二维核磁共振谱原理.pptx

2D 核磁共振谱COSY: Hypothetical CouplingCOSY: 1H-1H CouplingCOSY Spectrum of CodeineCoupling networks can be traced out, as shown in the figure below.? The colored arrows trace out coupling networks, corresponding to: H-3 — H-5 — H-10 — OHH-10 - H-9H-3 — H-16H-16 — H-11COSY Spectrum of CodeineshiftshiftAssignments 6.66.77 - 8 5.75.33 - 5 5.72.73 - 16 5.74.93-9 weak5.34.25 - 10 5.32.75 - 16 4.94.29 - 10 4.22.910 - OH 3.32.711- 16 3.32.411 - 14 3.32.311 - 18 3.02.418 - 14 3.02.318 - 18 2.62.413 - 13 2.62.113 - 17 2.61.913 - 17 2.42.113 - 17 2.41.913 - 17 2.11.917 - 17 Table of COSY correlationsWhat You See In a NOESY. . .突出表现NOE效应的NOESY谱NOESY. . .NOESY Spectrum of Codeine The sample is 3.3 mg of codeine in .65 ml CDCl3A contour plot of the NOESY spectrum is shown below.??As with all homonuclear 2D plots, the diagonal consists of intense peaks that match the normal spectrum, as do projections onto each axis.?? The interesting information is contained in the cross-peaks, which appear at the coordinates of 2 protons which have an NOE correlation.For small molecules, the NOE is negative.? Exchange peaks have the opposite sign from NOE peaks, making them easy to identify.? The water peak at 1.5 ppm exchanges with the OH at 2.9 ppm, shown here in red.The spectrum is phased with the large diagonal peaks inverted (shown in red here), so the NOE cross-peaks are positive.?NOESY Spectrum of CodeineExpansion of the upfield region:8 - 7, 127 - 18, 183 - 5, 105 - 11, 16, 189 - 10, 17, 1710 - 1611 - 18, 16, 14, 1818 - 13, 1816 - 14, 1713 - 14, 17, 1713 - 17, 1717 - 17??NOESY Spectrum of CodeineIn addition to confirming assignments, the NOESY spectrum allows stereospecific assignments of methylene Hs.? The 3 cross-peaks indicated in red on the plot below distinguish between the 3 CH2 pairs:Table of NOEs: ( indicates the more upfield of geminal CH2 protons)5 -1816 - 1718 - 132 D C-H相关谱（C-H COSY)2 D 远程C-H COSYHMQC and HMBCHeteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Mu