The Proton: Applications to Organic Chemistry

The Proton: Applications to Organic Chemistry deals with several aspects of the proton drawn from organic chemistry.

This book begins with an introductory chapter, followed by discussions on the strengths of neutral organic acids and neutral organic bases. The mode of transfer of hydrogen in its three forms—H+, H•, and H-, alternative sites of protonation or deprotonation of organic compounds, and acid-base chemistry of unstable and metastable species are also elaborated. This text concludes with a presentation of the activation induced in organic molecules by proton addition or removal and its catalytic effects.

This publication is intended for practicing organic chemists and researchers conducting work on protons.

Preface

1 Introduction

I. Water and the Reference State

II. Acid-Base Equilibria: Terms and Symbols

III. Limitations on Water as a Medium for Acid-Base Measurements

References

2 Strengths of Neutral Organic Acids

I. Introduction

II. Oxygen Acids

III. Sulfur Acids

IV. Carbon and Nitrogen Acids

References

3 Strengths of Neutral Organic Bases

I. Introduction

II. Amidines and Guanidines

III. Amines

IV. Amides

V. Oxygen Bases

VI. Carbon Bases

VII. Sulfur Compounds

VIII. Effect of Oxidation State on Basicity

References

4 Proton Transfer, Hydrogen Atom Transfer, and Hydride Transfer

I. Introduction

II. The Geometry of Hydrogen Transfer

III. Hydrogen Isotope Effects as a Criterion of Mechanism in Proton and Hydride Transfer

IV. Competition Among Proton, Hydrogen Atom, and Hydride Transfer Processes

References

5 Alternative Sites of Protonation and Deprotonation

I. Introduction

II. Alternative Sites of Protonation

III. Alternative Sites of Deprotonation

IV. Amphiprotic Systems That Form Zwitterions

References

6 Acidity and Basicity of Unstable and Metastable Organic Species

I. Introduction

II. Organic Free Radicals

III. Electronically Excited States

IV. Tetrahedral Intermediates

References

7 Activation of Organic Molecules by Acids and Bases

I. Introduction

II. Specific Acid and Specific Base Catalysis

III. General Acid and General Base Catalysis

IV. Reactions Conducted under Strongly Acidic or Strong