Chapter 8 Amines

1. Chapter 8Amines

2. Structure and Classification Amines are classified as 1°, 2°, or 3° depending on the number of carbon groups bonded to nitrogen. Aliphatic amine:All carbons bonded to nitrogen are derived from alkyl groups. See the three above.

3. Structure and Classification • Aromatic amine:One or more of the groups bonded to nitrogen are aryl groups.

4. Structure and Classification • Heterocyclic amine:An amine in which the nitrogen atom is part of a ring. • Heterocyclic aliphatic amine:A heterocyclic amine in which the ring is saturated (has no C=C bonds). • Heterocyclic aromatic amine:The amine nitrogen is part of an aromatic ring.

5. Nomenclature IUPAC names • We derive IUPAC names for aliphatic amines just as we did for alcohols. • Drop the final-eof the parent alkane and replace it by -amine. • Use a number to locate the amino group on the parent chain.

6. Nomenclature • IUPAC names (cont’d) • IUPAC nomenclature retains the common name aniline for C6H5NH2, the simplest aromatic amine. • Name simple derivatives of aniline by using numbers to locate substituents or, alternatively, use the prefixes ortho (o), meta (m), and para (p). • Several derivatives of aniline have common names that are still widely used; among them is toluidine:

7. Nomenclature IUPAC names (cont’d) • Name unsymmetrical secondary and tertiary amines as N-substituted primary amines. • Take the largest group bonded to nitrogen as the parent amine. • Name the smaller group(s) bonded to nitrogen, and show their location on nitrogen by using the prefix N- (indicating that they are bonded to nitrogen).

8. Nomenclature Common names • For most aliphatic amines, list the groups bonded to nitrogen in alphabetical order in one word ending in the suffix -amine.

9. Nomenclature Amine salts • When four atoms or groups of atoms are bonded to a nitrogen atom, as for example CH3NH3+, nitrogen bears a positive charge and is associated with an anion as a salt. • Name the compound as a salt of the corresponding amine. • Replace the ending –amine(or aniline or pyridine or the like) by -ammonium(or anilinium or pyridinium or the like) and add the name of the anion.

10. Examples • Draw the structures of the following compounds t-butylamine 3-methyl-1-butanamine 2,4,N,N-tetramehtyl-3-hexanamine

11. Physical Properties Like ammonia, low-molecular-weight amines have very sharp, penetrating odors. • Trimethylamine, for example, is the pungent principle in the smell of rotting fish. • Two other particularly pungent amines are 1,4-butanediamine (putrescine) and 1,5-pentanediamine (cadaverine).

12. Physical Properties Figure 11.1 Amines are polar compounds: • Both 1° and 2° amines have N-H bonds, and can form hydrogen bonds with one another. • 3° Amines have no N-H bond and cannot form hydrogen bonds with one another.

13. Physical Properties • An N-H---N hydrogen bond is weaker than an O-H---O hydrogen bond, because the difference in electronegativity between N and H (3.0 - 2.1 = 0.9) is less than that between O and H (3.5 - 2.1 = 1.4). • We see the effect of hydrogen bonding between molecules of comparable molecular weight by comparing the boiling points of ethane, methanamine, and methanol.

14. Physical Properties • All classes of amines form hydrogen bonds with water and are more soluble in water than are hydrocarbons of comparable molecular weight. • Most low-molecular-weight amines are completely soluble in water. • Higher-molecular-weight amines are only moderately soluble in water or are insoluble.

15. Basicity of Amines Like ammonia, amines are weak bases, and aqueous solutions of amines are basic. • The acid-base reaction between an amine and water involves transfer of a proton from water to the amine.

16. Basicity of Amines • The base dissociation constant, Kb, for the reaction of an amine with water has the following form, illustrated for the reaction of methylamine with water to give methylammonium hydroxide. • pKb is defined as the negative logarithm of Kb.

17. Basicity of Amines

18. Basicity of Amines • Aliphatic amines have about the same base strength, and are slightly stronger bases than NH3. • Aromatic and heterocyclic aromatic. • amines are considerably weaker bases than aliphatic amines. • Note that while aliphatic amines are weak bases by comparison with inorganic bases such as NaOH, they are strong bases among organic compounds.

19. Basicity of Amines • Given the basicities of amines, we can determine which form of an amine exists in body fluids, say blood. • In a normal, healthy person, the pH of blood is approximately 7.40, which is slightly basic. • If an aliphatic amine is dissolved in blood, it is present predominantly as its protonated (conjugated acid) form.

20. Basicity of Amines • Assume that the amine, RNH2, has a pKb of 3.50 and that it is dissolved in blood, pH 7.40 (pOH 6.60). • We first write the base dissociation constant for the amine and then solve for the ratio of RNH3+ to RNH2. Substituting values for Kb and OH- gives:

21. Basicity of Amines

22. Select the stronger base from each pair of amines

23. Reactions of Amines The most important chemical property of amines is their basicity. • Amines, whether soluble or insoluble in water, react quantitatively with strong acids to form water-soluble salts.

24. Basicity of Amines Example: Complete each acid-base reaction and name the salt formed.