Advanced organic chemistry : reactions and mechanisms / Maya Shankar Singh.

Format:

Book

Author/Creator:

Singh, Maya Shankar, 1960- author.

Series:

Always learning.

Always Learning

Language:

English

Subjects (All):

Chemistry, Organic.

Physical Description:

1 online resource (1 volume) : illustrations

Edition:

0

Place of Publication:

Delhi : Dorling Kindersley (India), [2007]

System Details:

text file

Summary:

Advanced Organic Chemistry: Reactions and Mechanisms covers the four types of reactions -- substitution, addition, elimination and rearrangement; the three types of reagents -- nucleophiles, electrophiles and radicals; and the two effects -- electroni

Contents:

Cover

Preface

Acknowledgements

Contents

Chapter 1: Concept of Acids and Bases

1.1 Introduction

1.1.1 What Is an Acid or a Base

1.1.2 Properties of Acids

1.1.3 Properties of Bases

1.2 Acidity and Basicity of Molecules

1.2.1 Acidity

1.2.2 Carbon Acids

1.2.3 Nitrogen Acids

1.2.4 Organosulphur Oxyacids

1.2.5 Basicity

1.2.6 Effects Decreasing Electron Density on Nitrogen

1.3 Definition of pka

1.4 pH Box

1.4.1 pka Box

1.4.2 pH of Strong Acids and Bases

1.4.3 Strong Acids

1.4.4 Weak Acids

1.4.5 Strong Bases

1.4.6 Weak Bases

1.4.7 pH of Weak Acids and Bases

1.5 Hard and Soft Acids and Bases

1.5.1 Lewis Acids and Bases

1.5.2 Hard and soft Acids

1.5.3 Hard and Soft Bases

1.5.4 Hard and Soft Acid-Base Classification

1.6 Effect of Structure on Strength of Acids and Bases

1.6.1 Field Effect

1.6.2 Resonance Effect

1.6.3 Periodic Table correlation

1.6.4 Statistical Effect

1.6.5 Hydrogen-bonding

1.6.6 Steric Effect

1.6.7 Hybridization

1.7 Effects of Medium on Acid and Base Strength

1.8 Levelling Effect

1.9 Summary

Problems

Objective Type Questions

Chapter 2: Delocalized Chemical Bonding and Electronic Effects

2.1 Introduction

2.2 Resonance

2.3 Resonance Energy

2.4 Resonance Effect

2.5 Hyperconjugation (Baker-N athan Effect)

2.5.1 Negative hyperconjugation

2.6 Tautomerism

2.6.1 Mechanism of Keto-Enol Interconversion

2.6.2 Differences between Tautomerism and Resonance

2.7 Nitro-acinitro System

2.8 Inductive Effect

2.9 Electromeric Effect

2.10 Steric Effect

2.11 Hydrogen Bonding

2.12 Summary

Chapter 3: Aliphatic Nucleophilic Substitution Reactions

3.1 Introduction

3.2 Mechanism of SN2 Reaction

3.3 Nucleophile in SN2 Reaction.

3.4 Leaving Group in SN2 Reaction

3.5 Interm olecular versus Intram olecular Reactions

3.5.1 Baldwin's Rules

3.6 Mechanism of SN1 Reaction

3.7 Leaving Group in SN1 Reaction

3.8 Nucleophile in SN1 Reaction

3.9 Carbocation Rearrangements

3.10 Stereochemistry of SN2 and SN1 Reactions

3.11 Role of Solvent in SN2 and SN1 Reactions

3.12 Solvation Effect

3.13 Effect of Solvent on Rate of Reaction

3.13.1 Effect of solvent on Rate of SN1 Reaction

3.13.2 Effect of Solvent on Rate of SN2 Reaction

3.14 Benzylic, Allylic, Vinylic and Aryl Halides

3.15 Competition between SN2 and SN1 Reactions

3.16 Mixed SN1 and SN2 Mechanism

3.17 Neighbouring Group Participation

3.18 Summary

Chapter 4: Elimination Reactions

4.1 Introduction

4.1.1 Substitution and Elimination

4.2 a-Elimination

4.2.1 Elimination When Nucleophile Attacks Hydrogen

4.2.2 Nucleophile Effects on Elimination and Substitution

4.3 E1 and E2 Mechanism s

4.4 Orientation of Double Bond

4.5 Role of Leaving Group

4.5.1 Stereoselective E1 Reactions

4.5.2 Regioselective E1 Reactions

4.5.3 Anti-periplanar Transition States of E2 Eliminations

4.5.4 Stereospecific E2 Eliminations

4.6 E2 Eliminations from Cyclohexanes

4.7 Regioselectivity of E2 Elim inations

4.8 E2 Elimination from Vinyl Halides: How to Make Alkynes

4.9 Anion-stabilizing Groups Allow E1cB

4.10 E1cB Rate Equation

4.11 E1cB Eliminations in Context

4.12 E1-E2 -E1cB Spectrum

4.13 Pyrolytic or Thermal Eliminations

4.14 Summary

Chapter 5: Addition Reactions

5.1 Introduction

5.2 Electrophilic Addition of HX and H2 to Alkenes

5.2.1 Experimental evidence

5.2.2 Product Analysis

5.3 M echanism of Electrophilic Addition

5 .3.1 Halonium Ions.

5.3.2 Stereochemistry

5.3.3 Stereospecific Electrophilic Addition to Stereoisomeric Alkenes

5.3.4 Regioselectivity in Unsymmetrical Electrophilic Addition to Alkenes

5.4 Acid-catalyzed Hydrolysis of Vinyl Ethers

5.5 Other Electrophilic Addition Reactions to Alkenes

5.5.1 Epoxidation

5.5.2 Sharpless Asymmetric Epoxidation

5.5.3 1,2-bis Hydroxylation

5.5.4 Hydroboration-oxidation

5.6 Electrophilic Addition to Alkynes

5.7 Nucleophilic Addition to Alkenes and Alkynes

5.7.1 Alkenes

5.7.2 Alkynes

5.8 Radical Addition to Alkenes

5.9 Diels-Alder Reaction

5.9.1 Solvent in Diels-Alder Reaction

5.9.2 Applications

5.10 Summary

Chapter 6: Free Radical Reactions

6.1 Introduction

6.1.1 Early Evidence for Existence of Radicals

6.1.2 Detection and Characterization of Radicals

6.2 Structure and Bonding of Radicals

6.3 Thermochemical Data of Radicals

6.4 Generation of Free Radicals

6.5 Radicals in Cars

6.6 Radical Stability

6.7 Reactions of Free Radicals

6.8 Stereochemistry of Radical Substitution Reactions

6.9 Summary

Chapter 7: Molecular Rearrangements

7.1 Introduction

7.2 Cationic Rearrangements

7.3 Wagner-Meerwein Rearrangement

7.4 Pinacol Rearrangement

7.5 Semipinacol Rearrangements

7.6 Demjanov Rearrangement

7.7 Baeyer-Villiger Oxidation

7.8 Fries Rearrangement

7.9 D ienone-Phenol Rearrangement

7.10 Rearrangement to Electron-deficient Nitrogen

7.10.1 Beckmann Rearrangement

7.11 Hofmann, Curtius, Schmidt and Lossen Rearrangements

7.11.1 Hofmann Rearrangement

7.11.2 Curtius Degradation (Rearrangement)

7.11.3 Schmidt Reaction

7.11.4 Lossen Rearrangement

7.12 Wolff Rearrangement

7.13 Electrophilic Rearrangements

7.13.1 Stevens Rearrangement.

7.13.2 Wittig Rearrangement

7.13.3 Favorskii Rearrangement

7.14 Summary

Chapter 8: Aromatic Substitution

8.1 Introduction

8.2 Electrophilic Aromatic Substitution (SEAr)

8.2.1 Nitration of Benzene

8.2.2 Halogenation of Benzene

8.2.3 Friedel-Crafts Alkylation

8.2.4 Friedel-Crafts Acylation

8.2.5 Sulphonation of Benzene

8.2.6 Protonation

8.3 Reactivity and Orientation in Electrophilic Aromatic Substitution

8.4 Groups Donating Electrons by Mesomeric Effect

8.5 Groups Withdrawing Electrons by Mesomeric Effect

8.6 Groups Withdrawing Electrons by Inductive Effect

8.7 Groups Donating Electrons by Inductive Effect

8.8 Ortho/Para Ratios

8.9 Effects of Multiple Substitution

