MECHANISM OF

ORGANIC
REACTIONS

B. R. THORAT
GOVT OF MAHARASHTRA

ISMAIL YUSUF ARTS, SCIENCE

AND
COMMERCE COLLEGE,
MUMBAI

Mechanism of organic reactions

1. Mechanism of a chemical reaction is the representation of series of
steps involve during the transformation of reactants to products.
2. Some of the intermediates are stable while some are unstable i.e.
mechanism is theoretical concept.

3. Since during the reaction, reactants are converted to product by

bond breaking/atom exchange/rearrangement/functional group
modification, etc.
4. The breaking of bond takes place either homolytically (free radical
formed) or heterolytically (forms ions cation and anion) i.e. during
cleavage of bond forming carbocation (carbonium), carbanions, free
radicals, transition state, etc.

Carbocations (carbonium)
The organic compound (ion) in which carbon carrying positive
charge is called as carbocation.
They are formed by heterolytically cleavage of C-X bond (X is atom
or group, more electronegative than carbon). It is also called as
carbonium ion having sp2 hybridization.

X
Heterolytically cleavage of -C-X bond

sp2 hybridisation
planar trigonal geometry
having six valance electrons

Different types of carbocations

a. Alkyl carbocations: Alkyl carbocations are stabilized by inductive effect of
substituted alkyl groups.

H + H
H
methyl

H + CH3

H + CH3

CH3

H
<

H3C + CH3

primary carbonium

<

secondary carbonium

CH3
<

tertiary carbonium

b. Allyl carbocation: It is stabilized by resonance effect of C=C bond.

+

c. Benzyl carbocation: It is stabilized by resonance effect of -Ph ring.

+CH
CH2
CH2
CH2
2
+

+
+

Carbocations (carbonium)
There are various reactions which are generated carbonium ion are1. SN1 Reactions:
It is first order nucleophilic substitution reaction having following rate law:
Rate [Substrate]
e.g. Consider hydrolysis of tert. Butyl bromide. This reaction has been
proceeds in two steps. (a) Ionization of substrate & (b) Nucleophilic
attack on carbonium ion. In the first step of reaction, substrate
undergoes ionization forming carbonium ion. It is planar, sp2
hybridized. Therefore, the solvent molecule or free electron rich
molecule or ion shows nucleophilic attack on both side of plane and
forming racemic product.
Step: I
H3C
H3C
H3C

Br

slow

CH3
+

H3C CH3
Planar, SP2 hydridized

Step: II
CH3
+
H3C CH3

fast

H3C
H3C
H3C

CH3
OH + HO

CH3
CH3

OH2

The carbonium ion is formed in such cases, where stabilization of

carbonium is possible. The primary alkyl halides shows SN2 mechanism
whereas tertiary substrate shows SN1 mechanism.

Carbocations (carbonium)
Electrophilic Addition reaction
The reaction in which site of unsaturation of product is lower than
reactant without elimination of by-product. OR The reactions in which
atoms or groups are added across the double, triple bonds or ring
without elimination of any by-products called addition reactions.
These reactions are electrophilic, nucleophilic or free radical.
The addition reaction involve initial addition of electrophile are called
electrophilic addition reactions. The electrophile get added to
double/triple bonds or ring.
E+
alkene

+
E

E+

X
E

+
E

alkyne

X
E

Carbocations (carbonium)
Electrophilic Addition reaction (mechanism):
The mechanism of this reaction has been divided in following steps:
1. Generation of electrophile: It is fast step.
E X

fast

E+

2. Attack of electrophile: It is slow step; involve the attack of electrophile

on bond of unsaturated bond or ring.
E+

slow
alkene

3.

+
E

Coupling of carbonium ion with nucleophile: It is fast step involve the

coupling of carbonium ion with associated nucleophile or solvent
molecule.
+
E

fast
X

If the reacting alkene is symmetric, one addition product is formed no matter

where is electrophile get attached. But in case of unsymmetric alkenes,
two different products are expected, one is major and another is minor
can be explain by Morkovnikov rule.

