Experimental Organic Chemistry: A Balanced Approach : Macroscale and Microscale

by Mohrig, Jerry R.; Hammond, Christina Noring; Morrill, Terence C.; Neckers, Douglas C.; Mohrig, Jerry R.

• ISBN13: 9780716728184
• ISBN10: 0716728184
• Format: Hardcover
• Copyright: 1997-08-01
• Publisher: W H Freeman & Co

Table of Contents

PREFACE	xx
INTRODUCTION: GETTING ACQUAINTED WITH THE LABORATORY	1	(12)
I.1 Experimental Organic Chemistry	1	(1)
1.2 Laboratory Safety	1	(1)
I.3 Cleanup Following an Experiment	2	(1)
I.4 Desk Equipment	3	(1)
I.5 Introduction to Macroscale and Microscale Laboratory Work	4	(1)
I.6 Using Handbooks	5	(4)
I.7 Your Laboratory Notebook	9	(4)
Part 1 Experiments	13	(340)
1 EXTRACTION OF CAFFEINE FROM TEA	15	(7)
2 PURIFICATION AND THIN-LAYER CHROMATOGRAPHIC ANALYSIS OF CAFFEINE	22	(5)
3 SYNTHESIS OF ETHANOL BY FERMENTATION OF SUCROSE	27	(5)
4 SYNTHESIS OF SALICYLIC ACID	32	(9)
5 SYNTHESIS OF ASPIRIN	41	(8)
Optional Experiment: Thin-Layer Chromatographic Analysis of Analgesics	47	(2)
6 RADICAL CHLORINATION REACTIONS	49	(5)
7 ISOLATION OF ESSENTIAL OILS AND THE THEORY OF ODOR	54	(13)
7.1 Isolation of S-(+)-Carvone from Caraway Seeds	56	(7)
7.2 Isolation of R-(+)-Limonene from Orange Peels	63	(4)
8 NUCLEOPHILIC SUBSTITUTION REACTIONS	67	(15)
8.1 S(N)1/S(N)2 Reactivity of Alkyl Halides	71	(5)
8.2 Preparation and Identification of Alkyl Bromides Synthesized from Unknown Alcohols	76	(6)
9 ADDITION REACTIONS OF ALKENES	82	(21)
9.1 Free Radical versus Ionic Addition of Hydrobromic Acid to Alkenes	83	(8)
9.2 Dimerization of 2-Methylpropene (Isobutylene)	91	(7)
9.3 Stereochemistry of Bromine Addition to trans-Cinnamic Acid	98	(5)
10 DEHYDROHALOGENATION OF 2-BROMOHEPTANE: VARIATION OF PROMOTING BASE	103	(5)
11 DEHYDRATION OF ALCOHOLS	108	(15)
11.1 Synthesis of Cyclohexene by Acid-Catalyzed Dehydration of Cyclohexanol	110	(6)
11.2 Dehydration of 2-Methylcyclohexanol	116	(7)
12 ETHER SYNTHESES	123	(11)
12.1 Williamson Ether Synthesis of Ethoxybutane	124	(5)
12.2 Synthesis and Analysis of a Propyl Benzhydryl Ether	129	(5)
13 GRIGNARD SYNTHESES	134	(26)
13.1 Synthesis of Phenylmagnesium Bromide and Its Use as a Synthetic Intermediate	138	(17)
13.1a Synthesis of Diphenylmethanol (Benzhydrol)	142	(6)
13.1b Synthesis of Triphenylmethanol	148	(3)
13.1c Synthesis of Benzoic Acid	151	(4)
13.2 Grignard Synthesis of a Triphenylmethane Dye: Crystal Violet or Malachite Green	155	(5)
14 PHASE TRANSFER CATALYSIS	160	(11)
14.1 Williamson Ether Synthesis of Bis-4-Chlorobenzyl Ether Using Phase Transfer Catalysis	162	(5)
14.2 Synthesis of Butyl Benzoate Using Phase Transfer Catalysis	167	(4)
15 OXIDATION REACTIONS	171	(17)
15.1 Oxidation of Cyclohexanol Using Sodium Hypochlorite	174	(5)
15.2 General Method for Oxidizing Secondary Alcohols to Ketones	179	(4)
15.3 Oxidation of Cinnamyl Alcohol Using Pyridinium Chlorochromate	183	(5)
16 DIELS-ALDER REACTIONS	188	(13)
16.1 Synthesis of Dimethyl 3,4,5,6-Tetraphenylphthalate from 2,3,4,5-Tetraphenylcyclopentadienone and Dimethyl Acetylene Dicarboxylate	189	(5)
