90433-15-1Relevant academic research and scientific papers
Photosubstitution of Dicyanobenzenes by Allylic Silanes, Germanes, and Stannanes via Photoinduced Electron Transfer
Nakanishi, Kazuhisa,Mizuno, Kazuhiko,Otsuji, Yoshio
, p. 2371 - 2379 (2007/10/02)
Photoreactions of 1,2- and 1,4-dicyanobenzenes (o- and p-DCB) with allylic silanes, germanes, and stannanes in acetonitrile were studied under various conditions.In these photoreactions, one of cyano groups of o- and p-DCB was replaced by allylic groups.W
PHOTOSUBSTITUTION OF DICYANOBENZENES BY GROUP 14 ORGANOMETALLIC COMPOUNDS VIA PHOTOINDUCED ELECTRON-TRANSFER. ADDITIVE AND MEDIUM EFFECTS ON PHOTOINDUCED ELECTRON TRANSFER REACTION
Mizuno, Kazuhiko,Nakanishi, Kazuhisa,Otsuji, Yoshio
, p. 1833 - 1836 (2007/10/02)
The phenanthrene-sensitized photoreaction of 1,2- and 1,4-dicyanobenzenes with group 14 organometallic compounds containing allylic and benzylic groups in CH3CN afforded the corresponding 1- and 4-allylated benzonitriles in high yields.These photoreactions were accelerated by the addition of Mg(ClO4)2 and benzene derivatives.
Photochemical reactivity of α-phenyl β,γ-enones. Singlet 1,3-acyl shift, triplet aromatic di-?-methane (DPM) rearrangement and triplet aryl-carbonyl bridging
Koppes, Margareth J. C. M.,Beentjes, Peter C. J.,Cerfontain, Hans
, p. 313 - 324 (2007/10/02)
The photochemistry of the series of α-phenyl β,γ-enones 6-10 has been studied under conditions of both direct (λ 300 nm) and triplet-sensitized irradiation with the aim of determining the reactivity patterns of these "multi"-chromophoric systems.Upon direct irradiation, the reactants exhibit the typical photoreactions of β,γ-enones, viz. the 1,3-acyl shift, affording the corresponding (E)- and (Z)-5-phenyl-4-hexen-3-ones, decarbonylation of the radicals formed by α-cleavage and recombination of the resulting alkyl radicals and, in addition, a new type of reaction from the triplet-excited state yielding small amounts of the corresponding acetophenones.The acetophenones are thought to be formed by initial β-bridging between the carbonyl and the phenyl group, followed by extrusion of the C4H6 fragment from the 1,4- or 1,3-oxa-diradical.Upon sensitized irradiation, the o-methoxy- and p-cyano-substituted reactants 9 and 10 exhibit the di-?-methane rearrangement, leading to mixtures of the corresponding cis- and trans-1-acetyl-1-methyl-2-phenylcyclopropanes, with quantum yields of 0.03 and 0.10, respectively.The formation of the 1,3-AS and decarbonylation products illustrates the occurrence of α-cleavage, whereas the acetophenones and di-?-methane products are formed via initial aryl-carbonyl and aryl-vinyl bridging, respectively.The inability of the other α-phenyl β,γ-enones to undergo photocyclopropanation is discussed in terms of excitation-energy partition.In the o-methoxy and p-cyano-substituted reactants, the excitation energy may be predominantly concentrated in the aryl moiety in contrast to the other two systems in which the excitation energy may be mainly localized on the β,γ-enone moiety.Subsequent triplet-energy dissipation by a free-rotor mechanism would then account for the stability of these systems.This was observed for (E)-7 which, upon triplet sensitization, affords only the (Z) isomer, whereas this process is degenerate for the other substrates studied.
A NOVEL PHOTOSUBSTITUTION OF DICYANOBENZENES BY ALLYLIC AND BENZYLIC SILANES
Mizuno, Kazuhiko,Ikeda, Munehiro,Otsuji, Yoshio
, p. 461 - 464 (2007/10/02)
The photosubstitution of o- and p-dicyanobenzenes by allylic and benzylic silanes in acetonitrile occurred efficiently, giving the corresponding mono-allylated and benzylated cyanobenzenes.
Reactivity of Aryl Vinyl Di-?-methane Systems. Mechanistic and Exploratory Organic Photochemistry
Zimmerman, Howard E.,Swafford, Richard L.
, p. 3069 - 3083 (2007/10/02)
The di-?-methane rearrangement of a series of meta and para substituted arylvinylmethane reactants was investigated with the aim of determiningthe patterns of reactivity in systems in which initial excitation is localized in the aryl moiety.Thus the photo
