Types of organic reaction

By Amresh Baitha
Types of reaction
• Addition reaction
• Substitution reaction
• Elimination reaction
• Condensation reaction
• Rearrangement reaction
• Pericyclic reaction
• Oxidation-Reduction reaction
General reaction:

Example:
 Addition reaction
➢ Addition reaction occurs when two or more
reactants combine to form a product without
the loss of any atoms present in the reactants.
➢ Addition reaction is common in compounds
that have unsaturated C-C bond, like double
(alkene) and triple (alkyne) bonds.
➢ The weaker π bond is converted into two new
stronger σ bonds.
➢ Alkenes can give rise to a wide variety of
products with various regioselectivity and
stereoselectivity depending on the reagent
and reaction conditions.
➢ There are typically two types of addition
reactions – electrophilic addition and
nucleophilic addition.
Examples of Addition Reaction
Addition Reaction of alkyne
Mechanism of Electrophilic Addition Reaction
Mechanism of Nucleophilic Addition Reaction
 Substitution reaction
➢Organic chemical reaction during which
a functional group replaces an atom or
another functional group attached to a
carbon atom in a compound.
Components of a Substitution Reaction
An electron-rich species donates a pair of electrons to an
electron-poor species and forms a new product and a new
base. Therefore, a substitution reaction contains four
components.
I. Nucleophile: the electron-rich species donating a pair
of electrons to carbon
II. Electrophile: the electron-deficient species accepting
a pair of electrons
III. Product: the species that is formed from a
substitution reaction
IV. Leaving group: the group that leaves the compound
Types of Substitution Reaction
 Nucleophilic substitution
When electron-rich species (nucleophile) provides an electron pair
for bonding with the compound being transformed, it is called
nucleophilic substitution. Some examples of nucleophiles are Cl–,
Br–, I–, OH–, RO–, CN–, H2O, and NH3.

Types of Nucleophilic Substitution:

• SN1 reaction
• SN2 reaction
• Nucleophilic aliphatic substitution
• Nucleophilic aromatic substitution
• Nucleophilic acyl substitution
 SN1 reaction
• The SN1 reaction is a type of nucleophilic substitution reaction in which an
electron-rich nucleophile displaces the halogen atom bonded to the central
carbon of an alkyl halide molecule.
• The halide ion that is displaced from the carbon atom is called the leaving
group.
• SN1 reaction takes place at the site of a saturated carbon atom.
• Some typical nucleophiles are halide (X–), hydroxy group (OH–), alkoxy group
(RO–), cyanide ion (CN–), hydrogen sulfide (H2S), ammonia (NH3), and water
(H2O).
General Reaction
 Characteristics of SN1 Reaction
• Two-step reaction process: 1. carbon-halogen bond breaks,
resulting in a positively charged carbon (carbocation)
and 2. nucleophile attacks the carbocation, forming a new bond
• Unimolecular and follows first-order kinetics
• Rate of the reaction depends on the concentration of the
substrate (alkyl halide)
• Has a racemization stereochemistry, i.e., both retention and
inversion products are formed
• Polar protic solvent is used to enhance the reactivity
• Mostly occurs in tertiary and secondary alkyl halide, with the
former having a higher reaction rate than the latter
Examples:
Mechanism of SN1 reaction
 SN2 reaction
• The SN2 reaction is a type of reaction in which an electron-rich
nucleophile displaces the halogen atom bonded to the central
carbon of an alkyl halide molecule.
• The halide ion that is displaced from the carbon atom is called
the leaving group.
• SN2 reaction takes place at the site of a saturated carbon atom.
• Some typical nucleophiles are halide (X–), hydroxy group (OH–),
alkoxy group (RO–), cyanide ion (CN–), hydrogen sulfide (H2S),
ammonia (NH3), and water (H2O).
General Reaction
 Characteristics of SN2 Reaction
• One-step reaction process, the reaction is concerted:
carbon-halogen bond breaking and carbon-nucleophile
bond formation takes place at the same time
• Bimolecular and follows second-order kinetics
• Rate of the reaction depends on the concentrations of the
substrate (alkyl halide) and the nucleophile
• Has an inversion stereochemistry at the reaction center
• Polar aprotic solvent is used to enhance the reactivity
• Mostly occurs in primary and secondary alkyl halides
Examples:
Mechanism of SN2 reaction
 Electrophilic substitution
When the substituent is electron-deficient (electrophile) and
accepts an electron pair for bonding with the compound to be
transformed, it is called electrophilic substitution. Some examples
of electrophiles are H3O+, NO2+, and SO3.

