Organic Structural Spectroscopy

by Lambert, Joseph B.; Shurvell, Herbert F.; Lightner, David; Cooks, Robert Graham

• ISBN13: 9780132586900
• ISBN10: 0132586908
• Edition: 1st
• Format: Hardcover
• Copyright: 1998-01-01
• Publisher: Prentice Hall

Summary

This book is the revision of a widely-respected book on spectroscopy. The book covers all four areas of organic spectroscopy including NMR, MS, electronic (including CD and optical rotary dispersion), and vibrational (which also includes Raman). The book is the most complete and comprehensive treatment on the subject. It covers currently used techniques for determining the structure of organic and biological compounds. It also has a strong emphasis on problem solving and is distinctly pedagogical. This book is ideal for any practicing or future organic or biochemist.

Table of Contents

Preface	vii
1 Introduction	1	(7)
1-1 The Spectroscopic Approach to Structure	1	(1)
1-2 Contributions of Different Forms of Spectroscopy	1	(2)
1-2a Nuclear Magnetic Resonance Spectroscopy	1	(1)
1-2b Vibrational Spectroscopy	2	(1)
1-2c Electronic Spectroscopy	2	(1)
1-2d Mass Spectrometry	3	(1)
1-3 The Electromagnetic Spectrum	3	(1)
1-4 Molecular Weight and Molecular Formula	4	(2)
1-5 Structural Isomers and Stereoisomers, 5 Problems	6	(2)
PART I NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY	8	(144)
2 Introduction and Experimental Methods	8	(29)
2-1 Magnetic Properties of Nuclei	8	(3)
2-2 The Chemical Shift	11	(3)
2-3 Excitation and Relaxation	14	(2)
2-4 Pulsed Experiments	16	(2)
2-5 The Coupling Constant	18	(5)
2-6 Quantitation	23	(2)
2-7 Commonly Studied Nuclides	25	(2)
2-8 Experimental Methods	27	(3)
2-8a The Spectrometer and the Sample	27	(1)
2-8b Optimizing the Signal	28	(1)
2-8c Spectral Parameters	28	(2)
2-9 Dynamic Effects	30	(2)
2-10 Spectra of Solids	32	(2)
Problems	34	(2)
Bibliography	36	(1)
3 The Chemical Shift	37	(27)
3-1 Factors That Influence Proton Shifts	37	(4)
3-2 Proton Chemical Shifts and Structure	41	(6)
3-2a Saturated Aliphatics	41	(2)
3-2b Unsaturated Aliphatics	43	(2)
3-2c Aromatics	45	(1)
3-2d Protons on Oxygen and Nitrogen	46	(1)
3-3 Factors That Influence Carbon Shifts	47	(2)
3-4 Carbon Chemical Shifts and Structure	49	(6)
3-4a Saturated Aliphatics	49	(4)
3-4b Unsaturated Compounds	53	(1)
3-4c Carbonyl Groups	54	(1)
3-5 Summary and Tables of Chemical Shifts	55	(2)
Problems	57	(6)
Bibliography	63	(1)
4 The Coupling Constant	64	(25)
4-1 First- and Second-Order Spectra	64	(1)
4-2 Chemical and Magnetic Equivalence	65	(3)
4-3 Signs and Mechanisms: One Bond Couplings	68	(2)
4-4 Geminal Couplings	70	(2)
4-5 Vicinal Couplings	72	(2)
4-6 Long-Range Couplings	74	(1)
4-7 Spectral Analysis	75	(4)
4-8 Tables of Coupling Constants	79	(3)
Problems	82	(6)
Bibliography	88	(1)
5 Further Topics in One-Dimensional NMR	89	(28)
5-1 Spin-Lattice and Spin-Spin Relaxation	89	(5)
