CHAPTER 10

Elimination Reactions
❖ The E2, E1 and E1CB Mechanisms
No organic reaction is capable of giving 100% yield of a single product only, including nucleophilic
substitutions. The reason for this type of behavior is the fact that nucleophilic substitution reactions are in
direct competition with the elimination reactions; and if the reagent and substrate carefully with a fine-tuning
of experimental conditions, elimination yield can even surpass the nucleophilic substitution product. In this
section, we will discuss some important elimination mechanisms like E2, E1, and E1CB-type.
➢ E2 (Bimolecular Elimination) Mechanism
An E2 elimination reaction is a type of organic reaction in which two substituents are removed from
a molecule in a one-step concerted mechanism. The numbers refer not to the number of steps in the mechanism,
but rather to the kinetics of the reaction which means that E2 is a bimolecular (second-order) reaction.
Illustrative reaction: The reaction of ethoxide ion with ethyl bromide falls into this category because the rate
of reaction depends only upon the concentration of the substrate as well as of reagent.

Mechanism involved: The proposed mechanism for the reaction given above involves one step which must
be discussed before we give salient features of the same.

It is worthy to recall that even though the reaction is shown as a two-step process, it is actually concerted in
nature where the bond breaking and bond-making occur simultaneously.

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 346 A Textbook of Organic Chemistry – Volume I

Salient Features: The main features of the mechanism involved in bimolecular elimination reactions are given
below.
i) E2 reactions follow second-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋][𝐵]

Where k is the rate constant. The symbol [𝑅𝑋] and [𝐵] represent the molar concentration of the alkyl halide
and base, respectively.
ii) E2 typically takes place with primary alkyl halides but is possible with some secondary alkyl halides.
iii) Because of the formation of a π-bond in the course of the E2 mechanism, the two leaving groups (often a
halogen and hydrogen) must be antiperiplanar. The reason for this is the fact that the antiperiplanar transition
state will have lower energy (staggered-conformation) than a synperiplanar transition state (eclipsed
conformation). In other words, the E2 reactions are favored by staggered conformation whereas the E1 by
eclipsed one.
iv) E2 typically uses a strong base. It must be strong enough to remove the weakly acidic hydrogen.
v) E2 competes with the SN2 reaction mechanism if the base can also act as a nucleophile (true for many
common bases).
➢ E1 (Unimolecular Elimination) Mechanism
An E1 elimination reaction is a type of organic reaction in which two substituents are removed from
a molecule in a two-step mechanism. The numbers refer not to the number of steps in the mechanism, but
rather to the kinetics of the reaction which means that E1 is a unimolecular (first-order) reaction.
Illustrative reaction: The reaction of NaOH with tert-butyl bromide falls into this category because the rate
of reaction depends only upon the concentration of the substrate.

Mechanism involved: The proposed mechanism for the reaction given above involves two steps which must
be discussed before we give salient features of the same.
i) Generation of carbocation: The aryl halide accepts an electron from a radical initiator to form radical anion.

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 CHAPTER 10: Elimination Reactions 347

ii) Removal of proton:

Salient Features: The main features of the mechanism involved in unimolecular elimination reactions are:
i) E1 reactions follow first-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋]

Where k is the rate constant. The symbol [𝑅𝑋] represents the molar concentration of the substrate.
ii) The E1 reactions generally occur with tertiary alkyl halides but are possible with some 2° alkyl halides.
iii) The E1 reaction typically takes place in the presence of a weak base or the base can be absent at all.
iv) E1 reactions compete with SN1 reactions because they share the same intermediate.
➢ E1CB (Conjugate Base Elimination) Mechanism
The E1CB elimination reaction is a type of chemical transformation where the elimination occurs in
the presence of a strong base, and the hydrogen to be removed is comparatively acidic, while the leaving group
(such as -OH or -OR) is a relatively poor one.
Illustrative reaction: An example of the E1CB reaction mechanism in the degradation of a hemiacetal under
basic conditions.

Mechanism involved: The proposed mechanism for the reaction given above involves two steps which must
be discussed before we give salient features of the same.
i) Proton abstraction: The aryl halide accepts an electron from a radical initiator to form a radical anion.

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348 A Textbook of Organic Chemistry – Volume I

ii) Detachment of leaving group:

Salient Features: The main features of the mechanism involved in unimolecular elimination conjugate-base
reactions are:
i) E1CB reactions follow first-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋]

Where k is the rate constant. The symbol [𝑅𝑋] represents the molar concentration of the substrate.
ii) The substrate must have acidic hydrogen on its β-carbon and a relatively poor leaving group on the α-
carbon.

❖ Orientation of the Double Bond

In this section, we will discuss the effect of the orientation of the double bond (regio- and
stereochemistry) on the reactivity of the elimination reaction.
➢ Regiochemistry of the Double Bond
The possibility of regioselectivity in elimination reactions arises if more than one carbon have β-
hydrogens. For instance, the sec-butyl halide (two types of β-hydrogen) can result in either 1- or 2-butene
whereas PhCH2CH2Br is not able to do so (only PhCH=CH2).

Therefore, the rules that dictate the major-minor products must be discussed for any stereochemical
rationalization first.

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 CHAPTER 10: Elimination Reactions 349

Rule 1: The double bond will not shift to a bridgehead carbon irrespective of the mechanism-type until the
ring size becomes quite big. This rule is also known as Bredt’s rule because it was given Julius Bredt in 1902,
and codification was completed in 1924.

Rule 2: If there is a possibility of a newly formed double bond to get into conjugation with some previously
present multiple bond or aromatic ring, it will always do so even if it leads to unfavorable stereochemistry.
Rule 3: The directional shift of the double bond in E1 reactions is always decided by the relative stabilities of
resulting products; which is because the initial departure of the leaving group leaves both possibilities open.
In other words, the double bond moves primarily toward the more substituted carbon (Zaitsev’s rule); which
can be explained on the basis of the heat of hydration or hyper-conjugative structure. For instance, 2,3-
dimethyl-2-pentene is formed from 3-bromo-2,3-dimethylpentane rather than either 3,4-dimethyl-2-pentene or
2-ethyl-3-methyl-1-butene.

Since the departure of the leaving group occurs first, the Zaitsev’s rule dictates the orientation of double bond
in E1 reaction irrespective of the leaving group's nature (neutral or positive); however, in case it cannot be said
for E2 reactions, where the orientation of the double bond and the departure of the leaving group takes place
simultaneously. Nevertheless, the non-Zaitsev product can also be the major product even in the case of E 1
eliminations because of reduced steric hindrance, or the formation of ion-pair.
Rule 4: It is quite a well-known fact that a trans β proton is required for the anti E2 mechanism to be active;
which is accessible only in one direction creating only one double-bond-shifting possibility. However, it is
limited to the cyclic systems because the molecule may free rotation about carbon-carbon single bond (if the
steric hindrance isn’t very high). On the other hand, if two or more carbons have trans-β hydrogens, two types
of products can be obtained; sometimes Zaitsev’s product (double bond shifting toward the more substituted
carbon), sometimes Hofmann’s product (double bond shifting toward the least substituted carbon).

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It has also been observed that Zaitsev’s rule is followed in all substrates if the compound has uncharged
nucleofuges (leaving as negative ions like Cl−); whereas Hofmann’s rule is followed if the compound has
charged nucleofuges (leaving as neutral ions like NR 3+) provided that the substrate is acyclic, otherwise
Zaitsev’s product (i.e., if the leaving group is connected to a benzene ring). Now because Zaitsev’s rule gives
rise to the thermodynamically stable product, its outranking by Hofmann’s rule in some compounds should
also be explained. This change of double bond orientation in acyclic systems can be rationalized in the terms
of two different factors.

The first one is that the β-hydrogen becomes less acidic due to the presence of the alkyl group, which in turn
favors Hoffman’s rule. The second one is the fact that positively charged groups are generally larger in size
than the neutral group, and therefore a CH 3 group (less substituted) is more prone to attack than a primary or
secondary carbon; in other words, steric effects dictate the final product.
Rule 5: It has been observed that the Hofmann orientation is significantly favored over the Zaitsev product in
syn-E2 eliminations.
Rule 6: The regioselectivity is of less importance as far as the E 1CB-type reactions are concerned because this
pathway is typically found in the systems with an electron-withdrawing group at β-site, attracting double bond
movement towards itself.
Rule 7: It is a well-known fact that E2C reactions are susceptible to Zaitsev orientation, and this preference is
of great importance as far as commercial production is concerned. However, the non-Zaitsev product is also
obtained in some cases where conjugation with the aromatic ring is obtainable.

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 CHAPTER 10: Elimination Reactions 351

➢ Stereochemistry of the Double Bond

If CHAB–CGGX or CH3–CABX type compounds undergo elimination, the resulting alkene cannot
show cis-, trans-isomers. However, the CH2E–CABX CHEG–CABX type compounds do have the ability to
give rise to cis- and trans- isomers after undergoing elimination. For instance, consider the following
transformation.

It has been observed that the threo- and erythro-compound gives rise to trans- and cis- alkene; respectively.
Furthermore, two conformations can be obtained for the transition state in the case of compound II, where two
isomers can be synthesized. Nevertheless, the eclipsing effects will dictate the major-minor one; like the
Zaitsev elimination of 2-bromopentane leads to the trans-isomer as major. This because confirmation A (Et is
in between H and Br) is more stable than conformation B (Et is in between Me and Br), and the effect becomes
more dominating as the groups get bigger.

Moreover, the ratio of cis/trans isomers in the anti-E2 reaction is also dictated by the solvent, nature of the
leaving group, the substrate, and the attacking base. The complete picture of these effects is still not clear as
far as the stereochemistry of the double bond is concerned. For instance, E1-system with a bigger D-E pair
opposite to the smaller AB pair is more stable if the carbocation free to rotate; and therefore, we should get the
corresponding alkene. On the other hand, E 2-like products will be formed if the carbocation formed is not
totally free; and the same is true for E1CB reactions.

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❖ Reactivity – Effects of Substrate Structures, Attacking Base, the Leaving

Group and The Medium
In this section, we will discuss the effects of substrate structures, attacking base, the leaving group,
and the nature of the medium on the reactivity of elimination reactions.
➢ Effect of Substrate Structure on the Reactivity of Elimination Reactions
The effects of substrate structures on the reactivity of elimination reactions can be divided into the
following categories.
1. Effect on the reaction Rate: Different Groups bonded to the α-carbon (C with nucleofuge i.e., C−X) or β-
carbon (C that loses proton i.e., C−H) can primarily exercise four types of influences as discussed below.
i) The emerging double bond can be stabilized or destabilized by these groups.
ii) The groups attached at β-carbon can affect the acidity of β-proton by stabilizing or destabilizing the
emerging negative charge.
iii) The groups attached at α-carbon can affect the stability of the emerging positive charge.
iv) The groups attached at α- and β-carbon can exert eclipsing effects (steric effects).
The first and fourth types of effects can affect all three kinds of elimination mechanisms, with steric
effects as most dominant in E2 reactions. Also, the second and third kinds of effects cannot be applied to E1
and E1CB, respectively. If the C=C bond formation is the rate-determining, the presence of C=C or aromatic
ring enhances the reaction rate in all mechanisms. Finally, the presence of electron-withdrawing groups at β-
position raises the acidity of leaving hydrogen but has little to no effect at α-sites provided that no multipole
bond conjugation available; making CN, Br, Cl, NO2, Ts, SR, and CN suitable E2-kind reactions.
2. Effect on E1 vs E2 vs E1CB: Since the presence of aryl or alkyl group at α-carbon can stabilize the
carbocation via resonance or inductive effect, A shift towards the E1 pathway should be observed in the same.
Also, the same shift can also be carried out by Alkyl groups at β-position by decreasing the acidity of the
hydrogen atom. Nevertheless, the presence of aryl groups at β-carbon will push the towards E1CB pathway by
carbanion’s stabilization. Conclusively, it has been observed that the presence of any electron-withdrawing
group at β-site always pushes the reaction E1CB pathway. Finally, it should also be remembered that E2C
reactions are also favored by the presence of alkyl groups at α-sites.

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 CHAPTER 10: Elimination Reactions 353

