Techniques and Experiments for Organic Chemistry

by Ault, Addison

• ISBN13: 9780935702767
• ISBN10: 0935702768
• Edition: 6th
• Format: Hardcover
• Copyright: 1998-06-01
• Publisher: Univ Science Books

Table of Contents

Preface to the Sixth Edition	xix	(2)
Preface to the Fifth Edition	xxi
PART I Laboratory Operations	3	(324)
Preliminary Topics
1. Safety	3	(13)
1.1 Fire	4	(1)
1.2 Explosions	5	(1)
1.3 Poisoning	6	(1)
1.4 Cuts	7	(1)
1.5 Spills	7	(1)
1.6 Chemicals in the Eye	8	(1)
1.7 A Short List of Hazardous Materials and Some of Their Properties	8	(8)
2. Glassware Used in the Organic Chemistry Laboratory	16	(5)
3. Cleaning Up	21	(3)
3.1 Care of Ground-Glass-Jointed Glassware	22	(1)
3.2 Separatory Funnels and Glassware with Stopcocks	23	(1)
3.3 Drying of Glassware	23	(1)
4. Collection and Disposal of Waste	24	(2)
4.1 Solid Waste	24	(1)
4.2 Liquid Waste	25	(1)
4.3 General Instructions for Collection of Waste	25	(1)
5. The Laboratory Notebook	26	(5)
6. The Chemical Literature	31	(7)
6.1 Secondary Sources for Physical Properties of Organic Compounds	32	(3)
6.2 Secondary Sources for Methods of Preparation of Organic Compounds	35	(1)
6.3 Collection of Spectra	36	(1)
6.4 Miscellaneous	37	(1)
7. Tables	38	(6)
7.1 Solutions of Acids	39	(1)
7.2 Solutions of Bases	40	(1)
7.3 Molecular Weights and Molar Volumes of Acids	40	(1)
7.4 Molar Weights of Bases	41	(1)
7.5 Molecular Weights, Densities, and Molar Volumes of Selected Liquid Reagents	41	(1)
7.6 Periodic Table of the Elements	42	(2)
Separation of Substances; Purification of Substances
8. Filtration	44	(4)
8.1 Gravity Filtration	44	(1)
8.2 Micro-Scale Gravity Filtration	45	(1)
8.3 Vacuum or Suction Filtration	45	(3)
9. Recrystallization	48	(14)
9.1 Choice of Solvent	49	(1)
9.2 Dissolving the Sample	49	(1)
9.3 Decolorizing the Solution	50	(1)
9.4 Hot Filtration	50	(2)
9.5 Cooling for Crystallization	52	(1)
9.6 Cold Filtration	53	(1)
9.7 Washing the Crystals	53	(1)
9.8 Drying the Crystals	54	(1)
9.9 More Techniques of Crystallization	55	(2)
9.10 Micro-Scale Recrystallization	57	(2)
9.11 Selection of a Suitable Solvent	59	(3)
10. Distillation	62	(18)
10.1 Vapor Pressure	63	(3)
10.2 Distillation of a Pure Liquid	66	(1)
10.3 Miscible Pairs of Liquids	67	(3)
10.4 Fractional Distillation	70	(2)
10.5 Azotropic Mixtures	72	(3)
10.6 Technique of Distillation	75	(2)
10.7 Small-Scale Distillation	77	(3)
11. Reduced-Pressure Distillation	80	(7)
11.1 Estimation of the Boiling Point at Reduced Pressure	81	(1)
11.2 Apparatus	82	(1)
11.3 Source of Vacuum	83	(1)
11.4 Pressure Measurement	84	(1)
11.5 Technique of Distillation Under Reduced Pressure	85	(2)
12. Distillation of Mixtures of Two Immiscible Liquids; Steam Distillation	87	(3)
12.1 Theory of Steam Distillation	87	(1)
12.2 Technique of Steam Distillation	88	(2)
13. Sublimation	90	(2)
13.1 Theory of Sublimation	90	(1)
13.2 Technique of Sublimation	91	(1)
14. Extraction by Solvents	92	(17)
14.1 Theory of Extraction	92	(2)
14.2 Extraction of Acids and Bases	94	(3)
14.3 Technique of Extraction	97	(4)
14.4 Micro-Scale Extraction	101	(8)
15. Chromatography	109	(20)
15.1 Theory of Column Chromatography	110	(3)
15.2 Technique of Column Chromatography	113	(3)
15.3 Theory of Thin-Layer Chromatography	116	(2)
15.4 Technique of Thin-Layer Chromatography	118	(2)
15.5 Theory of Paper Chromatography	120	(1)
15.6 Technique of Paper Chromatography	120	(2)
15.7 Theory of Vapor-Phase Chromatography	122	(4)
15.8 Technique of Vapor-Phase Chromatography	126	(2)
15.9 High-Pressure Liquid Chromatography	128	(1)
15.10 Batchwise Adsorption; Decolorization	129	(1)
16. Removal of Water; Drying	129	(9)
16.1 Drying of Solids	130	(2)
16.2 Drying of Solutions	132	(2)
16.3 Drying of Solvents and Liquid Reagents	134	(4)
Determination of Physical Properties
17. Boiling Point	138	(12)
17.1 Experimental Determination of Boiling Point	138	(3)
17.2 Boiling Point and Molecular Structure	141	(3)
17.3 Boiling Point and the Enthalpy and Entropy of Vaporization	144	(6)
18. Melting Point	150	(9)
18.1 Experimental Determination of the Melting Point	150	(4)
18.2 The Melting Point as a Criterion of Purity	154	(1)
18.3 The Melting Point as a Means of Identification and Characterization	155	(1)
18.4 Mixture Melting Points	155	(1)
18.5 Melting Point and Molecular Structure	155	(4)
19. Density; Specific Gravity	159	(2)
19.1 Experimental Determination of the Density	159	(1)
19.2 Density and Molecular Structure	160	(1)
20. Index of Refraction	161	(2)
20.1 Experimental Determination of the Index of Refraction	161	(1)
20.2 Index of Refraction and Molecular Structure	162	(1)
21. Optical Activity	163	(5)
21.1 Experimental Determination of Optical Rotation	163	(3)
21.2 Optical Activity and Molecular Structure	166	(2)
22. Molecular Weight	168	(1)
22.1 Molecular Weight Determination by Mass Spectrometry	168	(1)
22.2 Molecular Weight Determination by Other Methods	169	(1)
23. Solubility	169	(13)
23.1 Solubility of Liquids in Liquids	170	(4)
23.2 Solubility of Solids in Liquids	174	(1)
23.3 Classification of Compounds by Solubility; Relationships Between Solubility and Molecular Structure	175	(5)
23.4 Techniques for Determination of Solubility	180	(2)
24. Infrared Absorption Spectrometry	182	(19)
24.1 Wavelength, Frequency, and Energy of Electromagnetic Radiation	183	(1)
24.2 Units of Light Absorption	183	(2)
24.3 Infrared Light Absorption and Molecular Structure	185	(1)
24.4 Interpretation of Infrared Spectra	186	(5)
24.5 Sample Preparation	191	(10)
25. Ultraviolet-Visible Absorption Spectrometry	201	(6)
25.1 Ultraviolet-Visible Light Absorption and Molecular Structure	202	(1)
25.2 Interpretation of Ultraviolet-Visible Spectra	203	(1)
25.3 Color and Molecular Structure	203	(1)
25.4 Sample Preparation	204	(3)
26. Nuclear Magnetic Resonance Spectrometry	207	(24)
26.1 Shielding; Chemical Shift	208	(3)
26.2 Splitting	211	(8)
26.3 The Integral	219	(1)
26.4 Nuclear Magnetic Resonance and Molecular Structure	220	(2)
26.5 Interpretation of NMR Spectra	222	(4)
26.6 Sample Preparation	226	(5)
27. Mass Spectrometry	231	(10)
27.1 Theory of Mass Spectrometry	231	(3)
27.2 Interpretation of Mass Spectra	234	(2)
27.3 High-Resolution Mass Spectrometry	236	(5)
Determination of Chemical Properties: Qualitative Organic Analysis
28. Qualitative Tests for the Elements	241	(6)
28.1 Ignition Test; Test for Metals	241	(1)
28.2 Beilstein Test; Test for Halogens (Except Fluorine)	242	(1)
28.3 Sodium Fusion Test; Test for Nitrogen, Sulfur, and the Halogens	242	(5)
29. Qualitative Characterization Tests: Tests for the Functional Groups	247	(19)
29.1 Detection of Ammonia from Ammonium Salts, Primary Amides, and Nitriles	249	(1)
29.2 Benzenesulfonyl Chloride (Hinsberg's Test)	250	(2)
29.3 Bromine in Carbon Tetrachloride	252	(1)
29.4 Chromic Anhydride	253	(1)
29.5 2,4-Dinitrophenylhydrazine	253	(1)
29.6 Ferric Chloride Solution	254	(1)
29.7 Ferric Hydroxamate Test	255	(3)
29.8 Hydrochloric Acid/Zinc Chloride Test (Lucas's Test)	258	(1)
29.9 Iodoform Test	258	(2)
29.10 Aqueous Potassium Permanganate Solution (Baeyer's Test)	260	(1)
29.11 Alcoholic Silver Nitrate Solution	261	(1)
29.12 Sodium Hydroxide Test	262	(1)
29.13 Sodium Iodide in Acetone	263	(1)
29.14 Tollen's Reagent: Silver-Ammonia Complex Ion	263	(3)
30. Characterization Through Formation of Derivatives	266	(33)
30.1 Benzoates, p-Nitrobenzoates, and 3,5-Dinitrobenzoates of Alcohols	272	(1)
30.2 Hydrogen 3-Nitrophthalates of Alcohols	273	(1)
30.3 Phenyl-and Alpha-Naphthylurethans	274	(1)
30.4 Methone Derivations of Aldehydes	274	(1)
30.5 2,4-Dinitrophenylhydrazones	275	(1)
30.6 Semicarbazones	276	(1)
30.7 Oximes	276	(1)
30.8 Carboxylic Acids by Hydrolysis of Primary Amides and Nitriles	277	(1)
30.9 9-Acylamidoxanthenes from Amides	278	(1)
30.10 Hydrolysis of N-Substituted Amides	279	(1)
30.11 Substituted Acetamides from Amines	280	(1)
30.12 Substituted Benzamides from Amines	281	(1)
30.13 p-Toluenesulfonamides from Amines	282	(1)
30.14 Phenylthioureas and Alpha-Naphthylthioureas	282	(1)
30.15 Picrates	283	(2)
30.16 Quaternary Ammonium Salts: Methiodides and p-Toluenesulfonates	285	(1)
30.17 Carboxylic Acid Amides	285	(1)
30.18 Anilides, p-Toluidides, and p-Bromoanilides of Carboxylic Acids	286	(1)
30.19 Phenacyl and Substituted Phenacyl Esters of Carboxylic Acids	287	(2)
30.20 P-Nitrobenzyl Esters of Carboxylic Acids	289	(1)
30.21 N-Benzylamides from Esters	290	(1)
30.22 3,5-Dinitrobenzoates from Esters	290	(1)
30.23 Hydrolysis of Esters	291	(1)
30.24 Bromination of Aromatic Ethers	292	(1)
30.25 S-Alkylthiuronium Picrates	293	(1)
30.26 o-Aroylbenzoic Acids from Aromatic Hydrocarbons	294	(1)
30.27 Aromatic Acids by Oxidation by Permanganate	295	(1)
30.28 Anilides, p-Toluidides, and Alpha-Naphthalides from Alkyl Halides	295	(1)
30.29 2,4,7-Trinitrofluorenone Adducts of Aromatic Hydrocarbons	296	(1)
30.30 Bromination of Phenols	297	(1)
30.31 Aryloxyacetic Acids from Phenols	297	(2)
Apparatus and Techniques for Chemical Reactions
31. Assembling the Apparatus	299	(3)
32. Temperature Control	302	(3)
33. Methods of Heating and Cooling	305	(5)
33.1 Heating	305	(4)
33.2 Cooling	309	(1)
34. Stirring	310	(3)
35. Addition of Reagents	313	(2)
36. Control of Evolved Gases	315	(2)
37. Concentration; Evaporation	317	(1)
38. Use of an Inert Atmosphere	318	(1)
39. Working Up the Reaction; Isolation of the Product	319	(8)
PART II Experiments	327	(308)
Isolations and Purifications
E1 Isolation of Cholesterol from Gallstones	327	(2)
E2 Isolation of Lactose from Powdered Milk	329	(3)
E3 Isolation of Acetylsalicylic Acid from Aspirin Tablets	332	(3)
E4 Isolation of Ibuprofen from Ibuprofen Tablets	335	(2)
E5 Isolation of Caffeine from Tea and NoDoz	337	(3)
E6 Isolation of Piperine from Black Pepper	340	(2)
E7 Isolation of Trimyristin from Nutmeg	342	(2)
E8 Isolation of Clove Oil from Cloves	344	(2)
E9 Isolation of Eugenol from Clove Oil	346	(1)
E10 Isolation of (R)-(+)-Limonene from Grapefruit or Orange Peel	347	(3)
E11 Isolation of (R)-(-)-or (S)-(+)-Carvone from Oil of Spearmint or Oil of Caraway	350	(5)
E12 Resolution of Alpha-Phenylethylamine by (R),(R)-(+)-Tartaric acid	355	(8)
Transformations
Isomerizations	363	(8)
E13 Adamantane from endo-Tetrahydrodicyclopentadiene via the Thiourea Clathrate	364	(3)
E14 cis-Dibenzoylethyelene from trans-1,2-Dibenzoylethylene	367	(4)
Preparation of Cyclohexanol	371	(4)
E15 Cyclohexanol from Cyclohexene	371	(2)
E16 Cycohexanol from Cyclohexanone	373	(2)
Reactions of Cyclohexanol	375	(14)
E17 Cyclohexene from Cyclohexanol	376	(5)
E18 Dehydration of 2-Methylcyclohexanol: A Variation	381	(3)
E19 Cyclohexyl Bromide from Cyclohexanol	384	(3)
E20 Cyclohexanone from Cyclohexanol	387	(2)
Addition of Dichlorcarbene to Alkenes by Phase Transfer Catalysis	389	(8)
E21 Addition of Dichlorocarbene to Cyclohexene	392	(2)
E22 Addition of Dichlorocarbene to Styrene: A Variation	394	(2)
E23 Addition of Dichlorocarbene to 1,5-Cycloctadiene: Another Variation	395	(2)
Alkyl Halides from Alcohols	397	(20)
E24 Isoamyl Bromide from Isoamyl Alcohol	398	(4)
E25 n-Butyl Bromide from n-Butyl Alcohol: A Variation	402	(1)
E26 tert-Butyl Chloride from tert-Butyl Alcohol	403	(3)
E27 tert-Amyl Chloride from tert-Amyl Alcohol: A Variation	406	(1)
E28 Competitive Nucleophilic Substitution of Butyl Alcohols by Bromide and Chloride Ion	407	(3)
E29 Kinetics of the Hydrolysis of tert-Butyl Chloride	410	(7)
Isoamyl Acetate: A Component of the Alarm Pheromone of the Honey Bee	417	(10)
E30 Isoamyl Acetate from Isoamyl Bromide and Potassium Acetate	421	(3)
E31 Isoamyl Acetate from Isoamyl Alcohol and Acetic Acid; The Fischer Estrification	424	(3)
Liquid Crystals	427	(4)
E32 Cholesteryl Benzoate from Cholesterol	428	(3)
Acetylation of Glucose	431	(8)
E33 Alpha-D-Glucose Pentaacetate from Glucose	433	(1)
E34 Beta-D-Glucose Pentaacetate from Glucose	433	(1)
