Experimental Organic Chemistry

Daniel R. Palleros is the author of Experimental Organic Chemistry, published by Wiley.

• Section 1 The Basics 1Unit 1 Laboratory Safety 31.1 General Safety Guidelines 31.2 Chemical Toxicity 61.3 Dealing with Chemicals and Waste Disposal 71.4 Online Safety Resources 15Unit 2 Basic Concepts 192.1 Polarity and H-Bonds 192.2 Physical Data 232.3 Solvents 242.4 Balancing Chemical Equations 262.5 Concentration Units 282.6 Moles and Millimoles 292.7 Mineral Acids 312.8 Calculation of Yields 322.9 Scaling Up, Scaling Down 342.10 Keeping Lab Books and Writing Lab Reports 342.11 Chemical Literature 35Unit 3 Basic Operations 453.1 Handling Liquids 453.2 Heating 463.3 Filtration 473.4 Refluxing 513.5 Evaporation 533.6 Centrifugation 553.7 Caring for Glassware 553.8 Measuring Pressure 57Section 2 The Experiments 59Unit 4 Recrystallization and Melting Point 614.1 Overview 614.2 Recrystallization 624.3 Decolorizing Charcoal 694.4 Recrystallization from Mixed Solvents 704.5 Microscale Recrystallization 704.6 Melting Point 714.7 Sublimation 75Experiment 4 Recrystallization of Acetanilide and Urea 79E4.1 Recrystallization of Acetanilide 80E4.2 Microscale Recrystallization of Urea 82E4.3 Determination of Melting Points 82Unit 5 Extraction 865.1 Introduction 865.2 Solvent-Solvent Partitioning 865.3 Macroscale Liquid-Liquid Extraction 925.4 Microscale Liquid-Liquid Extraction 935.5 Drying the Organic Layer 945.6 Solid-Liquid Extraction 955.7 Countercurrent Distribution 97Experiment 5 Isolation of Caffeine from Tea 103E5.1 Tea, Coffee, and Caffeine 103E5.2 Caffeine from Tea: Overview of the Experiment 105E5.3 Isolation of Caffeine 109E5.4 Purification of Caffeine by Sublimation 110E5.5 Purification of Caffeine by Recrystallization (Alternative Procedure) 111Unit 6 Distillation — Separation and Purification of Organic Liquids 1136.1 Boiling Point 1136.2 Boiling Point and Molecular Structure 1146.3 Simple Distillation 1156.4 Fractional Distillation 1206.5 Ideal and Nonideal Solutions 1236.6 Azeotropic Mixtures 1246.7 Fractionating Columns 1256.8 Microscale Distillation 1266.9 Boiling Point Determination 1286.10 Vacuum Distillation 1296.11 Steam Distillation 130Experiment 6A Distillation of Alcohols 136E6A.1 Distillation of Methanol from a Mixture with Ferric Chloride 136E6A.2 Separation of Methanol-Water by Simple Distillation 137E6A.3 Separation of Methanol-Water by Fractional Distillation 138E6A.4 Analysis of the Distillation Fractions by Density 139Experiment 6B Isolation of Anise Oil 142E6B.1 Overview 142E6B.2 Isolation of Anise Oil 142Unit 7 Gas Chromatography 1447.1 Introduction 1447.2 The Chromatographic Methods 1447.3 Partition Chromatography 1467.4 Gas Chromatography 1497.5 The Gas Chromatograph 1517.6 Measuring the Retention Time 1557.7 Integration 1567.8 Quantitative Analysis 1577.9 Quantitative Analysis: A Closer Look (Advanced Level) 1587.10 Qualitative Analysis 1617.11 Running GC: Step by Step 1627.12 Gas Chromatography Do’s and Don’ts 163Experiment 7A Gas Chromatography of Alcohols 167E7A.1 Analysis of Alcohols 167E7A.2 Separation of Methanol and Water 