Referensi

Imyanitov, Naum S. (1993). "Is This Reaction a Substitution, OxidationReduction, or Transfer?". J. Chem. Educ. 70 (1): 1416
Fessenden, JR., Fessenden ,JS., 1982. Kimia Organik, Jilid 2, Edisi 3, Jakarta:
Erlangga, hal. 151
Bahl, Bs, Arun Bahl., 1985, Advanced Organic Chemistry, New Delhi: Chad
and Co.Ltd; pp. 541-567.
https://www.boundless.com/chemistry/definition/substitution
http://www.chemguide.co.uk/mechanisms/nucsub/whatis.html#top

Substitution reaction
Substitution reaction is also known as single displacement reaction and single
replacement reaction. In a substitution reaction, a functional group in a
particular chemical compound is replaced by another group.[1][2] In organic
chemistry, the electrophilic and nucleophilic substitution reactions are of prime
importance. Organic substitution reactions are classified in several mainorganic
reaction types depending on whether the reagent that brings about the substitution
is considered an electrophile or a nucleophile, whether a reactive
intermediate involved in the reaction is a carbocation, a carbanion or a free
radical or whether the substrate is aliphatic or aromatic. Detailed understanding of
a reaction type helps to predict the product outcome in a reaction. It also is helpful
for optimizing a reaction with regard to variables such as temperature and choice
of solvent.
A good example of a substitution reaction is
the photochemical chlorination of methane forming methyl chloride.

chlorination of methane by chlorine

Nucleophilic substitution
Nucleophilic substitution happens when the reagent is a nucleophile, which is a
molecule that can donate an electron pair to form a chemical bond in a reaction.
A nucleophile reacts with an aliphatic substrate in a nucleophilic aliphatic
substitution reaction. These substitutions can be produced by two different
mechanisms: unimolecular nucleophilic substitution (SN1) and bimolecular
nucleophilic substitution (SN2). The SN1 mechanism has two steps. In the first step,
the leaving group departs, forming a carbocation. In the second step, the
nucleophilic reagent attacks the carbocation and forms a sigma bond. This
mechanism can result in either inversion or retention of configuration; usually both
occur equally, resulting inracemization. An SN2 reaction has just one step. The
attack of the reagent and the expulsion of the leaving group happen simultaneously.
This mechanism always results in inversion of configuration.
When the substrate is an aromatic compound the reaction type is nucleophilic
aromatic substitution. Carboxylic acid derivatives react with nucleophiles
in nucleophilic acyl substitution. This kind of reaction can be useful in preparing
compounds.
Electrophilic substitution
Electrophiles are involved in electrophilic substitution reactions and particularly
in electrophilic aromatic substitutions.

Electrophilic aromatic substitution

Electrophilic reactions to other unsaturated compounds than arenes generally lead
to electrophilic addition rather than substitution.
Radical substitution

A radical substitution reaction involves radicals. An example is the Hunsdiecker

reaction.
Organometallic substitution
Coupling reactions are a class of metal-catalyzed reactions involving an
organometallic compound RM and an organic halide R'X that together react to a
compound of the type R-R' with formation of a new carbon-carbon bond. Examples
include the Heck reaction, Ullmann reaction, and WurtzFittig reaction. Many
variations exist.[3]
Substituted compounds
Substituted compounds are chemical compounds where one or
more hydrogen atoms of a core structure have been replaced with a functional
group like alkyl, hydroxy, or halogen.
For example benzene is a simple aromatic ring and substituted benzenes are
a heterogeneous group of chemicals with a wide spectrum of uses and properties:

compound

general formula

Benzene

C6H6

Toluene

C6H5-CH3

o-Xylene

C6H4(-CH3)2

Mesitylene

C6H3(-CH3)3

general structure

Phenol

C6H5-OH

Just a few substituted benzene compounds

The nucleophilic substitution reaction - an SN2 reaction

We'll talk this mechanism through using an ion as a nucleophile, because it's slightly
easier. The water and ammonia mechanisms involve an extra step which you can
read about on the pages describing those particular mechanisms.
We'll take bromoethane as a typical primary halogenoalkane. The bromoethane has
a polar bond between the carbon and the bromine.
We'll look at its reaction with a general purpose nucleophilic ion which
we'll call Nu-. This will have at least one lone pair of electrons.
Nu- could, for example, be OH- or CN-.

