CHAPTER 23

LIPIDS
23.1 INTRODCTION
Lipids are compounds of biological origin that dissolve in
nonopoler solvents.
Lipids are defined by the physical operation that we use to
isolate them.

Lipids include a variety of structure types, For example

O
H2C

HC

H2C

CH3

C
O

C
O

R'

R''

CH3

CH2OH
OH

CH3

CH(CH3)2

A fat or oil

CH3

Vitamin A

Menthol

( A

( )

O
H2C

HC
H2C

CH3

C
O

C
O

R'

OCH2CH2N+(CH3)3

O-

lecithin
()

H3C
H3C
CH3
H

H
H

HO

Cholesterol
( )

23.2 FATTY ACIDS AND TRIACYLGLYCEROLS

Triacylglycerols are the fats and oils of plant or animal origin.
Oils: Triacylglycerols that are liquids at room temperature.
Fats: Triacylglycerols that are solids at room temperature.
Same triacylglycerols: all three acyl groups in triacylglycerols
are the same.
mixed triacylglycerols: the acyl groups in triacylglycerols are
different.
Hydrolysis of a fat or oil produced a mixture of fatty acids.

O
H2C

C
O

HC

C
O

R'

H2C

R''

(1) OH- / H2O, heat

(2) H3

O+

H2C

OH

HC

OH

H2C

OH

RCOOH
+

R'COOH
R''COOH

A fat or oil

Glycerol

Fatty acids

( )

Most of fatty acids have unbrached chains and they have an even
number of carbon atoms.
The double bonds in unsaturated fatty acids are all cis and not
conjugated. Many naturally occurring fatty acids contain two or
three double bonds. Triple bond rarely occur in fatty acids.
Saturated fatty acids have relatively high points and unsaturated
fatty acids have relatively low points.

Triacylglycerols made up of large saturated fatty acids have high

melting points and are solid in room temperature, vice versa.
23.2A HYDROGENATION OF TRIACYLGLYCEROLS
Solid commercial cooking fats are manufactured by partial
hydrogenation of vegetable oils. Completed hydrogenation
of the oil is very hard and brittle. One commercial advantage
of partial hydrogenation is to give the fat a longer shelf-life.
23.2B BIOLOGICAL FUNCTION OF
TRIACYLGLYCEROLS
The primary function of triacylglycerols in animal is as an
energy reserve.

All of the saturated triacylglycerols of the body, and some of the

unsaturated ones, can be synthesized from carbohydrates and
proteins.
23.2C SAPONIFICATION OF TRIACYLGLYCEROLS
Alkaline hydrolysis of triacylglcerols produces glycerol and a
mixture of salts of long-chain carboxylic acids.
O
H2C
HC
H2C

O
O
O

C
O

C
O

R'

R''

+ 3NaOH

H2O

H2C

OH

HC

OH

H2C

OH

Glycerol
( )

RCOO-Na+
+

R'COO-Na+
R''COO-Na+
Sodium carboxylates
(

These salts of long-chain carboxylic acids are soaps and this

saponification reaction is the way most soaps are manufactured.
Soaps are almost completely miscible with water. Soaps micelles
in water are usually spherical clusters of carboxylate ions that are
dispersed throughout the aqueous phase with their negatively
charged carboxylate groups at the surface and with their nonpolar
hydrocarbon chains on the interior.
Thus soap solution are able to separate the dirt particles because
their hydrocarbon chains can dissolve in the oil layer.
Synthetic detergents function in the same way as soaps; they have
long nonpolar alkane chains with polar groups at the end.

