Nomenclature Esters

O
RCOR'

•name as alkyl alkanoates

•cite the alkyl group attached to oxygen first (R')
•name the acyl group second; substitute the suffix
-oate for the -e ending of the corresponding alkane
Esters

CH3COCH2CH3 ethyl ethanoate

O

CH3CH2COCH3 methyl propanoate

O
3-methylbutyl ethanoate
CH3COCH2CH2CH(CH3)2 (banana odor)
Esters of Glycerol

O
glycerol
CH2OH O CH2OC(CH2)16CH3

CH2OH CH3(CH2)16COCH

CH2OH CH2OC(CH2)16CH3

O
R, R', and R" can be the same or different
called "triacylglycerols," "glyceryl triesters," or
"triglycerides"
fats and oils are mixtures of glyceryl triesters
Preparation of Esters

Fischer esterification

from acyl chlorides

from carboxylic acid anhydrides

Baeyer-Villiger oxidation of ketones

Boiling Points of Esters

boiling • Esters have higher

CH3 point boiling points than
alkanes because they
CH3CHCH2CH3 28°C are more polar, but
O have lower boiling pts
CH3COCH3 57°C than alcohols because
they can’t form
OH
hydrogen bonds.
CH3CHCH2CH3 99°C
Reactions of Esters to Form Other COOH Derivatives

O
RCOR'
O

RCNR'2
O
RCO–
Reactions of Esters

Esters react with ammonia and amines

to give amides:

O O

RCOR' + R'2NH RCNR'2 + R'OH

O O
H2C CCOCH3 + NH3 H2C CCNH2 +
CH3 CH3
CH3OH
O

FCH2COCH2CH3 + NH2

heat

FCH2CNH + CH3CH2OH

(61%)
Saponification; Ester Hydrolysis in Aqueous Base

O O
RCOR' + HO– RCO– + R'OH

O
CH2OCCH3 + NaOH -> CH2OH +

CH3 CH3
O
CH3CONa
Soap-Making O

Basic hydrolysis O CH2OC(CH2)xCH3

of the glyceryl
triesters (from CH3(CH2)yCOCH
fats and oils) CH2OC(CH2)zCH3
gives salts of
long-chain O
carboxylic acids.
K2CO3, H2O, heat
These salts are
soaps.
O O O

CH3(CH2)xCOK CH3(CH2)yCOK CH3(CH2)zCOK

Polyesters; Contain many ester groups and are
made from difunctional compounds

Step 1: Formation of dimer

O O

Cl C CH2-CH2-CH2 C Cl + HO CH2-CH2-OH

O O

Cl C CH2-CH2-CH2 C O-CH2-CH2-OH
Step 2: Formation of Tetramer

O O
HO CH2-CH2-OH
Cl C CH2-CH2-CH2 C Cl

+ +
O O

Cl C CH2-CH2-CH2 C O-CH2-CH2-OH

Further reacts
Further reacts

O O O O
HO CH2-CH2-O- C CH2-CH2-CH2 C O-CH2-CH2-O C CH2-CH2-CH2 C Cl
Reactions of Esters with Nucleophiles
that Add Irreversibly

O OH
O
2) R'' MgBr 3) H+
R-C R'' R-C R''
R-C O R' + R'' MgBr

R''

O OH
O
3) H+
R-C O R' + LiAlH 4 R-C H R-C H

H
Nomenclature of Amide
Amides having an NH2 group

RCNH2

Replace –e of parent alkane with amide

Amides having an NH2 group

CH3CNH2 acetamide or ethanamide

O

(CH3)2CHCH2CNH2 3-methylbutanamide

CNH2 benzamide
Nomenclature of Amides
Amides having substituents on N

O O

RCNHR' and RCNR'2

•name the amide as before

•precede the name of the amide with the name of
the appropriate group or groups
•precede the names of the groups by the letter N-
(standing for nitrogen and used as a locant)
Amides having substituents on N

CH3CNHCH3 N-methylacetamide
O

CN(CH2CH3)2 N,N-diethylbenzamide

CH3CH2CH2CNCH(CH3)2

CH3 N-isopropyl-N-methylbutanamide
Physical Properties of Amides

1. Amides are very weak bases due to

delocalization of lone pair of N to O in
carbonyl group
( Amines are basic BUT amides are not basic)

