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 Contents vii

5.5 Using Two-Dimensional NMR Data to Assign Spectra 198

5.6 Using Two-Dimensional NMR Data to Determine
an Unknown Structure 208
5.7 Strategies for Using 2D NMR in Structure Determination 211
5.8 Use of NOESY and ROESY to Determine Relative
Stereochemistry and Conformations 214
5.9 Specialized Pulse Sequences 221
5.10 Configurational Analysis Based on Coupling Constants:
Experimental Measurement of 2,3JCH Couplings 230
5.11 Computer-Assisted Structure Elucidation 231
5.12 Future Prospects in Multidimensional NMR 233
Sources for Further Reading 235
Problems 236
More Challenging Problems 253

CHAPTER 6
MASS SPECTROMETRY: CORE TECHNIQUES AND
IONIZATION PROCESSES 273
6.1 A Glimpse of Mass Spectrometry 274
6.2 Measurement, Presentation of Data, and Nomenclature 276
6.3 Isotopes, Atomic Composition, Molecular Formulas,
and Ionic Mass; Low and High Resolution Measurements 277
6.4 Different Ionization Techniques in Mass Spectrometry 285
6.5 Different Techniques for Analyzing Ions in
Mass Spectrometry 304
6.6 Detectors in Mass Spectrometry 311
6.7 Hyphenated Mass Spectrometry 311
6.8 Tandem Mass Spectrometry 314
6.9 Future Prospects 316
Sources for Further Reading 319
Internet Resources 320
Problems 321
More Challenging Problems 323

CHAPTER 7
MASS SPECTROMETRY ANALYSIS OF SMALL AND
LARGE MOLECULES 325
7.1 A Glimpse of Molecular Ions Revisited 325
7.2 Small-Molecule Mass Spectral Analysis 327
7.3 Large-Molecule Mass Spectrometry Analysis 335
7.4 Future Prospects 343
Sources for Further Reading 344
Problems 345
More Challenging Problems 355
viii Contents

CHAPTER 8
FRAGMENTATION PROCESSES IN ELECTRON
IONIZATION MASS SPECTROMETRY 359
8.1 A Glimpse of Fragmentation in Mass Spectrometry 360
8.2 Interpreting a Low Resolution Electron Ionization
Mass Spectrum 361
8.3 Fragmentation Processes 363
8.4 Identification of Functionality from Fragmentation
Processes 371
8.5 Schematic Approach for the Interpretation of an EIMS 389
Sources for Further Reading 390
Problems 391
More Challenging Problems 398

CHAPTER 9
INFRARED SPECTROSCOPY 401
9.1 A Glimpse of Infrared Spectroscopy 402
9.2 Measurement and Presentation of Data 403
9.3 The Fundamentals 405
9.4 Identifying Functional Groups 410
9.5 Interpreted Infrared Spectra 421
9.6 Use of Infrared Databases 430
Sources for Further Reading 431
Problems 431
More Challenging Problems 435

CHAPTER 10
OPTICAL AND CHIROPTICAL TECHNIQUES:
ULTRAVIOLET SPECTROSCOPY 439
10.1 A Glimpse of Ultraviolet Spectroscopy 440
10.2 Measurement and Presentation of Data 441
10.3 The Fundamentals for Interpreting Spectra 442
10.4 Identifying Functional Groups 445
10.5 Theoretical Simulations of UV Spectra 451
10.6 The Behavior of Chiral Chromophores ORD/CD 453
10.7 The Exciton Chirality Method 457
10.8 Other Ways to Examine Chiral Chromophores 460
Sources for Further Reading 463
Problems 463
More Challenging Problems 465
 Contents ix

CHAPTER 11
STRATEGIES OF DETERMINING STRUCTURE AND
STEREOCHEMISTRY: SPECTROSCOPIC DATA
TRANSLATED INTO STRUCTURES 467
11.1 A Glimpse of the Combined Use of Spectroscopic Data 468
11.2 The Strategies of Determining Structure and Stereochemistry 468
11.3 Dereplication Strategies 470
11.4 Worked Examples of Deriving Structures from Spectroscopic Data 472
Using 13C NMR Data to Correct the Label of Unknown A
(Figure 11.1) 472
Using 1H NMR Data, Unknown B (Figure 11.2) 472
Using 13C NMR Data, Unknown C (Figure 11.3) 477
Combining 1H and 13C NMR Data, Unknown D (Figure 11.4) 477
Using UV Data, Unknown E (Figure 11.5) 479
Using NOE 1H NMR Data, Unknown F (Figure 11.6) 481
Combining MS and NMR Data, Unknown G (Figure 11.7) 481
Emphasis on 1H–1H COSY NMR Data, Unknown H
(Figure 11.8) 483
Emphasis on Combining 13C, DEPT-135, and INADEQUATE
NMR Data, Unknown I (Figure 11.9) 485
Emphasis on 1H–13C HMQC and HMBC NMR Data,
Unknown J, Guaiazulene (Figure 11.10) 487
Emphasis on a Limited Dataset to Solve a Structure,
Unknown K (Figure 11.11) 490
Emphasis on the Use of 1H–15N HSQC and HMBC Data,
Unknown L (Figure 11.12) 497

CHAPTER 12
PROBLEMS IN ORGANIC STRUCTURE ANALYSIS 503
12.1 A Glimpse of the Scope of the 51 Unknowns 503
12.2 Using the Spectra, Accompanying Information,
and Other Resources 504
Simple Monofunctional Compounds 505
More Challenging Mono or Higher Functionalized Compounds 536
Extremely Challenging Polyfunctionalized Compounds 567
Complex Natural Products 575
Index of Molecular Formulas and Structures 610

Appendix A: Collection of Spectra or Data Tables 613

Appendix B: Shape of MS Clusters 615
Appendix C: CAS Registry Numbers for Unknowns 617
Appendix D: Glossary and Abbreviations 621
Index 629
This page intentionally left blank
PREFACE

Introduction

This second edition of Organic Structure Analysis is the most up-to-date integrated
spectroscopy text for advanced undergraduates, graduate students, and practitioners. The
overall structure of the text is based on a problem-solving approach that follows the actual
information flow used by chemists solving molecular structures, as opposed to-the stan-
dard methods-based approach used in other texts. Another hallmark of this text is its
focus on the chemical structure. Thus, the text revolves around how relevant information
regarding skeleton, functional groups and stereochemistry can be derived and the benefits
and disadvantages of particular approaches. We refer to theory where doing so facilitates
an understanding of the method and where an understanding of areas in which problems
may occur will be helpful. This text does not dwell on theory in the abstract; instead, it
emphasizes the principles directly relevant to interpretation of analytical data.
All organic and many biological chemists repeatedly use physical properties to verify
or establish organic structures. The focus of this text is on four techniques: nuclear mag-
netic resonance (NMR), mass spectrometry (MS), infrared (IR), and ultraviolet–visible
(UV-VIS), which are used daily in establishing the structure of small to medium-sized
molecules. The major goal is to show how data from these methods can be efficiently
interpreted; however, the appearance of an NMR, MS, IR, or UV-VIS trace is dictated
by different rules. Each chapter provides different perspectives about how such data is
understood and used in the step-by-step process to establish structural features including
an overall carbon framework, determine the presence and location of functional groups,
deduce the regiochemistry and stereochemistry of substituents, and, finally, prove the
absolute stereochemistry of stereogenic (chiral) centers.
An ability to use spectroscopic data to evaluate organic structures is best gained by
combining practical experience and knowledge of the fundamentals. Many of the rules to
guide analysis of spectra have come from an empirical process by trial and error. In addi-
tion, using data of model compounds has been quite important in developing relationships
between structure and spectral data. Numerous correlation tables appearing throughout
the chapters should be useful both during and after a formal course on identification of
organic compounds. We also recommend using computer software that allows exten-
sive examination of predicted proton and carbon NMR parameters. Overall, the authors
believe all these elements combine to form a holistic and realistic representation of how
structure elucidation plays out in the real world.

