ORGANIC CHEMISTRY

Dr Nam T. S. Phan
Faculty of Chemical Engineering
HCMC University of Technology
Office: room 211, B2 Building
Phone: 38647256 ext. 5681
Email: [email protected]
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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 s bond in butane:
almost completely nonpolar

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

+
''+
'+
'''+

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

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

4
The more electropositive the Z, the stronger
the +I effect
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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 p-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

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-C +C
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 p-bond (s):

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

+C groups generally contain a lone pair of electrons

or a p-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

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-C
 INDUCTIVE vs CONJUGATION
EFFECTS
• C effects are generally stronger than I
effects
• C effects can be effective over much
longer distances than I effects –
provided that conjugation is present
• I effects are determined by distance, C
effects are determined by relative
positions
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HYPERCONJUGATION EFFECTS (H)

Electron density from Ca-H flows into the vacant p orbital

(in carbocation / C=C / CC) because orbitals can partially
overlap

Hyperconjugation effects (H) 16

•H effect of -CH3 is stronger than H effect of -CH2-
•H effect is generally stronger than I effect
H
H C CH HCl
CH CH2 CH3
+ 
H

CH3 CH CH2 CH2 CH3

Cl
Electron-donating ability of -CH3 is stronger
than that of -CH2CH3 17
 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

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22
 Electron-
donating
groups

Electron-
withdrawing
groups

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 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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Benzoic acid derivatives Position on benzene ring
pKa Ortho- Meta- Para-
CH3C6H4COOH 3.91 4.27 4.36
NH2C6H4COOH 4.97 4.78 4.92
FC6H4COOH 3.27 3.87 4.14
ClC6H4COOH 2.92 3.82 3.98
BrC6H4COOH 2.85 3.81 3.97
IC6H4COOH 2.86 3.85 4.02
HOC6H4COOH 2.97 4.06 4.48
CH3OC6H4COOH 4.09 4.09 4.47
NCC6H4COOH 3.14 3.84 3.55
NO2C6H4COOH 2.16 3.47 3.41 29
 -I is decreased over
long distance
+C dominates -I dominates

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

HC C COOH H3C C C COOH

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pKa = 1.84 pKa = 2.60
31
 Basicity X pKa of ammonium cation
of o- m- p-
XC6H4NH2 CH3 4.39 4.69 5.12
CH3O 4.49 4.20 5.29
C2H5O 4.47 4.17 5.25
C6H5 3.78 4.18 4.27
F 3.20 3.59 4.65
Cl 2.61 3.34 3.98
Br 2.60 3.51 3.91
I 2.60 3,61 3,78
CH3OCO 2,23 3.64 2.38
CF3 --- 3.50 2.60
CN --- 2.76 1.74
NO2 -0.29 2,50 1,02 32
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 RESONANCE CONTRIBUTORS &
HYBRID

RULES OF DRAWING RESONANCE

CONTRIBUTORS

1. Only electrons move. Nuclei never move.

2. Only p electrons/ lone-pair electrons can move.
3. Total number of electrons does not change.

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Moving p electrons  positive charge 35
Moving p electrons  p bond 36
Moving a lone pair  p bond
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 Allyl &
benzyl
radicals

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39
STABILITY OF RESONANCE CONTRIBUTORS

A>B

C=D

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F >> G > E
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 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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44
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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