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Identifier uch.chemistry.phd//1991DIS0174
Title Μηχανιστικές μελέτες και συνθετικές εφαρμογές καταλυτικών φωτοξειδώσεων
Author Στρατάκης, Μανόλης Γ
Thesis advisor Ορφανόπουλος, Μιχαήλ
Abstract In this course of this research, the Ene reaction of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) with alkanes. Trapping experiments, primary and secondary isotope effects have been studied. The major findings are the following: 1) PTAD reacts with unsymmetrical cis- and trans-alkenes with regioselective double-bond formation at the larger alkyl group. 2) The reaction with tetrasubstituted alkenes was found to favor hydrogen abstraction from the alkyl group that is geminal to the larger substituent of the double bond. 3) Electronic effects or rotational energy barriers of the alkyl substituents of the double bond appear to have almost no effect. 4) Syn addition of PTAD to trisubstituted alkenes. 5) Interception of the proposed diaziridinium imide intermediate (A.I.) in the reaction of isomeric alkenes with PTAD in methanol shows retention of stereochemistry and excludes isomerization of the reactans of the formation open carbocation. 6) Entropic control of the selectivity in the adduct of PTAD with alkenes in methanol and intermolecular competition between nucleophilic solvents suggest the existence of a "loose" SN2 type bimolecular transition state between th A.J. intermediate and the solvent. 7) Intra- and intermolecular primary and secondary isotope effect measurements suggest the formation of the A.I. intermediate at the rate determing step of this reaction. 8) Quantum mechanical "tunneling" in PTAD addition to sterically hindered alkanes.
Language Greek
Issue date 1991-10-01
Date available 1997-06-6
Collection   School/Department--School of Sciences and Engineering--Department of Chemistry--Doctoral theses
  Type of Work--Doctoral theses
Permanent Link https://elocus.lib.uoc.gr//dlib/f/6/1/metadata-dlib-1991DIS0174.tkl Bookmark and Share
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