title: Solvolysis of 14,17-etheno-bridged 16α-nitroestratrienyl acetate and lactam formation pathways studied by LC-NMR and LC-MS. Structures of minor products.
abstract: The ethanol solvolysis of 3-methoxy-14,17-etheno-16α-nitroestra-1,3,5(10)-trien-17β-yl acetate in the presence of NaHCO3 was studied by means of real-time NMR experiments, LC-SPE-NMR, and LC-MS. The pathway to form 3-methoxy-2'-oxopyrrolidino-[4',5':14β,15β]-estra-1,3,5(10)-trien-17-one was disclosed. The intermediacy of nitrile oxide and alkoxynitrone was postulated based on the analysis of the reaction products. The proposed mechanism of cleaving the bridge in the nitro compound is legal for the formation of N-acetoxylactams, nitriles, isoxazoles and isoxazolines.
authors: Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str. 5/2, 220143 Minsk, Belarus. Electronic address: baranovsky@iboch.bas-net.by.
authors: Alexander V
authors: AV
authors: Baranovsky
authors: Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich Str. 5/2, 220143 Minsk, Belarus.
authors: Dmitry A
authors: DA
authors: Bolibrukh
authors: Max Planck Institute for Chemical Ecology, Beutenberg Campus, Hans Knöll Str. 8, D-07745 Jena, Germany.
authors: Bernd
authors: B
authors: Schneider
mesh_terms: D002853:Chromatography, Liquid; D004958:Estradiol / Q000031:analogs & derivatives* / Q000737:chemistry; D007769:Lactams / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008968:Molecular Conformation; D011760:Pyrrolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D017693:Sodium Bicarbonate / Q000737:chemistry; D012995:Solubility
chemical_list: D007769:Lactams; D011760:Pyrrolidinones; D004958:Estradiol; D017693:Sodium Bicarbonate
keywords: Alkoxynitrone; Bridged steroid cleavage; Lactam; Nitrile oxide; Rearrangement