Premium
Preparation of onium salts of a reduced anthracenone crown ether macrocycle: a reactivity series involving pyridine, phosphine, thiophene, nitrile and primary amide nucleophiles
Author(s) -
Mariappan Kadarkaraisamy,
Caple Gerald,
Basa Prem N.,
Sykes Andrew G.
Publication year - 2012
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.2902
Subject(s) - chemistry , reactivity (psychology) , nucleophile , pyridine , nitrile , phosphonium , amide , thiophene , organic chemistry , medicinal chemistry , carbocation , medicine , alternative medicine , pathology , catalysis
Reaction of mineral acids with a cyclic macromolecule containing a secondary alcohol produces ammonium, phosphonium, thiophene, and amide adducts via a carbocation intermediate. X‐ray crystallography confirms the structures of the products, including those when two competing nucleophiles are present. A reactivity series that mirrors the nucleophilicity index, where reactivity decreases in the order thiophene > pyridine > primary amides > alkyl nitriles >> aromatic nitriles (unreactive), results. Addition of metal ions to ammonium adducts dissolved in acetonitrile produces secondary amides via the Ritter amide synthesis. Copyright © 2012 John Wiley & Sons, Ltd.