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Table of ContentsPreface xxi
Introduction 1
Important Features of the Organic Lab 1
Goals for the Organic Laboratory 1
Working in the Laboratory 2
Laboratory Safety 3
Material Safety Data Sheet (MSDS) 5
Your Laboratory Notebook 6
Laboratory Reports 6
How to Be a Successful Organic Laboratory Student 7Chapter One Techniques in the Organic Chemistry Laboratory 9
Technique A Glassware and Equipment: Heating and Cooling 9
Microscale Glassware and Related Equipment 9
Miniscale Glassware 11
Additional Glassware and Equipment 13
How to Clean Glassware 13
How to Heat and Cool Glass Reaction Vessels 14
Technique B Weighing and Measuring 17
How to Weigh Solids and Liquids 17
Introduction to Measuring Volumes of Liquids 17
How to Use a Calibrated Glass Pipet 18
How to Use an Automatic Delivery Pipet 19
How to Use a Syringe 19
Exercise B.1: Determining Density of an Aqueous Solution 20
Exercise B.2: Determining Density of an Organic Liquid 21
Exercise B.3: Calibrating a Pasteur Pipet 21
Technique C Melting Points 22
Mixed Melting Behavior 23
Melting Behavior of Solids 23
Calibration of the Thermometer 24
Apparatus for Measuring Melting Points 24
How to Determine a Melting Point 24
Exercise C.1: Calibration of a Thermometer 26
Exercise C.2: Melting Point of an Unknown Solid 26
Exercise C.3: Mixed Melting Point 27
Technique D Boiling Points 28
Intermolecular Attractions 28
How to Do a Microscale Boiling Point Determination 29
How to Do a Miniscale Boiling Point Determination 29
Exercise D.1: Determining the Micro Boiling Point of an Unknown Liquid 30
Exercise D.2: Determining the Boiling Point of an Unknown Liquid 30
Technique E Index of Refraction 32
How to Use the Abbe Refractometer 33
Exercise E.1: Measuring the Refractive Index of an Unknown Liquid 33
Technique F Recrystallization, Filtration, and Sublimation 34
Solvents for Recrystallization 35
Choosing a Solvent 38
Choosing a Solvent Pair 38
How to Do a Microscale Recrystallization 39
How to Do a Miniscale Recrystallization 41
Important Tips Concerning Recrystallization 42
Introduction to Filtration 43
How to Use a Microscale Filter Pipet 44
How to Do a Miniscale Suction Filtration 44
How to Do a Miniscale Gravity Filtration 44
Important Tips Concerning Filtration 45
Introduction to Sublimation 45
Exercise F.1: Recrystallizing an Impure Solid (microscale) 48
Exercise F.2: Recrystallizing an Impure Solid (miniscale) 48
Exercise F.3: Recrystallizing an Impure Solid with Hot Gravity Filtration 49
Exercise F.4: Purifying an Unknown Solid by Solvent-Pair Recrystallization 50
Exercise F.5: Sublimation of Caffeine 50
Exercise F.6: Sublimation of Caffeine 51
Technique G Distillation and Reflux 52
Microscale Apparatus for Simple Distillation and Assembly 56
How to Do a Simple Microscale Distillation 56
Important Tips Concerning Microscale Distillation 58
Miniscale Apparatus for Simple Distillation 59
How to Do a Simple Miniscale Distillation 59
Important Tips Concerning Miniscale Distillation 60
Introduction to Reflux 61
How to Do a Microscale Reaction with Reflux 61
How to Do a Miniscale Reaction with Reflux 62
Important Tips on Reflux 62
Evaporation of Solvents 62
Exercise G.1: Distilling a Mixture of Cyclohexane and Toluene (microscale) 63
Exercise G.2: Distilling a Mixture of Cyclohexane and Toluene (miniscale) 64
Technique H Fractional Distillation and Steam Distillation 65
How to Do a Miniscale Fractional Distillation 67
Practical Tips about Miniscale Fractional Distillation 68
Introduction to Steam Distillation 69
Exercise H.1: Miniscale Fractional Distillation of a Mixture of Cyclohexane and Toluene 70
Exercise H.2: Microscale Fractional Distillation of Cyclohexane and Toluene 70
Exercise H.3: Steam Distillation of Lemon Grass Oil (miniscale) 71
Technique I Extraction and Drying 72
How to Do a Microscale Extraction 74
How to Do a Miniscale Extraction 76
Important Tips Concerning Extraction 76
Drying and Drying Agents 78
How to Do Microscale Drying 78
How to Do Miniscale Drying 79
Important Tips Concerning Drying Agents 79
Exercise I.1: Determining the Distribution Coefficient of Caffeine (microscale) 80
Exercise I.2: Determining the Distribution Coefficient of Caffeine (miniscale) 80
Exercise I.3: Using Distribution Coefficients to Identify an Unknown Solid (microscale) 81
Technique J Gas-Liquid Chromatography 83
Gas-Liquid Chromatography Basics 83
Quantitative Analysis 87
How to Use the Gas Chromatograph 89
Exercise J.1: Determining Relative Detector Response Factors in GC 89
Exercise J.2: Determining Mass Percent of a Mixture Using GC 90
Exercise J.3: Determining Mass Percent of a Mixture of Alcohols 90
Technique K Thin-Layer, Column, and High-Performance Liquid Chromatography 92
Introduction to Thin-Layer Chromatography (TLC) 92
Introduction to Column Chromatography 97
How to Do a Miniscale Gravity Column Chromatography 98
How to Do Microscale Column Chromatography 99
Introduction to High-Performance Liquid Chromatography (HPLC) 99
Exercise K.1: Analysis of Analgesic Tablets by TLC 101
Exercise K.2: Separating Ferrocene and Acetylferrocene Using Column Chromatography (microscale) 101
Exercise K.3: Separating Ferrocene and Acetylferrocene Using Column Chromatography (miniscale) 102
Exercise K.4: HPLC Analysis of Benzaldehyde and Benzyl Alcohol 102
Technique L Polarimetry 103
Optical Purity and Enantiomeric Excess 104
How to Measure Optical Rotation 106
Exercise L.1: Determining the Optical Purity of an Unknown Liquid 107
Exercise L.2: Determining the Melting Points of Enantiomers and Racemates 107
Chapter Two Spectroscopic Methods and Molecular Modeling 109
Technique M Infrared Spectroscopy 110
General Approach to Solving an IR Spectrum 116
Recording an IR Spectrum 116
How to Prepare a Sample for IR Analysis 118
Important Tips Concerning IR 120
Exercise M.1: Recording the IR Spectrum of an Organic Liquid 122
Exercise M.2: Recording the IR Spectrum of an Organic Solid 122
Exercise M.3: Spectroscopic Identification of Unknowns 122
Technique N Nuclear Magnetic Resonance Spectroscopy 125
Chemical Shifts in 1H NMR Spectroscopy 127
Equivalence of Protons in 1H NMR Spectroscopy 129
Integration in 1H NMR Spectroscopy 130
Splitting (coupling) in 1H NMR Spectroscopy 131
Coupling Constants 134
Protons in a Chiral Environment 135
Diastereotopic Protons in Alkenes 136
Protons on Heteroatoms 137
Solvents for 1H NMR Spectroscopy 139
How to Prepare a Sample for 60–90 MHz CW1H NMR Spectroscopy 140
How to Prepare a Sample for FT NMR 140
Structural Identification from the NMR Spectrum 140
