Org. Chem - Rearrangement and Elimination Rxns.

1 Organic Chemistry II (P22CH11) Unit IV
ORGANIC CHEMISTRY II (P22CH11)
Unit IV _ Rearrangement and Elimination Reactions
Classification - mechanisms of the following rearrangements – Wagner-Meervein,

Dienone-phenol, Wolff, Favorski, Steven, Sommelet Hauser, Demjenov, Von-Richer, Schmidt,
Pummerer rearrangements. Mechanisms of E1, E2, E1CB - stereochemistry of elimination -
competition between elimination and substitution pyrolytic cis elimination - chugaev reaction
dehydration - dehydrohalogenation - Hofmann degradation – cope elimination, Bredt’s rule with
examples. Saytzeff’s rule and Hofmann rule.
Reference
1. I. L. Finar, “Organic Chemistry”, Volume-II, 5th Ed., (2006).

2. Structure and Mechanisms, F. Carey, R. Sundberg, “Advanced Organic Chemistry. Part-A”. 4th Ed.,
Kluwer Publishers, 2000.
3. V. K. Ahluwalia and R. K. Parashar, “Organic Reaction Mechanism”, Narosa, 2006.
𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑴. 𝑺𝒄. , 𝑷𝑮𝑫𝑪𝑨
REARRANGEMENT REACTIONS
INTRODUCTION
Rearrangement reactions are an interesting class of reactions wherein an atom or group of atoms
migrates from one carbon atom to another within a molecule or from one molecule to another. The
reaction often includes the breaking and making of C – C sigma bond. The migrating group may leave the
molecule during the reaction. The migrating group first gets completely detached from the molecule,
subsequently it gets reattached at some other reactive site of the molecule (intermolecular). In some cases,
the migrating group never leaves the molecule during migration (intramolecular).
Intermolecular Rearrangement: In intermolecular reactions, migration of group/atom can take place in

two separate molecules. Eg., Aromatic Rearrangement
Intramolecular Rearrangement: In intramolecular rearrangement reactions, the migration of a

group/atom can occurs within the same molecule. Eg., Free radical rearrangement
WAGNER – MEERVEIN REARRANGEMENT
Wagner proposed that the formation of Camphene from borneol or bornyl chloride involved
rearrangement. Meervein also found that molecular rearrangements occurred in the camphene hydrochloride-
isobornyl chloride interconversion. These types of rearrangement don’t occur in bicyclic terpenoids.
Reaction involving the change in the carbon skeleton through the rearrangement of carbocations as
intermediates, are collectively known as Wagner – Meervein Rearrangement. Eg., 3,3-dimethyl-1-butene
adds HCl to give 2-chloro-2,3-dimethylbutane as major (60 – 75%) and 2-chloro-3,3-dimethylbutane as
minor (25 – 40%) product.
The above rearrangement occur via carbocation intermediate and involve the migration of alkyl
group with its pair of electrons to an electron deficient carbon atom.
Wanger-Meervein rearrangement will occur if it leads to the new carbocation being more stable
than the original (3𝑜 > 2𝑜 > 1𝑜 ). This is the driving force of the alkyl migration. Eg., When neo-pentyl
bromide is hydrolyzed under 𝑆𝑁 1 condition, it is found that instead of neopentyl alcohol, 2-methyl-2-
butanol and 2-methyl-but-2-ene is formed.

Mechanism
Example 1,
𝛽 −hydrogen elimination reaction possible only with tertiary carbocation since the process need
beta-hydrogen that primary carbocation lacks. No such rearrangement takes place with its phenyl
analogue because the benzylic cation is stabilized by the phenyl group through delocalization.
Example 2,
Example 3,
The aryl group migrates faster than alkyl group, electron-releasing group in the aryl group increases
the rate of migration while electron-withdrawing group decreases the rate of migration. The order of
migration for few selected alkyl group is,
𝑃ℎ𝑒𝑛𝑦𝑙 > 𝑡 − 𝑏𝑢𝑡𝑦𝑙 > 𝑒𝑡ℎ𝑦𝑙 > 𝑚𝑒𝑡ℎ𝑦𝑙

WOLFF REARRANGEMENT
The 𝛼 − diazoketones undergoes rearrangement with elimination of very stable nitrogen molecule
in the presence of silver oxide (or Colloidal Pt or Cu) to form a ketene is known as Wolff rearrangement
reaction. The 𝛼 − diazoketones can be prepared by the reaction of acid chloride with diazo compounds in
a normal addition – elimination process.
The Wolff rearrangement generates ketene in the absence of nuclophile and therefore it can be
isolated in this reaction. However, when this rearrangement is carried out in the presence of water, alcohol
or amine, the ketene is converted into carboxylic acid, ester or amide respectively. This reaction is known
as Arndt – Eistert Synthesis which is useful for converting an acid, RCOOH into its next higher
homologue, RCH2COOH.
Mechanism
Step 1: Elimination of molecular nitrogen, R group migration and formation of ketene intermediate.
Step 2: Water attacks as nucleophile to the ketene.
Step 3: Transfer of proton
Step 4: Tautomerization gives the desired product.

