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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: Bis(trimethylsilyl)phosphates of 1,1,1,4,4,4-Hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol and 1,1,1,3,3-Pentafluoro-2-propenolThe monocyclic phosphorane (EtO)3P[OC(CF3)2C(CF3)2O] 1 was hydrolized to give a mixture of an acyclic and a cyclic phosphate, 3 and 4.The trihydroxyphosphorane 2 could not be obtained. Iodotrimethylsilane 6 converts 1 into the silylated derivative of 4 which was found also besides (Me3SiO)2P(O)OC(CF3)2C(CF3)2OSiMe3 8 in the reaction of 3 and 4 with Me3SiCl/(Me3Si)2NH. (Me3SiO)3P 10 and hexafluoroacetone did not yield the tris(trimethylsiloxy)phosphorane 5, but the phosphonate 11 which gave (Me3SiO)2P(O)OC(CF3) — CF2 12 upon heating with the loss of fluorotrimethylsilane.
    Notes: Das monozyklische Phosphoran (EtO)3P[OC(CF3)2C(CF3)2O] 1 hydrolysierte zu einem Gemisch zweier Phosphorsäureester, einem azyklischen 3 und einem zyklischer 4, ohne daß das Trihydroxyphosphoran 2 erhalten werden konnte.Iodtrimethylsilan 6 überführte 1 in das silylierte Derivat von 4, welches neben (Me3SiO)2P(O)OC(CF3)2OSiMe3 8 auch bei der Umsetzung von 3 und 4 mit Me3SiCl/(Me3Si)2NH entstand. Die Reaktion von (Me3SiO)3P 10 mit Hexafluoraceton ergab kein Tris(trimethylsiloxy)-phosphoran 5, sondern den Phosphonsäureester 11, der beim Erhitzen unter Fluortrimethylsilanabspaltung in (Me3SiO)2P(O)OC(CF3) — CF2 12 überging.
    Type of Medium: Electronic Resource
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