Spectrometric Identification of Organic Compounds, 7th Edition

by Robert M. Silverstein (State Univ. of New York, College of Environmental Science & Forestry); Francis X. Webster (State Univ. of New York, College of Environmental Science & Forestry); David Kiemle (State University of New York, College of Environmen

• ISBN13: 9780471393627
• ISBN10: 0471393622
• Edition: 7th
• Format: Hardcover
• Copyright: 2005-01-01
• Publisher: WILEY

Summary

Originally published in 1962, this was the first book to explore teh identification of organic compounds using spectroscopy. It provides a thorough introduction to the three areas of spectrometry most widely used in spectrometric identification: mass spectrometry, infrared spectrometry, and nuclear magnetic resonance spectrometry. A how-to, hands-on teaching manual with considerably expanded NMR coverage--NMR spectra can now be intrepreted in exquisite detail. This book: * Uses a problem-solving approach with extensive reference charts and tables. * Offers an extensive set of real-data problems offers a challenge to the practicing chemist

Table of Contents

Mass Spectrometry	1	(71)
Introduction	1	(1)
Instrumentation	2	(1)
Ionization Methods	3	(5)
Gas-Phase Ionization Methods	3	(1)
Electron Impact Ionization	3	(1)
Chemical Ionization	3	(1)
Desorption Ionization Methods	4	(1)
Field Desorption Ionization	4	(1)
Fast Atom Bombardment Ionization	4	(1)
Plasma Desorption Ionization	5	(1)
Laser Desorption Ionization	6	(1)
Evaporative Ionization Methods	6	(1)
Thermospray Mass Spectrometry	6	(1)
Electrospray Mass Spectrometry	6	(2)
Mass Analyzers	8	(5)
Magnetic Spector Mass Spectrometers	9	(1)
Quadrupole Mass Spectrometers	10	(1)
Ion Trap Mass Spectrometers	10	(2)
Time-of-Flight Mass Spectrometer	12	(1)
Fourier Transform Mass Spectrometer	12	(1)
Tandem Mass Spectrometry	12	(1)
Interpretation of El Mass Spectra	13	(6)
Recognition of the Molecular Ion Peak	14	(1)
Determination of a Molecular Formula	14	(1)
Unit-Mass Molecular Ion and Isotope Peaks	14	(1)
High-Resolution Molecular Ion	15	(1)
Use of the Molecular Formula. Index of Hydrogen Deficiency	16	(1)
Fragmentation	17	(2)
Rearrangements	19	(1)
Mass Spectra of Some Chemical Classes	19	(53)
Hydrocarbons	19	(1)
Saturated Hydrocarbons	19	(1)
Alkenes (Olefins)	20	(1)
Aromatic and Aralkyl Hydrocarbons	21	(1)
Hydroxy Compounds	22	(1)
Alcohols	22	(2)
Phenols	24	(1)
Ethers	24	(1)
Aliphatic Ethers (and Acetals)	24	(1)
Aromatic Ethers	25	(1)
Ketones	26	(1)
Aliphatic Ketones	26	(1)
Cyclic Ketones	26	(1)
Aromatic Ketones	27	(1)
Aldehydes	27	(1)
Aliphatic Aldehydes	27	(1)
Aromatic Aldehydes	28	(1)
Carboxylic Acids	28	(1)
Aliphatic Acids	28	(1)
Aromatic Acids	28	(1)
Carboxylic Esters	29	(1)
Aliphatic Esters	29	(1)
Benzyl and Phenyl Esters	30	(1)
Esters of Aromatic Acids	30	(1)
Lactones	31	(1)
Amines	31	(1)
Aliphatic Amines	31	(1)
Cyclic Amines	32	(1)
Aromatic Amines (Anilines)	32	(1)
Amides	32	(1)
Aliphatic Amides	32	(1)
Aromatic Amides	32	(1)
Aliphatic Nitriles	32	(1)
Nitro Compounds	33	(1)
Aliphatic Nitro Compounds	33	(1)
Aromatic Nitro Compounds	33	(1)
Aliphatic Nitrites	33	(1)
Aliphatic Nitrates	33	(1)
Sulfur Compounds	33	(1)
Aliphatic Mercaptans (Thiols)	34	(1)
Aliphatic Sulfides	34	(1)
Aliphatic Disulfides	35	(1)
Halogen Compounds	35	(1)
Aliphatic Chlorides	36	(1)
Aliphatic Bromides	37	(1)
Aliphatic Iodides	37	(1)
Aliphatic Fluorides	37	(1)
Benzyl Halides	37	(1)