FAVORSKII REARRANGEMENT
The Favorskii rearrangement reaction involves the conversion of 𝛼 − haloketones to carboxylic

acid and its derivatives in the presence of strong base (may be hydroxide or alkoxide). The rearrangement
of cyclic ketones involves ring contraction.
Mechanism
Step 1: Abstraction of α-H on the side of the ketone away from the chlorine atom forms an enolate.
Step 2: SN2-type reaction and formation of cyclopropanone ring intermediate.
Step 3: Hydroxide as a nucleophile attack at the ketone.
Step 4: Ring opening gives an anion.
Step 5: Proton transfers from water or solvent gives the final product.
Example 1,
Example 2,

SOMMELET-HAUSER REARRANGEMENT
Sommelet and Hauser found that benzhydryltrimethylammonium hydroxide rearranged to o-

benzylbenzyldimethylamine upon heating with Conc. NaOH.
Mechanism
When 2,4,6-trimethylbenzyltrimethylammonium iodide undergoes Sommelet-Hauser

rearrangement in liq. Ammonia in presence of sodamide, the product is not aromatic.
When dibenzyldimethylammonium salt is treated with phenyllithium in ether (Strong base) both the
Sommelet-Hauser rearrangement product and Steven rearrangement product are obtained. Both
rearrangements proceed via the same intermediate. At high temperature Steven’s rearrangement is
preferred, while at lower temperature, the yield of Sommelet rearrangement product increases.

VON-RICHTER REARRANGEMENT
Von – Richter rearrangement reaction involves the Cine-substitution of aromatic nitro compound to
produce aromatic carboxylic acid in the presence of strong cyanide. Eg., p-bromonitrophenol on reaction
with KCN to yield a m-nitrobenzoic acid.
Mechanism
In the first step the carbon ortho to the nitro group is attacked by cyanide which is followed by ring
closing through nucleophilic invasion at the cyano group result imidate intermediate. In this intermediate,
the nitrogen-oxygen bond breaking occurs to give ortho-nitroso benzamide which recyclizes to yield a
compound with N – N bond. The elimination of water results in a cyclic azoketone and it undergoes
nucleophilic attack by 𝑂𝐻 − to form a tetrahedral intermediate. Finally the intermediate rearranged and
lose a azo group to give the product m-bromobenzoic acid.

SCHMIDT REARRANGEMENT
The conversion of carboxylic acid to primary amine with hydrazoic acid in the presence of strong
acid having one carbon less is accomplished by Schmidt rearrangement reaction. Schmidt reaction is
mechanically related to Curtius rearrangement.
Salient features of Schemidt Rearrangement reaction
a) The acid-catalyzed reaction of hydrogen azide with electrophiles, such as carbonyl compounds,
tertiary alcohols or alkenes. After a rearrangement and extrusion of N2, amines, nitrites, amides or
imines are produced.
b) The conversion of a carboxylic acid into an amine with concomitant chain degradation by one
carbon atom. The reaction of hydrazoic acid with a ketone does not lead to chain degradation, but
rather to formation of an amide by formal insertion of an NH-group.
c) With long-chain, aliphatic carboxylic acids yields are generally good, while with aryl derivatives
yields are often low. The Schmidt reaction of ketones works best with aliphatic and alicyclic ketones;
alkyl aryl ketones and diaryl ketones are considerably less reactive.
d) The reaction is closely related to Hofmann and Curtius reactions, all of which involve the formation
of isocyanate intermediate through the migration of a group from carbon to nitrogen.
e) When applied to a cycloketone, the Schmidt reaction leads to formation of a ring-expanded lactam.

Mechanism
Mechanism for carboxylic acids to primary amine
Step 1: Protonation of carboxylic acid occurs followed by loss of water to form an acylium ion.
Step 2: Nucleophilic addition of hydrazoic acid to the acylium ion takes place.
Step 3: Loss of nitrogen molecule of step 2 product occurs.
Step 4: Deprotonation of step 3 product.
Step 5: The migration of R group occurs to form an isocyanate intermediate.
Step 6: The step 5 product hydrolyzed by water to produce the product primary amine.
Mechanism for ketones to secondary amine

Step 1: Protonation of carbonyl compound (Ketone) occurs.
Step 2: Nucleophilic addition of hydrazoic acid to the protonated ketone to give intermediate takes place.
Step 3: The intermediate is promoted by the protonation of the carbonyl oxygen and lose water molecule.
Step 4: The nitrilium ion is formed by migration of group ‘R’ and loss of azo group.
Step 5: The nitrilium ion is hydrolysed by water followed by deprotonation takes place.
Step 6: Tautomerization gives the desired product.
In the case of aldehyde, the intermediate in which migration of H will give nitrile and
migration of R will give formyl derivative.

PUMMERER REARRANGEMENT
The Pummerer rearrangement is referred to the formation of α-substituted sulfides from the
corresponding sulfoxides (must have at least one hydrogen atom at their α-position) in the presence of
𝐻𝐶𝑙, 𝐻2 𝑆𝑂4 , 𝑇𝑠𝑂𝐻, 𝐼2 /𝑀𝑒𝑂𝐻, 𝐴𝑐2 𝑂, 𝑇𝐹𝐴𝐴, 𝑡 − 𝐵𝑢𝐵𝑟, 𝑀𝑒3 𝑆𝑖𝑋, 𝑃𝐶𝑙3 , 𝑃𝐶𝑙5 or 𝑆𝑛(𝑂𝑇𝑓)2 and
nucleophile i.e., may be Water, alcohol.
Mechanism
Step 1: acylation of the sulfoxide oxygen to form an acyloxysulfonium salt

Step 2: loss of a proton from the α-carbon to afford an acylsulfonium ylide
Step 3: cleavage of the sulfur-oxygen bond to give sulfur-substituted carbocation (RDS)
Step 4: capture of the nucleophile by the carbocation.

DIENONE-PHENOL REARRANGEMENT
When 4,4-dialkyl cyclohexadienone is treated with acid, it is converted to phenol with migration of
one of the alkyl groups to the adjacent carbon. This is known as dienone–phenol rearrangement.
When one of the alkyl groups form a part of the cyclic system, either the alkyl group or the
ring methylene group may migrate. Phenol–dienone rearrangement (reverse) has been observed during
the electrophilic substitution in phenols in some cases. This mechanism is intramolecular rearrangement.
Mechanism
Step 1: Protonation of 4,4-dimethylcyclohexa-2,5-dienone takes place.
Step 2: Delocalization of pi electron occurs.
Step 3: Methyl group shifted to the adjacent carbon atom.
Step 4: Deprotonation of the step 3 product gives the 3,4-dimethylphenol.
STEVENS REARRANGEMENT
A quaternary ammonium salt, in which none of the alkyl group is having a 𝛽 − hydrogen atom but
one of the alkyl groups has an electron-withdrawing group 𝛽 – to the nitrogen atom, undergoes Stevens
rearrangement in the presence of a base to yield a tertiary amine.
The rearrangement involves migration of a group, without pair of electrons, from nitrogen to carbon
having negative charge.

