DEAN’S HANDBOOK
OF ORGANIC
CHEMISTRY
George W. Gokel, Ph.D.
Director, Program in Chemical Biology
Professor, Department of Molecular Biology and Pharmacology
Washington University School of Medicine
Professor, Department of Chemistry
Washington University
St. Louis Missouri

Second Edition

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PREFACE

The first edition of the Handbook of Organic Chemistry was edited by Professor John A.
Dean. It appeared in 1987 and has served as a widely used and convenient reference work

for more than 15 years. When Professor Dean asked if I would work with him to develop
a second edition, I was pleased to do so. I felt that as valuable as the first edition was, it
would be more broadly useful if it contained discussions of the data, the means by which
the data were acquired, and perhaps even how the data are applied in modern science. We
thus began the revision with enhanced usability as the foremost goal. Sadly, just as we were
beginning the effort, Professor Dean passed away. He will be sorely missed.
In following the original plan, many figures, structures, discussions of the methods, and
illustrations of the data have been incorporated. Some tables have been reorganized. In
some cases tables have been printed twice; although they contain the same data, they are
arranged by different criteria. The intent is to make the data easier for the researcher to
access and use. Some Internet addresses that can serve as a supplementary resource are
included. Despite the numerous additions, the volume remains compact and accessible.
As Professor Dean was not involved in producing this edition, I take responsibility
for errors of fact or omission. I hope the volume is error-free, but I would appreciate
being informed of any mistakes that are found. Finally, I wish to express my thanks to
Mrs. Jolanta Pajewska, who helped in improving the manuscript and the proofreading.
GEORGE W. GOKEL

iv

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ABOUT THE AUTHOR

George W. Gokel, Ph.D., is a professor of molecular biology and pharmacology and the
director of the Chemical Biology Program at Washington University School of Medicine.
He lives in Chesterfield, Missouri.

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Contents

Preface .............................................................................

iv

About the Author ...............................................................

v

1.

Organic Compounds ...............................................

1.1

Nomenclature of Organic Compounds .................................

1.2

Hydrocarbons and Heterocycles ..................................
Table 1.1 Names of Straight-Chain Alkanes .............
Table 1.2 Fused Polycyclic Hydrocarbons .................
Table 1.3 Specialist Nomenclature for
Heterocyclic Systems .........................................
Table 1.4 Suffixes for Specialist Nomenclature
of Heterocyclic Systems .....................................
Table 1.5 Trivial Names of Heterocyclic

Systems Suitable for Use in Fusion
Names ................................................................
Table 1.6 Trivial Names for Heterocyclic
Systems That Are Not Recommended for
Use in Fusion Names .........................................

1.2
1.2
1.8

Functionalized Compounds .........................................
Table 1.7 Characteristic Groups for Substitutive
Nomenclature .....................................................
Table 1.8 Characteristic Groups Cited Only as
Prefixes in Substitutive Nomenclature ................
Table 1.9 Functional Class Names Used in
Radicofunctional Nomenclature .........................

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1.12
1.12

1.13

1.16
1.18
1.19

1.21
1.24

iii


iv

Contents
Specific Functionalized Groups ...................................
Table 1.10 Retained Trivial Names of Alcohols
and Phenols with Structures ...............................
Table 1.11 Names of Some Carboxylic Acids ...........
Table 1.12 Parent Structures of PhosphorusContaining Compounds ......................................
Table 1.13 ..................................................................

1.25
1.26
1.33
1.40
1.44

Stereochemistry .......................................................... 1.47
Chemical Abstracts Indexing System .......................... 1.60
Physical Properties of Pure Substances ...............................

1.61

Table 1.14 Empirical Formula Index for Organic
Compounds ........................................................... 1.61

Table 1.15 Physical Constants of Organic
Compounds ........................................................... 1.80

2.

3.

Inorganic and Organometallic Compounds ..........

2.1

Table 2.1 Physical Constants of Inorganic
Compounds .....................................................................

2.2

Properties of Atoms, Radicals, and Bonds ...........

3.1

Nuclides .................................................................................

3.2

Table 3.1 Table of Nuclides .........................................

3.2

Electronegativity ....................................................................


3.9

Table 3.2A Electronegativities of the Elements ........... 3.10
Table 3.2B Electronegativities of the Groups ............... 3.10
Electron Affinity ......................................................................

3.11

Table 3.3 Electron Affinities of Elements,
Radicals, and Molecules ........................................ 3.11
Bond Lengths and Strengths ................................................

3.13

Table 3.4A Bond Lengths between Carbon and
Other Elements ...................................................... 3.14

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v

Table 3.4B Bond Lengths between Elements
Other Than Carbon ................................................ 3.17
Table 3.5 Bond Strengths ............................................ 3.19
Bond and Group Dipole Moments ........................................


