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Some Aspects the Baeyer-Villicer Reaction

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Some Aspects the Baeyer-Villicer Reaction SOME ASPECTS THE BAEYER-VILLICER REACTION - by - JOHN EDVARD BOLLIG-ER. B.So, CSyd.) A. Thesis submitted for the degree of MASTER OF SCIENCE - at the - UNIVERSITY OP NEW SOUTH WALES April, 1963- CONTENTS Page No. Summary . .. 1 The Baeyer-Villiger Reaction .. 2 Discussion: .. .. 26 Baeyer-Villiger Oxidation of 2-Bromocholestan-3-one 32 Baeyer-Villiger Oxidation of 2-Bromofriedelin 50 Baeyer-Villiger Oxidation of 2-Chlorocholestan-3-one 53 Baeyer-Villiger Oxidation of 2-Iodocholestan-3-one 54 Baeyer-Villiger Oxidation of Gerin 56 Experimental .. .. 61 Acknowledgments .. .. 87 Bibliography .. .. 88 1 SUMMARY V/ith a view to synthesising suitable inter­ mediates for intramolecular Darzen's glycidic ester syntheses, certain steroid and triterpenoid a- substituted ketones have been subjected to Baeyer- Yilliger oxidation. In some cases the oxidation yielded unexpected products and possible mechanisms for their formation are discussed. In other cases the expected products were obtained but readily under­ went an unusual rearrangement. The structures of the rearranged products have been chemically elucidated and the mechanism of the rearrangement is discussed. This thesis is prefaced by a discussion of the Baeyer-Villiger reaction. THE BAEYER-VTLLIGER REACTION The reaction of ketones with peracids to give esters was first observed by Baeyer and Villiger in 1899 . The scope of this reaction, now known as the Baeyer-Yilliger reaction, has since been widely extended and it has found many useful applications in organic chemistry. Among its representative uses, illustrated by many examples in p the literature , are the formation of esters from simple aliphatic or aromatic ketones, formate esters from aldehydes, anhydrides from o—diketones, lactones from alicyclic ketones and enol lactones from a,0-unsaturated alicyclic ketones. The reaction may be effected under mild conditions and using a wide range of peroxides including neutral, acidic or alkaline hydrogen peroxide, permono- or perdi-sulphuric acid, perbenzoic, monoperphthalic, peracetic or trifluoro- peracetic acids. It is usually carried out simply by dissolving the carbonyl compound in a suitable solvent, adding the peracid and leaving the mixture to stand at room temperature or with mild heating until reaction is complete. - 3 - With the highly reactive trifluoroperacetic acid the reaction is often complete within a few minutes. The mechanism of the reaction has been the subject of a number of publications 1*3-8,11,12,20^ The meohan- i ism was put forward by Baeyer and Villiger and involved the initial formation of an "oxoxide” intermediate which subsequently rearranged with group migration. R O7-H 0 Sr" C—0—R'--» R—C — 0—R7 X > R— Wittig and Pieper^ suggested an electrophilic attack of the carbonyl oxygen by OH* to give an intermediate peroxide which then rearranged. 0—H I > R—C—0—"R + a 5 Criegee , and Robertson and Waters , postulated nucleophilic attack of the carbonyl carbon by the peracid anion to give a hydroxy perester intermediate. Heterolysis - 4 - of the perester to eliminate an acid anion leaves an electron deficient oxygen atom which is stabilised by the migration of one of the groups. R .0—H 0-7-K H R—C—0—R * 0 —-0^—X The validity of this last mechanism was established 6 18 by the elegant experiment of Doering and Dorfman. Ox labelled benzophenone was reacted with perbenzoic acid to yield labelled phenyl benzoate. This was reduced with lithium aluminium hydride to phenol and benzyl alcohol and the distribution of 0X in these products determined. The Baeyer-Villiger mechanism would result in an equal dis- tribution of O1 ft between the phenol and benzyl alcohol l8 whereas that of wittig and Pieper would result in the 0 being exclusively in the phenol. Doering and Dorfmann, how- 1 ft ever, found the 0X to be exclusively in the benzyl alcohol, the result to be expected from the Griegee mechanism. The kinetics of the Baeyer-Villiger reaction have been closely examined by Hawthorne and Emmons'. These workers investigated the trifluoroperacetic acid oxidation of a series of ketones in the presence of trifluoroacetic acid. 5 - In a non-polar solvent, ethylene chloride, and using a large excess of ketone, the overall rate was found to depend on the identity of the ketone and on the concentrat­ ions of both acid catalyst and peracid but was independent of the ketone concentration. This suggested that the ketone was initially rapidly complexed with one of the other reactants. On mixing ethylene chloride solutions of ketone and trifluoroacetic acid the production of heat and shifts in the ultraviolet spectrum indicated that a complex such as the following was formed R In ethylene chloride the rate data were found to fit the second order expression: -d [CI',CO H) /dt = k2 [CP3C02H] [CP3C02H-R2C0j In a polar solvent, acetonitrile, complex formation was apparently inhibited due to solvation and the data were found to fit the 3rd. order expression: -d [CF3C03H]/dt = k3 [CP3C02H] [r2CQ1 [CF3CC>3h] 6 The rates of simple carbonyl addition reactions such as oximation and semicarbazone formation may be correlated by a simple linear free energy relationship. For a given series of ketones a similar relationship should exist be­ tween the free energy of activation for the Baeyer-Villiger reaction and the free energy of activation for oximation if the rate determining step of the former reaction were the slow addition of peracid to the carbonyl group. No such relationship was found by Hawthorne. The relative nucleophilicities of the anions of peracetic and trifluoro- peracetic acids are the reverse of the relative reactivities of the two acids in the Baeyer-Villiger oxidation, the latter being two hundred times faster than the former in the oxidation of phenyl cyclohexyl ketone . These facts exclude the peracid addition as the rate determining step and indeed point to its being the acid catalysed decomposition of the intermediate, for the relative reactivities of the tri- fluoroacetate and acetate anions respectively as leaving groups parallel the reactivities of their parent peracids in the Baeyer-Villiger reaction. The course of the Baeyer-Villiger reaction, i.e. the rate determining elimination of a negative ion to leave a positive centre to which the intramolecular migration of an atom or group then takes place, presents a distinct analogy to a class of ionic 1, 2 shift reactions represented by the - 7 - Pinacol, Wagner-Meerwein, Hofmann, Lossen, Curtis, Beckmann and other related reactions. In all these reactions the formation of a carhonium ion or atom having a sextet of electrons is followed by group migration, and it has been observed that factors which increase the rates of formation of the positive centres affect the overall rates of these reactions. For example, in the rearrangement of camphene hydrochloride (I) to isobornyl chloride (III), a reaction thought to involve the carbonium ion (II) the reaction rate was found to increase with increasing dielectric constant of the solvent . Compounds such as ferric chloride and mercuric chloride which can coordinate with a chloride ion 22 were found to be excellent catalysts . The analogy between these reactions and the Baeyer-Villiger reaction is further illustrated by certain other features of it. The migration of asymmetric groups in the Baeyer- - 8 - Villiger reaction has been investigated and found to proceed with retention of their configurations. Turner studied the perbenzoic acid oxidation of cis and trans 1-acetyl-2-methyl o cyclohexanone0. In both cases the 2-methyl cyclohexyl group migrated with complete retention of configuration to give respectively the cis and trans 2-methyl cyclohexanyl acetates. He obtained similar results with the cis and trans 1-acetyl-2-methylcyclopentanones. Mislow and Brenner found that in the peracetic acid oxidation of optically active methyl a-phenylethyl ketone, 0 II CrH- CH- — Chi > C^H-—CH—0 — C- 6 b I '6 b CH, CH3 the a-phenylethyl group migrated with complete retention of q its stereochemical configuration*^. A further example is the perbenzoic acid oxidation of both the 17a and 17ft isomers of 3a-acetoxy-pregnan-20-one to give respectively the 17a and 17ft isomers of 5ft-androstane-3a,17-diol 10 diacetate . This result is due to the migration with retention of configuration of the two epimeric atoms. In the Pinacol, Hofmann, Beckmann, and other reactions of the beforementioned class of 1, 2 shift reactions, migration - 9 - of asymmetric groups has been observed to occur without 2^-27 Walden inversion or racemisation The relative tendencies of various groups to migrate in the Baeyer-Villiger reaction, generally termed migrat- 11 12 ory aptitudes, have received considerable attention 9 These migratory aptitudes again parallel those observed for various migrating groups in the pinacol-^ and related reactions and may be rationalised by considering the mechanism of the rearrangement in a form that is somewhat simplified but best suited for the present argument. The elimination of an anion from the hydroxy perester inter­ mediate leaves an electron deficient oxygen atom which is stabilised by the migration to it of one of the groups (R, R') with its pair of bonding electrons. Which of these groups migrates will be determined by the relative electron densities, or nucleophilicities, of the two bonds x and y. If R and R* are alkyl groups the nucleophilicities of these bonds will depend upon induct­ ive effects and will, for example, be greater for bond q 10 - of the isopropyl group than for bond p of the t-butyl group. ? Thus one could expect that for alkyl groups migratory aptitudes would increase in the order primary secondary tertiary. Table I (p. 11) contains selected results from the work of various authors11’12’ which illustrate these tendencies. In the case of aryl group migration it may be seen that p-substituents such as the methoxyl group, which tend to render the phenyl group more prone to electrophilic substitution, also tend to enhance its migratory aptitude by increasing the electron density in the migrating bond.
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