叔胺及其 N-氧化物的 1H 和 13C 化学位移的观察和计算。

The observed and calculated 1H and 13C chemical shifts of tertiary amines and their N-oxides.

机构信息

Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague, Czech Republic.

出版信息

Magn Reson Chem. 2011 Jun;49(6):320-7. doi: 10.1002/mrc.2750. Epub 2011 Mar 31.

Abstract

A series of model tertiary amines were oxidized in situ in an NMR tube to amine N-oxides and their (1)H and (13)C NMR spectra were recorded. Next, the chemical shifts induced by oxidation (Δδ) were calculated using different GIAO methods investigating the influence of the method [Hartree-Fock (HF), Moeller-Plesset perturbation, density functional theory (DFT)], the functional applied in the DFT (B3LYP, BPW, OPBE, OPW91) and the basis set used [6-31G*, 6-311G**, 6-311 + + G** and 6-311 + + G(3df,3pd)]. The best results were obtained with the HF/6-311 + + G** and OPBE/6-311 + + G** methods. The computation/experiment comparison approach was used for the configuration prediction of chiral amine N-oxides-(R) and (S)-agroclavine-6-N-oxide.

摘要

一系列模型叔胺在 NMR 管中原位氧化为胺 N-氧化物，并记录其 (1)H 和 (13)C NMR 谱。然后，使用不同的 GIAO 方法计算氧化引起的化学位移（Δδ），考察方法[Hartree-Fock (HF)、Møller-Plesset 微扰、密度泛函理论（DFT）]、在 DFT 中应用的函数[B3LYP、BPW、OPBE、OPW91]和基组[6-31G*、6-311G**、6-311 + + G和 6-311 + + G(3df,3pd)]对氧化的影响。HF/6-311 + + G和 OPBE/6-311 + + G**方法得到了最好的结果。对于手性胺 N-氧化物-(R)和(S)-agroclavine-6-N-氧化物的构型预测，使用了计算/实验比较方法。