Salicylaldehyde derivatives and their imines are important building blocks in organic and supramolecular chemistry. In an effort to expand structural diversity in the current work we changed ortho-OH in salicylaldehyde to NH of amide/sulfonamide and investigated the effect of resulting intramolecular hydrogen bonds on imine dynamic covalent chemistry (DCC). A suite of ortho-aminobenzaldehydes were readily synthesized, and X-ray and NMR data validated the existence of NH⋯O intramolecular hydrogen bonds. The formation and exchange of imines were then studied in acetonitrile, and the acidity of OH/NH significantly influenced the thermodynamics and kinetics of imine reactions. Furthermore, the role of OH/NH⋯N hydrogen bonds on imines was elucidated by the shift of aldehyde exchange equilibrium. Finally, the formation of imines was achieved in aqueous solutions. The mechanistic insights could pave the way for future applications in assembly and labelling.

水杨醛衍生物及其亚胺是有机和超分子化学的重要组成部分。为了扩大当前工作中的结构多样性，我们将水杨醛中的邻位-OH更改为酰胺/磺酰胺的NH，并研究了分子内氢键对亚胺动态共价化学（DCC）的影响。一组邻氨基苯甲醛很容易合成，X射线和NMR数据证实了NH ⋯ O分子内氢键的存在。然后在乙腈中研究亚胺的形成和交换，OH / NH的酸度显着影响亚胺反应的热力学和动力学。此外，OH / NH的作用⋯通过醛交换平衡的移动阐明了亚胺上的N氢键。最后，在水溶液中形成亚胺。机械方面的见识可以为将来在装配和贴标中的应用铺平道路。