Reaction Mechanism

Examples
Carbocation
Carbocation are reactive intermediates in
Concept Ladder Note: Previous Year’s Question
which carbon bearing the positive charge, sp2
hybridised, plannar and having 6e- in their valence 1. Electron-withdrawing group increases
shell. Electrophiles are be electron stability whereas electron-releasing (R) group The radical, is aromatic
deficient species, looking to decreases the stability of carbanions.
Structure
attack an electron rich site because it has
2. The stability of carbanions increases with
(Nucleophilic Substrate). [NEET]
increase in 's' character (electron withdrawing).
These are classified as (1) 7 p-orbitals and 7 unpaired
follows: Stability of Carbanions
electrons
1. (2) 6 p-orbitals and 7 unpaired
electrons
2. (3) 6 p-orbitals and 6 unpaired
Example
+ + +
electrons
CH3 , CH2 = CHCH2 , C6H5 CH2 .....etc. Free Radicals (4) 7 p-orbitals and 6 unpaired
Note: Free radical are reactive intermediates in electrons
1. Alkyl group (R) disperse +ve charge over which carbon bearing the unpaired electron, sp2
carbon. hybridised, planar and having 7e- in their valence
Rack your Brain
2. Electron withdrawing groups pulls electron shell.
density away from C+ carbon which decreases How resonance is related to Strucutre
stability of carbocation. carbocation stability? Rack your Brain
3. More is the number of a-H attached to carbon
atom having +ve charge, more is the number What are ambident nucleophiles?
of hyperconjugative structures. Hence more
stable is carbocation.
Stability of carbocation Examples
Previous Year’s Questions

Carboanions The most stable carbocation,

Carboanions are reactive intermediates in among the following is
[NEET-2016] Note: Concept Ladder
which carbon bearing the negative charge, sp3 +

hybridised, pyramidal and having 8e- in their (1) ( CH3 ) C— CH— CH3 1. As the number of alpha H-atoms are increasing.
3 Nucleophile are electron
valence shell.
+
(2) CH3 — CH2 — CH — CH2 — CH3 The hyperconjugation effect is increasing and rich species, looking to
Structure + stability increasing. attack a +ve charged centre.
(3) CH3 — CH— CH2 — CH2 — CH3
Reaction Mechanism

Reaction Mechanism

+
Stability of Free Radicals Nucleophiles may be
(4) CH3 — CH2 — CH2 charged:- H-, OH-;
Neutral:- NH3 H2O;
Ambident:-CN-, O—N=O

1. 2.
Inductive Effect Order of + I effect
Displacement of an electron cloud along the Definitions
carbon atom chain due to the presence of an y
electron withdrawing groups or electron releasing Inductive Effect is the
groups in the carbon chain is known as Inductive phenomenon where a
Effect. permanent dipole arises in a
molecule due to the unequal y —CT3 > —CD3 > —CH3 (+ I effect)
Types of Inductive Effect Order of -I effect
sharing of the bonding electrons
(1) -I Effect (2) +I Effect in the molecule.
(1) -I Effect
Any atom or group which attracts electrons
more strongly than hydrogen is said to exert a Concept Ladder
negative effect (-I effect) Note: Complete positive charge > +d positive
(1) Inductive effect depends charge > EN Factor (-I effect) Rack your Brain
upon the hybridisation of Application of Inductive effect
carbon atom. (1) Stability of carbocation and free radical Why do alkyl groups show +I
(2) It is a distance dependent effect?
Ex. 1
effect, after 3 or 4 carbon.
(2) +I Effect
Inductive effect will be
An atom or group which attracts electrons zero.
less strongly than hydrogen is said to exert a (3) Any atom or group
positive inductive effect (+I effect). attracts electrons more
strongly than hydrogen is
said to exert a negative
effect (-I effect); an atom Stability of Carbocation: (III) > (II) > (I) Previous Year’s Question
or group which attracts Ex. 2
Features electrons less strongly Which of the following is correct
(1) Permanent Effect. than hydrogen is said to with respect to – I effect of the
(2) Inductive effect is a weak effect. exert a positive inductive substituents? (R = alkyl)
effect (I-effect) [NEET]
(1) –NH2 < –OR <– F
(2) –NR2 < –OR < –F
(3) –NH2 > –OR > –F
Stability of Carbocation: III > II > I
Hybridisation of C-atom sp3 sp2 sp (4) –NR2 > –OR > –F
Ex. 3
Reaction Mechanism

