Comprehensive biochemistry. Volume 2, Organic and physical

Mechanism of sulfur reactions (Pryor, William A.) Journal of Chemical Education. Campaigne. 1963 40 (3), p A224. Abstract | PDF w/ Links | Hi-Res PDF...
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BOOK REVIEWS does not duplicate other efforts, hut supplements them. He has summarized many studies on mechanisms of sulfur reactions, and offered selected example8 which supply evidence for these mechanisms. After sn introduction which includes nomenclature, the reactions and properties of elemental sulfur are considered. Then the whole group of thials, disulfides and polysulfides is discussed. First the physical characteristics, such as bond lengths, energies and angles, are reviewed, including a good summary of the evidence for d-orbital overlap in organic sulfur compounds. Then follows an excellent review of the evidence far homolytic cleavage of the disulfide bond. The discussion of

heterolytic cleavage is leas satisfactory. The author has relied heavily on recent articles in Chemieal Reviews for this section. The discussion of nucleophilic attack on the disulfide bond, which has heen reviewed by Parker and Kharasch, is well annotated, hut the suhject of electrophilic sttack is summarized in slightly more than two pages, and the whole system of acid catalyzed cleavage reactions is limited to a reference to chlorination of disulfide, which may or may not proceed via a sulfenium ion, as suggested on page 59. The fallowing five chapters deal with the authors special field of interest, the oxidation, dehydrogenation, and sulfuriaation of hydrocarbons and other organio compounds. Many industrially important reactions, such as vulcanization, are included. In this area Dr.

Pryor is a n obvious authority, and these chapters give the hook its greatest value. Chapters 10 and 11 provide a ueeful supplement of examples of experimental procedures, and a. table of several hundred compounds which have been oxidized by sulfur. Some of the products shown are remarkable, and will offer the arm-chair mechanist some real food fur thought. The text is clear and readable, and remarkably free from error for a hook whieh contains so many structural formulas. This hook mill he a useful source volume for advanced courses in mechanisms of reactions, and ss a library reference.

E. CAMPAIONE Indiana University Bloomingln Comprehensive Biochemistry. Volume 2, Organic and Physical Chemistry

Edited by Marcel Flmkin, University of Lihge, Belgium and Elmer H. Slot+ University of Rochester Sohool of Medicine and Dentistry, Rochester, New York. American Elsevier Pub lishing Co., Inc., New York, 1962. xii 328 pp. Figs. and tables. 15.5 X 23 cm. $14.50.

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This volume is the second in the section of "Comprehensive Biochemistry" devoted to physico-chemical and organic aspects of biochemistry. The hook contains three chapters: Mechanisms of Organic Reactions by M. L. Bender and R. Breslow; and Behaviour of Molecules in Solution; and Diffusion and Osmosis, by W. D. Stein. In the reviewerr8 ooinion. Bender's treatment of mechanism of organic reactions will prove invaluable to any biachemist who is concerned with the mechanism of an enzymatic process. This chapter represents one of the most complete reviews of analogies between organic and enzymatic systems to be found in the current literature. I t is understandable that most attention has been paid to non-oxidative reactions since the best enzyme models are to he found in this area. In the relatively brief section an oxidation-reduction systems no d i e cussion is made of flavaemyme catalysis. Albeit, the authors are to be commended for s n excellent review. The text is well complemented by clearly drawn formulas. The last two chapters in this volume, by Stein, are beautifully mitten. The discussion of solutions proceeds logically through four sections: small nonelectrolytes, small electrolytes, polymers, and finally, polyelectrolytes and protans. The last chapter is concerned with the molecular-kinetic basis of diffusion, osmasis, and viscosity. Although the various equations pertinent to these phenomena are not derived, adequate references are presented for this p lrpose. I t cannot be denied that "Comprehensive Biochemistry,'' when completed, will be an often consulted reference series for all biochemists "at the bench." I t will also he a welcome reference far the instructor and the more advanced student (Continued on page A228)

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Journal o f Chemical Education

BOOK REVIEWS of biology, biophysics, and biochemistry a t the undergraduate level.

University of Colorado School of Medicine

Orgmophosphorus Polymers

Monomers

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E. L. Geflw, Academy of Sciences, U.S.S.R. Translated by G. M. Kosolapoff, Auburn University, Alabama. Trans. ed. by Leon Jacolw, Associated Technical Services, Inc., Glen Ridge, New Jersey. Associated Technical 288 pp. Services, Inc., 1962. xix Figs. andtables. 17.5 X 26em. 814.75.

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The present monograph is the first to appear which deals with heteroorganic polymers other than those containing nitrogen and silicon. The author has attempted t o generalize and systematize the existing information concerning the synthesis and physical properties of polymers containing phosphorus ss a constituent in the main skeleton or in side chains. I n addition, considerable attention has been paid to synthetic methods leading t o monomers of use in palymerizatian reactions. Much of the information concerning both monomers and polymers is presented in easily accessible tahular farm; included here are such items a8 reaction conditions, nature of the reaction product, yields, analyses, and certain physical data. One very helpful feature is the inclusion of a section on nomenclature. The United Kingdom and United States of America, journals use the system proposed by joint agreement in 1952 and which has been recognized by the International Union of Pure and Applied Chemistry (1960). Although agreement on this score is far from unanimous and is not practiced in non-English-speaking countries, the translator has used the "new" 8ystem and included parenthetically same of the more familiar "old" names in preparing illustrations of name types. Part I of the monograph (136 pages) describes the chemistry and properties of starting materials used for the preparation of organophosphorus high polymers. Chapter I deals with unsaturated organophosphorus compounds. Included in the discussion are certain unsaturated acids and their derivatives such as esters formed from acids and unsaturated alcohols, vinyl compounds, and unsaturated phosphines, their oxides and related compounds. Chapter I1 concerns the preparation and properties of saturated organophosphorus compounds having reactive functional groups as, far example, the dichlorides of some saturated acids of phosphorus, polyhydroxyl compounds, palycarhoxylic acids and their esters, amides, etc. Chapter 111 provides tables of the refraction of some

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