Pysical Organic Chapter One

Structure, Reactivity and Mechanism
1
Atomic Orbitals
 An atomic orbital is defined as region in space around the nucleus
in which the probability of finding the electron is maximum
2
• These three p-orbitals designated as px, py and pz are
degenerate.
• For carbon, the e’s in the 2s and 2p orbitals are participated in

covalent bonding
3
Molecular Orbitals
According to MO theory, covalent bonds result from the
combination of atomic orbitals to form molecular orbitals.
When two in-phase atomic orbitals interact, a covalent

bond is formed
When two out-of-phase atomic orbitals interact, a node

is created between the two nuclei
An electron goes into the available molecular orbital

with the lowest energy, and only two electrons can occupy
a particular molecular orbital
4
5
6
7
8
9
10
Notice that hybridization of the above kind form single bonds.
11
Notice that hybridization of the above kind form pie bonds. This can be a double or
triple bonds depending on the number of p orbitals mixed with s.
12
Bonding in Carbon Compounds
 Bond formation between two atoms is visualized as the
progressive overlapping of an atomic orbital from each of the
participating atoms.
 The greater the overlap the stronger the bond so formed. The
relative overlapping of orbitals is as depicted below
 As seen above the bond formed by sp3 hybrid orbitals is strong

13
• C-C single bond is formed by the overlapping between
two sp3 hybridized carbon, to form strong sigma bond
14
Carbon-Carbon single bonds are as such not
reactive under normal condition. They do
undergo substitution reaction under drastic
conditions
Carbon-Carbon multiple bond (double and triple)

containing compounds, except aromatics, chiefly
under go addition reactions. Reason???
Aromatic compounds undergoes electrophilic

aromatic substitution
Home take assignment: Revise in detail 15

Factors Influencing Reactivity of Organic Compounds
Inductive Effect
 Inductive effect depends up on the “intrinsic” tendency of a
substituent to release or withdraw e’s through sigma bonds.
 Electronegative substituents like F, Cl, Br, I, OH, NH2, NO2 are

electronegative and hence exert electron withdrawing inductive
effects on carbon. The effect decreases through distance
+
+ H
C -
+ F
H
16
INDUCTIVE EFFECT AND RELATIVE STRENGTH OF CARBOXYLICACIDS
In the examples below you can observe the effect of the presence of chlorine groups
on the acidity of the carboxylic acid. As more chlorine groups which exert electron
withdrawing inductive effect exist, the acidity strength increases (bigger Ka Value)
O Ka
CH3 -5
C OH 1.75 x 10
O
-5
ClCH2 C OH 1.86 x 10
O
Cl2 HC -5
C OH 5530 x 10
O
Cl3C C OH -5
23,200 x 10
17
 The electron withdrawing inductive effect of groups reduces as the
group exists far from the reaction center. In the following example,
the electron withdrawing inductive effect of chlorine is having
little influence on the acidity strength as it is attached far from the
carboxylic functional group.
pKa
O
OH 4.82
O
OH
4.52
Cl
Cl O
OH 4.05
OH 2.86
Cl
18
Q???Arrange the following compounds in the order of
their reactivity towards nucleophilic addition
O O O
Cl OCH3 NH2
19
Resonance (Mesomeric) Effect
 This involves delocalization (pi) electrons and

non-bonded electrons.
 It has effects on the reactivity of compounds.
20
21
 Why benzene is not reactive towards addition reaction????
22
 Trophilium bromide ionizes in polar solvent to form trophilium
cation as shown below.
Polar solvent or
Br
Silver salt
 The resulting carbocation is stable via delocalization of electrons

through resonance. The stability of the cation is accounted to
aromaticity
23
Why is the p-methoxy aniline more basic than p-nitro aniline and aniline itself?
NH2 NH2 NH2
OCH3 NO2
 The methoxy-substituted aniline is more basic than the two other

compounds. Of course, p-nitro aniline is less basic because the
nitro group withdraws electrons inductively. This reduces the
charge density of the amino group making the lone pair electrons
less available for an electron deficient species.
24
ACIDITY
 The degree of strength of acidity can be compared in a similar

approach by using the concept of inductive and resonance effects.
O
CH3 C OH CH3CH2OH
Acetic acid Ethanol
Which one acetic acid or ethanol is more acidic? Why?
25
Exercises
Why compound drawn below undergo SN1 reaction at the

benzylic carbon rapidly?
CH2Br CH2Br
26
Hyperconjugation
27
28
29
30
31
Rationalize the following observation
N
N
N N
+
N
N
N
N N
No product
+
32
•Circle the most stable carbocation and rationalize
your answer
O O O
O
•Which one of the two arylphosphines shown below

is more basic? Explain.
H3C CH3 H3C CH3

P P
H3C CH3
Q R
33
The barrier to rotation around the carbon-carbon double
bond (arrows) is generally about 66 kcal/mol, as it is in
compound A. In compound B, however, the barrier to rotation
is much lower than the above value. Why?
A B
Assignment
34

Pysical Organic Chapter One

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Structure, Reactivity and Mechanism

• For carbon, the e’s in the 2s and 2p orbitals are participated in

When two in-phase atomic orbitals interact, a covalent

When two out-of-phase atomic orbitals interact, a node

An electron goes into the available molecular orbital

 As seen above the bond formed by sp3 hybrid orbitals is strong

Carbon-Carbon multiple bond (double and triple)

Aromatic compounds undergoes electrophilic

Home take assignment: Revise in detail 15

 Electronegative substituents like F, Cl, Br, I, OH, NH2, NO2 are

 This involves delocalization (pi) electrons and

 It has effects on the reactivity of compounds.

 The resulting carbocation is stable via delocalization of electrons

NH2 NH2 NH2

 The methoxy-substituted aniline is more basic than the two other

 The degree of strength of acidity can be compared in a similar

Which one acetic acid or ethanol is more acidic? Why?

Why compound drawn below undergo SN1 reaction at the

•Which one of the two arylphosphines shown below

H3C CH3 H3C CH3

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