ࣥ࢖࣑ࣥᆺᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡟ࡼࡿ㑏ඖ

࢟ࣀࣥ࢖࣑ࣥᆺᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡟ࡼࡿ㑏ඖ
᪥⨨⌮᝴ 㹙ᣦᑟᩍဨ㸸ṊᗜᕝዪᏊ኱Ꮫᩍᤵ ℩ཱྀ࿴⩏㹛
࣮࣮࢟࣡ࢻ㸸࢔ࢰᰁᩱ㸪㓟໬ᰁᩱ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ㸪㏥Ⰽ⏕ᡂ≀㸪㑏ඖ
⤖ᯝ࡜⪃ᐹ
⥴ゝ
⏕άࡢ୰࡟ࡣᵝࠎ࡞㑏ඖᛶ໬ྜ≀ࡀ࠶ࡿࠋ㑏ඖᛶ໬ྜ≀ࡣ㸪
Dye-1a ࡟ࡘ࠸࡚ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟⃰ᗘ 103 ಸ㸪50Υࡢ᮲
Ⰽ⣲࡜཯ᛂࡋ࡚ኚ㏥Ⰽࡸ⬺Ⰽ࡜࠸ࡗࡓ⌧㇟ࢆ㉳ࡇࡍࡇ࡜ࡀ࠶
௳࡛྾཰ࢫ࣌ࢡࢺࣝࡢኚ໬ࢆࡳࡿ࡜㸪ྍど㒊 λmax=530nm ࡢ
ࡿࠋࡋ࠿ࡋᰁᩱࡀ㑏ඖᛶ໬ྜ≀࡟ࡼࡗ࡚࡝ࡢࡼ࠺࡟ኚ໬ࡋ㸪
྾཰ࡀ᫬㛫࡜࡜ࡶ࡟పୗࡋ㸪8 ᫬㛫ᚋ࡟ࡣ㏥Ⰽࡋࡓ㸦ᅗ 1㸧
ࠋ
ኚ㏥Ⰽࢆ㉳ࡇࡍࡢ࠿࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡋࡓ◊✲ࡣࡁࢃࡵ࡚ᑡ
࡞ࡃ㸪᥎ ࡢᇦ࡟␃ࡲࡿࡶࡢࡶᑡ࡞ࡃ࡞࠸ࠋ
ᮏ◊✲ᐊ࡛ࡣ⏕άࡢ୰ࡢ≀㉁཰ᨭ࡟ࡘ࠸᳨࡚ウࡀຍ࠼ࡽࢀ
࡚ࡁࡓ
1-3)ࠋᮏ◊✲࡛ࡣ㸪㑏ඖᛶ໬ྜ≀࡜ࡋ࡚ࣃ࣮࣐ᾮࡸࢩ
Dye-1b㸪Dye-1e ࡟ࡘ࠸࡚ࡶྠᵝ࡟ྍど㒊ࡢ 536nm㸪
520nm ࡢ྾཰ࡀపୗࡋ㏥Ⰽࡋࡓࠋ୍᪉ Dye-1c ࡟ࡘ࠸࡚ࡣ
1a㸪1b㸪1e ࡼࡾࡍࡇࡋ᪩ࡃ 4~5 ᫬㛫࠿ࡅ࡚ λmax = 450nm
ࡢ྾ගᗘࡀపୗࡋ㏥Ⰽࡋࡓࠋࡇࢀࡣ 1a, 1b㸪1e ࡟ẚ࡭࢔࣑
ࣟࢭࢵࢺຍᕤ࡟⏝࠸ࡽࢀࡿࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ㸪ᰁᩱ࡟
ࣀᇶࡢሷᇶᛶࡀᙅ࠸ࡇ࡜࡟㉳ᅉࡍࡿ࡜᥎ ࡉࢀࡿࠋDye-1d
ࡣ࢟ࣀࣥ࢖࣑ࣥᆺᰁᩱ࡛࠶ࡿ࢔ࢰᰁᩱཬࡧᰁẟ࡟⏝࠸ࡽࢀࡿ
࡛ࡣࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࢆຍ࠼ࡿ࡜ 545nm ௜㏆ࡢᰁᩱࡢྍど
㓟໬ᰁᩱ
4)ࢆ㑅ࡧ㸪ᐇ㦂ⓗᡭἲࢆ⏝࠸࡚ኚ㏥Ⰽࡢヲ⣽࡞ࣉࣟ
㒊ࡢ྾ගᗘࡀῶᑡࡋ 15 ศ࡛࡯ࡰ㏥Ⰽࡀ᏶஢ࡋࡓࠋ1d ࡢ㏥Ⰽ
ࡔࡅࡀ␗ᖖ࡟㏿ࡃ㸪௚ࡢᰁᩱ࡜ࡣ㏥Ⰽࡢ࣓࢝ࢽࢬ࣒ࡀ኱ࡁࡃ
ࢭࢫࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆヨࡳࡓࠋ
࢔࣑ࣀ࢔ࢰᰁᩱ࡟ࡘ࠸࡚ࡣࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡟ࡼࡿ
␗࡞ࡿྍ⬟ᛶࡀ࠶ࡿࠋ
㏥Ⰽࢫ࣌ࢡࢺࣝࡢ ᐃ㸪㏥Ⰽ⏕ᡂ≀ࡢ༢㞳࡜ᵓ㐀Ỵᐃࢆ⾜࠸㸪
⏕ᡂ≀ࡣ༢࡟࢔ࢰᇶࡢ㑏ඖศゎ࡟ࡼࡿࡶࡢ࡛ࡣ࡞ࡃࢳ࢜ࢢࣜ
྾
ග
ᗘ
ࢥ࣮ࣝ㓟ࡀᵓ㐀࡟⤡ࢇࡔ」㞧࡞௜ຍ≀࡟ኚ໬ࡋ࡚࠸ࡿࡇ࡜ࢆ
᫂ࡽ࠿࡟ࡋࡓࠋ㓟໬ᰁᩱ࡟ࡘ࠸࡚ࡣᏳᐃᛶࡢḞዴ࠿ࡽࡑࡢᵓ
㐀࡟ࡘ࠸࡚ࡣ௒᪥࡛ࡶ᭕᫕࡞࡜ࡇࢁࡀ࠶ࡿࡢ࡛㸪௒ᅇ᪂ࡓ࡟
ྜᡂ࡟ᣮᡓࡋࡓࠋලయⓗ࡟ࡣ㸪㓟໬ᰁᩱࡢⓎⰍࢫ࣌ࢡࢺࣝࡢ
ᐃ࡜ⓎⰍ⏕ᡂ≀ࡢ༢㞳ࢆ⾜ࡗࡓࠋ
࢔࣑ࣀ࢔ࢰᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟࡟ࡼࡿ㏥Ⰽࢫ࣌ࢡࢺࣝ
ࡢኚ໬
ᐇ㦂᪉ἲ
(nm)
ᅗ '\HD ࡢ㏥Ⰽࢫ࣌ࢡࢺࣝࡢኚ໬㸦Υ㸧
ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡢ࢔ࢰᰁᩱ࡬ࡢ㏥Ⰽᛶࢆ᳨ウࡍࡿࡓࡵ㸪
࢔࣑ࣀ࢔ࢰᰁᩱ࡜ࡋ࡚ Dye-1a-e ࡜㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟
>D@ ™0㸪>D@ 0
㸦2a㸧ࢆ MeCN㸸Ỉ㸻1㸸1 ࡢ⁐፹୰࡛཯ᛂࡉࡏ㸪300600nm ࡢ྾཰ࢫ࣌ࢡࢺࣝࢆศගගᗘィ㸦Shimadzu UV-
࢔࣑ࣀ࢔ࢰᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡟ࡼࡿ㏥Ⰽ⏕ᡂ
2500 PC㸧࡛㐺ᐅ᫬㛫⤒㐣ࡈ࡜࡟ ᐃࡋࡓࠋ
≀ࡢྠᐃ
ᐇ㦂᪉ἲ
R1
N
1
2
3
1a: R , R , R =H
R2
N
1c: R1=H, R2=Ph, R3=H
N
R3
Dye-1
R
HS
1b: R1=H, R2=Me, R3=H
2
ᰁᩱࡣ Dye-1a-h ࢆ⏝࠸ࡓࠋࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡟ࡣ
ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟㸦2a㸧
㸪α-࣓ࣝ࢝ࣉࢺࣉࣟࣆ࢜ࣥ㓟㸦2b㸧
㸪
1e: R1, R2=H, R3=SO3Na
࣓ࣝ࢝ࣉࢺࡇࡣࡃ㓟㸦2c㸧ࢆ⏝࠸ࡓࠋᰁᩱ 100mg ࢆ⁐፹
1f: R1=H, R2=Me, R3=SO3Na
20ml㸦CH3CN:Ỉ㸻1㸸1 ࡲࡓࡣ 4㸸1㸧࡟⁐ゎࡋ㸪ᰁᩱࡢ 3
1g: R1=H, R2=Ph, R3=SO3Na
ಸ mol ࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయࢆຍ⇕㑏ὶୗ࡛ 4h ࠿ࡽ
