Techniques andExperiments forOrganic ChemistrySIXTH EDITIONAddison AultCornell College4 University Science BooksSausalito, California
ContentsPreface to the Sixth EditionxixPreface to the Fifth EditionxxiPARTILaboratory OperationsPreliminaryTopics1. oisoningCutsSpillsChemicals in the EyeA Short List of Hazardous Materials andSome of Their PropertiesGlassware Used in the Organic Chemistry LaboratoryCleaning Up3.1 Care of Ground-Glass-Jointed Glassware3.2 Separatory Funnels and Glassware with Stopcocks3.3 Drying of GlasswareCollection and Disposal of Waste4.1 Solid Waste4.2 Liquid Waste4.3 General Instructions for Collection of WasteThe Laboratory Notebook6. The Chemical Literature6.1 Secondary Sources for Physical Properties ofOrganic Compounds6.2 Secondary Sources for Methods of Preparation ofOrganic Compounds6.3 Collections of Spectra6.4 7
vi ContentsTables7.1 Solutions of Acids7.2 Solutions of Bases7.3 Molecular Weights and Molar Volumes of Acids7.4 Molar Weights of Bases7.5 Molecular Weights, Densities, and Molar Volumes ofSelected Liquid Reagents7.6 Periodic Table of the Elements38394040414142Separation of Substances;Purification of Substances8. Filtration8.1 Gravity Filtration8.2 Micro-Scale Gravity Filtration8.3 Vacuum or Suction Filtration444445459. Recrystallization9.1 Choiceof Solvent9.2 Dissolving the Sample9.3 Decolorizing the Solution9.4 Hot Filtration9.5 Cooling for Crystallization9.6 Cold Filtration9.7 Washing the Crystals9.8 Drying the Crystals9.9 More Techniques of Crystallization9.10 Micro-Scale Recrystallization9.11 Selection ofaSuitable Solvent48494950505253535455575910. Distillation10.1 Vapor Pressure10.2 Distillation of a Pure Liquid10.3 Miscible Pairs of Liquids10.4 Fractional Distillation10.5 Azotropic Mixtures10.6 Technique of Distillation10.7 Small-Scale Distillation626366677072757711. Reduced-Pressure Distillation11.1 Estimation of the Boiling Pointat Reduced Pressure11.2 Apparatus808182
Contents11.3 Source of Vacuum11.4 Pressure Measurement11.5 Technique of DistillationUnder Reduced Pressure83848512. Distillation of Mixtures of Two Immiscible Liquids;Steam Distillation12.1 Theory of Steam Distillation12.2 Technique of Steam Distillation87878813. Sublimation13.1 Theory of Sublimation13.2 Technique of Sublimation90909114. Extraction by Solvents14.1 Theory of Extraction14.2 Extraction ofAcids and Bases14.3 Technique of Extraction14.4 Micro-Scale Extraction15. Chromatography15.1 Theory of Column Chromatography15.2 Technique of Column Chromatography15.3 Theory ofThin-Layer Chromatography15.4 Technique ofThin-Layer Chromatography15.5 Theory of Paper Chromatography15.6 Technique of Paper Chromatography15.7 Theory ofVapor-Phase Chromatography15.8 Technique ofVapor-Phase Chromatography15.9 High-Pressure Liquid Chromatography15.10 Batchwise Adsorption; 2612812916. Removal of Water; Drying16.1 Drying of Solids16.2 Drying of Solutions16.3 Drying of Solvents and Liquid Reagents129130132134Determination of Physical Properties17. Boiling Point17.1 Experimental Determination of Boiling Point17.2 Boiling Point and Molecular Structure17.3 Boiling Point and the Enthalpy and Entropy ofVaporization138138141144vii
18. Melting Point18.1 Experimental Determination of the Melting Point18.2 The Melting Point as a Criterion of Purity18.3 The Melting Point as a Means of Identificationand Characterization18.4 Mixture Melting Points18.5 Melting Point and Molecular Structure19. Density; Specific Gravity19.1 Experimental Determination of the Density19.2 Density and Molecular Structure20. Index ofRefraction20.1 Experimental Determinationof the Index ofRefraction20.2 Index ofRefraction and Molecular Structure21. Optical Activity21.1 Experimental Determination of Optical Rotation21.2 Optical Activity and Molecular Structure22. Molecular Weight22.1 Molecular Weight Determinationby Mass Spectrometry22.2 Molecular Weight Determination byOtherMethods23. Solubility23.1 Solubility of Liquids in Liquids23.2 Solubility of Solids in Liquids23.3 Classification of Compounds by Solubility;Relationships Between Solubility andMolecular Structure23.4 Techniques for Determination of Solubility24. Infrared Absorption Spectrometry24.1 Wavelength, Frequency, andEnergy of Electromagnetic Radiation24.2 Units of Light Absorption24.3 InfraredLight Absorption and Molecular Structure24.4 Interpretation of Infrared Spectra24.5 Sample Preparation25. Ultraviolet-Visible Absorption Spectrometry25.1 Ultraviolet-Visible Light Absorptionand Molecular Structure25.2 Interpretation of Ultraviolet-Visible Spectra25.3 Color and Molecular Structure25.4 Sample 1202203203204
ContentsNuclear Magnetic Resonance Spectrometry26.1 Shielding; Chemical ShiftSplitting26.226.3 The Integral26.4 Nuclear Magnetic Resonance andMolecular Structure26.5 Interpretation of NMR Spectra26.6Sample PreparationMass Spectrometry27.1 Theory of Mass Spectrometry27.2 Interpretation of Mass Spectra27.3 High-Resolution Mass mination of Chemical Properties:Qualitative Organic Analysis28. Qualitative Tests for the Elements28.1 Ignition Test; Test for Metals28.2 Beilstein Test; Test for Halogens(Except Fluorine)28.3 Sodium Fusion Test; Test for Nitrogen,Sulfur, and the Halogens29. Qualitative Characterization Tests:Tests for the Functional Groups29.1 Detection of Ammonia from AmmoniumSalts, Primary Amides, and Nitriles29.2 Benzenesulfonyl Chloride (Hinsberg's Test)29.3 Bromine in Carbon Tetrachloride29.4 Chromic Anhydride29.5 2,4-Dinitrophenylhydrazine29.6 Ferric Chloride Solution29.7 Ferric Hydroxamate Test29.8 Hydrochloric Acid/Zinc Chloride Test(Lucas's Test)29.9 Iodoform Test29.10 Aqueous Potassium Permanganate Solution(Baeyer's Test)29.11 Alcoholic Silver Nitrate Solution29.12 Sodium Hydroxide Test29.13 Sodium Iodide in Acetone29.14 Tollen's Reagent: Silver-Ammonia Complex 1262263263ix
xContents30. Characterization Through Formation of Derivatives30.1 Benzoates, jb-Nitrobenzoates, and3,5-Dinitrobenzoates of Alcohols30.2 Hydrogen 3-Nitrophthalates of Alcohols30.3 Phenyl-and a-Naphthylurethans30.4 Methone Derivations ofAldehydes30.5 2,4-Dinitrophenylhydrazones30.6 Semicarbazones30.7 Oximes30.8 Carboxylic Acids by Hydrolysis of PrimaryAmides and Nitriles30.9 9-Acylamidoxanthenes from Amides30.10 Hydrolysis of N-Substituted Amides30.11 Substituted Acetamides from Amines30.12 Substituted Benzamides from Amines30.13 /i-Toluenesulfonamides from Amines30.14 Phenylthioureas and a-Naphthylthioureas30.15 Picrates30.16 Quaternary Ammonium Salts: Methiodides and/»-Toluenesulfonates30.17 Carboxylic Acid Amides30.18 Anilides, jb-Toluidides, and jb-Bromoanilidesof Carboxylic Acids30.19 Phenacyl and Substituted PhenacylEsters of Carboxylic Acids30.20 jö-Nitrobenzyl Esters of Carboxylic Acids30.21 N-Benzylamides from Esters30.22 3,5-Dinitrobenzoates from Esters30.23 Hydrolysis of Esters30.24 Bromination of Aromatic Ethers30.25 S-Alkylthiuronium Picrates30.26 o-Aroylbenzoic Acids fromAromatic Hydrocarbons30.27 Aromatic Acids by Oxidation by Permanganate30.28 Anilides, /»-Toluidides,and a-Naphthalides from Alkyl Halides30.29 2,4,7-Trinitrofluorenone Adducts of AromaticHydrocarbons30.30 Bromination of Phenols30.31 Aryloxyacetic Acids from 297
