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Advances in agronomy. Vol. XI
Book
Reviews
The Chemistry of Heterocyclic Compounds. Vol. XIII. s-Triazines and Derivatives. By EDWIN M. SMOLIN and LORENCE RAPOPORT, Central Research Division, American pany, Stamford, Connecticut. Inc., New York, N. Y., 1959. $30.00.
Few errors were found, hut the resonance energy of triazine cannot be both 82 (p. 18) and 40 (p. 7) kilocalories per mole. The higher value may perhaps belong to the whole molecule of cyanuric acid. This book is thoroughly recommended to the more chemically minded of biochemists who will see that triazines (because of the high ratio of -N= to -CH-) have many analogies with pteridines.
Cyanamid ComInterscience Publ. xxiv+ 644 pp. Price
The authors of this lucidly written book make much use of physical properties to record the abrupt. transitions in chemical behavior that accompany substitution in the triazine ring. It is becoming increasingly recognized that those heteroaromatic substances that have a doubly bound nitrogen atom differ considerably from their aromatic analogs. The nature of this difference lies in the strong pull exerted by the nitrogen atom on the r-electrons. These electrons are responsible for the aromatic stability of the molecule, and even a comparatively small localization, such as the single nitrogen atom causes in pyridine, makes the molecule less stable. In s-triazine (i.e., benzene in which every other -CH= group is replaced by-N=) this effect is seen in the highest degree. Indeed, s-triazine is so unstable that it is completely hydrolyzed (to formamidine) as soon as it is mixed with water. This picture of the excessive localization of T-electrons is completely changed by the insertion of electron-releasing groups. Thus melamine (triamino-s-triazine) and cyanuric acid (trihydroxy-s-triazine) are highly stable, even t.o concentrated alkali and acid. This book describes, in adequate detail, the preparation and reactions of the various s-triazines, with particular reference to melamine and the 2,4-diaminotriazines which have proved such valuable intermediates for some of the most useful of contemporary plastics. Much space is allot,ted also to 2,4,6-trichlorotriazine, which is an essential intermediate not only for the most durable of the “direct”’ dyes for cotton, but also for the valuable new herbicide “Simazine” (2.chloro-4,6bisethylaminotriazine). Triazine derivatives of biological interest are also included, such as the urinary antiseptic hexamethylenetetramine; also, the dihydrodiaminotriazines, antimalarial drugs which are not administered as such but in the form of precursors such as p-chlorophenylbiguanide (proguanil or “Paludrine”) which cyclize in the human body.
ADRIEN ALBERT, Canberra,
Advances in Agronomy.
Australia
Vol. XI. Edited
G. NORMAN, University of Michigan Michigan. Academic Press Inc., New 1959. x + 428 pp. Price $12.00.
Ann York,
by A. Arbor, N. Y.,
The most recent in the series sponsored by the American Society of Agronomy resembles the preceding ones in its authoritative coverage of a variety of topics of interest to those involved in teaching and research in the soil and plant sciences. Over one fourth of the volume is devoted to a definitive and critical examination of water and its relation to soil and crops. This is a contribution of a group of distinguished coauthors under the leadership of M. B. Russell. The importance of the subject and the comprehensive treatment justify a listing of the subsections and their authors. They are: “Water and The Hydrologic Cycle,” Russell, Hurlbut, Angus; “Interactions of Water and Soil,” Russell; “Plant-Water Relations,” Kramer and Russell; “Soil-Plant-Water Interrelations,” Hagan, Vaadia, Russell, Henderson, Burton. This up-to-date and thought-provoking section should be of great value to all those whose research and teaching deals with soils or plants. A most provocative article by P. G. Meijers discusses the land-use practices which have enabled the development of high levels of productivit,y on soils of the Netherlands, an area not so endowed by nature. Professor Meijers’ description of the soil, the problems, and the practices provides an excellent example of what can be accomplished through the development and application of intensive agronomic practices. In summarizing a number of observations re384
BOOK
lating to phosphate-nitrogen interaction in crop nutrition, D. L. Grunes considers the difficult subject dealing with the effects of nitrogen fertilization on phosphate availability. The remaining three articles deal with subjects which usually are not identified directly with soil and plant science. They include a comprehensive and altogether admirable treatment of fertilizer production and technology, by K. D. Jacob; a description of recent developments in agricultural machinery, by T. W. Edminster and H. F. Miller; and a discussion by R. D. Munson and J. P. Doll on the economics of fertilizer use. Finally, the volume contains cumulative author and subject indexes for Vols. VI-X.
X. T. COLEMAN, Raleigh,
North
Carolina
Lettr6 - Inhoff en - Tschesche: Ueber Steroide, Gallensiluren und verwandte Naturstoffe. (Sammlung Chemischer und Chemisch-Technischer Beitrage). Vol. 2. Second edition. Edited by H. H. INHOFFEN, Braunschweig. Ferdinand Enke Verlag, Stuttgart, 1959. xii + 708 pp. Price DM 220, paper-bound; DM 225, cloth bound. This book is the second volume of a new, completely revised edition of the old review with the same title that appeared in 1936. Apart from the title and the regrettable custom of dropping the initials of the given names of the authors in the literature references, the presentation of the new book is very different from the old one. The first four chapters give 587 pages of reviews on (1) androstanes (H. Heusser and H. Jahnke), (2) estranes and estrogenic carboxylic acids (H. Jahnke), (3) pregnanes without an 11-oxygen function (F. Blomeyer), and (4) 11-oxygenated steroids (J. Elks). These reviews are followed by shorter chapt,ers on (5) aldosterone (A. Wettstein), (6) conformational analysis (D. H. R. Bart,on), (7) aromatization react,ions in ring A (H. H. Inhoffen), and (8) the total synthesis of Vitamin D, (K. Irmscher). Owing to this more or less arbitrary division of the subject matter into groups treated independently by different authors, several publications are reviewed twice. The attempt to give as complete a coverage of the literature as possible diminishes the clarity and conciseness of the reviews, and in the first, chapters it might be difficult for anyone not familiar with the subject to distinguish the important from the less relevant facts. In the third chapter an interesting compilation of different react.ions as applied t,o various steroids is to be found, and the fourth chapter gives a clear and complete review of the chemical transformations and synthetic preparations of Il. oxygenated steroids. In general the above-men-
385
REVIEWS
tioned chapters are confined to the chemistry of the substances involved, and pharmacological importance and biological activity are only briefly and incompletely mentioned. The chapter on aldosterone describes not only the isolation, structutal elucidation, and total synthesis of this hormone, but also methods of biological testing, pharmacological properties, and possible pathways of biosynthesis. Barton’s article includes an introduction to conformat.ional analysis as well as discussion of the st,ability relationships in polycyclic cyclohexane systems and of t,he steric requirements of different. reactions with special reference to st,eroid chemistry. The chapter by Inhoffen gives an account of the t.herma1 and acid-catalyzed aromatization react,ions in rings A and B, and in the final chapter the problems of the total snnthesis of vitamin D3 , recently completed in Inhoffen’s laboratories, are discussed. For the specialist in the steroid field the book is a valuable addition to the numerous reviews already existing. The great progress achieved in the last few years especially in the corticoid is, however, not included in the book, because, although published in 1959, it only covers the literature up to 1955 (and a few references from 1956) at which date the manuscripts were put into the editors’ hands. Only the last chapter refers to more recent publications. The views given in the book should therefore only be considered in the light of the general knowledge of 1955. KARL HEUSLER, Basle, Switzerland
in Drug Research. Vol. I. By ERNST Pharmaceutical-Chemical Laboratory Sandoz Ltd., Basle, Switzerland. Birkhauser Verlag, Base1 and Stuttgart, 1959. 607 pp. The work to be reviewed here is the first volume of a new series of progress reports on research in the field of drugs comprising their basic chemical, physicochemical, and biological aspects. Written by experts in the specific fields and maintaining a high level of scientific thoroughness, t,he book will impress the reader as a gratifying attempt to present the development of the fundamentals in therapeutic achievements of the last years. Predominantly theoretical treatment of subjects such as “Ion Exchange” by J. Biichi (Zurich) and “Stereochemical Factors in Biological Activity” by A. H. Becket (London) alternates with reviews of biochemical and clinical character, e.g., on “Cholesterol and Its Relation to Atherosclerosis” by T.-M. Ling and K. K. Chen (Indianapolis, Ind.). The field of chemotherapy is represented by an instructive contribution on “Chemotherapy of Helminthic Infections” by H.-A. Oelkers (HamProgress
JUCKER,
Reviews
The Chemistry of Heterocyclic Compounds. Vol. XIII. s-Triazines and Derivatives. By EDWIN M. SMOLIN and LORENCE RAPOPORT, Central Research Division, American pany, Stamford, Connecticut. Inc., New York, N. Y., 1959. $30.00.
Few errors were found, hut the resonance energy of triazine cannot be both 82 (p. 18) and 40 (p. 7) kilocalories per mole. The higher value may perhaps belong to the whole molecule of cyanuric acid. This book is thoroughly recommended to the more chemically minded of biochemists who will see that triazines (because of the high ratio of -N= to -CH-) have many analogies with pteridines.
Cyanamid ComInterscience Publ. xxiv+ 644 pp. Price
The authors of this lucidly written book make much use of physical properties to record the abrupt. transitions in chemical behavior that accompany substitution in the triazine ring. It is becoming increasingly recognized that those heteroaromatic substances that have a doubly bound nitrogen atom differ considerably from their aromatic analogs. The nature of this difference lies in the strong pull exerted by the nitrogen atom on the r-electrons. These electrons are responsible for the aromatic stability of the molecule, and even a comparatively small localization, such as the single nitrogen atom causes in pyridine, makes the molecule less stable. In s-triazine (i.e., benzene in which every other -CH= group is replaced by-N=) this effect is seen in the highest degree. Indeed, s-triazine is so unstable that it is completely hydrolyzed (to formamidine) as soon as it is mixed with water. This picture of the excessive localization of T-electrons is completely changed by the insertion of electron-releasing groups. Thus melamine (triamino-s-triazine) and cyanuric acid (trihydroxy-s-triazine) are highly stable, even t.o concentrated alkali and acid. This book describes, in adequate detail, the preparation and reactions of the various s-triazines, with particular reference to melamine and the 2,4-diaminotriazines which have proved such valuable intermediates for some of the most useful of contemporary plastics. Much space is allot,ted also to 2,4,6-trichlorotriazine, which is an essential intermediate not only for the most durable of the “direct”’ dyes for cotton, but also for the valuable new herbicide “Simazine” (2.chloro-4,6bisethylaminotriazine). Triazine derivatives of biological interest are also included, such as the urinary antiseptic hexamethylenetetramine; also, the dihydrodiaminotriazines, antimalarial drugs which are not administered as such but in the form of precursors such as p-chlorophenylbiguanide (proguanil or “Paludrine”) which cyclize in the human body.
ADRIEN ALBERT, Canberra,
Advances in Agronomy.
Australia
Vol. XI. Edited
G. NORMAN, University of Michigan Michigan. Academic Press Inc., New 1959. x + 428 pp. Price $12.00.
Ann York,
by A. Arbor, N. Y.,
The most recent in the series sponsored by the American Society of Agronomy resembles the preceding ones in its authoritative coverage of a variety of topics of interest to those involved in teaching and research in the soil and plant sciences. Over one fourth of the volume is devoted to a definitive and critical examination of water and its relation to soil and crops. This is a contribution of a group of distinguished coauthors under the leadership of M. B. Russell. The importance of the subject and the comprehensive treatment justify a listing of the subsections and their authors. They are: “Water and The Hydrologic Cycle,” Russell, Hurlbut, Angus; “Interactions of Water and Soil,” Russell; “Plant-Water Relations,” Kramer and Russell; “Soil-Plant-Water Interrelations,” Hagan, Vaadia, Russell, Henderson, Burton. This up-to-date and thought-provoking section should be of great value to all those whose research and teaching deals with soils or plants. A most provocative article by P. G. Meijers discusses the land-use practices which have enabled the development of high levels of productivit,y on soils of the Netherlands, an area not so endowed by nature. Professor Meijers’ description of the soil, the problems, and the practices provides an excellent example of what can be accomplished through the development and application of intensive agronomic practices. In summarizing a number of observations re384
BOOK
lating to phosphate-nitrogen interaction in crop nutrition, D. L. Grunes considers the difficult subject dealing with the effects of nitrogen fertilization on phosphate availability. The remaining three articles deal with subjects which usually are not identified directly with soil and plant science. They include a comprehensive and altogether admirable treatment of fertilizer production and technology, by K. D. Jacob; a description of recent developments in agricultural machinery, by T. W. Edminster and H. F. Miller; and a discussion by R. D. Munson and J. P. Doll on the economics of fertilizer use. Finally, the volume contains cumulative author and subject indexes for Vols. VI-X.
X. T. COLEMAN, Raleigh,
North
Carolina
Lettr6 - Inhoff en - Tschesche: Ueber Steroide, Gallensiluren und verwandte Naturstoffe. (Sammlung Chemischer und Chemisch-Technischer Beitrage). Vol. 2. Second edition. Edited by H. H. INHOFFEN, Braunschweig. Ferdinand Enke Verlag, Stuttgart, 1959. xii + 708 pp. Price DM 220, paper-bound; DM 225, cloth bound. This book is the second volume of a new, completely revised edition of the old review with the same title that appeared in 1936. Apart from the title and the regrettable custom of dropping the initials of the given names of the authors in the literature references, the presentation of the new book is very different from the old one. The first four chapters give 587 pages of reviews on (1) androstanes (H. Heusser and H. Jahnke), (2) estranes and estrogenic carboxylic acids (H. Jahnke), (3) pregnanes without an 11-oxygen function (F. Blomeyer), and (4) 11-oxygenated steroids (J. Elks). These reviews are followed by shorter chapt,ers on (5) aldosterone (A. Wettstein), (6) conformational analysis (D. H. R. Bart,on), (7) aromatization react,ions in ring A (H. H. Inhoffen), and (8) the total synthesis of Vitamin D, (K. Irmscher). Owing to this more or less arbitrary division of the subject matter into groups treated independently by different authors, several publications are reviewed twice. The attempt to give as complete a coverage of the literature as possible diminishes the clarity and conciseness of the reviews, and in the first, chapters it might be difficult for anyone not familiar with the subject to distinguish the important from the less relevant facts. In the third chapter an interesting compilation of different react.ions as applied t,o various steroids is to be found, and the fourth chapter gives a clear and complete review of the chemical transformations and synthetic preparations of Il. oxygenated steroids. In general the above-men-
385
REVIEWS
tioned chapters are confined to the chemistry of the substances involved, and pharmacological importance and biological activity are only briefly and incompletely mentioned. The chapter on aldosterone describes not only the isolation, structutal elucidation, and total synthesis of this hormone, but also methods of biological testing, pharmacological properties, and possible pathways of biosynthesis. Barton’s article includes an introduction to conformat.ional analysis as well as discussion of the st,ability relationships in polycyclic cyclohexane systems and of t,he steric requirements of different. reactions with special reference to st,eroid chemistry. The chapter by Inhoffen gives an account of the t.herma1 and acid-catalyzed aromatization react,ions in rings A and B, and in the final chapter the problems of the total snnthesis of vitamin D3 , recently completed in Inhoffen’s laboratories, are discussed. For the specialist in the steroid field the book is a valuable addition to the numerous reviews already existing. The great progress achieved in the last few years especially in the corticoid is, however, not included in the book, because, although published in 1959, it only covers the literature up to 1955 (and a few references from 1956) at which date the manuscripts were put into the editors’ hands. Only the last chapter refers to more recent publications. The views given in the book should therefore only be considered in the light of the general knowledge of 1955. KARL HEUSLER, Basle, Switzerland
in Drug Research. Vol. I. By ERNST Pharmaceutical-Chemical Laboratory Sandoz Ltd., Basle, Switzerland. Birkhauser Verlag, Base1 and Stuttgart, 1959. 607 pp. The work to be reviewed here is the first volume of a new series of progress reports on research in the field of drugs comprising their basic chemical, physicochemical, and biological aspects. Written by experts in the specific fields and maintaining a high level of scientific thoroughness, t,he book will impress the reader as a gratifying attempt to present the development of the fundamentals in therapeutic achievements of the last years. Predominantly theoretical treatment of subjects such as “Ion Exchange” by J. Biichi (Zurich) and “Stereochemical Factors in Biological Activity” by A. H. Becket (London) alternates with reviews of biochemical and clinical character, e.g., on “Cholesterol and Its Relation to Atherosclerosis” by T.-M. Ling and K. K. Chen (Indianapolis, Ind.). The field of chemotherapy is represented by an instructive contribution on “Chemotherapy of Helminthic Infections” by H.-A. Oelkers (HamProgress
JUCKER,