Organic Chemistry

by Vollhardt and Schore

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Contents

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  1. Front Matter
  2. TitlePage
  3. InfoPage
  4. Table of Contents
  5. Licensing
  6. 1: Structure and Bonding in Organic Molecules
  7. 1.1: The Scope of Organic Chemistry
  8. 1.2: Coulomb Forces - A Simplified View of Bonding
  9. 1.3: Ionic and Covalent Bonds - The Octet Rule
  10. 1.4: Electron-Dot Model of Bonding - Lewis Structures
  11. 1.5: Resonance Forms
  12. 1.6: Atomic Orbitals: A Quantum Mechanical Description of Electrons Around the Nucleus
  13. 1.7: Molecular Orbitals and Covalent Bonding
  14. 1.8: Hybrid Orbitals: Bonding in Complex Molecules and Practice Problems
  15. 1.9: Structures and Formulas of Organic Molecules
  16. 1.E: Structure and Bonding in Organic Molecules (Exercises)
  17. 2: Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules
  18. 2.1: Kinetics and Thermodynamics of Simple Chemical Processes
  19. 2.2: Keys to Success: Using Curved "Electron Pushing" Arrows to Describe Chemical Reactions
  20. 2.3: Acids and Bases; Electrophiles and Nucleophiles
  21. 2.4: Functional Groups: Centers of Reactivity
  22. 2.5: Straight-Chain and Branched Alkanes
  23. 2.6: Naming the Alkanes
  24. 2.7: Structural and Physical Properties of Alkanes
  25. 2.8: Rotation about Single Bonds: Conformations
  26. 2.9: Rotation in Substituted Ethanes
  27. 2.E: Structure and Reactivity: Acids and Bases, Polar and Nonpolar Molecules (Exercises)
  28. 3: Reactions of Alkanes: Bond-Dissociation Energies, Radical Halogenation, and Relative Reactivity
  29. 3.1: Strength of Alkane Bonds: Radicals
  30. 3.2: Structure of Alkyl Radicals: Hyperconjugation
  31. 3.3: Conversion of Petroleum: Pyrolysis
  32. 3.4: Chlorination of Methane: The Radical Chain Mechanism
  33. 3.5: Other Radical Halogenations of Methane
  34. 3.6: Keys to Success: Using the "Known" Mechanism as a model for the "Unknown"
  35. 3.7: Chlorination of Higher Alkanes: Relative Reactivity and Selectivity
  36. 3.8: Selectivity in Radical Halogenation with Fluorine and Bromine
  37. 3.9: Synthetic Radical Halogenation
  38. 3.10: Synthetic Chlorine Compounds and the Stratospheric Ozone Layer
  39. 3.11: Combustion and the Relative Stabilities of Alkanes
  40. 3.E: Reactions of Alkanes (Exercises)
  41. 4: Cycloalkanes
  42. 4.1: Names and Physical Properties of Cycloalkanes
  43. 4.2: Ring Strain and the Structure of Cycloalkanes
  44. 4.3: Cyclohexane: A Strain-Free Cycloalkane
  45. 4.4: Substituted Cyclohexanes
  46. 4.5: Larger Cycloalkanes
  47. 4.6: Polycyclic Alkanes
  48. 4.7: Carbocyclic Products in Nature
  49. 4.E: Cycloalkanes (Exercises)
  50. 5: Stereoisomers
  51. 5.1: Chiral Molecules
  52. 5.2: Optical Activity
  53. 5.3: Absolute Configuration: R-S Sequence Rules
  54. 5.4: Fischer Projections
  55. 5.5: Molecules Incorporating Several Stereocenters: Diastereomers
  56. 5.6: Meso Compounds
  57. 5.7: Stereochemistry in Chemical Reactions
  58. 5.8: Resolution: Separation of Enantiomers
