高等波谱解析硕士生讲义NMR-北京大学.ppt

单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,硕士研究生课程,高等波谱解析,北京大学药学院,天然药物及仿生药物国家重点实验室,博士研究生导师,杨 秀 伟,天然化合物结构解析的一般程序,可,能,存,在,自,旋,方,向,预,期,图,谱,峰,强,度,比,苯丙素,类化合物,典型的苯丙素类的,1,H NMR,数据,典型的苯丙素类的,13,C-NMR,数据,香豆素类化合物,7.85,(1H,d,J=9.5Hz,H-4),7.45,(1H,d,J=8.3Hz,H-5),6.18,(1H,d,J=9.5Hz,H-3),6.79,(1,H,dd,J=2.2,8.3Hz,H-6),6.71,(1H,d,J=2.2Hz,H-8),The,1,H NMR Spectrum of,Umbelliferone,香豆素类化合物的,NMR,特征,木脂素,异叶南五味子素,G,的,1,H-,1,H COSY,谱,异叶南五味子素,G,的,1,H-,13,C COSY,谱,黄酮类,13.0,12.5,8.0,7.5,7.0,6.5,6.0,12.85 s,OH-5,8.06 d,J=7.9Hz,H-2,6,7.58 m,H-3,4,5,6.94 s,H-3,6.53 d,J=1.9Hz,H-8,6.23 d,J=1.9Hz,H-6,白杨素,13.0,12.5,8.0,7.5,7.0,6.5,12.89 s,OH-5,7.87,dd,J=1.6,8.0Hz,H-6,7.41,dt,J=1.6,8.0Hz,H-4,7.07,dd,J=2.0,8.0Hz,H-3,7.06 s,H-3,7.01,dt,J=1.6,8.0Hz,H-5,6.48 d,J=2.0Hz,H-8,6.22 d,J=2.0Hz,H-6,5,7,2,-trihydroxyflavone,13.0,12.5,8.0,7.5,7.0,6.5,12.82 s,OH-5,7.96 d,J=8.7Hz,H-2,6,7.65 t,J=8.3Hz,H-7,7.13 d,J=8.3Hz,H-8,6.97 d,J=8.7Hz,H-3,5,6.90 s,H-3,6.79 d,J=8.3Hz,H-6,5,4,-Dihydroxyflavone,8.0,7.5,7.0,6.5,4.0,3.5,7-Hydroxy-4,-methoxyflavone,8.01 d,J=8.9Hz,H-2,6,7.89 d,J=8.7Hz,H-5,7.10 d,J=8.9Hz,H-3,5,7.00 d,J=2.1Hz,H-8,6.93,dd,J=2.2,8.7Hz,H-6,6.79 s,H-3,3.84,s,-,OMe,8.5,8.0,7.5,7.0,6.5,2,-,Hydroxy-4-methoxy,chalcone,7.92 d(J=15.4Hz,H-,),7.84 d(J=15.4Hz,H-,),6.98-7.06 m,H-,3,-5,7.56,dd,J=1.3,8.0Hz,H-,4,8.26,dd,J=1.3,8.0Hz,H-,6,7.89 d,J=8.6Hz,H-,2,-6,7.04 d,J=8.6Hz,H-,3 or-5,7.01 d,J=8.6Hz,H-,5 or-3,12.70,br,s,3.84,br,s,12.5,12.0,7.0,6.5,6.0,3.0,3.23,t,J=7.4Hz,H-,2.77,t,J=7.4Hz,H-,12.24,br,s,H-,2,5.82,s,H-,3,H-5,7.03,d,J=8.4Hz,H-,2,-6,6.67,d,J=8.4Hz,H-,3,-5,Phloretin,12.0,7.0,6.5,6.0,5.5,3.5,3.0,5.43,dd,J=2.8,12.7Hz,H-,2,3.26,dd,J=12.7,17.1Hz,H-,3ax,2.69,dd,J=2.8,17.1Hz,H-,3eq,12.15 s,5.90 s,H-6,-8,7.32 d,J=8.5Hz,H-,2,6,6.81 d,J=8.5Hz,H-,3,5,Naringenin,12.0,6.5,6.0,5.5,5.0,4.5,4.99 d,J=11.1Hz,H-,2,4.51 d,J=11.1Hz,H-,3,11.90 s,5-OH,5.88 d,J=2.0Hz,H-,6,5.92 d,J=2.0Hz,H-,8,6.89 s,H-2,6.75 s,H-5,H-6,Taxifolin,化合物,黄 酮,黄酮醇,异黄酮,左栏化合物的,7-,O-,糖苷,二氢黄酮,二氢黄酮醇,左栏化合物的,7-,O-,糖苷,H-6,6.00,6.20 d,6.20,6.40 d,5.75,5.95 d,5.90,6.10 d,H-8,6.30,6.50,6.50,6.90 d,5.90,6.10 d,6.10,6.40 d,5,7-,二羟基黄酮类化合物的,H-6,和,H-8,的化学位移（,）,低场,位移,低场,位移,化合物,H-5,H-6,H-8,黄 酮,黄酮醇,异黄酮,7.90 8.20,d,6.70 7.10,dd,6.70 