Pavia Lampman Gain an understanding of Kriz Pavia | Lampman | Kriz | Vyvyan Vyvyan t h e l a t e s t a d va n c e s i n s p e c t r o s c o p y w i t h t h e t e x t t h a t ’s s e t t h e u n r i va l e d Spec t ros co p y standard for more than 30 years. Introduction to Pavia/Lampman/Kriz/Vyvyan’s Introduction to Spectroscopy, 4e, is a comprehensive resource that provides an unmatched, sys- tematic introduction to spectra and basic theoretical concepts in spectroscopic methods that creates a practical learning re- source, whether you’re an introductory student or someone who needs a reliable reference text on spectroscopy. This well-rounded introduction features updated spectra, a modernized presentation of one-dimensional Nuclear Magnetic Resonance (NMR) spectroscopy, the introduction of biological molecules in mass spectrometry, and inclusion of modern tech- niques alongside DEPT, COSY, and HECTOR. Count on this book’s exceptional presentation to provide the comprehensive cover- age needed to truly understand today’s spectroscopic techniques.
Visit us on the Web! Fourth a c a d e m i c. c o m /c h e m i s t r y Edition Introduction to For your course and learning solutions, visit academic.com Spectroscopy Four th Edition Purchase any of our products at your local college store or at our preferred online store www.com 9780495114789_cvr_se.indd 1 40 AM 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page i F O U R T H E D I T I O N INTRODUCTION TO SPECTROSCOPY Donald L. Vyvyan Department of Chemistry Western Washington University Bellingham, Washington Australia • Brazil • Japan • Korea • Mexico • Singapore • Spain • United Kingdom • United States 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page ii 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page iii TO ALL OF OUR “O-SPEC” STUDENTS 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page iv Introduction to Spectroscopy, © 2009, 2001 Brooks/Cole, Cengage Learning Fourth Edition ALL RIGHTS RESERVED. No part of this work covered by the copyright Donald L.
Lampman, herein may be reproduced, transmitted, stored, or used in any form George S. Kriz, and James R. Vyvyan or by any means graphic, electronic, or mechanical, including but not Acquisitions Editor: Lisa Lockwood limited to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval Development Editor: Brandi Kirksey systems, except as permitted under Section 107 or 108 of the 1976 Editorial Assistant: Elizabeth Woods United States Copyright Act, without the prior written permission of Technology Project Manager: Lisa Weber the publisher. Marketing Manager: Amee Mosley For product information and technology assistance, contact us at Marketing Assistant: Elizabeth Wong Cengage Learning Customer & Sales Support, 1-800-354-9706 Marketing Communications Manager: Talia Wise For permission to use material from this text or product, submit all requests online at cengage.com/permissions Project Manager, Editorial Production: Further permissions questions can be e-mailed to Michelle Cole permissionrequest@cengage.com Creative Director: Rob Hugel Art Director: John Walker Library of Congress Control Number: 2007943966 Print Buyer: Paula Vang ISBN-13: 978-0-495-11478-9 Permissions Editor: Bob Kauser ISBN-10: 0-495-11478-2 Production Service: PrePress PMG Photo Researcher: Susan Lawson Brooks/Cole Copy Editor: Kathleen Brown 10 Davis Drive Cover Designer: Dare Porter Belmont, CA 94002-3098 Cover Image: Eddie Gerald/Alamy USA Compositor: PrePress PMG Cengage Learning is a leading provider of customized learning solutions with office locations around the globe, including Singapore, the United Kingdom, Australia, Mexico, Brazil, and Japan.
Locate your local office at international.com/region Cengage Learning products are represented in Canada by Nelson Education, Ltd. For your course and learning solutions, visit academic.com Purchase any of our products at your local college store or at our preferred online store www.com Printed in the United States of America 1 2 3 4 5 6 7 12 11 10 09 08 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page v PREFACE T his is the fourth edition of a textbook in spectroscopy intended for students of organic chemistry. Our textbook can serve as a supplement for the typical organic chemistry lecture textbook, and it can also be used as a “stand-alone” textbook for an advanced undergraduate course in spectroscopic methods of structure determination or for a first-year graduate course in spectroscopy. This book is also a useful tool for students engaged in research.