168Experiment 7B Analysis of Anise Oil 170E7B Analysis of Anise Oil 170Unit 8 Thin-Layer Chromatography 1728.1 Overview 1728.2 The Adsorption Process 1738.3 Selection of TLC Conditions 1758.4 Running TLC Plates 1788.5 Adsorption Isotherms (Advanced Level) 1828.6 Applications of TLC 1848.7 Other Stationary Phases 1868.8 TLC Do’s and Don’ts 186Experiment 8 TLC Analysis of Vegetable Extracts 190E8.1 Plant Pigments 190E8.2 Isolation and Analysis of Plant Pigments 192Unit 9 Column Chromatography 1979.1 Overview 1979.2 Practical Aspects 1979.3 Applications 2029.4 Column Chromatography Do’s and Don’ts 203Experiment 9 Isolation of C60 from Fullerene Soot 206E9.1 Fullerenes 206E9.2 Isolation of Fullerenes 207E9.3 A Chemical Test for Fullerenes 208E9.4 Overview of the Experiment 209E9.5 Isolation of C60 from Fullerene Soot 209Unit 10 High-Performance Liquid Chromatography 21410.1 Overview 21410.2 HPLC Systems 21410.3 HPLC Versus GC 21510.4 Solvents 21610.5 Pumps 21710.6 Injection Port 21710.7 Columns 21810.8 Detectors 21910.9 Why is HPLC High Performance? 22010.10 Reversed-Phase Chromatography 22110.11 Other Chemically Bonded Stationary Phases 22210.12 Size-Exclusion Chromatography 22310.13 Quantitative Determinations: Standard Curve Method 22410.14 HPLC Do’s and Don’ts 224Experiment 10 Vitamin Analysis—A Quantitative Study 227E10.1 Water-Soluble and Fat-Soluble Vitamins 227E10.2 Vitamin Stability 229E10.3 International Units 230E10.4 Characterization of Vitamin A 230E10.5 Overview of the Experiment 231Unit 11 Refractometry and Polarimetry 23811.1 Refractive Index 23811.2 The Refractometer 23911.3 Measuring the Refractive Index 24011.4 Polarimetry 24211.5 The Polarimeter 24511.6 Measuring the Optical Rotation 24611.7 Optical Rotation of Mixtures 247Experiment 11A Analysis of Essential Oils 250E11A.1 Terpenoids 250E11A.2 Essential Oils 252E11A.3 Specific Rotation 253E11A.4 Refractive Index 253E11A.5 Composition of Essential Oils 253Experiment 11B Separation of Carvone and Limonene 255E11B.1 Carvone and Limonene 255E11B.2 Analysis of the Crude Oils 256E11B.3 Separation of Carvone and Limonene 257Unit 12 Alcohols and Alkenes 26112.1 Alkenes from Alcohols 26112.2 Dehydration Mechanisms 26212.3 Characterization of Alkenes 264Experiment 12 The Dehydration of Methylcyclohexanols 268E12.1 Overview 268E12.2 Dehydration of Methylcyclohexanols 269E12.3 Analysis of the Product Mixture 270Unit 13 Alkyl Halides 27313.1 Preparation 27313.2 Reactions 27413.3 Alkyl Halides from Alcohols 27413.4 Characterization Tests 276Experiment 13 Synthesis of n-ButyI Bromide and 2-ChIoro-2-MethyIbutane 280E13.1 Synthesis of n-Buty1 Bromide 280E13.2 Synthesis of 2-Ch1oro-2-Methy1butane 284E13.3 Characterizahon Tests 285Unit 14 Acid-Base Extraction 29214.1 Introduction 29214.2 Acids and Bases 29214.3 Structural Effects on Acid-Base Properties 29414.4 Acid-Base Extraction 29814.5 Overview 303Experiment 14A Isolation of Eugenol from Cloves 307E14A.1 Ancient Medicine 307E14A.2 Eugenol from Cloves: Overview of the Experiment 307E14A.3 Isolation of Eugenol 308E14A.4 GC and IR Analyses 310Experiment 14B Isolation of the