DARWIN Digitale Dissertationen German Version Strich

FU Berlin
Digitale Dissertation

Wolf Dietrich Neudorff :
Work on Synthesis and Properties of Belt Shaped Fluoranthenes
Arbeiten zu Synthese und Eigenschaften gürtelförmiger Fluoranthene

 FU Logo

|Abstract| |Table of Contents| |More Information|

Abstract

The synthesis and structural characterization of the double-stranded carbon skeleton of a C84 fullerenes belt region has been achieved. The synthetic methodology described is based on cyclic dimerization of diastereomeric AB-type monomers by non diastereospecific Diels-Alder reaction with isobenzofuran and acenaphthylene groups as reactive termini. Four diasteromeric monomer precursors have been prepared, using dihydropyracylene for the first time in a multi-step synthesis. The synthesis of dihydropyracylene itself has been optimized. This hydrocarbon, which shows essential structural features of the fullerenes was made available on the 10 g scale. The dimerization of the monomers showed a remarkable concentration independence under certain conditions, to give good yields of the cyclic dimer even in bulk. The belt-shaped macrocycle obtained from dimerization of the monomers has been partly aromatized by acid catalyzed dehydration reaction. This partly aromatized macrocycle differs from the fully unsatured belt by two ?water? molecules. Semiempirical AM1 calculations on electronic and thermodynamic properties of cyclic fluoranthenes, linear fluoranthenes, and cyclacens revealed strain energy as the essential reason for the incomplete aromatization. X-ray crystallographic structures in the crystals of the macrocycles, one of the monomers, and two diasteromeric epoxybenzo[k]fluoranthenes are also given. In addition, the first route to 8,9-didehydrofluoranthenes was developed and applied in the synthesis of a diphenylfluoranthenofluoranthene. The X-ray crystallographic structures in the crystals of the latter is given. This route is an important step toward the synthesis of the C60-fullerenes equator region and structurally related open chain polymers with the pattern of peri- and ortho-fused naphthalenic units.

Table of Contents

Download the whole PhDthesis as a zip-tar file or as zip-File

For download in PDF format click the chapter title

0. Titelblatt und Inhaltsverzeichnis
1. Einleitung 1
2. Aufgabenstellung 3
3. Syntheseplanung 6
4. Zielstruktur 17
5. Auswahl und Synthese der Grundbausteine 21
6. Synthese der Monomere 31
7. Cyclisierungsreaktionen 42
8. Aromatisierungsversuche 55
9. Zur Struktur des partiell aromatisierten Makrocyclus 64
10. AM1-Berechnung cyclischer Fluoranthene, Cyclacene und linearer Acene 66
11. Weiterführende Experimente 112
12. Zusammenfassung / Summary 124
13. Experimenteller Teil 128
14. Literatur 160

More Information:

Online available: http://www.diss.fu-berlin.de/2002/60/indexe.html
Language of PhDThesis: german
Keywords: Macrocycles; PAH; AM1; Fluoranthenes; Belt shaped PAHs; Fullerenes
DNB-Sachgruppe: 30 Chemie
Date of disputation: 09-Apr-2002
PhDThesis from: Fachbereich Biologie, Chemie, Pharmazie, Freie Universität Berlin
First Referee: Prof. Dr. Arnulf Dieter Schlüter
Second Referee: Prof. Dr. U.-H. Reißig
Contact (Author): w.d.neudorff@gmx.de
Contact (Advisor): adschlue@chemie.fu-berlin.de
Date created:22-Apr-2002
Date available:24-Apr-2002

 

|| DARWIN|| Digitale Dissertationen || Dissertation|| German Version|| FU Berlin|| Seitenanfang ||

Mail-Icon Fragen und Kommentare an:
darwin@inf.fu-berlin.de

© Freie Universität Berlin 1999