Revision Notes
Chapter-10- Haloalkanes and Haloarenes
HALOALKANES
Alkyl halides: General formula is RX, where R = alkyl group.
Classification:
1o,2o and 3o halides are formed when halogen atom is bonded to primary, secondary
or tertiary carbon atom of an alkyl group respectively.
Nomenclature
CH3CH2CH2Br- Common name for this compound is n-propyl bromide but the IUPAC
name is 1-Bromopropane.
Nature of C-X Bond
Halogen atom (can be represented as X) is more electronegative than carbon. So, the
C-X bond is polarized with C having a partial positive charge and X having a partial
negative charge.
As we go down the group from F to I, the size of the halogen atom increases.
Consequently, the carbon-halogen bond length also increases from C-F to C-I.
As we move from F to I, electronegativity decreases, therefore the polarity of C-X
bond decreases.
General methods of preparation
1. From alcohols:
– Action of hydrogen halides: Groove’s Process
• Order of reactivity of halogen acids
towards the above reaction is:
HI > HBr > HCl
• Order of reactivity of different alcohols
towards the above reaction is :
tertiary > secondary > primary
In Groove’s process, primary and secondary alcohols require the presence of a catalyst.
ZnCl2 acts as a catalyst to cleave the C-OH bond. ZnCl2 being a Lewis acid readily
coordinates with the O atom in C-OH bond. As a result, the C-O bond weakens and
finally breaks down to form carbocations. This carbocation then reacts with chloride
ion to form chloroalkanes.
H2SO4 is not used for the preparation of R-I as the HI formed in the process will be
oxidised back to I2 by H2SO4.
– Action of phosphorus halides:
– Action of thionyl chloride
Preferred because of the gaseous by-products.
Only for chloroalkanes, as SOBr2 is unstable and SOI2 doesn’t exist.
≫ Halogenation of alkanes:
Gives a mixture of haloalkanes
≫ Halide exchange method :
This is known as Finkelstein reaction.
– Fluoroalkanes can also be prepared by halide exchange method by reacting alkyl
chloride with inorganic fluorides like Hg2F2, AgF, SbF3 and CoF2. This is known as
Swart’s reaction.
≫ Addition of hydrogen halides to alkene :
Alkenes add on a molecule of hydrogen halide to form alkyl halide.
– Reaction follows electrophilic addition mechanism and takes place as per
Markownikoff’s rule. However, in presence of peroxide addition of HBr takes place as
per anti-Markownikoff’s rule.
Anti-Markownikoff’s rule is also known as Peroxide effect or Kharasch effect. HCl
and HI do not show peroxide effect.
Physical properties:
≫ Alkyl halides being polar in nature are insoluble in water as they cannot break H-
bonding already existing in water.
≫ They have higher melting and boiling points. For the same alkyl group, boiling
point follows the order as: R-I > R-Br > R-Cl > R-F
With increase in size and number of electrons in halogen atom, magnitude of van der
Waal’s force increases(size of dipoles increases).
≫ Decreasing order of boiling points among the isomeric alkyl halides follows the
order : 1° > 2° > 3° alkyl halides. Branching decreases surface area, which decreases
the van der Waal’s force.
≫ Decreasing order of density among the alkyl halides is RI > RBr > RCl > RF.
For alkyl iodide decreasing order of density is as follows :
CH3I > CH3CH2I > CH3CH2CH2I.
≫ Bond strength of C X bond follows the order
CH3F > CH3Cl > CH3Br > CH3I
i.e., bond strength of C X bond decreases as the size of halogen atoms increases.
≫ Correct stability order of RX is as follows :
R F > R Cl > R Br > R I
Chemical properties:
≫ Dehydrohalogenation:
≫ Friedel Crafts reaction:
≫Reaction with Mg metal to form Grignard reagent:
≫Wurtz reaction:
≫Reduction of alkyl halides :
>>Nucleophilic Substitutions Reactions
The replacement of the halogen atom (leaving group) by the attacking nucleophile is
called nucleophilic substitution reaction.
This reaction proceeds through two mechanisms i.e., SN2 and SN1.
Key Features of SN2Mechanism
1. Single step reaction.
2. Rate=k [ RX] [ Nu-]
3. No intermediate is formed. Reaction proceeds through one transition state where
one bond breaks and one is formed simultaneously.
4. Rearrangement is not observed.
5. Inversion of configuration is observed(Walden inversion)
6. Order of reactivity of alkyl halides:
1∘>2∘>3∘
As the size increases steric hindrance increases, so there is difficulty in
formation of transition state.
0. Favoured by aprotic solvents.
Key Features of SN1Mechanism
1. It is a two-step reaction. First step involves formation of carbocation as well
as its rearrangement such that the carbocation is at the most stable position, then
nucleophile attacks the carbocation to form the final product which is the second
step.
