Table Of Contents:
PREFACE xx
INTRODUCTION: GETTING ACQUAINTED WITH THE LABORATORY 1(12)
I.1 Experimental Organic Chemistry 1(1)
1.2 Laboratory Safety 1(1)
I.3 Cleanup Following an Experiment 2(1)
I.4 Desk Equipment 3(1)
I.5 Introduction to Macroscale and Microscale Laboratory Work 4(1)
I.6 Using Handbooks 5(4)
I.7 Your Laboratory Notebook 9(4)
Part 1 Experiments 13(340)

1 EXTRACTION OF CAFFEINE FROM TEA 15(7)

2 PURIFICATION AND THIN-LAYER CHROMATOGRAPHIC ANALYSIS OF CAFFEINE 22(5)

3 SYNTHESIS OF ETHANOL BY FERMENTATION OF SUCROSE 27(5)

4 SYNTHESIS OF SALICYLIC ACID 32(9)

5 SYNTHESIS OF ASPIRIN 41(8)

Optional Experiment: Thin-Layer Chromatographic Analysis of Analgesics 47(2)

6 RADICAL CHLORINATION REACTIONS 49(5)

7 ISOLATION OF ESSENTIAL OILS AND THE THEORY OF ODOR 54(13)

7.1 Isolation of S-(+)-Carvone from Caraway Seeds 56(7)

7.2 Isolation of R-(+)-Limonene from Orange Peels 63(4)

8 NUCLEOPHILIC SUBSTITUTION REACTIONS 67(15)

8.1 S(N)1/S(N)2 Reactivity of Alkyl Halides 71(5)

8.2 Preparation and Identification of Alkyl Bromides Synthesized from Unknown Alcohols 76(6)

9 ADDITION REACTIONS OF ALKENES 82(21)

9.1 Free Radical versus Ionic Addition of Hydrobromic Acid to Alkenes 83(8)

9.2 Dimerization of 2-Methylpropene (Isobutylene) 91(7)

9.3 Stereochemistry of Bromine Addition to trans-Cinnamic Acid 98(5)

10 DEHYDROHALOGENATION OF 2-BROMOHEPTANE: VARIATION OF PROMOTING BASE 103(5)

11 DEHYDRATION OF ALCOHOLS 108(15)

11.1 Synthesis of Cyclohexene by Acid-Catalyzed Dehydration of Cyclohexanol 110(6)

11.2 Dehydration of 2-Methylcyclohexanol 116(7)

12 ETHER SYNTHESES 123(11)

12.1 Williamson Ether Synthesis of Ethoxybutane 124(5)

12.2 Synthesis and Analysis of a Propyl Benzhydryl Ether 129(5)

13 GRIGNARD SYNTHESES 134(26)

13.1 Synthesis of Phenylmagnesium Bromide and Its Use as a Synthetic Intermediate 138(17)

13.1a Synthesis of Diphenylmethanol (Benzhydrol) 142(6)

13.1b Synthesis of Triphenylmethanol 148(3)

13.1c Synthesis of Benzoic Acid 151(4)

13.2 Grignard Synthesis of a Triphenylmethane Dye: Crystal Violet or Malachite Green 155(5)

14 PHASE TRANSFER CATALYSIS 160(11)

14.1 Williamson Ether Synthesis of Bis-4-Chlorobenzyl Ether Using Phase Transfer Catalysis 162(5)

14.2 Synthesis of Butyl Benzoate Using Phase Transfer Catalysis 167(4)

15 OXIDATION REACTIONS 171(17)

15.1 Oxidation of Cyclohexanol Using Sodium Hypochlorite 174(5)

15.2 General Method for Oxidizing Secondary Alcohols to Ketones 179(4)

15.3 Oxidation of Cinnamyl Alcohol Using Pyridinium Chlorochromate 183(5)

16 DIELS-ALDER REACTIONS 188(13)

16.1 Synthesis of Dimethyl 3,4,5,6-Tetraphenylphthalate from 2,3,4,5-Tetraphenylcyclopentadienone and Dimethyl Acetylene Dicarboxylate 189(5)

16.2 Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic Acid from Butadiene Sulfone and Maleic Anhydride 194(7)

