New olefin and oxiran syntheses from carbonyl compounds, and diethyl sodiophosphonate anions and 1-aminophosphonate amino-anions

Abstract

Reaction of aromatic aldehydes, and phthalic and thiophthalic anhydrides, with diethyl sodiophosphonate (1) gives the trans-stilbenes (3), 3,3′-biphthalidylidene (30), and 3,3′-bis-(2-thiophthalidylidene)(33). Similar treatment of fluorenone (8) and xanthone (17) with (1) leads to 9,9′-bis(fluororenylidene)(9) and 9,10-dihydro-9-oxophenanthrene-10-spiro-9′-fluorene (10), and to 9,9′-bixanthenylidene (18) and 9,9′-bixanthenyl (19), respectively, but the reaction using anthrone (11) as a carbonyl reagent yields only anthraquinone (12) and anthracene (13). Similar treatment using N-methylisatoic anhydride (34) and N-methylisatin (36) produces NN′dimethylisoindigo (35). Reaction of benzaldehyde and p-chlorobenzaldehyde with diethyl 1-[(N-sodio)anilino]cyclohexylphosphonate (40) gives mainly corresponding mixtures of trans-(41a, b) and cis-stilbene epoxides (42a, b), while similar treatment of p-nitrobenzaldehyde with (40) produces 4,4′-dinitrostilbene (3e). Reaction of (8) with (40), as well as with (1), gives (9) and (10). The mechanism of formation of these products is discussed.