154463-61-3Relevant academic research and scientific papers
Benzyl radicals from toluene by photosensitization with naphthalene-1,4- dicarbonitrile - Benzylation and hydroxymethylation of unsaturated compounds
Mella, Mariella,Fagnoni, Maurizio,Albini, Angelo
, p. 2137 - 2142 (2007/10/03)
In aprotic media, photoinduced electron transfer from toluene to 1,4- naphthalenedicarbonitrile (DCN) is followed by in-cage proton transfer and radical coupling. However, in the presence of a protic co-solvent, the radical ions diffuse out of the cage and deprotonation of the toluene radical cation takes place from the free solvated species. With (BuOH, this results in reductive benzylation of DCN through coupling of benzyl radicals with DCN-·. With MeOH, secondary hydrogen abstraction by PhCH2- yields hydroxymethyl radicals, which couple with DCN-·. Both benzyl and hydroxymethyl radicals are efficiently trapped by electrophilic alkenes. Thus, in the presence of dimethyl maleate, DCN-photosensitized benzylation - or hydroxy-methylation - of the substrate occurs through direct activation of the C-H bond. The same reaction has been accomplished with acrylonitrile, albeit with a lower yield.
Set Photochemical Reactions between 1,4-Naphthalenedicarbonitrile and Benzylic Donors. Medium Effects
Fasani, E.,d'Alessandro, N.,Albini, A.,Mariano, P. S.
, p. 829 - 835 (2007/10/02)
The electron transfer induced photochemical reactions 1,4-naphthalenedicarbonitrile (NDN) with toluene (1a), diphenylmethane (1b), p-methoxytoluene (1c), and benzyltrimethylsilane (1d) in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN were examined.The results were compared with those of reactions occurring in neat MeCN.Under the former conditions, the cation radical derived from 1a undergoes deprotonation after diffusion from (rather than within) the geminate ion pair (as in MeCN).The formed benzyl radical abstracts a hydrogen from MeOH leading to hydroxymethylation of NDN competitively with its benzylation.Under basis conditions MeO(-) adds to 1a(+.) yielding 1c.The reaction of 1b in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN is similar to that of 1a.However, in the reaction of 1c under these conditions, the arene cation radical undergoes deprotonation out of cage.Finally, desilylation of the cation radical from 1d is a fast process occurring from the geminate pair in all the media explored.
