Shiva Pandeya

Assistant Professor
Maharajgunj Medical College
TU,IOM
Electrophilic addition reaction

• An electrophilic addition reaction is an addition reaction where, in

a chemical compound , a π bond is broken and two new σ bonds are
formed.

• The substrate of an electrophilic addition reaction must have

a double bond or triple bond.

• The driving force for this reaction is the formation of

an electrophile X+ that forms a covalent bond with an electron-
rich unsaturated C=C bond.

• The positive charge on X is transferred to the carbon-carbon bond,

forming a carbocation during the formation of the C-X bond.
General Mechanism
Addition of HX to Alkenes

• First step is the protonation of the double bond. The

protonation step forms the most stable carbocation possible.

• In step 2, the nucleophile attacks the carbocation, forming an

alkyl halide.

• HBr, HCl, and HI can be added through this reaction

Let us suppose the reaction between propene-1 and HCl.

Here First intermediate i.e. secondary carbocation is formed rather

than second i.e. primary carbocation. So, major product formed is
2 chloro propane not 1 chloro propane .
Markovnikov’s Rule
When unsymmetrical reagent is added to unsymmetrical hydrocarbon
negative part of the reagent is added to that carbon which contain
least number of hydrogen atom.
Free-Radical Addition of HBr
• In the presence of peroxides, HBr adds to an alkene to form the “anti-
Markovnikov” product. Peroxides produce free radicals.
• Only HBr has the right bond energy.
• The HCl bond is too strong, so it will add according to Markovnikov’s rule,
even in the presence of peroxide.
• The HI bond tends to break heterolytically to form ions, but iodine free
radical recombine before propagating the reaction.

During electrophilic addition and free radical addition reaction there is

possibility of rearrangement if more stable carbocation can be formed
Steps of Anti –Markonikov`s Rule
Halogenation 
• It is the addition of halogen atoms to a π‐bond system. The reaction
mechanism for an alkene halogenation can be described as follows.
• In the first step of the reaction, a halogen molecule approaches the
electron-rich alkene  i.e. carbon–carbon double bond. The halogen
atom closer to the bond takes on a partial positive charge as
its electrons are repelled by the electrons of the double bond.
• The atom is electrophilic at this time and is attacked by the pi
electrons of the alkene [carbon–carbon double bond].
• It forms for an instant a single sigma bond to both of the carbon
atoms involved.
• The bonding of halogen is special in this intermediate. At this
moment the halogen ion is called halonium ion.
• When the first bromine is attacked by the carbon–carbon π-bond , it
leaves behind one of its electrons with the other bromine that it
was bonded to in Br2.
• That other atom is now a negative bromide anion and is attracted
to the slight positive charge on the carbon atoms.
• It is blocked from nucleophilic attack on one side of the carbon
chain by the first bromine atom and can only attack from the other
side. As it attacks and forms a bond with one of the carbons, the
bond between the first bromine atom and the other carbon atoms
breaks, leaving each carbon atom with a halogen substituent.
• In this way the two halogens add in an anti-addition fashion.
 Cl2 , Br2 , and sometimes I2 add to a double bond to form a vicinal
dibromide.
Heat of hydrogenation
• Enthalpy of hydrogenation is defined as the change in enthalpy, which
occurs when one mole of an unsaturated compound reacts with an excess
of hydrogen to become fully saturated at atmospheric pressure and room
temperature, the reactants and products being in their natural states
under these conditions.

• The amount of heat energy released when one mole of unsaturated alkene
is completely hydrogenated.

• It is the tool to predict the stability of alkene.

• The compound with greater heat of hydrogenation is less stable as

compared to other with low heat of hydrogenation.
• ∆Ho for the reaction is -30.3 Kcalmole-1 , it means standard heat of
hydrogenation of 1-butene is called as 30.3 Kcalmole-1. Heat of
hydrogenation of every alkene is fairly close to 30 for each double
bond in the compound.
• Based on heats of hydrogenation of alkenes, the trend in the
stability of carbon-carbon double bonds is

Tetra substituted > tri substituted > di substituted > mono

substituted > un substituted.
• Here 1-butene, cis 2-butene
and Trans 2-butene upon
hydrogenation gives the same
product n- butane.

• Heat of hydrogenation for 2-

butene is low than 1- butene
indicates that energy
associated with 2- butene is
low than 1- butene ,means 2
butene is more stable than 1
butene. (Disubstituted is more
stable than monosubstituted.)

