Foundations of Organic Chemistry: Unity and Diversity of Structures, Pathways, and Reactions

ISBN-13: 9781119656425 / Angielski / Twarda / 2020 / 1376 str.

David R. Dalton

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Prologue xixAcknowledgments xxiAbout the Companion Website xxiiiPart I Background 11. An Introduction to Structure and Bonding 5A. The Sources of Carbon Compounds 5I. How Do We Know a Material is Pure? 6B. More About Hydrocarbons: Heats of Combustion and Reaction 9I. Combustion: Heats of Reaction 9C. On The Nature of the Chemical Bond 12I. Ionic and Nonpolar Covalent Bonds 12II. Polar Covalent Bonds: Mixing Orbitals and Molecular Orbitals 17III. The Use of Orbital Hybridization and Molecular Orbitals 21a. Summary Comment on Bonding Models 37IV. Allotropes of Carbon 37V. Combination of Ionic and Covalent Bonding 37Notice to the Student 41Problems 41Notes and References 442. An Introduction to Spectroscopy and Selected Spectroscopic Methods in Organic Chemistry 49A. General Introduction. The Electromagnetic Spectrum 49B. X-Ray Crystallography 51C. Photon Spectroscopy 52I. General Introduction 52II. Ultraviolet and Visible Spectroscopy 54III. Infrared Spectroscopy 56IV. Raman Spectroscopy 58V. Microwave Spectroscopy 58VI. Magnetic Resonance Spectroscopy 59a. Nuclear Magnetic Resonance (NMR) 591. The Chemical Shift 622. Multiplicity (The Coupling Constant: Spin-Spin Splitting) 653. The Integrated Area 664. Expansion of the Principle 675. NMR in Two Dimensions 696. Double Resonance 707. ¯13C, ¯19F, and ¯31P NMR Spectroscopy 72b. Electron Spin Resonance (ESR) Spectroscopy or Electron Paramagnetic Resonance (EPR) Spectroscopy 74D. Mass Spectrometry 75I. Creation of Ions in the Mass Spectrometer: The Ionization Chamber 76II. The Separation of Ions by Mass: The Mass Analyzer 76III. Detecting the Ions 77Problems 77Notes and References 783. Structure: The Nomenclature of Hydrocarbons and the Shape of Things to Come 83A. Introduction 83B. Nomenclature and Spectroscopy 84I. Alkanes in Two and Three Dimensions 84a. Acyclic Alkanes 84b. Cyclic Alkanes 89II. Alkenes, Arenes, and Alkynes in Two and Three Dimensions 92a. Alkenes 93b. Arenes 97c. Alkynes 102C. Physical and Chemical Properties: Oxidation and Reduction of Hydrocarbons 104I. The Concept of Homology 105II. Oxidation and Reduction 105a. Oxidation 105b. Reduction 108Problems 112Notes and References 1154. An Introduction to Dynamics 119A. Introduction 119B. Review of Some Energy Considerations 120C. The Barrier Between Reactants and Products 121D. More About the Transition State 123E. Rotation About Sigma (Sigma) Bonds in Acyclic Alkanes, Alkenes, Alkynes, and Alkyl-Substituted Arenes 126I. Alkanes 126II. Alkenes, Alkynes, and Alkyl-Substituted Arenes 129F. Conformational Analysis of Medium-Ring Cyclic Alkanes 131G. The Conservation of Symmetry During Reactions 146H. The Measurement of Chirality 156I. The Wave Nature of Light 156II. Plane-Polarized Light and Handedness 157III. Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) 160Problems 162Notes and References 1655. Classes of Organic Compounds: A Survey Along with an Introduction to Solvents, Acids and Bases, and to More About Computational Chemistry 173A. Introduction 173B. General Characteristics of Functional Group Placement 175C. The Functional Groups, Their Names, and Some Physical and Spectroscopic Properties 176I. Hydrocarbons 176a. Alkanes 176b. Alkenes 176c. Alkynes 178d. Arenes 178II. Alkyl and Aryl Halides 179III. Alcohols and Phenols 183IV. Ethers 190V. Thiols, Thioethers, and Disulfides and Their Oxides 193VI. Amines, Hydrazines, and Other Nitrogenous Materials 196VII. Phosphines, Phosphonium Salts, and Other Phosphorus