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Chapter 7 - 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
Resonance Hybrids
e- can be moved only by
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
Examples To Examine
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.
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
Formed fastest
Most stable
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
Diels-Alder Stereochemistry
Otto Diels Kiel University Kiel Kurt Alder Cologne University Cologne
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
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