Optical activity without asymmetric carbon
Case of Allene
Allenes with even π bonds
Allenes with odd π bonds
groups at the end of allene structure lie in same plane
cis trans
Case of spiranes
spiranes with even rings
shows Optical isomerism
Spiranes with odd rings
Case of cycloalkylidene
Case of ortho-ortho-tetrasubstituted biphenyls
Chiral centres other than carbon
Asymmetric nitrogen : Amine inversion
(Interconvertible & non-resolvable)
invertomers
Nitrogen salts and cyclic amines will NOT undergo amine inversion
(non-Interconvertible & resolvable)
(non-Interconvertible & resolvable)
(non-Interconvertible & resolvable)
Calculation of number of stereoisomers
Stereocentre: Stereocentre is defined as an atom or bond bearing groups of such nature
that an interchange of any two group will produce a stereoisomer
Pseudo Chiral centre is an atom which is attached to two constitutionally like chiral groups and two other
distinct atoms/ groups.
Nature of compound No. of stereoisomers (n=No. of stereocenters)
Compound with dissimilar ends
Compound with Similar ends with even stereocenters
Compound with Similar ends with odd stereocenters
Compounds having similar ends with even chiral centres enantiomers = 2n-1 meso compounds =
then:
Compounds having similar ends with odd chiral centres Enantiomers= Meso=
then:
If the starting materials of a reaction are achiral and the products are chiral, then they
will be formed as a racemic mixture of two enantiomers
Conformers / Rotational Isomers / Conformational isomers
There are infinite arrangement (conformations) which arise due to free rotation around
carbon-carbon σ bond, out of them different conformations corresponding to energy
minima are called conformers .
The conformational isomerism arises due to free rotation along a bond
Dihedral angle :
The angle between C — X and C — Y in X—C — C — Y when it is visualised along C — C bond
H
H H
H H
H
H
H
H
Skew conformation: All conformations other than staggered or eclipsed are skew conformations
Stability order : Staggered > Ecilpsed
Conformational analysis of butane
rotation about the C2--C3
Energy profile of conformations of butane
stability order:
Anti > Gauche > Partially eclipsed > Fully eclipsed
Case of intramolecular hydrogen bonding
Stability order:
Gauche form > Anti form > Partially eclipsed > Fully eclipsed
ELECTRON DISPLACEMENT EFFECTS
PERMANENT TEMPORARY
EFFECT EFFECT
I, R, H E
(I) Inductive effect
Partial displacement of σ electrons towards more electronegative atom
1
𝑑𝑖𝑠𝑡𝑎𝑛𝑐𝑒
–I Effect
+I Effect
Resonance
When the properties of a molecule cannot be explained by a single Lewis structure,
More than one lewis structure are required to explain its properties
the phenomenon is known is known as resonance
Characteristics of resonance structures
(a)They are hypothetical.
(b)Each resonance structure will have same skeleton, net charge, paired/unpaired electrons,
approximate same energy.
(c) Hybridisation of atoms do not change.
(d)They will differ only in the distribution/delocalisation of π-electrons.
Positions of atomic nuclei is same
Out of two π bonds only one π bond will take part in delocalisation
drawing resonating structures
stability of different resonance structures
Resonating structure with more π bonds will be more stable or structures in which all of the atoms have a
complete (OCTET) valence shell of electrons (i.e., the noble gas structure) are especially stable and make large
contributions to the hybrid
Charge separation decreases stability
+ R/M effect
- R/M effect
SIR effect (Steric Inhibition of Resonance)
Restriction in exhibition of resonance due to steric hindrance is known as SIR effect
In case of 1,2-disubstituted benzene if the substitutents are bulky then due to steric repulsion (vander waal
repulsion) the group go out of plane with respect to benzene ring.
SIR effect ∝ Size of ortho substituent group
SIR effect order = III > IV > II > I.
Hyperconjugation (No bond resonance)
C–H bond of sp3 carbon will be in the conjugation with p-orbitals (alkene, alkyne, carbocation
and free radical)
A carbon intermediate which contain
three bond pair and a negative charge
Generally carbanions do not undergo rearrangement
Carbanions acts as lewis base or nucleophile
Free radicals An uncharged intermediate which has three bond pair and an unpaired electron
Homolysis of covalent bond results into free radical intermediates possess the unpaired electrons
It is generated in presence of Sun light, Peroxides or High temperature
1) It is neutral species with odd e¯
(2) It is paramagnetic in nature due to odd e¯ free radical is stabilised by:
(3) No rearrangement is observed generally. +I groups,
(4) Carbon atom having odd electron is in sp2 hybridised state
(5) Any reaction if it is carried out in the presence of sunlight, peroxide or Resonance,
high temperature it generally proceeds via free radical intermediate Hyperconjugation
Stability order
free radical is stabilised by:
+I groups,
Resonance,
Hyperconjugation
Stability order
free radical is stabilised by:
+I groups,
Resonance,
Hyperconjugation
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Stability order
Carbocations
A carbon intermediate which contain three bond pair & a positive charge on it is called carbocation.
Hybridisation : Carbocation may be sp2 & sp hybridised
Carbocations are electron deficient. They have only six electrons in their valence shell,
and because of this, carbocations act as Lewis acids
Because carbocations are electron seeking reagents, chemists call them electrophiles
Carbocations are Stabilized by: +I, + M effect, delocalisation of charge, Hyperconjugation
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Acidic Strength?
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Acidic strength
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