࢟ࣀ࣑ࣥࣥᆺᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయࡼࡿ㑏ඖ ᪥⨨⌮ 㹙ᣦᑟᩍဨ㸸ṊᗜᕝዪᏊᏛᩍᤵ ℩ཱྀ⩏㹛 ࣮࣮࢟࣡ࢻ㸸ࢰᰁᩱ㸪㓟ᰁᩱ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ㸪㏥Ⰽ⏕ᡂ≀㸪㑏ඖ ⤖ᯝ⪃ᐹ ⥴ゝ ⏕άࡢ୰ࡣᵝࠎ࡞㑏ඖᛶྜ≀ࡀ࠶ࡿࠋ㑏ඖᛶྜ≀ࡣ㸪 Dye-1a ࡘ࠸࡚ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟⃰ᗘ 103 ಸ㸪50Υࡢ᮲ Ⰽ⣲ᛂࡋ࡚ኚ㏥Ⰽࡸ⬺Ⰽ࠸ࡗࡓ⌧㇟ࢆ㉳ࡇࡍࡇࡀ࠶ ௳࡛྾ࢫ࣌ࢡࢺࣝࡢኚࢆࡳࡿ㸪ྍど㒊 λmax=530nm ࡢ ࡿࠋࡋࡋᰁᩱࡀ㑏ඖᛶྜ≀ࡼࡗ࡚ࡢࡼ࠺ኚࡋ㸪 ྾ࡀ㛫ࡶపୗࡋ㸪8 㛫ᚋࡣ㏥Ⰽࡋࡓ㸦ᅗ 1㸧 ࠋ ኚ㏥Ⰽࢆ㉳ࡇࡍࡢࡘ࠸࡚᫂ࡽࡋࡓ◊✲ࡣࡁࢃࡵ࡚ᑡ ࡞ࡃ㸪᥎ ࡢᇦ␃ࡲࡿࡶࡢࡶᑡ࡞ࡃ࡞࠸ࠋ ᮏ◊✲ᐊ࡛ࡣ⏕άࡢ୰ࡢ≀㉁ᨭࡘ࠸᳨࡚ウࡀຍ࠼ࡽࢀ ࡚ࡁࡓ 1-3)ࠋᮏ◊✲࡛ࡣ㸪㑏ඖᛶྜ≀ࡋ࡚ࣃ࣮࣐ᾮࡸࢩ Dye-1b㸪Dye-1e ࡘ࠸࡚ࡶྠᵝྍ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 ẚ࣑ ࣟࢭࢵࢺຍᕤ⏝࠸ࡽࢀࡿࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయ㸪ᰁᩱ ࣀᇶࡢሷᇶᛶࡀᙅ࠸ࡇ㉳ᅉࡍࡿ᥎ ࡉࢀࡿࠋDye-1d ࡣ࢟ࣀ࣑ࣥࣥᆺᰁᩱ࡛࠶ࡿࢰᰁᩱཬࡧᰁẟ⏝࠸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 ศ࡛ࡰ㏥Ⰽࡀࡋࡓࠋ1d ࡢ㏥Ⰽ ࡔࡅࡀ␗ᖖ㏿ࡃ㸪ࡢᰁᩱࡣ㏥Ⰽࡢ࣓࢝ࢽࢬ࣒ࡀࡁࡃ ࢭࢫࢆ᫂ࡽࡍࡿࡇࢆヨࡳࡓࠋ ࣑ࣀࢰᰁᩱࡘ࠸࡚ࡣࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయࡼࡿ ␗࡞ࡿྍ⬟ᛶࡀ࠶ࡿࠋ ㏥Ⰽࢫ࣌ࢡࢺࣝࡢ ᐃ㸪㏥Ⰽ⏕ᡂ≀ࡢ༢㞳ᵓ㐀Ỵᐃࢆ⾜࠸㸪 ⏕ᡂ≀ࡣ༢ࢰᇶࡢ㑏ඖศゎࡼࡿࡶࡢ࡛ࡣ࡞ࡃࢳ࢜ࢢࣜ ྾ ග ᗘ ࢥ࣮ࣝ㓟ࡀᵓ㐀⤡ࢇࡔ」㞧࡞ຍ≀ኚࡋ࡚࠸ࡿࡇࢆ ᫂ࡽࡋࡓࠋ㓟ᰁᩱࡘ࠸࡚ࡣᏳᐃᛶࡢḞዴࡽࡑࡢᵓ 