  59. 5.E: Stereoisomers (Exercises)
  60. 6: Bimolecular Nucleophilic Substitution in Haloalkanes
  61. 6.1: Physical Properties of Haloalkanes
  62. 6.2: Nucleophilic Substitution
  63. 6.3: Reaction Mechanisms Involving Polar Functional Groups: Using "Electron-Pushing'" Arrows
  64. 6.4: A Closer Look at the Nucleophilic Substitution Mechanism: Kinetics
  65. 6.5: Frontside or Backside Attack? Stereochemistry of the SN2 Reaction
  66. 6.6: Consequences of Inversion in SN2 Reactions
  67. 6.7: Structure and \(S_N2\) Reactivity: The Leaving Group
  68. 6.8: Structure and SN2 Reactivity: The Nucleophile
  69. 6.9: Keys to Success: Choosing Among Multiple Mechanistic Pathways
  70. 6.3: Reaction Mechanisms Involving Polar Functional Groups: Using "Electron-Pushing\\'" Arrows
  71. 6.10: Structure and SN2 Reactivity: The Substrate
  72. 6.11: The Sn2 Reaction at a Glance
  73. 6.E: Properties and Reactions of Haloalkanes: Bimolecular Nucleophilic Substitution (Exercises)
  74. 7: Further Reactions of Haloalkanes: Unimolecular Substitution and Pathways of Elimination
  75. 7.1: Solvolysis of Tertiary and Secondary Haloalkanes
  76. 7.2: Unimolecular Nucleophilic Substitution
  77. 7.3: Stereochemical Consequences of SN1 Reactions
  78. 7.4: Effects of Solvent, Leaving Group, and Nucleophile on Unimolecular Substitution
  79. 7.5: Effect of the Alkyl Group on the SN 1 Reaction: Carbocation Stability
  80. 7.6: Unimolecular Elimination: E1
  81. 7.7: Bimolecular Elimination: E2
  82. 7.8: Keys to Success: Substitutin Versus Elimination-Structure Determines Function
  83. 7.9: Summary of Reactivity of Haloalkanes
  84. 7.E: Further Reactions of Haloalkanes: Unimolecular Substitution (Exercises)
  85. 8: Hydroxy of Functional Group: Alcohols: Properties, Preparation, and Strategy of Synthesis
  86. 8.1: Naming the Alcohols
  87. 8.2: Structural and Physical Properties of Alcohols
  88. 8.3: Alcohols as Acids and Bases
  89. 8.4: Industrial Sources of Alcohols: Carbon Monoxide and Ethene
  90. 8.5: Synthesis of Alcohols by Nucleophilic Substitution
  91. 8.6: Synthesis of Alcohols: Oxidation-Reduction Relation Between Alcohols and Carbonyl Compounds
  92. 8.7: Organometallic Reagents: Sources of Nucleophilic Carbon for Alcohol Synthesis
  93. 8.8: Organometallic Reagents in the Synthesis of Alcohols
  94. 8.9: Keys to Success: An Introduction to Synthetic Strategy
  95. 9: Further Reactions of Alcohols and the Chemistry of Ethers
  96. 9.1: Reactions of Alcohols with Base: Preparation of Alkoxides
  97. 9.2: Reactions of Alcohols with Strong Acids: Alkyloxonium Ions in Substitution and Elimination Reactions of Alcohols
  98. 9.3: Carbocation Rearrangements
  99. 9.4: Organic and Inorganic Esters from Alcohols
  100. 9.5: Names and Physical Properties of Ethers
  101. 9.6: Williamson Ether Synthesis
  102. 9.7: Synthesis of Ethers: Alcohols and Mineral Acids
  103. 9.8: Reactions of Ethers
  104. 9.9: Reactions of Oxacyclopropanes
  105. 9.10: Sulfur Analogs of Alcohols and Ethers
  106. 9.11: Physiological Properties and Uses of Alcohols and Ethers
