Medium Effects on Zwitterionic‐Biradicaloid Intermediates from Two Phenyl‐‐α‐oxoamides. Irradiations in Fluid and Solid Protic Media, Neat Solid Phases, and the Solid, Smectic and Isotropic Phases of a Completely Saturated Phosphonium Salt at Different Temperatures †

The photochemical processes of two N,N ‐dialkyl phenyl‐α‐oxoamides, N,N ‐diisopropyl phenyl‐α‐oxoamide ( 1 ) and N,N ‐dibenzyl phenyl‐α‐oxoamide ( 2 ), are investigated at different temperatures in methanol and ethylene glycol (to probe the influences of H‐bonding and viscosity), in the solid phase of d ‐sorbitol at room temperature (to compare with the results in the liquid alcohols and to assess the influence of a poorly organized “stiff” environment), in the neat solid phase (to probe the influence of well‐ordered, “stiff” matrices), and in the solid, smectic A 2 and isotropic phases of methyl‐ tris‐ tetradecylphosphonium tetrafluoroborate (1P14BF4) (to assess the ability of the intermediates to respond to subtle changes in the order and polarity of their local environments). From differences between the activation parameters for product pathways from irradiations in methanol and in 1P14BF4, we conclude that the zwitterionic pre‐product intermediate from 1 is much more sensitive to the polarity, viscosity and order of its local environment than is the isomeric pre‐product biradicaloid intermediate or either of the pre‐product intermediates from 2 . A very sensitive balance among the medium parameters, as well as internal steric and electronic factors of 1 and 2 , controls the reactive pathways of the photochemically generated intermediates.