Fundamentals of Organic Chemistry, 5E, Study Guide and Solutions Manual

TopicA.pdf......Page 0
Table of Contents......Page 2
Dimethyl ether......Page 36
Electron-Pair Repulsion (VSEPR) Model......Page 45
Bonding......Page 47
Equivalent dash formulas for propyl alcohol ( same connectivity of the atoms......Page 48
Equivalent dash formulas for isopropyl alcohol ( same connectivity of the atoms......Page 49
Structure Is Everything......Page 52
Alkynes, and Aromatic Compounds......Page 53
Formula......Page 57
Isopropyl group......Page 59
Table 2.3  Important Families of Organic Compounds......Page 67
Table 2.4  Physical Properties of Representative Compounds......Page 68
Attractive energies......Page 72
Electric Force......Page 75
for Detecting Functional Groups......Page 76
Bending Vibrations......Page 79
How To Approach The Analysis of A Spectrum......Page 86
Shuttling the Protons......Page 88
Carbocations and Carbanions......Page 94
Conjugate Base......Page 99
Acetic acid Ethanol......Page 112
Acetate anion Ethoxide anion......Page 113
pKa = 4.75 pKa = 2.86......Page 114
Explanation......Page 116
Deuterium- and Tritium-Labeled Compounds......Page 122
Molecular structure Makes the difference......Page 123
4.1A Sources of Alkanes:  Petroleum......Page 124
and Alcohols......Page 128
SI Prefixes......Page 129
Butyl......Page 130
Name......Page 145
conformation conformation conformation conformation conforma......Page 148
Ring Strain......Page 150
Cycloalkane (CH2)n......Page 151
Cyclobutane:  Angle Strain and torsional Strain......Page 152
Energy cost......Page 158
M/L......Page 161
Substituents......Page 164
Compound......Page 167
Undecane 2-Methylheptadecane......Page 169
Specific Examples......Page 172
Specific Examples......Page 173
reactivity:  A Look toward Synthesis......Page 174
Chirality and Biological Activity......Page 185
5.6B The (R-S) System:  (Cahn-Ingold-Prelog System)......Page 190
5.7A Plane-Polarized Light......Page 193
5.7B The Polarimeter......Page 195
5.7C Specific Rotation:......Page 196
Specific Rotations of Some Organic Molecules......Page 197
5.8B Racemic Forms and Enantiomeric Excess (e.e.)......Page 199
5.11B Naming Compounds with More Than One Stereocenter......Page 201
5.12B Allowed motions for Fischer projection:......Page 202
5.12C Assigning R,S Configurations to Fischer Projections:......Page 204
5.9A Racemic Forms......Page 205
5.9B Enantioselective Syntheses......Page 207
5.13A Cyclohexane Derivatives......Page 210
5.14A Relative and Absolute Configurations......Page 216
5.15A Pasteur’s Method for Separating Enantiomers......Page 218
5.15B Current Methods for Resolution of Enantiomers......Page 219
Binaphthol......Page 220
6.1 Introduction......Page 221
Group......Page 225
6.3 Nucleophilic Substitution Reactions......Page 226
6.4 Nucleophiles......Page 227
6.5 Leaving Groups......Page 228
(mol L–1 s–1)......Page 229
6.7 A Mechanism for the SN2 Reaction......Page 230
6.8 Transiition State Theory:  Free-Energy Diagrams......Page 232
6.9 The Stereochemistry of SN2 Reactions......Page 238
Hydroxide Ion:  An SN1 Reaction......Page 240
6.10A Multistep Reactions and the Rate-determining Step......Page 241
A Mechanism for the SN1 Reaction......Page 242
6.12B The Relative Stabilities of Carbocations......Page 244
6.13A Reactions that Involve Racemization......Page 246
The SN1 reaction of (S)-3-bromo-3-methylhexane proceeds with......Page 247
6.13B Solvolysis......Page 248
6.14A The Effect of the Structure of the Substrate......Page 249
CH3X......Page 250
Relative rate of reaction......Page 251
Relative rate......Page 252
Nucleophile......Page 255
Protic and Aprotic Solvents......Page 256
The Ionizing Ability of the Solvents......Page 259