Distinctive Features of Organic Structure Analysis,

Second Edition

• Emphasis on structure. The second edition opens with the discussion of the
structural elements, followed by the characteristics of the spectroscopic methods
xii Preface

and their advantages and disadvantages. Unique to this text are the discussions
on the steps used in determining a molecular structure, as well as a presenta-
tion of limitations to organic structure determination by spectroscopic methods.
Table 1.4, a unique pairing of original and revised structures that also identifies
the real-world challenges that arise in the determination of determining structural
compounds, might be subtitled “Organic Structure Analyses Gone Bad.”
• Practical organization. The methods in most common use are covered first. For
example, in most cases a chemist obtains the NMR spectrum before doing any-
thing else. Thus, generating spectra is discussed before the more advanced steps
in problem solving, such as mass spectrometry. Optical methods such as infrared
and ultraviolet, which are less often used are covered last.
• Real-world problem-solving approach. The problem-solving approach used in
the second edition follows the actual information flow used by practitioners solv-
ing molecular structures, not the standard methods-based approach found in other
texts. The many worked examples in each chapter cover the most important appli-
cations of each method. The integrated use of methods is included in later chap-
ters and culminates in a chapter of solved problems. Approximately 20 problems
follow at the end of each of Chapters 1–10. Divided into regular and more chal-
lenging problems, these exercises will help you focus on key principles while also
extending the concepts presented. Nearly 300 problems at all levels of difficulty
are provided throughout the book.
• Capstone Chapter 12 presents 51 problems. The text approaches structure deter-
mination by using a variety of methods in an integrated way, revealing to students
the comprehensive nature behind structure identification. Chapter 12 contains 51
unknowns for solution, starting with molecules with single functional groups and
ending with complex multifunctional compounds of appreciable size. Each prob-
lem emphasizes a particular method. However, the problems increase in difficulty
throughout this chapter, and each successive problem requires students to think
in a more rigorous fashion as they are required to bring together many different
techniques to solve a single problem.

Organization

This book was written by three natural product chemists who deal every day with the
task of structure elucidation. The contents and its order are based on precepts we know
to be effective in helping students gain expertise in structure determination from spectra.
In problem solving, we have repeatedly found that, extensive practice, having access to
data of models, and a developing a firm understanding of spectral interpretation are the
ultimate combination. The cycle of making mistakes and then deriving corrections, often
after much further thought, is also a key part of the process. In fact, many of the problems
assembled herein will present this exact situation.
The first section of the text, which comprises 10 chapters, extensively covers each
of the individual spectroscopic methods. Chapter 1 opens with the discussion of the
structural elements, followed by the characteristics of the spectroscopic methods and
their advantages and disadvantages, ending with the graphic demonstration of “Organic
Structure Analyses Gone Bad” (Table 1.4).
The discussions and problems of Chapters 2–10 specifically present strategies for
assembling partial fragments to be merged into complete 3D structures. Throughout the
first section we emphasize the need to consider structural alternatives and to think about
how incorrect possibilities can be efficiently ruled out. A large amount of model com-
pound data is presented, as well as correlation tables. Such compilations cover a wide
breadth of substructures, and examples are given on their use.
 Preface xiii

You will notice from the table of contents that two techniques, NMR and MS, are
especially emphasized. These two methods, providing the best return of information from
the actual spectral data, continue to be the major focus for advances in instrumentation
and techniques. Underscoring the widespread appreciation of these methods is that they
continue to be the subjects of annual professional meetings and a main focus of some
research journals.
NMR is the subject of Chapters 2–5. Chapter 2 furnishes an introduction to the prin-
ciples of what nuclei can be examined and how their inherent differences affect the acqui-
sition and appearance of data. In Chapter 3 the use of peak areas (integrals) and chemical
shifts (
) is considered. The evaluation of coupling constants (J) and nuclear Overhauser
relaxation effects (NOE) are subjects of Chapter 4.
Multiple-pulse and multidimensional NMR methods are covered in Chapter 5.
This chapter has been extensively reworked to reflect instrumental advances, new pulse
sequences, and improved data processing techniques. One-dimensional methods that use
selective pulses are demonstrated with 1D TOCSY and 1D NOESY sequences. A section
on different strategies to solve unknown structures and their time and sample require-
ments ties in with a later section on computer-assisted structure elucidation. The chapter
explains the basics of NOESY and ROESY and their use in determining relative stereo-
chemistry and solution conformation. A section on specialized pulse sequences includes
edited sequences, sequences that can differentiate two-bond and three-bond C–H correla-
tions and 1H–15N sequences.
The biggest advances over the last decade have been in mass spectrometry techniques,
and these changes have prompted the inclusion of additional chapters not found in the first
edition. These chapters cover core techniques and ionization processes, analysis of small
and large molecules, and fragmentation processes. In Chapter 6, which covers the instru-
mental basis of the methods, the most often used ionization techniques are described in
detail, as well as the associated benefits and disadvantages. The coverage of ion analyzers
includes the very recent additions such as the orbitrap. Hyphenated and tandem techniques
are covered in greater detail than before, and we discuss the different scan modes.
Chapter 7 deals with the determination of the molecular formula and how this can be
achieved by using a combination of NMR and accurate mass methods. Recognition that
many organic chemists now work across the boundary between small and large molecules
means that the coverage of large-molecule MS will be welcomed. A section on derepli-
cation has been included, as chemoinformatics now plays a large part in the structure
elucidation process. Chapter 8, on fragmentation processes, has updated sections and
improved graphics.
The two remaining chapters in the first section deal with optical techniques: infra-
red spectroscopy, which is covered in Chapter 9, and ultraviolet as well as chiroptical
techniques, which are covered in Chapter 10. The chiroptical tools of ORD/CD con-
tinue to be especially important in defining 3D structural features. Computer simula-
tion of UV and CD spectra is introduced in Chapter 10 to alert the reader to these
emerging methods.
The second section of the text is Chapter 11, which consists of the worked-out solutions
of 12 problems. This chapter demonstrates how the strategies of organic structure analysis
are actually applied, often in iterative combination of all four types of analytical data. An
introductory section on dereplication shows the different routes to the interrogation of data-
bases to determine whether a compound being investigated is already known. The strategy
delineated in the chapter is to first use the raw data to construct a list of working structures,
an approach that will promote the best possible understanding of the thinking underlying
our solutions. We have chosen examples that emphasize the value of a combined approach
in which assorted pieces of data are weighted according to their value in deriving unknown
functionality, symmetry elements, or stereochemical relationships. Also exemplified is the
handling of data from different spectra that may, at first glance, be conflicting. Such situations
xiv Preface

often arise in research but are rarely addressed in texts. The final two worked problems
address the handling of samples available in limited amounts and value of 15N data.
The third section of the text is Chapter 12, which consists of 51 unsolved problems based
on combined spectra. The chapter offers the opportunity to test skills in solving a series of
simple to complex problems. The reader is expected to use actual spectra to deduce all
structures that are consistent. This section will help to sharpen and refine skills of translating
spectral observations into accurate conclusions about organic substructures and finally com-
plete structures. The 51 unknowns are organized in four groups according to their complexity.
The first group contains 22 problems that encompass the major organic functional groups.
The second group has 17 problems that are more challenging because of additional complex-
ity of the carbon framework, the higher functionalization, or a combination of these factors.
The 3 problems in the third group are extremely challenging because of their polyfunctional
nature. The fourth group comprises 9 complex natural products. Be forewarned that the solu-
tion of each of these problems could take days! Collectively, these 51 problems are valuable
because they provide an almost inexhaustible context to apply the many principles introduced
in Chapters 1–10.

