Introduction to Organic

Reaction Mechanism

M.Sc. Industrial Chemistry

Industrial Organic Chemistry

101310105
Unit 2 1
 Syllabus
• Unit-1: Preparations and applications of following reagents:
Aluminum tertiary butoxide, Boron tri fluoride, DCC, Ozone,
Platinum, Palladium, Selenium.
• Unit-2: Organic reaction mechanism: Introduction, meaning
of organic reaction mechanism, Nature of fission of covalent
bond, bond formation, types of organic reaction, classification
of reagents, reaction intermediate, concept used in organic
reaction mechanisms.
• Unit-3 Name reactions: Aldol condensation, Cannizzaro
reactions, Houben Hoesch, Knoevenagel, Wurtz, Wurtz-fittig.
• Unit 4: Name reactions: Diels alder reactions, Perkin, Dakin,
Wolf kishner, Leucarts, Meerwin pondorff verely.
2
 Meaning of organic reaction mechanism
• A chemical equation indicates the reactant and the final
products of the reaction.
• It nearly indicates how the reaction proceeds.
• The steps of an organic reaction depicting the breaking
and making of new bonds of carbon atoms in the reactant
• Substrate leading to the formation of the final products
through transitory intermediates are often referred to as
its mechanism.
• In brief, the mechanism of an organic reaction is the
detailed step by step know-how of a chemical reaction.
3
• Organic reaction mechanism may also be defined as the
description of the path followed by the reactants as
they are transformed into products.
• The description should be complete,
• It must cover the detailed changes that occur in the
positions of all atoms and bonds;
• The changes in the energy of the system and the
kinetics of the changes accompanying these various
processes.
• Very few reaction mechanism have been said to be
completely proved.
4
• All the same a proposed mechanism should explain the
following facts:
• Main products and side products
❑ Intermediates; observable where possible
❑ Relative reactivity of different reagents and substrates
❑ Stereo chemical aspects
❑ Variation in rate (and products) with different solvents
• The predictions based upon the basis of the reaction
mechanism should come true.
• The chief advantage of the mechanistic approach to organic
chemistry is to explain how a reaction proceeds and even
forecast the outcome of the conditions of a certain reaction.
5
• ELECTRON DISPLACEMENT EFFECTS
• There are four types of electron displacement
mechanisms frequently observed in organic
molecules
a. Inductive effect
b. Mesomeric effect;
c. Electromeric effect;
d. Hyper-conjugative effect.
• Inductive effect. When a carbon atom is joined to a hydrogen
atom by a covalent (σ) bond (C— H) such as in alkanes, the
shared electron-pair is symmetrically placed between them.

• Fig.: Electron cloud in the orbitals C—X and C—Y whose symmetry is disturbed in
the opposite directions.

• If a substituent X having higher electronegativity or electron-

attracting power than the C atom, in the bond C—X, the shared
electron pair will be displaced away from the carbon atom and
toward the more electronegative substituent X.
• As a result of the minor displacements of the bonding electron-pair,
the joined atoms develop small fractional charges on them as
illustrated below.

• The polarization thus induced in the substrate molecule is of a

permanent nature.

• The permanent effect whereby polarity is induced on the carbon atom

and the substituent attached to it due to minor displacement of
bonding electron pair caused by their different electronegativities, is
known as Inductive effect or simply as I-effect.
• When the substituent linked to carbon is electron-attracting (X), it
develops a negative charge and it is said to exert a negative inductive
effect or -I effect.

• If the substituent Y bonded to carbon atom is electron-releasing, it

acquires a positive charge and the inductive effect produced is called
+ I effect.
• Let us consider an organic molecule having a highly electron-
attracting substituent X attached to the terminal carbon atom.

• The substituent X pulls towards it the electron-pair between s-carbon

and X.
• This produces a slight positive charge (l) on the or-carbon.
• When a small positive charge is acquired by the α-carbon it will tend
to attract to itself the electron-pair linking it with β-carbon 9
• Denoting the decreasing magnitude of positive charge on α,
β and γ carbon atoms by δ+, δδ+ and δδδ+ the inductive
effect relayed along the carbon chain may be represented
as follows.

• With an electron-pumping substituent Y, the inductive

effect will be reversed and the situation would be
• Some common groups which cause negative or positive I-effect are
given below in order of their decreasing effect:
• (a) - I effect groups (electron-attracting)
NO2>F> COOH> Cl> Br >1> OH

• (b) +I effect groups (electron pumping)

• (CH3)2C- > (CH2)2CH- > CH3CH2- > CH3-

tertiary butyl > isopropyl > ethyl > methyl

• In general the Inductive effect of the alkyl groups is in the order 3° >
2° > 1°groups.
• In other words the electron-releasing power of a primary carbon (1°)
is less than that of a secondary carbon (2°), while that of a tertiary
carbon (3°) is the maximum.
• Electromeric Effect: Polarization produced in a substrate
molecule containing multiple bonds.
• When a double or a triple bond is exposed to attack by an
electrophilic reagent, a pair of bonding electrons is
transferred completely from one atom to the other.
• The atom that takes charge of the electron-pair becomes
negatively charged and the other positively charged.
• E.g.
• This is a purely temporarily effect and remains only in the
presence of the electrophilic reagent.
• As soon as the attacking reagent is removed, the polarized
molecule reverts to its original electronic state:

• The effect which causes a temporary polarization in the

substrate molecule at the seat of a multiple bond by shift of
an electron-pair from one atom (or part) to the other under
the influence of an elecirophilic reagent, is called
Electromeric effect (electro = electron meros = part).
• The electromeric effect differs from the inductive effect in
the following respects.
 Electromeric Effect Inductive Effect
➢ Shown by substrate molecules
➢ Shown by mclecules containing single.
containing double (C=C) or triple
Bonds
(CC) bonds
➢ Takes place under the influence of a
➢ Takes place when the molecule is substituent (electron-attracting or
ex electronpumping) linked to the terminal
carbon atom
➢ Polarity caused by complete
➢ Polarity caused by the displacement of
transfer of an electron-pair to one
bonding electron-pair from one atom
of the two atoms joined by multiple
towards the other
bond
➢ The charge developed by the carbon
➢ The charge acquired by the atom linked to the substituent is small
that gains the electron-pair is 4-1 fractional δ+ or δ- according as the
while the other gets —1. substituent is electron attracting or
electron pumping
➢ Temporary effect disappears with
➢ Permanent effect depending on the
the removal of the attacking
structure of the substrate molecule.
reagent.
• Mesomeric Effect: Causes permanent polarization.
• This electron displacement is relayed through π-electrons of
multiple bonds in the carbon chain of the molecule.
• The mesomeric effect is applicable to those systems which have
an extended chain with conjugate π bonds (alternate σ and π
bonds).
• For this reason this effect is also referred to as Conjugative
Effect.
• The π electrons get delocalized as a consequence of mesomeric
effect, giving a number of resonance structures of the molecule.
• When an electron pumping or electronic withdrawing group is
conjugated with a π bond or a set of alternately arranged σ and π
bonds, the electron displacement is transmitted through π
electrons in the chain.
• Consider a carbonyl group (>C=O) to be linked with a
conjugated system as CH2=CH-CH=CH-CH=O.
• The π electrons of the carbon-oxygen bond get displaced
toward oxygen—the more electronegative atom, giving the
resonance structures as

• In the whole molecule, this polarization can be tratnitted

further via the it electrons as
• Mesomenc effect like the inductive effect may be + or -
and is usually denoted by +M or —M.
• A group of atom is said to have +M effect when the
direction of electron displacement is away from it.
• Such groups have lone pair of electrons, furnish the pair for
conjugation with an attached unsaturated system.
• The groups have one or more lone pairs of electrons and
have + M effect.
• The presence of an amino group —NH, at the end of a
conjugate π bond system brings about electron
displacement as
• The +M effect of halogen atom (-Br:) accounts for low reactivity of
the halogen atom (getting attached by a double bond) in vinyl halides
and aryl halides.

• On the other hand, a group or atom is said to have -M effect when

the direction of electron displacements is toward it.
• The groups such as >C=O, -NO2, -C≡N, -SO3H etc., have -M effect
owing to the presence of a highly electronegative atom like oxygen
or nitrogen functioning as an electron sink’.
• The —M effect of the nitro group:
• Hyperconjugative Effect: Hyperconjugative effect results
in an electron displacement towards the double bond
carbon marked by an asterisk.
• Baker and Nathan suggested that Hyperconjugative effect
takes place through the interaction of σ-electrons of the
carbon-hydrogen bond with π electrons of the double
bond.
• The three C—H bonds of the methyl group in the
propylene molecule contribute to this effect as follows:
 Nature of the Fission of Covalent Bonds
• Most organic reactions involve the fission and formation of
covalent bonds.
• There is different ways in which a covalent bond can break.
• Depends upon
• The nature of the given organic compound,
• The nature of attacking reagent
• The reactions conditions
• A covalent bond (represented as a dash, —) between two
atoms of the given compound may be broken in two different
ways forming different types of reaction intermediates.
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• The different possibilities are illustrated below by
considering a covalent bond between two atoms C and X.
A. Homolytic cleavage or Homolytic fission or Homo-
polar fission
• The breaking of a covalent bond in a manner so that each of the two
species formed retains one electron of the shared pair is called a homolytic
fission.
Homolytic Fission ∙
𝐶: 𝑋 𝐶 + 𝑋∙
• This leads to the formation of highly reactive neutral species containing
odd or unpaired electrons.
• Such species are known as free radicals.
• The reactions which, proceed through homolytic cleavage, i.e. through the
formation of intermediate free radicals are known as free radical
reactions.
21
(b) Heterolytic fission or Heterolytic cleavage of Hetero-
polar fission
• The breaking of a covalent bond in manner in which ions are
formed as reaction intermediates is called heterolytic fission.
• This involves the breaking of a bond in such way that both the
electrons of the shared pair are carried away a one of them.
This can take place in two different ways
1. The molecule C:X breaks up in such a way that C retains the
covalently shared electron pair i.e. 𝐶:− , leaving X as
positively charged, i.e. 𝑋 + .
Heterolytic Fission −
𝐶: |𝑋 𝐶 : + 𝑋+

