22965-97-5Relevant academic research and scientific papers
Electronic and Conformational Effects in the Photochemistry of α-Alkenyl-Substituted Vinyl Halides
Krijnen, Erik S.,Zuilhof, Han,Lodder, Gerrit
, p. 8139 - 8150 (2007/10/02)
The photochemical reactions in methanol of the vinylic halides 2-halo-1-phenyl-1,3-butadienes 1-3Z-X (β-halo-β-alkenylstyrenes) and 1-halo-1,2-diphenylethenes 4Z-X (α-halostilbenes), with X = Cl or Br, have been studied quantitatively.E/Z isomerization, dehydrohalogenation, nucleophilic substitution, a -halogen shift, a -hydrogen shift, and oxidation are observed as the primary reactions.No reductive dehalogenation products are formed.The efficiencies of product formation are dependent on the halogen used, the electron-donating capacity of the α-substituent, the ground state conformation of the starting material, and the wavelength of excitation.Apart from the photoinduced E/Z isomerization and the oxidation reaction typical for alkenes, product formation occurs exclusively via vinyl-cationic intermediates, which are formed upon photolytic cleavage of the carbon-halogen bond.These ionic species, or part of them, are present as vinyl cation/halide anion-pairs.
THERMOLYSIS OF ALKYL-SUBSTITUTED 1,1-DIBROMO-2-PHENYLCYCLOPROPANES
Molchanov, A. P.,Kostikov, R. R.
, p. 2272 - 2275 (2007/10/02)
When alkyl-substituted gem-dibromophenylcyclopropanes are heated at 170-200 deg C under vacuum the three-membered ring is opened, and hydrogen bromide is released.The substituted 1,3-dienes are formed.
