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Intriguing structural chemistry of neutral and anionic layered monoalkylphosphates: single-source precursors for high-yield ceramic phosphates
CrystEngComm ( IF 3.1 ) Pub Date : 2017-08-01 00:00:00 , DOI: 10.1039/c7ce01066d
Gulzar A. Bhat 1, 2, 3, 4, 5 , Alok Ch. Kalita 1, 2, 3, 4, 5 , Ramaswamy Murugavel 1, 2, 3, 4, 5
Affiliation  

Building up on an available synthetic methodology, phosphate monoesters ROPO3H2 have been synthesized in good yields. The synthetic procedure employed features acetic anhydride mediated activation of phosphoric acid in the presence of alcohols, leading to the formation of phosphate monoesters. The products have been isolated as their cyclohexyl amine salts, [CyNH3]2[(MeO)PO3]·3H2O (1) and [CyNH3][(RO)PO3H] (Cy = cyclohexyl; R = Et (2), iPr (3), or tBu (4)). Neutralization of 1–4 by readily available inexpensive ion exchange resin Amberlite produces monoalkylphosphates (RO)P(O)(OH)2 (R = Me (5), Et (6), iPr (7), or tBu (8)). Thermally labile 1–4 and 7 have been structurally characterized by single crystal X-ray diffraction studies. Due to their intrinsic thermal instability due to β-H elimination, these compounds can be used as ligands for the preparation of single-source precursors for ceramic phosphates by reacting them with suitable metals ions. It is also possible to isolate co-crystals of the anionic and neutral forms of these phosphates as it has been demonstrated in the isolation and structural characterization of [(iPrO)PO3H2]·{[CyNH3][(iPrO)PO3H]} (9). To demonstrate the utility of these monoalkylphosphates in the low-temperature synthesis of metal phosphate bioceramics, isopropyl phosphate 7 has been employed to prepare calcium phosphate [{Ca((iPrO)PO3)(OH2)}·H2O]n (10), which undergoes neat thermal decomposition in two stages to lose water and propene to yield β-Ca2P2O7 at low temperatures (280 °C).

中文翻译:

有趣的中性和阴离子层状单烷基磷酸酯的结构化学:高产率陶瓷磷酸酯的单源前体

以可用的合成方法为基础,以高收率合成了磷酸单酯ROPO 3 H 2。所使用的合成方法的特征在于在醇存在下乙酸酐介导的磷酸活化,导致形成磷酸单酯。分离出产物为环己基胺盐[CyNH 3 ] 2 [(MeO)P​​O 3 ]·3H 2 O(1)和[CyNH 3 ] [(RO)PO 3 H](Cy =环己基; R = Et(2),iPr(3)或t Bu(4))。中和1-4通过容易获得的廉价离子交换树脂Amberlite可以生产磷酸单烷基酯(RO)P(O)(OH)2(R = Me(5),Et(6),iPr(7)或t Bu(8))。热不稳定1-47已经通过单晶X射线衍射研究对结构进行了表征。由于它们由于β-H消除而固有的热不稳定性,因此这些化合物可以用作配体,通过使它们与合适的金属离子反应,来制备陶瓷磷酸盐的单源前体。正如在[(iPrO)PO 3 H 2 ]·{[CyNH 3 ] [(iPrO)PO )的分离和结构表征中已证明的那样,也可以分离这些磷酸盐的阴离子和中性形式的共晶体。3 H]}(9)。为了证明这些单烷基磷酸酯在金属磷酸酯生物陶瓷的低温合成中的实用性,磷酸异丙酯7已用于制备磷酸钙[{Ca((iPrO)PO 3((OH 2)}·H 2 O] nn10),其经过两个阶段的纯热分解以损失水分和丙烯,从而生成β-Ca在低温(280°C)下为2 P 2 O 7
更新日期:2017-09-18
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