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Lecture 2_conformations

The document discusses conformational analysis, particularly focusing on ethane and propane, highlighting the stability of staggered versus eclipsed conformations and the energy barriers associated with bond rotation. It also covers types of molecular strain, including torsional, steric, and angle strain, and introduces cyclohexane conformations, specifically chair and boat forms. The concept of ring flipping in cyclohexane and its energetic implications are also explained.

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Brian Mackwan
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7 views

Lecture 2_conformations

The document discusses conformational analysis, particularly focusing on ethane and propane, highlighting the stability of staggered versus eclipsed conformations and the energy barriers associated with bond rotation. It also covers types of molecular strain, including torsional, steric, and angle strain, and introduces cyclohexane conformations, specifically chair and boat forms. The concept of ring flipping in cyclohexane and its energetic implications are also explained.

Uploaded by

Brian Mackwan
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Recap

= 3 4
=

Fischer Projection

Various representations

Ethane – 3D
Configurations & Conformations
Different configurations

Can be
separated

Different conformations
No animals were harmed in the making of this slide

Difficult to
separate
Conformational Analysis
Conformational Analysis is the study of energetics of
different conformers
Energy versus torsional angle (dihedral angle)

What is dihedral angle?

 = 180
Bond length between 2 atoms
Bond angle between 3 atoms
Dihedral angle between 4 atoms
Conformational Analysis - Ethane
Ethane has two major conformers – Staggered and Eclipsed
1 kcal

1 kcal 1 kcal

Staggered (S) Eclipsed (E) Staggered (S)


The eclipsed conformation of ethane is 3 kcal/mol less stable
than the staggered conformation. (1 kcal/mol for each eclipsed
H/H pair)
Rotation Around Bonds is Not “Free”
Barrier to rotation here 3 kcal/mol
Rotational Barrier in Ethane
Barrier of 3 kcal mol-1 due to steric and electronic effects

Transition state Most stable conformer


is eclipsed is staggered

5
Conformational Analysis - Ethane
Eclipsed conformer is 3.0 kcal/mol higher in energy than the
staggered conformer: eclipsing interactions H/H (1.0 kcal)

S E

6
Small Activity

Calculate the barrier of rotation for propane,


2-methyl propane and 2,2-dimethyl propane

Eclipsing interactions H/H (1.0 kcal) and Me/H (1.3 kcal)


Check your Answers
Eclipsing interactions H/H (1.0 kcal) and Me/H (1.3 kcal)

MeH MeH MeH

H H Me Me
H H H Me
H H H H

Calculated 3.3 kcal/mol 3.6 kcal/mol 3.9 kcal/mol


Observed 3.4 kcal/mol 3.9 kcal/mol 4.7 kcal/mol
Conformational Analysis - Propane
Note: eclipsing interactions H/H (1.0 kcal) and Me/H (1.3 kcal)
1.3 kcal

1 kcal 1 kcal

9
Lone Pairs Are Not Bad!

3 kcal 2 kcal 1 kcal


Conformational Analysis - Butane
A G

C E

B F
D

6 kcal 0.9kcal 3.6 kcal lowest 3.6 kcal 0.9kcal 6 kcal


totally gauche eclipsed anti eclipsed gauche totally
eclipsed eclipsed

4 kcal gauche interaction


0.9 kcal

A B C D E F G
Steric Strain

• The totally eclipsed conformation is higher in energy because it


forces the two end methyl groups so close together that their
electron clouds experience a strong repulsion

• This kind of interference between two bulky groups is called steric


strain or steric hindrance
Types of Molecular Strain
Torsional Strain: Extra energy of eclipsed conformation arising due
to the repulsion between bonding electrons of one substituent with
that of the other as they pass close to each other

Steric Strain: Strain induced when two atoms or groups in a


molecule are too close to each other, arising due to repulsion
between electron clouds of interacting atoms/groups

Angle Strain: Strain induced in molecules when the bond angles are
different from the desired tetrahedral bond angle of 109.5°
Cyclohexane
Both angle and torsional (eclipsing interactions) strains
can be avoided by ring puckering.

Ring puckering leads to “CHAIR” and “BOAT” conformers


Drawing Chair form

This end
“down” “up”

Equatorial bonds must be parallel to the C–C bond(s) “one over”


[not the attached one(s), but the next one(s)]
D.H.R. Barton Invents Conformational Analysis (1950)

  “up” ;   “down”
ERRORS? (for molecule in conventional orientation,
old-fashioned configuration notation, like cis / trans)

) (e) “equatorial”

(p) “polar” (now axial)

3-fold axis

(Nobel Prize 1969 for “development of the concept


of conformation and its application in chemistry”)
16
Ring Flipping in Cyclohexane
1

2 2 1

Hax and Heq are distinguishable at very low temp.


The Ring Flip Causes Equatorial-Axial Exchange

Gº = 0

The two structures are the same!

18
Ring Flip
Ring Flipping - Energetics
In monosubstituted (small groups) cyclohexanes the ring
flipping is of the order of 104 to 105 inversions/second

100,000 times/sec
Chair v/s Boat : Newman Projection
Chair Staggered form

Boat Eclipsed form

Rel E = 6.9 kcal


Relief by Twisting

But this is only part of its mobility. The molecule


“flips” from one chair to another chair form.
Ring Flip - Summary

The two structures are the same.


What happens in substituted cyclohexanes?

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