Recapitulation of Basics of Organic

Chemistry: Reactive Intermediates

DR SUNIL K. SINGH
Assistant Professor in Chemistry

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 Basic Strength
Basic strength of a species / molecule is its ability
to accept H+. The greater the ability of a species to
accept a H+ from another species, the greater
its basic strength (or basicity).

B: + H+ BH+

Basic strength directly depends on the

availability of lone pair for H+.
 Basic Strength
 Measured in terms of pKa value (sometimes in pKb value).
Higher the pKa value higher the basicity strength.
Smaller the pKb (or higher the Kb) value higher the basicity
strength.
The atom having the lone pair of electrons (here, nitrogen
atom) should be less electronegative, so that the lone pair is
readily donated.
More stable the conjugate acid of a base more is the basicity
strength of the base.
B: + H+ BH+

BH+ is the conjugate acid of base B and B

is the conjugate base of acid BH+.
 Alkyl amines are stronger bases than ammonia.
Aliphatic amines of all three classes have Kb values of about 10-3 to 10-4 (0.001 to
0.0001); they are thus somewhat stronger bases than ammonia (Kb = 1.8 x 10-5).
This can be explained in terms of an electron donating inductive effect of the alkyl
groups. Alkyl groups, by their electron donating effect, increase the electron density
on nitrogen and hence, make the lone pair of nitrogen more easily available to be
given to acids.
NH3 + H+ NH4+
Less Stable

H
R NH2 + H+ R N H
H
More Stable

R group is electron donating in nature,

hence stabilizes the conjugate acid.
 Basicity of 1o, 2o and 3-amines
Order of basicity on the basis of + I effect:
3o > 2o > 1o

+ I effect of methyl group increases the electron

density nearby nitrogen, making it more basic in
nature.

In H2O the basicity not only dependent on the ease of availability of lone pair of electron,
but also on the solvation of protonated amine by the water molecule. More the solvation
more is the stability of the conjugate acid of the amine; hence more is the basicity strength.
Basicity order on the basis of solvation effect: 1o > 2o > 3o

Overall Basicity order (Solvation

is important factor)
2o > 1o > 3o

(C2H5)2NH > (C2H5)3NH > C2H5NH2 >NH3

Tris(trifluoromethyl)amine is nonbasic in nature:
(CF3)3N is nonbasic in nature: Due to powerful –I effect of –CF3 group.

N N
H3C CH3 F3C CF3
CH3 CF3

Effect of hybridisation:

(Et)3N
H3C C N
N N
H Piperidine
1 2 3 4
Order of basicity: 3 > 4 > 2 > 1
Amidines are more basic than aliphatic amines:
More basic
NH NH
C C
R NH2 R NH2
The conjugate acid of the amidine is resonance stabilized:
NH NH2+ NH2
C + H+ C C
R NH2 R NH2 R NH2+

Guanidine is more basic than aliphatic amines and it is as

basic as ammonium hydroxide:
More basic
NH NH NH
C C C
H2N NH2 H2N NH2 H2N NH2
The conjugate acid of the guanidine is resonance stabilized:
NH NH2+ NH2 NH2
+ C C C
C + H
H2N NH2 H2N NH2 H2N NH2
H2N NH2
 Basicity of aliphatic amines vs aromatic amines
Aryl amines are weaker bases than ammonia and aliphatic amines both

Explanation: Due to + R effect the nitrogen lone pair of electron is delocalized into the aromatic ring, hence less
available for protonation. Aromatic amines have Kb values of 10-9 or less, they are thus weaker bases than
ammonia (Kb = 1.8 x 10-5). In aliphatic amines the alkyl group through + I effect increases the electron density on
nitrogen, hence it is more available for protonation.
Practice Problem: Arrange the following into decreasing order of their basicity.
O
NH2 NHCH3 HN C CH3

Aniline N-Methylaniline Acetanilide

Explanation: In acetanilide acetyl group is electron withdrawing in nature. Carbonyl group is
in conjugation with the nitrogen lone pair of electron. Due to resonance effect the electron
density at nitrogen is less, hence less available for protonation. Less the availability of lone
pair of electron less is the basicity. In N-methyl aniline the methyl group is electron donating
in nature and through + I effect it increases the electron density at nitrogen, hence making
the lone pair of electron more available for protonation.
O O
HN C CH3 HN C CH3

HN CH3
+ I effect of –CH3 group increase the electron density at nitrogen.
Practice Problem: Methyl amine is more basic than N,N-dimethylformamaide (DMF).

