[(2-{2-[2-(Bis-methoxycarbonylmethylamino)phenoxy]ethoxy}-4-benzimidazole-phenyl)methoxycarbonylmethylamino]acetic acid methyl ester
1-(2-Chloroethoxy)-2-nitrobenzene 1
1-Bromo-2-chloroethane (4.30 g, 0.03mol) and K2CO3 (2.07 g, 0.015 mol) were added to a solution of 2-nitrophenol (1.39 g, 0.01mol) in DMF (8 mL) at room temperature, the reaction was kept at 120 ºC for 5 h, cooled and diluted with EtOAc (20 mL), then washed with water (3 × 10 mL). The organic layer was collected and concentrated under vacuum, recrystallized in MeOH to give light yellow solid 1. Yield 93%;
m. p. 36-37 ºC;
1H NMR (CDCl3, 400 MHz) d 7.85 (m, 1H), 7.56 (m, 1H), 7.10 (m, 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.
1-Nitro-2-[2-(2-nitrophenoxy)ethoxy]benzene 2
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 ºC 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 ºC;
1H NMR (CDCl3, 400 MHz) δ 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);
IRν/cm-1 3051, 2956, 2931, 1606, 1582, 1518, 1359, 1278, 1159, 1090, 744, 671.
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 ºC;
1H NMR (CDCl3, 400 MHz) δ 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.
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 ºC; 1H NMR (CDCl3, 400 MHz) δ 6.85 (m, 8H), 4.27 (s, 4H), 4.15 (s, 8H), 3.56 (s, 12H); IRν/cm-1 3067, 2993, 2951, 2921, 2888, 1748, 1596, 1509, 1173, 742, 706.
[(2-{2-[2-(Bis-methoxycarbonylmethylamino)-5-methylphenoxy]ethoxy}-4-formyl-5-methyl-phenyl)methoxycarbonylmethylamino]acetic acid methyl ester 5
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 ºC 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 ºC; 1H NMR (CDCl3, 400 MHz) δ 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) δ190.5, 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-(Bis-methoxycarbonylmethylamino)phenoxy]ethoxy}-4-benzimidazole-phenyl)methoxycarbonylmethylamino]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 ºC for 30 min. After completion of the reaction, the reaction mixture was dissolved in EtOH (10 mL) and then poured into ice-water (30 mL). The pure solid product was filtered, 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 ºC;
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 (δ=C-H);
1H NMR (400 MHz, CDCl3) δ 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) δ 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.
The structure of 6 was characterized by IR, ESI-HRMS, PXRD, 1H and 13C NMR. IR spectrum of 6 shows typical secondary amine absorption (νN-H 3506 cm-1), aromatic absorption (ν=C-H 3033 cm-1; νC=C 1510, 1478 cm-1;δ=C-H 746 cm-1) and ester absorption (νC=O 1743 cm-1; νC-O 1171 cm-1). The HRMS m/z value, 1H and 13C NMR chemical shifts are in accordance with the structure of 6
http://www.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532014000100014&lng=en&nrm=iso&tlng=en
1H NMR PREDICT
13 C NMR PREDICT
Print version ISSN 0103-5053
J. Braz. Chem. Soc. vol.25 no.1 São Paulo Jan. 2014
http://dx.doi.org/10.5935/0103-5053.20130276
ARTICLE
Structural study and fluorescent property of a novel organic microporous crystalline material
Zhao Cheng; Bingqin Yang*; Meipan Yang; Binglin Zhang
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, 710069 Xi'an, China
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