1024 General Organic Chemistry

Examples : HF  H 2 O  NH 3  CH 4    
I Br Cl F
        
F   OH   NH 2  CH 3 Increasing basicity

Increasing order of nucleophilicity. Decreasing leaving ability
Types of organic reactions (iii) The leaving power of some nucleophilic
It is convenient to classify the numerous groups are given below in decreasing order,
reactions of the various classes of organic compound
O O O
into four types, ||  ||  || 
 Substitution reactions,  Addition reaction, CF3  S  O  Br S  O  CH 3 SO 
|| || ||
 Elimination reactions,  Rearrangement O O O
reactions, O O
||  || 
Substitution reactions C 6 H 5  S  O  CH 3  S  O
|| ||
Replacement of an atom or group of the substrate
O O
by any other atom or group is known as substitution
O O
reactions.   ||     || 
Substituting or  I  Br  CF3  C  O  H O  Cl  F  CH 3  C  O
Examples : Leaving group attacking (iv) In these reactions leaving group of the
group substrate is replaced by another nucleophile. If reagent
CH 3  CH 2  Br  NaOH  CH 3  CH 2 OH  NaBr is neutral then leaving group is replaced by negative
Ethyl bromide Ethyl alcohol
part of the reagent. Negative part of the reagent is
(Bromine atom is replaced by hydroxyl group) always nucleophilic in character.
    
E  Nu
Types of substitution reactions : On the basis of R  L    R  Nu  L ; R  L  Nu  R  Nu  L
the nature of attacking species substitution reactions (v) In S N reactions basicity of leaving group
are classified into following three categories, should be less than the basicity of incoming
(1) Nucleophilic substitution reactions nucleophilic group. Thus strongly basic nucleophilic
group replaces weakly basic nucleophilic group of the
(2) Electrophilic substitution reactions substrate.

(3) Free radical substitution reactions 
Example : R  Cl 
OH
 R  OH  Cl .....(A)
( NaOH )
(1) Nucleophilic substitution reactions
 
Basicity of OH is more than Cl hence OH replaces
(i) Many substitution reactions, especially at the

saturated carbon atom in aliphatic compounds such as Cl as Cl .
alkyl halides, are brought about by nucleophilic  
R  OH 
 R  Cl  OH ......(B)
Cl
reagents or nucleophiles. ( HCl )
  
R  X  OH   R  OH  X Basicity of Cl is less than OH , hence Cl will not
Substrate Nucleophil e Leaving group

replace OH as OH hence reaction (B) will not occur.
Such substitution reactions are called
(vi) Unlike aliphatic compounds having
nucleophilic substitution reactions, i.e., S N reactions (S
nucleophilic group as leaving group, aromatic
stands for substitution and N for nucleophile). compounds having same group bonded directly with
(ii) The weaker the basicity of a group of the aromatic ring do not undergo nucleophilic substitution
reaction under ordinary conditions.
substrate, the better is its leaving ability.
The reason for this unusual reactivity is the
Leaving power of the group 
1 presence of lone pair of electron or  bond on the key
Basicity of the group atom of the functional group. Another factor for the
low reactivity is nucleophilic character of aromatic
HI  HBr  HCl  HF
Example :          ring.
Decreasing acidity (vii) The S N reactions are divided into two
classes, S N 2 and S N 1 reactions.

Table : 23.5 Distinction between SN2 and SN1 reactions

 General Organic Chemistry 1025

Factors SN2 Reactions SN1 Reactions

 
Number of steps R : L  R   : L
Slow
One: R : L  : Nu  R : Nu  : L Two: (i)
(ii) R  : Nu  
 Fast
 R : Nu
Reaction rate and order Second order: First order:
Rate  [Substrate] [Nucleophile] or Rate  [Substrate] or Rate = K1 [RL]
Rate = K 2 [RL ][: Nu ]
Molecularity Bimolecular Unimolecular
 
TS of slow step    
: Nu    C   : L : Nu    C    L    Nu :
Reacting nucleophile The nucleophile attacks the carbon of The nucleophile can attack the carbon of the
the substrate exclusively from the substrate both from the back and front sides
back side. although the back side attack predominates.
Stereochemistry Complete inversion of configuration Inversion and retention takes place.
takes place.
Reactivity order of alkyl Methyl>1°>2°>3°halides. 3°>2°>1° > methyl halides. (I  Br  Cl  F)
halides (I  Br  Cl  F)

Rearrangement No rearranged product is formed Rearranged products can be formed.

