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STRATEGIES AND SOLUTIONS TO ADVANCED
ORGANIC REACTION MECHANISMS
 STRATEGIES AND
SOLUTIONS TO
ADVANCED ORGANIC
REACTION MECHANISMS
A New Perspective on McKillop’s Problems

ANDREI HENT
University of Toronto, Toronto, ON, Canada

JOHN ANDRAOS
CareerChem, Toronto, ON, Canada
Academic Press is an imprint of Elsevier
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 Dedication

To Paul, and to my parents—AH

To Mom, Ed, Riley, and Josh—JA
 Preface

THE PURPOSE OF WRITING THIS BOOK

Upon reading the title of this book one may wonder, “why write another book about reaction mechanism” among a
sea of already published books on this mature subject? We offer several reasons in the categories of pedagogy and
research.
With respect to pedagogy we point out the following issues. Pedagogical books on the subject of organic chemistry
do not contain references to the original literature. Disappointingly, authors do not take the time to explain how to draw
chemical structures and reaction schemes before introducing the plethora of chemistries according to functional group
characteristics. This is so vital and fundamental that the current osmotic “monkey-see-monkey-do” pedagogical
approach of copying an instructor’s motions without understanding is, we believe, the source of all frustrations
encountered by students, regardless of ability, in their study of organic chemistry. Instructors have forgotten that
the idea of learning the language of organic chemistry follows the same sense as how a child learns how to draw
the letters of the alphabet before learning how to pronounce them, read words, and then to construct sentences from
those words according to grammatical logic. In organic chemistry, two-dimension pictures of three-dimensional chem-
ical structures replace the function of words in sentences. The skill of reading and writing in organic chemistry is based
entirely on visual representation, communication, and understanding. Other missing aspects of pedagogy include: how
to problem solve, how to connect mechanisms with actual experimental evidence, and showing the evolution of various
proposed mechanisms for a given transformation and how each proposal is tested against experimental evidence.
Instead, in current pedagogical practice there is a strong emphasis on osmotic learning and rote memorization coupled
with a poor and nonchalant attitude to using curly arrow notation without regarding the arrow notation as a math-
ematical directed graph that follows strict rules. This is in sharp contrast to Henry E. Armstrong’s (the father of the con-
cept of valence) derisive comment that “a bent arrow never hit anything” when he described what he thought of the
concept of electron-pair displacement along conjugated systems.1 Some of these educational laments were nicely sum-
marized in a recent article in Chemical & Engineering News in 2016 based on a symposium entitled “Is There a Crisis in
Organic Chemistry Education” held at an ACS National Meeting in San Diego.2
With respect to research published in the literature there are the following issues. Modern scientific publications
show that scientists, particularly synthetic organic chemists, have a foggy understanding of reaction mechanism. They
are rather surprised, even shocked, to learn that the sum of elementary steps in a reaction mechanism must add up to
the overall stoichiometric balanced chemical equation for a given transformation. One of us (JA) recalls an amusing
situation at a conference of industrial process chemists when such a statement was made and the number of double
takes, unsettled frowns, and other facial contortions observed in the audience. Such reactions soon disappeared when
they saw illustrative examples from elementary organic chemistry learned in the undergraduate curriculum. Authors
of publications, particularly in communications, often represent mechanisms as a customary after-thought when con-
cluding their papers. They are left as a conjecture without any supporting experimental evidence. They are given as a
best educated guess with no serious follow-up to test hypotheses. It is perfectly acceptable for a synthetic chemist to
relinquish the task of supplying experimental verification for a reaction mechanism if they are not skilled in the kind of
techniques and instrumentation required to do so. However, it is not acceptable to put forward a conjectured mech-
anism without at least offering well-thought out suggestions as to how it can be tested given the fact that there exists
more than a century of well-established knowledge in the literature on mechanism elucidation techniques that form the
standard lexicon of the study of organic chemistry. This is consistent with the finding that more than two-thirds of
posed problems investigated in this work are based on conjectured mechanisms. Furthermore, we were surprised
to find some publications containing curly arrow notations that were sloppy and in some cases completely wrong,
which we believe is more telling of the peer review process than authors’ faux pas. We also point out that the modern
fad of depicting mechanisms as catalytic cycles, though it serves as convenient shorthand, obscures the visual

ix
x PREFACE

communication of mechanism because curly arrow notation for tracking electron flow cannot be used due to the
already used curly reaction arrows. Furthermore, authors do not always specify the oxidation states of metals in organ-
ometallic catalysts in these depictions. We suggest that authors who do not specify oxidation states in such represen-
tations likely do not know them, and therefore are not convincing readers of their papers that they know what they are
talking about.

WHAT THIS BOOK OFFERS

The main highlights of our contribution not mentioned by other books include the following:
• connecting the elementary steps in a reaction mechanism to the overall balanced chemical equation;
• depicting reaction mechanisms using the principle of conservation of structural aspect throughout the visual
display;
• balancing each elementary step in a mechanism according to number of elements and charges, and showing reaction
by-products along the way;
• showing care and rigor in using the curly arrow notation for one- and two-electron transfers;
• strongly connecting the experimental and theoretical evidences found that support a proposed mechanism for a
given reaction;
• showing how to problem solve when one is faced with the same question that is repeated 300 times in our book;
namely, given the following reaction with substrate structure A undergoing a reaction under conditions B that
yields product structure C, write out a mechanism that best satisfies the given evidence.
Our emphasis is on problem solving to showcase how to integrate all of the earlier ideas. The focus is on the how
aspect of problem solving. Problem solving is an active exercise that is a highly effective pedagogical tool to absorb,
assimilate, integrate, and implement tools learned, in contrast to the passive exercise of reading descriptive informa-
tion as is customary in the delivery of physical organic chemistry and reaction mechanism subjects in the current uni-
versity curriculum.
A key insight to contemplate is that a chemical drawing of a structure or mechanism is a representation of our
understanding of it. This statement is true for any kind of drawing beyond drawings of chemical structures. In our
experience over the course of this work we have found that the principle of conservation of structural aspect applied
to the drawing of structures in a mechanism scheme was the most powerful in directing our thought processes in writ-
ing out sensible and probable mechanisms. Time and time again the degree of clarity of presentation revealed a path to
a solution. Yet, amazingly this simple technique is never mentioned in all the books and pedagogical literature we have
found on the subject of organic chemistry. Well-displayed mechanistic schemes in truth do not need accompanying
text to explain what is going on in a chemical transformation. They can be read and understood readily without need
for redundant exposition.
With respect to balancing chemical equations, we point out that the equal sign notation was used in the 19th century
chemistry literature to keep track of atoms on the reactant and product sides without depicting chemical structures. In
those representations only molecular formulas were used for reactants and products. There was an obvious and strong
connection between the meaning of a balanced chemical equation and a mathematical one. The reaction arrow sign
was later adopted when equations were written out using chemical structures instead of molecular formulas. Borrow-
ing from van’t Hoff’s notation where arrows depicted the direction of a reaction from reactants to products, and there-
fore the kinetics and dynamics of reactions, the currently used representation of chemical equations resulted in
significant loss of information with respect to not specifying by-products and hence loss of information in deducing
reaction mechanism. In modern literature chemical equations are no longer balanced as before atom-by-atom. Syn-
thetic chemists adopted the reaction arrow notation since their focus was only on the substrate and product of interest
in a chemical reaction, and comparing their structures to see “what happened.”
Why would a research chemist investigate a reaction mechanism in the first place?
Some possible reasons include: (1) the product of the reaction they were carrying out yielded an unexpected prod-
uct—this could be a surprise or the result of a “failed” experiment toward an intended target product; (2) the reaction
has synthetic utility and knowledge of the mechanism can elucidate how to further optimize the reaction conditions to
a desired product outcome; (3) a reaction produces at least two desirable product outcomes depending on reaction
conditions and knowledge of the mechanism can exploit shunting the reaction in favor of each of these products in
high yield; or (4) the reaction is unusual and has no precedent in the database of known organic reactions. Rearrange-
ment and redox reactions are by far the two classes of reactions that generate the most interest and challenges in terms
 PREFACE xi
of reaction mechanism elucidation. Modern synthetic chemists are particularly keen on ring construction reactions that
can form more than one ring in a single step, and on reactions that are able to functionalize unactivated CH groups.
Regio- and stereoselectivity in reaction performance is also of very high interest and goes back a long way.
What constitutes “proof” or “evidence” in support of a proposed mechanism? What does it mean to say that you
understand how a reaction proceeds? There are some key philosophical aspects of providing evidence for a given
mechanism proposal that is thought to be operative for a given reaction that need mentioning. Experimental methods
used to study mechanisms are never 100% conclusive. Evidence is obtained from a consensus of experimental obser-
vations that are self-consistent and point in the same direction. Mechanisms can be disproved but not proved. This
statement needs some time to digest. From a set of mechanistic proposals for a given chemical transformation, rather
than proving directly which one is the mechanism, the approach is to devise a series of experiments to disprove them
until one is left standing that is most consistent with the available experimental evidence. This becomes the “accepted”
prevailing mechanism for the given transformation—for now. However, there is always the possibility of revision of
thinking based on new findings or extra verification pending the utilization of new, more efficient techniques or more
sensitive and accurate instrumentation or better computational methods that can become available in the future. Mech-
anisms are therefore regarded as tested models rather than ironclad theorems that are true for all time as is the case in
mathematics. This is a different line of thinking compared to mathematical proofs which can be constructed as deduc-
tive, inductive, or contradictive. The best evidence is to have a synergy between experimental and theoretical (com-
putational) support. Although our efforts may not achieve true certainty, they will undoubtedly produce much
opportunity.
Publications that demonstrate how mechanism informs organic synthesis, and vice versa, also demonstrate a complementary
and strengthened understanding of how reactions proceed. We point out that this key insight is often not practiced and hence
such papers are scarce in the literature. This may be a result of the personal rift between two giants in the development
of organic chemistry: Sir Robert Robinson (synthesis) versus Sir Christopher K. Ingold (mechanism).3–6 Unfortunately,
the two schools of thought that each man created had more of an antagonistic relationship between them than a coop-
erative one that survives to the present day. Their differing nomenclatures for the same ideas including opposing sign
conventions attached to substituent effects were a direct result of their mutual ego bashing and created in the early
days much unnecessary confusion for the rest of the chemistry community, hence delaying adoption of mechanistic
understanding and delaying advancement in science. Hard core mechanistic chemists are largely engaged in exploring
the minutia of mechanism details, such as the number of water molecules involved in the transition state of a hydration
reaction, which synthetic chemists would find no use for. On the other hand, hard core synthetic chemists have poor to
nonexistent mathematics skills which means they are unable to carry out and understand kinetics experiments and are
strained beyond their comfort zone in interpreting energy reaction coordinate diagrams. Mechanistic chemists, in turn,
do not routinely read the synthesis literature on natural products because they perceive their complex structures to be
outside the scope of their investigations. Yet, experimental problems often encountered in organic synthesis practice,
such as failed attempts to carry out intended reactions or the obtainment of unexpected products, can all be explained
and resolved by understanding the underlying reaction mechanism. A good example is the difficulty in trying to carry
out esterifications of salicylic acids due to the internal hydrogen bond that exists between the ortho juxtaposed carbox-
ylic acid and phenolic groups. A well-known synthetic chemist at Queen’s University in Canada “discovered” this
problem in his own research about a decade ago and thought that this was a “new” finding without knowing that
this problem was well described and investigated in the literature by mechanistic chemists several decades earlier.
The ideological tensions between synthetic and mechanistic chemists resulted in an identity crisis of Hamletian pro-
portions in the late 1990s when several heavyweights in physical organic chemistry convened a symposium to address
perceived declines in the field with respect to recruitment, scientific advancement, and funding. This crisis of relevance
to modern chemistry research led some to remind the community of its triumphs over many years in advancing basic
science and its connection to other emerging fields in chemistry. Others advocated for a complete rebranding of the
perceived “dead subject” to make it more palatable and ultimately marketable to chemists working in the well-funded
applied areas of biological chemistry and material science. The reader is referred to the second issue of Pure and Applied
Chemistry (1997) and the first issue of Israel Journal of Chemistry (2016) which are special issues containing several papers
discussing this ongoing debate albeit largely written by old-guard members of a bygone era. Another more recent
account traces historical highlights of the field.7
The main take-home message that we hope comes across to the reader in this book is that the intellectual exercise of
elucidating reaction mechanisms works hand-in-hand in the service, understanding, and ultimately improvement of
organic synthesis design and thinking. Putting problem solving as the main focus of human effort over base human
needs of recognition and attribution is more convincing to aspiring young scientists to join the enterprise to increase
xii PREFACE

human knowledge in the chemical sciences and ultimately to make serious contributions to addressing pressing prob-
lems that actually matter to the wider world.

ORGANIZATION OF BOOK AND LAYOUT OF SOLUTIONS

We present a brief synopsis of the topics covered in each chapter.
Chapter 1: Logic of Organic Reaction Mechanisms
• What constitutes a chemical reaction?
• The importance and meaning of a chemically balanced chemical equation and its connection to reaction mechanism
• What constitutes a reaction scheme?
• The principle of conservation of structural aspect
• Curly arrow notation convention and correct implementation for two- and one-electron transfer steps
• Illustration of the fundamental ideas of reaction mechanism using the Baeyer-Villiger oxidation reaction as a
worked example
• Survey of textbooks of physical organic chemistry
• Special topics: base strength and pKa, autoxidation
Chapter 2: Evidence for Organic Reaction Mechanisms
• What constitutes physical organic chemistry?
• Energy reaction coordinate diagrams—how to construct, read, interpret, and use them
• Summary of direct and indirect experimental evidences to support reaction mechanisms
• Illustration of the evolution of supporting experimental evidence using the Baeyer-Villiger oxidation reaction as a
worked example
Chapter 3: Problem Solving Organic Reaction Mechanisms
• Theoretical problem-solving strategies applied to reaction mechanism proposals
• Experimental problem-solving strategies to support reaction mechanism proposals
• Illustration of both kinds of problem-solving strategies using the acid-catalyzed cinenic acid to geronic acid
rearrangement as a complete case study
• Current state of pedagogy and research in physical organic chemistry
Chapters 4–9: Solutions to 300 Problems
Over the course of his teaching career Prof. Alexander McKillop surveyed the literature and collected interesting
examples on cards and used them in making up problem set exercises for his students. Most of the posed problems
originated from brief communications in the literature which contained transformations that could be classified as
either anomalous, curious, yielded unexpected results, were challenging to rationalize, were explained by dubious
mechanistic reasoning, or whose author-suggested mechanisms were outright incorrect. His original book publication
Advanced Problems in Organic Reaction Mechanisms (1998) was a transcription of these cards but did not include the
original references and the problems were listed in a random order. No doubt, these problems were a fertile training
ground for his students to think logically about proposing rational mechanisms, particularly for students pursuing
research in natural products synthesis and organic synthesis methodology. All of the chemistries highlighted offer
opportunities for further investigation which astute students could use to explore in their own research careers. Hence,
McKillop really offered his students ideas for their own research proposals if they were to pursue academic careers.
The good news is that there exists a never-ending supply of such examples in the literature for instructors and
researchers to draw upon for posing future problems as training exercises.
The following template protocol was used for displaying solutions.
(i) A problem statement is given showing structures of substrates and products, reaction yields, and reaction
conditions. Corrections to any structural errors introduced by the posed questions in McKillop’s original book are
made as appropriate.
(ii) The first solution given is the reaction mechanism as given by the authors.
(iii) All mechanisms are displayed according to the following convention: (1) all chemical structures are shown in the
same structural aspect for enhanced visual clarity, (2) each elementary step is element and charge balanced, (3) the
 PREFACE xiii
curly arrow notation is used to track all two- and one-electron movements, (4) reaction by-products are shown
directly below step reaction arrows, and (5) target synthesis bonds made are highlighted using bolded notation
throughout a given mechanism scheme.
(iv) At the conclusion of each mechanism an overall balanced chemical equation is provided which constitutes the
sum of all elementary steps.
(v) A reference citation on which the problem is based is given.
The “key steps explained” section to each solution contains the following information: (1) an accompanying word
description of the visual display of the mechanistic scheme showing descriptors of intermediate identification (enols,
carbenes, thiiranium ions, etc.); (2) inclusion of all experimental evidences in support of the authors’ mechanism; (3)
inclusion of alternative mechanisms not considered by the authors; (4) discussion of any controversies, errors, or weak
or lack of evidence; (5) inclusion of alternative mechanisms that better agree with the experimental results and reaction
conditions, or address our perceived errors in the authors’ posed mechanisms; (6) inclusion of ring construction map-
ping notation if the reaction produces at least one ring in the product structure; (7) suggestions for further work to
improve any authors’ shortcomings (e.g., other experiments based on techniques described in Chapter 2, and theoret-
ical (computational) work); and (8) inclusion of other circumstantial evidence found from our literature searches on
more recent related work to the problem posed.
Finally, additional resources for the reader to consider to learn more about the type of reaction posed in the problem,
synthetic utility, other applications, and so on, are given at the end of each solution.

ACKNOWLEDGMENTS

We thank Dr. Floyd H. Dean for suggesting the cinenic acid to geronic acid rearrangement as a key example to
illustrate problem-solving techniques and the application of the principle of conservation of structural aspect, and
for generously offering his time to discuss some of the more difficult problems and his help in resolving them. We
also thank Amy Clark, Senior Editorial Project Manager at Elsevier, and her successor Peter Llewellyn for their extraor-
dinary patience over the course of this 4-year odyssey. We have climbed many small mountains and have grown intel-
lectually along the way. We hope this book inspires others to follow our footsteps and climb even higher mountains of
their own.
In closing, we leave the reader with some interesting and relevant quotes from Justus von Liebig and Friedrich
W€ ohler, who occupy the same position as Abraham in the hierarchy of contributors to chemical science, that touch
on various points highlighted in this Preface. In these quotes the pronouns “he,” “his,” and “him” are used throughout,
but the reader should interpret them to include both genders.
As a student reading chemistry8:
“It developed in me the faculty, which is peculiar to chemists more than to other natural philosophers, of thinking in
terms of phenomena; it is not very easy to give a clear idea of phenomena to anyone who cannot recall in his imag-
ination a mental picture of what he sees and hears, like the poet and artist, for example. Most closely akin is the peculiar
power of the musician, who while composing thinks in tones which are as much connected by laws as the logically
arranged conceptions in a conclusion or series of conclusions. There is in the chemist a form of thought by which all
ideas become visible in the mind as the strains of an imagined piece of music. This form of thought is developed in
Faraday in the highest degree, whence it arises that to one who is not acquainted with this method of thinking, his
scientific works seem barren and dry, and merely a series of researches strung together, while his oral discourse when
he teaches or explains is intellectual, elegant, and of wonderful clearness.”
Letter to Berzelius on experiments9:
“The loveliest of theories are being overthrown by these damned experiments; it is no fun being a chemist
any more.”
ohler’s paper on the elucidation of the structure of the benzoyl group10:
Introduction to Liebig and W€
“When in the dark province of organic nature, we succeed in finding a light point, appearing to be one of those inlets
whereby we may attain to the examination and investigation of this province, then we have reason to congratulate
ourselves, although conscious that the object before us is unexhausted.”
xiv PREFACE

ohler’s paper prediction about the power of organic synthesis11:

Liebig and W€
“The philosophy of chemistry will draw the conclusion that the production of all organic substances no longer belongs
just to living organisms. It must be seen as not only probable, but as certain, that we shall be able to produce them in our
laboratories. Sugar, salicin, and morphine will be artificially produced. Of course, we do not yet know how to do this,
because we do not yet know the precursors from which these compounds arise. But we shall come to know them.”
Liebig’s view of scientific training12:
“It is only after having gone through a complete course of theoretical instruction in the lecture hall that the student
can with advantage enter upon the practical part of chemistry; he must bring with him into the laboratory a thorough
knowledge of the principles of the science, or he cannot possibly understand the practical operations. [For] if he is
ignorant of these principles, he has no business in the laboratory.”
Liebig’s view on science investigation13:
“In science all investigation is deductive, or a priori. The experiment is but the aid to the process of thought, as an
arithmetic operation is; and the thought, the idea, must always precede it – necessarily precede it – in every case where
a result of importance is looked at.”
ohler on organic chemistry14:
W€
“Organic chemistry nowadays almost drives me mad. To me it appears like a primeval tropical forest full of the
most remarkable things, a dreadful endless jungle into which one does not dare enter, for there seems no way out.”
A poignant account of ideological thinking and bias15:
“When Kathleen Lonsdale produced the X-ray crystallographic evidence of the planarity of the benzene ring, Ingold
declared that ‘one paper like this brings more certainty into organic chemistry than generations of activity by us pro-
fessionals’. That remark bears a striking resemblance to the recent affirmation by Chargaff: ‘amateurs often are better in
advancing science than are the professionals’. The point that lies behind such remarks is that ‘professionals’ have usu-
ally shared, to some degree at least, a perception of what is internal and what [is] external to their discipline. The self-
images, reinforced by institutional characteristics, have had an important bearing on the progress of organic chemistry
because they have determined the curves of the boundaries which, at different times, have separated it from other
disciplines. Where the boundary should be drawn has, of course, been another source of controversy. Too high a
degree of insularity has also had an adverse effect. A perspective which emerges very clearly from recent scholarship
is that the moat which at various times separated organic from physical chemistry acted like the other kind of mote.”

Andrei Hent and John Andraos

Toronto, Canada

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2. Halford B. Is there a crisis in organic chemistry education? Chem Eng News. 2016;94(13):24–25.
3. Saltzman MD. In: James LK, ed. Nobel Laureates in Chemistry 1901-1992. Washington, DC: American Chemical Society; 1993:312–313.
4. Ridd JH. Organic pioneer: Christopher Ingold’s insights into mechanism and reactivity established many of the principles or organic chemistry.
Chemistry World. 2008, December;50–53.
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2017:207–218. vol. 1. [chapter 9]. https://doi.org/10.1021/bk-2017-1262.ch009.
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11. Brock WH. Justus von Liebig—The Chemical Gatekeeper. Cambridge: Cambridge University Press; 1997:89.
12. Brock WH. Justus von Liebig—The Chemical Gatekeeper. Cambridge: Cambridge University Press; 1997:288.
13. Brock WH. Justus von Liebig—The Chemical Gatekeeper. Cambridge: Cambridge University Press; 1997:302.
14. Jaffe B. The Story of Chemistry: From Ancient Alchemy and Nuclear Fission. New Haven, CT: Fawcett Publications; 1957:119.
15. Brooke JH. Russell CA, ed. Recent Developments in the History of Chemistry. London: Royal Society of Chemistry; 1985:151.
 Chapter 1: The Logic of Organic Reaction
Mechanisms
In this chapter we explore the basic logical operations, concepts, and methods used to discuss and analyze organic
reaction mechanisms. For this purpose, we reference numerous works where readers can find detailed high quality
examples and discussions especially suitable for undergraduate organic chemistry students looking to establish a per-
sonal library of important works. Our standard of selection consists of filling in gaps, presenting new approaches, and
explaining why the field of physical organic chemistry is critical for understanding organic chemistry in a logical man-
ner. We consequently expect that readers of this textbook who might presently believe that study of organic chemistry
requires memorization of reaction details shall benefit the most from this introduction and the remainder of this book.
For the practicing research organic chemist, we emphasize that understanding and elucidating reaction mechanisms
both facilitates and strengthens the practice of organic synthesis. The bottom line is that reaction mechanism elucida-
tion works in the service of optimizing organic synthesis.

1.1 WHAT IS AN ORGANIC CHEMICAL REACTION?

Organic chemical reactions consist of processes in which starting materials interact with reagents under fixed condi-
tions to form new structures according to principles such as sterics, electronics, thermodynamics, and conservation of
mass and charge. Since these principles apply to any kind of chemical transformation, understanding them enables stu-
dents to categorize and recognize reactions without the mentally demanding task of having to remember disconnected
information about every single reaction they encounter. We note that today’s introductory chemistry textbooks and early
courses are designed to require students to remember details like product outcomes, starting materials, and reaction con-
ditions in a disconnected manner. Authors of such standard university textbooks1–5 only reinforce the memorization
approach when they organize transformations according to functional group classifications. To make matters worse, this
material is often presented without specifying original references or elucidating complete reaction mechanisms. Firstly,
we strongly emphasize presenting original references because it encourages students to access, use, and critique the lit-
erature. Students can thus build personal libraries and conceptual hierarchies from which they can connect ideas with the
real world of academics, scientific history, and laboratory successes and failures. Students can thus learn about how dis-
coveries are actually made and most importantly how carefully thought-out experiments guide scientists to the truth. In
fact, some of the greatest insights and advances in science can be attributed to understanding failures and unexpected
experimental results. Furthermore, original references demonstrate that ideas in science do not simply appear out of
nowhere and that they stand on their own merit and not simply because an author or instructor includes them. When
ideas are connected to reality in this way or through laboratory practice, one establishes a solid foundation for scientific
theory and for the hard work necessary for young scientists to find their place in the field of their endeavor. As the old
adage says, one does not know where one is going until one knows where one has come from.
From the standpoint of pedagogy, we thus encourage the reader to approach difficult problems and complex ideas by
identifying the large picture context of a chemical transformation and breaking it down into logically connected more
easily managed fragments such as elementary (i.e., mechanistic) steps followed by an overall reaction mechanism. Armed
with this knowledge a student will be prompted to write reaction mechanisms when given a novel transformation, an
approach which can assist in answering questions in other fields such as synthesis and green chemistry. Nevertheless, to
understand reaction mechanisms one must understand the available experimental and theoretical tools that constitute the

Strategies and Solutions to Advanced Organic Reaction Mechanisms 1 © 2019 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-812823-7.00301-3
2
body of evidence based on which a mechanism can be supported or rejected. This material is introduced here and covered
in further detail in Chapter 2. Afterward, a unified hierarchical approach for tackling problems of organic reaction mech-
anisms from both an analytical and an experimental standpoint is given in Chapter 3. As an illustrative example, we begin
by examining the old and well-established transformation shown in Scheme 1.1.

