Reaction Mechanism-I
In organic Chemistry, a reaction typically
involves an organic molecule (referred to as
the substrate) interacting with a suitable
attacking reagent. This interaction leads to
the formation of intermediate(s) and
ultimately product(s).
The substrate is the reactant that
contributes carbon to the new bond being
formed. The other reactant involved is
called the reagent. If both reactants
contribute carbon atoms to the new bond,
the choice of which one to call the
substrate is arbitrary; generally, the
substrate is the molecule that is the
primary focus of the reaction.
Reaction mechanism is a detailed account
of each step of the reaction including
descriptions of electron movement, the
energetics of bond breaking and forming,
and the kinetics - how the rate at which
reactants transform into products.
1.0Attacking Reagents
Attacking reagents in organic chemistry are
species that initiate reactions by forming
new bonds with other molecules.
A molecule whose carbon is involved in new
bond formation is called substrate and the
other one is called reagent. When a carbon-
carbon bond is formed, the choice of
naming the reactants as substrate and
reagent is arbitrary and depends on the
molecule under observation.
CH2=CH2 + Br2 →
CH2Br - CH2Br
Types of Attacking Reagent
In chemistry, particularly in organic
reactions, the term attacking reagent
refers to a species that attacks a substrate
molecule or an intermediate, leading to the
formation of a product. This attacking
reagent can be a nucleophile, an
electrophile, or a radical, depending on the
nature of the reaction. Main types of
Attacking reagents are:
1. Electrophiles
Electrophiles are "electron-loving"
species that seek electrons to complete
or stabilize their valence shell. They are
typically electron-poor and have a
positive or partial positive charge.
Electrophiles can act as Lewis acids.
Examples of electrophiles- H⊕, Br⊕, Cl⊕,
SO3, BF3, FeCl3
2. Nucleophiles
Nucleophiles are "nucleus-loving"
entities that are rich in electrons. They
are attracted to positive or partially
positive centers in other molecules,
where they can donate or share their
electrons.
Nucleophile is always a lewis base.
Examples of Nucleophiles- H⊖,OH⊖, O-R⊖,
R-NH2, NH3, H2O.
3. Amphiphile
Amphiphilic molecules, particularly
those containing a multiple bond
between carbon and a more
electronegative atom, exhibit versatile
chemical behavior that allows them to
act both as electrophiles and
nucleophiles.
Examples of Amphiphile- >C = O ,
CH3―C☰N
2.0Reaction Intermediates
In organic Chemistry, understanding
reaction mechanisms first, we need to
understand reaction intermediates. Here is
brief description of important
intermediates:
1. Carbon Free Radical: A carbon free
radical is an atom of carbon that
possesses an unpaired electron, making
it highly reactive. Free radicals are
typically generated through homolytic
bond cleavage and are involved in many
types of reactions, including
polymerizations and combustion
processes.
2. Carbocation: A carbocation is a
positively charged carbon ion, where
the positive charge is due to a carbon
atom having only six electrons in its
valence shell. Carbocations are
electrophilic and can be stabilized by
alkyl groups or resonance.
They are important intermediates in
reactions like electrophilic aromatic
substitution and alkene addition reactions.
3. Carbanion: A carbanion features a
negatively charged carbon atom with
three bonds and a lone pair of
electrons. Carbanions are nucleophilic
and can be stabilized by electron-
withdrawing groups and by resonance.
They play a significant role in various
organic reactions, including nucleophilic
substitution and elimination reactions.
4. Carbene: Carbenes are neutral
species with a carbon atom having two
non-bonded electrons and only six
valence electrons, making them highly
reactive.
Carbenes can insert into C-H bonds, add to
double bonds, and rearrange to form more
stable structures. They are used in
cyclopropanation reactions and in the
formation of ylides.
3.0Bond Clevage
A covalent bond can be cleaved in two
primary ways, which are fundamentally
different in their process and result. Let’s
learn how a bond fission takes place-
Heterolytic Cleavage
In heterolytic cleavage, the bond
between two atoms breaks unevenly.
One atom retains both electrons from
the shared pair, resulting in the
formation of an anion, while the other
atom loses both electrons, forming a
cation. This type of cleavage often
occurs in polar bonds where one atom is
significantly more electronegative than
the other.
