Organic Chemistry, 11th Edition

Francis A. Carey - eBook PDF

Go to download the full and correct content document:
https://ebooksecure.com/download/organic-chemistry-11th-edition-ebook-pdf-2/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

(eBook PDF) Organic Chemistry 11th Edition By Francis

Carey

http://ebooksecure.com/product/ebook-pdf-organic-chemistry-11th-
edition-by-francis-carey/

(eBook PDF) Organic Chemistry 10th Edition By Francis

Carey

http://ebooksecure.com/product/ebook-pdf-organic-chemistry-10th-
edition-by-francis-carey/

Organic Chemistry 12th 12th Edition Francis Carey -

eBook PDF

https://ebooksecure.com/download/organic-chemistry-12th-ebook-
pdf/

Organic Chemistry 11th Edition (eBook PDF)

http://ebooksecure.com/product/organic-chemistry-11th-edition-
ebook-pdf/
Organic Chemistry A Modern Approach 1st Edition - eBook
PDF

https://ebooksecure.com/download/organic-chemistry-a-modern-
approach-ebook-pdf/

Organic Chemistry—A Modern Approach (Volume-II) - eBook

PDF

https://ebooksecure.com/download/organic-chemistry-a-modern-
approach-volume-ii-ebook-pdf/

Essential Organic Chemistry - eBook PDF

https://ebooksecure.com/download/essential-organic-chemistry-
ebook-pdf/

Organic Chemistry 8th Edition (eBook PDF)

http://ebooksecure.com/product/organic-chemistry-8th-edition-
ebook-pdf/

Organic Chemistry 6th Edition (eBook PDF)

http://ebooksecure.com/product/organic-chemistry-6th-edition-
ebook-pdf/
Page i
Page ii
 Page iii

Organic
Chemistry ELEVENTH EDITION

Francis A. Carey
University of Virginia

Robert M. Giuliano
Villanova University

Neil T. Allison
University of Arkansas

Susan L. Bane
Binghamton University
 Page iv

ORGANIC CHEMISTRY, ELEVENTH EDITION

Published by McGraw-Hill Education, 2 Penn Plaza, New York, NY 10121. Copyright © 2020 by McGraw-Hill Education. All
rights reserved. Printed in the United States of America. Previous editions © 2017, 2014, and 2011. No part of this publication
may be reproduced or distributed in any form or by any means, or stored in a database or retrieval system, without the prior
written consent of McGraw-Hill Education, including, but not limited to, in any network or other electronic storage or
transmission, or broadcast for distance learning.

Some ancillaries, including electronic and print components, may not be available to customers outside the United States.

This book is printed on acid-free paper.

1 2 3 4 5 6 7 8 9 LWI 21 20 19

ISBN 978-1-260-14892-3
MHID 1-260-14892-0

Portfolio Manager: Michelle Hentz

Product Developers: Mary E. Hurley & Megan Platt
Marketing Manager: Tamara Hodge
Content Project Managers: Laura Bies, Rachael Hillebrand & Sandra Schnee
Buyer: Sandy Ludovissy
Design: Daivd W. Hash
Content Licensing Specialists: Lorraine Buczek
Cover Image: ©Ella Maru Studio
Compositor: Aptara, Inc.

All credits appearing on page or at the end of the book are considered to be an extension of the copyright page.

Library of Congress Cataloging-in-Publication Data

Names: Carey, Francis A., 1937- author. | Giuliano, Robert M., 1954- author.
| Allison, Neil T. (Neil Thomas), 1953- author. | Tuttle, Susan L. Bane,
author.
Title: Organic chemistry / Francis A. Carey (University of Virginia), Robert
M. Giuliano (Villanova University), Neil T. Allison (University of
Arkansas), Susan L. Bane Tuttle (Binghamton University).
Description: Eleventh edition. | New York, NY: McGraw-Hill Education, 2018.
| Includes index.
Identifiers: LCCN 2018024902| ISBN 9781260148923 (alk. paper) | ISBN
1260148920 (alk. paper)
Subjects: LCSH: Chemistry, Organic. | Chemistry, Organic—Textbooks
Classification: LCC QD251.3 .C37 2018 | DDC 547—dc23 LC record available at https://lccn.loc.gov/2018024902

The Internet addresses listed in the text were accurate at the time of publication. The inclusion of a website does not indicate an
endorsement by the authors or McGraw-Hill Education, and McGraw-Hill Education does not guarantee the accuracy of the
information presented at these sites.

mheducation.com/highered
 Page v

Each of the eleven editions of this text has benefited from the
individual and collective contributions of the staff at McGraw-Hill. They
are the ones who make it all possible. We appreciate their
professionalism and thank them for their continuing support.
 Page vii

About the Authors

Before Frank Carey retired in 2000, his career teaching chemistry was spent entirely at the University of Virginia.
In addition to this text, he is coauthor (with Robert C. Atkins) of Organic Chemistry: A Brief Course and (with
Richard J. Sundberg) of Advanced Organic Chemistry, a two-volume treatment designed for graduate students and
advanced undergraduates.
Frank and his wife Jill are the parents of Andy, Bob, and Bill and the grandparents of Riyad, Ava, Juliana, Miles,
Wynne, and Sawyer.

Robert M. Giuliano was born in Altoona, Pennsylvania, and attended Penn State (B.S. in chemistry) and the
University of Virginia (Ph.D., under the direction of Francis Carey). Following postdoctoral studies with Bert Fraser-
Reid at the University of Maryland, he joined the chemistry department faculty of Villanova University in 1982,
where he is currently Professor. His research interests are in synthetic organic and carbohydrate chemistry.
Bob and his wife Margot, an elementary school teacher he met while attending UVa, are the parents of Michael,
Ellen, and Christopher and the grandparents of Carina, Aurelia, Serafina, Lucia, and Francesca.

Neil T. Allison was born in Athens, Georgia, and attended Georgia College (B.S., 1975, in chemistry) and the
University of Florida (Ph.D., 1978, under the direction of W. M. Jones). Following postdoctoral studies with
Emanuel Vogel at the University of Cologne, Germany, and Peter Vollhardt at the University of California, Berkeley,
he joined the faculty of the Department of Chemistry and Biochemistry, University of Arkansas in 1980. His research
interests are in physical organometallic chemistry and physical organic chemistry.
Neil and his wife Amelia met while attending GC, and are the parents of Betsy, Joseph, and Alyse and the
grandparents of Beau.

Susan L. Bane was raised in Spartanburg, South Carolina, and attended Davidson College (B.S., 1980, in chemistry)
and Vanderbilt University (Ph.D., 1983, in biochemistry under the direction of J. David Puett and Robley C.
Williams, Jr.). Following postdoctoral studies in bioorganic chemistry with Timothy L. Macdonald at the University
of Virginia, she joined the faculty of the Department of Chemistry of Binghamton University, State University of
New York, in 1985. She is currently Professor of Chemistry and director of the Biochemistry Program. Her research
interests are in bioorganic and biophysical chemistry.
Susan is married to David Tuttle and is the mother of Bryant, Lauren, and Lesley.
 Page viii

Brief Contents
List of Important Features xix
Preface xxiii
Acknowledgements xxx
1 Structure Determines Properties 2
2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons 54
3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 98
4 Chirality 134
5 Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms 172
6 Nucleophilic Substitution 210
7 Structure and Preparation of Alkenes: Elimination Reactions 244
8 Addition Reactions of Alkenes 288
9 Alkynes 330
10 Introduction to Free Radicals 356
11 Conjugation in Alkadienes and Allylic Systems 384
12 Arenes and Aromaticity 426
13 Electrophilic and Nucleophilic Aromatic Substitution 476
14 Spectroscopy 532
15 Organometallic Compounds 600
16 Alcohols, Diols, and Thiols 638
17 Ethers, Epoxides, and Sulfides 676
18 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 714
19 Carboxylic Acids 764
20 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 800
21 Enols and Enolates 850
22 Amines 890
23 Carbohydrates 946
24 Lipids 996
25 Amino Acids, Peptides, and Proteins 1036
26 Nucleosides, Nucleotides, and Nucleic Acids 1098
27 Synthetic Polymers 1140

Appendix: Summary of Methods Used to Synthesize a Particular Functional Group A-1

Glossary G-1
Index I-1
 Page ix

Contents
List of Important Features xix
Preface xxiii
Acknowledgements xxx

CHAPTER 1
________________________________________________________
Structure Determines Properties 2
1.1 Atoms, Electrons, and Orbitals 3
Organic Chemistry: The Early Days 5
1.2 Ionic Bonds 7
1.3 Covalent Bonds, Lewis Formulas, and the Octet Rule 8
1.4 Polar Covalent Bonds, Electronegativity, and Bond Dipoles 11
Electrostatic Potential Maps 13
1.5 Formal Charge 14
1.6 Structural Formulas of Organic Molecules: Isomers 16
1.7 Resonance and Curved Arrows 20
1.8 Sulfur and Phosphorus-Containing Organic Compounds and the Octet Rule 24
1.9 Molecular Geometries 25
Molecular Models and Modeling 27
1.10 Molecular Dipole Moments 28
1.11 Curved Arrows, Arrow Pushing, and Chemical Reactions 29
1.12 Acids and Bases: The Brønsted–Lowry View 31
1.13 How Structure Affects Acid Strength 36
1.14 Acid–Base Equilibria 41
1.15 Acids and Bases: The Lewis View 44
1.16 Summary 45
Problems 48
Descriptive Passage and Interpretive Problems 1: Amide Lewis Structural Formulas 53

CHAPTER 2
________________________________________________________
Alkanes and Cycloalkanes: Introduction to Hydrocarbons 54
2.1 Classes of Hydrocarbons 55
2.2 Electron Waves and Chemical Bonds 55
2.3 Bonding in H2: The Valence Bond Model 56
2.4 Bonding in H2: The Molecular Orbital Model 57
2.5 Introduction to Alkanes: Methane, Ethane, and Propane 59
2.6 sp3 Hybridization and Bonding in Methane 60
Methane and the Biosphere 60
2.7 Bonding in Ethane 62
2.8 sp2 Hybridization and Bonding in Ethylene 63
2.9 sp Hybridization and Bonding in Acetylene 65
2.10 Bonding in Water and Ammonia: Hybridization of Oxygen and Nitrogen 66
2.11 Molecular Orbitals and Bonding in Methane 68
2.12 Isomeric Alkanes: The Butanes 68
2.13 Higher n-Alkanes 69
2.14 The C5H12 Isomers 70
2.15 IUPAC Nomenclature of Unbranched Alkanes 72
2.16 Applying the IUPAC Rules: The Names of the C6H14 Isomers 73
What’s in a Name? Organic Nomenclature 74
2.17 Alkyl Groups 75
2.18 IUPAC Names of Highly Branched Alkanes 77
2.19 Cycloalkane Nomenclature 78
2.20 Introduction to Functional Groups 79
2.21 Sources of Alkanes and Cycloalkanes 79
2.22 Physical Properties of Alkanes and Cycloalkanes 81
2.23 Chemical Properties: Combustion of Alkanes 83
Thermochemistry 86
2.24 Oxidation–Reduction in Organic Chemistry 86
2.25 Summary 88
Problems 93
Descriptive Passage and Interpretive Problems 2: Some Biochemical Reactions of Alkanes 96

CHAPTER 3
________________________________________________________
Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 98
3.1 Conformational Analysis of Ethane 99
3.2 Conformational Analysis of Butane 103
3.3 Conformations of Higher Alkanes 104
Computational Chemistry: Molecular Mechanics and Quantum Mechanics 105
3.4 The Shapes of Cycloalkanes: Planar or Nonplanar? 106
3.5 Small Rings: Cyclopropane and Cyclobutane 107
3.6 Cyclopentane 108
3.7 Conformations of Cyclohexane 109
3.8 Axial and Equatorial Bonds in Cyclohexane 110
3.9 Conformational Inversion in Cyclohexane 112
3.10 Conformational Analysis of Monosubstituted Cyclohexanes 113
Enthalpy, Free Energy, and Equilibrium Constant 115
Page x
3.11 Disubstituted Cycloalkanes: cis–trans Stereoisomers 116
3.12 Conformational Analysis of Disubstituted Cyclohexanes 117
3.13 Medium and Large Rings 122
3.14 Polycyclic Ring Systems 122
3.15 Heterocyclic Compounds 124
3.16 Summary 125
Problems 128
Descriptive Passage and Interpretive Problems 3: Cyclic Forms of Carbohydrates 133

CHAPTER 4
________________________________________________________
Chirality 134
4.1 Introduction to Chirality: Enantiomers 134
4.2 The Chirality Center 137
4.3 Symmetry in Achiral Structures 139
4.4 Optical Activity 140
4.5 Absolute and Relative Configuration 142
4.6 Cahn–Ingold–Prelog R,S Notation 143
Homochirality and Symmetry Breaking 146
4.7 Fischer Projections 147
4.8 Properties of Enantiomers 149
4.9 The Chirality Axis 150
Chiral Drugs 151
4.10 Chiral Molecules with Two Chirality Centers 152
4.11 Achiral Molecules with Two Chirality Centers 155
Chirality of Disubstituted Cyclohexanes 157
4.12 Molecules with Multiple Chirality Centers 157
4.13 Resolution of Enantiomers 159
4.14 Chirality Centers Other Than Carbon 161
4.15 Summary 162
Problems 165
Descriptive Passage and Interpretive Problems 4: Prochirality 169
CHAPTER 5
________________________________________________________
Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms 172
5.1 Functional Groups 173
5.2 IUPAC Nomenclature of Alkyl Halides 174
5.3 IUPAC Nomenclature of Alcohols 175
5.4 Classes of Alcohols and Alkyl Halides 176
5.5 Bonding in Alcohols and Alkyl Halides 176
5.6 Physical Properties of Alcohols and Alkyl Halides: Intermolecular Forces 177
5.7 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides 181
5.8 Reaction of Alcohols with Hydrogen Halides: The SN1 Mechanism 183
Mechanism 5.1 Formation of tert-Butyl Chloride from tert-Butyl Alcohol and Hydrogen Chloride 184
5.9 Structure, Bonding, and Stability of Carbocations 189
5.10 Effect of Alcohol Structure on Reaction Rate 192
5.11 Stereochemistry and the SN1 Mechanism 193
5.12 Carbocation Rearrangements 195
Mechanism 5.2 Carbocation Rearrangement in the Reaction of 3,3-Dimethyl-2-butanol with Hydrogen
Chloride 195
5.13 Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The SN2 Mechanism 197
Mechanism 5.3 Formation of 1-Bromoheptane from 1-Heptanol and Hydrogen Bromide 198
5.14 Other Methods for Converting Alcohols to Alkyl Halides 199
5.15 Sulfonates as Alkyl Halide Surrogates 201
5.16 Summary 202
Problems 204
Descriptive Passage and Interpretive Problems 5: More About Potential Energy Diagrams 208

CHAPTER 6
________________________________________________________
Nucleophilic Substitution 210
6.1 Functional-Group Transformation by Nucleophilic Substitution 210
6.2 Relative Reactivity of Halide Leaving Groups 213
6.3 The SN2 Mechanism of Nucleophilic Substitution 214
Mechanism 6.1 The SN2 Mechanism of Nucleophilic Substitution 215
6.4 Steric Effects and SN2 Reaction Rates 217
6.5 Nucleophiles and Nucleophilicity 219
Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl Halides 221
6.6 The SN1 Mechanism of Nucleophilic Substitution 222
Mechanism 6.2 The SN1 Mechanism of Nucleophilic Substitution 223
6.7 Stereochemistry of SN1 Reactions 224
6.8 Carbocation Rearrangements in SN1 Reactions 226
Mechanism 6.3 Carbocation Rearrangement in the SN1 Hydrolysis of 2-Bromo-3-methylbutane 226
6.9 Effect of Solvent on the Rate of Nucleophilic Substitution 227
6.10 Nucleophilic Substitution of Alkyl Sulfonates 230
6.11 Introduction to Organic Synthesis: Retrosynthetic Analysis 233
6.12 Substitution versus Elimination: A Look Ahead 234
6.13 Summary 235
Problems 236
Descriptive Passage and Interpretive Problems 6: Nucleophilic Substitution 241

Page xi
CHAPTER 7
________________________________________________________
Structure and Preparation of Alkenes: Elimination Reactions 244
7.1 Alkene Nomenclature 244
7.2 Structure and Bonding in Alkenes 246
Ethylene 247
7.3 Isomerism in Alkenes 248
7.4 Naming Stereoisomeric Alkenes by the E–Z Notational System 250
7.5 Physical Properties of Alkenes 251
7.6 Relative Stabilities of Alkenes 252
7.7 Cycloalkenes 254
7.8 Preparation of Alkenes: Elimination Reactions 256
7.9 Dehydration of Alcohols 256
7.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule 257
7.11 Stereoselectivity in Alcohol Dehydration 259
7.12 The E1 and E2 Mechanisms of Alcohol Dehydration 259
Mechanism 7.1 The E1 Mechanism for Acid-Catalyzed Dehydration of tert-Butyl Alcohol 260
7.13 Rearrangements in Alcohol Dehydration 261
Mechanism 7.2 Carbocation Rearrangement in Dehydration of 3,3-Dimethyl-2-butanol 262
Mechanism 7.3 Hydride Shift in Dehydration of 1-Butanol 263
7.14 Dehydrohalogenation of Alkyl Halides 264
7.15 The E2 Mechanism of Dehydrohalogenation of Alkyl Halides 266
Mechanism 7.4 The E2 Mechanism of 1-Chlorooctadecane 267
7.16 Anti Elimination in E2 Reactions: Stereoelectronic Effects 269
7.17 Isotope Effects and the E2 Mechanism 271
7.18 The E1 Mechanism of Dehydrohalogenation of Alkyl Halides 272
Mechanism 7.5 The E1 Mechanism for Dehydrohalogenation of 2-Bromo-2-methylbutane 273
7.19 Substitution and Elimination as Competing Reactions 274
7.20 Elimination Reactions of Sulfonates 277
7.21 Summary 278
Problems 281
Descriptive Passage and Interpretive Problems 7: A Mechanistic Preview of Addition Reactions
286