H 3C O O
H3 C
N C H N C H
H3 C H3C
DMF

In DMF the nitrogen lone pair of electron is in conjugation with the carbonyl group,
due to resonance effect the electron density at nitrogen decreases, hence it is less
available for protonation.

H3C NH2
In methylamine the methyl group through + I effect increases the electron density at
nitrogen, hence lone pair of electron is more available for protonation, making it more
basic than the DMF.
Practice Problem: Methyl amine is more basic than acetamide.

H3C NH2
In methylamine the methyl group through + I effect increases the electron density at
nitrogen, hence lone pair of electron is more available for protonation, making it
more basic than the DMF.

O O
H3C C NH2 H3C C NH2
Acetamide

In acetamide the nitrogen lone pair of electron on nitrogen is in conjugation with

the carbonyl group, hence resonance takes place and due to resonance effect the
electron density at nitrogen becomes less, hence less available for protonatoin.
Practice Problem: Arrange the following amines in the decreasing order of their basicity.

CH2NH2

NH3 CH3NH2

1 2 3
NH2 NH2

4 5
Hint: 2 > 4> 3 > 1> 5
 Basicity of aromatic amines/derivatives
NH2 NH3+

X + H+ X

Nature of substituent (-X) Effect on basicity strength

+ I effect Increaes
-I effect Decreases
+R Increases
-R Decreases
Ortho effect Always decreases (no matter, whether the
substituent is electron donating or
withdrawing in nature)
(R > H > I)
Practice Problem (s): Arrange the following aromatic amines in the decreasing order of their basicity.

NH2 NH2 NH2 NH2

NO2

NO2
1 2 3 4 NO2

Hint: 1>3> 4> 2

NH2 NH2 NH2 NH2

Cl

Cl
1 2 3 4
Cl
Hint: 1> 4> 3> 2 (-I > + R effect)
 NH2 NH2 NH2 NH2
Me

Me
1 2 3 4 Me

Hint: 4>3> 1> 2 NH2 NH2

NH2 NH2
OMe

OMe
OMe
1 2 3 4

Hint: 4>1> 2> 3

Practice Problems: Arrange the followibg in the decreasing order of their basicity:
1. Aniline, N-Methyl aniline, N,N-Dimethylaniline
2. Aniline, Diphenylamine, Triphenyl amine.
 Effect of Steric inhibition of resonance
1. 2,6-Dimethyl-N,N-dimethylaniline is stronger base than N,N-dimethyl aniline. Why ?
Out of plane, hence +
H3C CH3 R effect will be absent. H3C CH3

:
N

:
N Steric inhibition of resonance
The two planes
H3C CH3 H H are coplanar
The two planes
are not coplanar

Large steric repulsion bw –CH3 Explanation: In 2,6-Dimethyl-N,N-dimethylaniline the large steric

group (present at ortho-position) repulsion between the –CH3 of the N(CH3)2 group and -CH3 group
and CH3 group of –N(CH3)2 group, (present at ortho-position) bring -N(CH3)2 group out of the plane of
benzene ring. So that the resonance effect due to the -N(CH3)2 group
hence –N(CH3)2 group comes out of (+R effect) will be absent, hence no delocalisation of lone pair of
plane (not coplanar with the electron. Such type of prevention of the resonance effect due to
phenyl ring). steric repulsion is well known as steric inhibition of resonance.
Please note: The steric repulsion between –CH3 group and H atom in
the case of N,N-dimethyl aniline is almost negligible as the size of H
atom is small. So the –N(CH3)2 group is coplanar to the benzene ring,
exhibit delocalisation.
 Effect of Steric inhibition of resonance
2. 3,5-Dimethyl-4-nitroaniline is about 35 times stronger base than the 2,6-dimethyl-4-nitroaniline.
H H
N Size of H is small, so the steric H H
repulsion is negligible that is bw – N
H3C CH3 CH3 group (present at ortho-
The two
planes are
position) and H atom of –NH2
not coplanar
group.

