Experimental Organic Chemistry: A Miniscale and Microscale Approach

Front Cover......Page 1
Title Page......Page 7
Copyright......Page 8
Table of Contents......Page 10
1.1 Introduction......Page 29
1.2 Preparing For The Laboratory......Page 30
1.3 Working In The Laboratory......Page 31
1.5 General Protocol For The Laboratory Notebook......Page 32
1.6 Types Of Organic Experiments And Notebook Formats......Page 33
1.7 Sample Calculations For Notebook Records......Page 42
1.8 Safe Laboratory Practice: Overview......Page 44
1.9 Safety: General Discussion......Page 45
1.10 Safety: Material Safety Data Sheets......Page 47
1.11 Safety: Disposal Of Chemicals......Page 49
Historical Highlight: The Importance of Record Keeping......Page 52
2.1 Glassware: Precautions And Cleaning......Page 55
2.2 Standard-Taper Glassware For Miniscale Procedures......Page 56
2.3 Standard-Taper Glassware For Microscale Procedures......Page 57
2.4 Assembling Apparatus......Page 59
2.5 Measuring And Transferring Liquids......Page 60
2.6 Weighing Methods......Page 65
2.7 Melting-Point Methods And Apparatus......Page 66
2.8 Boiling-Point Methods And Apparatus......Page 69
2.9 Heating Methods......Page 71
2.10 Cooling Techniques......Page 79
2.11 Stirring Methods......Page 80
2.12 Centrifugation......Page 82
2.13 Simple Distillation......Page 83
2.14 Fractional Distillation......Page 86
2.15 Vacuum Distillation......Page 88
2.16 Steam Distillation......Page 92
2.17 Filtration Apparatus And Techniques......Page 94
2.18 Decolorizing Carbon......Page 100
2.20 Sublimation......Page 101
2.21 Extraction......Page 103
2.22 Heating Under Reflux......Page 109
2.23 Gas Traps......Page 111
2.24 Drying Agents......Page 113
2.26 Drying Solids......Page 115
2.28 Drying Apparatus......Page 116
2.29 Evaporating Solvents......Page 117
3.1 Introduction......Page 121
3.2 Recrystallization......Page 122
Recrystallization......Page 129
3.3 Physical Constants: Melting Points......Page 141
Melting Points......Page 145
Historical Highlight: Polymorphism......Page 150
4.2 Boiling Points Of Pure Liquids......Page 155
Boiling Points of Pure Liquids......Page 157
4.3 Simple Distillation......Page 159
Simple Distillation......Page 161
4.4 Fractional Distillation......Page 163
Fractional Distillation of a Binary Mixture......Page 169
4.5 Steam Distillation......Page 173
4.6 Steam Distillation: Isolation Of Citral From Lemon Grass Oil......Page 175
Steam Distillation of Citral from Lemon Grass Oil......Page 177
Historical Highlight: Reducing Automobile Emissions......Page 179
5.1 Introduction......Page 181
5.2 Theory Of Extraction......Page 182
5.3 Base And Acid Extractions......Page 184
Base and Acid Extractions......Page 189
5.4 Extraction Of A Natural Product: Trimyristin......Page 199
Isolation of Trimyristin from Nutmeg......Page 200
Historical Highlight: Natural Products......Page 203
6.1 Introduction......Page 207
6.2 Thin-Layer Chromatography......Page 208
Separation of Spinach Pigments by TLC......Page 212
Separation of Syn- and Anti-Azobenzenes by TLC......Page 214
6.3 Column Chromatography......Page 216
Column Chromatography......Page 220
6.4 Gas-Liquid Chromatography......Page 224
Historical Highlight: Who’s Taking What? Analysis of Biological Fluids for Illegal Substances......Page 238
7.1 Introduction......Page 241
7.2 Separation Of Diastereomeric 1, 2-Cyclohexanediols......Page 244
Separation of Diastereomeric 1,2-Cyclohexanediols......Page 245
