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(BQ) Part 2 book Introduction to spectroscopy has contents: Ultraviolet spectroscopy, mass spectrometry, combined structure problems, nuclear magnetic resonance spectroscopy. (BQ) Part 2 book Introduction to spectroscopy has contents: Ultraviolet spectroscopy, mass spectrometry, combined structure problems, nuclear magnetic resonance spectroscopy.
Pavia | Lampman | Kriz | Vyvyan Introduction to Spec t ros co p y Gain an understanding of 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 standard for more than 30 years Pavia Lampman Kriz Vyvyan Pavia/Lampman/Kriz/Vyvyan’s Introduction to Spectroscopy, 4e, is a comprehensive resource that provides an unmatched, systematic introduction to spectra and basic theoretical concepts in spectroscopic methods that creates a practical learning resource, 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 techniques alongside DEPT, COSY, and HECTOR Count on this book’s exceptional presentation to provide the comprehensive coverage needed to truly understand today’s spectroscopic techniques Visit us on the Web! a c a d e m i c c e n g a g e c o m /c h e m i s t r y Fourth Edition Introduction to Spectroscopy For your course and learning solutions, visit academic.cengage.com Four th Edition Purchase any of our products at your local college store or at our preferred online store www.ichapters.com 9780495114789_cvr_se.indd 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 Pavia Gary M Lampman George S Kriz James R 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, Fourth Edition Donald L Pavia, Gary M Lampman, George S Kriz, and James R Vyvyan Acquisitions Editor: Lisa Lockwood Development Editor: Brandi Kirksey Editorial Assistant: Elizabeth Woods Technology Project Manager: Lisa Weber © 2009, 2001 Brooks/Cole, Cengage Learning ALL RIGHTS RESERVED No part of this work covered by the copyright herein may be reproduced, transmitted, stored, or used in any form or by any means graphic, electronic, or mechanical, including but not limited to photocopying, recording, scanning, digitizing, taping, Web distribution, information networks, or information storage and retrieval systems, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without the prior written permission of the publisher Marketing Manager: Amee Mosley Marketing Assistant: Elizabeth Wong Marketing Communications Manager: Talia Wise Project Manager, Editorial Production: Michelle Cole For product information and technology assistance, contact us at Cengage Learning Customer & Sales Support, 1-800-354-9706 For permission to use material from this text or product, submit all requests online at cengage.com/permissions Further permissions questions can be e-mailed to permissionrequest@cengage.com Creative Director: Rob Hugel Art Director: John Walker Print Buyer: Paula Vang Permissions Editor: Bob Kauser Production Service: PrePress PMG Photo Researcher: Susan Lawson Copy Editor: Kathleen Brown Cover Designer: Dare Porter Cover Image: Eddie Gerald/Alamy Library of Congress Control Number: 2007943966 ISBN-13: 978-0-495-11478-9 ISBN-10: 0-495-11478-2 Brooks/Cole 10 Davis Drive Belmont, CA 94002-3098 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.cengage.com/region Cengage Learning products are represented in Canada by Nelson Education, Ltd For your course and learning solutions, visit academic.cengage.com Purchase any of our products at your local college store or at our preferred online store www.ichapters.com Printed in the United States of America 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 previous editions, we have tried to focus on the important aspects of each spectroscopic technique without 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 supplement 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 Explanations 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 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 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 6.19 and 6.20 A new section on determining the relative and absolute stereochemical configuration 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 bombardment (FAB), matrix-assisted laser desorption ionization (MALDI), and electrospray techniques Different types of mass analyzers are described as well Fragmentation in mass spectrometry is discussed 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 problems, so that students can develop skill in solving spectroscopy problems v 14782_FM_i-xvi pp3.qxd vi 2/7/08 9:11 AM Page 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 students 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 Pavia Gary M Lampman George S Kriz James R Vyvyan 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page vii CONTENTS CHAPTER MOLECULAR FORMULAS AND WHAT CAN BE LEARNED FROM THEM 1.1 1.2 1.3 1.4 1.5 1.6 Elemental Analysis and Calculations Determination of Molecular Mass Molecular Formulas Index of Hydrogen Deficiency The Rule of Thirteen A Quick Look Ahead to Simple Uses of Mass Spectra Problems 13 References 14 12 CHAPTER INFRARED SPECTROSCOPY 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 15 The Infrared Absorption Process 16 Uses of the Infrared Spectrum 17 The Modes of Stretching and Bending 18 Bond Properties and Absorption Trends 20 The Infrared Spectrometer 23 A Dispersive Infrared Spectrometers 23 B Fourier Transform Spectrometers 25 Preparation of Samples for Infrared Spectroscopy 26 What to Look for When Examining Infrared Spectra 26 Correlation Charts and Tables 28 How to Approach the Analysis of a Spectrum (Or What You Can Tell at a Glance) 30 vii 14782_FM_i-xvi pp3.qxd viii 2/7/08 9:11 AM Page viii Contents 2.10 2.11 2.12 2.13 2.14 2.15 2.16 2.17 2.18 2.19 2.20 2.21 2.22 Hydrocarbons: Alkanes, Alkenes, and Alkynes 31 A Alkanes 31 B Alkenes 33 C Alkynes 35 Aromatic Rings 43 Alcohols and Phenols 47 Ethers 50 Carbonyl Compounds 52 A Factors that Influence the CJO Stretching Vibration B Aldehydes 56 C Ketones 58 D Carboxylic Acids 62 E Esters 64 F Amides 70 G Acid Chlorides 72 H Anhydrides 73 Amines 74 Nitriles, Isocyanates, Isothiocyanates, and Imines 77 Nitro Compounds 79 Carboxylate Salts, Amine Salts, and Amino Acids 80 Sulfur Compounds 81 Phosphorus Compounds 84 Alkyl and Aryl Halides 84 The Background Spectrum 86 Problems 88 References 104 54 CHAPTER NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART ONE: BASIC CONCEPTS 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 105 Nuclear Spin States 105 Nuclear Magnetic Moments 106 Absorption of Energy 107 The Mechanism of Absorption (Resonance) 109 Population Densities of Nuclear Spin States 111 The Chemical Shift and Shielding 112 The Nuclear Magnetic Resonance Spectrometer 114 A The Continuous-Wave (CW) Instrument 114 B The Pulsed Fourier Transform (FT) Instrument 116 Chemical Equivalence—A Brief Overview 120 14782_FM_i-xvi pp3.qxd 2/7/08 9:11 AM Page ix Contents 3.9 3.10 3.11 3.12 3.13 3.14 3.15 3.16 3.17 3.18 3.19 ix Integrals and Integration 121 Chemical Environment and Chemical Shift 123 Local Diamagnetic Shielding 124 A Electronegativity Effects 124 B Hybridization Effects 126 C Acidic and Exchangeable Protons; Hydrogen Bonding 127 Magnetic Anisotropy 128 Spin–Spin Splitting (n + 1) Rule 131 The Origin of Spin–Spin Splitting 134 The Ethyl Group (CH3CH2I) 136 Pascal’s Triangle 137 The Coupling Constant 138 A Comparison of NMR Spectra at Low- and High-Field Strengths 141 Survey of Typical H NMR Absorptions by Type of Compound 142 A Alkanes 142 B Alkenes 144 C Aromatic Compounds 145 D Alkynes 146 E Alkyl Halides 148 F Alcohols 149 G Ethers 151 H Amines 152 I Nitriles 153 J Aldehydes 154 K Ketones 156 L Esters 157 M Carboxylic Acids 158 N Amides 159 O Nitroalkanes 160 Problems 161 References 176 CHAPTER NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY PART TWO: CARBON-13 SPECTRA, INCLUDING HETERONUCLEAR COUPLING WITH OTHER NUCLEI 177 4.1 4.2 4.3 The Carbon-13 Nucleus 177 Carbon-13 Chemical Shifts 178 A Correlation Charts 178 B Calculation of 13C Chemical Shifts 180 13 Proton-Coupled C Spectra—Spin–Spin Splitting of Carbon-13 Signals 181 14782_06_Ch6_p329-380.pp3.qxd 366 2/7/08 4:20 PM Page 366 Nuclear Magnetic Resonance Spectroscopy • Part Four The proton NMR spectrum of a compound with formula C5H10O is shown The peak at 2.1 ppm is solvent dependent The infrared spectrum shows a broad and strong peak at 3332 cm−1 The normal carbon-13, DEPT-135, and DEPT-90 spectra data are tabulated Normal Carbon 10 DEPT-135 DEPT-90 11 ppm Negative No peak 18 No peak No peak 21 Positive No peak 71 Negative No peak Determine the structure of the aromatic compound with formula C9H9ClO3 The infrared spectrum shows a very broad band from 3300 to 2400 cm−1 and a strong band at 1714 cm−1 The full proton NMR spectrum and expansions are provided The compound is prepared by a nucleophilic substitution reaction of the sodium salt of 3-chlorophenol on a halogen-bearing substrate Offset: 1.4 ppm 10 7.25 Page 367 2155.72 8:15 AM 2163.81 2/6/08 2171.90 14782_06_Ch6_p329-380.pp3.qxd 7.20 7.15 7.10 7.05 7.00 6.95 6.90 6.85 6.80 6.75 4.85 4.80 4.75 (ppm) 4.70 4.85 496.74 503.72 1425.13 1431.75 1438.74 1445.72 (ppm) 4.80 (ppm) 4.75 14782_06_Ch6_p329-380.pp3.qxd 368 2/7/08 4:20 PM Page 368 Nuclear Magnetic Resonance Spectroscopy • Part Four *9 Determine the structure of a compound with formula C10H15N The proton NMR spectrum is shown The infrared spectrum has medium bands at 3420 and 3349 cm−1 and a strong band at 1624 cm−1 The broad peak at 3.5 ppm in the NMR shifts when DCl is added, while the other peaks stay in the same positions triplet doublets triplet sextet quintet 10 *10 Determine the structure of a compound with formula C6H5Br2N The proton NMR spectrum is shown The infrared spectrum has medium bands at 3420 and 3315 cm−1 and a strong band at 1612 cm−1 The normal carbon, DEPT-135, and DEPT-90 spectra data are tabulated Normal Carbon DEPT-135 DEPT-90 109 ppm No peak No peak 119 Positive Positive 132 Positive Positive 142 No peak No peak doublet triplet 10 14782_06_Ch6_p329-380.pp3.qxd 2/7/08 4:21 PM Page 369 369 Problems 11 There are three spectra shown in this problem along with three structures of aromatic primary amines Assign each spectrum to the appropriate structure You should calculate the approximate chemical shifts (Appendix 6) and use these values along with the appearance and position of the peaks (singlet and doublets) to assign the correct