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 + 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 + CH3 H + CH3 H3C + CH3

H H CH3 CH3
methyl < primary carbonium < secondary carbonium < 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 are-
1. SN1 Reactions:
It is first order nucleophilic substitution reaction having following rate law: Rate
α [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 Step: II
CH3 CH3 H3C
H3C CH3
slow + + fast
Br H3C OH + HO
H3C CH3
H3C H3C CH3 H3C CH3 H3C CH3
Planar, SP2 hydridized
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+ + X E+ + X

E E X E E X
alkene alkyne
 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.
fast E+
E X + X
2. Attack of electrophile: It is slow step; involve the attack of electrophile on
π bond of unsaturated bond orE ring.
+
+
slow
E
alkene

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

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

E X E 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.
stepConsider
I the additionstep
of HBr
II H to propene. H H
CH3 CH3 H
fast H+ + +
H Br H + + Br H
+
H3C
H H slow H H H
H
secondary primary carbonium ion

The stability order of the carbonium ion is tertiary > secondary > primary >
methyl i.e. thisH reaction
CH3 proceeds
H Hvia more stable
H carbonium.
CH3 H H
+ + Br
+ Br + H C Br
H H3C H
H H H H fast H H 3
H H
major minor

Therefore rule can be modified as- ‘During the addition 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 α-elimination, 1,2- or β-elimination, 1,3- or
γ-elimination and so on. The 1,2- or β-elimination is most common
elimination.
H Cl 1,1-elimination Cl
Cl : + Cl2 Br
Cl Cl CH3 1,5-elimination

Br 1,2-elimination
H3C H3C + BrH
 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
HO
Step-I Step II H3C H
CH3 H H3C H H3C H
slow + + fast
H3C H H H + OH2
Br H H3C H H3C H H3C H
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. α-Pinene rearranges to bornyl chloride in presence of HCl.
H + 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 as-
H3C CH3 H3C H3C
ClH H2SO4
H3C H3C
Cl H3C OH H3C CH3
Substitution reaction Elimination reaction
 Carbocations (carbonium)
Wagner-Meerwein rearrangement: (mechanism)
The mechanism of WM rearrangement involves following steps-
a. 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 H3C
ClH +
H3C H3C + H3C CH2
H3C OH H3C O H
H3C
neopentyl alcohol H
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 H3C
+ 1,2-methyl shift +
H3C CH2
H3C H3C CH3
primary carbonium ion tertiary carbonium ion

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

carbonium ion either undergoes substitution or elimination reaction to give
H3C H2SO4 H3C H3C
rearranged product. + ClH
HC 3
H3C CH3 H3C CH3 Cl CH3
Elimination reaction tertiary carbonium ion Substitution reaction

d. 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
bonding pair. H CH -CHO
Base
CH -CHO
2 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 Base
H CH2-CHO CH2-CHO CH3-CO-CH2-H CH3-CO-CH2

H-CH2-NO2 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

[ 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
O O O
group such as nitro, cyano, carbonyl, etc.
+ Nu
Nu Nu

Many more methods are used to generate carbaions.

 Carbanions
Configuration of carbanion:-
The hybridization of carbon bearing negative charge (carbanion) is SP 3
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 R3 R1 R3
R2 R2
(Carbanion) Umbrella effect
It is assumed that, a carbanion which is stabilized by resonance effect
is SP2 hybridized having planar geometry.
R2
R1

R3 O
Planar hybrid structure
 Carbanions
There are several methods for the preparation of carbanion as-
1. 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.
Base R'-X
R/H H R/H M R/H R'
acetylene metal alkylide higher alkyne
terminal alkyne
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 O O O O
H R Base R R R R'-X R' R
H H H
R R R R H R
H
O O O O O
Active methylene group
 Carbanions
Stability of carbanion of active methylene group:
The hydrogen atom of methylene carbon in EAA is more acidic due to-
1. 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 O O O
O O O O
EtONa
H3C OEt H3C OEt
H3C OEt H3C OEt
H
EtOH Carbanion
 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 O O O O O
EtONa ClCH2 COOEt 1. NaOH OH
H3C OEt H3C OEt H3C OEt 2. H2O/H+ OH
H Carbanion 3.
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 O
H
NH2 EtO N
POCl3
O + O H
NH2 HO N
H
CH3
Urea EAA 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 COOEt COOEt +
H3O
COOH
EtONa R-COCl
H H R-CO R-CO
EtOH
H COOEt COOEt COOEt COOH
Diethyl malonate Carbanion -CO2
R-CO-CH2COOH
3-Keto acid
d. Synthesis of α,β-unsaturated acids:
Diethyl malonate reacts with carbonyl compound in presence of base
followed by hydrolysis and decarboxylation gives α,β-unsaturated
acid. COOEt EtONa COOEt
R-COR'
R COOEt HO
+ R COOH
3
H H
EtOH EtONa
H COOEt COOEt R' COOEt R' COOH
Diethyl malonate Carbanion -CO2
R H

R' COOH
Unsaturated acid
 Carbanions
e. Synthesis of α-amino acid:
Amino acid (e.g. alanine) can be synthesized by using diethyl malonate
by using following sequence of reactions.

