ISHCMC CHEMISTRY

H L O R G A N IC C H EM IS TR Y

20.1 TY P ES O F

G reat,am azing,super resources

1. Chemguide Organic
2. MSJ Chem - HL organic
3. Organic interactives

LEARN IN G O BJECTIVES 20.1

LEARN IN G O BJECTIVES 20.1

LEARN IN G O BJECTIVES 20.1

H L TY P ES O F
Organic reactions
to what
R EAareCorganised
TIO Naccording
S

happens (the type of reaction) and how it happens

(the mechanism of the reaction)
Different combinations of mechanisms and reaction
type are described in this section
Many mechanisms describe the reactants according
to electrophilic and nucleophilic behaviour

N ucleophiles and Electrophiles

Nucleophiles
are electron rich and attack areas of electron

deficiency.
They act as Lewis bases and donate a pair of
electrons in forming a new covalent bond
Examples: OH-, H2O and CN-

Electrophiles
are electron deficient & accept electron pairs

from a nucleophile
They act as Lewis acids
Examples: H+, Br+ and NO2+

N ucleophiles and Electrophiles

A convention used in depicting

mechanisms is the curly arrow it

shows the movement of an electron pair
The tail shows where the electron pair
have come from and the arrow head
showing where it is going

Video:
Thornley: SN1 and SN2

N ucleophilic substitution
reactions:halogenoalkanes
Shorthand used: SN substitution nucleophilic

The polar carbon-halogen bond in halogenoalkanes

means that the carbon atom is electron deficient

and it is attacked by nucleophiles such as OH As a result, the carbon-halogen bond breaks and
the halogen atom is released as a negative ion
(halide)

 This types of breakage where both the

shared electrons go to one of the products

is known as heterolytic fission
The halogen is known as the leaving group
The exact mechanism of these reactions
depends on whether the halogenoalkane is
primary,
secondary or
tertiary

Prim ary halogenoalkanes:

S N 2 m echanism
Primary halogenoalkanes have at least 2

hydrogen atoms attached to the carbon of

the carbon-halogen bond, eg chloroethane

The overall reaction that occurs with

NaOH is:

Prim ary halogenoalkanes:

S N 2 m echanism
As the hydrogen atoms are so small, the carbon

atom is relatively open to attack by the nucleophile

An unstable transition state is formed in which the
carbon is weakly bonded to the halogen & the
nucleophile
The carbon-halogen bond then breaks
heterolytically, releasing Cl- and forming the
alcohol product

 This is effectively a 1-step reaction with

an unstable transition state

The mechanism depends on the
concentration of both the halogenoalkane
and the OH- ion, so it is known as a
bimolecular reaction
Rate = k [halogenoalkane] [nucleophile]
Therefore the full name of this is
described as:

Prim ary halogenoalkanes:

S N 2 m echanism
Note: the nucleophile attacks the

elctrophilic carbon atom on the opposite

side from the leaving group which causes
an inversion of the arrangement of the
atoms around carbon

Prim ary halogenoalkanes:

S N 2 m echanism

The SN2 mechanism is favoured by polar

aprotic solvents (those which are not able to

form hydrogen bonds, although they may
contain strong dipoles)
This means that they solvate the metal cation
(eg Na+) rather than the nucleophile (OH -)
Suitable solvents include propanone (CH 3)2CO
and ethanentrile (CH3CN)

Tertiary halogenoalkane:
S N 1 m echanism
Tertiary halogenoalkanes have 3 alkyl

groups attached to the carbon of the

carbon-haologen bond, eg 2-chloro-2methylpropane

The overall reaction that occurs with

NaOH is:

Tertiary halogenoalkane:
S N 1 m echanism

Here the presence of the 3 alkyl groups

around the carbon of the carbon-halogen

bond causes what is called steric
hindrance
Meaning that these bulky groups make it
difficult for an incoming group to attack
this carbon atom

Tertiary halogenoalkane:S N 1 m echanism

Instead the first step of the reaction involves the

halogenoalkane ionizing by breaking its C-halogen bond

heterolytically
As the halide ion is detached, this leaves the carbon atom
with a temporary positive charge, which is known as a
carbocation intermediate
This is then attacked by the nucleophile in the second step
of the reaction, leading to the formation of a new bond

