Experimental Organic Chemistry: A Balanced Approach : Macroscale and Microscale : Flexible Connector Version

by Mohrig, Jerry R.

• ISBN13: 9780716733300
• ISBN10: 0716733307
• Edition: CD
• Format: Hardcover
• Copyright: 1998-08-01
• Publisher: W H Freeman & Co

Table of Contents

PREFACE	xv
INTRODUCTION: GETTING ACQUAINTED WITH THE LABORATORY	1	(12)
1.1 Experimental Organic Chemistry	1	(1)
1.2 Laboratory Safety	1	(1)
1.3 Cleanup Following an Experiment	2	(1)
1.4 Desk Equipment	2	(2)
1.5 Introduction to Macroscale and Microscale Laboratory Work	4	(1)
1.6 Using Handbooks	4	(1)
1.7 Your Laboratory Notebook	5	(8)
Part 1 Experiments	13	(286)
1 EXTRACTION OF CAFFEINE FROM TEA	15	(6)
2 PURIFICATION AND THIN-LAYER CHROMATOGRAPHIC ANALYSIS OF CAFFEINE	21	(4)
Optional Experiment: Evaluating TLC Parameters	24	(1)
3 SYNTHESIS OF ETHANOL BY FERMENTATION OF SUCROSE	25	(5)
4 SYNTHESIS OF SALICYCLIC ACID	30	(7)
5 SYNTHESIS OF ASPIRIN	37	(7)
Optional Experiment: Thin-Layer Chromatographic Analysis of Analgesics	43	(1)
6 RADICAL CHLORINATION REACTIONS	44	(5)
Optional Experiments: Additional Substrates	48	(1)
7 ISOLATION OF ESSENTIAL OILS AND THE THEORY OF ODOR	49	(10)
7.1 Isolation of S-(+)-Carvone from Caraway Seeds	50	(6)
7.2 Isolation of R-(+)-Limonene from Orange Peels	56	(3)
8 NUCLEOPHILIC SUBSTITUTION REACTIONS	59	(11)
8.1 S(N)1/S(N)2 Reactivity of Alkyl Halides	61	(5)
8.2 Preparation and Identification of Alkyl Bromides Synthesized from Unknown Alcohols	66	(4)
9 ADDITION REACTIONS OF ALKENES	70	(18)
9.1 Free Radical versus Ionic Addition of Hydrobromic Acid to Alkenes	82
9.2 Dimerization of 2-Methylpropene (Isobutylene)	78
9.3 Stereochemistry of Bromine Addition to trans-Cinnamic Acid	84	(4)
10 DEHYDROHALOGENATION OF 2-BROMOHEPTANE: VARIATION OF PROMOTING BASE	88	(4)
11 DEHYDRATION OF ALCOHOLS	92	(13)
11.1 Synthesis of Cyclohexene by Acid-Catalyzed Dehydration of Cyclohexanol	94	(7)
11.2 Dehydration of 2-Methylcyclohexanol	101	(3)
Optional Experiments	104	(1)
12 ETHER SYNTHESES	105	(10)
12.1 Williamson Ether Synthesis of Ethoxybutane	106	(4)
12.2 Synthesis and Analysis of a Propyl Benzhydryl Ether	110	(5)
13 GRIGNARD SYNTHESES	115	(19)
13.1 Synthesis of Phenylmagnesium Bromide and Its Use as a Synthetic Intermediate	118	(12)
13.1a Synthesis of Diphenylmethanol (Benzhydrol)	122	(4)
13.1b Synthesis of Benzoic Acid	126	(4)
13.2 Grignard Synthesis of a Triphenylmethane Dye: Crystal Violet or Malachite Green	130	(4)
14 PHASE TRANSFER CATALYSIS	134	(11)
14.1 Williamson Ether Synthesis of Bis-4-Chlorobenzyl Ether Using Phase Transfer Catalysis	135	(5)
14.2 Synthesis of Butyl Benzoate Using Phase Transfer Catalysis	140	(5)
15 OXIDATION REACTIONS	145	(16)
15.1 Oxidation of Cyclohexanol Using Sodium Hypochlorite	147	(6)
Optional Experiment: Derivative Synthesis	152	(1)
15.2 General Method for Oxidizing Secondary Alcohols to Ketones	153	(4)
15.3 Oxidation of Cinnamyl Alcohol Using Pyridinium Chlorochromate	157	(4)
16 DIELS-ALDER REACTIONS	161	(11)
16.1 Synthesis of Dimethyl 3,4,5,6-Tetraphenylphthalate from 2,3,4,5-Tetraphenylcyclopentadienone and Dimethyl Acetylene Dicarboxylate	162	(4)
16.2 Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic Acid from Butadiene Sulfone and Maleic Anhydride	166	(6)
17 ELECTROPHILIC AROMATIC SUBSTITUTION	172	(14)
17.1 Iodination of 1,2,4,5-Tetramethylbenzene Using Iodine and Periodic Acid	174	(4)
17.2 Bromination of Acetanilide	178	(5)
Optional Experiment: Removal of the Acetyl Protecting Group: Synthesis of a Bromoaniline	181	(2)
17.3 Rates of Electrophilic Aromatic Substitution	183	(3)
Optional Experiments	186	(1)
18 ACYLATION AND ALKYLATION OF AROMATIC COMPOUNDS	186	(16)
18.1 Acylation of Ferrocene	189	(5)
18.2 Synthesis of 4,4'-Di-tert-Butylbiphenyl	194	(5)
18.3 Synthesis of 1,4-Di-tert-Butyl-2,5-Dimethoxybenzene	199	(3)
19 REDUCTION REACTIONS OF 3-NITROACETOPHENONE	202	(7)
19.1 Reduction of 3-Nitroacetophenone Using Tin and Hydrochloric Acid	205	(2)
19.2 Reduction of 3-Nitroacetophenone Using Sodium Borohydride	207	(2)
20 PHOTOCHEMISTRY: PHOTOREDUCTION OF BENZOPHENONE AND REARRANGEMENT TO BENZPINACOLONE	209	(7)
21 ALDOL CONDENSATION: REACTION OF BENZALDEHYDE AND ACETONE	216	(6)
22 SYNTHESIS OF 2,3,4,5-TETRAPHENYLCYCLOPENTADIENONE	222	(6)
23 HORNER-EMMONS-WITTIG SYNTHESIS OF METHYL 4-METHOXY-E-CINNAMATE	228	(6)
24 KINETIC VERSUS THERMODYNAMIC CONTROL IN CHEMICAL REACTIONS	234	(13)
24.1 Semicarbazones of Cyclohexanone and 2-Furaldehyde	236	(6)
24.2 Fridel-Crafts Alkylation of Chlorobenzene	242	(4)
Optional Experiments: Roles of Nitromethane	246	(1)
25 SYNTHESIS OF ESTERS	247	(12)
25.1 Synthesis of Isopentyl Acetate (Banana Oil)	248	(5)
Optional Experiments: Propyl Ethanoate (Propyl Acetate) and 2-Methyl-1-Propyl Propanoate (Isobutyl Propionate)	252	(1)
25.2 Synthesis and Identification of an Ester from an Unknown Alcohol and Acetic Acid	253	(6)
26 AMIDE CHEMISTRY	259	(18)
26.1 Synthesis of Hippuric Acid	261	(5)
Optional Experiment: Solubilities of Benzoic Acid and Hippuric Acid	265	(1)
26.2 Synthesis of a Mosquito Repellent: N,N-Diethyl-meta-Toluamide (Deet)	266	(11)
27 POLYPHOSPHORIC ACID-CATALYZED BECKMANN REARRANGEMENT OF ACETOPHENONE OXIME	277	(5)
28 SYNTHESIS OF trans-1,2-DIBENZOCYCLOPROPANE BY RING CLOSURE	282	(5)
29 POLYMER CHEMISTRY	287	(12)
29.1 Synthesis of Polystyrene	290	(4)
Optional Experiment	294	(1)
29.2 Biodegradable Starch Films	295	(4)
Part 2 Projects	299	(122)
1 HYDROLYSIS OF AN UNKNOWN ESTER	301	(11)
1.1 Hydrolysis and Azeotropic Distillation	303	(2)
1.2 Extraction and Recrystallization	305	(4)
1.3 Distillation, Melting Points, and Identification	309	(3)
2 SYNTHESIS OF 1-BROMOBUTANE AND A GRIGNARD SYNTHESIS OF AN ALCOHOL	312	(11)
2.1 Synthesis of 1-Bromobutane from 1-Butanol	313	(4)
Optional Syntheses of Alkyl Halides	316	(1)
2.2 Grignard Synthesis of Secondary and Tertiary Alcohols	317	(4)
Optional Synthesis	321	(2)
3 SYNTHESIS AND DEHYDRATION OF 3,3-DIMETHYL-2-BUTANOL	323	(7)
3.1 Synthesis of 3,3-Dimethyl-2-Butanol by Reduction with Sodium Borohydride	324	(3)
3.2 Acid-Catalyzed Dehydration of 3,3-Dimethyl-2-Butanol with Rearrangement	327	(3)
4 INTERCONVERSION OF 4-tert-BUTYLCYCLOHEXANOL AND 4-tert-BUTYLCYCLOHEXANONE	330	(14)
4.1 Sodium Hypochlorite Oxidation of 4-tert-Butylcyclohexanol to 4-tert-Butylcyclohexanone	332	(6)
4.2 Sodium Borohydride Reduction of 4-tert-Butylcyclohexanone	338	(3)
Optional GC or NMR Experiment	341	(3)
5 ALDOL CONDENSATION USING AN UNKNOWN ALDEHYDE AND AN UNKNOWN KETONE: DERIVATIVE FORMATION AND IDENTIFICATION OF UNKNOWNS	344	(9)
5.1 Preparation of Aldol Condensation Product	348	(1)
5.2 Characterization of the Aldol Product	349	(4)
6 BENZOIN CHEMISTRY: SYNTHESIS OF AN ANTICONVULSANT DRUG USING BIOCHEMICAL CATALYSIS	353	(16)
6.1 Thiamine-Catalyzed Benzoin Condensation	353	(7)
6.2 Oxidation of Benzoin	360	(5)
6.3 Synthesis of 5,5-Diphenylhydantoin, an Anticonvulsant Drug	365	(4)
7 SYNTHESIS OF BENZOCAINE	369	(7)
7.1 Synthesis of p-Aminobenzoic Acid	371	(2)
7.2 Synthesis of Benzocaine	373	(3)
8 RESOLUTION OF (R,S)-BENZOYLAMINO ACIDS	376	(11)
8.1 Papain	377	(3)
8.2 Resolution of (R,S)-Benzoylamino Acids	380	(1)
8.3 Synthesis of the (R,S)-Benzoylamino Acid	381	(2)
8.4 Enzymatic Resolution: Synthesis of the (S)-Benzoylamino Acid Anilide	383	(3)
Further Investigations	386	(1)
9 MULTISTEP SYNTHESIS OF PARA RED FROM ACETANILIDE	387	(9)
9.1 Two-Step Synthesis of p-Nitroaniline	390	(3)
9.2 Preparation of Diazonium Salts	393	(3)
10 SYNTHESIS STARTING WITH ALKYL HALIDES	396	(3)
11 DIELS-ALDER CYCLOADDITIONS OF VARIOUS DIENOPHILES TO 2,3-DIMETHYL-1,3-BUTADIENE	399	(5)
11.1 Synthesis of cis-4,5-Dimethyl-1,2,3,6-Tetrahydrophthalic Anhydride	400	(1)
11.2 Addition of Various Dienophiles to 2,3-Dimethyl-1,3-Butadiene	401	(3)
12 MULTISTEP SYNTHESIS OF N-PHENYLTETRAPHENYL-PHTHALIMIDE	404	(8)
12.1 Synthesis of Tetraphenylcyclopentadienone	405	(1)
12.2 Synthesis of Dimethyl Tetraphenylphthalate	406	(1)
12.3 Synthesis of Tetraphenylphthalic Acid	407	(1)
12.4 Synthesis of Tetraphenylphthalic Anhydride	408	(2)
12.5 Synthesis of N-Phenyl-3,4,5,6 Tetraphenylphthalimide	410	(2)
13 SUGARS: THE GLUCOSE PENTAACETATES	412	(9)
13.1 Preparation of'Stereoisomers of D-Glucose	416	(2)
13.2 (1)H NMR Analysis of Alpha- and Beta-D-Glucose Pentaacetates	418	(1)
13.3 Optical Activity of Sugars	418	(1)
Further Investigations	419	(2)
Part 3 Organic Qualitative Analysis	421	(68)
1 IDENTIFICATION OF UNKNOWNS	423	(3)
2 PHYSICAL PROPERTIES	426	(1)
3 CLASSIFICATION BY SOLUBILITY AND ELEMENTAL ANALYSIS BY SODIUM FUSION	427	(10)
3.1 Classification by Solubility	427	(7)
3.2 Elemental Analysis by Sodium Fusion	434	(3)
4 INFRARED, NUCLEAR MAGNETIC RESONANCE, AND MASS SPECTROMETRIC ANALYSIS	437	(8)
4.1 Using Spectrometric Data	441	(4)
5 CLASSIFICATION TESTS FOR FUNCTIONAL GROUPS	445	(22)
5.1 Alcohols	446	(3)
5.2 Aldehydes and Ketones	449	(3)
5.3 Alkenes	452	(2)
5.4 Alkyl Halides	454	(2)
5.5 Amines	456	(3)
5.6 Aromatic Hydrocarbons (Arenes)	459	(1)
5.7 Aryl Halides	460	(1)
5.8 Carboxylic Acids	461	(1)
5.9 Carboxylic Acid Derivatives	462	(1)
5.9a Acyl Chlorides	462	(1)
5.9b Esters	462	(1)
5.10 Amides, Acyl Chlorides, Esters, and Nitriles	462	(3)
5.11 Ethers	465	(1)
5.12 Phenols	466	(1)
6 SYNTHESIS OF SOLID DERIVATIVES	467	(11)
6.1 Alcohols	468	(3)
6.2 Aldehydes and Ketones	471	(1)
6.3 Amines	472	(2)
6.4 Carboxylic Acids: Amides, Anilides Toluidides	474	(3)
6.5 Phenols	477	(1)
7 SEPARATION OF MIXTURES	478	(7)
7.1 Assaying the Number of Compounds	481	(1)
7.2 Separating the Mixture	481	(3)
7.3 Model Extraction Procedure	484	(1)
8 SUMMARY OF IDENTIFICATION PROCEDURE FOR AN UNKNOWN COMPOUND	485	(1)
9 SUMMARY OF THE ANALYSIS OF A MIXTURE OF UNKNOWN COMPOUNDS	486	(3)
Part 4 Spectrometric Methods	489	(94)
1 INFRARED SPECTROMETRY	491	(27)
1.1 Theory of Molecular Vibration	492	(1)
1.2 IR Spectrum	492	(3)
1.3 IR Instrumentation	495	(3)
1.4 Techniques of Sample Preparation	498	(4)
1.5 Interpreting Spectra	502	(16)
2 NUCLEAR MAGNETIC RESONANCE SPECTROMETRY	518	(48)
2.1 NMR Instrumentation	519	(3)
2.2 Chemical Shift	522	(5)
2.3 Spin-Spin Splitting	527	(3)
2.4 Detecting Chemical Equivalence	530	(1)
2.5 Integration	531	(2)
2.6 Preparing the NMR Sample	533	(2)
2.7 Recording an NMR Spectrum	535	(1)
2.8 Interpreting (1)H NMR Spectra	536	(2)
2.9 (13)C NMR	538	(6)
2.10 An Approach to Solving NMR Problems	544	(9)
2.11 Two-Dimensional NMR and Related Techniques (Special Topic)	553	(13)
3 MASS SPECTROMETRY	566	(9)
4 ULTRAVIOLET AND VISIBLE SPECTROMETRY	575	(7)
INTEGRATED PROBLEMS	582	(1)
Part 5 Techniques of the Organic Laboratory	583
1 SAFETY	585	(14)
1.1 Causes of Laboratory Accidents	585	(3)
1.2 Safety Features of Your Laboratory	588	(1)
1.3 Preventing Accidents	589	(1)
1.4 What to Do if an Accident Occurs	590	(1)
1.5 Chemical Toxicology	591	(2)
1.6 Where to Find Chemical Safety Information	593	(3)
1.7 Protecting The Environment	596	(3)
2 LABORATORY GLASSWARE	599	(6)
2.1 Standard Taper Glassware	599	(2)
2.2 Microscale Glassware	601	(1)
2.3 Cleaning Your Glassware	602	(2)
2.4 Pasteur Filter Pipets	604	(1)
3 HEATING METHODS	605	(9)
3.1 Boiling Stones	606	(1)
3.2 Heating Devices	606	(3)
3.3 Refluxing a Reaction Mixture	609	(5)
3.3a Refluxing a Reaction Mixture under Anhydrous Conditions	610	(4)
4 EXTRACTION AND DRYING AGENTS	614	(21)
4.1 Extraction: The Theory	615	(2)
4.2 Macroscale Extractions	617	(2)
4.3 Additional Information about Extractions	619	(3)
4.4 Summary of Macroscale Extraction from Water to an Organic Phase	622	(1)
4.5 Microscale Extractions	622	(7)
4.5a Extracting an Aqueous Solution with an Organic Solvent More Dense Than Water	624	(1)
4.5b Washing an Organic Liquid That Is More Dense Than Water	625	(1)
4.5c Extraction with an Organic Solvent Less Dense Than Water	626	(1)
4.5d Washing an Organic Liquid That Is Less Dense Than Water	626	(3)
4.6 Drying Organic Liquids	629	(3)
4.7 Methods for Separating Drying Agents and Organic Liquids	632	(1)
4.8 Recovery of the Organic Product from the Dried Extraction Solution	633	(2)
5 RECRYSTALLIZATION	635	(12)
5.1 Theory of Recrystallization	635	(3)
5.2 Selecting a Proper Recrystallization Solvent	638	(1)
5.2a Recrystallization from Mixed Solvent Pairs	639	(1)
5.3 Macroscale Procedure for Recrystallizing a Solid	639	(5)
5.3a Removing Impurities from the Recrystallization Solution	642	(2)
5.4 Summary of the Macroscale Recrystallization Procedure	644	(1)
5.5 Microscale Recrystallization	644	(1)
5.6 Summary of the Microscale Recrystallization Procedures	645	(1)
5.7 What to Do If No Crystals Appear in the Cooled Solution	645	(1)
5.8 Pointers for Successful Recrystallizations	646	(1)
6 MELTING POINTS AND MELTING RANGES	647	(9)
6.1 Melting Point Theory	647	(2)
6.2 Apparatus for Determining Melting Ranges	649	(3)
6.3 Determining Melting Ranges	652	(2)
6.4 Mixture Melting Points	654	(1)
6.5 Thermometer Calibration	655	(1)
6.6 Summary of Melting-Point Determination	655	(1)
7 BOILING POINTS, DISTILLATION, AND AZEOTROPES	656	(24)
7.1 Boiling Points	657	(2)
7.1a Determination of Boiling Points	658	(1)
7.2 Boiling Points and Separation of Mixtures	659	(4)
7.3 Simple Distillation	663	(5)
7.3a Short-Path Distillation	666	(1)
7.3b Microscale Distillation	667	(1)
7.4 Fractional Distillation	668	(3)
7.5 Azeotropic Distillation	671	(1)
7.6 Steam Distillation	672	(3)
7.7 Vacuum Distillation	675	(5)
8 SUBLIMATION	680	(3)
8.1 Assembling the Apparatus for a Sublimation	681	(1)
8.2 Carrying Out a Microscale Sublimation	682	(1)
9 REFRACTROMETRY	683	(4)
9.1 Theory of Refractometry	683	(1)
9.2 The Refractometer	684	(2)
9.3 Steps in Determining a Refractive Index	686	(1)
9.4 Temperature Correction	686	(1)
10 THIN-LAYER CHROMATOGRAPHY	687	(11)
10.1 Principles of Thin-Layer Chromatography	688	(3)
10.1a Determination of the R(f)	689	(2)
10.2 Plates for Thin-Layer Chromatography	691	(1)
10.3 Sample Application	692	(1)
10.4 Development and Choices of Developing Solvents	693	(3)
10.5 Visualization Techniques	696	(1)
10.6 Summary of TLC Procedure	697	(1)
11 GAS-LIQUID CHROMATOGRAPHY	698	(13)
11.1 Instrumentation	699	(2)
11.2 Columns and Liquid Stationary Phases	701	(3)
11.3 Detectors	704	(2)
11.4 Interpreting Chromatograms	706	(1)
11.5 Practical GC Operating Procedures	707	(2)
11.6 Identification of Components and Quantitative Analysis	709	(2)
12 LIQUID CHROMATOGRAPHY	711	(13)
12.1 Adsorbents	711	(1)
12.2 Elution Solvents	712	(2)
12.3 Choosing a Column	714	(1)
12.4 Making a Macroscale Column	715	(1)
12.5 Elution Techniques	716	(2)
12.6 Microscale Column Chromatography	718	(2)
12.7 Summary of Column Chromatography Techniques	720	(1)
12.8 Dry Column Chromatography	720	(1)
12.9 Flash Chromatography	720	(2)
12.10 High-Performance Liquid Chromatography	722	(2)
13 POLARIMETRY	724
13.1 Mixtures of Optical Isomers: Separation/Resolution	724	(4)
13.2 Polarimetric Instrumentation	728	(2)
13.3 Specific Rotation	730	(1)
13.4 Using the Polarimeter	731	(1)
13.5 Enantiomeric Excess (Optical Purity)	732
Appendix A DERIVATIVE TABLES FOR ORGANIC QUALITATIVE ANALYSIS	A-1
Appendix B THE LITERATURE OF ORGANIC CHEMISTRY	B-1
Index	I-1