HALOALKANES AND HALOARENES
Halo alkanes are the compounds containing halogen atom attached to the sp3 hybridized
carbon atom of an alkyl group.
Haloarenes are the compounds containing halogen atom attached to sp2 hybridized carbon
atom of an aryl group.
(a) Alkyl halides or halo alkanes (R—X)
They create a homologous series represented by CnH2n+1X and can be further classified as
primary, secondary or tertiary.
(b) Allylic halides :The compounds with halogen atoms bonded to sp3-hybridised carbon
to carbon-carbon double bond (C=C) i.e. to an allylic carbon.
(c) Benzylic halides :The halogen atom of these compounds is bonded to sp3-hybridised
carbon atom placed next to an aromatic ring.
d)Vinylic halides :The halogen atom of these compounds is bonded to sp2-hybridised
carbon atom of a carbon-carbon double bond (C = C).
(b) Aryl halides The halogen atom of these compounds is bonded to the sp2-hybridised
carbon atom of an aromatic ring.
Nomenclature
o Select the longest chain of carbon that contains the halogen atom.
o Give least possible number to the halogen atom.
o The carbon containing double or triple bond is given the least number.
o Place the suitable suffix like di, tri, tetra for 2, 3, 4 halogen atoms respectively.
o For Haloarene :Numerical prefixes (1,2) ; (1,3) ; (1,4) for [for positions of the compound
with respect to halogen atom.
o The halogen atom is given the least number.
Jishaalex pg. 1
Nature of C-X Bond
o Halogen atoms being more electronegative than carbon possess a polarized bond
between the carbon halogen of alkyl halide.
o The carbon atom of the alkyl halide possesses a partial positive charge. The halogen atom on
the other hand possesses a partial negative charge.
o The carbon-halogen bond length increases from C—F to C—I due to the increase in the
size of halogen atom while going down the group in a periodic table from fluorine to
iodine atom.
Methods of Preparation of haloalkanes
1.By halogenations of alkanes in presence of light, catalyst or heat:
o Alkane + Cl2 ------------------------------> chloroalkane
2.By halogenations of alkenes with HX : [ markonikoff’s rule: in electrophilic
addition H goes to the carbon having more H]
3 From alcohols:
Treatment of alcohol with HCl in the presence of anhydrous ZnCl2 phosphorous
pentachloride, PX3(P4 + X2)or SOCl2 leads to the preparation of alkyl halide.
1. By the action of halogen acids:
. Mixture of conc. HCl and anhydrous ZnCl2 is called Lucas reagent.
Jishaalex pg. 2
2.By the action of phosphorous halides:
3ROH + PX3 ------------------ 3RX + H3PO3. [X= Br,I]
Alkyl chlorides can be synthesized by the action of PCl3 or PCl5.
3.Alcohols by treating with reflux of thionyl chloride
Alkyl bromides and iodides cannot be prepared by this method. The reason behind this is
that thionyl bromide is unstable and thionyl iodide does not exist.
This method is preferred for preparing alkyl chlorides because here by-
products are gaseous SO2 and HCl which escape easily. But this does not happen in
the method involving phosphorous chloride; hence it is not used for preparing alkyl
chlorides.
4. Halogen exchange reaction :
Finkelstein reaction: Alkyl iodides are prepared by reaction of alkyl chloride or bromide
with NaI in dry acetone.[ NaX is precipitated in dry acetone to facilitate forward reaction]
R-X + NaI ------------> R-I + NaX
Swarts reaction : Reaction of alkyl chloride /bromide with metallic fluoride such as AgF,
HgF
R-X + AgF ------------> R-F + AgX
Preparation of aryl halides
o Halogenations:
This method can be used to prepare aryl chlorides and bromides. This is done by treatment
of arene with chlorine or bromine in the absence of sunlight and in the presence of halogen
carrier like AlCl3, FeCl3 etc. at low temperatures. It is an electrophilic substitution.
o From phenol: [ *C-O has a partial double bond character so difficult to
break]
Jishaalex pg. 3
However the yield of Chlorobenzene is very poor as the main product is Triphenyl
phosphate.
Sandmeyer reaction
Diazonium salts are highly reactive compounds used to prepare arene derivatives. Treating
diazonium salt with copper (I) chloride (Cu2Cl2) or copper (I) bromide (Cu2Br2) leads to the
formation of corresponding haloarene. This reaction is known as Sandmeyer reaction.
Physical Properties of halo alkanes
Alkyl halides are colorless in pure state.
Volatile halogen compounds possess a sweet smell.
Intermolecular forces of attraction of halogen derivatives are stronger due to
greater polarity and molecular mass as well compared to the parent
hydrocarbon thereby resulting in higher boiling points of chlorides, bromides
and iodides compared to hydrocarbons of equivalent molecular mass.
The boiling points of alkyl halides for same alkyl group follow the order:
RI> RBr> RCl> RF
due to the increase in size and mass of halogen atom thereby increasing the extent of van
der Waal forces.
