Naslov
Hammett correlation and reaction mechanisms in mechanochemical imine formation

Autori
Vugrin, Leonarda ; Carta, Maria ; Delogu, Francesco ; Halasz, Ivan

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
28HSKIKI : 28th Croatian Meeting of Chemists and Chemical Engineers and 6th Symposium Vladimir Prelog : Book of Abstracts / Rogošić, Marko - Zagreb : Hrvatsko društvo kemijskih inženjera i tehnologa (HDKI), 2023, 138-138

Skup
The 28th Croatian Meeting of Chemists and Chemical Engineers (28HSKIKI)

Mjesto i datum
Rovinj, Hrvatska, 28.03.2023. - 30.03.2023

Vrsta sudjelovanja
Poster

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
Imine ; mechanochemistry ; Hammett

Sažetak
Solution-based physical organic chemistry was marked by the development of Hammett correlation, which further served as a major tool for deciphering the mechanisms of organic reactions in solution. If applicable to mechanochemical reactions, it will provide support for understanding the reaction mechanisms and expansion of this important synthetic methodology. As a model system to test the validity of the Hammett equation under mechanochemical conditions, we focused on imine formation from an aromatic aldehyde and anilines. Using in situ Raman reaction monitoring and kinetic analysis, we find a linear relationship between the reaction probability and Hammett constants indicating that this classical concept of chemical reactivity is valid for reactions conducted by ball milling and could prove useful for optimization of mechanochemical reactions. The Hammett plot showed that the imine formation is sensitive to the nucleophilicity of the aniline partner with the reaction probability increasing with stronger electron donor substituents, as expected. We further explore reaction mechanism of imine formation on a catalysed reaction, in a contrast to the otherwise facile imine preparation by neat grinding.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA