UNIT-IV

Reactions
Mechanism
 REACTION MECHANISM

Substitution reactions: Nucleophilic substitution-SN1 and SN2 Mechanisms. Aromatic

electrophilic substitution: Nitration, sulphonation, Friedal-crafts alkylation and acylation.
Addition reactions: Electrophilic addition to alkenes, dienes- Diel’s–Alder reaction. Alkynes-
acidity alkynes-formation of acetylides
–addition of water with HgSO4 catalyst. Markownikoff rule, peroxide effect, Nucleophilic
addition to carbonyl group-cyanohydrin reaction, reduction with LiAlH4, preparation of
alkenes-Wittig reaction, holoform reaction, Michael addition, Darzens reaction, Simmons-
smith reaction, McMurry reaction, formation of Schiff base, aldol Condensation, Cannizzaro,
Claisen-Schmidt, Reformatsky, benzoin condensation, Wolf-Kishner and MPV reduction.
 Introduction
Reaction Mechanism:
Mechanism for any reaction is defined as collection of number of processes that
explains the overall reaction.

★ This is the actual method of completion of reaction as it gives the number of broken
bonds and the number of steps involved.
★ In a mechanism the positions of all atoms (stereochemistry), role of solvent
molecules and the energy of the system is specified.
★ It also helps in describing the reaction intermediate,
activated complex and
transition state involved in the whole reaction.
★ A mechanism accounts for all the reactants used, the function of a catalyst, all
products formed and their amount.
★ From a mechanism the rate law can be deduced
Substrate: In most reactions of organic compounds, one or more covalent bonds are broken. For most
reactions, it is convenient to call one reactant the attacking reagent and the other the substrate.
Nucleophile and Electrophile: Reagent having an electron pair is known as nucleophile and the
reaction is nucleophilic. A reagent that takes an electron pair is called an electrophile and the reaction is
electrophilic.

Leaving Group: In a reaction in which the substrate molecule becomes cleaved, part of it (the part not
containing the carbon) is usually called the leaving group. A leaving group that carries away an electron
pair is called a nucleofuge. If it comes away without the electron pair, it is called an electrofuge .

Reaction intermediates: Intermediates are those chemical species which are short-lived and unstable.
They are neither reactant nor product. They are said to be temporary products or reactants generally
free radicals or ions.
Transition states: It is an unstable intermediate molecular state with an unusual number of bonds
and/or unstable geometry.
Molecularity: It is defined as number of colliding molecular entities involved in a single reaction step.
★ Unimolecular reaction step involve only one molecular entity.
★ Bimolecular reaction step involve two molecular entities.
★ Termolecular reaction step involve three molecular entities.
Types of Reactions mechanism:
1. Polar or ionic Mechanism
2. Free radical Mechanism
Polar or Ionic Mechanism:

★ This is the type of mechanism applies to organic reactions in which

heterolytic bond fission takes place. Here the substrate molecule develop
polarity (positive and negative charged centres) by the displacements of
electrons due to inductive effect, mesomeric or electromeric effects.
These positive and negative centres can be attacked by electrophile or
nucleophiles.
★ The mechanism of reactions involving the attack of electrophilic or
nucleophilic reagents on the polar substrate molecules is referred to as
polar or ionic mechanism. The cardinal principle of electrostatic that the
unlike charges attract while like charges repel each other forms the basis
of all polar mechanisms.
★ The negatively charged nucleophiles attack the substrate molecule at the
positive centre causing a nucleophilic reaction. On the other hand, the
positively charged electrophile would attack the molecules at the negative
centre causing an electrophilic reaction.
Free Radical Mechanism:

This type of mechanism applies to organic reaction in which homolytic bond fission takes place.
The first step is formation of free radical (R .) from a reagent by homolytic fission. These free
radicals can then attack the substrate to give the product.

The free radicals carry no charge. They can attack any part of the substrate molecule regardless
of the electronic distribution of the substrate. The mechanism of reactions involving the attack of
the free radicals on the substrate molecule is referred to as free radicals mechanism
Reactions happen when electrons flow between molecules:
When, as results of these interactions, a pair of molecules find themselves close together, a reaction can take
place provided electrons moves from one molecule to another. This is what call the mechanism of the reaction-
the detailed description of the pathway the electrons take. We call the molecule that accepts the electrons that
electrophile (electron lover) for the obvious reasons. The molecules that donate the electrons is called
nucleophile.
This is a very important topic, which deals with the mechanism by which one molecule is converted into
another. It is a means of showing the way electrons (which make up bonds) move when one compound is
transformed into another. ‘Arrow pushing’ is employed to illustrate mechanisms in organic chemistry.

In this process, the lone pair of electrons on N has become a bonding pair in the product.
This is how we would show the reaction with a curved mechanistic arrow :

or

During protonation, the formal charge moves from the proton (H+) to the nitrogen atom

This makes sense because, in the protonation, the nitrogen has donated a full pair of electrons but in
the product shares a bonding pair, a net loss of 1 electron. The proton (H+), on the other hand, had no
electrons originally but now shares a bonding pair, a net gain of one electron (hence the drop in charge
from +1 to 0). We represent this movement of an electron pair as a ‘curly arrow’ – NOTE THE
DIRECTION OF FLOW
 Now let's look at the reverse direction, i.e. deprotonation:

The formal charge has moved from N to H. This is because the H was sharing an electron pair on the
left hand side, but has none on the right hand side, a net loss of 1 electron. This is how we would show
the reaction with a curved mechanistic arrow - note how it shows the bonding pair moving out of the
bond and towards the N atom :

In reality, a proton is usually removed by a base. This is

how it would be illustrated:
The formal charge also moves. N
goes from +1 to 0 because it gains
a net 1 electron. The oxygen goes
from -1 to 0 because overall it loses
1 electron
 Types of Organic
Reactions:
1. Substitution – replace one group with another, SN2, SN1 etc.
2. Elimination – take something off, E2, E1 etc. Usually, two groups come off and an alkene is
formed!
3. Addition – add something on Usually you add two groups to an alkene.
4. Rearrangement – make it look difference.

