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Radical Anions, Radicals and Anions

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Radical Anions, Radicals and Anions AN ABSTRACTOF THE THESISOF DOCTOR OF PHILOSOPHY Larry Lee Hutchinsonfor the degree of September 21, 1976 in CHEMISTRY presented on THE FORMA- Title:RADICAL ANIONS,RADICALS AND ANIONS. TION ANDSTEREOCHEMISTRY OFALKYL LITHIUM REAGENTS FROMLITHIUM 4,4'-DI-TERT-BUTYLBIPHENYL AND ALKYL HALIDES. ,Redacted for Privacy. Abstract approved: Peter K. Freeman The reactions of alkylhalides with metals andradical anion solutions were investigated. The reaction of exo-and endo-anti-3-chlorotricyclo , deuteroly- [3.2. 1.024joct-6-ene with magnesium inTHF followed by sis gave syn:antideuteriation ratios of 2.2and 0.42, respectively, Analysis of the exohydro- with 85% monodeuteriumincorporation. shift reagent study with carbon involvedepoxidation followed by a 4 chloro-exo-tricyclo[3. 2. 1.02,'octane Eu(fod)3.Reaction of anti-3- -78° in THF with a rate with lithium naphthalenedianion proceeded at lithium constant of 5.5 x10-21V11 min1, while under identical conditions -1 -1. naphthalene exhibited arate constant of1.0 Mmin Deuterolysis incorporation of the dianionsolution gave a syn toanti deuterium with greater than 50.In contrast,7-chloronorcarane in reacting lithium naphthalene in THF at-78° exhibited a rate constant of -1 0. 035 Mmin-1. Deuterolys is of the dianion solution gave a syn to anti deuterium incorporation greaterthan 50.In contrast, 7-chloro- norcarane in reactingwith lithium naphthalene in THE at-78° -1min-1 exhibited a rate constant of 0. 035M for the anti compound while the syn had a rate constantof 0.063. Upon deuterolysis, the deuterium incorporation was75%, with an anti:syn ratio of 7. naphthalene with Mg Brin THF Reaction of sodium or lithium 2 gave a dark precipitatewith properties expected for magnesium metal.Reaction of sodium anthracene withmagnesium bromide in THF, or reaction of magnesiummetals with anthracene in THF gave a yellow solutionof the sparingly soluble magnesiuma.nthracene dianion.Purification and crystallization gave an orangecrystalline solid with a composition of MgA3THF. Single crystal X-ray analy- 0 3 sis indicated the unit cell to betriclinic with a volume of 4668 A. The reactions of a wide variety ofalkyl halides with lithium naphthalene (N), biphenyl (B),di-tert-butylnaphthalene (DTBN) and 4, 41-di-tert-butylbiphenyl(DTBB) in THF were investigated.The reaction of LiDTBB with primary,secondary, tertiary and cyclo- propyl halides in THF at-78° gave 90% or higher yields ofthe cor- responding lithium reagent.LiDTBB was found to give less than3% to give a 97% alkylation products with halidesand reacted with CO2 recovery of DTBB,behaving in almost all respects as asolution of lithium metal in THF. The stereochemistry of theproduct lithium reagents from the reaction of a number of alkylhalides in THF at -78° was investigated. The stereochemistry of theproducts from the reaction ofcyclopropyl halides and LiDTBB was interpreted asbeing an exact copy of the radical stereochemistry.The reaction of syn- oranti-7-chloronor- carane gave an anti:synlithium incorporation of 10, asdetermined by metal halogen exchange with1, 2- dibromoethane.Similarly, anti-3- chloro-exo-tricyclo[3,3.1.02,4] octane gave a ratio of syn-Li to anti-Li of 200.Reaction of anti-7-bromo-7-methylnorcaranewith LiDTBB gave an anti-Li to syn-Liratio of 3 as determined by gc. The stereochemistry of the reactionof non-cyclopropyl secondary halides with LiDTBB wasinterpreted in terms of a map- ping of the vibrational structureof the radicals upon the potential energy surface of thecorresponding anion.For significantly pyra- midal radicals this is the radicalequilibrium.Reaction of syn-7- bromonorbornene gave an anti-Li:syn-Liof 3.8.The lithium reagents were shown to beconfigurationally stable at -78° in THFby preparation of the syn-Li compoundby metal halogen exchange of the bromide with tert-butyllithium.in THF at -50°, giving atleast 95% retention.Lithium stereochemistry wasdetermined by deuteriolysis followed by epoxidation and nmrshift reagent (Pr(fod)3) study. Treatment of anti-7-chlorobenzonorbornadiene with. LiDTBB was followed by deuterolysis.Analysis performed byhydroboration and shift study indicated 99%deuterium incorporation with an Pr(fod)3 anti:syn deuteration ratio of1.33.Treatment of exo-2-chloronor- _ bornane with LiDTBB followedby metal halogen exchangewith I, 2- dibromoethane gave a 10:1 ratio of exo toendo bromine incorpora- tion.Reaction of 4-chloro-tert-butylcyclohexanewith LiDTBB followed by deuterolysis gave a14:1 ratio of equatorial to axial deuterium incorporation as determinedby ir. Radical Anions, Radicalsand Anions.The Formation and Stereochemistry of AlkylLithium Reagents from Lithium 4, 4' -Di-tert-butylbiphenyland