Chemiluminescence From the Thermal Decomposition of 1,4-Diphenyl-1,4-Dioxa-2-Benzopyran-3-One. Direct and Indirect Luminescence Involving an Ortho-Xylylene Peroxide

135 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1981.1,4-Dipheny1-1,4-dioxa-2-benzopyran-3-one (37), an endoperoxide similar in structure to the endoperoxide proposed as an intermediate in the chemiluminescent reaction of luminol, is prepared by the addition of singlet oxygen to 1,4-diphenyl-2-benzopyran-3-one. This endoperoxide yields o-dibenzoyl-benzene and phenyl-(o-benzoyl) benzoate upon thermolysis in p-xylene at 112(DEGREES)C. Chemiluminescence is observed during the decomposition of the endoperoxide. Light is also produced when 37 is heated to 112(DEGREES)C in the presence of added fluorescers. The direct chemiluminescence is the result of electron-transfer (CIEEL) between two intermediates formed during the thermolysis of 37. One intermediate has been identified as 1,4-diphenyl-2,3-benzodioxin, the first of a new class of compounds we call o-xylylene peroxides. The other intermediate remains unidentified. The chemiluminescence in the presence of fluorescers is explained by the CIEEL mechanism with the fluorescer and the o-xylylene peroxide as the reactive species.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD