Systematic Identification of Organic Compounds

Systematic Identification of Organic Compounds ... 7.19 Nitro Compounds 291 ... 8.13 Hydrocarbon—Aromatic 372" 8.14 Nitriles 375 8.15 Nitro Compounds ...

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The Systematic Identification of Organic Compounds Seventh Edition

Ralph L. Shriner Christine K.F. Hermann Terence C. Morrill David Y. Curtin Reynold C. Fuson

John Wiley & Sons, Inc. NewYork • Chichester • Weinheim • Brisbane • Singapore • Toronto

Contents Chapter 1 1.1 1.2 1.3

The Systematic Identification of Organic Compounds: The Need for Organic Qualitative Analysis Suggestions to Students and Instructors Laboratory Safety and First Aid

Chapter 2 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10

Introduction

Identification

of U n k n o w n s

Preliminary Examination Physical Constants Molecular Weight Determination Molecular Formula Determination Solubility Tests Infrared and Nuclear Magnetic Resonance, and Spectra Analyses Classification Tests Preparation of a Satisfactory Derivatives Mixtures Report Forms

Chapter 3

P r e l i m i n a r y E x a m i n a t i o n , P h y s i c a l P r o p e r t i e s , and P u r i t y

1 3 5

8 12 12 12 13 13 14 14, 17 21 22

34

Determination 3.1

3.2

3.3

3.4

3.5

Preliminary Examination 3.1.1 Physical State 3.1.2 Color 3.1.3 Odor 3.1.4 Ignition Test 3.1.5 Summary and Applications Determination of Physical Properties 3.2.1 Melting Points 3.2.2 Boiling Points 3.2.3 Specific Gravity 3.2.4 Index of Refraction of Liquids Introduction to Chromatography 3.3.1 Thin-Layer Chromatography 3.3.2 Gas Chromatography Optical Rotation 3.4.1 Preparation of the Solution 3.4.2 Filling the Polarimeter Tube 3.4.3 The Use of the Polarimeter 3.4.4 Expression of Results 3.4.5 Enantiomeric Excess (Optical Purity) and Resolution Recrystallization

35 35 35 35 36 37 37 37 44 50 56 58 59 63 71 71 71 72 74 75 78

x

Contents

Chapter 4 4.1 4.2

Qualitative Elemental Analysis 4.1.1 Fusion of Organic Compounds with Sodium Quantitative Elemental Analysis 4.2.1 Combustion and Related Analyses 4.2.2 Formula Determination by Mass Spectrometry

Chapter 5 5.1

5.2

Classification

of O r g a n i c C o m p o u n d s by S o l u b i l i t y

Solubility in Water, Aqueous Acids and Bases, and Ether 5.1.1 Determination of Solubilities 5.1.2 Theory of Solubility 5.1.3 Theory of Acid-Base Solubility 5.1.4 Solubility in Water 5.1.5 Solubility in 5% Hydrochloric Acid Solution 5.1.6 Solubility in 5% Sodium Hydroxide and 5% Sodium Bicarbonate Solutions 5.1.7 Solubility of Amphoteric Compounds 5.1.8 Solubility in Cold, Concentrated Sulfuric Acid 5.1.9 Borderlines Between Solubility Classes Solubility in Organic Solvents

Chapter 6 6.1 6.2 6.3 6.4 6.5

D e t e r m i n a t i o n of M o l e c u l a r F o r m u l a

Spectrometric Methods

Mass Spectrometry Infrared (IR) Spectrometry Nuclear Magnetic Resonance Spectrometry Ultraviolet Spectrometry Problems

Chapter 7

C h e m i c a l Tests for F u n c t i o n a l G r o u p s

7.1 Acid Anhydrides 7.2 Acyl Halides 7.3 Alcohols 7.4 Aldehydes 7.5 Amides 7.6 Amines and Amine Salts 7.7 Amino Acids 7.8 Carbohydrates 7.9 Carboxylic Acids 7.10 . Esters 7.11 Ethers 7.12 Halides 7.13 Hydrocarbons-Alkanes 7.14 Hydrocarbons-Alkenes 7.15 Hydrocarbons-Alkynes 7.16 Hydrocarbons-Aromatic

82 83 83 90 90 93

94 95 97 98 103 106 106 107 110 111 112 115

118 119 126 155 175 188

200 204 211 213 228 236 238 253 255 264 265 266 270 275 276 283 284

• Contents 7.17 7.18 7.19 7.20 7.21

Ketones Nitriles Nitro Compounds Phenols Sulfonamides, Sulfonic Acids, Sulfonyl Chlorides