Alkyl Halides. by Larry Lee Hutchinson A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy June 1977 APPROVED: Redacted for Privacy Professor of Chemistry in charge of major Redacted for Privacy Chairman of Department of Chemistry Redacted for Privacy Dean of Graduate School Date thesis is presented September 21, 1976 Typed by Clover Redfern for Larry Lee Hutchinson ACKNOWLEDGMENTS I wish to sincerely thankDr. Peter K. Freeman forhis encouragement, guidance,patience and especially forthe freedom he allowed on thisresearch project. Thanks are also due to Dr.Carroll W. De Kock for his assistance with the X-raydiffraction work and for the loanof the DeKock Soxhlet extractor.In addition I would like tothank my father for his moral andfinancial support and would like toacknowl- edge helpful discussionswith Dr. Joseph W. Nib ler,Karl E. Swenson and E. Philip Sietz. Sincere appreciation is due toKim Wise for the correctionof my spelling andthe typing of the rough draft. TABLE OF CONTENTS Page HISTORICAL 1 Physical Properties of Radical Anions Ion Pairing in Radical AnionSolvation 4 Dianion Formation and Properties 15 Summary of the Physical Propertiesof Selected Radical Anions 19 Reaction of Naphthalene andAnthracene Radical Anions with Water 20 The Reaction of Alkyl Halides withRadical Anions 23 The Structure and Equilibria ofRadicals 57 RESULTS AND DISCUSSION 59 Introduction 59 Low Temperature PotassiumReduction of anti-23-C1 70 Reaction of anti-23-CI with LithiumNaphthalene 73 Reaction of anti-23-C1 with LithiumNaphthalene Dianion 78 Reaction of Magnesium Bromide withSodium Naphthalene 83 Magnesium Anthracene Dianion 87 Alkyl Lithium Reagents from AlkylHalides and Lithium Radical Anions 90 The Stereochemistry ofLiDTBB-Cyclopropyl Halide Reactions 104 The Reaction of Planar andRapidly Inverting Cyclic Radicals with LiDTBBTheoretical Considerations 115 The Reaction of Planar and RapidlyInverting Cyclic Radicals with LiDTBB- -Four Systems 122 134 EXPERIMENTAL General Laboratory Proceduresand Conditions 134 Special Conditions 165 BIBLIOGRAPHY 18 1 LIST OF FIGURES Figure Page 1.Nmr spectrum of7-deuteriobenzonorboren-2-ol 129 . with added Pr(fod)3 2.Lithium reagent configurations fromthe reaction of radicals with LiDTBB in 1HF at-78°. 133 3.Graph of In(23-Cl:C131-128) vs. time forthe reaction of 23-C1 with lithium naphthalenedianion. 151 137 4.A schematic drawing of the De Kocksoxhlet extractor. LIST OF TABLES Page Table 1.Reduction potentials ofselected aromatic hydro- carbons in DMF. 4 2.Rate constants for electronexchange of naphthalene radical anions at roomtemperature. 14 3.Comparison of the reaction oftriphenyltin hydride with 3, 5-cyclocholestan-6-y1chloride. 29 4.Electron transfer vs. couplingand extent of dialkylation in the reaction of pentyliodides with sodium naphthalene in THF. 36 5.Rates of electron transferreactions of radical anions with halides at 20-25°. 46 6.Partitioning between electrontransfer and coupling for selected halides andradical anions. 51 56 7.Vinyl radical trapping withsodium naphthalene in THF. S.The stereochemistry ofreduction of selected cyclopropyl halides with metals. 65 9.Stereochemistry of lithium reagentformation from 26 and 27. 69 96 10.Survey of lithium radicalanion-alkyl halide reactions. 112 11.The reaction of anti-31-Brwith electron donors in THF. 169 12.Reaction of 1-chlorooctanewith lithium radical anions. 169 13.Reaction of 1-bromooctanewith lithium radical anions. 170 14.Reaction of 2-bromooctanewith lithium radical anions. 170 15.Reaction of 2 -chlorooctanewith lithium radical anions. 16.Reaction of 3 chlo ro -3 -methylheotane with lithium radical anions. 171 Page Table 17. Reaction of 7-chlorcnorcaranewith lithium radical 171 anions. 18.Reaction of some selectedhalides with lithium di-tert-buty-lhiphenyl. 17 1 RADICAL ANIONS, RADICALSAND ANIONS. THE FORMATION AND STEREOCHEMISTRYOF ALKYL LITHIUMREAGENTS FROM LITHIUM 4,-DI-TERT-BUTYLBIPHENYL AND ALKYL HALIDES HISTORICAL Physical Properties of RadicalAnions Radical anions are very simplespecies, consisting only of an aromatic hydrocarbon to which anelectron has been added.The electron resides in the lowestpreviously unoccupied molecularorbital and is thus delocalized overthe entire 7 framework ofthe molecule. It is a very simple matter to prepareradical anions --a rather differ- ent situation than existswith most of the commonlystudied intermedi- ates of organic chemistry;carbonium ions, carbenes,radicals, and anions.The addition of any alkalimetal to any polycyclic aromatic hydrocarbon in an ether solventof moderate cation solvating power under an inert atmospherewill result in rapid dissolutionof the metal to form an intenselycolored and usually paramagneticsolution. The first reported formationof a radical anion may have appeared as
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