7.00,d,二氢黄酮,二氢黄酮醇,7.70 7.90,d,6.40 6.50,dd,6.30 6.40,d,7-,OH,黄酮类化合物的,H-5、H-6,和,H-8,的化学位移,(,),化合物,二 氢 黄 酮,H-2,-6,7.10 7.30 d,H-3,-5,二氢黄酮醇,异 黄 酮,7.20 7.40 d,7.20 7.50 d,查 耳 酮,橙 酮,7.40 7.60 d,7.60 7.80 d,6.50 7.10 d,黄 酮,黄 酮 醇,7.70 7.90 d,7.90 8.10 d,4,-,氧取代黄酮类化合物的,H-2,，,H-6,和,H-3,，-5,的化学位移,(,),化 合 物,H-2,H-6,黄 酮,(3,4,OH,及,3,-,OH,4-,OMe,),7.20 7.30 d,7.30 7.50,黄酮醇,(3,4,OH,及,3,-,OH,4-,OMe,),7.50 7.70 d,7.60 7.90 d,黄酮醇,(3,-,OMe，4-OH),7.60 7.80 d,7.40 7.60 d,黄酮醇,(3,4-,OH,3,-O-,糖),7.20 7.50 d,7.30 7.70 d,3，4,-,二氧取代黄酮类化合物的,H-2,和,H-6,的化学位移（,）,化合物,二氢黄酮,二氢黄酮醇,二氢黄酮醇,3-,O,-,糖苷,H-2,5.00,5.50,dd,4.80,5.00,dd,5.00,5.60,dd,H-3,接近,2.80,dd,4.10,4.30,d,4.30,4.60,d,二氢黄酮和二氢黄酮醇的,H-2,和,H-3,的化学位移,(,),168.6 169.8(s),137.8 140.7(d),122.1 122.3(s),异橙酮类,174.5 184.0(s),160.5 163.2(s),104.7 111.8(d),黄酮类,149.8 155.4(d),122.3 125.9(s),异黄酮类,147.9(s),136.0(s),黄酮醇类,182.5 182.7(s),146.1 147.7(s),111.6 111.9(d),(=CH-),橙酮类,188.0 197.0(s),136.9 145.4(d),116.6 128.1(d),查耳酮类,75.0 80.3(d),42.8 44.6(t),二氢黄酮类,82.7(d),71.2(d),二氢黄酮醇类,13,C NMR,谱中黄酮类结构的中央三碳核的信号特征,（化学位移，,，,in DMSO-d,6,）,200,100,150,50,197.1,161.1,159.0,153.9,150.1,146.5,129.3,125.5,116.4,115.9,113.2,102.4,93.0,74.5,60.5,56.3,41.5,4,7,5,9,5,2,8,1,3,4,6,10,6,2,3,6,3,4,6,2,7-OMe,8-OMe,3a,3b,6.62,dd,6.75,d,6.92,d,6.25,s,5.70,dd,2.80,dd,3.18,dd,13,C-,1,H COSY Spectrum of(2,S,)-5,2,5,-trihydroxy-7,8-dimethoxyflavone,197.1,161.1,159.0,153.9,150.1,146.5,129.3,125.5,116.4,4,115.9,113.2,102.4,93.0,74.5,60.5,56.3,41.5,4,7,5,9,5,2,8,1,3,6,10,6,2,3,6,3,4,6,2,7-OMe,8-OMe,5-OH,*,*,*,2-OH,5-OH,*,*,*,3a,3b,*,*,12.5,8.0,7.5,7.0,6.5,12.6,5-OH,7.79,J=8.7Hz,2,6 H,6.93,J=8.7Hz,3,5 H,6.42,J=2.0Hz,8 H,6.22,J=2.0Hz,6 H,R,1,R,2,R,3,R,5,R,4,R,6,OH,OH,OH,OH,G,1,G,6,G,4,G,3,G,5,G,2,OH,5.5,5.0,4.5,4.0,3.5,3.0,1.0,1,H NMR Spectrum of,Kaempferol,3-O-glucosyl(1-2),-,rhamnoside,H,2,O,3.00,3.50,4.00,4.50,5.00,5.50,3.00,3.50,4.00,4.50,5.00,5.50,R,1,G,1,R,2,R,3,G,6,G,2,G,5,G,3,G,4,R,4,R,5,1,H-,1,H COSY Spectrum of,Kaempferol-3-,O,-glucosyl,(1,2)rhamnoside,OH,OH,OH,OH,82,80,78,76,74,72,70,68,66,64,62,3.00,3.20,3.40,3.60,3.80,4.00,4.20,81.5,77.5,77.0,75.7,73.5,71.8,71.0,71.0,61.7,R,2,R,5,R,3,R,4,G,2,G,6,G,3,G,5,G,4,1,H-,13,C COSY Spectrum