REACTION MECHANISM

GRAVIITY ACADEMY
ORGANIC CHEMISTRY

CLEAVAGE OF COVALENT BOND

Organic reaction is a process in which breaking and formation of covalent bond/bonds take place. In
organic reaction, the main organic compound which is converted into a new compound by breaking
and formation of covalent bonds is known as the reactant or substrate and the new compound
formed is known as the product. The chemical species which causes the change is called the reagent.

CH3 – CH2 – Br + OH CH3 – CH2 – OH + Br

Substrate or Reagent Product
Reactant
Breaking of covalent bond of the compound is known as bond fission. A bond can be broken by
two ways:
(a) Homolytic fission or Homolysis
In this fission, the covalent bond is broke in such a way that each resulting species gets its own
electron. This leads to the formation of odd electron species known as free radical.

A: B A• + B•
free radical
The factor which favours homolysis is zero or a small difference in electronegativity between A
and B. Homolytic bond fission takes place in gaseous phase or in the presence of non polar
solvents (CCl4, CS2)
Condition for homolytic bond Fission : Homolysis takes place in the presence or peroxide. UV
light, heat ( 500ºC), electricity and free radical. The process is known as initiation of free radical
reaction.

(i) Peroxide
A: B Aº + Bº
(ii) h
(iii) 
(iv) Electricity
or
( v) Free radical

(i) Homolytic bond fission gives free radical as the reaction intermediate.
(ii) Reaction mechanism of the reaction is known as free radical or homolytic mechanism.
(b) Heterolytic Bond Fission or Heterolysis
In heterolysis, the covalent bond is broken in such a way that one species (i.e., less electronegative) is
deprived of its own electron, while the other species gains both the electrons.

A:B A+ B
 2 REACTION MECHANISM

Thus formation of opposite charged species takes place. In case of organic compounds, if positive
charge is present on the carbon then cation is termed as carbocation. If negative charge is present on
the carbon then anion is termed as carbanion. Carbocation and carbanion are the reaction intermediates.
The factor which favours heterolysis is a greater difference of electronegativity between A and B.
Thus
(1) Heterolytic bond fission gives carbocation or carbanion as reaction intermediate.
(2) Mechanism of the reaction in which heterolytic bond fission takes place is known as heterolytic
mechanism or ionic mechanism.
(3) The energy required for heterolytic bond fission is always greater than that for homolytic bond
fission due to electrostatic force of attraction between ions,

(c) Reaction Intermediates

A great majority of organic reactions are multistep processes involving intermediates whose life time are
usually very short. An understanding of the structures and properties of these intermediates which are
normal covalent compounds, ions or radical’s is of paramount importance to an understanding of organic
reaction mechanisms. As we shall see in the energy profile diagrams, intermediates possess sufficiently
low energy to be formed under the reaction conditions, but in most of the cases are not stable enough
to permit isolation. This is especially true of those intermediates in which carbon has fewer than four
covalent bonds. A brief description of some common kinds of intermediates is given below.

Carbocations
Carbocations are the key intermediates in several reactions and particularly in nucleophilic substitution
reactions.
Structure : Generally, in the carbocations the positively charged carbon atom is bonded to three
atoms and has no lone pairs on carbon. Carbon has six valence electrons. It is sp2 hybridized with a
planar structure and bond angles of about 120°.
R

C
R R
Orbital picture of carbocation

There is a vacant unhybridized p orbital which e.g., in the case of C H 3 lies perpendicular to the
sp2 hybridised plane..
Formation : Carbocations can be generated in a variety of way’s some of the reactions in which
carbocations are formed are summarized below.
1. Solvolyis of C—X bond (X = halogens, OBs, etc]
R — X   R  X–
2. Deamination of amines by nitrous acid.
HNO2
R — NH 2   RN 2   R   N2
3. Protonation of alcohols followed by dehydration
 
H
R — OH   R   H2O
R O H 2 

Stability: There is strong evidence, both physical and chemical, that alkyl groups are more electron-donating
than hydrogen. It , therefore, follows that when these groups are attached to the electron-deficient
carbon of the carbocation, they tend to release electrons and partially compensate for the electron-
deficiency of the positive carbon. The positive charge thus gets dispersed over all the alkyl groups and
this dispersal of charge increases the stability of the whole system. Accordingly, tertiary carbocations
REACTION MECHANISM
3
are more stable than secondary ones which in turn are stabler than primary carbocations.

