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These effects are a combination of
RESONANCE and INDUCTIVE
effects
The effects are also important in other reactions and properties (e.g.
acidity of the substituted benzoic acids).
Here are some general pointers for recognising the substituent
effects:
-
The H atom is the standard and is regarded as having no effect.
-
Activating groups increase the rate
-
Deactivating groups decrease the rate
-
EDG = electron donating group
-
EDG can be recognised by lone pairs on the atom adjacent to
the π system, eg: -OCH3
-
except -R, -Ar or -vinyl (hyperconjugation, π electrons)
-
EWG = electron withdrawing group
-
EWG can be recognised either by the atom adjacent to
the π system having several bonds to more electronegative atoms,
or,
having a formal +ve or δ +ve charge, eg: -CO2R, -NO2
-
EDG / activating groups direct ortho / para
-
EWG / deactivating groups direct meta
-
except halogens (-X) which are deactivating BUT
direct ortho / para
There are two main
electronic effects that substituents can exert:
RESONANCE effects are those that occur through the pi system and
can be represented by resonance structures. These can be either electron
donating (e.g. -OCH3) where pi electrons are pushed
toward the arene or electron withdrawing (e.g. -C=O) where pi
electrons are drawn away from the arene.
In certain cases, molecules can be represent by
more than one reasonable Lewis structure that differ only in the
location of π electrons.
Electrons in σ bonds have a fixed location and so they are said to be
localised.
In contrast, π electrons that can be drawn in different locations are
said to be delocalised.
Collectively these Lewis diagrams are then known as resonance
structures or resonance contributors or resonance
canonicals.
The "real" structure has characteristics of each of the contributors,
and is often represented as the resonance hybrid (think of a
hybrid breed which is a mixed breed). In a way, the resonance hybrid is
a mixture of the contributors.
(note that a resonance hybrid cannot
normally be written as an individual Lewis diagram !).
You should be able to draw all reasonable
resonance structures for a given organic molecule.
The best way to "derive" resonance structures is
by learning to "push"
curly arrows and starting from a reasonable
Lewis structure.
INDUCTIVE effects are those that occur through the sigma system
due to electronegativity effects. These too can be either electron
donating electron donating (e.g. -Me) where sigma electrons are
pushed toward the arene or electron withdrawing (e.g. -CF3,
+NR3) where sigma electrons are drawn away from the arene.
Electronegativity
- Electronegativity is defined as the
ability of an atom to attract electrons towards itself.
- It is one of the
most important properties for rationalising and
predicting reactivity etc.
- The partial periodic table below has the
Pauling electronegativities of some key elements.
H
2.1
|
|
He |
Li
1.0
|
Be
1.5
|
|
B
2.0
|
C
2.5
|
N
3.0
|
O
3.5
|
F
4.0
|
Ne |
Na
0.9
|
Mg
1.2
|
|
Al
1.5
|
Si
1.8
|
P
2.1
|
S
2.5
|
Cl
3.0
|
Ar |
K
0.8
|
Ca
1.0
|
Sc |
Ti |
V |
Cr |
Mn |
Fe |
Co |
Ni |
Cu |
Zn |
Ga |
Ge |
As |
Se |
Br
2.8
|
Kr |
|
Rb |
Sr |
Y |
Zr |
Nb |
Mo |
Tc |
Ru |
Rh |
Pd |
Ag |
Cd |
In |
Sn |
Sb |
Te |
I
2.5
|
Xe |
- Electronegativity increases left
to right across a row in the periodic table e.g.
C < N < O < F
(as you move left to right nuclear charge increases so
there is a greater attraction for electrons)
- Electronegativity decreases as you
move down a group in the periodic table e.g.
F > Cl > Br > I
(each step down a group increases the atomic radii as a "new
shell" of electrons are added and the nuclear charge is
further shielded by the core electrons, both factors decrease the
attraction for electrons)
- F is the most electronegative element
- Metals, e.g. Li and Mg, are less
electronegative than C (i.e. metals are electropositive
compared to C)
A simplified approach to
understanding substituent effects is provided, based on the "isolated
molecule approach". The text (as do most others) uses the
more rigourous approach of
drawing the resonance structures for each of the intermediate
carbocations formed by attack at each of the o-, m- and p- positions
and looking at how the initial substituent influences the stability of
the system.
We are going to break down
the types of substituents into various subgroups
based on the structural features of the
substituent immediately adjacent to the aromatic ring:
-
type 1 = substituents with lone pairs
(e.g. -OCH3, -NH2) on the atoms
adjacent to the pisystem.
-
type 2 = substituents that are CH systems
(i.e. -alkyl, -vinyl or -aryl).
-
type 3 = substituents that are C=C systems
(i.e. -vinyl or -aryl).
-
type 4 =
substituents with pi bonds to electronegative atoms (e.g.
-C=O, -CF3, -NO2)
-
type 5 =
substituents with several bonds to electronegative atoms
(e.g. -CF3)
-
type 6 =
substituents that are halogens systems (i.e. -F, -Cl,
-Br, -I)
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