22
II. The molecule C:X breaks up in such a way that X
retains the covalently shared electron pair, i.e. :X-,
leaving positively charged, i.e. C+.

Heterolytic Fission
𝐶|: 𝑋 𝐶 ++ ∶ 𝑋−
• The group which contains negatively charged carbon
atom as in the first type of heterolytic fission is called a
carbanion.
• The group which contains positively charged carbon
atom as in the second type of heterolytic fission is called
a carbonium ion.

23
• The reactions which proceed through heterolytic fission,
i.e. in which electron pairs are transferred from one
species to another in the substrates having at least one
covalent bond, are called polar or ionic reactions.
• Reactions in which carbonium ions are formed as
intermediates are said to proceed by a carbonium ion
mechanism.
• On the other hand, reactions in which carbanions are
formed at intermediates are said to proceed by carbanion
mechanism.

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• The carbon atom in carbonium ion, carbanion and free
radical is trivalent
• The number of electrons in the valence shell of carbon in
these species is 6, 8 and 7 respectively.
• But we know that carbon has tendency to acquire eight
electrons to attain stability.
• Therefore, carbonium ion, carbanion and free radical are
very reactive because carbon in these tends to acquire
eight electrons.

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• It can be concluded that there occurs the cleavage of covalent bond in
organic compounds either in heterolytic or homolytic way.
• However, certain reactions are known, especially those which are
taking place at high temperatures, the covalent bond may cleaved
simultaneously in homolytic as well as heterolytic ways.
• For example, cyclobutane on pyrolysis may form ethylene in both the
ways. Type equation here.

26
• Most of the organic reactions are known to proceed by
following either free radical mechanism or polar
mechanisms.
• However, certain reactions are known which occur by
electron transfer in cyclic order within a molecule or
between molecules.

Such mechanism is known as cyclic or molecular mechanism 27

 Bond formation
• Whenever a covalent bond in an organic reaction is cleaved, it is
immediately followed by the bond formation which may occur
I. Either in a next and separate step
II. Simultaneously with the help of bond fission
• For example, the two possibilities is the substitution reaction of an
:OH- ion with the molecule CH3Cl.

Bond Fission
𝐻3 𝐶|: 𝐶𝑙 𝐶𝐻3+ +∶ 𝐶𝑙 −

Bond Formation
𝐶𝐻3+ +∶ 𝑂𝐻 − 𝐶𝐻3 : 𝑂𝐻
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• In this case there occurs the formation of carbonium ion,
CH3+ as an intermediate species with a short lifetime.

29
• In this case the half-life of the intermediate species is
zero and is therefore, not formed.
• However, the reaction in such a case is assumed to
proceed through an intermediate "transitory state' in
which the cleavage of old bond and formation of new
bond take place simultaneously.
• This can be represented in a best manner as follows:

30
The characteristics of two main types of reactions which have been
classified on the basis of mechanism viz. free radical and ionic.
S.No. Free radical reaction
These are favoured by light, high
(i) temperature and such catalyst as
organic peroxides
These are inhibited by substances such
as quinol which combine with free
(ii)
radicals, thereby stopping the chain
mechanism
These reactions usually take place in
(iii)
vapour phase and non-polar solvents
These are frequently autocatalytic and
(iv) exhibit an induction period before
reaction commences
Aromatic substitution reactions of this
(v)
type may not follow orientation rules
These occur in gas (vapour) phase or in
(vi)
non-polar solvents
Ionic reaction
These are unaffected by light, free
radicals and peroxides
These are catalyzed by acids and bases
which promote ionization. These are not
inhibited by quinol. They take place in
polar solvents
These reactions rarely take place in
vapour phase. These are largely affected
by nature of the solvents
These usually follow 1st or 2nd order
kinetics but not autocatalytic. Rate of
reaction increases with temperature
Aromatic substitution of the ionic type
may follow orientation rules
Ionizing solvents are usually found to be
best media for such reactions
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 Types of Organic Reactions
• Reactions have been classified into two main categories
1. Heterolytic reactions
2. Homolytic reactions
Heterolytic reactions: These are the reactions which involve a
heterolytic fission of the bond resulting in the formation of a carbanion
or a carbonium ion as an intermediate
Homolytic reactions: These are the reactions which involve a
homolytic fission of the bond resulting in the formation of a free radical
as an intermediate
• Depending upon the nature of the reaction which the intermediate species
(carbanion, carbonium ion or free radical) undergoes the various types of organic
reactions which we across are as follows:
1. Substitution or displacement reactions
2. Addition reactions
3. Elimination reactions
4. Rearrangements
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5. Molecular reactions
1. Substitution reactions
• Reactions proceeding by the replacement or substitution of one or
more atoms or groups of a compound by other atoms or groups are
referred to as substitution reactions.
• They are known to proceed by a free radical or ionic mechanism.
• Free radical substitution. These reactions are initiated by free
radicals, The replacement of hydrogen atoms in alkane molecules
is probably the best example of this type.
ℎ𝜗
𝐶𝑙2 2𝐶𝑙 .
(free radicals)
ℎ𝜗
𝐶𝐻4 + 𝐶𝑙 . 𝐶𝐻3 𝐶𝑙
Methane Methyl chloride
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Ionic Substitution reactions
• Substitution reactions may be brought about by electrophiles or
nucleophiles acting as, attacking reagents.
• Most of such reactions are initiated by Nucleophiles, while
➢Substitution reactions involving electrophiles are very rare.
• (i) Electrophilic substitution (SE) When a substitution reaction involves
an attack by an electrophile, the reaction is referred to as SE (here S
stands for substitution and E for electrophile).
• The substitution reactions of benzene are the best examples of
electrophilic substitution e.g., the nitration of benzene is brought about
with the help of nitronium ion NO2+ (an electrophile).

• This type of reaction takes place mostly in aromatic systems where the
high electron density attracts electrophile.
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• (ii) Nucleophilic substitution (SN). If a substrate is attacked by a
nucleophile in a substitution reaction, the reaction is represented
as SN (S for substitution and N for a nucleophile).
• A general nucleophilic substitution reaction may be represented as
N: + R-X → N-R + X:
• where N is the attacking nucleophile, RX the substrate, NR the
substitution product and X is the leaving group.
• Such reactions may be classed into two further divisions viz ...
• SN1 and SN2 depending upon whether the reaction in question is a
first order or second order one.
• Familiar example's of the two types are:
• SN1 type. Conversion of a tertiary alkyl
• SN2 type. Conversion of primary alkyl halide into a primary
alcohol 35
• SN1 type: Conversion of a tertiary alkyl halide into a
tertiary alcohol by substitution of -OH group by Cl atom.

36
• SN2 type: Conversion of primary alkyl halide into a
primary alcohol.

• Some nucleophilic substitution reactions of primary

importance are cited below :

37
 2. Addition reactions
• An addition reaction is one in which two substances combine to form a
single compound.
• This type of reaction generally occurs if the substance contains either a
double or a triple bond.
• In addition reactions, the attacking species may be a nucleophile, an
electrophile or a free radical.
• Addition by electrophile is exemplified by the reaction of HBr with
ethylene.
• In this reaction, the electrophile H+ approaches a double bond when a
bond is formed by converting the pair of π electrons into σ bond.
• The resultant carbonium ion then combines with a nucleophile, forming
the addition product.

38
 • Addition by nucleophile is exemplified by the reaction of
HCN with acetone.
• In this reaction, the nucleophile 𝐶𝑁 − attacks the double
bond when π electrons of the double bond get shifted to the
adjacent atom.
• The reaction is then completed by the combination of this
anion with 𝐻+ .
𝐵𝑎𝑠𝑒
𝐻𝐶𝑁 𝐶𝑁 −

• Addition by free radicals is exemplified by addition of HBr to a

double bond in the presence of peroxides.
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 Elimination reaction
• Elimination reaction is a type of reaction that is mainly used to
transform saturated compounds (organic compounds which
contain single carbon-carbon bonds) to unsaturated compounds
(compounds which feature double or triple carbon-carbon bonds).
• Besides, it is an important method for the preparation of alkenes.

