SV - Organic Mechanisms - SN1 SN2 E1 E2

Reaction Mechanisms
Dr. Silviya Halacheva

Reaction Mechanisms
Reaction mechanisms are very simple once you understand the rules
Reaction Mechanisms
1. Curly arrows represent the movement of a pair of electrons
2. Curly arrows always begin on a bond or lone pair
3. Curly arrows always finish on an atom, either:
(a) resulting in a newly formed bond
(b) forming a negative charge
(c) neutralising an existing positive charge
4. Negative charges are attracted to positive charges
5. Atoms follow the normal valence rules: carbon has four bonds
(or three bonds plus a negative/positive charge), nitrogen has
three bonds (or four bonds plus a positive charge)… etc
Reaction Mechanisms
For inorganic reactions, we write the reactants, draw
an arrow, write the products, make sure the equation
is balanced and maybe add state symbols, e.g. (aq)
Reaction Mechanisms
The reaction between sodium hydroxide and
hydrochloric acid, forming sodium chloride and water:
Reaction Mechanisms
The reaction between ammonia and methanoic acid,
forming ammonium methanoate:
Reaction Mechanisms
The reaction between ammonia and methanoic acid,
forming ammonium methanoate:
For organic reactions like this one, we can add more

detail and (usually) draw a mechanism
Reaction Mechanisms
Electron pairs
Most mechanisms will involve just these five concepts…
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs Electrons are everything in organic
chemistry reactions, virtually
Bonds forming nothing happens which doesn’t
involve electrons
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming Most reactions involve bond
formation…
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Sometimes a reaction only involves
Bonds breaking forming bonds, but often reactions
require old bonds to break when
Positive charges new ones are formed
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Often the positive charge is on an H+
Positive charges ion or protonated nitrogen, but can
be on a protonated oxygen, or even a
Negative charges positively charged carbon atom
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
The negative charge is usually on an
Positive charges oxygen, halide ion or other anion,
sometimes on a negatively charged
Negative charges carbon atom
Reaction Mechanisms
Electron pairs
Reaction Mechanisms
Electron pairs
Reaction Mechanisms
Electron pairs
Reaction Mechanisms
Electron pairs
Bonds forming
Reaction Mechanisms
Electron pairs
Bonds forming
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Reaction Mechanisms
Electron pairs
Bonds forming
Bonds breaking
Positive charges
Negative charges
Types of Mechanism
The four types of mechanism which we will cover are:
1. Substitution
2. Addition
3. Elimination
4. Condensation
Types of Mechanism
1. Substitution
Types of Mechanism
2. Addition
Types of Mechanism
2. Addition
Types of Mechanism
3. Elimination
Types of Mechanism
4. Condensation
Types of Mechanism
4. Condensation
Nucleophiles and Electrophiles
Nucleophile = “nucleus loving” – literally, something that loves nuclei

Nucleophiles are either negatively charged or have a reactive lone pair

Nucleophiles are either negatively charged or have a reactive lone pair

Nucleophiles are also attracted to other positive things, such as:

Carbon atoms which are

bonded to electronegative
elements, such as halides
Carbon atoms which are Carbonyl groups of

bonded to electronegative aldehydes/ketones, acyl
elements, such as halides chlorides, anhydrides and
esters
Carbon atoms which are Carbonyl groups of Positively charged carbon

bonded to electronegative aldehydes/ketones, acyl atoms – which are known
atoms, such as halogens chlorides, anhydrides and as carbocations
esters
Carbon atoms which are Carbonyl groups of Positively charged carbon

bonded to electronegative aldehydes/ketones, acyl atoms – which are known
i.e. ELECTROPHILES
atoms, such as halogens chlorides, anhydrides and
esters
as carbocations
Electrophile = “electron loving” – literally, something that loves electrons

