10.5: Carbonyl substitution reactions
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Harper College Chemistry Department
Chemistry: Atoms First
Derived from Chemistry by
Carboxylic Acids and Esters
The odor of vinegar is caused by the presence of acetic acid, a carboxylic acid, in the vinegar. The odor of ripe bananas and many other fruits is due to the presence of esters, compounds that can be prepared by the reaction of a carboxylic acid with an alcohol. Because esters do not have hydrogen bonds between molecules, they have lower vapor pressures than the alcohols and carboxylic acids from which they are derived (see Figure 1 ).
Both carboxylic acids and esters contain a carbonyl group with a second oxygen atom bonded to the carbon atom in the carbonyl group by a single bond. In a carboxylic acid, the second oxygen atom also bonds to a hydrogen atom. In an ester, the second oxygen atom bonds to another carbon atom. The names for carboxylic acids and esters include prefixes that denote the lengths of the carbon chains in the molecules and are derived following nomenclature rules similar to those for inorganic acids and salts (see these examples):
The functional groups of carboxylic acid and ester are shown in red in these formulas.
The hydrogen atom in the functional group of a carboxylic acid will react with a base to form an ionic salt:
Carboxylic acids are weak acids (see the chapter on acids and bases), meaning they are not 100% ionized in water. Generally, only about 1% of the molecules of a carboxylic acid dissolved in water are ionized at any given time. The remaining molecules are undissociated in solution.
We prepare carboxylic acids by the oxidation of aldehydes or alcohols whose –OH functional group is located on the carbon atom at the end of the chain of carbon atoms in the alcohol:
Esters are produced by the reaction of acids with alcohols. For example, the ester ethyl acetate, CH 3 CO 2 CH 2 CH 3 , is formed when acetic acid reacts with ethanol:
The simplest carboxylic acid is formic acid, HCO 2 H, known since 1670. Its name comes from the Latin word formicus , which means “ant”; it was first isolated by the distillation of red ants. It is partially responsible for the pain and irritation of ant and wasp stings and is responsible for a characteristic odor of ants that can be sometimes detected in their nests.
Acetic acid, CH 3 CO 2 H, constitutes 3–6% vinegar. Cider vinegar is produced by allowing apple juice to ferment without oxygen present. Yeast cells present in the juice carry out the fermentation reactions. The fermentation reactions change the sugar present in the juice to ethanol, then to acetic acid. Pure acetic acid has a penetrating odor and produces painful burns. It is an excellent solvent for many organic and some inorganic compounds, and it is essential in the production of cellulose acetate, a component of many synthetic fibers such as rayon.
The distinctive and attractive odors and flavors of many flowers, perfumes, and ripe fruits are due to the presence of one or more esters ( Figure 2 ). Among the most important of the natural esters are fats (such as lard, tallow, and butter) and oils (such as linseed, cottonseed, and olive oils), which are esters of the trihydroxyl alcohol, glycerine, C 3 H 5 (OH) 3 , with large carboxylic acids, such as palmitic acid, CH 3 (CH 2 ) 14 CO 2 H, stearic acid, CH 3 (CH 2 ) 16 CO 2 H, and oleic acid, CH 3 ( C H 2 ) 7 CH = CH ( CH 2 ) 7 C O 2 H .
Oleic acid is an unsaturated acid; it contains a C = C double bond. Palmitic and stearic acids are saturated acids that contain no double or triple bonds.