1408252-59-4Relevant academic research and scientific papers
O2-functionalized methylamine diazeniumdiolates: Evidence for e ←2 Z equilibration in an acyclic system
Biswas, Debanjan,Holland, Ryan J.,Deschamps, Jeffrey R.,Cao, Zhao,Keefer, Larry K.,Saavedra, Joseph E.
, p. 10804 - 10810 (2012)
Diazeniumdiolates that have the structure RHNa-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 O2-benzyl derivative. To prepare enough for efficient characterization, we devised an alternate synthesis involving a novel N-dealkylation route. CH3HNa-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 CH3HNa-N(O)=NOEt. The results could lead the way to a fuller understanding of the chemistry of the acyclic (E)-diazeniumdiolates.
