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1、碩士研究生課程高等波譜解析天然藥物及仿生藥物國家重點實驗室 博士研究生導(dǎo)師 楊 秀 偉 1H NMR 譜（一維）CH, CH2, CH3中質(zhì)子信號的歸屬1H 化學(xué)位移相關(guān)二維 NMR 譜 （自旋體系的解析） 13C NMR 譜（一維）INEPT 譜（識別碳原子基團）1H-13C 化學(xué)位移相關(guān)二維 NMR 譜 確定碳原子骨架NOE 相關(guān)二維 NMR 譜 NOE 差譜（確定 1H 的空間排布） 確定分子結(jié)構(gòu)（ 1H 原子的歸屬） 13C 原子的歸屬天然化合物結(jié)構(gòu)解析的一般程序 H = H0 - 2HH = H0 + 2H H = H0 + 3HH = H0 + HH = H0 - HH = H0
2、- 3H H = H0 + H - H = H0H = H0 - H + H = H0H0 H0 CHHH CH HCl (Triplet) (Quarterlet) CHHCl CH HH 1:2:1 1:3:3:1 可能存在自旋方向 預(yù)期圖譜 峰強度比 7.85(1H, d, J=9.5Hz, H-4) 6.18(1H, d, J=9.5Hz, H-3) 7.45(1H, d, J=8.3Hz, H-5) 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 (1H, dd
3、, J=2.2, 8.3Hz, H-6) 6.71 (1H, d, J=2.2Hz, H-8) The 1H NMR Spectrum of UmbelliferoneO OHO 1 234567 8 4a8a 72 8a 4 5 634a 8 The 13C NMR Spectrum of Umbelliferone 155.4111.3102.1161.2113.0 129.6 144.4 111.3160.31O OHO 7.921HdJ=9.5Hz H-4 7.471Hs H-5 6.781Hs H-8 6.21 1HdJ=9.5HzH-3 4.711HtJ=8.8Hz H-2 3.1
4、9 2HdJ=8.8Hz H-3 1.163Hs H-5 1.143HsH-68a4a876 5 4 321O OOHO 2345 6 The 1H NMR Spectrum of Nodakenetin The 13C NMR Spectrum of Nodakenetin 72 8a 4 65 4a3 8 2 4 3 56 O OOHO 160.4111.1144.5112.0155.0123.8125.4163.296.728.790.969.924.8 25.8 7.941Hd J=9.5HzH-4 6.231HdJ=9.5HzH-37.491HsH-5 6.231HsH-8 4.91
5、1HtJ=8.8Hz H-2 4.891Hd J=7.3HzH-1 4.401Hd J=7.3HzH-1 7.941HdJ=9.5Hz H-4 7.491HsH-5 6.811Hs H-8 6.231HdJ=9.5Hz H-3 4.911HtJ=8.8Hz H-2 4.891HdJ=7.3Hz H-1 4.401HdJ=8.0HzH-6b 3.681HddJ=8.0, 12.5Hz H-6a 3.282HdJ=8.8Hz H-3 1.323HsH-5 1.193HsH-6 The 1H NMR Spectrum of Nodakenin 65 4 32 1 234567 8 4a8aOOHHO
6、HO OH O O OO234 56 1 5 2 4 3 7 2 8a 4 65 34a 81 642 354 3 5 62 The 13C NMR Spectrum of Nodakenin 97.261.2 76.970.376.6 73.5 OOHHOHO OH O O OO155.0111.296.8123.8 125.4 144.6 112.2160.489.729.177.023.2 20.6 163.0 The 1H NMR Spectrum of Forbesoside 4.972Ht J=8.8HzH-3 4.621Hd J=7.8HzG-1 4.491Hdd J=11.6H
7、zG-6b 4.351HddJ=11.6HzG-6a OH 3.80 OMe 3.611HdddJ=2.3, 8.0, 9.0Hz G-5 G-3 G-4 G-22 7.601Hd J=9.3HzH-4 7.461Hd J=16.1HzH-8 7.171Hs H-5 6.891HdJ=2.0HzH-2 6.791HddJ=2.0, 8.1Hz H-6 6.681Hd J=8.1HzH-5 6.521Hs H-8 6.171Hd J=16.1HzH-7 6.091Hd J=9.3HzH-3 1654 3 2 8a4a876 5 4 3212345 6 O OOOOHHOHO OO OHO OMe
8、 7 8 9 The 1H NMR Spectrum of Tetraacetyl6-O-(trans-Feruloyl)Nodakenin 1654 3 2 8a4a876 5 4 321091112 13 O OOOOAcAcOAcO OCH2OMeAcO OO7 8 9 6 1234 5 The 1H NMR Spectrum of Tetraacetyl6-O-(trans-Feruloyl)nodakenin 7.601HdJ=16.0Hz H-7 7.521HdJ=9.5Hz H-4 7.121HsH-5 7.03 (2H, d, J=3.2Hz, H-5, 6)7.02 (1H,
9、 s, 2) 6.651HsH-8 6.311HdJ=16.0HzH-8 6.161HdJ=9.5HzH-3 5.241HtJ=9.4Hz H-3 5.061HtJ=9.4Hz H-4 4.941HddJ=9.4Hz H-2 4.801HtJ=8.8Hz H-10 4.831HdJ=8.1Hz H-1 4.351HddJ=2.7, 12.0Hz H-6b 4.281HddJ=6.1, 12.0HzH-6a 3.821HdddJ=2.9, 6.1, 9.4Hz H-5 3.853HsOMe 3.17 2HdJ=8.8HzH-9 2.333HsAr-OAc (-Me) 2.053HsGlc-OAc
10、 (-Me) 1.993HsGlc-OAc (-Me) 1.863HsGlc-OAc (-Me) 1.353Hs 13 1.263Hs121654 3 2 8a4a876 5 4 321091112 13 O OOOOAcAcOAcO OCH2OMeAcO OO7 8 9 6 1234 5 The 1H NMR Spectrum of Tetraacetyl6-O-(trans-Feruloyl)nodakenin The 13C NMR Spectrum of Tetraacetyl6-O-(trans-Feruloyl)nodakenin CO O CH3 CO O CH3 9 7 2 8
11、a 3 4 74 65 1 5 6 8 24a3 8 1 10 11 3 524 6 OMe 9 13 12 OMeO OH H H H161.3112.9143.7112.9152.8126.2107.3160.2117.9 6.19(d)7.58(d)7.27(d)6.81(d) 7.55(dd) 7.24(d) 6.10(s)OHH H H RH O7.33(dd) 8.18(d) 香豆素類化合物的NMR特征 O O + +- - C3、C6、C8-H在較高場C4、C5、C7-H在較低場 核磁共振波譜規(guī)律1H-NMR受內(nèi)酯羰基吸電子共軛效應(yīng)的影響 O OH H4 3 H-3, d,6.16.4 J=9.5HzH-4, d,7.58.3 J=9.5Hz O OHRO 37 C-7有氧取代，C-3 -0.17ppm O OR H45 C-5有基團取代，H-4 -0.3 ppm，在7.9-8.2之間 O OOH H2 3 2 3 OO OH H 呋喃香豆素如果呋喃環(huán)上沒有取代 H-2,H-2 7.34-7.80 線型H-36.7，角型H-37.0 O O234567 8 8a4a 160.4116.4143.6118.8128.1124.4131.8 116.4有OR取代 直接相連的碳 +30ppm鄰碳 13ppm對碳 8ppm13C-NMR
北京大學(xué)藥學(xué)院高等波譜解析前言和香豆素類化合物