SCHEME 1.1 Baeyer-Villiger oxidation of benzophenone.

This reaction is called the Baeyer-Villiger oxidation (sometimes the Baeyer-Villiger rearrangement).6 It involves the
conversion of a ketone into an ester (or of a cyclic ketone into a lactone, in the case of cyclic rings) in the presence of an
oxidant such as a peroxy acid. It was discovered by Adolf von Baeyer and Victor Villiger in 1899,7, 8 which is the same
year that Julius Stieglitz introduced the concept of “carbocation” in the literature.9 Not surprisingly, the history of
physical organic chemistry also began in this early period.10, 11 To better appreciate this history, we highly recommend
that readers carefully study Refs. 10, 11 once they finish reading this chapter. As we shall see later when discussing its
mechanism, Baeyer and Villiger themselves adopted the word “carbocation” to describe a proposed early reaction
intermediate in the mechanism.12, 13 Later, in 1905, Baeyer was awarded the Nobel Prize in Chemistry “in recognition
of his services in the advancement of organic chemistry and the chemical industry,” thanks to his contributions to
organic dyes and hydroaromatic compounds.14 We note that at the time, reported yields for this transformation ranged
between 40% and 70%.7, 8 Over the next century, research on the Baeyer-Villiger oxidation has led to considerable
improvements in yield, the development of efficient catalysts, green chemistry conditions, and an improved under-
standing of its mechanism.15

1.2 THE BALANCED CHEMICAL EQUATION

Before looking at the mechanism however, we wish to emphasize certain rules of thumb with regard to how one
should read and draw reaction schemes. The first rule is that reaction schemes should be depicted to show the complete
balanced chemical equation for the transformation under consideration. In other words, every atom on the left-hand
side of the chemical equation should appear on the right-hand side, either in the structure of the desired product
(henceforth referred to as the product) or in the structure of the undesired product(s) (henceforth referred to as the
by-product(s)). We emphasize this rule for several reasons. First, the balanced chemical equation connects directly
to the reaction mechanism in that it constitutes the sum of the elementary mechanistic steps of the proposed mecha-
nism. This fact is important enough to warrant a statement of a theorem for the field of physical organic chemistry:

Theorem. The overall balanced chemical equation for a particular transformation constitutes the overall summation of the
elementary mechanistic steps of its proposed mechanism, each of which is mass and charge balanced. The overall balanced chem-
ical equation is thus itself charge and mass balanced.

We employ this theorem throughout the book by identifying complete balanced chemical equations for the trans-
formations considered in each of the problems discussed and their proposed mechanisms. Unfortunately, this practice
is generally omitted from most modern textbooks of organic chemistry, including, surprisingly, those considered to be
the gold standard for physical organic chemistry such as Anslyn and Dougherty and Carroll.16, 17 It is surprising in our
view because a balanced chemical equation motivates a host of valuable research practices both in the written analysis
and in experimental investigation. For instance, if by-product(s) can be identified experimentally then there exists
direct evidence supporting or contradicting a particular mechanistic proposal. This is because although atoms can
be counted and identified on both sides of a balanced chemical equation, one does not necessarily know the structures
of the by-products. If, for example, the reaction leads to gas evolution in the form of CO2 or N2, one can conclude that at
some point in the reaction mechanism such a gas is eliminated. One can then confidently reject an alternative mech-
anism where these atoms are eliminated as part of other structures. Therefore it is possible to say that every
 3
mechanistic proposal has its own unique balanced chemical equation. Note also that it is entirely possible, as we shall
see with the Baeyer-Villiger oxidation, that several proposed mechanisms will have the same balanced chemical equa-
tion. Nevertheless, in terms of proper depiction of reaction schemes, it would be entirely careless and bad practice to
draw the equation in Scheme 1.1 without showing the structure of the benzoic acid by-product. As will be seen
throughout this book, the concept of experimental by-product identification is one of the key strategies in elucidating
reaction mechanisms and is one of the best-kept secrets in the arsenal of tools used by practicing physical organic
chemists. Furthermore, identifying balanced chemical equations also respects the conservation of mass law which
Antoine Lavoisier, arguably the father of modern chemistry, discovered in 1775.18 Furthermore, a balanced chemical
equation also respects the conservation of charge law in that the sum of electronic charges depicted on the left-hand
side of the chemical equation is the same as the sum of the electronic charges appearing on the right-hand side.
Moreover, we note that a reaction Scheme can sometimes show multiple products thus making it impractical to rep-
resent a single balanced chemical equation. In this scenario, we distinguish between reaction product, by-product, and
side product in that a side product is a structure arising from a different mechanistic pathway as that which leads to the
reaction product. Such products are often depicted with percentage signs showing yields underneath the structures or
with the words “major” and “minor.” This means that multiple mechanistic paths exist and that one is more favorable
than the others. It also means that the difference between by-product and side product is that the two species may not
necessarily arise as a result of following the same mechanistic path. For example, the paths leading to product and side
product, respectively, may have the same by-product if the structures of the product and side product have the same
chemical formula. If the formulas are different, it means that mass has not been conserved and therefore each mechanistic
path would have different by-products with different masses. Nevertheless, we encourage the use of the terms “reaction
product,” “side product,” and “by-product” as a means of establishing clarity. Since these terms refer to different things,
they should not be used interchangeably as is currently the case in many modern textbooks of organic chemistry.

1.3 WHAT IS CONTAINED IN A REACTION SCHEME?

If we consider Scheme 1.1, we can observe that starting materials and products are labeled with numbers below the
chemical structures. In our systematized convention, we recommend the use of capital letters for structures of pro-
posed intermediates along a mechanistic pathway. Reagents, which are compounds that play a direct role in the reac-
tion mechanism, are shown above the reaction arrow while reaction conditions such as temperature, pressure, reaction
time, solvents, catalysts, and/or aqueous quench are shown below the reaction arrow. Commonly, the word “sub-
strate” refers to the starting material of interest whose structure in whole or in part definitely ends up in the product
structure, whereas the word “reagent(s)” refers to other starting materials that operate on the substrate, but which may
or may not end up incorporated in whole or in part in the product structure. It is thus possible to read a reaction scheme
and draw immediate conclusions about its mechanism by simply looking at these indicators. For example, in Scheme
1.1 we notice that an oxygen atom is introduced in the ketone group of benzophenone 1 thus giving the ester product 2.
We thus recognize this as a redox reaction where the ketone carbon atom in 1 undergoes oxidation from a +2 state to a
+3 state. This implies that something else must be reduced by 1 unit. Comparing the reagent used, peroxybenzoic acid
(another indication of a redox process since this is a well-known oxidizing reagent), to the benzoic acid by-product
drawn, we see that indeed the ester oxygen atom in the reagent is reduced from
1 to
2 in the benzoic acid by-
product. As a side note, we encourage the reader to familiarize oneself with oxidation number analysis because it
is very useful in understanding redox transformations.19 Other telling details about a transformation include high tem-
perature (a possible indication of a fragmentation process), photochemical energy or radical reagent (an indication of a
radical process), and acidic or basic reaction media as indications of proton transfer processes facilitated by acids or
bases, respectively. In addition, transformations without by-products may indicate that a rearrangement of the starting
substrate structure has taken place somewhere along the mechanistic path, particularly if the reaction is initiated ther-
mally, photochemically, or catalytically (e.g., by acid or base). Furthermore, reactions where starting materials lead to
products that have more atoms than are expected according to the conventionally written chemical equation should
prompt one to expect that several equivalents of the starting material or reagent react together to form the reaction
product. For such transformations, the corresponding balanced chemical equation will have nonunity stoichiometric
coefficients associated with those starting materials. It is also possible for an intermediate along a mechanistic pathway
to react with a starting material to form a combined structure which would then proceed to the final product. Such
cases of divergent and convergent reaction mechanisms as well as alternative mechanisms or partial alternative mech-
anisms are represented throughout this textbook and we hope they will help to expand the reader’s imagination with
4
regard to what is possible in organic reaction mechanisms. For now we wish to emphasize the fact that reaction
schemes have much to reveal about reaction mechanisms.

1.4 PRINCIPLE OF CONSERVATION OF STRUCTURAL ASPECT

Consider for a moment how Scheme 1.1 is illustrated and compare it with Scheme 1.2. We note that both Schemes
show the exact same transformation and that the only difference is the structural aspect. Which scheme is easier to read
and understand?

SCHEME 1.2 Baeyer-Villiger oxidation of benzophenone.

Clearly Scheme 1.1 is more easily understood. This is because the amount of information that can be stored in con-
scious awareness at any time is limited both in terms of available slots for storage (usually about seven) and the com-
plexity of the incoming information. For example, we can see that viewing structures 1 and 2 requires less mental
operations in Scheme 1.1 as opposed to Scheme 1.2. If rotation and inversion parameters were included in Scheme
1.2, the task of communication would be further complicated. We therefore view the practice of drawing complicated
schemes as unbecoming of those who wish to be understood. Unfortunately, this practice does appear in the literature
and also in university courses. We recommend a different approach. Rather than complicating the task of communi-
cating ideas by drawing unnecessarily complex structures in various structural aspects, chemists and academics
should consider adopting the principle of conservation of structural aspect. According to this principle, illustrations
of starting materials maintain a consistent structural aspect with that of reaction intermediates (in the case of a scheme
depicting a mechanism) and of desired products (in the case of standard reaction schemes). Advantages of such an
approach include: (1) the ability to easily map atoms of starting materials onto the structures of products, (2) better
identification of target bonds formed, (3) better identification and description of ring construction strategies, (4) higher
probability identification of reaction by-products, and (5) immediate expectations with regard to reaction mechanisms.
To further solidify this point, we provide two interesting examples where structural aspect was not maintained in the
original schemes (see Scheme 1.3).20, 21

SCHEME 1.3 Two example displays of transformations not following the principle of conservation of structural aspect. Example
1: acid-catalyzed dehydration with [1,2]-methyl migration; and Example 2: base-catalyzed Grob fragmentation.

Since these schemes do not respect the principle of conservation of structural aspect, their mechanisms, at first
glance, appear elusive. In fact, one has to consider the reaction conditions as a starting point for the mechanistic anal-
ysis given these illustrations. Based on reaction conditions the first example represents an acid-catalyzed rearrange-
ment whereas the second example shows a base-catalyzed fragmentation. By maintaining structural aspect with
respect to the starting material, we illustrate the mechanisms for these reactions in Scheme 1.4.
 5

SCHEME 1.4 Displays of mechanisms of transformations shown in Scheme 1.3 following the principle of conservation of struc-
tural aspect.

Seeing these mechanisms one can immediately spot how the products are formed without having to think
very hard. We also note that target bonds formed are represented as bolded bonds, not to be confused with stereo-
chemical representations which use dark and hashed wedges. We also note the interesting fact that the ketone
product in Example 2 can be drawn in several structural aspects which are manageable if one adopts numbering
of skeletal carbon atoms. The advantages of maintaining structural aspect consistent throughout a schematic
diagram are that each of the 300 problems solved in this textbook becomes considerably easier to understand
and to solve.

