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Organic Chemistry - Basic Concepts- Notes (1)

The document discusses isomerism in organic chemistry, detailing types such as structural isomerism, chain isomerism, position isomerism, functional group isomerism, and metamerism. It also covers fundamental concepts in organic reaction mechanisms, including covalent bond fission, nucleophiles, electrophiles, and various electron displacement effects like inductive, resonance, and electromeric effects. Additionally, it explains hyperconjugation and its role in stabilizing carbocations.

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Nuaym Al Jafri
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9 views

Organic Chemistry - Basic Concepts- Notes (1)

The document discusses isomerism in organic chemistry, detailing types such as structural isomerism, chain isomerism, position isomerism, functional group isomerism, and metamerism. It also covers fundamental concepts in organic reaction mechanisms, including covalent bond fission, nucleophiles, electrophiles, and various electron displacement effects like inductive, resonance, and electromeric effects. Additionally, it explains hyperconjugation and its role in stabilizing carbocations.

Uploaded by

Nuaym Al Jafri
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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BASIC CONCEPTS OF ORGANIC CHEMISTRY

ISOMERISM
The phenomenon of existence of two or more compounds possessing the same molecular formula
but different properties is known as isomerism.
Isomerism: Structural
Compounds having the same molecular formula but different structures are classified as structural
isomers.

Different types of structural isomerism:-

(i) Chain isomerism:


When two or more compounds have similar molecular formula but different carbon
skeletons.

(ii) Position isomerism:


When two or more compounds differ in the position of substituent atom or functional
group on the carbon skeleton, they are called position isomers.

(iii) Functional group isomerism:


Two or more compounds having the same molecular formula but different functional
groups are called functional isomers

(iv) Metamerism:
It arises due to different alkyl chains on either side of the functional group in the
molecule.
CH3-O-CH2CH2CH3 & CH3CH2-O-CH2CH3
FUNDAMENTAL CONCEPTS IN ORGANIC REACTION MECHANISM
In an organic reaction, the organic molecule (also referred as a substrate) reacts with an
appropriate attacking reagent and leads to the formation of one or more intermediate(s) and
finally product(s).

Fission of a Covalent Bond

Heterolytic cleavage:
In heterolytic cleavage, the bond breaks in such a fashion that the shared pair of electrons remains
with one of the fragments.
a) Formation of carbo cation:

A species having a carbon atom possessing sextext of electrons and a positive charge is called a
carbocation (carbonium ion). They are highly unstable and reactive species.
Carbocations are classified as
(i) primary - CH3CH2+
(ii) secondary – (CH3)2CH+
(iii) tertiary – (CH3)3C+
Alkyl groups directly attached to the positively charged carbon stabilise the carbocations due to
inductive and hyperconjugation effects. The order of stability is
b) Formation of carbo anion:
The heterolytic cleavage can also give a species in which carbon gets the shared pair of
electrons.

A carbon species carrying a negative charge on carbon atom is called carbanion. They are
also unstable and reactive species.
Homolytic cleavage:
One of the electrons of the shared pair in a covalent bond goes with each of the bonded
atoms. i.e. the movement of a single electron takes place instead of an electron pair. Such
cleavage results in the formation of neutral species which contains an unpaired electron.
These species are called free radicals. They are also unstable and reactive species.

The order of stability of free radical is


Nucleophiles and Electrophiles
Nucleophile (Nu:):
A reagent that brings an electron pair is called a nucleophile. A nucleophile attacks an
electrophilic centre of the substrate which is that specific atom or part of the electrophilethat is
electron deficient.
Examples of nucleophiles:
(i) The negatively charged ions with lone pair of electrons. OH-, CN-, CR3-
(ii) Neutral molecules such as H2O, NH3, R2NH (due to the presence of lone pair of
electrons)

Electrophile (E+):
A reagent that takes away an electron pair is called electrophile. The electrophiles attack at
nucleophilic centre, which is the electron rich centre of the substrate. Thus, the electrophiles
receive electron pair from nucleophile.
Examples of electrophiles:
(i) Carbocations
(ii) Neutral molecules having functional groups like carbonyl group or alkyl
halides.

Electron Displacement Effects in Covalent Bonds


The electron displacement in an organic molecule may take place either in the ground state
under the influence of an atom or a substituent group or in the presence of an appropriate
attacking reagent.
a) Inductive Effect
When a covalent bond is formed between atoms of different electronegativity, the electron
density is more towards the more electronegative atom of the bond. Such a shift of electron
density results in a polar covalent bond.

Polarisation of σ-bond caused by the polarisation of adjacent σ-bond is known as the


inductive effect. This effect is passed on to the subsequent bonds also but the effect
decreases rapidly as the number of intervening bonds increases and becomes vanishingly
small after three bonds.
Types of inductive effect:
(i) –I effect:
Shown by electron withdrawing groups like –NO2, -CN, -COOH etc.
(ii) +I effect:
Shown by electron donating groups like alkyl groups (-CH3, -C2H2)
b) Resonance Structure
There are many organic molecules whose behaviour cannot be explained by a single Lewis
structure. The resonance structures (canonical structures) are hypothetical and individually
do not represent any real molecule. They contribute to the actual structure in proportion to
their stability.
The energy of actual structure of the molecule (the resonance hybrid) is lower than that of
any of the canonical structures. The difference in energy between the actual structure and
the lowest energy resonance structure is called the resonance stabilisation energy or simply
the resonance energy. The more the number of important contributing structures, the more
is the resonance energy.

Resonance Effect:
It is defined as ‘the polarity produced in the molecule by the interaction of two π-bonds or
between a π-bond and lone pair of electrons present on an adjacent atom’.
Types of resonance effect:
(i) Positive Resonance Effect (+R effect):
In this effect, the transfer of electrons is away from an atom or substituent group
attached to the conjugated system. This electron displacement makes certain
positions in the molecule of high electron densities.
The atoms or substituent groups, which shows +R effect: Halogens, -OH, -OR, -NH2,
-COOR, -NHR etc
Eg: Aniline

(ii) Negative Resonance Effect (- R effect):


This effect is observed when the transfer of electrons is towards the atom or
substituent group attached to the conjugated system.
The atoms or substituent groups, which shows -R effect: -COOH, -CHO, -CO, -CN, -
NO2 etc.
Eg: Nitrobenzene

c) Electromeric Effect (E effect)


It is defined as the complete transfer of a shared pair of π-electrons to one of the
atoms joined by a multiple bond on the demand of an attacking reagent. It is a
temporary effect. The organic compounds having a multiple bond show this effect in
the presence of an attacking reagent only.
Types of electromeric effect:
(i) Positive Eelctromeric Effect (+E effect):
In this effect the π−electrons of the multiple bond are transferred to that atom
to which the reagent gets attached.
(ii) Negative Electromeric Effect (–E effect)
In this effect the π - electrons of the multiple bond are transferred to that atom
to which the attacking reagent does not get attached.

❖ When inductive and electromeric effects operate in opposite directions, the


electomeric effect predominates.
d) Hyperconjugation
It involves delocalisation of σ electrons of C—H bond of an alkyl group directly
attached to an atom of unsaturated system or to an atom with an unshared p orbital.
Hyperconjugation is a permanent effect.

This type of overlap stabilises the carbocation because electron density from the
adjacent σ bond helps in dispersing the positive charge.

In general, greater the number of alkyl groups attached to a positively charged


carbon atom, the greater is the hyperconjugation interaction and stabilisation of the
cation.
The order of relative stability of carbocations by hyperconjugation:

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