REACTION MECHANISM

CHAPTER
15
You mix a bunch of ingredients and once in a great while Chemistry
happens.

''Bill Watterson''

INTRODUCTION

R
eaction mechanism is the step by step sequence of elimentry reaction by which
overall chemical change occurs. A chemical mechanism is the theoritical conjec-
ture that tries to describe in detail what takes place at each stage of an overall
chemical reaction. The detailed steps of a reaction are not observable in most cases.
The conjectured mechanism is choosen because it is thermodynamically feasible
and has experimental support in isolated intermediates or other quantitative and
qualitative characteristics of the reaction. A complete mechanism must also ex-
plain the reason for the reactants and catalyst used, the stereochemistry observed
in reactants and products, all products formed and the amount of each.
CHEMISTRY FOR NEET & AIIMS
Types of Reactions
In organic chemistry the following types of reaction are more important,
(I) Substitution reaction
(II) Elimination reaction
(III) Addition reaction
(IV) Rearrangement reaction
(V) Isomerisation reactions

(I) Substitution Reaction:

Reactions in which one atom or a group of substrate is replaced by other atom or group are called as substitution
reactions.
(A) Electrophilic substitution reactions
(B) Nucleophilic substitution reactions
(C) Free radical substitution reactions
(A) Electrophilic substitution reactions[ESR] : Characteristic reaction of arenes is ESR
H E
Catalyst
+E – Nu

Mechanism :
  
Catalyst
Formation of E E – Nu  E N u


E E
E .........
Attack of E

H
 E E
Abstraction of H Nu
+ H – Nu

Ex. Give reactivity order for electrophilic substitution reaction.

:

NH2 OH
(i) >

Less EN of nitrogen Less + M of – OH

so more + M so more e– density due to more EN
So more reactive

NO2 C–H
(ii) <
O
More – M of – NO2 & more –1 less – M of – CHO & less –1
so e– density decrease so e– density decreases (less)
(more) so less reactive so more reactive.

NHCOCH3 NO2 F CN
(iii)
+M –M (more) –I –M (less)
ESR order I > III > IV > II

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 REACTION MECHANISM
NOTE:
(1) Ortho/para directing group or activating group : Group which direct electrophile on ortho and para position is
called as o/p directing group.
The group increases electron density or increases reactivity of benzene ring so are called activating group.
The group are:
gg gg gg gg gg gg gg gg
– N H 2 , – N HR, N R 2 , – O H, – O R, – N HCOCH 3 , – S H, – OCOR, –CH 3 , –CH 2 CH 3 , –CH(CH 3 )2

OH
:

OH OH

+E +
E E
o– p–

due to +M/+H of these groups electron density at ortho and para position is increased so electrophile easily attack
on ortho/para position.

(2) Meta directing or deactivating group : Due to –M/–H of groups electron density at ortho and para position is less
but more at meta position so electrophile attack on meta position. SO, groups which direct electrophile on meta
position are called as meta directing groups.
These groups decrease electron density in benzene ring and decrease reactivity of benzene ring so are called as
deactivating group.
– CHO, COOH, – COOR, – COR, – CN, – NO2, – SO3H, – CX3,


C –H E C –H
O O
E
–
More e density at meta position

(3) Halogens are o/p directing group due to +M effect but are deactivating group due to – I > +M.

(4) M and H effect does not depend on distance while I-effect depends on distance In given example.

(5) M-effect at meta position is considered zero.

 
:

OH OH OH
O

no effect at
meta position

Similarly
+

C–H
+
  O
+

no effect at meta position

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CHEMISTRY FOR NEET & AIIMS
Aromatic Electrophilic Substitution Reactions :
Like an alkene, benzene has clouds of pi electrons above and below its sigma bond framework. Although benzene’s
pi electrons are in a stable aromatic system still they are available to attack a strong electrophile to give a carbocation.
This resonance-stabilized carbocation is called a sigma complex because the electrophile is joined to the benzene
ring by a new sigma bond.
The sigma complex (also called an arenium ion) is not aromatic because the sp3 hybrid carbon atom interrupts the
ring of p orbitals. This loss of aromaticity contributes to the highly endothermic nature of thus first step. The sigma
complex regains aromaticity either by a reversal of the first step (returning to the reactants) or by loss of the proton
on the tetrahedral carbon atom, leading to the substitution product.
 
The overall reaction is the substitution of an electrophile (E ) for a proton (H) on the aromatic ring: electrophilic
aromatic substitution.

Attack of an electrophile on benzene ring forms the sigma complex

H E H E H E
H E

E
Slow rds

Resonance hybrid
[  – complex]
Arenium Ion

H NO 2
Conc. HNO3 + Conc. H2SO4
(i) Nitration : [Nitrating mixture]

.. + – H
HO
.. – NO2 + H – HSO4 O – NO2 + HSO4 NO2
Formation –H2O
H [Attacking species]
(Bronsted base) (Bronsted acid)

CH3 CH3 CH3

NO2
HNO3/H2SO4
+
[NO2]

NO2

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 REACTION MECHANISM

H Cl
FeCl3
(ii) Halogenation : + Cl2

CH2Cl

Cl2/h
. "FRSR"
CH3 Cl

CH3 CH3
Cl
Cl2/FeCl3
+ "ESR"
Cl
Cl

Note : CH3 group in toluene is o/p directing and activating group.

H Conc. H2SO4
SO3H
(iii) Sulphonation :

Mechanism : 2H2SO4 SO3 + HSO4 + H3O

H
SO3 SO3 SO3H
Attacking Species

CH3 CH3 CH3

SO3H
Conc. H2SO4
+

SO3H

(iv) Friedel crafts reaction [FCR] : Alkylation or acylation of arenes in presence of lewis acid
[FeCl3, AlCl3 or ZnCl2 ... ] is called as FCR.

AlCl3
CH3
+ CH3 – Cl

(Methylation or Alkylation)
CH3

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+ CH3 – C – Cl
AlCl3 C – CH3

O
O

CH3 – C

Intermediate carbocation is formed in FCR so rearrangement is possible.

CH3
AlCl3 CH
+ CH3 – CH2CH2 – Cl CH3

1,2-H shift Isopropyl benzene (Cumene)

CH3 – CH – CH3 CH3 – CH2 – CH2

CH3
AlCl3 C – CH3
+ CH3 – CHCH2 – Cl CH3
CH3
–H
CH3 – C – CH3 CH3 – CH – CH2

CH3 CH3

AlCl3 C – CH2 – CH3

+ CH3 – CH2 – C – Cl
O
O

CH3 – CH2 – C CH3 – CH2 – C O ..