R H H H

R C  R C  R C H C

R R H H
The greater stability of alkyl substituted carbocations is sometimes partly ascribed to the phenomenon
of hyperconjugation. According to this, the  electrons of an  C—H bond can be delocalized into
the unfilled p orbital of the positive carbon atom, thus spreading the charge over all such bonds. For an
alkyl-substituted carbocation, several hyperconjugative resonance forms can be written each having
the same number of covalent bonds as the first structure.
H H H H

H C CH2 H C CH2 H C CH2 H C CH2

H H H H

In case of a secondary carbocation, more equivalent structures can be written than for a primary
carbocation whereas still greater number of such structures can be written for a tertiary carbocation.

H H

H C H H C H
Five more eqivalent
H3C C H3C C structures

H H

H H

H C H H C H
Eight more eqivalent
H3C C H3C C structures

CH3 CH3

Resonance is an important factor that enhances the stability of a carbocation by delocalization of its
charge in systems like allyl and benzyl carbocations.
CH 2 = CH — CH 2 CH 2 — CH = CH 2

CH2 CH2 CH2 CH2


 
 


Triphenyl carbocation is so stable that when triphenylmethyl bromide is placed in liquid sulphur dioxide
(a solvent with which carbocation does not react) it is possible to determine it quantitatively by measuring
the electrical conductivity of the solution.
C6 H 5 C6 H 5
liquid SO2
H 5 C6 C Br   H 5 C6 C  Br

C6 H 5 C6 H 5
 4 REACTION MECHANISM

CPh2 
 CPh2 
 CPh2

etc. 
 CPh2

Steric effects also play key role in the ease of formation and stability of carbocations derived from
highly substituted substrates. The stability of such carbocations is attributed to the steric relief. In substrates
such as tri-isopropyl chloride, the three bulky isopropyl groups are pushed together due to sp3 angle of
109.5°. This pushing together results in a strain called B strain (or back strain). When this ionizes, the
angle expands from 109.5° ( sp3 ) to 120° ( sp 2 ) resulting in the relief of this strain due to increase in
space between the alkyl groups.

CH3 H3C CH3

H3C HC CH
109.5°
Cl H3C C
H3C CH 109.5° CH 120° CH
CH3
°

CH
9.5

H3C
10

H3C CH3
H3C CH3

Such a carbocation would resist addition of a nucleophle as it would result in the crowding of bulky
groups together.
NOTE- READ REARRANGEMENT REACTIONS -MODULE(REACTION MECHANISM)
PAGE NO - 14 to 17
Carbanions
Carbanions are anions of carbon, generated by the removal of one of the groups attached to a carbon
without removing the bonding electrons. Thus, every carbanion possesses one unshared pair of electrons
and three pairs of bonding electrons around the central carbon atom which is sp3 hybridized.
R
R' C
R"
We know that the non-bonding electron pair repels the bonding pair more than the bonding pairs repel
each other and because of this, there is reduction of the angle between bonding pairs to a value slightly
lesser than the tetrahedral value of 109.5°. The configuration of simple carbanions such as the methyl
anion thus appears to be pyramidal just like that of ammonia with which the methyl anion is isoelectronic.
With this picture of carbanion, one can infer that if the three substituents are different, the carboanion
should be asymmetric and consequently there should be retention of configuration in the reactions
involving a carbanion intermediate. However, it could not be demonstrated experimentally as the unshared
pair and the central carbon rapidly oscillate from one side of the plane to the other. This rapid equilibrium
between enantiomeric pyramidal structure thus explains the loss of optical activity associated with the
asymmetric carbanions.
R R H
R' C C R' H N
R" R" H
 REACTION MECHANISM
5
Formation : As there is little difference between the electro negativities of carbon and hydrogen (2.5 and
2.1, respectively) the polarity of the C—H bond is very small. The heterolytic fission of this covalent
bond to form an anion and a proton should then be a very difficult process. In other words, a
hydrogen atom bound to an sp3 carbon atom shows negligible acidity. However, the presence of
electron attracting substituents such as nitro, cyano or carbonyl groups on the same carbon renders the
hydrogen relatively acidic. The increase in acidity is not only due to the electron-withdrawing ability of
these substituents, but also due to their ability to delocalize the negative charge of the anion. Thus
hydrogens on the carbon atom alpha to nitro, cyano or carbonyl groups have acidic character and can
be removed as protons leaving resonance stabilized anions.

