National Higher School of Technology and Engineering- Annaba

Preparatory classes of sciences and technology

Second year
University year: 2024/2025

Organic chemistry course

Chapter 3 : Reactivity in organic chemistry
-Part 2-

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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 What is mesomeric effect?

Mesomeric effect is a permanent effect due to the delocalization

(displacement), to a single covalent bond, of :

 𝜋 electrons from multiple bonds (double or triple),

 lone pair of electrons 𝑛 of the heteroatoms or the anions.

Mesomeric effect occurs in unsaturated and especially conjugated compounds,

having alternating or conjugated systems giving a number of structures for the
molecule.

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 Conjugated systems
A conjugated system contains at least three parallel 𝒑 orbitals on three consecutive atoms
that may overlap laterally.
A conjugate system is defined by an alternation between:
 𝒏− 𝝈−𝛑
 𝛑− 𝝈−𝛑
 𝝅 − 𝝈 − 𝒆𝒎𝒑𝒕𝒚 𝒑 − 𝒐𝒓𝒃𝒊𝒕𝒂𝒍 Axial overlap Lateral overlap

 𝝅 − 𝝈 − 𝒔𝒊𝒏𝒈𝒍𝒆 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏
 𝒏 − 𝝈 − 𝒆𝒎𝒑𝒕𝒚 𝒑 − 𝒐𝒓𝒃𝒊𝒕𝒂𝒍
 𝒏− 𝝈−𝝅

resonance hybrid Resonance hybrid is a

real intermediate form
of the resonance forms

resonance hybrid

These molecules resonate between two fictitious limit forms, called resonance or
mesomeric forms, they have no physical reality or independent existence. 4
 Conjugated systems
 𝛑− 𝝈−𝛑

 𝝅 − 𝝈 − 𝒆𝒎𝒑𝒕𝒚 𝒑 − 𝒐𝒓𝒃𝒊𝒕𝒂𝒍

 𝝅 − 𝝈 − 𝒔𝒊𝒏𝒈𝒍𝒆 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏

 𝒏 − 𝝈 − 𝒆𝒎𝒑𝒕𝒚 𝒑 − 𝒐𝒓𝒃𝒊𝒕𝒂𝒍

𝝅 − empty orbital

The last system is not really conjugated, the delocalization is between two atoms only.
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However, it's a mesomerism.
 Types of mesomeric effect
The mesomeric effect is transmitted along a chain over to any distance. It is
long–distance conjugated system.

Cl atom is electron-
donating substituent (+M)

CO group is electron-
withdrawing substituent (–M)

The electron pairs are fully transferred, creating positive and negative charges at both ends.

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 Classification of mesomeric effect
 Atom or group, which donates electrons to a conjugated system, is denoted by (+M),
there are electron-donating by mesomeric effect.

(+M) atoms or groups contain often a lone electron pair.

 Atom or group, which withdraw electrons from a conjugated system towards

themself, is denoted by (–M), there are electron-withdrawing by mesomeric effect.

(-M) atoms or groups contain often an electronegative atom attached to a carbon atom or
a heteroatom with a multiple bond.

Certain aromatics and alkenes can have both a (+𝑴) and (−𝑴) effect, it depends on
the type of the conjugated system . 7
 Guidelines for drawing mesomeric forms
 In all forms, atoms maintain their same position, only electrons move.

 All the orbitals of the atoms participating in the resonance must be coplanar to ensure
orbital overlap.
 Respect the different arrows used;

not to be confused ⟷ × ⇌

 For a neutral, positively or negatively charged molecule, all the limit forms must have
the same net charge.
 All the forms have the same number of unpaired electrons.

 In the charged formulas, place the charges on the corresponding atoms, taking into
account their electronegativities.
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 Applications of mesomeric effect
-bond length -
Consider the two molecules represented below:
d = 180 nm d = 156 nm

C-Cl bond is simple

C-Cl bond is partially double

Resonance hybrid

The decrease in bond length is due to the electron-donating by mesomeric effect of the
chlorine atom.
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 Applications of mesomeris effect
-Resonance energy-
The resonance energy is defined as a difference in energy between resonance hybrid and
the most contributor structure. It represents the stabilization of the molecule due to the
delocalization of electrons

The two forms are identical and equivalent in terms The two forms don’t contribute equally to
of their relative contribution to the hybrid structure. the resonance hybrid