5-2 Reactions on the NMR Time Scale	94	(2)
5-3 Multiple Resonance	96	(5)
5-4 The Nuclear Overhauser Effect	101	(4)
5-5 Spectral Editing	105	(2)
5-6 Sensitivity Enhancement	107	(3)
5-7 Carbon Connectivity	110	(2)
5-8 Phase Cycling and Composite Pulses	112	(2)
Problems	114	(1)
Bibliography	115	(2)
6 Two-Dimensional NMR	117	(35)
6-1 Proton-Proton Correlation Through Coupling	117	(4)
6-2 Proton-Heteronucleus Correlation	131	(4)
6-3 Proton-Proton Correlation Through Space or Chemical Exchange	135	(3)
6-4 Carbon-Carbon Correlation	138	(2)
6-5 Higher Dimensions	140	(2)
6-6 Pulsed Field Gradients	142	(2)
6-7 Summary of Two-Dimensional Methods	144	(1)
Problems	145	(5)
Bibliography	150	(2)
PART II VIBRATIONAL SPECTROSCOPY	152	(100)
7 Introduction and Experimental Methods	152	(23)
7-1 Introduction	152	(1)
7-2 Vibrations of Molecules	153	(1)
7-3 Vibrational Spectra: Infrared and Raman	154	(3)
7-4 Units and Notation	157	(1)
7-5 Infrared Spectroscopy: Dispersive and Fourier Transform	158	(4)
7-5a Dispersive Infrared Spectrometers	158	(1)
7-5b Fourier Transform Infrared Spectrometers	159	(3)
7-6 Sampling Methods for Infrared Transmission Spectra	162	(3)
7-6a Liquids and Solutions	163	(1)
7-6b Solids	164	(1)
7-7 Raman Spectroscopy: Dispersive and Fourier Transform	165	(2)
7-7a Dispersive Raman Spectrometers	166	(1)
7-7b FT-Raman Spectrometers	167	(1)
7-8 Raman Sampling Methods	167	(3)
7-8a Liquids and Solutions	168	(1)
7-8b Solids	169	(1)
7-8c Depolarization Measurements	170	(1)
7-9 Special Techniques in Infrared Spectroscopy	170	(4)
7-9a Gas Phase Infrared Spectroscopy	170	(1)
7-9b Microsampling	171	(1)
7-9c Infrared Reflection Spectroscopy	171	(2)
7-9d Gas Chromatography and Infrared Spectroscopy (GC-IR)	173	(1)
Problems	174	(1)
Bibliography	174	(1)
8 Group Frequencies: Infrared and Raman	175	(26)
8-1 Introduction to Group Frequencies	175	(1)
8-2 Factors Affecting Group Frequencies	176	(11)
8-2a Symmetry	177	(2)
8-2b Mechanical Coupling of Vibrations	179	(1)
8-2c Fermi Resonance	180	(1)
8-2d Hydrogen Bonding	181	(1)
8-2e Ring Strain	182	(1)
8-2f Electronic Effects	183	(1)
8-2g Constitutional Isomerism	184	(1)
8-2h Stereoisomerism	185	(1)
8-2i Conformational Isomerism	186	(1)
8-2j Tautomerism (Dynamic Isomerism)	187	(1)
8-3 Infrared Group Frequencies	187	(1)
8-4 Raman Group Frequencies	188	(11)
Problems	199	(1)
Bibliography	200	(1)
9 Structural Analysis	201	(51)
9-1 Introduction	201	(1)
9-2 Preliminary Analysis	202	(6)
9-2a Introduction	202	(1)
9-2b Hydrocarbons or Hydrocarbon Groups	203	(1)
9-2c Compounds Containing Oxygen	204	(3)
9-2d Compounds Containing Nitrogen	207	(1)
9-3 The CH Stretching Region (3340-2700 cm(-1))	208	(3)
9-3a Introduction	208	(1)
9-3b Alkynes	208	(1)
9-3c Aromatic Compounds	208	(1)
9-3d Unsaturated Nonaromatic Compounds	209	(1)
9-3e Saturated Hydrocarbon Groups	210	(1)
9-3f Aldehydes	210	(1)
9-4 The Carbonyl Stretching Region (1850-1650 cm(-1))	211	(3)
