Spectrometric Identification of Organic Compounds

Автор(ы):Silverstein M.
06.10.2007
Год изд.:1963
Описание: This book was originally written to teach the organic chemist how to identify organic compounds from the synergistic information afforded by the combination of mass (MS), infrared (IR), nuclear magnetic resonance (NMR), and ultraviolet (UV) spectra. Essentially, the molecule is perturbed by these energy probes and the molecule's responses are recorded as spectra. In the present edition, the goal remains unchanged, but the format has evolved to respond to the remarkable evolution of instrumentation. NMR, without question, has become the most sophisticated tool available to the organic chemist, and it now requires four chapters to do it justice.
Оглавление:
Spectrometric Identification of Organic Compounds — обложка книги. Обложка книги.
CHAPTER 1 Introduction [1]
CHAPTER 2 Mass Spectrometry [2]
  2.1 Introduction [2]
  2.2 Instrumentation [2]
    2.2.1 Magnetic Field Only (A.1) [3]
    2.2.2 Double Focusing (Electrostatic and Magnetic Fields) (A.2) [4]
    2.2.3 Quadrupole Mass Filter (B.1) [4]
    2.2.4 Quadrupole Ion Storage (Ion Trap) (B.2) [5]
    2.2.5 Time of Flight (C) [5]
    2.2.6 FT-ICR (Fourier Transform-Ion Cyclotron Resonance) (D) (Also termed FT-MS) [6]
    2.2.7 MS/MS (Tandem Mass Spectrometry) (E) [6]
  2.3 The Mass Spectrum [6]
  2.4 Determination of a Molecular Formula [7]
    2.4.1 Unit-Mass Molecular Ion and Isotope Peaks [7]
    2.4.2 High-Resolution Molecular Ion [8]
  2.5 Recognition of the Molecular Ion Peak [8]
    2.5.1 Other Useful Ionization Techniques [9]
      2.5.1.1 Chemical lonization (CI) [9]
      2.5.1.2 Field Desorption (FD) [10]
      2.5.1.3 Fast Ion Bombardment (FAB) [10]
      2.5.1.4 Electrospray lonization (ESI) [11]
      2.5.1.5 Matrix Assisted Laser Desorption/Ionization (MALDI) [11]
  2.6 Use of the Molecular Formula. Index of Hydrogen Deficiency [11]
  2.7 Fragmentation [12]
  2.8 Rearrangements [14]
  2.9 Derivatives [15]
  2.10 Mass Spectra of Some Chemical Classes [15]
    2.10.1 Hydrocarbons [15]
      2.10.1.1 Saturated Hydrocarbons [15]
      2.10.1.2 Alkenes (Olefins) [17]
      2.10.1.3 Aromatic and Aralkyl Hydrocarbons [17]
    2.10.2 Hydroxy Compounds [18]
      2.10.2.1 Alcohols [18]
      2.10.2.2 Phenols [20]
    2.10.3 Ethers [20]
      2.10.3.1 Aliphatic Ethers (and Acetals) [20]
      2.10.3.2 Aromatic Ethers [22]
    2.10.4 Ketones [22]
      2.10.4.1 Aliphatic Ketones [22]
      2.10.4.2 Cyclic Ketones [23]
      2.10.4.3 Aromatic Ketones [23]
    2.10.5 Aldehydes [24]
      2.10.5.1 Aliphatic Aldehydes [24]
      2.10.5.2 Aromatic Aldehydes [24]
    2.10.6 Carboxylic Acids [26]
      2.10.6.1 Aliphatic Acids [26]
      2.10.6.2 Aromatic Acids [26]
    2.10.7 Carboxylic Esters [27]
      2.10.7.1 Aliphatic Esters [27]
      2.10.7.2 Benzyl and Phenyl Esters [28]
      2.10.7.3 Esters of Aromatic Acids [28]
    2.10.8 Lactones [29]
    2.10.9 Amines [29]
      2.10.9.1 Aliphatic Amines [29]
      2.10.9.2 Cyclic Amines [30]
      2.10.9.3 Aromatic Amines (Anilines) [30]
    2.10.10 Amides [30]
      2.10.10.1 Aliphatic Amides [30]
      2.10.10.2 Aromatic Amides [31]
    2.10.11 Aliphatic Nitriles [31]
    2.10.12 Nitro Compounds [31]
      2.10.12.1 Aliphatic Nitro Compounds [31]
      2.10.12.2 Aromatic Nitro Compounds [31]
    2.10.13 Aliphatic Nitrites [32]
    2.10.14 Aliphatic Nitrates [32]
    2.10.15 Sulfur Compounds [32]
      2.10.15.1 Aliphatic Mercaptans (Thiols) [32]
      2.10.15.2 Aliphatic Sulfides [33]
      2.10.15.3 Aliphatic Disulfides [34]
    2.10.16 Halogen Compounds [34]
      2.10.16.1 Aliphatic Chlorides [34]
      2.10.16.2 Aliphatic Bromides [35]
      2.10.16.3 Aliphatic Iodides [35]
      2.10.16.4 Aliphatic Fluorides [35]
      2.10.16.5 Benzyl Halides [36]
      2.10.16.6 Aromatic Halides [36]
    2.10.17 Heteroaromatic Compounds [36]
    2.10.18 Natural Products [37]
      2.10.18.1 Amino Acids [37]
      2.10.18.2 Steroids [38]
      2.10.18.3 Triglycerides [38]
      2.10.19 Miscellaneous Classes [39]
References [39]
Problems [40]
Appendices [45]
        A. Formula Masses [45]
        B. Common Fragment Ions [66]
        C. Common Fragments Lost [69]
CHAPTER 3 Infrared Spectrometry [71]
  3.1 Introduction [71]
  3.2 Theory [71]
    3.2.1 Coupled Interactions [74]
    3.2.2 Hydrogen Bonding [75]
  3.3 Instrumentation [76]
    3.3.1 Dispersion IR Spectrometer [76]
    3.3.2 Fourier Transform Infrared Spectrometer (Interferometer) [76]
  3.4 Sample Handling [77]
  3.5 Interpretation of Spectra [79]
  3.6 Characteristic Group Absorptions of Organic Molecules [81]
    3.6.1 Normal Alkanes (Paraffins) [81]
      3.6.1.1 С—Н Stretching Vibrations [82]
      3.6.1.2 C—H Bending Vibrations [82]
    3.6.2 Branched-Chain Alkanes [83]
      3.6.2.1 C—H Stretching Vibrations [83]
      3.6.2.2 C—H Bending Vibrations [83]
    3.6.3 Cyclic Alkanes [83]
      3.6.3.1 C—H Stretching Vibrations [83]
      3.6.3.2 C—H Bending Vibrations [84]
    3.6.4 Alkenes [84]
      3.6.4.1 C=C Stretching Vibrations [84]
      3.6.4.2 Alkene C—H Stretching Vibrations [85]
      3.6.4.3 Alkene C—H Bending Vibrations [85]
    3.6.5 Alkynes [85]
      3.6.5.1 C=C Stretching Vibrations [85]
      3.6.5.2 C—H Stretching Vibrations [86]
      3.6.5.3 C—H Bending Vibrations [86]
    3.6.6 Mononuclear Aromatic Hydrocarbons [86]
      3.6.6.1 Out-of-Plane C—H Bending Vibrations [86]
    3.6.7 Polynuclear Aromatic Hydrocarbons [87]
    3.6.8 Alcohols and Phenols [87]
      3.6.8.1 O—H Stretching Vibrations [87]
      3.6.8.2 С—О Stretching Vibrations [90]
      3.6.8.3 O—H Bending Vibrations [90]
    3.6.9 Ethers, Epoxides, and Peroxides [90]
      3.6.9.1 С—О Stretching Vibrations [90]
    3.6.10 Ketones [92]
      3.6.10.1 C=O Stretching Vibrations [92]
      3.6.10.2 (?) Stretching and Bending Vibrations [94]
    3.6.11 Aldehydes [94]
      3.6.11.1 C=О Stretching Vibrations [94]
      3.6.11.2 C—H Stretching Vibrations [94]
    3.6.12 Carboxylic Acids [95]
      3.6.12.1 O—H Stretching Vibrations [95]
      3.6.12.2 C=O Stretching Vibrations [96]
      3.6.12.3 С—О Stretching and O—H Bending Vibrations [96]
    3.6.13 Carboxylate Anion [96]
    3.6.14 Esters and Lactones [97]
      3.6.14.1 C=O Stretching Vibrations [97]
      3.6.14.2 С—О Stretching Vibrations [98]
    3.6.15 Acid Halides [99]
      3.6.15.1 C=О Stretching Vibrations [99]
    3.6.16 Carboxylic Acid Anhydrides [99]
      3.6.16.1 C=O Stretching Vibrations [99]
      3.6.16.2 С—О Stretching Vibrations [99]
    3.6.17 Amides and Lactams [99]
      3.6.17.1 N—H Stretching Vibrations [101]
      3.6.17.2 C=O Stretching Vibrations (Amide I Band) [101]
      3.6.17.3 N—H Bending Vibrations (Amide II Band) [101]
      3.6.17.4 A Other Vibration Bands [101]
      3.6.17.5 C=O Stretching Vibrations of Lactams [101]
    3.6.18 Amines [102]
      3.6.18.1 N—H Stretching Vibrations [102]
      3.6.18.2 N—H Bending Vibrations [102]
      3.6.18.3 C—N Stretching Vibrations [102]
    3.6.19 Amine Salts [103]
      3.6.19.1 N—H Stretching Vibrations [103]
      3.6.19.2 N—H Bending Vibrations [103]
    3.6.20 Amino Acids and Salts of Amino Acids [103]
    3.6.21 Nitriles [104]
    3.6.22 Isonitriles (R—N(?)(?)(?)), Cyanates (R—O—C=N), Isocyanates (R—N=C=O), Thiocyanates (R—S—C=N), and Isothiocya-nates (R—N=C=S) [104]
    3.6.23 Compounds Containing —N=N—Group [104]
    3.6.24 Covalent Compounds Containing Nitrogen-Oxygen Bonds [104]
      3.6.24.1 N(?)О Stretching Vibrations [105]
    3.6.25 Organic Sulfur Compounds [106]
      3.6.25.1 S—H Stretching Vibrations [106]
      3.6.25.2 C—Sand C=S Stretching Vibrations [106]
    3.6.26 Compounds Containing Sulfur-Oxygen Bonds [107]
      3.6.26.1 S=O Stretching Vibrations [107]
    3.6.27 Organic Halogen Compounds [108]
    3.6.28 Silicon Compounds [108]
      3.6.28.1 Si—H Vibrations [108]
      3.6.28.2 SiO—H and Si—О Vibrations [108]
      3.6.28.3 Silicon-Halogen Stretching Vibrations [108]
    3.6.29 Phosphorus Compounds [109]
      3.6.29.1 P=O and P—О Stretching Vibrations [109]
    3.6.30 Heteroaromatic Compounds [109]
      3.6.30.1 C—H Stretching Vibrations [109]
      3.6.30.2 N—H Stretching Frequencies [109]
      3.6.30.3 Ring Stretching Vibrations (Skeletal Bands) [109]
      3.6.30.4 C—H Out-of-Plane Bending [109]
References [109]
Problems [111]
Appendices [120]
        A. Transparent Regions of Solvent and Mulling Oils [120]
        B. Spectra of Common Laboratory Substances [121]
        C. Characteristic Group Absorptions [136]
        D. Absorptions for Alkenes [141]
        E. Absorptions for Phosphorus Compounds [142]
        F. Absorptions for Heteroaromatics [143]
CHAPTER 4 Proton Magnetic Resonance Spectrometr [144]
  4.1 Introduction [144]
  4.2 Continuous-Wave (CW) NMR Spectrometry [145]
  4.3 Relaxation [146]
  4.4 Pulsed Fourier Transform Spectrometry [148]
  4.5 Rotating Frame of Reference [149]
  4.6 Instrumentation and Sample Handling [149]
  4.7 Chemical Shift [151]
  4.8 Simple Spin Coupling [157]
  4.9 Protons on Oxygen, Nitrogen, and Sulfur Atoms [163]
    4.9.1 Protons on an Oxygen Atom [163]
      4.9.1.1 Alcohols [163]
      4.9.1.2 Water [165]
      4.9.1.3 Phenols [165]
      4.9.1.4 Enols [165]
      4.9.1.5 Carboxylic Acids [166]
    4.9.2 Protons on Nitrogen [166]
    4.9.3 Protons on Sulfur [168]
  4.10 Protons on or Near Chlorine, Bromine, or Iodine Nuclei [168]
  4.11 Coupling of Protons to Other Important Nuclei ((?)F, D, (?)P, (?)Si, and (?)C) [168]
    4.11.1 Coupling of Protons to (?)F [168]
    4.11.2 Coupling of Protons to D [168]
    4.11.3 Coupling of Protons to (?)P [169]
    4.11.4 Coupling of Protons to (?)Si [169]
    4.11.5 Coupling of Protons to (?)C [169]
  4.12 Chemical Shift Equivalence [170]
    4.12.1 Determination of Chemical Shift Equivalence by Interchange Through Symmetry Operations [170]
      4.12.1.1 Interchange by Rotation Around a Simple Axis of Symmetry (С(?)) [170]
      4.12.1.2 Interchange by Reflection Through a Plane of Symmetry ((?)) [170]
      4.12.1.3 Interchange by Inversion Through a Center of Symmetry ((?)) [170]
      4.12.1.4 No Interchangeability by a Symmetry Operation [171]
    4.12.2 Determination of Chemical Shift Equivalence by Tagging (or Substitution) [172]
    4.12.3 Chemical Shift Equivalence by Rapid Interconversion of Structures [172]
      4.12.3.1 Keto-Enol Interconversion [172]
      4.12.3.2 Interconversion Around a "Partial Double Bond" (Restricted Rotation) [173]
      4.12.3.3 Interconversion Around the Single Bonds of Rings [174]
      4.12.3.4 Interconversion Around the Single Bonds of Chains [174
  4.13 Magnetic Equivalence (Spin-Coupling Equivalence) [174]
  4.14 AMX, ABX, and ABC Rigid Systems with Three Coupling Constants [178]
  4.15 Conformationally Mobile, Open-Chain Systems. Virtual Coupling [179]
    4.15.1 Unsymmetrical Chains [171]
      4.15.1.1 1-Nitropropane [179]
      4.15.1.2 1-Hexanol [179]
    4.15.2 Symmetrical Chains [181]
      4.15.2.1 Dimethyl Succinate [181]
      4.15.2.2 Dimethyl Glutarate [181]
      4.15.2.3 Dimethyl Adipate [181]
    4.15.3 Less Symmetrical Chains [182]
      4.15.3.1 3-Methylglutaric Acid [182]
  4.16 Chirality [183]
    4.16.1 One Chiral Center [183]
    4.16.2 Two Chiral Centers [185]
  4.17 Vicinal and Geminal Coupling [185]
  4.18 Long-Range Coupling [187]
  4.19 Spin Decoupling [187]
  4.20 Nuclear Overhauser Effect Difference Spectrome-try, (?)H(?)H Proximity Through Space [189]
  4.21 NMR Shift Reagents [191]
  4.22 Addendum—Analysis of First-Order Patterns [191]
References [193]
Problems [194]
Appendices [200]
        A. Chart A.1 Chemical Shifts of Protons on a Carbon Atom Adjacent (a Position) to a Functional Group in Aliphatic Compounds (M—Y) [200]
          Chart A.2 Chemical Shifts of Protons on a Carbon Atom Once Removed ((?) Position) from a Functional Group in Aliphatic Compounds (M—C—Y) [202]
