Reaction Intermediates

Keywords
Homolysis, heterolysis, carbocations, carbanions, free radicals, carbenes, nitrene, benzyne.

Introduction
The highly reactive, energetic and unstable intermediates formed by the action of reagent on
substrate by involving the cleavage of a covalent bond in a multistep reaction is called reaction
intermediate.

[Substrate] + reagent [reaction intermediate] product/s

Generally, the step which involves the formation of reaction intermediate is the slowest step of multistep
reaction and determines the rate of overall reaction. For example, the rate determining step for chlorination
of methane in presence of sunlight is given below.
. . Cl2
CH3 H + Cl [CH3] CH3Cl + Cl·
[Substrate] reagent HCl [reaction intermediate] product/s
A covalent bond can be cleaved in one of two ways-heterolytic or homolytic.
Homolysis: It involves homolytic fission of a sigma bond.
. .
X + Y (Free radicals)
X Y

Heterolysis: It involves heterolytic fission of a sigma or a pi bond.

+ -
X Y X + Y
electrophile nucleophile
Homolysis produces free radicals that are electrically neutral, while heterolysis results in the formation of an
electrophile and nucleophile. Homolysis or heterolysis of a bond involving carbon results in carbon free
radicals, carbocations or carbanions etc. reaction intermediates. We shall discuss the various aspects of
these intermediates in detail in the following sections.
Carbocations
Carbocations are positively charged trivalent carbon species, formed by heterolytic cleavage of a  bond or
by the addition of a cationic species to a  system involving carbon atoms. The carbocations are classified as
primary (1), secondary (2) and tertiary (3) carbocations on the basis of position of carbon atom bearing
the positive charge. Examples of carbocations are given below.
+ + +
CH3CH2 CH2CH CH2 C6H5CH2
ethylcarbocation (1o) allylcarbocation (1o) benzylcarbocation (1o)
+ +
CH3CHCH3 (CH3)3C
isopropylcarbocation (2o) t-butylcarbocation (3o)
Methods of formation of carbocations
The following methods are commonly employed for obtaining carbocations.

1
Alkyl halides
The hydrolysis of t-alkylhalides give carbocations.

+ X ..
X H2O +

Alkenes
The protonation of alkenes yields corresponding carbocation
+
H+
R R
2o carbocation
Alcohols
The protonation of alcohols followed by elimination of water molecule give carbocations.
+ H
+
R OH + H R O R+
H H2O
carbocation
oxonium ion
Diazonium salts
The decomposition of certain diazonium salts gives carbocations.
+
N N Cl N N +

Cl N2
benzene diazonium chloride phenyl carbocation
Acid chloride
The acylium ions are formed when acid chlorides are heated with strong Lewis acid like anhydrous
aluminium chloride.
O
heat +
R C Cl + AlCl3 R C O + AlCl4
acylium ion

R3C + X ..
ionisation +
(a) R3C X

+
H
(b) + H
+

Since the species involved are ions, carbocation chemistry is invariably solution chemistry, the solvent(s)
being polar in nature, most often the medium is acidic and sometimes neutral.

Types of Carbocations
Carbocations are positively charged trivalent carbon species, formed by heterolytic cleavage of a  bond or
by the addition of a cationic species to a  system involving carbon atoms. The carbocations are classified as
primary (1), secondary (2) and tertiary (3) carbocations on the basis of position of carbon atom bearing
the positive charge. Examples of carbocations are given below.
The carbocations are classified as follows:
Alkyl carbocations
The electron deficient carbon represents alkyl group

2IIT1718CM7C 2
 + + + +
CH3 CH3 CH2
+
methyl ethyl propyl isopropyl t-butyl
carbocation carbocation carbocation carbocation carbocation
(1o) (1o) (2o) (3o)
Alkenyl carbocations: The electron deficient carbon represents alkenyl group. They may be
Allylic carbocations: The positively charged carbon atom is at allylic position
+
+ +
allyl
carbocation (1o) (2o) (3o)
Vinylic carbocations: The positively charged carbon atom is bonded to a multiple bond
+ + +
CH2 CH
Ph
vinyl carbocation
Acetalyde carbocation: The carbon atom with positive charge is linked with a triple bond.
+ + +
H C C CH3 C C Ph C C

Acylic carbocations: The carbonyl carbon atom of acylic group is electron deficient.
+
+ O C O
CH3 C O
+

Benzylic carbocations: The electron efficient carbon is at benzylic position

+ + +
CH2

benzyl carbocation (1o) (2o) (3o)

Aryl carbocations: The carbon atom with positive charge is present in the arenes
+ +

phenyl carbocation -naphthyl carbocation

Aromatic carbocation: Non-benzenoid carbocations are aromatic carbocations
+

+
cyclopropenyl tropylium
carbocation carbocation
Methods of Formation
Alkyl halides
The action of base like alkali, or Lewis acid like AlCl3, BF3 etc. on haloalkanes give carbocations
 ..
CH 3Cl  AlCl3  C H 3  AlCl4
..
HO (aq)
.. +
Br Br
The hydrolysis of t-alkylhalides also give carbocations.
X H2O + + X

