22.1: Structure and Physical Properties of Amines
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Amines typically have three bonds and one pair of lone pair electrons. This makes the nitrogen sp3 hybridized, trigonal pyramidal, with a bond angle of roughly 109.5o.
Single-bonded nitrogen is pyramidal in shape, with the non-bonding electron pair pointing to the unoccupied corner of a tetrahedral region. Since the nitrogen in these compounds is bonded to three different groups, it is stereogenic and its configuration is chiral. The non-identical mirror-image configurations are illustrated in the following diagram (the remainder of the molecule is represented by R, and the electron pair is colored yellow). If these configurations were stable, there would be four additional stereoisomers of ephedrine and pseudoephedrine. However, pyramidal nitrogen is normally not configurationally stable. It rapidly inverts its configuration (equilibrium arrows) by passing through a planar, sp2-hybridized transition state, leading to a mixture of interconverting R and S configurations. If the nitrogen atom were the only chiral center in the molecule, a 50:50 (racemic) mixture of R and S configurations would exist at equilibrium. If other chiral centers are present, as in the ephedrin isomers, a mixture of diastereomers will result. The take-home message is that nitrogen does not contribute to isolable stereoisomers.
Amines are classified according to the number of alkyl or aryl groups attached to nitrogen. Amines are classified differently from alkyl halides and alcohols because nitrogen has a neutral bonding pattern of three bonds with a single lone pair. To classify amines, we look at the nitrogen atom of the amine and count the number of alkyl groups bonded to it. This number is the classification of the amine.
There are two additional classifications of amines. When the nitrogen is double bonded to carbon, then it is call am imine. When nitrogen is part of a ring that includes double bonds, then it is classified as heterocyclic, as seen in the aromatic nitrogen bases shown below.
Boiling Point and Water Solubility
It is instructive to compare the boiling points and water solubility of amines with those of corresponding alcohols and ethers. The dominant factor here is hydrogen bonding, and the first table below documents the powerful intermolecular attraction that results from -O-H---O- hydrogen bonding in alcohols (light blue columns). Corresponding -N-H---N- hydrogen bonding is weaker, as the lower boiling points of similarly sized amines (light green columns) demonstrate. Alkanes provide reference compounds in which hydrogen bonding is not possible, and the increase in boiling point for equivalent 1º-amines is roughly half the increase observed for equivalent alcohols.
The second table illustrates differences associated with isomeric 1º, 2º & 3º-amines, as well as the influence of chain branching. Since 1º-amines have two hydrogens available for hydrogen bonding, we expect them to have higher boiling points than isomeric 2º-amines, which in turn should boil higher than isomeric 3º-amines (no hydrogen bonding). Indeed, 3º-amines have boiling points similar to equivalent sized ethers; and in all but the smallest compounds, corresponding ethers, 3º-amines and alkanes have similar boiling points. In the examples shown here, it is further demonstrated that chain branching reduces boiling points by 10 to 15 ºC.
The water solubility of 1º and 2º-amines is similar to that of comparable alcohols. As expected, the water solubility of 3º-amines and ethers is also similar. These comparisons, however, are valid only for pure compounds in neutral water. The basicity of amines (next section) allows them to be dissolved in dilute mineral acid solutions, and this property facilitates their separation from neutral compounds such as alcohols and hydrocarbons by partitioning between the phases of non-miscible solvents.
The free base form of amines can be quite odiferous. The foul smell of dying flesh is primarily from the amines released during decomposition of the proteins in an organism. The common names for the amines below emphasize this aspect of amines. It is also useful to note that common names frequently indicate the presence of an amine with the "ine" suffix.
The smell of amines can be reduced by reacting them with strong acids to form the ammonium salts. For example, the acid from lemons can be used to disguise the smell of fish that is past optimum freshness. While the free base forms of amines can be thermally unstable and smelly, the ammonium salt formed from the conjugate acid of the amine have increased thermal stability and reduced odor. If the amine is not soluble as a free base, its ammonium salt will be water soluble.
1. Draw the structures for the following amines in order of decreasing water solubility: methanamine, 2-octanamine, 2-butanamine.
2. Draw the for the following amines in order of decreasing boiling point: cyclohexanamine, 2-octanamine, 2-butanamine.
3. Classify the following amines.
3. a) primary b) secondary c) secondary d) tertiary
Contributors and Attributions
Dr. Dietmar Kennepohl FCIC (Professor of Chemistry, Athabasca University)
Prof. Steven Farmer (Sonoma State University)
William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry