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IG I;(-.,

CHE-MISTRY
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a
Part B: Reactions and Synthesis
Advanced Organic V

Chemistry EDITION
FOURTH

PLirt R: Reactions and Synthesis

Advanced Organic Chemistry
PART A : Structure and Mechanisms
PART H : Reactions and Synthesi\
Advanced Organic
Chemistry FOURTH
EDITION

Part B: Reactions and Synthesis

FRANCIS A. CAREY
and RICHARD J. SUNDBERG
University of Wrginia
Charlottesville, Virginia

Kluwer Academic 1Plenum Publishers

New York, Boston, Dordrecht, London, Moscow
 Library of Congress Cataloging-in-Publicat1011
Data
-

Carey, Francis A,, 1937-

Advanced organic chemisttylFrancis A. Carey and Richard J. Sundberg.-4th ed.
p. cm.
Includes bibliographical references and index.
Contents: pt. B. Reactions and synthesis
ISBN 00-306-46244-3 (Hardcover)-ISBN 0-306-46245-1 (pbk.)
I. Sundberg, Richard J., 1938- 11. Tltle.

The front cover shows the key orbital interactions in the Diels-Alder reaction. The highest-occupiedmolecular orbital
(HOMO) of 1,3-butadiene and the lowest-unoccupiedmolecular orbital (LUMO) of ethylene overlap in phase with one
another allowing the reaction to occur in a single step.

ISBN: 0-306-46244-3 (Hardbound)

ISBN: 0-306-46245-1 (Paperback)
02001, 1990, 1984, 1977 Kluwer Academic/Plenum Publishers, New York
233 Spring Street, New York, New York 10013

A C.I.P. record for this book is available from the Library of Congress
All rights rc?~e~ed
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form
or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise,
without written permission from the Publisher.
Printed in the United States of America
Preface to the Fourth Edition

Part B emphasizes the most important reactions used in organic synthesis. The material is
organized by reaction type. Chapters 1 and 2 discuss the alkylation, conjugate addition and
carbonyl addition/condensation reactions of enolates and other carbon nucleophiles.
Chapter 3 covers the use of nucleophilic substitution, both at saturated carbon and at
carbonyl groups, in functional group of interconversions. Chapter 4 discusses electrophilic
additions to alkenes and allcynes, including hydroboration. Chapter 5 discusses reduction
reactions, emphasizing alkene and carbonyl-group reductions. Concerted reactions,
especially Diels-Alder and other cycloadditions and sigmatropic rearrangements, are
considered in Chapter 6. Chapters 7, 8, and 9 cover organometallic reagents and
~ntermediatesin synthesis. The main-group elements lithium and magnesium as well as
zinc are covered in Chapter 7. Chapter 8 deals with the transition metals, especially copper,
palladium, and nickel. Chapter 9 discusses synthetic reactions involving boranes, silanes,
and stannanes. Synthetic reactions which involve highly reactive intermediates-carboca-
tlons, carbenes, and radicals-are discussed in Chapter 10. Aromatic substitution by both
electrophilic and nucleophilic reagents is the topic of Chapter 1 1 . Chapter 12 discusses the
most important synthetic procedures for oxidiiing organic compounds. In each of these
chapters, the most widely used reactions are illdstrated by a number of specific examples
of typical procedures. Chapter 13 introduces the concept of synthetic planning, including
the use of protective groups and synthetic equivalents. Multistep syntheses are illustrated
with several syntheses of juvabione, longifolene, Prelog-Djerassi lactone, Taxol, and
epothilone. The chapter concludes with a discussion of solid-phase synthesis and its
application in the synthesis of polypeptides and oligonucleotides, as well as to combina-
torial synthesis.
The control of reactivity to achieve specific syntheses is one of the overarching goals
of organic chemistry. In the decade since the publication of the third edition, major
advances have been made in the development of efficient new methods, particularly
catalytic processes, and in means for control of reaction stereochemistry. For example, the
scope and efficiency of palladium- catalyzed cross coupling have been greatly improved by
optimization of catalysts by ligand modification. Among the developments in stereocontrol
are catalysts for enantioselective reduction of ketones, improved methods for control of the
 stereoselectivity of Diels-Alder reactions, and improved catalysts for enantioselective
hydroxylation and epoxidation of alkenes.
PREFACE TO THE
FOURTH EDITION This volume assumes a level of familiarity with structural and mechanistic concepts
comparable to that in the companion volume, Part A, Structure and Mecha~lisms.Together,
the two volumes are intended to provide the advanced undergraduate or beginning
graduate student in chemistry a sufficient foundation to comprehend and use the research
literature in organic chemistry.
Contents of Part B

.
Chapter 1 Alkylation of Nucleophilic Carbon Intermediates . . . . . . . . . . . 1

1.1. Generation of Carbanions by Deprotonation . . . . . . . . . . . . . . . . . . . . . 1

1.2. Regioselectivity and Stereoselectivity in Enolate Formation. . . . . . . . . . . 5
1.3. Other Means of Generating Enolates . . . . . . . . . . . . . . . . . . . . . . . . . . 10
1.4. Alkylation of Enolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1.5. Generation and Alkylation of Dianions . . . . . . . . . . . . . . . . . . . . . . . . 20
1.6. Medium Effects in the Alkylation of Enolates. . . . . . . . . . . . . . . . . . . . 20
1.7. Oxygen versus Carbon as the Site of Alkylation . . . . . . . . . . . . . . . . . . 23
1.8. Alkylation of Aldehydes, Estegs, Amides, and Nitriles . . . . . . . . . . . . . . 28
1.9. The Nitrogen Analogs of Enols and Enolates-Enamines and Imine
Anions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.10. Alkylation of Carbon Nucleophiles by Conjugate Addition . . . . . . . . . . . 39
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

.
Chapter 2 Reaction of Carbon Nucleophiles with Carbonyl Groups . . . . . . 57

2.1. Aldol Addition and Condensation Reactions . . . . . . . . . . . . . . . . . . . . . 57

2.1.1. The General Mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
2.1.2. Mixed Aldol Condensations with Aromatic Aldehydes . . . . . . . . 60
2.1.3. Control of Regiochemistry and Stereochemistry of Mixed Aldol
Reactions of Aliphatic Aldehydes and Ketones . . . . . . . . . . . . . 62
2.1.4. Intramolecular Aldol Reactions and the Robinson Annulation . . . 89
2.2. Addition Reactions of Imines and Iminium Ions . . . . . . . . . . . . . . . . . . 96
2.2.1. The Mannich Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
2.2.2. Arnine-Catalyzed Condensation Reactions . . . . . . . . . . . . . . . . . 100
2.3. Acylation of Carbanions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
vii
viii 2.4. The Wittig and Related Reactions of Phosphorus-Stabilized Carbon
Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
CONTENTS OF PART B
2.5. Reactions of Carbonyl Compounds with a-Trirnethylsilylcarbanions. . . . . . 120
2.6. Sulfur Ylides and Related Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . 122
2.7. Nucleophilic Addition-Cyclization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

.
Chapter 3 Functional Group Interconversion by Nucleophilic Substitution . . 141

3.1. Conversion of Alcohols to Allcylating Agents . . . . . . . . . . . . . . . . . . . . 141

3.1.1. Sulfonate Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
3.1.2. Halides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
3.2. Introduction of Functional Groups by Nucleophilic Substitution at
Saturated Carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.2.1. General Solvent Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
3.2.2. Nitriles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2.3. Azides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
3.2.4. Oxygen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
3.2.5. Nitrogen Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
3.2.6. Sulfur Nucleophiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
3.2.7. Phosphorus Nucleophiles . . . . .". . . . . . . . . . . . . . . . . . . . . . . . 158
3.2.8. Summary of Nucleophilic Substitution at Saturated Carbon . . . . . . 159
3.3. Nucleophilic Cleavage of Carbon-Oxygen Bonds in Ethers and Esters . . . . 159
3.4. Interconversion of Carboxylic Acid Derivatives . . . . . . . . . . . . . . . . . . . 164
3.4.1. Preparation of Reactive Reagents for Acylation . . . . . . . . . . . . . . 166
3.4.2. Preparation of Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
3.4.3. Preparation of Amides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180

.
Chapter 4 Electrophilic Additions to Carbon-Carbon Multiple Bonds . . . . . 191

Addition of Hydrogen Halides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191

Hydration and Other Acid-Catalyzed Additions of Oxygen Nucleophiles . . 195
Oxymercuration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Addition of Halogens to Alkenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
Electrophilic Sulfur and Selenium Reagents. . . . . . . . . . . . . . . . . . . . . . 209
Addition of Other Electrophilic Reagents . . . . . . . . . . . . . . . . . . . . . . . 216
Electrophilic Substitution Alpha to Carbonyl Groups. . . . . . . . . . . . . . . . 216
Additions to Allenes and Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
Addition at Double Bonds via Organoborane Intermediates . . . . . . . . . . . 226
4.9.1. Hydroboration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
4.9.2. Reactions of Organoboranes . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.9.3. Enadoselective Hydroboration. . . . . . . . . . . . . . . . . . . . . . . . . 236
4.9.4. Hydroboration of Alkynes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
 General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240 ix
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
CONTENTS OF PART B

.
Chapter 5 Reduction of Carbonyl and Other Functional Groups . . . . . . . . 249

Addition of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249

5.1.1. Catalytic Hydrogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
5.1.2. Other Hydrogen-Transfer Reagents . . . . . . . . . . . . . . . . . . . . . 262
Group I11 Hydride-Donor Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
5.2.1. Reduction of Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . . 262
5.2.2. Stereoselectivity of Hydnde Reduction . . . . . . . . . . . . . . . . . . . 273
5.2.3. Reduction of Other Functional Groups by Hydride Donors . . . . . 280
Group IV Hydride Donors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 286
Hydrogen-Atom Donors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 288
Dissolving-Metal Reductions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 290
5.5.1. Addition of Hydrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
5.5.2. Reductive Removal of Functional Groups . . . . . . . . . . . . . . . . . 296
5.5.3. Reductive Carbon-Carbon Bond Formation . . . . . . . . . . . . . . . . 299
Reductive Deoxygenation of Carbonyl Groups . . . . . . . . . . . . . . . . . . . 307
Reductive Elimination and Fragmentation . . . . . . . . . . . . . . . . . . . . . . 310
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 315
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316

.
Chapter 6 Cycloadditions. Unimolecular Rearrangements. and Thermal
Eliminations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331

6.1.1. The Diels-Alder Reaction: General Features . . . . . . . . . . . . . . . 332
6.1.2. The Diels-Alder Reaction: Dienophiles . . . . . . . . . . . . . . . . . . 339
6.1.3. The Diels-Alder Reaction: Dienes . . . . . . . . . . . . . . . . . . . . . . 345
6.1.4. Asymmetric Diels-Alder Reactions . . . . . . . . . . . . . . . . . . . . . 349
6.1.5. Intramolecular Diels-Alder Reactions . . . . . . . . . . . . . . . . . . . . 353
Dipolar Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
+
[2 21 Cycloadditions and Other Reactions Leading to Cyclobutanes . . . 367
Photochemical Cycloaddition Reactions . . . . . . . . . . . . . . . . . . . . . . . . 370
[3,31 Sigmatropic Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
6.5.1. CopeRearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
6.5.2. Claisen Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
[2,31 Sigmatropic Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
Ene Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Unimolecular Thermal Elimination Reactions . . . . . . . . . . . . . . . . . . . . 403
6.8.1. Cheletropic Elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
6.8.2. Decomposition of Cyclic Azo Compounds . . . . . . . . . . . . . . . . 405
6.8.3. fl Eliminations Involving Cyclic Transition States. . . . . . . . . . . . 408
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
Alkylation of Nucleophilic
Carbon Intermediates

Introduction

Carbon-carbon bond formation is the basis for the construction of the molecular frame-
xork of organic molecules by synthesis. One of the fbndamental processes for carbon-
carbon bond formation is a reaction between a nucleophilic carbon and an electrophilic
one. The focus in this chapter is on enolate ions, imine anions, and enamines, which are
the most usefbl kinds of carbon nucleo~hiles,and on their reactions with alkylating agents.
\fechanistically, these are usually SN2reactions in which the carbon nucleophile displaces
a halide or other leaving group. Successful carbon-carbon bond formation requires that the
SN2 alkylation be the dominant reaction. The crucial factors which must be considered
include (1) the conditions for generation of the carbon nucleophile; (2) the effect of the
reaction conditions on the structure and reactivity of the nucleophile; (3) the regio- and
stereoselectivity of the alkylation reaction; and (4) the role of solvents, counterions, and
other components of the reaction media that can influence the rate of competing
reactions.

1.1. Generation of Carbanions by Deprotonation

A very important means of generating carbon nucleophiles involves removal of a

proton from a carbon by a Brransted base. The anions produced are carbanions. Both the
rate of deprotonation and the stability of the resulting carbanion are enhanced by the
presence of substituent groups that can stabilize negative charge. A carbonyl group bonded
directly to the anionic carbon can delocalize the negative charge by resonance, and
carbonyl compounds are especially important in carbanion chemistry. The anions formed
by deprotonation of the carbon alpha to a carbonyl group bear most of their negative
1
x .
Chapter 7 Organometallic Compounds of the Group I. 11. and I11 Metals . . 433
CONTENTS OF PART B
7.1. Preparation and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 433
7.2. . Reactions of Organomagnesium and Organolithium Compounds . . . . . . . . 445
7.2.1. Reactions with Alkylating Agents . . . . . . . . . . . . . . . . . . . . . . . 445
7.2.2. Reactions with Carbonyl Compounds . . . . . . . . . . . . . . . . . . . . 446
7.3. Organic Derivatives of Group IIB and Group IIIB Metals . . . . . . . . . . . . 458
7.3.1. Organozinc Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459
7.3.2. Organocadmium Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . 463
7.3.3. Organomercury Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . 464
7.3.4. Organoindium Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 465
7.4. Organolanthanide Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 467
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 468

.
Chapter 8 Reactions Involving the Transition Metals . . . . . . . . . . . . . . . . . 477

8.1. Organocopper Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

8.1.1. Preparation and Structure of Organocopper Reagents . . . . . . . . .
8.1.2. Reactions Involving Organocopper Reagents and Intermediates . . .
8.2. Reactions Involving Organ~palladium~Intermediates ................
8.2.1. Palladium-Catalyzed Nucleophilic Substitution and Alkylation . . . .
8.2.2. The Heck Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8.2.3. Palladium-Catalyzed Cross Coupling . . . . . . . . . . . . . . . . . . . . .
8.2.4. Carbonylation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8.3. Reactions Involving Organonickel Compounds. . . . . . . . . . . . . . . . . . . .
8.4. Reactions Involving Rhodium and Cobalt . . . . . . . . . . . . . . . . . . . . . . .
8.5. Organometallic Compounds with n: Bonding . . . . . . . : . . . . . . . . . . . . .
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
Chapter 9 Carbon-Carbon Bond-Forming Reactions of Compounds of
Boron. Silicon. and Tin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547

9.1. Organoboron Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 547

9.1.1. Synthesis of Organoboranes . . . . . . . . . . . . . . . . . . . . . . . . . . . 547
9.1.2. Carbon-Carbon Bond-Forming Reactions of Organoboranes . . . . . 549
9.2. Organosilicon Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
9.2.1. Synthesis of Organosilanes . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
9.2.2. Carbon-Carbon Bond-Forming Reactions . . . . . . . . . . . . . . . . . . 567
9.3. Organotin Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
9.3.1. Synthesis of Organostannanes. . . . . . . . . . . . . . . . . . . . . . . . . . 576
9.3.2. Carbon-Carbon Bond-Forming Reactions . . . . . . . . . . . . . . . . . . 579
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 585
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
 .
Chapter 10 Reactions Involving Carbocations. Carbenes. and Radicals as xi
Reactive Intermediates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
595 CONTENTS OF PART B

IReactions Involving Carbocation Intermediates . . . . . . . . . . . . . . . . . . .

1
10.1.1. Carbon-Carbon Bond Formation Involving Carbocations . . . . . .
10.1.2. Rearrangement of Carbocations . . . . . . . . . . . . . . . . . . . . . . .
10.1.3. Related Rearrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.1.4. Fragmentation Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . .
) 2.
I Reactions Involving Carbenes and Nitrenes . . . . . . . . . . . . . . . . . . . . .
10.2.1. Structure and Reactivity of Carbenes . . . . . . . . . . . . . . . . . . .
10.2.2. Generation of Carbenes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2.3. Addition Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2.4. Insertion Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2.5. Generation and Reactions of Ylides by Carbenoid Decomposition
10.2.6. Rearrangement Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2.7. Related Reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.2.8. Nitrenes and Related Intermediates . . . . . . . . . . . . . . . . . . . . .
10.2.9. Rearrangements to Electron-Deficient Nitrogen . . . . . . . . . . . .
:0.3. Reactions Involving Free-Radical Intermediates . . . . . . . . . . . . . . . . . .
10.3.1. Sources of Radical Intermediates . . . . . . . . . . . . . . . . . . . . . .
10.3.2. Introduction of Functionality by Radical Reactions . . . . . . . . . .
10.3.3. Addition Reactions of Radicals to Substituted Alkenes . . . . . . .
10.3.4. Cyclization of Free-Radical Intermediates . . . . . . . . . . . . . . . .
10.3.5. Fragmentation and Rearrangement Reactions . . . . . . . . . . . . . .
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
Chapter 11 Aromatic Substitution Reactions ......................
1 1.1. Electrophilic Aromatic Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.1.1. Nitration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.1.2. Halogenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.1.3. FriedelLCrafts Alkylations and Acylations . . . . . . . . . . . . . . . .
11.1.4. Electrophilic Metalation . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1 1.2. Nucleophilic Aromatic Substitution . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.2.1. Aryl Diazonium Ions as Synthetic Intermediates . . . . . . . . . . . .
11.2.2. Substitution by the Addition-Elimination Mechanism . . . . . . . .
11.2.3. Substitution by the Elimination-Addition Mechanism . . . . . . . .
1 1.2.4. Transition-Metal-Catalyzed Substitution Reactions . . . . . . . . . .
1 1.3. Aromatic Radical Substitution Reactions . . . . . . . . . . . . . . . . . . . . . . .
1 1.4. Substitution by the SRNlMechanism . . . . . . . . . . . . . . . . . . . . . . . . .
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

.
Chapter 12 Oxidations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

12.1. Oxidation of Alcohols to Aldehydes. Ketones. or Carboxylic Acids . . . . .

12.1.1. Transition-Metal Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . .
12.1.2. Other Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
xii 12.2. Addition of Oxygen at Carbon-Carbon Double Bonds . . . . . . . . . . . . . . 757
12.2.1. Transition-Metal Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
CONTENTS OF PART B
12.2.2. Epoxides from Alkenes and Peroxidic Reagents . . . . . . . . . . . . . 767
12.2.3. Transformations of Epoxides . . . . . . . . . . . . . . . . . . . . . . . . . 772
12.2.4. Reaction of Alkenes with Singlet Oxygen . . . . . . . . . . . . . . . . . 782
12.3. Cleavage of Carbon-Carbon Double Bonds . . . . . . . . . . . . . . . . . . . . . . 786
12.3.1. Transition-Metal Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . 786
12.3.2. Ozonolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 788
12.4. Selective Oxidative Cleavages at Other Functional Groups . . . . . . . . . . . . 790
12.4.1. Cleavage of Glycols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
12.4.2. Oxidative Decarboxylation . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
12.5. Oxidation of Ketones and Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . 794
12.5.1. Transition-Metal Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . 794
12.5.2. Oxidation of Ketones and Aldehydes by Oxygen and
Peroxidic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 798
12.5.3. Oxidation with Other Reagents . . . . . . . . . . . . . . . . . . . . . . . . 802
12.6. Allylic Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
12.6.1. Transition-Metal Oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . 803
12.6.2. Other Oxidants . . . i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805
12.7. Oxidations at Unfunctionalized Carbon . . . . . . . . . . . . . . . . . . . . . . . . . 807
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809

.
Chapter 13 Planning and Execution of bfultistep Syntheses . . . . . . . . . . . . 821

13.1. Protective Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 822

13.1.1. Hydroxyl-Protecting Groups . . . . . . . . . . . . . . . . . . . . . . . . . . 822
13.1.2. Amino-Protecting Groups. . . . . . . . . . . . . . . . . . . . . . . . . . . . 831
13.1.3. Carbonyl-Protecting Groups . . . . . . . . . . . . . . . . . . . . . . . . . . 835
13.1.4. Carboxylic Acid-Protecting Groups . . . . . . . . . . . . . . . . . . . . . 837
13.2. Synthetic Equivalent Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
13.3. Synthetic Analysis and Planning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
13.4. Control of Stereochemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
13.5. Illustrative Syntheses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
13.5.1. Juvabione . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
13.5.2. Longifolene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 859
13.5.3. Prelog-Djerassi Lactone. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 869
13.5.4. Tax01 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
13.5.5. Epothilone A . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
13.6. Solid-Phase Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 897
13.6.1. Solid-Phase Synthesis of Polypeptides . . . . . . . . . . . . . . . . . . . 897
13.6.2. Solid-Phase Synthesis of Oligonucleotides. . . . . . . . . . . . . . . . . 900
13.7. Combinatorial Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 903
General References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 909
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 910

References for Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 923

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 947
Advanced Organic
Chemistry FOURTH
EDITION

Part B: Reactions and Synthesis

Alkylation of Nucleophilic
Carbon Intermediates

Introduction

Carbon-carbon bond formation is the basis for the construction of the molecular frame-
xork of organic molecules by synthesis. One of the fbndamental processes for carbon-
carbon bond formation is a reaction between a nucleophilic carbon and an electrophilic
one. The focus in this chapter is on enolate ions, imine anions, and enamines, which are
the most usefbl kinds of carbon nucleo~hiles,and on their reactions with alkylating agents.
\fechanistically, these are usually SN2reactions in which the carbon nucleophile displaces
a halide or other leaving group. Successful carbon-carbon bond formation requires that the
SN2 alkylation be the dominant reaction. The crucial factors which must be considered
include (1) the conditions for generation of the carbon nucleophile; (2) the effect of the
reaction conditions on the structure and reactivity of the nucleophile; (3) the regio- and
stereoselectivity of the alkylation reaction; and (4) the role of solvents, counterions, and
other components of the reaction media that can influence the rate of competing
reactions.

1.1. Generation of Carbanions by Deprotonation

A very important means of generating carbon nucleophiles involves removal of a

proton from a carbon by a Brransted base. The anions produced are carbanions. Both the
rate of deprotonation and the stability of the resulting carbanion are enhanced by the
presence of substituent groups that can stabilize negative charge. A carbonyl group bonded
directly to the anionic carbon can delocalize the negative charge by resonance, and
carbonyl compounds are especially important in carbanion chemistry. The anions formed
by deprotonation of the carbon alpha to a carbonyl group bear most of their negative
1
 charge on oxygen and are referred to as enolates. Several typical examples of proton-
abstraction equilibria are listed in Scheme 1.1. Electron delocalization in the correspond-
CHAPTER 1
ALKUTION OF ing carbanions is represented by the resonance structures presented in Scheme 1.2.
NUCLFDPHILIC
CARBON
INTERMmIATES
Scheme 1.3. Generation of Carbon Nucleophiles by
Deprotonation

0 0
II II
1 RCH2CR' + NH2- = -
RCHCR' + NH3
0 0
II II
2 RCH2COR' + m: = RCHCOR' + HNR~
0 0 0 0
II II I1 I1
3 R'OCCH2COR' + R'O- = R'OCCHCOR' + R'OH
0 0 0 0
II II I1 I1
4 CH3CCH2COR' + R'O- === CH3CCHCOR' + R'OH
0 ^- r 0
II I1
5 N5CCH2COR' + R'O- = N= CCHCOR'
- + R'OH
6 RCH2N02 + HO- -- RCHNO;! + H20
-

Scheme 1.2. Resonance in Some Carbanions

1 Enolate of ketone
0
II
RCH-CR' -
2 Enolate of ester
0-
I
RCH=CRf

0
II
RCH-COR' - 0-
I
RCH=COR'
3 Malonic ester anion
0
1
I
0-
I
R'OC- CHZCOR' -
4 Acetoacetic ester anion
0
II
R'OC-CH-
0
II
COR' - 0-
I
0
II
R'OCZCH- COR'

0
II
0-
I
CH3C-CHZCOR' - 0
I1
0
I1
CH3C-CH-COR' - 0-
I
0
II
CH3C=CH-COR'
5 Cyanoacetic ester anion

6 Nitronate anion

Rg-N
+//
\
0

0-
- RCH=N
+/
\
0-

0-
 The efficient generation of a significant equilibrium concentration of a carbanion
requires choice of a proper Brunsted base. The equilibri~imwill favor carbanion formation
SECTION 1 1
only when the acidity of the carbon acid is greater than that of the conjugate acid CiENEMI'ION O F
corresponding to the base used for deprotonation. Acidity is quantitatively expressed as C'ARBANIONS BY
DEPROTONAI'ION
pK,, which is equal to -logK, and applies, by definition, to dilute aqueous solution.
Because most important carbon acids are quite weak acids (pK, > 15), accurate measure-
ment of their acidity in aqueous solutions is impossible, and acidities are determined in
organic solvents and referenced to the pK, in an approximate way. The data produced are
not true pK, 's, and their approximate nature is indicated by referring to them as simply pK
values. Table 1.1 presents a list of pK data for some typical carbon acids. The table also
includes examples of the bases which are ofien used for deprotonation. The strongest acids
appear at the top of the table, and the strongest bases at the bottom. A favorable
cquilibrium between a carbon acid and its carbanion will be established if the base
which is used appears below the acid in the table. Also included in the table are pK values
determined in dimethyl sulfoxide (pKDMSO).The range of acidities that can be directly
measured in dimethyl sulfoxide (DMSO) is much greater than in aqueous media, thereby
allowing direct comparisons between compounds to be made more confidently. The pK
values in DMSO are normally greater than in water because water stabilizes anions more
effectively, by hydrogen bonding, than does DMSO. Stated another way, many anions
are more strongly basic in DMSO than in water. At the present time, the pKDMso
scale includes the widest variety of structural types of synthetic interest.' From the pK
values collected in Table 1.1, an ordering of some important substituents with respect to
their ability to stabilize carbanions can be established. The order suggested is
N02>COR>CN-C02R> S02R> SOR> P h - S R > H > R .
By comparing the approximate pK values of the conjugate acids of the bases with
those of the carbon acid of interest, it is possible to estimate the position of the acid-base
equilibrium for a given reactant-base combination. If we consider the case of a simple
alkyl ketone in a protic solvent, for example, it can be seen that hydroxide ion and primary
alkoxide ions will convert only a small fraction of such a ketone to its anion.

The slightly more basic tertiary alkoxides are comparable to the enolates in basicity, and a
somewhat more favorable equilibrium will be established with such bases:

0 0-
I1 I
RCCH + R3C0 = RC=CH2 + R3C0H K=1

To obtain complete conversion of ketones to enolates, it is necessary to use aprotic

solvents so that solvent deprotonation does not compete with enolate formation. Stronger
bases, such as amide anion ( NH2), the conjugate base of DMSO (sometimes referred to
-

as the "dimsyl" a n i ~ n ) and

, ~ triphenylmethyl anion, are capable of effecting essentially
complete conversion of a ketone to its enolate. Lithium diisopropylamide (LDA), which is
generated by addition of n-butyllithium to diisopropylamine, is widely used as a strong

1. F. G. Bordwell, Acc. Chem. Res. 21:456 (1988).

2. E. J. Corey and M. Chaykovsky, J Am. C'hem. Soc. 87:1345 (1965).
CHAPTER 1
ALKYLATION OF Carbon acid PK ~KDMSO Common bases pK pK~~so
NUCLEOPHILIC
CARBON 02NCH2NO2
INTERMEDIATES CH3COCH2N02
PhCHzN02
CH3CH2N02
CH3COCH2COCH3
PhCOCH2COCH3
CH3N02
CH3COCH2C02CH2CH3
CH3COCH(CH3)COCH3
NCCH2CN
CHZ(SOZCH~CH~)~
PhCH2N02
CH~(CO~CHZCH~)Z
Cyclopentadiene
PhSCH2COCH3
PhCH2COCH3
CH3CH2CH(C02CH2CH3)2
PhSCH2CN
PhCH2CN
(PhCH2)zS02
PhCOCH3
CH3COCH3
CH3CH2COCH2CH3
Fluorene
PhS02CH3
PhCH2SOCH3
CH3CN
Ph2CH2
Ph3CH

PhCH3 43
cH4 56
a. F. G. Bordwell, Acc. Chem. Res. 21:456 (1988).

base in synthetic procedures.3 It is a very strong base, yet it is sufficiently bulky so as to be

relatively nonnucleophilic, a feature that is important in minimizing side reactions. The
lithium, sodium and potassium salts of hexamethyldisilazane, [(CH3)3Si]2NI-I,are easily
prepared and handled compounds with properties similar to those of lithium diisopropyl-
amide and also find extensive use in synthesis.4 These bases must be used in aprotic
solvents such as ether, tetrahydrofuran (THF), or dimethoxyethane (DME).

0 OLi
II I
RCCH3 + [(CH3)2CH]2NLi = RC=CH2 + [(CH3)2CH]2NH K > 1
LDA

3. H. 0. House, W. V Phillips, T. S. B. Sayer, and C.-C. Yau, 1 Org. Chem. 43:700 (1978).
4. E. H. Amonoco-Neizer, R. A. Shaw, D. 0. Skovlin, and B. C. Smith, 1 Chem. Soc. 19692997; C. R. Kruger
and E. G. Rochow, 1 Organmet. Chem. 1:476 (1964).
Sodium hydride and potassium hydride can also be used to prepare enolates from ketones. 5
The reactivity of the metal hydrides is somewhat dependent on the means of preparation
SECTION 1.2.
and purification of the hydride.5 REGIOSELECTNITY
The data in Table 1.1 allow one to estimate the position of the equilibrium for any of AND
STEREOSELECTNITY
the other carbon acids with a given base. It is important to keep in mind the position of IN ENOLATE
such equilibria as other aspects of reactions of carbanions are considered. The base and FORMATION
solvent used will determine the extent of deprotonation. There is another important
physical characteristic which needs to be kept in mind, and that is the degree of
aggregation of the carbanion. Both the solvent and the cation will lduence the state of
aggregation, as wiIl be discussed further in Section 1.6.

1.2. Regioselectivity and Stereoselectivity in Enolate Formation

An unsymmetrical dialkyl ketone can form two regioisomeric enolates on deprotona-

tion:

0
II
R2CHCCH2R' - B-
0-
I
0-
I
R2C=CCH2R' or R2CHC=CHR'

In order to exploit fully the synthetic potential of enolate ions, control over the
regioselectivity of their formation is required. Although it may not be possible to direct
deprotonation so as to form one enolate to the exclusion of the other, experimental
conditions can often be chosen to provide a substantial preference for the desired
regioisomer. To understand why a particular set of experimental conditions leads to the
preferential formation of one enolate while other conditions lead to the regioisomer, we
need to examine the process of enolate generation in more detail.
The composition of an enolate mixture may be governed by kinetic or thermodynamic
factors. The enolate ratio is governed by kinetic control when the product composition is
determined by the relative rates of the two or more competing proton-abstraction reactions.

Kinetic conml of isomeric enolate composition

On the other hand, if enolates A and B can be interconverted readily, equilibrium is

established and the product composition reflects the relative thermodynamic stability of the
5. C. A. Brown, 1 Org. Chem. 39:1324 (1974); R. Pi. T.Friedl, P. v. R. Schleyer, P. Klusener, and L. Brandsma,
1 Org. Chem. 52:4299 (1987); T.L. Macdonald K. J. Natalie, Jr., G. Prasad and J. S. Sawyer, 1 Org. Chem.
51:1124 (1986).
 Scheme 1.3. Composition of Enolate Mitures

CHAPER 1
ALKYLATION OF
NUCLEOPHZIC
CARBON
INTERMEDIATES

Kinetic control (Pb3CLiI

dimethoxyethane)
Thermodynamic contml (Ph3CLi/
equilibration in the presence
of excess ketone)

Kinetic control (LDN

dimethoxyethane)
Thermodynamic wntml
(Et3NIDMF)

Kinetic wntml (LDA/tetrahydrofuran, - 7 0 " ~ ) ~

Thennodynamiccontrol (KH, tet~ahydrofuran)~ . Only enolate
Only ewlate

Kinetic control (Ph3CL.i/

dimethoxyethane)
Thermodynamic control
(equilibration in the presence
of excess ketone)

Kinetic control ( L D N t e t r a h y d m ~ -78°C)

, Only enolate

Kinetic contml (lithium

2,2,6,6tetramethylpi@dide/
tetrahydmiiuan)
Thermodynamic contml
(equilibration in the presence
of excess ketone)
 Scheme 1.3. (continued)

SECTION 1.2.
REGIOSELECTIVITY
AND
STEREOSELECTIVITY
IN ENOLATE
FORMATION
ffinetic control (LDN
tetrahydrofuran)

Kinetic control (LDN

tetrahydrofuran)

Kinetic control (LDA,-78°C) 74 26

Kinetic control (LDA TMSC1) 95 5
ffinetic control fNDA/tetramethylenediamine) 91 9
Thermodynamic control (KH. 46 54
tetrahydrofuran, 20°C)

a. H. 0 . House and B. M. Trost, 1Urg. Chem. 30: 1341 (1965).

b. H. 0. House, M. Gall, and H. D. Olmstead, 1 Urg. Chem. 36:2361 (1971).
2. H. 0 . House, L. J. Czuba, M. Gall, and H. D. Olmstead, 1 Org. Chem.34:2324 (1969).
d. E. Vedejs, 1 Am. Chem. Soc. W.5944 (1974); H. J. Reich, J. M. Renga, and I. L. Reich, 1 Am. Chem. Soc.
97:5434 (1975).
c . G. Stork, G. A. b u s , and G. A. Garcia, 1 Org. Chem. 39:3459 (1974).
f Z. A. Fataftah, I. E. Kopka, and M. W. Rathke, 1Am. Chem. Soc. 102:3959 (1980); Y. Balamraju, C. D. Sharp,
W. GammiU, N. Manue, and L. M. Pratt, Tetrnhedmn 54:7357 (1998).
g. C. H. Heathcock, C. T. Buse, W. A. Kleschick, M. C. Pinung, J. E. Sohn, and J. Lampe, 1Org. Chem.
45:1066 (1980).
h. R. D. Clark and C. H. Heathwck, 1Org. Chem. 41:1396 (1976); C. A. Bmwn, 1Org. Chem. 39:3913 (1974);
E. J. Corey and A. W. Gross, Tetmhedmn Lgn.25:495 (1984); F! C. Andrews, N. D. R. Barnett, R. E. Malvey,
W. Clegg, F! A. D. Neil, D. Barr, L. Couton, A. J. Dawson, and B. J. Wakefield, 1Orgonomet. Chem. 518:85
(1996).

molates. The enolate ratio is then governed by thermodynamic control.

I
R2CHC=CHR'
B
Thermodynamic control of isomeric enolate composition

By adjusting the conditions under which an enolate mixture is formed from a ketone,
it is possible to establish either kinetic or thermodynamic control. Ideal conditions for
kinetic control of enolateformation are those in which deprotonation is rapid, quantitative,
8 and irrever~ible.~ This ideal is approached experimentally by using a very strong base such
as LDA or hexamethyldisilyamide (HMDS) in an aprotic solvent in the absence of excess
CHAPTER 1
ALKYLATION OF ketone. Lithium is a better counterion than sodium or potassium for regioselective
NUCLEOPHILIC generation of the kinetic enolate. Lithium maintains a tighter coordination at oxygen
CARBON
INTERMEDIATES and reduces the rate of proton exchange. Aprotic solvents are essential because protic
solvents permit enolate equilibration by reversible protonationAeprotonation, which gives
rise to the thermodynamically controlled enolate composition. Excess ketone also
catalyzes the equilibration by proton exchange. Scheme 1.3 shows data for the regio-
selectivity of enolate formation for several ketones under various reaction conditions.
A quite consistent relationship is found in these and related data. Conditions of kinetic
control usuallyfavor the less substituted enolate. The principal reason for this result is that
removal of the less hindered hydrogen is faster, for steric reasons, than removal of more
hindered protons. Removal of the less hindered proton leads to the less substituted enolate.
Steric factors in ketone deprotonation can be accentuated by using more highly hindered
bases. The most widely used base is the hexamethyldisilylamide ion, as a lithium or
sodium salt. Even more hindered disilylamides such as hexaethyldisilylamide7 and
bis(dimethylphenylsilyl)amide8may be useful for specific cases. On the other hand, at
equilibrium the more substituted aolate is usually the dominant species. The stability of
carbon-carbon double bonds increases with increasing substitution, and this effect leads to
the greater stability of the more substituted enolate.
The terms kinetic control and thermodynamic control are applicable to other reactions
besides enolate formation; the general concept was covered in Part A, Section 4.4. In
discussions of other reactions in this chapter, it may be stated that a given reagent or set of
conditions favors the "thermodynamic proddct." This statement means that the mechanism
operating is such that the various possible products are equilibrated after initial formation.
When this is true, the dominant product can be predicted by considering the relative
stabilities of the various possible products. On the other hand, if a given reaction is under
"kinetic control," prediction or interpretation of the relative amounts of products must be
made by analyzing the competing rates of product formation.
For many ketones, stereoisomeric as well as regioisomeric enolates can be formed, as
is illustrated by entries 6 , 7, and 8 of Scheme 1.3. The stereoselectivity of enolate
formation, under conditions of either kinetic or thermodynamic control, can also be
controlled to some extent. We will return to this topic in more detail in Chapter 2.
It is also possible to achieve enantioselective enolate formation by using chiral bases.
Enantioselective deprotonation requires discrimination between two enantiotopic hydro-
gens, such as in cis-2,6-dimethylcyclohexanoneor 4-(t-buty1)cyclohexanone.

6. For a review, see J. d'hgelo, Tetmhedron 32:2979 (1976).

7. S. Masamune, J. W. Ellingboe, and W. Choy, . Am. Chem. Soc. 104:5526 (1982).
I
8. S. R. Angle, J. M. Fevig, S. D. Knight, R. W.Marquis, Jr., and L. E. Ovennan, J Am. Chem. Soc. 115:3966
(1993).
The most studied bases are chiral amides such as C-F.9 9
SECTION 1.2.
CH3 GH3 Li REGIOSELECTIVITY
AND
cN>Abc(cH3)3 STEREOSELECTWRY
Li IN ENOLATE
I Fh FORMATION
Li

Enantioselective enolate formation can also be achieved by kinetic resolution by prefer-

ential reaction of one of the enantiomers of a racemic chiral ketone such as 2-(t-
butyl)cyclohexanone (see Part A, Section 2.2 to review the principles of kinetic resolu-
tion).

3 ) 3Hc ( c - b - R*2m im ~.s~t~c(cH3)3 +

Ref. 14
trimethylsilyl
chloride

45%.yield, 908 e.e. 51% yield, 94%e.e.

(e.e. = enantiomeric excess)

Such enantioselective deprotonations depend upon kinetic selection between prochiral or

enantiomeric protons and the chiral base resulting from differences in diastereomeric
transition states." For example, transition state G has been proposed for deprotonation of
4-substituted cyclohexanones by base l?16

93'Li H

CHzC(CH3)3

Kinetically controlled deprotonation of a$-unsaturated ketones usually occurs

preferentially at the a' carbon adjacent to the carbonyl group. The polar effect of the

9. P. O'Brien, 1 Chem. Soc., Perkin Trans 1 1998:1439; H. J. Geis, Methods of Organic Chemistry (Houben-
Weyl), Vol. E21a, G. Thiemer, Stuttgart, 1996, p. 589.
10. P. J. Cox andN. S. Simpkins, Tetmhedmn Asymmetry, 2:1(1991); N. S. Simpkins, Pure Appl. Chem. 68:691
(1996); B. J. Bunn and N. S. Simpkins, 1 Org. Chem. 58:533 (1993).
1 1 . C. M. Cain, R. P. C. Cousins, G. Coumbarides, and N. S. Simpkins, Tetmhedmn 46:523 (1990).
12. D. Sato, H. Kawasaki, T. Shimada, Y. Arata, K. Okamura, T. Date, and K. Koga, 1Am. Chem. Soc. 114:761
(1992); T. Yamashita, D. Sato, T. Kiyoto, A. Kumar, and K. Koga, Teirehedmn Len. 37:8195 (1996); H .
Chatani, M. Nakajima, H. Kawasah, and K. Koga, Hetemcycles 46:53 (1997); R. Shlrai, D. Sato, K. Aoki,
M. Tanaka, H. Kawasaki, and K. Koga, Tetrahedron 53:5963 (1997).
13. M. Asami, Bull. Chem. Soc. Jpn. 63:721 (1996).
14. H. Kim, H. Kawasaki, M. Nakajima, and K. Koga, Tetmhedmn Lea 30:6537 (1989); D. Sato, H. Kawasaki,
T. Shimada, Y. Arata, K. Okamura, T. Date, and K. Koga, 1Am. Chem. Soc. 114:761 (1992).
15. A. Cormble, J.-Y. Valnot, J. Maddaluno, Y. Prigent, D. Davoust, and P. Duhamel, 1Am. Chem. Soc.
119:10042 (1997); D. Sato, H. Kawasaki, and K. Koga, Chem. Phann. Bull. 45:1399 (1997); K . Sugasawa,
M. Shindo, H. Noguchi, and K. Koga, Tetmhedmn Len. 37:7377 (1996).
16. M. Toriyama, K. Sugasawa, M. Shindo, N. Tokutake, and K. Koga, Tetmhedmn Lea 38:567 (1997).
10 carbonyl group is probably responsible for the faster deprotonation at this position.
CHAPTER 1
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDlATES Ref. 17

CH3
(only enolate)

Under conditions of thermodynamic control, however, it is the enolate corresponding to

deprotonation of the y carbon that is present in the greater amount.

CH3

CH3/B
II
0
'C=CHCCH3
a a'
-
NaNHz

NH3
CHI=C-gH=CCkII
r I
I
O-
>
CHI,

CH3
/
I
0-
C=CH-C=CH2
a a'
Ref. 18

7 CH3 Y
maior enolate (less stable)
(more stable)
El *
These isomeric enolates differ in stability in that H is fully conjugated, whereas the TC
system in I is cross-conjugated. In isomer I, the delocalization of the negative charge is
restricted to the oxygen and the a' carbon, whereas in the conjugated system of H, the
negative charge is delocalized on oxygen and both the a and the y carbon.

1.3. Other Means of Generating Enolates

The recognition of conditions under which lithium enolates are stable and do not
equilibrate with regioisomers allows the use of other reactions in addition to proton
abstraction to generate specific enolates. Several methods are shown in Scheme 1.4.
Cleavage of trimethylsilyl en01 ethers or en01 acetates by methyllithium (entries 1 and 3,
Scheme 1.4) is a route to specific enolate formation that depends on the availability of
these starting materials in high purity. The composition of the trirnethylsilyl en01 ethers
prepared from an enolate mixture will reflect the enolate composition. If the enolate
formation can be done with high regioselection, the corresponding trimethylsilyl en01 ether
can be obtained in high purity. If not, the silyl en01 ether mixture must be separated.
Trimethylsilyl en01 ethers can be cleaved by tetraalkylammonium fluoride salts (entry 2,
Scheme 1.4). The driving force for this reaction is the formation of the very strong Si-F
bond, which has a bond energy of 142kcal/m01.'~
Trimethylsilyl en01 ethers can be prepared directly from ketones. One procedure
involves reaction with trimethylsilyl chloride and a tertiary arnine." This procedure gives
the regioisomers in a ratio favoring the thermodynamically more stable en01 ether. Use of

17. R. A. Lee, C. McAndrews, K. M. Patel, and W. Reusch, TetMhedmn Lett. 1973:965.

18. G. Biichi and H. Wuest, 1 Am. Chem. Soc. 96:7573 (1974).
19. For reviews of the chemistry of 0-siiyl en01 ethers, see J. K. Rasmusse~Synthesis 1977:91; P. Brownbridge,
Synthesis 1:85 (1983); I . Kuwajima and E. Nakamura, Acc. Chem. Res. 18:181 (1985).
20. H. 0.House, L. J. Czuba, M. Gall, and H. D. Olmstead, 1 Org. Chem. 34:2324 (1969);R. D. Miller and D. R.
McKean, Synthesis 1979:730.
t-butyldimethylsilyl chloride with potassium hydride as the base also seems to favor the 11
thermodynamic product.21 Trimethylsilyl trifluoromethanesulfonate (TMS triflate), which
SECTION 1.4.
is more reactive, gives primarily the less substituted trimethylsilyl en01 ether.22 Higher ALKYLATION OF
ratios of less substituted to more substituted en01 ether are obtained by treating a mixture ENOLATES
of ketone and trirnethylsilyl chloride with LDA at - 7 8 " ~ Under
. ~ ~ these conditions, the
kinetically preferred enolate is immediately trapped by reaction with trimethylsilyl
chloride. Even greater preferences for the less substituted silyl en01 ether can be obtained
by using the more hindered arnide from t-octyl-t-butylamine.
Trimethylsilyl en01 ethers can also be prepared by 1,4-reduction of enones using
silanes as reductants. Several effective catalysts have been found.24The most versatile of
these catalysts appears to be a Pt complex of divinyltetramethyldisiloxane.2sThis catalyst
gives good yields of substituted silyl en01 ethers.

Lithium-ammonia reduction of a$-unsaturated ketones (entry 6, Scheme 1.4) provides a

very useful method for generating specific e n o l a t e ~The
. ~ ~ desired starting materials are
often readily available, and the position of the double bond in the enone determines the
structure of the resulting enolate. This and other reductive methods for generating enolates
from enones will be discussed more filly in Chapter 5. Another very important method for
specific enolate generation, the addition of organometallic reagents to enones, will be
discussed in Chapter 8.

1.4. Alkylation of Enolates

Alkylation of enolate is an important synthetic method.27The alkylation of relatively

acidic compounds such as P-diketones, 8-ketoesters, and esters of malonic acid can be
carried out in alcohols as solvents using metal alkoxides as bases. The presence of two
electron-withdrawing substituents facilitates formation of the enolate resulting from
removal of a proton from the carbon situated between them. Alkylation then occurs by
an SN2process. Some examples of alkylation reactions involving relatively acidic carbon
acids are shown in Scheme 1.5. These reactions are all mechanistically similar in that a

21. J. Orban. J. \! 'hner, and B. Twitchin, Tetrahedmn Len. 255099 (1984).

22. H. Emde, A. Giitz, K. Hofmann, and G. Simchen, Justus Liebigs Ann. Chem. 1981:1643; see also E. J. Corey,
H. Cho, C. Riicker, and D. Hua Tetrahedmn Lett. 1981:3455.
23. E. J. Corey and A. W. Gross, Tetrahedmn Lett. 25:495 (1984).
24. I. Ojima and T. Kogure, Organometallics 1:1390 (1982); T. H. Chan and G. Z. Zheng, Tetrahedmn Lett.
34:3095 (1993); D. E. Cane and M. Tandon, Tetrahedmn Lett. 355351 (1994).
25. C. R. Johnson and R. K. Raheja, J Org. Chem. 59:2287 (1994).
26. For a review of a$-enone reduction, see D. Caine, Org. React. 23:l (1976).
27. D. Caine, in Carbon-Carbon Bond Formation, Vol. 1, R. L. Augustine, ed., Marcel Dekker, New York, 1979,
Chapter 2.
 Scheme 1.4. Generation of Specific Enolates

CHAPTER 1 A. Cleavage of trimethylsilyl en01 esters

ALKYLATION OF
NUCLEOPHILIC la
CARBON
INTERMEDIATES
dimethoxyethane
+ (CH3)4Si
CH3
CH3

B. Cleavage of en01 acetates

3C 0

C. Regioselective silylation of ketones by in situ enolate trapping

D. Reduction of a,b-unsaturated ketones

a. G. Stork and P. F. Hudrlik, 1Am. Chem. Soc. 90:4464 (1968); see also H. 0 . House, L. J. Czuba M. ~ a and
k
H. D. Olmstead, 1 Org. Chem. 34:2324 (1969).
b. I. Kuwajima and E. Nakarnura, 1Am. Chem. Soc. 97:3258 (1975).
c. G. Stork and S. R. Dowd, Org. Synth. 5 5 4 6 (1976); see also H. 0 . House and B. M. Trost, 1Org. Chem.
30:2502 (1965).
d. E. J. Corey and A. W.Gross, Tetrahedmn Len. 25495 (1984).
e. H. Emde, A. Gotz, K. Hofmann, and G. Simchen, Jushlr Liebigs Ann. Chem. 1981:1643.
f. G. Stork, P. Rosen, N. Goldman, R. V Coombs, and J. Tsuji, 1 Am. Chem. Soc. 87:275 (1965).
g. C. R. Johnson and R. K. Raheja, 1 Org. Chem. 59:2287 (1994).
carbanion, formed by deprotonation using a suitable base, reacts with an electrophile by an 13
SN2mechanism. The alkylating agent must be reactive toward nucleophilic displacement.
SECTION 1.4.
Primary halides and sulfonates, especially allylic and benzylic ones, are the most ALKYLATION OF
reactive alkylating agents. Secondary systems react more slowly and often give only ENOLATES
moderate yields because of competing elimination. Tertiary halides give only elimination
products.
Methylene groups can be dialkylated if sufficient base and alkylating agent are used.
Dialkylation can be an undesirable side reaction if the monoalkyl derivative is the desired
product. Use of dihaloalkanes as the alkylating reagent leads to ring formation, as
illustrated by the diethyl cyclobutanedicarboxylate synthesis (entry 7) shown in Scheme
1.5. This example illustrates the synthesis of cyclic compounds by intramolecular
alkylation reactions. The relative rates of cyclization for w-haloalkyl malonate esters are
650,000 : 1 : 6500 : 5 for formation of three-, four-, five-, and six-membered rings,
respectively.28 (See Section 3.9 of Part A to review the effect of ring size on SN2
reactions.)
Relatively acidic carbon acids such as malonic esters and B-keto esters were the first
class of carbanions for which reliable conditions for alkylation were developed. The reason
being that these carbanions are formed using easily accessible alkoxide ions. The
preparation of 2-substiuted 8-keto esters (entries 1, 4, and 8) and 2-substituted derivatives
of malonic ester (entries 2 and 7) by the methods illustrated in Scheme 1.5 are usekl for
the synthesis of ketones and carboxylic acids, since both B-ketoacids and malonic acids
undergo facile decarboxylation:

\
p = keto acid: X = alkyl or aryl = ketone
substituted malonic acid: X = OH = $!$",%

Examples of this approach to the synthesis of ketones and carboxylic acids are
presented in Scheme 1.6. In these procedures, an ester group is removed by hydrolysis and
decarboxylation after the alkylation step. The malonate and acetoacetate carbanions are the
synthetic equivalents of the simpler carbanions lacking the ester substituents. In the
preparation of 2-heptanone (entries 1, Schemes 1.5 and 1.6), for example, ethyl
acetoacetate functions as the synthetic equivalent of acetone. It is also possible to use
the dilithium derivative of acetoacetic acid as the synthetic equivalent of acetone en01ate.~~
In this case, the hydrolysis step is unnecessary, and decarboxylation can be done directly
on the alkylation product.

Li+
0
II
CH3CCH2C02H -2 n-BuLi
0-
I
0
11 I) R-X
CH3C=CHCO-Li+ , ) ,
0
II
,CH3CCH2R
(402)

18. A. C. Knipe and C. J. Stirling, J Chem. Soc., B 1968:67; for a discussion of factors which affect
intramolecular alkylation of enolates, see J. Janjatovic and Z. Majerski, J Org. Chem. 45:4892 (1980).
29. R. A. Kjonaas and D. D. Patel, Teimhedron Lett. 255467 (1984).
 Scheme 1.5. Alkylations of Relatively Acidic Carbon Acids

CHAPTER 1
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDIATES

C02CH3 C02CH3
+ BICH~(CH~)~CO~C~H~
DMF CH~(CH~)~COZC~H~
85% on I-mol scale

a. C. S. Marvel and F. D. Hager, Org. Synth. I:248 (1941).

b. R. B. Moffett, 0%.Synth. IV:291 (1963).
c. A. W. Johnson, E. Markham, and R. Price, Org. Synth. 42:75 (1962).
d. H. Adkins, N. lsbell, and B. Wojcik, 0%.Synth. II:262 (1943).
e. C. R. Hauser and W. R. Dunnavant, Org. Synfh. IW962 (1963).
f. E. M. Kaiser, W. G. Kenyon, and C. R. Hauser, 0% Synth. 47:72 (1967).
g. R. P. Mariella and R. Raube, Org. Synth. IW288 (1963).
h. K. E Bernardy. J. F. Poletto, J. Nocera, l? Miranda, R. E. Schaub, and M. J. Weiss, 1 Org. Chem. 45:4702
(1980).

Similarly, the dilithiurn salt of monoethyl malonic dianion is easily alkylated and the
product decarboxylates on a~idification.~'
The use of p-ketoesters and malonic ester enolates has largely been supplanted by the
development of the newer procedures based on selective enolate formation that permit
direct alkylation of ketone and ester enolates and avoid the hydrolysis and decarboxylation
of ketoesters intermediates. Most enolate alkylations are carried out by deprotonating the
ketone under conditions that are appropriate for kinetic or thermodynamic control.
Enolates can also be prepared from silyl en01 ethers and by reduction of enones (see
Section 1.3). Alkylation also can be carried out using silyl en01 ethers by reaction with
fluoride ion.31 Tetraalkylammoniurn fluoride salts in anhydrous solvents are normally the

30. J. E. McMuny and J. H. Musser, J Org. Chem. 40:2556 (1975).

3 1. I.Kuwajima, E. Nakamura, and M. Shimizu, .
IAm. Chem. Soc. 104:1025 (1982).
 Scheme 1.6. Synthesis of Ketones and Carboxylic Acid Derivatives via
Alkylation Followed by Decarboxylation
SECTION 1.4.

la CH3COCHCO2C2HS
I
-
Hz0 -OH
CH3COCHC02-
I
H+
; CH3CO(CH2)4CH3 5241%
ALKYLATION OF
ENOLATES

(CHz)3CH3 (CH2)3CH3
(see Scheme 1.5)

2b CH2(C02C2H5)2+ C7HI5Br -
NaOBu
C7H15CH(C02C2H5)2

C~HISCH(COZC~HS)Z -
H20, D H
+
H+
C~HI~CH(COZH)Z
C7H15CH(C02H)2 k C8Hl7CO2H + C 0 2 6675%

(see Scheme 1.5)

a. J. R. Johnson and F. D. Hager, Org. Synth. I:351 (1941).

b. E. E. Reid and 5. R. Ruhoff, Org. Synth. n:474 (1943).
c. G. B. Heisig and E H. Stodola, Org. Synth. U1:213 (1955).
d. J. A. Skorcz and F. E. Kaminski, Org. Synth. 48:53 (1968).
e. F. Elsinger, Org. Synth. V:76 (1973).

fluoride ion source.

1 1 Ref. 32

Several examples of alkylation of ketone enolates are given in Scheme 1.7.

32. A. B. Smith I11 and R. Mewshaw, J: Org. Chem. 49:3685 (1984).

16 Scheme 1.7. Regioselective Enolate Alkylation
CHAPTER 1
ALKYLATION OF
la
NUCLEOPHILIC
CARBON
INTERMEDIATES
0 JJJ* Li+-0b H
B O q d 3 %

(CH2)3CH3

4d

C H 3 4 Lm
Tw,-78°C
___t c H 3 d - C H 3 n &J
-B@c
/ 79%

5e
bcH3
bcH30
0-Li+ cH2=CHcH2B~ &
=H
c:I2

45%
Iramlcis -2011

- &
6f (CH3)3Si0

&cH(cH~)~ 1) MeLi CH(CH3)2

2) CH31 80%
H3C H3C

79 OSi(CH3)3

"-0 1) MeLi
2) ICH~CH=CCH,
COzC(CH3i3
CH2CH=CCH3
I
COzC(CH3)3
90%

0""' I) W+F,
THF
2) PhCHzBr
 Scheme 1.7. (continued)
SECTION 1.4.
ALKnATION OF
ENOLATES I

a. G. Stork, I? Rosen, N. Goldman, R. \! Coomhs, and J. Tsujii, 1 Am. Chem. Soc. 87:275 (1965).
b. H. A. Smith, B. J. L. Huff, W. 1. Powers 111, and D. Caine, 1 Org. Chem. 32:2851 (1967).
c. M. Gall and H. 0 . House, Org. Synth. 52:39 (1972).
d. S. C. Welch and S. Chayahunjonglerd, 1Am. Chem. Soc. 101:6768 (1979).
e. D. Caine, S. T. Chao, and H. A. Smith, Org. S p t h . 56:52 (1977).
f. G. Stork and P. F. Hudrlik, 1 Am. Chem. Soc. 90:4464 (1968).
g. P. L. Stotter and K. A. Hill, J. Am. Chem. Soc. 96:6524 (1974).
h. I. Kuwajima, E. Nakamura, and M. Shimizu, 1Am. Chem. Soc. 104:1025 (1982).
i. A. B. Smith III and R. Mewshaw, 1 Org. Chem. 49:3685 (1984).

The development of conditions for stoichiometric formation of both kinetically and

thermodynamically controlled enolates has permitted the extensive use of enolate alkyla-
tion reactions in multistep synthesis of complex molecules. One aspect of the reaction
which is crucial in many cases is the stereoselectivity. The alkylation step has a
stereoelectronic preference for approach of the electrophile perpendicular to the plane
of the enolate, since the electrons which are involved in bond formation are the n electrons.
A major factor in determining the stereoselectivity of ketone enolate alkylations is the
difference in steric hindrance on the two faces of the enolate. The electrophile will
approach from the less hindered of the two faces, and the degree of stereoselectivity
depends upon the steric differentiation. For simple, conformationally based cyclohexanone
enolates such as that from 4-t-butylcyclohexanone, there is little steric differentiation. The
ablation product is a nearly 1 : 1 mixture of the cis and trans isomers.

Ref. 33

The cis product must be formed through a transition state with a twistlike
conformation to adhere to the requirements of stereoelectronic control. The fact that this
pathway is not disfavored is consistent with other evidence that the transition state in
enolate alkylations occurs early and reflects primarily the structural features of the
reactant, not the product. A late transition state should disfavor the formation of the cis
isomer because of the strain energy associated with the nonchair conformation of the
product.
The introduction of an a w l substituents at the cr carbon in the enolate enhances
stereoselectivity somewhat. This is attributed to a steric effect in the enolate. To minimize
steric interaction with the solvated oxygen, the alkyl group is distorted somewhat from
coplanarity. This biases the enolate toward attack from the axial direction. The alternative
approach from the upper face would enhance the steric interaction by forcing the alkyl

33. H. 0. House, B. A. Terfertiller, and H. D. Olmstead, 1 Org. Chem. 33:935 (1968).

18 group to become eclipsed with the enolate oxygen.34
CHAPTER 1
ALKYLATION OF
NUCLEOPHILIC
CARBON (CH313C
INTERMEDIATES CH3
k ~ 3
83% 17%

When an additional methyl substituent is placed at C-3, there is a strong preference for
alkylation anti to the 3-methyl group. This can be attributed to the conformation of the
enolate, which places the methyl in a pseudoaxial conformation because of allylic strain
(see Part A, Section 3.3.) The C-3 methyl then shields the lower face of the e n ~ l a t e . ~ ~

disfavored favored

The enolates of 1- and Zdecalone derivatives provide further insights into the factors
governing stereoselectivity in enolate alkylations. The l(9)-enolate of 1-decalone shows a
preference for alkylation to give the cis ring juncture. This is believed to be due primarily
to a steric effect. The upper face of the enolate presents three hydrogens in a 1,3-diaxial
relationship to the approaching electrophile. The corresponding hydrogens on the lower
face are equatorial.36

The 2(1)-enolate of trans-2-decalone is preferentially alkylated by an axial approach of the

electrophile.

The stereoselectivity is enhanced if there is an alkyl substituent at C-1. The factors

operating in this case are similar to those described for 4-t-butylcyclohexanone. The trans-
decalone framework is conformationally rigid. Axial attack from the lower face leads
directly to the chair conformation of the product. The 1-alkyl group enhances this
34. H. 0.House and M. J. Umen, 1 Org. Chem.38:1000 (1973).
35. R. K. Boeckman, Jr., J 0%.Chem.38:4450 (1973).
36. H. 0.House and B. M. Trost, 1 Org. Chem.30:2502 (1965).
s t e m x e l ~ t ~n t ybecause a steric interaction u ~ t hthe solvated enolate oxygen distorts the
enolate In such a way as to favor the axial attack.'- The placement of an axial methyl group
SECTION 1.4.
at C-10 In a 2(1)-decalone enolate introduces a 1.3diaxial interaction with the approach- ALKYLATION OF
ing electrophile. The preferred alkylation product results from approach on the upper face ENOLATES
of the enolate.

The prediction and interpretation of alkylation stereochemistry also depends on

consideration of conformational effects in the enolate. The decalone enolate 1 was found
to have a strong preference for alkylation to give the cis ring junction, with alkylation
occurring syn to the t-butyl s ~ b s t i t u e n t . ~ ~

According to molecular mechanics calculations, the minimum-energy conformation of the

enolate is a twist-boat conformation (because the chair leads to an axial orientation of the t-
butyl group). The enolate is convex in shape, with the second ring shielding the lower face
of the enolate, and alkylation therefore occurs from the top.

If the alkylation is intramolecular, additional confotmational restrictions on the

direction of approach of the electrophile to the enolate become important. Baldwin et
al. have summarized the general principles that govern the energetics of intramolecular
ring-closure reactions.39 (See Part A, Section 3.9). The intramolecular alkylation reaction
of 2 gives exclusively 3.40 The transition state must achieve a geometry that permits
interaction of the R orbital of the enolate to achieve an approximately collinear alig lent
with the sulfonate leaving group. The alkylation probably occurs through a transitic. state
like J. The transition state K for formation of the trans ring junction would more

37. R. S. Mathews, S. S. Grigenti, and E. A. Fokers, 1 Chem. Soc., Chem. Commun. 1970:708; P. Lansbury and
G. E. DuBois, Tetrahedron Lett. 1972:3305.
38. H. 0. House, W. \! Phillips, and D. Van Derveer, 1 Org. Chem. 44:2400 (1979).
39. J. E. Baldwin, R. C. Thomas, L. I. Kruse, and L. Silberman, J Org. Chem. 42:3846 (1977).
40. J. M. Conia and E Rouessac, Tetrahedron 16:45 (1961).
20 strained because of the necessity to span the opposite face of the enolate n system.
CHAPTER l
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDIATES

These examples illustrate the issues which must be considered in analyzing the
stereoselectivity of enolate alkylation. The major factors are the conformation of the
enolate, the stereoelectronic requirement for an approximately perpendicular trajectory,
. and the steric preference for the least hindered path of approach.

1.5. Generation and Alkylation of Dianions

In the presence of a sufficiently strong base, such as an alkyllithium, sodium or

potassium hydride, sodium or potassium amide, or LDA, 1,3-dicarbonyl compounds can
be converted to their dianions by two sequential deprotonations.41For example, reaction of
benzoylacetone with sodium amide leads first to the enolate generated by deprotonation at
the methylene group between the two carbonyl groups. A second equivalent of base
deprotonates the benzyl methylene group to give a diendiolate.

0
11
0
11
PhCH2CCH2CCH3 -
2NaNHz
Li+O-
I
o-L~+
I
PhCH=C -CH= C -CH3 -
P ~IC H C H ~
C1
0
11
0
11
PhCHCCH2CCH3
I
PhCHCH3
Ref. 42

Alkylation reactions of dianions occur at the more basic carbon. This technique allows
alkylation of 1,3-dicarbonyl compounds to be carried out cleanly at the less acidic
position. Because, as discussed earlier, alkylation of the monoanion occurs at the
carbon between the two carbonyl groups, the site of monoalkylation can be controlled
by choice of the amount and nature of the base. A few examples of the formation and
alkylation of dianions are collected in Scheme 1.8.

1.6. Medium Effects in the Alkylation of Enolates

The rate of alkylation of enolate ions is strongly dependent on the solvent in which
the reaction is carried The relative rates of reaction of the sodium enolate of diethyl
n-butylmalonate with n-butyl bromide are shown in Table 1.2.

41. For reviews, see T. M. Harris and C. M. Harris, Org. React. 17:155 (1969); E. M. Kaiser, J. D. Petty, and P. L.
A. Knutson, Synthesis 1977509; C. M . Thompson and D. L. C. Green, Tetrahedron47:4223 (1991); C. M.
Thompson, Dianion Chemistry in Organic Synthesis, CRC Press, Boca Raton, Florida, 1994.
42. D. M. von Schriltz, K. G . Hamton, and C. R. Hauser, 1 Org. Chem. 34:2509 (1969).
43. For reviews, see (a) A. J. Parker, Chem. Rev 69:l (1969); (b) L. M. Jaclanamn and B. C. Lange, Tetrahedron
33:2737 (1977).
 Scheme 1.8. Generation and Alkylation of Dianions

SECTION 1.6.
MEDIUM EFFECTS IN
THE ALKYLATlON OF
ENOLATES

81-829
3C

BuBr
___)
2 equtv

4d 0 0- 0- 0
1I I ) NaH I I 1 ) EtBr 11
CH3CCH2C02CH3~)RLI CH2=CCH=COCH3 CH3(CH2)2CCH2C02CH3
2) H]O+
84%

5e 0- 0- 0
I I II
CH2=CCH=COCH3 + (CH3)2C=CHCH2Br --) (CH3)2C=CHCH2CH2CCH2C02CH3
85%

a. T. M. Hams, S. Boatman, and C. R. Hauser, J Am Chem. Soc. 85:3273 (1963); S. Boatman, T. M. Hams, and C. R.
Hauser, J Am. Chem. Soc. 87:82 (1965); K. G. Hampton, T. M. Harris, and C. R. Hauser, J Org. Chem. 28:1946
(1963).
b. K. G. Hampton, T. M. Hams, and C. R. Hauser, Org. Svnth. 47:92 (1967).
c. S. Boatman, T. M. Hanis, and C. R. Hauser, Org. Synth. 48:40 (1968).
d. S. N. Huckin and L. Weiler, J Am. Chem. Sac. 96:1082 (1974).
e. F. W. Sum and L. Weiler. J Am. Chem. Soc. 101:4401 (1979).

DMSO and N,N-dimethylformamide (DMF) are particularly effective in enhancing

the reactivity of enolate ions, as Table 1.2 shows. Both of these compounds belong to the
polar aprotic class of solvents. Other members of this class that are used as solvents in
reactions between carbanions and alkyl halides include N-methylpyrrolidone (NMP) and
hexamethylphosphoric triamide (HMPA). Polar aprotic solvents, as their name implies, are
materials which have high dielectric constants but which lack hydroxyl groups or other
Table 1.2 Relative Alkylation Rates of Sodium Diethyl
n-Butylmalonate in Various Solventsa

Solvent Dielectric constant, E Relative rate

Benzene 2.3 1
Tetrahydrofuran 7.3 14
Dimethoxyethane 6.8 80
Dimethylformamide 37 970
Dimethyl sulfoxide 47 1420

a. From H. E. Zaugg, J Am. Chem. Soc. 83:837 (1961)

 hydrogen-bonding groups. Polar aprotic solvents possess excellent metal-cation coordina-
tion ability, so they can solvate and dissociate enolates and other carbanions from ion pairs
CHAPTER 1
ALKYLATION OF and clusters.
NUCLEOPHILIC
CARBON
INTERMEDIATES

d~methyl~ u l l o x ~ d(DMSOI
e N.N-drmethylfurmamIde (UMF) N-methylpyl~ol~dant.
(NMP) hrx~rnethylphosphoric
s=37 e = 37 e = 32 t n a m ~ d e(HMPA)
e = 30

The reactivity of alkali-metal (Li+, Na+ , K+) enolates is very sensitive to the state of
aggregation, which is, in turn, influenced by the reaction medium. The highest level of
reactivity, which can be approached but not achieved in solution, is that of the "bare"
unsolvated enolate anion. For an enolate-metal ion pair in solution, the maximum
reactivity would be expected in a medium in which the cation was strongly solvated
and the enolate was very weakly solvated. Polar aprotic solvents are good cation solvators
and poor anion solvators. Each one (DMSO, DMF, HMPA, and NMP) has a negatively
polarized oxygen available for coordination to the alkali-metal cation. Coordination to the
enolate ion is much less effective because the positively polarized atom of these molecules
is not nearly as exposed as the oxygen. Thus, these solvents provide a medium in which
enolate-metal ion pairs are dissociated to give a less encumbered, more reactive enolate.

O M solvent + H0 + [M(solvent).]'

aggregated Ions di\soc~atedlonc

Polar protic solvents also possess a pronounced ability to separate ion pairs but are
less favorable as solvents for enolate alkylation reactions because they coordinate to both
the metal cation and the enolate ion. Solvation of the enolate anion occurs through
hydrogen bonding. The solvated enolate is relatively less reactive because the hydrogen-
bonded enolate must be disrupted during alkylation. Enolates generated in polar protic
solvents such as water, alcohols, or ammonia are therefore less reactive than the same
enolate in a polar aprotic solvent such as DMSO.

solvated Ion5

THF and DME are slightly polar solvents which are moderately good cation solvators.
Coordination to the metal cation involves the oxygen lone pairs. These solvents, because
of their lower dielectric constants, are less effective at separating ion pairs and higher
aggregates than are the polar aprotic solvents. The crystal structures of the lithium and
potassium enolates of methyl t-butyl ketone have been determined by X-ray crystal-
lography.44The structures are shown in Figs. 1.1 and 1.2. While these represent the solid- 23
state structural situation, the hexameric clusters are a good indication of the nature of the
SECTION 1.7.
enolates in relatively weakly coordinating solvents. Despite the somewhat reduced OXYGEN VERSUS
reactivity of aggregated enolates, THF and DME are the most commonly used solvents CARBON AS THE SITE
OF ALKYLATION
for synthetic reactions involving enolate alkylation. They are the most suitable solvents for
kinetic enolate generation and also have advantages in terms of product workup and
purification over the polar aprotic solvents. Enolate reactivity in these solvents can often be
enhanced by adding a reagent that can bind alkali-metal cations more strongly. Popular
choices are HMPA, tetramethylethylenediamine (TMEDA), and the crown ethers.45
TMEDA can chelate metal ions through the electron pairs on nitrogen. The crown
ethers can coordinate metal ions in structures in which the metal ion is encapsulated by
the ether oxygens. The 18-crown-6 structure is of such a size as to allow sodium or
potassium ions to fit comfortably in the cavity. The smaller 12-crown-4 binds ~ i +
preferentially. The cation complexing agents lower the degree of aggregation of the
enolate-metal-cation ion pairs and result in enhanced reactivity.
The reactivity of enolates is also affected by the metal counterion. Among the most
commonly used ions, the order of reactivity is M ~ <~Li++ < ~ a <+K+ . The factors that
are responsible for this order are closely related to those described for solvents. The
smaller, harder M~~~ and Lif cations are more tightly associated with the enolate than are
the ~ a and+ K+ ions. The tighter coordination decreases the reactivity of the enolate and
gives rise to more highly associated species.

1.7. Oxygen versus Carbon as the Site of Alkylation

Enolate anions are ambident nucleophiles.Alkylation of an enolate can occur at either

carbon or oxygen. Because most of the negative charge of an enolate is on the oxygen
atom, it might be supposed that 0-alkylation would dominate. A number of factors other
than charge density affect the C/O-alkylation ratio, and it is normally possible to establish
reaction conditions that favor aikylation on carbon.

0- 0
I II
C-alkylatlon RC=CH2 + R'X + RCCH2R'

0-alkylat~on
0-
I
RC=CH2 + R'X - OR'
I
RC=CH2

0-Alkylation is most pronounced when the enolate is dissociated. When the

potassium salt of ethyl acetoacetate is treated with diethyl sulfate in the polar aprotic
solvent HMPA, the major product (83%) is the 0-alkylated one. In THF, where ion
clustering occurs, all of the product is C-alkylated. In t-butanol, where the acetoacetate

44. I? G. Williard and G. B. Carpenter, 1 Am. Chem. Soc. 108:462 (1986)

45. C. L. Liotta and T. C. Caruso, Tetrahedron Lett. 26:1599 (1985).
CHAPTER 1
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDIATES

Fig. 1.1. Unsolvated hexameric

aggregate of lithium enolate of
methyl t-butyl ketone; large
circles = oxygen, small circles =
lithium. (Reproduced with permis-
sion from Ref. 44. Copyright 1986
American Chemical Society.)

Fig. 1.2. Potassium enolate of methyl t-butyl ketone; large

cirlces = oxygen, small circles =potassium. (a) Left-hand plot
shows only methyl t-butyl ketone residues. (b) Right-hand plot
shows only the solvating THF molecules. The crystal is a
composite of these two structures. (Reproduced with permission
from Ref. 44. Copyright 1986 American Chemical Society.)

anion is hydrogen-bonded by solvent, again only C-alkylation is observed.46

in HMPA 15% (2%dialkyl)

In r-butanol 94% (6%dialkyl)
in THF 94% (6% dialkyl)

46. A. L. Kurts, A. Masias, N. K. Genkina, I. P. Beletskaya, and 0. A. Reutov, Dokl. Akad. Nauk. SSR (Engl.
Transl.) 187:595 (1969).
Higher C/O-alkylation ratios are observed with alkyl halides than with alkyl sulfonates 25
and sulfates. The highest C/O-alkylation ratios are obtained with alkyl iodides. For
SECTION 1.7.
ethylation of the potassium salt of ethyl acetoacetate in HMPA, the product compositions OXYGEN VERSUS
shown below were obtained.47 CARBON AS THE SITE
OF ALKYLATION

X = OTs 11% (1% dialkyl)

X=CI 32% (8% dialkyl)
X = Br 38% (23%dialkyl)
X=I 71% (16% dialkyl)

Leaving-group effects on the ratio of C- to 0-alkylation can be correlated by

reference to the "hard-soft-acid-base" (HSAB) rationale.48 Of the two nucleophilic
sites in an enolate ion, oxygen is harder than carbon. Nucleophilic substitution reactions
of the SN2 type proceed best when the nucleophile and leaving group are either both hard
or both soft.49Consequently, ethyl iodide, with the very soft leaving group iodide, reacts
preferentially with the softer carbon site rather than the harder oxygen. Oxygen leaving
groups, such as sulfonate and sulfate, are harder, and alkyl sulfonates and sulfates react
preferentially at the hard oxygen site of the enolate. The hard-hard combination is favored
by an early transition state, where the charge distribution is the most important factor. The
soft-soft combination is favored by a later transition state, where partial bond formation is
the dominant factor. The C-alkylation product is more stable than the 0-alkylation product
+
(because the bond energy of C=O C-C is greater than that of C=C C-0). +
Therefore, conditions that favor a dissociated, more reactive enolate favor 0-alkylation.
Similar effects are also seen with enolates of simple ketones. For isopropyl phenyl
ketone, the inclusion of one equivalent of 12-crown-4 in a DME solution of the lithium
enolate changes the C/O-alkylation ratio from 1.2: 1 to 1 :3, with methyl sulfate as the
alkylating agent.50 With methyl iodide as the alkylating agent, C-alkylation is strongly
favored with or without 12-crown-4.

favored by added
crown ether

To summarize, the amount of 0-alltylation is maximized by use of an alkyl sulfate or

alkyl sulfonate in a polar aprotic solvent. The amount of C-alltylation is maximized by use
of an alkyl halide in a less polar or protic solvent. The majority of synthetic operations
involving ketone enolates are carried out in THF or DME using an alkyl bromide or alkyl
iodide, and C-alkylation is favored.

47. A. L. Kurts, N. K. Genkina, A. Masias, I. F! Beletskaya, and 0. A. Reutov, Tetrahedron 27:4777 (1971).
48. T.-L. Ho, Hard and Soft Acids and Bases Principle in Organic Chemistry, Academic Press, New York, 1977.
49. R. G. Pearson and J. Songstad, J Am. Chem. Soc. 89:1827 (1967).
50. L. M. Jackman and B. C. Lange, J Am. Chem. Soc. 103:4494 (1981).
26 Intramolecular alkylation of enolates leads to formation of cyclic products. In
addition to the other factors that govern C/O-alkylation ratios, the element of stereoelec-
CHAPTER I
ALKYLKrION OF tronic control comes into play in such cases. The following reactions illustrate this point.51
NUCLEOPHILIC
CARBON
INTERMEDIATES

CH3

ether

(onl) product)

-
ether
via
0 CH3 Br 0 0A -CH2
7 Br
(only product)

In order for C-alkylation to occur, the p orbital at the a carbon must be aligned with the
C-Br bond in the linear geometry associated with the SN2transition state. When the ring
to be closed is six-membered, this geometry is accessible, and cyclization to the
cyclohexanone occurs. With five-membered rings, colinearity cannot be achieved easily.
Cyclization at oxygen then occurs faster than does cyclopentanone formation. The
transition state for 0-alkylation involves an oxygen lone-pair orbital and is less strained
than the transition state for C-alkylation.

geometry requlred for ~ntrdmolecular geometry requ~rcdfor intramolecular

C-alklatlon of enolatc 0-alklat~onof enolatr

In enolates formed by proton abstraction from a$-unsaturated ketones, there are three
potential sites for attack by electrophiles: the oxygen, the a carbon, and the y carbon. The
kinetically preferred site for both protonation and alkylation is the a carbon.

51. J. E. Baldwin and L. I. Kruse, .J Chum. Sor., Chem. Commun. 1977:233.

Protonation of the enolate provides a method for converting a,p-unsaturated ketones and 27
esters to the less stable B,y-unsaturated isomers.
SECnON 1.I.
OXYGEN VERSUS
CARBON AS THE SlTE

(major) (minor)

Ref. 52

CH3CH=CHC02C2H5 --
LiI'JP.2 H20
CH2=CHCH2C02C2H5
87%
+ CH3CH=CHCO2C2HS
13%
Ref. 53

Alkylation also takes place selectively at the a carbon.17 The selectivity for electrophilic
attack at the u carbon presumably reflects a greater negative charge, as compared with the y
carbon.

Phenoxide ions are a special case related to enolate anions but with a strong
preference for 0-alkylation because C-alkylation disrupts aromatic conjugation.

Phenoxides undergo 0-allcylation in solvents such as DMSO, DMF, ethers, and alcohols.
In water and trifluoroethanol, however, extensive C-alkylation occurs.54 These latter
solvents form particularly strong hydrogen bonds with the oxygen atom of the phenolate

52. J. H. Ringold and S. K. Malhotra, Teimhedmn Lett. 1962:669; S . K. Malhotra and H. I Ringold, 1 Am.
Chem. Soc. 85: 1538 ( 1 963).
53. M. W.Rathke and D. Sullivan, Teimhedmn Lett. 1972:4249.
54. N . Komblum, P.J. Bemgan, and W. J. LeNoble, J Am. Chem. Soc. 8 5 1 141 (1963); N. Komblum, R. Seltzer,
and F! Haberfield, 1 Am. Chem. Soc. 85:1148 (1963).
 anion. This strong solvation decreases the reactivity at oxygen and favors C-ablation.
CHAPTER 1
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDIATES

1.8. Alkylation of Aldehydes, Esters, Amides, and Nitriles

Among the compounds capable of forming enolates, the alkylation of ketones has
been most widely studied and used synthetically. Similar reactions of esters, amides, and
nitriles have also been developed. Alkylation of aldehyde enolates is not very common.
One limitation is the fact that aldehydes are rapidly converted to aldol condensation
products by base (see Chapter 2 for more discussion of this reaction). Only when the
enolate can be rapidly and quantitatively formed is aldol condensation avoided. Success
has been reported using potassium arnide in liquid and potassium hydride in
THE Alkylation via enamines or enamine anions provides a more general method for
alkylation of aldehydes. These reactions will be discussed in Section 1.9.
I ) KH, THF
(CH3)ZCHCHO 2) BrCH2CH=C(CH3);
(CH~)~CCHZCH=(CH~)Z Ref. 56
I
CHO
88%

Alkylations of simple esters require a strong base because relatively weak bases such
as alkoxides promote condensation reactions (see Chapter 2). The successful formation of
ester enolates typically involves an amide base, usually LDA or potassium hexamethyldi-
silylamide (KHMDS) at low temperature.57 The resulting enolates can be successfully
alkylated with alkyl bromides or iodides. HMPA is sometimes added to accelerate the
reaction. Some examples are given in Scheme 1.9.
Carboxylic acids can be directly alkylated by conversion to dianions by two
equivalents of LDA. The dianions are alkylated at the a carbon as would be expected.58

(CH3)2CHC02H -ZLDA CH3,

CH3
,C=C,
/O-Li+
o-Li+
CH3(CH2)3Br

H'
CH3
I
* CH3(CH2)3C-C02H
I
CH3

55. S. A. G. De Graaf, P. E. R. Oosterhof, and A. van der Gen, Tetrahedron Len. 1974:1653.
56. F! Groenewegen, H. Kallenberg, and A. van der Gen, Tetrnhedmn Lett. 1978:491.
57. (a) M. W. Rathke and A. Lindert, 1 Am. Chem. Soc. 93:2318 (1971); (b)R. J. Cregge, J. L. Henmann, C. S.
Lee, J. E. Richman, and R. H. Schlessinger, Tetmhedmn Lett. 1973:2425; (c) J. L. Henmann and R. H.
Schlessinger, 1 Chem. Soc., Chem. Commun. 1973:711.
58. F! L. Creger, 1 Am. Chem. Soc. 89:2500 (1967); F! L. Creger, Org. Synth. 5058 (1970); F! L. Creger, 1Org.
Chem. 37: 1907 (1972).
 Scheme 1.9. Alkylation of Esters, Amides, Imides and Nitriles

C02CH3
1) LDA,THF,-7O'C
2) ~ ~ 3 ( m z ) d , 256 o(cH2)6 C02CH3
-90%
SECTION 1.8.
ALKnATION OF
ALDEHYDES, ESTERS,
AMIDES, AND NITRILES

3C
I)LDA,DME
O 2) CK+~H(CH,& 0 86%
3) LDA, DME
CH~ 4) CHd

se H q
'., CH3Q

P 0
I ) 2 LDA, THF,-78'C
2) 2 CHd. HMPA.-4SPC
cH3
0
65%

79

.u
Phi:
,
,G
-
1) LDA

. .b CH2Ph
CH3 phi: CH3 78%
 Scheme 1.9. (continued)

a. T. R. Williams and L. M. Sirvio, 1 Org. Chem. 455082 (1980).

b. M.W. Rathke and A. Lindert, 1 Am. Chem. Soc. 93:2320 (1971).
c. S. C. Welch, A. S. C. Prakasa Rao, C. G. Gibbs, and R. Y. Wong, J: Org Chem. 454077 (1980).
d. W. H. Pirkle and P. E. Adams, 1Org. Chem. 4541 11 (1980).
e. H.-M. Shieh and G. D. Restwich, J: Org. Chem. 46:4319 (1981).
f. D. Kim, H. S. Kim, and J. Y.Yoo, Tetrahedron Len. 32:1577 (1991).
g. D. A. Evans, M.D. Ennis, and D. J. Mathre, 1 Am. Chem. Soc. 104:73 (1982).
h. A. Fadel, Synlett. 1992:48.
i. L. A. Paquette, M. E. Okazaki, and J.-C. Caille, 1 Org. Chem. 53:477 (1988).

A method for enantioselective synthesis of carboxylic acid derivatives is based on

alkylation of the enolates of N-acyl oxa~olidinones.~~ The lithium enolates have the
structures shown because of the tendency for the metal cation to form a chelate.

In 4 the upper face is shlelded by the isopropyl group whereas in 5 the lower face is
shielded by the methyl and phenyl groups. As a result, alkylation of the two derivatives
gives products of the opposite configuration. Subsequent hydrolysis or alcoholysis
provides acids or esters in enantiomerically enriched form. The initial alkylation product
59. D. A. Evans, M.D. Ennis, and D. J. Mathre, 1 Am. Chem. Soc. 104:1737 (1982);D. J. Ager, I. Prakash, and D.
R. Schaad, Chem. Rev. 96:835 (1996); D. J. Ager, I. Prakash, and D. R. Schaad, Aldrichimica Acta 30:3
(1997).
 ratios are typically 95 :5 in favor of the major isomer. Because the intermediates are 31
diastereomeric mixtures, they can be separated. The fmal products can then be obtained in
SECTION 1.9
>99% enantiomeric purity. Several other oxazolidinones have been developed for use as THE NITROGEP
chiral auxiliaries. 5,5-Diary1 derivatives are quite promising.60 ANALOGS OF ENOL!
AND ENOLATES--
ENAMINES AND IMINI
0
II ? ANION5
C
O/C\NH o/ 'NH

Naph

Acetonitrile (fiMSO = 3 1.3) can be deprotonated, provided a strong nonnucleophilic

base such as LDA is used.

CH3C= N
LDA
LiCH2CEN -Y-7
1) 0
2) (CH3)3SiCI
(CHs)3SiOCH2CH2CH2CI N
78%
Ref. 61

Phenylacetonitrile (PKDMSO = 21.9) is considerably more acidic than acetonitrile. Depro-

tonation can be done with sodium amide. Dialkylation has been used in the synthesis of
/i meperidine, an analgesic substance.62

1.9. The Nitrogen Analogs of Enols and Enolates-Enamines and Imine

Anions

The nitrogen analogs of ketones and aldehydes are called imines, azomethines, or
Schzflbases. Imine is the preferred name and will be used here. These compounds can be
prepared by condensation of primary amines with ketones and aldehydes.63

0 N-R
II II
R-C-R +R m -t R-C-R + H20

60. T. Hintermann and D. Seebach, Helv. Chim. Acta 81:2093 (1998); C . L. Gibson, K. Gillon, and S. Cook,
Tetmhedron Lett. 39:6733 (1998).
61. S. Murata and I. Matsuda, Synthesis 1978:221.
62. 0.Eisleb, Berichte 74:1433 (1941); cited in H. Kagi and K. Miescher, Helv. Chim. Acta 32:2489 (1949).
63. For general reviews of imines and enamines see F! Y. Sollenberger and R. B.Martin, in The Chemisw of the
Amino Group, S. Patai, ed., John Wiley & Sons, 1968, Chapter 7; G. Pitacco and E. Valentin, in The
Chemistry of Amino, Nitroso and Nitro Groups and Their Derivatives, Part 1 , S. Patai, ed., John Wiley &
Sons, New York, 1982, Chapter 15; P.W. Hickmott, Tehahedron 38:3363 (1982); A. G. Cook, ed., Enamines:
Synthesis, Structure and Reactions, Marcel Dekker, New York, 1988.
32 When secondary amines are heated with ketones or aldehydes in the presence of an acidic
catalyst, a related condensation reaction occurs and can be driven to completion by
CHAPTER 1
ALKYLATIONOF removal of water by azetropic distillation or use of molecular sieves. The condensation
NUCLEOPHILIC product is a substituted vinylamine or enamine.
CARBON
INTERMEDIATES
0 OH
II +
RCCHR, + R ~ N H = RiN-L-CHR2
I
H+
= R;N=c-cHR~
I
-Hf
= R2N-C=CR2
I
R R R

There are other methods for preparing enamines from ketones that utilize strong
dehydrating reagents to drive the reaction to completion. For example, mixing carbonyl
compounds and secondary arnines followed by addition of titanium tetrachloride rapidly
gives enamines. This method is especially applicable to hindered a m i n e ~Triethoxysi-
.~~
lane can also be used.65 Another procedure involves converting the secondary amine to its
N-trimethylsilyl derivative. Because of the higher a f i t y of silicon for oxygen than
nitrogen, enamine formation is favored and takes place under mild condition^.^^

The /?-carbon atom of an enamine is a nucleophilic site because of conjugation with

the nitrogen atom. Protonation of enamines takes place at the /? carbon, giving an iminium
ion.

The nucleophilicity of the /?-carbon atoms permits enamines to be used in synthetically

useful alkylation reactions:

The enamines derived from cyclohexanones have been of particular interest. The
pyrrolidine enamine is most frequently used for synthetic applications. In the enamine
mixture formed from pyrrolidine and 2-methylcyclohexanone, structure 6 is predomi-
nant.67 The tendency for the less substituted enamine to predominate is quite general. A
steric effect is responsible for this preference. Conjugation between the nitrogen atom and
the K orbitals of the double bond favors coplanarity of the bonds that are darkened in the
structures. A serious nonbonded repulsion (A',~strain) destabilizes isomer 7. Furthermore,
in isomer 6 the methyl group adopts a quasi-axial conformation to avoid steric interaction

64. W. A. White and H. Weingarten, 1Org. Chem. 32:213 (1967); R Carlson, R. Phan-Tan-Luu, D. Mathieu, E.
S. Ahounde, A. Babadjamiau, and J. Meager, Acta Chem. Scand. B32:335 (1978); R Carlson, A. Nilsson,
and M. Stromqvist,Acta Chem. Scand. B37:7 (1983);R. Carlson and A. Nilsson, Acta Chem. Scand. B38:49
(1984); S. Schubert, l? Renau4 F!-A. Carmpt, and K. Schenk, Helv. Chim. Acta 76:2473 (1993).
65. B.E. h e and J. Ren, 1 Org.Chem. 58:5556 (1993).
66. R. Corni, R W. Franck, M. Reitano, and S. M. Weinreb, Tetmhediwn Lett.1973:3107.
67. W. D.Gumwitz and M. A. Joseph, 1 Org. Chem. 32:3289 (1967).
with the amine sub~tituents.~~
SECTION 1.9.
THE NITROGEN
ANALOGS OF ENOLS
AND ENOLATES-
ENAMINES AND IMINE
ANIONS

Because of the predominance of the less substituted enamine, alkylations occur

primarily at the less substituted a carbon. Synthetic advantage can be taken of this
selectivity to prepare 2,6-disubstituted cyclohexanones. The iminium ions resulting from
C-alkylation are hydrolyzed in the workup procedure.

CH2CH=CCH3 Ref. 69
I
C02H
52%

Alkylation of enamines requires relatively reactive alkylating agents for good results.
Methyl iodide, allylic and benzylic halides, a-haloesters, a-haloethers, and a-haloketones
are the most successful alkylating agents. Some typical examples of enamine alkylation
reactions are shown in Scheme 1.10.
Enarnines also react with electrophilic alkenes. This aspect of their chemistry will be
described in Section 1.10.
Itnines can be deprotonated at the a carbon by strong bases to give the nitrogen
analogs of enolates. Originally, Grignard reagents were used for deprotonation, but LDA is
now commonly used. These anions are usually referred to as imine anions or metalloe-
narnine~.~' Irnine anions are isoelectronic and structurally analogous to both enolates and
ally1 anions and can also be called azaallyl anions.
NR'
II
nc-cm; -
base
NR'
II
RC-CR; - - NR'
nL=cn;
Spectroscopic investigations of the lithium derivatives of cyclohexanone N-phenyli-
mine indicate that it exists as a dimer in toluene and that as a better donor solvent, THF, is
added, equilibrium with a monomeric structure is established. The monomer is favored at
high THF c~ncentrations.~~ A crystal structure determination has been done on the

68. F. Johnson, L. G. Duquette, A. Whitehead, and L. C. Dorman, Tetmhedmn 30:3241 (1974); K . Muller, F.
Previdoli, and H. Desilvestro,Helv Chim. Acta 642497 (198 1); J. E. Anderson, D. Casarini, and L. Lunwi,
Tehahedron Len. 25:3141 (1988).
69. P. L. Stotter and K. A. Hill, .
IAm. Chem. Soc. 96:6524 (1974).
70. For a general review of imine anions, see J. K. Whitesell and M. A. Whitesell, Synthesis 1983:517.
 Scheme 1.10. Enamine Alkylation

CHAPTER l
ALKYLATION OF
NUCLEOPHILIC
CARBON
INTERMEDIATES

'";";"'
5e

g 1 - 0
0
1) pyrrolidine

2) CH2= CCHZCI,Nal, diisopropylamine

3) Hz0
CI

CH2=CCH2
C1I 0 I
CH2C=CH2
C1
91%

a. G. Stork, A. Brizzolara, H. Landesman, J. Smuszkovicz, and R. T a l l , 1 Am. Chem. Soc. 85:207 (1963).
b. D. M.Locke and S. W. Pelletier, 1 Am. Chem. Soc. 80:2588 (1958).
c. K. Sisido. S. Kurozumi, and K. Utimoto, 1 Am. Chem. Soc. 34:2661 (1969).
d. G. Stork and S. D. Darling, 1 Am. C h m . Soc. 86:1761 (1964).
e. J. A. Marshall and D. A. Flynn, 1 Org. Chem. 44:1391 (1979).

lithiated N-phenylimine of methyl t-butyl ketone. It is a dirneric structure with the lithium
cation positioned above the nitrogen and closer to the phenyl ring than to the carbon of
the imine anion.72The structure is shown in Fig. 1.3.
Just as enarnines are more nucleophilic than enols, irnine anions are more nucleo-
philic than enolates and react efficiently with alkyl halides. One application of imine

71. N. KaiIman and D. B. Collum, J. Am. Chem. Soc. 109:7466 (1987).

72. H. Dietrich, W. Mahdi, and R Knorr, J Am. Chem. Soc. 108:2462 (1986).
 SECTION 1.9.
THE NlTROGEN
ANALOGS OF ENOLS
AND ENOLATES-
ENAMINES AND IMINE
ANIONS

Fig. 1.3. Crystal structure of dimer of lithium

derivative of N-phenyl irnine of methyl t-butyl
ketone. (Reproduced with permission fkom
Ref. 72. Copyright 1986 American Chemical
Society.)

anions is for the alkylation of aldehydes.

(CH3)zCHCH=NC(CH3)3 -
WgBr
(CH3)2C=CH-N,
/
MgBr

Ref. 73

fi30
(CH3)2CCH= 0 (CH3)2C-CH=NC(CH3)3
I I
CHzPh CHzPh
80%overall yield

Ketone irnine anions can also be alkylated. The prediction of the regioselectivity of
lithioenamine formation is somewhat more complex than for the case of kinetic ketone
enolate formation. One of the complicating factors is that there are two imine stereo-
isomers, each of which can give rise to two regioisomeric imine anions. The isomers in

73. G. Stork and S. R. Dowd, 1 Am. Chem.Soc. 85:2178 (1963).

74. T. Kametani, Y.Suzuki, H. Furuyama, and T. Honda, 1Org. Chem. 48:31 (1983).
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I now come to the following statement, made by a gentleman who
for more than thirty years has been familiar with all matters
connected with the coal-merchants’ trade. “I cannot say,” he began,
“that the condition of the coalporter (not referring to his earnings,
but to his moral and intellectual improvement) is much amended
now, for he is about the same sort of man that he was thirty years
ago. There may be, and I have no doubt is, a greater degree of
sobriety, but I fear chiefly on account of the men’s earnings being
now smaller, and their having less means at their command. Thirty-
five years ago, before the general peace, labourers were scarce, and
the coalporters then had full and ready employment, earning from
2l. to 3l. a-week. I have heard a coalporter say that one week he
earned 5l.; indeed, I have heard several say so. After the peace, the
supply of labour for the coal-trade greatly increased, and the
coalporters’ earnings fell gradually. The men employed in a good
establishment thirty years ago, judging from the payments in our
own establishment as a fair criterion, were in the receipt of nearly 3l.
a-week on the average. At that time coal was delivered by the
chaldron. A chaldron was composed of 12 sacks containing 36
bushels, and weighing about 25 cwt. (a ton and a-quarter). For the
loading of the waggons a gang of four men, called ‘fillers,’ was, and
is, employed. They were paid 1s. 4d. per chaldron; that is, 4d. per
man. This was for measuring the coal, putting it into sacks, and
putting the sacks into the waggon. The men in this gang had
nothing to do with the conveyance of the coal to the customers. For
that purpose two other men were employed; a ‘waggoner,’ and a
man known as a ‘trimmer,’ or ‘trouncer,’ who accompanied the
waggoner, and aided him in carrying the sacks from the waggon to
the customers’ coal-cellar, and in arranging the coal when delivered,
so as properly to assort the small with the large, or indeed making
any arrangement with them required by the purchaser. The
waggoner and the trimmer were paid 1s. 3d. each per chaldron for
delivery, but when the coal had to be carried up or down-stairs any
distance, their charge was an extra shilling—2s. 3d. Many of the
men have at that time, when work was brisk, filled and delivered
fifteen chaldrons day by day, provided the distance for delivery was
not very far. Drink was sometimes given by the customers to the
waggoner and trimmer who had charge of the coal sent to their
houses—perhaps generally given; and I believe it was always asked
for, unless it happened to be given without asking. At that time I did
not know one teetotaler; I do not know one personally among those
parties now. Some took the pledge, but I believe none kept it. In
this establishment we discourage drunkenness all that we possibly
can. In 1832, wages having varied from the time of the peace until
then, a great change took place. Previous to that time a reduction of
4d. per ton had been made in the payment of the men who filled the
waggons (the fillers), but not in that of the waggoner or the trimmer.
The change I allude to was that established by Act of Parliament,
providing for the sale of all coal by the merchant being by weight
instead of by measure. This change, it was believed, would benefit
the public, by ensuring them the full quantity for which they
bargained. I think it has benefited them. Coal was, under the former
system, measured by the bushel, and there were frequently
objections as to the way in which the bushel was filled. Some
dealers were accused of packing the measure, so as to block it up
with large pieces of coal, preventing the full space being filled with
the coal. The then Act provided that the bushel measure should be
heaped up with the coal so as to form a cone six inches above the
rim of the measure. When the new Act came into operation the
coalporters were paid 10d. a-ton among the gang of four fillers, and
the same to the waggoner and trimmer. Before two years this
became reduced generally to 9d. The gang could load twenty-five
tons a-day without extra toil; forty tons, and perhaps more, have
been loaded by a gang: but such labour continued would exhaust
strong men. With extra work there was always extra drink, for the
men fancy that their work requires beer ‘for support.’ My opinion is
that a moderate allowance of good malt liquor, say three pints a-day
when work is going on all day, is of advantage to a coalporter. In the
winter they fancy it necessary to drink gin to warm them. At one
time all the men drank more than now. I estimate the average
earnings of a coalporter fully employed now at 1l. a-week. There are
far more employed at present than when I first knew the trade, and
the trade itself has been greatly extended by the new wharfs on the
Regent’s Canal, and up and down the river.”
I had heard from so many quarters that “beer” was a necessity of
the coal-labourers’ work, that finding the coalwhippers the most
intelligent of the whole class, I thought it best to call the men
together, and to take their opinion generally on the subject.
Accordingly I returned to the basketmen’s waiting-room at the
coalwhippers’ office, and, as before, it was soon crowded. There
were eighty present. Wishing to know whether the coalbacker’s
statement already given, that the drinking of beer was a necessity of
hard labour, was a correct one, I put the question to the men there
assembled: “Is the drinking of fermented liquors necessary for
performing hard work? How many present believe that you can work
without beer?” Those who were of opinion that it was necessary for
the performance of their labour, were requested to hold up their
hands, and four out of the eighty did so.
A basketman who had been working at the business for four years,
and for two of those years had been a whipper, and so doing the
heaviest labour, said that in the course of the day he had been one
of a gang who had delivered as many as 189 tons. For this he had
required no drink at all; cocoa was all he had taken. Three men in
the room had likewise done without beer at the heaviest work. One
was a coalwhipper, and had abstained for six years. Some difference
of opinion seemed to exist as to the number in the trade that
worked without beer. Some said 250, others not 150. One man
stated that it was impossible to do without malt liquor. “One shilling
a day properly spent in drink would prolong life full ten years,” he
said. This was received with applause. Many present declared that
they had tried to do without beer, and had injured themselves
greatly by the attempt. Out of the eighty present, fourteen had tried
teetotalism, and had thrown it up after a time on account of its
injuring their health. One man, on the other hand, said he had given
the total-abstinence principle a fair trial for seven months, and had
never found himself in such good health before. Another man stated,
that to do a day’s work of ninety-eight turns, three pints of beer
were requisite. All but three believed this. The three pints were
declared to be requisite in winter time, and four pints, or two pots,
were considered to be not too much in a hot summer’s day. Before
the present office was instituted, each man, they told me, drank
half-a-pint of gin and six pots of beer daily. That was the average—
many drank more. Then they could not do their work so well; they
were weaker from not having so much food. The money went for
drink instead of meat. They were always quarrelling on board a ship.
Drunken men could never agree. “A portion of beer is good, but too
much is worse than none at all.” This was the unanimous
declaration.
Since this meeting I have been at considerable pains to collect a
large amount of evidence in connexion with this most important
question. The opinion of the most intelligent of the class seems to
be, that no kind of fermented drink is necessary for the performance
of the hardest labour; but I have sought for and obtained the
sentiments of all classes, temperate and intemperate, with the view
of fairly discussing the subject. These statements I must reserve till
my next letter. At present I shall conclude with the following story of
the sufferings of the wife of one of the intemperate class:—
“I have been married nineteen or twenty years. I was married at
Penton, in Oxfordshire. We came to London fifteen years ago. My
husband first worked as a sawyer. For eleven years he was in the
coal-trade. He was in all sorts of work, and for the last six months he
was a ‘scurf.’ What he earned all the time I never knew. He gave me
what he liked, sometimes nothing at all. In May last he only gave me
2s. 8d. for the whole month, for myself and two children. I buried
four children. I can’t tell how we lived then. I can’t express what
we’ve suffered, all through drink. He gave me twenty years of misery
through drink. [This was repeated four or five times.] Some days
that May we had neither bit nor sup; the water was too bad to drink
cold, and I had to live on water put through a few leaves in the
teapot—old leaves. Poor people, you know, sir, helps poor people;
and but for the poor neighbours we might have been found dead
some day. He cared nothing. Many a time I have gone without bread
to give it to the children. Was he ever kind to them, do you say, sir?
No; they trembled when they heard his step; they were afraid of
their very lives, he knocked them about so; drink made him a
savage; drink took the father out of him.” This was said with a flush
and a rapid tone, in strong contrast with the poor woman’s generally
subdued demeanour. She resumed:—“Twenty miserable years
through drink! I’ve often gone to bring him from the public-house,
but he seldom would come. He would abuse me, and would drink
more because I’d gone for him. I’ve often whispered to him that his
children was starving: but I durstn’t say that aloud when his mates
was by. We seldom had a fire. He often beat me. I’ve 9s. in pawn
now. Since we came to London I’ve lost 20l. in the pawnshop.”
This man had died a fortnight before, having ruptured a blood-
vessel. He lay ill six days. The parish doctor attended him. His
comrades “gathered” for his burial, but the widow had still some
funeral expenses to pay by instalments. The room she and the
children occupied was the same as in the husband’s lifetime. There
was about the room a cold damp smell, arising from bad ventilation
and the chilliness of the weather. Two wretched beds almost filled
the place. No article was worth a penny, nor could a penny have
been obtained at a sale or a pawnshop. The woman was cleanly
clad, but looked sadly pinched, miserable, and feeble. She earns a
little as a washerwoman, and did earn it while her husband lived.
She bears an excellent character. Her repetition of the words,
“twenty years of misery through drink,” was very pitiful. I refrained
from a prolonged questioning, as it seemed to excite her in her weak
state.
 BALLAST-MEN.
Having finished with the different classes of coal-labourers in London—the whippers, backers, pull-
backs, trimmers, and waggoners—I purpose now dealing with the ballast-men, including the ballast-
getters, the ballast-lightermen, and the ballast-heavers of the metropolis. My reason for passing from
the coal to the ballast-labourers is, because the latter class of the work-people are suffering under the
same iniquitous and pernicious system of employment as that from which the coal-labourers have
recently been emancipated, and the transition will serve to show not only the present condition of the
one class of men, but the past state of the other.
After treating of the ballast-labourers, I purpose inquiring into the condition and income of the
stevedores, or men engaged in the stowing or unstowing of vessels; and of the lumpers and riggers, or
those engaged in the rigging and unrigging of them. It is then my intention to pass to the corn-
labourers, such as the corn-porters, corn-runners, and turners, touching incidentally upon the corn-
meters. After this, I mean to devote my attention to the timber-labourers engaged at the different
timber-docks—as, for instance, the Commercial, the Grand Surrey, and the East Country Docks. Then, in
due course, I shall come to the wharf-labourers and porters, or men engaged at the different wharfs in
London; thence I shall digress to the bargemen and lightermen, or men engaged in the transit of the
different cargoes from the ships to their several points of destination up or down the river; and finally, I
shall treat of the watermen, the steamboat-men, and pier-men, or those engaged in the transit of
passengers along the Thames. These, with the dock-labourers, of whom I have before treated, will, I
believe, exhaust the subject of the long-shore labourers; and the whole will, I trust, form, when
completed, such a body of facts and information, in connexion with this particular branch of labour, as
has never before been collected. I am happy to say, that, with some few exceptions, I have received
from the different official gentlemen not only every courtesy and consideration, but all the assistance
and co-operation that it lay in their power to afford me. Every class seems to look upon the present
inquiry as an important undertaking, and all, save the Clerk of the Coal Exchange and the Deputy-
Superintendent of the London Docks, have shown themselves not only willing, but anxious, to lend a
hand towards expediting the result.
Before quitting the subject of the coal-market, let me endeavour to arrive at an estimate as to the
amount of wealth annually brought into the port of London by means of the colliers, and to set forth, as
far as possible, the proportion in which it is distributed. I have already given some statistics, which,
notwithstanding the objections of a coal-merchant, who, in a letter to a journal, stated that I had
reckoned the number of ships at twice the real quantity, were obtained from such sources, and, I may
add, with so much care and caution, as to render them the most accurate information capable of being
procured at present on the subject. The statistics of the number of tons of coals brought into the port of
London in the year 1848, the number of vessels employed, of the voyages made by those vessels
collectively, and of the seamen engaged in the traffic, were furnished by the Clerk of the Coal Exchange
at the time of the opening of the new building. Had the coal-merchant, therefore, made it his duty to
devote the same time and care to the investigation of the truth of my statements that I have to the
collection of them, he would not only have avoided committing the very errors he condemns, but would
have displayed a more comprehensive knowledge of his business.
In 1848 there were imported into the London coal market 3,418,340 tons of coal. These were sold to
the public at an average rate all the year round of 22s. 6d. a ton. Hence the sum expended in the
metropolis for coal in that year was 3,845,632l. 10s.
There are 21,600 seamen engaged in the coal trade, and getting on an average 3l. 10s. £624,240 0 0
per man per voyage. Each of these men makes between 4 and 5 voyages in the course of
the year. Hence the average earnings of each man per year will be 15l. 18s., exclusive of
his keep; calculating that at 5s. per week, or 13l. per year, we have 28l. 18s. for the
expense of each of the seamen employed. Hence, as there are 21,600 sailors in the coal
trade, the total yearly cost would be
There are 170 coal-meters, earning, on an average, 2l. per week, or 104l. per year each
man. This would make the total sum paid in the year to the coal-meters 17,680 00
There are 2000 coal-whippers, earning 15s. 1½d. each per week, or 39l. 6s. 6d. per
man. Hence the total sum paid in the course of last year to the coal-whippers was 78,650 00
There are 3000 coal-porters earning, on an average, 1l. per week, or 52l. per year per
man, so that they receive annually 156,000 00
Hence the total amount paid per year to the working-men engaged in bringing and
delivering coals in the London market is £876,570 00
The area of all the coal-fields of Great Britain has been roughly estimated at 9000 square miles. The
produce is supposed to be about 32,000,000 tons annually, of which 10,000,000 tons are consumed in
the iron-works, 8,500,000 tons are shipped coastwise, 2,500,000 tons are exported to foreign countries,
and 11,000,000 tons distributed inland for miscellaneous purposes. Near upon 4,000,000 tons were
brought to London by ships and otherwise in the year 1848, and it is computed that about one-eighth
part of this, or 500,000 tons, were consumed by the gas-works.
The price of coals as quoted in the London market is the price up to the time when the coals are
whipped from the ships to the merchants’ barges. It includes, 1st. the value of the coals; 2d. the
expense of transit from the pit to the ship; 3d. the freight of the ship to London; 4th. the Thames’ dues;
and 5th. the whipping. The difference between the market price and that paid by the consumer is made
up of the expense incurred by the coal-merchant for barges, wharfs, waggons, horses, wages, coal-
porters, &c., to his profit and risk. In 1836 the expenses incurred by the merchant from the time he
bought a ship-load of coals to the deposition of them in the cellars of his customers amounted, on an
average, it was said, to 7s. a ton. These expenses comprise commission, lighterage, porterage, cartage,
shooting, metage, market-dues, land-metage, and other items. At the present time the expenses must
be considerably lower, the wages of the labourers and the meters having been lowered full 50 per cent,
though the demand for and consumption of coal has increased at nearly the same rate; indeed the law
of the coal-market appears to be, that in proportion as the demand for the article rises, so do the wages
of the men engaged in the supply of it fall.
As the ballast-heavers are under the thraldom of the same demoralising and oppressive system as that
which the coal-whippers recently suffered under, it may be as well, before going further, to lay before
the reader the following concise account of the terms on which the latter were engaged before the
Coal-whippers’ Office was established.
Until the last few years the coal-whippers suffered themselves to be duped in an extraordinary way by
publicans and petty shopkeepers on shore. The custom was, for the captain of a coal-ship, when he
required a cargo to be whipped, to apply to one of these publicans for a gang; and a gang was
accordingly sent from the public-house. There was no professed or pre-arranged deduction from the
price paid for the work; the captain paid the publican, and the publican paid the coal-whippers; but the
middleman had his profit another way. The coal-whipper was expected to come to the public-house in
the morning; to drink while waiting for work, to take drink with him to the ship, to drink again when the
day’s work was over, and to linger about and in the public-house until almost bed-time before his day’s
wages were paid. The consequence was, that an enormous ratio of his earnings went every week to the
publican. The publicans were wont to divide their dependants into two classes—the constant men and
the stragglers, of whom the former were first served whenever a cargo was to be whipped; in return for
this they were expected to spend almost the whole of their spare time in the public-house, and even to
take up their lodgings there.
The captains preferred applying to the publicans to engaging the men themselves, because it saved
them trouble; and because (as was pretty well understood) the publicans curried favour with them by
indirect means; grocers and small shopkeepers did the same, and the coal-whippers had then to buy
bad and dear groceries instead of bad and dear beer and gin. The Legislature tried by various means to
protect the coal-whippers, but the publicans contrived means to evade the law. At length, in 1843, an
Act was passed, which has placed the coal-whippers in a far more advantageous position.
The transition from coal-labour to ballast-labour is gradual and easy, and would be even if the labourers
were not kindred in suffering.
The coal-ships, when discharged by the whippers, must get back to the north; and as there are not
cargoes enough from London to freight them, they must take in ballast to make the ships heavy enough
to sail in safety. This ballast is chiefly ballast or sand, dredged up from the bed of the Thames at and
near Woolwich Reach. The Trinity House takes upon itself this duty. The captain, when he requires to
sail, applies to the Ballast Office, and the required weight of ballast is sent to the ship in lighters
belonging to the Trinity House, the captain paying so much a ton for it. About 80 tons on an average
are required for each vessel, and the quantity thus supplied by the Trinity House is about 10,000 tons
per week. Some of the ships are ballasted with chalk taken from Purfleet; all ballast taken from higher
up the river than that point must be supplied by the Trinity House. When the ship reaches the Tyne, the
ballast is of no further use, but it must not be emptied into that river; it has, therefore, to be deposited
on the banks, where huge mounds are now collected two or three hundred feet high.
New places on the banks of the river have to be discovered for this deposit as the ballast mounds keep
increasing, for it must be recollected that the vessels leave these ports—no matter for what destination
—with coal, and may return in ballast. Indeed a railway has been formed from the vicinity of South
Shields to a waste place on the sea-shore, hard by the mouth of the Tyne, where the ballast may be
conveyed at small cost, its further accumulation on the river bank being found an incumbrance. “It is
really something more than a metaphor,” it has been said, “to designate this a transfer of the bed of the
Thames to the banks of the Tyne.” We may add as another characteristic, that some of the older ballast
mounds are overgrown with herbage. As the vessels from foreign ports returning to the coal-ports in
ballast, have not unfrequently to take soil on board for ballast, in which roots and seeds are contained,
some of there struggle into vegetation, so that Italian flowers not unfrequently attempt to bloom in
Durham, Yorkshire, or Northumberland, while some have survived the climate and have spread around;
and thus it is that botanists trace the history of plants which are called indigenous to the ballast-hills.
Before treating of the ballast labourers themselves I shall give a brief history of the ballast laws.
Ships are technically said to be in ballast when they sail without a cargo, having on board only the
stores and other articles requisite for the use of the vessel and crew, as well as of any passengers who
may be proceeding with her upon the voyage. In favour of vessels thus circumstanced it is usual to
dispense with many formalities at the custom-houses of the ports, and to remit the payment of the dues
and charges levied upon ships having cargoes on board. A foreign vessel proceeding from a British port
may take chalk on board as ballast. Regulations have at various times been made in different ports and
countries, determining the modes in which ships may be supplied with ballast, and in what manner they
may discharge the same, such regulations being necessary to prevent injury to harbours. Charles I.
published a proclamation in 1636, ordering that none shall buy any ballast out of the river Thames but a
person appointed by him for that purpose. And this appointment was sold for the king’s profit. Since
then the soil of the river Thames has been vested in the corporation of the Trinity House, and a fine of
10l. may be recovered for every ton of ballast taken out of the river without the authority of the
corporation. Ships may take on board land-ballast from any quarries or pits east of Woolwich by paying
1d. per ton to the Trinity House. For river-ballast the corporation are authorised by Act of Parliament to
make other charges. The receipts of the Trinity House from this source were 33,591l. in the year 1840,
and their expenses were 31,622l., leaving a clear profit of 1969l. The ballast of all ships or vessels
coming into the Thames must be unladen into a lighter, and if any ballast be thrown into the river the
master of the vessel whence it is thrown is liable to a fine of 20l. Some such regulation is usually
enforced at every port.
Before proceeding further with my present subject, it is proper that I should express my
acknowledgments of the ready courtesy with which the official information necessary for the full
elucidation of my subject was supplied to me by the Secretary of the principal Ballast Office at Trinity
House, Tower Hill. I have always observed, that when the heads of a department willingly supply
information to go before the public, I find in the further course of my investigations that under such
departments the claims of the labourer are not only acknowledged but practically allowed. On the other
hand, if official gentlemen neglect (which is to refuse) to supply the returns and other information, it is
because the inquiry is unpalatable to them, as the public may find that in their departments the fair
claims of the labourers are not allowed. Were the poor ballast-heavers taken under the protection of the
corporation of the Trinity House (something in the same way that Parliament has placed the coal-
whippers under the guardianship of a board of commissioners) the good done would be great indeed,
and the injury would be none: for it cannot be called an injury to prevent a publican forcing a man to
buy and swallow bad drink.
By charter of Queen Elizabeth in the 36th year of her reign, the lastage and ballastage, and office of
lastage and ballastage, of all ships and other vessels betwixt the bridge of the city of London and the
main sea, I am informed by the Secretary of the Trinity Company, was granted to the Master Wardens
and Assistants of the Trinity House of Deptford Strond. This was renewed, and the gravel, sand, and soil
of the river Thames granted to the said master wardens, &c. for the ballasting of ships and vessels in
the 15th year of Charles II., and again in the 17th year of the reign of that monarch. This last-named
charter remains in force, and has been confirmed by Acts of Parliament at different times; by which Acts
also various regulations in relation to the conduct of the ballast service, the control of the persons
employed therein, and the prices of the ballast supplied, have been established. The Act now in force is
the 6th and 7th Vict. cap. 57.
The number of men employed in lighters as ballast-getters, or in barges conveying it from the dredgers,
is 245, who are paid by the ton raised.
The number of vessels entered for ballast in the year 1848 was:
Colliers 6,480
British merchant vessels 3,690
Aliens 1,054
Total vessels 11,224

The total quantity of ballast supplied to shipping in the year 1848 was 615,619 tons, or thereabouts;
such ballast being gravel raised from the bed of the river Thames and delivered alongside of vessels,
either lying in the different docks or being afloat in the stream between London-bridge and Woolwich.
The number of vessels employed in this service is 69, viz:—
Men.
3 steam dredging-vessels, having 8 men in each 24
43 lighters, having 4 men in each 172
9 lighters, having 5 men in each 45
14 barges, having 2 men in each 28
69 Total 269
The ballast is delivered into the vessels from the lighters and barges by men called ballast-heavers, who
are employed by the vessel, and are not in the service of the Trinity House.
I now come to the nature of the ballast labour itself. This is divisible into three classes: that performed
by the ballast-getters, or those who are engaged in raising it from the bed of the Thames; by the
ballast-lighters, or those who are engaged in carrying it from the getters to the ships requiring it; and
by the ballast-heavers, or those who are engaged in putting it on board of such ships. The first and
second of these classes have, according to their own account, “nothing to complain of,” being employed
by gentlemen who, judging by the wanton neglect of labouring men by their masters, so general in
London, certainly exhibit a most extraordinary consideration and regard for their work-people; and the
change from the indifference and callousness of the coal-merchants to the kindness of the corporation
of the Trinity House is most gratifying. The ballast-heavers constitute an entirely different class. They
have every one, to a man, deep and atrocious wrongs to complain of, such as I am sure are unknown,
and which, when once made public, will at once demand some remedy.

I must, however, first deal with

The Ballast-Getters.
Of these there are two sub-classes, viz. those engaged in obtaining the ballast by steam power, and
those who still procure it as of old by muscular power.
Of seven dredging-engines employed in the collecting of ballast from the bed of the Thames there are
three, the Hercules, the Goliath, and the Samson. These are now stationed respectively in Barking
Reach, Half Reach near Dagenham, and the bottom of Half-way Reach off Rainham. Most persons who
have proceeded up or down the Thames will have perceived black unshapely masses, with no visible
indications that they may be classed with steam-vessels except a chimney and smoke. These are the
dredging-vessels; they are of about 200 tons burden. The engines of the Hercules and the Samson are
of 20-horse power,—those of the Goliath are 25. When the process of dredging is carried on, the use of
the dredging-vessel is obvious to any spectator; but I believe that most persons imagine the object to
be merely to deepen the river by removing inequalities in its bed, and so to render its navigation easier
by equalizing its depth, and in some degrees checking the power of cross-currents. Few are aware that
an ulterior object is gained. I visited one of these steam-dredgers, and was very courteously shown
over it. The first feeling was an impression of the order, regularity, and trimness that prevailed. In the
engineers’ department, too, there was an aspect, as well as a feeling, of extreme snugness, the more
perceptible both to the eye and the body from its contrast with the intense cold on the muddy river
outside, then running down in very strong ebb. In the engineers’ department there was more than
cleanliness; there was a brightness about the brass-handles attached to the machinery, and, indeed,
about every portion of the apparatus at all susceptible of brightness, which indicated a constant and
systematic attention by well-skilled hands. Each dredger carries eight men, the master (called the
captain, commonly enough, on the river), two engineers, an engineer’s assistant, two legsmen (who
attend to the ladders), and three men for general purposes. They are all called engine-men. The master
of the dredger I visited had the weather-beaten look of the experienced seaman, and the quiet way of
talking of past voyages which is found generally in men who have really served, whether in the
merchant service or royal navy. He resided on board the dredger with his wife and family, the principal
cabin being a very comfortable parlour. All the men live on board, having their turns for visit to the
shore from Saturday morning, noon, or evening (as their business permits), to Monday morning. Their
sleeping-places are admirable for cleanliness. All the dredgers are under the control of the corporation
of the Trinity House. They are, as it was worded to me, as strong as wood and iron can make them. But
for secure anchorage these dredgers would soon go adrift. Colliers beating up or down occasionally run
against the dredgers: this happens mostly in light winds, when the masters of these colliers are afraid
to let go their anchors. The machinery consists of a steam-engine and spur-gear for directing the
buckets. The application of the steam-power I need not minutely describe, as it does not differ from
other applications where motion has to be communicated. It is connected with strong iron beams,
having cogged and connected wheels, which when put into operation give upward and downward
motion to the buckets. These buckets are placed on ladders as they are called, one on each side the
vessel. These ladders (or shafts) consist of three heavy beams of wood, firmly bolted together and
fitted with friction-wheels. To each ladder 29 buckets are attached, each bucket holding 2½ cwt. of
gravel. Each bucket is attached by joints to the next, and a series of holes permits the water drawn up
with the deposit to ooze out. When the bucket touches the bottom of the river it dips, as it is called. A
rotary motion being communicated, the construction ensures the buckets being brought up flat on the
ladder until a due height is attained, when the rotary (or circular) motion again comes into play, and the
contents of the bucket are emptied into a lighter moored alongside, and the empty bucket is driven
down to be refilled. The contents so drawn up are disposed of for ballast, which is the ulterior purpose I
have alluded to. Upon an average the buckets revolve once in two minutes. That time, however, varies,
from the nature of the bed of the river. The Goliath and the Samson being fitted up with marine engines
drive the fastest. The three vessels have for the last year worked within a circle of a mile. The quantity
of ballast raised depends upon the demand, as well as upon the character of the deposit at the bottom
of the river. Between 900 and 1000 tons have been raised in 7½ hours, sometimes in a like period less
than 300 tons have been raised. The dredger I was on board of has taken in a year from 180,000 to
190,000 tons. A stratum of mud 2½ feet had been raised, then 3 feet of gravel, and a chalk bottom was
anticipated. In some places 15 feet have been so cleared away to a chalk bottom. In others 15 feet
have been so worked off, and no bottom but gravel reached. The gravel lies in shoals. Sometimes the
dredgers come to hard conglomerate gravel, as compact as a rock. No fossils have been found. In a few
places a clay bottom has been met with. The men in the dredgers are paid according to the number of
tons raised, the proceeds being duly apportioned. They work as frequently by night as by day, their
labour depending upon the time when an order for a supply of ballast is received. Each lighter holds 60
tons of ballast. The dredgers above bridge are the property of individuals working with the concurrence
of the civic corporation of London. Those below bridge are, as I have said, under the control of the
corporation of the Trinity House. The Hercules was the first Trinity House dredger worked by steam.
Private individuals, however, employed steam sooner than the Trinity House authorities to draw up
materials to mix with lime for building purposes. The first Trinity House steam-dredger was started in
1827.
I had some conversation with a man employed on one of the steam-dredgers. He described the process
carried on there as I have given it, estimating the tons of ballast raised at about 4000 a-week. He
expressed a sense of his good fortune in having the employment he had; he was well used, and
wouldn’t like to change. He declined stating his earnings (otherwise than that he had his fair share)
until he saw his master, and of course I did not press him further on the subject.
The ballast-getters are men employed in raising ballast from the bed of the river by bodily labour. The
apparatus by which this is effected consists of a long staff or pole, about thirty-five feet in length. At the
end of this is an iron “spoon” or ring, underneath which is a leathern bag holding about 20 cwt. The
ballast is raised on board the working-lighters by means of this spoon. The working-lighters carry six
hands: that is, a staffsman whose duty it is to attend to the staff; a bagman, who empties the bag; a
chainsman, who hauls at the chain; a heelsman, who lets go the pall of the winch; and two trimmers,
who trim the ballast in the lighter as fast as it comes in. Previous to the men getting at work, the
staffsman takes hold of the spoon to feel whereabout the ballast-bed lies. When this is found, he puts
down his “sets,” as it is termed,—that is to say, he drives the iron-tipped spars that he has with him in
the lighter into the ground, so as to steady the craft. This done, the staffsman seizes hold of the middle
of the staff, while the bargeman takes the bag and the chainsman the chain, which is fastened to the
iron ring or spoon; the staff is thus thrown overboard into the water, about midway of the lighter, and
the tide carries the spoon down towards the stern. The staffsman then fastens the staff to the lighter by
means of the gaff-string or rope attached to the side of the vessel. At the same time the men go
forward to heave at the winch, round the roll of which the chain attached to the spoon itself is wound.
All the men, with the exception of the staffsman, then heave away, and so drag the spoon along the
bed of the river. When the staffsman feels that the bag is full, he leaves go of the gaff-string and goes
forward to heave with the men as well. Immediately the gaff-string is undone the top part of the staff
falls back on an oar that projects from the after-part of the vessel, and the bag is then raised by means
of the winch and chain to the level of the gunwale of the craft; then the bagsman hauls it in and
empties it into the lighter, while the two trimmers spread the ballast discharged. The spoon can only be
worked when the tide is nearly down, because the water would be too deep for the set to bring the
craft steady. To hoist the 20 cwt. of ballast in the bag will require the whole force of the six men; and
none but the very strongest are of use. The ballast-getters are all very powerful men; they are mostly
very tall, big-boned, and muscular. Many of them are upwards of six feet high, and have backs two feet
broad. “I lifted seven half-hundredweights with one of my hands,” said one whom I saw. He was a man
of thirty-nine years of age, and stood half an inch over six feet, while another was six feet two inches.
They were indeed extraordinarily fine specimens of the English labourer, making our boasted Life-
guardsman appear almost weak and effeminate in comparison with them. Before the steam dredging-
engines were introduced, I am informed the ballast-getters were even bigger and heavier men than
they are now. The ballast-getters seldom or never fish up anything besides ballast. Four or five years
back they were lucky enough to haul up a box of silver plate; but they consider a bit of old iron or a bit
of copper very good luck now. The six men generally raise sixty tons eighteen feet high in the course of
the tide, which is at the rate of 22,400lbs. each man in three hours: this makes the quantity raised per
hour by each man upwards of 7400 lbs. The price paid is 8d. per ton, or 2l. for sixty tons; this is shared
equally among five of the men, who receive 8s. a-piece as their proportion, and out of this they pay 3s.
6d. a tide to the stern-trimmer, whom they employ—the Trinity Company allowing only five men and the
ballast-getters engaging the sixth man themselves. Upon an average the ballast-getters do about three
loads in the week throughout the year,—this, deducting the money paid to the sixth man, makes the
earnings of each ballast-getter come to about 22s. throughout the year. The staffsman is allowed 20l. a-
year to keep the craft in gear. The ballast-getters usually work above the dredging-engines, mostly
about Woolwich; there the cleanest ballast is to be got. The Trinity Company they speak most highly of;
indeed the corporation are universally spoken of as excellent masters: the men say they have nothing to
complain of. They get their money on every Friday night, and have no call to spend a farthing of their
earnings otherwise than as they please. They only wish, they add, that the ballast-heavers were as well
off. “It would be a good job if they was, poor men,” say one and all.
The second class of ballast-labourers are

The Ballast-Lightermen.
These are men engaged by the Trinity Company to carry the ballast in the company’s barges and
lighters from the steam dredging-engines to the ship’s side. The corporation has fifty-two lighters and
fourteen barges, all sixty-ton craft. Each lighter carries four men, and there are two men in each barge;
so that altogether 108 lightermen and 28 bargemen are employed in bringing the ballast from the
engines. These men are not required to have a license from the Waterman’s Company, like other
lightermen and bargemen on the Thames, and that is one of the reasons for my dealing with them at
present. They form a class of labourers by themselves, and I treat of them here because it appears the
fittest place for a statement of their condition and earnings. Besides the lightermen and bargemen
engaged in carrying the ballast from the steam dredging-machines, there are others employed on board
what are called the working-lighters; these are vessels in which ballast is got up from the bed of the
river by muscular labour. There are ten of these working-lighters, and six men engaged in each, or in all
sixty men employed in raising ballast by such means. There are three steam dredging-engines
employing each eight men, or twenty-four in all; so that there are altogether 220 labouring men
engaged in the ballast service of the Trinity Company. Each of the carrying lighters has a staffsman or
master and three men. The lighters all carry sixty tons of ballast, and make upon an average between
three and four voyages a-week, or about seven in the fortnight. There is no place of deposit for the
ballast brought up the river from the engines; it is left in the lighter until required. The ballast chiefly
consists of gravel; indeed the ships will mostly refuse anything else. When there is a plentiful supply of
ballast they will refuse clay in particular. Clayey ballast is what is termed bad ballast. Upon an average
there are thirty loads, or 1800 tons of ballast, brought up by the lighters every day from the engines. In
the course of the year there are between 550,000 and 600,000 tons of ballast supplied by the three
steam dredging-machines. “It is about three-and-twenty years since the steam dredging-engine first
came out,” said the party who gave me the above information. “For the last twenty years I should think
the company have been raising about 500,000 tons of gravel from the bed of the river. Thirty years ago
I thought the ballast would soon be out, but there appears to be little or no difference; and yet the
shoals do not fill up again after being once taken away. In Barking Reach I am sure there is six feet
more water now than there was thirty years ago; there was at that time a large shoal in that part of the
river, called Barking Shelf; it was certainly a mile long and half a mile wide. The vessels would ground
upon it long before low water. At some tides it used to strip dry, and at low tide generally there was
about six foot of water over it. That part of the river is now the deepest about Barking, and as deep as
the best of places in the Thames. When I first came to London we were prevented from getting the
ballast from anywhere else than Barking, on account of the great shoals there; but now the great
ballast-bed is between four and five miles lower down. The river has been very nearly cleared of shoals
by the dredging-engines, from Limehouse Reach to the bottom of Half Reach. The only shoal in the way
of the navigation below the Pool is what is called Woolwich Shelf: there is indeed another shoal, but this
consists of stiff clay or conglomerate, and the engines cannot work through it.” The men on board the
carrying-lighters are paid 5d. a-ton for bringing the ballast from the dredging-engines to the ships; this
is equally divided among the four men. The staffsman, in addition to his fourth share, receives 10l. a-
year for his extra duties; but out of this he has to buy oars for the boat and lighter, locks, fenders, and
shovels. Upon an average the cost of these will be about 30s. a-year. Each man’s share of the sixty-ton
load is 6s. 3d.; and there are about seven loads brought up by each lighter in the fortnight. Some
weeks the men can earn as much as 37s., but at others they cannot get more than 12s. 6d. “I did
myself only two load last week,” said my informant. “When there is little or no ‘vent,’ as we call it, for
the ballast—that is, but a slight demand for it—we have but little work. Upon an average, each
lighterman makes from 21s. to 22s. a-week. At the time of the strike among the pitmen in the North,
the lightermen, generally, only did about two load a-week throughout the year; but then the following
year we had as much as we could do. The Trinity Company, whom I serve, and have served for thirty
years, are excellent masters to us when we are sick or well. The corporation of the Trinity House allow
the married lightermen in their service 10s. and the single ones 7s. 6d. a-week, as long as they are ill. I
have known the allowance given to men for two years, and for this we pay nothing to any benefit
society or provident fund. If we belong to any such society we have our sick money from them
independent of that. The superannuation money is now 6l. a-year; but I understand,” continued the
man, “that the company intend increasing it next Tuesday. Some of the old men were ordered up to the
house a little while ago, and were asked what they could live comfortably upon, and one of the
gentlemen there promised them that no more of us should go to the workhouse. They do not provide
any school for our children; a great many of the lightermen neither read nor write. I never heard any
talk of the company erecting a school, either for the instruction of their men or their men’s families. All I
can say is, that in all my dealings with the Trinity Corporation I have found them very kind and
considerate masters. They are always ready to listen to the men, and they have hospitals for the sick in
their employ and midwives for the wives of the labourers; and they bury, free of expense, most of the
men that die in their service. To the widows of their deceased servants they allow 6l. a-year; and if
there be any children, they give 2s. a-month to each under fourteen years old. I never knew them to
reduce the lightermen’s wages; they have rather increased than lowered them. After the introduction of
the steam-dredging machines we were better off than we were before. Previous to that time the
lightermen were getters as well, and then the labour was so hard that the expenses of the men for
living were more than they are now.”

I now come in due order to

The Ballast-Heavers.
Of these I can at present give but a general description. The individual instances of oppression that I
have sought out I must reserve for a subsequent page, when I most heartily hope that the publication
of the iniquity of which these poor fellows are the victims, will be at least instrumental in putting an end
to a most vile and wicked plan for the degradation and demoralization of our fellow-creatures. The tales
I have to tell are such as must rouse every heart not positively indurated by the love of gain. I must,
however, be here content, as I said before, with merely describing the system.
The duty of the ballast-heaver is to heave into the holds of the ship the ballast brought alongside the
vessel by the Trinity-lighters from the dredging-engines. The ships take in ballast either in the docks or
in the Pool. When the ship is cranky-built, and cannot stand steady after a portion of her cargo has
been discharged, she usually takes in what is called shifting or stiffening ballast. The ballast is said to
stiffen a cranky vessel, because it has the effect of making her firm or steady in the water. The quantity
of ballast required by cranky vessels depends upon the build of the ships. Sixty tons of cargo will stiffen
the most cranky vessel. I am informed by those who have been all their lives at the business, that they
never knew a vessel, however cranky, but what 60 tons’ weight would stiffen her. Some vessels are so
stiff-built, that they can discharge the whole of their cargo without taking in any ballast at all. These are
generally flat-bottomed vessels, whereas cranky vessels are built sharp towards the keel. The colliers
are mostly flat-bottomed vessels, and could in calm weather return to the north without either ballast or
cargo in them. This, however, is not allowed by the owners. The generality of ships discharge all their
cargo before they take in any ballast. The cranky-built ships form the exception, and begin taking in
ballast when they are about three-parts discharged. When a ship requires ballast, the owner or one of
his agents or servants applies to the Trinity House for the quantity needed. If the ship belong to the
merchant service, and is lying in any of the docks, the owner has to pay 1s. 7d. per ton to the Trinity
Company for the ballast supplied: but if the merchant vessel be lying in the Pool, then the price is 1s.
3d. per ton, and if the vessel be a collier, the price is 1s. per ton. On application being made at the
Ballast Office, the party is supplied with a bill, specifying the name and situation of the vessel, the
quantity of ballast required for her, and the price that has been paid for it. The bill is then taken to the
Ruler’s Office, where it is entered in a book, and the ship supplied with the ballast, according to the
place that she has on the books. If the weather is rough, a ship has often to remain three or four days
without receiving the ballast she wants. The application for ballast is seldom made directly from the
captain or shipowner himself. There are parties living in the neighbourhood of Wapping and Ratcliffe
who undertake, for a certain sum per score of tons, to have the requisite quantity of ballast put aboard
the ship. These parties are generally either publicans, grocers, butchers, lodging-house keepers or
watermen, and they have a number of labourers dealing with them whom they employ to heave the
ballast on board. The publicans, butchers, grocers, or lodging-house-keepers, are the ballast-
contractors, and they only employ those parties who are customers at their houses. It is the owner or
captain of the vessel who contracts with these “truckmen” for the ballasting of the ship at a certain
price per score of tons, and the truckmen for that sum undertake not only to procure the ballast from
the Trinity Company, and save the owner or captain all the trouble of so doing, but also to carry it from
the Trinity-lighters on board the ship. The reason of the publicans, grocers, butchers, or lodging-house-
keepers, undertaking the job is to increase the custom at their shops, for they make it a rule to employ
no heavers but those who purchase their goods from them. The price paid to these truckmen varies
considerably. Their principal profit, however, is made out of the labourers they employ. The highest price
paid to the contractors for putting the ballast on board colliers (exclusive of the cost of the ballast itself)
is 10s. per score tons. Many contractors charge less than this—not a few indeed undertake to do it for
9s., and there are one or two who will do it for 8s. the score. But these, I am informed, “are men who
are trying to get the work away from the other contractors.” The highest price paid to the contractors
for ballasting small merchant vessels is 12s. per score as well. For large vessels the price varies
according to their size, and, consequently, the number of heavers required to put the ballast on board.
The lowest price paid per score to the contractors for small merchant vessels is 10s. Eight or nine years
ago the price for ballasting small merchant vessels was much higher. Then the highest price paid to the
contractor was 15s. Since that time the prices both for merchant vessels and colliers have been
continually falling. This, I am told, arises from the number of contractors increasing, and their continual
endeavours to underwork one another. Before the establishment of the Coal-whippers’ Office, the
contractors for ballast were solely publicans; and they not only undertook to put ballast on board, but to
deliver the coals from the ships as well. At this time the publicans engaged in the business made rapid
and large fortunes, and soon became shipowners themselves, but after the institution of the Coal-
whippers’ Office, the business of the publicans, who had before been the contractors, declined. Since
that period the contracts for ballasting ships have been undertaken by butchers and grocers, as well as
publicans, and the number of these has increased every year, and according as the number of the
contractors has increased, so have the prices decreased, for each one is anxious to undersell the other.
In order to do this, the contractors have sought everywhere for fresh hands, and the lodging-house-
keepers in particular have introduced labouring men from the country, who will do the work at a less
price than those who have been regularly brought up to the business: and I am credibly informed, that
whereas nine or ten years ago every ballast-heaver was known to his mates, now the strangers have
increased to such an extent that at least two-thirds of the body are unacquainted with the rest. There is
treble the number of hands at the work now, I am told, to what there was but a few years back. The
prices paid by the contractors to the ballast-heavers are very little below what the owners pay to them,
indeed some of the publicans pay the heavers the same price that they themselves receive, and make
their profit solely out of the beer and spirits supplied to the workmen. The butchers and grocers
generally pay the men 6d. and some 1s. in the score less than they themselves get; but, like the
publican, their chief profit is made out of the goods they supply. The lodging-house-keepers seldom
contract for the work. They are generally foremen employed by the publican, butcher, or grocer
contracting, and they make it a rule that the ballast-heavers whom they hire shall lodge at their house,
as well as procure their beer, meat, or grocery, as the case may be, from the shop of the contractor by
whom they are employed. All the English ships that enter the port of London are supplied with ballast in
this manner. The owners always make it a rule to contract with some publican, butcher, grocer, or
lodging-house-keeper for the ballasting of their vessels, and it is impossible for the ballast-heaver to
obtain employment at his calling but by dealing at the shops of some or other of these parties.
According to the Government returns there were 170 ballast-heavers in the metropolis in 1841, and I
am assured that there are more than double that number at present, or nearly 400 labourers engaged
in the business. There are now 27 publicans who make a regular business of contracting for the supply
of ballast. Besides these there are four butchers, the same number of grocers, and as many lodging-
house-keepers. Further than this, there is a foreman attached to each of the public-houses, or butchers’
or grocers’ shops, and these foremen are mostly lodging-house-keepers as well. The foremen in general
have the engagement of the heavers, and the first hands they employ are those who lodge at their
houses: these hands are expected also to deal with the contractor under whose foreman they serve.
The heavers generally, therefore, are obliged to lodge at the house of some foreman, and to obtain
their meat, beer, and grocery from the different ballast-contractors, in order to obtain work; indeed,
with the exception of clothing, the heaver is compelled to obtain almost every article he consumes
through the medium of some contractor. The greater the number of contractors the heaver deals with,
the greater is his chance of work. The rule with each of the contractors is to give credit to the hands
they employ, and those who are the most in debt with them have the preference in labour. The butchers
and grocers generally charge 1d. per lb. extra for everything they sell to the heavers, and the publicans
make it up in adulteration. Each of the publicans, butchers, and grocers, who make a rule of contracting
for the supply of ballast, has, on an average, two gangs of men dealing at his house, and if he have
more ships to supply than his regular hands are capable of doing, then he sends the foreman to either
of the places of call where the unemployed men wait for hire throughout the day. Each ship requires
from four to six heavers to put the ballast on board, and the men generally ship about 50 tons in the
course of the day. They often do as much as 100 tons, and sometimes only 20 in the day. The heavers
are divided into constant and casualty men.
The constant men are the first gang working out of the public-house, or butchers’ or grocers’ shops.
The constant men with the publicans are those that are the best customers. “If they didn’t drink,” said
my informant, “they’d be thought of very little use.” These constant men make three times as much as
the casualty men, or, in other words, they have three times as much to drink. Generally, one-fifth part of
what the publican’s constant men earn is spent in drink. The casualty men are those who belong to no
regular houses; but these, if taken on by a publican, are expected to spend the same amount in drink
as the constant men. There are no ballast-heavers who are teetotalers. “Indeed it would be madness,”
says my informant, “for a man to think of it, for to sign the pledge would be entirely to deprive himself
and his family of bread.”
To complete the different classes of ballast-labourers, I will conclude with the statement of a casualty
man:—
“I am about 57,” (said my informant, who was 6 feet high, and looked like a man far older than 57,)
“and have been 35 years a ballast-heaver, with the exception of seven or eight years, when I had the
care of some horses used in coal-waggons. When I first knew the trade, earnings was good. I might
clear my 1l. a-week. On that I brought up four sons and one daughter—all now married. At that time, I
mean when I first worked at ballast-heaving, the men were not so much employed by publicans and
other tradesmen. A gang of men could then get work on their own account, a good deal easier than
they can get it now through the tradesmen who supply the ballast. As the trade got more and more into
the hands of the publicans and such-like, it grew worse and worse for such as me. We earned less, and
were not anything like to call free men. Instead of my 1l. I had to stir myself to make 15s. or as low as
12s. a-week. Lately I have been what is called a casualty man. There’s constant men and casualties.
Each publican has a foreman to look out, and get men, and see after them. These foremen—all of them
that I know of—keeps lodgers, charging them 2s. 6d. or 3s. a-week for a room they could get but for
this tie, for 2s.—ay, that they could. Suppose now a publican has a ship to supply with ballast, he
acquaints his foreman, and the foreman calls on his lodgers, and sets them to work. These are the
constant men. They have always the first turn out of the house. If they return from work at 4, and
there’s another job at 5, they get it. That’s interest you see, sir. The more such men earn this way, the
more they’re expected to spend with the publican. It’s only bad stuff they have to drink at a full price.
It’s only when all the constant men are at work, and a job must be done at once, that me, and such as
me, can get work. If I hear of a chance of a job I call on the foreman. If I have money, why, I must
drink myself, and treat the foreman with a drop of gin, or what he fancies. If I haven’t the money, I
have the worse chance for a job. Suppose I get a job and earn 6s. out of 60 tons of ballast; out of that
6s. I may have 4s., or, at most, 4s. 6d. to take home with me, after paying for what I must drink at the
publican’s—what I’m forced to spend. Casualty men have sad trouble to get any work. Those that
belong to the houses have all the call. Last week I was on the look-out every day, and couldn’t get a
single job, nor earn a single farthing. Last night I had to get a bite of supper at my son’s, and a bite of
breakfast this morning as well, and I had to borrow a pair of shoes to come out in. The best week’s
work I’ve had this winter was 15s. I had five days in one ship. For that five days I was entitled, I fancy,
to 20s., or may be 21s., so that the difference between that and the 15s. went for drink. I only wanted
a pint of beer now and then at my work—two or three a day. The worst of it is, we don’t get drink at
our work so much as at the public-house we’re employed from. If we want to go home, some of the
constant men want to have more and more, and so the money goes. Other weeks I have carried home
10s., 8s., 5s., and many a week nothing, living as I could. It would be a deal better for poor men, like
me, if tradesmen had nothing to do with ballast work. If the men that did the work were paid by the
gentlemen what wants the ballast, there might then be a living for a poor man. As it is, it’s a very bad,
hateful system, and makes people badly off. A ballast-man may sit in a tap-room, wet, and cold, and
hungry, (I’ve felt it many a time,) and be forced to drink bad stuff, waiting to be paid. It always
happens, unless they’re about shutting up, that we have to wait. We have no sick-fund or benefit
societies. I declare to you, that if anything happened to me—if I was sick—I have nothing to call my
own but what I’ve on; and not all that, as I’ve told you—and there’s nothing but the parish to look to.
(Here the man somewhat shuddered.) I pay 2s. a-week rent.
“Then again, sir, there’s the basket-men at the docks—all the docks. They’re as bad to the poor man as
the publican, or worse. The way they do is this. They’re not in any trade, and they make it their
business to go on board ships—foreign ships—American generally. In better times, twenty or twenty-five
years ago, there used to be 1s., and as high as 1s. 6d. paid for a ton from such ships to a gang of six
ballast-men. I’ve earned six, seven, and eight shillings a-day myself then. We heaved the ballast out of
the lighters with our shovels on to a stage, and from that it was heaved into the hold. Two men worked
in the lighter, two on the stage, and two in the hold of the vessel. The basket-men manage to fill the
hold now by heaving the ballast up from the lighter in baskets by means of a windlass. The basket-man
contracts with the captain, and then puts us poor men at the lowest rate he can get; he picks them up
anywhere, anything in the shape of men. For every half-crown he pays these men he’ll get 9s. for
himself, and more. An American liner may require 300 tons of ballast, and, maybe, a captain will give a
basket-man 8d. a-ton: that would be 10l. The basket-man employs six men, and he makes another. He
never works himself—never—not a blow: but he goes swaggering about the ship when his men are at
work, and he’s on the look-out in the streets at other times. For the 10l. he’ll get for the 300 tons, he’ll
pay his men each 2s. 6d. for 60 tons, that is 3l. 15s., and so there’s 6l. 5s. profit for him. Isn’t that a
shame, when so many poor men have to go without dinner or breakfast? There’s five basket-men to my
knowledge. They are making money all out of poor men that can’t help themselves. The poor suffers for
all.”
In order to assure myself of the intensity of the labour of ballast-heaving, of which I heard statements
on all sides, I visited a gang of men at work, ballasting a collier in the Pool. My engagements prevented
my doing this until about six in the evening. There was a very dense fog on the river, and all along its
banks; so thick was it, indeed, that the water, which washed the steps where I took a boat, could not
be distinguished, even with the help of the adjacent lights. I soon, however, attained the ballast-lighter I
sought. The ballast-heavers had established themselves alongside a collier, to be filled with 43 tons of
ballast, just before I reached them, so that I observed all their operations. Their first step was to tie
pieces of old sail, or anything of that kind, round their shoes, ankles, and half up their legs, to prevent
the gravel falling into their shoes, and so rendering their tread painful. This was rapidly done; and the
men set to work with the quiet earnestness of those who are working for the morrow’s meal, and who
know that they must work hard. Two men stood in the gravel (the ballast) in the lighter; the other two
stood on “a stage,” as it is called, which is but a boarding placed on the partition-beams of the lighter.
The men on this stage, cold as the night was, threw off their jackets, and worked in their shirts, their
labour being not merely hard, but rapid. As one man struck his shovel into the ballast thrown upon the
stage, the other hove his shovelful through a small porthole in the vessel’s side, so that the work went
on as continuously and as quickly as the circumstances could possibly admit. Rarely was a word spoken,
and nothing was heard but an occasional gurgle of the water, and the plunging of the shovel into the
gravel on the stage by one heaver, followed instantaneously by the rattling of the stones in the hold
shot from the shovel of the other. In the hold the ballast is arranged by the ship’s company. The
throwing of the ballast through the porthole was done with a nice precision. A tarpaulin was fixed to
prevent any of the ballast that might not be flung through the porthole being wasted by falling into the
river, and all that struck merely the bounds of the porthole fell back into the lighter; but this was the
merest trifle. The men pitched the stuff through most dexterously. The porthole might be six feet above
the stage from which they hove the ballast; the men in the lighter have an average heave of six feet on
to the stage. The two men on the stage and the two on the lighter fill and discharge their shovels
twelve times in a minute; that is, one shovelful is shot by each man in every alternate five seconds; so
that every one of the four men engaged at the work flings the height of 36 feet every minute, or 2160
feet in an hour; and in that time, according to the concurrent computation of the heavers, the four men
may easily fling in 10 tons, or 5600 lbs. a man. The men work with the help of large lanterns, being
employed mostly by night.
I shall now state the sentiments of the men generally, and then individually, upon the subject of their
grievances.
To be certain as to the earnings of the men, to see their condition, and to hear from a large number of
them their own statements as to the hardships they suffered, and the sums they gained, I met two
bodies of the ballast-heavers, assembled without pre-arrangement. At one station 50 were present, at
the other 30. The men were chiefly clad in coarse, strong jackets; some of them merely waistcoats, with
strong, blue flannel sleeves, and coarse trowsers, thick with accumulated grease from long wear. They
had, notwithstanding their privations, generally a hardy look. There was nothing squalid in their
appearance, as in that of men who have to support life on similar earnings with in-door employment.
Their manners were quiet, and far from coarse. At the first meeting 50 were present. One man said,
“Well, I think I am the oldest man at present, and I don’t get above 5s. a-week; but that’s because I’m
an old man, and cannot work with the young ones.” Upon an average the common men earned 10s. a-
week the year through, and took home 5s. I inquired, “Are you all compelled to spend a great part of all
you earn in drink with the publican?” The answer was simultaneously, “All of us—all—all!” Of the
remainder of their earnings, after the drink deductions, the men were all satisfied they spent so much,
that many only took 2s. 6d. a-week home to their wives and families on an average. Last week two
earned 20s., the publican taking 10s. from each. Three earned 15s.; one of these took 1s. 6d. home,
the other 3s., both working for publicans; the third, who worked for a grocer, took home 13s.; the other
2s. being spent in tea and sugar, he being a single man. Three earned 10s.; one, working for a
publican, carried home 6s., the difference going in compulsory drink; another 4s., and another 5s. Six
did one load of ballast, receiving 7s. 6d. each for it; one took home 4s. 11d.; another 6s. 6d. (a private
job); another, who did a load for 5s. 3d., took home 2s. 3d.; the other two took home 5s. each. One
man earned 3s., and took it all home, having worked at a private job for a foreigner. Fifteen earned
nothing in the course of the last week. For the last fortnight nine had earned nothing. There were nine
present that had earned something in the last three weeks. “The fortnight before Christmas,” said one,
“I didn’t earn 5s. all that fortnight.” “Nor I, nor I,” said several others. On being asked, “Are you
compelled to spend half of your earnings in drink?” there was a general cry of, “More than that, sir;
more than that.” I asked if men were forced to become drunkards under this system; there was a
general cry of, “We are; and blackguards, too.” Seventeen were married men. Of them, 3 had no
children; 3 had one child; 4 had 2 children; 2 had 3; 3 had 4; one had 5; one had 6. The men all said,
that to get away from the publican would be “a new life to them—all to their benefit—no force to waste
money in drink—and the only thing that would do them good.” Many threw away the drink they had
from the publicans, it was so bad; they drank Thames water rather. They were all satisfied “they earned
10s. a-week the year through, spending of that sum what they must spend, and what they were
induced to spend, from 5s. to 7s. 6d. a-week.” “Another thing,” they said, “if you get a job, the publican
will advance 1s.—now and then he may. They hate to give money; there’s trust for as much grog as you
like.” All hailed with delight the least possible chance of being freed from the publican. One man said he
was compelled often enough to pawn something of his own or his wife’s to go and spend it at the
public-house, or he would have no chance of a job. All declare “such a system never was known to have
been carried on for years.” Many said, “We shall be discharged if they know we have told you the truth.”
They stated that the ballast-heavers numbered between 300 and 400. There were 60 craft, each
requiring 4 heavers; and many men were idle when all the others were at work. Thirty were present
when I counted the other meeting. A man said there might be three times that number looking for work
then, and as many at work belonging to that station alone. In 1841 the census returns showed that
there were 170 ballast-heavers; the men assembled declared that their numbers had more nearly
trebled than doubled since then. Within the last two or three years many new hands had got to work,
on account of the distress in Ireland. The men agreed with the others I had seen that they earned, one
week with another, 10s., taking home but 5s. at the outside, and often only 2s. 6d. In answer to my
questions they said, the winter is the best season; the trade is very slack in summer. Earnings in winter
are pretty well double what they are in summer. Many agricultural labourers work among the heavers in
winter, when they cannot be employed on the land. Of this body all said they were sober men till they
took to ballast-heaving, and would like to become sober men again. (A general assent.) Three of the
men had taken the pledge before becoming ballast-heavers, and were obliged to break it to get work.
They had to drink five pots of beer, they declared, where, if they were free men, they would only drink
one. When asked if the present system made drunkards, they answered with one voice, “All; every
ballast-heaver in it.” Twenty were married men. All their wives and children suffered (this was affirmed
generally with a loud murmur), and often had nothing to eat or drink while their husbands had but the
drink. It was computed (with general concurrence) that 150 ballast-heavers paid foremen for lodgings,
not half of them ever seeing the bed they paid for. About twelve years ago they could earn twice or
three times as much as they can now; but prices were higher (12s. per score, for what is now 8s.), and
the men were far less numerous. The following is a precise statement of the sums to which each
ballast-heaver present was entitled, followed by the amount he had carried home the week before, after
payment of his compulsory drinkings, and of what he might be induced to drink at the house of his
employer while waiting to be paid:—
Earned. Took home.
£0 12 0 £0 7 6
0 70 0 3 6
0 15 0 0 9 0
0 12 0 0 6 0
 0 13 0 0 4 0
0 11 0 0 5 0
0 50 0 2 6
0 80 0 5 0
0 96 0 5 0
1 00 0 10 0
0 12 6 0 3 6
1 00 0 9 0
0 12 0 0 4 0
0 15 0 0 9 0
0 15 0 0 8 6
0 16 0 0 6 0
0 15 0 0 5 0
Nothing Nothing
„ „
„ „
„ „
0 12 0 0 2 6
0 90 0 5 0
1 00 0 4 6
1 00 0 10 0
0 10 0 0 3 0
0 10 0 0 5 0
0 12 0 0 2 6
0 80 0 3 6
0 14 0 0 9 0
£16 13 0 £7 7 0
This statement shows, out of 11s. 1½d. earnings, a receipt of less than 5s. a-week.
According to the returns of the Trinity House, there were 615,619 tons of ballast put on board 11,234
ships in the year 1848. The ballast-heavers are paid at the rate of 6d. per ton for shovelling the ballast
out of the Trinity Company’s lighters into the holds of vessels. Hence, the total earnings of the ballast-
heavers in that year were 15,390l. 9s. 6d. And calculating two-thirds (the men say they always get rid
of a half, and often three-fourths, of their earnings in drink) of this sum to have been spent in liquor, it
follows that as much as 10,260l. 6s. 4d. went to the publican, and only 5,130l. 3s. 2d. to the labouring
men. According to this estimate of their gross earnings, if we calculate the body of the ballast-heavers
as numbering 350 men, the average wages of the class are about 16s. 6d. per week each man; or if we
reckon the class at 400, then the average wages of each person would be about 14s. 6d. per week.
From all I can learn this appears to be about the truth—the earnings of the men being about 15s. a-
week, and their real income about 5s.

The men shall now speak for themselves.

The first that I saw were two of the better class of foremen, who volunteered to give me an account of
the system.
“I am a foreman or ganger of the ballast-heavers,” said one. “I work under a man who is a publican and
butcher; and I also work under another who is only a butcher. I, moreover, work under a grocer. I
engage the different gangs of men for the parties under whom I work. I also pay the men. The
publican, butcher, or grocer, as the case may be, agrees to give me 9s. a score tons. The foremen often
give the men the same money as they themselves receive, barring a pot of beer or a quartern of gin
that they may have out of the job. Some foremen take much more.”
Another foreman, who was present while I was taking the statement of this man, here observed, that
“Many foremen claim tow-tow, or a ‘fifth-handed’ proportion—that is, they will have 10s. when the
working men have only 5s. There is a great deal of imposition on the working-classes here, I can assure
you; the general thing, when we go to a job out of a public-house is, that the publican expects the men
to drink to the amount of 4s. out of every 1l., and 6s. out of every 30s. that’s coming to them—that is,
one-fifth part of the men’s money must be spent in liquor. The drink is certainly not the best; indeed, if
there is any inferior stuff they have it: it’s an obligation on them that they drink. If they refuse to drink,
they won’t get employed, and that’s the plain truth of it. Oh, it’s long wanted looking to; and I’m glad at
last to find some one inquiring into it. If they went to get the regular beer from the fair public-houses
they would have to pay 3d. a pot for it; and at the contracting publicans’ they must give 4d. a pot, and
have short measure, and the worst of stuff too. Every six pots of beer they give to the men is only five
pots fair measure; and the rum they charge them 2d. half-a-pint more than the regular public-houses
would, and far worse rum into the bargain. Besides the profit on their drink, some publicans charge 6d.
per score tons as well. Out of the money coming to the men after the publican has been paid his score,
many foremen claim one-fifth part over and above their regular share; or, in other words, the foremen
takes two shares, and the men only one each. When the men have been paid, the publican paying them
expects them to spend a further sum in drink, looking black at the man who goes away without calling
for his pint or his pot, and not caring if they drink away the whole of their earnings. There’s a good
many would be glad if the men sat in their houses and spent their last farthing, and then had to go
home penniless to their wives and families.”
“I am a ‘ganger’ to a butcher as well as a publican,” said one of the foremen. “His practice is just the
same as the publican’s. He receives 10s. per score tons, and pays me for the men 9s. The men and
myself are all expected to spend about one-half of our earnings with the butcher in meat. He charges
6½d. per lb.; and at other houses, with ready money, I and the men might get it for 4d. as good. His
meat is at least one-third dearer than other butchers’. I am also ganger to a grocer, and he gets about
the same profit out of the men he employs—that is to say, the articles he supplies the men with are at
least one-third dearer than at other shops. If anything, he makes more out of the men than the
butcher; for if any man goes a score (which he always encourages) he stops the whole out the man’s
earnings, and often leaves him without a penny after the job is done. When the publican, grocer,
butcher, or lodging-house keeper has a contract for ballast, he directs the foreman working under him
to get together the gang that regularly work from his house. This gang are men who always deal at the
shop, and the contractor would dismiss me if I was to engage any other men than those who were his
regular customers. Many a time a publican has told me that some man was a good, hard drinker, and
directed me to engage him whenever I could. If a man sticks up a score, he also tells me to put him on
first of all: the grocer and the butcher do the same. This system is the cause, I know, of much distress
and misery among the men; the publicans make the men drunkards by forcing them to drink. I know
many wives and children who starve half their time through it. They haven’t a bit of shoe or clothing,
and all through the publican compelling the men to spend their earnings in drink. After the gang is paid,
at least three out of the four get drunk; and, often, the whole four. Many a time I have seen the whole
of the men reeling home without a penny to bless themselves, and the wife and children have to suffer
for all this; they are ill-treated and half-starved: this I can safely say from my own knowledge.”
I next saw two men, who stated that they were oppressed by the publican, and the foreman also. The
first said, “I work under a publican, and have to pay the foreman one-fifth of my earnings; I only have
fourpence out of every shilling I earn, and I must be a sober man indeed to get that. Both the publican
and the foreman get eightpence out of a shilling, and make their money out of my sweat. Nine years
ago I was left, to my sorrow, with nine motherless children, and I am the slave of the publican. He is
my destruction, and such are my sufferings, that I don’t care what I do if I can destroy the system; I
shall die happy if I can see an end to it. I would go to bed supperless to-night, and so should my
children, if I could stop it. After I have had a job of work, many’s the time I have not had a penny to
take home to my children, it has all gone betwixt the foreman and the publican; and what is more, if I
had brought anything home I should have stood a worse chance of work the next day. If I had gone
away with sixpence in my pocket, the work that should have come to me would have gone to those who
had spent all in the house. I can solemnly say that the men are made regular drunkards by the
publicans. I am nine-and-twenty years dealing with this oppression, and I wish from my heart I could
see an end to it, for the sake of my children and my fellow-creatures’ children as well. But I suffer quite
as much from the foreman as I do from the publican. I am obliged to treat him before I can get a job of
work. The man who gives him the most drink he will employ the first. Besides this, the foreman has
two-fifth parts of the money paid for the job; he has twice as much as the men if he does any of the
work; and if he does none of the work he takes one-fifth of the whole money: besides this, the men do
three times the foreman’s labour. If I could get the full value of my sweat, I could lay by to-morrow, and
keep my family respectably. In the room of that, now, my family want bread often—worse luck, for it
hurts my feelings. I have been idle all to-day; for hearing of this, I came to make my statement, for it
was the pride of my heart to do all that I could to put an end to the oppression. The publicans have had
the best of me, and when the system is done away with I shan’t be much the better for it. I have been
nine-and-twenty years at it, and it has ruined me both body and soul; but I say what I do for the
benefit of others, and those who come after me.”
The other man said that he worked under a publican, and a grocer as well, and lodged with a foreman.
“I pay 2s. a week for my lodgings,” he said; “there are two beds in the room, and two men in each. The
room where we all sleep is not more than seven feet long by five feet wide, and barely seven feet high.
There is no chimney in it. It is a garret, with nothing in it but the two beds. There hadn’t need be much
more, for it wouldn’t hold even a chair besides. There’s hardly room, in fact, for the door to open. I find
it very close sleeping there at night-time, with no ventilation, but I can’t help myself. I stay there for the
job of work. I must stay; I shouldn’t get a day’s work if I didn’t. The lodgings are so bad, I’d leave them
to-morrow if I could. I know I pay twice as much as I could get them for elsewhere. That’s one way in
which I, for one, am robbed. Besides this, I am obliged to treat the foreman; I am obliged to give him
two glasses of rum, as well as lodging at his house, in order to get employment. I have also to drink at
the public-house; one-fifth of my money is kept, first and foremost, by the publican. That goes for the
compulsory drink—for the swash which he sends us on board, and that we think the Thames-water is
sweet and wholesome to it. It is expressly adulterated for our drink. If we speak a word against it we
should be left to walk the streets, for a week and more forward. Even if we were known to meet a
friend, and have a pint or a pot in another public-house, we should be called to an account for it by the
publican we worked under, and he would tell us to go and get work where we spent our money; and,
God knows, very little money we would have coming out of his house after our hard sweat. After the
compulsory drink, and the publican has settled with us, and his fifth part of our hard-earned money for
the swash—it’s nothing else—that he has given us to drink, then I should be thought no man at all if I
didn’t have two pots of beer, or half-a-pint of gin, so that I would count myself very lucky indeed if I
had a couple of shillings to take home, and out of that I should have to spend two-thirds of it to get
another job. I am a married man, and my wife and three children are in Ireland. I can’t have them over,
for it is as much as I can do to support myself. I came over here thinking to get work, and to send them
money to bring them over after me, but since I have been here I have been working at the ballast-
work, and I have not been able to keep myself. I don’t complain of what is paid for the work; the price
is fair enough; but we don’t get a quarter of what we earn, and the Irish ballast-heavers suffer more
here than in their own country. When I came over here I had a good suit of clothes to my back, and
now I’m all in rags and tatters, and yet I have been working harder, and earning more money, that I did
in all my life. We are robbed of all we get by the foremen and publicans. I was eight years a teetotaler
before I went to ballast-work, and now I am forced to be a drunkard, to my sorrow, to get a job of
work. My wife and children have a bit of land in Ireland to keep them, and they’re badly off enough,
God knows. I can neither help them, nor send money to bring them over to me; nor can I get over to
them myself. The grocers whom we work under rob us in the same manner. I have worked under one.
He supplied bread, butter, tea, sugar, coffee, candles, tobacco, cheese, &c. It is a larger kind of
chandlers’ shop. He charges us 5½d. for the same bread as I can buy for 4½d. at other shops. The tea,
sugar, and other articles he supplies us with are at the same rate; they are either worse or dearer than
at other shops. They generally manage to get a fifth part of our earnings wherever we go; but the
grocers are best of all, for they don’t ruin our health, as what they give us don’t make us sick. I work
for these two houses because the foreman that I lodge with has work out of both houses, and we are
obliged to deal at the houses that he works under; if we didn’t we shouldn’t get the job, so that if we
are not robbed by the publican we are by the grocer. They will have it out of the poor hard-working
man, and the foreman must have the gain out of it as well. I only wish to God it was done away with,
for it is downright oppression to us all, and if I never have another stroke of work I will strive all I can
to have it done away with for the sake of my fellow-men.”

