Darstellung und Kristallstrukturuntersuchungen einiger Biureto(thio)phosphate

Abstract

Bei der Oxydation von Ammonium‐biuretodithiophosphat 1 (NH4—BDP) entstehen Ammonium‐biuretomonothiophosphat‐Hydrat 2 (NH4—BMP · H2O) und Ammonium‐biuretooxophosphat 3 (NH4—BOP). Die Darstellung Von 2 gelingt einfacher durch Hydrolyse des Biuretothiophosphoryl‐mercaptoessigsäuremethylesters in wäßriger NH4HCO3‐Lösung. Aus den Ammoniumsalzen werden die Natrium‐ und Kaliumverbindungen bzw. deren Hydrate über die freien Säuren hergestellt. Die Hydrate K—BDP · H2O, NH4—BMP · H2O, Na—BMP · 2 H2O und K—BMP · H2O lassen sich ohne Zersetzung des cyclischen Anions entwässern. Die Ergebnisse der Kristallstrukturuntersuchungen an K—BDP · H2O, K—BMP · H2O und NH4—BOP werden vorgestellt. Die beiden Kaliumsalze erweisen sich als eng verwandt in ihrer Struktur.

A Systematic Approach to Alkali Biuretooxophosphates

“…[20,21] The corresponding sodium salt (3b) was synthesized by ion exchange in aqueous solution. [20,21] The corresponding sodium salt (3b) was synthesized by ion exchange in aqueous solution.…”

“…[20,21] The corresponding sodium salt (3b) was synthesized by ion exchange in aqueous solution. [20] We have developed a novel approach to synthesize alkali biuretooxophosphates [except the lithium salt (3a), which was obtained by ion exchange] in crystalline form by the controlled hydrolysis of 1,1,3,5-tetrachloro-1-phospha-2,4,6-s-triazine [23] in the presence of the corresponding acetate (according to the synthesis of the alkali trimetaphosphimates, Scheme 4). Previous synthesis of 3d by oxidation of NH 4 + -biuretodithiophosphate.…”

“…[20,21] We are now targeting a thorough characterization of biuretooxophosphates as possible precursors for the synthesis of new C/P/O/N-containing compounds. [20,21] We are now targeting a thorough characterization of biuretooxophosphates as possible precursors for the synthesis of new C/P/O/N-containing compounds.…”

“…The first biuretooxophosphate, namely NH 4 [PO 2 (NH) 3 (CO) 2 ] ( 3d ), was described in 1986 by Neels 20,21. We are now targeting a thorough characterization of biuretooxophosphates as possible precursors for the synthesis of new C/P/O/N‐containing compounds.…”

Ca[PO2(NH)3(CO)2]2 – The First Biuretooxophosphate with a Divalent Cation

“…Whereas cyanurates and trimetaphosphimates were first mentioned in the 19th century,11–14 biuretooxophosphates are a relatively new class of compounds. The ammonia salt was described by Neels in 1986 as by‐product of the synthesis of COS starting from urea and P 2 S 5 , the corresponding sodium salt was synthesized by ion‐exchange 15–17. Only recently, a detailed structural and spectroscopic characterization of all alkali biuretooxophosphates has been given 18.…”