Multiscale Operational Organic Chemistry : A Problem-Solving Approach to the Laboratory Course

by Lehman, John W.

• ISBN13: 9780130154958
• ISBN10: 0130154954
• Edition: 1st
• Format: Hardcover
• Copyright: 2009-01-01
• Publisher: Prentice Hall

Summary

This practical laboratory book provides both microscale and multiscale experiments. It encourages readers to think in the laboratory by solving a scientific problem in the process of carrying out an experiment. An "operational" approach is featured, equipping readers to master the major lab operations as they carry out problem solving experiments. Over 400 problems and exercises are provided. A valuable reference for organic chemists and chemical technicians.

Table of Contents

Preface	viii
To the Instructor	viii
Introduction	1	(8)
Laboratory Safety	9	(10)
Part I Mastering the Operations	19	(88)
Learning Basic Operations. The Effect of pH on a Food Preservative	20	(8)
Extraction and Evaporation. Separating the Components of ``Panacetin''	28	(7)
Recrystallization and Melting-Point Measurement. Identifying a Constituent of ``Panacetin''	35	(5)
Heating Under Reflux. Synthesis of Salicylic Acid from Wintergreen Oil	40	(9)
Simple Distillation, Gas Chromatography. Preparation of Synthetic Banana Oil	49	(9)
Fractional Distillation. Separation of Petroleum Hydrocarbons	58	(7)
Addition, Mixing, Sublimation, Preparation of Camphor	65	(7)
Boiling Point, Refractive Index. Identification of a Petroleum Hydrocarbon	72	(6)
Column Chromatography, UV-VIS Spectrometry. Isolation and Isomerization of Lycopene from Tomato Paste	78	(9)
Steam Distillation, Infrared Spectrometry. Isolation and Identification of the Major Constituent of Clove Oil	87	(7)
Thin-Layer Chromatography, NMR Spectrometry. Identification of Unknown Ketones	94	(7)
Vacuum Distillation, Optical Rotation. Optical Activity of α-Pinene	101	(6)
Part II Correlated Laboratory Experiments	107	(352)
Investigation of a Chemical Bond by Infrared Spectrometry	108	(7)
Properties of Common Functional Groups	115	(8)
Thin-Layer Chromatographic Analysis of Drug Components	123	(5)
Separation of an Alkane Clathrate	128	(7)
Isomers and Isomerization Reactions	135	(6)
Structures and Properties of Stereoisomers	141	(8)
Bridgehead Reactivity in an SN1 Solvolysis Reaction	149	(7)
Reaction of Iodoethane with Saccharin, an Ambident Nucleophile	156	(6)
Dehydration of Methylcyclohexanols	162	(10)
Synthesis of 7,7-Dichloronorcarane Using a Phase-Transfer Catalyst	172	(9)
Stereochemistry of the Addition of Bromine to trans-Cinnamic Acid	181	(7)
Preparation of Bromotriphenylmethane and the Trityl Free Radical	188	(8)
Chain-growth Polymerization of Styrene and Methyl Methacrylate	196	(9)
Synthesis of Ethanol by Fermentation	205	(8)
Reaction of Butanols with Hydrobromic Acid	213	(10)
Borohydride Reduction of Vanillin to Vanillyl Alcohol	223	(9)
Synthesis of Triphenylmethanol and the Trityl Carbocation	232	(11)
Identification of a Conjugated Diene from Eucalyptus Oil	243	(7)
Spectral Identification of Terpenoids	250	(7)
Synthesis and Spectral Analysis of Aspirin	257	(8)
Preparation of Nonbenzenoid Aromatic Compounds	265	(10)
Mechanism of the Nitration of Arenes by Nitronium Fluoborate	275	(7)
Friedel-Crafts Acylation of Anisole	282	(9)
Structure of a Natural Product in Anise Oil	291	(7)
Identification of an Oxygen-containing Organic Compound	298	(7)
Wittig Synthesis of 1,4-Diphenyl-1,3-butadiene	305	(8)
Effect of Reaction Conditions on the Condensation of Furfural with Cyclopentanone	313	(9)
Haloform Oxidation of 4'-Methoxyacetophenone	322	(7)
Electronic Effect of a para-Iodo Substituent	329	(9)
Synthesis and Identification of an Unknown Carboxylic Acid	338	(6)
Preparation of the Insect Repellent N, N-Diethyl-meta-toluamide	344	(11)
Synthesis of Dimedone and Measurement of its Tautomeric Equilibrium Constant	355	(8)
Preparation of Para Red and Related Azo Dyes	363	(9)
Reaction of Phthalimide with Sodium Hypochlorite	372	(9)
Identification of an Unknown Amine	381	(7)
Preparation and Mass Spectrum of 2-Phenylindole	388	(10)
Nucleophilic Strength and Reactivity in SNAr Reactions	398	(7)
Structure of an Unknown D-Hexose	405	(9)
Fatty Acid Content of Commerical Cooking Oils	414	(8)
Structure of an Unknown Dipeptide	422	(10)
Multistep Synthesis of Benzilic Acid from Benzaldehyde	432	(10)
Using the Chemical Literature in an Organic Synthesis	442	(7)
A Research Project in Organic Chemistry	449	(10)
Part III Minilabs	459	(54)
