Preface
Introduction: Getting Acquainted with the Laboratory
Experimental Organic Chemistry
Laboratory Safety
Cleanup Following an Experiment
Desk Equipment
Introduction to Macroscale and Microscale Laboratory Work
Using Handbooks
Your Laboratory Notebook
I. Experiments
1. Extraction of Caffeine from Tea
2. Purification and Thin-Layer Chromatographic Analysis of Caffeine
3. Synthesis of Ethanol by Fermentation of Sucrose
4. Synthesis of Salicylic Acid
5. Synthesis of Aspirin
Optional Experiment: Thin-Layer Chromatographic Analysis of Analgesics
6. Radical Chlorination Reactions
7. Isolation of Essential Oils and the Theory of Odor
Isolation of S-(+)-Carvone from Caraway Seeds
Isolation of R-(+)-Limonene from Orange Peels
8. Nucleophilic Substitution Reactions
SN1/SN2 Reactivity of Alkyl Halides
Preparation and Identification of Alkyl Bromides Synthesized from Unknown Alcohols
9. Addition Reactions of Alkenes
Free Radical versus Ionic Addition of Hydrobromic Acid to Alkenes
Dimerization of 2-Methylpropene (Isobutylene)
Stereochemistry of Bromine Addition to trans-Cinnamic Acid
10. Dehydrohalgenation of 2-Bromoheptane: Variation of Promoting Base
11. Dehydration of Alcohols
Synthesis of Cyclohexene by Acid-Catalyzed Dehydration of Cyclohexanol
Dehydration of 2-Methylcyclohexanol
12. Ether Syntheses
Williamson Ether Synthesis of Ethoxybutane
Synthesis and Analysis of a Propyl Benhydryl Ether
13. Grignard Syntheses
Synthesis of Phenylmagnesium Bromide and Its Use as a Synthetic Intermediate
Grignard Synthesis of a Triphenylmethane Dye: Crystal Violet or Malachite Green
14. Phase Transfer Catalysis
Williamson Ether Synthesis of Bis-4-Chlorobenzyl Ether Using Phase Transfer Catalysis
Synthesis of Butyl Benzoate Using Phase Transfer Catalysis
15. Oxidation Reactions
Oxidation of Cyclohexanol Using Sodium Hypochlorite
General Method for Oxidizing Secondary Alcohols to Ketones
Oxidation of Cinnamyl Alcohol Using Pyridinium Chlorochromate
16. Diels-Alder Reactions
Synthesis of Dimethyl 3,4,5,6-Tetraphenylphthalate from 2,3,4,5-Tetraphenylcyclopentadienone and Dimethyl Acetylene Dicarboxylate
Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic Acid from Butadiene Sulfone and Maleic Anhydride
17. Electrophilic Aromatic Substitution
Iodination of 1,2,4,5-Tetramethylbenzene Using Iodine and Periodic Acid
Bromination of Acetanilide
Optional Experiment: Removal of the Acetyl Protecting Group: Synthesis of a Bromoaniline
Rates of Electrophilic Aromatic Substitution
18. Acylation and Alkylation of Aromatic Compounds
Acylation of Ferrocene
Synthesis of 4,4´-Di-tert-Butylbiphenyl
Synthesis of 1,4-Di-tert-Butyl-2,5-Dimethoxybenzene
19. Reduction Reactions of 3-Nitroacetophenone
Reduction of 3-Nitroacetophenone Using Tin and Hydrochloric Acid
Reduction of 3-Nitroacetophenone Using Sodium Borohydride
20. Photochemistry: Photoreduction of Benzophenone and Rearrangement to Benzpinacolone
21. Aldol Condensation: Reaction of Benzaldehyde and Acetone
22. Synthesis of 2,3,4,5-Tetraphenylcyclopentadienone
23. Horner-Emmons-Wittig Synthesis of Methyl 4-Methoxy-E-cinnamate
24. Kinetic versus Thermodynamic Control in Chemical Reactions
Semicarbazones of Cyclohexanone and 2-Furaldehyde
Friedel-Crafts Alkylation of Chlorobenzene
Optional Experiments
25. Synthesis of Esters
Synthesis of Isopentyl Acetate (Banana Oil)
Optional Experiments: Propyl Ethanoate (Propyl Acetate) and 2-Methyl-1-Propyl Propanoate (Isobutyl Propionate)
