3463-79-4Relevant academic research and scientific papers
Absorption Spectra and Photochemical Rearrangements of the 1,2-Benzotropilidene Molecule and Parent Cation in Solid Argon
Kelsall, Benuel J.,Andrews, Lester,Trindle, Carl
, p. 4898 - 4903 (2007/10/02)
Argon matrix samples of 1,2-benzotropilidene have been subjected to near- and vacuum-ultraviolet photolysis.Near-UV radiation initiated rearrangement to benzonorcaradiene and methylnaphthalene isomers.Vacuum-UV radiation produced a broad 20300-cm-1 band, which is assigned to the 1,2-benzotropilidene parent cation in agreement with the spectrum calculated by the CNDO method.Visible photolysis rearranged the parent cation to the benzonorcaradiene cation and then to the 1-hydro-2-methylenenaphthalene cation; near-UV radiation produced the methylnaphthalene cations.
PHOTOCHEMISTRY OF BENZOTRICYCLO2,7>HEPTENE: SINGLET EXCITED STATE REACTIONS DERIVED FROM CYCLOPROPANE RING CLEAVAGE
Johnson, Richard P.,Davis, Katherine Schlimgen
, p. 3171 - 3174 (2007/10/02)
Direct irradiation of the title hydrocarbon in cyclohexane affords 2-vinylindene and benzonorcaradiene as major primary photoproducts.Deuterium labeling is used to determine reaction mechanisms.
THE PHOTOCHEMISTRY OF BENZOTRICYCLO2,6>HEX-3-ENE
Kouwenhoven, Arjan P.,Noort, Paul C. M. van,Cerfontain, Hans
, p. 1745 - 1748 (2007/10/02)
Irradiation of 1 in methanol with λ 254 nm yields 3 and 4 as the main primary products which result from the excited singlet state by initial cyclopropane bond homolysis, but no primary photosolvolysis products.
Conversion of Benzo- and Naphthonorcaradien-7-yl to Benzo- and Naphthotropyl Radicals
Pomerantz, Martin,Dassanayake, N. L.
, p. 678 - 682 (2007/10/02)
Thermal decompositions of tert-butyl 2,3-benzonorcaradiene-7-percarboxylate (7), tert-butyl 2,3-(2',3'-naphtho)norcaradiene-7-percarboxylate (8), bis(2,3-benzonorcaradiene-7-carbonyl) peroxide (9), and bis peroxide (10) have been studied with particular attention paid to the hydrocarbon products, 2,3-benzonorcaradiene (11) and 1,2-benzotropilidene (12) from 7 and 9, and 2,3-(2',3'-naphtho)norcaradiene (14) and 1,2-(2',3'-naphtho)tropilidene (15) from 8 and 10.The variation of product ratio with solvent from 7 and 8 suggests that the intermediate benzo- and naphthonorcaradien-7-yl radicals competitively abstract a hydrogen atom or undergo ring opening to the corresponding tropyl radical.A similar study of 9 and 10 suggests that there is an additional, polar component to formation of seven-membered ring products 12 and 15.Since the hydrocarbon products are free radical in origin, it is suggested that the intermediates, whether highly polarized species or free cations, must revert back to free radicals before giving these products.It is further suggested that the greater degree of ring opening from the diacyl peroxides, 9 and 10, is due to the greater allowedness of the ring opening of the norcaradienyl type cations relative to the corresponding radicals.It is also demonstrated that benzonorcaradienyl intermediates undergo ring opening more readily than the corresponding naphthonorcaradienyl intermediates.
