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March's Advanced Organic Chemistry - Reactions, Mechanisms, and Structure
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March's Advanced Organic Chemistry - Reactions, Mechanisms, and Structure
von: Michael B. Smith
Wiley, 2019
ISBN: 9781119371786
2141 Seiten, Download: 86865 KB
 
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Inhaltsverzeichnis

  March's Advanced Organic Chemistry 3  
  Contents 7  
  New Reaction Sections Correlation: 7th edition ? 8th edition 17  
     7th ? 8th 17  
  Preface 23  
  Common Abbreviations 27  
  Biographical Statement 33  
  New Features of the 8th Edition 35  
  PART I INTRODUCTION 37  
     1 Localized Chemical Bonding 39  
        1.A Covalent Bonding 39  
        1.B Multiple Valence 43  
        1.C Hybridization 43  
        1.D Multiple Bonds 45  
        1.E Photoelectron Spectroscopy 48  
        1.F Electronic Structures of Molecules 51  
        1.G Electronegativity 53  
        1.H Dipole Moment 55  
        1.I Inductive and Field Effects 56  
        1.J Bond Distances 59  
        1.K Bond Angles 63  
        1.L Bond Energies 65  
     2 Delocalized Chemical Bonding 69  
        2.A Molecular Orbitals 70  
        2.B Bond Energies and Distances in Compounds Containing Delocalized Bonds 73  
        2.C Molecules that have Delocalized Bonds 75  
        2.D Cross Conjugation 80  
        2.E The Rules of Resonance 82  
        2.F The Resonance Effect 84  
        2.G Steric Inhibition of Resonance and the Influences of Strain 84  
        2.H p??????–d?????? Bonding: Ylids 88  
        2.I Aromaticity 90  
           2.I.i Six-Membered Rings 94  
           2.I.ii Five-, Seven-, and Eight-Membered Rings 98  
           2.I.iii Other Systems Containing Aromatic Sextets 103  
        2.J Alternant and Nonalternant Hydrocarbons 104  
        2.K Aromatic Systems with Electron Numbers Other Than Six 106  
           2.K.i Systems of Two Electrons 108  
           2.K.ii Systems of Four Electrons: Antiaromaticity 109  
           2.K.iii Systems of Eight Electrons 112  
           2.K.iv Systems of Ten Electrons 113  
           2.K.v Systems of More than Ten Electrons: 4n+2 Electrons 116  
           2.K.vi Systems of More Than Ten Electrons: 4n Electrons 121  
        2.L Other Aromatic Compounds 125  
        2.M Hyperconjugation 128  
        2.N Tautomerism 132  
           2.N.i Keto–Enol Tautomerism 133  
           2.N.ii Other Proton-Shift Tautomerism 136  
     3 Bonding Weaker Than Covalent 141  
        3.A Hydrogen Bonding 141  
        3.B ??????–?????? Interactions 149  
        3.C Addition Compounds 150  
           3.C.i Electron Donor–Acceptor (EDA) Complexes 150  
           3.C.ii Crown Ether Complexes and Cryptates 153  
           3.C.iii Inclusion Compounds 158  
           3.C.iv Cyclodextrins 161  
        3.D Catenanes and Rotaxanes 163  
        3.E Cucurbit[n]Uril-Based Gyroscane 167  
     4 Stereochemistry and Conformation 169  
        4.A Optical Activity and Chirality 169  
        4.B Dependence of Rotation on Conditions of Measurement 171  
        4.C What Kinds of Molecules Display Optical Activity? 172  
        4.D The Fischer Projection 183  
        4.E Absolute Configuration 184  
           4.E.i The Cahn-Ingold-Prelog System 186  
           4.E.ii Methods Of Determining Configuration 188  
        4.F The Cause of Optical Activity 192  
        4.G Molecules with more than One Stereogenic Center 193  
        4.H Asymmetric Synthesis 197  
        4.I Methods of Resolution 202  
        4.J Optical Purity 209  
        4.K Cis–Trans Isomerism 211  
           4.K.i Cis–Trans Isomerism Resulting from Double Bonds 211  
           4.K.ii Cis–Trans Isomerism of Monocyclic Compounds 215  
           4.K.iii Cis–Trans Isomerism of Fused and Bridged Ring Systems 216  
        4.L Out–In Isomerism 217  
        4.M Enantiotopic and Diastereotopic Atoms, Groups, and Faces 219  
        4.N Stereospecific and Stereoselective Syntheses 222  
        4.O Conformational Analysis 223  
           4.O.i Conformation in Open-Chain Systems 224  
           4.O.ii Conformation in Six-Membered Rings 230  
           4.O.iii Conformation in Six-Membered Rings Containing Heteroatoms 235  
           4.O.iv Conformation in Other Rings 238  
        4.P Molecular Mechanics 240  
        4.Q Strain 242  
