Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021)

Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021) Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021) Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021) Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021) Preview Spectroscopic Methods in Organic Chemistry, 3rd Edition by Hesse–Meier–Zeeh (2021)

Prefixes used with SI units UV/Vis Spectroscopy Infrared and Raman Spectra Nuclear Magnetic Resonance Spectroscopy Mass Spectrometry Handling of Spectra and Analytical Data: Practical Examples Hesse–Meier–Zeeh Spectroscopic Methods in Organic Chemistry Prof Dr Stefan Bienz Department of Chemistry University of Zurich Winterthurerstrasse 190 CH-8057 Zurich Switzerland Prof Dr Laurent Bigler Department of Chemistry University of Zurich Winterthurerstrasse 190 CH-8057 Zurich Switzerland Dr Thomas Fox Department of Chemistry University of Zurich Winterthurerstrasse 190 CH-8057 Zurich Switzerland Prof Dr Herbert Meier Department of Chemistry Johannes-Gutenberg-University Duesbergweg 18-14 D-55099 Mainz Germany 3rd fully revised and extended Edition 335 Figures, 132 Tables, 59 Schemes, 10 Graphical representations of full analytical datasets Georg Thieme Verlag Stuttgart · New York Library of Congress Cataloging-in-Publication Data is available from the publisher This book is an extended authorized translation of the 9th German edition published and copyrighted 1979, 1984, 1987, 1991, 1995, 2002, 2005, 2012, 2016 by Georg Thieme Verlag, Stuttgart, Germany Title of the German edition: Spektroskopische Methoden in der organischen Chemie © 2021 Thieme All rights reserved, Georg Thieme Verlag KG Rỹdigerstraòe 14, 70469 Stuttgart, Germany www.thieme-chemistry.com Cover: â Thieme Images: © Stefan Bienz and Laurent Bigler, Zurich, Switzerland Printed in Germany by Firmengruppe Appl, Aprinta Druck GmbH, Senefelderstraße 3–11, 86650Wemding ISBN (print) 978-3-13-243408-0 ISBN (ePDF) 978-3-13-243410-3 ISBN (ePUB) 978-3-13-243411-0 DOI 10.1055/b000000049 Some of the product names, patents and registered designs referred to in this book are in fact registered trademarks of proprietary names even though specific reference to this fact is not always made in text Therefore, the appearance of a name without designation as proprietary is not to be construed as a representation by the publisher that it is in the public domain This book, containing all parts thereof, is legally protected by copyright Any use, exploitation or commercialization outside the narrow limits set by copyright legislation, without the publisher’s consent, is illegal and liable to prosecution This applies in particular to photostat reproduction, copying, mimeographing or duplication of any kind, translating, preparation of microfilms, and electronic data processing and storage Preface Already more than 10 years have passed since the second edition of this textbook on spectroscopic methods appeared in 2008 Time has not been standing still, however, and organic analytics have again experienced a tremendous development Not only did the instruments get refined, delivering better spectra and more data with lesser amounts of sample material, but also, hand in hand, computer technology made a big step forward, allowing us to handle and process efficiently the enormous amount of data arising with modern instruments and experiments—in particular with nuclear magnetic resonance (NMR) and mass spectrometry (MS) analyses The book Spektroskopische Methoden in der organischen Chemie by Manfred Hesse, Herbert Meier and Bernd Zeeh took account of these developments in the German version by two subsequent editions that appeared in 2012 and 2016 Even though the authorship has partly changed after more than 32 years, the textbook remained devoted to its original objective It is still meant as a straightforward read and source of reference to complement lecture and laboratory courses devoted to structure elucidation and analytical characterization of organic compounds It shall still offer enough information also to make it a reliable companion for Bachelor, Master, and PhD students, as well as for professionals in chemical teaching and