3. Effect on elimination vs substitution: In bimolecular elimination reaction, the rate of reaction increases as
the branching increases. This behavior can easily be rationalized in terms of statistical and steric factors. In
other words, the increased α-branching leads to more base-attackable hydrogens, and increased steric
hindrance opposes the attack at the carbon simultaneously. Moreover, the increased α-branching also supports
unimolecular elimination over unimolecular nucleophilic substitution. The E 2 pathway is also favored over
SN2 when branching at the β-carbon is raised because of the suppression of the latter. Similarly, The E1
pathway is also favored over SN1 when the branching at the β-carbon is raised because of the steric factors. If
the leaving group has a charge on it, the branching at the β-carbon will slow down the rate of E 2 reactions
(Hofmann’s rule). Also, the presence of electron-withdrawing groups at the β-site supports E2-pathway with
the simultaneous shift towards the E1CB route but (upsurging the elimination/substitution ratio).
➢ Effect of Attacking Base on the Reactivity of Elimination Reactions
The effects of attacking base on the reactivity of elimination reactions can be divided into the
following two categories.
1. Effect on E1 vs E2 vs E1CB: The outside base isn’t required in E1 reaction under typical conditions because
itself can act as the base. Therefore, the reaction pathway shifts from E1 to E2 when the outside bases is mixed.
Furthermore, adding more outside stronger base will shift the pathway even towards E1CB. Nevertheless, weak
bases are also capable of yielding elimination reactions with some particular substrate-types. Bases (besides
organic) yielding normal E2 reactions are given below.
NH2−, OR−, OAr−, CO32−, LiAlH4, CN−, H2O, NR3, OH−, OAc−, I−
It should also be noted that not all the bases are useful as far the practical synthetic route is concerned; for
instance, NH2−, OR− and OH− are valuable for normal E2 reaction; whereas the bases like OAc−, Cl− and RS−are
useful in preparing quaternary salts.
2. Effect on elimination vs substitution: Besides supporting E2 over E1, strong bases also assist elimination
over substitution reactions. The concentrated solution of strong bases in a nonionizing solvent not only favors
E2 but also helps them to outrank the SN2 pathway. On the other hand, dilute basic solutions in ionizing solvents
not only favor E1 but also help them to outrank the SN1 pathway. It was also deduced from the nucleophilic
substitution studies that stronger bases aren’t necessarily stronger nucleophile; and therefore, a weaker
nucleophile but stronger base will prefer elimination over substation. Nevertheless, weak bases can also lead
to elimination if the solvent used is polar and aprotic.
➢ Effect of Leaving Group on the Reactivity of Elimination Reactions
The effects of leaving-group on the reactivity of elimination reactions can be divided into the
following categories.
1. Effect on the general reactivity: Despite the different nature of the pathways, the leaving groups in both
cases behave pretty much similar. Leaving groups in E2 are NO2, F, Cl, Br, I, NR3+, OHR+, SO2R, PR3+, SR2+,
OSO2R, OOR, OCOR, OOH, and CN; leaving groups in E1 are NR3+, OSO2R, SR2+, OH2+, OHR+, Br, I, OCOR,
Cl, and N2+.

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2. Effect on E1 vs E2 vs E1CB: Since the better leaving groups make the ionization easier, they will move the
pathway towards E1 reactions, which can be confirmed via ρ-values. Furthermore, positively charged or poor
leaving groups will shift the pathway towards the E1CB reactions, which can be attributed to the increased
acidity β-protons that arises from the strong field effects of electron-withdrawing nature. Finally, it has also
been observed that good leaving groups support E 2C reaction.
3. Effect on elimination vs substitution: Since the reaction pathway (elimination or substitution) is decided
only after the departure of the leaving group in the reactions following first-order kinetics, the leaving group
will not be able to prefer elimination over substitution, and vice-versa. Nevertheless, if ion-pair formation had
taken place, the leaving group will affect the final product. Therefore, the elimination to substitution ratio (e/s)
is largely independent of a halide as leaving group with only a minor raise in elimination to Cl < Br < I. On
the other hand, the substitution pathway is strongly favored if the leaving group is like OTs. For instance, n-
C18H37Br treated with t-BuOK results in 85% elimination, whereas n-C18H37OTs gives rise to 99% substitution
under similar experimental conditions. Conversely, leaving groups with a positive charge will increase the
elimination yield.
➢ Effect of Medium on the Reactivity of Elimination Reactions
The effects of the medium on the reactivity of elimination reactions can be divided into the following
categories.
1. Effect on E1 vs E2 vs E1CB: It is quite a well-known fact that reaction-rate increases with solvents polarity
increases if the intermediates involved are ionic in nature. Furthermore, it has also been observed that the rate
of E1 and E1CB pathways are also supported by increasing solvent’s polarity and ionic strength, even if the
leaving group is neutral in nature. Lastly, aprotic polar solvents encourage E 2C reactions with some particular
substrates.
2. Effect on elimination vs substitution: The SN2 pathway is favored at the cost of E2 one if the solvent
polarity is increased. For instance, KOH results in more elimination in alcohol but favors substitution in water
as a solvent; which can partially be explained via the charge-dispersal phenomenon. On the other hand, the
SN1 pathway is encouraged over E1 in most of the solvent mediums. Nevertheless, in the polar solvents with
low nucleophilic character, the E 1 pathway become more prominent than the usual (like dipolar aprotic
mediums). Finally, it has also been observed in the gas-phase studies (i.e., no medium) that when MeO− reacts
with1-bromopropane exclusively via the elimination-route even if the substrate used in the process are only
primarily substituted.
3. Effect of temperature: It has been proven again and again that raising the reaction temperature almost
always supports the elimination over substitution despite the order of the reaction (first or second-order). This
behavior can simply be attributed to the higher activation energies of eliminations than those of substitutions,
arising from larger bonding-alteration.

