ᚑくᄢቇℂᎿቇ⎇ⓥႎ๔
J. Fac. Sci. Tech., Seikei Univ.
Vol.47 No.2 (2010) pp.41-48
㧔․೎⎇ⓥ⾌ߦଥࠆ⺰ᢥ㧕Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ⊒శㇱ૏ࠍᜰะߒߚ
ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ߩวᚑߣಽశቇ⊛․ᕈ⹏ଔ᧻᧛ ᦭㉿ሶ 㧘ᳯᧄ ᱜᄥ㇢ 㧘᫪↰ ⩿ᵤ⟤ ࡮ᩙ↰ ᕺテ Synthesis of Aminoquinoxaline Derivatives and Evaluation of Their
Photophysical Properties as Fluorophores for Fluorescent Thermosensors
Yuriko MATSUMURA㧖1, Shotaro EMOTO㧖2, Natsumi MORITA㧖3, Keisuke KURITA㧖4,
ABSTRACT㧦 Three kinds of 6-aminoquinoxalines bearing 4’-substituted phenyl group, two kinds of
1,4-benzoxazine-fused 8-aminoquinoxalines, and 1,4-benzothiazine-fused 8-aminoqunoxaline weresynthesized as a fluorophore for fluorescent thermosensors. All of the aminoquinoxalines showedpolarity-sensitive fluorescence and linear relationship between the fluorescence maximum wavelengthand dielectric constant of the solvent. These findings suggest that they were applicable as a fluorophore
for fluorescent thermosensors and 1,4-benzothiazine-fused 8-aminoqunoxaline was the most suitable ofthe six compounds.
Keywords㧦fluorescent thermosensor, quinoxaline derivative, fluorescent characteristics
㧔Received September 22, 2010㧕ߡએ᧪  㧘ࡍ࡝࡟ࡦߣࠫࡔ࠴࡞ࠕࡒࡁࡌࡦ࠯ࡦߣߩࠛࠠ

㧝㧚ߪߓ߼ߦ

ࠨࠗࡊ࡟࠶ࠢࠬ⊒శࠍ೑↪ߒߚ࠮ࡦࠨ࡯ ߿㊄ዻࠗࠝࡦ ↢๮⃻⽎ߩ⛽ᜬߦߪήᢙߩൻቇ෻ᔕ߇ଥߞߡ߅ࠅ㧘ߘ߿ࠕ࠾ࠝࡦ╬ߩࠗࠝࡦ⒳ࠍ↪޿ߡⰯశᒝᐲࠍᄌൻߐߖࠆ࠮

ߩ㊀ⷐߥ࿃ሶߩ৻ߟߣߒߡ‫ޟ‬᷷ᐲ‫߇ޠ‬⠨߃ࠄࠇࠆ੐߆ࠄ㧘ࡦࠨ࡯ 㧘Ǫгࠪࠢࡠ࠺ࠠࠬ࠻࡝ࡦߣࠫࡔ࠴࡞ࠕࡒࡁࡌࡦ࠱

ᦨㄭ㧘᷷ᐲࠍ᷹ቯኻ⽎ߣߔࠆⰯశᕈ࠮ࡦࠨ࡯ߦᵈ⋡߇㓸࠾࠻࡝࡞ߣߩ൮៨ൻว‛ࠍ೑↪ߒߡⰯశᒝᐲࠍᄌൻߐߖࠆ

߹ߞߡ޿ࠆ‫ޕ‬ታ㓙㧘ᱜᏱ⚦⢩ࠃࠅ≸⚦⢩ߩᣇ߇⚦⢩ౝߩ࠮ࡦࠨ࡯ ߇㐿⊒ߐࠇߡ߈ߡ޿ࠆ‫ߒ߆ߒޕ‬㧘ߎࠇࠄߩ࠮ࡦ

෻ᔕߩᵴᕈ߇㜞ߊ㧘ᾲ↢ᚑ߇ᄢ߈޿੐߇⍮ࠄࠇߡ޿ࠆ

‫ޕ‬ࠨ࡯ߪ᦭ᯏṁᇦਛߢߒ߆ᯏ⢻ࠍ␜ߐߥ޿ߛߌߢߥߊ㧘᷷ᐲߒ߆ߒ㧘⚦⢩ߪ 10 ޯ10 O ߶ߤߩᭂ߼ߡዊߐ޿ࠨࠗ࠭

ᄌൻߦኻߔࠆⰯశ․ᕈߩᄌൻ߇ዊߐ޿ߚ߼ߦࠊߕ߆ߥ᷷

ߢ޽ࠆߚ߼㧘ߎࠇ߹ߢߦ㐿⊒ߐࠇߚᣢሽߩ᷷ᐲ⸘ߢߪ⚦ᐲᄌൻࠍߣࠄ߃ࠆߎߣ߇࿎㔍ߢ޽ࠆߣ޿߁ᰳὐ߇޽ࠆ‫ޕ‬⢩ౝߩ᷷ᐲࠍ᷹ቯߔࠆ੐ߪ࿎㔍ߢ޽ࠆ‫ߢߎߘޕ‬ᵈ⋡ߐࠇ ߘߎߢ⠨᩺ߐࠇߚߩ߇ᗵ᷷ㇱ૏ߣ⊒శㇱ૏ߣࠍಽ㔌ߔࠆߩ߇ಽሶࠨࠗ࠭ࠝ࡯࠳࡯ߩⰯశᕈ࠮ࡦࠨ࡯ߢ޽ࠆ‫ޕ‬ࠆ᭎ᔨߢ޽ࠆ (KIWTG  ‫ޕ‬Ԙᄖㇱ߆ࠄߩ᷷ᐲᖱႎࠍ߹ ৻⥸ߦⰯశᕈ࠮ࡦࠨ࡯ߣߪ㧘޽ࠆ․ቯߩ㊄ዻࠗࠝࡦ߿

ߕᗵ᷷ㇱ૏߇⹺⼂ߒߡԙ⊒శㇱ૏ߢ޽ࠆⰯశ࿅߇⹺⼂นࠕ࠾ࠝࡦ㧘R* ╬ߩൻቇ⊛ೝỗ㧘߹ߚߪᾲ╬ߩ‛ℂ⊛ೝỗ⢻ߥᖱႎ㧔଀߃߫ᭂᕈߩᄌൻ㧕ߦᄌ឵ߔࠆ‫ޕ‬Ԛߘߩᖱႎ

ߦᔕ╵ߒߡⰯశ᜼േ㧔Ⱟశᵄ㐳߿Ⱟశᒝᐲ㧕ࠍᄌൻߐߖ

ࠍⰯశ࿅ߦવ㆐ߒߡԛ⊒శㇱ૏߆ࠄߩ⊒శ᜼േ߇ᄌൻߔ

ࠆ‛⾰ߩߎߣߢ޽ࠅ㧘㔚ሶ⒖േ߿ࠛࡀ࡞ࠡ࡯⒖േߦࠃࠆ

ࠆ⸳⸘ߦߥߞߡ߅ࠅ㧘᷷ᐲߩᄌൻࠍ⊒శ᜼േߩᄌൻߣߒ

ᶖశࠍ೑↪ߒߚ᦭ᯏ⦡⚛♽࠮ࡦࠨ࡯߿㧘(4'6㧔(NWQTGUEGPEG

ߡ಴ജߔࠆಽሶࠨࠗ࠭ߩ᷷ᐲ࠮ࡦࠨ࡯ߣߥࠆ‫ޕ‬ᗵ᷷ㇱ૏

4GUQPCPEG'PGTI[6TCPUHGT㧕ㆊ⒟ࠍ೙ᓮߔࠆߎߣߢⰯశ

ߦߪ᳓ṁᶧਛߦ߅޿ߡ⋧ォ⒖᷷ᐲએਅߩ᷷ᐲߢߪ᳓๺ߦ

-6-4᜼േࠍᄌൻߐߖࠆ࠮ࡦࠨ࡯ߦ㑐ߔࠆ⎇ⓥ଀߇ᦨ߽ᄙ޿‫ޕ‬․ߦ㧘᷷ᐲࠍኻ⽎ߣߒߚ᦭ᯏ⦡⚛♽࠮ࡦࠨ࡯ߣߒߡࡇ࡟
ࡦಽሶߩࠛࠠࠪࡑ࡯⊒శࠍ೑↪ߒߚ࠮ࡦࠨ࡯߇ႎ๔ߐࠇ
㧦‛⾰↢๮ℂᎿቇ⑼ഥᢎ (matsumura@st.seikei.ac.jp)㧦Ꮏቇ⎇ⓥ⑼ୃੌ↢*3㧦‛⾰↢๮ℂᎿቇ⑼තᬺ↢*4
㧦‛⾰↢๮ℂᎿቇ⑼ቴຬᢎ᝼(kurita@st.seikei.ac.jp)*1*2(KIWTG%QPEGRVQHVJGHNWQTGUEGPVVJGTOQUGPUQTDCUGFQPVJGVJGTOQTGURQPUKXGWPKVCPFHNWQTGUEGPEGWPKV

㧙㧙


 ᰴߦ 1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ߹ߚߪ 1,4-ࡌࡦ࠱࠴ࠕࠫࡦ

ࠃࠅ᳓ߦṁ⸃ߒߡ޿ࠆ߇㧘ߘࠇએ਄ߩ᷷ᐲߦߥࠆߣ⣕᳓๺߇⿠ߎࠅ⇹᳓ᕈ⋧੕૞↪ߦࠃࠅਇṁൻߔࠆᕈ⾰ࠍ᦭ߔ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ(13-15)ߪ㧘ൻว‛ 2 ߣኻᔕߔࠆᗵᾲᔕ╵ᕈ㜞ಽሶࠍ↪޿㧘⊒శㇱ૏ߦߪ૏⟎ߔࠆ႐ߩࠆࠕࡒࡁࡈࠚࡁ࡯࡞߹ߚߪࠕࡒࡁ࠴ࠝࡈࠚࡁ࡯࡞ࠍ෻ᔕ

ᭂᕈ߿ⷫ࡮⇹᳓ᕈߩᄌൻߦࠃࠅⰯశ᜼േ㧔⊒శᒝᐲ࡮⊒ߐߖߡ 1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ߹ߚߪ 1,4-ࡌࡦ࠱࠴ࠕࠫࡦ

శᵄ㐳㧕ࠍᄌൻߐߖࠆⰯశಽሶࠍ↪޿ࠆߎߣߢ᳓ਛߢᯏ

O2N

N
Cl

O2N

N
(1)
or
N
N

Cl

⢻ߔࠆⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ㐿⊒߇น⢻ߣߥࠆ‫ߩߎޕ‬᭎ᔨࠍ↪޿ߡ᳓᷷߇৻ቯߩ᷷ᐲએ਄ߦ㜞ߊߥࠆߣⰯశᒝᐲ
߇⪺ߒߊჇടߔࠆ࠮ࡦࠨ࡯8)߿․ቯߩ᷷ᐲ㗔ၞߩߺߢ⊒9)శߔࠆ࠮ࡦࠨ࡯ ߇ႎ๔ߐࠇߡ޿ࠆ‫ߒ߆ߒޕ‬㧘ߎࠇ߹ߢ(2)ߩߣߎࠈⰯశᵄ㐳ࠍᄌൻߐߖࠆⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩႎ
๔଀ߪߥ޿‫ޕ‬ࡁࠠࠨ࡝ࡦ(Qx)߇ᇦ૕ߩᲧ⺃㔚₸(εr)߇ૐਅߔࠆߣߣ

O2N

߽ߦⰯశᭂᄢᵄ㐳(λFl)߇⍴ᵄ㐳஥ߦࠪࡈ࠻ߒ㧘εr ߣλFlᄌൻߔࠆⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ࠍ㐿⊒ߒߚ 10) (Figure 2)‫ޕ‬

N

N

Qx

O

O

H
N

N
H
O

N

N

N

N

QxAlaMAor

H2 / 10%Pd-C or PtO2N

or(KIWTG %JGOKECNUVTWEVWTGUQH3ZCPF3Z#NC/#

N

R1(5a): R1 = OCH3(5b): R1 = SCH3(5c): R1 = CN

OCH3

N

H2N

N

O

OCH3

(4)

O

H2 N

N

R1

(3a): R1 = OCH3(3b): R1 = SCH3(3c): R1 = CNಽሶߣㅪ⚿ߐߖࠆߎߣߢ㧘᷷ᐲᄌൻߦᔕ╵ߒߡ⊒శ⦡ߩ

N

O2 N

N

㊀วᕈߩቭ⢻ၮࠍዉ౉ߒߚ QxAlaMA ࠍᗵᾲᔕ╵ᕈ㜞

N

OCH3

N

ߣߩ㑆ߦ৻ᰴߩ⋧㑐㑐ଥ߇޽ࠆߎߣࠍ⷗಴ߒ㧘Qx ߦ

N

R1

Na2CO3 / PPh3, Pd(PPh3)2Cl2
in aqueous dioxane ߎࠇ߹ߢߦ╩⠪ࠄߪ㧘2,3-ࠫࡕ࡞ࡎ࡝ࡁ-6-ࠕࡒࡁࠠ

H2 N

HO
B
HO

+

Cl

OCH3

(6)

ߘߎߢᧄ⎇ⓥߢߪ㧘ࠃࠅ㐳ᵄ㐳஥ߦ⊒శᏪࠍ߽ߟ⊒శㇱ
Scheme 1૏ߣߒߡ㧘2 ૏߹ߚߪ 2㧘3 ૏ߦ⟎឵ࠕ࡝࡯࡞ၮࠍ᦭ߔࠆ

6-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ߣ 1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ߹ߚߪ

O2N

1,4-ࡌࡦ࠱࠴ࠕࠫࡦ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ࠍวᚑ

(2)ߒ㧘ߘࠇࠄߩಽశቇ⊛․ᕈࠍ⹏ଔߔࠆߣߣ߽ߦⰯశᕈ᷷

N

Cl

N

Cl
XH

ᐲ࠮ࡦࠨ࡯ߩ⊒శㇱ૏ߣߒߡߩ᦭↪ᕈࠍᬌ⸛ߒߚ‫ޕ‬

R2

H2N

㧞㧚⚿ᨐߣ⠨ኤO2N

㧙㧚Ⱟశᕈࠠࡁࠠࠨ࡝ࡦ㘃ߩวᚑ 2 ૏߹ߚߪ 2㧘3 ૏ߦ⟎឵ࡈࠚ࠾࡞ၮࠍ᦭ߔࠆ 6ࠕࡒ
ࡁࠠࡁࠠࠨ࡝ࡦ㘃 5a-c, 6 ߪ㧘ᣢሽߩᣇᴺߢวᚑߒߚൻ

N

X

N

N
H

R2

+

O2N

(7): X = O, R2 = H(9): X = O, R2 = CH3(11):X = S, R2 = Hว‛ 111)߹ߚߪ 212)ߦ㋈ᧁгችᶆࠞ࠶ࡊ࡝ࡦࠣᴺࠍ↪޿ࠆߎߣߢ⟎឵ࡈࠚ࠾࡞ࡏࡠࡦ㉄ߣ෻ᔕߐߖߡ 6࠾࠻ࡠࠠ

౉ߒߚൻว‛ 3a-c,4 ࠍᓧߚᓟ㧘10%ࡄ࡜ࠫ࠙ࡓ὇⚛߹

H2N

N

X

N

N
H

R2

ߚߪ㉄ൻ⊕㊄ࠍ⸅ᇦߣߒߡ↪޿ߡ᳓⚛ᷝടߔࠆߎߣߦࠃ
ࠅวᚑߒߚ (Scheme 1)‫ߒ߆ߒޕ‬ൻว‛ 5b ߪ㧘෻ᔕᤨ㑆߿⸅ᇦࠍᄌൻߐߖߡ߽ 6 ૏ߩ࠾࠻ࡠၮ߇ࠕࡒࡁၮ߹ߢቢ

(13): X = O, R2 = H(14): X = O, R2 = CH3(15): X = S, R2 = H

ోߦㆶరߐࠇߕᄙᢙߩਛ㑆૕߇ᷙ࿷ߒߚ⁁ᘒߢᓧࠄࠇ㧘

Scheme 2න㔌ߔࠆߎߣ߇ߢ߈ߥ߆ߞߚ‫ޕ‬

㧙㧙

H
N

N

X

(8): X = O, R2 = H(10):X = O, R2 = CH3(12):X = S, R2 = H

H2 / 10%Pd-C

ࡁࠠࠨ࡝ࡦߩ 2 ૏߹ߚߪ 2㧘3 ૏ߦ⟎឵ࡈࠚ࠾࡞ၮࠍዉ

N

R2


ᵄ㐳(λFl)ߪ 4 nm 㐳ᵄ㐳஥ߦࠪࡈ࠻ߒߚ‫ޕ‬ൻว‛ 5a ߩ 3❗Ⅳ 8-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ㘃(7,9,11)ࠍวᚑߒߚᓟ㧘10%ࡄ࡜ࠫ࠙ࡓ὇⚛⸅ᇦሽ࿷ਅߢ᳓⚛ᷝടࠍⴕ߁ߎߣߢวᚑ

૏ߦࡔ࠻ࠠࠪࡈࠚ࠾࡞ၮ߇ዉ౉ߐࠇߡ߽(ൻว‛ 6)㧘ๆ෼

ߒߚ(Scheme 2)‫ޕ‬1 Ბ㓏⋡ߩ෻ᔕߦ߅޿ߡ㧘޿ߕࠇߩൻว

߅ࠃ߮Ⱟశࠬࡍࠢ࠻࡞ߦᄢ߈ߥᄌൻߪߥߊ㧘Ⱟశᒝᐲ߇
ᷫዋߒߚ‫ߚ߹ޕ‬㧘ൻว‛ 5a㧘5c㧘6 ߩⰯశ㊂ሶ෼₸(Φf)‛߽ࠊߕ߆ߢߪ޽ࠆ߇᭴ㅧ⇣ᕈ૕(8,10,12)ߩሽ࿷߇⏕⹺ߐࠇߚ‫ߚ߹ޕ‬㧘ൻว‛ 9 ߩ X ✢⚿᥏᭴ㅧ⸃ᨆߩ⚿ᨐࠃࠅ㧘ߪߘࠇߙࠇ 0.22㧘0.12㧘0.13 ߣߥࠅ㧘QxAlaMA(0.66)߶ߤ

㜞޿୯ߣߪߥࠄߥ߆ߞߚ‫ޕ‬ࠠࡁࠠࠨ࡝ࡦⅣߣࡌࡦ࠯ࡦⅣ߇ห৻ᐔ㕙਄ߦ޽ࠆߎߣ߇
ࠊ߆ߞߚ(Figure 3, Table 1)‫ߪߣߎߩߎޕ‬㧘Ǹ㔚ሶ߇ࠠࡁࠠ

(a)

ࠨ࡝ࡦⅣߣࡌࡦ࠯ࡦⅣ਄ߦᐢߊ㕖ዪ࿷ൻߒߡ߅ࠅ㧘⟎឵ၮߩ㔚ሶଏਈ⢻ࠍᄌൻߐߖߡࡊ࠶ࠪࡘгࡊ࡞ဳߩಽሶߣ
ߔࠆߎߣߢ QxAlaMA ࠃࠅ㐳ᵄ㐳஥ߢṁᇦߩᭂᕈߩᄌൻ
ߦࠃࠅⰯశᵄ㐳ߩᄌൻߔࠆⰯశᕈಽሶߩวᚑ߇น⢻ߢ޽ࠆߎߣࠍ␜ໂߒߡ޿ࠆ‫ޕ‬
O
O

H
C

N

C

H

C
C

C
C

H

N

N

C
C

H

O

C

N

C

H

H
C

C

C
C

C

H
H

H

(b)

H

(KIWTG146'2FTCYKPIQHEQORQWPF
6CDNG %TKUVCNNQITCRJKEFCVCHQTEQORQWPF
㪝㫆㫉㫄㫌㫃㪸㩷
㪤㩷㪚㪈㪌㪟㪈㪇㪥㪋㪦㪊㩷㪉㪐㪋㪅㪉㪎㩷

㪚㫉㫐㫊㫋㪸㫃㩷㫊㫐㫊㫋㪼㫄㩷㪦㫉㫋㪿㫆㫉㪿㫆㫄㪹㫀㪺㩷㪪㫇㪸㪺㪼㩷㪾㫉㫆㫌㫇㩷㪧㪹㪺㪸㩿㩺㪍㪈㪀㩷㪸㪆㷬㩷㪍㪅㪐㪍㪌㪐㩿㪉㪀㩷㪹㪆㷬㩷㪈㪉㪅㪋㪇㪈㪉㩿㪌㪀㩷㪺㪆㷬㩷㩷 㩷 㪉㪐㪅㪌㪎㪏㪏㩿㪈㪊㪀㩷㪊㪉㪌㪌㪌㪅㪉㩿㪉㪀㩷㪩㪈㩷㪲㪠㪕㪉σ㩿㪠㪀㪴㩷㪇㪅㪇㪌㪉㩷

㫎㪩㪉㩷㪇㪅㪈㪊㪐㩷㪭㪆㷬 㩷(KIWTG #DUQTRVKQP C CPFHNWQTGUEGPEGURGEVTC D QHCOKPQSWKPQZCNKPGFGTKXCVKXGU CECPF C г E г࡮г CPF гг  C Eµ/KP&/(
CPF D Eµ/KPOGVJCPQN 1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ(13)ߪ㧘THF ਛߦ߅޿ߡ 411 nm ߦ╙৻ๆ෼Ꮺࠍ߽ߟๆ෼ࠬ

ࡍࠢ࠻࡞ߣ 482 nm ߦᭂᄢࠍ߽ߟࡉࡠ࡯࠼ߥⰯశࠬࡍࠢ
࠻࡞ࠍ␜ߒ㧘Φf ߪ 0.61 ߢ޽ߞߚ‫ޕ‬3 ૏ߦࡔ࠴࡞ၮࠍ᦭ߔ

㧙㧚Ⱟశᕈࠠࡁࠠࠨ࡝ࡦ㘃ߩಽశቇ⊛․ᕈ⹏ଔࠆൻว‛ 14 ߩ λabs ߣ λFl ߪ޿ߕࠇ߽ൻว‛ 13 ࠃࠅࠊߕ ᗵ᷷ㇱ૏ߣ⊒శㇱ૏ࠍಽ㔌ߒߚಽሶ⸳⸘ߦၮߠߊⰯశ
ᕈ᷷ᐲ࠮ࡦࠨ࡯ߪ㧘ᾲೝỗߦࠃࠆᗵ᷷ㇱ૏ߩᒻᘒᄌൻߦ

6CDNG #DUQTRVKQPCPFHNWQTGUEGPEGURGEVTCNFCVC
QHCOKPQSWKPQZCNKPGFGTKXCVKXGUࠃࠅ⺃⿠ߐࠇࠆⷫ࡮⇹᳓ᕈᄌൻࠍⰯశ࿅߇ᗵ⍮ߔࠆߎߣߢᯏ⢻ߔࠆߎߣ߆ࠄ㧘⊒శㇱ૏ߦߪṁᇦߩᭂᕈߣ⊒శ․ᕈߣߩ㑆ߦ૗ࠄ߆ߩ⋧㑐㑐ଥࠍ᦭ߔࠆߎߣ߇ᔅⷐߢ޽ࠆ‫ޕ‬એਅߦൻว‛ 5a, 5c, 6, 13-15 ߩๆ෼߅ࠃ߮Ⱟశ․ᕈࠍ
␜ߔ(Table 2)‫ޕ‬ 4’૏ߦࡔ࠻ࠠࠪၮࠍ߽ߟൻว‛ 5a ߪ㧘DMF ਛߦ߅޿

ߡ 410 nm ઃㄭߦ╙৻ๆ෼Ꮺ(λabs)ࠍ߽ߟๆ෼ࠬࡍࠢ࠻࡞

ࠍ␜ߒ㧘ࡔ࠲ࡁ࡯࡞ਛߦ߅޿ߡ 450ޯ600 nm ઃㄭߦᝄേ
᭴ㅧߩߥ޿ࡉࡠ࡯࠼ߥⰯశࠬࡍࠢ࠻࡞ࠍ␜ߒߚ(Figure4)‫ޕ‬4’૏ߩࡔ࠻ࠠࠪၮ߇㔚ሶ᳞ᒁᕈߩࠪࠕࡁၮߦߥࠆߣ

(ൻว‛ 5c) λabs ߪ 14 nm 㐳ᵄ㐳஥߳ࠪࡈ࠻ߒ㧘Ⱟశᭂᄢ

㧙㧙


߆ߦ㐳ᵄ㐳஥ߦ૏⟎ߔࠆ߽ߩߩΦf ߪ 0.58 ߣߥࠅ 3 ૏ߩࡔ߽ߟⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ࠍวᚑߒ㧘ߘߩⰯశ․ᕈࠍ⹏ଔ

࠴࡞ၮߪࠬࡍࠢ࠻࡞․ᕈߦᓇ㗀ࠍਈ߃ߥ޿ߎߣ߇ࠊ߆ࠆ‫ޕ‬ߔࠆߎߣߢⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ⊒శㇱ૏ߦߥࠅᓧࠆ߆

৻ᣇ㧘
5 ૏ߩ㉄⚛ේሶ߇⎫㤛ේሶߦߥࠆߣ(ൻว‛ 15)㧘λabs⹏ଔߒߚ‫Ⱟޕ‬శᕈ᷷ᐲ࠮ࡦࠨ࡯ߩᗵ᷷ㇱ૏ߦߪ㧘᳢↪ߩߣ λFl ߪߘࠇߙࠇ 448 nm ߅ࠃ߮ 520 nm ߣൻว‛ 13 ࠃᗵᾲᔕ╵ᕈ㜞ಽሶߢ޽ࠆࡐ࡝(N-ࠗ࠰ࡊࡠࡇ࡞ࠕࠢ࡝࡞

ࠅ㐳ᵄ㐳஥ߦࠬࡍࠢ࠻࡞ࠍ␜ߒߚ‫⎫ߦ⥸৻ޕ‬㤛ේሶߪⰯࠕࡒ࠼)(PNIPAM)ࠍ↪޿ࠆߎߣߣߒߚ‫ޕ‬㧘ൻว‛ 15㧞г㧟г㧝㧚Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩวᚑ

శᕈࠍᷫᒙߐߖࠆߎߣ߇⍮ࠄࠇߡ޿ࠆ߇

13, 14)ߩΦf ߪ 0.46 ߣൻว‛ 13 ߦᲧߴࠊߕ߆ߦૐ޿୯ߦߥߞߚ ൻว‛ 15 ߣ NIPAM ࡙࠾࠶࠻ࠍㅪ⚿ߔࠆߚ߼ߦ㧘ൻวߎߣߪ⥝๧ᷓ޿‫ޕ‬‛ 15 ߦ࠻࡝ࠛ࠴࡞ࠕࡒࡦሽ࿷ਅߢႮൻࠕࠢ࡝ࡠࠗ࡞ࠍ วᚑߒߚ 6 ⒳ߩࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ߩλFl ߪ㧘޿ߕࠇ෻ᔕߐߖࠆߎߣߦࠃࠅ㊀วᕈߩቭ⢻ၮࠍዉ౉ߒߚൻว‛19.92(ࠗ࠰ࡊࡠࡄࡁ࡯࡞)߆ࠄ 55.61(᳓-ࡔ࠲ࡁ࡯࡞ᷙวṁ(15)

16 ࠍวᚑߒߚ(Scheme 3)‫ޕ‬߽ ⒳ ‫ ࡞ ࡯ ࠦ ࡞ ࠕ ߩ ޘ‬ṁ ᇦ ਛ ߢ ṁ ᇦ ߩ Ყ ⺃ 㔚 ₸ (εr) ߇acryloyl chloride,Et3N