3.30

Table 3.6 Bond Dipole Moments ................................. 3.30
Table 3.7 Group Dipole Moments ................................ 3.31

4.

Physical Properties .................................................

4.1

Solubilities .............................................................................

4.2

Table 4.1 Solubility of Gases in Water .........................

4.2

Vapor Pressures ....................................................................

4.8

Table 4.2 Vapor Pressure of Mercury ..........................

4.8

Table 4.3 Vapor Pressure of Water for
Temperatures from –10 to 120°C .......................... 4.10

Table 4.4 Vapor Pressure of Deuterium Oxide ............ 4.12
Boiling Points .........................................................................

4.12

Table 4.5A Boiling Points for Common Organic
Solvents ................................................................ 4.12
Table 4.5B Boiling Points for Common Organic
Solvents ................................................................ 4.15
Table 4.5C Boiling Point for Common Organic
Solvents ................................................................ 4.17
Table 4.6 Molecular Elevation of the Boiling
Point ...................................................................... 4.23
Table 4.7 Binary Azeotropic (Constant-Boiling)
Mixtures ................................................................. 4.25
Table 4.8 Ternary Azeotropic Mixtures ........................ 4.46
Freezing Points .....................................................................

4.52

Tables 4.9A and B Molecular Lowering of the
Melting or Freezing Point ....................................... 4.52
Viscosity, Dielectric Constant, Dipole Moment, Surface
Tension, and Refractive Index ........................................
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Contents
Table 4.10 Viscosity, Dielectric Constant, Dipole
Moment and Surface Tension of Selected
Organic Substances .............................................. 4.57
Table 4.11 Viscosity, Dielectric Constant, Dipole
Moment, and Surface Tension of Selected
Inorganic Substances ............................................ 4.94
Table 4.12 Refractive Index, Viscosity, Dielectric
Constant, and Surface Tension of Water at
Various Temperatures ........................................... 4.98
Combustible Mixtures ............................................................

4.99

Table 4.13 Properties of Combustible Mixtures
in Air ...................................................................... 4.99

5.

Thermodynamic Properties ....................................

5.1

Enthalpies and Gibbs (Free) Energies of Formation,
Entropies, and Heat Capacities ......................................

5.2


Table 5.1 Enthalpies and Gibbs (Free) Energies
of Formation, Entropies, and Heat Capacities
of Organic Compounds ..........................................

5.3

Table 5.2 Heats of Melting and Vaporization
(or Sublimation) and Specific Heat at Various
Temperatures of Organic Compounds ................... 5.44
Critical Phenomena ...............................................................

5.75

Table 5.3 Critical Properties ........................................ 5.75
Table 5.4 Group Contributions for the Estimation
of Critical Properties .............................................. 5.88

6.

Spectroscopy ...........................................................

6.1

Ultraviolet-Visible Spectroscopy ...........................................

6.3

Table 6.1 Electronic Absorption Bands for
Representative Chromophores ..............................


6.5

Table 6.2 Ultraviolet Cutoffs of Spectrograde
Solvents ................................................................

6.6

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vii

Table 6.3 Absorption Wavelength of Dienes ................

6.7

Table 6.4 Absorption Wavelength of Enones and
Dienones ...............................................................

6.7

Table 6.5 Solvent Correction for UV–VIS
Spectroscopy .........................................................

6.8


Table 6.6 Primary Band of Substituted Benzene
and Heteroaromatics .............................................

6.9

Table 6.7 Wavelength Calculation of the Principal
Band of Substituted Benzene Derivatives ..............

6.9

Photoluminescence ...............................................................

6.10

Table 6.8 Fluorescence Spectroscopy Data of
Some Organic Compounds .................................... 6.11
Table 6.9 Fluorescence Quantum Yield Values ........... 6.17
Table 6.10 Phosphorescence Spectroscopy of
Some Organic Compounds .................................... 6.17
Infrared Spectroscopy ...........................................................

6.21

Table 6.11 Absorption Frequencies of Single
Bonds to Hydrogen ................................................ 6.21
Table 6.12 Absorption Frequencies of Triple
Bonds .................................................................... 6.28
Table 6.13 Absorption Frequencies of Cumulated
Double Bonds ........................................................ 6.29

Table 6.14 Absorption Frequencies of Carbonyl
Bonds .................................................................... 6.31
Table 6.15 Absorption Frequencies of Other
Double Bonds ........................................................ 6.35
Table 6.16 Absorption Frequencies of Aromatic
Bonds .................................................................... 6.39
Table 6.17 Absorption Frequencies of
Miscellaneous Bands ............................................. 6.40
Table 6.18 Absorption Frequencies in the Near
Infrared .................................................................. 6.47

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Contents
Table 6.19 Infrared Transmitting Materials .................. 6.49
Table 6.20 Infrared Transmission Characteristics
of Selected Solvents .............................................. 6.51
Raman Spectroscopy ............................................................

