Reactive intermediates in organic chemistry : structure and mechanism / Maya Shankar Singh.

Format:

Book

Author/Creator:

Singh, Maya Shankar.

Language:

English

Subjects (All):

Chemical reactions.

Intermediates (Chemistry).

Physical Description:

1 online resource (295 pages) : illustrations (some color), tables

Edition:

1st ed.

Place of Publication:

Weinheim, Germany : Wiley-VCH Verlag, 2014.

Summary:

Most reactions in organic chemistry do not proceed in a single step but rather take several steps to yield the desired product. In the course of these multi-step reaction sequences, short-lived intermediates can be generated that quickly convert into other intermediates, reactants, products or side products. As these intermediates are highly reactive, they cannot usually be isolated, but their existence and structure can be proved by theoretical and experimental methods. Using the information obtained, researchers can better understand the underlying reaction mechanism of a certain organic transformation and thus develop novel strategies for efficient organic synthesis. The chapters are clearly structured and are arranged according to the type of intermediate, providing information on the formation, characterization, stereochemistry, stability, and reactivity of the intermediates. Additionally, representative examples and a problem section with different levels of difficulty are included for self-testing the newly acquired knowledge. By providing a deeper understanding of the underlying concepts, this is a musthave reference for PhD and Master Students in organic chemistry, as well as a valuable source of information for chemists in academia and industry working in the field. It is also ideal as primary or supplementary reading for courses on organic chemistry, physical organic chemistry or analytical chemistry.

Contents:

Intro

Reactive Intermediates in Organic Chemistry

Contents

Preface

Chapter 1 Introduction

1.1 Reaction Mechanism and Reaction Arrows

1.2 Properties and Characteristics of a Reaction

1.2.1 Reactants and Reagents

1.2.2 Product Selectivity

1.2.3 Reaction Characteristics

1.2.4 Factors that Influence Reactions

1.3 Summary

Further Reading

Chapter 2 Carbocations

2.1 Introduction

2.2 History

2.2.1 Carbonium Ions and Carbenium Ions

2.3 Structures and Geometry of Carbocations

2.4 Generation of Carbocation

2.4.1 From a Halide

2.4.2 From an Alcohol

2.4.3 From an Amine

2.4.4 From an Alkene

2.4.5 From Carbonyl Compounds

2.4.6 Solvent Effects

2.5 Carbocation Stability

2.6 Detection of Carbocations

2.7 Fate of Carbocations

2.7.1 Reaction with a Nucleophile

2.7.2 Elimination of a Proton

2.7.3 Rearrangements of Carbocations

2.7.4 Cationic Polymerization

2.8 Nonclassical Carbocations

2.9 Radical Cations

2.10 Summary

Chapter 3 Carbanions

3.1 Structure and Geometry of Carbanions

3.2 Generation of Carbanions

3.2.1 Reduction of C-X Bond with Metal

3.2.2 Deprotonation from a C-H Bond

3.2.3 Reaction of a Metal with an Alkene

3.2.4 A Negative Ion Adds to a Carbon-Carbon Double or Triple Bond

3.3 Stability of Carbanions

3.4 Reactions of Carbanions

3.5 Enolate Reactions with Carbonyl Groups

3.5.1 Aldol Condensation

3.5.2 Enamine Additions

3.5.3 Robinson Ring-Forming Reaction

3.6 Rearrangements of Carbanions

3.6.1 Homoallylic Rearrangements

3.7 Chiral Carbanions

3.8 Carbanions and Tautomerism

3.8.1 Mechanism of Keto-Enol Interconversion

3.9 Summary

Chapter 4 Radicals

4.1 Introduction

4.2 Detection and Characterization of Radicals

4.3 Structure and Bonding of Radicals.

4.4 Generation of Free Radicals

4.5 Stability of Radicals

4.6 Reactions of Free Radicals

4.7 Stereochemistry of Radical Reactions

4.7.1 Cyclization by Intramolecular Addition Reactions

4.8 Biradicals

4.9 Summary

Chapter 5 Carbenes

5.1 Structure and Geometry of Carbenes

5.2 Generation of Carbenes

5.2.1 Thermolysis or Photolysis of Diazo Compounds

5.2.2 Reaction of N-Nitrosoureas with Base

5.2.3 Reaction of Tosylhydrazone with Base

5.2.4 Carbene Formation by α-Elimination

5.2.5 Generation of Carbenoids (Simmons-Smith Reaction)

5.2.6 Formation of Carbenes under Neutral Conditions

5.2.7 Generation of Carbenes from Small Rings

5.3 Reactions of Carbenes

5.3.1 Addition Reactions

5.3.2 Cycloaddition to 1,2-Dienes (Allenes)

5.3.3 Cycloaddition to 1,3-Diene

5.3.4 Cycloaddition to Alkynes

5.3.5 Insertion Reactions

5.3.6 Rearrangement of Carbenes

5.3.6.1 Wolff Rearrangement

5.3.7 Reactions of Carbenes with Nucleophiles

5.4 Carbenes and Carbene Ligands in Organometallic Chemistry

5.5 Summary

Chapter 6 Nitrenes

6.1 Introduction

6.2 Structure and Reactivity

6.3 Generation of Nitrenes

6.3.1 Azides

6.3.2 Isocyanates

6.3.3 Ylides

6.3.4 Small Rings

6.3.5 Heterocycles

6.3.6 α-Elimination

6.3.7 Reduction of Nitro and Nitroso Compounds

6.3.8 Oxidation of Amines

6.3.9 From Sulfinylamines

6.4 Reactions of Nitrenes

6.4.1 Cycloaddition Reactions of Nitrenes

6.4.1.1 Cycloaddition to Alkenes

6.4.1.2 Cycloaddition to 1,3-Dienes

6.4.1.3 Cycloaddition to Alkynes

6.4.1.4 Cycloaddition to Arenes

6.4.2 Insertion Reactions of Nitrenes

6.4.3 Rearrangement of Nitrenes

6.4.4 Reactions of Nitrenes with Nucleophiles

6.5 Summary

Chapter 7 Miscellaneous Intermediates

7.1 Arynes.

7.1.1 Introduction

7.1.2 Structure and Reactivity

7.1.3 Generation of Arynes

7.1.4 Reactions of Arynes

7.1.4.1 Nucleophilic Addition to Arynes

7.1.4.2 Regiochemistry of the Triple Bond Formation

7.1.4.3 Cycloaddition Reactions of Arynes (Diels-Alder Reaction)

7.1.4.4 1,3-Dipolar Cycloaddition

7.1.5 Uses of Arynes in Organic Synthesis

7.2 Ketenes and Cumulenes

7.2.1 Introduction

7.2.2 Generation of Ketenes

7.2.3 Photochemical Generation of Ketenes

7.2.4 Reactions of Ketenes

7.3 ortho-Quinone Methides

7.4 Zwitterions and Dipoles

7.5 Antiaromatic Systems

7.6 Tetrahedral Intermediates

7.6.1 Acetals and Hemiacetals

7.6.2 Weinreb Amides

7.6.3 Applications in Biomedicine

7.7 Summary

Index.

Notes:

Includes bibliographical references at the end of each chapters and index.

Description based on online resource; title from PDF title page (ebrary, viewed February 6, 2014).

Description based on publisher supplied metadata and other sources.

ISBN:

352767828X

9783527678280

OCLC:

869520228