Marchs Advanced Organic Chemistry Reactions Mechanisms And Structure 8Th Edition by MICHAEL B. SMITH, JOHN WILEY

Description

JOHN WILEY Marchs Advanced Organic Chemistry Reactions Mechanisms And Structure 8Th Edition by MICHAEL B. SMITH

The completely revised and updated, definitive resource for students and professionals in organic chemistry_x000D__x000D__x000D_The revised and updated 8th edition of March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure explains the theories of organic chemistry with examples and reactions. This book is the most comprehensive resource about organic chemistry available. Readers are guided on the planning and execution of multi-step synthetic reactions, with detailed descriptions of all the reactions_x000D__x000D__x000D_The opening chapters of March's Advanced Organic Chemistry, 8th Edition deal with the structure of organic compounds and discuss important organic chemistry bonds, fundamental principles of conformation, and stereochemistry of organic molecules, and reactive intermediates in organic chemistry. Further coverage concerns general principles of mechanism in organic chemistry, including acids and bases, photochemistry, sonochemistry and microwave irradiation. The relationship between structure and reactivity is also covered. The final chapters cover the nature and scope of organic reactions and their mechanisms. _x000D__x000D_This edition:_x000D__x000D__x000D__x000D__x000D__x000D_Provides revised examples and citations that reflect advances in areas of organic chemistry published between 2011 and 2017_x000D__x000D_Includes appendices on the literature of organic chemistry and the classification of reactions according to the compounds prepared_x000D__x000D_Instructs the reader on preparing and conducting multi-step synthetic reactions, and provides complete descriptions of each reaction _x000D__x000D__x000D__x000D_The 8th edition of March's Advanced Organic Chemistry proves once again that it is a must-have desktop reference and textbook for every student and professional working in organic chemistry or related fields._x000D_ _x000D_ New Reaction Sections Correlation: 7th Edition 8th Edition xv_x000D_ _x000D_ _x000D_ Preface xxi_x000D_ _x000D_ _x000D_ Common Abbreviations xxv_x000D_ _x000D_ _x000D_ Biographical Statement xxxi_x000D_ _x000D_ _x000D_ New Features of the 8th Edition xxxiii_x000D_ _x000D_ _x000D_ Part I Introduction 1_x000D_ _x000D_ _x000D_ 1. Localized Chemical Bonding 3_x000D_ _x000D_ _x000D_ 1.A. Covalent Bonding 3_x000D_ _x000D_ _x000D_ 1.B. Multiple Valence 7_x000D_ _x000D_ _x000D_ 1.C. Hybridization 7_x000D_ _x000D_ _x000D_ 1.D. Multiple Bonds 9_x000D_ _x000D_ _x000D_ 1.E. Photoelectron Spectroscopy 12_x000D_ _x000D_ _x000D_ 1.F. Electronic Structures of