114
Structural Study and Fluorescent Property of a Novel Organic Microporous Crystalline Material
J. Braz. Chem. Soc.
2H), 4.40 (t, 2H, J 12 Hz), 3.86 (t, 2H, J 12 Hz); IR ν/cm-1
2926, 2875, 1608, 1522, 1343, 1276, 1026, 745, 667.
4.15 (s, 8H), 3.56 (s, 12H); IR ν/cm-1 3067, 2993, 2951,
2921, 2888, 1748, 1596, 1509, 1173, 742, 706.
1-Nitro-2-[2-(2-nitrophenoxy)ethoxy]benzene 2
[(2-{2-[2-(Bis-methoxycarbonylmethylamino)-
5-methylphenoxy]ethoxy}-4-formyl-5-methyl-phenyl)
methoxycarbonylmethylamino]acetic acid methyl ester 5
To a solution of 1 (2.01 g, 0.01 mol) in DMF (10 mL)
at room temperature, 2-nitrophenol (1.39 g, 0.01 mol)
and K2CO3 (2.50 g, 0.018 mol) were added. The reaction
mixture was stirred at 140 °C for 4 h, cooled and poured into
cold water (20 mL). The formed yellow solid was filtered
and washed with water (3 × 5 mL). The crude product was
recrystallized in MeOH to give yellow solid 2.Yield 95%;
m.p. 168-169 °C; 1H NMR (CDCl3, 400 MHz) d 7.83 (d,
2H, J 8 Hz), 7.57 (t, 2H, J 8 Hz), 7.24 (t, 2H, J 8 Hz), 7.08
(t, 2H, J 8 Hz), 4.54 (s, 4H); IR ν/cm-1 3051, 2956, 2931,
1606, 1582, 1518, 1359, 1278, 1159, 1090, 744, 671.
POCl3 (2.4 mL) was added dropwise over 40-45 min
into a dry three-necked flask which contained anhydrous
DMF (20 mL). The POCl3/DMF mixture was stirred at
room temperature for 1-2 h and added dropwise into a
DMF (20 mL) solution of compound 4 (5.32 g, 0.01mol)
afterwards. The reaction mixture was heated at 75 °C
for 4 h, concentrated in vacuo, and then poured into ice
water. The suspension was filtered and purified by column
chromatography (silica gel, V(EtOAc):V(hexane) = 1:1
as eluent) to afford white solid 5.20 Yield 85%; m.p.
131-132 °C; 1H NMR (CDCl3, 400 MHz) d 9.80 (s, 1H),
7.38 (m, 2H), 6.86 (m, 4H), 6.76 (d, 1H, J 8.3 Hz), 4.31 (m,
2H), 4.27 (m, 2H), 4.24 (s, 4H), 4.15 (s, 4H), 3.57 (s, 6H),
3.56 (s, 6H); 13C NMR (CDCl3, 101 MHz) d 190.5, 171.9,
171.2, 150.1, 149.6, 145.0, 139.3, 129.9, 126.7, 122.2,
121.6, 116.5, 112.9, 110.5, 77.3, 77.0, 76.7, 67.3, 66.6,
53.4, 53.2, 52.0, 51.9, 51.6; IR ν/cm-1 3015, 2954, 2928,
1746, 1681, 1593, 1509, 1245, 1164, 747; HRMS calcd.
for C27H32N2O11: 560.2006, (M+Na)+ calcd.: 583.1898,
(M+Na)+ found: 583.1894.
2-[2-(2-Aminophenoxy)ethoxy]benzenamine 3
Iron powder (3.36 g, 0.06 mol), concentrated
hydrochloric acid (0.2 mL), and anhydrous ethanol (10 mL)
were added into a dried three-necked flask equipped with a
magnetic stirrer. When the mixture was heated to boiling,
2 (3.04 g, 0.01mol) was added in three portions. The
mixture was refluxed for 4 h, and then made alkaline to
litmus by addition of 15% alcoholic potassium hydroxide
solution, the iron powder was removed by filtration
afterwards. Into the filtrate, 6 mol L-1 sulfuric acid was
added and white precipitate was obtained. After filtration,
the precipitate was dissolved in 40 mL of warm water and
made alkaline to pH = 8 with saturated sodium hydroxide
solution. The generated light yellow solid was collected and
recrystallized in MeOH to give white solid 3. Yield 88%;
m.p. 116-117 °C; 1H NMR (CDCl3, 400 MHz) d 6.98 (m,
8H), 4.36 (s, 4H), 3.82 (s, 4H); IR ν/cm-1 3432, 3355, 3059,
2934, 1612, 1507, 1461, 1276, 1217, 941, 739.
[(2-{2-[2-(Bis-methoxycarbonylmethylamino)phenoxy]
ethoxy}-4-benzimidazole-phenyl)methoxycarbonyl-
methylamino]acetic acid methyl ester 6
A mixture of 1,2-phenylenediamine (0.11 g, 1 mmol),
compound 5 (0.56 g, 1 mmol), H2O2 (30%, 4 mmol, 0.4 mL)
and Fe(NO3)3·9 H2O (0.04 g, 0.1 mmol) was heated at 50 °C
for 30 min. After completion of the reaction, the reaction
mixture was dissolved in EtOH (10 mL) and then poured into
ice-water(30mL).Thepuresolidproductwasfiltered, washed
with ice-water, dried and subsequently purified by column
chromatography (silica gel, V(EtOAc):V(hexane) = 1:1 as
eluent)21,22 to afford white solid 6.Yield 80%; m.p. 72-73 °C;
IR (KBr, cm-1) 3505 (νN-H), 3033 (ν=C-H), 2906 (νC-H), 1743
(νC=O), 1509 (νC=C), 1478 (νC=C), 1170 (νC-O), 746 (d=C-H);
1H NMR (400 MHz, CDCl3) d 7.68 (d, 1H, J 8 Hz), 7.56 (s,
3H), 7.17 (s, 2H), 6.87 (m, 2H), 6.83 (m, 1H), 6.70 (m, 2H),
4.13 (s, 8H), 3.91 (m, 3H), 3.85 (s, 2H), 3.54 (s, 6H), 3.51
(s, 6H); 13C NMR (100 MHz, CDCl3) d 172.2, 171.7, 152.2,
150.2, 149.9, 140.8, 138.7, 122.4, 121.4, 120.3, 118.9, 118.2,
112.8, 111.3, 77.4, 77.1, 76.8, 66.9, 66.5, 53.4, 53.3, 51.8;
HRMS calcd. for C33H36N4O10: 648.2431, (M+H)+ calcd.:
649.2504, (M+H)+ found: 649.2487.
1,2-Bis(2-aminophenoxy)ethyl-N,N,N’,N’-acetic acid methyl
ester 4
Compound 3 (2.44 g, 0.01 mol) was dissolved in MeCN
(10 mL), then (i-Pr)2NEt (6 mL) and methyl bromoacetate
(3 mL) were added to the mixture with stirring. The
reaction mixture was refluxed for 24 h. After the reaction,
the mixture was cooled down, poured into EtOAc (20
mL), and filtered to remove the generated white solid.
The combined EtOAc filtrates were concentrated in vacuo
to give an oily solid, then adding a little methanol, white
solid was generated, filtered, air dried and recrystallized
in MeOH to give white solid 4.Yield 87%; m.p. 94-95 °C;
1H NMR (CDCl3, 400 MHz) d 6.85 (m, 8H), 4.27 (s, 4H),