Our aim is not only to teach students to interpret spectra, but also to present basic theoretical concepts. As with the previ- ous editions, we have tried to focus on the important aspects of each spectroscopic technique with- out dwelling excessively on theory or complex mathematical analyses. This book is a continuing evolution of materials that we use in our own courses, both as a supple- ment to our organic chemistry lecture course series and also as the principal textbook in our upper division and graduate courses in spectroscopic methods and advanced NMR techniques. Explana- tions and examples that we have found to be effective in our courses have been incorporated into this edition.
This fourth edition of Introduction to Spectroscopy contains some important changes. The discussion of coupling constant analysis in Chapter 5 has been significantly expanded. Long-range couplings are covered in more detail, and multiple strategies for measuring coupling constants are presented. Most notably, the systematic analysis of line spacings allows students (with a little practice) to extract all of the coupling constants from even the most challenging of first-order multiplets.
Chapter 5 also includes an expanded treatment of group equivalence and diastereotopic systems. Discussion of solvent effects in NMR spectroscopy is discussed more explicitly in Chapter 6, and the authors thank one of our graduate students, Ms. Natalia DeKalb, for acquiring the data in Figures 6. A new section on determining the relative and absolute stereochemical con- figuration with NMR has also been added to this chapter.
The mass spectrometry section (Chapter 8) has been completely revised and expanded in this edition, starting with more detailed discussion of a mass spectrometer’s components. All of the common ionization methods are covered, including chemical ionization (CI), fast-atom bombard- ment (FAB), matrix-assisted laser desorption ionization (MALDI), and electrospray techniques. Different types of mass analyzers are described as well. Fragmentation in mass spectrometry is dis- cussed in greater detail, and several additional fragmentation mechanisms for common functional groups are illustrated.
Numerous new mass spectra examples are also included. Problems have been added to each of the chapters. We have included some more solved prob- lems, so that students can develop skill in solving spectroscopy problems. v 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page vi vi Preface The authors are very grateful to Mr.
Charles Wandler, without whose expert help this project could not have been accomplished. We also acknowledge numerous contributions made by our stu- dents who use the textbook and who provide us careful and thoughtful feedback. We wish to alert persons who adopt this book that answers to all of the problems are available on line from the publisher. Authorization to gain access to the web site may be obtained through the local Cengage textbook representative.
Finally, once again we must thank our wives, Neva-Jean, Marian, Carolyn, and Cathy for their support and their patience. They endure a great deal in order to support us as we write, and they deserve to be part of the celebration when the textbook is completed! Donald L. Vyvyan 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page vii CONTENTS CHAPTER 1 MOLECULAR FORMULAS AND WHAT CAN BE LEARNED FROM THEM 1 1.1 Elemental Analysis and Calculations 1 1.2 Determination of Molecular Mass 5 1.4 Index of Hydrogen Deficiency 6 1.5 The Rule of Thirteen 9 1.6 A Quick Look Ahead to Simple Uses of Mass Spectra 12 Problems 13 References 14 CHAPTER 2 INFRARED SPECTROSCOPY 15 2.1 The Infrared Absorption Process 16 2.2 Uses of the Infrared Spectrum 17 2.3 The Modes of Stretching and Bending 18 2.4 Bond Properties and Absorption Trends 20 2.5 The Infrared Spectrometer 23 A. Dispersive Infrared Spectrometers 23 B.
Fourier Transform Spectrometers 25 2.6 Preparation of Samples for Infrared Spectroscopy 26 2.7 What to Look for When Examining Infrared Spectra 26 2.8 Correlation Charts and Tables 28 2.9 How to Approach the Analysis of a Spectrum (Or What You Can Tell at a Glance) 30 vii 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page viii viii Contents 2.10 Hydrocarbons: Alkanes, Alkenes, and Alkynes 31 A.12 Alcohols and Phenols 47 2. Factors that Influence the CJO Stretching Vibration 54 B.16 Nitriles, Isocyanates, Isothiocyanates, and Imines 77 2.18 Carboxylate Salts, Amine Salts, and Amino Acids 80 2.21 Alkyl and Aryl Halides 84 2.22 The Background Spectrum 86 Problems 88 References 104 CHAPTER 3 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART ONE: BASIC CONCEPTS 105 3.1 Nuclear Spin States 105 3.2 Nuclear Magnetic Moments 106 3.3 Absorption of Energy 107 3.4 The Mechanism of Absorption (Resonance) 109 3.5 Population Densities of Nuclear Spin States 111 3.6 The Chemical Shift and Shielding 112 3.7 The Nuclear Magnetic Resonance Spectrometer 114 A. The Continuous-Wave (CW) Instrument 114 B. The Pulsed Fourier Transform (FT) Instrument 116 3.8 Chemical Equivalence—A Brief Overview 120 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page ix Contents ix 3.9 Integrals and Integration 121 3.10 Chemical Environment and Chemical Shift 123 3.11 Local Diamagnetic Shielding 124 A.