Reaction Mechanism

% of s-character 25% 33% 50%

sp3 < sp2 < sp (greater the s-character, greater will

EN of C-atom
be the EN of the C-atom)
Stability of Free radical : III > II > I

3. 4.
Ex. 4 y Acid strength ∝ – I effect
CH3COOH < Cl–CH2COOH < Cl2CH–COOH < Cl3C–COOH
y Halogen having stronger –I effect makes an acid stronger. For example
F–CH2COOH > Cl –CH2–COOH > Br–CH2–COOH > I–CH2–COOH
y Increase in the number of halogen atoms on the a–carbon atom exerts greater inductive
effect, thus increasing the –OH bond polarity, Consequently the acid becomes stronger.
CCI3–COOH < CBr3–COOH < CCl3–COOH < CF3–COOH
(Weakest acid) (Strongest acid)

Stability of Carbocation: I > II > III (Distance factor) Acidic strength acc. to periodic table
(a) Acidic strength in period
tertiary (3°) carbocation is more stable than that of secondary (2°) carbocation which is
stable than that of primary (1°) carbocation. It is due to +I effect of the methyl group. Rack your Brain

(2) Stability of Anion

Acidic strength of halogen acids
Ex. 1
increases down the group. Why?

Stability of Carbocation: (I) > (II) > (III) > (IV) (b) Acidic strength acc. to group
Ex. 2 Concept Ladder

1. Stability of anion
∝ -I effect or 1/+I effect.
2. 
Stability of unsaturated Concept Ladder
anion > Stability of
Stability of Carbocation: (III) > (IV) > (II) > (I) saturated anion
A Lewis acid is any species
(3) Acidic Strength (molecule or ion) that can
accept a pair of electrons,
1
Acid strength ∝ Basicity of amines : and a Lewis base is any
+I effect
Basicity of aliphatic primary amines : In species (molecule or ion)
CH3 that can donate a pair of
aliphatic amines, R – NH2, the +I effect of alkyl
Reaction Mechanism

Reaction Mechanism

|
HCOOH > CH3COOH > CH3 —CH2 —COOH> CH3 — CH — COOH > CH3 — C — COOH group increases the electron density on nitrogen electrons.
| | atom of –NH2 group. As a result, its tendency to
CH3 CH3
donate the electron pair to a proton increases.
basic strength of aliphatic primary amines is : NH3 < RNH2

5. 6.
Basic strength of amine in different medium Basic strength of amine in aqueous medium
(1) Basic Strength of amine in gaseous state (1) Basic strength of amine in case of methyl
amine.

(2) Basic strength of amine in case of ethyl amine

Concept Ladder
Note:
1
(1) Basic strength ∝ +I effect ∝
(2) Basic strength of amine in case of non-polar medium −I effect The formula of the
(2) Basic strength ∝ Tendency donate lone pair of conjugate base is the
electrons to H+ ion. formula of the acid less
(3) Basic strength ∝ Stability of cation. one hydrogen. The formula
Resonance of the conjugate acid is the
y When properties of a molecules can not explain formula of the base plus
by single lewis dot structure even some time, one hydrogen ion.
Reaction Mechanism

Reaction Mechanism

we made more than 1 lewis dot structure

that all structure canonical/resonating/
contributing structure but real structure is
resonating hybrid. Which can explain all pp

7. 8.
 and cp of molecule, for a resonance comp. (2) =/- at conjugated position
must have conjugated system.