Mechanism
The rearrangement is formulated to proceed via an intermediate radical-pair or ion-pair. The

initial step is the formation of a nitrogen-ylide by deprotonation of the ammonium species with a strong
base. The abstraction of a proton from the α – carbon is facilitated by an electron withdrawing group i.e.,
Acid, ester or Phenyl.
Ion-pair mechanism: A heterolytic cleavage of the N-R bond will lead to the ion-pair, held together in a
solvent cage.
Radical pathway: A homolytic cleavage of the N-R bond. The rearrangement proceeds via an
intermediate radical-pair to yield the tertiary amine. The order of migration is propargyl > allyl > benzyl >
alkyl. Eg.,
Proton removal is facilitated by the positive charge in the cationic substrate and also by the
enolate ion formation Migrating groups are generally benzyl or allyl system.
DEMJANOV REARRANGEMENT
This rearrangement involves the reaction of primary amine with nitrous acid to form
rearranged alcohols. The reaction proceeds via diazotization followed by ring expansion or ring
contraction.Eg.,
Mechanism
Step 1: The nitrosonium ion reacts with the primary amine.

Step 2: Abstraction of proton from the amine.
Step 3: Protonation of step 2 product takes place.

Step 4: Deprotonation of step 3 occurs.

Step 5: Protonation.
Step 6: Elimination of water and formation of diazonium ion.
Step 7: Rearrangement and formation of carbocation.
Step 8: Nucleophilic attacks by water.
Step 9: Deprotonation and formation of the product.
Formation of Cyclopentanol
Formation of Cyclobutylmethanol
Tiffeneau – Demjanov Rearrangement

ELIMINATION REACTIONS
INTRODUCTION
The elimination reactions are reverse of addition reactions. In these reactions two atoms or groups
attached to adjacent carbon atoms of the substrate molecule are eliminated to form multiple bonds i.e.,
double or triple bond. In these reactions a atoms or group from 𝛼-carbon atom and a proton from the 𝛽-
carbon are eliminated. This method is commonly used for the preparation of alkenes or alkynes. In these
reactions, the presence of one hydrogen on the 𝛽-carbon atom is necessary.
These reactions are carried out in presence of acid or base or some time through pyrolysis. During
elimination reactions two sigma bonds are broken and a pi bond is formed. In most organic elimination
reactions, at least one hydrogen is lost to form the double bond. An important class of elimination
reactions is those involving alkyl halides, and alcohols. The halogens are considered to be good leaving
group. When the substrate molecule is asymmetric; the regioselective products are formed in elimination
reaction. The elimination reactions occur via three distinct mechanisms, viz; E1, E2, E1CB. Eg.,
There are three fundamental events in these elimination reactions:

(i) Removal of a proton
(ii) Formation of the C-C π bond
(iii) Breaking of the bond to the leaving group

E1 REACTION MECHANISM
𝐸1 indicates unimolecular elimination reaction. In these reactions the rate of elimination depends
only on the concentration of the substrate and independent of the concentration of the nucleophile and the
reaction is of First order. These reactions are non-stereospecific and it follows Saytzeff rule. 𝐸1 reactions
don’t occur with primary halides. Like 𝑆𝑁 1 reaction the 𝐸1 also two step process.
▪ The first step is the slow ionization of alkyl halide to give the carbocation.
▪ The second step involves the abstraction of a proton from the adjacent beta-carbon atom giving
rise to the formation of alkene.
Effect of ‘R’ group
• The reactivity order of alkyl group is as, (𝐶𝐻3 )3 𝐶 → (𝐶𝐻3 )2 𝐶𝐻−> 𝐶𝐻3 𝐶𝐻2 −> 𝐶𝐻3
• The rate determining step is the loss of leaving group to form the intermediate carbocation.
• The greater the stability of carbocation, the more will be the rate of the reaction.
• The rate of the reaction increases s the number of R groups on the carbon with leaving group
increases.
Leaving group
• Since the loss of leaving group is the rate determining step, better the leaving group, faster the 𝐸1
reaction.
• In the acid catalyzed reactions of alcohols, the -OH is protonated first to give an oxonium ion,
providing the much better leaving group i.e., water.
• Base is not involved in the rate of 𝐸1 reaction, the nature of base is unimportant in these reactions.
• Favored by weaker bases such as water and alcohol.
Type of solvent
Favored by polar protic solvents, which can stabilize the ionic intermediates.
𝑬𝟏 mechanism for Alcohols
Step 1: Protonation of the alcoholic oxygen to make a better leaving group i.e., water. This step is very
fast and reversible.
Step 2: The loss of water molecule occurs to form carbocation intermediate. Deprotonation by water to
the carbocation leads to create a -C=C- centre. (bond breakage is exothermic).

