化作为一种温和而活跃的贝克曼重组催化剂
Yoshiro Furuya1, Kazuaki Ishihara, Hisashi Yamamoto
1Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa, Nagoya 464-8603, Japan.
Journal of the American Chemical Society
|August 11, 2005
概括
氨酸化物使得第一个一般的有机催化贝克曼重新排列基托克西姆到胺. 这种高效的方法,使用诸如化之类的酸作为催化剂,产生诸如尼龙-12前体之类的有价值产品.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成化学 合成化学
背景情况:
- 贝克曼重组是合成基托克西姆胺胺的关键反应.
- 为这种转变开发高效和选择性的催化系统仍然是一个活跃的研究领域.
- 有机催化剂为各种有机转化提供了一个无金属的替代方案.
研究的目的:
- 开发第一个用于氧化物贝克曼重新排列的一般器官催化系统.
- 探索化作为这种反应中的有机催化剂的功效.
- 研究使用辅助催化剂来提高反应的效率.
主要方法:
- 使用化作为主要的有机催化剂.
- 使用诸如HCl和ZnCl2之类的酸作为辅助催化剂.
- 在各种ketoximes上执行贝克曼重组,包括100毫摩尔尺度上的cyclododecanoneoxime.
主要成果:
- 首次成功实现了基托克西姆的第一个一般的有机催化贝克曼重组.
- 证明化,与诸如ZnCl2之类的酸相结合,是非常有效的.
- 使用0.5mol%的化和1mol%的ZnCl2获得了尼龙-12的前体阿扎西克洛特里德-2-,其定量产量为0.5mol%的化和1mol%的 ZnCl2.
结论:
- 化是贝克曼重组的多功能和有效的有机催化剂.
- 开发的方法提供了一种新且高效的途径,可以从ketoximes中获得胺.
- 这种有机催化方法为合成有价值的化学中间体提供了一个可持续和可扩展的替代方案.
相关概念视频
Metal-Ligand Bonds
The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Structural Isomerism
Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can be...
Complexation Equilibria: The Chelate Effect
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
EDTA: Chemistry and Properties
Polydentate ligands are most widely used in complexometric titrations because they form more stable complexes with the metal ions than mono- or bidentate ligands due to the chelate effect. Examples of polydentate ligands are ethylenediaminetetraacetic acid (EDTA), crown ethers, and cryptands. The most important feature of optimal polydentate ligands is the ability to form 1:1 complexes in a single-step process. Amino carboxylic acid derivatives are frequently used as complexing agents. EDTA is...
Complexation Equilibria: Factors Influencing Stability of Complexes
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
Complexometric Titration: Ligands
Different monodentate and polydentate ligands are used as complexing agents in complexometric titration reactions. The formation of complexes by mono- and bidentate ligands involves two or more intermediate steps, limiting their use as complexing agents. In comparison, polydentate ligands can form complexes with metal ions in a single-step process, facilitating sharper end points. This means polydentate ligands, such as amino carboxylic acid derivatives, are most commonly employed in...