Complete octet RS
O
..

..

CH3CH2CH2 – Cl/AlCl3

CH3CH(Cl)CH3/AlCl3

CH3

CH3 – CH – CH3 CH
CH3CH2CH2 –OH/H
CH3

CH3CH(OH)CH3/H


CH3 – CH = CH2/H

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 REACTION MECHANISM

CH3
conc. H2SO4 C – CH3
+ CH2 = C – CH3
CH3
CH3

CH3 – C – CH3
CH3

CH2Cl2/AlCl3 Ph – H
Ph – CH2Cl Ph – CH2 – Ph
–HCl AlCl3
diphenyl methane

CHCl3/AlCl3
Ph3CH
Triphenyl methane
O
Cl –C – Cl/AlCl3
Ph – C – Ph

(v) Gatterman’s Koch Reaction :

CH = O
AlCl3
+ CO + HCl

CH = O H – C – Cl
O

(vi) Gatterman’s Aldehyde synthesis :

CH = NH CH = O
AlCl3 H3O
+ HCN + HCl

Cl – CH = NH

CH = NH

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CHEMISTRY FOR NEET & AIIMS

ETOOS KEY POINTS

The important electrophiles used in the aromatic substitution are the following -
Electrophilic Source Name of substitution reaction
Cl+(Chloronium) Cl2 + AlCl3 or FeCl3 Chlorination
+
Br (Bromonium) Br2 + AlBr3 or FeBr3 Bromination
NO 2 (Nitronium) (conc. HNO3 + H2SO4) Nitration
SO3 conc. H2SO4, fuming Sulphonation
(Sulphertrioxide) sulphuric acid
+
R (Alkyl carbonium) RX + AlX3(X = Cl or Br) Friedel crafts (Alkylation)
+
ROH + H
R – C = O(Acyl carbonium) RCOCl + AlCl3 Friedel crafts (Acylation)

(B) Nucleophilic Substitution Reaction (SN) : Due to electronegativity difference the – C – X bond is polarised

+ –
bond. – C – X

  
Thus the C-atom of the C  X bond becomes centre to attack by a nucleophile (Nu) .


X  ion from R – X molecule is substituted by a (Nu) . ie.SN reaction are the most common reactions in R – X.

R – X + Nu R – Nu + X
Two mechanisms are observed in SN reaction:
(a) SN2 mechanism (b) SN1 mechanism

SN2 mechanism : SN2 stands for bimolecular nucleophilic substitution. In this type of nucleophilic substitution
reaction, bond making and bond breaking process occur simultaneously.

H
H H
Slow – H
OH Br HO C Br HO – C – H + Br
H H H
Walden inversion
H
Transition state
2
(i) Reactivity of alkyl halides in SN substitution is governed by steric factors. The bulkier the group, that less
reactive it will be.
(ii) Reactivity order of alkyl halide varies as follows.
allyl halide > CH3X > 1o halide > 2o halide > 3o halide

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(iii) The order of reactivity among 1– alkyl halides is : CH3X > C2H5X > C3H7X etc.
Remember that in case alkyl halide is optically active, SN2 reactions lead to walden inversion.
(iv) For a given alkyl group the order of reactivity is - (for SN1 and SN2 both) : RI > RBr > RCl > RF
(v) In addition to substitution reaction alkyl halide also undergo elimination reaction to form alkene with the
removal of a molecule of hydrogen halide (dehydrohalogenation). In dehydrohalogenation, hydrogen and
halogen atoms are eliminated from two adjacent carbon atoms, the reaction also known as -elimination it may
proceed by E1 or E2 mechanism (analogous to SN1 and SN2 mechanism)
The order of elimination reaction is :3º halides > 2º halides > 1º halides

Energetics of the reaction

Figure : A free energy diagrams for SN2 reaction

Examples of SN2 reactions of alkyl halide

aq.KOH
Ex. CH3–Cl   CH3–OH + Cl–
(:OH - )strong nucleophile

NaOH+DMF
Ex. CH3–CH2–CH2–Br   CH3–CH2–CH2–OH + Br–

CH3 CH3

KOH+DMSO
Ex. H Br  HO H

CH2 CH3 CH2CH3

CH 3 CH 3
| |
Ex. PCl 3
CH 3 – CH 2 – CH – CH 2 – OH   CH 3 – CH 2 – CH – CH 2 – Cl

H3C H H3C Cl
Ex. PCl
5
 
H OH H H

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CHEMISTRY FOR NEET & AIIMS
SN1 Mechanism : SN1 stands for uni molecular nucleophilic substitution,. The mechanism involves two steps. Consider the
hydrolysis of tert. butyl bromide with aqueous NaOH.
Step-1 : The alkyl halide ionises to give a planar corbonium ion. The corbonium ion is planar because the central
positively charged carbon is sp2 hybridized.

R R R
Show C
C – Br
R +Br
R
R

Step-2 : The nucleophile can attack the planar carbonium ion from either side to give the product.

R
R R R
C Fast OH + OH
C C
R R
R R
– R
OH t-alkyl acohol t-alkyl alcohol

(i) Ionisation is the rate determining step because it is the slow step. In other words, the rate at which alcohol is
formed depends upon the concentration of tertiary alkyl halide alone.
Rate = K[R3C – Br]
(ii) The reactivity order for SN1 reaction  stabil stability of carbocations formed by halides. reactivity order of
halides (SN1) varies as follows.
Benzyl halide > Allyl 3º halide > Allyl 2º halide > Allyl 1º halide > 3º halide > 2 º halide > 1º halide > methyl
halide
(iii) Remember that in case alkyl halide is optically active, SN1 reactions lead to racemisation.
(iv) Energetics of the SN1

Figure : Free energy diagram for the SN1 reaction.

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Properties SN1 SN2

Reactivity of halide RI > RBr > RCl > RF RI > RBr > RCl > RF
leaving groups
Effect of structure R3CX > R2CHX > RCH2X > CH3X CH3X > RCH2X > R2CHX > R3CX
Rate is governed by stability of Rate is governed by stearic effect
carbocation that is formed in (crowding in transition state).
ionization step.
Effect of solvent Rate increases with increasing Rate depends on both nature and
polarity of solvent. concentration of nucleophile.
Effect of nucleophile Rate of substitution is independent Polar aprotic solvents give fastest
of both concentration and nature rates of substitution; solvent of Nu1:
of nucleophile by its dielectric is maximum and nucleophilicity is
constant . greatest.
Stereochemistry Not stereospecific ; racemization Stereospecific; 100 percent inversion
accompanies inversion when of configuration at reaction site.
leaving group is present at a Nucleophile attacks carbon from side
stereogenic centre opposite bond to leaving group.