BALLAST-HEAVERS AT WORK IN THE POOL.

[From a Sketch.]

After these two cases came one who said,—“I have been three years a ballast-heaver. Just before that I
came to this country. When I came I got to be a lodger with a foreman to a publican. I paid him 2s. 6d.
a-week. My family, a wife and two children, came over when I had got work as a ballast-heaver. I
couldn’t take them to the lodgings I then had; they were all for single men: so I had to take another
place, and there I went to live with my family; but to keep my work I had to pay the foreman of the
publican—him that lets these lodgings to the ballast-heaver—2s. 6d. a-week all the same as if I had
been living there. That I had, and I had to do it for two years. Yes, indeed. I didn’t earn enough to pay
for two lodgings, so two or three months back I refused to pay the 2s. 6d. a-week for a place I hadn’t
set my foot in for two years, and so I lost my work under that foreman and his publican. If me and my
children was starving for want of a bite of bread, neither of them would give me a farthing. There’s
plenty as bad as them, too, and plenty used like me, and it’s a murdering shame to tax poor men’s
labour for nothing.”
This man reiterated the constant story of being compelled to drink against his will, hating the stuff
supplied to him, being kept for hours waiting before he was paid, and being forced to get drunk,
whether he would or no. The man also informed me that he now works under a butcher, who pays 8s. a
score to the hands he employs, he (the butcher) receiving from the captain 10s.
“Suppose,” he said, “I have a 60-ton job, I’d be entitled to 7s. 6d. without beer, or such-like; but under
this butcher I get only 5s. 3d., and out of that 5s. 3d.—that’s all I get in hard money—I’m expected to
spend 4s. or thereabouts in meat, such as he chooses to give. I have no choice; he gives what he likes,
and charges me 6½d. a-pound for what I could buy at 4d. in a regular way. Very inferior stuff he keeps.
Working under a butcher, we must all live on this poor meat. We can’t afford bread or vegetables to it.”
This same butcher, I was afterwards informed, had been twice fined for using false weights to
customers, such as the man whose statement I have given; he even used wooden weights made to look
like lead.
The following is an instance of the injustice done to the men by those who contract to whip rather than
to heave the ballast on board.
“I now work,” said the man, whom I was referred to as an exponent of the wrong, “for Mr. ——, a
publican who contracts to supply ships with ballast by the lump. He’ll contract to supply a ship with all
the ballast she’ll want by the lump—that is, so much money for all she wants, instead of so much by the
ton; or he may contract with a ship at 2s. 6d. a-ton. We—that is a gang of eight men—may put two
loads or 120 tons on board in the course of a day. For those 120 tons he will receive 120 half-crowns,
that’s 15l. For putting in those 120 tons we—that is, the eight ballast-heavers employed—receive 2s. 6d.
a-day of 12 or 14 hours; that is 8 half-crowns or 20 shillings, with 3s. 6d. a-day for a basket-man, in
addition to the eight, so leaving the publican a profit of 13l. 16s. 6d.” I could hardly believe in the
existence of such a system—yielding a mere pittance to the labourer, and such an enormous profit to
the contractor, and I inquired further into the matter. I found the statement fully corroborated by many
persons present; but that was not all I learned. When the men, by incessant exertion, get in 120 tons in
a day, as they often do, nothing is charged them for the beer they have had, four or five pints a-day
each; but if only 60 tons be got in, as sometimes happens, through the weather and other
circumstances, then the men employed on the half-a-crown a-day must pay for their own beer and pay
their private scores for treating a friend, or the like. “There’s no chance of a job,” said my informant;
“not a bit of it.” He continued: “Very bad drink it is—the worst—it makes me as sick as a dog. There’s
two brothers there what they call blood-hounds; they’re called so because they hunt up the poor men
to get them to work, and to see that they spend their money at their employer’s public-house when
work’s done. If you don’t spend something, no bread to cut the next morning—not a bit of it—and no
chance of another job there. He employs us ballast-heavers, when we are not at the ballast, in backing
coals into the steamers.”
I have given the statement of a ballast-heaver as to the system pursued by those whom he called
basket-men. The employer here alluded to is one of that class, the difference being, that the ballast-
heavers shovel the ballast out of the lighter on to the stage, and from the stage through a port-hole into
the hold. Four men are thus employed, two on the lighter, and two on the stage. With a large ship five
men are employed, and two stages. When the basket-man or the man contracting by the lump is
employed, this process is observed:—There are two men in the lighter alongside the vessel to be
ballasted, whose business it is to fill five baskets. There are five men at the winch aboard ship employed
heaving up these baskets, and a basket-man to turn them over and empty out their contents.
To ascertain that there was no provident fund—no provision whatever for sickness—I investigated the
case of a man who, in consequence of illness occasioned by his trade, was afflicted with a pulmonary
complaint. This man was formerly one of the wine-cellarmen in the London Dock; he was then made a
permanent man at the St. Katherine’s Dock, and was dismissed for having taken a lighted pipe in while
at his work; and for the last fourteen years and upwards he has been a ballast-heaver. I now give his
wife’s statement:—“My husband has been ill for three months, and he has been six weeks in Guy’s
Hospital, and I am afraid he’ll never get out again, for he kept up as long as he could for the sake of the
children. We have five at home; one of them (twelve years old) I hope to get to sea, having two older
sons at sea, and being the mother of twelve children altogether. I will tell you what led to my poor
husband’s illness; he was a kind husband to me. I consider it was his hard work that made him ill, and
his not getting his rights—not his money when entitled to it. After doing a heavy day’s work he had to
go and sit in a cold tap-room, drinking bad beer; but it wasn’t beer—muck, I call it—and he had to wait
to be paid, ay, and might have had to wait till the day after, and then come home cold and have to go
to bed without a bit of victuals. His illness is owing to that; no horse could stand it long. Ballast-men are
worse than slaves in the West Indies. When at work he earned what the others did. He only drank what
he couldn’t help—the worst of stuff. No drink, no work. Six weeks ago he went to the hospital, I
conveying him. When I returned home I found three strange men had turned my four children into the
street, doing it in a brutal way. I rushed into the house, and one said, ‘Who are you?’ I seized the fellow
who said this by the handkerchief, and put him out. One of them said, ‘Be off, you old Irish hag, you
have no business here; we have possession.’ When I saw the children in the street, passion made me
strong, and so I put him out. The collector of the rent, who employed the broker, is a publican, for
whom my husband worked as a ballast-heaver until he was unable to work from illness. I was given into
custody for an assault, and taken before Mr. Yardley. He considered the assault proved, and as an
honest woman I couldn’t deny it, and so I had fourteen days with bread and water. The children were
placed in the workhouse, where they were well treated. I was very glad they were so taken care of. As
soon as I got out I went to see about my children; that was the first thing I did. I couldn’t rest till I did
that. I brought them home with me, though it was only to bread and water, but I was with them. I only
owed about 15s. rent, and had been four years in the house at the time the publican put the broker in.
We paid 6s. 6d. a-week; it was no use asking such a man as that any mercy. He was in the habit of
employing ballast-heavers for many years; and if that doesn’t harden a man’s heart, nothing will. In
general these ballast publicans are cruel and greedy. At present I go out washing or charing, or doing
anything I can to maintain my children, but work’s very slack. I’ve had a day and a-half this fortnight,
earning 2s. 6d., that’s all for a fortnight; the parish allows me four loaves of bread a-week. The
children, all boys, just get what keeps a little life in them. They have no bed at night, and are starved
almost to death, poor things. I blame the system under which my husband had to work—his money
going in drink—for leaving me destitute in the world. On Christmas-day we lived on a bit of workhouse
bread—nothing else, and had no fire to eat it by. But for the money gone in drink we might have had a
decent home, and wouldn’t so soon have come to this killing poverty. I have been tenderly reared, and
never thought I should have come to this. May God grant the system may be done away with, for poor
people’s sake.”
I now give the statement of two women, the wives of ballast-heavers, that I may further show how the
wives and families of these men are affected by the present system.
“I have been 11 years married,” said one, “and have had five children, four being now living.”
The other woman had been married 23 years, but has no children living.
“We are very badly off,” said the woman with a family, “my husband drinking hard. When I first knew
him—when we were sweethearts in a country part of Ireland—he was a farm-labourer and I was a
collier’s daughter, he was a sober and well-behaved man. Two years after we were married, and he was
a sober man those two years still. We came to London to better ourselves, worse luck. The first work he
got was ballast-heaving. Then he was obligated to drink or he couldn’t get work; and so, poor man, he
got fond of it. This winter oft enough he brings me and the children home 2s. or 1s. 6d. after a job; and
on that we may live for two or three days,—we’re half starved, in course. The children have nothing to
eat. It’s enough to tear any poor woman’s heart to pieces. What’s gone into the publican’s till would get
the children bread, and bedding, and bits of clothes. Nothing but his being employed at ballast-heaving
made him a drunkard, for he is a drunkard now. He often comes home and ill-uses me, but he doesn’t
ill-use the children. He beats me with his fists; he strikes me in the face; he has kicked me. When he
was a sober man he was a kind, good husband; and when he’s sober now, poor man, he’s a kind, good
husband still. If he was a sober man again with his work, I’d be happy and comfortable to what I am
now. Almost all his money goes in drink.”
“We can’t get shoes to our feet,” said the second woman.
“When my husband is sober and begins to think,” (continued the first,) “he wishes he could get rid of
such a system of drinking,—he really does wish it, for he loves his family, but when he goes out to work
he forgets all that. It’s just the drink that does it. I would like him to have a fair allowance at his work,
he requires it; and beyond that it’s all waste and sin: but he’s forced to waste it, and to run into sin, and
so we all have to suffer. We are often without fire. Much in the pawn-shop do you say, sir? Indeed I
haven’t much out.”
“We,” interposed the elder woman, “haven’t a stitch but what’s in pawn except what wouldn’t be taken.
We have 50s. worth in pawn altogether—all for meat and fire.”
“I can’t, I daren’t,” the younger woman said, “expect anything better while the present system of work
continues. My husband’s a slave, and we suffer for it.”
The elder woman made a similar statement. After his score is paid, she said, her husband has brought
her 4s., 3s., 2s., 1s., and often nothing, coming home drunk with nothing at all. Both women stated
that the drink made their husbands sick and ill, and for sickness there was no provision whatever. They
could have taken me to numbers of women situated and used as they were. The rooms are four bare
walls, with a few pieces of furniture and bedding such as no one would give a penny for. The young
woman was perfectly modest in manner, speech, and look, and spoke of what her husband was and still
might be with much feeling. She came to me with a half-clad and half-famished child in her arms.
I then took, for the sake of avoiding repetition, the statements of two ballast-heavers together—
constant men—working under different publicans. The account they gave me of the way in which the
publicans contracted to ballast a ship was the same as I have given elsewhere.
“I have been twenty years a ballast-heaver,” said one, “and all that time I have worked for a publican,
and haven’t a coat to my back. Twenty years ago the publicans had the same number of hands, but had
more work for them, and I might then earn 20s. a-week; but I couldn’t fetch that home from the
publican. He expected me to spend one-half of my earnings with him; and when I left his house drunk,
I might spend the other half. I’ve drunk gallons of drink against my will. I’ve drunk stuff that was poison
to me. I turned teetotaler about six months ago, and the publican, my employer, sacked me when he
found it out, saying, ‘He’d be d——d if he’d have such men as me—he didn’t make his living by
teetotalers.’”
“Yes,” added the other man, “and so my publican told me; for I turned teetotaler myself somewhere
about seven years ago, and took the pledge from Father Mathew in the Commercial-road. The publican
told me, that if Father Mathew chose to interfere with me, why Father Mathew might get employment
for me, for he—that’s the publican—wouldn’t. So I was forced to break my pledge to live—me and my
youngsters—I had six then, and I’ve buried two since.”
“Work,” resumed the man who first gave me the statement, “keeps getting worse. Last week I carried
only 8s. home, and if I’d got paid by the captain of the ship for the amount of work I did, and on the
same terms as the publican, I should have taken home at the very least 16s. The publican that employs
us gives us only 8s. a-score, and receives 10s. from the captain. All the publicans don’t do this; some
give what they get from the captain, but some publicans takes two-thirds, and that’s the truth. (The
second man assented.) One week with another I’ve taken home, this winter, from 12s. to 13s., and but
for this shameful starvation system, having to work for a publican’s profit, and to drink his drink, I’d
take home my 20s. every week. It makes a man feel like a slave; indeed, I’m not much better. We
should be in heaven if we got away from the publican or butcher either; it’s compulsion one’s life
through. Some of the publicans have as many as sixty single men lodging in their houses, paying half-a
crown a-week; ay, and men that don’t lodge with them, when the house is full, must pay half-a-crown
all the same, to get a job of work, as well as paying for the places where they do lodge.”
The first man continued:—
“The gin and rum is the worst that can be supplied; but we must drink it or waste it. We often spill it on
the ballast, it’s that bad”—[“Often, often,” was the response of the other man.] “And that’s not the
worst. When we get a job of putting sixty tons of ballast on board, we are forced to take six pots of
beer with us to our work; but only four pots are supplied, and we must pay for six. We are robbed on
every side. I cannot describe how bad it is; a man would hardly believe it; but all will tell you the same
—all the men like us.” [So, indeed, the poor fellows did afterwards.] “When we call to be paid, we are
kept for hours in a cold tap-room, forced to drink cold stuff without being let have a strike of fire to take
the chill off it.”
The other man then made a further statement.
“I’ve been forced to put my sticks in pawn—what I had left—for I was better off once, though I was
always a ballast-heaver and have worked for the same publican fourteen years. I have 3l. in pawn now,
I blame this present system for being so badly off—sorrow a thing else! Now just look at this: A single
man, a lodger, will go into a publican’s and call for 1s. worth of rum, and the publican will call me a
scaly fellow, if I don’t do the same; that will be when I’d rather be without his rum, if I got it for
nothing.” One publican (the men gave me this account concurrently, and it was fully confirmed by a host
of others,) married the niece of a waterman employed to pull the harbour-master about the river. He
kept a public-house, and carried on the system of lodgers for ballast-heaving, making a great deal of
money out of them; by this means he got so much work at his command, that the rest of the publicans
complained to the harbour-master, and the man was forced to give up his public-house. When he had to
give it up he made it over to his niece’s husband, and that man allowed him 1s. for every ship he
brought him to ballast. “I’ve known him—that’s the publican that succeeded the man I’ve been telling
you of—have 40 ships in a day: one week with another he has had 100 ships; that’s 5l., and he has
them still. It’s the same now. We’ve both worked for him. His wife’s uncle (the harbour-master’s
waterman) says to the captains, and he goes on board to see them after the harbour-master’s visit to
them,—‘Go to ——; get your ballast of him, and I’ll give you the best berth in the river.’”
I next obtained an interview with a young man who was the victim of a double extortion. He made the
following statement:—
“I work under a publican, and lodge in his house. I have done so for five years. I pay 2s. 6d. a-week,
there being ten of us in two rooms. We’re all single men. These two rooms contain four beds, three in
the larger room and one in the other. We sleep two in a bed, and should have to sleep three in some;
only two of the men don’t occupy the lodgings they pay for. The bigger room may be 16 feet by 10; the
smaller about a quarter that size. You cannot turn in it—the bed cannot be brought out of the room
without being taken to pieces. We must cook in the tap-room, which is a room for the purpose; it
contains forms and an old table, with a large grate. We are found fryingpans and gridirons, and pans,
and fire, and candle; but we must find our own knives and forks. The room is shamefully dirty—I mean
the tap (cooking) room. It looks as if it hadn’t been washed for years. It’s never been washed to my
knowledge. The bed-rooms are very little better. The bedding is very bad—a flock bed, with a pair of
blankets and quilt, and a sort of sheet clean once a-fortnight. There’s very bad ventilation and very
unpleasant smells. It’s a horrid den altogether. None of us would stop there if we could help it—but we
can’t help it, for if we leave we get no work. We are forced to find locks for our rooms, to keep our bits
of things from being stolen. One man was robbed; my clothes was in the box with his; the box was
broken open, but the clothes was left, and a few halfpence put away in the box was taken. There’s lots
of bugs; we can only sleep after hard work, and we must drink when we’re at work. I’ve poured my
beer into the river many a time, it was so bad—it tasted poisonous. We’ve drank Thames water rather
than the bad beer we’re all forced to drink. To show how we’re treated I’ll tell you this: I owe so much,
and so much a week’s stopped to pay it; but it never gets less, I am always charged the same. There it
is, the same figures are on the slate, keep paying, paying off as you will. They won’t rub it off, or if they
do rub it off it’s there again the next time. Only last week a man was discharged for grumbling, because
he objected to paying twice over. He hasn’t had a day’s work since.”
Then came one who was the employé of a publican and grocer. He said:
“I work under a publican and grocer. I’m any man’s man. I stand with my fingers in my mouth at
Ratcliff-cross watching, and have done it these last nine years. Half of us is afraid to come and speak to
you. When I volunteered, the big-whiskered and fat-faced men (foremen) were looking at me and
threatening me for coming to you. No matter, I care for nobody. Worse nor I am I can’t be. No more I
can’t. I go to one publican’s to work 60 tons, and for that I get 4s., but 6s. is my rights. The remainder
2s. is left—I’m forced to leave it—for me to drink out on Sunday night. If I was in a fair house the
publican would pay me 7s. 6d.; as it is I get 4s. and 2s. must be drunk,—it’s the rule at that house—
he’s in opposition and works low. If I was at liberty it wasn’t to his house I’d go for a drink. The
hardest-drinking man gets work first, and when a man’s drunk he doesn’t care what stuff he puts into
his belly. Before we go to a job the four of us are expected to drink half-a-pint of rum or gin; the
publicans expect it. If I was a teetotaler I must pay my whack and the other men may drink it, for the
score against the ship is divided among the men equal.
“Suppose two foremen were to meet and have a drop of rum or brandy together, and a little talk about
a ship’s ballast, that’s charged to us poor fellows—it’s stuck up to us—but we mustn’t say nothing,
though we know we never had a sup of it; but if we say a word it’s all up—no more work.
“Once on a time I worked for a publican close by here, and when I came to the house I had nothing to
drink. My oldest mate whispered to me as we were on our way from the London Dock, and told me to
speak my mind, for he knew there was a false score chalked against the ship; and the others was afraid
to say a word. Well, I did speak when I got into the house, and the foreman was there, and he asked
me what business I had to speak more than another? There was 6s. charged to the score for drink that
we never touched or ever saw,—not a sup of it. He—that’s the foreman—told me I shouldn’t go to finish
the ship; I said I would, in spite of him. I told the missus I expected she wouldn’t give any more drink
but what we had ourselves, or would get when we came home; and she said she wouldn’t; and that’s
two years ago; but I haven’t had a job from them parties since.
“Suppose I get to the public-house for my money at six in the evening, I am forced to wait there till
eleven, until I am drunk very often—drunk from vexation; stopt when I’m hungry after five or six hours’
work on the river, and not let take the money home to my wife and family, nor let have anything to eat,
for I’m waiting for that money to get a bit of grub; but when I’m half drunk the hunger goes off just for
a time. I must go and drink in a morning if my children go without breakfast, and starve all day till I
come home at night. I can get nothing from my employers but drink. If I ask them for a shilling I can’t
get it. I’ve finished my load of ballast without breaking my fast but on the beer we’re forced to take with
us.
“I’ve found grocers better to work under than publicans,—there’s a great deal more honesty in them.
They charge a middling fair price; but they’ll have tow-row out of it,—that’s dry money—so much a
score. They’ll stop 6d. a score only for giving us a job. I can get as good sugar as I get of them at 4d.
for 3½d.; but then the difference between the grocer and publican is, that the wife and family can have
a bit of something to eat under the grocer, but not under the publican. All goes in drink with the
publican; but we cannot carry drink home. When I go home drunk from the publican’s, I tumble on the
floor, perhaps, and say, ‘Is there anything to eat for me?’ and my old woman says, ‘Where’s the money?
give me that and I’ll give you something to eat.’ Then a man gets mad with vexation, and the wife and
children runs away from him; they are glad to get away with their lives, they’re knocked about so. It
makes a man mad with vexation to see a child hungry,—it kills me; but what the foreman gives me I
must take; I dare never say no. If I get nothing—if all is gone in drink—I must go from him with a blithe
face to my starving children, or I need never go back to him for another job.”
I shall now set forth as fully as possible the nature of the system by which the ballast-heaver is either
forced by the fear of losing all chance of future employment, or induced by the hope of obtaining the
preference of work from the publican, his employer, to spend at least one half of his earnings every
week in intoxicating drinks. Let me, however, before proceeding directly to the subject of my present
communication, again lay before the reader the conclusions which I lately drew from the Metropolitan
Police returns for 1848, concerning the intemperance of the labouring classes of London. It is essential
that I should first prove the fact, and show its necessary consequences. This done, the public will be
more ready to perceive the cause, and to understand that until this and similar social evils are removed,
it is worse than idle to talk of “the elevation of the masses,” and most unjust, to use the mildest term,
to condemn the working men for sins into which they are positively forced. To preach about the virtues
of teetotalism to the poor, and yet to allow a system to continue that compels them to be drunk before
they can get work—not to say bread—is surely a mockery. If we would really have the industrious
classes sober and temperate men, we must look first, it seems, to their employers. We have already
seen that the intemperance of the coal-labourer is the fault of the employer, rather than the man; but
we have only to go among the ballast-labourers to find the demoralization of the working man arising,
not from any mere passive indifference, but from something like a positive conspiracy on the part of the
master.
According to the criminal returns for the metropolis, there were 9197 males and 7264 females, making
altogether a total of 16,461 individuals, charged with drunkenness in the year 1848. This makes one in
every 110 individuals in London a drunkard—a proportion which, large as it seems, is still less than one-
half what it was some ten or fifteen years back.
For the sake of comparison I subjoin, in the following page, a Table, taken from the Government Report
on Drunkenness; being a return of the number of charges of drunkenness which have been entered
upon the books of the Metropolitan Police in the years 1831, 1832, and 1833, with the number of
officers employed in, and the locality of, each division: also the amount of population in each, according
to the Parliamentary returns of 1831.
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