Reference Books on Spectroscopy / NMR Notes / Advanced NMR / Table of Exact Masses / Optical Activity

REFERENCE BOOKS ON SPECTROSCOPY

A. General Instructional Books

Introduction to Organic Spectroscopy; Lambert, J. B.; Shurvell, H. F.; Lightner, D. A.; Cooks, R. G.; Prentice Hall: Upper Saddle River, NJ, 1998.

Spectrometric Identification of Organic Compounds; Silverstein, R. M.; Webster, F. X.; John Wiley: New York, 1998.

Organic Spectroscopy; Crews, P.; Rodríguez, J.; Jaspars, M.; Oxford University Press: New York, 1998.

Organic Spectroscopy; Kemp, W.; W. H. Freeman: New York, 1991.

Interpreting Spectra of Organic Molecules; Sorrell, T. N.; University Science: Mill Valley, 1988.

Organic Spectroscopy; Brown, D. W.; Floyd, A. J.; Sainsbury, M.; John Wiley: New York, 1988.

Spectrometric Identification of Organic Compounds; Williams, D. H.; Fleming, I.; McGraw-Hill: New York, 1987.

Introduction to Spectroscopy: A Guide for Students of Organic Chemistry; Pavia, D. L.; Lampman, G. M.; Kriz, G. S.; W. B. Saunders: Philadelphia, 1979.

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B. Books on NMR Theory

ABCs of FT-NMR; Roberts, J. D.; University Science Books: Sausalito, California, 2000.

Principles of Nuclear Magnetic Resonance in One and Two Dimensions; Ernst, R. R.; Bodenhausen, G.; Wokaun, A.; Clarendon Press: Oxford, England, 1987.

Two Dimensional Nuclear Magnetic Resonance in Liquids; Bax, A.; D. Reidel Publishing Co.: Dordrecht, Holland, 1982.

C. Books on NMR Interpretation

Applications of Dynamic NMR Spectroscopy to Organic Chemistry; Oki, M.; VCH: New York, 1985, Methods in Stereochemical Analysis, Vol. 4.

Biological Applications of Magnetic Resonance; Shulman, R. G., Ed.; Academic Press: New York, 1979.

Carbon-13 NMR Based Organic Spectral Problems; Fuchs, P. L.; Bunnell, C. A.; John Wiley: New York, 1979.

Carbon-13 NMR Data for Organometallic Compounds; Mann, B. R.; Taylor, B. F. Academic: New York, 1981.

Carbon-Carbon and Carbon-Proton NMR Couplings: Applications to Organic Stereochemistry and Conformational Analysis; Marshall, J. L.; VCH: New York, 1983, Methods in Stereochemical Analysis, Vol. 2.

Chemical Shift Ranges in Carbon-13 NMR Spectroscopy; Bremser, W.; Franke, B.; Wagner, H.; VCH: New York, 1982.

Lanthanide Shift Reagents in Stereochemical Analysis; Morrill, T. C.; VCH: New York, 1987, Methods in Stereochemical Analysis, Vol. 5.

Modern NMR Spectroscopy; Sanders, J. K. M.; Hunter, B. K.; Oxford: New York, 1993.

Modern NMR Spectroscopy: A Workbook of Chemical Problems; Sanders, J. K. M.; Constable, E. C.; Hunter, B. K.; Oxford: New York, 1990.

Modern NMR Techniques for Chemistry Research; Derome, A. E.; Pergamon:New York, 1987.

NMR of Proteins and Nucleic Acids; Wüthrich, K.; Wiley and Sons: New York, 1986.

Phosphorous-31 NMR Spectroscopy in Stereochemical Analysis; Verkade, J.G., Quin, L.D., Eds.; VCH: New York, 1987.

Structure Elucidation by Modern NMR; Pretsch, E.; Clerc, T.; Seibl, J.; Simon, W.; Springer-Verlag: New York, 1989.