𝑬𝟏 mechanism for Alkyl halides
Step 1: Cleavage of 𝐶 − 𝑋 bond allows the loss of leaving group 𝐵𝑟 − to give a carbocation intermediate.
(bond breakage is endothermic).
Step 2: Deprotonation by alkoxide ion (base) to the carbocation leads to the formation of -C=C- centre.
E2 REACTION MECHANISM
𝐸2 indicates bimolecular elimination reaction. In these elimination reactions, the rate depends on the
concentration of the both the substrate and the nucleophile and the reaction is of second order. Like 𝑆𝑁 2
reaction the 𝐸2 also one step process. In these reactions, abstraction of proton from 𝛽-carbon atom and the
expulsion of an atom or group from the 𝛼-carbon atom occurs simultaneously.
Effects of ‘R’ group
• The reactivity order of ‘R’ group is as, (𝐶𝐻3 )3 𝐶 → (𝐶𝐻3 )2 𝐶𝐻−> 𝐶𝐻3 𝐶𝐻2 −> 𝐶𝐻3 .
• These reactions transform 2 𝑠𝑝3 carbon atoms into 𝑠𝑝2 carbon atoms. These decreasing the steric
interactions.
• The more, highly substituted systems undergo 𝐸2 elimination more rapidly as in 𝐸1 reactions.
• The number of ‘R’ groups on the carbon with the leaving group increases, the rate of the 𝐸2 reaction
increases.
Leaving Group
• The C-LG bond is broken during the rate determining step, so the rate does depend on the nature of
the leaving group.
• However, if the leaving group is too good, then an 𝐸1 reaction may result.
• The order of the rate of reaction, 𝑅 − 𝐼 > 𝑅 − 𝐵𝑟 > 𝑅 − 𝐶𝑙 > 𝑅 − 𝐹.
Base
• These reactions are favored by strong bases.

• Since, base is involved in the rate determining step.
• More reactive bases will favor an 𝐸2 reaction.

Example 1,
Example 2,
The above two reaction is a one step process and passes through a transition state. This reaction is
also known as 1,2-elimination or 𝛽-elimination.
Difference between 𝑬𝟏 and 𝑬𝟐 Mechanism
𝑬𝟏 𝒎𝒆𝒄𝒉𝒂𝒏𝒊𝒔𝒎 𝑬𝟐 𝒎𝒆𝒄𝒉𝒂𝒏𝒊𝒔𝒎
Unimolecular reaction Bimolecular reaction
Two step reaction Single step reaction
Carbocation intermediate formed No intermediate formed. However, the
mechanism takes place via transition state.
Reactivity order of RX is 3𝑜 > 2𝑜 > 1𝑜 Reactivity order of RX is 3𝑜 > 2𝑜 > 1𝑜 . No
steric effect
Polar protic solvent is good because stabilized Polar aprotic solvent best
ionic intermediate.
No stereospecific Trans elimination because low energy
consumption
Rearrangement may take place No rearrangement take place
Rate of reaction depends only on the Rate of reaction depends on the concentration
concentration of the substrates. of both the substrate and nucleophile.
Rate of reaction increases when concentration Rate of reaction increases if the nucleophile
of substrate decreases attack strongly
Follow saytzeff rule Antiperiplanar attack
Hydrogen eliminates wherever possible. Hydrogen eliminates from beta carbon
Phenyl group and alkyl group influence Phenyl group influence elimination because
elimination. product alkene stabilized by resonance.

STEREOCHEMISTRY OF ELIMINATION REACTION
Stereochemistry of 𝑬𝟐 reaction
The transition state of an E2 reaction consists of four atoms from the substrate (one
hydrogen atom, two carbon atoms, and the leaving group, X) aligned in a plane. There are two ways for
the C—H and C—X bonds to be coplanar.
▪ E2 elimination occurs most often in the anti-periplanar geometry. This arrangement allows the
molecule to react in the lower energy staggered conformation, and allows the incoming base and
leaving group to be further away from each other.
▪ The anti-periplanar geometry also allows direct interaction between the bonding electrons of C — H
bond and the antibonding orbital of the C —X bond.
▪ Diastereomeric starting compounds yield diastereomeric products after an E2 reaction.
Stereochemistry of 𝑬𝟐 mechanism
In the case of bimolecular elimination reaction there are two eliminations possible namely, syn and
anti-elimination.
Syn elimination: If the groups are eliminated from the same side i.e. syn in position the elimination is
known as syn elimination.
Anti elimination: If the groups are eliminated from the opposite sides i.e. anti in position the elimination
is known as anti-elimination.
In anti E substrate has staggered conformation while that of in syn is eclipsed. In staggered
conformation C‐X, C‐C and C‐H bonds are in the same plane making an angle of 1800, therefore electron
pair to B carbon is made easily available for the formation of new bond.

E2 reactions are highly stereospecific and anti-elimination is preferred over syn elimination
as substrate has to adopt an eclipsed conformation, which is higher in energy, eliminating groups are
eclipsing in position making 00 angle.
The reaction is facile when both the leaving groups and the carbon bearing them are in the
same plane (trans coplanar). Eg., In threo-2-bromo-2,3-diphenylbutane, when two leaving groups are
planar there are two conformations,
i) The two groups are in trans position (anti-periplanar)

ii) The two are in cis position (syn-periplanar)
The elimination may proceed as follows,
On examination of the Newmann projections of the trans (staggered) and cis (eclipsed)
conformations, we found the elimination is more facile than trans conformation than from the cis
conformation. This is because in trans conformation the base approaches from the farthest side of the
leaving group while in cis conformation the attack is from the same side of the leaving group, which
causes repulsion. Also the elimination occurs from the lower energy staggered conformation than from
the higher energy eclipsed conformation.
Evidence for 𝑬𝟐 elimination
Consider 1-bromo-1,2-diphenylpropane as example. The molecule 1-bromo-1,2-diphenylpropane

can exist in both erythron and threo enantiomers. In anti-elimination atoms or groups are removed from
opposite sides. Erythro isomer undergoes elimination to give Z‐isomer and threo isomer gives E‐isomer
as a product.