 Another reason which favours this

mechanism in tertiary halogenoalkanes is

that the carbocation is stabilized by the
presence of the 3 alkyl groups, as each of
these has an electron-donating or
positive inductive effect (shown by the
blue arrows)
This stabilizing effect helps the

 Because the slow step of this reaction, the

rate-determining step, is determined by

the concentration only of the
halogenoalkane, it is described as a
unimolecular reaction
Rate = k [halogenoalkane]
Therefore this reaction mechanism is
known as:

Tertiary halogenoalkane:S N 1 m echanism

The carbocation intermediate has a planar shape which

means that the nucleophile can attack from any position

this means that the SN1 reaction is not stereospecific (it
can give rise to racemic mixtures more on this later)
The influence of solvents is mostly a result of their stability
to stabilize the carbocation intermediate anything that
stabilizes the intermediate will favour the reaction
Polar, protic solvents contain OH or NH and so are able to
form hydrogen bonds
They are effective in stabilizing the positively charged
intermediate by solvation involving ion-dipole interactions
Suitable solvents include water, alcohols & carboxylic acids

Secondary halogenoalkanes
It is not possible to be precise about

the mechanism of nucleophilic

substitution in secondary
halogenoalkanes, as data show that
they usually undergo a mixture of both
SN1 and SN2 mechanisms

Com parison of the

rates of
nucleophilic
substitution
reactions

Com parison ofthe rates of

nucleophilic substitution reactions
In this section we will compare the rates
of the nucleophilic substitution reactions
by looking at:
1. The effect of the mechanism

2. The influence of the leaving group

(halogen)
3. Choice of solvent

1.The eff
ect ofthe m echanism
Experimental data have shown that the

SN1 mechanism proceeds more quickly

than the SN2
So substitution reactions occur more
quickly with tertiary halogenoalkanes
than with primary
Secondary halogenoalkanes show an
intermediate rate of reaction as they use
both mechanisms
When all other variables are kept
constant, the relative rate of the 3

2.Infl
uence ofthe leaving group
There are 2 possible factors to consider:
a) The polarity of the carbon-halogen bond

- As the electronegativity of the halogens

decreases when going down the group, the
carbon of the carbon-halogen bond
becomes less electron deficient & so less
vulnerable to nucleophilic attack
-

2.Infl
uence ofthe leaving group
b) The strength of the carbon-halogen bond
Bond energy data shows that he carbon-

halogen bond decreases in strength from

fluorine to iodine
As the substitution reaction involves breaking
this bond, we would expect the ease of
breaking bonds to be:
Reaction rate data indicate that b) wins this

battle
The relative rate of reaction of the different
halogens in halogenoalkanes when all other

2.Infl
uence ofthe leaving group

3.Choice ofsolvent
Recall that the SN1 mechanism is favoured by polar,

protic solvents while the SN2 mechanism is favoured

by polar, aprotic solvents
So, overall, the fastest reactions will occur with
tertiary iodoalkanes in polar, protic solvents
Nucleophilic substitution reactions of
halogenoalkanes can be followed by the appearance
of the halide ion
Silver nitrate solution added to the reaction mixture
reacts with the halide ion, forming a precipitate of
the silver halide, each with a distinct colour

Video:
Thornley

- Rates of nucleophilic substitution

Sum m ary of dif e

frences in the 2
m echanism s of nucleophilic substitution
reactions

Electrophilic addition reactions:

alkenes
As you hopefully know, alkenes are unsaturated

molecules and are important in many synthesis

pathways because they readily undergo addition
reactions
To understand the mechanism of these reactions
it is useful to focus first on some key features of
the carbon-carbon double bond

Video:
thornley - reaction pathways

Electrophilic addition reactions:

alkenes

The nature of the double bond in alkenes is:

The C atoms of the double bond are sp 2
hybridized, forming a planar triangular shape
(bond angle is 12o0)
This is a fairly open structure (easy for attack)
The pi bond represents an area of electron
density above and below the plane of the bond
axis because electrons in the pi bond are less
closely associated with the nuclei, it is weaker
than the sigma bond and so breaks more easily
during the addition reactions
The pi bond is attractive to electrophiles

Electrophilic addition reactions:

alkenes

When this bond breaks, reactants attach at

each carbon atom:

Reactions between these reagents and

alkenes are known as electrophilic

addition reactions
Examples include the addition of halogens
and hydrogen halides to alkenes
In these reactions, the electrophile is
produced through heterolytic fission

Electrophilic addition reactions:

ethene and brom ine

When ethene gas is bubbled through

bromine at room temperature, the brown

colour of the bromine fades as it reacts to
form the saturated 1,2-dibromoethane

Youtube

Electrophilic addition reactions:

ethene and brom ine

The mechanism for the reaction is as follows:
Bromine is a non-polar molecule, but as it
approaches the electron rich region of the alkene, it
becomes polarized by electron repulsion

The bromine atom nearest the alkenes double bond

gains a 8+ charge and acts as the electrophile

The bromine molecule splits heterolytically, forming
Br+ and Br-, and the initial attack on the ethene in
which the pi bond breaks is carried out by the Br +

Electrophilic addition reactions:

ethene and brom ine

This step is slow, resulting in an unstable

carbocation intermediate in which the carbon

atom has a share in only 6 outer electrons and
carries an overall positive charge
This unstable species then reacts rapidly with
the negative bromide ion, Br-, forming the
product 1,2-dibromoethane

Electrophilic addition reactions:

ethene and brom ine

Overall the equation for the reaction is:

Similar reactions take place with other

alkenes, eg propene

Electrophilic addition reactions:

ethene and hydrogen brom ide

When ethene gas is bubbled through a

concentrated aqueous solution of

hydrogen bromide, HBr, an addition
reaction occurs fairly readily at room
temperature, forming bromoethane

Electrophilic addition reactions:

ethene and hydrogen brom ide

The reaction is similar to ethene and bromine

HBr as a polar molecule undergoes heterolytic

fission to form H+ and Br-, and the electrophile,

H+, makes the initial attack on the alkenes
double bond
The unstable carbocation intermediate that
forms from this step then reacts quickly with
Br- to form the addition product

Electrophilic addition reactions:

ethene and hydrogen brom ide

The mechanism is as follows:

One piece of evidence that supports this mechanism is

that the reaction is favoured by a polar solvent that

facilitates the production of ions from heterolytic fission
The other hydrogen halides react similarly with alkenes
HI reacts more readily than HBr due to its weaker
bond

Electrophilic addition reactions:

propene + hydrogen brom ide

(unsym m etric addition)
When an unsymmetric alkene such as propene is

reacted with a hydrogen halide such as HBr,

there are theoretically 2 different products that
can form
These are isomers of each other and they result
from 2 possible pathways through the
electrophilic addition mechanism described
previously

Electrophilic addition reactions:

propene + hydrogen brom ide(unsym m etric
addition)

The difference between these 2 depends on

whether the attacking electrophile (H+ formed

from heterolytic fission of HBr) is more likely to
bond to the carbon labelled 2 or 1
So which is more likely? The answer comes
from considering which pathway will give the
most stable carbocation during the addition

Electrophilic addition reactions:

propene + hydrogen brom ide(unsym m etric
addition)
Recall that alkyl groups around a carbon
stabilize it somewhat due to their positive
inductive effects meaning that they push
electron density away from themselves and so
lessen the density of the +ve charge
In a) below, the carbo cation is a primary
carbocation and is stabilized by one one such
positive inductive effect, whereas in b), a
secondary carbocation forms in which there
are two such effects and the stabilization is
greater

Electrophilic addition reactions:

propene + hydrogen brom ide(unsym m etric
addition)
Consequently, the more stable carbocation in
b) will be more likely to persist and react with
Br-, leading to 2-bromopropane as the main
product of the reaction

Therefore the correct mechanism for the

reaction is:

M arkovnikovs R ule
We can predict such an outcome for any reaction

involving addition of a hydrogen halide to assymetric

alkenes by using Markovnikovs rule
This states: the hydrogen will attach to the carbon
that is already bonded to the greater number of
hydrogens
this is based on the fact that the mechanism that
proceeds via the most stable carbocation will be
favoured
In more general terms it can be stated as the more
electropositive part of the reacting species bonds to
the least highly substituted carbon atom in the alkene
(the one with the smaller number of carbons attached)

M arkovnikovs R ule

W orked
exam ple:

Q uestions

Electrophilic substitution reactions:

B enzene
Despite its high saturation, benzene does not behave like

alkenes in its reactions

Its unusual and highly stable aromatic ring determines that
substitution is favoured
However, like alkenes it is attractive to electrophiles
because its ring is a region of electron density
The delocalized electron cloud of pi electrons seeks electron
deficient species & forms a new bond as a H atom is lost
The reactions are therefore electrophilic substitution

Electrophilic substitution reactions:

B enzene
The reaction has high activation energy and so

proceeds rather slowly this is because the first

step in the mechanism, in which an electron pair
from the benzene is attracted to the electrophile,
leads to a disruption of the symmetry of the
delocalized pi system
This unstable carbocation intermediate that forms
has both the entering atom or group and the
leaving hydrogen temporarily bonded to the ring

 E+ is used to represent an electrophile

The incomplete circle inside the ring

shows its loss of symmetry, with the

positive charge distributed over the bulk
of the molecule
Loss of hydrogen ion, H+, from this
intermediate leads to the electrically
neutral substitution product as two
electrons from the C-H bond move to
regenerate the aromatic ring

Electrophilic substitution reactions:

B enzene
This product is more stable, as shown below

The reactions can be used with different electrophiles eg nitration

N itration of B enzene
The nitration of benzene is the

substitution of H by NO2 to form

nitrobenzene, C6H5NO2
The electrophile for the reaction is NO2+
This is generated by using nitrating

mixture (a mixture of concentrated nitric

and sulfuric acids)
The stronger of the acids, sulfuric
protonates the nitric acid, which then
loses a molecule of water to produce NO2+

N itration of B enzene

NO2+ is a strong electrophile & reacts with the pi

electrons of the benzene ring to form the

carbocation intermediate
Loss of a proton from this leads to reformation of
the arene ring in the product nitrobenzene, which
appears as a yellow oil
The hyrogen ion released reacts with the base
HSO4- to reform sulfuric acid, H2SO4

N itration of B enzene

R eduction
reactions

It is convenient in organic chem to analyse redox

reactions in terms of gain and loss of hydrogen

(rather than electrons)
In the following reactions, reduction can be
identified where hydrogen is gained by a reactant

R eduction of C arbonyl
com
pounds
We previously
saw that the oxidation of alcohols
to carbonyl compounds (those that contain
C=O) takes place in the presence of a suitable
oxidizing agent and yields different products
depending on the alcohol and the conditions
Primary alcohol aldehyde carboxylic acid
Secondary alcohol ketone

We can reverse these reactions using a suitable

reducing agent:
1. Sodium borohydride, NaBH4, in aqueous or alcoholic

solutions
2. Lithium aluminium hydride, LiAlH 4, in anhydrous
conditions, such as dry ether followed by aqueous
acid

R eduction of C arbonyl
com pounds N aB H 4 and LiA lH 4
Both reagents produce the hydride ion, H-, which

acts as a nucleophile on the electron-deficient

carbonyl carbon
NaBH4 tends to be the safer reagent but it is not
reactive enough to reduce the carboxylic acids
so LiAlH4 must be used for this
[+H] represents reduction

The reaction cannot be stopped at the aldehyde as it reacts readily

R eduction of C arbonyl
com pounds N aB H 4 and LiA lH 4
Conditions for this reaction: heat with LiAlH 4 in dry ether

Conditions for this reaction: heat with

NaBH4

R eduction of
Nitrobenzene,
C H NO , can be converted
ni
trobenzene
6

into phenylamine, C6H5NH2, in a 2 stage

reduction

Q uestions

20.2
S ynthetic
routes

Learning
O bjectives

Sum m ary of reactions of this

chapter

Synthetic routes
The development of new

organic compounds from

drugs to dyes, clothing to
construction materials is vitally
important
Organic chemists typically have
to convert compounds from one
form to another in sequence
(often the product from one is
the reactant in the next)
The series of discrete steps
involved is known as a
synthetic route

Retro-synthesis:W orking backw ards

The desired product, known as the target

molecule, can serve as the starting point

By studying its functional group, it can be
strategically broken down into
progressively smaller fragments known as
precursors
Each precursor then becomes the target
for further analysis, eventually yielding a
familiar molecule which the synthetic
sequence can start

W orked
Exam ple

W orked
Exam ple

q uestions