ᇦ(1/1))߹ߢჇടߔࠆߣ⍴ᵄ㐳஥ߦࠪࡈ࠻ߔࠆᕈ⾰ࠍ᦭
ߒߚ(Figure 5)‫ޕ‬λFl ߣṁᇦߩᲧ⺃㔚₸(εr)ߣߩ㑆ߩ㑐ଥᑼ

HNࠍᦨዊੑਸ਼ᴺߦࠃࠅ᳞߼ߚߣߎࠈ㧘5a :λFl [nm] = 0.3398εr + 507.22 (r = 0.994)

(1)

6 :

λFl [nm] = 0.3161εr + 504.10 (r = 0.998)

(3)

5c :
13 :

λFl [nm] = 0.3310εr + 511.64 (r = 0.999)

O

(2)

N

S

N

N
H

(16)

λFl [nm] = 0.2523εr + 505.24 (r = 0.996)(4)

Scheme 3λFl [nm] = 0.2476εr + 534.46 (r = 0.995)(6)

 Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯(poly(16-co-NIPAM))ߪ㧘ᗵ᷷ㇱ૏ߣߥࠅ㧘৻ᰴߩ⋧㑐㑐ଥ߇⷗ࠄࠇߚ‫ߒ߆ߒޕ‬㧘ߎߩߎߣߩᗵᾲᔕ╵ᕈࠍ଻ᜬߔࠆߚ߼ߦൻว‛ 16 ߩ઀ㄟߺ⚵ᚑߦኻߔࠆℂ⺰⊛ߥᩮ᜚ߪ੹ߩߣߎࠈਇ᣿ߢ޽ࠆ‫ޕ‬એ਄ࠃࠍᗵ᷷ㇱ૏ߦኻߒߡ 0.1 mol%ߣߥࠆࠃ߁ߦ⺞ᢛߒߡ㧘࡜

14 :
15 :

λFl [nm] = 0.2598εr + 508.57 (r = 0.999)(5)ࠅวᚑߒߚ㧢⒳ߩࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ߪ޿ߕࠇ߽Ⱟశ

ࠫࠞ࡞㊀วᴺߦࠃࠅวᚑߒߚ‫࡞࡯ࡁ࠲ࡔޕ‬ਛߢߩๆశᐲ

ᕈ࠮ࡦࠨ࡯ߩⰯశㇱ૏ߦߥࠅᓧࠆߎߣ߇␜ໂߐࠇߚ‫ޕ‬ࠃࠅ᳞߼ߚ poly(16-co-NIPAM)ߦ߅ߌࠆ 16 ߩ฽㊂ߪ㧘

NIPAM 660 ࡙࠾࠶࠻ߦኻߒߡ 1 ࡙࠾࠶࠻ߢ޽ߞߚ‫ޕ‬㧙㧙㧚Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ․ᕈ⹏ଔ

 Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯poly(16-co-NIPAM)ߩⰯశ․ᕈࠍ
⹏ଔߔࠆߩߦవ┙ߜ㧘ൻว‛ 16 ߩๆ෼߅ࠃ߮Ⱟశ․ᕈ

ߩ⹏ଔࠍⴕߞߚ‫ޕ‬ൻว‛ 16 ߪ THF ਛߦ߅޿ߡ 434 nm

(ε=5700)ߦ╙৻ๆ෼Ꮺࠍ߽ߟๆ෼ࠬࡍࠢ࠻࡞ߣ㧘514 nmઃㄭߦᭂᄢࠍ߽ߟⰯశࠬࡍࠢ࠻࡞ࠍ␜ߒ㧘޿ߕࠇߩࠬࡍ
ࠢ࠻࡞߽ൻว‛ 15 ࠃࠅ⍴ᵄ㐳஥ߦ૏⟎ߒߚ‫ߪࠇߎޕ‬㧘ൻว‛ 15 ߩ 8 ૏߇㔚ሶଏਈᕈߩࠕࡒࡁၮߢ޽ࠆߩߦኻߒ㧘ൻว‛ 16 ߢߪࠕࡒ࠼⚿วߣߥࠆߚ߼⓸⚛ේሶߩ㕖౒᦭㔚ሶኻߩ㔚ሶଏਈ⢻߇ૐਅߒߚߚ߼ߣ⠨߃ࠄࠇࠆ‫ޕ‬߹ߚ㧘Ⱟశ㊂ሶ෼₸ߪ 0.37 ߣൻว‛ 15 ࠃࠅࠊߕ߆ߦૐ

޿୯ߣߥࠆ߽ߩߩ㧘(7)ᑼߦ␜ߔࠃ߁ߦ λFl ߣṁᇦߩᲧ⺃

(KIWTG 2NQVUQHλ(.QHEQORQWPFC ٌ E ٠   ً  ٤  ٨  ‫ غ‬CUCHWPEVKQPQH
 FKGNGEVTKEEQPUVCPV εT QHVJGUQNXGPV㔚₸(εr)ߣߩ㑆ߩ⋧㑐㑐ଥߪ଻ᜬߐࠇߡ޿ߚ‫ޕ‬16:λFl [nm] = 0.2221εr + 527.77 (r = 0.994) (7)㧙㧚Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ⊒శㇱ૏ߣߒߡߩ⹏ଔ ᰴߦൻว‛ 16 ߇ᗵ᷷ㇱ૏ߩᗵᾲᔕ╵ᕈߦਈ߃ࠆᓇ㗀 วᚑߒߚ 6 ⒳ߩࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㘃ߩਛߢ 1,4-ࡌࡦߦߟ޿ߡᬌ⸛ߒߚ‫ޕ‬poly(16-co-NIPAM)᳓ṁᶧߩ 600 nm஥ߦๆ෼߅ࠃ߮Ⱟశࠬࡍࠢ࠻࡞ࠍ␜ߒ㧘Ⱟశ㊂ሶ෼₸߇

Lower Critical Solution Temperature) એ ਄ ߢ ૐ ਅ ߒ 㧘࠱࠴ࠕࠫࡦ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ(15)߇ᦨ߽㐳ᵄ㐳ߦ߅ߌࠆㅘㆊ₸ߪ㧘ᶧ᷷ࠍ਄᣹ߐߖࠆߣ 32˚C(LCST;㜞ߊ㧘Ⱟశᭂᄢᵄ㐳ߣṁᇦߩᲧ⺃㔚₸ߣߩ㑆ߦ 1 ᰴߩ⋧

PNIPAM ߣห᭽ߩᄌൻࠍ␜ߒߚ(Figure 6, open symbol)‫ޕ‬㑐㑐ଥࠍ᦭ߔࠆߎߣ߆ࠄ㧘ൻว‛ 15 ࠍ⊒శㇱ૏ߣߒߡߎߩߎߣ߆ࠄ poly(16-co-NIPAM)ߩᗵᾲᔕ╵ᕈߦൻว‛

㧙㧙


㧠㧚ታ㛎ᣇᴺ㧙㧚↪޿ߚ⹜⮎ߣ᷹ቯⵝ⟎ Ⲣὐߪ Mel-Temp apparatus ࠍ↪޿ߡ᷹ቯߒߚ‫⿒ޕ‬ᄖๆ෼ࠬࡍࠢ࠻࡞ ߪ㧘JASCO FT/IR-230 Fourier Transform

Infrared Spectrometer ࠍ㧘⚡ᄖนⷞๆ෼ࠬࡍࠢ࠻࡞߅ࠃ߮

Ⱟశࠬࡍࠢ࠻࡞ߪ㧘ߘࠇߙࠇᕡ᷷࠮࡞ࡎ࡞࠳࡯ઃ߈ߩ
JASCO V-550 UV/VIS Spectrophotometer ߅ࠃ߮ JASCO

FP-777 Spectrofluorometer ࠍ↪޿ߡⴕߞߚ‫ޕ‬1H-NMR ࠬࡍࠢ࠻࡞ߪ JEPL LNM-LA400D FT-NMR Spectrometer ࠍ(KIWTG 6TCPUOKVVCPEGCVPO QRGPU[ODQNU CPFHNWQTGUEGPEGλ(N UQNKFU[ODQNU QH
YX CSWGQWU UQNWVKQP QH RQN[OGTU CU C
HWPEVKQP QH VGORGTCVWTG 20+2#/ ‫  غ‬CPF
RQN[ EQ0+2#/ ٤٨ λGZPO↪޿ߡ᷹ቯߒ㧘Me4Si ࠍౝㇱᮡḰߣߒߡ↪޿ߚ‫ޕ‬ర⚛ಽᨆߪ Perkin Elmer 2400 Series II CHNS/O ࠍ↪޿ߡⴕߞߚ‫ޕ‬᷷ᐲ᷹ቯߪࠢࡠࡔ࡞−ࠕ࡞ࡔ࡞ᾲ㔚ኻࠍ↪޿ߡⴕߞߚ‫ޕ‬