Electrophiles are either positively charged, have a vacant orbital – or both

nitronium ion
bromoalkane
aldehyde / ketone
tert-butyl carbocation
nitronium ion
bromoalkane
aldehyde / ketone under some circumstances,
Cl2 and Br2 can also act as
tert-butyl carbocation
electrophiles
Nucleophilic Substitution: SN2
SN2 stands for ‘nucleophilic substitution bimolecular’
NOTE: the superscripted double-dagger symbol ‡ means ‘transition state’

Transition States and Intermediates
Nucleophilic Substitution: SN1
SN1 stands for ‘nucleophilic substitution unimolecular’
Transition States and Intermediates
Nucleophilic Addition To Carbonyl
R1 and R2 can be alkyl or aryl groups – making the structure a ketone
One or both R-groups can be a hydrogen, in which case it will be an aldehyde
Aldehydes and ketones usually react the same way towards nucleophiles, but aldehydes are
more reactive because the hydrogen atom is small and the carbonyl carbon more exposed
The cyanide anion is a good nucleophile and will readily attack the electrophilic carbonyl carbon
The cyanide anion is a good nucleophile and will readily attack the electrophilic carbonyl carbon
This tetrahedral intermediate forms – the carbonyl carbon and oxygen are now sp3 hybridised
Once the reaction is finished, some dilute acid is added in order to protonate the oxygen…
…and a cyanohydrin has been formed

(the reaction is not stereoselective)


The mechanism of the reaction between an aldehyde or ketone

and any generic nucleophile will follow the same pattern
Such as sodium borohydride, which reduces aldehydes and

ketones to primary and secondary alcohols, respectively
In effect, a hydride ion – “H-minus” – is transferred from the borohydride ion as the B–H bond breaks
A similar tetrahedral intermediate is formed

The reaction is typically carried out in the presence of water, or an alcohol

such as methanol or ethanol, in order to provide a proton source
And the aldehyde/ketone has been reduced to an alcohol


A 50:50 mixture of two enantiomers is called a racemic mixture, or a racemate

(pronounced in a similar way to “fascinate”)
When a chiral compound is present as a racemate, the mixture can be represented with a wavy
bond to show that neither isomer predominates
Whenever a chiral structure is drawn with a plain bond,

it is assumed to be present as a racemate
Elimination Reactions: The E2 Mechanism
Like the SN2 mechanism, the E2 mechanism is short for ‘elimination bimolecular’
For an elimination reaction to occur, we need a base, such as hydroxide…

…and a hydrogen on an sp3 carbon atom with a good leaving group one position along
The base begins to remove the proton (i.e. hydrogen atom without its electron)…
…as the electrons from the C–H bond begin to form an alkene bond…
…and the leaving group leaves (avoiding having a carbon atom with five bonds)
This all happens in one smooth action – known as an E2 elimination reaction

This all happens in one smooth action – known as an E2 elimination reaction
If sodium hydroxide was the base, water and sodium bromide are the other products
Like the SN1 mechanism, the E1 mechanism is short for ‘elimination unimolecular’
and typically only occurs with tertiary halogenoalkanes or when the cation can be stabilised
The leaving group leaves first, taking its electrons and leaving a positive charge – i.e. forming a carbocation
The base then removes a proton from the intermediate in a separate second step
And an alkene is formed – note the regioselectivity…

…the base has a choice of hydrogen atoms which can be removed, however…
If a hydrogen atom from one of the methyl

groups is removed, the alkene which forms is
less substituted, less stable and less favoured
Depending upon the identity of the R-group,

both alkenes will be formed but the terminal
alkene (in red) will always be the minor product
MAJOR
MINOR
Stability of Alkenes
In general, the stability of substituted hydrocarbon alkenes

increases in the following order:
> > >

Stability of Alkenes
Also, (E)-alkenes are more stable than (Z)-alkenes
>
Condensation Reactions
In a condensation reaction, two molecules are joined together with the
elimination of a small molecule (usually water in a biological system)
In a condensation reaction, two molecules are joined together with the
elimination of a small molecule (usually water in a biological system)
For example, esters are formed by acid-catalysed reaction of a carboxylic

