140667-03-4Relevant academic research and scientific papers
Radicals through Photoinduced Electron Transfer. Addition to Olefin and Addition to Olefin-Aromatic Substitution Reactions
Mella, Mariella,Fagnoni, Maurizio,Albini, Angelo
, p. 5614 - 5622 (2007/10/02)
The radical cations of 2,2-dialkyl- and 2-alkyl-2-aryl-1,3-dioxolanes, when generated in solution by photoinduced electron transfer to 1,2,4,5-benzenetetracarbonitrile (TCB), fragment to yield alkyl radicals.These are trapped by electron-withdrawing substituted alkenes (acrylonitrile, methyl acrylate, methyl vinyl ketone, as well as dimethyl maleate and fumarate).The radicals thus formed are either reduced by the TCB radical anion or add to it.In the first process (observed only with the diesters) the end result is reductive alkylation of the olefin, while the latter process results in an addition to the olefin-aromatic substitution reaction.The selectivity of the process is explained on the basis of steric hindrance, since the radicals react when still in the cage with the aromatic radical anion.
Photochemical Reaction of Arenecarbonitriles in the Presence of Alkylsilanes, Silyl Ethers and Silyl Amines
Mella, Mariella,d'Alessandro, Nicola,Freccero, Mauro,Albini, Angelo
, p. 515 - 519 (2007/10/02)
The irradiation of benzene-1,2,4,5-tetracarbonitrile, and benzene-1,2,4- as well as benzene-1,3,5-tricarbonitrile in the presence of various tetraalkylsilanes, alkoxytrialkylsilanes, hexamethyldisiloxane or heptamethyldisilazane leads to alkylation of the aromatics.The more substituted alkyl group is selectively fragmented, and the attack takes place at the position(s) of highest spin density in the nitrile radical anion.The reaction involves electron transfer to the nitrile's singlet excited state, and the radical cation appears to cleave mainly in the initial radical ion pair.
Electron-donating Behaviour of Aliphatic Carboxylic Acids in the Photoreaction with 1,2,4,5-Tetracyanobenzene
Tsujimoto, Kazuo,Nakao, Nobuhisa,Ohashi, Mamoru
, p. 366 - 367 (2007/10/02)
Irradiation of an acetonitrile solution of 1,2,4,5-tetracyanobenzene with aliphatic carboxylic acids gives 2,4,5-tricyanoalkylbenzenes efficiently; electron transfer from the carboxylic acids to the excited tetracyanobenzene is essential.