1h: R1, R2=Me, R3=SO3Na
10h ཯ᛂࡉࡏࡓࠋᰁᩱࡢⰍࡢᾘኻᚋ࡟ຍ⇕ࢆṆࡵ㸪ᐊ ࡲ࡛
ᨺ෭ᚋ࡟⏕ࡌࡓỿẊࢆࢁ㐣ࡋࡓࠋ㏥Ⰽ⏕ᡂ≀ࡣ MeOH ࡲࡓ
2a:R=H
COOH
1d: R1, R2=Me, R3=H
2b:R=Me
2c:R=CH2COOH
ࡣ MeOH㸭࣊࢟ࢧ࡛ࣥ෌⤖ᬗࡋ㸪1H-NMR㸪13C-NMR㸪㉁
㔞ศᯒ㸦MS㸧
㸪㉥እ྾཰ࢫ࣌ࢡࢺࣝ㸦IR㸧
㸪ඖ⣲ศᯒ࡟ࡼࡾ
ᵓ㐀ࢆỴᐃࡋࡓࠋ
生活環境学研究 No.3
42 2015
Dye-1a ࡜ 2b ࡢ཯ᛂ࡛ࡣ㸪2b ࡢ 2 ศᏊ௜ຍ⎔໬≀㸦6a㸧
⤖ᯝ࡜⪃ᐹ
Dye-1a ࡜ 2a ࡜ࡢ཯ᛂ࡛ࡣ㸪ΰྜᾮࢆຍ⇕㑏ὶࡍࡿ࡜ᰁᩱ
࡜㸦཰⋡ 25%㸧
㸪 1 ศᏊ௜ຍ⎔໬≀㸦7a㸧ࡀ⏕ᡂࡋࡓ㸦཰⋡
ࡢ㉥Ⰽࡢ࿊Ⰽࡀ 5h ࡯࡝࡛ᾘኻࡋ㸪཯ᛂࡢ⤊Ⅼ࡛ࡣ⅊Ⰽࡢỿ
19%㸧
ࠋDye-1b㸪Dye-1c ࡜ 2b㸪2c ࡜ࡢ཯ᛂ࡟࠾࠸࡚ࡶ㸪㏥
Ẋࡀ⏕ࡌࡓࠋᚓࡽࢀࡓ⏕ᡂ≀ࡣ㸪1H-NMR㸦DMSO-d6㸧࡟
Ⰽ⏕ᡂ≀ࡣᑐᛂࡍࡿ 1 ศᏊ௜ຍ⎔໬≀࡜ 2 ศᏊ௜ຍ⎔໬≀ࡢ
࠾࠸࡚ δ=3.03㸦s㸧࡟࣓ࢳࣞࣥࣉࣟࢺࣥ 㸦CH2㸧
㸪10.30
୧᪉㸪ࡲࡓࡣ 1 ศᏊ௜ຍ⎔໬≀ࡢࡳࡀ⏕ࡌࡓࠋDye-1d ࡜ 2b
㸦s㸧࡟Ỉ⣲ ಶศࡢ࢔࣑ࢻࣉࣟࢺࣥ 㸦NHC=O㸧ࡀࡳࡽࢀ
ࡢ཯ᛂ࡛ࡣ㸪⨨᥮య 6d ࡀ཰⋡ 38%࡛⏕ᡂࡋࡓࠋࡲࡓ Dye-
ࡿࡇ࡜࠿ࡽ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟 2 ศᏊࡀᰁᩱ࡟௜ຍ⎔໬ࡋ࡚
1e-g ࡜ 2b㸪2c ࡜ࡢ཯ᛂ࡛ࡶᑐᛂࡍࡿ 1 ศᏊ௜ຍ⎔໬≀㸪2
⏕ࡌࡓ⎔≧࢔࣑ࢻㄏᑟయ㸦3a㸧࡛࠶ࡿ࡜᥎ᐃࡋࡓ㸦཰⋡
ศᏊ௜ຍ⎔໬≀ࢆᚓࡓࠋ
26%㸧
ࠋࡲࡓ 13C-NMR㸪IR ࡶࡇࡢᵓ㐀ࢆᨭᣢࡋࡓࠋ
ࢁᾮഃࡢ⏕ᡂ≀ࡣ 1H-NMR ࡟࠾࠸࡚ δ=2.93㸦s㸧࡟࣓ࢳ
ࣞࣥࣉࣟࢺࣥ㸪5.20㸦bs㸧࡟࢔࣑ࣀࣉࣟࢺࣥ㸦NH2㸧
㸪6.12
R
O
R
R
O
ಶศࡢ࢔࣑ࢻࣉࣟࢺࣥࡀᏑᅾࡍࡿࡇ࡜࠿ࡽ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ
6
㓟ࡀᰁᩱ࡟ 1 ศᏊ௜ຍ⎔໬ࡋ࡚࡛ࡁࡓ⎔≧࢔࣑ࢻㄏᑟయ
㸪IR ࡶࡇ
㸦4a㸧࡛࠶ࡿ࡜᥎ᐃࡋࡓࠋ13C-NMR㸦DMSO-d6㸧
ࡢᵓ㐀ࢆᨭᣢࡋࡓ㸦཰⋡ 9%㸧
ࠋ
R
S
HN
Me
O
HN
CH2COOH
N
S
S
HN
ࡀ 26%㸪1 ศᏊ௜ຍ⎔໬≀㸦4b㸧ࡀ 24%ࡢ཰⋡࡛⏕ᡂࡋ㸪
HN
S
㸦s㸧࡟ 1 ಶศࡢ࣋ࣥࢮࣥ⎔ࡢࣉࣟࢺࣥ㸪9.75㸦s㸧࡟Ỉ⣲ 1
ࡲࡓ㸪Dye-1b ࡟࠾࠸࡚ࡶྠᵝࡢ 2 ศᏊ௜ຍ⎔໬≀㸦3b㸧
Me
N
O
7
S
S
Me
HN
O
HN
CH2COOH
CH2COOH
O
8
9
Me
S
COOH
a:R1=H, R2=H
b:R1=H, R2=Me
N N
c:R1=H, R2=Ph
Dye-1c ࡛ࡣ 1 ศᏊ௜ຍ⎔໬≀㸦4c㸧ࡢࡳࡀ 67%ࡢ཰⋡࡛ᚓ
6d
ࡽࢀࡓࠋ
཯ᛂᚋࡢΰྜ≀ࡢ 1H-NMR ࡢ NH ࡢࣆ࣮ࢡࡢ✚ศẚ࡟ࡼ
R1
O
R1
N
N
a:R1=H, R2=H
S
S
S
ࡾ Dye-1a-c㸪Dye-1e-g ࡜ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ࡜ࡢ཯ᛂ
R2
O
3 4
2
b:R =H, R =Me
c:R1=H, R2=Ph
HN
HN
1
O
Dye-1d ࡟ࡘ࠸࡚ 2a ࢆῧຍᚋ࡟ຍ⇕㑏ὶࡍࡿ࡜ᰁᩱ࡟ࡼࡿ
࡟࠾ࡅࡿ 1 ศᏊ௜ຍ⎔໬≀㸪2 ศᏊ௜ຍ⎔໬≀ࡢ⏕ᡂࡢ๭ྜ
ࢆ⟬ฟࡋࡓ⤖ᯝࢆ⾲ 1 ࡟♧ࡍࠋ࢔࣑ࣀᇶ㒊ศࡢ⨨᥮ᇶࡢ࠿ࡉ
ࡀ㧗ࡃ࡞ࡿ࡯࡝㸦H→Me→Ph㸧2 ศᏊ௜ຍ≀ࡀ⏕ᡂࡋ࡟ࡃ
࠸ഴྥࢆ♧ࡋࡓࠋ
⾲ ㏥Ⰽ≀ࡢ⏕ᡂẚ㸦 ศᏊ௜ຍయ㸸 ศᏊ௜ຍయ㸧
㉥Ⰽࡢ࿊Ⰽࡀ 5h ࡯࡝࡛ᶳⰍ࡟ኚ໬ࡋ㸪ࡑࢀ௨ୖࡢ㏥Ⰽࡣㄆ
ࡵࡽࢀ࡞࠿ࡗࡓࠋỈࢆຍ࠼࡚ᚓࡽࢀࡓῐᶳⰍࡢ⏕ᡂ≀ 5d ࡣ㸪
1H-NMR
࡟࠾࠸࡚ Dye-1d ࡢࢪ࣓ࢳࣝ࢔࣑ࣀࣉࣟࢺࣥࡀᾘኻ
ࡋ㸪௦ࢃࡾ࡟ δ=3.83㸦s㸧࡟࣓ࢳࣞࣥࣉࣟࢺࣥ㸦CH2㸧
㸪ࣇ
࢙ࢽࣝࣉࣟࢺࣥࡀ 11 ಶศᏑᅾࡍࡿࡇ࡜࠿ࡽ㸪ࢳ࢜ࢢࣜࢥ࣮
ࣝ㓟ࡀᰁᩱࡢࢪ࣓ࢳࣝ࢔࣑ࣀᇶ࡜⨨᥮ࡋ࡚⏕ࡌࡓ≀㉁㸦5d㸧
࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓ㸦཰⋡ 35%㸧ࠋ13C-NMR㸦DMSO-d6㸧㸪
IR ࡶࡇࡢᵓ㐀ࢆᨭᣢࡋࡓࠋ
S
཯ᛂࡢ࣓࢝ࢽࢬ࣒ࢆᅗ 2 ࡟♧ࡍࠋDye-1a-c㸪Dye-1e-g ࡜
COOH
5d: R=H
N N
R
5h: R=SO3Na
5
2a ࡜ࡢ཯ᛂ࡛ࡣ㸪࢔ࢰᆺࡢ஫ኚ␗ᛶయࡢࣄࢻࣛࢰࣥᆺ㸪ࡘ
ࡲࡾ࢟ࣀࣥࢪ࢖࣑ࣥᆺࡢᰁᩱࡢ஧㔜⤖ྜ㒊ศࡢ 3 ఩࡟ࡲࡎࢳ
࣮࢜ࣝࡀ࣐࢖ࢣࣝ௜ຍࢆ㉳ࡇࡍࠋศᏊෆ࡛⬺Ỉ࡟ࡼࡾ⎔໬ࡋ㸪
2 ఩࡟ࡶ࠺ 1 ศᏊࡢࢳ࣮࢜ࣝࡀ࣐࢖ࢣࣝ௜ຍᚋ㸪ศᏊෆ⬺Ỉ
Dye-1e ࡜ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡢ཯ᛂ࡛ࡣ㸪1 ศᏊ௜ຍ⎔໬
ࡋ࡚⎔໬ࡋࡓࡶࡢࡣ 2 ศᏊ⎔໬௜ຍ≀㸦3㸧࡟㸪 N 㒊ศ࡟௜
≀㸦4a㸧ࢆ 35%㸪2 ศᏊ௜ຍ⎔໬≀㸦3a㸧ࢆ 9%ࡢ཰⋡࡛ᚓ
ຍᚋຍỈศゎࢆ㉳ࡇࡍ࡜ 1 ศᏊ௜ຍ⎔໬≀㸦4㸧࡟࡞ࡿ࡜᥎
ࡓࠋDye-1f ࡟ࡘ࠸࡚ࡶ 1 ศᏊ௜ຍ⎔໬≀㸦4b㸧ࢆ 40%㸪2
ࡋ࡚࠸ࡿࠋ
ศᏊ௜ຍ⎔໬≀㸦3b㸧ࢆ 15%ࡢ཰⋡࡛ᚓࡓࠋDye-1g ࡟ࡘ࠸
ࡇࡢ࡜ࡁ㸪 Dye-1c㸪1g ࡣ⨨᥮ᇶࡢ࠿ࡉࡀ኱ࡁࡍࡂ࡚㸪2
࡚ࡶ Dye-1c ࡜ྠࡌࡼ࠺࡟ 1 ศᏊ௜ຍ⎔໬≀㸦4c㸧ࡢࡳࢆ
఩࡟ 2 ศᏊ┠ࡢࢳ࣮࢜ࣝ㢮ࡀ௜ຍࡉࢀ࡟ࡃࡃ཯ᛂࡀ 1 ศᏊ௜
67%ࡢ཰⋡࡛ᚓࡓࠋDye-1h ࡟ࡘ࠸࡚ࡣ⏕ᡂ≀ࡢ༢㞳ࢆヨࡳ
ຍ⎔໬࡬㐍ࡴࡶࡢ࡜ᛮࢃࢀࡿࠋ࢔࣑ࣀᇶࡢỈ⣲ 1 ศᏊࢆ࣓ࢳ
ࡓࡀᅔ㞴࡛࠶ࡗࡓࡓࡵ㸪⣸እྍど྾཰ࢫ࣌ࢡࢺ࡛ࣝࢳ࢜ࢢࣜ
ࣝᇶ࡛⨨᥮ࡋࡓ Dye-1b㸪1f ࡀ↓⨨᥮ࡢ Dye-1a㸪1e ࡼࡾࡶ
ࢥ࣮ࣝ㓟࡟ࡼࡿ㏥Ⰽࡢ㐣⛬ࢆ㏣㊧ࡋࡓ⤖ᯝ㸪Dye-1d ࡜ྠᵝ
2 ศᏊ௜ຍ⎔໬≀ࡢ⏕ᡂࡢ๭ྜࡀᑡ࡞࠸⌮⏤ࡶྠᵝ࡟⪃࠼ࡽ
ࡢ⨨᥮⏕ᡂ≀ 5h ࡀ⏕ᡂࡋ࡚࠸ࡿ࡜᥎ ࡋࡓࠋ
ࢀࡿࠋ
生活環境学研究 No.3 2015 43
Dye-1d ࡛ࡣ㸪ࢳ࣮࢜ࣝ㢮ࡀᰁᩱࡢࢪ࣓ࢳࣝ࢔࣑ࣀᇶ࡜⨨
㸦C㸧ࢆ➼ࣔࣝ㔞㸦1.0™10-4mol㸧ࢆ EtOH㸸Ỉ㸻1㸸1 ࡢ⁐
᥮ࡋࡓ⏕ᡂ≀ࡀᚓࡽࢀࡓࠋࡇࡢ཯ᛂࡣ཯ᛂࡢ㏿ࡉ࠿ࡽࡶศ࠿
፹ 40ml ୰࡟⁐࠿ࡋ㸪Ⅳ㓟ࢼࢺ࣒࡛ࣜ࢘ pH9 ࡟ㄪ〇ࡋ㸪⁐
ࡿ㏻ࡾ㸪ࢪ࣓ࢳࣝ࢔࣑ࣀᇶࡢ⬺㞳ᇶࡢࡋࡸࡍࡉࡀ࠶ࡿࡢ࡛㸪
ᾮ࡟✵Ẽࢆ࣏ࣥࣉ࡛㏦ࡾ࡞ࡀࡽ✵Ẽ㓟໬࡟ࡼࡾᩘ᫬㛫཯ᛂࡉ
๓㏙ࡢ௜ຍ⎔໬ࡼࡾ㏿ࡸ࠿࡟㉳ࡇࡿࡶࡢ࡜ᛮࢃࢀࡿࠋ௜ຍ⎔
ࡏࡓࠋ཯ᛂᚋࡣ⁐ᾮࢆ୰ᛶ࡟ࡋ㸪ỿẊࡋࡓ㓟໬ᰁᩱࢆᚓࡓࠋ
໬཯ᛂࡼࡾ⨨᥮཯ᛂࡀ㏿ࡸ࠿࡟㉳ࡇࡾ㸪⨨᥮యࢆ⏕ࡌࡓ࡜ᛮ
ⓎⰍ⏕ᡂ≀ࡢ༢㞳㸪⢭〇ࡣ㸪P-1a-d㸭C-2b ࡢ⤌ࡳྜࢃࡏ࡟
ࢃࢀࡿࠋ
ࡘ࠸࡚ࡣ཯ᛂ⁐ᾮࢆ࢚ࣂ࣏࣮ࣞࢱ࣮࡟ࡼࡾ⃰⦰ࡋ⁐፹ࢆ㝖ཤ
ࡋ㸪MeOH ࡟ࡼࡾ෌⤖ᬗࢆ⾜ࡗࡓࠋP-1a ࡜ C-1a ࡣࢡ࣐ࣟ
ࢺࢺࣟࣥ㸦CH2Cl2㸭࣊࢟ࢧࣥ㸧࡟ࡼࡾ⏕ᡂ≀ࢆ༢㞳ࡋ㸪ࡑ
ࢀࡒࢀ MeOH ࡟ࡼࡾ෌⤖ᬗࢆࡋࡓࠋ⢭〇ࡋࡓ㓟໬ᰁᩱࡣ
1H-NMR㸪13C-NMR㸪㉁㔞ศᯒ㸦MS㸧
㸪㉥እ྾཰ࢫ࣌ࢡࢺ
ࣝ㸦IR㸧
㸪ඖ⣲ศᯒ࡟ࡼࡾᵓ㐀ࢆỴᐃࡋࡓࠋࡲࡓ㸪୍㒊ࡢ㓟
໬ᰁᩱ࡟ࡘ࠸࡚ࡣ↓Ỉ㓑㓟࡜ࣆࣜࢪࣥ࡟ࡼࡿ࢔ࢭࢳࣝ໬ࡶ⾜
ࡗࡓࠋ
⤖ᯝ࡜⪃ᐹ
P-1a ࡜ C-1a ࡢ⤌ࡳྜࢃࡏ࡛ࡣ᫬㛫ࡢ⤒㐣࡟ࡼࡾ
3
λmax=623nm ࡢ྾཰ࡀቑ኱ࡋ㸪 ᫬㛫࡯࡝࡛㟷Ⰽ࡟╔Ⰽࡋࡓࠋ
C-1b ࡛ࡣ λmax=625nm ࡛㟷Ⰽ࡟㸪m-࢔࣑ࣀࣇ࢙ࣀ࣮ࣝ㢮ࡢ
C-2a㸪C-2b ࡣࡑࢀࡒࢀ λmax=600nm, 575nm ࡛㟷⣸㹼⣸࡟㸪
4
ࣞࢰࣝࢩࣥ㢮࡟ࡘ࠸࡚ࡣ㸪C-3a㸪3b㸪3d ࡣࡑࢀࡒࢀ λmax =
