Organic_Chemistry.pdf - Organic chemistry ORGANIC CHEMISTRY methane to macromolecules JOHN D ROBERTS California ~nsiiitkeof Technology ROSS STEWART

Organic_Chemistry.pdf - Organic chemistry ORGANIC CHEMISTRY...

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Unformatted text preview: Organic chemistry ORGANIC CHEMISTRY methane to macromolecules JOHN D. ROBERTS California ~nsiiitkeof Technology ROSS STEWART University of British Columbia MARJORIE C. CASERIO University of California, Irvine W. A. BENJAMIN, INC. New York 1971 Organic chemistry: Methane t o macromolecules Copyright 0 1971 by W. A. Benjamin, Inc. All rights reserved Standard Book Number 8053-8332-8 Library of Congress Catalog Card Number 71-130356 Manufactured in the United States of America 12345K54321 Portions of this book appeared previously in Modern Organic Chemistry by John D. Roberts and Marjorie C. Caserio, published by W. A. Benjamin, Inc. 1967, New York W. A. BENJAMIN, INC. New York. New York 10016 preface The success achieved by this book's forerunners, Basic Principles of Organic Chemistry and Modern Organic Chemistry, was to a considerable extent due to the rigor with which the subject of organic chemistry was presented. In the present work we have tried to paint an interesting, relevant, and up-to-date picture of organic chemistry while retaining the rigorous approach of the earlier books. Organic chemistry sometimes appears to be enormously complex to the beginning student, particularly if he must immediately grapple with the subjects of structural isomerism and nomenclature. We have attempted to avoid this difficulty in the following way. Chapter 1 briefly relates carbon to its neighbors in the Periodic Table and reviews some fundamental concepts. Chapter 2 deals with the four C, and C , hydrocarbons-methane, ethane, ethene, and ethyne-and discusses their conformational and configurational properties and some of their chemical reactions. The reader thus makes an acquaintance with the properties of some important organic compounds before dealing in an open-ended way with families of compounds-alkanes, alcohols, etc. A heavy emphasis on spectroscopy is retained but the subject is introduced somewhat later than in the earlier books. Important additions are chapters dealing with enzymic processes and metabolism and with cyclization reactions. Many of the exercises of the earlier books have been retained and have been supplemented with drill-type problems. It seems a shame to burden the mind of the beginning student with trivial names, some of them quite illogical, and throughout we have stressed IUPAC nomenclature, which is both logical and easy to learn. The instructor, who may well carry lightly the excess baggage of redundant names, may occasionally find this irritating but we ask him to consider the larger good. As a further aid to the student, each chapter concludes with a summary of important points. The simple introduction to the subject and the emphasis on relevance, particularly to living systems, should make the book appealing to the general student. At the same time we hope that the up-to-date and more advanced topics that are included-the effect of orbital symmetry on cyclization reactions, for example-will also appeal to the chemistry specialist. We should like to acknowledge the help of many persons who read all or parts of the manuscript and offered sound advice. Professor George E. Hall read the manuscript at several stages of revision and we are particularly preface vi grateful to him. Others who helped us were Drs. E. Caress, L. D. Hall, D. N. Harpp, J. P. Kutney, T. Money, M. Smith, T. Spencer, and L. S. Weiler. We conclude this preface on a mildly philosophical note. The world of tomorrow will result from the interplay of powerful forces-some social, some technological. Responsible public action requires public knowledge and there are few areas of science that impinge more on the life around us than does organic chemistry. We hope that those who study this book will utilize their knowledge responsibly