General terms in reaction mechanism

Types of Carbon
 Carbon in organic compounds are classified into four types
based on the number of other carbons bonded to it.
 A primary (1o) carbon is bonded to no or one other C atom.
 A secondary (2o) carbon is bonded to two other C atoms.
 A tertiary (3o) carbon is bonded to three other C atoms.
 A quaternary (4o) carbon is bonded to four other C atoms.

ethane isopropane isobutane neopentane

 Electronegativity
 It is a measure of the tendency of an atom to attract a
bonding pair of electrons. The Pauling scale is the most
commonly used. According to this scale, fluorine is the most
electronegative element with a value of 4.0 and cesium is
the least electronegative element with a value of 0.7
 Order of electronegativity: S < H < C < N < O < F
 Example: In C-F bond, fluorine is much more
elcectronegative than carbon. So electron pair of the
covalent bond are pulled towards fluorine atom.
.F
C .
 Inductive effect
 When a covalent bond is formed between atoms of different
electronegativity, the electron density moves towards the
more electronegative atom or group. It introduces polarity in
the covalent bond.

 Polarity developed in the molecule as a result of high

electronegativity of one atom compared to other.

 In Bormomethane (CH3Br) in which the C–Br bond is a polar

covalent bond. The bonding electrons of the C - Br bond will
be pulled towards atom Br will exhibit a partial negative
charge.

δ+ δ-
C Br
 Hyperconjugation in carbocation
(Stabilizing interaction)
 It is the interaction of the electrons in a σ-bond (usually C-H or C-C)
with an adjacent empty or partially filled p-orbital. It involves
shifting the bonding electrons from adjacent C-H bond to the
electron deficient carbon. Hence, positive charge originally on
carbon is dispersed to the hydrogen which increase in the stability
of the molecule. .
Ex: Hyperconjugation in ethyl carbo cation (CH3CH2+)
P-orbital
σ -electrons

 The more the number of alkyl groups on the carbocation, more is

the number of α C – H σ bonds and hence more are the possibilities
for hyperconjugation which makes the carbocation more stable.
 The order of stability of the Carbocations is: 3oalkyl carbocation >
2oalkyl carbocation > 1oalkyl carbocation > methyl carbocation
 Breaking bonds in organic reactions
 Homolysis
The breaking of covalent bond in such a way that, each of
the two fragments retains their own bonded electrons. By
homoytic fission, free radical is formed.

Cl2 Cl. + Cl.

Free radical
 Heterolysis
The breaking of covalent bond in such a way that, one of
the two fragments retains both bonded electrons. As a
result, one fragment acquires positive charge while the
other got negative charge.

HCl H+ + Cl-
Charged ion
 Reaction Mechanism
 Most organic reactions involve the conversion of one organic
compound to another by the attack of a reagent.
Organic compound which reacts with a reagent to generate a
product- Substrate
The reagent which attack or reacts with substrate to give
product- Attacking reagent. eg. Nucleophile, electrophile.

Substrate + Attacking Product

reagent
(organic compd)
[Intermediate]

 Steps of reaction which involves the conversion of substrate

to product through the formation of transitory intermediate.
During the process, breaking of chemical bonds in reactant
molecules and formation of new chemical bonds in product
molecules take place.
 Attacking reagents
Nucleophile or nucleophillic reagent (Nu:)
 In greek, Nucleo = nucleous (positive charge) and
phallic = loving or attracting.
It indicates that nucleophile attacks positive charged
centres (regions of low electron density) in the substrate
molecule.
 It is defined as electron rich chemical species that can
donate electron pairs in the chemical reaction.
 Due to their ability to donate electrons, it is also called
Lewis base.
 It may be negative ion including carbanion or neutral
molecule with free electron pair.
 For example:
 Negatively charged nucleophiles such as OH-, CN-, X-, OR-
, CH3- (carbanium ion) etc
 Neutral nucleophiles: NH3, H2O, ROH, ROR, RNH2, etc.
 Electrophile or Electrophillic reagent (E+)
 In greek, Electro means electron (negative charge) and
phallic means loving or attracting.
It indicates that, electrophile attacks negative charged
centres (region of high electron density) in the substrate
molecule.
 It is defined as electron deficient chemical species that
can accept electron pairs in the chemical reaction.
 Due to their ability to accept electrons, it is also called
Lewis acid.
 It may be positive ion including carbonium ion or neutral
molecule with electron deficient centres.
 For example:
 Positively charged electrophiles: H+, H3O+, Br+, CH3+
(carbonium ion) NO2+, etc.
 Neutral electrophiles: AlCl3, BF3, FeCl3, SO3 etc.
Types of organic reaction
 The reactions of organic compounds can be classified as:
 Substitution reaction
 Elimination reaction
 Addition reaction
 Rearrangement reaction
 Substitution (replacement) reaction:
 Chemical reaction which involves the replacement of
one atom or a group of atoms in an organic compound
with another atom or group of atoms.
 For example: Chlorination of methane.
hµ,
CH4 + Cl2 CH3Cl + HCl
H3-C-H+ Cl- Cl CH3Cl + HCl

In the reaction, the hydrogen atom of methane are replaced by

chlorine atom forming methyl chloride.
 Elimination reaction:
 Chemical reaction in which atoms or groups from two
adjacent carbon atoms in the substrate molecule are
removed and multiple bond is formed.
 For example: Dehydration of ethyl alcohol.

β α
H 2O

 Here, hydrogen and hydroxide ion of the ethyl alcohol is

removed and a double bond is formed between those
carbons.
 Nucleophilic Substitution (SN reaction)
In alkyl halides
 When the substitution reaction involves the attack by a
nucleophile, then the reaction is known as SN reaction. For
example: Hydrolysis of alkyl halide by aqueous alkali.

Leaving group
hydrolysis
R X + OH- R OH + X-
Alkyl halide Nucleophile Alcohol Halide ion
(substrate) (Attacking sps.)

 In this process, nucleophile OH- substitutes or replaces halide

ion of alkyl halide.
 It requires three components. (a) Substrate (b) Attacking
species and (c) leaving group.
 Nucleophilic Substitution (SN reaction)
In alkyl halides
 Substrate: The compound on which substitution reaction takes
place. The substrate consists of two parts, alkyl group and
leaving group.
 Attacking species: atom or groups of atoms which acts on the
substrate and sometime initiate a reaction.
 Leaving group: atom or group that departs from the molecule
with a pair of bonding electron via heterolytic bond cleavage.

 Depending upon the kinetics of the reaction, the nucleophilic

substitution reactions are divided into two classes.
 Bimolecular nucleophillic substitution reaction (SN2)
 Unimolecular nucleophillic substitution reaction (SN1)
 Bimolecular nucleophillic substitution reaction
(SN2 reaction)
 Bimolecular: Two molecules participate in rate determinng
step (slowest step of reaction).
 SN2 reaction is generally followed by primary alkyl halides.
 For example:
Hydrolysis of methyl bromide (primary alkyl halide) by
aqueous alkali [NaOH (caustic soda) or KOH (caustic potash)].
hydrolysis
CH3 -Br + Na-OH CH3 -OH + NaBr
Methyl aq. Methyl
bromide alcohol

Or

CH3Br + OH- CH3OH + Br-

substrate product
Nucleophile Leaving group