supplementary materials
The Spectroscopic Data of Lotusine,Liensinine, Isoliensinine and NeferineIsolated from LotusPlumule (Nelumbo nucifera Gaertn)
Guangming Yang, Weidong Li, Yang Pan, Xia Tu
Our group has previously elucidated the structure of lotusine, liensinine, isoliensinine and neferine isolated from lotus plumule (Nelumbo nucifera Gaertn) by UV, IR, 1H NMR, 13C NMR, DEPT, two-dimensional NMR, TOF-MS and EI-MS spectra.
Lotusine (1)
Chemical name for compound 1is 1-(p-hydroxybenzyl)-2,2-dimethyl-7-methoxy-1,2,3,4-tetrahydro-6-isoquinolinol, molecular formula C19H24O3N. Colorless cubical crystals or amorphous powders (dehydrated ethanol); mp 214–215 °C; UVnm(log ):228.6(4.15) and 283.0(3.65). The former is K absorption of substituted aromatic rings by chromophores, and the later is B characteristic absorbing peak of aromatic compounds.IRcm–1:3550, 3115, 3010, and 2975[br., ν(O–H)], 1618, 1598, 1520[frame vibration of benzene ring, ν(C=C)], 1265, 1242[ν(C–O–C)], 1118, 910, 880 and840.It suggests the presence of benzene rings, hydroxyl and ether groups, without carbonyl group.Its NMR signals are completely assigned by 1H NMR (500 MHz, D2O),13C NMR(125 MHz, D2O), DEPT, HSQC, 1H–1H COSYand HMBCdata, see Table 1 and Figure 1.Positive TOF–HRMS shows molecular ion peak at m/z314.1796 (M+),ESIat m/z 269([M–45]+) and 221, and EI–MSat m/z 220 ([M–94]+), 147, 121 and 100, the fragment pathways, seeFigure2 and Figure3. [1, 2]
Table 1 The 1HNMR(500 MHz) and13CNMR(125 MHz)data for1(in D2O)
Assignment / H(ppm) / C(ppm) / Assignment / H(ppm) / C(ppm)C1 / 4.54dd, 1H, J= 10.7,3.8 Hz / 75.16 / C / 2.84m, 1H / 39.22
C3 / 3.58m, 1H / 57.06 / 3.64m, 1H
3.93m, 1H / C1’ / － / 129.80
C4 / 3.15m, 1H / 25.38 / C2’ / 6.79s, 1H / 134.43
C4a / － / 124.06 / C3’ / 6.82s, 1H / 118.16
C5 / 6.78s, 1H / 117.51 / C4’ / － / 157.41
C6 / － / 147.74 / C5’ / 6.85s, 1H / 118.16
C7 / － / 147.89 / C6’ / 6.81s, 1H / 134.43
C8 / 5.64s, 1H / 115.70 / N(CH3)2 / 3.12s, 3H / 53.34
C8a / － / 124.11 / 3.44s, 3H / 55.06
OCH3 / 3.37s, 3H / 58.26
Fig. 1 The protons coupled with the respective carbons observed in the HMBC spectrum of 1
Fig. 2The major ESIFragments of 1
Fig.3The major EI–MS Fragments of 1
Liensinine(2)
