碩士生講義NMR2006資料

碩士研究生課程高等波譜解析北京大學(xué)藥學(xué)院天然藥物及仿生藥物國家重點(diǎn)實(shí)驗(yàn)室

博士研究生導(dǎo)師

楊秀偉天然化合物結(jié)構(gòu)解析的一般程序

可能存在自旋方向

預(yù)期圖譜

峰強(qiáng)度比

苯丙素類化合物典型的苯丙素類的1HNMR數(shù)據(jù)

典型的苯丙素類的13C-NMR數(shù)據(jù)

香豆素類化合物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(1H,dd,J=2.2,8.3Hz,H-6)6.71(1H,d,J=2.2Hz,H-8)The1HNMRSpectrumofUmbelliferone香豆素類化合物的NMR特征木脂素異葉南五味子素G的1H-1HCOSY譜異葉南五味子素G的1H-13CCOSY譜黃酮類13.012.58.07.57.06.56.012.85s

OH-58.06dJ=7.9Hz

H-2',6'7.58m

H-3',4',5'6.94s

H-36.53dJ=1.9Hz

H-86.23dJ=1.9Hz

H-6白楊素13.012.58.07.57.06.512.89s

OH-57.87ddJ=1.6,8.0Hz

H-6'7.41dtJ=1.6,8.0Hz

H-4'7.07ddJ=2.0,8.0Hz

H-3'7.06s

H-37.01dtJ=1.6,8.0Hz

H-5'6.48dJ=2.0Hz

H-86.22dJ=2.0Hz

H-65,7,2'-trihydroxyflavone13.012.58.07.57.06.512.82s

OH-57.96dJ=8.7Hz

H-2',6'7.65tJ=8.3Hz

H-77.13dJ=8.3Hz

H-86.97dJ=8.7Hz

H-3',5'6.90s

H-36.79dJ=8.3Hz

H-65,4'-Dihydroxyflavone8.07.57.06.54.03.57-Hydroxy-4'-methoxyflavone8.01dJ=8.9Hz

H-2',6'7.89dJ=8.7Hz

H-57.10dJ=8.9Hz

H-3',5'7.00dJ=2.1Hz

H-86.93ddJ=2.2,8.7Hz

H-66.79s

H-33.84s-OMe8.58.07.57.06.52'-Hydroxy-4-methoxychalcone7.92d(J=15.4Hz,H-)7.84d(J=15.4Hz,H-)6.98-7.06mH-3',-5'7.56ddJ=1.3,8.0HzH-4'8.26ddJ=1.3,8.0HzH-6'7.89dJ=8.6HzH-2,-67.04dJ=8.6HzH-3or-57.01dJ=8.6HzH-5or-312.70brs3.84brs12.512.07.06.56.03.03.23tJ=7.4HzH-2.77tJ=7.4HzH-12.24

brsH-2'5.82sH-3'H-5'7.03dJ=8.4HzH-2,-66.67dJ=8.4HzH-3,-5Phloretin12.07.06.56.05.53.53.05.43ddJ=2.8,12.7HzH-23.26ddJ=12.7,17.1HzH-3ax2.69ddJ=2.8,17.1HzH-3eq12.15s5.90sH-6,-87.32dJ=8.5HzH-2',6'6.81dJ=8.5HzH-3',5'Naringenin12.06.56.05.55.04.54.99dJ=11.1Hz

H-2

4.51dJ=11.1HzH-311.90s5-OH5.88dJ=2.0Hz

H-65.92dJ=2.0Hz

H-8

6.89sH-2'

6.75sH-5',H-6'

Taxifolin化合物黃酮黃酮醇異黃酮左欄化合物的7-O-糖苷二氫黃酮二氫黃酮醇左欄化合物的7-O-糖苷H-66.00~6.20d6.20~6.40d5.75~5.95d5.90~6.10dH-86.30~6.506.50~6.90d5.90~6.10d6.10~6.40d5,7-二羥基黃酮類化合物的H-6和H-8的化學(xué)位移（）低場位移低場位移化合物H-5H-6H-8黃酮黃酮醇異黃酮7.90~8.20d6.70~7.10dd6.70~7.00d二氫黃酮二氫黃酮醇7.70~7.90d6.40~6.50dd6.30~6.40d7-OH黃酮類化合物的H-5、H-6和H-8的化學(xué)位移()化合物二氫黃酮H-2',-6'7.10~7.30dH-3',-5‘二氫黃酮醇異黃酮7.20~7.40d7.20~7.50d查耳酮橙酮7.40~7.60d7.60~7.80d6.50~7.10d黃酮黃酮醇7.70~7.90d7.90~8.10d4'

-氧取代黃酮類化合物的H-2'

，H-6'和H-3'，-5'的化學(xué)位移()化合物H-2'H-6'黃酮(3',4'–OH

及3'-OH,4'-OMe)7.20~7.30d7.30~7.50黃酮醇(3',4'–OH

及3'-OH,4'-OMe)7.50~7.70d7.60~7.90d黃酮醇(3'-OMe，4'-OH)7.60~7.80d7.40~7.60d黃酮醇(3',4'-OH,3-O-糖)7.20~7.50d7.30~7.70d3'，4'

-二氧取代黃酮類化合物的

H-2'和H-6'的化學(xué)位移（）化合物二氫黃酮二氫黃酮醇二氫黃酮醇3-O-糖苷H-25.00~5.50dd4.80~5.00dd5.00~5.60ddH-3接近2.80dd4.10~4.30d4.30~4.60d二氫黃酮和二氫黃酮醇的H-2和H-3的化學(xué)位移()168.6~169.8(s)137.8~140.7(d)122.1~122.3(s)異橙酮類174.5~184.0(s)160.5~163.2(s)104.7~111.8(d)黃酮類149.8~155.4(d)122.3~125.9(s)異黃酮類147.9(s)136.0(s)黃酮醇類182.5~182.7(s)146.1~147.7(s)111.6~111.9(d)(=CH-)橙酮類188.0~197.0(s)136.9~145.4(d)116.6~128.1(d)查耳酮類75.0~80.3(d)42.8~44.6(t)二氫黃酮類82.7(d)71.2(d)二氫黃酮醇類13CNMR譜中黃酮類結(jié)構(gòu)的中央三碳核的信號(hào)特征

（化學(xué)位移，，inDMSO-d6）20010015050197.1161.1159.0153.9150.1146.5129.3125.5116.4115.9113.2102.493.074.560.556.341.547595‘2‘81‘3‘4‘6‘106236‘3‘4‘627-OMe8-OMe3a3b6.62,dd6.75,d6.92,d6.25,s5.70,dd2.80,dd3.18,dd13C-1HCOSYSpectrumof(2S)-5,2',5'-trihydroxy-7,8-dimethoxyflavone197.1161.1159.0153.9150.1146.5129.3125.5116.44‘115.9113.2102.493.074.560.556.341.547595‘2‘81‘3‘6‘106236‘3‘4‘627-OMe8-OMe5-OH***2‘-OH5‘-OH***3a3b**12.58.07.57.06.512.65-OH7.79J=8.7Hz2’,6’–H6.93J=8.7Hz3’,5’–H

6.42J=2.0Hz8–H

6.22J=2.0Hz6–HR1R2R3R5R4R6OHOHOHOHG1G6G4G3G5G2OH5.55.04.54.03.53.01.01HNMRSpectrumofKaempferol3-O-glucosyl(1-2)-rhamnosideH2O3.003.504.004.505.005.503.003.504.004.505.005.50R1G1R2R3G6G2,G5G3,G4,R4R51H-1HCOSYSpectrumofKaempferol-3-O-glucosyl(1→2)rhamnosideOHOHOHOH82807876747270686664623.003.203.403.603.804.004.2081.577.577.075.773.571.871.071.061.7R2R5R3R4G2G6G3G5G41H-13CCOSYSpectrumofKaempferol-3-O-glucosyl(1→2)rhamnosideG2,G5G3,G4

,R4R5G6R3G1R2化合物糖基H-1黃酮醇3-O-葡萄糖苷5.70~6.00黃酮類7-O-葡萄糖苷4.80~5.20黃酮類4'-O-葡萄糖苷黃酮類5-O-葡萄糖苷黃酮類6-及8-C-葡萄糖苷黃酮醇3-O-鼠李糖苷5.00~5.10二氫黃酮醇3-O-葡萄糖苷4.10~4.30二氫黃酮醇3-O-鼠李糖苷4.00~4.20黃酮苷類化合物的糖基H-1的化學(xué)位移苷化位置苷元的苷化位移平均值23456789101'2'3'4'5'6'7-O-糖+0.8-1.4+1.1+1.77-O-鼠李糖+0.8-2.4+1.0+1.73-O-糖+9.2-2.1+1.5+0.4+1.0-0.8+1.1-0.3+0.7-0.4+1.53-O-鼠李糖+10.3-1.1+2.0+0.6+1.15-O-葡萄糖-2.8+2.2-6.0-2.7+4.4-3.0+3.2+1.4+4.3-1.3-1.2-0.4-0.8-1.0-1.23'-O-葡萄糖-0.5+0.4+1.6+1.4+0.4+3.24'-O-葡萄糖+0.1+1.0+3.7+0.4+2.0-1.2+1.4黃酮類化合物13CNMR譜苷化位移（）二萜1HNMRSpectrumof

Andrographolide20185161692771119a319b151517b17a1412121417b,17a151519b319a1177296161518201H-1HCOSYSpectrumof

Andrographolide13CNMRSpectrumofAndrographolide

DEPTSpectrumofAndrographolide15.115.123.723.724.324.324.924.928.928.937.237.238.138.155.255.256.356.356.355.275.475.479.865.979.879.865.965.964.164.1108.8108.8147.0147.0147.0HMQCSpectrumofAndrographolide20201866611112211777104559919a19b191414151515331717b17a1312812HMQCSpectrumofAndrographolide118HMBCSpectrumof

Andrographolide161281317153141995410712116182020516181692771119a319b151517a17b14121HNMRSpectrumof

Neoandrographolide13CNMRSpectrumof

Neoandrographolide145.4145.4106.9106.9105.5105.578.778.778.478.475.375.372.672.670.670.671.771.762.862.856.756.756.256.239.039.038.738.736.436.428.228.224.622.122.124.625.025.019.319.315.415.4DEPTSpectrumof

Neoandrographolide1HNMRSpectrumof

14-Deoxyandrographolide-19--D-Glucoside13CNMRSpectrumof

14-Deoxyandrographolide-19--D-Glucoside61517b120a20b19a19b913514b11b2ab183a12ab14a3b11a17aOHC20H26O5C20H34O320181971791553114612112三萜3'5'2'6‘a(chǎn)6‘b3‘4‘121'62.798.1C-K-1C-K-1NaOMe/MeOHC16H32O2MW=256EI-MSm/z:270ESI-MSm/z:861甾類ABFig.21HNMRSpectrumofBudesonide-R13CNMRandDEPTSpectraofBudesonide-RC9H9CH,CH3:12C–9C=CH3x3→C12H18CH2x7→C7H14C:25C–19C→C6C25H34O6OOOOOOOHOH124162221b1121a66871215121'1415192'793'1812422171611219141310121'715681918,2'3'HSQCSpectrumofBudesonide-R124162221b1121a66871215121‘1415192'793'18203512422171611219141310123'18,2'1981'615,7HMBCSpectrumofBudesonide-R1122441616222221b,1121b1121a21a666688771212151512,1',14,15121'141519192'2'779918,3'183'1H-1HCOSYSpectrumofBudesonide-R9?1112?1112?1122?1'16?152‘?3'6?78?97?76?76?71122441616222221b1121b,1121a21a6666887712121515121'141512,1',14,1519192'2'99773'183',18NOESYSpectrumofBudesonide-R1?191?11椅式1?26?4椅式16?2218?16*生物堿AB****1H-NMR波譜法在雜質(zhì)檢查或純度試驗(yàn)中的應(yīng)用22(R)-Budesonide-R:22(S)-Budesonide-R=99.91:0.091HNMRSpectrumofEvodiamineN-HN-MeN-MeN-H6ab6ab5a5a5b5b331610181810161111121217,917919191H-1HCOSYSpectrumofEvodiamine19191717991212111118181016101613CNMRSpectrumofEvodiamine19.519.536.436.440.840.869.769.7111.6111.6133.4133.4128.0128.0121.8120.3118.9121.8120.3118.9118.2117.4118.2117.4DEPTSpectrumofEvodiamineCH3x1CH2x2CHx9C19H17N3O6abN-Me5a5b3181016111217919N-HN-Me65312,716910811181921713152120HMQCSpectrumofEvodiamineN-119179121118101635b5a6abN-Me53N-Me7,1216910201811819217131521HMBCSpectrumofEvodiamine1HNMRSpectrumofRutaecarpine13CNMRSpectrumofRutaecarpine18.918.940.840.8112.5119.9119.7112.5119.9119.7124.7124.7125.9125.9126.4126.4126.6126.6134.4134.41919101011111818121291616,91717N-HN-H55661H-1HCOSYSpectrumofRutaecarpine191917171616991212181811111010N-H19191717161699121218181111101056651212779910102020118181619217172191331521HMQCSpectrumofRutaecarpineN-H19191010111812916171711651271271010992020118181619217133152156HMBCSpectrumofRutaecarpine181221HNMRSpectrumofDehydroevodiamine65651010101111111212121891716191916179181916,179,18101112189171619N-HN-H1H-1HCOSYSpectrumofDehydroevodiamineN-MeN-Me13CNMRSpectrumofDehydroevodiamine18.518.540.940.942.142.1113.6113.6118.6118.6121.6121.6127.7127.7128.6128.7128.6128.7136.7136.7DEPTSpectrumofDehydroevodiamine65N-MeN-H10111218917161965N-Me12169,101918,1117213131528720HMQCSpectrumofDehydroevodiamine1011121891716199,10871918,1121715131612201010111112121818991717161619196556N-HN-MeN-Me121216162020779,109,1088191918,1118,1122171715151313332121HMBCSpectrumofDehydroevodiamine1011121891716196556N-HN-MeN-Me12162079,1081918,112171513321HMBCSpectrumofDehydroevodiamine11101218916171912162079,1081918,11217151332119161791812111012162079,1081918,112171513321HMBCSpectrumofDehydroevodiamine7.47.37.2