Theory and Practice in the Organic Laboratory

by Landgrebe, John A.

• ISBN13: 9780534168544
• ISBN10: 053416854X
• Edition: 4th
• Format: Hardcover
• Copyright: 1993-05-01
• Publisher: Brooks/Cole Pub Co

Summary

Integrating 52 microscale and standard scale procedures and experiments, this comprehensive organic laboratory text allows all schools-even those that cannot afford a large investment in commercial kits-to do effective microscale experiments. You'll also find standard scale experiments that expose students to techniques and apparatus. This edition covers treatment of safety and hazardous waste disposal; coverage of laboratory techniques for the handling, synthesis, separation, and purification of organic compounds; and inclusion of spectroscopic methods for the identification of compounds.

Table of Contents

Preface
A Word to the Instructor
Part I Tools for the Organic Laboratory
Introduction to the Organic Laboratory	1	(5)
Preparation	2	(1)
Wise Use of Laboratory Time	2	(1)
Neatness	2	(1)
Scientific Notebook	2	(2)
Sources of Information on Properties of Compounds	4	(1)
Units	4	(1)
Calculation of Yield	4	(2)
Emergency Procedures and Safe Laboratory Practices	6	(23)
Emergency Procedures and First Aid	6	(2)
Person Splashed with Burning Liquid or Corrosive Chemical---Treatment of Burns	6	(1)
Corrosive Substance in the Eye	7	(1)
Breathing Stopped	7	(1)
Electric Shock	7	(1)
Ingestion of Chemicals	8	(1)
Severe Bleeding	8	(1)
Minor Cuts and Punctures	8	(1)
Reporting Accidents and Injuries	8	(1)
General Safety Equipment and Orientation	8	(3)
Eye and Face Protection	9	(1)
Clothing	9	(1)
Emergency Fire Equipment	10	(1)
Fire Safety	11	(5)
Characteristics of Burning Solvents	11	(2)
Flammable-Solvent Handling and Storage	13	(1)
Fires and Fire Extinguishers	14	(2)
Chemical Hazards	16	(5)
Toxic and Corrosive Properties	17	(1)
Reactive and Other Chemical Hazards	18	(3)
Hazardous Waste Management	21	(3)
Use of Sanitary Sewers	21	(2)
Other Methods of Disposal or Recycling	23	(1)
Safe Laboratory Procedures	24	(2)
General Behavior, Working Hours, and Housekeeping	24	(1)
Fume Hoods and Safety Shields	25	(1)
Labeling and Storage of Chemicals	26	(1)
Questions and Exercises	26	(3)
Selected Bibliography	27	(2)
General Laboratory Procedures	29	(17)
Weighing and Transferring on a Microscale	29	(3)
Solids	30	(1)
Liquids	30	(2)
Transfer of Solids and Liquids on a Macroscale	32	(1)
Solids	32	(1)
Liquids	32	(1)
Stirring and Mixing	33	(1)
Heating and Temperature Control	34	(4)
Heating Devices	34	(4)
Liquids at Reflux	38	(1)
Solvent Evaporation	38	(2)
Connections	40	(3)
Glass Tubing	40	(1)
Cork and Rubber Stoppers	41	(1)
Flexible Tubing	42	(1)
Ground-Glass Joints	42	(1)
Inspection and Care of Laboratory Apparatus	43	(1)
Questions and Exercises	44	(2)
Examination of Pure Compounds	46	(16)
Melting Points	46	(5)
Experimental Methods	46	(2)
Phase Behavior	48	(3)
Method of Mixed Melting Points	51	(1)
Decomposition Points	51	(1)
Thermometer Calibration	51	(1)
Boiling Points	51	(5)
Experimental Methods	52	(1)
Pressure Effects on Boiling Points	53	(3)
Density of Liquids	56	(1)
Refractive Index	57	(1)
Experimental Method	57	(1)
Optical Rotation	58	(3)
Instrumentation	58	(1)
Sample Preparation	58	(2)
Treatment of Data	60	(1)
Questions and Exercises	61	(1)
Chromatography	62	(47)
