Chapter III.

STRUCTURAL
EFFECTS
TRẦN THANH HƯƠNG
VŨ THỊ NGỌC LAN
Contents
III.1.Importal structural effects: electron and steric effects
III.2. Hammett equation and Hammett electron constants
III.3. Taft equation. Inductive and conjugated constants
Learning outcomes
At the end of this chapter, you will:
o Classify the structural effects: electron and steric effects
o Describe the characteristics of organic compounds by structure
o Apply Hammett equation and Taft equation to explain for the
fomations
III.1. Importalstructural effects:
electron and steric effects.
a) Inductive effects
b) Conjugative effects
c) Hyperconjugation
d) Steric Effect
A. Inductive effects
1.Concept
• An inductive effect is an electronic effect due to the polarization of σ
bonds within a molecule or ion. This is typically due to an
electronegatvity difference between the atoms at either end of the
bond.
• The more electronegative atom, the more it pulls the electrons in
the bond towards itself creating some bond polarity
• Basis here is the polarity.
.
• Three considerations:
1) electronegativity,
2) bonding order and charge and
3) position within a structure
2.Classification
Electron attracting or Withdrawing Inductive Effect
• Has a Negative inductive effect (-I)
• Electrons are draw on towards atoms with:
1. Excess positive charges
2. Electronegative atoms
3. Atoms with increased electronegativity due to more electrons
2.Classification
Electron donating inductive effect
• Has a positive inductive effect ( + I)
• Electrons are repelled by:
1. Less electronegative atoms (ex. C)
2. Negatively charged functional groups
- The effect (-I) of atoms or groups of atoms absorbing e (Cl, OH,
NO2...) increases with increasing negative
Electricity: –I < - Br < - Cl < - F or –NH2 < - OH < - F
- The effect (+ I) of alkyl groups increases with the order of the
group:
- CH3 < - CH2CH3 < - CH(CH3)2 < - C(CH3)3
B.Conjugative effects
1, The polarization of π bonding
- The π bonding between two atoms with different
electronegativity is always polarized towards the atom of which
element has the greater electronegativity.
- The polarization of π bonding is described by the common arrow
and also quantitatively evaluated the polarity moment table.
- Example: CH2= CH2 µ = 0,00 D
CH2= O µ =2,27 D
 Conjugative effects
2.Conjugated system and conjugation effect
- The system of π-bonds interspersed with residential bonds to
form MO π that is common to the whole molecule is called
conjugation system.
- Example : butadiene
B. Conjugative effects
2.Conjugated system and conjugation effect
- If replacing a group = CH2, in the above molecule is = 0, the
conjugate relationship is always polarized towards = 0, which we can
denote by the curved arrows
2.Conjugated system and conjugation
effect
- The polarization phenomenon on the conjugate as above is called
the conjugate effect, and denoted by the letter C (from Conjugation
Effect).
- The -CH = 0 group that causes the conjugation effect by pulling the
electron towards it (or the electron attraction) is considered the
negative conjugation group (symbol - C).
2.Conjugated system and conjugation effect
- Example : CH2=CH-Cl

-The chlorine atom in the above example that causes the

conjugation effect by shifting electrons towards π bond is
considered to be the positive conjugation group (symbol + C).
2.Conjugated system and conjugation effect
- Considering the strength of the – C effect
> C=O > >C= NH > >C=CH2
- Considering the strength of the + C effect
-F > -Cl > -Br > -I
-NH2 > -OH > -F
C. Hyperconjugation effect
1. Concept
- Is the conjugation effect of σ C-H bonds or small saturated rings
with C = C multiples, C≡C separates from C-H bonds or small
saturated 1 single bond.
2.Classification
2.1. Positive hyperconjugation
- Reaction :
CH3-CH=CH-CH2 -CH3 + HCl
+, If in terms of + I : main product is CH3-CH2-CHCl- CH2-CH3
However, in fact, due to the effect of +H , the product is:
2.1. Positive hyperconjugation
+ H is stronger when the number of H atoms in Cꭤ is more:

+ The hyperconjugation effect increases with the number of C –H bonds in position

ꭤ.
CH3 > CH3CH2 > (CH3)2CH > (CH3)3C
Ch3 ncxcxncjsdkdvCH3), CH-> (CH3), C.
2.2 Negative conjugation effect
- Negative conjugation effect (-H) Is the interaction of the residential
electrons of the Ca - F bond with the electronic system π (C = C,
-C6H5 ...)
D. Steric effect
1. The SN1 reaction
- Due to the large substituents, occupying a considerable amount of space 
prevent a certain functional group in the molecule from interacting with other
molecules or ions
D. Steric effect
2. The SN2 reaction :
- Due to the large potential groups -> the conjugation loses its flatness -> does
not give some reactions.

- R= H : reaction occurs
- R = -CH3 ,: conjugate loses flatness  + C of -N(CH3)2 decrease  reaction
does not occur
D. Steric effect
3. Ortho effect
- Caused by substituent groups in the ortho position in the benzene
 exerts special effect compared with substituents at other
- Ortho effect :mixture of many factors (S1, S2, I , H bond )
- Depending on the case, some of them are more dominant
III.2. Hammett equation and
Hammett electron constants
The equation also holds for reaction rates k of a series of
reactions with meta- and para- substituted benzene derivatives:

◦ k0 is the reference reaction rate of the unsubstituted reactant, and k

that of a substituted reactant.
◦ substituent constant σ which depends only on the specific
substituent X
◦ reaction constant ρ which depends only on the type of reaction but
not on the substituent used
Substituent constants
 σ- Hammett” constant characterizes total electron effects of
one substituent at meta- or para- positions

=> The more the stronger its effects; the less– the weaker.
 EDGs:
◦ NH2 > CH3O

Substituent
constants

For example:
EWGs:
◦ F < NO2
  When a substituent X, an aromatic ring and
a reaction center Y create a conjugated
system and X, Y have strong reversal each
Substituent to other conjugative effects, we should use
constants “through-conjugation” constants ( or )

“Through-
“Through- Subtituent Reaction center conjugation” constant
conjugated” +C -C
Hammett constants:
-C +C
Reaction constants
 “Rho” constant:
◦ The more [] - the more the influence of substituent X to the reaction
center Y (the more sensitivity)
ρ>1, the reaction is more sensitive to substituents than the reaction
center and negative charge is built during the reaction (or positive
charge is lost).
0<ρ<1, the reaction is less sensitive to substituents than the reaction
center and negative charge is built (or positive charge is lost).
ρ=0, no sensitivity to substituents, and no charge is built or lost.
ρ<0, the reaction builds positive charge (or loses negative charge).
 Reaction X Y
1
1 -OH
-OH Phenol
Phenol +2.11
+2.11
Reaction 2
2 -OH
-OH Benzoic
Benzoic ester
ester +2.54
+2.54
constants

For example:  
Reactions I & 2 are nucleophilic (>0)
Reaction 2 is more sensitive than 1 (2 >1)
III.3. Taft equation. Inductive and
conjugated constants
 As a modification of the Hammett equation for acyclic systems

Example: RCOOC2H5

Constants Taft * and * are similar to and constants in the Hammett

equation (* includes
inductive and steric effects only).
  R = H:

Constants Taft