102396-68-9Relevant academic research and scientific papers
SELECTIVITY IN THE PHOTOPRODUCT RATIOS FROM NORRISH II REACTIONS OF A HOMOLOGOUS SERIES OF 2-ALKANONES IN THEIR MELT AND SOLID PHASES. COMPARISON WITH OTHER ENVIRONMENTS
Weiss, Richard G.,Chandrasekhar, Sosale,Vilalta, Patricia M.
, p. 142 - 152 (2007/10/02)
The product ratios from Norrish II reactions of 2-tridecanone, 2-tetradecanone, 2-pentadecanone, 2-hexadecanone, 2-heptadecanone, and 2-nonadecanone have been measured at low percents of conversion in the melt and solid phases.Although elimination/cyclization photoproduct ratios from the neat crystals are > 60 in optimal cases, the ratios of cyclobutanol diastereomers (cyclization products) remain near those observed from melt irradiations.From comparisons of the photoproduct selectivities in the neat solids and in their solid solutions, where the solvent molecules are similar in size and shape to the 2-alkanones, it is concluded that the crystalline lattices of some foreign hosts offer environments to the pre-product biradical intermediates, which are at least as restrictive as the environments of the solid 2-alkanones.
LIQUID-CRYSTALLINE SOLVENTS AS MECHANISTIC PROBES. 23. NORRISH II REACTIONS OF 2- AND SYM-ALKANONES IN THE ISOTROPIC, SMECTIC B, AND CRYSTALLINE PHASES OF n-BUTYL STEARATE.
Treanor, Richard L.,Weiss, Richard G.
, p. 1371 - 1392 (2007/10/02)
n-Alkanones with the carbonyl group at the 2 or central positions (1 and 2, respectively) have been irradiated in the isotropic, smectic B, and two solid phases of n-butyl stearate (BS).The lengths of the ketones were varied from 11 to 31 carbons.The ratios of elimination/cyclization products and diastereomeric cyclobutanol products were measured for each as a function of temperature and BS phase.The effect of 1 and 2 on the phase transition temperatures of BS has been correlated with changes in the product ratios.The experiments demonstrate that a very sensitive cooperative relationship exists between the ease with which 1 and 2 fit into the ordered phases of BS and the degree to which the solvent matrices influence ketone photochemistry.The influence of solvent order on the product ratios is distinctly different for 1 and 2, and for the two product ratios from one ketone.