CH3(CH2)nCH2SO2 O-Na+
Sodium alkanesulonates
(

CH3(CH2)nCH2OSO2O-Na+
Sodium alkyl sulfates
(
CH3

+Na-OO S
2

CH(CH2)nCH2CH3

Sodium alkylbenzenesulfonates
(

Synthesis of detergents offer an advantage over soaps; they

function well in hard water.
23.2D REACTIONS OF THE CARBOXYL GROUP
OF FATTY ACIDS

Fatty acids undergo reactions typical of carboxylic acids.they react

with LiAlH4 to form alcohols, with alcohols and mineral acid to
form esters, with thionyl chloride to form acyl chlorides:
(1)LiAlH4, diethyl ether
(2) H2O

RCH2COOH

CH3OH, H+
SOCl2
Pyridine

RCH2CH2 OH
RCH2 COOCH3
RCH2COCl

23.2E REACTIONS OF THE ALKYL CHAIN OF

SATURATED FATTY ACIDS
Fatty acids undergo specific halogenation when they are treated
with bromine or chlorine in the presence of phosphorus.

RCH2COOH +

(1) X2, P4

RCHXCOOH + HX

(2) H2O

23.2F REACTIONS OF THE ALKENYL CHAIN OF

UNSATURATED FATTY
The double bonds of the carbon chains of fatty acids undergo
characteristic alkene addition reactions.
H2
Ni

CH3(CH2)nCH=CH(CH2)mCO2H

Br2
CCl4
(1) OsO4
(2) NaHSO3
HBr

CH3(CH2)nCH2

CH2(CH2)mCO2H

CH3(CH2)nCHBrCHBr(CH2)m CO2 H
CH3(CH2)nCHOH

CHOH(CH2)mCO2H

CH3(CH2)nCH2CHBr(CH2)m CO2 H
+
CH3 (CH2 )nCHBrCH2(CH2)mCO2H

23.3 TERPENES AND TERPENOIDS

Hydrocarbons known generally as terpenes and oxygen-containing
compounds called terpenoids are the most important constitutents
of essential oils.
Most terpenes have skeletons of 10,15,20 or 30 carbon atoms
and are classified in the following way.
10

Monoterpenes

20

Diterpenes

15

Sesquiterpenes

30

Triterpenes

Recognition of the isoprene unit as a component of the structure

of terpenes has been a great aid in elucidating their structures.

CH2
C

H2C
H2C

CH
C

H3C
CH3
H2C
H2C
H3C

C
H

H2
C

CH H2C
C

CH

CH3

CH
C

CH3

CH3

CH2

or

or
CH
CH2

Many terpenes also have isoprene units linked in rings, and

others(terpenoids) contain oxygen.

OH

Limonene

-Pinene

()

(
)

Geraniol

Menthol

( )

( )

The carotenes are tetraterpenes. They can be thought of as two

diterpenes linked in tail-to-tail fashion.
H3C
CH3

H3C

CH3

CH3

H3C

CH3

CH3

-Carotene
( )

CH3

CH3

H3C
CH3

H3C

CH3

CH3

H3C

CH3

CH3

CH3

-Carotene
( )

CH3

H3C

H3C

CH3

CH3
CH3

CH3

H3C

CH3

CH3

CH3

-Carotene
( )

The catotenes all can be converted to vitamin A by enzymes in

the liver.

23.3A NATURAL RUBBER

The isoprene units of natural rubber are all linked in a head-to-tail

fashion and all of the bonds are cis.
H3C

H
H2C

etc

CH2

H2C

CH2

CH2

CH2
H3C

H3C

etc

Narura rubber
(

Pure rubber is soft and tacky, so it must be vulcanized by heating

with sulfur. A reaction takes place that produces cross-links
between the cis-polyisoprene chains and makes the robber much
harder.

23.4 STEROIDS
Steroids are important biological regulators that nearly always
show dramatic physiological effects when they are administered
to living organisms.
23.4A ATRUCTURE AND SYSTEMATIC
NOMENCLATURE OF STEROIDS
Steroids are derivatives of the following
perhydrocyclopentanophenanthrene ring system
18
12
19
1
2

A
3
4

11

CH3
10
5

B
6

CH317

13

D
14

8
7

16
15

In most steroids the B, C and C, D ring junctions are trans. The

A, B ring junction may be either cis or trans.
18
18

CH3

19
11

CH3
2

10

1
4

A
5

13

12
9

6
7

C
14

19

CH3

R
17

15

all ring junctions are trans

16

10

5
4

CH3

11
9

13

12

C
14

17

D
15

16

A, B ring junctions is cis

Angular methyl groups: The methyl groups that are attached at

points of ring junction
substituents: other groups that lie on the same general side of the
Molecule as the angular methyl groups.
substituents: groups that lie on the bottom.

