{"id":{"repo_id":"cent-lancashire","oai_identifier":"oai:clok.uclan.ac.uk:7918"},"canonical_url":"https://search.dev.ndltd.org/etd/cent-lancashire/oai:clok.uclan.ac.uk:7918","repository":{"repo_id":"cent-lancashire","name":"University of Central Lancashire","base_url":"https://clok.uclan.ac.uk/cgi/oai2"},"display":{"title":"The Chemistry of some Di- and Tri-Phenylmethane dyes","abstract":"Two series of dyes have been prepared: a comprehensive series of novel, unsymmetrical Malachite Green type dyes containing different amino substituents in the 4-positions of the phenyl rings and a series of symmetrical Michier's Hydrol Blue type dyes. Both series of dyes have been synthesised from the relevant carbinols or hydrols. The amino substituents used were dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino and N-methylpiperazino. The rates of ailcalirie hydrolysis of the dyes at various hydroxide ion concentrations and temperatures have been investigated with a view to elucidating the reaction mechanism and the nature of substituent effects. The rate data obtained for each dye studied have been used to obtain thermodynamic activation parameters and to test the applicability of an isokinetic relationship in the dye systems. The various methods of computation and their results have been compared and discussed in relation to literature data for similar dyes. A stopped-flow technique was used for the kinetic investigation of the fast reactions associated with the unstable dyes studied. The analysis of kinetic data using single substituent parameter regression techniques has enabled substituent constants for piperidine, thiomorpholine and N-methylpiperazine to be interpolated. The steric and electronic effects of the terminal amino substituents on the visible absorption spectra of the dyes have been examined in solvents of varying acidity. The steric and electronic symmetry of the Malachite Green type dyes has been investigated and is discussed. The results from the spectral investigation and the kinetic study indicate that diphenylmethane dyes are considerably less stable than the corresponding triphenylmethane dyes and the reasons for this behaviour are discussed. In addition, piperidino, morpholino, thiomorpholino and N-methylpiperazino are less able to stabilise a dye by electron donation than dimethylamino, diethylamino and pyrrolidino and the reasons for this behaviour are also discussed. The 'H and 13C nmr spectra of the dyes and carbinols have been recorded. Certain chemical shifts have been used to determine the relative electron donor ability of the terminal amino groups. The results from the 'H and 13C nmr spectra are discussed in relation to the steric and electronic effects of the heterocycic moieties.","abstract_html":"Two series of dyes have been prepared: a comprehensive series of novel, unsymmetrical Malachite Green type dyes containing different amino substituents in the 4-positions of the phenyl rings and a series of symmetrical Michier's Hydrol Blue type dyes. Both series of dyes have been synthesised from the relevant carbinols or hydrols. The amino substituents used were dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino and N-methylpiperazino. The rates of ailcalirie hydrolysis of the dyes at various hydroxide ion concentrations and temperatures have been investigated with a view to elucidating the reaction mechanism and the nature of substituent effects. The rate data obtained for each dye studied have been used to obtain thermodynamic activation parameters and to test the applicability of an isokinetic relationship in the dye systems. The various methods of computation and their results have been compared and discussed in relation to literature data for similar dyes. A stopped-flow technique was used for the kinetic investigation of the fast reactions associated with the unstable dyes studied. The analysis of kinetic data using single substituent parameter regression techniques has enabled substituent constants for piperidine, thiomorpholine and N-methylpiperazine to be interpolated. The steric and electronic effects of the terminal amino substituents on the visible absorption spectra of the dyes have been examined in solvents of varying acidity. The steric and electronic symmetry of the Malachite Green type dyes has been investigated and is discussed. The results from the spectral investigation and the kinetic study indicate that diphenylmethane dyes are considerably less stable than the corresponding triphenylmethane dyes and the reasons for this behaviour are discussed. In addition, piperidino, morpholino, thiomorpholino and N-methylpiperazino are less able to stabilise a dye by electron donation than dimethylamino, diethylamino and pyrrolidino and the reasons for this behaviour are also discussed. The 'H and 13C nmr spectra of the dyes and carbinols have been recorded. Certain chemical shifts have been used to determine the relative electron donor ability of the terminal amino groups. The results from the 'H and 13C nmr spectra are discussed in relation to the steric and electronic effects of the heterocycic moieties.","abstract_has_math":false,"creators":["Gorman, Stephen Anthony"],"institution":"University of Central Lancashire","degree_name":"phd","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1998,"date_issued":"1998-11","date_published":"1998-11","updated_at":"2026-07-24T01:35:42Z","subjects":[],"languages":["en"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Gorman, Stephen Anthony"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1998-11"]},{"key":"dc:date.issued","label":"Date","values":["1998-11"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Environmental Management"]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["University of Central Lancashire"]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://knowledge.lancashire.ac.uk/id/eprint/7918/"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"dc:type.qualificationlevel","label":"Dc Type Qualificationlevel","values":["doctoral"]},{"key":"dc:type.qualificationname","label":"Dc Type Qualificationname","values":["phd"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://knowledge.lancashire.ac.uk/id/eprint/7918/1/Stephen%20Anthony%20Gorman%20Nov98%20the%20chemistry%20of%20some%20di-%20and%20tri-phenylmethanie%20dyes%20Doctor%20of%20%20Philosophy%20unpublished%20Nov98%20University%20of%20Central%20Lancashire%20Environmental%20Management%20332.pdf","https://knowledge.lancashire.ac.uk/id/eprint/7918/5/Stephen%20Gorman.