Carbocations (carbonium)
Electrophilic Addition reaction: (Morkovnikov rule)
Russian Chemist Valdimir Morkovnikov put rule for the addition of
unsymmetric reagent to unsymmetric alkene.
During the addition of unsymmetrical reagent to unsymmetrical alkene, the
positive part of the reagent become attached to a carbon bearing more number
of hydrogen (more substituted carbon).
e.g. Consider the addition of HBr to propene.
step II H

step I
H Br

fast

H + + Br

CH3

H+

+
H

slow

CH3

H
H
secondary

H3C

H
H
primary carbonium ion

The stability order of the carbonium ion is tertiary > secondary > primary >
methyl i.e. this reaction proceeds via more stable carbonium.
H

+
H

CH3

+
H

+
H3C

H
H

Br
fast

H
H

CH3
H

Br + H C
3

H
Br
H

Therefore rule can be modified as- Duringmajor

the addition minor
of unsymmetrical
reagent to unsymmetrical alkene, the reaction can be proceeds via more stable
carbonium ion.

Carbocations (carbonium)
Elimination reactions:
The reaction in which the site of unsaturation goes on increasing are
called as elimination reactions.
The reaction in which two atoms or group of atoms (of same or
adjacent or any two carbon atom) are removed from the molecule result
the formation of double bond or ring. During the elimination reaction,
in most of cases, one eliminating atom is hydrogen.
According to the position of eliminating atom, the elimination reaction
has been calssify as 1,1- or -elimination, 1,2- or -elimination, 1,3- or
-elimination and so on. The 1,2- or -elimination is most common
elimination.
Cl

H
Cl
H3C

1,1-elimination

Cl
Br

Cl
Cl

Cl2
CH3

1,2-elimination

H3C

+ BrH

Br
1,5-elimination

Carbocations (carbonium)
Electrophilic Elimination reaction: (E1 Mechanism)
It is two step first order mechanism of elimination reaction. The first
step (ionization step) is slow forming carbonium ion while second step
of reaction is fast in which base abstract the proton forming elimination
product.
e.g. Dehydrobromination of 1-bromopropane
Step-I

CH3 H

H3C

H
Br

slow

H3C
H3C

Step II

HO
H3C

H
H

H3C

H
H
H

fast

H3C

H
+ OH2

H3C

Carbonium ion

The first step is slow, therefore rate of reaction is only depends on

concentration of substrate but not on base concentration. During this
mechanism forming intermediate planar carbonium ion.
As substrate changes from primary to secondary to tertiary, the
reactivity of substrate via E1 mechanism goes on increasing. It does
not depends on nature and concentration of base.

Carbocations (carbonium)
Wagner-Meerwein rearrangement:
This reaction has been first observed in bicyclic monoterpenes , when
they are subjected to addition, substitution or elimination reaction, they
undergoes rearrangement reaction to rearranged product.
e.g. -Pinene rearranges to bornyl chloride in presence of HCl.
H

Cl

ClH
alpha-pinene

carbonium ion

bornylchloride

Now Wagner - Meerwein reaction has been extended to acyclic and

highly branched aliphatic compounds such as neopentyl compounds.
e.g. Neopentyl chloride on substitution/elimination gives rearranged
product asH3C

CH3

H3C
Cl
Substitution reaction

ClH

H3C
H3C
H3C

H2SO4
OH

H3C
H3C
CH3
Elimination reaction

Carbocations (carbonium)
Wagner-Meerwein rearrangement: (mechanism)
The mechanism of WM rearrangement involves following stepsa. Formation of carbonium ion: The OH of neopentyl alcohol is converted to good
leaving by protonation and lose water molecule forming primary carbonium ion.
H3C

H3C

ClH

H3C

H3C
H3C

H3C
OH
H3C
neopentyl alcohol

+
O H

+
CH2

H3C
H3C
primary carbonium ion

b. 1,2- shift / migration of adjecent group (stabilisation of carbonium ion): For the
stabilization of carbonium ion, alkyl group shows 1,2-migration along with
bonding pair; result the formation of more stable tertiary carbonium ion.
H3C

+
CH2

H3C
H3C
primary carbonium ion

c.

H3C

CH3

tertiary carbonium ion

Formation of product by combination with nucleophile or loss of proton: The

stable carbonium ion either undergoes substitution or elimination reaction to give
rearranged product. H3C
H3C
H3C
H SO
2

H3C
CH3
Elimination reaction

c.

H3C

1,2-methyl shift

H3C
CH3
tertiary carbonium ion

ClH

H3C
CH3
Cl
Substitution reaction

Nature of base and stability of carbonium ion decides the final product.

Carbanions
Organic compound (ion) in which carbon carries negative charge is
called carbanion.
A carbanion is formed by removal of one atom or group of atoms
(which are singly bonded) without bonding pair of electrons i.e.
heterolytic cleavage of bond such that atom or group leaves without
Base
bonding pair.
H CH -CHO
CH -CHO
2

Nomenclature:Named parent alkyl group and adding word carbanion.

CH3-CH2(CH3)2CH-.
(Ethyl carbanion)
(Isopropyl carbanion).
Due to presence of electron pair, they act as Lewis bases or strong
nucleophiles. The acidity of carbon is increased by attaching it to group
which stabilizes the negative charge on it after deprotonation of proton.

Carbanions
Preparation of carbanions:1) Heterocyclic fission of co-valent bond in such a way that a carbon atom
carries a bonding
pair of electrons and carries negative charge.
Base
H

CH2-CHO

CH2-CHO

CH3-CO-CH2-H

H-CH2-NO2

Base

CH3-CO-CH2

CH2-NO2

2) By breaking of polar carbon-metal bond:Generally nature of carbon metal bond is depends on electro-negativity of
metal and nature of organic part. The metal is less electronegative than
organic part and after breaking of bond gives carbanion.
+

M+

[ M - Li, Na, Al, Mg, B, etc]

3) By adding negative ion or nucleophile across C=C bond gives carbanion.

Such addition is takes place in presence of conjugated electron withdrawing
group such as nitro, cyano, carbonyl, etc. O
O

Nu
Nu

Many more methods are used to generate carbaions.

Nu

Carbanions
Configuration of carbanion:The hybridization of carbon bearing negative charge (carbanion) is SP3
having pyramidal shape as like ammonia. The optical activity
associated with asymmetric carbanion can be explained by pyramidal
structure by using Umbrella effect.
R1

R3

R2
R1
R2

R1
R2

R3

*
R3

Umbrella effect

(Carbanion)

It is assumed that, a carbanion which is stabilized by resonance effect

is SP2 hybridized having planar geometry.
R2

R3

R1

O
Planar hybrid structure

Carbanions
There are several methods for the preparation of carbanion as1. Alkylation of carbon acids:
a.

Terminal alkynes: Alkynes shows acidic character. In presence of strong bases,

alkyne forming carbanion which can be reacted with alkyl halide forming higher
alkyne. The alkyne carbon is sp hybridized so it stabilizes negative charge.
R/H

Base

R/H

acetylene
terminal alkyne

R'-X

R/H

R'

higher alkyne

metal alkylide

Main advantage of this method is, it is used to convert lower alkyne to higher alkyne
without change in functional group.
b. Reactive methylene compounds:
The acidic character of methylene group (-CH2-) can be increased by attaching it to
more electron withdrawing groups such as CN, -COOR, -CO-, -NO2, etc. After
donation of proton by methylene group forming carbanion, the negative charge
on carbon can be stabilized by R (resonance) effect.
O

H
H

R
R

Base

O
Active methylene group

R
R

H
O

R
R

H
O

R
R

H
O

R'-X

R'