Aromatic Halides	37	(1)
Heteroaromatic Compounds	37	(1)
References	38	(1)
Student Exercises	39	(8)
Appendices	47	(1)
Formulas Masses	47	(21)
Common Fragment Ions	68	(2)
Common Fragments Lost	70	(2)
Infrared Spectrometry	72	(55)
Introduction	72	(1)
Theory	72	(6)
Coupled Interaction	75	(1)
Hydrogen Bonding	76	(2)
Instrumentation	78	(1)
Dispersion IR Spectrometer	78	(1)
Fourier Transform Infrared Spectrometer (Interferometer)	78	(1)
Sample Handling	79	(1)
Interpretations of Spectra	80	(2)
Characteristic Group Absorption of Organic Molecules	82	(45)
Normal Alkanes (Paraffins)	82	(1)
C---H Stretching Vibrations	83	(1)
C---H Bending Vibrations Methyl Groups	83	(1)
Branched-Chain Alkanes	84	(1)
C---H Stretching Vibrations Tertiary C---H Groups	84	(1)
C---H Bending Vibrations gem-Dimethyl Groups	84	(1)
Cyclic Alkanes	85	(1)
C---H Stretching Vibrations	85	(1)
C---H Bending Vibrations	85	(1)
Alkenes	85	(1)
C---C Stretching Vibrations Unconjugated Linear Alkenes	85	(1)
Alkene C---H Stretching Vibrations	86	(1)
Alkene C---H Bending Vibrations	86	(1)
Alkynes	86	(1)
C---C Stretching Vibrations	86	(1)
C---H Stretching Vibrations	87	(1)
C---H Bending Vibrations	87	(1)
Mononuclear Aromatic Hydrocarbons	87	(1)
Out-of-Plane C---H Bending Vibrations	87	(1)
Polynuclear Aromatic Hydrocarbons	87	(1)
Alcohols and Phenols	88	(1)
O---H Stretching Vibrations	88	(1)
C---O Stretching Vibrations	89	(1)
O---H Bending Vibrations	90	(1)
Ethers, Epoxides, and Peroxides	91	(1)
C---O Stretching Vibrations	91	(1)
Ketones	92	(1)
C---O Stretching Vibrations	92	(2)
C---C(=O)---C Stretching and Bending Vibrations	94	(1)
Aldehydes	94	(1)
C---O Stretching Vibrations	94	(1)
C---H Stretching Vibrations	94	(1)
Carboxylic Acids	95	(1)
O---H Stretching Vibrations	95	(1)
C=O Stretching Vibrations	95	(1)
C---O Stretching and O---H Bending Vibrations	96	(1)
Carboxylate Anion	96	(1)
Esters and Lactones	96	(1)
C=O Stretching Vibrations	97	(1)
C---O Stretching Vibrations	98	(1)
Acid Halides	98	(1)
C=O Stretching Vibrations	98	(1)
Carboxylic Acid Anhydrides	98	(1)
C=O Stretching Vibrations	98	(1)
C---O Stretching Vibrations	98	(1)
Amides and Lactams	99	(1)
N---H Stretching Vibrations	99	(1)
C=O Stretching Vibrations (Amide I Band)	100	(1)
N---H Bending Vibrations (Amide II Band)	100	(1)
Other Vibration Bands	101	(1)
C=O Stretching Vibrations of Lactams	101	(1)
Amines	101	(1)
N---H Stretching Vibrations	101	(1)
N---H Bending Vibrations	101	(1)
C---N Stretching Vibrations	102	(1)
Amine Salts	102	(1)
N---H Stretching Vibrations	102	(1)
N---H Bending Vibrations	102	(1)
Amino Acids and Salts of Amino Acids	102	(1)
Nitriles	103	(1)
Isonitriles (R---N=C), Cyanates (R---O---C=N), Isocyanates (R---N=C=O), Thiocyanates (R---S---C=N), Isothiocyanates (R---N=C=S)	104	(1)
Compounds Containing---N=N	104	(1)
Covalent Compounds Containing Nitrogen-Oxygen Bonds	104	(1)
N=O Stretching Vibrations Nitro Compounds	104	(1)
Organic Sulfur Compounds	105	(1)
S=H Stretching Vibrations Mercaptans	105	(1)
C---S and C=S Stretching Vibrations	106	(1)
Compounds Containing Sulfur---Oxygen Bonds	106	(1)
S=O Stretching Vibrations Sulfoxides	106	(1)
Organic Halogen Compounds	107	(1)
Silicon Compounds	107	(1)
Si---H Vibrations	107	(1)
SiO---H and Si---O Vibrations	107	(1)
Silicon---Halogen Stretching Vibrations	107	(1)
Phosphorus Compounds	107	(1)
P=O and P---O Stretching Vibrations	107	(1)
Heteroaromatic Compounds	107	(1)
C---H Stretching Vibrations	107	(1)