16.2 Synthesis of 4-Cyclohexene-cis-1,2-Dicarboxylic Acid from Butadiene Sulfone and Maleic Anhydride	194	(7)
17 ELECTROPHILIC AROMATIC SUBSTITUTION	201	(16)
17.1 Iodination of 1,2,4,5-Tetramethylbenzene Using Iodine and Periodic Acid	203	(5)
17.2 Bromination of Acetanilide	208	(6)
Optional Experiment: Removal of the Acetyl Protecting Group: Synthesis of a Bromoaniline	212	(2)
17.3 Rates of Electrophilic Aromatic Substitution	214	(3)
18 ACYLATION AND ALKYLATION OF AROMATIC COMPOUNDS	217	(19)
18.1 Acylation of Ferrocene	220	(6)
18.2 Synthesis of 4,4'-Di-tert-Butylbiphenyl	226	(6)
18.3 Synthesis of 1,4-Di-tert-Butyl-2,5-Dimethoxybenzene	232	(4)
19 REDUCTION REACTIONS OF 3-NITROACETOPHENONE	236	(8)
19.1 Reduction of 3-Nitroacetophenone Using Tin and Hydrochloric Acid	239	(2)
19.2 Reduction of 3-Nitroacetophenone Using Sodium Borohydride	241	(3)
20 PHOTOCHEMISTRY: PHOTOREDUCTION OF BENZOPHENONE AND REARRANGEMENT TO BENZPINACOLONE	244	(8)
21 ALDOL CONDENSATION: REACTION OF BENZALDEHYDE AND ACETONE	252	(7)
22 SYNTHESIS OF 2,3,4,5-TETRAPHENYLCYCLOPENTADIENONE	259	(8)
23 HORNER-EMMONS-WITTIG SYNTHESIS OF METHYL 4-METHOXY-E-CINNAMATE	267	(8)
24 KINETIC VERSUS THERMODYNAMIC CONTROL IN CHEMICAL REACTIONS	275	(14)
24.1 Semicarbazones of Cyclohexanone and 2-Furaldehyde	276	(8)
24.2 Friedel-Crafts Alkylation of Chlorobenzene	284	(5)
Optional Experiments	289	(1)
25 SYNTHESIS OF ESTERS	289	(16)
25.1 Synthesis of Isopentyl Acetate (Banana Oil)	291	(6)
Optional Experiments: Propyl Ethanoate (Propyl Acetate) and 2-Methyl-1-Propyl Propanoate (Isobutyl Propionate)	296	(1)
25.2 Synthesis and Identification of an Ester from an Unknown Alcohol and Acetic Acid	297	(8)
26 AMIDE CHEMISTRY	305	(22)
26.1 Synthesis of Hippuric Acid	306	(7)
Optional Experiment: Solubilities of Benzoic Acid and Hippuric Acid	312	(1)
26.2 Synthesis of a Mosquito Repellent: N,N-Diethyl-meta-Toluamide (Deet)	313	(14)
27 POLYPHOSPHORIC ACID-CATALYZED BECKMANN REARRANGEMENT OF ACETOPHENONE OXIME	327	(6)
28 SYNTHESIS OF trans-1,2-DIBENZOCYCLOPROPANE BY RING CLOSURE	333	(6)
29 POLYMER CHEMISTRY	339	(14)
29.1 Synthesis of Polystyrene	342	(7)
Optional Experiment	348	(1)
29.2 Biodegradable Starch Films	349	(4)
Part 2 Projects	353	(144)
1 HYDROLYSIS OF AN UNKNOWN ESTER	355	(14)
1.1 Hydrolysis and Azeotropic Distillation	357	(3)
1.2 Extraction and Recrystallization	360	(4)
1.3 Distillation, Melting Points, and Identification	364	(5)
2 SYNTHESIS OF 1-BROMOBUTANE AND A GRIGNARD SYNTHESIS OF AN ALCOHOL	369	(14)
2.1 Synthesis of 1-Bromobutane from 1-Butanol	370	(5)
Optional Syntheses of Alkyl Halides	374	(1)
2.2 Grignard Synthesis of Secondary and Tertiary Alcohols	375	(8)
Optional Synthesis	380	(3)
3 SYNTHESIS AND DEHYDRATION OF 3,3-DIMETHYL-2-BUTANOL	383	(9)
3.1 Synthesis of 3,3-Dimethyl-2-Butanol by Reduction with Sodium Borohydride	384	(3)
3.2 Acid-Catalyzed Dehydration of 3,3-Dimethyl-2-Butanol with Rearrangement	387	(5)