for 'the benefit of all who come after. JOHN D. ROBERTS ROSS STEWART MARJORIE C. CASERIO Pasadena, California Vancouver, British Columbia Irvine, California contents Chapter I Introduction 1.1 Bonding in Organic Compounds 1.2 Methane, Ammonia, Water, and Hydrogen Fluoride Summary Exercises Chapter 2 The C, and C, hydrocarbons 2.1 Molecular Shape of CH, , C2H6, C2H4, and C,H, 2-2 Rotational Conformations of Ethane 2.3 Space-Filling Models Chemical Reactions of the C , and C, Hydrocarbons 2.4 Combustion 2.5 Substitution Reactions of Saturated Hydrocarbons 2.6 Addition Reactions of Unsaturated Hydrocarbons Summary Exercises Chapter 3 Alkanes Nomenclature Physical Properties of Alkanes-Concept Alkanes and Their Chemical Reactions 3.4 Cycloalkanes Summary Exercises of Homology Chapter 4 Alkenes 4.1 4.2 4-3 4.4 Nomenclature lsomerism in C,H, Compounds Cis and Trans Isomers Chemical Reactions of Alkenes Summary Exercises Chapter 5 Alkynes 5.1 Nomenclature 5-2 Physical Properties of Alkynes vii contents 5.3 5.4 5.5 5.6 viii Ethyne Addition Reactions of Alkynes Alkynes as Acids Synthesis of Organic Compounds Summary Exercises Chapter 6 Bonding in conjugated unsaturated systems 6.1 6.2 6.3 6.4 6.5 6.6 6-7 Bonding in Benzene Conjugate Addition Stabilization of Conjugated Dienes Stabilization of Cations and Anions Vinyl Halides and Ethers Rules for the Resonance Method Molecular Orbital Method of Hiickel Summary Exercises Chapter 7 Isolation and identification of organic compounds 151 7.1 Isolation and Purification 7.2 Identification of Organic Compounds Spectroscopy 7.3 7.4 7.5 7.6 159 Absorption of Electromagnetic Radiation Infrared Spectroscopy Ultraviolet and Visible Spectroscopy (Electronic Spectroscopy) N ~ ~ c l e aMagnetic r Resonance Spectroscopy Summary Exercises 159 161 165 168 179 180 Chapter 8 Nucleophilic displacement and elimination reactions 8.1 Organic Derivatives of Inorganic Compounds 8.2 Alcohol Nomenclature 8.3 Ether Nomenclature 8.4 Carboxylic Acid Nomenclature 8.5 The Use of Greek Letters to Denote Substituent Positions 8.6 Single- or Multiple-Word Names Nucleophilic Displacenzent Reactions 8.7 8.8 8.9 8.10 8.1 1 General Considerations Mechanisms of S, Displacements Energetics of S,1 and S,2 Reactions Stereochemistry of S,2 Displacements Structural and Solvent Effects in S, Reactions 185 187 187 190 190 191 191 192 contents Elimination Reactions 205 8.12 The E2 Reaction 8.13 The El Reaction Summary Exercises Chapter 9 Alkyl halides and organometallic compounds 9-1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 Physical Properties Spectra Preparation of Alkyl Halides Reaction of Alkyl Halides Vinyl Halides Allyl Halides Polyhalogen Compounds Fluorinated Alkanes Organometallic Compounds Summary Exercises Chapter 10 Alcohols and ethers 10.1 Physical Properties of Alcohols 10.2 Spectroscopic Properties of Alcohols-Hydrogen 10.3 Preparation of Alcohols Bonding Chemical Reactions of Alcohols 10.4 10-5 10.6 10.7 10-8 Reactions Involving the 0-H Bond Reactions Involving the C-0 Bond of Alcohols Oxidation of Alcohols Polyhydroxy Alcohols Unsaturated Alcohols Ethers 10.9 Preparation of Ethers 10.10 Reactions of Ethers 10.1 1 Cyclic Ethers Summary Exercises Chapter a I Aldehydes and ketones P. Reactions at the carbonyl group 11.1 11.2 11.3 11.4 Nomenclature of Aldehydes and Ketones Carbonyl Groups of Aldehydes and Ketones Preparation of Aldehydes and Ketones Reactions of Aldehydes and Ketones Summary Exercises ix conte Chapter 12 Aldehydes and ketones 11. Reactions involving substituent groups. Polycarbonyl compounds 12-1 Halogenation of Aldehydes and Ketones 12.2 Reactions of Enolate Anions Unsaturated Carbonyl Compounds 12.3 +Unsaturated 12.4 Ketenes Aldehydes and Ketones Polycarbonyl Compounds 12.5 1,2-Dicarbonyl Compounds 12.6 1,3-Dicarbonyl Compounds Summary Exercises Chapter 13 Carboxylic acids and derivatives 13.1 13.2 13.3 13.4 13.5 13.6 13-7 Physical Properties of Carboxylic Acids Spectra of Carboxylic Acids Preparation of Carboxylic Acids Dissociation of Carboxylic Acids Reactions