Derivatives 199VIII. An Introduction to Organometallic Compounds 201IX. Compounds Containing Unsaturated Functional Groups 204a. Aldehydes 204b. Ketones 210c. Nitrogen, Sulfur, and Phosphorus Analogues of Aldehydes and Ketones 212d. Carboxylic Acids 213e. Carboxylic Acid Derivatives 2171. Carboxylic Acid Halides (Acyl Halides) 2182. Carboxylic Acid Anhydrides 2193. Carboxylic Acid Esters and Lactones 2214. Amides, Lactams, Imides, Hydroxamic Acids, and Ureas 2275. Nitriles 236D. An Introduction to Solvents 237I. Protic and Aprotic Solvents 238II. Polar and Nonpolar Solvents 238III. Polarizability 239IV. Choosing a Solvent 240a. Solvents for Spectroscopy 2401. Solvents for UV Spectroscopy 2402. Solvents for IR and Raman Spectroscopy 2403. Solvents for NMR Spectroscopy 240b. Immiscible Liquids 241c. Organic Compounds That Dissolve in Water 241d. Phase Transfer Catalysts 242E. Acids and Bases 242I. Brønsted Acids and Bases 243II. Lewis Acids and Bases 245III. Hard and Soft Acids and Bases (HSAB) 248F. Computational Methods 250I. Molecular Mechanics 251a. Stretching Energy Contribution (Estretch) 251b. Bending Energy Contribution (Ebend) 251c. Stretch-Bend Energy Contribution (Estretch-bend) 251d. Van der Waals Energy Contribution (Evan der Waals) 252e. Torsional Energy Contribution (Etorsional) 252f. Dipole Interaction Energy and Dipole Moment Contribution (Edipole) 252Problems 253Notes and References 255Part II Middleground 2616. The Reactions of Hydrocarbons: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 271A. Introduction 271B. Alkanes 271I. Oxidation 271II. Reduction 276III. Substitution 276IV. Rearrangement 280C. Alkenes 280I. Oxidation 280II. Reduction 286III. Addition 292a. Electrophilic Addition 2941. The Stereochemistry of Electrophilic Addition 2952. The Regiochemistry of Electrophilic Addition 2983. The Kinetics of Electrophilic Addition 3114. Cationic Polymerization: Electrophilic Addition in the Absence of a Reactive Nucleophile 3155. Electrophilic Addition to Dienes and Polyenes 3176. Special Cases: The Oxo and Ritter Reactions 321b. Nucleophilic Addition to Alkenes, Dienes, and Polyenes 323c. Radical Addition to Alkenes, Dienes, and Polyenes 327d. Intermolecular Cheletropic and Other Cycloaddition Reactions 329IV. Substitution 340V. Rearrangements 343D. Alkynes 353I. Oxidation 353II. Reduction 354III. Addition 355a. Electrophilic Addition 356b. Nucleophilic Addition to Alkynes and Conjugated Ene-Ynes 362c. Radical Addition to Alkynes 365d. Intermolecular Cheletropic and Other Cycloaddition Reactions 365E. Arenes and Aromaticity: Special Introduction 370I. Oxidation 377a. Oxidation of the Aromatic Ring 377b. Oxidation of Alkyl Substituents on the Aromatic Ring 381II. Reduction 382III. Addition 384IV. Substitution 385a. Electrophilic Aromatic Substitution 386b. Nucleophilic Aromatic Substitution 405c. Free Radical Substitution 405Problems 407Notes and References 4107. The Reactions of Alkyl, Alkenyl, and Aryl Halides: Oxidation, Reduction, Substitution, Addition, Elimination, and Rearrangement 423A. Introduction 423B. Fluorocarbons 426I. Freons and Halons 427II. Polymers of Highly Fluorinated Monomers 428III. Use of Fluorocarbons to Carry Oxygen 428C. Oxidation 428D. Reduction of Alkyl, Alkenyl, and Aryl Halides 430I. Dehalogenation and Reductions at Carbon 430a. Hydrogenolysis 431b. Substitution of Hydride for Halide 431c. Radical Replacement of Halogen by Hydrogen 431d. Reaction of Alkyl, Alkenyl, and Aryl Halides with Metals 4331. Organomercurials 4332. Organomagnesium Compounds (Grignard Reagents) 4343. Alkyl, Alkenyl, and Aryl Lithium Reagents 437II. Reductions at Halogen 439E. Nucleophilic Substitution 440I. Nucleophiles and