波谱分析 研究生6.pptVIP

第五节. 基类重要得2D NMR Spectra的应用 Application of Two-Dimensional NMR 1H-1H COSY谱 实例: NOESY 实例1: C-H异核相关谱给出碳氢的偶合关系-HMQC 实例2: 四.应用举例: 2. 一化合物的分子式为 C10H16NO, 所有图谱如下,试推出结构. 3. 一化合物的分子式为 C8H12NO6Br, 所有图谱如下,试推出结构. 课外练习: * C15H12ClNO2 C15H12ClNO2 C15H12ClNO2 例： C4H4O 150 100 50 1 0 1: 109.7 2: 143.0 2 例： C4H4O3 150 100 50 2 1 0 1: 28.6 2: 172.9 例： C6H6O3 IR 中有酯基吸收 150 100 50 4 6 3 2 1 0 5 1: 51.7 2: 111.9 3:117.9 4:144.8 5:146.4 6:159.0 例： C7H10O3 环氧化合物 150 100 50 5t 7s 4t 2t 1q 0 6s 1: 20.7 2: 43.9 3:50.4 4:65.7 5:126.4 6:138.0 7:167.7 3d 例： C9H18O3 IR 示有羟基吸收 150 100 50 5t 8d 4t 2t 1q 0 7t 1: 10.7 2: 20.9 3 :41.0 4: 63.7 5: 70.4 6: 72.5 7: 115.7 8: 132.2 3s 6t 2D NMR 谱图常以轮廓图表示而不用三维的方式.相同情况同样使用在地图上 10 20 30 40 50 60 20 40 60 0.5 1 1.5 2 10 20 30 40 50 60 10 20 30 40 50 60 1.2D COSY(Correlated Spectroscopy) N C H C H C O H H Cross peaks exist in the 2-D COSY spectrum where there is spin-spin coupling between hydrogens. 2D COSY 谱中,交叉峰 f1=a, f2=d 表明a与b有自旋-自旋偶合作用.投影图将给出一般的氢谱 5 4 3 2 1 0 5 4 3 2 1 0 C交叉峰s 对角线峰 a a b b c d e e d c 2. NOESY—空间相关谱 (Nuclear Overhauser Effect Spectroscopy) N C H C H C O H H N C H C H C O H H correlate nuclei through space (distance0.5nm) Noesy的交叉峰表示原子相互在空间上相邻.其强度可用来估算原子间距并以此推断分子的空间结构. Ha Hb 0 1 2 3 4 5 0 1 2 3 4 5 fa fb fc Hc 3. HMQC (Heteronuclear Multiple Quantum Correlation) The HMQC experiment provides correlation between protons and their attached heteronuclei through the heteronuclear scalar coupling. 100 80 60 40 20 0 2 5 4 3 1 0 1H 13C C-H异核相关谱给出碳氢的偶合关系- 实例1: 异核相关谱可通过观测碳(1H-13C Hetcor) 或观测氢 (HMQC, HSQC). 观测氢的实验也称做反相实验. 13C-1H HMQC of Sucrose in D2O 13C 1H HSQC: Heteronuclear Single Quantum Correlation HMQC实例: Each proton-carbon pair has a single crosspeak. 13C nuclei that have diasteriotopic protons have two correlations (some of these crosspeak pairs are boxed in the spectrum below). HMBC 4: HMBC (Heteronuclear Multiple Bond Correlation) The HMBC experiment detects lo