62880-92-6Relevant academic research and scientific papers
Cyclisation reactions of 2-substituted benzoylphosphonates with trialkyl phosphites via nucleophilic attack on a carbonyl-containing ortho substituent
Cheong, Yuen-Ki,Duncanson, Philip,Griffiths, D. Vaughan
, p. 2329 - 2338 (2008/09/18)
Dimethyl 2-acetoxy- and dimethyl 2-benzoyloxy-benzoylphosphonate undergo cyclisation and deoxygenation in the presence of excess trimethyl phosphite to give dimethyl (3-methyl-1-benzofuran-2-yl)phosphonate and dimethyl (3-phenyl-1-benzofuran-2-yl)phosphonate, respectively. The reaction pathway has been shown to involve phosphite attack on initially formed tricyclic dioxaphospholane intermediates with the subsequent loss of two molecules of trimethyl phosphate. In the absence of additional trimethyl phosphite the initially formed tricyclic dioxaphospholane intermediates lose one molecule of trimethyl phosphate and then undergo a novel rearrangement to give β-ketophosphonates. The mechanism for this reaction helps explain some previously reported epoxide rearrangements. In contrast, the initially formed anionic intermediate from the reaction of dimethyl 2-benzoyloxymethylbenzoylphosphonate with trimethyl phosphite undergoes decomposition to give a carbene intermediate which is trapped by the trimethyl phosphite to give an ylidic phosphonate.
Pyridoxal-Mediated Dephosphonylation of 1-Amino Phosphonic Acids
Calvo, Kim C.
, p. 3654 - 3658 (2007/10/02)
The reaction between pyridoxal and α-amino phosphonic acids is reported.Under the proper conditions, the amino phosphonates can be induced to undergo a pyridoxal-promoted cleavage of the P-C bond.The reaction requires a metal ion and a phosphonic acid that possesses a chelating heteroatom in a position β to the amino group.At 100 deg C and pH 8.8, the dephosphonylation reaction is a first-order process, producing orthophosphate and an aldehyde from the amino phosphonate and pyridoxamine from the pyridoxal.The mechanism proposed for this reaction is based on an analogy with the pyridoxal-catalyzed decarboxylation of α-amino acids.The reactions reported represent the first observation of an α dephosphonylation mediated by pyridoxal.
