Module 4:Identification of products

Dr. Rangappa S. Keri

Assistant Professor & Group Leader
Organic Chemistry & Drug Discovery Lab 
Centre for Nano and Material Sciences
Jain University, 
Jain Global Campus, Bangalore 1

CNMS, Jain University, Bangalore

 Module 4:Identification of products
Syllabus
1. Formation, structure, stability, detection and reactions of-
a) Carbocations (classical and non-classical),
b) Carbanions,
c) Free radicals,
d) Carbenes,
e) Nitrenes,
f) Nitrile oxides,
g) Nitrile imines,
h) Nitrile ylides and
i) Arynes.
2. Determination of reaction intermediates,
isotope labeling and effects of cross over experiments.
3. Kinetic and stereochemical evidence, solvent effect.
4. Linear free energy relationship-Hammet equation and Taft treatment

CNMS, Jain University, Bangalore

Definition
Carbo
cation
 A carbocation  is an ion with a positively charged carbon atom.

s
 Also defined as “A carbon cation, or molecule that contains a trivalent,
positively charged carbon having six electrons in its outer shell.

 Among the simplest examples

CH
are  C2H5 C3H7
3

methenium  ethanium propanium 

 For many years these species were called ‘carbonium ions’. However, now they
are referred to as carbocations.

 Carbocations are generally unstable because they do not have eight electrons to
satisfy the octet rule. 3
 Structure
 The charged carbon atom in a carbocation is a "sextet", i.e. it has only six electrons in its
outer valence shell instead of the eight valence electrons that ensures maximum stability (
octet rule).
 Therefore, carbocations are often reactive, seeking to fill the octet of valence electrons as
well as regain a neutral charge. 
 The carbon atom in a carbocation is sp2 hybridized and it uses all its thee hybridized orbitals
for forming bonds with other atoms.
 The Pz, orbitals is empty and is perpendicular to the plane of the other three bonds.
 A carbocation may be described as planer (trigonal coplaner) with bond angle 120o
 Because carbocation assumes a planer structure, its formation is inhibited in compounds
which do not permit attainment of a planer geometry as bridge dead compounds.

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 Classification
 A primary carbocation is one in which there is one carbon group attached to
the carbon bearing the positive charge.

A secondary carbocation is one in which there are two carbons attached to the carbon
bearing the positive charge.

Likewise, a tertiary carbocation is one in which there are three carbons attached to the carbon
bearing the positive charge.

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 If the carbon bearing the positive charge is immediately adjacent to a benzene ring,
the carbocation is termed a benzylic carbocation. The simplest case is called the
benzyl carbocation.

 If the carbon bearing the positive charge is part of an alkene, the carbocation is
termed a vinylic carbocation. The simplest case is called the vinyl carbocation.

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 If the carbon bearing the positive charge is part of a benzene ring, the carbocation
is termed an aryl carbocation. The simplest case is called the phenyl carbocation.

 If the carbon bearing the positive charge is immediately adjacent to a carbon-

carbon double bond, the carbocation is termed an allylic carbocation.
 The simplest case (all R =H) is called allyl carbocation.

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 Carbocation Stability
 3° carbocation is more stable than a 2° carbocation and 2° carbocation is, in turn,
more stable than a 1° carbocation.
• The reason is that, if electron-releasing group such as alkyl group is present
adjacent to the carbon atom bearing positive charge, thereby delocalize the positive
charge of the cation, then the stability of the carbocaton increases.

• The alkyl groups attached to the positively charged carbon are electron-releasing
and thereby delocalize the positive charge of the cation
• The methyl cation is so unstable that it is never observed in solution.
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• The higher the degree, the lower the activation energy needed for its formation .
 Carbocation Stability

• The stability of carbocations is dependent on a few factors.

(1) Resonance

(2) Inductive effect, and

(3 Hyperconjugation

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(1) Resonance

 Resonance is a stabilizing feature to a carbocation because it delocalizes the positive

charge and creates additional bonding between adjacent atoms.

 Decreasing the electron deficiency increases the stability.

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 By resonance the positive charge on the central carbon atom gets dispersed over other
carbon atoms and this renders stability to the carbocation.
 This explains why benzyl (C6H5CH2+) carbocation and allyl carbocations are more stable

than propyl carbocation (CH3CH2CH2+)

CH 2 CH 2 CH2 CH 2

benzyl carbocation

(Four canonical strututres)

H
H 2C CH H2 C H2 C C
H2 C

Allyll carbocation

(Twocanonical strututres)

 The more the canonical structures for a carbocation , the more stable it will be.
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 The basic requirement for the carbocation to be stable is that, it should be planer, as it is
only in this configuration that effective delocalization can occur.
 The stability of such carbocation is explained in terms of resonance, i.e. the positive
charge on the carbon is distributed uniformly throughout a number of structures.
 In other words, a number of canonical structures are possible. For example,
triphenylmethyl carbocation.

triphenylmethyl carbocation


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 In certain cases, the carbocations are so stable that their solid salts have been
isolated.
 For example, triphenylmethyl perchlorate exists as a red crystalline solid and
tropyllium bromide has been isolated as a yellow solid.
 The tropylium bromide is stabilized by aromatization. The tropylium cation is
planer and has 6pi electrons like benzene.

