核磁共振_俞

核磁共振在化学研究中的实际应用简介例一ppm(t1)0.01.02.03.04.05.06.07.08.09.08.1918.1707.9247.9127.9037.8916.9836.9615.5974.4494.4314.4144.3961.4491.4311.4132.043.992.000.932.033.05实测氢谱例一ChemDraw预测的氢谱例二ppm(t1)0.05.010.08.6588.6408.5728.5518.4168.3968.0448.0247.8607.8417.8214.1784.1594.1403.8383.8213.8043.7861.8631.8441.8251.8041.2271.2091.1920.7660.7450.7241.001.011.011.011.042.096.082.099.152.09例三ppm(t1)0.05.010.013.0428.3987.9077.8477.8277.4187.4007.3806.8826.8736.8616.8556.8353.3492.5001.001.000.981.071.022.04ppm(t1)7.007.508.008.508.3987.9077.8477.8277.4187.4007.3806.8826.8736.8616.8556.8351.000.981.071.022.04ppm(t1)050100150172.605161.603134.568128.555118.829117.887114.80540.62040.41240.20439.99539.78739.57839.370核磁共振的应用范围——测定有机化合物分子结构氢谱——获取有机物分子的碳氢结构信息碳谱——获取有机物分子的基本骨架信息杂原子谱—获取有机物分子中其他原子的结构信息COSY——获取有机分子中H原子之间的相关信息HQSC——获取有机分子中C,H原子间的相关信息HMBC——获取有机分子中C,H间的远程相关信息…………核磁共振原理简述0BELarmor频率化学位移自旋-自旋偶合化学信息:Larmor频率原子核化学位移:结构测定(功能团)J-偶合:结构测定(原子的相关性)偶极偶合:结构测定(空间位置关系)B0yxz磁性核的NMR频率同位素自旋丰度(%)在不同磁场下的NMR频率(T)4.69757.04639.359011.744014.09261H1/299.98200.000300.000400.000500.000600.00013C1/21.10850.28875.432100.577125.721150.86415N1/20.3720.26530.39840.53150.66460.79617O5/20.03727.11340.67054.22767.78481.34019F1/2100188.154282.231376.308470.385564.46227Al5/210052.11478.172104.229130.287156.34429Si1/24.739.73059.59579.46099.325119.19031P1/210080.961121.442161.923202.404242.884有机化合物中氢谱的化学位移质子类型结构化学位移,ppmCyclopropaneC3H60.2PrimaryR-CH30.9SecondaryR2-CH21.3TertiaryR3-C-H1.5VinylicC=C-H4.6-5.9Acetylenictriplebond,C≡C-H2-3AromaticAr-H6-8.5BenzylicAr-C-H2.2-3AllylicC=C-CH31.7FluoridesH-C-F4-4.5ChloridesH-C-Cl3-4BromidesH-C-Br2.5-4IodidesH-C-I2-4质子类型结构化学位移,ppmAlcoholsH-C-OH3.4-4EthersH-C-OR3.3-4EstersRCOO-C-H3.7-4.1EstersH-C-COOR2-2.2AcidsH-C-COOH2-2.6CarbonylCompoundsH-C-C=O2-2.7AldehydicR-(H-)C=O9-10HydroxylicR-C-OH1-5.5PhenolicAr-OH4-12EnolicC=C-OH15-17CarboxylicRCOOH10.5-12AminoRNH21-5有机化合物中氢谱的化学位移Phenols-OHAlcohols-OHThioalcohols-OHAmines-NH2Carboxylicacids-OHAldehydesHeteroaromaticAromaticAlkenesAlcoholsAlkinesX-CH3-CH2-CyclopropylM-CH3ppm((TMS)1211109876543210碳谱的化学位移酮C=O醛-CHO酸-COOH酯，酰胺-COOR硫酮C=S偶氮甲烷C=N腈CN杂芳环C-N烯C=C芳环Ar杂芳环C=C炔C≡四级CC-CC-OC-NC-SC-X三级CC-CC-OC-NC-SC-Xppm(TMS)2202102001901801701601501401301201101009080706050403020100四级CC-CC-OC-NC-SC-X三级CC-CC-OC-NC-SC-X二级CC-CC-OC-NC-SC-X一级CC-CC-OC-NC-SC-Xppm(TMS)2202102001901801701601501401301201101009080706050403020100碳谱的化学位移偶合自旋-自旋n+1规律偶合常数J1J：如13C-1H2J：如同碳二氢3J：邻碳二氢JH-C-C-H长程偶合：不饱和体系、芳环芳杂环一级谱与二级谱体系AB体系：环上孤