Alkyl Halide

Capital University of Science and Technology

Department of Pharmacy
Date = 06/12/2022
Alkyl Halide
• Alkyl halides are derivatives of alkanes in which hydrogen atom is
replaced by halogen atom F, Cl, Br or I.
• Alkyl Halides are represented by R-X, alkyl halide, X-halogen like
Fluoro, Bromo and Iodo group.
Classification
• Alkyl Halides are classified as Primary (1°), Secondary (2°) or
Tertiary (3°), depending upon whether the X-atom is attached to a
primary, secondary or a tertiary carbon.
• Alkyl halides are among the most useful organic compounds. They are
frequently used to introduce alkyl group into other molecule.
Structure
• Let us consider methyl chloride (CH3Cl) for illustrating the orbital make up of
alkyl halides. In methyl chloride, the carbon atom is sp3 hybridized .
• The chlorine atom has a half-filled p orbital in its valence shell.
• The C-Cl bond is formed by the overlap of an sp3 orbital of carbon and the half-
filled p-orbital of chlorine atom. Each C-H bond is formed by the overlap of an
sp3 orbital of carbon and the s orbital of hydrogen . All bond are sigma bond . The
H-C-H and H-C-Cl bond angles are approximately tetrahedral.
Method of Preparation
1) Direct halogenation of Alkane
2) Addition of Hydrogen Halide to alkenes and alkynes
3) Action of Hydrogen Halide on alcohol
4) Action of Phosphorous Halides on Alcohols
5) Action of Thionyl Chloride on Alcohols
6) Halogen Exchange
7) The Hundsdiecker Reaction
1. Halogenation of alkane
• It involves the substitution of H-atoms of alkanes by as many halogen
atoms i.e, by chlorine (chlorination), bromine (bromination) by iodine
(iodination).

• Methane react with chlorine in the presence of ultraviolet-light or at

high temperature (300°C) to yield methyl chloride or chloromethane
and hydrogen chloride
2. Addition of Hydrogen Halides
1. Alkenes react with hydrogen halides (HCl, HBr and HI) to form
alkyl halides.
3. Action of Halogen acid on Alcohol
• Alcohol react with HBr or HI to produce alkyl bromides or alkyl
halides.
4. Action of Phosphorous Halides on Alcohol
• Alcohols react with phosphorous halides to produce alkyl halides.
5. Action of thionyl chloride on alcohol
• Alcohols react with thionyl chloride in the presence of pyridine to
produce alkyl halides.
6. Halogen exchange reaction
• The alkyl bromide is heated with concentrated solution of sodium
iodide in acetone to form alkyl iodide.
7.Hundiekar Reaction
• Silver salt of carboxylic acid react with halogen to give unstable
intermediate which is decarboxylated to form alkyl halides.
Reaction of Alkyl Halides
1. Nucleophilic Substitution Reaction
2. Reduction
3. Elimination Reaction
4. Wurtz Reaction
5. Reaction with Metals
Nucleophilic Substitution Reaction
• Nucleophile : Any reagent that donates an unshared pair of electrons to
form new covalent bond
• Nucleophilic substitution reaction in which one nucleophile is
substituted for another.
Two type of nucleophilic substitution reaction
• 1) SN1 : Unimolecular Nucleophilic Substitution
• 2) SN2 : Bimolecular Nucleophilic Substitution
SN1:Unimolecular Nucleophilic Substitution
• In this reaction, bond breaking between carbon and leaving group is
complete before bond formation with nucleophile.
• Tertiary alkyl halides undergo substitution by SN1 mechanism
• This type of reaction is classified as unimolecular because only the
alkyl halide is involved in rate determining step.
• Rate : k[alkyl halide].
SN2: bimolecular Nucleophilic Substitution
• It is concerted process, bond forming and bond breaking takes place
simultaneously
• This type of reaction is classified as bimolecular because the alkyl
halide and nucleophile are involved in rate-determining step.
• Rate = k [alkyl halide] [Nucleophile]
Mechanism of SN2
• The nucleophile attacks the reactive centre from the opposite side of
leaving groups, backside attack by the nucleophile
• SN2 reaction is driven by the attraction between negative charge of
nucleophile and positive charge on leaving group.
I. Substitution by Hydroxyl Group
• Alkyl halide react with aqueous sodium hydroxide to form alcohol.
Substitution by amino group
• Alkyl halides react with alcoholic solution of ammonia to form
amines.
Substitution by alkoxy group
• Alkyl halide react with sodium methoxide to form ethers
• Sodium alkoxide is prepared by dissolving sodium in alcohol.
Substitution by thiol group
• Alkyl Halide react with potassium hydrosulfide to form thiols.
Reaction with potassium sulphide
• Alkyl Halide react with potassium sulphide to form dialkyl sulphides
Reaction with silver salt of carboxylic acid
• Alkyl Halide react with silver salt of carboxylic acid to form ester.
Reaction with sodium cyanide
• Alkyl halide react with sodium cyanide in ethanol to form alkyl
cyanides.
2. Reduction of Alkyl Halides
• Alkyl halide undergo reduction with Nascent hydrogen in the presence
of reducing agent like Zn/HCl to form alkanes.
Elimination: Dehydrohalogenation of alkyl halides

• When alkyl halide is heated with alcoholic solution of sodium

hydroxide to form alkene and hydrogen halide.
Wurtz Reaction:
• Higher alkanes are produced by heating an alkyl halide with sodium
metal in dry ether. Two molecules of alkyl halide lose their halogen
atoms as NaX.
• These net result is the joining of two alkyl group to yield symmetrical
alkane having even number of carbon atoms.
Reaction with Metal: Formation of Grignard Reagent

• Alkyl magnesium halides (RMgX) Grignard reagent are obtained by

treating alkyl halides with magnesium in anhydrous ether to give alkanes.
Application of Alkyl Halides
• Propellants:
One major use of CFCs has been as propellants in aerosol inhalers for
drugs used to treat asthma.
The conversion of these devices and treatments from CFC to
halocarbons that do not have the same effect on the ozone layer is well
under way.
Many pesticides including DDT contain halogens.
Reagents for the synthesis of other compounds.
Halothane CF3CHClBr, is an Anesthetic.
CHCl3 used originally (toxic and carcinogenic).
Assignment Topic
Difference between SN1
and SN2 reaction mechanism
Date : 14/December/2022