21903-43-5Relevant academic research and scientific papers
Heterolytic (2 e) vs Homolytic (1 e) Oxidation Reactivity: N?H versus C?H Switch in the Oxidation of Lactams by Dioxirans
Annese, Cosimo,D'Accolti, Lucia,Fusco, Caterina,Licini, Giulia,Zonta, Cristiano
supporting information, p. 259 - 262 (2017/01/17)
Dioxiranes are powerful oxidants that can act via two different mechanisms: 1) homolytic (H abstraction and oxygen rebound) and 2) heterolytic (electrophilic oxidation). So far, it has been reported that the nature of the substrate dictates the reaction mode independently from the dioxirane employed. Herein, we report an unprecedented case in which the nature of the dioxirane rules the oxidation chemoselectivity. In particular, a switch from C?H to N?H oxidation is observed in the oxidation of lactams moving from dimethyl dioxirane (DDO) to methyl(trifluoromethyl)dioxirane (TFDO). A physical organic chemistry study, which combines the oxidation with two other dioxiranes methyl(fluoromethyl)dioxirane, MFDO, and methyl(difluoromethyl)dioxirane, DFDO, with computational studies, points to a diverse ability of the dioxiranes to either stabilize the homo or the heterolytic pathway.
PROCESS FOR PRODUCTION OF LACTAM
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Page/Page column 4, (2008/12/07)
Disclosed is a process for production of a lactam (particularly, an industrially useful lactam, e.g., laurolactam) with high selectivity, comprising hydrogenating a cyclic dicarboxylic acid imide having a large of ring members (particularly, a 8-membered or more cyclic dicarboxylic acid imide) to produce a corresponding. The process is characterized by hydrogenating a 8-membered or more cyclic dicarboxylic acid imide in the presence of ruthenium of platinum. In the process, the ruthenium or platinum may be supported on activated charcoal and an alcohol may be used as a reaction solvent.
