New Reaction Sections Correlation: 8th Edition → 9th Editions xiii Preface xix Common Abbreviations xxi Biographical Statement xxvii New Features of the 9th Edition xxix Part I Introduction 1 1. Localized Chemical Bonding 3 1.a. Covalent Bonding 3 1.b. Multiple Valence 6 1.c. Hybridization 6 1.

d. Multiple Bonds 7 1.e. Photoelectron Spectroscopy 9 1.f. Electronic Structures of Molecules 11 1.g. Electronegativity 13 1.

h. Dipole Moment 15 1.i. Inductive and Field Effects 16 1.j. Bond Distances 19 1.k. Bond Angles 22 1.

l. Bond Energies 23 2. Delocalized Chemical Bonding 27 2.a. Molecular Orbitals 28 2.b. Bond Energies and Distances in Compounds Containing Delocalized Bonds 31 2.c.

Molecules that have Delocalized Bonds 32 2.d. Cross- Conjugation 35 2.e. The Rules of Resonance 36 2.f. The Resonance Effect 37 2.g.

Steric Inhibition of Resonance and the Influences of Strain 37 2.h. pπ-dπ Bonding. Ylids 40 2.i. Aromaticity 42 2.I.i.

Six- Membered Rings 45 2.I.ii. Five- , Seven- , and Eight- Membered Rings 48 2.I.iii. Other Systems Containing Aromatic Sextets 52 2.j.

Alternant and Nonalternant Hydrocarbons 54 2.k. Aromatic Systems with Electron Numbers other than Six 54 2.K.i. Systems of Two Electrons 55 2.K.ii.

Systems of Four Electrons: Antiaromaticity 56 2.K.iii. Systems of Eight Electrons 59 2.K.iv. Systems of Ten Electrons 60 2.K.

v. Systems of More than Ten Electrons: 4n + 2 Electrons 62 2.K.vi. Systems of More than Ten Electrons: 4n Electrons 66 2.l. Other Aromatic Compounds 70 2.M.

Hyperconjugation 72 2.n. Tautomerism 75 2.N.i. Keto- Enol Tautomerism 75 2.N.ii.

Other Proton- Shift Tautomerism 79 3. Bonding Weaker Than Covalent 83 3.a. Hydrogen Bonding 83 3.b. π-π Interactions 90 3.c. Addition Compounds 91 3.

C.i. Electron Donor-Acceptor Complexes 92 3.C.ii. Crown Ether Complexes and Cryptates 94 3.C.iii.

Inclusion Compounds 99 3.C.iv. Cyclodextrins 102 3.d. Catenanes and Rotaxanes 104 3.e. Cucurbit[n]Uril- Based Gyroscane 107 4.

Stereochemistry and Conformation 109 4.a. Optical Activity and Chirality 109 4.b. Dependence of Rotation on Conditions of Measurement 111 4.c. What kinds of Molecules Display Optical Activity? 112 4.d.

The Fischer Projection 121 4.e. Absolute Configuration 121 4.E.i. The Cahn-Ingold-Prelog System 122 4.E.ii.

Methods of Determining Configuration 125 4.f. Optical Purity 128 4.g. The Cause of Optical Activity 130 4.h. Molecules with more than One Stereogenic Center 131 4.i.

Asymmetric Synthesis 134 4.j. Methods of Resolution 137 4.k. Cis-Trans Isomerism 142 4.K.i. Cis-Trans Isomerism Resulting from Double Bonds 142 4.

K.ii. Cis-Trans Isomerism of Monocyclic Compounds 145 4.K.iii. Cis-Trans Isomerism of Fused and Bridged Ring Systems 146 4.l. Out-In Isomerism 147 4.

M. Enantiotopic and Diastereotopic Atoms, Groups, and Faces 149 4.n. Stereospecific and Stereoselective Syntheses 151 4.o. Conformational Analysis 152 4.O.i.

Conformation in Open- Chain Systems 153 4.O.ii. Conformation in Six- Membered Rings 158 4.O.iii. Conformation in Six- Membered Rings Containing Heteroatoms 162 4.O.

iv. Conformation in Other Rings 164 4.p. Molecular Mechanics 166 4.q. Strain 168 4.Q.i.

Strain in Small Rings 168 4.Q.ii. Strain in Other Rings 172 4.Q.iii. Unsaturated Rings 174 4.Q.

iv. Strain Due to Unavoidable Crowding 177 5. Carbocations, Carbanions, Free Radicals, Carbenes, and Nitrenes 181 5.a. Carbocations 182 5.A.i. Nomenclature 182 5.

A.ii. Stability and Structure of Carbocations 182 5.A.iii. The Generation and Fate of Carbocations 190 5.b. Carbanions 192 5.

B.i. Stability and Structure 192 5.B.ii. The Structure of Grignard Reagents and Organolithium Reagents 198 5.B.iii.

The Generation and Fate of Carbanions 201 5.c. Free Radicals 202 5.C.i. Stability and Structure 202 5.C.ii.

The Generation and Fate of Free Radicals 212 5.C.iii. Radical Ions 215 5.d. Carbenes 217 5.D.i.

Stability and Structure 217 5.D.ii. The Generation and Fate of Carbenes 220 5.D.iii. N- Heterocyclic Carbenes 223 5.e.