If you understand the mechanisms of these processes then this will greatly assist your knowledge
of organic chemistry.

1. Substitution Reactions:

A reaction in which one group or atoms replaced by another is called substitution reactions.
The incoming group is bonded to the same carbon atom to which the leaving group is
attached or bonded. Substitution reactions has been classified according to the nature of the
substituents involved or initiated by the nucleophile, electrophile, free radicals.
 1
.

2
.

It will be seen
3 that in all types of substitutions, the displaced species belong to the class as
the attacking
. species.
Free-Radical Substitution Reactions:

Initiation steps Propagation steps

Termination steps
Electrophilic Substitution Reactions (Common in Aromatic Compounds):

When a substitution reaction involves the attack by an electrophile, the reactions is

referred to as electrophilic substitution reaction.

Example: The bromination of benzene in the presence of FeBr3

 Nucleophilic Substitution Reactions (Common in aliphatic
compounds) :
When substitution reaction involves the attack by the nucleophile, the reaction is
referred to SN (S stands for the substitution and N for a nucleophile). A nucleophile
replaces a leaving group on an sp3 hybridized Carbon.

Example: The hydrolysis of alkyl halides by aq NaOH

★ One sigma bond is broken and one sigma bond is

formed
Mechanisms of substitutions reactions:
There are two major mechanisms of substitution reactions.
★ SN2 Reactions
★ SN1 Reactions

SN2 Reactions Bimolecular Nucleophilic Substitution Reactions:

The first is called the SN2 mechanism – Substitution, Nucleophilic, Bimolecular

What do these three terms mean?

It is a single step mechanism; the nucleophilic

adds and the leaving group is simultaneously displaced in
the same step. A concerted mechanism.

When the rate of a nucleophilic substitution reaction depends on the concentration of both
substrate and the nucleophile, the reaction is of second order and is represented as SN2.

Rate ⍺ [ substrate] [Nucleophile]

 Evidently, the rate-determining step involves the participation of both the substrate and the
nucleophile.

The Hydrolysis of methyl bromide by aq. NaOH. The reaction and the transition state
are represented as below.:

★ The reaction of methyl bromide with hydroxide ion follows S N2

mechanism. The hydroxide ion approaches the substrate carbon
from the side opposite the bromine atom (back side). This is because
both hydroxide and bromine atom are electron rich. It is natural that
these stay as far apart as possible (like charges repel).
★ When the transition state is reached, the central carbon atom has gone from its
initial sp3 hybridisation to a sp2 state with an approximately perpendicular p orbital.
There are two lobes of p-orbital, one overlaps with the leaving group and the other
with nucleophile. Hydroxide ion has a diminished negative charge because it has
started to share its electrons with the substrate carbon.

★ The bromine atom also carries a negative charges because it has started to
removing the its shared pair of electrons from the carbon atom. In the transition
state,the three C-H bonds lie in one plane. The C-OH and C-Br bonds are
perpendicular to the plane of C-H bonds. The energy is need for the cleavage of C-
Br bond is partially provided by the energy liberated by the C-OH bond formations.

★ During transition state the three non-reacting substituents and the central carbon
are in a same plane. In the course of the reaction , the configuration of the carbon
is inverted, rather like an umbrella blown inside out. The changes in configuration is
called Walden inversion.
Stereochemistry of SN2 Reactions:
In SN2 Reactions, attack of the nucleophile (e.g OH ion) takes place from the back om
i.e, fr
the side remote form the leaving group (Br) and hence reactions are always
attended by inversion of configuration jus in the same as an umbrella turns inside out in a
strong gale. Consequently, if an optically active alkyl halide is hydrolysed, the product
would also be optically active. Thus , (+) chlorosuccinic acid on hydrolysis with KOH
gives (- Malic acid)
Most of the primary
aliphatic alkyl halides
undergo hydrolysis
only by this
mechanism
In the SN2 reaction, a nucleophile attacks a carbon (usually an alkyl halide) at the backside. The reaction
is concerted (happens all at once), and the stereochemistry proceeds with inversion of
configuration. The big barrier to the SN2 is steric hindrance, because the nucleophile has to do a
backside attack. This is why the rate is favored for primary > secondary >> tertiary alkyl halides,
strong nucleophiles, and polar aprotic solvents.
 SN1 Reactions- Unimolecular Nucleophilic Substitution
When the rate of the nucleophilic Reactions:
reaction depends only on the concentration of the alkyl
halide, the reaction is of first order and is represented as SN1 .
Rate ⍺ [ substrate]
The reaction consists of two steps. The first steps involves the slow ionisation of the alkyl
halide to produce the carbonium ion and is obviously the rate determining step. The second
step involves the fast attack of the nucleophile onto the carbonium ion. then the nucleophile
adds in the second step. Thus the hydrolysis of tertiary butyl bromide is may shown as
under:

Step 1. The alkyl ionizes to give the carbonium ion. This s rate determining step

First step involving the cleavage of

C-Br bond is energy consuming. The
energy is needed for this rupture is
provided by the the energy is
released by the solvation of the two
ions (Carbonium ion and Br)
 Step 2.
The nucleophile can attack the planar carbonium ion from either side to give t-butyl
alcohol.

