The condensation of dialkyl α-hydroxy-benzylphosphonates with dialkyl phosphites and that of α-hydroxybenzyl-diphenylphosphine oxide with diphenylphosphine oxide unexpectedly gave the corresponding phosphorylated α-hydroxy derivatives. This new reaction proved to be general. The formation of the two products may be similar and involves the attack of the hydroxy group of the α-hydroxyphosphonate or α-hydroxyphosphine oxide on the phosphorus atom of the trivalent tautomer form (Y₂POH) of the Y₂P(O)H reagent (Y= MeO, EtO, or Ph) going with the elimination of an alcohol and water molecule, respectively. The mechanism was supported by DFT computations at the M062X/6-31G (d,p) level of theory, including suitable proton transfer networks. The condensations discussed are typical autocatalytic reactions promoted by the alcohol or water molecules formed. The initial promoters are the traces of water inevitably present in the mixture. In the reaction of α-hydroxyphosphonates with dialkyl phosphites, the −P(O)(OR)H derivative is the primary product that is partially hydrolyzed to the −P(O)(OH)H species by the traces of water under the conditions of the reaction. Arbuzov reaction of diethyl α-bromobenzylphosphonate with ethyl diphenyphosphinite afforded the target-like phenylmethylene-phosphine oxide─phosphonate derivative.

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二烷基 α-羟基苄基膦酸盐与亚磷酸二烷基酯的意外反应和一些相关反应


二烷基 α-羟基苄基膦酸盐与二烷基亚磷酸酯的缩合以及 α-羟基苄基-二苯基膦氧化物与二苯基膦氧化物的缩合出乎意料地得到了相应的磷酸化 α-羟基衍生物。事实证明，这种新的反应是普遍的。两种产物的形成可能相似，涉及 α-羟基膦酸盐或 α-羟基膦氧化物的羟基对 Y₂P（O）H 试剂（Y= MeO、EtO 或 Ph）的三价互变异构体形式 （Y₂POH） 的磷原子的攻击，并消除醇和水分子， 分别。该机制得到了 M062X/6-31G （d，p） 理论水平的 DFT 计算的支持，包括合适的质子转移网络。讨论的缩合是由形成的醇或水分子促进的典型自催化反应。初始促进剂是混合物中不可避免地存在的微量水。在 α-羟基膦酸盐与亚磷酸二烷基反应中，−P（O）（OR）H 衍生物是初级产物，在反应条件下，微量水被痕量水部分水解成 −P（O）（OH）H 物质。α-溴苄基膦酸二乙酯与二苯膦酸乙酯的 Arbuzov 反应得到了目标样苯基亚甲基-氧化膦-膦酸盐衍生物。