༤ኈㄽᩥ

᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firmaࠊࢡࣟࢱ࢟
࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᡂศ◊✲2020ᗈᓥ኱Ꮫ኱Ꮫ㝔་ṑ⸆ಖ೺Ꮫ◊✲⛉  ⸆Ꮫ⛉ᑓᨷ⏕⸆Ꮫ◊✲ᐊ
ᖹᡂ 29 ᖺᗘධᏛ  NGUYEN HOANG UYEN
୺ᣦᑟᩍဨᯇᾉ ຾⩏┠ḟ
➨ 1 ❶ ᗎㄽ ·······················································································1➨ 2 ❶ ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firma ࡢᡂศ◊✲ ····································2➨ 1 ⠇ ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firma ࡟ࡘ࠸࡚ ·································2➨ 2 ⠇ ᢳฟࠊศ㞳ཬࡧ⢭〇 ·····························································3➨ 3 ⠇ ᪂つ໬ྜ≀࡟ࡘ࠸࡚ ·····························································5➨ 1 㡯 ᪂つ໬ྜ≀ Compound 2 ࡢᵓ㐀Ỵᐃ ·····································5➨ 2 㡯 ᪂つ໬ྜ≀ Compound 11 ࡢᵓ㐀Ỵᐃ ·································· 10➨ 4 ⠇ ᪤▱໬ྜ≀࡟ࡘ࠸࡚ ··························································· 15➨ 1 㡯 ᪤▱໬ྜ≀ Compound 1 ࡢᵓ㐀Ỵᐃ ··································· 16➨ 2 㡯 ᪤▱໬ྜ≀ Compound 3 ࡢᵓ㐀Ỵᐃ ··································· 18➨ 3 㡯 ᪤▱໬ྜ≀ Compound 4 ࡢᵓ㐀Ỵᐃ ··································· 19➨ 4 㡯 ᪤▱໬ྜ≀ Compound 5 ࡢᵓ㐀Ỵᐃ ··································· 21➨ 5 㡯 ᪤▱໬ྜ≀ Compound 6 ࡢᵓ㐀Ỵᐃ ··································· 23➨ 6 㡯 ᪤▱໬ྜ≀ Compound 7 ࡢᵓ㐀Ỵᐃ ··································· 25➨ 7 㡯 ᪤▱໬ྜ≀ Compound 8 ࡢᵓ㐀Ỵᐃ ··································· 27➨ 8 㡯 ᪤▱໬ྜ≀ Compound 9 ࡢᵓ㐀Ỵᐃ ··································· 29➨ 9 㡯 ᪤▱໬ྜ≀ Compound 10 ࡢᵓ㐀Ỵᐃ ·································· 31➨ 10 㡯 ᪤▱໬ྜ≀ Compound 12 ࡢᵓ㐀Ỵᐃ ·································· 33➨ 11 㡯 ᪤▱໬ྜ≀ Compound 13 ࡢᵓ㐀Ỵᐃ ·································· 35➨ 12 㡯 ᪤▱໬ྜ≀ Compound 14 ࡢᵓ㐀Ỵᐃ ·································· 37➨ 13 㡯 ᪤▱໬ྜ≀ Compound 15 ࡢᵓ㐀Ỵᐃ ·································· 39➨ 14 㡯 ᪤▱໬ྜ≀ Compound 16 ࡢᵓ㐀Ỵᐃ ·································· 40➨ 15 㡯 ᪤▱໬ྜ≀ Compound 17 ࡢᵓ㐀Ỵᐃ ·································· 42➨ 16 㡯 ᪤▱໬ྜ≀ Compound 18 ࡢᵓ㐀Ỵᐃ ·································· 44➨ 17 㡯 ᪤▱໬ྜ≀ Compound 19 ࡢᵓ㐀Ỵᐃ ·································· 45➨ 18 㡯 ᪤▱໬ྜ≀ Compound 20 ࡢᵓ㐀Ỵᐃ ·································· 47➨ 3 ❶ ᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢᡂศ◊✲ ···················· 49➨ 1 ⠇ ᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡟ࡘ࠸࡚ ················· 49➨ 2 ⠇ ᢳฟࠊศ㞳ཬࡧ⢭〇 ··························································· 50➨ 3 ⠇ ᪂つ໬ྜ≀࡟ࡘ࠸࡚ ··························································· 52➨ 1 㡯 ᪂つ໬ྜ≀ Compound 21 ࡢᵓ㐀Ỵᐃ ·································· 52

➨ 2 㡯 ᪂つ໬ྜ≀ Compound 22 ࡢᵓ㐀Ỵᐃ ·································· 57➨ 4 ⠇ ᪤▱໬ྜ≀࡟ࡘ࠸࡚ ··························································· 61➨ 1 㡯 ᪤▱໬ྜ≀ Compound 23 ࡢᵓ㐀Ỵᐃ ·································· 62➨ 2 㡯 ᪤▱໬ྜ≀ Compound 24 ࡢᵓ㐀Ỵᐃ ·································· 64➨ 3 㡯 ᪤▱໬ྜ≀ Compound 25 ࡢᵓ㐀Ỵᐃ ·································· 66➨ 4 㡯 ᪤▱໬ྜ≀ Compound 26 ࡢᵓ㐀Ỵᐃ ·································· 68➨ 5 㡯 ᪤▱໬ྜ≀ Compound 27 ࡢᵓ㐀Ỵᐃ ·································· 70➨ 6 㡯 ᪤▱໬ྜ≀ Compound 28 ࡢᵓ㐀Ỵᐃ ·································· 72➨ 7 㡯 ᪤▱໬ྜ≀ Compound 29 ࡢᵓ㐀Ỵᐃ ·································· 74➨ 8 㡯 ᪤▱໬ྜ≀ Compound 30 ࡢᵓ㐀Ỵᐃ ·································· 76➨ 9 㡯 ᪤▱໬ྜ≀ Compound 31 ࡢᵓ㐀Ỵᐃ ·································· 78➨ 10 㡯 ᪤▱໬ྜ≀ Compound 32 ࡢᵓ㐀Ỵᐃ ·································· 80➨ 11 㡯 ᪤▱໬ྜ≀ Compound 33 ࡢᵓ㐀Ỵᐃ ·································· 82➨ 12 㡯 ᪤▱໬ྜ≀ Compound 34 ࡢᵓ㐀Ỵᐃ ·································· 84➨ 13 㡯 ᪤▱໬ྜ≀ Compound 35 ࡢᵓ㐀Ỵᐃ ·································· 86➨ 14 㡯 ᪤▱໬ྜ≀ Compound 36 ࡢᵓ㐀Ỵᐃ ·································· 88➨ 15 㡯 ᪤▱໬ྜ≀ Compound 37 ࡢᵓ㐀Ỵᐃ ·································· 90➨ 16 㡯 ᪤▱໬ྜ≀ Compound 38 ࡢᵓ㐀Ỵᐃ ·································· 92➨ 17 㡯 ᪤▱໬ྜ≀ Compound 39 ࡢᵓ㐀Ỵᐃ ·································· 94➨ 18 㡯 ᪤▱໬ྜ≀ Compound 40 ࡢᵓ㐀Ỵᐃ ·································· 96➨ 19 㡯 ᪤▱໬ྜ≀ Compound 41 ࡢᵓ㐀Ỵᐃ ·································· 98➨ 20 㡯 ᪤▱໬ྜ≀ Compound 42 ࡢᵓ㐀Ỵᐃ ································· 100➨ 21 㡯 ᪤▱໬ྜ≀ Compound 43 ࡢᵓ㐀Ỵᐃ ································· 102➨ 22 㡯 ᪤▱໬ྜ≀ Compound 44 ࡢᵓ㐀Ỵᐃ ································· 104➨ 23 㡯 ᪤▱໬ྜ≀ Compound 45 ࡢᵓ㐀Ỵᐃ ································· 106➨ 24 㡯 ᪤▱໬ྜ≀ Compound 46 ࡢᵓ㐀Ỵᐃ ································· 108➨ 25 㡯 ᪤▱໬ྜ≀ Compound 47 ࡢᵓ㐀Ỵᐃ ································· 110➨ 26 㡯 ᪤▱໬ྜ≀ Compound 48 ࡢᵓ㐀Ỵᐃ ································· 112➨ 27 㡯 ᪤▱໬ྜ≀ Compound 49 ࡢᵓ㐀Ỵᐃ ································· 114➨ 28 㡯 ᪤▱໬ྜ≀ Compound 50 ࡢᵓ㐀Ỵᐃ ································· 116➨ 29 㡯 ᪤▱໬ྜ≀ Compound 51 ࡢᵓ㐀Ỵᐃ ································· 118➨ 30 㡯 ᪤▱໬ྜ≀ Compound 52 ࡢᵓ㐀Ỵᐃ ································· 120➨ 31 㡯 ᪤▱໬ྜ≀ Compound 53 ࡢᵓ㐀Ỵᐃ ································· 122➨ 32 㡯 ᪤▱໬ྜ≀ Compound 54 ࡢᵓ㐀Ỵᐃ ································· 124➨ 4 ❶ ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᡂศ◊✲➨ 1 ⠇ ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡟ࡘ࠸࡚························· 126

➨ 2 ⠇ ᢳฟࠊศ㞳ཬࡧ⢭〇 ·························································· 127➨ 3 ⠇ ᪂つ໬ྜ≀࡟ࡘ࠸࡚ ·························································· 129➨ 1 㡯 ᪂つ໬ྜ≀ Compound 55 ࡢᵓ㐀Ỵᐃ ································· 129➨ 2 㡯 ᪂つ໬ྜ≀ Compound 56 ࡢᵓ㐀Ỵᐃ ································· 132➨ 2 㡯 ᪂つ໬ྜ≀ Compound 57 ࡢᵓ㐀Ỵᐃ ································· 136➨ 4 ⠇ ᪤▱໬ྜ≀࡟ࡘ࠸࡚ ·························································· 140➨ 1 㡯 ᪤▱໬ྜ≀ Compound 58 ࡢᵓ㐀Ỵᐃ ································· 141➨ 2 㡯 ᪤▱໬ྜ≀ Compound 59 ࡢᵓ㐀Ỵᐃ ································· 143➨ 3 㡯 ᪤▱໬ྜ≀ Compound 60 ࡢᵓ㐀Ỵᐃ ································· 145➨ 4 㡯 ᪤▱໬ྜ≀ Compound 61 ࡢᵓ㐀Ỵᐃ ································· 147➨ 5 㡯 ᪤▱໬ྜ≀ Compound 62 ࡢᵓ㐀Ỵᐃ ································· 149➨ 6 㡯 ᪤▱໬ྜ≀ Compound 63 ࡢᵓ㐀Ỵᐃ ································· 151➨ 7 㡯 ᪤▱໬ྜ≀ Compound 64 ࡢᵓ㐀Ỵᐃ ································· 153➨ 8 㡯 ᪤▱໬ྜ≀ Compound 65 ࡢᵓ㐀Ỵᐃ ································· 155➨ 9 㡯 ᪤▱໬ྜ≀ Compound 66 ࡢᵓ㐀Ỵᐃ ································· 157➨ 10 㡯 ᪤▱໬ྜ≀ Compound 67 ࡢᵓ㐀Ỵᐃ ································· 159➨ 11 㡯 ᪤▱໬ྜ≀ Compound 68 ࡢᵓ㐀Ỵᐃ ································· 161➨ 12 㡯 ᪤▱໬ྜ≀ Compound 69 ࡢᵓ㐀Ỵᐃ ································· 163➨ 13 㡯 ᪤▱໬ྜ≀ Compound 70 ࡢᵓ㐀Ỵᐃ ································· 165➨ 5 ❶ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂 ···················································· 166➨ 1 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂࡟ࡘ࠸࡚ ······································· 166➨ 2 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ἲ ················································ 167➨ 3 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ࡢ⤖ᯝ ·········································· 168➨ 6 ❶ Tyrosinase 㜼ᐖάᛶヨ㦂 ··························································· 169➨ 1 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂࡟ࡘ࠸࡚ ············································· 169➨ 2 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂ἲ ······················································ 170➨ 3 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂ࡢ⤖ᯝ ················································ 171➨ 7 ❶ α-Amylase 㜼ᐖάᛶヨ㦂··························································· 172➨ 1 ⠇ α-Amylase 㜼ᐖάᛶヨ㦂࡟ࡘ࠸࡚ ············································· 172➨ 2 ⠇ α-Amylase 㜼ᐖάᛶヨ㦂ἲ ······················································ 173➨ 3 ⠇ α-Amylase 㜼ᐖάᛶヨࡢ⤖ᯝ ··················································· 174➨ 8 ❶ A549 ⒴⣽⬊ቑṪᢚไάᛶヨ㦂 ·················································· 175➨ 1 ⠇ A549 ⒴⣽⬊ቑṪᢚไάᛶヨ㦂࡟ࡘ࠸࡚ ····································· 175➨ 2 ⠇ A549 ⒴⣽⬊ቑṪᢚไάᛶヨ㦂ἲ ·············································· 176

➨ 3 ⠇ A549 ⒴⣽⬊ቑṪᢚไάᛶヨ㦂ࡢ⤖ᯝ ········································ 177➨ 9 ❶ ࡲ࡜ࡵ ················································································· 178➨ 10 ❶ ᐇ㦂ࡢ㒊 ·············································································· 183ཧ⪃ᩥ⊩ ·························································································· 194
ㅰ㎡ ································································································ 200

ᮏᩥ୰࡛౑⏝ࡋࡓ୺࡞␎ྕ㸯

H NMR: Proton Nuclear Magnetic Resonance

13

C NMR: Carbon-13 Nuclear Magnetic Resonance

HR-ESI-MS: High Resolution Electro Spray Ionization Mass Spectroscopy
COSY: HH-Correlation Spectroscopy
HMBC: Heteronuclear Multiple Bond Connectivity
HSQC: Heteronuclear Single Quantum Coherence
IR: Infrared Spectroscopy
UV: Ultraviolet Spectroscopy
HPLC: High-Performance Liquid Chromatography
CC: Column Chromatography
TLC: Thin Layer Chromatography
ODS: Octadecylsilanized Silica gel
Cpd: Compound
fr.: fraction
br.: broads: singlet
d: doublet
t: triplet
q: quartet
m: multiplet➨ 1 ❶ ᗎㄽ௒᪥ࡲ࡛ே㢮ࡣࠊ᳜≀ࡸື≀ࠊ㖔≀➼ࡢᵝࠎ࡞ኳ↛≀ࢆᕦࡳ࡟฼⏝ࡋࠊ⸆⏝㈨※࡜ࡋ࡚⏝࠸࡚ࡁࡓࠋኳ↛≀ࡣࠊᡃࠎ࡟ࡣ᝿ീࡶࡘ࠿࡞࠸ࡼ࠺࡞ᵓ㐀ࡸ⸆⌮స⏝ࢆᣢࡘྍ⬟ᛶࢆ⛎ࡵ࡚࠾ࡾࠊ⌧ᅾ⮫ᗋ࡛౑⏝ࡉࢀ࡚࠸ࡿ་⸆ရࡢ᭷ຠᡂศ࡟ࡶࠊኳ↛࠿ࡽ༢㞳ࡉࢀࡓࡶࡢࠊ
࠶ࡿ࠸ࡣࡑࢀࡽࢆ࣮ࣜࢻ໬ྜ≀࡜ࡋ࡚ྜᡂࡉࢀࡓࡶࡢࡀᑡ࡞ࡃ࡞࠸ࠋ་⸆ရ࡟㝈ࡽࡎࠊ໬⢝ရࡸ㤶ᩱࠊ೺ᗣ㣗ရ࡞࡝ኳ↛≀ࡣᖜᗈࡃ฼⏝ࡉࢀ࡚࠾ࡾࠊᡃࠎࡢ⏕ά࡟ᐤ୚ࡋ࡚࠸ࡿࠋ
ࡑࡢࡓࡵ᪂ࡋ࠸᭷⏝㈨※ࢆ᥈⣴ࡋࠊᮍ฼⏝᳜≀ࡢᡂศ◊✲ࠊ⏕≀άᛶ࡟ࡘ࠸᳨࡚ウࢆ⾜࠺ࡇ࡜ࡣ㔜せ࡛࠶ࡿࠋ
᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firmaࠊࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡟㛵ࡍࡿ໬Ꮫⓗ◊✲ࡢሗ࿌౛ࡣ࡯࡜ࢇ࡝࡞ࡃࠊࡑࡢྵ᭷ᡂศࡢ໬Ꮫ
ᵓ㐀࠾ࡼࡧ⏕≀άᛶ࡟⯆࿡ࡀᣢࡓࢀࡓࡓࡵࠊࡇࢀࡽࡢ᳜≀ࡢᡂศ◊✲ࢆ⾜࠺ࡇ࡜࡜ࡋࡓࠋ

1

➨ 2 ❶ ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firma ࡢᡂศ◊✲➨ 1 ⠇ ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firma ࡟ࡘ࠸࡚Ꮫྡ㸸Silene firma Sieb. Et Zucc.
࿴ྡ㸸ࣇࢩࢢࣟ
⛉ྡ㸸Caryophyllaceae (ࢼࢹࢩࢥ⛉)ᒓྡ㸸Silene (࣐ࣥࢸ࣐ᒓ)ศᕸ㸸ᮏᕞࠊᅄᅜࠊ஑ᕞࠊᮅ㩭ࠊ୰ᅜࠊࣟࢩ࢔
ⰼᮇ㸸6㹼9 ᭶ⲡ୔㸸50㹼100 cm≉ᚩ㸸 ⱼࡣ┤❧ࡋࠊẟࡀᐦ⏕ࡍࡿࠋⴥࡣᑐ⏕ࡋࠊ㛗ࡉ 4㹼10 cmࠊᖜ 0.8㹼2.5 cm ࡢᢨ㔪ᙧ㹼㛗ᴃ෇ᙧࠊ⦕ẟࡀ࠶ࡾࠊඛࡀᑤࡿࠋⱖࡣ⊃ᢨ㔪ᙧࠋⱼ㡬ࡸⴥ⭆࡟ⓑⰍ㹼ࣆࣥࢡࡢᑠࡉ࡞ⰼࢆࡘࡅࡿࠋⰼ᯶ࡣ㛗ࡉ 5㹼20 mmࠋⰼᘚࡣ㛗ࡉ 2㹼3 mm ࡜ᑠࡉࡃࠊඛࡀ
2 ⿣ࡍࡿࠋ㞝ࡋ࡭ 10 ಶࠋⰼᰕ 3 ಶࠋⴟࡣ㛗ࡉ 7㹼10 mm ࡢ༸ᙧࠊඛࡀὸࡃ 5 ⿣ࡋ(5ṑ)ࠊ10 ⬦ࡀ࠶ࡾࠊᯝ᫬࡟ࡶṧࡗ࡚㛗ࡉ 10㹼12 mm ࡜ࡸࡸ኱ࡁࡃ࡞ࡿࠋᯝᐇࡣ㛗ࡉ8㹼11 mmࠊ⇍ࡍ࡜ඛࡀⰼᰕࡢ 2 ಸᩘࡢ 6 ಶ࡟⿣㛤ࡍࡿࠋ✀Ꮚࡣ⅊〓Ⰽࠊ㛗ࡉ⣙ 1
mmࠋ1)
ᮏ᳜≀ⴥ㒊ࠊⱼ㒊࠿ࡽࡣࠊࡇࢀࡲ࡛࡟ࣇࣛ࣎ࣀ࢖ࢻࡸࢧ࣏ࢽࣥ࡞࡝ࡀ༢㞳ࡉࢀ࡚
࠸ࡿࠋ2)Picture: http://www.okadanouen.com/zukan/fusiguro/fusiguro23.8.13-1.jpg

2

➨ 2 ⠇ ᢳฟࠊศ㞳࠾ࡼࡧ⢭〇ࣇࢩࢢࣟࡢᆅୖ㒊 10.6 kg ࢆ࣓ࢱࣀ࣮࡛ࣝᢳฟࡋࠊᖖἲ࡟ᚑ࠸ࠊn-࣊࢟ࢧࣥࠊ㓑㓟࢚ࢳ
ࣝࠊ1-ࣈࢱࣀ࣮ࣝࠊỈ࡛㡰ḟศ㓄ࡋࡓࠋᚓࡽࢀࡓ n-࣊࢟ࢧࣥྍ⁐⏬ศ࡜㓑㓟࢚ࢳࣝྍ⁐⏬
ศ (164.8g) ࢆ㡰┦ࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊODS-HPLC ࡟ࡼࡾศ㞳ࠊ⢭〇ࡋࠊ20 ✀㢮ࡢ໬ྜ≀ࢆ༢㞳ࡋࡓࠋࡑࡢ࠺ࡕ compound 2, 11 ࡣ᪂つ໬ྜ≀ࠊcompound 1,
3-10, 12-20 ࡣ ᪤▱໬ྜ≀࡜ྠᐃࡋࡓࠋ      Dried aerial parts of Silene firma(10.6 kg)
Extracted with MeOH
Concentrated
Partitioned with n-Hexane, EtOAc, 1-BuOH

n-Hexane layer

1-BuOH layer(76.0 g)EtOAc layer(164.8 g)

3

Aq. layer(411.8 g)

n-Hexane and EtOAc layer from aerial parts ofSilene firma (164.8 g)

Chart 1: Isolated compounds from the aerial parts of Silene firma4➨ 3 ⠇  ᪂つ໬ྜ≀࡟ࡘ࠸࡚➨ 1 㡯 ᪂つ໬ྜ≀ Compound 2 ࡢᵓ㐀Ỵᐃ
Cpd 2 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C42H46O20 ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋCpd 2 ࡣ
NMR ࢫ࣌ࢡࢺࣝࡼࡾ⢾㒊ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡓࡓࡵࠊNaOCH3 ࡛࢔ࣝ࢝ࣜຍ
Ỉศゎࢆ⾜࠸ࠊ㐟㞳ࡋࡓ⢾࡟ࡘ࠸࡚᪕ගᗘ᳨ฟჾ௜ࡁ HPLC ࢆ⏝࠸࡚⢾ศᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊCpd 2 ࡟ࡣ sucrose ࡀྵࡲࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣ 13C NMR ࡟࠾࠸࡚ sucrose࡟⏤᮶ࡍࡿ 12 ᮏࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜࡜୍⮴ࡋࡓࠋࡑࡢ௚࡟ࡶ 13C NMR ࡟࠾࠸࡚ 111.8~150.9 ppm ࡟ⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ168.6ࠊ
168.9 ࠊ169.2 ppm ࡟࢚ࢫࢸࣝ⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ115.0ࠊ115.31ࠊ115.33ࠊ147.3ࠊ
147.6ࠊ147.9 ppm ࡟஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ56.5 ppm ࡟ 3 ᮏࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࢝ࢵࣉࣜࣥࢢᐃᩘ (15.9 Hz) ࡼࡾࠊtrans ஧㔜⤖ྜࡀᏑᅾࡍࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋ࣋ࣥࢮࣥ⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾ 3 ࡘࡢ feruloyl ᇶࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࡓࠋࡲࡓࠊ
IR ࢫ࣌ࢡࢺࣝ࠿ࡽࠊỈ㓟ᇶࠊ࢝ࣝ࣎ࢽࣝᇶࠊⰾ㤶⎔ཬࡧ࢚࣮ࢸࣝ⤖ྜ࡟⏤᮶ࡍࡿ྾཰ࡀほࡉࢀࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ
㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋࡉࡽ࡟㒊ศᵓ㐀ྠኈࡢ⤖ྜࢆ௓ࡋࡓ┦㛵ࡀほ ࡉࢀࠊ
glucose ࡢ 2'఩ࠊfructose ࡢ 3 ఩ࠊ6 ఩࡟ 3 ࡘࡢ feruloyl ᇶࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ
ࡲࡓࠊ୕ࡘࡢⰾ㤶⎔ࡢ 6''఩ࠊ6'''఩ࠊ6''''఩࠿ࡽ 4''఩ࠊ4'''఩ࠊ4''''఩࡬ࡢ┦㛵ࡀࡑࢀࡒࢀ☜ㄆࡉࢀࡓࡇ࡜࠿ࡽࠊࣇ࢙ࣝࣛ㓟ࡀᏑᅾࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
௨ୖࡼࡾࠊCompound 2 ࢆ Fig. 1 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

5

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Colorless amorphous powder
HR-ESI-MS (negative)
m/z: 869.2501 [M-H](calcd for C42H45O20: 869.2501)[α]D26 = +54.4 (c = 0.93, MeOH)
IR (film, cm-1): 3344, 2923, 2851, 1716, 1697, 1686, 1519, 1508, 1270, 1161,
1028
UV λmax (MeOH) nm (log ε): 237 (4.18), 264 (3.69), 300 (4.17), 327 (4.34)

Fig. 1 Structure and physical data of Compound 2




6

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COSY

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HMBC

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Fig. 2 COSY and HMBC correlations of Compound 2
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7

Table 1. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 2 in CD3OD

position
1

13

1

C
64.4

2
3
4
5
6
1'
2'
3'
4'
5'
6'

105.9
78.7
74.9
81.2
66.1
91.4
74.7
72.4
71.8
74.2
62.6

R-3 γ''
α''
β''
1''
2''
3''
4''
5''
6''
OCH3
R-6 γ'''
α'''
β'''
1'''
2'''
3'''
4'''
5'''
6'''
OCH3
R-2' γ''''

168.6
147.9
115.0
127.7
112.1
149.4
150.7
116.6
124.4
56.5
169.2
147.3
115.31
127.8
111.8
149.5
150.7
116.6
124.4
56.5
168.9

H
3.62 (1H, d, J=12.0 Hz)
3.49 (1H, d, J=12.0 Hz)
5.54 (1H, d, J= 8.3 Hz)
4.42 (1H, t, J= 8.3 Hz)
4.12 (1H, m)
4.46 (2H, d, J=5.4 Hz)
5.65 (1H, d, J= 3.7 Hz)
4.68 (1H, dd, J= 3.7, 10.0 Hz)
3.94 (1H, m)
3.48 (1H, t, J= 9.1 Hz)
3.95 (1H, m)
3.87 (1H, m)
3.76 (1H, m)
7.65 (1H, d, J= 15.9 Hz)
6.45 (1H, d, J= 15.9 Hz)
7.20 (1H, d, J= 1.9 Hz)

6.73 (1H, d, J= 8.3 Hz)
7.08 (1H, dd, J= 1.9, 8.3 Hz)
3.86 (3H, s)
7.61 (1H, d, J= 15.9 Hz)
6.34 (1H, d, J= 15.9 Hz)
7.13 (1H, d, J= 1.9 Hz)

6.79 (1H, d, J= 8.2 Hz)
7.02 (1H, dd, J= 1.9, 8.2 Hz)
3.75 (3H, s)

8



α''''
147.6
β''''
115.33
1''''
127.8
2''''
112.0
3''''
149.3
4''''
150.9
5''''
116.6
6''''
124.1
OCH3
56.5
m: multiplet or overlapped signals

7.70 (1H, d, J= 15.9 Hz)
6.31 (1H, d, J= 15.9 Hz)
6.98 (1H, d, J= 1.9 Hz)

6.70 (1H, d, J= 8.2 Hz)
6.92 (1H, dd, J= 1.9, 8.2 Hz)
3.84 (3H, s)

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9

➨ 2 㡯 ᪂つ໬ྜ≀ Compound 11 ࡢᵓ㐀Ỵᐃ
Cpd 11 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C44H48O21 ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋCpd 11 ࡟
ࡣ NMR ࢫ࣌ࢡࢺࣝࡼࡾ⢾ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡓࡓࡵࠊNaOMe ࡛࢔ࣝ࢝ࣜຍỈศゎࢆ⾜࠸ࠊ㐟㞳ࡋࡓ⢾࡟ࡘ࠸࡚᪕ගᗘ᳨ฟჾ௜ࡁ HPLC ࢆ⏝࠸࡚⢾ศᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
Cpd 11 ࡟ࡣ sucrose ࡀྵࡲࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣ 13C NMR ࡟࠾࠸࡚ sucrose ࡟⏤᮶ࡍࡿ 12 ᮏࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜࡜୍⮴ࡋࡓࠋࡑࡢ௚࡟ࡶ 13C NMR ࡟࠾࠸࡚ 112.0~151.0ppm ࡟ⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ168.6ࠊ
168.8ࠊ169.1 ppm ࡟࢚ࢫࢸࣝ⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ114.9ࠊ115.2ࠊ115.5ࠊ147.3ࠊ147.7ࠊ
148.1 ppm ࡟஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ56.6ࠊ56.7ࠊ56.7 ppm ࡟ 3 ᮏࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ173.0ࠊ21.0 ppm ࡟࢔ࢭࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀほ ࡉࢀࡓࠋࡲࡓࠊ1
H NMR ࡟࠾࠸࡚ࠊ࢝ࢵࣉࣜࣥࢢᐃᩘ (ca. 16 Hz)ࡼࡾࠊtrans య࡛࠶ࡿ࡜Ỵᐃࡉࢀࠊ࣋ࣥࢮ
ࣥ⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾ 3 ࡘࡢ feruloyl ᇶࡀ⤖ྜࡋ࡚࠸ࡿ࡜᥎ ࡋࡓࠋࡲࡓࠊIR ࢫ࣌ࢡࢺࣝ࠿ࡽࠊỈ㓟ᇶࠊ࢝ࣝ࣎ࢽࣝᇶࠊⰾ㤶⎔ཬࡧ࢚࣮ࢸࣝ⤖ྜ࡟⏤᮶ࡍࡿ྾཰ࡀほ ࡉࢀࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋࡉࡽ࡟㒊ศᵓ㐀㛫ࡢ⤖ྜࢆ♧ࡍ┦㛵ࡀほ ࡉࢀࠊ
glucose ࡢ 2' ఩ࠊfructose ࡢ 3 ఩ࠊ6 ఩࡟ 3 ࡘࡢ feruloyl ᇶࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊ3 ࡘࡢⰾ㤶⎔ࡢ 6''఩ࠊ6'''఩ࠊ6''''఩࠿ࡽ 4''఩ࠊ4'''఩ࠊ4''''఩࡬ࡢ┦㛵ࡀࡑࢀࡒࢀ
☜ㄆࡉࢀࡓࡇ࡜࠿ࡽࠊ࢖ࢯࣇ࢙ࣝࣛ㓟࡛࡞ࡃࠊࣇ࢙ࣝࣛ㓟ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟
࡞ࡗࡓࠋ௨ୖࡼࡾࠊCompound 11 ࢆ Fig. 3 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ
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10

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Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 935.2581 [M+Na]+(calcd for C44H48O21Na: 935.2580)[α]D26 = +46.9 (c = 1.03, MeOH)
IR (film, cm-1): 3344, 2921, 2851, 1717, 1699, 1684, 1520, 1507, 1270, 1161, 1030
UV λmax (MeOH) nm (log ε): 237 (4.06), 264 (3.62), 300 (4.12), 327 (4.25)

Fig. 3 Structure and physical data of Compound 11
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11

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COSY

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Fig. 4 COSY and HMBC correlations of Compound 11
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12

HMBC

Table 2.