Nucleophilicity 441II. Substitution, Nucleophilic, Unimolecular (SN1) 442a. The Kinetics 443b. Electronegativity Differences 446c. The Structure of the Alkyl Group 447d. The Role of the Solvent 448e. The Substrate Stereochemistry Attending the SN1 Reaction 449III. Substitution, Nucleophilic, Bimolecular (SN2) 452a. The Kinetics 454b. The Stereochemistry Attending the SN2 457c. The Nature of the Leaving Group 459d. The Nature of the Nucleophile 459e. The Nature of the Solvent 460IV. The SN2' Reaction 460V. Nucleophilic Aromatic Substitution 460a. The Elimination-Addition Pathway (Benzyne) 461b. The Addition-Elimination Pathway (SNAr Substitution) 462VI. Electrophilic Aromatic Substitution 463VII. Substitution by Carbon 464VIII. Photochemically Induced Substitution of Vinyl and Aryl Halides 468F. Addition Reactions 468I. Addition Reactions to Vinyl and Allyl Halides 469G. Elimination Reactions of Alkyl and Alkenyl Halides 473I. alpha-Elimination (1,1-Elimination) 474a. alpha-Elimination of HX (X = Cl, Br) from Alkyl and Alkenyl Halides 474b. alpha-Elimination of X2 (X = Cl) from Alkyl Dihalides 475II. ß-Elimination (1,2-Elimination) 475a. ß-Elimination of HX (X = F, Cl, Br, I) from Alkyl and Alkenyl Halides 4751. Elimination, Unimolecular (E1) 4762. Elimination, Unimolecular, conjugate base (E1cb) 4823. Elimination, Bimolecular (E2) 4844. 1,2-Elimination and the Primary Deuterium Isotope Effect 498b. 1,2- or alpha,ß-Elimination of X2 (X = Cl, Br) from Alkyl and Alkenyl Dihalides 501III. gamma-Elimination (1,3-Elimination) and delta-Elimination (1,4-Elimination) 502a. gamma-Elimination of HX (X = Cl, Br, I) from Alkyl and Alkenyl Halides 502b. gamma-Elimination of X2 (X = Cl, Br, I) from Alkyl Halides 502c. delta-Elimination of X2 (X = Cl, Br, I) from Alkenyl Halides 503H. Rearrangement Reactions of Alkyl and Alkenyl Halides 503Problems 510Notes and References 5128. Part I. The Reactions of Alcohols, Enols, and Phenols: Oxidation, Reduction, Substitution, Addition, Elimination, and RearrangementPart II. EthersPart III. Selected Reactions of Alkyl and Aryl Thiols and Thioethers 523Special Introduction 523Part I. Alcohols, Enols, and Phenols 526A. Acidity and Basicity 526B. Oxidation of Alcohols, Enols, and Phenols 533I. Introduction 533II. Oxidation at the Hydroxyl-Bearing Carbon 534a. Chemical Oxidation of Alcohols 534b. Biological Oxidation of Alcohols 547III. Oxidation at Sites That Do Not Bear the Hydroxyl 549a. Oxidation of Enols 549b. Oxidation of Phenols 553c. Oxidation at the Double Bond of Allylic Alcohols 555C. Reduction of Alcohols, Enols, and Phenols 559I. Reduction of Alcohols 559II. Reduction of Enols and Phenols 560D. Substitution Reactions of Alcohols, Enols, and Phenols 563I. Introduction 563II. Substitution Reactions of Alcohols, Enols, and Phenols at Oxygen 564III. Substitution Reactions of Alcohols at Carbon 566a. Formation of Alkyl Halides 566b. Replacement of the Hydroxyl (-OH) Functional Group by Other Substituents 567c. Replacement of the Hydroxyl (-OH) Functional Group by Carbon 5711. An Example from Nature 571IV. Substitution Reactions of Enols and Phenols at Carbon 572a. Substitution at the Carbon-Bearing Oxygen 572b. Electrophilic Aromatic Substitution of Phenols 574E. Addition Reactions of Alcohols, Enols, and Phenols 581I. Introduction 581II. Addition of the Oxygen of Alcohols to Carbon (with Loss of Hydrogen) 583F. Elimination Reactions of Alcohols, Enols, and Phenols 599I. Introduction 599II. Acid-Catalyzed Elimination of Water 601III. Elimination from Derivatives of Alcohols 604G. Rearrangement Reactions of Alcohols, Enols, and Phenols 614I. Introduction 614Part II. Ethers 624A. Introduction 624B. The Reactions of Ethers 625Part