17 ELECTROPHILIC AROMATIC SUBSTITUTION 201(16)

17.1 Iodination of 1,2,4,5-Tetramethylbenzene Using Iodine and Periodic Acid 203(5)

17.2 Bromination of Acetanilide 208(6)

Optional Experiment: Removal of the Acetyl Protecting Group: Synthesis of a Bromoaniline 212(2)

17.3 Rates of Electrophilic Aromatic Substitution 214(3)

18 ACYLATION AND ALKYLATION OF AROMATIC COMPOUNDS 217(19)

18.1 Acylation of Ferrocene 220(6)

18.2 Synthesis of 4,4'-Di-tert-Butylbiphenyl 226(6)

18.3 Synthesis of 1,4-Di-tert-Butyl-2,5-Dimethoxybenzene 232(4)

19 REDUCTION REACTIONS OF 3-NITROACETOPHENONE 236(8)

19.1 Reduction of 3-Nitroacetophenone Using Tin and Hydrochloric Acid 239(2)

19.2 Reduction of 3-Nitroacetophenone Using Sodium Borohydride 241(3)

20 PHOTOCHEMISTRY: PHOTOREDUCTION OF BENZOPHENONE AND REARRANGEMENT TO BENZPINACOLONE 244(8)

21 ALDOL CONDENSATION: REACTION OF BENZALDEHYDE AND ACETONE 252(7)

22 SYNTHESIS OF 2,3,4,5-TETRAPHENYLCYCLOPENTADIENONE 259(8)

23 HORNER-EMMONS-WITTIG SYNTHESIS OF METHYL 4-METHOXY-E-CINNAMATE 267(8)

24 KINETIC VERSUS THERMODYNAMIC CONTROL IN CHEMICAL REACTIONS 275(14)

24.1 Semicarbazones of Cyclohexanone and 2-Furaldehyde 276(8)

24.2 Friedel-Crafts Alkylation of Chlorobenzene 284(5)

Optional Experiments 289(1)

25 SYNTHESIS OF ESTERS 289(16)

25.1 Synthesis of Isopentyl Acetate (Banana Oil) 291(6)

Optional Experiments: Propyl Ethanoate (Propyl Acetate) and 2-Methyl-1-Propyl Propanoate (Isobutyl Propionate) 296(1)

25.2 Synthesis and Identification of an Ester from an Unknown Alcohol and Acetic Acid 297(8)

26 AMIDE CHEMISTRY 305(22)

26.1 Synthesis of Hippuric Acid 306(7)

Optional Experiment: Solubilities of Benzoic Acid and Hippuric Acid 312(1)

26.2 Synthesis of a Mosquito Repellent: N,N-Diethyl-meta-Toluamide (Deet) 313(14)

27 POLYPHOSPHORIC ACID-CATALYZED BECKMANN REARRANGEMENT OF ACETOPHENONE OXIME 327(6)

28 SYNTHESIS OF trans-1,2-DIBENZOCYCLOPROPANE BY RING CLOSURE 333(6)

29 POLYMER CHEMISTRY 339(14)

29.1 Synthesis of Polystyrene 342(7)

Optional Experiment 348(1)

29.2 Biodegradable Starch Films 349(4)
Part 2 Projects 353(144)

1 HYDROLYSIS OF AN UNKNOWN ESTER 355(14)

1.1 Hydrolysis and Azeotropic Distillation 357(3)

1.2 Extraction and Recrystallization 360(4)

1.3 Distillation, Melting Points, and Identification 364(5)

2 SYNTHESIS OF 1-BROMOBUTANE AND A GRIGNARD SYNTHESIS OF AN ALCOHOL 369(14)

2.1 Synthesis of 1-Bromobutane from 1-Butanol 370(5)

Optional Syntheses of Alkyl Halides 374(1)

2.2 Grignard Synthesis of Secondary and Tertiary Alcohols 375(8)

Optional Synthesis 380(3)

3 SYNTHESIS AND DEHYDRATION OF 3,3-DIMETHYL-2-BUTANOL 383(9)

3.1 Synthesis of 3,3-Dimethyl-2-Butanol by Reduction with Sodium Borohydride 384(3)

3.2 Acid-Catalyzed Dehydration of 3,3-Dimethyl-2-Butanol with Rearrangement 387(5)

4 INTERCONVERSION OF 4-tert-BUTYLCYCLOHEXANOL AND 4-tert-BUTYLCYCLOHEXANONE 392(16)

4.1 Sodium Hypochlorite Oxidation of 4-tert-Butylcyclohexanol to 4-tert-Butylcyclohexanone 394(6)

4.2 Sodium Borohydride Reduction of 4-tert-Butylcyclohexanone 400(5)

Optional GC or NMR Experiment 405(3)