           4.Q.i Strain in Small Rings 243  
           4.Q.ii Strain in Other Rings 249  
           4.Q.iii Unsaturated Rings 251  
           4.Q.iv Strain Due to Unavoidable Crowding 254  
     5 Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 259  
        5.A Carbocations 260  
           5.A.i Nomenclature 260  
           5.A.ii Stability and Structure of Carbocations 260  
           5.A.iii The Generation And Fate Of Carbocations 270  
        5.B Carbanions 273  
           5.B.i Stability and Structure 273  
           5.B.ii The Structure Of Organometallic Compounds 280  
           5.B.iii The Generation And Fate Of Carbanions 285  
        5.C Free Radicals 286  
           5.C.i Stability and Structure 286  
           5.C.ii The Generation and Fate of Free Radicals 297  
           5.C.iii Radical Ions 301  
        5.D Carbenes 302  
           5.D.i Stability and Structure 302  
           5.D.ii The Generation and Fate of Carbenes 305  
           5.D.iii N-Heterocyclic Carbenes (NHCs) 310  
        5.E Nitrenes 312  
     6 Mechanisms and Methods of Determining Them 315  
        6.A Types of Mechanism 315  
        6.B Types of Reaction 316  
        6.C Thermodynamic Requirements for Reaction 319  
        6.D Kinetic Requirements for Reaction 320  
        6.E The Baldwin Rules for Ring Closure 324  
        6.F Kinetic and Thermodynamic Control 326  
        6.G The Hammond Postulate 327  
        6.H Microscopic Reversibility 327  
        6.I Marcus Theory 328  
        6.J Methods of Determining Mechanisms 329  
           6.J.i Identification of Products 329  
           6.J.ii Determination of the Presence of an Intermediate 330  
           6.J.iii The Study of Catalysis 331  
           6.J.iv Isotopic Labeling 332  
           6.J.v Stereochemical Evidence 332  
           6.J.vi Kinetic Evidence 333  
           6.J.vii Isotope Effects 340  
        6.K Catalyst Development 344  
     7 Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 349  
        7.A Photochemistry 350  
           7.A.i Excited States and the Ground State 350  
           7.A.ii Singlet and Triplet States: “Forbidden” Transitions 352  
           7.A.iii Types of Excitation 353  
           7.A.iv Nomenclature and Properties of Excited States 354  
           7.A.v Photolytic Cleavage 355  
           7.A.vi The Fate of the Excited Molecule: Physical Processes 356  
           7.A.vii The Fate of the Excited Molecule: Chemical Processes 361  
           7.A.viii The Determination of Photochemical MechanismsFor a review, see Calvert, J.G. 366  
        7.B Sonochemistry 367  
        7.C Microwave Chemistry 370  
        7.D Flow Chemistry 372  
        7.E Mechanochemistry 374  
     8 Acids and Bases 375  
        8.A Brønsted Theory 375  
           8.A.i Brønsted Acids 376  
           8.A.ii Brønsted Bases 383  
        8.B The Mechanism of Proton Transfer Reactions 386  
        8.C Measurements of Solvent Acidity 388  
        8.D Acid and Base Catalysis 391  
        8.E Lewis Acids and Bases 393  
           8.E.i Hard–Soft Acids–Bases 395  
        8.F The Effects of Structure on the Strengths of Acids and Bases 397  
        8.G The Effects of the Medium on Acid and Base Strength 406  
     9 Effects of Structure and Medium on Reactivity 411  
        9.A Resonance and Field Effects 411  
        9.B Steric Effects 413  
        9.C Quantitative Treatments of the Effect of Structure on Reactivity 416  
        9.D Effect of Medium on Reactivity and Rate 426  
        9.E High Pressure 426  
        9.F Water and Other Nonorganic Solvents 427  
        9.G Ionic Liquid Solvents 429  
        9.H Solventless Reactions 431  
  PART II INTRODUCTION 433  
     II.A IUPAC Nomenclature for Transformations 434  
     II.B IUPAC System for Symbolic Representation of Mechanisms 434  
        Step 1, First Symbol 435  
        Step 1, Second Symbol 435  
        Step 1, Combined Symbols 435  
        Step 2 436  
        Overall 436  
     II.C Organic Syntheses References 436  
     10 Aliphatic Substitution, Nucleophilic and Organometallic 439  
        10.A Mechanisms 440  
           10.A.i The SN2 Mechanism 440  
           10.A.ii The SN1 Mechanism 446  
           10.A.iii Ion Pairs in the SN1 Mechanism 450  
           10.A.iv Mixed SN1 and SN2 Mechanisms 454  
        10.B SET Mechanisms 456  
        10.C The Neighboring-Group Mechanism 458  