13

C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 11 in CD3OD
13

position
1

C
64.8

2
3
4
5
6
1'
2'
3'
4'
5'
6'

105.6
78.5
74.3
81.4
65.4
90.7
74.6
72.3
72.1
72.1
65.4

OAc-6'

173.0
21.0
168.6
148.1
114.9
127.8
112.0
149.5
151.0
116.7
124.6
56.6
169.1
147.3
115.5
128.0
112.0
149.6
150.8
116.6
124.4

R-3 γ''
α''
β''
1''
2''
3''
4''
5''
6''
OCH3
R-6 γ'''
α'''
β'''
1'''
2'''
3'''
4'''
5'''
6'''

1

H
3.64 (1H, d, J=12.0 Hz)
3.45 (1H, d, J=12.0 Hz)
5.58 (1H, d, J= 8.5 Hz)
4.50 (1H, t, J= 8.5 Hz)
4.12 (1H, m)
4.50 (2H, m)
5.70 (1H, d, J= 3.8 Hz)
4.69 (1H, dd, J= 3.8, 10.1 Hz)
3.92 (1H, m)
3.38 (1H, t, J= 9.3 Hz)
4.19 (1H, m)
4.56 (1H, m)
4.16 (1H, m)
2.08 (3H, s)
7.71 (1H, d, J= 15.8 Hz)
6.48 (1H, d, J= 15.8 Hz)
7.27 (1H, d, J= 1.8 Hz)

6.76 (1H, d, J= 8.2 Hz)
7.13 (1H, dd, J= 1.8, 8.2 Hz)
3.83 (3H, s)
7.67 (1H, d, J= 16.0 Hz)
6.40 (1H, d, J= 16.0 Hz)
7.21 (1H, d, J= 1.8 Hz)

6.82 (1H, d, J= 8.2 Hz)
7.00 (1H, dd, J= 1.8, 8.2 Hz)

13

OCH3
56.7
R-2' γ''''
168.8
α''''
147.7
β''''
115.2
1''''
127.8
2''''
112.1
3''''
149.6
4''''
150.9
5''''
116.5
6''''
124.3
OCH3
56.7
m: multiplet or overlapped signals

3.90 (3H, s)
7.64 (1H, d, J= 15.9 Hz)
6.36 (1H, d, J= 15.9 Hz)
7.01 (1H, d, J= 1.8 Hz)

6.82 (1H, d, J= 8.2 Hz)
7.10 (1H, m)
3.90 (3H, s)

14

➨ 4 ⠇  ᪤▱໬ྜ≀࡟ࡘ࠸࡚ࣇࢩࢢࣟᆅୖ㒊ࡢ n- ࣊࢟ࢧࣥྍ⁐⏬ศ࡜㓑㓟࢚ࢳࣝྍ⁐⏬ศࢆศ㞳ࠊ⢭〇ࡍࡿ㐣⛬࡛ࠊ᪂つ໬ྜ≀࡜࡜ࡶ࡟ࠊ᪤▱໬ྜ≀ 18 ✀ࢆ༢㞳ࡋࡓࠋྛ໬ྜ≀ࡢ NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆ
ᩥ⊩್࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࢀࡒࢀ௨ୗ࡟♧ࡍ᪤▱໬ྜ≀࡛࠶ࡿ࡜ྠᐃࡋࡓࠋ

Compound 1: Helonioside A 3)
Compound 3: Vanillin 4)
Compound 4: (3R, 6R, 7E)-3-Hydroxy-4,7-megastigmadien-9-one 5)
Compound 5: Scopoletin 6)
Compound 6: (9S, 12S, 13S)-E-9,12,13-Trihydroxy-10-octadecaenoic acid 7)
Compound 7: 20-Hydroxy-ecdysone 8)
Compound 8: Luteolin 3'-O-methyl-6-C-β-D-glucopyranoside 9)
Compound 9: Apigenin-6-C-β-D-glucopyranoside 10)
Compound 10: Maltol β-D-glucopyranoside 6'-O-Benzoatein 11)
Compound 12: 22-O-acetyl 20-hydroxy-ecdysone 12)
Compound 13: 3-Hydroxy-1-(4-hydroxy-3-methoxyphenyl) propan-1-one 13)
Compound 14: (6S,9R)-Vomifoliol 14)
Compound 15: 4-Hydroxybenzaldehyde 15)
Compound 16: (+)-dehydrovomifoliol 16)
Compound 17: 3-(4-Hydroxy-3-methoxyphenyl) propanoic acid 17)
Compound 18: Indole-3-carboxaldehyde 18, 19)Compound 19: Isovanillic acid 20)
Compound 20: grasshopper ketone 21)15➨ 1 㡯 ᪤▱໬ྜ≀ Compound 1 ࡢᵓ㐀Ỵᐃ
Cpd 1 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C32H38O17 ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋCpd 1 ࡟ࡣ NMR ࢫ࣌ࢡࢺࣝࡼࡾ⢾ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡓࡓࡵࠊNaOMe ࡛࢔ࣝ࢝ࣜຍỈศゎࢆ⾜࠸ࠊ㐟㞳ࡋࡓ⢾࡟ࡘ࠸࡚᪕ගᗘ᳨ฟჾ௜ࡁ HPLC ࢆ⏝࠸࡚⢾ศᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
Cpd 1 ࡟ࡣ sucrose ࡀྵࡲࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣ 13C NMR ࡟࠾࠸࡚ sucrose ࡟⏤᮶ࡍࡿ 12 ᮏࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜࡜୍⮴ࡋࡓࠋࡑࡢ௚࡟ࡶ 13C NMR ࡟࠾࠸࡚ 112.0~150.9 ppm ࡟ⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ168.5ࠊ
169.2 ppm ࡟࢚ࢫࢸࣝ⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ115.1ࠊ115.3ࠊ147.4ࠊ148.0 ppm ࡟஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࠊ56.7 ppm ࡟ 2 ᮏࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࢝ࢵࣉࣜࣥࢢᐃᩘ (15.9 Hz)ࡼࡾࠊtrans ஧㔜⤖ྜ࡛࠶ࡿ࡜Ỵᐃࡉࢀࠊ࣋ࣥࢮࣥ⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ2 ࡘࡢ
feruloyl ᇶࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 3)࡜ẚ㍑ࡋࡓ
࡜ࡇࢁࠊCpd 1 ࢆ helonioside A ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 693.2031 [M-H](calcd for C32H37O17: 693.2031)
Fig. 5 Structure and physical data of Compound 1

16

Table 3. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 1 in CD3OD
position
1
2
3
4
5
6
1'
2'
3'
4'
5'
6'
R-3 γ''
α''
β''
1''
2''
3''
4''
5''
6''
OCH3
R-6 γ''
α'''
β'''
1'''
2'''
3'''
4'''
5'''
6'''
OCH3

13

C           1H
65.3
3.53 (1H, m)
3.59 (1H, m)
105.3
79.4
5.42 (1H, d, J= 7.7 Hz)
75.2
4.37 (1H, t, J= 7.7 Hz)
81.4
4.10 (1H, m)
66.4
4.45 (2H, d, J=3.7 Hz)
93.2
5.38 (1H, d, J= 3.7 Hz)
74.5
3.90 (1H, m)
75.1
4.37 (1H, m)
71.5
3.34 (1H, m)
73.4
3.36 (1H, m)
62.8
3.80 (1H, d, J=2.5 Hz)
3.85 (1H, d, J=2.5 Hz)
168.5
148.0
7.64 (1H, d, J= 15.9 Hz)
115.1
6.36 (1H, d, J= 15.9 Hz)
127.9
112.3
7.16 (1H, d, J= 1.9 Hz)
149.5
150.9
116.7
6.75 (1H, d, J= 8.2 Hz)
124.4
7.02 (1H, dd, J= 1.9, 8.2 Hz)
56.7
3.86 (3H, s)
169.2
147.4
7.58 (1H, d, J= 15.9 Hz)
115.3
6.32 (1H, d, J= 15.9 Hz)
127.9
112.0
7.12 (1H, d, J= 2.0 Hz)
149.6
150.9
116.7
6.75 (1H, d, J= 8.2 Hz)
124.4
7.06 (1H, dd, J= 2.0, 8.2 Hz)
56.7
3.75 (3H, s)

m: multiplet or overlapped signals17

➨ 2 㡯 ᪤▱໬ྜ≀ Compound 3 ࡢᵓ㐀Ỵᐃ
Cpd 3 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C8H8O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR ࡟࠾࠸࡚ࠊ111.5 ࠿ࡽ 154.9 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶
ࡾࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ193.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ࡢ proton ࡀ ABX
ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4 ఩࡟⨨᥮ᇶࡢࡘ࠸ࡓ࣋ࣥࢮࣥᵓ㐀ࢆ᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 4)࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 3 ࢆ vanillin ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 151.1394 [M-H](calcd for C8H7O3: 151.1393)
Fig. 6 Structure and physical data of Compound 3

Table 4. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 3 in CD3OD
position
1
2
3
4
5
6
1-CHO
3-OCH3

13

1

C
130.8
111.5
149.9
154.9
116.5
128.1
193.1
56.6

H

7.44 (1H, d, J=1.9 Hz)

6.94 (1H, d, J=7.9 Hz)
7.44 (1H, dG, J=7.9, 1.9 Hz)
9.75 (1H, s)
3.92 (3H, s)

18

➨ 3 㡯 ᪤▱໬ྜ≀ Compound 4 ࡢᵓ㐀Ỵᐃ
Cpd 4 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H20O2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ
200.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡑࡋ࡚ࠊ1H NMR ࡟࠾
࠸࡚ࠊ6.57 ppm ࡟࢝ࢵࣉࣜࣥࢢᐃᩘ 16.0 Hz ࡜ 10.3 Hz ࡢ dd ࡢࣆ࣮ࢡࠊ6.04 ppm ࡟࢝ࢵࣉࣜࣥࢢ 16.0 Hz ࡢࣆ࣮ࢡࡀぢࡽࢀࡓࡇ࡜ࡼࡾࠊ୍ࡘࡢ trans ࡢ஧㔜⤖ྜ࡜୍ࡘࡢ࢝ࣝ࣎ࢽࣝ
ࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 5)࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ
Cpd 4 ࢆ(3R,6R,7E)-3-hydroxy-4,7-megastigmadien-9-one ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 231.1356 [M+Na]+(calcd for C13H20O2Na: 231.1356)

Fig. 7 Structure and physical data of Compound 4

19

Table 5. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 4 in CD3OD
position
1
2

13

1

C
35.1
45.2

H

1.71 (1H, dd, J= 13.2, 5.9 Hz)
1.29 (1H, dd, J= 13.2, 7.1 Hz)
4.12 (1H, m)
5.50 (1H, m)

3
66.1
4
127.5
5
136.0
6
55.7
2.48 (1H, d, J=10.3 Hz)
7
149.9
6.57 (1H, dd, J= 16.0, 10.3 Hz)8
134.8
6.04 (1H, d, J= 16.0 Hz)
9
200.9
10
27.2
2.17 (3H, s)11
29.9
0.91 (3H, s)
1224.6
0.80 (3H, m)
13
22.9
1.52 (3H, s)
m: multiplet or overlapped signals20

➨ 4 㡯 ᪤▱໬ྜ≀ Compound 5 ࡢᵓ㐀Ỵᐃ
Cpd 5 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H8O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ104.2 ࠿ࡽ 153.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ57.0 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ112.6 ppm ࡜ 146.3 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ164.2 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ7.86 ppm ࡟࢝ࢵࣉࣜࣥࢢᐃᩘ 9.4 Hz ࡢ d ࡢࣆ࣮ࢡࠊ6.20
ppm ࡟࢝ࢵࣉࣜࣥࢢᐃᩘ 9.4 Hz ࡢࣆ࣮ࢡࡀぢࡽࢀࡓࡇ࡜ࡼࡾࠊ୍ࡘࡢ cis ࡢ஧㔜⤖ྜ࡜࣋ࣥࢮࣥ⎔ࡢᏑᅾࢆ᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 6)࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 5 ࢆscopoletin ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 193.0494 [M+H]+(calcd for C10H9O4: 193.0495)

Fig. 8 Structure and physical data of Compound 5

21

Table 6. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 5 in CD3OD
position
2
3
4
5
6
7
8
9
10
-OCH3

13

C
164.2
112.6
147.2
110.1
147.2
151.7
104.2
153.3
112.6
57.0

22

1

H

6.20 (1H, d, J= 9.4 Hz)
7.86 (1H, d, J= 9.4 Hz)
7.11 (1H, s)

6.77 (1H, s)

3.91 (3H, s)➨ 5 㡯 ᪤▱໬ྜ≀ Compound 6 ࡢᵓ㐀Ỵᐃ
Cpd 6 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C18H34O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ࢔ࣝ࢟ࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 15 ᮏࠊ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏ,
178.7 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾ୍ࡘࡢ஧㔜⤖ྜ࡜୍ࡘࡢ࢝ࣝ࣎ࢽࣝᇶࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱཬࡧ᪕ග ᗘ ࢆ ᩥ ⊩ ್ 7) ࡜ ẚ ㍑ ࡋ ࡓ ࡜ ࡇ ࢁ ࠊ Cpd 6 ࢆ (9S,12S,13S)-E-9,12,13-trihydroxy-10octadecaenoic acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 353.2299 [M+Na]+(calcd for C18H34O5Na: 353.2298)[α]D26 = -9.0 (c = 1.07, MeOH)

Fig. 9 Structure and physical data of Compound 6

23

Table 7. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 6 in CD3OD
13
position
C
1
178.7
2
35.8
3
26.5
4
30.4
5
30.6-30.7
6
7
26.6
8
38.5
9
73.2
10
136.2
11
131.2
12
76.8
13
75.9
14
33.7
15
26.7
16
33.3
17
23.8
18
14.6
m: multiplet or overlapped signals

24

1

H

2.26 (2H, t, J= 7.5 Hz)
1.60 (2H, m)
1.27-1.56 (10H, m)

4.05 (1H, m)
5.69 (1H, m)
5.70 (1H, m)
3.91 (1H, m)
3.41 (1H, m)
1.27-1.56 (8H, m)
0.91 (3H, t, J=6.9 Hz)➨ 6 㡯 ᪤▱໬ྜ≀ Compound 7 ࡢᵓ㐀Ỵᐃ
Cpd 7 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H44O7 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ࢔ࣝ࢟ࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 26 ᮏ, 206.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏ ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ୍ࡘࡢ࢝ࣝ࣎ࢽࣝᇶࢆ᭷ࡋࡓ steroid ᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 8) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 7 ࢆ 20-hydroxyecdysone ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 503.2972 [M+Na]+(calcd for C27H44O7Na: 503.2979)

Fig. 10 Structure and physical data of Compound 7

25

Table 8. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 7 in CD3OD
13

position
1

C
37.5

2
3
4

68.8
68.7
33.0

5
6
7
8
9
10
11

51.9
206.6
122.3
168.1
35.7
39.4
21.6

12

32.7

13
14
15

48.7
85.4
31.9

16

21.6

17
18
19
20
21
22
23

50.7
18.2
24.5
78.1
21.2
78.6
27.5

24

42.5

25
26
27

71.5
29.1
29.8

1

H
1.42
1.79
3.84 (1H, ddd, J= 11.8, 4.0, 3.2 Hz)
3.95 (1H, m)
1.69
1.76
2.37 (1H, m)
5.81 (1H, d, J= 2.3 Hz)
3.15 (1H, m)
1.71
1.80
2.13 (1H, ddd, J= 12.9, 12.9, 4.6 Hz)
1.88

1.60
1.96
1.78
1.99
2.38 (1H, m)
0.90 (1H, s)
0.97 (1H, s)
1.20 (1H, s)
3.34 (1H, m)
1.30
1.66
1.80
1.44
1.19 (1H, s)
1.20 (1H, s)

m: multiplet or overlapped signals26

➨ 7 㡯 ᪤▱໬ྜ≀ Compound 8 ࡢᵓ㐀Ỵᐃ
Cpd 8 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C22H22O11 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ63.0 ࠿ࡽ 95.6 ppm ࡟ࢢࣝࢥ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ56.8 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ184.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝ
ࡀ 1 ᮏほ ࡉࢀࡓࠋࡑࡋ࡚ࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4 ఩࡟⨨᥮ᇶࡀࡘ࠸ࡓ flavonoid ᵓ㐀ࢆ᥎ ࡋࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 9)࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 8 ࢆ luteolin 3'-O-methyl-6-C-β-Dglucopyranoside ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (positive)
m/z: 485.1051 [M+Na]+(calcd for C22H22O11Na: 485.1054)

Fig. 11 Structure and physical data of Compound 827

Table 9. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 8 in CD3OD
position
2
3
4
5
6
7
8
9
10
1'
2'
3'
4'
5'
6'
glucose
1''
2''
3''
4''
5''
6''

13

C
166.1
104.3
184.0
162.1
109.5
165.9
95.6
158.9
105.1
123.6
110.7
149.7
152.4
117.0
121.9

1

80.3
72.7
75.5
71.9
82.7
63.0

3.49 (1H, m)
4.19 (1H, m)
4.90 (1H, d, J= 10 Hz)
3.49 (1H, m)
3.42 (1H, m)
3.88 (1H, dd, J= 2.2, 12.1 Hz)
3.75 (1H, dd, J= 5.3, 12.1 Hz)
3.94 (3H, s)

H

6.58 (1H, s)

6.46 (1H, s)

7.45 (1H, d, J= 2.1 Hz)

6.91 (1H, d, J= 8.3 Hz)
7.46 (1H, dd, J= 2.1, 8.3 Hz)

OCH3
56.8
m: multiplet or overlapped signals28

➨ 8 㡯 ᪤▱໬ྜ≀ Compound 9 ࡢᵓ㐀Ỵᐃ
Cpd 9 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C21H20O10 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ63.0 ࠿ࡽ 95.8 ppm ࡟ࢢࣝࢥ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ184.0
ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋ௨ୖࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 10)࡜ẚ㍑ࡍࡿࡇ࡜࡟ࡼࡾࠊCpd 9 ࢆ apigenin-6-C-β-D-glucopyranoside ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (positive)
m/z: 455.0947 [M+Na]+(calcd for C21H20O10Na: 455.0949)

Fig. 12 Structure and physical data of Compound 929

Table 10. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 9 in CD3OD
position
2
3
4
5
6
7
8
9
10
1'
2'
3'
4'
5'
6'
glucose
1''
2''
3''
4''
5''
6''

13

C
166.2
103.9
184.0
162.2
109.6
166.1
95.8
159.0
104.9
123.6
129.5
117.3
163.1
117.3
129.4

1

75.5
72.7
80.4
71.9
82.7
63.0

4.90 (1H, d, J= 9.9 Hz)
4.19 (1H, dd, J=9.9, 8.9 Hz)
3.45 (1H, m)
3.45 (1H, m)
3.42 (1H, m)
3.87 (1H, dd, J= 2.0, 12.1 Hz)
3.75 (1H, dd, J= 5.3, 12.1 Hz)

H

6.57 (1H, s)

6.47 (1H, s)

7.83 (1H, d, J= 8.9 Hz)
6.92 (1H, d, J= 8.9 Hz)
6.92 (1H, d, J= 8.9 Hz)
7.83 (1H, d, J= 8.9 Hz)

m: multiplet or overlapped signals30

➨ 9 㡯 ᪤▱໬ྜ≀ Compound 10 ࡢᵓ㐀Ỵᐃ
Cpd 10 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C19H20O9 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ64.9 ppm ࠿ࡽ 104.2 ppm ࡟ࢢࣝࢥ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡ࡜ࠊ129.7 ࠿ࡽ
134.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ176.9 ppm ࡜167.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝ 4 ᮏ
ࡀほ ࡉࢀࡓࠋNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 11) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 10 ࢆ maltol βD-glucopyranoside 6'-O-benzoate ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 415.0994 [M+Na]+(calcd for C19H20O9Na: 415.1000)

Fig. 13 Structure and physical data of Compound 10

31

Table 11. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 10 in CD3OD
position
1
2
3
4
5
6
7
1'
2'
3'
4'
5'
6'

13

1

C

164.6
142.8
176.9
117.2
157.1
15.8
104.2
75.3
77.6
71.7
75.7
64.9

H

6.31 (1H, d, J= 5.6 Hz)
7.78 (1H, d, J=5.6 Hz)
2.19 (3H, s)
4.86 (1H, d, J= 7.8 Hz)
3.43 (1H, m)
3.52 (1H, m)
3.45 (1H, m)
3.59 (1H, m)
4.57 (1H, dd, J= 11.8, 2.3 Hz)
4.48 (1H, dd, J= 11.8, 6.9 Hz)

1''
130.9
2''
130.5
3''
129.7
4''
134.5
5''
129.7
6''
130.5
7''
167.9
m: multiplet or overlapped signals

7.87 (2H, dd, J= 8.2, 1.1 Hz)
7.40 (2H, m)
7.54 (1H, m)
7.40 (2H, m)
7.87 (2H, dd, J= 8.2, 1.1 Hz)

32➨ 10 㡯 ᪤▱໬ྜ≀ Compound 12 ࡢᵓ㐀Ỵᐃ
Cpd 12 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C29H46O8 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ࢔ࣝ࢟ࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 26 ᮏ, 206.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏ, 173.4 ppm ࡜ 21.3 ppm ࡢ࢔ࢭࢺ࢟ࢩᇶࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜
ࡼࡾࠊ୍ࡘࡢ࢔ࢭࢺ࢟ࢩᇶࢆ⤖ྜࡋࡓ steroid ᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮
ࢱࢆᩥ⊩್ 12)࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 12 ࢆ 22-O-acetyl 20-hydroxy-ecdysone ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 545.3080 [M+Na]+(calcd for C29H46O8Na: 545.3085)

Fig. 14 Structure and physical data of Compound 12

33

Table 12.

13

C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 12 in CD3OD
13

position
1

C
37.5

2
3
4

68.8
68.7
33.0

5
6
7
8
9
10
11

51.9
206.6
122.3
167.9
35.2
39.4
21.6

12

32.7

13
14
15

85.3
31.9

16

21.6

17
18
19
20
21
22
23

51.1
18.2
24.5
77.7
21.3
80.8
26.4

24

41.7

25
26
27
C=O
CH3CO-

71.1
29.1
29.6
173.5
21.3

m: multiplet or overlapped signals
34

1

H
1.32
1.69
3.84 (1H, m)
3.95 (1H, m)
1.60
1.65
2.37 (1H, m)
5.84 (1H, d, J= 2.4 Hz)
3.16 (1H, m)
1.59
1.70
2.04 (1H, m)
1.78 (1H, m)
1.52
1.89
1.71
1.60
2.38 (1H, m)
0.89 (3H, s)
0.96 (3H, s)
1.20 (1H, s)
4.87 (1H, m)
1.37
1.65
1.33
1.28
1.18 (3H, s)
1.30 (3H, s)
2.10 (3H, s)➨ 11 㡯 ᪤▱໬ྜ≀ Compound 13 ࡢᵓ㐀Ỵᐃ
Cpd 13 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H12O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ112.0 ppm ࠿ࡽ 153.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ199.8 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝ 1ᮏࡀほ ࡉࢀࡓࠋࡑࡋ࡚ࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ࡢ protonࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4 ఩࡟⨨᥮ᇶࡀࡘ࠸ࡓ࣋ࣥࢮ
ࣥᵓ㐀ࢆ᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 13) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 13 ࢆ 3hydroxy-1-(4-hydroxy-3-methoxyphenyl) propan-1-one ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 219.0627 [M+Na]+(calcd for C10H12O4Na: 219.0628)

Fig. 15 Structure and physical data of Compound 13

35

Table 13. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 13 in CD3OD
position
1
2
3
4
5
6
7
8
9
3-OCH3

13

1

C
130.7
112.0
149.2
153.5
115.9
124.9
199.8
41.8
59.0
56.5

H

7.54 (1H, d, J=2.0 Hz)

6.86 (1H, d, J= 8.3 Hz)
7.58 (1H, dd, J= 8.3, 2.0 Hz)
3.16 (2H, t, J= 6.2 Hz)
3.94 (2H, t, J= 6.2 Hz)
3.91 (3H, s)36➨ 12 㡯 ᪤▱໬ྜ≀ Compound 14 ࡢᵓ㐀Ỵᐃ
Cpd 14 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H20O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ
201.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࡀほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾
࠸࡚ࠊ5.81 ppm ࡟࢝ࢵࣉࣜࣥࢢᐃᩘ 16.9 Hz ࡜ 6.0 Hz ࡢ dd ࡢࣆ࣮ࢡࠊ5.79 ppm ࡟࢝ࢵࣉࣜ
ࣥࢢᐃᩘ 16.9 Hz ࡢࣆ࣮ࢡࡀぢࡽࢀࡓࡇ࡜ࡼࡾࠊ୍ࡘࡢ trans ࡢ஧㔜⤖ྜ࡜୍ࡘࡢ࢝ࣝ࣎ࢽ
ࣝᇶࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱཬࡧ᪕ගᗘࢆᩥ⊩್ 14) ࡜ẚ
㍑ࡋࡓ࡜ࡇࢁࠊCpd 14 ࢆ(6S,9R)-vomifoliol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 247.1305 [M+Na]+(calcd for C13H20O3Na: 247.1305)[α]D26 = +141 (c = 1.00, MeOH)

Fig. 16 Structure and physical data of Compound 14

37

Table 14. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 14 in CD3OD
13

position
1
2

C
42.6
50.8

3
4
5
6
7
8
9
10
11
12
13

201.5
127.2
167.7
80.1
130.0
137.0
68.8
19.7
24.6
24.0
23.6

1

H

2.16 (1H, d, J= 16.9 Hz)
2.48 (1H, d, J= 16.9 Hz)
5.88 (1H, brs)

5.78 (1H, d, J= 16.9 Hz)
5.81 (1H, dd, J= 16.9, 6.0 Hz)
4.57 (1H, brs)
1.24 (3H, d, J=6.4 Hz)
1.02 (3H, s)
1.04 (3H, s)
1.92 (3H, d, J=1.1 Hz)38➨ 13 㡯 ᪤▱໬ྜ≀ Compound 15 ࡢᵓ㐀Ỵᐃ
Cpd 15 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C7H6O2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ117.0 ppm ࠿ࡽ 165.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ193.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ
1ࠊ4 ఩࡟⨨᥮ᇶࡢࡘ࠸ࡓ࣋ࣥࢮࣥᵓ㐀ࢆ᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 15) ࡜ẚ
㍑ࡋࡓ࡜ࡇࢁࠊCpd 15 ࢆ 4-hydroxybenzaldehyde ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 121.0296 [M-H](calcd for C7H5O2: 121.0295)
Fig. 17 Structure and physical data of Compound 15

Table 15. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 15 in CD3OD
position
1
2
3
4
5
6
CHO

13

1

C
130.4
133.6
117.0
165.3
117.0
133.6
193.0

H

7.77 (1H, d, J= 8.7 Hz)
6.91 (1H, d, J= 8.6 Hz)
6.91 (1H, d, J= 8.6 Hz)
7.77 (1H, d, J= 8.7 Hz)
9.76 (1H, s)39➨ 14 㡯 ᪤▱໬ྜ≀ Compound 16 ࡢᵓ㐀Ỵᐃ
Cpd 16 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H18O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ
200.5 ppmࠊ200.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H
NMR ࡟࠾࠸࡚ࠊ6.99 ppm ࡟࢝ࢵࣉࣜࣥࢢᐃᩘ 15.8 Hz ࡢ d ࡢࣆ࣮ࢡ࡜ 6.44 ppm ࡟࢝ࢵࣉࣜ
ࣥࢢᐃᩘ 15.8 Hz ࡢ d ࡢࣆ࣮ࢡࡀぢࡽࢀࡓࡇ࡜ࡼࡾࠊ୍ࡘࡢ trans ஧㔜⤖ྜ࡜஧ࡘࡢ࢝ࣝ࣎
ࢽࣝᇶࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱཬࡧ᪕ගᗘࢆᩥ⊩್ 16) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 16 ࢆ(+)-dehydrovomifoliol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 245.1148 [M+Na]+(calcd for C13H18O3Na: 245.1148)

Fig. 18 Structure and physical data of Compound 16

40

Table 16. 13C NMR (125MHz) and 1H NMR (500 MHz) data for Cpd 16 in CD3OD
13

position
1
2

C
42.8
50.7

3
4
5
6
7
8
9
10
11
12
13

200.5
128.2
164.8
80.1
148.5
131.9
200.9
27.8
23.7
24.9
19.3

1

H

2.60 (1H, d, J= 17.1 Hz)
2.28 (1H, d, J= 17.1 Hz)
5.93 (1H, s)

6.99 (1H, d, J= 15.8 Hz)
6.44 (1H, d, J= 15.8 Hz)
2.30 (3H, s)
1.06 (3H, s)
1.02 (3H, s)
1.90 (3H, d, J=1.4 Hz)

41

➨ 15 㡯 ᪤▱໬ྜ≀ Compound 17 ࡢᵓ㐀Ỵᐃ
Cpd 17 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H12O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ113.2 ppm ࠿ࡽ 149.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ177.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ࡢ protonࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4 ఩࡟⨨᥮ᇶࡀࡘ࠸ࡓ࣋ࣥࢮ
ࣥᵓ㐀ࢆ᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 17) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 17 ࢆ 3-(4-hydroxy-3-methoxyphenyl) propanoic acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 195.0664 [M-H](calcd for C10H11O4: 195.0663)

Fig. 19 Structure and physical data of Compound 17

42

Table 17. 13C NMR (125MHz) and 1H NMR (500 MHz) data for Cpd 17 in CD3OD
position
1
2
3
4
5
6
7
8
9
3-OCH3

13

1

C
134.0
113.2
149.0
145.9
116.3
121.8
32.0
37.7
177.6
56.5

H

6.80 (1H, d, J=1.8 Hz)

6.70 (1H, d, J= 8.0 Hz)
6.64 (1H, dd, J= 8.0, 1.9 Hz)
2.82 (2H, t, J= 7.7 Hz)
2.54 (2H, t, J= 7.7 Hz)
3.83 (3H, s)

43➨ 16 㡯 ᪤▱໬ྜ≀ Compound 18 ࡢᵓ㐀Ỵᐃ
Cpd 18 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C9H7ON ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ113.3 ppm ࠿ࡽ 139.1 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ187.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 18ࠊ19) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 18 ࢆ indole-3-carboxaldehyde࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Pale yellow amorphous powder
HR-ESI-MS (positive)
m/z: 146.0599 [M+H]+(calcd for C9H8ON: 146.0600)
Fig. 20 Structure and physical data of Compound 18

Table 18.