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CHAPTER 10: Elimination Reactions 355

❖ Mechanism and Orientation in Pyrolytic Elimination

The pyrolytic elimination or Ei (elimination internal/intramolecular) mechanism is a special kind of
elimination reaction where two vicinal groups on an alkane framework leave simultaneously through a cyclic
transition state to form an alkene with a syn-elimination, and that is why they also called as pericyclic syn-or
thermal syn elimination.
➢ Mechanism in Pyrolytic Elimination
The pyrolytic elimination is a unique type of elimination because it is activated thermally and does
not need additional reagents unlike regular eliminations where an acid, a base, or charged intermediates is
needed; and as the name suggests, it is often found in pyrolysis.
Illustrative reaction: one of the most common examples of pyrolytic elimination reaction is shown below for
more clear understanding.

Mechanism involved: The proposed mechanism for the reaction given above involves one step which must
be discussed before we give salient features of the same.

The elimination must be syn and the atoms coplanar for five and four-membered transition states, but
coplanarity is not needed in the case where six-membered transition states are involved.

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 356 A Textbook of Organic Chemistry – Volume I

Salient Features: The main features of the mechanism involved in elimination internal (or intramolecular
elimination) reactions are given below.
i) Ei reactions follow first-order kinetics with the rate law

𝑅𝑎𝑡𝑒 = 𝑘[𝑅𝑋]

Where k is the rate constant. The symbol [𝑅𝑋] represents the molar concentration of the substrate.
ii) Elimination internal is thermally activated and does not need additional reagents unlike typical eliminations
pathways where an acid or base is required, or sometimes involve charged intermediates.
iii) The elimination mode must be syn and the atoms must be coplanar for five and four-membered transition
states; nevertheless, the coplanarity is not necessary for six-membered transition states.
iv) The rate of the reactions is not affected by the use of free-radical inhibitors.
➢ Orientation in Pyrolytic Elimination
Just like in normal elimination reactions, Bredt’s rule is also applicable in the case of pyrolytic
elimination. Nevertheless, conjugated systems are preferred non-conjugated systems (if allowed sterically) if
a double bond is available. Furthermore, some more conclusive remarks regarding orientation in pyrolytic
elimination are also of great importance.
1. The pyrolytic elimination requires a β-hydrogen in cis position; and therefore, the double bond will have
only one direction to move in cyclic systems with only cis-hydrogen. Nevertheless, the condition of the leaving
groups to be cis isn’t required in six-membered transition states (due to non-coplanarity). Consequently, the
hydrogen must be at the equatorial site if the leaving group is present at the axial position because the transition
state cannot be comprehended with both at the axial positions. On the other hand, the leaving group will
become able to create a transition state with β-hydrogen if it occupies an equatorial site. Conclusively, we can
say if the leaving group is at the axial site, the double bond formation will not take place in the carbethoxyl
group’s direction due to the lack of equatorial hydrogen. Therefore, compound A will result in 100% C;
whereas 50% of each type of alkene will be obtained if an equatorial leaving group is present.

2. It has been observed that the more stable alkene product dominates (Zaitsev’s rule) in many cases,
particularly with cyclic reactants. For instance, more of Hofmann product was expected menthyl acetate due
to the presence of cis-β hydrogen on both sides, but the experimental yield is opposite i.e., 65% Zaitsev and
35% Hofmann product.
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3. In many cases, it has also been observed that steric effects also dictate the elimination’s direction since
minimum steric interactions are favorable in both transition state and ground state of the substrate.
4. If all the three effects mentioned above are absent, the orientation dictation will be statistical in nature, and
therefore, will be controlled by the number of β-hydrogens (Hofmann’s rule). For instance, 60% 1-butene and
40% 2-butene were obtained from sec-butyl acetate where the hydrogens present are also in the 3:2 ratio.