(3) = / at conjugated position

y Hypothetical concept.
y Permanent effect. Concept Ladder
y General resonance is stabilizing phenomenon. Concept Ladder
y In resonance we can’t change position of (4) =/Free radical at conjugated position
Resonance structures are
atom. It involve only delocalisation of p-e-s/ Resonance is a way of not in equilibrium with
lone pair/ -ve charge/ free radical and +ve describing delocalized each other, they represent
charge. electrons within certain contributions to an overall
y Resonance is a intermolecular phenomenon. molecules or polyatomic resonance “Hybrid”.
y Atoms or orbital which are participate in ions where the bonding
resonance must be in the same plane (comp. cannot be expressed by (5) =/conjugated with D.B.
must be planer or innerly planer only in a single Lewis formula. A (a)
resonance area) molecule or ion with such
y In resonance pure p-orbital/ pure d-orbitals delocalized electrons is
are participated (anhydride orbitals) represented by several
y Hybrid orbital never participate in resonance. resonance structures. In 1, 3-butadine resonance takes place in both the directions so it is bidirectional
y More stable resonating structure will give
(b)
more contribution resonating hybrid.

Note:
y Formal charge never participate in resonance.

Condition for resonance/Mesmeric effect.

Reaction Mechanism

Reaction Mechanism

(1) Double bond/+ at conjugated position

9. 10.
y Any compound must have 3 parallel p-orbitals Extended Resonance
for resonance.
(a)
y For ions must have two parallel p-orbital
Different Resonating Structures Rack your Brain
(1)
(I) (II) Why carboxylic acids (RCOOH)
Stability: I > II are less stable than carboxylate
(b) ions (RCOO-) ions?

(2) (I) (II) Stability: I > II

Note:
y In linear molecule, resonance effect observed
at both terminal position .
y In benzene molecule, resonance effect
observed at ortho and para position. Concept Ladder
Equivalent Resonance
y It more effective than normal resonance. Resonance structures are
not in equilibrium with
(a) O O
|| || each other, they represent
CH3 − C − OH  CH3 − C − O− + H+ contributions to an overall
resonance “Hybrid”.
Acetic Acid Acetate ion

(1) +M/+R effect

(b) H2CO3  2H+ + CO3−2
Reaction Mechanism

Reaction Mechanism

+M/+R groups

11. 12.
(2) -M/-R effects Examples:
(1)

-M/-R groups Previous Year’s Question

Stability: I > II Which of the following

—NO2—SO3H, —CHO, —COOH, —C ≡ CH, etc. (2) carbocations is expected to be
Note: most stable? [NEET]
1
Stability of anion ∝ − M / −I ∝ ∝ extent of resonance
+M / + I
(1) (2)
Steric inhibition of Resonance [SIR]
Whenever bulky group at ortho position of
triangular group due to steric repulsion triangular Stability: II > I
group change its plane [Out of plane] so tendency (3)
of resonance with benzene decrease this is (3) (4)
known as SIR.
Previous Year’s Question

A tertiary butyl carbocation is

more stable than asecondary
butyl carbocation because of
which of the following? Stability: II > I
[NEET] Note:
(1)–I effect of – CH3 groups Ortho Effect (For only aromatic carboxylic acid)
(2)+R effect of – CH3 groups 1. Ortho effect is the application of SIR.
(3)–R effect of –CH3 groups 2. Ortho substituted aromatic acid is more acidic
(4)Hyperconjugation than para and meta substituted carboxylic
Rack your Brain
acid, this effect is known as ortho effect.
Example
(a) All triangular group (1) Ortho substituted aromatic acid
is more acidic than para and
meta substituted carboxylic
acid. Why?
Reaction Mechanism

Reaction Mechanism

(b) Bulky group

All triangular group + all alkyl group

13. 14.
Note:
1
Basic Strength ∝
Resonating Structures
1
Basic Strength ∝
% s − Character of Donor atom
1
Basic Strength ∝ +I/+M ∝
−I / −M
Aromatic Non-Aromatic Anti-aromatic

(2) Concept Ladder Compound must be cyclic Out of four, as disscoused Compound must be cycle
in aromatic condition. If any
There are thousands of one of condition violated
aromatic compounds then compound behave as
(3) that are not monocyclic non-aromatic
such as naphthalene, Compound must be planer Compound must be planer
azzulene, anthracene etc.
are polycyclic aromatic Compound must have cyclic Compound must have
hydrocarbons. resonance over the entire cyclic resonance
cyclic

Compound must follow Compound must follow

Aromaticity (Huckel’s Rule) Huckel’s rule Hucket’s rule
(4n + 2) p e- (4n) p e-

n = 0,1,2,3,4,5,……., etc. n = 1,2,3,4,5,……., etc.