ᅗ '\H ࡜ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡢ཯ᛂ࣓࢝ࢽࢬ࣒
545nm, 530nm, 565nm ࡛⣸㹼㉥⣸Ⰽࡢ╔ⰍࡀぢࡽࢀࡓࠋC3c ࡟࠾࠸࡚ࡣ࡯࡜ࢇ࡝╔Ⰽࡀぢࡽࢀ࡞࠿ࡗࡓࠋ
ࡋ࠿ࡋ C-3a㸪3b㸪3d ࡟ࡘ࠸࡚㸪╔Ⰽࡀ㉳ࡇࡗࡓᚋࡶ⁐ᾮ
㓟໬ᰁᩱࡢⓎⰍ㐣⛬࡜ྜᡂ
ࢆࡋࡤࡽࡃᨺ⨨ࡍࡿ࡜㸪ࡺࡗࡃࡾ࡜㏥Ⰽࡀ㉳ࡁࡿࡇ࡜ࡀศ࠿
ᐇ㦂᪉ἲ
ࣉ࣮ࣞ࢝ࢧ࣮࡜ࡋ࡚ p-࢔࣑ࣀࣇ࢙ࣀ࣮ࣝㄏᑟయࡢ P-1a-d
ࡗࡓࠋᅗ 3 ࡟♧ࡍ P-1a ࡜ C-3d ࡛ࡢ཯ᛂ࡛ࡣ㸪㛤ጞ࠿ࡽ 50
ࢆ㸪࢝ࢵࣉ࣮ࣛ࡟ࡣ ࢼࣇࢺ࣮ࣝㄏᑟయ C-1a㸪b ࡜ m-࢔࣑
ศ⤒㐣ࡋࡓ᫬Ⅼ࡛ λmax ࡀపἼ㛗⛣ືࡋ㸪ⴭࡋ࠸྾ගᗘࡢప
ࣀࣇ࢙ࣀ࣮ࣝㄏᑟయ C-2a㸪b㸪ࣞࢰࣝࢩࣥㄏᑟయ C-3a-d ࢆ
ୗࡀぢࡽࢀࡓࠋࡇࢀࡣ╔Ⰽ≀ࡀࡺࡗࡃࡾ࡜ศゎࡋ࡚࠸ࡿࡇ࡜
⏝࠸ࡓࠋ
ࢆ♧ࡋ࡚࠸ࡿࠋ
1a:X, Y=H
1b:X=Me, Y=H
1d:X=Cl, Y=H
1c:X=H, Y=Me
྾
ග
ᗘ
P
1a:X=H
2a:X=H
1b:X=OH
2b:X=Me
(nm)
ᅗ 3D㸭&G ΰྜ⣔ࡢⓎⰍ࡜㏥Ⰽ
3a:X, Y, Z=H
3b:X, Y=H, Z=Me
>3@㸪>&G@ ™0
3c:X=H, Y=Me, Z=H
3d:X=Cl, Y, Z=H
C
➼ࣔࣝ⃰ᗘࡢࣉ࣮ࣞ࢝ࢧ࣮㸦P㸧࡜࢝ࢵࣉ࣮ࣛ㸦C㸧ࢆ
ⓎⰍᚋ࡟㏥Ⰽࡀ㉳ࡇࡿཎᅉࡀⓎⰍ㐣⛬࡛ᚲせ࡞࢔ࣝ࢝ࣜ
๣ࡢ࢔ࣥࣔࢽ࢔࡟࠶ࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼㸪࢔ࣝ࢝ࣜ๣ࢆⅣ
㓟ࢼࢺ࣒ࣜ࢘࡟ኚ࠼࡚ᐇ㦂ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝ㸪≉࡟㏥Ⰽࡀ
EtOH㸸Ỉ㸻1㸸1 ࡢ⁐፹୰࡛㸪✵Ẽ㓟໬࡟ࡼࡾⓎⰍࡉࡏࡓࠋ
ぢࡽࢀࡓࣞࢰࣝࢩࣥ㢮࡛ࡢ㏥Ⰽࢆᢚไࡍࡿࡇ࡜ࡀ࡛ࡁࡓࠋ౛
࢔ࣝ࢝ࣜ๣࡟ࡣ࢔ࣥࣔࢽ࢔Ỉࢆ⏝࠸㸪⁐ᾮ඲యࢆ pH9 ࡜ࡋ
࠼ࡤ㸪ᅗ 4 ࡟♧ࡋࡓ P-1 ࡜ C-3d ࡢ཯ᛂ࡛ࡣ㏥Ⰽࡀᢚไࡉࢀ㸪
ࡓࠋ200-700nm ࡢ྾཰ࢫ࣌ࢡࢺࣝࢆศගගᗘィ࡛㐺ᐅ᫬㛫
NH3 ࡛ࡢ཯ᛂ࡛ λmax ࡢ྾ගᗘࡣ᭱኱࡛ࡶ 0.49 ࡛࠶ࡗࡓࡢ࡟
⤒㐣ࡈ࡜࡟ ᐃࡋࡓࠋࡲࡓ㸪࢔ࣝ࢝ࣜ๣ࢆⅣ㓟ࢼࢺ࣒ࣜ࢘Ỉ
ᑐࡋ㸪Ⅳ㓟ࢼࢺ࣒࡛ࣜ࢘ࡢᐇ㦂࡛ࡣ 0.74 ࡲ࡛ୖ᪼ࡋࡓࠋࡲ
⁐ᾮ࡟ኚ᭦ࡋࡓᐇ㦂ࡶ⾜ࡗࡓࠋ
ࡓ㸪཯ᛂ㛤ጞ࠿ࡽ 5h ⤒㐣ࡋ࡚ࡶ඲ࡃ㏥Ⰽࡣ㉳ࡇࡽ࡞࠿ࡗࡓࠋ
㓟໬ᰁᩱࡢྜᡂࡣ㸪ࣉ࣮ࣞ࢝ࢧ࣮㸦P㸧࡜࢝ࢵࣉ࣮ࣛ
生活環境学研究 No.3
44 2015