R
R

H
O

Carbanions
Stability of carbanion of active methylene group:
The hydrogen atom of methylene carbon in EAA is more acidic due to1. The electron withdrawing (-I) effect of oxygen atoms, and
2. The resonance stabilisation (-R) of carbanion.
The negative charge on the carbon atom of methylene can be stabilized
by I and R effect of the electron withdrawing groups such as
CN, -COOR, -CO-, -CHO, etc.
O

EtONa

OEt

H3C
H

H3C
EtOH

OEt
Carbanion

H3C

O
OEt

H3C

O
OEt

Carbanions
Applications of ethyl acetoacetate (having reactive methylene group):
a. Synthesis of Succinic acids:
Sodium salt of ethyl acetoacetate reacts with ethyl chloroacetate
followed by hydrolysis gives succinic acid.
O

O
EtONa

OEt

H3C
H

ClCH2COOEt

OEt

H3C

1. NaOH

OH

2. H2O/H+
3.

OH

OEt

H3C

Carbanion

EtOH

CH2CO2Et

O
Succinic acid

b. Synthesis of 4-methyl uracil:

Ethyl acetoacetate (enol form) can be reacts with urea in presence of
phosphoryl chloride to give 4-methyl uracil.
O
EtO

NH2
+

O
NH2
Urea

HO
EAA CH3

POCl3

H
N

O
H

O
N
H

CH3
4-methy uracil

Carbanions
c. Synthesis of keto acids:
Sodium diethyl malonate reacts with alkyl halides followed by
hydrolysis and decarboxylation gives 3-keto acid.
COOEt
H
H

EtONa
EtOH

COOEt
H

COOEt
Diethyl malonate

R-COCl

COOEt
R-CO

COOEt
Carbanion

COOH

H 3O

R-CO
COOH

COOEt
-CO2

R-CO-CH2COOH
3-Keto acid

d. Synthesis of ,-unsaturated acids:

Diethyl malonate reacts with carbonyl compound in presence of base
followed by hydrolysis and decarboxylation gives ,-unsaturated acid.
COOEt
H
H

EtONa
EtOH

COOEt
Diethyl malonate

COOEt
H
COOEt
Carbanion

R-COR'
EtONa

COOEt

R'

COOEt

H3O

R
R'
-CO2
R

COOH
COOH
H

COOH
R'
Unsaturated acid

Carbanions
e. Synthesis of -amino acid:
Amino acid (e.g. alanine) can be synthesized by using diethyl malonate
by using following sequence of reactions.
COOEt
H
H

EtONa
EtOH

COOEt
Diethyl malonate

COOEt
RX

H
COOEt
Carbanion

COOEt
R

Br2

COOEt

COOEt

Br

COOEt

H 3O

COOH

Br

COOH

-CO2
R
R = CH3 : alanine

COOH
H2 N

Amino acid

NH3

R
COOH
Br

Carbanions
Applications of Grignard's reagent:
Organometallic compounds generate the carbanion by breaking C-M
bond heterolytically.
Mg

+
MgX

CH2COOEt +

ZnX CH2COOEt

+
ZnX

This carbanion can be added to carbon of carbonyl group gives wide

range of synthetically important compounds. e.g. Grignards reagent.
Grignards reagent reacts with aldehydes and ketones followed by
hydrolysis gives alcohols.
O

- +
O MgX
R

Mg X
R

Aldehydes/ketones

alkoxide intermediate

H2O/H+

OH
+

MgX(OH)

R
pri/sec/tert alcohol

Carbanions
Grignard's reagent:
Reaction of Grignards reagent with variety of aldehydes and ketones
forming variety of alcohols. e.g. It can react with formaldehyde /
aldehydes / ketones forming corresponding primary / secondary
/tertiary alcohols.
- +
O MgI

H3C

Mg I
H

H
H
Formaldehyde

H3C

Mg I
H3C

H
H3C
Acetaldehyde
O

H3C
CH3

Acetone

CH3

alkoxide intermediate
- +
O MgI
Mg I
CH3
H3C
H3C
alkoxide intermediate

MgI(OH)