Who Should Use This Text

The format of this text makes it useful for advanced undergraduates, graduate students,
and practicing chemists. We presume that the reader possesses knowledge of introductory
organic chemistry. Likewise, an elementary understanding of how to interpret spectra of
simple organic compounds is assumed. Early on, suggestions are given about sources to
consult if a brief review is needed on general principles. Lecture courses on spectroscopy,
or organic structure determination could employ this as a basic text. Advanced chemistry
courses that treat analytical organic chemistry could also incorporate this as a supple-
ment. Laboratory courses such as qualitative organic or advanced experimental organic
chemistry could also use this as a supplemental text. Finally, the extensive problems con-
tained here make this a very useful source for independent study.

Overview of Revisions in the Second Edition

In the 12 years since the last edition, there have been significant changes in spectroscopic
instrumentation. These modernizations are reflected throughout this new edition, particu-
larly in the chapters on 2D nuclear magnetic resonance methods and mass spectrometric
methods. The same 12-year period saw advances in many methods now in regular use by
practitioners: data processing methods, computer prediction of spectroscopic data, and
computer-aided structure elucidation. These changes have been included in the text, and
their utility is discussed so that the reader can judge where these are best applied. New
sections have been included where the first edition omitted coverage, and spectra have
been reacquired or reprocessed to improve the quality of reproduction. Many of the other
graphics have been updated for the same reason and also to improve their didactic value.
Additional examples and nearly 80 new problems have been included, covering all sec-
tions; references have been updated throughout.

What Is New in the Second Edition

Coverage of Latest Instrumental and Computational Advances

The use of modern instruments available in most laboratories is emphasized, and for each
analytical technique, we cover the advantages and disadvantages of available methods.
 Preface xv

The new edition presents the use of such modern data processing and computer-assisted
structure elucidation techniques as the following.

• Updated and expanded coverage of NMR. The four chapters covering NMR
have been extensively revised: Chapter 5, which covers multipulse and multidi-
mensional NMR methods has had a major overhaul; we demonstrate the use of
selective pulses applied in 1D TOCSY and 1D NOESY sequences; we have added
a comprehensive new section on the use of NOESY and ROESY in determining
relative stereochemistry and solution conformation.
• Expanded coverage of mass spectrometry. The second edition includes a
new chapter on mass spectrometry, increasing the text’s coverage of the subject
(Chapters 6–8) from two chapters to three. New ionization techniques, tandem
MS techniques, combining NMR with MS, discussion of large molecule MS,
chemoinformatics, and more are now presented.

Increased Number of Problems

Each chapter contains a large number of problems, emphasizing the different topics cov-
ered in the chapter; sections of more challenging problems have been added, as well.
Chapter 11 now includes two new problems that cover the new methods of multipulse
and multidimensional NMR. In one of these the use of a superconducting probe on a very
small sample allows one to obtain 2D data even though a 13C NMR spectrum is not avail-
able. The last problem in Chapter 11 achieves the full assignment of all 1H, 13C and 15N
NMR chemical shifts for a dipeptide. Chapter 12 gives a revised set of problems, many of
which have been selected for greater pedagogical impact.

Improved Data Sets

Many of the experimental traces including all those presented in Chapters 11 and 12, have
been reprocessed or reacquired. A simpler template is used to give the basic information
for each problem. The 2D data have been reproduced with sufficient expansions to allow
them to be easily analyzed.

Appendices and Ancillary Materials

Instructor’s Resource CD-ROM

The second edition of Organic Structure Analysis is accompanied by an instructor’s
resource CD-ROM that includes all the images from the text in electronic format and all
the solutions to the text’s exercises and problems.

New Software and Structure References

Access to data of model compounds, to tools that simplify the interpretation of data, and
to actual spectra of simple compounds can be extremely valuable. There are several pack-
ages that we highly recommend to accompany this text. Many of the chemical drawing
packages available can predict 1H and 13C chemical shifts, and the choice must be made
by balancing features needed and price. Many of the relevant software packages and
Internet resources are listed at the end of each chapter and in Appendix A.
• MS. Very useful mass spectrometry calculation software tools can be obtained as
free-ware at several locations; some are listed at the end of Chapters 6 and 7. The
most useful can be found by searching the Internet for James Deline’s Molecular
xvi Preface

Fragment Calculator (MFCalc), which allows the rapid determination of molecu-

lar formulas from accurate mass measurements.
• Structures. A wealth of information is available from the Merck Index and the
Aldrich Chemical Company catalog. Most university libraries have the former, and
the latter can be found online at www.sigmaaldrich.com. The Aldrich catalog pro-
vides another valuable resource, namely, the listing of many specimen IR and NMR
spectra of compounds. A framework molecular model set is also a handy tool, which
will be useful to visualize three-dimensional relationships of examples presented
both in the text and in the problems. Many commercial computer packages are avail-
able that support either simple molecular modeling or more complex model building.
These tools provide energy estimates for various conformational alternatives.

Acknowledgments

We take pleasure in thanking the many people who have offered help and suggestions
during the long period preceding the final publication of this edition. Most important
are our wives, Peggy (PC), Rosa (JR), and Sally (MJ), and children, Darren, Mitch, and
Neil (PC), Sergio and Iago (JR), and Alice and Henry (MJ), who provided encourage-
ment and constant understanding. Thanks go to our research groups, who were patient
when we were busy revising the book and provided spectra that appear in this edition.
The staff at Oxford University Press (New York), especially Chemistry Editor Jason Noe
(who has a very apt name for this book—see Chapters 4 and 5) and his assistant Melissa
Rubes. We would also like to express appreciation to everyone at Oxford Press: Patrick
Lynch, Editorial Director; John Challice, Publisher and Vice President; Adam Glazer,
Director of Marketing; Preeti Parasharami, Product Manager; Steven Cestaro, Production
Director; Brian Black, Production Editor; Paula Schlosser, Art Director; Dan Niver and
Binbin Li, Designers. Finally we thank Brian Black, and Brenda Griffing, who turned the
writings of an American, A Spaniard and a Dutchman into English. Several companies
provided figures for this edition. We would like to thank Sigma-Aldrich, Thermo-Fisher,
Applied Biosystems and Varian for their assistance.
A host of reviewers provided valuable comments on this edition. These were:

Aaron Aponick, University of Florida

Ronald K. Castellano, University of Florida
Thomas Cole, San Diego State University
Charles W. DeBrosse, Temple University
Roman Dembinski, Oakland University
Malcolm D. E. Forbes, University of North Carolina, Chapel Hill
Stefan France, Georgia Institute of Technology
Daniel Freedman, State University of New York, New Paltz
Albert J. Fry, Wesleyan University
Deryn Fogg, University of Ottawa
John Grutzner, Purdue University
Zhongwu Guo, Wayne State University
David R. Haines, Wellesley College
Robert Hammer, Louisiana State University
Robin B. Kinnel, Hamilton College
Jennifer Koviach-Côté, Bates College
Kirk Manfredi, University of Northern Iowa
John Masnovi, Cleveland State University
 Preface xvii

Satomi Niwayama, Texas Tech University

Sandra L. Olmsted, Augsburg College
Joshua J. Pak, Idaho State University
Bala Ramjee, Old Dominion University
Tomikazu Sasaki, University of Washington
Barry B. Snider, Brandeis University
M. Cameron Sullards, Georgia Institute of Technology
T. Andrew Taton, University of Minnesota
Laren M. Tolbert, Georgia Institute of Technology
John D. Tovar, Johns Hopkins University
Scott Van Bramer, Widener University
Bernhard Vogler, University of Alabama–Huntsville
Jiong Yang, Texas A&M University

These reviewers provided valuable comments and encouragement on the first edition:

Bill Aalbersberg, University of the South Pacific

Harold M. Bell, Virginia Polytechnic Institute and State University
Cliff Chang, University of West Florida
Tad H. Koch, University of Colorado at Boulder
G. Marc Loudon, Purdue University
Lee Magid, University of Tennessee
David C. Myles, University of California, Los Angeles
Roy Okuda, San Jose State University
“Fritz” Schmitz, University of Oklahoma
Larry Scott, Boston College

It took many years to complete this text, which was started by Phil Crews, professor of
chemistry at UC Santa Cruz, during the 1980s. In 1995 the other two coauthors, who were
researchers in residence at UC Santa Cruz, were invited to participate in transforming
the working draft into a final manuscript. The second edition was prompted by the over-
whelming changes in organic spectroscopy over the last decade and the need for a current
text on organic structure analysis using an integrated approach. We thank our colleagues
who asked for this new edition at every international meeting. Indeed, the final reason for
the second edition was our need to stop hearing the phrase “When are you guys bringing
out a new edition of the book?” We trust that this new edition is even more user-friendly
than the first edition, and we want to continue to improve it. Thus, your help will be appre-
ciated as we plan future revisions; so, please contact any of us at our current institutions
about errors, suggestions for additional examples, or questions that you might have. We
can be reached as follows: Phillip Crews, University of California at Santa Cruz (phil@
chemistry.ucsc.edu); Jaime Rodríguez, Universidade da Coruña, Spain (jaimer@udc.es);
and Marcel Jaspars, University of Aberdeen, Scotland, UK (m.jaspars@abdn.ac.uk).

March 2009
Phillip Crews
Jaime Rodríguez
Marcel Jaspars
This page intentionally left blank
 1
Using Spectroscopic and
Analytical Data in Organic
Structure Analysis

C H A P T E R O U T L I N E

1.1 A Glimpse of the Methods in Common Use 1

1.2 Characteristics of the Methods in Common Use 6
1.3 Steps in Establishing a Molecular Structure 11
1.4 Molecular Formula (MF) and Unsaturation Number (UN) 13
1.5 Substructures, Working Structures, and Final Structures 14
1.6 Limitations of Spectroscopic Data in Structure Analysis 16
Sources for Further Reading 19
Problems 20
More Challenging Problems 23

rawings of molecular structures are information packed, and these images, rather

D than a formal name, crisply describe all the features of an organic substance. Such
imagery is so important that the use of molecular structures is ubiquitous both
in oral presentations and in the literature of organic chemistry. These pictures reveal a
molecule’s major structural elements divided into the two-dimensional structure—the
carbon skeleton, the various functional groups, and their locations (regiochemistry)—
and three-dimensional features—relative or absolute stereochemistry of substituents.
Establishing molecular structural parameters is something both research students and
professional organic chemists must repeatedly do, and it is a job greatly facilitated by
analytical equipment.

1.1 A Glimpse of the Methods in Common Use

Four primary instrument-based techniques have been in use since the early 1960s. They
are nuclear magnetic resonance (NMR), infrared (IR), ultraviolet-visible (UV-VIS), and
mass spectrometry (MS).1–3 Each of these methods will be featured here because all are
used daily by most organic chemists: they require a minuscule amount of material, and

1
2 Using Spectroscopic and Analytical Data in Organic Structure Analysis

for the most part they are nondestructive. These methods are also in common use because
they provide information vital to defining a molecular structure. Complete formulas can
be established by identifying the molecular ion during an MS determination. The count
of C and H atoms can also be ascertained by NMR, and this data also provides infor-
mation about functional groups. NMR spectroscopy often provides an alternative to the
classic way to identify functional groups through IR and UV-VIS data. It is important to
recognize that combining insights from all these methods is often essential to completely
define a molecular structure. An alternative, single-step approach employs X-ray crystal-
lography; this however, usually requires well-formed crystals, as liquids or powders are
not appropriate for analysis.
Compounds with molecular weights of less than ∼1500 amu are excellent candi-
dates for study by the methods of organic spectroscopy. It is generally believed that the
unequivocal structure analysis of such small organic compounds is now a routine task.
The powerful tools widely available, consisting of multidimensional NMR, ultra-high
resolution mass spectrometry, tandem mass spectrometry, and chiroptical measurements,
should all be used in combination. As an illustration, collecting one or more pieces of
such data allows an environmental scientist to rapidly recognize the presence of the anti-
coagulant factor, dicoumarol (1) (336.1 amu, C19H12O6), produced when fungi infect white
sweet clover. The plant is a danger to grazing cattle, and the molecular structure of dicou-
marol, with slight modification, was the inspiration for warfarin, used in rat abatement. A
data set consisting of a mass spectrum and an 1H NMR spectrum would help distinguish
this structure from other nonharmful coumarin analogs, which are also ubiquitous in feed
grains. A synergistic approach of using MS, 1H, and 13C data provides immense power,
especially in the characterization of substances rich in H atoms and methyl groups. For
example, utilizing data so acquired makes it possible to completely assemble the struc-
ture of such glycoside-steroids as the plant-derived cardiotoxin digoxin (2) (780.4 amu,
C41H64O14).

O
OH
O

O O HO

Dicoumarol (1)

O
O
OH

H
HO HO O
O O
H OH
O
HO O HO O
H

Digoxin (2)

Representative of far-reaching successes in using one or more of the tools, NMR, IR,
UV-VIS, and MS, are descriptions of the molecular architecture of exceedingly complex
 1.1 A Glimpse of the Methods in Common Use 3

natural products. Perhaps at the top of the list is the intricate structure of the polyether
natural product palytoxin (3) of mass 2678.5 amu and molecular formula C129H223N3O54.
Its seemingly never-ending structure was initially proposed based on spectroscopic data.
But the process of collecting the appropriate data, making unambiguous interpretations,
and reweighing the data, including information obtained from total synthesis, took some
20 years!

OH
O
H2N O
O OH
OH OH
HO OH
OH
O OH
OH

HO OH
OH OH
OH
OH
OH
HO OH O
O O OH OH
OH
OH OH
HO N N O
H H
OH OH OH HO
HO
O OH
OH O
O OH HO
OH
OH
O
OH
OH OH OH
HO OH
OH

Palytoxin (3)

The use of multiple pieces of analytical data is the best recipe to efficiently estab-
lish or validate an important molecular structure. A brief review of selected examples
from several compound classes provides some useful lessons. The cholesterol biosyn-
thesis inhibitor lovastatin (4) (404.3 amu, C24H36O5) is a fungal polyketide; its signature
functional groups, identified from NMR, IR and UV data, include a conjugated diene, a
secondary alcohol, a lactone, and an ester group. Laying out the complete list of the func-
tional groups of artemisinin (5) (282.3 amu, C15H22O5), a sesquiterpene of plant origin and
a powerful antimalarial drug, could be especially challenging and requires the insight that
there are no heteroatom protons. The dipeptide-like structure of E7974 (6) (437.3 amu,
C24H43N3O4), a synthetic antitumor agent, is rich in methyl and carbonyl residues. Great
atom diversity is present in the major disaccharide 7 (577.0 amu, C12H19NO19S3), obtained
from the enzymatic degradation of heparin. In recent years advances in NMR and MS
instrumentation and in experimental strategies have made it possible to tackle even the
structure elucidation of very complex compounds, made up of nonrepeating biosynthetic
subunits. However, connoisseurs of this subject recognize that even when all these tools
are applied, errors can be made and other considerations, including synthesis, may be
needed. Later in this chapter, we shall discuss cases taken from the literature in which
difficulties were encountered in deriving correct molecular structures.
4 Using Spectroscopic and Analytical Data in Organic Structure Analysis

HO2C OH

O
OH OSO3H
H
N O
HO3S

HO O
OSO3H

Disaccharide (7)

