Poly-aryl ferrocenes and related compounds

McVey, Samuel (1964) Poly-aryl ferrocenes and related compounds. PhD thesis, University of Glasgow.

Abstract

The syntheses of phenyl substituted ferrocenes from the corresponding cyclopentadienes by throe routes are described. The first involved treatment of the sodium salt of the cycolopentadiene with ferrous chloride and the other two involved the high temperature interaction of the oyclopentadiene with iron pentacarbonyl and dicyclopentadienyldi-iron tetra-carbonyl This last route yielded the symmetrical (i.e. both rings substituted) and the unsymmetrical (i.e one ring unsubstituted) ferrocenes, in addition to ferrocene ituelf. The moot not feature of this work was the failure to obtain decaphenylferrocene. The syntheses of two new cyclopentadienes, 1,4-dimethy1-2,3-diphenyl- and 2,5-rimoy1-34henl-dpy Gyclopentadinp are dusted. These two products have been converted to the corresponding ferrocones. Reaction of iron pentacarbo4y1 with 5-bromo-1,2,3,4-tetraphenyl- and 5-bromo pentaphenyloyclopentadiene gave 1,2,3,4-tetraphenylcyclopenta-dienyliron dicarbonyl bromide and the pentaphenyl-analogue respectively. The reactions of this latter product are described detail. Steric effects operative in this series of poly aryl ferrocienes are discussed. In order to complete the above series, a route to the unknown hydrocarbon 1,2-diphenyloyclopentadiene was sought. The dehydration of eithcr 1-hydroxy-3,4-diphenyl- 1 cyclopont-2-ene or 1,2-dihydroxy-1,2-diphenylcyclopentane was found to give the dimeric bis(1,2-diphenyloyc1opentadiene). pyrolysis of this product gave the exo-isomer, while under more stringent conditions 1,4-diphonylcyclopentadiene was obtained Bis-(1,2-diphenylcyolopentadiene) on treatment with iron pentacarbonyl gave a black crystalline product C19A16Fe the structure of which was not determine, with molybdenum hexa-oarbonyl bis-(1,2-diphenylcyclopentadienylmolybdenum tricarbonyi) was obtained. Attempted syntheses of 1,2-diphony1cyclopenta dienes bearing a labile gouping, such as an cater or methoxy groups, are described. Anhydroacetonebenzil and its substituted analogues were chosen as convenient starting materials. During the course of this work a new route to phenylcyclopentenones giving high yields, was developed The N.M.R. spectra of various cyoloDentadienes9 phenyl substituted cyclopentenones and bis-(3,4-diphenyloyclopentadienene) are discussed and analysed. Several clarifications of dubious structures are made. The attempted conversion of 1,1-bis(chloromercuri)- ferrocene to 1,1-dimothoxyferrocene is described. Reductive cleavage of methovferrocene followed by treatment with ferrous chloride gave only trace amounts of 1,1-dimethoxy ferrocene. The acetylation of monomethoxyferrocene, under conditions which did not promote demethoxy1ation, and the attempted separation of the isomeric components by vapour phase and ordinary chromatographic techniques are described hainomethylation of 1,1g-dimethoxyferrocene gave isomeric mixtures of mono and diamine hy1ated products. The first on rechromatograpkw gave to component, whose structures wewe not asuigned. Reduction of the latter to dimethoxy-dimethylferrocenes followed by chromatography in petroleum ether failed to achieve any separation.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Additional Information: Adviser: P L Pauson
• Keywords: Organic chemistry
• Date of Award: 1964
• Depositing User: Enlighten Team
• Unique ID: glathesis:1964-73331
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 14 Jun 2019 08:56
• Last Modified: 14 Jun 2019 08:56
• URI: https://theses.gla.ac.uk/id/eprint/73331