Synthesis and Identification of an Ester from an Unknown Alcohol and Acetic Acid
Amide Chemistry
Synthesis of Hippuric Acid
Optional Experiment: Solubilities of Benzoic Acid and Hippuric Acid
Synthesis of a Mosquito Repellent: N,N-Diethyl-meta-Toluamide (Deet)
27. Polyphosphoric Acid-Catalyzed Beckmann Rearrangement of Acetophenone Oxime
28. Synthesis of trans-1,2-Dibenzocyclopropane by Ring Closure
29. Polymer Chemistry
Synthesis of Polystyrene
Optional Experiment
Biodegradable Starch Films
II. Projects
1. Hydrolysis of an Unknown Ester
Hydrolysis and Azeotropic Distillation
Extraction and Recrystallization
Distillation, Melting Points, and Identification
2. Synthesis of 1-Bromobutane and a Grignard Synthesis of an Alcohol
Synthesis of 1-Bromobutane from 1-Butanol
Optional Syntheses of Alkyl Halides
Grignard Synthesis of Secondary and Tertiary Alcohols
Optional Synthesis
3. Synthesis and Dehydration of 3,3-Dimethyl-2-Butanol
Synthesis of 3,3-Dimethyl-2-Butanol by Reduction with Sodium Borohydride
Acid-Catalyzed Dehydration of 3,3-Dimethyl-2-Butanol with Rearrangement
4. Interconversion of 4-tert-Butylcyclohexanol and 4-tert-Butylcyclohexanone
Sodium Hypochlorite Oxidation of 4-tert-Butylcyclohexanol to 4-tert-Butylchclohexanone
Sodium Borohydride Reduction of 4-tert-Butylcyclohexanone
Optional GC or NMR Experiment
5. Aldol Condensation Using an Unknown Aldehyde and an Unknown Ketone: Derivative Formation and Identification of Unknowns
Preparation of Aldol Condensation Product
Characterization of the Aldol Product
6. Benzoin Chemistry: Synthesis of an Anticonvulsant Drug Using Biochemical Catalysis
Thiamine-Catalyzed Benzoin Condensation
Oxidation of Benzoin
Synthesis of 5,5-Diphenylhydantoin, an Anticonvulsant Drug
7. Synthesis of Benzocaine
8. Resolution of R,S-Benzoylamino Acids
Papain
Resolution of R,S-Benzoylamino Acids
Synthesis of the R,S-Benzoylamino Acid
Synthesis of the S-Benzoylamino Acid Anilide: Enzymatic Resolution
Optical Activity of S-Benzoylamino Acid Anilide
Further Experiments
9. Multistep Synthesis of Para Red From Acetanilide
Two-Step Synthesis of p-Nitroaniline
Preparation of Diazonium Salts
10. Syntheses Starting with Alkyl Halides
11. Diels-Alder Cycloadditions of Various Dienophiles to 2,3-Dimethyl-1,3-Butadiene
Synthesis of cis-4,5-Dimethyl-1,2,3,6-Tetrahydrophthalic Anhydride
Addition of Various Dienophiles to 2,3-Dimethyl-1,3-Butadiene
12. Multistep Synthesis of N-Phenyltetraphenylphthalimide
Synthesis of Tetraphenylcyclopentadienone
Synthesis of Dimethyl Tetraphenylphthalate
Synthesis of Tetraphenylphthalic Acid
Synthesis of Tetraphenylphthalic Anhydride
Synthesis of N-Phenyl-3,4,5,6-Tetraphenylphthalimide
13. Sugars: The Glucose Pentaacetates
Preparation of Stereoisomers of D-Glucose
1H NMR Analysis of a- and b-D-Glucose Pentaacetates
Optical Activity of Sugars
Further Investigations
III. Organic Qualitative Analysis
1. Identification of Unknowns
2. Physical Properties
3. Classification by Solubility and Elemental Analysis by Sodium Fusion
Classification by Solubility
Elemental Analysis by Sodium Fusion
4. Infrared, Nuclear Magnetic Resonance, and Mass Spectrometric Analysis
Using Spectrometric Data
5. Classification Tests for Functional Groups
Alcohols
Aldehydes and Ketones
Alkenes
Alkyl Halides
Amines
Aromatic Hydrocarbons (Arenes)
Aryl Halides
Carboxylic Acids
Carboxylic Acid Derivatives
Amides, Acyl Chlorides, Esters, and Nitriles
Ethers
