5336-95-8Relevant articles and documents
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Kauffmann,Burger
, p. 1662,1664 (1954)
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Synthetic Diversity from a Versatile and Radical Nitrating Reagent
Zhang, Kun,Jelier, Benson,Passera, Alessandro,Jeschke, Gunnar,Katayev, Dmitry
supporting information, p. 12929 - 12939 (2019/09/17)
We leverage the slow liberation of nitrogen dioxide from a newly discovered, inexpensive succinimide-derived reagent to allow for the C?H diversification of alkenes and alkynes. Beyond furnishing a library of aryl β-nitroalkenes, this reagent provides unparalleled access to β-nitrohydrins and β-nitroethers. Detailed mechanistic studies strongly suggest that a mesolytic N?N bond fragmentation liberates a nitryl radical. Using in situ photo-sensitized, electron paramagnetic resonance spectroscopy, we observed direct evidence of a nitryl radical in solution by nitrone spin-trapping. To further exhibit versatility of N-nitrosuccinimide under photoredox conditions, the late-stage diversification of an extensive number of C?H partners to prepare isoxazolines and isoxazoles is presented. This approach allows for the formation of an in situ nitrile oxide from a ketone partner, the presence of which is detected by the formation of the corresponding furoxan when conducted in the absence of a dipolarophile. This 1,3-dipolar cycloaddition with nitrile oxides and alkenes or alkynes proceeds in a single-operational step using a mild, regioselective, and general protocol with broad chemoselectivity.
Succinimidylation and nitration of aromatic compounds by photolysis with N-nitrosuccinimide
Calvert, Jane,Eberson, Lennart,Hartshorn, Michael P.,Svensson, Jan O.
, p. 645 - 652 (2007/10/02)
N-Nitrosuccinimide (S-NO2) engages in weak charge transfer complexes with aromatic compounds (ArH).Upon photolysis with light of λ > 345 nm in dichloromethane, electron transfer within the charge transfer complex leads to the triad -NO2>from which products of eventual succinimidylation and/or nitration develop by initial attack of succinimide anion upon the radical cation.Photolysis in the presence of trifluoroacetic acid (0.4 mol dm-3) causes inactivation of S- by protonation, making EPR detection of ArH-radical cations or radicals cations formed by its further transformations possible.In acetonitrile, trifluoroacetic acid is too weak effectively to protonate S-, whereas addition of stronger acids again leads to the development of EPR spectra of ArH-radical cation in the case of 9,10-dimethylanthracene, the intensity increasing with decreasing pK of the acid.An X-ray crystal structure is reported for N-nitrosuccinimide.