J. N. Levy, C. McKenna
Dec 1, 1993
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Influential Citations
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Journal
Phosphorus Sulfur and Silicon and The Related Elements
Abstract
Abstract Oxidation of the methylidene double bond in triethyl α-phosphonoacrylate 2 by O3, catalytic RuO4 (RuO2/NaOCI, RuO2/NaIO4) and stoichiometric RuO4 was investigated as a route to α-oxygenated phosphonoacetate derivatives. Ozonation of 2 gave a mixture of products containing, in one experiment, triethyl phosphonoglyoxylate 1 as a minor (<5%) component. Efforts to prepare ethylidene compounds analogous to 2 (as alternative ozonation substrates) using known routes for synthesis of corresponding diethyl oxomalonate derivatives were unsuccessful. Treatment of 2 in biphasic H2O/CCI4 with catalytic RuO4 using NaOCI as co-oxidant or with NaOCI alone produced a novel epoxide product, triethyl α-phosphonoacrylate oxide (7) in up to 79% isolated yield. When NaOCI was replaced with NaIO4 as the RuO2, reoxidant (H2O/CHCI3), the major reaction product in the aqueous phase was identified by 13C and 13P NMR as triethyl dihydroxyphosphonoacetate 8, the hydrate of the ketone 1. Reaction of 2 with stoichiometric RuO4...