Diisophorone and Related Compounds, Part 28 [1] Diisophorane-4-spiro-2-(oxiranes)
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چکیده
tions: The methyl ester 4, preformed from 2 by chromic acid oxidation [4], yields the identical product 5 with uptake of one mole of diazo methane. The discharge of the yellow colour of the reactants 3, 4 indicates the disruption of the a,ßdiketo-chromophore by the action of the second molecule of diazomethane. Its incorporation as a spiro-oxirane ring at C-4 is indicated by the l3C NM R spectrum of 5: this is virtually coincident with that of the precursor 4, except for the signals of C-4 and its immediate environment (Table I). The 4-keto-signal (of 4, Ö, 180.9 ppm) is replaced by a high-field singlet of chemical shift (62.8 ppm) within the range of oxirane spiro-carbons [8], The distinct upfield displacements of the C-3 and C-5 signals reflect the increased electron densities at these positions, due to the removal of the adjacent electron-attracting 4-oxo-group. The triplet of the newly introduced 3'-methylene-group (r)\ 48.2 ppm) appears in the correct range of oxirane-methylene carbons [9], The IR spectrum of 5 contains bands confirming the presence of the «^-conjugated ring-enone-system (1665, 1635 cm "1) as well as the carboxylic ester group (1725, 1245 cm“1).
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