55337-80-9Relevant academic research and scientific papers
Intramolecular Reactivity of Arylcarbenes: Derivatives of o-Tolylcarbene
Kirmse, Wolfgang,Konrad, Wolfgang,Schnitzler, Dirk
, p. 3821 - 3829 (2007/10/02)
Various CH2X groups have been attached to the ortho position of phenylcarbene.If 2'- or 3'-C-H bonds are present, as in 23 (X = Me), 71 (X = CMe3), and 58 (X = SiMe3), C-H insertion leading to five- or six-membered rings predominates in the gas phase and competes with intermolecular reactions in solution.The formation of benzocyclobutenes via insertion into 1'-C-H bonds is a very minor reaction path of 23 and 71.In contrast, 58 produces substantial amounts of the benzocyclobutene 59 by way of C-Si insertion, particularly in the gas phase.Insertion into the Si-Me bonds of 58 also occurs while the C-F bonds of 37 (X = CF3) and 50 (X = F) are inert.In the gas phase, 37 and 50 give mainly benzocyclobutenes whereas intermolecular reactions prevail in solution.The effects of sensitization and of solvent polarity suggest that benzocyclobutenes arise from singlet arylcarbenes.The amount of carbene-carbene rearrangement decreases in the order 7 (X = H) > 37 (X = CF3) > 23 (X = Me); no rearrangement was observed with 50 (X = F), 58 (X = SiMe3), and 71 (X = CMe3).
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.
Photolysis and Flash Thermolysis of some 1,3-Dihydrobenzothiophen 2,2-Dioxides
Durst, Tony,Lancaster, Michael,Smith, David J. H.
, p. 1846 - 1848 (2007/10/02)
The thermolysis and photolysis of the title compounds (7) have been studied.Benzocyclobutenes (8) are the major products at lower temperatures whereas alkenes (9), derived from a hydride shift, predominante at higher temperatures and on photolysis.