Molecular formulafor compound2is C37H42O6N2.White amorphous powders (diethyl ether); mp 94–96 °C; UVnm(log ):211.0(4.77), 283.3(4.09).IRcm–1:3550, 3115, 3010, 2975[br., ν(O–H)], 1618, 1598, 1520[frame vibration of benzene ring, ν(C=C)], 1265, 1242, 1217[ν(C–O–C)], 1118, 1020, 1000, 880, 860, 840 and 810. Its NMR signals are completely assigned by 1H NMR (500 MHz, CDCl3),13C NMR(125 MHz, CDCl3), DEPT, HSQC, 1H–1H COSYand HMBCdata, see Table 2.Positive TOF–MS shows molecular ion peakat m/z 611.3113([M+H]+). [1, 3]
Table2The 1HNMR(500 MHz) and13CNMR(125 MHz)data for 2(in CDCl3)
Assignment / H(ppm) / C(ppm) / Assignment / H(ppm) / C(ppm)C1 / 3.68dd, 1H,J= 9.9,2.7 Hz / 64.54 / C1’ / 3.52dd,1H, J= 2.3,9.3 Hz / 65.11
C3 / 2.40m,1H
2.98m,1H / 44.45 / C3’ / 2.74m, 1H
3.19m, 1H / 47.60
C4 / 2.64m, 1H
2.94m,1H / 21.98 / C4’ / 2.81m, 2H / 26.20
C4a / － / 126.68 / C4’a / － / 123.54
C5 / 5.73s,1H / 111.43 / C5’ / 6.56s,1H / 111.31
C6 / － / 147.66 / C6’ / － / 146.26
C7 / － / 148.19 / C7’ / － / 146.75
C8 / 6.36(1H，s) / 118.04 / C8’ / 6.66s,1H / 112.16
C8a / － / 130.32 / C8’a / － / 129.53
C9 / 2.64m, 1H
3.13dd,1H,J= 13.1,2.2 Hz / 42.15 / C9’ / 2.71m, 1H
3.16m,1H / 39.71
C10 / － / 130.58 / C10’ / － / 130.54
C11 / 6.92d,1H,J= 8.3 Hz / 130.83 / C11’ / 6.75d,1H,J= 2.0 Hz / 121.45
C12 / 6.75d,1H,J= 8.2 Hz / 116.54 / C12’ / － / 143.23
C13 / － / 155.56 / C13’ / － / 143.99
C14 / 6.75d, 1H,J= 8.2 Hz / 116.54 / C14’ / 6.72d,1H,J= 8.1 Hz / 115.48
C15 / 6.92d,1H,J= 8.3 Hz / 130.83 / C15’ / 6.41dd, 1H, J= 1.9,8.2 Hz / 127.13
C2–NCH3 / 2.51s, 3H / 42.42 / C2’ –NCH3 / 2.54s, 3H / 40.51
C6–OCH3 / 3.42s,3H / 55.33 / C6’ –OCH3 / 3.85s, 3H / 55.88
C7’ –OCH3 / 3.82s, 3H / 55.71
Isoliensinine(3)
Molecular formulafor compound3is C37H42O6N2.White amorphous powders (diethyl ether); mp 70–72 °C.Its NMR signals are completely assigned by 1H NMR (500 MHz, CDCl3),13C NMR(125 MHz, CDCl3), DEPT, HSQC, 1H–1H COSYand HMBCdata, see Table 3.Positive TOF–MS shows molecular ion peakat m/z611.3113([M+H]+). [1, 3]
Table 3The 1HNMR(500 MHz) and13CNMR(125 MHz)data for 3(in CDCl3)
Assignment / H(ppm) / C(ppm) / Assignment / H(ppm) / C(ppm)C1 / 3.70t,1H,J= 6.2 Hz / 63.95 / C1’ / 3.60t,1H, J= 5.8Hz / 64.13
C3 / 2.82m, 1H
3.14m, 1H / 46.05 / C3’ / 2.69m, 1H
3.12m, 1H / 46.84
C4 / 2.52m,1H
2.74m, 1H / 24.75 / C4’ / 2.66m, 1H / 25.48
2.87m, 1H
C4a / － / 130.17 / C4’a / － / 125.64
C5 / 6.30s, 1H / 110.56 / C5’ / 6.46s, 1H / 112.39
C6 / － / 143.43 / C6’ / － / 143.43
C7 / － / 145.14 / C7’ / － / 145.14
C8 / 6.33s, 1H / 113.75 / C8’ / 6.46s, 1H / 118.66
C8a / － / 130.67 / C8’a / － / 130.17