1.5 CURLY ARROW NOTATION

With these ground rules established, we turn to representation of reaction mechanisms by means of the logic of
curly arrow notation which was introduced by Sir Robert Robinson in 1922 as a convenient bookkeeping device for
tracking electron flow.22 We note that this concept is intricately based on the electronic theory of organic chemistry
which was also advanced by Robinson and several others (see supplementary information of Ref. 11) in 1926.23 It is
also important to mention that Robinson was a well-known Nobel Prize winning synthetic organic chemist, not a bone
fide physical organic chemist like his colleague and competitor Sir Christopher Ingold. Nevertheless, Robinson saw
the value of reaction mechanism in understanding product outcomes in the service of synthetic organic chemistry.
According to curly arrow notation therefore, processes involving two-electron transfers should be depicted using
curly arrows (full arrows) based on the following set of criteria: (1) arrow heads always point toward electrophilic
centers; (2) arrow tails always point toward nucleophilic centers; (3) electron flow proceeds from a nucleophilic
source to an electrophilic sink; and (4) a series of arrows are unidirectional in the sense that an arrow head is always
followed by an arrow tail, meaning that two arrow heads or two arrow tails never meet. To concretize these rules, we
highlight several examples of correct and incorrect use of curly arrow notation for two-electron transfer processes in
Schemes 1.5 and 1.6.
We see from these examples that the correct (or clearer) diagrams usually imply a greater number of mechanistic
steps. Sometimes, as in the incorrect diagram in Example 4, there are several arrows in close proximity which create
confusion if one does not identify the order of the arrows. Depicting a slightly longer stepwise mechanism can
eliminate such confusion in addition to providing for a more correct illustration.
Similar rules can be extended to mechanisms involving one-electron transfer processes (i.e., radical-type
mechanisms). In essence we have that: (1) curly arrows with half heads represent one-electron transfer steps,
6

SCHEME 1.5 Three examples showing juxtaposed incorrect and correct uses of curly arrow notation to depict reaction mecha-
nisms. Example 1: curly arrows depicting two-electron transfers, Example 2: bromination of olefins, and Example 3: oxidation
of sulfides to sulfones.

(2) a bond is formed whenever two half arrow heads come together, (3) homolytic bond fragmentation occurs
whenever two arrow tails emerge from a bond, and (4) a series of arrows are not unidirectional (this rule is the
opposite of that for the two-electron transfer process). To illustrate these rules, we provide several examples in
Scheme 1.7.
Lastly, we chose these examples because they still appear in some textbooks and so we wanted to show how our
approach clarifies some of these more unique reaction mechanisms. For more in-depth discussion of proper curly
arrow notation, including unique cases, see Appendix 5.4 in Ref. 16. We also recommend Refs. 24–27.

1.6 BAEYER-VILLIGER OXIDATION MECHANISM

Having considered the principles and rules for depicting reaction schemes and mechanisms, it is now possible to
represent the currently accepted mechanism for the Baeyer-Villiger oxidation originally shown in Scheme 1.1 (see
Scheme 1.8).6
 7

SCHEME 1.6 Three examples showing juxtaposed incorrect and correct uses of curly arrow notation to depict reaction mecha-
nisms. Example 4: epoxidation of olefins, Example 5: amidation of esters, and Example 6: generation of isocyanates.

Thus the proposed mechanism begins with protonation of the ketone group of benzophenone 1 via the peroxy acid
reagent which forms oxonium ion A which is then attacked by the newly generated oxyanion in a nucleophilic manner at
the electrophilic carbon atom (masked carbocation) to form the tetrahedral intermediate B. This intermediate in turn
undergoes protonation via the peroxy acid reagent to form intermediate C which undergoes base-mediated ketonization,
migration of the phenyl group onto the oxygen atom, and concomitant elimination of benzoic acid by-product to gen-
erate the final ester product 2. This mechanism is not as clearly presented in Wang6 nor in Anslyn and Dougherty16 nor do
these resources reference key experimental evidence which supports the mechanism. In fact, the reaction mechanism is
generally never connected with the historical development of physical organic chemistry apart from loose fragmentary
mentions of 18O-labeling experiments that support it (see, for instance, page 681 in Anslyn and Dougherty).16
Unfortunately, these authors also do not provide references for these experiments. Under this kind of approach, it is
not surprising that physical organic chemistry today has not received the serious treatment it deserves in both pedagogy
and the literature. For example, the reader might not know that Baeyer and Villiger originally proposed a different
mechanism for this transformation.7, 8 In these initial reports, there was no mention of a tetrahedral intermediate and
8

SCHEME 1.7 Three examples showing juxtaposed incorrect and correct uses of curly arrow notation to depict reaction mecha-
nisms. Example 7: curly arrows depicting one-electron transfers, Example 8: epoxidation of olefins using nitroxyl radical reagents,
and Example 9: epoxidation of olefins using peroxide reagents.

SCHEME 1.8 Mechanism of Baeyer-Villiger oxidation reaction of benzophenone.

the proposed mechanism, which was not shown in its entirety, involved formation of a dioxirane intermediate via attack
of peroxy acid onto the oxygen atom in 1 (which was hypothesized based on reports at the time concerning the Beckmann
rearrangement). We will present these mechanisms in Chapter 2 and discuss them in greater detail.
As for the historical background, once Stieglitz proposed the concept of carbocation,9 the history of which is itself
interesting and worth revisiting,10, 11 the term had immediately appeared in subsequent reports by Baeyer and Villi-
ger.12, 13 It was not until 1940 that the Baeyer-Villiger mechanism was challenged, this time by Georg Wittig and Gus-
tav Pieper who suggested formation of a peroxide intermediate following attack of the ketone group of 1 onto the
hydroxyl group of the peroxy acid reagent.28 It is worth mentioning that Georg Wittig was another Chemistry Nobel
Prize laureate in 1979 along with Herbert C. Brown for their work on boron and phosphorus-containing products.14 As
we can see, neither of these mechanisms became the generally accepted mechanism. This is because a third challenge
occurred in 1948 when Rudolf Criegee proposed carbon attack via the peroxyacid reagent followed by formation of the
tetrahedral intermediate B.29 It is worth mentioning that Criegee has a rearrangement named after him which was
 9
discovered in 1944 and which involves the oxidation of a tertiary alcohol into a ketone product plus primary alcohol
by-product when peroxy acid reagents are used.30, 31 One can thus see the similarities between the Criegee rearrange-
ment and the mechanism that Criegee proposed for the Baeyer-Villiger oxidation. Nevertheless, with three mechanistic
proposals in the literature it became clear that experimental evidence was needed to resolve the problem of which
mechanism was operating. This evidence came in 1953 when a team of American chemists from Columbia University,
Doering and Dorfman, performed an eloquent 18O-labeling experiment which directly supported the Criegee mech-
anism and contradicted the other two proposals.32 Since then, intermediate B has been named the Criegee intermediate
and subsequent research has focused on attempting to trap this intermediate and obtain indirect or direct experimental
evidence for its existence.33 With this background in mind and the wealth of history behind this transformation, it is
possible to develop a much greater appreciation for the work of analyzing and understanding reaction mechanisms, so
that one can subsequently apply such understanding to other difficult problems in organic chemistry. Nevertheless,
when textbooks present mechanisms without any historical background or references that one can easily access and
consult, using diagrams that create confusion rather than clarity and without mentioning experimental evidence, then
the entire wealth of knowledge and value provided by the field of physical organic chemistry is lost. To counter this
problem, we have gathered examples of textbooks on reaction mechanisms and categorized them in “recommended”
and “not recommended” columns along with our reasons so that the reader may easily judge which ones are worth
considering and adding to one’s personal library of physical organic chemistry (see Table 1.1).

TABLE 1.1 Enumeration of Recommended Textbooks on Physical Organic Chemistry and Mechanistic Analysis.
Recommend (R)
Author(s) (Ref. #) Strengths Weaknesses Not Recommend (NR)

Alder et al. (34) Rigorous approach, presents Examples are not current R
references
Alonso-Amelot (35) Presents logical principles and Does not show balanced chemical equations R
problem solving strategy clearly

Anslyn and Dougherty Excellent at outlining concepts of Does not provide references for ideas and examples R (only as modern
(16) physical organic chemistry, good for discussed in every chapter! Provides additional reading reference on physical
experiments, not good for references disconnected from solved examples. Balanced organic chemistry)
mechanistic analysis chemical equations are absent
Badea (36) Rigorous, mathematical and Does not have enough schemes and is not current R
methodological
Bansal (37) Attempts to be comprehensive Not rigorous NR
Bruckner (38) Great for visualization, contains Does not show balanced chemical equations R
numerous Schemes
Butler (39) Great for problems and solutions. Not current, curly arrow notation not well represented R
References are provided
Carroll (17) Excellent for problems and solutions, Does not provide historical background and does not R
references and topics covered, also show balanced chemical equations
current
Edenborough (40) Chapters 5, 17, and 22 are highly Introductory, does not identify by-products, does not R (only for Chapters 5,
recommended provide balanced chemical equations 17, 22)
Gardiner (41) Excellent presentation of rates of Does not show many organic reaction schemes or R
reactions, mathematical, and rigorous mechanisms
Grimshaw (42) Adequate coverage of Not comprehensive in terms of mechanisms NR
electrochemical reactions
Hammett (43) Foundational textbook for physical Not current, but historically highly relevant Highly R
organic chemistry with focus on
methodology
Harwood (44) Numerous mechanistic schemes, Specific topics, not general nor comprehensive R
good primer for polar
rearrangements
Continued
10
TABLE 1.1 Enumeration of Recommended Textbooks on Physical Organic Chemistry and Mechanistic Analysis.—cont’d
Recommend (R)
Author(s) (Ref. #) Strengths Weaknesses Not Recommend (NR)

Hassner and Illustrates 750 named reactions with Mechanisms are largely conjectured, by-products not R (only as a desk
Namboothiri (45) references and mechanisms identified, balanced chemical equations are not shown reference)
Hoever (46) Best and only textbook which Not current Highly R
attempts to do what we are doing in
this textbook, contains extensive
discussion and analysis
Ingold (47) Foundational textbook for physical Not current, but historically highly relevant Highly R
organic chemistry with a focus on
structure
Karty (48) Textbook is organized by mechanism Does not provide references or balanced chemical NR
with good coverage of pKA and H+ equations
transfer
Lavoisier (18) Excellent starting point historically Not current Highly R
for chemistry
Lawrence et al. (49) Good primer for foundations of Does not show mechanism schemes or concretize R (only for
physical organic chemistry such as ideas with examples of mechanisms introduction of
energetics and kinetics concepts)
Lawrence et al. (50) Contains worked examples for Does not show mechanism schemes or concretize ideas R (only for
foundations of physical organic with examples of mechanisms introduction of
chemistry such as energetics and concepts)
kinetics
Maskill (51) Good introduction and coverage of Does not show mechanism schemes or concretize ideas R (only for
rudimentary reaction categories (e.g., with examples of mechanisms introduction of
substitutions) concepts)
Maskill (52) Good introduction to structure and Does not show many mechanism schemes R (only for
reactivity introduction of
concepts)

Menger and Mandell Contains many examples that cover Level is beginning to intermediate, curly arrow notation R (only for
(24) electronic basis of organic chemistry needs improvement, does not show balanced chemical introductory level)
equations
Miller (25) Contains good explanation of curly Does not identify by-products or balanced chemical R
arrow notation and examples equations
Perkins (26) Good coverage of radical chemistry. This is just a primer so it is not extensive Highly R
Chapter 5 is recommended.
Ruff and Csizmadia (27) Excellent resource—comprehensive, Could use more mechanism schemes Highly R
with examples and references
Savin (53) Modern work Does not provide references or balanced chemical NR
equations
Scudder (54) Great coverage of electron flow and Does not provide references R (only for theory)
logic for reaction mechanisms
Smith (55) Recommend Chapter 6 for Does not provide exercises R
mechanisms and methods to
determine them
Stewart (19) Good coverage of redox mechanisms Not current R
including oxidation number analysis
Wang (6) Comprehensive and excellent as Not great for proposed mechanisms since most are R
guide to named organic reactions conjectured and sometimes key mechanism references
are absent
 11

1.7 TABLE OF RECOMMENDED TEXTBOOKS ON PHYSICAL ORGANIC CHEMISTRY

In addition to these textbooks specializing in reaction mechanisms, we wish to recommend other valuable resources
specializing in topics like green chemistry,56, 57 chemicals and reagents,58 aromatic heterocyclic chemistry,59 side reac-
tions,60 redox reactions,61 reaction intermediates,62–65 organic chemistry foundations,66, 67 organic stereochemistry,68
aromatic chemistry,69 ion-radical organic chemistry,70 and finally an excellent introduction to physical organic chem-
istry by Kosower.71 Lastly, we wish to conclude the chapter by covering two interesting concepts that are not well
covered elsewhere and which appear frequently in the advanced solutions that follow in Chapters 4 through 9. These
concepts are base strength in relation to pKA and autoxidation.