4 INTERCONVERSION OF 4-tert-BUTYLCYCLOHEXANOL AND 4-tert-BUTYLCYCLOHEXANONE	392	(16)
4.1 Sodium Hypochlorite Oxidation of 4-tert-Butylcyclohexanol to 4-tert-Butylcyclohexanone	394	(6)
4.2 Sodium Borohydride Reduction of 4-tert-Butylcyclohexanone	400	(5)
Optional GC or NMR Experiment	405	(3)
5 ALDOL CONDENSATION USING AN UNKNOWN ALDEHYDE AND AN UNKNOWN KETONE: DERIVATIVE FORMATION AND IDENTIFICATION OF UNKNOWNS	408	(11)
5.1 Preparation of Aldol Condensation Product	413	(1)
5.2 Characterization of the Aldol Product	414	(5)
6 BENZOIN CHEMISTRY: SYNTHESIS OF AN ANTICONVULSANT DRUG USING BIOCHEMICAL CATALYSIS	419	(16)
6.1 Thiamine-Catalyzed Benzoin Condensation	419	(8)
6.2 Oxidation of Benzoin	427	(4)
6.3 Synthesis of 5,5-Diphenylhydantoin, an Anticonvulsant Drug	431	(4)
7 SYNTHESIS OF BENZOCAINE	435	(8)
8 RESOLUTION OF R,S-BENZOYLAMINO ACIDS	443	(13)
8.1 Papain	444	(4)
8.2 Resolution of R,S-Benzoylamino Acids	448	(1)
8.3 Synthesis of the R,S-Benzoylamino Acid	449	(3)
8.4 Synthesis of the S-Benzoylamino Acid Anilide: Enzymatic Resolution	452	(1)
8.5 Optical Activity of S-Benzoylamino Acid Anilide	453	(2)
8.6 Further Experiment	455	(1)
9 MULTISTEP SYNTHESIS OF PARA RED FROM ACETANILIDE	456	(11)
9.1 Two-Step Synthesis of p-Nitroaniline	459	(4)
9.2 Preparation of Diazonium Salts	463	(4)
10 SYNTHESES STARTING WITH ALKYL HALIDES	467	(4)
11 DIELS-ALDER CYCLOADDITIONS OF VARIOUS DIENOPHILES TO 2,3-DIMETHYL-1,3-BUTADIENE	471	(5)
11.1 Synthesis of cis-4,5-Dimethyl-1,2,3,6-Tetrahydrophthalic Anhydride	471	(2)
11.2 Addition of Various Dienophiles to 2,3-Dimethyl-1,3-Butadiene	473	(3)
12 MULTISTEP SYNTHESIS OF N-PHENYLTETRAPHENYL-PHTHALIMIDE	476	(10)
12.1 Synthesis of Tetraphenylcyclopentadienone	478	(1)
12.2 Synthesis of Dimethyl Tetraphenylphthalate	479	(1)
12.3 Synthesis of Tetraphenylphthalic Acid	480	(2)
12.4 Synthesis of Tetraphenylphthalic Anhydride	482	(2)
12.5 Synthesis of N-Phenyl-3,4,5,6-Tetraphenylphthalimide	484	(2)
13 SUGARS: THE GLUCOSE PENTAACETATES	486	(11)
13.1 Preparation of Stereoisomers of D-Glucose	491	(2)
13.2 (1)H NMR Analysis of XXX- and XXX-D-Glucose Pentaacetates	493	(1)
13.3 Optical Activity of Sugars	493	(1)
13.4 Further Investigations	494	(3)
Part 3 Organic Qualitative Analysis	497	(80)
1 IDENTIFICATION OF UNKNOWNS	499	(3)
2 PHYSICAL PROPERTIES	502	(2)
3 CLASSIFICATION BY SOLUBILITY AND ELEMENTAL ANALYSIS BY SODIUM FUSION	504	(12)
3.1 Classification by Solubility	504	(8)
3.2 Elemental Analysis by Sodium Fusion	512	(4)
4 INFRARED, NUCLEAR MAGNETIC RESONANCE, AND MASS SPECTROMETRIC ANALYSIS	516	(8)
4.1 Using Spectrometric Data	520	(4)
5 CLASSIFICATION TESTS FOR FUNCTIONAL GROUPS	524	(27)
5.1 Alcohols	526	(3)
5.2 Aldehydes and Ketones	529	(4)
5.3 Alkenes	533	(2)
5.4 Alkyl Halides	535	(3)
5.5 Amines	538	(3)
5.6 Aromatic Hydrocarbons (Arenes)	541	(2)
5.7 Aryl Halides	543	(1)
5.8 Carboxylic Acids	543	(1)
5.9 Carboxylic Acid Derivatives	544	(1)
5.9a Acyl Chlorides	544	(1)
5.9b Esters	544	(1)
5.10 Amides, Acyl Chlorides, Esters, and Nitriles	545	(4)
