SÁCH hóa nước NGOÀI TỔNG hợp george w gokel deans handbook of organic chemistry second edition

SÁCH hóa nước NGOÀI TỔNG hợp george w gokel deans handbook of organic chemistry second edition

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 MCGRAW-HILL New York Chicago San Francisco Lisbon London Madrid Mexico City Milan New Delhi San Juan Seoul Singapore Sydney Toronto Cataloging-in-Publication Data is on file with the Library of Congress Copyright © 2004, 1987 by The McGraw-Hill Companies, Inc All rights reserved Printed in the United States of America Except as permitted under the United States Copyright Act of 1976, no part of this publication may be reproduced or distributed in any form or by any means, or stored in a data base or retrieval system, without the prior written permission of the publisher DOC/DOC ISBN 0-07-137593-7 The sponsoring editor for this book was Kenneth P McCombs and the production supervisor was Sherri Souffrance It was set in Times Roman by Newgen Imaging Systems (P) Ltd The art director for the cover was Anthony Landi Printed and bound by RR Donnelley McGraw-Hill books are available at special quantity discounts to use as premiums and sales promotions, or for use in corporate training programs For more information, please write to the Director of Special Sales, McGraw-Hill Professional, Two Penn Plaza, New York, NY 10121-2298 Or contact your local bookstore This book is printed on recycled, acid-free paper containing a minimum of 50% recycled, de-inked fiber Information contained in this work has been obtained by The McGraw-Hill Companies, Inc (“McGraw-Hill”) from sources believed to be reliable However, neither McGraw-Hill nor its authors guarantee the accuracy or completeness of any information published herein and neither McGraw-Hill nor its authors shall be responsible for any errors, omissions, or damages arising out of use of this information This work is published with the understanding that McGraw-Hill and its authors are supplying information but are not attempting to render engineering or other professional services If such services are required, the assistance of an appropriate professional should be sought 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 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 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 SECTION 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 1.2 1.2 1.2 1.8 1.12 1.12 1.13 1.16 1.18 1.19 1.21 1.24 1.25 1.26 1.34 1.40 1.44 1.47 1.60 1.61 1.61 1.80 1.2 SECTION 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 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 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 1.4 SECTION 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 ¨ 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 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 ¨ CH ˆ CH ¨ CH2 CH2 ¨ CHC ˜ CCH ¨ CH2 1,5-Hexadiene-3-yne CH3CH ¨ CHCH2C ˜ CH 4-Hexen-1-yne CH ˜ CCH2CH ¨ 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 ¨ CH2 Allene CH2 ¨ C ¨ 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 Examples: 2-Propenyl CH2 ¨ CH ˆ CH2 ˆ CH3 ˆ C ˜ C ˆ 1-Propynyl CH3 ˆ C ˜ C ˆ CH2CH ¨ CH2 ˆ 1-Hexen-4-ynyl These names are retained: Vinyl (for ethenyl) CH2 ¨ CH ˆ Allyl (for 2-propenyl) CH2 ¨ CH ˆ CH2 ˆ Isopropenyl (for 1-methylvinyl but for unsubstituted radical only) CH2 ¨ C(CH3) ˆ 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 ˆ CH ¨ CH ˆ 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: 1.6 SECTION 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: I.41 Index terms Links Tension, aqueous (see Vapor pressure) Ternary azeotropic mixtures Thermal conductivity of plastics Thermal neutron absorption cross section of nuclides Thermal properties of plastics Thermodynamic properties of organic materials 4.46 10.24 3.2 10.24 5.2 Thermoplastic elastomers: description of 10.22 properties of 10.50 Thermoplastic polyester properties of Thermosetting polymers properties of 10.42 10.2 10.44 Thiophene azeotropes 4.45 Tin bond strengths 3.28 Torsional asymmetry 1.56 Transformations (conversion factors) 11.7 Triple bonds: infrared absorption frequencies of 6.28 Raman frequencies of 6.59 U Ultraviolet cutoffs: of chromatographic solvents 9.6 of spectrograde solvents 6.6 Ultraviolet stabilizers for polymers 10.7 Ultraviolet-visible, absorption bands 6.3 Ultraviolet-visible spectroscopy 6.3 Urea formaldehyde resin 10.23 properties of 10.56 Urethane rubber 10.63 properties of 10.64 This page has been reformatted by Knovel to provide easier navigation 10.56 I.42 Index terms Links V Vapor pressure of water at various temperatures Vapor pressures Vaporization, enthalpy of 4.10 4.8 5.44 of mercury 4.8 of salt solutions 9.3 of water 4.10 Vinyl butyral polymers: description of 10.23 properties of 10.58 Vinyl chloride polymers: description of 10.22 properties of 10.56 10.58 Vinyl chloride-vinyl acetate copolymers: description of 10.22 properties of 10.56 Vinyl fluoride polymer 10.14 Vinyl polymers: description of 10.22 properties of 10.56 Vinylidene chloride polymers: description of 10.23 properties of 10.58 Vinylidene fluoride polymers: description of 10.13 properties of 10.34 Viscosity of chromatographic solvents 4.55 9.6 of inorganic compounds 4.94 of organic compounds 4.57 Vitamins, nomenclature of 1.43 This page has been reformatted by Knovel to provide easier navigation 10.58 I.43 Index terms Links