8.10 Hammett Equation

8 .11 Nucleophilic Aromatic Substitution

8.11.1 By Addition -Elimination Mechanism (SNAr)

8.11.2 By Elimination-Addition Mechanism

8.12 IPSO Substitution

8.13 Summary

Chapter 9: Stereochemistry

9.1 Introduction

9.2 Simple Molecules: Hybridization, Conformation and Configuration

9.2.1 Hybridization: Methane

9.2.2 Hybridization: Ethene and Alkenes

9.2.3 Hybridization: Ethyne

9.2.4 Bonding and Anti-bonding Orbitals

9.2.5 Conformation: Ethane

9.2.6 Conformation of propane and n-butane

9.2.7 Cydohexane: Chair Conformation

9.2.8 Cyclohexane: Boat Conformation

9.2.9 inversion of Cyclohexane

9.2.10 Monosubstituted Cyclohexanes

9.2.11 Disubstituted Cydohexanes

9.3 Chiral Molecules

9.3.1 Chirality, Enantiomers and Optical Activity

9.3.2 How to Specify a Configuration

9.3.3 cahn-lngold-Prelog R/S Conventions

9.3.4 Enantiomers and Diastereoisomers

9.3.5 Racemization

9.3.6 Meso Configuration

9.3.7 Erythro/Threo and Syn/Anti Configurations

9.4 Homochiral Molecules.

9.5 Caged Compounds with Two Stereogenic Bridgehead Carbons

9.6 Epimers and Nomenclature of Bicyclic Compounds

9.7 Separation of Enantiomers: Resolution

9.7.1 Mechanical Separation-crystallization Method

9.7.2 Resolution through Formation of Diastereomers

9.7.3 Separation of Enantiomers by Chromatography

9.7.4 Resolution with Enzymes

9.8 Summary

Chapter 10: Buckminsterfullerene (Soccer Ball, Bucky Ball)

10.1 Introduction

10.2 Synthesis and Isolation of C60

10.3 Reactions of Fullerenes

10.4 Application

10.4.1 Superconductors

10.4.2 HIV Protease Inhibitor

10.4.3 Carbon Nanotubes and Nanowires

10.4.4 Catalysis

10.4.5 Polymerization Reactions

10.4.6 Carbon Chemistry

Chapter 11: Pericyclic Reactions

11.1 Introduction

11.2 Electrocyclic Reactions

11.3 Theoretical Explanation

11.4 Conservation of Orbital Symmetry

11.5 Cycloaddition Reactions

11.6 Frontier Molecular Orbital Approach

11.7 Sigmatropic Rearrangements

11.8 Summary

Chapter 12: Aromaticity

12.1 Introduction

12.2 Concept of Aromaticity

12.3 Anti-aromaticity

12.4 Annulenes

12.5 Aromaticity in Charged Rings

12.6 Homoaromaticity

12.7 Fused-ring Systems

12.8 Aromatic Hydrocarbons

12.9 Heterocyclic Rings

12.10 Summary

Glossary

Index.

Notes:

Description based on online resource; title from title page (Safari, viewed January 27, 2015).

ISBN:

9789332500679

9332500673

OCLC:

901690677