Techniques and
Experiments for
Organic Chemistry
SIXTH EDITION
Addison Ault
Cornell College
4>
University Science Books
Sausalito, California
Contents
Preface to the Sixth Edition
xix
Preface to the Fifth Edition
xxi
PART
I
Laboratory Operations
Preliminary
Topics
1. Safety
1.1
1.2
1.3
1.4
1.5
1.6
1.7
2.
3.
4.
5.
Fire
Explosions
Poisoning
Cuts
Spills
Chemicals in the Eye
A Short List of Hazardous Materials and
Some of Their Properties
Glassware Used in the Organic Chemistry Laboratory
Cleaning Up
3.1 Care of Ground-Glass-Jointed Glassware
3.2 Separatory Funnels and Glassware with Stopcocks
3.3 Drying of Glassware
Collection and Disposal of Waste
4.1 Solid Waste
4.2 Liquid Waste
4.3 General Instructions for Collection of Waste
The Laboratory Notebook
6. The Chemical Literature
6.1 Secondary Sources for Physical Properties of
Organic Compounds
6.2 Secondary Sources for Methods of Preparation of
Organic Compounds
6.3 Collections of Spectra
6.4 Miscellaneous
3
4
5
6
7
7
8
8
16
21
22
23
23
24
24
25
25
26
31
32
35
36
37
vi Contents
Tables
7.1 Solutions of Acids
7.2 Solutions of Bases
7.3 Molecular Weights and Molar Volumes of Acids
7.4 Molar Weights of Bases
7.5 Molecular Weights, Densities, and Molar Volumes of
Selected Liquid Reagents
7.6 Periodic Table of the Elements
38
39
40
40
41
41
42
Separation of Substances;
Purification of Substances
8. Filtration
8.1 Gravity Filtration
8.2 Micro-Scale Gravity Filtration
8.3 Vacuum or Suction Filtration
44
44
45
45
9. Recrystallization
9.1 Choiceof Solvent
9.2 Dissolving the Sample
9.3 Decolorizing the Solution
9.4 Hot Filtration
9.5 Cooling for Crystallization
9.6 Cold Filtration
9.7 Washing the Crystals
9.8 Drying the Crystals
9.9 More Techniques of Crystallization
9.10 Micro-Scale Recrystallization
9.11 Selection ofaSuitable Solvent
48
49
49
50
50
52
53
53
54
55
57
59
10. Distillation
10.1 Vapor Pressure
10.2 Distillation of a Pure Liquid
10.3 Miscible Pairs of Liquids
10.4 Fractional Distillation
10.5 Azotropic Mixtures
10.6 Technique of Distillation
10.7 Small-Scale Distillation
62
63
66
67
70
72
75
77
11. Reduced-Pressure Distillation
11.1 Estimation of the Boiling Point
at Reduced Pressure
11.2 Apparatus
80
81
82
Contents
11.3 Source of Vacuum
11.4 Pressure Measurement
11.5 Technique of Distillation
Under Reduced Pressure
83
84
85
12. Distillation of Mixtures of Two Immiscible Liquids;
Steam Distillation
12.1 Theory of Steam Distillation
12.2 Technique of Steam Distillation
87
87
88
13. Sublimation
13.1 Theory of Sublimation
13.2 Technique of Sublimation
90
90
91
14. Extraction by Solvents
14.1 Theory of Extraction
14.2 Extraction ofAcids and Bases
14.3 Technique of Extraction
14.4 Micro-Scale Extraction
15. Chromatography
15.1 Theory of Column Chromatography
15.2 Technique of Column Chromatography
15.3 Theory ofThin-Layer Chromatography
15.4 Technique ofThin-Layer Chromatography
15.5 Theory of Paper Chromatography
15.6 Technique of Paper Chromatography
15.7 Theory ofVapor-Phase Chromatography
15.8 Technique ofVapor-Phase Chromatography
15.9 High-Pressure Liquid Chromatography
15.10 Batchwise Adsorption; Decolorization
92
92
94
97
101
109
110
113
116
118
120
120
122
126
128
129
16. Removal of Water; Drying
16.1 Drying of Solids
16.2 Drying of Solutions
16.3 Drying of Solvents and Liquid Reagents
129
130
132
134
Determination of Physical Properties
17. Boiling Point
17.1 Experimental Determination of Boiling Point
17.2 Boiling Point and Molecular Structure
17.3 Boiling Point and the Enthalpy and Entropy of
Vaporization
138
138
141
144
vii
18. Melting Point
18.1 Experimental Determination of the Melting Point
18.2 The Melting Point as a Criterion of Purity
18.3 The Melting Point as a Means of Identification
and Characterization
18.4 Mixture Melting Points
18.5 Melting Point and Molecular Structure
19. Density; Specific Gravity
19.1 Experimental Determination of the Density
19.2 Density and Molecular Structure
20. Index ofRefraction
20.1 Experimental Determination
of the Index ofRefraction
20.2 Index ofRefraction and Molecular Structure
21. Optical Activity
21.1 Experimental Determination of Optical Rotation
21.2 Optical Activity and Molecular Structure
22. Molecular Weight
22.1 Molecular Weight Determination
by Mass Spectrometry
22.2 Molecular Weight Determination byOtherMethods
23. Solubility
23.1 Solubility of Liquids in Liquids
23.2 Solubility of Solids in Liquids
23.3 Classification of Compounds by Solubility;
Relationships Between Solubility and
Molecular Structure
23.4 Techniques for Determination of Solubility
24. Infrared Absorption Spectrometry
24.1 Wavelength, Frequency, and
Energy of Electromagnetic Radiation
24.2 Units of Light Absorption
24.3 InfraredLight Absorption and Molecular Structure
24.4 Interpretation of Infrared Spectra
24.5 Sample Preparation
25. Ultraviolet-Visible Absorption Spectrometry
25.1 Ultraviolet-Visible Light Absorption
and Molecular Structure
25.2 Interpretation of Ultraviolet-Visible Spectra
25.3 Color and Molecular Structure
25.4 Sample Preparation
150
150
154
155
155
155
159
159
160
161
161
162
163
163
166
168
168
169
169
170
174
175
180
182
183
183
185
186
191
201
202
203
203
204
Contents
Nuclear Magnetic Resonance Spectrometry
26.1 Shielding; Chemical Shift
Splitting
26.2
26.3 The Integral
26.4 Nuclear Magnetic Resonance and
Molecular Structure
26.5 Interpretation of NMR Spectra
26.6
Sample Preparation
Mass Spectrometry
27.1 Theory of Mass Spectrometry
27.2 Interpretation of Mass Spectra
27.3 High-Resolution Mass Spectrometry
207
208
211
219
220
222
226
231
231
234
236
Determination of Chemical Properties:
Qualitative Organic Analysis
28. Qualitative Tests for the Elements
28.1 Ignition Test; Test for Metals
28.2 Beilstein Test; Test for Halogens
(Except Fluorine)
28.3 Sodium Fusion Test; Test for Nitrogen,
Sulfur, and the Halogens
29. Qualitative Characterization Tests:
Tests for the Functional Groups
29.1 Detection of Ammonia from Ammonium
Salts, Primary Amides, and Nitriles
29.2 Benzenesulfonyl Chloride (Hinsberg's Test)
29.3 Bromine in Carbon Tetrachloride
29.4 Chromic Anhydride
29.5 2,4-Dinitrophenylhydrazine
29.6 Ferric Chloride Solution
29.7 Ferric Hydroxamate Test
29.8 Hydrochloric Acid/Zinc Chloride Test
(Lucas's Test)
29.9 Iodoform Test
29.10 Aqueous Potassium Permanganate Solution
(Baeyer's Test)
29.11 Alcoholic Silver Nitrate Solution
29.12 Sodium Hydroxide Test
29.13 Sodium Iodide in Acetone
29.14 Tollen's Reagent: Silver-Ammonia Complex Ion
241
241
242
242
247
249
250
252
253
253
254
255
