Power point presentation

Nidhi Sathyadas
 Haloalkanes and Haloarenes
Mono haloalkane
Hydrogen atom of alkane is replaced by
halogen.
General IUPAC nomenclature
Haloalkane
General common name
Alkyl halide
 Primary carbon atom -Carbon atom
attached directly to one carbon atom.

Secondary carbon atom – Carbon atom

attached directly to two other carbon
atoms.
Tertiary carbon atom – Carbon atom
attached directly to three other carbon
atoms.
Preparation of Haloarenes
 From diazonium salt
When primary amines are heated with nitrous
acid at low temperature gives diazonium salt.
Diazonium salt is unstable . So when it is treated
with cuprous chloride or cuprous bromide
produce corresponding haloarenes. This
reaction is known as Sandmeyer reaction.
Iodoarenes are obtained by shaking diazonium
salt with potassium iodide.
Reactions of Haloarenes
During halogenation, a carbocation is formed as
intermediate. In the above reaction secondary
carbocation is more stable than primary.
The replacement of hydrogen is in the order
Tertiary carbocation > secondary carbocation>
primary carbocation
 Enantionmer

Stereo isomers which are

mirror images of each other
and are non super imposable
are called enantiomer.
eg 2-hydroxy propanoicacid
 Assymetric carbon

If all the substituents attached to a

carbon are different, such a
carbon is called assymetric
carbon or stereocentre or chiral
carbon.
 Optically active compounds.
Certain compounds rotate the plane
polarised light ( produced by passing
ordinary light through Nicol prism) when
it is passed through their solutions. Such
compounds are called optically active
compounds.
The angle by which the plane polarised
light is rotated is measured by an
instrument called polarimeter.
 d- form and l- form
If the compound rotates the plane
polarised light to the right , it is
called dextrorotatory or d form
indicated by a positive sign.
If the compound rotates the plane
polarised light to the left , it is called
leavorotatory or l form indicated by a
negative sign.
Such isomers of a compound are
called optical isomers and the
phenomena is known as optical
isomerism.
 Optical isomers

Compounds having the same

formula ,but are mirror images of
each other and differ in optical
activity are known as optical
isomers.
 Retention of configuration
Spatial arrangement of bonds at chiral carbon
centre in a chiral molecule remains same
before and after the reaction is said to
proceed with retention of configuration.
If equal mixture of A and B is
formed then the product is a
racemic mixture and it is optically
inactive.
Mechanism of nucleophilic
substitution reaction
Substitution nucleophilic bimolecular
( SN2)
Rate of the reaction depends on
the concentration of alkyl halide
and the nucleophile. This reaction
takes place in one step and their
happens an inversion of
configuration. SN2 is followed by
inversion of configuration
Substitution nucleophilic unimolecular
( SN1)
Reaction takes place in two steps and rate of the
reaction depends upon one of the reactant.
 Alkyl halide undergoes fission to form a
carbocation in presence of a nucleophile.
 Reaction of 2- bromobutane with
aqueous NaOH to give butan-2-ol