(except for allylic).
Nature of nucleophiles Favoured by strong and high Favoured by mild and low concentration of
concentration of nucleophiles. nucleophiles.
Polarity Favoured by solvents of low polarity. Favoured by solvents of high polarity.
Reaction rate determining By steric hindrance. 
By electronic factor (stability of R ).
factor
Catalysis Not catalysed by any catalyst (phase Catalysed by Lewis and Bronsted acids, e.g.,
transfer). 
Ag , AlCl 3 , ZnCl 2 and strong HA.

(2) Electrophilic substitutions reactions : of reaction is 1, it is written as S E 1 (unimolecular)and

Electrophilic substitution involves the attack by an if the order is 2, it is S E 2 (Bimolecular).
electrophile. It is represented as SE (S stands for
substitution and E stands for elctrophile). If the order
SE1 Reaction mechanism : Electrophilic substitution in SE2 Reaction mechanism : Electrophilic
aliphatic compounds are very rare; some of the important substitution is very common in benzene nucleus
examples are: (aromatic compounds) in which -electrons are
(i) Replacement of the metal atom in an organometallic highly delocalized and an electrophile can attack
  this region of high electron density.
compound by hydrogen : R  M  H  R  H  M In all electrophilic aromatic substitution
 reactions, it involves:

 MgBr H
e.g., CH 3  CH 2  MgBr   CH 3  CH 2  CH 3  CH 3 

Step 1. The formation of an electrophile, E, i.e.,

 
CH 3  CH 2  MgBr  H  Br  CH 3  CH 2 
H
CH 3  CH 3  MgBr2
In halogenation; Cl  Cl  FeCl 3  Cl  Fe Cl 4
CH 3  CH 2 Na  C6 H6  CH 3  CH 3  C6 H5 Na
In nitration;
(ii) Decarboxylation of silver salt of carboxylic acid by means   
HNO 3  2 H 2 SO 4  NO 2  2 HSO 4  H 3 O
of bromine:
 
    In sulphonation; 2 H 2 SO 4  SO 3  HSO 4  H 3 O
R3 C  C  OAg  Br  Br  R3 C  C  O  Br  Br  Ag
|| || In Friedel-crafts reaction;
O O  
R  Cl  AlCl 3  R  AlCl 4
 R3C  Br  CO2  AgBr
 
(iii) Isotopic exchange of hydrogen for deuterium or tritium: RCOCl  AlCl 3  RCO  AlCl 4
H E
Step 2. The electrophile H E theHaromatic
attacks E
  
E

Benzene +

H E
E
 1026 General Organic Chemistry
  ring to form carbonium ion (or arenium ion)
RH D⇋ RDH which is stabilized by resonance.
 
R  H T ⇋ R T H

Step 3. Carbonium ion loses the proton to form

substitution product.

The bromination of benzene in the

presence of FeBr 3 is a example of electrophilic
substitution reaction.
Similarly, Nitration, sulphonation and
Friedel-Crafts reaction…..etc., in benzene
nucleus are the other examples of electrophilic
substitution reactions.