Nucteophilic substitution reaction (SN) in alkyl halide :

(i) R – X 
HOH(Boil)
 R – OH (alcohol) + HX
(ii) R – X 
KOHaq.
 R – OH (alcohol) + KX
(iii) R – C 
moistAg O
 R – OH (alcohol) + AgX
2

(iv) Reaction with KCN and AgCN :

    Alc.
R – X K C N R – C  N + KX

Ionic bond cyanide (major)

.. Alc.
R–X + Ag – CN R – N C + Ag – X
covalent bond isocyanide (major)

(v) Reaction with NH3:

R–X R–X
Ex. (a) R – X + NH3  R – NH2  R – NH – R  R–N–R
R
R – X
R

R–N–R X (Quatemery salt)
R

(b) R – X + NH3  R – NH2 + H – X

(excess) (Major)

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(c) R – X + NH3  R4NX (Major)

(excess)

(d) CH 3  CH 2  Cl  NH 3 
 CH 3  CH 2  NH 2  HCl

(e) CH3 – CH – CH3 + NH3  CH3 – CH – CH3 + HCl

Cl NH2

CH3 CH2
(f) CH3 – C – Cl + NH3  CH3 – C + NH4Cl
CH3 CH3
more reactive (Elimination is more)
towards elimination

(vi) Reaction with KNO2 and AgNO2:

    Alc.
R – X  K O– N  O R– O – N = O + KX

Ionic bond (Alkyl nitrites) (major)

.. Alc.
O
R–X + Ag – O – N = O R–N + Ag – X
O
covalent bond Nitroalkane (major)
(vii) NSR reaction of alcohol
(a) Reaction with HX:
H–X
R– CH2 – OH RCH2 – X

Mechanism :

H+  –H2O 
X
R – CH2 – OH (H –X)
R –CH2 – O – H R – CH2 R – CH2 – X
H
(Unstable) (Product)

In this reaction intermediate carbocation is formed so rearrangement can take place.

anhy. ZnCl2 act as dehydrating agent and absorbs H2O from the reaction so good yield of halide is obtained.
Also it generates H+ from HCl.

HCl + ZnCl2  ZnCl3  H 

Reactivity order for alcohol :
Reactivity  stability of intermediate carbocation , so reactivity order : Tert. alc. > Sec. alc. > Pri. alc.
Reactivity order of H – X is : HI > HBr > HCl
HI is maximum reactive so it reacts readily with 1º, 2º and º alcohol.
R – OH + HI R – I + H2O
HCl and also 1º alcohol are less reactive so ZnCl2 or some amount of H2SO4 is needed to increase the reactivity .
ZnCl2
CH3 – CH2 – OH + HCl CH3 – CH2 – Cl

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At normal condition :
CH3 – CH2 – OH + HCl X(no reaction)
Note : [HCl(conc.) + ZnCl2(anhydrous)] is callede as lucas reagent, alcohol gives turbidity with lucas reagent.
Reactivity towards lucas reagent (difference in 1º, 2º and 3º alcohol).
1º alcohol 2º alcohol 3º alcohol
Time to in 30 min. in 5 min. in 2-3 second
give turbidity on heating

(b) Reaction with phosphorus halides :

R – OH + PCl5 R – Cl + POCl3 + HCl
3R – OH + PCl3 3RCl + H3PO3
PBr3 and PI3 are less stable, thus for bromides and iodides, (P + Br2) Or (P + I2) mixture is uses.

(c) Reaction with thionyl chloride - (Darzen’s procedure):

Pyridine
R – OH + SOCl2 (1 mole)
R – Cl + SO2 + HCl

one mole one mole

(viii) NSR reaction in ether :

Reaction with HX : Reactivity of HX HI > HBr > HCl
(A) Reaction with cold conc. HX : Ethers forms oxonium salt with cold and conc. HCl (less react cold conc. HI HBr
(more reavtive) break C – O bond.
(B) Reaction with conc. HI or conc. HBr :
CH3CH2 – O – CH3 hot and conc HI CH3CH2 – I + CH3 – I

Nucleophilic substitution in aromatic compound

(ix) NSR reaction in halobenzene :

Cl OH

300ºC
+Aq. NaOH High pressure + NaCl

• Presence of deactivating group at ortho and para position makes the nucleophilic substitution easier.
• This reaction is characteristic reaction of arylhalides with ortho or para electron withdrawing substituent. The
reaction mechanism can be visualised as :

X Nu

Θ
Step-I –X (fast)
+ Nu   
RDS Step-II

NO2 NO2

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Intermediate ion is stabilized by resonance.

Nu X Nu X Nu X
: :

NO2 NO2 NO2

Cl OH
KOH + KCl
Ex.
NO2 NO2

Br OCH3
NO2 NO2
CH 3O– –
+ Br
Ex.
NO2 NO2

Reactivity order : (Towards nucleophilic substitution )

Cl Cl Cl Cl
NO2 NO2 NO2
> > >

NO2 NO2 NO2

(x) NSR in Acid derrivatives :

Example. Hydrolysis of acid derrivatives

Nu
Nu –Z
R–C–Z R–C–Z R – C – Nu

O O O

Where Z = – Cl, – OR, – NH2, – O – C – R

O
here Z is a good leaving group

ETOOS KEY POINTS

1. SN2/E2 is favoured by high conc. of good neucleophile or strong base. (CH3O, HO )

Rate of Reaction  (substrate) (Reagent)
2. SN1/E1 is favoured by low conc. of poor neucleophile or weak base (CH3OH, H2O)
3. If an alkyl halide, undergoes SN2/SN1 then SN2 reaction will be favoured by high conc. of good neucleophile
(negetively charged) in presence of polar aprotic solvent where as SN1 – reaction is fovoured by low conc. of
poor neucleophile (neutral) in presence of polar protic solvent.

