Module – 3 (part – 2)
Introduction to reactions involving
Substitution, Addition, Elimination,
Oxidation, Reduction, Cyclization, Ring
openings, Synthesis of a commonly used
drug molecule.
Substitution
Addition
Elimination
Organic Reaction Oxidation
Reduction
Cyclization
Ring Openings
Substitution Reactions
In a substitution
reaction, generally, one
atom or a group of
atoms take place of
another atom or a
group of atoms which
leads to the formation of
an altogether new
substance.
SN2 Mechanism
SN2 reactions are bimolecular in rate of reaction and
have a concerted mechanism.
The process involves simultaneous bond formation by the
nucleophile and bond cleavage by the leaving group.
For reactivity using an SN2 mechanism, primary >>
secondary >> tertiary carbon centers.
SN1 Mechanism
Unimolecular in rate of reaction
Two steps
First step – Bond Cleavege by Leaving group (LG)
Generate a carbocation intermediate.
Second step, the electronegative nucleophile attacks the
carbocation to form the product.
The nucleophile can attach either side of the carbocation, which
adopts an sp2-hybridized orbital with a trigonal planar geometry,
For reactivity using an SN1 mechanism, tertiary >> secondary
>>> primary carbon centers.
Addition Reaction
The most common chemical transformation of a carbon-carbon
double bond is the addition reaction.
Oxidation and reduction Reaction
Oxidation - Addition of Oxygen or removal of hydrogen
Reduction – Removal of Oxygen of addition of Hydrogen
Heteroatoms such as oxygen and nitrogen
are more electronegative than carbon, so when
a carbon atom gains a bond to a heteroatom, it
loses electron density and is thus being
oxidized.
Conversely, hydrogen is less
electronegative than carbon, so when a carbon
gains a bond to a hydrogen, it is gaining
electron density, and thus being reduced.
Two important reagents for the reduction of aldehydes and
ketones to alcohols are sodium borohydride (NaBH 4) and lithium
aluminum hydride (LiAlH4)
Elimination Reactions
There are certain reactions which involve the
elimination and removal of the adjacent atoms. After these
multiple bonds are simultaneously formed and there is a
release of small molecules as products as a result.
One of the examples of a typical elimination reaction is the
conversion of ethyl chloride to ethylene.
CH3CH2Cl → CH2= CH2 + HCl
In the above reaction, the eliminated molecule is HCl, which
can form out of the combination of H+ from the carbon atom
which is on the left side and Cl– from the carbon atom which is
on the right side.
[Link]
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
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
Ring-Opening
Epoxides are three-membered rings containing an oxygen atom. They
are associated with high ring tension and this is the basis of their
reactivity towards nucleophiles despite lacking a good leaving group
Epoxide Ring-Opening by Other Nucleophiles
cyclization reaction
The Nazarov cyclization reaction (often referred to as
simply the Nazarov cyclization) is a chemical reaction used
in organic chemistry for the synthesis of cyclopentenones.
Cyclization reaction (Dieckmann condensation)
The Dieckmann condensation is the intramolecular chemical
reaction of diesters with base to give β-ketoesters.
It is named after the German chemist Walter Dieckmann
(1869–1925).
cyclic β-keto esters,
1,6 diesters
Ref.:
[Link]
nic_Chemistry)/Reactions/Organic_Reactions/Dieckmann_Condensation