• An elimination reaction is a type of chemical reaction where several

atoms either in pairs or groups are removed from a molecule. The
removal usually takes place due to the action of acids and bases
or the action of metals. It can also happen through the process of
heating at high temperatures. 40
• Important Methods of Elimination Reaction
• Normally, elimination reactions are distinguished by the kind of
atoms or groups of atoms that leave the molecule. Due to this,
there are two main methods involved in this type of reaction;
• Dehydration
• Dehydrohalogenation
• In the dehydration method, there is the elimination of a water
molecule mostly from compounds such as alcohol. Sometimes,
this method is also called a Beta elimination reaction where the
leaving group and H are placed at neighbouring carbon atoms.
On the other hand, in dehydrohalogenation, there is a removal
of a hydrogen atom and a halogen atom.
• Some other common types of elimination reactions are α-
elimination and γ- and δ-elimination.
41
• Mechanism Of Elimination Reaction
• The elimination reaction consists of three fundamental
events, and they are;
1. Proton removal.
2. Formation of C-C pi bond.
3. Removal of the leaving group.
• Depending on the reaction kinetics, elimination reactions
can occur mostly by two mechanisms namely E1 or E2
where E is referred to as elimination and the number
represents the molecularity.

42
• E1 Reaction
• In the E1 mechanism which is also known as unimolecular elimination, there are usually
two steps involved – ionization and deprotonation.
• During ionization, there is a formation of carbocation as an intermediate. In deprotonation,
a proton is lost by the carbocation.
• This happens in the presence of a base which further leads to the formation of a pi-bond in
the molecule.
• In E1, the reaction rate is also proportional to the concentration of the substance to be
transformed.
• It exhibits first-order kinetics.

• The E1 mechanism shares the features of the SN1 reaction .

• The initial step is the formation of a carbocation intermediate through the loss of the
leaving group.
• This slow step becomes the rate-determining step for the whole reaction. 43
• E2 Reaction
• In an E2 mechanism which refers to bimolecular elimination is
basically a one-step mechanism.
• Here, the carbon-hydrogen and carbon-halogen bonds mostly break
off to form a new double bond.
• However, in the E2 mechanism, a base is part of the rate-determining
step and it has a huge influence on the mechanism.
• The reaction rate is mostly proportional to the concentrations of
both the eliminating agent and the substrate.
• It exhibits second-order kinetics.
• The E2 mechanism can generally be represented as below. In the
below-mentioned representation, B stands for base and X stands for
halogen.

44
 4. Rearrangement reactions
• A rearrangement reaction is one in which there occurs the
movement of an atom or a group from one atom to another within
the molecule.
• The migrating groups are carbanions, carbonium ions or free
radicals. Some examples of rearrangements are as follows
I. When n-alkanes are heated with AlCl3 at 300oC, they undergo
rearrangement to form branched-chain alkanes

II. When alkyl halides are heated at about 300oC or at a lower

temperature in the presence of AlCl3 as catalyst, they undergo
rearrangement, e.g.1-bromobutane yields 2-bromobutane
45
 CLASSIFICATION OF REAGENTS
• When a reaction takes place between two substances, one
of the substances is generally regarded as the attacking
reagent while the other is considered to be a substrate, i.e.
the substance which gets attacked.
• The substances formed as a result of the reaction are
known as the products.
𝑆𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒 + 𝐴𝑡𝑡𝑎𝑐𝑘𝑖𝑛𝑔 𝑟𝑒𝑎𝑔𝑒𝑛𝑡 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
• Attacking reagent and substrate are purely relative terms.
• A particular substance may be treated as an attacking
reagent in one reaction and as a substrate in another. 46
 CLASSIFICATION OF REAGENTS
• The reactant represents the substance which is attacked
and is usually known as substrate.
• The substance due to whose presence the substrate
undergoes a change is called attacking reagent.
• It is the usual convention that in reactions involving an
organic substance and inorganic substance, the inorganic
substance is always taken as the attacking reagent and the
organic substance as the substrate, e.g.,
➢In the reaction between iodoethane (ethyl iodide) and aqueous
potassium hydroxide, it is the iodoethane which is the substrate.
𝐶2 𝐻5 𝐼 + 𝐾𝑂𝐻𝑎𝑞 → 𝐶2 𝐻5 𝑂𝐻 + 𝐾𝐼
Substrate 47
• When the reaction is taking place between two organic substances,
the molecule supplying the carbon atom to the new bond is called
the substrate while the other attacking reagent.
• For example, in the reaction between ethanoic acid (acetic acid) and
ethanol, it is ethanoic acid which is the substrate because it is
supplying the carbon atom towards the formation of the new C-O
bond.