Acidic and Exchangeable Protons; Hydrogen Bonding 127 3.13 Spin–Spin Splitting (n + 1) Rule 131 3.14 The Origin of Spin–Spin Splitting 134 3.15 The Ethyl Group (CH3CH2I) 136 3.17 The Coupling Constant 138 3.18 A Comparison of NMR Spectra at Low- and High-Field Strengths 141 1 3.19 Survey of Typical H NMR Absorptions by Type of Compound 142 A. Nitroalkanes 160 Problems 161 References 176 CHAPTER 4 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART TWO: CARBON-13 SPECTRA, INCLUDING HETERONUCLEAR COUPLING WITH OTHER NUCLEI 177 4.1 The Carbon-13 Nucleus 177 4.2 Carbon-13 Chemical Shifts 178 A. Calculation of 13C Chemical Shifts 180 13 4.3 Proton-Coupled C Spectra—Spin–Spin Splitting of Carbon-13 Signals 181 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page x x Contents 4.4 Proton-Decoupled 13C Spectra 183 4.5 Nuclear Overhauser Enhancement (NOE) 184 4.6 Cross-Polarization: Origin of the Nuclear Overhauser Effect 186 13 4.7 Problems with Integration in C Spectra 189 4.8 Molecular Relaxation Processes 190 4.9 Off-Resonance Decoupling 192 4.10 A Quick Dip into DEPT 192 4.11 Some Sample Spectra—Equivalent Carbons 195 4.12 Compounds with Aromatic Rings 197 4.13 Carbon-13 NMR Solvents—Heteronuclear Coupling of Carbon to Deuterium 199 4.14 Heteronuclear Coupling of Carbon-13 to Fluorine-19 203 4.15 Heteronuclear Coupling of Carbon-13 to Phosphorus-31 204 4.16 Carbon and Proton NMR: How to Solve a Structure Problem 206 Problems 210 References 231 CHAPTER 5 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART THREE: SPIN–SPIN COUPLING 233 5.1 Coupling Constants: Symbols 233 5.2 Coupling Constants: The Mechanism of Coupling 234 1 A. One-Bond Couplings ( J) 235 B.
Two-Bond Couplings (2J) 236 3 C. Three-Bond Couplings ( J) 239 4 n D. Long-Range Couplings ( J– J) 244 5.4 Spectra of Diastereotopic Systems 252 A. Diastereotopic Methyl Groups: 4-Methyl-2-pentanol 252 B.
Diastereotopic Hydrogens: 4-Methyl-2-pentanol 254 5.5 Nonequivalence within a Group—The Use of Tree Diagrams when the n + 1 Rule Fails 257 5.6 Measuring Coupling Constants from First-Order Spectra 260 A. Simple Multiplets—One Value of J (One Coupling) 260 B. Is the n + 1 Rule Ever Really Obeyed? 262 C. More Complex Multiplets—More Than One Value of J 264 5.7 Second-Order Spectra—Strong Coupling 268 A.
First-Order and Second-Order Spectra 268 B. Spin System Notation 269 C. The A2, AB, and AX Spin Systems 270 D. A2X2 Spin Systems 270 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page xi Contents xi E.
Simulation of Spectra 272 F. The Absence of Second-Order Effects at Higher Field 272 G. Deceptively Simple Spectra 273 5.9 Measuring Coupling Constants—Analysis of an Allylic System 281 5.10 Aromatic Compounds—Substituted Benzene Rings 285 A. para-Disubstituted Rings 288 C.11 Coupling in Heteroaromatic Systems 293 Problems 296 References 328 CHAPTER 6 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART FOUR: OTHER TOPICS IN ONE-DIMENSIONAL NMR 329 6.1 Protons on Oxygen: Alcohols 329 6.