The Systematic Identification of Organic Compounds E-Book

Christine K. F. Hermann

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 935

Veröffentlichungsjahr: 2023

Beschreibung

The Systematic Identification of Organic Compounds A comprehensive introduction to the identification of unknown organic compounds Identifying unknown compounds is one of the most important parts of the study of chemistry. From basic characteristics such as melting and/or boiling point to more complex data generated through cutting-edge techniques, the range of possible methods for identifying unknown organic compounds is substantial. The utility of a research reference which compiles known techniques and characteristics of possible compounds is clear. The Systematic Identification of Organic Compounds provides such a reference, designed to teach a hands-on approach in the chemistry lab. It takes readers step-by-step through the process of identifying an unknown compound and elucidating its structure from infrared, nuclear magnetic resonance, and mass spectra in addition to solubility characteristics, melting point, boiling point, and classification tests. The result is an essential overview for advanced chemistry students looking to understand this exciting area of laboratory work. Readers of the ninth edition of The Systematic Identification of Organic Compounds will also find: * A detailed chapter on safety, personal protection equipment, chemical storage, safety data sheets, and other safety concerns * New NMR, IR, and mass spectra with detailed explanations on interpretation * Questions at the end of each chapter designed to facilitate and reinforce progression, keyed to a companion website for instructors * Tables of known compounds including data relevant for identification * Companion website with structural problems from experimental data for students to practice how to reason and solve The Systematic Identification of Organic Compounds is a useful reference for advanced undergraduates and graduate students studying organic chemistry, organic spectroscopy, and related subjects.

Leseprobe

Table of Contents

Cover

Title Page

Copyright Page

Preface

About the Companion Website

Chapter 1: Introduction

1.1 SYSTEMATIC IDENTIFICATION OF ORGANIC COMPOUNDS: THE NEED FOR ORGANIC QUALITATIVE ANALYSIS

1.2 SUGGESTIONS TO STUDENTS AND INSTRUCTORS

Chapter 2: Laboratory Safety

2.1 WORKING SAFELY IN THE LABORATORY

2.2 TRAINING

2.3 PERSONAL PROTECTION EQUIPMENT

2.4 SAFETY DATA SHEETS

2.5 STORAGE OF CHEMICALS

2.6 DISPOSAL OF CHEMICALS

2.7 SAFELY USING EQUIPMENT IN THE LABORATORY

Chapter 3: Identification of Unknowns

3.1 DISCUSSION OF REPORT FORM

3.2 PRELIMINARY EXAMINATION

3.3 PHYSICAL PROPERTIES

3.4 MOLECULAR WEIGHT DETERMINATION

3.5 MOLECULAR FORMULA DETERMINATION

3.6 SOLUBILITY TESTS

3.7 INFRARED, NUCLEAR MAGNETIC RESONANCE, AND MASS SPECTRA ANALYSES

3.8 CLASSIFICATION TESTS

3.9 PREPARATION OF A SATISFACTORY DERIVATIVE

3.10 MIXTURES

3.11 REPORT FORMS

Chapter 4: Preliminary Examination, Physical Properties, and Elemental Analysis

4.1 PRELIMINARY EXAMINATION

4.2 DETERMINATION OF PHYSICAL PROPERTIES

4.3 OPTICAL ROTATION

4.4 RECRYSTALLIZATION

4.5 QUALITATIVE ELEMENTAL ANALYSIS

4.6 QUANTITATIVE ELEMENTAL ANALYSIS

Chapter 5: Classification of Organic Compounds by Solubility

5.1 SOLUBILITY IN WATER, AQUEOUS ACIDS AND BASES, AND ETHER

5.2 SOLUBILITY IN ORGANIC SOLVENTS

Chapter 6: Separation of Mixtures

6.1 PRELIMINARY EXAMINATIONS OF MIXTURES

6.2 DISTILLATION AND SUBLIMATION

6.3 EXTRACTIONS: SEPARATIONS BASED UPON SALT FORMATION

6.4 CHROMATOGRAPHY

Chapter 7: Nuclear Magnetic Resonance Spectrometry

7.1 THEORY OF NUCLEAR MAGNETIC RESONANCE

7.2 PREPARATION OF THE SAMPLE

7.3 PROTON SPECTRA

7.4

13

C SPECTRA

7.5 DEPT

7.6 COSY

7.7 HSQC

Chapter 8: Infrared Spectrometry

8.1 THEORY OF INFRARED SPECTROMETRY

8.2 PREPARATION OF THE SAMPLE

8.3 FUNCTIONAL GROUP IDENTIFICATION

Chapter 9: Mass Spectrometry

9.1 THEORY OF MASS SPECTROMETRY

9.2 CLEAVAGE REACTIONS

Chapter 10: Chemical Tests for Functional Groups

10.1 ACID ANHYDRIDES

10.2 ACYL HALIDES

10.3 ALCOHOLS

10.4 ALDEHYDES

10.5 AMIDES

10.6 AMINES AND AMINE SALTS

10.7 AMINO ACIDS

10.8 CARBOHYDRATES

10.9 CARBOXYLIC ACIDS

10.10 ESTERS

10.11 ETHERS

10.12 HALIDES

10.13 HYDROCARBONS—ALKANES

10.14 HYDROCARBONS—ALKENES

10.15 HYDROCARBONS—ALKYNES

10.16 HYDROCARBONS—AROMATIC

10.17 KETONES

10.18 NITRILES

10.19 NITRO COMPOUNDS

10.20 PHENOLS

10.21 SULFONAMIDES, SULFONIC ACIDS, SULFONYL CHLORIDES

Chapter 11: The Preparation of Derivatives

11.1 CARBOXYLIC ACIDS, ACID ANHYDRIDES, ACID HALIDES

11.2 ALCOHOLS

11.3 ALDEHYDES AND KETONES

11.4 AMIDES

11.5 AMINES

11.6 AMINO ACIDS

11.7 CARBOHYDRATES

11.8 ESTERS

11.9 ETHERS—ALIPHATIC

11.10 ETHERS—AROMATIC

11.11 HALIDES—ALKYL

11.12 HALIDES—AROMATIC

11.13 HYDROCARBONS—AROMATIC

11.14 NITRILES

11.15 NITRO COMPOUNDS

11.16 PHENOLS

11.17 SULFONIC ACIDS, SULFONYL CHLORIDES, SULFONAMIDES

Chapter 12: Chemical Literature

12.1 HANDBOOKS

12.2 COMPENDIA

12.3 SPECTRAL COLLECTIONS

12.4 JOURNALS

12.5 ABSTRACTS AND INDEXES

12.6 MONOGRAPHS

Appendix I: Handy Tables for the Organic Laboratory

Appendix II: Table of Derivatives

Appendix II: Table of Derivatives (Continued)