Active Ingredients in an Analgesic Tablet 315E14B.1 Overview 315E14B.2 Separation of the Active Ingredients in Excedrin 317E14B.3 Analysis 317Unit 15 Phenols and Ethers 32315.1 Phenols and Ethers 32315.2 Williamson Ether Synthesis 32315.3 Characterization of Phenols: Ferric Chloride Test 32415.4 IR and NMR of Phenols and Ethers 325Experiment 15 Medicinal Chemistry: From Tylenol to a Banned Chemical 327E15.1 Analgesics 327E15.2 The Experiment: Overview 329E15.3 Conversion of Acetaminophen into Phenacetin 330E15.4 Ferric Chloride Test 332E15.5 Analysis of Analgesics by TLC 332Unit 16 Electrophilic Aromatic Substitution 33616.1 Mechanism of Electrophilic Aromatic Substitution 33616.2 Nitration and Halogenation 33716.3 Effects of Substituents 338Experiment 16A lodinatian of Tyrosine 342E16A.1 Synthesis of 3,5-Diiodotyrosine 342Experiment 16B Two Substitution Puzzles 350E16B.1 Overview 350E16B.2 NMR Analysis 351E16B.3 Nitration of Phenacetin 352E16B.4 Bromination of Phenacetin 353Unit 17 Nucleophilic Aromatic Substitution 35517.1 Nucleophilic Aromatic Substitution 35517.2 Dinitroanilines 356Experiment 17 Dinitrocompounds—Herbicides 360E17.1 Synthesis of Trifluralin 360E17.2 Synthesis of N -(n-Buty1) -2,4-Dinitroani1ine 361E17.3 Herbicide Effects of Trifluralin and N -(n-Butyl) -2,4-Dinitroaniline 362Unit 18 Chemical Kinetics 36818.1 Mechanistic Studies 36818.2 Chemical Kinetics 36818.3 Experimental Aspects 37018.4 Integrated Rate Equations 37018.5 Reaction Half-Life 37218.6 Transition States 37218.7 Dependence of the Rate Constant with Temperature: Arrhenius Equation 37518.8 Following the Kinetics 37518.9 Best Fit 377Experiment 18 Nucleophilic Aromatic Substitution Kinetics 381 E18.1 The Problem 381E18.2 To Follow the Kinetics 383E18.3 Overview of the Experiment 383E18.4 Synthesis of 2,4-Dinitroanisole 384E18.5 Visible Spectrum of N-(n-Butyl) -2,4-Dinitroaniline 384E18.6 Beer’s Law of N-(n-Butyl) -2,4-Dinitroaniline 385E18.7 Kinetics of the Reaction of 2,4-Dinitroanisole with n-Butylamine in Methanol 385Unit 19 Diels-Alder Reaction 39119.1 Diels—Alder Reaction 39119.2 Endo versus Exo 39219.3 Solvent Effects 39319.4 Experimental Considerations: Following the Reaction 395Experiment 19A Diels—Alder Reactions in Toluene 398E19A.1 Reaction of 9-Anthraldehyde with Maleic Anhydride 398E19A.2 Reaction of Phencyclone with Norbornadiene 400Experiment 19B Diels—Alder Reaction in Water 408E19B.1 Reaction of 9-Anthracenemethanol with N-Ethylmaleimide 408E19B.2 Kinetics of the Reaction of 9-Anthracenemethanol with NEM 409Unit 20 Aldehydes and Ketones 41520.1 Introduction 41520.2 Preparation 41620.3 Reactions of Aldehydes and Ketones 41620.4 IR and NMR of Aldehydes and Ketones 423Experiment 20A Identification of Aldehydes and Ketones 427E20A.1 Characterization Tests 428E20A.2 Preparation of Derivatives 430E20A.3 The Unknown 430Experiment 20B Synthesis of trans-Cinnamic Acid 433 E20B Synthesis of trans-Cinnamic Acid: Perkin Condensation, 433Unit 21 Oxidation-Reduction 438 21.1 Overview 43821.2 Selectivity 43921.3 Oxidations 44021.4 Phase Transfer Catalysis 44421.5 Reductions 445Experiment 21 