7575-82-8Relevant articles and documents
Chemoselectivity of Nitroxylation of Cage Hydrocarbons
Ivleva, E. A.,Klimochkin, Yu. N.,Leonova, M. V.
, p. 1702 - 1710 (2020/12/01)
Abstract: The composition of reaction mixtures obtained by nitroxylation of 13 cage hydrocarbons with 100% nitric acid and its mixtures with acetic acid, acetic anhydride, and methylene chloride has been studied. More reactive substrates react with lowest
Aerobic oxidations with N-hydroxyphthalimide in trifluoroacetic acid
Gunchenko, Pavel A.,Li, Jing,Liu, Bifu,Chen, Hongyan,Pashenko, Alexander E.,Bakhonsky, Vladyslav V.,Zhuk, Tatyana S.,Fokin, Andrey A.
, p. 72 - 79 (2018/02/13)
The potential of highly polar trifluoroacetic acid as a media for the metal-free aerobic oxidations propagated by phthalimide N-oxyl- (PINO) radical was demonstrated experimentally utilizing N-hydroxyphthalimide (NHPI) as a catalyst and HNO3 or NaNO2 as promoters. The oxidations of toluene, cyclohexane, adamantane, diamantane, and 3-oxadiamantane gave, respectively, benzaldehyde, adipic acid, 1-hydroxyadamantane, 1-hydroxydiamantane, and 9-hydroxy-3-oxadiamantane with up to 90% selectivities under high conversions of starting material. From the density functional theory computations at the M06-2X and B3LYP-D3 levels the polarized transition structures (TS) for the hydrogen abstraction from toluene and benzyl alcohol with highly electrophilic PINO-radical are substantially stabilized by non-covalent interactions (π–π stacking). Such additional stabilization is not present in the TS for the H-abstraction from benzaldehyde thus retarding its over-oxidation to benzoic acid.
The synthesis and evaluation of new α-hydrogen nitroxides for 'living' free radical polymerization
Braslau, Rebecca,O'Bryan, Greg,Nilsen, Aaron,Henise, Jeff,Thongpaisanwong, Thanchanok,Murphy, Erin,Mueller, Laura,Ruehl, Jean
, p. 1496 - 1506 (2007/10/03)
Three N-alkoxyamines were synthesized for use in nitroxide-mediated radical polymerization. Upon thermolysis, they generate new acyclic α-hydrogen nitroxides: one adamantyl substituted and two diol-containing nitroxides. The initiators were tested in polymerization reactions in direct comparison with the initiator derived from the nitroxide TIPNO. Georg Thieme Verlag Stuttgart.