Appendix III: Equipment and Chemicals for the Laboratory

AIII.1 APPARATUS

AIII.2 CHEMICALS NEEDED IN THE LABORATORY

AIII.3 UNKNOWNS

Index

End User License Agreement

List of Tables

Chapter 4

Table 4.1 Melting Point Standards

Table 4.2 Boiling Point Changes per Slight Pressure Change

Table 4.3 Boiling Points (°C) at Reduced Pressures

Table 4.4 Boiling Point and Chain‐Length for Straight‐Chain Alkanes

Table 4.5 Boiling Point and Hydroxyl Group Substitution

Table 4.6 The Effect of the Addition of Ether Linkages to Boiling Point

Table 4.7 Comparison of the Boiling Points of Oxygen Derivatives with Their ...

Table 4.8 Comparison of the Boiling Points of Ethers and Thiols

Table 4.9 Alcohol Boiling Point and Branching

Table 4.10 Specific Gravity and Double Bond Position

Table 4.11 Boiling Point and Specific Gravity of Aryl Halides

Table 4.12 Specific Gravity Change per Number of Chlorine or Oxygen Atoms

Table 4.13 Common Solvents for Recrystallization of Standard Functional Clas...

Table 4.14 Solvents and Solvent Pairs for Recrystallization of Common Deriva...

Chapter 5

Table 5.1 Organic Compounds Comprising the Solubility Classes of Figure 5.1

Table 5.2 Dielectric Constants of Common Organic Solvents

Table 5.3 Water Solubility of Dicarboxylic Acids, HOOC(CH

2

)

x

COOH

Table 5.4 Water Solubility of Various Organic Compounds

Table 5.5 Solubility Classes of Various Organic Acids

Table 5.6 Borderlines Between Solubility Classes

Table 5.7 Common Organic Solvents

Chapter 6

Table 6.1 Solubility and Steam Distillation

TABLE 6.2 Chromatographic Solvents

TABLE 6.3 Polarity Classifications of Organic Compounds for GC Analysis

Table 6.4 Activity of Alumina with 4‐Aminoazobenzene

Table 6.5 Activity of Silica Gel with 4‐

N,N

‐Dimethylaminoazobenzene or 1,4‐D...

Table 6.6 Volume of Solvent for Development of Various Sizes of Dry Chromato...

Table 6.7 Column Diameter Needed for Flash Chromatography

Chapter 7

Table 7.1

1

H Chemical Shifts of Common NMR Solvents

Table 7.2

13

C Chemical Shifts of Common NMR Solvents

Table 7.3 Proton Magnetic Resonance Frequencies

Table 7.4 Hydrogen Chemical Shift Correction Factors for Groups on sp

3

‐Hybri...

Table 7.5 Hydrogen Chemical Shift Correction Factors for Groups on Alkenes...

Table 7.6 Hydrogen Chemical Shift Correction Factors for Groups on Substitut...

Table 7.7 Carbon─13 Magnetic Resonance Frequencies

Table 7.8 Chemical Shifts of Carbons in Straight‐ and Branched‐Chain Alkanes

Table 7.9

13

C Shift Effect Due to Replacement of H by Functional Groups (R) ...

Table 7.10 Chemical Shift Correction Factors for Groups on Alkenes

Table 7.11 Effect of Substituents on the

13

C Shift of Benzene Ring Carbons...

Chapter 8

Table 8.1 Characteristic Infrared Absorption Frequencies

Chapter 9

Table 9.1 Isotope Abundances Based on the Common Isotope Set at 100%

Table 9.2 Isotope Abundance Aspects of Methane (CH

4

)

Table 9.3 Masses and Isotope Abundance Ratios for Combinations of C, H, N, a...

Table 9.4 Exact Masses of Isotopes

Table 9.5 Distinguishing Elements in a Mass Spectrum

Chapter 10

Table 10.1 Classification Tests, Listed by Functional Group

Table 10.2 Experiments for Classification of Functional Groups

Table 10.3 Approximate Times for Reduction of Red Ce(IV) Complexes at 20°C t...

Table 10.4 Chemical Tests for Amino Acids

Chapter 11

Table 11.1 Index to Characterization Procedures for Functional Group Classes...

Table 11.2 Specific Rotations of α‐Amino Acids

Appendix I

Table AI.1 Composition and Properties of Common Acids and Bases

Table AI.2 Composition of Common Buffer Solutions

Table AI.3 Pressure‐Temperature Nomongraph for Vacuum Distillations

Table AI.4 Elution Solvents for Chromatography

Table AI.5 Salt‐Ice Mixtures for Cooling Baths

Table AI.6 Liquid Media for Heating Baths

Table AI.7 Solvents for Extractions of Aqueous Solutions

Table AI.8 Drying Agents of Moderate Strength for Organic Solvents

Table AI.9 More Powerful Dehydrating Agents for Organic Liquids

Appendix II

Table AII.1 Acid Anhydrides (Liquids)

Table AII.2 Acid Anhydrides (Solids)

Table AII.3 Acid Halides (Liquids)

Table AII.4 Acid Halides (Solids)

Table AII.5 Alcohols (Liquids)

Table AII.6 Alcohols (Solids)

Table AII.7 Aldehydes (Liquids)

Table AII.8 Aldehydes (Solids)

Table AII.9 Amides (Liquids)

Table AII.10 Amides (Solids)

Table AII.11 Amines—Primary and Secondary (Liquids)

Table AII.12 Amines—Primary and Secondary (Solids)

Table AII.13 Amines—Tertiary (Liquids)

Table AII.14 Amines—Tertiary (Solids)

Table AII.15 Amino Acids

Table AII.16 Carbohydrates

Table AII.17 Carboxylic Acids (Liquids)

Table AII.18 Carboxylic Acids (Solids)

Table AII.19 Esters (Liquids)

Table AII.20 Esters (Solids)

Table AII.21 Ethers—Aliphatic (Liquids)