research outside of universities The new English edition appears in a completely new guise Not only has the layout been changed to a more lucid, modern, and colorful look, but also the content has been updated significantly, reflecting important developments in organic analytics The major changes as compared with the previous edition are summarized shortly below In the Ultraviolet/Visible Spectroscopy (UV/Vis) chapter, attended by Herbert Meier (University of Mainz), the fundamentals of allowed and symmetry-forbidden electronic transitions are newly discussed by means of simple molecules In addition, acknowledging the increasing importance of optoelectronic materials, the section about compounds with larger conjugated systems (aromatics, heteroaromatics, and open-chained oligomers) has been extended More room is also given to determination of solvent polarities in the chapter on applications of UV/Vis spectroscopy Thomas Fox (University of Zurich) has taken over the authorship of the chapter of IR and Raman spectroscopy from Bernd Zeeh He particularly revised and complemented the parts describing the basics of these spectroscopic methods For instance, the relationships between bond strengths and vibration frequencies or between molecule symmetries and resulting IR and Raman activities are newly presented With regard to the instrumental part, the construction of IR and Raman spectrometers is discussed in more detail, giving special attention also to the laser technology that became increasingly important A new section dedicated to the interpretation of spectra was added, considering more deeply vibration couplings, overtones, Fermi resonance, and combination and difference bands Adaptions were also done to enhance the efficiency of the interpretation of IR spectra by use of already well-approved sample spectra The important absorption bands are now directly linked to the tables of the characteristic group frequencies, which are completely revised and partly reorganized for even more effective use Major changes have been made in the NMR chapter, authored by Herbert Meier Great emphasis is placed on modern one- and two-dimensional NMR techniques such as DEPT, APT, COSY, DQFCOSY, Ph-COSY, E-COSY, TOCSY, NOESY, ROESY, EXSY, HETCOR, HSQC, HSQC-TOCSY, HSQC-NOESY, HMBC, and INADEQUATE The description of earlier methods, however, has not been forgone because their knowledge is required to be able to understand less recent publications Since organic molecules are mainly constructed on the basis of carbon frameworks, 13C NMR signals play a crucial role in the characterization of organic compounds It is striking to observe, however, that respective signal assignments are omitted or erroneous in many publications It thus became a special issue to deeply discuss electronic, steric, and anisotropic factors that affect the chemical shifts of 13C signals in open-chain as well as cyclic compounds Several respective tables have been added, and the graphical table with the compilation of 1H and 13C chemical shifts—displayed with compounds ordered according to substance classes—has been significantly extended and complemented with examples of more rare substance classes In the NMR spectra shown, two opposing tendencies are taken into account: on the one hand there is the trend towards high field strengths; on the other hand,bench spectrometers with, e.g 60 MHz became more important Stefan Bienz and Laurent Bigler (both University of Zurich) are the new authors of the MS chapter, replacing Manfred Hesse who died in 2011 Performance and user friendliness of mass spectrometers have tremendously advanced over the recent decades New and sophisticated ion generation, ion separation, and ion detection methods, and many new accessories such as coupled separation and automatization modules, sample preparation kits, and evaluation software led to a fresh affection for the MS method and to a broad spread of MS instruments as routine and open-access equipment throughout many chemical facilities To account for these developments, the MS chapter was completely redesigned: the content was fully regrouped, freed of obsolete techniques and methods, and complemented with information