Organic Chemistry

Chapter 7 - Resonance

Electron Delocalization and Resonance

Localized electrons =
restricted to a particular region

Delocalized electrons do not belong to a single atom or exclusively to a bond between 2 atoms

Kekule Structure
Benzene
C 6H 6
Rapid Equilibrium between 2 structures Proposed by Fredrich Kekule (1865 German chemist)

Rapid Equilibrium

Kekules Dream
*

Benzene Structure
Kekule Structures of Benzene were accepted in the 1930s when X-ray studies showed ALL SIX C-H bonds equal and ALL SIX C-C bonds equal!
H H H H H H

Bonding in Benzene
Each C is sp2 hybridized Each C has an unhybridized p orbital perpendicular to the plane of the ring The 6 p orbitals overlap to form a cloud

Resonance Hybrid
A compound with delocalized e- is said to have resonance
resonance contributor resonance structure contributing resonance structure

Resonance Hybrid
Benzene
contributing resonance structures

Resonance Hybrids
Drawing resonance hybrids
1) Only e- move (not atoms) 2) Only

and non-bonding e move

-

3) Total # e- stays same (as does unpaired e-)

Resonance Hybrids
e- can be moved only by

e move toward + or toward bond

-

Resonance Hybrids
e- can be moved only by
Nonbonding pair e- toward a

bond

Resonance Hybrids
e- can be moved only by
Nonbonding single e- toward a

bond

Resonance Hybrids
Drawing resonance hybrids

Resonance Hybrids

Practice Drawing Resonance

Practice Practice Practice

 What makes a Resonance Structure Have Decreased Stability?

1) an atom with an incomplete octet 2) a negative charge that is not on the most electronegative atom 3) a positive charge not on the most electropositive atom 4) charge separation

Examples To Examine

B is less stable than A

Equal Stability

Resonance Energy
1) The greater the predicted stability of a resonance contributor, the more it contributes to the resonance hybrid. 2) The greater the number of relatively stable resonance contributors, the greater the resonance energy. 3) The more nearly equivalent the resonance contributors, the greater the resonance energy.

Resonance Energy

The more nearly equivalent the resonance contributors, the greater the resonance energy

Stability of Dienes

Stability of butadiene

Butadiene Example
H3C O ]

H3C
Br

H3C O O

H3C O

Br

Br

Br

Allylic Cations
Allylic cations have delocalized e They are more stable due to resonance contributors:

Benzylic Cations
Benzylic cations have delocalized e They are more stable due to resonance contributors:

Stability of Cations
*

Consequences
Because of the allyl and benzyl cations and radicals are more stable, some products can be formed easier.

Mechanisms Mechanisms Mechanisms Look at how conjugation affects reactions

Effects on pKa
Carboxylic acids are stronger acids than alcohols due to resonance effects

Phenol
Why is this alcohol as acidic as it is?
-OH is on an sp2 hybridized C In phenol, some resonance contributors have a + charge on O 3 of phenols structures have separated charges

Molecular Orbital Theory

Molecular Orbital Theory can also help explain increased stability
READ THROUGH THIS SECTION OF THE BOOK

Thermodynamic vs. Kinetic Control

If the kinetic product and thermodynamic product differ, the major product will depend on reaction conditions. If carried out at mild (low-temp) conditions, the reaction will be irreversible and the kinetic product will be favored. If carried out at sufficiently vigorous (hi-temp) conditions, the reaction will be reversible and the thermodynamic product will be favored.

Thermodynamic vs. Kinetic Control

Kinetic product and thermodynamic product:

Formed fastest

Most stable

Thermodynamic vs. Kinetic Control

Reaction conditions control products!
Kinetic product low temp

Thermodynamic product high temp

Diels-Alder Reaction
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

This reaction makes new carbon carbon bonds Uses a conjugated diene and a dienophile

Diels-Alder Reaction
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

Electron withdrawing groups (O or N) increases the reactivity of the dienophile and increase the reactivity

acts as an electrophile

Diels-Alder Reaction
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

1,4 addition to a conjugated diene

Diels-Alder Stereochemistry
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

If a chiral center is created, equal amounts of R, S produced (racemic)

Diels-Alder Stereochemistry
Stereospecific: cis dienophile remains cis
trans dienophile remains trans
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

Diels-Alder Examples
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne

Dienophiles can also be C triple bond C

Bicycloalkanes
Nomenclature
parent is the alkane of the same number of carbons as are in two rings number from a bridgehead, along longest bridge back to the bridgehead, then along the next longest bridge, etc. show the lengths of bridges in brackets, from longest to shortest

1 6 7 2

5
4

bicyclo[2.2.1]heptane

Bicyclics - Nomenclature
Examples

Bicyclics - Nomenclature
Examples