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Chem320 Conformational Analysis Lecture Notes 1

The document discusses conformational and configurational analysis in organic chemistry, highlighting the differences between structures that can be interconverted by rotation around single bonds (conformations) and those that require bond breaking (configurations). It details the energy differences between various conformations of ethane, propane, butane, and cyclohexane, including the stability of staggered versus eclipsed forms. Additionally, it explains the implications of these conformations on NMR signals and molecular interactions.

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456 views23 pages

Chem320 Conformational Analysis Lecture Notes 1

The document discusses conformational and configurational analysis in organic chemistry, highlighting the differences between structures that can be interconverted by rotation around single bonds (conformations) and those that require bond breaking (configurations). It details the energy differences between various conformations of ethane, propane, butane, and cyclohexane, including the stability of staggered versus eclipsed forms. Additionally, it explains the implications of these conformations on NMR signals and molecular interactions.

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noluvoluvo419
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We take content rights seriously. If you suspect this is your content, claim it here.
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Conformational Analysis

Clayden, Chapter 18
Conformation and configuration

Conformation: Structures that can be interconverted simply by rotation about single bonds

Different bonds have different barriers of rotation. For example, –C-N rotation
is slow (80KJ/mol) than C-C bond (12 KJ/mol) at 20oC.
An energy barrier of 100KJ/mol allow conformations to exist as different compounds.
O

CH3
H3C N Two methyl signals in NMR
CH3

Configuration: Structures that have restricted rotation and can be interconverted only when one or more bonds are broken
Conformations of Ethane

Staggered conformation is 12KJ/mol lower in energy than the eclipsed conformation.


Two reasons:
(1) The electronic repulsion in eclipsed conformation is greater that increases its energy.l;’

(2) There is some stabilizing interaction between C-H s bonding orbital on one carbon and the C-H s* antibonding
Orbital on the other carbon.

Eclipsed
Staggered
F ille d o rb ita ls re p e l e a c h o th e r
HH
H A
ne
m
p
ty
H
H s
C
-
Hb
on
d H
s
C
-
H
b
on
d
H
H H
H H
H H
Conformations of propane
C-C-C bond angle is 112.4o not 109.5o
So, H-C-H bond angle on the central carbon is 106.1o not the ideal angle (109.4o).
Reason: Being larger in size, there is more repulsion between C-C than C-H bonds.
Conformations of Butane
Six important conformations when central C-C bond rotates in 60o intervals:
Energy rotation graph

Syn-periplanar: eclipsed, highest energy conformation, all carbons in plane, dihedral angle is 0o, methyl groups eclipsing
each other.
Synclinal or Gauche: Staggered conformation, local energy minima, dihedral angle 60 or 300o.
Anticlinal: eclipsed conformation, comparatively lower in energy, dihedral angle 120 or 240o, methyl eclipsing hydrogens.
Anti-periplanar: Staggered conformation, methyl groups are furthest, most stable (global energy minima), all carbons are in one
plane, dihedral angle 180.
Cyclohexane: not planar molecule, no eclipsing hydrogens, fully staggered hydrogens, strain-free
Three conformations: Chair, boat and twist boat.
Chair and twist boat are low energy conformations of cyclohexane

Chair conformation

Boat conformation

Hydrogens eclipsed, bad interaction between the 1,4 “flagstaff” hydrogens


Twist boat: more stable than boat by 4kj/mol

Ring flips, so equivalent protons, one NMR signal at 1.40 ppm

Even mono-substituted cyclohexane gives one signal at room


temperature in NMR
Axial-axial (or equatorial-equatorial) represent trans when at 1,2-1,4
and 1,6-arrangement, whilst axial-equatorial represent cis for the same
positions
Axia-axial represent cis when at 1,3 and 1,5 arrangement
Axial-equatorial represent trans for the same positions.
Conformation can be locked in decalins
O T s S P h

+ P h S

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