Introduction to 13C NMR Spectroscopy 143
Solvents for 13C NMR Spectroscopy 146
How to Prepare a Sample for 13C NMR Spectroscopy 146
General Approach to Determining an Unknown Structure 146
Exercise N.1: Recording a 1H NMR Spectrum 148
Exercise N.2: Recording a 13C NMR Spectrum 148
Exercise N.3: 1H NMR Spectral Problems 148
Exercise N.4: 13C NMR Spectral Problems 150
Exercise N.5: Spectral Identification Using 1H and 13C NMR 151
Technique O Ultraviolet and Visible Spectroscopy 154
Uses of UV-Visible Spectroscopy 156
How to Operate a Spectronic 20 158
How to Operate a UV-Visible Spectrometer 159
Technique P Mass Spectrometry 160
Principles of Mass Spectrometry 160
Fragmentation Patterns 163
Molecular Ion Peak 166
Isotopes 167
Gas Chromatography/Mass Spectrometry (GC/MS) 167
Strategy for Solving Structural Problems Using MS, IR, and NMR 168
Mass Spectrometric Analysis Guidelines 168
Exercise P.1: Solving Problems in Mass Spectrometry 172
Technique Q Molecular Modeling 173
Organic Molecular Models 174
Drawing Organic Molecules Using Computer Software 174
Molecular Modeling Using Computer Software 174
Molecular Mechanics 175
Quantum Mechanics 178
Exercises 180
Exercise Q.1: Conformational Analysis of Butane and Other Molecules 180
Exercise Q.2: Conformational Analysis of Propane 180
Exercise Q.3: Conformational Analysis of 2-Methylbutane 181
Exercise Q.4: Identifying Reactive Sites 181
Exercise Q.5: Heats of Formation and Dipole Moments 181
Exercise Q.6: LUMO Energies of Alkenes 181
Exercise Q.7: Conformational Analysis of 3-Fluoropropene 182
Chapter Three
Applications Using Laboratory Resources and Techniques 183
Experiment 3.1 Scavenger Hunt: Introduction to Chemical Data Reference Books and Calculations 184
Part A: Scavenger Hunt in the Chemical Reference Books 187
Part B: Scavenger Hunt and Stoichiometric Calculations 188
Experiment 3.2 Identification of Organic Liquids by Physical Properties 189
General Directions 190
Part A: Boiling Point Determination 190
Part B: Refractive Index Determination 190
Experiment 3.3 Relationships Between Structure and Physical Properties 192
Part A: Determination of the Effect of Structure on Boiling Point 194
Part B: Determination of the Effect of Structure on Refractive Index 194
Part C: Determination of the Effect of Structure on Melting Point 194
Experiment 3.4 Properties of Solvents and Recrystallization of Organic Solids 197
Part A: Selecting an Appropriate Solvent 198
Part B: Microscale Recrystallization of an Organic Solid 199
Experiment 3.5 Separations Based upon Acidity and Basicity 200
Part A: Determination of Solubilities 202
Part B: Microscale Separation of Naphthalene, Benzoic Acid, and Ethyl 4-Aminobenzoate 203
Part C: Miniscale Separation of Benzoic Acid and Ethyl 4-Aminobenzoate 204
Experiment 3.6 Isolation of a Natural Product 205
Part A: Miniscale Extraction of Caffeine from Tea Leaves 207
Part B: Miniscale Extraction of Caffeine from Instant Coffee 208
Part C: Miniscale Isolation of Caffeine from NoDoz 209
Part D: Miniscale Isolation of Cholesterol from Simulated Gallstones 209
Experiment 3.7 Solvent and Polarity Effects in Thin-layer Chromatography (TLC) 210
Part A: Determining the Effect of Polarity on Elution 212
Part B: Separation and Identification of Components of a Mixture of trans-Stilbene, 9-Fluorenone, and Benzoic Acid 214
Experiment 3.8 Purification and Analysis of a Liquid Mixture: Simple and Fractional Distillation 216
Part A: Microscale Distillation 217
Part B: Microscale Fractional Distillation 218
Part C: Miniscale Distillation 218
Part D: Miniscale Fractional Distillation 219
Chapter Four Alcohols and Alkyl Halides 221
Experiment 4.1 Synthesis of an Alkyl Halide from an Alcohol 221
Experiment 4.2 Selectivity of Free Radical Chlorination of 2,3-Dimethylbutane 224
Chapter Five Synthesis of Alkenes 229
Experiment 5.1 Alkenes Via Acid-catalyzed Dehydration of Alcohols 229
Part A: Microscale Synthesis of Alkenes Via Acid-catalyzed Dehydration of 3-Methyl-3-pentanol 231
Part B: Miniscale Synthesis of Alkenes Via Acid-catalyzed Dehydration of 3,3-Dimethyl-2-butanol 231
Part C: Microscale Synthesis of Alkenes Via Acid-catalyzed Dehydration of an Unknown Alcohol 232
Experiment 5.2 Alkenes Via Base-Induced Elimination of Alkyl Halides 234
Chapter Six Alkene Addition Reactions 237
Experiment 6.1 Catalytic Hydrogenation of Alkenes 237
Part A: Microscale Hydrogenation of 1-Decene 239
Part B: Microscale Hydrogenation of Allylbenzene 240
Part C: Microscale Partial Hydrogenation of Olive Oil 241
Experiment 6.2 Hydration of Alkenes 242
Part A: Microscale Hydration of 2-Ethyl-1-butene 244
Part B: Microscale Hydration of Norbornene 245
Part C: Miniscale Hydration of Norbornene 245
Experiment 6.3 Preparation of Alcohols from Alkenes by Hydroboration-oxidation 246
Part A: Microscale Hydroboration-oxidation of 3,3-Dimethyl-1-butene 249
Part B: Miniscale Hydroboration-oxidation of 3,3-Dimethyl-1-butene 249
Experiment 6.4 Addition Polymers: Preparation of Polystyrene and Polymethyl Methacrylate 251
Part A: Miniscale Polymerization of Styrene (Bulk Method) 253
Part B: Microscale Polymerization of Styrene (Solution Method) 253
Part C: Miniscale Polymerization of Methyl Methacrylate (Bulk Method) 253
Chapter Seven Stereochemistry 255
Experiment 7.1 Stereochemistry of Alkenes and Derivatives 255
Part A: Microscale Cis-Trans Isomerization of an Alkene 258
Part B: Microscale Addition of Bromine to Fumaric Acid 258
Part C: Determining the Mechanism of the Isomerization of Dimethyl Maleate to Dimethyl Fumarate (Miniscale) 259
Chapter Eight
Introduction to Nucleophilic Substitution Reactions 261
Experiment 8.1 Relative Rates of Nucleophilic Substitution Reactions 261
Part A: Determination of Factors Affecting the Relative Rates of SN2 Reactions 263
Part B: Determination of Factors Affecting the Relative Rates of SN1 Reactions 264
Experiment 8.2 Nucleophilic Aliphatic Substitution: Synthesis of 1-Bromobutane 267
Part A: Microscale Synthesis of 1-Bromobutane 268
Part B: Miniscale Synthesis of 1-Bromobutane 269
Chapter Nine Dienes and Conjugation 271
Experiment 9.1 Dienes and the Diels-Alder Reaction 271
Part A: Microscale Reaction of 1,3-Butadiene with Maleic Anhydride 276
Part B: Miniscale Reaction of 2,3-Dimethyl-1,3-butadiene with Maleic Anhydride 277
Part C: Microscale Reaction of Cyclopentadiene with Maleic Anhydride 277
Part D: Miniscale Reaction of Cyclopentadiene with Maleic Anhydride 277
Part E: Miniscale Reaction of Anthracene with Maleic Anhydride 278
Chapter Ten Qualitative Organic Analysis I 281