N---H Stretching Frequencies	108	(1)
Ring Stretching Vibrations (Skeletal Bands)	108	(1)
C---H Out-of-Plane Bending	108	(1)
References	108	(2)
Student Exercises	110	(9)
Appendices	119	(1)
Transparent Regions of Solvents and Mulling Oils	119	(1)
Characteristic Group Absorptions	120	(5)
Absorptions for Alkenes	125	(1)
Absorptions for Phosphorus Compounds	126	(1)
Absorptions for Heteroaromatics	126	(1)
Proton Magnetic Resonance Spectrometry	127	(77)
Introduction	127	(1)
Theory	127	(8)
Magnetic Properties of Nuclei	127	(1)
Excitation of Spin 1/2 Nuclei	128	(2)
Relaxation	130	(5)
Instrumentation and Sample Handling	135	(2)
Instrumentation	135	(1)
Sensitivity of NMR Experiments	136	(1)
Solvent Selection	137	(1)
Chemical Shift	137	(6)
Spin Coupling, Multiplets, Spin Systems	143	(17)
Simple and Complex First Order Multiplets	145	(1)
First Order Spin Systems	146	(1)
Pople Notions	147	(1)
Further Examples of Simple, First-Order Spin Systems	147	(1)
Analysis of First-Order Patterns	148	(12)
Protons on Oxygen, Nitrogen, and Sulfur Atoms. Exchangeable Protons	160
Protons on an Oxygen Atom	150	(1)
Alcohols	150	(3)
Water	153	(1)
Phenols	153	(1)
Enols	153	(1)
Carboxylic Acids	153	(1)
Protons on Nitrogen	153	(2)
Protons on Sulfur	155	(1)
Protons on or near Chlorine, Bromine, or Iodine Nuclei	155	(1)
Coupling of Protons to Other Important Nuclei (19F, D, 31P, 29Si, and 13C)	155	(2)
Coupling of Protons to 19F	155	(1)
Coupling of Protons to D	155	(1)
Coupling of Protons to 31P	156	(1)
Coupling of Protons to 29Si	156	(1)
Coupling of Protons to 13C	156	(1)
Chemical Shift Equivalence	157	(5)
Determination of Chemical Shift Equivalence by Interchange Through Symmetry Operations	157	(1)
Interchange by Rotation Around a Simple Axis of Symmetry (Cn)	157	(1)
Interchange by Reflection Through a Plane of Symmetry (σ)	157	(1)
Interchange by Inversion Through a Center of Symmetry (i)	158	(1)
No Interchangeability by a Symmetry Operations	158	(1)
Determination of Chemical Shift Equivalence by Tagging (or Substitution)	159	(1)
Chemical Shift Equivalence by Rapid Interconversion of Structures	160	(1)
Keto-Enol Interconversion	160	(1)
Interconversion Around a ``Partial Double Bond'' (Restricted Rotation)	160	(1)
Interconversion Around the Single Bond of Rings	160	(1)
Interconversion Around the Single Bonds of Chains	161	(1)
Magnetic Equivalence (Spin-Coupling Equivalence)	162	(2)
AMX, ABX, and ABC Rigid Systems with Three Coupling Constants	164	(1)
Confirmationally Mobile, Open-Chain Systems. Virtual Coupling	165	(4)
Unsymmetrical Chains	165	(1)
1-Nitropropane	165	(1)
1-Hexanol	165	(2)
Symmetrical Chains	167	(1)
Dimethyl Succinate	167	(1)
Dimethyl Glutarate	167	(1)
Dimethyl Adipate	167	(1)
Dimethyl Pimelate	168	(1)
Less Symmetrical Chains	168	(1)
3-Methylglutaric Acid	168	(1)
Chirality	169	(2)
One Chiral Center, Ipsenol	169	(2)
Two Chiral Centers	171	(1)
Vicinal and Geminal Coupling	171	(1)
Low-Range Coupling	172	(1)
Selective Spin Decoupling. Double Resonance	173	(1)
Nuclear Overhauser Effect, Difference Spectrometry, 1H 1H Proximity Through Space	173	(2)
Conclusion	175	(29)
References	176	(1)
Student Exercises	177	(11)
Appendices	188	(1)
Chemicals Shifts of a Proton	188	(3)
Effect on Chemical Shifts by Two or Three Directly Attached Functional Groups	191	(2)
Chemical Shifts in Alicyclic and Heterocyclic Rings	193	(1)
Chemical Shifts in Unsaturated and Aromatic Systems	194	(3)