SN1 mechanism is followed by

racemisation
 Order of reactivity in SN2
Bulky group around the carbon inhibits the
attack of nucleophile and therefore the order
of reactivity is
Primary alkyl halide > secondary alkyl halide >
tertiary alkyl halide
 Order of stability of carbocation
Greater the stability of carbocation ,greater will
be its ease of formation from alkyl halide and
faster will be the rate of reaction.
Benzyl carbocation > allyl carbocation>tertiary
carbocation > secondary carbocation >
primary carbocation
 Order of reactivity in SN1
Benzyl halide > allyl halide > tertiary halide >
secondary halide > primary halide
Under SN1 mechanism , allyl chloride undergo to
form an intermediate which is stable due to
resonance
Which one undergo SN2 reaction
easily?
Which one undergo SN1 reaction
easily?
Order of reactivity of alcohol with HX is in the
order 30 > 20 > 10.. The reaction of 10 and 20
alcohol with HX requires the presence of
catalyst ZnCl2 but 30 alcohol, the reaction
takes place at room temperature by shaking
with conc. HCl.
ROH + SOCl2 → RCl
The reaction takes place only if R is an alkyl
group. If R is an aryl group, reaction does not
takes place
Phenol + SOCl2 → No reaction
Because carbon oxygen bond in phenol has a
partial double bond character and it is difficult
to break since double bonds are stronger than
single bond.
Resonating structures of phenol
Aryl halides are less reactive towards
nucleophilic substitution reaction.
When Cl is attached to alkyl group ,on reaction
with aq NaOH substitution takes place.
CH3Cl + aq NaOH → CH3OH +NaCl
When Cl is attached to aryl group ,on reaction
with aq NaOH substitution does not takes
place.
Phenol + aq NaOH → No reaction
 Aryl halides are less reactive towards
nucleophilic substitution reaction
1.CCl bond aquires a partial double bond character
due to resonance.
2.Because of the possible repulsion , it is less likely
for the electron rich nucleophile to approach
electron rich arenes.
3.Phenyl cation formed is not stabilized by
resonance
4.CCl bond length in alkyl halide is 177pm and in
aryl halide is 169 pm. It is difficult to break a
shorter bond . So aryl halides are less reactive.
CCl bond aquires a partial double bond
character due to resonance.
Why sulphuric acid not used during the reaction
of alcohol with NaI to prepare RI ?
Sulphuric acid is a strong oxidizing agent. It
oxidizes HI produced to I2 and prevents the
reaction with alcohol and HI.
NaI + H2SO4→ HI + NaHSO4
HI + H2SO4→ I2 + 2H2O + SO2
Alkyl halides are immisicible with water. Why ?

Alkyl halide molecules are held by dipole –

dipole force. When added to water , new force
of attraction developed between alkyl halides
and water is weak and hence alkyl halides are
immisicible with water.
Ambident Nucleophiles
Group which possess two nucleophilic centres
are called Ambident Nucleophiles.
Eg CN
The linkage through carbon atom results in the
formation of alkyl cyanide and through
nitrogen atom results in isocyanide.
NO2
The linkage through oxygen results in alkyl
nitrites while linkage through nitrogen results
in nitroalkanes.
CH3CH2Br + aq KCN → CH3CH2CN. Why
CH3CH2NC is not formed ?
CN is an ambident nucelophile. Both carbon
and nitrogen can form bond with alkyl group.
But alkyl –CN bond is stronger than alkyl- NC
bond. So cyanide is formed instead of
isocyanide.
Physical properties of alkyl halide
Boiling point of alkyl halides are higher than the
parent hydrocarbon due to greater polarity as
well as higher molecular mass.
RI > RBr > RCl > RF
Boiling point of alkyl halides decrease with
increase in branching
Boiling point of alkyl halides decrease with
increase in branching.
Arrange the following in incrasing order of
boiling point.
A ) CH3CH2CH2Cl B) CH3CH( CH3)2 C)
CH3CH2CH2CH2Cl
B<A< C
Alkyl halides react with KCN to form alkyl cyanide
while if it reacts with AgCN the product is
isocyanide. Why ?
KCN is ionic in nature. So both carbon and nitrogen
can donate electron, the attack takes place
through carbon atom since alkyl- carbon bond is
stronger. But AgCN is covalent in nature. So only
nitrogen is free to donate electron and gives
isocyanide.
CH3Cl + KCN → CH3CN + KCl

CH3Cl + AgCN → CH3NC + AgCl

C6H5CH2Cl or C6H5ClC6H5. Which one is more easily
hydrolysed by aq KOH ?

Under SN2 mechanism , reactivity depends on

steric hindrance. So C6H5CH2Cl get hydrolysed
more easily.
Under SN1 mechanism depends on stability of
intermediate. Since there are two phenyl
groups, more resonating structures will be
formed. So C6H5ClC6H5 get hydrolysed easily.
Chlorobenzene can be converted
to phenol by heating with aq NaOH
at a temperature of 623 K and a
pressure of 300 atm.
Thank you

Nidhi Sathyadas