1.8 BASE STRENGTH AND pKA

In this short section we seek to clarify the relationship between base strength and pKA (at its core it is a measure of
acid strength). This is because when it comes to mechanisms of reactions involving acidic or basic conditions, it is
important to identify which species are present in solution because those are the compounds that should appear in
the reaction mechanism. Once identified, one must then judge which bases are strongest. Doing so can help elucidate
mechanisms which involve deprotonations. The likelihood of deprotonation events depends on the properties of acid
dissociation and base strength. For this purpose, the concept of pKA is crucial and so we begin from where this concept
originated, namely, the Henderson-Hasselbalch equation. Essentially, this equation focuses on the acid dissociation
constant Ka, which for an acid (generic HA) dissociation equilibrium in aqueous solution is defined as:

This expression was written by Lawrence J. Henderson in 1908.72, 73 A derivation which contained logarithmic
terms appeared in 1916 in an article by Karl A. Hasselbalch.74 Thus the derivation became known as the
Henderson-Hasselbalch equation:

We note that another expression for the Henderson-Hasselbalch equation is:

12
We can thus see that a strong acid (HA) implies a greater dissociation into its ions which implies a higher ([A
] [H+]/
[HA]) term. The same holds true when logarithms are taken of both sides. Nevertheless, log Ka is defined as (
pKA). In
this context a higher Ka term implies a higher log Ka term which implies a higher (
pKA) term which implies a lower
pKA. Thus strong acids have low pKA values. From the standpoint of reaction mechanism, this means that if an acid or
an acidic proton has a low pKA associated with it, then this acid or proton will readily react with a weak base and even
more readily with a stronger base (if both species are present in solution).
To judge base strength, one may start by judging acid strength in terms of pKA. We first recall that a weak acid has a
strong conjugate base while a strong acid has a weak conjugate base. Thus a strong acid which has a low pKA will have
a weak conjugate base. Correspondingly, a weak acid which has a high pKA will have a strong conjugate base. There-
fore given two anions A


1 and A2 , it is possible to assess base strength by considering the pKA’s of HA1 and HA2.
Suppose these are pKA1 and pKA2, respectively. Therefore if pKA1 > pKA2 we can draw two equally valid conclusions:
(1) HA1 is a weaker conjugate acid than HA2; and (2) A


1 is a stronger base than A2 anion. If, on the other hand,
pKA1 < pKA2 we have: (1) HA1 is a stronger conjugate acid than HA2; and (2) A1 is a weaker base than A



2 . We
can restate this conclusion in simpler terms: the higher the pKA of its conjugate acid, the stronger the base; and the
lower the pKA of its conjugate acid, the weaker the base. The inverse relationship exists between pKA and acid strength,
namely: the higher its pKA, the weaker the acid; and the lower its pKA, the stronger the acid. Once these relationships
are firmly established, it is possible to consult desk references and databases75, 76 which contain pKA values for various
“HA” compounds and to draw the correct mechanistic conclusions based on these values. We should also emphasize
that if the pKA of a particular CdH bond in a compound is less than the pKA of the conjugate acid of the base under
consideration, the deprotonation will occur. This is because a higher pKA implies a stronger conjugate base while a
lower pKA implies a stronger acid. Strong bases react with strong acids. If the reverse is true (i.e., the pKA of a
CdH bond is higher than the pKA of the conjugate acid of the base under consideration) then the deprotonation will
not occur. Once again, this is because a high pKA implies a weak acid while a low pKA implies a weak conjugate base.
Weak acids do not react with weak bases.
To illustrate and reinforce these concepts more concretely we show the following selected equilibria data given in
Table 1.2.

TABLE 1.2 Example Equilibria for Various Acids.

Equilibrium pKA pKB


H2O ¼ H + OH
+
15.7
1.7

NH+4 ¼ H+ + NH3 9.24 4.76

NH2NH+3 ¼ H+ + NH2NH2 8.12 5.88


HOAc ¼ H + OAc
+
4.76 9.24


CF3COOOH ¼ H + CF3COOO +
3.64 10.36


CF3COOH ¼ H + CF3COO+
0.23 13.77
H3O ¼ H + H2O
+ +

1.7 15.7


HBr ¼ H + Br
+

9 23

From Table 1.2 we note that all the equilibria are written in the form HA ¼ H+ + A
and we observe that the strongest
acid (HA) in the list is hydrobromic acid with a pKA of
9 since it has the lowest pKA value. By contrast, the weakest
acid is water with a pKA of 15.7. In order to find out which conjugate base is the strongest or the weakest, we use the
relationship pKA + pKB ¼ 14. From the resulting pKB values appearing in the third column we observe that hydroxide
ion is the strongest base with a pKB of
1.7 and bromide ion is the weakest base with a pKB of 23. We can therefore
make the following general statements:
A low pKA value means a stronger acid for HA.
A low pKA value means a higher pKB value for conjugate base A
.
A low pKB value means a stronger base for A
.
A low pKB value means a higher pKA value for acid HA.
 13
We can also make the following specific comparative statements based on the data given in Table 1.2:
NH2NH+3 is a stronger acid than NH3.
NH3 is a stronger base than NH2NH2.
H3O+ is a stronger acid than H2O.
OH– is a stronger base than H2O.
CF3COOH is a stronger acid than HOAc.
OAc
is a stronger base than CF3COO
.
H3O+ is a stronger acid than CF3COOH.
CF3COO
is a stronger base than H2O.
We conclude this section by highlighting several excellent compilations where reliable pKA values may be found in
the literature.75–83

1.9 AUTOXIDATION

The last topic considered in this chapter is one which frequently appears in articles that do not present complete
reaction mechanisms. In such articles, the authors typically present a conjectured mechanism of how they believe
“things might occur” which tends to omit the details of a last or penultimate mechanistic step where a reaction
intermediate undergoes some kind of oxidation process to generate the final product. Authors explain such a
process by simply stating “autoxidation” without showing which compounds react together by means of curly
arrow notation.
Autoxidation generally consists of a radical-type process which leads to the desired oxidized product. For example,
authors will typically omit the structure of O2 gas (originating from air) from reaction mechanisms. This is particularly
true for literature depictions of multicomponent reactions in which a pair of hydrogen atoms is unaccounted for when
such reactions result in an aromatic product structure. Such discrepancies reveal themselves when reagent structure
mappings onto the product structure are made and corresponding balanced chemical equations are sought after
for such transformations. It is important to note that O2 gas can be relevant to transformations carried out in aerobic
conditions. Due to the fact that oxygen gas exists as a ground state triplet (diradical), it can participate in a transfor-
mation in the role of an oxidant via one-electron transfer processes. Consider problem 30 in this textbook. Here, the
authors had drawn a mechanism where the final step was the air oxidation of intermediate I to form the final product 4
(Scheme 1.9).

SCHEME 1.9 Example of air oxidation transformation.

We consider this an unnecessary short cut which confuses more than it clarifies the reaction mechanism. The com-
plete sequence we have provided in Solution 30 is that shown in Scheme 1.10. This mechanism illustrates the exact logic
behind the oxidation of I to 4. Indeed we see that triplet state O2 reacts in a radical-type manner to abstract a proton
from I which in turn undergoes electron reshuffling to form radical intermediate J. The newly formed HOO radical is
then able to abstract a hydrogen atom from J to generate final product 4 and hydrogen peroxide by-product. The
hydrogen peroxide is then expected to undergo homolytic bond cleavage to form two equivalents of hydroxyl radical
species which can abstract hydrogen atoms from I and/or J in another mechanistic cycle to form water molecule as a
reaction by-product. This by-product would be reflected in the overall balanced chemical equation corresponding to
the proposed reaction mechanism.
14

SCHEME 1.10 Mechanism of air oxidation reaction shown in Scheme 1.9.

We emphasize this level of detail not just for the purpose of having a complete logical sequence to a proposed reac-
tion mechanism but also because of the implications of such a mechanism. For example, if the authors decided to inves-
tigate experimentally whether air (i.e., oxygen gas) was critical for the success of their transformation, as the proposed
mechanism requires, they could undertake the same transformation in anaerobic conditions devoid of oxygen gas. The
expected outcome of such an experiment (which would directly support the proposed autoxidation sequence) is that
product 4 would not be formed. If it is formed, this autoxidation mechanism would be rejected and the search for a
different oxidation reagent to help convert I to 4 would commence. In the absence of such evidence, the proposed
mechanism cannot be rejected because it is supported by chemical logic. In conclusion, we recommend an industrial
example of an autoxidation process and its mechanism (see pages 32–34 of Ref. 38).
We hope that this chapter has helped convey the importance of chemical logic and of reaction mechanisms to
readers interested in developing a better understanding of organic chemistry. We regret that because of space require-
ments and because the concept only appeared in one of the 300 problems solved, we could not include a section on
kinetics here. Nevertheless, we recognize the study of kinetics as central to the study of physical organic chemistry due
to its value for elucidating reaction mechanisms.

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 Chapter 2: Evidence for Organic Reaction
Mechanisms
This chapter will explore various experimental and theoretical tools available to chemists who seek to elucidate
reaction mechanisms. These ideas will be concretized by revisiting the Baeyer-Villiger oxidation introduced in the pre-
vious chapter. In this context we will show how experiments can be designed to help differentiate and support or reject
proposed mechanisms. We will then contrast the benefits of this approach with the numerous drawbacks encountered
throughout the 300 solutions illustrated in this book. Our hope is for readers to absorb this material and conclude that
experimental and theoretical evidence is crucial for understanding reaction mechanisms. It is often the case that the
best published research papers in the literature are those that connect experimental evidence with a rigorous compu-
tational backing to tell a complete and convincing story about a reaction mechanism and its reaction energy profile for
a given reaction.

2.1 WHAT IS PHYSICAL ORGANIC CHEMISTRY?

Physical organic chemistry can be defined as the study of organic chemistry in terms of the principles of physical
chemistry. We can put this definition in perspective by depicting a Venn diagram which shows how the fields are con-
nected (see Fig. 2.1). This discipline thus encompasses areas such as kinetics, thermodynamics, reaction conditions,
energetics, sterics, and the effects of structure on reactivity. Within these areas chemists apply experimental tools like
spectroscopy (used to characterize reactions and products), time resolved methods (used to study what happens
between the stages of reactants and products), synthesis (used to vary substrate and reagent structures to determine
parameters that affect reaction performance), stoichiometry (used to characterize the beginning and end of a reaction),
and change of conditions (i.e., media, catalyst(s), temperature, and time) to gauge their effect on reaction performance
and product outcomes. When applied in conjunction with the logical principles discussed in the previous chapter, these
experimental techniques can help support a proposed reaction mechanism by means of providing evidence for corre-
sponding intermediates, rate law, and overall balanced chemical equation (which is the sum of elementary steps).
Once reaction mechanisms are proposed, they are tested and revised until they agree with all evidence obtained
from such experiments as: trapping experiments (used to isolate otherwise unstable intermediates), isotopic labeling
experiments (used to differentiate mechanisms based on comparisons between expected and actual positions of atomic
isotope labels in reactants relative to products), crossover experiments (used to differentiate between intramolecular
and intermolecular processes), kinetic studies (used to determine substituent, kinetic isotope, and solvent effects, as
well as direct observation of intermediates along with quenching using diagnostic trapping reagents), by-product
identification experiments (used to help support a balanced chemical equation and its associated mechanism), and
theoretical studies (used to calculate energies of geometrically optimized structures along mechanistic pathways
and energy barriers which can then be translated into an energy reaction coordinate diagram).
We provide an example of an energy reaction coordinate diagram for a generic mechanism 1 ! A ! B ! 2 in
Fig. 2.2. Viewing this diagram we see that energy (i.e., Gibbs free energy, G) is plotted on the y-axis and that reaction
progress is shown on the x-axis. We specifically point out that the energy axis is quantitatively defined in a rigorous
manner; however, the reaction progress axis is not. The term “reaction coordinate” formally pertains to the set of bond
lengths, bond angles, and dihedral angles that are changed in each elementary step during the course of their asso-
ciated reactions. These cannot be plotted quantitatively since it would lead to a multidimensional diagram. Therefore

Strategies and Solutions to Advanced Organic Reaction Mechanisms 17 © 2019 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-812823-7.00302-5
18

FIG. 2.1 Venn diagram showing the connection between the subjects of physical and organic chemistries.

FIG. 2.2 Example energy reaction coordinate diagram.

the often-used term “energy reaction coordinate” diagram is really tracking the sequence of intermediates and inter-
vening transition states from step to step in a mechanism along the x-axis; hence the term “reaction progress.” These
points are not well communicated in the pedagogical literature on physical organic chemistry and can lead to confu-
sion in reading and interpreting the information conveyed in these highly simplified diagrams.
Thus in Fig. 2.2 we can see that reactant 1, product 2, and intermediates A and B are represented by energy minima
while transition states between each elementary step are represented as energy maxima. In fact, transition states are
mathematically described as saddle points on a multidimensional potential energy surface; whereas reactants, prod-
ucts, and all intervening intermediates are local minima. Most relevant however is the difference in energy between a
proposed intermediate and the subsequent transition state between that intermediate and the next structure in the
mechanistic sequence. This energy difference corresponds to the activation energy needed to be supplied so that
the proposed elementary mechanistic step in question will occur. If, for instance, an amount of energy equal to
G1 ! A ‡ is supplied (e.g., in the form of external heat) we would expect (according to Fig. 2.2) that 1 will be converted
into intermediate A. Once intermediate A is formed, if we supply energy greater than GA ! 1 ‡ but less than GA ! B ‡,
we can expect that A will not be converted into B but would likely revert back to 1. This occurs because there has been
enough energy supplied to meet the energy demand for the reverse process (A to 1) but not enough for the forward
process (A to B). We can thus see that every elementary step in a reaction mechanism has its own energy constraints.
 19
Some steps, as the ones depicted in Fig. 2.2, will be endergonic (ΔG > 0) thus requiring added energy to proceed
whereas other steps may be exergonic (ΔG < 0). Last, the difference in energy between reactants and products consti-
tutes the energy difference ΔG term for the entire transformation (not to be confused with energy of activation).
When ΔG is negative (as in Fig. 2.2, i.e., reactants are higher in energy than products), the transformation is
exergonic (ΔGrxn ¼Gprod  Greact < 0) whereas when ΔG is positive, the transformation is endergonic
(ΔGrxn ¼Gprod  Greact > 0). If the y-axis is replaced by enthalpic energy, ΔH, instead of free energy, then the terms
exergonic and endergonic are replaced by the terms exothermic (ΔHrxn ¼Hprod  Hreact < 0) and endothermic
(ΔHrxn ¼Hprod  Hreact > 0), respectively. Lastly, the highest magnitude G ‡ (activation energy) corresponds to the
rate-determining step, which in Fig. 2.2 is the A to B transformation. This is consistent with Murdoch’s excellent article
on how to find the rate-determining step from an energy reaction coordinate diagram corresponding to a reaction
comprised of several elementary steps.1 We point out that such an elementary step does not always correspond to
the one having the highest energy transition state.
Energy reaction coordinate diagrams also clarify the precise meaning of the ubiquitously used term “stability”
which is a comparative term. On one hand “stability” can be used to describe the relative energy of an initial state
to a final state process regardless of the pathway between them (i.e., thermodynamic stability). One can also use “sta-
bility” to describe the relative energy barriers of two elementary steps having different transition states where the
transformation is path dependent (i.e., kinetic stability). In Fig. 2.2, we observe that intermediate B is more thermo-
dynamically stable than intermediate A because it has a lower free energy value. Similarly, product 2 is more thermo-
dynamically stable than reactant 1. Thermodynamically stable chemical species are associated with more negative free
energies or more negative enthalpic energies. By contrast, we observe that intermediate A is more kinetically stable that
reactant 1 because the energy barrier for the step A to B is larger in magnitude than that for step 1 to A. From the
diagram we observe that in the forward sense (i.e., reading the diagram from left to right) intermediate A is overall
the most kinetically stable species since it is associated with the rate-determining step (A to B) and reactant 1 is the least
kinetically stable. In the reverse sense (i.e., reading the diagram from right to left) intermediate B is the most kinetically
stable since it is associated with the largest energy barrier for the B to A step. Moreover, intermediate A is the least
kinetically stable since it is associated with the smallest energy barrier for the step A to 1. Kinetically stable chemical
species are those associated with large energy barriers, small rate constants, and hence slow reaction rates. This dis-
cussion immediately leads to the very important concept of thermodynamic and kinetic control, which is operational
when a given starting material leads to two different products depending on reaction conditions. This strategy of
changing reaction conditions so that one product outcome is favored preferentially allows for great versatility in syn-
thesis methodology and has been exploited extensively. In Fig. 2.3 we show the four possible energy reaction coor-
dinate diagrams for a generic reaction leading to two products (i.e., 1 is converted to 2 and 3) along with their

FIG. 2.3 Possible energy reaction coordinate diagram scenarios pertaining to thermodynamic control (TC) and kinetic control
(KC) for a generic reaction leading to two products: 1 is converted into 2 and 3.
Another random document with
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insurance—Euthanasia, I suppose? Really, the Euthanasia’s been
responsible for more crimes than psychoanalysis.”
“Yes, I’m afraid you’ve got it all right. What did he die of?”
“Something that generally means suicide—or rather, you think it
does. The old sleeping draught business? Veronal?”
“No stupid, gas. The gas left turned on. And where’s Chilthorpe,
please?”
“It’s on the railway. If my memory serves me right, it is Chilthorpe
and Gorrington, between Bull’s Cross and Lowgill Junction. But the
man, you say, belongs somewhere else?”
“Pullford; at least it sounded like that. In the Midlands
somewhere, he said.”
“Pullford, good Lord, yes. One of these frightful holes. They make
perambulators or something there, don’t they? A day’s run, I should
think, in the car. But of course it’s this Chilthorpe place we want to
get to. You wouldn’t like to look it up in the gazetteer while I just get
this row finished, would you?”
“I shan’t get your sock finished, then. On your own foot be it! Let’s
see, here’s Pullford all right. . . . It isn’t perambulators they make, it’s
drain-pipes. There’s a grammar school there, and an asylum; and
the parish church is a fine specimen of early Perp., extensively
restored in 1842; they always are. Has been the seat of a Roman
Catholic Bishopric since 1850. The Baptist Chapel”——
“I did mention, didn’t I, that it was Chilthorpe I wanted to know
about?”
“All in good time. Let’s see, Chilthorpe—it isn’t a village really, it’s
a ship town. It has 2,500 inhabitants. There’s a lot here about the
glebe. It stands on the River Busk, and there is trout fishing.”
“Ah, that sounds better.”
“Meaning exactly?”
“Well, it sounds as if the fellow had done himself in by accident all
right. He went there to fish—you don’t go to a strange village to
commit suicide.”
“Unless you’ve got electric light in your house and want to commit
suicide with gas.”
“That’s true. What was the name of the inn, by the way?”
“The Load of Mischief. Such a jolly dedication, I think.”
 “Now let’s try the map.”
“I was coming to that. Here’s the Busk all right. I say, how funny,
there’s a place on the Busk called ‘Mottram.’ ”
“Anywhere near Chilthorpe?”
“I haven’t found it yet. Oh, yes, here it is, about four miles away.
Incidentally, it’s only twenty miles or so from Pullford. Well, what
about it? Are we going by car?”
“Why not? The Rolls is in excellent condition. Two or three days
ought to see us through; we can stay, with any luck, at the Load of
Mischief, and the youthful Francis will be all the better for being left
to his nurse for a day or two. You’ve been feeding him corn, and he
is becoming obstreperous.”
“You don’t deserve to have a son. However, I think you’re right. I
don’t want to trust you alone in a ship town of 2,500 inhabitants,
some of them female. Miles, dear, this is going to be one of your big
successes, isn’t it?”
“On the contrary, I shall lose no time in reporting to the directors
that the deceased gentleman had an unfortunate accident with the
gas, and they had better pay up like sportsmen. I shall further point
out that it is a great waste of their money keeping a private spy at
all.”
“Good, then I’ll divorce you! I’m going to bed now. Not beyond the
end of that second row, mind; we shall have to make an early start
to-morrow.”
 Chapter III.
At the Load of Mischief
By next morning Bredon’s spirits had risen. He had received by
the early post a confidential letter from the company describing Mr.
Mottram’s curious offer, and suggesting (naturally) that the state of
his health made suicide a plausible conjecture. The morning was
fine, the car running well, the road they had selected in admirable
condition. It was still before tea time when they turned off from its
excellent surface onto indifferent by-roads, through which they had
to thread their way with difficulty. The signposts, as is the wont of
English signposts, now blazoned “Chilthorpe,” “Chilthorpe,”
“Chilthorpe,” as if it were the lodestone of the neighbourhood, now
passed it over in severe silence, preferring to call attention to the fact
that you were within five furlongs of Little Stubley. They had fallen,
besides, upon hill country, with unexpected turns and precipitous
gradients; they followed with enforced windings the bleak valley of
the Busk, which swirled beneath them over smooth boulders
between desolate banks. It was just after they had refused the fifth
invitation to Little Stubley that the County Council’s arrangements
played them false; there was a clear issue between two rival roads,
with no trace of a signpost to direct their preference. It was here that
they saw, and hailed, an old gentleman who was making casts into a
promising pool about twenty yards away.
“Chilthorpe?” said the old gentleman. “All the world seems to be
coming to Chilthorpe. The County Council does not appear to have
allowed for the possibility of its becoming such a centre of fashion. If
you are fond of scenery, you should take the road to the left; it goes
over the hill. If you like your tea weak, you had better take the valley
road to the right. Five o’clock is tea time at the Load of Mischief, and
there is no second brew.”
 Something in the old gentleman’s tone seemed to invite
confidences. “Thank you very much,” said Bredon. “I suppose the
Load of Mischief is the only inn that one can stop at?”
“There was never much to be said for the Swan. But to-day the
Load of Mischief has added to its attractions; it is not everywhere
you can sleep with the corpse of a suicide in the next room. And the
police are in the house, to satisfy the most morbid imagination.”
“The police? When did they come?”
“About luncheon time. They are understood to have a clue. I am
only afraid, myself, that they will want to drag the river. The police
always drag the river if they can think of nothing else to do.”
“You’re staying at the inn, I gather?”
“I am the surviving guest. When you have tasted the coffee in the
morning you will understand the temptation to suicide; but so far I
have resisted it. You are not relatives, I hope, of the deceased?”
“No; I’m from the Indescribable. We insured him, you know.”
“It must be a privilege to die under such auspices. But I am afraid
I have gone beyond my book: when I say poor Mottram committed
suicide I am giving you theory not fact.”
“The police theory?”
“Hardly. I left before they arrived. It is the landlady’s theory, and
when you know her better you will know that it is as well not to
disagree with her; it provokes discussion.”
“I am afraid she must be very much worried by all this.”
“She is in the seventh heaven of lamentation. You could knock
her down, she tells me, with a feather. She insists that her custom is
ruined for ever; actually, you are the second party to stay at the inn
as the result of this affair, and the jug and bottle business at mid-day
was something incredible. The Band of Hope was there en masse,
swilling beer in the hope of picking up some gossip.”
“The other party, were they relations?”
“Oh no, it’s a policeman; a real policeman from London. The
secretary, I suppose, must have lost his head, and insisted on
making a cause célèbre of the thing. I forgot him, by the way, a little
chap called Brinkman; he’s at the Load too. A thousand pardons, but
I see a fish rising. It is so rare an event here that I must go and
attend to it.” And, nodding pleasantly, the old gentleman made his
way to the bank again.
Chilthorpe is a long, straggling village with the business part
(such as it is) at the lower end. The church is here, and the Load of
Mischief, and a few shops; here, too, the Busk flows under a wide
stone bridge—a performance which at most times of the day attracts
a fair crowd of local spectators. The houses are of grey stone, the
roofs of blue slate. The rest of the village climbs up along the valley
all in one street; the houses stand perched on the edge of a steep
slope, too steep almost for the cultivation of gardens, though a few
currant and gooseberry bushes retain a precarious foothold. The
view has its charms; when mists hang over it in autumn, or when the
smoke of the chimneys lingers idly on a still summer evening, it has
a mysterious and strangely un-English aspect.
The hostess, presumably to be identified with “J. Davis, licensed
to sell wines, spirits and tobacco,” met them on the threshold,
voluble and apparently discouraging. Her idea seemed to be that she
could not have any more guests coming and committing suicide in
her house. Bredon, afraid that his patience or his gravity would break
down, put Angela in charge of the conversation, and so delicate was
her tact, so well-placed her sympathy, that within ten minutes their
arrival was being hailed as a godsend, and Mrs. Davis, ordering the
barmaid to bring tea as soon as it could be procured, ushered them
into a private room, assuring them of accommodation upstairs when
she could put things to rights. It had been one thing after another,
she complained, all day, she didn’t really hardly know which way to
turn, and her house always a respectable one. There was not much
custom, it seemed, at Chilthorpe, lying so far away from the main
road and that—you would have supposed that in a R.A.C. Listed
Hotel suicides were a matter of daily occurrence, and the
management knew how to deal with them. Whereas Mrs. Davis
hadn’t anybody but the girl and the Boots, and him only with one
arm. And those boys coming and looking in through the front
window; “disgraceful,” she called it; and what were the police for if
they couldn’t put a stop to it? And the reporters—six of them she’d
turned away that very day—coming and prying into what didn’t
concern them. They didn’t get a word out of her, that was one thing.
 Though, mark you, if Mrs. Davis didn’t know poor Mr. Mottram,
who did? Coming there regular year after year for the fishing, poor
gentleman; such a quiet gentleman too, and never any goings-on.
And how was she to know what would come of it? It wasn’t that the
gas leaked; time and again she’d had those pipes seen to, and no
complaints made. If there had have been anything wrong, Mr.
Pulteney, he’d have let her hear about it, he was one for having
everything just as he liked, and no mistake. . . . Yes, that would be
him, he was a great one for the fishing. Such a queer gentleman too,
and always taking you up short. Why, yesterday morning, when she
went to tell him about what had happened in the night he was as
cool as anything; all he said was, “In that case, Mrs. Davis, I will fish
the Long Pool this morning,” like that he said. Whereas Mr.
Brinkman, that was the secretary, he was in a great taking about it,
didn’t hardly know what he said or did, Mr. Brinkman didn’t. And to
think of all the gas that was wasted; on all night it was, and who was
to pay for it was more than she knew. Summing up, Mrs. Davis was
understood to observe that it was a world for sorrow, and man was
cut down like a flower, as the sparks fly upward. However, there was
them above as knew, and what would be would be.
Of all this diatribe Bredon was a somewhat languid auditor. He
recognized the type too well to suppose that any end was to be
gained by cross-examination. Angela cooed and sighed, and dabbed
her eyes now and again at appropriate moments, and in so doing
won golden opinions from the tyrannous conversationalist. It was a
strong contrast when the maid came in with the tea things; she
plumped them down in silence, tossing her head defiantly, as who
should imply that somebody had recently found fault with her behind
the scenes, but she was not going to take any notice of it. She was a
strapping girl, of undeniable good looks, spoilt (improved, the Latins
would have said) by a slight cast in one eye. In the absence of any
very formidable competition it was easy to imagine her the belle of
the village. So resolute did her taciturnity appear that even Angela,
who could draw confidences from a stone, instinctively decided that
it would be best to question her later on. Instead, she whiled away
the interminable interval which separates the arrival of the milk jug
from that of the teapot by idly turning over the leaves of the old-
fashioned visitors’ book. The Misses Harrison, it appeared, had
received “every attention” from their kind and considerate hostess.
The Pullford Cycling Club had met for its annual outing, and the
members pronounced themselves “full to bursting, and coming back
next year.” An obviously newly married couple had found the
neighbourhood “very quiet”; a subsequent annotator had added the
words “I don’t think!!!” with the three marks of exclamation. The
Wotherspoon family, a large one, testified to having had a “rattling
good time” at this old-world hostelry. The Reverend Arthur and Mrs.
Stump would carry away “many pleasant memories” of Chilthorpe
and its neighbourhood.
Miles was wandering aimlessly about the room inspecting those
art treasures which stamp, invariably and unmistakably, the best
room of a small country inn. There was the piano, badly out of tune,
with a promiscuous heap of dissenting hymn-books and forgotten
dance tunes reposing on it. There were the two pictures which
represent a lovers’ quarrel and a lovers’ reconciliation, the hero and
heroine being portrayed in riding costume. There was a small
bookshelf, full of Sunday-school prizes, interspersed with one or two
advanced novels in cheap editions, clearly left behind by earlier
visitors. There was a picture of Bournemouth in a frame of repulsive
shells. There was a photograph of some local squire or other on
horseback. There were several portraits which were intended to
perpetuate the memory of the late Mr. Davis, a man of full bodily
habit, whose clothes, especially his collar, seemed too tight for him.
There were a couple of young gentlemen in khaki on the
mantelpiece; there was a sailor, probably the one who had collected
the strange assortment of picture post-cards in the album under the
occasional table; there were three wedding groups, all apparently in
the family—in a few words, a detective interested in such problems
might have read there, a picture, the incredibly long and complicated
annals of the poor.
To Bredon it was all a matter of intense irritation. When he visited
the scene of some crime or some problem, he was fond of poking his
way round the furniture, trying to pick up hints from the books and
the knickknacks about the character of the people he was dealing
with. At least, he would say, if you cannot pick up evidence about
them you can always catch something of their atmosphere. Mottram
had hardly played the game when he died in a country inn where he
had not been able to impress his surroundings with any touch of his
own quality; this inn parlour was like any other inn parlour, and the
dead body upstairs would be a problem in isolation, torn away as it
was from its proper context. The bedroom doubtless would have a
text over the washing-stand, a large wardrobe stuffed with family
clothes and mothballs, a cheap print of the “Soul’s Awakening”; it
would just be an inn bedroom, there would be no Mottram about it.
“I say,” Angela interrupted suddenly, “Mottram seems to have
visited this place pretty regularly, and always for the fishing season.
There are some fine specimens of his signature; the last only written
two days ago.”
“Eh? What’s that?” said Bredon. “Written his signature in already,
had he? Any date to it?”
“Yes, here it is, ‘J. W. Mottram, June 13th to’—and then a blank.
He didn’t know quite how long he would be staying, I suppose.”
“Let’s see. . . . Look here, that’s all wrong, you know. This isn’t a
hotel register; it’s just a visitors’ book. And people who write in a
visitors’ book don’t write till the day they leave.”
“Necessarily?”
“Invariably. Look here: look at Arthur Stump. You can see from
his style and his handwriting what a meticulous fellow he is. Well, he
came here on May twenty-first, and stayed till May twenty-six. The
Wilkinsons came here a day later, on the twenty-second, and left on
the twenty-fourth. But the Wilkinson entry comes first, and that’s
because they left first, don’t you see? And here is Violet Harris doing
the same; she puts her name before the Sandeman party. Look at
Mottram’s entry last year. He didn’t leave a blank then, and fill in his
date of departure afterward; you can always tell when a thing is filled
in afterward because the spacing is never quite exact. No; Mottram
did something quite foreign to his habit when he wrote June
thirteenth to blank, and quite foreign to the habits of every one I
know.”
“You get these little ideas sometimes. No; you can’t have tea till
you come and sit at the table. I don’t want you sloshing it about all
over the place. Now, what can have been the idea of writing that
entry? Nobody wanted proof that he’d been there. Could it be a
forgery, done from last year’s entry? That would mean that it isn’t
Mottram upstairs at all, really.”
“We shall know that soon enough. . . . No; there’s only one idea
that seems to me to make sense. He came to this place knowing that
he was never going to leave it alive. And consequently he wanted to
put an entry in the book which would make it look as if he had been
paying just an ordinary visit, and was expecting to leave it alive.
People will never see that they’re overreaching themselves when
they do that kind of thing. It’s absurd to go on such slight indications,
but so far as I can see the presumption is this: Mottram meant to
commit suicide, and meant to make it look as if he hadn’t.”
“The date’s all right, I suppose?”
“Bound to be. No sense in falsifying it when it could always be
verified from the bill. Landladies have a habit of knowing what night
guests arrived.”
“Let’s see, then. He arrived on the thirteenth; and he was found
dead in the morning, that’s yesterday morning, Tuesday. The
thirteenth was Monday—he’d only been here one night.”
“Well, we’ll hope we can find all that part out from the secretary. I
don’t much want another hour of Mrs. Davis. Meanwhile, let’s see if
you can knock any more out of that teapot; I’m as thirsty as a fish.”
 Chapter IV.
The Bedroom
They did not escape another dose of Mrs. Davis, who appeared
soon afterward to announce that the big room upstairs was ready for
them, and would they step up and mind their heads please, the stairs
were that low. It was indeed a rambling sort of house, on three or
four different levels, as country inns are wont to be; it did not seem
possible to reach any one room from any other without going down
and up again or up and down again. At the head of the stairs Mrs.
Davis turned dramatically and pointed to a door marked “5”. “In
there!” she said, the complicated emotion in her voice plainly
indicating what was in there. To her obvious confusion the door
opened as she spoke, and a little, dark man, whom they guessed
then and knew afterward to be the secretary, came out into the
passage. He was followed by a policeman—no ingenuity could have
doubted the fact—in plain clothes. Bredon’s investigations were
ordinarily made independently of, and for the most part unknown to,
the official champions of justice. But on this occasion Fate had
played into his hands. “By Gad!” he cried, “it’s Leyland!”
It was, and I will not weary the reader by detailing the
exclamations of surprise, the questionings, the reminiscences, the
explanations which followed. Leyland had been an officer in the
same battalion with Bredon for more than two years of the war. It
was at a time when the authorities had perceived that there were not
enough well-dressed young men in England to go round, and a
Police Inspector who had already made a name for efficiency easily
obtained commissioned rank; with equal ease he returned to the
position of an Inspector when demobilized. Their memories of old
comradeship promised to be so exhaustive and, to the lay mind, so
exhausting, that Brinkman had gone downstairs and Angela Bredon
to their room long before it was over; nay, Mrs. Davis herself,
outtalked for once, retired to her kitchen.
“Well, this is Al,” said Leyland at last. “Sure to be left down here
for a few days until I can clear things up a bit. And if you’re working
on the same lay, there’s no reason why we should quarrel. Though I
don’t quite see what your people sent you down for to start with.”
“Well, the man was very heavily insured, you know; and, for one
reason or another, the company is inclined to suspect suicide. Of
course if it’s suicide it doesn’t pay up.”
“Well, you’d better lie low about it and stay on for a few days.
Good for you and Mrs. Bredon to get a bit of a holiday. But of course
suicide is right off the map.”
“People do commit suicide, don’t they, by leaving the gas on?”
“Yes, but they don’t get up and turn the gas off and then go back
to bed to die. They don’t open the window, and leave it open”——
“The gas turned off? The window opened? You don’t mean”——
“I mean that if it was suicide it was a very rum kind of suicide, and
if it was accident it was a very rum kind of accident. Mark you, I’m
saying that to you; but don’t you go putting it about the place. Some
of these people in the inn may know more about it than they ought
to. Mum’s the word.”
“Yes, I can see that. Let’s see, who were there in the house? This
secretary fellow, and the old gentleman I saw down by the river, I
suppose, and Mrs. Davis and the barmaid and the Boots—that’s all
I’ve heard of up to now. That’s right, keep ’em all under suspicion.
But I wish you’d let me see the room; it seems to me there must be
points of interest about it.”
“Best see it now, I think. They’re going to fix up the corpse
properly to-night; so far they’ve left things more or less untouched.
There’s just light enough left to have a look round.”
The inn must at some time have known better days, for this room
was generously proportioned, and could clearly be used as a bed-
sitting room. But the wall-paper had seen long service; the
decorations were mean, the furniture shabby; it was not the sort of
accommodation that would attract a rich man from Pullford but for
the reputation the place had for fishing and, perhaps, the want of any
rival establishment. Chilthorpe, in spite of its possibilities of water-
power, had no electric light; but the inn, with one or two neighbouring
houses, was lighted by acetylene gas from a plant which served the
vicarage and the parish hall. These unpleasant fumes, still hanging
in the air after two days, were responsible, it seemed, for the tragic
loading of the bed which stood beside them.
To this last, Bredon paid little attention. He had no expert medical
knowledge, and the cause of death was unquestioned; both the local
man and a doctor whom the police had called in were positive that
the symptoms were those of gas poisoning and that no other
symptoms were present; that there were no marks of violence, no
indications even of a struggle; the man had died, it seemed, in his
sleep as if from an overdose of anæsthetic. Beside his bed stood a
glass slightly encrusted with some whitish mixture; Bredon turned
toward Leyland with an inquiring look as his eye met it.
“No good,” said Leyland. “We had it analysed, and it’s quite a
mild sort of sleeping draught. He sometimes took them, it seems,
because he slept badly, especially in a strange bed. But there’s no
vice in the thing; it wouldn’t kill a man however heavily he doped
himself with it, the doctor says.”
“Of course it explains why he slept so soundly and didn’t notice
the gas leaking.”
“It does that; and, if it comes to that, it sets me wondering a little.
I mean, supposing it was murder, it looks as if it was done by
somebody who knew Mottram’s habits.”
“If it was murder, yes. But if it was suicide, it’s easy to understand
the man doping himself, so that he should die off more painlessly.
The only thing it doesn’t look like is accident, because it would be
rather a coincidence that he should happen to be laid out by a
sleeping draught just on the very night when the gas was left on. I’d
like to have a look at this gas.”
There was a bracket on the wall, not far from the door, which
originally had been the only light in the room. But for bed-sitting room
purposes a special fitting had been added to this giving a second
vent for the gas; and this new vent was connected by a long piece of
rubber tubing with a standard lamp that stood on the writing-table
near the window. There were thus three taps in all, and all of these
close together on the bracket. One opened the jet on the bracket
itself, one led to the rubber tubing and the standard lamp and the
third was the oldest and closest to the wall, serving to cut off the
supply of gas from both passages at once. This third main tap was
turned off now; of the other two, the one on the bracket was closed,
the one which led to the standard lamp stood open.
“Is this how the taps were when the body was first found?” asked
Bredon.
“Exactly. Of course we’ve turned them on and off since to make
certain that the jets were both in working order. They were, both of
them. And we tried the taps for finger-prints—with powder, you
know.”
“Any results?”
“Only on the main tap. We could just trace where it had been
turned on, with the thumb pressing on the right-hand side. But there
were no marks of fingers turning it off.”
“That’s damned queer.”
“Gloves?”
“Oh, of course you think it was murder. Still, if it was murder it
should have been the murderer who turned it on and off. Why did he
conceal his traces in one case and not in the other?”
“Well, as a matter of fact, it was Mottram who turned the gas on.
At the main, that is. The tap of the standard seems to have been on
all the time, at least there were no marks on it. That’s queer too.”
“Yes, if he wanted it to be known that he committed suicide. But if
he didn’t, you see, the whole business may have been bluff.”
“I see, you want it to be suicide masquerading as accident. I want
it to be murder masquerading as suicide. Your difficulty, it seems to
me, is explaining how the tap came to be turned off.”
“And yours?”
“I won’t conceal it. The door was locked, with the key on the
inside.”
“How did anybody get in, then, to find the corpus?”
“Broke down the door. It was rotten, like everything else in this
house, and the hinges pulled the screws out. You can see, there,
where we’ve put fresh screws in since.”
“Door locked on the inside. And the window?” Bredon crossed to
the other side of the room. “Barred, eh?” It was an old-fashioned
lattice window with iron bars on the inside to protect it from
unauthorized approach. The window itself opened outward, its
movement free until it reached an angle of forty-five degrees; at that
point it passed over a spring catch which made it fast. It was so
made fast now that Bredon examined it.
“This too?” he asked. “Was the window just like this?”
“Just like that. Wide open, so that it’s hard to see why the gas
didn’t blow out of doors almost as soon as it escaped; and there was
a high wind on Monday night, Pulteney tells me. And yet, with those
bars, it seems impossible that any one should have come in through
it.”
“I think you’re going to have difficulties over your murder theory.”
“So are you, Bredon, over your suicide theory. Look at that shirt
over there; the studs carefully put in overnight; and it’s a clean shirt,
mark you; the outside buttonholes haven’t been pierced. Do you
mean to tell me that a man who is going to commit suicide is going to
let himself in for all that tiresome process of putting studs in before
he goes to bed?”
“And do you mean to tell me that a man goes out fishing in a
boiled shirt?”
“Yes, if he’s a successful manufacturer. The idea that one wears
special clothes when one is going to take exercise is an upper-class
theory. I tell you, I’ve seen a farmer getting in the hay in a dickey,
merely to show that he was a farmer, not a farm labourer.”
“Well, grant the point; why shouldn’t a man who wants to commit
suicide put studs in his shirt to make it look as if it wasn’t suicide?
Remember, it was a matter of half a million to his heirs. Is that too
heavy a price for the bother of it?”
“I see you’re convinced; it’s no good arguing with you. Otherwise,
I’d have pointed out that he wound up his watch.”
“One does. To a man of methodical habit it’s an effort to leave a
watch unwound. Was he a smoker?”
“Brinkman says not. And there are no signs of it anywhere.”
“The law ought to compel people to smoke. In bed, especially—
we should have got some very nice indications of what he was really
up to if he had smoked in bed. But I see he wasn’t a bedroom
smoker in any case; here’s a solitary match which has only been
used to light the gas—he hasn’t burnt a quarter of an inch of it.”
“That match worries me too. There’s a box on the mantelpiece,
but those are ordinary safeties. This is a smaller kind altogether, and
I can’t find any of them in his pockets.”
“The maid might have been in before him and lighted the gas.”
“They never do. At least, Mrs. Davis says they never do.”
“It was dark when he went to bed?”
“About ten o’clock, Brinkman says. You would be able to see your
way then, but not much more. And he must have lit the gas, to put
the studs in his shirt—besides, he’s left some writing, which was
probably done late that night, though we can’t prove it.”
“Writing! Anything important?”
“Only a letter to some local rag at Pullford. Here it is, if you want
to read it.” And Leyland handed Bredon a letter from the blotting-pad
on the table. It ran:

To the Editor of the Pullford Examiner:

Dear Sir:
Your correspondent, “Brutus,” in complaining of the closing of
the Mottram Recreation Grounds at the hour of seven p.m.,
describes these grounds as having been “presented to the town
with money wrung from the pockets of the poor.” Now, Sir, I
have nothing to do with the action of the Town Council in
opening the Recreation Grounds or closing same. I write only as
a private citizen who has done my best to make life amenable
for the citizens of Pullford, to know why my name should be
dragged into this controversy, and in the very injurious terms he
has done. Such recreation grounds were presented by me
twelve years ago to the townspeople of Pullford, not as “blood-
money” at all, but because I wanted them, and especially the
kiddies, to get a breath of God’s open air now and again. If
“Brutus” will be kind enough to supply chapter and verse,
showing where or how operatives in my pay have received less
pay than what they ought to have done——
 At this point the letter closed abruptly.
“He wasn’t very handy with his pen,” observed Bredon. “I
suppose friend Brinkman would have had to get onto this in the
morning and put it into English. Yes, I know what you’re going to say:
if the man had foreseen his end he either wouldn’t have taken the
trouble to start the letter or else he’d have taken the trouble to finish
it. But I tell you, I don’t like this letter—I say, we must be getting
down to dinner; attract suspicion, what, if we’re found nosing round
up here too long? All right, Leyland, I won’t spoil your sport. What
about having a fiver on it—suicide or murder?”
“I don’t mind if I do. What about telling one another how we get
on?”
“Let’s be quite free about that. But each side shall keep notes of
the case from day to day, putting down his suspicions and his
reasons for them, and we’ll compare notes afterward. Ah, is that Mrs.
Davis? All right, we’re just coming.”
 Chapter V.
Supper, and Mr. Brinkman
Mrs. Davis’s cuisine, if it did not quite justify all the ironic
comments of the old gentleman, lent some colour to them. With the
adjectival trick of her class she always underestimated quantity,
referring to a large tureen as “a drop of soup,” and overestimated
quality, daily suggesting for her guests’ supper “a nice chop.” The
chop always appeared; the nice chop (as the old gentleman pointed
out) would have been a pleasant change. As surely as you had eggs
and bacon for breakfast, so surely you had a chop for supper; “and
some nice fruit to follow” heralded the entrance of a depressed
blanc-mange (which Mrs. Davis called “shape,” after its principal
attribute) and some cold green-gages. These must have come from
Alcinous’s garden, for at no time of the year were they out of season.
If Angela had stayed in the house for a fortnight, it is possible that
she would have taken Mrs. Davis in hand and inspired her with
larger ideas, As it was, she submitted, feeling that a suicide in the
house was sufficiently unsettling for Mrs. Davis without further
upheavals.
The coffee room at the Load of Mischief was not large enough to
let the company distribute itself at different tables, each party
conversing in low tones and eyeing its neighbours with suspicion. A
single long table accommodated them all, an arrangement which
called for a constant exercise of forced geniality. Bredon and Leyland
were both in a mood of contemplation, puzzling out the secret of the
room upstairs; Brinkman was plainly nervous, and eager to avoid
discussing the tragedy; Angela knew, from experience in such
situations, the value of silence. Only the old gentleman seemed quite
at his ease, dragging in the subject of Mottram with complete sang-
froid and in a tone of irony which seemed inseparable from his
personality. Brinkman parried these topical references with
considerable adroitness, showing himself as he did so a travelled
man and a man of intelligence, though without much gift of humour.
Thus, in reply to a conventional question about his day’s sport,
the old gentleman returned, “No, I cannot say that I caught any. I
think, however, that I may claim without boasting to have frightened
a few of them. It is an extraordinary thing to me that Mottram, who
was one of your grotesquely rich men, should have come down for
his fishing to an impossible place like this, where every rise deserves
a paragraph in the local paper. If I were odiously rich, I would go to
one of these places in Scotland, or Norway, even, though I confess
that I loathe the Scandinavians. I have never met them, but the
extravagant praise bestowed upon them by my childhood’s
geography books makes them detestable to me.”
“I think,” said Brinkman, “that you would find some redeeming
vices among the Swedes. But poor Mottram’s reason was a simple
one; he belonged to these parts; Chilthorpe was his home town.”
“Indeed,” said the old gentleman, wincing slightly at the
Americanism.
“Oo, yes,” said Angela, “we saw Mottram on the map. Was he a
sort of local squire, then?”
“Nothing of that sort,” replied Brinkman. “His people took their
name from the place, not the other way round. He started here with a
big shop, which he turned over to some relations of his when he
made good at Pullford. He quarrelled with them afterward, but he
always had a sentimental feeling for the place. It’s astonishing what
a number of group names there are still left in England. There is no
clan system to explain it. Yet I suppose every tenth family in this
place is called ‘Pillock.’ ”
“It suggests the accident of birth,” admitted the old gentleman,
“rather than choice. And poor Mottram’s family, you say, came from
the district?”
“They had been here, I believe, for generations. But this habit of
naming the man from the place is curiously English. Most nations
have the patronymic instinct; the Welsh, for example, or the
Russians. But with us, apparently, if a stranger moved into a new
district, he became John of Chilthorpe, and his descendants were
Chilthorpes for ever.”
“A strange taste,” pursued the old gentleman, harping on the
unwelcome subject, “to want to come and lay your bones among
your ancestors. It causes so much fuss and even scandal. For
myself, if I ever decided to put a term to my own existence, I should
go to some abominable place—Margate, for example—and try to
give it a bad name by being washed up just underneath the pier.”
“You would fail, sir,” objected Brinkman; “I mean, as far as giving
it a bad name was concerned. You do not give things a good name
or a bad name nowadays; you only give them an advertisement. I
honestly believe that if a firm advertised its own cigarettes as beastly
it would draw money from an inquisitive public.”
“Mrs. Davis has had an inquisitive public to-day. I assure you,
when I went out this morning I was followed for a considerable
distance by a crowd of small boys who probably thought that I
intended to drag the river. By the way, if they do drag the river, it will
be interesting to find out whether there were, after all, any fish in it.
You will let me be present, sir?” turning to Leyland, who was plainly
annoyed by the appeal. Angela had to strike in and ask who was the
character in Happy Thoughts who was always asking his friends to
come down and drag the pond. So the uneasy conversation
zigzagged on, Mr. Pulteney always returning to the subject which
occupied their thoughts, the rest heading him off. Bredon was
deliberately silent. He meant to have an interview with Brinkman
afterward, and he was determined that Brinkman should have no
chance of sizing him up beforehand.
The opportunity was found without difficulty after supper;
Brinkman succumbed at once to the offer of a cigar and a walk in the
clear air of the summer evening. Bredon had suggested sitting on
the bridge, but it was found that at that hour of the evening all the
seating accommodation was already booked. Brinkman then
proposed a visit to the Long Pool, but Bredon excused himself on the
ground of distance. They climbed a little way up the hill road, and
found one of those benches, seldom occupied, which seem to issue
their invitation to travellers who are short of breath. Here they could
rest in solitude, watching cloud after cloud as it turned to purple in
the dying sunlight and the shadows gathering darker over the hill
crests.
“I’m from the Indescribable, you know. Expect Mrs. Davis has told
you. I’d better show you my cardcase so that you can see it’s
correct. They send me to fool round, you know, when this sort of
thing happens. Have to be careful, I suppose.” (“This Brinkman,” he
had said to Angela, “must take me for a bit of a chump; if possible,
worse than I am.”)
“I don’t quite see”—— began Brinkman.
“Oh, the old thing, suicide, you know. Mark you, they don’t
absolutely bar it. I’ve known ’em pay up when a fellow was obviously
potty. But their rules are against it. What I say is, If a man has the
pluck to do himself in he ought to get away with the stakes, Well, all
this must be a great nuisance to you, Mr. Brickman”——
“Brinkman.”
“Sorry, always was a fool about names. Well, what I mean is, it
can’t be very pleasant for you to have so many people nosing round;
but it’s got to be done somehow, and you seem to be the right man
to come to. D’you think there was anything wrong in the upper
story?”
“The man was as sane as you or I. I never knew a man with such
a level head.”
“Well, that’s important. You don’t mind if I scribble a note or two?
I’ve got such a wretched memory. Then, here’s another thing: was
the old fellow worried about anything? His health, for example?”
There was an infinitesimal pause; just for that fraction of a
second which is fatal, because it shews that a man is making up his
mind what to say. Then Brinkman said: “Oh, there can be no doubt of
that. I thought he’d been and told your people about it. He went to a
doctor in London and was told that he’d only two more years to live.”
“Meaning, I suppose”——
“He never told me. He was always a peculiar man about his
health; he got worried even if he had a boil on his neck. No, I don’t
think he was a hypochondriac; he was a man who’d had no
experience of ill-health, and the least thing scared him. When he told
me about his interview with the specialist he seemed all broken up,