9-4a Introduction	211	(3)
9-4b Compounds Containing a Single C = O Group	211	(2)
9-4c Compounds Containing Two C = O Groups	213	(1)
9-5 Aromatic Compounds	214	(2)
9-5a General	214	(1)
9-5b Substituted Aromatic Compounds	214	(1)
9-5c Raman Spectra of Aromatic Compounds	215	(1)
9-6 Compounds Containing Methyl Groups	216	(2)
9-6a General	216	(1)
9-6b Isopropyl and tert-Butyl Groups	217	(1)
9-7 Compounds Containing Methylene Groups	218	(1)
9-7a Introduction	218	(1)
9-7b CH(2) Bending (Scissoring)	218	(1)
9-7c CH(2) Wagging and Twisting	218	(1)
9-7d CH(2) Rocking	219	(1)
9-7e CH(2) Wagging in Vinyl and Vinylidene Compounds	219	(1)
9-7f Relative Numbers of CH(2) and CH(3) Groups	219	(1)
9-8 Unsaturated Compounds	219	(4)
9-8a The C = C Stretching Mode	219	(1)
9-8b Cyclic Compounds	219	(1)
9-8c The C = C Stretching Mode	220	(1)
9-8d CH = and CH(2) = Bending Modes	220	(3)
9-9 Compounds Containing Oxygen	223	(3)
9-9a General	223	(1)
9-9b Ethers	224	(1)
9-9c Alcohols and Phenols	224	(2)
9-9d Carboxylic Acids and Anhydrides	226	(1)
9-9e Esters	226	(1)
9-10 Compounds Containing Nitrogen	226	(5)
9-10a General	226	(1)
9-10b Amino Acids, Amines, and Amine Hydrohalides	226	(3)
9-10c Anilines	229	(1)
9-10d Nitriles	229	(1)
9-10e Nitro Compounds	230	(1)
9-10f Amides	230	(1)
9-10g Oximes	230	(1)
9-11 Compounds Containing Phosphorus and Sulfur	231	(4)
9-11a General	231	(1)
9-11b Phosphorus Acids and Esters	231	(1)
9-11c Aromatic Phosphorus Compounds	231	(1)
9-11d Compounds Containing C-S, S-S, and S-H Groups	232	(1)
9-11e Compounds Containing S=O Groups	233	(2)
9-12 Heterocyclic Compounds	235	(2)
9-12a General	235	(2)
9-12b Aromatic Heterocycles	237	(1)
9-12c Pyrimidines and Purines	236	(1)
9-12d Five-Membered Ring Compounds	236	(1)
9-12e NH Stretching Bands	236	(1)
9-13 Compounds Containing Halogens	237	(1)
9-13a General	237	(1)
9-13b CH(2)X Groups	238	(1)
9-13c Haloalkyl Groups	238	(1)
9-13d Aromatic Halogen Compounds	238	(1)
9-14 Boron, Silicon, and Organometallic Compounds	238	(1)
9-15 Isotopically Labeled Compounds	239	(1)
9-15a The Effect of (2)H and (13)C Isotopic Substitution on Stretching Modes	239	(1)
9-15b The Effect of Deuterium Substitution on Bending Modes	239	(1)
9-16 Using the Literature on Vibrational Spectra	240	(2)
9-16a Collections of Spectra	240	(1)
9-16b Infrared Spectra	241	(1)
9-16c Raman Spectra	241	(1)
9-16d Sources of References to Published Spectra	242	(1)
Problems	242	(8)
Bibliography	250	(2)
PART III ELECTRONIC ABSORPTION AND CHIROPTICAL SPECTROSCOPY	252	(94)
10 Introduction and Experimental Methods	252	(22)
10-1 Introduction	252	(2)
10-2 Measurement of Ultraviolet-Visible Light Absorption	254	(4)
10-2a Wavelength and XXX(max')	255	(1)
10-2b Beer-Bouger-Lambert Law and XXX(max')	255	(1)
10-2c Shape of Absorption Curves: The Franck-Condon Principle	256	(1)
10-2d Solvent Effects and XXX(max) Shifts	257	(1)
