Recherches dans la série de la quinoléine: Préparation et oxydation du chlorhydrate de (1-quinoléinio)acétate

Reaction of quinoline with chloroacetic acid yields N-carboxymethyl-quinolinium chloride ( 1 ) (75%), which is oxidised by K₃Fe(CN)₆ in the presence of a base to N-carboxymethyl- 2 -quinolone ( 2 ) (70%). If 2 is heated in pure form at 300°, 1,3-Bis(2-quinolon-1-yl)acetone ( 4 ) (43%) is obtained; the expected N-methyl-2-quinolone ( 5 ) is formed by decarboxylation of 2 in benzyl benzoate at 275° (34%).     

Structures de deux β-énaminoesters cycliques: l'α-(tétrahydropyrrolidinylidéne-2) acétate d'éthyle et l'α-(hexahydroazepinylidéne-2) acétate d'éthyle

The structure of ethyl α-(tetrahydro-2-pyrrolidinylidene) and α-(hexahydro-2-azepinylidene) acetates has been determined from the X-ray crystallographic analysis. The results show that, in a solid state, these compounds exist as β-enaminoesters which have a Z configuration. They also show the presence of intra and intermolecular hydrogen bonding.     

Hydroxylation de l''estrone et de son acétate par le peroxyde d''hydrogéne en milieu superacide

Estrone 1a and its acetate 1b react with hydrogen peroxide in SbF₅-HF to give hydroxylated compounds. The formation of the dienone 2 can be accounted for by reaction of the electrophile H₃O₂⁺ on the neutral substrate, whereas formation of compound 3b implies electrophilic attack on the protonated ester 1b. Higher acidity favours rearrangement of the resulting ion 9 to yield, through a spiro intermediate, the ester 4b. Under the reaction conditions esters 3b and 4b]are slowly converted into the corresponding phenols 3a and 4a.