24182-35-2Relevant academic research and scientific papers
Preparation of multisubstituted allenes from allylsilanes
Ogasawara, Masamichi,Ge, Yonghui,Uetake, Koichi,Fan, Liyan,Takahashi, Tamotsu
, p. 3871 - 3876 (2007/10/03)
A three-step route of converting allylsilanes to functionalized allenes was developed. Thermal decomposition of 1,1-dibromo-2-(silylmethyl)cyclopropanes, which were quantitatively prepared by treatment of allylsilane derivatives with CHBr3/KOs
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.