CHAPTER 8
________________________________________________________
Addition Reactions of Alkenes 288
8.1 Hydrogenation of Alkenes 288
8.2 Stereochemistry of Alkene Hydrogenation 289
Mechanism 8.1 Hydrogenation of Alkenes 290
8.3 Heats of Hydrogenation 291
8.4 Electrophilic Addition of Hydrogen Halides to Alkenes 293
Mechanism 8.2 Electrophilic Addition of Hydrogen Bromide to 2-Methylpropene 295
Rules, Laws, Theories, and the Scientific Method 297
8.5 Carbocation Rearrangements in Hydrogen Halide Addition to Alkenes 298
8.6 Acid-Catalyzed Hydration of Alkenes 299
Mechanism 8.3 Acid-Catalyzed Hydration of 2-Methylpropene 299
8.7 Thermodynamics of Addition–Elimination Equilibria 301
8.8 Hydroboration–Oxidation of Alkenes 303
8.9 Mechanism of Hydroboration–Oxidation 305
Mechanism 8.4 Hydroboration of 1-Methylcyclopentene 306
Mechanism 8.5 Oxidation of an Organoborane 307
8.10 Addition of Halogens to Alkenes 308
Mechanism 8.6 Bromine Addition to Cyclopentene 309
8.11 Epoxidation of Alkenes 312
Mechanism 8.7 Epoxidation of Bicyclo[2.2.1]-2-heptene 313
8.12 Ozonolysis of Alkenes 314
8.13 Enantioselective Addition to Alkenes 315
8.14 Retrosynthetic Analysis and Alkene Intermediates 316
8.15 Summary 318
Problems 321
Descriptive Passage and Interpretive Problems 8: Oxymercuration 327

CHAPTER 9
________________________________________________________
Alkynes 330
9.1 Sources of Alkynes 330
9.2 Nomenclature 332
9.3 Physical Properties of Alkynes 332
9.4 Structure and Bonding in Alkynes: sp Hybridization 333
9.5 Acidity of Acetylene and Terminal Alkynes 335
9.6 Preparation of Alkynes by Alkylation of Acetylene and Terminal Alkynes 337
9.7 Preparation of Alkynes by Elimination Reactions 339
9.8 Reactions of Alkynes 340
9.9 Hydrogenation of Alkynes 340
9.10 Addition of Hydrogen Halides to Alkynes 342
9.11 Hydration of Alkynes 343
Mechanism 9.1 Conversion of an Enol to a Ketone 344
9.12 Addition of Halogens to Alkynes 345
Some Things That Can Be Made from Acetylene . . . But Aren’t 346
9.13 Ozonolysis of Alkynes 346
9.14 Alkynes in Synthesis and Retrosynthesis 347
9.15 Summary 347 Page xii
Problems 350
Descriptive Passage and Interpretive Problems 9: Thinking Mechanistically About Alkynes 354

CHAPTER 10
________________________________________________________
Introduction to Free Radicals 356
10.1 Structure, Bonding, and Stability of Alkyl Radicals 357
10.2 Halogenation of Alkanes 360
From Bond Enthalpies to Heats of Reaction 361
10.3 Mechanism of Methane Chlorination 362
Mechanism 10.1 Free-Radical Chlorination of Methane 363
10.4 Halogenation of Higher Alkanes 364
10.5 Free-Radical Addition of Hydrogen Bromide to Alkenes and Alkynes 368
Mechanism 10.2 Free-Radical Addition of Hydrogen Bromide to 1-Butene 369
10.6 Metal–Ammonia Reduction of Alkynes 371
Mechanism 10.3 Sodium–Ammonia Reduction of an Alkyne 372
10.7 Free Radicals and Retrosynthesis of Alkyl Halides 372
10.8 Free-Radical Polymerization of Alkenes 373
Mechanism 10.4 Free-Radical Polymerization of Ethylene 374
Ethylene and Propene: The Most Important Industrial Organic Chemicals 375
10.9 Summary 377
Problems 378
Descriptive Passage and Interpretive Problems 10: Free-Radical Reduction of Alkyl Halides 381
CHAPTER 11
________________________________________________________
Conjugation in Alkadienes and Allylic Systems 384
11.1 The Allyl Group 385
11.2 SN1 and SN2 Reactions of Allylic Halides 388
Mechanism 11.1 SN1 Hydrolysis of an Allylic Halide 389
11.3 Allylic Free-Radical Halogenation 392
Mechanism 11.2 Allylic Chlorination of Propene 394
11.4 Allylic Anions 395
11.5 Classes of Dienes: Conjugated and Otherwise 396
11.6 Relative Stabilities of Dienes 397
11.7 Bonding in Conjugated Dienes 398
11.8 Bonding in Allenes 400
11.9 Preparation of Dienes 401
Diene Polymers 402
11.10 Addition of Hydrogen Halides to Conjugated Dienes 403
Mechanism 11.3 Addition of Hydrogen Chloride to 1,3-Cyclopentadiene 403
11.11 Halogen Addition to Dienes 405
11.12 The Diels–Alder Reaction 406
11.13 Intramolecular Diels–Alder Reactions 409
11.14 Retrosynthetic Analysis and the Diels–Alder Reaction 410
11.15 Molecular Orbital Analysis of the Diels–Alder Reaction 411
Pericyclic Reactions in Chemical Biology 412
11.16 The Cope and Claisen Rearrangements 413
11.17 Summary 414
Problems 417
Descriptive Passage and Interpretive Problems 11: 1,3-Dipolar Cycloaddition 423

CHAPTER 12
________________________________________________________
Arenes and Aromaticity 426
12.1 Benzene 427
12.2 The Structure of Benzene 427
12.3 The Stability of Benzene 429
12.4 Bonding in Benzene 430
12.5 Substituted Derivatives of Benzene and Their Nomenclature 432
12.6 Polycyclic Aromatic Hydrocarbons 434
Fullerenes, Nanotubes, and Graphene 436
12.7 Physical Properties of Arenes 437
12.8 The Benzyl Group 438
12.9 Nucleophilic Substitution in Benzylic Halides 439
Triphenylmethyl Radical Yes, Hexaphenylethane No 442
12.10 Benzylic Free-Radical Halogenation 443
12.11 Benzylic Anions 444
12.12 Oxidation of Alkylbenzenes 444
12.13 Alkenylbenzenes 446
12.14 Polymerization of Styrene 448
Mechanism 12.1 Free-Radical Polymerization of Styrene 448
12.15 The Birch Reduction 449
Mechanism 12.2 The Birch Reduction 450
12.16 Benzylic Side Chains and Retrosynthetic Analysis 451
12.17 Cyclobutadiene and Cyclooctatetraene 452
12.18 Hückel’s Rule 453
12.19 Annulenes 455
12.20 Aromatic Ions 457
12.21 Heterocyclic Aromatic Compounds 461
12.22 Heterocyclic Aromatic Compounds and Hückel’s Rule 462
12.23 Summary 464
Page xiii
Problems 468
Descriptive Passage and Interpretive Problems 12: Substituent Effects on Reaction
Rates and Equilibria 473

CHAPTER 13
________________________________________________________
Electrophilic and Nucleophilic Aromatic Substitution 476
13.1 Representative Electrophilic Aromatic Substitution Reactions of Benzene 477
13.2 Mechanistic Principles of Electrophilic Aromatic Substitution 478
13.3 Nitration of Benzene 479
Mechanism 13.1 Nitration of Benzene 480
13.4 Sulfonation of Benzene 481
Mechanism 13.2 Sulfonation of Benzene 481
13.5 Halogenation of Benzene 482
Mechanism 13.3 Bromination of Benzene 483
Biosynthetic Halogenation 484
13.6 Friedel–Crafts Alkylation of Benzene 485
Mechanism 13.4 Friedel–Crafts Alkylation 485
13.7 Friedel–Crafts Acylation of Benzene 487
Mechanism 13.5 Friedel–Crafts Acylation 488
13.8 Synthesis of Alkylbenzenes by Acylation–Reduction 489
13.9 Rate and Regioselectivity in Electrophilic Aromatic Substitution 490
13.10 Rate and Regioselectivity in the Nitration of Toluene 492
13.11 Rate and Regioselectivity in the Nitration of (Trifluoromethyl)benzene 494
13.12 Substituent Effects in Electrophilic Aromatic Substitution: Activating Substituents 496
13.13 Substituent Effects in Electrophilic Aromatic Substitution: Strongly Deactivating Substituents 500
13.14 Substituent Effects in Electrophilic Aromatic Substitution: Halogens 503
13.15 Multiple Substituent Effects 504
13.16 Retrosynthetic Analysis and the Synthesis of Substituted Benzenes 506
13.17 Substitution in Naphthalene 508
13.18 Substitution in Heterocyclic Aromatic Compounds 509
13.19 Nucleophilic Aromatic Substitution 511
13.20 The Addition–Elimination Mechanism of Nucleophilic Aromatic Substitution 512
Mechanism 13.6 Nucleophilic Aromatic Substitution in p-Fluoronitrobenzene by the Addition–
Elimination Mechanism 514
13.21 Related Nucleophilic Aromatic Substitutions 515
13.22 Summary 516
Problems 520
Descriptive Passage and Interpretive Problems 13: Benzyne 528