at the Carbonyl Carbon of Carboxylic Acids Decarboxylation of Carboxylic Acids Reactions at the 2 Positiod of Carboxylic Acids Functional Derivatives of Carboxylic Acids 13.8 Displacement Reactions of Acid Derivatives 13.9 Reactions at the 2 Position (a position) of Carboxylic Acid Derivatives 13.10 Reactions of Unsaturated Carboxylic Acids and Their Derivatives 13.11 Dicarboxylic Acids Summary Exercises Chapter 14 Optical isomerism. Enantiomers and diastereomers 14.1 14-2 14.3 14.4 Plane-Polarized Light and the Origin of Optical Rotation Specific Rotation Optically Active Compounds with Asymmetric Carbon Atoms Optically Active Compounds Having No Asymmetric Carbon Atoms 14.5 Absolute and Relative Configuration 14.6 Separation or Resolution of Enantiomers 14.7 Asymmetric Synthesis and Asymmetric Induction contents 14.8 Racemization 14.9 Inversion of Configuration 14.10 Optical Rotatory Dispersion Summary Exercises Chapter 15 Carbohydrates 15.1 15.2 15.3 15.4 15.5 15.6 15.7 15.8 15.9 Classification of Carbohydrates Glucose Cyclic Structures Mutarotation Glycosides Disaccharides Polysaccharides Vitamin C Immunologically Important Carbohydrates Summary Exercises Chapter 16 Organic nitrogen compounds 16.1 16.2 16.3 16.4 16.5 16.6 Amines Amides Nitriles Nitroso Compounds Nitro Compounds Some Compounds with Nitrogen-Nitrogen Bonds Summary Exercises Chapter 17 Amino acids, proteins, and nucleic acids 17.1 17.2 17.3 17.4 17.5 17.6 17.7 17.8 Amino Acids Lactams Peptides Protein Structures Biosynthesis of Proteins The Structure of DNA Genetic Control and the Replication of DNA Chemical Evolution Summary Exercises Chapter 18 Enzymic processes and metabolism 18.1 Catalysis in Organic Systems 18.2 Enzymes and Coenzymes 18.3 Hydrolytic Enzymes xi contents 18.4 Oxidative Enzymes 18.5 The Energetics of Metabolic Processes Summary Exercises Chapter 19 Organic compounds of sulfur, phosphorus, silicon and boron 19.1 19.2 19.3 19.4 19-5 d Orbitals and Chemical Bonds Types and Nomenclature of Organic Compounds of Sulfur Phosphorus Compounds Organosilicon Compounds Organoboron Compounds Summary Exercises Chapter 20 Arenes. Electrophilic aromatic substitution 20.1 20.2 20.3 20.4 20.5 Nomenclature of Arenes Physical Properties of Arenes Spectroscopic Properties of Arenes Reactions of Aromatic Hydrocarbons Effect of Substituents on Reactivity and Orientation in Electrophilic Aromatic Substitution 20.6 Substitution Reactions of Polynuclear Aromatic Hydrocarbons 20.7 Nonbenzenoid Conjugated Cyclic Compounds Summary Exercises Chapter 2I Aryl halogen compounds. Nucleophilic aromatic substitution 21.1 21.2 21.3 21.4 Physical Properties of Aryl Halogen Compounds Preparation of Aryl Halides Reactions of Aryl Halides Organochlorine Pesticides Summary Exercises Chapter 22 Aryl nitrogen compounds Aromatic Nitro Compounds 22-1 22.2 22.3 22.4 Synthesis of Nitro Compounds Reduction of Aromatic Nitro Compounds Polynitro Compounds Charge-Transfer and TC Complexes Aromatic Amines 22.5 General Properties xii contents 22.6 Aromatic Amines with Nitrous Acid Diazonium Salts 22.7 Preparation and General Properties 22.8 Replacement Reactions of Diazonium Salts 22.9 Reactions of Diazonium Compounds that Occur Without Loss of Nitrogen Summary Exercises Chapter 23 Aryl oxygen compounds 23.1 23.2 23.3 23.4 23.5 Synthesis and Physical Properties of Phenols Some Chemical Properties of Phenols Polyhydric Phenols Quinones Tropolones and Related Compounds Summary Exercises Chapter 24 Aromatic side-chain derivatives Preparation of Aromatic Side-Chain Compounds 24.1 24.2 24.3 24.4 Aromatic Carboxylic Acids Preparation of Side-Chain Aromatic Halogen Compounds Side-Chain Compounds Derived from Arylmethyl Halides Preparation of Aromatic Side-Chain Compounds by Ring Substitution Properties of Aromatic Side-Chain Derivatives 24.5 Arylmethyl Halides. Stable Carbonium Ions, Carbanions, and Radicals 24.6 Aromatic Aldehydes 24.7 Natural Occurrence and Uses of Aromatic Side-Chain Derivatives 24.8 Electron Paramagnetic Resonance (epr) Spectroscopy 24.9 Linear