Reaction of meso‐2,3‐dibromobutane in presence of iodide ion as base gives trans‐2‐ butene, where
iodide ion abstracts the Br+ as base abstracts the proton, and Br‐ departs as a leaving group. dl-2,3‐
Dibromobutane under same condition gives cis‐2‐butene. Meso compound undergoes reaction at the
double rate than dl pair as bulky methyl groups are in opposite sides (threo), while that of dl pair are in
the same side (erythro) lowering the rate of reaction.
Eclipsing effect
▪ Lowering the rate of reaction in 𝐸2 reaction due to steric effect is known as eclipsing effect in 𝐸2 .
▪ If 𝐶𝐻3 groups are replaced by phenyl groups, rate of reaction decreases 100 times. Steric effect
lowering the rate of 𝐸2 is known as eclipsing effect in 𝐸2 .
▪ Reaction of 2-bromo-1-phenylpropane in presence of alkoxide as base gives styrene. Here, threo
isomer gives trans while the erythron isomer gives cis product. Among these threo undergo faster
reaction rate.
In threo isomer they are on the opposite side. While in erythreo isomer bulky Ph and Me
groups are on the same side, that causes steric effect leading to the partial eclipsing conformation, which
is less stable conformer and undergoes reaction at a lower rate than threo isomer. In this case eclipsing
effect plays important role.

Problems
1. Cis‐tert‐butylcyclohexylbromide under goes elimination reaction to give Cis‐tertbutylcyclohexene,

whereas its trans isomer does not undergo reaction at all‐justify.
• E2 elimination in six membered ring proceeds best when adjacent trans group can adopt
antiperiplanar conformation, even if this is higher energy conformation.
• The stable conformation having bulky tert-butyl in equatorial position and bromide in axial
position, in which Br-C, C-C and C-H bonds have antiperiplanar relationship and can easily
undergo E2 reaction to give cis-tert-butylcyclohexene.
• Whereas, in case of trans-tert-butylcyclohexylbromide aa or ee conformations are possible. The
stable conformation having bulky tert-butyl and bromide both in equatorial position.
• To adopt antiperiplanar relationship for Br-C, C-C and C-H bonds, ee conformation to be
converted aa conformation, where tert-butyl group has to be equatorial, that is sterically
unfavorable, therefore it cannot undergo E2 elimination at all.
2. Neomenthyl bromide when undergoes E2 elimination reaction to give 1-menthene (more stable, major
prod 75%) and 2 menthene (less stable minor prod 25%), while menthyl bromide under goes E2
elimination reaction to give only 2-menthene as a product-justify.
• E2 elimination in six membered ring proceeds best when adjacent trans group can adopt
antiperiplanar conformation, even if this is higher energy conformation.
• In neomenthyl bromide bulky iso‐propyl group tends to remain equatorial, Br is axial and two
axial H atoms on neighboring carbon are axial and anti to Br for E2 anti elimination.
• Where as in menthylchloride bulky iso‐propyl group tends to remain equatorial, Br is also
equatorial. For Br, to become axial it has to convert iso‐prop group from equatorial to axial
which is sterically unfavorable, and can have only one axial H atom on neighboring carbon anti
to Br for E2 anti-elimination.
• In addition, 1‐menthene is obtained as a major product according to Sayzeff’s orientation rule.

MECHANISM FOR E1CB REACTION
This one begins with a rapid loss of proton to base. Loss of proton leads to a stabilized
carbanion. The carbanion is then converted to an alkene, conversion of carbanion to an alkene is the rate
determining step. This elimination, since it proceeds through the conjugate base of the starting material, is
known as E1CB. The E1CB reaction competes with the E2 reactions. However, E1CB reactions are much
less common then are E2 reactions because of the greater instability of carbanions. Indeed, only a very
small percentage of eliminations follow this path way.
The E1CB reaction is first order in base and first order in substrate just like the E2 reaction.
𝑅𝑎𝑡𝑒 = 𝐾 [𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒] [𝐵𝑎𝑠𝑒]

Thus, the reaction is second order reaction, first order with respect to the substrate and first
order with respect to the base. But the reaction is unimolecular reaction because reaction velocity depends
only on the concentration of the conjugate base of the substrate. The use of deuterium labelling can help
to distinguish the E1CB reaction from the E2 pathway. If an E2 reaction is carried out in a solvent which
could act as deuterium source, and the reaction is interrupted before it has gone to completion, recovered
starting material is free from any deuterium. This happens because there is no way by which deuterium
could become incorporated into the starting material.
(i) E1CB mechanism is limited to substrates which can stabilize the carbanion intermediate
i.e., β-carbon should contain stabilizing group like carbonyl, nitro, cyano, sulphonyl.
(ii) Product formation generally takes place by Hofmann rule.
(iii) Leaving group of the substrate is generally poor leaving group.
(iv) β-Hydrogen should be highly acidic so that the carbanion formation may take place easily.
(v) Reaction takes place in the presence of a strong base.

Example.
Problem
Propose the mechanism for the following reaction.
Mechanism
COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION
Elimination and substitution reactions are closely related and competitive but form different
products. However, substitution becomes favourable as it involves less bond reorganization and
energetically being more favourable. Eg., 𝑆𝑁 1 and 𝐸1 reaction of 2-methylpropane.
SN1 and E1 reactions have exactly the same first step is a formation of a carbocation. They differ in
what happens to the carbocation. Since in both the reactions, the rate determining steps are the same, they
cannot be individually controlled. Because E1 reactions often occur with a competing SN1 reaction, E1
reactions of alkyl halides are much less useful than E2 reactions.

Substitution vs Elimination
Primary alkyl halides
With strong nucleophiles: Substitution via 𝑆𝑁 2 mechanism
With strong sterically hindered bases: Elimination occurs via 𝐸2 mechanism.

Secondary alkyl halides
With strong bases and nucleophiles: A mixture of 𝑆𝑁 2 and 𝐸2 products are formed.
With strong sterically hindered bases: Elimination occurs via 𝐸2 mechanism.
With weak nucleophiles or bases: A mixture of 𝑆𝑁 1 and 𝐸1 products are formed.