to newest instrumental and methodical advances Because the MS techniques became more and more different and facetted, a new chapter has been introduced, which gives guidance for selecting proper sample preparations and appropriate measuring procedures The newest methods for the structural elucidation of small molecules up to biopolymers are introduced, based on accurate mass measurements (high-resolution MS, HR-MS) and collision-induced dissociation (CID) Although not in detail, fragmentation mechanisms and fragmentation patterns for CID processes are addressed along broad lines, which is relevant in connection with structural elucidations of unknown analytes, where information can often be gained from conclusions by analogy The completely new final chapter of the textbook, Handling of Spectra and Analytical Data: Practical Examples, is also authored by Stefan Bienz and Laurent Bigler It shows by means of 10 real cases how analytical data are described and what kind of strategies could be followed to come up with these data to reasonable structural proposals The compounds were measured without any exception with modern instruments, and the examples were chosen to demonstrate the information gain that can be acquired by the most commonly applied analytical methods, including two-dimensional NMR and HR-MS As a supplement, a set of freely accessible exercises is provided online For the preparation of the new English edition, which embraces also the preparation of the two German editions of 2012 and 2016, we owe our gratitude to many colleagues First of all, the marvelous groundwork of the two former authors, Manfred Hesse and Bernd Zeeh, is warmly acknowledged Special thanks are also due to Heinz Berke and Ferdinand Wild (both University of Zurich), as well as Klaus Bergander (University of Münster) for their contributions to the IR/Raman chapter; Heinz Kolshorn, Johannes Liermann, and Ingrid Schermann (all University of Mainz) for their supports for the NMR chapter; and Urs Stalder, Armin Guggisberg, Yvonne Forster, Jrène Lehmann, and the students of the advanced chemical laboratory courses (all University of Zurich) for their inputs, analytical measurements, and samples that were used for the MS chapter, the practical examples in Chapter 5, and the electronic supplements Stefan Bienz in the name of the authors Contents UV/Vis Spectroscopy 1.1 1.1.1 1.1.2 Theoretical Introduction Electromagnetic Waves and Electron Transitions in Molecules Light Absorption and the Spectrum 1.2 Sample Preparation and Measurement of Spectra 1.3 1.3.1 1.3.2 1.3.3 1.3.4 1.3.5 1.3.6 1.3.7 Chromophores Individual Chromophoric Groups and Their Interactions Olefins and Polyenes Benzene and Benzenoid Aromatics Heteroaromatics (Hetarenes) Carbonyl Compounds Conjugated Oligomers and Polymers Aggregated Molecules, Charge-Transfer Complexes 1.4 Applications of UV/Vis Spectroscopy 1.5 Derivative Spectroscopy 1.6 Chiroptical Methods Supplementary Literature UV/Vis spectroscopy Chiroptical Methods Infrared and Raman Spectra 2.1 Introduction 2.2 Basic Principles 2.3 2.3.1 2.3.2 Infrared Spectrometer Classical (Scanning) Infrared Spectrometers Fourier Transform Spectrometer 2.4 2.4.1 Sample Preparation Sample Preparation for Measurements in Transmission 2.4.2 2.4.3 Reflection Measurements Raman Measurements 2.5 2.5.1 2.5.2 Infrared Spectrum Number and Types of Vibrations Spectrum Interpretation 2.6 Characteristic Absorptions: An Overview 2.7 2.7.1 2.7.2 Infrared Absorptions of Single Bonds with Hydrogen (C–H) Absorption (O–H) and (N–H) Absorptions 2.8 Infrared Absorptions of Triple Bonds and Cumulated Double Bonds 2.9 Infrared Absorptions of Double Bonds C=O, C=N, C=C, N=N, and N=O 2.10 Infrared Absorption of Aromatic Compounds 2.11 Infrared Absorption in the Fingerprint Range 2.12 Examples of Infrared Spectra 2.13 Information Technology Assisted Spectroscopy 2.14 Quantitative Infrared Spectroscopy 2.15 2.15.1 2.15.2 2.15.3 2.15.4 2.15.5 Raman Spectroscopy Excitation Mechanisms Selection Rules Raman Spectrometer Applications Comparison of Infrared and Raman Literature Raman Spectroscopy Particular Techniques Databases and Application Nuclear Magnetic Resonance Spectroscopy 