  107. 10: Using Nuclear Magnetic Resonance Spectroscopy to Deduce Structure
  108. Front Matter
  109. TitlePage
  110. InfoPage
  111. 10.1: Physical and Chemical Tests
  112. 10.2: Defining Spectroscopy
  113. 10.3: Hydrogen Nuclear Magnetic Resonance
  114. 10.4: Using NMR Spectra to Analyze Molecular Structure: The Proton Chemical Shift
  115. 10.5: Tests for Chemical Equivalence
  116. 10.6: Integration
  117. 10.7: Spin-Spin Splitting: The Effect of Nonequivalent Neighboring Hydrogens
  118. 10.8: Spin-Spin Splitting: Some Complications
  119. 10.9: Carbon-13 Nuclear Magnetic Resonance
  120. Back Matter
  121. Index
  122. 11: Alkenes: Infrared Spectroscopy and Mass Spectrometry
  123. 11.1: Naming the Alkenes
  124. 11.2: Structure and Bonding in Ethene: The Pi Bond
  125. 11.3: Physical Properties of Alkenes
  126. 11.4: Nuclear Magnetic Resonance of Alkenes
  127. 11.5: Catalytic hydrogenatin of Alkenes: Relative Stability of Double Bonds
  128. 11.6: Preparation of Alkenes from Haloalkanes and Alkyl Sufonates: Bimolecular Elimination Revisited
  129. 11.7: Preparation of Alkenes by Dehydration of Alcohols
  130. 11.8: Infrared Spectroscopy
  131. 11.9: Measuring the Molecular Mass of Organic Compounds: Mass Spectrometry
  132. 11.10: Fragmentation Patterns of Organic Molecules
  133. 11.11: Degree of Unsaturation: Another Aid to Identifying Molecular Structure
  134. 12: Reactions to Alkenes
  135. 12.1: Why Addition Reactions Proceed: Thermodynamic Feasibility
  136. 12.2: Catalytic Hydrogenation
  137. 12.3: Nucleophilic Character of the Pi Bond: Electrophilic Addition of Hydrogen Halides
  138. 12.4: Alcohol Synthesis by Electrophilic Hydration: Thermodynamic Control
  139. 12.5: Electrophilic Addition of Halogens to Alkenes
  140. 12.6: The Generality of Electrophilic Addition
  141. 12.7: Oxymncuration-Demercuration: A Special Elcctrophilic Addition
  142. 12.8: Hydroboration-Oxidation: A Stereospecific Anti-Markovnikov Hydration
  143. 12.9: Diazomethane, Carbenes, and Cyclopropane Synthesis
  144. 12.10: Oxacyclopropane ( Epoxide) Synthesis: Epoxidation by Peroxycarboxylic Acids
  145. 12.11: Vicinal SYn Dihydroxylation with Osmium Tetroxide
  146. 12.12: Oxidative Cleavage: Ozonolysis
  147. 12.13: Radical Additions: Anti-Markovnikov Product Formation
  148. 12.14: Dimerization, Oligomerization. and Polymerization of Alkenes
  149. 12.15: Synthesis of Polymers
  150. 12.16: Ethene: An Important Industrial Feedstock
  151. 12.17: Alkenes in Nature - Insect Pheromones
  152. 13: Alkynes: The Carbon
  153. 13.1: Naming the Alkynes
  154. 13.2: Properties and Bonding in the Alkynes
  155. 13.3: Spectroscopy of the Alkynes
  156. 13.4: Preparation of Alkynes by Double Elimination
  157. 13.5: Preparation of Alkynes from Alkynyl Anions
  158. 13.6: Reduction of Alkynes: The Relative Reactivity of the Two \(\pi\) Bonds
  159. 13.7: Electrophilic Addition Reactions of Alkynes
  160. 13.8: Anti-Markovnikov Additions to Triple Bonds
  161. 13.9: Chemistry of Alkenyl Halides
  162. 13.10: Ethyne as an Industrial Starting Material