6.54

Table 6.21 Raman Frequencies of Single Bonds
to Hydrogen and Carbon ....................................... 6.54
Table 6.22 Raman Frequencies of Triple Bonds .......... 6.59
Table 6.23 Raman Frequencies of Cumulated

Double Bonds ........................................................ 6.60
Table 6.24 Raman Frequencies of Carbonyl
Bonds .................................................................... 6.61
Table 6.25 Raman Frequencies of Other Double
Bonds .................................................................... 6.63
Table 6.26 Raman Frequencies of Aromatic
Compounds ........................................................... 6.66
Table 6.27 Raman Frequencies of Sulfur
Compounds ........................................................... 6.67
Table 6.28 Raman Frequencies of Ethers ................... 6.69
Table 6.29 Raman Frequencies of Halogen
Compounds ........................................................... 6.70
Table 6.30 Raman Frequencies of Miscellaneous
Compounds ........................................................... 6.71
Nuclear Magnetic Resonance Spectroscopy .......................

6.71

Table 6.31 Nuclear Properties of the Elements ........... 6.73
Table 6.32 Proton Chemical Shifts of Reference
Compounds Relative to Tetramethylsilane ............. 6.74
Table 6.33 Common NMR Solvents ............................ 6.75
Table 6.34 Proton Chemical Shifts .............................. 6.76
Table 6.35 Estimation of Chemical Shift for
Proton of —CH2— and >CH— Groups .................. 6.79
Table 6.36 Estimation of Chemical Shift of Proton
Attached to a Double Bond .................................... 6.80

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ix

Table 6.37 Chemical Shifts in Monosubstituted
Benzene ................................................................ 6.81
Table 6.38 Proton Spin Coupling Constants ................ 6.82
Table 6.39 Carbon-13 Chemical Shifts ........................ 6.83
Table 6.40 Estimation of Chemical Shifts of
Alkane Carbons ..................................................... 6.86
Table 6.41 Effect of Substituent Groups on Alkyl
Chemical Shifts ...................................................... 6.87
Table 6.42 Estimation of Chemical Shift of
Carbon Attached to a Double Bond ....................... 6.88
Table 6.43 Carbon-13 Chemical Shifts in
Substituted Benzenes ............................................ 6.89
Table 6.44 Carbon-13 Chemical Shifts in
Substituted Pyridines ............................................. 6.90
Table 6.45 Carbon-13 Chemical Shifts of
Carbonyl Group ..................................................... 6.91
Table 6.46 One-Bond Carbon–Hydrogen Spin
Coupling Constants ............................................... 6.92
Table 6.47 Two-Bond Carbon–Hydrogen Spin
Coupling Constants ............................................... 6.93
Table 6.48 Carbon–Carbon Spin Coupling
Constants .............................................................. 6.93
Table 6.49 Carbon–Fluorine Spin Coupling

Constants .............................................................. 6.94
Table 6.50 Carbon-13 Chemical Shifts of
Deuterated Solvents .............................................. 6.95
Table 6.51 Carbon-13 Spin Coupling Constants
with Various Nuclei ................................................ 6.96
Table 6.52 Boron-11 Chemical Shifts .......................... 6.96
Table 6.53 Nitrogen-15 (or Nitrogen-14) Chemical
Shifts ..................................................................... 6.97

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Contents
Table 6.54 Nitrogen-15 Chemical Shifts in
Monosubstituted Pyridine ...................................... 6.100
Table 6.55 Nitrogen-15 Chemical Shifts for
Standards .............................................................. 6.101
Table 6.56 Nitrogen-15 to Hydrogen-1 Spin
Coupling Constants ............................................... 6.101
Table 6.57 Nitrogen-15 to Carbon-13 Spin
Coupling Constants ............................................... 6.102
Table 6.58 Nitrogen-15 to Fluorine-19 Spin
Coupling Constants ............................................... 6.102
Table 6.59 Fluorine-19 Chemical Shifts ....................... 6.102
Table 6.60 Fluorine-19 Chemical Shifts for
Standards .............................................................. 6.104

