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AN ABSTRACT OF THE THESIS OF DALE DAVID DIXON for the DOCTOR OF PHILOSOPHY (Name) (Degree) in "CHEMISTRY (ORGANIC)" presented on\--Wicl j 1(1Wi (Major) (Date) T itle: STEROID DIALKYLCARBENE REACTIONS Abstract approved: Dr. F. T. Bond Steroid carbenes have been investigated as synthetic inter- mediates. Basic decomposition of 4-en-3-one tosylhydrazones (and other A-ring systems) gives varying amounts of 2, 4-dienes, and solvent derived products with diglyme, heptane, tetrachloroethylene, carbon tetrachloride, benzene and cyclohexene. A method for separating complex product mixtures was developed and a study of the effect of reaction conditions carried out. Butyl lithium decom- position gives a high yield of the homoannular diene. Sterically hindered carbenes give only intramolecular products. Saturated steroid carbenes have been shown to give widely varying y Ií insertion ratios. Decomposition of cholestan -3 -one tosylhydrazone in tetrachloroethylene results in the formation of a solvent derieved pyrazoline. The possible role of pyrazolines in other carbene reactions is discussed, A facile route to interesting fused ring pyrazoles has been developed in the l6-en-20-one tosylhydrazone system. With a 16- methyl system the pyrazolenine was isolated and investigated. The 'possible biological properties of these compounds are discussed. Steroid Dialkylcarbene Reactions by Dale David Dixon A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1968 APPROVED: Assistant Professor of Chemistry in charge of major Chairman of the Department of Chemistry Dean of Graduate School Date thesis is presented / / 1 6 S Typed by Gwendolyn Hansen for Dale David Dixon ACKNOWLEDGEMENTS I wish to express my appreciation to Dr. F. Thomas Bond for his instruction, encouragement, and scientific perspective which have contributed immeasurably to the success of this work. I am grateful to my wife Kathy whose support and sacrifice have made possible the completion of this study. TABLE OF CONTENTS Page INTRODUC TION 1 Spin States of Carbenes 1 Electrophilic Character of Carbenes 3 Carbenoid Reactions 6 Formation of Dialkylcarbenes 9 Reactions of Dialkylcarbenes 17 Synthetic Utility of Dialkylcarbenes 22 Stabilized Carbenes 27 Stable Carbenes From Tosylhydrazones 34 Steroid Carbene Reactions 38 Steroid Justification 43 RESULTS AND DISCUSSION 48 Cyclization onto the C -18 and C -19 Methyl Groups 49 Cyclization onto C -18 49 Cyclization onto C-19 55 a,ß- Unsaturated Carbenes 58 Decomposition of 4- Cholestenone Tosylhydrazone 57 in Toluene. 61 Decomposition of 4- Cholestenone Tosylhydrazone 57 in Benzene. 63 Decomposition of 4- Cholestenone Tosylhydrazone 57 in Diglyme and in Heptane 75 Decomposition of 4- Cholestenone Tosylhydrazone 57 in Celite and in Carbon Tetrachloride 77 Decomposition of 4- Cholestenone Tosylhydrazone 57 in Cyclohexene and in Tetrachloroethylene 81 Decomposition of Cholestanone Tosylhydrazone 138 in p- Xylene and in Tetrachloroethylene 85 Decomposition of 19- Nortestosterone Acetate Tosylhydrazone 146 and Testosterone Tosyl- hydrazone 148 90 Cholesta -2, 4 -diene 109 from Butyl Lithium Treatment of 4- Cholestenone Tosylhydrazone 57 92 Decomposition of Cholest- l -en -3 -one Tosylhydra- zone 58 and Androst- 2 -en -1 -one Tosylhydrazone 159 93 Page Decomposition of 7- Keto- cholesteryl- acetate tosylhydrazone 54 98 Decomposition of 16- Dehydro -pregnenolone Tosylhydrazone 167 and 16- Methyl -l6- dehydro- pregnenolone acetate Tosylhydrazone 170 100 Rearrangements of Spirosteroids on Alumina Column Chromatography 106 Conclusions 110 EXPERIMENTAL 111 5 -Andros tene- 3p- 01-17- one p- Toluene sulfonyl - hydrazone 78 112 Pyrolysis of 5- Androstene- 3p -o1 -17 -one p- Toluenesulfonylhydrazone 78 with Sodium Methoxide in Diglyme 113 Pyrolysis of 5- Androstene- 3p -o1 -17 -one p- Toluenesulfonylhydrazone 78 with Varying Amounts of Sodium Methoxide in p- Xylene 114 13p, 17p- Methylene- androstane -3p -ol 88 116 Photolysis of 5- Androstene- 3p -o1 -17 -one p- Toluenesulfonylhydrazone 78 with Sodium Methoxide in Tetrahydrofuran 118 5a- And rostane- 3p -ol -17 -one 118 5a- Andros Lane -- 3p- ol- 3- acetate -17 -one p- Toluenesulfonylhydrazone 8 6 119 Pyrolysis of 5a- Androstane- 3p -ol -3- acetate 17- one 'p- Toluenesulfonylhydrazone 8 6 with Sodium Methoxide in Diglyme 119 Cholestan -l - one p-Toluenesulfonylhydrazone I -103 121 Pyrolysis of Cholestan - l -one p- Toluenesulfonyl - hydrazone I -103 with Sodium Methoxide in Celite 121 Cholestan - 3p- of I -95 123 Cholestan -3 -one I -96 123 2a- Bromo- Cholestan -3 -one I -97 124 1- Choles ten- 3- one 1-98 124 1 , 2a- Oxido- choles tan- 3- one I- 99 125 2-Cholesten-la-l-ol I-100 125 2- Chole s ten-1- one I -101 126 Cholestan -1 -one I -102 127 4-Cholesten-3-one 'p- Toluenesulfonylhydrazone 57 127 Page Pyrolysis of 4- Cholestene -3 one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Benzene 127 Pyrolysis of 4-Cho les ten- 3- one p- Toluenesulfonyl - hydrazone 57 with Varying Amounts of Sodium Methoxide in Benzene 130 Pyrolysis of 4- Chole s ten- 3- one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Varying Amounts of Benzene 131 Pyrolysis of 4- Cholesten - 3- one p- Toluenesulfonyl- hydrazone 57 with Sodium Hydride in Benzene 133 Pyrolysis of 4-Choles ten- 3- one p- Toluenesulfonyl- hydrazone 57 with Varying Amounts of Sodium Hydride in Benzene 133 Alumina- catalyzed Aromatization of Spiro(cyclo- 135 heptatriene- 7' , 3- choles t- 4 -ene) 11 6 3- Phenylcholes tan- 3a- of and 3- Phenylcholes tan - 3p -ol 123 138 3- Phenylcholes t- 2 - ene 124 138 Alumina - catalyzed Reaction of Cholest -4 -en- 3a-ol- 3- methyl ether 117 139 Alumina- catalyzed Reaction of Cholest -4 -en- 3(3- o1-3- methyl ether 118 140 Cholest- 4- en -3a -ol 113 and Cholest- 4- en -3p -ol 114 141 Pyrolysis of 4- Choles ten- 3- one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Diglyme 142 Pyrolysis of 4- Cholesten -3 -one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Heptane 143 Pyrolysis of 4- Choles ten- 3- one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Celite 145 Pyrolysis of 4- Cholesten -one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Carbon Tetrachloride 146 Pyrolysis of 4- Choles ten- -one Tosylhydraz one 57 with Sodium Hydride in Carbon Tetrachloride 148 Pyrolysis of Cholest- 4 - en- 3 -one p- Toluenesulfonyl- hydrazone 57 with Sodium Methoxide in Cyclo- hexene 149 Alumina - catalyzed Rearrangement of endo- Spiro(4- cholestene- 3, 7' -bicyclo[ 4. 1. 0] heptane) 132 153 Alumina- catalyzed Rearrangement of exo- Spiro(4 - cholestene- 3, 7' -bicyclo[ 4. 