258
258
260
261
262
263
263
ix
x
Contents
30. Characterization Through Formation of Derivatives
30.1 Benzoates, jb-Nitrobenzoates, and
3,5-Dinitrobenzoates of Alcohols
30.2 Hydrogen 3-Nitrophthalates of Alcohols
30.3 Phenyl-and a-Naphthylurethans
30.4 Methone Derivations ofAldehydes
30.5 2,4-Dinitrophenylhydrazones
30.6 Semicarbazones
30.7 Oximes
30.8 Carboxylic Acids by Hydrolysis of Primary
Amides and Nitriles
30.9 9-Acylamidoxanthenes from Amides
30.10 Hydrolysis of N-Substituted Amides
30.11 Substituted Acetamides from Amines
30.12 Substituted Benzamides from Amines
30.13 /i-Toluenesulfonamides from Amines
30.14 Phenylthioureas and a-Naphthylthioureas
30.15 Picrates
30.16 Quaternary Ammonium Salts: Methiodides and
/»-Toluenesulfonates
30.17 Carboxylic Acid Amides
30.18 Anilides, jb-Toluidides, and jb-Bromoanilides
of Carboxylic Acids
30.19 Phenacyl and Substituted Phenacyl
Esters of Carboxylic Acids
30.20 jö-Nitrobenzyl Esters of Carboxylic Acids
30.21 N-Benzylamides from Esters
30.22 3,5-Dinitrobenzoates from Esters
30.23 Hydrolysis of Esters
30.24 Bromination of Aromatic Ethers
30.25 S-Alkylthiuronium Picrates
30.26 o-Aroylbenzoic Acids from
Aromatic Hydrocarbons
30.27 Aromatic Acids by Oxidation by Permanganate
30.28 Anilides, /»-Toluidides,
and a-Naphthalides from Alkyl Halides
30.29 2,4,7-Trinitrofluorenone Adducts of Aromatic
Hydrocarbons
30.30 Bromination of Phenols
30.31 Aryloxyacetic Acids from Phenols
266
272
273
274
274
275
276
276
277
278
279
280
281
282
282
283
285
285
286
287
289
290
290
291
292
293
294
295
295
296
297
297
Apparatus and Techniques
for Chemical Reactions
31. Assembling the Apparatus
32. Temperature Control
33. Methods of Heating and Cooling
33.1 Heating
33.2 Cooling
34. Stirring
35. Addition of Reagents
36. Control of Evolved Gases
37. Concentration; Evaporation
38. Use of an Inert Atmosphere
39. Working Up the Reaction; Isolation of the Product
PART
II
299
302
305
305
309
310
313
315
317
318
319
Experiments
Isolations and Purifications
El
E2
E3
E4
E5
E6
E7
E8
E9
E10
Ell
El2
Isolation of Cholesterol from Gallstones
Isolation ofLactose from Powdered Milk
Isolation of Acetylsalicylic Arid from Aspirin Tablets
Isolation of Ibuprofen from Ibuprofen Tablets
Isolation of Caffeine from Tea and NoDoz
Isolation of Piperine from Black Pepper
Isolation of Trimyristin from Nutmeg
Isolation of Clove Oil from Cloves
Isolation ofEugenol from Clove Oil
Isolation of (R)-(+)-Limonene from Grapefruit
or Orange Peel
Isolation of (R)-(-)-or (S)-(+)-Carvone from Oil
of Spearmint or Oil of Caraway
Resolution of a-Phenylethylamine
by (R),(R)-(+)-Tartaricarid
327
329
332
335
337
340
342
344
346
347
350
355
Transformations
Isomerizations
E13 Adaman tane frora
tfwdo-Tetrahydrodicyclopentadiene
via the Thiourea Clathrate
El4 os-Dibenzoylethyelene from
<rare5-l,2-Dibenzoylethylene
Preparation of Cyclohexanol
E15 Cyclohexanol from Cyclohexene
El 6 Cycohexanol from Cyclohexanone
Reactions of Cyclohexanol
El 7
E18
E19
E20
Cyclohexene from Cyclohexanol
Dehydration of 2-Methylcyclohexanol: A Variation
Cyclohexyl Bromide from Cyclohexanol
Cyclohexanone from Cyclohexanol
Addition of Dichlorcarbene to Alkenes
by Phase Transfer Catalysis
E21 Addition of Dichlorocarbene to Cyclohexene