Trick 2pe , 6pe , 10 pe , 14 pe ,

- - - -
Trick 4pe-, 8pe-, 12 pe-, etc
22 pe- etc
Examples of Aromatic Compounds:
Example: (1)
(a)

Rack your Brain

Rack your Brain (2)
In case of anti aromatic species
How % s-character of donor atom delocalisation of p-electrons
is related to basic strength? Examples of Non Aromatic Compounds: dows not takes place. Why?
Reaction Mechanism

Reaction Mechanism

(1)

15. 16.
 (c)
(2)
Previous Year’s Question Rack your Brain

Cyclic hydrocarbon ‘A’ has Benzyl anion, Benzyl free radical,

Examples of Anti Aromatic Compounds:
all the carbon and hydrogen aniline, phenol and benzyl cation
(1)
atomsinasingleplane. are all aromatic compounds.
Allthecarbon–carbonbondshave Why?
the same length, less than 1.54Å,
but more than 1.34Å. The bond
(2) angle will be [AIPMT]

Q.1 Write down the stability of the following species?

(1) 109°28']
(2) 100°
(3) 180°
Quasi aromatic compound
(4) 120°
y Ionisied aromatic compound is known as
Quasi aromatic compound.
y Quasi aromatic compound have always non- A.1 Stability: III > I > II
zero dipole moment.
y Quasi aromatic compound soluble in polar
Rack your Brain
solvent. Q.2 Write down the stability of the following species?
Examples:
Why tropylium ion is aromatic in
(a)
nature?

Concept Ladder A.2 Stability: III > II > I

(b)
Q.3 Write down the stability of the following species?
Reaction Mechanism

Reaction Mechanism

A.3 Stability: III > II > I

17. 18.
Bredt’s Rule
It states that a double bond cannot be placed Previous Year’s Question
at the bridgehead of bridged ring system, unless
the ring are large enough.
Which amongst the following is
Applications
1. Stability of carbocation the most stable carbocation?
(i) [NEET]
+ +
(1) CH3 (2) CH3 CH2
CH3
+ |
(3) CH3 — CH (4) CH3 — C+
(ii)
| |
CH3 CH3
Note:
Dancing Resonance
(a) Only in cyclo proply methyl cation.
(b) Generally dancing resonance is more effective
than normal resonance.
Hyper-conjugation Effect (+H effect) II > I > III
(iii)

Previous Year’s Question Rack your Brain

Consider the following Why 3° allyl cation is more stable

Compounds : then that of 2° allyl cation?

y Permanent effect. 2. Stability of alkene

y Hypothetical concept. (i)
y In H.C. effect unparallel p-orbital participate.
Concept Ladder
y H.C. is week effect than resonance.
y H.C effect explain stability of carbo cation, In order to achieve stabililty,
free Radical, alkene which have atleast one Stability: I > II carbocation go through
a-hydrogen atom alkyl having at least 1 a (ii) rearrangement through
hydrogen. Hyperconjugation occurs in
shift of hydride ion (H-) or
y H.C effect can not explain stability of [NEET]
methide ion (CH3-) from
carboanion due to repulsion factor. (1) III only (2) I and III
adjacent carbon atom.
Reaction Mechanism

Reaction Mechanism

y H.C. effect also known as Natnan Bekar effect/ (3) I only (4) II only
Stability: II > I These shift are known as 1,
No bond Resonance. 2 shifts.
y Following conjugator system given hyper
conjugation effect.

19. 20.
(iii)
Q.5 Write down the stability of the following species?

Previous Year’s Question

Which of the following is the most

Stability: I > III > II stable carbocation (carbonium
(iv) ion)?
[NEET]
+ +
A.5
(1) CH3 CH2 (2) (CH3 )2 CH2
Stability: I > III > II
+ +
(3) ( CH3 )3 C (4) C6H5 CH2

Stability: I > II > III

Q.6 Discuss the bond energy of the following species.

Q.4 Write down the stability of the following species?

A.6

A.4

Q.7 Write down the stability of the following species?

