ESTERS

Carboxylic acids contain the carboxyl group on carbon.

In esters the hydrogen from the carboxyl group replaced by an
alkyl or aryl group.
Lactones are cyclic esters produced by intramolecular
O
O
C H
3
H
O
O
R
C H
3
Lactones are cyclic esters produced by intramolecular
esterification
C C
C
C C
C
O
C
C
C
H
H
H
C
H
H
H
H
H
H H
O
H
H
H
H
Wine lactone
An ester with a sweet coconut odour was recently found
to cause the smell and flavour of many white wines.
Introduction
Esters are sweet smelling organic compound.
Esters give their pleasant fragrances to fruits and
flavors.
Generally, there are several esters present in fruits
Pears contain propyl acetate; CH
3
COOCH
2
CH
2
CH
3
Pears contain propyl acetate; CH
3
COOCH
2
CH
2
CH
3
Raspberries contain ethyl formate; HCOOCH
2
CH
3
Pineapples contain ethyl butyrate;
CH
3
CH
2
CH
2
COOCH
2
CH
3
Simple esters and the fragrance with which they
are associated.
pheromones are mixtures of chemical substances released by individual bees into the hive
or environment that cause changes in the physiology and behaviour of other bees
*
*
3)
4)
Intermolecular Esterification
Intramolecular Esterification.
Carboxylic acid group and Hydroxyl group are from one compound.
Intermolecular Esterification.
Carboxylic acid group and Hydroxyl group are from two different
compounds.
4)
Intramolecular Esterification
Compound that contains both hydroxyl group and a carboxylic
function may give intramolecular esterification (produce lactones).
Lactones are stable if they contain a 5 or 6 membered ring ( and -
lactones). They are in equilibrium (note the difference!) with the
parent acid
Intermolecular Esterification
There are three ways to obtain esters through
intermolecular esterification.
1. FromAcids and Alcohols.
2. FromAcyl chlorides and Alcohol. 2. FromAcyl chlorides and Alcohol.
3. FromAcid Anhydrides and Alcohol.
The fourth way to obtain esters by intermolecular
reaction is the transesterification
Intermolecular Esterification
Formed from two different compounds by removing a
mole of water in presence of an acid catalyst.
It is also called Fisher Esterification (a classical
transformation).
Condensation process. Condensation process.
It is a reversible reaction.
Esterification
H
+
(catalyst)
(a reversible
condenstation
reaction)
Ester
O
R OH
R OH
O
R O
R
Alcohol Carboxylic Acid
H
2
O
Fischer Esterification
The cheapest way of synthesis
This is a reversible reaction; the equilibrium constant is
only slightly greater than unity (between 1 and 10).
To be successful, this reaction requires that one be able
to shift the equilibrium to the right to shift the equilibrium to the right
This is accomplished by:
removing water by azeotropic distillation
using an excess of whichever reagent is inexpensive.
Key Features of Mechanism
Activationof carbonyl groupby protonation
Nucleophilic
addition of
alcohol to
the C=O the C=O
group forms
a tetrahedral
intermediate
H
2
O elimination from tetrahedral intermediate
restores the carbonyl group
C
O
OH
isovaleric acid
+ CH
3
CH
2
OH
ethyl alcohol
H
+
C
O
O
ethyl isovalerate
+ H
2
O
1. Direct esterification is reversible and requires use of
LeChateliers principle to shift the equilibrium towards the products
(by removing water as an azeotropic mixture with benzene, or using
a drying agent like molecular sieves, or by the use of excess alcohol).
1.
isovaleric acid
ethyl isovalerate
SOCl
2
C
O
Cl
isovaleryl chloride
+ CH
3
CH
2
OH
ethyl alcohol
C
O
O
ethyl isovalerate
+ HCl
2.Indirect pathway, via acyl halides is non-reversible.
2.
Intermolecular Esterification
Advantages of acyl chloride and acid anhydride methods
over Fisher Esterification:
1. Fast.
2. High yield.
3. Mild condition. 3. Mild condition.
4. Not reversible.
Advantages of Fischer method over acyl chloride and
anhydride method of esterification:
! The cheapest way of synthesis
In transesterification, an ester is made from another ester by exchanging
the alcohol function, in both H
+
and RO
-
catalysis (best results in base).