O O O

–H
H3C N   H2C N 
 H2C N

O O O

–H
CH 3 — C  N   CH 2 — C  N 
 CH 2   N 

O O O

H3C C H –H
  H2 C C H  H2C
 C H

Carboanions are also formed when a nucleophile adds to a carbon-carbon double bond.

 C2 H5 OCH 2 — CH — C  N 
 
C2 H5 O  CH 2  CH — C  N  


 C2 H5 OCH 2 — C  C  N 

H
Stability : As we have already seen, carboanions are stabilized by electron-withdrawing substitutents.
Generally speaking, a carbanion is stabilized by resonance if a double bond is located  to the anionic
carbon. This explains the stability of the allylic and benzylic carbanions.

R—CH  CH—CH 2 R—CH—CH  CH 2

CH2 CH2 CH2 CH2

(2) (1) (3)

Ready conversion of triphenylmethane to the triphenylmethyl carbanion can be similarly explained.
Na
(C6 H5 )3 CH   (C6 H5 )3 C : Na 

(C6H5)2 C (C6H5)2 C etc

The order of stability of the simple carbanions is : methyl > primary > secondary > tertiary
Another factor that contributes to the stability of carbanions is the extent of s-character of the bonding
orbitals of the carboanionic carbon. Carbanion stability, thus, has been found to be in the order:
RC  C  R 2 C  CH   R 3C — CH 2 . We have already seen that the carbon atom in acetylene is
 6 REACTION MECHANISM

sp hybridized (50% s character) and hence hydrogen atom attached to it should be more acidic than
that of ethylene where the carbon is sp 2 hybridized (33% s character).
An interesting example is cyclopentadiene which readily loses a proton to form the cyclolpentadienyl
anion.
–
CH3O
  

H H
H H
The unusual stability of cyclopentadienyl anion is explained by the fact that although it has only four 
electrons, two more electrons become available to it by the heterolysis of the C—H bond thus forming
a system of six electrons. These electrons are spread over all the five carbon atoms like the delocalized
aromatic system of benzene ring, thus conferring on it stability so characteristic of the aromatic compounds.

Free Radicals
There are two possible structures for simple alkyl radicals. Either a free radical may be a planar species
(A) in which the carbon atom bearing the odd electron in sp 2 hybridized (as in carbocations) and the
odd electron remains in the p-orbital, or it could have a shape resembling a shallow pyramid (B)
which is neither planar nor tetrahedral and the orbital containing unpaired electron is some sort of a
hybrid between a p and an sp3 orbital.

R' R" R R
fast
C or R' C C R'
R" R"
R
(A) (B)

The question as to whether free radicals exist in a planar configuration or in a rapid equilibrium
between the two pyramidal forms (B) is difficult to answer with certainty. However, available evidence
indicates that the unpaired electron is in a p orbital. Resonance stabilized free radicals certainly exist in
planar configuration.

Formation : Free radicals are often produced when a molecule is supplied with sufficient energy—thermal or
photochemical—to cause homolysis of a covalent bond. In addition oxidation-reduction reactions
involving the gain or loss of a single electron can also generate radicals. Some typical reactions producing
free radicals are given below:

(CH 3 ) 4 Pb   4CH 3  Pb

CH 3 — N  N — CH3   2CH3  N 2

C6 H 5CO — O — OCOC6 H5   2C6 H 5COO 
 2C6 H 5 2CO 2
hv
CH 3COCH 3   CH 3 COCH 3 
 CH3  CO

O O
anode
R C O 
– e–
R C O 
 R  CO 2
Stability: In general, it has been found that the stability of alkyl radicals is in the order
(CH 3)3C  (CH3)2CH  CH3 – CH2 . The reason for the stabilizing influence of alkyl groups is not far
to seek if we consider that in going from methyl to t-butyl, there is increasing tendency for electron
release due to hyperconjugation. As we have seen that the carbon atom carrying an unpaired electron
has a half-filled orbital that gives the radical its characteristic unstability; the hyperconjugative
 REACTION MECHANISM
7
mechanism tends to fill this orbital and thus stabilizes the radical to some extent. Various
hyperconjugative contributing forms of tert-butyl radical are given below :
CH3 CH2 H CH3

C C C etc
H3C CH3 H3C CH3 H3C CH2 H
Allyl and benzyl radicals are particularly stable because of resonance involving  electrons of the
double bond or aromatic ring.
CH 2  CH — CH 2 
 CH 2 — CH  CH 2
IX

CH2 CH2 CH2

Another factor that is responsible for the increased stability of tertiary radicals may be steric. Formation
of a tert-butyl radical by the removal of a hydrogen atom from isobutane, (CH 3 )3 CH , is favoured as
the steric repulsion between the methyl groups is relieved to a certain extent by an increase in bond
angles from 109.5° to about 120°. Clearly this steric relief should be the greatest in the formation of a
tertiary radical.