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(C) Free radical substitution reaction
Characteristic reaction of alkanes are free radical substitution reaction, these reactions are generally chain reactions
which are completed in three steps :
(a) chain initiation (b) chain propagation. (c) chain termination

UV Light or temp
(i) Halogenation : R–H + X2 
 R–X + HX
250° – 400°C

Mechanism :
UV or temp. • •
(a) Chain initiation : X2 
 X + X
250° – 400°C

• rds •
(b) Chain propagation : X +R–H   R + HX
• •
R + X – X  R – X + X

• •
(c) Chain termination : X + X  X2
• •
R + R  R – R
• •
R + X  R – X

Reactivity of X2 : F2 > Cl2 > Br2 > I2

Reactivity of H : 3°H > 2°H > 1° H

Cl2
CH3 – CH2 – CH2 – CH3  + CH 3 – CH 2 – CH 2 – CH 2 – Cl
light, 25°C CH 3 – CH 2 – CH – CH 3
| (Minor)
Cl
(Major)

Br2
CH3 – CH2 – CH3   CH 3  CH 2  CH 2  Br + CH 3 – CH – CH 3
heat, 127°C
(Minor) |
Br
(Major)

CH 3
|
Br2
CH 3 – CH – CH 3   CH 3  CH  CH 2 Br + CH 3 – C – Br
heat, 127°C
| | |
CH CH 3 CH 3
3
(Minor) (Major)

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(ii) Nitration : (Vapour phase nitration) This involves the substitution of a hydrogen atom of alkane with – NO2 group.
At ordinary temperature, alkanes do not react with HNO3. But reacts with vapours of Conc. HNO3 at 450º C and in
pressure.
400 – 500ºC
R – H + HO – NO2 pressure R – NO2 + H2O
Since the reaction is carried at high temperature and in pressure, so the C – C bonds of alkanes also break during
the reaction and a mixture of nitroalkanes is forned.
Ex. CH3 – CH3 + HNO3 450ºC CH3CH2NO2 + CH3NO2 + H2O

450 ºC
CH3 – CH2CH3 + HNO3 1-Nitro propane
2-Nitro propane (major)

Nitro ethane
Nitromethane

(iii) Sulphonation : Replacement of H atom of alkane by – SO3H is known sulphonation. Alkane react with fuming H2SO4
or oleum (H2S2O7).

CH3 CH3

CH3 – C – H + HO – SO3H CH3 – C – SO3H + H2O

Ex.
CH3 CH3
2-Methyl propane

The reactivity order for sulphonation is tert. H > Sec. H > prim. H
Note : The reaction is observed in higher alkanes and the alkanes having 3º H.

(iv) Chlorosulphonation (Reed reaction) : Reaction with a mixture of SO2 and Cl2 at ordinary temp. in the presence of
UV light is called chlorosulphonation.
C3H8 + SO2 + Cl2 UV C3H7SO2Cl + HCl
Propane sulphonyl Chloride

(II) Elimination Reactions : The reactions are brought about elimination of small molecule from the substrate
Elimination

-elimination
or 1, 1-elimination or 1, 2-elimination

-Elimination (1, 1-Elimination): Removal of H and X from one C-atom

Ex. CHCl3 KOH : CCl2 (dichlora carbene)
Mechanism :

Cl Cl
OH
H – C – Cl –H2O
C – Cl
(acidic H) Cl Cl

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Cl
–Cl CCl
C – Cl  2
Cl
 Elimination (-elimination) : Removal of H and X from adjacent C-atoms
E1 unimolecular elimination

E 2 bimolecular elimination

(a) Unimolecular elimination (E1) :

95%H2SO4
CH3 – CH2 – OH 443ºK
CH2 = CH2

Mechanism of Reaction : The acidic dehydration of alcohol proceeds through the formation of a carbocation
intermediate and is explained as follows :
Step I : Alcohol being a Lewis base accepts a proton (H+) from the acid in a reversible step as follows:

..
CH3 – CH2 – .O. – H + H CH3 – CH2 – O – H
H
Ethanol (From acid) Protonated ethanol

Step II : Due to presence of positive charge on electronegative oxygen, its electron accepting tendency increases.
As a result C – O bond becomes weak and cleaves as follow:

.. Slow
CH3 – CH2 – O – H RDS
CH3 – CH2 + H2O
H
Ethyl carbocation
This is a slow and is regarded as rate determining step in E1 reaction.

Step III: Base removes H(proton) from cabocation and changes it into ethene in a fast step as following
 Base
H – CH2 – CH2 fast
CH2 = CH 2
Ethene

Saytzeff rule : When two possible alkenes are obtained by the elimination rection then that alkene containing
maximum number of alkyl group on double bonded C-atoms is called Saytzeff’s product and formed as major
product.

Note : The alkene having less number of alkyl groups on double bonded C-atoms is called Hofmann’s product.

OH
H2SO4
Ex. (i) CH3 – CH2 – CH – CH3 CH3 – CH = CH – CH3 + CH3 – CH2 – CH = CH2
2-butanol main product 1-butene
2-butene 80 % 20%
Saytzeff's (Hoffmann's product)

H2SO4
(ii) CH3 – CH2 – CH2 – CH2 – OH CH3 – CH = CH – CH3 + CH3CH2CH = CH2

1-butanol 2-butene80% 1-butene 20%

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Mechanism : Acid catalyzed dehydration of alkanols proceeds via the formation of more stable carbonium ion.
..
CH 3CH 2CH 2 – CH 2 – O
.. – H + H CH3CH2 CH 2CH2OH2

CH3 – CH2CH2 CH2OH2 CH3CH2CH2 – CH2 + H2O

Primary Carbonium ion

H H H H
Re arrangement by
CH3 – C – C – C– H CH3 – C – C – C – H
1, 2, hydride ion shift
H H H H H H
1º Carbonium 2º Carbonium more stable

H H CH3 – CH = CH – CH3
Elim ination of
CH3 – C – C – C– H a proton 2-butene (major Product)
H H H
CH3 – CH2 – CH = CH2
2º Carbonium 1-butene (minor product)

OH
H3PO4
+ H2O
(iii) 
Cyclohexanol Cyclohexene

Reactivity order of acidic dehydration of alcohols is : 3º > 2º > 1o R–OH

• Rate of reaction  [substrate]
• Molecularity of reaction = 1 (So reaction is called as E1)
• In reaction intermediate carbocation is formed, So carbocation rearrangement is possible.

