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

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.     

Azocoupling reactions of enaminocarbonyl derivatives of 1,2,3,4-tetrahydroisoquinoline with diazonium salts

It has been shown that enamino amide and enamino ketone derivatives of 1,2,3,4-tetrahydroisoquinoline react with diazonium salts to form azo compounds. Depending on the enamine structure they can exist just as azo dyes or as azohydrazone tautomers. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1382–1387, September, 2006.     

弱碱作用下从叔醇简便地合成烯烃

用甲磺酸酐和三乙胺作为脱水剂, 发展了一种从叔醇合成烯烃的简便方法, 反应时间短, 温和的条件和高产率使该方法可以快速地从叔醇合成烯烃.     

N_(235)萃取HCl体系中TBP消除第三相的作用机理

通过测定萃取有机相的电导率变化研究叔胺N235(三烷基胺)萃取盐酸体系中第三相的形成及改性剂消除第三相的作用机理。实验结果表明,无改性剂时萃取体系在各种条件下均出现第三相。第三相组成为R3NH (H2O)3·Cl-,具有导电性。加改性剂TBP(磷酸三丁酯)后,第三相消失。本文认为改性剂TBP消除第三相的作用机理是TBP能够将萃合物R3NH (H2O)3·Cl-拆分为可溶于惰性稀释剂的R3NH (H2O)3·O=P(OC4H9)3大阳离子,Cl-离子则以抗衡离子分散于稀释剂中。