CH3
H
pri (ethanol) alcohol

CH3

alkoxide intermediate
- +
O MgI

H3C

OH

H2O/H+

OH

H2O/H+

MgI(OH)

H3C

CH3
H
Sec (2-propanol) alcohol
H2O/H+

OH
+

MgI(OH)

H3C
CH3
H3C
Tert (2-methyl-2-propanol) alcohol

Carbanions
Aldol condensation:
Aldehydes or ketones containing -hydrogen atom undergoes self
condensation or with other molecule of aldehyde or ketone in presence
of base (10% NaOH) forming -hydroxyaldehyde or ketone (called
aldol). The word aldol is obtained from aldehyde and alcohol.
e.g. Two molecules of acetaldehyde are condensed in presence of dilute
NaOH to form 3-hydroxybutanal.
O
H3C

O
H

Acetaldehyde

H
C
H2
Acetaldehyde

O
NaOH

OH
H
CH3

3-hydroxybutanal (aldol)

Carbanions
Aldol condensation: Mechanism
This reaction is reversible; involves the following steps:
1. Formation of carbanion (stabilised by enolisation; resonance stable)
HO -

H
H2C
Carbanion

NaOH

H
C
H2
Acetaldehyde

H
H2C
enolate ion

2. The enolate ion attacks to another molecule of aldehyde

O

O
H3C

Acetaldehyde

H2C

O-

H
CH3
H
alkoxide of aldol

enolate ion

3. Protonation of the product

O

O-

H
CH3
H
alkoxide of aldol

H OH
H

OH
H
CH3

3-hydroxybutanal (aldol)

Carbon radicals
The C-C or C-X bond undergoes homolytical cleavage forming intermediate in which
both bonding atoms carries one electron called as free radical. These intermediates
are neutral.
.
C

Free radicals are obtained by using reagent such as halogens, AIBN, Me3SiI, etc
photochemically or thermally.
e.g. Chlorination of alkane such as methane.
Cl2

CH4 + Cl2

CH3Cl

Cl2

Cl2

CH2Cl2

CHCl3

HCl

HCl

Mechanism: Initiation

CCl4
HCl

HCl

2 Cl
Cl2
Propogation: Chlorine radical abstract hydrogen from alkane. The reaction proceeds
to give mixture of
CH3Cl, CH2Cl2, CHCl3, CCl4.
CH4 +

.
Cl

CH3 + HCl
CH3Cl + Cl

CH3 + Cl2

CH3Cl + Cl
CH2Cl + Cl2

CH2Cl + HCl
CH2Cl2 +
Cl

Termination: The chain termination takes place by combination of two radicals.

Cl

+ Cl

Cl2

CH3 + CH3

CH3-CH3

Carbon radicals
Reaction of free radicals:
a. Addition to C=C bond:
Free radicals such as chlorine adds to C=C bond forming another
new free radical. It is further reacts chlorine radical or C=C bond
forming new alkyl radical and so on.

H2C CH2 +

.
Cl

Cl2

.CH

Cl

+ Cl

CH2-Cl

Cl

Cl-CH2

CH2-Cl

.CH

CH2-Cl
Cl-CH2-CH2-CH2-CH2-Cl
2

The new alky radical formed is more reactive and reacts

immediately forming new hydrocarbon at low temperature and
pressure or polymer molecules.

Carbon radicals
b. Disproportionation:
At high temperature most of alkyl radicals undergoes disproportion
(one molecule gain hydrogen and second lost hydrogen) forming
alkene and alkane.

.
CH CH
3

hydrogen donor

.
CH CH
3

CH2=CH2

CH3-CH3

hydrogen acceptor

There is competition between combination and disproportion

reactions. Most of the experimental studies shows that, combination
reaction is predominant in unbranched radicals while disproportion is
occurs in branched alkyl radicals.
c. Combination:
Alkyl radicals are combine themselves and forming higher
hydrocarbon.