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 Effect of heteroatom
 The carbocation stability also increased due to the presence of heteroatom
having unshared pair of electrons.
 For example, oxygen, nitrogen and halogen, adjacent to the cationic centre.
Such carbocations are stabilized by resonance.

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 Effect of conjugation

 When the positive carbon is in conjugation with a double bond the stability of the

carbocation is greater due to increased delocalization of positive charge, which spreads

over two atoms instead of being concentrated on one.

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2) Inductive effect

 The electron-donating inductive effect of alkyl group, the more the alkyl

group attached to the C, the greater is the stabilizing effect.

+
H3 C
+
C CH3
+

H3 C
+

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3) Hyperconjugation

 By hyperconjugation some charge delocalization occurs between the p orbital of

positively charged carbon and sigma of the β C-H.

 However the presence of the electron attracting groups (like NO 2, C=O etc)
adjacent to the carbon atom bearing positive charge makes the carbocation less
stable.
 Thus, NO2CH2CH2+ is less stable then CH3CH2CH2+

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 When considering the importance of hyperconjugation versus resonance as the more
important stabilizing feature, resonance usually wins out.
 For example, a primary carbocation with resonance is more stable than a secondary
carbocation without resonance.
 A secondary carbocation with resonance is usually more stable than a tertiary carbocation
without resonance
 The order of stability of some carbocations is given below-

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The general rules for carbocation stability can be summarized as follows

 Increasing substitution increases stability.

CH3+ (methyl; least stable) < RCH2+ (1o) < R2CH+ (2o) < R3C+ (3o; most stable)

 Resonance is more important than substitution. For example, a secondary

carbocation without resonance is generally less stable than a primary carbocation
with resonance. More the resonance structure more is the stability.

 The carbocation stability also increased due to the presence of heteroatom.

 Stability of a cation is influenced by the electronegativity, the more

electronegative the atom the less stable the cation.
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 Formation/Generation of carbocation

a) Ionization of a Carbon - Leaving Group Bond

b) Electrophilic Addition to a π Bond

c) Decomposition of diazonium ion

d) From alcohols

e) From acyl halides

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a) Ionization of a Carbon - Leaving Group Bond

 When a bond between a carbon atom and a leaving group ionizes, the leaving group accepts
the pair of electrons that used to be shared in the covalent bond.
 This may leave the carbon atom with an open octet, resulting in a carbocation.

 Better leaving groups or formation of a more stable carbocation result in lower activation
energy and faster ionization.
 Carbon - leaving group bonding ionization is illustrated using an oxonium ion.
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b) Electrophilic Addition to a π Bond

• When an electrophile attacks a π bond, the π electron pair may form a new σ

bond to the electron-deficient atom of the electrophile.

• The other π bond carbon no longer shares the π electron pair, resulting in a

carbocation.

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c) Decomposition reaction:

The alkyl diazonium ions are unstable and decomposes at room temperature carbocations.

alkyl diazonium ions carbocation

d) From alcohols:

Alcohols on treatment with conc. acids gets protonated and the protonated alcohols loses a

molecule of water to form carbocations.

H 2O
R-OH + H ROH2 R
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carbocation
protonated alcohol
Alcohol
e) From acyl halides:

The acyl halides on treatment with anhydrous aluminium chloride gives a complex,
which decomposes to give alkyl carocations

AlCl3
RCOCl R CO......ClAlCl3 R CO + AlCl4
acyl halides complex alkyl carocations

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 Reactions of carbocation

 The carbocations being very reactive and unstable, undergo reactions, as soon as they are
formed to give the stable products.
 In general carbocations undergo the following types of reactions.

a) Elimination of a proton

b) Reaction with nucleophiles

c) Addition to unsaturated compounds

d) Molecular rearrangement

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 a) Elimination of a proton

 A carbocation may lose a proton to form an alkene.

 Thus, 1-propyl carbocation (which can be generated from 1-amino propane by
diazotization, followed by decomposition of formed diazonium salt) may be eliminate a
hydrogen ion to form alkene (propane).
 Alternatively, 1-propyl carbocation may rearrange to more stable secondary carbocation,
which lose a proton to give propene.
NaNO2
CH 3CH2CH 2NH2 CH 3CH2CH 2N N
HCl
(1-Aminopropane) (Propyl diazonium cation)

-H +
CH 3CH2CH 2 CH 3CH=CH2
(1 o cation) (propane)

-H +
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CH 3CHCH 3
b) Reaction with nucleophiles

 A carbocation may combine with a nuclophile to form a new bond.

 For ex- Propyl carbocation on reaction with Br (bromide ion) forms n-propyl bromide.
 Similarly 2o propyl carbocation reacts with chloride ion to form isopropyl chloride

 A carbocation with a neutral nucleophile such as a water gives a protonated alcohol.

 3o butyl carbocation reacts with water (neutral nuclophile ) to give the protonated 3 o butyl
alcohol, which eliminates a proton gives 3o alochol.