III. Thiols, Thioethers, and Some Products of Their Oxidation 638Problems 648Notes and References 6499. Part I. The Reactions of Aldehydes and Ketones : Oxidation, Reduction, Addition, Substitution, and RearrangementPart II. The Reactions of Carboxylic Acids and Their Derivatives: Oxidation, Reduction, Addition, Substitution, Elimination, and Rearrangement 667Introduction 667Part I. Aldehydes and Ketones 676A. Oxidation of Aldehydes and Ketones 676B. Reduction of Aldehydes and Ketones 687I. Introduction 687II. Reduction of Aldehydes and Ketones to Hydrocarbons 688III. Reduction of Aldehydes and Ketones to Alcohols 688C. Addition to Aldehydes and Ketones 700I. Introduction 700II. Photochemical Reactions of Aldehydes and Ketones 703a. Nonconjugated Carbonyl Compounds 703b. Conjugated Carbonyl Compounds 704III. Thermal Electrocyclic and Related Reactions of Aldehydes and Ketones 706a. Nonconjugated Carbonyl Compounds 706b. Conjugated Carbonyl Compounds 710c. The Carbonyl "Ene" Reaction 711IV. Nucleophilic Addition Reactions Retaining the Carbonyl Oxygen 711a. General Comments 711b. Addition of H-X 713c. Addition of Carbon Nucleophiles 7151. Hydrogen Cyanide 7152. Organometallic Reagents 7163. The Aldol Reaction (Without Dehydration) 7194. The Darzens Glycidic Ester Condensation 7275. Epoxide Syntheses 728V. Nucleophilic Addition Reactions with Loss of the Carbonyl Oxygen 734a. General Comments 734b. Formation of Acetals, Ketals, and Thioketals 735c. Reaction of Aldehydes and Ketones with Nitrogen Nucleophiles 737d. Replacement of the Carbonyl Oxygen by Halogen and Sulfur 746e. Replacement of the Oxygen of the Carbonyl by Carbon 749f. Addition to the Carbon Alpha (alpha) to the Carbonyl (C=O) 7611. Halogenation 7612. Alkylation 7623. C-Alkylation Versus O-Alkylation 7624. Regioselectivity 7645. Stereoselectivity 7686. Enamine-Assisted Alkylation of Ketones 768D. Substitution Reactions Producing Aldehydes and Ketones 770I. Introduction 770II. Reimer-Tiemann Synthesis. 770III. Gattermann-Koch (Friedel-Crafts) Formylation 770IV. The Pauson-Khand Reaction 773E. Rearrangement Reaction of Aldehydes and Ketones 773I. Introduction 773II. The Benzilic Acid Rearrangement 773III. The Dienone-Phenol Rearrangement 775IV. Anionic Rearrangements 776Part II. Carboxylic Acids and Their Derivatives 778A. General Introduction 778B. Oxidation 780C. Reduction 786D. Substitution: Addition and Elimination 793E. Additional Reactions and Rearrangements of Esters and ß-Dicarbonyl Compounds 840Problems 848Notes and References 85310. Part I. The Reactions of Amines: Oxidation, Reduction, Addition, Substitution, and RearrangementPart II. Some Organophosphorus ChemistryPart III. Some Organosilicon Chemistry 865Part I. The Reactions of Amines: Introduction and Comments on the Synthesis of Amines 865A. Oxidation of Amines 876I. Oxygen and Peroxide Oxidation 876II. Other Oxidizing Agents. 882a. General 882b. Oxidation by Halogen 884c. Oxidation with Nitrous Acid 885B. Reduction of Amines 886C. Addition and Substitution Reactions of Amines with a General Introduction 889D. Addition and Rearrangement Reactions of Amines 898Part II. Some Organophosphorus Chemistry 915Part III. Some Organosilicon Chemistry 921Problems 934Notes and References 935Part III Foreground 94111. An Introduction to Carbohydrates, Acetogenins, and Steroids 945A. Introduction 945B. The Calvin Cycle 945C. Carbohydrates 955I. Biosynthesis 955II. Chemistry 955III. Oligosaccharides 969IV. Polysaccharides 972D. Acetogenins 974I. Acetyl Coenzyme A (CH3COS-CoA) 974II. Acetyl-CoA (CH3CO-SCoA) to Fatty Acids and Related Compounds 979III. Isoprenoids: To Dimethylallyl Diphosphate and Beyond 983a. Dimethylallyl Diphosphate from Acetyl