Mechanism
:

First of all, the slow step should be formation of the (unstable) carbocation – which only depends
on the substrate, not the nucleophile. Furthermore, since the stability of carbocations depends
tremendously on substitution pattern (tertiary carbocations are more stable than secondary, which
are more stable than primary) this also conveniently explains the dependence of the reaction rate on
substitution pattern. Any factor which stabilizes the carbocation, increases the rate at which the
leaving group can leave.
 Stereochemistry of SN1
In SN1 Reactions:
reactions, Carbonium ions are the intermediates and these are planar
chemicals species (an sp2 hybridized carbon with molecular geometry is trigonal
planar). The of the nucleophile on these carbonium ion can take place with equal ease
from either face of this flat ion. Thus, if the alkyl halide is optically active, the product
would not be optically active but it would be a racemic mixture..

Different degrees of racemization in the hydrolysis of 1-

halogenoethylbenzenes.
Remember that the primary alkyl halides undergo hydrolysis by SN2 mechanism. The tertiary
alkyl halides undergo hydrolysis by SN1 mechanism. This is because attack of the hydroxide ion
on the crowded t-alkyl halide is quite difficult.

The big barrier to the SN1 is carbocation stability,

which is why it is favored for tertiary > secondary
>> primary alkyl halides and polar aprotic protic
solvents. Also, since the carbocation is such a
reactive electrophile, we only need a weak
nucleophile.

Secondary alkyl halides may undergo hydrolysis reaction by either S N1 or SN2

mechanism
Rate of an SN1 reaction depends on the

★ Carbon skeleton
★ The leaving group
Along with the usual factors of temperature and solvent but NOT the nucleophile.
 AROMATIC ELECTROPHILIC SUBSTITUTION
REACTION
❖ Nitration,
❖ Sulphonation,
❖ Friedal-crafts alkylation
❖ Friedal-crafts acylation

Benzene undergoes electrophilic substitution reactions

the benzene ring with its delocalized 𝝅 electrons is an
electron rich system. It is attacked by electrophiles,
giving the substitution products..

Reaction in which hydrogen atom of

the aromatic ring is replace by an
electrophile are called electrophilic
substitution reactions
 Regardless of the electrophile used, all the electrophilic aromatic substitution reactions occur by the
same three step mechanism- addition of electrophile E+ to from a resonance -stabilized
carbocation, followed by deprotonation with base .
★ The second step in electrophilic aromatic substitution forms a carbocation ,for which three
resonance structure can be drawn

★ Always draw in the H atom on the carbon bonded to E. This serves as reminder that it
is only sp3 hybridized carbon in the carbocation intermediate

★ Notice that the positive charge in a give resonance structure is always located ortho
or para to the new C-E bond. In the hybrid, the charge is delocalized over three atoms
of the ring
Why benzene undergoes electrophilic substitution reaction whereas alkenes
undergo addition reactions?

Both benzene and alkenes are susceptible to electrophilic attack because of their exposed 𝝅
electrons. Both react with electrophile to form stable carbonium ions.

But similarity is end at this point. The carbonium ion produced from the alkene usually
combines with nucleophile to give the overall addition product.
 If this happened to benzene, the product would not no longer be aromatic. The resonance energy
(stabilization energy) of the benzene would be lost. Instead, the nucleophile removes a proton from
the carbonium ion intermediate. The loss of proton allows the electrons from the C-H bond to go
back in to the ring and regenerate the aromatic 𝝅 system. Net change is the replacement of a
hydrogen atom by an electrophile.

It is important to note that although it delocalised, this cation is not aromatic: there is no cyclic array
of p orbitals because the ring contains a single tetrahedral (sp3 hybridized) carbon atom. We have
emphasized this tetrahedral atom by drawing in the hydrogen atom at the point of substitution-
one that will be lost when aromaticity is regained.
 Nitration Reaction:
Benzene reacts with Conc. nitric acid in the presence of Conc.sulphuric acid at 60oC to
form nitrobenzene. The combination of these both acid it produce the electrophile Nitronium
ion (NO2 +)

Step 1. Formation of the electrophile (NO2 )

+

Step 2. The electrophile attacks the benzene ring to form a carbonium ion
 Step 3: Loss of proton yields
Nitrobenzene

Sulfonation:

Benzene reacts with the Conc sulphuric acid at 120 oC or fuming sulfuric acid at room temperature
to give benzenesulfonic acid. Note: Fuming sulfuric acid is concentrated acid that contains added
sulfur trioxide
Mechanism:

Step 1. Electrophile is formed. In this reaction the electrophile sulfur trioxide (SO 3). In Conc.
sulfuric acid , SO3 is produced as follows. In fuming sulfuric acid, this step is unimportant
because the dissolved SO3 reacts directly.

Step 2. The electrophile attacks the benzene ring to form a carbonium ion
Step 3. Loss of
proton

Step 4. Addition of proton give benzene sulfonic

acid.
 Friedel-Crafts
Reaction:
A Friedel-Crafts reaction is an organic coupling reaction involving an electrophilic aromatic
substitution that is used for the attachment of substituents to aromatic rings. The two primary
types of Friedel-Crafts reactions are the alkylation and acylation reactions. These reactions were
developed in the year 1877 by the French chemist Charles Friedel and the American chemist James
Crafts.
Friedel-Crafts Alkylation:
Friedel-Crafts Alkylation refers to the replacement of an aromatic proton with an alkyl
group. This is done through an electrophilic attack on the aromatic ring with the help of
a carbocation. The Friedel-Crafts alkylation reaction is a method of generating
alkylbenzenes by using alkyl halides as reactants.