H3 C CH3
N The two planes Large Steric repulsion.
O O are coplanar
Out of plane O N O –R effect of –NO2
group will be absent.
Explanation: In 3,5-Dimethyl-4-nitroaniline the large steric repulsion between
the O atom of the –NO2 group and -CH3 group (present at ortho-position) Large steric repulsion bw –CH3
bring –NO2 group out of the plane of benzene ring consisting-NH2 group. So
group ((present at ortho-position)
that the resonance effect due to the –NO2 group (-R effect) will be absent.
Such type of prevention of the resonance effect due to steric repulsion is well ) and O atom of –NO2 group,
known as steric inhibition of resonance. which brings –NO2 group is out of
Please note: The steric repulsion between –CH3 group (present at ortho- plane (not coplanar with the
position) and H atom in of –NH2 group the case of 2,6-dimethyl-4-nitroaniline phenyl ring), hence –R effect will
is almost negligible as the size of H atom is small as compared to O atm. So be absent.
the –NO2 group is coplanar to the benzene ring consisting –NH2 group.
 3. N,N-Dimethyl-2,4,6-trinitroaniline is more 4x104 times more basic than 2,4,6-trinitroaniline.
Out of plane
H H
N Size of H is small, so the
O steric repulsion is negligible H3C CH3
O N O
O
N N - that is bw O of –NO2 group
O (present at ortho-position) N N - The two planes
-O and H atom of –NH2 group. O
-O are not coplanar
The two planes
are coplanar
O N O
O N O
Steric inhibition of resonance
Explanation: In N,N-Dimethyl-2,4,6-trinitroanilene the large
steric repulsion between the O atom of the –NO2 group and –- Large steric repulsion bw –CH3 group of
oxygen of the -NO2 group bring –N(CH3)2 group out of the plane the –NMe2 group (present at ortho-
of benzene ring consisting-NO2 groups. So that the resonance position) and O atom of –NO2 group,
effect due to the –N(CH3)2 group (+R effect) will be absent. Such hence –N(CH3)2 group comes out of
type of prevention of the resonance effect due to steric plane (not coplanar with the phenyl
repulsion is well known as steric inhibition of resonance. Hence ring), hence + R effect due to –N(CH3)2
nitrogen lone pair of electron will be more available for group is absent.
protonation.
Pyridine is more basic than pyrrole.
Nitrogen lone pair of electron
is involved to complete the
aromaticity sextet of the
molecule, hence not available
for protonation.
Practice Problem: Arrange the following molecules pyridine, piperidine and pyrrole in the decreasing order of their
basicity.
 Homolytic and heterolytic cleavage of a
covalent bond
Bond cleavage is the splitting of a chemical bond. There are two types of
bond cleavage: homolytic and heterolytic. In homolytic cleavage, the two electrons in
the bond are divided equally between the products. In heterolytic cleavage, one atom
gets both of the shared electrons.

Ions are formed

(Carbocatios /
carbanions)

Free
readicals
 Carbocations
The heterolytic cleavage in an organic molecule where
carbon donates the shared pair of electrons to the leaving
group results in the development of positive charge on the
carbon atom. Such species where covalency of carbon is
three are called carbenium ions or carbocations (e.g. CH3+).
The carbon atom of carbocation is sp2 hybridised and it uses
the three sp2 hybridised orbitals for single bonding to three
substituents; the remaining p-orbital is empty.
However, the pentacoordinated positively charged species
such as CH5+ is called carbonium ion. This nomenclature was
proposed by G. A. Olah.
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 Structure of Carbocations
Vacant p-orbital

Carbon bearing +ve

charge is sp2 hybridized.

