Syntheses of Polycyclic Structures

Campbell, Joan E (1949) Syntheses of Polycyclic Structures. PhD thesis, University of Glasgow.

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Part 1. An attempt to synthesise s-hexahydrochrysene (XIV) using the inactive alphabeta-diphenylglutaric acid (XX) of higher m. p. as staring material, is described. Cyclisation of the anhydride of this acid produced alpha-phenyl-1-indanone-3-acetic acid (XXXV) instead of the expected derivative of tetralone, (XXI). A stereoisomer of (XXXV) was prepared by esterification and hydrolysis. Clemmensen redaction and chain lengtlening by the Arndt-Eistert procedure, of both these isomers produced two forms of beta-phenyl-beta-l-indanepropionic acid (LIX). Cyclisation and reduction of the two homo-acids gave two hydrocarbons, 1-phenyl-1:2:3:9-tetrahydroacenaphthene, (LXl), the structure of which was shown by dehydrogenation and oxidation of the product to 2-phenyl-1:8-naphthalic anhydride (LXVIII). Part 11. d1-alphabeta-Di-1-naphthyIsuccinic acid (I) has been synthesised from naphthalene as follows: Chloromethyl-naphthalene (IX) was prepared and converted into naphthyl-acetic acid via the nitrile. The sodium derivative of the ester of this acid underwent self-condensation by means of iodine to give the racemic and me so forms of ethyl-alphabeta-dinaphthyIsuccinate (XII), both of which were hydrolysed to the corresponding racemic acid (I). In the hope of obtaining a hexacyclicdihydric phenol (II), several attempts have been made to cyclise the anhydride of (1). Aluminium chloride in a variety of solvents was used, and anhydrous hydrofluoric acid, but all these attempts were unsuccessful and the line was abandoned. Part III. An attempt has been made to prepare the as yet unknown 4:5-dimethylphenanthrene. (IV), from pyrene (I) by the use of two different reactions. Treatment with osmium tetroxide gave a diol (II) which was oxidised to a substance believed to be phenanthrene-4:5-dialdehyde (XVII). This compound could not be reduced to the required hydrocarbon (IV). Ozonisation of pyrene gave phenanthrene-4-aldehyde-5-carboxylic acid (III. The aldehyde group of this acid could not be reduced in a straightforward manner. The methyl ester, however, was reduced using lithium aluminium hydride to 4:5-dihydroxymethylphenanthrene (XXVI), which did not yield the expected dichloromethyl compound on treatment with hydrochloric acid but instead produced a cyclic ether through loss of water. This work is still in progress.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1949
Depositing User: Enlighten Team
Unique ID: glathesis:1949-79763
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 03 Mar 2020 10:38
Last Modified: 03 Mar 2020 10:38

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