Continuous-Flow Electrophilic Amination of Arenes and Schmidt Reaction of Carboxylic Acids Utilizing the Superacidic Trimethylsilyl Azide/Triflic Acid Reagent System.
Chen, Yuesu; Gutmann, Bernhard; Kappe, C Oliver
2016 • In Journal of Organic Chemistry, 81 (19), p. 9372 - 9380
[en] A continuous flow protocol for the direct stoichiometric electrophilic amination of aromatic hydrocarbons and the Schmidt reaction of aromatic carboxylic acids using the superacidic trimethylsilyl azide/triflic acid system is described. Optimization of reagent stoichiometry, solvent, reaction time, and temperature led to an intensified protocol at elevated temperatures that allows the direct amination of arenes to be completed within 3 min at 90 °C. In order to improve the selectivity and scope of this direct amination protocol, aromatic carboxylic acids were additionally chosen as substrates. Selected carboxylic acids could be converted to their corresponding amine counterparts in good to excellent yields (11 examples, 55-83%) via a Schmidt reaction employing similar flow reaction conditions (<5 min at 90 °C) and a similar reactor setup as for the amination. The safety issues derived from the explosive, toxic, and volatile hydrazoic acid intermediate, the corrosive nature of triflic acid, and the exothermic quenching were addressed by designing a suitable continuous flow reaction setup for both types of transformations.
Disciplines :
Chemistry
Author, co-author :
Chen, Yuesu ; Université de Liège - ULiège > Molecular Systems (MolSys) ; Institute of Chemistry, University of Graz , NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria
Gutmann, Bernhard; Research Center Pharmaceutical Engineering GmbH (RCPE), Inffeldgasse 13, 8010 Graz, Austria
Kappe, C Oliver; Institute of Chemistry, University of Graz , NAWI Graz, Heinrichstrasse 28, A-8010 Graz, Austria
Language :
English
Title :
Continuous-Flow Electrophilic Amination of Arenes and Schmidt Reaction of Carboxylic Acids Utilizing the Superacidic Trimethylsilyl Azide/Triflic Acid Reagent System.
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