Reactions of Amines

You may use these summaries and problems but you may NOT download them for use at another site, nor may you charge for access to them. Copyright Linda M. Sweeting 1997

The following example reactions are organized by type, with references to text chapters. Links within these summaries (which may show up as boxes around reagents) will provide further information about the reagents and their other reactions. Return to Reaction Summary menu for other functional group choices.

All reactions are dominated by the basicity / nucleophilicity of the nitrogen

As Bronsted bases

Note that the pK_a of the conjugate acid is most commonly used instead of pK_b of the amine.
McMurry 24.6, Fessenden 18.6, Schmid 22.5

As nucleophiles - with sp³ carbon

Reaction is very hard to control
Mechanism!
McMurry 11.2, 11.5, 24.6, Fessenden 18.7, Schmid 22.8

As nucleophiles - with sp² carbon

+ HCl
Anhydrides react similarly yielding one mole of the carboxylic acid instead of HCl
Mechanism!
McMurry 21.7, 24.7, Fessenden 18.7, Schmid 16.5, 22.18
To other reactions of acid chlorides

An imine. Anhydrous conditions needed. This reaction works better if the amine has an electron-withdrawing group to make it less basic. In that case, the acid protonates the carbonyl, making it more reactive. Examples include substituted hydrazines (NH₂NHR), where the other nitrogen makes the one on the left less basic.
Mechanism!
McMurry 23.12, Fessenden 13.5A, Schmid 14.13 - 14.15
To other reactions of aldehydes and ketones

An enamine, which reacts like an enolate. Anhydrous conditions needed.
McMurry 23.12, Fessenden 13.5B, Schmid 14.13, 17.14
To other reactions of aldehydes and ketones