• Among isomeric 2- butenes,

the cis isomer has a heat of
• Therefore, if trans evolves 1 kcal
hydrogenation of 28.6 kcal,
the trans has 27.6. Both of less energy than cis isomer, it can
them consume one mole of only mean that it contains 1 kcal
hydrogen and yield the same less energy: in other words, the
product n butane. trans isomer is more stable by 1
• cis isomer. Kcal than cis isomer.
Each set above of isomeric alkenes yields the same alkene on
hydrogenation. . The difference in heat of hydrogenation must
therefore be due to difference in stability. In each case, the greater
the number of alkyl groups attached to doubly-bonded carbon
atoms, the more stable the alkene.

R2C=CR2 > R2C=CHR > R2C=CH2 > RCH=CHR > RCH=CH2 >CH2=CH2
Halohydrin formation

• A halohydrin (also a halo alcohol or β-halo alcohol) is a functional group in

which a halogen and a hydroxyl are bonded to adjacent carbon atoms

•  Halohydrin formation involves addition of a halogen and a hydroxyl  to

adjacent carbon atoms.

• Halohydrins are usually prepared by treatment of an alkene with a

halogen, in the presence of water. The reaction is a form of electrophilic
addition, similar to the halogen addition reaction and proceeds with anti-
addition, leaving the newly added X and OH groups in a trans
configuration.

• If the alkene is unsymmetrical, the halogen is added to the carbon atom

with the greater number of hydrogen atoms
Dienes
• A diene is a hydrocarbon that contains two carbon double bonds.

• Dienes can be divided into three classes, depending on the relative

location of the double bonds:

• Cumulated dienes have the double bonds sharing a common atom as in

a group of compounds called allenes. i.e. two double bonds are not
separated by any carbon- carbon single bond.
CH3-CH=C=CH-CH3
• Conjugated dienes have double bonds separated by one carbon-carbon
single bond.
CH2=CH-CH=CH-CH3
• Isolated dienes have the double bonds separated by two or more
carbon- carbon single bonds
CH2=CH-CH2-CH=CH2.
Addition of HCl to butadiene
• Addition of HBr to 1,3- butadiene yields both 1,2 and the 1,4
products where the proportion of product formed is affected by
temperature.

• At low temperature ( - 80oC) 80% of 1,2 product and 20% 1,4

product is formed.

• At high temperature (400C) 20%1,2 and 80%1,4 product is formed.

• At intermediate temperature mixture of intermediate compositions

are obtained .Although each product is stable at low temperature
prolonged heating of either products give the same mixture.
•  Bonding of an electrophilic atom or group to one of the end carbon
atoms of a conjugated diene ( carbon 1 in the figure below)
generates an allyl cation intermediate. Such cations are stabilized by
charge delocalization, and it is this delocalization that accounts for
the 1,4-addition product produced in such addition reactions. As
shown in the diagram, the positive charge is distributed over
carbons 2 and 4 so it is at these sites that the nucleophilic
component bonds. Resonance stabilization of the allyl cation is
greater than comparable stabilization of 1,3-butadiene, because
charge is delocalized in the former, but created and separated in the
latter.
An explanation for the temperature influence is shown in the following
energy diagram for the addition of HBr to 1,3-butadiene. The initial
step in which a proton bonds to carbon 1 is the rate determining step,
as indicated by the large activation energy (light gray arrow). The
second faster step is the product determining step, and there are two
reaction paths (colored blue for 1,2-addition and magenta for 1,4-
addition). The 1,2-addition has a smaller activation energy than 1,4-
addition - it occurs faster than 1,4 addition, because the bromide
nucleophile is closer to carbon 2 then to carbon 4.  However,  the 1,4-
product is more stable than the 1,2-product. At low temperatures, the
products are formed irreversibly and reflect the relative rates of the
two competing reactions. This is termed kinetic control. At higher
temperatures, equilibrium is established between the products, and
the thermodynamically favored 1,4-product dominates.
When a conjugated diene is attacked by an electrophile, the resulting
products are a mixture of 1,2 and 1,4 isomers. Kinetics and Thermodynamics
control a reaction when there are two products under different reaction
conditions. The Kinetic product (Product A) will be formed fast, and the
Thermodynamic product (Product B) will be formed more slowly. Usually the
first product formed is the more stable favored product, but in this case, the
slower product formed is the more stable product; Product B.