㏥Ⰽࡀᢚไ࡛ࡁࡓせᅉࡣⅣ㓟ࢼࢺ࣒ࣜ࢘ࡢỈ⁐ᾮ୰ࡢ OH-࡟
ࡼࡿồ᰾཯ᛂ࡟ࡼࡿศゎࡀ㸪࢔ࣥࣔࢽ࢔࡟ࡼࡿồ᰾཯ᛂ࡟ࡼ
ࣝࢡ࣐ࣟࢺࢢࣛࣇࢆ⾜ࡗࡓࡀ⏕ᡂ≀ࡀᏳᐃ࡛࡞ࡃࢡ࣐ࣟࢺࢢ
ࡿศゎࡼࡾࡺࡿࡸ࠿࡟㉳ࡇࡿࡓࡵ࡛ࡣ࡞࠸࠿࡜᥎ ࡋ࡚࠸ࡿࠋ ࣛࣇ࢕࣮୰࡟ศゎࡋ࡚ࡋࡲࡗࡓࡢ࡛Ᏻᐃ໬ࡢࡓࡵ࡟ΰྜ≀ࡢ
≧ែ࡛࢔ࢭࢳࣝ໬ࢆ⾜ࡗࡓࠋ཯ᛂᚋࡢ⁐ᾮࡣ࢚ࣂ࣏࣮ࣞࢱ࣮
࡛⃰⦰ᚋ㸪TLC ࡟ࡼࡾᶳ࡜㯤ࡢ 2 ࡘࡢࢫ࣏ࢵࢺࢆ☜ㄆࡋ㸪
྾
ග
ᗘ
ࢡ࣐ࣟࢺࢺࣟࣥ࡟ࡼࡾ⏕ᡂ≀ In-g㸪In-i ࢆศ㞳ࡋࡓࠋᶳࡢ⏕
ᡂ≀ In-g ࡣ 1H-NMR ࡟࠾࠸࡚ δ2.23㸦s㸧
㸪δ2.25㸦s㸧࡟࢔
ࢭࢳࣝᇶࡢࣉࣟࢺࣥࡀྛ 3 ಶศ☜ㄆ࡛ࡁ㸪ࣇ࢙ࢽࣝࣉࣟࢺࣥ
ࡣ 12 ಶศ࠶ࡿࡇ࡜MS m/z M㸩=440 ࡛࠶ࡿࡇ࡜࠿ࡽ P-1a
2 ศᏊࡀ C-1a 1 ศᏊ࡜཯ᛂࡋࡓᵓ㐀࡛࠶ࡿ࡜᥎ᐃࡋࡓࠋ13CNMR ཬࡧඖ⣲ศᯒࡶ᥎ᐃࡢᵓ㐀ࢆᨭᣢࡋ࡚࠸ࡿࠋ୍᪉㸪㯤
㸪2.47㸦s㸧࡟
ࡢ⏕ᡂ≀ In-i ࡣ 1H-NMR ࡟࠾࠸࡚ δ2.28㸦s㸧
(nm)
࢔ࢭࢳࣝᇶࡢࣉࣟࢺࣥࡀྛ 3 ಶศ☜ㄆ࡛ࡁ㸪ࣇ࢙ࢽࣝࣉࣟࢺ
ᅗ 3D㸭&G ΰྜ⣔ࡢⓎⰍ࡜㏥Ⰽ
ࣥࡣ 14 ಶศ࠶ࡿࡇ࡜㸪MS m/z M㸩=476 ࡛࠶ࡿࡇ࡜࠿ࡽࡇ
>3@㸪>&G@ ™0
ࡢ⏕ᡂ≀ࡣ P-1a 1 ศᏊ࡜ C-1a 2 ศᏊࡀ཯ᛂࡋ࡚࠸ࡿ࡜᥎ᐃ
ࡋࡓࠋ13C-NMR ཬࡧඖ⣲ศᯒࡶᵓ㐀ࢆᨭᣢࡋ࡚࠸ࡿࠋIn-a-
P-1b-d ࡜㸪ྛ࢝ࢵࣉ࣮ࣛ࡜ࡢⓎⰍ࡟ࡼࡿ྾཰ࢫ࣌ࢡࢺࣝ
e㸪In-g㸪In-i ࡢ࠸ࡎࢀࡶ㸪ศᏊෆ࡟࢟ࣀࣥࣔࣀ࢖࣑ࣥࡢ㦵
ࡶྠᵝ࡟㏣㊧ࡋࡓࠋP-1b-c ࡜ྛ࢝ࢵࣉ࣮ࣛ࡟ࡼࡿⓎⰍࡣ P-
᱁ࢆᣢࡘ࢟ࣀࣥ࢖࣑ࣥᆺᰁᩱ࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓ㸪
1a ࡟ࡼࡿⓎⰍ࡜ྠᵝ࡟ྍど㒊࡟኱ࡁ࡞྾཰ࢆ♧ࡋ㸪ࡑࡢ
P-1a ࡜ C-1a ࡢⓎⰍ⏕ᡂ≀ࡣ㸪ᩥ⊩ 4)࡛ᥦၐࡉࢀ࡚࠸ࡓࣉࣞ
λmax ࡣ⨨᥮ᇶຠᯝ࡛ 23nm~35nm ⛬ᗘ㛗Ἴ㛗ഃ࡟⛣ືࡋࡓࠋ
࣮࢝ࢧ࣮2 ศᏊ࡜࢝ࢵࣉ࣮ࣛ1 ศᏊࡢ 3 ᰾య㸦In-g㸧ࡢࡳ࡛
C-2b ࢆ┬ࡁ㸪P-1b ࡼࡾ P-1c ࡢ᪉ࡀࡼࡾ㛗Ἴ㛗⛣ືࡍࡿഴ
ࡣ࡞ࡃ㸪࢝ࢵࣉ࣮ࣛ2 ศᏊ࡜ 1 ศᏊࡢ 3 ᰾య㸦In-i㸧ࡶ⏕ᡂ
ྥࡀぢࡽࢀࡓࠋ୍᪉㸪P-1d ࡟ࡼࡿⓎⰍࡣ㸪C-1a≏b≏C-2a≏
ࡍࡿࡇ࡜ࡀ᪂ࡓ࡟ศ࠿ࡗࡓࠋ௒ᚋࡣ㓟໬ᰁᩱ࡟ࡘ࠸࡚ࡶ㏥Ⰽ
b ࡜ࡢ⤌ࡳྜࢃࡏ࡛ࡣ λmax ࡣ 5~26nm ⛬ᗘ▷Ἴ㛗⛣ືࡋࡓࠋ
⏕ᡂ≀ࢆ༢㞳㸪ᵓ㐀ゎᯒࡋ᭦࡟⪃ᐹࢆ῝ࡵ࡚࠸ࡃࠋ
C-3a-d ࡜ࡢ⤌ࡳྜࢃࡏ࡛ࡣࢩࣙࣝࢲ࣮ࢆᣢࡘࢫ࣌ࢡࢺࣝᙧ