In isomeric haloalkanes the boiling points decreases with increase in branching.
Para-isomers possess high melting point compared to ortho and meta-isomers due to the
symmetry of para-isomers fitting in crystal lattice better than ortho- and meta-isomers.
Jishaalex pg. 4
Density increases with increase in number of carbon atoms, halogen atoms and atomic
mass of the halogen atoms. Consequently the density of Bromo, iodo and polychloro
derivatives of hydrocarbons is greater than water.
The haloalkanes are only very slightly soluble in water due to release of less
energy during the setup of new attractions between the haloalkane and the water molecules
which in turn is insufficient to overcome the attractions between the haloalkane molecules
and break the hydrogen bonds between water molecules.
Haloalkanes dissolves easily in organic solvents due to the new intermolecular forces of
attractions between haloalkanes and solvent molecules having equivalent strength as the
one that is broken in separate haloalkane and solvent molecules.
Substitution reaction in halo alkanes :Nucleophilic substitution reactions are most
common reactions of alkyl halides.
Following are some examples:
Jishaalex pg. 5
Ambident nucleophile :The nucleophiles that can attack nucleophilic centres through
two different sites are known as ambident nucleophiles.
For example, cyanide ion : Forms Nitrile ,through C and Isonitrile through N
. NO2 : Forms alkyl nitrite [ONO ] and Nitro [NO2]
Nucleophilic substitution may take place in two ways:
1. SN1 Mechanism 2. SN2 Mechanism
SN1 mechanism
The tertiary alkyl halides react by SN1 mechanism via formation of carbocation as
intermediate.
The reactivity order for SN1 reaction is Benzyl > Allyl > 3 > 2 > 1 > CH3X.
3 > 2 > 1 As 3 electron releasing alkyl group stabilizes the carbocation, benzylic
and allylic carbocation are stabilised by resonance
SN2 mechanism
In case of SN2 reactions the halide ion leaves from the front side whereas the nucleophiles
attacks from the back side; due to this reason SN2 reactions are always accompanied by the
inversion of configuration.
The rate of reaction 1 > 2 > 3 , presence of 3 alkyl group does not allow the nucleophile to
reach the carbon.
Jishaalex pg. 6
Order of reaction RI ˃ RBr ˃ RCl
because RI bond length is longer and weaker, so it can break easily.
b. Elimination reaction: Dehydrohalogentaion( - elimination):
When a haloalkane with β-hydrogen atom is heated with alcoholic solution of potassium
hydroxide, there is elimination of hydrogen atom from β-carbon and a halogen atom from
the α-carbon atom.
As a result, an alkene is formed as a product.
Zaitsev rule (also pronounced as Saytzeff) is followed.It states that ―In dehydrohalogenation
reactions, the preferred product is that alkene which has the greater number of alkyl groups
attached to the doubly bonded carbon atoms.‖
c. Reaction with metals:
Reaction with Magnesium
Grignard’s reagent is formed: R X + Mg ---------- RMgX
Wurtz reaction: R-X + 2 Na + R-X → R-R + 2 NaX
STEREOCHEMICAL ASPECTS
STEREOISOMERS: Isomerism exhibited by two or more compounds with same molecular
formula but different spatial arrangements of atoms
PLANE POLARISED LIGHT: beam of light which oscillates in one plane only.It is obtained
by passing a monochromatic light through nicol prism.
OPTICALLY ACTIVE COMPOUNDS: Compounds which rotate plane polarized light [they
must have chiral(asymmetric ) carbon
DEXTROROTATORY[d, +] : compounds which rotate plane polarised light to right.
Jishaalex pg. 7
LAEVOROTATORY[ l , - ] compounds which rotate plane polarised light to left
ASYMMETRIC / CHIRAL CARBON; carbon which is attached to four different atoms or
groups of atom around it.
CHIRAL: Objects which are non-superimposable mirror image are said to be chiral and
property is known as chirality.
ENANTIOMER: The stereoisomer which are non-superimposable mirror images are called
enantiomers.
RACEMIC MIXTURE: The equimolar mixture of dextro and laevo form is called racemic
mixture.
RACEMISATION: The process of conversion of enantiomers to racemic mixture.
Retention of configuration: A process in which the relative configuration of an atom is
retained.
Inversion of configuration: A process in which the relative configuration of an atom is
changed. The new group is attached opposite to the leaving group.
HALOARENES:
Aryl halides are extremely less reactive towards Nucleophilic substitution reactions due to
i) Resonance effect: C-X gets a partial double bond character so difficult to break
ii)sp2 hybridised C has more s character Therefore the C-X bond in haloarenes is
strong and stable and hence difficult to break. Hence the Nucleophilic substitution in
haloarenes is difficult. Hhaloalkane has sp3 hybrid C
iii): Unstable cation : the phenyl carbocation formed is not stabilized by resonance so
SN1 is not possible
REACTIONS OF HALOARENES :
Replacement by hydroxyl group
Jishaalex pg. 8
The presence of an electron withdrawing group (-NO2 ) at ortho- and para-positions increases the
reactivity of haloarenes.
