Development of New oxidation Processes Utilizing New Low toxic Oxidizing Agent "Bromocopper (II) t-butoxide"
使用新型低毒氧化剂“叔丁醇溴铜(II)”开发新的氧化工艺
基本信息
- 批准号:07555277
- 负责人:
- 金额:$ 5.25万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (A)
- 财政年份:1995
- 资助国家:日本
- 起止时间:1995 至 1996
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
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.
本文研究了利用溴铜(II) t-丁醇氧化新工艺的发展,以及叔胺制备廉价的铜(II)氧化剂。α -羟基和α -氨基酸的氧化伴随脱羧:α -二取代α -羟基羧酸通过2等量的溴铜(II) t-丁醇处理氧化伴随脱羧得到相应的酮。另一方面,在α -氨基酸的情况下,氨基氧化成亚胺基和氧化脱羧所产生的α -亚胺羧酸依次进行,以高产率生产烷腈。腙氧化转化为宝石二卤化物:在不污染卤化乙烯的情况下,通过处理腙可以选择性地生成宝石二卤化物,而在分子筛4A存在下,用铜(II)卤化物和t-丁氧基锂处理醛和酮很容易制备。二腙制炔:用铜(II)氧化剂处理1,2-二酮制的二腙,定量产率得到相应的炔。氧化裂解法合成不对称1,6-和1,5-二酮:由相应的环烷- 1,2-二酮和格氏试剂制备环己烷-和环戊烷- 1,2-二醇,用铜(II)试剂氧化生成高收率的二酮。新型氧化剂“溴化铜-三乙胺”的研制及其在腙氧化中的应用:卤化铜与三乙胺复合使用,将腙转化为二卤化宝石,收率较高。这种新型氧化剂比溴化铜(II) - t-丁醇锂更便宜,由1,2-二酮制备的二腙也能转化为炔。
项目成果
期刊论文数量(5)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Takeshi Takeda: "Transformation of Ketones and Aldehydes to gem-Dihalides Using Copper (II) Halides" Tetrahedron. 53(2). 557-566 (1997)
Takeshi Takeda:“使用铜 (II) 卤化物将酮和醛转化为宝石二卤化物”四面体。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Takeshi Takeda: "Oxidation of Hydrazones with Copper(II) Bromide-Lithium t-Butoxide.A Convenient Method for the Transformation of Ketones and Aldehydes to gem-Dibromides" SynLett. (印刷中). (1996)
Takeshi Takeda:“用溴化铜(II)-叔丁醇锂氧化腙。将酮和醛转化为二溴化物的便捷方法”SynLett(出版中)。
- DOI:
- 发表时间:
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- 影响因子:0
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- 通讯作者:
Takeshi Takeda: "Transformation of Ketones and Aldehydes to gem-Dihalides Using Copper(II) Halides" Tetrahedron. 53. 557-566 (1997)
Takeshi Takeda:“使用铜(II)卤化物将酮和醛转化为宝石二卤化物”四面体。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Takeshi Takeda: "Oxidative Decarboxylation of alpha-Amino and alpha-Hydroxy Acids Using Copper (II) Bromide-Lithium t-Butoxide" Synthesis. (5). 600-602 (1996)
Takeshi Takeda:“使用溴化铜 (II)-叔丁醇锂对 α-氨基酸和 α-羟基酸进行氧化脱羧”合成。
- DOI:
- 发表时间:
- 期刊:
- 影响因子:0
- 作者:
- 通讯作者:
Takeshi Takeda: "Transformation of Ketones and Aldehydes to gem-Dihalides Using Copper (II) Halides" Tetrahedron. 53・2. 557-566 (1997)
Takeshi Takeda:“使用铜 (II) 卤化物将酮和醛转化为宝石二卤化物”四面体 53・2 (1997)。
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TAKEDA Takeshi其他文献
TAKEDA Takeshi的其他文献
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{{ truncateString('TAKEDA Takeshi', 18)}}的其他基金
Highly Stereocontrolled Construction of Acyclic Systems Utilizing Titanocene Complexes as Synthetic Devices
利用二茂钛配合物作为合成器件高度立体控制非循环系统的构建
- 批准号:
21350026 - 财政年份:2009
- 资助金额:
$ 5.25万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Formation of Titanium-Metallacycles and Exploration of Their Reactivities
钛金属环的形成及其反应活性的探索
- 批准号:
18350018 - 财政年份:2006
- 资助金额:
$ 5.25万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Exploration of Unique Reactivity of Organotitanocene Complexes and Its Application to Organic Synthesis
有机二茂钛配合物独特反应活性的探索及其在有机合成中的应用
- 批准号:
14340228 - 财政年份:2002
- 资助金额:
$ 5.25万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Development of Highly Efficient Methods for the Construction of Carbon Frameworks Utilizing Titanium-Carbene Complexes
开发利用钛-卡宾配合物构建碳骨架的高效方法
- 批准号:
11440213 - 财政年份:1999
- 资助金额:
$ 5.25万 - 项目类别:
Grant-in-Aid for Scientific Research (B)