3
Alkenes
The addition of proton (protonation) on alkenes yields corresponding carbocation
+
H+
R R
2o carbocation
The protonation of alkynes gives vinyl carbocations
H+ +
HC CH CH2 CH
+ +
Ph C C H Ph C CH2 + PhCH CH
Alcohols
The protonation of alcohols followed by elimination of water molecule give carbocations.
+ H
+
R OH + H R O R+
H H2O
carbocation
oxonium ion
The order of formation of carbocations is 3 > 2 > 1
Diazonium salts
The decomposition of certain diazonium salts give carbocations.
+
N N Cl N N +

Cl N2
benzene diazonium chloride phenyl carbocation

N H2 + O N OH + ..
H2O N N OH + N2 + H O
iso propyl
carbocation

This method is suitable for the preparation of alkyl and aryl carbocations.
Acid chloride
The acylium carbocations are formed when acid chlorides are heated with strong Lewis acid like anhydrous
aluminium chloride.
O
heat +
R C Cl + AlCl3 R C O + AlCl4
acylium ion

Structure and Stability of Carbocations

 The carbocations are electron deficient with six electrons in valence shell.
 They are positively charged and diamagnetic.
 The alkyl carbocations are planar, electron deficient and sp2 hybridised with vacant p-orbital.

2IIT1718CM7C 4
 H
vacant p-orbital

sp2 +
C H
hybridised
H
methyl carbocation
 Alkyl, allyl, benzyl and aromatic carbocations are sp2-hybridised with vacant p-orbital.
 Vinyl and aryl carbocations are sp2-hybridised with vacant, sp2-hybrid orbital.
 Acetalyde carbocations are sp-hybridised with vacant sp-hybrid orbital.
 Acyl carbocation is sp-hybridised with vacant p-orbitals.

Stability of carbocations
The parameters which determines the stability of carbocations are as follows
Inductive effect
An alkyl group is electron releasing to the carbocationic carbon, (which is sp2 hybridised). This is a
consequence of the difference in electronegativities between sp3-and sp2-hybridised carbons, where the latter
is more electronegative by virtue of higher percentage of s-character in the hybridised orbital.
CH3 CH3 CH3 H
+ + + +
C C C C
H 3C CH3 H CH3 H H H H
t-butyl iso-propyl ethyl methyl

Thus, the stability order is tertiary (3) > secondary (2) > primary (1) > methyl
Hyperconjugation
More CH bonds positioned vicinal to the carbocationic carbon, higher the stability of that carbocation.
H
+ H+
C C C C

From this again the stability order is: tertiary (3) > secondary (2) > primary (1) > methyl
Resonance
Where the carbocationic carbon is in conjugation with -system, the positive charge gets delocalised, thus
stabilising the carbocation. Allyl carbocations, benzyl carbocations, acylium ions, etc are stabilised by
resonance.
Allyl carbocations

1+ + 1
+ +
2 2
Benzyl carbocation
+ +
CH2 CH2 CH2 CH2

+ +

5
Acylium ions
+ .. +
CH3 C ..
O CH3 C ..O
Aromaticity
This is a special case of resonance where the positive charge is part of a cyclic, conjugated and planar
-system with (4n + 2) electrons (where n is an integer including zero) imparts extra stability through
delocalisation.

+ Br
..
+
Br

Tropylium bromide is water soluble and ionises, producing the tropylium carbocation (which is stabilised by
aromaticity) and bromide ion.
Hybridisation state
Higher the ‘s’ character, lesser the stability.
+ + + +
R C C < < R CH CH < R3C

Cyclopropyl methyl carbocations

The cyclopropyl carbocations are highly stable and their stability is higher than that of benzyl carbocations.
The exceptionally high stability of these carbocations is due to the conjugation between the bent orbitals of
the cyclopropyl ring and vacant p-orbitals of the cationic carbon.
H
C+
H
cyclopropyl methyl carbocation
The order of stability of a few carbocations is as follows
+ R
CH2 + +
+
+ > CH2 > > + > R R > R R >

+ + + +
R + > CH3 > CH CH > > HC C

Reactions and Rearrangements

Reactions of carbocations
Carbocations react mainly to neutralise the positive charge, which they may accomplish by reacting with a
nucleophile or by expelling a proton.
.. Cl
Combination with a nucleophile + + Cl
H
+
Expelling a proton (E1 elimination) -H +

2IIT1718CM7C 6
Rearrangements
Some carbocations may undergo rearrangement before undergoing one of the above two reactions. The
rearrangement converts a less stable carbocation to a more stable one. The rearrangement may involve a
hydride shift or an alkyl or aryl shift. A few examples are given below.

The hydride shift of 1 carbocation gives 2 carbocation which is more stable.