Electrophilic substitution reactions
Due to resonance, the electron density increases more at ortho- and para-positions than at meta-
positions. Further, the halogen atom because of its –I effect has some tendency to withdraw
electrons from the benzene ring. As a result, the ring gets somewhat deactivated as compared to
benzene and hence the electrophilic substitution reactions in haloarenes occur slowly and require
more drastic conditions as compared to those in benzene.
(i) Halogenation
(ii) Nitration
(iii) Sulphonation
(iv) Friedel-Crafts reaction
Reaction with metals
Wurtz-Fittig reaction :A mixture of an alkyl halide and aryl halide gives an alkylarene when treated
with sodium in dry ether and is called Wurtz-Fittig reaction.
Fittig reaction Aryl halides also give analogous compounds when treated with sodium in dry ether,
in which two aryl groups are joined together. It is called Fittig reaction
Jishaalex pg. 9
POLYHALOGENO COMPOUND:
1. Dichloromethane[ CH2Cl2]
Uses :i) as a solvent
ii) as a propellent in aerosol
Harmful effect: i) causes dizziness , nausea
ii) on contact with skin causes burning
iii) can burn cornea if in contact with eye
2. Chloroform:[ trichloromethane CHCl3]
Uses: i) was used as anesthesia
ii) used in production of Freon
Harmful effect: i) causes dizziness and headache
ii)damages liver
Q.Name the poisonous gas obtained from chloroform/haloalkane OR why is
chloroform stored in dark coloured bottles completely filled?
a. chloroform is slowly oxidized by air in presence of light to form a poisonous gas
carbonyl chloride (phosgene)
CHCl3 + O2 --------------------> 2 COCl2 + 2 HCl
3. Iodofrom [CHl3]
Uses : was used as an antiseptic but it is now replaced by tincture of iodine due to the
bad smell of iodoform.
4. Tetrachloromethane :
Uses: i)used in the manufacture of refrigerant
ii) used as asolvent
Harmful effect: i) causes dizziness and headache
ii) causes depletion of ozone layer
5. Freon [ chlorofluorocarbon CFC ]
Uses:i)used as coolent in refrigerator and AC
ii) as a propellent in aerosol
Harmful effect: i) causes skin cancer, eye disease
ii) causes depletion of ozone layer
6. P-dichlorodiphenyltrichloroethane [DDT] : the first chlorinated organic
insecticide]
The chemical stability and low fat solubility of DDT causes it to be deposited in the fatty
tissues of animals and enters the food chain.
Q1. Why haloalkanes are more reactive than haloarenes.
Ans. In haloarenes, there is partial double bond character b/w carbon and halogen due to +
resonance effect which makes it less reactive.
Jishaalex pg. 10
Q2. Why do haloalkenes undergo nucleophillic substitution whereas
haloarenes under go electophillic substitution .
Ans. Due to more electro negative nature of halide atom in haloalkanes carbon atom
becomes slightly positive and is easily attacked by nucleophillic reagents.
While in haloarenes due to resonance, carbon atom becomes slightly negative and attacked
by electrophillic reagents.
Q3. When an alkyl halide is treated with ethanolic solution of KCN, the major
product is alkyl cyanide where as if alkyl halide is treated with AgCN,the major
product is alkyl isocyanide.
Ans. KCN is ionic they can attach through C or N but C-C bond is strong than C-N bond. So
alkyl cyanide is the major product but AgCN is covalent so more electronegative N can
attach to C and forms isocyanides.
Q.4. Aryl halides cannot be prepared by the action of sodium halide in the
presence H2SO4 .Why?
Ans. Due to resonance the carbon- oxygen bond in phenols has partial double bond and it is
stronger than carbon oxygen single bond.
Q5. Why Grignard reagent should be prepared under anhydrous conditions.?
Ans. Grignard reagent react with H2O to form alkanes , therefore they are prepared under
anhydrous condition.
Q6. Why is Sulphuric acid not used during the reaction of alcohols with KI ?
Ans. It is because HI formed will get oxidized to I2 by concentrated Sulphuric acid which is
an oxidizing agent.
Q7. p- dichlorobenzene has highest m.p. than those of ortho and m-isomers.?
Ans. p- dichlorobenzene is symmetrical, fits into crystal lattice more readily and has higher
melting point.
Q8. Although chlorine is an electron- withdrawing group, yet it is ortho and
para directing in electrophillic aromatic substitution reactions. Why
Ans.Chlorobenzene is resonance hybrid such that there is –ve charge at ortho and para
positions, electrophillic substitution reaction will take place at ortho and para position due
to +R effect. +R effect is dominating over – I effect. .
Q9. Explain why vinyl chloride is unreactive in nucleophillic substitution
reaction?
Ans. Vinyl chloride is unreactive in nucleophillic substitution reaction because of double
bond character between C=Cl bond which is difficult to break.
Jishaalex pg. 11