5.11 Ethers	549	(1)
5.12 Phenols	549	(2)
6 SYNTHESIS OF SOLID DERIVATIVES	551	(13)
6.1 Alcohols	552	(3)
6.2 Aldehydes and Ketones	555	(2)
6.3 Amines	557	(3)
6.4 Carboxylic Acides: Amides, Anilides, Toluidides	560	(2)
6.5 Phenols	562	(2)
7 SEPARATION OF MIXTURES	564	(8)
7.1 Assaying the Number of Compounds	567	(1)
7.2 Separating the Mixture	568	(3)
7.3 Model Extraction Procedure	571	(1)
8 SUMMARY OF IDENTIFICATION PROCEDURE FOR AN UNKNOWN COMPOUND	572	(1)
9 SUMMARY OF ANALYSIS OF A MIXTURE OF UNKNOWN COMPOUNDS	573	(4)
Part 4 Spectrometric Methods	577	(110)
1 INFRARED SPECTROMETRY	579	(31)
1.1 Theory of Molecular Vibration	580	(1)
1.2 Infrared Spectrum	581	(3)
1.3 Infrared Instrumentation	584	(4)
1.4 Techniques of Sample Preparation	588	(5)
1.5 Interpreting Infrared Spectra	593	(17)
2 NMR SPECTROMETRY	610	(54)
2.1 NMR Instrumentation	612	(2)
2.2 Chemical Shift	614	(7)
2.3 Spin-Spin Splitting	621	(3)
2.4 Detecting Chemical Equivalence	624	(2)
2.5 Integration	626	(1)
2.6 Preparing the NMR Sample	627	(3)
2.7 Recording the NMR Spectrum	630	(1)
2.8 Interpreting (1)H NMR Spectra	630	(4)
2.9 (13)C NMR	634	(6)
2.10 An Approach to Solving NMR Problems	640	(10)
2.11 Two-Dimensional NMR and Related Techniques (Special Topic)	650	(14)
3 MASS SPECTROMETRY	664	(11)
4 ULTRAVIOLET AND VISIBLE SPECTROMETRY	675	(8)
5 INTEGRATED PROBLEMS	683	(4)
Part 5 Techniques of the Organic Laboratory	687
1 SAFETY	689	(17)
1.1 Causes of Laboratory Accidents	689	(3)
1.2 Safety Features of Your Laboratory	692	(2)
1.3 Preventing Accidents	694	(2)
1.4 What to Do if an Accident Occurs	696	(1)
1.5 Chemical Toxicology	697	(1)
1.6 Where to Find Chemical Safety Information	698	(5)
1.7 Protecting The Environment	703	(3)
2 LABORATORY GLASSWARE	706	(8)
2.1 Standard Taper Glassware	706	(4)
2.2 Microscale Glassware	710	(1)
2.3 Cleaning Your Glassware	711	(1)
2.4 Pasteur Filter Pipets	712	(2)
3 HEATING METHODS	714	(10)
3.1 Boiling Stones	714	(1)
3.2 Heating Devices	715	(4)
3.3 Refluxing a Reaction Mixture	719	(5)
3.3a Refluxing a Reaction Mixture under Anhydrous Conditions	720	(4)
4 EXTRACTION AND DRYING AGENTS	724	(25)
4.1 Extraction: The Theory	726	(2)
4.2 Macroscale Extractions	728	(2)
4.3 Additional Information about Extractions	730	(4)
4.4 Summary of Macroscale Extraction from Water to an Organic Solution	734	(1)
4.5 Microscale Extractions	734	(8)
4.5a Extracting an Aqueous Solution with an Organic Solvent More Dense Than Water	736	(1)
4.5b Washing an Organic Liquid That Is More Dense Than Water	737	(4)
4.5c Extraction with an Organic Solvent Less Dense Than Water	741	(1)
4.5d Washing an Organic Liquid That Is Less Dense Than Water	741	(1)
4.6 Drying Organic Liquids	742	(3)
4.7 Methods for Separating Drying Agents and Organic Liquids	745	(1)
4.8 Recovery of the Organic Product from the Dried Extraction Solution	746	(3)
5 RECRYSTALLIZATION	749	(16)
5.1 Theory of Recrystallization	749	(3)
5.2 Selecting a Proper Recrystallization Solvent	752	(2)
5.2a Recrystallization from Mixed Solvent Pairs	753	(1)
