VIET NAM NATIONAL UNIVERSITY HO CHI MINH CITY

INTERNATIONAL UNIVERSITY
SCHOOL OF BIOTECHNOLOGY

ISOMERISM
Course: Organic Chemistry
Lecturer: Hoang Le Son
Ph.D
Group 4:
1. Hoang Ngo Linh Chi BTWE08005
2. Cai Anh Duong BTIU08155
3. Nguyen Ngoc Minh Chau BTWE08004
4. Nguyen Tran Thuy Linh BTUN08089
5. Pham Thi Truc Linh BTIU08087
6. Tran Thi Anh Thuy. BTIU08114
OUTLINE:
I. Definition
1. Isomer.
2. Constitutional isomers.
3. Stereochemistry
4. Stereoisomers.
5. Symmetry
III. Classification
IV. Stereoisomers:
1. Chirality
a) Chiral and achiral
b) Stereogenic center
c) planes of symmetry
d) Number of stereogenic center
2. Enantiomers
a) Examples
b) Properties
c) Nomenclature: R-S convention
 Priority rules
 Cyclic Compounds

3. Diastereomers
a) Examples
b) Properties
3. Compare between enantiomers and
diastereomers
5. Plane-Polarized Light

a) Ordinary light
b) Plane-polarized light

c) Rotation of Polarized Light

 dextrorotatory.
 levorotatory

a) Optically active
b) Optical purity
6. Resolution
 Racemic mixture
 Resolution

6. Fischer projections

V. References
I. DEFINITION:
1. Isomer
2. Constitutional isomers
3. Stereoisomers
4. Stereochemistry
5. Configurational isomers
6. Symmetry
1. ISOMER:
 Same molecular formula.
 Different compounds.
2. CONSTITUTIONAL ISOMERS:
 Same molecular formulas
 Differ in connectivity.
 3. STEREOISOMERS:
The same connectivity, same molecular formula, but are arranged
differently in space.
Diastereomer and Enantiomer
 4. STEREOCHEMISTRY:

Study of the relative spatial arrangement

of atoms within molecules.
An important branch is the study of
chiral molecules.
6. SYMMETRY:
II. CLASSIFICATION :
STEREOISOMERS
I. CHIRALITY OR HANDEDNESS
CHIRAL MOLECULES
 Chiral is used to describe an object that is non-
superposable on its mirror image
 MIRROR IMAGE
 Mirror image is a reflection in reverse
 Mirror image may or may not be superimposable
A HUMAN HAND IS CHIRAL OBJECT
ACHIRAL MOLECULE

Molecule that
are
superposable on
their mirror
image are
achiral
EXAMPLE
STEREOGENIC CENTER
 A carbon atom with four different atoms or group
of atoms bonded to it : chiral carbon atom

In this case: stereogenic center is chiral center

 Any location where an interchange of
groups leads to a stereoisomers is
stereogenic center
Chiral Achiral
non-superposable on their superposable on their
mirror image mirror image

No plane of symmetry contain plane of

symmetry
 Plane of symmetry: is an imaginary plane that
divide a molecule in half, such that one half is the
mirror image of other half

 A center of symmetry: is an imaginary

point that any straight line extends to point
on opposites surfaces at equal distances

Br
H

Cl
Cl

H center of  
Br symmetry
 How Many Stereoisomers
Are Possible?

maximum number of stereoisomers

sometimes fewer = 2 n
,
than this number
will exist

where n = number of stereocenters

(sterogenic carbons)
2,3,4-Trihydroxybutanal
two chiral centers
22 = 4 stereoisomers exist; two pairs of
enantiomers

CHO CHO CHO CHO

H C OH HO C H H C OH HO C H

H C OH HO C H HO C H H C OH

CH2 OH CH2 OH CH2 OH CH2 OH

A pair of enantiomers A pair of enantiomers
(Erythreose) (Threose)
 ENANTIOMERS
 Stereoisomers.
 Non-superimposable mirror images of each other.

 Always Chiral molecules.

