Hemiaminal


A hemiaminal is a functional group or type of chemical compound that has a hydroxyl group and an amine attached to the same carbon atom: -C-. R can be hydrogen or an alkyl group. Hemiaminals are intermediates in imine formation from an amine and a carbonyl by alkylimino-de-oxo-bisubstitution.

Examples

A hemiaminal is the first step in the reaction of an aldehyde or ketone with an amine. Being one of the most reactive carbonyls, formaldehyde is well known to give carbinolamines. Illustrative is the reaction of the weakly basic secondary amine carbazole with formaldehyde.
As is typical with a secondary amine derivative, this carbinol converts readily to the methylene-linked bis.
Ammonia adds to hexafluoroacetone to give a stable hemiaminal, 2CNH2.
Those generated from primary amines and ammonia are usually unstable to the extent that they have never been isolated and very rarely been observed directly. A hemiaminal trapped in the cavity of a host–guest complex exhibited chemical half-life of 30 minutes. Because both amine and carbonyl group are isolated in a cavity, hemiaminal formation is favored due to a high forward reaction rate comparable to an intramolecular reaction and also due to restricted access of external base to the same cavity which would favor elimination of water to the imine.
Hemiaminal formation is a key step in an asymmetric total synthesis of saxitoxin:
In this reaction step the alkene group is first oxidized to an intermediate acyloin by action of osmium chloride, oxone and sodium carbonate.

Ammonia-aldehydes

The adducts formed by the addition of ammonia to aldehydes have long been studied. This class of compounds contain both a primary amino group and a hydroxyl group bonded to the same carbon atom. These species have rarely been detected, much less isolated in bulk. They are invoked as intermediates in the formation of Schiff bases and related imines from the reaction of ammonia and aldehydes and ketones.