structure NH2 NH2 NH2 CH3 NO2 CH3 NO2 CH3 NO2 NH2 10 6 5 NH2 10 NH2 10 14782_06_Ch6_p329-380.pp3.qxd 370 2/6/08 8:15 AM Page 370 Nuclear Magnetic Resonance Spectroscopy • Part Four *12 When aniline is chlorinated, a product with the formula C6H5NCl2 is obtained The spectrum of this compound is shown The expansions are labeled to indicate couplings, in Hertz Determine the structure and substitution pattern of the compound and assign each set of peaks Explain the splitting patterns 300 MHz 10 2.3 Hz 8.6 Hz Small splittings 2.3 Hz 7.23 ppm 7.02 ppm 6.65 ppm *13 A naturally occurring amino acid with the formula C3H7NO2 gives the following proton NMR spectrum when determined in deuterium oxide solvent The amino and carboxyl protons merge into a single peak at 4.9 ppm in the D2O solvent (not shown); the peaks of each multiplet are separated by Hz Determine the structure of this amino acid 14782_06_Ch6_p329-380.pp3.qxd 2/7/08 4:21 PM Page 371 371 Problems 4.4 4.3 4.2 4.1 4.0 3.9 3.8 3.7 3.6 3.5 3.4 3.3 3.2 3.1 3.0 2.9 2.8 2.7 2.6 2.5 2.4 2.3 2.2 2.1 2.0 1.9 1.8 1.7 1.6 1.5 (ppm) 14 Determine the structure of a compound with formula C7H9N The proton NMR spectrum is shown, along with expansions of the region from 7.10 to 6.60 ppm The three-peak pattern for the two protons at about ppm involves overlapping peaks The broad peak at 3.5 ppm shifts when DCl is added, while the other peaks stay in the same positions The infrared spectrum shows a pair of peaks near 3400 cm−1 and an out-of-plane bending band at 751 cm−1 10 14782_06_Ch6_p329-380.pp3.qxd 372 2/7/08 4:21 PM Page 372 Nuclear Magnetic Resonance Spectroscopy • Part Four 7.10 7.00 6.90 6.80 6.70 6.60 (ppm) 15 A naturally occurring amino acid with the formula C9H11NO3 gives the following proton NMR spectrum when determined in deuterium oxide solvent with DCl added The amino, carboxyl, and hydroxyl protons merge into a single peak at 5.1 ppm (4 H) in D2O Determine the structure of this amino acid and explain the pattern that appears in the range 3.17 to 3.40 ppm, including coupling constants 10 I I I I I I I j I I I I j I I I I j I I I I j I I 11 j 11 7.10 7.00 I I 6.90 I I I I I 4.50 (ppm) I 1313.71 1319.46 I I I I j II I I j I I I I j I I 4.40 (ppm) II II I I I I I I I I I I I I 959.48 I I I I 966.99 I 7.20 974.18 I I I I 981.69 I 996.71 I I I I 1002.14 I 7.30 1011.41 I I I I I II I I 1016.84 I 1326.65 Page 373 2084.95 8:15 AM 2093.42 2/6/08 2176.83 2185.45 14782_06_Ch6_p329-380.pp3.qxd i I I I I I j I I I I j I I I I j I I I I j I I iljl 3.40 3.30 (ppm) 3.20 4.30 14782_06_Ch6_p329-380.pp3.qxd 374 2/7/08 4:22 PM Page 374 Nuclear Magnetic Resonance Spectroscopy • Part Four 16 Determine the structure of a compound with formula C6H10O2 The proton NMR spectrum with expansions is provided Comment regarding why the proton appearing at 6.91 ppm is a triplet of quartets, with spacing of 1.47 Hz Also comment on the “singlet” at 1.83 that shows fine structure The normal carbon, DEPT-135, and DEPT-90 spectral results are tabulated Normal Carbon DEPT-135 DEPT-90 Positive No peak 13 Positive No peak 22 Negative No peak 127 No peak No peak 147 Positive Positive 174 No peak No peak 12 ppm Offset: 2.7 ppm 10 1.86 1.84 (ppm) 6.86 1.82 6.88 1.80 6.86 2.28 2.26 1.10 (ppm) 2.24 1.08 2.22 (ppm) 1.06 2.20 1.04 651.90 650.80 666.97 659.25 666.97 665.87 674.33 673.59 682.05 680.95 8:15 AM 311.43 6.82 2070.05 2068.94 2067.47 2066.00 2077.77 2076.30 2074.83 2073.36 2/6/08 319.15 6.94 326.50 6.96 551.15 549.68 2085.12 