Tertiary halides
With strong bases: Elimination occurs via 𝐸2 mechanism.
With weak nucleophiles or bases: A mixture of 𝑆𝑁 1 and 𝐸1 products are formed.

1. Basicity and Nucleophilicity
For elimination reaction basicity of nucleophile or base is important while for substitution it
is nucleophilicity that matters more. Therefore, strongly basic conditions favour elimination reaction.
If some compounds which are not strong bases but are good nucleophiles are used, then substitution
predominates. Use of strong and slightly polarizable base such as amide or alkoxide favours
elimination over substitution. Eg.,
2. Structure of the substrate

Crowded reactant favours elimination reaction over substitution due to hindrance to
approach of nucleophile. In primary alkyl halides, easy approach of nucleophile is possible and hence,
substitution is favoured. In secondary alkyl halides, substitution is difficult due to steric hindrance and
elimination is favoured. Whereas, in case of tertiary halides SN2 reaction is not possible, elimination is
favoured particularly at elevated temperature. If substitution occurs, then it is by SN1 pathway.
Elimination can also be favoured by stability of product formed. Eg.,

3. Nature of the base

Structure of base has similar effect on the ratio of substitution or elimination reaction. A
more crowded base of similar strength favours elimination. Therefore, tert-butoxide gives more of
elimination product than substitution whereas ethoxide shows opposite effect altogether.
4. Nature of the solvent

Here, charge is more dispersed due to which less polar solvents favour E2 elimination over
SN2 reaction. (Similar is the case with E1 reaction).
5. Effect of temperature
Elimination reactions are favoured at higher temperature than substitution reaction because
elimination reaction has high free energies of activation than substitution due to higher degree of bond
reorganization (or change in the bonding pattern) i.e., more bonds are broken and formed.

PYROLYTIC ELIMINATION
Some substrates such as esters and amine oxides do not require any external agent for elimination,
simply heating such substrates provides elimination product. These reactions are known as pyrolytic
Elimination. These reactions are suggested to proceed through a concerted, cyclic, six membered
transition state. They are often designated as Ei (Elimination internal). These reactions follow
stereospecific syn elimination pathway i.e., leaving group must assume syn periplanar conformation with
respect to each other. Eg.,
Examples for Pyrolytic elimination reaction

CHUGAEV ELIMINATION
In these reactions, O-alkyl-S-methyl xanthates are pyrolyzed to olefin, (oxysulfide and

methanethiol) at about 200oC. These reactions are of particular use due to its relatively milder reaction
conditions as compared to other pyrolytic eliminations. Using this method, alkenes which are labile or
tend to undergo rearrangement can be prepared. These reactions take place via six membered cyclic
transition state and generally proceed through syn elimination, although anti elimination is also reported.
Examples,
COPE ELIMINATION
Pyrolytic elimination of amine oxide can be done under mild conditions, to give olefin. This
reaction is called as Cope reaction.
Internal base attacks beta-proton, so highly basic nucleophile is not required.

EXAMPLES FOR ELIMINATION REACTIONS
• Dehydration of alcohols
Dehydration of alcohols via elimination reaction favoured at higher temperature in the
presence of acids i.e., 𝐻2 𝑆𝑂4 , 𝐻𝐶𝑙, 𝐻3 𝑃𝑂4 , 𝑃𝐵𝑟3 , 𝑆𝑂𝐶𝑙2 ,etc. For secondary and tertiary alcohols, the
mechanism goes through carbocation intermediate, (E1 reaction).
The dehydration of primary alcohol is supposed to proceed through E2 mechanism. In a

protonated alcohol, the Lewis base removes β-hydrogen, simultaneously an olefinic bond is formed
and protonated hydroxyl group is departing as ‘water’.
Metal oxides are excellent and widely used catalysts for dehydration of alcohol. Different
products are formed due to different catalytic properties of these oxides or different reaction
conditions.
• Dehalogenation
In a reaction of NaI with 1,1,2-tribromocyclohexane, syn elimination will give labelled
product (bromine with a * is the labelled one). Whereas, anti-elimination will give non labelled
product. It is found that debromination using NaI is purely anti. However, with zinc, the major
product is anti, but some syn is also formed elimination.

Another example is, meso-stilebene dibromide gives E-stilbene and d,l-stilbenedibromide

gives Z-stilbene.
It is important to realize that the anti-periplanar geometries of H and Br are required for this
elimination. In the given stereoisomer, this is possible and hence it leads to a E-stilbene as the
product.
For the anti-periplanar arrangement in this stereoisomer, the molecule should rotate along
the C-C bond first such that both Ph comes on the same side and hence it leads to a Z-stilbene as the
product.
• Hofmann Degradation
Pyrolysis of a quaternary ammonium hydroxide salts, derived from an amine having alkyl
group that is larger than the methyl group, gives an olefin and a tertiary amine. This type of
elimination reaction known as Hofmann elimination or Hofmann degradation. Eg., when
trimethylproprylammonium hydroxide is heated, it decomposes to trimethylamine and propene.
Mechanism
The quaternary ammonium halides on treating with moist silver oxide form corresponding
hydroxides. The hydroxide ion acts as a strong base and abstracts the 𝛽-hydrogen of the larger alkyl
group and pi-bond is formed via expulsion trialkylamine (𝐸2 elimination). Hofmann elimination
products are generally the less substituted alkenes (Hofmann rule). Here, the least substituted alkene
is the predominant product. This kind of elimination follows Saytzeff rule n which the more stable
alkene is the major product.
Another example as follows,