Oxidation-Reduction 451E21.1 Reduction of Benzophenone 451E21.2 Oxidation of Benzhydrol 452E21.3 Reduction of trans-Cinnamaldehyde 453E21.4 Oxidation of trans-Cinnamyl Alcohol 454E21.5 Reduction of Camphor 455E21.6 Oxidation of Isoborneol 456E21.7 Synthesis of Terephthalic Acid 456E21.8 Monoreduction of m-Dinitrobenzene 458Unit 22 Esters 47322.1 Esters in Nature and Society 47322.2 Preparation of Esters 47422.3 Acetylation 47622.4 Ester Hydrolysis 47622.5 Characterization of Esters 47722.6 IR and NMR of Esters and Carboxylic Acids 477Experiment 22A Preparation of Fruity Fragrances 480E22A.1 Preparation of Methyl trans-Cirinamate: A Component of Strawberry Aroma 480E22A.2 Preparation of n-Propy1 Acetate and Isoamyl Acetate 482E22A.3 Hydroxamic Acid Test 484Experiment 22B Transforming Bengay into Aspirin 491E22B.1 Overview 491E22B.2 Separation of Methyl Salicylate, 493E22B.3 Hydrolysis of Methyl Salicylate, 493E22B.4 Synthesis of Aspirin 494E22B.5 Analysis 494Unit 23 Multistep Synthesis 49923.1 Overview 49923.2 Multistep Synthesis 50023.3 Retrosynthetic Analysis 50223.4 Planning a Multistep Synthesis 50723.5 Linear versus Convergent Synthesis 508Experiment 23A Synthesis of an Ant Alarm Pheromone: 2-Methyl-4-Heptanone 511E23A.1 Overview 511E23A.2 Synthetic Route 511E23A.3 Grignard Reactions 512E23A.4 Oxidation of Secondary Alcohols 514E23A.5 Synthesis of 2-Methyl-4-Heptanol 514E23A.6 Synthesis of 2-Methyl-4-Heptanone 516E23A.7 Vacuum Distillation 516Experiment 23B Synthesis of Ionones: An Open-Ended Experiment 520E23B.1 lonones 520E23B.2 Synthetic Pathway 520E23B.3 Characterization of lonones 522E23B.4 Preparation of Pseudoionones 523E23B.5 Cyclization with Sulfuric Acid-Acetic Acid 524E23B.6 Cyclization with Phosphoric Acid 525Unit 24 Molecules of Life 53224.1 Proteins 53224.2 Carbohydrates 539Experiment 24 Chemistry of Milk 546E24.1 Composition of Milk 546E24.2 Isolation and Characterization of Casein 549E24.3 Isolation and Characterization of Lactose 552Unit 25 Lipids 55625.1 Fats and Oils 55625.2 Characterization of Oils 55825.3 Uncommon Fatty Acids and Related Compounds 55925.4 Saponification 56025.5 Steroids 56025.6 Bile Acids 56225.7 Inclusion Compounds 562Experiment 25 Lipids 566E25.1 Analysis of Oils 566E25.2 Trimyristin From Nutmeg 567E25.3 Preparation of Azelaic Acid from Castor Oil 569E25.4 Urea Complexes of Fatty Acids 570E25.5 Solubility of Cholesterol 570E25.6 Bile Acids 571Unit 26 Polymers 57726.1 Introduction 57726.2 Chain-Reaction Polymerization 57926.3 Step-Reaction Polymerization 58126.4 Polymer Structure 58326.5 Some Typical Polymers 58426.6 Plasticizers 58826.7 Applications and Recycling 58926.8 Identification of Plastics 590Experiment 26 Synthesis and Analysis of Polymers 595 E26.1 Overview 595E26.2 Emulsion Polymerization of Styrene with Persulfate 596E26.3 Emulsion Polymerization of Methyl Methacrylate 597E26.4 Bulk Copolymerization of Styrene and Divinylbenzene: Effect of a Plasticizer 598E26.5 Bulk Polymerization of Methyl Methacrylate 599E26.6 Cellulose Triacetate 599E26.7 Phenolic Resins 601E26.8 Preparation of Nylon 6.6: The Nylon Rope Trick 601E26.9 