74663-99-3Relevant articles and documents
Rhodium(III)-catalyzed regioselective C–H nitrosation/annulation of unsymmetrical azobenzenes to synthesize benzotriazole N-oxides via a RhIII/RhIII redox-neutral pathway
Zhang, Yuanfei,Chen, Zhe-Ning,Su, Weiping
supporting information, (2021/05/19)
A Rh(III)-catalyzed regioselective C–H nitrosation/annulation reaction of unsymmetrical azobenzenes with [NO][BF4] has been developed to achieve high-yielding syntheses of benzotriazole N-oxides with excellent functional group tolerance. Computational studies have revealed that this oxidative C–H functionalization reaction involves an interesting redox-neutral Rh(III)/Rh(III) pathway without the change of Rh oxidation state.
Photochemistry and thermal decarboxylation of α-phosphoryloxy-p- nitrophenylacetates
Corrie, John E. T.,Munasinghe, V. Ranjit N.,Rudbeck, Maria,Barth, Andreas
experimental part, p. 1089 - 1096 (2010/07/15)
α-Carboxy-4-nitrobenzyl phosphate 4 and its derived monomethyl phosphate ester 5 were synthesized and purified by anion-exchange chromatography. A gradient of LiCl was necessary for elution of the anion-exchange column to avoid unexpected thermal decarbox
Methylenecyclopropane Rearrangement as a Probe for Free Radical Substituent Effects. σ·Values for Potent Radical-Stabilizing Nitrogen-Containing Substituents
Creary, Xavier,Engel, Paul S.,Kavaluskas, Natasha,Pan, Li,Wolf, Allison
, p. 5634 - 5643 (2007/10/03)
A series of nitrogen-containing 2-aryl-3,3-dimethylmethylenecyclopropanes have been prepared and rearrangement rates to the corresponding 2-arylisopropylidenecyclopropanes have been measured. These rates are dependent on the nature of the nitrogen-containing group in the para-position of the aryl group. Rearrangement rates have been used to calculate σ· values, which are a measure of the radical stabilizing ability of the substituent. Groups such as p-N=N-Bu-t, p-CH=N-Bu-t, p-NH2, p-CH=N-OH, and p-CH=N-OCH3, are "good" radical stabilizers. We have also classified groups such as p-CH=N-NMe2, p-N=N-Ph, p-N=N(O)-Bu-t, p-CH=N(O)-Bu-t, and p-CH=N-O- M+, which have an extraordinarily large radical stabilizing effect, as "Super Stabilizers". These substituents stabilize the transition state of the methylenecyclopropane rearrangement by extensive spin delocalization. In the case of the latter three substituents, nitroxyl type stabilization is proposed. Density functional calculations (B3LYP/6-31G*) have been carried out on a series of nitrogen-containing substituted benzylic radicals. Rates of the methylenecyclopropane rearrangement correlate with radical stabilization energies (ΔE) determined from an isodesmic reaction of substituted benzylic radicals with toluene. These calculations confirm substantial spin delocalization onto the nitrogen-containing substituents on the para-position of the benzylic radical.