acid and an alcohol, with the elimination of a molecule of water
Mechanism of ester formation
The Reactivity of Acyl Chlorides
Due to the high electronegativity of chlorine and good leaving group ability of the chloride ion,
acyl chlorides are highly reactive. Most aliphatic acyl chlorides give off fumes of hydrogen
chloride when exposed to traces of moisture in the air, re-forming the parent carboxylic acid:
The reaction proceeds by attack of the highly delta-positive carbonyl carbon by water, kicking out
a chloride ion, which then combines with the excess proton to form hydrogen chloride.
Try drawing the mechanism of this reaction.

Replacing the water with an alcohol, R2OH, leads to the formation of an ester, with hydrogen
chloride as a byproduct – the mechanism is virtually the same.
The reaction between an acyl chloride and an amine is a common method to synthesise an
amide in the laboratory.
Nature’s method of amide bond formation
However, in biological systems it is not possible to utilise reactive intermediates such as acyl
chlorides for the synthesis of amide bonds.
Instead, the carboxylic acid of an amino acid is first converted into an activated ester and reacted
with the amine group of another amino acid under enzymatic catalysis to form an amide bond,
i.e. a peptide, with overall elimination of water.
The net transformation is therefore:

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Reaction Mechanisms

Dr. Silviya Halacheva

For organic reactions like this one, we can add more

Nucleophile = “nucleus loving” – literally, something that loves nuclei

Nucleophile = “nucleus loving” – literally, something that loves nuclei

Nucleophiles are either negatively charged or have a reactive lone pair

Nucleophile = “nucleus loving” – literally, something that loves nuclei

Nucleophiles are either negatively charged or have a reactive lone pair

Nucleophiles are also attracted to other positive things, such as:

Nucleophiles are also attracted to other positive things, such as:

Carbon atoms which are

Nucleophiles are also attracted to other positive things, such as:

Carbon atoms which are Carbonyl groups of

Nucleophiles are also attracted to other positive things, such as:

Carbon atoms which are Carbonyl groups of Positively charged carbon

Nucleophiles are also attracted to other positive things, such as:

Carbon atoms which are Carbonyl groups of Positively charged carbon

Electrophile = “electron loving” – literally, something that loves electrons

Electrophile = “electron loving” – literally, something that loves electrons

Electrophiles are either positively charged, have a vacant orbital – or both

Electrophile = “electron loving” – literally, something that loves electrons

Electrophiles are either positively charged, have a vacant orbital – or both

Electrophile = “electron loving” – literally, something that loves electrons

Electrophiles are either positively charged, have a vacant orbital – or both

NOTE: the superscripted double-dagger symbol ‡ means ‘transition state’

R1 and R2 can be alkyl or aryl groups – making the structure a ketone

One or both R-groups can be a hydrogen, in which case it will be an aldehyde

…and a cyanohydrin has been formed

(the reaction is not stereoselective)

(the reaction is not stereoselective)

The mechanism of the reaction between an aldehyde or ketone

Such as sodium borohydride, which reduces aldehydes and

A similar tetrahedral intermediate is formed

The reaction is typically carried out in the presence of water, or an alcohol

And the aldehyde/ketone has been reduced to an alcohol

(the reaction is not stereoselective)

A 50:50 mixture of two enantiomers is called a racemic mixture, or a racemate

Whenever a chiral structure is drawn with a plain bond,

For an elimination reaction to occur, we need a base, such as hydroxide…

This all happens in one smooth action – known as an E2 elimination reaction

This all happens in one smooth action – known as an E2 elimination reaction

And an alkene is formed – note the regioselectivity…

If a hydrogen atom from one of the methyl

Depending upon the identity of the R-group,

In general, the stability of substituted hydrocarbon alkenes

> > >

Also, (E)-alkenes are more stable than (Z)-alkenes

For example, esters are formed by acid-catalysed reaction of a carboxylic

Try drawing the mechanism of this reaction.

The net transformation is therefore:

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