.
CH CH
3

CH3CH2

CH3CH2-CH2CH3
Higher hydrocarbon

Carbon radicals
d. Addition of HBr to alkene in presence of peroxide:
The addition of HBr to alkene in presence of air, peroxide and light forming less
substituted product which is contradictory to Markonownikoffs rule. This
phenomenon is called as peroxide effect.
It is only observed in bromide not in the chloride and iodide indicates the reaction
proceeds through free radical intermediate (free radical mechanism).
CH3-CHBr-CH3

In absence
of peroxide

In presence

CH3-CH=CH2 +

HBr

of peroxide

CH3-CH2-CH2Br

Mechanism:- 1. Initiation: Peroxides are thermally/phototchemically unstable and

undergoes dissociation to free alkoxy radical which is then react with HBr forming
bromine radical. This is initiation step where peroxide is called initiators.
RO OR

2 RO

RO + HBr

ROH + Br

2. Propagation: The bromine radical reacts with alkene forming more stable allky
radical.
R-CH=CH2 +

.
Br

.
R-CH-CH Br
2

sec. radical (stable)

.
R-CHBr-CH

prim. radical (less stable)

Carbon radicals
3. Termination:
The newly formed alky radical (tertiary > secondary > primary) reacts further with
HBr and get terminated and forming bromine radical. Continue this process further.

.
R-CH-CH Br

+
sec. radical (stable)
2

HBr

RCH2CH2Br + Br

e. Polymerisation:
Free radical are very reactive (short lived) and reacts with the unsaturated system
forming new radical which is again reacts with alkene and so on forming higher
wieght radical. It is get terminated at the end of reaction.
e.g.: Initiation
RO OR

2 RO

Propogation:

.
ROCH -CH
2

+ CH2=CH2

Termination
RO(CH2CH2) CH2CH2
n

CH2=CH2 + RO

ROCH2CH2CH2CH2

ROCH2-CH2
CH2=CH2

and so on

R-H
RO(CH2CH2) CH2CH3

termination can be done by disproportion, combination, by using trapping agent etc.

Carbon radicals
f. Redox reaction:
Oxidation and reduction with inorganic ions that can change their
valence state by gain or loss of a single electron can be used for the
production of free radical.
e.g. Fe2+ can be used catalyst for the oxidation in presence peroxide.
Ferrous can be convert to ferric (oxidation), so peroxide is convert to
hydroxide anion and free radical (Fentons reagent).
Hydroxide radical abstract hydrogen from hydrocarbon forming new
carbon radical. 2+
3+
.
Fe

+ H2O2

C6H5-CH3 +

Fe + HO

C6H5-CH2

HO

HO

OH2

Similarly reduction of inorganic ions also produced radical. E.g.

3+
C6H5-CHO + Fe

.
C H -CO +
6

Fe

2+

+ H+

Carbon radicals
f. Redox reaction (Kolbes Electrolytic method):
Concentrated aqueous solution of sodium salt of carboxylic acids are
electrolyzed forming alkene called as Kolbes reaction.
R-CCONa
2 R-COOAt cathode: 2 Na+ + 2 e
At anode:

2 Na + 2 OH2

R-COO - +

Na+

R-R + 2 CO2 + 2 e
2 Na
2 NaOH + H 2

Carbene
A compound containing carbon having six valence shell electrons (in
which two are unpaired) is called carbene. It can be formed by
homolytic / heterolytic fission of two bonds. It is neutral (chargeless) &
divalent.
X

C:

C
Y

Y X

or

+
X +

Carbene

According to the orientation of electrons, there are two types of

carbene singlet (opposite spin) and triplet (parallel spin) of electrons.
Formation of carbene:
1. Decomposition of diazomethane: Diazomethane undergoes
thermolysis or photolysis forming singlet carbene, but in higher
dilution singlet carbene is converted to triplet carbene.
CH2N2
R
R