13

C NMR (125MHz) and 1H NMR (500 MHz) data for Cpd 18 in CD3OD

position
2
3
4
5
6
7
8
9
CHO
m: multiplet or overlapped signals

13

1

C
139.9
120.3
122.5
123.8
125.2
113.3
125.9
139.1
187.6

H
8.10 (1H, s)
8.16 (1H, d, J= 7.9 Hz)
7.20-7.30 (2H, m)
7.48 (1H, d, J= 8.0 Hz)

9.89 (1H, s)

44➨ 17 㡯 ᪤▱໬ྜ≀ Compound 19 ࡢᵓ㐀Ỵᐃ
Cpd 19 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C8H8O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ113.9 ࠿ࡽ 152.8 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ170.2 ppm ࡢ࢝ࣝ࣎ࢽࣝ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ
࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX
ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࡀᏑᅾࡋ࡚࠸ࡿ࡜᥎ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 20) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 19 ࢆ isovanillic acid ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (negative)
m/z: 167.0352 [M-H](calcd for C8H7O4: 167.0350)

Fig. 21 Structure and physical data of Compound 19

45

Table 19.

13

C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 19 in CD3OD

position
1
2
3
4
5
6
1-COOH
4-OCH3

13

1

C
125.4
116.0
148.8
152.8
113.9
123.2
170.2
56.5

H

7.56 (1H, d, J= 1.9 Hz)

6.84 (1H, d, J= 8.7 Hz)
7.55 (1H, dd, J= 8.7, 1.9 Hz)
3.88 (3H, s)

46

➨ 18 㡯 ᪤▱໬ྜ≀ Compound 20 ࡢᵓ㐀Ỵᐃ
Cpd 20 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H20O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ201.0 ppm ࡢ࢝ࣝ࣎ࢽࣝ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ101.3ࠊ120.1ࠊ211.7
ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ64.6ࠊ72.6 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 2 ᮏࠊ49.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ26.7ࠊ29.5ࠊ30.9ࠊ
32.4 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ
࣮ࢱࢆᩥ⊩್ 21) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 20 ࢆ grasshopper ketone ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 247.1304 [M+Na] +(calcd for C13H20O3Na: 247.1305)[α]D25 = -33.5 (c = 0.79, MeOH)

Fig. 22 Structure and physical data of Compound 20

47

Table 20. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 20 in CD3OD
13

position
1
2

C
37.1
49.9

3
4

64.6
-

5
6
7
8
9
10
11
12
13

72.6
120.1
211.7
101.3
201.0
26.7
29.5
32.4
30.9

1

H

1.93 (1H, ddd, J= 2.1, 4.1, 12.5 Hz)
1.41 (1H, m)
4.22 (1H, m)
2.22 (1H, dd, J= 2.1, 4.1 Hz)
1.33 (1H, m)

5.83 (1H, s)
2.19 (3H, s)
1.15 (3H, s)
1.38 (3H, m)
1.38 (3H, m)

m: multiplet or overlapped signals48

➨ 3 ❶ ᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢᡂศ◊✲➨ 1 ⠇ ᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡟ࡘ࠸࡚Ꮫྡ㸸Hosiea japonica࿴ྡ㸸ࢡࣟࢱ࢟࢝ࢬࣛ
⛉ྡ㸸Icacinaceae (ࢡࣟࢱ࢟࢝ࢬࣛ⛉)ᒓྡ㸸Hosiea (ࢡࣟࢱ࢟࢝ࢬࣛᒓ)≉ᚩ㸸 5-6 ᭶ࡈࢁ 5 ᘚࡢⷧ࠸㯤⥳ࡢᑠⰼࢆᩘಶဏ࠿ࡏࡿࠋ㞤㞝␗ᰴࠊⴥࡣ኱ࡁࡵ࡛㗬ṑࡢᙧࡀ≉ᚩࠊᒣᆅ࡟⏕࠼ࡿࡘࡿᛶⴠⴥపᮌ࡛ࡘࡿࡣᩘ m ࡟࡞ࡿࠋ9-10 ᭶ࡈࢁ㛗ࡉ 1520 mm ⛬ᗘࡢ⥮Ⰽࡢᐇࢆᆶࡽࡏࡿࠋྡ๓ࡣᅄᅜࡢ㯮⁪ᒣ࡛Ⓨぢࡉࢀࡓࡇ࡜࡟⏤᮶ࡋࠊⲔⰍࡢࡘࡿ࡟ࡣⓑ࠸ᩬⅬࡀ࠶ࡿࠋ22) ᮏ᳜≀࠿ࡽࡣࠊࡇࢀࡲ࡛࡟ᡂศ◊✲ࡢሗ࿌ࡣ࡞࠸ࠋ

http://kanon1001.web.fc2.com/foto_sinrin/K_kurotaki_kazura/kurotaki_kazura/kurotaki_kazura.htm

49➨ 2 ⠇ ᢳฟࠊศ㞳࠾ࡼࡧ⢭〇ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢࡘࡿࡢ㓑㓟࢚ࢳࣝᢳฟ≀㸦37.6 g㸧ࠊࢡࣟࢱ࢟࢝ࢬࣛ
Hosiea japonica ࡢⴥ㒊ࡢ㓑㓟࢚ࢳࣝᢳฟ≀㸦27.3 g㸧࡟ࡘ࠸࡚ᡂศ◊✲ࢆ⾜ࡗࡓࠋࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢࡘࡿࡢ㓑㓟࢚ࢳࣝྍ⁐⏬ศ㸦37.6 g㸧ࢆࠊࢩࣜ࢝ࢤࣝ
࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊODS ࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊཬࡧ ODS-HPLC ࢆ⏝࠸࡚ศ㞳ࠊ⢭〇ࡋࠊ23 ✀ࡢ໬ྜ≀ࢆ༢㞳ࡋࡓࠋࡑࡢෆ Compound 21 ࡣ᪂つ໬ྜ≀࡜ྠᐃࡋࡓࠋ
(Chart 2)ࡲࡓࠊࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢⴥ㒊ࡢ㓑㓟࢚ࢳࣝྍ⁐⏬ศ㸦27.3 g㸧ࢆࠊ㡰┦
ཬࡧ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊODS ࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊཬࡧ
ODS-HPLC ࢆ⏝࠸࡚ศ㞳ࠊ⢭〇ࡋࠊ11 ✀ࡢ໬ྜ≀ࢆ༢㞳ࡋࡓࠋࡑࡢෆ Compound 22 ࡣ᪂つ໬ྜ≀࡜ྠᐃࡋࡓࠋ(Chart 3)

Dried vines and leaves of Hosiea japonica
Extracted with MeOH
Partitioned with n-Hexane

MeOH layer
Evaporated
Suspended in H2OPartitioned with EtOAc

n-Hexane layer

Partitioned with 1-BuOH

EtOAc layer

1-BuOH layer

50

Aqueous layer

Chart 2: Isolated compounds from vine

Chart 3: Isolated compounds from leaves51➨ 3 ⠇  ᪂つ໬ྜ≀࡟ࡘ࠸࡚➨ 1 㡯 ᪂つ໬ྜ≀ Compound 21 ࡢᵓ㐀Ỵᐃ
Cpd 21 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࡑࡢศᏊᘧࢆ C20H34O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊⅣ⣲⥲ᩘ 20 ᮏࡢ࠺ࡕࠊ67.2ࠊ68.4ࠊ72.2ࠊ75.0ࠊ76.6 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 5 ᮏࠊࡑࢀ௨እ࡟ࠊ23.8ࠊ27.5ࠊ27.6ࠊ27.7ࠊ30.5ࠊ33.1ࠊ36.2
ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 6 ᮏࠊ31.6ࠊ34.4ࠊ38.8 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊຍ࠼࡚ 40.3ࠊ41.3ࠊ50.5 ppm ࡢ 4 ⣭Ⅳ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏほࡉࢀࡓࠋ13C NMR ࢫ࣌ࢡࢺࣝࡢ⤖ᯝ࠾ࡼࡧࠊศᏊᘧࡢせồࡍࡿ୙㣬࿴ᗘࢆ຺᱌ࡋࠊCpd
21 ࡣ aphidicolin ᆺࢪࢸࣝ࣌ࣥ࡜᥎ ࡋࡓࠋࡲࡓࠊIR ࢫ࣌ࢡࢺࣝ࠿ࡽࠊỈ㓟ᇶ࡟⏤᮶ࡍࡿࣆ࣮ࢡࡀほ ࡉࢀࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊ15
఩࡜ 17 ఩ࠊ12 ఩࡜ 17 ఩ࠊ12 ఩࡜ 15 ఩, 15 ఩࡜ 16 ఩࡟ࡑࢀࡒࢀ HMBC ┦㛵ࡀほ ࡉࢀࡓࡇ࡜࡞࡝࠿ࡽࠊ3 ఩ࠊ15 ఩ࠊ16 ఩ࠊ17 ఩ࠊ18 ఩࡟ࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡑࡢ௚ࠊྛ㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࠊࡉࡽ࡟㒊ศᵓ㐀ྠኈࡢ⤖ྜࢆ௓ࡋࡓ┦㛵ࡀほ ࡉࢀࠊFig. 24 ࡢࡼ࠺࡞ᖹ㠃ᵓ㐀࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ❧య㓄⨨ࢆỴࡵࡿࡓࡵࠊNOESY ࢆ ᐃࡋࡓ࡜ࡇࢁࠊH15 ࡜ H12ࠊH15 ࡜ H11ࠊH3 ࡜ H1 ࡟ࡑࢀࡒࢀ┦㛵ࡀほ ࡉࢀࡓࠋ௨ୖࡼࡾࠊCompound 21 ࢆ Fig. 23 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋࡋ࠿ࡋࠊ⤯ᑐ㓄⨨࡟ࡘ࠸࡚ࡣᨵⰋ Mosher ἲࡢ㐺ᛂ࡞࡝࡛௒ᚋࠊゎᯒࡍࡿᚲせࡀ࠶ࡿࠋ




52















Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 377.2298 [M+Na] +(calcd for C20H34O5Na: 377.2298)[α]D20 = -16.0 (c = 0.1, MeOH)
IR (film, cm-1): 3346, 2938, 2864, 1708, 1606, 1510, 1456, 1272, 1225, 1123, 1022

Fig. 23 Structure and physical data of Compound 21




53

















COSY




HMBC




Fig. 24 COSY and HMBC correlations of Compound 21






54






2



15

1



16

3

11




17
4

12






NOESY

Fig. 25 NOESY correlations of Compound 21








55

Table 21.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 21 in pyridine-d5

position
1
2
3
4
5
6
7
8
9
10
11

13

C
27.6
27.7
76.6
41.3
34.4
23.8
27.5
40.8
50.5
40.3
33.1

12
13
14

41.7
30.5
36.2

15
16
17

68.4
75.0
67.2

18

72.2

19
18.4
20
16.0
m: multiplet or overlapped signals

1H

1.00 - 2.50 (4H, m)
3.92 (1H, brs)
2.96 (1H, dd, J= 12.8, 3.1 Hz)
1.00 - 2.50 (4H, m)
1.99 (1H, m)

2.34 (1H, d, J= 10.8 Hz)
1.43 (1H, m)
2.74 (1H, dd, J= 7.8, 5.7 Hz)
1.17 - 1.33 (2H, m)
2.76 (1H, dd, J= 5.8, 3.1 Hz)
2.26 (1H, m)
4.17 (1H, dd, J= 11.2, 5.9 Hz)
4.28 (1H, d, J= 10.9 Hz)
4.00 (1H, d, J= 10.9 Hz)
3.79 (1H, d, J= 10.9 Hz)
3.64 (1H, d, J= 10.9 Hz)
0.79 (3H, s)
1.04 (3H, s)







56

➨ 2 㡯 ᪂つ໬ྜ≀ Compound 22 ࡢᵓ㐀Ỵᐃ
Cpd 22 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C25H46O11 ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋCpd
22 ࡟ࡣ NMR ࢫ࣌ࢡࢺࣝࡼࡾ⢾ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡓࡓࡵࠊ1M HCl ࡛ຍỈศゎࢆ⾜࠸ࠊ㐟㞳ࡋࡓ⢾࡟ࡘ࠸࡚᪕ගᗘ᳨ฟჾ௜ࡁ HPLC ࢆ⏝࠸࡚⢾ศᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
Cpd 22 ࡟ࡣ D-glucose ࡜ L-rhamnose ࡀྵࡲࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣࠊ13C NMR ࡟࠾࠸࡚ glucose ࡜ rhamnose ࡟⏤᮶ࡍࡿ 12 ᮏࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜࡜୍⮴ࡋࡓࠋࡑࡢ௚࡟ࡶ 13C NMR ࡟࠾࠸࡚࢔ࢢࣜࢥࣥ㒊ศ࡟ࡘ࠸࡚ࡣ 67.6ࠊ76.1 ppm ࡢࣄࢻࣟ࢟ࢩ
ᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡀ 2 ᮏࠊ25.7ࠊ38.8ࠊ46.6ࠊ51.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼ
ࣝࡀ 4 ᮏࠊ35.0ࠊ54.3 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ36.9 ppm ࡢ 4 ⣭Ⅳ⣲ࡀ
ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊD-glucose ࡜ L-rhamnose ࡀࡘ࠸࡚࠸ࡿ࣓࢞ࢫࢸ࢕ࢢ࣐ࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ
㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋᮎ➃ࡢ rhamnose ࡢ 1 ఩࠿ࡽࢢࣝࢥ࣮ࢫࡢ 2 ఩ࠊ
glucose ࡢ 1 ఩࠿ࡽ࢔ࢢࣜࢥࣥࡢ 9 ఩࡟ࡑࢀࡒࢀ HMBC ┦㛵ࡀほ ࡉࢀࡓࡇ࡜࠿ࡽ, Dglucose ࡜ L-rhamnose ࡢ⤖ྜ఩⨨ࡀ☜ㄆࡉࢀࡓࠋࡉࡽ࡟ࠊ11 ఩࡜ 1 ఩ࠊ12 ఩࡜ 1 ఩ࠊ13 ఩
࡜ 5 ఩࡟ࡑࢀࡒࢀ HMBC ┦㛵ࡉࢀࡓࡇ࡜࠿ࡽࠊ11 ఩ࠊ12 ఩࡜ 13 ఩ࡢ࣓ࢳࣝᇶࡀ 1 ఩࡜ 5఩࡟⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ9 ఩ࡢ⤯ᑐ㓄⨨࡟ࡘ࠸࡚ࡣࡑࡢࢣ࣑࢝ࣝࢩࣇࢺ್࠿
ࡽ 9R ࡜Ỵᐃࡋࡓࠋ23) ⎔㒊ศࡢࢣ࣑࢝ࣝࢩࣇࢺ್ࡣᮎ➃⢾ࡢ✀㢮ࠊ⤖ྜ఩⨨ࡢࡳ␗࡞ࡿ
sedumoside E2 ࠾ࡼࡧ E3 24) ࡜Ⰻ࠸୍⮴ࢆ♧ࡋ࡚࠸ࡿࡇ࡜࠿ࡽ┦ᑐ❧య໬Ꮫࢆᅗࡢࡼ࠺࡟᥎
ᐃࡋࡓࠋ௨ୖࡼࡾࠊCompound 22 ࢆ Fig. 26 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋࡋ࠿ࡋࠊ⤯ᑐ㓄⨨࡟ࡘ࠸࡚ࡣᨵⰋ Mosher ἲࡢ㐺ᛂ࡞࡝࡛௒ᚋࡉࡽ࡟ゎᯒࡍࡿᚲせࡀ࠶ࡿࠋ







57














Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 545.2928 [M+Na] +(calcd for C25H46O11Na: 545.2932)[α]D24 = -38.6 (c = 0.07, MeOH)
IR (film, cm-1): 3368, 2965, 2918, 1647, 1464, 1368, 1076, 1042

Fig. 26 Structure and physical data of Compound 22




58

















COSY









Fig. 27 COSY and HMBC correlations of Compound 22





59

HMBC

Table 22.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 22 in CD3OD

position
1
2

13

1

C
36.9
51.9

3
4

67.6
46.6

5
6
7

35.0
54.3
25.7

8

38.8

9
10
11
12
13
1'
2'
3'
4'
5'
6'

76.1
21.4
21.7
31.6
21.7
101.0
79.1
79.6
72.1
78.0
62.9

H

1.63 (1H, m)
1.09 (1H, m)
3.70 (1H, m)
1.88 (1H, m)
0.90 (1H, m)
1.46 (1H, m)
0.57 (1H, ddd, J= 10.8, 4.9, 2.4 Hz)
1.40 (1H, m)
1.03 (1H, m)
1.79 (1H, m)
1.43 (1H, m)
3.86 (1H, m)
1.22 (1H, m)
0.84 (1H, s)
0.96 (1H, s)
0.99 (1H, d, J= 6.5 Hz)
4.41 (1H, d, J= 7.7 Hz)
3.36 (1H, dd, J= 9.1, 7.7 Hz)
3.45 (1H, t, J= 9.1 Hz)
3.27 (1H, m)
3.21 (1H, ddd, J= 9.9, 5.9, 2.4 Hz)
3.84 (1H, m)
3.65 (1H, dd, J= 11.8, 5.9 Hz)
5.21 (1H, d, J= 1.4 Hz)
3.91 (1H, dd, J= 3.3, 1.4 Hz)
3.68 (1H, m)
3.38 (1H, t, J= 9.5 Hz)
4.07 (1H, dd, J= 9.5, 6.2 Hz)
1.22 (1H, m)

1''
102.3
2''
72.3
3''
72.6
4''
74.1
5''
69.9
6''
18.1
m: multiplet or overlapped signals60➨ 4 ⠇  ᪤▱໬ྜ≀࡟ࡘ࠸࡚᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ⴥ㒊࡜ࡘࡿࡢ㓑㓟࢚ࢳࣝྍ⁐⏬ศࢆศ㞳㸬⢭〇ࡍࡿ㐣⛬࡛ࠊ᪂つ໬ྜ≀࡜࡜ࡶ࡟ࠊ᪤▱໬ྜ≀ 32 ✀ࢆ༢㞳ࡋࡓࠋྛ໬ྜ≀ࡢ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࢀࡒࢀ௨ୗ࡟♧ࡍ᪤▱໬ྜ≀࡛࠶ࡿ࡜ྠᐃࡋࡓࠋ
Compound 23: Salicifoliol 25,26)
Compound 24: cyclo(D)-Pro-(D)-Leu 27)
Compound 25: (+)-Epiloliolide 28)
Compound 26: (+)-Syringaresinol 29)
Compound 27: N-trans-feruloylmethoxytyramine 30)
Compound 28: Ficusequilignan A 31)
Compound 29: Frangulin A 32)
Compound 30: (+)-Dehydrovomifoliol 33)
Compound 31: (+)-Medioresinol 34)
Compound 32: Terrestribisamide 35)
Compound 33: trans-N-p-Coumaroyl tyramine 36)
Compound 34: 7-Hydroxy-1-(4-hydroxy-3-methoxyphenyl)-N2, N3-bis(4-hydroxyphenethyl)-6methoxy-1,2-dihydronaphthalene-2,3-dicarboxamide 37)
Compound 35: Cannabisin E 38)
Compound 36: Grossamide K 39)
Compound 37: Cannabisin G 40)
Compound 38: N-trans-Feruloyl tyramine 41)
Compound 39: trans-Ferulic Acid 42, 43)Compound 40: 5(S)-5-Carboxystrictosidine 44)
Compound 41: Glucofragulin A 45)
Compound 42: Vanillic acid 46)
Compound 43: Neo-olivil (a racemic mixture) 47)
Compound 44: 3-Hydroxy-1-( 4-hydroxy-3-methoxyphenyl) propan-1-one 48)
Compound 45: Syringic acid 49)
Compound 46: (6S,9R)-Vomifoliol 50)
Compound 47: Vanillin 51)
Compound 48: Umbelliferone 52)
Compound 49: Methyl protocatechuate 53)
Compound 50: 3,4-Dihydro-10-hydroxy-7-methoxy-3-(R)-methyl-1H-3,4-dihydronaphtho-[2,3c]pyran-1-one-9-O-ș-D-glucopyranosyl-(1Ѝ6)-glucopyranoside 54)
Compound 51: Narcissin 55)
Compound 52: Kaempferol 3-β-rutinoside 56)
Compound 53: Emodin 57)
Compound 54: Tribulusamide A 58)

61

➨ 1 㡯 ᪤▱໬ྜ≀ Compound 23 ࡢᵓ㐀Ỵᐃ
Cpd 23 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࡑࡢศᏊᘧࢆ C13H14O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ111.1 ࠿ࡽ 149.4 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࠊ
181.3 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࢆ 1 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 25) 26) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 23 ࢆ salicifoliol࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (negative)
m/z: 249.0768 [M-H](calcd for C13H13O5: 249.0768)[α]D25 = +4.8 (c = 0.43, MeOH)
Fig. 28 Structure and physical data of Compound 23

62

Table 23. 13C NMR (125 MHz) and 1H NMR (500 MHz) data for Cpd 23 in CD3OD
position
1
2
3
4
5
6
7
8

13

C
49.4
87.9

1

71.1

4.30 (1H, t, J= 8.7 Hz)
4.08 (1H, dd, J= 9.1, 3.4 Hz)
3.55 (1H, m)

H
3.21 (1H, m)
4.67 (1H, d, J= 7 Hz)

47.7
181.3
72.0

4.54 (1H, dd, J= 9.6, 6.9 Hz)
4.36 (1H, dd, J= 9.6, 1.9 Hz)

1'
132.4
2'
111.1
3'
149.4
4'
147.9
5'
116.3
6'
120.3
3'-OCH3
56.6
m: multiplet or overlapped signals

6.96 (1H, d, J= 1.7 Hz)

6.78 (1H, d, J= 8.1 Hz)
6.83 (1H, dd, J= 8.1, 1.7 Hz)
3.86 (3H, s)

63➨ 2 㡯 ᪤▱໬ྜ≀ Compound 24 ࡢᵓ㐀Ỵᐃ
Cpd 24 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C11H19O2N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ169.1ࠊ172.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࢆ 2 ᮏࠊ23.8ࠊ
29.2ࠊ39.6ࠊ46.6 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ25.9ࠊ54.8ࠊ60.4 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್
27)
࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 24 ࢆ cyclo-(D)-Pro-(D)-Leu ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous solid
HR-ESI-MS (positive)
m/z: 211.1438 [M+H] +(calcd for C11H19O2N2: 211.1441)

Fig. 29 Structure and physical data of Compound 24

64

Table 24.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 24 in CD3OD

position
1
2
3
4

13

C
169.1

1

46.6
23.8

3.52 (2H, m)
1.93 (1H, m)
2.03 (1H, m)
2.03 (1H, m)
2.31 (1H, m)
4.26 (1H, t, J= 7.7 Hz)

5

29.2

6
7
8
9
10

60.4
172.9
54.8
39.6

H

4.13 (1H, m)
1.91 (1H, m)
1.52 (1H, m)
1.88 (1H, m)
0.96 (3H, m)
0.96 (3H, m)

11
25.9
12
23.4
13
22.4
m: multiplet or overlapped signals65➨ 3 㡯 ᪤▱໬ྜ≀ Compound 25 ࡢᵓ㐀Ỵᐃ
Cpd 25 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C11H16O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ174.1 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ113.9ࠊ184.1 ppm
ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ65.4 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏࠊ49.2ࠊ50.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 28) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 25 ࢆ (+)-epiloliolide ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous solid
HR-ESI-MS (positive)
m/z: 219.0987 [M+Na] +(calcd for C11H16O3Na: 219.0992)

Fig. 30 Structure and physical data of Compound 25

66

Table 25. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 25 in CD3OD
position
2
3
3a
4
5
6
7

13

C
174.1
113.9
184.1
36.3
50.9
65.4
49.2

7a
88.7
8
30.4
9
25.9
10
25.5
m: multiplet or overlapped signals

1H

5.78 (1H, m)

2.00 (1H, ddd, J= 13, 4.3, 2.2 Hz)
1.29 (1H, m)
4.10 (1H, m)
2.47 (1H, ddd, J= 11.7, 4.0, 2.1 Hz)
1.42 (1H, td, J= 11.7, 0.6 Hz)
1.59 (3H, s)
1.31 (3H, s)
1.29 (3H, s)67➨ 4 㡯 ᪤▱໬ྜ≀ Compound 26 ࡢᵓ㐀Ỵᐃ
Cpd 26 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C22H26O8 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ104.7 ࠿ࡽ 149.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ57.0 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ72.9ࠊ87.7 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 2 ᮏࠊ55.7 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ ࡜ ࡼ ࡾ ࠊ NMR ࢫ ࣌ ࢡ ࢺ ࣝ ࢹ ࣮ ࢱ ࢆ ᩥ ⊩ ್ 29) ࡜ ẚ ㍑ ࡋ ࡓ ࡜ ࡇ ࢁ ࠊ Cpd 26 ࢆ (+)syringaresinol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous solid
HR-ESI-MS (positive)
m/z: 441.1518 [M+H] +(calcd for C22H26O8Na: 441.1520)[α]D25 = +10.8 (c = 1.33, MeOH)

Fig. 31 Structure and physical data of Compound 26

68

Table 26.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 26 in CD3OD

position
1, 5
2, 6
4, 8

13

C
55.7
87.7
72.9

1', 1''
133.3
2', 2'', 6', 6''
104.7
3', 3'', 5', 5''
149.5
4', 4''
136.4
3', 3'', 5', 5''-OMe
57.0
m: multiplet or overlapped signals

1H
3.13 (2H, m)
4.71 (2H, d, J= 4.3 Hz)
4.25 (2H, dd, J= 6.9, 9.0 Hz)
3.87 (2H, dd, J= 3.6, 9.2 Hz)
6.65 (4H, s)

3.86 (12H, s)69➨ 5 㡯 ᪤▱໬ྜ≀ Compound 27 ࡢᵓ㐀Ỵᐃ
Cpd 27 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C19H21O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ111.7 ࠿ࡽ 150.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.3 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ118.9ࠊ142.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࡀᏑᅾࡋ࡚࠸ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮
ࢱࢆᩥ⊩್ 30) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 27 ࢆ N-trans-feruloylmethoxytyramine ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 366.1313 [M+Na]+(calcd for C19H21O5Na: 366.1312)

Fig. 32 Structure and physical data of Compound 27

70

Table 27. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 27 in CD3OD
position
1

13

C
169.3

1

2
3
4
5
6
7
8
9
6-OCH3
1'
2'
3'
4'
5'
6'
7'
8'
5'-OCH3

118.9
142.2
132.2
111.7
150.0
149.1
116.6
123.3
56.5
42.6
36.3
128.4
113.6
149.4
146.2
116.4
122.4
56.5