Table AII.22 Ethers—Aromatic (Liquids)

Table AII.23 Ethers—Aromatic (Solids)

Table AII.24 Halides—Alkyl, Cycloalkyl, and Aralkyl (Liquids)

Table AII.25 Halides—Aromatic (Liquids)

Table AII.26 Halides—Aromatic (Solids)

Table AII.27 Hydrocarbons—Aromatic (Liquids)

Table AII.28 Hydrocarbons—Aromatic (Solids)

Table AII.29 Ketones (Liquids)

Table AII.30 Ketones (Solids)

Table AII.31 Nitriles (Liquids)

Table AII.32 Nitriles (Solids)

Table AII.33 Nitro Compounds (Liquids)

Table AII.34 Nitro Compounds (Solids)

Table AII.35 Phenols (Liquids)

Table AII.36 Phenols (Solids)

Table AII.37 Sulfonamides (Solids)

Table AII.38 Sulfonic Acids (Solids)

Table AII.39 Sulfonyl Chlorides (Solids)

List of Illustrations

Chapter 2

Figure 2.1 The GHS pictograms for chemicals.

Chapter 3

Figure 3.1 Example of a systematic approach to the identification of an unkn...

Figure 3.2 Example of a systematic approach to the identification of an unkn...

Chapter 4

Figure 4.1 Charging (a) and packing (b, c) capillary melting point tubes.

Figure 4.2 METTLER TOLEDO Melting Point System MP55.

Figure 4.3 Thiele tube melting point apparatus.

Figure 4.4 BUCHI melting point M‐560 apparatus.

Figure 4.5 Melting point calibration curve.

Figure 4.6 Simple freezing point apparatus.

Figure 4.7 A small‐scale simple distillation apparatus. Sand has been used t...

Figure 4.8 Boiling point determination: Procedure B.

Figure 4.9 Micro boiling point tube.

Figure 4.10 Ultramicro boiling point. (a) Preparation of a small glass bell;...

Figure 4.11 Relationship between boiling point and molecular weight.

Figure 4.12 Micropycnometer.

Figure 4.13 Specific gravity bulb (small volumetric flask).

Figure 4.14 Relationship between specific gravity and molecular weight.

Figure 4.15 Relationship between specific gravity and molecular weight (line...

Figure 4.16 Refraction of light.

Figure 4.17 The Reichert Abbe Mark III Refractometer.

Figure 4.18 Leica Abbe Mark II Refractometer schematic.

Figure 4.19 Correct adjustment of the light and dark halves coinciding with ...

Figure 4.20 Koehler polarimeter tube.

Figure 4.21 Schematic of PerkinElmer® 341 polarimeter.

Figure 4.22 Abderhalden drying pistol.

Chapter 5

Figure 5.1 Classification of organic compounds by solubility: determination ...

Chapter 6

Figure 6.1 Kugelrohr distillation apparatus.

Figure 6.2 Short‐path distillation apparatus with stirbar.

Figure 6.3 Hickman–Hinkle still head with a round‐bottom flask, air condense...

Figure 6.4 Microscale distillation apparatus.

Figure 6.5 Distillation columns and condensers: (a) Vigreux column, (b) Alli...

Figure 6.6 A fractional distillation apparatus.

Figure 6.7 Microscale spinning band column.

Figure 6.8 Hickman flask.

Figure 6.9 Vacuum distillation apparatus. Another option involves the replac...

Figure 6.10 Sand bath with Variac.

Figure 6.11 Aluminum block on hot‐plate stirrer.

Figure 6.12 A rotary evaporator.

Figure 6.13 Steam distillation apparatus (macroscale).

Figure 6.14 Sublimation apparatus.

Figure 6.15 Separation of a water insoluble mixture as described in Procedur...

Figure 6.16 Separation of a water insoluble mixture as described in Procedur...

Figure 6.17 Separation of a water soluble mixture as described in Procedure ...

Figure 6.18 Separation of a water soluble mixture containing esters as descr...

Figure 6.19 Separation of a mixture, Example 1.

Figure 6.20 Separation of a mixture, Example 2.

Figure 6.21 Separation of a mixture, Example 3.

Figure 6.22 Preparation of a TLC capillary tube, (a) While rotating the tube...

Figure 6.23 Determination of solvent for thin layer chromatography. (a) Good...

Figure 6.24 Preparation for TLC.

Figure 6.25 Chromatographic development unit.

Figure 6.26 Iodine TLC spot‐marking chamber.

Figure 6.27 Thin‐layer chromatogram; reaction mixture analysis.

Figure 6.28 Determination of

R

f

value on the TLC chromatogram.

Figure 6.29 A schematic diagram of a gas chromatograph.

Figure 6.30 GOW‐MAC 400 series academic gas chromatograph.

Figure 6.31 Gas chromatogram.

Figure 6.32 (a) Typical dimensions of open tubular column for GC. (b) Alumin...

Figure 6.33 Common stationary phases. See polarity classifications in Table ...

Figure 6.34 Syringe.

Figure 6.35 Calculation of retention time.

Figure 6.36 Calculation of peak area and molar percent composition.

Figure 6.37 Collection devices for GC: (a) capillary size; (b) centrifuge tu...

Figure 6.38 Illustration of separating a mixture in chromatography: (a) init...

Figure 6.39 Chromatography columns: (a) plain; (b) with a ground glass joint...

Figure 6.40 Packed chromatography column.

Figure 6.41 Flash chromatography columns: (a) with joints, (b) with thread c...

Figure 6.42 Microscale chromatography columns: (a) from a Pasteur pipet; (b)...

Figure 6.43 Schematic of a high‐performance liquid chromatography column.

Chapter 7

Figure 7.1 (a) The magnetic field associated with a spinning proton. (b) The...

Figure 7.2 (a) In the absence of a magnetic field, the magnetic moments of p...

Figure 7.3 The energy difference between the two spin states of a proton dep...

Figure 7.4 In benzene (a), the induced field reinforces the applied field an...

Figure 7.5 Different types of NMR tubes, (a) Ultra‐thin NMR tube. (b) Step‐d...

Figure 7.6

1

H NMR spectrum of 2‐chloropropanoic acid.

Figure 7.7

1

H NMR spectrum of styrene.

Figure 7.8

1

H NMR spectrum of acetophenone.

