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Alternative and Eco-Friendly Synthesis of Tetrakis(Aminomethyl)Calix-[4]-Resorcinarene
Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
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
Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
- 1 Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
- 2 Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
- 3 Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
- 4 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
- 5 Department of Chemistry, Laboratory of Catalysis, Organometallic and Materiels LCOM, Lebanese University, Faculty of Sciences I, Hadath, Lebanon
International Journal of Organic Chemistry·Volume 07 (2017)·Pages 403–411·Published 25 October 2017·DOI10.4236/ijoc.2017.74032
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Abstract
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 CH 2 BrCl, which is a non-eco-friendly substance with high ozone depletion potential, and on replacing it by CH 2 Cl 2 as a readily available reagent with much less dangerous effects. Secondly, this method engages acetone or CH 2 Cl 2 as the solvent of the bromination step in the place of the very toxic CCl 4 , 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.
KeywordsBridged Calix-[4]-ResorcinareneEco-Friendly SynthesisCatalytic HydrogenationAtom EconomyRadical SubstitutionNucleophilic SubstitutionCH<sub>2</sub>Cl<sub>2</sub>
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