H (elimination)
OH + H+
H +
H2O + Br
1-propanol Br (nucleophilic
1o carbocation 2o carbocation substitution)
(less stable) (More stable)
The alkyl shift generally favours formation of stable 3 carbocation from 2 or 1 carbocation.
+
OH H methyl +
H 2O + shift
1-propanol 3o carbocation
1o carbocation
In the following reactions, intermediate carbocation involves in the rearrangement
Wagner-Meerwein rearrangement
The migration of hydrogen, alkyl or aryl groups in carbocations to form more stable carbocations are often
called Wagner-Meerwein rearrangement. The driving force of the rearrangement is the stability of
carbocation.
H+ +
H2 O + H+
OH
+
+ +

N N
N2 H+

Dienone-phenol rearrangement
The acid catalysed rearrangement involving 1,2-migration of one of the alkyl groups in cyclohexadienone
having two alkyl groups at position-4 forming corresponding phenol is called dienone-phenol rearrangement.
The driving force in the overall reaction is the creation of an aromatic ring. This rearrangement takes place in
presence of sulphuric acid.
+
H
O O OH OH
+
H
+ H+
H
Several studies have shown that 1,3-migration in dienone-phenol rearrangements actually result from two
successive 1,2-migration.
H+ +

HO
+ H+ HO
O HO + HO

Dienol-benzene rearrangement
The cyclohexadienols are acid sensitive compounds that easily rearrange to form aromatic rings.

7
 OH
+
+
H+
+
H2O H

OH
HCl
H2O
Cl

Pinacol-pinacolone rearrangement
The substituted vicinal diols are called pinacols. In presence of an acid (conc. H2SO4), a rearrangement
reaction takes place forming ketone called pinacolone and the rearrangement is known as pinacol-pinacolone
rearrangement. The simplest pinacol is 2,3-dimethyl-2,3-butanediol.
H
HO OH HO O CH3 O CH3
+ +
H + H
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3 CH3 C C CH3
H2O +
CH3 CH3 CH3 CH3 CH3 CH3
pinacol pinacolone
In case of mixed pinacol, the migratory optitude of aryl group is much greater than alkyl group. Among the
aryl groups the migratory optitude increases as the aromatic nucleus is made increasingly electron rich. The
order of migratory optitude of some groups is p-methoxyphenyl > p-tolyl > phenyl > p-chlorophenyl > H >
alkyl. (among alkyl groups  3 > 2 > 1 > CH3).
O HO O
ph OH H+
H+ ph ;
H2 O H2 O
HO ph ph OH
This rearrangement is also accompanied with ring expansion or ring contraction.
Ring expansion Ring contraction
O
OH +
OH +
H H
H
H 2O H2O
HO OH
O

2IIT1718CM7C 8
 Concept map Carbocations

Classification Preparation Structure Stability Reactions


primary (1) CH 3  C H 2 (Hybridised state
attack of
of carbon with +ve
+ nucleophile
alkyl secondary (2) alkyl halide charge)

Substituted products
tertiary (3) + alkyl allyl benzyl aromatic
acylhalides
Deprotonation
allyl +

+
alkenes with empty p-orbital alkenes
CH2
rearrangement
benzyl sp2-hybridised
alcohols
(trigonal planar)
+
vinyl CH2 CH
diazonium with empty sp2-orbital
+
salts
aryl (phenyl)
Generally the order of
+ vinyl aryl stability of different types
aromatic of carbocations is:
sp-hybridised aromatic > by overlap of
(linear)
antiaromatic empty and filled orbitals >
+
resonance >
with empty p-orbital with empty sp-orbital hyperconjugation > I effect >
  
acyl (R  C  O) acetylide R  C  C alkyl (3 > 2 > 1) > C H 3
> sp2-hybridised >
sp-hybridised > antiaromatic

9
Illustrations
Conceptual questions
1. Write the structure of stable reaction intermediate formed in the following reactions.
+
N N heat
H+
(a) OH (b)
Solution
(a) The secondary carbocation is formed
.. H+ +
O
H +
..OH H 2O
1o carbocation
+
2o carbocation
H
+
(b) The phenyl carbocation is formed N N heat +
N2

2. Pick up the stable carbocation in the following pairs and give reasons.
+
+ CH2 +
(a) and (b) and
+

+ +
(c) and (d) Cl and Cl
+ +

Solution
(a) The allyl carbocation ( ) is more stable as it is stabilised by resonance.
+

(b) The benzyl carbocation is stabilised by resonance which is not possible in phenyl carbocation hence
later is less stable.
(c) The cyclopropenyl carbocation is aromatic hence its stability is higher than cyclopropyl carbocation.
.. .
.. ..
+
(d) Cl is stabilised by resonance hence more stable. .. .
Cl Cl
+ +

3. Arrange the following in the increasing order of stability.

+ + +
(a) +
a b c d
+ + + +

(b)
O2N Cl CH3-O
e f g h

Solution
(a) More the number of -hydrogen, higher the hyperconjugation and greater the stability. The order of
stability is d < c< a < b.
(b) The electron releasing group on benzene ring increases the stability while electron withdrawing
group decreases the stability of carbocations. Hence, order of stability is f < e < g < h.

2IIT1718CM7C 10
Multiple choice questions
1. Tertiary butyl carbocation is very stable due to
(A) inductive effect (B) hyperconjugation (C) both (A) and (B) (D) resonance
Ans (C)
The carbocation is stabilised by I-effect and hyperconjugation.
2. Which of the carbocations below is stabilized by resonance?
+
+ + CH2
(A) R C O (B) (C) (D) none of these
Ans (A)
The acylcarbocation is stabilised by resonance.
..
O .. O ..
+ +
R C R C

3. Which of the following species is planar

(A) (B) ethyl carbocation (C) (D) all of these

. ..
Ans (B)
The carbocation is sp2-hybridised hence it is planar.
4. Benzyl chloride can be used to generate
(A) carbanion only (B) carbocation only
(C) Both carbanion and carbocation (D) a free radical
Ans (C)
+
Ag+
Cl benzylcarbocation

.. +
benzylchloride Mg/ether MgCl
reflux
benzylcarbanion

5. Select the most stable carbocation from the following

+
(A) (B) +

+
(C) + (D)

Ans (C)
The carbocation of (C) is tertiary carbocation and hence it is most stable while (A) and (D) are
secondary, (B) is primary carbocations hence less stable.
6. The increasing order of stability of the following carbocations is

+
(I) (II) (III) (IV)
+ +
+
(A) II < III < I < IV (B) III < II < I < IV (C) IV < II < I < III (D) I < III < II < IV

11
 Ans (D)
The carbocation (I) is antiaromatic and hence least stable. The secondary carbocation (III) is more stable
compared to (I). The carbocations (II) and (IV) are aromatic hence more stable than (III). Further,
structure (II) is more strained than (IV), therefore, (IV) is more stable. Hence, answer (D) is correct.
7. Find the least stable carbocation among the following
+ + +
CH2 CH2 CH2
+
(A) HC C (B) (C) (D)
H3CO
Ans (A)
The least stable carbocation is that which is not resonance stabilized and that which has the positive
charge in an orbital with maximum ‘s’ character, namely the sp-hybrid orbital. This is the case with
choice (A), (B) is resonance stabilized, (C) is stabilized by inductive effect of the cyclohexyl group and
by hyperconjugation due to one CH bond, (D) is the most stabilized of the four because of
electron-donation by the OCH3 group by resonance through the benzene ring.

Think Further
(i) Among the given carbocations A, B, C and D. The carbocation with (a) vacant hybrid orbital is
____ (b) vacant p-orbital is _______
(ii) The order of stability of the given carbocations is ______
(iii) In which carbocation +R effect of substituent reinfore resonance stabilization
1
2
8. The site of protonation in the following molecule is 3
4

(A) C1 (B) C2 (C) C3 (D) C4

Ans (A)
Whichever carbocation is the most stable one, the corresponding carbon will be the most preferred site
of protonation. The numbered carbon atoms in the given structure are the sites of protonation. The
carbon atoms that are not number are identical with C-3 and C-4 by symmetry. The four carbocations
that are possible after protonated are as follows
+
+
+
+
(a) (b) (c) (d)
Of all these, b is the most stabilized carbocation. It is stabilized by
(i) resonance with two C=C
(ii) hyperconjugation of the methyl group
(iii) inductive effect of the methyl group.
Thus, the preferred site of protonation is C1

9. Most stable carbocation among the following is

+ + +
(A) (B) + (C) CH2 CN (D)
Ans (B)

2IIT1718CM7C 12
 Carbocations, stabilised by aromaticity are the most stable. Thus, the choice is between (A) and (B).
Since (A) suffers from angle strain, (B) is more stable.
Think Further
(i) The carbocation with vacant sp2 hybrid orbital among the carbocations is ______
(ii) Which of the given carbocations is most readily formed?
(iii) Identify the carbocation formed in the following reactions.
+
NCl heat alcohol
(a) (b) Cl
N

10. Consider the following reaction

HCl
X

The major product (X) of the reaction is

Cl
Cl Cl
(A) (B) (C) (D)
Cl
Ans (C)
Mechanism for the formation of product (C) is as follows.
+
H+ + Cl Cl

Think Further
(i) The given reaction is an example of _____ reaction
(ii) The order of given reaction is ______
(iii) Write the structure of most stable carbocation formed as the reaction intermediate
(iv) The deportonation of stable carbocation yields _____
11. The product (X) of the following reaction is
HO
N2
H+
X
N2
O OH O
HO
(A) (B) (C) (D)

Ans (D)
H
HO O O
N2 HO + +

N2 H+

13
 Think Further
(i) Consider the following reactions.
OH
HNO2
NH2 X Y
heat H+
The product (Y) is _____
(ii) The major product (X) of following reaction is