7.3 Isomerization Of Dimethyl Maleate To Dimethyl Fumarate......Page 247
Isomerization of Dimethyl Maleate to Dimethyl Fumarate......Page 248
7.4 Properties Of The Enantiomers Of Carvone......Page 251
Properties of the Enantiomeric Carvones......Page 253
7.5 Polarimetry......Page 255
7.6 Resolution Of Racemic 1-Phenylethanamine......Page 257
Resolution of Racemic 1-Phenylethanamine......Page 259
Historical Highlight: Discovery of Stereoisomers......Page 262
8.1 Introduction......Page 265
8.2 Infrared (IR) Spectroscopy......Page 268
8.3 Nuclear Magnetic Resonance (NMR) Spectroscopy......Page 289
8.4 Ultraviolet And Visible Spectroscopy......Page 325
8.5 Mass Spectrometry......Page 332
Historical Highlight: Medical Diagnostics via Nuclear Magnetic Resonance Spectroscopy......Page 339
9.1 Introduction......Page 341
9.2 Chlorination Using Sulfuryl Chloride......Page 342
Free-Radical Chain Chlorination of l-Chlorobutane......Page 345
9.3 Bromination: Selectivity Of Hydrogen Atom Abstraction......Page 352
Relative Rates of Free-Radical Chain Bromination......Page 354
Historical Highlight: Keeping It Cool......Page 361
10.1 Introduction......Page 365
10.2 Dehydrohalogenation Of Alkyl Halides......Page 366
Base-Promoted Elimination of an Alkyl Halide......Page 368
10.3 Dehydration Of Alcohols......Page 376
Dehydration of Alcohols......Page 380
10.4 Addition Reactions Of Alkenes: Overview......Page 392
10.5 Addition Of Hydrobromic Acid To Alkenes......Page 395
Addition of Hydrogen Bromide to 1-Hexene......Page 396
10.6 Bromination Of Alkenes......Page 404
Bromination of (E)-Stilbene......Page 405
10.7 Acid-Catalyzed Hydration Of Alkenes......Page 412
Hydration of Norbornene......Page 413
10.8 Hydroboration-Oxidation Of Alkenes......Page 417
Hydroboration-Oxidation of (+)- -Pinene......Page 420
Historical Highlight: Additions Across Carbon-Carbon  - Bonds......Page 427
11.1 Introduction......Page 431
11.2 Dehydrohalogenation Of 1, 2 -Dihaloalkanes......Page 432
Dehydrobromination of Meso-Stilbene Dibromide......Page 433
11.3 Addition Reactions Of Alkynes......Page 438
Preparation of 3-Hydroxy-3-methyl-2-Butanone......Page 440
11.4 Terminal Alkynes As Acids......Page 444
Formation of a Silver Acetylide and Its Decomposition......Page 445
Historical Highlight: Acetylene: A Valuable Small Molecule......Page 446
12.1 Introduction......Page 449
12.2 Mechanistic And Stereochemical Aspects......Page 450
12.3 Applications Of Diels-Alder Reactions......Page 452
Diels-Alder Reaction......Page 454
Historical Highlight: Discovery of the Diels-Alder Reaction......Page 470
13.1 Introduction......Page 473
13.2 Formation Of Semicarbazones Under Kinetic And Thermodynamic Control......Page 476
Kinetic and Thermodynamic Control of a Reaction......Page 478
14.1 General Concepts......Page 489
14.2 Classification Of Nucleophilic Substitution Reactions......Page 490
14.3 Competition Between Substitution And Elimination......Page 492
14.4 Preparation Of 1-Bromobutane: An SN2 Reaction......Page 493
Preparation of 1-Bromobutane......Page 495
14.5 Preparation Of 2-Chloro-2-Methylbutane: An SN1 Reaction......Page 501
Preparation of 2-Chloro-2-Methylbutane......Page 503
14.6 Chemical Kinetics: Evidence For Nucleophilic Substitution Mechanisms......Page 509
Kinetics of Solvolysis of 2-Chloro-2-Methylbutane......Page 512
15.1 Introduction......Page 519
15.2 Friedel-Crafts Alkylation Of p-Xylene With 1-Bromopropane......Page 520
