Weitkamp Robin F, Neumann Beate, Stammler Hans-Georg, Hoge Berthold
Centrum für Molekulare Materialien, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, 33615, Bielefeld, Germany.
Angew Chem Int Ed Engl. 2019 Oct 7;58(41):14633-14638. doi: 10.1002/anie.201908589. Epub 2019 Sep 9.
The reaction of a strongly basic phosphazene (Schwesinger base) with water afforded the corresponding metastable hydroxide trihydrate [OH(OH ) ] salt. This is the first hydroxide solvate that is not in contact with a cation and furthermore one of rare known water-stabilized hydroxide anions. Thermolysis in vacuum results in the decomposition of the hydroxide salt and quantitative liberation of the free phosphazene base. This approach was used to synthesize the Schwesinger base from its hydrochloride salt after anion exchange in excellent yields of over 97 %. This deprotonation method can also be used for the phosphazene-base-catalyzed preparation of the Ruppert-Prakash reagent Me SiCF using fluoroform (HCF ) as the trifluoromethyl building block and sodium hydroxide as the formal deprotonation agent.
强碱性磷腈（施韦辛格碱）与水反应生成了相应的亚稳态三水合氢氧化物[OH(OH ) ]盐。这是第一种不与阳离子接触的氢氧化物溶剂化物，也是已知的罕见的水稳定氢氧根阴离子之一。在真空中进行热解会导致氢氧化物盐分解并定量释放出游离的磷腈碱。该方法用于在阴离子交换后从其盐酸盐合成施韦辛格碱，产率极高，超过97%。这种去质子化方法还可用于以氟仿（HCF ）为三氟甲基结构单元、氢氧化钠为正式去质子化剂，通过磷腈碱催化制备鲁珀特 - 普拉卡什试剂Me SiCF 。
