Chem 605 - Structure Determination Using Spectroscopic Methods

Instructor: Hans J. Reich

Syllabus

B. Basic ¹H NMR 
  1. Chemical Shift 
  2. Integration 
  3. J-coupling - first order multiplets 

C. Combining NMR with other spectroscopic methods to solve structure problems - IR, UV, MS. 

D. Carbon-13 NMR 
  1. Basic multinuclear NMR - sensitivity, spins, natural abundance 
  2. Spectral simplification - decoupling 
  3. Attached proton test - APT, DEPT, etc. 
  4. The pulsed NMR experiment: FT, FID, simple pulse sequences. 
  5. C-13 chemical shifts 
    a) Substituent effects - parameters, chemical shift calculations 
    b) g-Effect - stereochemical assignment 
    c) Individual functional groups - rings, sp, sp², sp³ carbons 

E. Proton-Proton J-Coupling 
  1. Dipolar and scalar coupling 
  2. Nomenclature for coupled spin systems - magnetic equivalence 
  3. Coupled two-spin systems: AX and AB patterns 
  4. Analyzable three spin systems: AX₂, AB₂, AMX, ABX systems. Second order effects and "virtual coupling" 
  5. More complicated patterns: ABXY, AA'BB', ABC 
  6. Interpretation of J-coupling constants 
    a) Two bond (gem) coupling, MO theory of coupling 
    b) Three bond (vicinal) coupling - Karplus curves 
    c) Long range coupling (W-coupling) 

F. Proton Chemical Shifts 
  1. Electronegativity 
  2. Steric compression 
  3. Magnetic anisotropy 
  4. Shift reagents and solvent induced shifts 

G. Coupling Constants involving carbon 
  1. One bond C-H coupling-hybridization 
  2. Two bond C-H coupling 
  3. Three bond C-H coupling 
  4. C-C couplings. Applications 

H. Relaxation 
  1. T₁ and T₂ in ¹H, ¹³C, and other nuclei 
  2. The Nuclear Overhauser Effect 

I. Multinuclear NMR 
  1. The spin ½ nuclei 
  2. Quadrupolar nuclei, quadrupolar relaxation 
  3. Isotopic labeling, isotope shifts 

J. Dynamic NMR. Measurement of conformational and chemical exchange rates 
  1. Line broadening - variable temperature NMR spectra 
  2. The Forsen experiment - saturation transfer 

K. 2D NMR 
  1. The spin-echo experiment, multi-pulse NMR 
  2. Homonuclear correlation experiments (COSY, etc) 
  2. Heteronuclear correlation (HETCOR, HMQC, etc) 
  3. NOE experiments (NOESY, HOESY, ROESY, etc) 
  4. Others (INADEQUATE, EXSY, etc) 

L. Mass spectrometry

Web Resources in NMR

NMR Bibliography Hans J. Reich, University of Wisconsin, Madison
NMR Spectra exercises Craig Merlic, UCLA
NMR Spectra exercises Notre Dame
NMR Spectra exercises Rider University
Advanced NMR A course on 2D NMR and the product operator formalism taught by Visiting Professor Gerd Gemmecker in 1999
Pulse Sequences Biochem 800 Course Notes (Milo Wesler, NMR Facility, University of Wisconsin, Madison)
Basics of NMR Physics and Technique of NMR Spectroscopy (Joseph P. Hornak, Rochester Institute of Technology)
NMR Resources
NMR Nuclei The NMR periodic table
WINDNMR Computer program for NMR simulation

NMR Data

Proton Chemical Shifts A compilation of proton chemical shifts and coupling constants
C-13 Chemical Shifts A compilation of carbon chemical shifts
NMR Solvents

General Textbooks

"Spectroscopic Methods in Organic Chemistry," D. H. Williams , I. Fleming, 4th Ed. 1987 (QD 272 S6 W54 1987).

"Structural Methods in Inorganic Chemistry," E. A. V. Ebsworth, D. W. H. Rankin, S. Cradock; Blackwell. (QD/95/E29/1987). 

"Spectrometric Identification of Organic Compounds," R. M. Silverstein, G. C. Bassler, T. C. Morrill, John Wiley & Sons, New York, 5th Ed. 1991. (QD/272/S6/S55/1991). 

"Introduction to Organic Spectroscopy," J. B. Lambert, H. F. Shurvell, D. Lightner, R. G. Cooks, McMillan, 1987 (QD 272 S6 I54 1987). 

"Organic Spectroscopy, Principles and Applications," Mohan, J. CRC Press, 2000 (). 

NMR Textbooks

"Basic One- and Two-Dimensional NMR Spectroscopy," H. Friebolin, 2nd Ed., VCH, 1993 (QP 519.9 N83 F7513 1993).

“Structure Elucidation by NMR in Organic Chemistry: a Practical Guide,” Breitmaier, E. (QD476/B67/2002)

“ABCs of FT-NMR,” Roberts, John D. (QD96 N8 R63 2000).

"A Complete Introduction to Modern NMR Spectroscopy," R. S. Macomber, Wiley NY 1998 (QD96/N8 M3/1998).

"Structure Elucidation by NMR in Organic Chemistry: a Practical Guide," Breitmaier, E. (QD476/B67/2002).