• Dehydrohalogenation
Consider the Dehydrohalogenation of cis-1-Chloro-2-methylcyclohexane.
The conformer with Cl in an axial orientation reacts to give two alkenes. The alkene that is
more substituted is the major product.
Consider another example, Dehydrohalogenation of cis-1-Chloro-2-methylcyclohexane
The conformer with Cl in an axial orientation has just one β-H atom. Only one product is
formed, which is not what is predicted by the Saytzeff rule.
In conclusion, with substituted cyclohexanes, E2 elimination should occur with a trans

diaxial arrangement of the leaving group and the β-H, and as a result of this requirement, the more
substituted alkene is not necessarily the major product.
Examples,

BREDT’S RULE
The Bredt’s rule states that “A double bond cannot be placed at the bridgehead of a bridged ring
system, unless the rings are large enough”. It primarily relates to bridgeheads with carbon – carbon and
carbon – nitrogen double bonds.
For example, two of the following isomers of norbornene violate Bredt's rule, which makes them
too unstable to prepare.
Bredt's rule is a consequence of the fact that having a double bond on a bridgehead would be
equivalent to having a trans double bond on a ring, which is not stable for small rings (fewer than eight
atoms) due to a combination of ring strain, and angle strain (nonplanar alkene). The p orbitals of the
bridgehead atom and adjacent atoms are orthogonal and thus are not aligned properly for the formation of
pi bonds. Fawcett quantified the rule by defining ‘S’ as the number of non-bridgehead atoms in a ring
system, and postulated that stability required S ≥ 9 in bicyclic systems and S ≥ 11 in tricyclic systems.
There has been an active research program to seek compounds inconsistent with the rule, and for bicyclic
systems a limit of S ≥ 7 is now established with several such compounds having been prepared. The
above norbornene system has S ≥ 5 and so they are not preparable.
Bredt’s rule can be useful for predicting which isomer is obtained from an elimination
reaction in a bridged ring system. It can also be applied to reaction mechanisms that go via carbocations
and, to a lesser degree, via free radicals, because these intermediates, like carbon atoms involved in a
double bond, prefer to have a planar geometry with 120o angles and sp2 hybridization.
For example, bicyclo[5.3.1] undecane-11-one-1-carboxylic acid undergoes decarboxylation

on heating to 132°C, but the similar compound bicycle[2.2.1] heptan-7-one-1-carboxylic acid remains
stable beyond 500°C, despite both being β-keto acids with the carbonyl group on a one-carbon bridge and
the carboxylate group on the bridgehead. The mechanism of decarboxylation involves an enolate
intermediate, which is an S>9 species in the former case and an S>5 species in the latter, preventing the
decarboxylation in the smaller ring system. An anti-bredt molecule is one that is found to exist and be
stable (within certain parameters) despite this rule. A recent (2006) example of such a molecule is 2-
quinuclidonium tetrafluoroborate. Bridgehead double bonds can be found in some natural products,
discussed in a review at bridgehead alkenes more generally.

SAYTZEFF RULE
In case of unsymmetrical alkyl halides i.e., 2-bromobutane, the course of elimination is determined by
Saytzeff rule. According to this rule, hydrogen eliminated preferentially from the carbon atom which has lesser
number of hydrogen atoms and so highly substituted alkene is the major product.
The more substituted alkene product is more stable than the less substituted product. The stability of the
more substituted alkene is a result of number of different contributing factors, including hyperconjugation.
Each alkyl group that can involve in hyperconjugation with the double bond stabilizes it by approximately 6
kcal/mol.
In order to explain the highly substituted alkene consider the transition state of the substituted
alkenes. The transition state of both the less and more substituted alkene have partial double bond
character. However, the transition state leading to more stable alkene is more stabilized and is of
lower energy. Thus, the more stable alkene is formed as the major product.
Mechanism

HOFMANN RULE
This rule is applicable for those substrates in which 𝛼-carbon atom is attached to a positively
charged atom. According to this rule, “In the elimination of the positively charged species, the major
product will be the alkene which is least substituted”. Hofmann elimination is observed for compounds
containing bulky leaving groups such as quaternary ammonium or sulfonium salts.
Reason for leading to Hofmann products,
• The steric bulk of the base.

• The association of the base with the solvent molecules make it even larger.
• tert-Butoxide removes one of the more exposed (1°) hydrogen atoms instead of the internal (2°)
hydrogen atoms due to its greater crowding in the transition state.
Hofmann elimination reaction takes place in the following four cases
• When the base is bulky.

• When the leaving group is a poor leaving group such as F, NR3+ and SR2+
• Steric hindrance at β-carbon, and
• When the alkyl halide contains one or more double bonds.
Example,
This rule can be explained by considering the mechanism of elimination reaction of quaternary
ammonium hydroxide.
In the above mechanism, the strong EWG makes the hydrogens of the 𝛽-carbon more acidic for
facile abstraction by the base. In this compound, the another 𝛽-carbon is less acidic due to +I effect of the
methyl group. Hence, the more acidic hydrogen is removed and give the alkene (ethene) by route ‘a’.

Further examples for Hofmann rule as given below,
Model Questions
1. Which Intermediate is formed in Wolff’s reaction?

a) Ketene b) Carbene c) Carbocation d) Carbanion
2. In which medium Favorskii rearrangement occurs?
a) Acidic b) Neutral c) Basic d) Alkaline
3. With accompanying 1, 2-rearrangement in Wolff rearrangement, an α-diazocarbonyl compound is
converted into a ketene by loss of which of the following compound?
a) Dioxygen b) Disulphur c) Dinitrogen d) Ammonia
4. In which of the following rearrangements, acyl azide is an intermediate?
a) Hoffmann b) Schmidt c) Lossen d) Claisen
5. The Intermediate formed in Wolff’s reaction is _________.
a) Carbene b) Ketene c) Carbocation d) Carbanion
6. Which type of catalytic reaction, does Dienone phenol rearrangement reaction belong?
a) Acid catalysed b) Base catalysed c) Acidic d) Neutral
7. Which among the following rearrangement does not involve the formation of isocyanate
a) Schmidt b) Favorski c) Curtius d) Lossen
8. Favorskii rearrangement involves the transformation of ________ into esters
a) α-haloaldehyde b) α-haloketone c) α-haloester d) β-haloester
9. Migration of hydrogen from one atom to the adjacent atom is called________
a) 1,2-hydride shift b) 1,1-hydride shift c) 2,2-hydride shift d) 1,1- shift
10. 2-chlorocyclobutanone undergoes Favorskii rearrangement and it gives
a) Cyclopropane carboxylic acid b) Cyclopropenone
c) Cyclobutenone d) Cyclopropanol

