57766-96-8Relevant academic research and scientific papers
Picosecond radical kinetics. Rate constants for ring openings of (2-alkoxy-3-phenylcyclopropyl)methyl radicals
Tadic-Biadatti, Marie-Helene Le,Newcomb, Martin
, p. 1467 - 1474 (2007/10/03)
Rate constants for ring openings of the (trans,trans-2-methoxy-3-phenylcyclopropyl)methyl radical (1M) and the (trans,trans-2-tert-butoxy-3-phenylcyclopropyl)methyl radical (1B) have been determined between -21 and 37 deg C by indirect kinetics employing benzeneselenol trapping as the composition reaction.Radicals 1 were formed in chain reactions of the appropriate 'PTOC esters', 2-thioxopyridine-N-oxy derivatives of the corresponding carboxylic acids, the syntheses of which are reported.Radicals 1 rearrange with rate constants of 8 * 1011 s-1 (1M) and 5 * 1011 s-1 (1B) at 25 deg C with predominant (160:1 and 60:1, respectively) cleavage to give benzylic radical products.The rate constants for ring openings to the minor, alkoxy-substituted radical products represent the first measurements of the kinetic effects of alkoxy substitution on cyclopropylcarbinyl radical ring openings.Precursors to radicals 1 can be employed in mechanistic probe studies that permit differentiation between radical and cationic intermediates.
Photochemistry of Arylbutadienes. Part 2. Preparation and Photochemistry of 1-(Substituted-aryl)butadienes. A Ground-state Substituent Effect on an Excited-state Reaction
Baldry, Peter J.
, p. 805 - 808 (2007/10/02)
Yields and quantum yields are reported for the photoaddition of methanol to 1-phenylbutadiene and eight substituted 1-phenylbutadienes.For allyl and homoallyl products log Φ correlates more satisfactorily with ground-state substituent constants than with excited-state constants; for cyclopropylmethyl products, no correlation is observed with either set of constants.
Photochemistry of Arylbutadienes. Part 3. Mechanisms of Photoaddition of Methanol to 1-Arylbutadienes
Baldry, Peter
, p. 809 - 815 (2007/10/02)
The mechanism of formation of methyl ethers from irradiation of 1-arylbutadienes in methanol has been studied by deuterium labelling, fluorescence quenching, sensitisation, and kinetic studies.Cyclopropylmethyl ethers arise by a bicyclobutane mechanism; allyl and homoallyl ethers are formed by reaction of methanol with the 1Bu-like excited singlet diene to produce carbocation intermediates.