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❖ Problems
Q 1. Define elimination reactions.
Q 2. Discuss E1 and E2 mechanisms. How they are different from SN 1 and SN2 pathways?
Q 3. State and explain E1CB pathway of elimination reactions.
Q 4. What is pyrolytic elimination? How would you explain the orientation effect in the same?
Q 5. Discuss the reactivity of elimination reactions with special reference to substrate structure and attacking
base.
Q 6. How does a leaving group affect the rate of elimination reactions?
Q 7. Write a short note on the reactivity of elimination reactions with special reference to reaction medium.

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CHAPTER 10: Elimination Reactions 359

❖ Bibliography
1. M. B. Smith, March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, John Wiley &
Sons, Inc., New Jersey, USA, 2013.
2. H. Zimmerman, Quantum Mechanics for Organic Chemists, Academic Press, New York, USA, 1975.
3. M.S. Singh, Reactive Intermediates in Organic Chemistry, John Wiley & Sons, Inc., New Jersey, USA,
2014.
4. D. Klein, Organic Chemistry, John Wiley & Sons, Inc., New Jersey, USA, 2015.
5. J. Clayden, N. Greeves, S. Warren, Organic Chemistry, Oxford University Press, Oxford, UK, 2012.
6. R. L. Madan, Organic Chemistry, Tata McGraw Hill, New Delhi India, 2013.
7. C. A. Coulson, B. O'Leary, R. B. Mallion, Hückel Theory for Organic Chemists, Academic Press,
Massachusetts, USA, 1978.

