Neue Synthesen Und Reaktionen in Der Adamantan-Reihe
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Der Kohlenwasserstoff Adamantan der Summenformel C H 10 16 enthalt als Kohlenstoffgerust die kleinste Kohlenstoff- einheit, die man aus dem Diamantgitter herausschalen kann und bei der die Kohlenstoffatome in der fur das Diamantgit- ter charakteristischen Lage fixiert sind. Der Kohlenwasser- stoff ist frei von Spannung und bietet eine Fulle von inter- essanten physikalischen und chemischen Eigenschaften. Funktionelle Gruppen an diesem Ringsystem zeichnen sich in der Regel durch herabgesetzte Reaktionsfahigkeit aus. Der Grund hierfur ist einmal ein sterischer Effekt, be- dingt durch die Raumerfullung des Adamantyl-Restes, zum anderen aber auch die durch den groBen hydrophoben Rest bedingte St6rung der Solvatation. In der vorliegenden Arbeit wurden im ersten Teil Umlage- rungen untersucht, die bei der Umsetzung von Aryl-Gring- nard-Verbindungen von I-Brom-adamantan beobachtet wurden. Im zweiten Teil wurde die Verwendung von l-Adamantyl-Resten enthaltenden Schutzgruppen in der Synthese von Aminosauren und Peptiden untersucht. Im letzten Teil der Arbeit wurden Adamantyl-Reste ent- haltende a-Aminosauren und ihre Derivate hergestellt. Von besonderem Interesse waren hierbei die Herstellung und Untersuchungen von a-Lactamen. - 2 - A Ober Metallorganische Reaktionen mit 1-Bromadamantan In unserem Arbeitskreis wurde fruher gefunden, daB bei der Umsetzung von 2,6-Diethylphenylmagnesiumbromid mit 1-Bromadamantan, als einziges Substitutionsprodukt 1-(3,5-Diethylphenyl)adamantan gewonnen werden kann. Als Grund fur die Umlagerung waren Substituenteneinflusse verantwortlich gemacht. In dieser Arbeit wurden die Einflusse anderer Substi- en ten untersucht. Die nachfolgende Tabelle gibt Auskunft daruber, wie stark eine Grignard-Verbindung aufgrund sterischen und elektro- nischen Effekten der Substituenten zur Umlagerung neigt.
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