Development of New oxidation Processes Utilizing New Low toxic Oxidizing Agent "Bromocopper (II) t-butoxide"

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In this study, the development of new oxidation processes utilizing bromocopper (II) t-butoxide and preparation of an inexpensive copper (II) oxidizing agent using tertiary amine were examined.1. Oxidation of alpha-hydroxy and alpha-amino acids accompanied with decarboxylation : alpha-Disubstituted alpha-hydroxy carboxylic acids were oxidized with decarboxylation by the treatment with 2 equiv of bromocopper (II) t-butoxide to give the corresponding ketones. On the other hand, in the case of alpha-amino acids, oxidation of an amino group to an imino group and oxidative decarboxylation of the resulting alpha-imino carboxylic acid proceeded successively to produce alkanenitriles in high yields.2. Oxidative transformation of hydrazones to gem-dihalides : gem-Dihalides were selectively produced without contamination of vinyl halides by the treatment of hydrazones, which were easily prepared by the treatment of aldehydes and ketones with hydrazine hydrate in the presence of molecular sieves 4A,with copper (II) halide and t-butoxylithium.3. Transformation of dihydrazones to alkynes : The treatment of dihydrazones prepared from 1,2-diketones with copper (II) oxidizing agent gave the corresponding alkynes in quantitative yields.4. Synthesis of unsymmetrical 1,6- and 1,5-diketones by the oxidative cleavage : Cyclohexane- and cyclopentane- 1,2-diols, prepared from the corresponding cycloakane- 1,2-dioned and Grignard reagents, were oxidized with copper (II) agent to form diketones in high yields.5. Development of new oxidizing agent "copper (II) bromide-triethylamine" and its application to the oxidation of hydrazones : By the combined use of copper (II) halides and triethylamine, hydrazones were tranformed to gem-dihalides in good yields. Dihydrazones prepared from 1,2-diketones also converted to alkynes using this new oxidizing agent which is less inexpensive than copper (II) bromide-lithium t-butoxide.