Classification	62	(4)
The Chromatogram	65	(1)
Polarity of Molecules	66	(2)
Liquid Chromatography	68	(15)
Adsorbents and Solvents	68	(1)
Thin-Layer Chromatography	69	(6)
Reverse-Phase Thin-Layer Chromatography	75	(1)
Paper Chromatography	76	(1)
Classic Adsorptive Column Chromatography	76	(3)
Flash Column Chromatography	79	(2)
Ion Exchange Chromatography	81	(2)
High-Performance Liquid Chromatography	83	(6)
Instrumentation	83	(2)
Stationary Phases and Columns	85	(2)
Chiral Stationary Phases	87	(1)
Practical Considerations in HPLC	88	(1)
Gas Chromatography	89	(13)
Instrumentation	89	(2)
Columns, Supports, and Stationary Phases	91	(5)
Experimental Factors That Affect GC Resolution	96	(1)
Qualitative Analysis and Collecting Effluent Vapors	97	(1)
Quantitative Analysis	97	(4)
Operating Procedures and Techniques	101	(1)
Theoretical Considerations	102	(1)
Column Efficiency and the van Deemter Equation	102	(1)
Selectivity	103	(1)
Capacity Factor	103	(1)
Questions and Exercises	104	(5)
Selected Bibliography	107	(2)
Crystallization and Filtration	109	(14)
Solubility of Organic Compounds	109	(2)
Temperature Effects	109	(1)
Molecular Structural Effects on Water Solubility	110	(1)
Crystallization Procedures	111	(12)
Choice of Solvent and Solvent Mixtures	111	(1)
Macroscale Techniques	112	(3)
Use of Mixed Solvents	115	(1)
Microscale Techniques	115	(2)
Induction of Crystal Formation	117	(1)
Rate of Crystal Growth and Purity	117	(1)
Oils	118	(1)
Decolorizing with Activated Carbon	118	(1)
Filter Aids	119	(1)
Fractional Crystallization	119	(1)
Use of the Centrifuge	119	(1)
Microscale Crystallization with a Craig Tube	120	(1)
Questions and Exercises	121	(2)
Extraction and Drying	123	(19)
Introduction and Background	123	(9)
Macroscale Procedures	124	(1)
Microscale Procedures	125	(2)
Utilizing Acid---Base Properties in Extractions	127	(2)
Multiple Extractions	129	(3)
Salting Out	132	(1)
Emulsions	132	(1)
Continuous Extraction	132	(1)
Countercurrent Extraction	133	(2)
Drying Organic Liquids	135	(5)
General Considerations of Hydrate-Forming Agents	136	(1)
Specific Hydrate-Forming Agents	136	(2)
Other Agents for Drying Organic Liquids	138	(2)
Questions and Exercises	140	(2)
Distillation and Related Techniques	142	(21)
Nonvolatile Solutes	142	(1)
Vapor Pressure Effects	142	(1)
Volatile Solutes	143	(3)
Consequences of Raoult's Law	143	(2)
Fractionation Efficiency	145	(1)
Distillation Apparatus and Procedures	146	(11)
Simple Distillations	146	(2)
Condensers	148	(1)
Fractional Distillations	149	(3)
Distillations at Reduced Pressure	152	(3)
Vacuum Fractional Distillations	155	(1)
Special Distillation Requirements	156	(1)
Azeotropes---Deviations from Raoult's Law	157	(1)
Sublimation	158	(2)
Steam Distillation	160	(1)
Questions and Exercises	161	(2)
Introduction to Spectroscopy; Organic Structure Determination	163	(8)
The Electromagnetic Spectrum	163	(1)
Hydrogen Deficiency Index	164	(1)
Chemical Methods for Structure Determination	165	(6)
Preliminary Observations	165	(1)
Solubility Properties	165	(2)
Qualitative Elemental Analysis	167	(1)
Classification Tests	168	(2)
Derivative Preparation	170	(1)
Nuclear Magnetic Resonance Spectroscopy	171	(71)
Introduction	171	(2)
Proton Chemical Shift	173	(8)
Local Diamagnetic Shielding	175	(1)
