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1st Yr Lec 7
1st Yr Lec 7
ring-flip
HA
HB
HB
Chair conformation
flagpole hydrogens
0
1.8 A
Boat conformation
HH
H
H
H
H
to make their separation impossible at r.t. At room temperature approx. 1 million introversions occur
each other second.
More than 99% of the molecules are estimated to be in chair conformation at any given time
Monosubstituted cyclohexane
X
X
This conformation is lower in energy
Why?
1,3-diaxial interaction
H
H
X
H
H
H
H
H
H
H
H
H
Me
Et
i-Pr
t-Bu
OMe
Ph
1
19
20
42
>3000
2.7
110
0
7.3
7.5
9.3
>20
2.5
11.7
50
95
95
98
>99.3
73
99
OH
OH
Preferred
conformation
t-butyl group
- a locking
group
OH
Preferred
conformation
OH
disfavoured
OH
i-Pr
Me
OH
favoured
Me
OH
CH3
CH3
CH3
CH3
CH3
CH3
1 gauche-butane interaction
0.9 kcal/mol
CH3
4 gauche-butane interaction
4 x 0.9 kcal/mol = 3.6 kcal/mol
CH3
CH3
CH3
CH3
CH3
H 3C
CH3
CH3
CH3
H3C
CH3
CH3
CH3
CH3
H3C
CH3
CH3
It is a resolavable molecule
2-gauche-butane interaction = 1.8 kcal/mol
CH3
CH3
H3C
CH3
CH3
CH3
CH3
CH3
H3C
CH3
CH3
plane of symmetry
CH3
Why is the eclipsed conformation higher in energy than the staggered conformation?
As two nonpolar groups approach each other,
the van der Waals attractive force increases to
a maximum,then decreases and becomes
repulsive
The van der Waals radius one-half the
distance between two equivalent atoms at
the point of the energy minimum
1.2
1.5
1.4
1.35
CH2
2.0
CH3
2.0
P
1.9
S
1.85
Cl
1.8
Br
1.95
I
2.15