  163. 13.11: Naturally Occurring and Physiologically Active Alkynes
  164. 14: Delocalized Pi Systems: Investigation by Ultraviolet and Visible Spectroscopy
  165. 14.1: Overlap of Three Adjacent p Orbitals: Electron Delocalization in the 2-Propenyl (Allyl) System
  166. 14.2: Radical Allylic Halogenation
  167. 14.3: Nucleophilic Substitution of Allylic Halides: SN1 and SN2
  168. 14.4: Allylic Organometallic Reagents: Useful Three-Carbon Nucleophiles
  169. 14.5: Two Neighboring Double Bonds: Conjugated Dienes
  170. 14.6: Electrophilic Attack on Conjugated Dienes: Kinetic and Thermodynamic Control
  171. 14.7: Delocalization among More than Two Pi Bonds: Extended Conjugation and Benzene
  172. 14.8: A Special Transformation of Conjugated Dienes: Diels-Alder Cycloaddition
  173. 14.9: Electrocyclic Reactions
  174. 14.10: Polymerization of Conjugated Dienes: Rubber
  175. 14.11: Electronic Spectra: Ultraviolet and Visible Spectroscopy
  176. 15: Benzene and Aromaticity: Electrophilic Aromatic Substitution
  177. 15.1: Naming the Benzenes
  178. 15.2: Structure and Resonance Energy of Benzene: A First Look at Aromaticity
  179. 15.3: Pi Molecular Orbitals of Benzene
  180. 15.4: Spectral Characteristics of the Benzene Ring
  181. 15.5: Polycyclic Aromatic Hydrocarbons
  182. 15.6: Other Cyclic Polyenes: Huckel 's Rule
  183. 15.7: Huckel's Rule and Charged Molecules
  184. 15.8: Synthesis of Benzene Derivatives: Electrophilic Aromatic Substitution
  185. 15.9: Halogenation of Benzene: The Need for a Catalyst
  186. 15.10: Nitration and Sulfonation of Benzene
  187. 15.11: Friedel-Crafts Alkylation
  188. 15.12: Limitations of Friedel-Crafts Alkylations
  189. 15.13: Friedel-Crafts Alkanoylation (Acylation)
  190. 16: Electrophilic Attack on Derivatives of Benzene: Substituents Control Regioselectivity
  191. 16.1: Activation or Deactivation by Substituents on a Benzene Ring
  192. 16.2: Directing Inductive Effects of Alkyl Groups
  193. 16.3: Directing Effects of Substituents in Conjugation with the Benzene Ring
  194. 16.4: Electrophilic Attack on Disubstituted Benzenes
  195. 16.5: Synthetic Strategies Toward Substituted Benzenes
  196. 16.6: Reactivity of Polycyclic Benzenoid Hydrocarbons
  197. 16.7: Polycyclic Aromatic Hydrocarbons and Cancer
  198. 17: Aldehydes and Ketones - The Carbonyl Group
  199. 17.1: Naming the Aldehydes and Ketones
  200. 17.2: Structure of the Carbonyl Group
  201. 17.3: Spectroscopic Properties of Aldehydes and Ketones
  202. 17.4: Preparation of Aldehydes and Ketones
  203. 17.5: Reactivity of the Carbonyl Group: Mechanisms of Addition
  204. 17.6: Addition of Water to Form Hydrates
  205. 17.7: Addition of Alcohols to Form Hemiacetals and Acetals
  206. 17.8: Acetals as Protecting Groups
  207. 17.9: Nucleophilic Addition of Ammonia and Its Derivatives
  208. 17.10: Deoxygenation of the Carbonyl Group
  209. 17.11: Addition of Hydrogen Cyanide to Give Cyanohydrins
  210. 17.12: Addition of Phosphorus Ylides: The Wittig Reaction
  211. 17.13: Oxidation by Peroxycarboxylic Acids: The Baeyer- Villiger Oxidation
