Charles M. Hall

Microbial oxygenation of dialkylbenzenes (I)

Abstract The use of the microorganism Sporotrichum sulfurescens (ATCC 7159) to oxygenate organic molecules has been extended to several dialkylbenzenes. Oxygenation of 1,4-di- t -butylbenzene ( 1 ) gave 4- t -butyl(1-hydroxy-2-methyl)isopropylbenzene ( 2 ) and 1,4-di-(1-hydroxy-2-methyl)isopropylbenzene ( 3 ); of 1,4-diisopropylbenzene ( 4 ) gave ( R,R )-1,4-di-(1-hydroxy)isopropylbenzene ( 5 ); of 1,3-diisopropylbenzene ( 6 ) gave 1,3-di-(2-hydroxy)isopropylbenzene ( 7 ), 3-(1-hydroxy)isopropyl-(2-hydroxy)isopropylbenzene ( 8 ), and 1,3-di-(1-hydroxy)isopropylbenzene ( 9 ); and of p -isobutylisopropylbenzene ( 20 ) gave 1-( p -2-hydroxyisopropylphenyl)-2-methylpropan-2-ol ( 15 ) and 1-( p -1-hydroxyisopropylphenyl)-2-methylpropan-2-ol ( 16 ). Monohydroxydialkylbenzenes also served as useful substrates in this reaction as suggested by the fact that 2 is an intermediate in the formation of 3 from 1 . Oxygenation of 1-( p -isopropylphenyl)-2-methylpropan-2-ol ( 14 ), conveniently prepared from 2-( p -isopropylphenyl)propene ( 12 ) via oxygenative isomerization with thallium trinitrate to 13 followed by addition of methyl magnesium bromide, gave 15 and 16 . Oxygenation of 2-( p -isobutylphenyl)propan-2-ol ( 18 ) gave 15 , 2-( p -isobutylphenyl)-propan-1,2-diol ( 21 ), and 1-( p -2-hydroxyisopropylphenyl)-2-methylpropan-3-ol ( 22 ). Compound 16 , obtained from substrate 14 , was converted to (2 R )-2-[4-(2-hydroxy-2-methylpropyl)phenyl]propionic acid ( 11 ), the enantiomer of a metabolite of the antiinflammatory agent, 2-(4- i -butyl)phenylpropionic acid ( 10 ).

Dihalocarbenes Rrom Thallium (I) Ethoxide and Haloforms

Abstract It has been known for many years that dihalocarbenes may be generated by the reaction of strong bases with haloforms and that the resulting dihalocarbenes react rapidly with alkenes to produce dihalocyclopropane derivatives.1 The procedures reported to date suffer from two disadvantages in that they require: 1) the use of a date solvent or the necessity of a two-phase system when a hydrocarbon solvent is used, and 2) the use of covalent nature and unique solubility properties of thallium (I) ethoxide suggested that its use might eliminate, or at least minimize, these diffculties in the generation of dichalocarbenes.