Date of Award
Bachelor of Science
The thermal or photolytic decomposition of diazo compounds is known to produce a carbonyloxide in the presence of oxygen. Analogously, ∝-diazoketones should produce acyl carbonyloxides. This intermediate is identical to one proposed for the ozonolysis of alkynes and its substantiation is the purpose of this study. By examining the products of the thermal, copper catalyzed phenylbenzoyldiazomethane decomposition, one should be able to determine the intermediate’s presence. Benzoic anhydride, benzil and methyl diphenyl-acetate have been identified as products and tetraphenylglycolide is also thought to be present. Methyl diphenyl-acetate is the result of Wolff rearrangement, while the other three are proposed to be derived from oxygen addition to a ketocarbene, i.e. the acyl carbonylacetate. The product's formation is speculated to be connected to the triplet and/ or singlet nature of the intermediate. The triplet state is thought to produce tetraphenylglycolide exclusively, while the singlet yields benzil and benzoic anhydride. These latter two products are also produced for diphenylacetylene ozonolysis; a noted singlet process. The presence of the singlet state is attributed to intersystem crossing promoted by the copper catalyst as the singlet’s attributed products are not found in the non-catalyzed runs.
Sawyer, Joy A ., "The decomposition of phenyl-benzoyl-diazamethane and its relevance to alkyne ozonolysis" (1977). Honors Theses. 1859.