2. Amides are acidic since ion formed when H

removed is stabalized by resonance.
Preparation of Amides

Amides are prepared from amines by acylation

with:

acyl chlorides

anhydrides
esters
Proteins are Polyamides
Amino Acids are Difunctional Monomers

R O
Amino Acid
H2N C C OH

R O R O R O
R O

+ H2N C C OH H2N C C N C C OH
H2N C C OH

H H H H
H

Dipeptide
R O
R O

H2N C C OH
H2N C C OH

H
H
+
+ R O R O

H2N C C N C C OH

H H H

polypeptide
R O R O R O R O

H2N C C HN C C N C C HN C C OH

H H H H H
Polymerization vs. Cyclization of
Difunctional Molecules

• Cyclization is preferred over polymerization if

a 5 or 6-membered ring is formed.
Amide react with water
• in basic medium to produce carboxylate ion
• in acidic medium to produce carboxylic acids

RCNR'2
O
RCO–
Hydrolysis of Amides

Hydrolysis of amides is irreversible. In acid

solution the amine product is protonated to
give an ammonium salt.
O O
+ +
RCNHR' + H2O + H RCOH + R'NH3

In basic solution the carboxylic acid product

is deprotonated to give a carboxylate ion.
O O
– –
RCNHR' + HO RCO + R'NH2
O O
CH3CH2CHCNH2 CH3CH2CHCOH

H2O +
+ NH4 HSO4–
H2SO4
heat
O
CH3CNH NH2
O
KOH
CH3COK+
H2O
heat
Br Br
Reactions of Acyl Chlorides with
Nucleophiles that Add Irreversibly

O
O

+ R'' MgBr R-C NH- + R''H + (MgBr) -

R-C NH2

O H
+
R-C NH2 + LiAlH 4 R-C NH2 R-C NH2

H H
Nomenclature of Nitriles
add the suffix -nitrile to the name of the parent hydrocarbon
chain (including the triply bonded carbon of CN)
ethanenitrile
CH3C N or: acetonitrile
or: methyl cyanide

C6H5C N benzonitrile

CH3CHCH3 2-methylpropanenitrile
C N or: isopropyl cyanide
Hydrolysis of Nitriles

Acidic Solution O
+ +
RCN + 2H2O + H RCOH + NH4

Basic Solution
O
– –
RCN + H2O + HO RCO + NH3
O

CH2CN CH2COH

H2O
H2SO4
heat
NO2 NO2

O
1. KOH, H2O, heat
CH3(CH2)9CN CH3(CH2)9COH
2. H+
Mechanism of Hydrolysis of Nitriles

O O
H2O H2O
RC N RCNH2 RCOH

Hydrolysis of nitriles proceeds via the

corresponding amide.
We already know the mechanism of amide
hydrolysis.
Therefore, all we need to do is to see how
amides are formed from nitriles under the
conditions of hydrolysis.
Mechanism of Hydrolysis of Nitriles
Step 1: Nucleophilic Attack of Electrophilic Carbon
H
H •• O••
•• O •–
•• • RC N •• RC
•• N ••
Step 2: Protonation of –
negative ion by water
H H
• O •• O ••
•
••
RC H RC H
•• N •• H O •• •• N H • O ••
– •• – • ••
Step 3: Hydroxide ion removes H
of alcohol and reforms C=O.

H
H •• O ••
•• O •• •• •
– •• O• H

H RC
O •• –
•• N H
•• ••
RC

•• N H
Step 4: Formation of intermediate amide
by protonating negative ion.

•• • •• •
O• O•

RC RC
–
•• N H •• N H
•• •• – ••
H O •• •O•
• •
H
H H
Step 5; Hydrolysis of Amide to form carboxylate ion.
Addition of Grignard Reagents to Nitriles

NMgX NH
R'MgX H2O
RC N RCR' RCR'
diethyl
ether H3O+

1. Grignard reagents add to carbon-

nitrogen triple bonds to produce an O
imine.
RCR'
2. Imines are readily hydrolyzed to
ketones.
Example

C N + CH3MgI

F3C 1. diethyl ether

2. H3O+, heat

CCH3 (79%)

F3C