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  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement of Alkyl Groups in N-phosphorylated AlkoxyphosphazenesWith diazomethane the tetrachloride as well as the tetraethylester of imidodiphosphoric acid form mixtures of O- and N-methyl derivatives. However diazoethane reacts with the tetraethyl ester only by O-ethylation yielding triethoxyphosphazene phosphoryl diethyl ester. Trichlorophosphazene phosphoryl dichloride reacts with methyl or ethyl alcohol in the molar ratio of 1:1 forming alkoxydichlorophosphazene phosphoryl dichlorides. The rearrangement of the O-alkyl derivatives to the N-alkyl isomers has been proved by 1H- and 31P-n.m.r. spectroscopy. In the case of triethoxyphosphazene phosphoryl diethyl ester it only occurs in the presence of ethyl iodide as catalyst.
    Notes: Sowohl das Tetrachlorid als auch der Tetraäthylester der Imidodiphosphorsäure bilden mit Diazomethan Gemische der O- und N-Methylderivate. Diazoäthan jedoch reagiert mit dem Tetraäthylester ausschließlich unter O-Äthylierung zum Triäthoxyphosphazenphosphoryldiäthylester. Trichlorphosphazenphosphoryldichlorid reagiert mit Methanol bzw. Äthanol im Molverhältnis 1:1 zu den Alkoxydichlorphosphazenphosphoryldichloriden. Die Umlagerung der O-Alkylderivate in die N-Alkylisomeren wurde mittels 1H- und 31P-NMR-Spektroskopie bewiesen. Im Falle des Triäthoxyphosphazenphosphoryldiäthylesters erfolgt sie nur in Gegenwart von Äthyljodid als Katalysator.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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