NOTE

C H E M I S T R Y

GENERAL ORGANIC CHEMISTRY

CURIOUS CASES OF HYPERCONJUGATION
AND BREDT’S RULE

What you already know

• Resonance • Hyperconjugation in carbocations

• Hyperconjugation • Hyperconjugation in free radicals

What you will learn

• Hyperconjugation in alkenes • Reverse hyperconjugation

• Hyperconjugation in benzenoid compounds • Applications of hyperconjugation
• Bredt’s rule

MAIN BOARDS
Hyperconjugation in Alkenes

• Hyperconjugation exists in alkenes as well.

• More the number of α-hydrogen atoms (attached to sp3 hybridised carbon) around the
double bond, more is the hyperconjugation. It results in increased stability.
• Since propene has three α-hydrogen atoms, it has four hyperconjugative structures.
Hyperconjugation in propene is given as follows:
H H H+ H H
H
H C C C H C C C H
H

H H

H H H H H H

H+ C C C H H C C C H

H+
H
Hyperconjugation in propene
• There is no bond between α carbon atoms and one of the α-hydrogen atoms.
Hence, hyperconjugation is also known as no-bond resonance.
• Due to delocalisation of 𝞂 and 𝝿 bonds, a positive charge develops on the α-hydrogen atom
and a negative charge develops on carbon as shown in fig. 1.

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A three-dimensional representation of hyperconjugation in propene is shown in fig. 1.

+
H H +

H H H
H H –
C C H H
C C – H C C
H C H
C H
C H

H H H
H

Fig. 1: Three-dimensional representation of hyperconjugation in propene

Based on hyperconjugation

What is the order of stability of the given compounds?

CH3 CH3 CH3

H3C C C CH3 H3C C CH CH3

A B

Solution

Here, compound A has 12 α-hydrogens and compound B has 9 α-hydrogens. Since

compound A has more number of α-hydrogens, it has more hyperconjugative structures.

α α α
CH3 CH3 CH3
α α α α
H3C C C CH3 H3C C CH CH3
A B

12 α–Hydrogens 9 α–Hydrogens

Hence, compound A is more stable than B.

CH3 CH3 CH3

H3C C C CH3 > H3C C CH CH3

Thus, the order of stability is A > B.

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Based on hyperconjugation

What is the order of stability of the given compounds?

A B

Solution

Here, compound A has six 𝛂-hydrogens and compound B has three 𝛂-hydrogens. Since compound
A has more number of 𝛂-hydrogen atoms, it has more hyperconjugative structures.
α
H
α
H α
α H
H
α α α
H H H
α α
H H
A CH3 B

6 α-hydrogens 3 α-hydrogens

Hence, compound A is more stable than B.

>

Thus, the order of stability is A > B.

Based on hyperconjugation

What is the order of stability of the given compounds?

A B C

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Solution

Here, compound A has nine α-hydrogens, compound B has five α-hydrogens, and compound C
has two α-hydrogens. Since A has more number of α-hydrogens, it has more hyperconjugative
structures. Hence, A is more stable than B, which in turn is more stable than C.

α α
CH3 H α
H
H
α
αH

α α
H3C CH3
α
CH3
A B C
9 α-hydrogens 5 α-hydrogens 2 α-hydrogens

Thus, the order of stability is A > B > C.

> >

Based on the hyperconjugation in alkenes

Which of the following is the decreasing order of stability of the given alkenes?
CH3
H3C CH3 H3C CH3
CH3
H2C CH3 H3C
H H H3C CH3

(i) (ii) (iii) (iv)

(a) (i) > (ii) > (iii) > (iv) (b) (i) > (iii) > (ii) > (iv) (c) (iv) > (iii) > (ii) > (i) (d) (ii) > (i) > (iii) > (iv)

Solution

Here, (i) has three α-hydrogens, (ii) has six α-hydrogens, (iii) has nine α-hydrogens, and (iv) has 12
α-hydrogens.

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α
α α CH3 α α
H3C CH3 α H3C CH3
α CH3
H2C CH3 α
H H H3C CH3
H3C
α α

(i) (ii) (iii) (iv)

3 α-hydrogens 6 α-hydrogens 9 α-hydrogens 12 α-hydrogens

As the number of α-hydrogens increases, the stability of the alkene increases. Since (iv) has the
maximum number of α-hydrogens, it is the most stable compound among the given alkenes.
Thus, the order of stability is as follows: (iv) > (iii) > (ii) > (i)

H3C CH3 CH3 H3C CH3

> CH3 > > H2C CH3
H3C CH3 H H
H3C

Therefore, option (c) is the correct answer.

MAIN BOARDS
Hyperconjugation in Benzenoid Compounds

H C H
Hyperconjugation exists in benzenoid compounds like toluene.

