Experimental Organic Chemistry

by Palleros, Daniel R.

• ISBN13: 9780471282501
• ISBN10: 0471282502
• Edition: 1st
• Format: Hardcover
• Copyright: 2000-02-04
• Publisher: Wiley

Summary

This cutting-edge lab manual takes a multiscale approach, presenting both micro, semi-micro, and macroscale techniques. The manual is easy to navigate with all relevant techniques found as they are needed. Cutting-edge subjects such as HPLC, bioorganic chemistry, multistep synthesis, and more are presented in a clear and engaging fashion.

Author Biography

Daniel R. Palleros is the author of Experimental Organic Chemistry, published by Wiley.

Table of Contents

SECTION 1 THE BASICS	1	(58)
Laboratory Safety	3	(16)
General Safety Guidelines	3	(3)
Chemical Toxicity	6	(1)
Dealing with Chemicals and Waste Disposal	7	(8)
Online Safety Resources	15	(4)
Basic Concepts	19	(26)
Polarity and H-Bonds	19	(4)
Physical Data	23	(1)
Solvents	24	(2)
Balancing Chemical Equations	26	(2)
Concentration Units	28	(1)
Moles and Millimoles	29	(2)
Mineral Acids	31	(1)
Calculation of Yields	32	(2)
Scaling Up, Scaling Down	34	(1)
Keeping Lab Books and Writing Lab Reports	34	(1)
Chemical Literature	35	(10)
Basic Operations	45	(14)
Handling Liquids	45	(1)
Heating	46	(1)
Filtration	47	(4)
Refluxing	51	(2)
Evaporation	53	(2)
Centrifugation	55	(1)
Caring for Glassware	55	(2)
Measuring Pressure	57	(2)
SECTION 2 THE EXPERIMENTS	59	(608)
Recrystallization and Melting Point	61	(25)
Overview	61	(1)
Recrystallization	62	(7)
Decolorizing Charcoal	69	(1)
Recrystallization from Mixed Solvents	70	(1)
Microscale Recrystallization	70	(1)
Melting Point	71	(4)
Sublimation	75	(11)
Recrystallization of Acetanilide and Urea	79	(1)
Recrystallization of Acetanilide	80	(2)
Microscale Recrystallization of Urea	82	(1)
Determination of Melting Points	82	(4)
Extraction	86	(27)
Introduction	86	(1)
Solvent-Solvent Partitioning	86	(6)
Macroscale Liquid-Liquid Extraction	92	(1)
Microscale Liquid-Liquid Extraction	93	(1)
Drying the Organic Layer	94	(1)
Solid-Liquid Extraction	95	(2)
Countercurrent Distribution	97	(16)
Isolation of Caffeine from Tea	103	(1)
Tea, Coffee, and Caffeine	103	(2)
Caffeine from Tea: Overview of the Experiment	105	(4)
Isolation of Caffeine	109	(1)
Purification of Caffeine by Sublimation	110	(1)
Purification of Caffeine by Recrystallization (Alternative Procedure)	111	(2)
Distillation---Separation and Purification of Organic Liquids	113	(31)
Boiling Point	113	(1)
Boiling Point and Molecular Structure	114	(1)
Simple Distillation	115	(5)
Fractional Distillation	120	(3)
Ideal and Nonideal Solutions	123	(1)
Azeotropic Mixtures	124	(1)
Fractionating Columns	125	(1)
Microscale Distillation	126	(2)
Boiling Point Determination	128	(1)
Vacuum Distillation	129	(1)
Steam Distillation	130	(14)
Distillation of Alcohols	136	(1)
Distillation of Methanol from a Mixture with Ferric Chloride	136	(1)
Separation of Methanol-Water by Simple Distillation	137	(1)
Separation of Methanol-Water by Fractional Distillation	138	(1)
Analysis of the Distillation Fractions by Density	139	(3)
Isolation of Anise Oil	142	(1)
Overview	142	(1)
Isolation of Anise Oil	142	(2)
Gas Chromatography	144	(28)
Introduction	144	(1)
The Chromatographic Methods	144	(2)
Partition Chromatography	146	(3)
Gas Chromatography	149	(2)
The Gas Chromatograph	151	(4)
Measuring the Retention Time	155	(1)
Integration	156	(1)
Quantitative Analysis	157	(1)
Quantitative Analysis: A Closer Look (Advanced Level)	158	(3)
Qualitative Analysis	161	(1)
Running GC: Step by Step	162	(1)
Gas Chromatography Do's and Don'ts	163	(9)
Gas Chromatography of Alcohols	167	(1)
Analysis of Alcohols	167	(1)
Separation of Methanol and Water	168	(2)
Analysis of Anise Oil	170	(1)
Analysis of Anise Oil	170	(2)
Thin-Layer Chromatography	172	(25)
Overview	172	(1)
The Adsorption Process	173	(2)
Selection of TLC Conditions	175	(3)
Running TLC Plates	178	(4)
Adsorption Isotherms (Advanced Level)	182	(2)
Applications of TLC	184	(2)
Other Stationary Phases	186	(1)
TLC Do's and Don'ts	186	(11)
TLC Analysis of Vegetable Extracts	190	(1)
Plant Pigments	190	(2)
Isolation and Analysis of Plant Pigments	192	(5)
Column Chromatography	197	(17)
Overview	197	(1)
Practical Aspects	197	(5)
Applications	202	(1)
Column Chromatography Do's and Don'ts	203	(11)
Isolation of C60 from Fullerene Soot	206	(1)
Fullerenes	206	(1)
Isolation of Fullerenes	207	(1)
A Chemical Test for Fullerenes	208	(1)
Overview of the Experiment	209	(1)
Isolation of C60 from Fullerene Soot	209	(5)
High-Performance Liquid Chromatography	214	(24)
Overview	214	(1)
HPLC Systems	214	(1)
HPLC Versus GC	215	(1)
Solvents	216	(1)
Pumps	217	(1)
Injection Port	217	(1)
Columns	218	(1)
Detectors	219	(1)
Why is HPLC High Performance?	220	(1)
Reversed-Phase Chromatography	221	(1)
Other Chemically Bonded Stationary Phases	222	(1)
Size-Exclusion Chromatography	223	(1)
Quantitative Determinations: Standard Curve Method	224	(1)
HPLC Do's and Don'ts	224	(14)
Vitamin Analysis---A Quantitative Study	227	(1)
Water-Soluble and Fat-Soluble Vitamins	227	(2)
Vitamin Stability	229	(1)
International Units	230	(1)
Characterization of Vitamin A	230	(1)
Overview of the Experiment	231	(7)
Refractometry and Polarimetry	238	(23)
Refractive Index	238	(1)
The Refractometer	239	(1)
Measuring the Refractive Index	240	(2)
Polarimetry	242	(3)
The Polarimeter	245	(1)
Measuring the Optical Rotation	246	(1)
Optical Rotation of Mixtures	247	(14)
Analysis of Essential Oils	250	(1)
Terpenoids	250	(2)
Essential Oils	252	(1)
Specific Rotation	253	(1)
Refractive Index	253	(1)
Composition of Essential Oils	253	(2)
Separation of Carvone and Limonene	255	(1)
Carvone and Limonene	255	(1)
Analysis of the Crude Oils	256	(1)
Separation of Carvone and Limonene	257	(4)
Alcohols and Alkenes	261	(12)
Alkenes from Alcohols	261	(1)
Dehydration Mechanisms	262	(2)
Characterization of Alkenes	264	(9)
The Dehydration of Methylcyclohexanols	268	(1)
Overview	268	(1)
Dehydration of Methylcyclohexanols	269	(1)
Analysis of the Product Mixture	270	(3)
Alkyl Halides	273	(19)
Preparation	273	(1)
Reactions	274	(1)
Alkyl Halides from Alcohols	274	(2)
Characterization Tests	276	(16)
Synthesis of n-Butyl Bromide and 2-Chloro-2-Methylbutane	280	(1)
Synthesis of n-Butyl Bromide	280	(4)
Synthesis of 2-Chloro-2-Methylbutane	284	(1)
Characterization Tests	285	(7)
Acid-Base Extraction	292	(31)
Introduction	292	(1)
Acids and Bases	292	(2)
Structural Effects on Acid-Base Properties	294	(4)
Acid-Base Extraction	298	(5)
Overview	303	(20)
Isolation of Eugenol from Cloves	307	(1)
Ancient Medicine	307	(1)
Eugenol from Cloves: Overview of the Experiment	307	(1)
Isolation of Eugenol	308	(2)
GC and IR Analyses	310	(5)
Isolation of the Active Ingredients in an Analgesic Tablet	315	(1)
Overview	315	(2)
Separation of the Active Ingredients in Excedrin	317	(1)
Analysis	317	(6)
Phenols and Ethers	323	(13)
Phenols and Ethers	323	(1)
Williamson Ether Synthesis	323	(1)
Characterization of Phenols: Ferric Chloride Test	324	(1)
IR and NMR of Phenols and Ethers	325	(11)
Medicinal Chemistry: From Tylenol to a Banned Chemical	327	(1)
Analgesics	327	(2)
The Experiment: Overview	329	(1)
Conversion of Acetaminophen into Phenacetin	330	(2)
Ferric Chloride Test	332	(1)
Analysis of Analgesics by TLC	332	(4)
Electrophilic Aromatic Substitution	336	(19)
Mechanism of Electrophilic Aromatic Substitution	336	(1)
Nitration and Halogenation	337	(1)
Effects of Substituents	338	(17)
Iodination of Tyrosine	342	(1)
Synthesis of 3,5-Diiodotyrosine	342	(8)
Two Substitution Puzzles	350	(1)
Overview	350	(1)
NMR Analysis	351	(1)
Nitration of Phenacetin	352	(1)
Bromination of Phenacetin	353	(2)
Nucleophilic Aromatic Substitution	355	(13)
Nucleophilic Aromatic Substitution	355	(1)
Dinitroanilines	356	(12)
Dinitrocompounds-Herbicides	360	(1)
Synthesis of Trifluralin	360	(1)
Synthesis of N-(n-Butyl)-2,4-Dinitroaniline	361	(1)
Herbicide Effects of Trifluralin and N-(n-Butyl)-2,4-Dinitroaniline	362	(6)
Chemical Kinetics	368	(23)
Mechanistic Studies	368	(1)
Chemical Kinetics	368	(2)
Experimental Aspects	370	(1)
Integrated Rate Equations	370	(2)
Reaction Half-Life	372	(1)
Transition States	372	(3)
Dependence of the Rate Constant with Temperature: Arrhenius Equation	375	(1)
Following the Kinetics	375	(2)
Best Fit	377	(14)
Nucleophilic Aromatic Substitution Kinetics	381	(1)
The Problem	381	(2)
To Follow the Kinetics	383	(1)
Overview of the Experiment	383	(1)
Synthesis of 2,4-Dinitroanisole	384	(1)
Visible Spectrum of N-(n-Butyl)-2,4-Dinitroaniline	384	(1)
Beer's Law of N-(n-Butyl)-2,4-Dinitroaniline	385	(1)
Kinetics of the Reaction of 2,4-Dinitroanisole with n-Butylamine in Methanol	385	(6)
Diels-Alder Reaction	391	(24)
Diels-Alder Reaction	391	(1)
Endo versus Exo	392	(1)
Solvent Effects	393	(2)
Experimental Considerations: Following the Reaction	395	(20)
Diels-Alder Reactions in Toluene	398	(1)
Reaction of 9-Anthraldehyde with Maleic Anhydride	398	(2)
Reaction of Phencyclone with Norbornadiene	400	(8)
Diels-Alder Reaction in Water	408	(1)
Reaction of 9-Anthracenemethanol with N-Ethylmaleimide	408	(1)
Kinetics of the Reaction of 9-Anthracenemethanol with NEM	409	(6)
Aldehydes and Ketones	415	(23)
Introduction	415	(1)
Preparation	416	(1)
Reactions of Aldehydes and Ketones	416	(7)
IR and NMR of Aldehydes and Ketones	423	(15)
Identification of Aldehydes and Ketones	427	(1)
Characterization Tests	428	(2)
Preparation of Derivatives	430	(1)
The Unknown	430	(3)
Synthesis of trans-Cinnamic Acid	433	(1)
Synthesis of trans-Cinnamic Acid:Perkin Condensation	433	(5)
Oxidation-Reduction	438	(35)
Overview	438	(1)
Selectivity	439	(1)
Oxidations	440	(4)
Phase Transfer Catalysis	444	(1)
Reductions	445	(28)
Oxidation-Reduction	451	(1)
Reduction of Benzophenone	451	(1)
Oxidation of Benzhydrol	452	(1)
Reduction of trans-Cinnamaldehyde	453	(1)
Oxidation of trans-Cinnamyl Alcohol	454	(1)
Reduction of Camphor	455	(1)
Oxidation of Isoborneol	456	(1)
Synthesis of Terephthalic Acid	456	(2)
Monoreduction of m-Dinitrobenzene	458	(15)
Esters	473	(26)
Esters in Nature and Society	473	(1)
Preparation of Esters	474	(2)
Acetylation	476	(1)
Ester Hydrolysis	476	(1)
Characterization of Esters	477	(1)
IR and NMR of Esters and Carboxylic Acids	477	(22)
Preparation of Fruity Fragrances	480	(1)
Preparation of Methyl trans-Cinnamate: A Component of Strawberry Aroma	480	(2)
Preparation of n-Propyl Acetate and Isoamyl Acetate	482	(2)
Hydroxamic Acid Test	484	(7)
Transforming Bengay into Aspirin	491	(1)
Overview	491	(2)
Separation of Methyl Salicylate	493	(1)
Hydrolysis of Methyl Salicylate	493	(1)
Synthesis of Aspirin	494	(1)
Analysis	494	(5)
Multistep Synthesis	499	(33)
Overview	499	(1)
Multistep Synthesis	500	(2)
Retrosynthetic Analysis	502	(5)
Planning a Multistep Synthesis	507	(1)
Linear versus Convergent Synthesis	508	(24)
Synthesis of an Ant Alarm Pheromone: 2-Methyl-4-Heptanone	511	(1)
Overview	511	(1)
Synthetic Route	511	(1)
Grignard Reactions	512	(2)
Oxidation of Secondary Alcohols	514	(1)
Synthesis of 2-Methyl-4-Heptanol	514	(2)
Synthesis of 2-Methyl-4-Heptanone	516	(1)
Vacuum Distillation	516	(4)
Synthesis of Ionones: An Open-Ended Experiment	520	(1)
Ionones	520	(1)
Synthetic Pathway	520	(2)
Characterization of Ionones	522	(1)
Preparation of Pseudoionones	523	(1)
Cyclization with Sulfuric Acid-Acetic Acid	524	(1)
Cyclization with Phosphoric Acid	525	(7)
Molecules of Life	532	(24)
Proteins	532	(7)
Carbohydrates	539	(17)
Chemistry of Milk	546	(1)
Composition of Milk	546	(3)
Isolation and Characterization of Casein	549	(3)
Isolation and Characterization of Lactose	552	(4)
Lipids	556	(21)
Fats and Oils	556	(2)
Characterization of Oils	558	(1)
Uncommon Fatty Acids and Related Compounds	559	(1)
Saponification	560	(1)
Steroids	560	(2)
Bile Acids	562	(1)
Inclusion Compounds	562	(15)
Lipids	566	(1)
Analysis of Oils	566	(1)
Trimyristin From Nutmeg	567	(2)
Preparation of Azelaic Acid from Castor Oil	569	(1)
Urea Complexes of Fatty Acids	570	(1)
Solubility of Cholesterol	570	(1)
Bile Acids	571	(6)
Polymers	577	(34)
Introduction	577	(2)
Chain-Reaction Polymerization	579	(2)
Step-Reaction Polymerization	581	(2)
Polymer Structure	583	(1)
Some Typical Polymers	584	(4)
Plasticizers	588	(1)
Applications and Recycling	589	(1)
Identification of Plastics	590	(21)
Synthesis and Analysis of Polymers	595	(1)
Overview	595	(1)
Emulsion Polymerization of Styrene with Persulfate	596	(1)
Emulsion Polymerization of Methyl Methacrylate	597	(1)
Bulk Copolymerization of Styrene and Divinylbenzene: Effect of a Plasticizer	598	(1)
Bulk Polymerization of Methyl Methacrylate	599	(1)
Cellulose Triacetate	599	(2)
Phenolic Resins	601	(1)
Preparation of Nylon 6.6: The Nylon Rope Trick	601	(1)
Analysis of Polymers	602	(9)
Dyes and Pigments	611	(24)
Dyes, Pigments, and Colors	611	(1)
Azo Dyes	612	(1)
Synthesis of Azo Dyes	613	(2)
Cationic Dyes	615	(1)
Anthraquinone Dyes	616	(1)
Indigo Dyes	617	(1)
Other Dyes	618	(1)
Mode of Application	619	(1)
Dyeing	620	(15)
Colored Chemistry	626	(1)
Direct Dyes	627	(3)
Mordant Dyeing	630	(1)
Ingrain Dyes	630	(2)
Vat Dyes	632	(1)
Dye Fastness	633	(2)
Bioorganic Chemistry	635	(18)
Enzymes: Biological Catalysts	635	(1)
How Enzymes Work	635	(2)
Using Enzymes	637	(2)
Prochiral Molecules	639	(1)
Reduction of Ketones	640	(2)
Enantiomeric Excess	642	(11)
Asymmetric Synthesis with Baker's Yeast: An Open-Ended Experiment	645	(1)
Overview	645	(1)
Investigating the Course of the Reaction	646	(1)
Conformational Analysis: Determining Whether the Diol is Threo or Erythro (Advanced Level)	647	(2)
Reduction of 1-Phenyl-1,2-Propanedione with Baker's Yeast	649	(1)
Analysis	650	(3)
Molecules of Heredity	653	(14)
Nucleosides and Nucleotides	653	(3)
Base Pairing	656	(1)
Purine and Pyrimidine Bases	657	(1)
Chemical Transformations	658	(9)
Analysis of Nucleosides	662	(1)
Overview of the Experiment	662	(1)
Analysis of an RNA Digest	662	(2)
Deamination of Cytidine to Uridine	664	(3)
SECTION 3 SPECTROSCOPY	667	(136)
Absorption Spectroscopy	669	(6)
The Nature of Light	669	(1)
Interaction between Electromagnetic Radiation and Matter	670	(2)
Absorption Spectroscopy	672	(3)
Infrared Spectroscopy	675	(32)
Molecular Vibrations	675	(2)
Stretching and Bending Vibrations	677	(2)
IR and Dipole Moment	679	(1)
Regions of the IR Spectrum	680	(1)
Experimental Aspects	681	(4)
Interpreting IR Spectra	685	(8)
Case Studies	693	(2)
Concentration and Solvent Effects on IR	695	(2)
Instrumentation	697	(10)
Ultraviolet-Visible Spectroscopy	707	(12)
Electronic Transitions	707	(2)
Chromophores and Auxochromes	709	(1)
Structural Effects on UV-Visible Spectra: Woodward-Fieser Rules	710	(1)
Applications of UV-Visible Spectroscopy	711	(3)
Spectrophotometers	714	(5)
Nuclear Magnetic Resonance	719	(64)
Nuclear Spin	719	(2)
The Resonance Phenomenon: A Closer Look	721	(3)
Obtaining the NMR Spectrum	724	(2)
1H-NMR	726	(1)
Electronic Shielding	727	(2)
The Chemical Shift	729	(1)
Effect of Pi Electrons	730	(2)
Hydrogen Equivalence: A Closer Look	732	(1)
Integrals	732	(2)
Spin-Spin Splitting	734	(5)
Typical Coupling Patterns	739	(1)
The Coupling Constant	739	(3)
Coupling: A Closer Look	742	(8)
Chemical Shift Correlations	750	(6)
Coupling of Hydrogens Attached to Heteroatoms	756	(2)
13C-NMR	758	(2)
13C-NMR Chemical Shifts	760	(5)
Aromatic Systems	765	(3)
Effect of Chirality on the NMR	768	(3)
Running the Spectrum	771	(1)
Two-Dimensional NMR	772	(2)
Interpreting 1H-NMR Spectra	774	(9)
Mass Spectrometry	783	(20)
Overview	783	(1)
Instrumentation	784	(1)
The Molecular Ion	785	(4)
Charge Localization	789	(1)
Fragmentations	790	(6)
MS Case Studies	796	(2)
Interpreting Mass Spectra	798	(2)
High-Resolution Mass Spectra	800	(3)
Answers to Odd-Numbered Exercises	803	(18)
Credits	821	(2)
Index	823