 The carbocation has a flat structure having all the three covalent bonds are in
plane with a bond angle of 120o between them.
 The positively charged carbon is trivalent, The positive carbon has sextet of
electron thus it is electron deficient. The order of stability of carbocations is
3o>2o>1o> methyl carbocation.
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 Generation of Carbocations
1. During solvolysis an alkyl halides ionizes to the intermediate carbocation and the
corresponding anion.

R X R+ + X-
2. Reaction of alkyl fluorides with SbF5
SO2 (l)
(CH3)2CHF + SbF5 (CH3)2CH + SbF6

3. Reaction of alcohol with superacid

(FSO3H·SbF5)
CH2OH CH2
or
96% H2SO4
or
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FSO 3H-SO
SUNIL 2-SbF
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 Stability of Carbocations: stability of 1o, 2o and 3o carbocations
1. Hyperconjugation effect
H3C CH H3C H H3C H H H
C+ 3 C+ C+ C+
CH3 CH3 H H
I II III IV

No. of -H 9 6 3 0
No. of Hyperconjugative str. 10 7 4
Stability order: I > II > III > IV
Hyperconjugative structures of I (3o-carbocation: tert-butyl carbocation)
H H H+
H H H H3C
H3C C H+ C
CH3
H3C C H
C+ H H3C
C
C H C H3C C H+ +
CH3 C H C H
CH3 CH3 H H
CH3

H3C CH3
H+ H H H3C CH3 C
H CH3 CH3 CH3 C
C C H+ C C C C C
H H H+ C H
CH3
H H+ H H H+
CH3 CH3 H
2. The methyl group is electron releasing (+ I effect) in nature, which decreases the intensity of the +ve charge.
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 Stability of benzyl carbocations
 Multiple bond or lone pair of electron is in Conjugation with the carbon bearing
+ve charge (it contains vacant p-orbital) increases the stability of a carbocation via
p-pi or p-p overlapping (or resonance effect).
 For example, triphenylmethyl carbocation is more stable than diphenylmethyl
carbocation, which in turn is more stable than benzyl carbocation. This due to
greater delocalization of positive charge in case of triphenylmethyl cation as it has
more number of resonating structures. More is the number of resonating structure
more is the stability of carbocation.
Order of stability
C CH CH2

> >

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 Resonating structures of triphenylmethyl carbocation
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Stability of 1o, 2o and 3o-benzyl carbocation /analogs
Order of stability
CH3 CH3 H
C > C > C
CH3 H H
3o-benzylic 2o-Benzylic Benzyl carbocation
Stabilized by resonance and Stabilized by resonance and Stabilized by resonance effect only
hyperconjugation effect (6-H) hyperconjugation effect (3-H)

Order of stability

H3CO CH2 > H3C CH2 > CH2 > O2N CH2

Stabilized by + R effect Stabilized by hyperconjugation

effect -R effect of –NO2 group destabilizes

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 Stability of allyl carbocations

Resonance stabilization of Allyl carbocation

Benzyl cation is more stable than allyl cation. In both the cases the vacant p orbital of
carbon bearing positive charge is in conjugation with p bond (s) and delocalization of
positive charge occurs through p-p overlapping. In benzyl cation, the number of
resonating structures are more as compared to allyl cation.
Stability of carbocation  No. of resonating structures

Order of stability CH2 > CH2+

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 Stability of 3o, 2o and 1o-allyl carbocations
H H H
C Me C Me C H
> >
H2C H2C H2C
Me H H

Practice Problem: Arrange the following carbocations in the increasing order of their stability ?

1 2 3 4

2o-carbocation vinylic carbocation 3o-allylic 1o-carbocation

Order of stability: 3 > 1 > 4 > 2
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 Stability of Alkoxyalkyl carbocations / analogs
Delocalization of lone pair of electron into vacant p-orbital: p-p overlapping is more
effective as compared to p-p overlapping.