16 ዉ౉ߩᓇ㗀߇ߥ޿ߎߣ߇ࠊ߆ࠆ‫ߩߎޕ‬᳓ṁᶧࠍ 451 nm

㧙㧚วᚑᣇᴺ

శࠬࡍࠢ࠻࡞ࠍ␜ߒߚ‫ޕ‬ᶧ᷷ࠍ਄᣹ߐߖࠆߣ LCST ઃㄭ 2-ࡅ࠼ࡠࠠࠪࠠࡁࠠࠨ࡝ࡦ(4.40 g, 30 mmol)ߦ᳖ᶎਛ

full symbol)‫ߩߎޕ‬⍴ᵄ㐳ࠪࡈ࠻ߪ㧘NIPAM ࡙࠾࠶࠻ߩᾲ

mmol)ࠍ 30 ಽ㑆߆ߌߡዋߒߕߟട߃㧘ቶ᷷ߢ 2 ᤨ㑆ᠣᜈ෻ᤋߒߡ޿ࠆ߽ߩߢ޽ࠅ㧘ᗵ᷷ㇱ૏ߣ⊒శㇱ૏ࠍಽ㔌ߒỹㆊߒߡᓧߚᓟ㧘᳓ߢᵞᵺߒ㧘㈶㉄߆ࠄౣ⚿᥏ߔࠆߎߣ

ߚ᭎ᔨߦၮߠߊⰯశᕈ᷷ᐲ࠮ࡦࠨ࡯ߣߒߡᯏ⢻ߒߡ޿ࠆߢ᷆㤛⦡ߩ㊎⁁⚿᥏ߣߒߡ 2-ࡅ࠼ࡠࠠࠪ-6-࠾࠻ࡠࠠࡁ

ߩశߢബ⿠ߒߚߣߎࠈ㧘ൻว‛ 16 ↱᧪ߩࡉࡠ࡯࠼ߥⰯ

2-ࠢࡠࡠ-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(1)ߩวᚑ 11)ߩ 30ޯ32˚C ߢλFl ߪᕆỗߦ⍴ᵄ㐳ࠪࡈ࠻ߒߚ(Figure 6,ߢỚ⎫㉄(51 mL)ࠍട߃ߚᓟ㧘⎣㉄ࠞ࡝࠙ࡓ(3.31 g, 30⋧ォ⒖ߦࠃࠅ 16 ࡙࠾࠶࠻ㄭறߩᭂᕈ߇ૐਅߒߚߎߣࠍ

ߒߚ‫ޕ‬෻ᔕṁᶧࠍ᳖(300 g)ߦᵈ߉౉ࠇ㧘ᨆ಴ߒߚ࿕૕ࠍ

ࠠࠨ࡝ࡦ(4.86 g, 85%)ࠍᓧߚ‫ޕ‬ᰴߦ㧘2-ࡅ࠼ࡠࠠࠪ-6-࠾࠻

ߎߣ߇␜ໂߐࠇࠆ‫Ⱟޕ‬శᕈ᷷ᐲ࠮ࡦࠨ࡯ߣߒߡߩᗵᐲࠍ
1˚C ߩ᷷ᐲ਄᣹ߦࠃࠅ 3%એ਄ߩⰯశᵄ㐳ߩᄌൻ߇⹺߼

ࡠࠠࡁࠠࠨ࡝ࡦ(3.98 g, 20.8 mmol)ࠍή᳓ࠫࠝࠠࠨࡦߣή

᳓ DMF ߩᷙวṁᇦ(20/1, 84 mL) ߦṁ⸃ߒ㧘᳖ᶎਛߢႮ

ࠄࠇࠆ᷷ᐲ㗔ၞࠍᗵ⍮น⢻ߥ᷷ᐲ▸࿐ߣቯ⟵ߔࠆߣ㧘ൻ࠴ࠝ࠾࡞(15 mL, 209 mmol)ࠍṢਅߒߚᓟ㧘90ƷC ߢ 25

poly(16-co-NIPAM)ߪ㧘28.5ޯ32.5˚C ߢᯏ⢻ߒ㧘ߎߩ᷷ᐲ▸࿐ߦ߅޿ߡ 1˚C ޽ߚࠅߩᵄ㐳ᄌൻ߇ 2.8 nm ߢ޽ࠆⰯశ

ᤨ㑆ടᾲᠣᜈߒߚ‫ޕ‬෻ᔕṁᶧࠍ᳖಄ߒߡᨆ಴ߒߚ࿕૕ࠍ

ᕈ᷷ᐲ࠮ࡦࠨ࡯ߢ޽ࠆߎߣ߇ࠊ߆ߞߚ‫ޕ‬ỹขߔࠆߎߣߢ⋡⊛ൻว‛(1)ࠍ᷆㤛⦡ߩ㊎⁁⚿᥏(2.82
g, 64%) ߣ ߒ ߡ ᓧ ߚ ‫ ޕ‬mp: 199˚C(decomp.); 1H-NMR(δ,CDCl3, 400 MHz): 8.20 (1H, d, J = 9.2 Hz, C8-H), 8.60 (1H,㧟㧚✚ ᜝

dd, J = 2.4 and 9.2 Hz, C7-H), 8.95 (1H, s, C3-H), and 9.04

ppm (1H, d, J = 2.4 Hz, C5-H).; IR(KBr): 3052(νC-H), 1527

 Ⱟశᕈ᷷ᐲ࠮ࡦࠨ࡯ߩ⊒శㇱ૏ߣߒߡ㧘⟎឵ࡈࠚ࠾࡞

and 1354 (νNO ), and 743 cm-1(νC-Cl).

ၮࠍ᦭ߔࠆ 3 ⒳ߩ 6-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㧘2 ⒳ߩ 1,4-ࡌ

2ࡦ࠱ࠝࠠࠨࠫࡦ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ㧘1 ⒳ߩ 1,4-

2,3-ࠫࡕ࡞ࡎ࡝ࡁ-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(2)ߩวᚑ 12)ࡌࡦ࠱࠴ࠕࠫࡦ❗Ⅳ 8-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦࠍวᚑߒߚ‫ޕ‬

 4-࠾࠻ࡠ-1,2-ࡈࠚ࠾࡟ࡦࠫࠕࡒࡦ(5 g, 33 mmol)ߣࠪࡘ

Ⱟశࠬࡍࠢ࠻࡞ࠍ␜ߒ㧘λFl ߣεr ߣߩ㑆ߦߪ㧝ᰴߩ⋧㑐㑐

160˚C ߢ 3 ᤨ㑆ടᾲㆶᵹߒߚ‫ޕ‬෻ᔕṁᶧࠍቶ᷷߹ߢ಄ළ

޿ߕࠇߩൻว‛߽ QxAlaMA ࠃࠅ㐳ᵄ㐳஥ߦๆ෼߅ࠃ߮

ଥ߇޽ߞߚ‫ߩߘޕ‬ਛߢ߽ൻว‛ 15 ߇ᦨ߽㐳ᵄ㐳஥ߦ૏࠙㉄ੑ᳓๺‛(15 g, 166 mmol)ࠍ੃㋬ߢဋ৻ߦᷙวߒߚᓟ㧘ߒ㧘3M Ⴎ㉄᳓ṁᶧ(8 mL) ࠍട߃ߡỹㆊߒߚᓟ㧘ᱷᷲࠍ᳓(50 mL3)ߣࡔ࠲ࡁ࡯࡞(50 mL)ߢᵞᵺߒߡ㧘᳓߆ࠄౣ⟎ߔࠆߎߣ߇ࠊ߆ߞߚ‫੹ޕ‬࿁วᚑߒߚⰯశᕈ᷷ᐲ࠮ࡦࠨ

⚿᥏ߔࠆߎߣߢ 1,4-ࠫࡅ࠼ࡠ-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ-2,3-࡯(poly(16-co-NIPAM))ߪ㧘28.5ޯ32.5˚C ߩ▸࿐ߦ߅޿ߡ
2.8 nm/˚C ߩᄌൻ₸ߢᯏ⢻ߔࠆ࠮ࡦࠨ࡯ߢ޽ࠆߎߣ߇ࠊ

ࠫࠝࡦࠍⶊ⦡☳ᧃ(5.9 g, 87%)ߣߒߡᓧߚ‫ޕ‬ᰴߦ 1,4-ࠫࡅ࠼ࡠ-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ-2,3-ࠫࠝࡦ(4 g, 19 mmol)ࠍ

߆ߞߚ‫ޕ‬

ੇ῎ࠫࠝࠠࠨࡦߣੇ῎ DMF ߩᷙวṁᇦ(6/1, 70 mL)ߦṁ⸃ߒߚᓟ㧘᳖ᶎਛߢႮൻ࠴ࠝ࠾࡞(12 mL, 167 mmol) ࠍṢਅߒߡ 110˚C ߢ 3 ᤨ㑆ടᾲㆶᵹߒߚ‫ޕ‬෻ᔕṁᶧࠍቶ᷷߹

㧙㧙


Hz, C8-H), 8.40(2H, d, J = 8.4 Hz, C3’-H and C5’-H), 8.60(1H,ߢ಄ළߒߡᷫ࿶⇐෰ߒߚᓟ㧘ᱷᷲࠍ㈶㉄ࠛ࠴࡞(150 mL)

dd, J = 2.6 and 9.2 Hz, C7-H), 9.07(1H, d, J = 2.6 Hz, C5-H),

ߦṁ⸃ߒߡ᳓(100 mL3)ߣ㘻๺㘩Ⴎ᳓(100 mL)ߢᵞᵺ

and 9.52 ppm(1H, s, C3-H); IR(KBr): 3060 and 2924(νC-H),ߒߚ‫᦭ޕ‬ᯏጀࠍή᳓⎫㉄࠽࠻࡝࠙ࡓߢੇ῎ߒߡṁᇦࠍᷫ

2228(νC-N), 1534 and 1350(νNO ), and 848 cm-1(γC-H); Anal.
2࿶⇐෰ߒߚᓟࡋࠠࠨࡦ߆ࠄౣ⚿᥏ߒߡ⋡⊛ൻว‛(2)ࠍ
⊕ ⦡ ࿕ ૕ (3 g, 63 %) ߣ ߒ ߡ ᓧ ߚ ‫ ޕ‬mp: 151-153˚C;

Calcd for C15H8N4O2࡮0.4H2O: C, 63.56; H, 3.13; N, 19.77.