6.41 (1H, d, J= 15.7 Hz)
7.44 (1H, d, J= 15.7 Hz)

H

7.10 (1H, d, J= 1.9 Hz)

6.80 (1H, d, J= 8.2 Hz)
7.01 (1H, dd, J= 8.2, 1.9 Hz)
3.86 (3H, s)
3.48 (2H, t, J= 7.3 Hz)
2.76 (2H, t, J= 7.3 Hz)
6.81 (1H, d, J= 1.9 Hz)

6.72 (1H, d, J= 8.0 Hz)
6.66 (1H, dd, J= 8.0, 1.9 Hz)
3.81 (3H, s)

71➨ 6 㡯 ᪤▱໬ྜ≀ Compound 28 ࡢᵓ㐀Ỵᐃ
Cpd 28 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C31H36O11 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ104.4 ࠿ࡽ 154.7 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 16 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ56.5ࠊ56.9ࠊ56.9 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ61.9ࠊ72.9ࠊ
73.1ࠊ74.2ࠊ87.5ࠊ87.6ࠊ87.6 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 7 ᮏࠊ55.4ࠊ55.4
ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆᣢ
ࡘࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 31) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ
Cpd 28 ࢆ ficusequilignan A ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 607.2151 [M+Na] +(calcd for C31H36O11Na: 607.2151)
Fig. 33 Structure and physical data of Compound 28

72

Table 28.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 28 in CD3OD
position
1
2
3
4
5
6
7
8
9

13

C
136.3
104.4
154.7
139.1
154.7
104.4
87.6
55.4
72.9

1'
2'
3'
4'
5'
6'
7'
8'
9'

134.0
111.2
149.3
147.5
116.3
120.3
87.6
55.4
73.1

1''
2''
3''
4''
5''
6''
7''
8''
9''

134.0
111.6
148.8
147.0
115.8
120.9
74.2
87.5
61.9

3,5-OCH3
56.9
3'-OCH3
56.5
3''-OCH3
56.9
m: multiplet or overlapped signals

73

1

H

6.68 (1H, s)

6.68 (1H, s)
4.73 (1H, d, J= 3.1 Hz)
3.16 (1H, m)
3.89 (1H, m)
4.27 (1H, m)
6.95 (1H, d, J= 1.9 Hz)

6.81 (1H, m)
6.82 (1H, m)
4.73 (1H, m)
3.16 (1H, m)
3.89 (1H, m)
4.27 (1H, m)
6.96 (1H, m)

6.73 (1H, d, J= 8.1 Hz)
6.73 (1H, dd, J= 8.1, 1.7 Hz)
4.90 (1H, m)
4.27 (1H, m)
3.89 (1H, m)
3.59 (1H, dt, J= 12.0, 3.8 Hz)
3.83 (6H, s)
3.86 (3H, s)
3.83 (3H, s)➨ 7 㡯 ᪤▱໬ྜ≀ Compound 29 ࡢᵓ㐀Ỵᐃ
Cpd 29 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C21H20O9 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ17.9 ࡟ຍ࠼ࠊ69.8 ࠿ࡽ 98.5 ppm ࡟ rhamnose ࡜⪃࠼ࡽࢀࡿ 5 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ
108.6 ࠿ࡽ 163.7 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 12 ᮏࠊ181.2ࠊ190.2 ppm ࡢ࢝ࣝ࣎ࢽࣝ
Ⅳ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ21.6 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 32) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 29 ࢆ frangulin A࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (negative)
m/z: 415.1035 [M-H](calcd for C21H19O9: 415.1035)

Fig. 34 Structure and physical data of Compound 29

74

Table 29. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 29 in DMSO-d6
13
position
C
1
161.5
2
124.3
3
148.7
4
120.7
5
108.6
6
162.7
7
109.2
8
163.7
9
190.2
10
181.2
11
135.0
12
110.9
13
113.5
14
132.9
15
21.6
1'
98.5
2'
69.8
3'
70.2
4'
71.6
5'
70.2
6'
17.9
1-OH
8-OH
m: multiplet or overlapped signals

1H

7.19 (1H, brs)
7.52 (1H, brs)
7.28 (1H, d, J= 2.4 Hz)
6.93 (1H, d, J= 2.4 Hz)

2.42 (3H, s)
5.63 (1H, d, J=0.9 Hz)
3.38-3.90 (4H, m)
1.12 (1H, d, J=6.1 Hz)
12.07 (1H, s)
11.93 (1H, s)75

➨ 8 㡯 ᪤▱໬ྜ≀ Compound 30 ࡢᵓ㐀Ỵᐃ
Cpd 30 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H18O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ200.5ࠊ200.8 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࢆ 2 ᮏࠊ128.2ࠊ
131.9ࠊ148.5ࠊ164.8 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ80.1 ppm ࡢࣄࢻࣟ࢟ࢩᇶ
ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡀ 1 ᮏࠊ50.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ ࡜ ࡼ ࡾ ࠊ NMR ࢫ ࣌ ࢡ ࢺ ࣝ ࢹ ࣮ ࢱ ࢆ ᩥ ⊩ ್ 33) ࡜ ẚ ㍑ ࡋ ࡓ ࡜ ࡇ ࢁ ࠊ Cpd 30 ࢆ (+)dehydrovomifoliol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 245.1146 [M+Na]+(calcd for C13H18O3Na: 245.1148)[α]D24 = +34.7 (c 0.05, MeOH)

Fig. 35 Structure and physical data of Compound 30

76

Table 30. 13C NMR (150MHz) and 1H NMR (600MHz) data for Cpd 30 in CD3OD
position
1
2
3
4
5
6
7
8
9
10
11
12
13

13

C
42.8
50.7
200.5
128.2
164.8
80.1
148.5
131.9
200.8
27.8
23.7
24.9
19.3

77

1

H

2.60 (1H, d, J= 16.9 Hz)
2.28 (1H, d, J= 16.9 Hz)
5.93 (1H, s)
6.99 (1H, d, J= 15.8 Hz)
6.44 (1H, d, J= 15.8 Hz)
2.30 (3H, s)
1.06 (3H, s)
1.02 (3H, s)
1.90 (3H, d, J=1.4 Hz)➨ 9 㡯 ᪤▱໬ྜ≀ Compound 31 ࡢᵓ㐀Ỵᐃ
Cpd 31 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C21H24O7 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ104.7 ࠿ࡽ 149.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 10 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ56.6ࠊ56.7 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ72.8ࠊ72.9ࠊ87.6ࠊ
87.8 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 4 ᮏࠊ55.5ࠊ55.7 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆᣢࡘࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 34) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 31 ࢆ (+)-medioresinol࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 411.1417 [M+Na] +(calcd for C21H24O7Na: 411.1414)[α]D24 = +10.9 (c = 0.11, MeOH)

Fig. 36 Structure and physical data of Compound 31

78

Table 31.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 31 in CD3OD

position
1
2
3
4
5
6
7
8
9
1'
2', 6'
3', 5'
4'
7'
8'
9'

13

1

C
134.0
111.2
149.3
147.5
116.3
120.2
87.8
55.5
72.9

H

6.95 (1H, d, J= 1.8 Hz)

6.77 (1H, d, J= 8.1 Hz)
6.82 (1H, dd, J= 8.1, 1.9 Hz)
4.72 (1H, d, J= 4.4 Hz)
3.14 (1H, m)
3.88 (1H, m)
4.25 (1H, m)

133.3
104.7
149.5
136.4
87.6
55.7
72.8

6.66 (2H, s)

4.72 (1H, d, J= 4.4 Hz)
3.14 (1H, m)
3.88 (1H, m)
4.25 (1H, m)
3.86 (3H, s)
3.85 (6H, s)

3-OCH356.6
3', 5'-OCH3
57.0
m: multiplet or overlapped signals79➨ 10 㡯 ᪤▱໬ྜ≀ Compound 32 ࡢᵓ㐀Ỵᐃ
Cpd 32 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C24H28O6N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ111.8 ࠿ࡽ 150.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.4 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ118.9ࠊ142.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࡀ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 35) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 32 ࢆ terrestribisamide ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 463.1836 [M+Na]+(calcd for C24H28O6N2Na: 463.1840)

Fig. 37 Structure and physical data of Compound 32

80

Table 32.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 32 in CD3OD

13
1
position
C
H
1
128.5
2
111.8
7.11 (2H, d, J= 1.7 Hz)
3
149.4
4
150.0
5
116.7
6.79 (2H, d, J= 8.1 Hz)
6
123.3
7.02 (2H, dd, J= 8.1, 1.7 Hz)
7142.2
7.44 (2H, d, J= 15.6 Hz)
8
118.9
6.43 (2H, d, J= 15.6 Hz)
9
169.4
10
40.3
3.31 (4H, m)
11
28.1
1.62 (4H, m)
3, 3'-OCH3
56.6
3.87 (6H, s)
m: multiplet or overlapped signals81➨ 11 㡯 ᪤▱໬ྜ≀ Compound 33 ࡢᵓ㐀Ỵᐃ
Cpd 33 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C17H17O3N ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋC NMR ࡟࠾࠸࡚ࠊ116.4 ࠿ࡽ 160.6 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 8 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.4 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ118.6ࠊ141.9 ppm
ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ35.9ࠊ42.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝ
ࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ
࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,4-⨨᥮࣋ࣥࢮࣥࢆᣢࡘᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 36) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 33 ࢆ trans-N-p-coumaroyl tyramine ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ
13

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 306.1101 [M+Na] +(calcd for C17H17O3NNa: 306.1101)

Fig. 38 Structure and physical data of Compound 33

82

Table 33. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 33 in CD3OD
position
1
2, 6
3, 5
4
7
8
9
1'
2', 6'
3', 5'
4'
7'
8'

13

1

C
127.9
130.7
116.4
160.6
141.9
118.6
169.4
131.5
130.9
116.9
157.1
35.9
42.7

H

7.30 (2H, d, J= 8.6 Hz)
6.69 (2H, d, J= 8.6 Hz)
7.34 (1H, d, J= 15.7 Hz)
6.28 (1H, d, J= 15.7 Hz)

6.95 (2H, d, J= 8.4 Hz)
6.62 (2H, d, J= 8.4 Hz)
3.36 (2H, t, J= 7.4 Hz)
2.65 (2H, t, J= 7.4 Hz)83➨ 12 㡯 ᪤▱໬ྜ≀ Compound 34 ࡢᵓ㐀Ỵᐃ
Cpd 34 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C36H36O8N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ112.7 ࠿ࡽ 157.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 20 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ170.6ࠊ174.7 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ127.8ࠊ134.8
ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ35.6ࠊ35.8ࠊ42.5ࠊ42.8 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ56.5ࠊ56.8 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࢆᣢࡘᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 37) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 34 ࢆ 7-hydroxy-1(4-hydroxy-3-methoxyphenyl)-N2,N3-bis(4-hydroxyphenethyl)-6-methoxy-1,2dihydronaphthalene-2,3-dicarboxamide ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 647.2363 [M+Na] +(calcd for C36H36O8N2Na: 647.2364)[α]D24 = +2.0 (c = 0.2, MeOH)
Fig. 39 Structure and physical data of Compound 34

84

Table 34. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 34 in CD3OD
13
position
C
1
125.1
2
113.4
3
148.3
4
149.8
5
117.3
6
132.8
7
134.8
8
127.8
9
170.6
3-OCH3
56.8
1'
136.1
2'
112.7
3'
149.0
4'
146.4
5'
116.2
6'
121.6
7'
47.8
8'
51.1
9'
174.7
3'-OCH3
56.5
1''
131.5
2'', 6''131.0
3'', 5''
116.4
4''
157.0
7''
35.8
8''
42.8
1'''
131.3
2''', 6'''
130.9
3''', 5'''
116.4
4'''
156.9
7'''
35.6
8'''
42.5
m: multiplet or overlapped signals

85

1

H

6.88 (1H, s)

6.53 (1H, s)
7.21 (1H, s)

3.89 (3H, s)
6.70 (1H, d, J= 1.9 Hz)

6.68 (1H, d, J= 8.2 Hz)
6.42 (1H, dd, J= 8.2, 1.9 Hz)
4.35 (1H, d, J= 4.0 Hz)
3.69 (1H, d, J= 4.0 Hz)
3.75 (3H, s)
6.97 (2H, d, J= 8.4 Hz)
6.65 (2H, d, J= 8.4 Hz)
2.70 (2H, t, J= 7.3 Hz)
3.35 (2H, m)
6.82 (2H, d, J= 8.4 Hz)
6.65 (2H, d, J= 8.4 Hz)
2.48 (2H, t, J= 6.9 Hz)
3.23 (2H, m)➨ 13 㡯 ᪤▱໬ྜ≀ Compound 35 ࡢᵓ㐀Ỵᐃ
Cpd 35 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C36H38O9N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ111.9 ࠿ࡽ 157.1 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 20 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ121.0ࠊ141.3 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ75.2ࠊ87.4 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 2 ᮏࠊ35.7ࠊ35.9ࠊ42.2ࠊ42.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.5ࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࡀ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 38) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 35 ࢆ cannabisin
E ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 665.2472 [M+Na] +(calcd for C36H38O9N2Na: 665.2470)[α]D24 = -35 (c = 0.17, MeOH)

Fig. 40 Structure and physical data of Compound 35

86

Table 35. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 35 in CD3OD
13
position
C
1
133.5
2
111.9
3
149.1
4
147.5
5
116.1
6
120.8
7
75.2
8
87.4
9
N.D.
1'
131.4
2'
112.4
3'
151.6
4'
150.4
5'
118.0
6'
122.5
7'
141.3
8'
121.0
9'
N.D.
α
42.2
α'
42.7
β
35.7
β'
35.9
1''
130.9
2'', 6''130.8
3'', 5''
116.4
4''
157.1
1'''
131.1
2''', 6'''
130.8
3''', 5'''
116.4
4'''
157.1
3-OCH356.5
3'-OCH3
56.5
m: multiplet or overlapped signals

1H

7.10 (1H, d, J= 2.0 Hz)

6.77 (1H, d, J= 8.2 Hz)
6.90 (1H, m)
5.13 (1H, dd, J= 6.8, 3.5 Hz)
4.56 (1H, d, J= 3.5 Hz)

7.10 (1H, d, J= 2.0 Hz)

6.39 (1H, d, J= 8.4 Hz)
6.94 (1H, m)
7.42 (1H, d, J= 15.7 Hz)
6.44 (1H, d, J= 15.7 Hz)
3.41 (2H, m)
3.45 (2H, m)
2.60 (2H, m)
2.75 (2H, t, J= 7.3 Hz)
7.05 (2H, d, J= 8.4 Hz)
6.61 (2H, m)

6.89 (2H, m)
6.71 (2H, m)
3.81 (3H, s)
3.79 (3H, s)87➨ 14 㡯 ᪤▱໬ྜ≀ Compound 36 ࡢᵓ㐀Ỵᐃ
Cpd 36 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C28H29O7N ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ110.8 ࠿ࡽ 157.1 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 16 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.2 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ120.0ࠊ142.1 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ64.9ࠊ89.9 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 2 ᮏࠊ35.9ࠊ42.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.6ࠊ56.9 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ protonࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ
⊩್ 39) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 36 ࢆ gossamide K ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 514.1833 [M+Na]+(calcd for C28H29O7NNa: 514.1833)[α]D24 = -7.7 (c = 0.13, MeOH)

Fig. 41 Structure and physical data of Compound 36

88

Table 36.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 36 in CD3OD

13
position
C
2
89.9
3
55.0
4
118.6
5
130.4
6
113.5
7
145.9
8
151.5
9
130.9
1'
134.4
2'
110.8
3'
149.3
4'
147.9
5'
116.4
6'
120.0
1''
64.9
1'''
142.1
2'''
120.0
1''''
42.7
2''''
35.9
1'''''
130.9
2''''', 6'''''
130.9
3''''', 5'''''
116.4
4'''''
157.1
7-OCH356.9
3'-OCH3
56.6
C=O
169.2
m: multiplet or overlapped signals

89

1

H
5.56 (1H, d, J= 6.5 Hz)
3.53 (1H, d, J= 6.5 Hz)
7.13 (1H, s)
7.07 (1H, d, J= 1.4 Hz)

6.93 (1H, d, J= 1.9 Hz)

6.78 (1H, d, J= 8.1 Hz)
6.83 (1H, dd, J= 8.1, 1.9 Hz)
3.82 (2H, m)
7.47 (1H, d, J= 15.7 Hz)
6.43 (1H, d, J= 15.7 Hz)
3.47 (2H, t, J= 7.2 Hz)
2.75 (2H, t, J= 7.2 Hz)
7.05 (2H, d, J= 8.5 Hz)
6.72 (2H, d, J= 8.5 Hz)➨ 15 㡯 ᪤▱໬ྜ≀ Compound 37 ࡢᵓ㐀Ỵᐃ
Cpd 37 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C36H36O8N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ113.7 ࠿ࡽ 157.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 10 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ168.1 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ128.1ࠊ142.3 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ35.6ࠊ43.1 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ
2 ᮏࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜
ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 40) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 37 ࢆ cannabisin G ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 647.2367 [M+Na] +(calcd for C36H36O8N2Na: 647.2369)

Fig. 42 Structure and physical data of Compound 37

90

Table 37.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 37 in CD3OD
position
1, 1'
2, 2'
3, 3'
4, 4'
5, 5'
6, 6'
7, 7'
8, 8'
9, 9'
α, α'
β, β'

13

1

C
127.5
113.7
150.1
149.2
116.6
126.5
142.3
128.1
168.1
43.1

H

7.17 (2H, d, J= 2.0 Hz)

6.78 (2H, d, J= 8.4 Hz)
7.03 (2H, dd, J= 8.4, 2.0 Hz)
7.84 (2H, s)

3.19 (2H, m)
3.40 (2H, m)
2.37 (2H, dt, J= 14.1, 7.2 Hz)
2.45 (2H, dt, J= 14.1, 7.2 Hz)

35.6

1'', 1'''
131.2
2'', 2''', 6'', 6'''
130.7
3'', 3''', 5'', 5'''116.4
4'', 4'''157.0
3, 3'-OCH3
56.5
m: multiplet or overlapped signals

6.81 (4H, d, J= 8.5 Hz)
6.61 (4H, d, J= 8.5 Hz)
3.74 (6H, s)91➨ 16 㡯 ᪤▱໬ྜ≀ Compound 38 ࡢᵓ㐀Ỵᐃ
Cpd 38 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C18H19O4N ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ111.8 ࠿ࡽ 157.1 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.3 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ119.1ࠊ142.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ35.7ࠊ42.5 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ
2 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜
ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 41) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 38 ࢆ N-trans-feruloyl tyramine ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 336.1207 [M+Na] +(calcd for C18H19O4NNa: 336.1206)

Fig. 43 Structure and physical data of Compound 38

92

Table 38. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 38 in CD3OD
13
position
C
1
169.3
2
119.1
3
142.2
1'
128.5
2'
111.8
3'
149.5
4'
150.0
5'
116.7
6'
123.3
1''
42.5
2''
35.7
1'''
131.4
2''', 6'''
130.9
3''', 5'''
116.4
4'''
157.1
3'-OCH3
56.6
m: multiplet or overlapped signals

1H

6.42 (1H, d, J= 15.4 Hz)
7.43 (1H, d, J= 15.4 Hz)
7.12 (1H, d, J= 1.8 Hz)

6.79 (1H, d, J= 8.2 Hz)
7.05 (1H, m)
3.40 (2H, t, J= 7.7 Hz)
2.70 (2H, t, J= 7.7 Hz)
7.05 (2H, d, J= 8.5 Hz)
6.74 (2H, d, J= 8.5 Hz)
3.87 (3H, s)93➨ 17 㡯 ᪤▱໬ྜ≀ Compound 39 ࡢᵓ㐀Ỵᐃ
Cpd 39 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H10O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ111.9 ࠿ࡽ 150.6 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ171.3 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ116.6ࠊ146.9 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮
ࢱࢆᩥ⊩್ 42,43) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 39 ࢆ trans-ferulic Acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 193.0507 [M+H] +(calcd for C10H9O4: 193.0506)

Fig. 44 Structure and physical data of Compound 39

94

Table 39. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 39 in CD3OD
position
1
2
3
1'
2'
3'
4'
5'
6'
3'-OCH3

13

1

C
171.3
116.6
146.9
128.0
111.9
149.5
150.6
116.3
124.1
56.6

H

6.31 (1H, d, J= 15.9 Hz)
7.59 (1H, d, J= 15.9 Hz)
7.18 (1H, d, J= 1.9 Hz)

6.81 (1H, d, J= 8.2 Hz)
7.06 (1H, dd, J= 8.2, 1.9 Hz)
3.89 (3H, s)95➨ 18 㡯 ᪤▱໬ྜ≀ Compound 40 ࡢᵓ㐀Ỵᐃ
Cpd 40 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C28H34O11N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ63.3 ࠿ࡽ 100.6 ppm ࡟ࢢࣝࢥ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ172.0ࠊ
173.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ108.5ࠊ108.8ࠊ120.8ࠊ130.7ࠊ
135.4ࠊ157.4 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 6 ᮏࠊ24.2ࠊ34.8 ppm ࡢ࣓ࢳࣞࣥᇶ࡟
⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ53.0 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ ࡼࡾ ࠊ NMR ࢫ࣌ ࢡࢺ ࣝࢹ ࣮ࢱ ࢆᩥ ⊩್ 44) ࡜ ẚ㍑ ࡋࡓ࡜ ࡇࢁ ࠊ Cpd 40 ࢆ 5(S)-5carboxystrictosidine ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋPale yellow amorphous powder
HR-ESI-MS (positive)
m/z: 575.2239 [M+H] +(calcd for C28H35O11N2: 575.2235)[α]D24 = -47.5 (c = 0.16, CHCl3)

Fig. 45 Structure and physical data of Compound 40

96

Table 40. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 40 in CD3OD
position
2
3
5
6

13

C
130.7
53.2
59.7
24.2

7
8
9
10
11
12
13
14

108.5
127.7
119.3
120.8
123.6
112.4
138.7
34.8

15
16
17
18

32.9
108.8
157.4
120.8

19
20
21
5-COOH
16-COOOCH3
1'
2'
3'
4'
5'
6'

135.4
45.5
97.5
173.6
172.0
53.0
100.6
74.8
78.1
71.9
79.0
63.3

1

H

4.67 (1H, d, J= 12.3 Hz)
3.96 (1H, dd, J= 12.1, 5.1 Hz)
3.04 (1H, m)
3.46 (1H, m)

7.49 (1H, d, J= 7.9 Hz)
7.05 (1H, m)
7.13 (1H, m)
7.31 (1H, d, J= 8.1 Hz)
2.24 (1H, m)
2.44 (1H, m)
3.09 (1H, m)
7.83 (1H, s)
5.27 (1H, d, J= 10.7 Hz)
5.38 (1H, d, J= 17.4 Hz)
5.85 (1H, ddd, J= 17.4, 10.7, 7.5 Hz)
2.79 (1H, m)
5.92 (1H, d, J= 9.2 Hz)

3.80 (3H, s)
4.82 (1H, d, J= 7.9 Hz)
3.24 (1H, m)
3.43 (1H, m)
3.26 (1H, m)
3.31 (1H, m)
3.57 (1H, dd, J= 11.7, 7.2 Hz)
4.02 (1H, dd, J= 11.7, 1.9 Hz)

m: .multiplet or overlapped signals97➨ 19 㡯 ᪤▱໬ྜ≀ Compound 41 ࡢᵓ㐀Ỵᐃ
Cpd 41 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H30O14 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ18.3 ࡜ 62.6 ࠿ࡽ 104.1 ppm ࡟ࢢࣝࢥ࣮ࢫཬࡧ࣒ࣛࣀ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 12ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ110.8 ࠿ࡽ 163.9 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 12 ᮏࠊ183.4ࠊ
188.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ22.1 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 45) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 41 ࢆ glucofragulin A ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (positive)
m/z: 601.1531 [M+Na] +(calcd for C27H30O14Na: 601.1528)

Fig. 46 Structure and physical data of Compound 41

98

Table 41. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 41 in CD3OD
position
1
2
3
4
5
6
7
8
9
10
11
12
13
14
3-CH3
Rha-1
2
3
4
5
6
Glu-1
2
3
4
5
6

13

1

C
163.9
125.6
149.3
121.2
110.8
163.3
112.2
162.2
188.9
183.4
138.3
117.8
116.1
133.9
22.1
100.1
71.7
72.2
73.7
71.6
18.3
104.1
74.9
77.7
71.3
78.9
62.6

H

7.08 (1H, brs)
7.51 (1H, brs)
7.41 (1H, d, J= 2.4 Hz)
7.61 (1H, d, J= 2.4 Hz)

2.42 (3H, s)
5.67 (1H, d, J= 1.5 Hz)
4.07 (1H, m)
3.86 (1H, dd, J= 9.1, 3.4 Hz)
3.48 (1H, m)
3.57 (1H, m)
1.26 (1H, d, J= 6.1 Hz)
5.01 (1H, d, J= 7.7 Hz)
3.68 (1H, t, J= 8.4 Hz)
3.54 (1H, m)
3.45 (1H, m)
3.50 (1H, m)
3.96 (1H, dd, J= 12.1, 1.7 Hz)
3.75 (1H, dd, J= 12.1, 5.7 Hz)

m: multiplet or overlapped signals99➨ 20 㡯 ᪤▱໬ྜ≀ Compound 42 ࡢᵓ㐀Ỵᐃ
Cpd 42 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C8H8O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ116.0 ࠿ࡽ 152.8 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ170.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ
ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆࡶࡘᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 46) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 42 ࢆ vanillic acid࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (negative)
m/z: 167.0352 [M-H](calcd for C8H7O4: 167.0350)

Fig. 47 Structure and physical data of Compound 42

100

Table 42. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 42 in CD3OD
position
1
2
3
4
5
6
1-COOH
3-OCH3
m: multiplet or overlapped signals

13

C
125.4
114.0
152.8
148.8
116.0
123.4
170.5
56.6

101

1

H

7.54-7.57 (1H, m)

6.84 (1H, d, J= 8.7 Hz)
7.54-7.57 (1H, m)
3.89 (3H, s)➨ 21 㡯 ᪤▱໬ྜ≀ Compound 43 ࡢᵓ㐀Ỵᐃ
Cpd 43 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C20H24O7 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ111.6 ࠿ࡽ 149.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡ
ࡀ࠶ࡾࠊ63.5ࠊ64.1ࠊ83.2ࠊ84.3 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 4 ᮏࠊ56.7ࠊ
56.7 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ
ⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 47) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ
Cpd 43 ࢆ neo-olivil (a racemic mixture) ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 399.1415 [M+Na]+(calcd for C20H24O7Na: 399.1414)[α]D24 = 0.0 (c = 0.08, MeOH)

Fig. 48 Structure and physical data of Compound 43

102

Table 43. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 43 in CD3OD
position
1
2
3
4
5
6
7
8
9
1'
2'
3'
4'
5'
6'
7'
8'
9'

13

1

C
132.0
111.6
149.0
147.2
116.3
120.5
83.2
51.0
64.1

H

6.98 (1H, d, J= 1.8 Hz)

6.79 (1H, d, J= 8.1 Hz)
6.85 (1H, dd, J= 8.1, 1.8 Hz)
5.11 (1H, d, J= 8.1 Hz)
2.57 (1H, m)
3.23 (1H, m)
3.17 (1H, m)

134.0
111.8
149.3
147.6
116.1
120.8
84.3
55.7
63.5

7.12 (1H, d, J= 1.8 Hz)

6.83 (1H, d, J= 8.1 Hz)
6.97 (1H, m)
4.66 (1H, d, J= 8.7 Hz)
2.28 (1H, m)
3.72 (1H, dd, J= 11.0, 4.4 Hz)
3.65 (1H, dd, J= 11.0, 6.8 Hz)
3.86 (3H, s)
3.89 (3H, s)

3-OCH356.7
3'-OCH3
56.7
m: multiplet or overlapped signals103➨ 22 㡯 ᪤▱໬ྜ≀ Compound 44 ࡢᵓ㐀Ỵᐃ
Cpd 44 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H12O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ112.1 ࠿ࡽ 153.6 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ199.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ41.8ࠊ59.1 ppm ࡢ࣓ࢳࣞࣥ
ᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮
ࢱࢆᩥ⊩್ 48) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 44 ࢆ 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl) propan1-one ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 219.0626 [M+Na] +(calcd for C10H12O4Na: 219.0628)

Fig. 49 Structure and physical data of Compound 44

104

Table 44. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 44 in CD3OD
position
1
2
3
4
5
6
7
8
9
3-OCH3

13

1

C
130.8
112.1
149.3
153.6
116.0
124.9
199.9
41.8
59.1
56.6

H

7.55 (1H, d, J= 2.0 Hz)

6.87 (1H, d, J= 8.3 Hz)
7.58 (1H, dd, J= 8.3, 2.0 Hz)
3.16 (2H, t, J= 6.2 Hz)
3.94 (2H, t, J= 6.2 Hz)
3.91 (3H, s)105➨ 23 㡯 ᪤▱໬ྜ≀ Compound 45 ࡢᵓ㐀Ỵᐃ
Cpd 45 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C9H10O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ108.5 ࠿ࡽ 149.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ170.4 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟
⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 49) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 45 ࢆ syringic acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 197.0456 [M-H](calcd for C9H9O5: 197.0455)