Stereochemical Applications of NMR Studies in Rigid Bicyclic Systems; Marchand, A. P.; VCH: New York, 1982, Methods in Stereochemical Analysis, Vol. 1.

Structure Elucidation by Modern NMR; Duddeck, H.; Dietrich, W.; Springer-Verlag: New York, 1989.

The Nuclear Overhauser Effect in Structural and Conformational Analysis; Neuhaus, D.; Williamson, M.; VCH: New York, 1989.

Two-Dimensional NMR Methods for Establishing Molecular Connectivity; Martin, G. E.; Zektzer, A. S.; VCH: New York, 1988.

Two-Dimensional NMR Spectroscopy Applications for Chemists and Biochemists; Croasmun, W. R.; Carlson, R. M. K.; VCH: New York, 1987, Methods in Stereochemical Analysis, Vol. 9.

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NMR NOTES

NMR Water Signals

Solvent d of H2O (or HOD)

Acetone 2.7
Acetonitrile 2.1
Benzene 0.4
Chloroform 1.6
Dimethyl Sulfoxide 3.3
Methanol 4.8
Pyridine 4.9
Water 4.7

Effects of Steric Compression

Proton signals shift to lower field

Carbon signals shift to higher Field

Commonly Found Impurities

Ether Hydroperoxide
Approximate chemical shifts:
1.0 (3H, t), 1.3 (3H, d), 3.8 (2H, m (two quartets)), 5.0 (1H, q).

Tygon Tubing Plastisizer - Diisooctylphthalate
0.8 - 1.0 (12H, m); 1.2-1.8 (18H, m); 4.1-4.3 (4H, m); 7.5-7.6 (2H, m); 7.7-7.8 (2H, m).

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ADVANCED NMR

ONE DIMENSIONAL NMR TECHNIQUES

DEPT (Distortionless Enhancement of NMR Signals by Polarization Transfer)
A procedure which enhances the intensities of 13C signals and also provides information on the number of attached protons. Quaternary carbons are not observed. The 135o pulse results in positive signals for CH and CH3 groups and negative signals for CH2 groups. The 90o pulse results in positive signals for CH groups and null signals for CH2 and CH3 groups. The 45o pulse results in positive signals for CH, CH2 and CH3 groups.

INEPT (Insensitive Nuclei Enhanced by Polarization Transfer)
A precursor to DEPT that gives similar results, although often not as well.

NOE (Nuclear Overhauser Effect)
Irradiation at specific frequencies before signal aquisition enhances the intensities of nearby nuclei. Nearby nuclei induce relaxation, which leads to signal enhancement, through dipole-dipole interactions. The effect usually diminishes as a function of 1/r6.

TWO DIMENSIONAL NMR TECHNIQUES

NOESY (Nuclear Overhauser Effect Spectroscopy)
The 2D version of the NOE experiment yields a display of all atoms that are close in space. The diagonal and the projection on each axis are the one-dimensional spectrum. The off- diagonal peaks indicate Overhauser enhancements between pairs of protons.

ROESY (Rotating Frame Overhauser Enhancement Spectroscopy)
Advanced form of NOESY ideal for large molecules.

COSY (Correlated Spectroscopy)
A 2D experiment that yields a display of all coupled protons. The diagonal and the projection on each axis are the one-dimensional spectrum. The off-diagonal peaks indicate the presence of coupling between pairs of protons.

COLOC (Correlated Spectroscopy for Long-Range Couplings)
Experiment correlating the 13C spectrum on one axis and 1H spectrum on the other. Cross peaks indicate long-range C-H connectivity.

SECSY (Spin Echo Spectroscopy)
Technique that yields the same information as the COSY procedure, but with a different display format.

EXTASY (Exchange Interaction Spectroscopy)
Useful procedure for determining sites that undergo chemical exchange.

J-Resolved 2D NMR
A 2D technique that results in the normal spectrum projected on one axis and coupling projected on to the other axis.

