Synthesis, Structure and Reactivity of a Cyapho-Cyanamide Salt
Synthesis, Structure and Reactivity of a Cyapho-Cyanamide Salt
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氰基氰酰胺盐的合成、结构和反应性
DOI：
10.1002/ange.202111619
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发表时间：
2021
影响因子：
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通讯作者：
Ergöçmen D
中科院分区：
文献类型：
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作者：
Ergöçmen D
本文描述了由[Na(18‐crown‐6)][PH2]（18‐crown‐6=1,4,7,10,13,16‐六氧基环十六烷）与二甲基N‐氰碳酰咪酯（MeO）2C=N（CN）反应合成cyapho‐氰酰胺盐[Na(18‐crown‐6)][N(CN)(CP)]。反应继续进行，消除了两个当量的甲醇。仔细调整反应条件，可以分离和表征theN‐氰基（羧酸酯）磷化物中间体[HP{C(OMe)N(CN)}]−。由于甲醇在这些反应混合物中的不利影响，可以通过添加碱（LiHMDS）来中和生成的醇来实现[Na(18‐crown‐6)][N(CN)(CP)]的大规模合成。对该阴离子的进一步反应性研究表明，磷原子的官能化是可行的，可以产生一个新的氰化物官能化磷杂环家族。
We describe a facile synthesis of the cyapho‐cyanamide salt [Na(18‐crown‐6)][N(CN)(CP)] from reaction of [Na(18‐crown‐6)][PH2] (18‐crown‐6=1,4,7,10,13,16‐hexaoxacyclooctadecane) with dimethylN‐cyanocarbonimidate, (MeO)2C=N(CN). The reaction proceeds with elimination of two equivalents of methanol. Careful tuning of the reaction conditions allowed for the isolation and characterization of theN‐cyano(carboximidate)phosphide intermediate [HP{C(OMe)N(CN)}]−. Due to the adverse effects of methanol in these reaction mixtures, a bulk scale synthesis of [Na(18‐crown‐6)][N(CN)(CP)] could be achieved by addition of a base (LiHMDS) to neutralize the resulting alcohol. Further reactivity studies of this anion reveal that functionalization at the phosphorus atom is viable to yield a new family of cyanide‐functionalised phosphorus heterocycles.