2. Rate=k [ RX] Rate=k [ RX]
3. Intermediate is formed which is carbocation.
4. Rearrangement is commonly observed.
5. Racemic mixture is obtained.
6. Order of reactivity of alkyl halides:
3∘>2∘>1∘
This can be attributed to the stability of the carbocation that is formed.
0. Favoured by polar protic solvents.
The nucleophiles that can attack through two different sites are known as
ambident nucleophiles. For example, cyanide ion is an ambident nucleophile. It
can attack through either C atom or N atom to form alkyl cyanide or alkyl
isocyanide.
≫Primary allylic and primary benzylic halides show higher reactivity in SN 1 reactions
than other primary alkyl halides due to the greater stabilisation of allylic and benzylic
carbocation intermediates by resonance.
≫Vinylic and aryl halides are unreactive in nucleophilic substitution reactions. This is
because of the double bond character of C-X bond due to resonance.
Enantiomerism
≫Optical isomer is known as dextrorotatory isomer (latin: dexter means right) (d-form
or +ve) if it rotates the plane polarised light to the right (clockwise) and laevorotatory
isomer (latin: laevo means left) (l-form or –ve) if it rotates the plane polarised light to
the left (anticlockwise).
≫An equimolar mixture of the d- form and l-form will be optically inactive and is
called racemic mixture (or dl- form or (±)-mixture).
≫The process of conversion of an enantiomer into racemic mixture is known as
racemisation.
≫Chirality: The compound is said to have chirality if the central carbon atom is
attached to four different groups and this centre is called chiral (asymmetric) centre or
stereogenic centre or stereocentre.
≫Achirality: The compound is said to have achirality if the central carbon atom has at
least two identical groups and this centre is called achiral (symmetric).
≫If molecule has a plane of symmetry, it is achiral (not chiral) and if molecule has no
plane of symmetry, it is chiral.
≫Enantiomers/ d and l isomers: They are the optical isomers which are non-
superimposable mirror images (or dissymmetric).
≫Diastereomers: They are the optical isomers which are not mirror images of each
other. They have different physical properties and magnitude of specific rotation.
HALOARENES
≫Aryl halides: General formula is ArX, where Ar = aryl group.
General methods of preparation:
From benzenediazonium salt:
By direct halogenation of benzene:
HIO3 or HNO3 is used in the preparation of iodobenzene to counteract the reduction of
iodobenzene to benzene by the HI formed as by-product.
Physical properties:
≫Aryl halides are colourless stable liquids with pleasant odour.
≫These are insoluble in water but readily miscible with organic solvents.
≫Most of them are volatile, heavier than water.
≫Their boiling points are higher than corresponding alkyl halides. The boiling points
rise gradually from fluoro to iodo compounds.
p-dichlorobenzene has higher m.p. than those of o- and m-isomers due to its greater
symmetry that fits in the crystal better as compared to ortho and meta-isomers.
Chemical properties :
≫Nucleophilic substitution reactions :
Happens very slowly due to the following reasons.
1. Partial double bond character of C-X due to resonance
2. Higher electronegativity of C in C-X due to its sp2 hybridisation.
3. Electronic repulsion between the electron rich ring and nucleophile
Dow’s process
The presence of an electron withdrawing group (NO2) at ortho- and para-positions
increases the reactivity of haloarenes.
Electrophilic substitution reactions :
– Halogenation :
– Nitration:
– Sulphonation:
– Friedal-Crafts reaction:
≫Wurtz-Fittig reaction:
≫Fittig reaction:
Uses and environmental effects of some important compounds:
(1) Chloroform (CHCl3)
Uses
– Its major use is in the production of Freon refrigerant, R-22.
– It is used as a solvent for resins, rubbers, oils and fats, alkaloids, iodine and many
other substances.
– In the past, it was extensively used as anaesthetic for surgery but now it is rarely
used as it causes liver damage.
– It is used in preparation of chloretone (drug) and chloropicrin (insecticide).
– It is used to preserve anatomical species.
Effects
– It is oxidised to poisonous gas, carbonyl chloride, known as phosgene.
Phosgene gas causes liver and kidney damage– Inhaling chloroform vapours depresses
the central nervous system, causes dizziness, fatigue and headache.
(2) Iodoform (CHI3)
Uses
– It is used as an antiseptic in the dressing of wounds due to liberation of iodine.
– It is used as a methylating agent in organic synthesis.
Effects
– It has a strong smell.
(3) Freons
– They are used as refrigerants, blowing agents, propellants in medical applications
and degreasing solvent.
– Freons cause disruption of the ozone layer by initiating radical chain reactions in the
stratosphere.
– This anthropogenic compound is a greenhouse gas and its effect is more than CO2.
(4) DDT
Uses
– In 1940, it was used as a pesticide.
Effects
– It is a persistent organic pollutant, strongly absorbed by soil.
– It is lipophilic so has a high potential to bioaccumulate.
– It may be directly genotoxic but may also induce enzymes to produce other
genotoxic intermediates and DNA adducts.