Experiment 10.1 Qualitative Analysis of Alkyl Halides, Alkenes, Dienes, and Alkynes 281
Chapter Eleven Reactions of Aromatic Side Chains 290
Experiment 11.1 Benzylic Oxidation: Benzoic Acid from Toluene; A Phthalic Acid from an Unknown Xylene 290
Part A: Microscale Oxidation of Toluene to Benzoic Acid 292
Part B: Microscale Oxidation of a Xylene to a Phthalic Acid 293
Chapter Twelve Electrophilic Aromatic Substitution 298
Experiment 12.1 Activating and Deactivating Effects of Aromatic Substituents: Relative Rates of Bromination 299
Experiment 12.2 Nitration of Methyl Benzoate or an Unknown 304
Part A: Microscale Nitration of Methyl Benzoate 306
Part B: Miniscale Nitration of Methyl Benzoate 306
Part C: Miniscale Nitration of an Unknown Aromatic Compound 307
Experiment 12.3 Friedel-Crafts Acylation Reactions 310
Part A: Microscale Procedure for Acetylation of Biphenyl 312
Part B: Microscale Procedure for Acetylation of Phenanthrene with TLC Analysis 313
Part C: Microscale Benzoylation of Ferrocene with Column Chromatography 314
Experiment 12.4 Aromatic Bromination 316
Part A: Microscale Bromination of Acetanilide 317
Part B: Microscale Bromination of p-Methylacetanilide with TLC and Column Chromatography or HPLC Analysis 319
Part C: Experimental Design of a Procedure for Bromination of an Acetanilide Derivative 320
Chapter Thirteen Combined Spectroscopy and Advanced Spectroscopy 323
Experiment 13.1 Infrared and Nuclear Magnetic Resonance Spectroscopy of Alcohols, Ethers, and Phenols 323
Part A: Experimental Procedure for Infrared Spectroscopy 326
Part B: Experimental Procedure for IR and NMR Spectroscopy 326
Part C: Exercises for IR and NMR Spectroscopy 327
Experiment 13.2 Combined Spectral Analysis: Infrared, Ultraviolet, and Nuclear Magnetic Resonance Spectroscopy and Mass Spectrometry 332
Solved Examples of the Use of Combined Spectroscopy 333
Part A: Purification of the Unknown 341
Part B: Preparation of the Sample and Spectroscopic Analysis 341
Part C: Spectroscopic Exercises 342
Chapter Fourteen Organometallics 351
Experiment 14.1 Grignard Synthesis: Preparation of Triphenylmethanol and 3-Methyl-2-phenyl- 2-butanol 351
Part A: Microscale Synthesis of Triphenylmethanol from Benzophenone 354
Part B: Miniscale Synthesis of Triphenylmethanol from Ethyl Benzoate 355
Part C: Microscale Synthesis of 3-Methyl-2-phenyl-2-butanol 358
Experiment 14.2 Using Indium Intermediates: Reaction of Allyl Bromide with an Aldehyde 360
Chapter Fifteen Alcohols and Diols 364
Experiment 15.1 Stereoselective Reduction of Ketones with Sodium Borohydride 364
Part A: Microscale Reduction of Benzil 366
Part B: Microscale Reduction of (1R)-(+)-Camphor 366
Experiment 15.2 Experimental Design for an Alcohol Oxidation 369
Experiment 15.3 Photochemical Oxidation of Benzyl Alcohol 373
Chapter Sixteen Ethers 376
Experiment 16.1 Ether Synthesis by SN2 Displacement 376
Part A: Microscale Preparation of an Alkyl Halophenyl Ether 378
Part B: Miniscale Preparation of Benzyl tert-Butyl Ether 379
Experiment 16.2 Nucleophilic Aliphatic Substitution Puzzle: Substitution Versus Elimination 380
Chapter Seventeen Aldehydes and Ketones 385
Experiment 17.1 Stereoselective Synthesis of Alkenes 386
Part A: Microscale Wittig Synthesis of trans-9-(2-phenylethenyl)anthracene 388