Figure 7.9 H

A

sees H

B

as aligned with or against the applied field. Therefor...

Figure 7.10 H

B

sees H

A

as aligned with or against the applied field. Since t...

Figure 7.11 H

B

sees H

A

as aligned with or against the applied field. Since t...

Figure 7.12 Pascal’s triangle. Relative order of first‐order multiplicities;...

Figure 7.13

1

H NMR spectrum of propanoic acid.

Figure 7.14

1

H NMR spectrum of 2‐propanol.

Figure 7.15 The coupling constant,

J

, between the peaks of the doublet (a) i...

Figure 7.16

13

C NMR spectrum of propanoic acid.

Figure 7.17

13

C NMR spectrum of 2‐chloropropanoic acid.

Figure 7.18

13

C NMR spectrum of styrene.

Figure 7.19

13

C NMR spectrum of acetophenone.

Figure 7.20

1

H NMR spectrum of unknown ester, C

9

H

10

O

2

.

Figure 7.21

13

C NMR spectrum of unknown ester, C

9

H

10

O

2

.Splitting: A = q,...

Figure 7.22

1

H NMR spectrum of unknown compound, C

9

H

11

NO

2

.

Figure 7.23

13

C NMR spectrum of unknown compound, C

9

H

11

NO

2

.Splitting:

A

...

Figure 7.24 Problem 1

1

H NMR spectrum of unknown compound, C

3

H

7

Br.

Figure 7.25 Problem 1

13

C NMR spectrum of unknown compound, C

3

H

7

Br.

Figure 7.26 DEPT signal as a function of the variable pulse angle.

Figure 7.27 DEPT 135 spectrum of propanoic acid.

Figure 7.28 DEPT 90 spectrum of propanoic acid.

Figure 7.29 DEPT 45 spectrum of propanoic acid.

Figure 7.30 DEPT 135 spectrum of benzocaine.

Figure 7.31 DEPT 90 spectrum of benzocaine.

Figure 7.32 DEPT 45 spectrum of benzocaine.

Figure 7.33 Problem 2

13

C NMR spectrum of C

5

H

12

O.

Figure 7.34 Problem 2 DEPT 135 spectrum of C

5

H

12

O.

Figure 7.35 Problem 2 DEPT 90 spectrum of C

5

H

12

O.

Figure 7.36 Problem 2 DEPT 45 spectrum of C

5

H

12

O.

Figure 7.37 Problem 3

1

H NMR spectrum of C

5

H

10

O.

Figure 7.38 Problem 3

13

C NMR spectrum of C

5

H

10

O.

Figure 7.39 Problem 3 DEPT 135 spectrum of C

5

H

10

O.

Figure 7.40 Problem 3 DEPT 90 spectrum of C

5

H

10

O.

Figure 7.41 Problem 3 DEPT 45 spectrum of C

5

H

10

O.

Figure 7.42 Problem 4

1

H NMR spectrum of C

8

H

8

O

3

.

Figure 7.43 Problem 4

13

C NMR spectrum of C

8

H

8

O

3

.

Figure 7.44 Problem 4 DEPT 135 spectrum of C

8

H

8

O

3

.

Figure 7.45 Problem 4 DEPT 90 spectrum of C

8

H

8

O

3

.

Figure 7.46 Problem 4 DEPT 45 spectrum of C

8

H

8

O

3

.

Figure 7.47 COSY spectrum of propanoic acid.

Figure 7.48 COSY spectrum of benzocaine.

Figure 7.49 HSQC spectrum of propanoic acid.

Figure 7.50 HSQC spectrum of benzocaine.

Figure 7.51

1

H NMR spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.52 Expanded region of

δ

1.95 for

1

H NMR spectrum of unknown co...

Figure 7.53 Expanded region of

δ

5.56–6.11 for

1

H NMR spectrum of unkno...

Figure 7.54

13

C NMR spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.55 DEPT 135 spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.56 DEPT 90 spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.57 DEPT 45 spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.58 COSY spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.59 HSQC spectrum of unknown compound, C

5

H

8

O

2

.

Figure 7.60 Problem 5

1

H NMR spectrum of unknown compound, C

7

H

9

N.

Figure 7.61 Problem 5

13

C NMR spectrum of unknown compound, C

7

H

9

N.

Figure 7.62 Problem 5 DEPT 135 spectrum of unknown compound, C

7

H

9

N.

Figure 7.63 Problem 5 DEPT 90 spectrum of unknown compound, C

7

H

9

N.

Figure 7.64 Problem 5 DEPT 45 spectrum of unknown compound, C

7

H

9

N.

Figure 7.65 Problem 5 COSY spectrum of unknown compound, C

7

H

9

N.

Figure 7.66 Problem 5 HSQC spectrum of unknown compound, C

7

H

9

N.

Figure 7.67 Problem 6

1

H NMR spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.68 Problem 6

13

C NMR spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.69 Problem 6 DEPT 135 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.70 Problem 6 DEPT 90 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.71 Problem 6 DEPT 45 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.72 Problem 6 COSY spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.73 Problem 6 HSQC spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.74 Problem 7

1

H NMR spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.75 Problem 7

13

C NMR spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.76 Problem 7 DEPT 135 spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.77 Problem 7 DEPT 90 spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.78 Problem 7 DEPT 45 spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.79 Problem 7 COSY spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.80 Problem 7 HSQC spectrum of unknown compound, C

10

H

13

NO

2

.

Figure 7.81 Problem 8

1

H NMR spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.82 Problem 8

13

C NMR spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.83 Problem 8 DEPT 135 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.84 Problem 8 DEPT 90 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.85 Problem 8 DEPT 45 spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.86 Problem 8 COSY spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.87 Problem 8 HSQC spectrum of unknown compound, C

4

H

8

O

2

.

Figure 7.88 Problem 9

1

H NMR spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.89 Problem 9

13

C NMR spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.90 Problem 9 DEPT 135 spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.91 Problem 9 DEPT 90 spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.92 Problem 9 DEPT 45 spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.93 Problem 9 COSY spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.94 Problem 9 HSQC spectrum of unknown compound, C

7

H

5

ClO.

Figure 7.95 Problem 10

1

H NMR spectrum of unknown compound, C

4

H

10

O.

