Syntheses of Polycyclic Aromatic Hydrocarbons

Kelly, William (1958) Syntheses of Polycyclic Aromatic Hydrocarbons. PhD thesis, University of Glasgow.

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1: 9-5:10-Diperinaphthyleneanthracene was synthesised by ring closure of 1:5-dichloro-9:10-di-1'-naphthylanthracene with potassium hydroxide in quinoline. The hydrocarbon was compared with the previously known 1:9-4:10 isomer, which was also resynthesised by the above method. The spectrum of the 1:9-5:10 isomer did not agree with the theoretical predictions of Dewar (J. Chem. Soc. , 1952,3539). 1:9-5:10-Diperinaphthyleneanthracene forms an endocyclic mono addition product with maleic anhydride, but on prolonged heating with maleic anhydride and chloranil two molecules of the anhydride are irreversibly condensed with the hydrocarbon and the dianhydride of dinaphtho (7':1'-1:13) (1":7"-6:8)peropyrene tetracarboxylic acid is formed. Decarboxylation of this acid with copper powder and quinoline gave the dinaphthoperopyrene, but if soda lime was used a second hydrocarbon was also obtained. This was shown by X-ray crystaliographic studies to be circumanthracene, the third member of the series formed by coronene and ovalene. In the course of an attempted alternative synthesis of circumanthracene, the hydrocarbon 3:4-5:6-10:11-12:13-tetrabenzoperopyrene was prepared. The structural and spectral relationship of several dioxides of increasing degree of condensation, derived from 1:5-di-2'-naphthyloxyanthraquinone was studied, and a hydrocarbon obtained by reduction and dehydrogenation of one of them was shown by an independent synthesis to be 1:2-benzoperylene. Terrylene was synthesised by an unambiguous route and shown to be similar to the hydrocarbon alleged to be quaterrylene by Zinke et al. (Monatsh. 1955,86,853) but different from the terrylene previously prepared by Clar (Chem. Ber., 1948,81,52). A hydrocarbon which is considered to be quaterrylene was synthesised by condensation of perylene. The condensation of phenanthrene and chrysene with phthalic anhydride and with o-toluoyl chloride under the influence of aluminium chloride at high temperatures and using tetrachloroethane as solvent was studied. This resulted in the synthesis of heptaphene and 2:3-8:9-dibenzopicene from phenanthrene and 2:3-benzopicene from chrysene. Throughout these investigations, spectra were recorded and in many cases were invaluable in assigning correct structures.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1958
Depositing User: Enlighten Team
Unique ID: glathesis:1958-79265
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 31 Mar 2020 09:09
Last Modified: 31 Mar 2020 09:09

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