• When a carbon-carbon bond is formed, then one of them is

arbitrarily chosen as the substrate, e.g. in the reaction between
iodoethane and sodium salt of diethyl propanedioate (diethyl
malonate) it is the former (ethyl iodide) which is taken as the
substrate.
𝐶𝐻3 𝐶𝐻2 𝐼 + 𝑁𝑎𝐶𝐻2 (𝐶𝑂𝑂𝐶2 𝐻5 )2 → 𝐶𝐻3 𝐶𝐻2 𝐶𝐻(𝐶𝑂𝑂𝐶2 𝐻5 )2 + 𝑁𝑎𝐼 48
• In a reaction when the substrate becomes cleaved
(broken), then the part of the molecule not containing the
carbon is known as leaving group.
• Depending upon their nature, the attacking reagents may
be classified into three categories
1. Electrophilic reagents
2. Nucleophilic reagents
3. Free radicals

49
 1. Electrophilic reagents
• An electrophile or an electrophilic reagent is a species having an atom
with incomplete octet and attacks an area of high electron density in the
substrate.
• Electrophilic means electron-loving, i.e. these reagents are in search of
high electron density sites in the substrate.
• Such reagents can accept a share in an electron pair belonging to other
atoms in a molecule. Therefore, these are also known as Lewis acids.
• In general, the electrophile include all cations, dipolar molecules or
molecules that can be readily polarized, Lewis acids, i.e. molecules
which have atoms with incomplete octet, etc.
• However these electrophiles can be broadly classified into two types
I. Positive electrophiles
II. Neutral electrophiles

50
 i. Positive electrophiles
• They are those species which carry positive charge.
Examples of these are proton, cations and the carbon
radicals carrying a positive charge (carbonium ions).
Some Important examples of positive electrophiles are as
follows :
𝐻 + , 𝐵𝑟 + , 𝐶𝑙 + , 𝑁𝑂2+ , 𝑁𝑂+ , 𝑁𝐻4+ , 𝐻3 𝑂+ , 𝑅3 𝐶 + , 𝐴𝑟 − 𝑁 ≡ 𝑁 +
• The positive electrophile attacks the substrate, rich in
electrons and accepts an electron pair for sharing, and
form neutral molecule.

51
 ii. Neutral electrophiles
• They are those species which lack positive charge. Examples
of these are BF3, AlCl3, ZnCl2 and carbon radicals having six
electrons in the outermost orbit.
• All these behave as electron seeking reagents because they are
short of a pair of electrons to attain stable configuration.

The star indicates the atom which is accepting electrons from the substrate. 52
• A neutral electrophile attacks the electron rich
substrate, forming a negatively charged molecule.

• Reactions involving electrophilic reagents are known

as electrophilic reactions.

53
 2. Nucleophilic reagents
• A nucleophilic reagent or a nucleophile (i.e. nucleus loving) is a
reagent having at least one unshared pair of valence electrons.
• Due to the presence of unshared pair of electrons, such a reagent is
in search of an electron deficient site where it can share its
electrons.
• In general, nucleophiles include all those anions and molecules
(Lewis base) with unshared electron pair and which have a tendency
to donate electron pair.
• As the nucleophiles are capable of donating electron pairs, they are
considered as Lewis bases.
• Like electrophiles, nucleophiles are also of two types, namely
• 1. Negative nucleophiles
• 2. Neutral nucleophiles
54
i. Negative nucleophiles
• They are the species which carry an excess of electron pair
and carry negative charge.
• Examples of these are halide ions, alkoxy ions, hydroxyl ion,
and the carbon radicals carrying a negative charge
(carbanion).
• Some important example of negative nucleophiles are as
follows:

• Negative nucleophiles attack on the positively charged substrate

forming a neutral molecule, e.g.

55
 ii. Neutral nucleophiles
• They are the species which are rich in electrons due to the presence
of unshared electrons pair, but they are electrically neutral.
• Important examples are as follows:

• Neutral nucleophiles attack on the positively charged substrates

forming positively charged product.

• The reactions which involve the attack of nucleophiles are known

as nucleophilic reactions, e.g. nucleophilic addition and substitution
reactions.
56
• The reactions which involve the attack of nucleophiles are known as
nucleophilic reactions, e.g. nucleophilic addition and substitution reactions.
• The differences between nucleophiles and electrophiles are as under
S.No Nucleophilic entities Electrophilic entities
(Nucleophiles) (Electrophiles)
(i) They are electron rich They are electron deficient
(ii) They provide an electron pair They accept an electron pair
(iii) They attack on electron deficient They attack on electron-rich atoms.
atoms
(iv) They are Lewis bases They are Lewis acids
(v) They have an unshared pair of They have an empty orbital which
electrons not holding too strongly receives the electrons pair from the
to the atomic nucleus (generally nucleophile
atoms of groups V and VI of the
periodic table)
(vi) They increase their covalency by They form an extra or alternative bond
one unit with the nucleophile
(vii) They are often anions They are often cations
57
 REACTION INTERMEDIATES
• The nature of the intermediates that are supposed to be formed in
the intervening steps between the reactants and the products are
important.
• These transient intermediates are known as reaction intermediates.
• The reaction intermediates vary in their stabilities.
• Their half-lives range from fraction of a second to several minutes.
• All the intermediates cannot be isolated but their existence is
proved by spectroscopic studies.
• The most important of these intermediates are molecules having
carbon atoms in abnormal valence states.
• They are called free radicals, carbonium ions, carbanions,
enamines, carbenes, nitrenes, benzynes.
58
 1. Free radicals
• Any species which is having an odd or unpaired electron
is called a free radical.
• Free radicals are electrically neutral. But they have
unpaired electrons.
• Therefore, they have tendency to pair up and hence these
are highly reactive species.
• The methyl free radical has planar structure in which
carbon is in sp2 hybridized state.

59
• The three sp2 hybrid orbitals of carbon form bonds with
the three alkyl groups whereas the odd electron is lying in
the unused p-orbital.
• The relative order of stabilities of the common free
radicals is as follows
• Benzyl > Allyl > Tertiary > Secondary > Primary >
Methyl > Vinyl
• Extra stability of the aromatic and allyl radicals has been
attributed to their resonance.
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 2. Carbonium ions
• A carbonium ion is a cation in which the positive charge is
carried by a carbon having only six electrons in its valence
shell, i.e. carbon atom lacks a pair of electrons in its valence
shell.
• A carbonium ion may be assumed to be a fragment of a
molecule in which an atom or group bonded to a carbon has
been removed along with the pair of bonding electrons.
• For example, a methyl carbonium ion would be formed if a
hydroxide ion is removed from a molecule of methyl alcohol.

61
• Carbonium ions have been classified as primary, secondary or
tertiary according as the carbon having the positive charge is
primary, secondary or tertiary in nature.
• In addition, methyl carbonium ion having only one carbon is
regarded as a special case.

• The carbonium ions which are formed as reaction

intermediates are very reactive.
• The reason for their reactivity is that the central carbon atom
has only six electrons in the outer shell and has a marked
tendency to complete its octet.
62
 Formation of Carbonium ions
• The carbonium ions may be formed in solution, either in
free state or as ion pairs.
• Some more stable ones have been obtained as solid states.
• The carbonium ions are formed in the following ways
I. Direct ionization
II. By protonation of unsaturated compounds
III. By the protonation of atom having loan pair of electrons
IV. By the protonation of alkyl or acyl halides
V. By the decomposition of less stable cations

63
 3. Carbanions
• Carbanions are considered to be derived by the heterolytic fission of the
C-X bond in an organic molecule, in which carbon is more
electronegative than the atom X.
• In this fission the carbon takes away the bonding electron pair and
acquires a negative charge and X acquires a positive charge (X+).

• The species with a negative charge on the central carbon atom having a
pair of electrons is called a carbanion.
• A carbanion can be considered as a species containing a trivalent carbon
with a lone pair of electrons and the carbon is negatively charged. 64
• There are 8 electrons around the carbon atom and so it is
not electron deficient.
• The geometry of simple carbanions is found to be
pyramidal.
• The central carbon atom is sp3 hybridized with the
unshared pair

• However, when the carbanion is stabilized by

delocalization, it assumes sp2 hybridization for effective
resonance. occupying one apex of the tetrahedron.
65
• Generation of carbanions
• Carbanions have been generated as intermediates in a large
number of organic reactions.
• Following methods are generally used for their generation.
• (a) Abstraction of H by a base:
• An appropriate organic substrate having a C—H bond on
treatment with a suitable base results in abstraction of
hydrogen to generate a carbanion.

66
(b) From unsaturated compounds: Addition of a
nucleophile to an unsaturated C—C bond generates a
carbanion.

(c) From alkyl halides: Reaction of alkyl halide with Mg

turning in presence of anhydrous ether as solvent
generates Grignard reagent. The Grignard reagent behaves
like a carbanion.

67
• Reactions of carbanions
• Being very reactive in nature, the carbanions undergo reactions as
soon as they are formed.
• Carbanions take part in the usual types of reactions, viz., addition,
elimination, displacement, rearrangement etc.
• (a) Addition reactions The carbanions being electron rich behave
like nucleophiles. These add to the carbonyl group of aldehydes.