Figure 7.96 Problem 10

13

C NMR spectrum of unknown compound, C

4

H

10

O.

Figure 7.97 Problem 10 DEPT 135 spectrum of unknown compound, C

4

H

10

O.

Figure 7.98 Problem 10 DEPT 90 spectrum of unknown compound, C

4

H

10

O.

Figure 7.99 Problem 10 DEPT 45 spectrum of unknown compound, C

4

H

10

O.

Figure 7.100 Problem 10 COSY spectrum of unknown compound, C

4

H

10

O.

Figure 7.101 Problem 10 HSQC spectrum of unknown compound, C

4

H

10

O.

Figure 7.102 Problem 11

1

H NMR spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.103 Problem 11

13

C NMR spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.104 Problem 11 DEPT 135 spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.105 Problem 11 DEPT 90 spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.106 Problem 11 DEPT 45 spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.107 Problem 11 COSY spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.108 Problem 11 HSQC spectrum of unknown compound, C

7

H

6

O

2

.

Figure 7.109 Problem 12

1

H NMR spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.110 Problem 12

13

C NMR spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.111 Problem 12 DEPT 135 spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.112 Problem 12 DEPT 90 spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.113 Problem 12 DEPT 45 spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.114 Problem 12 COSY spectrum of unknown compound, C

8

H

9

NO

2

.

Figure 7.115 Problem 12 HSQC spectrum of unknown compound, C

8

H

9

NO

2

.

Chapter 8

Figure 8.1 Schematic of an FTIR spectrometer.

Figure 8.2 Various types of vibrational modes.

Figure 8.3 Schematic of attenuated total reflectance (ATR).

Figure 8.4 UATR accessory for frontier diamond/ZnSe spectrometer.

Figure 8.5 Salt plates and sample holder. A drop is placed between the salt ...

Figure 8.6 (a) Specac omni cell demountable cell for IR spectroscopy(b) ...

Figure 8.7 Correct way to fill a sealed cell.

Figure 8.8 Transparent regions of IR solvents and mulling oils. The open reg...

Figure 8.9 Econo‐press kit.

Figure 8.10 Quick press KBr pellet kit.

Figure 8.11 Correlation of IR absorption with organic functional groups. Row...

Figure 8.12 Colthup chart correlating IR absorption with organic functional ...

Figure 8.13 IR spectrum of Nujol.

Figure 8.14 IR spectrum of cyclohexene.

Figure 8.15 IR spectrum of 1‐hexyne.

Figure 8.16 Schematic representation of the 1667–2000 cm

−1

IR region f...

Figure 8.17 IR spectrum of toluene.

Figure 8.18 IR spectrum of ethanol.

Figure 8.19 IR spectrum of 4‐methoxyphenol.

Figure 8.20 IR spectrum of diethyl ether.

Figure 8.21 IR spectrum of acetone.

Figure 8.22 IR spectrum of acetophenone.

Figure 8.23 IR spectrum of benzaldehyde.

Figure 8.24 IR spectrum of propanoic acid.

Figure 8.25 IR spectrum of ethyl acetate.

Figure 8.26 IR spectrum of acetyl chloride.

Figure 8.27 IR spectrum of acetic anhydride.

Figure 8.28 IR spectrum of

N,N

‐dimethylformamide.

Figure 8.29 IR spectrum of aniline.

Figure 8.30 IR spectrum of diethyl amine.

Figure 8.31 IR spectrum of acetonitrile.

Figure 8.32 IR spectrum of 4‐nitrotoluene.

Figure 8.33 IR spectrum of chloroform.

Figure 8.34 IR spectrum of unknown compound with formula of C

7

H

5

ClO.

Figure 8.35 Problem 1 IR spectrum of unknown compound with formula of C

4

H

10

O...

Figure 8.36 Problem 2 IR spectrum of unknown compound with formula of C

4

H

8

O

2

Figure 8.37 Problem 3 IR spectrum of unknown compound with formula of C

7

H

5

NO

Figure 8.38 Problem 4 IR spectrum of unknown compound with formula of C

4

H

10

O...

Figure 8.39 Problem 5 IR spectrum of unknown compound with formula of C

4

H

8

O....

Figure 8.40 Problem 6 IR spectrum of unknown compound with formula of C

8

H

8

O

3

Figure 8.41 Problem 7 IR spectrum of unknown compound with formula of C

8

H

9

NO

Figure 8.42 Problem 8 IR spectrum of unknown compound with formula of C

7

H

9

N....

Chapter 9

Figure 9.1 A diagram of an electron ionization mass spectrometer.

Figure 9.2 Mass spectrum of CH

4

in both bar graph and tabular form.

Figure 9.3 Peaks in molecular ion region of bromo and chloro compounds. Cont...

Figure 9.4 Mass spectrum of hexane.

Figure 9.5 Mass spectrum of 1‐bromopropane.

Figure 9.6 Mass spectrum of 1‐chlorododecane.

Figure 9.7 Mass spectrum of toluene.

Figure 9.8 Mass spectrum of 3‐methyl‐1‐butanol.

Figure 9.9 Mass spectrum of diethylamine.

Figure 9.10 Mass spectrum of pentanal.

Figure 9.11 Problem 3 Mass spectrum of 1‐butanol.

Figure 9.12 Problem 4 Mass spectrum of 2‐pentanone.

Figure 9.13 Problem 5 Mass spectrum of methyl

t

‐butyl ether.

Figure 9.14 Problem 6 Mass spectrum of 2‐bromopropane.

Figure 9.15 Problem 7 Mass spectrum of 2‐propanamine.

Figure 9.16 Problem 8 Mass spectrum of propanoic acid.

Chapter 11

Figure 11.1 Apparatus for Procedure 25.

Guide

Cover Page

Title Page

Copyright Page

Preface

About the Companion Website

Table of Contents

Begin Reading

Appendix I: Handy Tables for the Organic Laboratory

Appendix II: Table Of Derivatives

Appendix III: Equipment and Chemicals for the Laboratory

Index

Wiley End User License Agreement

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THE SYSTEMATIC IDENTIFICATION OF ORGANIC COMPOUNDS

Ninth Edition

CHRISTINE K. F. HERMANN

TERENCE C. MORRILL

RALPH L. SHRINER

REYNOLD C. FUSON

Copyright © 2023 by John Wiley & Sons, Inc. All rights reserved.