Analysis of Polymers 602Unit 27 Dyes and Pigments27.1 Dyes, Pigments, and Colors 61127.2 Azo Dyes 61227.3 Synthesis of Azo Dyes 61327.4 Cationic Dyes 61527.5 Anthraquinone Dyes 61627.6 Indigo Dyes 61727.7 Other Dyes 61827.8 Mode of Application 61927.9 Dyeing 620Experiment 27 Colored Chemistry 626E27.1 Direct Dyes 627E27.2 Mordant Dyeing 630E27.3 Ingrain Dyes 630E27.4 Vat Dyes 632E27.5 Dye Fastness 633Unit 28 Bioorganic Chemistry 63528.1 Enzymes: Biological Catalysts 63528.2 How Enzymes Work 63528.3 Using Enzymes 63728.4 Prochiral Molecules 63928.5 Reduction of Ketones 64028.6 Enantiomeric Excess 642Experiment 28 Asymmetric Synthesis with Baker’s Yeast: An Open-Ended Experiment 645E28.1 Overview 645E28.2 Investigating the Course of the Reaction 646E28.3 Conformational Analysis: Determining Whether the Diol is Threo or Erythro (Advanced Level) 647E28.4 Reduction of 1-Pheny1-1,2-Propanedione with Baker’s Yeast 649E28.5 Analysis 650Unit 29 Molecules of Heredity 65329.1 Nucleosides and Nucleotides 65329.2 Base Pairing 65629.3 Purine and Pyrimidine Bases 65729.4 Chemical Transformations 658Experiment 29 Analysis of Nucleosides 662E29.1 Overview of the Experiment 662E29.2 Analysis of an RNA Digest 662E29.3 Deamination of Cytidine to Uridine 664Section 3 Spectroscopy 667Unit 30 Absorption Spectroscopy 66930.1 The Nature of Light 66930.2 Interaction between Electromagnetic Radiation and Matter 67030.3 Absorption Spectroscopy 672Unit 31 Infrared Spectroscopy 67531.1 Molecular Vibrations 67531.2 Stretching and Bending Vibrations 67731.3 IR and Dipole Moment 67931.4 Regions of the IR Spectrum 68031.5 Experimental Aspects 68131.6 Interpreting IR Spectra 68531.7 Case Studies 69331.8 Concentration and Solvent Effects on IR 69531.9 Instrumentation 697Unit 32 Ultraviolet-Visible Spectroscopy 70732.1 Electronic Transitions 70732.2 Chromophores and Auxochromes 70932.3 Structural Effects on UV-Visible Spectra: Woodward—Fieser Rules 71032.4 Applications of UV-Visible Spectroscopy 71132.5 Spectrophotometers 714Unit 33 Nuclear Magnetic Resonance 71933.1 Nuclear Spin 71933.2 The Resonance Phenomenon: A Closer Look 72133.3 Obtaining the NMR Spectrum 72433.4 1H-NMR 72633.5 Electronic Shielding 72733.6 The Chemical Shift 72933.7 Effect of Pi Electrons 73033.8 Hydrogen Equivalence: A Closer Look 73233.9 Integrals 73233.10 Spin-Spin Splitting 73433.11 Typical Coupling Patterns 73933.12 The Coupling Constant 73933.13 Coupling: A Closer Look 74233.14 Chemical Shift Correlations 75033.15 Coupling of Hydrogens Attached to Heteroatoms 75633.16 13C-NMR 75833.17 13C-NMR Chemical Shifts 76033.18 Aromatic Systems 76533.19 Effect of Chirality on the NMR 76833.20 Running the Spectrum 77133.21 Two-Dimensional NMR 77233.22 Interpreting 1H-NMR Spectra 774Unit 34 Mass Spectrometry 78334.1 Overview 78334.2 Instrumentation 78434.3 The Molecular Ion 78534.4 Charge Localization 78934.5 Fragmentations 79034.6 MS Case Studies 79634.7 Interpreting Mass Spectra 79834.8 High-Resolution Mass Spectra 800Answers to Odd-Numbered Exercises 803Credits 821Index 823Index of Spectra 834

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