Table 6.61 Fluorine-19 to Fluorine-19 Spin
Coupling Constants ............................................... 6.104
Table 6.62 Silicon-29 Chemical Shifts ......................... 6.104
Table 6.63 Phosphorus-31 Chemical
Shifts ..................................................................... 6.105
Table 6.64 Phosphorus-31 Spin Coupling
Constants .............................................................. 6.109
Electron Spin Resonance ...................................................... 6.110
Table 6.65 Spin–Spin Coupling (Hyperfine
Splitting Constants) ............................................... 6.111
Ionization Potentials .............................................................. 6.114
Table 6.66A Ionization Potentials of Molecular
Species ................................................................. 6.114
Table 6.66B Alphabetical Listing of Ionization
Potentials of Molecular Species ............................. 6.120
Table 6.67 Ionization Potentials of Radical
Species ................................................................. 6.122
X-Ray Diffraction ................................................................... 6.122

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7.

xi

Physiochemical Relationships ...............................


7.1

Linear Free Energy Relationships .........................................

7.2

Table 7.1 Hammett and Taft Substituent
Constants ..............................................................

7.3

Table 7.2 pKA and Rho (p) Values for the
Hammett Equation .................................................

7.8

Table 7.3 pKA and Rho (p) Values for the Taft
Equation ................................................................ 7.10
Table 7.4 Special Hammett Sigma
Constants .............................................................. 7.10

8.

Electrolytes, Electromotive Force, and
Chemical Equilibrium ..............................................

8.1

Equilibrium Constants ...........................................................


8.2

Table 8.1 pKA Values of Organic Materials in
Water at 25°C ........................................................

8.3

Table 8.2 Proton-Transfer Reactions of Inorganic
Materials in Water at 25°C ..................................... 8.61
Table 8.3 Selected Equilibrium Constants in
Aqueous Solution at Various Temperatures ........... 8.64
Table 8.4 Indicators for Aqueous Acid–Base
Titrations ............................................................... 8.72
Buffer Solutions .....................................................................

8.74

Table 8.5 National Institute of Standards and
Technology (Formerly National Bureau of
(Standards U.S.)) Reference pH Buffer
Solutions ................................................................ 8.74
Table 8.6 Compositions of National Institute of
Standards and Technology. Standard pH
Buffer Solutions ..................................................... 8.75
Table 8.7 pH Values of Buffer Solutions for
Control Purposes ................................................... 8.76

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Contents
Reference Electrodes ............................................................

8.77

Table 8.8 Potentials of Reference Electrodes (in
Volts) as a Function of Temperature ...................... 8.77
Table 8.9 Potentials of Reference Electrodes (in
Volts) at 25°C for Water–Organic Solvent
Mixtures ................................................................. 8.79
Electrode Potentials ..............................................................

8.80

Table 8.10 Potentials of Selected Half-Reactions
at 25°C .................................................................. 8.80
Table 8.11 Half-Wave Potentials (vs. Saturated
Calomel Electrode) of Organic Compounds
at 25°C .................................................................. 8.82

9.

Data Useful in Laboratory Manipulations and
Analysis ....................................................................


9.1

Cooling Mixtures ....................................................................

9.2

Table 9.1 Cooling Mixtures Made from Dry Ice
and Salts ...............................................................

9.2

Table 9.2 Dry Ice or Liquid Nitrogen Slush Baths ........

9.2

Humidification and Drying .....................................................

9.2

Table 9.3 Humidity (%) Maintained by Saturated
Solutions of Various Salts at Specified
Temperatures ........................................................

9.3

Table 9.4 Humidity (%) Maintained by Saturated
Solutions of Common Salts at Specified
Temperatures ........................................................

9.3


Table 9.5 Drying Agents ..............................................

9.4

Separation Methods ..............................................................

9.5

Table 9.6 Solvents of Chromatographic Interest ..........

9.5

Table 9.7 Solvents Having the Same Refractive
Index and the Same Density at 25°C .....................

9.7

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xiii

Table 9.8 McReynolds’ Constants for Stationary
Phases in Gas Chromatography ............................ 9.10


10. Polymers, Rubbers, Fats, Oils, and Waxes ........... 10.1
Polymers ................................................................................

10.2

Table 10.1 Plastic Families ......................................... 10.7
Formulas and Key Properties of Plastic Materials ................

10.9

Table 10.2 Properties of Commercial Plastics ............. 10.24
Formulas and Advantages of Rubbers ................................. 10.60
Table 10.3 Properties of Natural and Synthetic
Rubbers ................................................................. 10.64
Chemical Resistance ............................................................ 10.65
Table 10.4 Resistance of Selected Polymers and
Rubbers to Various Chemicals at 20°C .................. 10.65
Table 10.5 Common Abbreviations Used in
Polymer Chemistry ................................................ 10.67
Gas Permeability ................................................................... 10.70
Table 10.6 Gas Permeability Constants (1010P) at
25°C for Polymers and Rubbers ............................ 10.70
Table 10.7 Vapor Permeability Constants (1010P)
at 35°C for Polymers ............................................. 10.73
Fats, Oils, and Waxes ........................................................... 10.73
Table 10.8 Constants of Fats and Oils ........................ 10.73
Table 10.9 Constants of Waxes .................................. 10.76

11. Abbreviations, Constants, and Conversion
Factors ...................................................................... 11.1

Physical Constants ................................................................