3.
4.
Suppose we have a sample of a fat.
R
1
C O
O
CH
2
R
2
C O CH
O
R
3
C O CH
2
O
Use of transesterification
What are R
1
, R
2
, and R
3
?
1 2 3
With what frequency do they appear in a sample of the fat?
What is their relative distribution in the sample?
We cant analyze the fat sample directly, because it isnt very
soluble and it isnt volatile.
We need to convert it from a glycerol ester to some more
convenient form of ester. This is made by TRANSESTERIFICATION
Transesterification
R
1
C O
O
CH
2
R
2
C O CH
O
R
3
C O CH
2
O
CH
3
O
-

CH
3
OH
R
1
C O
O
+
R
2
C O
O
+
O
CH
3
CH
3
The methyl
esters are much
more volatile.
R
3
C O
O
CH
3
+ glycerol
The transesterified fat sample can now be
analyzed by gas chromatography.
Polyvinyl alcohol (PVOH, PVA, or PVAl) is a water-soluble
synthetic polymer for wall paints (not to be confused with
polyvinyl acetate, a popular wood glue-Aracet).
Formal obtaining: polymerization of vinyl alcohol
But vinyl alcohol DOES NOT EXIST!!!! But vinyl alcohol DOES NOT EXIST!!!!
Tautomerism to acetaldehyde
SOLUTION:
Esters with drug action:
aspirin and acetaminophen (Tylenol)
O
O
H
O
H
salicylic acid
H
3
C
O
O
O
CH
3
O
O
H
O
O CH
3
H
3
C
O
O
H
salicylic acid
3
aspirin
N
HO
H
H
H
3
C
O
O
O
CH
3
N
HO
H
O
CH
3
H
3
C
O
O
H
acetaminophen
(Tylenol)
OTHER ESTERS WITH PRACTICAL IMPORTANCE
The sweet smell
of new mown
hay hay
Esters, reactions:
1) Conversion into acids and derivatives
a) hydrolysis (in H
+
pH; in HO
-
pH is called saponification)
b) ammonolysis
c) alcoholysis (the transesterification)
2) Reaction with Grignard reagents
3) Reduction
a) catalytic
b) chemical
4) Claisen condensation
Most common mechanism is reverse of Fischer esterification
reaction
Protonation of carboxyl oxygen activates ester toward
nucleophilic attack
Nucleophilic addition of water occurs
A proton is removed from the water oxygen
The alcohol oxygen is protonated making it a better
leaving group
Alcohol is eliminated forming the carboxylic acid
Hydrolysis -acidic and basic- to carboxylic acids and alcohols
R
E
V
E
R
S
I
B
L
E
Alcohol is eliminated forming the carboxylic acid
Saponification
Basic ester hydrolysis
Named after the Latin word sapo, meaning soap
Soap is made from boiling animal fat with base
Basic hydrolysis occurs through nucleophilic acyl
substitution pathway
Occurs by cleavage of C-OR bond rather than the CO-R
bond
I
R
E
V
E
R
S
I
B
L
E
Hydrolysis of an ester in aqueous base (saponification)
requires for each mol of ester 1 mol of base; for this reason,
ester hydrolysis in aqueous base is said to be base-
+
+
O
O
RCOCH
3
NaOH
RCO
-
Na
+
CH
3
OH
H
2
O
H
H
+
-OH
Hydrolysis of an esters in aqueous acid pH leads to an
equilibrium with the initial reagents of the Fischer esterification
ester hydrolysis in aqueous base is said to be base-
promoted (not catalyzed)
Hydrolysis of an ester involves formation of a tetrahedral
carbonyl addition intermediate followed by collapse and
proton transfer (nucleophilic acyl substitution)
+
+
O
O
RCOCH
3
NaOH
RCO
-
Na
+
CH
3
OH
H
2
O
--
Lipids
= group of biological molecules that are
insoluble in aqueous solutions and soluble in
organic solvents
structural components of biological membranes
The identity of lipids is defined on the basis of a physical property
and not by the presence of a particular functional group
structural components of biological membranes
energy reserves, predominantly in the form of
triacylglycerols (TAG)
excellent mechanical and thermal insulators
biologically active compounds
(vitamins, hormones, bile acids, visual pigment)
Introduction
Lipids can be categorized as hydrolyzable and nonhydrolyzable.