68
(b) Elimination reactions
Carbanions are involved as intermediates in elimination
reactions. For example, β-phenylethyl bromide on
treatment with a suitable base (like NaOEt) results in the
formation of styrene.
The reaction proceeds via the formation of a carbanion
intermediate.

69
70
4. Enamines
• Vinylamines or α, β-unsaturated amines are generally known as
enamines.
• These are obtained by the condensation of a carbonyl compound having
at least one α-hydrogen atom with a secondary amine.

• Enamines obtained from primary amines are unstable because they

possess hydrogen on the nitrogen, thus readily rearranging to the imine.
• On the other hand, enamines obtained from secondary amines do not
have any hydrogen on the nitrogen.
• Therefore, they cannot undergo this type of rearrangement and hence are
stable.
71
 5. Carbenes
• Carbenes may be defined as neutral, divalent carbon intermediates
in which a carbene is covalently bonded to two atoms.
• The simplest carbene is called methylene and is generated by the
decomposition of diazomethane.
𝐶𝐻2 𝑁2 → 𝑁2 + ∶ 𝐶𝐻2
• A carbene has two non-bonded orbitals having two electrons
between them.
• A carbene may exist in its ground electronic state as a singlet or a
triplet depending on whether the two unbounded electrons are,
respectively in the same molecular orbital with paired spins or in
two orbitals of equal energy with parallel spins.

72
6. Nitrenes or Imidogens
• Nitrenes are the nitrogen analogues of carbenes.
• These are electrons-deficient monovalent nitrogen species.
• The nitrogen atom in nitrenes has a sextet of electrons.
• The nitrenes exist in singlet and triplet states.

• Generation of nitrenes:
• (a) From azides: Thermal or photolytic decomposition of azides
give nitrenes.

73
74
75
7. Benzyne(1,2-Dehydrobenzene or Aryne)
• Benzynes are neutral, highly reactive reaction intermediates, in
which the aromatic character is not markedly disturbed.
• Benzynes (or arynes) contain a carbon-carbon triple bond and may
be regarded as aromatic counterpart of acetylene.
• Benzyne is benzene minus two o-hydrogens and so it is also called
dehydrobenzene.
• The new bond of benzyne is formed by the overlap of sp2 orbitals
belonging to two neighbouring carbon atoms.
• As the sideways overlapping is not very effective, the new bond is
weak and so the benzyne is highly reactive species.

76
Generation of benzynes

77
78
• Reactions of benzynes
• Benzyne is an extremely reactive species and is generated in situ for
obtaining various products.
• (a) Reaction with nucleophiles: Aryl halides on treatment with
KNH2 (strong base) generates benzyne. When KNH2 is used, the
available nucleophile (NH2-) reacts with the generated benzyne to
give aniline:

79
(b) Synthesis of simple molecules:
• A number of products can be synthesized by the reaction of
benzyne with simple reagents.

80
• (c) Synthesis of an unusual type of product:
• Several types of compounds that are difficult to obtain or cannot be obtained by
other methods can be conveniently obtained via benzyne intermediate:

• Reaction with furan

• Conversion of chlorobenzene to phenol and aniline derivatives

81
 QUIZ
Q1: A chemical equation indicates:
a. Electrophile and anion
b. Reactants and Reagent
c. Nucleophile and reagent
d. Reactants and Products
Q2: The description of the path followed by the
reactants as they are transformed into products is
termed as:
a. Chemical reaction
b. Reaction Mechanism
c. Transformation
d. None
82
Q3. The breaking of a covalent bond in a manner so that
each of the two species formed retains one electron of the
shared pair is called:
a. Homolytic fission
b. Heterolytic fission
c. Reaction mechanism
d. Free radical

Q4. The ions are formed in

a. homolytic fission
b. Heterolytic fission
c. Chemical reaction
d. Mechanism
83
Q5. The number of electrons in the valence shell of
carbon in free radical
a. 6
b. 7
c. 8
d. 2
Q6. In nucleophilic substitution reaction, conversion of
a tertiary alkyl is the example of
a. SN1
b. SN2
c. E1
d. E2

84
Q7. There occurs the movement of an atom or a group
from one atom to another within the molecule
a. Substitution or displacement reactions
b. Addition reactions
c. Elimination reactions
d. Rearrangements
Q8. BF3 is the example of:
a. Neutral electrophiles
b. Positive electrophiles
c. Neutral Nucleophiles
d. Positive Nucleophiles

85
Q9. The number of electrons in the valence shell of
carbon in carbonium ion
a. 6
b. 7
c. 8
d. 2
Q10. α, β-unsaturated amines are generally known as:
a. Enamines
b. Carbenes
c. Imidogens
d. Benzyne

86