Acyclic tertiary amines as nucleophiles in substitution reactions of aromatic and heteroaromatic halides

Predicting solvent effects in ionic liquids: Extension of a nucleophilic aromatic substitution reaction on a benzene to a pyridine

“…Triethylamine is considered to be a non‐nucleophilic base and usually tertiary amines require harsher conditions than those used here to participate in S N Ar reactions, although there are reports of tertiary amines acting as nucleophiles for S N Ar reactions for activated electrophiles . To overcome the problem of reaction of the pyridine 3 with triethylamine, the concentration of triethylamine was decreased (to 1.1 equivalents of pyridine 3 ) in solution.…”

Tertiary Alkylamines as Nucleophiles in Substitution Reactions at Heteroaromatic Halide During the Synthesis of the Highly Potent Pirinixic Acid Derivative 2-(4-Chloro-6-(2,3-dimethylphenylamino)pyrimidin-2-ylthio)octanoic Acid (YS-121)

“…As far as the formation of byproduct 8 is concerned, a disubstitution would have only been possible in step (iii a), if diethylamine or diethylamine-related reactive intermediates had been present next to 2,3-dimethylaniline as nucleophiles as well. Either that byproduct formation is the result of a diethylamine impurity of the used commercially available reagents triethylamine, 2,3-dimethylaniline or EtOH in step (iii a) or it is a further indication that triethylamine could react as a nucleophile during nucleophilic aromatic substitution reactions at heteroaromatic halides as previously described by Matsumoto et al [ 15 ].…”

Ring opening of bicyclic tertiary amines with cyclic chlorocarbaphosphazenes: reactions of (ClCN)2(Cl2PN) with 1,4-diazabicyclo[2.2.2]octane and quinuclidine †

“…While amine hydrochloride is reported as the only isolable side product from these reactions of carbaphosphazenes with trialkylamines, 4 the formation of tetraalkylammonium halide as well as alkyl halide has been envisaged for dealkylation reactions involving various amines and heteroaromatic halides. [5][6][7][8][9] The present work has been designed so as to trap the cleaved alkyl group of tertiary amines as part of the product molecule in reactions involving cyclocarbaphosphazene and tertiary amines. Reports on dealkylations involving cyclic tertiary amines like N-methylmorpholine and N-methylpiperidine have shown the preference for the formation of products resulting from the cleavage of the methyl groups thereby indicating the extra stability of cyclic amines.…”