A Lewis acid catalyst such as FeCl3 or AlCl3 is employed in this reaction in order to form a
carbocation by facilitating the removal of the halide. The resulting carbocation
undergoes a rearrangement before proceeding with the alkylation reaction.
 Step 1. Formation of the electrophile

Step 2. The electrophile attacks the benzene ring to give a

carbocation

Step 3. The loss of proton gives alkyl

benzene.
 ★ An excess of the aromatic compound must be used in these reactions in order to avoid
polyalkylation (addition of more than one alkyl group to the aromatic compound).

★ Aromatic compounds that are less reactive than mono-halobenzenes do not participate in the
Friedel-Crafts alkylation reaction.

It is important to note that this reaction is prone to carbocation rearrangements, as is the case with
any reaction involving carbocations .

This is because the Friedel-Crafts

alkylation involves the
carbonium ion (step.1). These carbonium
formation

of
 Friedel-Crafts Acylation:
The Friedel-Crafts acylation reaction involves the addition of an acyl group to an aromatic ring.
Typically, this is done by employing an acid chloride (R-(C=O)-Cl) and a Lewis acid catalyst
such as AlCl3. In a Friedel-Crafts acylation reaction, the aromatic ring is transformed into a
ketone.

An acid anhydride can be used as an alternative to the acyl halide in Friedel-Crafts acylations. The
halogen belonging to the acyl halide forms a complex with the Lewis acid, generating a highly
electrophilic acylium ion, which has a general formula of RCO+ and is stabilized by resonance.
Since alkyl benzenes other than methyl, ethyl, or t-alkyl cannot be prepared from alkyl halide
without rearrangement. They are best prepared by Friedel-Crafts Acylation- Clemmensen
Reduction sequence.
Limitations
Despite overcoming some limitations of the related alkylation reaction (such as carbocation rearrangement and
polyalkylation), the Friedel-Crafts acylation reaction has a few shortcomings.
★ The acylation reaction only yields ketones. This is because formyl chloride (H(C=O)Cl)
decomposes
into CO and HCl when exposed to these conditions.
★ The aromatic compoundcannot participatein this reaction if
it is less reactive than a mono-halobenzene.
★ Aryl amines cannot be used in this reaction because they form highly unreactive complexes
with the Lewis acid catalyst.

The acylations can take place on the nitrogen or oxygen atoms when amine or alcohols are used.
Addition reactions:
Addition reactions are those in which atoms or groups of atoms are simply added to a double or triple bond
without elimination of any atoms or other molecules. These reactions may be initiated by electrophile,
nucleophile, or free radicals.

The 𝝅 electrons of a double bond are less firmly bound to the carbon nuclei. They are more
exposed.
Step 1. Formation of electrophile and nucleophile . Hydrogen bromide give a proton (H+) and Bromide ion (Br-)

Step 2. Attack of the 𝝅 bond on the electrophile

forms carbocations.

Step 3. Attack by the nucleophile gives the addition

product.

E+ is usually : H+. Br+, Or Cl+ Nucleophile is

usually : Br-, Cl-, OH-
Electrophilic addition to alkenes:
When an addition reaction involves the initial attack by an electrophile, the reaction is referred to as
electrophilic addition reactions. Compounds containing carbon-carbon double and triple bonds
undergoes such reactions. The addition of HBr to ethylene is an example of electrophilic addition reactions.

The mechanism of the above reaction involve the following

steps:
Step 1. Hydrogen bromide give a proton (H+) and Bromide ion (Br-)

Step 2. The proton (Electrophile) attacks the 𝝅 bond of ethylene to give a carbonium ion
 Step 3. The bromide (Nucleophile) attacks the carbonium ion to give the addition product.

When an alkene is symmetrical about the double bond, as ethylene is, the product formed in addition
reactions is the same no matter which way the reagent becomes attached to the alkene

★ Other reagents like HCl, HOCl,

H2SO4, H2O, Br2, Cl2 add to alkenes.

Both the alkene and the adding reagent are

unsymmetrical, two alternatives are possible :
Experimentally it have been found that isopropyl
bromide is the major product.
In an electrophilic addition that can lead to two products, one product usually predominates over the other. After
studying the large number of such addition reactions, in 1869, the Russian Chemist Valdimir Markovnikov put forward
the following rule.

Markovnikov Rule: If an alkene is unsymmetrical (that is, the groups attached to the two sp 2 hybridized
carbons different), there is the possibility of two different products from HX addition. In additions of HX to
unsymmetrical alkenes, the H+ of HX goes to the double bonded carbon that already has the greatest
number of hydrogen. Which means, the addition of an unsymmetrical reagent to an unsymmetrical
double bonds proceeds in such a way as to involve the most stable carbonium ions.

According to the his rule, we would predict that the reaction of HCl with propene yields 2-chloropropene (not the 1-
chloro isomer).
 Explanation: Markovnikov formulated this empirical rule because of experimental observations. We can
explain this rule on the basis of mechanism of HX addition . Consider the reactions of propene with HBr

Step.1. Formation of a carbocation. Notice that for propene, two carbocations are
possible.
Step.2. Bromide ion attacks the more stable secondary carbocation to give the major product.

The order of stability of carbocations 3° > 2° > 1°. Addition of a reagent to an unsymmetrical alkene
proceeds by the way of more stable carbocation. This is the reason that markovnikov’s rules is followed.