Fig. 50 Structure and physical data of Compound 45

106

Table 45. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 45 in CD3OD
position
1
2, 6
4
3, 5
1-COOH
3, 5-OCH3

13

C
122.5
108.5
149.0
141.8
170.4
56.9

107

1

H

7.33 (2H, s)

3.88 (6H, s)➨ 24 㡯 ᪤▱໬ྜ≀ Compound 46 ࡢᵓ㐀Ỵᐃ
Cpd 46 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C13H20O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ201.4 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࢆ 1 ᮏࠊ127.3ࠊ130.3ࠊ137.1ࠊ
167.6 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ68.9ࠊ80.1 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ
࡚࠸ࡿⅣ⣲ࡀ 2 ᮏࠊ50.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ19.7ࠊ23.6ࠊ24.0ࠊ
24.6 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ
࣮ࢱࢆᩥ⊩್ 50) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 46 ࢆ (6S,9R)-vomifoliol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 247.1305 [M+Na] +(calcd for C13H20O3Na: 247.1305)[α]D24 = +54.6 (c = 0.3, MeOH)

Fig. 51 Structure and physical data of Compound 46

108

Table 46. 13C NMR (150MHz) and 1H NMR (600 MHz) data for Cpd 46 in CD3OD
position
1
2
3
4
5
6
7
8
9
10
11
12
13

13

1

C
42.6
50.9

H

2.16 (1H, d, J= 16.9 Hz)
2.48 (1H, d, J= 16.9 Hz)

201.4
127.3
167.6
80.1
130.3
137.1
68.9
19.7
24.6
24.0
23.6

5.88 (1H, brs)

5.78 (1H, d, J= 16.9 Hz)
5.81 (1H, dd, J= 16.9, 6.0 Hz)
4.57 (1H, brs)
1.24 (3H, d, J= 6.4 Hz)
1.02 (3H, s)
1.04 (3H, s)
1.92 (3H, d, J= 1.1 Hz)

109➨ 25 㡯 ᪤▱໬ྜ≀ Compound 47 ࡢᵓ㐀Ỵᐃ
Cpd 47 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C8H8O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ111.5 ࠿ࡽ 155.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ193.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.6 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟
⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 51) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 47 ࢆ vanillin ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (negative)
m/z: 151.0404 [M-H](calcd for C8H7O3: 151.0401)

Fig. 52 Structure and physical data of Compound 47

110

Table 47. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 47 in CD3OD
position
1
2
3
4
5
6
1-CHO
3-OCH3

13

1

C
130.8
111.5
149.9
155.0
116.5
128.1
193.0
56.6

H

7.45 (1H, d, J= 1.8 Hz)

6.95 (1H, d, J= 7.9 Hz)
7.44 (1H, dd, J= 7.9, 1.8 Hz)
9.75 (1H, s)
3.92 (3H, s)

111

➨ 26 㡯 ᪤▱໬ྜ≀ Compound 48 ࡢᵓ㐀Ỵᐃ
Cpd 48 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C9H6O3 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ103.6 ࠿ࡽ 163.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ163.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ114.7ࠊ146.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 52) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 48 ࢆ umbelliferone ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 185.0208 [M+Na]+(calcd for C9H6O3Na: 185.0209)

Fig. 53 Structure and physical data of Compound 48

112

Table 48. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 48 in CD3OD
position
2
3
4
5
6
7
8
9
10

13

1

C
163.9
114.7
146.2
130.8
112.5
163.3
103.6
157.4
113.3

H

6.18 (1H, d, J= 9.4 Hz)
7.85 (1H, d, J= 9.4 Hz)
7.45 (1H, d, J= 8.5 Hz)
6.79 (1H, dd, J= 8.5, 2.3 Hz)
6.71 (1H, d, J=2.3 Hz)

113

➨ 27 㡯 ᪤▱໬ྜ≀ Compound 49 ࡢᵓ㐀Ỵᐃ
Cpd 49 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C8H8O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ116.0 ࠿ࡽ 151.9 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ169.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ52.4 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟
⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 53) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 49 ࢆ methyl
protocatechuate ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 167.0350 [M-H](calcd for C8H7O4: 167.0350)

Fig. 54 Structure and physical data of Compound 49

114

Table 49. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 49 in CD3OD
13
position
C
1
122.8
2
117.6
3
146.3
4
151.9
5
116.0
6
123.8
7
169.0
7-OCH352.4
m: .multiplet or overlapped signals

115

1

H

7.42 (1H, brs)

6.80 (1H, d, J= 8.0 Hz)
7.41 (1H, m)
3.83 (3H, s)➨ 28 㡯 ᪤▱໬ྜ≀ Compound 50 ࡢᵓ㐀Ỵᐃ
Cpd 50 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H34O15 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ62.9 ࠿ࡽ 105.2 ppm ࡟ࢢࣝࢥ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ
102.7 ࠿ࡽ 163.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 10 ᮏࠊ172.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ21.1 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.3 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ36.0 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほࡉࢀࡓࡇ࡜ࡼࡾࠊ2 ࡘࡢࢢࣝࢥ࣮ࢫࡀ⤖ྜࡋ࡚࠸ࡿᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 54) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 50 ࢆ 3,4-dihydro-10-hydroxy-7-methoxy-3-(R)methyl-1H-3,4-dihydronaphtho-[2,3c]-pyran-1-one-9-O-β-D-glucopyranosyl-(1Ѝ6)glucopyranoside ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 621.1789 [M+Na]+(calcd for C27H34O15Na: 621.1790)

Fig. 55 Structure and physical data of Compound 50

116

Table 50. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 50 in CD3OD
position
1
3
4

13

C
172.9
77.8
36.0

1

5
6
7
8
9
10
11
4a
5a
9a
10a
7-OCH3Glu-1'
2'
3'
4'
5'
6'

117.2
102.7
163.3
105.4
159.5
163.3
21.1
136.2
142.0
112.0
102.7
56.3
104.0
75.3
77.7
71.8
77.6
70.6

7.03 (1H, s)
6.87 (1H, d, J= 2.3 Hz)

Glu-1''
2''
3''
4''
5''
6''

105.2
75.3
78.1
71.8
78.2
62.9

m: .multiplet or overlapped signals

117

H

4.76 (1H, m)

7.03 (1H, d, J= 2.3 Hz)

1.51 (3H, d, J= 6.3 Hz)

3.93 (3H, s)
5.01 (1H, d, J= 7.7 Hz)
3.64 (1H, m)
3.50 (1H, t, J= 9.1 Hz)
3.45 (1H, m)
3.79 (1H, m)
3.86 (1H, m)
4.19 (1H, dd, J= 11.6, 2.0 Hz)
4.37 (1H, d, J= 7.7 Hz)
3.25 (1H, m)
3.33 (1H, m)
3.30 (1H, m)
3.23 (1H, m)
3.64 (1H, m)
3.85 (1H, m)➨ 29 㡯 ᪤▱໬ྜ≀ Compound 51 ࡢᵓ㐀Ỵᐃ
Cpd 51 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C28H32O16 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ18.0 ࡜ 68.7-104.6 ppm ࡟ࢢࣝࢥ࣮ࢫཬࡧ࣒ࣛࣀ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ95.1 ࠿ࡽ 166.2 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 12 ᮏࠊ179.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ135.6ࠊ159.0 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼ
ࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣇࣛ࣎ࣀ࢖ࢻ࡛࠶ࡿ࡜᥎ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 55) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 51 ࢆ narcissin ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (positive)
m/z: 647.1581 [M+Na] +(calcd for C28H32O16Na: 647.1583)

Fig. 56 Structure and physical data of Compound 51

118

Table 51.

13

C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 51 in CD3OD

position
2
3
4
5
6
7
8
9
10
1'
2'
3'
4'
5'
6'
3'-OCH3
Glu-1
2
3
4
5
6

13

1

C
159.0
135.6
179.5
163.1
100.1
166.2
95.1
158.6
105.8
124.2
114.7
148.4
151.0
116.3
124.2
56.9
104.6
76.1
77.5
71.8
78.3
68.7

H

6.20 (1H, d, J= 1.8 Hz)
6.39 (1H, d, J= 1.8 Hz)

7.94 (1H, d, J= 1.9Hz)

6.91 (1H, d, J= 8.4 Hz)
7.62 (1H, dd, J= 8.4, 1.9 Hz)
3.95 (3H, s)
5.23 (1H, d, J= 7.3 Hz)

3.27-3.50 (5H, m)

3.82 (1H, dd, J= 1.2, 11.1 Hz)
4.53 (1H, d, J= 1.1 Hz)

Rha-1
102.7
2
72.2
72.4
3
4
74.0
5
69.9
6
18.0
m: .multiplet or overlapped signals

3.27-3.50 (4H, m)
1.10 (3H, d, J= 6.2 Hz)

119➨ 30 㡯 ᪤▱໬ྜ≀ Compound 52 ࡢᵓ㐀Ỵᐃ
Cpd 52 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H30O15 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊ18.0 ࡜ 68.7-104.7 ppm ࡟ࢢࣝࢥ࣮ࢫཬࡧ࣒ࣛࣀ࣮ࢫ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ95.1 ࠿ࡽ 166.2 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 10 ᮏࠊ179.6 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ135.6ࠊ161.6 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼ
ࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣇࣛ࣎ࣀ࢖ࢻ࡛࠶ࡿ࡜᥎ ࡋࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 56) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 52 ࢆ kaempferol 3-β-rutinoside࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (positive)
m/z: 617.1476 [M+Na] +(calcd for C27H30O15Na: 617.1477)

Fig. 57 Structure and physical data of Compound 52

120

Table 52. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 52 in CD3OD
position
2
3
4
5
6
7
8
9
10
1'
2'
3'
4'
5'
6'
Glu-1
2
3
4
5
6

13

1

C
161.6
135.6
179.6
163.2
100.1
166.2
95.1
158.7
105.8
122.9
132.5
116.3
159.6
116.3
132.5
104.7
75.9
78.3
71.6
77.4
68.7

H

6.22 (1H, d, J= 2.0 Hz)
6.41 (1H, d, J= 2.0 Hz)

8.07 (1H, d, J= 8.9 Hz)
6.90 (1H, d, J= 8.9 Hz)
6.90 (1H, d, J= 8.9 Hz)
8.07 (1H, d, J= 8.9 Hz)
5.13 (1H, d, J= 7.3 Hz)
3.43 (1H, m)
3.42 (1H, m)
3.24 (1H, m)
3.33 (1H, m)
3.81 (1H, dd, J= 11.0, 1.4 Hz)
3.38 (1H, m)
4.52 (1H, brs)
3.63 (1H, m)
3.52 (1H, dd, J= 9.5, 3.4 Hz)
3.27 (1H, m)
3.44 (1H, m)
1.12 (3H, d, J= 6.2 Hz)

Rha-1
102.6
2
72.3
3
72.5
4
74.1
5
69.9
6
18.0
m: .multiplet or overlapped signals121➨ 31 㡯 ᪤▱໬ྜ≀ Compound 53 ࡢᵓ㐀Ỵᐃ
Cpd 53 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C15H10O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ109.2 ࠿ࡽ 166.7 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 12 ᮏࠊ183.3ࠊ192.0 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ22.2 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 57) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 53 ࢆ
emodin ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Yellow amorphous powder
HR-ESI-MS (negative)
m/z: 269.0457 [M-H](calcd for C15H9O5: 269.0455)

Fig. 58 Structure and physical data of Compound 53

122

Table 53. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 53 in CD3OD
13
position
C
1
163.7
2
125.4
3
149.8
4
121.9
5
110.2
6
167.3
7
109.2
8
166.7
9
192.0
10
183.3
11
137.0
12
110.7
13
115.0
14
134.8
15
22.2
m: .multiplet or overlapped signals

1H

7.08 (1H, brs)
7.55 (1H, brs)
7.17 (1H, d, J= 2.3 Hz)
6.56 (1H, d, J= 2.3 Hz)

2.43 (3H, brs)123

➨ 32 㡯 ᪤▱໬ྜ≀ Compound 54 ࡢᵓ㐀Ỵᐃ
Cpd 54 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C36H36O8N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ110.7 ࠿ࡽ 157.1 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 20 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.2ࠊ173.1 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ120.2ࠊ141.9
ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ90.1 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏࠊ35.5ࠊ35.9ࠊ42.4ࠊ42.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ56.6ࠊ
57.1 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ
ⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ཬࡧ AX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ
1,3,4-⨨᥮࣋ࣥࢮࣥཬࡧ 1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 58) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 54 ࢆ tribulusamide A ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (negative)
m/z: 623.2396 [M-H](calcd for C36H35O8N2: 623.2399)[α]D24 = -2.0 (c = 0.2, MeOH)

Fig. 59 Structure and physical data of Compound 54

124

Table 54. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 54 in CD3OD
position
1
2
3
4
5
6
7
8
9
3-OCH31'
2'
3'4', 8'
5', 7'
6'
1''
2''
3''
4''
5''
6''
7''
8''
9''
3''-OCH3
1'''
2'''
3'''
4''', 8'''5''', 7'''
6'''

13

1

C
130.6
113.4
146.2
151.4
129.6
118.3
141.9
120.2
169.2
57.1
42.7
35.9
131.5
131.0
116.6
157.1
132.8
110.7
148.3
149.4
116.5
119.6
90.1
58.9
173.1
56.6
42.4
35.5
131.2
130.9
116.4
157.0

H

7.11 (1H, s)

6.75 (1H, s)
7.43 (1H, d, J= 15.8 Hz)
6.39 (1H, d, J= 15.8 Hz)
3.89 (3H, s)
3.47 (2H, s)
2.75 (2H, m)
7.04 (2H, m)
6.77-7.09 (2H, m)

6.77-7.09 (1H, m)

6.77-7.09 (1H, m)
5.89 (1H, d, J= 8.4 Hz)
4.15 (1H, d, J= 8.4 Hz)
3.82 (3H, s)
3.33 (1H, m)
2.65 (2H, m)
6.77-7.09 (2H, m)

m: .multiplet or overlapped signals125➨ 4 ❶ ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᡂศ◊✲➨ 1 ⠇ ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡟ࡘ࠸࡚Ꮫྡ㸸Heliciopsis terminalis࿴ྡ㸸࡞ࡋ(ࢱ࢖࡛ࡣ࣒࢔ࢺࢥࣥ࡜࿧ࡤࢀ࡚࠸ࡿࠋ)⛉ྡ㸸Proteaceae (࣐ࣖࣔ࢞ࢩ⛉)ᒓྡ㸸Heliciopsis≉ᚩ㸸 ᮌᮏ࡛㧗ࡉࡣ 8-10 mࠋ༢ⴥࡢ㛗ࡉࡣ 14-23 cmࠊᖜ 4-8 cm ࡢಽ༸ᆺ࡛ⴥ᯶ࡣ 1-2 cmࠋᯝᐇࡣ᰾ᯝ࡛ࠊ✀Ꮚࡣ 1-2 ಶࠋ ⰼᮇࡣ 5-6 ᭶ࠋཎ⏘ᆅ࣭ศᕸࡣ࢖ࣥࢻ࣭ᮾ༡࢔ࢪ࢔
࡞࡝ࠋ59)
୰ᅜ࡛ࡣ⭈⮚ࡢ⑓Ẽ࡟౑⏝ࡉࢀࡿࠋ

http://tplant.web.fc2.com/3yamamo_heliciopsis.html

126➨ 2 ⠇ ᢳฟࠊศ㞳࠾ࡼࡧ⢭〇࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ᮏ᳜≀ࡢᶞ⓶ࢆ࣓ࢱࣀ࣮࡛ࣝᢳฟࡋࠊᖖἲ࡟ᚑ
࠸ࠊn-࣊࢟ࢧࣥࠊ㓑㓟࢚ࢳࣝࠊ1-BuOHࠊỈ࡛㡰ḟศ㓄ࡋࡓࠋ࣋ࢺࢼ࣒⏘᳜≀ H. terminalis ࡢᶞ⓶ࡢ㓑㓟࢚ࢳࣝྍ⁐⏬ศ㸦118.28 g㸧ࢆࠊࢩࣜ࢝ࢤ
ࣝࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊODS ࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮ࠊཬࡧ ODS-HPLC ࢆ⏝࠸࡚ศ㞳ࠊ⢭〇ࡋࠊ15 ✀ࡢ໬ྜ≀ࢆ༢㞳ࡋࡓࠋࡑࡢෆ compound 55ࠊ56ࠊ57 ࡣ᪂つ໬ྜ≀࡜ุ᫂ࡋࡓࠋ
(Chart 4)

127

Chart 4: Isolated compounds from the bark of H. terminalis128➨ 3 ⠇  ᪂つ໬ྜ≀࡟ࡘ࠸࡚➨ 1 㡯 ᪂つ໬ྜ≀ Compound 55 ࡢᵓ㐀Ỵᐃ
Cpd 55 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C10H12O6 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊⅣ⣲⥲ᩘ 10 ಶࡢ࠺ࡕࠊ108.5 ࠿ࡽ 159.9 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࠊ168.3 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ64.3ࠊ
71.4 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡀ 2 ᮏࠊࡲࡓࠊ67.1 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡑࡋ࡚ࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ proton ࡢ࢝ࢵࣉࣜࣥࢢࣃࢱ࣮ࣥ࠿ࡽࠊ1,3,5-⨨᥮࣋ࣥࢮࣥࢆ᭷ࡍࡿᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋࡉࡽ࡟㒊ศᵓ㐀ࡢ⤖ྜ఩⨨࡟㛵ࡍࡿ┦㛵ࡀほ ࡉࢀࠊ
9 ఩ࠊ10 ఩࡟ࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋࡲࡓࠊ8 ఩࠿ࡽ 7 ఩࢝ࣝ࣎ࢽࣝⅣ⣲࡬ࡢ┦㛵࠿ࡽ࢚ࢫࢸࣝ⤖ྜࡢ఩⨨ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ୍᪉ࠊⰾ㤶⎔㒊ศࡢ⨨᥮ᵝᘧࡀ␗࡞ࡿ㢮ఝ໬ྜ≀࡛ࡣ࠸ࡎࢀࡶ 9R 㓄⨨ࡀ㈇ࡢ᪕ගᛶࠊ9S 㓄⨨ࡀṇࡢ᪕ගᛶࢆ♧ࡍࡓࡵࠊ᪕ගᗘࢆ ᐃࡋࡓ⤖ᯝࠊ㈇ࡢ᪕ගᛶࢆ♧ࡋࡓࡇ࡜࠿ࡽ 9 ఩ࡢ❧య㓄⨨ࡣ R ࡜Ỵᐃࡋࡓࠋ௨ୖࡼࡾࠊCompound 55 ࢆ Fig. 60 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

129

R

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 251.0526 [M+Na] +(calcd for C10H12O6Na: 251.0526)[α]D20 = -21.5 (c = 0.13, MeOH)
IR (film, cm-1): 3360, 2946, 1702, 1600, 1457, 1348, 1239, 1165, 1110, 1056, 1008
UV λmax (MeOH) nm (log ε): 200 (4.36), 218 (4.05), 252 (3.42), 307 (2.74)

Fig. 60 Structure and physical data of Compound 55

130









COSY







HMBC

Fig. 61 COSY and HMBC correlations of Compound 55

Table 55. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 55 in CD3OD
position
1
2, 6
3, 5
4
7
8
9
10

13

1

C
133.2
109.1
159.9
108.5
168.3
67.1

H

6.97 (1H, d, J= 2.4 Hz)
6.48 (1H, d, J= 2.4 Hz)
4.34 (1H, dd, J= 4.5, 11.3 Hz)
4.27 (1H, dd, J= 6.2, 11.3 Hz)
3.95 (1H, m)
3.65 (2H, dq, J= 5.6, 11.3 Hz)

71.4
64.3

m: .multiplet or overlapped signals131➨ 2 㡯 ᪂つ໬ྜ≀ Compound 56 ࡢᵓ㐀Ỵᐃ
Cpd 56 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C18H24O9 ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋCpd 56
࡟ࡣ NMR ࢫ࣌ࢡࢺࣝࡼࡾ⢾㒊ࡀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ᝿ᐃࡉࢀࡓࡓࡵࠊ1M HCl ࡛ຍỈศゎࢆ⾜࠸ࠊ㐟㞳ࡋࡓ⢾࡟ࡘ࠸࡚᪕ගᗘ᳨ฟჾ௜ࡁ HPLC ࢆ⏝࠸࡚⢾ศᯒࢆ⾜ࡗࡓ࡜ࡇࢁࠊ
Cpd 56 ࡟ࡣ D-glucose ࡀྵࡲࢀࡿࡇ࡜ࡀ♧ࡉࢀࡓࠋࡇࡢࡇ࡜ࡣࠊ13C NMR ࡟࠾࠸࡚Ⅳ⣲⥲
ᩘ 18 ಶࡢ࠺ࡕࠊ65.0 ࠿ࡽ 104.1 ppm ࡢ glucose ࡟⏤᮶ࡍࡿ 6 ᮏࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜࡜୍⮴ࡋࡓࠋ
ࡑࡢ௚࡟ࡶ 13C NMR ࡟࠾࠸࡚ࠊ102.0 ࠿ࡽ 155.0 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜
⪃࠼ࡽࢀࡿ 6 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ169.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ
129.6ࠊ139.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ12.2ࠊ14.6 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ56.7 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲ
ࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥ⣔ࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋ࢔ࢩࣝᇶ࡟ࡘ࠸࡚ࡣ 2D NMR ┦㛵ࡸࢣ࣑࢝ࣝࢩࣇࢺࡢ
್࡞࡝ࡶ⪃៖ࡍࡿࡇ࡜࡛ࢳࢢࣜࣥ㓟࡛࠶ࡿࡇ࡜ࡀุ᫂ࡋࡓࠋࡲࡓࠊ⤖ྜ఩⨨࡟㛵ࡋ࡚ࡣ 1
఩࡜ 1'఩ࠊ6'఩࡜ 1''఩࡟ࡑࢀࡒࢀ┦㛵ࡀほࡉࢀࡓࡇ࡜ࡼࡾ glucose ࡜ⰾ㤶⎔࡜࢝ࣝ࣎ࢽࣝ

Ⅳ⣲ࡢ⤖ྜ఩⨨ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋ
௨ୖࡼࡾࠊCompound 56 ࢆ Fig. 62 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ132

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 407.1305 [M+Na] +(calcd for C18H24O9Na: 407.1313)
IR (film, cm-1): 3360, 2932, 2830, 1695, 1640, 1593, 1511, 1450, 1266, 1205,
1123, 1069, 1022
UV λmax (MeOH) nm (log ε): 204 (4.36), 218 (4.15), 230 (3.96), 282 (3.38)

Fig. 62 Structure and physical data of Compound 56

133




COSY







Fig. 63 COSY and HMBC correlations of Compound 56

134

HMBC

Table 56. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 56 in CD3OD
position
1
2
3
4
5
6
1'
2'
3'
4'
5'
6'

13

1

C
140.9
102.0
152.2
155.0
120.6
107.6
104.1
75.1
77.9
72.1
75.6
65.0

H

6.47 (1H, d, J= 2.8 Hz)

6.93 (1H, d, J= 8.7 Hz)
6.24 (1H, dd, J= 8.7, 2.8 Hz)
4.69 (1H, d, J= 7.6 Hz)
3.46 (1H, m)
3.46 (1H, m)
3.36 (1H, m)
3.57 (1H, m)
4.48 (1H, dd, J= 11.8, 2.2 Hz)
4.22 (1H, dd, J= 11.8, 7.3 Hz)

1''
169.5
2''
129.6
3''
139.2
4''
14.6
5''
12.2
3-OCH356.7
m: .multiplet or overlapped signals

6.85 (1H, m)
1.80 (3H, m)
1.81 (3H, m)
3.80 (3H, s)135➨ 3 㡯 ᪂つ໬ྜ≀ Compound 57 ࡢᵓ㐀Ỵᐃ
Cpd 57 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H26O11 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ 13C
NMR ࡟࠾࠸࡚ࠊⅣ⣲⥲ᩘ 27 ಶࡢ࠺ࡕࠊ105.2 ࠿ࡽ 157.6 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ
࡜⪃࠼ࡽࢀࡿ 14 ᮏࡢࣆ࣮ࢡࠊ171.1 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ
66.9 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡀ 1 ᮏࠊ29.9ࠊ37.6 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ36.5ࠊ66.9ࠊ79.8 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ56.6ࠊ
60.9 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ
࣋ࣥࢮࣥ⎔ࡢ proton ࢝ࢵࣉࣜࣥࢢࣃࢱ࣮ࣥ࠿ࡽࠊ1,3,4,5-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࡓࠋࡲࡓࠊIR ࢫ࣌ࢡࢺࣝ࠿ࡽࠊỈ㓟ᇶࠊ࢝ࣝ࣎ࢽࣝᇶࠊⰾ㤶⎔࡟⏤᮶ࡍࡿࣆ࣮ࢡࡀほ ࡉࢀࡓࠋࡼࡾヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵ࡟ 2D NMR (HSQC, HMBC, COSY) ࢆ ᐃࡋࡓ࡜ࡇࢁࠊྛ
㒊ศᵓ㐀ࢆᨭᣢࡍࡿ┦㛵ࡀᚓࡽࢀࡓࠋࡉࡽ࡟㒊ศᵓ㐀ྠኈࡢ⤖ྜࢆ௓ࡋࡓ┦㛵ࡀほ ࡉࢀࠊ
7''఩࡜ 2''఩ࠊ2 ఩࡜ 2'఩ࠊ7''఩࡜ 9''఩࡟ࡑࢀࡒࢀ┦㛵ࡀほ ࡉࢀࡓࡇ࡜࠿ࡽࠊⰾ㤶⎔ A ࡢ
1''఩࡜ⰾ㤶⎔ B ࡢ 1'఩ࡀ 7''఩࡜ 2 ఩࡟ࡑࢀࡒࢀ⤖ྜࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋᩥ⊩᳨⣴ࢆ⾜ࡗࡓ࡜ࡇࢁࠊB ⎔ࡢ 5’఩࡟Ỉ㓟ᇶࢆᣢࡓ࡞࠸㛵㐃໬ྜ≀ smiglabrone A60)࡜ B ⎔ࢆ㝖࠸࡚Ⰻ࠸୍⮴ࢆ♧ࡋࡓࡇ࡜࠿ࡽ┦ᑐ㓄⨨ࢆ᥎ᐃࡋࠊࡲࡓࠊ⤯ᑐ㓄⨨࡟㛵ࡋ࡚ࡣ CD ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ 232 nm ࡜ 283 nm ࡟㈇ࡢࢩࢢࢼࣝࡀࠊࡲࡓ 261 nm ࡟ṇࡢࢩࢢࢼࣝࡀほ ࡉࢀࡓࡇ࡜ࡼࡾ smiglabrone A ࡜ྠࡌ❧య໬Ꮫ࡛࠶ࡿࡇ࡜ࡀ♧၀ࡉࢀࡓࠋ
௨ୖࡼࡾࠊCompound 57 ࢆ Fig. 64 ࡟♧ࡍᵓ㐀࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ136

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 549.1368 [M+Na] +(calcd for C27H26O11Na: 549.1367)[α]D24 = -132 (c = 0.13, MeOH)
IR (film, cm-1): 3313, 2959, 2844, 1742, 1620, 1518, 1450, 1375, 1328, 1117
UV λmax (MeOH) nm (log ε): 213 (4.51), 229 (4.35), 276 (3.53)

Fig. 64 Structure and physical data of Compound 57

137















COSY







Fig. 65 COSY and HMBC correlations of Compound 57

138

HMBC

Table 57. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 57 in CD3OD
position
2
3
4
5
6
7
8
9
10
1'
2', 6'
3', 5'
4'
1''2'', 6''3'', 5''
4''
7''
8''

13

1

C
79.8
66.9
29.9

H
4.76 (1H, s)
4.27 (1H, m)
2.84 (1H, dd, J= 17.3, 2.5 Hz)
2.92 (1H, m)

157.6
96.5
151.7
106.3
153.6
105.6
136.5
107.1
151.8
136.3
135.4
105.2
149.3
135.3
36.5
37.6

6.20 (1H, s)

6.61 (2H, s)

6.45 (2H, s)

4.61 (1H, d, J= 7.2 Hz)
2.92 (1H, m)
3.13 (1H, dd, J= 15.9, 7.5 Hz)

9''
171.1
4'-OCH3
60.9
3'', 5''-OCH3
56.6
m: .multiplet or overlapped signals

3.80 (3H, s)
3.61 (6H, s)139➨ 4 ⠇  ᪤▱໬ྜ≀࡟ࡘ࠸࡚࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᶞ⓶ࡢ㓑㓟࢚ࢳࣝྍ⁐⏬ศࢆศ㞳ࠊ⢭〇ࡍࡿ㐣⛬࡛ࠊ᪂つ໬ྜ≀࡜࡜ࡶ࡟ࠊ᪤▱໬ྜ≀ 13 ✀ࢆ༢㞳ࡋࡓࠋྛ໬ྜ≀ࡢ NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್࡜ẚ㍑ࡍࡿࡇ࡜࡛ࠊࡑࢀࡒࢀ௨ୗ࡟♧ࡍ᪤▱໬ྜ≀࡛࠶ࡿ࡜ྠᐃࡋࡓࠋ
Compound 58: Aurantiamide 61)
Compound 59: Aurantiamide acetate 62)
Compound 60: Asperphenamate 63)
Compound 61: Evofolin B 64)
Compound 62: 4'-O-Methylgallocatechin 65)
Compound 63: Androst-1,4-dien-3,17-dione 66)
Compound 64: (8'Z)-1,3-Dihydroxy-5-[16'-(3'',5''-dihyroxyphenyl)-8'-hexadecen-1'-yl] benzen 67)
Compound 65: 6'-[(E)-2''-Hydroxymehthyl, 2''-butenoyl] arbutin 68)
Compound 66: (+)-1-Hydroxysyringaresinol 69)
Compound 67: (+)-1-Hydroxypinoresinol 69)
Compound 68: Vladinol F 70, 71)
Compound 69: 4’-Dihydrophaseic acid 72)
Compound 60: 3,5-Dihydroxybenzenepentanoic acid 73)

