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11.从一种植物中得到一个黄色针状结晶,酸水解后,苷元经理化性质和波谱数据推断为3,5,7,4'-四羟基黄酮,纸色谱检查表明该化合物含有葡萄糖和鼠李糖,经质谱测定表明该化合物是一个双糖苷类化合物。该化合物及苷元的13C-NMR数据如下所示,请根据该化合物及苷元的13C-NMR数据推断出该化合物的化学结构。NO苷元苷NO苷元苷NO苷元苷2146.1156.62'129.3130.966.93135.5133.53'111.5115.2100.64175.7177.54'159.0159.970.35160.0161.35'115.3115.270.7698.298.86'129.3130.972.07163.8164.2糖101.568.1893.493.874.217.19160.5156.976.510102.9104.270.11'121.6121.175.8葡萄糖甲苷鼠李糖甲苷编号δ编号δ1104.01102.6274.1272.1376.8372.7470.6473.8576.8569.5661.8618.6OOOHOHOHHOOOHOOHHOOHOOHOOOHOOHHOHOH3C22.从一种中药材中分得一个三萜类化合物,酸水解后,经纸色谱检查表明该化合物含有β-D-葡萄糖,经质谱测定推算该化合物含有两个六碳醛糖,酸水解后所获苷元通过理化性质和波谱数据推测其苷元的结构如下式所示。该化合物及苷元的13C-NMR数据如下所示,请根据该化合物及苷元的13C-NMR数据推断出该化合物的化学结构。碳的编号苷元苷碳的编号苷元苷碳的编号苷元苷139.539.71625.825.8糖103.6228.127.81749.549.579.9378.478.01817.817.978.6440.340.31917.217.371.7561.961.52087.087.179.9667.779.92126.927.163.0747.545.02232.632.4103.9841.241.22328.729.076.0950.250.42488.488.478.61039.339.72570.070.172.41132.232.42626.626.779.91270.871.02729.029.063.51349.149.22831.932.41452.252.32916.516.81532.632.43018.117.93OOHHOOHHO葡萄糖甲苷的数据1105.4274.8378.1471.4578.1662.5123456891011121314151617181920212223242526272829307OOHOOHHO123456891011121314151617181920212223242526272829307OHOHOOOHOHOHOOHOH43.某化合物C10H8O3,有蓝色荧光。1H-NMR(CDCl3)δ:7.58(1H,d,J=9.5Hz),6.17(1H,d,J=9.5Hz),6.78(1H,dd,J=8,2.5Hz),6.72(1H,d,J=2.5Hz),7.32(1H,d,J=8Hz),3.82(3H,s).试写出化合物结构,并归属各质子信号。4.某化合物C15H16O3,有蓝紫色荧光。1H-NMR(CDCl3)δ:1.66(3H,s),1.81(3H,s),3.52(2H,d,J=7Hz),3.92(3H,s),5.22(1H,t,J=7Hz),6.20(1H,d,J=9Hz),6.81(1H,d,J=8Hz),7.27(1H,d,J=8Hz),7.59(1H,d,J=9Hz).试写出化合物结构,并归属各质子信号。5.