Diamagnetic Anisotropic Shielding and Deshielding	176	(5)
Proton--Proton Coupling	181	(10)
Proton Exchange	188	(3)
Molecular Structure from Proton NMR Spectra	191	(9)
Variable Chemical Shifts	199	(1)
Carbon-13 Spectra	200	(13)
Further Considerations of Proton-Proton Coupling	213	(11)
Other than First-Order Spectra	216	(5)
Long-Range Coupling	221	(2)
Virtual Coupling	223	(1)
Sample Preparation	224	(2)
Special Experimental Procedures	226	(5)
High Fields	226	(1)
Lanthanide Shift Reagents	226	(3)
Chiral Lanthanide Shift Reagents	229	(1)
Homonuclear Decoupling	230	(1)
Further Considerations of NMR Theory	231	(11)
Relaxation	235	(1)
Pulsed Fourier Transform Methods	236	(2)
Tables of Chemical Shift Values	238	(3)
Selected Bibliography	241	(1)
Infrared Spectroscopy	242	(41)
Introduction	242	(3)
Experimental Measurements	245	(6)
Instrumentation	245	(2)
Sampling Techniques	247	(4)
Interpretation of Spectra	251	(13)
Factors Affecting Infrared Absorption Frequency	264	(19)
Selected Bibliography	282	(1)
Mass Spectrometry	283	(22)
Introduction	283	(1)
Fate of the Molecular Ion	284	(1)
Determining Molecular Mass and Formula	285	(5)
Odd and Even Parent Ions	286	(1)
Isotopic Clusters	286	(2)
High-Resolution Spectra---Molecular Formula	288	(2)
Fragmentation of Ions	290	(12)
Odd-Electron and Even-Electron Ions	290	(1)
Types of Fragmentation	290	(1)
Simple Bond Cleavage	291	(1)
Expulsion of Neutral Molecules	292	(1)
McLafferty Rearrangement	293	(1)
Other Cleavages with Rearrangement	294	(8)
Other Ionization Methods	302	(3)
Chemical Ionization	302	(1)
Desorption Ionization	303	(1)
Selected Bibliography	303	(2)
Ultraviolet-Visible Spectroscopy	305	(11)
Electronic Excitation	305	(2)
Quantitative Aspects of the Ultraviolet Spectrum	307	(1)
Experimental Method	308	(1)
Structural Effects	309	(7)
Selected Bibliography	314	(2)
Special Laboratory Procedures	316	(26)
Drying Solids and Gases	316	(3)
Solids	316	(1)
Gases	317	(2)
Azeotropic Dehydration	319	(1)
Using Compressed Gases	319	(1)
Addition of Liquids and Solids to Reaction Vessels	320	(2)
Inert Atmospheres and Anhydrous Reaction Conditions	322	(2)
Constant Temperature Control	324	(1)
Hydrogenation	324	(7)
Techniques at Atmospheric Pressure	325	(4)
Low-Pressure Hydrogenation	329	(1)
High-Pressure Hydrogenation	330	(1)
Pyrolysis	331	(2)
Photochemistry	333	(3)
Apparatus	334	(1)
Sensitization	334	(2)
Solvent Purification	336	(6)
Selected Bibliography	341	(1)
The Organic Chemical Literature	342	(223)
Primary and Secondary Sources of Information	342	(3)
Research Journals	342	(2)
Review Journals and Monographs	344	(1)
On-Line Computer Searches	345	(5)
CAS ON-LINE	345	(1)
Computer Search Strategies	346	(4)
Other Search Methods	350	(4)
Abstract Journals	350	(2)
Guides to the Current Literature	352	(1)
Searching Procedures	352	(2)
Useful References	354	(2)
Laboratory Techniques and Procedures	354	(1)
Nomenclature	355	(1)
Chemical and Physical Properties	355	(1)
Questions and Exercises	356	(4)
Part II Experiments
Experiment 1 Introduction to Organic Microtechniques	360	(3)
Experiment 2 Thin-Layer Chromatography	363	(2)
Experiment 3 Determination of Melting Point	365	(1)
Experiment 4 Column Chromatography	366	(3)
Experiment 5 High-Performance Liquid Chromatography on a Reverse-Phase Column; Natural Products from Spices	369	(3)