Friedel-Crafts Alkylation of p-Xylene......Page 523
15.3 Friedel-Crafts Acylation Of m-Xylene......Page 531
Friedel-Crafts Acylation of m-Xylene with Phthalic Anhydride......Page 533
15.4 Nitration Of Bromobenzene......Page 541
Nitration of Bromobenzene......Page 543
15.5 Relative Rates Of Electrophilic Aromatic Substitution......Page 550
Relative Rates of Electrophilic Aromatic Bromination......Page 553
Historical Highlight: Discovery of the Friedel-Crafts Reaction......Page 561
16.1 Introduction......Page 565
16.2 Preparation Of Aldehydes And Ketones By Oxidation Of Alcohols......Page 567
Oxidation of Alcohols......Page 571
16.3 Base-Catalyzed Oxidation-Reduction Of Aldehydes: The Cannizzaro Reaction......Page 581
Base-Catalyzed Oxidation-Reduction of Aldehydes by the Cannizzaro Reaction......Page 583
Historical Highlight: Green Chemistry......Page 588
17.1 Introduction......Page 591
17.2 Catalytic Hydrogenation Of The Carbon-Carbon Double Bond......Page 593
Hydrogenation of 4-Cyclohexene-cis-1,2-dicarboxylic Acid......Page 595
17.3 Reduction Of Imines; Preparation Of Amines......Page 599
Formation and Reduction of N-Cinnamylidene-m-nitroaniline......Page 601
17.4 Reduction Of Carbonyl Compounds; Preparation Of Alcohols......Page 609
Reduction of 9-Fluorenone......Page 610
17.5 Enzymatic Reduction: A Chiral Alcohol From A Ketone......Page 615
Enzymatic Reduction of Methyl Acetoacetate......Page 616
17.6 Determining Optical Purity......Page 621
Determining Optical Purity of Methyl (S)-(+)-3- Hydroxybutanoate......Page 622
Historical Highlight: Chiral Drugs......Page 624
18.1 Introduction......Page 629
18.2 The Wittig And Related Reactions......Page 631
Wittig and Horner-Wadsworth-Emmons Reactions......Page 634
18.3 Reactions Of Stabilized Carbanions From Carbonyl Compounds......Page 645
Preparation of trans-p-Anisalacetophenone......Page 647
18.4 Conjugate Addition To An α, β-Unsaturated Ketone......Page 653
Preparation of 4,4-Dimethyl-2-Cyclohexen-1-One......Page 656
Historical Highlight: The Wittig Reaction......Page 664
19.1 Introduction......Page 667
19.2 Grignard Reagents: Preparation......Page 668
Preparation of Grignard Reagents......Page 671
19.3 Grignard Reagents: Reactions......Page 677
19.4 Special Experimental Techniques......Page 679
Reactions of Grignard Reagents......Page 680
Historical Highlight: Grignard and the Beginnings of Modern Organometallic Chemistry......Page 694
20.1 Introduction......Page 697
20.2 Esters And The Fischer Esterification......Page 700
Preparation of Benzocaine......Page 701
20.3 Amides And Insect Repellents......Page 707
Preparation of N,N-Diethyl-m-toluamide......Page 709
20.4 Amides And Chemiluminescence......Page 716
Preparation and Chemiluminescence of Luminol......Page 721
Historical Highlight: Evolution of Synthetic Analgesics......Page 727
21.1 Introduction......Page 731
21.2 Sulfanilamide: Discovery And Synthesis Of The First Antibiotic......Page 732
Synthesis of Sulfanilamide......Page 739
21.3 Synthesis Of 1-Bromo-3-Chloro-5-Iodobenzene......Page 754
Synthesis of 1-Bromo-3-Chloro-5-Iodobenzene......Page 759
21.4 Lidocaine: Synthesis Of An Anesthetic Agent......Page 775
Synthesis of Lidocaine......Page 779
Historical Highlight: Discovery of Sulfa Drugs......Page 790
22.1 Introduction......Page 793
22.2 Chain-Reaction Polymerization......Page 795
Preparation of Polystyrene......Page 798