Types of Electrophilic Substitution:

• Electrophilic aliphatic substitution
• Electrophilic aromatic substitution
 Radical Substitution
Radical substitution takes place when an atom or group of
atoms in a molecule is replaced by a free radical. Some
examples of free radicals are Br, Cl, I, and OH.
Applications of Radical Substitution:
• Barton-McCombie deoxygenation
• Wohl-Ziegler reaction
• Hunsdiecker reaction
• Dowd-Beckwith reaction
• Barton reaction
• Minisci reaction
 Elimination reaction
• The elimination reaction is an organic reaction in which
two substituents are removed from a molecule to form
a new product.
• The process takes place in the presence of acid, base,
metal, and sometimes through heating.
• Through this process, it is possible to synthesize
unsaturated (double or triple bond between
carbon atoms) organic compounds from saturated
(single C-C bonds) ones.
• The elimination reaction is mechanically the reverse of
the addition reaction
The elimination reaction involves three fundamental steps:
• Removal of proton
• Formation of C=C pi (π) bond
• Breaking of the bond to the leaving group

Nomenclatures Used in Elimination Reaction:

• When a hydrogen atom is removed from the compound as a
proton (H+), the process is called deprotonation.
• If a halogen is removed, then it is called dehalogenation.
• If both hydrogen and halogen are removed, then it is called
dehydrohalogenation.
• If hydrogen and oxygen are removed together, as in the case
of alcohols, then it is a dehydration reaction or β-elimination.
 Types of Elimination Reaction
There are three types of elimination reaction
1. E1 type

• two-step removal mechanism process

• also known as unimolecular elimination
• formation of an intermediate
• the reaction rate is proportional to the concentration
of the compound to be transformed – first-order
kinetics
• regioselective and follows Zaitsev’s rule, i.e., favors
the formation of Zaitsev product
2. E2 type
• one step removal mechanism process
• also known as bimolecular reaction
• carbon-leaving group and carbon-hydrogen bonds break off
simultaneously
• the reaction rate is proportional to both the compound to be
transformed and the transferring agent – second-order kinetics
stereoselective and regioselective
3. E1cb type
• two-step elimination mechanism
• also known as unimolecular conjugate base elimination
• the compound has an acidic hydrogen atom and a weak leaving
group (e.g., -OH)
• standard in the dehydration reaction
Examples of elimination reaction for alkyl halide
Examples of elimination reaction for alcohol
Mechanism of Elimination reaction for alkyl halide
Mechanism of Elimination reaction for alcohol
E1 Vs E2 Reaction
 Condensation Reactions
• A reaction in which two molecules combine to form a single
molecule.
• A small molecule, often water, is usually removed during a
condensation reaction.
• Amino acids are important biological molecules that have an
amine functional group on one end of the molecule and a
carboxylic acid functional group on the other end.
• When two amino acids combine in a condensation reaction, a
covalent bond forms between the amine nitrogen of one amino
acid and the carboxyl carbon of the second amino acid.
• A molecule of water is then removed as a second product.
Example of condensation reaction
 Applications of condensation reaction
• Aldol condensation reaction
• Claisen condensation
• Knoevenagel condensation
 Aldol condensation
Condensation reaction in organic chemistry in which an enol or an
enolate ion reacts with a carbonyl compound to form a β-
hydroxyaldehyde or β-hydroxyketone (an aldol reaction), followed by
dehydration to give a conjugated enone.
 Claisen condensation
The Claisen condensation is a carbon–carbon bond forming reaction
that occurs between two esters or one ester and another carbonyl
compound in the presence of a strong base, resulting in a β-keto ester
or a β-diketone.
 Knoevenagel condensation
A Knoevenagel condensation is a
nucleophilic addition of an active
hydrogen compound to a carbonyl group
followed by a dehydration reaction in
which a molecule of water is eliminated
(hence condensation). The product is
often an α,β-unsaturated ketone (a
conjugated enone).
 Rearrangement Reactions
A rearrangement is a reaction in which the reactant and the
products are constitutional isomers and the reactant is
converted to the product by the migration of one or more
ligands from one point of the reactant to another.
Examples:
Beckmann rearrangement for oxime
 Pericyclic reaction

Pericyclic reactions are the concerted Cycloaddition reactions: Diels-Alder reaction

reactions involving reorganization of
electrons which occur by the way of a
single cyclic transition state.

Sigmatropic reaction

Electrocyclic reactions
Types of pericyclic reaction
 Characteristics of Pericyclic reactions

➢ The pericyclic reactions occur in single step and hence

there is no intermediate formed during the reaction.
➢ The breaking and making of bonds (both σ & π) occur
simultaneously in a cyclic transition state.
➢ The configuration of the product depends on
1. the configuration of reactants
2. the number of electron pairs undergoing reorganization
and
3. the reaction conditions (like thermal or photochemical).
 Oxidation-Reduction reaction
Oxidation reaction
When a carbon atom in an organic compound loses a bond to hydrogen and gains a
new bond to a heteroatom (or to another carbon), we say the compound has been
dehydrogenated, or oxidized. A very common biochemical example is the oxidation of
an alcohol to a ketone or aldehyde:
Reduction reaction
When a carbon atom in an organic compound gains a bond to hydrogen and loses a
bond to a heteroatom (or to another carbon atom), we say that the compound has
been hydrogenated, or reduced. The hydrogenation of a ketone to an alcohol, for
example, is overall the reverse of the alcohol dehydrogenation. Illustrated below is
another common possibility, the hydrogenation (reduction) of an alkene to an
alkane.
Methane, with four carbon-hydrogen bonds, is highly reduced. Next in the series
is methanol (one less carbon-hydrogen bond, one more carbon-oxygen bond),
followed by formaldehyde, formate, and finally carbon dioxide at the highly
oxidized end of the group.