(b) Bimolecular elimination (E2) :

(i) Dehydrohalogenation of halides by alcoholic KOH/NaNH2 :
CH3 – CH2 – Cl + KOH(alc.)  CH2 = CH2 + KBr + H2O
Mechanism:
H H
HO + H – C – C – H H2C = CH 2
H Cl

• Reate of reaction a [substrate][base]

• Order of reaction =2 [So reaction is E2]
• In E2 reaction intermediate (carbocation) is not formed. So there will be no carbocation rearrangement.
Alc.
CH3 – CH – CH 3 CH2 = CH – CH3
(KOH)

Cl
Alc.
CH3 – CH2 – CH2 – CH2 – Cl (KOH)
CH3 – CH2 – CH = CH2

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CH3 – CH – CH2– CH3 KOH
CH3 – CH = CH – CH3 + CH2 = CH – CH2 – CH3
Cl (minor) (Hoffmann's product)
(major)(Saytzeff's product)

(ii) Pyrolysis of tera alkyl ammonium ion :

CH3 H CH3
OH
CH3 – N – CH2 – CH2 CH3 – N + CH2 = CH2 + H2O

CH3 CH3

CH – CH2 – CH3
CH3
CH2
OH
Ex. CH3 – N – CH – CH2 – CH3 major product
–H2O
CH = CH – CH3
CH3CH3
CH3 minor product

CH3
CH3 = CH – CH3 (minor)
Ex. –OH
CH3 – N – CH2 – CH2 – CH3
–H2O CH2 = CH2 (major)
CH2 – CH3

Note :- Hoffmann’s product is formed as major product.

Competition between substitution and elemination reacrtions

Reactivity order of alkyl halides : E1 - Reaction : 1º < 2º < 3º

E2 - Reaction : 1º < 2º < 3º
SN1 - Reaction : 1º < 2º < 3º
SN2 - Reaction : 1º > 2º > 3º

(III) Addition reactions : it is also of three types

(A) Electrophilic addition reactions
(B) Free radical addition reactions
(C) Nucleophilic addition reactions
(A) Electrophilic addition reaction :

C=C + AB –C–C–

A B
Alkene Attacking molecule Addition product (Adduct)

From mechanism point of view, the addition in alkenes is generally electrophilic in nature which means that
attacking reagent which carries the initial attack is an electrophile (E+). This is quite expected also as there is
high electron density in the double bond. The mechanism proceeds in two steps.

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Step-I : The p-electron cloud of the double bond causes the polarisation of the attacking molecule (E-Nu) which
cleaves to release the electrophile (E+) for the attack. The double bond simultaneously undergoes electromeric
effect and the attack by the electrophile is accomplished in slow step (also called rate determining step) to form
a carbocation intermediate.

E
(Slow) fast
C=C + E – Nu C–C + :Nu– C–C
Rate determining step (RDS)

E Nu
Addition product

Step-II : The nucleophile (:Nu–) released in the slow step combines with the carbocation to give the desired
addition product in the fast step.

(i) Addition of Halogen : It is a electrophilic addition reaction.

X
R – CH = CH2 + X2 R – CH – CH2

X
(Vicinal halides)

(a) The addition of Br2 on alkenes provides a useful test for unsaturation in molecule. The brown colour
of the bromine being rapidly discharged. Thus decolarization of 5% Br2 in CCl4 by a compound
suggest unsaturation in it. Colourless dibromo compound is formed.
(b) I2 reacts with alkenes to form vicinal di-iodides which are unstable and I2 gets eliminated to give
original alkane.

CH3 – CH = CH2 + I2 CH3 – CH – CH2

X
Unstable

(Slow)
Mechanism : CH2 = CH2 + Br – Br CH2 – CH2 + Br
Br
It is interesting to note that product which is mainly formed as a result of addition is trans in nature whereas
the cis isomer is obtained in relatively smaller proportions. Since carbocation intermediate is planar (sp2 hybridised),
both cis and trans addition products must be formed almost in equal proportions. The trans product can be justified
in case a cyclic ion is formed by the initial electrophile attack.

(Slow)
Br – Br + CH2 = CH2 CH2 – CH2 CH2 – CH2

: Br
.. Br
–
The attack of Br ion on the cyclic ion takes place from the side opposite to side where bromine atom is present
in order to minimise steric hindrace.

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H2C (Fast)
Br + Br Br – H2C
H2C
CH2 – Br
1,2, - Dibromoethane(Anti)

Br
Br 2
Ex. CH3 – CH – CH = CH2 CH3 – CH – CH – CH2

CH3 CH3 Br
Anti addition
No carbocation rearrangement and anti addition product.

(ii) Addition of halogen acid :

X
R – CH = CH – R + HX R – CH2 – CH – R

R – CH = CH2 + HX R – CH – CH3

Markovnikov’s Rule :
First Rule : When molecule of HX add up on unsymmetrical unsaturated hydrocarbon, the electrophile (H+) goes
to the unsaturated carbon atom bearing more number of hydrogen atoms.

X
CH3 – CH = CH2 + HX CH3 – CH – CH2
H
Mechanism : It is electrophilic addition and is illustrated by the action of HCl to propene.

Slow
CH3 – CH = CH2 + H – Cl CH3 – CH – CH3 + Cl–
Secondary carbocation

Fast
Cl– + CH3 – CH – CH3 CH3 – CH – CH3

Cl
2-Chloropropane

Primary carbocation (CH – CH – CH ) is also formed but only in very small proportion since it is less stable
3 2 2

than the secondary carbocation. Markovnikov’s rule is based on stability of carbocation.

Note :- The electrophilic addition to unsymmetrical alkenes always occurs through the formation of a more
stable carbocation intermediate.

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Second Rule : In the addition of HX to vinyl halide and analogous compounds, the halogen attaches itself to
the carbon atom, on which the halogen atom is already present.
CH2 = CH – Cl + HCl CH3 – CH – Cl
Cl
Ethylidene chloride

Cl
H Cl
Mechanism : CH2 = CH – Cl CH3 – CH – Cl CH3 – CH – Cl

All polar reagents of the general structure Y Z (such as H – X, H – OH H – SO3H, XOH) add on unsymmetrical
unsaturated compound in accordance with Markovnikov’s rules. Such additions are called normal Markovnikov’s
rule, where as additions in the opposite manner are referred to as abnormal or anti markovnikov’s additions.

(iii) Addition of water (Hydration of alkenes) : Propene and higher alkenes react with water in the presence of acid
to form alcohol. This reaction is known as acidic hydration reaction. Intermediate in this reaction is carbocation,
so rearrangement may take palce.
+
H
(i) CH3 – CH = CH2 + H2O CH3 – CH – CH3
Propene
OH
Propan-2-ol

OH
+
H
(ii) CH3 – C = CH2 + H2O CH3 – C – CH3

CH3 CH3
2-Methylpropene 2 -Methylpropan-2-ol

Mechanism:
+ (Slow)
CH3 CH = CH2 + H CH3 – CH – CH3
Carbocation(2º)

.. (Fast) –H+
CH3 – CH – CH3 + H – O
.. – H CH3 – CH – CH2 CH3 – CH – CH3
H–O
.. – H O–H
Propan-2-ol

(iv) Hydroboration Oxidation : Borane readily reacts with alkenes giving trialkyl boranes. The reaction is called
hydroboration.