Carbenes
Carbenes can be defined as neutral, divalent carbon intermediates in which a carbon is covalently
bonded to two atoms and has two non-bonding orbitals containing two electrons between them.
Theoretical considerations suggest that there are two possible kinds of carbenes, singlet and triplet
carbenes. In the singlet state, a carbon atom is presumed to approximate sp2 hybridization. Two of the
three sp2 hybrid orbitals are utilized in forming two covalent bonds whereas the third hybrid orbital
contains the unshared pair of electrons. The unhybridized p orbital remains vacant. Thus singlet carbene
(A) resembles a carbocation very closely. On the other hand, carbon atom of a triplet carbene (B) is sp
hybridized and it is a linear or near-linear species. These two hybrid orbitals are involved in the bond
formation with two groups and the two electrons are placed one each, in the equivalent, mutually
perpendicular py and pz orbitals . Since these electrons have parallel spins, a carbene with this
structure is said to be in a triplet state.

(A) (B)

At first sight, it appears that a singlet carbene has lower energy as the unshared electron pair is in a sp2
hybrid orbital ; but the considerations of the electron repulsion energy that must be overcome to pair
two electrons in a single orbital places it at the higher energy level than a triplet structure. It is, therefore,
reasonable to believe that the triplet state of a carbene is more stable than the singlet state and should be
expected to be the ground state.
Formation : Photochemical or thermal cleavage of cyclopropanes and oxiranes is a common method for the
generation of carbenes.
 8 REACTION MECHANISM

H 5 C6 CH2
hv
C CH2 
or 
H 2 C  C6 H5CH  CH 2
H

H 5 C6 O O
hv
C CH   C6 H5 HC  HC — C6 H5
H C6 H 5

Stability: Carbenes in which the carbene carbon is attached to two atoms, each bearing an unshared pair of
electrons, are somewhat more stable due to resonance.

R2 N R2 N R2 N
C 
 C 
 C
R2 N R2 N R2 N

Nitrenes
Nitrenes are electron-deficient monovalent nitrogen species in which the nitrogen atom has a sextet of
electrons in its outer shell. There are two possible forms in which a nitrene can exist, the singlet and
triplet states.

R—N R—N
singlet triplet

Arynes
Arynes may be defined as aromatic compounds containing a formal carbon-carbon triple bond. The
best known aryne is benzyne which may be regarded as the aromatic counterpart of acetylene or in
other words, it is benzene minus two ortho hydrogens and can also be called as dehydrobenzene.

The benzyne bond is not like the triple bond of acetylene where the two carbons form a  bond using
sp orbitals and the remaining p orbitals are used to form  bonds. Such a structure is not possible in
benzyne because of the hexagonal geometry associated with the benzene ring. Most probably the new
bond of benzyne is formed by the overlap of sp2 orbitals belonging to two neighbouring carbon atoms.
These sp2 orbitals are orthogonal to the  molecular orbital of the benzene ring.

Formation: Benzyne has been shown to be intermediate in several important organic reactions. For example,
in the presence of a strong base, aryl halides eliminate HX from 1, 2-positions to produce benzyne
 REACTION MECHANISM
9
which then rapidly reacts with the available nucleophile to regenerate the aromatic system.

Br
 NH 2 
  NH 3 Br
H

NH3 NH2
 NH 3 
 


Stability: The new bond of benzyne, formed by the overlap of sp 2 orbitals belonging to two neighbouring
carbon atoms in unstable, and therefore benzynes are extremely reactive chemical species.

3. NATURE OF ATTACKING REAGENTS

Organic reagents can be classified in two categories:
Electrophile : Electron deficient species or electron acceptor to form a covalent bond is electrophile.
Nucleophile : Electron rich species or electron donor to form a covalent bond is nucleophile.

