Synthesis of phosphaformamidines and phosphaformamidinates.
Synthesis of phosphaformamidines and phosphaformamidinates.
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磷甲脒和磷甲脒的合成。
DOI：
10.1002/asia.200700103
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发表时间：
2007
期刊：
影响因子：
--
通讯作者：
Bertrand,Guy
中科院分区：
文献类型：
--
作者：
Song,Maoying;Donnadieu,Bruno;Soleilhavoup,Michele;Bertrand,Guy
报道了一种大规模合成各种磷酰亚胺和磷酰胺酸酯的路线，这是一种以前已知的制备磷酰亚胺和磷酰胺酸酯的方法无法获得的衍生物。热稳定性较好的N-芳基甲酸乙酯1(ArNCH(OEt)，Ar=2，4，6-(Me)3Ph或2，6-(Ipr)2Ph)与二烷基和二芳基磷酰亚胺反应生成N-芳基磷酰亚胺，产率分别为80%和60 %，而与芳基(硅基)磷酰亚胺锂反应得到芳基-N-硅基磷酰胺(产率60 %)。在1中加入初级芳基膦酸锂，然后加入化学计量比的nBuLi得到相应的磷酰亚胺(产率为70-88 %)。产物经甲基化得到芳基-N-氢磷酰亚胺(产率90-95 %)。本文还给出了其中一种磷酰亚胺的固态结构。
A large‐scale synthetic route to a variety of phosphaformamidines and phosphaformamidinates, a type of derivative that was not accessible by the methods previously known for preparing phosphaamidines and phosphaamidinates, is reported. Thermally stable ethylN‐arylformimidates1(ArNCH(OEt), Ar=2,4,6‐(Me)3Ph or 2,6‐(iPr)2Ph) readily reacted with lithium dialkyl‐ and diarylphosphanides to afford the correspondingN‐aryl phosphaformamidines in 80 and 60 % yield, respectively, whereas with lithium (aryl)(silyl)phosphanide, theN‐aryl‐N‐silylphosphaformamidine (60 % yield) was obtained. Addition of primary lithium arylphosphanides to1followed by addition of a stoichiometric amount ofnBuLi gave rise to the respective phosphaformamidinates (70–88 % yield). Methanolysis of the products afforded theN‐aryl‐N‐hydrogenophosphaformamidines (90–95 % yield). The solid‐state structure of one of the phosphaformamidinates is also presented.