Naming Carboxylic Acids

Alkane Alkanoic Acid (no 1 needed, since carboxylic acids are terminal groups) O

O OH pentane pentanoic acid

O H OH methane methanoic acid

HO CH3

hexane hexanoic acid S-2-methylhexanoic acid

If carboxylic acid is attached to a ring, use the cycloalkane as the parent, and add the phrase carboxylic acid (note: -COOH or -CO2H is used as an abbreviation for a carboxylic acid) O
CO2H COOH OH

cyclohexane

cyclohexane carboxylic acid

Four carboxylic acids are so commonly encountered that they have accepted common names, which you should memorize. These may be used as parent carboxylic acids: O O

O H OH formic acid

OH
HO

O CH3

O HO OH carbonic acid

OH Cl 2-chlorobenzoic acid (or ortho-chlorobenzoic acid)

benzoic acid

acetic acid

In carboxylic acids that contain a ketone or aldehyde the carboxylic acid takes precedence and the aldehyde or ketone group is labeled as an oxo substituent. Diacids are called dioic acids. O
OH O O 3-methyl-2,4-dioxohexanoic acid
HO O O OH

3-methylpentanedioic acid

Physical Properties of Carboxylic Acids

Carboxylic acids have both a polar carbonyl group AND an -OH group. Carboxylic acids have some of the strongest intermolecular forces of any functional group. This gives them high boiling points and high melting points (many carboxylic acids are solids at room temperature.) Their high polarity and especially their hydrogen-bonding ability makes them quite water-soluble. water solubility: boiling point: CH3CH2CH2CH2CH3 insoluble 35 C CH3CH2OCH2CH3 7.5 g / 100 mL 40 C CH3CH2CH2CH2OH 9 g / 100 mL 117 C CH3CH2CO2H infinite 141 C

Acidity of Carboxylic Acids

O OH + OH H2O + O O O O -Two Resonance Forms -Both have on oxygen, an electronegative atom

Carboxylate anion Two factors are important when discussing electronic effects: 1. Resonance (more important): rearrangement of electrons moves full + and charges 2. Induction (real, though less important than resonance): donation or withdrawal of electron density through bonds.

The Inductive Effect in Carboxylic Acids When a carboxylic acid undergoes deprotonation to form a carboxylate ion, electronegative atoms can withdraw electron density to help stabilize the carboxylate ion. A more stable carboxylate ion explains a stronger carboxylic acid.

CASE 1: The more electronegative the element, the more effective its electron withdrawal.
O OH -H O O
Br O OH -H Br O O

acetic acid (pKa = 4.7)

bromoacetic acid (pKa = 2.9)

(the second reaction works better--electronegative bromine withdraws electron density, stabilizing the carboxylate ion)

CASE 2: Greater number of electronegative atoms provides more effective withdrawal of electrons from the carboxylate ion.
O F OH -H O F O
O F F F OH O -H F F F O

fluoroacetic acid (pKa = 2.6)

trifluoroacetic acid (pKa = 0.2)

(the second reaction works better--three electronegative fluorines withdraw electron density more effectively than one)

CASE 3: The closer the electronegative atom is to the carboxylate end the more effective its electron withdrawing ability. An electronegative element several atoms away has almost no effect.
O Cl OH -H O Cl O
Cl O OH -H O Cl O

chloroacetic acid (pKa = 2.9)

4-chloroacetic acid (pKa = 4.5)

(first reaction works better-- electronegative atom closer to carboxylate is more effective at withdrawing electron density)
O
O OH F -H O O F
F O OH -H O O

OH -H

o-fluorobenzoic acid (pKa = 3.3)

m-fluorobenzoic acid (pKa = 3.9)

p-fluorobenzoic acid (pKa = 4.1)

(first reaction works best-- electronegative atom closer to carboxylate is more effective at withdrawing electron density) (Note: pKa of benzoic acid is 4.2)