(a) Electrophiles
It can be classified into two categories:
(A) Charged electrophiles (B) Neutral electrophiles
(A) Charged electrophiles : Positively charged species in which central atoms has incomplete
octet is charged electrophile.
O
H, X, R, N , N==O , SO3H
O
 Note : All cations are charged electrophiles except cations of I A , II A group elements ,
Al+++ and NH4
(B) Neutral electrophiles : It can be classified into three categories:
(I B) Neutral covalent compound in which central atom has incomplete octet is neutral electrophile.
BeCl2, BH3, ZnCl2, AlX3, FeX3, CH3, CH2 , CX2
(II B) Neutral covalent compound in which central atom has complete or expended octet and central
atom has unfilled-d-sub-shell is neutral electrophile
SnCl4, SiCl4, PCl5, SF6, IF7
(III B) Neutral covalent compound in which central atom is bonded only with two or more than two
electronegative atoms is neutral electrophile.
BeCl2, BX3, AlX3, FeX3, SnCl4, PCl3
PCl5, NF3, CX2 , CO2, SO3, CS2, CX4
 Note : (i) Cl2, Br2 and I2 also behave as neutral electrophiles.
(ii) Electrophiles are Lewis acids.

(b) Nucleophiles
Nucleophiles can be classified into three categories:
10 REACTION MECHANISM

(A) Charged nucleophiles: Negatively charged species are charged nucleophiles.

H, OH, R—O, CH3, X, SH, R—S
(B) Neutral nucleophiles: It can be classified into two categories:
(I B) Neutral covalent compound, in which central atom has complete octet, has at least one lone
pair of electrons an all atoms present on central atom should not electronegative, is neutral
nucleophile.
NH3, RNH2, R2NH, R3N, NH2—NH2 (nitrogen nucleophile)
H– O –H, R– O –H, R– O –R (Oxygen nucleophiles)
H–S –H, R–S –H, R–S –R (Sulphur nucleophiles
PH3 , RPH2 , R2PH, R3 P (Phosphorus nucleophiles)
(II B) Organic compound containing carbon, carbon multiple bond/bonds behaves as nucleophile.
Alkenes, Alkynes, Benzene, CH2=CH–CH=CH2, CH2=CH–CCH

(C) Ambident nucleophiles: Species having two nucleopilic centres, one is neutral (complete
octet and has at least one lone pair of electrons) and other is charged (negative charge) behaves
as ambident nucleophile
O
C  N, O—N=O, O—S—OH
O
Note : (1) Organometallic compounds are nucleophiles.
(2) Nucleophiles are lewis bases.
Organic compounds which behave as electrophile as well as nucleophile: Organic compound in
which carbon is bonded with electronegative atom (O, N, S) by multiple bond/bonds behaves as
electrophile as well as nucleophile.
O O O O
R—C—H , R—C—R , R—C—OH , R—C—Cl ,
O O
R—C—OR , R—C—NH2 , R—C NH2 , R—N C
Note : During the course of chemical reaction electrophile reacts with nucleophile.
 REACTION MECHANISM
11

NUCLEOPHILE & NUCLEOPHILICITY

1. NUCLEOPHILE : It is the e– rich species having atleast one lone pair of electrons. It can be neutral
or –vely changed it is always a lewis base.

BASICITY : It is the tendency to donate e– pair to ion.

All bases are nucleophiles, but all nucleophlies are not base all the time.

(i)

(ii)

1.1 NUCLEOPHILICITY :
The tendency to give e– pair to an electron deficient carbon atom is defined as nucleophilicity.

(i) Criteria for Nucleophilicity :

1. The factors which increases e– density at ‘donor atom increases nucleophilicity’.
2. The more polarisable donar atom is a better nucleophile. Therefore, large size of donor atom
increases nucleophilicity.

(ii) Periodicity :
Nucleophilicity decreases from left to right in a period.

 In a group, nucleophilicity increases from top to bottom due to increases in size of donor atom, but
basicity decreases from top to bottom.
Acid strength : HI > HBr > HCl > HF
Basic strength : F¯ > Cl– > Br– > I–
Nucleophilicity : F¯ < Cl– < Br– < I–

(iii) Steric effects on nucleophilicity

Stronger base, yet weaker

nucleophile cannot approach
the carbon atom so easily.
(iv) The effect of the solvent  In polar protic solvent large nucleophiles are good, and the halide ions
show the following order

In DMSO, the relative order of reactivity of halide ions is

> > >

This effect is related to the strength of the interaction between nucleophile and solvent molecules of polar
protic solvent forms hydrogen bond to nucleophiles in the following manner :
 12 REACTION MECHANISM

(v) Relative nucleophilicity in polar protic solvent

> > > > > > > > > H2O

(vi)
Nucleophilicity Basicity Remarks
1. CH3¯ > NH2¯ > OH¯ > I¯ CH3¯ > NH2¯ > OH¯ > I¯ If donor atomis belong to
same period, nuclephilicity
and basicity order is same

2. SiH3¯ > PH2¯ > SH¯ > Cl¯ SiH3¯ > PH2¯ > SH¯ > Cl¯

3. F¯< Cl¯ < Br¯ < I¯ F¯> Cl¯ > Br¯ > I¯ In a group nucleophilicity
increases while basicity
decreases. on moving top to
bottom.