Nitrenes 225 6. Mechanisms and Methods of Determining Them 229 6.a. Types of Mechanism 229 6.b. Types of Reaction 230 6.c. Thermodynamic Requirements for Reaction 232 6.

d. Kinetic Requirements for Reaction 233 6.e. The Baldwin Rules for Ring Closure 236 6.f. Kinetic and Thermodynamic Control 238 6.g. The Hammond Postulate 238 6.

h. Microscopic Reversibility 239 6.i. Marcus Theory 239 6.j. Methods of Determining Mechanisms 240 6.J.i.

Identification of Products 241 6.J.ii. Determination of the Presence of an Intermediate 241 6.J.iii. The Study of Catalysis 242 6.J.

iv. Isotopic Labeling 243 6.J.v. Stereochemical Evidence 243 6.J.vi. Kinetic Evidence 244 6.

J.vii. Isotope Effects 250 6.k. Catalyst Development 253 7. Irradiation Processes and Techniques that Influence Reactions in Organic Chemistry 257 7.a. Photochemistry 257 7.

A.i. Excited States and the Ground State 257 7.A.ii. Singlet and Triplet States: "Forbidden" Transitions 259 7.A.iii.

Types of Excitation 260 7.A.iv. Nomenclature and Properties of Excited States 262 7.A.v. Photolytic Cleavage 262 7.A.

vi. The Fate of the Excited Molecule: Physical Processes 263 7.A.vii. The Fate of the Excited Molecule: Chemical Processes 267 7.A.viii. The Determination of Photochemical Mechanisms 271 7.

b. Sonochemistry 272 7.c. Microwave Chemistry 274 7.d. Flow Chemistry 275 7.e. Mechanochemistry 276 8.

Acids and Bases 279 8.a. Brønsted Theory 279 8.A.i. Brønsted Acids 280 8.A.ii.

Brønsted Bases 286 8.b. The Mechanism of Proton Transfer Reactions 289 8.c. Measurements of Solvent Acidity 290 8.d. Acid and Base Catalysis 293 8.e.

Lewis Acids and Bases 295 8.E.i. Hard-Soft Acids-Bases 296 8.f. The Effects of Structure on the Strengths of Acids and Bases 298 8.g. The Effects of the Medium on Acid and Base Strength 306 9.

Effects of Structure and Medium on Reactivity 309 9.a. Resonance and Field Effects 309 9.b. Steric Effects 311 9.c. Quantitative Treatments of the Effect of Structure on Reactivity 313 9.d.

Effect of Medium on Reactivity and Rate 320 9.e. High Pressure 321 9.f. Water and other Nonorganic Solvents 321 9.g. Ionic Liquid Solvents 323 9.h.

Solventless Reactions 325 Part II Introduction 327 10. Aliphatic Substitution: Nucleophilic and Organometallic 329 10.A. Mechanisms 330 10.A.i. The S N 2 Mechanism 330 10.A.

ii. The S N 1 Mechanism 334 10.A.iii. Ion Pairs in the S N 1 Mechanism 338 10.A.iv. Mixed S N 1 and S N 2 Mechanisms 340 10.

B. Set Mechanisms 342 10.C. The Neighboring- Group Mechanism 344 10.C.i. Neighboring- Group Participation by π and σ Bonds: Nonclassical Carbocations 347 10.D.

The S N I Mechanism 359 10.E. Nucleophilic Substitution at an Allylic Carbon: Allylic Rearrangements 360 10.F. Nucleophilic Substitution at an Aliphatic Trigonal Carbon: The Tetrahedral Mechanism 363 10.G. Reactivity 366 10.G.

i. The Effect of Substrate Structure 366 10.G.ii. The Effect of the Attacking Nucleophile 374 10.G.iii. The Effect of the Leaving Group 378 10.

G.iv. The Effect of the Reaction Medium 382 10.G.v. Phase- Transfer Catalysis 387 10.G.vi.

Influencing Reactivity by External Means 389 10.G.vii. Ambident (Bidentant) Nucleophiles: Regioselectivity 390 10.G.viii. Ambident Substrates 393 10.H.

Reactions 394 11. Aromatic Substitution: Electrophilic 491 11.A. Mechanisms 491 11.A.i. The Arenium Ion Mechanism 491 11.B.

Orientation and Reactivity 496 11.B.i. Orientation and Reactivity in Monosubstituted Benzene Rings 496 11.B.ii. The Ortho/Para Ratio 499 11.B.

iii. Ipso Attack 500 11.B.iv. Orientation in Benzene Rings with more than one Substituent 501 11.B.v. Orientation in Other Ring Systems 502 11.

C. Quantitative Treatments of Reactivity in the Substrate 504 11.D. A Quantitative Treatment of Reactivity of the Electrophile: The Selectivity Relationship 505 11.E. The Effect of the Leaving Group 507 11.F. Reactions 507 12.

Aliphatic, Alkenyl, and Alkynyl Substitution: Electrophilic and Organometallic 555 12.A. Mechanisms 555 12.A.i. Bimolecular Mechanisms: S E 2 and S E I 556 12.A.ii.

The S E 1 Mechanism 558 12.A.iii. Electrophilic Substitution Accompanied by Double- Bond Shifts 560 12.A.iv. Other Mechanisms 561 12.B.

Reactivity 561 12.C. Reactions 562 13. Aromatic Substitution: Nucleophilic and Organometallic 617 13.A. Mechanisms 617 13.A.i.

The S N Ar Mechanism 618 13.A.ii. The S N 1 Mechanism 620 13.A.iii. The Benzyne Mechanism 621 13.A.

iv. The S RN 1 Mechanism 623 13.A.v. Other Mechanisms 624 13.B. Reactivity 625 13.B.

i. Th.