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["Two series of dyes have been prepared: a comprehensive series of novel, unsymmetrical Malachite Green type dyes containing different amino substituents in the 4-positions of the phenyl rings and a series of symmetrical Michier's Hydrol Blue type dyes. Both series of dyes have been synthesised from the relevant carbinols or hydrols. The amino substituents used were dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino and N-methylpiperazino. The rates of ailcalirie hydrolysis of the dyes at various hydroxide ion concentrations and temperatures have been investigated with a view to elucidating the reaction mechanism and the nature of substituent effects. The rate data obtained for each dye studied have been used to obtain thermodynamic activation parameters and to test the applicability of an isokinetic relationship in the dye systems. The various methods of computation and their results have been compared and discussed in relation to literature data for similar dyes. A stopped-flow technique was used for the kinetic investigation of the fast reactions associated with the unstable dyes studied. The analysis of kinetic data using single substituent parameter regression techniques has enabled substituent constants for piperidine, thiomorpholine and N-methylpiperazine to be interpolated. The steric and electronic effects of the terminal amino substituents on the visible absorption spectra of the dyes have been examined in solvents of varying acidity. The steric and electronic symmetry of the Malachite Green type dyes has been investigated and is discussed. The results from the spectral investigation and the kinetic study indicate that diphenylmethane dyes are considerably less stable than the corresponding triphenylmethane dyes and the reasons for this behaviour are discussed. In addition, piperidino, morpholino, thiomorpholino and N-methylpiperazino are less able to stabilise a dye by electron donation than dimethylamino, diethylamino and pyrrolidino and the reasons for this behaviour are also discussed. The 'H and 13C nmr spectra of the dyes and carbinols have been recorded. Certain chemical shifts have been used to determine the relative electron donor ability of the terminal amino groups. The results from the 'H and 13C nmr spectra are discussed in relation to the steric and electronic effects of the heterocycic moieties."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["The Chemistry of some Di- and Tri-Phenylmethane dyes"]}]}],"canonical_facts":{"dc:creator":["Gorman, Stephen Anthony"],"dc:date":["1998-11"],"dc:date.issued":["1998-11"],"dc:description.abstract":["Two series of dyes have been prepared: a comprehensive series of novel, unsymmetrical Malachite Green type dyes containing different amino substituents in the 4-positions of the phenyl rings and a series of symmetrical Michier's Hydrol Blue type dyes. Both series of dyes have been synthesised from the relevant carbinols or hydrols. The amino substituents used were dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino, thiomorpholino and N-methylpiperazino. The rates of ailcalirie hydrolysis of the dyes at various hydroxide ion concentrations and temperatures have been investigated with a view to elucidating the reaction mechanism and the nature of substituent effects. The rate data obtained for each dye studied have been used to obtain thermodynamic activation parameters and to test the applicability of an isokinetic relationship in the dye systems. The various methods of computation and their results have been compared and discussed in relation to literature data for similar dyes. A stopped-flow technique was used for the kinetic investigation of the fast reactions associated with the unstable dyes studied. The analysis of kinetic data using single substituent parameter regression techniques has enabled substituent constants for piperidine, thiomorpholine and N-methylpiperazine to be interpolated. The steric and electronic effects of the terminal amino substituents on the visible absorption spectra of the dyes have been examined in solvents of varying acidity. The steric and electronic symmetry of the Malachite Green type dyes has been investigated and is discussed. The results from the spectral investigation and the kinetic study indicate that diphenylmethane dyes are considerably less stable than the corresponding triphenylmethane dyes and the reasons for this behaviour are discussed. In addition, piperidino, morpholino, thiomorpholino and N-methylpiperazino are less able to stabilise a dye by electron donation than dimethylamino, diethylamino and pyrrolidino and the reasons for this behaviour are also discussed. The 'H and 13C nmr spectra of the dyes and carbinols have been recorded. Certain chemical shifts have been used to determine the relative electron donor ability of the terminal amino groups. The results from the 'H and 13C nmr spectra are discussed in relation to the steric and electronic effects of the heterocycic moieties."],"dc:format":["application/pdf"],"dc:identifier.uri":["https://knowledge.lancashire.ac.uk/id/eprint/7918/1/Stephen%20Anthony%20Gorman%20Nov98%20the%20chemistry%20of%20some%20di-%20and%20tri-phenylmethanie%20dyes%20Doctor%20of%20%20Philosophy%20unpublished%20Nov98%20University%20of%20Central%20Lancashire%20Environmental%20Management%20332.pdf","https://knowledge.lancashire.ac.uk/id/eprint/7918/5/Stephen%20Gorman.pdf"],"dc:language":["en"],"dc:publisher.department":["Department of Environmental Management"],"dc:publisher.institution":["University of Central Lancashire"],"dc:relation.isreferencedby":["https://knowledge.lancashire.ac.uk/id/eprint/7918/"],"dc:title":["The Chemistry of some Di- and Tri-Phenylmethane dyes"],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T01:35:42Z"}