,,
4. OH¯ < SH¯ OH¯ > SH¯

,,
5. RO¯ < RS¯ RO¯ > RS¯

6. RO¯ > HO¯ Same If donor atom is same,

nucleophilicity and basicity
have same order
,,
7. , PhO¯, HO¯, RO¯ RO¯ > HO¯ > PhO¯ >

8. > (tetrahedral) (more resonance (extensive). [d–d bonds]

9. HO¯ > H2O

NH2¯ > NH3

CF3SO3¯ < PhCOO¯ < PhO¯ < RO¯ (Nucleophilicity)

 REACTION MECHANISM
13

2. Leaving group Ability/Nucleofugality :

The best leaving groups are those that become the most stable ion after they leave, because leaving group
generally leave as a negative ion, so those leaving group are good, which stabilise negative charge most
effectively and weak base do this best, so weaker bases are good leaving groups. A good leaving group
always stabilize the transition state and lowers its free energy of activation and there by increases the rate
of the reaction.
(a) Order of leaving ability of halide ion

> > >

(b) Other leaving groups are

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

(strong base)

(It is not a 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. F¯ < Cl¯ < Br¯ < I¯

2. CH3¯ < NH2¯ < OH¯ < F¯

3. R–COO¯ > PhO¯ > HO¯ > RO¯

4. SH¯ > OH¯

5. >
 14 REACTION MECHANISM

Nucleophilic substitution reaction (SN1)

3. Nucleophilic substitution reaction.

General reaction (RX + Nu¯  RNu + X¯)

3.1 Unimolecular nucleophilic substitution reaction (SN1) :

Nucleophilic substitution which involves two step process
(a) First step : - Slow step involves ionisation to form carbocation
R–g  R+ + g –
(b) Second step : - Fast attack of nucleophile on carbocation to result into product .
R+ + Nu –  R–Nu

3.1.1 SN1 Reaction of alkyl halide

Ionisation of
alkyl halide
    
Slow step (rds)

Characteristics of SN1 reactions :

1. It is unimolecular, two step process.
2. Carbocation intermediate is formed so rearrangement is possible in SN1 reaction.
3. It is first order reaction
4. Kinetics of the reaction Rate  [Alkyl halide]
Rate = k [(CH3)3C – X]
1
Rate of SN reaction is independent of concentration and reactivity of nucleophile.
5. Energetics of the SN1

Figure : Free energy diagram for the SN1 reaction.

6. Factor's affecting the rates of SN1
(i) The structure of the substrate : The Rds of the SN1 reaction is ionization step, in this step form a
carbocation. This ionisation is strongly endothermic process, rate of SN1 reaction depends strongly on
carbocation stability because carbocation is the intermediate of SN1 reaction which determines the
energy of activation of the reaction.
SN1 reactivity : 3° > 2° > 1° > CH3 – X
(ii) Concentration and reactivity of the nucleophile  The rate of SN1 reactions are unaffected by the
concentration and nature of the nucleophile
(iii) Nature of nucleophile:-
 Weak, neutral, mostly solvents (protic) itself functions as nucleophiles in SN1 reaction.
# In SN1 reaction, mostly the solvent functions as nucleophile. So SN1 reaction are termed as solvolysis
reaction.
water  hydrolysis
C2H5OH  ethanolysis
REACTION MECHANISM
15
CH3COOH  acetolysis
NH3  ammonolysis
SN2 reaction is disfavoured by strong, anionic nucleophiles which attacks faster before ionisation takes
place leading to SN2 mechanism.
For SN1 reactions, weak neutral nucleophiles are suitable and mostly solvent molecules function as
nucleophiles with oxygen and nitrogen as donor atoms.
OH2 + – H
R – X + H2O  R+ R – O – H    R – OH + HX

–
H
(iv) Effect of the solvent : the ionizing ability of the solvent :
Because to solvate cations and anions so effectively the use of a polar protic solvent will greatly increase
the rate of ionization of an alkyl halide in any SN1 reaction. It does this because solvation stabilizes the
transition state leading to the intermediate carbocation and halide ion more than it does the reactant,
thus the energy of activation is lower.

