- PHOTOLYSIS OF 5-DIAZO-2,2-DIMETHYL-4,6-DIOXO-1,3-DIOXANE (DIAZOISOPROPYLIDENEMALONIC ACID)
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The principal pathway in the photochemical (λ > 210 nm) transformation of 5-diazo-2,2-dimethyl-4,6-dioxo-1,3-dioxane in an aqueous medium (or in methanol) is splitting out of nitrogen and the Wolff rearrangement to give the stable 2,2-dimethyl-5-oxo-1,3-dioxolane-4-carboxylic acid (or its methyl ester), which undergoes decarboxylation only at temperature above 150 deg C, whereas it undergoes hydrolysis to a hydroxymalonic acid in the presence of trifluoroacetic acid.
- Nikolaev, V. A.,Khimich, N. N.,Korobitsyna, I. K.
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- Chemistry of diazocarbonyl compounds: XXV. Comparative photochemistry of diazo compounds and sulfur ylides of the 1,3-dioxane-4,6-dione series
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Photochemical decomposition of 2,2-dialkyl-5-diazo-1,3-dioxane-4,6-diones in the presence of pyridine, methanol, or dimethyl sulfide as carbene traps involves mainly the Wolff rearrangement which is likely to follow a concerted pattern, while the yield of the "carbene" products does not exceed 27-28%. No carbene intermediates are formed in the photolysis of the corresponding dioxo sulfonium ylides under analogous conditions, and the main photochemical process is 1,2-methyl shift (Stevens rearrangement), followed by photochemical transformations of the primary products according to the Norrish type II pattern. Pleiades Publishing, Inc., 2006.
- Nikolaev,Shevchenko,Platz,Khimich
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p. 815 - 827
(2007/10/03)
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