(3) Free radical substitution reactions : Free CH 2  CO

radical substitution reactions involves the attack by a CH 3  CH  CH 2  N  Br  
CCl 4

free radical. These reactions occurs by free radical Propene

CH 2  CO
mechanism which involves Initiation, Propagation and NBS
Termination steps. Examples,
CH 2  CO
(i) Chlorination of methane : The chlorination of
Br  CH 2  CH  CH 2  NH
methane in the presence of ultraviolet light is an Ally lbromide
CH 2  CO
examples of free radical substitution. Succinimide

CH 4  Cl 2 
 CH 3 Cl  HCl
UV Addition reactions
Methane light Methylchloride
These reactions are given by those compounds
(ii) Arylation of aromatic compounds (Gomberg which have at least one  bond,
reaction) : The reaction of benzene diazonium halide O
||
with benzene gives diphenyl by a free radical i.e., ( C  C ,C  C , C , C  N ). In such
substitution reaction.
reaction there is loss of one  bond and gain of two 
C6 H 5  H  C6 H 5 N 2 X   C6 H 5  C6 H 5  N 2  HX
Alkali bonds. Thus product of the reaction is generally more
Benzene diazonium halide Diphenyl stable than the reactant. The reaction is a spontaneous
reaction.
(iii) Wurtz reaction : Ethyl bromide on treatment
Types of addition reactions : Addition reactions
with metallic sodium forms butane, ethane and
can be classified into three categories on the basis of
ethylene by involving free radical mechanism.
the nature of initiating species.
(iv) Allylic bromination by NBS (N-
(1) Electrophilic additions
Bromosuccinimide) : NBS is a selective brominating
(2) Nucleophilic additions
agent and it normally brominates the ethylenic
compounds in the allylic (CH 2  CH  CH 2 ) position. (3) Free radical additions

This type of reaction involving substitution at the alpha (1) Electrophilic addition reactions
carbon atom with respect to the double bond is termed (i) Such reactions are mainly given by alkenes
Allylic substitution. It is also used for benzylic and alkynes.
bromination. Some examples are: (ii) Electrophilic addition reactions of alkenes
and alkynes are generally two step reactions.
 General Organic Chemistry 1027

(iii) Alkenes and alkynes give electrophilic Cl

|
addition with those reagents which on dissociation CH 2  CH  CHO  HCl 
 CH 2  CH 2  CHO
Anti- Markowniko ff's addition

gives electrophile as well as nucleophile.

(vii) Mechanism of electrophilic addition
(iv) If the reagent is a weak acid then
reactions is as follows,
electrophilic addition is catalysed by strong acids
  |
(Generally H 2 SO 4 ). CC  E  
Slow
C C E
Olefin Electrophile |
(v) Unsymmetrical alkenes and alkynes give Carbonium ion

addition reactions with unsymmetrical reagents  |  |

according to Markownikoff’s rule. C C E  X 

Fast
C  C E
| Nucleophile | |

The negative part of the addendum adds on that X

Addition product
doubly bonded carbon of the alkene which has least
(2) Nucleophilic addition reactions : When the
number of hydrogen atom.
addition reaction occurs on account of the initial attack
This rule can be used only in those alkenes which of nucleophile, the reaction is said to be a nucleophilic
fulfil the following conditions: addition reaction. Due to presence of strongly
(a) Alkene should be unsymmetrical. electronegative oxygen atom, the  -electrons of the
(b) Substituent/substituents present on doubly carbon-oxygen double bond in carbonyl group ( C  O )
bonded carbon/(s) should only be +I group. get shifted towards the oxygen atom and thereby such
bond is highly polarised. This makes carbon atom of the
(c) If phenyl group is present on doubly bonded
carbonyl group electron deficient.
carbon, then both doubly bonded carbons should be
   
substituted by phenyl groups. CO  C O  C O
For example, the following alkenes will give
addition according to the Markownikoff’s rule. Example : The addition of HCN to acetone is an
example of nucleophilic addition.
CH 3
CH 3 CH 3 OH
CH 3  CH  CH 2 , C  CH 2 ,
C  O  HCN  C
CH 3
CH 3 CH 3 CN
C6 H 5 Acetone Acetone cy anohy drin

C  CH  C6 H 5, C6 H 5  CH  CH 2 The mechanism of the reaction involves the

following steps:
C6 H 5


Following alkenes will not give addition reaction Step 1. HCN gives a proton (H ) and a nucleophile,

according to Markownikoff’s rule. cyanide ion (CN ) .
R R HCN  H   CN 
CH 2  CH 2 , R  CH  CH  R, CC , Step 2. The nucleophile (CN ) attacks the
R R
positively charged carbon so as to form an anion [ H 
C6 H 5 C6 H 5 does not initiate the negatively charged oxygen as
CC anion is more stable than cation].