CHAPTER 14
________________________________________________________
Spectroscopy 532
14.1 Principles of Molecular Spectroscopy: Electromagnetic Radiation 533
14.2 Principles of Molecular Spectroscopy: Quantized Energy States 534
14.3 Introduction to 1H NMR Spectroscopy 534
14.4 Nuclear Shielding and 1H Chemical Shifts 536
14.5 Effects of Molecular Structure on 1H Chemical Shifts 539
Ring Currents: Aromatic and Antiaromatic 544
14.6 Interpreting 1H NMR Spectra 545
14.7 Spin–Spin Splitting and 1H NMR 547
14.8 Splitting Patterns: The Ethyl Group 550
14.9 Splitting Patterns: The Isopropyl Group 551
14.10 Splitting Patterns: Pairs of Doublets 552
14.11 Complex Splitting Patterns 553
14.12 1H NMR Spectra of Alcohols 556
Magnetic Resonance Imaging (MRI) 557
14.13 NMR and Conformations 557
14.14 13C NMR Spectroscopy 558
14.15 13C Chemical Shifts 559
14.16 13C NMR and Peak Intensities 562
14.17 13C–1H Coupling 563
14.18 Using DEPT to Count Hydrogens 563
14.19 2D NMR: COSY and HETCOR 565
14.20 Introduction to Infrared Spectroscopy 567
Spectra by the Thousands 568
14.21 Infrared Spectra 569
14.22 Characteristic Absorption Frequencies 571
14.23 Ultraviolet-Visible Spectroscopy 575
14.24 Mass Spectrometry 577
14.25 Molecular Formula as a Clue to Structure 582
14.26 Summary 583
Problems 586
Descriptive Passage and Interpretive Problems 14: More on Coupling Constants 596

CHAPTER 15
________________________________________________________
Organometallic Compounds 600
15.1 Organometallic Nomenclature 601
15.2 Carbon–Metal Bonds 601
15.3 Preparation of Organolithium and Organomagnesium Compounds 603
15.4 Organolithium and Organomagnesium Compounds as Brønsted Bases 604
15.5 Synthesis of Alcohols Using Grignard and Organolithium Reagents 605
15.6 Synthesis of Acetylenic Alcohols 608
15.7 Retrosynthetic Analysis and Grignard and Organolithium Reagents 608
Page xiv
15.8 An Organozinc Reagent for Cyclopropane Synthesis 609
Mechanism 15.1 Similarities Between the Mechanisms of Reaction of an Alkene with
lodomethylzinc lodide and a Peroxy Acid 610
15.9 Carbenes and Carbenoids 611
15.10 Transition-Metal Organometallic Compounds 612
An Organometallic Compound That Occurs Naturally: Coenzyme B12 615
15.11 Organocopper Reagents 616
15.12 Palladium-Catalyzed Cross-Coupling 618
15.13 Homogeneous Catalytic Hydrogenation 621
Mechanism 15.2 Homogeneous Catalysis of Alkene Hydrogenation 623
15.14 Olefin Metathesis 624
Mechanism 15.3 Olefin Cross-Metathesis 626
15.15 Ziegler–Natta Catalysis of Alkene Polymerization 627
 Mechanism 15.4 Polymerization of Ethylene in the Presence of Ziegler–Natta Catalyst 629
15.16 Summary 630
Problems 632
Descriptive Passage and Interpretive Problems 15: Allylindium Reagents 636

CHAPTER 16
________________________________________________________
Alcohols, Diols, and Thiols 638
16.1 Sources of Alcohols 639
16.2 Preparation of Alcohols by Reduction of Aldehydes and Ketones 641
16.3 Preparation of Alcohols by Reduction of Carboxylic Acids 644
16.4 Preparation of Alcohols from Epoxides 644
16.5 Preparation of Diols 645
16.6 Reactions of Alcohols: A Review and a Preview 647
16.7 Conversion of Alcohols to Ethers 648
Mechanism 16.1 Acid-Catalyzed Formation of Diethyl Ether from Ethyl Alcohol 648
16.8 Esterification 649
16.9 Oxidation of Alcohols 651
Sustainability and Organic Chemistry 654
16.10 Biological Oxidation of Alcohols 656
16.11 Oxidative Cleavage of Vicinal Diols 657
16.12 Thiols 658
16.13 Spectroscopic Analysis of Alcohols and Thiols 661
16.14 Summary 663
Problems 666
Descriptive Passage and Interpretive Problems 16: The Pinacol Rearrangement 672

CHAPTER 17
________________________________________________________
Ethers, Epoxides, and Sulfides 676
17.1 Nomenclature of Ethers, Epoxides, and Sulfides 676
17.2 Structure and Bonding in Ethers and Epoxides 678
17.3 Physical Properties of Ethers 678
17.4 Crown Ethers 680
17.5 Preparation of Ethers 681
Polyether Antibiotics 682
17.6 The Williamson Ether Synthesis 683
17.7 Reactions of Ethers: A Review and a Preview 685
17.8 Acid-Catalyzed Cleavage of Ethers 686
 Mechanism 17.1 Cleavage of Ethers by Hydrogen Halides 687
17.9 Preparation of Epoxides 688
17.10 Conversion of Vicinal Halohydrins to Epoxides 689
17.11 Reactions of Epoxides with Anionic Nucleophiles 690
Mechanism 17.2 Nucleophilic Ring Opening of an Epoxide 692
17.12 Acid-Catalyzed Ring Opening of Epoxides 692
Mechanism 17.3 Acid-Catalyzed Ring Opening of an Epoxide 694
17.13 Epoxides in Biological Processes 695
17.14 Preparation of Sulfides 695
17.15 Oxidation of Sulfides: Sulfoxides and Sulfones 696
17.16 Alkylation of Sulfides: Sulfonium Salts 697
17.17 Spectroscopic Analysis of Ethers, Epoxides, and Sulfides 698
17.18 Summary 700
Problems 703
Descriptive Passage and Interpretive Problems 17: Epoxide Rearrangements and the NIH Shift
711

CHAPTER 18
________________________________________________________
Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 714
18.1 Nomenclature 715
18.2 Structure and Bonding: The Carbonyl Group 717
18.3 Physical Properties 719
18.4 Sources of Aldehydes and Ketones 719
18.5 Reactions of Aldehydes and Ketones: A Review and a Preview 723
18.6 Principles of Nucleophilic Addition: Hydration of Aldehydes and Ketones 724
Mechanism 18.1 Hydration of an Aldehyde or Ketone in Basic Solution 727
Mechanism 18.2 Hydration of an Aldehyde or Ketone in Acid Solution 728
18.7 Cyanohydrin Formation 728
Page xv
Mechanism 18.3 Cyanohydrin Formation 729
18.8 Reaction with Alcohols: Acetals and Ketals 731
Mechanism 18.4 Acetal Formation from Benzaldehyde and Ethanol 733
18.9 Acetals and Ketals as Protecting Groups 734
18.10 Reaction with Primary Amines: Imines 735
Mechanism 18.5 Imine Formation from Benzaldehyde and Methylamine 737
18.11 Reaction with Secondary Amines: Enamines 738
Imines in Biological Chemistry 739
Mechanism 18.6 Enamine Formation 741
18.12 The Wittig Reaction 742
18.13 Stereoselective Addition to Carbonyl Groups 745
18.14 Oxidation of Aldehydes 746
18.15 Spectroscopic Analysis of Aldehydes and Ketones 747
18.16 Summary 749
Problems 752
Descriptive Passage and Interpretive Problems 18: The Baeyer–Villiger Oxidation 760

CHAPTER 19
________________________________________________________
Carboxylic Acids 764
19.1 Carboxylic Acid Nomenclature 765
19.2 Structure and Bonding 767
19.3 Physical Properties 767
19.4 Acidity of Carboxylic Acids 768
19.5 Substituents and Acid Strength 770
19.6 Ionization of Substituted Benzoic Acids 772
19.7 Salts of Carboxylic Acids 773
19.8 Dicarboxylic Acids 775
19.9 Carbonic Acid 776
19.10 Sources of Carboxylic Acids 777
19.11 Synthesis of Carboxylic Acids by the Carboxylation of Grignard Reagents 779
19.12 Synthesis of Carboxylic Acids by the Preparation and Hydrolysis of Nitriles 780
19.13 Reactions of Carboxylic Acids: A Review and a Preview 781
19.14 Mechanism of Acid-Catalyzed Esterification 782
Mechanism 19.1 Acid-Catalyzed Esterification of Benzoic Acid with Methanol 782
19.15 Intramolecular Ester Formation: Lactones 785
19.16 Decarboxylation of Malonic Acid and Related Compounds 786
Enzymatic Decarboxylation of a β-Keto Acid 788
19.17 Spectroscopic Analysis of Carboxylic Acids 789
19.18 Summary 790
Problems 792
Descriptive Passage and Interpretive Problems 19: Lactonization Methods 797

CHAPTER 20
________________________________________________________
Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 800
20.1 Nomenclature of Carboxylic Acid Derivatives 801
20.2 Structure and Reactivity of Carboxylic Acid Derivatives 802
20.3 Nucleophilic Acyl Substitution Mechanisms 805
20.4 Nucleophilic Acyl Substitution in Acyl Chlorides 806
20.5 Nucleophilic Acyl Substitution in Acid Anhydrides 808
Mechanism 20.1 Nucleophilic Acyl Substitution in an Anhydride 810
20.6 Physical Properties and Sources of Esters 810
20.7 Reactions of Esters: A Preview 811
20.8 Acid-Catalyzed Ester Hydrolysis 813
Mechanism 20.2 Acid-Catalyzed Ester Hydrolysis 814
20.9 Ester Hydrolysis in Base: Saponification 816
Mechanism 20.3 Ester Hydrolysis in Basic Solution 819
20.10 Reaction of Esters with Ammonia and Amines 820
20.11 Reaction of Esters with Grignard and Organolithium Reagents and Lithium Aluminum Hydride 821
20.12 Amides 823
20.13 Hydrolysis of Amides 826
Mechanism 20.4 Amide Hydrolysis in Acid Solution 827
Mechanism 20.5 Amide Hydrolysis in Basic Solution 829
20.14 Lactams 830
β-Lactam Antibiotics 830
20.15 Preparation of Nitriles 832
20.16 Hydrolysis of Nitriles 833
Mechanism 20.6 Nitrile Hydrolysis in Basic Solution 834
20.17 Addition of Grignard Reagents to Nitriles 835
20.18 Spectroscopic Analysis of Carboxylic Acid Derivatives 835
20.19 Summary 837
Problems 840
Descriptive Passage and Interpretive Problems 20: Thioesters 847

CHAPTER 21
________________________________________________________
Enols and Enolates 850
21.1 Aldehyde, Ketone, and Ester Enolates 851
21.2 The Aldol Condensation 854
Mechanism 21.1 Aldol Addition of Butanal 855
21.3 Mixed and Directed Aldol Reactions 858
From the Mulberry Tree to Cancer Chemotherapy 859
21.4 Acylation of Enolates: The Claisen and Related Condensations 860
Mechanism 21.2 Claisen Condensation of Ethyl Propanoate 861
Page xvi
21.5 Alkylation of Enolates: The Acetoacetic Ester and Malonic Ester Syntheses 864
21.6 Enol Content and Enolization 867
Mechanism 21.3 Acid-Catalyzed Enolization of 2-Methylpropanal 869
21.7 The Haloform Reaction 871
Mechanism 21.4 The Haloform Reaction 872
21.8 Some Chemical and Stereochemical Consequences of Enolization 873
21.9 Conjugation Effects in α,β-Unsaturated Aldehydes and Ketones 874
21.10 Summary 878
Problems 880
Descriptive Passage and Interpretive Problems 21: The Knoevenagel Reaction 887

CHAPTER 22
________________________________________________________
Amines 890
22.1 Amine Nomenclature 891
22.2 Structure and Bonding 893
22.3 Physical Properties 895
22.4 Basicity of Amines 895
Amines as Natural Products 900
22.5 Tetraalkylammonium Salts as Phase-Transfer Catalysts 901
22.6 Reactions That Lead to Amines: A Review and a Preview 902
22.7 Preparation of Amines by Alkylation of Ammonia 904
22.8 The Gabriel Synthesis of Primary Alkylamines 905
22.9 Preparation of Amines by Reduction 906
Mechanism 22.1 Lithium Aluminum Hydride Reduction of an Amide 909
22.10 Reductive Amination 910
22.11 Reactions of Amines: A Review and a Preview 911
22.12 Reaction of Amines with Alkyl Halides 913
22.13 The Hofmann Elimination 913
22.14 Electrophilic Aromatic Substitution in Arylamines 915
22.15 Nitrosation of Alkylamines 917
22.16 Nitrosation of Arylamines 919
22.17 Synthetic Transformations of Aryl Diazonium Salts 920
22.18 Azo Coupling 924
From Dyes to Sulfa Drugs 924
22.19 Spectroscopic Analysis of Amines 926
22.20 Summary 928
Problems 934
Descriptive Passage and Interpretive Problems 22: Synthetic Applications of Enamines 943

CHAPTER 23
________________________________________________________
Carbohydrates 946
23.1 Classification of Carbohydrates 947
23.2 Fischer Projections and D,L Notation 947
23.3 The Aldotetroses 948
23.4 Aldopentoses and Aldohexoses 950
23.5 A Mnemonic for Carbohydrate Configurations 952
23.6 Cyclic Forms of Carbohydrates: Furanose Forms 952
23.7 Cyclic Forms of Carbohydrates: Pyranose Forms 956
23.8 Mutarotation 958
Mechanism 23.1 Acid-Catalyzed Mutarotation of D-Glucopyranose 959
23.9 Carbohydrate Conformation: The Anomeric Effect 960
23.10 Ketoses 962
23.11 Deoxy Sugars 963
23.12 Amino Sugars 964
23.13 Branched-Chain Carbohydrates 965
23.14 Glycosides: The Fischer Glycosidation 965
Mechanism 23.2 Preparation of Methyl D-Glucopyranosides by Fischer Glycosidation 967
23.15 Disaccharides 969
23.16 Polysaccharides 971
How Sweet It Is! 973
23.17 Application of Familiar Reactions to Monosaccharides 974
23.18 Oxidation of Carbohydrates 977
23.19 Glycosides: Synthesis of Oligosaccharides 980
Mechanism 23.3 Silver-Assisted Glycosidation 981
23.20 Glycobiology 982
Oligosaccharides in Infectious Disease 985
23.21 Summary 986
Problems 987
Descriptive Passage and Interpretive Problems 23: Emil Fischer and the Structure of (+)-
Glucose 992

CHAPTER 24
________________________________________________________
Lipids 996
24.1 Acetyl Coenzyme A 997
24.2 Fats, Oils, and Fatty Acids 998
24.3 Fatty Acid Biosynthesis 1001
24.4 Phospholipids 1003
24.5 Waxes 1006
24.6 Prostaglandins 1007
Nonsteroidal Antiinflammatory Drugs (NSAIDs) and COX-2 Inhibitors 1009
24.7 Terpenes: The Isoprene Rule 1010
24.8 Isopentenyl Diphosphate: The Biological Isoprene Unit 1013
24.9 Carbon–Carbon Bond Formation in Terpene Biosynthesis 1013
Page xvii
24.10 The Pathway from Acetate to Isopentenyl Diphosphate 1016
24.11 Steroids: Cholesterol 1018
Mechanism 24.1 Biosynthesis of Cholesterol from Squalene 1020
24.12 Vitamin D 1021
Good Cholesterol? Bad Cholesterol? What’s the Difference? 1021
24.13 Bile Acids 1022
24.14 Corticosteroids 1022
24.15 Sex Hormones 1023
24.16 Carotenoids 1024
Crocuses Make Saffron from Carotenes 1024
24.17 Summary 1026
Problems 1028
Descriptive Passage and Interpretive Problems 24: Polyketides 1032

CHAPTER 25
________________________________________________________
Amino Acids, Peptides, and Proteins 1036
25.1 Classification of Amino Acids 1037
25.2 Stereochemistry of Amino Acids 1042
25.3 Acid–Base Behavior of Amino Acids 1043
Electrophoresis 1046
25.4 Synthesis of Amino Acids 1048
25.5 Reactions of Amino Acids 1049
25.6 Peptides 1051
25.7 Introduction to Peptide Structure Determination 1054
25.8 Amino Acid Analysis 1054
25.9 Partial Hydrolysis and End Group Analysis 1054
25.10 Insulin 1056
25.11 Edman Degradation and Automated Sequencing of Peptides 1058
Mechanism 25.1 The Edman Degradation 1058
25.12 Mass Spectrometry of Peptides and Proteins 1060
Peptide Mapping and MALDI Mass Spectrometry 1061
25.13 The Strategy of Peptide Synthesis 1062
25.14 Amino and Carboxyl Group Protection and Deprotection 1064
25.15 Peptide Bond Formation 1066
Mechanism 25.2 Amide Bond Formation Between a Carboxylic Acid and an Amine Using N,N′-
Dicyclohexylcarbodiimide 1067
25.16 Solid-Phase Peptide Synthesis: The Merrifield Method 1068
25.17 Secondary Structures of Peptides and Proteins 1070
25.18 Tertiary Structure of Polypeptides and Proteins 1073
25.19 Protein Quaternary Structure: Hemoglobin 1075
25.20 Enzymes 1077
Mechanism 25.3 Carboxypeptidase-Catalyzed Hydrolysis 1078
25.21 Coenzymes in Reactions of Amino Acids 1079
Mechanism 25.4 Pyridoxal 5′-Phosphate-Mediated Decarboxylation of an α-Amino Acid 1080
Mechanism 25.5 Transamination: Biosynthesis of L-Alanine from L-Glutamic Acid and Pyruvic Acid
1084
Oh NO! It’s Inorganic! 1086
25.22 G-Protein-Coupled Receptors 1086
25.23 Summary 1087
Problems 1089
Descriptive Passage and Interpretive Problems 25: Amino Acids in Enantioselective Synthesis
1094

CHAPTER 26
________________________________________________________
Nucleosides, Nucleotides, and Nucleic Acids 1098
26.1 Pyrimidines and Purines 1099
26.2 Nucleosides 1101
26.3 Nucleotides 1103
26.4 Bioenergetics 1105
26.5 ATP and Bioenergetics 1106
26.6 Phosphodiesters, Oligonucleotides, and Polynucleotides 1108
26.7 Phosphoric Acid Esters 1109
26.8 Deoxyribonucleic Acids 1111
26.9 Secondary Structure of DNA: The Double Helix 1112
“It Has Not Escaped Our Notice . . .” 1112
26.10 Replication of DNA 1114
26.11 Ribonucleic Acids 1116
26.12 Protein Biosynthesis 1120
26.13 AIDS 1121
26.14 DNA Sequencing 1122
26.15 The Human Genome Project 1124
26.16 DNA Profiling and the Polymerase Chain Reaction 1124
26.17 Recombinant DNA Technology 1127
26.18 Summary 1128
Problems 1131
 Descriptive Passage and Interpretive Problems 26: Oligonucleotide Synthesis 1134

CHAPTER 27
________________________________________________________
Synthetic Polymers 1140
27.1 Some Background 1140
From Bakelite to Nylon 1141
27.2 Polymer Nomenclature 1142
27.3 Classification of Polymers: Reaction Type 1143
27.4 Classification of Polymers: Chain Growth and Step Growth 1145
27.5 Classification of Polymers: Structure 1146
Page xviii
27.6 Classification of Polymers: Properties 1149
27.7 Addition Polymers: A Review and a Preview 1149
27.8 Chain Branching in Free-Radical Polymerization 1152
Mechanism 27.1 Branching in Polyethylene Caused by Intramolecular Hydrogen Transfer 1153
Mechanism 27.2 Branching in Polyethylene Caused by Intermolecular Hydrogen Transfer 1154
27.9 Anionic Polymerization: Living Polymers 1154
Mechanism 27.3 Anionic Polymerization of Styrene 1155
27.10 Cationic Polymerization 1156
Mechanism 27.4 Cationic Polymerization of 2-Methylpropene 1157
27.11 Polyamides 1158
27.12 Polyesters 1159
27.13 Polycarbonates 1160
27.14 Polyurethanes 1160
27.15 Copolymers 1161
Conducting Polymers 1163
27.16 Summary 1164
Problems 1167
Descriptive Passage and Interpretive Problems 27: Chemically Modified Polymers 1168

Appendix: Summary of Methods Used to Synthesize a Particular Functional Group A-1

Glossary G-1
Index I-1
Another random document with
no related content on Scribd:
The Project Gutenberg eBook of Too close to the
forest
This ebook is for the use of anyone anywhere in the United States
and most other parts of the world at no cost and with almost no
restrictions whatsoever. You may copy it, give it away or re-use it
under the terms of the Project Gutenberg License included with this
ebook or online at www.gutenberg.org. If you are not located in the
United States, you will have to check the laws of the country where
you are located before using this eBook.

Title: Too close to the forest

Author: Bryce Walton

Al Reynolds

Release date: April 8, 2024 [eBook #73356]

Language: English

Original publication: New York, NY: King-Size Publications, Inc, 1954

Credits: Greg Weeks, Mary Meehan and the Online Distributed

Proofreading Team at http://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK TOO CLOSE

TO THE FOREST ***
Too close to the forest

By Bryce Walton & Al Reynolds

The dazzling difference between failure and

success hung from a spidery thread. And
established a barrier no ESP could sever.

We roll out the red carpet for

Bryce Walton and Al Reynolds.
New to us—but not to you.
Their's is the delicate tale of a
sensitive mind, the mind of Dr.
Marsten who tried frantically to
reach his colleagues. Only to
prove that over-familiarity with
a subject, reiteration of detail,
may obliterate the essential
vital point to success of a great
scientific experimentation.
 [Transcriber's Note: This etext was produced from
Fantastic Universe July 1954.
Extensive research did not uncover any evidence that
the U.S. copyright on this publication was renewed.]
I won't forget that evening of the big experiment. If the truth is ever
known about that evening maybe the world will never forget it either.
I got there first, and went into the hall they'd let Dr. Marsten have for
the evening on the Revere University Campus. Dr. Marsten was
sitting there alone behind a table with a few papers in front of him. A
single lamp burned that spotlighted his face like some old classic
sculpture in a gallery.
That's the way I remember him. Small, with delicate yet lined
features, and his hair, still dark, and his eyes bright and even darker
from peering beyond the frontiers of the human mind.
I never saw him again after that night, not in any way I want to
remember.
He offered his hand. It was hot and damp and shaking a little.
Tension had drawn his mouth tight, even when he managed to smile
at me and indicate a chair. I sat down.
"I'm so glad you're here, Max," he said. "It is right that you share in
this triumph." I could feel the tension behind his words. It was the
climax of his life. He would either vindicate himself or go, disgraced,
into oblivion.
He didn't have to explain any of this to me. I guess I was closer to
Dr. Marsten than anyone had ever been, except his wife, of course.
She had died ten years before. From that time on he lived for his
work in experimental psychology. Until finally, much to everyone's
shock and disbelief, he turned to parapsychology. And I worked with
him against the heartbreakingly rigid demands of the scientific
method.
I was only a graduate student working for my Doctor's degree at the
time. A term paper I'd done had impressed Marsten and he had
gotten me a scholarship. During the four years after that I was his
assistant and confidant.
That is, I was until he got completely wrapped up in parapsychology,
Extra Sensory Perception. At that point he abruptly dismissed me.
I knew why. I argued about it but he was adamant. He knew what
experiments in a field tinged with mysticism and the supernatural
might do to my scientific professional career. As it finally did to his.
He didn't want to involve me.
He was ostracized, dismissed from the University as a faculty
member. The scientific world depends on its open mind, within the
bounds of its own techniques. But the unknown worlds of the human
mind are sometimes very hard to fit into the rigid scientific disciplines
and methodologies.
Rhine's experiments satisfy those who want desperately, many of
them for highly personal reasons and needs, to believe in Extra
Sensory Perception. It doesn't satisfy the scientific mind. Its
"scientific validity," based on averages greater than those of
"chance," are not adequate for the scientific method. Too many
variables. But Marsten had told me he had gone much further than
Rhine or his disciples. And now he'd ask me to be here for the
culmination of his ten years of work.
"My theories will now be proven," he'd written me. "I want you to see
the proof I shall offer on the opening of new worlds of the human
mind...."
He'd published books on the subject but the world of science labeled
them pseudo-science, stuff for the psychic research societies and
those who take photographs of ectoplasm.
I believed in Marsten to an extent. But at the same time I doubted
that he could prove his contentions. I knew he was staking
everything on his faith in himself tonight. The biggest men in science
—men who had respected Marsten as a scientific mind until he went
off the deep end, they thought—were going to appear, allow him to
use them in his experiment to prove his theories.
They were big men in heart as well as reputation. But Marsten had
done some remarkable work in experimental psychology in the past
and I guess no one, outside of myself, wanted to see him regain his
professional respect and reputation as much as did those men: De
Vaca, Professor of English Literature; H. Morrison, Professor of
Biology; M. Borinsky, Professor of History and specialist in the
History of Russia; Billingsley, Professor of Theosophy; Marian Adler,
Psychology Professor who happened to have the same surname as
Freud's disciple, and there were others.
They had all agreed to Marsten's request to be a part of his final
experiment to prove the existence of mental telepathy.
"I'll prove mental telepathy tonight so they'll have to believe it,"
Marsten said softly. "And think what that will mean. New fields of
research will open the gates to human freedom and escape from
man's sad mental limitations. It will bring official, legalized scientific
research into the mind that will end the ills of mankind!" He leaned
forward and gripped my wrist. His forehead was wet. His voice was
hoarse. "It'll work tonight, Max!"
"And if it doesn't?" I asked.
He sat back, shook his head. "It will," he said. "I know because I've
proven it to myself. But—but if it doesn't—" He shrugged. "I'm
through. It will be the end of the road for me."
The way he said it, more than the words, frightened me. I knew how
intense he was, how much his work meant to him. And when he
spoke like that I knew—I feared—that Marsten had become
emotionally unbalanced.
"That's ridiculous," I said. "You can go ahead with your work,
regardless. Some of the greatest scientific advances have been
made against the popular grain. In fact, most scientific work!
Remember Galileo, Newton...."
He shrugged. "Matter of temperament. I know my own limitations, my
weaknesses. But I know this experiment tonight will work! Listen,
Max—I don't care about publicity. I've invited no reporters. I want
only these scientists to know, that's all. They're the ones who have to
be convinced. To give the field of parapsychology respectability so
that the vast resources and brains of science can be turned loose on
it, that's all I want."
He looked at me intense, earnest. "Max," he whispered, "the rumors
that are circulating about me—I've heard about them. They think I'm
unbalanced mentally! You've heard that?"
I was embarrassed. I had heard. Everyone had. I said, "You're
respected as an honest and scholarly man, a genius in the field of
psychology. These men, if they speculate at all along that line, think
you've deluded yourself by the 'will to believe' in your own
experiments. Wishful thinking, some call it. I don't believe anyone
thinks your capabilities in normal psychological work have
diminished. If anything, they're probably stronger."
He managed a thin laugh. "Well," he said. "Tonight will prove
something, anyway."
I remember the greetings when the other scientists arrived, the
slightly embarrassed attempts at conviviality. Within half an hour all
of the nine men arrived and were seated before Marsten's table. All
his former co-professors at the University where Marsten no longer
taught. I could see that Marsten was obsessed almost as much with
proving that these men's lack of faith in him was wrong, as he was in
proving his own theories right.
I felt apprehensive as Marsten started to talk. But as his self-
confidence, his obvious faith in himself began to show, I felt better.
His enthusiasm and confidence was so contagious that it even
affected the nine scientists so that they, too, became more interested
than embarrassed.
"Gentlemen," Marsten was saying, "you know from my letters why
you have been asked here. Needless to say, I am grateful beyond
words that you came to be shown proof of what you've refused so far
to believe—and with good cause. Tonight I shall demonstrate
scientifically the existence of mental telepathy. I shall prove to all of
you in an interrelated and undeniable way so that there will be no
doubt concerning my facts. No doubt whatsoever."
No one else said anything. Feet shuffled and there was a cough or
two. All of them knew what this would mean if Marsten could prove
his theories; what it would mean to him if he failed.
Marsten went on. "If I show that you can read my mind, that should
prove my theories to your satisfaction. I shall do this without any
hypnotic suggestion.
"I have not told anyone of the techniques which I've worked out over
a period of years, not even Max Reinach here. This will be my first
group demonstration of my theories. Until I was ready to give
conclusive scientific proof I did not confide fully to anyone, even to
Max, my closest associate."
He had told me a little, that is true. So little, in fact, that I knew not
much more about his theories than the rest of the scientists gathered
here tonight.
"... and so, gentlemen, I shall get the experiment over with as quickly
as possible. There are two rooms, as you see, one at each end of
the hall. I shall go into one room and lock the door. It is impossible
for me to see or hear anything that goes on outside that room.
Before the experiment starts I shall ask you to examine that room
yourselves, in any way you like."
De Vaca and Dr. Morrison went into the room, examined it
thoroughly. Then one of them stayed inside while the other came
out, closed the door, tested for sound. Finally, Morrison said, "We
agree—it is a sound-proof room. It is bare inside. There is no
opening other than this door."
"Thank you," Marsten said. "Max, will you hand each of these
gentlemen one of these cards and a pencil." I took the cards and
pencils from his table and handed them out.
"Now," Marsten said, "one by one, you will go, in any sequence you
desire, into that other room and lock the door. I will be locked in this
room that you checked. A bell in the room you are in will ring. That
will be the signal for you to leave the room and for someone else to
go in.
"During the time each of you is in that room, please keep your minds
open, receptive for a thought impression you will receive from me.
That's all there is to the experiment. Excepting this—" he lifted a
sealed envelope from the table. "This contains proof which will verify
the success of this experiment. I leave it here. You will, as a
committee, lock it in the safe upstairs in the business office. Take it
from the safe only after the experiment is over."
So the experiment started. I sat over by the wall, watching their
faces. I observed the way each man, in his own highly personalized
way, got up and played his part in an experiment which he believed
to be ridiculous.
I remember how each of them looked and acted as they, one by one,
went into that room, locked the door, and came out later when the
bell rang. I studied closely their faces as each came out. They went
in embarrassed silence back to their chairs and sat down, each
holding a card upon which they had written the thought supposedly
received from Marsten.
I felt the terrific tension. The room seemed hot and stifling as
Marsten came out of his room finally and went over to the table. His
face was pale and moist. His hair was wet and stringy around his
ears and over his forehead.
The ticking of the clock suddenly sounded louder and louder. The
breathing of the nine men seated there got louder. I could hear my
own heart going like a turbine in my chest. Now we waited for
Marsten to speak.
He glanced at me, motioned to me. I got up and went over to the
table. His eyes were dark and bright. "Collect the cards will you
please, Max, and give them to me?"
I did that. I didn't want to give them to him. I had a crazy idea of
running out of there with the cards. Then it would be my fault that
Marsten had failed. I didn't believe in Marsten then. I wanted to. I'd
worked with him, knew his greatness, his integrity and sincerity. I
knew he might be emotionally unstable. I wanted to believe, but I
wasn't convinced at all. Man is ever credulous in the wrong place, at
the wrong time, about the wrong things. We swallow the emotional
screamings of demagogues, reject the quiet discoveries of great
men who only do not know the techniques of salesmanship, of
propaganda.
But I put the cards on the table beside Marsten. Then, as he picked
them up I began to feel differently. I don't know why. Perhaps his
bravery, his courage and tenacity, his faith in his own beliefs,
overwhelmed me suddenly.
I was with him then. Somehow, all at once, I knew he was right.
Suddenly I had all the old confidence and trust in his genius that I
had had years before when I'd worked with him so closely.
The silence in the room then was paralyzing, a thick binding tension.
The nine professors stood up as if sitting now was untenable.
Professors of English literature, Biology, Astronomy, Music,
Medicine, Psychiatry, History, Physical Education, Religion. They
stood there waiting for Marsten to check their written thoughts on the
cards.
Marsten spread them out like a hand of bridge and looked at them.
His muscles jerked once, as from a galvanic reflex, like a man
suddenly touched with a high-tension wire.
He cried out, as from deep and wracking mental pain. The sound hit
into the room's silence like metal into flesh. He dropped the cards
abruptly and they spilled over the table. He stared at the floor
between the table and the nine men facing him.
His voice sounded far away, muffled. "Gentlemen, I've—failed. I've—
failed—miserably!"
He swayed. I ran around the table and caught him to stop his falling.
His muscles quivered under my hands.
He pushed me away. His eyes were hot and a little wild. Then he
stood up straight, like an old soldier at bay.
"I'm sorry you have had your valuable time imposed upon so
inexcusably. No need—no need now, I assure you, even to open the
sealed envelope. I missed—missed in every case except that of
Professor Adler. My success with him I attribute entirely to chance."
He took a step backward and whispered, "Goodnight, gentlemen.
Goodnight and—goodbye."
I called out, but he went on out the door. I ran after him into the hall,
but he had ducked out a side door. I followed him across the
darkening campus. But his car roared away before I could reach him.
I did not have a car so I could not follow.
I didn't talk to the others. I went home. And I began to phone, trying
to locate Marsten. I called every few minutes and I called the police
and everyone who knew him. The police said they would put out a
dragnet if he didn't show up within the next twenty-four hours. I had
explained he was in great distress, that I was afraid of what he might
do.
I didn't sleep well that night. There was no word about Marsten's
whereabouts in the morning. I began to think that perhaps suicide
was the only way out for him now. I doubted that he would be able to
face the failure of that experiment he had planned for so long, and
on which he had staked all of what remained of his reputation.

