HU ET AL.
7
butylamine (0.513 g 2.77 mmol) was added under N2
atmosphere. The reaction mixture was stirred for 48 hr.
After being cooled, the solvent was then removed by
rotary evaporation. Subsequently, the obtained residue
was dissolved in CH3CN (50 ml), and AgBF4 (0.275 g
1.41 mmol) was added under a N2 atmosphere. The solu-
tion was stirred at room temperature for24 hr and then
filtered through Celite. The solvent was removed in
vacuo. The resulting solid was further treated with anhy-
drous ether to afford compound 11 as a yellow solid. The
yield was 73.6%. IR(KBr): 3,428 cm−1 (Ar-OH), 1,617 cm−1
(C=N). 1H-NMR (400 MHz, DMSO): δ = 13.11 (s, 2H, Ar-
OH), 8.88 (s, 2H, N=CH), 7.40–7.46 (m, 4H, Ar-H), 7.32 (s,
2H, Ar-H), 7.20 (s, 2H, Ar-H), 3.20–3.11 (m, 4H, CH2Cl),
3.10–2.94 (m, 12H, NCH2), 2.91–2.84 (m, 12H, CH2),
2.58–2.51 (m, 4H, Ar-CH2), 2.17 (s, 6H, Ar-CH3), 1.67–1.56
(m, 12H, CH2), 1.58–1.22 (m, 8H, CH2CH2), 0.90 (t, J =
7.3Hz, 9H, CH3).
3.2.8 | Synthesis of 16
The compound synthesized using the same conditions
and procedure as those for 13, starting with 12. A light
yellow oil was obtained in quantitative yield. IR(KBr):
3,421 cm−1 (Ar-OH), 1,616 cm−1 (C=N). H-NMR (400
1
MHz, DMSO): δ = 13.19 (s, 1H, Ar-OH), 13.11 (s, 1H, Ar-
OH), 8.86 (m, 2H, N=CH), 7.36 (d, J = 8.1 Hz, 1H, Ar-H),
7.32 (s, 1H, Ar-H), 7.30 (s, 1H, Ar-H), 7.25 (s, 1H, Ar-H),
7.19 (s, 1H, Ar-H), 7.18 (s, 1H, Ar-H), 7.17 (d, J = 8.6 Hz,
1H, Ar-H), 3.14–3.09 (m, 4H, CH2Cl), 3.10–2.90 (m, 12H,
NCH2), 2.91–2.82 (m, 12H, CH2), 2.76–2.64 (m, 4H, Ar-
CH2), 2.40 (s, 3H, Ar-CH3), 2.20–2.14 (m, 6H, Ar-CH3),
1.68–1.59 (m, 12H, CH2), 1.58–1.19 (m, 8H, CH2CH2),
0.95–0.80 (m, 9H, CH3).
3.2.9 | Synthesis of 1
Compound 13 (0.2 g 0.20 mmol) and anhydrous cobalt
(II) acetate (0.035 g 0.20 mmol) were dissolved in MeOH
(50 ml) under N2 atmosphere. The reaction mixture was
stirred at room temperature for 6 hr. Then, the product
was separated by celite, and the precipitate was triturated
in diethyl ether. Subsequently, the obtained residue was
dissolved in CH2Cl2 (50 ml), and 2,4-dinitrophenol
(0.036g, 0.20 mmol) was added under O2 atmosphere.
After the solution was stirred at room temperature for
approximately 12 hr, sodium 2,4-dinitrophenolate (0.12 g,
0.60 mmol) was added and stirred for further 24 hr, and
then filtered through Celite. The solvent was removed in
vacuo. The resulting solid was further treated with anhy-
drous ether to afford compound 1 as a brown solid (0.33
g, 86.2%).1H-NMR (400 MHz, DMSO) δ = 8.78 (s, 2H,
N=CH), 8.58 (d, J = 13.7 Hz, 3H, Ar-H), 7.82 (d, J = 8.3
Hz, 3H, Ar-H), 7.54–7.47 (m, 2H, Ar-H), 7.39 (s, 2H, Ar-
H), 7.27 (s, 2H, Ar-H), 6.98–6.88 (m, 2H, Ar-H), 6.38 (s,
3H, Ar-H), 2.94–2.88 (m, 4H, CH2Cl), 2.88–2.82 (m, 12H,
NCH2), 2.68 (s, 6H, Ar-CH3), 2.60–2.54 (m, 12H, CH2),
2.52–2.49 (m, 4H, Ar-CH2), 1.70–1.60 (m, 12H, CH2),
1.59–1.24 (m, 8H, CH2CH2), 0.95–0,78 (m, 9H, CH3).
Anal. Calc.(C72H95CoN10O17): C, 60.43; H, 6.63; N, 9.79.
Found: C, 60.35; H, 6.58; N, 9.84.
3.2.6 | Synthesis of 14
The compound synthesized using the same conditions
and procedure as that for 13, starting with 10. A light
yellow oil was obtained in quantitative yield. IR(KBr):
3,423 cm−1 (Ar-OH), 1,617 cm−1 (C=N), 688 cm−1 (Ar-
1
Cl). H-NMR (400 MHz, DMSO): δ = 12.94 (s, 1H, Ar-
OH), 12.83 (s, 1H, Ar-OH), 8.92 (s, 1H, N=CH), 8.88
(s, 1H, N=CH), 7.59 (s, 1H, Ar-H), 7.51–7.43 (m, 2H,
Ar-H), 7.35–7.29 (m, 2H, Ar-H), 7.24–7.18 (m, 2H,
Ar-H), 3.14–3.05 (m, 4H, CH2Cl), 3.04–2.92 (m, 12H,
NCH2), 2.91–2.80 (m, 12H, CH2), 2.62–2.54 (m, 4H,
Ar-CH2), 2.20–2.12 (m, 6H, Ar-CH3), 1.68–1.58
(m, 12H, CH2), 1.58–1.16 (m, 8H, CH2CH2), 0.90–0.73
(m, 9H, CH3).
3.2.7 | Synthesis of 15
The compound synthesized using the same conditions
and procedure as those for 13, starting with 11. A light
yellow oil was obtained in quantitative yield. IR(KBr):
3,419 cm−1 (Ar-OH), 1,617 cm−1 (C=N), 1,495 cm−1 (Ar-
OCH3). 1H-NMR (400 MHz, DMSO): δ = 13.26 (s, 1H, Ar-
OH), 13.03 (s, 1H, Ar-OH), 8.90 (s, 1H, N=CH), 8.86 (s,
1H, N=CH), 7.45 (d, J = 8.7 Hz, 1H, Ar-H), 7.34 (s, 1H,
Ar-H), 7.30 (s, 1H, Ar-H), 7.21 (s, 1H, Ar-H), 7.16 (s, 1H,
Ar-H), 7.12 (s, 1H, Ar-H), 7.02 (d, J = 8.7 Hz, 1H, Ar-H),
3.85 (s, 3H, OCH3), 3.17–3.12 (m, 4H, CH2Cl), 3.11–2.96
(m, 12H, NCH2), 2.94–2.82 (m, 12H, CH2), 2.62–2.54 (m,
2H, Ar-CH2), 2.28–2.07 (m, 6H, Ar-CH3), 1.68–1.59 (m,
12H, CH2), 1.59–1.15 (m, 8H, CH2CH2), 0.95–0.78 (m,
9H, CH3).
3.2.10 | Synthesis of 2
The compound synthesized using the same conditions
and procedure as those for 1, starting with 10. A brown
1
solid was obtained in quantitative yield. H-NMR (400
MHz, DMSO): δ = 8.84 (s, 1H, N=CH), 8.77 (s, 1H,
N=CH), 8.58 (d, J = 12.8 Hz, 3H, Ar-H), 7.81 (d, J = 7.7
Hz, 3H, Ar-H), 7.58 (d, J = 8.7 Hz, 1H, Ar-H), 7.43 (s, 1H,