[1] Hydrolyzable lipids can be cleaved into smaller molecules by
hydrolysis with water. Many hydrolyzable lipids contain an ester
unit.
Lipids
25
[2] Nonhydrolyzable lipids cannot be cleaved into smaller units by
aqueous hydrolysis.
Waxes
Waxes are esters (RCOOR) formed from a high molecular weight
alcohol (ROH) and a fatty acid (RCOOH).
Lanolin, a wax composed of a complex mixture of high molecular
weight esters, coats the wool fibers of sheep.
Spermaceti wax, isolated from the heads of sperm whales, is largely
CH
3
(CH
2
)
14
COO(CH
2
)
15
CH
3
. The three-dimensional structure of this
compound shows how small the ester group is compared to the long
hydrocarbon chains.
Lipids
26
hydrocarbon chains.
Triacylglycerols (triglycerides)
Lipids
27
Simple triacylglycerols are composed of three identical fatty
acid side chains, whereas mixed triacylglycerols have two or
three different fatty acids.
Triacylglycerols (triglycerides)
Lipids
28
Triacylglycerols (triglycerides)
All fatty acid chains are unbranched, but they must be
saturated or unsaturated.
Naturally occurring fatty acids have an even number of
carbon atoms.
All double bonds in naturally occurring fatty acids have the Z
configuration.
Lipids
29
configuration.
The melting point of a fatty acid depends on the degree of
unsaturation.
The most common saturated fatty acids are palmitic and
stearic acid. The most common unsaturated fatty acid is
oleic acid.
Linoleic and linolenic acids are called essential fatty acids
because we cannot synthesize them and must acquire them
from our diets.
Fats and oils (Triglycerides)
CH
2
C H O C R
O C R O
O
O
The human body uses fats as energy storage compounds (esters ).They
contain less oxygen than carbohydrates and are thus less oxidized so
that they release more energy when metabolised in glycolysis.
Fats are mixtures of different compounds since
the fat acids may be different (R, R, R), or
identical (example below, tristearate)
WWU-Chemistry
C
CH
2
H O C R
O C R
O
C
H
O C
O
(CH
2
)
16
CH
3
H
H (CH
2
)
16
CH
3
O
C O C
H (CH
2
)
16
CH
3
O
C O
H
C
Tristearate
The unsaturated acids found inn these esters have the cis-
configuration at the double bond. This means that the
molecules have relatively uncompact structures, so that
intermolecular forces between unsaturated triglyceride
molecules are weaker than those in the corresponding
saturated triglycerides, meaning that vegetable and fish oils,
which contain a high proportion of unsaturated triglycerides, are
liquid at room temperature, whilst the saturated triglycerides
found in animals tend to be solids at room temperature (fats)
H
2
CO
2
C
HCO
2
C
H
2
CO
2
C
Unsaturated triglyceride
Hydrogenation of Fats
CH
2
CH OCOR'
O C
O
(CH
2
)
7
CH CH R
H
2
Butter supply shortage led to necessity of replacement with a
similar solid fat
WWU-Chemistry
CH
CH
2
OCOR"
OCOR'
CH
2
CH
CH
2
OCOR"
OCOR'
O C
O
(CH
2
)
7
CH CH R
H H
Pt
Margarine, halvarine
Hydrogenation of Fats
The hydrogenation of an unsaturated fat converts it
into a saturated fat.
This is an important process in the food industry,
where unsaturated (liquid) fats are converted into where unsaturated (liquid) fats are converted into
saturated (solid) fats to replace natural butter.