Chapter 8 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 8.10 8.11 8.12 8.13 8.14 8.15 8.16 8.17

9.1 9.2 9.3

289 290 291 294 299

T h e P r e p a r a t i o n of D e r i v a t i v e s

301

Carboxylic Acids, Acid Anhydrides, Acid Halides Alcohols Aldehydes and Ketones Amides Amines Amino Acids Carbohydrates Esters Ethers—Aliphatic Ethers—Aromatic Halides—Alkyl Halides—Aromatic Hydrocarbon—Aromatic Nitriles Nitro Compounds Phenols Sulfonic Acids, Sulfonyl Chlorides, Sulfonamides

Chapter 9

Structural Problems-Solution

304 314 319 325 331 339 345 348 359 360 364 369 372" 375 380 381 385

Methods and E x e r c i s e s

Compounds with Structures Previously Described in the Literature Determination of the Structures of New Compounds Not Described in the Chemical Literature Problems

C h a p t e r 10

xi

391

391 402 405

S e p a r a t i o n of M i x t u r e s

441

Preliminary Examinations of Mixtures Distillation and Sublimation 10.2.1 Distillation 10.2.2 Steam Distillation 10.2.3 Sublimation 10.3 Extractions: Separations Based Upon Salt Formation 10.3.1 Extraction of Water Insoluble Mixtures 10.3.2 Extraction of Water Soluble Mixtures 10.4 Chromatography 10.4.1 Column Chromatography 10.4.2 High-Performance Liquid Chromatography (HPLC) 10.4.3 Gas Chromatography

442 444 444 449 451 452 454 457 461 463 471 474

10.1 10.2

xii

Contents

C h a p t e r 11 11.1 11.2 11.3 11.4 11.5 11.6

Chemical Literature

Handbooks Compendia Spectral Collections Journals Abstracts and Indexes Monographs

Appendix I

Handy Tables for the O r g a n i c L a b o r a t o r y

477 478 479 480 481 482 483

484

Composition and Properties of Common Acids and Bases Composition of Common Buffer Solutions Pressure-Temperature Nomograph for Vacuum Distillations Elution Solvents for Chromatography Salt-Ice Mixtures for Cooling Baths Liquid Media for Heating Baths Solvents for Extraction of Aqueous Solutions Drying Agents for Organic Solvents More Powerful Dehydrating Agents for Organic Liquids

485 486 486 487 488 489 489 490 491

A p p e n d i x II

492

E q u i p m e n t and C h e m i c a l s for the L a b o r a t o r y

Apparatus Individual Desk Equipment Suggested Locker Equipment Suggested Supplementary Kit Suggested Supplementary Microscale Kit General Laboratory Equipment Special Laboratory Equipment Items Obtained on Temporary Loan from Instructor or Stockroom Waste Containers Needed in the Laboratory Chemicals Needed in the Laboratory Organic Compounds Inorganic Compounds Acids and Bases Solutions Indicators Other Items Unknowns

492 492 492 493 493 493 494 494 494 495 495 496 497 497 498 498 499

Appendix III

500

Acid Acid Acyl Acyl

T a b l e s of D e r i v a t i v e s

Anhydrides (Liquids) Anhydrides (Solids) Halides (Liquids) Halides (Solids)

501 502 505 509

Contents Alcohols (Liquids) Alcohols (Solids) Aldehydes (Liquids) Aldehydes (Solids) Amides (Liquids) Amides (Solids) Amines-Primary and Secondary (Liquids) Amines-Primary and Secondary (Solids) Amines-Tertiary (Liquids) Amines-Tertiary (Solids) Amino Acids Carbohydrates Carboxylic Acids (Liquids) Carboxylic Acids (Solids) Esters (Liquids) Esters (Solids) Ethers-Aromatic (Liquids) Ethers-Aromatic (Solids) Halides-Alkyl, Cycloalkyl, and Aralkyl (Liquids) Halides-Aromatic (Liquids) Halides-Aromatic (Solids) Hydrocarbons-Aromatic (Liquids) Hydrocarbons-Aromatic (Solids) Ketones (Liquids) Ketones (Solids) Nitriles (Liquids) Nitriles (Solids) Nitro Compounds (Liquids) Nitro Compounds (Solids) Phenols (Liquids) Phenols (Solids) Sulfonamides Sulfonic Acids Sulfonyl Chlorides

xiii 511 515 517 520 523 524 541 545 556 559 561 563 565 567 576 593 600 602 603 605 606 607' 608 609 613 618 623 631 632 634 636 646 650 653