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7.
Using the given molecular formula (C4H8O), write four different functional isomers
with their names. (2 Marks)
8.
9.
10.
What is a carbocation? Discuss their structure, formation, and stability? (1.5 Marks)
11.
Write the name of the given compound using both cis/trans and E/Z notation. (2 Marks)
12.
a)
b)
OH
HO
13. What should be the observed specific rotation of a sample having 82% eeR?
(The pure S enantiomer in the sample has a specific rotation of 23.7)
(1 Marks)
###############*********************##################***********************
H
H
Cyclopropane
H H
H
H
H
H
H
Prop
But
Pent
Hex
Hept
10
Oct
Non
Dec
Naming Cycloalkanes
Rule 1 Find the parent: Count the number carbons in the chain and the substituents. If
the substituents is longer then the ring then the parent name is the substituent. If the ring
is longer then the ring is the parent.
CH3
1-Methylcyclopentane
CH2CH2CH2CH3
1-Cyclopropylbutane
If we look at the molecule on the left. A pentane ring has 5 carbons compared to its substituent (1 carbon)
a methyl. So the parent is the cyclopentane. However on the molecules on the right butane (4 carbons) is
larger than cyclopropane (3 carbons) so the butane is the parent name.
CH 3
4
5
1
H 3C
CH 3
1,2,4-trimethylcyclopentane
Not 1,3,4-trimethylcyclopentane
Rule 3: If two or more alkyl groups have potentially the same number, number
alphabetically.
CH3
1-ethyl-2-methylcyclohexane
CH2CH3
Not 1-methyl-2-ethylcyclohexane
1-Bromo-2-methylcyclohexane
Stereoisomers
Unlike Constitutional Isomers which have the same molecular formula but a
different orientation.
Stereoisomers have the same order of connection but differ in spatial (or
three dimensional 3D) orientation.
Cis Isomers are when two atoms are on the same side of a ring.
Trans Isomers are when two atoms are on different side of a ring.
H
H
H
H
Cis Isomers
Trans Isomers
60
~109.5o
Torsional Strain
Is the strain due to eclipsing of bonds on neighboring atoms.
When atoms are eclipsed then there is a natural tendency to
move away from each other this is called torsional strain.
H H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Steric Strain
Steric strain focuses on the strain of functional groups bound due to size onto
the cyclic ring. Because rings dont rotate freely in space like linear chains then
energy is higher when they are on the same side.
repulsive interactions between nonbonded atoms in close proximity
For example: cyclopropane
H
H
H
H
Higher Energy
Lower Energy
1.5 nO2
Ring Size
Long-Chain Alkane
157.4
0.0
0.0
166.6
9.2
27.6
164.0
6.6
26.4
158.7
1.3
6.5
157.4
0.0
0.0
158.3
0.9
6.3
158,6
1.2
9.6
Baeyer (1885): since carbon prefers to have bond angles of approximately 109, ring sizes other than
five and six may be too strained to exist
Rings from 3 to 30 Cs do exist but are strained due to bond bending distortions and steric interactions
Conformations of Cycloalkanes
Cyclopropane
3-membered ring must have planar structure, The most ring strained alkane ring
Symmetrical with CCC bond angles of 60 instead of 109.5o.
Requires that sp3 based bonds are bent (and weakened)
All C-H bonds are eclipsed
Bonds are weaker and more reactive than any other cycloalkanes.
Cyclobutane
Cyclobutane has less angle strain than cyclopropane but more torsional strain
because of its larger number of ring hydrogens
Cyclobutane is slightly bent out of plane - one carbon atom is about 25 above
The bend increases angle strain but decreases torsional strain
Because of the increased torsional strain the total energy of cyclopropane
and cyclobutane are the same.
Cyclopentane
Planar cyclopentane would have no angle strain but very high torsional strain so
it twists to a puckered non-planar configuration.
Actual conformations of cyclopentane are nonplanar, reducing torsional strain
Four carbon atoms are in a plane
The fifth carbon atom is above or below the plane looks like an envelope
Conformations of Cyclohexane
Cyclohexane is strain free which means that it is stable.
Substituted cyclohexanes occur widely in nature
The cyclohexane ring is free of angle strain and torsional strain
The conformation is has alternating atoms in a common plane and
tetrahedral angles between all carbons
Adopt 2 three-dimensional structures or conformations (Chair and Boat).
5%
0.0 kcal/mol
95%
Other Substituents
X
X
X
Eaxial Eequatorial
kcal/mol
-H
0.0
-F
0.24
-CN
0.2
-Cl
0.50
-Br
0.50
-CH3
1.8
-CH2CH3
1.9
-CH(CH3)2
2.2
-C(CH3)3
5.4
1,3-Diaxial Interactions
Difference between axial and equatorial conformers is due to steric strain caused by
1,3-diaxial interactions
Hydrogen atoms of the axial methyl group on C1 are too close to the axial hydrogens
three carbons away on C3 and C5, resulting in 7.6 kJ/mol of steric strain
H3C
CH3
equatorial axial
cis-1,2-dimethylcyclohexane
CH3
H3C
equatorial - axial
trans-1,3-dimethylcyclhexane
CH3
CH3
axial-axial or diaxial
trans-1,4-dimethylcyclohexane
Drawing Structures
CYCLIC ALKANES: Substituents on a cycloalkane can be cis or trans to
each other. You should draw the ring in the plane of the paper (solid lines)
and use dashes and wedges to show whether substitutents are above or
below the plane of the ring.
correct
cis
incorrect
trans
a
a
b
b
bottom face
trans
trans
trans
incorrect
trans
cis
cis
cis
trans
cis
Cyclohexane Stereochemistry
Cis -Trans Isomers
a = axial; e = equatorial
Position
1,2
cis
e,a or a,e
trans
e,e or a,a
1,3
e,e or a,a
a,e or e,a
e,a or a,e
e,e or a,a
1,4
Trans-1,2-Dimethylcyclohexane
Methyl groups are on opposite faces of the ring
One trans conformation has both methyl groups equatorial and only a gauche butane interaction between
methyls (3.8 kJ/mol) and no 1,3-diaxial interactions
The ring-flipped conformation has both methyl groups axial with four 1,3-diaxial interactions
Steric strain of 4 3.8 kJ/mol = 15.2 kJ/mol makes the diaxial conformation 11.4 kJ/mol less favorable than the
diequatorial conformation
trans-1,2-dimethylcyclohexane will exist almost exclusively (>99%) in the diequatorial conformation