Remember: The tertiary (30) carbonium ion are more stable than the secondary carbonium ion.
Secondary carbonium ions turn are more stable than primary carbonium
ions.
Peroxide effect : Markovnikov rule is quite general but not universal. In 1933, the american chemist,
M.S. kharasch discovered that the addition of HBr to unsymmetrical alkenes in the presence of organic
peroxides (R-O-O-R) takes a course opposite to that suggested by Markovnikov rules. This phenomenon
of anti-markovnikov addition of HBr caused by the presence of of peroxide is known as peroxide effect.
For example: when propylene reacts with HBr in the presence of peroxide, the major product is n-propyl
bromide. Whereas in the absence of a peroxide the major product is isopropyl bromide.
Mechanism: Propylene reacts with HBr in the presence of a peroxide by a free radicals mechanism.
Following steps are involved:
Step 1. Peroxide dissociates to give the alkoxy free radicals.

Step 2. Alkoxy free radicals attacks HBr to form a bromine atom (as free radical)
 Step 3. Bromine atom (free radical) can attack propylene to give a primary free radicals and a secondary
free radical.

The order of stability of carbocations 3° > 2° > 1°. Therefore , the more stable 2° free radical is formed
predominantly.

Step 4. More stable 2° free radical attacks the HBr molecule to form anti-Markovnikov product and
bromine atom. The bromine atom goes back to the step 3.
Remember that HCl and HI do not give the same reaction in the presence of peroxides. This is
because :

1.The HCl bond (103 kcal/mol) is stronger than HBr bond (87 kcal/mol). It is not broken by the alkoxy
free radicals obtained from peroxides.

2.The HI bond (71 kcal/mol) is weaker than HBr bond (87 kcal/mol). It is not broken by the alkoxy free
radicals obtained from peroxides. But iodine atoms so formed readily combine with each other to yield
iodine molecules rather than attack the double bond alkenes .
 DIENES
Alkenes containing two carbon- carbon double are called dienes or alkadienes

1.If the double bonds are separated by more than one single bond, the diene is called isolated or non
conjugated dienes
2.If the double bonds are separated by one single bond, the diene is called conjugated dienes
3.If the double bonds are adjacent to each other, the diene is called cumulated dienes

Dienes are name by the IUPAC system in the same way as alkenes excepted that ending -adiene is
used. The position of the double bonds are numbered to give the first carbon of each double bond a
minimum number.

The most important class of dienes is that of conjugated dienes. Their chemical properties are different
from those of ordinary alkenes.
 1, 3-
Butadiene: This is most important conjugated
diene.

Structure:
All the four carbon atoms in 1,3 butadiene are sp 2
hybridized. The sp2 hybrid orbitals over with each
other and with s orbitals of the hydrogen atoms to
form C-C and C-H sigma bonds. Since the bonds
results from the overlap of trigonal sp2 orbitals , all
the carbon atoms and hydrogen atom lies in one
plane.

★ Also each carbon atom in 1,3 butadiene possesses an unhybridized p orbital. The p orbitals are
perpendicular to the plane of sigma bonds.
★ The p orbital on C-2 can overlap with p orbitals on C-1 and C-3. The p orbital on C-3 can overlap
with the p orbitals on C-2 and C-4. that is , all four p orbitals overlap to form a lager 𝝅 molecular
orbital (Fig) .
★ Each pair of 𝝅 electrons is thus attracted , not by two but all four carbons.
 The overlap of p orbitals of C-2 and C-3 in both directions, which shows 𝝅 electrons to be
spread over a larger area, is referred to as Delocalisation. This delocalisation of 𝝅 electrons
is responsible for greatest stability of 1,3-butadiene.
Diels-Alder reactions:
This involves the treatment of 1,3-butadiene (or any other conjugated diene) with an alkene or alkyne.
No catalyst required for carry out this reaction. The Diels-Alder reaction is an important organic chemical
reaction where the reactants include a substituted alkene and a conjugated diene. This substituted
alkene or alkyne is commonly referred to as a dienophile (diene lover). This reaction gives rise to a
substituted derivative of cyclohexene. The product of Diels-alder reaction is called adduct.

The Diels-Alder reaction is a very good example of pericyclic reactions which proceed via
concerted mechanisms (i.e. all bond breakage and bond formation occurs in a single step). The net
result of the formation of two new sigma bond and one new 𝝅 bond at the expense of three
original 𝝅 bond.

This reaction was discovered by the German chemists O. Diels and K. Alder in the year 1928, for
which they received the Nobel Prize in Chemistry in the year 1950. The Diels-Alder reaction can be used to
form six-membered rings since there is a simultaneous construction of two new carbon-carbon bonds.

★ It can be observed that two 𝝅 bonds were converted into two sigma bonds.
★ This occurs due to the concerted bonding of two
independent 𝝅-electron systems.
★ The Diels-Alder reaction involves the shift of four
𝝅 electrons of the diene and two 𝝅 electrons of the dienophile.
 Since the Diels-Alder reaction mechanism is concerted, the reaction proceeds in a single step cycloaddition
reaction. Here, two unsaturated molecules combine to form a cyclic adduct. There is a net reduction in bond
multiplicity. All the bond formations and bond breakages happen simultaneously.

Dienes:

Dienophile:
Although dienophile can be a simple alkene, electron -attracting groups (such as -CN, -
CHO, COR, -COOH, -COOR) facilitate the reaction. This Diels-Alder reaction is
widely used in the synthesis of six membered ring compounds.