E22 Addition of Dichlorocarbene to Styrene:
A Variation
E23 Addition of Dichlorocarbene
to 1,5-Cyclooctadiene: Another Variation
Alkyl Halides from Alcohols
E24
E25
E26
E27
E28
E29
Isoamyl Bromide from Isoamyl Alcohol
n-Butyl Bromide from n-Butyl Alcohol:
A Variation
tert-Butyl Chloride from tert-Butyl Alcohol
tert-Amyl Chloride from teri-Amyl Alcohol:
A Variation
Competitive Nucleophilic Substitution
of Butyl Alcohols by Bromide and Chloride Ion
Kinetics of the Hydrolysis of tert-Buty\ Chloride
363
364
367
371
371
373
375
376
381
384
387
389
392
394
395
397
398
402
403
406
407
410
Contents
Isoamyl Acetate: A Component
of the Alarm Pheromone of the Honey Bee
E30 Isoamyl Acetate from Isoamyl Bromide
and Potassium Acetate
E31 Isoamyl Acetate from Isoamyl Alcohol
and Acetic Acid; The Fischer Estrification
424
Liquid Crystals
E32 Cholesteryl Benzoate from Cholesterol
427
428
Acetylation of Glucose
E33 a-D-Glucose Pentaacetate from Glucose
E34 ß-D-Glucose Pentaacetate from Glucose
E35 Acetylation of Glucose
in iV-Methylimidazole: A Variation
E36 Preparation of Methyl Benzoate, Oil of Niobe
431
433
433
The Grignard Reaction
E37 Aliphatic Alcohols: Preparation
by Grignard Synthesis
Preparation of Triphenylmethanol
E38 Preparation of Triphenylmethanol
from Benzophenone
E39 Preparation of Triphenylmethanol
from Methyl Benzoate
E40 Preparation of Triphenylmethanol
from Dimethyl Carbonate
E41 Preparation of Aniline from Nitrobenzene
Preparation of Amides
E42 Acetanilide from Aniline
E43 7V,iV-Diethyl-m-Toluamide
from »i-Toluic Acid; A Mosquito Repellant: "Off
Electrophilic Substitution Reactions
of Benzene Derivatives
E44 Methyl m-Nitrobenzoate from Methyl Benzoate
E45 jb-Bromoacetanilide from Acetanilide
E46 2,4-Dinitrobromobenzene from Bromobenzene
417
421
434
436
439
440
444
446
448
451
454
456
457
461
463
464
466
469
xiii
xiv Contents
Nucleophilic Aromatic Substitution Reactions
of 2,4-Dinitrobromobenzene
E47 2,4-Dinitroaniline
E48 2,4-Dinitrophenylhydrazine
E49 2,4-Dinitrodiphenylamine
E50 2,4-Dinitrophenylpiperidine
E51 4-Substituted 2,4-Dinitrophenylanilines:
A Variation
Oiazonium Salts of Aromatic Amines
E52 Benzenediazonium Chloride from Aniline
E53 jö-Nitrobenzenediazonium Sulfate
from/»-Nitroaniline
472
473
474
475
477
478
480
481
482
Replacement Reactions of Diazonium Salts
E54 Chlorobenzene from
Benzenediazonium Chloride
482
483
Reactions of Vanillin
E55 Acetylvanillin from Vanillin
E56 5-Bromovanillin from Vanillin
E57 5-Nitrovanillin from Vanillin
E58 Vanillin Oxime from Vanillin
E59 Vanillin Semicarbazone from Vanillin
E60 Vanillyl Alcohol from Vanillin
E61 Vanillideneacetone from Vanillin
485
486
487
489
490
491
493
494
Synthesis of Dyes
E62 Benzenediazonium Chloride and ß-Naphthol:
l-Phenylazo-2-Naphthol (Sudan I)
E63 jb-Nitrobenzenediazonium Sulfate and Phenol:
jb-(4-nitrobenzeneazo)-phenol
E64 ^-Nitrobenzenediazonium Sulfate and
ß-Naphthol: l-(/;-nitrophenylazo)-2-naphthol
(Para Red; American Flag Red)
E65 ^-Nitrobenzenediazonium Sulfate
and Dimethylaniline:
/K4-nitrobenzeneazo)-A'',Af-Dimethylaniline
498
499
502
503
505
The Diels-Alder Reaction
507
E66 Butadiene (from 3-Sulfolene) and Maleic Anhydride 508
E67 Cyclopentadiene and Maleic Anhydride
510
E68 Furan and Maleic Anhydride
514
