Syntheses of Functionalised [2.2]Paracyclophanes: Structure and Reactivity Studies

[2.2]Paracyclophane, a strained sandwich structured molecule, possessing bent benzene rings due to the short ethano bridges, has interested chemists, theoreticians and industrialists over many years. It has found a wide variety of application in stereoselective synthesis, material science, basic organic and supramolecular chemistry are a few to mention. It is also a multi ton industrial product used as a monomer in polymer chemistry. In this thesis, the syntheses of various functionalised [2.2]paracyclophane derivatives possessing different substitution patterns are described. Also a new class of indanono- and indenonophanes have been described. The functionalised cyclophanes structural, chemical, mechanistic and spectroscopic properties have been studied carefully and extensively. These functionalised cyclophanes were also subjected to polymerisation by chemical vapour deposition.[2.2]Paracyclophan, ein gespanntes Molekuel mit sandwichartiger Struktur, welches aufgrund der kurzen Ethanobruecken bootfoermig verzerrte Benzolringe aufweist ist seit Jahren von Interesse für Chemiker, Theoretiker und die Chemische Industrie. Anwendungsbereiche sind unter anderem stereoselektive Synthese, Materialwissenschaften, Organische und Supramolekulare Chemie. Dieses im multi Tonnen Maßstab industriell gefertigte Produkt wird als Monomer in der Polymerchemie verwendet. In dieser Dissertation wird die Synthese einer Vielzahl funktionalisierter [2.2]Paracyclophanderivate mit einem breiten Spektrum an Substitutionsmustern beschrieben. Ebenfalls wird eine neue Klasse von Indanono- und Indenonophanen beschrieben. Die strukturellen, chemischen, mechanistischen und spektroskopischen Eigenschaften der funktionalisierten Cyclophane wurde eingehend untersucht. Darüber hinaus wurden dieser funktionalisierten Cyclophane für die Polymerisation durch Chemical Vapour Deposition genutzt

Five-membered ring annelation in [2.2]paracyclophanes by aldol condensation

Under basic conditions 4,5,12,13-tetraacetyl[2.2]paracyclophane (9) cyclizes by a double aldol condensation to provide the two aldols 12 and 15 in a 3:7 ratio. The structures of these compounds were obtained from X-ray structural analysis, spectroscopic data, and mechanistic considerations. On acid treatment 12 is dehydrated to a mixture of the condensed five-membered [2.2]paracyclophane derivatives 18–20, whereas 15 yields a mixture of the isomeric cyclopentadienones 21–23. The structures of these elimination products are also deduced from X-ray and spectroscopic data. The sequence presented here constitutes the simplest route so far to cyclophanes carrying an annelated five-membered ring

The preparation of new functionalized [2.2]paracyclophane derivatives with N-containing functional groups

The two isomeric bis(isocyanates) 4,12- and 4,16-di-isocyanato[2.2]paracyclophane, 16 and 28, have been prepared from their corresponding diacids by simple routes. The two isomers are versatile intermediates for the preparation of various cyclophanes bearing substituents with nitrogen-containing functional groups, e.g., the pseudo-ortho diamine 8, the bis secondary amine 23, and the crownophanes 18 and 19. Several of these new cyclophane derivatives (18, 19, 22, 26, 28) have been characterized by X-ray structural analysis