Phenols
6. Synthesis of Solid Derivatives
Alcohols
Aldehydes and Ketones
Amines
Carboxylic Acids: Amides, Anilides, Toluidides
Phenols
7. Separation of Mixtures
Assaying the Number of Compounds
Separating the Mixture
Model Extraction Procedure
8. Summary of Identification Procedure for an Unknown Compound
9. Summary of Analysis of a Mixture of Unknown Compounds
IV. Spectrometric Methods
1. Infrared Spectrometry
Theory of Molecular Vibration
Infrared Spectrum
Infrared Instrumentation
Techniques of Sample Preparation
Interpreting Infrared Spectra
2. NMR Spectrometry
3. Mass Spectrometry
4. Ultraviolet and Visible Spectrometry
V. Techniques of the Organic Laboratory
1. Safety
Causes of Laboratory Accidents
Safety Features of Your Laboratory
Preventing Accidents
What to Do if an Accident Occurs
Chemical Toxicology
Where to Find Chemical Safety Information
Protecting The Environment
2. Laboratory Glassware
Standard Taper Glassware
Microscale Glassware
Cleaning Your Glassware
Pasteur Filter Pipets
3. Heating Methods
Boiling Stones
Heating Devices
Refluxing a Reaction Mixture
4. Extraction and Drying Agents
Extraction: The Theory
Macroscale Extractions
Additional Information about Extractions
Summary of Macroscale Extraction from Water to an Organic Solution
Microscale Extractions
Drying Organic Liquids
Methods for Separating Drying Agents and Organic Liquids
Recovery of the Organic Product from the Dried Extraction Solution
5. Recrystallization
Theory of Recrystallization
Selecting a Proper Recrystallization Solvent
Macroscale Procedure for Recrystallizing a Solid
Summary of the Macroscale Recrystallization Procedure
Microscale Recrystallization
Summary of the Microscale Recrystallization Procedures
What to Do If No Crystals Appear in the Cooled Solution
Pointers for Successful Recrystallizations
6. Melting Points and Melting Ranges
Melting Point Theory
Apparatus for Determining Melting Ranges
Determining Melting Ranges
Mixture Melting Points
Thermometer Calibration
Summary of Melting-Point Determination
7. Boiling Points, Distillation, and Azeotropes
Boiling Points
Boiling Points and Separation of Mixtures
Simple Distillation
Fractional Distillation
Azeotropic Distillation
Steam Distillation
Vacuum Distillation
8. Sublimation
Assembling the Apparatus for a Sublimation
Carrying Out a Microscale Sublimation
9. Refractometry
Theory of Refractometry
The Refractometer
Steps in Determining a Refractive Index
Temperature Correction
10. Thin-Layer Chromatography
Principles of Thin-Layer Chromatography
Plates for Thin-Layer Chromatography
Sample Application
Choices of Developing Solvent
Visualization Techniques
Summary of TLC Procedure
11. Gas-Liquid Chromatography
Instrumentation
Columns and Liquid Stationary Phases
Detectors
Interpreting Chromatograms
Practical GC Operating Procedures
Identification of Components and Qualitative Analysis
12. Liquid Chromatography
Adsorbents
Elution Solvents
Choosing a Column
Making a Macroscale Column
Elution Techniques
Microscale Column Chromatography
Summary of Column Chromatography Techniques
Dry Column Chromatography
Flash Chromatography
High-Performance Liquid Chromatography
13. Polarimetry
Mixtures of Optical Isomers: Separation/Resolution
Polarimetric Instrumentation
Specific Rotation
Using the Polarimeter
Enantiomeric Excess (Optical Purity)
Appendix A Derivative Tables for Organic Qualitative Analysis
Appendix B The Literature of Organic Chemistry
Index
