ATOOCV1!3!11 Generation Structure Stability and Reactivity of Carbocations Carbanions Free Radicals Carbenes and Nitrenes

176 A Textbook of Organic Chemistry – Volume I
❖ Generation, Structure, Stability and Reactivity of Carbocations,

Carbanions, Free Radicals, Carbenes and Nitrenes
A number of chemical reactions proceed via the formation of certain chemical species which are
formed somewhere during the overall pathway. These species are called as reaction intermediates and are
actual molecules that are short-lived and unstable. Sometimes they are called temporary reactants or products
because they are neither present in actual reactants nor the actual products. Here, we will study the generation,
structure, stability, reactivity of carbocations, carbanions, free radicals, carbenes, and nitrenes.
➢ Carbocations
The term carbocations in organic chemistry may simply be defined as the chemical species that
carries a positive charge on the carbon with only six valence electrons.
Since the carbon in carbocations has only six electrons, it is electron deficient; and therefore, acts as
an electrophile in chemical reactions.
1. Generation of carbocations: The heterolytic cleavage of the covalent bond is responsible for the generation
of most of the carbocation species. Some reactions involving the production of carbocations are given.
i) Ionization of alkyl halides in polar solvents:
ii) Protonation of alcohols followed by dehydration:
iii) Protonation of unsaturated systems:
iv) Action of super acids on alkyl fluorides:
v) Deamination of primary aliphatic amines by nitrous acid:
Copyright © Mandeep Dalal

CHAPTER 3: Reaction Mechanism: Structure and Reactivity 177
2. Structure of carbocations: It has been experimentally found that the carbocations are trigonal planar
around the carbon bearing positive charge. Now valence bond theory, as well as molecular orbital theory,
easily accounted for such structure, it is more comfortable to discuss the valence bond approach. The carbon
with a positive charge is in sp2 hybridization with three hybrid orbitals oriented at 120° in a plane with an
empty pz orbital at the perpendicular.
Figure 9. Orbital structure of carbocation.
3. Stability of carbocations: Before we discuss the stability of carbocations, we need to classify them on the
basis of saturation. The first case is alkyl carbocations which are given below.
The second case is of unsaturated carbocations where the carbon bearing positive charge is directly connected
to a carbon participating in multiple bond i.e.
Since the carbon in carbocations has only six electrons, it is electron deficient; and therefore, any effect that
can compensate for the deficiency will stabilize the carbocation.
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i) Stability of alky carbocations on the basis of inductive effect:

Since the alkyl group has an electron donating effect (+I), the stability of the carbocation will increase
as the number of donating ability of the attached group increases. The stability order of alky carbocations on
the basis of inductive effect is given below.
ii) Stability of alky carbocations on the basis of hyperconjugation:

The existence of the hyperconjugation effect can be used to rationalize the relative stability of
different carbocations as shown below.
Hence, as far as the number of possible hyper-conjugative structures possible is concerned, tertiary carbocation
should be more stable than secondary, which in turn should be more stable than primary.

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iii) Stability of alky carbocations on the basis of steric effect:

Since the alkyl carbocations are primarily obtained from alkyl halides with tetrahedral geometry, a
link between the steric relief and carbocation formed can be established. During the formation of carbocations
in such cases, the carbon-carbon bond angles change from 109°28’ to 120°. Therefore, the carbon with bulky
groups around is expected to get more relief from this carbocationic conversion. The stability order of alky
carbocations on the basis of steric effect is given below.
iv) Stability of ally and benzyl carbocations:

The stability of the carbocations in which the carbon bearing positive charge is adjacent to the double
or triple bond can be rationalized in terms of resonance effect. First of all, let us draw the resonance structures
allyl and benzyl carbocations.
Now, as the number of phenyl groups attached to carbon bearing positive charge increases, the number of
resonating structures will also increase, and hence the stability.

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Therefore, the expected order of the stability of unsaturated systems with carbon bearing positive charge should
be as given below.
Similarly, the order of stability in phenylcyclopropenyl, diphenylcyclopropenyl and triphenylcyclopropenyl

should follow the following order.

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v) Stability of substituted benzyl carbocations: Since the carbon is electron bearing positive charge is electron
deficient in nature, any group with +R effect will stabilize the system and vice-versa. The order of stability of
some typically substituted carbocations is given below.
vi) Stability of tropylium ion: The cycloheptatrienyl cation or tropylium ion is exceptionally stable due to its
aromatic character (planar and 4n+2 π electrons). According to molecular orbital theory, its delocalization
energy is significantly greater than the delocalization energy of its acyclic counterpart. Similarly, the valence
bond theory can also explain its exceptional stability of the basis of resonance as given below.
vii) Instability of cyclopentadienyl cation: The cyclopentadienyl cation is very unstable due to its antiaromatic
character (planar and 4n π electrons). According to molecular orbital theory, its delocalization energy is
significantly less than the delocalization energy of its acyclic counterpart.
viii) Stability of alkoxyalkyl cation: if the positive charge bearing carbon in the carbocationic species is
connected to a hetero atom with lone pair of electrons, the resonance will get it stabilized.

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ix) Stability of acyl cation: Just like alkoxyalkyl cation, the resonance will also stabilize the acyl cation as
shown below.
x) Instability of phenyl and vinyl cation: If the positive charge is on the double-bonded carbon atom, the system
cannot be stabilized because the sp2 orbital carrying positive charge will be perpendicular to the orbital of the
double bond.
4. Reactivity of carbocations: The principal routes by which the carbocations can react to give rise to stable
products are given below.
i) Nucleophilic attack: In these types of reactions, a carbocation may combine with a species by accepting an
electron pair. Furthermore, it should also be noted that if all the three groups on the carbocation are different,
a racemic mixture will be obtained.
ii) Proton removal: In these types of reactions, a carbocation may result in the removal of a proton from the
adjacent atom forming a double bond.

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iii) Rearrangement reaction: 1-2 methyl shit or 1-2 hydride shifts are very common in carbocation chemistry
to attain a more stable counterpart. For instance, a primary carbocation will prefer to rearrange itself into a
more stable tertiary carbocation.
iv) Addition reactions: A carbocation may attack at the triangular face of a double bond to create a new
positively charged center as shown below.
➢ Carbanions
The term carbanions in organic chemistry may simply be defined as the chemical species that carries
a negative charge on the carbon with only eight valence electrons.
Since the carbon in carbanions has its octet complete, it is electron-rich; and therefore, acts as a
nucleophile in chemical reactions.
1. Generation of carbanions: The heterolytic cleavage of the covalent bond is responsible for the generation
of most of the carbanions species. Some reactions involving the production of carbanions are given.
i) Hydrogen abstraction by a strong base from the carbon alpha to cyano, nitro, or carbonyl groups:

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ii) Nucleophilic addition to α, β-unsaturated species:
iii) Abstraction of terminal hydrogen from acetylene:
2. Structure of carbanions: It has been experimentally found that the carbanions are trigonal pyramidal
around the carbon bearing negative charge. Now valence bond theory, as well as molecular orbital theory,
easily accounted for such structure, it is more comfortable to discuss the valence bond approach. The carbon
with a negative charge is in sp3 hybridization with three hybrid orbitals forming bonds and the fourth hybrid
orbital containing lone pair of electrons.
Figure 10. Orbital structure of carbonation.
Furthermore, it should also be kept in mind that if the carbon bearing negative charge is adjacent to multiple
bonds, the carbanions will adopt a planar structure to get stable by dispersing the negative charge.
Figure 11. The planar structure of allyl carbanion.

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3. Stability of carbanions: Before we discuss the stability of carbanions, we need to classify them on the basis
of saturation. The first case is alkyl carbanions which are given below.
The second case is of unsaturated carbanions where the carbon bearing negative charge is directly connected
to a carbon participating in multiple bonds i.e.
Since the carbon in carbanions has eight valence electrons, it is electron-rich; and therefore, any effect that can
compensate the electron density accumulation will stabilize the carbanions.
i) Stability of alky carbanions on the basis of inductive effect:
Since the alkyl group has an electron donating effect (+I), the stability of the carbocation will increase
as the number of donating ability of the attached group increases. The stability order of alky carbocations on
the basis of inductive effect is given below.

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ii) Stability of carbanions on the basis of hybridization:

The nature and type of hybridization effect can be used to rationalize the relative stability of different
carbanions as shown below.
Hence, we can say that as the s-character of carbon bearing negative charge increases, the lone pair gets better
stabilization; and therefore, overall carbanionic stability also increases.
iii) Stability of ally and benzyl carbanions:
The stability of the carbanions in which the carbon bearing negative charge is adjacent to the double
or triple bond can be rationalized in terms of resonance effect. First of all, let us draw the resonance structures
of allyl and benzyl carbanions.
Now, as the number of phenyl groups attached to carbon bearing negative charge increases, the number of
resonating structures will also increase, and hence the stability.

