Abstract
Preparation of Phosphorus— and Fluorine‐Containing Calix[4]arene Derivatives. Conformational Analysis, Separation of the Conformers, and X‐Ray Crystal Structure Analysis of a Cone ConformerHerrn Professor Helmut Werner zum 60. Geburtstag gewidmet. The Calix[4]arene 1 reacts with hexamethyldisilazane or (diethylamino)trimethylsilane to form the bis‐trimethylsilyl‐ated derivative 2. Treatment of 2 with PF2C1 gives the mono‐and bis‐difluorophosphites 3 and 4, which react with elimination of Me3SiF or PF3 to yield the monofluorophosphite derivative 5. All four OH hydrogen atoms in 1 are replaced by lithium on reaction with nBuLi with formation of the tetrali‐thiated product 6. This has been allowed to react with the Pchlorophosphorinanones 7–9. From 7 the cone conformer 10a is formed, whereas in the case of 8 and 9 a mixture of all four possible conformars 11a‐d and 12a‐d is obtained. The pure conformers 12a‐d are isolated. By refluxing the cone conformer 12a in tetrachloroethane a conformational conversion is effected. In order to evaluate its coordinating ability, 12a was allowed to react with dichloro(cycloocta‐1, 5‐diene)platinum(II) to form the trans‐disubstituted complex 13. In the case of 12a (acetonitrile solvate) a single‐crystal X‐ray structure analysis has been conducted. The molecule displays a cone conformation, whereby two of the opposing phenyl rings are approximately parallel and the other two approximately perpendicular to each other.
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