Chapter 2
Chapter 2
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]
1
Chapter 2: ELECTRONIC &
STERIC EFFECTS
Effects
Steric Electronic
Inductive Hyperconjugation
Conjugation / Mesomeric
2
INDUCTIVE EFFECTS (I)
C-C s bond in butane:
almost completely nonpolar
C-C s bond in 1-
fluorobutane: polarized -
+
''+
'+
'''+
4
The more electropositive the Z, the stronger
the +I effect
5
Through a period in a periodic table
-I
Through a
group in a
periodic
table
-I
6
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
8
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
9
C CH CH CH CHR
-C +C
C O R
-C +C
R CH CH CH CH O R
10
-C +C
OH +C O H -C
-C +C
N
NH2 -C
+C
-C +C
11
-C groups generally contain an electronegative atom (s)
or / and a p-bond (s):
Cl, Br, OH, OR, SH, SR, NH2, NHR, NR2, aromatics, alkenes
+C
Through a
group in a
periodic
table
+C
13
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
14
-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
15
HYPERCONJUGATION EFFECTS (H)
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
19
Steric
hindrance
20
ACIDITY & BASICITY
21
22
Electron-
donating
groups
Electron-
withdrawing
groups
23
Electron-
donating
groups
Electron-
withdrawing
groups
24
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
OH OH OH
CH3
> >
CH3
CH3
pKa = 10.08 10.14 10.28
27
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
28
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
34
Moving p electrons positive charge 35
Moving p electrons p bond 36
Moving a lone pair p bond
37
Allyl &
benzyl
radicals
38
39
STABILITY OF RESONANCE CONTRIBUTORS
A>B
C=D
40
F >> G > E
41
STABILITY OF CARBOCATIONS
+H & +I
42
Allylic & benzylic carbocations
+C +C
45
Relative stability of carbocations
46
STABILITY OF RADICALS
47
STABILITY OF CARBANIONS
48