Direction of enolization of 1:3-diketones by mass spectrometry

Abstract

A novel method of establishing the direction of enolization of a 1:3-diketone is to examine of the mass spectrum of the isoxazole obtained from it by hydroxylamine treatment. Thus, the products obtained from five 1:3 diketones,viz. l-(2-naphthyl)-3-phenylpropane-l :3-dione and its 3-p-toluyl,p-methoxyphenyl,p-nitrophenyl andp-chlorophenyl analogues, consist of both the possible isomeric 3:5-disubstituted isoxazoles in each case, indicating that each diketone exists in both the enolic forms. The percentage of the enols was derived, in a qualitative manner, from the ratio between the percentage abundances of the aroyl and naphthoyl cation peaks present in the mass spectrum of the product from each diketone. In four out of the five cases, each possible isomeric isoxazole was synthesised by the unambiguous chalconedibromide method and examination of the mass spectrum in each case revealed that either the aroyl or the naphthoyl cation peak was exhibited depending on whether the 5-substituent was an aryl or a naphthyl group respectively. A re-examination of the direction of enolization of 4-methoxydibenzoylmethane revealed that it existed in both the enolic forms, contrary to earlier observations.