Protic (hydroxylic) solvents......Page 260
6.14E The Nature of the Leaving Group......Page 261
6.14F Summary: SN1 versus SN2......Page 263
Transformations Using SN2 Reactions......Page 264
The Chemistry of.…......Page 265
6.16B Bases Used in Dehydrohalogenation......Page 267
6.16C Mechanisms of Dehydrohalogenations......Page 268
A Mechanism for the E2 Reaction......Page 269
6.18 The E1 Reaction......Page 270
A Mechanism for the E1 Reaction......Page 271
6.19A SN2 versus E2......Page 272
6.19B Tertiary Halides: SN1 versus E1......Page 273
RR’CHX......Page 274
Substrate structure......Page 275
7.2 Nomenclature of Alkenes and Cycloalkenes......Page 276
Diastereomers......Page 277
7.3A Heats of Hydrogenation......Page 278
7.3B Relative Stabilities from Heats of Combustion......Page 280
7.3C Overall Relative Stabilities of Alkenes......Page 281
7.4 Cycloalkenes......Page 282
7.6 Dehydrohalogenation of Alkyl Halides......Page 283
Product Zaitsev’s Rule......Page 284
of Groups in the Transition State......Page 287
A Mechanism for the Elimination Reaction of Neomenthyl Chlor......Page 289
A Mechanism for the Elimination Reaction of Menthyl Chloride......Page 290
7.7 Dehydration of Alcohols......Page 291
7.7A Mechanism of Alcohol Dehydration: An E1 Reaction......Page 292
7.7B Carbocation Stability and the Transition State......Page 293
Acid-Catalyzed Dehydration of Secondary or Tertiary Alcohols......Page 294
7.8 Carbocation Stability and the Occurrence of......Page 296
Alcohols......Page 297
Alcohol......Page 299
A Mechanism for the Reaction......Page 300
A Mechanism for the Reaction......Page 301
7.10 Synthesis of Alkynes by Elimination Reactions......Page 302
A Mechanism for the Reaction......Page 303
Relative Basicity of hydrogen compounds of the first-row ele......Page 304
Terminal Alkynes......Page 305
7.13 Hydrogenation of Alkenes......Page 306
7.14 Hydrogenation: The Function of the Catalyst......Page 307
7.14A Syn and Anti Additions......Page 308
7.15A Syn Addition of Hydrogen: Synthesis of Cis-Alkenes......Page 309
7.15B Anti Addition of Hydrogen: Synthesis of Trans-Alkenes......Page 310
The Index of Hydrogen Deficiency......Page 311
of Alkenes and Alkynes......Page 314
of Alkenes and Alkynes......Page 315
Natural Products......Page 316
8.1 Introduction:  Additions to Alkenes......Page 318
Markovnikov’s Rule......Page 321
Addition of a Hydrogen Halide an Alkene......Page 323
Addition of HBr to 2-Methylpropene......Page 326
8.4 Addition of Sulfuric Acid to Alkenes......Page 328
Acid-Catalyzed Hydration......Page 330
Acid-Catalyzed Hydration of an Alkene......Page 331
8.6 Addition of Bromine and Chlorine to Alkenes......Page 333
Addition of Bromine to an Alkene......Page 334
Alkenes......Page 335
Addition of Bromine to cis- and trans-2-Butene......Page 339
Step 2 and 3......Page 340
The Chemistry of Regiospecificity in Unsymmetrically Substit......Page 341
8.9 Divalent Carbon Compounds:  Carbenes......Page 344
8.10 Oxidation of Alkenes: syn-Hydroxylation......Page 346
8.11 Oxidative Cleavage of Alkenes......Page 348
Ozonide Formation from an Alkene......Page 349
8.12 Addition of Bromine and Chlorine to Alkynes......Page 350
8.13 Addition of Hydrogen Halides to Alkynes......Page 351
8.14 Oxidative Cleavage of Alkynes......Page 352
8.15 Synthetic Strategies Revisited......Page 353
The Chemistry of Cholesterol Biosynthesis: Elegant and Famil......Page 356
Summary of Addition Reactions of Alkenes......Page 359
Summary of Addition Reactions of Alkynes......Page 361
Slicing the Backbone of DNA......Page 362
10.1 Introduction:......Page 364
The Chemistry of Radicals in Biology, Medicine, and Industry......Page 365
10.2 Homolytic Bond Dissociation Energies......Page 368
(a 2° radical)......Page 369
