CARBOXYLIC ACIDS Carboxyl group:

O C OH

Nomenclature Structure H-COOH CH3-COOH CH3CH2-COOH CH3(CH2)2-COOH CH3(CH2)3-COOH CH3(CH2)4-COOH Common Name formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, IUPAC methanoic acid ethanoic acid propanoic acid butanoic acid pentanoic acid hexanoic acid

Positions along the chain are indicated by Greek letters (common names) or numbers (IUPAC).

Br

-bromovaleric

acid

CH3 CHCH2CH2 C OH 5 4 3 2 1

4-bromopentanoic acid

Dicarboxylic acids Structure HOOC-COOH HOOC-CH2-COOH Common Name oxalic acid, malonic acid, IUPAC ethanedioic acid propanedioic acid butanedioic acid pentanedioic acid hexanedioic acid

HOOC-(CH2)2-COOH succinic acid, HOOC-(CH2)3-COOH glutaric acid, HOOC-(CH2)4-COOH adipic acid, Aromatic acids
O C OH O C C O phthalic acid OH OH OH O isophthalic acid C O C

O OH O C OH terephthalic acid C OH

benzoic acid

Salts Name cation followed by acid name with -ic changed to -ate, eg
Na+ -O C O sodium benzo ate

Physical Properties Lower molecular weight acids are soluble in H2O: hydrogen bonding. Usually soluble in organic solvents. Sodium and potassium salts of lower molecular weight acids are soluble in H2O and not soluble in organic solvents of low polarity. The salts of longchain carboxylic acids are soaps. Sodium and potassium soaps form micelles in water. A Micelle Carboxylic acids form dimers (pronounced die'-mers) in the liquid phase --O H O R C C R These dimers also O H O exit to some extent in the gas phase, consequently, carboxylic acids have high boiling points for a given molecular weight.

Acidity
O R C O H O R C Keq = R C O H pKa = -log K a OO H3O
+

O + H 2O R C OO R Ka = H2O R C O H C OO H3O
+

+ H3O

Compare acidity of carboxylic acids with alcohols: CH3CH2OH CH3COOH CH3CH2O- + H+, Ka ~ 10-16 CH3COO- + H+, Ka ~ 10-5

Reason Carboxylate anion is more stable compared to carboxylic acid than alkoxide ion is compared to alcohol. Neither alcohol nor alkoxide ion are stabilized by resonance, but the situation is different for a carboxylic acid O O and its anion; R C R C in this case the O H O H anion is stabilized more important less important more than the acid:
O R C O equally important R C O O

Substituent groups Those which stabilize the anion more than its conjugate acid (electron withdrawing) increase acid strength. Those which destabilize anion more than acid (electron donating) decrease acid strength.
5

Synthesis of Carboxylic Acids Oxidation of Primary Alcohols or Alkylbenzenes

KMnO 4 RCH2OH heat Ar-R KMnO4 heat

[RCHO]

RCOOH

Ar-COOH, where R is 1o or 2o

Grignard Synthesis --O C + R O eg MgBr + CO 2 H3O

+

O C R O MgX HX MgX

O C R O H + MgX 2

COOH

This method results in a product which has one carbon more than the reactant.

Nitrile Hydrolysis May be carried out under acidic or basic conditions conditions used may depend on other functional groups present.
H2O, H2SO4 heat R C N H2O, NaOH heat RCOOH + (NH4)2SO4 RCOO- Na + + NH3

Mechanism
Acidic Hydrolysis:
H 3O
+

C N

C N H

R C N H H2O H N H H2O H

C N H

H2O

H R C HO HO H R C N H R HO H HO C HO N H

H2O R C HO

R C N H HO

H + N H H R

O C HO +

H H N H H

Basic Hydrolysis:
OH R C N R

OH C N H 2O R

OH C N H R

O C OH N H H

O R C N H R

O C OH + N H H R

O C O + H N H H

OH H

Aliphatic Nitrile Synthesis

DMSO

RX

K+CN-

RC N

K+X -

Best if R is primary, a disaster if it is tertiary. eg DMSO CH3CH2CH2CH 2Br + CN CH3CH2CH2CH 2CN SN2 but CH3 CH3 DMSO H3C C Br + CN+ HCN H2C C E2 CH3 CH3

Reactions of Carboxylic Acids Reduction to Primary Alcohols

R-COOH (or Ar)

1. LiAlH 4 2. H 3O+

R-CH 2OH

In addition to reducing the carboxyl group, LiAlH4 will reduce nitro, nitrile, and various carbonyl groups, among others. If any of these groups are present, they must be protected or another method must be used to reduce the carboxylic acid.