E35 Acetylation of Glucose in N-Methylimidazole: A Variation	434	(2)
E36 Preparation of Methyl Benzoate, Oil of Niobe	436	(3)
The Grignard Reaction	439	(5)
E37 Aliphatic Alcohols: Preparation by Grignard Synthesis	439	(5)
Preparation of Triphenylmethanol	444	(12)
E38 Preparation of Triphenylmethanol from Benzophenone	446	(2)
E39 Preparation of Triphenylmethanol from Methyl Benzoate	448	(3)
E40 Preparation of Triphenylmethanol from Dimethyl Carbonate	451	(3)
E41 Preparation of Aniline from Nitrobenzene	454	(2)
Preparation of Amides	456	(7)
E42 Acetanilide from Aniline	457	(4)
E43 N,N-Diethyl-m-Toluamide from m-Toluic Acid; A Mosquito Repellant: "Off"	461	(2)
Electrophilic Substitution Reactions of Benzene Derivatives	463	(9)
E44 Methyl m-Nitrobenzoate from Methyl Benzoate	464	(2)
E45 p-Bromoacetanilide from Acetanilide	466	(3)
E46 2,4-Dinitrobromobenzene from Bromobenzene	469	(3)
Nucleophilic Aromatic Substitution Reactions of 2,4-Dinitrobromobenzene	472	(8)
E47 2,4-Dinitroaniline	473	(1)
E48 2,4-Dinitrophenylhydrazine	474	(1)
E49 2,4-Dinitrodiphenylamine	475	(2)
E50 2,4-Dinitrophenylpiperidine	477	(1)
E51 4-Substituted 2,4-Dinitrophenylanilines: A Variation	478	(2)
Diazonium Salts of Aromatic Amines	480	(2)
E52 Benzenediazonium Chloride from Aniline	481	(1)
E53 p-Nitrobenzenediazonium Sulfate from p-Nitroaniline	482	(1)
Replacement Reactions of Diazonium Salts	482	(3)
E54 Chlorobenzene from Benzenediazonium Chloride	483	(2)
Reactions of Vanillin	485	(13)
E55 Acetylvanillin from Vanillin	486	(1)
E56 5-Bromovanillin from Vanillin	487	(2)
E57 5-Nitrovanillin from Vanillin	489	(1)
E58 Vanillin Oxime from Vanillin	490	(1)
E59 Vanillin Semicarbazone from Vanillin	491	(2)
E60 Vanillyl Alcohol from Vanillin	493	(1)
E61 Vanillideneacetone from Vanillin	494	(4)
Synthesis of Dyes	498	(9)
E62 Benzenediazonium Chloride and Beta-Naphthol: 1-Phenylazo-2-Naphthol (Sudan I)	499	(3)
E63 p-Nitrobenzenediazonium Sulfate and Phenol: p-(4-nitrobenzeneazo)-phenol	502	(1)
E64 p-Nitrobenzenediazonium Sulfate and Beta-Naphthol: 1-(p-nitrophenylazo)-2-naphthol (Para Red; American Flag Red)	503	(2)
E65 p-Nitrobenzenediazonium Sulfate and Dimethylaniline: p-(4-nitrobenzeneazo)-N,N-Dimethylaniline	505	(2)
The Diels-Alder Reaction	507	(10)
E66 Butadiene (from 3-Sulfolene) and Maleic Anhydride	508	(2)
E67 Cyclopentadiene and Maleic Anhydride	510	(4)
E68 Furan and Maleic Anhydride	514	(1)
E69 Alpha-Phellandrene and Maleic Anhydride	515	(2)
The Writing Reaction	517	(10)
E70 The Preparation of trans-Stilbene	519	(5)
E71 Preparation of trans, trans-1, 4-Diphenylbutadiene: A Variation	524	(3)
Analgesics: Aspirin, Phenacetin, and Tylenol	527	(9)
E72 Acetylsalicylic Acid from Salicylic Acid: Preparation of Aspirin	527	(2)
E73 p-Acetamidophenol from p-Aminophenol: Preparation of Tylenol	529	(2)
E74 p-Ethoxyacetanilide from p-Ethoxyaniline: Preparation of Phenacetin	531	(4)