≧࡟࡞ࡗࡓࠋ౛࠼ࡤ C-3d ࡛ࡣࢩ࣮ࣕࣉ࡞ λmax =587nm ࡢ྾
O
AcO
཰࡜࡜ࡶ࡟㸪550nm ௜㏆࡟ࢩࣙࣝࢲ࣮ࡀ☜ㄆ࡛ࡁࡿࠋࡲࡓ㸪
P-1a-c ࡛ࡣⓎⰍࡀࡳࡽࢀ࡞࠿ࡗࡓ C-3c ࡜ࡢ⤌ࡳྜࢃࡏ࡛ࡶ
O
N
ⓎⰍࡋࡓࠋࡲࡓ㸪P-1d ࡜ C-3a-d ࡟ࡼࡿⓎⰍࡣ⺯ගࢆᣢࡗ࡚
N
H
OAc
N
࠸ࡓࠋ
OAc
㓟໬ᰁᩱࡢⓎⰍ⏕ᡂ≀ࡢ༢㞳࡟ࡣ࢔ࣝ࢝ࣜᛶ཯ᛂ⁐ᾮࢆ୰
ᛶ࡟ࡍࡿᚲせࡀ࠶ࡿࡓࡵ㸪ⓎⰍࡉࡏࡓ⁐ᾮࡢ pH ࡢኚ໬࡟ࡼ
g OAc
i
In
ࡿᏳᐃᛶࢆㄪ࡭ࡓࠋࡑࡢ⤖ᯝ㸪pH ࡢኚ໬࡟ᑐࡋ࡚ẚ㍑ⓗᏳ
ᐃ࡛࠶ࡗࡓ P-1a-d/C-2b㸪࠶ࡿ࠸ࡣ P-1a㸭C-1a ࡜ࡢ⤌ࡳྜ
ࢃࡏ࡛ᚓࡽࢀࡿⓎⰍ⏕ᡂ≀࡟ࡘ࠸࡚㸪ⓎⰍ⏕ᡂ≀ࡢ༢㞳ࢆヨ
ཧ⪃ᩥ⊩
ࡳࡓࠋC-2b ࡜ྛ p-࢔࣑ࣀࣇ࢙ࣀ࣮ࣝㄏᑟయࡢ⏕ᡂ≀࡟ࡘ࠸
1) K.Seguchi, M.Iwata, T.Machida, S.Tanaka, J.Soc.
࡚ࡣ TLC ࡟ࡼࡾᶳࡢ 1 Ⅼࡢࢫ࣏ࢵࢺࡀ☜ㄆࡉࢀࡓࡢ࡛
Dyers&Colour., 116, 16-22 (2000)
MeOH ࡛෌⤖ᬗᚋ㸪NMR ➼࡟ࡼࡿᶵჾศᯒࢆ⾜ࡗࡓࠋࡑࡢ
2) N.Itoh, S.Tanaka, K.Seguchi, Bull. Mukogawa Women’s Univ.
⤖ᯝ C-2b ࡜ P-1a-d ࡢ⏕ᡂ≀ࡣ඲࡚ࣉ࣮ࣞ࢝ࢧ࣮࡜࢝ࢵࣉ
Nat.Sci., 54, 13-18 (2006)
࣮ࣛࡀ 1 ศᏊࡎࡘ཯ᛂࡋࡓ࢖ࣥࢻࣇ࢙ࣀ࣮ࣝㄏᑟయ㸦In-a-
3) S.Abe, K.Seguchi, Anal. Sci., 23, x7-x8 (2007)
d㸧࡛࠶ࡿࡇ࡜ࡀศ࠿ࡗࡓࠋࡲࡓ㸪In-d ࢆ࢔ࢭࢳࣝ໬ࡍࡿ࡜
4)C. R. Robbins,ᒣཱྀ┿୺ヂࠕẟ㧥ࡢ⛉Ꮫࠖ 355-393 (2006)
In-e ࡀ 60%ࡢ཰⋡࡛ᚓࡽࢀࡓࠋ
5) IR,NMR,MS ゎᯒR.M.Silverstein, G.C.Bassler, T.C.Morrill,
O
Me
Ha
Hb
NH2
N
X
Y
Ⲩᮌಇヂࠕ᭷ᶵ໬ྜ≀ࡢࢫ࣌ࢡࢺࣝ࡟ࡼࡿྠᐃἲ➨ ∧ࠖᮾி໬
a:X, Y,=H, Z=OH
b:X=Me, Y=H, Z=OH
c:X=H, Y=Me, Z=OH
Ꮫྠே (1976)
d:X=Cl, Y=H, Z=OH
e: X=Cl, Y=H, Z=OAc
Z
In
C-1a㸭P-1a ࡢ⏕ᡂ≀ࡣ TLC㸦CH2Cl2㸭㓑㓟࢚ࢳࣝ㸧࡟ࡼ
ࡾ 2 Ⅼࡢࢫ࣏ࢵࢺࡀ☜ㄆࡉࢀࡓࡢ࡛㸪༢㞳ࡢࡓࡵ࡟ࢩࣜ࢝ࢤ
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