香豆素

§3.2香豆素------香豆素的波谱特征OOAB123456789101、香豆素的结构类型OOHOAB12345678910OOOAB123456789101'2'3'COOOAB123456789101'2'3'COOOAB123456789101'2'3'C4'5'6'OOOOHOH6'5'4'C3'2'1'10987654321BAOOHOOH10987654321BA2、香豆素的紫外光谱特征无含氧取代274nm(loge4.03,II带)311nm(loge3.72,I带)含氧取代7-氧取代217,330(s),240,255(w)位移试剂峰位强度+乙酸钠：7-OH红移增强6，8-OH红移降低+AlCl3：邻二羟基红移10987654321BAOOIII3、香豆素的红外光谱特征3025-3175cm-1呋喃香豆素nC-H1700-1750cm-1nC=OKBr片：1720cm-11500-1600cm-1n苯环1600-1650cm-1nC=COOAB123456789104、香豆素的1HNMR规律B环质子影响因素：2-羰基影响：如（d-）所示7-OH影响：如（d-）所示H3,H6,H8电子云密度H3,H6,H8在高场H4,H5,H7电子云密度H3,H6,H8在低场OOHOAB12345678910d-d-d-d-d+d-d+d+d+d+d-d-d-d6.1-6.4(d,9.5Hz)d7.5-8.3(d,9.5Hz)d7.38（d,9.0Hz）d6.87(dd,9.0,2.0Hz)OOHOAB12345678910d6.87(d,2.0Hz)C3'2'1'10987654321BAOOOd6.7(d,J=2.3Hz)d7.3-7.8(d,J=2.3Hz)呋喃香豆素OOOAB123456789101'2'3'Cd7.3-7.8(d,J=2.5Hz)d7.0(d,J=2.5Hz)AB123456789101'2'3'C4'5'6'OOOOHOH吡喃香豆素1HNMR特征3’4’顺式羟基：4’-H:d5.18(d,J=5.5Hz)3’-H:d3.80(d,J=5.5Hz)CH3:d1.40/1.44(Dd0.08ppm)3’4’反式羟基：4’-H:d4.90(d,J=6.0Hz)3’-H:d3.73(d,J=6.0Hz)CH3:d1.25/1.44(Dd0.08ppm)CH3CH2OCH3Hd1.6-1.9d1.6-1.9(s)d5.1-5.7(1H,t,J=7Hz)d4.3-5.3(2Hm,d,J=7Hz)d1.6-1.9d1.6-1.9(s)d5.1-5.7(1H,t,J=7Hz)d3.3-3.8(2Hm,d,J=7Hz)CH3CH2CH3HCH2OHCH3CH2CH2OHCH3CH2CH3CH2OABCDHOEOFComa-Hb-Hc-HCH3=CH2A3.104.30-1.83s4.80B4.35m4.35-1.71s4.86s5.06sC4.173.20-1.755.03mD-6.4-1.704.995.01E6.886.32-1.44s-F4.00-2.811.21-香豆素分子中的远程偶合OOHOHH10987654321BAC3'2'1'10987654321BAOOOHHH5J3’,8=0.6-1.0Hz5J4,8=0.6-1.0Hz5J4,8=0.6-1.0Hz5、香豆素的13CNMR规律羰基受共轭影响出现在:d160C3、C4受受羰基影响:dC3=116dC4=143C6,C8,C10羰基、OH影响:dC6=113dC8=103dC10=112C5,C7,C9羰基、OH影响:dC5=130dC7=162dC9=1564-OH取代：dC2=162dC3=91.4dC4=1663-OH取代：dC2=158dC3=142dC4=115d-d-d-d-d+d-d+d+d+d-d-d-OOHOAB12345678910d+C3'2'1'10987654321BAOOOd106.6d147.0呋喃香豆素d99.9d125.0(+12)OOOAB123456789101'2'3'Cd104.0d145.9d116.9(+15)d148.5(-4.3)C3'2'1'10987654321BAOOO4'5'6'd20.8d28.4d166.3d97.2d108.2d122.76、香豆素的MS规律简单香豆素母体香豆素分子离子峰强易产生一系列失CO碎片离子10987654321BAOO+.-COBO146(76%)-COC7H6+.118(100%)90(43%)+.OOAB12345678910-CH3-C4H7+.OOAB12345678910214(78%)M-15+.AOO具有异戊烯基侧链10987654321BAOOOOH+.+HO10987654321BAOOHOHCH2+.+10987654321BA+.+OOHOCH2-H竹叶防风根（2Kg）95%乙醇渗滤己烷溶解己烷可溶部分90%甲醇分配90%甲醇可溶解部分硅胶柱色谱氯仿-丙酮梯度洗脱硅胶制备薄层色谱无色针晶mp.68-70结构研究实例元素分析：C21H22O7[a]D20–26.2°(c=1.5,CHCl3)UV下显示蓝色荧光UVlmax(甲醇)：256，295，320IRnmaxcm-1(CHCl3)：3000,1740,1730,1615,1450,1220EI-MS(m/z):386(M+),326,311,286,226,213,198,186,158,102,8310987654321BAOOOOAcOO1'2'3'4'5'6'12345(M+-HOAC)(M+-C5H8O2)(M+-C5H8O2-HOAC)1HNMR(CDCl3)d:7.62(1H,d,J=9.7Hz)6.24(1H,d,J=9.7Hz)7.42(1H,d,J=8.4Hz)6.86(1H,d,J=8.4Hz)7.01(1H,d