H+
X
12. The reaction intermediate (X) formed in the following reaction may be

OH H+
(X)
H2O

+
+
(A) (B) (C) (D)
+
+
Ans (A), (B) and (D)
Carbocation (C) cannot be formed
Choose the most appropriate entry from column II to match each of the entries of the
column I.
13. Column  I Column  II
(i) (P) 3 carbocation
+

+
(ii) (Q) aromatic carbocation

(iii) (R) 2 carbocation

+

(iv) + (S) 1 carbocation

(T) allylic carbocation

Ans (i)  (R); (ii)  (T); (iii)  (Q); (iv)  (P)

14. Column  I Column  II

H+ +
(i) OH (P)

H+ +
(ii) (Q)

(iii) (R) +

Br

2IIT1718CM7C 14
 HO
H+ +
(iv) (S)

(T)
+

Ans (i) (R), (S); (ii)  (T); (iii)  (Q); (iv)  (P)

Carbanions
The carbanions are anions of carbon generated by the removal of one of the substituents bonded to carbon
atom without removing the bond pair of electrons. Thus a carbanion is a reaction intermediate with a
negative charge on a trisubstituted carbon. Examples of carbanion are given below.
CH3
..
CH2
.. .. ..
CH3 CH3 CH CH3 CH3 C CH3 CH2 CH CH2
..
methyl carbanion isopropyl carbanion t-butyl carbanion allyl carbanion benzyl carbanion

Like carbocations, carbanion chemistry is solution chemistry. Most often, medium is basic or sometimes
neutral.
Methods of formation of carbanions
From carbon acids
The carbon acids are compounds containing acidic hydrogen bonded to carbon. The carbanions are obtained
by abstracting proton from carbon acids by the action of base. A few examples are given below.

O O O O ..O O
Na2CO3
R R or HO
.. R .. R R R'
H H2O
 -diketones carbanion enolate ion

O O O O .. O O
Na2CO3
R OR or HO
.. R .. OR R OR
H H2O
-ketoester carbanion enolate

H
Na2CO3 .. O O..
R NO2 or HO
.. R
N R N
H2O O O

HO .. ..
CH3 C N CH2 C N CH2 C N
H2O

NaOCH3
+ CH3OH

(unsaturated and
.. Na+
conjugated hydrocarbon)

15
 O O O
..
NaOCH3
CH3OH ..
(ketone)

NaNH ..
R
C C H 2
R C CNa+ + NH3
(alkyne)
From alkyl, alkenyl or aryl halides using a metal (Grignard reagents)
.. +
CH3 I + Mg CH3 MgI

I + Mg MgI

I MgI
+ Mg

ether ..
R X + 2Li RLi + + LiX
heat

Br ether
+ 2 Li + + LiBr
heat .. Li
Bromides also can be used in place of iodides and among metals, magnesium is the most chosen, although
other metals are used.

From dithianes
Hydrogens on a carbon attached to two sulphur atoms are acidic enough to be abstracted by strong bases
such as a hydrides.
NaH
S S H2 S S
.. Na+
H

From phosphonium salt (Wittigs’ reagent)

CH3 I + PPh3 [CH3
+
PPh3] I
..
Phosphonium salt (phosphonium ylide)
base (NaNH2)
HI

.. +
[H2C PPh3 H2C PPh3]
Wittigs' reagent (ylide)
Structure of carbanions
Carbanionic carbon has three bonds and a non-bonding pair of electrons. Of the two possibilities with
regards to hybridization-one, being sp2 with the non-bonding pair in the unhybridised p-orbital and the other,
sp3 hybridisation with the non-bonding pair in the hybrid-orbital. The sp3 hybridisation is the preferred one
because the non-bonding electron will be in a orbital with some ‘s’ character. Consequently, a carbanion is
pyramidal-shaped with the lone pair of electrons occupying the apex of the pyramid. The tendency to possess

2IIT1718CM7C 16
sp3-hybridisation is high in sterically hindered alkyl carbanions. The carbon atom of carbanion is
sp2-hybridised if unshared electron pair is in conjugation with multiple bonds. The carbanion of bridge head
carbon is sp3-hybridised.
.. unshared
electron pair ..
R
C R ..
R sp2-hybridised
sp3-hybridised
sp3-hybridised (pyramidal)
 The carbanions contain eight electrons in valence shell, hence, more stable than carbocations and free
radicals.
 They are diamagnetic and move towards cathode under the influence of electrical field.
 The hybridized state of electron rich carbon of different types of carbanions is given below.
 Alkyl carbanions may be sp2/sp3 hybridised
 Allyl, aromatic and benzyl carbanions sp2-hybridised with filled p-orbital
 Vinyl and aryl carbanions sp2-hybridised with filled sp2-hybrid orbital
 Bridged-head carbanions sp3-hybridised with filled sp3-hybrid orbital.

