16929-73-0Relevant academic research and scientific papers
SUBSTITUENT EFFECTS IN THE PHOTOSOLVOLYSIS OF BENZYL DERIVATIVES. GENERAL STRUCTURE-REACTIVITY RELATIONSHIPS.
Wan, Peter,Chak, Becky,Li, Carrier
, p. 2937 - 2940 (2007/10/02)
The relative reactivity of photosolvolysis of a number of substituted benzyl acetates is in the order ortho > meta > para, these substitutent effects being apparently additive, as suggested by the relative reactivity of photomethanolysis of several dimethoxy-susbstituted benzyl alcohols.
Structure-Reactivity Studies and Catalytic Effects in the Photosolvolysis of Methoxy-substituted Benzyl Alcohols
Wan, Peter,Chak, Becky
, p. 1751 - 1756 (2007/10/02)
The photosolvolysis of several methoxy-, dimethoxy-, and hydroxy-substituted benzyl alcohols has been studied in aqueous solution.The primary photochemical event is photodehydroxylation, to give a benzyl cation intermediate, which can be trapped by added external nucleophiles.The reaction is via the singlet excited state, based on observation of fluorescence quenching by hydronium ion in a complementary manner with acid catalysis of reaction observed for several derivatives.Solvent isotope effects on fluorescence efficiency and reaction for (7) and (8) provide additional support of singlet-state reactivity for these compounds.Dimethoxy-substituted alcohols are more reactive than monosubstituted compounds, with quantum yields of methanolysis of up to 0.31 for the most reactive compound, 2,6-dimethoxybenzyl alcohol (8).Using a kinetic argument, the quantum yields of the primary photodehydroxylation process has been estimated to be 1.0 +/- 0.1 for this compound.The results observed for the dimethoxy-substituted derivatives suggest the existence of additivity of substituent effects in these photodehydroxylation reactions.