用化学或波谱方法区分下列各组化合物(1)OHOOAOOBOCH3(2)OHOOAOOBHOH3CO(3)OOOAOOBH3COHOHOGlc(4)5OH3COOAOOH3COH3COOCH3B(5)OOOOOOOOOOOAB(6)OOOOCH3OCH3H3COOAOOOOCH3OCH3H3COOB(7)6OOOOCH3OCH3H3COOAOOOOCH3OCH3H3COBO一、写出下列反应产物的结构式或各反应试剂条件。OOOHCOOHOHOH1.CH2N2/Et2OOOOHCH2OHOH2.OOOAcCH2OAcOHA+BH2O7OOOHCH2OHOHOHHOOHAc2O回流2min3.OOCH2OHCHOOHOH4.OOCH2OMeCH(OMe)2OMeOMeCOOOHCH2OHHOH3BO3Ac2ODH2OE5.OOCOOHOHOHMe2SO4/K2CO3Me2CO6.二、某中药中存在下列化合物,经下列流程分离后,各出现在何部位?简述理由。(A)大黄酸(B)大黄酚(C)大黄酚葡萄糖苷8OOOCH3CH3OHOCH3DHOEOOOHCH3OHOCH3F药材粗粉95%乙醇提取不溶物甲Et2O溶液醇提物5%NaHCO3萃取碱水液Et2O溶液酸化黄色沉淀乙5%Na2CO3萃取碱水液Et2O溶液酸化黄色沉淀丙1%NaOH萃取碱水液Et2O溶液酸化黄色沉淀丁5%NaOH萃取碱水液Et2O溶液已酸化黄色沉淀戊三、总蒽醌的乙醚提取液进一步分离后,得到以下六种成分。请在下面的分离9流程图括号内填入正确的化合物代号。OOOHOHOOOHOHH3COHCH3ABOOOHOHOOOHOHH3COOHCH3CDOOOHOHHOOOOHOHHOH2CCHOCOOHEF水层Et2O层总蒽醌的乙醚提取液5%NaHCO3水液萃取水层Et2O层硅胶柱层析5%Na2CO3水液萃取硅胶柱层析先洗下次洗下后洗下先洗下后洗下(2)(3)(4)(5)(6)(1)氯仿-甲醇梯度洗脱氯仿-甲醇梯度洗脱10结构鉴定一种蒽醌苷,经酸水解后生成芦荟大黄素和D-葡萄糖,苷的红外光谱显示1626cm-1,1674cm-1吸收峰。苷全甲基化合物经甲醇解后得到甲基苷元,其IR显示1665cm-1,3480cm-1吸收峰。苷的全甲基化衍生物有δ4.88(1H,d,J=7.2Hz)信号。回答:1.IR光谱全甲基化前后数据的不同之处。2.糖的连接位置。3.糖的构型。4.写出此蒽醌苷的结构。OOOHOHHOH2C用化学方法区分下列化合物OOOHHOOHOHAOHOOHHOOHOHB1.11OOOHH3COOHAOOHOOHOHB2.OOH3COOHOHCOOOHHOOCH3AOOHOOHOHB3.OOHOOHCOHOHOOOHHOOAOOHOOHOHB4.OOHOOHCOHOHOHOOH12OOOHH3COOCH3AOOH3COOCH3OB5.OOH3COOHCOHOHOHOCH3OCH3OCH3OCH3glcOOH3COOHDOHOHOHOOOHHOOCH3AOOHOOHOHB6.OHOCH3OOOHH3COOHAOOH3COOHOHB7.OOH3COOHCOHOOOHHOOAOOHOOHOHB8.OOHOOHCOHOHOHOOHOH13用Sephadex-LH20凝胶柱色谱,分离下列黄酮类化合物,以甲醇-水溶剂系统进行洗脱。请说明流出柱的先后顺序,并说明其原理。OOOHglc-OOHAOOHOOHOBOOHOOHCOHOHO-glc-rhaglc-rhaOOHOOHDOHOHOOHOOHEOHOOHOOHFOHOHOHOCH3OHO-glc用聚酰胺柱色谱,分离下列黄酮类化合物,以乙醇-水溶剂系统进行洗脱。请说明流出柱的先后顺序,并说明其原理。14OOOHrha-glc-OOHAOOglc-OOHOHBOOHOOHCOHOHOHOOHOOHDOHOHOOrha-glc-OOHEOHOOHOOHFOHOHOHOHO-glc某中药含有如下成分:A多糖、B芦丁、C槲皮素,若采用下列流程进行分离,请将各成分填入括号内。药材粗粉水煎煮后,过滤残渣滤液浓缩后,加入5倍量乙醇沉淀上清液聚酰胺柱以水,水液稀浓度醇洗液高浓度醇洗液含水醇洗脱()()()()151.