Coenzyme A via Mevalonate 983b. Dimethylallyl Diphosphate from Pyruvate and Glyceraldehyde 9901. The 1-Deoxy-d-xylulose 5-Phosphate Pathway 990c. Terpenes 991d. Loose Ends 10191. Cannabinoid Biosynthesis 10192. Iridoids (Loganin and Secologanin) 10203. Shikimic Acid, Isoshikimic Acid, and Prephenic Acid 10214. The Citric Acid Cycle (or the Tricarboxylic Acid [TCA] Cycle or the Krebs Cycle) 1027Problems 1034Notes and References 103512. An Introduction to Amino Acids, Peptides and Proteins, Enzymes, and Coenzymes and Metabolic Processes 1045A. Introduction 1045B. Amino Acids 1050I. Biosynthesis 1050II. Synthesis 1080C. Peptides and Proteins: Introduction 1103I. Amino Acids from Peptides 1105II. Peptides from Amino Acids: In Vivo 1113III. Peptides from Amino Acids: In Vitro 1121D. The Coenzymes 1129I. Pyridoxal Phosphate 1129II. Lipoic Acid 1132III. Thiamine Diphosphate 1134a. 4-Amino-5-hydroxymethyl-2-methylpyrimidine 1134b. 4-Methyl-5-(2-phosphonooxyethyl)thiazole 1135c. 3-[(4-Amino-2-methylpyrimidin-5-yl)methyl]-5-(2-diphosphoethyl)-4-methyl-1,3-thiazolium 1136IV. Biotin 1140V. Adenosine 1143VI. Nicotinamide Adenine Dinucleotide 1149VII. Coenzyme A (CoA-SH) 1152VIII. Flavin Adenine Dinucleotide 1157IX. S-Adenosylmethionine 1160X. Tetrahydrofolate 1162Notes and References 116813. An Introduction to Alkaloids and Some Other Heterocyclic Compounds 1179A. Introduction 1179B. Tropane Alkaloids 1181I. Chemistry of Hyoscyamine 1181II. Chemistry of Nicotine 1187III. Biosynthesis of Hyoscyamine and Nicotine 1192a. The Common Feature 1192b. The Biosynthesis of Nicotine 1194c. The Biosynthesis of Hyoscyamine 1194d. The Biosynthesis of Tropic Acid 1196C. Morphine (and Codeine and Thebaine) 1197I. Chemistry of Morphine (and Codeine and Thebaine) 1197II. The Biosynthesis of Morphine (and Codeine and Thebaine) 1212III. The Synthesis of Morphine 1217D. Vinblastine 1222I. Chemistry of Vinblastine 1222II. Biosynthesis of Vinblastine 1230E. Caffeine 1233I. Some History and the Synthesis of Caffeine 1233II. Biosynthesis of Caffeine 1236Notes and References 124214. Part I. On the Genetic Code: Unity and DiversityPart II. The Tetrapyrrolic Cofactors and Other Metal-Organic Frameworks 1249A. Introduction 1249Part I. The Genetic Code 1249Part II. Metal-Organic Frameworks 1250Part I. On The Genetic Code: Unity and Diversity 1250A. The Bases of Deoxyribonucleic Acid (Dna) and Ribonucleic Acid (RNA) 1250I. Adenine (A) 1250II. Guanine (G) 1251III. Uracil (U) and Thymine (T) 1254IV. Cytosine (C) 1255B. Deoxynucleotides 1259C. The Role of Phosphate 1262D. The Sequencing of DNA 1265E. Chemical Synthesis of DNA 1265F. Modification to DNA 1269I. Zinc Finger Nucleases (ZFNs) 1272II. Transcription Activator-Like Effector Nucleases (TALENs) 1272III. Clustered Regularly Interspaced Short Palindromic Repeats (CRISPR) and Associated Enzymes (Cas) 1273Part II. The Tetrapyrrolic Cofactors and Other Metal-Organic Frameworks 1274A. Introduction to Metals in an Organic Framework 1274B. Some Early Pyrrole Chemistry 1276C. Current Biosynthetic Understanding 1281Notes and References 1291Epilogue 1297Appendix I The Schrödinger Equation 1299Appendix II The Literature 1303Index 1305

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DAVID R. DALTON received his Ph.D. in Organic Chemistry from the University of California, Los Angeles and is a Professor Emeritus at Temple University. He has held visiting professorships (1972-1973) at Israel Institute of Technology (Technion), Haifa, Israel; (1976-1977) Yale University, New Haven, Connecticut; (1988-1989) Bryn Mawr College, Bryn Mawr, Pennsylvania; and in 1992, he was the visiting master teacher in Residence, Clemson University, Clemson, South Carolina.