加州大学伯克利分校有机化学第十章.pptVIP

? University of California ? Univesity of California Chapter 10: Nuclear Magnetic Resonance (NMR) Spectroscopy A General Spectrometer Protons as Tiny Magnets Line Up With and Against an External Magnetic Filed Absorption of Light, Spin Flip, and Resonance ? Spectral Line A Hypothetical NMR Spectrum: Active Elements Absorb at Differing Frequencies The NMR Spectrometer High Resolution NMR! The Chemical Shift δ Application of δ Integration Spin-Spin Splitting (N+1) Rule Summary Points Complex Splitting Patterns Ribonuclease A, 40 MHz “Sequential” [N+1] Rule Stereocenters and Methylene Groups H Bonded/Acidic Protons:OH, SH, N H 13C NMR Spectroscopy Symmetry Chemical Shift Range Advanced Techniques Two Dimensional NMR MRI : Magnetic Resonance Imaging MRI of Human Abdomen Brain Tumor About to be Zapped My Brain Cross Sections of 3-D Image Coupling is restored on cooling, because proton exchange is “frozen” (on the NMR time scale). CH3OH OH peak often broad; disappears on addition of D2O to the sample (H/D exchange). Only 1% 13C in nature: No 13C—13C splitting, since chances of finding two 13C adjacent are small (~0.01%). (For the same reason: No 13C—H seen in 1H NMR. 99% of sample is 12C). Large Js 13C H J ~ 100-150 Hz 13C C H J ~ 5-10 Hz But: 13C—H visible in 13C NMR. Triplet of quartets Quartet of triplets Coupling to H can be removed by “broad band” irradiation of all Hs Hence: all lines are singlets ! averages Hα/β C7H14 isomers Number of Cs: 5 5 4 4 3 1 7 Chemical shift range : 200 ppm (1H: 10 ppm) Rules for deshielding same as in 1H NMR (multiply by a factor of 10-20) Distortionless polarization transfer (“DEPT”) 13C NMR spectrum. Tells us whether the carbon is attached to 3, 2, 1 or no hydrogen, i.e. CH3, CH2, CH, or C. Requires running the spectrum in three different ways (using specific laser pulse sequences). Example : Limonene. Normal spectrum DEPT-90 spectrum: only CH DEPT-135 spectrum: CH and CH3 positive CH2 negative peaks N equ