8.60(1H, dd, J = 2.4 and 9.3 Hz, C7-H), and 9.84 ppm(1H, d,

2,3-ࠫ(4’-ࡔ࠻ࠠࠪࡈࠚ࠾࡞)-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(7):1Found: C, 63.37; H, 2.89; N, 19.85.

H-NMR(δ, CDCl3, 400 MHz): 8.21(1H, d, J = 9.3 Hz, C3-H),

J = 9.3 Hz, C5-H); IR(KBr): 3057(νC-H), 1527 and 1356(νNO ),2෼₸ 63%; mp: 151-153˚C; 1H-NMR(δ, CDCl3, 400 MHz):2-߹ߚߪ 2,3-ࡆࠬ(4’-⟎឵ࡈࠚ࠾࡞)-6-࠾࠻ࡠࠠࡁࠠࠨ࡝

7.54-7.58 (4H, m, C2’-H and C6’-H), 8.22(1H, d, J = 9.4 Hz,

917 and 833(γC-H), and 741 cm-1(νC-Cl).

3.86(6H, s, CH3), 6.89-6.92 (4H, m, C3’-H and C5’-H),
C8-H), 8.48(1H, dd, J = 2.6 and 9.4 Hz, C7-H), and 9.01

ࡦߩวᚑ

ppm(1H, d, J = 2.6 Hz, C5-H); IR(KBr): 3064(νC-H), 1523 andઍ⴫଀㧦2-(4’-ࡔ࠻ࠠࠪࡈࠚ࠾࡞)-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ

1341(νNO ), 1248 and 1028(νC-O), and 841 cm-1(γC-H); Anal.
2(3a)ߩวᚑ

 2-ࠢࡠࡠ-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(1)(421 mg, 2.0 mol) ߣCalcd for C22H17N3O4࡮0.3H2O: C, 67.27; H, 4.52; N, 10.70.

࡝ࡈࠚ࠾࡞ࡎࠬࡈࠖࡦ)ࡄ࡜ࠫ࠙ࡓ(II)ࠫࠢࡠ࡝࠼(74 mg,

2-߹ߚߪ 2,3-ࡆࠬ(4’-⟎឵ࡈࠚ࠾࡞)-6-ࠕࡒࡁࠠࡁࠠࠨ࡝

Found: C, 67.31; H, 4.38; N, 10.41.

p-ࡔ࠻ࠠࠪࡈࠚ࠾࡞ࡏࡠࡦ㉄(336 mg, 2.2 mmol)㧘ࡆࠬ(࠻0.1 mmol)㧘࠻࡝ࡈࠚ࠾࡞ࡎࠬࡈࠖࡦ(52 mg, 0.2 mmol)ߦ

ࡦߩวᚑࠫࠝࠠࠨࡦ(20 mL)ߣ 2M ὇㉄࠽࠻࡝࠙ࡓ᳓ṁᶧ(2 mL)ࠍઍ⴫଀㧦2-(4’-ࡔ࠻ࠠࠪࡈࠚ࠾࡞)-6-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ

ᓟ㧘ᨆ಴ߒߚ࿕૕ࠍỹ೎ߒ㧘ᱷᷲࠍࠢࡠࡠࡎ࡞ࡓ(150 mL)

 10%ࡄ࡜ࠫ࠙ࡓ὇⚛(30 mg) ߦή᳓ THF (10 mL)ࠍട

ട߃ 17 ᤨ㑆ടᾲㆶᵹߒߚ‫ޕ‬෻ᔕṁᶧࠍቶ᷷߹ߢ಄ළߒߚ

(4a)ߩวᚑ

߃᳓⚛㔓࿐᳇ਅߢ 30 ಽ㑆೨ㆶరߒߚᓟ㧘2-(4’-ࡔ࠻ࠠࠪߦṁ⸃ߒߡ᳓(100 mL3)ߣ㘻๺㘩Ⴎ᳓(100 mL)ߢᵞᵺࡈ ࠚ ࠾ ࡞ )-6- ࠾ ࠻ ࡠ ࠠ ࡁ ࠠ ࠨ ࡝ ࡦ (3a) (101 mg, 0.34ߒߚ‫᦭ޕ‬ᯏጀࠍή᳓⎫㉄࠽࠻࡝࠙ࡓߢੇ῎ߒߚᓟ㧘ṁᇦmmol)ߩή᳓ THF ṁᶧࠍട߃ 30 ಽ㑆᳓⚛ᷝടࠍⴕߞߚ‫ޕ‬ࠍᷫ࿶⇐෰ߒߡ⋡⊛ൻว‛(3a)ࠍ㤛⦡࿕૕(472 mg, 84%)ߣߒߡᓧߚ‫ޕ‬mp: 236˚C(decomp.); 1H-NMR(δ, CDCl3, 400

⸅ᇦࠍỹ೎ߒߡṁᇦࠍᷫ࿶⇐෰ߒߚᓟ㧘ࠕ࡞ࡒ࠽ࠞ࡜ࡓ

MHz): 3.93(3H, s, CH3), 7.12(2H, d, J = 8.8 Hz, C3’-H andࠢࡠࡑ࠻ࠣ࡜ࡈࠖ࡯(ዷ㐿ṁᇦ㧦㈶㉄ࠛ࠴࡞㧦ࡋࠠࠨࡦ =J = 8.8 Hz, C8-H), 8.54(1H, dd, J = 2.9 and 8.8 Hz, C7-H),

17%) ߣ ߒ ߡ ᓧ ߚ ‫ ޕ‬mp: 198˚C(decomp.);

C5’-H), 8.23(2H, d, J = 8.8 Hz, C2’-H and C6’-H), 8.26(1H, d,

2 : 1)ߦࠃࠅ♖⵾ߒ㧘⋡⊛ൻว‛(4a)ࠍ㤛⦡࿕૕(15 mg,

DMSO-d6, 400 MHz): 3.84(3H, s, NH2), 6.94(1H, d, J = 2.3

9.00(1H, d, J = 2.9 Hz, C5-H), and 9.46 ppm(1H, s, C3-H);
IR(KBr): 3053 and 2901(νC-H), 1523 and 1341(νNO ), 1256

Hz, C5-H), 7.09(2H, d, J = 8.8 Hz, C3’-H and C5’-H), 7.23(1H,

2dd, J = 2.3 and 9.0 Hz, C7-H), 7.75(1H, d, J = 9.0 Hz, C8-H),

and 1028(νC-O), and 833 cm (γC-H); Anal. Calcd for-1

H-NMR(δ,1

C15H11N3O3࡮0.05H2O: C, 63.85; H, 3.97; N, 14.89. Found: C,

8.16(2H, d, J = 8.8 Hz, C2’-H and C6’-H), and 9.21 ppm(1H, s,

2-(4’-ࡔ࠴࡞࠴ࠝࡈࠚ࠾࡞)-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(3b):1021(νC-O), and 837 cm-1(γC-H).

63.59; H, 3.90; N, 14.84.

CH3); IR(KBr): 3646 and 3336(νN-H), 3062(νC-H), 1233 and෼ ₸ 67%; mp: 232˚C; 1H-NMR(δ, CDCl3, 400 MHz):2-(4’-ࠪࠕࡁࡈࠚ࠾࡞)-6-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ(4c): ෼₸

8.22(2H, d, J = 8.7 Hz, C2’-H and C6’-H), 8.26(1H, d, J = 9.2

MHz): 6.94 (1H, d, J = 2.4 Hz, C5-H), 7.28(1H, dd, J = 2.4

2.59(3H, s, CH3), 7.44(2H, d, J = 8.7 Hz, C3’-H and C5’-H),

quant.; mp: 232˚C(decomp.); 1H-NMR(δ, DMSO-d6, 400

Hz, C8-H), 8.55(1H, dd, J = 2.4 and 9.2 Hz, C7-H), 9.01(1H, d,

J = 2.4 Hz, C5-H), and 9.47 ppm(1H, s, C3-H); IR(KBr): 3053

and 2923(νC-H), 1548 and 1341(νNO ), 1411, 1296 and2

and 8.7 Hz, C7-H), 7.80-7.86(2H, m, C2’-H and C6’-H),

7.96-7.99(2H, m, C3’-H and C5’-H), 8.39(1H, d, J = 8.7 Hz,

C8’-H), 9.33 ppm(1H, s, C3-H); IR(KBr): 3418(νN-H),

670(νS-C), and 824 cm-1(γC-H); Anal. Calcd for C15H11N3O2

2222(νC-N), 1621(δN-H), and 828 cm-1(γC-H).

4.07; N, 13.41.