           10.C.i Neighboring-Group Participation by ?????? and ?????? Bonds: Nonclassical Carbocations 461  
        10.D The SNi Mechanism 476  
        10.E Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 477  
        10.F Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 481  
        10.G Reactivity 485  
           10.G.i The Effect of Substrate Structure 485  
           10.G.ii The Effect of the Attacking Nucleophile 493  
           10.G.iii The Effect of the Leaving Group 500  
           10.G.iv The Effect of the Reaction Medium 505  
           10.G.v Phase-Transfer Catalysis 510  
           10.G.vi Influencing Reactivity by External Means 513  
           10.G.vii Ambident (Bidentant) Nucleophiles: Regioselectivity 514  
           10.G.viii Ambident Substrates 517  
        10.H Reactions 519  
           10.H.i Oxygen Nucleophiles 519  
           10.H.ii Sulfur Nucleophiles 542  
           10.H.iii Nitrogen Nucleophiles 548  
           10.H.iv Halogen Nucleophiles 570  
           10.H.v Carbon Nucleophiles 581  
     11 Aromatic Substitution, Electrophilic 643  
        11.A Mechanisms 643  
           11.A.i The Arenium Ion Mechanism 644  
           11.A.ii The SE1 Mechanism 649  
        11.B Orientation and Reactivity 650  
           11.B.i Orientation and Reactivity in Monosubstituted Benzene Rings 650  
           11.B.ii The Ortho/Para Ratio 654  
           11.B.iii Ipso Attack 656  
           11.B.iv Orientation in Benzene Rings With More Than One Substituent 657  
           11.B.v Orientation in Other Ring Systems 658  
        11.C Quantitative Treatments of Reactivity in the Substrate 660  
        11.D A Quantitative Treatment of Reactivity of the Electrophile 662  
        11.E The Effect of the Leaving Group 664  
        11.F Reactions 665  
           11.F.i Hydrogen as the Leaving Group in Simple Substitution Reactions 665  
           11.F.ii Hydrogen As The Leaving Group In Rearrangement Reactions 711  
           11.F.iii Other Leaving Groups 716  
     12 Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 723  
        12.A Mechanisms 723  
           12.A.i Bimolecular Mechanisms. SE2 and SEi 724  
           12.A.ii The SE1 Mechanism 727  
           12.A.iii Electrophilic Substitution Accompanied by Double-Bond Shifts 730  
           12.A.iv Other Mechanisms 731  
        12.B Reactivity 731  
        12.C Reactions 733  
           12.C.i Hydrogen as Leaving Group 733  
           12.C.ii Metals as Leaving Groups 769  
           12.C.iii Halogen as Leaving Group 782  
           12.C.iv Carbon Leaving Groups 787  
           12.C.v Electrophilic Substitution At Nitrogen 796  
     13 Aromatic Substitution: Nucleophilic and Organometallic 803  
        13.A Mechanisms 804  
           13.A.i The SNAr Mechanism 804  
           13.A.ii The SN1 Mechanism 807  
           13.A.iii The Benzyne Mechanism 808  
           13.A.iv The SRN1 Mechanism 810  
           13.A.v Other Mechanisms 812  
        13.B Reactivity 812  
           13.B.i The Effect of Substrate Structure 812  
           13.B.ii The Effect of the Leaving Group 814  
           13.B.iii The Effect of the Attacking Nucleophile 815  
        13.C Reactions 815  
           13.C.i All Leaving Groups Except Hydrogen And N2+ 815  
           13.C.ii Hydrogen as Leaving Group 859  
           13.C.iii Nitrogen as Leaving Group 860  
           13.C.iv Rearrangements 870  
     14 Radical Reactions 875  
        14.A Mechanisms 875  
           14.A.i Radical Mechanisms in General 875  
           14.A.ii Free-Radical Substitution Mechanisms 880  
           14.A.iii Mechanisms at an Aromatic Substrate 881  
           14.A.iv Neighboring-Group Assistance in Free-Radical Reactions 883  
        14.B Reactivity 884  
           14.B.i Reactivity for Aliphatic Substrates 884  
           14.B.ii Reactivity at a Bridgehead 889  
           14.B.iii Reactivity in Aromatic Substrates 890  
           14.B.iv Reactivity in the Attacking Radical 891  
           14.B.v The Effect of Solvent on Reactivity 892  
        14.C Reactions 892  
           14.C.i Hydrogen as Leaving Group 892  
           14.C.ii Metals as Leaving Groups 916  
           14.C.iii Halogen as Leaving Group 919  
           14.C.iv Sulfur as Leaving Group 919  
           14.C.v Carbon as Leaving Group 921  
     15 Addition to Carbon–Carbon Multiple Bonds 927  
        15.A Mechanisms 928  