COOEt COOEt COOEt COOEt + COOH

EtONa RX Br2 R H3 O R
H H R
EtOH
H COOEt COOEt COOEt Br Br
COOEt COOH
Diethyl malonate Carbanion
-CO2
R R
R = CH3 : alanine NH3
COOH COOH
H2N Br
Amino acid
 Carbanions
Applications of Grignard's reagent:
Organometallic compounds generate the carbanion by breaking C-M
bond heterolytically.
- +
Mg X R + MgX
R
- +
ZnX CH2COOEt CH2COOEt + ZnX

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

range of synthetically important compounds. e.g. Grignard’s reagent.
Grignard’s reagent reacts with aldehydes and ketones followed by
hydrolysis gives alcohols.
- +
O O MgX OH
R Mg X H2O/H +
+ MgX(OH)
R R
Aldehydes/ketones pri/sec/tert alcohol
alkoxide intermediate
 Carbanions
Grignard's reagent:
Reaction of Grignard’s 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 O MgI OH
H3C Mg I H2O/H +
+ MgI(OH)
H H H CH3 H CH3
H H
Formaldehyde
alkoxide intermediate pri (ethanol) alcohol
- +
O O MgI OH
H3C Mg I H2O/H +
+ MgI(OH)
H3C H H3C CH3 H3C CH3
H H
Acetaldehyde Sec (2-propanol) alcohol
alkoxide intermediate
- +
O O MgI OH
H3C Mg I H2O/H +
+ MgI(OH)
H3C CH3 H3C CH3 H3C CH3
H3C H3C
Acetone
alkoxide intermediate Tert (2-methyl-2-propanol) alcohol
 Carbanions
Aldol condensation:
Aldehydes or ketones containing α-hydrogen atom undergoes self
condensation or with other molecule of aldehyde or ketone in presence
of base (10% NaOH) forming β-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 O O OH
+ H NaOH H
H3C H C H H CH3
H2
Acetaldehyde
Acetaldehyde 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 - O O O
H NaOH -
C H H2C H H2C H
H2
Carbanion enolate ion
Acetaldehyde
2. The enolate ion attacks to another molecule of aldehyde
O -
O O O-
+ H
H3C H H2C H
H CH3
Acetaldehyde
3. Protonation of the product enolate ion alkoxide of aldol

O- H OH O OH
O
H
H
H CH3
H CH3
alkoxide of aldol 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 C
. 2 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 Cl2 Cl2
CH4 + Cl2 CH3Cl CH2Cl2 CHCl3 CCl4

HCl HCl HCl HCl

Mechanism: Initiation
Cl2 2 Cl
.
Propogation: Chlorine radical abstract hydrogen from alkane. The reaction proceeds
to give mixture of CH3Cl, CH2Cl2, CHCl3, CCl4.
. . CH3Cl + Cl
. .
CH2Cl + HCl
CH4 +
.
CH3 + Cl2
Cl CH +
CH3Cl +
3 HCl
Cl
. .
CH2Cl + Cl2 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.
Cl2 Cl
. + Cl
.
. .CH .
Cl
H2C CH2 + Cl 2
CH2-Cl Cl-CH2 CH2-Cl
.CH
CH2-Cl
2
Cl-CH2-CH2-CH2-CH2-Cl

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
. CH2=CH2 + CH3-CH3
CH CH
3 2
+ 3 2
hydrogen donor 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
.
CH CH
3 2 + 3 2 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 Markonownikoff’s 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).
In absence In presence
CH3-CHBr-CH3 CH3-CH=CH2 + HBr CH3-CH2-CH2Br
of peroxide of peroxide
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 R-CHBr-CH 2
sec. radical (stable) 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 .
2 + HBr RCH2CH2Br + Br
sec. radical (stable)

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
. CH2=CH2 + RO
. .
ROCH2-CH2
Propogation:
. . CH2=CH2
ROCH -CH
2 2 + CH2=CH2 ROCH2CH2CH2CH2 and so on
Termination
. R-H
RO(CH2CH2) CH2CH3
RO(CH2CH2) CH2CH2
n
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 (Fenton’s reagent).
Hydroxide radical abstract hydrogen from hydrocarbon forming new
carbon radical. 2+ 3+ - .
Fe + H2O2 Fe + HO + HO

C6H5-CH3 + HO
. .
C6H5-CH2 + OH2

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

3+ . 2+
C6H5-CHO + Fe C H -CO +
6 5 Fe + H+
 Carbon radicals
f. Redox reaction (Kolbe’s Electrolytic method):
Concentrated aqueous solution of sodium salt of carboxylic acids are
electrolyzed forming alkene called as Kolbe’s reaction.

