Carboxylic Acids

y The characteristic functional group in a carboxylic

acid is the carboxy group.

O R C OH

y Carboxylic acids and their derivatives rank with

aldehydes and ketones among the most important organic compounds because their occur widely in nature, and because they serve important roles in organic synthesis.

Carboxylic Acid
y ALIPHATIC ACID

has an alkyl group bonded to the

carboxyl group y AROMATIC ACID has an aryl group; the simplest acid is formic acid, with a proton bonded to the carboxyl group y FATTY ACIDS are long-chain aliphatic acids derived from the hydrolysis of fats and oils

BOILING POINTS
y Carboxylic acid boils at considerably higher

temperature than do alcohols, ketones or aldehydes of similar molecular weights. y High boiling points of carboxylic acids result from formation of a stable hydrogen-bonded dimmer. y This dimmer contains an eight-membered ring joined by two hydrogen bonds, effectively doubling

MELTING POINTS
y Avoid containing more than 8 carbon atoms are

generally solids, unless they contain double bonds. y The presence of double bonds (especially as double bonds) in a long chain impedes the formation of a stable crystal lattice, resulting in a lower melting point. y Dicarboxylic acid melting point is relatively high

y Carboxylic acids may be prepared by the oxidation of

primary alcohols aor of aldehydes

FORMIC ACID HCO2H

y Simplest carboxylic acid y Comes from Latin word

formicus, for ant y It was first isolated by the distillation of red ants. y It is partially responsible for the irritation of ant bites and bee stings.

ACETIC ACID, CH3CO2H

y Constitutes 3-6% vinegar y Cider vinegar is produced by allowing apple juice to

ferment, which changes the sugar present to ethanol. y Pure acetic acid has a penetrating odor and produces painful burns

OXALIC ACID
y Is a dicarboxylic acid with the formula (CO2H2) or

H2C2O4. y Its molecule consists of two carboxyl groups ( dicarboxylic) bonded together.

BENZOIC ACIDsolid 6H5CO2H) (C y Colorless crystalline

with a cyclic structure y It is a monocarboxylic acid that occurs in cranberries and coal tar. y Sodium salt of benzoic acid, sodium benzoate, is used to preserve foods such as tomato ketchup and fruit juices.

Common Nomenclature
y The characteristic functional group in a carboxylic acid is the carboxy group.

O R C OH

Common Nomenclature
y Common names for aliphatic carboxylic acids are often

derived from the name of a natural substance from which the acid can be isolated.

Common Nomenclature of Carboxylic Acids

y Common nomenclature is widely used for the simpler carboxylic acid. y A carboxylic acid is named by adding the suffix ic and the word acid to the prefix for the appropriate functional groups.
O

O
OH

H3C

OH

Acet + ic acid = acetic acid Benzo + ic acid = benzoic acid

Common Nomenclature of Carboxylic Acids

y Substitution in the common system is denoted by

Greek letters rather than numbers. y The position adjacent to the carboxy group is denoted by E.

O H3C
3

CH2 CH
2 1

OH

E-bromobutyric acid

Br

Common Nomenclature of Carboxylic Acids

y Carboxylic acid two carboxy groups are called dicarboxy acids. y The unbranched dicarboxylic acid are particularly important, and are invariably known by their common names. y Some of the important dicarboxylic acids include:
CH 3

HOOC

CH2 CH2
Succinic acid

COOH

HOOC

CH 2 C CH 3

CH 2 COOH

F,F-dimethylglutaric acid

Common Nomenclature of Carboxylic Acids

y The mnemonic device to remember the names of

dicarboxylic acids is the phrase, Oh, My, Such Good Apple Pie which stands for oxalic, malonic, succinic, glutaric, adipic and pimelic acids.

Common Nomenclature of Carboxylic Acids

y Phthalic acid is an important aromatic dicarboxylic

acid.
COOH
Phthalic acid

COOH

Common Nomenclature of Carboxylic Acids

y Many carboxylic acids are known even before the

system of nomenclature existed. These include:

HOOC CH CH OH OH COOH

Ph

CH

CH

COOH

Cinnamic acid
COOH

Tartaric acid

Salicyclic acid

OH

Substitutive Nomenclature of Carboxylic Acids

y A carboxylic acid is named systematically by

dropping the final e from the name of the hydrocarbon with the same number of carbon atoms and adding the suffix oic and the word acid.

O H3C CH2 C OH
Propan + oic acid = propanoic acid

Substitutive Nomenclature of Carboxylic Acids

y The final e is not dropped in the name of the

dicarboxylic acids.
HOOC CH2 CH2 CH2 CH2 CH2 CH2 CH2 COOH

Nonanedioic acid

Substitutive Nomenclature of Carboxylic Acids

y When a carboxylic is derived from a cyclic

hydrocarbon, the suffix carboxylic and the word acid are added to the name of the hydrocarbon.
COOH

COOH
HOOC

Cyclohexanecarboxylic acid

COOH

1,2,4-benzenetricarboxylic acid

Substitutive Nomenclature of Carboxylic Acids

y The principal chain in substituted carboxylic acids

is numbered, as in aldehydes, by assigning number one to the carbonyl group.

CH3 H3C CH2 CH

5 4 3

CH2
2

COOH
1

3-methylpentanoic acid

Substitutive Nomenclature of Carboxylic Acids

yIn carboxylic acids derived from cyclic hydrocarbon,

numbering begins at the ring carbon bearing the carboxy group.

