{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70222"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70222","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Part One: Ozonolysis of Diphenylvinylene Carbonate. Synthesis and Thermolysis of Dibenzoyl Monoperoxycarbonate. Part Two: Singlet Oxygen: The Lifetime of Singlet Oxygen in Solution and Its Reaction With Ene-Type Olefins","abstract":"The reaction of ozone and diphenylvinylene carbonate is found to give dibenzoyl monoperoxycarbonate in good yield. A mechanism for the formation of this peroxide is proposed and is consistent with the Criegee mechanism for ozonolysis of most olefins. The thermolysis of dibenzoyl monoperoxycarbonate in benzene is also reported. The products of that thermolysis are very similar to the products of benzoyl peroxide thermolysis, but the rate of decay is significantly faster. The activation parameters for the decay of dibenzoyl monoperoxycarbonate were found to be consistent with the simultaneous cleavage of two bonds in the initial step.","abstract_html":"The reaction of ozone and diphenylvinylene carbonate is found to give dibenzoyl monoperoxycarbonate in good yield. A mechanism for the formation of this peroxide is proposed and is consistent with the Criegee mechanism for ozonolysis of most olefins. The thermolysis of dibenzoyl monoperoxycarbonate in benzene is also reported. The products of that thermolysis are very similar to the products of benzoyl peroxide thermolysis, but the rate of decay is significantly faster. The activation parameters for the decay of dibenzoyl monoperoxycarbonate were found to be consistent with the simultaneous cleavage of two bonds in the initial step.","abstract_has_math":false,"creators":["Hurst, John Robert"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:17:57Z","date_published":"2014-12-15T23:17:57Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Organic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8324579"],"render_values":[{"text":"(UMI)AAI8324579","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70222","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Hurst, John Robert"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:17:57Z","10000-01-01","1983"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Organic"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70222","(UMI)AAI8324579"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The reaction of ozone and diphenylvinylene carbonate is found to give dibenzoyl monoperoxycarbonate in good yield. A mechanism for the formation of this peroxide is proposed and is consistent with the Criegee mechanism for ozonolysis of most olefins. The thermolysis of dibenzoyl monoperoxycarbonate in benzene is also reported. The products of that thermolysis are very similar to the products of benzoyl peroxide thermolysis, but the rate of decay is significantly faster. The activation parameters for the decay of dibenzoyl monoperoxycarbonate were found to be consistent with the simultaneous cleavage of two bonds in the initial step.","By using a germanium photodiode detector, the emission of singlet oxygen at 1270 nm was monitored and the lifetimes of singlet oxygen in several solvents were determined. A mechanism for solvent quenching of singlet oxygen is proposed which accounts for the large solvent and solvent deuterium isotope effects on the lifetime of singlet oxygen. The relative radiative rates were also investigated and were found to be increased by aromatic solvents relative to non-aromatic solvents.","The singlet oxygen quenching rate constants for several ene-type olefins were determined and were found to depend on the structure of the olefin. This quenching is entropy dominated, and the overall rate depends on the presence of absence of hydrogen atoms on cis substituents, such that the olefins with the hydrogen containing substituents are found to quench singlet oxygen faster.","Made available in DSpace on 2014-12-15T23:17:57Z (GMT). No. of bitstreams: 1 8324579.pdf: 10649433 bytes, checksum: dc67b20cee215ab593a50de37feab319 (MD5) Previous issue date: 1983","Embargo set by: Seth Robbins for item 70388 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","352 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983."]},{"key":"dc:title","label":"Title","values":["Part One: Ozonolysis of Diphenylvinylene Carbonate. Synthesis and Thermolysis of Dibenzoyl Monoperoxycarbonate. Part Two: Singlet Oxygen: The Lifetime of Singlet Oxygen in Solution and Its Reaction With Ene-Type Olefins"]}]}],"canonical_facts":{"dc:creator":["Hurst, John Robert"],"dc:date":["2014-12-15T23:17:57Z","10000-01-01","1983"],"dc:description":["The reaction of ozone and diphenylvinylene carbonate is found to give dibenzoyl monoperoxycarbonate in good yield. A mechanism for the formation of this peroxide is proposed and is consistent with the Criegee mechanism for ozonolysis of most olefins. The thermolysis of dibenzoyl monoperoxycarbonate in benzene is also reported. The products of that thermolysis are very similar to the products of benzoyl peroxide thermolysis, but the rate of decay is significantly faster. The activation parameters for the decay of dibenzoyl monoperoxycarbonate were found to be consistent with the simultaneous cleavage of two bonds in the initial step.","By using a germanium photodiode detector, the emission of singlet oxygen at 1270 nm was monitored and the lifetimes of singlet oxygen in several solvents were determined. A mechanism for solvent quenching of singlet oxygen is proposed which accounts for the large solvent and solvent deuterium isotope effects on the lifetime of singlet oxygen. The relative radiative rates were also investigated and were found to be increased by aromatic solvents relative to non-aromatic solvents.","The singlet oxygen quenching rate constants for several ene-type olefins were determined and were found to depend on the structure of the olefin. This quenching is entropy dominated, and the overall rate depends on the presence of absence of hydrogen atoms on cis substituents, such that the olefins with the hydrogen containing substituents are found to quench singlet oxygen faster.","Made available in DSpace on 2014-12-15T23:17:57Z (GMT). No. of bitstreams: 1 8324579.pdf: 10649433 bytes, checksum: dc67b20cee215ab593a50de37feab319 (MD5) Previous issue date: 1983","Embargo set by: Seth Robbins for item 70388 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","352 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1983."],"dc:identifier":["http://hdl.handle.net/2142/70222","(UMI)AAI8324579"],"dc:subject":["Chemistry, Organic"],"dc:title":["Part One: Ozonolysis of Diphenylvinylene Carbonate. Synthesis and Thermolysis of Dibenzoyl Monoperoxycarbonate. Part Two: Singlet Oxygen: The Lifetime of Singlet Oxygen in Solution and Its Reaction With Ene-Type Olefins"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:26:02Z"}