C9 / 2.78m, 1H
2.97dd,1H, J= 5.3,14.1 Hz / 40.10 / C9’ / 2.74m, 1H
3.08m, 1H / 38.81
C10 / － / 131.83 / C10’ / － / 131.41
C11 / 6.90d, 1H, J= 8.6 Hz / 130.06 / C11’ / 6.64s, 1H / 110.74
C12 / 6.70d, 1H, J= 8.6 Hz / 113.16 / C12’ / － / 148.96
C13 / － / 142.80 / C13’ / － / 157.76
C14 / 6.70d, 1H, J= 8.6 Hz / 113.16 / C14’ / 6.82d,1H, / 115.05
C15 / 6.90d, 1H, J= 8.6 Hz / 130.06 / C15’ / 6.74dd,J= 8.2,1.7 Hz / 124.88
C2–NCH3 / 2.41s, 3H / 42.09 / C2’ –NCH3 / 2.52s, 3H / 42.03
C6–OCH3 / 3.73s, 3H / 54.74 / C6’ –OCH3 / 3.81s, 3H / 55.54
C13–OCH3 / 3.79s,3H / 55.39
Neferine(4)
Molecular formulafor compound4is C38H44O6N2.Yellowishamorphous powders (diethyl ether); mp 59–61 °C.Its NMR signals are completely assigned by 1H NMR (500 MHz, CDCl3),13C NMR(125 MHz, CDCl3), DEPT, HSQC, 1H–1H COSYand HMBCdata, see Table 4.Positive TOF–MS shows molecular ion peakat m/z625.3179([M+H]+). [1, 3]
Table 4The 1HNMR(500 MHz) and13CNMR(125 MHz)data for 4(in CDCl3)
Assignment / H(ppm) / C(ppm) / Assignment / H(ppm) / C(ppm)C1 / 3.64m,1H / 64.35 / C1’ / 3.64m,1H / 64.74
C3 / 2.75m, 1H
3.16m, 1H / 46.54 / C3’ / 2.75m,1H
3.16m,1H / 47.11
C4 / 2.57m, 1H
2.81m, 1H / 24.99 / C4’ / 2.63m,1H / 25.99
2.81m,1H
C4a / － / 128.60 / C4’a / － / 125.38
C5 / 6.50s, 1H / 111.14 / C5’ / 5.98s, 1H / 110.96
C6 / － / 147.29 / C6’ / － / 145.53
C7 / － / 148.93 / C7’ / － / 146.35
C8 / 6.62s, 1H / 112.32 / C8’ / 6.36s, 1H / 119.32
C8a / － / 130.89 / C8’a / － / 130.22
C9 / 2.67m, 1H
3.09m, 1H / 40.56 / C9’ / 2.78m,1H
3.00dd,1H,J= 13.9,5.3 Hz / 39.82
C10 / － / 131.52 / C10’ / － / 131.24
C11 / 6.89d, 1H, J= 8.6 Hz) / 130.42 / C11’ / 6.53d, 1H, J= 1.9 Hz / 120.00
C12 / 6.68d, 1H, J= 8.7 Hz / 113.40 / C12’ / － / 142.84
C13 / － / 144.74 / C13’ / － / 157.79
C14 / 6.68d, 1H, J= 8.7 Hz / 113.40 / C14’ / 6.84d,1H,J= 8.2 Hz / 115.53
C15 / 6.89d, 1H, J= 8.6 Hz / 130.42 / C15’ / 6.69dd,J= 7.7,2.0 Hz / 125.30
C2–NCH3 / 2.50s, 3H / 42.57 / C2’ –NCH3 / 2.47s, 3H / 42.31
C6–OCH3 / 3.71s, 3H / 55.42 / C6’ –OCH3 / 3.78s, 3H / 55.82
C13–OCH3 / 3.51s, 3H / 55.06 / C7’ –OCH3 / 3.80s, 3H / 55.68
References
1.Pan Y, CaiBC(2004)Dissertation of Doctoral Degree ofNanjingUniversity of ChineseTraditional Medicine.Nanjing, China p50.
2.Pan Y, Yang GM, CaiBC, Ding G(2004)China Tradit Herb Drugs 35:501.
3. Pan Y, Yang GM, CaiBC(2005)J Nanjing Univ TCM (Nat Sci Ed) 21:371.
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