Voltammetric half-wave potentials 8.82 Volume, molar, critical 5.75 estimation of Vulcanization of polymers 5.88 10.7 W Water: absorption by plastics dielectric constant at various temperatures 10.24 4.98 permeability of polymers and rubbers to 10.70 refractive index at various temperatures 4.98 surface tension at various temperatures 4.98 vapor pressure at various temperatures 4.10 viscosity at various temperatures 4.98 Wavelength maxima of acid-base indicators Waxes, constants of Woodward–Fieser rules Work function and electronegativity 8.72 10.77 6.7 3.11 X Xenon: bond strengths solubility in water at various temperatures X-ray diffraction 3.28 4.7 6.112 Z Z(cis)-configuration 1.53 Zinc bond strengths 3.29 This page has been reformatted by Knovel to provide easier navigation Contents Preface iv About the Author v 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 This page has been reformatted by Knovel to provide easier navigation 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 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 This page has been reformatted by Knovel to provide easier navigation Contents 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 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 This page has been reformatted by Knovel to provide easier navigation 4.55 vi 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 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 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 This page has been reformatted by Knovel to provide easier navigation Contents 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 This page has been reformatted by Knovel to provide easier navigation viii 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 This page has been reformatted by Knovel to provide easier navigation Contents 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 This page has been reformatted by Knovel to provide easier navigation x 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 This page has been reformatted by Knovel to provide easier navigation Contents 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 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 This page has been reformatted by Knovel to provide easier navigation xii 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 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 This page has been reformatted by Knovel to provide easier navigation Contents 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 This page has been reformatted by Knovel to provide easier navigation 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 This page has been reformatted by Knovel to provide easier navigation I.1 [...]... 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... 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... 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... DNA chains are shown in the lower panel of the figure Hollow arrows indicate the points at which the 5Ј-hydroxyl group is esterified to the 3Ј-phosphate group to form the so-called “sugar–phosphate” backbone Note the hydroxyl group (arrow) that is present on ribose but missing in deoxyribose The structural frameworks of DNA and RNA are organized by hydrogen bond formation between pairs of purine and pyrimidine... 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... the lowest numbers at the first point of difference in the expression for ring junctions, (h) the lowest state of hydrogenation, (i) the lowest-numbered locant for indicated hydrogen, ( j) the lowestnumbered locant for point of attachment (if a radical), (k) the lowest-numbered locant for an attached group expressed as a suffix, (l) the maximum number of substituents cited as prefixes, (m) the lowest-numbered... Characteristic groups will now be treated briefly in order to expand the terse outline of substitutive nomenclature presented in Table 1.7 Alternative nomenclature will be indicated whenever desirable Acetals and Acylals Acetals, which contain the group ϾC(OR)2, where R may be different, are named (1) as dialkoxy compounds or (2) by the name of the corresponding aldehyde or ketone followed by the name of the hydrocarbon... preceding rules lead to inconvenient names, then (1) the unaltered name of the base may be used followed by the name of the anion or (2) for salts of hydrohalogen acids only the unaltered name of the base is used followed by the name of the hydrohalide An example of the latter would be 2-ethyl-p-phenylenediamine monohydrochloride Azo Compounds When the azo group ( ˆ N ¨ N ˆ ) connects radicals derived from... for use only when other nomenclature systems are difficult to apply in the naming of chains containing heteroatoms When no group is present that can be named as a principal group, the longest chain of carbon and heteroatoms terminating with carbon is chosen and named as though the entire chain were that of an acyclic hydrocarbon The heteroatoms within this chain are identified by means of prefixes aza-,... number of heteroatoms first listed in Table 1.3 If there is a choice between components of the same size containing the same number and kind of heteroatoms, choose as the base component that one with the lower numbers for the heteroatoms before fusion When a fusion position is occupied by a heteroatom, the names of the component rings to be fused are selected to contain the heteroatom Common Names of Heterocycles