ORGANIC CHEMISTRY

OCHE220203
Lecturer: Dat P. Nguyen, Ph.D
Email: datnp@hcmute.edu.vn
Department of Chemical Technology
Faculty of Chemical and Food Technology
 CHAPTER 2
ELETRONIC EFFECTS

2
 CONTENTS

1. Inductive Effect
1.1. Electronegativity and Bond Polarization
1.2. Molecular Polarity
1.3. Inductive Effect
2. Resonance Effect
2.1. Resonance Effect
2.2. Resonance Structures
3. Acid-Base
3.1. Acid-Base Theories
3.1.1. Bronsted-Lowry Theory
3.1.2. Lewis Theory
3.2. Quantification of Acidity/Basicity
3.3. Acidity/Basicity Comparison
3
1. Inductive Effect
1.1. Electronegativity and Bond Polarization

4
 1. Inductive Effect
1.1. Electronegativity and Bond Polarization

Electronegativity Difference (ΔEN)

< 0.5 0.5–1.7 > 1,7

Non-polar Polar
Ionic bond
covalent bond covalent bond

5
 1. Inductive Effect
1.1. Electronegativity and Bond Polarization

Non-polar covalent bond (ΔEN < 0.5)

6
 1. Inductive Effect
1.1. Electronegativity and Bond Polarization

Polar covalent bond (0.5 < ΔEN < 1.7)

EN = 2.5
EN = 3.5

dipole moment (vector)

7
Dipole - Practice

8
 1. Inductive Effect
1.2. Molecular Polarity

Large dipole moment 🡪 dipole moment = 0 🡪

polar molecule non-polar molecule
9
 1. Inductive Effect
1.2. Molecular Polarity

Step 1: Draw the shape of the molecules, considering the

hybridization of atoms
Step 2: Draw the dipole moments of all polar covalent bonds
Step 3: Calculate the molecule dipole moment (µ), which is the
vector sum of all dipole moments
Step 4: Molecular polarity:
- µ = 0 🡪 non-polar
- µ ≠ 0 🡪 polar
(1) (2) (3) (4) (5)

10
 1. Inductive Effect
1.2. Molecular Polarity

How to determine the hybridization of an atom?

• Step 1: Draw Lewis structure
• Step 2: Count the number (n)
– Number of σ bonds to other atoms
– Number of lone electron pairs
– Do not count the number of π bonds
• Step 3: Determine the hybridization -C≡ or =C=
– n=2 → sp, straight line

– n=3 → sp2, trigonal planar

>C=

– n=4 → sp3, tetrahedral

>C<
 Molecular Polarity - Practice
Determine the hybridization of all carbons and the
molecular polarity

12

12
1. Inductive Effect
1.3. Inductive Effect

• More electronegative X →
stronger –I effect
• -I groups:
X: F, Cl, Br, I, NO2, OH/OR,
SH/SR, NH2/NHR/NR2,
CHO/(C=O)R, COOH/COOR…

13
1. Inductive Effect
1.3. Inductive Effect

• More electropositive Z →
stronger +I effect
• +I groups:
Z: alkyl, aryl, or metal (Li, Na,
K, Mg, Al…)

14
1. Inductive Effect
1.3. Inductive Effect

15
 2. Resonance Effect
2.1. Resonance Effect

Electron delocalization in a conjugated system

16
 2. Resonance Effect
2.1. Resonance Effect

Electron delocalization in a conjugated system

• O is more electronegative than C → Electrons move

through π-bond network towards C=O
• The conjugated system is polarized
• C=O has negative resonance effect (-R)
17
 2. Resonance Effect
2.1. Resonance Effect

Electron delocalization in a conjugated system

-R +R

-R +R

-R +R 18
 2. Resonance Effect
2.1. Resonance Effect

Electron delocalization in a conjugated system

+R -R

-R +R

-R
+R

-R +R

19
 2. Resonance Effect
2.1. Resonance Effect

-R groups generally contain +R groups generally contain

electronegative atoms and/or a lone pair of electrons
π-bonds: or a π-bond (s):

Examples: CHO, C(O)R, Example: Cl, Br, OH, OR, SH,

COOH, COOR, NO2 , CN SR, NH2 , NHR, NR2

Aromatics or alkenes can be both +R and -R

20
 2. Resonance Effect
2.2. Resonance Structures

• Resonance allows the delocalization of electron pairs across

two or more atoms.
• This delocalization of electron density increases the stability of
the molecule.
• A molecule with two or more resonance structures is
considered to have stable resonance.
21
 2. Resonance Effect
2.2. Resonance Structures

Resonance structures vs. isomers

22
 2. Resonance Effect
2.2. Resonance Structures

Formal charges:
• Lose electron 🡪 positive
• Gain electron 🡪 negative

23
 2. Resonance Effect
2.2. Resonance Structures

Formal charges: Calculate from Lewis structure

• Formal charge = Valence electrons – ½ bonded
electrons – unbonded electrons

Consider O atom:
• Valence electrons = 6 (O in group VI)
• Bonded electrons = 2 (1 bond with C) → Formal charge = 6 – 2/2 – 6 = –1
• Unbonded electrons = 6 (3 lone pairs)
24
 Formal Charges - Practice

Determine the formal charges for atoms

25
 2. Resonance Effect
2.2. Resonance Structures

Rules:
▪ Rule 1: Position of atoms and σ bonds are fixed. Only
the π bonds and lone pairs change.
▪ Rule 2: All resonance structures must have the same
number of unpaired electron.
▪ Rule 3: All resonance structures must follow octet rule.