The lone pair on the Nu- ion will be strongly attracted to the + carbon, and will
move towards it, beginning to make a co-ordinate (dative covalent) bond. In the
process the electrons in the C-Br bond will be pushed even closer towards the
bromine, making it increasingly negative.
Technically, this is known as an SN2 reaction. S stands for
substitution, N for nucleophilic, and the 2 is because the initial
stage of the reaction involves two species - the bromoethane
and the Nu- ion. If your syllabus doesn't refer to SN2 reactions
by name, you can just call it nucleophilic substitution.

Some examiners like you to show the transition state in the

mechanism, in which case you need to write it in a bit more
detail - showing how everything is arranged in space.

Be very careful when you draw the transition state to make a

clear difference between the dotted lines showing the half-made
and half-broken bonds, and those showing the bonds going back
into the paper.
Notice that the molecule has been inverted during the reaction rather like an umbrella being blown inside-out.

Note: If you aren't happy about the various ways

of drawing bonds, it is important to follow this link
to find out exactly what the various symbols
mean.
It is also important to know which of these ways
of drawing the mechanism your particular
examiners want you to use. If you haven't already
checked your syllabus, recent exam papers and
mark schemes, you must do so! At the time of
writing, Edexcel, for example, wanted the
transition state included, and that isn't obvious
from their syllabus. You haveto check mark
schemes and examiners reports.
Use the BACK button on your browser to return to
this page.

Nucleophilic substitution in tertiary halogenoalkanes

Warning! Check your syllabus, past papers and

any support material published by your examiners
to find out whether you need this. If there's no
mention of tertiary halogenoalkanes or SN1
reactions, then you probably don't need it.

Remember that a tertiary halogenoalkane has three alkyl groups

attached to the carbon with the halogen on it. These alkyl
groups can be the same or different, but in this section, we shall
just consider a simple one, (CH3)3CBr - 2-bromo-2methylpropane.
The nucleophilic substitution reaction - an SN1
reaction
Once again, we'll talk this mechanism through using an ion as a
nucleophile, because it's slightly easier, and again we'll look at
the reaction of a general purpose nucleophilic ion which we'll
call Nu-. This will have at least one lone pair of electrons.
Why is a different mechanism necessary?
You will remember that when a nucleophile attacks a primary
halogenoalkane, it approaches the + carbon atom from the
side away from the halogen atom.
With a tertiary halogenoalkane, this is impossible. The back of
the molecule is completely cluttered with CH3 groups.

Since any other approach is prevented by the bromine atom, the

reaction has to go by an alternative mechanism.
If your examiners want you to show the transition state, draw
the mechanism like this:

The reaction of tertiary halogenoalkanes with hydroxide ions

The facts
The facts of the reaction are exactly the same as with primary
halogenoalkanes. If the halogenoalkane is heated under reflux
with a solution of sodium or potassium hydroxide in a mixture of
ethanol and water, the halogen is replaced by -OH, and an
alcohol is produced.
For example:

Or if you want the full equation rather than the ionic one:

The mechanism
This mechanism involves an initial ionisation of the
halogenoalkane:

followed by a very rapid attack by the hydroxide ion on the

carbocation (carbonium ion) formed:

This is again an example ofnucleophilic substitution.

This time the slow step of the reaction only involves one species
- the halogenoalkane. It is known as an SN1 reaction.

The reaction of secondary halogenoalkanes with hydroxide ions

The facts
The facts of the reaction are exactly the same as with primary or
tertiary halogenoalkanes. The halogenoalkane is heated under
reflux with a solution of sodium or potassium hydroxide in a
mixture of ethanol and water.
For example:

The mechanism
Secondary halogenoalkanes use both SN2 and SN1 mechanisms.
For example, the SN2 mechanism is:

Should you need it, the two stages of the SN1 mechanism are: