Chemistry of the Carbohydrates

PrefaceI. Introduction 1. Development of Carbohydrate Chemistry 2. General Chemistry A. Stereoisomerism B. Activation by Carbonyl Groups C. Intermolecular Reactions D. The Glycosidic Hydroxyl and Polymeric Carbohydrates 3. Nomenclature and Definitions A. Scope and General Definitions B. Configurational and Trivial Names C. D- and L-Series D. Alpha-Beta DesignationsII. Structure and Stereochemistry of the Monosaccharides 1. Structures of Glucose and Fructose 2. Stereochemistry A. General Principles B. Establishment of the Configuration of Glucose and Some Other Sugars C. D,L Nomenclature 3. Ring Structures of the Sugars A. Necessity for Ring Structures B. Proof of Ring Structure C. Configuration of the Anomeric Carbon Atom D. The Representation of the Ring Structures of the Sugars E. Nomenclature of Anomers (α-ß Non-enclature) 4. Homomorphous Sugars A. Homomorphology B. Nomenclature of the Higher Sugars 5. The Sugars in Solution A. In the Absence of Strong Acids or Alkalies; Mutarotation B. In the Presence of Acids C. In the Presence of Alkalies D. Behavior of the Sugars with Short Carbon Chains 6. Optical Superposition, the Isorotation Rules, and the Influence of Structure on Optical RotationIII. Occurrence, Properties, Synthesis and Analysis of the Monosaccharides 1. Naturally Occurring Monosaccharides A. Introduction B. Properties, Identification, Origin and Preparation of Naturally Occurring Monosaccharides 2. Synthetic Sugars A. Complete Synthesis of the Sugars B. Methods for Lengthening the Carbon Chains of the Sugars C. Methods for Shortening the Carbon Chains of Sugars D. Methods for the Synthesis of Sugars with Terminal Methyl Groups (Methyloses) E. Synthetic Methods Based on Changing the Configuration of Other Sugars F. Preparation of Ketoses by Biochemical Oxidation of Alcohols G. Aldose to Ketose Conversion Utilizing the Osones 3. The identification and the Quantitative Determination of Carbohydrates A. Qualitative Identification B. Quantitative DeterminationIV. Esters 1. Acetyl Derivatives A. Cyclic Acetates B. Acyclic Sugar Acetates (Aldehydo Derivatives) C. Acetates with a Heptanose Ring D. Derivatives of Orthoacetic Acid E. Acetyl Migration 2. Acetylglycosyl Halides (Halogeno Acetyl Sugars) A. Cyclic Forms B. Optical Rotation and Atomic Dimension C. Acyclic Analogs of the Acetylglycosyl Halides 3. Benzoyl Derivatives 4. Galloyl Derivatives and Tannins 5. Other Organic Esters 6. Tosyl and Mesyl Derivatives 1. Nitric Acid Esters 2. Sugar Carbonates 3. Phosphate Esters 4. Esters of Arsenous Acids 5. Sulfate Esters 6. Boric Acid Esters 7. Halogeno EstersV. Glycosides, Full Acetals and Thioacetals 1. Glycosides A. Methods for Synthesis B. Properties of Glucosides C. Determination of the Structures of Glycosides 2. Glycosans (Inner Glycosides) A. Preparation B. Difructose Anhydrides C. Structures D. Reactions 3. Acetal and Mercaptal Derivatives of Acyclic Sugars A. Mercaptals B. Acetals 4. Reactions of Carbohydrates with Aldehydes and Ketones A. Methylene (Formal) Derivatives B. Benzylidene Derivatives C. Condensation with Acetaldehyde and Furfuraldehyde D. Isopropylidene (Acetone) Derivatives E. Acetoacetic Ester DerivativesVI. The Polyols Part I. Acyclic Polyols (Glykitols) 1. Configurations, Occurrence and Preparation 2. Proofs of Structure and Configuration 3. Synthesis 4. Reactions 5. Desoxy Polyols Part II. The Inositols and Related Compounds 1. Isomerization and Representation of Configuration 2. Occurrence and Synthesis 3. Proofs of Structure and Configuration 4. Reactions 5. BiochemistryVII. Acids and Oxidation Products of Carbohydrates 1. Preparation and Reactions A. Aldonic Acids B. Saccharic (Aric) Acids C. Uronic Acids D. Keto Aldonic Acids E. Ascorbic Acids F. Osones 2. Oxidation Agents A. Halogen Oxidations B. Reagents Cleaving Glycols C. Nitric Acid and Nitrogen Oxides D. Oxygen in Alkaline or Neutral Solution E. Hydrogen Peroxide F. Relatively Unspecific Oxidants G. Microbial OxidationsVIII. Ethers, Anhydrides and Unsaturated Derivatives 1. Ether Derivatives (External) A. Alkylation Methods B. Trityl Derivatives 2. Carbohydrate Inner Ethers (Anhydrides) A. Five-membered Rings. 