New Reaction Sections Correlation: 7th Edition → 8th Edition xv Preface xxi Common Abbreviations xxv Biographical Statement xxxi New Features of the 8th Edition xxxiii Part I Introduction 1 1. Localized Chemical Bonding 3 1.A. Covalent Bonding 3 1.B. Multiple Valence 7 1.C. Hybridization 7 1.

D. Multiple Bonds 9 1.E. Photoelectron Spectroscopy 12 1.F. Electronic Structures of Molecules 15 1.G. Electronegativity 17 1.

H. Dipole Moment 19 1.I. Inductive and Field Effects 20 1.J. Bond Distances 23 1.K. Bond Angles 27 1.

L. Bond Energies 29 2. Delocalized Chemical Bonding 33 2.A. Molecular Orbitals 34 2.B. Bond Energies and Distances in Compounds Containing Delocalized Bonds 37 2.C.

Molecules that have Delocalized Bonds 39 2.D. Cross Conjugation 44 2.E. The Rules of Resonance 46 2.F. The Resonance Effect 48 2.G.

Steric Inhibition of Resonance and the Influences of Strain 48 2.H. p π- d π Bonding: Ylids 52 2.I. Aromaticity 54 2.I.i. Six-Membered Rings 58 2.

I.ii. Five-, Seven-, and Eight-Membered Rings 62 2.I.iii. Other Systems Containing Aromatic Sextets 67 2.J. Alternant and Nonalternant Hydrocarbons 68 2.

K. Aromatic Systems with Electron Numbers Other Than Six 70 2.K.i. Systems of Two Electrons 72 2.K.ii. Systems of Four Electrons: Antiaromaticity 73 2.

K.iii. Systems of Eight Electrons 76 2.K.iv. Systems of Ten Electrons 77 2.K.v.

Systems of More than Ten Electrons: 4 n + 2 Electrons 80 2.K.vi. Systems of More Than Ten Electrons: 4 n Electrons 85 2.L. Other Aromatic Compounds 89 2.M. Hyperconjugation 92 2.

N. Tautomerism 96 2.N.i. Keto-Enol Tautomerism 97 2.N.ii. Other Proton-Shift Tautomerism 100 3.

Bonding Weaker Than Covalent 105 3.A. Hydrogen Bonding 105 3.B. π-π Interactions 113 3.C. Addition Compounds 114 3.C.

i. Electron Donor-Acceptor (EDA) Complexes 114 3.C.ii. Crown Ether Complexes and Cryptates 117 3.C.iii. Inclusion Compounds 122 3.

C.iv. Cyclodextrins 125 3.D. Catenanes and Rotaxanes 127 3.E. Cucurbit[ n ]Uril-Based Gyroscane 131 4. Stereochemistry and Conformation 133 4.

A. Optical Activity and Chirality 133 4.B. Dependence of Rotation on Conditions of Measurement 135 4.C. What Kinds of Molecules Display Optical Activity? 136 4.D. The Fischer Projection 147 4.

E. Absolute Configuration 148 4.E.i. The Cahn-Ingold-Prelog System 150 4.E.ii. Methods of Determining Configuration 152 4.

F. The Cause of Optical Activity 156 4.G. Molecules with More Than One Stereogenic Center 157 4.H. Asymmetric Synthesis 161 4.I. Methods of Resolution 166 4.

J. Optical Purity 173 4.K. Cis - Trans Isomerism 175 4.K.i. Cis - Trans Isomerism Resulting from Double Bonds 175 4.K.

ii. Cis - Trans Isomerism of Monocyclic Compounds 179 4.K.iii. Cis - Trans Isomerism of Fused and Bridged Ring Systems 180 4.L. Out - In Isomerism 181 4.M.

Enantiotopic and Diastereotopic Atoms, Groups, and Faces 183 4.N. Stereospecific and Stereoselective Syntheses 186 4.O. Conformational Analysis 187 4.O.i. Conformation in Open-Chain Systems 188 4.

O.ii. Conformation in Six-Membered Rings 194 4.O.iii. Conformation in Six-Membered Rings Containing Heteroatoms 199 4.O.iv.

Conformation in Other Rings 202 4.P. Molecular Mechanics 204 4.Q. Strain 206 4.Q.i. Strain in Small Rings 207 4.

Q.ii. Strain in Other Rings 213 4.Q.iii. Unsaturated Rings 215 4.Q.iv.

Strain Due to Unavoidable Crowding 218 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 223 5.A. Carbocations 224 5.A.i. Nomenclature 224 5.A.

ii. Stability and Structure of Carbocations 224 5.A.iii. The Generation and Fate of Carbocations 234 5.B. Carbanions 237 5.B.

i. Stability and Structure 237 5.B.ii. The Structure of Organometallic Compounds 244 5.B.iii. The Generation and Fate of Carbanions 249 5.

C. Free Radicals 250 5.C.i. Stability and Structure 250 5.C.ii. The Generation and Fate of Free Radicals 261 5.

C.iii. Radical Ions 265 5.D. Carbenes 266 5.D.i. Stability and Structure 266 5.

