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

本研究主要探讨了叔丁醇溴化铜氧化新工艺的开发和叔胺法廉价铜氧化剂的制备.伴随脱羧的α-羟基和α-氨基酸的氧化：通过用2当量的溴代叔丁醇铜（II）处理脱羧来氧化α-二取代的α-羟基羧酸，得到相应的酮。另一方面，在α-氨基酸的情况下，氨基氧化成亚氨基和所得α-亚氨基羧酸的氧化脱羧连续进行，以高产率制备烷腈。腙氧化转化为偕二卤代物：在分子筛4A存在下，由醛和酮与水合肼反应制备的腙，经卤化铜和叔丁氧基锂处理，选择性地生成偕二卤代物，而不污染卤代乙烯。二腙转化为炔：由1，2-二酮制备的二腙与铜（II）氧化剂反应，得到定量的炔.氧化裂解法合成不对称1，6-和1，5-二酮：由相应的环烷烃-1，2-二酮和格氏试剂制备的环己烷-1，2-和环戊烷-1，2-二醇用铜试剂氧化，高产率地生成二酮.新型氧化剂“溴化铜-三乙胺”的研制及其在腙类化合物氧化中的应用：卤化铜与三乙胺联用，可使腙类化合物高产率地转化为偕二卤化物。由1，2-二酮制备的二腙也使用这种比溴化铜（II）-叔丁醇锂便宜的新氧化剂转化为炔。

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.