Molecules 15_x000D_ _x000D_ _x000D_ 1.G. Electronegativity 17_x000D_ _x000D_ _x000D_ 1.H. Dipole Moment 19_x000D_ _x000D_ _x000D_ 1.I. Inductive and Field Effects 20_x000D_ _x000D_ _x000D_ 1.J. Bond Distances 23_x000D_ _x000D_ _x000D_ 1.K. Bond Angles 27_x000D_ _x000D_ _x000D_ 1.L. Bond Energies 29_x000D_ _x000D_ _x000D_ 2. Delocalized Chemical Bonding 33_x000D_ _x000D_ _x000D_ 2.A. Molecular Orbitals 34_x000D_ _x000D_ _x000D_ 2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds 37_x000D_ _x000D_ _x000D_ 2.C. Molecules that have Delocalized Bonds 39_x000D_ _x000D_ _x000D_ 2.D. Cross Conjugation 44_x000D_ _x000D_ _x000D_ 2.E. The Rules of Resonance 46_x000D_ _x000D_ _x000D_ 2.F. The Resonance Effect 48_x000D_ _x000D_ _x000D_ 2.G. Steric Inhibition of Resonance and the Influences of Strain 48_x000D_ _x000D_ _x000D_ 2.H. p -d Bonding: Ylids 52_x000D_ _x000D_ _x000D_ 2.I. Aromaticity 54_x000D_ _x000D_ _x000D_ 2.I.i. Six-Membered Rings 58_x000D_ _x000D_ _x000D_ 2.I.ii. Five-, Seven-, and Eight-Membered Rings 62_x000D_ _x000D_ _x000D_ 2.I.iii. Other Systems Containing Aromatic Sextets 67_x000D_ _x000D_ _x000D_ 2.J. Alternant and Nonalternant Hydrocarbons 68_x000D_ _x000D_ _x000D_ 2.K. Aromatic Systems with Electron Numbers Other Than Six 70_x000D_ _x000D_ _x000D_ 2.K.i. Systems of Two Electrons 72_x000D_ _x000D_ _x000D_ 2.K.ii. Systems of Four Electrons: Antiaromaticity 73_x000D_ _x000D_ _x000D_ 2.K.iii. Systems of Eight Electrons 76_x000D_ _x000D_ _x000D_ 2.K.iv. Systems of Ten Electrons 77_x000D_ _x000D_ _x000D_ 2.K.v. Systems of More than Ten Electrons: 4n + 2 Electrons 80_x000D_ _x000D_ _x000D_ 2.K.vi. Systems of More Than Ten Electrons: 4n Electrons 85_x000D_ _x000D_ _x000D_ 2.L. Other Aromatic Compounds 89_x000D_ _x000D_ _x000D_ 2.M. Hyperconjugation 92_x000D_ _x000D_ _x000D_ 2.N. Tautomerism 96_x000D_ _x000D_ _x000D_ 2.N.i. Keto-Enol Tautomerism 97_x000D_ _x000D_ _x000D_ 2.N.ii. Other Proton-Shift Tautomerism 100_x000D_ _x000D_ _x000D_ 3. Bonding Weaker Than Covalent 105_x000D_ _x000D_ _x000D_ 3.A. Hydrogen Bonding 105_x000D_ _x000D_ _x000D_ 3.B. - Interactions 113_x000D_ _x000D_ _x000D_ 3.C. Addition Compounds 114_x000D_ _x000D_ _x000D_ 3.C.i. Electron Donor-Acceptor (EDA) Complexes 114_x000D_ _x000D_ _x000D_ 3.C.ii. Crown Ether Complexes and Cryptates 117_x000D_ _x000D_ _x000D_ 3.C.iii. Inclusion Compounds 122_x000D_ _x000D_ _x000D_ 3.C.iv. Cyclodextrins 125_x000D_ _x000D_ _x000D_ 3.D. Catenanes and Rotaxanes 127_x000D_ _x000D_ _x000D_ 3.E. Cucurbit[n]Uril-Based Gyroscane 131_x000D_ _x000D_ _x000D_ 4. Stereochemistry and Conformation 133_x000D_ _x000D_ _x000D_ 4.A. Optical Activity and Chirality 133_x000D_ _x000D_ _x000D_ 4.B. Dependence of Rotation on Conditions of Measurement 135_x000D_ _x000D_ _x000D_ 4.C. What Kinds of Molecules Display Optical Activity? 