78800-80-3Relevant academic research and scientific papers
Gas-Phase Wittig Rearrangement of Carbanions Derived from Benzyl Ethers
Eichinger, Peter C. H.,Bowie, John H.,Blumenthal Thomas
, p. 5078 - 5082 (2007/10/02)
The CA mass spectra of ions PhC-HOR and Ph(R)CH-O- (R = alkyl and phenyl) are very similar, suggesting that the Wittig rearrangement PhC-HOEt -> Ph(Et)CH-O- occurs in the gas phase.Major fragmentation can be interpreted in terms of 1,2-elimination of groups from the Wittig product ion.For example, 2H labeling of PhC-HOEt and Ph(Et)CH-O- show that the major processes produce Me-CH=CH-O- + C6H6 and (C6H4)-CHO + C2H6, with the latter process involving prior scrambling of phenyl hydrogens.An analogous process, Ph2CH-O- -> (C6H4)-CHO + C6H6 gives the major peak in the spectrum of "PhC-HOPh".
Absorption Spectra and Photochemical Rearrangements in Phenylalkene Cations in Solid Argon
Andrews, Lester,Harvey, James A.,Kelsall, Benuel J.,Duffey, Donald C.
, p. 6415 - 6422 (2007/10/02)
Matrix photoionization experiments with phenylalkenes produced and trapped the parent molecular cations in solid argon at 20 K.In the substituted styrene cation cases, structure was resolved in red and ultraviolet absorption bands and assigned to Ph-C stretching and Ph-C=C bending modes.Molecular ion rearrangements were observed during sample formation and upon the photolysis of the cold sample; allylbenzene cation rearranged to β-methylstyrene cation and indan cation with 290 nm irradiation.The matrix absorption bands were substantially sharper than photodissociati on spectra, which suggests that excess internal energy may contribute substantially to the bandwidth of gaseous molecular ions produced by electron impact.