140➨ 1 㡯 ᪤▱໬ྜ≀ Compound 58 ࡢᵓ㐀Ỵᐃ
Cpd 58 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C25H26O3N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ127.4 ࠿ࡽ 139.6 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ170.2ࠊ173.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ64.1 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏࠊ38.0ࠊ38.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ54.3ࠊ56.8 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾ 3 ࡘࡢⰾ㤶⎔ࢆ᭷ࡍࡿᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 61) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 58 ࢆ aurantiamide ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 425.1832 [M+Na]+(calcd for C25H26O3N2Na: 425.1836)[α]D24 = - 66.0 (c = 0.1, MeOH)

Fig. 66 Structure and physical data of Compound 58

141

Table 58. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 58 in CD3OD
13

1

2
4
5
7
8

54.3
173.5
56.8
170.2
38.9

4.66 (1H, m)

9

38.0

1'
2', 6'
3',5'
4'
1"2", 6''
3", 5''
4"1'"2'", 6'''3'", 5'''
4'"
m: .multiplet or overlapped signals

135.1
127.4
129.5
133.2
138.6
130.5
129.6
128.5
139.6
130.5
129.5
127.4

position
1

C
64.1

142

H
3.95 (1H, m)
3.22 (1H, m)
4.07 (1H, m)

3.18 (1H, m)
3.01 (1H, m)
2.81 (1H, m)
2.56 (1H, m)
7.68 (1H, d, J= 10.2 Hz)
7.45 (1H, t, J= 10.2 Hz)
7.54 (1H, t, J= 10.2 Hz)
7.20 (1H, d, J= 10.2 Hz)
7.26 (1H, t, J= 10.2 Hz)
7.20 (1H, t, J= 10.2 Hz)
7.01 (1H, d, J= 10.2 Hz)
7.10 (1H, t, J= 10.2 Hz)
7.05 (1H, t, J= 10.2 Hz)➨ 2 㡯 ᪤▱໬ྜ≀ Compound 59 ࡢᵓ㐀Ỵᐃ
Cpd 59 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C27H28O4N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ126.8 ࠿ࡽ 136.9 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ167.3ࠊ170.6ࠊ173.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ37.5ࠊ
38.6ࠊ64.7 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ49.5ࠊ55.1 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾ 3 ࡘࡢⰾ㤶⎔ࡀ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 62) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 59 ࢆ aurantiamide acetate ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 467.1937 [M+Na]+(calcd for C27H28O4N2Na: 467.1941)[α]D24 = -21.0 (c = 1.4, CHCl3)

Fig. 67 Structure and physical data of Compound 59

143

Table 59. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 59 in CDCl3
position
1
2
3-a
3-b
4
5, 9
6, 8
7
1’
2’
3’, 7’
4’, 6’
5’1”
2”
3”4”, 8’’
5”, 7’’
6”
9”-a
9”-b
α-NH
β-NH
COCH3
COCH3

13

C
170.6
55.1
38.6
136.9
128.6
129.4
127.2
167.3
133.8
128.7
127.1
132.0
49.5
37.5
136.7
128.8
129.2
126.8
64.7

170.9
20.9

m: .multiplet or overlapped signals

144

1

H

4.84 (1H, m)
3.20 (1H, dd, J= 16.2, 7.8 Hz)
3.10 (1H, dd, J= 16.2, 9.6 Hz)

7.25 (5H, m)

7.71 (2H, d, J= 9.0 Hz)
7.41 (2H, t, J= 9.0 Hz)
7.50 (1H, t, J= 8.4 Hz)
4.34 (1H, m)
2.73 (2H, m)
7.05 (2H, m)
7.13 (2H, m)
3.91 (1H, dd, J= 13.8, 6.0 Hz)
3.84 (1H, dd, J= 13.8, 4.8 Hz)
6.41 (1H, d, J= 10.2 Hz)
6.98 (1H, d, J= 9.6 Hz)
2.73 (3H, s)➨ 3 㡯 ᪤▱໬ྜ≀ Compound 60 ࡢᵓ㐀Ỵᐃ
Cpd 60 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C32H30O4N2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C
NMR ࡟࠾࠸࡚ࠊ126.2 ࠿ࡽ 137.3 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 16 ᮏࡢࣆ࣮ࢡࡀ࠶ࡾࠊ167.4ࠊ167.6ࠊ172.1 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ37.4ࠊ
37.7ࠊ65.6 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ50.4ࠊ54.6 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ4 ࡘࡢⰾ㤶⎔ࢆ᭷ࡍࡿᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 63) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 60 ࢆ asperphenamate ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 529.2095 [M+Na]+(calcd for C32H30O4N2Na: 529.2098)[α]D24 = -45.0 (c = 0.2, MeOH)

Fig. 68 Structure and physical data of Compound 60

145

Table 60. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 60 in CDCl3
position
1
2
3
4
5
6
7

13

C
137.3
129.0
128.8
126.9
128.8
129.0

8
9

54.6
65.6

N-H1
1’
2’, 6’
3’, 5’
4’
7’

135.9
129.3
128.5
126.2
37.4

1

H

7.52 (5H, m)

3.60 (1H, dd, J= 13.8, 7.8 Hz)
3.52 (1H, dd, J= 13.8, 7.8 Hz)
5.23 (1H, q, J= 6.6 Hz)
4.84 (1H, dd, J= 11.4, 3.6 Hz)
4.34 (1H, dd, J= 11.4, 4.8 Hz)
6.92 (1H, d, J= 6.6 Hz)

8’
50.4
9’
172.1
2
N-H
1”
134.4
2”, 6’’
127.5
3”, 5’’
128.8
4”
132.2
7”
167.6
1’”
133.5
2’”, 2’’’
127.2
3’”, 5’’’
128.8
4’”
131.5
7”’
167.4
m: .multiplet or overlapped signals

7.53 (5H, m)
3.25 (1H, dd, J= 13.8, 7.8 Hz)
3.02 (1H, dd, J= 13.8, 7.8 Hz)
4.93 (5H, m)
7.01 (1H, d, J= 8.4 Hz)
7.96 (2H, dd, J= 7.2, 1.2 Hz)
7.62 (2H, td, J= 7.2, 1.2 Hz)
7.74 (1H, tt, J= 7.2, 1.2 Hz)

8.01 (2H, dd, J= 7.2, 1.2 Hz)
7.54 (2H, td, J= 7.2, 1.2 Hz)
7.69 (1H, tt, J= 7.2, 1.2 Hz)
7.81 (1H, m)

146

➨ 4 㡯 ᪤▱໬ྜ≀ Compound 61 ࡢᵓ㐀Ỵᐃ
Cpd 61 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C17H18O6 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ112.7 ࠿ࡽ 149.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡࠊ
199.8 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ65.6 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜ
ࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏࠊ56.4 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ56.5ࠊ
56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ
ⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥ
ࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 64) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ
Cpd 61 ࢆ evofolin B ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 341.0994 [M+Na] +(calcd for C17H18O6Na: 341.0996)[α]D24 = -15.0 (c = 0.13, MeOH)

Fig. 69 Structure and physical data of Compound 61

147

Table 61. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 61 in CD3OD
position
1
2
3
4
5
6
7
1’
2’
3’
4’
5’
6’
7’
8’

13

1

C
130.6
112.7
149.1
149.1
115.9
125.3
199.8
130.0
112.9
147.0
149.5
116.7
122.3
56.4
65.6

H

7.46 (1H, d, J= 1.8 Hz)

6.76 (1H, m)
7.51 (1H, dd, J= 8.4, 1.8 Hz)

6.80 (1H, d, J= 1.8 Hz)

6.70 (1H, m)
6.73 (1H, m)
4.65 (1H, dd, J= 8.4, 5.4 Hz)
4.14 (1H, dd, J= 9.0, 8.4 Hz)
3.61 (1H, dd, J= 10.8, 5.4 Hz)
3.72 (3H, s)
3.76 (3H, s)

3-OCH356.5
3’-OCH3
56.5
m: .multiplet or overlapped signals148➨ 5 㡯 ᪤▱໬ྜ≀ Compound 62 ࡢᵓ㐀Ỵᐃ
Cpd 62 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C16H16O7 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ96.5 ࠿ࡽ 157.8 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 10 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ68.7 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏࠊ28.1 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ60.9 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ࡢ proton ࡢ࢝ࢵࣉࣜࣥࢢࣃࢱ࣮ࣥࠊ13C NMRࡢ್࠿ࡽࠊࣇࣛ࣎ࣀ࢖ࢻ࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 65) ࡜ẚ㍑ࡋࡓ
࡜ࡇࢁࠊCpd 62 ࢆ 4'-O-methylgallocatechin ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋPale yellow amorphous powder
HR-ESI-MS (positive)
m/z: 343.0788 [M+Na] +(calcd for C16H16O7Na: 343.0788)[α]D24 = -28.0 (c = 0.1, MeOH)

Fig. 70 Structure and physical data of Compound 62

149

Table 62. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 62 in CD3OD
position
2
3
4

13

C
82.6
68.7
28.1

5
157.8
6
96.5
7
157.6
8
95.7
9
156.7
10
100.8
1'
136.7
2', 6'
107.6
3', 5'
151.6
4'
136.5
4'-OCH3
60.9
m: .multiplet or overlapped signals

1H
4.58 (1H, d, J= 7.2 Hz)
3.99 (1H, m)
2.81 (1H, dd, J= 15.6, 5.4 Hz)
2.53 (1H, dd, J= 15.6, 7.4 Hz)
5.97 (1H, d, J= 2.4 Hz)
5.92 (1H, d, J= 2.4 Hz)

6.43 (2H, s)

3.83 (3H, s)

150➨ 6 㡯 ᪤▱໬ྜ≀ Compound 63 ࡢᵓ㐀Ỵᐃ
Cpd 63 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C19H24O2 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ188.8 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ124.3ࠊ127.9ࠊ159.3ࠊ
173.2 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ23.0ࠊ23.1ࠊ32.6ࠊ33.3ࠊ33.8ࠊ36.4 ppm
ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 6 ᮏࠊ36.7ࠊ51.8ࠊ54.2 ppm ࡢ࣓ࢳࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ14.4ࠊ19.2 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ
NMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 66) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 63 ࢆ androst-1,4-dien-3,17-dione࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 307.1669 [M+Na] +(calcd for C19H24O2Na: 307.1669)[α]D24 = +22.5 (c = 0.16, CHCl3)

Fig. 71 Structure and physical data of Compound 63

151

Table 63. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 63 in CD3OD
13
position
C
1
159.3
2
127.9
3
188.8
4
124.3
5
173.2
6
33.8
7
32.6
8
36.7
9
54.2
10
45.5
11
23.1
12
33.3
13
49.2
14
51.8
15
23.0
16
36.4
17
N.D.
18
14.4
19
19.2
m: .multiplet or overlapped signals

1H
7.13 (1H, d, J= 9.6 Hz)
6.05 (1H, d, J= 9.6 Hz)
5.90 (1H, s)

0.80 (3H, s)
1.14 (3H, s)152➨ 7 㡯 ᪤▱໬ྜ≀ Compound 64 ࡢᵓ㐀Ỵᐃ
Cpd 64 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C28H40O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ99.9 ࠿ࡽ 158.2 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ127.9 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ26.6ࠊ28.9ࠊ28.9ࠊ29.0ࠊ29.2ࠊ
30.7ࠊ35.3 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 7 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ proton ࡢ࢝ࢵࣉࣜࣥࢢࣃࢱ࣮ࣥࡼࡾࠊ1,3,5-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 67) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 64 ࢆ(8'Z)1,3-dihydroxy-5-[16'-(3'',5''-dihyroxyphenyl)-8'-hexadecen-1'-yl] benzene ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 463.2814 [M+Na] +(calcd for C28H40O4Na: 463.2819)

Fig. 72 Structure and physical data of Compound 64

153

Table 64. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 64 in DMSO-d6
position
1, 3, 3'', 5''2, 4''
4, 6, 2'', 6''
5, 1''
1', 16'2', 15'3', 14'4', 13'5', 12'6', 11'
7', 10'8', 9'
1, 3", 3, 5"-OH
m: .multiplet or overlapped signals

13

C
158.2
99.9
106.4
144.3
35.3
30.7
28.8
28.9
29.0
29.2
26.6
129.7

154

1

H

6.01 (2H, brs)
6.01 (4H, brs)
2.34 (1H, t, J= 6.6 Hz)
1.48 (2H, m)
1.27 (2H, m)
1.27 (2H, m)
1.27 (2H, m)
1.48 (2H, m)
1.96 (2H, m)
5.32 (1H, t, J= 4.8 Hz)
9.00 (4H, s)➨ 8 㡯 ᪤▱໬ྜ≀ Compound 65 ࡢᵓ㐀Ỵᐃ
Cpd 65 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C17H22O9 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ 65.2 ࠿ࡽ 103.6 ppm ࡢ glucose ࡟⏤᮶ࡍࡿ 12 ᮏࡢࢩࢢࢼࣝࡀ࠶ࡾࠊ116.7 ࠿ࡽ 154.1
ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ168.5 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼ
ࣝࡀ 1 ᮏࠊ133.7ࠊ143.4 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ14.6 ppm ࡢ࣓ࢳࣝᇶ
࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ AXࢫࣆࣥࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 68) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 65 ࢆ 6'-[(E)-2''hydroxymehthyl-2''-butenoyl] arbutin ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 393.1153 [M+Na] +(calcd for C17H22O9Na: 393.1156)

Fig. 73 Structure and physical data of Compound 65

155

Table 65. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 65 in CD3OD
C
152.3
119.7
116.7
154.1
103.6
75.1

1

3'

78.1

3.23 (1H, m)

4'

72.1

3.18 (1H, m)

5'
6'

75.5
65.2

3.75 (1H, m)
4.12 (1H, dd, J= 11.4, 6.0 Hz)
4.42 (1H, dd, J= 11.4, 1.6 Hz)

position
1
2, 6
3, 5
4
1'
2'

13

H

6.80 (1H, d, J= 9.6 Hz)
6.54 (1H, d, J= 9.6 Hz)
4.60 (1H, d, J= 7.6 Hz)
3.52 (1H, m)

1"
168.5
2"
133.7
3"
143.4
4"
14.6
5"
56.3
m: .multiplet or overlapped signals

6.91 (1H, m)
1.83 (2H, d, J= 7.2 Hz)
4.35 (2H, s)156

➨ 9 㡯 ᪤▱໬ྜ≀ Compound 66 ࡢᵓ㐀Ỵᐃ
Cpd 66 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C22H26O9 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ106.4 ࠿ࡽ 149.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 8 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ57.0 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ62.6ࠊ76.3ࠊ88.0ࠊ89.6 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 4 ᮏࠊ93.0 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊ࣋ࣥࢮࣥ⎔ proton ࡢ࢝ࢵࣉࣜࣥࢢ
ࣃࢱ࣮ࣥࡼࡾࠊ1,3,4,5-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 66) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 66 ࢆ (+)-1-hydroxysyringaresinol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 457.1469 [M+Na] +(calcd for C22H26O9Na: 457.1469)[α]D24 = +24.4 (c = 0.36, CHCl3)

Fig. 74 Structure and physical data of Compound 66

157

Table 66. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 66 in CD3OD
position
1
5
4

13

C
92.9
62.6
72.2

8
72.2
2
62.6
6
88.0
1’
128.4
1”
133.0
106.4
2’
2”
105.2
3’
148.9
3”
149.1
4’
136.6
4”
136.6
5’
149.0
5”
149.5
106.4
6’
6”
105.2
3’, 5’, 3’’, 5’’-OCH3
57.0
m: .multiplet or overlapped signals

158

1

H

2.95-3.08 (1H, m)
4.48 (1H, dd, J= 8.7, 8.7 Hz)
3.68-4.00 (1H, m)
3.68-4.00 (2H, m)
4.84 (2H, s, m)

6.73 (2H, s)

6.75 (2H, s)
3.86 (12H, s)➨ 10 㡯 ᪤▱໬ྜ≀ Compound 67 ࡢᵓ㐀Ỵᐃ
Cpd 67 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C20H22O7 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ111.4 ࠿ࡽ 149.2 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡ
ࡀ࠶ࡾࠊ56.5ࠊ56.5 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ62.5ࠊ72.2ࠊ87.9ࠊ89.3
ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 4 ᮏࠊ92.9 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸
ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 1 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥࡢࢩࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 69) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 67 ࢆ (+)-1hydroxypinoresinol ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 397.1254 [M+Na] +(calcd for C20H22O7Na: 397.1258)[α]D24 = +16.4 (c = 0.67, MeOH)

Fig. 75 Structure and physical data of Compound 67

159

Table 67. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 67 in CD3OD
position
1
5
4

13

1

C
93.0
62.6
72.2

8
72.2
2
62.6
6
88.0
1'
128.4
1"
133.0
106.4
2'
2"
105.2
3'
1498.9
3"
149.1
4'
136.6
4"
136.6
5'
149.0
149.5
5"
6'
106.4
6"
105.2
3', 3''-OCH3
57.0
m: .multiplet or overlapped signals

160

H

3.06-3.13 (1H, m)
4.45-4.49 (1H, m)
3.76-4.06 (1H, m)
3.76-4.06 (2H, m)
4.87 (1H, s)
4.70 (1H, d, J= 6.3 Hz)

6.81-7.08 (2H, m)

6.81-7.08 (4H, m)
3.87(6H, s)➨ 11 㡯 ᪤▱໬ྜ≀ Compound 68 ࡢᵓ㐀Ỵᐃ
Cpd 68 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C20H24O6 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ110.7 ࠿ࡽ 149.2 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 12 ᮏࡢࣆ࣮ࢡ
ࡀ࠶ࡾࠊ56.5ࠊ56.9 ppm ࡢ࣓ࢺ࢟ࢩᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏࠊ62.4ࠊ65.1 ppm ࡢࣄࢻࣟ࢟ࢩᇶࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 2 ᮏࠊ33.0ࠊ35.9 ppm ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 2 ᮏほ ࡉࢀࡓࠋࡲࡓࠊ1H NMR ࡟࠾࠸࡚ࠊⰾ㤶⎔ࡢ proton ࡀ ABX ࢫࣆࣥࡢࢩ
ࢢࢼࣝ࡜ࡋ࡚ほ ࡉࢀࡓࡇ࡜ࡼࡾࠊ1,3,4-⨨᥮࣋ࣥࢮࣥࢆ⤖ྜࡋࡓࣜࢢࢼࣥ㢮࡛࠶ࡿ࡜᥎ࡋࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 70, 71) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 68 ࢆ vladinol F ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ

Colorless amorphous powder
HR-ESI-MS (positive)
m/z: 383.1461 [M+Na] +(calcd for C20H24O6Na: 383.1465)[α]D24 = -22 (c = 0.1, MeOH)

Fig. 76 Structure and physical data of Compound 68

161

Table 68. 13C NMR (150 MHz) and 1H NMR (600 MHz) data forCpd 68 in CD3OD
position
1
2
3
4
5
6

13

1

C
134.9
110.7

H

6.82 (1H, d, J= 1.8 Hz)
6.77 (1H, brs)

149.2
147.6
116.3
119.9

6.72 (1H, d, J= 8.1 Hz)
6.82 (1H, dd, J= 8.1, 1.8 Hz)
6.95 (1H, dd, J= 8.1, 1.8 Hz)
5.49 (1H, d, J= 6.5 Hz)
3.57 (1H, ddd, J= 8.1, 6.5, 4.8 Hz)
3.75-3.84 (2H, m)

7
89.1
8
55.5
9
65.1
1'
137.1
2'
114.2
3'
145.3
4'
147.6
5'
130.0
6'
118.1
7'
33.0
8'
35.9
9'
62.4
3-OCH356.5
3'-OCH3
56.9
m: .multiplet or overlapped signals

2.62 (1H, t, J= 6.8 Hz)
1.81 (1H, tt, J= 6.8, 6.8 Hz)
3.76 (2H, t, J= 6.8 Hz)
3.80 (1H, s)
3.84 (1H, s)162➨ 12 㡯 ᪤▱໬ྜ≀ Compound 69 ࡢᵓ㐀Ỵᐃ
Cpd 69 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C15H22O5 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ120.6ࠊ132.1ࠊ134.8ࠊ150.5 ppm ࡢ஧㔜⤖ྜ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏࠊ66.2ࠊ
77.4ࠊ83.4ࠊ88.0 ppm ࡢ㓟⣲ࡀ⤖ྜࡋ࡚࠸ࡿⅣ⣲ࡢࢩࢢࢼࣝࡀ 4 ᮏࠊ44.7ࠊ46.2ࠊ77.4 ppm
ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏࠊ16.5ࠊ19.8ࠊ21.3 ppm ࡢ࣓ࢳࣝᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 3 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆᩥ⊩್ 72) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊ
Cpd 69 ࢆ 4’-dihydrophaseic acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 305.1358 [M+Na] +(calcd for C15H22O5Na: 305.1359)[α]D24 = -33.7 (c = 0.19, MeOH)

Fig. 77 Structure and physical data of Compound 69

163

Table 69. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 69 in CD3OD
position
1
2
3
4

13

1

C
N.D.
44.7

H

1.85 (1H, dd, J= 13.2, 6.4 Hz)
1.66 (1H, dd, J= 13.2, 2.4 Hz)
4.11 (1H, m)
2.04 (1H, dd, J= 13.3, 7.2 Hz)
1.74 (1H, dd, J= 13.3, 3.3 Hz)

66.2
46.2

5
88.0
6
83.4
7
134.8
8
132.1
9
150.5
10
120.6
11
N.D.
12
77.4
13
16.5
14
19.8
15
21.3
m: .multiplet or overlapped signals

6.49 (1H, d, J= 15.8 Hz)
7.96 (1H, d, J= 15.8 Hz)
5.79 (1H, br s)
3.81 (1H, d, J= 7.0 Hz)
3.71 (1H, d, J= 7.0 Hz)
0.93 (3H, s)
1.15 (3H, s)
2.08 (3H, brs)164➨ 13 㡯 ᪤▱໬ྜ≀ Compound 70 ࡢᵓ㐀Ỵᐃ
Cpd 70 ࡣ HR-ESI-MS ࡢ⤖ᯝ࠿ࡽࠊࡑࡢศᏊᘧࢆ C11H14O4 ࡛࠶ࡿ࡜Ỵᐃࡋࡓࠋ13C NMR࡟࠾࠸࡚ࠊ101.2 ࠿ࡽ 159.5 ppm ࡢⰾ㤶⎔࡟⏤᮶ࡍࡿࢩࢢࢼࣝ࡜⪃࠼ࡽࢀࡿ 4 ᮏࡢࣆ࣮ࢡࡀ
࠶ࡾࠊ177.9 ppm ࡢ࢝ࣝ࣎ࢽࣝⅣ⣲࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 1 ᮏࠊ25.9ࠊ32.0ࠊ35.1ࠊ36.8 ppm
ࡢ࣓ࢳࣞࣥᇶ࡟⏤᮶ࡍࡿࢩࢢࢼࣝࡀ 4 ᮏほ ࡉࢀࡓࡇ࡜ࡼࡾࠊNMR ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࢆ
ᩥ⊩್ 73) ࡜ẚ㍑ࡋࡓ࡜ࡇࢁࠊCpd 70 ࢆ 3,5-dihydroxybenzenepentanoic acid ࡛࠶ࡿ࡜ỴᐃࡋࡓࠋColorless amorphous powder
HR-ESI-MS (positive)
m/z: 209.0821 [M+H] +(calcd for C11H13O4: 209.0819)
Fig. 78 Structure and physical data of Compound 70

Table 70. 13C NMR (150 MHz) and 1H NMR (600 MHz) data for Cpd 70 in CD3OD
position
1
2
3
4
5
1'
2', 6'
3', 5'
4'

13

1

C
177.9
35.1
25.9
32.0
36.8
146.0
108.1
159.5
101.2

H

2.30 (1H, m)
1.61 (1H, m)
1.61 (1H, m)
2.47 (1H, m)
6.13 (1H, d, J= 2.0 Hz)
6.08 (1H, t, J= 2.0 Hz)

m: .multiplet or overlapped signals165➨ 5 ❶ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂➨ 1 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂࡟ࡘ࠸࡚άᛶ㓟⣲ࡸࣇ࣮ࣜࣛࢪ࢝ࣝࡣ⏕య࡟ᵝࠎ࡞㞀ᐖࢆᘬࡁ㉳ࡇࡍࠋࡑࡢࡓࡵࠊᢠ㓟໬άᛶࢆᣢࡘ≀㉁ࡣ⏕య࡟࡜ࡗ࡚㠀ᖖ࡟㔜せ࡞ᙺ๭ࢆᯝࡓࡋ࡚࠸ࡿࠋᢠ㓟໬≀㉁࡜ࡋ࡚ࡣࠊ
Vitamin C ࡸ Eࠊ࢝ࣟࢸࣀ࢖ࢻ࡞࡝ࡢ௚ࠊࣇࣛ࣎ࣀ࢖ࢻ࡞࡝ࡀ▱ࡽࢀ࡚࠸ࡿࠋ
௒ᅇࠊ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firmaࠊࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ
࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓ 70 ✀㢮ࡢ໬ྜ≀࡟ࡘ࠸࡚ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ࢆ⾜ࡗࡓࠋ
DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂࡜ࡣࠊᮏ᮶ᴟࡵ࡚୙Ᏻᐃ࡛࠶ࡿࣛࢪ࢝ࣝࢆேᕤⓗ࡟Ᏻᐃ໬ࡉࡏࡓ 1,1-diphenyl-2-picrylhydrazyl㸦DPPH㸧ࣛࢪ࢝ࣝࢆ⏝࠸ࡓᢠ㓟໬άᛶ ᐃ᪉ἲ࡛࠶
ࡿࠋ
DPPH ࣛࢪ࢝ࣝࡣྍど㒊࡟྾཰ࢆᣢࡕࠊᢠ㓟໬≀㉁࠿ࡽ౪୚ࡉࢀࡓỈ⣲ࣛࢪ࢝ࣝࢆᤕ
ᤊࡍࡿ࡜྾཰ࢆ♧ࡉ࡞ࡃ࡞ࡿ࡜࠸࠺≉ᚩࢆࡶࡗ࡚࠸ࡿ㸦Fig.79㸧ࠋࡇࡢ≉ᚩࢆ฼⏝ࡋࠊ
micro plate reader ࡛ẚⰍᐃ㔞ࡋࠊࡑࡢ ᐃ್ࢆᢠ㓟໬≀㉁࡛࠶ࡿࣅࢱ࣑ࣥ E ㄏᑟయࠊα-ࢺࢥࣇ࢙࣮ࣟࣝ㓑㓟࢚ࢫࢸࣝ㸦Trolox㸧ࢆ࣏ࢪࢸ࢕ࣈࢥࣥࢺ࣮ࣟࣝ࡜ࡋ࡚⏝࠸࡚ホ౯ࡋࡓࠋRadical scavenger

TroloxFig. 79 DPPH ࣛࢪ࢝ࣝ཯ᛂᶵᵓ

166

➨ 2 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ἲ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firmaࠊࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒
⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓィ 70 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊDPPH ࣛࢪ࢝ࣝࢆ
౑⏝ࡋࡓ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ࢆ⾜࠸ࠊᢠ㓟໬άᛶࢆㄪ࡭ࡓࠋ
96 well plate ࡟࡚ DPPH ⁐ᾮ㸦200 μM㸧࡟ 100 μg/mL ࡢ⤊⃰ᗘ࡜࡞ࡿࡼ࠺ㄪᩚࡋࡓ
ྛ✀⿕᳨≀㉁ࢆస⏝ࡉࡏࠊᐊ ࠊᬯᡤ࡟࡚ 30 ศ㛫཯ᛂࡉࡏࡓࠋ྾ගᗘࡢኚ໬ࢆ microplate
reader㸦515nm㸧࡟࡚ ᐃࡋࠊᢚไ⋡ࡣ௨ୗࡢィ⟬ᘧ࡟ࡼࡾ⟬ฟࡋࡓࠋࢧࣥࣉࣝࡢ⁐ゎ࡟ࡣ DMSO ࢆ౑⏝ࡋ⤊⃰ᗘ 1㸣࡟⤫୍ࡋࡓࠋᢚไ⋡㸦㸣㸧[1-㸦Asample-Ablank㸧/㸦ADMSO-Ablank㸧] x 100
Ablank㸸DPPH ῧຍ๓ࡢ྾ගᗘࠊADMSO: DMSO ࡢࡳ

100
80
60
40
20
0
1 2 3 4 5 6 7 8 9 101112131415181920

100 μg/mL

100
80
60
40
20
0
56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 P.C

DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶInhibition (%)

n=3

DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶ

100 μg/mL

Inhibition (%)

Inhibition (%)

DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶ

P.C: Trolox

100 μg/mL

100
90
80
70
60
50
40
30
20
10
0
21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54

ࡇࡇ࡛ᢚไ⋡ࡀ 50㸣ࢆ㉸࠼ࡓࡶࡢ࡟ࡘ࠸࡚ࡣࠊࡉࡽ࡟ 100ࠊ50ࠊ25 μg/mL ࡢ 3 ⃰ᗘ࡛ྠᵝࡢヨ㦂ࢆ⾜࠸ࠊIC50 ࢆ⡆᫆ἲ㸦50㸣ࢆࡲࡓࡄ 2 Ⅼࢆ㑅ࡧࠊ50㸣࡜ࡢ஺Ⅼ࠿ࡽồࡵࡿ㸧࡟࡚⟬ฟࡋࡓࠋ
167

➨ 3 ⠇ DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨࡢ⤖ᯝ
DPPH ࣛࢪ࢝ࣝ㝖ཤάᛶヨ㦂ࢆᐇ᪋ࡋࡓ࡜ࡇࢁ Compound 1ࠊ2ࠊ11ࠊ26ࠊ27ࠊ28ࠊ
31ࠊ32ࠊ34ࠊ37ࠊ38ࠊ39ࠊ45ࠊ49ࠊ56ࠊ57ࠊ66ࠊ67 ࡟ẚ㍑ⓗᙉ࠸άᛶࡀぢࡽࢀࡓࠋࡑࡢ௚
ࡢ໬ྜ≀࡟ࡘ࠸࡚ࡣ࡯࡜ࢇ࡝άᛶࡣぢࡽࢀ࡞࠿ࡗࡓࠋ

Table 71.

