{"id":{"repo_id":"sheffield-hallam","oai_identifier":"oai:shura.shu.ac.uk:19405"},"canonical_url":"https://search.dev.ndltd.org/etd/sheffield-hallam/oai:shura.shu.ac.uk:19405","repository":{"repo_id":"sheffield-hallam","name":"Sheffield Hallam University","base_url":"https://shura.shu.ac.uk/cgi/oai2"},"display":{"title":"Studies in pyrimidine chemistry.","abstract":"The synthesis of a series of 2-chloro-5-(hetero)arylpyrimidines and 5-(hetero)arylpyrimidines has been investigated. The aryl substituted pyrimidines are readily obtainable from [3-(dimethylamino)-2-aryl allylidene] dimethylammonium perchlorates whilst the heteroaryl substituted pyrimidines are best prepared by the photolysis of the appropriate 5-iodopyrimidine in the presence of a heteroarene.The photolysis of a series of 5-idopyiraidines in heteroarene solutions has been investigated, the reaction giving high yields except for the case of 4-chloro-5-iodopyrimidine, this result being apparently due to the high reactivity of the 4-chloro substituent.The kinetics of the reaction between piperidine and a series of 2-chloro-5-(hetero)arylpyrimidines in aqueous dioxan has been investigated. The order of electron-withdrawing ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl < phenyl < 2-thienyl 2-furyl. This result is shown to be consistent with current ideas on the nature of these substituents.The kinetics of the reaction between phenacylbromide and a series of 5-(hetero)-arylpyrimidines in acetonitrile was investigated. The order of electron-donating ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl > 2-furyl> 2-thienyl > phenyl. An explanation is proposed for this order. The molecular structure of 2,4-diazido-5-iodopyrimidine was determined by single crystal X-ray crystallographic studies. The molecule was found to exist in the diazido form rather than one of the several possible tretrazolo tautomers. 2,4-Diazidopyrimidines are usually found to exist in one of the tetrazolo forms, the 5-iodo substituent is shown to stabilize the diazido tautomer. An attempt was made to determine the molecular structure of 2,4-diazido-6-methylpyrimidine which has been the subject of some controversy but due to crystal, twinning an X-ray crystallographic study could not be completed.","abstract_html":"The synthesis of a series of 2-chloro-5-(hetero)arylpyrimidines and 5-(hetero)arylpyrimidines has been investigated. The aryl substituted pyrimidines are readily obtainable from [3-(dimethylamino)-2-aryl allylidene] dimethylammonium perchlorates whilst the heteroaryl substituted pyrimidines are best prepared by the photolysis of the appropriate 5-iodopyrimidine in the presence of a heteroarene.The photolysis of a series of 5-idopyiraidines in heteroarene solutions has been investigated, the reaction giving high yields except for the case of 4-chloro-5-iodopyrimidine, this result being apparently due to the high reactivity of the 4-chloro substituent.The kinetics of the reaction between piperidine and a series of 2-chloro-5-(hetero)arylpyrimidines in aqueous dioxan has been investigated. The order of electron-withdrawing ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl &lt; phenyl &lt; 2-thienyl 2-furyl. This result is shown to be consistent with current ideas on the nature of these substituents.The kinetics of the reaction between phenacylbromide and a series of 5-(hetero)-arylpyrimidines in acetonitrile was investigated. The order of electron-donating ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl &gt; 2-furyl&gt; 2-thienyl &gt; phenyl. An explanation is proposed for this order. The molecular structure of 2,4-diazido-5-iodopyrimidine was determined by single crystal X-ray crystallographic studies. The molecule was found to exist in the diazido form rather than one of the several possible tretrazolo tautomers. 2,4-Diazidopyrimidines are usually found to exist in one of the tetrazolo forms, the 5-iodo substituent is shown to stabilize the diazido tautomer. An attempt was made to determine the molecular structure of 2,4-diazido-6-methylpyrimidine which has been the subject of some controversy but due to crystal, twinning an X-ray crystallographic study could not be completed.","abstract_has_math":false,"creators":["Buckland, David J."],"institution":"Sheffield Hallam University (United Kingdom).","degree_name":"phd","degree_level":"doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1978,"date_issued":"1978","date_published":"1978","updated_at":"2026-07-24T06:31:14Z","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":["Buckland, David J."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1978"]},{"key":"dc:date.issued","label":"Date","values":["1978"]},{"key":"dc:publisher.commercial","label":"Dc Publisher Commercial","values":["Sheffield Hallam University,"]},{"key":"dc:publisher.department","label":"Dc Publisher Department","values":["Department of Chemistry."]