෼₸ quant.; 1H-NMR(δ, DMSO-d6, 400 MHz): 3.77(6H, s,S࡮0.6H2O: C, 58.47; H, 3.99; N, 13.64. Found: C, 58.74; H,

2,3-ࠫ(4’-ࡔ࠻ࠠࠪࡈࠚ࠾࡞)-6-ࠕࡒࡁࠠࡁࠠࠨ࡝ࡦ(6):CH3), 6.05(2H, s, NH2), 6.87-6.92(4H, m, C3’-H and C5’-H),

2-(4’-ࠪࠕࡁࡈࠚ࠾࡞)-6-࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦ(3c): ෼₸
55%; mp: 254-256˚C;

6.94(1H, d, J = 2.5 Hz, C5-H), 7.22(1H, dd, J = 2.5 and 8.9

H-NMR(δ, CDCl3, 400 MHz):1

7.91(2H, d, J = 8.4 Hz, C2’-H and C6’-H), 8.33(1H, d, J = 9.2

Hz, C7-H), 7.31-7.38(4H, m, C2’-H and C6’-H), and 7.44

㧙㧙


ppm(1H, d, J = 8.9 Hz, C8-H); IR(KBr): 3438 and 3378(νN-H),

6.79 (1H, d, J = 8.2 Hz, C4-H), 6.81 (1H, s, C1-H), 7.57 (1H, d,(γC-H).

C7-H), and 10.8 ppm (1H, s, NH); IR (KBr): 1518 and

1606(δN-H), 1295(νC-N), 1244 and 1026(νC-O), and 835 cm

J = 8.8 Hz, C10-H), 8.00 (1H, d, J = 8.8 Hz, C9-H), 8.06 (1H, s,-11342(νNO ), 1080(νC-O), 972 and 813 cm-1(γC-H).

1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ߹ߚߪ 1,4-ࡌࡦ࠱࠴ࠕࠫࡦ❗Ⅳ 8-

28-࠾࠻ࡠ-12H-5-࠴ࠕ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲࠮ࡦ (11):࠾࠻ࡠࠠࡁࠠࠨ࡝ࡦߩวᚑ

෼₸ 85%; mp: 327˚C (decomp.); 1H-NMR (δ, DMSO-d6, 400

ઍ⴫଀: 8-࠾࠻ࡠ-12H-5-ࠝࠠࠨ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲

MHz): 6.87 (1H, d, J = 7.6 Hz, C2-H), 6.91 (1H, d, J = 7.6 Hz,

࠮ࡦ(7)ߩวᚑ ࠕ࡞ࠧࡦ㔓࿐᳇ਅߢ㧘2,3-ࠫࠢࡠࡠ-6-࠾࠻ࡠࠠࡁࠠࠨ
࡝ࡦ(2) (245 mg, 10. mmol)ߣ 2-ࠕࡒࡁࡈࠚࡁ࡯࡞(110 mg,

C1-H), 7.06 (2H, d, J = 7.6 Hz, C3-H and C4-H), 7.44 (1H, d, J
= 9.0 Hz, C10-H), 8.11 (1H, dd, J = 2.7 and 9.0 Hz, C9-H),

1.0 mmol)ࠍή᳓ DMF ਛ㧘὇㉄ࠞ࡝࠙ࡓ(210 mg, 1.5

8.20 (1H, d, J = 2.4 Hz, C7-H), and 10.8 ppm (1H, s, NH). IR

ߚᓟ㧘ᱷᷲࠍ THF (130 mL)ߦṁ⸃ߒ㘻๺㘩Ⴎ᳓(30 mL)

833 and 742 cm-1(γC-H); Anal. Calcd for C14H8N4O2S: C,(KBr): 3374 and 3311(νN-H), 1616(δN-H) 1543 and 1350(νNO ),mmol)ሽ࿷ਅߢ 3 ᤨ㑆ടᾲㆶᵹߒߚ‫ޕ‬ṁᇦࠍᷫ࿶⇐෰ߒ

256.75; H, 2.72; N, 18.91. Found: C, 56.88; H, 2.47; N, 18.68.

ߢᵞᵺߒ㧘᦭ᯏጀࠍή᳓⎫㉄ࡑࠣࡀࠪ࠙ࡓߢੇ῎ߒߚ‫ޕ‬8-࠾࠻ࡠ-5H-12-࠴ࠕ-5,6,11-࠻࡝ࠕࠩ࠽ࡈ࠲࠮ࡦ(12): ෼ṁᇦࠍᷫ࿶⇐෰ߒߚᓟ㧘ࠪ࡝ࠞࠥ࡞ࠞ࡜ࡓࠢࡠࡑ࠻ࠣ࡜
ࡈࠖ࡯(ዷ㐿ṁᇦ㧦࠻࡞ࠛࡦ㧦㈶㉄ࠛ࠴࡞ = 7 : 1)ߢ♖⵾₸ 12%; mp: 320˚C; 1H-NMR (δ, DMSO-d6, 400 MHz): 6.91

ᓧߚ‫ߚ߹ޕ‬㧘᭴ㅧ⇣ᕈ૕ߢ޽ࠆ 8-࠾࠻ࡠ-12H-5-ࠝࠠࠨC1-H and C4-H), 7.65 (1H, dd, J = 2.3 and 8.9 Hz, C10-H),ߒߡᓧߚ‫(ޕ‬7) mp: 350˚C (decomp.); H-NMR (δ, DMSO-d6,

and 10.6 ppm (1H, s, NH); IR (KBr): 3377 and 3309(νN-H),

8.8 Hz, C1-H), 6.95 (1H, d, J = 7.1 Hz, C3-H), 6.99 (1H, d, J =1,4-ࡌࡦ࠱ࠝࠠࠨࠫࡦ߹ߚߪ 1,4-ࡌࡦ࠱࠴ࠕࠫࡦ❗Ⅳ 8-(2H, d, J = 8.5 Hz, C2-H and C3-H), 7.08 (2H, d, J = 7.3 Hz,ߔࠆߎߣߢ⋡⊛ൻว‛(7)ࠍ㤛⦡࿕૕(56 mg, 20 %)ߣߒߡ

8.00 (1H, dd, J = 2.7 and 8.8 Hz, C9-H), 8.05 (1H, s, C7-H),-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲࠮ࡦ(8)ࠍ㤛⦡࿕૕(8 mg, 3%) ߣ11617(γN-H), 1522 and 1350(νNO2), 831 and 742 cm-1(γC-H).

400 MHz): 6.83 (1H, d, J = 7.6 Hz, C2-H), 6.90 (1H, d, J =8.0 Hz, C4-H), 7.48 (1H, d, J = 8.8 Hz, C10-H), 8.11 (1H, dd, Jࠕࡒࡁࠠࡁࠠࠨ࡝ࡦߩวᚑ

= 2.3 and 8.8 Hz, C9-H), 8.15 (1H, s, C7-H), and 11.1 ppm

ઍ⴫଀㧦8-ࠕࡒࡁ-12H-5-࠴ࠕ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲࠮

(1H, s, N12-H); IR (KBr): 1515 and 1355(νNO ), 1080(νC-O),

ࡦ(15)ߩวᚑ

and 744 cm (γC-H); Anal. Calcd for C14H8N4O3࡮0.49H2O: C, 10%ࡄ࡜ࠫ࠙ࡓ὇⚛(62 mg) ߦή᳓ THF (10 mL)ࠍട

2-1

58.17; H, 3.13; N, 19.38. Found: C, 58.34; H, 2.69; N, 19.02.

߃᳓⚛㔓࿐᳇ਅߢ 30 ಽ㑆೨ㆶరߒߚᓟ㧘8-࠾࠻ࡠ-12H-5-

6.80 (1H, d, J = 7.8 Hz, C3-H), 6.85 (1H, d, J = 7.8 Hz, C2-H),mmol)ߩή᳓ THF ṁᶧ(200 mL)ࠍട߃ 45 ᤨ㑆᳓⚛ᷝടࠍࠝ ࠠ ࠨ -6,11,12- ࠻ ࡝ ࠕ ࠩ ࠽ ࡈ ࠲ ࠮ ࡦ (7)(429 mg, 1.45(8) mp: 350˚C (decomp.); H-NMR (δ, DMSO-d6, 400 MHz):1

6.95 (1H, d, J = 3.9 Hz, C4-H), 6.97 (1H, d, J = 4.6 Hz, C1-H),ⴕߞߚ‫⸅ޕ‬ᇦࠍỹ೎ߒߡṁᇦࠍᷫ࿶⇐෰ߒߚᓟ㧘ࠢࡠࡠ

7.57 (1H, d, J = 8.8 Hz, C10-H), 8.00 (1H, dd, J = 2.6 and 8.8ࡎ࡞ࡓ߆ࠄౣ⚿᥏ߔࠆߎߣߦࠃࠅ⋡⊛ൻว‛(15)ࠍⶊ⦡

Hz, C9-H), 8.07 (1H, s, C7-H), and 10.9 ppm (1H, s, NH); IR࿕૕(315 mg, 82%)ߣߒߡᓧߚ‫ޕ‬mp: 326˚C; 1H-NMR (δ,(KBr): 1516 and 1343(νNO ), 1080(νC-O), 971 and 838

cm (γC-H).
-1

DMSO-d6, 400 MHz): 5.49 (2H, s, N8-H), 6.60 (1H, dd, J =2

2.2 Hz, C4-H), 6.75 (1H, t, J = 7.6 Hz, C3-H), 6.80 (1H, d, J =3-ࡔ࠴࡞-8-࠾࠻ࡠ-12H-5-ࠝࠠࠨ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲

࠮ࡦ(9): ෼₸ 10%; mp: 295-296˚C; H-NMR (δ, DMSO-d6,
1

7.6 Hz, C1-H), 6.86 (1H, dd, J = 2.4 and 8.8 Hz, C2-H), 6.97

(1H, dd, J = 2.4 and 8.8 Hz, C9-H), 7.01 (1H, d, J = 8.8 Hz,

400 MHz): 2.18 (3H, s, CH3), 6.70 (1H, d, J = 7.6 Hz, C1-H),

C7-H), 7.18 (1H, d, J = 8.8 Hz, C10-H), and 9.70 ppm (1H, s,

J = 7.3 Hz, C10-H), 8.09 (1H, d, J = 9.5 Hz, C9-H), 8.12 (1H, s,

917, 823, and 747 cm-1(γC-H); Anal. Calcd for C14H10N4S࡮

6.77 (1H, d, J = 6.7 Hz, C2-H), 6.80 (1H, s, C4-H), 7.44 (1H, d,
C7-H), and 11.0 ppm (1H, s, NH); IR (KBr): 1518 and1335(νNO ), 1101(νC-O), 965 and 810 cm (γC-H); Anal. Calcd-1

2

N12-H); IR(KBr): 3449 and 3339(νN-H), 1477 and 1301(νC-N),

0.06H2O: C, 63.14; H, 3.78; N, 21.04. Found: C, 62.88; H,
3.81; N, 20.95.

for C15H10N4O3 ࡮ 0.03H2O:C, 61.22;H, 3.43;N, 19.04.

8-ࠕࡒࡁ-12H-5-ࠝࠠࠨ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲࠮ࡦ(13):Found: C,61.11 ;H, 3.44;N, 19.04.

෼₸ 21%; mp: 267˚C (decomp.); 1H-NMR (δ, DMSO-d6, 400

3-ࡔ࠴࡞-8-࠾࠻ࡠ-5H-12-ࠝࠠࠨ-5,6,11-࠻࡝ࠕࠩ࠽ࡈ࠲

MHz): 5.37 (2H, s, N8-H), 6.57 (1H, s, C7-H), 6.71 (1H, d, J =400 MHz): 2.19 (3H, s, CH3), 6.70 (1H, d, J = 8.2 Hz, C3-H),

C9-H), 6.88 (2H, d, J = 8.0 Hz, C2-H and C3-H), 7.17 (1H, d, J

7.1 Hz, C1-H), 6.74 (1H, d, J = 8.0 Hz, C10-H), 6.78 (1H, s,࠮ࡦ(10): ෼₸ 4%; mp: 300˚C; H-NMR (δ, DMASO-d6,
1

㧙㧙


= 8.5 Hz, C4-H), and 9.92 ppm (1H, s, N12-H); IR (KBr): 3301

ෳ⠨ᢥ₂3-ࡔ࠴࡞-8-ࠕࡒࡁ-12H-5-ࠝࠠࠨ-6,11,12-࠻࡝ࠕࠩ࠽ࡈ࠲

1㧕 J.E. Silva, Physiol. Rev., 86, 435 (2006).

and 3221(νN-H), 1199(νC-O), 824 and 746 cm (γC-H).
-1

࠮ ࡦ (14): ෼ ₸ quant.; mp: 306-307˚C;

2㧕 M. Karnebogen, D. Singer, M. Kallerhoff, and

H-NMR (δ,1

R.-H. Ringert, Thermochin. Acta, 229, 147

DMSO-d6, 400 MHz): 2.15 (3H, s, CH3), 5.33 (2H, s, N8-H),(1993).

6.55 (1H, d, J = 2.4 Hz, C7-H), 6.59 (1H, d, J = 7.8 Hz, C2-H),

6.69 (1H, d, J = 8.4 Hz, C4-H), 6.70 (1H, s, C1-H), 6.76 (1H,

3㧕 J. Lou, T.A. Hatton, and P.E. Laibinis, Anal.

and 9.80 ppm (1H, s, N12-H); IR (KBr): 3318 and 3216(νN-H),

4㧕 N. Chandrasekharan and L.A. Kelly, J. Am. Chem.

8-(ࠕࠢ࡝ࡠࠗ࡞)ࠕࡒࡁ-12H-5-࠴ࠕ-6,11,12-࠻࡝ࠕࠩ࠽

5㧕 M. Engeser, L. Fabbrizzi, M. Licchelli, and D.

Chem., 69, 1262 (1997).

dd, J = 2.4 and 8.4 Hz, C9-H), 7.14 (1H, d, J = 8.4 Hz, C10-H),

Soc., 123, 9898 (2001).

2916(νC-H), 1200(νC-O), 858 and 830 cm (γC-H).
-1

Sacchi, Chem. Commun., 1191 (1999).

ࡈ࠲࠮ࡦ(16)ߩวᚑ
 ൻว‛ 15 (52 mg, 0.20 mmol)ߣ࠻࡝ࠛ࠴࡞ࠕࡒࡦ(416㧕 I.D. Figueroa, M. El Baraka, E. Quiñones, and O.

࡞(24 µL, 0.29 mmol)ࠍട߃ߡ 8 ᤨ㑆ቶ᷷ߢᠣᜈߒߚ‫ޕ‬ṁ

7㧕 S. Uchiyama, Y. Matsumura, A.P. de Silva, and K.

Rosario, Anal. Chem., 70, 3974(1998).

µL, 0.29 mmol)ߩή᳓ DMF ṁᶧ(5 mL)ߦႮൻࠕࠢ࡝ࡠࠗ

Iwai, Anal. Chem., 75, 5926(2003).

ᇦࠍᷫ࿶⇐෰ߒߚᓟ㧘ࠕ࡞ࡒ࠽ࠞ࡜ࡓࠢࡠࡑ࠻ࠣ࡜ࡈࠖ

8㧕 Y. Shiraishi, R. Miyamoto, and T. Hirai, Langmuir,࡯(ዷ㐿ṁᇦ㧦㈶㉄ࠛ࠴࡞㧦ࡋࠠࠨࡦ㧩2:1)ߢ♖⵾ߒߡ⋡24, 4273 (2008).

⊛ൻว‛(16)ࠍᯍ⦡࿕૕(29 mg, 46%)ߣߒߡᓧߚ‫ޕ‬mp:

287˚C; H-NMR(δ, DMSO-d6, 400 MHz): 5.79(1H, dd, J =9㧕 Y. Shiraishi, R. Miyamoto, X. Zhang, and T. Hirai,

CH2=CH), 6.45(1H, dd, J = 10 and 17 Hz, CH2=CH),

10㧕 Y. Matsumura and A. Katoh, J. Lumin., 128, 625

C2-H and C4-H), 7.40(1H, d, J = 8.8 Hz, C10-H), 7.63(1H, dd,

11 㧕 D.W.Rangnekar and P.V.Tagdiwala, Dyes and10.1(1H, s, N12-H), and 10.3 ppm(1H, s, CONH); IR(KBr):

12㧕 A. Katoh, M. Takahashi, J. Ohkanda, Chem. Lett.,

cm (νC=O).

13㧕L.D. Patsenker and Y.Y. Artyukhova, J. Mol.

 N-ࠗ࠰ࡊࡠࡇ࡞ࠕࠢ࡝࡞ࠕࡒ࠼(NIPAM; 280 mg, 5

14㧕 N. Mizuyama, Y.Tominaga, S. Kohra, K. Ueda, S.

1Org. Lett., 9, 3921 (2007).

1.8 and 10 Hz, CH2=CH), 6.29(1H, dd, J = 2.0 and 17 Hz,(2008).

6.83-6.85(2H, m, C1-H and C3-H), 7.04(2H, t, J = 7.6 Hz,

Pigments, 7, 445 (1986).

J = 2.3 and 8.9 Hz, C9-H), 8.03(1H, d, J = 2.2 Hz, C7-H),

25, 369 (1996).

3282(νN-H), 3061 and 3005 (νC-H), 2956(νC=O), and 1678
-1

Struct., 655, 311 (2003).

poly(16-co-NIPAM)ߩวᚑ

Hirayama and Y. Shigemitsu, Bull. Chem. Soc.

mmol)㧘ൻว‛ 16 (0.8 mg, 5 µmol)㧘α,α’-ࠕ࠱ࡆࠬࠗ࠰ࡉ

Jpn., 79, 602 (2006)࠴ࡠ࠾࠻࡝࡞(4.1 mg, 50 µmol)ࠍࠫࠝࠠࠨࡦ(10 mL)ߦṁ⸃ߒߚ‫ޕ‬෻ᔕṁᶧࠍࠟ࡜ࠬ⵾ߩࠕࡦࡊ࡞࠴ࡘ࡯ࡉߦ౉ࠇ
ߡ 5˚C ߢ 30 ಽ㑆⓸⚛ࡃࡉ࡞ࠍⴕߞߚᓟ㧘60˚C ߢ 8 ᤨ㑆.

㊀วࠍⴕߞߚ‫ޕ‬᳖಄ߒߚᓟ㧘෻ᔕᶧࠍࠫࠛ࠴࡞ࠛ࡯࠹࡞
(200 mL)ߦᵈ߉㧘ṁ⸃ౣᴉᠲ૞ࠍⴕ߁ߎߣߢ㧘poly(16-coNIPAM)ࠍ 82%ߩ෼₸ߢᓧߚ‫ޕ‬㧙㧙