1. 16 16-1 © 2006 Thomson Learning, Inc. All rights reserved General, Organic, and Biochemistry, 8e Bettelheim, Brown Campbell, & Farrell

2. 16 16-2 © 2006 Thomson Learning, Inc. All rights reserved Chapter 16 Amines Amines

3. 16 16-3 © 2006 Thomson Learning, Inc. All rights reserved Structure & Classification Amines are classified as 1°, 2°, or 3° depending on the number of carbon groups bonded to nitrogen. aliphatic amine:aliphatic amine: All carbons bonded to nitrogen are derived from alkyl groups. aromatic amine:aromatic amine: One or more of the groups bonded to nitrogen are aryl groups.

4. 16 16-4 © 2006 Thomson Learning, Inc. All rights reserved Structure & Classification heterocyclic amine:heterocyclic amine: An amine in which the nitrogen atom is part of a ring. heterocyclic aliphatic amine:heterocyclic aliphatic amine: A heterocyclic amine in which the ring is saturated (has no C=C bonds). heterocyclic aromatic amine:heterocyclic aromatic amine: The amine nitrogen is part of an aromatic ring.

5. 16 16-5 © 2006 Thomson Learning, Inc. All rights reserved Nomenclature IUPAC names We derive IUPAC names for aliphatic amines just as we did for alcohols. -e- amine.Drop the final -e of the parent alkane and replace it by - amine. Use a number to locate the amino group on the parent chain.

6. 16 16-6 © 2006 Thomson Learning, Inc. All rights reserved Nomenclature IUPAC names (cont’d) IUPAC nomenclature retains the common name aniline for C 6 H 5 NH 2, 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. 16 16-7 © 2006 Thomson Learning, Inc. All rights reserved 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. 16 16-8 © 2006 Thomson Learning, Inc. All rights reserved Nomenclature Common names amineFor most aliphatic amines, list the groups bonded to nitrogen in alphabetical order in one word ending in the suffix -amine.

9. 16 16-9 © 2006 Thomson Learning, Inc. All rights reserved Nomenclature Amine salts When four atoms or groups of atoms are bonded to a nitrogen atom, as for example CH 3 NH 3 +, nitrogen bears a positive charge and is associated with an anion as a salt. Name the compound as a salt of the corresponding amine. -amine -ammoniumReplace 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. 16 16-10 © 2006 Thomson Learning, Inc. All rights reserved 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).

11. 16 16-11 © 2006 Thomson Learning, Inc. All rights reserved Physical Properties 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.

12. 16 16-12 © 2006 Thomson Learning, Inc. All rights reserved 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.

13. 16 16-13 © 2006 Thomson Learning, Inc. All rights reserved 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.

14. 16 16-14 © 2006 Thomson Learning, Inc. All rights reserved 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.

15. 16 16-15 © 2006 Thomson Learning, Inc. All rights reserved Basicity of Amines The base dissociation constant, K b, for the reaction of an amine with water has the following form, illustrated for the reaction of methylamine with water to give methylammonium hydroxide. pK b is defined as the negative logarithm of K b

16. 16 16-16 © 2006 Thomson Learning, Inc. All rights reserved Basicity of Amines Aliphatic amines have about the same base strength, and are slightly stronger bases than NH 3. 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.

17. 16 16-17 © 2006 Thomson Learning, Inc. All rights reserved Basicity of Amines Assume that the amine, RNH 2, has a pK b 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 RNH 3 + to RNH 2. substituting values for K b and OH - gives:

18. 16 16-18 © 2006 Thomson Learning, Inc. All rights reserved 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.

19. 16 16-19 © 2006 Thomson Learning, Inc. All rights reserved 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.

20. 16 16-20 © 2006 Thomson Learning, Inc. All rights reserved Reactions of Amines example:example: Complete each acid-base reaction and name the salt formed.

21. 16 16-21 © 2006 Thomson Learning, Inc. All rights reserved Reactions of Amines example:example: Complete each acid-base reaction and name the salt formed. solution:solution:

22. 16 16-22 © 2006 Thomson Learning, Inc. All rights reserved End Chapter 16 Amines