Synthesis of oximes, aziridines, and allyl alcohols derived from substituted 1-phenyl-1-nonen-3-ones as potential cytotoxic and antitumor agents.

A number of nuclear-substituted 1-phenyl-1-nonen-3-one oximes were synthesized. Reduction of several of these compounds with lithium aluminum hydride yielded the corresponding 1-phenyl-2,3-epiminononanes, shown by 100-MHz NMR spectroscopy to be the cis-geometrical isomers. When several ring-substituted 4-dimethylaminomethyl-1-phenyl-1-nonen-3-ones were treated with hydroxylamine hydrochloride under forcing conditions, the product isolated was the corresponding oxime. Reaction under mild conditions led only to the isolation of the Michael addition product of the oxime in low yield. Reduction of some nuclear-substituted 4-dimethylaminomethyl-1-phenyl-1-nonen-3-ones with sodium borohydride led to the formation of the corresponding allyl alcohols, and the products were shown by 1H- and 13C-NMR spectroscopy to be the threo-isomers or, alternatively, a mixture of erythro- and threo-isomers. Reaction of phosphoric acid with one of the substituted allyl alcohols led to a diolefin, shown by NMR spectroscopy to be a mixture of (E, E)- and (E, Z)-isomers in a ratio of 65:35.