Orientation influence of the methyl group due to hyperconjugation

Toluene has three α-hydrogens. Hyperconjugation in toluene results in a positive charge on an

α-hydrogen and a negative charge on the carbon atom of the benzene ring (structure A). This
negative charge undergoes conjugation with the double bond. Hence, resonance occurs. The
resonating structures (B and C) are depicted as follows:

H H H H
H C H H+ C H H+ C H H+ C H

Structure A Structure B Structure C

Hyperconjugation in toluene

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Hyperconjugation in toluene results in the accumulation of negative charge in the ortho and
para positions of the benzene ring. Hence, toluene has a +H effect.

Baker-Nathan effect

• The phenomenon of hyperconjugation was originally observed by Baker and Nathan.

Therefore, hyperconjugation is also known as the Baker-Nathan effect.
• The Baker-Nathan effect explains that hyperconjugation dominates over inductive effect.

Based on the hyperconjugation in benzenoid compounds

Determine the order of electron density on the given phenyl rings.

CH3 CH3

CH3 CH2 CH3 CH CH3 CH3 C CH3

A B C D

Solution

The number of α-hydrogens present in each of these compounds can be given as follows:
CH3 CH3

α α α
CH3 CH2 CH3 CH CH3 CH3 C CH3

A B C D
3 α–hydrogens 2 α–hydrogens 1 α–hydrogen 0 α–hydrogen

As the number of α-hydrogens increases, the number of hyperconjugative structures increases.

Hence, the stability of the compound increases. The compound with more hyperconjugative
structures has more electron density on the phenyl rings.

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Hence, the order of electron density on the phenyl rings can be given as follows:
CH3 CH3

CH3 CH2 CH3 CH CH3 CH3 C CH3

> > >

Based on the hyperconjugation

In which of the following compounds does the hyperconjugation occur?

CH3 Ph

CH3 C CH
Ph C Ph
CH3
CH3
(I) (II) (III)

(a) (II) (b) (I) and (III) (c) (III) (d) (I)

Solution
α
We know that the necessary condition for a compound to H
show hyperconjugation is the presence of α-hydrogens.
Here, (I) and (II) have zero α-hydrogens and (III) has two
α-hydrogens. Hence, hyperconjugation does not occur in (I)
and (II). However, in (III) hyperconjugation takes place because
of α-hydrogen present at the carbon to which methyl group is Hα
attached. Please note that in (III), the α-hydrogen present at
the bridgehead position do not show hyperconjugation. CH3
Thus, option (c) is the correct answer.

Based on the hyperconjugation

Compare the stabilities of but-2-ene and 2-methylprop-1-ene

H3C CH CH CH3 H3C C CH2

CH3
But-2-ene 2-Methylprop-1-ene

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Solution

But-2-ene and 2-methylpropene have the same molecular formula (C 4 H 8 ), but they have
different structural formulas. Hence, they are isomers. Here, both the compounds have
six α-hydrogens. So, to determine stability, we have to analyse their hyperconjugative
structures. The hyperconjugative structures of but-2-ene are as follows:

H H+

H C CH CH CH3 H C CH C CH3

H H H

2° Carbanion

The hyperconjugative structures of 2-methylprop-1-ene are follows:

H H+

H C C CH2 H C C CH2

H CH3 H CH3

1° Carbanion

Hyperconjugation results in the formation of two types of carbanions. A 2o carbanion forms

due to hyperconjugation in but-2-ene, and a 1o carbanion forms due to hyperconjugation in
2-methylprop-1-ene. Due to the inductive effect of methyl group, the negative charge on the 2o
carbanion intensifies. Hence, it is less stable when compared to 1o carbanion.
Hence, 2-methylprop-1-ene is more stable than but-2-ene.

H3C CH CH CH3 > H3C C CH2

CH3

Note

• Generally, the effect due to hyperconjugation is less dominating than the mesomeric effect.
However, it is more dominating than the inductive effect (i.e., R > H > I).
• The M effect and H effect operate only at ortho/para positions and not at meta positions.

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MAIN BOARDS
Reverse Hyperconjugation (–H Effect)

• When a compound has only halogen atoms in α positions of the double bond, then it shows
reverse hyperconjugation.
α
Cl
• An example is given in which three Cl–atoms are present in
the α position with respect to the double bond. In such α Cl C CH CH2
systems, the hyperconjugation effect operates in the reverse
direction. Cl
α
• Hence, the hyperconjugation in such systems is known as the reverse or negative hyperconjugation.
• In hyperconjugation, electrons flow from the 𝛔-orbital to the empty π-orbital of carbon as shown
in propene.

