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Conjugation, Resonance and Aromaticity

This document discusses conjugation, resonance, and aromaticity in propene. Propene can undergo both polar and radical reactions faster than ethane or ethene due to the methyl group affecting the reactivity of the double bond and vice versa. Propene has two reaction sites: the double bond and the allylic methyl group. The allyl radical formed from propene is more stable than the vinyl radical due to resonance delocalization of the single electron over three carbons. Resonance theory can explain unexpected products from reactions of unsaturated compounds. Hyperconjugation also contributes to radical stability by delocalizing an electron into empty sp3 orbitals.

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224 views6 pages

Conjugation, Resonance and Aromaticity

This document discusses conjugation, resonance, and aromaticity in propene. Propene can undergo both polar and radical reactions faster than ethane or ethene due to the methyl group affecting the reactivity of the double bond and vice versa. Propene has two reaction sites: the double bond and the allylic methyl group. The allyl radical formed from propene is more stable than the vinyl radical due to resonance delocalization of the single electron over three carbons. Resonance theory can explain unexpected products from reactions of unsaturated compounds. Hyperconjugation also contributes to radical stability by delocalizing an electron into empty sp3 orbitals.

Uploaded by

vijay
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Conjugation, Resonance and Aromaticity

Simple alkenes eg Propene can behave like normal alkenes:


Br

Br2

Polar Reaction
Br

but can also give unexpected products:

Br2

Br

Radical Reaction

Peroxide
both reactions faster than for equivalent reactions on ethene or propane
Clearly methyl group affecting reactivity of double bond and vice versa
Propene actually has two different sites which can be attacked:
H
H

Polar
Attack

C
H2

can divide propene into two regions:


(i)

double bond

(ii)

allylic methyl group

Br

Radical
Attack

+ HBr

Free radical substitution on alkenes


First step in radical attack abstraction of hydrogen atom ( H )
But why remove hydrogen from methyl group only?
Comparing how easily hydrogen atoms can be abstracted from various
carbon centres gives this order:

>
Allylic

>
Tertiary

>
Secondary

>
Primary

Vinyl

so allylic hydrogens much more easily removed compared to vinylic


hydrogens hence

much more easily formed than


allyl radical

or
vinyl radicals

allyl radical is formed more easily due to extra stability relative to vinyl
radical.
Stability due to ability to delocalise the single electron over all three
carbons:

Allyl radical actually exists as a resonance hybrid of two forms and the
real structure is better represented as:

It is a general rule in organic chemistry that the greater the area over which a
charge can be delocalised the more stable the species becomes
Allyl radical resulting from propene is symmetrical, but if unsymmetrical
alkenes used the effect of resonance on reaction products can be seen:

Br2 / Peroxide
Br

and

Br

rearranged

expected

two products arise due to resonance of intermediate radical:

Br
Br

bromine can form bond at either end of resonance hybrid giving two
products

Resonance Theory developed to explain unexpected experimental results


with certain unsaturated compounds
Molecules exhibiting resonance exist as hybrids of all the possible resonance
structures (also called canonical structures)
Resonance hybrids are more stable than any of the contributing resonance
structures the increase in stability is the resonance stabilisation energy
Compare radicals generated from propane and propene:
H (kcal mol-1 )
+98

+88

Allyl radical more stable by 10 kcal mol-1 due to ability to delocalise the
single electron
Resonance requires good overlap of orbital with single electron with other
orbitals into which it can move:

efficient ovelap of orbital containing single


electron with p orbitals of double bond

more efficient the overlap the greater the contribution to stability

Resonance theory can also explain some effects which do not involve
multiple bonds
Consider stability of alkyl radicals:

>
Tertiary

>
Primary

Secondary

for multiple bonds the orbital containing the single electron overlapped with
p orbitals forming double bond.
Orbital containing single electron can also overlap with sp3 orbitals on
adjacent carbon termed hyperconjugation
overlap of p and sp3 orbitals

thus theoretical resonance structures can be drawn for overlap with each sp3
orbital:
H

H
H

CH2
H

CH2

H
H

this can be done for each sp3 orbital, so 3x for a primary radical

the orbital containing the single electron can overlap with 3 sp3 orbitals for
primary radicals, but what about secondary and tertiary?
H

H
H

H
H

Secondary

Tertiary

by hyperconjugation single electron can be delocalised into 6 orbitals for


secondary radicals and 9 orbitals for tertiary
orbital overlap in hyperconjugation less efficient than for overlap with p
orbitals of double bonds, but stabilisation energies still show contribution:

Radical

Stabilisation energy (kcal mol-1)

Primary

Secondary

Tertiary

12

Stabilisation energy is directly proportional to the number of orbitals which


the single electron can be delocalised into ie the area of space over which it
can be spread

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