        B. Effect on Chemical Shifts by Two or Three Directly Attached Functional Groups [203]
        C. Chemical Shifts in Alicyclic and Heterocyclic Rings [205]
        D. Chemical Shifts in Unsaturated and Aromatic Systems [206]
        E. Protons on Heteroatoms [211]
        F. Proton Spin-Coupling Constants [212]
        G. Chemical Shifts and Multiplicities of Residual Protons in Commercially Available Deuterated Solvents (Merck & Co., Inc.) [214]
        H. Properties of Several Nuclei [216]
CHAPTER 5 (?)C NMR Spectrometry [217]
  5.1 Introduction [217]
  5.2 Peak Assignments [221]
    5.2.1 Peak Intensity [221]
    5.2.2 Deuterium Substitution [222]
    5.2.3 Chemical Shift Equivalence [222]
  5.3 Chemical Classes and Chemical Shifts [222]
    5.3.1 Alkanes [223]
      5.3.1.1 Linear and Branched Alkanes [223]
    5.3.2 Effects of Substituents on Alkanes [225]
    5.3.3 Cycloalkanes and Saturated Heterocyclics [225]
    5.3.4 Alkenes [226]
    5.3.5 Alkynes [227]
    5.3.6 Aromatic Compounds [228]
    5.3.7 Heteroaromatic Compounds [230]
    5.3.8 Alcohols [230]
    5.3.9 Ethers, Acetals, and Epoxides [230]
    5.3.10 Halides [232]
    5.3.11 Amines [232]
    5.3.12 Thiols, Sulfides, and Disulfides [232]
    5.3.13 Functional Groups Containing Carbon [232]
      5.3.13.1 Ketones and Aldehydes [232]
      5.3.13.2 Carboxylic Acids, Esters, Chlorides, Anhydrides, Amides, and Nitriles [233]
      5.3.13.3 Oximes [233]
  5.4 (?)С—(?)Н Spin Coupling (J values) [223]
  5.5 DEPT [236]
  5.6 Quantitative Analysis [236]
References [239]
Problems [239]
Appendices [245]
        A. The (?)C Chemical Shifts, Couplings, and Multiplicities of Common NMR Solvents [245]
        B. Comparison of (?)H and (?)C Chemical Shifts [246]
        C. The (?)C Correlation Chart for Chemical Classes [247]
        D. (?)C NMR Data for Several Natural Products (?) [249]
CHAPTER 6 Correlation NMR Spectrometry [250]
  6.1 Introduction [250]
  6.2 Theory [250]
  6.3 Correlation Spectrometry [253]
  6.4 (?)H—(?)H COSY [255]
  6.5 Double-Quantum Filtered (?)H—(?)H COSY [255]
    6.5.1 Ipsenol [256]
    6.5.2 Caryophyllene oxide [258]
  6.6 (?)H—(?)C COSY: HETCOR [259]
  6.7 Proton-Detected HETCOR: HMQC [262]
  6.8 Proton-Detected, Long-Range (?)H—(?)C Heteronuclear Correlation: HMBC [263]
  6.9 (?)С—(?)С Correlations: INADEQUAТЕ [268]
  6.10 Relayed Coherence Transfer: TOCSY [270]
  6.11 Gradient Field NMR [273]
References [274]
Problems [274]
CHAPTER 7 Spectrometry of Other Important Nuclei [280]
  7.1 Introduction [280]
  7.2 (?)N Nuclear Magnetic Resonsance [281]
  7.3 (?)F Nuclear Magnetic Resonance [287]
  7.4 (?)Si Nuclear Magnetic Resonance [289]
  7.5 (?)P Nuclear Magnetic Resonance [291]
  7.6 Conclusions [293]
References [295]
Problems [296]
CHAPTER 8
        A. Introduction [301]
References [302]
        B. Solved Problems [303]
CHAPTER 9
        A. Introduction [325]
        B. Assigned Problems [326]
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