Derivatives of Carboxylic Acids

-the derivatives of COOH can be interconverted.

-whereby more reactive acid derivatives are easily
converted to less reactives.
A. Esters
-Reaction of a COOH with an ROH under acidic conditions
will produce the corresponding ester.

NOMENCLATURE OF ESTERS
i. Common Name
-The names of esters consist of two words that reflect their
composite structure.
-the R grp attached to the carboxyl oxygen is stated first,
followed by the name of the acid, with ‘ic acid’ replace with
‘ate’.
-cyclic esters are called lactone whereby 4-membered ring
lactones are called β-lactones, 5-membered called γ-
lactones and 6-membered rings are δ-lactones.
-Salts of COOH are named by naming the cation first,
followed by the name of the acid, with ‘ic acid’ replaced by
‘ate’.

ii. IUPAC
-follow the name of alkane homolog series.
-cite the R grp attached to the carboxyl O atom first
followed by the name of the acid, with ‘ic acid’ replace with
‘oate’.
Examples:

O O

O
O

IUPAC: 2-oxacyclopentanone 2-oxacclohexanone

Common: γ-butyrolactone δ-valerolactone

CH2CH3

IUPAC: 3-methyl-2-oxacclohexanone
Common: δ-caprolactone
 SYNTHESIS OF ESTERS
-Reaction of a COOH with an ROH under acidic conditions
will produce the corresponding ester.
General Equation:

REACTION OF ESTERS
Examples:
1. Hydrolysis
a. Acid Hydrolysis
O O
HCl
H2O CH3CH2OH
H3C OCH2 CH3 H3C OCH3

b. Base Hydrolysis (Saponification)

OR

O -
OH O
H2O CH3OH
H3C OCH3 H3C O-
Mechanism of base-catalyzed hydrolysis:

2. Ester Amide
- Rxn of NH3 or a 1o amine with an ester gives an equivalent
of amide and an equivalent of ROH.
General equation & Mechanism of rxn:
3. Ester Ester (Transesterification Rxn)
-When an ester is treated with a different ROH in the
presence of an acid catalyst, the 2 ROH groups can
interchange.
-An equilibrium results, and the equilibrium can be driven
toward the desired ester by using a large excess of the
desired alcohol or by removing the other alcohol.
Transesterification can also occur under basic
conditions using an alkoxide.
Reaction Mechanism of Acid-Catalyzed Transesterification
 ACYL HALIDES
SYNTHESIS OF ACYL HALIDES

-acyl halides are prepared from the rxn below:

Nomenclature of Acyl Halides

i. Common Name
-name using the acid name by replacing ‘ic acid’ with ‘yl
bromide’.
ii. IUPAC name
-for acids ending with carboxylic acid, ‘carboxylic acid’ is
replaced with ‘carbonyl chloride.
Examples:
O O

H3C Cl Cl

IUPAC: ethanoyl chloride cyclopentyl carbonyl chloride

Common: acetyl chloride -

REACTIONS OF ACYL HALIDES

I. Nucleophilic acyl substitution
-Acid chlorides are often the best synthetic route to an
ester, anhydride, or amide. Examples:
Examples:
Acyl halide to to Carboxylic Acid
Example:

b. Acyl Chloride to Ester

-Attack of the alcohol at the electrophilic C= group gives a
tetrahedral intermediate.
-Loss of a chloride and deprotonation gives an ester.
-Esterification of an acyl chloride is more efficient than the
Fischer esterification.

c. Acyl Chloride to Amide

d. Acyl Chloride to Anhydride

II. Reaction of Acid Halides with Organometallics

III. Friedel-Crafts Acylation
-In the presence of aluminum chloride, acyl halides acylate
benzene, halobenzenes, and activated benzene derivatives.
 ANHYDRIDES

SYNTHESIS OF ACID ANHYDRIDES

-The most generalized method for making anhydrides is the
reaction of an RCOCl with a COOH or a carboxylate salt.
Notes:
Pyridine is sometimes used to deprotonate the acid and
form the carboxylate.
-The carboxylate attacks the carbonyl carbon, forming the
tetrahedral intermediate. Expulsion of the chloride gives
the anhydride.
General equation:

Examples:

Nomenclature of Acid Anhydrides

i. Common Name
-anhydride means ‘no water’ due to loss of 2 moles of water
to form anhydride.
-if 2 COOH molecules used to form acid anhydride are the
same, a symmetrical anhydride is obtained.
-use acid name and replace ‘acid’ with ‘anhydride’.
ii. IUPAC name
-used the alkane homolog name by replacing ‘ane’ with ‘oic
anhydride’.
Examples:

O O O O

H3C O CH3 H3C O H

IUPAC: ethanoic anhydride ethanoic methanoic anhydride
Common: acetic anhydride acetic formic anhydride
(symmetrical) (non-symmetrical)

O O

O CH3

IUPAC: benzoic ethanoic anhydride

Common: acetic benzoic anhydride
 REACTIONS OF ACID ANHYDRIDES
I. Nucleophilic Acyl Substitution Rxn
Acid anhydrides can be converted to carboxylic acids,
esters, or amides.
General Equations:

Mechanism for Conversion of Acid Anhydride to ester

and RCOOH
O O O O-
C C ROH C C R
R O R R O
OR ROH
H
ROH -ROH2

H
O O O O-
C C C C R
R O- OR R R O
ester OR
-ROH

O
C
R OH
carboxylic acid
II. Friedel-Crafts Acylation Using Anhydrides
-Catalyst may be AlCl3, polyphosphoric acid (PPA), or other
acidic reagents.
-Using a cyclic anhydride allows only one of the acid groups
to react, leaving the 2nd acid group free to undergo further
rxns. General Equation:

AMIDES

SYNTHESIS OF AMIDES
Amides can be synthesized directly from carboxylic acids,
although the acid chloride procedure uses milder condition
and often gives better yields
General Equation:
 Nomenclature of Amides
i. IUPAC Name C & Common
-name by taking the acid name and replace ‘oic acid & ‘ic
acid’ or ‘ylic acid’ with ‘amide’.
Examples:
O

O
NH2

H3C NH2
IUPAC: ethanamide benzenecarboxinamide
Common: acetanamide benzamide
 O

NH2

CH2CH3

IUPAC: cis-2-ethylcyclohexanecarbonamide
Common: -

-when a substituent is bonded to the N atom, the

substituent is stated first (if more than 1 substituent, they
are stated by alphabetical order).
-the name of each substituent is preceeded by letter N to
indicate that the substituent is bonded to a N atom on the
amide.
O
O

H3CH2C N CH2CH3
H3CH2C N
CH2CH3
H
IUPAC: N-cyclohexylpropanamide N,N-diethylbutanamide
-cyclic amides are called lactams. IUPAC uses the word ‘aza’
to denote N atome.
-For common names, length C is indicated by the common
name of COOH & a Greek letter specifies the C atom that
the N atom is attached.
O
O
a NH a
NH
b b

IUPAC: 2-azacyclohexanone 2-azacyclopentanone

Common: δ-valerolactam γ-butyrolactam
 REACTIONS OF AMIDES
General Equations:

(Dehydration)