E75 p-Ethoxyacetanilide from p-Acetamidophenol: Another Preparation of Phenacetin	535	(1)
Nitration of Phenacetin	536	(2)
E76 2-Nitrophenacetin form Phenacetin	536	(2)
Esterification of Salicylic Acid	538	(2)
E77 Preparation of Methyl Salicylate: Oil of Wintergreen	538	(2)
Coconut Aldehyde; Gamma-Nonanolactone	540	(6)
E78 3-Nonenoic Acid from Heptaldehyde and Malonic Acid	541	(2)
E79 Coconut Aldehyde from 3-Nonenoic Acid	543	(4)
Catalysis by Thiamine	546	(6)
E80 Thiamine-Catalyzed Formation of Benzoin from Benzaldehyde	546	(6)
A Model for the Reducing Agent NADH	552	(7)
E81 1-Benzylnicotinamide Chloride from Nicotinamide	554	(2)
E82 1-Benzyldihydronicotinamide form 1-Benzylnicotinamide Chloride	556	(1)
E83 Reduction of Malachite Green by 1-Benzyl-dihydronicotinamide	557	(2)
Two Thermochronic Compounds	559	(5)
E84 Dixanthylene from Xanthone	560	(1)
E85 Dianthroquinone from Anthrone via 9-Bromoanthrone	561	(3)
A Photochromic Compound: 2-(2, 4-Dinitrobenzyl) pyridine	564	(14)
E86 A Photochromic Compound: 2-(2, 4-Dinitrobenzyl) pyridine	564	(3)
E87 A Chemiluminescent Compound: Luminol	567	(11)
Synthetic Sequences: Experiments that Use a Sequence of Reactions
Steroid Transformations	578	(11)
E88 Cholesterol Dibromide from Cholesterol	580	(2)
E89 5Alpha, 6Beta-Dibromocholestane-3-one from Cholesterol Dibromide	582	(1)
E90 Delta5-Cholestene-3-one from 5Alpha, 6Beta-Dibromocholestane-3-one	583	(4)
E91 Delta4-Cholestene-3-one from Delta5-Cholestene-3-one	587	(2)
Tetraphenylcyclopentadienone: A Purple Compound	589	(8)
E92 Benzoin from Benzaldehyde	591	(1)
E93 Benzil from Benzoin	592	(1)
E94 Dibenzylketone from Phenylacetic Acid	593	(2)
E95 Tetraphenylcyclopentadienone form Benzil and Dibenzyl Ketone	595	(2)
Sulfanilamide	597	(10)
E96 p-Acetamidobenzenesulfonyl Chloride from Acetanilide	602	(2)
E97 p-Acetamidobenzenesulfonamide from p-Acetamidobenzenesulfonyl Chloride	604	(1)
E98 Sulfanilamide from p-Acetamidobenzenesulfonamide	605	(2)
A Bootstrap Synthesis: p-Phenetidine from p-Phenetidine	607	(8)
E99 Ethyldioxyazobenzene from p-Phenetidine	608	(2)
E100 Diethyldioxyazobenzene from Ethyldioxyazobenzene	610	(1)
E101 p-Phenetidine from Diethyldioxyazobenzene	611	(4)
1-Bromo-3-Chloro-5-iodobenzene	615	(12)
E102 2-Chloro-4-Bromoacetanilide from 4-Bromoacetanilide	617	(3)
E103 2-Chloro-4-Bromoaniline from 2-Chloro-4-Bromoacetanilide	620	(2)
E104 2-Chloro-4-Bromo-6-iodoaniline from 2-Chloro-4-Bromoaniline	622	(2)
E105 1-Bromo-3-chloro-5-Iodobenzene from 2-Chloro-4-bromo-6-iodoaniline	624	(3)
MOED: A Merocyanine Dye	627	(8)
E106 1,4-Dimethylpyridinium Iodide from 4-Methylpyridine and Methyl Iodide	629	(1)
E107 Preparation of 4-(p-Hydroxystyryl)-1-Methylpyridinium Iodide from 1-4-Dimethylpyridinium Iodide and p-Hydroxybenzaldehyde	630	(2)
E108 1-Methyl-4 [(Oxocyclohexadienylidene)-Ethylidene]-1, 4-Dihydropyridine (MOED) from 4-(p-Hydroxystyryl)-1-Methyl-pyridinium Iodide	632	(3)
Appendix	635	(12)
Chemical Substance Index	647	(8)
General Subject Index	655