Apparatus and Techniquesfor Chemical Reactions31. Assembling the Apparatus32. Temperature Control33. Methods of Heating and Cooling33.1 Heating33.2 Cooling34. Stirring35. Addition of Reagents36. Control of Evolved Gases37. Concentration; Evaporation38. Use of an Inert Atmosphere39. Working Up the Reaction; Isolation of the rimentsIsolations and PurificationsElE2E3E4E5E6E7E8E9E10EllEl2Isolation of Cholesterol from GallstonesIsolation ofLactose from Powdered MilkIsolation of Acetylsalicylic Arid from Aspirin TabletsIsolation of Ibuprofen from Ibuprofen TabletsIsolation of Caffeine from Tea and NoDozIsolation of Piperine from Black PepperIsolation of Trimyristin from NutmegIsolation of Clove Oil from ClovesIsolation ofEugenol from Clove OilIsolation of (R)-( )-Limonene from Grapefruitor Orange PeelIsolation of (R)-(-)-or (S)-( )-Carvone from Oilof Spearmint or Oil of CarawayResolution of a-Phenylethylamineby (R),(R)-( )-Tartaricarid327329332335337340342344346347350355
TransformationsIsomerizationsE13 Adaman tane froratfwdo-Tetrahydrodicyclopentadienevia the Thiourea ClathrateEl4 os-Dibenzoylethyelene from rare5-l,2-DibenzoylethylenePreparation of CyclohexanolE15 Cyclohexanol from CyclohexeneEl 6 Cycohexanol from CyclohexanoneReactions of CyclohexanolEl 7E18E19E20Cyclohexene from CyclohexanolDehydration of 2-Methylcyclohexanol: A VariationCyclohexyl Bromide from CyclohexanolCyclohexanone from CyclohexanolAddition of Dichlorcarbene to Alkenesby Phase Transfer CatalysisE21 Addition of Dichlorocarbene to CyclohexeneE22 Addition of Dichlorocarbene to Styrene:A VariationE23 Addition of Dichlorocarbeneto 1,5-Cyclooctadiene: Another VariationAlkyl Halides from AlcoholsE24E25E26E27E28E29Isoamyl Bromide from Isoamyl Alcoholn-Butyl Bromide from n-Butyl Alcohol:A Variationtert-Butyl Chloride from tert-Butyl Alcoholtert-Amyl Chloride from teri-Amyl Alcohol:A VariationCompetitive Nucleophilic Substitutionof Butyl Alcohols by Bromide and Chloride IonKinetics of the Hydrolysis of tert-Buty\ 395397398402403406407410
ContentsIsoamyl Acetate: A Componentof the Alarm Pheromone of the Honey BeeE30 Isoamyl Acetate from Isoamyl Bromideand Potassium AcetateE31 Isoamyl Acetate from Isoamyl Alcoholand Acetic Acid; The Fischer Estrification424Liquid CrystalsE32 Cholesteryl Benzoate from Cholesterol427428Acetylation of GlucoseE33 a-D-Glucose Pentaacetate from GlucoseE34 ß-D-Glucose Pentaacetate from GlucoseE35 Acetylation of Glucosein iV-Methylimidazole: A VariationE36 Preparation of Methyl Benzoate, Oil of Niobe431433433The Grignard ReactionE37 Aliphatic Alcohols: Preparationby Grignard SynthesisPreparation of TriphenylmethanolE38 Preparation of Triphenylmethanolfrom BenzophenoneE39 Preparation of Triphenylmethanolfrom Methyl BenzoateE40 Preparation of Triphenylmethanolfrom Dimethyl CarbonateE41 Preparation of Aniline from NitrobenzenePreparation of AmidesE42 Acetanilide from AnilineE43 7V,iV-Diethyl-m-Toluamidefrom »i-Toluic Acid; A Mosquito Repellant: "OffElectrophilic Substitution Reactionsof Benzene DerivativesE44 Methyl m-Nitrobenzoate from Methyl BenzoateE45 jb-Bromoacetanilide from AcetanilideE46 2,4-Dinitrobromobenzene from 7461463464466469xiii
xiv ContentsNucleophilic Aromatic Substitution Reactionsof 2,4-DinitrobromobenzeneE47 2,4-DinitroanilineE48 2,4-DinitrophenylhydrazineE49 2,4-DinitrodiphenylamineE50 2,4-DinitrophenylpiperidineE51 4-Substituted 2,4-Dinitrophenylanilines:A VariationOiazonium Salts of Aromatic AminesE52 Benzenediazonium Chloride from AnilineE53 jö-Nitrobenzenediazonium 1482Replacement Reactions of Diazonium SaltsE54 Chlorobenzene fromBenzenediazonium Chloride482483Reactions of VanillinE55 Acetylvanillin from VanillinE56 5-Bromovanillin from VanillinE57 5-Nitrovanillin from VanillinE58 Vanillin Oxime from VanillinE59 Vanillin Semicarbazone from VanillinE60 Vanillyl Alcohol from VanillinE61 Vanillideneacetone from Vanillin485486487489490491493494Synthesis of DyesE62 Benzenediazonium Chloride and ß-Naphthol:l-Phenylazo-2-Naphthol (Sudan I)E63 jb-Nitrobenzenediazonium Sulfate and Phenol:jb-(4-nitrobenzeneazo)-phenolE64 -Nitrobenzenediazonium Sulfate andß-Naphthol: l-(/;-nitrophenylazo)-2-naphthol(Para Red; American Flag Red)E65 -Nitrobenzenediazonium Sulfateand ylaniline498499502503505The Diels-Alder Reaction507E66 Butadiene (from 3-Sulfolene) and Maleic Anhydride 508E67 Cyclopentadiene and Maleic Anhydride510E68 Furan and Maleic Anhydride514E69 a-Phellandrene and Maleic Anhydride515
