84064-96-0Relevant academic research and scientific papers
Temperature-dependent photochemistry of 1,3-diphenylpropenes. The di-π-methane reaction revisited
Lewis,Zuo,Kalgutkar,Wagner-Brennan,Miranda,Font-Sanchis,Perez-Prieto
, p. 11883 - 11889 (2007/10/03)
The temperature-dependent photochemical behavior of 1,3-diphenylpropene and several of its 3-substituted derivatives has been investigated over a wide temperature range. The singlet state is found to decay via two unactivated processes, fluorescence and intersystem crossing, and two activated processes, trans,-cis isomerization and phenyl-vinyl bridging. The latter activated process yields a diradical intermediate which partitions between ground-state reactant and formation of the di-π-methane rearrangement product. Kinetic modeling of temperature-dependent singlet decay times and quantum yields of fluorescence, isomerization, di-π-methane rearrangement, and nonradiative decay provides rate constants and activation parameters for each of the primary and secondary processes. Substituents at the 3-position are found to have little effect on the electronic spectra or unactivated fluorescence and intersystem crossing pathways. However, they do effect the activated primary and secondary processes. Thus, the product ratios are highly temperature dependent.
Solvent Effects on the Singlet - Triplet Equilibrium and Reactivity of a Ground Triplet State Arylalkyl Carbene
Garcia-Garibay, Miguel A.,Theroff, Craig,Shin, Steve H.,Jernelius, Jesper
, p. 8415 - 8418 (2007/10/02)
Results from intramolecular singlet and triplet specific reactivity in solvents of different polarity suggest that the spin state equilibrium of 1,2-diphenyl-1-butylidene, a triplet ground state carbene, is largely susceptible to solvent polarity.The results are consistent with stabilization of the zwitterionic singlet state in solvents of high polarity.
STREREOSPECIFIC CYCLOPROPANE SYNTHESIS FROM γ-STANNYL ALCOHOLS
Fleming, Ian,Urch, Christopher J.
, p. 173 - 192 (2007/10/02)
γ-Stannyl tertiary alcohols and γ-stannyl benzyl alcohols form cyclopropanes strereospecifically on treatment with acid, with inversion of configugation at both carbon atoms.
Ionicity in Anionic Photoexcited States. The Effect of the Covalent Character of the Carbon-Metal Bond on the Photochemical Ring Opening of Cyclopropyl Anions
Fox, Marye Anne,Chen, Chia-Chung,Campbell, Kay A.
, p. 321 - 326 (2007/10/02)
Although 1-cyano- and 1-carbomethoxy-substituted trans-2,3-diphenylcyclopropyllithiums ring open to the corresponding allyllithiums upon photoexcitation, the analogous 1-vinyl- and 1-bromo-substituted cyclopropyllithiums do not.Shifts of the oxidative peak potential in the cyclic voltammetric scans of the photoreactive cyclopropyllithiums imply that they exist as ion pairs at low temperature in THF solution.The importance of the ionic character of the carbon-metal bond in determining the efficiency of photorearrangement is also implied by MNDO reaction path calculations.