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Addition to unsaturated compounds
 A carbocation may react with an alkene to produce another carbocation.

d) Molecular rearrangements
 A carbocation undergoes molecular rearrangement to produce a more stable carbocation.
 a) 1o carbocation on rearrangement gives a more stable carbocation (2 o/3o)

b) 2o carbocation on rearrangement gives a 3o

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The above rearrangements take place either by migration of a hydrogen with its pair of
bonding electrons or by migration of an alkyl group with its pair of bonding electrons.
Mechanism

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 Some of the useful reactions involving carbocation as an intermediate.

1) Baeyer-Villiger Oxidation
2) Beckmann rearrangement
3) Pinacol-pinacolone rearrangement
4) Wagner–Meerwein rearrangement

CNMS, Jain University, Bangalore 30

 1) Baeyer-Villiger Oxidation

 The Baeyer–Villiger oxidation is an  reaction in which a ketone is oxidized to an ester by

treatment with peroxy acids (triflouroacetic acid, perbenzoic acid, peracetic acid,
permonosulphuric acid) or hydrogen peroxide

Mechanism

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 2) Beckmann rearrangement
 It is an acid-catalyzed rearrangement of an oxime to an amide. Cyclic oximes
yield lactams.
 The reaction is catalyzed by acidic reagents such as H2SO4, SOCl2, SO3, P2O5, PCl5,
C6H5SO2Cl +
R1 N H H
OH R2 N
R1
R2
O

The reaction involves the migration of a group from carbon to electron deficient nitrogen

Mechanism
The reaction mechanism of the Beckmann rearrangement is in general believed to
consist of an alkyl migration with expulsion of the hydroxyl group to form a nitrilium
ion followed by hydrolysis

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 3) Pinacol-pinacolone rearrangement
 The acid-catalysed rearragement of vic diols (1,2 diols) to ketones or aldehydes with a
elimination of water.

Mechanism

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 4) Wagner-Meerwein rearrangement

 A Wagner-Meerwein rearrangement reaction, in which the carbon skeleton of a reactant

changes due to one or more rearrangements involving carbocations.

Mechanism

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 Non classical Carbocations

 Carbocation which are more than tri-coordinate are called non-classical carbocations.

 These carbocation are cyclic, bridged ions and possess a three centre bond in which three
atoms share electrons (three-centre, two-electron bonding)

 Ex- the norbornyl carbocation

 It is well known that acetolysis of both exo-2-norbornyl brosylate and endo-2-norbornyl
brosylate produce extensively exo-2-norbornyl acetate.

 The exo-brosylate is more reactive than the endo isomer.

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CNMS, Jain University, Bangalore

 Both acetolysis proceed via formation of a carbocation. The rate of ionization of the endo-
brosylate was considered normal, since it reactivity is comparable to that of cyclohexyl
brosylate.

 Ionization of the exo-brosylate is assisted by the C1-C6 bonding electrons. And led to
formation of the non-classical carbocation as an intermediate.

 This intermediate is achiral and has a plane of symmetry passing through C4, C5,
C6 and the mid point of C1-C2 bond. Carbon-6 is penta co-ordinate and as serves
as briding atom in the cation.

 The non classical carbocation can be formed only from the exo-brosylate, because
it has the proper anti-relationship between C1-C6 bond and the leaving group. 36
 Example for Non-classical carbocation

Summarize ：
 Nonclassical or bridged structure are readily attainable intermediate or transition state for
many cations.

 For norbornyl cation, the bridged structure is an intermediate. tertiary cation is nearly
always classical cation.

 Primary cation can rearrange to more stable secondary or tertiary carbocation, with
bridged structure as T.S
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CNMS, Jain University, Bangalore

 Question from carbocations
1) What are carbocations? Explain with examples. (2)

2) What are carbocations and explain their structure. (4)

3) Why tertiary carbocation is more stable than secondary and primary carbocation? (2)

4) Explain the stability of carbocation? (6)

5) What are the factors affecting the stabilty of carbocation? (4-6)

Or
How do you explain the stability of t-butyl and benzyl crbocations ? (4)
6) Write a note reactions of carbocations (4) or give the reactions involving carbocation as
reaction intermediate?

7) Write an account of the structure, formation and stability of carbocations. (6)

8) Give any two methods of formation/generation of carcations (2)
9) How do you explain the stability of t-butyl and benzyl cations ? (4)
10) What are non-classical carbocations ? (2)
11) Write a note non-classical carbocations with example (4)
12) Explain carbocation rearrangement reactions?
13) Give any four reactions involving carbocation? 38
 1st Assignment
1) What are carbocations? Explain with examples.

2) Explain the structure of carbocations.

3) Explain why tertiary carbocation is more stable than secondary and primary carbocation? (2)

4) How do you explain the stability of t-butyl and benzyl carbocations ?

5) Give any four methods of formation/generation of carbocations

6) Explain the stability of carbocation?

7) Give any four reactions involving carbocation?

8) Explain the molecular rearrangement reactions of carbocation

9) What are non-classical carbocations ?

10) Write a note non-classical carbocations with example

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