To be successful in the task of organic structure analysis, especially when an exotic

compound is in hand, requires several attributes. In addition to chemical common sense,4
it is helpful to have experience in five other areas. First, a general knowledge about princi-
ples of organic structures is a must. You should also have an understanding about common
functional groups. Being able to pick out the isoquinoline alkaloid substructure present
in morphine (8) provides a simple illustration about dealing with functional groups. It is
important to have facility for conceptualizing structures that are especially stable, such
as homoazulene (9) (a nonbenzenoid aromatic); exceedingly unstable, for instance pen-
talene (10) (a planar 4n p-electron system); or immensely strained, such as cyclopentyne
(11). Having familiarity with functionality prone to convert into something else is also
essential. One such case is dicoumarol, whose b-dicarbonyl residue can transform by tau-
tomerization between such forms as 1, 1a, and 1b. Similarly, an equilibrium through an
electrocyclic rearrangement of the polyene chromophore interconverts norcaradiene (12a)
and 1,3,5-cycloheptatriene (12b). Second, an organized and systematic approach must be
applied. Third, understanding of how to interpret a spectral trace is essential. Fourth, an
appreciation of the dangers of using negative or unreliable data to make positive conclu-
sions about a molecular structural feature is important. Fifth, being able to maintain a
proper perspective when conflicting data sets seem to be in hand is necessary, since under
such circumstances it is helpful to draw on experience gained from past success in prob-
lem solving. Finally, to simultaneously use data from NMR, IR, UV-VIS, and MS and
to look repeatedly for multiple pieces of data to support individual conclusions might be
considered to be a universal goal. Taking time to reevaluate a conclusion will also help to
avoid mistakes. This can be accomplished by defending the logic of how a structure was
elucidated before a critical audience (e.g., the practice of peer review).
Determining a complete organic molecular structure begins with the isolation, syn-
thesis, or purchase of a pure compound. Spectroscopic data is then obtained to derive
the following information: (1) molecular formula, (2) identities of functional groups,
 1.1 A Glimpse of the Methods in Common Use 5

O O O
OH O O
O O O

O O HO O O HO O O O

Dicoumarol (1) (1a) (1b)

(3) carbon connectivities, (4) positions of substituent and functional groups on the carbon
framework, and (5) stereochemical properties, including dynamic and static aspects. The
overall flow of information processing is summarized in Figure 1.1.
The step-by-step approach actually used in an organic structure determination will
vary greatly as a function of several variables, such as the source of the material under
study. For example, if the sample is a commercial compound, then limited physical prop-
erties might be measured in connection with a quality assurance determination. For a
synthetic reaction product, reasonable assumptions might also be made about the molecu-
lar formula, the functional groups present, and the overall carbon skeleton to which func-
tional groups are attached. Consequently, only a few pieces of spectroscopic data might
be sought. By contrast, an extensive data set must be obtained for a newly isolated natural
product when its structure is presumed to be unknown. Examples of other important fac-
tors that often come up include the amount of sample on hand, instrument time available
versus time needed to obtain spectroscopic data of various types, personal experience
and/or preference for data derived from a particular technique, general insights gained
from practice in problem solving by means of spectroscopic data, and the ability to find
appropriate empirical reference data to back up a conclusion.
Undertaking a complete analysis of all the data from each of the four spectroscopic
methods is not always the most effective way to proceed. An infrared or a mass spectrum
can contain more information than can be correlated with specific elements of organic
6 Using Spectroscopic and Analytical Data in Organic Structure Analysis

FIGURE 1.1 Overall flow of information.

FIGURE 1.2 A sampling of candidate structures 13–16

for C 4H4O2, C5H8O, or C6H12.

structure, so only a portion of the data obtained is useful. Also, data from the four spec-
troscopic techniques are not equivalent in the extent to which they will aid the identifi-
cation of various organic structural elements. For example, spectroscopic analysis of an
unknown whose mass is 84 amu provides the following: MS, 1 or more peaks; IR, 12
peaks; 1H NMR, 1 peak; 13C NMR, 1 peak; UV-VIS, no peaks. There are many candidate
molecular formulas consistent with the MS peak (assumed to be the molecular ion: see
Chapters 6–8), and the three most obvious formulas are C4H4O2, C5H8O, and C6H12. Four
structures, 13–16, plus several others, could be drawn to fit this list of formulas, and these
four are shown in Figure 1.2. We find that UV-VIS spectrum (Chapter 10) shows only
what is not present, no conjugated unsaturation; and this information is helpful in decid-
ing to set aside possibility 13. Close inspection of IR data (Chapter 9) could eventualy
reveal the absence of heteroatom protons and the presence of C–C and C–H groups only,
thereby ruling out candidate 14. Important information comes from observation of just
one resonance in the 1H NMR spectrum (Chapter 2), which introduces the requirement of
one or more elements of symmetry among all the protons. This is consistent with struc-
tures 15 or 16 (and 13, ruled out earlier). Last, the single peak observed in the 13C NMR
spectra (Chapters 2–5) indicates that only cyclohexane (16) is uniquely consistent with all
the preceding data. This discussion illustrates the trial-and-error process we will use in
deducing organic structures from data sets.

1.2 Characteristics of the Methods in Common Use

It is useful to focus on specific characteristics of the major spectroscopic meth-

ods. Summarized in Table 1.1 are properties of nuclear magnetic resonance (NMR),
Another random document with
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 To arrive there in time we should have to take the train next
morning. I went accordingly to the princess, who was the only person
whom I knew in Roumania, to ask her if she would come to my
assistance.
I called on her at nine o’clock in the morning. I was taken to the
second storey of the palace, to a room that was even prettier, if
possible, than the one in which I had been received the first time.
The princess received me. She was in her night-robe, and had
put on a dressing-gown of white silk over which her beautiful
dishevelled hair hung. She was still engaged in her toilet when I
arrived, but in order not to make me wait, she bade me come into
her little boudoir, where no one would disturb us. The room, filled
with well-chosen first editions, was in charming taste. Everywhere
there were little draped statuettes on pedestals. Beside the fireplace
was a very comfortable corner. In the midst of all these beautiful
objects one might have thought oneself in a miniature museum.
I asked her what she liked best among all the things there and
she replied, “the rosaries,” of which she had quite a collection. What
an artist she must be to bring together all these beautiful things.
“This is my room,” she said, while we were talking, “in which
whatever happens no one is permitted to bother me. I take refuge
here from time to time, and remain until I feel myself ready to face
the world once more.”
I then told her my troubles. She rang a bell, and gave an order to
let M. X—— know immediately that Miss Fuller would come to see
him with a card from her, and that M. X—— would kindly do
everything in his power to assist Miss Fuller.
I looked at her for some time and then I said to her:
“I should have liked greatly to know you without being aware that
you were a princess.”
“But,” she said, “it is the woman whom you now know and not the
princess.”
 And that was true. I felt that I was in the presence of some one
who was really great, even if her birth had not made her so. I am
certain that she would have accomplished great things if she had not
found her career already mapped out for her from the day of her birth
in her father’s palace.
Everyone knows that a princess’ life precludes liberty, and
contains no possibility of breaking with the conventions for the sake
of doing something extraordinary or notable. These chains are so
strong that if one contrives to break them, it generally happens under
the impulse of despair, as a result of irritation and not for the sake of
a purely inspired work.
When I arose to take leave of the princess she kissed me and
said:
“If ever I come to Paris I shall call on you at your studio.”
She caused an attendant to accompany me to the master of
ceremonies, with whom I was to go to the bank. There the master of
ceremonies communicated Princess Marie’s order to the effect that I
was to be accommodated in any way I might desire.
The money I needed was advanced in return for a cheque, and I
left Bucharest.
The journey was full of troubles. Vexatious delays occurred.
Finally I arrived at Rome, where my appearance had to be
postponed until my baggage, lost in transit, had been found. Three
thousand people, who had come to my first performance, went away
without seeing me. That certainly was very hard luck. If I had been
able to foresee all that, I should never have ventured to intrude upon
the Princess.
In that case I should not have discovered what an admirable
woman she is.
 XV
SEVERAL SOVEREIGNS

I N the course of my travels about the world, east, west, north and
south, over oceans and across continents, I have had the
experience of seeing or of encountering many persons of
distinction, including not a few sovereigns and members of royal
households.
It has seemed to me that it might be interesting to bring together
at this point some of the most typical of the incidents that occur to
me. Just as they come, drawn haphazard from memory, without
order or sequence, and with no thought of literary composition, I am
going to put them simply on paper, one by one.

