硫代四配位磷化物与邻氨基酚反应

在三乙胺存在下,多种硫代磷酰二氯与邻氨基酚反应,经磷硫双键断开并以σ键与磷相连的基团被置换下来等过程,最终生成双环五配位磷化物.苯基硫代环膦酸酯与邻氨基酚反应分别生成螺环五配位磷化物.苯氧基或烷氧基硫代环磷酸酯与邻氨基酚反应,除磷硫键断裂以及苯氧基、烷氧基被置换外,还发生邻亚氨基苯氧基与邻苯二氧基进行相互交换反应.这些反应机理依据磷原子的电负性,氢质子的活泼性以及P-X键的稳定性进行了讨论.

The reaction of tetracoordinated thiophosphoryl compounds with p-aminophenol

The reaction of RP(S)Cl2 (R = PhO, EtO, Me2CHO, Et2N, MeS, Cl) with o-aminophenol in the presence of triethylamine involved the cleavage of phosphorus-sulfur double bond and the displacement of some P-R bonds to give a pentacoordinated phosphorus compound I. The cyclic thiophosphonates II (Z = NH, O) reacted with o-aminophenol to yield spirophosphoranes III, resp. The cyclic thiophophates IV (Z1, R1 = NH, Me2CHO; O, PhO) which contain phenoxy and alkoxy groups underwent exchange reaction between o-iminophenoxy and o-phenylenedioxy groups in addition to the cleavage of phosphorus-sulfur double bond and the displacement of phenoxy and alkoxy groups. The mechanism of these reactions were discussed with respect to the electronegativity of phosphorus, the activity of hydrogen and the stability of P-R bond.