Stability: I > II > III > IV

A.7
Reaction Mechanism

Reaction Mechanism

Stability: I > II > III

21. 22.
 Note:
Q.8 Write down the stability of the following species?
1. Heat of combustion ∝ No of carbon atom
2. If number of carbon atoms are equal then
1 Rack your Brain
Heat of combustion ∝
stability of comp.
Why heat of combustion is
Examples
A.8 (1)
inversely proportional to stability
of the compound?
Stability: I > II > III

H.O.C: I > II
Reverse hyper conjugation or -H effect (2)

H.O.C: I > II Previous Year’s Questions

(3)

2-Methyl-2-butene will be
represented as
H.O.C: II > I CH3 [NEET]
Note:
(4) |
y Reverse hyper conjugation Results decrease
(1) CH3 — CH — CH2CH4
in electron density. Rack your Brain
y It deactivat the ring. (2) CH3 — C = CH — CH4
H.O.C: I > II
|
y Reverse hyper conjugation shown by Bond energy is inversely Heat of Hydrogenation (H.O.H) CH3
m-directing group. proportional to stability of free Amoung of heat release when 1 mole
Bond Energy radical. Why? of unsotaurated hydrocarbon completely (3) CH3 — CH2 — C = CH2
|
1 hydrogenated into saturated compound. CH3
Bond Energy ∝
Stability of free radical Note:
Heat of hydrogenation number of p-bond (4) CH3 — CH2 — CH = CH2
Note: |
(Except aromatic) CH3
y If number of p-bond are equal, then heat of
1
hydrogenation ∝ .
Stability of alkene
Definitions
Examples
Heat of combustion is defined (1)
as the amount of heat liberated
Reaction Mechanism

Reaction Mechanism

when a given amount of

Heat of combustion (H.O.C)
the substance undergoes
Amount of heat released when a substance
combustion.
undergoes complete combustion with oxygen
HOH: I > II > III
under standard candtion.

23. 24.
(2) Observe that E+ (electrophile) adds to the atom
(group) where electrons are transferred. Such
Concept Ladder effect is known as +E effect i.e., when the transfer
HOH: I > II > III of electrons takes place towards the attacking
(3) reagent. . Rack your Brain
Keto-enol tautomerism
is possible only in those -E Effect: In polar bonds, in presence of attacking
ketones and aldehydes reagent, a complete transfer of electron (one of p Why electromeric effect is a
HOH: II > I e- pair) to more electronegative atom takes place,
in which at least one temporary polarising effect?
Note: a-hydrogen atom is present e.g., in presence of nucleophiles like R-,
Order of Effect so that it may convert the
carbonyl group to enol CN-, HSO3-, p electrons shifts over to O.
Resonance > Hyper conjugation > -I Effect
group.
Order of +M effect

Observe that CN- (nucleophile) adds to the atom

(group) from where electrons are transferred.
Order of -M effect Such effect is known as -E effect i.e., when the
transfer of electrons takes place away from the
attacking reagent. Previous Year’s Questions
Tautomerism (Chemistry of a-H)
Compound having same. molecular formula Given
but different structural formula due to transfer
of acidic Hydrogen is known as tautomer’s and
Electromeric effect (E effect) phenomenon is Tautomerism.
y Temporary effect
y It involve complete delocalization of electrons.
Previous Year’s Questions Which of the given compounds
y It operates only in molecules having
can exhibit tautomerism?
p-electrons (i.e, multiple bonded compounds).
y It induced by the attracking reagents Which of the following statements
[NEET]
(nucleophiles & electrophiles) in a chemical is not correct for a nucleophile?
(1) II and III
reaction. Two tautomers have dynamic equation
y (2) I, II and III
Type of Electromeric effect [NEET]
that’s why tautomerism also known as (3) I and II
1. +E effect 2. –E effect (1) Ammonia is a nucleophile
Desmotropism. (4) I and III
+E Effect: In presence of electrophiles (E+), p-ele. (2) Nucleophiles attack low e–
y Due to rapid shifting of H+ ion tautomerism
ctrons shifts to other carbon to make adjustment density sites
also known as cationotropy/ prototropy.
for the incoming electrophile to be added. (3) Nucleophiles are not electron
Reaction Mechanism

Reaction Mechanism

y All tautomer also have functional group I but

seeking
periorty given to tautomerism.
(4) Nucleophile is a Lewis acid
y Two tautomeric structure are real in
nature while two resonanting structure are
hypothetical.