136_x000D_ _x000D_ _x000D_ 4.D. The Fischer Projection 147_x000D_ _x000D_ _x000D_ 4.E. Absolute Configuration 148_x000D_ _x000D_ _x000D_ 4.E.i. The Cahn-Ingold-Prelog System 150_x000D_ _x000D_ _x000D_ 4.E.ii. Methods of Determining Configuration 152_x000D_ _x000D_ _x000D_ 4.F. The Cause of Optical Activity 156_x000D_ _x000D_ _x000D_ 4.G. Molecules with More Than One Stereogenic Center 157_x000D_ _x000D_ _x000D_ 4.H. Asymmetric Synthesis 161_x000D_ _x000D_ _x000D_ 4.I. Methods of Resolution 166_x000D_ _x000D_ _x000D_ 4.J. Optical Purity 173_x000D_ _x000D_ _x000D_ 4.K. Cis-Trans Isomerism 175_x000D_ _x000D_ _x000D_ 4.K.i. Cis-Trans Isomerism Resulting from Double Bonds 175_x000D_ _x000D_ _x000D_ 4.K.ii. Cis-Trans Isomerism of Monocyclic Compounds 179_x000D_ _x000D_ _x000D_ 4.K.iii. Cis-Trans Isomerism of Fused and Bridged Ring Systems 180_x000D_ _x000D_ _x000D_ 4.L. Out-In Isomerism 181_x000D_ _x000D_ _x000D_ 4.M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 183_x000D_ _x000D_ _x000D_ 4.N. Stereospecific and Stereoselective Syntheses 186_x000D_ _x000D_ _x000D_ 4.O. Conformational Analysis 187_x000D_ _x000D_ _x000D_ 4.O.i. Conformation in Open-Chain Systems 188_x000D_ _x000D_ _x000D_ 4.O.ii. Conformation in Six-Membered Rings 194_x000D_ _x000D_ _x000D_ 4.O.iii. Conformation in Six-Membered Rings Containing Heteroatoms 199_x000D_ _x000D_ _x000D_ 4.O.iv. Conformation in Other Rings 202_x000D_ _x000D_ _x000D_ 4.P. Molecular Mechanics 204_x000D_ _x000D_ _x000D_ 4.Q. Strain 206_x000D_ _x000D_ _x000D_ 4.Q.i. Strain in Small Rings 207_x000D_ _x000D_ _x000D_ 4.Q.ii. Strain in Other Rings 213_x000D_ _x000D_ _x000D_ 4.Q.iii. Unsaturated Rings 215_x000D_ _x000D_ _x000D_ 4.Q.iv. Strain Due to Unavoidable Crowding 218_x000D_ _x000D_ _x000D_ 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 223_x000D_ _x000D_ _x000D_ 5.A. Carbocations 224_x000D_ _x000D_ _x000D_ 5.A.i. Nomenclature 224_x000D_ _x000D_ _x000D_ 5.A.ii. Stability and Structure of Carbocations 224_x000D_ _x000D_ _x000D_ 5.A.iii. The Generation and Fate of Carbocations 234_x000D_ _x000D_ _x000D_ 5.B. Carbanions 237_x000D_ _x000D_ _x000D_ 5.B.i. Stability and Structure 237_x000D_ _x000D_ _x000D_ 5.B.ii. The Structure of Organometallic Compounds 244_x000D_ _x000D_ _x000D_ 5.B.iii. The Generation and Fate of Carbanions 249_x000D_ _x000D_ _x000D_ 5.C. Free Radicals 250_x000D_ _x000D_ _x000D_ 5.C.i. Stability and Structure 250_x000D_ _x000D_ _x000D_ 5.C.ii. The Generation and Fate of Free Radicals 261_x000D_ _x000D_ _x000D_ 5.C.iii. Radical Ions 265_x000D_ _x000D_ _x000D_ 5.D. Carbenes 266_x000D_ _x000D_ _x000D_ 5.D.i. Stability and Structure 266_x000D_ _x000D_ _x000D_ 5.D.ii. The Generation and Fate of Carbenes 269_x000D_ _x000D_ _x000D_ 5.D.iii. N-Heterocyclic Carbenes (NHCs) 274_x000D_ _x000D_ _x000D_ 5.E. Nitrenes 276_x000D_ _x000D_ _x000D_ 6. Mechanisms and Methods of Determining Them 279_x000D_ _x000D_ _x000D_ 6.A. Types of Mechanism 279_x000D_ _x000D_ _x000D_ 6.B. Types of Reaction 280_x000D_ _x000D_ _x000D_ 6.C. Thermodynamic Requirements for Reaction 283_x000D_ _x000D_ _x000D_ 6.D. Kinetic Requirements for Reaction 284_x000D_ _x000D_ _x000D_ 6.E. The Baldwin Rules for Ring Closure 288_x000D_ _x000D_ _x000D_ 6.F. Kinetic and Thermodynamic Control 290_x000D_ _x000D_ _x000D_ 6.G. The Hammond Postulate 291_x000D_ _x000D_ _x000D_ 6.H. Microscopic Reversibility 291_x000D_ _x000D_ _x000D_ 6.I. Marcus Theory 292_x000D_ _x000D_ _x000D_ 6.J. Methods of Determining Mechanisms 293_x000D_ _x000D_ _x000D_ 6.J.i. Identification of Products 293_x000D_ _x000D_ _x000D_ 6.J.ii. Determination of the Presence of an Intermediate 294_x000D_ _x000D_ _x000D_ 6.J.iii. The Study of Catalysis 295_x000D_ _x000D_ _x000D_ 6.J.iv. Isotopic Labeling 296_x000D_ _x000D_ _x000D_ 6.J.v. Stereochemical Evidence 296_x000D_ _x000D_ _x000D_ 6.J.vi. Kinetic Evidence 297_x000D_ _x000D_ _x000D_ 6.J.vii. Isotope Effects 304_x000D_ _x000D_ _x000D_ 6.K. Catalyst Development 308_x000D_ _x000D_ _x000D_ 7. Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 313_x000D_ _x000D_ _x000D_ 7.A. Photochemistry 314_x000D_ _x000D_ _x000D_ 7.A.i. Excited States and the Ground State 314_x000D_ _x000D_ _x000D_ 7.A.ii. Singlet and Triplet States: "Forbidden" Transitions 316_x000D_ _x000D_ _x000D_ 7.A.iii. Types of Excitation 317_x000D_ _x000D_ _x000D_ 7.A.iv. Nomenclature and Properties of Excited States 318_x000D_ _x000D_ _x000D_ 7.A.v. Photolytic Cleavage 319_x000D_ _x000D_ _x000D_ 7.A.vi. The Fate of the Excited Molecule: Physical Processes 320_x000D_ _x000D_ _x000D_ 7.A.vii. The Fate of the Excited Molecule: Chemical Processes 325_x000D_ _x000D_ _x000D_ 7.A.viii. The Determination of Photochemical Mechanisms 330_x000D_ _x000D_ _x000D_ 7.B. Sonochemistry 331_x000D_ _x000D_ _x000D_ 7.C. Microwave Chemistry 334_x000D_ _x000D_ _x000D_ 7.D. Flow Chemistry 336_x000D_ _x000D_ _x000D_ 7.E. Mechanochemistry 338_x000D_ _x000D_ _x000D_ 8. Acids and Bases 339_x000D_ _x000D_ _x000D_ 8.A. Bronsted Theory 339_x000D_ _x000D_ _x000D_ 8.A.i. Bronsted Acids 340_x000D_ _x000D_ _x000D_ 8.A.ii. Bronsted Bases 347_x000D_ _x000D_ _x000D_ 8.B. The Mechanism of Proton Transfer Reactions 350_x000D_ _x000D_ _x000D_ 8.C. Measurements of Solvent Acidity 352_x000D_ _x000D_ _x000D_ 8.D. Acid and Base Catalysis 355_x000D_ _x000D_ _x000D_ 8.E. Lewis Acids and Bases 357_x000D_ _x000D_ _x000D_ 8.E.i. Hard-Soft Acids-Bases 359_x000D_ _x000D_ _x000D_ 8.F. The Effects of Structure on the Strengths of Acids and Bases 361_x000D_ _x000D_ _x000D_ 8.G. The Effects of the Medium on Acid and Base Strength 370_x000D_ _x000D_ _x000D_ 9. Effects of Structure and Medium on Reactivity 375_x000D_ _x000D_ _x000D_ 9.A. Resonance and Field Effects 375_x000D_ _x000D_ _x000D_ 9.B. Steric Effects 377_x000D_ _x000D_ _x000D_ 9.C. Quantitative Treatments of the Effect of Structure on Reactivity 380_x000D_ _x000D_ _x000D_ 9.D. Effect of Medium on Reactivity and Rate 390_x000D_ _x000D_ _x000D_ 9.E. High Pressure 390_x000D_ _x000D_ _x000D_ 9.F. Water and Other Nonorganic Solvents 391_x000D_ _x000D_ _x000D_ 9.G. Ionic Liquid Solvents 393_x000D_ _x000D_ _x000D_ 9.H. Solventless Reactions 395_x000D_ _x000D_ _x000D_ Part II Introduction 397_x000D_ _x000D_ _x000D_ 10. Aliphatic Substitution, Nucleophilic and Organometallic 403_x000D_ _x000D_ _x000D_ 10.A. Mechanisms 404_x000D_ _x000D_ _x000D_ 10.A.i. The SN2 Mechanism 404_x000D_ _x000D_ _x000D_ 10.A.ii. The SN1 Mechanism 410_x000D_ _x000D_ _x000D_ 10.A.iii. Ion Pairs in the SN1 Mechanism 414_x000D_ _x000D_ _x000D_ 10.A.iv. Mixed SN1 and SN2 Mechanisms 418_x000D_ _x000D_ _x000D_ 10.B. SET Mechanisms 420_x000D_ _x000D_ _x000D_ 10.C. The Neighboring-Group Mechanism 422_x000D_ _x000D_ _x000D_ 10.C.i. Neighboring-Group Participation by and Bonds: Nonclassical Carbocations 425_x000D_ _x000D_ _x000D_ 10.D. The SNi Mechanism 440_x000D_ _x000D_ _x000D_ 10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 441_x000D_ _x000D_ _x000D_ 10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 445_x000D_ _x000D_ _x000D_ 10.G. Reactivity 449_x000D_ _x000D_ _x000D_ 10.G.i. The Effect of Substrate Structure 449_x000D_ _x000D_ _x000D_ 10.G.ii. The Effect of the Attacking Nucleophile 457_x000D_ _x000D_ _x000D_ 10.G.iii. The Effect of the Leaving Group 464_x000D_ _x000D_ _x000D_ 10.G.iv. The Effect of the Reaction Medium 469_x000D_ _x000D_ _x000D_ 10.G.v. Phase-Transfer Catalysis 474_x000D_ _x000D_ _x000D_ 10.G.vi. Influencing Reactivity by External Means 477_x000D_ _x000D_ _x000D_ 10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 478_x000D_ _x000D_ _x000D_ 10.G.viii. Ambident Substrates 481_x000D_ _x000D_ _x000D_ 10.H. Reactions 483_x000D_ _x000D_ _x000D_ 10.H.i. Oxygen Nucleophiles 483_x000D_ _x000D_ _x000D_ 10.H.ii. Sulfur Nucleophiles 506_x000D_ _x000D_ _x000D_ 10.H.iii. Nitrogen Nucleophiles 512_x000D_ _x000D_ _x000D_ 10.H.iv. Halogen Nucleophiles 534_x000D_ _x000D_ _x000D_ 10.H.v. Carbon Nucleophiles 545_x000D_ _x000D_ _x000D_ 11. Aromatic Substitution, Electrophilic 607_x000D_ _x000D_ _x000D_ 11.A. Mechanisms 607_x000D_ _x000D_ _x000D_ 11.A.i. The Arenium Ion Mechanism 608_x000D_ _x000D_ _x000D_ 11.A.ii. The SE1 Mechanism 613_x000D_ _x000D_ _x000D_ 11.B. Orientation and Reactivity 614_x000D_ _x000D_ _x000D_ 11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings 614_x000D_ _x000D_ _x000D_ 11.B.ii. The Ortho/Para Ratio 618_x000D_ _x000D_ _x000D_ 11.B.iii. Ipso Attack 620_x000D_ _x000D_ _x000D_ 11.B.iv. Orientation in Benzene Rings with More Than One Substituent 621_x000D_ _x000D_ _x000D_ 11.B.v. Orientation in Other Ring Systems 622_x000D_ _x000D_ _x000D_ 11.C. Quantitative Treatments of Reactivity in the Substrate 624_x000D_ _x000D_ _x000D_ 11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 626_x000D_ _x000D_ _x000D_ 11.E. The Effect of the Leaving Group 628_x000D_ _x000D_ _x000D_ 11.F. Reactions 629_x000D_ _x000D_ _x000D_ 11.F.i. Hydrogen as the Leaving Group in Simple Substitution Reactions 629_x000D_ _x000D_ _x000D_ 11.F.ii. Hydrogen as the Leaving Group in Rearrangement Reactions 675_x000D_ _x000D_ _x000D_ 11.F.iii. Other Leaving Groups 680_x000D_ _x000D_ _x000D_ 12. Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 687_x000D_ _x000D_ _x000D_ 12.A. Mechanisms 687_x000D_ _x000D_ _x000D_ 12.A.i. Bimolecular Mechanisms. SE2 and SEi 688_x000D_ _x000D_ _x000D_ 12.A.ii. The SE1 Mechanism 691_x000D_ _x000D_ _x000D_ 12.A.iii. Electrophilic Substitution Accompanied by Double-Bond Shifts 694_x000D_ _x000D_ _x000D_ 12.A.iv. Other Mechanisms 695_x000D_ _x000D_ _x000D_ 12.B. Reactivity 695_x000D_ _x000D_ _x000D_ 12.C. Reactions 697_x000D_ _x000D_ _x000D_ 12.C.i. Hydrogen as Leaving Group 697_x000D_ _x000D_ _x000D_ 12.C.ii. Metals as Leaving Groups 733_x000D_ _x000D_ _x000D_ 12.C.iii. Halogen as Leaving Group 746_x000D_ _x000D_ _x000D_ 12.C.iv. Carbon Leaving Groups 751_x000D_ _x000D_ _x000D_ 12.C.v. Electrophilic Substitution At Nitrogen 760_x000D_ _x000D_ _x000D_ 13. Aromatic Substitution: Nucleophilic and Organometallic 767_x000D_ _x000D_ _x000D_ 13.A. Mechanisms 768_x000D_ _x000D_ _x000D_ 13.A.i. The SNAr Mechanism 768_x000D_ _x000D_ _x000D_ 13.A.ii. The SN1 Mechanism 771_x000D_ _x000D_ _x000D_ 13.A.iii. The Benzyne Mechanism 772_x000D_ _x000D_ _x000D_ 13.A.iv. The SRN1 Mechanism 774_x000D_ _x000D_ _x000D_ 13.A.v. Other Mechanisms 776_x000D_ _x000D_ _x000D_ 13.B. Reactivity 776_x000D_ _x000D_ _x000D_ 13.B.i. The Effect of Substrate Structure 776_x000D_ _x000D_ _x000D_ 13.B.ii. The Effect of the Leaving Group 778_x000D_ _x000D_ _x000D_ 13.B.iii. The Effect of the Attacking Nucleophile 779_x000D_ _x000D_ _x000D_ 13.C. Reactions 779_x000D_ _x000D_ _x000D_ 13.C.i. All Leaving Groups Except Hydrogen and N2+ 779_x000D_ _x000D_ _x000D_ 13.C.ii. Hydrogen as Leaving Group 823_x000D_ _x000D_ _x000D_ 13.C.iii. Nitrogen as Leaving Group 824_x000D_ _x000D_ _x000D_ 13.C.iv. Rearrangements 834_x000D_ _x000D_ _x000D_ 14. Radical Reactions 839_x000D_ _x000D_ _x000D_ 14.A. Mechanisms 839_x000D_ _x000D_ _x000D_ 14.A.i. Radical Mechanisms in General 839_x000D_ _x000D_ _x000D_ 