A new, practical, synthesis of β-ketophosphonates relying on the conversion of the organolithium reagentfrom a dialkyl methylphosphonate into the correspondingorganocopperreagent, and its reaction with acylchlorides is described. The structure of the intermediate organocopperreagents is discussed.
Abstract Two original acid derivatives of methylene diphosphonic acid (MDP) with two inequivalent phosphorus atoms have been synthesised: [(thiophosphonato)-methyl]phosphonic acid, (MDPS), and [(isopropyiamido phosphonato)-methyl] phosphonic acid, (MDPN). A poten- tiometric study allowed to define the stoechiometry of the complex formed between MDP and magnesium (II) in alcaline medium and a 31P NMR
摘要 合成了具有两个不等价磷原子的亚甲基二膦酸 (MDP) 的两种原始酸衍生物:[(硫代膦酸酯)-甲基]膦酸 (MDPS) 和 [(异丙酰氨基膦酸酯)-甲基] 膦酸 (MDPN) . 一项电位研究允许定义在碱性介质中 MDP 和镁 (II) 之间形成的复合物的化学计量,31P NMR 研究证明了这种 MDPMg2+ 复合物的不对称结构。Black Eriochrome T 和镁 (II) 之间的配位平衡的位移允许比较 MDP、MDPS 和 MDPN 与阳离子 Mg2+ 的配位强度。
One-Pot Alkylidenediphosphorylation of Nucleophiles
Direct phosphonylalkylidenephosphinylation of nucleophiles is achieved by one-pot mono dialkylphosphonoalkylation of dichlorophosphates or methylphosphonic dichloride followed, in situ, by nucleophilic substitution of the chlorine atom of the alkylidenediphosphorylated intermediate.