Unless otherwise stated, all images in this file have been reproduced from:
Blackman, Bottle, Schmid, Mocerino and Wille,
Chemistry, 2012 (John Wiley & Sons)
ISBN: 9 78047081 0866
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Mechanisms: overview
Lecture 05 Lecture 06 Lecture 07
Elimination reactions: Overview of Structure elucidation
E1 & E2 mechanisms Mass spectrometry
Nucleophiles are attracted to electrophiles
Electrophile
Seeks a lone pair. Is electron deficient. Nucleophile’s arrow goes there.
Nucleophile
Donates lone pair. Is electron rich. Arrow starts there.
Worksheet Q1
3
Curly arrows show electrons moving
A curly arrow indicates electron pair movement
– A curly arrow starts at the electron pair that moves and ends
at the atom to which the electron pair has moved
O O
H OH O
H H
– An arrow from a bond indicates breaking of that bond; an
arrow between two species indicates a bond is formed between
the species
O H O
H O
R O O R O H H
H H
Worksheet Q2 4
Five types of organic reaction
1. Acid/ base reactions
2. Substitution
3. Addition
4. Elimination
5. Oxidation & Reduction
5
Electrophiles add to alkenes
Two steps
▪ An unstable intermediate carbocation is formed
Terminology: We say this is an electrophilic addition since the thing that is reacting with
Worksheet Q3
the organic starting material is an electrophile 6
More substituted carbocations are more stable
Alkyl groups help to spread the positive charge a little along the bonds – an Inductive Effect
Adjacent C-H bonds donate a little electron density through space – Hyperconjugation
Worksheet Q4 7
From CHEM1111:
Benzene and related compounds are aromatic
Aromatic systems are conjugated
but also
the conjugated system is cyclic
AND
the conjugated system contains
4n+2 p electrons
(i.e. 2, 6, 10… etc electrons)
(this last bit is called Huckel’s Rule)
Which of these molecules is aromatic?
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Aromaticity brings stability
Instead – Electrophilic Aromatic Substitution – SEAr
the aromatic ring attacks an electrophile with its mobile electron cloud
We usually need to add a catalyst, like a Lewis acid, to make the
electrophile more reactive
Same mechanism for bromination, nitration (where E+ is NO2+) etc. Useful reactions.
Worksheet Q5 9
SN1: Carbocation intermediate
Reaction goes, but rate found to be proportional only to
concentration of alkyl bromide, not methanol.
From Worksheet to Lecture 4 …
Carbocation needs to be okay
favoured for 3° alkyl halides
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SN2: Direct attack of the nucleophile
Nucleophile needs access favoured for 1° alkyl halides
We refer to this as Substitution – Nucleophilic – Second Order
or SN2
Reaction rate proportional to concentrations of both nucleophile and
electrophile
Worksheet Q6 11
E2: Alkyl halide + strong base
Measured rate: proportional to concentrations of bromopropane
AND hydroxide
and
Wouldn’t expect to see unstable primary carbocation
So what shall we call it?
How about Elimination – Second Order
Or E2
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Selectivity depends on the size of the base
If there’s a choice of double bond in E2…
The more substituted double bond forms (Again. Cool. Next year.)
Unless you use a great big bulky base:
In which case it just takes off the sterically most available H
(Some people call this Hofmann’s Rule.) 13
E1: Elimination via a carbocation
So carbocation intermediates can also lead to elimination products
So the rate of this reaction will be proportional to the concentration of
the starting material only.
And it’s an Elimination reaction.
So what shall we call it?
How about Elimination – First Order
Worksheet Q7 / Q8 Or E1 14
Learning outcomes
After this lecture you should be able to
▪ Identify nucleophiles and electrophiles, and understand how
they are likely to react with each other.
▪ Use curly arrows to draw mechanisms for reactions you’ve
seen before.
▪ Think about applying your understanding of nucleophiles,
electrophiles and curly arrows to explain reactions you’ve not
seen before.
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