D.ii. The Generation and Fate of Carbenes 269 5.D.iii. N -Heterocyclic Carbenes (NHCs) 274 5.E. Nitrenes 276 6.

Mechanisms and Methods of Determining Them 279 6.A. Types of Mechanism 279 6.B. Types of Reaction 280 6.C. Thermodynamic Requirements for Reaction 283 6.D.

Kinetic Requirements for Reaction 284 6.E. The Baldwin Rules for Ring Closure 288 6.F. Kinetic and Thermodynamic Control 290 6.G. The Hammond Postulate 291 6.H.

Microscopic Reversibility 291 6.I. Marcus Theory 292 6.J. Methods of Determining Mechanisms 293 6.J.i. Identification of Products 293 6.

J.ii. Determination of the Presence of an Intermediate 294 6.J.iii. The Study of Catalysis 295 6.J.iv.

Isotopic Labeling 296 6.J.v. Stereochemical Evidence 296 6.J.vi. Kinetic Evidence 297 6.J.

vii. Isotope Effects 304 6.K. Catalyst Development 308 7. Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 313 7.A. Photochemistry 314 7.A.

i. Excited States and the Ground State 314 7.A.ii. Singlet and Triplet States: "Forbidden" Transitions 316 7.A.iii. Types of Excitation 317 7.

A.iv. Nomenclature and Properties of Excited States 318 7.A.v. Photolytic Cleavage 319 7.A.vi.

The Fate of the Excited Molecule: Physical Processes 320 7.A.vii. The Fate of the Excited Molecule: Chemical Processes 325 7.A.viii. The Determination of Photochemical Mechanisms 330 7.B.

Sonochemistry 331 7.C. Microwave Chemistry 334 7.D. Flow Chemistry 336 7.E. Mechanochemistry 338 8. Acids and Bases 339 8.

A. Brønsted Theory 339 8.A.i. Brønsted Acids 340 8.A.ii. Brønsted Bases 347 8.

B. The Mechanism of Proton Transfer Reactions 350 8.C. Measurements of Solvent Acidity 352 8.D. Acid and Base Catalysis 355 8.E. Lewis Acids and Bases 357 8.

E.i. Hard-Soft Acids-Bases 359 8.F. The Effects of Structure on the Strengths of Acids and Bases 361 8.G. The Effects of the Medium on Acid and Base Strength 370 9. Effects of Structure and Medium on Reactivity 375 9.

A. Resonance and Field Effects 375 9.B. Steric Effects 377 9.C. Quantitative Treatments of the Effect of Structure on Reactivity 380 9.D. Effect of Medium on Reactivity and Rate 390 9.

E. High Pressure 390 9.F. Water and Other Nonorganic Solvents 391 9.G. Ionic Liquid Solvents 393 9.H. Solventless Reactions 395 Part II Introduction 397 10.

Aliphatic Substitution, Nucleophilic and Organometallic 403 10.A. Mechanisms 404 10.A.i. The SN2 Mechanism 404 10.A.ii.

The SN1 Mechanism 410 10.A.iii. Ion Pairs in the SN1 Mechanism 414 10.A.iv. Mixed SN1 and SN2 Mechanisms 418 10.B.

SET Mechanisms 420 10.C. The Neighboring-Group Mechanism 422 10.C.i. Neighboring-Group Participation by π and σ Bonds: Nonclassical Carbocations 425 10.D. The SNi Mechanism 440 10.

E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 441 10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 445 10.G. Reactivity 449 10.G.i.

The Effect of Substrate Structure 449 10.G.ii. The Effect of the Attacking Nucleophile 457 10.G.iii. The Effect of the Leaving Group 464 10.G.

iv. The Effect of the Reaction Medium 469 10.G.v. Phase-Transfer Catalysis 474 10.G.vi. Influencing Reactivity by External Means 477 10.

G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 478 10.G.viii. Ambident Substrates 481 10.H. Reactions 483 10.

H.i. Oxygen Nucleophiles 483 10.H.ii. Sulfur Nucleophiles 506 10.H.iii.

Nitrogen Nucleophiles 512 10.H.iv. Halogen Nucleophiles 534 10.H.v. Carbon Nucleophiles 545 11. Aromatic Substitution, Electrophilic 607 11.

A. Mechanisms 607 11.A.i. The Arenium Ion Mechanism 608 11.A.ii. The SE1 Mechanism 613 11.

B. Orientation and Reactivity 614 11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings 614 11.B.ii. The Ortho / Para Ratio 618 11.

B.iii. Ipso Attack 620 11.B.iv. Orientation in Benzene Rings With More Than One Substituent 621 11.B.v.

Orientation in Other Ring Systems 622 11.C. Quantitative Treatments of Reactivity in the Substrate 624 11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 626 11.E. The Effect of the Leaving Group 628 11.F.

Reactions 629 11.F.i. Hydrogen as the Leaving Group in Simple Substitution Reactions 629 11.F.ii. Hydrogen as the Leaving Group in Rearrangement Reactions 675 11.F.

iii. Other Leaving Groups 680 12. Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 687 12.A. Mechanisms 687 12.A.i. Bimolecular Mechanisms.

SE2 and SEi 688 12.A.ii. The SE1 Mecha.