Protons on Heteroatoms	197	(1)
Proton Spin-Coupling Constants	198	(2)
Chemical Shifts and Multiplicities of Residual Protons in Commercially Available Deuterated Solvents	200	(1)
1H NMR Data	201	(2)
Proton NMR Chemical Shifts of Amino Acids in D2O	203	(1)
Carbon-13 NMR Spectrometry	204	(41)
Introduction	204	(1)
Theory	204	(7)
1H Decoupling Techniques	204	(1)
Chemical Shift Scale and Range	205	(1)
T1 Relaxation	206	(1)
Nuclear Overhauser Enhancement (NOE)	207	(2)
13C---1H Sping Coupling (J Values)	209	(1)
Sensitivity	210	(1)
Solvents	210	(1)
Interpretation of a Simple 13C Spectrum: Diethyl Phthalate	211	(2)
Quantitative 13C Analysis	213	(1)
Chemical Shift Equivalence	214	(1)
DEPT	215	(2)
Chemical Classes and Chemical Shifts	217	(28)
Alkanes	218	(1)
Linear and Branched Alkanes	218	(1)
Effect of Substituents on Alkenes	218	(2)
Cycloalkanes and Saturated Heterocyclics	220	(1)
Alkenes	220	(1)
Alkynes	221	(1)
Aromatic Compounds	222	(1)
Heteroaromatic Compounds	223	(1)
Alcohols	223	(2)
Ethers, Acetals, and Epoxides	225	(1)
Halides	225	(1)
Amines	226	(1)
Thiols, Sulfides, and Disulfides	226	(1)
Functional Groups Containing Carbon	226	(1)
Ketones and Aldehydes	227	(1)
Carboxylic Acids, Esters, Chlorides, Anhydrides, Amides, and Nitriles	227	(1)
Oximes	227	(1)
References	228	(1)
Student Exercises	229	(11)
Appendices	240	(1)
The 13C Chemical Shifts, Couplings and Multiplicities of Common NMR Solvents	240	(1)
13C Chemical Shift for Common Organic Compounds in Different Solvents	241	(1)
The 13C Correlation Chart for Chemical Classes	242	(2)
13C NMR Data for Several Natural Products (δ)	244	(1)
Correlation NMR Spectrometry; 2-D NMR	245	(71)
Introduction	245	(1)
Theory	246	(3)
Correlation Spectrometry	249	(2)
1H---1H Correlation: COSY	250	(1)
Ipsenol: 1H---1H COSY	251	(8)
Ipsenol: Double Quantum Filtered 1H---1H COSY	251	(3)
Carbon Detected 13C---1H COSY: Hector	254	(1)
Proton Detected 1H---13C COSY: HMQC	254	(1)
Ipsenol: Hector and HMQC	255	(2)
Ipsenol: Proton-Detected, Long Range 1H---13C Heteronuclear Correlation: HMBC	257	(2)
Caryophyllene Oxide	259	(6)
Caryophyllene Oxide: DQF-COSY	259	(1)
Caryophyllene Oxide: HMQC	259	(4)
Caryophyllene Oxide: HMBC	263	(2)
13C---13C Correlations: Inadequate	265	(2)
Inadequate: Caryophyllene Oxide	266	(1)
Lactose	267	(3)
DQF-COSY: Lactose	267	(3)
HMQC: Lactose	270	(1)
HMBC: Lactose	270	(1)
Relayed Coherence Transfer: TOCSY	270	(5)
2-D TOCSY: Lactose	270	(3)
1-D TOCSY: Lactose	273	(2)
HMQC -- TOCSY	275	(1)
HMQC -- TOCSY: Lactose	275	(1)
Roesy	275	(3)
Roesy: Lactose	275	(3)
VGSE	278	(4)
COSY: VGSE	278	(1)
TOCSY: VGSE	278	(1)
HMQC: VGSE	278	(3)
HMBC: VGSE	281	(1)
ROESY: VGSE	282	(1)
Gradient Field NMR	282	(34)
References	285	(1)
Student Exercises	285	(31)
NMR Spectrometry of Other Important Spin 1/2 Nuclei	316	(25)
Introduction	316	(1)
15N Nuclear Magnetic Resonance	317	(6)
19F Nuclear Magnetic Resonance	323	(3)
29Si Nuclear Magnetic Resonance	326	(1)
31P Nuclear Magnetic Resonance	327	(3)
Conclusion	330	(11)
References	332	(1)
Student Exercises	333	(5)
Appendices	338	(1)
Properties of Magnetically Active Nuclei	338	(3)
Solved Problems	341	(40)
Introduction	341	(40)
Problem 7.1 Discussion	345	(4)
Problem 7.2 Discussion	349	(4)
Problem 7.3 Discussion	353	(7)
Problem 7.4 Discussion	360	(7)
Problem 7.5 Discussion	367	(6)
Problem 7.6 Discussion	373	(1)
Student Exercises	374	(7)
Assigned Problems	381
Introduction	381
Problems	382