Alternative and Eco-Friendly Synthesis of Tetrakis(Aminomethyl)Calix-[4]-Resorcinarene  

作　　者：S. Ali Moussaoui Ziad Damaj Moheddine Wehbie Stéphane Pellet Rostaing Iyad Karamé 

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

出　　处：《International Journal of Organic Chemistry》2017年第4期403-411,共9页有机化学国际期刊（英文）

摘　　要：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.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.

关 键 词：Bridged -Resorcinarene ECO-FRIENDLY Synthesis Catalytic Hydrogenation Atom Economy Radical SUBSTITUTION Nucleophilic SUBSTITUTION CH2CL2 

分 类 号：O6[理学—化学]