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Therefore, the expected order of the stability of unsaturated systems with carbon bearing negative charge
should be as given below.
iv) Stability of substituted benzyl carbanions: Since the carbon is electron bearing negative charge is electron-
rich in nature, any group with −R effect will stabilize the system and vice-versa. The order of stability of some
typically substituted carbanions is given below.
v) Instability of cyclopentadienyl anion: The cyclopentadienyl anion is very unstable due to its aromatic
character (planar and 4n+2 π electrons). According to molecular orbital theory, its delocalization energy is
significantly greater than the delocalization energy of its acyclic counterpart.

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vi) Stability of carbanions with electron-withdrawing groups: The presence of electron-withdrawing group will
distribute the charge over a wider range; and therefore, will result in a greater stabilization.
4. Reactivity of carbanions: The principal routes by which the carbanions can react to give rise to stable
i) Lone pair donation: One of the most common pathways of carbanions reaction is the donation of electrons
to a positive species like proton, or some species with an empty orbital.
ii) Associative reaction: The carbanions can bond with a tetra-coordinated carbon followed by displacement
of one of the previously attached groups.
iii) Rearrangement reaction: Like carbocations, the carbanions can also undergo rearrangement reaction
although it is not very common.
iv) Addition reactions: A carbonation may attack at the triangular face of a double bond to create a new
negatively charged center as shown below.

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➢ Free Radicals
The term free radicals in organic chemistry may simply be defined as the chemical species that
carries odd or unpaired electrons on the carbon with only seven valence electrons.
Since the carbon in free radicals has only seven electrons, it is electron deficient; and therefore, acts
as an electrophile in chemical reactions.
1. Generation of free radicals: The homolytic cleavage of the covalent bond is responsible for the generation
of most of the free radicals species. Some reactions involving the production of free radicals are given below.
i) Thermal cleavage:
ii) Photochemical Cleavage:
2. Structure of free radicals: It has been experimentally found that the free radicals are trigonal planar around
the carbon bearing odd electron. Now valence bond theory, as well as molecular orbital theory, easily
accounted for such structure, it is more comfortable to discuss the valence bond approach. The carbon with the
odd electron is in sp2 hybridization with three hybrid orbitals oriented at 120° in a plane perpendicular to pz
orbital occupied by the odd electron.

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Figure 12. Orbital structure of free radical.
3. Stability of free radicals: Before we discuss the stability of free radicals, we need to classify them on the
basis of saturation. The first case is alkyl free radicals which are given below.
The second case is of unsaturated free radicals where the carbon bearing odd electron is directly connected to
a carbon participating in multiple bonds i.e.
Since the carbon in free radicals has only seven electrons, it is electron deficient; and therefore, any effect that
can compensate for the deficiency will stabilize the carbocation.
i) Stability of alky free radicals on the basis of inductive effect:
Since the alkyl group has an electron-donating effect (+I), the stability of the free radicals will
increase as the number of donating groups attached increases. The stability order of alky free radicals on the
basis of inductive effect is given below.

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ii) Stability of alky free radicals on the basis of hyperconjugation:

The existence of the hyperconjugation effect can be used to rationalize the relative stability of
different free radicals as shown below.
Hence, as far as the number of possible hyper-conjugative structures possible is concerned, tertiary free radicals
should be more stable than secondary, which in turn should be more stable than primary.

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iii) Stability of ally and benzyl free radicals:

The stability of the free radicals in which the carbon bearing odd electron is adjacent to the double or
triple bond can be rationalized in terms of resonance effect. First of all, let us draw the resonance structures
of allyl and benzyl free radicals.
Now, as the number of phenyl groups attached to carbon bearing electron increases, the number of resonating
structures will also increase, and hence the stability.

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Therefore, the expected order of the stability of unsaturated systems with carbon bearing odd electron should
be as given below.
4. Reactivity of free radicals: The principal routes by which the free radicals can react to give rise to stable
i) Decomposition reactions: One of the most common examples of this type of process is the decomposition
of the benzoxy radical.
ii) Hydrogen abstraction: In these types of reactions, a free radical may result in the removal of a proton from
the same (intermolecular process) or another molecule (intramolecular process).
iii) Rearrangement reaction: Free radicals may undergo rearrangement reactions to yield different but stable
free radical counterparts.