The Diels-Alder reactions have a one step concerted mechanism. A diene reacts
with an electron poor alkene to form a new cyclohexene ring

❖ The Diels-Alder reaction include its role in the production of vitamin B6 and the
role of its reverse-reaction in the production of cyclopentadiene on an
industrial scale
Hetero Diels-Alder Reaction:
❖These reactions involve one or more heteroatoms (any atom other than carbon or hydrogen).
❖When carbonyl groups are reacted with dienes, dihydropyran products are formed.
❖The aza Diels-Alder reaction involves the use of imines as the dienophile (or diene substituents). The product
formed in this reaction is an N-heterocyclic compound.
❖If a nitroso compound is used as the dienophile, the resulting reaction with the diene yields oxazines
Alkynes:
❖ Alkynes are unsaturated hydrocarbons which consist of at least one triple bond
between carbon atoms.
❖ There are two types of alkynes: terminal and internal.
❖ Terminal alkynes are triple bonded compounds in which a carbon atom shares the
triple bond with the carbon at the end of the chain.
❖ Internal alkynes are compounds in which the triple bond is between two carbon
atoms, none of which are terminal.
❖ The general molecular formula of alkynes is CnH2n-2.
❖ They are highly reactive compounds and probably the most reactive of all
compounds, especially when compared to alkanes as well as alkenes

Acetylene: In acetylene, each carbon atom is attached to one hydrogen atom by a single
covalent bond and to another carbon atoms by a triple bond. Since each carbon is attached to two
other atoms it uses sp hybrid orbitals plus to unhybridized 2p orbitals (py and pz) to form its
bonds
Orbital structure of Ethyne Bonding in
Ethyne

The Combustion of acetylene

provides tremendous amounts of
heat, sufficient to cut metal using an
oxyacetylene torch
Alkynes-Acidity alkynes:

Acetylene and 1-alkynes are more acidic in nature because they readily donate protons to
strong bases.

Moreover , acetylene is stronger acid than ethylene, which in turn is a stronger acid than ethane.
The acidity of acetylene or 1-alkynes can be explained by the atomic orbital description of the C-H
bond. We know that s electrons are closer to the nucleus than are p electrons. Therefore , the
more s character there is in a hybrid atomic orbital, the closer the electrons of the bond are to the
nucleus. The amount of s character in various hybrid orbital is as follows:
 The s character of the C-H bond of the acetylene or 1-alkynes ( sp-s sigma bond) is greater
than that of an alkene C-H bond (sp2 -s sigma bond), or an alkane C-H bond (sp3-s sigma
bond). Thus the electrons of the C-H bond in 1-alkynes are more strongly held by the
carbons nucleus. This makes it easier to remove the hydrogen (= C-H) as a proton.

Hybridization of the carbon attached to H affects acidity. Acetylene is more acidic than
ethylene or ethane

The general trend of acidity in alkynes is presented:

HC≡CH > CH3–C≡CH > CH3–C≡C–CH3

Understanding the relative Acidity of Alkynes:

★ Alkynes are acidic because of their potential of dropping hydrogen atoms for creating alkynide ions.
Hence, alkynes acts as Bronsted-Lowry acids.

★ As has already been pointed out earlier, alkynes contain a triple bonded atom of carbon which is
called “sp'' hybridized.

★ Because of the maximum percentage or around 50% of the “s” character present in alkynes, “sp”
hybridized orbitals of the atom of carbon in alkynes display high electronegativity. The orbitals
attract C-H linkages of alkynes to a considerable extent.

★ It is one of the most important reasons why the molecules of alkyne can lose hydrogen atoms very
easily, thus making way for alkynide ions.

★ Therefore, you can rightly say that the atom of hydrogen attached to the triple bonded atom of
carbon is acidic. It proves the presence of acidic hydrogen in alkynes
★ In this case, the electronegativity of the atom of carbon is lesser when compared to alkynes. It is
only because of this reason that alkenes and alkanes do not react with bases for liberating
hydrogen gas.
★ It should be noted that only the atom of hydrogen attached to the triple linked atom of carbon is
acidic and not the other atoms of hydrogen present within the alkyne series.
Understanding the Acidic Character of Alkynes:
Formation of sodium Acetylides (Salt formation):
Hydrogen in acetylene or 1-alkyne are more acidic, that can be easily replaced by metal to
form salt known as acetylides. ★ Sodium acetylides reacts with primary
alkyl halides to yield the higher alkynes.

★ The acidic character of alkynes is also dependent on the unchanging nature of the formed conjugate
base to a considerable extent.
★ When the terminal alkynes happen to lose protons, the process gives way to the formation of
acetylide ions that acts in the form of a steady conjugate base. As has already been pointed out,
sp-hybridized carbon has an electronegative nature.
★ This is mainly because it contains 50% of the s-character and thus can hold a negative charge most
effectively. Therefore, terminal alkynes are acidic.
Formation of Copper and Silver Acetylides: Acetylene and 1-alkynes react with
ammoniacal solution of cuprous chloride and silver nitrate to form acetylides of
these metals

Copper and silver acetylides are very sensitive when it is dry and may explode
violently. However, they can be decomposed by acids to regenerate alkynes. Since
2-alkynes do not form acetylides, this reaction may be used to distinguish 2-alkynes form
1-alkynes.
 Hydration Reaction of Alkyne:
Alkynes react with water in the presence of mercuric sulphate and sulfuric
acid to form an aldehyde or ketone

If you use acetylene under the same when can able get the
conditions acetaldehyde.
Nucleophilic addition to carbonyl group-cyanohydrin reaction, reduction with LiAlH 4,
preparation of alkenes-Wittig reaction, haloform reaction, Michael addition, Darzens reaction,
Simmons-smith reaction, McMurry reaction

Nucleophilic addition to carbonyl group:

Aldehydes and Ketones contains a carbon -oxygen double bond

.
Nucleophilic addition Reactions:

Nucleophilic oxygen reacts with acid and

Electrophiles

Electrophilic carbon reacts with base

and Nucleophiles
General
mechanism:
 Base-catalysed addition reactions:
Base is converted a weak neutral nucleophile to a stable one by removing a proton. The strong
nucleophile then adds to the carbonyl group .