Free-Energy Relations Summary Exercises Chapter 25 Heterocyclic compounds 25-1 Aromatic Character of Pyrrole, Furan, and Thiophene 25.2 Chemical Properties of Pyrrole, Furan, Thiophene, and Pyridine 25.3 Polycyclic and Polyhetero Systems Heterocyclic Natural Products 25.4 Natural Products Related to Pyrrole 25.5 Natural Products Related to Indole 25.6 Natural Products Related to Pyridine, Quinoline, and Isoquinoline 25.7 Natural Products Related to Pyrimidine xiii 616 contents 25.8 Natural Products Related to Purine and Pteridine 25.9 Natural Products Related to Pyran 25.10 Polyhetero Natural Products Summary Exercises Chapter 26 Photochemistry Light Absorption, Fluorescence, and Phosphorescence Light Absorption and Structure Photodissociation Reactions Photochemical Reduction Photochemical Oxidation Photochemical Isomerization of Cis- and TransUnsaturated Compounds 26.7 Photochemical Cycloadditions Summary Exercises 26.1 26.2 26.3 26.4 26.5 26.6 Chapter 27 Cyclization reactions 27.1 27.2 27.3 27.4 27.5 Cyclization Reactions of Carbonyl Compounds Cycloaddition Reactions of Carbon-Carbon Multiple Bonds Fluxional Systems Annulenes Orbital Symmetry and Cycloaddition Chapter 28 Polymers 28.1 Types of Polymers Physical Properties of Polymers 28.2 Forces Between Polymer Chains 28.3 Correlation of Polymer Properties with Structure Preparation of Syzthetic Polymers 28.4 28.5 28.6 28.7 Condensation Polymers Addition Polymers Naturally Occurring Polymers Dyeing of Fibrous Polymers Chapter 29 Some aspects of the chemistry of natural products 29-1 Civetone 29.2 Spectroscopic Methods in the Determination of the Structures of Natural Products 29-3 Terpenes 29.4 Steroids 29.5 Biogenesis of Terpenes and Steroids Index xiv 686 686 688 688 689 chap 1 introduction 3 Twenty-two centuries ago the Greek mathematician Euclid wrote a textbook on geometry that is still in use today. Some 300 years ago Isaac Newton discovered the principles of mechanics that can still be applied with great precision to most macroscopic systems. By contrast, chemistry, and in particular organic chemistry, is in its infancy as a precise science. The study of molecular science-because this is what chemistry essentially is-depends on inferences about submicroscopic bodies drawn from observations of macroscopic behavior. The speculations of the early chemists are best described as "haywire " rather than as "incorrect " and it was only in the last century that the foundations of chemical theory became firmly established. Since that time enormous strides have been made in extending chemical knowledge. And today, some 1,100,000 organic compounds alone (compounds containing carbon) have been prepared, their structures elucidated, and their properties examined. The flowering of organic chemistry in the past hundred years followed two events during the last century. The first occurred in 1828, when the German chemist Wohler discovered that ammonium cyanate ( N H 4 @ C ~ O Q could ) be 0 1I converted to the compound urea (NH2CNH2).The former was a typical salt and is considered part of the mineral world, whereas urea was a product of animal metabolism and therefore part of the living or organic world. The realization gradually followed that the boundary between living and nonliving systems could be crossed, and this provided the impetus for intensive investigation of the substances found in nature: the term " organic " was thus applied to all compounds of carbon whether they were found in nature or were prepared in the laboratory. The second important occurrence in the last century as far as organic chemistry was concerned was the recognition, achieved between 1858 and 1872, that unique, three-dimensional structures could be drawn for the molecules of every known compound of carbon. This realization followed essentially the work of six men: Avogadro, Cannizzaro, Kekul6, Couper, LeBel, and van't Hoff. Avogadro and Cannizzaro distinguished between what we would now call empirical and molecular formulas. Avogadro's hypothesis that equal volumes of gases contained