C6 H 5 C6 H 5 CH 3 CH 3 O
 CH 3 
(vi) Unsymmetrical alkenes having the following CN C  O  CN C  O or C
general structure give addition according to anti CH CH CH CN
3 3 3
Markownikoff’s rule.
CH 2  CH  G , where G is a strong –I group such Step 3. The proton (H  ) combines with anion to
as form the addition product.
O CH 3
||
 CX 3 , NO 2,  CN ,CHO ,COR ,COOH , C  Z CH 3 | CH 3 OH

CN C  O  H  NC  C  OH or C
(Z  Cl, OH, OR, NH 2 ) CH 3 | CH 3 CN
Example: CH 3
 1028 General Organic Chemistry
(I) -elimination reactions or 1,1-elimination
In C  O compounds, the addition of liquid HCN
reactions: A reaction in which both the groups or atoms
gives cyanohydrin and the addendum is CN  ion and are removed from the same carbon of the molecule is
not HCN directly (addition is catalysed by bases or salts called - elimination reaction. This reaction is mainly
of weak acids and retarded by acids or unaffected by given by gem dihalides and gem trihalides having at
neutral compounds). least one - hydrogen.

   O  OH Alc. KOH /
.. 
H CN   CN H CHX 3   CX 2  X  H
C  O    C  O  C 
 C
( A. R.) CN CN Product of the reaction is halocarbenes or
Nucleophilic addition (AN) reactions on carbonyl dihalocarbenes. which are key intermediates in a wide
compounds will be in order: variety of chemical and photochemical reactions.

H H 3C H 3C (II) -elimination reactions or 1, 2-elimination

C O  C O  C O reactions: Consider the following reactions,
H H H 3C  
CH 3  CH 2  CH 2  L  CH 3  CH  CH 2  H  L
Decreasing order of nucleophilic addition in some  

species.
A reaction in which functional group (i.e., leaving
O
||
O
|| group) is removed from - carbon and other group
C 6 H 5 CH 2 COCH 3  CH 3 COCH 3  C 6 H 5  C  CH 3  C 6 H 5  C  C 6 H 5  CHO  (Generally hydrogen atom) from the - carbon is called
COCH 3  COCl  COOCH 3  CONH 2  COOH - elimination reaction. In this reaction there is loss of
two  bonds and gain of one  bond. Product of the
(3) Free radical addition reactions : Those
reaction is generally less stable than the reactant.
reactions which involve the initial attack by a free
radical are known as free radical reactions. Addition of (1) Types of - elimination reactions : In
hydrogen bromide to alkenes (say, propylene) in the analogy with substitution reactions, - elimination
presence of peroxide (radical initiator) follows free reactions are divided into three types:
radical mechanism. Free radical reactions generally
(i) E1 (Elimination unimolecular) reaction, (ii) E2
take place in non-polar solvents such as CCl 4 , high
(Elimination bimolecular) reaction and (iii) E1cb
temperature, in presence of light or a free radical (Elimination unimolecular conjugate base) reaction
producing substance like O 2 and peroxides.
(i) E1 (Elimination unimolecular) reaction :
Elimination reactions Consider the following reaction,
Elimination reactions are formally the reverse of CH 3  CH 3
addition reactions and involve the removal of the two | C H O/  
groups (Generally, one being a proton) from one or two CH 3  C  Cl 
2 5  CH 2 C  C 2 H 5 OH  Cl
|
carbon atoms of a molecule to form an unsaturated CH 3 CH 3
linkage or centre.
(a) Reaction velocity depends only on the
Elimination reaction is given by those compounds
concentration of the substrate; thus reaction is
which have a nucleophilic group as leaving group,
unimolecular reaction.
  R R
  Rate  [Substrate]
i.e., X, OH, OR, N 2 , N 3 , H 3 O, N R, S
R R (b) Product formation takes place by the
Elimination reactions are generally endothermic formation of carbocation as reaction intermediate (RI).
and take place on heating. (c) Since reaction intermediate is carbocation,
Elimination reactions are classified into two rearrangement is possible in E1 reaction.
general types,
(d) Reaction is carried out in the presence of
(I) - elimination reactions or 1, 1-elimination polar protic solvent.
reactions.
(e) The E1 reaction occurs in two steps,
(II) - elimination reaction or 1, 2-elimination
reactions. Step 1.
 General Organic Chemistry 1029