2083.65 2082.18 2080.71 14782_06_Ch6_p329-380.pp3.qxd Page 375 (ppm) 2.18 1.02 2.16 14782_06_Ch6_p329-380.pp3.qxd 376 2/6/08 8:15 AM Page 376 Nuclear Magnetic Resonance Spectroscopy • Part Four 17 The following proton NMR spectrum is of a discontinued analgesic drug, phenacetin (C10H13NO2) Phenacetin is structurally related to the very popular and current analgesic drug acetaminophen Phenacetin contains an amide functional group Two tiny impurity peaks appear near 3.4 and 8.1 ppm Give the structure of this compound and interpret the spectrum 300 MHz 7.5 7.4 7.3 7.2 7.1 (ppm) 7.0 6.9 6.8 6.7 4.1 4.0 426.14 419.16 412.17 1210.78 1203.79 1196.80 1189.82 10 3.9 (ppm) 3.8 1.5 1.4 1.3 (ppm) 1.2 14782_06_Ch6_p329-380.pp3.qxd 2/6/08 8:15 AM Page 377 Problems 18 The proton NMR spectrum shown in this problem is for a common insect repellent, N,N-diethyl-m-toluamide, determined at 360 K This problem also shows a stacked plot of this compound determined in the temperature range of 290 to 360 K (27–87°C) Explain why the spectrum changes from two pairs of broadened peaks near 1.2 and 3.4 ppm at low temperature to a triplet and quartet at the higher temperatures 6H 3H 4H 7.5 4H 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 (ppm) 360K 350 340 330 310 290 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 (ppm) 2.0 1.8 1.6 1.4 1.2 1.0 0.8 377 14782_06_Ch6_p329-380.pp3.qxd 378 2/7/08 4:22 PM Page 378 Nuclear Magnetic Resonance Spectroscopy • Part Four 19 The proton NMR spectral information shown in this problem is for a compound with formula C4H7Cl Expansions are shown for each of the unique protons The original “quintet” pattern centering on 4.52 ppm is simplified to a doublet by irradiating (decoupling) the protons at 1.59 ppm (see Section 6.10) In another experiment, decoupling the proton at 4.52 ppm simplifies the original pattern centering on 5.95 ppm to the four-peak pattern shown The doublet at 1.59 ppm becomes a singlet when the proton at 4.52 ppm is irradiated (decoupled) Determine the coupling constants and draw the structure of this compound Notice that there are 2J, 3J, and 4J couplings present in this compound Draw a tree diagram for the proton at 5.95 ppm (nondecoupled) and explain why irradiation of the proton at 4.52 ppm simplified the pattern Assign each of the peaks in the spectrum 5.28 5.24 5.20 5.16 (ppm) 5.12 5.08 1.64 1.60 (ppm) 475.04 481.66 1525.51 1524.78 1523.67 1535.81 1534.70 1533.97 1568.90 1567.79 1567.06 1585.81 1584.71 1583.97 10 1.56 6.00 5.96 5.92 5.88 4.56 4.52 (ppm) 5.92 4.56 1355.28 1362.64 irradiation of proton at 1.59 ppm 1775.17 1785.09 1802.01 1792.08 5.96 (ppm) 4.48 (ppm) irradiation of proton at 4.52 ppm 6.00 1342.77 1349.39 1356.75 1363.36 1369.98 Page 379 1768.92 1776.27 8:15 AM 1778.84 1785.83 2/6/08 1793.18 1795.76 1803.48 14782_06_Ch6_p329-380.pp3.qxd 4.52 (ppm) 4.48 14782_06_Ch6_p329-380.pp3.qxd 380 2/6/08 8:15 AM Page 380 Nuclear Magnetic Resonance Spectroscopy • Part Four 20 In Problem 11, calculations proved to be a good way of assigning structures to the spectra of some aromatic amines Describe an experimental way of differentiating between the following amines: NH2 NH2 CH3 NO2 NO2 CH3 *21 At room temperature, the NMR spectrum of cyclohexane shows only a single resonance peak As the temperature of the sample is lowered, the sharp single peak broadens until at −66.7°C it begins to split into two peaks, both broad As the temperature is lowered further to −100°C, each of the two broad bands