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Imine formation: the mechanism, step by step

The amine adds to the carbonyl, the resulting alcohol-amine loses water, and a carbon–nitrogen double bond is left.

rule-derived3 stepsNot a record of what was observed

The pathway runs in 3 steps. What sits between them is a real structure: it is what the reaction passes through, and on a bad day it is what you isolate instead of the product.

Below is the sequence as it is taught. On the platform it is drawn on whatever structures you supply, with the curly arrows resolved to the actual atoms involved rather than to a general case with R groups on it.

The steps

  1. The amine adds to the carbonyl

    The nitrogen shares its pair of electrons with the carbon of the C=O group, and the double bond's electrons move up onto the oxygen.

    Addition of the amine lone pair into the carbonyl π*, giving a zwitterion with a negative oxygen and a positive nitrogen.

  2. The proton moves from nitrogen to oxygen

    The spare hydrogen on the nitrogen hops across to the oxygen. Now there is a hydroxyl group and a neutral nitrogen.

    Proton transfer giving the neutral hemiaminal. In the flask this happens through the solvent rather than directly.

  3. Water leaves and the double bond forms

    The nitrogen pushes its electrons into the bond to carbon, making a double bond, and that forces the water off.

    The nitrogen lone pair forms the C=N π bond as the C–O bond breaks, the oxygen leaving as water.

What this drawing assumes

Read these before you quote the mechanism
  • Drawn without the acid catalysis that normally carries it: in practice the hydroxyl is protonated before it leaves, and the rate is fastest at mildly acidic pH.
  • The proton transfers between nitrogen and oxygen are collected into one step rather than drawn individually.

Other pathways this class runs by

  • Under strongly acidic conditions the carbonyl is protonated first, which makes the addition faster but ties up the amine as its salt.

A class is not one pathway. Which of these runs depends on the substrate, the solvent and what else is in the flask, and the drawing above does not decide that for you.

Run it on your own structures

Enter the reactants and the product you expect. If the transformation is one the engine can perform and this pathway reaches that product from those structures, it is drawn on them — with the arrows on the right atoms and the intermediates you would actually pass through. If it does not reach the product, you are told that instead of being shown a drawing that does not apply.