 Have no plane of symmetry.

a)Condition:
 occur only with compounds whose molecules are chiral.

b)Examples:
 Lactic acid
ENANTIOMERS
c) Properties:

 Physical properties:
 same physical properties : melting point, boiling point, color,
hardness, density.
 EXCEPT : they rotate the plane-polarized light by equal
amounts but in opposite directions.
ENANTIOMERS
 Chemical properties:
• have identical chemical properties.
ENANTIOMERS

d) Optical activity:
One enantiomer will rotate the light clockwise and the other
will rotate the light counterclockwise by an equal amount.
 This ability of enantiomers to rotate light is called optical
activity.
ENANTIOMERS
e) Naming: R-S convention

 Priority rules (Cahn, Ingold, Prelog)

• The higher the atomic number, the higher the priority

Increasing Priority
ENANTIOMERS

e) Naming: R-S convention

If priority cannot be assigned on the basis of the atoms

bonded to the stereocenter  look to the next set of atoms.
ENANTIOMERS

e) Naming: R-S convention

• Atoms participating in a double or triple bond are

considered to be bonded to an equivalent number of similar
atoms by single bonds
ENANTIOMERS

e) Naming: R-S convention

• Atoms participating in a double or triple bond are

considered to be bonded to an equivalent number of similar
atoms by single bonds
ENANTIOMERS
e) Naming: R-S convention
1. Locate the stereocenter
2. Assign a priority to each substituent from 1 (highest) to 4 (lowest)
3. Orient the molecule so that the group of lowest priority (4) is
directed away from you
4. Read the three groups projecting toward you in order from highest
(1) to lowest priority (3)
5. If reading is clockwise, configuration is R (from the Latin rectus).
If it is counterclockwise, configuration is S (from the Latin
sinister).
D-L SYSTEM
 Commonly used by biochemistry.
 The D-L system is most frequently used for
sugars and amino acids.
D-L SYSTEM
D-L SYSTEM
ENANTIOMERS
 Cyclic Compounds
 DIASTEREOMERS :
 Stereoisomers.
 Not mirror images.
 Non-superimposable
 Have plane of symmetry
 Cis-trans isomers

Condition

 Stereoiosmers that are not mirror images

 Stereoiosmers that are not enantiomers
b) EXAMPLES

Cis-2 butene Trans-2 butene

The cis versions: means “ same side”

The trans versions: means “opposide side”
 CH3CHCHCH3
Cl Br
2-BROMO-3-CHLOROBUTANE

mirror
Cl Br Br Cl

43
S R S R
CH3 CH3 CH3 CH3
H H H H
enantiomers 1
diastereomers
Cl Br Br Cl
S S R R
CH3 H H CH3
H CH3 CH3 H
enantiomers 2
 CH3CHCHCH3
Cl Cl
2,3-DICHLOROBUTANE

Cl Cl Cl Cl

44
S R mirror image
CH3 CH3 CH3 is identicalCH3
H H H H
meso
diastereomers
Cl Cl Cl Cl
S S R R
CH3 H H CH3
H CH3 CH3 H
enantiomers
DIASTEREOMERS :

c) Properties:
• they have different physical
properties 
• they have different chemical
properties
• Example
Cis-2-buten Trans-2-buten
Molecular fomular: C4H8 Molecular fomular: C4H8

Physical properties Physical properties

• Boiling point: 4°C •Boiling point: 1°C
•Melting point: -139°C •Melting point: -105°C
•Vapour pressure, kPa at 21°C: 188 •Vapour pressure, kPa at 20°C: 212

Chemical property Chemical property

  
Meso compound
 are achiral by virtue of a symmetry plane, but contain a
stereogenic center.
 ENANTIOMERS DIASTEREOMERS

 are stereoisomers that are non-superposable  are stereoisomers that are

Definitio mirror images of each other. non-superposable, non mirror
n images of each other.

Condition  occur only with compounds whose molecules  Stereoiosmers that are not
are chiral. mirror images and not
enantiomers.

Properties  Physical properties: Physical properties:

 have the same physical properties .  have different physical
 EXCEPT : they rotate the plane-polarized properties 
light by equal mounts but in opposite
directions.
 Chemical properties: Chemiscal properties:
 have identical chemical properties,  have different chemical
 EXCEPT they interact with another chiral / biological properties
molecule differently
PLANE POLARIZED LIGHT

 Ordinary light: light vibrating in all planes

perpendicular to its direction of propagation

 Plane polarized light: is the vector sum of left

and right circularly polarized light
PLANE-POLARIZED LIGHT BEAM

λ
wavelength

SIDE
. END
VIEW
VIEW
polarized beam
NOT PLANE-POLARIZED

Sine waves
are not aligned
in the same
plane.
52
unpolarized
beam
PLANE POLARIZED LIGHT