Published by John Wiley & Sons, Inc., Hoboken, New Jersey.Published simultaneously in Canada.

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Library of Congress Cataloging‐in‐Publication Data:Names: Hermann, Christine K. F., author. | Morrill, Terence C., author. | Shriner, Ralph Lloyd, 1899‐1994. The systematic identification of organic compounds. | Fuson, Reynold C. (Reynold Clayton), 1895‐1979. The systematic identification of organic compounds.Title: The systematic identification of organic compounds / Christine K.F. Hermann, Terence C. Morrill, Ralph L. Shriner, Reynold C. Fuson.Description: Ninth edition. | Hoboken, NJ : Wiley, 2023. | Revised edition of: The systematic identification of organic compounds / Ralph L. Shriner … [et al.]. 8th ed. c2004. | Includes bibliographical references and index.Identifiers: LCCN 2022051312 (print) | LCCN 2022051313 (ebook) | ISBN 9781119799665 (paperback) | ISBN 9781119799672 (adobe pdf) | ISBN 9781119799689 (epub)Subjects: LCSH: Chemistry, Organic–Laboratory manuals.Classification: LCC QD261 .S965 2023 (print) | LCC QD261 (ebook) | DDC 547.0078–dc23/eng20230117LC record available at https://lccn.loc.gov/2022051312LC ebook record available at https://lccn.loc.gov/2022051313

Cover Design: WileyCover Images: Cover image photographs courtesy of Laura Angell; Cover images of spectra courtesy of Sydney R. Fisher

Preface

Ralph Shriner and Reynold Fuson wrote the first edition of “The Identification of Organic Compounds” in 1935. In those days, students had to identify organic compounds by solubility tests, physical properties, elemental tests, classification tests, and by preparing a derivative. The classification tests, the derivative experiments, and the derivative tables were expanded in the second edition in 1940 and in the third edition in 1948. The solubility tables were also redrawn in the third edition. David Curtin was added as author in the fourth edition in 1956. The title of the book was changed, in the fourth edition, to “The Systematic Identification of Organic Compounds.” Infrared spectroscopy was added, with correlation tables. A discussion of ultraviolet spectroscopy was added. Raman spectroscopy and nuclear magnetic resonance spectroscopy were mentioned as “show promise of becoming increasingly important.”

In the fifth edition, in 1964, 712 new entries were added to the original 2000 entries in the derivative tables. In the preface to this edition, proton magnetic resonance was considered second in importance to infrared spectroscopy. Proton nuclear magnetic resonance, including chemical shifts, peak areas, and spin–spin coupling, was described. Terence Morrill wrote the majority of the sixth edition, in 1980. Ralph Shriner provided the well‐tried and chemical tests, in addition to providing advice from years of teaching organic chemistry and qualitative organic analysis. The chemical tests, the preparation of derivatives, and spectroscopy were combined into one large chapter. More infrared spectra and proton nuclear magnetic resonance spectra were included. The discussion of carbon‐13 nuclear magnetic resonance spectroscopy, including spectra, was in a later chapter.

The seventh edition, in 1998, was written by Terence Morrill and Christine Hermann. Spectroscopy, the classification tests, and the preparation of derivatives were separated into three chapters. An introduction section was added to each set of functional groups in the classification tests and preparation of derivatives chapters. Cleaning up instructions were added at the end of each experiment. Many new drawings of apparatus were included. Almost all of these drawings were done by Christine Hermann’s husband, Richard Hermann. The derivative tables were greatly expanded. A solutions manual was written to accompany this book.

The eighth edition was written by Christine Hermann. The photographs were new for this edition. Chromatography, which had been previously in several chapters, was combined into Chapter 4. Chapter 4 also contains the separation of mixtures, based upon extractions and distillation techniques. Spectroscopy is now divided into three chapters. Chapter 6 describes NMR spectrometry, including DEPT, COSY, and HETCOR. IR spectrometry is discussed in Chapter 7. Chapter 8 discusses mass spectrometry and ultraviolet spectrometry. Chapters 6, 7, 8, and 11 contain all new spectra for this edition. More problems have been added throughout the book. Thomas Glass (Virginia Tech) and Geno Iannoccone (Virginia Tech) contributed several NMR spectra for this edition. Vernon Miller (Roanoke College) contributed mass spectra. Terra Hosp (Radford University) contributed IR spectra and tested the new classification tests in the laboratory. A solutions manual was written with the answers to all of the problems.

The ninth edition was written by Christine Hermann. A new chapter on laboratory safety was added. The separations of mixtures chapter were moved later after the solubility chapter. Discussions on instrumentation have been updated. All spectra are new for this edition. The HETCOR discussion has been replaced with HSQC. A discussion of ATR was added for this edition. Any experiments including picric acid were removed since picric acid is dangerous. Many new problems have been added throughout the chapters.

I am grateful to several chemists for contributing their time and ideas to this edition.

Sydney Fisher (Radford University) contributed all of the spectra that appear in this edition of the textbook. She is acknowledged under each spectrum in the textbook. I thank Laura Angell for creating cover for this textbook. I owe a special debt of gratitude to Steve Pond, for his patience during the preparation of this manuscript.

In summary, I hope that I have provided a book that is useful in the identification of organic compounds. I would appreciate input from faculty, students, and professional chemists on the value of the book and any comments about the book.

Christine K. F. Hermann

Radford University

About the Companion Website

This book is accompanied by a companion website.

www.wiley.com/go/hermann/identorganiccomp9e 

This website includes:

Chapter 13 with structural problems from experimental data for students to practice how to reason and solve.

Chapter 1Introduction

1.1 SYSTEMATIC IDENTIFICATION OF ORGANIC COMPOUNDS: THE NEED FOR ORGANIC QUALITATIVE ANALYSIS

Qualitative organic chemistry has been in use since long before the advent of modern spectroscopy. Modern spectroscopic techniques have assisted the chemist by providing spectra that can be interpreted to give more detail about the interaction between atoms and functional groups. Some students have difficulty identifying structures using exclusively nuclear magnetic resonance (NMR) spectra, infrared (IR) spectra, and mass spectra. The information obtained through chemical tests allows the student to narrow down the possible functional groups. Additionally, by taking a course in qualitative organic chemistry, a student is given the freedom of selecting, for himself or herself, the functional group classification tests that are needed to identify a compound.