R-CCONa R-COO - + Na+

-
At anode: 2 R-COO- R-R + 2 CO2 + 2 e
-
At cathode: 2 Na+ + 2 e 2 Na
2 Na + 2 OH2 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: or + Y
C + Y X X +
Y
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 CH2 + N2
R R R
+
N N + N N
R
: + N2
R R
carbene
 Carbene
Formation of carbene:
2. From Ketene: Ketene undergoes photochemical decomposition to
carbene. R hv R

R
O
R
: + CO

Ketene Singlet/triplet

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
R1 R2 + R3
R2 R2

singlet carbene triplet carbonium

 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 + : CX 2
CX2

H X X

H + : CX2 . + . CX H
2
H

X X
b. Intramolecular:-
R'' R'
R' H R'' CH2
R + R
R H HC : 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 non-
stereospecifically. The stereo-chemistry of the product was very important for the
detection of singlet or triplet carbene.
R R R R
+ CH2 (cis)
H H
H H
R H
R H
+ CH2 (trans)
H R
H R
R R R R R H
+ CH2 +
H H H H H R
(cis) (trans)
Singlet carbene is added to olefin forming cyclopropane derivative by the
simultaneous formation of two σ-bonds.
R R
R R X R R H H
H H
+
X
H H X X
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 R
R R X R R R R H H
H H spin H H
+
X X2C inversion
H H X2C X X
1. Rotn. about 2. Spin inversion (cis)
C-C bond.
H R
H R R H
R H

X2C X X
(Trans)
 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 α-hydrogen
atom are exist in two isomeric forms keto-form and enol-form.
O OH

H
keto form 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, 1,3-
ketoacids 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 α-proton is
more acidic and therefore easily removed by weak base forming enol.
+OH
O OH
COOEt H+ COOEt COOEt
H3C H3C H3C
H H
keto form acid form of ketone 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.
O O O
OH
COOEt Base slow COOEt COOEt H+
H3C H3C H3C COOEt
enolate ion fast H3C
H carbanion enol form
keto form
 Tautomerism (enolisation)
There are various carbonyl compounds having enol form:
1. β- 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.
O OH O OH
COOEt COOEt
H3C H3C H3C OEt
H enol form enol form
keto form

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

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

H3C CH3 H3C CH3 H3C CH3 H3C CH3

H stabilized by cyclisation
enol form enol form
keto form
 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:
CH3
ClH
1. (CH3)3C-CH2OH H3C CH2CH3
Cl
H3C
1. ether
2. CH3CHO + CH3MgI H3C OH
2. H2O/HCl
H
OH O
10% NaOH
3. 2 CH3CHO
H3C H
hv
4. CH4 + Cl2 CH3Cl + CH2Cl2 + CHCl3 + CCl4
NaOH
5. (CH3)3C-Br (CH3)2C=CH2
 Test No 2 (10 Marks)
Answers
1. H3C
ClH
H3C H3C
+
H3C
+ 1,2-methyl shift H3C
+
H3C H3C + CH2 H3C CH2
OH H3C
H3C H3C O H H3C H3C CH3
H3C
neopentyl alcohol H primary carbonium ion tertiary carbonium ion
primary carbonium ion

H3C H2SO4 H3C H3C

+ ClH
H3C
H3C CH3 H3C CH3 Cl CH3
Elimination reaction tertiary carbonium ion Substitution reaction

2. O
- +
O MgI
H2O/H +
OH
H3C Mg I + MgI(OH)
H3C H H3C CH3 H3C CH3
H H
Acetaldehyde Sec (2-propanol) alcohol
alkoxide intermediate

3. HO - O O O
-
O -
H -
O O O-
NaOH
C H H2C H H2C H + H
H2 H3C H H2C H
Carbanion enolate ion H C
Acetaldehyde Acetaldehyde enolate ion alkoxide of ald
OH
O O- H OH O
H
H
H CH3
H CH3
alkoxide of aldol 3-hydroxybutanal (aldol)
 Test No 2 (10 Marks)
Answers
4. Cl2 2 Cl
.
. . CH3Cl + Cl
. .
CH2Cl + HCl
CH4 +
.
CH + Cl
Cl CH +
CH3Cl +
3
HCl
Cl
. CH2Cl + Cl2
. CH2Cl2 + Cl
.
3 2

CH2Cl2 + Cl
. .CHCl + HCl CHCl3 + Cl
. .
CCl3 + HCl
.CHCl CHCl3 +
2
. . .
2 + Cl2 Cl CCl3 + Cl2 CCl4 + Cl
5.
e.g. Dehydrobromination of 1-bromopropane
HO
Step-I Step II H3C H
CH3 H H3C H H3C H
slow + + fast
H3C H H H + OH2
Br H H3C H H3C H H3C H
Carbonium ion
Thanks for your good Attention