10-3 Measurements Using Polarized Light	258	(8)
10-3a Ordinary Absorption and Chiroptical Spectroscopy	261	(1)
10-3b Circular Birefringence and Circular Dichroism	261	(2)
10-3c Optical Rotatory Dispersion (ORD) and Circular Dichroism (CD) Quantities	263	(1)
10-3d ORD and CD Spectra and Cotton Effects	264	(2)
10-3e Relative Advantages of ORD and CD	266	(1)
10-4 Quantitative Measurements	266	(3)
10-4a Difference Spectroscopy	266	(2)
10-4b Deviations From Beer's Law	268	(1)
10-4c Isosbestic Points	268	(1)
10-5 Experimental Aspects	269	(3)
10-5a Solvents	269	(1)
10-5b Cells (Cuvettes) and Sample Preparation	269	(2)
10-5c Calibration of ORD and CD Instruments	271	(1)
10-5d Possible Sources of Error	271	(1)
Problems	272	(1)
Bibliography	273	(1)
11 UV-Vis, CD, and ORD	274	(30)
11-1 Electronic Transitions and Chromophores	274	(5)
11-1a Classification of Electronic Transitions	275	(2)
11-1b Singlet and Triplet States	277	(1)
11-1c Allowed and Forbidden Transitions	277	(1)
11-1d Absorption Intensity: Oscillator and Rotatory Strengths	278	(1)
11-2 Isolated Chromophores	279	(6)
11-2a Carbonyl: Ketone and Aldehyde Absorption	279	(2)
11-2b Carbonyl: Ketone ORD and CD	281	(1)
11-2c Carbonyl: Acid, Ester, and Amide Absorption	281	(2)
11-2d Alkenes	283	(2)
11-3 Conjugated Chromophores	285	(2)
11-3a Dienes and Polyenes	285	(1)
11-3b XXX, XXX-Unsaturated Carbonyls	286	(1)
11-4 Aromatic Compounds	287	(5)
11-5 Important Naturally Occurring Chromophores	292	(7)
11-5a Amino Acids, Peptides, and Proteins	292	(4)
11-5b Nucleic Acids and Polynucleotides	296	(1)
11-5c Porphyrins and Metalloporphyrins	296	(3)
11-6 Worked Problems	299	(2)
Problems	301	(2)
Bibliography	303	(1)
12 Structural Analysis	304	(42)
12-1 Applications of the Woodward-Fieser Rules	304	(5)
12-1a Conjugated Dienes and Polyenes	304	(3)
12-1b Conjugated Ketones, Aldehydes, Acids, and Esters	307	(2)
12-2 Determination of Absolute Configuration	309	(8)
12-2a The Octant Rule	309	(3)
12-2b Exciton Coupling and the Exciton Chirality Rule	312	(5)
12-3 Steric Effects	317	(1)
12-4 Solvent Effects and Tautomerism	318	(2)
12-5 Conformational Analysis	320	(2)
12-6 Hydrogen Bonding Studies	322	(1)
12-7 Homoconjugation	323	(2)
12-8 Charge Transfer Bands	325	(2)
12-9 Worked Problems	327	(10)
Problems	337	(7)
Bibliography	344	(2)
PART IV MASS SPECTROMETRY	346	(133)
13 Ionization and Mass Analysis	346	(46)
13-1 Scope and Applications of Mass Spectrometry	346	(2)
13-2 Sample Introduction	348	(2)
13-2a Direct Introduction	349	(1)
13-2b Introduction via Gas or Liquid Chromatographs	349	(1)
13-2c Other Sample Introduction Methods	350	(1)
13-3 Ionization	350	(24)
13-3a Electron Ionization (EI)	351	(4)
13-3b Chemical Ionization (CI)	355	(7)
13-3c Desorption Ionization (DI) Including Matrix-Assisted Laser Desorption Ionization (MALDI)	362	(7)
13-3d Spray Ionization (SI) Including Electrospray Ionization (ESI)	369	(5)