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iv) Addition reactions: The free radical obtained from an alkene may attack the triangular face of the double
bond of another alkene molecule, and the process continues to yield polymers.
➢ Carbenes
The term carbenes in organic chemistry may simply be defined as the chemical species that carries
two non-bonding electrons (paired or unpaired) on the carbon with a total of six valence electrons.
Since the carbon in carbenes has only six electrons, it is electron deficient; and therefore, acts as an
electrophile in chemical reactions.
1. Generation of carbenes: Some of the most common pathways involving the production of carbenes are
given below.
i) Decomposition of ketones or diazoalkanes:
ii) Thermal or photolytic cleavage of cyclopropanes and oxiranes:
iii) Attack of strong base on chloroform:

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2. Structure of carbenes: Before we discuss the structure of carbenes, it is better to understand how carbenes
can be classified on the basis of the distribution of non-bonding electrons. There are primarily two types
carbenes; singlet carbenes and triplet carbenes.
It has been experimentally found that the singlet carbenes are V-shaped and are derivatives of trigonal
planar geometry. Now valence bond theory, as well as molecular orbital theory, easily accounted for such
structure, it is more comfortable to discuss the valence bond approach. The central carbon is in sp2
hybridization with three hybrid orbitals oriented at 120° in a plane; two half-filled orbitals participating in
bonding whilst the third hybrid orbital contains the lone pair. The pz orbital remains empty and is perpendicular
to the molecular plane.
Figure 13. Orbital structure of singlet carbenes.
The triplet carbenes are either linear or V-shaped (depending upon the reaction requirement). Now
valence bond theory, as well as molecular orbital theory, easily accounted for such structure, it is more
comfortable to discuss the valence bond approach. The central carbon in linear triplet carbene is in sp
hybridization with two hybrid orbitals oriented at 180° along the z-axis participating in bonding; whilst the
atomic px and py atomic orbital containing the unpaired electrons.
Figure 14. Orbital structure of triplet carbenes.
The central carbon in bent triplet carbene is in sp2 hybridization with three hybrid orbitals oriented at 120° in
a plane; two half-filled orbitals participating in bonding whilst the third hybrid orbital contains an unpaired
electron. The other unpaired electron is in the atomic pz orbital perpendicular molecular plane.

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3. Stability of carbenes:
In the case of simple hydrocarbons, triplet carbenes typically have energies 8 kcal/mol less than
singlet carbenes due to Hund's rule of maximum multiplicity; and therefore, as a whole, we can conclude that
the triplet is the ground state and singlet one is the excited state entities. Also, groups that can donate electron
pairs can stabilize the singlet carbene by delocalizing the pair into an empty pz orbital. Furthermore, the singlet
state can become the ground state if its energy is significantly reduced. However, triplet carbenes cannot be
stabilized by this strategy. A carbene 9-fluorenylidene is found to exist in a rapid equilibrating mixture of
triplet and singlet states with an energy difference of roughly 1.1 kcal/mol. Nevertheless, it is disputed if diaryl
carbenes like fluorene carbene are true carbenes since the electrons can be delocalized to such a level that they
become biradicals in nature. The experimental studies have suggested that triplet carbenes can be stabilized
thermodynamically with heteroatoms of electropositive nature (like in silyl and silyloxy carbenes).
4. Reactivity of carbenes: The principal routes by which the carbenes can react to give rise to stable products
are given below.
i) Addition reactions: besides the carbon-carbon double bonds (including aromatic systems), carbenes may
also add to carbon-heteroatom multiple bonds.
ii) Insertion reaction: In these reactions, carbenes get inserted into CH bonds to give stable products.

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iii) Dimerization reaction: Carbenes may undergo dimerization to form an alkene; however, it is more likely
to arise from the attack by a carbene on a molecule of a carbene precursor.
iv) Rearrangement reactions: The carbenes can also undergo rearrangement reactions to yield very stable
products as given below.
v) Fragmentation reactions: many substitutions and elimination products are obtained from the fragmentation
reactions of alicyclic oxychlorocarbenes as given below.
vi) Rearrangement reactions: Triplet carbenes are also able to abstract hydrogen or any other groups or atoms
to yield free radicals’ products as given below.
➢ Nitrenes
The term nitrenes in organic chemistry may simply be defined as the chemical species that carries
four non-bonding electrons (paired or unpaired) on the nitrogen with a total of six valence electrons.
Since the nitrogen in carbenes has only six electrons, it is electron deficient; and therefore, acts as an
electrophile in chemical reactions.
1. Generation of nitrenes: Some of the most common pathways involving the production of nitrenes are given
below.
i) Photochemical or thermal decomposition of isocyanates or azides:

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ii) Elimination of sulphonate ion from certain compounds:
2. Structure of nitrenes: Before we discuss the structure of nitrenes, it is better to understand how nitrenes
can be classified on the basis of the distribution of non-bonding electrons. There are primarily two types of
nitrenes; singlet nitrenes and triplet nitrenes.
It has been experimentally found that the singlet nitrenes are linear and are derivatives of trigonal
planar geometry. Now valence bond theory, as well as molecular orbital theory, easily accounted for such
structure, it is more comfortable to discuss the valence bond approach. The nitrogen is in sp2 hybridization
with three hybrid orbitals oriented triangularly in a plane; one half-filled hybrid orbital participating in bonding
with carbon whilst the second and third hybrid orbitals contain the lone pairs. The pz orbital remains empty
and is perpendicular to the above-mentioned triangular plane.
Figure 15. Orbital structure of singlet nitrenes.
The triplet nitrenes are also linear. The nitrogen in triplet nitrenes is in sp hybridization with two
hybrid orbitals oriented at 180° along the z-axis; one hybrid orbital (half-filled) participating in bonding whilst
the other hybrid orbital contains a lone pair. The atomic px and py atomic orbital containing the unpaired
electrons.
Figure 16. Orbital structure of triplet nitrenes.

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3. Stability of nitrenes:
Although nitrenes are too reactive to isolate under normal conditions, in 2019, an authentic triplet
nitrene was isolated by Betley and Lancaster, stabilized by coordination to a copper center in a bulky ligand.
Furthermore, triplet nitrenes are thermodynamically more stable but react stepwise allowing free rotation and
thus producing a mixture of stereochemistry. They are usually detected by adding carbon monoxide as it can
form isocyanates with nitrenes which can be isolated easily.
4. Reactivity of nitrenes: The principal routes by which the nitrenes can react to give rise to stable products
are given below.
i) Addition reactions: Nitrenes may add to carbon-carbon multiple bonds to give rise to some stable product.
ii) Insertion reaction: In these types of reactions, nitrenes get inserted into CH bonds to give stable products.
iii) Dimerization reaction: Nitrenes may undergo dimerization to form diamide.
iv) Rearrangement reactions: The nitrenes can also undergo rearrangement reactions to yield very stable
products as given below.
v) Hydrogen abstraction: Nitrenes are also able to abstract hydrogen or any other groups or atoms to yield free
radicals’ as given below.

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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

ATOOCV1!3!11 Generation Structure Stability and Reactivity of Carbocations Carbanions Free Radicals Carbenes and Nitrenes

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ATOOCV1!3!11 Generation Structure Stability and Reactivity of Carbocations Carbanions Free Radicals Carbenes and Nitrenes

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176 A Textbook of Organic Chemistry – Volume I

❖ Generation, Structure, Stability and Reactivity of Carbocations,

ii) Protonation of alcohols followed by dehydration:

iii) Protonation of unsaturated systems:

iv) Action of super acids on alkyl fluorides:

v) Deamination of primary aliphatic amines by nitrous acid:

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Figure 9. Orbital structure of carbocation.

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i) Stability of alky carbocations on the basis of inductive effect:

ii) Stability of alky carbocations on the basis of hyperconjugation:

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iii) Stability of alky carbocations on the basis of steric effect:

iv) Stability of ally and benzyl carbocations:

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Similarly, the order of stability in phenylcyclopropenyl, diphenylcyclopropenyl and triphenylcyclopropenyl

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ii) Nucleophilic addition to α, β-unsaturated species:

iii) Abstraction of terminal hydrogen from acetylene:

Figure 10. Orbital structure of carbonation.

Figure 11. The planar structure of allyl carbanion.

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ii) Stability of carbanions on the basis of hybridization:

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ii) Photochemical Cleavage:

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Figure 12. Orbital structure of free radical.

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ii) Stability of alky free radicals on the basis of hyperconjugation:

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iii) Stability of ally and benzyl free radicals:

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ii) Thermal or photolytic cleavage of cyclopropanes and oxiranes:

iii) Attack of strong base on chloroform:

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Figure 13. Orbital structure of singlet carbenes.

Figure 14. Orbital structure of triplet carbenes.

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ii) Elimination of sulphonate ion from certain compounds:

Figure 15. Orbital structure of singlet nitrenes.

Figure 16. Orbital structure of triplet nitrenes.

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iii) Dimerization reaction: Nitrenes may undergo dimerization to form diamide.

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