Part B: Miniscale Wittig Synthesis of trans-9-(2-phenylethenyl)anthracene 389
Part C: Microscale Horner-Emmons Reaction of Diethylbenzyl Phosphonate and Benzaldehyde 390
Experiment 17.2 Conversion of Cyclohexanone to Caprolactam 393
Part A: Microscale Conversion of Cyclohexanone to Caprolactam 395
Part B: Miniscale Conversion of Cyclohexanone to Caprolactam 395
Experiment 17.3 Pinacol Rearrangement and Photochemical Synthesis of Benzopinacol 399
Part A: Microscale Synthesis of Pinacolone 400
Part B: Miniscale Photoreduction of Benzophenone 401
Part C: Miniscale Synthesis of Benzopinacolone 402
Chapter Eighteen Enols, Enolates, and Enones 404
Experiment 18.1 Preparation of α,β-Unsaturated Ketones Via Mixed Aldol Condensation 404
Part A: Miniscale Synthesis of 1,9-Diphenyl-1,3,6,8- nonatetraen-5-one (Dicinnamalacetone) 407
Part B: Microscale Synthesis of Dibenzalacetone (1,5-Diphenyl-1,4-pentadien-3-one) 408
Part C: Identification of a Mixed Aldol Product from the Miniscale Condensation of an Unknown Aromatic Aldehyde with a Ketone 410
Experiment 18.2 Reduction of Conjugated Ketones with Sodium Borohydride 411
Part A: Microscale Reduction of 2-Cyclohexenone 412
Part B: Microscale Reduction of trans-4-Phenyl-3-buten-2-one 413
Experiment 18.3 Identification of Products of Catalytic Transfer Hydrogenation of an Enone 414
Part A: Microscale Reaction of 2-Cyclohexenone 416
Part B: Miniscale Reaction of 2-Cyclohexenone 416
Chapter Nineteen Carboxylic Acids 419
Experiment 19.1 Synthesis and Identificatoin of an Unknown Carboxylic Acid 419
Experiment 19.2 Synthesis of trans-Cinnamic Acid Via the Haloform Reaction 425
Chapter Twenty Carboxylic Acid Esters 430
Experiment 20.1 Combinatorial Chemistry and the Synthesis of Fruity Esters 430
Part A: Combinatorial Selection 432
Part B: Microscale Synthesis of an Ester 433
Experiment 20.2 Synthesis of Esters by Baeyer-Villiger Oxidation 436
Part A: Microscale Oxidation of an Unknown Cyclic Ketone 437
Part B: Miniscale Oxidation of Cyclohexanone 438
Chapter Twenty-One
Dicarbonyl Compounds 441
Experiment 21.1 Base-Catalyzed Condensations of Dicarbonyl Compounds 441
Part A: Microscale Preparation of Coumarin or a Coumarin Derivative 444
Part B: Miniscale Preparation of Coumarin or a Coumarin Derivative 444
Experiment 21.2 Reactions of Diketones: Synthesis of 2,5-Dimethyl-1-phenylpyrrole and Preparation of an Unknown Pyrrole 445
Part A: Microscale Synthesis of 2,5-Dimethyl-1-phenylpyrrole 447
Part B: Microscale Preparation of an Unknown Pyrrole 448
Chapter Twenty-Two
Amines 450
Experiment 22.1 Relating Color to Structure: Synthesis of Azo Dyes 450
Part A: Miniscale Diazotization of an Aromatic Amine 454
Part B.1: Miniscale Coupling with a Phenol 455
Part B.2: Miniscale Coupling with an Amine 455
Part C: Direct Dyeing with an Azo Dye 455
Part D: Recording the UV-Visible Spectrum of the Prepared Dyes 455
Part E: Determining the pH Indicator Range of the Prepared Dyes 455
Part F: Determining Antibacterial Properties of the Dye 456
Experiment 22.2 Synthesis of Pyrazole and Pyrimidine Derivatives 457
Part A: Microscale Synthesis of a Five-Member Ring Heterocycle from Hydrazine and an Unknown Diketone 461
Part B: Miniscale Synthesis of a Five-Member Ring Heterocycle from Hydrazine and an Unknown Diketone 461
