18 A Textbook of Organic Chemistry – Volume I

❖ Resonance
The concept of resonance is an extension of valence bond theory to explain the nature of the
“delocalized bond” in a lot of organic compounds which cannot be described by a single Lewis structure.
The valence bond approach to delocalized bonds is to consider many possible Lewis structures and
then averaging out them all. These possible Lewis structures are generally called as canonical or resonating
structures, and this phenomenon is labeled as “resonance”. For instance, let us consider the case of the benzene
molecule. If we treat it by the first extension of valence bond theory, three carbon-carbon bonds should be
shorter and three carbon-carbon bonds should be longer due to their double and single bond order character.

Figure 9. Different resonating structures of the benzene molecule.

However, in the actual molecule, all the bond lengths and bond angles were found equal. All this can be
explained only after considering the phenomenon of resonance in which all the possible resonating structures
are given in ‘Figure 8’. It has been found that after quantum mechanical calculations that Dewar structures (I–
III) contribute only 7.33% each whereas Kekule structures (IV and V) contribute approx. 39% each to the
resultant structure of benzene in which all the bond lengths and bond angles are equal. The bond order of
carbon-carbon bonds is greater than one but less than two showing an averaged strength for the resonance
hybrid. The resonance phenomena in some other molecules is given below.

Figure 10. Resonance phenomena in carbon dioxide and acetic acid.

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 CHAPTER 1: Nature of Bonding in Organic Molecules 19

Calculation of resonance energy: It is also worthy to note that the energy of resonance hybrid is always less
than the most stable resonating structure, and the energy difference between the two is simply called as
resonance energy.

Figure 11. The depiction of resonance hybrid, most stable canonical form, and resonance energy in
benzene molecule.

Since the Lewis structures are not real ones, the resonance energy for the benzene molecule can be obtained
via two routes as discussed below.
i) From heat of hydrogenation: The hypothetical six-membered cyclic ring system with no resonance would
be cyclohexatriene whose heat of hydrogenation should be three times of cyclohexene molecule.

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 20 A Textbook of Organic Chemistry – Volume I

Now since the enthalpy of hydrogenation of the actual benzene molecule is less than its hypothetical localized
version (358.98 – 208.36 = 150.62 kJ mol−1), the extra stabilization can be attributed to the phenomena of
delocalization easily.
ii) From heat of formation: The hypothetical six-membered cyclic ring system with no resonance would be
cyclohexatriene (Kekule structure) whose heat of formation should be the sum of the bond energies of different
carbon-carbon and carbon-hydrogen bonds.

𝛥𝐻𝑐𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 = 6 × 𝐵𝑜𝑛𝑑 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝐶 − 𝐻 𝑏𝑜𝑛𝑑 (1)

+ 3 × 𝐵𝑜𝑛𝑑 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝐶 − 𝐶 𝑏𝑜𝑛𝑑
+ 3 × 𝐵𝑜𝑛𝑑 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝐶 = 𝐶 𝑏𝑜𝑛𝑑

= 6 × 413.3 𝐾𝐽 𝑚𝑜𝑙 −1 + 3 × 347.7 𝐾𝐽 𝑚𝑜𝑙−1 + 606.7 𝐾𝐽 𝑚𝑜𝑙−1 (2)

= 5343 𝐾𝐽 𝑚𝑜𝑙−1

Now since the experimental enthalpy of formation of the actual benzene molecule is −5494.84 kJ mol−1 which
is more than its hypothetical localized version (−5343 kJ mol−1), the extra stabilization of −151.84 kJ mol−1
can be attributed to the phenomena of delocalization easily.
Conditions for resonance: In order to show the phenomenon of resonance, the following condition must be
satisfied by the molecule under consideration.
1. Different canonical forms of the molecule should differ only with respect to the position of electrons and
not the nuclei.

2. All the participating atoms must lie in the same plane.

3. All resonating structures must possess the same number of unpaired and paired electrons.
4. If two resonating structures are having the same energy, they will contribute equally to the resonance hybrid.
5. More stable resonating structure will contribute higher to the resonance hybrid.

6. Greater is the number of canonical structures, higher will be the stability of corresponding resonance hybrid.

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 CHAPTER 1: Nature of Bonding in Organic Molecules 21

7. The following factors must be taken into consideration before we decide the relative stability of participating
canonical structure:
i) Resonating structures with a greater number of covalent bonds will be more stable, and therefore, will show
more contribution towards resonance hybrid.

ii) Structures with charge separation will be less stable, and therefore, will contribute less towards the
resonance hybrid.

iii) Structures violating the octet rule should not be considered (involving second-period elements).

iv) Resonating structures with the negative charge on a more electronegative atom will be less stable, and
therefore, will contribute less to the resonance hybrid.

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 22 A Textbook of Organic Chemistry – Volume I

v) If a structure helps to delocalize the positive charge will contribute significantly toward the resonance hybrid
even if the positive charge is on the electronegative atom.

vi) Resonating structures with like charges on adjacent atoms in space will be less stable sterics, and therefore,
will contribute less towards the resonance hybrid.

Resonance effect:
The resonance or mesomeric effect in organic compounds may simply be defined as the polarity
produced in the molecule due to resonance phenomena.
The effect is used in a qualitative way and describes the electron-withdrawing or releasing properties
of substituents based on relevant resonance structures and is symbolized by the letter R or M. The resonance
effect is negative (–R) when the substituent is an electron-withdrawing group and the effect is positive (+R)
when the substituent is an electron releasing group. A detailed explanation of the two effects with some typical
examples is given below.
i) +R effect: Some groups release the electron density to the multiple bonds through resonance and are said to
have a +M or +R effect in general.

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 CHAPTER 1: Nature of Bonding in Organic Molecules 23

It is also worthy to mention that groups showing the +R effect are having lone pair of the electron that can be
put into conjugation with the double of the chain or ring to which it gets attached with. Some of the typical
groups showing the +R effect are given below.
–O− > –NH2 > –NHR > –OR > –NHCOR > –OCOR > –Ph > –F > –Cl > –Br > –I
ii) −R effect: Some groups withdraw the electron density to the multiple bond through resonance, and are said
to have −M or −R effect in general.

It is also worthy to mention that groups showing the −R effect are having a double bond that can be put into
conjugation with the double of the chain or ring to which it gets attached with. Some of the typical groups
showing the −R effect are given below.
–NO2 > –CN > –S(=O)2−OH > –CHO > –C=O > –COOCOR > –COOR > –COOH > –CONH2 > –COO−
It should also be noted that the resonance is different from the inductive effect and can exert its
electron-withdrawing or electron releasing effect in a direction along or opposite to the inductive effect. Unlike
inductive effect which can also act in saturated molecules, the resonance effect is observed only in conjugated
systems. Furthermore, the inductive effect involves σ-electrons and is operative only up to four carbon atoms,
whereas the resonance effect involves unpaired or π-electrons which can get delocalized over longer distances.

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 24 A Textbook of Organic Chemistry – Volume I

Applications of resonance effect: Some of the important applications of the resonance or mesomeric effect
that affect the properties to a great extent are given below.
i) Low reactivity of vinyl and aryl halides: The existence of the +R effect in vinyl and aryl halides makes them
less reactive towards the nucleophilic substitution reaction due to the partial double character of the carbon-
halogen bond as shown below.

ii) High reactivity of allyl and benzyl halides: The existence of the −R effect in allyl and benzyl halides makes
them more reactive towards the nucleophilic substitution reaction due to the formation resonance stabilized
cation bond as shown below.

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 CHAPTER 1: Nature of Bonding in Organic Molecules 25

iii) Acidic character of carboxylic acid: The existence of charge separation in one of the resonating structures
of carboxylic acid makes it less stable than the carboxylate anion which is formed by the loss of a proton.

iv) Acidic strength of alcohols and phenols: Alcohols are less acidic than phenols because, unlike alkoxide
ion, the phenoxide (formed by the loss of proton) resonance stabilized.

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 26 A Textbook of Organic Chemistry – Volume I

v) Basic strength of ethylamine and aniline: Ethylamine is more basic than aniline because the electron pair in
aniline is less available for donation due to resonance. On the other hand, the +I effect of the ethyl group
increases the electron density on the nitrogen atom making it more basic.

vi) Basic strength of ethylamine and acetamide: Ethylamine is more basic than acetamide because the electron
pair in acetamide is less available for donation due to resonance. On the other hand, the +I effect of the ethyl
group in ethylamine increases the electron density on the nitrogen atom making it more basic.

vii) Effect on dipole moments: The dipole moments of different organic molecules are also affected by the
resonance effect to a very large extent. For instance, the dipole moment of vinyl chloride is found to be only
1.69D which is much less than the value expected from a large inductive effect (2.05D).

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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