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

1 UV/Vis Spectroscopy

2 Infrared and Raman Spectra

3 Nuclear Magnetic Resonance Spectroscopy

4 Mass Spectrometry

5 Handling of Spectra and Analytical Data: Practical Examples

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

Rüdigerstraße 14, 70469 Stuttgart, Germany

www.thieme-chemistry.com

Cover: © 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 1 2

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.

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

1 UV/Vis Spectroscopy

1.1.1 Electromagnetic Waves and Electron Transitions in Molecules 1.1.2 Light Absorption and the Spectrum

1.3.1 Individual Chromophoric Groups and Their Interactions

1.3.2 Olefins and Polyenes

1.3.3 Benzene and Benzenoid Aromatics

1.3.4 Heteroaromatics (Hetarenes)

1.3.5 Carbonyl Compounds

1.3.6 Conjugated Oligomers and Polymers

1.3.7 Aggregated Molecules, Charge-Transfer Complexes

Supplementary Literature

UV/Vis spectroscopy

Chiroptical Methods

2 Infrared and Raman Spectra

2.3.1 Classical (Scanning) Infrared Spectrometers

2.3.2 Fourier Transform Spectrometer

2.4.1 Sample Preparation for Measurements in Transmission

2.4.2 Reflection Measurements

2.4.3 Raman Measurements

2.5.1 Number and Types of Vibrations

2.5.2 Spectrum Interpretation

2.7.1 (C–H) Absorption

2.7.2 (O–H) and (N–H) Absorptions

Double Bonds

N=N, and N=O

2.15.1 Excitation Mechanisms

2.15.2 Selection Rules

2.15.3 Raman Spectrometer

2.15.4 Applications

2.15.5 Comparison of Infrared and Raman

Literature

Raman Spectroscopy

Particular Techniques

Databases and Application

3 Nuclear Magnetic Resonance Spectroscopy

3.1 Physical Principles

3.1.1 The Resonance Phenomenon

3.1.2 Chemical Shift

3.1.3 Spin–Spin Coupling

3.1.4 Linewidths

3.1.5 Intensity

3.2.1 Molecules with “Rigid” Atomic Positions

3.2.2 Intramolecular Motion

3.2.3 Chemical Exchange Processes

3.3.1 Sample Preparation and Measurement of 1H NMR Spectra 3.3.2 1H Chemical Shifts

3.3.3 1H,1H Coupling

3.3.4 Coupling to Other Nuclei

3.3.5 Correlation of 1H Shifts with Structural Features

3.3.6 Increment Systems for Estimating 1H Chemical Shifts

3.3.7 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

3.4.1 Sample Preparation and Measurement of Spectra

3.4.2 13C Chemical Shifts

3.4.3 Correlation of 13C Chemical Shifts with Structural Features 3.4.4 Increment Systems for the Estimation of 13C Chemical Shifts 3.4.5 13C,1H Couplings

3.4.6 Coupling of 13C to Other Nuclei (D, F, N, and P)

3.4.7 13C,13C Couplings

3.4.8 Special Techniques

3.4.9 Multidimensional 13C NMR Spectra

3.4.10 Solid-State Spectra

3.5.1 Complete Assignment of 1H and 13C NMR Signals

3.5.2 Use of Databases

3.5.3 1H and 13C NMR Data of Representatives of the Most

Important Classes of Compounds

3.6.1 19F NMR Spectroscopy

3.6.2 31P NMR Spectroscopy

3.6.3 15N NMR Spectroscopy

3.6.4 Complete Assignment of the NMR Signals of a Compound

Containing 1H, 13C, 15N, …

3.6.5 Other Nuclei

Literature

General Works

Special Methods and Effects

Special Compound Classes, Applications

Catalogues

Serials, Periodicals

4 Mass Spectrometry

4.2.1 The Principle of Mass Spectrometry

4.2.2 The Mass Spectrum

4.3.1 Sample Introduction (Injection) and Ion Types

4.3.2 Ionization Methods

4.3.3 Mass Analyzers

4.3.4 Detectors

4.3.5 Tandem Mass Spectrometry

4.3.6 Coupling of Mass Spectrometry with Chromatographic

Methods

4.3.7 Ion-Mobility Mass Spectrometry

4.3.8 Selection of the Appropriate Method

4.4.1 Preparation for the Interpretation

4.4.2 Structural Information from HR-MS

4.4.3 Fragmentation Reactions in EI-MS

4.4.4 Collision-Induced Dissociation

4.4.5 Neighboring Group Participation and Stereoisomerism

4.4.6 Spectral Libraries

4.4.7 Special Techniques

4.4.8 Elucidation of Fragmentation Mechanisms

4.5.1 Purification, Preparation, and Enrichment

4.5.2 Sample Submission and Declaration of Sample Properties 4.5.3 Specific Preparations for the Measurement

4.6.1 Memory Effect

4.6.2 Formation of Artifacts in the Ion Source

4.6.3 Identification of Artifacts

4.6.4 Prevention of Artifact Formation

4.7.1 Frequently Detected Ions

4.7.2 Frequently Detected Mass Differences

4.7.3 Isotope Distributions of Halogenated Compounds

4.7.4 Solvents and Frequent Impurities

4.7.5 Isotopes of Naturally Occurring Elements

Literature

5 Handling of Spectra and Analytical Data: Practical Examples