           15.A.i Electrophilic Addition 928  
           15.A.ii Nucleophilic Addition 931  
           15.A.iii Free-Radical Addition 932  
           15.A.iv Cyclic Mechanisms 934  
           15.A.v Addition to Conjugated Systems 934  
        15.B Orientation and Reactivity 935  
           15.B.i Reactivity 935  
           15.B.ii Orientation 938  
           15.B.iii Stereochemical Orientation 940  
           15.B.iv Addition to Cyclopropane Rings 942  
        15.C Reactions 944  
           15.C.i Isomerization of Double and Triple Bonds 944  
           15.C.ii Reactions in Which Hydrogen Adds to One Side 946  
           15.C.iii Reactions in Which Hydrogen Adds to Neither Side 1028  
           15.C.iv Cycloaddition Reactions 1063  
     16 Addition to Carbon–Heteroatom Multiple Bonds 1123  
        16.A Mechanism and Reactivity 1123  
           16.A.i Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 1125  
        16.B Reactions 1130  
           16.B.i Reactions in Which Hydrogen or a Metallic Ion Adds to the Heteroatom 1131  
           16.B.ii Acyl Substitution Reactions 1254  
           16.B.iii Reactions in Which Carbon Adds to the Heteroatom 1293  
           16.B.iv Addition to Isocyanides 1300  
           16.B.v Nucleophilic Substitution at a Sulfonyl Sulfur Atom 1302  
     17 Elimination Reactions 1309  
        17.A Mechanisms and Orientation 1309  
           17.A.i The E2 Mechanism 1310  
           17.A.ii The E1 Mechanism 1316  
           17.A.iii The E1cB Mechanism 1317  
           17.A.iv The E1-E2-E1cB Spectrum 1322  
           17.A.v The E2C Mechanism 1323  
        17.B Regiochemistry of the Double Bond 1324  
        17.C Stereochemistry of the Double Bond 1326  
        17.D Reactivity 1327  
           17.D.i Effect of Substrate Structure 1327  
           17.D.ii Effect of the Attacking Base 1329  
           17.D.iii Effect of the Leaving Group 1330  
           17.D.iv Effect of the Medium 1330  
        17.E Mechanisms and Orientation in Pyrolytic Eliminations 1331  
           17.E.i Mechanisms 1331  
           17.E.ii Orientation in Pyrolytic Eliminations 1334  
           17.E.iii 1,4 Conjugate Eliminations 1334  
        17.F Reactions 1335  
           17.F.i Reactions in Which C=C and C?C Bonds Are Formed 1335  
           17.F.ii Fragmentations 1357  
           17.F.iii Reactions in Which C?N or C=N Bonds Are Formed 1361  
           17.F.iv Reactions in Which C=O Bonds Are Formed 1364  
           17.F.v Reactions in Which N=N Bonds Are Formed 1365  
           17.F.vi Extrusion Reactions 1365  
     18 Rearrangements 1371  
        18.A Mechanisms 1372  
           18.A.i Nucleophilic Rearrangements 1372  
           18.A.ii The Actual Nature of the Migration 1373  
           18.A.iii Migratory Aptitudes 1376  
           18.A.iv Memory Effects 1379  
        18.B Longer Nucleophilic Rearrangements 1380  
        18.C Free-Radical Rearrangements 1381  
        18.D Carbene Rearrangements 1385  
        18.E Electrophilic Rearrangements 1385  
        18.F Reactions 1386  
           18.F.i 1,2-Rearrangements 1386  
           18.F.ii Non 1,2-Rearrangements 1425  
     19 Oxidations and Reductions 1475  
        19.A Mechanisms 1476  
        19.B Reactions 1478  
           19.B.i Oxidations 1478  
           19.B.ii Reductions 1546  
  Appendix A The Literature of Organic Chemistry 1643  
     A Primary Sources 1644  
        A.i Journals 1644  
        A.ii Patents 1645  
     B Secondary Sources 1649  
        B.i Listings of Titles 1649  
        B.ii Abstracts 1650  
        B.iii Beilstein 1653  
        B.iv Tables of Information 1655  
     C Reviews 1658  
        C.i Annual Reviews 1659  
        C.ii Awareness Services 1660  
        C.iii General Treatises 1661  
        C.iv Monographs and Treatises on Specific Areas 1663  
        C.v Textbooks 1663  
        C.vi Other Books 1664  
     D Literature Searching 1666  
        D.i Literature Searching Using Printed Materials 1666  
        D.ii Literature Searching Online 1668  
        D.iii Sci-Finder – the CAS database 1669  
        D.iv Science Citation Index 1671  
        D.v How to Locate Journal Articles 1675  
        D.vi Reaxys® 1676  
  Appendix B Classification of Reactions by Type of Compounds Synthesized 1681  
  Author Index 1705  
  Subject Index 1953  
  EULA 2141  


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