R – X (Solvolysis)

Solvated ions
(v) The nature of the leaving group  In the SN1 reaction the leaving group begins to acquire a negative
charge as the transition state is reached stabilisation of this developing negative charge at the leaving
group stabilizes the transition state and ; this lowers the free energy of activation and thereby increases
the rate of reaction.

leaving ability of halogen is > > > >

7. Stereochemistry of SN1 reactions  In the SN1 mechanism, the carbocation intermediate is sp2
hybridized and planar, A nucleophile can attack on the carbocation from either face, if reactant is chiral
than after attack of nucleophile from both faces gives both enantiomers of the product, which is called
racemization.
Mechanism of racemization (SN1  

e.g. H2 O acetone
   + HBr (3° alkyl halide hence no SN2 reaction)

e.g. (Racemic Mixture)

 16 REACTION MECHANISM

Nucleophilic substitution reaction (SN2)

4. SN2 Reaction of alkyl halide :

Mechanism :

 +

Characteristic of SN2
1. It is bimolecular, one step process
2. It is second order reaction because in the RDS two species are involved
3. Kinetics of the reaction  rate  [alkyl halide] [nucleophile]
rate = k[alkyl halide] [nucleophile]
If the concentration of alkyl halide in the reaction mixture is doubled, the rate of the nucleophilic
substitution reaction is double. If the concentration of nucleophile is doubled the rate of reaction is also
double. If the concentration of both are doubled then the rate of the reaction quadriples.
4. Energetics of the reaction :

Figure : A free energy diagrams for SN2 reaction

5. No intermediates are formed in the SN2 reaction, the reaction proceeds through the formation of an
unstable arrangment of atoms or group called transition state.
6. The stereochemistry of SN2 reactions  As we seen earlier, in an SN2 mechanism the nucleophile
attacks from the back side, that is from the side directly opposite to the leaving group. This mode
of attack causes an inversion of configuration at the carbon atom that is the target of nucleophilic
attack. This inversion is also known as walden inversion.

Inversion
  

7. Factor's affecting the rate of SN2 reaction  Number of factors affect the relative rate of SN2 reaction,
the most important factors are
(i) Effect of the structure of the substrate 
Order of reactivity in SN2 reaction : – CH3 > 1° > 2° >> 3° (unreactive)
the important factor behind this order of reactivity is a steric effect. Very large and bulky groups can
often hinder the formation of the required transition state and crowding raises the energy of the transition
state and slows down reaction.
(ii) Concentration and reactivity of the nucleophile
As nucleophilicity of nucleophile increases rate of SN2 increases.
– Anionic nucleophiles mostly give SN2 reaction
– A stronger nucleophile attacks upon -carbon with faster rate than the rate of departing of leaving
group. R– > NH2– > OH– > F–
 REACTION MECHANISM
17
–
RO > ROH
NaOH > H2O
NH3 > H2O

Table :

(iii) The effect of the solvent: Polar aprotic solvent have crowded positive centre, so they do not solvate
the anion appreciably therefore the rate of SN2 reactions increased when they are carried out in polar
aprotic solvent.
(iv) The nature of the leaving group  Weaker bases are good leaving groups. A good leaving group always
stabilize the transition state and lowers its free energy of activation and thereby increases the rate of
the reaction. Order of leaving ability of halide ion F¯ < Cl¯ < Br¯ < I¯
KOH
e.g. (CH3)2CHCH2CH2 – Br  
 (CH3)2CHCH2CH2 – OH
H2O

e.g.

Na PhCH Br CH2 – O – CH3

e.g. MeOH 
 2
   
Benzylmethyl ether
1 2
Comparision between SN / SN reaction
Conditions/ Characteristics :
SN2 SN1

1. Energetic

2. Kinetics r  [RX] [NU:] r  [RX]

3. Stereochemistry inversion racemisation
4. Rearrangement not possible possible
5. Activation energy Ea S > Ea SN1 (more) less
N2

6. Nature of R – X Me – X > R– CH2 –X > R2 – CH – X > R3–CX R3CX > R2CHX > RCH2X > CH3X

7. Nucleophile strong anionic Weak neutral

 18 REACTION MECHANISM

R– > NH2– > OR– > OH– H2O > MeOH > EtOH > NH3
8. Leaving group – > Br– > Cl– > F– (same)
SN2 SN1
9. Solvent Polar aprotic Polar protic

10. Temperature High Low

Elimination reaction (E1)

5. Elimination reactions :
In an elimination reaction two atoms or groups (YZ) are removed from the substrate and generally
resulting into formation of  bond.
| |
E lim ination
CC    
 YZ
| |
Y Z
-elimination : When two groups are lost from the same carbon atom to give a carbene (or nitrene).
This is also called 1–1 elimination.
 C–C

-elimination : When two groups are lost from adjacent atoms so that a new  bond is formed. This
is also called 1–2 elimination.
 C=C

–elimination : It is also called 1–3 elimination, In this a three membered ring is formed.