ContentsThe Wittig ReactionE70 The Preparation of trans-SülbeneE71 Preparation oftrans, rans-l,4-Diphenylbutadiene:A Variation517519Analgesics: Aspirin, Phenacetin, and TylenolE72 Acetylsalicylic Acid from Salicylic Acid:Preparation of AspirinE73 jb-Acetamidophenol from jö-Aminophenol:Preparation of TylenolE74 /»-Ethoxyacetanilide from jf?-Ethoxyaniline:Preparation of PhenacetinE75 jö-Ethoxyacetanilide from /»-Acetamidophenol:Another Preparation of Phenacetin527529Nitration of PhenacetinE76 2-Nitrophenacetin from Phenacetin536536Esterification of Salicylic AcidE77 Preparation of Methyl Salicylate:Oil of Wintergreen538Coconut Aldehyde; y-NonanolactoneE78 3-Nonenoic Acid from Heptaldehydeand Malonic AcidE79 Coconut Aldehyde from 3-Nonenoic AcidCatalysis by ThiamineE80 Thiamine-Catalyzed Formation of Benzoin fromBenzaldehydeA Model for the Reducing Agent NADHE81 1-Benzylnicotinamide Chloride fromNicotinamideE82 1-Benzyldihydronicotinamide from1-Benzylnicotinamide ChlorideE83 Reduction of Malachite Green by 1-BenzyldihydronicotinamideTwo Thermochronic CompoundsE84 Dixanthylene from XanthoneE85 Dianthroquinone from Anthronevia 9-Bromoan 9560561xv
xvi ContentsA Photochromic Compound: 2-(2,4-Dinitrobenzyl)PyridineE86 A Photochromic Compound:2-(2,4-Dinitrobenzyl) pyridineE87 A Chemiluminescent Compound: Luminol564564567Synthetic Sequences:Experiments that Use a Sequenceof ReactionsSteroid TransformationsE88 Cholesterol Dibromide from CholesterolE89 5 x,6ß-Dibromocholestane-3-onefrom Cholesterol DibromideE90 A 5 -Cholestene-3-onefrom 5a,6ß-Dibromocholestane-3-oneE91 A 4 -Cholestene-3-one fromA 6 -Cholestene-3-oneTetraphenylcyclopentadienone:A Purple CompoundE92 Benzoin from BenzaldehydeE93 Benzil from BenzoinE94 Dibenzylketone from Phenylacetic AcidE95 Tetraphenylcyclopentadienone from Benziland Dibenzyl KetoneSulfanilamideE96 / -Acetamidobenzenesulfonyl Chloridefrom AcetanilideE97 jb-Acetamidobenzenesulfonamidefrom jö-Acetamidobenzenesulfonyl ChlorideE98 Sulfanilamide from/»-AcetamidobenzenesulfonamideA Bootstrap Synthesis: p-Phenetidinefrom p-PhenetidineE99 Ethyldioxyazobenzene from jö-PhenetidineEl00 Diethyldioxyazobenzenefrom EthyldioxyazobenzeneElOl jb-Phenetidine from 95597602604605607608610611
Contents1-Bromo-3-Chloro-5-iodobenzeneEl02 2-Chloro-4-Bromoacetanilidefrom 4-Bromoace tanilideE103 2-Chloro-4-Bromoanilinefrom 2-Chloro-4-BromoacetanilideE104 2-Chloro-4-Bromo-6-iodoanilinefrom 2-Chloro-4-BromoanilineEl05 l-Bromo-3-chloro-5-Iodobenzenefrom 2-Chloro-4-bromo-6-iodoanilineMOED: A Merocyanine DyeE106 1,4-Dimethylpyridinium lodidefrom 4-Methylpyridine and Methyl lodideE107 Preparation of4- ( -Hydroxystyryl) -1 -Me thylpyridiniumlodide from 1-4-Dimethylpyridinium lodideand j&-HydroxybenzaldehydeE108 l-Methyl-4[ (Oxocyclohexadienylidene)-E thylidene ] -1,4-Dihydropyridine(MOED) from 4-(/ -Hydroxystyryl)-l-Methylpyridinium al Substance Index647General Subject Index655xvii
18.1 Experimental Determination of the Melting Point 150 18.2 The Melting Point as a Criterion of Purity 154 18.3 The Melting Point as a Means of Identification . E7 Isolation of Trimyristin from Nutmeg 342 E8 Isolation of Clove Oil from Cloves 344 E9 Isolation ofEugenol from Clove Oil 346 E10 Isolation of (R)-( )-Limonene from Grapefruit .
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