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pyrrolidine or titanium ethoxide [Ti(OEt)₄] have been shown to catalyse imine formation.

Rarer than primary amines is the use of ammonia to give a primary imine. In the case of hexafluoroacetone, the hemiaminal intermediate can be isolated.

From nitriles

Primary ketimines can be synthesized via a Grignard reaction with a nitrile.

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