5.3 Macroscale Procedure for Recrystallizing a Solid	754	(5)
5.3a Removing Impurities from the Recrystallization Solution	756	(3)
5.4 Summary of the Macroscale Recrystallization Procedure	759	(1)
5.5 Microscale Recrystallization	759	(4)
5.5a Recrystallizing 150 to 500 Milligrams of a Solid	759	(2)
5.5b Recrystallizing Less than 150 to 500 Milligrams of a Solid in a Craig Tube Apparatus	761	(2)
5.6 Summary of the Microscale Recrystallization Procedures	763	(1)
5.7 What to Do If No Crystals Appear in the Cooled Solution	763	(1)
5.8 Pointers for Successful Recrystallizations	764	(1)
6 MELTING POINTS AND MELTING RANGES	765	(11)
6.1 Melting Point Theory	766	(2)
6.2 Apparatus for Determining Melting Ranges	768	(3)
6.3 Determining Melting Ranges	771	(2)
6.4 Mixture Melting Points	773	(1)
6.5 Thermometer Calibration	774	(1)
6.6 Summary of Melting-Point Determination	775	(1)
7 BOILING POINTS, DISTILLATION, AND AZEOTROPES	776	(29)
7.1 Boiling Points	777	(2)
7.1a Determination of Boiling Points	778	(1)
7.2 Boiling Points and Separation of Mixtures	779	(4)
7.3 Simple Distillation	783	(8)
7.3a Short-Path Distillation	788	(1)
7.3b Microscale Distillation	789	(2)
7.4 Fractional Distillation	791	(3)
7.5 Azeotropic Distillation	794	(2)
7.6 Steam Distillation	796	(2)
7.7 Vacuum Distillation	798	(7)
8 SUBLIMATION	805	(3)
8.1 Assembling the Apparatus for a Sublimation	806	(1)
8.2 Carrying Out a Microscale Sublimation	807	(1)
9 REFRACTROMETRY	808	(5)
9.1 Theory of Refractometry	809	(1)
9.2 The Refractometer	810	(1)
9.3 Steps in Determining a Refractive Index	811	(1)
9.4 Temperature Correction	812	(1)
10 THIN-LAYER CHROMATOGRAPHY	813	(13)
10.1 Principles of Thin-Layer Chromatography	815	(2)
10.2 Plates for Thin-Layer Chromatography	817	(1)
10.3 Sample Application	818	(2)
10.4 Choices of Developing Solvent	820	(3)
10.5 Visualization Techniques	823	(2)
10.6 Summary of TLC Procedure	825	(1)
11 GAS-LIQUID CHROMATOGRAPHY	826	(15)
11.1 Instrumentation	827	(2)
11.2 Columns and Liquid Stationary Phases	829	(3)
11.3 Detectors	832	(3)
11.4 Interpreting Chromatograms	835	(1)
11.5 Practical GC Operating Procedures	836	(3)
11.6 Identification of Components and Qualitative Analysis	839	(2)
12 LIQUID CHROMATOGRAPHY	841	(16)
12.1 Adsorbents	842	(2)
12.2 Elution Solvents	844	(1)
12.3 Choosing a Column	845	(2)
12.4 Making a Macroscale Column	847	(1)
12.5 Elution Techniques	848	(2)
12.6 Microscale Column Chromatography	850	(1)
12.7 Summary of Column Chromatography Techniques	851	(1)
12.8 Dry Column Chromatography	852	(1)
12.9 Flash Chromatography	852	(2)
12.10 High-Performance Liquid Chromatography	854	(3)
13 POLARIMETRY	857
13.1 Mixtures of Optical Isomers: Separation/Resolution	857	(5)
13.2 Polarimetric Instrumentation	862	(2)
13.3 Specific Rotation	864	(2)
13.4 Using the Polarimeter	866	(1)
13.5 Enantiomeric Excess (Optical Purity)	867
Appendix A DERIVATIVE TABLES FOR ORGANIC QUALITATIVE ANALYSIS	A-1
Appendix B THE LITERATURE OF ORGANIC CHEMISTRY	B-1
Index	I-1