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Perspectives on Structure and Mechanism in Organic Chemistry

Felix A. Carroll (Author)

9781119808619, Wiley

Hardback, published 26 May 2023

864 pages
28.5 x 22.4 x 5.3 cm, 2.223 kg

PERSPECTIVES ON STRUCTURE AND MECHANISM IN ORGANIC CHEMISTRY

“Beyond the basics” physical organic chemistry textbook, written for advanced undergraduates and beginning graduate students

Based on the author’s first-hand classroom experience, Perspectives on Structure and Mechanism in Organic Chemistry uses complementary conceptual models to give new perspectives on the structures and reactions of organic compounds, with the overarching goal of helping students think beyond the simple models of introductory organic chemistry courses. Through this approach, the text better prepares readers to develop new ideas in the future.

In the 3rd Edition, the author thoroughly updates the topics covered and reorders the contents to introduce computational chemistry earlier and to provide a more natural flow of topics, proceeding from substitution, to elimination, to addition. About 20% of the 438 problems have been either replaced or updated, with answers available in the companion solutions manual.

To remind students of the human aspect of science, the text uses the names of investigators throughout the text and references material to original (or accessible secondary or tertiary) literature as a guide for students interested in further reading.

Sample topics covered in Perspectives on Structure and Mechanism in Organic Chemistry include:

  • Fundamental concepts of organic chemistry, covering atoms and molecules, heats of formation and reaction, bonding models, and double bonds
  • Density functional theory, quantum theory of atoms in molecules, Marcus Theory, and molecular simulations
  • Asymmetric induction in nucleophilic additions to carbonyl compounds and dynamic effects on reaction pathways
  • Reactive intermediates, covering reaction coordinate diagrams, radicals, carbenes, carbocations, and carbanions
  • Methods of studying organic reactions, including applications of kinetics in studying reaction mechanisms and Arrhenius theory and transition state theory

A comprehensive yet accessible reference on the subject, Perspectives on Structure and Mechanism in Organic Chemistry is an excellent learning resource for students of organic chemistry, medicine, and biochemistry. The text is ideal as a primary text for courses entitled Advanced Organic Chemistry at the upper undergraduate and graduate levels.

Preface xi

Chapter 1 Fundamental Models of Organic Chemistry 1

1.1 Atoms and Molecules 1

1.2 Heats of Formation and Reaction 8

1.3 Bonding Models 18

1.4 Complementary Models for the Double Bond 41

1.5 The Role of Complementary Models in Organic Chemistry 46

Problems 47

Chapter 2 Introduction to Computational Chemistry 53

2.1 Hückel Molecular Orbital Theory 53

2.2 Aromaticity 75

2.3 Contemporary Computational Methods 95

2.4 Localized Molecular Orbitals 100

2.5 Density Functional Theory 112

2.6 Another Look at Valence Bond Theory 114

Problems 119

Chapter 3 Stereochemistry 127

3.1 Representations of Three-Dimensional Structures 127

3.2 Stereoisomerism 130

3.3 Physical Manifestations of Chirality 159

3.4 Stereotopicity 167

Problems 172

Chapter 4 Molecular Geometry and Steric Energy 183

4.1 Designation of Molecular Conformation 183

4.2 Conformational Analysis 187

4.3 Molecular Mechanics 204

4.4 Anomeric Effect 221

4.5 Strain and Molecular Stability 225

Problems 237

Chapter 5 Reactive Intermediates 243

5.1 Reaction Coordinate Diagrams 243

5.2 Radicals 244

5.3 Carbenes 263

5.4 Carbocations 272

5.5 Carbanions 290

5.6 Choosing Models of Reactive Intermediates 298

Problems 299

Chapter 6 Determining Reaction Mechanisms 305

6.1 Reaction Mechanisms 305

6.2 Methods to Determine Reaction Mechanisms 306

6.3 Applications of Kinetics in Studying Reaction Mechanisms 319

6.4 Arrhenius Theory and Transition State Theory 326

6.5 Reaction Barriers and Potential Energy Surfaces 337

6.6 Kinetic Isotope Effects 348

6.7 Substituent Effects 363

6.8 Linear Free Energy Relationships 368

Problems 383

Chapter 7 Acid and Base Catalysis of Organic Reactions 393

7.1 Acidity and Basicity of Organic Compounds 393

7.2 Acid and Base Catalysis of Chemical Reactions 413

7.3 Acid and Base Catalysis of Reactions of Carbonyl Compounds and Carboxylic

Problems 441

Chapter 8 Substitution Reactions 449

8.1 Introduction 449

8.2 Nucleophilic Aliphatic Substitution 450

8.3 The SN1 Reaction 453

8.4 The SN2 Reaction 471

8.5 Quantitative Measures of Nucleophilicity 480

8.6 Electrophilic Aromatic Substitution 495

8.7 Nucleophilic Aromatic and Vinylic Substitution 504

8.8 Substitution Involving Benzyne Intermediates 511

8.9 Radical-Nucleophilic Substitution 518

8.10 The Impermanence of Mechanistic Labels 521

Problems 521

Chapter 9 Elimination Reactions 529

9.1 Introduction 529

9.2 Dehydrohalogenation and Related 1,2-Elimination Reactions 534

9.3 Other 1,2-Elimination Reactions 558

Problems 578

Chapter 10 Addition Reactions 587

10.1 Introduction 587

10.2 Addition of Halogens to Alkenes 588

10.3 Other Addition Reactions 618

Problems 656

Chapter 11 Pericyclic Reactions 661

11.1 Introduction 661

11.2 Electrocyclic Transformations 665

11.3 Sigmatropic Reactions 678

11.4 Cycloaddition Reactions 691

11.5 Other Pericyclic Reactions 705

11.6 A General Selection Rule for Pericyclic Reactions 711

11.7 Alternative Conceptual Models for Pericyclic Reactions 713

11.8 Reaction Dynamics and Potential Energy Surfaces 729

Problems 735

Chapter 12 Organic Photochemistry 745

12.1 Energy and Electronic States 745

12.2 Photophysical Processes 747

12.3 Photochemical Kinetics 763

12.4 Physical Properties of Excited States 770

12.5 Representative Photochemical Reactions 777

12.6 Applications of Organic Photochemistry 811

Problems 822

References for Selected Problems 831

Index 837 

Subject Areas: Chemistry [PN]

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