When and designation are applied to the hydrogen atom at

position 5,the ring system in which the A, B ring junction is
trans become the 5 series; and the ring system in which the
A, B ring junction is cis becomes the 5 series.
In systematic nomenclature of the R group at position 17 determines
the base name of an individual steroid.
R
H3C 18
17
19

CH3
H
H

For example:

H
H

20

Androstane

-H

(() )
21

20

22

23

21

Pregnane

-CH2CH3
24

( )

Cholane

-CH(CH3)CH2CH2CH3

( )

The following two examples illustrate the way these base names
are used.
CH(CH3)(CH2)3CH(CH3) 2
H
H3C 18

CH2CH3
H
18
H3C
19

CH3
H

17

17

19

CH3
H

5 -Pregnan-3-one
(5--3-

H
H

5 -Cholest-1-en-3-one
(5 - -1--3-

23.4B CHOLESTEROL
Cholesterol can be isolated by extraction of nearly all animal tissues.
part of the difficulty in assigning an absolute structure to cholesterol
is that cholesterol contains eight tetrahedral. For example:
H
H3C
H3C
CH3
H

HO

H
H

Cholesterol is known to serve as an intermediate in the biosynthesis

of all of the steroids of the body.

23.4C SEX HORMONES

The sex hormones can be classified into three major groups:
(1) The female sex hormones, or setrogens.
(2) The male sex hormones, or androgens.
(3) The pregnancy hormones, or progestins.
The first sex hormone to be isolated was an estrogen, estrone.
OH
H3C

H3C

HO

HO

Estradiol
()

Estrone
( )

The examples of the second sex hormones:

O
H3C
CH3

H
HO

H3C
H3C

Anfrosterone
( )

OH

H
H

Testosterone
( )

Testosterone and estradiol are the chemical compounds from which

maleness and femaleness are derived. The differ of their
structure is slightly.
Progesterone and norethindrone are the most important progestin.

H3C
H3C

COCH3
H3C

H
H

H3C

CH

OH

Progesterone

Norethindrone

( )

( )

23.4D ADRENOCORTICAL HORMONES

At least 28 different hormones have isolated from the adrenal cortex.
Included in this group are the following two steroids:
H3C

O
H3C

COCH2OH
OH

H
H

H3C

HO
H3C

H
H

Cortisone
()

Cortisol
(

COCH2OH
OH

Most of adrenocortical steroids have an oxygen at position 11.

cortisol is the major hormone synthesized by the human adrenal
cortex.
23.4E D VITAMINS
The following reaction can produce vitamin D2. The photochemical
reaction that takes place is one in which the dienoid ring B of
ergosterol opens to produce a conjugated triene.

H3C

H3C

UV light,
room tempreature

H3C

H
HO

CH2

HO

Vitamin D2

( D2

23.4F OTHER STRUCTURE

Digitoxigenin is a cardiac aglycone that can be isolated by
hydrolysis of digitalis.
Cholic acid is the most abundant acid obtained from the hydrolysis
of human or oxbile.
O

H3C
CH3
H
HO

H3C
CH2CH2COOH
CH
HO
H3C

H3C
OH

Digitoxigenin
()

H
H

HO

H
OH

Cholic acid
(

Stigmasterol is a widely occurring plant steroid that is obeained

commercially from soybean oil
Diosgenin is obtained from a Mexican vine, cabeza de negro,
Genus Dioscorea. It is used as the starting material for a
commercial synthesis of cortisone and sex hormones.
CH3
H3C
CH3
H

H3C

H3C
OH

H3C
H
HO

HO

Stigmasterol

diosgenin
( )

23.4G REACTIONS OF STEROIDS

The stereochemistry of steroid reactions is often quite complex. It
is strongly influenced by the steric hindrance presented at the face
of the molecular methyl groups. But many reagent react preferentially
relatively at the face (the formula on next page).
When the epoxide ring of 5 ,6 -Epoxycholestan-3 -ol is opened,
Attack by chloride ion must occur from the face, but it takes place
at the more open 6 position.
CH3
H
HO