H3C O CH2 H3C O CH2

H
H3C N CH2 H3C N CH2
H

Order of stability: CH3NHCH2+ > CH3OCH2+ Nitrogen is less electronegative than oxygen.

Practice Problem: Arrange the following in the decreasing order of their stability.

O CH2+ CH2+ CH3CH2CH2+

O
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Stability of Acylium ion Stability of vinyl cation
p-p orbital delocalization

CH2=CH
Unstable as the + ve charge is on sp-
hybridized carbon atom, which is more
electronegative as compared to sp2 and
sp3.
Order of stability
Resonance stabilization of acylium ion
Stability of phenyl cation CH3-CH2 > CH2=CH > CH3
sp-hybridised

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Stability of Tropylium cation or cycloheptatrienyl cation

Resonating structures of Tropylium cation

 It is resonance stabilized.
 It is aromatic in nature, and aromaticity provide it extra stability.
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 Stability of cyclopropenyl cation

Resonating structures of cyclopropenyl cation

 It is resonance stabilized.
 It is aromatic in nature, and aromaticity provide it extra stability.

Practice problem: Arrange the following carbocations in the increasing order of their stability.

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 Unusual Stability of cyclopropylmethyl carbocation
 Cyclopropylmethyl carbocations are more stable than the benzyl type
carbocations.
 The unusual stability of cyclopropylmethyl carbocation is because of the
overlapping between the bent orbital of the cyclopropyl ring and the
vacant p-orbital.
 This special stability, which increases with each additional cyclopropyl
group, is a result of conjugation between the bent orbital of the
cyclopropyl rings and the vacant p-orbital of the cationic carbon (well
known as Dancing resonance).

C > C > C H
H
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H
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 Unusual Stability of cyclopropylmethyl carbocation
 The NMR and other studies
shown that the vacant p-orbital
lies parallel to the C-2, C-3 bond
3 of the cyclopropane ring and not
2
perpendicular to it.
 The electrons in these orbitals
(bent orbital) are at relatively
higher energy than normal-
electrons and are therefore
particularly effective in
interacting with the vacant p-
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orbital of the carbocation. 110
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Cyclopropylmethyl carbocation is symmetrically stabilized, that is, both
the 2,3 and 2,4-sigma bonds help to stabilize the + ve charge,

2 CH2
4 1
Resonating structures of cyclopropylmethyl carbocation:
Note: more the no. of cyclopropyl ring more will be the number of resonating structures.

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 Overall order of stability of carbocations
CH3 H
> C > C > CH > >
CH3-C=O H3C C > H3C N CH2 >
~ CH3

CH3 H
H3C O CH2
> CH2 >H3C C > CH2=CH-CH2 > H3C C > CH2=CH > > CH3
H H
Note: Although the primary resonance stabilized carbocations (methoxymethyl cation,
benzyl cation and allyl carbocation) are less stable than the tert-butyl carbocation, but the
secondary and tertiary resonance stabilized carbocations are more stable than the tert-
butyl carbocation. CH3
H3C O CH > CH > CH2=CH-CHCH3 > H3C C
CH3 CH3 CH3
CH3
H3C O C CH3
> C CH3 > CH2=CH-CH(CH3)2 > H3C C
CH3
CH3 CH3
 Tricyclopropylcyclopropenyl carbocations is 103
more stable than the tropylium cation

>

Most stable carbocation

Isolated as white solid.

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 Measurement of stability of Carbocation:

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 Ref: Carey and Sundberg; Advanced Organic Chemistry : Part A

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Practice Problems:
1. Which carbocation in each of the following pair is more stable:

(i) CH3OCH2+ or CH3NHCH2+ (ii) CH3OCH2CH2+ or CH3OCH2+

H H
(iv) C C
CH3 .or CH3
(iii) .or

(v) CF3+ or CCl3+ (vi) (CH3)3C+ or (CD3)3C+

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 THANKS

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