Microscale techniques for the organic laboratory / Dana W. Mayo, Peter Trumper, Ronald M. Pike.

Format:

Book

Author/Creator:

Mayo, Dana W.

Contributor:

Trumper, Peter K., 1955-

Pike, Ronald M.

Language:

English

Subjects (All):

Chemistry, Organic--Laboratory manuals.

Chemistry, Organic.

Genre:

Laboratory manuals.

Handbooks and manuals.

Physical Description:

xvii, 319 pages : : illustrations ; 25 cm

Edition:

Second edition.

Other Title:

Microscale

Place of Publication:

New York : Wiley, 2001.

Contents:

General Rules for the Microscale Laboratory 3

The Organic Chemistry Laboratory 4

Chapter 2 Safety 6

Making the Laboratory a Safer Place 6

Nature of Hazards 7

Reduction of Risks 7

Precautionary Measures 9

Thinking about the Risks in Using Chemicals 9

Disposal of Chemicals 10

Material Safety Data Sheets 10

Alternate Sources of Information 14

Estimating the Risks from Vapors 14

Concluding Thoughts 16

Chapter 3 Introduction to Microscale Organic Laboratory Equipment and Techniques 19

Microglassware Equipment 20

Standard Taper Joints 20

Conical Vials 22

Condensers 22

Distillation Heads 22

Recrystallization Tubes 22

Miscellaneous Items 23

Gas Chromatographic Fraction Collection Items 23

Standard Experimental Apparatus 23

Heating and Stirring Arrangements 23

Sand Bath Technique/Hotplate Calibration 23

Metal Heat-Transfer Devices 25

Stirring 25

Reflux Apparatus 25

Distillation Apparatus 27

Moisture-Protected Reaction Apparatus 29

Specialized Pieces of Equipment 30

Microscale Laws 32

Rules of the Trade for Handling Organic Materials at the Microscale Level 32

Rules for Working with Liquids at the Microscale Level 32

Rules for Working with Solids at the Microscale Level 36

The Laboratory Notebook 36

Example of a Laboratory Notebook Entry 38

Calculation of Yields 40

Chapter 4 Determination of Physical Properties 42

Liquids 43

Ultramicro-Boiling Point 43

Density 47

Refractive Index 49

Solids 52

Melting Points 52

Simple Capillary Melting Point 52

Evacuated Melting Points 53

Mixture Melting Points 55

Chapter 5 Microscale Laboratory Techniques 57

Technique 1 Microscale Separation of Liquid Mixtures by Preparative Gas Chromatography 57

GC Instrumentation 58

Procedure for Preparative Collection 62

Example [1A] The Separation of a 25-[mu]L Mixture of Heptanol (bp 153 [degree]C) and Cyclohexanol (bp 160 [degree]C) by Gas Chromatography 64

Example [1B] The Separation of a 40-[mu]L Mixture of (1S)-(

)

[alpha]-Pinene (bp 156 [degree]C) and (1S)-(

)-[beta]-Pinene (bp 165 [degree]C) by Gas Chromatography 69

Example [1C] The Separation of a 40-[mu]L Mixture of 2-Heptanone (bp 149-150 [degree]C) and Cyclohexanol (bp 160-161 [degree]C) by Gas Chromatography 70

Example [1D] The Separation of a 40-[mu]L Mixture of d-Limonene (bp 175-176 [degree]C) and Cyclohexyl acetate (bp 173 [degree]C) by Gas Chromatography 70

Techniques 2 and 3: Distillation 72

Technique 2 Simple Distillation at the Semimicroscale Level 73

Example [2A] Simple Semimicroscale Distillation: Separation of Hexane and Toluene 76

Technique 3 Fractional Semimicroscale Distillation 79

Example [3A] Fractional Semimicroscale Distillation: Separation of 2-Methylpentane and Cyclohexane Using a Spinning-Band Column 83

Example [3B] Fractional Semimicroscale Distillation: Separation of 2-Methylpentane and Cyclohexane Using a Spinning-Band in a Hickman-Hinkle Still 87

Technique 4 Solvent Extraction 90

Solubility 90

Partition Coefficient 94

Extraction 96

Liquid-Liquid Extraction 96

Microscale Extraction 96

Separatory Funnel

Semimicroscale Macroscale Extraction 100

Continuous Liquid-Liquid Extraction 101

Separation of Acids and Bases 102

Salting Out 104

Solid-Liquid Extraction 104

Drying Agents 106

Solid-Phase Extraction 108

Technique 5 Crystallization 110

General Crystallization Procedure 111

Simple Crystallization 112

Filtration Techniques 113

Use of the Hirsch Funnel 113

A Hirsch Funnel Alternative

Nail-filter Funnel 116

Craig Tube Crystallizations 116

Technique 6 Chromatography 119

Technique 6A Column, Flash, High-Performance, Liquid, Paper, and Thin-Layer Chromatography 119

