BITS Pilani
Pilani Campus
CHEM F111 : General Chemistry
II-Semester: AY 2018-19
Lecture 31 (03-04-2019)
BITS Pilani, Pilani Campus
Summary of Lecture 30
Conformational isomers (conformers).
Rotating about bonds (Bond breaking not required)
Configurational isomers: (Bond breaking required)
Enantiomers.
Diastereomers
Conformations of ethane, propane and butane
Eclipsed Staggered Skew
Torsional Strain: It is the resistance to twisting (torsion) as molecule
rotates toward an eclipsed conformation.
Miscellaneous examples: X-C-C-Y containing compounds (where X
and Y are electronegative groups) adopt gauche rather than anti
conformations.
Hydrogen bonding
Stabilization accrues from σ → σ* interactions
Solvent polarity affect
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conformations of cycloalkanes
In cyclopropane or cyclobutane, one pair of bonds to each carbon
cannot assume the tetrahedral angle, but must be compressed to
600 or 900 to fit the geometry of the ring.
These deviations of bond angles from the “normal” tetrahedral
value cause the molecule to be strained, and hence to be unstable
compared with molecules in which the bond angles are tetrahedral.
An increase in energy when bond angles deviate from the
optimum tetrahedral angle of 109.5° is called angle strain.
Cycloalkanes with more than three carbon atoms in the ring are
not flat molecules. They are puckered to reduce strain.
Ring strain
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Cyclopropane and Cyclobutane
Angle strain
Necessarily Planer Torsional strain because of eclipsed hydrogens
Ring Strain = Angle strain + Torsional strain
Torsional strain partially
relieved by ring-puckering
(non-planar)
Ring opening reactions relieves the strain leads to more stable open
chain compounds. More strained means more unstable and more prone to
undergo ring opening reactions.
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Cyclopentane
• If planar, angles would be 108o but all hydrogens would
be eclipsed.
Newman
projection
• Puckered conformer reduces torsional strain. Puckering
from planar cyclopentane reduces torsional strain, but
increases angle stain (~105o).
• The conformation of minimum energy is a puckered
“envelope” conformation.
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Cyclohexane
The angles of a regular hexagon (120o) considered to be planar, are
some what larger than the tetrahedral angle. Thus, cyclohexane
molecule should have an angles strain of 10.5o. In reality, cyclohexane
adopts a puckered “chair” conformation, which is more stable than any
possible other conformation.
Planar cyclohexane
Chair conformation
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Cyclohexane
Boat conformation: A puckered conformation of a cyclohexane
ring in which carbons 1 and 4 are bent toward each other.
• There are four sets of eclipsed C-H interactions
• Another destabilizing feature is the fact that two of the “axial”
hydrogens become flagpole hydrogens.
• A boat conformation is less stable than a chair conformation by
27 kJ (6.5 kcal)/mol.
1 4
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Cyclohexane
Twist-boat conformation
The twist relieves some of the torsional strain of the
boat and moves the flag-pole hydrogens further apart
reducing the steric strain. Consequently the twist boat is
slightly more stable than the boat.
• 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
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conformational analysis of cyclohexane
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interconversion of cyclohexane chair conformation
Flipping Chair Conformations
• All axial bonds become equatorial
• All equatorial bonds become axial
• All “up” bonds stay up
• All “down” bonds stay down
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monosubstituted cyclohexanes
Strain of one H-X 1,3-diaxial interaction in kJ/mol
X
X Eaxial – Eequatorial X Eaxial – Eequatorial
-H 0.0 -COOH 2.9
-CN 0.4 -CH3 3.8
-F 0.5 -CH2CH3 4.0
-Cl 1.0 -CH(CH3)2 4.6
-Br 1.0 Ph 6.3
-OH 2.1 -C(CH3)3 11.4
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1-methylcyclohexane
Less stable more stable by 7.6 kJmol-1
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Disubstituted Cyclohexanes
cis-1,2-Dimethylcyclohexane
Two CH3-H 1,3-diaxial interaction Two CH3-H 1,3-diaxial interaction
+ One CH3-CH3 gauche + One CH3-CH3 gauche
(7.6 kJ/mol + 3.8 kJ/mol) (7.6 kJ/mol + 3.8 kJ/mol)
Total strain =11.4 kJ/mol Total strain =11.4 kJ/mol
trans-1,2-Dimethylcyclohexane
Four CH3-H 1,3-diaxial interaction One CH3-CH3 gauche interaction
(15.2 kJ/mol) (3.8 kJ/mol)
Relative 11.4 kJ/mol Relative 0.0 kJ/mol
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Disubstituted Cyclohexanes
trans-1,3-Dimethylcyclohexane cis-1,3-Dimethylcyclohexane
Most stable conformation
Two CH3-H 1,3-diaxial interaction Relative 0.0 kJ/mol
(7.6 kJ/mol); Total strain =7.6 kJ/mol
trans-1,4-Dimethylcyclohexane cis-1,4-Dimethylcyclohexane
Two CH3-H 1,3-diaxial interaction
Relative 0.0 kJ/mol (7.6 kJ/mol); Total strain =7.6 kJ/mol
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Disubstituted Cyclohexanes
Can you name these dimethylcyclohexanes?
CH3
CH3
H3C
H3C
CH3 CH3
cis-1,2-dimethylcyclohexane trans-1,3-dimethylcyclhexane trans-1,4-dimethylcyclohexane
equatorial - axial equatorial - axial axial-axial or diaxial
Which of these represent the most stable conformation possible?
What is energy difference in the corresponding most stable and
least stable conformation?
Stable conformation
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Effect of Hydrogen bonding on conformation stability
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