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An empirical analysis of c.d. data for steroidal and related transoidαβ-unsaturated ketones substantially confirms existing helicity ‘rules’ for the n→π* and π→π* Cotton effects, and shows that the signs and magnitudes of Δε depend essentially upon the structural class of the bicyclic component containing the chromophore. The third c.d. band, in the region 200–220 nm, has the characteristics expected for the olefinic πx→πy* transition, and is relatively insensitive to the immediate environment of the carbonyl group.


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