Synthesis of Compounds Related to Fluoranthene

Stubbs, H. W. D (1951) Synthesis of Compounds Related to Fluoranthene. PhD thesis, University of Glasgow.

Abstract

Part 1a. The known 4-methylfluoranthene and 4-phenylfluoranthene have been synthesised by condensation of methyl and phenyl vinyl ketones, or the corresponding Mannich bases, methyl 2-morpholinoethyl ketone and 2-diethylaminoethyl phenyl ketone respectively, with methyl fluorene-9-carboxylate, followed by hydrolysis and decarboxylation, reduction, cyclisation, and dehydrogenation. Unsuccessful attempts to evolve a new synthesis of methyl fluorene-9-carboxylate were made. Part lb. 1:2:5:6-Dibenzpyracylene was synthesised by a crossed Ullmann reaction between 4-iodofluoranthene and 2-bromonitrobenzene, followed by reduction, diazotisation, and ring-closure. An attempt at synthesis by the method described in Part la failed. The ultra-violet absorption spectrum is reported and discussed, especially in relation to Clar's Anellation Theory. Part 2. 2:3-Benzfluoranthene has been synthesised from o-diphenylenephthalide by Clar's zinc dust-zinc chloride fusion method. An attempt to synthesise 2:3-benzfluoranthene by cyclisation of 9-bromo-9-o-bromo-o-tolylfluorene gave a compound believed, in the light of spectrographic and analytical evidence, to be 1:9-diphenylanthracene. The spectrum of 2:3-benzfluoranthene is reported and discussed, especially in relation to the Anellation Theory. Part 3. 3:4-Dimethylfluoranthene was obtained by the Grignard reaction on 4-keto-3-methyl-1:2:3:4-tetra-hydrofluoranthene, followed by dehydration-dehydrogenation. 2-Methoxyfluoranthene was synthesised by a crossed Ullmann reaction between 1-iodo-2-methoxynaphthalene and o-bromonitrobenzene, followed by reduction, diazotisation, and ring-closure. Part 4. The ultra-violet absorption spectra of several mono-, di-, and trimethylfluoranthenes, methoxy-fluoranthenes, and 4-phenylfluoranthene, not previously recorded, have been measured. They are shown to be of value in characterisation of the pure compounds. Distortion due to overlapping of the substituent methyl- or methoxyl- group with a hydrogen atom in the 2- or 10- substituted derivatives appears to produce corresponding distortions in the ultraviolet absorption curve.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Organic chemistry
• Date of Award: 1951
• Depositing User: Enlighten Team
• Unique ID: glathesis:1951-78887
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 30 Jan 2020 14:44
• Last Modified: 30 Jan 2020 14:44
• URI: https://theses.gla.ac.uk/id/eprint/78887