Contributor
form
Contributor
form

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 Applications of mesomeric effect
-How to find the contributor form ?-
Not all resonance structures contribute equally to the resonance hybrid, the most
stable limit form with the lowest energy is the one that contributes the most to the
real molecule (resonance hybrid).
 Structures with a greater number of bonds or a maximum number of atoms that respect
the octet rule are the most important.

minor major
 Structures without charges or with smallest charge separation are the most important.

major minor
 Charges should preferably be located on atoms corresponding to their electronegativity.

major minor
The major contributor form is used to represent the compound, but the minor contributor
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form is sometimes useful to explain the reactivity of compounds.
 Applications of mesomeric effect
-molecules' stability-
More electrons are delocalized, and more the number of resonance forms is greater, more
the molecule is stabilized.
Example. Comparison of stability of diketone and ketone

(Three resonance forms

versus two)

More stable less stable

The electrons in the diketone are delocalized over five atoms versus three atoms in ketone,
the electron density is less on the carbon of diketone than in simple ketone. 12
 Applications of mesomeric effect
-Acidity strength-
 Electron-withdrawing by mesomeric effect (-M) increases acidity, because the anion
formed on deprotonation is stabilized by delocalization of the negative charge.
 Electron-donating by mesomeric effect (+M) decreases acidity because the anion is
destabilized by increasing the negative charge.
The conjugate base with the most mesomeric forms is the most stable and it corresponds
to the most acidic specie.
Example. Comparison of the acidity of two alcohols.

1 2

Alcohol (a) is the most acid because its alcoolate anion has more mesomeric forms.
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 Applications of mesomeric effect
-Basicity strength -
 Electron-donating by mesomeric effect (+M) increases basicity, it increases electron
density on the nitrogen, the lone pair of nitrogen is more available to accept a proton.
 Electron-withdrawing by mesomeric effect (-M) decreases basicity, it decreases electron
density on the nitrogen, the lone pair of nitrogen is less available to accept a proton.
Example. Comparison of the basicity of an amine and an amide.

(+I) (-M)

The carbonyl group (-M) in ethanamide stabilizes the electron pair of nitrogen by
resonance, so it is less available. It is a very weak base.
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 Applications of mesomeric effect
-Stability of intermediates-
A carbocation and a carboradical are electron-deficient species.
 An electron-donating (+M) substituent stabilize the carbocation and the carboradical.
 An electron-withdrawing (-M) substituent destabilize the carbocation and the
carboradical.
Example 1.

Electron-donating by mesomeric effect of OMe

stabilizes the carbocation by delocalization

Electron-withdrawing by mesomeric effect of CO

destabilizes the carbocation by deacreasing its electron
density

The effect (-M) of CO destabilizes less the carbocation, CO

is further to the positive charge

Limit forms with more than two charges are unstable, especially when the presence of two charges of
the same type on two bonded atoms.
Increasing order of stability: b < 𝑐 < 𝑎 15
 Applications of mesomeric effect
-Stability of intermediates-

Example 2.

Electron-donating by mesomeric effect of C=C

stabilizes the carboradical by delocalization

Electron-donating by inductive effect stabilizes the carboradical

The carboradical is more stabilized by delocalization

The single electron is more dispersed
Increasing order of stability: b < 𝑎 < 𝑐 16
 Applications of mesomeric effect
-Stability of intermediates-
A carbanion possesses unshared pair of electrons and is therefore a base.
 An electron-donating (-M) substituent stabilize the carbanion.
 An electron-withdrawing (+M) substituent destabilize the carbanion.

Example 3.

Electron-withdrawing by mesomeric effect of C=C

stabilizes the carbanion by delocalization

Electron-withdrawing by inductive effect stabilizes the carbanion

Powerful electron-withdrawing mesomeric effect of

NO2 stabilizes more the carbanion by delocalization

Increasing order of stability: b < 𝑎 < 𝑐 17

 Inductive effect vs Mesomeric effect
Effect Inductive effect Mesomeric effect
Compound It operates in saturated or It operates in unsaturated compounds
unsaturated compounds having conjugated system
Bond It involves electrons of sigma It involves electrons of 𝜋 bonds, lone
bonds pair or single electrons
Cause Polarization Delocalization
Charge Partial charge separation appears Full charge separation appears
Electron Electrons don’t leave their The displaced electron leave their
molecular orbitals orbitals and attain a new position
Distance It is short operating distance It is not distance dependent

Mesomeric effect is generally stronger and dominant than inductive effect, it stabilizes
molecules more effectively.
Mesomeric and inductive effects of a substituent can also act in opposition.

Example: OH group is –I and +M, but it acts as a net electron-donating group.

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