1, 0] heptane) 133 154 Page Pyrolysis of 4- Choles ten- 3- one p- Toluenesulfonyl - hydrazone 57 with Sodium Methoxide in Tetra- chloroethylene 154 Pyrolysis of 4- Chole s ten- 3- one p- Toluene sulfonyl- hydrazone 57 with Sodium Hydride in Tetra- chloroethylene 1 56 Alumina- catalyzed Rearrangement of Spiro(4- cholestene- 3, 1' - tetrachlorocyclopropane) 1 36 1 56 Pyrolysis of 4- Cholestene -3 -one p- Toluenesulfonyl - hydrazone 57 with Sodium Methoxide in an Equimolar Mixture of Tetrachloroethylene and Cyclohexane 157 Cholestan 3- one p- Toluene s ulf onylhyd raz one 138 1 58 Pyrolysis of Cholestan- 3-one p- Toluenesulfonyl - hydrazone 138 with Sodium Methoxide in p- Xylene 159 Pyrolysis of Cholestan- 3 -one p- Toluenesulfonyl - hydrazone 138 with Sodium Methoxide in Tetra- chloroethylene 159 Alumina-catalyzed Conversion of Spiro(Nß- tetra- chloropyraz oline- 3' , 3- chole s tane) 141 to 2- Cholestene 48 1 61 Photolysis of Spiro(Nß- tetrachloropyrazoline - 3' , 3- cholestane 141 162 19- Nor - androst- 4 -ene- 173- o1 -17- acetate -3 -one p- Toluenesulfonylhydrazone 146 1 62 Pyrolysis of 19- Nor - androst- 4- ene- 17p- o1 -17- acetate- 3 -one p- Toluenes ulfonylhyd raz one 146 with Sodium Methoxide in Diglyme 162 4- And rostene -17p- ol- 3 -one p- Toluene sulfonyl- hydrazone 148 164 Pyrolysis of 4- Androstene- 17ß -3 -one p- Toluenesulfonylhydrazone 148 with Sodium Methoxide in Diglyme 1 64 Pyrolysis of 4- Androstene -173- o1 -17- acetate- 3 -one p- Toluenesulfonylhydrazone 150 with Sodium Hydride in Tetrachloroethylene 165 1- Cholesten- 3- one p- Toluenesulfonylhydrazone 58 1 66 Pyrolysis of 1-Cholesten-3-one p- Toluenesul- fonylhydrazone 58 with Sodium Methoxide in Benzene 166 Pyrolysis of 1- Cholesten -3 -one p- Toluenesulfonyl - hydrazone 58 with Sodium Hydride in Benzene 169 Alumina-catalyzed Aromatization of Spiro(cyclo- heptatriene- 7' , 3- chose s t -1- ene) 15 3 170 Page Alumina - catalyzed Reaction of Cholest -1 -en- 3a-ol- 3-- methyl ether 154 171 Alumina- catalyzed Reaction of Cholest -l - en- 3p- ol- 3- methyl ether 155 172 Cholest- l- en -3a -ol and Cholest- l- en -3p -ol 157 172 2- Cholesten -1 -one p- Toluene s ulfonylhyd raz one 178 173 Pyrolysis of 2- Cholesten -1 -one p- Toluenesulfonyl - hydrazone 178 with Sodium Methoxide in Diglyme 173 2- Androsten -1-one p- Toluene sulfonylhydrazone 159 175 Pyrolysis of 2- Androsten -l -one p- Toluene- su.lfonylhydrazone 159 with Sodium Methoxide in Diglyme 176 Pyrolysis of 2- Androsten -l -one p- Toluenesulfonyl - hydrazone 159 with Sodium Methoxide in Benzene 178 5- Androstene- 3p -ol II-94 179 Andros tan- 3p -ol II -95 180 Androstanone II -96 180 2a- B r omo-Andr os tan- 3- one II -97 181 1- Androsten -3 -one II -98 182 la, 2a- Oxido- Androstanone II-99 182 2 -Andros ten -1 a- of II -100 183 2- Androsten -1 -one II -101 184 5- Cholestene- 3p -oi -3- acetate -7 -one 184
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    A Theoretical Stereoselectivity Model of Photochemical Denitrogenations of Diazoalkanes Towards Strained 1,3-Dihalogenated Bicyclobutanes Jingbai Li, Rachel Stein, and Steven A. Lopez* Department of Chemistry & Chemical Biology, Northeastern University, 360 Huntington Ave, Boston MA, 02115 Abstract Photochemical reactions exemplify ‘green’ chemistry and are essential for synthesizing highly strained molecules with mild conditions with light. The light-promoted denitrogenation of bicyclic azoalkanes affords functionalized, stereoenriched bicyclo[1.1.0]butanes. We revisited these reactions with multireference calculations and non-adiabatic molecular dynamics (NAMD) simulations for a series of diazabicyclo[2.1.1]hexenes to predict the photophysics, reactivities, and stereoselectivities. We used complete active space self-consistent field (CASSCF) calculations with an (8,8) active space and ANO-S-VDZP basis set; the CASSCF energies were corrected with CASPT2(8,8)/ANO-S-VDZP. The excitation is consistently n→π* and ranges from 3.77–3.91 eV for the diazabicyclo[2.1.1]hexenes. Minimum energy path calculations showed stepwise C–N bond breaking and led to a minimum energy crossing point, which favors the stereochemical ‘double inversion’ bicyclobutane product. Wigner sampling of 1 provided Franck- Condon points for 692 NAMD trajectories. We identified competing complete stereoselective and stereochemical scrambling pathways. The stereoselective pathways feature concerted bicyclobutane inversion and N2 extrusion. The stereochemical scrambling pathways involve N2 extrusion followed by bicyclobutane planarization, leading to non-stereoselective outcomes. The predicted diastereomeric excess almost exactly match experiment (calc.d.e.=46% vs. exp.d.e.=47%). Our NAMD simulations with 672, 568, and 596 trajectories for 1-F, 1-Cl, and 1- Br predicted diastereomeric excess (d.e.) of 94–97% for the double inversion products.
  • Synthesis and Trypanocidal Activity of Salicylhydrazones and P-Tosylhydrazones of S-(+)-Carvone and Arylketones on African Trypanosomiasis

    Synthesis and Trypanocidal Activity of Salicylhydrazones and P-Tosylhydrazones of S-(+)-Carvone and Arylketones on African Trypanosomiasis

    Journal of Applied Pharmaceutical Science Vol. 5 (06), pp. 001-007, June, 2015 Available online at http://www.japsonline.com DOI: 10.7324/JAPS.2015.50601 ISSN 2231-3354 Synthesis and trypanocidal activity of salicylhydrazones and p-tosylhydrazones of S-(+)-carvone and arylketones on African trypanosomiasis Bienvenu GLINMA 1.2.4, Fernand A. GBAGUIDI 1.2.3*, Urbain C. KASSEHIN 3, Salomé D.S. KPOVIESSI1, Alban HOUNGBEME 2, Horrhus D. HOUNGUE3, Georges C. ACCROMBESSI 1 and Jacques H. POUPAERT3 1Laboratoire de Chimie Organique Physique et de Synthèse, Département de Chimie, Faculté des Sciences et Techniques, Université d’Abomey-Calavi, 01 BP 4521 Cotonou, République Bénin. 2Laboratoire de Pharmacognosie/Institut de Recherche et d’Expérimentation en Médecine et Pharmacopée Traditionnelles (IREMPT) / Centre Béninois de la Recherche Scientifique et Technique (CBRST)/ UAC, 01 BP 06 Oganla Porto-Novo. 3Laboratoire de Chimie Pharmaceutique Organique, Ecole de Pharmacie, Faculté des Sciences de la Santé, Université d'Abomey-Calavi, Campus du Champ de Foire, 01 BP 188, Cotonou, Bénin. 4Louvain Drug Research Institute (LDRI), School of Pharmacy, Université Catholique de Louvain, B1 7203 Avenue Emmanuel Mounier 72, B-1200 Brussels, Belgique. ABSTRACT ARTICLE INFO Article history: Hydrazones are nowadays considered to be good candidates for various pharmaceutical applications. Here, we Received on: 06/03/2015 have synthesized two series of hydrazones: salicylhydrazones (GS1-4) and p-tosylhydrazones (GT1-4) from S- Revised on: 09/04/2015 (+)-carvone and three aryketones with good yields (57-91%). Molecules were characterized by elemental Accepted on: 22/04/2015 analyses; TLC, NMR 1H, NMR 13C and MS. Submitted, in vitro, to their antiparasitic testing on Trypanosoma Available online: 27/06/2015 brucei brucei, and toxicity on Artemia salina Leach, all compounds except GT2 showed significant antitrypanosomal activity IC50 ranging from 1 to 34 micromolar (µM).