29539-01-3Relevant academic research and scientific papers
Direct C(sp2)?H Amination to Synthesize Primary 3-aminoquinoxalin-2(1H)-ones under Simple and Mild Conditions
Yang, Qiming,Yang, Zibing,Tan, Yushi,Zhao, Jiquan,Sun, Qian,Zhang, Hong-Yu,Zhang, Yuecheng
, p. 1662 - 1667 (2019)
A convenient C?H amination of quinoxalin-2-ones has been developed. This transformation provides concise access to 3-aminoquinoxalin-2(1H)-ones with a broad tolerance of functional groups, utilizing TMSN3 as an amino source under simple and mild conditions. The target 3-aminoquinoxalin-2(1H)-ones are important intermediates for the synthesis of biologically active 3-N-substituted quinoxalin-2-one derivatives. (Figure presented.).
The synthesis of alkyl aryl nitriles from N-(1-arylalkylidene)-cyanomethylamines. Part 2. Mechanism
Perosa, Alvise,Selva, Maurizio,Tundo, Pietro
, p. 1033 - 1037 (2007/10/03)
The mechanism of the rearrangement of N-(1-arylalkylidene)cyanomethylamines ArC(=NCH2CN)R 1 to the corresponding nitriles ArCH(CN)R2 (in DMF, at 150°C, with K2CO3) is described. Reaction 1 → 2 was investigated for different types of imine 1, and it was found that with a leaving group other than CN- the reaction does not proceed to yield the nitrile, whereas imines such as PhC(=NCH2CN)H, prepared starting from aldehydes rather than ketones, yield the expected phenylacetonitrile even at temperatures as low as 120°C. Evidence for the mechanism comes from a study of the reactivity of the postulated intermediates: 2-cyano-3-phenylaziridine 4c, and 2,2-diphenyl-2H-azirine 5b. The route involving aziridine 4c is ruled out, since this compound does not react at all under the investigated conditions. The 2H-azirine 5b instead, yields the corresponding diphenylacetonitrile in DMF with K2CO3, at 150°C. The transformation seems to involve an initial deprotonation, followed by an intramolecular ring closure-CN elimination step, which yields the 2H-azirine. The azirine then isomerizes to the nitrile. Additional evidence for the intermediacy of the 2H-azirine, based on 1H NMR monitoring of the reaction 1 → 2, is described. Finally, the results of a simple isotope exchange experiment provide a rationale for the previously observed scrambling of labels, and further confirm the proposed mechanism.