+ – T.H.F.
R – CH = CH2 + BH3 (R – CH2 – CH2)BH2

R – CH = CH2
R– CH = CH2
(R – CH2 – CH2)3B (R – CH2 – CH2)2BH
Trialkylborane

BH3 does not exist or stable as monomer so a solvent THF (tetra hydro furane) is used.

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H
THF
Ex. 3CH3 – CH = CH2 + B – H (CH3 – CH2 – CH2)3B
H
BHR2 also can be taken.

Ex. CH3 – CH = CH2 + BHR2 CH3 – CH2 – CH2– BR2

+
H2O/H
3CH3 – CH2 – CH3 + H3BO3
Propane
(CH3 – CH2 – CH2)3B
Tripropyl Borane
H2O2/OH
CH3 – CH2 – CH2 – OH
Propanol
(1º alcohol)

BH 3
3R – C C–R THF
(R – C = C –) 3B
H R

H
R–C C–R+B H R – CH = C – BH2
H
R

R – CH = C – BH2 + 2R – C C–R (R –CH = C –)3B

R R

Note : The overall process appears to be addition of water according to anti Markovnikov’s rule and involves
syn. addition.

(v) Oxymercuration - demercuration : Mercuric acetate in water is treated with an alkene. The addition product
on reduction with sodium Boro hydride in aqueous NaOH Solution gives alcohol. It follows the Markovnikov’s
CH3 – CH CH2  CH3 – CH – CH3
OH
(i) (AcO)2 Hg/H2O (Mercuric acetate) or (CH3COO)2 Hg/H2O
(ii) NaBH4
CH3 – COO H2 O – +
Hg  CH 3 – COO + CH 3 – COOHg (Electrophile)
CH3 – COO

+ +
CH3 – CH CH2 + HgOOCCH3  CH3 – CH – CH2
HgOOCCH3 


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+
CH3 – CH – CH2 H2O H–O–H –H OH
HgOOCCH3 CH3 – CH – CH2 CH3 – CH – CH2
HgOOCCH3 HgOOCCH3
(cyclic cation)
(Oxymercuration)
OH

NaBH 4
CH3 – CH – CH2 + CH3COO + Hg
H
(Product)

+
OH
H /H2O with rearrangement
CH3 – C – CH2 – CH3 markownikoff's rule
CH3

OH
(i)BH3/THF without rearrangement
CH3 – CH – CH = CH2 CH3 – CH – CH – CH2 anti-markownikoff's rule
(ii) H2O2/OH
CH3 CH3 H

Cl
HCl
CH3 – C – CH2 – CH3 with rearrangememt
markonikoff's rule
CH3

OH
(i) (AcO)2Hg/H2O without rearrangement
CH3 – CH – CH – CH2 markownikoff's rule
(ii) NaBH4
CH3 H
HBr CH3 – CH – CH – CH2 without rearrangement
Peroxide anti-markownikoff's rule
CH3 H Br

(B) Free Radical Addition Reactions : Addition of HBr on alkene or alkyne in presence of peroxide.
HBr( )
CH3 CH CH2 ROOR

Anti Markovnikov’s rule or peroxide effect or Kharasch rule

(i) In the presence of peroxide the addition of HBr on unsaturated unsymmetrical compound takes place contrary
to Markovnikov’s rule. This is called peroxide effect and is due to the difference in the mechnism of the
addition.
(ii) In the normal Markovnikov’s addition the mechanism is ionic.

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(iii) In the presence of peroxide the addition of HBr takes place via free radicals.
(iv) Peroxide effect is not observed in case of H-F, HCl and HI. Reactions follows electrophilic addition mechanism.

HBr
CH3 CH CH3 Markownikoff's addition

CH3 CH CH2 Isopropyl bromide

HBr
CH3 CH2 CH2 Br Anti Markownikoff's addition
R O O R
n–Propyl bromide

Mechanism :
Chain initiation :
(a) R  O  O  R  2RO

(b) HBr  RO  ROH  Br 

Chain propagation :

CH3 CH CH2Br HBr CH3CH2CH2Br + Br

2° free radical more stable (major)
CH3 CH CH2 + Br

HBr
CH3 CH2 CH2 CH3CHCH3 + Br
1° free radical less stable

Chain termination :

R  C H  CH 2  Br  Br   R  CH(Br)  CH 2  Br 

 
R  C H  CH 2  Br  R  C H  CH 2  Br  R CH CH 2 Br
R CH CH2 Br

Br   Br  Br  Br

HBr
Ex. CH3 CH CH2 ROOR CH3 CH CH3
Cl
Sol. no effect simple EAR

(C) Nucleophilic Addition Reaction :

(i) NAR in Alkyne : In these reactions some heavy metal cation like Hg+2, Pb+2, Ba+2 are used. These cation attracts
the – e– of alkynes and decrease the e– density and hence a nucleophile can attack an alkynes.
(a) Addition of dil. H2SO4 (Hydration) : The addition of water takes place in the presence of Hg2+, and H2SO4
[1% HgSO4 + 40% H2SO4].

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CH CH + H OH CH2 CH OH CH3 CHO

(Enol)

OH H
CH3 C CH + H OH CH3 C CH CH3 C CH3
enol O

(b) Addition of alcohols : In presence of BF3 and HgO alkynes react with alcohols and form acetal and
ketal

OCH3
BF3 CH 3OH
CH CH + CH3OH HgO CH2 CHOCH3 CH3 CH
OCH3
Methylal (acetal)

OCH3 OCH3
BF3 CH 3OH
R C CH + CH3 OH HgO R C CH2 R C CH3
OCH3
Ketal
(c) Addition of AsCl3 : In presence of AlCl3 or HgCl2 acetylene combines with AsCl3 to yield Lewsite gas. It is
four times poisonous than mustard gas.

CH CH + Cl AsCl2 CH Cl
CHAsCl2
2-Chlorovinyl dichloro arsine (Lewisite gas)
(ii) NAR in Aldehyde & Ketone : Due to strong electronegativity of oxygen, the mobile  electrons pulled strongly
towards oxygen, leaving the carbon atom deficient of electrons. Carbon is thus readily attacked by Nu. The
negatively by Nu. The negatively charged oxygen is attacked by electron deficient (electrophile) E+.

