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- W2316397925 abstract "Diazeniumdiolates that have the structure RHN-N(O)═NOR' are of interest as prodrug (caged) forms of the bioeffectors nitric oxide (NO) and nitroxyl (HNO). Previous work has focused on examples possessing α-branched R groups, with isopropylamine (IPA)/NO (R = isopropyl) being the smallest examined to date. To probe the effect of minimizing the alkyl-group size on the chemistry of IPA/NO, we prepared the corresponding methylamine derivative as a sodium salt that was highly unstable but could be trapped in very low overall yield as the stable O(2)-benzyl derivative. To prepare enough for efficient characterization, we devised an alternate synthesis involving a novel N-dealkylation route. CH(3)HN-N(O)═NOBn, synthesized in high yield and crystallized as the Z isomer as determined by X-ray crystallography, was observed to exist as a 11:1 mixture of two isomeric forms in dynamic equilibrium in solution. Similar results were seen for the O(2)-ethyl derivative, whose two equilibrium constituents were partially separated by HPLC to reveal essentially identical UV and mass spectra, indicating them to be Z and E isomers of CH(3)HN-N(O)═NOEt. The results could lead the way to a fuller understanding of the chemistry of the acyclic (E)-diazeniumdiolates." @default.
- W2316397925 created "2016-06-24" @default.
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- W2316397925 date "2012-11-20" @default.
- W2316397925 modified "2023-09-25" @default.
- W2316397925 title "O2-Functionalized Methylamine Diazeniumdiolates: Evidence for E ⇄ Z Equilibration in an Acyclic System" @default.
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- W2316397925 doi "https://doi.org/10.1021/jo3020837" @default.
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