"NMR Spectroscopy - Basic Principles, Concepts and Applications in Chemistry" H. Günther, John Wiley. (QD/96/N8/G8313/1995). 

"Modern NMR Spectroscopy, A Guide for Chemists," J. K. M. Sanders and B. K. Hunter, 2nd Ed. Oxford 1993 (QD/96/N8/S25). 

"Modern NMR Techniques for Chemistry Research," A. E. Derome, Pergamon Press, 1987 (QD/96/N8/D47/1987). 

"High-resolution NMR techniques in organic chemistry" T. D. W. Claridge, 1999 (QD272/S6/C53/1999)

"Introduction to NMR Spectroscopy," R. J. Abraham, J. Fischer, P. Loftus, Wiley, 1988 (QD/96/N8/A27/1988). 

"Spectroscopic Techniques for Organic Chemists," J. W. Cooper, John Wiley, New York, 1980 (QD272/56/C66). 

"Nuclear Magnetic Resonance Spectroscopy," R. K. Harris, Pitman (QD/96/N8/H37/1983). 

"NMR: Basic Principles," Atta-ur-Rahman, Springer, 1986 (QD/96/N8/R34/1986). 

"NMR General Concepts and Applications," W. W. Paudler, Wiley, 1987 (QC/762/P38). 

"Introduction to Multinuclear Magnetic Resonance," C. H. Yoder and C. D. Schaeffer, Jr., Benjamin/Cummings, Menlo Park, CA 1987 (QD/96/N8/Y63/1987). 

"High Resolution NMR. Theory and Chemical Applications," E. D. Becker, Academic Press, 2nd Ed. 1980 (QD/96/N8/B43). 

"Nuclear Magnetic Resonance Spectroscopy," F. A. Bovey, 2nd Ed., Academic Press (QD/96/N8/B68/1988). 

"Laboratory Guide to Proton NMR Spectroscopy," S. A. Richards, Blackwell, 1988 (QD/96/P7/R53). 

"Structure Elucidation by Modern NMR," H. Duddeck and W. Dietrich, Springer Verlag, 1989 (QD96/N8/D813/1989). 
 

Spectroscopic Data Tables

"Tables of Spectral Data for Structure Determination of Organic Compounds," E. Pretsch, P. Bühlmann, C. Affolter, Springer Verlag, 2000 (QC462.85/T313/2000)

Problem Books

“Structure Elucidation by NMR in Organic Chemistry: A Practical guide,” E. Breitmeier, Wiley, 1993 ()

"Spectral Problems in Organic Chemistry," R. Davis and C. H. J. Wells, Chapman & Hall, New York, 1984. (QD/272/S6/D38/1984) 

"Organic Structures from Spectra," S. Sternhall and J. R. Kalman, 1995 (QD272/S6/S74/1995). 

"Modern NMR Spectroscopy: A Workbook of Chemical Problems," J. K. M. Sanders, E. C. Constable, B. K. Hunter, Oxford, 1989 (QD96/N8/S25/1989). 

"One-dimensional and Two-dimensional NMR Spectra by Modern Pulse Techniques," K. Nakanishi, Ed., University Science Books, Mill Valley CA, 1990 (QD96/N8/O54/1990). 

"Structure Elucidation by Modern NMR, A Workbook," H. Duddeck, W. Dietrich, Springer Verlag, New York, 1989 (QD96/N8/D813/1989). 

"Solving Problems with NMR Spectroscopy," Rahman, Atta-ur, Academic Press, 1996, (QC/762/R34/1996) 

Special Techniques in NMR

"Carbon-13 Nuclear Magnetic Resonance Spectroscopy," G. C. Levy, R. L. Lichter and G. L. Nelson, Wiley, 1980. (QD272/S6/L474/1980) 

"Interpretation of Carbon-13 NMR Spectra," F. W. Wehrli and T. Wirthlin, Heyden, London, 1976. (QD272/S6/W44) 

"¹³C NMR Spectroscopy, High Resolution Methods and Applications in Organic Chemistry and Biochemistry," E. Breitmaier and W. Voelter, Verlag Chemie, Weinheim, 1987. (QD96/N8/B73) 

"Fourier Transform NMR Spectroscopy," D. Shaw, Elsevier Scientific Publishing Co., New York, 1976. (Res. QC/762/S45/2/1984) 

"NMR and Chemistry: An Introduction to the Fourier Transform Multinuclear Era," 2nd Ed., J. W. Akitt, Chapman, New York, 1983. (QD96/N8/A37) 

"Dynamic NMR Spectroscopy," J. Sandström, Academic Press, New York, 1982. (QD/96/N8/S26/1982) 

"Two Dimensional NMR Spectroscopy," W. R. Croasmun, R. M. K. Carlson. (QD/96/N8/T87/1987) 

"Nuclear Overhauser Effect in Structural and Conformational Analysis," D. Neuhaus, VCH, 1989 (QP481/N46/1989). 

"One and Two Dimensional NMR Spectroscopy," T. I. Atta-ur-Rahman, Elsevier, Amsterdam, 1989, 578 (QD96/N8/R35/1989).