In roughly two dozen chapters or more of a standard organic text, the student encounters many chemical reactions. Literally, millions of different organic compounds have been synthesized. Chemical companies sell thousands of compounds, and industrial‐scale production generates thousands of different compounds on various scales. Characterization of organic compounds can be done by a handful of physical and chemical observations if it is done in a systematic manner. The list of more common and readily available chemicals is much smaller than the millions that are possible.

In this text, we have focused our attention on an even smaller list of compounds that can be used as “unknowns.” The melting point‐boiling point tables give a very accurate idea of the focus of this book. Instructors using this book may very well use other references, such as the CRC reference volumes,1 the Millipore Sigma website, the Fisher Scientific website, and others, for a more extensive list of possibilities for “unknown” compounds.

Organic chemists are often confronted with either of the following extreme situations:

Determination of the identity of a compound that has no prior history. This is often the case for a natural‐products chemist who must study a very small amount of sample isolated from a plant or an animal. A similar situation applies to the forensic chemist who analyzes very small samples related to a lawsuit or crime.

The industrial chemist or college laboratory chemist who must analyze a sample that contains a major

expected

product and minor products, all of which could be expected from a given set of reagents and conditions. It is entirely possible that such a sample with a well‐documented history will allow one to have a properly preconceived notion as to how the analysis should be conducted.

The theory and technique for identifying organic compounds constitute an essential introduction to research in organic chemistry. This study organizes the accumulated knowledge concerning physical properties, structures, and reactions of thousands of carbon compounds into a systematic, logical identification scheme. Although its initial aim is the characterization of previously known compounds, the scheme of attack constitutes the first stage in the elucidation of structure of newly prepared organic compounds.

If, for example, two known compounds A and B are dissolved in a solvent C, a catalyst D is added, and the whole subjected to proper reaction conditions of temperature and pressure, a mixture of new products plus unchanged starting materials results.

Immediately two questions arise:

What procedure should be chosen to separate the mixture into its components?

How are the individual compounds (E through K) to be positively characterized? Which ones are unchanged reactants? Which compounds have been described previously by other chemists? Finally, which products are new?

These two problems are intimately related. Separations of organic mixtures use both chemical and physical processes and are dependent on the structures of the constituents.

The present course of study focuses on the systematic identification of individual compounds first. The specific steps are given in Chapter 3. Physical properties are described in Chapter 4. The use of these principles for devising efficient procedures for the separation of mixtures is outlined in Chapter 5. Solubility techniques are described in Chapter 6. Spectroscopy methods are discussed in Chapters 7–9. The classification tests for functional groups are given in Chapter 10, and the preparation of derivatives is given in Chapter 11.

In recent years, the question of scale has become an issue. Scale has always been a focal point for qualitative analysis. The issue has been recognized at an even earlier point in the chemistry curriculum, and a very large number of colleges now incorporate some sort of microscale or miniscale approach into their sophomore organic courses. Organic qualitative analysis has always been a test tube subject and thus should philosophically be in tune with the microscale revolution. Most of our experiments are at the scale of the past editions of this text and thus many chemistry instructors may wish to scale down. Scaling down to 1/2, 1/5, or 1/10 of the cited amount should be very straightforward in most cases, and thus scale is the option of the course coordinator. The only warning is that certain reactions (for example, conversion of a carboxylic acid to an amide or of an alcohol to a 3,5‐dinitrobenzoate) are notoriously sensitive to the purity of the reagents. Thus, a larger‐scale reaction is likely desirable here.

Cleanup and Waste Disposal

A related, and in some ways bigger, issue is that of waste disposal. The trend at most colleges in recent years is to have waste disposal done by a licensed company under contract with the college. Most instructors are not qualified to dispose of waste and thus they can only provide cleanup guidelines. We have attempted to prepare this edition with that in mind. It is usually the job of the instructor to provide containers for waste disposal. Waste disposal vessels are usually labeled as to their use, such as solids vs. liquids and inorganic vs. organic compounds. Special containers are used for especially toxic wastes such as halogenated organic compounds or heavy metal solutions. Additionally, there are usually special containers for broken glass equipment. There may be places to recycle paper, and finally, there are simple trash cans for garbage. There is usually a classification decision for every act of discarding material. Most importantly, the students should receive instructions from their lab instructors that are in accordance with local regulations.

1.2 SUGGESTIONS TO STUDENTS AND INSTRUCTORS

Schedule

An exact time schedule applicable to all schools cannot be set because of the varied use of semester, quarter, trimester, and summer session terms of instructions. However, for a semester of 15 weeks, two 3‐hr laboratory periods per week plus one “lab lecture” per week work well. Modifications can be made to adapt the course to individual schools.

Lecture Material

The first lecture should emphasize safety and all safety protocols as described in Chapter 2. Next, the course overview is described as outlined in Chapter 3. Next, a review of spectroscopic techniques, including operating instructions, should be discussed (Chapters 7–9). Physical properties (Chapter 4), including melting point and boiling point, should be described next. Solubility of the unknown should be reviewed (Chapter 5). Recrystallization (Section 4.4) and separation of mixtures (Chapter 6) could be explained. It is not necessary to lecture on all the experiments and procedures (Chapters 10 and 11), but an introduction to the most common tests should be discussed.

After the first one or two unknowns have been completed, it will be valuable to work on some of the problems of Chapter 13 (available on book companion website) in class and discuss the structure correlation with chemical reactions and spectral data. It is the instructor's choice whether or not to make the Solutions Manual available to the students.

Laboratory Work—Unknowns

By use of spectroscopic data and chemical reactions, it is possible for students to work out six to eight single compounds and two mixtures (containing two or three components each) in a 15‐week semester.

To get a rapid start and illustrate the systematic scheme, it may be useful to give a titratable acid to each student for a first unknown. The student is told that the substance is titratable and that he or she is to get the elemental analysis, melting or boiling point, and neutralization equivalent and to calculate the possible molecular weights. Then, if the unknown contains halogen or nitrogen, the student is to select and try three or four (but no more) classification tests. Next, a list of possible compounds with derivatives is prepared by consulting the table of acids (Appendix II). One derivative is made and turned in with the report (Sections 3.1 and 3.11). This first unknown should be completed in two 3‐hr laboratory periods.