  212. 17.14: Oxidative Chemical Tests for Aldehydes
  213. 18: Enols, Enolates, and the Aldol Condensation: a,b-Unsaturated Aldehydes and Ketones
  214. 18.1: Acidity of Aldehydes and Ketones: Enolate Ions
  215. 18.2: Keto-Enol Equilibria
  216. 18.3: Halogenation of Aldehydes and Ketones
  217. 18.4: Alkylation of Aldehydes and Ketones
  218. 18.5: Attack by Enolates on the Carbonyl Function: Aldol Condensation
  219. 18.6: Crossed Aldol Condensation
  220. 18.7: Keys to Success: Competitive Rection Pathways and the Intramolecular Aldol Condensation
  221. 18.8: Properties of a,b-Unsaturated Aldehydes and Ketones
  222. 18.9: Conjugate Additions to a,b-Unsaturated Aldehydes and Ketones
  223. 18.10: 1,2- and 1,4-Additions of Organometallic Reagents
  224. 18.11: Conjugate Additions of Enolate Ions: Michael Addition and Robinson Annulation
  225. 19: Carboxylic Acids
  226. 19.1: Naming the Carboxylic Acids
  227. 19.2: Structural and Physical Properties of Carboxylic Acids
  228. 19.3: Spectroscopy and Mass Spectrometry of Carboxylic Acids
  229. 19.4: Acidic and Basic Character of Carboxylic Acids
  230. 19.5: Carboxylic Acid Synthesis in Industry
  231. 19.6: Methods for Introducing the Carboxy Functional Group
  232. 19.7: Substitution at the Carboxy Carbon: The Addition-Elimination Mechanism
  233. 19.8: Carboxylic Acid Derivatives: Alkanoyl (Acyl) Halides and Anhydrides
  234. 19.9: Carboxylic Acid Derivatives: Esters
  235. 19.10: Carboxylic Acid Derivatives: Amides
  236. 19.11: Reduction of Carboxylic Acids by Lithium Aluminum Hydride
  237. 19.12: Bromination Next to the Carboxy Group: The Hell-Volhard-Zelinsky Reaction
  238. 19.13: Biological Activity of Carboxylic Acids
  239. 20: Carboxylic Acid Derivatives
  240. 20.1: Relative Reactivities, Structures, and Spectra of Carboxylic Acid Derivatives
  241. 20.2: Chemistry of Alkanoyl Halides
  242. 20.3: Chemistry of Carboxylic Anhydrides
  243. 20.4: Chemistry of Esters
  244. 20.5: Esters in Nature: Waxes, Fats, Oils, and Lipids
  245. 20.6: Amides: The Least Reactive Carboxylic Acid Derivatives
  246. 20.7: Amidates and Their Halogenation: The Hofmann Rearrangement
  247. 20.8: Alkanenitriles: A Special Class of Carboxylic
  248. 21: Amines and Their Derivatives
  249. 21.1: Naming the Amines
  250. 21.2: Structural and Physical Properties of Amines
  251. 21.3: Spectroscopy of the Amine Group
  252. 21.4: Acidity and Basicity of Amines
  253. 21.5: Synthesis of Amines by Alkylation
  254. 21.6: Synthesis of Amines by Reductive Amination
  255. 21.7: Synthesis of Amines from Carboxylic Amides
  256. 21.8: Quaternary Ammonium Salts: Hofmann Elimination
  257. 21.9: Mannich Reaction: Alkylation of Enols by Iminium Ions
  258. 21.10: Nitrosation of Amines
  259. 22: Chemistry of the Benzene Substituents: Alkylbenzenes, Phenols, and Benzenamines
  260. 22.1: Reactivity at the Phenylmethyl (Benzyl) Carbon: Benzylic Resonance Stabilization
  261. 22.2: Benzylic Oxidations and Reductions
  262. 22.3: Names and Properties of Phenols
