Molecules 2021, 26, 3817
11 of 14
0
3.2.3. 2,2 -({4-[(4-nitrophenyl)ethynyl]phenyl}azanediyl)di(ethane-2,1-diyl)dipropianate (10
2,20-({4-[(4-nitrophenyl)ethynyl]phenyl}azanediyl)di(ethan-1-ol) (
) (1 g, 3.67 mmol,
1 equiv) was dissolved in THF (5 mL); then propionic acid ( ) (1 mL, 13.5 mmol) was added
)
8
9
to this solution and was stirred. The resulting solution was treated with pyridine (0.5 mL,
1 equiv) and this was followed by the addition of propylphosphonic anhydride solution
◦
(T3P®) (2 mL, 3 equiv). The mixture was heated at 50 C under nitrogen for 48 h; the
solvent was concentrated under reduced pressure and after was neutralized with sodium
carbonate solution. The product was purified by column chromatography on silica gel
1
(7:3 hexane/AcOEt) to afford the desired product in 79% yield (from
NMR (300 MHz, CDCl3)
2H, J = 9 Hz), 6.74 (d, 2H, J = 9 Hz), 4.27 (t, 4H, J = 6 Hz), 3.67 (t, 4H, J = 6 Hz), 2.33 (q, 4H,
J = 9 Hz), 1.13 (t, 3H, J = 6 Hz). 13C NMR (75 MHz, CDCl3)
(ppm): 174.4, 148, 146.3, 133.5,
8) as orange oil. H
δ
(ppm): 8.17, (d, 2H, J = 9 Hz), 7.60 (d, 2H, J = 9 Hz), 7.42 (d,
δ
131.7, 123.6, 111.7, 109.5, 96.5, 86.6, 61.1, 49.5, 27.5, 9.1. FT-IR (KBr),
ν
(cm−1): 3297, 2927,
2857, 2209, 1719, 1607, 1518, 1380, 1339, 1231, 861, 809.
0
3.2.4. 2,2 -({4-[(4-aminophenyl)ethynyl]phenyl}azanediyl) di(ethane-2,1-diyl)dipropianate (11
)
2,20-({4-[(4-nitrophenyl)ethynyl]phenyl}azanediyl)di(ethane-2,1-diyl)dipropianate (10
)
(0.5 g, 1.629 mmol) was dissolved in MeOH (30 mL), then an excess of sodium hydrosulfite
salt (NaHSO3, 7 g, 40 mmol) in H2O (40 mL) was added to this solution and stirred. The
resulting solution was stirred at room temperature under nitrogen for 24 h. After, the solvent
was concentrated under reduced pressure, and the residue was taken up in water (40 mL)
and was extracted with AcOEt (3
MgSO4 and was concentrated under reduced pressure. The product was purified by column
×
150 mL). The ethyl acetate was dried over anhydrous
chromatography on silica gel (1:1 hexane/AcOEt) to afford the desired product in 82% yield
1
(from 10) as yellow oil. H NMR (300 MHz, CDCl3)
δ (ppm): 7.29, (d, 2H, J = 9 Hz), 7.21
(d, 2H, J = 9 Hz), 6.63 (d, 2H, J = 9 Hz), 6.56 (d, 2H, J = 9 Hz), 4.18 (t, 4H, J = 6 Hz), 3.56 (t,
4H, J = 9 Hz), 2.25 (q, 4H, J = 9 Hz), 2.02 (s, 2H), 1.05 (t, 6H, J = 9 Hz). FT-IR (KBr),
ν
(cm−1):
3317, 3061, 2958, 2928, 2210, 1722, 1682, 1583, 1465, 1355, 1266, 1165, 735.
3.2.5. {4-[(1E)-3-(1H-indol-3-yl)-3-oxoprop-1-en-1-yl]phenoxy} acetic acid (14)
{4-[(1E)-3-(1H-indol-3-yl)-3-oxoprop-1-en-1-yl]phenoxy} acetic acid (14) was prepared
according to the procedure described in reference [6].
3.2.6. 2,20-[(4-{[4-({4-[(1. E)-3-(1H-indol-3-yl)-3-oxoprop-1-en-1-yl]phenoxy}acetamido)
phe-nyl]ethynyl}phenyl)azanediyl]di(ethane-2,1-diyl)dipropionate (15)
A mixture of compound {4-[(1E)-3-(1H-indol-3-yl)-3-oxoprop-1-en-1-yl]phenoxy}-
0
acetic acid (14) (0.5 g, 1.557 mmol) and 2,2 -({4-[(4-aminophenyl)ethynyl]phenyl}azanediyl)
bis(ethane-2,1-diyl)dipropianate (11) (0.5 g, 1.225 mmol) was dissolved in THF (10 mL)
and was stirred. Then, the solution was treated with pyridine (1.5 mL, 1 equiv) and was
followed by the addition of propylphosphonic anhydride solution (T3P®) (2.5 mL, 3 equiv).
◦
The mixture was heated at 50 C under nitrogen for 24 h and was concentrated under
reduced pressure after. The product was purified by column chromatography on silica gel
(1:1 hexane/AcOEt, added 5% of MeOH, followed by elution 6:4 hexane/AcOEt,) to afford
1
the desired product in 83% yield (from 11) as yellow oil. H NMR (300 MHz, CDCl3)
δ
(ppm): 9.87 (s, 1H), 8.83 (s, 1H), 8.33-8.30 (m, 1H), 8.18 (s, 1H), 7.87–7.82 (m, 2H), 7.79 (d,
1H, J = 3 Hz), 7.52–7.49 (m, 2H), 7.44–7.41 (m, 2H), 7.34–7.30 (m, 3H), 7.23–7.20 (m, 3H),
7.08–7.03 (m, 2H), 6.67–6.62 (m, 2H), 4.63 (s, 2H), 4.19 (t, 4H, J = 6 Hz), 3.58 (t, 4H, J = 9 Hz),
2.26 (q, 4H, J = 6 Hz), 1.05 (t, 6H, J = 6 Hz). 13C NMR (75 MHz, CDCl3)
δ
(ppm): 190.8, 174.6,
165.3, 148.2, 148.1, 147.4, 136.1, 132.5, 132.4, 131.8, 123.9, 123.7, 122.9, 122.6, 120.9, 120.1,
115.4, 111.9, 111.6, 109.6, 91.4, 87.3, 67.7, 61.4, 49.7, 29.9, 27.7, 9.7. FT-IR (KBr),
(cm−1):
3350, 3041, 2977, 2940, 2202, 2124, 1736, 1680, 1602, 1520, 1439, 1383, 1038, 1155, 827, 812.
ν