+ – 
Nu E
C=O RDS C O fast C OE
Nu Nu

Reactivity  Magnitude of +ve charge

of carbonyl group  –1 effect

 1
–1 effect

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Ex. Arrange the following for reactivity in decreasing order
H CH3 CH3
(a) (i) C O (ii) C O (iii) C O
H H CH3
(b) (i) ClCH2CHO (ii) NO2CH2CHO (iii) CH3CHO (iv) CH3CH2CHO
(c) (i) CH3CHO (ii) ClCH2CHO (iii) HCCl2CHO (iv) CCl3CHO

CH3 CH3CH2 (CH3)2CH CCl3

(d) (i) C O (ii) C O (iii) C O (iv) C O
CH3 CH3 CH3 CH 3

Solution. (a) I > II > III (b) II > I > III > IV
(c) IV > III > II > I (c) IV > I > II > III
CH3 - is + I group, decreases the intensity of ve charge on C-atom of > C = O group.
Cl - is -I group increases the intensity of ve charge on C-atom of > C = O group.
(a) Addition of HCN :

H 2O/OH
CH3 CH3 * Partial hydrolysis CH3
C O + HCN C OH C OH
H H H
CN CONH2
Acetaldehyde Cyanohydrin Lactamide (2-Hydroxy propanamide)
+
* (Racemic mixture) 2H2O/H
Complete CH3
hydrolysis
C OH
H
COOH
Lactic acid (2-Hydroxy propanoic acid)

CH3
LiAlH4 C
Reduction
OH
H
CH2NH2
1-Amino-2-Propanol

(b) Addition of NaHSO3 : This reaction is utilized for the separation of carbonyl compounds from non-carbonyl
compounds.

C O + NaHSO3 C OH
SO3Na
Sodium bi sulphite Bisulphite compound
(white Crystalline)

(c) With Alcohol :

H H OH ROH H OR
C O + ROH C C
R R OR R OR
Hemi-acetal (unstable) Acetal

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(d) Reaction with sodium alkynide :

C Acid
O + HC CNa C ONa C OH
Sodium
C CH C CH
Alkynide
Acetylinic alcohol

(e) Reaction with Grignard reagent :

H H H 2O I
C O + CH3Mgl C OMgl CH3CH2OH + Mg
H H OH
CH3
Ethanol (1° alcohol)

OMgl OH
H2O OH
CH3CHO + CH3Mgl CH3 C H CH3 C H + Mg
I
CH3 CH3
2-Propanol (2° alcohol)

OMgl OH
CH3 H2O I
C O + CH3Mgl CH3 C CH3 CH3 C CH3 + Mg
CH3 OH
CH3 CH3
2-Methyl-2-propanol (3° alcohol)

(f) Reaction with glycol :

H O CH2 Weak acidic medium O CH2

C O+ (–H2O)
C
H O CH2 O CH2
(neutral) Cyclic acetal / ketal

(g) Reaction with H2O :

Weak acidic OH
C O + H2O C
(–H2O) OH
(neutral) unstable hydrate
Note : Chloral (Cl3C–CH= O) forms stable hydrate [CCl3 – CH(OH)2 (chloral hydrate)]

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(h) Reaction with ammonia derivatives : These are condensation or addition elimination reaction. These proceeds
well in weakly acidic medium.
NH3  NH2Z (Ammonia derivative)
H
C O + H2 N Z C N Z + H2O
Addition - elimination (Condensation)

Ammonia derivatives (NH2Z) :

Z= OH  NH2OH (Hydroxyl amine)

Z= NH2  NH2NH2 (hydrazine)
Z= NHC6H5 NH2NHC6H5 (Phenyl hydrazine)

NO2 NO2

Z= NH NO2 NH2 NH NO2

2, 4-Dinitro phenyl hydrazine (2, 4 -DNP) Brady's reagent

Z= NHCONH2 NH2NHCONH2
Semi Carbazide.

R R
C O + H2 NOH C NOH (Aldoxime)
H H

R R
C O + H2 NNH2 C NNH2 (Hydrazone)
H H

R R
C O + H2 NNHC6H5 C NNHC6H5 (Phenyl hydrazone)
H H

NO2 NO2

R R
C O + H2 N NH NO2 C N NH NO2
H H

2, 4 - dinitro phenyl hydrazone (Red organge ppt.)

R R
C O + H2 NNHCONH2 C NNHCONH2 (Semi Carbazone)
H H

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(IV) Rearranement reaction :
It may be defined as the reaction involving reshuffling of the sequence of atom to form a new structure :
Beckmann rearrangement

In this reaction ketoxime reacts with H2SO4(conc.) to give a product by alkyl migration.

Bayer-villiger rearrangement
The reaction involve the oxidation of ketone to ester by the treatment with peracids such as peracetic acid,
perbenzoic acid, pertrifluro acetic acid, etc. In this case best migratory group migrate to electron deficient oxygen.

Migratory order : 3° > 2° > 1° > CH3°

CH3–O– – > CH3– –> – > Cl– – > O2N– –

Acid-catalysted decomposition of cumene hydroxide

Benzylic acid rearrangement

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Fries rearrangement
The phenyl esters on treatment with anhydrous AlCl3 undergo fries rearrangement to give o - and p - hydroxy
ketones.

COOCH3 OH OH
AlCl3(Anhydrous) COCH3
+
Heat

Phenyl acetate COCH3

o- p-
Hydroxy acetophenone

Claisen rearrangement
This is the rearrangement of allyl aryl ether to allyl phenols. No catalyst is required and it occurs when the substrate
is heated alone to about 200°C or in some inert solvent like diphenyl ether. Allyl group migrates to ortho-position
and if ortho-position is already occupied, para-isomer is obtained.

O–CH2CH=CH2 OH
CH2CH=CH2
200°C
(Diphenyl ether)

Allyl phenyl ether o-Allyl phenol

O–CH2CH=CH2 OH
H3C CH3 H3C CH3
200°C

CH2CH=CH2

Hydride transfer reaction

(i) Meerween ponndorf verley reduction
i
Al(OPr )3
=O i
–OH
Pr OH

(ii) Oppenauer oxidation

Al(OBut.)
–OH (CH ) C=O3 =O
3 2

(iii) Tischenko Reaction

O O
Al(OEt)3
CH3 – C – H CH3 – C – O – CH 2 – CH3
(iv) Cannizzaro reaction

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(V) ISOMERIZATION REACTIONS :
These reaction involves the interconversion of one isomer into the another isomer.
For example :
AlCl3
CH3 – CH2 – CH2 – CH3 CH3 – CH – CH3
+HCl
(i)
CH3

Al2(SO4)3
CH3 – CH2 – CH CH2 CH3 – C = CH2 + CH3 – CH = CH – CH3
(ii)
CH3
Alc. KOH
(iii)

Reaction at a glance :
S.N Class of compounds Types of reac tions
1. Alka ne Fre e ra dic al substitution
2. Alke ne, a lkyne E le ctroph ilic addition
3. Alkyl h alide N ucleophilic substitution
4. Alde hyde , ketone N ucleophilic addition
5. Add and th eir deriva tive s N ucleophilic substitution
6. Arom atic compounds E le ctroph ilic substitution

Types of solvents
(a) Non polar
(b) Polar (i) polar protic (ii) polar aprotic

(i) Polar protic : A polar solvent which has acidic hydrogen.