26
 2. Resonance Effect
2.2. Resonance Structures

Rule 1: Position of atoms and σ bonds are fixed. Only the π

bonds and lone pairs change.

27
 2. Resonance Effect
2.2. Resonance Structures

Rule 2: All resonance structures must have the same number

of unpaired electron.

28
 2. Resonance Effect
2.2. Resonance Structures

Rule 3: All resonance structures must follow octet rule.

Exception: formal charges

29
 2. Resonance Effect
2.2. Resonance Structures

Curved arrows: movement of electron

• From electron rich position 🡪 electron poor position
• Tail: Start from the electron pair of a π bond or a lone pair
• Head: Point toward the new position of that electron pair

30
2. Resonance Effect
2.2. Resonance Structures

Allylic anion

?
31
2. Resonance Effect
2.2. Resonance Structures

Allylic cation

?
32
2. Resonance Effect
2.2. Drawing Resonance Structures

Lone pair next to cation

?
33
2. Resonance Effect
2.2. Resonance Structures

C=O or C=N π bond

?
34
2. Resonance Effect
2.2. Resonance Structures

Aromatic ring

?
35
 Resonance Structures - Practice

Draw resonance structures

36
 Resonance Structures - Practice

Draw resonance structures

37
 Resonance Structures - Practice

Draw resonance structures

38
 Inductive Effect vs. Resonance Effect

■ Inductive effect: bond polarization along the σ bonds

🡪 straight arrow

■ Resonance effect: delocalization of electrons (π bonds

and lone pairs) 🡪 curved arrow

■ Resonance effect has stronger influence than

inductive effect on molecular properties

■ Resonance effect is effective over long distance, while

Inductive effect diminish greatly over long distance
39
 3. Acid-Base
3.1. Acid-Base Theories
3.1.1. Bronsted-Lowry Theory
donating H+

accepting H+

donating H+

accepting H+

40
 3. Acid-Base
3.1. Acid-Base Theories
3.1.1. Bronsted-Lowry Theory

Acid-base reaction

41
 Acid-Base Reaction - Practice

Draw mechanism of acid-base reactions

42
 3. Acid-Base
3.1. Acid-Base Theories
3.1.2. Lewis Theory

43
3. Acid-Base
3.2. Quantification of Acidity/Basicity

pKa = - logKa
large Ka or
→ strong acid
small pKa
44
 3. Acid-Base
3.2. Quantification of Acidity/Basicity

pKa values of organic acids and their conjugate base

45
 3. Acid-Base
3.3. Acidity/Basicity Comparison

Compare acidity based on pKa:

pKa= 4.75 > pKa= 19.2

stronger acid weaker acid
46
 3. Acid-Base
3.3. Acidity/Basicity Comparison

Compare basicity based on pKa:

📫 Determine the conjugate acids and compare them using pKa
📫 Stronger conjugate acid → weaker base

X Y

47
 3. Acid-Base
3.3. Acidity/Basicity Comparison

If pKa values are unknown → General approach: Compare the

stability of charged species

Compare acidity of neutral Compare basicity of

acids without pKa: neutral bases without pKa:
📫 Determine the conjugate 📫 Determine the conjugate
bases (negatively acids (positively
charged) and compare charged) and compare
their stability their stability
📫 Stronger conjugate base 📫 Stronger conjugate acid
→ weaker acid → weaker base

48
 3. Acid-Base
3.3. Acidity/Basicity Comparison

To compare stability of different compounds,

remember the following mnemonic: ARIO

• A: Atom – electronegativity and size of the atom

• R: Resonance – resonance effect
• I: Induction – inductive effect
• O: Orbital – hybridization of the orbitals

49
 3. Acid-Base
3.3. Acidity/Basicity Comparison

A: Atom
• same period (row) →
consider electronegativity
• same group (column) →
consider size

50
 3. Acid-Base
3.3. Acidity/Basicity Comparison

A: Atom – Same period

<

C (EN = 2.5) < O (EN = 3.5)

→ hold negative charge better
less stable more stable
51
 3. Acid-Base
3.3. Acidity/Basicity Comparison

A: Atom – Same group

<

Size of O < Size of S

→ disperse negative
charge better
less stable more stable 52
 3. Acid-Base
3.3. Acidity/Basicity Comparison

R: Resonance

<

charge is charge is
localized delocalize
less stable more stable
53
 3. Acid-Base
3.3. Acidity/Basicity Comparison

I: Induction

<

no EWG have EWGs

→ disperse negative
charge better
less stable more stable 54
 3. Acid-Base
3.3. Acidity/Basicity Comparison

O: Orbital

< <

sp3 sp2 sp
→ more s-orbital characteristic
→ hold negative charge better
less stable more stable
55
 3. Acid-Base
3.3. Acidity/Basicity Comparison

Important notes about ARIO mnemonic:

- Only qualitative, not quantitative
- Not always true, may have some exceptions

Example of exception:

>
pKa = 25 pKa = 38

56
 Acidity/Basicity - Practice

Compare acidity

57
 Acidity/Basicity - Practice

Compare basicity

58
 Acidity/Basicity - Practice

Compare acidity of protons

59
 Acidity/Basicity - Practice

Compare acidity of protons

60
 Acidity/Basicity - Practice

Compare acidity

61
 Acidity/Basicity - Practice

Find the most acidic proton

62
 Acidity/Basicity - Practice

Compare acidity of protons

63