25. 26.
y Due to rapid shifting of H+ ions between two According to Bredt's rule a double bond cannot
atoms of same molecule due to acid/ base be placed at the bridgehead of a bridged ring
rxn is known as tautomerism. system, unless the rings are large enough.
Previous Year’s Questions

Which among the given molecules

can exhibit tautomerism?

Note:
y If acidic character in C—H bond increasing, Type of tautomerism [AIPMT]
then stability of Anion Increasing, Rate Keto–enol tautomerism (1) III only
determing step should be fast, reaction 1. (2) Both I and III
Previous Year’s Questions
farours to the forward direction and enol (3) Both I and II
content increasing. (4) Both II and III
The enolic form of ethyl
Example:
acetoacetate as shown below has
(1)

2. Nitro – Aci fom

(2) Concept Ladder

[NEET]
(1) 9 sigma bonds and 2 pi-bonds
(2) 9 sigma bonds and 1 pi-bond Keto-enol equilibrium more
(3) 18 sigma bonds and 2 pi- Nitro form Aci form fvavourable by stabilizing the
bonds enol form such as extended
(4) 16 sigma bonds and 1 pi-bond 3. Amido–imido form tauto conjugation, intramolecular
(3)
H-bonding and aromatic
characters etc.

Bredt's Rule in tautomerism Amido form Imido form

If Bredt's rule violate in enol form then compound
does not exit tautomerism. Q.9 Which of the following species has maximum enol content.
Reaction Mechanism

Reaction Mechanism

(I) (II)
A.9 enol content: I > II

27. 28.
4. Cyano–isocyano tauto Enol content

Previous Year’s Questions

Tautomerism is exhibited by

[AIPMT]
(1) R3CNO2
(2) RCH2NO2
(3) (CH3)3CNO
Keto-enol content (4) (CH3)2NH
y Generally keto form is more stable than its enol
form because (C = 0) is thermodynamically Q.10 Draw the possible resonance structure for CH3 − O
+
 − CH and predict which of
2

more stable bond. the structures is more stable. Give the reason for your answer.
y It as covalent as well as extra ionic character
that why reaction favours to direction of (C
= 0). A.10
y Enol form may be stable than its keto form
Concept Ladder
if following factors are present in enol form.
1. Hydrogen bonding The structure A is less stable than that of the structure C because structure
2. Resonance Keto-enol tautomerism
is possible only in those C has complete octet of all the atoms, whereas, in structure A, carbon atom
3. Armoaticity
4. Acidic character in C—H bond. ketones and aldehydes have a positive charge and incomplete octet (8 electrons in its valence shell).
Note: in which at least one
Active methylene a-hydrogen atom is present
so that it may convert the
Whenever CH2 having strong e- withdrawing
goup then it is called active methylene. carbonyl group to enol Q.11 Which of the following ions is more stable? Use resonance to explain your
answer.
In case of active methylene enol content form group.
always more than 50%.
Electron withdrawing group:

allylic > 3° > 2° > 1° > methyl

enol content > 50% A.11
Rack your Brain The stability of carbocation is decided by hyperconjugation, resonance and
Note:
Generally acid and acid derivaties formed less inductive effect.
In most of the cases, the keto
Reaction Mechanism

Reaction Mechanism

enol content. As structure A is having a primary (allylic) carbocation, whereas the carbocation
form is more stable than the
Ex. enol form. Why? in structure B has secondary (allylic) carbocation.

29. 30.
Q.12 The structure of triphenylmethyl cation is given below. This is very stable and
Q.15 Draw the resonance structures of the following compounds.
some of its salts can be stored for months. Explain the cause of the high 
CH=2 CH − Cl:
stability of this cation. 