of,Kaempferol-3-,O,-glucosyl,(12)rhamnoside,G,2,G,5,G,3,G,4,R,4,R,5,G,6,R,3,G,1,R,2,化 合 物,糖基,H-1,黄酮醇,3-,O,-,葡萄糖苷,5.70 6.00,黄酮类,7-,O,-,葡萄糖苷,4.80 5.20,黄酮类,4,-,O,-,葡萄糖苷,黄酮类,5-,O,-,葡萄糖苷,黄酮类,6-及8-,C,-,葡萄糖苷,黄酮醇,3-,O,-,鼠李糖苷,5.00 5.10,二氢黄酮醇,3-,O,-,葡萄糖苷,4.10 4.30,二氢黄酮醇,3-,O,-,鼠李糖苷,4.00 4.20,黄酮苷类化合物的糖基,H-1,的化学位移,苷化位置,苷 元 的 苷 化 位 移 平 均 值,2,3,4,5,6,7,8,9,10,1,2,3,4,5,6,7-,O-,糖,+0.8,-1.4,+1.1,+1.7,7-,O-,鼠李糖,+0.8,-2.4,+1.0,+1.7,3-,O-,糖,+9.2,-2.1,+1.5,+0.4,+1.0,-0.8,+1.1,-0.3,+0.7,-0.4,+1.5,3-,O-,鼠李糖,+10.3,-1.1,+2.0,+0.6,+1.1,5-,O-,葡萄糖,-2.8,+2.2,-6.0,-2.7,+4.4,-3.0,+3.2,+1.4,+4.3,-1.3,-1.2,-0.4,-0.8,-1.0,-1.2,3,-,O-,葡萄糖,-0.5,+0.4,+1.6,+1.4,+0.4,+3.2,4,-,O-,葡萄糖,+0.1,+1.0,+3.7,+0.4,+2.0,-1.2,+1.4,黄酮类化合物,13,C NMR,谱苷化位移（,）,二萜,1,H NMR Spectrum of,Andrographolide,20,18,5,1,6,1,6,9,2,7,7,11,19,a,3,19,b,15,15,17,b,17a,14,12,12,14,17,b,17a,15,15,19,b,3,19,a,11,7,7,2,9,6,1,6,1,5,18,20,1,H-,1,H COSY Spectrum,of,Andrographolide,13,C NMR Spectrum of,Andrographolide,DEPT Spectrum of,Andrographolide,15.1,15.1,23.7,23.7,24.3,24.3,24.9,24.9,28.9,28.9,37.2,37.2,38.1,38.1,55.2,55.2,56.3,56.3,56.3,55.2,75.4,75.4,79.8,65.9,79.8,79.8,65.9,65.9,64.1,64.1,108.8,108.8,147.0,147.0,147.0,HMQC Spectrum of,Andrographolide,20,20,18,6,6,6,11,11,2,2,1,1,7,7,7,10,4,5,5,9,9,19a,19b,19,14,14,15,15,15,3,3,17,17b,17a,13,12,8,12,HMQC Spectrum of,Andrographolide,1,18,HMBC Spectrum of,Andrographolide,16,12,8,13,17,15,3,14,19,9,5,4,10,7,1,2,11,6,18,20,20,5,1,6,18,1,6,9,2,7,7,11,19,a,3,19,b,15,15,17,a,17,b,14,12,1,H NMR Spectrum of,Neoandrographolide,13,C NMR Spectrum of,Neoandrographolide,145.4,145.4,106.9,106.9,105.5,105.5,78.7,78.7,78.4,78.4,75.3,75.3,72.6,72.6,70.6,70.6,71.7,71.7,62.8,62.8,56.7,56.7,56.2,56.2,39.0,39.0,38.7,38.7,36.4,36.4,28.2,28.2,24.6,22.1,22.1,24.6,25.0,25.0,19.3,19.3,15.4,15.4,DEPT Spectrum of,Neoandrographolide,1,H NMR Spectrum of,14-,Deoxyandrographolide,-19-,-D-,Glucoside,13,C NMR Spectrum of,14-,Deoxyandrographolide,-19-,-D-,Glucoside,6,15,17,b,1,20,a,20,b,19a,19b,9,13,5,14b,11b,2ab,18,3a,12ab,14a,3b,11a,17,a,OH,C,20,H,26,O,5,C,20,H,34,O,3,20,18,19,7,17,9,15,5,3,1,14,6,12,11,2,三萜,3,5,2,6,a,6,b,3,4,12,1,62.7,98.1,C-K-1,C-K-1,NaOMe,/,MeOH,C,16,H,32,O,2,MW=256,EI-MS m/z:270,ESI-MS m/z:861,甾 类,A,B,Fig.2,1,H