Often, in an effort to retain some of the nutritional
benefits of an unsaturated fat, food manufacturers
will only partially hydrogenate a liquid fat, just
sufficiently for the material to turn semi-solid. This
would be a hydrogenated fat.
Problem: !!
Isomerization of
C C
H
CH
2
H
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
C
OH
O
CH CH
CH
2
Platinum catalyst
surface
cis-Oleic Acid
CH
3
CH
3
H
2
WWU-Chemistry
Isomerization of
Fatty Acids
C C
H
CH
2
CH
2
H CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
C
OH
O
surface
trans-Oleic Acid
The Fatty Acids
O
C OH (CH
2
)
10
CH
3
O
C OH (CH
2
)
12
CH
3
O
C OH (CH
2
)
14
CH
3
O
C OH (CH
2
)
16
CH
3
CH
3
(CH
2
)
7
CH CH (CH
2
)
7
C OH
O
Lauric acid Myristic acid Palmitic acid
3 2 7 2 7
CH CH (CH
2
)
7
C OH
O
CH
2
CH CH CH
3
(CH
2
)
4
CH CH (CH
2
)
7
C OH
O
CH
2
CH CH CH CH CH
2
CH
3
Stearic acid Oleic acid
Linoleic acid
Linolenic acid
irreversible
The carboxylate is no longer reactive for a Nucl Acyl Subst. with
the alcohol
PhospholipidsPhosphoacylglycerols
Phosphoacylglycerols (phosphoglycerides) are the second most
abundant type of lipid.
They form the principal lipid component of most cell membranes.
Their structure resembles that of triacylglycerols except that in
phosphoacylglycerols, only two of the hydroxy groups of glycerol are
esterified with fatty acids. The third OH group is part of a
phosphodiester, which is also bonded to a low molecular weight
alcohol.
Lipids
40
alcohol.
Strcture of lipids
The figure is found at http://courses.cm.utexas.edu/archive/Spring2002/CH339K/Robertus/overheads-2/ch11_lipid-struct.jpg
(Jan 2007)
PhospholipidsPhosphoacylglycerols
The phosphorus side chain of the phosphoacylglycerol makes it
different from a triacylglycerol.
The two fatty acids form two nonpolar tails that lie parallel to
each other, while the phosphodiester end of the molecule is a
charged or polar head.
Lipids
42
When these phospholipids are mixed with water, they assemble
in an arrangement called a lipid bilayer. The ionic heads are
oriented on the outside and the nonpolar tails on the inside.
When the fatty acids are saturated, they pack well in the interior
of the lipid bilayer, and the membrane is quite rigid. When there
are many unsaturated fatty acids, the nonpolar tails cannot
pack as well and the bilayer is more fluid.
Cell membranes are composed of these lipid bilayers.
PhospholipidsPhosphoacylglycerols
Lipids
Figure 29.3
Three-dimensional structure
of a phosphoacylglycerol
43
In an aqueous environment, phospholipids form a lipid bilayer, with
the polar heads oriented toward the aqueous exterior and the
nonpolar tails forming a hydrophobic interior. This layer is the wall
between the inside and outside of the cell.
Cell membranes are
composed largely of
this lipid bilayer, a
highly impermeable
structure
Esters, reaction with Grignard reagents to tertiary alcohols
R C
O
O R''
+ R'MgX
H
2
O
R C R'
OH
R'
+ R''OH
3
o
alcohol
nucleophilic
acyl substitution
O
nucleophilic
* Write the
mechanism
* 1)
R C R'
O
ketone
+ R'MgX
nucleophilic
addition
mechanism
*
2)
Esters, reduction
a) catalytic
b) chemical
R
O R'
O
+ H
2
, Ni
NR
R
O R'
O
H
2
, CuO, CuCr
2
O
4
150
o
, 5000 psi
RCH
2
OH + R'OH
R
O R'
O
LiAlH
4
H
+
RCH
2
OH + R'OH
NB Sodium borohydride (NaBH
4
) will not attack esters.
e.g. Nylon 6,6
C
O
(CH
2
)
4
C
O
HO OH