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 This International Student Edition is for use outside of the U.S.

Organic TWELFTH EDITION

Chemistry
H3CO O
NHCCH3
H3CO
H3CO
O
OCH3

FRANCIS A. CAREY ROBERT M. GIULIANO

NEIL T. ALLISON SUSAN L. BANE
 THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY

Acceptable Name(s) Characteristic

Example of Example Reaction Type

Hydrocarbons
Alkanes CH3CH3 Ethane Free-radical substitution of
hydrogen by halogen
Alkenes H 2C CH2 Ethene or ethylene Electrophilic addition to
double bond
Alkynes HC CH Ethyne or acetylene Electrophilic addition to
triple bond
Dienes H2C CHCH CH2 1,3-Butadiene Electrophilic addition to
double bonds
Arenes Benzene Electrophilic aromatic
substitution

Halogen-substituted derivatives of hydrocarbons

Alkyl halides CH3CH2Cl Chloroethane or Nucleophilic substitution;
ethyl chloride elimination
Alkenyl halides H2C CHCl Chloroethene or Electrophilic addition to
vinyl chloride double bond; elimination
Aryl halides C6H5Cl Chlorobenzene Electrophilic aromatic
substitution; nucleophilic
aromatic substitution

Oxygen-containing organic compounds

Alcohols CH3CH2OH Ethanol or ethyl Dehydration; conversion
alcohol to alkyl halides;
esterification
Phenols C6H5OH Phenol Electrophilic aromatic
substitution
Ethers CH3CH2OCH2CH3 Ethoxyethane or Cleavage by hydrogen
diethyl ether halides
Epoxides H2C CH2 Epoxyethane or Nucleophilic ring opening
ethylene oxide or
O
oxirane
O
Aldehydes CH3CH Ethanal or acetal- Nucleophilic addition to
dehyde carbonyl group
O
Ketones CH3CCH3 2-Propanone or Nucleophilic addition to
acetone carbonyl group
O
Carboxylic acids CH3COH Ethanoic acid or Ionization of carboxyl;
acetic acid esterification
 THE PRINCIPAL FUNCTIONAL GROUPS OF ORGANIC CHEMISTRY

Acceptable Name(s) Characteristic

Example of Example Reaction Type

Carboxylic acid derivatives

O
Acyl halides CH3CCl Ethanoyl chloride Nucleophilic acyl
or acetyl chloride substitution
O O
Acid anhydrides CH3COCCH3 Ethanoic anhydride Nucleophilic acyl
or acetic anhydride substitution
O
Esters CH3COCH2CH3 Ethyl ethanoate or Nucleophilic acyl
ethyl acetate substitution
O
Amides CH3CNHCH3 N-Methylethanamide Nucleophilic acyl
or N-methylacetamide substitution

Nitrogen-containing organic compounds

Amines CH3CH2NH2 Ethanamine or Nitrogen acts as a base or
ethylamine as a nucleophile
Nitriles CH3C N Ethanenitrile or Nucleophilic addition to
acetonitrile carbon–nitrogen triple
bond
Nitro compounds C6H5NO2 Nitrobenzene Reduction of nitro group
to amine

Sulfur-containing organic compounds

Thiols CH3CH2SH Ethanethiol Oxidation to a sulfenic,
sulfinic, or sulfonic acid
or to a disulfide
Sulfides CH3CH2SCH2CH3 Diethyl sulfide Alkylation to a sulfonium
salt; oxidation to a
sulfoxide or sulfone
 Organic
Chemistry T W E LF TH E D ITI O N

Francis A. Carey
University of Virginia

Robert M. Giuliano
Villanova University

Neil T. Allison
University of Arkansas

Susan L. Bane
Binghamton University
ORGANIC CHEMISTRY
Published by McGraw Hill LLC, 1325 Avenue of the Americas, New York, NY 10019. Copyright ©2024 by
McGraw Hill LLC. All rights reserved. Printed in the United States of America. 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 LLC, 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 28 27 26 25 24 23
ISBN 978-1-266-15924-4
MHID 1-266-15924-X
Cover Image: David W. Tuttle, Susan Bane Tuttle/McGraw Hill

All credits appearing on page are considered to be an extension of the copyright page.
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 LLC, and McGraw Hill LLC does not guarantee
the accuracy of the information presented at these sites.

mheducation.com/highered
Each of the twelve 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.
About the Authors

Frank Carey spent an entire career teaching chemistry 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). Fol-
lowing 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 published undergraduate research with his mentor E. Waali. Neil received
a Ph.D. at the University of Florida under the direction of W. M. Jones in 1978. Following
postdoctoral studies with Emanuel Vogel at the University of Cologne, Germany, and Peter
Vollhardt at the University of California, Berkeley, Neil became a faculty member at the
University of Arkansas. He pursues research in physical organometallic chemistry, physi-
cal organic chemistry, and chemical education. In addition to this text, Neil is the author of
Tap OChem, an organic chemistry iPhone and iPad application.
As a chemistry professor at UA, Neil is recognized as a Master Teacher in the Fulbright
College of Arts and Sciences and a Fellow in the university’s Teaching Academy. Neil’s teach-
ing incorporates active learning techniques in his undergraduate and graduate organic chem-
istry classes. Neil and partner Amelia met and married while attending GC. They are the
parents of Betsy, Joseph, and Alyse and the grandparents of Beau, Benjamin, and Brighton.

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.
vii
 Brief Contents

List of Important Features xix

Preface xxiii
Acknowledgements xxx

1 Structure Determines Properties 2

2 Alkanes and Cycloalkanes: Introduction to Hydrocarbons 56
3 Alkanes and Cycloalkanes: Conformations and cis–trans Stereoisomers 100
4 Chirality 136
5 Alcohols and Alkyl Halides: Introduction to Reaction Mechanisms 174
6 Nucleophilic Substitution 212
7 Structure and Preparation of Alkenes: Elimination Reactions 246
8 Addition Reactions of Alkenes 290
9 Alkynes 332
10 Introduction to Free Radicals 358
11 Conjugation in Alkadienes and Allylic Systems 386
12 Arenes and Aromaticity 428
13 Electrophilic and Nucleophilic Aromatic Substitution 478
14 Spectroscopy 534
15 Organometallic Compounds 602
16 Alcohols, Diols, and Thiols 640
17 Ethers, Epoxides, and Sulfides 678
18 Aldehydes and Ketones: Nucleophilic Addition to the Carbonyl Group 716
19 Carboxylic Acids 766
20 Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution 802
21 Enols and Enolates 854
22 Amines 894
23 Carbohydrates 950
24 Lipids 1000
25 Amino Acids, Peptides, and Proteins 1040
26 Nucleosides, Nucleotides, and Nucleic Acids 1102
27 Synthetic Polymers 1138

Appendix: 
Summary of Methods Used to Synthesize a Particular Functional
Group A-1
Glossary G-1
Index I-1

viii
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Contents

List of Important Features xix 2.5 Introduction to Alkanes: Methane, Ethane, and
Preface xxiii Propane 61
Acknowledgements xxx 2.6 sp3 Hybridization and Bonding in Methane 62
Methane and the Biosphere 62

C H A P T E R 1 2.7
2.8
2.9
Bonding in Ethane 64
sp2 Hybridization and Bonding in Ethylene 65
sp Hybridization and Bonding in Acetylene 67
2.10 Bonding in Water and Ammonia: Hybridization of Oxygen
and Nitrogen 68
Structure Determines Properties 2 2.11 Molecular Orbitals and Bonding in Methane 70
1.1 Atoms, Electrons, and Orbitals 3 2.12 Isomeric Alkanes: The Butanes 70
Organic Chemistry: The Early Days 5 2.13 Higher n-Alkanes 71
1.2 Ionic Bonds 6 2.14 The C5H12 Isomers 72
1.3 Covalent Bonds, Lewis Formulas, and the Octet Rule 8 2.15 IUPAC Nomenclature of Unbranched Alkanes 74
1.4 Polar Covalent Bonds, Electronegativity, and Bond 2.16 Applying the IUPAC Rules: The Names of the C6H14
Dipoles 10 Isomers 75
Electrostatic Potential Maps 12 What’s in a Name? Organic Nomenclature 76
1.5 Formal Charge 13 2.17 Alkyl Groups 77
1.6 Structural Formulas of Organic Molecules: Isomers 16 2.18 IUPAC Names of Highly Branched Alkanes 79
Curved Arrows and “Electron Pushing” 20 2.19 Cycloalkane Nomenclature 80
1.7 Resonance and Arrows 21 2.20 Introduction to Functional Groups 81
1.8 Sulfur and Phosphorus-Containing Organic Compounds 2.21 Sources of Alkanes and Cycloalkanes 81
and the Octet Rule 25 2.22 Physical Properties of Alkanes and Cycloalkanes 83
1.9 Molecular Geometries 26 2.23 Chemical Properties: Combustion of Alkanes 85
Molecular Models and Modeling 28 Thermochemistry 88
1.10 Molecular Dipole Moments 29 2.24 Oxidation–Reduction in Organic Chemistry 88
1.11 Curved Arrows, Arrow Pushing, and Chemical 2.25 Summary 91
Reactions 30 Problems 95
1.12 Acids and Bases: The Brønsted–Lowry View 32 Descriptive Passage and Interpretive Problems 2:
1.13 How Structure Affects Acid Strength 37 Some Biochemical Reactions of Alkanes 98
1.14 Acid–Base Equilibria 42

3
1.15 Acids and Bases: The Lewis View 45
1.16 Summary 46
Problems 49 C H A P T E R
Descriptive Passage and Interpretive Problems 1:
Amide Lewis Structural Formulas 54
Alkanes and Cycloalkanes: Conformations
and cis–trans Stereoisomers 100

C H A P T E R 2 3.1
3.2
3.3
Conformational Analysis of Ethane 101
Conformational Analysis of Butane 105
Conformations of Higher Alkanes 106
Computational Chemistry: Molecular Mechanics and
Alkanes and Cycloalkanes: Introduction to Quantum Mechanics 107
3.4 The Shapes of Cycloalkanes: Planar or Nonplanar? 108
Hydrocarbons 56 3.5 Small Rings: Cyclopropane and Cyclobutane 109
2.1 Classes of Hydrocarbons 57 3.6 Cyclopentane 110
2.2 Electron Waves and Chemical Bonds 57 3.7 Conformations of Cyclohexane 111
2.3 Bonding in H2: The Valence Bond Model 58 3.8 Axial and Equatorial Bonds in Cyclohexane 112
2.4 Bonding in H2: The Molecular Orbital Model 59 3.9 Conformational Inversion in Cyclohexane 114
ix
x Contents

3.10 Conformational Analysis of Monosubstituted 5.7 Preparation of Alkyl Halides from Alcohols and Hydrogen
Cyclohexanes 115 Halides 183
Enthalpy, Free Energy, and Equilibrium Constant 117 5.8 Reaction of Alcohols with Hydrogen Halides: The SN1
3.11 Disubstituted Cycloalkanes: cis–trans Stereoisomers 118 Mechanism 185
3.12 Conformational Analysis of Disubstituted Mechanism 5.1 Formation of tert-Butyl Chloride from
Cyclohexanes 119 tert-Butyl Alcohol and Hydrogen Chloride 186
3.13 Medium and Large Rings 124 5.9 Structure, Bonding, and Stability of Carbocations 191
3.14 Polycyclic Ring Systems 124 5.10 Effect of Alcohol Structure on
3.15 Heterocyclic Compounds 126 Reaction Rate 194
3.16 Summary 127 5.11 Stereochemistry and the SN1 Mechanism 195
Problems 130 5.12 Carbocation Rearrangements 197
Descriptive Passage and Interpretive Problems 3:  Mechanism 5.2 Carbocation Rearrangement in the
Cyclic Forms of Carbohydrates 135 Reaction of 3,3-Dimethyl-2-butanol with Hydrogen
Chloride 197

4 5.13 Reaction of Methyl and Primary Alcohols with Hydrogen

Halides: The SN2 Mechanism 199
C H A P T E R Mechanism 5.3 Formation of 1-Bromoheptane from
1-Heptanol and Hydrogen Bromide 200
5.14 Other Methods for Converting Alcohols to Alkyl
Chirality 136 Halides 201
5.15 Sulfonates as Alkyl Halide Surrogates 203
4.1 Introduction to Chirality: Enantiomers 136
5.16 Summary 204
4.2 The Chirality Center 139
Problems 206
4.3 Symmetry in Achiral Structures 141
Descriptive Passage and Interpretive Problems 5:
4.4 Optical Activity 142
More About Potential Energy Diagrams 210

6
4.5 Absolute and Relative
Configuration 144
4.6 Cahn–Ingold–Prelog R,S Notation 145
C H A P T E R
Homochirality and Symmetry Breaking 148
4.7 Fischer Projections 149
4.8 Properties of Enantiomers 151
Nucleophilic Substitution 212
Chiral Drugs 152
4.9 Chiral Molecules with Two Chirality Centers 153 6.1 Functional-Group Transformation by Nucleophilic
Substitution 212
4.10 Achiral Molecules with Two Chirality Centers 155
6.2 Relative Reactivity of Halide Leaving Groups 215
Chirality of Disubstituted Cyclohexanes 157
6.3 The SN2 Mechanism of Nucleophilic Substitution 216
4.11 Molecules with Multiple Chirality Centers 158
Mechanism 6.1 The SN2 Mechanism of Nucleophilic
4.12 Resolution of Enantiomers 159 Substitution 217
4.13 The Chirality Axis 161 6.4 Steric Effects and SN2 Reaction Rates 219
4.14 Chirality Centers Other Than Carbon 163 6.5 Nucleophiles and Nucleophilicity 221
4.15 Summary 164
Enzyme-Catalyzed Nucleophilic Substitutions of Alkyl
Problems 167 Halides 223
Descriptive Passage and Interpretive Problems 4:
6.6 The SN1 Mechanism of Nucleophilic Substitution 224
Prochirality 171
Mechanism 6.2 The SN1 Mechanism of Nucleophilic

5
Substitution 225
6.7 Stereochemistry of SN1 Reactions 226
C H A P T E R 6.8 Carbocation Rearrangements in SN1 Reactions 228
Mechanism 6.3 Carbocation Rearrangement in the SN1
Hydrolysis of 2-Bromo-3-methylbutane 228
Alcohols and Alkyl Halides: Introduction 6.9 Effect of Solvent on the Rate of Nucleophilic
Substitution 229
to Reaction Mechanisms 174 6.10 Nucleophilic Substitution of Alkyl Sulfonates 232
5.1 Functional Groups 175 6.11 Introduction to Organic Synthesis: Retrosynthetic
5.2 IUPAC Nomenclature of Alkyl Halides 176 Analysis 235
5.3 IUPAC Nomenclature of Alcohols 177 6.12 Substitution versus Elimination: A Look Ahead 236
5.4 Classes of Alcohols and Alkyl Halides 178 6.13 Summary 237
5.5 Bonding in Alcohols and Alkyl Halides 178 Problems 238
5.6 Physical Properties of Alcohols and Alkyl Halides: Descriptive Passage and Interpretive Problems 6:
Intermolecular Forces 179 Nucleophilic Substitution 243
 Contents xi

7
Mechanism 8.1 Hydrogenation of Alkenes 292
8.3 Heats of Hydrogenation 293
C H A P T E R 8.4 Electrophilic Addition of Hydrogen Halides to
Alkenes 295
Mechanism 8.2 Electrophilic Addition of Hydrogen
Structure and Preparation of Alkenes: Bromide to 2-Methylpropene 297
Elimination Reactions 246 Rules, Laws, Theories, and the Scientific Method 299
8.5 Carbocation Rearrangements in Hydrogen Halide
7.1 Alkene Nomenclature 246
Addition to Alkenes 300
7.2 Structure and Bonding in Alkenes 248
8.6 Acid-Catalyzed Hydration of Alkenes 301
Ethylene 249 Mechanism 8.3 Acid-Catalyzed Hydration of
7.3 Isomerism in Alkenes 250 2-Methylpropene 301
7.4 Naming Stereoisomeric Alkenes by the E–Z Notational 8.7 Thermodynamics of Addition–Elimination Equilibria 303
System 252 8.8 Hydroboration–Oxidation of Alkenes 305
7.5 Physical Properties of Alkenes 253 8.9 Mechanism of Hydroboration–Oxidation 307
7.6 Relative Stabilities of Alkenes 254 Mechanism 8.4 Hydroboration of
7.7 Cycloalkenes 256 1-Methylcyclopentene 308
7.8 Preparation of Alkenes: Elimination Reactions 258 Mechanism 8.5 Oxidation of an Organoborane 309
7.9 Dehydration of Alcohols 258 8.10 Addition of Halogens to Alkenes 310
7.10 Regioselectivity in Alcohol Dehydration: The Zaitsev Mechanism 8.6 Bromine Addition to
Rule 259 Cyclopentene 311
7.11 Stereoselectivity in Alcohol Dehydration 261 8.11 Epoxidation of Alkenes 314
7.12 The E1 and E2 Mechanisms of Alcohol Dehydration 261 Mechanism 8.7 Epoxidation of
Mechanism 7.1 The E1 Mechanism for Acid-Catalyzed Bicyclo[2.2.1]-2-heptene 315
Dehydration of tert-Butyl Alcohol 262 8.12 Ozonolysis of Alkenes 316
7.13 Rearrangements in Alcohol Dehydration 263 8.13 Enantioselective Addition to Alkenes 317
Mechanism 7.2 Carbocation Rearrangement in 8.14 Retrosynthetic Analysis and Alkene Intermediates 318
Dehydration of 3,3-Dimethyl-2-butanol 264 8.15 Summary 320
Mechanism 7.3 Hydride Shift in Dehydration of Problems 323
1-Butanol 265 Descriptive Passage and Interpretive Problems 8:
7.14 Dehydrohalogenation of Alkyl Halides 266 Oxymercuration 329
7.15 The E2 Mechanism of Dehydrohalogenation of Alkyl
Halides 268

9
Mechanism 7.4 The E2 Mechanism of
1-Chlorooctadecane 269
7.16 Anti Elimination in E2 Reactions: Stereoelectronic
Effects 271 C H A P T E R
7.17 Isotope Effects and the E2 Mechanism 273
7.18 The E1 Mechanism of Dehydrohalogenation of Alkyl
Halides 274 Alkynes 332
Mechanism 7.5 The E1 Mechanism for 9.1 Sources of Alkynes 332
Dehydrohalogenation of 2-Bromo-2-methylbutane 275 9.2 Nomenclature 334
7.19 Substitution and Elimination as Competing 9.3 Physical Properties of Alkynes 334
Reactions 276 9.4 Structure and Bonding in Alkynes:
7.20 Elimination Reactions of Sulfonates 279 sp Hybridization 335
7.21 Summary 280 9.5 Acidity of Acetylene and Terminal Alkynes 337
Problems 283 9.6 Preparation of Alkynes by Alkylation of Acetylene and
Descriptive Passage and Interpretive Problems 7: Terminal Alkynes 339
A Mechanistic Preview of Addition Reactions 288 9.7 Preparation of Alkynes by Elimination Reactions 341
9.8 Reactions of Alkynes 342

C H A P T E R 8 9.9
9.10
9.11
Hydrogenation of Alkynes 342
Addition of Hydrogen Halides to Alkynes 344
Hydration of Alkynes 345
Mechanism 9.1 Conversion of an Enol to a Ketone 346
9.12 Addition of Halogens to Alkynes 347
Addition Reactions of Alkenes 290 Some Things That Can Be Made from Acetylene . . . But
8.1 Hydrogenation of Alkenes 290 Aren’t 348
8.2 Stereochemistry of Alkene Hydrogenation 291 9.13 Ozonolysis of Alkynes 348
xii Contents

9.14 Alkynes in Synthesis and Retrosynthesis 349 11.10 Addition of Hydrogen Halides to Conjugated
9.15 Summary 349 Dienes 405
Problems 352 Mechanism 11.3 Addition of Hydrogen Chloride to
Descriptive Passage and Interpretive Problems 9: 1,3-Cyclopentadiene 405
Thinking Mechanistically About Alkynes 356 11.11 Halogen Addition to Dienes 407
11.12 The Diels–Alder Reaction 408

10
11.13 Intramolecular Diels–Alder Reactions 411
11.14 Retrosynthetic Analysis and the
C H A P T E R Diels–Alder Reaction 412
11.15 Molecular Orbital Analysis of the
Diels–Alder Reaction 413
Introduction to Free Radicals 358 Pericyclic Reactions in Chemical Biology 414
11.16 The Cope and Claisen Rearrangements 415
10.1 Structure, Bonding, and Stability of Alkyl Radicals 359
11.17 Summary 416
10.2 Halogenation of Alkanes 362
Problems 419
From Bond Enthalpies to Heats of Reaction 363 Descriptive Passage and Interpretive Problems 11:
10.3 Mechanism of Methane Chlorination 364 1,3-Dipolar Cycloaddition 425
Mechanism 10.1 Free-Radical Chlorination of
Methane 365
10.4 Halogenation of Higher Alkanes 366
10.5 Free-Radical Addition of Hydrogen Bromide to Alkenes

12
and Alkynes 370
Mechanism 10.2 Free-Radical Addition of Hydrogen
Bromide to 1-Butene 371
C H A P T E R
10.6 Metal–Ammonia Reduction of Alkynes 373
Mechanism 10.3 Sodium–Ammonia Reduction of an
Alkyne 374
Arenes and Aromaticity 428
10.7 Free Radicals and Retrosynthesis of Alkyl Halides 374
10.8 Free-Radical Polymerization of Alkenes 375 12.1 Benzene 429
Mechanism 10.4 Free-Radical Polymerization of 12.2 The Structure of Benzene 429
Ethylene 376 12.3 The Stability of Benzene 431
Ethylene and Propene: The Most Important Industrial 12.4 Bonding in Benzene 432
Organic Chemicals 377 12.5 Substituted Derivatives of Benzene and Their
10.9 Summary 379 Nomenclature 434
Problems 380 12.6 Polycyclic Aromatic Hydrocarbons 436
Descriptive Passage and Interpretive Problems 10: F  ree- Fullerenes, Nanotubes, and Graphene 438
Radical Reduction of Alkyl Halides 383 12.7 Physical Properties of Arenes 439
12.8 The Benzyl Group 440

11
12.9 Nucleophilic Substitution in Benzylic Halides 441
Triphenylmethyl Radical Yes,
C H A P T E R Hexaphenylethane No 444
12.10 Benzylic Free-Radical Halogenation 445
12.11 Benzylic Anions 446
Conjugation in Alkadienes and Allylic 12.12 Oxidation of Alkylbenzenes 447
Systems 386 12.13 Alkenylbenzenes 448
12.14 Polymerization of Styrene 450
11.1 The Allyl Group 387 Mechanism 12.1 Free-Radical Polymerization of
11.2 SN1 and SN2 Reactions of Allylic Halides 390 Styrene 451
Mechanism 11.1 SN1 Hydrolysis of an Allylic Halide 391 12.15 The Birch Reduction 451
11.3 Allylic Free-Radical Halogenation 394 Mechanism 12.2 The Birch Reduction 452
Mechanism 11.2 Allylic Chlorination of Propene 396 12.16 Benzylic Side Chains and Retrosynthetic Analysis 453
11.4 Allylic Anions 397 12.17 Cyclobutadiene and Cyclooctatetraene 454
11.5 Classes of Dienes: Conjugated and Otherwise 398 12.18 Hückel’s Rule 455
11.6 Relative Stabilities of Dienes 399 12.19 Annulenes 457
11.7 Bonding in Conjugated Dienes 400 12.20 Aromatic Ions 459
11.8 Bonding in Allenes 402 12.21 Heterocyclic Aromatic Compounds 463
11.9 Preparation of Dienes 403 12.22 Heterocyclic Aromatic Compounds and Hückel’s
Diene Polymers 404 Rule 464
 Contents xiii

14
12.23 Summary 466
Problems 470
Descriptive Passage and Interpretive Problems 12: C H A P T E R
Substituent Effects on Reaction Rates and
Equilibria 475
Spectroscopy 534
14.1 Principles of Molecular Spectroscopy: Electromagnetic

13
Radiation 535
14.2 Principles of Molecular Spectroscopy: Quantized Energy
C H A P T E R States 536
14.3 Introduction to 1H NMR Spectroscopy 536
14.4 Nuclear Shielding and 1H Chemical Shifts 538
Electrophilic and Nucleophilic Aromatic 14.5 Effects of Molecular Structure on 1H Chemical Shifts 541
Substitution 478 Ring Currents: Aromatic and Antiaromatic 546
14.6 Interpreting 1H NMR Spectra 547
13.1 Representative Electrophilic Aromatic Substitution 14.7 Spin–Spin Splitting and 1H NMR 549
Reactions of Benzene 479
14.8 Splitting Patterns: The Ethyl Group 552
13.2 Mechanistic Principles of Electrophilic Aromatic
14.9 Splitting Patterns: The Isopropyl Group 553
Substitution 480
14.10 Splitting Patterns: Pairs of Doublets 554
13.3 Nitration of Benzene 481
14.11 Complex Splitting Patterns 555
Mechanism 13.1 Nitration of Benzene 482 1
14.12 H NMR Spectra of Alcohols 558
13.4 Sulfonation of Benzene 483
Magnetic Resonance Imaging (MRI) 559
Mechanism 13.2 Sulfonation of Benzene 483
13.5 Halogenation of Benzene 484 14.13 NMR and Conformations 559
13
Mechanism 13.3 Bromination of Benzene 485 14.14 C NMR Spectroscopy 560
13
14.15 C Chemical Shifts 561
Biosynthetic Halogenation 486 13
14.16 C NMR and Peak Intensities 564
13.6 Friedel–Crafts Alkylation of Benzene 487 13 1
14.17 C H Coupling 565
Mechanism 13.4 Friedel–Crafts Alkylation 487
14.18 Using DEPT to Count Hydrogens 565
13.7 Friedel–Crafts Acylation of Benzene 489
14.19 2D NMR: COSY and HETCOR 567
Mechanism 13.5 Friedel–Crafts Acylation 490
14.20 Introduction to Infrared Spectroscopy 569
13.8 Synthesis of Alkylbenzenes by Acylation–Reduction 491
Spectra by the Thousands 570
13.9 Rate and Regioselectivity in Electrophilic Aromatic
Substitution 492 14.21 Infrared Spectra 571
13.10 Rate and Regioselectivity in the Nitration of Toluene 494 14.22 Characteristic Absorption Frequencies 573
13.11 Rate and Regioselectivity in the Nitration of 14.23 Ultraviolet-Visible Spectroscopy 577
(Trifluoromethyl)benzene 496 14.24 Mass Spectrometry 579
13.12 Substituent Effects in Electrophilic Aromatic Substitution: 14.25 Molecular Formula as a Clue to Structure 584
Activating Substituents 498 14.26 Summary 585
13.13 Substituent Effects in Electrophilic Aromatic Substitution: Problems 588
Strongly Deactivating Substituents 502 Descriptive Passage and Interpretive Problems 14: 
13.14 Substituent Effects in Electrophilic Aromatic Substitution: More on Coupling Constants 598
Halogens 505

15
13.15 Multiple Substituent Effects 506
13.16 Retrosynthetic Analysis and the Synthesis of Substituted
Benzenes 508
C H A P T E R
13.17 Substitution in Naphthalene 510
13.18 Substitution in Heterocyclic Aromatic Compounds 511
13.19 Nucleophilic Aromatic Substitution 512 Organometallic Compounds 602
13.20 The Addition–Elimination Mechanism of Nucleophilic
Aromatic Substitution 514 15.1 Organometallic Nomenclature 603
Mechanism 13.6 Nucleophilic Aromatic Substitution in 15.2 Carbon–Metal Bonds 603
p-Fluoronitrobenzene by the Addition–Elimination 15.3 Preparation of Organolithium and Organomagnesium
Mechanism 516 Compounds 605
13.21 Related Nucleophilic Aromatic Substitutions 517 15.4 Organolithium and Organomagnesium Compounds as
13.22 Summary 518 Brønsted Bases 606
Problems 522 15.5 Synthesis of Alcohols Using Grignard and Organolithium
Descriptive Passage and Interpretive Problems 13: Reagents 607
Benzyne 530 15.6 Synthesis of Acetylenic Alcohols 610
xiv Contents

17
15.7 Retrosynthetic Analysis and Grignard and Organolithium
Reagents 610
15.8 An Organozinc Reagent for Cyclopropane Synthesis 611 C H A P T E R
Mechanism 15.1 Similarities Between the Mechanisms of
Reaction of an Alkene with lodomethylzinc lodide and a
Peroxy Acid 612 Ethers, Epoxides, and Sulfides 678
15.9 Carbenes and Carbenoids 613
17.1 Nomenclature of Ethers, Epoxides, and Sulfides 678
15.10 Transition-Metal Organometallic Compounds 614
17.2 Structure and Bonding in Ethers and Epoxides 680
An Organometallic Compound That Occurs Naturally: 17.3 Physical Properties of Ethers 680
Coenzyme B12 617
17.4 Crown Ethers 682
15.11 Organocopper Reagents 618 17.5 Preparation of Ethers 683
15.12 Palladium-Catalyzed Cross-Coupling 620
Polyether Antibiotics 684
15.13 Homogeneous Catalytic Hydrogenation 623
17.6 The Williamson Ether Synthesis 685
Mechanism 15.2 Homogeneous Catalysis of Alkene
17.7 Reactions of Ethers: A Review and a Preview 687
Hydrogenation 625
17.8 Acid-Catalyzed Cleavage of Ethers 688
15.14 Olefin Metathesis 626
Mechanism 17.1 Cleavage of Ethers by Hydrogen
Mechanism 15.3 Olefin Cross-Metathesis 628
Halides 689
15.15 Ziegler–Natta Catalysis of Alkene Polymerization 629
17.9 Preparation of Epoxides 690
Mechanism 15.4 Polymerization of Ethylene in the
17.10 Conversion of Vicinal Halohydrins to Epoxides 691
Presence of Ziegler–Natta Catalyst 631
17.11 Reactions of Epoxides with Anionic Nucleophiles 692
15.16 Summary 632
Mechanism 17.2 Nucleophilic Ring Opening of an
Problems 634
Epoxide 694
Descriptive Passage and Interpretive Problems 15:
17.12 Acid-Catalyzed Ring Opening of Epoxides 694
Allylindium Reagents 638
Mechanism 17.3 Acid-Catalyzed Ring Opening of an
Epoxide 696
17.13 Epoxides in Biological Processes 697
17.14 Preparation of Sulfides 697
17.15 Oxidation of Sulfides: Sulfoxides and Sulfones 698
17.16 Alkylation of Sulfides: Sulfonium Salts 699

C H A P T E R 16 17.17

17.18
Spectroscopic Analysis of Ethers, Epoxides, and
Sulfides 700
Summary 702
Problems 705
Descriptive Passage and Interpretive Problems 17:
Alcohols, Diols, and Thiols 640 Epoxide Rearrangements and the NIH Shift 713
16.1 Sources of Alcohols 641
16.2 Preparation of Alcohols by Reduction of Aldehydes and

18
Ketones 643
16.3 Preparation of Alcohols by Reduction of Carboxylic
Acids 646
C H A P T E R
16.4 Preparation of Alcohols from Epoxides 646
16.5 Preparation of Diols 647
16.6 Reactions of Alcohols: A Review and a Preview 649
Aldehydes and Ketones: Nucleophilic
16.7 Conversion of Alcohols to Ethers 650
Mechanism 16.1 Acid-Catalyzed Formation of Diethyl Addition to the Carbonyl Group 716
Ether from Ethyl Alcohol 650 18.1 Nomenclature 717
16.8 Esterification 651 18.2 Structure and Bonding: The Carbonyl Group 719
16.9 Oxidation of Alcohols 653 18.3 Physical Properties 722
Sustainability and Organic Chemistry 656 18.4 Sources of Aldehydes and Ketones 722
16.10 Biological Oxidation of Alcohols 658 18.5 Reactions of Aldehydes and Ketones:
16.11 Oxidative Cleavage of Vicinal Diols 659 A Review and a Preview 726
16.12 Thiols 660 18.6 Principles of Nucleophilic Addition: Hydration of
16.13 Spectroscopic Analysis of Alcohols and Thiols 663 Aldehydes and Ketones 727
16.14 Summary 665 Mechanism 18.1 Hydration of an Aldehyde or Ketone in
Problems 668 Basic Solution 730
Descriptive Passage and Interpretive Problems 16: Mechanism 18.2 Hydration of an Aldehyde or Ketone in
The Pinacol Rearrangement 674 Acid Solution 731
 Contents xv

20
18.7 Cyanohydrin Formation 731
Mechanism 18.3 Cyanohydrin Formation 732
18.8 Reaction with Alcohols: Acetals and Ketals 734 C H A P T E R
Mechanism 18.4 Acetal Formation from Benzaldehyde
and Ethanol 736
18.9 Acetals and Ketals as Protecting Groups 737 Carboxylic Acid Derivatives: Nucleophilic
18.10 Reaction with Primary Amines: Imines 738 Acyl Substitution 802
Mechanism 18.5 Imine Formation from Benzaldehyde and
Methylamine 740 20.1 Nomenclature of Carboxylic Acid Derivatives 803
18.11 Reaction with Secondary Amines: Enamines 741 20.2 Structure and Reactivity of Carboxylic Acid
Derivatives 804
Imines in Biological Chemistry 742
Reaction Trends: Aldehydes and Ketones vs. Carboxylic
Mechanism 18.6 Enamine Formation 744
Acid Derivatives 805
18.12 The Wittig Reaction 745
20.3 Nucleophilic Acyl Substitution Mechanisms 808
18.13 Stereoselective Addition to Carbonyl Groups 748
20.4 Nucleophilic Acyl Substitution in Acyl Chlorides 809
18.14 Oxidation of Aldehydes 749
20.5 Nucleophilic Acyl Substitution in Acid Anhydrides 811
18.15 Spectroscopic Analysis of Aldehydes and Ketones 750
Mechanism 20.1 Nucleophilic Acyl Substitution in an
18.16 Summary 752
Anhydride 813
Problems 755
20.6 Physical Properties and Sources of Esters 813
Descriptive Passage and Interpretive Problems 18:
20.7 Reactions of Esters: A Preview 814
The Baeyer–Villiger Oxidation 763
20.8 Acid-Catalyzed Ester Hydrolysis 816
Mechanism 20.2 Acid-Catalyzed Ester Hydrolysis 817

19
20.9 Ester Hydrolysis in Base: Saponification 819
The Ball Method 821
Mechanism 20.3 Ester Hydrolysis in Basic Solution 823
C H A P T E R
20.10 Reaction of Esters with Ammonia and Amines 824
20.11 Reaction of Esters with Grignard and Organolithium
Reagents and Lithium Aluminum Hydride 825
Carboxylic Acids 766
20.12 Amides 826
19.1 Carboxylic Acid Nomenclature 767 20.13 Hydrolysis of Amides 830
19.2 Structure and Bonding 769 Mechanism 20.4 Amide Hydrolysis in Acid Solution 831
19.3 Physical Properties 769 Mechanism 20.5 Amide Hydrolysis in Basic
19.4 Acidity of Carboxylic Acids 770 Solution 833
19.5 Substituents and Acid Strength 772 20.14 Lactams 834
19.6 Ionization of Substituted Benzoic Acids 774 β-Lactam Antibiotics 834
19.7 Salts of Carboxylic Acids 775 20.15 Preparation of Nitriles 836
19.8 Dicarboxylic Acids 777 20.16 Hydrolysis of Nitriles 837
19.9 Carbonic Acid 778 Mechanism 20.6 Nitrile Hydrolysis in Basic Solution 838
19.10 Sources of Carboxylic Acids 779 20.17 Addition of Grignard Reagents to Nitriles 839
19.11 Synthesis of Carboxylic Acids by the Carboxylation of 20.18 Spectroscopic Analysis of Carboxylic Acid
Grignard Reagents 781 Derivatives 839
19.12 Synthesis of Carboxylic Acids by the Preparation and 20.19 Summary 841
Hydrolysis of Nitriles 782 Problems 844
19.13 Reactions of Carboxylic Acids: A Review and a Descriptive Passage and Interpretive Problems 20:
Preview 783 Thioesters 851
19.14 Mechanism of Acid-Catalyzed Esterification 784

21
Mechanism 19.1 Acid-Catalyzed Esterification of Benzoic
Acid with Methanol 784
19.15 Intramolecular Ester Formation: Lactones 787
C H A P T E R
19.16 Decarboxylation of Malonic Acid and Related
Compounds 788
Enzymatic Decarboxylation of a
β-Keto Acid 790
Enols and Enolates 854
19.17 Spectroscopic Analysis of Carboxylic Acids 791 21.1 Aldehyde, Ketone, and Ester Enolates 855
19.18 Summary 792 21.2 The Aldol Condensation 858
Problems 794 Mechanism 21.1 Aldol Addition of Butanal 859
Descriptive Passage and Interpretive Problems 19: 21.3 Mixed and Directed Aldol Reactions 862
Lactonization Methods 799 From the Mulberry Tree to Cancer Chemotherapy 863
xvi Contents

23
21.4 Acylation of Enolates: The Claisen and Related
Condensations 864
Mechanism 21.2 Claisen Condensation of Ethyl C H A P T E R
Propanoate 865
21.5 Alkylation of Enolates: The Acetoacetic Ester and Malonic
Ester Syntheses 868 Carbohydrates 950
21.6 Enol Content and Enolization 871
23.1 Classification of Carbohydrates 951
Mechanism 21.3 Acid-Catalyzed Enolization of
23.2 Fischer Projections and d,l Notation 951
2-Methylpropanal 873
23.3 The Aldotetroses 952
21.7 The Haloform Reaction 875
23.4 Aldopentoses and Aldohexoses 954
Mechanism 21.4 The Haloform Reaction 876
23.5 A Mnemonic for Carbohydrate Configurations 956
21.8 Some Chemical and Stereochemical Consequences of
Enolization 877 23.6 Cyclic Forms of Carbohydrates: Furanose Forms 956
21.9 Conjugation Effects in α,β-Unsaturated Aldehydes and 23.7 Cyclic Forms of Carbohydrates: Pyranose Forms 960
Ketones 878 23.8 Mutarotation 962
21.10 Summary 882 Mechanism 23.1 Acid-Catalyzed Mutarotation of
Problems 884 d-Glucopyranose 963
Descriptive Passage and Interpretive Problems 21: 23.9 Carbohydrate Conformation: The Anomeric Effect 964
The Knoevenagel Reaction 891 23.10 Ketoses 966
23.11 Deoxy Sugars 967
23.12 Amino Sugars 968
23.13 Branched-Chain Carbohydrates 969

22
23.14 Glycosides: The Fischer Glycosidation 969
Mechanism 23.2 Preparation of Methyl
d-Glucopyranosides by Fischer Glycosidation 971
C H A P T E R 23.15 Disaccharides 973
23.16 Polysaccharides 975
How Sweet It Is! 977
Amines 894
23.17 Application of Familiar Reactions to
22.1 Amine Nomenclature 895 Monosaccharides 978
22.2 Structure and Bonding 897 23.18 Oxidation of Carbohydrates 981
22.3 Physical Properties 899 23.19 Glycosides: Synthesis of Oligosaccharides 984
22.4 Basicity of Amines 899 Mechanism 23.3 Silver-Assisted Glycosidation 985
Amines as Natural Products 904 23.20 Glycobiology 986
22.5 Tetraalkylammonium Salts as Phase-Transfer Oligosaccharides in Infectious Disease 989
Catalysts 905 23.21 Summary 990
22.6 Reactions That Lead to Amines: A Review and a Problems 991
Preview 906 Descriptive Passage and Interpretive Problems 23:
22.7 Preparation of Amines by Alkylation of Ammonia 908 Emil Fischer and the Structure of (+)-Glucose 996
22.8 The Gabriel Synthesis of Primary Alkylamines 909
22.9 Preparation of Amines by Reduction 910
Mechanism 22.1 Lithium Aluminum Hydride Reduction

24
of an Amide 913
22.10 Reductive Amination 914
22.11 Reactions of Amines: A Review and a Preview 915
C H A P T E R
22.12 Reaction of Amines with Alkyl Halides 917
22.13 The Hofmann Elimination 917
22.14 Electrophilic Aromatic Substitution in Arylamines 919
22.15 Nitrosation of Alkylamines 921
Lipids 1000
22.16 Nitrosation of Arylamines 923 24.1 Acetyl Coenzyme A 1001
22.17 Synthetic Transformations of Aryl Diazonium Salts 924 24.2 Fats, Oils, and Fatty Acids 1002
22.18 Azo Coupling 928 24.3 Fatty Acid Biosynthesis 1005
From Dyes to Sulfa Drugs 928 24.4 Phospholipids 1007
22.19 Spectroscopic Analysis of Amines 930 24.5 Waxes 1010
22.20 Summary 932 24.6 Prostaglandins 1011
Problems 938 Nonsteroidal Antiinflammatory Drugs (NSAIDs) and
Descriptive Passage and Interpretive Problems 22: COX-2 Inhibitors 1013
Synthetic Applications of Enamines 947 24.7 Terpenes: The Isoprene Rule 1014
 Contents xvii

24.8 Isopentenyl Diphosphate: The Biological Isoprene Mechanism 25.3 Carboxypeptidase-Catalyzed

Unit 1017 Hydrolysis 1082
24.9 Carbon–Carbon Bond Formation in Terpene 25.21 Coenzymes in Reactions of Amino Acids 1083
Biosynthesis 1017 Mechanism 25.4 Pyridoxal 5′-Phosphate-Mediated
24.10 The Pathway from Acetate to Isopentenyl Decarboxylation of an α-Amino Acid 1084
Diphosphate 1020 Mechanism 25.5 Transamination: Biosynthesis of
24.11 Steroids: Cholesterol 1022 l-Alanine from l-Glutamic Acid and Pyruvic Acid 1088
Mechanism 24.1 Biosynthesis of Cholesterol from Oh NO! It’s Inorganic! 1090
Squalene 1024 25.22 G-Protein-Coupled Receptors 1090
24.12 Vitamin D 1025 25.23 Summary 1091
Good Cholesterol? Bad Cholesterol? What’s the Problems 1093
Difference? 1025 Descriptive Passage and Interpretive Problems 25:
24.13 Bile Acids 1026 Amino Acids in Enantioselective Synthesis 1098
24.14 Corticosteroids 1026

26
24.15 Sex Hormones 1027
24.16 Carotenoids 1028
Crocuses Make Saffron from Carotenes 1028
C H A P T E R
24.17 Summary 1030
Problems 1032
Descriptive Passage and Interpretive Problems 24: Nucleosides, Nucleotides,
Polyketides 1036
and Nucleic Acids 1102

25 26.1 Pyrimidines and Purines 1103

26.2 Nucleosides 1105
C H A P T E R 26.3 Nucleotides 1107
26.4 Bioenergetics 1109
26.5 ATP and Bioenergetics 1110
Amino Acids, Peptides, and Proteins 1040 26.6 Phosphodiesters, Oligonucleotides, and
25.1 Classification of Amino Acids 1041 Polynucleotides 1112
25.2 Stereochemistry of Amino Acids 1046 26.7 Phosphoric Acid Esters 1113
25.3 Acid–Base Behavior of Amino Acids 1048 26.8 Deoxyribonucleic Acids 1115
Electrophoresis 1051 “It Has Not Escaped Our Notice . . .” 1116
25.4 Synthesis of Amino Acids 1052 26.9 Secondary Structure of DNA: The Double Helix 1117
25.5 Reactions of Amino Acids 1053 26.10 Replication of DNA 1118
25.6 Peptides 1055 26.11 Ribonucleic Acids 1120
25.7 Introduction to Peptide Structure Determination 1058 mRNA Therapeutics 1125
25.8 Amino Acid Analysis 1058 26.12 Protein Biosynthesis 1125
25.9 Partial Hydrolysis and End Group Analysis 1058 26.13 DNA Sequencing 1126
25.10 Insulin 1060 26.14 Summary 1128
25.11 Edman Degradation and Automated Sequencing Problems 1130
of Peptides 1062 Descriptive Passage and Interpretive Problems 26:
Mechanism 25.1 The Edman Degradation 1062 Oligonucleotide Synthesis 1133
25.12 Mass Spectrometry of Peptides and Proteins 1064

27
Peptide Mapping and MALDI Mass Spectrometry 1065
25.13 The Strategy of Peptide Synthesis 1066
25.14 Amino and Carboxyl Group Protection and C H A P T E R
Deprotection 1068
25.15 Peptide Bond Formation 1070
Mechanism 25.2 Amide Bond Formation Between a Synthetic Polymers 1138
Carboxylic Acid and an Amine Using
N,N′-Dicyclohexylcarbodiimide 1071 27.1 Some Background 1138
25.16 Solid-Phase Peptide Synthesis: The Merrifield From Bakelite to Nylon 1139
Method 1072 27.2 Polymer Nomenclature 1140
25.17 Secondary Structures of Peptides and Proteins 1074 27.3 Classification of Polymers:
25.18 Tertiary Structure of Polypeptides and Proteins 1077 Reaction Type 1141
25.19 Protein Quaternary Structure: Hemoglobin 1079 27.4 Classification of Polymers: Chain Growth and Step
25.20 Enzymes 1081 Growth 1143
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xviii Contents

27.5 Classification of Polymers: Structure 1144 27.13 Polycarbonates 1158

27.6 Classification of Polymers: Properties 1147 27.14 Polyurethanes 1158
27.7 Addition Polymers: A Review and a Preview 1147 27.15 Copolymers 1159
27.8 Chain Branching in Free-Radical Polymerization 1150 Conducting Polymers 1161
Mechanism 27.1 Branching in Polyethylene Caused by 27.16 Summary 1162
Intramolecular Hydrogen Transfer 1151 Problems 1165
Mechanism 27.2 Branching in Polyethylene Caused by Descriptive Passage and Interpretive Problems 27:
Intermolecular Hydrogen Transfer 1152 Chemically Modified Polymers 1166
27.9 Anionic Polymerization: Living Polymers 1152
Mechanism 27.3 Anionic Polymerization of Styrene 1153 Appendix: 
Summary of Methods Used to Synthesize a
27.10 Cationic Polymerization 1154 Particular Functional Group A-1
Mechanism 27.4 Cationic Polymerization of
2-Methylpropene 1155 Glossary G-1
27.11 Polyamides 1156 Index I-1
27.12 Polyesters 1157
List of Important Features

Mechanisms 15.2 Homogeneous Catalysis of Alkene Hydrogenation 625

15.3 Olefin Cross-Metathesis 628
5.1 Formation of tert-Butyl Chloride from tert-Butyl Alcohol 15.4 Polymerization of Ethylene in the Presence of
and Hydrogen Chloride 186 Ziegler–Natta Catalyst 631
5.2 Carbocation Rearrangement in the Reaction of 16.1 Acid-Catalyzed Formation of Diethyl Ether from
3,3-Dimethyl-2-butanol with Hydrogen Chloride 197 Ethyl Alcohol 650
5.3 Formation of 1-Bromoheptane from 1-Heptanol and 17.1 Cleavage of Ethers by Hydrogen Halides 689
Hydrogen Bromide 200
17.2 Nucleophilic Ring Opening of an Epoxide 694
6.1 The SN2 Mechanism of Nucleophilic Substitution 217
17.3 Acid-Catalyzed Ring Opening of an Epoxide 696
6.2 The SN1 Mechanism of Nucleophilic Substitution 225
18.1 Hydration of an Aldehyde or Ketone in Basic
6.3 Carbocation Rearrangement in the SN1 Hydrolysis of Solution 730
2-Bromo-3-methylbutane 228
18.2 Hydration of an Aldehyde or Ketone in Acid Solution 731
7.1 The E1 Mechanism for Acid-Catalyzed Dehydration of
18.3 Cyanohydrin Formation 732
tert-Butyl Alcohol 262
18.4 Acetal Formation from Benzaldehyde and Ethanol 736
7.2 Carbocation Rearrangement in Dehydration of
18.5 Imine Formation from Benzaldehyde and
3,3-Dimethyl-2-butanol 264
Methylamine 740
7.3 Hydride Shift in Dehydration of 1-Butanol 265
18.6 Enamine Formation 744
7.4 The E2 Mechanism of 1-Chlorooctadecane 269
19.1 Acid-Catalyzed Esterification of Benzoic Acid with
7.5 The E1 Mechanism for Dehydrohalogenation of
Methanol 784
2-Bromo-2-methylbutane 275
20.1 Nucleophilic Acyl Substitution in an Anhydride 813
8.1 Hydrogenation of Alkenes 292
20.2 Acid-Catalyzed Ester Hydrolysis 817
8.2 Electrophilic Addition of Hydrogen Bromide to
20.3 Ester Hydrolysis in Basic Solution 823
2-Methylpropene 297
20.4 Amide Hydrolysis in Acid Solution 831
8.3 Acid-Catalyzed Hydration of 2-Methylpropene 301
20.5 Amide Hydrolysis in Basic Solution 833
8.4 Hydroboration of 1-Methylcyclopentene 308
20.6 Nitrile Hydrolysis in Basic Solution 838
8.5 Oxidation of an Organoborane 309
21.1 Aldol Addition of Butanal 859
8.6 Bromine Addition to Cyclopentene 311
21.2 Claisen Condensation of Ethyl Propanoate 865
8.7 Epoxidation of Bicyclo[2.2.1]-2-heptene 315
21.3 Acid-Catalyzed Enolization of 2-Methylpropanal 873
9.1 Conversion of an Enol to a Ketone 346
21.4 The Haloform Reaction 876
10.1 Free-Radical Chlorination of Methane 365
22.1 Lithium Aluminum Hydride Reduction of an Amide 913
10.2 Free-Radical Addition of Hydrogen Bromide to
1-Butene 371 23.1 Acid-Catalyzed Mutarotation of d-Glucopyranose 963
10.3 Sodium–Ammonia Reduction of an Alkyne 374 23.2 Preparation of Methyl d-Glucopyranosides by Fischer
Glycosidation 971
10.4 Free-Radical Polymerization of Ethylene 376
23.3 Silver-Assisted Glycosidation 985
11.1 SN1 Hydrolysis of an Allylic Halide 391
24.1 Biosynthesis of Cholesterol from Squalene 1024
11.2 Allylic Chlorination of Propene 396
25.1 The Edman Degradation 1062
11.3 Addition of Hydrogen Chloride to
1,3-Cyclopentadiene 405 25.2 Amide Bond Formation Between a Carboxylic Acid and an
Amine Using N,N′-Dicyclohexylcarbodiimide 1071
12.1 Free-Radical Polymerization of Styrene 451
25.3 Carboxypeptidase-Catalyzed Hydrolysis 1082
12.2 The Birch Reduction 452
25.4 Pyridoxal 5′-Phosphate-Mediated Decarboxylation of an
13.1 Nitration of Benzene 482
α-Amino Acid 1084
13.2 Sulfonation of Benzene 483
25.5 Transamination: Biosynthesis of l-Alanine from l-Glutamic
13.3 Bromination of Benzene 485
Acid and Pyruvic Acid 1088
13.4 Friedel–Crafts Alkylation 487
27.1 Branching in Polyethylene Caused by Intramolecular
13.5 Friedel–Crafts Acylation 490 Hydrogen Transfer 1151
13.6 Nucleophilic Aromatic Substitution in p-Fluoronitrobenzene 27.2 Branching in Polyethylene Caused by Intermolecular
by the Addition–Elimination Mechanism 516 Hydrogen Transfer 1152
15.1 Similarities Between the Mechanisms of Reaction of an 27.3 Anionic Polymerization of Styrene 1153
Alkene with Iodomethylzinc Iodide and a Peroxy
27.4 Cationic Polymerization of 2-Methylpropene 1155
Acid 612

xix
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 Around the shrine of Olaf in Throndtjem, in which, in spite of
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Sketches in Holland and Scandinavia (London, 1885).

 LEANING TOWER OF PISA.
CHARLES DICKENS.

FROM the summit of a lofty hill beyond Carrara, the first view of the
fertile plain in which the town of Pisa lies—with Leghorn a purple
spot in the flat distance—is enchanting. Nor is it only distance that
lends enchantment to the view; for the fruitful country, and rich
woods of olive-trees through which the road subsequently passes,
render it delightful.
The moon was shining when we approached Pisa, and for a long
time we could see, behind the wall, the Leaning Tower, all awry in
the uncertain light; the shadowy original of the old pictures in
school-books, setting forth “The Wonders of the World.” Like most
things connected in their first associations with school-books and
school-times, it was too small. I felt it keenly. It was nothing like so
high above the wall as I had hoped. It was another of the many
deceptions practised by Mr. Harris, Bookseller, at the corner of St.
Paul’s Church-yard, London. His Tower was a fiction, but this was
reality—and, by comparison, a short reality. Still, it looked very well,
and very strange, and was quite as much out of the perpendicular as
Harris had represented it to be. The quiet air of Pisa, too; the big
guard-house at the gate, with only two little soldiers in it; the
streets, with scarcely any show of people in them; and the Arno,
flowing quaintly through the centre of the town; were excellent. So,
I bore no malice in my heart against Mr. Harris (remembering his
good intentions), but forgave him before dinner, and went out, full of
confidence, to see the Tower next morning.
 THE LEANING TOWER OF PISA.

I might have known better; but, somehow, I had expected to

see it casting its long shadow on a public street where people came
and went all day. It was a surprise to me to find it in a grave, retired
place, apart from the general resort, and carpeted with smooth
green turf. But, the group of buildings clustered on and about this
verdant carpet; comprising the Tower, the Baptistery, the Cathedral,
and the Church of the Campo Santo; is perhaps the most remarkable
and beautiful in the whole world; and, from being clustered there
together away from the ordinary transactions and details of the
town, they have a singularly venerable and impressive character. It is
the architectural essence of a rich old city, with all its common life
and common habitations pressed out, and filtered away.
Simond compares the Tower to the usual pictorial representations
in children’s books of the Tower of Babel. It is a happy simile, and
conveys a better idea of the building than chapters of laboured
description. Nothing can exceed the grace and lightness of the
structure; nothing can be more remarkable than its general
appearance. In the course of the ascent to the top (which is by an
easy staircase), the inclination is not very apparent; but, at the
summit, it becomes so, and gives one the sensation of being in a
ship that has heeled over, through the action of an ebb tide. The
effect upon the low side, so to speak—looking over from the gallery,
and seeing the shaft recede to its base—is very startling; and I saw
a nervous traveller hold on to the Tower involuntarily, after glancing
down, as if he had some idea of propping it up. The view within,
from the ground—looking up, as through a slanted tube—is also very
curious. It certainly inclines as much as the most sanguine tourist
could desire. The natural impulse of ninety-nine people out of a
hundred, who were about to recline upon the grass below it to rest,
and contemplate the adjacent buildings, would probably be, not to
take up their position under the leaning side; it is so very much
aslant.

Pictures from Italy (London, 1845).

THE CATHEDRAL OF CANTERBURY.
W. H FREMANTLE.

THE foundation of St. Martin’s Church and the lower part of its walls,
which are Roman, stood in 598 as they stand to-day; and they were
the walls of the little church which had been given to the Christian
Queen Bertha and her chaplain Bishop Luithart, by her pagan
husband King Ethelbert. When Augustine passed towards the city, as
described by the Venerable Bede, with his little procession headed
by the monk carrying a board on which was a rough picture of
Christ, and a chorister bearing a silver cross, his heart, no doubt,
beat high with hope: but his hope would have grown into exultation
could he have looked forward through the centuries, and beheld the
magnificent Cathedral which was to spring up where his episcopal
throne was fixed, and the energetic and varied Christian life which
has issued from this first home of Anglo-Saxon Christianity. To us the
scene is full of historical recollections. Between the place where we
are standing and the Cathedral are the city walls, on the very site
which they occupied in the days of Ethelbert, and the postern-gate
through which Queen Bertha came every day to her prayers; in the
nearer distance, a little to the right of the Cathedral, are the remains
of the great abbey which Augustine founded; to our left is the
Pilgrims’ Way, by which, after Becket’s canonization, those who
landed at Dover made their way to the shrine of St. Thomas.
 THE CATHEDRAL OF CANTERBURY.

The eye glances over the valley of the Stour, enclosed between
the hill on which we are placed and that of St. Thomas, crowned by
the fine buildings of the Clergy Orphan School; and ranges from
Harbledown (Chaucer’s “little town under the Blean ycleped Bob-up-
and-down”) on the left to the Jesuit College at Hale’s Place farther to
the right; and thence down the valley to Fordwich, where formerly
the waters of the Stour joined those of the Wantsome, the estuary
separating Thanet from the mainland. This town at the Domesday
epoch was a port with flourishing mills and fisheries. There the Caen
stone was landed to build the Cathedral, and the tuns of wine from
the monks’ vineyards in France were lifted out of the ships by the
mayor’s crane....
But it is time that we go into the Cathedral precincts. Making use
of a canon’s key, we pass, by Queen Bertha’s Postern, through the
old city walls, along a piece of the ancient Queningate lane—a
reserved space between the walls of the city and the precincts,
along which the citizens and troops could pass freely for purposes of
defence: through the Bowling Green, where the tower of Prior
Chillenden is seen to have been used as a pigeon-house, into the
Cathedral Yard. In so doing we pass under a Norman archway of the
date of Lanfranc and the Conqueror, which formerly stood in a wall
separating the cemetery of the monks from that of the laity; then
along the south side of the Cathedral, passing Anselm’s chapel, and
the beautiful Norman tower attached to the south-eastern transept,
with its elaborate tracery, which shows how delicate Norman work
could be; past the south porch, over which is a bas-relief of the altar
where the sword of Becket’s murderer was preserved; and round,
past the western door, into the cloister.
The cloister occupies the same space as the Norman cloister
built by Lanfranc, but of the Norman work only a doorway remains
at the north-east corner; there is some Early English arcading on the
north side, but the present tracery and fan-worked roof belong to
the end of the Fourteenth Century, when Archbishops Sudbury,
Arundell, and Courtenay, and Prior Chillenden (1390–1411) rebuilt
the nave, the cloister and the chapter-house. The later work cuts
across the older in the most unceremonious way, as is seen
especially in the square doorway by which we shall presently enter
the “Martyrdom,” which cuts into a far more beautiful portal of the
decorated period....
If from the place at which we have in imagination been
standing, at the north-west corner of the cloister, we look for a
moment behind us, we see in the wall a blocked-up door, with a
curious door at the side of it. The hole is said to have been made in
order to pass bottles and other articles through from the cellarer’s
lodgings, which were on the other side of the wall. The doorway was
the entrance from the Archbishop’s Palace, which occupied the space
a little further to the west; and through it Becket passed out to his
death, on the 29th of December, 1170....
 Henry had to do penance, and practically to concede the clerical
immunities for which Becket had contended; and Becket became a
saint, “the holy, blissful martyr,” himself the worker of a thousand
miracles, and his shrine the goal of pilgrimages from all parts of
England and of Europe. But, whatever we may think of this, his
death was certainly the making of Canterbury and its Cathedral. Four
years after Becket’s death the choir was burned down (1174): but
the treasure which was poured into the martyr’s church enabled the
monks to rebuild it in its present grander proportions; and the city,
which before was insignificant, became wealthy, populous, and
renowned.
The crypt was the first place of Becket’s interment, and into the
crypt we now pass.... The pavement in the centre of the Trinity
Chapel (the part east of the screen) is very rough, being composed
of the stones which formed the steps and pavement of the shrine;
but the marble pavement around it is still as it was when the shrine
was standing, and a perceptible line marks the impress of the
pilgrims’ feet as they stood in a row to see the treasures. The shrine
stood upon a platform approached by three marble steps, some
stones of which, grooved by the pilgrims’ knees, are still seen in the
flooring. The platform was paved with mosaic and medallions,
specimens of which may still be seen in the present pavement.
Above this platform was the chased and gilded coffin of the saint,
supported by three arches, which were hung with votive offerings of
extreme richness, and between two of which sick persons were
allowed to pass, so that by rubbing themselves against the stones
they might draw forth virtue from the relics of the saint. The whole
was covered with an oaken case richly decorated, which at a given
signal from the monk whom Erasmus styles the mystagogus, or
master of the mysteries, was drawn up and revealed the riches
within to the wondering gaze of the pilgrims. In the painted windows
of the chapel are the records of the miracles wrought by the
intercession of St. Thomas: here, a dead man being carried out to
burial is raised; there, the parents of a boy who has been drowned
in the attempt to catch frogs in the river are informed of their loss by
his companions with eager gestures, and he too is restored to life;
and in each case offerings of gold and silver are poured upon the
shrine; the madman is seen coming back in his right mind; “Amens
accedit, sanus recedit:” and on several occasions the saint himself
comes on the scene to heal the sick man on his bed, in one case
flying forth from the shrine in his episcopal robes. The worship of
Becket was the favourite cultus of the unreformed Church of
England; yet, strange to tell, from the day when Henry gave orders
to demolish the shrine, and to expunge his name from all the service
books and his memorials from all the churches, no one seems to
have thought anything more about him. The blow which, to adapt
the language of the Old Testament, “destroyed Becket out of Israel,”
though violent, was timely.
The Black Prince, whose wife was the Fair Maid of Kent, was
especially attached to Canterbury, and founded two chantries in the
crypt or undercroft. These now form the entrance to the French
Church, where the descendants of the Walloon and Huguenot
refugees still worship in the forms of their ancestors. The Prince had
desired to be buried below; but, partly from the special devotion
which he had to the Trinity, partly that so great a man might have
the place of honour, his tomb was erected at the side of Becket’s
shrine. He left to the Church of Canterbury his velvet coat
embroidered with lions and lilies, his ornamental shield, his lion-
crested helmet, his sword and his gauntlets, all of which still hang
above his bronze effigy, except the sword, which is said to have
been removed by Cromwell, and of which only part of the scabbard
remains. The effigy is believed to be a good likeness. It was placed
upon the tomb where the body lies soon after his death, which
occurred on the 8th of June, 1376, the feast of the Trinity, as
recorded in the inscription in the French of his own Aquitaine. The
Prince of Wales’s feathers and the lions and lilies, with the Prince’s
two mottoes, “Ich diene,” (I serve), and “Houmout,” (High Courage),
form the ornaments of the tomb, which is also surrounded by some
French verses chosen by the Prince himself, and describing the
vanity of earthly glory....
 And now we leave the Cathedral, and pass out of the precincts
by the Christ Church Gate, still beautiful even in its defacement, and
through the narrow Mercery Lane, where stood in old times the
booths for the sellers of relics and of the little leaden bottles
supposed to contain in their water some drops of St. Thomas’s
blood; where also stood the Chequers of the Hope, at which
Chaucer’s pilgrims regaled themselves, and of which one fragment,
marked by the Black Prince’s emblem of the lion with protruding
tongue, may still be seen at the corner of the lane; down the High
Street, where we pass the old East Bridge Hospital, founded by
Lanfranc, endowed by Becket, and saved from confiscation by
Cranmer, with its low Norman doorway and the crypt under its hall;
and leave the city by the West Gate, which was erected by
Archbishop Sudbury on the line where the eastern wall ran along the
Stour; and past the Falstaff Inn, where the sign of the roystering old
knight hangs out on some beautiful ancient iron-work, and welcomes
the cyclists who specially affect his inn; and so on to the South
Eastern Railway Station.
We entered Canterbury on foot with Augustine, we leave it by a
modern railway.

Farrar, Our English Minsters (London, 1893).

 THE ALHAMBRA.
THÉOPHILE GAUTIER.

HAVING passed through the gate, you enter a large square called
Plaza de las Algives in the centre of which you find a well whose
curb is surrounded by a kind of wooden shed covered with spartium
matting and where, for a cuarto, you can have a glass of water, as
clear as a diamond, as cold as ice, and of the most delicious flavour.
The towers of Quebrada, the Homenaga, the Armeria, and of the
Vela, whose bell announces the hours when the water is distributed,
and stone-parapets, on which you can lean to admire the marvellous
view which unfolds before you, surround one side of the square; the
other is occupied by the Palace of Charles V., an immense building of
the Renaissance, which you would admire anywhere else, but which
you curse here when you remember that it covers a space once
occupied by a portion of the Alhambra which was pulled down to
make room for this heavy mass. This Alcazar was, however,
designed by Alonzo Berruguete; the trophies, the bas-reliefs, and the
medallions of its façade have been accumulated by means of a
proud, bold, and patient chisel; the circular court with its marble
columns, where, in all probability, the bull-fights took place, is
certainly a magnificent piece of architecture, but non erat hic locus.
You enter the Alhambra through a corridor situated in an angle
of the Palace of Charles V., and, after several windings, you arrive in
a large court, designated indifferently under the names of Patio de
los Arraynes (Court of Myrtles), of the Alberca (of the Reservoir), or
of the Mezouar (an Arabian word signifying bath for women).
When you issue from these dark passages into this large space
flooded with light, the effect is similar to that produced by a
diorama. You can almost fancy that an enchanter’s wand has
transported you to the Orient of four or five centuries ago. Time,
which changes everything in its flight, has altered nothing here,
where the apparition of the Sultana Chaîne des cœurs and of the
Moor Tarfe in his white cloak would not cause the least surprise....
The antechamber of the Hall of the Ambassadors is worthy of
the purpose for which it was intended: the boldness of its arches,
the variety and interlacing of its arabesques, the mosaics of its walls,
and the work on its stuccoed ceiling, crowded like the stalactite roof
of a grotto and painted with azure, green, and red, traces of which
colours are still visible, produce an effect both charming and bizarre.
On each side of the door which leads to the Hall of the
Ambassadors, in the jamb of the arch itself and where the facing of
glazed tiles, whose triangles of glaring colours adorn the lower
portion of the walls, are hollowed out, like little chapels, two niches
of white marble sculptured with an extreme delicacy. It was here
that the ancient Moors left their Turkish slippers before entering, as
a mark of deference, just as we remove our hats in places that
demand this respect.
 THE ALHAMBRA.

The Hall of the Ambassadors, one of the largest in the Alhambra,

fills the whole interior of the tower of Comares. The ceiling,
composed of cedar, shows those mathematical combinations so
common to the Arabian architect: all the bits are arranged in such a
way that all their converging or diverging angles form an infinite
variety of designs; the walls disappear under a network of
ornaments, so packed together and so inextricably interwoven that I
can think of no better comparison than pieces of lace placed one
above the other. Gothic architecture, with its stone lace-work and its
perforated roses, cannot compare with this. Fish-slices and the
paper embroidery cut out with a punch, which the confectioners use
to decorate their sweets, can alone give you any idea of it. One of
the characteristics of the Moorish style is that it offers very few
projections and profiles. All the ornamentation is developed on flat
surfaces and is hardly ever more than four or five inches in relief; it
is really like a kind of tapestry worked on the wall itself. One feature
in particular distinguishes it—the employment of writing as a motive
of decoration; it is true that Arabian letters, with their mysteriously
winding forms, lend themselves remarkably to this use. The
inscriptions, which are almost always suras of the Koran, or eulogies
to various princes who have built and decorated these halls, unfold
upon the friezes, on the jambs of the doors, and round the arches of
the windows interspersed with flowers, boughs, network, and all the
wealth of Arabian calligraphy. Those in the Halls of the Ambassadors
signify “Glory to God, power and wealth to believers,” or consist of
praises to Abu Nazar, who, “if he had been taken into Heaven while
living, would have diminished the brightness of the stars and
planets,” a hyperbolical assertion which seems to us a little too
Oriental.
Other bands are filled with eulogies to Abu Abd Allah, another
Sultan who ordered work upon this part of the Palace. The windows
are bedizened with verses in honour of the limpid waters of the
reservoir, of the freshness of the shrubbery, and the perfume of the
flowers which ornament the Court of the Mezouar, which in fact is
seen, from the Hall of the Ambassadors through the doors and little
columns of the gallery.
The loop-holes of the interior balcony, pierced at a great height
from the ground, and the ceiling of woodwork, devoid of ornaments
except the zig-zags and the interlacings formed by the joining of the
pieces, give the Hall of the Ambassadors a more severe aspect than
any other halls in the Palace, and more in harmony with its purpose.
From the back window you can enjoy a marvellous view over the
ravine of the Darro....
From the Hall of the Ambassadors you go down a corridor of
relatively modern construction to the tocador, or dressing-room of
the queen. This is a small pavilion on the top of a tower used by the
sultanas as an oratory, and from which you can enjoy a wonderful
panorama. You notice at the entrance a slab of white marble
perforated with little holes in order to let the smoke of the perfumes
burned beneath the floor to pass through. You can still see on the
walls the fantastic frescoes of Bartholomew de Ragis, Alonzo Perez,
and Juan de la Fuente. Upon the frieze the ciphers of Isabella and
Philip V. are intertwined with groups of Cupids. It is difficult to
imagine anything more coquettish and charming than this room,
with its small Moorish columns and its surbased arches, overhanging
an abyss of azure, the bottom of which is studded with the roofs of
Grenada and into which the breeze brings the perfumes from the
Generalife,—that enormous cluster of oleanders blossoming in the
foreground of the nearest hill,—and the plaintive cry of the peacocks
walking upon the dismantled walls. How many hours have I passed
there in that serene melancholy, so different from the melancholy of
the North, with one leg hanging over the precipice and charging my
eyes to photograph every form and every outline of this beautiful
picture unfolded before them, and which, in all probability, they will
never behold again! No description in words, or colours, can give the
slightest hint of this brilliancy, this light, and these vivid tints. The
most ordinary tones acquire the worth of jewels and everything else
is on a corresponding scale. Towards the close of day, when the
sun’s rays are oblique, the most inconceivable effects are produced:
the mountains sparkle like heaps of rubies, topazes, and carbuncles;
a golden dust bathes the ravines; and if, as is frequent in the
summer, the labourers are burning stubble in the field, the wreaths
of smoke, which rise slowly towards the sky, borrow the most
magical reflections from the fires of the setting sun....
The Court of Lions is 120 feet long and 73 feet wide, while the
surrounding galleries do not exceed 20 feet in height. These are
formed by 128 columns of white marble, arranged in a symmetrical
disorder of groups of fours and groups of threes; these columns,
whose highly-worked capitals retain traces of gold and colour,
support arches of extreme elegance and of a very unique form....
To the left and midway up the long side of the gallery, you come
to the Hall of the Two Sisters, the pendant to the Hall of the
Abencerrages. The name of las Dos Hermanas is given to it on
account of two immense flag-stones of white Macael marble of equal
size and exactly alike which you notice at once in the pavement. The
vaulted roof, or cupola, which the Spanish very expressively call
media naranja (half an orange), is a miracle of work and patience. It
is something like a honey-comb, or the stalactites of a grotto, or the
soapy grape-bubbles which children blow through a pipe. These
myriads of little vaults, or domes, three or four feet high, which grow
out of one another, intersecting and constantly breaking their
corners, seem rather the product of fortuitous crystallization than
the work of human hands; the blue, the red, and the green still
shine in the hollows of the mouldings as brilliantly as if they had just
been laid on. The walls, like those in the Hall of the Ambassadors,
are covered from the frieze to the height of a man with the most
delicate embroideries in stucco and of an incredible intricacy. The
lower part of the walls is faced with square blocks of glazed clay,
whose black, green and yellow angles form a mosaic upon the white
background. The centre of the room, according to the invariable
custom of the Arabs, whose habitations seem to be nothing but
great ornamental fountains, is occupied by a basin and a jet of
water. There are four fountains under the Gate of Justice, as many
under the entrance-gate, and another in the Hall of the
Abencerrages, without counting the Taza de los Leones, which, not
content with vomiting water through the mouths of its twelve
monsters, tosses a jet towards the sky through the mushroom-cap
which surmounts it. All this water flows through small trenches in
the floors of the hall and pavements of the court to the foot of the
Fountain of Lions, where it is swallowed up in a subterranean
conduit. Certainly this is a species of dwelling which would never be
incommoded with dust, but you ask how could these halls have been
tenanted during the winter. Doubtless the large cedar doors were
then shut and the marble floors were covered with thick carpets,
while the inhabitants lighted fires of fruit-stones and odoriferous
woods in the braseros, and waited for the return of the fine season,
which soon comes in Grenada.
We will not describe the Hall of the Abencerrages, which is
precisely like that of the Two Sisters and contains nothing in
particular except its antique door of wood, arranged in lozenges,
which dates from the time of the Moors. In the Alcazar of Seville you
can find another one of exactly the same style.
The Taza de los Leones enjoys a wonderful reputation in Arabian
poetry: no eulogy is considered too extravagant for these superb
animals. I must confess, however, that it would be hard to find
anything which less resembles lions than these productions of
Arabian fantasy; the paws are simple stakes like those shapeless
pieces of wood which one thrusts into the bellies of pasteboard dogs
to make them keep their equilibrium; their muzzles streaked with
transverse lines, very likely intended for whiskers, are exactly like
the snout of a hippopotamus, and the eyes are so primitive in design
that they recall the crude attempts of children. However, if you
consider these twelve monsters as chimeræ and not lions, and as a
fine caprice in ornamentation, producing in combination with the
basin they support a picturesque and elegant effect, you will then
understand their reputation and the praises contained in this Arabian
inscription of twenty-four verses and twenty-four syllables engraved
on the sides of the lower basin into which the waters fall from the
upper basin. I ask the reader’s pardon for the rather barbarous
fidelity of the translation:

“O thou, who lookest upon the lions fixed in their place!

remark that they only lack life to be perfect. And you to whom
will fall the inheritance of this Alcazar and Kingdom, take them
from the noble hands of those who have governed them without
displeasure and resistance. May God preserve you for the work,
which you will accomplish, and protect you forever from the
vengeance of your enemy! Honour and glory be thine, O
Mohammed! our King, endowed with the high virtues, with
whose aid thou hast conquered everything. May God never
permit this beautiful garden, the image of thy virtues, to be
surpassed by any rival. The material which covers the substance
of this basin is like mother-of-pearl beneath the shimmering
waters; this sheet of water is like melted silver, for the limpidity
 of the water and the whiteness of the stone are unequalled; it
might be called a drop of transparent essence upon a face of
alabaster. It would be difficult to follow its course. Look at the
water and look at the basin, and you will not be able to tell if it
is the water that is motionless, or the marble which ripples. Like
the prisoner of love whose face is full of trouble and fear when
under the gaze of the envious, so the jealous water is indignant
at the marble and the marble is envious of the water. To this
inexhaustible stream we may compare the hand of our King
which is as liberal and generous as the lion is strong and
valiant.”

Into the basin of the Fountain of Lions fell the heads of the
thirty-six Abencerrages, drawn there by the stratagem of the Zegris.
The other Abencerrages would have shared the same fate if it had
not been for the devotion of a little page who, at the risk of his own
life, ran to warn the survivors from entering the fatal court. Your
attention will be attracted by some large red spots at the bottom of
the basin—an indelible accusation left by the victims against the
cruelty of their murderers. Unfortunately, the learned declare that
neither the Abencerrages nor the Zegris existed. Regarding this fact,
I am entirely guided by romances, popular traditions, and
Chateaubriand’s novel, and I solemnly believe that these crimson
stains are blood and not rust.
We established our headquarters in the Court of the Lions; our
furniture consisted of two mattresses which were rolled up in a
corner during the day, a copper lamp, an earthenware jar, and a few
bottles of sherry which we placed in the fountain to cool. Sometimes
we slept in the Hall of the Two Sisters, and sometimes in that of the
Abencerrages, and it was not without some slight fear that I,
stretched out upon my cloak, looked at the white rays of the moon
which fell through the openings of the roof into the water of the
basin quite astonished to mingle with the yellow, trembling flame of
a lamp.
 The popular traditions collected by Washington Irving in his Tales
of the Alhambra came into my memory; the story of the Headless
Horse and of the Hairy Phantom solemnly related by Father
Echeverria seemed very probable to me, especially when the light
was out. The truth of legends always appears much greater at night
when these dark places are filled with weird reflections which give a
fantastic appearance to all objects of a vague outline: Doubt is the
son of day, Faith is the daughter of the night, and it astonishes me
to think that St. Thomas believed in Christ after having thrust his
finger into his wounds. I am not sure that I did not see the
Abencerrages walking through the moonlit galleries carrying their
heads under their arms: anyhow the shadows of the columns always
assumed forms that were diabolically suspicious, and the breeze as it
passed through the arches made me wonder if it was not a human
breath.

Voyage en Espagne (Paris, new ed., 1865).

 FOOTNOTES
1
The outside of Notre-Dame has been restored since Victor
Hugo wrote his famous romance.—E. S.
2
I scarcely know how to trust myself with the mention of that
most appalling, unprecedented, act of a one-third madman
and two-thirds rogue—Jonathan Martin by name—who set fire
to the choir of York Minster: a fire which was almost
miraculously stopt in its progress towards the destruction of
the entire Cathedral. This had been a result which Martin
would have rejoiced to have seen effected. This horrid deed, at
the very thought of which the heart sickens, took place on the
2d of February, 1829.
3
I gather the following from the abridged English version
(1693) of Dugdale’s Monasticon as quoted by Drake. Where is
even the Protestant bosom that does not heave heavily as it
reads it? “To this Cathedral did belong abundance of jewels,
vessels of gold and silver, and other ornaments; rich vestments
and books,—amongst which were ten mitres of great value,
and one small mitre set with stones for the ‘Boy Bishop.’ One
silver and gilt pastoral staff, many pastoral rings, amongst
which one for the bishop of the boys. Chalices, viols, pots,
basons, candlesticks, thuribles, holy-water pots, crosses of
silver—one of which weighed eight pounds, six ounces.
Images of gold and silver; relicts in cases extremely rich; great
bowls of silver; an unicorn’s horn; a table of silver and gilt,
with the image of the Virgin enamelled thereon, weighing nine
 pounds, eight ounces, and a half. Several Gospellaries and
Epistolaries, richly adorned with silver, gold, and precious
stones. Jewels, affixed to shrines and tombs, of an almost
inestimable value. Altar cloths and hangings, very rich; copes
of tissue, damask, and velvet, white, red, blue, green, black,
and purple. Besides this, there was a great treasure, deposited
in the common chest in gold chains, collars of the Order of the
Garter, with large sums of old gold and silver.”
4
The spires of the Cathedral were finished in 1880, and the
completion of the edifice was celebrated before the Emperor
William I. on October 15th of that year.—E. S.
5
Remigius was a monk of Fescamp in Normandy, and brought
over here by William the Conqueror. He was worthy of all
promotion. Brompton tells us that he began to build the
Cathedral in 1088, and finished it in 1092, when it was
consecrated; but the founder died two days before its
consecration.
6
This must have been “Great Tom,” the First, cast in 1610;
preceded probably by one or more Great Toms, to the time of
Geoffrey Plantagenet. “Great Tom,” the Second, was cast by
Mr. Mears of Whitechapel in 1834, and was hung in the central
tower in 1835. Its weight is 5 tons, 8 cwt.; being one ton
heavier than the great bell of St. Paul’s Cathedral.... “Great
Tom,” the First, was hung in the north-west tower.
7
Robert Bloet was a worthy successor of Remigius, the founder.
Bloet was thirty years a bishop of this see—largely endowing it
with prebendal stalls, and with rich gifts of palls, hoods, and
silver crosses. He completed the western front—and, perhaps,
finished the Norman portion of the nave, now replaced by the
Early English.... Geoffrey Plantagenet was a natural son of
Henry II., and was elected in 1173.... The latter years of his
life seem to be involved in mystery, for he fled the kingdom
 five years before his death, which happened at Grosmont, near
Rouen, in 1212.
8
It has been estimated that every stone of these huge
Pharaonic temples cost, at least, one human life.
9
The arms of Cœur were what are called parlantes: azure, fess
or, charged with three shells or (recalling those of St. James
his patron), accompanied by three hearts, gules, in allusion to
his name.
10
The fortune of Jacques Cœur became proverbial: they said:
“Riche comme Jacques Cœur.”
11
The word cœurs is indicated by hearts.
12
Chateaubriand, La Vie de Rancé.
13
Pliny xxxv. 15.
14
Tac. Ann. xv. 44.
15
See Rio.
16
Arnold Boulin, master-joiner (menuisier) at Amiens, solicited
the enterprise, and obtained it in the first months of the year
1508. A contract was drawn and an agreement made with him
for the construction of one hundred and twenty stalls with
historical subjects, high backings, crownings, and pyramidal
canopies. It was agreed that the principal executor should
have seven sous of Tournay (a little less than the son of
France) a day, for himself and his apprentice, (threepence a
day the two—say a shilling a week the master, and sixpence a
week the man,) and for the superintendence of the whole
work, twelve crowns a year, at the rate of twenty-four sous the
crown; (i. e. twelve shillings a year). The salary of the simple
workman was only to be three sous a day. For the sculptures
and histories of the seats, the bargain was made separately
with Antoine Avernier, image cutter, residing at Amiens, at the
 rate of thirty-two sous (sixteen pence), the piece. Most of the
wood came from Clermont en Beauvoisis, near Amiens; the
finest, for the bas-reliefs from Holland, by St. Valery and
Abbeville.
17
The ravages committed by the Calvinists throughout nearly the
whole of the towns of Normandy, and especially in the
Cathedrals towards the year 1560, afford a melancholy proof
of the effects of religious animosity. But the Calvinists were
bitter and ferocious persecutors. Pommeraye in his quarto
volume Histoire de l’Église Cathedrale de Rouen (1686) has
devoted nearly one hundred pages to an account of Calvinistic
depredations.
18
M. Licquet says each clustered pillar contains thirty-one
columns.
19
Within three years of writing it, the spire was consumed by
lightning. The newspapers of both France and England were
full of this melancholy event; and in the year 1823 M.
Hyacinthe Langlois of Rouen, published an account of it,
together with some views of the progress of the burning.
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