㐀ࡘ࠸࡚ࡣ᪥࡛ࡶ᭕࡞ࡇࢁࡀ࠶ࡿࡢ࡛㸪ᅇ᪂ࡓ ྜᡂᣮᡓࡋࡓࠋලయⓗࡣ㸪㓟ᰁᩱࡢⓎⰍࢫ࣌ࢡࢺࣝࡢ ᐃⓎⰍ⏕ᡂ≀ࡢ༢㞳ࢆ⾜ࡗࡓࠋ ࣑ࣀࢰᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡼࡿ㏥Ⰽࢫ࣌ࢡࢺࣝ ࡢኚ ᐇ㦂᪉ἲ (nm) ᅗ '\HD ࡢ㏥Ⰽࢫ࣌ࢡࢺࣝࡢኚ㸦Υ㸧 ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡢࢰᰁᩱࡢ㏥Ⰽᛶࢆ᳨ウࡍࡿࡓࡵ㸪 ࣑ࣀࢰᰁᩱࡋ࡚ 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- ࣑ࣀࢰᰁᩱࡢࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయࡼࡿ㏥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ㄏᑟయࡣ 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 ᛂࡉࡏࡓࠋᰁᩱࡢⰍࡢᾘኻᚋຍ⇕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⣲ศᯒࡼࡾ ᵓ㐀ࢆỴᐃࡋࡓࠋ 生活環境学研究 No.3 42 2015 Dye-1a 2b ࡢᛂ࡛ࡣ㸪2b ࡢ 2 ศᏊຍ⎔≀㸦6a㸧 ⤖ᯝ⪃ᐹ Dye-1a 2a ࡢᛂ࡛ࡣ㸪ΰྜᾮࢆຍ⇕㑏ὶࡍࡿᰁᩱ 㸦⋡ 25%㸧 㸪 1 ศᏊຍ⎔≀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 ࡢᛂ࠾࠸࡚ࡶ㸪㏥ Ẋࡀ⏕ࡌࡓࠋᚓࡽࢀࡓ⏕ᡂ≀ࡣ㸪1H-NMR㸦DMSO-d6㸧 Ⰽ⏕ᡂ≀ࡣᑐᛂࡍࡿ 1 ศᏊຍ⎔≀ 2 ศᏊຍ⎔≀ࡢ ࠾࠸࡚ δ=3.03㸦s㸧࣓ࢳࣞࣥࣉࣟࢺࣥ 㸦CH2㸧 㸪10.30 ୧᪉㸪ࡲࡓࡣ 1 ศᏊຍ⎔≀ࡢࡳࡀ⏕ࡌࡓࠋDye-1d 2b 㸦s㸧Ỉ⣲ ಶศࡢ࣑ࢻࣉࣟࢺࣥ 㸦NHC=O㸧ࡀࡳࡽࢀ ࡢᛂ࡛ࡣ㸪⨨య 6d ࡀ⋡ 38%࡛⏕ᡂࡋࡓࠋࡲࡓ Dye- ࡿࡇࡽ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟 2 ศᏊࡀᰁᩱຍ⎔ࡋ࡚ 1e-g 