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Table of Contents
CHAPTER 1 ................................................................................................................................................. 11
Nature of Bonding in Organic Molecules ............................................................................................... 11
❖ Delocalized Chemical Bonding ...................................................................................................... 11
❖ Conjugation .................................................................................................................................... 14
❖ Cross Conjugation .......................................................................................................................... 16
❖ Resonance....................................................................................................................................... 18
❖ Hyperconjugation ........................................................................................................................... 27
❖ Tautomerism ................................................................................................................................... 31
❖ Aromaticity in Benzenoid and Nonbenzenoid Compounds ............................................................ 33
❖ Alternant and Non-Alternant Hydrocarbons ................................................................................... 35
❖ Huckel’s Rule: Energy Level of π-Molecular Orbitals ................................................................... 3 7
❖ Annulenes ....................................................................................................................................... 44
❖ Antiaromaticity ............................................................................................................................... 46
❖ Homoaromaticity ............................................................................................................................ 48
❖ PMO Approach ............................................................................................................................... 50
❖ Bonds Weaker Than Covalent ........................................................................................................ 58
❖ Addition Compounds: Crown Ether Complexes and Cryptands, Inclusion Compounds,
Cyclodextrins ................................................................................................................................. 65
❖ Catenanes and Rotaxanes ............................................................................................................... 75
❖ Problems ......................................................................................................................................... 79
❖ Bibliography ................................................................................................................................... 80
CHAPTER 2 ................................................................................................................................................. 81
Stereochemistry ........................................................................................................................................ 81
❖ Chirality .......................................................................................................................................... 81
❖ Elements of Symmetry ................................................................................................................... 86
❖ Molecules with More Than One Chiral Centre: Diastereomerism .................................................. 90
❖ Determination of Relative and Absolute Configuration (Octant Rule Excluded) with Special
Reference to Lactic Acid, Alanine & Mandelic Acid ..................................................................... 92
❖ Methods of Resolution.................................................................................................................. 102
❖ Optical Purity ............................................................................................................................... 104
❖ Prochirality ................................................................................................................................... 105
❖ Enantiotopic and Diastereotopic Atoms, Groups and Faces ......................................................... 107
❖ Asymmetric Synthesis: Cram’s Rule and Its Modifications, Prelog’s Rule .................................. 113
❖ Conformational Analysis of Cycloalkanes (Upto Six Membered Rings) ...................................... 116
❖ Decalins ........................................................................................................................................ 122
❖ Conformations of Sugars .............................................................................................................. 126
❖ Optical Activity in Absence of Chiral Carbon (Biphenyls, Allenes and Spiranes) ....................... 132
❖ Chirality Due to Helical Shape ..................................................................................................... 137
❖ Geometrical Isomerism in Alkenes and Oximes ........................................................................... 140
❖ Methods of Determining the Configuration .................................................................................. 146
 ❖ Problems ....................................................................................................................................... 151
❖ Bibliography ................................................................................................................................. 152
CHAPTER 3 ............................................................................................................................................... 153
Reaction Mechanism: Structure and Reactivity .................................................................................. 153
❖ Types of Mechanisms ................................................................................................................... 153
❖ Types of Reactions ....................................................................................................................... 156
❖ Thermodynamic and Kinetic Requirements .................................................................................. 159
❖ Kinetic and Thermodynamic Control ........................................................................................... 161
❖ Hammond’s Postulate ................................................................................................................... 163
❖ Curtin-Hammett Principle ............................................................................................................ 164
❖ Potential Energy Diagrams: Transition States and Intermediates ................................................. 166
❖ Methods of Determining Mechanisms .......................................................................................... 168
❖ Isotope Effects .............................................................................................................................. 172
❖ Hard and Soft Acids and Bases ..................................................................................................... 174
❖ Generation, Structure, Stability and Reactivity of Carbocations, Carbanions, Free Radicals, Carbenes
and Nitrenes................................................................................................................................. 176
❖ Effect of Structure on Reactivity .................................................................................................. 200
❖ The Hammett Equation and Linear Free Energy Relationship ...................................................... 203
❖ Substituent and Reaction Constants .............................................................................................. 209
❖ Taft Equation ................................................................................................................................ 215
❖ Problems ....................................................................................................................................... 219
❖ Bibliography ................................................................................................................................. 220
CHAPTER 4 ............................................................................................................................................... 221
Carbohydrates ........................................................................................................................................ 221
❖ Types of Naturally Occurring Sugars ........................................................................................... 221
❖ Deoxy Sugars ............................................................................................................................... 227
❖ Amino Sugars ............................................................................................................................... 229
❖ Branch Chain Sugars .................................................................................................................... 230
❖ General Methods of Determination of Structure and Ring Size of Sugars with Particular Reference
to Maltose, Lactose, Sucrose, Starch and Cellulose ...................................................................... 231
❖ Problems ....................................................................................................................................... 239
❖ Bibliography ................................................................................................................................. 240
CHAPTER 5 ............................................................................................................................................... 241
Natural and Synthetic Dyes ................................................................................................................... 241
❖ Various Classes of Synthetic Dyes Including Heterocyclic Dyes ................................................. 241
❖ Interaction Between Dyes and Fibers ........................................................................................... 245
❖ Structure Elucidation of Indigo and Alizarin ................................................................................ 247
❖ Problems ....................................................................................................................................... 252
❖ Bibliography ................................................................................................................................. 253
