Chem 605 

Chem 605 - Structure Determination Using Spectroscopic Methods

Instructor: Hans J. Reich

This course is taught once a year, currently in the spring semester. It is available for minor credit for all graduate students.



A. Introduction - the electromagnetic spectrum 

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) γ-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, ABX3, 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. 2D NMR 
  1. The spin-echo experiment, multi-pulse NMR 
  2. Homonuclear correlation experiments (COSY, etc) 

I. Relaxation 
  1. T1 and T2 in 1H, 13C, and other nuclei 
  2. The Nuclear Overhauser Effect (NOESY, ROESY experiments) 

J. Multinuclear NMR 
  1. The spin 1/2 nuclei 
  2. Quadrupolar nuclei, quadrupolar relaxation 
  3. Isotopic labeling, isotope shifts 
  4. Heteronuclear correlation (HETCOR, HMQC, etc) 

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

L. Mass spectrometry (?)

Course Texts

The textbooks listed below are not required, but you may find them useful, especially if you do not already have a general structure determination textbook (such as the Lambert or Silverstein books). There are extensive handouts which will cover most aspects of the course.

“Basic One- and Two-Dimensional NMR Spectroscopy,” H. Friebolin, 5th Ed., VCH, 2010 (ISBN 3527327827)

“Tables of Spectral Data for Structure Determination of Organic Compounds,” E. Pretsch, P Bülmann, M. Badertscher 4rd Ed. Springer Verlag, 2009 (ISBN 3540938095)

Office Hours

Office hours for Chem 605: Thurs 1:30-2:30, room 8112

Problems Sets, Quizzes, and Examinations

There will be two “midterm” exams, to be held on Saturday (10:00 AM) on March 10 and April 19. The final exam will be on ?, all in room 1315 (the classroom). These exams are “open book” - you may bring any written materials you find useful to the exam. Calculators are fine, but computer devices and internet use is not allowed. Weekly problem sets will be handed out, typically on Wednesdays, to be handed in (in whole or in part, as announced) the next Wednesday. The problems will be looked at, but not graded in detail, and will be covered in class the following Friday. Short take-home quizzes will be handed out sporadically, especially during the first part of the course. They will be covered in the next lecture, with class participation.

Web Resources in NMR

Advanced NMR A course on 2D NMR and the product operator formalism taught by Visiting Professor Gerd Gemmecker in 1999
Basics of NMR Physics and Technique of NMR Spectroscopy (Joseph P. Hornak, Rochester Institute of Technology)

Reserve List for Chem 605 (Reich)
Fall 2013

General Textbooks

  “Organic Structural Analysis,” P. Crews, J. Rodriguez, M. Jaspars. Oxford University Press, 2010.
  “Organic Spectroscopy, Principles and Applications,” J. Mohan, CRC Press, 2000 ().
  "Organic Structural Spectroscopy,” J. B. Lambert, H. F. Shurvell, D. A. Lightner, R. G. Cooks, Prentice Hall, 1998 (QD ?).
  “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, 1987 (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).

NMR Textbooks

  “Basic One- and Two-Dimensional NMR Spectroscopy,” H. Friebolin, 5th Ed., VCH, 2010 (ISBN 3527327827).
  "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)
  “ABCs of FT-NMR,” Roberts, John D. (QD96 N8 R63 2000).
  "NMR Spectroscopy - Basic Principles, Concepts and Applications in Chemistry” H. Günther, John Wiley. (QD/96/N8/G8313/1995).
  “100 and More Basic NMR Experiments – A Practical Course.” S. Braun, H. -O. Kalinowski, S. Berger, VCH Verlag, 1996 (QD96/N8/B727)
  "High-resolution NMR Techniques in Organic Chemistry" T. D. W. Claridge, 1999 (QD272/S6/C53/1999)
  “NMR and Chemistry. An Introduction to Modern NMR Spectroscopy.” J. W. Akitt, B. E. Mann, Stanley Thornes Publishers, UK, 4th Ed. 2000.
  "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). 
  "Introduction to NMR Spectroscopy," R. J. Abraham, J. Fischer, P. Loftus, Wiley, 1988 (QD/96/N8/A27/1988). 
  "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 ISBN 3-540-67815-8)

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) 
  "ABCs of FT-NMR," J. D. Roberts, Sausalito CA, University Science Books, 2000 (QD96 N8 R63 2000)
  "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).