E69 a-Phellandrene and Maleic Anhydride
515
Contents
The Wittig Reaction
E70 The Preparation of trans-Sülbene
E71 Preparation of
trans,<rans-l,4-Diphenylbutadiene:
A Variation
517
519
Analgesics: Aspirin, Phenacetin, and Tylenol
E72 Acetylsalicylic Acid from Salicylic Acid:
Preparation of Aspirin
E73 jb-Acetamidophenol from jö-Aminophenol:
Preparation of Tylenol
E74 /»-Ethoxyacetanilide from jf?-Ethoxyaniline:
Preparation of Phenacetin
E75 jö-Ethoxyacetanilide from /»-Acetamidophenol:
Another Preparation of Phenacetin
527
529
Nitration of Phenacetin
E76 2-Nitrophenacetin from Phenacetin
536
536
Esterification of Salicylic Acid
E77 Preparation of Methyl Salicylate:
Oil of Wintergreen
538
Coconut Aldehyde; y-Nonanolactone
E78 3-Nonenoic Acid from Heptaldehyde
and Malonic Acid
E79 Coconut Aldehyde from 3-Nonenoic Acid
Catalysis by Thiamine
E80 Thiamine-Catalyzed Formation of Benzoin from
Benzaldehyde
A Model for the Reducing Agent NADH
E81 1-Benzylnicotinamide Chloride from
Nicotinamide
E82 1-Benzyldihydronicotinamide from
1-Benzylnicotinamide Chloride
E83 Reduction of Malachite Green by 1-Benzyldihydronicotinamide
Two Thermochronic Compounds
E84 Dixanthylene from Xanthone
E85 Dianthroquinone from Anthrone
via 9-Bromoan throne
524
527
531
535
538
540
541
543
546
546
552
554
556
557
559
560
561
xv
xvi Contents
A Photochromic Compound: 2-(2,4-Dinitrobenzyl)
Pyridine
E86 A Photochromic Compound:
2-(2,4-Dinitrobenzyl) pyridine
E87 A Chemiluminescent Compound: Luminol
564
564
567
Synthetic Sequences:
Experiments that Use a Sequence
of Reactions
Steroid Transformations
E88 Cholesterol Dibromide from Cholesterol
E89 5<x,6ß-Dibromocholestane-3-one
from Cholesterol Dibromide
E90 A 5 -Cholestene-3-one
from 5a,6ß-Dibromocholestane-3-one
E91 A 4 -Cholestene-3-one from
A 6 -Cholestene-3-one
Tetraphenylcyclopentadienone:
A Purple Compound
E92 Benzoin from Benzaldehyde
E93 Benzil from Benzoin
E94 Dibenzylketone from Phenylacetic Acid
E95 Tetraphenylcyclopentadienone from Benzil
and Dibenzyl Ketone
Sulfanilamide
E96 />-Acetamidobenzenesulfonyl Chloride
from Acetanilide
E97 jb-Acetamidobenzenesulfonamide
from jö-Acetamidobenzenesulfonyl Chloride
E98 Sulfanilamide from
/»-Acetamidobenzenesulfonamide
A Bootstrap Synthesis: p-Phenetidine
from p-Phenetidine
E99 Ethyldioxyazobenzene from jö-Phenetidine
El00 Diethyldioxyazobenzene
from Ethyldioxyazobenzene
ElOl jb-Phenetidine from Diethyldioxyazobenzene
578
580
582
583
587
589
591
592
593
595
597
602
604
605
607
608
610
611
Contents
1-Bromo-3-Chloro-5-iodobenzene
El02 2-Chloro-4-Bromoacetanilide
from 4-Bromoace tanilide
E103 2-Chloro-4-Bromoaniline
from 2-Chloro-4-Bromoacetanilide
E104 2-Chloro-4-Bromo-6-iodoaniline
from 2-Chloro-4-Bromoaniline
El05 l-Bromo-3-chloro-5-Iodobenzene
from 2-Chloro-4-bromo-6-iodoaniline
MOED: A Merocyanine Dye
E106 1,4-Dimethylpyridinium lodide
from 4-Methylpyridine and Methyl lodide
E107 Preparation of
4- (^-Hydroxystyryl) -1 -Me thylpyridinium
lodide from 1-4-Dimethylpyridinium lodide
and j&-Hydroxybenzaldehyde
E108 l-Methyl-4[ (Oxocyclohexadienylidene)
-E thylidene ] -1,4-Dihydropyridine
(MOED) from 4-(/>-Hydroxystyryl)-l-Methylpyridinium lodide
615
617
620
622
624
627
629
630
632
Appendix
635
Chemical Substance Index
647
General Subject Index
655
xvii