equal numbers of molecules was actually made in 1811 but it was not until 1860 that the Italian chemist Cannizzaro made use of this idea to distinguish between different compounds having the same composition. Thus, the distinction between the molecules C2H4 and C,H, became clear, and it was realized that neither had the molecular formula CH, , though both had this empirical formula. At about the same time KekulC, a German, and Couper, a Scot, suggested that carbon was tetravalent, always forming four bonds. Two young chemists, LeBel and van't Hoff, then independently provided convincing proof that these four bonds are tetrahedrally arranged around the carbon atom (Section 14.6). Part of the fascination of organic chemistry comes from the knowledge that the whole complex edifice has been built up from indirect study of molecular behavior, that is, microscopic understanding from macroscopic observation. The advent in recent years of sophisticated instrumental techniques for ex- chap 1 introduction 4 amining structure has confirmed the vast majority of the structures assigned to organic compounds in the late nineteenth century. Spectroscopy and X-ray crystallography, in particular, have become powerful tools for checking previously assigned structures and for elucidating structures of compounds newly prepared in the laboratory or found in nature. Considerable use will be made in this book of spectroscopy-the study of how "light" (to be more exact, electromagnetic radiation) is absorbed by matter. The infrared, ultraviolet, and nuclear magnetic resonance spectra may permit the correct structure of a fairly complex compound to be assigned in a matter of hours. If, at this point, a search of the chemical literature reveals that the compound with the suspected structure has been previously prepared, it is only necessary to compare the reported physical or spectroscopic properties with those of the substance being examined. However, if the compound has not been previously reported, it must be synthesized from starting materials of known structure before its structure is really considered to be proven. Organic chemistry occupies a central position in the undergraduate science curriculum. It is, of course, an important branch of knowledge in its own right, but in addition it is the foundation for basic studies in botany, zoology, microbiology, nutrition, forestry, agricultural sciences, dentistry, and medicine. Antibiotics, vitamins, hormones, sugars, and proteins are only a few of the important classes of chemical substances that are organic. In addition, many industrially important products are organic-plastics, rubber, petroleum products, most explosives, perfumes, flavors, and synthetic fibers. It is little wonder that there are more organic chemists than chemists of any other kind. Of the 2000 or so Ph.D.'s awarded each year in chemistry in North America, about half go to those whose research has been in organic chemistry. The research may have involved the synthesis of a new compound of unusual structure, the elucidation of the structure of a new compound extracted from a plant, or the discovery of the reaction path that is followed when one compound is converted to another. Only a few years ago most people regarded the effects of chemical technology as being wholly beneficial. Pesticides, herbicides, plastics, and synthetic drugs all seemed to contribute in large or small measure to human welfare. Recently we have come to realize, however, that our environment cannot indefinitely accommodate all the products that are being added to it without being damaged. A pesticide may be extremely effective at eradicating some of man's enemies but may seriously endanger some of man's friends. A cogent example is the way the potent insecticide DDT (Section 24.7) causes bird egg shells to become thin. Further, a synthetic plastic may be immune to sunlight, rain, and bacterial decay but this is a doubtful benefit after the object made from it has been discard...
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