National Higher School of Technology and Engineering- Annaba
Preparatory classes of sciences and technology
Second year
University year: 2023/2024
Organic chemistry course
Chapter 3 : Reactivity in organic chemistry
-Part 1-
Dr. A. AMIRA
Email : [Link]@[Link]
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Reactivity & Electronic effects
The reactivity of organic molecules is linked to their structures and electronic
effects. A chemical group can have different effects based on the distribution of a
molecule's electron density.
The two types of electronic effects to be studied in this chapter are:
Electronic effects
Inductive effect Mesomeric effect
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Origin of inductive effect
-Polarization of the simple covalent bond-
A covalent bond is formed by sharing of electrons pair between two atoms.
non-polar covalent bond polar covalent bond
The pair of electrons is shared equally The difference of electonegativity is moderate
between two atoms with similar between two atoms 0,4 < ∆𝑥 < 1,7
electronegativity or ∆𝑥 < 0,4 . The electron density is greater around the
more electronegative atom.
Electronegativity is a measure of the
capacity of an atom A to attract a
bonding pair of electrons it shares with
another atom B.
It is a dimensionless quantity noted 𝑥,
commonly referred to as the Pauling scale.
𝑥 (A)> 𝑥 (B) A B
Direction of increase in electronegativity
in the periodic table 3
Origin of inductive effect
-Polarization of the simple covalent bond-
The asymmetrical charge distribution in a polar molecule produces a dipole moment.
Partial negative charge Partial positive charge
x (A)> x (B)
polar covalent bond
Direction of electric dipole moment 𝝁
What is an inductive effect?
It is a permanant intramolecular effect. It may create permanent dipole in the molecule.
It concerns only sigma (𝜎) polar bonds, no pi (𝜋) bond are involved.
This is an electronic polarization effect caused by a difference in electronegativity
between two atoms. 4
Types of inductive effect
Example 1 : chloromethane
𝑥 𝐶 = 2.55, 𝑥 𝐶𝑙 = 3.16
Cl atom is electron
withdrawing (-I)
Me group is electron-
donating (+I)
The effect is represented by an arrow pointing towards the more electronegative atom.
Example 2 : propylmagnesium chloride
MgCl is electron-
𝑥 (𝑀𝑔) = 1.31 donating (+I)
Pr group is electron-
withdrawing (-I)
𝛿 + = 𝛿1− + 𝛿2− + 𝛿3− and 𝛿1− > 𝛿2− > 𝛿3−
The polarization between 𝐶 − 𝑀𝑔𝐶𝑙 is transmitted along carbon chain, it induces polarity in
subsequent bonds, but it decreases rapidly and becomes negligible at 3rd or 4th carbon atom.
The inductive effect is also called transmission effect.
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Classification of inductive effect
The substituents are classified on two types of inductive effect, on the basis of electron
withdrawing or donating power compared to hydrogen possessing zero inductive effect.
The atoms or groups which withdraw electron density are noted (-I) groups.
The approximate decreasing order of (-I) strength for various substituents is as follow:
The atoms or groups which donates electron density are noted (+I) groups.
The increasing order of (+I) strength for various substituents is as follow:
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Applications of inductive effect
-bond length and dipole moment-
Generally, the increase in inductive effect decreases in bond length and increases
in dipole moment.
ℎ𝑎𝑙𝑜𝑔𝑒𝑛𝑜𝑚𝑒𝑡ℎ𝑎𝑛𝑒
Increase in inductive effect (-I)
𝑥 of halogen 2.66 2.96 3.16 4
Increase in electronegativity
Bond length of C-X (Å) 2.14 1.9 1.78 1.38
deacrease in bond length
Dipole moment (D) 1.64 1.79 1.87 1.81
Increase in dipole moment
The dipole moment of 𝐶𝐻3𝐶𝑙 is greater than that of 𝐶𝐻3 𝐹 because the bond length of C-Cl is
the greatest, and the dipole moment is the product of the magnitude separated charge (𝛿e)
and the distance (d). 7
Applications of inductive effect
-Strength of carboxylic acid-
The strength of an acid depends on its ability to give a proton.
The difference in the strength of various aliphatic acids may be explained on the basis of
the polarization of 𝑂𝐻 bond and the inductive effect of 𝑅 group.
Electron-donating group (+I) decreases the polarization of OH group (the OH bond is
strengthened), by donation of electron density, the acidity is decreasing and the pKa
value is increasing.
