二维核磁共振谱原理
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2D 核磁共振谱
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
COSY: Hypothetical Coupling
二维核磁共振谱原理
COSY: 1H-1H Coupling
二维核磁共振谱原理
二维核磁共振谱原理
COSY Spectrum of Codeine
Coupling "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 —> OH H-10 -> H-9 H-3 —> H-16 H-16 —> H-11
二维核磁共振谱原理
NOESY Spectrum of Codeine
In addition to confirming assignments, the NOESY spectrum allows stereospecific assignments of methylene Hs. The 3 crosspeaks 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 -18' 16 - 17 18 - 13
二维核磁共振谱原理
COSY Spectrum of Codeine
shift
shift
Table of COSY correlations
6.6
6.7
5.7
5.3
5.7
2.7
5.7
4.9
5.3
4.2
5.3
2.7
4.9
4.2
4.2
2.9
3.3
2.7
Biblioteka Baidu
3.3
2.4
3.3
2.3
3.0
2.4
3.0
2.3
2.6
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
What You See In a NOESY. . .
二维核磁共振谱原理
突出表现NOE效应的NOESY谱
二维核磁共振谱原理
二维核磁共振谱原理
NOESY. . .
二维核磁共振谱原理
NOESY Spectrum of Codeine
二维核磁共振谱原理
NOESY Spectrum of Codeine
Expansion of the upfield region:
8 - 7, 12 7 - 18, 18' 3 - 5, 10 5 - 11, 16, 18' 9 - 10, 17, 17' 10 - 16 11 - 18, 16, 14, 18' 18 - 13, 18' 16 - 14, 17 13 - 14, 17, 17' 13' - 17, 17' 17 - 17'
HMQC is selective for direct C-H coupling HMBC will give longer range couplings (2-4 bond coupling).
The sample is 3.3 mg of codeine in .65 ml CDCl3 A 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.
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
2 D C-H相关谱（C-H COSY)
二维核磁共振谱原理
2 D 远程C-H COSY
二维核磁共振谱原理
HMQC and HMBC
Heteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Multiple Bond Coherence (HMBC): 2-D inverse H,C correlation techniques that allow for the determination of carbon (or other heteroatom) to hydrogen connectivity.
2.4
2.6
2.1
2.6
1.9
2.4
2.1
2.4
1.9
二维核磁共振谱原理 2.1
1.9
Assignments
7 -8 3 -5 3 - 16 3-9 weak 5 - 10 5 - 16 9 - 10 10 - OH 11- 16 11 - 14 11 - 18' 18 - 14 18 - 18' 13 - 13' 13 - 17 13 - 17' 13' - 17 13' - 17' 17 - 17'
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
COSY: Hypothetical Coupling
二维核磁共振谱原理
COSY: 1H-1H Coupling
二维核磁共振谱原理
二维核磁共振谱原理
COSY Spectrum of Codeine
Coupling "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 —> OH H-10 -> H-9 H-3 —> H-16 H-16 —> H-11
二维核磁共振谱原理
NOESY Spectrum of Codeine
In addition to confirming assignments, the NOESY spectrum allows stereospecific assignments of methylene Hs. The 3 crosspeaks 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 -18' 16 - 17 18 - 13
二维核磁共振谱原理
COSY Spectrum of Codeine
shift
shift
Table of COSY correlations
6.6
6.7
5.7
5.3
5.7
2.7
5.7
4.9
5.3
4.2
5.3
2.7
4.9
4.2
4.2
2.9
3.3
2.7
Biblioteka Baidu
3.3
2.4
3.3
2.3
3.0
2.4
3.0
2.3
2.6
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
What You See In a NOESY. . .
二维核磁共振谱原理
突出表现NOE效应的NOESY谱
二维核磁共振谱原理
二维核磁共振谱原理
NOESY. . .
二维核磁共振谱原理
NOESY Spectrum of Codeine
二维核磁共振谱原理
NOESY Spectrum of Codeine
Expansion of the upfield region:
8 - 7, 12 7 - 18, 18' 3 - 5, 10 5 - 11, 16, 18' 9 - 10, 17, 17' 10 - 16 11 - 18, 16, 14, 18' 18 - 13, 18' 16 - 14, 17 13 - 14, 17, 17' 13' - 17, 17' 17 - 17'
HMQC is selective for direct C-H coupling HMBC will give longer range couplings (2-4 bond coupling).
The sample is 3.3 mg of codeine in .65 ml CDCl3 A 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.
二维核磁共振谱原理
二维核磁共振谱原理
二维核磁共振谱原理
2 D C-H相关谱（C-H COSY)
二维核磁共振谱原理
2 D 远程C-H COSY
二维核磁共振谱原理
HMQC and HMBC
Heteronuclear Multiple Quantum Coherence (HMQC) and Heteronuclear Multiple Bond Coherence (HMBC): 2-D inverse H,C correlation techniques that allow for the determination of carbon (or other heteroatom) to hydrogen connectivity.
2.4
2.6
2.1
2.6
1.9
2.4
2.1
2.4
1.9
二维核磁共振谱原理 2.1
1.9
Assignments
7 -8 3 -5 3 - 16 3-9 weak 5 - 10 5 - 16 9 - 10 10 - OH 11- 16 11 - 14 11 - 18' 18 - 14 18 - 18' 13 - 13' 13 - 17 13 - 17' 13' - 17 13' - 17' 17 - 17'