CH 3 CH 3 Cl
| 
   2 |
|
Alc.KOH / 
CH 3  C  Cl  CH 3  C - - - - - Cl    CH 3  C  CH 3  Cl
Slow step
CH 3  CH  CH  CH 3 
 CH 3  C  CH  CH 3
| | | |  1  HCl |
CH 3 CH 3 CH 3 CH 3 CH
(TS 1 ) ( RI )
3
Saytzeff p roduct

Step 2.
(ii) Hofmann rule : According to this rule, major
  product is always least substituted alkene i.e., major
 
..    product is formed from - carbon which has maximum
B  H  CH 2  C  CH 3   B - - - - H - - - -CH 2 - - - - C  CH 3 
|

|
 number of hydrogen. Product of the reaction in this
CH 3 CH 3
  case is known as Hofmann product.
 TS 2 

CH 3 CH 3 Br CH 3
 | |
Alc.KOH / 
|

 B H  CH 2  C
fast CH 3  C  CH 2  CH  CH 3  CH 3  C  CH 2  CH  CH 2
| 2  1 |
CH 3 CH 3 CH 3
Hofmann product
(ii) E2 (Elimination bimolecular) reaction :
Consider the following reaction,  In E1 reactions, product formation always takes
place by Saytzeff rule.
 
CH 3  CH 2  CH 2  Br   CH 3  CH  CH 2  H  Br
Base ( B)
  In E1cb reactions, product formation always
(a) Reaction velocity depends only on the takes place by Hofmann rule.
concentration of the substrate and the base used; thus  In E2 reactions, product formation takes place
reaction is bimolecular reaction. Rate [Substrate] by Saytzeff as well as Hofmann rule. In almost all E2
[Base]
reactions product formation take place by Saytzeff rule.
(b) Since the reaction is a bimolecular reaction,
the product formation will take place by formation of (3) Examples of  - elimination reactions
transition state (TS). (i) Dehydrohalogenation is removal of HX from
(c) Rearrangement does not take place in E2 alkyl halides with alcoholic KOH or KNH 2 or ter- BuOK
reaction but in case of allylic compound rearrangement (Potassium tertiary butoxide) and an example of -
is possible. elimination,

(d) Reaction is carried out in the presence of e.g., CH 3  CH 2 X   H 2 C  CH 2 ;

Alc.KOH
( HX ) Ethene
polar aprotic solvent.
CH 3  CH  CH 3   CH 3 CH  CH 2
Alc.KOH
(e) The E2 reaction occurs in one step, | ( HX ) Propene
.. X
B H H  B  - - - - H   H 
| |   |  CH 3  CH 2  CH  CH 3   CH 3  CH  CH  CH 3 
Alc.KOH

CH 3  C  C  H   CH 3  C
Slow step
C  H | ( HX ) 2 - Butene (Major)
| |  |   X
H Br  H Br 
 TS  CH 3  CH 2  CH  CH 2
1- Butene (Minor)

 CH 3  CH  CH 2  BH  Br
fast
(ii) Dehydration of alcohol is another example of
(2) Orientation in  - elimination reactions : If elimination reaction. When acids like conc. H 2 SO 4 or
substrate is unsymmetrical, then this will give more
H 3 PO 4 are used as dehydrating agents, the mechanism
than one product. Major product of the reaction can be
is E1 . The proton given by acid is taken up by alcohol.
known by two emperical rules.
Dehydration is removal of H 2 O from alcohols,
(i) Saytzeff rule : According to this rule, major
product is the most substituted alkene i.e., major e.g.,
 Conc. H 2 SO 4 , 170 C
CH 3  CH 2  OH    H 2 C  CH 2
product is obtained by elimination of H from that - ( H 2 O )

carbon which has the least number of hydrogen.

