92545-12-5Relevant academic research and scientific papers
Reaction of tert-alkoxyl and alkyl radicals with styrene studied by the nitroxide radical-trapping technique
Nakamura, Tomoyuki,Busfield, W. Ken,Jenkins, Ian D.,Rizzardo, Ezio,Thang, San H.,Suyama, Shuji
, p. 5578 - 5582 (2007/10/03)
The reactions of tert-alkyl peroxypivalates 1 (R = methyl, ethyl, and n- propyl) with styrene in the presence of the free-radical scavenger (1,1,3,3- tetramethyl-2,3-dihydro-1H-isoindol-2-yl)oxyl (2) have been studied at 60 °C. tert-Butyl and tert-alkoxyl radicals (tert-butoxyl, tert-pentyloxyl, and tert-hexyloxyl radicals) were generated from the thermolysis of 1, and the derivative alkyl radicals (methyl, ethyl, n-propyl, and 4-hydroxy-4- methylpentyl radicals) were formed by subsequent unimolecular reactions (β- scission and 1,5-H shift) of the corresponding tert-alkoxyl radicals. The extent of the unimolecular reactions of the tert-alkoxyl radicals (versus addition to styrene) and the relative reactivity of alkyl radicals toward addition to styrene were obtained from the competitive addition/trapping reactions. The absolute rate constants for the addition of tert-butyl, ethyl, methyl, and n-propyl radicals to styrene at 60 °C were estimated to be (7.4, 4.7, 5, and 5.4) x 105 M-1 s-1, respectively.
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.
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.
