Issue 30, 2012

Organic reactivity in liquid ammonia


Liquid ammonia is a useful solvent for many organic reactions including aliphatic and aromatic nucleophilic substitution and metal-ion catalysed reactions. The acidity of acids is modified in liquid ammonia giving rise to differences from conventional solvents. The ionisation constants of phenols and carbon acids are the product of those for ion-pair formation and dissociation to the free ions. There is a linear relationship between the pKa of phenols and carbon acids in liquid ammonia and those in water of slope 1.68 and 0.7, respectively. Aminium ions exist in their unprotonated free base form in liquid ammonia. The rates of solvolysis and aminolysis by neutral amines of substituted benzyl chlorides in liquid ammonia show little or no dependence upon ring substituents, in stark contrast with the hydrolysis rates of substituted benzyl halides in water which vary 107 fold. However, the rates of the reaction of phenoxide ions and amine anions with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1 and 0.93, respectively. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Brønsted βnuc = 0.21 whereas those for substituted phenoxide ions generate a Brønsted βnuc = 0.40. The rates of aromatic nucleophilic substitution reactions in liquid ammonia are much faster than those in protic solvents indicating that liquid ammonia behaves like a typical dipolar aprotic solvent in its solvent effects on organic reactions. Nitrofluorobenzenes (NFB) readily undergo solvolysis in liquid ammonia but oxygen nucleophiles, such as alkoxide and phenoxide ions, displace the fluorine of 4-NFB in liquid ammonia to give the corresponding substitution product with little or no competing solvolysis product. The Brønsted βnuc for the reaction of 4-NFB with para-substituted phenoxides is 0.91, indicative that the decomposition of the Meisenheimer σ-intermediate is rate limiting. The aminolysis of 4-NFB occurs without general base catalysis by the amine and the second order rate constants generate a Brønsted βnuc of 0.36, which is also interpreted in terms of rate limiting breakdown of the Meisenheimer σ-intermediate.

Graphical abstract: Organic reactivity in liquid ammonia

Article information

Article type
10 Jan 2012
07 Mar 2012
First published
26 Apr 2012

Org. Biomol. Chem., 2012,10, 5732-5739

Organic reactivity in liquid ammonia

P. Ji, J. Atherton and M. I. Page, Org. Biomol. Chem., 2012, 10, 5732 DOI: 10.1039/C2OB25064K

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