Acid-catalysed addition reactions:

Step.1 : The hydrogen ion from the acid attacks the negatively charged carbonyl oxygen to give
protonated carbonyl group. The protonated carbonyl group is resonance stabilized.

Step.2:
The nucleophile attacks the
protonated carbonyl group to
from the addition product.
Notice that the addition product is the same whether the reaction is acid-catalyzed or base
catalyzed. The nucleophile always adds to the carbonyl carbon and the proton (electrophile), to
the oxygen. Ketones are less reactive than aldehydes in nucleophilic addition reactions.

A carbon atom next to the carbonyl group is called 𝞪- carbon. A hydrogen atom attached to an 𝞪-
Acidity of 𝞪- hydrogens:

carbon is referred to as an 𝞪- hydrogen. The 𝞪- hydrogen of the aldehyde and ketones are acidic in nature.
The acidity is due to the fact that the anion, which results from the removal of an 𝞪- hydrogen by a base
B:, is stabilized by resonance. The resonance - stabilized anion is called Enolate ion.

𝞪- carbon of the enolate ion is negatively charged. It can act as electrophile. The formation of the
enolate ion followed by addition to a carbonyl group is the process involved in all the condensation
reactions of aldehydes and ketones.
 Addition of Hydrogen Cyanide:
Aldehydes and ketones react with hydrogen cyanide to form Cyanohydrins. This reaction is
carried out in the presence of base catalyst.

HCN is very poisonous gas. It is

produced by in situ by the action of
dilute sulfuric acid on potassium
cyanide
Mechanism:
Acetaldehyde reacts with HCN to form acetaldehyde cyanohydrin. Three steps are
involved. (1). The base removes the proton from HCN to give cyanide ion. ; (2) the cyanide
ion attacks the carbonyl carbon of acetaldehyde to form an anion; (3). The proton from the
solvent(usually water) combines with the anion to give cyanohydrin.

Acetone reacts with HCN to form acetone cyanohydrin. Three steps are involved. (1). The
base removes the proton from HCN to give cyanide ion; (2) the cyanide ion attacks the
carbonyl carbon of acetone to form an anion; (3). The proton from the solvent(usually
water) combines with the anion to give cyanohydrin.
Like other nitriles, cyanohydrin can be hydrolysed to give 𝞪- hydroxy carboxylic acid.
Reduction to alcohols:
Aldehydes and ketones can be reduced to alcohols by treatment with hydrogen and Ni or Pt
catalyst.
 Wittig Reaction: In this reaction, aldehyde and ketones are react with phosphorus ylides to form
alkenes.

An ylides is a molecule with adjacent opposite charges. Phosphorus ylides are prepared from primary alkyl
halides and triphenylphosphine.

(An ylide is a neutral dipolar molecule containing a negatively charged atom directly attached to a positively
charged heteroatom, in which the negatively charged atom is a nucleophilic center and the onium group is usually a
good leaving group)

An onium compound, or onium ion, is a cation formally obtained by the protonation of mononuclear
parent hydride of elements of the nitrogen group, chalcogens, or halogens
Mechanism:
Step.1. The negative carbon of the ylide attacks the carbonyl carbon to form a betaine. A betaine is
molecule having non-adjacent opposite charges.

Step.2. The betaine undergoes elimination of triphenylphosphine oxide to give the

alkene.

The Wittig reaction is an excellent method of making alkenes from aldehydes and ketones.
Haloform reactions:

Acetaldehydes and methyl ketones react rapidly with halogen in the presence of alkali to form haloform.

Step.1. Three hydrogen atoms on the 𝝰- carbon are successively replaced by the halogen atoms

Step.2. 𝝰,𝝰,𝝰- tri haloketone molecule is cleaved to give a trihalomethane.

The haloform reaction is used as a diagnostic test for the presence of -COCH3 group. For this purpose, a
solution of iodine is added to an unknown compound in an aqueous alkali solution. A positive test will yield a
bright yellow precipitate of iodoform (chloroform, bromoform are liquids). This is known as iodoform
test and is given by methyl ketones and acetaldehydes. Ethyl alcohol and secondary alcohols also
give positive iodoform test. This is because ethyl alcohol is converted to acetaldehyde and secondary
alcohol are converted into methyl ketones under the conditions used for the test.

The haloform reaction also be used to distinguish methyl ketones from other ketones
 Michael Addition Reaction:
(Conjugate addition: A nucleophile adds to a C=C double bond, is called conjugate
addition)
Michael Addition (1,4 addition or conjugate addition) can be defined as the nucleophilic addition of a
carbanion or another nucleophile to an 𝛼,𝛽-unsaturated carbonyl compound containing electron
withdrawing group, and it belongs to a group of reactions that are considered very useful in the mild
formation of carbon-carbon bonds. It is thermodynamically controlled reactions. In this reaction donors are
active methylene such as malonates and nitroalkanes and acceptors are activated olefins such as α,β-
unsaturated carbonyl compounds.

★ Conjugate additions occur only when the C=C double bond is immediately adjacent to the
C=O group. They don’t occur to C=C bonds that aren’t conjugated
★ Compounds with double bonds adjacent to a C=O group are known as α,β-unsaturated
carbonyl compounds. Many α,β-unsaturated carbonyl compounds have trivial names.
A well-known Michael reaction is the synthesis of warfarin from 4-hydroxycoumarin
and benzylideneacetone
Aldol Condensation:

When aldehyde and ketones having 𝛼- hydrogens atoms are treated with alkali, they
undergo self addition between two molecules to form 𝛽-hydroxy aldehyde or 𝛽-hydroxy
ketone (aldol)

❖This addition is usually followed by elimination of a water molecule resulting in over all
condensation reaction.

❖Essentially this is a nucleophilic addition of a carbanion, generated by the abstraction of a

proton from 𝛼-position of an aldehyde or ketone by a base, to the carbonyl group.

❖The reaction can occur bwn two or more molecules of same or different aldehyde or
ketone, and bwn one or more molecules each of an aldehyde and a ketone.

❖Also an aldehyde or ketone having no 𝛼- hydrogen atom may condense with another
aldehyde or ketone having 𝛼- hydrogen atoms.
Mechanism:
Step.1.
Step.2
.

Step.3
.
Cannizzaro Reactions:
Aldehydes having no hydrogen at 𝝰-carbon atom (with respect to -CHO group), when treated with
concentrated sodium/potassium hydroxide, undergo self oxidation and reduction to form mixture of
an alcohol and a salt of the corresponding carboxylic acid. This reaction is known as cannizzaro
reaction. Ketones do not give this reaction

1.Formaldehyde undergoes cannizzaro reaction to form a mixture of methyl alcohol and salt of formic
acid
2.Benzaldehyde gives a mixture of benzyl alcohol and salt of benzoic acid
★ Cannizzaro reaction is shown by all aromatic aldehydes with -CHO group attached to the
nucleus and also by those aliphatic aldehydes, which do not have 𝝰- hydrogen atoms like
formaldehydes, trimethyl acetaldehyde etc.

★ If the mixture of two such aldehydes (having no 𝝰- hydrogen atom) is subjected to Cannizzaro
reaction, it results in the formation of all possible products and is referred to as crossed
Cannizzaro reaction.

★ In crossed Cannizzaro reaction if one of the aldehyde used in formaldehyde, it gives a mixture of
sodium formate and the corresponding to other aldehyde.

★ This greater tendency of formaldehyde to undergo oxidation readily makes this reaction an important
synthetic tool for the preparation of various aromatic alcohol.
 Certain aldehydes having hydrogen at 𝝰- hydrogen can be made to undergo Cannizzaro reaction,
when heated with sodium hydroxide at high temperature.

Mechanism:

Step 1 :
The first step involves nucleophilic addition of a hydroxide to polar carbonyl group of the aldehyde resulting in
the formation of an anion.
Step: 2:
The negative charge on this anion and the tendency to restore the condition before the electromeric
shifts facilitate the transfer of a hydride ion form the electron rich carbon (presumably because it is
attached to two oxygens-one carrying extra pair of electrons) to second molecule of aldehyde in the second
step. The carboxylic acid and the anion of alcohol formed thus, by a simple proton transfer, give anion
and the alcohol.

Step:
3
Application: Cannizzaro reaction is used for the
preparation of aromatic alcohols and acids.
Particularly, the crossed Cannizzaro reaction with
formaldehyde is very useful in the preparation of
aromatic alcohols.
Benzoin condensation:

The benzoin condensation involves the treatment of an aromatic aldehyde, furfural with aqueous
alcoholic KCN (or NaCN) and refluxed, undergo dimerization to form keto-alcohols. The products are
𝝰-hydroxy ketones.

1. Benzaldehyde react with alcoholic KCN to form benzoin,. (Note: Two part of benzaldehyde
take part in the the reaction)

2. Furfural react with alcoholic KCN to form furoin.

Note: Nitro, hydroxy benzaldehyde and

cinnamaldehyde do not undergo benzoin
condensation reaction
 Mechanism :
The cyanide ion reacts readily with benzaldehyde, and enables the form formation of carbanion(A)

The carbanion (A) can then react with

another benzaldehyde molecule.
Subsequent proton transfer and loss of
the cyanide ion gives benzoin.

Application: it is used for the preparation of

keto-alcohols of aromatic series of the type
of benzoin. It is also used as the first step in
the preparation of benzil and benzilic acid
from benzaldehyde.
 Reformatsky reaction:
This reaction involves the treatment of an aldehyde or ketone, ester with 𝝰- bromo ester in the presence

the formation of an intermediate organozinc compound of 𝝰- bromo ester which can adds to the carbonyl
of zinc in ether solution. The product (after acid hydrolysis) is a 𝝱-hydroxy ester. The reaction involves

groups of aldehyde or ketones

Mechanism : Three steps are involved

Step 1: Formation of zinc salt of enol of ester

Organozinc compound
 Step 2: The zinc salt reacts with the carbonyl
compound

Step 3: Acid hydrolysis give the 𝝱-hydroxy

ester.
 Wolff-Kishner Reduction Reaction:
Aldehyde and ketone can be reduced to corresponding hydrocarbon. The reaction is carried
out by heating the hydrazone of aldehydes/ketones with base like NaOH/KOH at elevated
temperature (refulxed)
Mechanism of Wolff-Kishner Reduction: Three steps are involved in this process

Step 1: Formation of hydrazone when ketone/ aldehyde reacts with hydrazine, followed by a
series of proton transfer steps with the expulsion of water.
Step 2 : Deprotonation of the terminal nitrogen by a strong base, followed by bond formation with
the neighboring nitrogen, resulting in formation of carbanion ( slow step).

Step 3 : Protonation of carbon by water molecule, followed by deprotonation of the terminal

nitrogen and subsequent release of nitrogen gas. The resulting carbanion is protonated by water
molecule giving the desired alkane as product.