I managed to get three of the nine scientists to be with me when I

went to the office at the university and opened the safe and took out
that sealed envelope next morning. De Vaca, a small nervous man
with constant flighty gestures, Morrison, biology professor, a solemn,
bald little man, and Billingsley who had a jaw like a prizefighter, and
was big and gruff, but brilliant.
They, too, were worried about Marsten's disappearance, considering
his state of mind. Now we all wanted to know what that envelope
contained. Maybe its contents would assist us in helping Marsten—if
we found him.
After examining the contents of the sealed envelope, we sat around
the table and no one said anything for what seemed a long time.
Finally De Vaca said, "He failed all right. But it was a wonderful plan,
and certainly we could no longer deny the existence of mental
telepathy had this idea worked out as he planned it."
Morrison said, "But we must find Marsten before he kills himself. He
should be institutionalized, now, his mental unbalance treated...."
The others agreed. They began to discuss where to begin the search
for Marsten.
I thought about what we had found in that sealed envelope. Marsten
had had a great idea all right. Although the professors had selected
their own order of going into the testing room, Professor Marsten had
arbitrarily numbered each of them from 1 to 9. Using the subjects
which they taught instead of their names, he expected to prove
mental telepathy. In the envelope he had left this list:
1. Thackeray——Professor of English Literature
2. Evolution——Professor of Biology
3. Lungs——Professor of Anatomy
4. Elgar——Professor of Music
5. Phenobarbital——Professor of Medicine
6. Adler——Professor of Psychology
7. Trotsky——Professor of Russian History
8. Hockey——Professor in Physical Education
9. Yuletide——Professor in Theology
Each participant was to have received a specific word or name which
was directly connected with his field of teaching. The first letter of
each word, formed an acrostic reading down which spelled out:
T-E-L-E-P-A-T-H-Y

The cards the professors had handed in were also there beside us
on the table. I went through those cards again, slowly, while De Vaca
and Morrison and Billingsley debated as to the best way of locating
Marsten.
I wanted to do more than just find Marsten. I wanted to be able to
help him when he was found. The cards the professors had handed
in listed what they thought they had received from Marsten via
mental telepathy. This is what they had written:
 1. Shakespeare——Professor of English Literature
2. Darwin——Professor of Biology
3. Kidney——Professor of Anatomy
4. Debussey——Professor of Music
5. Opiate——Professor of Medicine
6. Adler——Professor of Psychology
7. Stalin——Professor in Russian History
8. Golf——Professor in Physical Education
9. Xmas——Professor in Theosophy.
Each professor had written something similar in meaning to what
Marsten had tried, through mental telepathy, to put into their minds.
Except in the case of the Professor of Psychology. And in that one
case there was a direct hit, as Marsten had said.
Oddly enough, Marian Adler had the same surname as the great
psychoanalyst, Alfred Adler, whom Marsten had chosen for one of
his projected thoughts. To me, the results did not seem the complete
failure Marsten thought them. But of course Marsten had wanted to
hit it one hundred percent. Nothing less would have satisfied a
scientific mind like his in such an experiment.
The acrostic: S-D-K-D-O-A-S-G-X formed by the words apparently
received by the Professors in that locked room was merely a jumble
of letters, spelling out nothing of any meaning.
Finally, we parted to go our separate ways. I took the envelope and
cards and went home. The others, with cars, would search for
Marsten. I'd forgotten my work, my thesis, everything. I wanted to
figure out something, but I didn't even know what it was. I had a
most unscientific idea—a hunch!
All day I thought and sweated over that envelope's contents, the
cards, the two acrostics:
T-E-L-E-P-A-T-H-Y
and
S-D-K-D-O-A-S-G-X
I worked all that day and through the night, but I could make no
connection between the two acrostics.
Meanwhile, the search continued for Marsten, but there was no sign
of him or his car. I sweated it out, trying to convince myself that he
wasn't already dead, that when he was found I, meanwhile, would
have found something in the remains of that experiment to give him
new zest, new hope.
But I didn't know the technique he had used. I kept thinking of that
one successful hit in the case of Doctor Adler. Here, I thought
desperately, might be the clue to his technique.... I stayed up and
worked at it another day, and into another night. If I could only prove
that the experiment hadn't failed completely, then that information
could be broadcast, televised, and maybe Marsten would see or
hear, if he still lived, and then would want to keep on living.
It was odd how positive I was that there was something there that
would prove Marsten right. Maybe we're all aware of much more
than we think we are—and could have greater awareness if we could
only raise a few mental curtains....
I pounded my brains out on that Adler angle. She was the only
woman in the group. Maybe that had meaning. I went through some
of Marsten's notes, but there weren't enough of them, and they
weren't the basic ones. I skimmed through books on Extra Sensory
Perception. But I didn't get anywhere....
And then the phone rang and I answered it. It was Police Lieutenant
Walters, at the local precinct station. He had promised to let me
know at once if they found any trace of Marsten.
"We found him," Walters said tersely. "He's on a ledge outside a
window of the Loeb Building at Fifth and Pinehurst!"
I said, "My God!" Then, "Will you pick me up?"
He said, "Yes. Maybe you can talk him out of it. You were close to
him. We've sent the emergency squads over. Never know when
they'll jump when they're like that. One move at the wrong time and
that makes them jump. I'll be there in five minutes...."
I felt sick with panic and hopelessness. Then, in that moment, out of
nowhere, came the flash—the key—it shone there before me all at
once, the answer I'd been looking for! I knew it had been there all
along and my mind had gone around it time and again. And suddenly
it was there, conscious and clear.
I arranged it all in my mind as we rode over to Fifth and Pinehurst,
the police lieutenant intent on driving speedily through the heavy
traffic.
If I could get to Marsten in time, I could save him! I'd had the
explanation all along—I'd read it in a scientific journal, in reports I'd
skimmed through on ESP. Marsten would understand—if I could get
to him in time! He hadn't been wrong. And I could give him proof....
A big crowd was gathered in the early dawn, standing silently in the
street, staring upward at the small figure on the ledge. The wind was
cold and steady and in the early morning greyness I saw Marsten,
thirty stories up, hunched against the side of the building. He wasn't
a man to exhibit himself for melodramatic recognition. Therefore, I
knew he must be very far out of his normal mind.
I am sure he went up there to jump immediately. But he had been
there an hour, now. Perhaps, I thought, he was trying to figure, in a
last desperate moment, where his experiment had failed. Trying to
find in the mysterious, senseless chaos of embryonic human
thought, a reason why he should not die....
The police got me through the crowd, inside the building and into an
elevator. I ran down the hall of the thirtieth floor to the room where
policemen were working with ropes and steel hooks. I heard one of
them say, "We can't reach him. It's no use."
I stuck my head out the window, called Marsten's name. But the wind
tore the words away, sent them in the opposite direction. He didn't
turn his head. I could barely make out his features, dead white and
void of expression.
"Don't jump, for God's sake!" I called over and over. "Professor, you
were right! The experiment was a success! Listen to me! It was a
success!"
I could see the uplifted faces down below, a blanket, a net they had
stretched down there, both looking no bigger than a checker square.
Marsten didn't seem to hear me, but I kept yelling, trying to make
him hear. I fought the wind, and whatever barrier there was between
Marsten and myself. But he didn't turn, didn't seem to hear me,
seemed unaware of me, of anything that went on around him.
I shouted the explanation to him of what I'd suddenly realized:
In these ESP tests the receiving impressions are the symbols on the
various cards in a deck. Basically, the tests in ESP experiments all
come down to one thing—the participants try, without seeing the
cards, to identify the symbols on each card in a deck as they draw
them from the pack.
In reviewing the results of these tests, it often happens that
participants, extra-ordinarily gifted with what is called 'psychic ability,'
have long runs of picking exact cards. But these runs are sometimes
on the cards—before the one that is being turned, or on the one after
the one turned.
In other words, if cards A-B-C-D-E-F-G have been turned, many
times the participant will call B when C is turned, C when D is turned,
E when F is turned, and so forth. There are various theories for the
cause of this factor. It is a factor that comes up time and again.
Marsten knew that. But in that intense moment he must have
overlooked it. It hadn't occurred to any of the others there, either. We
were all too close to the forest to see the trees....
And I screamed at the Professor against the wind and the morning:
S-D-K-D-O-A-S-G-X form an acrostic, and they are all one letter in
the alphabet before the letters that spell out T-E-L-E-P-A-T-H-Y!
Except in the letter A, for Adler. There could not be a letter before A
in the alphabet. So, there was no displacement factor on Adler's
card.
"Marsten, listen to me! Can you hear? Can't you understand? The
displacement factor, Marsten! The Displacement Factor—"
He never saw me, never heard me of that I am certain. Everything
seemed too late for Marsten. I saw him lean forward, drop off the
ledge. My words followed him crazily down as he fell: "The
displacement factor—"
Maybe before he struck the concrete down there he realized that he
had been right, that the experiment had not failed. I hope so. But I
think, in view of his tragic death, that Professor Marsten deserves
this explanation, this proof that his work was not in vain. And
because of what his hypothesis may mean to scientists of the future.
It isn't conclusive enough for the strictly disciplined scientific method.
But though others may think his experiment inconclusive, I know that
Professor Marsten proved the existence of Mental Telepathy.
So I'm going to take up where Marsten ended his experiment—and
his life—and I'm going to do it even though it may mean the end of
my career in orthodox science.
And maybe if I keep working at it, and thinking about it long enough
and steadily enough, Marsten will receive my thought. Then,
wherever he is now, if he doesn't already know, maybe I'll be able to
tell him that he didn't fail....