ESTERS

James M. Mortel BS Chemistry 2

BRIEF INTRODUCTION
ESTERS

 Are derivatives of carboxylic acids (organic or inorganic) in

which at least one –OH (hydroxyl group) is replaced by an O-
alkyl (alkoxy group).

 German chemist Leopold Gmelin – introduced the word

“ester” in 19th century from the contraction of the German
word “Essigather” which means “acetic ester.”
FUNCTIONAL GROUP

ESTER

CARBOXYLIC
ACID
General Formula

RCOOR’

where R may be a hydrogen atom, an alkyl

group or an aryl group, and

R’ may be an alkyl group or an aryl group but

not a hydrogen atom (if R’ is hydrogen, then
the compound will be carboxylic acid).
Stucture and Bonding
 Esters contain a carbonyl center, which gives rise to 120
degree C-C-O and O-C-O bond angles due to
sp2 hybridization.
Unlike amides, esters are structurally flexible
functional groups because rotation about the C-O-C
bonds has a lower energy barrier.

Their flexibility and low polarity affects their physical

properties on a macroscopic scale; they tend to be less
rigid, leading to a lower melting point, and more
volatile, leading to a lower boiling point, than the
corresponding amides. 
NOMENCLATURE
1. First, identify the oxygen that is part of the continuous
chain and bonded to carbon on both sides. (On one side of
this oxygen there will be a carbonyl present but on the other
side there won't be.)

2. Second, begin numbering the carbon chains on either side

of the oxygen identified in step 1.
3. Next, use this format: [alkyl on side further from the carbonyl]
(space) [alkane on the side with the carbonyl] - (In this case:
[methyl] [methane])

4. Finally, change the ending of the alkane on the same side as

the carbonyl from -e to -oate. (In this case: methyl
methanoate)
 

5. When an ester group is attached to a ring, the ester is named as

a substituent on the ring.
Isopropyl benzoate

Ethyl benzoate
Lactones (Carboxylic esters)
• are cyclic carboxylic esters, containing a 1-oxacycloalkan-2-
one structure (–(C=O)–O–), or analogues having unsaturation
or heteroatoms replacing one or more carbon atoms of the
ring.

• Lactones with three- or four-membered rings (α-lactones and

β-lactones) are very reactive, making their isolation difficult
 Nomenclature of Lactones
First, the number of carbons between the carbon double bond
oxygen and the oxygen are counted. If there is one carbon, it is
an alpha lactone. If there are two carbons, it is called a beta
lactone. If there are three carbons, a gamma lactone. This
continues thru the Greek alphabet.
 Nomenclature of Lactones
In the second method, the ester name is generated by dropping
the word -acid from the carboxylic acid and adding –olide.
Esters can also be named by adding the word –olactone
instead of –olide and by using a Greek letter. Some examples
follow. Common and IUPAC names are both used.
PROPERTIES
Table 1. Physical Properties of some esters
Melting Point Boiling Point
Condensed Structural Formula Name Molar Mass Aroma
(°C) (°C)

HCOOCH3 methyl formate 60 −99 32

HCOOCH2CH3 ethyl formate 74 −80 54 rum

CH3COOCH3 methyl acetate 74 −98 57

CH3COOCH2CH3 ethyl acetate 88 −84 77

CH3CH2CH2COOCH3 methyl butyrate 102 −85 102 apple

CH3CH2CH2COOCH2CH3 ethyl butyrate 116 −101 121 pineapple

CH3COO(CH2)4CH3 pentyl acetate 130 −71 148 pear

CH3COOCH2CH2CH(CH3)2 isopentyl acetate 130 −79 142 banana

CH3COOCH2C6H5 benzyl acetate 150 −51 215 jasmine

CH3CH2CH2COO(CH2)4CH3 pentyl butyrate 158 −73 185 apricot

BOILING POINTS
o Esters are moderately polar, with dipole moments in the 1.5 to
2.0-D range.
o Dipole–dipole attractive forces give esters higher boiling points
than hydrocarbons of similar shape and molecular weight.
o Ester molecules cannot form hydrogen bonds to each other
and have lower boiling points than alcohols of comparable
molecular weight.
SOLUBILITY
• They participate in hydrogen bonds as hydrogen bond acceptors, but
cannot act as hydrogen bond donors, unlike their parent alcohols and
carboxylic acids. This ability to participate in hydrogen bonding
confers some water-solubility, depending on the length of the alkyl
chains attached. 
• Water solubility decreases as the carbon content of the ester increases.
Many esters occur naturally. Those of low molecular weight are fairly
volatile, and many have pleasing odors.
• Borderline solubility occurs in those molecules that have three to
five carbon atoms.
Table 1. Solubility of common esters
solubility (g per
ester formula
100 g of water)
ethyl methanoate HCOOCH2CH3 10.5
ethyl ethanoate CH3COOCH2CH3 8.7
ethyl propanoate CH3CH2COOCH2CH3 1.7
PREPARATION OF ESTERS

1. Fischer esterification
an acid-catalyzed nucleophilic acyl substitution of
carboxylic acid.
PREPARATION OF ESTERS

2. via SN2 Reactions

When treated with a strong base followed by an alkyl halide,

carboxylic acids are converted into esters
PREPARATION OF ESTERS

3. Via Acid Chlorides

Esters can also be prepared by treating an acid chloride with

an alcohol.
REACTIONS OF ESTERS
A. Hydrolysis Reaction

An ester reacts with water to form a carboxylic acid and

an alcohol. A reaction with water that converts one
compound into two compounds is called a hydrolysis
reaction (lysis is Greek for “breaking down”).
B. Transesterification

An ester reacts with an alcohol to form a new ester and a new

alcohol called alcoholysis reaction. This particular alcoholysis
reaction is also called a transesterification reaction because
one ester is converted to another ester.
C. Aminolysis

An ester reacts with an amine to form an amide. Notice that the aminolysis of an ester

requires only one equivalent of amine, unlike the aminolysis of an acyl halide, which

requires two equivalent. This is because the leaving group of an ester (RO-) is more

basic than the amine, so the alkoxide ion—rather than unreacted amine—picks up the

proton generated in the reaction.

 
USES
• Esters form a significant fraction of natural
scents of fruits and flowers.
SOURCES
ODORS OF ESTERS
Esters have pleasant fruity smells. In fact, the odors of many
fruits are due to esters. For example, ethyl ethanoate is found
in pineapples, 3-methylbutyl ethanoate in apples and bananas,
3-methylbutyl 3-methylbutanoate in apples, and octyl
ethanoate in oranges.

Octyl ethanoate
In nature also, it occurs as a communication channel for
insects.
3-methylbutyl 3-methylbutanoate

3-methylbutyl 3-methylethanoate

Ethyl ethanoate
USES
Ethyl acetate, for instance, is a commonly used solvent,
and dialkyl phthalates are used as plasticizers to keep
polymers from becoming brittle.
• Waxes – Wax esters (esters of fatty acid and fatty alcohol)
• Wine – Ethyl acetate
• Scents and Plants
• Lavender – Linalyl acetate
• Soaps – Glyceryl esters
• Material Science- Polyesters

Polyester
ANALYSIS
• Esters are generally identified by gas chromatography
because of their volatility.

• IR spectra also exist in analysis of ester compounds.

QUIZ
Nomenclature (IUPAC) (A-C)
A.

C.

B.

D.
Common Name*

II. Draw the structure of 2-bromobutyl 4-amino-3-

methoxypentanoate.
 ANSWERS
A. 2-methylpropyl methanoate
B. phenyl benzoate
C. methyl 2-hydroxybenzoate
D. γ-Lactone
II.