5 ALDOL CONDENSATION USING AN UNKNOWN ALDEHYDE AND AN UNKNOWN KETONE: DERIVATIVE FORMATION AND IDENTIFICATION OF UNKNOWNS 408(11)

5.1 Preparation of Aldol Condensation Product 413(1)

5.2 Characterization of the Aldol Product 414(5)

6 BENZOIN CHEMISTRY: SYNTHESIS OF AN ANTICONVULSANT DRUG USING BIOCHEMICAL CATALYSIS 419(16)

6.1 Thiamine-Catalyzed Benzoin Condensation 419(8)

6.2 Oxidation of Benzoin 427(4)

6.3 Synthesis of 5,5-Diphenylhydantoin, an Anticonvulsant Drug 431(4)

7 SYNTHESIS OF BENZOCAINE 435(8)

8 RESOLUTION OF R,S-BENZOYLAMINO ACIDS 443(13)

8.1 Papain 444(4)

8.2 Resolution of R,S-Benzoylamino Acids 448(1)

8.3 Synthesis of the R,S-Benzoylamino Acid 449(3)

8.4 Synthesis of the S-Benzoylamino Acid Anilide: Enzymatic Resolution 452(1)

8.5 Optical Activity of S-Benzoylamino Acid Anilide 453(2)

8.6 Further Experiment 455(1)

9 MULTISTEP SYNTHESIS OF PARA RED FROM ACETANILIDE 456(11)

9.1 Two-Step Synthesis of p-Nitroaniline 459(4)

9.2 Preparation of Diazonium Salts 463(4)

10 SYNTHESES STARTING WITH ALKYL HALIDES 467(4)

11 DIELS-ALDER CYCLOADDITIONS OF VARIOUS DIENOPHILES TO 2,3-DIMETHYL-1,3-BUTADIENE 471(5)

11.1 Synthesis of cis-4,5-Dimethyl-1,2,3,6-Tetrahydrophthalic Anhydride 471(2)

11.2 Addition of Various Dienophiles to 2,3-Dimethyl-1,3-Butadiene 473(3)

12 MULTISTEP SYNTHESIS OF N-PHENYLTETRAPHENYL-PHTHALIMIDE 476(10)

12.1 Synthesis of Tetraphenylcyclopentadienone 478(1)

12.2 Synthesis of Dimethyl Tetraphenylphthalate 479(1)

12.3 Synthesis of Tetraphenylphthalic Acid 480(2)

12.4 Synthesis of Tetraphenylphthalic Anhydride 482(2)

12.5 Synthesis of N-Phenyl-3,4,5,6-Tetraphenylphthalimide 484(2)

13 SUGARS: THE GLUCOSE PENTAACETATES 486(11)

13.1 Preparation of Stereoisomers of D-Glucose 491(2)

13.2 (1)H NMR Analysis of XXX- and XXX-D-Glucose Pentaacetates 493(1)

13.3 Optical Activity of Sugars 493(1)

13.4 Further Investigations 494(3)
Part 3 Organic Qualitative Analysis 497(80)

1 IDENTIFICATION OF UNKNOWNS 499(3)

2 PHYSICAL PROPERTIES 502(2)

3 CLASSIFICATION BY SOLUBILITY AND ELEMENTAL ANALYSIS BY SODIUM FUSION 504(12)

3.1 Classification by Solubility 504(8)

3.2 Elemental Analysis by Sodium Fusion 512(4)

4 INFRARED, NUCLEAR MAGNETIC RESONANCE, AND MASS SPECTROMETRIC ANALYSIS 516(8)

4.1 Using Spectrometric Data 520(4)

5 CLASSIFICATION TESTS FOR FUNCTIONAL GROUPS 524(27)

5.1 Alcohols 526(3)

5.2 Aldehydes and Ketones 529(4)

5.3 Alkenes 533(2)

5.4 Alkyl Halides 535(3)

5.5 Amines 538(3)

5.6 Aromatic Hydrocarbons (Arenes) 541(2)

5.7 Aryl Halides 543(1)

5.8 Carboxylic Acids 543(1)

5.9 Carboxylic Acid Derivatives 544(1)

5.9a Acyl Chlorides 544(1)

