70951-50-7Relevant articles and documents
Carbene-Catalyzed Reductive Coupling of Nitrobenzyl Bromide and Nitroalkene via the Single-Electron-Transfer (SET) Process and Formal 1,4-Addition
Wang, Yuhuang,Du, Yu,Huang, Xuan,Wu, Xingxing,Zhang, Yuexia,Yang, Song,Chi, Yonggui Robin
supporting information, p. 632 - 635 (2017/02/10)
A carbene-catalyzed reductive 1,4-addition of nitrobenzyl bromides to nitroalkenes is disclosed. The reaction proceeds via a carbene-enabled single-electron-transfer process that generates radicals as key intermediates. The present study expands the potentials of carbene catalysis and offers unusual transformations for common substrates in organic synthesis.
The kinetics and mechanism of the reaction of p-nitrocumyl bromide with azide ions in dimethyl sulfoxide. Evidence for a heterolytic reaction
Paine, Stuart W.,Ridd, John H.
, p. 2571 - 2575 (2007/10/03)
The reaction of p-nitrocumyl bromide 1 with azide ions in [2H6]dimethyl sulfoxide does not show the strong photochemical catalysis and inhibition by electron acceptors and radical traps characteristic of the reactions of the corresponding chloride in dipolar aprotic solvents and used as evidence for a SRN1 reaction. Instead, the bromide reacts by a heterolytic mechanism that is approximately first-order with respect to both the substrate and the lithium azide. The results can be interpreted in terms of the preassociation mechanism proposed by Richard and Amyes for the reaction of p-nitrocumyl chloride with azide ions in aqueous trifluoroethanol but there is some evidence for the participation of the azide ion in heterolysis of the C-Br bond.
Electronic Effects on Triplet and Singlet Excited-State Carbonyl Formation in the Thermolysis 3-Aryl-3-methyl-1,2-dioxetanes
Richardson, William H.,Stiggal-Estberg, Diana L.
, p. 4173 - 4179 (2007/10/02)
A series of para- and meta-substituted 3-aryl-3-methyl-1,2-dioxetanes (1) was studied in order to evaluate the electronic effect of substituents on the efficiencies of excited-state carbonyl production.All substituents reduced the efficiency of triplet carbonyl production.Several correlations point to the formation of a triplet carbonyl exciplex, originating from a triplet biradical, in the thermolysis of 1.It also appears that substituent variation in the proacetophenone portion of 1 results in triplet efficiency changes primarily in formaldehyde, which can be rationalized in terms of a triplet exciplex.Substituent effects on singlet (S1) efficiency are markedly different from those observed with triplet efficiencies.The possibility of heavy-atom effects in 1 was pursued with p-Br and m-Br substituents.No detectable heavy-atom effect was observed with singlet (S1) efficiencies, but the p-Br substituent appeared to decrease the triplet efficiency.This suggests that a p-Br heavy-atom effect may operate from the triplet exciplex, providing the approximations used in the evaluations of the heavy-atom effect are valid.The effect of substituents on rate of thermolysis of 1 provides further evidence for a biradical mechanism.