 Compounds that are optically active

contain molecules that are chiral.
 Polarimeter: a device for measuring
the extent of rotation of plane
polarized light

53
POLARIMETER
α

Na vapor lamp

sample molecule

polarizer analyzer

54
OPTICAL ACTIVITY

 Optical activity describes the phenomenon

by which chiral molecules are observed to
rotate polarized light in either a clockwise or
counterclockwise direction.
 Observed rotation: the number of degrees,
α , through which a compound rotates the
plane of polarized light
 Dextrorotatory (+): rotation of the plane of
polarized light to the right
 Levorotatory (-): rotation of the plane of
polarized light to the left
55
• Recrystallized
tartaric acid
• Two different kinds of
crystals that were
mirror images.
• Each type of crystal
rotated light in
opposite directions
 OH OH meso
TARTARIC
HOOC ACIDCOOH
H H

OH OH OH OH

57
HOOC H H COOH
H COOH HOOC H

(+)-tartaric acid (-)-tartaric acid

enantiomers

OH OH m eso
HOOC COOH
H H
meso -tartaric acid
OH OH OH OH
OPTICAL ACTIVITY
α
 specific
rotation: [α ] T
D =
Calculated in this
cl
α = observed rotation
way is a physical
property of an c = concentration ( g/mL )
optically active l = length of cell ( dm )
substance
D = yellow light from sodium lamp

T = temperature ( Celsius )

58
OPTICAL ACTIVITY
 For a pair of enantiomers, the value of the
specific rotation of each is the same, but
opposite in sign
OH HO

C C
H H
CH3 CH2 CH3 H3 C CH2 CH3
(S)­(+)­2­Butanol (R)­(­)­2­Butanol
25 25
[α] D   +13.52 [α] D   ­13.52
59
 COOH COOH
C H H C
H3 C OH CH3
HO
(S)­(+)­Lactic acid (R)­(­)­Lactatic acid
21 21
[α]D = +2.6° [α]D = ­2.6°
OPTICAL PURITY
 Optical
purity: a way of describing the
composition of a mixture of enantiomers
[α]sam ple
Percent optical purity = x 100
[α]pure enantio mer

 Enantiomericexcess: the difference

between the percentage of two
enantiomers in a mixture
[R] ­ [S]
Enantiomeric excess (ee) = x 100 = %R ­ %S
[R] + [S]
 opticalpurity is numerically equal to
enantiomeric excess, but is experimentally
62
determined
 RACEMIC MIXTURE

Racemic mixture

 Contains (R) and (S) enantiomers with

equal amount.
 optically inactive

 Is often designated as being (+_)

Ex : the racemix mixture of (R)-2-butanol

and (S)-2-butanol :
( +- )2-butanol
RESOLUTION
 the separation of a racemic mixture into its
enantiomers
 Methods :
 Pasteur method
 Resolution by enzymes

 Chromatography using chiral media

FISCHER PROJECTION
FORMULAS
 Represent structures for chiral
molecules with two-dimensional
formulas.
 Used to depict acyclic forms of simple
carbohydrates.
 FISCHER PROJECTION FORMULA

 Vertical lines : bonds that project behind the

plane of the paper.
 Horizontal lines : bonds project out of the
plane of the paper.
 Intersection : carbon atom – stereogenic
center.
FISCHER PROJECTIONS
Draw your formula with the vertical line project away from you.
Flatten it to two dimensions

COOH COOH

67
H OH H OH
CH3 CH3
 FISCHER PROJECTION FORMULA

we can rotate by 180o but by no other angle.

DO NOT FLIP THEM OVER
COOH COOH CH3
CH 3
H OH 180 HO H
=H OH HO H =
CH 3
COOH CH3 COOH
COOH COOH
H
H
H OH 90 H 3C COOH
=H OH H 3C COOH =
CH3 CH3 OH OH

(R)-lactic acid (S)-lactic acid

APPLICATIONS
 Chromium(III)Chloride
[Cr(H20)6]Cl3
purple
[CrCl(H2O)5]Cl2.H2O
blue-green
[CrCl2(H2O)4]Cl.2H2O
green
 Lemon and orange
 thalidomine

S optical isomer R optical isomer

Bad Good
REFERENCE:

www.vnchem.com.vn
www.thuvienkhoahoc.com
www.youtube.com
www.chemvn.net
Book: Solomon & Rhymthe
Thanks for
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