Making Useful Laboratory Items	460	(1)
Extraction of Iodine by Dichloromethane	461	(1)
Purification of an Unknown Compound by Recrystallization	462	(1)
Developing and Testing a Hypothesis	462	(2)
Preparation of Acetate Esters	464	(1)
Gas Chromatographic Analysis of Commercial Xylene	465	(1)
Isolation of Caffeine from No-Doz Tablets	466	(1)
A Missing-Label Puzzle	466	(1)
Paper Chromatography of Dyes in Commercial Drink Mixes	467	(2)
Gas Chromatographic Analysis of an Essential Oil from Orange Peel	469	(1)
Identification of an Unknown Felt-Tip-Pen Ink by TLC	470	(1)
Optical Rotation of Turpentine	471	(1)
The Structures of Organic Molecules	472	(1)
Who Else Has My Compound?	473	(1)
Isomers and Molecular Structure	474	(1)
Reactivities of Alkyl Halides in Nucleophilic Substitution Reactions	475	(2)
An SN1 Reaction of Bromotriphenylmethane	477	(1)
Preparation and Properties of a Gaseous Alkene	478	(2)
The Addition of Iodine to α-Pinene	480	(1)
Unsaturation in Commercial Products	481	(1)
Free-Radical Bromination of Hydrocarbons	482	(1)
The Nylon Rope Trick	483	(2)
Nucleophilic Substitution Rates of Alcohols	485	(1)
Photoreduction of Benzophenone to Benzopinacol	486	(1)
Oxidation of Alcohols by Potassium Permanganate	487	(1)
Preparation of a Fluorescent Dye	488	(1)
Diels--Alder Reaction of Maleic Anhydride and Furan	489	(2)
Identification of an Unknown Arene by NMR Spectrometry	491	(1)
Interpretation of a Mass Spectrum	492	(1)
Nitration of Naphthalene	493	(1)
Preparation of Trityl Cations by the Friedel-Crafts Reaction	494	(1)
Air Oxidation of Fluorene to 9-Fluorenone	495	(1)
A Nucleophilic Addition-Elimination Reaction of Benzil	496	(2)
Preparation of Aldol Condensation Products	498	(1)
A Spontaneous Reaction of Benzaldehyde	499	(1)
Acid--Base Strengths of Organic Compounds	500	(2)
Hydrolysis Rates of Esters	502	(1)
Preparation of Benzamide	503	(1)
Synthesis of Dimedone Derivatives of Benzaldehyde	504	(1)
A Diazonium Salt Reaction of 2-Aminobenzoic Acid	505	(1)
Beckmann Rearrangement of Benzophenone Oxime	506	(1)
Dyeing with Indigo	507	(1)
Reaction of Monosaccharides with Phenols	508	(2)
Extraction of Trimyristin from Nutmeg	510	(1)
Preparation of a Soap Using a Phase-Transfer Catalyst	511	(1)
Isolation of a Protein from Milk	512	(1)
Part IV Qualitative Organic Analysis	513	(46)
An Overview of Qual Organic	514	(1)
Preliminary Work	515	(2)
Purification	515	(1)
Measurement of Physical Constants	515	(1)
Physical Examination	516	(1)
Ignition Test	516	(1)
Classification	517	(20)
Solubility Tests	517	(3)
Classification Tests	520	(17)
Spectral Analysis	537	(1)
Infrared Spectra	537	(1)
NMR Spectra	537	(1)
Identification	538	(19)
List of Possibilities	538	(1)
Additional Tests and Data	539	(1)
Preparation of Derivatives	540	(17)
Exercises	557	(2)
Part V The Operations	559	(238)
Basic Operations	560	(1)
Cleaning and Drying Glassware	560	(1)
Using Specialized Glassware	561	(4)
Using Glass Rod and Tubing	565	(3)
Weighing	568	(2)
Measuring Volume	570	(3)
Making Transfers	573	(4)
Operations for Conducting Chemical Reactions	577	(1)
Heating	577	(13)
Cooling	590	(1)
Temperature Monitoring	591	(1)
Mixing	592	(2)
Addition of Reactants	594	(3)
Separation Operations	597	(1)
Gravity Filtration	597	(3)
Vacuum Filtration	600	(3)
Centrifugation	603	(2)
Extraction	605	(10)
Evaporation	615	(5)
Steam Distillation	620	(6)
Column Chromatography	626	(11)
Thin-Layer Chromatography	637	(7)
Paper Chromatography	644	(4)
Washing and Drying Operations	648	(1)
Washing Liquids	648	(2)
Drying Liquids	650	(5)
Drying Solids	655	(2)
Drying and Trapping Gases	657	(4)
Purification Operations	661	(1)
Recrystallization	661	(15)
Sublimation	676	(3)
Simple Distillation	679	(13)
Vacuum Distillation	692	(11)
Fractional Distillation	703	(11)
Measuring Physical Constants	714	(1)
Melting Point	714	(6)
Boiling Point	720	(5)
Refractive Index	725	(3)
Optical Rotation	728	(4)
Instrumental Analysis	732	(1)
Gas Chromatography	732	(9)
High-Performance Liquid Chromatography	741	(4)
Infrared Spectrometry	745	(24)
Nuclear Magnetic Resonance Spectrometry	769	(14)
Ultraviolet-Visible Spectrometry	783	(5)
Mass Spectrometry	788	(9)
Appendixes and Bibliography	797	(38)
I Laboratory Equipment	798	(4)
II Keeping a Laboratory Notebook	802	(1)
III Writing a Laboratory Report	803	(5)
IV Calculations for Organic Synthesis	808	(2)
V Planning an Experiment	810	(2)
VI Properties of Organic Compounds	812	(10)
VII The Chemical Literature	822	(13)
Bibliography	835	(6)
Index	841

