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Classification
:Based on the number of halogen atoms .1
.Mono, di or polyhalogens according to number of halogen atoms
Nomenclature
Common name – Alkyl halides and arylhalides. IUPAC – Haloalkane and haloarene
e.g. CH3 – CH2 – CH2 – Br n-Propyl bromide
Bromopropane (IUPAC) Isobutyl chloride – 1
Chloro – 2 – methylpropane – 1
Nature of C -X Bond
Since the halogen atom is more electronegative than C, the C – X bond of
.alkylhalide is polarised
Methods of Preparation
:From Alcohols .1
The -OH group of an alcohol is replaced by halogen on reaction with halogen acids
.(HX), PX3, PCl5, SOCl2, etc
:From Hydrocarbons .2
:Free RadicalHalogenation )a(
.Free radical chlorination or bromination of alkanes gives mixture of isomers
Mixing the solution of the freshly prepared diazonium salt with cuprous chloride
(Cu2Cl2) or cuprous bromide (Cu2 Br2) results in the replacement of the diazo group
.by -Cl or -Br
HALOALKANES AND HALOARENES
.Aryl iodide is prepared by shaking the diazonium salt with potassium iodide
:Halogen Exchange .3
Finkelstein Reaction: Alkyl iodides are prepared by the reaction of alkyl
.chlorides/bromides with Nal in dry acetone
R – X + Nal → R – I + NaX (X = Cl, Br)
:Swarts Reaction
Alkyl fluorides are prepared by heating an alkyl chloride/bromide in the presence
.of a metallic fluoride such as AgF, Hg2F2, CoF2 or SbF3
.R – Br + AgF → R – F + AgBr
Physical Properties
Melting and Boiling Points: Lower members are gases and higher members are
liquid or solids. Intermolecular forces of attraction are stronger in the halogen
derivatives. Hence bp of chlorides, bromides and iodides are higherthan that of
.parent hydrocarbon
The boiling points of alkyl halides decrease in the order Rl > RBr > RCI > RF. The bp
of isomeric haloalkanes decrease with increase in branching. The bp of p-isomeric
.dihalobenzenes are higher than that of o- and m- isomers
:Solubility
Haloalkanes are only very slightly soluble in water. But they, are soluble in organic
.solvents
Chemical Reactions
:a. Reactions of Haloalkanes: divided into three
HALOALKANES AND HALOARENES
Nucleophilic substitution .1
Elimination reaction .2
:Mechanism
:Substitution Nucleophilic Bimolecular (SN2) )a(
Reaction between R – X and Nu follows second order kinetics, i.e., rate depends
upon the concentration of both the reactants. Consider the reaction of CH 3 – Cl &
–
OH
The incoming nucleophilic interacts with alkyl halide causing the C-X bond to break
while forming a new C-OH bond. After the completion of reaction, the
configuration of the carbon atom inverts. This process is called inversion of
.configuration
The breaking and forming of bond take place simultaneously in a single step and no
.intermediate is formed. But a transition state is formed
alkyl halides are the least reactive because bulky groups hinder the approaching 3°
.of nucleophile. Order of reactivity: 1° > 2° > 3° halides
Allylic and benzylic halides show high reactivity towards SN1 reaction because the
.carbocation formed gets stabilised through resonance
Laevo rotatory, l-form or (-)- compound which rotate plane polarised light to the
.right (anticlockwise direction)
The (+) and (-) isomers of a compound are called optical isomers and the
.phenomenon is termed as optical isomerism
:Chirality
Objects which are non-super impossable on their mirror image are said to be chiral
HALOALKANES AND HALOARENES
and this property is known as chirality. The objects which are super impossible
.mirror images are called achiral
:Enantiomers
Stereo isomers related to each other as non-super impossible mirror images of
each other and which rotate the plane polarised light equally but in opposite
.directions
They have identical physical properties. They only differ with respect to the
rotation of plane polarised light. If one of the enantiomers is dextrorotary, the
.other will be laevo rotatory
SN2 & SN1 Reactions of Optically Active Alkyl Halides: The product formed as a
result of SN2 mechanism has the inverted configuration as compared to the
reactant because the Nu attaches itself on the side opposite to the one where the
HALOALKANES AND HALOARENES
halogen atom is present. SN1 reactions are accompanied by racemisation due to
.planar structure of carbocation
:Elimination Reactions .2
When a haloalkanes with β – H atom is heated with alcoholic solution of KOH,
there is elimination of H from β – C and a halogen atom from the α – C. Since β – H
.atom is involved in elimination, it is called β – elimination
:Wurtz Reaction
Alkyl halide react with sodium in dry ether give hydrocarbons with even number of
.carbon atoms, i.e., double the number of carbon atoms present in the halide
2R – X + 2Na R → R + 2 NaX
C-Cl bond acquires a partial double bond character. Hence, cleavage of C – X bond
.is difficult
Haloarenes Haloalkane
C sp3 hybridised
Instability of phenyl cation: the phenyl cation formed as a result of self- )iii(
.ionization will not be stabilized by resonance
Steric repulsion: it is less likely for the electron-rich nucleophile to approach )iv(
.electron-rich arenes
:Replacement by Hydroxyl Group
HALOALKANES AND HALOARENES
The presence of an electron-withdrawing group (-NO2) at
:Nitration )ii(
HALOALKANES AND HALOARENES
:Sulphonation )iii(
:Fittig Reaction
Aryl halides when treated with sodium in dry ether, diaryls are formed in which the
.aryl groups are joined together
Polyhalogen Compounds
:Dichloromethane (Methylene Chloride), CH2Cl2 )1(
Used as a solvent, as a paint remover, as propellent in aerosols and in manufacture
of drugs. It is harmful to human central nervous system. It causes dizziness,
.nausea, direct contact with the eyes can burn the cornea
HALOALKANES AND HALOARENES
:Trichloromethane (Chloroform), CHCl3 )2(
Employed as a solvent for fats, alkaloids. It was once used as general anaesthetic.
Inhaling it depresses central nervous system. It is slowly oxidised by air in presence
of light to form an extremely poisonous gas, carbonyl chloride known as phosgene.
.Hence it is stored in dark coloured bottles completely filled so that air is kept out
:Freons )5(
The chloroflurocarbon compounds of methane and ethane are collectively known
as freons. Freon 12 (CCl2Fl2) is one of the most common freons in industrial use. It
.causes ozone depletion