N-(dialkylphosphinoyl)hydroxylamines : Preparation using N,O-bis(trimethylsilyl)hydroxylamine and migration of simple alkyl groups in the rearrangements of their O-p-nitrobenzenesulphonates
作者:Martin J.P. Harger、P.Andrew Shimmin
DOI:10.1016/s0040-4020(01)90367-9
日期:1992.9
Treatment of Pri2P(O)Cl with Me3SiNHOSiMe3 gives Pri2P(O)NHOSiMe3, which is desilylated by methanol giving Pri2P(O)NHOH. The O-p-nitrobenzenesulphonyl derivative of this rearranges with KOBut in ButOH, an isopropyl group migrating from P to N and the phosphonamidate PriP(O)(OBut)NHPri being formed quantitatively. Rearrangement also occurs in other alcohols (MeOH, EtOH, PriOH), but not quite as cleanly
用Me 3 SiNHOSiMe 3处理Pr i 2 P(O)Cl产生Pr i 2 P(O)NHOSiMe 3,其被甲醇甲硅烷基化,得到Pr i 2 P(O)NHOH。所述ø - p此重排用的甲部衍生物-nitrobenzenesulphonyl吨在卜吨OH,异丙基迁移从P到N和镨的磷酰胺酯我P(O)(OBU吨)NHPr我被定量地形成。重排也发生在其他的醇(甲醇,乙醇,镨我OH),但不是很干净。在卜Ť NH2所述phosphinoylhydrazine镨我2 P(O)NHNHBu吨形成以及重排产物,镨我P(O)(NHBu吨)NHPr我。与Me 3 SiNHOSiMe 3相似地制备的Et 2 P(O)NHOH和Pr i MeP(O)NHOH的对硝基苯磺酰基衍生物也与Bu t OH-KOBu t进行了定量重排。在后一种情况下,两个烷基(Pr i和Me)的迁移能力几乎相同。