  263. 22.4: Preparation of Phenols: Nucleophilic Aromatic Substitution
  264. 22.5: Alcohol Chemistry of Phenols
  265. 22.6: Electrophilic Substitution of Phenols
  266. 22.7: An Electrocyclic Reaction of the Benzene Ring: The Claisen Rearrangement
  267. 22.8: Oxidation of Phenols: Benzoquinones
  268. 22.9: Oxidation-Reduction Processes in Nature
  269. 22.10: Arenediazonium Salts
  270. 22.11: Electrophilic Substitution with Arenediazonium Salts: Diazo Coupling
  271. 23: Ester Enolates and the Claisen Condensation
  272. 23.1: B-Dicarbonyl Compounds: Claisen Condensations
  273. 23.2: B-Dicarbonyl Compounds as Synthetic Intermediates
  274. 23.3: B-Dicarbonyl Anion Chemistry: Michael Additions
  275. 23.4: Alkanoyl (Acyl) Anion Equivalents: Preparation of a-Hydroxyketones
  276. 24: Carbohydrates: Polyfunctional Compounds in Nature
  277. 24.1: Names and Structures of Carbohydrates
  278. 24.2: Conformations and Cyclic Forms of Sugars
  279. 24.3: Anomers of Simple Sugars - Mutarotation of Glucose
  280. 24.4: Polyfunctional Chemistry of Sugars: Oxidation to Carboxylic Acids
  281. 24.5: Oxidative Cleavage of Sugars
  282. 24.6: Reduction of Monosaccharides to Alditols
  283. 24.7: Carbonyl Condensations with Amine Derivatives
  284. 24.8: Ester and Ether Formation: Glycosides
  285. 24.9: Step-by-Step Buildup and Degradation of Sugars
  286. 24.10: Relative Configurations of the Aldoses: An Exercise in Structure Determination
  287. 24.11: Complex Sugars in Nature: Disaccharides
  288. 24.12: Polysaccharides and Other Sugars in Nature
  289. 25: Heterocycles: Heteroatoms in Cyclic Organic Compounds
  290. 25.1: Naming the Heterocycles
  291. 25.2: Nonaromatic Heterocycles
  292. 25.3: Structure and Properties of Aromatic Heterocyclopentadienes
  293. 25.4: Reactions of the Aromatic Heterocyclopentadienes
  294. 25.5: Structure and Preparation of Pyridine: An Azabenzene
  295. 25.6: Reactions of Pyridine
  296. 25.7: Quinoline and Isoquinoline: The Benzopyridines
  297. 25.8: Alkaloids: Physiologically Potent Nitrogen Heterocycles in Nature
  298. 26: Amino Acids, Peptides, Proteins, and Nucleic Acids: Nitrogen-Containing Polymers in Nature
  299. 26.1: Structure and Properties of Amino Acids
  300. 26.2: Synthesis of Amino Acids: A Combination of Amine and Carboxylic Acid Chemistry
  301. 26.3: Synthesis of Enantiomerically Pure Amino Acids
  302. 26.4: Peptides and Proteins: Amino Acid Oligomers and Polymers
  303. 26.5: Determination of Primary Structure: Amino Acid Sequencing
  304. 26.6: Synthesis of Polypeptides: A Challenge in the Application of Protecting Groups
  305. 26.7: Merrifield Solid-Phase Peptide Synthesis
  306. 26.8: Polypeptides in Nature: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
  307. 26.9: Biosynthesis of Proteins: Nucleic Acids
  308. 26.10: Protein Synthesis Through RNA
  309. 26.11: DNA Sequencing and Synthesis: Cornerstones of Gene Technology
  310. Back Matter
  311. Front Matter
  312. TitlePage
  313. InfoPage
  314. Index
  315. Glossary
  316. Detailed Licensing
  317. Back Matter
  318. Index