A.15

Triphenylmethyl cation is tertiary carbocation and the positive charge is on

A.12 Q.16 Why does SO3 act as an electrophile?
the carbon atom which is stabilized by three phenyl group by resonance. Due
to the resonance the stability increases. Oxygen is more EN than sulphur. The electron density at S in SO3 is reduced
A.16
by the oxygen atoms therefore to suppress the partial positive charge SO3
Q.13 Identify the most stable species in the following set of ions giving reasons.
acts as an electrophile
+ + + +
CH3 , CH2Br, CHBr2 , CBr3
− − − −
CH3 , CH2Cl, CHCl 2 , C Cl 3 Q.17 Write down the stability of the following species.
+ + +

(i) Bromine atom is an electron-accepting (electron-withdrawing) group and C6H5 — C— C6H5 , C6H5 — CH2 , C6H5 — CH — C6H5
A.13 |
has a lone pair of electrons, Br-atom destabilizes the positive charge on a C6H5
C-atom. Hence CH3+ will be more stable. More is the number of resonanting strucutres dispersing the +ve charge over
(ii) CCl 3 will be most stable because Cl is electron-accepting (electron-
A.17
carbon, more is teh carbocation stability e.g.
+ + +
withdrawing) atom and the negative charge on C-atom will be stabilized by C6H5 — C— C6H5 > C6H5 — CH — C6H5 > C6H5 — CH2
|
the Cl-atom. As the number of Cl-atom attached to carbocation increases the C6H5
stability also increases.

Q.14 Give two points of difference between the inductive effect and resonance
effect. Q.18 Hybridisation of nitrogen I and II in the following compound is:

A.14 Inductive Effect Resonance Effect

The transmission of the electron The transmission occurs from

In pyridine ring electron pair of N atom is localized due to sp2 hybridization
is only from sigma bond. both sigma and pi bond. A.18
Reaction Mechanism

Reaction Mechanism

and it is not the part of close loop. While in pyrrole electron pair of N is
delocalized and it is part of close loop, hence hybridization state of this N
It is possible when the It is possible only if the system
atom is sp2 not sp3.
polarization of bond takes place. is conjugated.

31. 32.
Q.19 Explain the hyperconjugative stability of tert-butyl cation and 2-butene?
Chapter Summary

1. Bond length
Hyperconjugation is tert-butyl carbocation refers to delocalisation of
A.19 (i) C 3 − C 3 > C 2 − C 2 > C( sp) − C( sp)
s-electrons of C—H bond over the empty p-orbital of carbocation. In 2-butene, ( )
sp sp ( )
sp sp ( ) ( )
1.54Å 1.48Å 1.38Å
it refers to delocalisation of s-electrons of C—H bond over the p* orbitals of
C=C. (ii) C − C > C = C > C = C
1.5Å 1.34Å 1.20Å

(iii) Benzene - C—C bond length = 1.34Å

Resonance energy of benzene = 36.0 K cal/mol = 150.62 KJ.

2. (i) Electron withdrawing group showing –I effect (decreasing order)

R3N+ > NO2 > CN > COOH > F > Cl > Br > I > OCH3 > OH

(ii) Electron donating group showing +I effect (decreasing order)

O− > COO− > ( CH3 )3 C > ( CH3 )2 CH > CH3CH2CH2 > CH3

3. Hyperconjugation effect is weaker than resonance effect.

4. Resonance effect is powerful than inductive effect.

5. Stability of carbocations:
+ + + + +
(i) (C6H5 )3 C > (C6H5 )2 CH > C6H5 CH2 > CH2 = CH — CH2 > R — C = CH2 >
+ + ⊕ ⊕
CH3 CH2 > R — CH = CH > C6H5+ > CH3 > HC = C

(ii) 3° benzylic > 2° benzylic > 1° benzylic

6. Aromatic: Cyclic, planar, complete conjugation (4n + 2)p e-s, where n = 0, 1, 2....

7. Anti-aromatic: Cyclic planar, complete conjugation, 4np e-s, where n = 1, 2 ....

8. Non-aromatic: Not cyclic or not planar or not completely conjugated.

9. Resonance: When a ion/molecule can be represented by two or more different type

of structures but the same arrangement of atomic nuclei but differ in distribution of
Reaction Mechanism

Reaction Mechanism

electrons, the phenomenon is called as Resonance.

10. Hyperconjugation is also known as no-bond resoancne.

33. 34.