22.3 Step-Growth Polymerization......Page 804
Preparation of Nylon-6,10......Page 808
Historical Highlight: Discovery of Polyethylene and Nylon......Page 813
23.1 Introduction......Page 815
23.2 Monosaccharides: General Principles......Page 816
23.3 Disaccharides: Hydrolysis Of Sucrose......Page 817
Hydrolysis of Sucrose......Page 819
23.4 Carbohydrates: Their Characterization And Identification......Page 822
Classification Tests for Carbohydrates......Page 823
Historical Highlight: Emil Fischer: Carbohydrate Chemist Extraordinaire......Page 827
24.1 Introduction......Page 831
24.2 Synthesis Of Peptides And Polypeptides......Page 834
24.3 Synthesis Of The Protected Dipeptide Ala–Phe–OMe......Page 835
A Preparation of N-tert-Butoxycarbonyl L-Alanine......Page 839
B Preparation of Methyl L-Phenylalaninate Hydrochloride......Page 841
C Preparation of Methyl N-tert-Butoxycarbonyl L-Alanyl-L-phenylalaninate......Page 843
D Preparation of Methyl L-Alanylphenyl-L-Alaninate Trifluoroacetate......Page 845
Historical Highlight: Invention of a Method for Solid-Phase Peptide Synthesis......Page 856
25.1 Introduction......Page 861
25.2 Overview Of Organic Analysis......Page 862
25.3 Classic Qualitative Analysis Procedure To Identify A Pure Compound......Page 863
Elemental Analysis......Page 865
25.4 Separating Mixtures Of Organic Compounds......Page 875
Separating Mixtures on the Basis of Solubility......Page 876
25.5 Applying Spectroscopic Methods To Qualitative Organic Analysis......Page 878
25.7 Aldehydes And Ketones......Page 884
2,4-Dinitrophenylhydrazine Test for Aldehydes and Ketones......Page 885
Schiff’s Test for Aldehydes......Page 887
Tollens’s Test for Aldehydes......Page 888
Chromic Acid Test for Aldehydes and 1° and 2° Alcohols 861 Iodoform Test......Page 889
Iodoform Test......Page 892
Preparation of Semicarbazones......Page 893
Preparation of Oximes......Page 894
Bromine Test for Unsaturation......Page 895
25.9 Alkyl Halides......Page 897
Silver Nitrate Test for Alkyl Halides......Page 898
Sodium Iodide Test for Alkyl Chlorides and Bromides......Page 899
25.10 Aromatic Hydrocarbons And Aryl Halides......Page 900
Friedel-Crafts Reaction for Detecting Arenes......Page 901
Preparation of Nitroarenes......Page 902
Side-Chain Oxidation of Arenes......Page 903
25.11 Alcohols......Page 905
Lucas Test for Alcohols......Page 906
Preparation of Urethanes......Page 907
Preparation of 3,5-Dinitrobenzoates......Page 908
25.12 Phenols......Page 910
Bromine Water Test for Phenols......Page 911
Ferric Chloride Test for Phenols and Enols......Page 912
Preparation of Bromophenols......Page 913
Determination of Equivalent Mass of an Acid......Page 914
Preparation of Amides......Page 915
25.14 Amines......Page 917
Hinsberg Test for Amines......Page 919
Ramini and Simon Tests for Amines......Page 921
Preparation of Benzamides, Benzenesulfonamides, and Methiodides......Page 922
25.15 Nitro Compounds......Page 923
Reduction of Nitro Compounds......Page 924
25.16 Esters......Page 925
Hydroxylamine Test for Esters......Page 926
Determination of Saponification Equivalent......Page 927
Base-Promoted Hydrolysis of Esters......Page 928
Hydroxylamine Test for Nitriles......Page 929
Hydrolysis of Nitriles......Page 930
25.18 Amides......Page 931
Base-Promoted Hydrolysis of Amides......Page 932
26.2 Classification Of The Literature......Page 933
26.3 Using The Literature Of Organic Chemistry......Page 944
Index......Page 953