,J=6.8Hz)5.31(1H,d,J=6.8Hz)6.07(1H,q,J=6.0Hz)1.97(3H,d,J=6.0Hz)2.06(3H,s),1.86(3H,br.s)1.76(3H,s),1.68(3H,s)H-4H-3H-5H-6H-3’H-2’H-3”H-4”CH3-AcCH3-5”H-5’,6’10987654321BAOOOOAcOO1'2'3'4'5'6'1234513CNMR(CDCl3)d:168.6166.0163.6160.0152.0144.3137.7131.3128.0116.6113.1112.7112.688.680.368.627.622.521.720.815.6C-2C-3C-4C-9C-7Ac-C=OC-1”C-3”C-5C-10C-8C-6C-2”C-3’C-2’C-4’Ac-CH3C-5’C-6’C-5”C-4”10987654321BAOOOOAcOO1'2'3'4'5'6'12345Oroselone(I),浅黄色针晶，mp184-186℃(EtOH)。HRMSm/z:226.0559(M+,C14H10O3,理论值226.0630)。1HNMR(CDCl3)：7.79(1H,d,J=9.5Hz),7.37(1H,d,J=8.5Hz),7.33(1H,d,J=8.5Hz),6.96(1H,s),6.38(1H,d,J=9.5Hz),5.84(1H,brs),5.26(1H,brs),2.15(3H,s).13CNMR(CDCl3)：160.8,158.0,157.0,148.2,144.5,132.3,124.0,118.4,114.6,114.0,113.6,108.4,99.7,19.2(VIII),浅黄色针晶，mp200-201℃(EtOH)。HRMSm/z:228.00404(M+,C13H8O4,理论值228.0423)。1HNMR(CDCl3)：7.82(1H,d,J=9.5Hz),7.83(1H,s),7.57(1H,d,J=8.5Hz),7.51(1H,d,J=8.5Hz),6.45(1H,d,J=9.5Hz),2.65(3H,s).VIII的13CNMR(CDCl3)：160.1,153.2,157.5,149.7,144.1,187.8,127.6,117.0,115.0,114.1,109.5,110.1,26.5Oroselone(I),浅黄色针晶，mp184-186℃(EtOH)。HRMSm/z:226.0559(M+,C14H10O3,理论值226.0630)。1HNMR(CDCl3)：7.79(1H,d,J=9.5Hz),7.37(1H,d,J=8.5Hz),7.33(1H,d,J=8.5Hz),6.96(1H,s),6.38(1H,d,J=9.5Hz),5.84(1H,brs),5.26(1H,brs),2.15(3H,s).AB12345678910OOHOHHHH??CH3CH2HOOroselone(I),浅黄色针晶，mp184-186℃(EtOH)。HRMSm/z:226.0559(M+,C14H10O3,理论值226.0630)。1HNMR(CDCl3)：7.79(1H,d,J=9.5Hz),7.37(1H,d,J=8.5Hz),7.33(1H,d,J=8.5Hz),6.96(1H,s),6.38(1H,d,J=9.5Hz),5.84(1H,brs),5.26(1H,brs),2.15(3H,s).AB12345678910OOO1'2'3'4'5'6'Oroselone13CNMR(CDCl3)：160.8,158.0,157.0,148.2,144.5,132.3,124.0,118.4,114.6,114.0,113.6,108.4,99.7,19.2AB12345678910OOO1'2'3'4'5'6'C-2C-3C-4C-5C-6C-7C-9C-2’C-3’C-8C-10C-5’C-4’C-6’(VIII),浅黄色针晶，mp200-201℃(EtOH)。HRMSm/z:228.00404(M+,C13H8O4,理论值228.0423)。1HNMR(CDCl3)：7.82(1H,d,J=9.5Hz),7.83(1H,s),7.57(1H,d,J=8.5Hz),7.51(1H,d,J=8.5Hz),6.45(1H,d,J=9.5Hz),2.65(3H,s).AB12345678910OOO1'2'3'VIII的13CNMR(CDCl3)：160.1,153.2,157.5,149.7,144.1,187.8,127.6,117.0,115.0,114.1,109.5,110.1,26.5C-2C-3C-4C-5C-6C-7C-9C-2’C-3’C-8C-10C-4’C-5’5'4'3'2'1'OOOO10987654321BA氯仿H2OH-4H-3H-bH-aC1'2'3'4'5'H-1’H-2’OO？OaOOO？氯仿H2O长链脂肪酸H-4H-3H-aH-bOOOH2O丙酮长链脂肪酸OHOOOOH甲醇H2OOOHOCH3OCH3OOOOOCH3氯仿H2OCH3OH-1’H-2’C1'2'3'4'5'OOOOCH3OOOOOOOOHOH4'5'2'1'3''4''5''H-1’H-2’H-3’’H-4’’,5’’OOOOOOHOH4'5'2'1'3''4''5''H-1’H-2’H-2’’OOOOOHOOH4'5'2'1'2''4''5''H-5’’H-4’’OOOOOHOOH4'5'2'1'2''4''5''OOOOOOO4'5'2'1'2''4''5''OOOOOOO4'5'2'1'2''4''5''OOOOOOO4'5'2'1'2''3''4''OOOOOOO4'5'2'1'2''3''4''OOOOOOO4'5'2'1'2''3''4''1’’Ac-C=O3’’,4’’1’2