Stability of carbanions
A carbanion is stabilised by the following polar effects.
Inductive Effect
Electron-withdrawing groups like halogens promote the formation of a negative charge on a carbon,
provided the halogens are enough in number.
For example: HO.. ..
H CCl3 CCl3
H2O

Resonance
This is the most important parameter that stabilises a carbanion through conjugation involving -system.
.. ..

.. O O..

.. .. ..
CH2 CH2 CH2 CH2 CH2
.. ..
O
The functionalities that help in stabilising a carbanion by resonance are carbonyl group C (aldehyde,
ketone, ester, anhydride, amide etc), nitro group (NO2), nitrile (CN), C=C system, etc.
Higher the delocalisation of negative charge by resonance, greater the stability of carbanions.

17
Aromaticity
Cyclopentadiene is acidic although it is a hydrocarbon, because the conjugate base is aromatic.
+
H

..
cyclopentadiene cyclopentadienyl anion
(not aromatic) (aromatic)

Hybridisation state of the carbon bearing the hydrogen

CH3CH2H: Ethane with sp3-hybridised carbon (25% s-character)
H2C=CHH: Ethylene with sp2-hybridised carbons (33.3% s-character)
HCCH: Ethyne with sp-hybridised carbons (50% s-character)
Of the above three hydrocarbons, it is only ethyne which has an acidic hydrogen. The reason for this is that
the carbanion, the acetylide anion, is stabilised because of the higher ‘s’ character of the hybridised orbital.
Higher ‘s’ character means that the electrons of the anion are closer to the nucleus and hence stabilised.
.. .. ..
The order of stability is CH3 CH2 < CH2 CH < CH C

In general, order of stability of different types of carbanions is as follows.

..
CH2
.. .. .. .. .. .. ..
> > .. > HC C > > CH2 CH > CH3 > CH3 CH2 > >
.. allyl acetylide phenyl vinyl alkyl carbanions
aromatic benzyl
carbanion carbanion carbanion carbanion
carbanion carbanion

Reactions of carbanions
All carbanions are bases as well as nucleophiles. It follows from this that carbanions cannot be generated
from compounds which have acidic hydrogens i.e., compounds which have the functionalities like OH,
NH, COOH, SH etc.

(i) Carbanions are very useful to make new CC bonds by reacting with compounds with electrophilic
carbon atoms like alkyl halides, carbonyl compounds, nitriles etc.

R
.. + R' X R R' + X ..
For example
O O–
R.. +
R1 R2 R R1 R2
The carbanion reaction intermediate is formed in Aldol reaction, Reformatsky reaction, Perkins’
reaction, Claisen ester condensation, Wittigs’ reaction etc.
(ii) With an appropriate leaving group at the -position, a carbanion may undergo elimination reaction

O2N O2N
+
..OPh
.. OPh

2IIT1718CM7C 18
Rearrangements
Rearrangements are not usually encountered with carbanions, although observed in some cases. This may be
because carbanions, with an octet electronic configuration, are not as unstable as carbocations. However, the
common carbanion rearrangements are Wittigs’ rearrangement, Steven rearrangement, Favorskii
rearrangement, Neber rearrangement, etc.

Favorskii rearrangement
In this rearrangement, -haloketones react with base to give enolates which rearranges to acids or esters via
cyclopropanones.
H .. ..
HO
Ph Br Ph Br
O
H2 O
O
.. .. O
H2O
O
HO
Ph Ph OH Ph OH
Br .. Br Br HO
..
HO .. O
Ph H2 O Ph
O O

The ,-dihaloketones and ,/-dihaloketones produce , -unsaturated acids or esters.

Br Br .. Br Br .. Br H .. Br H
HO HO
Ph H2O Ph Br Ph
Ph
O O OH
,-dibromoketone
O ..O
Br

Ph H

HO O
Br Br .. Br Br Br .. Br H
EtO .. H HO
H
EtOH Br OH
O O
O ..O OH O
,-dibromoketone

The ring contraction takes place when cyclic -haloketones are treated with base forming acids or esters.
O O O O O
Br .. Br .. ..
HO .. HO OH H 2O OH
H2 O Br HO ..

The following rearrangements involves the formation of carbanion as reaction intermediate.

Wittig’s rearrangement
The base catalysed rearrangement of allylethers or benzyl ethers into corresponding alcohols is called Wittigs
 rearrangement. Strong bases like RLi, NaNH2 etc., are employed. This rearrangement takes place by free
radical mechanism.

19
 .. ..
O RLi O O
. . O.. H+ OH
+ CH3

O NaNH2 O O .. H+ OH
..
Stevens rearrangement
The sulphonium or quaternary ammonium ion with carbonyl group at -position containing
-hydrogen when heated in the presence of strong base in inert solvent, corresponding 3 amine or thioether is
formed. This reaction involves rearrangement of carbanion.
O O O
+ Ph RLi S Ph RLi
Ph N Ph Ph Ph + Ph Ph
O N S

The mechanism of this rearrangement is summarised as follows.

