10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物的合成及其可变熔点现象

Synthesis and Changeable Melting Points of 10-Methoxy- 5,10-Dihydrophenophosphazine 10-Oxide

10 羟基 5,10 二氢磷杂吖嗪 10 氧化物(Ⅰ)与过量氯化亚砜回流1～1 5h,定量得到次膦酸酰氯(Ⅱ),Ⅱ与甲醇钠在甲醇中回流反应2～3h,以70%产率生成熔点为226 59℃的次膦酸甲酯(Ⅲ);若将Ⅱ直接与甲醇回流则得到双熔点(112 71℃,216 88℃)的Ⅲ(产率35%)。用粉末X ray衍射研究了Ⅲ的晶相结构,结果表明,单熔点Ⅲ具有单一晶相结构,双熔点Ⅲ则具有混合晶相结构。用1HNMR和MS确认了Ⅲ的结构。

10-Hydroxy-5,10-dihydrophenophosphazine 10-oxide (Ⅰ) was refluxed in an excess of SOCl_2 for 1～1.5 h to give quantitatively a phosphinic acid chloride (Ⅱ).When treated with MeONa in MeOH at a refluxing temperature for 2～3 h,Ⅱ can further be converted to the corresponding methyl phosphinate,10-methoxy-5,10-dihydrophenophosphazine 10-oxide (Ⅲ, 70%),with single melting point (SMP) of 226.59 ℃.The same compound Ⅲ with double melting points (DMP) of 112.71 ℃ and 216.88 ℃,however,can also be obtained in 35% yield with MeOH in lieu of MeONa during the above process.Investigation with powder X-ray diffraction revealed that Ⅲ with SMP has a single crystal phase and Ⅲ with DMP has mixed crystal phases.The structure of Ⅲ was also determined by NMR and MS.