Spectrometric Identification of Organic Compounds Sixth Edition Robert M. Silverstein Francis X. Webster State University of New York College of Environmental Science & Forestry ® John Wiley & Sons, Inc.PREFACE The authors welcome this opportunity to include new ‘material, discard the old, and improve the presentation. Overall, the following major items are noteworthy: + The continuing advances in NMR spectrometry are acknowledged by major revisions in three NMR chapters and by the addition of a fourth NMR chap- ter entitled “Spectrometry of Other Important Nu- clei.” + Spectra have been upgraded throughout —the NMR spectra in particular; almost all were run at 300 or 500 MHz (75.5 and 126.0 MHz for "C), and the "H peaks have been expanded as insets. + An overall List of Spectra has been added to the Contents. Detailed explanations have been added to the more complicated tables and charts throughout. The thorough Index provides accessibility; acronyms are included. New end-of-chapter problems have been adde + Asaconsequence of the advances in NMR, UV spec- trometry has been further marginalized for our pur- poses, and the UV chapter has been dropped —a dif- ficult decision (nostalgia perhaps) because UV spectrometry is widely used for other purposes. Stu- dents should understand the relationship between absorption of visible-UV frequencies and molecular structure. But such general understanding is pre- sented in most first-year organic texts, We cannot jus- tify 26 pages of text and tables (0 describe a tech- nique that is outmoded for structure elucidation and, in practice, virtually abandoned except for special sit- vations. Major changes in each chapter are summarized be- low. Mass Spectrometry (Chapter 2) Recent advances in instrumentation and ionization techniques are described briefly. Several sections have been rewritten and expanded for greater clarity. The useful Table of Formula Masses (four decimal places) has been shortened by eliminating entries that are un- likely in the present context, The Table is convenient for selecting tentative molecular formulas and frag- ments on the basis of unit-mass peaks. Given high- resolution peaks, specific molecular or fragment form- ulas can be selected Infrared Spectrometry (Chapter 3) Modifications have been made in the full chart of char- acteristic absorptions. A simplified chart of common functional groups has also been included for rapid scan- ning. Students are advised to start with the simplified chart and to avoid the full chart until further leads are obtained from the mass and NMR spectra Proton Magnetic Resonance Spectrometry (Chapter 4) This chapter has been extensively revised and expanded to clarify difficult concepts because the narrow discrete peaks of a high-resolution proton NMR are subject to interpretation in detail by inspection, NMR, without question, has become the most use ful tool available to the organic chemist. It is possible to interpret the 300 MHz and 500 MHz spectra (with expanded insets), presented throughout the book, ine quisite detail. But to do so requires an appreciation of the relationship between chemical structure and spec- tra—which means to understand how a spectrum is pro- duced and what its promises and limitations are. We realize that the organic chemist wants to get on with the task of identifying compounds without first mastering arcane areas of electronic engincering and quantum mechanies. But the alternative “black box” ap- proach is not acceptable either. We believe that a pic- torial, nonmathematical approach to spectra has been satisfactory for our purposes through five editions, We propose that elaboration of the same approach—to- gether with coverage of current techniques—will be welcomed in the Sixth Edition. The undergraduate stu- dent will be engaged, and the graduate student chal- lenged. : The following fevisions are noted: + Interpretation of NMR spectra depends on the con- cept of chemical-shift equivalence, an understanding of which depends on stereochemical concepts; these are reviewed with special emphasis on interchange through symmetry operations within the molecule, and through rapid structural changes. + For pedagogical and practical reasons, this chapter treats only protons. !\C NMR spectrometry is treated in Chapter 5, and other useful nuclei are treated in Chapter 7. Chapter 6 is devoted to 2-D NMR. + Pulsed Fourier transform spectrometry follows theiv Preface brief discussion of the more intuitively obvious con- tinuous-wave scanning NMR. + Although “chirality” is mentioned in the stereo- chemistry discussion, it warrants a separate section. + “Virtual coupling” is always a challenge for stu- dents—and for teachers and authors. We have given it appropriate emphasis. + A separate section is devoted to the concept of mag netic equivalence. + The utility of NOE difference spectrometry for ster- cochemical problems is demonstrated. + Ithas recently beeh pointed out that the usual “stick” diagrams of a first-order pattern explain the pattern after the fact, but students are not taught to analyze the pattern, A brief addendum addresses this topic. + Several tables for the prediction of chemical shifts for substituted CH,, CH, and CH groups have been updated. Earlier tables for substituted CH groups in particular have not been satisfactory. + A number of 300 MHz spectra are included in the Problems at the end of the chapter. 13C NMR Spectrometry (Chapter 5) Outdated sections have been condensed or deleted, in- cluding off-resonance decoupling and selective proton decoupling, A section on the very useful DEPT proce- dure has been added. Several sections have been re~ vised, and Problems (at 75.5 MHz) have been added Correlation NMR Spectrometry (Chapter 6) Chapter 6 has been almost completely rewritten. There is more emphasis on pulse sequences and on the use of inverse detection (e.g, HMQC and HMBC experi- ments). Some experiments from the Fifth Edition have been eliminated (e.g., J-Resolved), and others have been added. The chapter has been renamed “Correla- tion NMR Spectrometry” to better reflect the emphasis of the chapter. Because of this name change, the DEPT experiment has been moved to Chapter 5; the APT ex- periment has been eliminated. Gradient field NMR is presented as a recent development. Problems are as- signed. By its nature, correlation spectrometry poses a chal- lenge even at the graduate level, as do the latter prob- Jems in Chapter 9 that depend heavily on correlated spectra, Spectrometry of Other Important Nuclei (Chapter 7) This is a completely new chapter. Over the past decade or so, NMR spectrometry of several nuclei besides "H and ''C have played an increasing role in the identifi cation and analysis of organic compounds. Chapter 7 introduces the student to the most important of these nuclei with spectra, discussion, and Problems. Nuclei discussed are SN, #F, *Si, and P, Solved Problems (Chapter 8) Chapter 8 consists of an Introduction to Solved Prob- ems (Chapter 8A), followed by four solved Problems (Chapter 8B). Our suggested approaches to problem solving have been expanded and should be helpful to students. We have refrained from being overly prescriptive. Students are urged to develop their own approaches, but sugges- tions are offered and caveats posted. ‘The four Problems are arranged in increasing order of difficulty. They involve several common functional ‘groups, a highly substituted aromatic ring, a substituted heteroatom ring with a chiral center, and a diunsatur- ated terpenol. Extensive use is made of 2-D spectra, Assigned Problems (Chapter 9) -- Following a brief introduction (Chapter 9A), Chapter 9B represents the culmination: spectrometric identifi cation of organic compounds by the students. These 55 Problems are arranged in increasing order of difficulty; the early Problems are designed to build confidence, and the later Problems challenge at the graduate level. ‘The Problems are represented by the following spectra (H NMR spectra at 300 or 500 MHz, 3C NMR at 75.5 MHz or 126.0 MHz): No. of Spect Ms (EI) 55 Ms (Cl) 7 IR 35 'H (with expanded insets) 55 BCIDEPT (or APT) 30 ‘cosy 26 HETCOR (or HMQC) 19 HMBC. 5 INADEQUATE, 2 Difference NOE. 3