ORGANIC CHEMISTRY

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Chapter 2: ELECTRONIC &
STERIC EFFECTS
Effects

Steric Electronic

Inductive Hyperconjugation

Conjugation / Mesomeric
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 INDUCTIVE EFFECTS (I)
C-C  bond in butane:
almost completely nonpolar

C-C  bond in 1-
fluorobutane: polarized -

+
''+
'+
'''+

C1 is more positive than C2 as a result of electron-

attracting ability of F 3
 The more electronegative the X,
the stronger the -I effect

Common -I groups:
- positive charged groups
- groups with electronegative atoms
- groups with double or triple bonds
 Ex: -Br, -Cl, -OH, -OR, -NH2, -NHR, -NR2, -NO2, -CF3, -SO3H,
-CN, -COOH, -CHO, -COR, -CH=CH2, -C6H5, -C≡CH, -N+R3,...
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 The more electropositive the Z,
the stronger the +I effect

Common +I groups:
- negative charged groups
- alkyl groups
- metals
 Ex: -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)2, -C(CH3)3, -Li, -Mg,...

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Through a period in a periodic table

-I

Through a
group in a
periodic
table

-I
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 Ka.105
CH3CH2CH2COOH 1.5
CH3CH2CH(Cl)COOH 139 Strong -I
CH3CH(Cl)CH2COOH 8.9
ClCH2CH2CH2COOH 3.0 weak -I 7
 CONJUGATION / MESOMERIC
EFFECTS (C / M)
Electron delocalization in a conjugated system:
Alternating
single &
multiple
bonds

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 O is more electronegative than C
Electrons move through -bond network towards
C=O
The conjugated system is polarized
C=O has negative conjugation / mesomeric effect
(-C / -M) on the conjugated system

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 C CH CH CH CHR

-C +C
C O R

-C +C

R CH CH CH CH O R

-C +C
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OH +C O H -C

-C +C

N
NH2 -C
+C

-C +C

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 -C groups generally contain an electronegative atom (s)
or / and a -bond (s):

CHO, C(O)R, COOH, COOR, NO2, CN, aromatics, alkenes

+C groups generally contain a lone pair of electrons

or a -bond (s):

Cl, Br, OH, OR, SH, SR, NH2, NHR, NR2, aromatics, alkenes

Aromatics or alkenes can be both +C and-C 12

Through a period in a periodic table

+C

Through a
group in a
periodic
table

+C
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 INDUCTIVE vs CONJUGATION
EFFECTS
O
H CH CH CH CH CH CH C
H

O
H CH CH CH CH C
H
O
Mobility of hydrogen H CH CH C
atoms: almost the same
H

-C
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 INDUCTIVE vs CONJUGATION
EFFECTS

- C effect is generally stronger than I effect

- C effect can be effective over much
longer distances than I effect - provided
that conjugation is present
- I effect decreases rapidly along with the
distance

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RESONANCE CONTRIBUTORS & HYBRID

RULES OF DRAWING
RESONANCE CONTRIBUTORS

1. Only eletrons move. Nuclei never move

2. Only /lone pair electrons can move

3. Total number of electrons does not change

 Resonance contributors

Resonance hybrid

Moving  electrons → positive charge

 Resonance contributors

Resonance hybrid

Moving  electrons →  bond

 Resonance contributors

Resonance hybrid

Resonance contributors

Resonance hybrid

Moving a lone pair →  bond

Resonance contributors

Resonance hybrid

Resonance contributors

Resonance hybrid
Allyl & benzyl radicals
STABILITY OF RESONANCE CONTRIBUTORS

RESONANCE CONTRIBUTORS
WILL BE LESS STABLE IF:

1. An atom with an incomplete octet

2. A negative charge that is not on the most

electronegative atom or a positive charge
that is not on the least electronegative atom

3. Charge separation
STABILITY OF RESONANCE CONTRIBUTORS

A>B

C=D

F>G>E
HYPERCONJUGATION EFFECTS (H)

- Electron density from C-H (or C -C) flows into the empty orbital
of carbocation / C=C / CC) because orbitals can partially overlap
 +H effect
- Generally, H effect is stronger than I effect but weaker than
C effect 16
 STERIC EFFECTS
• A steric effect is an effect on relative rates caused
by space-filling properties of those parts of a
molecule attached at / near the reacting site

• Steric hindrance: the spatial arrangement of the

atoms / groups at / near the reacting site hinders /
retards a reaction

• Generally, very large & bulky groups can hinder

the formation of the required transition state
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Steric hindrance

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 Steric
hindrance

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 ACIDITY & BASICITY

• The more the H-A bond is polarized,

the easier the proton of H-A can separate.

• The better A can bear negative charge,

the more stable the conjugated base A- is.