+
N N

CH2
R
+ N N
R

+
R
R

N2

carbene

N2

Carbene
Formation of carbene:
2. From Ketene: Ketene undergoes photochemical decomposition to
carbene.
R
R
hv

CO

R
Singlet/triplet

Ketene

Structure of carbene:
The carbene contain two non-bonding electrons and also two orbitals.
According to the nature of these (non-bonding) electrons, carbene can
be classified into singlet or a triplet state. These electrons are exist
either in one orbital with opposite spins (paired) or in two orbitals of
equal energy with parallel spins.
R1

R1

R2

R1

R2

R2
singlet

carbene

triplet

carbonium

R3

Carbene
Structure of carbene:
Carbene

Hybridization

Bond angle

Singlet

SP2

1200

Triplet

SP

125-1400

Carbonium ion

SP2

1200

In the singlet carbene, the electron repulsion energy is higher than the
triplet state carbene. The triplet state carbene is more stable than the
singlet carbene present at ground state (triplet state). This can be
confirmed by electron spin resonance (esr) study. The aryl and diaryl
carbene is present at triplet state in ground state. The triplet carbene is
not linear but bond angle of 125-1400.

Carbene
Reaction of carbene:1. Insertion reaction : Carbene undergoes insertion reactions in which
carbenes are inserted into a C-H bond. The reaction may be
intermolecular or intramolecular.
a. Intermolecular:H
H

CX2

: CX

X X

H
H

: CX

. CX H
2

X X

b. Intramolecular:R' H
R

R'

R''
R''
H HC

CH2
R

R'

R
R''

c. Carbene can be reacted with many nucleophiles. e.g.:- Diphenyl

carbene can be inserted into the OH group of alcohol.
Ph2C

R-O-H

R-O-CHPh2

Carbene
Reaction of carbene:- Cycloaddition reaction
When carbene is added to the alkene forming cyclopropane derivatives. The singlet
carbene is added stereo-specifically whereas triplet carbene is added nonstereospecifically. The stereo-chemistry of the product was very important for the
detection of singlet or triplet carbene.
R

R
+

H
R

CH2

(cis)
H
R

H
H

H
H
+

H
R

CH2

R
R

R
+

(trans)
R

CH2

+
H

H
(cis)

(trans)

Singlet carbene is added to olefin forming cyclopropane derivative by the

simultaneous formation of two -bonds.
R

+
H

R
H

X
X

Carbene
Reaction of carbene:- Cycloaddition reaction
The addition of triplet carbene to alkene involves stepwise process.
These involve first formation of triplet diradical species which
undergoes spin inversion by C-C bond rotation before get convert into
cyclopropane. The C-C bond rotation is faster than spin inversion
hence we obtain a non-stereo specific product.
R

+
H

H
X2C

1. Rotn. about
C-C bond.
H

spin
inversion

X
X
(Trans)

R
H

H
X2C

H
X2C

2. Spin inversion
R

X
X
(cis)

Tautomerism
A phenomenon by which single compound can be exist two or more
easily interconvertable forms, these structures or forms are markedly
differ the relative positions of at least one atom (generally hydrogen) is
called as tautomerism and the structures are called tautomers of each
others.
1. Keto enol system: All aldehydes or ketones containing -hydrogen
atom are exist in two isomeric forms keto-form and enol-form.
O
H
keto form

OH

enol form

In case of aldehydes and monoketones, amount of enol form is very

less as compared to keto form because of easy interconversion with
keto form (more stable).
But enol form is exist in 1,3-diketones, 1,3-ketoaldehydes, 1,3ketoacids or esters, etc.

Tautomerism
Mechanism of enolisation:
During the enolisation elimination & addition takes place in two different steps. The
enolisation has been catalyzed by acid or base.