Column Chromatography 119

Packing the Column 120

Sample Application 121

Elution of the Column 122

Fraction Collection 123

Flash Chromatography 123

Thin-Layer Chromatography 125

Paper Chromatography 128

High-Performance Liquid Chromatography 129

Technique 6B Concentration of Solutions 130

Distillation 130

Evaporation with Nitrogen Gas 130

Removal of Solvent Under Reduced Pressure 131

Technique 7 Collection and Control of Gaseous Products 134

Water Insoluble Gases 134

Trapping Byproduct Gases 135

Technique 8 Measurement Of Specific Rotation 137

Theory 137

The Polarimeter 139

Inaccurate Measurements 141

High-Performance Polarimeters and Optical Rotary Dispersion 141

Applications to Structure Determination in Natural Products 141

Technique 9 Sublimation 142

Sublimation Theory 143

Experimental Set-up 143

Precautions 144

Technique 10 Introduction to Infrared Spectroscopy 146

Introduction to Group Frequencies: Interpretation of Infrared Spectra 148

Strategies for Interpreting Infrared Spectra 149

A Survey of Group Frequencies Identified in Organic Molecules 150

Group Frequencies of the Hydrocarbons 151

Alkanes 151

Alkenes C=C Stretching 153

Alkene C

H 153

Alkynes 153

Arenes 154

Group Frequencies of Carbonyl Groups 154

Factors that Raise the C=O Frequency 154

Factors that Lower the C=O Frequency 155

Group Frequencies of the Heteroatom Functional Groups 156

Hexane 156

Alcohols 156

Aldehydes 157

Ketones 157

Esters 157

Acyl Halides 157

Carboxylic Acids 157

Anhydrides 158

Ethers 159

Primary Amines 159

Nitriles 159

Primary Amides 159

Secondary Amides 160

Isocyanates 161

Thiols 161

Alkyl Halides 161

Aryl Halides (Chlorobenzene) 162

Infrared Spectroscopy: Instrumentation and Sample Handling 162

Instrumentation 162

Sample Handling in the Infrared 163

Liquid Samples 163

Solution Spectra and Spectra of Materials Boiling Below 100 [degree]C 164

Solid Samples 164

Infrared Analysis: Reduction of Ketones Using a Metal Hydride Reagent: Cyclohexanone to Cyclohexanol 166

A Spectral Comparison of Reactant and Product 166

Infrared Analysis: An Additional Example of the Reduction of t-Butylcyclohexanone 168

Technique 11 Introduction to Nuclear Magnetic Resonance Spectroscopy 179

Nuclear Spin 179

Instrumentation 180

Chemical Shift 183

Spin-Spin Coupling 184

Intensities 188

Second-Order Effects 188

Interpretation of [superscript 1]H NMR Spectra 189

[superscript 1]H Chemical Shifts 192

Spin-Spin Coupling 194

Geminal Coupling 194

Vicinal Coupling 194

Long-Range Coupling 195

Examples of Complex, Yet First-Order, Coupling 196

Ethyl Vinyl Ether 196

Allyl Acetate 198

4-tert-Butylcyclohexanol 201

[superscript 13]C NMR Spectroscopy 203

Two-Dimensional Nuclear Magnetic Resonance Spectroscopy 209

Nuclear Magnetic Resonance Spectroscopy Sampling 212

Technique 12 Introduction to Ultraviolet-Visible Spectroscopy Absorption Spectroscopy: Theory 218

UV-Vis Spectroscopy 220

Applications to Organic Molecules 222

Instrumentation 231

Sample Preparation 234

Technique 13 Introduction to Mass Spectrometry 237

Instrumentation 240

Ion Source 240

Mass Analyzer 241

Detector 243

Tuning the Mass Spectrometer 244

Sample Introduction 244

Gas Chromatography/Mass Spectrometry 245

Capillary Columns 245

Split Injection 246

Split/Splitless Injection 246

Features of the Mass Spectrum 248

Isotope Peaks 248

Recognizing the Molecular Ion 249

Mass Spectral Interpretation 252

Case Study: Synthesis of Methyl Benzoate 253

Chapter 10 Qualitative Identification of Organic Compounds Organic Qualitative Analysis 259

Preliminary Tests 261

Separation of Impurities 264

Detection of Elements Other Than Carbon, Hydrogen, and Oxygen 264

Solubility Characteristics 270

The Classification Tests 272

Preparation of Derivatives 289

Carboxylic Acids 290

Alcohols 292

Aldehydes and Ketones 294

Amines 295

Acid Chlorides and Anhydrides 296

Aromatic Hydrocarbons 297

Nitriles 297

Phenols 298

Aliphatic Hydrocarbons, Halogenated, Hydrocarbons, Amides, Nitro Compounds, Ethers, and Esters 298.

Notes:

Includes bibliographical references and index.

ISBN:

0471249092

OCLC:

45804718

Online:

Table of Contents