立的CH2，二取代乙烯，四取代苯等AMX体系：最简单的三核体系ABX体系：ABC体系：AA’BB’体系：例如邻二氯苯ppm(f1)7.007.508.008.508.3987.9077.8477.8277.4187.4007.3806.8826.8736.8616.8556.8352.0021.0001.0850.9140.981ppm(f1)6.8006.8506.9006.8826.8736.8616.8556.8352.0021,3241,3DMSO_d6=ppm(f1)6.806.907.007.107.207.307.407.507.4497.4317.4117.3827.3637.2557.0106.9896.8826.8636.8451.0001.0801.0191.032CDCl212437.2845.6295.6175.6065.3335.3265.2735.2665.2605.2534.5944.5884.5634.5574.4264.4164.4044.3944.2964.2904.2714.2644.2014.1884.1714.1572.4862.4802.4742.0962.0932.0782.0361.6072.161.081.111.102.251.101.006.633.273.291.121.094.4587654321PPM5.6295.6175.6065.3335.3265.2735.2665.2605.2534.5944.5884.5634.5574.4264.4164.4044.3944.2964.2904.2714.2644.2014.1884.1714.1572.161.081.111.102.251.101.095.65.45.25.04.84.64.44.2PPM4.5944.5884.5634.5574.4264.4164.4044.3944.3354.3294.2964.2904.2714.2644.2324.2254.2014.1884.1714.1571.002.031.001.004.64.54.44.34.24.1PPM核磁共振信号的数量级核的共振频率108Hz化学位移104Hz偶合100~1HzNMR氢谱的简单解析杂质峰、溶剂峰、旋转边带、13C卫星峰结合分子式，计算不饱和度确定各峰组对应的氢原子数对称性化学位移d、偶合J、峰形组合可能的结构式指认各官能团对应的峰组2221NXHCΩNMR碳谱的简单解析溶剂峰、杂质峰对称性谱线数=碳原子数，无对称谱线数碳原子数，有一定对称，偶然重合确定各碳原子化学位移d，分区羰基或叠烯区d150ppm不饱和碳d=90~160ppm脂肪链碳d100ppm碳原子级数DEPT推出结构单元指认各碳原子对应的峰二维谱的简单解析COSY—H-H相关NOESY—H-H空间相关HQSC—C-H相关HMBC—C-H远程相关NNH2ONOOHOHHHHHHOHH单取代苯环对位二取代苯环对位二取代苯环邻位二取代苯环邻位二取代苯环间位二取代苯环单取代杂环——吡啶单取代杂环——吡咯单取代杂环——呋喃乙烯基乙烯基烷烃CH3-CH2-CH2-CH2-CH2-CH3NMR谱图的简单解析实例氢谱1H碳谱13C二维相关谱氢氢相关COSY碳氢相关HSQC远程相关HMBC实例一由四个碳的原料，看是否得到了羧酸衍生物R-COOH？ppm(f1)0.05.010.07.2603.2951.7271.6261.5131.0532.0002.0083.0591.965CDCl3ppm(f1)05010015020077.72377.40577.08759.80524.58920.26714.18614.093CDCl3159.07224.24319.77413.73Assign.Shift(ppm)A3.40B1.68C1.45D1.02实例二8-羟基喹啉衍生物上增加了一个醛基，测定增加在什么位置上。即产物为以下三个结构式中的哪一个？NOHCH3CHONOHCH3CHONOHCH3OHCppm(f1)0.05.010.010.1069.5429.5207.9257.9057.5247.5027.2607.2457.2252.758-0.0001.0000.9951.0541.0711.0363.145CDCl3ppm(f1)7.508.007.9257.9057.5247.5027.2607.2457.2251.0541.0711.036ppm(f1)9.4509.5009.5509.6009.5429.5200.995溶剂CDCl3实例三指认2,3-二氨基吩嗪的分子结构NNNH2NH2HHHHHHppm(t1)0.01.02.03.04.05.06.07.08.07.8857.8767.8697.8607.5337.5257.5167.5086.8946.2293.3432.4822.4782.4741.001.001.001.98ZPDDMSO-d6ppm(t1)7.507.607.707.807.908.007.8857.8767.8697.8607.5337.5257.5167.508ppm(t1)050100150144.051142.041140.286127.863126.416102.19040.15939.95339.74339.53539.32639.11838.908DMSO-d6ppm(t2)6.006.507.007.508.00100110120130140150ppm(t1)HSQC实例四确认是否得到了以下结构的化合物？OHONHOppm(f1)0.01.02.03.04.05.06.07.08.09.08.9726.8246.8036.7106.7056.6276.6216.6066.6004.7784.7663.9103.8953.8813.5063.4983.49