},{"key":"dc:publisher.institution","label":"Dc Publisher Institution","values":["Sheffield Hallam University (United Kingdom)."]},{"key":"dc:relation.isreferencedby","label":"Dc Relation Isreferencedby","values":["https://shura.shu.ac.uk/19405/"]},{"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://shura.shu.ac.uk/19405/1/10694286.pdf"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The synthesis of a series of 2-chloro-5-(hetero)arylpyrimidines and 5-(hetero)arylpyrimidines has been investigated. The aryl substituted pyrimidines are readily obtainable from [3-(dimethylamino)-2-aryl allylidene] dimethylammonium perchlorates whilst the heteroaryl substituted pyrimidines are best prepared by the photolysis of the appropriate 5-iodopyrimidine in the presence of a heteroarene.The photolysis of a series of 5-idopyiraidines in heteroarene solutions has been investigated, the reaction giving high yields except for the case of 4-chloro-5-iodopyrimidine, this result being apparently due to the high reactivity of the 4-chloro substituent.The kinetics of the reaction between piperidine and a series of 2-chloro-5-(hetero)arylpyrimidines in aqueous dioxan has been investigated. The order of electron-withdrawing ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl < phenyl < 2-thienyl 2-furyl. This result is shown to be consistent with current ideas on the nature of these substituents.The kinetics of the reaction between phenacylbromide and a series of 5-(hetero)-arylpyrimidines in acetonitrile was investigated. The order of electron-donating ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl > 2-furyl> 2-thienyl > phenyl. An explanation is proposed for this order. The molecular structure of 2,4-diazido-5-iodopyrimidine was determined by single crystal X-ray crystallographic studies. The molecule was found to exist in the diazido form rather than one of the several possible tretrazolo tautomers. 2,4-Diazidopyrimidines are usually found to exist in one of the tetrazolo forms, the 5-iodo substituent is shown to stabilize the diazido tautomer. An attempt was made to determine the molecular structure of 2,4-diazido-6-methylpyrimidine which has been the subject of some controversy but due to crystal, twinning an X-ray crystallographic study could not be completed."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Studies in pyrimidine chemistry."]}]}],"canonical_facts":{"dc:creator":["Buckland, David J."],"dc:date":["1978"],"dc:date.issued":["1978"],"dc:description.abstract":["The synthesis of a series of 2-chloro-5-(hetero)arylpyrimidines and 5-(hetero)arylpyrimidines has been investigated. The aryl substituted pyrimidines are readily obtainable from [3-(dimethylamino)-2-aryl allylidene] dimethylammonium perchlorates whilst the heteroaryl substituted pyrimidines are best prepared by the photolysis of the appropriate 5-iodopyrimidine in the presence of a heteroarene.The photolysis of a series of 5-idopyiraidines in heteroarene solutions has been investigated, the reaction giving high yields except for the case of 4-chloro-5-iodopyrimidine, this result being apparently due to the high reactivity of the 4-chloro substituent.The kinetics of the reaction between piperidine and a series of 2-chloro-5-(hetero)arylpyrimidines in aqueous dioxan has been investigated. The order of electron-withdrawing ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl < phenyl < 2-thienyl 2-furyl. This result is shown to be consistent with current ideas on the nature of these substituents.The kinetics of the reaction between phenacylbromide and a series of 5-(hetero)-arylpyrimidines in acetonitrile was investigated. The order of electron-donating ability of the heteroaryl substituents was found to be 1-methylpyrrol-2-yl > 2-furyl> 2-thienyl > phenyl. An explanation is proposed for this order. The molecular structure of 2,4-diazido-5-iodopyrimidine was determined by single crystal X-ray crystallographic studies. The molecule was found to exist in the diazido form rather than one of the several possible tretrazolo tautomers. 2,4-Diazidopyrimidines are usually found to exist in one of the tetrazolo forms, the 5-iodo substituent is shown to stabilize the diazido tautomer. An attempt was made to determine the molecular structure of 2,4-diazido-6-methylpyrimidine which has been the subject of some controversy but due to crystal, twinning an X-ray crystallographic study could not be completed."],"dc:format":["application/pdf"],"dc:identifier.uri":["https://shura.shu.ac.uk/19405/1/10694286.pdf"],"dc:language":["en"],"dc:publisher.commercial":["Sheffield Hallam University,"],"dc:publisher.department":["Department of Chemistry."],"dc:publisher.institution":["Sheffield Hallam University (United Kingdom)."],"dc:relation.isreferencedby":["https://shura.shu.ac.uk/19405/"],"dc:title":["Studies in pyrimidine chemistry."],"dc:type":["Thesis"],"dc:type.qualificationlevel":["doctoral"],"dc:type.qualificationname":["phd"]},"updated_at":"2026-07-24T06:31:14Z"}