Part C: Microscale Synthesis of a Substituted Pyrimidine 462
Part D: Miniscale Synthesis of a Substituted Pyrimidine 462
Experiment 22.3 Synthesis of Heterocyclic Compounds 464
Part A: Miniscale Reaction of Benzaldehyde and Pyrrole 466
Part B: Microscale Reaction of o-Phenylenediamine and Formic Acid 467
Experiment 22.4 Synthesis of Heterocycles and Kinetics by Spectroscopic Analysis 469
Part A: Miniscale Preparation of Lophines (2-Aryl-4,5-diphenylimidazoles) 471
Part B: Miniscale Synthesis of Substituted Lophinyl (2-Aryl-4,5-diphenylimidazole) Dimers 471
Part C: Kinetics of the Recombination Reaction 472
Chapter Twenty-Three Aryl Halides 475
Experiment 23.1 Nucleophilic Aromatic Substitution 475
Part A: Microscale Reaction of Sodium Ethoxide with 1-Bromo-2,4-dinitrobenzene 477
Part B: Microscale Reaction of Sodium Ethoxide with p-Fluoronitrobenzene 477
Chapter Twenty-Four Phenols 480
Experiment 24.1 Exploring Structure-function Relationships of Phenols: Synthesis of Salicylic Acid, Aspirin, and Vanillin Derivatives 480
Part A: Miniscale Reactions of Vanillin 483
PartB: Miniscale Hydrolysis of Methyl Salicylate 485
Part C: Miniscale Synthesis of Acetylsalicylic Acid 486
Chapter Twenty-Five Carbohydrates 489
Experiment 25.1 Classification of Sugars and Identification of an Unknown Sugar 490
General Instructions for the Microscale Identification of an Unknown Sugar 495
Part A: Osazone Formation 496
Part B: Chemical Tests 496
Experiment 25.2 Esterification of Sugars: Preparation of Sucrose Octaacetate and α- and β-D-Glucopyranose Pentaacetate 498
Part A: Miniscale Preparation of D-Sucrose Octaacetate 500
Part B: Microscale Preparation of β-D-Glucopyranose Pentaacetate 501
Part C: Microscale Conversion of β-D-Glucopyranose Pentaacetate to the a-Anomer 502
Part D: Miniscale Preparation of
α-D-Glucose Pentaacetate and Measurement of Optical Rotation 503
Chapter Twenty-Six Lipids 507
Experiment 26.1 Soap from a Spice: Isolation, Identification, and Hydrolysis of a Triglyceride 507
Part A: Miniscale Isolation of a Triglyceride from Nutmeg 509
Part B: Microscale Hydrolysis of a Triglyceride 510
Part C: Determination of Properties of the Soap from Nutmeg 511
Experiment 26.2 Preparation of Esters of Cholesterol and Determination of Liquid Crystal Behavior 512
Chapter Twenty-Seven Amino Acids and Derivatives 518
Experiment 27.1 Conversion of an Amino Acid to a Sunscreen: Multistep Preparation of Benzocaine or a Benzocaine Analog 518
Part A: Miniscale Synthesis of p-Methylacetanilide 521
Part B: Miniscale Synthesis of p-Acetamidobenzoic Acid 522
Part C: Miniscale Synthesis of p-Aminobenzoic Acid 523
Part D: Microscale Esterification of p-Aminobenzoic Acid 525
Part E: Determining the Effectiveness of the p-Aminobenzoic Acid Ester as a Sunscreen 526
Chapter Twenty-Eight
Qualitative Organic Analysis II 529
Experiment 28.1 Designing a Classification Scheme for Characterizing an Organic Compound 529
Part A: Microscale Solubility Tests 530
Part B: Microscale Chemical Tests 531
Part C: Microscale Classification of an Unknown Compound 536
Experiment 28.2 Experimental Methods of Qualitative Organic Analysis 537
Introduction to Qualitative Organic Analysis 537
Overall Approach to Identifying the Unknown 538
Step 1: Purify 538
Step 2: Determine the Physical Properties 538