IC50 of active compounds

Compound

IC50 (μM)

Compound

IC50 (μM)

137.9 ± 4.6

44366.2 ± 4.7

2

33.4 ± 4.7

4543.5 ± 1.5

11
23
26
27
28
31
32
33
34
35
36
37
38
39
42
43

39.1 ± 4.6
240.3 ± 3.6
7.2 ± 0.2
29.1 ± 0.8
53.1 ± 1.3
29.8 ± 0.5
38.5 ± 1.6
216.2 ± 5.6
73.5 ± 2.1
106.5 ± 3.6
130.4 ± 2.7
67.8 ± 2.1
77.2 ± 0.7
52.3 ± 0.9
470.7 ± 4.9
103.6 ± 3.6

46
47
48
49
54
56
57
61
62
66
67
68
69
70
P.C (Trolox)

252.3 ± 3.9
394.1 ± 5.6
352.5 ± 6.9
16.8 ± 0.6
158.4 ± 2.2
61.2 ± 0.4
39.8 ± 1.8
232.2 ± 5.9
113.9 ± 2.2
39.3 ± 0.5
78.9 ± 0.7
131.7 ± 1.4
210.6 ± 2.7
291.9 ± 3.6
36.4 ± 0.2

168➨ 6 ❶ Tyrosinase 㜼ᐖάᛶヨ㦂➨ 1 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂࡟ࡘ࠸࡚⫙ࡢ᪥↝ࡅࠊࢩ࣑࡞࡝ࡢཎᅉ࡜࡞ࡾ࠺ࡿ࣓ࣛࢽࣥⰍ⣲ࡢỿ╔ࡣࠊ⣸እ⥺࡞࡝ࡢ่⃭࡟ࡼࡾࠊ⫙ࡢᇶᗏ⭷࡟Ꮡᅾࡍࡿ࣓ࣛࣀࢧ࢖ࢺ࠿ࡽ࣓ࣛࢽࣥⰍ⣲ࡀᨺฟࡉࢀࠊỿ╔ࡍࡿࡇ࡜࡛
⏕ࡌࡿࠋ࣓ࣛࢽࣥྜᡂ㓝⣲ࡢࡦ࡜ࡘ࡛࠶ࡿࠊtyrosinase ࡀ㛵୚ࡍࡿࠊL-tyrosine ࠿ࡽࢻ࣮ࣃ
࢟ࣀࣥ࡬ࡢኚ᥮ࡣࠊ࣓ࣛࢽࣥྜᡂ⤒㊰ࡢᚊ㏿ẁ㝵࡜⪃࠼ࡽࢀ࡚࠾ࡾࠊࡇࢀࡲ࡛ࠊᮏ㓝⣲ࡢ㜼ᐖ๣ࡢ᥈⣴◊✲ࡣከࡃ࡞ࡉࢀࠊ⌧ᅾࠊ୍⯡ⓗ࡟໬⢝ရࡢ⨾ⓑ᭷ຠᡂศ࡜ࡋ࡚౑⏝ࡉࢀ࡚࠸ࡿ໬ྜ≀࡜ࡋ࡚ࠊhydroquinoneࠊarbutinࠊvitamine C ㄏᑟయ࡞࡝ࡀᣲࡆࡽࢀࡿࠋ74)ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firmaࠊࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓィ 70 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊ
tyrosinase 㜼ᐖάᛶヨࢆ⾜ࡗࡓࠋFig. 81 L-tyrosine ࠿ࡽࢻ࣮ࣃ࢟ࣀࣥ࡬ࡢኚ᥮཯ᛂ

Fig. 80 ࣓ࣛࢽࣥ⏕ᡂ࣭ỿ╔ࡢ࣓࢝ࢽࢬ࣒

169

➨ 2 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂ἲᮏᐇ㦂࡟࠾࠸࡚ࡣࠊᇶ㉁࡜ࡋ࡚ L-tyrosine ࢆ⏝࠸ࠊpositive control ࡜ࡋ࡚ࡣࠊ⨾ⓑ᭷ຠᡂศ࡜ࡋ࡚ᗈࡃ⏝࠸ࡽࢀ࡚࠸ࡿ arbutin ࢆ౑⏝ࡋࡓࠋྛ sample ࡜ arbutin ࡣࠊ⤊⃰ᗘࡀ 250ࠊ125ࠊ62.5 μg/mL ࡢ 3 ẁ㝵࡜࡞ࡿࡼ࠺࡟ࠊணࡵDMSO ࡟⁐ゎࡋ࡚ᕼ㔘⣔ิࢆసᡂࡋࡓࠋ
96 well ࣐࢖ࢡࣟࣉ࣮ࣞࢺࡢྛ well ࡟ࠊsample ࡢྛᕼ㔘⣔ิ 10μL ࡜ࠊ0.25 mg/mL ࡟ㄪ〇ࡋࡓ L-tyrosine ධࡾ buffer ࢆ 40 μL ࡎࡘຍ࠼ࠊ࣐࢖ࢡࣟࣉ࣮ࣞࢺ࣮ࣜࢲ࣮ࢆ⏝࠸࡚ 475 nm࡟࠾ࡅࡿ background ࡢ྾ගᗘࢆ ᐃࡋࡓࠋ⥆࠸࡚ྛ well ࡟ࠊbuffer ࡛ 100 units/mL ࡟ㄪ〇ࡋࡓ mushroom tyrosinase ࢆ 50 μL ࡎࡘຍ࠼࡚ࠊ25℃࡛ 10 ศ㛫཯ᛂࡉࡏࡓࠋ10 ศᚋ࡟ࠊ෌
ᗘ 475 nm ࡟࠾ࡅࡿ྾ගᗘࢆ ᐃࡋࠊࡇࡢ್࠿ࡽ background ࢆᘬ࠸ࡓ್ࢆᇶ࡟ࠊ㓝⣲㜼ᐖ⋡ࢆ⟬ฟࡋࡓࠋ
࡞࠾ࠊࡇࡢᐇ㦂࡟࠾࠸࡚ buffer ࡜ࡋ࡚ࡣࠊpH 6.8 ࡢ 0.05M K-phosphate buffer ࢆ⏝࠸ࡓࠋᢚไ⋡㸦㸣㸧[1-㸦Asample-Abackground㸧/㸦Acontrol-Abackground㸧] x 100
Asample: sample ⱝࡋࡃࡣ arbutin ࡜ࠊtyrosinase ࢆῧຍ᫬ࡢ྾ගᗘ
Acontrol: DMSO control (sample ࢆྵࡲ࡞࠸) ࡟ tyrosinase ࢆῧຍ᫬ࡢ྾ගᗘ
A background: tyrosinase ࢆῧຍࡍࡿ๓ࡢ྾ගᗘ

0.25mg/mL L-Tyrosine 40 μL
Sample 10 μL
Mushroom tyrosinase
100 unit/mL 50 μL

10 min at 25℃

྾ගᗘ ᐃ
475 nmFig. 82 Tyrosinase 㜼ᐖάᛶヨ㦂ࣉࣟࢺࢥ࣮ࣝ

170

➨ 3 ⠇ Tyrosinase 㜼ᐖάᛶヨ㦂ࡢ ⤖ᯝTyrosinase 㜼ᐖάᛶヨ㦂ࢆᐇ᪋ࡋࡓ࡜ࡇࢁࠊ௨ୗࡢ໬ྜ≀࡟ẚ㍑ⓗᙉ࠸άᛶࡀぢࡽࢀࡓࠋࡑࡢ௚ࡢ໬ྜ≀࡟ࡘ࠸࡚ࡣ࡯࡜ࢇ࡝άᛶࡣぢࡽࢀ࡞࠿ࡗࡓࠋࡑࡢ࠺ࡕࠊCompound 40ࠊ49ࠊ
54ࠊ64 ࡣ Arbutin ࡟༉ᩛࡍࡿࠊ࠶ࡿ࠸ࡣࡑࢀ௨ୖࡢάᛶࢆ♧ࡋࡓࠋ

Inhibition (%)

Tyrosinase㜼ᐖάᛶヨ㦂

n=3

100
90
80
70
60
50
40
30
20
10
0

5

15

40

48

250 μg/ml

Compound
5
15
40
48
49

49

50

125 μg/ml

IC 50(μM)
1030.0 ± 3.0
1090.0 ± 0.1
120.7 ± 1.6
1302.4 ± 3.5
30.8 ± 0.1

5462.5 μg/ml

64

70

P.C.

P.C: Arbutin

Compound
IC 50 (μM)
50431.4 ± 1.1
54144.5 ± 13.064
8.4 ± 0.23701309.0 ± 6.7
P.C (Arbutin) 167.8 ±0.5

54

40
49

64
171

➨ 7 ❶ α-Amylase 㜼ᐖάᛶヨ㦂➨ 1 ⠇ α-Amylase 㜼ᐖάᛶヨ㦂࡟ࡘ࠸࡚
α-Amylase ࡣ㸪α -1,4-ࢢࣜࢥࢩࢻ⤖ྜ࡟స⏝ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࢹࣥࣉࣥࢆࢢࣝࢥ࣮ࢫ
࡟ศゎࡍࡿຍỈศゎ㓝⣲ࡢ୍✀࡛࠶ࡿࠋࡲࡓࠊα-amylase ࡣၚᾮࡸ⮅ᾮࡢ୺せ࡞ᾘ໬㓝⣲࡛࠶ࡿࠋຍỈศゎ࡟ࡼࡗ࡚⏕ᡂࡍࡿࢢࣝࢥ࣮ࢫࡸ࣐ࣝࢺ࣮ࢫࡢ㐣๫ᦤྲྀࡣయෆ࡛࢖ࣥࢫࣜ
ࣥࡸ⾑⢾್ࡢୖ᪼ࢆᘬࡁ㉳ࡇࡋࠊ⢾ᒀ⑓ࡸ⫧‶ࡢཎᅉ࡟࡞ࡿࠋࡑࡢࡓࡵࠊα-amylase 㜼ᐖ๣ࡣ⫧‶ࡸ⢾ᒀ⑓ࢆ἞⒪࣭ண㜵ࡍࡿ⸆๣ࡸᶵ⬟ᛶ㣗ရ࡜ࡋ࡚᭷ᮃ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ
ᮏ◊✲࡛ࡣࠊࢡࣟࢱ࢟ ࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis
terminalis ࠿ࡽ༢㞳ࡉࢀࡓィ 50 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊα-Amylase 㜼ᐖάᛶࢆホ౯ࡋࡓࠋࡇࡢ
ヨ㦂࡛ࡣ࣐ࣝࢺࢺ࣮ࣜ࢜ࢫࡢ⤖ྜࡋࡓⓎⰍᇶ㉁ CNPG3 ࢆ⏝࠸࡚ホ౯ࡋࡓࠋα-amylase

MaltoseStarchCNPG3:
2-Chloro-4-nitrophenyl α-D-maltotrioside172➨ 2 ⠇ α-Amylase 㜼ᐖάᛶヨ㦂ἲᮏ◊✲࡛ࡣࠊ50 ✀㢮ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊα-Amylase 㜼ᐖάᛶࢆホ౯ࡋࡓࠋࡇࡢヨ㦂࡛ࡣ࣐ࣝࢺࢺ࣮ࣜ࢜ࢫࡢ⤖ྜࡋࡓⓎⰍᇶ㉁ CNPG3 ࢆ⏝࠸࡚ホ౯ࡋࡓࠋྛ sample ࡣࠊ⤊⃰ᗘࡀ 200ࠊ100ࠊ50 μg/mL ࡢ 3 ẁ㝵࡜࡞ࡿࡼ࠺࡟ࠊணࡵ DMSO ࡟⁐ゎࡋ࡚ᕼ㔘⣔ิࢆసᡂࡋࡓࠋ
96 well ࣐࢖ࢡࣟࣉ࣮ࣞࢺࡢྛ well ࡟ࠊsample ࡢྛᕼ㔘⣔ิࢆ 1 μL ࡜ࠊ1 mg/mL ࡟ㄪ〇ࡋࡓ CNPG3 ࢆ 50 μL ࡎࡘຍ࠼ࠊ⥆࠸࡚ࠊ10 units/mL ࡟ㄪ〇ࡋࡓ α-amylase ධࡾ buffer ཬࡧ㓝⣲୙ྵ buffer (background) ࢆ 50 μL ࡎࡘຍ࠼࡚ࠊ37℃࡛ 30 ศ㛫཯ᛂࡉࡏࡓࠋ30 ศᚋ࡟ࠊ405 nm ࡟࠾ࡅࡿ྾ගᗘࢆ ᐃࡋࡓࠋ࡞࠾ࠊࡇࡢᐇ㦂࡟࠾࠸࡚ buffer ࡜ࡋ࡚ࡣࠊpH 6.4 ࡢ 0.05M K-phosphate buffer ࢆ⏝࠸ࡓࠋᢚไ⋡㸦㸣㸧[1-㸦Asample (enz+㸧- Asample (enz-) /㸦ADMSO (enz+㸧- ADMSO(enz-)㸧] x 100
Asample (enz+㸧: sample ࠊpositive control ࡢ enzyme (+)
Asample (enz-㸧: sample ࠊpositive control ࡢ enzyme (-)
ADMSO (enz+㸧: DMSO ࡢ enzyme (+)
ADMSO (enz-㸧: DMSO ࡢ enzyme (-)

1 mg/mL CNPG3 50 μL
Sample 1 μL
10units/mL α-amylase 50 μL in buffer
and buffer (for background) 50 μL

30 min at 37℃

྾ගᗘ ᐃ
405 nmFig. 83 α-Amylase 㜼ᐖάᛶヨ㦂ࣉࣟࢺࢥ࣮ࣝ

173

➨ 3 ⠇ α-Amylase 㜼ᐖάᛶヨ㦂ࡢ ⤖ᯝ
α-Amylase 㜼ᐖάᛶヨ㦂ࢆᐇ᪋ࡋࡓ࡜ࡇࢁࠊCompound 34ࠊ37ࠊ54ࠊ64 ࡟άᛶࡀぢࡽࢀࡓࠋࡑࡢ௚ࡢ໬ྜ≀࡟ࡘ࠸࡚ࡣ࡯࡜ࢇ࡝άᛶࡣぢࡽࢀ࡞࠿ࡗࡓࠋ

n=3α-Amylase 㜼ᐖάᛶヨ㦂Inhibition (%)

100
80
60
40
20
0
32

34

35

200 μg/mL

36

37

100 μg/mL

38

54

64

50 μg/mL

Compound

IC50 (μM)

Compound

IC50 (μM)

32
34
35
36

322.6 ± 5.6
151.4 ± 4.8
226.3 ± 2.5
270.5 ± 3.9

37
38
54
64
P.C (Acarbose)

173.9 ± 6.5
428.1± 10.4
151.8 ± 4.1
122.7 ± 0.2
9.3 ± 0.2

37

34

64

174

54

➨ 8 ❶ A549 ⣽⬊ቑṪᢚไヨ㦂➨ 1 ⠇ MTT assay ࡟ࡘ࠸࡚MTT assay ࡜ࡣࠊᇵ㣴⣽⬊⏕Ꮡ⋡ࠊቑṪ⋡ࢆ☜ㄆࡍࡿヨ㦂᪉ἲ࡛ࠊ MTT (3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolinm bromideࠊyellow tetrazole㸧ࢆ⏝࠸ࡓẚⰍᐃ㔞ἲ࡛࠶ࡿࠋᮏᡭἲ࡛⏝࠸ࡽࢀࡿ MTT ࡢࢸࢺࣛࢰ࣒ࣜ࢘ሷࡀ࣑ࢺࢥࣥࢻࣜ࢔࡟Ꮡᅾࡍࡿ
succinate-tetrazolium reductase㸦ࢥࣁࢡ㓟ࢸࢺࣛࢰ࣒ࣜ࢘㑏ඖ㓝⣲㸧࡟ࡼࡾ࣐࣍ࣝࢨࣥ࡟㑏ඖࡉࢀࡿࠋ⏕⣽⬊୰࡛ࡣࡇࡢ㓝⣲άᛶࡀ㧗࠸ࡓࡵ࡟࿊Ⰽ཯ᛂࡀㄆࡵࡽࢀࡿࡀࠊ⣽⬊Ṛࡀ㉳ࡇࡿ࡜ࡇࡢάᛶࡀపୗࡍࡿࡓࡵ࡟࿊Ⰽࡋ࡞࠸ࠋ௦ㅰάᛶࡢ࠶ࡿ⏕⣽⬊ᩘ࡜࣐࣍ࣝࢨࣥⰍ⣲ࡢ⃰ᗘࡣṇࡢ┦㛵ࢆ♧ࡍࡓࡵ࡟ࠊࡇࡢ࣐࣍ࣝࢨࣥⰍ⣲ࡢ྾ගᗘ ᐃࢆ⾜࠺ࡇ࡜࡟ࡼࡾ⣽⬊ࡢ⏕Ꮡ⋡ࡸቑṪᢚไ⋡ࢆホ౯ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ
ᮏ◊✲࡛ࡣࠊࢡࣟࢱ࢟ ࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis
terminalis ࠿ࡽ༢㞳ࡉࢀࡓィ 50 ✀ࡢ໬ྜ≀ࢆࠊࣄࢺ⫵⬊ᇶᗏୖ⓶⭢⒴⣽⬊࡛࠶ࡿ A549 ᇵ㣴ᾮ୰࡟ῧຍࡋࠊ72hr ᇵ㣴ᚋࡢ⏕Ꮡ⋡ࢆ MTT assay ࡟ࡼࡾホ౯ࡍࡿࡇ࡜࡛ࠊࡀࢇ⣽⬊ቑṪᢚไάᛶᡂศ࡟ࡘ࠸࡚ࡢ᳨ウࢆ⾜ࡗࡓࠋ175

➨ 2 ⠇ A549 ⣽⬊ቑṪᢚไヨ㦂ἲᇵ㣴ࠊཬࡧ ᐃ࡟ࡣ 96 well plate ࢆ౑⏝ࡋࡓࠋControl ࡣ sample ࢆྵࡲ࡞࠸ DMSO ⁐ᾮࢆ⏝࠸ࠊpositive control ࡜ࡋ࡚ࢻ࢟ࢯࣝࣅࢩࣥࢆ⏝࠸ࡓࠋࢧࣥࣉࣝࡣ DMSO ⁐ᙼ࡛ྛ✀⃰ᗘ࡜࡞ࡿࡼ࠺࡟⁐ゎࡋࡓࠋྛ well ࡟ࢧࣥࣉࣝ⁐ᾮࢆ 1
μl ຍ࠼ࠊࡇࢀࡽ࡟ 5.0 x 103 cells / 99μl ࡜࡞ࡿࡼ࠺࡟ㄪ〇ࡋࡓ A549 ࢆྵࡴ ᇵᆅ 99μl ࢆຍ࠼ࡓࠋࡑࡢᚋࠊ37℃ ᮲௳ୗ࡛ 72 ᫬㛫࢖࣮ࣥ࢟ࣗ࣋ࢺࡋࡓࠋ96well plate ୰ࡢᇵᆅࢆ྾ᘬᚋࠊ
MTT㸦0.5 mg / ml㸧ࢆྵࡴᇵᆅ 100 μl ࢆຍ࠼ࡓᚋࠊࡉࡽ࡟ 1.5 ᫬㛫 ࢖࣮ࣥ࢟ࣗ࣋ࢺࢆ⾜ࡗ
ࡓࠋMTT ࢆྵࡴᇵᆅࢆ྾ᘬᚋࠊDMSO ⁐ᾮ 100μl ࢆຍ࠼࡚ plate mixer ࡟࡚⁐ゎࠋࡑࡢᚋࠊ
plate reader ࡛ 540 nm ࡢ྾ගᗘࢆ ᐃࡋࡓࠋቑṪᢚไ⋡ࡣୗグࡢᘧࢆ⏝࠸࡚⟬ฟࡋࠊsample ࡢ A549 ⣽⬊ቑṪᢚไάᛶࢆホ౯ࡋࡓࠋቑṪᢚไ⋡㸦㸣㸧[1-㸦Asample-Ablank㸧/㸦Acontrol-Ablank㸧] x 100

A sample: ࢧࣥࣉࣝῧຍ᫬ࡢ྾ගᗘ
A blank: ⣽⬊ࢆຍ࠼࡚࠸࡞࠸ DMSO ᇵᆅࡢ྾ගᗘ
A control: ࢧࣥࣉࣝࢆῧຍࡋ࡚࠸࡞࠸ DMSO ᇵᆅࡢ྾ගᗘ

Sample + A549
(5×103 cells/ 100μl)

0.5 mg/ml MTT 100 μl྾ගᗘ ᐃ
72 hours at 37℃

15 hours at 37℃

Fig. 84 A549 ⣽⬊ቑṪᢚไヨ㦂ἲࣉࣟࢺࢥ࣮ࣝ

176

540 nm➨ 3 ⠇ A549 ⣽⬊ቑṪᢚไヨ㦂ࡢ ⤖ᯝࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࠾ࡼࡧ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓィ 50 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊA549 ⣽⬊ቑṪᢚไヨ㦂ࢆᐇ᪋ࡋࡓ࡜ࡇࢁࠊCompound64 ࡟ẚ㍑ⓗᙉ࠸άᛶࡀぢࡽࢀࡓࠋ

A549⣽⬊ቑṪᢚไヨ㦂

n=3Inhibition (%)

100
80
60
40
20
0

21

31

36

37
100 μg/ml

49
50 μg/ml

54

58

25 μg/ml

59

64

P.C: Doxorubicin

Compound

IC50 (μM)

Compound

IC50 (μM)

21136.5 ± 0.6

54133.1 ± 1.9

31166.9 ± 0.6

58134.3 ± 1.2

36157.6 ± 1.2

59187.6 ± 0.7

37126.0 ± 0.4

6456.8 ± 3.7

49403.6 ± 1.1

P.C (Doxorubicin)

0.65 ± 0.2

64

177

PC

➨ 9 ❶ ࡲ࡜ࡵ᪥ᮏ⏘᳜≀ࣇࢩࢢࣟ Silene firma ᆅୖ㒊ࡢᡂศ◊✲ࢆ⾜࠸ࠊ᪂つ໬ྜ≀ 2 ✀ࢆྵࡴ໬ྜ
≀ 20 ✀㸦Compounds 1-20㸧ࢆ༢㞳ࡋࠊྛ✀ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࡸ໬Ꮫⓗᡭἲࢆ⏝࠸࡚ࠊࡑࡢᵓ㐀ࢆỴᐃࡋࡓࠋ
᪥ᮏ⏘᳜≀ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢⴥ㒊࡜ࡘࡿࡢᡂศ◊✲ࢆ⾜࠸ࠊ᪂つ໬ྜ≀ 2 ✀ࢆྵࡴ໬ྜ≀ 34 ✀㸦Compounds 21-54㸧ࢆ༢㞳ࡋࠊྛ✀ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࡸ໬Ꮫⓗᡭἲࢆ⏝࠸࡚ࠊࡑࡢᵓ㐀ࢆỴᐃࡋࡓࠋࡲࡓࠊ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᶞ⓶ࡢᡂศ◊✲ࢆ⾜࠸ࠊ᪂つ໬ྜ≀ 3 ✀ࢆྵࡴ໬ྜ≀ 16 ✀㸦Compounds 55-70㸧ࢆ༢㞳ࡋࠊྛ✀ࢫ࣌ࢡࢺࣝࢹ࣮ࢱࡸ໬Ꮫⓗᡭἲࢆ⏝࠸࡚ࠊࡑࡢᵓ㐀ࢆỴᐃࡋࡓࠋࡉࡽ࡟ࠊࣇࢩࢢࣟࠊࢡࣟࢱ࢟࢝ࢬࣛࠊ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉ
ࢀࡓ 70 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࠊᢠ㓟໬άᛶࠊࢳࣟࢩࢼ࣮ࢮάᛶヨ㦂ࢆ⾜ࡗࡓࠋࡲࡓࠊࢡࣟ
ࢱ࢟࢝ࢬࣛࠊ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓ 50 ✀ࡢ໬ྜ≀࡟ᑐࡋ࡚ࡣࡉࡽ࡟ࠊα ࢔࣑࣮ࣛࢮάᛶࠊࡀࢇ⣽⬊ቑṪᢚไάᛶヨ㦂ࡶ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊࣇࢩࢢࣟࠊ
ࢡࣟࢱ࢟࢝ࢬࣛࠊ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࠿ࡽ༢㞳ࡉࢀࡓ໬ྜ≀ࡢ୰࡟ࠊᢠ㓟໬άᛶࠊtyrosinase άᛶࠊα-amylase άᛶࠊࡀࢇ⣽⬊ቑṪᢚไάᛶࢆ♧ࡍ໬ྜ≀ࢆぢฟࡋࡓࠋࡇࢀࡽࡢάᛶ໬ྜ≀ࡣࠊ໬⢝ရ⣲ᮦࡸ೺ᗣቑ㐍ᡂศ࡜ࡋ࡚᭷⏝࡞⣲ᮦ࡟࡞ࡿࡇ࡜ࡀᮇᚅࡉ
ࢀࡿࠋ

178

Fig. 85 Isolated compounds from the aerial parts of Silene firma
179

Fig. 86 Isolated compounds from the vine of Hosiea japonica
180

Fig. 87 Isolated compounds from the leaves of Hosiea japonica

181

Fig. 88 Isolated compounds from the bark of Heliciopsis terminalis
182➨ 10 ❶ ᐇ㦂ࡢ㒊ᮦᩱ᳜≀ࣇࢩࢢࣟ Silene firma ࡢᆅୖ㒊ࡣឡ፾┴ࡢ௒἞ᕷ࡛᥇㞟ࡋࡓࠋࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica ࡢⴥ㒊࡜ࢶࣝࡣ 1990 ᖺ 6 ᭶ࠊᗈᓥ┴ẚ፠㒆㧗㔝⏫ᗉཎᕷ࡛᥇㞟ࡋࡓࠋ
࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᶞ⓶ࡣ࣋ࢺࢼ࣒ࡢ໭㒊࡛᥇㞟ࡋࡓࠋ୍⯡ἲ
1. ᪕ගᗘ
᪕ගᗘࡣ P-1030㸦᪥ᮏศගᕤᴗ㸧ࢹࢪࢱࣝ᪕ගᗘィࢆ⏝࠸࡚ࡣࠊྛ ᐃ್࡟௜グࡋࡓࠋᐃࡋࡓࠋ ᐃ⁐፹ཬࡧᗘ

2. ᰾☢Ẽඹ㬆㸦NMR㸧ࢫ࣌ࢡࢺࣝ
㸦1H NMR㸸400 MHzࠊ13C NMR㸸100 MHz㸧ࡲࡓࡣ㸦1H NMR㸸600 MHzࠊ13C NMR㸸150
MHz㸧ࠋ࠸ࡎࢀࡶ⁐፹୰ࡢ D ࢩࢢࢼࣝࢆ internal lock signal ࡜ࡋࡓࠋࢣ࣑࢝ࣝࢩࣇࢺ್ࡢ⾲♧ࡣࠊෆ㒊ᶆ‽≀㉁ࢸࢺ࣓ࣛࢳࣝࢩࣛࣥ㸦TMS㸧࠿ࡽࡢG ್㸦ppm㸧࡛♧ࡋࠊ1H NMR ࢫ࣌ࢡࢺࣝ࡟࠾ࡅࡿ⤖ྜᐃᩘࡣᣓᘼෆ࡟ Hz ༢఩࡛グࡋࡓࠋ
3. ㉁㔞㸦MS㸧ศᯒHR-ESI-MS ࡣࠊ㧗ᛶ⬟ࣁ࢖ࣈࣜࢵࢻᆺ㉁㔞ศᯒࢩࢫࢸ࣒ (Thermo Fisher Scientific 〇 – LTQ
Orbitrap XL) ࢆ⏝࠸࡚ ᐃࡋࡓࠋ4. ㉥እ྾཰㸦IR㸧ࢫ࣌ࢡࢺࣝHORIBA FT-710㸦ᇼሙ〇సᡤ㸧ศගගᗘィࢆ౑⏝ࡋࠊࣇ࢕࣒ࣝἲ࡟࡚ ᐃࡋࡓࠋ5. ⣸እ྾཰㸦UV㸧ࢫ࣌ࢡࢺࣝ
JASCO V-520㸦᪥ᮏศගᕤᴗ㸧ศගගᗘィࢆ౑⏝ࡋࠊᒙ㛗 1 cm ࡢ▼ⱥࢭࣝࢆ⏝࠸࡚
ࡓࠋ

183

ᐃࡋ

࣒࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮
1.

ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮
㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ࡣࠊ70-230 mesh ࡢ silica gel 60 (Merck)ࢆ
౑⏝ࡋࡓࠋ
㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ࡣࠊCosmosil 75 C18-OPN (Nacalai Tesque)ࢆ౑⏝ࡋࡓࠋ
2.

㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮
ศྲྀ⏝࣒࢝ࣛ࡟ Inertsil ODS (6.0×250 mm)ࠊInertsil ODS (10×250 mm)ࠊȧNAP (10×250mm)ࠊCholester (10×250 mm)ࡢ࠸ࡎࢀ࠿ࢆ౑⏝ࡋࠊ᳨ฟ࡟ RI 2031㸦᪥ᮏศගᕤᴗ㸧ࠊ⁐፹࡟࢔ࢭࢺࣥỈ⣔ࢆ⏝࠸࡚ࠊInertsil ODS (6.0×250 mm)࡛ࡣὶ㏿ 1.6 mL/ min ࡛ࠊInertsil ODS(10×250 mm)࠶ࡿ࠸ࡣ πNAP (10×250 mm)࡛ࡣὶ㏿ 2.8 mL/ min ࡛ࠊCholester (10×250 mm)࡛ࡣὶ㏿ 2.5 mL/ min ࡛⾜ࡗࡓࠋ3.

ⷧᒙࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦TLC㸧
TLC ࣉ࣮ࣞࢺ࡟ཌࡉ 0.25 cm ࡢࢩࣜ࢝ࢤࣝ 60F254㸦࣓ࣝࢡ㸧ࣉ࣮ࣞࢺࢆ⏝࠸ࠊࢡࣟࣟ
࣒࣍ࣝ㸸࣓ࢱࣀ࣮ࣝ㸻10: 1 ࠶ࡿ࠸ࡣࢡ࣒ࣟࣟ࣍ࣝ㸸࣓ࢱࣀ࣮ࣝ㸸Ỉ㸻15: 6: 1 ࡢΰྜ⁐፹ࢆᒎ㛤⁐፹࡜ࡋࡓࠋᒎ㛤ᚋࡢࢫ࣏ࢵࢺࡣ UV (254 nm) ↷ᑕ࠾ࡼࡧࠊ10 % ◲㓟ࢆᄇ㟝ᚋຍ⇕ࡋ࿊Ⰽࡉࡏ᳨࡚ฟࡋࡓࠋ
4.

⢾ศᯒ㸦HPLC㸧ศᯒ⏝࣒࢝ࣛ࡟ Shodex NH2P-50㸦᫛࿴㟁ᕤ㸧ࢆ౑⏝ࡋࠊ᳨ฟ࡟ OR-2090㸦᪥ᮏศගᕤ
ᴗ㸧᪕ගᗘ᳨ฟィࢆ⏝࠸ࠊ⁐፹࡟࢔ࢭࢺࢽࢺ̺ࣜࣝỈ⣔ࢆ⏝࠸࡚ࠊὶ㏿ 1mL/min ࡛⾜ࡗࡓࠋ184ᢳฟࠊ༢㞳ࠊ⢭〇 (ࣇࢩࢢࣟ Silene firma)
஝⇱ࡉࡏࡓࣇࢩࢢࣟࡢᆅୖ㒊㸦10.6 kg㸧ࢆ࣓ࢱࣀ࣮࡛ࣝ 3 ᅇ㸦45 L㸧ᢳฟࡋࠊ1.5 L ࡟⃰⦰ᚋࠊ࣊࢟ࢧࣥ 1.5 L ࡛ศ㓄ࡋࡓࠋ࣓ࢱࣀ࣮ࣝᒙࢆ⃰⦰ᚋࠊỈ 1.5 L ࡛ᠱ⃮ࡋࠊ㓑㓟࢚ࢳ
ࣝࠊ1-ࣈࢱࣀ࣮ࣝࢆࡑࢀࡒࢀ 1.5 L ࡛㐃⥆ⓗ࡟ศ㓄ࠊ⃰⦰ࡋࠊ࣊࢟ࢧࣥᒙ࡜㓑㓟࢚ࢳࣝᒙ
㸦164.8 g㸧ࠊ1-ࣈࢱࣀ࣮ࣝᒙ㸦76 g㸧ࠊỈᒙ㸦411.8 g㸧ࢆᚓࡓࠋࡇࡢ࠺ࡕࠊ࣊࢟ࢧࣥᒙ࡜㓑㓟࢚ࢳࣝᒙ㸦164.8 g㸧ࢆ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢ
ࣛࣇ࢕࡟௜ࡋࠊࢡ࣒ࣟࣟ࣍ࣝ㸦3 L㸧ࠊࢡ࣒ࣟࣟ࣍ࣝ - ࣓ࢱࣀ࣮ࣝ㸦95: 5, 3 L㸧ࠊ㸦9: 1, 3
L㸧ࠊ㸦85: 15, 3 L㸧ࠊ㸦8: 2, 3L㸧ࠊ㸦7: 3, 3 L㸧ࠊ㸦6: 4, 3 L㸧ࠊ㸦5: 5, 3 L㸧ࠊ࣓ࢱࣀ࣮ࣝ
㸦3 L㸧ࡢ㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋCompounds 3, 4, 5㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 1, 46.5 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟௜ࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ30㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 1, 567.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛ
ࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻25㸸75ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 18 ศࡢࣆ࣮ࢡ࠿ࡽ compound 3㸦6.0 mg㸧ࠊಖᣢ᫬㛫 22 ศࡢࣆ࣮ࢡ࠿ࡽ
compound 4㸦2.3 mg㸧ࠊಖᣢ᫬㛫 28 ศࡢࣆ࣮ࢡ࠿ࡽ compound 5㸦2.7 mg㸧ࢆᚓࡓࠋCompounds 13, 14, 15, 16, 17, 18
㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 2, 22.65 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ30㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 1, 1.67 g㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢ
ࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻25㸸75ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 15 ศࡢࣆ࣮ࢡ࠿ࡽ compound 13㸦11.4 mg㸧ࠊಖᣢ᫬㛫 19 ศࡢࣆ࣮ࢡ࠿
ࡽ compound 14㸦17.5 mg㸧ࠊಖᣢ᫬㛫 23 ศࡢࣆ࣮ࢡ࠿ࡽ compound 15㸦20.0 mg㸧ࠊಖᣢ᫬㛫 28 ศࡢࣆ࣮ࢡ࠿ࡽ compound 16 + compound 17㸦18.3 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 689.1 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻35㸸65ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 17 ศࡢࣆ࣮ࢡ࠿ࡽ
compound 18㸦3.8 mg㸧ࢆᚓࡓࠋ
185

Compounds 10, 11㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 3, 14.09 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ30㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 853.5 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻35㸸65ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 14 ศࡢࣆ࣮ࢡ࠿ࡽ compound 10㸦300 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 855.4 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻40㸸60ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 20 ศࡢࣆ࣮ࢡ࠿ࡽ
compound 11㸦16.2 mg㸧ࢆᚓࡓࠋCompounds 1, 2, 6㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 4, 13.43 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 4, 1.29 g㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢ
ࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻60㸸40ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 15 ศࡢࣆ࣮ࢡ࠿ࡽ compound 1㸦12.0 mg㸧ࠊಖᣢ᫬㛫 25 ศࡢࣆ࣮ࢡ࠿
ࡽ compound 2㸦70.0 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࠊ60㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 928.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻50㸸50ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 9 ศࡢࣆ࣮ࢡ࠿ࡽ
compound 6㸦20.0 mg㸧ࢆᚓࡓࠋCompounds 7, 12㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 5, 10.31 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 878.4 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻30㸸70ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 21 ศࡢࣆ࣮ࢡ࠿ࡽ compound 7㸦15.0 mg㸧ࢆᚓࡓࠋ186

ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 630.1 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻35㸸65ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 27 ศࡢࣆ࣮ࢡ࠿ࡽ
compound 12㸦7.6 mg㸧ࢆᚓࡓࠋCompounds 8, 9㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙ
ࣥ 6, 9.23 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ20㸣࣓ࢱࣀ࣮ࣝ→100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 715.3 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻25㸸75ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.8 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 17 ศࡢࣆ࣮ࢡ࠿ࡽ compound 8㸦8.8 mg㸧ࠊಖᣢ᫬㛫 23 ศࡢࣆ࣮ࢡ࠿
ࡽ compound 9㸦4.5 mg㸧ࢆᚓࡓࠋᢳฟࠊ༢㞳ࠊ⢭〇 (ࢡࣟࢱ࢟࢝ࢬࣛ Hosiea japonica)
஝⇱ࡉࡏࡓࢡࣟࢱ࢟࢝ࢬࣛⴥ㒊࡜ࡘࡿࢆ࣓ࢱࣀ࣮࡛ࣝ 3 ᅇ㸦45 L㸧ᢳฟࡋࠊ1.5 L ࡟⃰⦰ᚋࠊ࣊࢟ࢧࣥ 1.5 L ࡛ศ㓄ࡋࡓࠋ࣓ࢱࣀ࣮ࣝᒙࢆ⃰⦰ᚋࠊỈ 1.5 L ࡛ᠱ⃮ࡋࠊ㓑㓟࢚ࢳ
ࣝࠊ1㸫ࣈࢱࣀ࣮ࣝࢆࡑࢀࡒࢀ 1.5 L ࡛㐃⥆ⓗ࡟ศ㓄ࠊ⃰⦰ࡋࠊ࣊࢟ࢧࣥᒙ࡜㓑㓟࢚ࢳࣝᒙࠊ
1㸫ࣈࢱࣀ࣮ࣝᒙࠊỈᒙࢆᚓࡓࠋ
ࡇࡢ࠺ࡕࠊࡘࡿࡢ㓑㓟࢚ࢳࣝᒙ (32.5 g) ࢆ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮
࡟௜ࡋࠊࢡ࣒ࣟࣟ࣍ࣝ㸦3 L㸧ࠊࢡ࣒ࣟࣟ࣍ࣝ - ࣓ࢱࣀ࣮ࣝ㸦95 : 5, 1 L㸧ࠊ㸦9 : 1, 1 L㸧ࠊ㸦85 : 15, 1 L㸧ࠊ㸦8 : 2, 1 L㸧ࠊ㸦7 : 3, 1 L㸧ࠊ㸦6 : 4, 1 L㸧ࠊ㸦5 : 5, 1 L㸧ࠊ࣓ࢱࣀ࣮ࣝ
㸦1 L㸧ࡢ㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋࡲࡓࠊⴥ㒊ࡢ㓑㓟࢚ࢳࣝᒙ (27.3g) ࢆ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟௜
ࡋࠊࢡ࣒ࣟࣟ࣍ࣝ㸦3 L㸧ࠊࢡ࣒ࣟࣟ࣍ࣝ - ࣓ࢱࣀ࣮ࣝ㸦95 : 5, 1 L㸧ࠊ㸦9 : 1, 1 L㸧ࠊ㸦85 :15, 1 L㸧ࠊ㸦8 : 2, 1 L㸧ࠊ㸦7 : 3, 1 L㸧ࠊ㸦6 : 4, 1 L㸧ࠊ㸦5 : 5, 1 L㸧ࠊ࣓ࢱࣀ࣮ࣝ㸦1 L㸧ࡢ㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 9 ࢆᚓࡓࠋCompounds 26, 31
ࡘࡿࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 1, 6.01 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟௜ࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋ187

ࡑࡢ࠺ࡕࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 40.9 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻35㸸65ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 18 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 26㸦19.9 mg㸧ࠊಖᣢ᫬㛫 22 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 31㸦2.7 mg㸧ࢆᚓࡓࠋCompounds 27, 28, 44, 45, 46, 47, 48, 49, 54
ࡘࡿࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 6.87 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 139.9 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 20㸸80ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 22 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 44㸦2.0 mg㸧ࠊಖᣢ᫬㛫 27 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 45㸦8.1 mg㸧ࠊಖᣢ᫬㛫 36 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 46㸦7.7 mg㸧ࠊಖᣢ᫬㛫 46 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 47㸦3.0 mg㸧ࠊಖᣢ᫬㛫 1 ᫬㛫 1 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 48㸦3.1 mg㸧ࠊಖᣢ᫬㛫 1᫬㛫 5 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 49㸦8.2mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 4, 955.9 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 35㸸65ࠊ
࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 24 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 27㸦19.5 mg㸧ࠊಖᣢ᫬㛫 54 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 28㸦4.2 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ60㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 292.5 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 45㸸55ࠊ
࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 23 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 54㸦7.3 mg㸧ࢆᚓࡓࠋCompounds 32, 33, 34, 35, 36, 37, 38, 39, 42, 43
ࡘࡿࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 1.99 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 78.1 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 25㸸75ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 40 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 39㸦3.2 mg㸧ࠊಖᣢ᫬㛫 24 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 42㸦6.0 mg㸧ࠊಖᣢ᫬㛫 31 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 43㸦2.2 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 4, 353.4 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 36㸸64ࠊ

188

࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 16 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 32㸦30.9 mg㸧ࠊಖᣢ᫬㛫 25 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 33㸦9.8 mg㸧ࠊಖᣢ᫬㛫
32 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 34㸦12.4 mg㸧ࠊಖᣢ᫬㛫 36 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 35
㸦4.9 mg㸧ࠊಖᣢ᫬㛫 38 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 36㸦14.8 mg㸧ࠊಖᣢ᫬㛫 42 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 37㸦13.2 mg㸧ࠊಖᣢ᫬㛫 19 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 38㸦9.5 mg㸧ࢆᚓࡓࠋCompound 21
ࡘࡿࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 1.42 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ60㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 132.5 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 45㸸55ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 14 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 21㸦12.0 mg㸧ࢆᚓࡓࠋCompound 40
ࡘࡿࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 7 and 8, 1.68 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟
ᑐࡋࠊ࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛
10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 116.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 30㸸70ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 9 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 40㸦5.3 mg㸧ࢆᚓࡓࠋCompounds 23, 24, 25, 30, 53ⴥ㒊ࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 2.82 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ20㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 1, 28.8 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 20㸸80ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 28 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 23㸦6.5 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 121.0 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 30㸸70ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 15 ศࡢࣆ࣮ࢡ࠿ࡽ
189

Compound 24㸦2.6 mg㸧ࠊಖᣢ᫬㛫 19 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 25㸦6.4 mg㸧ࠊಖᣢ᫬㛫
25 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 30㸦2.3 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ90㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 8, 27.1 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 70㸸30ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 20 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 53㸦44.4 mg㸧ࢆᚓࡓࠋCompound 29ⴥ㒊ࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 1.49 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ70㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 6, 150.0 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 65㸸35ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 12 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 29㸦14.6 mg㸧ࢆᚓࡓࠋCompounds 22, 41, 50, 51, 52ⴥ㒊ࡢ㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡࣟࣟ࣍ࣝ
࣒⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 6, 1.51 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ
࣓ࢱࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 4, 134.0 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺ
ࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 30㸸70ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 24 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 22㸦3.2 mg㸧ࠊಖᣢ᫬㛫 20 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 50㸦2.9 mg㸧ࠊಖᣢ᫬㛫 31 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 51㸦15.2 mg㸧ࠊಖᣢ᫬㛫 37 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 52㸦5.7 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ60㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 92.9 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 40㸸60ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 14 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 41㸦4.4 mg㸧ࢆᚓࡓࠋᢳฟࠊ༢㞳ࠊ⢭〇 (࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis)
஝⇱ࡉࡏࡓ࣋ࢺࢼ࣒⏘᳜≀ Heliciopsis terminalis ࡢᶞ⓶ࢆ࣓ࢱࣀ࣮࡛ࣝ 3 ᅇ㸦45 L㸧ᢳฟࡋࠊ1.5 L ࡟⃰⦰ᚋࠊ࣊࢟ࢧࣥ 1.5 L ࡛ศ㓄ࡋࡓࠋ࣓ࢱࣀ࣮ࣝᒙࢆ⃰⦰ᚋࠊỈ 1.5 L ࡛ᠱ⃮ࡋࠊ㓑㓟࢚ࢳࣝࠊ1㸫ࣈࢱࣀ࣮ࣝࢆࡑࢀࡒࢀ 1.5 L ࡛㐃⥆ⓗ࡟ศ㓄ࠊ⃰⦰ࡋࠊ࣊࢟ࢧࣥᒙ
࡜㓑㓟࢚ࢳࣝᒙࠊ1㸫ࣈࢱࣀ࣮ࣝᒙࠊỈᒙࢆᚓࡓࠋ
190

ࡇࡢ࠺ࡕࠊ㓑㓟࢚ࢳࣝᒙ (118.28 g) ࢆ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࡟௜ࡋࠊ
ࢡ࣒ࣟࣟ࣍ࣝ㸦3 L㸧ࠊࢡ࣒ࣟࣟ࣍ࣝ - ࣓ࢱࣀ࣮ࣝ㸦30 : 1, 3 L㸧ࠊ㸦20 : 1, 3 L㸧ࠊ㸦10 : 1,
3 L㸧ࠊ㸦7 : 1, 3 L㸧ࠊ㸦5 : 1, 3 L㸧ࠊ㸦3 : 1, 3 L㸧ࠊ㸦3 : 2, 3 L㸧ࠊ㸦2 : 1, 3 L㸧ࠊ࣓ࢱࣀ࣮ࣝ㸦3 L㸧ࡢ㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 - 10 ࢆᚓࡓࠋCompounds 58, 59, 60, 63㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 1.93 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ࣓ࢱ
ࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ30㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ
step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 – 9 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ50㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 5.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢ
ࣛࣇ࢕࣮ࢆ฼⏝ࡏࡎ࡟ࠊCompound 63㸦5.7 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ60㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 66.7 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 60㸸40ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 16 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 58㸦10.8 mg㸧ࠊಖᣢ᫬㛫 25 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 59㸦31.5 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ70㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 95.9 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 60㸸40ࠊ࢝
࣒ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 45 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 60㸦14.3 mg㸧ࢆᚓࡓࠋCompounds 66, 67
㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 4, 10.41 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ࣓ࢱ
ࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ
step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 – 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 181.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 30㸸
70ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 24 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 66㸦10.8 mg㸧ࠊಖᣢ᫬㛫 33 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 67㸦31.5 mg㸧ࢆᚓࡓࠋCompounds 56, 57, 61, 68, 69, 70
㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 5, 65.18 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ࣓ࢱ

191

ࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ
step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 – 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ30㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 875.6 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 40㸸
60ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 40 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 57㸦4.0 mg㸧ࠊಖᣢ᫬㛫 42 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 61㸦7.2 mg㸧ࠊಖᣢ᫬㛫 21 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 69㸦5.2 mg㸧ࠊಖᣢ᫬㛫 15 ศࡢࣆ࣮ࢡ࠿ࡽ Compound70㸦4.5 mg㸧ࢆᚓࡓࠋ
ࡲࡓࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ40㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 3, 7595.1 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 26㸸74ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 50 ศࡢࣆ࣮ࢡ࠿ࡽ
Compound 56㸦22.0 mg㸧ࠊಖᣢ᫬㛫 71 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 68㸦35.6 mg㸧ࢆᚓࡓࠋCompound 64㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 6, 9.10 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ࣓ࢱ
ࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ20㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ
step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 – 10 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ80㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 7, 1365.5 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ㸻70㸸
30ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 20 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 64㸦10.3 mg㸧ࢆᚓࡓࠋCompounds 55, 62, 65
㓑㓟࢚ࢳࣝᒙࡢ㡰┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࢡ࣒ࣟࣟ࣍ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 7, 11.60 g㸧ࢆ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟ᑐࡋࠊ࣓ࢱ
ࣀ࣮ࣝ㸫Ỉࡢΰྜ⁐፹㸦ྛ 500 mL ࠊ10㸣࣓ࢱࣀ࣮ࣝЍ100㸣࣓ࢱࣀ࣮ࣝࡲ࡛ 10㸣้ࡳࡢ
step gradient +࢔ࢭࢺࣥ㸧ࢆ⏝࠸࡚㡰࡟⁐ฟࡉࡏࠊࣇࣛࢡࢩࣙࣥ 1 – 11 ࢆᚓࡓࠋࡑࡢ࠺ࡕࠊ㏫┦ࢩࣜ࢝ࢤ࣒ࣝ࢝ࣛࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮࡟࠾ࡅࡿࠊ20㸣࣓ࢱࣀ࣮ࣝ⁐ฟ⏬ศ㸦ࣇࣛࢡࢩࣙࣥ 2, 319.5 mg㸧ࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕࣮㸦࢔ࢭࢺࣥ㸸Ỉ 㸻 10㸸
90ࠊ࣒࢝ࣛ㸸ODSࠊὶ㏿㸸2.0 mL/min㸧ࢆ⏝࠸࡚⢭〇ࡋࡓ࡜ࡇࢁࠊಖᣢ᫬㛫 24 ศࡢࣆ࣮ࢡ
࠿ࡽ Compound 55㸦11.1 mg㸧ࠊಖᣢ᫬㛫 42 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 62㸦52.6 mg㸧ࠊಖᣢ᫬㛫 35 ศࡢࣆ࣮ࢡ࠿ࡽ Compound 65㸦13.2 mg㸧ࢆᚓࡓࠋ192

Compound 1, 2, 11 ࡢ࢔ࣝ࢝ࣜຍỈศゎ࡜⢾ศᯒ
100 mM NaOCH3 solution 200 μL ࡜࣓ࢱࣀ࣮ࣝ 1800 μL ࢆΰྜࡋࡓ⁐ᾮࢆࠊ஝⇱ࡉࡏࡓCompound 1㸦2 mg㸧࡟ຍ࠼ࠊⰋࡃ⁐࠿ࡋ࡚ᐊ ࡛㟼⨨ࡋࡓࠋ15 ศẖ࡟᣺ࡾΰࡐࠊTLC㸦ᒎ㛤⁐፹ࢡ࣒ࣟࣟ࣍ࣝ㸸࣓ࢱࣀ࣮ࣝ㸸Ỉ = 15㸸6㸸1㸧࡛཯ᛂࡢ⛬ᗘࢆ☜ㄆࡋࡓ࡜ࡇࢁࠊ㛤ጞ30 ศ࡛཯ᛂ⤊஢࡜ุ᩿ࡋࡓࠋ⥆࠸࡚ࠊ㝧࢖࢜ࣥ஺᥮ᶞ⬡㸦AMBERLITE IR 120B NA㸧ࢆ⏝࠸࡚୰࿴ࡋࠊᚓࡽࢀࡓ⁐ᾮࢆ⃰⦰ࡋࡓࠋ㓑㓟࢚ࢳࣝ 0.2 mL ࡜Ỉ 0.2 mL ࢆຍ࠼࡚ศ㓄ࢆ⾜ࡗࡓࠋୖᒙ࡛࠶ࡿ㓑㓟࢚ࢳࣝᒙࢆ㝖ཤࡋࠊᚓࡽࢀࡓỈᒙࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕-࡟࡚ศᯒࡋࡓࠋࡑࡢ㝿࡟⁐ฟ⁐፹࡜ࡋ࡚ࡣࠊ࢔ࢭࢺࢽࢺࣜࣝỈࡢΰྜ⁐፹㸦75㸣CH3CN㸧ࢆ౑⏝ࡋࠊศᯒ⏝࣒࢝ࣛ࡜ࡋ࡚ Shodex NH2P-50㸦᫛࿴㟁ᕤ㸧ࠊ᳨ฟჾ࡜ࡋ࡚ OR-2090 ᪕ගᗘ᳨ฟィ㸦᪥ᮏศග㸧ࢆ౑⏝ࡋࡓࠋࡲࡓࠊὶ㏿ࡣ 1.0 mL/minࠋsample ࡢ injection volume ࡣ10 μL ࡜ࡋ࡚⢾ศᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊಖᣢ᫬㛫 6 ศ࡛⌧ࢀࡓࣆ࣮ࢡࡀṇࡢ᪕ගᛶࢆ♧ࡋࡓࡇ࡜࠿ࡽࠊCompound 1 ࡣ sucrose ࢆ᭷ࡍࡿ࡜ุ᩿ࡋࡓࠋ
࡞࠾ Compound 1 ࡜ྠ᮲௳ୗ࡛ࠊᶆရ࡜ࡋ࡚ sucrose ࢆ 10 μL injection ࡋࡓ࡜ࡇࢁࠊ
sucrose ࡣಖᣢ᫬㛫 6 ศࡢࣆ࣮ࢡ࡟࠾࠸࡚ṇࡢ᪕ගᛶࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ
Compound 2ࠊ11 ࠿ࡽࡣྠᵝ࡟ࡋ࡚ࠊ࢔ࣝ࢝ࣜຍỈศゎ࡜⢾ศᯒࢆ⾜࠸ࠊsucrose ࢆ᭷ࡍࡿࡇ࡜ࡶ☜ㄆࡋࡓࠋCompound 22, 56 ࡢຍỈศゎ࡜⢾ศᯒ
1M HCl solution 0.2 mL ࢆࠊ஝⇱ࡉࡏࡓ Compound 22㸦1 mg㸧࡟ຍ࠼ࠊ90ºC ࡛ 2 ᫬㛫཯ᛂࡉࡏࡓࠋࡑࡢ࠶࡜ࠊᐊ ࡟ᡠࡋࠊ࢖࢜ࣥ஺᥮ᶞ⬡ࢆ⏝࠸࡚୰࿴ࡋࠊᚓࡽࢀࡓ⁐ᾮࢆ⃰⦰ࡋࡓࠋ㓑㓟࢚ࢳࣝ 0.2 mL ࡜Ỉ 0.2 mL ࢆຍ࠼࡚ศ㓄ࢆ⾜ࡗࡓࠋୖᒙ࡛࠶ࡿ㓑㓟࢚ࢳࣝᒙࢆ
㝖ཤࡋࠊᚓࡽࢀࡓỈᒙࢆ㧗㏿ᾮయࢡ࣐ࣟࢺࢢࣛࣇ࢕-࡟࡚ศᯒࡋࡓࠋࡑࡢ㝿࡟⁐ฟ⁐፹࡜ࡋ࡚ࡣࠊ࢔ࢭࢺࢽࢺࣜࣝ-Ỉࡢΰྜ⁐፹㸦75㸣 CH3CN㸧ࢆ౑⏝ࡋࠊศᯒ⏝࣒࢝ࣛ࡜ࡋ࡚
Shodex NH2P-50㸦᫛࿴㟁ᕤ㸧ࠊ᳨ฟჾ࡜ࡋ࡚ OR-2090 ᪕ගᗘ᳨ฟィ㸦᪥ᮏศග㸧ࢆ౑⏝ࡋࡓࠋࡲࡓࠊὶ㏿ࡣ 1.0 mL/minࠋsample ࡢ injection volume ࡣ 10 μL ࡜ࡋ࡚⢾ศᯒࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊಖᣢ᫬㛫 6 ศ࡛⌧ࢀࡓࣆ࣮ࢡ࠾ࡼࡧಖᣢ᫬㛫 8 ศ࡛⌧ࢀࡓࣆ࣮ࢡࡀ㈇࠾ࡼࡧṇࡢ᪕ගᛶࢆ♧ࡋࡓࡇ࡜࠿ࡽࠊCompound 22 ࡣ L-rhamnose ࡜ D-glucose ࢆ᭷ࡍࡿ࡜ุ᩿ࡋࡓࠋ
࡞࠾ Compound 22 ࡜ྠ᮲௳ୗ࡛ࠊᶆရ࡜ࡋ࡚ L-rhamnose ࡜ D-glucose ࢆ 10 μL injectionࡋࡓ࡜ࡇࢁࠊL-rhamnose ࡣಖᣢ᫬㛫 6 ศࡢࣆ࣮ࢡ࠾ࡼࡧ D-glucose ࡣಖᣢ᫬㛫 8 ศࡢࣆ࣮ࢡ
࡟࠾࠸࡚㈇࠾ࡼࡧṇࡢ᪕ගᛶࢆ♧ࡍࡇ࡜ࢆ☜ㄆࡋ࡚࠸ࡿࠋ
Compound 56 ࠿ࡽࡣྠᵝ࡟ࡋ࡚ࠊຍỈศゎ࡜⢾ศᯒࢆ⾜࠸ࠊD-glucose ࢆ᭷ࡍࡿࡇ࡜ࡶ
☜ㄆࡋࡓࠋ

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Cosmetic, external skin preparation, and medical instrument, (2015)

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ᮏ◊✲ࢆ⾜࠺࡟࠶ࡓࡾࠊࡲࡓᮏㄽᩥࡢసᡂ࡟㛵ࡋࠊ⤊ጞᚚ᠓ษ࡞ࡿࡈᣦᑟࡈ㠴᧡ࢆ㈷ࡾࡲࡋࡓࠊᗈᓥ኱Ꮫ ኱Ꮫ㝔་⣔⛉Ꮫ◊✲⛉ ⸆⛉Ꮫᑓᨷ ๰⸆⛉Ꮫㅮᗙ ⏕⸆Ꮫ◊✲ᐊ ᯇᾉ ຾
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