begins to give a splitting pattern of its own Explain the origin of these two families of bands *22 In cis-1-bromo-4-tert-butylcyclohexane, the proton on carbon-4 is found to give resonance at 4.33 ppm In the trans isomer, the resonance of the C4 hydrogen is at 3.63 ppm Explain why these compounds should have different chemical shift values for the C4 hydrogen Can you explain the fact that this difference is not seen in the 4-bromomethylcyclohexanes except at very low temperature? REFERENCES Crews, P., J Rodriguez, and M Jaspars, Organic Structure Analysis, Oxford University Press, New York, 1998 Friebolin, H., Basic One- and Two-Dimensional NMR Spectroscopy, 3rd ed., Wiley-VCH, New York, 1998 Gotlieb, H E., V Kotlyar, and A Nudelman “NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities,” Journal of Organic Chemistry 62 (1997): 7512–7515 Gunther, H., NMR Spectroscopy, 2nd ed., John Wiley and Sons, New York, 1995 Jackman, L M., and S Sternhell, Applications of Nuclear Magnetic Resonance Spectroscopy in Organic Chemistry, 2nd ed., Pergamon Press, London, 1969 Lambert, J B., H F Shurvell, D A Lightner, and R G Cooks, Organic Structural Spectroscopy, Prentice Hall, Upper Saddle River, NJ, 1998 Macomber, R S., NMR Spectroscopy—Essential Theory and Practice, College Outline Series, Harcourt, Brace Jovanovich, New York, 1988 Macomber, R S., A Complete Introduction to Modern NMR Spectroscopy, John Wiley and Sons, New York, 1997 Pople, J A., W C Schneider, and H J Bernstein, High Resolution Nuclear Magnetic Resonance, McGraw–Hill, New York, 1969 Pouchert, C and J Behnke, Aldrich Library of 13C and 1H FTNMR Spectra, Aldrich Chemical Co., Milwaukee, WI, 1993 Rothchild, R., “NMR Methods for Determination of Enantiomeric Excess,” Enantiomer (2000): 457–471 Rychnovsky, S D., B N Rogers, and G Yang, “Analysis of Two Carbon-13 NMR Correlations for Determining the Stereochemistry of 1,3-Diol Acetonides,” Journal of Organic Chemistry 58 (1993): 3511–3515 Rychnovsky, S D., B N Rogers, and T I Richardson, “Configurational Assignment of Polyene Macrolide Antibiotics Using the [13C] Acetonide Analysis,” Accounts of Chemical Research 31 (1998): 9–17 Sanders, J K M., and B K Hunter, Modern NMR Spectroscopy—A Guide for Chemists, 2nd ed., Oxford University Press, Oxford, England, 1993 Seco, J M., E Quinoa, and R Riguera, “The Assignment of Absolute Configuration by NMR,” Chemical Reviews 104 (2004): 17–117 and references therein Silverstein, R M., F X Webster, and D J Kiemle, Spectrometric Identification of Organic Compounds, 7th ed., John Wiley and Sons, New York, 2005 Yoder, C H., and C D Schaeffer, Introduction to Multinuclear NMR, Benjamin–Cummings, Menlo Park, CA, 1987 In addition to these references, also consult textbook references, compilations of spectra, computer programs, and NMR-related Internet addresses cited at the end of Chapter ... acyclic, saturated compound: C2H6, C2H6O, C C H H H H C C H H –2H C2H6O2, C (also compare –4H C C CHOH to H2C CH2 C O) C CH2 H 2C C2H6O3 CH2 CH2 H CH2 H –2H H2C CH2 CH2 H2C CH2 F I G U R E Formation... excess O2 ⎯→ 9.83 mg x CO2 + y /2 H2O 23 .26 mg 9. 52 mg 23 .26 mg CO2 = 0. 528 5 mmoles CO2 millimoles CO2 = ᎏᎏ 44.01 mg/mmole mmoles CO2 = mmoles C in original sample (0. 528 5 mmoles C)( 12. 01 mg/mmole... 147 82_ FM_i-xvi pp3.qxd viii 2/ 7/08 9:11 AM Page viii Contents 2. 10 2. 11 2. 12 2.13 2. 14 2. 15 2. 16 2. 17 2. 18 2. 19 2. 20 2. 21 2. 22 Hydrocarbons: Alkanes, Alkenes, and Alkynes 31 A Alkanes 31 B Alkenes