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Isomerism: Chemistry 31
Isomerism: Chemistry 31
Isomerism
UNIVERSITY OF THE PHILIPPINES MANILA
Padre Faura, Ermita, Manila
SS, 2009 – 2010
Ms. Anjelyn del Rosario
chem31 adr 1
Isomerism
Isomers
Compounds that have the same molecular formula but are
not identical
chem31 adr 2
Isomerism
The Two Major Classes of Isomers:
• The two major classes of isomers are constitutional isomers and
stereoisomers.
Constitutional/structural isomers have different IUPAC names,
the same or different functional groups, different physical
properties and different chemical properties.
Stereoisomers differ only in the way the atoms are oriented in
space. They have identical IUPAC names (except for a prefix like
cis or trans). They always have the same functional group(s).
• A particular three-dimensional arrangement is called a
configuration. Stereoisomers differ in configuration.
Isomerism
4
Constitutional Isomers
Structural Isomerism
• Structural isomers are molecules CH2 CH2
with the same chemical formulas CH3 CH2 CH3
but different molecular structures n-pentane, C5H12
- different “connectivity”.
• They arise because of the many
CH2 CH3
ways to create branched CH3 CH
hydrocarbons.
• a.k.a. “Constitutional Isomers” CH3
2-methylbutane, C5H12
The First 10 “Normal” Alkanes
Name Formula M.P. B.P. # Structural Isomers
• Methane CH4 -183 -162 1
• C1 - C4 are Gases
Ethane C2H6 -172 -89 1
• Propane C3H8 -187 -42 1
•
at Room Temperature
Butane C4H10 -138 0 2
• Pentane C5H12 -130 36 3
• Hexane C6H14 -95 68 5
• C5 - C16 are Liquids
Heptane C7H16 -91 98 9
• Octane C8H18 -57 126 18
•
at Room Temperature
Nonane C9H20 -54 151 35
• Decane C10H22 -30 174 75
Constitutional Isomers
1. Chain Isomers
have the same number of C and H atoms but different points
of attachment
CH2 CH2
CH3 CH2 CH3
n-pentane, C5H12
CH2 CH3
CH3 CH
CH3
2-methylbutane, C5H12
Constitutional Isomers
2. Position Isomers
Differ in the positions of substituents or multiple bonds
Constitutional Isomers
3. Functional Isomers
Differ in their functional groups.
2. Stereochemistry
Stereochemistry
the study of the spatial arrangement of atoms in molecules.
chem31 adr 10
Stereochemistry
Example of Stereoisomers:
Stereoisomers differ
only in the way the
atoms are oriented in
space. They have
identical IUPAC names
(except for a prefix like
cis or trans). They
always have the same
functional group(s).
Conformational Isomers
I. Rotation about
Single Bonds
Conformational Isomers
Example: Ethane
Conformational Isomers: Rotation about Single Bonds
Example: Ethane
H
H H
H H
H
Conformational Isomers: Rotation about Single Bonds
Example: Ethane
H
H
H
H HH
Conformational Isomers: Rotation about Single Bonds
Conformational Isomers: Rotation about Single Bonds
• Torsional strain
– also called eclipsed interaction strain
– strain that arises when nonbonded atoms separated by three
bonds are forced from a staggered conformation to an eclipsed
conformation
– the torsional strain between eclipsed and staggered ethane is
approximately 12.6 kJ (3.0 kcal)/mol
+12.6 kJ/mol
Conformational Isomers: Rotation about Single Bonds
Eclipsed Butane
– calculated energy difference between (a) the non-energy-
minimized and (b) the energy-minimized eclipsed
conformations is 5.6 kJ (0.86 kcal)/mol
Conformational Isomers: Rotation about Single Bonds
• anti conformation
– a conformation about a single bond in which the groups lie at
a dihedral angle of 180°
CH 3
H H
H H
CH 3
Conformational Isomers: Rotation about Single Bonds
Angle strain
the strain induced in a molecule when the bond angles are
different from the ideal tetrahedral bond angle of 109.5°.
Torsional strain
the strain caused by repulsion between the bonding electrons of
one substituent and the bonding electrons of a nearby
substituent.
Steric strain
strain caused by atoms or groups of atoms approaching each
other too closely.
Conformational Isomers: Rotation about Single Bonds
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
1. Cyclopropane
• Large ring strain due to angle compression
• Very reactive, weak bonds
• Torsional strain because of eclipsed hydrogens
27
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclobutane
– puckering from planar cyclobutane reduces torsional strain
but increases angle strain
– the conformation of minimum energy is a puckered
“butterfly” conformation
– strain energy is about 110 kJ (26.3 kcal)/mol
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
3. Cyclopentane
– puckering from planar cyclopentane reduces torsional
strain, but increases angle stain
– the conformation of minimum energy is a puckered
“envelope” conformation
– strain energy is about 42 kJ (6.5 kcal)/mol
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclohexane
• Chair conformation: the most stable puckered conformation
of a cyclohexane ring
– all bond C-C-C bond angles are 110.9°
– all bonds on adjacent carbons are staggered
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclohexane
Axial and equatorial
ring flip
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclohexane
• Boat conformation: carbons 1 and 4 are bent toward each
other
– there are four sets of eclipsed C-H interactions and one flagpole interaction
– a boat conformation is less stable than a chair conformation by 27 kJ (6.5
kcal)/mol
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclohexane
• Twist-boat conformation
– approximately 41.8 kJ (5.5 kcal)/mol less stable than a chair conformation
– approximately 6.3 kJ (1.5 kcal)/mol more stable than a boat conformation
Conformational Isomers: Cycloalkanes
Cycloalkanes: Ring Strain
2. Cyclohexane
• Half-chair conformation
Conformational Energy
Chapter 3 35=>
Conformational Isomers
II. Amine Inversion
Conformational Isomers
Amine Inversion
• The lone-pair electrons on nitrogen allow an amine to turn
“inside out” rapidly at room temperature.
Exercise
Configurational Isomers
“If the hydrogens are on the same side of the double bond, it is the cis isomer;
if they are on opposite sides of the double bond, it is the trans isomer.”
The cis isomer has its substituents on the same side of the ring.
The trans isomer has its substituents on opposite sides of the ring.
Configurational Isomers
I. Cis-Trans Isomers
cyclic alkanes
Configurational Isomers
Exercise:
Determine whether each of the following compounds is a cis isomer
or a trans isomer: