Basic Derivatives of Fluorene and Anthracene, and Isomerisation Reactions with Hydrogen Fluoride

Aitken, Roxburgh R (1950) Basic Derivatives of Fluorene and Anthracene, and Isomerisation Reactions with Hydrogen Fluoride. PhD thesis, University of Glasgow.

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Part I. Attempts to prepare the basic esters beta-diethyl-aznino ethyl 1,2,3,4,10,11-hexahydrof luorene-9-carboxylate and beta-diethylaminoethyl 1,2,3,4,9,10,11,12-octahydro-anthracene-9-carboxylate for testing as antispasmodic drugs have been made. These compounds have certain structural features which, in similar compounds, have been found to enhance the antispasmodic properties of these compounds. The reduction of fluorene-9-carboxylic acid has been studied with limited success. Hexahydrofluorene-9-carboxylic acid, an intermediate required in the synthesis of the former ester, has been obtained but only in poor yield. A further acid of unknown structure and several neutral by-products have also been isolated. Other synthetic methods failed due to the reluctance of hexahydro-fluorenone to form a cyanhydrin and the ease with which 9-halogene-hexahydrofluorenes decomposed. trans- as-hexahydroanthrone did not form a cyanhydrin so that trans- as- octahydroanthracene-9-carboxylio acid, an intermediate in the synthesis of the latter ester, was not obtained. The basic ethers, beta-diethylaminoethyl fluorenyl-9-ether. beta-diethylsaminoethyl hexahydrofluorenyl-9-ether and beta-diethylaminoethyl trans-as-octahydroanthranyl-9-ether, also required for testing as antispasmodic drugs, were obtained by condensation of the sodio-derivatives of the alcohols 9-fluorenol, hexahydrofluoren-9-ol and 9-hydroxy-traus-as-octahydroanthracene, respectively, with beta-diethylaminoethyl chloride. Summary, Part II. A study of a new type of isomerisation reaction (68, 69) using hydrogen fluoride as catalyst has been extended to durene (1,2,4,5-tetramethylbenzene) and penta-methylbenzene derivatives. It has been confirmed that migration of methyl groups in this reaction occurs only when accompanied by cyclisation. Durene, durylcarboxylic acid and durylacetic acid were unaffected by treatment with hydrogen fluoride at room temperature . Under similar conditions beta-durylpropionic acid was partially converted to a mixture of 4,5,7-trimethyl-indan-l-one and 4,5,6,7-tetramethylindan-l-one. The latter ketone was also obtained from beta-pentamethylphenylpropionio acid under identical conditions. Similarly 1-durylbutyric acid yielded 5,6,7,8-tetramethyl-1,2,3,4-tetrahydroanphthalen-l-one. l-pentamethylphenylbutyric acid was recovered un- changed on similar treatment. Similarities between this type of reaction and previously described isomerisation reactions have been noted though migration in this new type of isomerisation reaction appears to be much more limited in extent. A possible mechanism for the new type of reaction, based on these similarities, has been evolved. A partial isomerisation in the durene nucleus under the influence of aluminium chloride under mild conditions has been noted and correlated to a similar isomerisation in the s-octahydroanthracene nucleus and to the Jacobsen reaction.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Organic chemistry
Date of Award: 1950
Depositing User: Enlighten Team
Unique ID: glathesis:1950-79808
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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