H H+

H C CH CH2 H C CH CH2

H H

• In reverse hyperconjugation, electrons flow from the π-orbital or p-orbital to the empty π*-orbital
of chlorine. The reverse hyperconjugation in (Cl)3C–HC=CH2 is given as follows:

Cl Cl –
+
Cl C CH CH2 Cl C CH CH2

Cl Cl

Cl Cl
+ +
Cl C CH CH2 Cl– C CH CH2

Cl – Cl

• In reverse hyperconjugation, a negative charge develops on the chlorine atoms present in α

 position and a positive charge develops on the carbon.
• This positive charge on carbon results in an incomplete octet in each of these resonance
structures. Thus, reverse hyperconjugation is a destabilising effect.
• A three-dimensional illustration of reverse hyperconjugation in (Cl)3C–HC=CH2 is given in
fig. 2.

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– –
Cl Cl

Cl
H H
H
H + H
H
C C
C Cl C C + Cl C C Cl
H H C H C

Cl Cl Cl

Fig. 2: Three-dimensional representation of reverse hyperconjugation

Reverse hyperconjugation in benzenoid systems

Reverse hyperconjugation is shown by benzenoid systems as well.

Example:
Cl Cl Cl Cl

Cl C Cl Cl C Cl – Cl C Cl – Cl C Cl –

+ +

+
(I) (II) (III) (IV)
• Reverse hyperconjugative results in structure (II). Since a positive charge develops on thring, the
 resonance occurs. (III) and (IV) are the resonating structures.
• Can be observed that a positive charge develops on the benzene ring that decreases the
electron density in the benzene ring. Hence, it destabilises the system.
• Also, positive charge develops in the ortho and the para positions.Thus,reverse
hyperconjugation is a –H effect.

Conditions for reverse hyperconjugation

• Reverse hyperconjugation (-H effect) does not occur in the presence of α-hydrogens.
• In the given example, both α-halogen and α-hydrogens are present in the compound. These
compounds show hyperconjugation due to the presence of α-hydrogens.
• Here, hyperconjugation dominates over reverse hyperconjugation.

H H H H
α α
C C H C C H
H C H C
α α
α α H
Cl Cl Cl

1 α-hydrogen 2 α-hydrogens
2 α-halogens 1 α-halogen

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MAIN BOARDS
Applications of Hyperconjugation

The major applications of hyperconjugation are given as follows:

Stability of carbocations, free radicals, and alkenes

Explains heat of combustion and heat of hydrogenation

Explains acidic and basic strength

A detailed discussion of each of these applications is given as follows:

Hyperconjugation determines the stability of carbocations, free radicals, and alkenes

• An analogy is given for a better understanding. A person is holding a fireball in his hand as
shown in fig. 3.
• For momentary relief, he can throw this ball in the air and catch it after a few seconds. By doing
this, his hands will be temporarily relieved from the pain due to this fireball.
• This analogy can be related to hyperconjugation. When the person holds the ball in his hand, he
is experiencing the pain (lack of stability).
• Throwing the ball in the air can be related as no-bond resonance (i.e., no connection between
the hands of the person and the ball). Thus, it attains stability.

Person holding a fireball Person throwing a fireball

which results in experiencing in the air and getting momentary
pain i.e., lack of stability. relief i.e., attain stability.

Fig. 3: Analogy to understand hyperconjugation

Hyperconjugation explains heat of combustion and heat of hydrogenation

• The addition of hydrogen is known as hydrogenation.

• The heat evolved per mole by the addition of hydrogen to form a saturated hydrocarbon is
known as the heat of hydrogenation (ΔH°HOH).

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For a better understanding, the heats of hydrogenation of some alkenes along with the product
formed after hydrogenation are given as follows:
α
CH3

α H2 , Ni
H3C ΔH°HOH = 26.9 kcal/mol
α
CH3

α
CH3
α
H H2 , Ni
ΔH°HOH = 28.5 kcal/mol
α
H

α
H
H2 , Ni
ΔH°HOH = 30.3 kcal/mol

• The preceding three catalytic hydrogenation reactions form the same alkane as the product.
• However, the three reactions have different heats of hydrogenation. So, the three alkenes must
have different energies. Hence, they have different stabilities.
• The alkene with higher number of α-hydrogens has greater stability. Hence, the heat of
hydrogenation is less.

1
Heat of hydrogenation ∝
Stability of alkenes

• Greater the number of 𝝿 bonds, greater is the heat of hydrogenation.

Heat of hydrogenation ∝ Number of pi(π)bonds

Stability of polyenes

Hydrocarbons with two double bonds are known as dienes. Hydrocarbons with at least more than
two double bonds are known as polyenes. Dienes can be conjugated, isolated, or cumulative.
• Conjugated double bonds are separated by one single bond.
• Isolated double bonds are separated by more than one single bond.

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• Cumulative double bonds are adjacent to each other.

