Conformations of Acyclic Molecules
Contents
• Conformation of unsaturated acyclic and miscellaneous molecules
Conformations /
Constellation
(German) /
Rotamers
(Chemical Physics)
1
organic Chemistry
4.8 Sigma Bonds and Bond Rotation
❑ Two groups bonded by only a single bond can undergo rotation about that bond with respect
to each other.
❑ The temporary molecular shapes that result from such a rotation are called conformations of
the molecule.
❑ When a molecule has a number of conformations that correspond to energy minima, then
they are called conformers.
❑ An analysis of the energy changes that occur as a molecule undergoes rotations about single
bonds is called a conformational analysis.
American
chemist
Melvin
Spencer
Newman Sawhorse meaning a
rack supporting
wood for sawing
2
Solomon’s organic Chemistry
Sigma Bonds and Bond Rotation
3
Solomon’s organic Chemistry
Nomenclature for Distinguishing Conformations of Organic Molecules
❑ Dihedral Angle ❑ Torsion Angle
In a system attached atoms X-A-B-Y, where neither X nor Y is collinear with A
and B, the smaller angle subtended by the bonds X-A and Y-B in a plane
projection obtained by looking the system along the axis A-B is called torsion
angle. Torsion angle has a range of value from 0° to ± 180°.
https://www.youtube.com/watch?v=3RwnA- 4
Z1m2g&ab_channel=InteractiveOrganic Solomon’s organic Chemistry
Origin of torsional barrier in ethane attributed to σ–σ* hyperconjugation
5
Torsion angles and dihedral angles for two enantiomers
6
American and British system of nomenclature for distinguishing different
conformations
7
Solomon’s organic Chemistry
Kyne-Prelog Conformational Terminology based on Torsion Angle
8
organic Chemistry
Kyne-Prelog Conformational Terminology based on Torsion Angle
9
organic Chemistry
Conformation of Simple Acyclic Molecules
10
organic Chemistry
Conformation of Simple Acyclic Molecules
❑ Summary Table
11
Conformational analysis of ethane 1 kcal = 4.18 kJ
12
organic Chemistry
Conformational analysis of propane 1 kcal = 4.18 kJ
13
Conformational Analysis of Butane
14
organic Chemistry
P-M Descriptors for Conformations having axial chirality: Helical Nomenclature
❑ Conformations of 2,3-dimethylbutane
❑ Conformations of of n-propyl chloride
15
Conformation of ethane, propane, 2-methylpropane, and 2, 2-dimethylpropane
∑ E, P, MP, and MMP
(Ps) stand for ethane,
propane, 2-
methylpropane, and 2,
2-dimethylpropane and
s and e for staggered
and eclipsed
conformations
respectively in Figure
16
Population of conformers: anti ⇄ gauche for n-butane
❑In this case there is a statistical factor of 2 which favors the gauche form (since
there are two enantiomorphic gauche conformers) leading to an entropy
advantage of Rlan2 for the later. The above ∆H is for n-butane.
17
Bisecting and Eclipsing Conformations: Conformation of Alkene
❑ Conformations of propene
❑ Conformations
of 1-butene:
❑ (A) Preferred
eclipsed
conformers (cis
and gauche);
❑ (B) Bisecting
transition
structure (TS)
conformations.
18
organic Chemistry
Bisecting and Eclipsing Conformations: Conformation of Carbonyl
compounds
❑ Conformations of (A)
acetaldehyde, (B) propanal
and (C) acetone and 2-
butanone.
֍ The conformational situation in
acetaldehyde is similar to that of
propene; the eclipsed conformation
being more stable than the bisecting
conformation. The energy barrier is 1.17
kcalmol-1, which is less than that in
propene. This is probably due to less
repulsive filled/filled (σC-H/πC=O)
interaction in the bisecting
↘ The stability of the eclipsed form is explained on the basis of
conformation because of less π
character of the C=O bond (C=O ↔ C+-
electrostatic attraction between O of >C=O and H of CH3 group due to
O-). hyperconjugation, O=C-CH2-H ↔ -O-C=CH2 H+
∑ For propanal (MeCH2CHO),the conformational preference is different from that of 1-butene. Here the cis conformation
(O/Me eclipsing) is preferred over the gauche form by 0.7–1.2 kcalmol-1. The steric factor dominates in case of
19
Me3CCH2CHO, making its gauche form preferred over the cis by 0.25 kcalmol-1.
Conformation and intramolecular hydrogen bonding in acyclic molecules
20
↘ The most preferred
Conformations of Acetone and diethyl ketone conformation is one in
which one -CH3 group is
eclipsed with the >C=O
group. But it shows a long
flat region in the potential
energy curve where ω =
120° - 90° (torsion angle). It
appears that in this region,
the almost equi-energy
state is attained close to
compensation of decreasing
steric strain between the
methyl groups and at the
same time increase in
energy by the loss of
eclipsing interaction
between the methyl groups
and at the same time
increase in energy by the
loss of the eclipsing
interaction between one of
the methylene 21hydrogen
Conformations of oxime and hydrazone
22
Conformations of Enolethers, Esters and Acids
23
Conformations of Enolethers, Esters and Acids
24
Conformations of Enolethers, Esters and Acids
Trans (Z)
cis (E)
25
Conformations of Enolethers, Esters and Acids
26
Conformations of Amides
27
Conformations of (A) esters and (B) amides: Relook
28
Conformations of Haloalkanes
29
Conformations of Haloalkanes (X = F)
30
Conformations of Haloalkanes (4CH3-3CH2-2CH2-1CH2-X, X = Cl and Br: C-1/C-2 and C-
2/C-3 rotation possible)
C-1/C-2 C-2/C-3
31
Conformations of Haloalkanes (Isobutyl bromide and Isobutyl chloride: C-
1/C-2 rotation)
Preferred
Preferred
32
Conformations of 1,1,2-trichloroethane
❑ I and II are enantiomorphic and thus same in energy. I or II is the preferred conformation
33
Conformations of hexahalogenated ethanes
❑ Reason is out of syllabus 34
Conformations of Alkylbenzenes
35
Conformations of 1,3-diethylbenzene
36
Conformations of Halohydrins
37
Gauche Effect
38
Gauche Effect
39
Conformation of conjugated systems
This is 180
40
Conformation of α,β-unsaturated carbonyl compounds
41
Conformation of diastereomeric stilbene-1,2-dichloride (meso and dl-pair)
42
