Tertiary amines with very high steric congestion
Tertiary amines with very high steric congestion
批准号:
319881353
负责人:
Dr. Andreas Ihle, since 11/2020
金额:
$0.0万
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
项目状态:
已结题
起止时间:
2015-12-31 至 2020-12-31
中文摘要
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。它们用于制备各种其他产品,例如自旋标签化合物。空间位阻胺作为光稳定剂在高分子材料中的应用也具有重要的定量意义。在基础研究中,结构的特殊特征,如三异丙胺金字塔结构的扁平程度,被深入研究和有争议的讨论。具有明显更高位阻的简单三烷基胺,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。新产物必须从单晶的堆积和分子结构以及溶液中的构象平衡(动态核磁共振光谱和15N核磁共振)的角度进行分析。我们认为,到目前为止,这些叔胺的位阻充血被低估了。因此,出乎意料的高反应性,例如,在容易发生裂解成仲胺和烯烃,将是后果。
英文摘要
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.
期刊论文(4)
专著(0)
科研奖励(0)
会议论文
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
影响因子:
--
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
影响因子:
--
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
海外基金