NUCLEOPHILIC SUBSTITUTION

REACTIONS
DR.MOHAMAD NASIR OTHMAN
 Nucleophile
• A nucleophile is a reagent that seeks a positive
center. Reagent is a substance that acts on
another in a chemical reaction.
• The word nucleophile comes from nucleus, the
positive part of an atom, plus –phile from the
Greek word philos , meaning to love.
• When a nucleophile reacts with an alkyl halide,
the positive center that the nucleophile seeks is
the carbon atom that bears the halogen atom.
• This carbon atom carries a partial positive
charge because the electronegative halogen
pulls the electrons of the carbon-halogen
bond in its direction.
• A nucleophile is any negative ion or any
molecule that has at least one unshared
electron pair (Solomon & Craig, 2008)
• Nucleophile is a chemical species that donates
an electron pair to an electrophile to form a
chemical bond in relation to a reaction. All
molecules or ions with a free pair of electrons
or at least one pi bond can act as nucleophiles.
• In this type of reaction a nucleophile, a species
with unshared electron pairs, reacts with an alkyl
halide by replacing the halogen substituent.
• A substitution reaction takes place and the
halogen substituent, called the leaving group
departs as a halide ion.
• Because the substitution reaction is initiated by a
nucleophile, it is called a nucleophilic
substitution reaction.
 Alkyl Halides Reactions with Nucleophilic
Reagents
• An important aspect of the chemistry of alkyl
halides is the ease of substitution its halogen by
nucleophiles.
• Reaction is carried out by refluxing the alkyl
halides with the nucleophile.
• An ethanol and water mixture is used as the
reaction medium so that both the alkyl halides,
which is alcohol soluble and the nucleophile,
which is water soluble, can mix and react.
 1. HYDROLYSIS OF ALKYL HALIDES
• Hydrolysis is carried out by boiling the alkyl
halides with aqueous sodium hydroxide.
R – X + OH-  R—OH + X-
Example:
CH3 CH2Br + NaOH  CH3 CH2OH + NaBr
• Primary and secondary alkyl halides need an
alkali for hydrolysis, but water alone is
sufficient to hydrolyse tertiary alkyl halides.
Mechanism for Alkyl Halide Hydrolysis
SN 1
R – X + OH-  R—OH + X-
2. Reaction with sodium cyanide
3. Ammonolysis
Elimination Reaction of Alkyl Halides
Elimination of hydrogen halide from
haloalkane give an alkene
The E2 Reaction
Methods for Differentiating Alkyl Halides
Synthesis of Organometallic compounds

• Organohalides, RX react with magnesium

metal in ether or tetrahydrofuran (THF)
solvent to yield organomagnesium halides,
RMgX.
• The products, called Grignard reagents after
their discoverer, Victor Grignard, are examples
of organometallic compounds because they
contain a carbon-metal bond.
• R-X + Mg  RMgX
• CH3 CH2 I + Mg  CH3 CH2 MgI
Uses of alkyl halides