S. Watanabe et al.
Bull. Chem. Soc. Jpn., 77, No. 3 (2004)
573
absorption spectra were recorded on a JASCO Ubset-560 or Shi-
madzu UV-2500PC spectrophotometer. Fluorescence spectra were
recorded on a Hitachi F4500 fluorescence spectrophotometer.
Flash column chromatography was performed by using a Wakogel
C-200 (70–150 mm, Wako Pure Chemical Co.). Elemental analyses
were performed at the Center of Instrumental Analysis of Gunma
University. Melting points are uncorrected. Special grade chloro-
form and acetonitrile (Kanto Chemicals) were used without further
purification.
We thank one of the referees for his precise comments. This
work was supported in part by a Grant-in-Aid for Scientific Re-
search from the Ministry of Education, Culture, Sports, Science
and Technology.
References
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Synthesis of 2-[3-(benzoylthioureidomethyl)benzylamino]-4-
butylamino-6-diethylamino]-s-triazine. To a solution of ammo-
nium isothiocyanate (0.60 g, 8.2 mmol) in acetone (50 mL), benzyl
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6-diethylamino-s-triazine6a (1.60 g, 4.47 mmol) in acetone (20
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by column chromatography (CH2Cl2–AcOEt = 5:1). Yield 0.95 g
2
V. Massey and P. Hemmerich, Biochem. Soc. Trans., 8, 256
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3
Chem. Acc., 102, 355 (1999). b) Y.-J. Zheng and R. L. Orstein,
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4
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1
(41%, yellow oil). H NMR (CDCl3) ꢁ 0.90 (3H, t, J ¼ 7:3 Hz,
5
Y. Yano, Rev. Heteroatom Chem., 22, 151 (2000); Y. Yano,
NHCH2CH2CH2CH3), 1.10 (6H, t, J ¼ 6:2 Hz, N(CH2CH3)2),
1.34 (2H, m, NHCH2CH2CH2CH3), 1.52 (2H, m, NHCH2-
CH2CH2CH3), 3.32 (2H, q, J ¼ 6:2 Hz, NHCH2CH2CH2CH3),
3.50 (4H, J ¼ 7:0 Hz, N(CH2CH3)2), 4.56 (2H, d, J ¼ 5:9 Hz,
C6H4CH2NHC(=S)NH–), 4.88 (2H, m, C6H4CH2NH–), 5.26
(1H, bs, NH), 7.26–7.32 (4H, m, C6H4), 7.45–7.80 (5H, m, C6H5),
11.0 (1H, bs, NHCOC6H5).
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6
a) T. Kajiki, H. Moriya, K. Hoshino, T. Kuroi, S.-I. Kondo,
T. Nabeshima, and Y. Yano, J. Org. Chem., 64, 9679 (1999). b) H.
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2229.
Receptor 2. A mixture of the above triazine (0.8 g, 1.54 mmol)
in 1,4-dioxane (10 mL) and 10% NaOH (5 mL) was refluxed at 90
ꢃC for 4 h. After cooling, the solution was extracted with CHCl3
(30 mL ꢆ 3). The CHCl3 layer was washed with water and dried
over Na2SO4. After evaporating the solvent in vacuo, the residue
was recrystallized from EtOH. Yield 0.35 g (55%), mp 151–152
ꢃC. 1H NMR (CDCl3) ꢁ 0.90 (3H, t, J ¼ 7:2 Hz, NHCH2CH2-
CH2CH3), 1.10 (6H, t, J ¼ 6:6 Hz, N(CH2CH3)2), 1.34 (2H, m,
NHCH2CH2CH2CH3), 1.47 (2H, q, J ¼ 7:5 Hz, NHCH2-
CH2CH2CH3), 3.27 (2H, q, J ¼ 6:3 Hz, NHCH2CH2CH2CH3),
3.47 (4H, q, J ¼ 6:9 Hz, N(CH2CH3)2), 4.59 (2H, m,
CH2C6H4CH2), 5.05 (1H, bs, NH), 5.63 (1H, bs, NH), 6.22 (2H,
bs, C(=S)NH2), 7.12–7.26 (4H, m, C6H4). Found: C, 57.66; H,
7.80; N, 26.70%. Calcd for C20H32N8S: C, 57.66; H, 7.74; N,
26.90%.
Receptor 3. A mixture of 2 (0.22 g, 0.53 mmol) and MeI
(0.032 mL, 0.60 mmol) in MeOH (30 mL) was stirred overnight
at room temperature. After evaporating the solvent, the residue
was washed with diethyl ether (10 mL ꢆ 2) and recrystallized from
diethyl ether–acetone. Yield 0.13 g (44%), mp 130–131 ꢃC.
1H NMR (CDCl3) ꢁ 0.92 (3H, t, J ¼ 7:3 Hz, NHCH2-
CH2CH2CH3), 1.15 (6H, t, J ¼ 6:6 Hz, N(CH2CH3)2), 1.38 (2H,
m, NHCH2CH2CH2CH3), 1.53 (2H, q, J ¼ 7:5 Hz, NHCH2-
CH2CH2CH3), 2.61 (3H, s, SCH3), 3.35 (2H, q, J ¼ 6:3 Hz,
NHCH2CH2CH2CH3), 3.55 (4H, q, J ¼ 6:9 Hz, N(CH2CH3)2),
4.56 (4H, d, J ¼ 5:6 Hz, CH2C6H4CH2), 7.23–7.34 (4H, m, C6H4).
Found: C, 45.00; H, 6.28; N, 19.73%. Calcd for C21H35IN8S: C,
45.16; H, 6.32; N, 20.06%.
7
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9
2240.
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13 The reaction scheme and rate equation are as follows:
k2[BNAH]
K'
Product
C
8-AzaFl + R
k3[PhSH]2[Bu3N]
Flavin Mimics. 10-Dodecylisoalloxazine (Fl), 5-deaza-10-do-
decylisoalloxazine (5-DeazaFl), 6-AzaFl, and 8-aza-10-dodecyl-
isoalloxazine (8-AzaFl) were supplied from our previous study.6,14
Determination of Binding and Rate Constants. Experimen-
tal procedures were the same as described previously.6a
or k [PhSH]2[Bu N]
ko[BNAH]
o
3
R: Receptor