1. Electrophilic Aromatic Substitution Reactions..................9
1.1 Introduction to aromaticity and stability of aromatic systems
1.1.1 General Mechanism of electrophilic aromatic substitution
1.2 Mechanism of Electrophilic Aromatic Substitution reactions
1.2.1 Nitration
1.2.2 Sulfonation
1.2.3 Halogenation
1.2.4 Friedel-Crafts alkylation Reactions
1.2.5 Friedel-Crafts acylation Reactions.
1.3 Effect of Substituent Groups
1.3.1 Orientation and reactivity in monosubstituted Benzene
1.4 Classification of Substituent Groups
1.4.1 Activating Groups or and ortho/para/meta-Directors
1.4.2 Deactivating Groups or and ortho/para/meta-Directors
1.4.3 Multiple substitutions
1.4.4 Steric and electronic effects
1.4.5 Electrophilic substitution in polycyclic aromatic hydrocarbons
2. Heterocyclic Chemistry..................................................34
2.1 Introduction and classification of heterocyclic compounds.
2.1.1 Classification of heterocyclic compounds
2.1.2 Representative structures
2.1.3. Nomenclature
2.1.4. Numbering of pyrrole, furan, thiophene, and pyridine
2.2 Aromaticity in heterocycles.
2.2.1 Hückel’s rule
2.2.2 Electron counting in heterocycles
2.2.3 Why is pyrrole a weak base, but pyridine is moderately basic
2.2.4 Aromatic stabilisation energies (ASE)
2.3 Structure, aromatic character and Reactivity of five-membered heterocycles: pyrrole, furan and thiophene.
2.3.1 Bond lengths and bond angles
2.3.2 Resonance structures
2.3.3 Dipole moments
2.3.4 Reactivity order
2.4 Paal–Knorr synthesis
2.4.1 Paal–Knorr furan synthesis
2.4.2 Paal–Knorr pyrrole synthesis
2.4.3 Paal–Knorr thiophene
2.5 Electrophilic substitution reactions of pyrrole, furan and thiophene: Reactivity and orientation,
2.5.1 Electrophilic substitution reactions- (a) Nitration (b) Halogenation
(c) Sulfonation (d) Friedel–Crafts acylation (e) Vilsmeier-Haack formylation
2.6 Structure of pyridine: basicity, effect of nitrogen on reactivity, Electrophilic and nucleophilic substitution reactions of pyridine.
2.6.1 Structure of pyridine
2.6.2 Pyridine as a base
2.6.3 Electrophilic substitution: prefers C-3 (β)
2.6.4 Nucleophilic substitution- (a) Chichibabin amination
(b) Other Nucleophilic Substitutions of Pyridine (SNAr Reactions)
3. Named Reactions and Rearrangements.........................58
3.1 Aldol condensation
3.2 Cannizzaro reaction
3.3 Perkin reaction
3.4 Reformatsky reaction
3.5 Diels-Alder reaction
3.6 Wittig reaction
3.7 Pinacol-pinacolone rearrangement
3.8 Beckmann rearrangement
3.9 Hofmann rearrangement
3.10 Baeyer-Villiger oxidation
3.11 Benzil-Benzillic acid rearrangement
3.12 Curtius and Schmidt rearrangements
3.12.1 Curtius rearrangement
3.12.2 Schmidt rearrangement
4. Stereochemistry.............................................................86
4.0 Introduction
4.1 Optical isomerism in compound with and without stereocenters;
4.1.1 Optical isomerism in compound with Stereo-centers
4.1.2 Optical isomerism in compound without stereo-centers
4.2 optical isomerism without a classical stereogenic center; axial chirality and its origin;
4.2.1 The Origin of Axial Chirality
4.2.2 The Origin
4.3 Optical Isomerism in Allenes and substituted biphenyl
4.3.1 Optical Isomerism in Allenes
4.3.2 Optical Isomerism in substituted biphenyl
4.4 Restricted rotation and atropisomerism
4.4.1 Chiralty and Atropisomerism
4.5 Atropisomerism; helical and planar chirality (introductory)
4.5.1 Axial Chirality
4.5.2 Planar Chirality
4.5.3. Helical Chirality
4.6 Structural feactures of fused ring systems; conformation of cis-decalin and trans-decalin
5. Retrosynthetic Analysis..............................................108
5.1 Introduction to retrosynthesis and synthetic planning.
5.2 Concepts and terminology: target molecule (TM), retrosynthetic analysis, disconnection approach, functional group interconversion (FGI), functional group addition (FGA), synthon and synthetic equivalent,
5.3 One-group and two-group disconnections.
5.3.1 Retrosynthetic analysis of acetophenone,
5.3.2 Retrosynthetic analysis of ethyl acetoacetate,
5.3.3 Retrosynthetic analysis of 1,3-diphenyl-2-propen-1-one,
5.3.4 Retrosynthetic analysis of cinnamic acid,
5.3.5 Retrosynthetic analysis of 1-(4-methoxy-3-nitrophenyl)ethan-1-one