11.2

Table 11.1 Fundamental Physical Constants ............... 11.2
Greek Alphabet .....................................................................

11.5

Table 11.2 Greek Alphabet .......................................... 11.5

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xiv

Contents
Prefixes ..................................................................................

11.5

Table 11.3 Prefixes for Naming Multiples and
Submultiples of Units ............................................. 11.5
Table 11.4 Numerical Prefixes .................................... 11.5
Transformations ....................................................................

11.6


Table 11.5 Conversion Formulas for Solutions
Having Concentrations Expressed in Various
Ways ..................................................................... 11.6
Table 11.6 Conversion Factors ................................... 11.7
Statistics ................................................................................ 11.14
Table 11.7 Values of t ................................................. 11.14

Index ................................................................................

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I.1


SECTION 1

ORGANIC COMPOUNDS

NOMENCLATURE OF ORGANIC COMPOUNDS . . . . . . . .
Hydrocarbons and Heterocycles . . . . . . . . . . . . . . . . .
Table 1.1 Names of Straight-Chain Alkanes . . . . . . . .
Table 1.2 Fused Polycyclic Hydrocarbons . . . . . . . . .
Table 1.3 Specialist Nomenclature for Heterocyclic
Systems . . . . . . . . . . . . . . . . . . . . . .
Table 1.4 Suffixes for Specialist Nomenclature of
Heterocyclic Systems . . . . . . . . . . . . . . .
Table 1.5 Trivial Names of Heterocyclic Systems Suitable
for Use in Fusion Names . . . . . . . . . . . . .

Table 1.6 Trivial Names for Heterocyclic Systems that are
Not Recommended for Use in Fusion Names . .
Functionalized Compounds . . . . . . . . . . . . . . . . . . .
Table 1.7 Characteristic Groups for Substitutive
Nomenclature . . . . . . . . . . . . . . . . . . .
Table 1.8 Characteristic Groups Cited Only as Prefixes
in Substitutive Nomenclature . . . . . . . . . . .
Table 1.9 Functional Class Names Used in Radicofunctional
Nomenclature . . . . . . . . . . . . . . . . . . .
Specific Functionalized Groups . . . . . . . . . . . . . . . . .
Table 1.10 Retained Trivial Names of Alcohols and Phenols
with Structures . . . . . . . . . . . . . . . . . .
Table 1.11 Names of Some Carboxylic Acids . . . . . . . .
Table 1.12 Parent Structures of Phosphorus-containing
Compounds . . . . . . . . . . . . . . . . . . . .
Table 1.13
. . . . . . . . . . . . . . . . . . . . . . . . . . .
Stereochemistry . . . . . . . . . . . . . . . . . . . . . . . . . .
Chemical Abstracts Indexing System . . . . . . . . . . . . . .
PHYSICAL PROPERTIES OF PURE SUBSTANCES . . . . . . .
Table 1.14 Empirical Formula Index for Organic
Compounds . . . . . . . . . . . . . . . . . . . .
Table 1.15 Physical Constants of Organic Compounds . . .

1.1

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1.2
1.2
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1.12

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1.12

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1.13


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1.16
1.18

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1.19

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1.21

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1.24
1.25

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1.26
1.34

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1.40
1.44
1.47
1.60
1.61

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1.61
1.80

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1.2

SECTION 1


NOMENCLATURE OF ORGANIC COMPOUNDS
The following synopsis of rules for naming organic compounds and the examples given in
explanation are not intended to cover all the possible cases. For a more comprehensive and
detailed description, see J. Rigaudy and S. P. Klesney, Nomenclature of Organic
Chemistry, Sections A, B, C, D, E, F, and H, Pergamon Press, Oxford, 1979. This publication contains the recommendations of the Commission on Nomenclature of Organic
Chemistry and was prepared under the auspices of the International Union of Pure and
Applied Chemistry (IUPAC).
Hydrocarbons and Heterocycles
Alkanes. The saturated open-chain (acyclic) hydrocarbons (CnH2n ϩ 2) have names ending
in -ane. The first four members have the trivial names methane (CH4), ethane (CH3CH3
or C2H6), propane (C3H8), and butane (C4H10). For the remainder of the alkanes, the first
portion of the name is derived from the Greek prefix (see Table 11.4) that cites the number
of carbons in the alkane followed by -ane with elision of the terminal -a from the prefix,
as shown in Table 1.1.
TABLE 1.1 Names of Straight-Chain Alkanes
n*