3.1 3.1.1 3.1.2 3.1.3 3.1.4 3.1.5 Physical Principles The Resonance Phenomenon Chemical Shift Spin–Spin Coupling Linewidths Intensity 3.2 3.2.1 3.2.2 3.2.3 NMR Spectra and Molecular Structure Molecules with “Rigid” Atomic Positions Intramolecular Motion Chemical Exchange Processes 3.3 3.3.1 3.3.2 3.3.3 3.3.4 3.3.5 3.3.6 3.3.7 1H 3.4 3.4.1 3.4.2 3.4.3 3.4.4 3.4.5 3.4.6 3.4.7 13C NMR Spectroscopy Sample Preparation and Measurement of 1H NMR Spectra 1H Chemical Shifts 1H,1H Coupling Coupling to Other Nuclei Correlation of 1H Shifts with Structural Features Increment Systems for Estimating 1H Chemical Shifts 1H NMR Data of Representatives of Common Classes of Compounds 3.3.8 Specialized Techniques 3.3.9 Two-Dimensional 1H NMR Spectroscopy 3.3.10 Simulation of 1H NMR Spectra 3.3.11 NMR Spectra of Oriented Phases and Solids 3.3.12 Combination of Separation Methods with NMR Measurements NMR Spectroscopy Sample Preparation and Measurement of Spectra 13C Chemical Shifts Correlation of 13C Chemical Shifts with Structural Features Increment Systems for the Estimation of 13C Chemical Shifts 13C,1H Couplings Coupling of 13C to Other Nuclei (D, F, N, and P) 13C,13C Couplings 3.4.8 Special Techniques 3.4.9 Multidimensional 13C NMR Spectra 3.4.10 Solid-State Spectra 3.5 3.5.1 3.5.2 3.5.3 Combination of 1H and 13C NMR Spectroscopy Complete Assignment of 1H and 13C NMR Signals Use of Databases 1H and 13C NMR Data of Representatives of the Most Important Classes of Compounds 3.6 3.6.1 3.6.2 3.6.3 3.6.4 NMR of other Nuclei 19F NMR Spectroscopy 31P NMR Spectroscopy 15N NMR Spectroscopy Complete Assignment of the NMR Signals of a Compound Containing 1H, 13C, 15N, … Other Nuclei 3.6.5 Literature General Works Special Methods and Effects Special Compound Classes, Applications Catalogues Serials, Periodicals Mass Spectrometry 4.1 Introduction 4.2 4.2.1 4.2.2 General Aspects of Mass Spectrometry The Principle of Mass Spectrometry The Mass Spectrum 4.3 4.3.1 4.3.2 4.3.3 4.3.4 Instrumental Aspects Sample Introduction (Injection) and Ion Types Ionization Methods Mass Analyzers Detectors 4.3.5 4.3.6 4.3.7 4.3.8 Tandem Mass Spectrometry Coupling of Mass Spectrometry with Chromatographic Methods Ion-Mobility Mass Spectrometry Selection of the Appropriate Method 4.4 4.4.1 4.4.2 4.4.3 4.4.4 4.4.5 4.4.6 4.4.7 4.4.8 Interpretation of Spectra and Structural Elucidation Preparation for the Interpretation Structural Information from HR-MS Fragmentation Reactions in EI-MS Collision-Induced Dissociation Neighboring Group Participation and Stereoisomerism Spectral Libraries Special Techniques Elucidation of Fragmentation Mechanisms 4.5 4.5.1 4.5.2 4.5.3 Sample Preparation Purification, Preparation, and Enrichment Sample Submission and Declaration of Sample Properties Specific Preparations for the Measurement 4.6 4.6.1 4.6.2 4.6.3 4.6.4 Artifacts Memory Effect Formation of Artifacts in the Ion Source Identification of Artifacts Prevention of Artifact Formation 4.7 4.7.1 4.7.2 4.7.3 4.7.4 4.7.5 Tables to the Mass Spectrometry Frequently Detected Ions Frequently Detected Mass Differences Isotope Distributions of Halogenated Compounds Solvents and Frequent Impurities Isotopes of Naturally Occurring Elements Literature Handling of Examples Spectra and Analytical Data: Practical 5.1 Introduction 5.2 Characterization of Compounds Example Example 5.3 Structure Elucidation of Allegedly Known Compounds and of Products Arising from Syntheses Example Example Example 5.4 Structure Elucidation Compounds Example Example Example Example Example 10 Literature Index of Completely Unknown ... spectroscopic methods appeared in 2008 Time has not been standing still, however, and organic analytics have again experienced a tremendous development Not only did the instruments get refined, delivering... Spectroscopy Infrared and Raman Spectra Nuclear Magnetic Resonance Spectroscopy Mass Spectrometry Handling of Spectra and Analytical Data: Practical Examples Hesse–Meier–Zeeh Spectroscopic Methods in Organic. .. exception with modern instruments, and the examples were chosen to demonstrate the information gain that can be acquired by the most commonly applied analytical methods, including two-dimensional