Step 3: Examine the Physical State 538
Step 4: Perform Solubility Tests 538
Step 5: Identify the Functional Groups Present 540
Step 6: Select an Appropriate Derivative 551
Step 7: Prepare and Purify the Derivative 552
Step 8: Identify the Unknown 557
Experimental Procedure 557
Part A: Purification of the Unknown 559
Part B: Solubility Tests 559
Part C: Chemical Tests (Arranged Alphabetically) 560
Part D: Derivatives 566
Part E Qualitative Organic Analysis of Unknowns 574
Part E.1: Qualitative Analysis of Aldehydes and Ketones 574
Part E.2: Qualitative Analysis of Alcohols and Phenols 575
Part E.3: Qualitative Analysis of Amines and Carboxylic Acids 575
Part E.4: Qualitative Analysis of a General Unknown 575
Part E.5: Qualitative Analysis and Spectroscopic Analysisof a General Unknown 575
Chapter Twenty-Nine
Projects 578
Experiment 29.1 Multistep Synthesis of 1-Bromo-3-chloro-5-iodobenzene from Aniline 579
Part A: Synthesis of Acetanilide from Aniline 583
Part B: Miniscale Synthesis of 4-Bromoacetanilide from Acetanilide 585
Part C: Synthesis of 4-Bromo-2-chloroacetanilide from 4-Bromoacetanilide 586
Part D: Synthesis of 4-Bromo-2-chloroaniline from 4-Bromo-2-chloroacetanilide 587
Part E: Miniscale Synthesis of 4-Bromo-2-chloro-6-iodoaniline from 4-Bromo-2-chloroaniline 589
Part F: Synthesis of 1-Bromo-3-chloro-5-iodobenzene from 4-Bromo-2-chloro-6-iodoaniline 590
Experiment 29.2 Multistep Synthesis of Sulfanilamide Derivatives as Growth Inhibitors 592
Part A: Preparation of Acetanilide 594
Part B: Preparation of p-Acetamidobenzenesulfonyl Chloride 595
Part C: Reaction of p-Acetamidobenzenesulfonyl Chloride with an Amine 595
Part D: Hydrolysis of the Acetamido Group 596
Part E: Bacterial Testing of Antibiotic Susceptibility 596
Part A: Miniscale Synthesis of Acetanilide 597
Part B: Miniscale Synthesis of p-Acetamidobenzenesulfonyl Chloride 597
Part C: Miniscale Synthesis of Sulfonamides 598
Part D: Miniscale Synthesis of Sulfanilamides 599
Part E: Bacterial Testing of Antiobiotic Susceptibility 600
Experiment 29.3 Structural Determination of Isomers Using Decoupling and Special NMR Techniques 602
Part A: Homonuclear Decoupling of a Known Alkene and Determination of Coupling Constants 612
Part B: Characterization of an Unknown Compound Using Homonuclear Decoupling in 1H NMR 612
Part C: Characterization of an Unknown Compound Using 1H NMR, 13C NMR, 1H-1H (COSY) and HETCOR (1H-13C COSY) 613
Experiment 29.4 The Library-Laboratory Connection 614
Part A: Chemical Abstracts (CA) and Beilstein 614
Part B: Searching Science Library Databases 619
Part C: Searching on the Web 620
Experiment 29.5 Stereochemistry, Molecular Modeling, and Conformational Analysis 621
Part A: Molecular Models Using a Model Kit 624
Part B: Computer Modeling 625
Part C: Conformational Analysis of Rotational Isomers 625
Part D: Using Molecular Modeling to Analyze Rotational Conformations of Stereoisomers 625
Appendix A Tables of Derivatives for Qualitative Organic Analysis 627
Appendix B Laboratory Skills and Calculations 632
Appendix C Designing a Flow Scheme 637
Appendix D Material Safety Data Sheet 639
Appendix E Tables of Common Organic Solvents and Inorganic Solutions 643
Index 645 |
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2004 McGraw-Hill Higher Education