Electron-withdrawing group (-I) increases the polarization of OH group (the OH bond is
weakened), by attracting of electron density, the acidity is increasing and the pKa
value is decreasing.
ethanoic acid formic acid chloroethanoic acid
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Applications of inductive effect
-Strength of carboxylic acid-
The strength of acidity can be explained on the basis of stability of conjugate base. When the
acid is stronger, its conjugate base is more stable and their pKa value (acid/base) is low, and
vice-versa.
the negative charge the negative charge
order of increasing conjugate base stability
is intensified is dispersed
Factors affecting acidity strength
Example 1. increase in power of (+I) effect of alkyl groups
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decrease in acid strength (increase of pKa value)
Applications of inductive effect
-Strength of carboxylic acid-
Example 2. decrease in (-I) effect of halogens due to the decrease of electronegativity
decrease in acid strength (increase of pKa values)
Example 3. increase in (-I) effect due to the decrease in the distance between COOH and Cl
increase in acid strength (decrease of pKa values)
Example 4. increase in (-I) effect of halogens due to the additive (cumulative) effect
increase in acid strength (decrease of pKa values) 10
Applications of inductive effect
-Strength of alcohols
The strength of an alcohol depends on its ability to give a proton.
The difference in the strength of alcohols may be explained on the basis of inductive effect of
R group using the same principle as carboxylic acid.
Electron-donating group (+I) as Et, decreases the polarization of OH group, which makes
deprotonation more difficult, the acidity is decreasing and the pKa value is increasing.
Electron-withdrawing group (-I) as Cl, increases the polarization of OH group, which
makes deprotonation faster, the acidity is increasing and the pKa value is decreasing.
The additive effect of 2 Cl atoms, increases more the acidity.
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Applications of inductive effect
-Basic strength of amines-
The basic strength of amines can be defined as their ability to share a pair of electrons to
capture a proton.
The difference in the strength of amines may be explained on the basis of the availability of
electron pair on nitrogen and the inductive effect of alkyl group.
Electron-donating group (+I) increases the availability of electron pair on nitrogen
atom, by donation of electron density, the basicity is increasing and the pKa value is
increasing.
Electron-withdrawing group (-I) decreases the availability of electron pair on nitrogen
atom, by attracting of electron density, the basicity is decreasing and the pKa value is
decreasing.
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Applications of inductive effect
-Basic strength of amines-
decrease in basicity strength (decrease of pKa values)
In this case, the inductive effect don’t explain alone the basicity order, although tertiary
amine contains three methyl group (+I) but is less basic than secondary and primary
amines. It is due to steric effect of three methyl groups to donate pair electron of nitrogen.
The strength of basicity can be explained on the basis of stability of conjugate acid. When
the base is stronger, its conjugate acid is more stable and their pKa value (acid/base) is high
(pKb value is low) and vice-versa.
the positive charge the positive charge
order of decreasing conjugate acid stability
is less intensified is more intensified
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Applications of inductive effect
-Stability of carbocation intermediate-
A carbocation is an ion in which carbon atom is positively charged, it is hybridized 𝑠𝑝2 .
The unhybridized p-orbital remains vacant.
A carbocation is is very electron-poor intermediate, it don’t satisfy the octet rule.
An electron-donating (+I) substituent stabilize the carbocation.
An electron-withdrawing (-I) substituent destabilize the carbocation.
Example 1.
Most stable Least stable
Example 2.
More the positive charge of the carbocation is further from the destabilizing fluorine,
electron-withdrawing atom, the carbocation is more stable. 14
Applications of inductive effect
-Stability of carbanion intermediate-
A carbanion is an ion in which carbon atom is negatively charged, it is hybridized 𝑠𝑝3 . It
has un unshared pair of electrons.
A carboanion satisfies the octet rule.
An electron-withdrawing (-I) substituent stabilize the carboanion.
An electron-donating (+I) substituent destabilize the carboanion.
Example 1.
Least stable Most stable
Example 2.
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Applications of inductive effect
-Stability of radical intermediate-
A carboradical is a neutral entity, in which carbon atom has a single electron in p-orbital, it
is hybridized 𝑠𝑝2 .
A carboradical is electron-deficient intermediate, it it don’t satisfy the octet rule. its stability
is based on the same principle as carbocation.
An electron-donating (+I) substituent stabilize the carboradical.
An electron-withdrawing (-I) substituent destabilize the carboradical.
Example 1.
Most stable Least stable
Example 2.
Least stable Most stable
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