10.3 The Reactions of Alkanes with Halogens......Page 371
10.4 Chlorination of Methane: Mechanism of Reaction......Page 373
Radical Chlorination of Methane......Page 374
10.5 Chlorination of Methane: Energy Changes......Page 375
Chain Termination......Page 376
Chain Propagation......Page 378
Chain Propagation......Page 381
Chain Propagation......Page 382
Chain Propagation......Page 383
Radical Chlorination of Ethane......Page 384
10.7 The Geometry of Alkyl Radicals......Page 386
Stereocenters......Page 387
The Stereochemistry of Chlorination at C2 of Pentane......Page 388
The Stereochemistry of Chlorination at C3 of (S)-2-Chloropen......Page 389
Addition of Hydrogen Bromide......Page 390
Anti-Markovnikov Addition......Page 391
Chain-Growth Polymers......Page 392
Chain Branching......Page 393
10.11 Other Important Radical Chain Reactions......Page 394
Molecular Hosts......Page 401
11.1 Structure and Nomencalture......Page 402
11.2 Physical Properties of Alcohols and Ethers......Page 405
Formula......Page 406
Monohydroxy Alcohols......Page 407
11.3 Important Alcohols and Ethers......Page 408
11.4 Synthesis of Alcohols from Alkenes......Page 411
Step 2: Demercuration......Page 412
Oxymercuration......Page 414
11.6 Hydroboration: Synthesis of Organoboranes......Page 415
Hydroboration......Page 417
Oxidation of Trialkylboran......Page 418
11.8 Reactions of Alcohols......Page 421
Acid......Page 422
Tosylatess......Page 423
Conversion of an Alcohol into an Alkyl Methanesulfonate......Page 424
11.11 Mesylates and Tosylates in SN2 Reactions......Page 425
The Chemistry of Alkyl Phosphates......Page 426
11.12 Conversion of Alcohols into Alkyl Halides......Page 427
Hydrogen Halides......Page 428
PBr3 or SOCl2......Page 431
11.15 Synthesis of Ethers......Page 432
Intermolecular Dehydration of Alcohols to Form an Ether......Page 433
The Williamson Ether Synthesis......Page 434
11.16 Reactions of Ethers......Page 436
Ether Cleavage by Strong Acids......Page 437
Alkene Epoxidation......Page 438
The Chemistry of The Sharpless Asymmetric Epoxidation......Page 440
Acid-Catalyzed Ring Opening of an Epoxide......Page 442
Base-Catalyzed Ring Opening of an Epoxide......Page 443
The Chemistry of Epoxides, Carcinogens, and Biological Oxida......Page 444
11.19 Anti Hydroxylation of Alkenes via Epoxides......Page 447
Solvents by Phase-Transfer Catalysis......Page 449
and Ethers......Page 455
The Two Aspects of the Coenzyme NADH......Page 457
12.1 Introduction......Page 458
Chemistry......Page 461
12.3 Alcohols by Reduction of Carbonyl Compounds......Page 462
Reduction of Aldehydes and Ketones by Hydride Transfer......Page 464
The Chemistry of Alcohol Dehydrogenase......Page 465
The Chemistry of Stereoselective Reductions of Carbonyl Grou......Page 466
12.4 Oxidation of Alcohols......Page 470
Chromate Oxidations: The Oxidation Step......Page 473
12.5 Organometallic Compounds......Page 476
Organomagnesium Compounds......Page 478
Organomagnesium Compounds......Page 480
The Grignard Reaction......Page 482
12.8 Alcohols from Grignard reagents......Page 483
Whitesides-House Synthesis......Page 489
12.11 Summary of Reactions......Page 492
Their Synthetic Lineage (Ancestry)......Page 495
13.2 allylic Substitution and the allyl Radical......Page 496
Ethene Vinyl radical......Page 498
13.3 The Stability of the Allyl Radical......Page 501
13.4 The Allyl Cation......Page 505
13.5 Summary of Rules for Resonance......Page 507
13.6 Alkadienes and Polyunsaturated Hydrocarbons......Page 510
13.7 1,3-Butadiene:  Electron Delocalization......Page 511
13.8 The Stability of Conjugated Dienes......Page 514
1,4-Addition......Page 516
A.1 Introduction......Page 521
A.2 Stereochemistry of Chain-Growth Polymerization......Page 530