Name

n*

Name

n*

Name

1
2

3
4
5
6
7
8
9
10

Methane
Ethane
Propane
Butane
Pentane
Hexane
Heptane
Octane
Nonane†
Decane

11
12
13
14
15
16
17
18
19
20


Undecane‡
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecane
Icosane§

21
22
23

Henicosane
Docosane
Tricosane

30
31
32

Triacontane
Hentriacontane
Dotriacontane

40
50


Tetracontane
Pentacontane

n*
60
70
80
90
100
110
120
121

Name
Hexacontane
Heptacontane
Octacontane
Nonacontane
Hectane
Decahectane
Icosahectane
Henicosahectane

*n ϭ total number of carbon atoms.
† Formerly called enneane.
‡ Formerly called hendecane.
§ Formerly called eicosane.

For branching compounds, the parent structure is the longest continuous chain present in

the compound. Consider the compound to have been derived from this structure by replacement of hydrogen by various alkyl groups. Arabic number prefixes indicate the carbon to which
the alkyl group is attached. Start numbering at whichever end of the parent structure that results
in the lowest-numbered locants. The arabic prefixes are listed in numerical sequence, separated
from each other by commas and from the remainder of the name by a hyphen.
If the same alkyl group occurs more than once as a side chain, this is indicated by the
prefixes di-, tri-, tetra-, etc. Side chains are cited in alphabetical order (before insertion of
any multiplying prefix). The name of a complex radical (side chain) is considered to begin
with the first letter of its complete name. Where names of complex radicals are composed
of identical words, priority for citation is given to that radical which contains the lowestnumbered locant at the first cited point of difference in the radical. If two or more side chains
are in equivalent positions, the one to be assigned the lowest-numbered locant is that cited
first in the name. The complete expression for the side chain may be enclosed in parentheses for clarity or the carbon atoms in side chains may be indicated by primed locants.

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ORGANIC COMPOUNDS

1.3

H H H H H H H H H H
H C C C C C C C C C C H
H H H H H H H H H H
H3C

CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH3

FIGURE 1.1

Projections for n-decane


If hydrocarbon chains of equal length are competing for selection as the parent, the
choice goes in descending order to (1) the chain that has the greatest number of side chains,
(2) the chain whose side chains have the lowest-numbered locants, (3) the chain having the
greatest number of carbon atoms in the smaller side chains, or (4) the chain having the leastbranched side chains.
These trivial names may be used for the unsubstituted hydrocarbons only:
Isobutane (CH3)2CHCH3
Isopentane (CH3)2CHCH2CH3

Neopentane (CH3)4C
Isohexane (CH3)2CHCH2CH2CH3

Univalent radicals derived from saturated unbranched alkanes by removal of hydrogen
from a terminal carbon atom are named by adding -yl in place of -ane to the stem name.
Thus the alkane ethane becomes the radical ethyl. These exceptions are permitted for
unsubstituted radicals only:
Isopropyl (CH3)2CH—
Isobutyl (CH3)2CHCH2 ˆ
sec-Butyl CH3CH2CH(CH3) ˆ
tert-Butyl (CH3)3C ˆ

Isopentyl (CH3)2CHCH2CH2ˆ
Neopentyl (CH3)3CCH2 ˆ
tert-Pentyl CH3CH2C(CH3)2 ˆ
Isohexyl (CH3)2CHCH2CH2CH2 ˆ

Note the usage of the prefixes iso-, neo-, sec-, and tert-, and note when italics are employed.
Italicized prefixes are never involved in alphabetization, except among themselves; thus
sec-butyl would precede isobutyl, isohexyl would precede isopropyl, and sec-butyl would
precede tert-butyl.
Examples of alkane nomenclature are