The stability of dienes can be given as follows:
> >
Conjugated Isolated Cumulative

H 2C HC HC CH CH3 H 2C CH CH2 CH CH2 H 3C HC C CH CH3

The order of heats of hydrogenation of dienes is given as follows:
Conjugated < Isolated < Cumulative

Based on the heat of hydrogenation

Compare the heats of hydrogenation (HOH) of the following molecules:

A B C D

Solution

We know that HOH depends on the stability of alkenes (i.e., on the number of α-hydrogens in an
alkene). The number of α-hydrogens in each of these compounds is given as follows:
α α α
H α
H
H H α
H
α
CH α
CH
3 3
α
H α
H
α
H
α
H
α α
H
CH 3
α
H Hα
α
H Hα CH3

A B C D
10 α-hydrogens 6 α-hydrogens 4 α-hydrogens 3 α-hydrogens
The increasing order of HOH is given as follows:

< < <

Stability decreases
Heat of hydrogenetion increases
Thus, the order of heats of hydrogenation is A < B < C < D.

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Based on the heat of hydrogenation

Compare the heats of hydrogenation of the following molecules:

H3C CH3 H3C

C C C CH CH3 H3C CH CH CH3 H3C CH CH2
H3C CH3 H3C
A B C D

Solution

The number of α-hydrogens in each of these molecules can be given as follows:

α α α
H3C CH3 H3C α α α α
C C C CH CH3 H 3
C CH CH CH 3
H 3
C CH CH2
α α α
HC CH H3C
3 3

12 α-hydrogens 9 α-hydrogens 6 α-hydrogens 3 α-hydrogens

Stability decreases
Heat of hydrogenetion increases
As the number of α-hydrogens in an alkene increases, the stability of the alkene increases, and the
heat of hydrogenation decreases. Hence, the increasing order of heats of hydrogenation is given
as follows:
H3C CH3 H3C
< < <
C C C CH CH3 H3C CH CH CH3 H3C CH CH2
H3C CH3 H3C

Thus, the order of the heats of hydrogenation is A < B < C < D.

Heat of combustion

• The amount of heat released during combustion is known as the heat of combustion.
• Combustion of hydrocarbons (CxHy) produces CO2 and H2O. A balanced chemical equation
for the combustion of hydrocarbons (CxHy) is given as follows:

[ ]
CxHy(s) + x +
y
4
O2(g) xCO2(g) +
y
H O(I)
2 2

The heat of combustion depends upon the number of carbon atoms in an alkene and the stability
of the alkenes.

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Heat of combustion ∝ Number of carbon atoms

If the number of carbon atoms is the same

1
Heat of combustion ∝
Stability of alkenes

The heats of combustion of 2-Methylprop-1-ene and But-2-ene are given as follows:

H3C
C CH2 + 6O2 4CO2 + 4H2O ΔH°HOC= –2402 kcal/mol
H3C
2–Methylprop-1-ene

+ 6O2 4CO2 + 4H2O ΔH°HOC = –2404 kcal/mol

But-2-ene

• A lesser amount of heat is liberated during the combustion of 2-Methylprop-1-ene

(–2402 kcal mol–1) when compared to that of But-2-ene (–2404 kcal mol–1).
• Since the heat of combustion and the stability of alkenes are inversely related,
2-Methylprop-1-ene is more stable than But-2-ene.

BOARDS MAIN ADVANCED

Bredt’s Rule

Bicyclic molecules (two or more rings) having a bridge cannot have sp2 hybridised bridgehead
carbons as they are rigid and cannot have a planar structure.

+
+

A positive charge on a
bridgehead carbon makes the
system much more strained and unstable

• The bridgehead positions are already strained. A positive charge on a bridgehead carbon
makes the system much more strained and unstable.
• The possibility of formation of multiple bonds, intermediates (cation and radical), transition
states at the bridgehead position is negligible because it creates a strain at the already
strained position.
• Generally, it is applicable for eight or less-membered rings. It is not applicable for fused rings
as well as for more than eight-membered rings.
• To apply Bredt’s rule, at least one carbon should be present separating the two bridgehead
carbons.

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Based on Bredt’s rule

Compare the stability of the given carbocations.

+ +

A B C

Solution

In compound C since there is a positive charge on the bridgehead carbon. Hence, according
to Bredt’s rule C is the least stable carbocation among the given carbocations. Compound A is
a 1o carbocation with one α-hydrogen, and compound B is a 2o carbocation with two α-hydro-
gens.We know that a 2o carbocation is more stable than a 1o carbocation. Hence, compound B
is more stable than compound A.
α α
H +
H

CH3
+
+

H
α
A B C
1o carbocation 2o carbocation Positive charge on the
1 α-hydrogen 2 α-hydrogens bridgehead carbon
Least stable carbocation
Thus, the order of stability of carbocations is B > A > C.

+ +

> >

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