有机波谱-CNMR.pptVIP

2、电子效应 诱导效应 CH4 CH3Cl CH2Cl2 CHCl3 CCl4 ? / ppm： –2.6 24.9 52 77 96 重原子效应 CH3I CH3Br CH3Cl CH3F ? / ppm： –20.7 20.0 24.9 80 0.0 0.0 0.0 –6.8 7.8 70.1 F ?? 0.0 0.0 –0.5 –5.1 10.0 31.0 Cl ?? 0.0 0.0 –0.7 –3.8 10.2 19.7 Br ?? 0.0 0.0 –0.9 –1.5 10.9 –7.2 I ?? 13.7 22.8 31.9 31.9 22.8 13.7 H ? ppm 共轭效应 氢键 3、空间效应 取代烷基的密集性 ?–旁位效应 CH3CH3 CH2(CH3)2 CH(CH3)3 C(CH3)4 ? / ppm： –5.7 15.4 24.3 31.4 五、13C 化学位移的经验计算 ?c / ppm 4、各种羰基碳 ?–? 效应 ?–? 共轭效应 5、碳上未共用电子对 §5.4 13C NMR 谱图解析 1、识别谱图中的溶剂峰和杂质峰 7 t t t t 7 7 s t 峰形 39.5 123.5 135.5 149.9 128.0 49.0 29.8 206.0 77.0 ? /ppm CD3SOCD3 C5D5N C6D6 CD3OD CD3COCD3 CDCl3 氘代溶剂 2、分子对称性分析 3、碳原子δ值的分区 4、碳原子级数的确定 5、推出结构单元并组装成若干可能的结构 一、一般步骤 6、进行对谱图的指认 二、谱图解析举例 a b c d e a b c d e a b c d e a b c d e a b c d e e d DMSO-d6 C6H10O2 练习 C5H11Br C5H11Br C5H11Br Problem 5-1. A compound with the formula C3H6O2 gives the following proton-decoupled and off-resonance-decoupled spectra. Determine the structure of the compound. Problem 5-2. Predict the number of peaks that you would expect in the proton-decoupled 13C spectrum of each of the following compounds. Problems 2a and 2b are provided as examples. Dots are used to show the nonequivalent carbon atoms in these two examples. Problem 5-3. Following are proton-decoupled 13C spectra for three isomeric alcohols with the formula C4H10O. A DEPT or an off-resonance analysis yields the multiplicities shown; s = singlet, d = doublet, t = triplet, and q = quartet. Identify the alcohol responsible for each spectrum and assign each peak to an appropriate carbon atom or atoms. Problem 5-4. The following spectrum is of an ester with formula C5H8O2. Multiplicities are indicated. Draw the structure of the compound and assign each peak. Probl