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1.4

SECTION 1

Bivalent radicals derived from saturated unbranched alkanes by removal of two hydrogen
atoms are named as follows: (1) If both free bonds are on the same carbon atom, the ending
-ane of the hydrocarbon is replaced with -ylidene. However, for the first member of the
alkanes it is methylene rather than methylidene. Isopropylidene, sec-butylidene, and
neopentylidene may be used for the unsubstituted group only. (2) If the two free bonds are
on different carbon atoms, the straight-chain group terminating in these two carbon atoms is
named by citing the number of methylene groups comprising the chain. Other carbons groups
are named as substituents. Ethylene is used rather than dimethylene for the first member of
the series, and propylene is retained for CH3 ˆ CH ˆ CH2 ˆ (but trimethylene is ˆ CH2 ˆ
|
CH2 ˆ CH2 ˆ ).
Trivalent groups derived by the removal of three hydrogen atoms from the same carbon
are named by replacing the ending -ane of the parent hydrocarbon with -ylidyne.
Alkenes and Alkynes. Each name of the corresponding saturated hydrocarbon is converted to the corresponding alkene by changing the ending -ane to -ene. For alkynes the
ending is -yne. With more than one double (or triple) bond, the endings are -adiene, -atriene,
etc. (or -adiyne, -atriyne, etc.). The position of the double (or triple) bond in the parent chain
is indicated by a locant obtained by numbering from the end of the chain nearest the double (or triple) bond; thus CH3CH2CH ă CH2 is 1-butene and CH3C CCH3 is 2-butyne.
For multiple unsaturated bonds, the chain is so numbered as to give the lowest possible locants to the unsaturated bonds. When there is a choice in numbering, the double

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ORGANIC COMPOUNDS

1.5

bonds are given the lowest locants, and the alkene is cited before the alkyne where both
occur in the name. Examples:
1,3-Octadiene
CH3CH2CH2CH2CH ă CH CH ă CH2
CH2 ă CHC CCH ă CH2
1,5-Hexadiene-3-yne
CH3CH ă CHCH2C CH
4-Hexen-1-yne
CH CCH2CH ă CH2
1-Penten-4-yne
Unsaturated branched acyclic hydrocarbons are named as derivatives of the chain that
contains the maximum number of double and/or triple bonds. When a choice exists, priority goes in sequence to (1) the chain with the greatest number of carbon atoms and (2)
the chain containing the maximum number of double bonds.
These nonsystematic names are retained:
Ethylene
CH2 ă CH2
Allene
CH2 ă C ă CH2
Acetylene
HC CH
An example of nomenclature for alkenes and alkynes is

Univalent radicals have the endings -enyl, -ynyl, -dienyl, -diynyl, etc. When necessary,
the positions of the double and triple bonds are indicated by locants, with the carbon atom
with the free valence numbered as 1. Examples:
2-Propenyl

CH2 ă CH CH2
CH3 C C
1-Propynyl
CH3 C C CH2CH ă CH2
1-Hexen-4-ynyl
These names are retained:
Vinyl (for ethenyl)
CH2 ă CH
Allyl (for 2-propenyl)
CH2 ă CH CH2
Isopropenyl (for 1-methylvinyl but for unsubstituted radical only)

CH2 ă C(CH3)

Should there be a choice for the fundamental straight chain of a radical, that chain is
selected which contains (1) the maximum number of double and triple bonds, (2) the
largest number of carbon atoms, and (3) the largest number of double bonds. These are in
descending priority.
Bivalent radicals derived from unbranched alkenes, alkadienes, and alkynes by removing a hydrogen atom from each of the terminal carbon atoms are named by replacing the
endings -ene, -diene, and -yne by -enylene, -dienylene, and -ynylene, respectively.
Positions of double and triple bonds are indicated by numbers when necessary. The name
vinylene instead of ethenylene is retained for CH ă CH .
Monocyclic Aliphatic Hydrocarbons. Monocyclic aliphatic hydrocarbons (with no side
chains) are named by prefixing cyclo- to the name of the corresponding open-chain hydrocarbon having the same number of carbon atoms as the ring. Radicals are formed as with
the alkanes, alkenes, and alkynes. Examples:

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1.6


SECTION 1

Cyclohexyl- (for the radical)
1-Cyclohexenyl- (for the radical with the free
valence at carbon 1)
Cyclohexadienyl- (the unsaturated carbons are
given numbers as low as possible, numbering from
the carbon atom with the free valence given the
number 1)
For convenience, aliphatic rings are often represented by simple geometric figures:
a triangle for cyclopropane, a square for cyclobutane, a pentagon for cyclopentane,
a hexagon (as illustrated) for cyclohexane, etc. It is understood that two hydrogen atoms
are located at each corner of the figure unless some other group is indicated for one or both.
Monocyclic Aromatic Compounds. Except for six retained names, all monocyclic substituted aromatic hydrocarbons are named systematically as derivatives of benzene.
Moreover, if the substituent introduced into a compound with a retained trivial name is
identical with one already present in that compound, the compound is named as a derivative of benzene. These names are retained:

The position of substituents is indicated by numbers, with the lowest locant possible
given to substituents. When a name is based on a recognized trivial name, priority for lowest-numbered locants is given to substituents implied by the trivial name. When only two
substituents are present on a benzene ring, their position may be indicated by o- (ortho-),
m- (meta-), and p- (para-) (and alphabetized in the order given) used in place of 1,2-, 1,3-,
and 1,4-, respectively.
Radicals derived from monocyclic substituted aromatic hydrocarbons and having the
free valence at a ring atom (numbered 1) are named phenyl (for benzene as parent, since
benzyl is used for the radical C6H5CH2 ˆ ), cumenyl, mesityl, tolyl, and xylyl. All other
radicals are named as substituted phenyl radicals. For radicals having a single free valence
in the side chain, these trivial names are retained:

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ORGANIC COMPOUNDS

Benzyl C6H5CH2
Benzhydryl (alternative to
diphenylmethyl) (C6H5)2CH
Cinnamyl C6H5CH ă CH CH2

1.7

Phenethyl C6H5CH2CH2
Styryl C6H5CH ă CH
Trityl (C6H5)3C ˆ

Otherwise, radicals having the free valence(s) in the side chain are named in accordance
with the rules for alkanes, alkenes, or alkynes.
The name phenylene (o-, m-, or p-) is retained for the radical ˆ C6H4 ˆ . Bivalent radicals formed from substituted benzene derivatives and having the free valences at ring
atoms are named as substituted phenylene radicals, with the carbon atoms having the free
valences being numbered 1,2-, 1,3-, or 1,4-, as appropriate.
Radicals having three or more free valences are named by adding the suffixes -triyl,
-tetrayl, etc. to the systematic name of the corresponding hydrocarbon.
Fused Polycyclic Hydrocarbons. The names of polycyclic hydrocarbons containing the
maximum number of conjugated double bonds end in -ene. Here the ending does not
denote one double bond. Names of hydrocarbons containing five or more fixed benzene
rings in a linear arrangement are formed from a numerical prefix (see Table 11.4) followed
by -acene. A partial list of the names of polycyclic hydrocarbons is given in Table 1.2.
Many names are trivial.
Numbering of each ring system is fixed, as shown in Table 1.2, but it follows a systematic pattern. The individual rings of each system are oriented so that the greatest number of rings are (1) in a horizontal row and (2) the maximum number of rings are above
and to the right (upper-right quadrant) of the horizontal row. When two orientations meet

these requirements, the one is chosen that has the fewest rings in the lower-left quadrant.
Numbering proceeds in a clockwise direction, commencing with the carbon atom not
engaged in ring fusion that lies in the most counterclockwise position of the uppermost
ring (upper-right quadrant); omit atoms common to two or more rings. Atoms common to
two or more rings are designated by adding lowercase roman letters to the number of the
position immediately preceding. Interior atoms follow the highest number, taking a clockwise sequence wherever there is a choice. Anthracene and phenanthrene are two exceptions
to the rule on numbering. Two examples of numbering follow:

When a ring system with the maximum number of conjugated double bonds can exist
in two or more forms differing only in the position of an “extra” hydrogen atom, the name
can be made specific by indicating the position of the extra hydrogen(s). The compound
name is modified with a locant followed by an italic capital H for each of these hydrogen
atoms. Carbon atoms that carry an indicated hydrogen atom are numbered as low as possible. For example, 1H-indene is illustrated in Table 1.2; 2H-indene would be

Names of polycyclic hydrocarbons with less than the maximum number of noncumulative double bonds are formed from a prefix dihydro-, tetrahydro-, etc., followed by the

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1.8

SECTION 1

name of the corresponding unreduced hydrocarbon. The prefix perhydro- signifies full
hydrogenation. For example, 1,2-dihydronaphthalene is

TABLE 1.2 Fused Polycyclic Hydrocarbons
Listed in order of increasing priority for selection as parent compound
Asterisk after a compound denotes exception to systematic numbering.


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ORGANIC COMPOUNDS

1.9

TABLE 1.2 Fused Polycyclic Hydrocarbons (continued )
Listed in order of increasing priority for selection as parent compound
Asterisk after a compound denotes exception to systematic numbering.

Examples of retained names and their structures are as follows:

Polycyclic compounds in which two rings have two atoms in common or in which one
ring contains two atoms in common with each of two or more rings of a contiguous series
of rings and which contain at least two rings of five or more members with the maximum
number of noncumulative double bonds and which have no accepted trivial name (Table 1.2)
are named by prefixing to the name of the parent ring or ring system designations of the
other components. The parent name should contain as many rings as possible (provided it
has a trivial name) and should occur as far as possible from the beginning of the list in
Table 1.2. Furthermore, the attached component(s) should be as simple as possible. For
example, one writes dibenzo phenanthrene and not naphthophenanthrene because the
attached component benzo- is simpler than naphtho-. Prefixes designating attached components are formed by changing the ending -ene into -eno-; for example, indeno- from

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