Chapter 2: ELECTRONIC & INDUCTIVE EFFECTS (I)

STERIC EFFECTS C-C bond in butane:

almost completely nonpolar
Effects

Steric Electronic C-C bond in 1-

fluorobutane: polarized -

+
Inductive Hyperconjugation ''+
'+
'''+

Conjugation / Mesomeric
C1 is more positive than C2 as a result of electron-
2
attracting ability of F 3

The more electronegative

the X, the stronger the –I
effect

The more electropositive the Z, the stronger

the +I effect
4 5
Through a period in a periodic table

-I

Through a
group in a
periodic
table

Ka.105
CH3CH2CH2COOH 1.5
CH3CH2CH(Cl)COOH 139 Strong -I
-I CH3CH(Cl)CH2COOH 8.9
6 ClCH2CH2CH2COOH 3.0 weak -I 7

CONJUGATION / MESOMERIC O is more electronegative than C

EFFECTS (C / M) Electrons move through -bond network towards

C=O
Electron delocalization in a conjugated system:
The conjugated system is polarized
Alternating
single & C=O has negative conjugation / mesomeric effect
multiple (-C / -M) on the conjugated system
bonds

8 9
 OH +C O H -C
C CH CH CH CHR
-C +C
-C +C
C O R
N
NH2 -C
-C +C +C

R CH CH CH CH O R
-C +C

10 11
-C +C

-C groups generally contain an electronegative atom (s)

Through a period in a periodic table
or / and a -bond (s):
+C

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

group in a
+C groups generally contain a lone pair of electrons periodic
or a -bond (s): table

Cl, Br, OH, OR, SH, SR, NH2, NHR, NR2, aromatics, alkenes
+C
Aromatics or alkenes can be both +C and-C 12 13
 INDUCTIVE vs CONJUGATION INDUCTIVE vs CONJUGATION
EFFECTS EFFECTS
O
H CH CH CH CH CH CH C • C effects are generally stronger than I
H
effects
O • C effects can be effective over much
H CH CH CH CH C longer distances than I effects –
H provided that conjugation is present
O • I effects are determined by distance, C
Mobility of hydrogen H CH CH C effects are determined by relative
atoms: almost the same
H positions
14 15
-C

HYPERCONJUGATION EFFECTS (H) •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
δ+ δ−
H

CH3 CH CH2 CH2 CH3

Electron density from C -H flows into the vacant p orbital
(in carbocation / C=C / C C) because orbitals can partially
Cl
overlap
Electron-donating ability of -CH3 is stronger
Hyperconjugation effects (H) 16 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 Steric hindrance
the formation of the required transition state
18 19

Steric
hindrance ACIDITY & BASICITY

20 21
 Electron-
donating
groups

Electron-
withdrawing
groups

22 23

If –C groups are introduced at ortho- & para

position on phenol rings:
+ The anion (-O-) can be further stabilized by
Electron- delocalization through the conjugated system as
donating
groups
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
Electron-
withdrawing
groups
Acidity of phenols is generally
increased
24 25
 OH OH OH
If –I groups are introduced on phenol rings, the
NO2
effect will depend on the distance: > >
+ The closer the –I group is to the negative NO2
charge (-O-), the greater the stabilizing effect is NO2
pKa = 7.15 7.23 8.4
+ The closer the –I group is to the –OH, the O-H
bond is more polarized OH OH OH
CH3
> >
Acidity of phenols is generally CH3
increased CH3
pKa = 10.08 10.14 10.28
Note: there might be ortho-effects
26 27

OH Benzoic acid derivatives Position on benzene ring

OH OH
OCH3 pKa Ortho- Meta- Para-
> >
CH3C6H4COOH 3.91 4.27 4.36
OCH3 NH2C6H4COOH 4.97 4.78 4.92
OCH3
pKa = 9.65 9.98 FC6H4COOH 3.27 3.87 4.14
10.21
OH ClC6H4COOH 2.92 3.82 3.98
OH OH
BrC6H4COOH 2.85 3.81 3.97
Cl
> > IC6H4COOH 2.86 3.85 4.02
Cl HOC6H4COOH 2.97 4.06 4.48
Cl
CH3OC6H4COOH 4.09 4.09 4.47
pKa = 8.48 9.02 9.38
NCC6H4COOH 3.14 3.84 3.55
28
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

pKa = 1.84 pKa = 2.60 30 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 33
 Allylic & benzylic carbocations
STABILITY OF CARBOCATIONS

+H & +I
+C +C

Allylic & benzylic carbocations are generally stable

due to the electron delocalization (+C effects)
34 35

Not all allylic & benzylic carbocations have the

same stability

36 37
 Relative stability of carbocations STABILITY OF RADICALS

38 39

STABILITY OF CARBANIONS

40