How I Failed to see Queen Victoria.

One day at Nice some one came and asked me to dance before
Queen Victoria. She had just arrived on the Riviera to pass the
winter months, as she was accustomed to do every year.
It may well be believed that I was flattered by such a request. I
assented, naturally, and set myself to work making all my
preparations for this important event.
There was a knock at the door. A maid brought a telegram. It was
signed by my manager, and was couched in the following words:
“Take train this evening, to sail day after to-morrow; destination, New
York.”
I replied with a message pleading for a delay, for the purpose of
dancing before Queen Victoria.
I received simply the following laconic telegram:
“Impossible. Leave at once. Time is money.”
 That’s why I did not dance before Queen Victoria.

I stop the Queen of the Belgians in the Street.

I was engaged for some performances at Spa. The evening of my
first appearance the Queen and Princess Clementine were in the
royal box. That was a gala evening, one on which the hall was
resplendent with magnificent gowns and jewels.
Everything went off perfectly.
Next morning I went for a walk with my mother. We were crossing
the causeway when a carriage, drawn by two spirited horses driven
by a middle-aged woman, bore down upon us.
Frightened on account of my mother, I threw up my arms in front
of the carriage, which stopped.
The lady allowed us to pass and, while thanking her, I remarked
to myself that a woman ought not to drive such lively horses.
I had forgotten the incident when, shortly after my return to the
hotel, I saw the same carriage go by.
Two gentlemen were talking on the landing near us.
“See. There is the Queen,” said one of them.
It was the Queen whom I had stopped!

Princely Simplicity.
At the Hague I was asked to give a performance before the
Grand Duke and Duchess of Mecklenburg, Princess Victoria of
Schaumburg-Lippe and their retinue.
The hall was well filled. I had the Philharmonic Society’s
orchestra.
This was a gala evening, and in every way a very successful one
for me.
 Next day on coming down from my room I encountered on the
stairway of the hotel a lady with a very sweet expression, who asked
me:
“You are Miss Loie Fuller? Your dances interest me greatly. My
husband has gone out on the beach. Wouldn’t you like to come and
talk to him about your lighting effects. I am sure that would prove
very interesting to him.”
I gladly acquiesced and followed her.
I was delighted to talk to this woman and her husband, who
proved to be a most delightful man. I explained to them all my
schemes of lighting and my dances. I then took my leave and joined
my mother, who was waiting for me.
When I returned to the hotel the proprietor came to me and said:
“You met with great success yesterday, Miss Fuller, and with
even greater this morning.”
“This morning?”
“Yes. Do you know who the gentleman is with whom you have
just been talking?”
“No. Who is he?”
“The Grand Duke of Mecklenburg.”
This same day I boarded a street car.
On the car several people appeared to know me. One lady came
and sat beside me and began to talk.
When we arrived at our destination I asked her if she would not
tell me her name.
“Victoria de Schaumburg-Lippe.”
One evening when I was dancing at the Hague the princess was
in the hall with Major Winslow and others of her retinue. She sent for
me, and asked me to show her one of my robes.
I brought her the robe which I put on for the butterfly dance.
 She took the stuff in her hand and said:
“The robe is really wonderful, but it is after all only what you do
that counts.”
I remember that she asked me to sign a photograph for her. And
when I returned to the hotel the manager of the Kurhaus handed to
me an exceedingly pretty watch, on the cover of which were
engraved these words:
“In memory of the performance given for Princess Victoria.”

The Curiosity of the Archduchesses of Austria.

I was once at the Swedish gymnasium at Carlsbad, where
machines with electrical vibrations shock you from head to foot. I
was just about to dress myself when one of the women of the place
came to me, and said:
“Won’t you please return to the hall, and pretend to take the
electric treatment again in order that the archduchesses, who are
there, with a whole crowd of court ladies, may see you?”
I replied: “Tell the archduchesses that they can see me this
evening at the theatre.”
The poor woman then declared to me that she had been
forbidden to mention their Royal Highnesses, and that they had
bidden her get me back into the hall on some pretext or other.
She was so grieved at not having succeeded that I returned to
the machines, and had my back massaged, in order that the noble
company might look at me at their ease, as they would survey an
interesting animal.
They looked at me, all of them, smiling, and while they viewed
me I never turned my eyes away from them.
The odd thing was that they did not know that I knew them. I was,
therefore, as much amused by them, and without their perceiving it,
as they were amused by me.
 How I was not decorated with the Order of the Lion
and the Sun of Persia.
During one of the visits that the Shah of Persia pays to Paris, the
Marquis and Marquise d’Oyley, who were great friends of the
Sovereign and who were very fond of my dancing, brought the Shah
to one of my performances at Marigny.
After my appearance on the stage the Marquis and Marquise,
accompanied by some dignitaries of the sovereign’s retinue, came to
my dressing-room and brought me a Persian flag, which they
begged me to use in one of my dances.
What could I do with that heavy flag? In vain I racked my brain. I
could not discover any way. I could not refuse, and I was unable on
the other hand to convince them that it was impossible to try
anything so impromptu without running the risk of a failure.
More and more perplexed I made my entrance for the last dance.
I had the great flag in my arms. I tried to wave it gracefully, but I did
not succeed. I tried to strike a noble attitude, still holding the flag.
Again I failed. It was a woollen banner and would not float. Finally I
stood stock still, holding the staff upright, in as imposing an attitude
as possible. Then I bowed until the curtain fell.
My friends were surprised to observe that my last dance had
displeased his Majesty. The Shah finally told them that he did not
see why the Persian flag had been desecrated. No one dared to tell
him that the idea had not come from me, but from persons of his
retinue, or to inform him how I had received the flag.
My friends, the d’Oyleys, consoled me by saying that my pose
had been very noble and that even the flag, falling around me in
heavy folds, had produced a very striking effect.
The Shah decorates everybody who has attracted his attention;
that is a habit he has acquired. For my part, thanks to the brilliant
idea of the dignitaries from the court of Teheran, I have never seen
either the tail of the Lion or a ray of the Sun peculiar to Persian
decoration.
 I have been told on other authority that on this evening the
Shah’s first thought was of a bomb which, so it had been announced,
was to be thrown at him in the hall. He was thinking of this rather
than of my person, my dances or even of the Persian flag I
“profaned.”

My Adventure with a Negro King.