Since many schools run organic qualitative analysis in a lab course connected to the second semester (or last term) of the traditional sophomore course, the decision about how to order the functional groups possible for the unknown may very well depend upon the order of coverage of these groups in the lecture course.

The other unknowns should be selected to provide experience with compounds containing a wide variety of functional groups.

It is recommended to check the student's progress after the preliminary tests, solubility classification, and elemental analyses have been completed. This checking procedure is highly recommended for the first one or two unknowns for each student. It is best to give deadlines throughout the semester for the submission of lab reports. It is not in the best interest of the student to have everything due at the end of the semester.

Purity of Unknowns Although every effort is made to provide samples of compounds with a high degree of purity, students and instructors should recognize that many organic compounds decompose or react with oxygen, moisture, or carbon dioxide when stored for a considerable time. Such samples will have wide melting or boiling point ranges, frequently lower than the literature values. Hence, for each unknown, the student should make a preliminary report of the observed value for melting or boiling point. The instructor should verify these data and if necessary tell the student to purify the sample by recrystallization or distillation and to repeat the determination of the physical constant in question. This avoids the waste of time and frustration from conflicting data.

Amounts of Unknowns As a general guide, the following amounts are suggested:

Unknown No. 1, a titratable acid, 4 g of a solid or 10 mL of a liquidUnknown No. 2, 3 g of a solid or 8 mL of a liquidUnknown No. 3, 2 g of a solid or 5 mL of a liquidUnknown No. 4, 1 g of a solid or 3 mL of a liquid

Mixtures should contain 4–5 g of each component. Note: If purification of a sample is required, an additional amount should be furnished to the student.

The amounts listed above are essentially macroscale unknowns; the use of analytical techniques and instrumentation such as thin‐layer chromatography and gas chromatography may very well allow sample sizes of unknowns to be ca. 20% of that listed above. In such cases—that is, for microscale samples—it is imperative that chemical test and derivatization procedures described in Chapters 10 and 11 be scaled down correspondingly.

Toward the end of the term, when the student's laboratory technique has been perfected and the facility in interpreting reactions has been obtained, it is possible to work with still smaller samples of compounds by using smaller amounts of reagents in the classification tests and by using a smaller scale in the derivatization procedure.

Timesaving Hints

It is important to plan laboratory work in advance. This can be done by getting the elemental analyses, physical constants, solubility behavior, and IR and NMR spectra on several unknowns during one laboratory period. This information should be carefully recorded in the notebook and then reviewed, along with the discussion in each of these steps, the evening before the next laboratory period. A list of a few selected classification tests to be tried is made and carried out in the laboratory the next day. In some cases, a preliminary list of possible compounds and desirable derivatives can be made. It is important to note that a few of the 47 classification tests should be run on a given compound. It should not be necessary to make more than two derivatives; usually, one derivative will prove to be unique. The object is to utilize the sequence of systematic steps outlined in Chapter 3 in the most efficient manner possible.

The instructor should guide the students so that the correct identification results from a process of logical deductive reasoning. Once the structure of the unknown is established, an understanding of the test reactions and spectra becomes clear. Practice in this phase of reasoning from laboratory observations to structure is facilitated by early guidelines in Chapter 13 (available on book companion website). One method for developing this ability is for the instructor to write a structural formula on the chalkboard and ask the students to predict the solubility behavior and select the appropriate classification tests.

To tie together the identification work in this course with actual research, the instructor can select a few typical examples of naturally occurring compounds, such as nicotine, D‐ribose, quinine, penicillin G, and vitamin B1, and review the identifying reactions used to deduce these structures. The recent literature also furnishes examples of the value of IR and NMR spectra in establishing structures. Knowledge of the mechanisms of the reactions used for classification tests and for preparing derivatives requires an understanding of the functional groups and their electronic structures.

Throughout this book, references to original articles, monographs, and reference works are given. Many of these will not be used during a one‐semester course. However, the citations have been selected to furnish valuable starting sources for future work and are of great use in senior and graduate research.

The use of this manual will be greatly facilitated by the preparation of a set of index tabs for each chapter and parts of chapters. The time spent in preparing the index tabs is more than recovered in speeding up the location of experiments for functional groups, derivatization procedures, and tables of derivatives.

Note

1

For example, Z. Rappaport (editor),

Handbook of Tables for Organic Compound Identification,

3rd ed. (CRC Press, Boca Raton, 1996).

Chapter 2Laboratory Safety

2.1 WORKING SAFELY IN THE LABORATORY

At all times, the instructor and students should observe safety rules. They should always wear safety glasses in the laboratory and should become familiar with emergency treatment.

Laboratories are places of great responsibility. Careful practice and mature behavior can prevent most mishaps. The following are all very important. Treating the lab with respect makes it far less dangerous. The following list is a set of rules that must be followed in a laboratory.

Eye Protection Chemical splash goggles must be worn at all times. Eyeglasses, with shatterproof glass, are inadequate without goggles or safety glasses. Side shields are required for all protective eyewear.

Shoes Closed‐toe and closed‐heel shoes that completely cover the feet are required in the laboratory.

Protective Clothing A protective apron or lab coat is recommended in the laboratory. If any chemical is spilled on your skin or clothing, it must be washed off immediately.

Food and Drink Food and beverage are strictly prohibited in the laboratory. Do not taste or smell any chemicals.

No Unauthorized Experiments Unauthorized experiments are forbidden in the laboratory. Do not work alone in the laboratory. Chemicals, supplies, or equipment must not be removed from the laboratory. All experiments must be approved by the instructor.

Smoking Smoking is prohibited in the laboratory.

Personal Items No bookbags, coats, or books, except the lab book, should be brought into the laboratory. Ask your instructor where these items can be stored while you are in the laboratory. Laptop computers may be used in a designated area that is free from chemicals and equipment. Bring in only the items that are needed during the laboratory period. These items can be damaged by the chemicals in the laboratory.

Use of Equipment Do not use any equipment until the instructor has shown you how to use it.

Glassware Do not use any broken, chipped, or cracked glassware. Get replacement glassware from your instructor. Ask your instructor where to place broken glassware.

Bench Cleanup At the end of the laboratory period, put away all equipment, clean the laboratory bench, and wash your hands.

Use of Chemicals Take only the amount that is needed. Leave all bottles in their proper places. Place the lids on the bottles after use. Clean up all spilled chemicals immediately.

Careful Reading of Labels