有一黄色结晶(I),盐酸镁粉反应显红色,Molish反应(+),FeCl3反应(+),ZrOCl2反应呈黄色,但加入枸橼酸后黄色褪去。(I)的UVλmaxnm:MeOH252267(sh)346NaOMe261399AlCl3272426AlCl3/HCl260274357385NaOAc254400NaOAc/H3BO3256378(I)的1H-NMR(DMSO-d6)δ:7.20(1H,d,J=3Hz),6.92(1H,dd,J=8,3Hz),6.70(1H,d,J=8Hz),6.62(1H,d,J=2Hz),6.43(1H,d,J=2Hz),6.38(1H,s),5.05(1H,d,J=7Hz),其余略。(I)酸水解后检出D-葡萄糖和苷元,苷元的分子式为C15H10O6,FAB-MS示分子中含一分子葡萄糖。写出(I)的结构。162.有一黄色结晶粉末(II),盐酸镁粉反应显红色,Molish反应(+),FeCl3反应(+),纸色谱只检测出D-葡萄糖。(II)的UVλmaxnm:MeOH254267(sh)349NaOMe268395AlCl3273298(sh)330(sh)425AlCl3/HCl270296(sh)360385NaOAc257405NaOAc/H3BO3258371(II)的1H-NMR(DMSO-d6)δ:12.93(1H,br.s),10.21(1H,br.s),9.80(1H,br.s),7.20(1H,dd,J=8,2Hz),7.40(1H,d,J=2.0Hz),6.90(1H,d,J=8Hz),6.8(1H,d,J=2.1Hz),6.7(1H,s),6.5(1H,d,J=2.1Hz),5.2(1H,d,J=7.0Hz),4.50(1H,d,J=7.8Hz),3.3~3.8(m,12H);(II)的部分13C-NMR(DMSO-d6)δ:181.9164.6162.8161.6156.9150.6146.1121.1119.1116.1113.1105.4103.399.795.1两组葡萄糖碳信号如下:No.Glc1No.Glc198.51104.6282.7274.7375.7376.2469.6469.2576.9576.9660.6660.1FAB-MS:611[M+H]+,449,2871)推导此化合物结构,并写出详细的推导过程。2)对其氢谱信号加以归属。3.从分株紫萁(Osmundaasiatica)中得到一新的黄酮醇苷类成分(I),含有D-glc,分子式为C21H20O11.17(I)的UVλmaxnm:MeOH267352NaOMe275326402↑AlCl3274301352398AlCl3/HCl276303347400NaOAc275305(sh)NaOAc/H3BO3266300(sh)353(I)的1H-NMR(DMSO-d6)δ:3.2~3.9(6H),3.9~5.1(4H,加D2O后均消失),5.68(1H,d,J=8Hz),6.12(1H,d,J=2Hz),6.42(1H,d,J=2Hz),6.86(2H,d,J=9Hz),8.08(2H,d,J=9Hz).写出其结构。4化合物以2%H2SO4水解,从其水解液中检出葡萄糖和鼠李糖.A分子式为C27H30O16,它的1H-NMR(DMSO-d6)数据如下5.另一黄酮类化合物分子式为C16H14O7,UV谱在NaOAc作用下带II红移20nm,其氢谱数据如下:7.32(1H,d,J=8.0Hz),6.42(1H,dd,J=8.0,2.0Hz),6.40(1H,d,J=2.0Hz),6.20(1H,d,J=2.5Hz),6.18(1H,d,J=2.5Hz),5.08(1H,d,J=3.5Hz),4.26(1H,d,J=3.5Hz),3.76(3H,s).质谱中有m/z109,166两个主要碎片。推断此化合物结构,分析其碎片结构。6.从中药黄独中分离到一化合物(II),HCl-Mg反应(+)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