Experimental Organic Chemistry : A Balanced Approach, Macroscale And Microscale / With Cd - 98 edition

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 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
Iondine 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 E-4-Methoxycinnamate
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

26. 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: Enzymatic Resolution
Optical Activity of S-Benzoylamino Acid Anilide
Optional Experiments

9. Multistep Synthesis of Para Red Acentanilide

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
KPentaacetates
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

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
Mixed 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