(ii) Polar aprotic : A polar solvent which has no acidic hydrogen.

Solvents Polar Protic Aprotic

1. H2O   –
2. CH3OH   –
3. CH3CH2OH   –
4. H–COOH   –
5. CH3–COOH   –
6. NH3   –
7. CH3 CH3  × 
C
O
(acetone)

8. CH3 CH3  ×  DMSO – Dimethyl sulphoxide

S
O
(DMSO)

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CH3
9. H C N  ×  DMF – Dimethyl formamide
CH3
O
(DMF)

CH3
10. CH3 C N  ×  DMA –Dimethyl acetamide
CH3
O
(DMA)

11.  × 

12.  × 

13. CH3–CH2–CH2–CH2–CH3  × 

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1. Rate determining step

The slowest step of the mechanism known as rate determining step of the reaction.Order of reaction or rate law of
reaction is calculated with the help of mechanism of the reaction and generally using rate determine step (R.D.S).
An organic reaction can be represented as
solvent
Reactant (substrate) + Reagent  Product

Homolytic bond dissociation

Ex. A–B  Aº + Bº
Hetrolytic bond dissociation

Ex. A–B  A + B

2. Types of Reagents
A reagent generates three type of attacking species. Which are nucleophile, electrophile and radical.
(a) Electrophiles (b) Nucleophiles (c) Radicals
(a) Electrophiles : Electrophiles are electron deficient species.
    
Ex. H Cl , Br , NO2 , CH3 (positively charged species), PCl5, SO2, SO3 BH3(species with vacant orbital at
central atom, carbenes) etc.

(b) Nucleophiles : It is the electron rich species having atleast one unshared pair of electron. It can be neutral
or negativetely charged it is always a lewis base.
– – – –
Ex. CN , OH , Br , I , NH3 , H2O etc.

(c) Radicals : It is electron deficient species with seven electrons around an atom.
Ex. CH3 C2H5, C2H5O, CH3COO, X etc.

3. Nucleophilicity
The tendency to give e– pair to an electron deficient carbon atom is defined as nucleophilicity.
Leaving group Ability/Nucleofugality
(a) Order of leaving ability of halide ion

> > >

(b) Other good leaving groups are

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(c) Strongly basic ions rarely act as leaving group 

- -
Br + R – OH R – Br + OH (strong base / poor leaving group)

- -
Nu + CH3 – CH3 CH3 – Nu + CH3 (It is not a leaving group)

-
O O
+ -
O -
O
Nu +R X Nu R + X
Leaving group

(d) The weaker bases are better leaving groups.

(e) The leaving group should have lower bond energy with carbon.
(f) Negative charge should be more stable either by dispersal or declocalization.
(g) Leaving group ability :

1. CH3¯ < NH2¯ < OH¯ < F¯

2. R–COO¯ > PhO¯ > HO¯ > RO¯

3. SH¯ > OH¯

4. >

4. Types of solvents
(a) Non polar
(b) Polar (i) polar protic (ii) polar aprotic

(i) Polar protic : A polar solvent which has acidic hydrogen.

(ii) Polar aprotic : A polar solvent which has no acidic hydrogen.

5. Types of Reactions
In organic chemistry the following types of reaction are more important,
(I) Substitution reaction (II) Elimination reaction
(III) Addition reaction (IV) Rearrangement reaction (V) Isomerisation reaction

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Nucleophilic Substitution Reaction

Properties SN1 SN2

Reactivity of halide RI > RBr > RCl > RF RI > RBr > RCl > RF
leaving groups

Effect of structure R3CX > R2CHX > RCH2X > CH3X CH3X > RCH2X > R2CHX > R3CX
Rate is governed by stability of Rate is governed by stearic effect
carbocation that is formed in (crowding in transition state).
ionization step.

Effect of solvent Rate increases with increasing Rate depends on both nature and
polarity of solvent. concentration of nucleophile.

Effect of nucleophile Rate of substitution is independent Polar aprotic solvents give fastest
of both concentration and nature rates of substitution; solvent of Nu1:
of nucleophile by its dielectric is maximum and nucleophilicity is
constant . greatest.

Stereochemistry Not stereospecific; racemization Stereospecific; 100 percent inversion

accompanies inversion when of configuration at reaction site.
leaving group is present at a Nucleophile attacks carbon from side
stereogenic centre opposite bond to leaving group.

SN1 reactivity 3° > 2° > 1°

SN2 reactivity 1° > 2° > 3°

6. Condition for acyl nucleophilic substitution reaction

O O O O O
|| || || || ||
Reactivity order : R—C— CI  R—C—O—C—R > R—C— OR > R—C—NH2

Saytzeff Rule : It states that neutral substrates (alkyl halides or sulphonates) capable of forming a double bond
in either direction of the chain preferably yield that alkene in which there is greater number of alkyl groups
attached to the double bond. This rule applies to E1 reaction and to most of E2 reactions. The following examples
are typical.

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C2 H5OH
C2H5O1 + CH3CH2 CH CH3   CH3CH=CHCH3 + CH3CH2CH=CH2
Br (80% of alkenes) (20% of alkenes) + substitution product

Hofmann Rule : Suggests usually less substituted products if leaving group are positively charged
( ) and fluorine, Actually more acidic -hydrogen is abstracted to produce alkene.

(i)

H
KOH
(ii) CH3 — CH2 — CH — CH2 CH3 — CH2 — CH CH2 1
C2H5OH
Hofmann product
F

Free radical substitution reaction : Characteristic reaction of alkanes are free radical substitution reaction,
these reactions are generally chain reactions which are completed in three steps :
(i) chain initiation (ii) chain propagation (iii) chain termination

Reactivity of X2 : F2 > Cl2 > Br2 > I2

Reactivity of H : 3°H > 2°H > 1° H

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