Engelhardt Institute of Molecular Biology, Russian Academy of Sciences, 11991 Moscow, Russia.
School of Pharmacy, Biocenter Kuopio, University of Eastern Finland, P.O. Box 1627, FI-70211 Kuopio, Finland.
Molecules. 2017 Jun 23;22(7):1040. doi: 10.3390/molecules22071040.
Derivatives of methylenediphosphonic acid possess wide spectra of biological activities and are used in enzymology as research tools as well as in practical medicine. Carbonyl diphosphonic acid is a promising starting building block for synthesis of functionally substituted methylenediphosphonates. Investigation of the interaction of carbonyl diphosphonic acid with hydroxylamine clearly demonstrates that it is impossible to isolate oxime within the pH range 2-12, while only cyanophosphonic and phosphoric acids are the products of the fast proceeding Beckmann-like fragmentation. In the case of -alkylhydroxylamines, corresponding alcohols are found in the reaction mixtures in addition to cyanophosphonic and phosphoric acids. Therefore, two residues of phosphonic acid being attached to a carbonyl group provide new properties to this carbonyl group, making its oximes very unstable. This principally differs carbonyl diphosphonic acid from structurally related phosphonoglyoxalic acid and other α-ketophosphonates.
亚甲基二膦酸衍生物具有广泛的生物活性，在酶学中被用作研究工具，也在实际医学中得到应用。羰基二膦酸是合成功能取代的亚甲基二膦酸盐的有前途的起始构建块。对羰基二膦酸与羟胺相互作用的研究清楚地表明，在 pH 值 2-12 范围内不可能分离出肟，而只有氰基膦酸和磷酸是快速进行贝克曼样断裂的产物。在 -烷基羟胺的情况下，除了氰基膦酸和磷酸外，反应混合物中还发现了相应的醇。因此，两个膦酸残基连接到羰基上为该羰基提供了新的性质，使其肟非常不稳定。这使得羰基二膦酸与结构上相关的膦氧乙酸和其他α-酮膦酸酯明显不同。