Experiment 6 Fractional Distillation; Gas Chromatography	372	(4)
Experiment 7 Natural Products by Extraction; Trimyristin and Cholesterol	376	(4)
Experiment 8 Isolation of an Alkaloid; Caffeine	380	(5)
Experiment 9 Extraction and Crystallization; Acid-Base Properties	385	(2)
Experiment 10 Extraction and Crystallization; Acid-Base Properties	387	(3)
Experiment 11 Free-Radical Halogenation; Relative Reactivity by Product Analysis	390	(5)
Experiment 12 2-Chloro-2-Methylbutane (tert-Amyl Chloride)	395	(3)
Experiment 13 Kinetic Investigation of Unimolecular Solvolysis	398	(5)
Experiment 14 Resolution of a Racemic Modification	403	(3)
Experiment 15 Methylcyclohexenes; Alcohol Dehydration	406	(3)
Experiment 16 Diphenylacetylene from Stilbene	409	(4)
Experiment 17 Oxymercuration and Demercuration	413	(3)
Experiment 18 Hydroboration-Oxidation of 1-Hexene	416	(3)
Experiment 19 Divalent Carbon Intermediates; Phase-Transfer Catalysis	419	(5)
Experiment 20 Homophthalic Acid; Oxidative Cleavage of a Double Bond	424	(3)
Experiment 21 Triphenylcarbinol; Addition of a Grignard Reagent to a Ketone	427	(5)
Experiment 22 The Diels-Alder Reaction of Maleic Anhydride and 1,3- Diphenylisobenzofuran	432	(3)
Experiment 23 Rates of Conversion of Alcohols to Alkyl Bromides	435	(4)
Experiment 24 Oxidation of (-)-Borneol to (-)-Camphor; Specific Rotation	439	(3)
Experiment 25 Selective Oxidations of Alcohols with Collins Reagent and Acidic Dichromate	442	(5)
Experiment 26 Kinetic and Thermodynamic Reaction Conditions	447	(3)
Experiment 27 Heat of Reaction; Measurement of Resonance Energy	450	(5)
Experiment 28 Acetanilide to p-Nitroaniline	455	(3)
Experiment 29 Selective Reductions of m-Nitroacetophenone with Tin and Sodium Borohydride	458	(4)
Experiment 30 Introduction to Infrared Spectroscopy	462	(2)
Experiment 31 Introduction to Nuclear Magnetic Resonance Spectroscopy	464	(2)
Experiment 32 4-Methylbenzophenone; Friedel-Crafts Acylation	466	(4)
Experiment 33 Photoreduction of Aromatic Ketones	470	(4)
Experiment 34 Carbocation Rearrangements	474	(2)
Experiment 35 Aryl Migratory Aptitudes in Carbocation Rearrangements	476	(4)
Experiment 36 Synthesis of Sulfa Drugs; Using a Protected Amino Group	480	(3)
Experiment 37 2-Nitroresorcinol; Use of a Blocking Group	483	(3)
Experiment 38 Phenanthridone; Beckmann Rearrangement	486	(3)
Experiment 39 Chemiluminescence	489	(4)
Experiment 40 Benzoic Acid; Carbonation of a Grignard Reagent	493	(4)
Experiment 41 Fischer Esterification	497	(3)
Experiment 42 Capryl Chloride; Capramide	500	(2)
Experiment 43 Synthetic Organic Polymers	502	(8)
Experiment 44 Complex Metal Hydride Reductions; Benzyl Alcohol	510	(3)
Experiment 45 Conjugate (Michael) Addition to &alfa; β-Unsaturated Carbonyl	513	(7)
Experiment 46 9-Benzal- and 9-Benzylfluorene; Aldol and Cannizzaro-Type Reactions	520	(5)
Experiment 47 Electronic Effects of Substituents in Reactions; Acidity Constant Determination	525	(3)
Experiment 48 Synthetic Dyes	528	(9)
Experiment 49 Forensic Chemistry; Detecting Traces of Blood	537	(5)
Experiment 50 Qualitative Organic Analysis; Classification Tests	542	(12)
Experiment 51 Qualitative Organic Analysis; Unknown Identification	554	(8)
Experiment 52 Spectroscopic Identification of an Unknown	562	(3)
Appendix Answers to Selected Chapter Exercises	565	(8)
Index	573