2-methylene-2-dodecene, methyl-10,11- methylene-9-undecenoate, and ethyl-10,11-methylene- 9-undecenoate have been synthesized by the Wittig vili ix reaction from cyelopropyltriphenylphosphonium bromide and the corresponding aldehydese Their structures have been verified by infrared and nmr spectra, by addition reactions such as hydrogenation, bromination, and hydrobromination, and by their gas chromatographic times as compared with those of the corresponding aldehydes0 The absorption frequencies at 3010, 1040, ttxa 963, and 935 cm". were present in the infrared spectra of the methylenecyclopropanes reported here* These bands are among the numerous typical bands reported in the literature for substituted methylenecyclopropane» The bands at 3010, 1000, 963? and 935 cm""*" did not appear in the infrared spectra of the hydrogenated, brpminated, and hydrobrominated derivatives of these methylenecyclopropaneso It is very interesting, in­ deed, to know that hydrogenation of these compounds resulted in a shift of