CHAPTER 6 ............................................................................................................................................... 254
Aliphatic Nucleophilic Substitution ...................................................................................................... 254
❖ The SN2, SN1, Mixed SN1 and SN2, SNi, SN1′, SN2′, SNi′ and SET Mechanisms ......................... 254
 The Neighbouring Group Mechanisms ......................................................................................... 263
❖
Neighbouring Group Participation by π and σ Bonds . .................................................................. 2 65
❖
Anchimeric Assistance ................................................................................................................. 269
❖
Classical and Nonclassical Carbocations ...................................................................................... 272
❖
Phenonium Ions ............................................................................................................................ 283
❖
Common Carbocation Rearrangements ........................................................................................ 284
❖
Applications of NMR Spectroscopy in the Detection of Carbocations ......................................... 286
❖
Reactivity – Effects of Substrate Structure, Attacking Nucleophile, Leaving Group and Reaction
❖
Medium ........................................................................................................................................ 288
❖ Ambident Nucleophiles and Regioselectivity ............................................................................... 294
❖ Phase Transfer Catalysis ............................................................................................................... 297
❖ Problems ....................................................................................................................................... 300
❖ Bibliography ................................................................................................................................. 301
CHAPTER 7 ............................................................................................................................................... 302
Aliphatic Electrophilic Substitution ...................................................................................................... 302
❖ Bimolecular Mechanisms − SE2 and SEi ...................................................................................... 3 02
❖ The SE1 Mechanism ..................................................................................................................... 305
❖ Electrophilic Substitution Accompanied by Double Bond Shifts ................................................. 307
❖ Effect of Substrates, Leaving Group and the Solvent Polarity on the Reactivity .......................... 308
❖ Problems ....................................................................................................................................... 310
❖ Bibliography ................................................................................................................................. 311
CHAPTER 8 ............................................................................................................................................... 312
Aromatic Electrophilic Substitution ..................................................................................................... 312
❖ The Arenium Ion Mechanism ....................................................................................................... 312
❖ Orientation and Reactivity ............................................................................................................ 314
❖ Energy Profile Diagrams .............................................................................................................. 316
❖ The Ortho/Para Ratio .................................................................................................................... 317
❖ ipso-Attack ................................................................................................................................... 319
❖ Orientation in Other Ring Systems ............................................................................................... 320
❖ Quantitative Treatment of Reactivity in Substrates and Electrophiles .......................................... 321
❖ Diazonium Coupling..................................................................................................................... 325
❖ Vilsmeier Reaction ....................................................................................................................... 326
❖ Gattermann-Koch Reaction .......................................................................................................... 327
❖ Problems ....................................................................................................................................... 329
❖ Bibliography ................................................................................................................................. 330
CHAPTER 9 ............................................................................................................................................... 331
Aromatic Nucleophilic Substitution ...................................................................................................... 331
❖ The ArSN1, ArSN2, Benzyne and SRN1 Mechanisms.................................................................... 331
❖ Reactivity – Effect of Substrate Structure, Leaving Group and Attacking Nucleophile................ 336
❖ The von Richter, Sommelet-Hauser, and Smiles Rearrangements ................................................ 339
❖ Problems ....................................................................................................................................... 343
❖ Bibliography ................................................................................................................................. 344
CHAPTER 10 ............................................................................................................................................. 345
Elimination Reactions ............................................................................................................................ 345
❖ The E2, E1 and E1CB Mechanisms ................................................................................................ 345
❖ Orientation of the Double Bond.................................................................................................... 348
❖ Reactivity – Effects of Substrate Structures, Attacking Base, the Leaving Group and The Medium
....................................................................................................................................................352
❖ Mechanism and Orientation in Pyrolytic Elimination ................................................................... 355
❖ Problems ....................................................................................................................................... 358
❖ Bibliography ................................................................................................................................. 359
CHAPTER 11 ............................................................................................................................................. 360
Addition to Carbon-Carbon Multiple Bonds ....................................................................................... 360
❖ Mechanistic and Stereochemical Aspects of Addition Reactions Involving Electrophiles,
Nucleophiles and Free Radicals .................................................................................................... 360
❖ Regio- and Chemoselectivity: Orientation and Reactivity ............................................................ 370
❖ Addition to Cyclopropane Ring .................................................................................................... 374
❖ Hydrogenation of Double and Triple Bonds ................................................................................. 375
❖ Hydrogenation of Aromatic Rings ................................................................................................ 377
❖ Hydroboration .............................................................................................................................. 378
❖ Michael Reaction .......................................................................................................................... 379
❖ Sharpless Asymmetric Epoxidation .............................................................................................. 380
❖ Problems ....................................................................................................................................... 382
❖ Bibliography ................................................................................................................................. 383
CHAPTER 12 ............................................................................................................................................. 384
Addition to Carbon-Hetero Multiple Bonds ......................................................................................... 384
❖ Mechanism of Metal Hydride Reduction of Saturated and Unsaturated Carbonyl Compounds, Acids,
Esters and Nitriles ......................................................................................................................... 384
❖ Addition of Grignard Reagents, Organozinc and Organolithium Reagents to Carbonyl and
Unsaturated Carbonyl Compounds ............................................................................................... 400
❖ Wittig Reaction ............................................................................................................................. 406
❖ Mechanism of Condensation Reactions Involving Enolates: Aldol, Knoevenagel, Claisen, Mannich,
Benzoin, Perkin and Stobbe Reactions .......................................................................................... 411
❖ Hydrolysis of Esters and Amides .................................................................................................. 433
❖ Ammonolysis of Esters ................................................................................................................. 437
❖ Problems ....................................................................................................................................... 439
❖ Bibliography ................................................................................................................................. 440
INDEX......................................................................................................................................................... 441