STRUCTURA

L EFFECTS

Gladys I. Bathan

STRUCTURAL EFFECTS
Effect of the structure on
STABILITY and
REACTIVITY of the organic
compound

STRUCTURAL EFFECTS
I.
II.
III.
IV.

Resonance
Inductive effect
Steric effect
Hydrogen bonding

I. RESONANCE
A molecules structure
can have several forms
that differ only in the
placement of electrons

I. RESONANCE
Electrons are shared
between more than two
atoms (electrons are
delocalized)

I. RESONANCE
Structural forms are called
contributing structures
or resonance structures
or canonical structures

I. RESONANCE
TRUE STRUCTURE
Hybrid of all contributing
or resonance structures

http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/

I. RESONANCE
How to show the movement
of electrons?

http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/

I. RESONANCE
Allowed movement of electrons
bond
lone pair
lone
pair bond
bond
bond

* Only bonds are broken or formed

I. RESONANCE
bond

lone pair

http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/

I. RESONANCE
lone

pair bond

http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/

I. RESONANCE
bond

bond

http://www.masterorganicchemistry.com/2011/11/30/introduction-to-resonance-2-curved-arrows/

I. RESONANCE
Types of electron delocalization
A. electron delocalization
B. lone pair delocalization
C. electron delocalization
(C-H hyperconjugation)

A. electron delocalization
Electrons - electrons found in a
pi bond
electron delocalization is
observed in compounds
containing conjugated double or
triple bonds.

A. electron delocalization

isolated
alkene

conjugated cumulated
alkene
alkene

A. electron delocalization

Klein, Organic Chemistry 2e

B. lone pair delocalization

Lone pairs from O

Klein, Organic Chemistry 2e

B. lone pair delocalization

Lone pairs from N

Klein, Organic Chemistry 2e

B. lone pair delocalization

Allylic lone pairs (Atom with lone
pair next to a pi bond)

Klein, Organic Chemistry 2e

B. lone pair delocalization

..
NH2

..
CH
O
C
3
..
..
NH2

:O:
C
..
O
.. H

B. lone pair delocalization

:O:

:O:
C H

..
:O

.. :O:
N+

..
NH2

C. Hyperconjugation
Electron delocalization involving
sigma bonds (C-C, C-H) and pi
bonds.
More canonical structures lead to
better stability of the molecule

C. Hyperconjugation

Klein, Organic Chemistry 2e

C. Hyperconjugation
H

H C H

H C H

H
H C H

..

..
-

How many canonical structures?

C. Hyperconjugation
H

H
O
H C C
H
H

H C C
H

How many canonical structures?

I. RESONANCE
Molecules with resonance structures meet the ff
criteria:
Criterion 1: Have at least one pi bond.
Criterion 2: Have at least one of the following
a) a second, conjugated pi bond, or
b) an allylic or -atom with at least one lone
pair of electrons, or
c) an allylic atom with a vacant p-orbital.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

1. Does the molecule have at least

one pi bond?
YES : a. number the two atoms of
the pi bond 1 and 2
b. go to step 2.
NO : molecule does not have
resonance.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

2. Circle the atom(s) directly bonded

to atom 1.
3. Circle the atom(s) directly bonded
to atom 2.
4. Label the circled atoms 3, 4,
5, and 6.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

5. Is atom 3, 4, 5 or 6 part of
another pi bond?
YES : molecule has resonance
NO : Go to step 6.

http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

6. Does atom 3, 4, 5 or 6 have at

least one lone pair of electrons
or a single unpaired electron?
YES : the molecule has resonance
NO : Go to step 7.
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

7. Does atom 3, 4, 5 or 6 have a

vacant p-orbital (usually a
carbocation)?
YES : molecule has resonance
NO : molecule has no resonance
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

Identifying structures with resonance

7. Does atom 3, 4, 5 or 6 have a

vacant p-orbital (usually a
carbocation)?
YES : molecule has resonance
NO : molecule has no resonance
http://www.organicchem.org/oc2web/lecture/outlines/resonance.pdf

II. INDUCTIVE EFFECT

Electronic effects of an atom or
functional group contributed
through single bonds
Factors: electronegativity,
position within the structure

II. INDUCTIVE EFFECT

Inductive effect weakens with
increasing distance from the
substituent
Inductive effect weakens with
decreasing electronegativity of
the substituent

II. INDUCTIVE EFFECT

A substituent may WITHDRAW or
RELEASE electrons
ELECTRON-WITHDRAWING
SUBSTITUENT
-helps to offset negative charge
ELECTRON-RELEASING
SUBSTITUENT
-helps to offset the positive charge

Electron attracting/withdrawing
with effect
excess positive charges
inductive
+

R N R

NH3

NO2

R
those with electronegative atoms
NH2

OH

OCH3

Cl
Br
groups exhibiting orbital electronegativity
C N

N N

those with easily polarizable valence electrons

I

Electron attracting/withdrawing
inductive effect
CH3

CH3

CH2

Cl

H3C N CH3
--

H3C Cl

CH3

CH2

Electron releasing/donating
inductive
effect
alkyl groups
CH3
negative groups
-

COO

O
H3C C

--

H3C

H3C

CH C N
H3C

O
R C

O
C

O
O

R S O
O

III. STERIC EFFECT

Effect of atom or functional

group on CROWDING in the
molecule

III. STERIC
Most stable conformation has the least
EFFECT
Van der Waals repulsion

http://www.utdallas.edu/~scortes/ochem/OChem1_Lecture/Class_Materials/08_conform_anal.pdf

III. STERIC
EFFECT