Conc. H 2SO 4 , 170 C
Product of the reaction in this case is known as Saytzeff CH 3  CH 2  CH 2  OH    CH 3  CH  CH 2
Propan -1 - ol ( H 2 O ) Propene
product.
 1030 General Organic Chemistry
 Dehydration of alcohols is in the order: Y  B
Tertiary  Secondary  Primary
| |
Y | | | |
 C  C    C  C    C  C 
(3) (2) (1) | | | |
X: X
 2° and 3° alcohol by E1 process and 1° alcohol
Bridged or
by E2 process. Alcohols leading to conjugated alkenes
non-classical carbocation
are more easily dehydrated than the alcohols leading to X= Nucleophilic species, Y = Electronegative
non-conjugated alkenes. CH 2  CH  CH  CH 3 is easily group, B = Another nucleophile.
|
OH (2) Rearrangement or migration to electron
dehydrated than rich atoms (Electrophilic rearrangement) : Those
CH 3  CH 2  CH  CH 3 and so rearrangement reactions in which migrating group is
|
electrophile and thus migrates to electron rich centre.
OH
OH OH OH
(3) Rearrangement or migration to free radical
>
species (Free radical rearrangement) : Those
>
rearrangement reactions in which the migrating group
moves to a free radical centre. Free radical
rearrangements are comparatively rare.
(iii) Dehalogenation : It is removal of halogens,
(4) Aromatic rearrangement : Those
e.g., CH 2  CH 2  Zn dust   H 2 C  CH 2
in CH 3 OH , heat

| | (-ZnBr2 ) Ethy lene rearrangement reactions in which the migrating group

Br Br moves to aromatic nucleus. Aromatic compounds of the
Ethy lene bromide
type (I) undergo rearrangements in the manner
X–Y X–H X–H
(iv) Dehydrogenation : It is removal of hydrogen, mentioned below,
Y
Cu , 300 C
e.g., CH 3  CH  CH 3    CH 3  C  CH 3  +
| ( H 2 ) ||
OH O +
Isopropy l alcohol Acetone
(I) Y
Rearrangement reactions
The reactions, which involve the migration of an The element X from which group Y migrates may
atom or group from one site to another within the be nitrogen or oxygen.
molecule (nothing is added from outside and nothing is Isomerism
eliminated) resulting in a new molecular structure, are
known as rearrangement reactions. The new compound Organic compounds having same molecular
is actually the structural isomer of the original one. formula but differing from each other at least in some
physical or chemical properties or both are known as
It is convenient to divide rearrangement
isomers (Berzelius) and the phenomenon is known as
reactions into following types:
isomerism.
(1) Rearrangement or migration to electron
The difference in properties of isomers is due to
deficient atoms (Nucleophilic rearrangement) : Those
the difference in the relative arrangements of various
rearrangement reactions in which migrating group is
atoms or groups present in their molecules. Isomerism
nucleophilic and thus migrates to electron deficient
can be classified as follows:
centre which may be carbon, nitrogen and oxygen.
B:
Isomerism

X
Constitutional or structural Configurational or stereo isomerism
isomerism The isomerism arises due to different arrangement
Without referring to space, the isomers
of atoms or groups in space. It deals with the
differ in the arrangement of atoms within
the molecule is called structural structure of molecules in three dimensions. Thus
isomerism. Thus structural isomers have: stereoisomers have:

Chain Position Ring Functiona Meta Tauto - Geometric Optical Conformation

isomeris isomeris chain l merism merism al isomeris al
m m isomeris isomeris isomerism m isomerism
m m