2b㸪2c ࡢᛂ࡛ࡶᑐᛂࡍࡿ 1 ศᏊຍ⎔≀㸪2 ⏕ࡌࡓ⎔≧࣑ࢻㄏᑟయ㸦3a㸧࡛࠶ࡿ᥎ᐃࡋࡓ㸦⋡ ศᏊຍ⎔≀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 ಶศࡢ࣑ࢻࣉࣟࢺࣥࡀᏑᅾࡍࡿࡇࡽ㸪ࢳ࢜ࢢࣜࢥ࣮ࣝ 6 㓟ࡀᰁᩱ 1 ศᏊຍ⎔ࡋ࡚࡛ࡁࡓ⎔≧࣑ࢻㄏᑟయ 㸪IR ࡶࡇ 㸦4a㸧࡛࠶ࡿ᥎ᐃࡋࡓࠋ13C-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 ศᏊຍ⎔≀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 ศᏊຍ⎔≀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 ศᏊຍ⎔≀㸦4c㸧ࡢࡳࡀ 67%ࡢ⋡࡛ᚓ 6d ࡽࢀࡓࠋ ᛂᚋࡢΰྜ≀ࡢ 1H-NMR ࡢ NH ࡢࣆ࣮ࢡࡢ✚ศẚࡼ R1 O R1 N N a:R1=H, R2=H S S S ࡾ Dye-1a-c㸪Dye-1e-g ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ㄏᑟయࡢᛂ R2 O 3 4 2 b:R =H, R =Me c:R1=H, R2=Ph HN HN 1 O Dye-1d ࡘ࠸࡚ 2a ࢆῧຍᚋຍ⇕㑏ὶࡍࡿᰁᩱࡼࡿ ࠾ࡅࡿ 1 ศᏊຍ⎔≀㸪2 ศᏊຍ⎔≀ࡢ⏕ᡂࡢྜ ࢆ⟬ฟࡋࡓ⤖ᯝࢆ⾲ 1 ♧ࡍࠋ࣑ࣀᇶ㒊ศࡢ⨨ᇶࡢࡉ ࡀ㧗ࡃ࡞ࡿ㸦H→Me→Ph㸧2 ศᏊຍ≀ࡀ⏕ᡂࡋࡃ ࠸ഴྥࢆ♧ࡋࡓࠋ ⾲ ㏥Ⰽ≀ࡢ⏕ᡂẚ㸦 ศᏊຍయ㸸 ศᏊຍయ㸧 ㉥Ⰽࡢ࿊Ⰽࡀ 5h ࡛ᶳⰍኚࡋ㸪ࡑࢀ௨ୖࡢ㏥Ⰽࡣㄆ ࡵࡽࢀ࡞ࡗࡓࠋỈࢆຍ࠼࡚ᚓࡽࢀࡓῐᶳⰍࡢ⏕ᡂ≀ 5d ࡣ㸪 1H-NMR ࠾࠸࡚ Dye-1d ࡢࢪ࣓ࢳ࣑ࣝࣀࣉࣟࢺࣥࡀᾘኻ ࡋ㸪௦ࢃࡾ δ=3.83㸦s㸧࣓ࢳࣞࣥࣉࣟࢺࣥ㸦CH2㸧 㸪ࣇ ࢙ࢽࣝࣉࣟࢺࣥࡀ 11 ಶศᏑᅾࡍࡿࡇࡽ㸪ࢳ࢜ࢢࣜࢥ࣮ ࣝ㓟ࡀᰁᩱࡢࢪ࣓ࢳ࣑ࣝࣀᇶ⨨ࡋ࡚⏕ࡌࡓ≀㉁㸦5d㸧 ࡛࠶ࡿࡇࡀศࡗࡓ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 ࡢᛂ࡛ࡣ㸪ࢰᆺࡢኚ␗ᛶయࡢࣄࢻࣛࢰࣥᆺ㸪ࡘ ࡲࡾ࢟ࣀࣥࢪ࣑ࣥᆺࡢᰁᩱࡢ㔜⤖ྜ㒊ศࡢ 3 ࡲࡎࢳ ࣮࢜ࣝࡀ࣐ࢣࣝຍࢆ㉳ࡇࡍࠋศᏊෆ࡛⬺Ỉࡼࡾ⎔ࡋ㸪 2 ࡶ࠺ 1 ศᏊࡢࢳ࣮࢜ࣝࡀ࣐ࢣࣝຍᚋ㸪ศᏊෆ⬺Ỉ Dye-1e ࢳ࢜ࢢࣜࢥ࣮ࣝ㓟ࡢᛂ࡛ࡣ㸪1 ศᏊຍ⎔ ࡋ࡚⎔ࡋࡓࡶࡢࡣ 2 ศᏊ⎔ຍ≀㸦3㸧㸪 N 㒊ศ ≀㸦4a㸧ࢆ 35%㸪2 ศᏊຍ⎔≀㸦3a㸧ࢆ 9%ࡢ⋡࡛ᚓ ຍᚋຍỈศゎࢆ㉳ࡇࡍ 1 ศᏊຍ⎔≀㸦4㸧࡞ࡿ᥎ ࡓࠋDye-1f ࡘ࠸࡚ࡶ 1 ศᏊຍ⎔≀㸦4b㸧ࢆ 40%㸪2 ࡋ࡚࠸ࡿࠋ ศᏊຍ⎔≀㸦3b㸧ࢆ 15%ࡢ⋡࡛ᚓࡓࠋDye-1g ࡘ࠸ ࡇࡢࡁ㸪 Dye-1c㸪1g ࡣ⨨ᇶࡢࡉࡀࡁࡍࡂ࡚㸪2 ࡚ࡶ Dye-1c ྠࡌࡼ࠺ 1 ศᏊຍ⎔≀㸦4c㸧ࡢࡳࢆ 2 ศᏊ┠ࡢࢳ࣮࢜ࣝ㢮ࡀຍࡉࢀࡃࡃᛂࡀ 1 ศᏊ 67%ࡢ⋡࡛ᚓࡓࠋDye-1h ࡘ࠸࡚ࡣ⏕ᡂ≀ࡢ༢㞳ࢆヨࡳ ຍ⎔㐍ࡴࡶࡢᛮࢃࢀࡿࠋ࣑ࣀᇶࡢỈ⣲ 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 ศᏊຍ⎔≀ࡢ⏕ᡂࡢྜࡀᑡ࡞࠸⌮⏤ࡶྠᵝ⪃࠼ࡽ ࡢ⨨⏕ᡂ≀ 5h ࡀ⏕ᡂࡋ࡚࠸ࡿ᥎ ࡋࡓࠋ ࢀࡿࠋ 生活環境学研究 No.3 2015 43 Dye-1d ࡛ࡣ㸪ࢳ࣮࢜ࣝ㢮ࡀᰁᩱࡢࢪ࣓ࢳ࣑ࣝࣀᇶ⨨ 㸦C㸧ࢆ➼ࣔࣝ㔞㸦1.010-4mol㸧ࢆ EtOH㸸Ỉ㸻1㸸1 ࡢ⁐ ࡋࡓ⏕ᡂ≀ࡀᚓࡽࢀࡓࠋࡇࡢᛂࡣᛂࡢ㏿ࡉࡽࡶศ ፹ 40ml ୰⁐ࡋ㸪Ⅳ㓟ࢼࢺ࣒࡛ࣜ࢘ pH9 ㄪ〇ࡋ㸪⁐ ࡿ㏻ࡾ㸪ࢪ࣓ࢳ࣑ࣝࣀᇶࡢ⬺㞳ᇶࡢࡋࡸࡍࡉࡀ࠶ࡿࡢ࡛㸪 ᾮ✵Ẽࢆ࣏ࣥࣉ࡛㏦ࡾ࡞ࡀࡽ✵Ẽ㓟ࡼࡾᩘ㛫ᛂࡉ ๓㏙ࡢຍ⎔ࡼࡾ㏿ࡸ㉳ࡇࡿࡶࡢᛮࢃࢀࡿࠋຍ⎔ ࡏࡓࠋᛂᚋࡣ⁐ᾮࢆ୰ᛶࡋ㸪ỿẊࡋࡓ㓟ᰁᩱࢆᚓࡓࠋ ᛂࡼࡾ⨨ᛂࡀ㏿ࡸ㉳ࡇࡾ㸪⨨యࢆ⏕ࡌࡓᛮ ⓎⰍ⏕ᡂ≀ࡢ༢㞳㸪⢭〇ࡣ㸪P-1a-d㸭C-2b ࡢ⤌ࡳྜࢃࡏ ࢃࢀࡿࠋ ࡘ࠸࡚ࡣᛂ⁐ᾮࢆ࢚ࣂ࣏࣮ࣞࢱ࣮ࡼࡾ⃰⦰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⣲ศᯒࡼࡾᵓ㐀ࢆỴᐃࡋࡓࠋࡲࡓ㸪୍㒊ࡢ㓟 ᰁᩱࡘ࠸࡚ࡣ↓Ỉ㓑㓟ࣆࣜࢪࣥࡼࡿࢭࢳࣝࡶ⾜ ࡗࡓࠋ ⤖ᯝ⪃ᐹ P-1a C-1a ࡢ⤌ࡳྜࢃࡏ࡛ࡣ㛫ࡢ⤒㐣ࡼࡾ 3 λmax=623nm ࡢ྾ࡀቑࡋ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ࡢᛂ࣓࢝ࢽࢬ࣒ 