NMR Spectrum of,Budesonide,-,R,13,C NMR and DEPT Spectra of,Budesonide,-,R,C,9,H,9,CH,CH,3,:12C 9C=CH,3,x 3 C,12,H,18,CH,2,x 7 C,7,H,14,C:25C 19C C,6,C,25,H,34,O,6,O,O,O,O,O,O,OH,OH,1,2,4,16,22,21,b,11,21,a,6,6,8,7,12,15,12,1,14,15,19,2,7,9,3,18,1,2,4,22,17,16,11,21,9,14,13,10,12,1,7,15,6,8,19,18,2,3,HSQC Spectrum of,Budesonide,-,R,1,2,4,16,22,21,b,11,21,a,6,6,8,7,12,15,12,1,14,15,19,2,7,9,3,18,20,3,5,1,2,4,22,17,16,11,21,9,14,13,10,12,3,18,2,19,8,1,6,15,7,HMBC Spectrum of,Budesonide,-,R,1,1,2,2,4,4,16,16,22,22,21,b,11,21,b,11,21,a,21,a,6,6,6,6,8,8,7,7,12,12,15,15,12,1,14,15,12,1,14,15,19,19,2,2,7,7,9,9,18,3,18,3,1,H-,1,H COSY Spectrum of,Budesonide,-,R,911,1211,1211,221,1615,2,3,67,89,77,67,67,1,1,2,2,4,4,16,16,22,22,21,b,11,21,b,11,21,a,21,a,6,6,6,6,8,8,7,7,12,12,15,15,12,1,14,15,12,1,14,15,19,19,2,2,9,9,7,7,3,18,3,18,NOESY Spectrum of,Budesonide,-,R,119,111,椅式,12,6,4,椅式,16,22,18,16,*,生 物 碱,A,B,*,*,*,*,1,H-NMR,波谱法在杂质检查或纯度试验中的应用,22(,R,)-,Budesonide,-R:22(,S,)-,Budesonide,-R=99.91:0.09,1,H NMR Spectrum of,Evodiamine,N-H,N-Me,N-Me,N-H,6ab,6ab,5a,5a,5b,5b,3,3,16,10,18,18,10,16,11,11,12,12,17,9,17,9,19,19,1,H-,1,H COSY Spectrum,of,Evodiamine,19,19,17,17,9,9,12,12,11,11,18,18,10,16,10,16,13,C NMR Spectrum of,Evodiamine,19.5,19.5,36.4,36.4,40.8,40.8,69.7,69.7,111.6,111.6,133.4,133.4,128.0,128.0,121.8,120.3,118.9,121.8,120.3,118.9,118.2,117.4,118.2,117.4,DEPT Spectrum of,Evodiamine,CH,3,x 1,CH,2,x 2,CH x 9,C,19,H,17,N,3,O,6,ab,N-Me,5a,5b,3,18,10,16,11,12,17,9,19,N-H,N-Me,6,5,3,12,7,16,9,10,8,11,18,19,2,17,13,15,21,20,HMQC Spectrum of,Evodiamine,N-1,19,17,9,12,11,18,10,16,3,5b,5a,6ab,N-Me,5,3,N-Me,7,12,16,9,10,20,18,11,8,19,2,17,13,15,21,HMBC Spectrum of,Evodiamine,1,H NMR Spectrum of,Rutaecarpine,13,C NMR Spectrum of,Rutaecarpine,18.9,18.9,40.8,40.8,112.5,119.9,119.7,112.5,119.9,119.7,124.7,124.7,125.9,125.9,126.4,126.4,126.6,126.6,134.4,134.4,19,19,10,10,11,11,18,18,12,12,9,16,16,9,17,17,N-H,N-H,5,5,6,6,1,H-,1,H COSY Spectrum,of,Rutaecarpine,19,19,17,17,16,16,9,9,12,12,18,18,11,11,10,10,N-H,19,19,17,17,16,16,9,9,12,12,18,18,11,11,10,10,5,6,6,5,12,12,7,7,9,9,10,10,20,20,11,8,18,16,19,2,17,17,2,19,13,3,15,21,HMQC Spectrum