O
+ Ph RLi/C6H6 + .. Ph
Ph N Ph N Ph Ph

O O N
nitrogen ylide
O O O
RLi/C6H6 S Ph
S Ph
Ph + Ph .. + Ph Ph
S
sulphur ylide
Sommelet Hauser rearrangement
Benzyl quaternary ammonium salts undergo rearrangement on treatment with strong base (RLi or NaNH2)
forming orthosubstituted products.
Ph H Ph Ph H
+ .. + +
N NaNH2 N N SNAr Ph Ph
NH3 N N
CH3 CH2
.. H

2IIT1718CM7C 20
 Concept map Carbanions

Classification Preparation Structure Stability Reactions

.. from
primary (1)CH3 CH2 (Hybridised state of
alkyl secondary (2)
.. haloalkanes
carbon with ve charge) nucleophilic
substitution
tertiary (3) .. sp2/sp3-alkyl carbanion
haloarenes
nucleophilic
2 addition
allyl .. carbonyl sp -allyl, benzyl, aromatic
compounds electron pair in p-orbital
.. Wittig’s reaction
CH2 2
benzyl nitriles sp -vinyl, aryl, enolate
(electron pair in sp2-orbital) rearrangements

vinyl CH2 CH
.. alkynes ..
sp-acetylide HC C

.. Wittig’s reagent
sp3-bridge head carbanion
aryl

aromatic Generally the order of stability of different types of carbanions is

.. ..
.. aromatic > resonance > sp-hybridised > sp2-hybridised > alkyl OCH3 (1 > 2 > 3)
antiaromatic > antiaromatic. [Stronger the carbon acid, stable is the carbanion]

Illustrations
Conceptual questions
15. Predict the stable carbanion formed in the following reactions.
O
HO .. O O ..
HO
(a) (b) O

(c) NaH (d) NaNH2

H

Br Mg/THF
(e) (f) Cl Li/ether

Solution
The carbanions formed in the given reactions are as follows.
O O O
(a) (b) (c) (d) ..
.. .. O ..
.. ..
CH2
(e) (f)

21
16. Identify the stable carbanion in the following pairs and give reasons.
.. ..
(a) .. and (b) .. and

.. O O
and
.. and ..
(c) (d)
..
Solution
(a) The 1 carbanion is more stable than 2 carbanion, hence, .. is more stable.
..
(b) The stability of is higher than .. as it is stabilised by resonance.

(c) phenyl carbanion is stable as unshared electron pair is present on more electronegative carbon.
O
(d) The carbanion stabilised by resonance is more stable.
..
17. Arrange the following carbanions in the increasing order of stability.

.. ..
(i) .. ..
(a) (b) (c) (d)
.. .. .. ..

(ii) O Cl O2N
e f g h
Solution
(a) The electron releasing substituent decreases stability of carbanion and among the alkyl carbanions
order of stability is 1 > 2 > 3. The order of stability of given carbanion is b < c < d < a.
(b) The electron with drawing group on benzene ring increases the stability of carbanions while electron
releasing substituent decreases the stability. The order of stability of given benzyl carbanions is
e < g < f < h.

Multiple choice questions with one correct alternative

18. Intermediate carbanion (P) formed in the following reaction is
F

Br Mg/ether
P
Cl
F F F
..Br
.. Br Br Br
(A) (B) (C) (D)
Cl .. Cl
Cl
Br
..
Br Br
Ans (D)
Greater the stability, higher the ease of formation.

2IIT1718CM7C 22
19. Which of the following ions are more stable than their corresponding protonated species?
O O
..
(I) H C O (II) H C CH2 O .. (III) (IV)
.. ..
(A) I and IV (B) II and IV (C) I and III (D) II and III
Ans (A)
The structures (I) and (IV) are stabilised by resonance hence they are more stable than the corresponding
protonated molecules.
20. Identify the least stable resonance structure from the following.
O O
(A) O (B) .. O
+
O O..
(C) .. O (D) O
+ +
Ans (B)
The structure (B) is least stable as charge separation is less and negative charge is on less electronegative
carbon.
21. Which of the following reaction intermediate is planar?
(A) ethyl carbanion (B) benzyl carbanion (C) t-butyl carbanion (D) isopropyl carbanion
Ans (B)
Carbanion in conjugation with double bond is sp2 hybridised hence planar.
22. The sp3 hybridised carbanion is
.. ..
(A) (B) Ph .. (C) .. (D)
Ans (D)
23. Which of the following carbanions is resonance stabilized?
.. ..
.. ..
(A) (B) (C) C6H5CH2CH2 (D) C6H5CH2
Ans (D)
The cyclopropylcarbanion is antiaromatic, delocalisation of negative charge is not favoured.
Remember that only electron is p-orbital can take part in resonance.
In the phenyl anion, the negative charge is in sp2 orbital. Again, no possibility for resonance.
In the phenethyl carbanion, the negative charge is separated from the  system i.e., the phenyl ring and
hence not in conjugation. Thus, only in the benzyl anion, there is resonance as shown below.
.. ..
CH2 CH2 CH2 CH2
.. ..
Think Further
(i) Among the given carbanions, an antiaromatic carbocation is _____
(ii) In which carbanions, sp2 hybrid orbital contains unshaired electron pair?
(iii) The order of stability of given carbanions is ______
(iv) Name the most acidic conjugate acid of the given carbanions