5.1 E1 Reaction : Proton and leaving group depart in two different step.
(a) First step : - Slow step involves ionisation to form carbocation
(b) Second step : Abstraction of proton

5.1.1 E1 Reaction of alkyl halide :

Mech.

Step 1 : Formation of the carbocation (RDS)

Step 2 : Base ( ) abstracts a proton (fast)

+ B – H

Characteristics of E1 reaction :
(i) It is unimolecular, two step process.
 REACTION MECHANISM
19
(ii) It is first order reaction.
(iii) Reaction intermediate is carbocation, so rearrangment is possible
(iv) In the second step, a base abstracts a proton from the carbon atom adjacent to the carbocation,
and forms alkene.
(v) Kinetics  Rate  [Alkylhalide]
Rate = k [Alkylhalide]

(vi) Energetics  The free energy diagram for the E1 reaction is similar to that for the SN1 reaction.

CH3
|
e.g. CH3  CH2  C  CH3  +
|
Br

e.g. 

e.g.

Elimination reaction (E2)

6. E2 Reaction :
6.1 E2 Reaction of alkyl halide :
Dehydrohalogenation is the elimination of a hydrogen and a halogen from an alkyl halide to form an
alkene. Dehydrohalogenation can take place by E1 and E2 mechanism.

(i) Hot alcoholic solution of KOH EtO¯ / EtOH (ii) NaNH2 (iii) t-BuO¯ K in t-BuOH
Mechanism

  + BH
20 REACTION MECHANISM

Characteristics of E2 reaction 
1. This is a single step, bimolecular reaction
2. It is a second order reaction
3. Kinetics  Rate  [R – X] [Base]

Rate = k [R – X] [ ]
4. Rearrangment is not possible
5. For the lower energy of activation, transition state must be stable
6. E2 follows a concerted mechanism
7. The orientation of proton & leaving group should be antiperiplanar.
8. Here  – H is eliminated by base hence called  elimination
9. Positional orientation of elimination  In most E1 and E2 eliminations where there are two or more
possible elimination products, the product with the most highly substituted double bond will predominate.
This rule is called the saytzeff or zaitsev rule.

For example : Dehydrohalogenation of 2-bromo-2-methylbutane can yield two products.

Reactivity towards E2  R – I > R – Br > R – Cl > R – F

e.g. +

CH3
|
e.g. CH3  C  Br +  + H 2O +
|
CH3
 REACTION MECHANISM
21
Formation of the Hoffmann product
Bulky bases can also accomplish dehydrohalogenations that do not follow the saytzeff rule. Due to
steric hindrance, a bulky base abstracts the proton that leads to the most highly substituted alkene.
In these cases, it abstracts a less hindered proton, often the one that leads to formation of the least
highly substituted product, called the Hoffmann product.

H CH3
| |
CH3  C  C  CH2 +
| | |
H Br H

Stereospecific E2 reactions
The E2 is stereospecific because it normally goes through an anti and coplanar transition state. The
products are alkene, and different diastereomers of starting materials commonly give different diastereomers
of alkenes.

Base
H
Ph Ph
Ph H

CH3 Ph
H CH3
Br H
Br

CH3
Ph H
Ph Ph
CH3 Ph
H

E1 Cb Reaction (Unimolecular conjugate base reaction)

7. E1 Cb Reaction (Unimolecular conjugate base reaction)

In the E1 Cb, H leaves first and then the X. This is a two step process, the intermediate is a carbanion.

Mechanism :

Step - I Consists of the removal of a proton, , by a base generating a carbanion

H
| |
CC X
| |
Step - II Carbanion looses a leaving group to form alkene

 –C  C –
| |
22 REACTION MECHANISM

Condition : For the E1 CB, substrate must be containing acidic hydrogens and poor leaving groups.

e.g. 

e.g.  X2C = CF2

e.g.  R2–C = O +