Table Of ContentTHE CARBOHYDRATES
Chemistry, Biochemistry, Physiology
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THE CARBOHYDRATES
Chemistry, Biochemistry, Physiology
Edited by
WARD PIGMAN
Department of Biochemistry
University of Alabama Medical Center
Birmingham, Alabama
1957
ACADEMIC PRESS INC · PUBLISHERS
NEW YORK
COPYRIGHT 1957 BY ACADEMIC PRESS INC.
ALL RIGHTS RESERVED
NO PART OF THIS BOOK MAY BE REPRODUCED IN ANY FORM
BY PHOTOSTAT, MICROFILM, OR ANY OTHER MEANS,
WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS.
ACADEMIC PRESS INC.
Ill FIFTH AVENUE
NEW YORK 3, N. Y.
United Kingdom Edition
Published by
ACADEMIC PRESS INC. (LONDON) LTD.
BERKELEY SQUARE HOUSE, LONDON W. 1
First Printing, 1957
Second Printing, 1962
Library of Congress Catalog Card Number: 57-8879
PRINTED IN THE UNITED STATES OF AMERICA
CONTRIBUTORS
C. E. BALLOU, University of California, Department of Plant Biochemistry, Berkeley,
California (pp. 172, 478)
MARY GRACE BLAIR, University of Alabama, Medical Center, Arthritis and Rheumatism
Research Laboratory, Birmingham, Alabama (p. 60)
HELMUT BAUMANN, Silikose-Forschungsinstitut der Bergbau-Berufsgenossenschaft,
Bochum, Germany (p. 686)
W. M. CORBETT, British Rayon Research Organization, Heald Green Laboratories,
Wythenshane, Manchester, England (p. 641)
HARRY G. DAY, Indiana University, Department of Chemistry. Bloomington, Indiana
(p. 779)
DAVID G. DOHERTY, Oak Ridge National Laboratory, Biology Division, Oak Ridge,
Tennessee (pp. 424, 480, 441)
JOHN W. GREEN, Institute of Paper Chemistry, Appleton, Wisconsin (p. 299)
W. Z. HASSID, University of California, Department of Plant Biochemistry, Berkeley,
California (pp. 172, 478)
ROLLAND L. LOHMAR, JR., United States Department of Agriculture, Northern Utiliza-
tion Research Branch, Peoria, Illinois (p. 241)
ROBERT W. MOWRY, University of Alabama, Medical Center, Department of Pathology,
Birmingham, Alabama (p. 624)
G. RAY NOGGLE, C. F. Kettering Foundation, Yellow Springs, Ohio (pp. 602, 788)
JANE REID PATTON, Howard College, Department of Chemistry, Birmingham, Alabama
(p. 466)
WARD PIGMAN, University of Alabama Medical Center, Biochemistry Department,
Birmingham, Alabama (pp. 1, 406, 686, 709, 779)
DAVID PLATT, University of Alabama Medical Center, Department of Biochemistry,
Birmingham, Alabama (pp. 446', 709)
JAMES W. PRATT, National Institute of Arthritis and Metabolic Diseases, Bethesda,
Maryland (p. 861)
LAWRENCE ROSEN, University of Alabama Medical Center, Department of Biochemis-
try, Birmingham, Alabama (pp. 407, 462)
JOHN C. SOWDEN, Washington University, Department of Chemistry, St. Louis, Mis-
souri (pp. 77, 867)
ALVA THOMPSON, The Ohio State University, Department of Chemistry, Columbus,
Ohio (pp. 188, 188)
ELLIOTT VOLKIN, Oak Ridge National Laboratory, Biology Division, Oak Ridge, Ten-
nessee (pp. 480, 441)
ROY L. WHISTLER, Purdue University, Department of Biochemistry, Lafayette, Indiana
(p. 64D
M. L. WOLFROM, The Ohio State University, Chemistry Department, Columbus, Ohio
(pp. 188,188)
v
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PREFACE
"The Carbohydrates" is a complete revision and expansion in scope of
the earlier "Chemistry of the Carbohydrates."* Two new chapters have
been added covering photosynthesis and metabolism (Chapter XIII) and
nutritional aspects (Chapter XIV). These additions and the general in-
crease in the coverage of biochemical and physiological aspects reflect the
great progress made in biochemistry during the past decade and the im-
portant position of the carbohydrates in the processes of life. Marked ad-
vances have also been made in recent years especially in reaction mecha-
nisms, stereochemistry of strainless rings, transglycosylation, development
of methods for the synthesis of radioactive sugars and their analysis, chro-
matography and related methods of analysis, identification of tissue carbo-
hydrates in situ (histochemistry), and isolation and characterization of
animal polysaccharides and their protein complexes. These developments
have been brought into the present work.
The vast accumulated literature and the almost terrifying rate of growth
create new problems continually. In this volume references are given to
about 4500 individual articles, representing the result of the careful exami-
nation through much of 1956 of several times this number of articles. In
turn, these represent only a small fraction of the actual carbohydrate
literature. As a result, considerable selection of material was necessary,
and the fullness of the treatment varies. Subjects such as the sugars and
their derivatives are discussed in detail, whereas such subjects as the poly-
saccharides, which have been considered satisfactorily in other monographs,
have been condensed. References to more detailed treatments help to in-
crease the coverage.
The relatively scanty general coverage by the current eleven volumes
of the "Advances in Carbohydrate Chemistry" is witness to the broad
scope and depth of the subject of the carbohydrates. The literature and
the available knowledge in the field of carbohydrates, like those of the
corresponding fields of the proteins and of the enzymes, are similar in
magnitude to those in such broad fields as medicine and dentistry. Prepa-
ration of a monograph on starch alone involves dealing with more research
material and more basic literature than some specialized branches of
medicine.
In order to prevent this new book from being simply an expansion of the
old one, considerable borderline material was deleted, and the polysaccha-
* W. W. Pigman and R. M. Goepp, Jr., "Chemistry of the Carbohydrates." Academic
Press, New York, 1948.
vii
viii PREFACE
ride chapters were condensed. The older edition contains additional mate-
rial of permanent value and should be used in conjunction with the current
book.
Presumably this volume will have its main use as a reference work by
chemists, biochemists, industrialists, biologists, histochemists, students,
and medical and dental research workers. It should be useful as a basic
text for graduate courses in the subject. It may have value as a text, with
readings assigned to some of the references, for a general advanced course
for some departments of biochemistry and microbiology; the integration
of the research viewpoint with physical and organic chemistry and bio-
chemistry and with physiology and biology may provide the basis of a
useful and practical course, especially for small departments not well pre-
pared for offering advanced courses in special fields of chemistry. The sub-
ject cuts across all of these classical disciplines and others such as tech-
nology and commerce.
Since the publication of the previous edition, there has been considerable
standardization of nomenclature. The new official rules have been fol-
lowed closely. In areas in which agreement on nomenclature has not been
reached, notably nomenclature of some acids (especially ascorbic acids),
biologically important nitrogenous compounds, and polysaccharides, arbi-
trary choices have been made.
The present work has been made possible only by the wholehearted re-
sponse of some of the important workers in the field who aided in the revi-
sion of the material in the previous volume. Acknowledgment of their
valuable help is indicated by the authorship of the chapters and some
shorter sections. Several associates, including graduate students, cooper-
ated in preparing some sections and gave valuable assistance generally.
The general editorial assistance of Dr. Grace Blair was of great help
Doctors James Woods, Robert Teague, and Joseph Volker read some of
the material and provided valuable advice. Others who have helped in this
or similar ways are B. F. Helferich, J. Goerdeler, M. L. Wolfrom, S. Rose-
man, C. Ballou, and G. E. McCasland.
The onerous task of preparing the subject index was accepted by Dr.
James Pratt to whom special thanks are due. Dr. Hewitt Fletcher gave im-
portant assistance in the reading of page proof and in his comments.
The University of Alabama provided indirect support and encourage-
ment essential to the preparation of this book. The whole-hearted coopera-
tion of Academic Press eased the solution of the many editorial and pub-
lication problems.
WARD PIGMAN
June 1957
Birmingham, Alabama
CONTENTS
List of Contributors v
Preface vii
I. Introduction: Structure and Stereochemistry of the Monosaccharides BY
WARD PIGMAN 1
1. General Relations 1
2. Some Definitions 2
3. Nomenclature 5
4. Development of Carbohydrate Chemistry 5
5. Structures of Glucose and Fructose 7
6. Stereochemistry 8
A. General Principles 8
B. Establishment of the Configuration of Glucose and Some Other Sugars. 13
C. D- and L-Nomenclature 21
7. Ring Structures of the Sugars 29
A. Necessity for Ring Structures 29
B. Proof of Ring Structure 31
C. Configuration of the Anomeric Carbon Atom 35
D. The Representation of the Ring Structures of the Sugars 37
E. Nomenclature of Anomers (a-ß Nomenclature) 42
8. Homomorphous Sugars 44
A. Homomorphology 44
B. Nomenclature for Higher Sugars and for Compounds with Numerous
Asymmetric Atoms in a Carbon Chain 44
9. The Sugars in Solution 49
A. In the Absence of Strong Acids or Alkalies; Mutarotation 49
B. In the Presence of Acids 57
C. In the Presence of Alkalies BY MARY GRACE BLAIR 60
D. Behavior of the Sugars with Short Carbon Chains 69
10. Optical Superposition, the Isorotation Rules, and the Influence of Structure
on Optical Rotation 70
II. Occurrence, Properties, and Synthesis of the Monosaccharides BY JOHN
SOWDEN 77
1. Naturally Occurring Monosaccharides 77
A. Introduction 77
B. Origin and Preparation of Some Naturally Occurring Monosaccharides. 79
2. Synthetic Sugars 103
A. Complete Synthesis of the Sugars 103
B. Methods for Lengthening the Carbon Chain of the Sugars 106
C. Methods for Shortening the Carbon Chain of Sugars 118
ix