11. Rearrangement of allyl aryl ethers to allyl phenol is known as _______.

a) Schmidt rearrangement b) Claisen rearrangement
c) Neber rearrangement d) Sommelet-Hauser rearrangement
12. The following reaction is named as ______.
a) Hoffmann bromamide rearrangement b) Carbylamine reaction

c) Hoffman elimination d) Baeyer-Villiger oxidation
13. Which of the following reacts by E1 mechanism in ethanol most readily?
a) CH3CH2CH(Br)CH3 b) (CH3)2CHCH2Br c) (CH3)3CBr d) CH3CH2CH2CH2Br
14. Which one of the reagents is used in elimination reaction of Halogenoalkanes?
a) Ethanoic acid b) Ethanolic sodium hydroxide c) Ethanoate d) Ethane
15. What is stereo chemical requirement of E2 elimination? With suitable example explain.
16. What is Favorski rearrangement? Give the mechanism (3).
17. What is E1CB Mechanism? Which substrates are very prone to react by this mechanism? Illustrate with
suitable example (2).
18. Explain the mechanism of Dienone-phenol rearrangement.
19. Discuss the mechanism of E1, E2 (2).
20. Describe the Sommelet Hauser rearrangements with mechanism (2).
21. Explain the Schmidt rearrangement with mechanism.
22. Explain Von-Richer rearrangement and Demjenov rearrangement with mechanism (2).
23. Describe the Pummerer rearrangementwith mechanism.
24. Explain the Steven rearrangement with mechamism (2).
25. Explain the Hofmann rearrangement with mechanism (2).
26. Describe about the Wagner Meerwein and Wolff rearrangement with mechanism.
27. State and explain Bredt’s rule with example.
28. Predict the name and mechanism for the following rearrangement
29. Outline the mechanism for the following reaction.
30. Explain the orientation of Double bond according to Saytzeff rule (2).


Org. Chem - Rearrangement and Elimination Rxns.

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1 Organic Chemistry II (P22CH11) Unit IV

ORGANIC CHEMISTRY II (P22CH11)

Unit IV _ Rearrangement and Elimination Reactions

Classification - mechanisms of the following rearrangements – Wagner-Meervein,

1. I. L. Finar, “Organic Chemistry”, Volume-II, 5th Ed., (2006).

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Intermolecular Rearrangement: In intermolecular reactions, migration of group/atom can take place in

Intramolecular Rearrangement: In intramolecular rearrangement reactions, the migration of a

WAGNER – MEERVEIN REARRANGEMENT

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑃ℎ𝑒𝑛𝑦𝑙 > 𝑡 − 𝑏𝑢𝑡𝑦𝑙 > 𝑒𝑡ℎ𝑦𝑙 > 𝑚𝑒𝑡ℎ𝑦𝑙

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

The Favorskii rearrangement reaction involves the conversion of 𝛼 − haloketones to carboxylic

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Sommelet and Hauser found that benzhydryltrimethylammonium hydroxide rearranged to o-

When 2,4,6-trimethylbenzyltrimethylammonium iodide undergoes Sommelet-Hauser

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Salient features of Schemidt Rearrangement reaction

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Mechanism for ketones to secondary amine

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Step 1: acylation of the sulfoxide oxygen to form an acyloxysulfonium salt

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Step 1: Protonation of 4,4-dimethylcyclohexa-2,5-dienone takes place.

Step 2: Delocalization of pi electron occurs.

Step 3: Methyl group shifted to the adjacent carbon atom.

Step 4: Deprotonation of the step 3 product gives the 3,4-dimethylphenol.

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

The rearrangement is formulated to proceed via an intermediate radical-pair or ion-pair. The

Step 1: The nitrosonium ion reacts with the primary amine.

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Step 4: Deprotonation of step 3 occurs.

Tiffeneau – Demjanov Rearrangement

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

There are three fundamental events in these elimination reactions:

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Effect of ‘R’ group

𝑬𝟏 mechanism for Alcohols

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑬𝟏 mechanism for Alkyl halides

Effects of ‘R’ group

• These reactions are favored by strong bases.

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Difference between 𝑬𝟏 and 𝑬𝟐 Mechanism

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

STEREOCHEMISTRY OF ELIMINATION REACTION

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

i) The two groups are in trans position (anti-periplanar)

The elimination may proceed as follows,

Evidence for 𝑬𝟐 elimination

Consider 1-bromo-1,2-diphenylpropane as example. The molecule 1-bromo-1,2-diphenylpropane

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

1. Cis‐tert‐butylcyclohexylbromide under goes elimination reaction to give Cis‐tertbutylcyclohexene,

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

MECHANISM FOR E1CB REACTION

𝑅𝑎𝑡𝑒 = 𝐾 [𝑠𝑢𝑏𝑠𝑡𝑟𝑎𝑡𝑒] [𝐵𝑎𝑠𝑒]

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅

Propose the mechanism for the following reaction.

COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION

𝑴𝒓. 𝑷. 𝑱𝒆𝒆𝒗𝒂𝒏𝒂𝒏𝒕𝒉𝒂𝒎 ̅̅̅̅̅̅̅