At the Colonial exposition in Marseilles in 1907 I was with some
friends in the pavilion of one of the exhibitors when a magnificent
negro, six feet high, who looked like some prince from the Thousand
and One Nights, came upon the terrace where we sat. He was
accompanied by a large retinue. The other negroes were dressed
the same as he, but none of them had his magnificent presence.
Some French officials accompanied the visitors, who, naturally,
created a tremendous effect with their costumes, which were simple
but exquisitely finished. When they came near I exclaimed:
“He might be called a king out of a fairy tale!”
They passed before us and took their places in the reception hall.
The proprietor presently came to our group, and asked us if we
would not like to assist him in receiving the King of Djoloff in
Senegal.
“He is visiting the Exposition as a private citizen,” he added. “If
you would like to make his acquaintance come and I will present
you.”
I was charmed.
When I was in the presence of the king, I said quietly to my
friends, in a distinct voice and in French:
“What a handsome savage; I wonder if they are all built on this
model in Africa.”
I was presented to the king. He extended his hand, and, to my
consternation, I heard him say in very good French:
 “I am delighted to make your acquaintance, Miss Fuller. I have
applauded you frequently. My education was gained in Paris.”
I could not repress an exclamation.
“Good heavens! Then you heard what I said, and you never
raised an eyelash!”
“No, since you did not suppose that I understood you.”
I looked at him for a minute or two to find out whether he had
been irritated or not. He smiled diplomatically and I felt that we
should be friends.
I was dancing at Marseilles at that time. He came to the theatre
to see me after the performance.
“What can we do that will give you pleasure in exchange for the
great satisfaction that your dances have just brought us?” he asked
me.
I thought the matter over a minute.
“I should like it very much if I might be present at one of your
religious ceremonies.”
The black chief promised to come to my hotel, and to give me an
idea of the ritualistic practices of his country.
The next day, accordingly, I made preparations for a tea-party in
the hotel garden. Rugs were spread on the grass and everything
was in readiness to receive the monarch.
“When will the ceremony begin?” I asked the king as soon as he
had arrived.
“We shall say our prayer at six o’clock, just at sunset.”
As night came on I observed that the king and his followers
began to survey the sky in every direction, and I wondered why.
Noting my wonderment, the king told me that they were
endeavouring to get their bearings in order to be certain of the point
toward which the sun was tending at the end of his journey.
 “We are required,” he said, “always to pray with our faces toward
the setting sun.”
He gave the order to begin the ceremony then and there. I wish I
could describe it as perfectly as I saw it.
The unity of the motions of all these men was simply wonderful.
All together they said the same brief prayer, and with mechanical
precision made the same movement, which, from the point of view of
devotion, seemed to have similar importance to the words of their
ritual. The large white cloaks, spread over long blue blouses, waved
round their bodies. The men prostrated themselves, touched the
ground with their foreheads and then raised themselves together.
The rhythm and precision were most impressive. It was really very,
very beautiful.
After the prayers the king told me that his father had been
dethroned and then exiled from Senegal by the French Government.
As for himself, in his turn he had been nominated chief of his tribe,
for in reality there was no longer a king. He was a French subject,
and in his country, which was tributory to France, he was no more
than chief of his clan.
But the majesty remained, nevertheless, magnificently expressed
in his features.
While we were conversing I asked permission to put some
indiscreet questions. After he had consented, all the while smiling his
peculiarly winning smile, I asked him if he was married?
He replied in the affirmative. He had four wives. As I appeared to
be surprised to note that he travelled without them, especially in a
country where there are so many pretty women, he, in his turn,
looked at me for some time, and replied:
“From the point of view of my wives a white woman has neither
charm nor beauty.”
This surprised me greatly, and I asked him whether that was
because they had never seen any white women.
 “Oh,” he replied, “in any case they would not be jealous of a white
woman. It seems to them absolutely impossible that a pale-faced
woman can play any part in my life.”
“And you? Are you so sure of that? If a white woman with long
blonde hair should suddenly appear in your country, among your
black women, would she not be taken for an angel?”
“Oh, no. She would be taken for a devil. Angels are black in our
Paradise.”
This, I must confess, opened new vistas in the domain of religion.
It had never before appeared so clear to me that men make their
gods in their own image, rather than that the gods make men after
theirs.

How the Empress of China Degraded a Mandarin on

my Account.
I was dancing in New York when several of Li Hung Chang’s
followers came to the theatre. Some friends presented me to the
American military attaché, Mr. Church, who accompanied the
Viceroy.
Thanks to Mr. Church I was able to satisfy my curiosity and
become acquainted with these high Chinese dignitaries. When they
left for their own country my manager went with them, in the hope
that, through their good offices, I might dance at the Chinese court in
the presence of the dowager Empress and her son.
As soon as my representative was in China, he cabled me that
everything had been arranged and that I was to take the first
steamer leaving Vancouver.

After crossing the continent I was on the point of embarking with

my mother, when the state of her health caused me the keenest
anxiety. Her prostration was so complete that I was obliged to send a
message to China, indicating the impossibility of keeping my
engagement.
My manager rejoined us utterly dejected.
At Pekin a magnificent reception had been prepared for me. I
was to dance before the Emperor and Empress and then in Japan I
was to appear before the Mikado. The theatre of the best Japanese
actor, Danjero, was to be put at my disposal. And all that to no
purpose whatever. My manager brought back from this oriental
country the most marvellous of embroideries, which Li Hung Chang
had sent over for me.
I experienced genuine regret at the failure of this trip, then I forgot
all about it.
One evening in London one of my friends at dinner found herself
seated next to a very high Chinese official. Apropos of the rich
colouring of the mandarin’s garments, they came to speak about me
and my coloured dances, and my friend said to her companion:
“You are acquainted with Loie Fuller, I presume.”
“Well, yes, madam,” he replied. “I am only too well acquainted
with her, if I may say so.”
“How is that?”
“I went to the United States with Li Hung Chang. Loie Fuller’s
manager accompanied us on our return to China, and, through the
influence of the Viceroy, we gained permission for Loie Fuller to
appear before the Empress. Just as she was about to leave for
Pekin she broke her agreement. It fell upon me to inform her Majesty
that Loie Fuller was unable to obey the Imperial mandate. The
Empress had me degraded! That was eight years ago. I lost my
yellow jacket, which has only recently been restored to me.”
My friend pleaded my case, alleging the condition of my mother’s
health, and the seriousness of her malady at the time of my failure to
report in the celestial empire.
I suppose that it would be too much to expect of His Excellency
to ask him to forgive my mistake. If I had known that my failure to
appear would be attended with such consequences, I should,
instead of cabling to my manager, have forwarded a long dispatch to
the Empress herself, telling her the reasons for my failure to keep an
engagement. A woman with a heart, even if she be an Empress,
could not blame a daughter for doing her duty towards her mother.

How Queen Alexandra did not fail to see me.

One morning the papers said that the King and Queen of
England were going to spend several days in Paris.
I was then dancing at the Hippodrome and, remembering what
Princess Marie of Roumania had told me, I decided not to let this
occasion slip, and I wrote to the Queen herself, asking if she would
be kind enough to set aside an hour in which I might give a
performance, at her own convenience and whenever she chose.
I should never, indeed, have supposed it possible to ask her to
come to the Hippodrome. One of her maids of honour answered the
note, saying that Her Majesty’s stay was of limited duration, and that
she had already accepted too many invitations to undertake any new
engagements.
After that I thought no more of the Queen.
Arriving at a matinee one Thursday, I noticed in front of the
Hippodrome quite an impressive line of carriages, all displaying the
royal insignia.
“The Queen has sent some one to my matinee,” I thought. “She
wants to know whether my dances are really worth seeing. If I make
a pleasant impression the Queen will perhaps some day ask me to
dance before her.”
I went into my dressing-room. I had nearly finished my
preparations when the manager rushed in post haste calling out:
“It’s four o’clock and the Queen has been waiting since half-past
two.”
“What! The Queen is here! Why didn’t you inform me sooner?”
 He was too unnerved to make a lengthy explanation. I hurried
down and two minutes later I was on the stage.
In the middle of my dance the Queen arose and left the theatre
with all her attendants. I saw her rise and go!
I thought the floor would open and engulf me. What had I done to
offend her? Was she indignant that I had made her wait? Was this
her way of punishing me for my discourtesy, or did my dances
displease her? What was I to think?
I went home in utter despair.
I had just realised one of my dearest wishes, that of dancing
before the Queen. Never had I experienced such dejection. I should
have preferred a thousand times that she had not come.
I learned afterward at the theatre that a telephone message had
come shortly after noon to the effect that the Queen wished to see
Loie Fuller, but that she would have to leave at four o’clock.
The manager, who had supposed that the Queen was coming to
see the Hippodrome, had not attached any importance to the
intimation regarding me, and did not even take the trouble to find out
whether I was there or not.
Next morning all the papers recorded that the Queen of England
had come to the Hippodrome, despite her many appointments and
engagements made some time earlier, and so forth and so forth.
There was not a word about me.
However, as I had written to the Queen to ask her to come it
seemed to me that I ought to excuse myself for my apparent
discourtesy. I wrote to her accordingly, telling her how distressed I
was at my failure to appear earlier—a failure that would not have
occurred if some one had come to apprise me. I regretted that the
message had not been forwarded to me instead of to the manager.
That same evening one of my friends came to tell me that she
had written the day before to one of the Queen’s maids of honour,
whom she knew personally, asking her to come and see me dance
at the Hippodrome.
Photo Lafitte
THE DANCE OF THE BUTTERFLY
“That will make your new dances celebrated all over the world,”
said my friend. “The Queen will come, I am certain of it, if it is at all
possible.”
Overcome with surprise, I looked at my friend, and exclaimed:
“Well, then, that is why she came this afternoon!”
“Has she already come to see you? I should not have expected
such promptness.”
“She came to the matinee.”
And I told my friend the whole story in detail.
She still could not understand why the Queen had left so hastily,
and enquired into the reason.
Presently everything was explained.
The Queen had agreed to visit a painter’s studio at half-past
three and then, at four o’clock, to call upon M. and Mme. Loubet.
Nevertheless she remained at the Hippodrome until ten minutes past
four. The King went alone to the studio and the Queen arrived late at
the President’s house.
After that I fully appreciated her kindness, her patience. I still feel
endless gratitude to her for having waited so long, for not having left
the theatre without seeing, if it was only for a moment, Loie Fuller
and her dances.
As for the manager, he is still convinced that the Queen did not
come to see Loie Fuller, but the Hippodrome, and only the
Hippodrome.
 XVI
OTHER MONARCHS

I SHALL always remember with great pleasure my six hundredth

appearance in Paris.
I was then dancing at the Athénée. The whole house had been
bought up by students. When I came on the stage each spectator
threw a bunch of violets at me. It took five minutes to gather up the
flowers.
When I had finished dancing, a fresh avalanche of flowers poured
upon the stage. During the performance I received from my
admirers, along with an album of sketches signed with names,
several of which are now famous, an exquisite statuette representing
me in a characteristic attitude.
When I was ready to leave the theatre, the students took my
horses out of the shafts and drew my carriage themselves. At the
Madeleine the crowd was so dense that the police warned us to
stop. But as soon as they had learned that it was “La Loie” in whose
honour the triumphal procession was decreed, we had permission to
go our way without interruption. The young men drew my carriage all
the way to Passy, where I lived. They conscientiously awakened all
the inhabitants with their outcries.
Finally we reached the house. I did not know what I was going to
do with these boys, but they themselves solved the problem without
delay.
After they had rung the bell and as soon as my gate had swung
on its hinges they emitted a shout all together, and started to run
away as if possessed. I could hear them for a long time afterwards,
shouting: “Vive l’art! Vive La Loie!”
I have often wondered whether the police were as lenient on their
return.
 In Marseilles, at the time of the Colonial Exposition, one of the
commissioners of fine arts asked me if I would not like to perform
out-of-doors.
That was one of my dearest wishes, and I consented readily.
Preparations were made at once for my performance, which was
to be given in the same place where we had admired the King of
Cambodia’s dancers. The stage was built opposite to the Grand
Palais.
The director of the Exposition had placed behind the platform
some great plants, in order that I might be relieved against a
background of green foliage, which would be particularly favourable
to the brilliancy of the figures in the foreground. Below the stage
were two little ponds, with sparkling fountains.
The evening of my first appearance arrived. I was feverishly
impatient.
Nothing had been done to advertise it to the public of Marseilles,
for we regarded this first evening as a kind of rehearsal, which we
should repeat a week later, if it met with success. It was only this
next performance that we expected to announce formally.
It was a starlight night. There were at least thirty thousand visitors
at the Exposition.
The lights were put out and the crowd rushed towards the
platform. In spite of its impromptu character the performance was a
remarkable success, and the committee decided from this time on to
continue to give outdoor performances.
During the second evening, just as the lights were about to be
extinguished, a man came and said to me as I was on my way to the
stage:
“Just look, before they put the lights out, at the human wave
curling at your feet.”
I had never seen anything like it.
 After the electric lights had been shut off I began to dance. The
rays of light enveloped me. There was a movement in the crowd,
which reverberated in echoes like the mutterings of a storm.
Exclamations followed, “Ohs” and “Ahs,” which fused into a sort
of roar, comparable to the wailing of some giant animal.
You can hardly imagine anything like it. It seemed to me that on
my account alone this spectacle was presented by all this moving
crowd before me.
A calm ensued. The orchestra, not a very large one, seemed to
me utterly ineffective in such a space. The audience, which was
seated on the other side of the fountains, certainly could not hear it.
The first dance came to its close. The extinguishing of my lighting
apparatus left us, the public and me, in utter darkness. The uproar of
the applause became something fantastic in the dead of night. It was
like the beating of a single pair of hands, but so powerful that no
noise in the world could be compared with it.
I danced four times, and the different sensations expressed by
the audience were most remarkable. They gave me the most vivid
impression I have ever experienced. It was something immense,
gigantic, prodigious.
That day I had a feeling that the crowd was really the most
powerful of monarchs.
There are other monarchs as well as kings and crowds. Certain
emotions are kings, too.
At Nice, at the Riviera Palace Hotel, I noticed one day at a table
near mine a young man of distinguished appearance whose glance
met my own several times successively, almost, one would fancy, in
spite of himself. During the following days we surveyed each other
again and again at meal times, but without progressing further
towards acquaintance.
I had a number of friends with me. He was alone. Gradually my
heart went out to him, although we had never exchanged a word. I
did not know who he was, and I had no notion of seeking his
acquaintance. Yet his brown eyes and his type of personality, calm
and simple, exerted a sort of fascination over me. A week later I
discovered, to my great confusion, that I was perpetually haunted by
his eyes and that I could not forget his smile.
One evening there was a ball at the hotel. I was invited, of
course.
As I have already said, I had a great many friends there. All at
once, in a corner, I noticed my neighbour of the dining-hall. He spoke
to no one. He was not dancing. I began to feel sorry to see him so
entirely alone. My sympathy went out more than ever towards him.
Some days later I was engaged for a performance that was to
take place at the hotel in honour of a Russian grand duke, two kings
and an empress.
I remember that Patti was in the front row. When I appeared
before this choice assembly, a single figure persisted in detaching
itself from the rest of the crowd. It was the figure of my unknown
young man. Who could he be to be noted thus, in the role of an
invited guest, among these princes and princesses? He rested his
elbow on the back of his chair. His hand was under his chin. His legs
were crossed with easy negligence. He looked at me continuously.
Everybody applauded over and over again. He alone did not lift a
finger.
Who was this man? Why did his countenance haunt me? Why
did he watch me so insistently? Why did he not join in the applause?
The next day, on the verandah, I was comfortably seated in a
rocking-chair, all the while wondering who my handsome dark man
could be. Coming back to earth I saw him there by my side,
ensconced in one of those odd willow seats that enclose you as in a
sentry box.
His eyes again met mine. We did not speak, but both of us
experienced a deep desire to exchange greetings. Just at that
moment the hotel manager came up and began to talk to us. Then,
observing that we were not acquainted, he introduced us. I learned
then that he was son of an industrial leader of international standing