13-3e Ionization Summary	374	(1)
13-4 Mass Analysis	374	(12)
13-4a Magnetic Sectors	374	(2)
13-4b Time-of-Flight(TOF) Analyzers	376	(1)
13-4c Quadrupole Mass Filters	377	(2)
13-4d Quadrupole Ion Traps	379	(1)
13-4e Ion Cyclotron Resonance (ICR)	380	(2)
13-4f High Resolution Mass Spectrometers	382	(1)
13-4g Tandem Mass Spectrometers	382	(2)
13-4h Ion Detection and Data Handling	384	(2)
13-5 Worked Problems	386	(3)
Problems	389	(1)
Bibliography	390	(2)
14 Fragmentation and Ion Chemistry	392	(46)
14-1 General Principles of Fragmentation	392	(5)
14-1a Energetics of Dissociation	392	(1)
14-1b Odd- and Even-Electron Ions	393	(1)
14-1c Stevenson's Rule	394	(1)
14-1d Rearrangement vs. Simple Cleavage	394	(1)
14-1e Ions of High Internal Energy	395	(1)
14-1f Proximate vs. Remote Fragmentation	395	(1)
14-1g Distonic Ions	396	(1)
14-1h Charge Localization	396	(1)
14-1i Characteristic Fragment Ions and Neutral Fragments	396	(1)
14-2 Amine and Ether Type Fragmentation	397	(13)
14-2a Amines	397	(4)
14-2b Ethers	401	(5)
14-2c Alcohols and Phenols	406	(4)
14-2d Halides	410	(1)
14-3 Ketone and Aldehyde Type Fragmentation	410	(4)
14-4 Fragmentation of Other Functional Groups	414	(3)
14-4a Carboxylic Acids	414	(1)
14-4b Esters	414	(3)
14-4c Amides	417	(1)
14-4d Aliphatic Hydrocarbons	417	(1)
14-4e Aromatic Hydrocarbons	417	(1)
14-5 Negative Ion Fragmentation	417	(2)
14-6 Fragmentation in CI, DI, and SI	419	(2)
14-7 Ion Chemistry	421	(11)
14-7a Unimolecular Fragmentation	421	(5)
14-7b Ion-Molecule Reactions	426	(3)
14-7c Advanced Ion Chemistry	429	(3)
14-8 Worked Problems	432	(4)
Problems	436	(1)
Bibliography	437	(1)
15 Chemical Analysis	438	(35)
15-1 Molecular Weight Determination	438	(1)
15-2 Molecular Structure Determination	439	(2)
15-3 Molecular Formula Determination (Exact Mass Measurement)	441	(1)
15-4 Isotopic Analysis	442	(7)
15-4a Recognition of Elements: Isotopic Signatures	442	(1)
15-4b Number of Carbon Atoms in a Molecule	442	(1)
15-4c Calculation of Ion Abundance Ratios From the Molecular Formula	443	(1)
15-4d Typical Molecular Ion Isotopic Profiles for Organic and Biological Compounds	444	(2)
15-4e Determination of Molecular Formula From Isotopic Abundances	446	(1)
15-4f Isotopic Purity Determination	447	(2)
15-5 Quantitative Analysis	449	(1)
15-6 Mixture Analysis	450	(5)
15-6a Chromatography-Mass Spectrometry	450	(2)
15-6b Tandem Mass Spectrometry (MS-MS)	452	(3)
15-7 Thermochemical Determinations: Heats of Formation and Ion Affinities	455	(1)
15-8 Other Applications of Mass Spectrometry	456	(2)
15-8a Industrial Applications and Process Control	456	(1)
15-8b Isotope Ratio Mass Spectrometry	456	(1)
15-8c Elemental Analysis	457	(1)
15-8d Surface Elemental Analysis	457	(1)
15-9 Worked Problems	458	(9)
Problems	467	(5)
Bibliography	472	(1)
Appendix to Part IV	473	(6)
PART V INTEGRATED PROBLEMS	479	(78)
16 Integrated Problems	480	(77)
Index	557