HetCor (Heteronuclear Shift Correlation)
Experiment correlates the 13C spectrum on one axis and 1H spectrum on the other. Cross peaks indicate C-H connectivity.

HMBC (Heteronuclear Multiple Bond Correlation)
Advanced inverse detected experiment correlating the 13C spectrum on one axis and 1H spectrum on the other. Cross peaks indicate long-range C-H connectivity.

HMQC (Heteronuclear Multiple Quantum Coherence)
Advanced inverse detected version of HetCor. Experiment correlates the 13C spectrum on one axis and 1H spectrum on the other. Cross peaks indicate C-H connectivity.

HOHAHA (Homonuclear Hartmann Hahn)
Experiment that takes COSY a step further by correlating protons with small coupling constants as occurs with long range coupling. Identifies spin sets. Similar to TOCSY.

INADEQUATE (Incredible Natural Abundance Double Quantum Transfer Experiment)
Procedure used to directly obtain carbon-carbon connectivities and, ultimately, the carbon skeleton of a molecule.

INSIPID (Inadequate Sensitivity Improvement by Proton Indirect Detection)
A reverse detection INADEQUATE experiment that greatly reduces the aquisition time.

TOCSY (Total Correlation Spectroscopy)
Experiment that takes COSY a step further by correlating protons with small coupling constants as occurs with long range coupling. Identifies spin sets. Similar to HOHAHA.

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TABLE OF EXACT MASSES

Al 100 26.9815
Ag (107) 51.8 106.9051
Ag (109) 48.2 108.9047
As 100 74.9216
Au 100 196.9666
B (10) 19.8 10.0129
B (11) 80.2 11.0093
Ba 71.7 137.9050
Be 100 9.0122
Br (79) 50.5 78.9183
Br (81) 49.5 80.9163
C 98.89 12.0000
C (13) 1.11 13.0034
Ca 96.9 39.9626
Cd 28.9 113.9036
Cl (35) 75.5 34.9689
Cl (37) 24.5 36.9659
Co 100 58.9332
Cr 83.8 51.9405
Cs 100 132.9051
Cu 69.1 62.9298
D 0.01 2.0141
F 100 18.9984
Fe 91.7 55.9349
Ga 60.4 68.9257
Ge 36.5 73.9219
H 99.99 1.007825
Hg 29.8 201.9706
I 100 126.9004
Ir 62.6 192.9633
K 93.1 38.9637
Li 92.6 7.0160

Mg 78.7 23.985

Mn 100 54.938

Mo 23.8 97.9055

N 99.6 14.0031

Na 100 22.9898

Nb 100 92.9060

Ni 68.3 57.9353

O 99.8 15.994915

Os 40.0 191.9622

P 100 30.97376

Pb 52.3 207.9766

Pd 27.3 105.9032
Pt 33.8 194.9648

Rb 72.2 84.9117

Re 62.5 186.9560

Rh 100 102.9048

Ru 31.6 101.9037

S 95.0 31.97207

Sb 57.3 120.9038

Sc 100 44.9559

Se 49.8 79.9165

Si 92.2 27.9769

Sn 24.0 117.9018

Sr 82.6 87.90565

Te 34.5 129.9067

Ti 73.9 47.9479

Tl 70.5 204.9745

V 99.8 50.9440

W 30.6 183.9510

Zn 48.9 63.9291

Zr 51.5 89.9043

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OPTICAL ACTIVITY

Specific optical rotation ( [a] ) is corrected for concentration and pathlength, so different samples can be compared. Note that rotations are solvent and wavelength dependent.

[a]tl = 100a/lc

a = observed rotation
l = pathlength in decimeters
c = concentration in g/100 mL
t = temperature in oC
l = wavelength in nm

Example of reporting a specific rotation:

[a]22589 = 24.5 (c = 1.1, MeOH)

Enantiomeric Excess = Optical Purity = Optical Yield

ee = | % R - % S | = [a]tl (obs) x 100 / [a]tl (pure)

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