1,4 and 3,6 Types B. Isohexides (1,4-3,6-Hexides) C. 2,5-Anhydro Compounds D. 1,5-Ether Rings E. Epoxy Derivatives F. Biochemistry and Reactions of Sugar Alcohol Anhydrides (Glykitans) 3. Unsaturated Sugars (Glycals and Glycoseens) A. Glycals B. GlycoseensIX. Nitrogenous Derivatives 1. Glycosylamines A. Osimines or Primary Glycosylamines B. N-Glycosides 2. Nucleotides A. Preparation and Structure B. Adenosine Di- and Tri-phosphoric Acids C. Biologically Important Substances Related to the Nucleotides 3. Nucleic Acids A. Thymus Desoxyribonucleic Acid B. Yeast Ribonucleic Acid 4. Reactions of the Sugars with Substituted Hydrazines and Hydroxylamine A. Hydrazones and Osazones B. Oximes 5. Derivatives in Which an Amino Group Replaces a Primary or Secondary Hydroxyl Group A. Amino Sugars (Glycosamines) B. Glycamines and Desoxy Amino Glykitols 6. Combinations of Sugars with Amino Acids and Proteins A. Preparation B. Protein-Carbohydrate Compounds as Synthetic AntigensX. Oligosaccharides 1. Individual Oligosaccharides and Their Classification 2. Synthesis of Oligosaccharides A. From Naturally Occurring Oligosaccharides B. Condensation of Two Monosaccharide Molecules 3. Determination of Structure 4. Ease of Acid Hydrolysis 5. Preparation, Properties and Structures of Some Natural Oligosaccharides A. Disaccharides B. Tri- and TetrasaccharidesXI . Naturally Occurring Glycosides and Glycosidases 1. Anthocyanidin and Flavanol Glycosides 2. Indican 3. Aglycons Related to Phenanthrene A. Cardiac glycosides B. Saponins 4. Substituted-Phenyl Glycosides 5. Vanillin and Coumarin Glucosides 6. Cyanogenetic Glycosides 7. Hydroxyanthraquinone Glycosides 8. Sugar Components of Natural Plant Glycosides 9. Thioglycosides and thiosugars 10. Streptomycin 1. Introduction and Classification 2. Mechanism of Action A. Kinetic Equations and Effect of Substrate Concentrations B. Mechanism C. Influence of Hydrogen Ion Concentration D. Measurement of Activity and Influence of Enzyme Concentration E. Temperature Influences 3. Chemical Composition of Glycosidases A. ß-Glucosidase B. Yeast Invertase 4. Enzymes of Almond Emulsin A. Preparation and Purification B. Optimal pH C. Enzymes Present D . Specificity of the ß-Glucosidase 5. Occurrence and Specificity of Other ß-Glucosidases 6. Alfalfa and Coffee Emulsins 7. Yeast Glycosidases 8. Enzymic Synthesis of Glycosides 9. In Vivo Synthesis of Glycosides 10. Bourquelot Biochemical Determination of Glycosides and Oligosaccharides in Plant MaterialsXII. Classification and Determination of Structure of the Polysaccharides 1. Structural Classification of the Polysaccharides 2. Classification Based on Biological Function 3. General Procedures for the Determination of the Structures of the Polysaccharides A. End Group Analysis B. Structure of a Bacterial Dextran (an Example of Structural Analysis) 4. General Procedures for the Determination of the Molecular Weight of High Polymers A. Osmotic Pressure Method B. Ultracentrifuge C. Viscosity Measurements D. Light Scattering Method E. Other MethodsXIII. Cellulose 1. Occurrence and Structure A. Occurrence B. Chemical Evidence for Structure C. Molecular Weights of Cellulose and Derivatives D. Crystalline Structure 2. Reactions of Cellulose A. Reactions with Bases, Acids and Salts B. Cellulose Xanthate C. Oxycellulose D. Cellulose Esters E. Cellulose Fathers F. Methylene Derivatives G. Hydrolysis by EnzymesXIV. The Starches and Starch Substances 1. Introduction 2. Composition A. General Composition of Starch Granules B. Amylose and Amylopectin C. Soluble Starches D. Chemical Evidence for Structure E. Molecular Weight of Starches F. End Group Assay and Molecular Structure G. X-Ray Diffraction Studies of Starch 3. Starch Esters 4. Ether Derivatives 5. Oxidation Products 6. The Action of Enzymes on Starch A. Saccharogenic or ß-Amylases B. Liquefying Amylases C. Schardinger Dextrins D. "Synthetic" Starches and Phosphoamylases 7. Industrial Preparation and Utilization of Starch and Starch Products 8. GlycogenXV. Polyuronides, Hemicelluloses, Plant Gums, Microbial Polysaccharides and Related Substances 1. Homopolysaccharides A. Glucose Polymers B. Fructose Polymers C. Galacturonic Acid Polymers (Pectins) D. Polymers of Other Hexoses, Pentoses and Uronic Acids E. Polymers of Glucosamine (Chitin) 2. Heteropolysaccharides Derived from Several Sugar Types A. Hemicelluloses and Cell-wall Polysaccharides B. Mucilages, Gums and Gel-forming Substances C. Polysaccharides Associated with Proteins and/or Microorganisms D. Mucopolysaccharides E. Bacterial and Fungal Polysaccharides F. GlycoproteinsAuthor IndexSubject Index