1. Acid catalyzed:
The proton adds to ketonic group forming conjugate acid in which the -proton is
more acidic and therefore easily removed by weak base forming enol.
+ OH

H+

COOEt

H3C

OH
COOEt

H3C

COOEt

H3C
H

acid form of ketone

keto form

enol form

2. Base catalyzed: Base remove the proton in slow step forming enolate anion which
is protonated in fast step of reaction gives enol.

H3C

O
COOEt Base slow

H
keto form

H3C

COOEt

carbanion

COOEt

H3C
enolate ion

OH

H+
fast

H3C

COOEt
enol form

Tautomerism (enolisation)
There are various carbonyl compounds having enol form:
1. - Ketoester: The keto and enol forms are different in different
solvents. The enol form is maximum in non-polar solvent and
minimum in polar solvent.
OH

O
H3C

COOEt

H3C

H
keto form

OH

O
COOEt

OEt

H3C
enol form

enol form

2. - diketones: The -diketones exhibit keto-enol toutomerism due to

conjugated carbonyl groups. The enol is 92% in hexane & 15% in
water.
O

H3C
H
keto form

OH
CH3

H3C
enol form

O
CH3

OH

H3C
enol form

CH3

O
H3C

O
CH3

stabilized by cyclisation

Tautomerism (enolisation)
3. Phenol:
Phenol exist 100% in enolic form (phenolic ring) due to extra
stabilization due to resonance (15 kcal/mol of energy) than the keto
form.
OH

OH

O
H
H

enol form

enol form

keto form

Test No 2 (10 Marks)

Suggest the mechanism for the following reaction:
1.

CH3

ClH

(CH3)3C-CH2OH

H3C

CH2CH3
Cl

1. ether

2.

CH3CHO

5.

2. H2O/HCl

OH

10% NaOH

3. 2 CH3CHO
4. CH4

CH3MgI

H3C
H3C
H
OH O

H3C
Cl2

(CH3)3C-Br

hv

CH3Cl + CH2Cl2 + CHCl3

NaOH

(CH3)2C=CH2

+ CCl4

Test No 2 (10 Marks)

Answers

1.

H3C

H3C

ClH

H3C

H3C
H3C

H3C
OH
H3C
neopentyl alcohol

+
O H

H2SO4

H3C
CH3
Elimination reaction

2.

- +
O MgI
H3C

Mg I
H3C

H
H3C
Acetaldehyde

3.

HO -

alkoxide intermediate

O
H

H
C
H2
Acetaldehyde

CH3

H
H2C
Carbanion

O-

H
CH3
H
alkoxide of aldol

H3C

1,2-methyl shift

H3C

CH3

tertiary carbonium ion

H3C

ClH

H3C
CH3
Cl
Substitution reaction

H3C
CH3
tertiary carbonium ion
OH

H2O/H+
H3C

+
CH3

MgI(OH)

H
Sec (2-propanol) alcohol

O
NaOH

H3C

+
CH2

H3C
H3C
primary carbonium ion

H3C
H3C
primary carbonium ion

H3C

H3C

+
CH2

H
H2C
enolate ion

H OH
H

O
H3C

Acetaldehyde
OH
H
CH3

3-hydroxybutanal (aldol)

H2C

O
H

enolate ion

O-

H
C
H
alkoxide of ald

Test No 2 (10 Marks)

4.

Cl2
CH4 +

.
Cl

2 Cl

+ Cl

CH2Cl2

.CHCl

.
.

CH3 + HCl
CH3Cl + Cl

.
CH + Cl
3

Answers

.CHCl

CHCl3 +

+ Cl2

Cl

CH2Cl + HCl
CH2Cl2 +
Cl

CH3Cl + Cl
CH2Cl + Cl2

+ HCl

CHCl3

CCl3

+ Cl

CCl3
CCl4

+ Cl2

Cl

+ HCl

5.
e.g. Dehydrobromination of 1-bromopropane
Step-I

CH3 H

H3C

H
Br

slow

H3C
H3C

Step II

HO
H3C

H
H

Carbonium ion

H3C

H
H
H

fast

H3C

H
+ OH2

H3C