Acidity of H-A increases

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 ACIDITY & BASICITY

• Carboxylic acids (RCOOH) and p-toluene-sulfonic acid (p-TsOH)

are the most common organic acids (p-TsOH is much stronger
than RCOOH).
• Alcohols, especially phenols, are weakly acidic (phenols is much 29
weaker than RCOOH).
 ACIDITY & BASICITY
How the atom attaching to hydrogen in an acid
affects its acidity
When atoms attaching to hydrogen are similar in size, the stronger acid has its
hydrogen attached to the more electronegative atom.

When atoms attaching to hydrogen are very different in size, the stronger acid
has its hydrogen attached to the larger atom.

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 ACIDITY & BASICITY
How the substituent on the acid affects its acidity

- The substituent can cause inductive, conjugation, or

hyperconjugation effect on the acid. These effects can be
electron withdrawing (-I, -C, -H) or electron donating (+I, +C,
+H).
- Generally, the more electron withdrawing the substituent is,
the more it stabilizes the conjugated base by decreasing the
electron density about the atom that bears the negative
charge in the conjugated base, thereby making the acid
stronger. Oppositely, the more electron donating the
substituent is, the weaker the acid becomes.

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 ACIDITY & BASICITY
How the substituent on the acid affects its acidity

NOTE:
- One substituent can cause more than one effect in
opposite directions. To decide whether the overall effect is
electron withdrawing or donating, remember that generally
C effect > H effect > I effect.
Example: -OCH3 group on the benzene ring can donate electron to
the ring by conjugation effect (+C) and withdraw electron from the
ring by inductive effect (-I) but +C effect dominates (C effect > I effect).
Overall effect caused by -OCH3 group to the benzene ring is therefore
electron donating.
- Important exception: generally I effect > C effect in case of
halogens. 32
Electronegativity

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 -I is decreased over
long distance
-I and +C -I

CH3CH2CH CHCOOH < CH2 CHCH2CH2COOH < CH3CH CHCH2COOH

pKa = 4.83 pKa = 4.68 pKa = 4.48

+C and -I but +C and -I but

-I dominates -I dominates

H3C C C COOH HC C COOH

pKa = 2.60 pKa = 1.84 30
 Electron-
donating
groups

Electron-
withdrawing
groups

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If –C groups are introduced at ortho- & para
position on phenol rings:
+ The anion (-O-) can be further stabilized by
delocalization through the conjugated system as
the negative charge can be spread onto the -C
groups
+ The O-H bond is more polarized as electron
density on –OH can be spread onto the -C groups

Acidity of phenols is generally

increased
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If –I groups are introduced on phenol rings, the
effect will depend on the distance:
+ The closer the –I group is to the negative
charge (-O-), the greater the stabilizing effect is
+ The closer the –I group is to the –OH, the O-H
bond is more polarized

Acidity of phenols is generally

increased

Note: there might be ortho-effects

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 OH OH OH
NO2
> >
NO2
NO2
pKa = 7.15 7.23 8.4

OH OH OH
CH3
> >
CH3
CH3
pKa = 10.08 10.14 10.28

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 OH
OH OH
OCH3
> >

OCH3
OCH3
pKa = 9.65 9.98 10.21
OH OH
OH
Cl
> >
Cl
Cl
pKa = 8.48 9.02 9.38

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 Electron-
donating
groups

Electron-
withdrawing
groups

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 BE CAREFUL!!!
Compare acidity of compounds have:

1. the same acid functional group with different substituents

(B) > (C) > (A)

(C) > (A) > (B)

2. different acid functional group

(A) > (C) > (B)

(C) > (B) > (A)
 BE CAREFUL!!!
Ester group: -COOR or -OCOR

Acidity:
BE CAREFUL!!!
Acidity:

But
Exercise
Compare acidity of following compounds:
Acidity: (8) < (9) < (5) < (6) < (4) < (7) < (2) < (1) < (3) < (10)
Exercise
Compare acidity of following compounds:
Acidity: (10) < (9) < (5) < (6) < (4) < (7) < (2) < (3) < (1) < (8)
48
 BE CAREFUL!!!
Replace H: Basicity:
- by alkyl group will increase basicity
- by phenyl group will decrease basicity Replace benzene ring by alkyl
group (example: cyclohexyl
group) will increase basicity

Generally,
- R group which is electron donating will increase basicity
- R group which is electron withdrawing will decrease basicity
Exercise
Compare basicity of following compounds:
Basicity: (1) < (4) < (6) < (9) < (10) < (8) < (2) < (7) < (5) < (3)
Exercise
Compare basicity of following compounds:
Basicity: (1) < (9) < (8) < (10) < (5) < (6) < (4) < (3) < (2) < (7)
 STABILITY OF CARBOCATIONS

+H & +I

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 Allylic & benzylic carbocations

+C +C

Allylic & benzylic carbocations are generally stable

due to the electron delocalization (+C effects)
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56
Not all allylic & benzylic carbocations have the
same stability

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Relative stability of carbocations

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STABILITY OF RADICALS

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STABILITY OF CARBANIONS

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