5.9b Esters 544(1)

5.10 Amides, Acyl Chlorides, Esters, and Nitriles 545(4)

5.11 Ethers 549(1)

5.12 Phenols 549(2)

6 SYNTHESIS OF SOLID DERIVATIVES 551(13)

6.1 Alcohols 552(3)

6.2 Aldehydes and Ketones 555(2)

6.3 Amines 557(3)

6.4 Carboxylic Acides: Amides, Anilides, Toluidides 560(2)

6.5 Phenols 562(2)

7 SEPARATION OF MIXTURES 564(8)

7.1 Assaying the Number of Compounds 567(1)

7.2 Separating the Mixture 568(3)

7.3 Model Extraction Procedure 571(1)

8 SUMMARY OF IDENTIFICATION PROCEDURE FOR AN UNKNOWN COMPOUND 572(1)

9 SUMMARY OF ANALYSIS OF A MIXTURE OF UNKNOWN COMPOUNDS 573(4)
Part 4 Spectrometric Methods 577(110)

1 INFRARED SPECTROMETRY 579(31)

1.1 Theory of Molecular Vibration 580(1)

1.2 Infrared Spectrum 581(3)

1.3 Infrared Instrumentation 584(4)

1.4 Techniques of Sample Preparation 588(5)

1.5 Interpreting Infrared Spectra 593(17)

2 NMR SPECTROMETRY 610(54)

2.1 NMR Instrumentation 612(2)

2.2 Chemical Shift 614(7)

2.3 Spin-Spin Splitting 621(3)

2.4 Detecting Chemical Equivalence 624(2)

2.5 Integration 626(1)

2.6 Preparing the NMR Sample 627(3)

2.7 Recording the NMR Spectrum 630(1)

2.8 Interpreting (1)H NMR Spectra 630(4)

2.9 (13)C NMR 634(6)

2.10 An Approach to Solving NMR Problems 640(10)

2.11 Two-Dimensional NMR and Related Techniques (Special Topic) 650(14)

3 MASS SPECTROMETRY 664(11)

4 ULTRAVIOLET AND VISIBLE SPECTROMETRY 675(8)

5 INTEGRATED PROBLEMS 683(4)
Part 5 Techniques of the Organic Laboratory 687

1 SAFETY 689(17)

1.1 Causes of Laboratory Accidents 689(3)

1.2 Safety Features of Your Laboratory 692(2)

1.3 Preventing Accidents 694(2)

1.4 What to Do if an Accident Occurs 696(1)

1.5 Chemical Toxicology 697(1)

1.6 Where to Find Chemical Safety Information 698(5)

1.7 Protecting The Environment 703(3)

2 LABORATORY GLASSWARE 706(8)

2.1 Standard Taper Glassware 706(4)

2.2 Microscale Glassware 710(1)

2.3 Cleaning Your Glassware 711(1)

2.4 Pasteur Filter Pipets 712(2)

3 HEATING METHODS 714(10)

3.1 Boiling Stones 714(1)

3.2 Heating Devices 715(4)

3.3 Refluxing a Reaction Mixture 719(5)

3.3a Refluxing a Reaction Mixture under Anhydrous Conditions 720(4)

4 EXTRACTION AND DRYING AGENTS 724(25)

4.1 Extraction: The Theory 726(2)

4.2 Macroscale Extractions 728(2)

4.3 Additional Information about Extractions 730(4)

4.4 Summary of Macroscale Extraction from Water to an Organic Solution 734(1)

4.5 Microscale Extractions 734(8)

4.5a Extracting an Aqueous Solution with an Organic Solvent More Dense Than Water 736(1)

4.5b Washing an Organic Liquid That Is More Dense Than Water 737(4)

4.5c Extraction with an Organic Solvent Less Dense Than Water 741(1)

4.5d Washing an Organic Liquid That Is Less Dense Than Water 741(1)

4.6 Drying Organic Liquids 742(3)

4.7 Methods for Separating Drying Agents and Organic Liquids 745(1)

4.8 Recovery of the Organic Product from the Dried Extraction Solution 746(3)

5 RECRYSTALLIZATION 749(16)

5.1 Theory of Recrystallization 749(3)

5.2 Selecting a Proper Recrystallization Solvent 752(2)

5.2a Recrystallization from Mixed Solvent Pairs 753(1)

5.3 Macroscale Procedure for Recrystallizing a Solid 754(5)

5.3a Removing Impurities from the Recrystallization Solution 756(3)

5.4 Summary of the Macroscale Recrystallization Procedure 759(1)

5.5 Microscale Recrystallization 759(4)

5.5a Recrystallizing 150 to 500 Milligrams of a Solid 759(2)

5.5b Recrystallizing Less than 150 to 500 Milligrams of a Solid in a Craig Tube Apparatus 761(2)

5.6 Summary of the Microscale Recrystallization Procedures 763(1)

5.7 What to Do If No Crystals Appear in the Cooled Solution 763(1)

5.8 Pointers for Successful Recrystallizations 764(1)

6 MELTING POINTS AND MELTING RANGES 765(11)

6.1 Melting Point Theory 766(2)

6.2 Apparatus for Determining Melting Ranges 768(3)

6.3 Determining Melting Ranges 771(2)

6.4 Mixture Melting Points 773(1)

6.5 Thermometer Calibration 774(1)

6.6 Summary of Melting-Point Determination 775(1)

7 BOILING POINTS, DISTILLATION, AND AZEOTROPES 776(29)

7.1 Boiling Points 777(2)

7.1a Determination of Boiling Points 778(1)

7.2 Boiling Points and Separation of Mixtures 779(4)

7.3 Simple Distillation 783(8)

7.3a Short-Path Distillation 788(1)

7.3b Microscale Distillation 789(2)

7.4 Fractional Distillation 791(3)

7.5 Azeotropic Distillation 794(2)

7.6 Steam Distillation 796(2)

7.7 Vacuum Distillation 798(7)

8 SUBLIMATION 805(3)

8.1 Assembling the Apparatus for a Sublimation 806(1)

8.2 Carrying Out a Microscale Sublimation 807(1)

9 REFRACTROMETRY 808(5)

9.1 Theory of Refractometry 809(1)

9.2 The Refractometer 810(1)

9.3 Steps in Determining a Refractive Index 811(1)

9.4 Temperature Correction 812(1)

10 THIN-LAYER CHROMATOGRAPHY 813(13)

10.1 Principles of Thin-Layer Chromatography 815(2)

10.2 Plates for Thin-Layer Chromatography 817(1)

10.3 Sample Application 818(2)

10.4 Choices of Developing Solvent 820(3)

10.5 Visualization Techniques 823(2)

10.6 Summary of TLC Procedure 825(1)

11 GAS-LIQUID CHROMATOGRAPHY 826(15)

11.1 Instrumentation 827(2)

11.2 Columns and Liquid Stationary Phases 829(3)

11.3 Detectors 832(3)

11.4 Interpreting Chromatograms 835(1)

11.5 Practical GC Operating Procedures 836(3)

11.6 Identification of Components and Qualitative Analysis 839(2)

12 LIQUID CHROMATOGRAPHY 841(16)

12.1 Adsorbents 842(2)

12.2 Elution Solvents 844(1)

12.3 Choosing a Column 845(2)

12.4 Making a Macroscale Column 847(1)

12.5 Elution Techniques 848(2)

12.6 Microscale Column Chromatography 850(1)

12.7 Summary of Column Chromatography Techniques 851(1)

12.8 Dry Column Chromatography 852(1)

12.9 Flash Chromatography 852(2)

12.10 High-Performance Liquid Chromatography 854(3)

13 POLARIMETRY 857

13.1 Mixtures of Optical Isomers: Separation/Resolution 857(5)

13.2 Polarimetric Instrumentation 862(2)

13.3 Specific Rotation 864(2)

13.4 Using the Polarimeter 866(1)

13.5 Enantiomeric Excess (Optical Purity) 867
Appendix A DERIVATIVE TABLES FOR ORGANIC QUALITATIVE ANALYSIS A-1
Appendix B THE LITERATURE OF ORGANIC CHEMISTRY B-1
Index I-1