Author(s)

S. Ali Moussaoui¹, Ziad Damaj¹, Moheddine Wehbie^1,2, Stéphane Pellet Rostaing², Iyad Karamé^1*

¹Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon.
²Institut de Chimie Séparative de Marcoule, ICSM, UMR 5257 - CEA/CNRS/UM2/ENSCM Site de Marcoule, Batiment 426, F-30207 Bagnols sur Cèse Cedex, France.

A cleaner and eco-friendly method was developed for the preparation of tetrakis(aminomethyl)calix-[4]-resorcinarene via a synthetic pathway of five steps starting from methylresorcinol. This alternative methodology is firstly based on avoiding the use of CH₂BrCl, which is a non-eco-friendly substance with high ozone depletion potential, and on replacing it by CH₂Cl₂ as a readily available reagent with much less dangerous effects. Secondly, this method engages acetone or CH₂Cl₂ as the solvent of the bromination step in the place of the very toxic CCl₄, leading to tetrakis(bromomethyl)calix-[4]-resorcinarene. The brominated intermediate has been reacted with sodium azide in acetone instead of the high-boiling solvent DMSO to produce tetrakis(azidomethyl) calix-[4]-resorcinarene without the need of tedious purification. Lastly, this work reports an efficient hydrogenation method of the versatile azido adduct employing Pt/C (5%) as the catalyst for the preparation of the amino cavitand as an alternative route with high atom economy that can replace the classical methods used currently.

Bridged Calix-[4]-Resorcinarene, Eco-Friendly Synthesis, Catalytic Hydrogenation, Atom Economy, Radical Substitution, Nucleophilic Substitution, CH₂Cl₂

Moussaoui, S. , Damaj, Z. , Wehbie, M. , Rostaing, S. and Karamé, I. (2017) Alternative and Eco-Friendly Synthesis of Tetrakis(Aminomethyl)Calix-[4]-Resorcinarene. International Journal of Organic Chemistry, 7, 403-411. doi: 10.4236/ijoc.2017.74032.