545nm, 530nm, 565nm ࡛⣸㹼㉥⣸Ⰽࡢ╔ⰍࡀぢࡽࢀࡓࠋC3c ࠾࠸࡚ࡣࢇ╔Ⰽࡀぢࡽࢀ࡞ࡗࡓࠋ ࡋࡋ C-3a㸪3b㸪3d ࡘ࠸࡚㸪╔Ⰽࡀ㉳ࡇࡗࡓᚋࡶ⁐ᾮ 㓟ᰁᩱࡢⓎⰍ㐣⛬ྜᡂ ࢆࡋࡤࡽࡃᨺ⨨ࡍࡿ㸪ࡺࡗࡃࡾ㏥Ⰽࡀ㉳ࡁࡿࡇࡀศ ᐇ㦂᪉ἲ ࣉ࣮ࣞ࢝ࢧ࣮ࡋ࡚ p-࣑ࣀࣇ࢙ࣀ࣮ࣝㄏᑟయࡢ P-1a-d ࡗࡓࠋᅗ 3 ♧ࡍ P-1a C-3d ࡛ࡢᛂ࡛ࡣ㸪㛤ጞࡽ 50 ࢆ㸪࢝ࢵࣉ࣮ࣛࡣ ࢼࣇࢺ࣮ࣝㄏᑟయ C-1a㸪b m-࣑ ศ⤒㐣ࡋࡓⅬ࡛ λmax ࡀపἼ㛗⛣ືࡋ㸪ⴭࡋ࠸྾ගᗘࡢప ࣀࣇ࢙ࣀ࣮ࣝㄏᑟయ C-2a㸪b㸪ࣞࢰࣝࢩࣥㄏᑟయ C-3a-d ࢆ ୗࡀぢࡽࢀࡓࠋࡇࢀࡣ╔Ⰽ≀ࡀࡺࡗࡃࡾศ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࡞ࣝ࢝ࣜ ࡢࣥࣔࢽ࠶ࡿࡢ࡛ࡣ࡞࠸⪃࠼㸪ࣝ࢝ࣜࢆⅣ 㓟ࢼࢺ࣒ࣜ࢘ኚ࠼࡚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㏥Ⰽࢆᢚไࡍࡿࡇࡀ࡛ࡁࡓࠋ ࣝ࢝ࣜࡣࣥࣔࢽỈࢆ⏝࠸㸪⁐ᾮయࢆ pH9 ࡋ ࠼ࡤ㸪ᅗ 4 ♧ࡋࡓ P-1 C-3d ࡢᛂ࡛ࡣ㏥Ⰽࡀᢚไࡉࢀ㸪 ࡓࠋ200-700nm ࡢ྾ࢫ࣌ࢡࢺࣝࢆศගගᗘィ࡛㐺ᐅ㛫 NH3 ࡛ࡢᛂ࡛ λmax ࡢ྾ගᗘࡣ࡛᭱ࡶ 0.49 ࡛࠶ࡗࡓࡢ ⤒㐣ࡈ ᐃࡋࡓࠋࡲࡓ㸪ࣝ࢝ࣜࢆⅣ㓟ࢼࢺ࣒ࣜ࢘Ỉ ᑐࡋ㸪Ⅳ㓟ࢼࢺ࣒࡛ࣜ࢘ࡢᐇ㦂࡛ࡣ 0.74 ࡲ࡛ୖ᪼ࡋࡓࠋࡲ ⁐ᾮኚ᭦ࡋࡓᐇ㦂ࡶ⾜ࡗࡓࠋ ࡓ㸪ᛂ㛤ጞࡽ 5h ⤒㐣ࡋ࡚ࡶࡃ㏥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᰾ᛂࡼࡿศゎࡀ㸪ࣥࣔࢽࡼࡿồ᰾ᛂࡼ ࣝࢡ࣐ࣟࢺࢢࣛࣇࢆ⾜ࡗࡓࡀ⏕ᡂ≀ࡀᏳᐃ࡛࡞ࡃࢡ࣐ࣟࢺࢢ ࡿศゎࡼࡾࡺࡿࡸ㉳ࡇࡿࡓࡵ࡛ࡣ࡞࠸᥎ ࡋ࡚࠸ࡿࠋ ࣛࣇ࣮୰ศゎࡋ࡚ࡋࡲࡗࡓࡢ࡛Ᏻᐃࡢࡓࡵΰྜ≀ࡢ ≧ែ࡛ࢭࢳࣝࢆ⾜ࡗࡓࠋᛂᚋࡢ⁐ᾮࡣ࢚ࣂ࣏࣮ࣞࢱ࣮ ࡛⃰⦰ᚋ㸪TLC ࡼࡾᶳ㯤ࡢ 2 ࡘࡢࢫ࣏ࢵࢺࢆ☜ㄆࡋ㸪 ྾ ග ᗘ ࢡ࣐ࣟࢺࢺࣟࣥࡼࡾ⏕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࠶ࡿࡇMS m/z M㸩=440 ࡛࠶ࡿࡇࡽ P-1a 2 ศᏊࡀ C-1a 1 ศᏊᛂࡋࡓᵓ㐀࡛࠶ࡿ᥎ᐃࡋࡓࠋ13CNMR 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 ࡛࠶ࡿࡇࡽࡇ >3@㸪>&G@ 0 ࡢ⏕ᡂ≀ࡣ P-1a 1 ศᏊ C-1a 2 ศᏊࡀᛂࡋ࡚࠸ࡿ᥎ᐃ ࡋࡓࠋ13C-NMR ཬࡧඖ⣲ศᯒࡶᵓ㐀ࢆᨭᣢࡋ࡚࠸ࡿࠋIn-a- P-1b-d 㸪ྛ࢝ࢵࣉ࣮ࣛࡢⓎⰍࡼࡿ྾ࢫ࣌ࢡࢺࣝ e㸪In-g㸪In-i ࡢ࠸ࡎࢀࡶ㸪ศᏊෆ࢟ࣀࣥࣔࣀ࣑ࣥࡢ㦵 ࡶྠᵝ㏣㊧ࡋࡓࠋP-1b-c ྛ࢝ࢵࣉ࣮ࣛࡼࡿⓎⰍࡣ P- ᱁ࢆᣢࡘ࢟ࣀ࣑ࣥࣥᆺᰁᩱ࡛࠶ࡿࡇࡀศࡗࡓࠋࡲࡓ㸪 1a ࡼࡿⓎⰍྠᵝྍ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 ศᏊ࢝ࢵࣉ࣮ࣛ1 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≏ ࡍࡿࡇࡀ᪂ࡓศࡗࡓࠋᚋࡣ㓟ᰁᩱࡘ࠸࡚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ࡣࣝ࢝ࣜᛶᛂ⁐ᾮࢆ୰ ᛶࡍࡿᚲせࡀ࠶ࡿࡓࡵ㸪ⓎⰍࡉࡏࡓ⁐ᾮࡢ pH ࡢኚࡼ g OAc i In ࡿᏳᐃᛶࢆㄪࡓࠋࡑࡢ⤖ᯝ㸪pH ࡢኚᑐࡋ࡚ẚ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≀ࡣ࡚ࣉ࣮ࣞ࢝ࢧ࣮࢝ࢵࣉ Nat.Sci., 54, 13-18 (2006) ࣮ࣛࡀ 1 ศᏊࡎࡘᛂࡋࡓࣥࢻࣇ࢙ࣀ࣮ࣝㄏᑟయ㸦In-a- 3) S.Abe, K.Seguchi, Anal. Sci., 23, x7-x8 (2007) d㸧࡛࠶ࡿࡇࡀศࡗࡓࠋࡲࡓ㸪In-d ࢆࢭࢳࣝࡍࡿ 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᭷ᶵྜ≀ࡢࢫ࣌ࢡࢺࣝࡼࡿྠᐃἲ➨ ∧ࠖ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ࡢࡓࡵࢩࣜ࢝ࢤ 生活環境学研究 No.3 2015 45
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