23
24. Identify the most stable carbanion among the following
.. .. .. ..
(A) CH2 CH CH2 (B) CH2 CH NH (C) CH2 CH O (D) CH2 CH2 CH3
Ans (C)
The propyl carbanion [option (D)] is the only one among the four that is not resonance stabilized
because the electrons of the negative charge are not in the p orbital. Among others, it is only in (C) that
the negative charge gets transferred to oxygen, the most electronegative one in the lot.
Think Further
(i) The carbanion is most readily formed among the given carbanions is _____
(ii) The order of stability of these carbanions is _____
(iii) The hybridised state of electron rich carbon of carbanion (A) is _____
(iv) The product (Y) of following reactions is _____
O
NaNH2 Br
X Y
HBr
(v) Write the IUPAC name of the product (Y) formed in the following reactions

ph3P O
Br X Y
HBr Ph3PO

25. Which of the following can be used to generate a carbanion by the action of sodamide?
(A) ethane (B) ethanol (C) ethene (D) ethyne
Ans (D)
Only acetylene has a hydrogen that is acidic enough to be abstracted, resulting in a carbanion.
base ..
H C C H HC C

Ethanol (choice b) also has an acidic hydrogen, abstraction of which results in an ethoxide ion, not a
carbanion
C 2 H5 O H
base
C 2H 5O
.. (ethoxide ion)

26. Consider following sequence of reactions

O
Br HO CH3OH
X Y

The product ‘Y’ of the reaction is

O Br O
O O
O
(A) (B) (C) (D) O
OH

Ans (D)
O O O O
HO + H Br .. Br CH3OH O
H 2O Br

2IIT1718CM7C 24
 Think Further
(i) The resonance structures of intermediate (X) are ______
(ii) Name the major product formed when given reactions are repeated for 1-bromo-1-phenylpropanone
(iii) Identify the product (Y) of following reactions
Br ..
OD/D2O H3O+
Ph X Y
heat
O

Choose the most appropriate entry from column II to match each of the entries of the
column I.
27. Column  I Column  II

(i)
.. (P) allyl carbanion

(ii) .. (Q) enoate ion

..
(iii) (R) acyl carbanion
O O ..
..
(iv) (S) alkyl carbanion

(T) benzyl carbanion

Ans (i)  (S), (ii)  (P), (iii)  (Q), (iv)  (T)

28. Column  I Column  II

(i) Grignard reagent (P)

(ii) Gilman reagent (Q) CH3Li

(iii) Wittigs’ reagent (R) CH3MgI
(iv) Carbon acid (S) (CH3)2CuLi
(T) CH2=PPh3
Ans (i)  (R), (ii)  (S), (iii)  (T), (iv)  (P)
Free Radicals
The intermediates formed by homolytic fission of a covalent bond, which are highly reactive and electrically
neutral species containing unshared electron are called free radicals. In carbon free radicals, carbon atom
bears the unshared electron. It contains seven electrons in outermost shell. Examples of carbon free radicals
are given below. .
. . . . . CH2
CH3 CH3CH3 CH3CHCH3 CH3 C CH3 CH2 CH CH2
methyl ethyl isopropyl CH3 allyl
free radical free radical free radical benzyl
free radical t-butyl
free radical
free radical
Since free radicals are electrically neutral, they can be generated in gaseous phase as well as in solution.

25
Methods of formation of free radicals
From hydrocarbons
When halogen molecules are exposed to electromagnetic radiations, homolytic fission of sigma bond takes
place forming halogen free radicals. The halogen free radical initiates the formation of carbon free radical.

X X
sun light
2X
.
or hv
halogen free radical

Cl Cl
hv
2Cl
.
. .
CH4 + Cl CH3 + HCl
methyl free radical
.
+ Cl + HCl
isopropyl free radical
.
+ Cl
. + HCl

Decomposition of peroxides
Thermal or photochemical decomposition of dibenzoyl peroxide yields phenyl free radical.
O O .
.
C O O C 2 C O
CO2
O
phenyl free radical
Decomposition of azo compounds
The photochemical decomposition of azo compounds give corresponding free radicals.
hv .
CH3 N N CH3 2 CH3 + N2
heat
azobis methane

CN CN .
2 + N2
N N CN
azobisisobutyronitrile (AIBN)

Decarbonylation of aldehydes and ketones

The photochemical decomposition of methyl ketones gives free radical.
hv . . .
CH3COCH3 CH3 + COCH3 CH3 + CO
heat

From sodium carboxylate

Free radicals are formed at the anode during electrolysis of sodium carboxylates in solution.

O O
R C O .. anode R C
.
O .
R
-e -CO2
free radical

2IIT1718CM7C 26