Excerpts

To the Instructor This book is a multiscale laboratory textbook based on the third edition of Operational Organic Chemistry. -A Problem-Solving Approach to the Laboratory Course. Every experiment and minilab can be performed by students using either standard scale glassware, such as that available in an organic chemistry lab kit with 19/22 standard-taper joints, or microscale glassware, such as that in a microscale lab kit with 14hO standard-taper joints and threaded connectors. Most of the microscale experiments could be performed successfully with alternative microscale glassware, such as that provided in a Williamson lab kit (described in Microscale and Macroscale Organic Experiments, D.C. Heath and Co.). However, some might need to be scaled down further, and the instructor would have to provide additional instructions regarding the use of the glassware. Some organic chemists regard a microscale experiment as one involving approximately 0.1 g of the limiting reactant. Dealing with such small quantities can be discouraging to students with standard scale fingers, who tend to end up with a drop or a few grains of product, if any. I have adopted a more flexible definition of a microscale experiment as one that can be performed with the glassware available in a typical microscale lab. In writing this textbook, I have been guided by my convictions that students (1) perform better in the organic laboratory course if they master the major lab operations early and apply them throughout, (2) learn organic chemistry better if they keep their minds engaged by approaching each experiment as a problem-solving exercise, and (3) perform any task better if they are sufficiently motivated. Part I of this book is devoted to experiments designed to teach the basic laboratory operations, where an operation, as used here, is a process that uses one or more basic lab techniques-such as heating, cooling, or vacuum filtration-to accomplish some end, such as the purification of a solid. Once students have mastered the major operations by completing the appropriate experiments in Part I, they should be ready to apply those operations in Part II, which contains a large selection of experiments that are correlated with topics found in most organic chemistry lecture textbooks. This operational approach helps students understand that an organic synthesis, for example, is not a unique phenomenon that can be experienced only by mechanically following a detailed "recipe." Rather, it is the outcome of a logical sequence of interrelated operations adapted to the requirements of the synthesis. In addition to teaching lab skills, the experiments in this book are designed to help students develop the observational and critical thinking skills that are essential prerequisites for a successful career in science and in virtually every other profession. From the student's viewpoint, the purpose of each major experiment is the solution of a problem through the application of scientific methodology. Before each experiment, the student must first define the problem based on information provided in a hypothetical Scenario. After a preliminary reading of the experiment, the student should be able to develop a working hypothesis regarding its outcome. During the experiment, the student gathers and evaluates evidence bearing on the problem and, as necessary, reevaluates and revises the hypothesis based on experimental observations and data. Finally, the student tests the hypothesis by obtaining a melting point, a spectrum, a gas chromatogram, or by some other means, and arrives at a conclusion. Because of the level at which most undergraduate organic chemistry are taught, the problems must, of necessity, be kept relatively simple and (with a few exceptions) should not be compared to "real" research problems tackled by professional chemists. It is not the intent of this book to make every student a research chemist; most students who tak