CH3
HCl

H
HO

5 ,6 -Epoxycholestan-3 -ol
(only product)

+O

CH3

+ Cl-

HO

OH

H
6

Cl

CH3
H2, Pt
HO

5
4

5 -Cholestan-3 -ol
(85-95%)
CH3
H3C
CH3
HO

C6H5COOOH
5

HO

H
H

H
6

5 ,6 -Epoxycholestan-3 -ol
(only product)
CH3

Cholesterol
( )

(1) THF: BH3

(2) H2O2, OH-

H
HO

OH

5 -Cholestane-3 ,6 -diol
(78%)

The relative openness of equatorial groups also influences the

stereochemical course of steroid reactions.
CH3
HO

CH3

4
3

C2H5OCOCl
(excess)

OH

C2H5OOCO

H
H

OH

23.5 PROSTAGLANDINS
Prostagkandins are C20-carboxylic acids that contain a fivemembered ring, at least one double bond, and several oxygenContaining functional groups. Two of the active prostaglandins
are prostaglandin E2 and prostaglandin F1.

9
11

HO

HO

CO2H

CO2H
CH3

15

CH3

20

HO

OH

Prostaglandin E2

OH

Prostaglandin F1

(E2)

(E2)

The biosynthesis of prostaglandins of the 2 series begins with a

C20 polyenoic acid, arachidonic acid.
CO2H

2O2

cyclooxygenase
CH3

Arachidonic acid
( )

H
O

several
CH3 steps

CO2H

O
H

PGE2 and other prostalandins

O2H

PGC2
(

23.6 PHOSPHOLIPIDS AND CELL MEMBRANES

Most phospholipids acid are structurally derived from a glycerol
derivative known as a phosphatidic acid.
CH2OCOR

From fatty acid

CHOCOR'
O
CH2

P
OH

OH

From phosphoric acid

In a phosphatidic acid, two hydroxyl groups of glycerol are joined

in ester linkages to fatty acids and one terminal hyfroxyl group is
joined in an ester linkage to phosphoric acid.
23.6A PHOSPHATIDES
In phosphatides, the phosphate group of a phosphatidic acid is bound
through another phosphate ester linkage to one of the following
nitrogen-containing compounds.
NH3+
CO2-

HOCH2

HOCH2CH2N+(CH3)3 HOCholine
( )

HOCH2CH2NH2
2-Aminoethanol
(2-)

L-Serine
(L-)

The most important phosphatides are the lecithins, cephalins,

phosphatidyl serines, and plasmalogens.
O

H2C

C
O

H2C

C
O

HC

C
O

R'

HC

C
O

R'

H2C

OCH2CH2N+(CH3)3

H2C

OCH2CH2NH3+

O-

O-

Lecithins

Cephalins

()

()

O
H2C

H2C

C
O

HC

C
O

R'

H2C

OCH2CHNH3+

O-

Plasmalogen

OR
O
O

C
O

R'

H2C

OCH2CH2NH3+

()

CO2

phosphatidyl serines

HC

O-

()

Like soaps and detergents phosphatides dissolve in aqueous media

by forming micelles.
The hydrophilic and hydrophobic portion of phosphaides form a
portion of a structure unit that creates an interface between an
organic and an aqueous environment.
23.6B DERIVATIVES OF SPJINGODINE
Another important group of lipids is derived from sphingosine.
On hydrolysis, sphingomyelins yield sphingosine, choline,
phosphoric acid, and a C24 fatty acid called lignoceric acid.

H3C(H2C)12
H3C(H2C)12

CHOH
CHNH2
CH2OH

H
CHOH
CHNHCO(CH2)22CH3
O
CH2OPOCH2CH2N+(CH3)3
O

Sphingosine

Sphingomyelin

()

()

23.7 WAXES
Most waxes are esters of long-chain fatty acids and long-chain
alcohols. Waxes are found as protective coatings on the skin,
fur, or feathers of animals, and on the leaves and fruits of plants.