The outcome is the formation of ions,
which can be stabilized by solvents in
solution. Heterolytic cleavage is
common in reactions that occur in polar
solvents, which help stabilize the
charged species.
Homolytic Cleavage
Homolytic cleavage involves the even
splitting of a covalent bond, where each
atom takes away one electron from the
bonded pair. This results in the
formation of two radicals, each bearing
an unpaired electron.
Radicals are highly reactive due to their
unpaired electrons and can rapidly
engage in further chemical reactions.
Homolytic cleavage is often facilitated
by high energy conditions such as heat
or light (photochemical reactions).
4.0Types of Reactions and Reaction
Mechanism
Each type of bond cleavage plays an
important role in determining the path and
products of chemical reactions, influencing
how molecules interact and transform
under various conditions.
Organic reactions are varied and complex,
but they can be broadly categorized into
four main types, each involving distinct
changes in the molecular structure and
bonding. Here's a brief description of each:
Substitution Reactions
In nucleophilic substitution reactions,
the nucleophile targets the electron-
deficient part of the substrate molecule.
This type of reaction occurs when a
nucleophile displaces an existing
nucleophile within a molecule.
Haloalkanes commonly serve as the
substrates in these reactions. Here, the
nucleophile reacts with a haloalkane,
where the carbon atom bonded to the
halogen carries a partial positive
charge. During the reaction, the
halogen atom, acting as the leaving
group, is expelled as a halide ion. This
process is specifically termed a
nucleophilic substitution reaction
because it is initiated by the nucleophile
attacking the electron-deficient carbon.
Nucleophilic Subtitution of Alkyl Halides
(R-X) will be-
R-X + Nu– ⟶ R-
Nu + X–
Mechanisms:
Substitution reactions can proceed via two
primary mechanisms:
SN1 (Unimolecular Nucleophilic
Substitution): Involves the formation of
an intermediate carbocation, followed
by a nucleophilic attack. It is common in
tertiary substrates where carbocations
are stable.
Example:
SN2 (Bimolecular Nucleophilic
Substitution): Involves a single step
where the nucleophile attacks the
substrate from the opposite side of the
leaving group, leading to inversion of
configuration.
Characteristics:
The nucleophile attacks the substrate
from the side directly opposite the
leaving group.
During the transition state, the
hybridization of the carbon where the
substitution takes place shifts from sp3
to sp2.
The reaction is bimolecular and occurs
as a one-step concerted process.
Addition Reactions
Addition reactions involve two or more
molecules combining to form a single
product. This type of reaction is
characteristic of alkenes and alkynes,
where the pi bond is broken and new sigma
bonds are formed.
Mechanisms:
These reactions can be:
Electrophilic Addition: Typical of alkenes
and alkynes, where the pi bond
electrons are attracted to an
electrophile, followed by nucleophilic
attack.
Nucleophilic Addition: Common in
carbonyl chemistry, where a nucleophile
adds to the carbon of the carbonyl
group.
Elimination Reactions
Elimination reactions result in the
removal of two atoms or groups from a
molecule, leading to the formation of a
double or triple bond. These are the
reverse of addition reactions.
Mechanisms:
E1 (Unimolecular Elimination): Involves
the formation of a carbocation
intermediate followed by the loss of a
leaving group.’
E2 (Bimolecular Elimination): Occurs in a
single concerted step where a base
removes a hydrogen atom, leading to
the formation of a double bond as the
leaving group exits.
Rearrangement Reactions
Rearrangement reactions involve a
structural reordering of the molecular
framework. Atoms or groups within a
molecule move to different positions,
leading to a new molecular structure.
Characteristics: These reactions often
involve the formation of more stable or
more functional molecules. They can
occur as part of other reaction
processes (like during an SN1 reaction)
or can be initiated by heat or light.
For example- The Benzil-Benzilic Acid
rearrangement is a well-known organic
reaction in which a 1,2-diketone (benzil)
undergoes a rearrangement to form an
α-hydroxy-carboxylic acid (benzilic acid)
under the influence of a base. This
reaction is a type of 1,2-rearrangement,
a fundamental transformation in organic
synthesis.
