Tertiary amines with very high steric congestion

空间拥挤度非常高的叔胺

• 批准号: 319881353
• 负责人: Dr. Andreas Ihle, since 11/2020
• 金额: --
• 依托单位: Max-Planck-Institut für Kohlenforschung
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/319881353?language=en
• 关键词: Tertiary; amines; very; steric; congestion

Sterically hindered amines play an important part in organic synthesis, for example, as bases with low nucleophilicity. They are utilized to prepare a variety of other products, for instance, spin-label compounds. The application of sterically hindered amines as light stabilizers in polymeric materials is also quantitatively of great importance. In basic research, special features of structures, such as the degree of flattening in the pyramidal structure of triisopropylamine, were intensively investigated and controversially discussed. Simple trialkylamines with significantly higher steric hindrance, for example, tri-tert-butylamine, are unknown and should be prepared within the project via nine different methods of synthesis for the first time. The novel products have to be analyzed in view of the packing and molecular structures in single crystals and in connection with conformational equilibria in solution (dynamic NMR spectroscopy and 15N NMR). We assume that the steric congestion in these tertiary amines has been underestimated up to now. Therefore, an unexpectedly high reactivity, for instance, in the easily occurring cleavage into a secondary amine and an alkene, will be the consequence.

位阻胺在有机合成中起着重要的作用，例如，作为低亲核性的碱。它们被用来制备各种其他产品，例如自旋标记化合物。空间位阻胺作为光稳定剂在聚合物材料中的应用在数量上也是非常重要的。在基础研究中，结构的特殊性，如三异丙胺金字塔结构的扁平化程度，被深入研究和有争议的讨论。空间位阻明显更高的简单三烷基胺，例如三叔丁胺，是未知的，应该在项目内首次通过九种不同的合成方法制备。新产品必须根据单晶中的堆积和分子结构以及溶液中的构象平衡进行分析（动态NMR光谱和15 N NMR）。我们认为，在这些叔胺的空间拥挤被低估了。因此，结果是出乎意料的高反应性，例如在容易发生的裂解成仲胺和烯烃中。

项目成果

Record-Breaking Steric Crowding in Trialkylamines Prepared by Oxidative Ring Opening

氧化开环制备三烷基胺的空间拥挤现象创纪录

• DOI: 10.1055/s-0040-1707294
• 发表时间: 2020
• 期刊: Synthesis
• 作者: K. Banert;M. Heck;A. Ihle;E. Michael;R. Weber
• 通讯作者: R. Weber

Synthesis of Trialkylamines with Extreme Steric Hindrance and Their Decay by a Hofmann-like Elimination Reaction.

具有极端空间位阻的三烷基胺的合成及其通过类霍夫曼消除反应的衰变

• DOI: 10.1021/acs.joc.0c01790
• 发表时间: 2020
• 期刊: The Journal of organic chemistry
• 作者: K. Banert;M. Hagedorn;M. Heck;R. Hertel;A. Ihle;I. Müller;T. Pester;T. Shoker;P. R. Rablen
• 通讯作者: P. R. Rablen