2 3 4 1

COOH

COOH

H3C

4-methylcyclohexanecarboxylic acid
Br

4-bromobenzoic acid or p-bromobenzoic acid

Substitutive Nomenclature of Carboxylic Acids

yWhen carboxylic acids contain other functional groups, the carboxy group receive priority over aldehydes and ketone carbonyl group, over hydroxy group and over mercapto groups for citation as the principal group.
O HC C H C CH OH H O CH2 CH2 C OH

4-hydroxy-7-oxo-5-heptenoic acid

Substitutive Nomenclature of Carboxylic Acids

HOOC CH2 HOOC
1

CH2 HC
2 3

CH2 CH2 COOH

4 5 6

3-(carboxymethyl)hexane-1,6-dioic acid

Fatty Acids
y Long, unbranched carboxylic acids, most commonly

consisting of 12 to 20 carbons. y Derived from the hydrolysis of animal fats, vegetable oils, or the phospholipids of biological membrane. y Can saturated or unsaturated fatty acids. y Used in the preparation of detergents and soap. (saponification)

Carboxylic Acid Derivatives

y Carboxylic acid derivatives are compounds that can

be hydrolyzed under acidic or basic conditions to give a related carboxylic acid.

Classification and Nomenclature (ESTERS)

yEster is a functional group wherein a crabonyl group

bonded to an OR group. yEsters are named as derivatives of their parent carboxylic acid by applying a variation of the system used in naming carboxylate salts. yThe group attached to the carboxylate oxygen is named first as a simple alkyl or aryl group. yThis name is followed by the name of the parent carboxylate which is constructed by dropping the final ic from the name of the acid and adding the suffix ate.

Classification and Nomenclature (ESTERS)

O

Ethyl acetate ( Common)

H3C

C2H5

Phenyl hexanoate ( Substitutive)

O Ph O C CH2 CH2 CH2 CH2 CH2 CH3

Classification and Nomenclature (ESTERS)

ySubstitution is indicated by numbering the acid

portion of the ester as in carboxylic acid nomenclature, beginning with the carbonyl as carbon-1 (substitutive nomenclature) or with the adjacent carbon as the E-position (common nomenclature). yThe alkyl or aryl group is numbered from the point of attachment to the carboxylate oxygen.

Classification and Nomenclature (ESTERS)

Common name: F-bromopropyl F-chlorobutyrate Substitutive name: 2-bromopropyl 3- chlorobutanoate

O H3C CH CH2
4 3 2

C
1

CH2 CH CH3
1 2 3

Cl

Br

Classification and Nomenclature (ANHYDRIDES)

yAnhydride is a functional group which is consist of

two carbonyl groups bonded to the same oxygen atom. yTo name an anhydride, the name of the parent acid O is followed byO word anhydride. the

Ph

Ph

Benzoic anhydride

Classification and Nomenclature (ANHYDRIDES)

O H9C4 C O O C C4H9

valeric anhydride (common) Pentanoic anhydride (substitutive)

O H 3C C O

O C H

Acetic formic anhydride ( a mixed anhydride)

Classification and Nomenclature (ANHYDRIDES)

O O Cl O

4-chlorophthalic anhydride ( a cyclic anhydride)

yMixed anhydrides are named by citing the two

parent acids in alphabetical order.

Classification and Nomenclature (NITRILES)

yNitriles are organic compounds where 3 hydrogen

atoms bonded to a carbon atom is replaced by a nitrogen atom. yNitriles are named in the common system by dropping the ic or oic from the name of the acid with the same number of carbon atoms (counting the nitrile carbon) and adding the suffix onitrile. yIn substitutive nomenclature, the suffix nitrile is added to the name of the hydrocarbon with the same number of carbon atoms.

Classification and Nomenclature (NITRILES)

Ph C
H3C C
CH3 H3C CH CH2 C

N
N

Benzonitrile ( benz + onitrile ) Acetonitrile ( acet + onitrile ) Isovaleronitrile (common) N 3-methylbutanenitrile (substitutive) succinonitrile (common) butanedinitrile (substitutive)

C CH2 CH2 C

Classification and Nomenclature (NITRILES)

y The name of the three-carbon-nitrile is shortened

in common nomenclature:
CH3CH2 CN propionitrile (not propiononitrile)

When the nitrile group is attached to a ring, a special carbonitrile nomenclature is used.

Classification and Nomenclature (NITRILES)

When the nitrile group is attached to a ring, a special carbonitrile nomenclature is used.

CH3
2-methylcyclobutanecarbonitrile

Classification and Nomenclature (AMIDES)

yThe functional group of an amide is a carbonyl

group bonded to a nitrogen atom ySimple amides are named in any system by replacing the ic or oic suffix of the acid name with the suffix amide. O
C NH2

Benzamide (benz + amide )

Classification and Nomenclature (AMIDES)

O H3C CH CH2 CH2 C Cl
K-chlorovaleramide (common) 4-chloropentanamide (substitutive)

NH2

Classification and Nomenclature (AMIDES)

yWhen the amide functional group is attached to a

ring; the suffix carboxamide is used.

CH3 C NH

2-methylcyclopentanecarboxamide

Classification and Nomenclature (AMIDES)

yAmides are classified as primary, secondary or

tertiary according to the number of hydrogens on the amide nitrogen.

O R N

H
R

O N

H
R

O N

R''

H
Primary amide

R'

R'

secondary amide tertiary amide

Classification and Nomenclature (AMIDES)

yNotice that this classification, unlike that of alkyl

halides and alcohols, refers to substitution at nitrogen rather than substitution at carbon. ySubstitution on nitrogen in secondary and tertiary amides is designated with the letter N (italicized or underlined).

Classification and Nomenclature (AMIDES)

O H3C C N
Cl

C 2H 5

C 2H 5
N,N-diethylacetamide

O C HN CH3

N-methyl-4-chlorocyclohexane carboxamide