14.A.ii. Free-Radical Substitution Mechanisms 844_x000D_ _x000D_ _x000D_ 14.A.iii. Mechanisms at an Aromatic Substrate 845_x000D_ _x000D_ _x000D_ 14.A.iv. Neighboring-Group Assistance in Free-Radical Reactions 847_x000D_ _x000D_ _x000D_ 14.B. Reactivity 848_x000D_ _x000D_ _x000D_ 14.B.i. Reactivity for Aliphatic Substrates 848_x000D_ _x000D_ _x000D_ 14.B.ii. Reactivity at a Bridgehead 853_x000D_ _x000D_ _x000D_ 14.B.iii. Reactivity in Aromatic Substrates 854_x000D_ _x000D_ _x000D_ 14.B.iv. Reactivity in the Attacking Radical 855_x000D_ _x000D_ _x000D_ 14.B.v. The Effect of Solvent on Reactivity 856_x000D_ _x000D_ _x000D_ 14.C. Reactions 856_x000D_ _x000D_ _x000D_ 14.C.i. Hydrogen as Leaving Group 856_x000D_ _x000D_ _x000D_ 14.C.ii. Metals as Leaving Groups 880_x000D_ _x000D_ _x000D_ 14.C.iii. Halogen as Leaving Group 883_x000D_ _x000D_ _x000D_ 14.C.iv. Sulfur as Leaving Group 883_x000D_ _x000D_ _x000D_ 14.C.v. Carbon as Leaving Group 885_x000D_ _x000D_ _x000D_ 15. Addition to Carbon-Carbon Multiple Bonds 891_x000D_ _x000D_ _x000D_ 15.A. Mechanisms 892_x000D_ _x000D_ _x000D_ 15.A.i. Electrophilic Addition 892_x000D_ _x000D_ _x000D_ 15.A.ii. Nucleophilic Addition 895_x000D_ _x000D_ _x000D_ 15.A.iii. Free-Radical Addition 896_x000D_ _x000D_ _x000D_ 15.A.iv. Cyclic Mechanisms 898_x000D_ _x000D_ _x000D_ 15.A.v. Addition to Conjugated Systems 898_x000D_ _x000D_ _x000D_ 15.B. Orientation and Reactivity 899_x000D_ _x000D_ _x000D_ 15.B.i. Reactivity 899_x000D_ _x000D_ _x000D_ 15.B.ii. Orientation 902_x000D_ _x000D_ _x000D_ 15.B.iii. Stereochemical Orientation 904_x000D_ _x000D_ _x000D_ 15.B.iv. Addition to Cyclopropane Rings 906_x000D_ _x000D_ _x000D_ 15.C. Reactions 908_x000D_ _x000D_ _x000D_ 15.C.i. Isomerization of Double and Triple Bonds 908_x000D_ _x000D_ _x000D_ 15.C.ii. Reactions in Which Hydrogen Adds to One Side 910_x000D_ _x000D_ _x000D_ 15.C.iii. Reactions in Which Hydrogen Adds to Neither Side 992_x000D_ _x000D_ _x000D_ 15.C.iv. Cycloaddition Reactions 1027_x000D_ _x000D_ _x000D_ 16. Addition to Carbon-Heteroatom Multiple Bonds 1087_x000D_ _x000D_ _x000D_ 16.A. Mechanism and Reactivity 1087_x000D_ _x000D_ _x000D_ 16.A.i. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 1089_x000D_ _x000D_ _x000D_ 16.B. Reactions 1094_x000D_ _x000D_ _x000D_ 16.B.i. Reactions in Which Hydrogen or a Metallic Ion Adds to the Heteroatom 1095_x000D_ _x000D_ _x000D_ 16.B.ii. Acyl Substitution Reactions 1218_x000D_ _x000D_ _x000D_ 16.B.iii. Reactions in Which Carbon Adds to the Heteroatom 1257_x000D_ _x000D_ _x000D_ 16.B.iv. Addition to Isocyanides 1264_x000D_ _x000D_ _x000D_ 16.B.v. Nucleophilic Substitution at a Sulfonyl Sulfur Atom 1266_x000D_ _x000D_ _x000D_ 17. Elimination Reactions 1273_x000D_ _x000D_ _x000D_ 17.A. Mechanisms and Orientation 