20679-59-8Relevant articles and documents
REGIOSPEZIFISCHES UMLAGERUNGSVERHALTEN BUTADIENYL- UND VINYLSUBSTITUIERTER CYCLOPRPILYDENE
Fleischhauer, Ilona,Brinker, Udo H.
, p. 3205 - 3208 (1983)
The reaction of the mono- and bis-dibromocarbene adducts of trans- and cis-hexatriene with methyllithium proceed regiospecifically.The results are supported by labelling (12C > 99.95percent) experiments.
The stepwise nature of the γ-hydrogen rearrangement in unsaturated ions
Ture?ek, Franti?ek,Drinkwater, Donald E.,McLafferty, Fred W.
, p. 993 - 997 (2007/10/02)
The mechanism of acetaldehyde elimination from the benzyl ethyl ether cation radical (1) yielding C7H8?+ ions is re-examined. A distonic ion intermediate (2) pertinent to a stepwise route is generated independently by dissociative ionization of 3-methyl-2,4-dioxaspiro[5.5]undeca-8,10-diene and by reaction of the methylenecyclohexa-2,4-diene cation radical with acetaldehyde. Metastable 1 and 2 differ in the kinetic energy released upon dissociation (Tav=7.0 and 1.1 kJ mol-1, respectively), indicating an energy barrier to the isomerization 1 → 2. During low-energy dissociation of 2 another C7H8?+ isomer, probably the more stable toluene cation radical, is also formed. This apparently takes place in an ion-molecule complex with acetaldehyde via reversible hydrogen transfer involving the acetaldehyde oxygen atom and represents an entropy bottleneck of the elimination. These competing second steps should produce D/H and the 18O/16O isotope effects in addition to the D/H effect of the first step 1 → 2, accounting for the observations by Bowie, Derrick, et al. attributed to a concerted mechanism; we believe this to be the first case involving this mechanism for a double isotope effect in a stepwise reaction. The kinetic energy release data, intermediate preparation and dissociation, and product characterization by collisionally activated dissociation spectra support a stepwise mechanism.
Absorption Spectra and Photochemical Rearrangements of Alkyl- and Dialkylbenzene Cations in Solid Argon
Kelsall, Benuel J.,Andrews, Lester
, p. 5893 - 5898 (2007/10/02)
Matrix photoionization of alkyl- and dialkylbenzenes produced and trapped the parent radical cations.Irradiation in the visible parent cation absorption induced α-H transfer to the cation ring to give substituted methylenecyclohexadiene cations.The ease of 1,3-hydrogen transfer in these experiments suggests that this may be an important rearrangement in gaseous alkylbenzene cations.Subsequent ultraviolet photolysis of these samples produced substituted styrene cations.