of,Rutaecarpine,N-H,19,19,10,10,11,18,12,9,16,17,17,11,6,5,12,7,12,7,10,10,9,9,20,20,11,8,18,16,19,2,17,13,3,15,21,5,6,HMBC Spectrum of,Rutaecarpine,18,12,2,1,H NMR Spectrum of,Dehydroevodiamine,6,5,6,5,10,10,10,11,11,11,12,12,12,18,9,17,16,19,19,16,17,9,18,19,16,17,9,18,10,11,12,18,9,17,16,19,N-H,N-H,1,H-,1,H COSY Spectrum,of,Dehydroevodiamine,N-Me,N-Me,13,C NMR Spectrum of,Dehydroevodiamine,18.5,18.5,40.9,40.9,42.1,42.1,113.6,113.6,118.6,118.6,121.6,121.6,127.7,127.7,128.6,128.7,128.6,128.7,136.7,136.7,DEPT Spectrum of,Dehydroevodiamine,6,5,N-Me,N-H,10,11,12,18,9,17,16,19,6,5,N-Me,12,16,9,10,19,18,11,17,21,3,13,15,2,8,7,20,HMQC Spectrum of,Dehydroevodiamine,10,11,12,18,9,17,16,19,9,10,8,7,19,18,11,2,17,15,13,16,12,20,10,10,11,11,12,12,18,18,9,9,17,17,16,16,19,19,6,5,5,6,N-H,N-Me,N-Me,12,12,16,16,20,20,7,7,9,10,9,10,8,8,19,19,18,11,18,11,2,2,17,17,15,15,13,13,3,3,21,21,HMBC Spectrum of,Dehydroevodiamine,10,11,12,18,9,17,16,19,6,5,5,6,N-H,N-Me,N-Me,12,16,20,7,9,10,8,19,18,11,2,17,15,13,3,21,HMBC Spectrum of,Dehydroevodiamine,11,10,12,18,9,16,17,19,12,16,20,7,9,10,8,19,18,11,2,17,15,13,3,21,19,16,17,9,18,12,11,10,12,16,20,7,9,10,8,19,18,11,2,17,15,13,3,21,HMBC Spectrum of,Dehydroevodiamine,7.4,7.3,7.2,7.1,7.0,7.45,1H,d,J=8.0Hz,7.34,1H,d,J=8.0Hz,7.09,1,H,ddd,J=1.0,7.5,7.5Hz,7.00,1,H,ddd,J=1.0,7.5,7.5Hz,4.52,1,H,dd,J=6.5Hz,3.61,1,H,dd,J=4.8,11.8Hz,3.16,1,H,dd,J=4.8,14.8Hz,2.78,1,H,ddd,J=2.5,12.4,15.6Hz,1.62,1H,d,J=6.5Hz,8.76,1,H,br,s,11.10,1H,s,17.0,23.2,49.0,57.6,106.8,111.2,118.0,118.8,121.4,126.1,132.2,136.4,169.4,The HMBC Spectrum of AP-6,17.0,23.2,49.0,57.6,The HSQC Spectrum of AP-6,106.8,111.2,118.0,118.8,121.4,126.1,The,1,H-,1,H COSY Spectrum of AP-6,The,1,H-,1,H COSY Spectrum of AP-6,The NOE Spectrum of AP-6,11.10,7.45,7.34,7.09,7.00,4.52,3.61,3.16,2.78,1.62,1.62,2.78,3.16,3.61,4.52,7.00,7.09,7.34,7.45,11.10,2.78,3.16,3.61,4.52,4.52,3.61,3.16,2.78,1.62,1.62,The NOE Spectrum of AP-6,构型和构象不同，化学位移也不同。,II,II,II,II,I,1,3,5,4,2,6,I,I,I,I,+,II,1,N,-CH,3,2,3,构型和构象,不同，化学位移,也不同。,l,-Ephedrine(,I,),d,-,Pseudoephedrine,(,II,),Stephacidin,A,ORTEP drawing of,stephacidin,A,来源：赭曲霉,(,Aspergillus,ochraceus,),Structure of,sieboldine,A,来源：,鳞叶马尾杉(,Lycopodium,sieboldii,),ORTEP drawing of,sieboldine,A,