1273_x000D_ _x000D_ _x000D_ 17.A.i. The E2 Mechanism 1274_x000D_ _x000D_ _x000D_ 17.A.ii. The E1 Mechanism 1280_x000D_ _x000D_ _x000D_ 17.A.iii. The E1cB Mechanism 1281_x000D_ _x000D_ _x000D_ 17.A.iv. The E1-E2-E1cB Spectrum 1286_x000D_ _x000D_ _x000D_ 17.A.v. The E2C Mechanism 1287_x000D_ _x000D_ _x000D_ 17.B. Regiochemistry of the Double Bond 1288_x000D_ _x000D_ _x000D_ 17.C. Stereochemistry of the Double Bond 1290_x000D_ _x000D_ _x000D_ 17.D. Reactivity 1291_x000D_ _x000D_ _x000D_ 17.D.i. Effect of Substrate Structure 1291_x000D_ _x000D_ _x000D_ 17.D.ii. Effect of the Attacking Base 1293_x000D_ _x000D_ _x000D_ 17.D.iii. Effect of the Leaving Group 1294_x000D_ _x000D_ _x000D_ 17.D.iv. Effect of the Medium 1294_x000D_ _x000D_ _x000D_ 17.E. Mechanisms and Orientation in Pyrolytic Eliminations 1295_x000D_ _x000D_ _x000D_ 17.E.i. Mechanisms 1295_x000D_ _x000D_ _x000D_ 17.E.ii. Orientation in Pyrolytic Eliminations 1298_x000D_ _x000D_ _x000D_ 17.E.iii. 1,4 Conjugate Eliminations 1298_x000D_ _x000D_ _x000D_ 17.F. Reactions 1299_x000D_ _x000D_ _x000D_ 17.F.i. Reactions in Which C C and C C Bonds are Formed 1299_x000D_ _x000D_ _x000D_ 17.F.ii. Fragmentations 1321_x000D_ _x000D_ _x000D_ 17.F.iii. Reactions in Which C N or C N Bonds are Formed 1325_x000D_ _x000D_ _x000D_ 17.F.iv. Reactions in Which C O Bonds are Formed 1328_x000D_ _x000D_ _x000D_ 17.F.v. Reactions in Which N N Bonds are Formed 1329_x000D_ _x000D_ _x000D_ 17.F.vi. Extrusion Reactions 1329_x000D_ _x000D_ _x000D_ 18. Rearrangements 1335_x000D_ _x000D_ _x000D_ 18.A. Mechanisms 1336_x000D_ _x000D_ _x000D_ 18.A.i. Nucleophilic Rearrangements 1336_x000D_ _x000D_ _x000D_ 18.A.ii. The Actual Nature of the Migration 1337_x000D_ _x000D_ _x000D_ 18.A.iii. Migratory Aptitudes 1340_x000D_ _x000D_ _x000D_ 18.A.iv. Memory Effects 1343_x000D_ _x000D_ _x000D_ 18.B. Longer Nucleophilic Rearrangements 1344_x000D_ _x000D_ _x000D_ 18.C. Free-Radical Rearrangements 1345_x000D_ _x000D_ _x000D_ 18.D. Carbene Rearrangements 1349_x000D_ _x000D_ _x000D_ 18.E. Electrophilic Rearrangements 1349_x000D_ _x000D_ _x000D_ 18.F. Reactions 1350_x000D_ _x000D_ _x000D_ 18.F.i. 1,2-Rearrangements 1350_x000D_ _x000D_ _x000D_ 18.F.ii. Non 1,2-Rearrangements 1389_x000D_ _x000D_ _x000D_ 19. Oxidations and Reductions 1439_x000D_ _x000D_ _x000D_ 19.A. Mechanisms 1440_x000D_ _x000D_ _x000D_ 19.B. Reactions 1442_x000D_ _x000D_ _x000D_ 19.B.i. Oxidations 1442_x000D_ _x000D_ _x000D_ 19.B.ii. Reductions 1510_x000D_ _x000D_ _x000D_ Appendix A: The Literature of Organic Chemistry 1607_x000D_ _x000D_ _x000D_ Appendix B: Classification of Reactions by Type of Compounds Synthesized 1645_x000D_ _x000D_ _x000D_ Indexes_x000D_ _x000D_ _x000D_ Author Index 1669_x000D_ _x000D_ _x000D_ Subject Index 1917_x000D_ show more