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CAS No. : | 23218-93-1 | MDL No. : | MFCD00461253 |
Formula : | C8H8N2O4 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | HZVBRLJDOZZHFL-UHFFFAOYSA-N |
M.W : | 196.16 | Pubchem ID : | 2756518 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With diammonium sulfide; In methanol; for 5h;Reflux; | The solution of (NH4)2S23 used for this reaction was prepared by adding a solution of Na2S·9H2O (15.00g, 62.47mmol) in 100mL of MeOH to a suspension of NH4Cl (13.40g, 250.50mmol) in 100mL of MeOH and separating the solid material after 30min of stirring at room temperature. The resulting solution was added within 40min to a solution of 16 (6.20g, 27.42mmol) in 250mL of boiling MeOH and heated at reflux for 5h. After cooling down, the resulting precipitate of sulfur was filtered off and the pH was adjusted to 5 with 1M HCl and the solvent was removed under vacuum. The crude product was extracted with 250mL of AcOEt, washed with water, brine and dried over MgSO4 and concentrated in vacuo. Purification by silica gel column chromatography (30% acetone in hexane) afforded pure product 17 (4.73g, 88%) as an orange solid. 1H and 13C NMR data are in agreement with published data.24 1H NMR (400MHz, acetone-d6) delta: 7.93 (1H, dd, J 2.1, 1.4Hz, arom.), 7.71 (1H, t, J 2.2Hz, arom.), 7.67 (1H, dt J 2.2, 0.8Hz, arom.), 5.66 (2H, s, NH2), 3.91 (3H, s, OMe). 13C NMR (100MHz, acetone-d6) delta: 166.0, 151.1, 150.3, 133.1, 20.9, 112.2, 111.9, 52.8. Rf (30% acetone/hexane) 0.37. MS(EI): m/z (%)=197.1 (10), 196.1 (100, M+), 165.1 (33), 150.1 (20), 138.1 (8), 135.1 (22), 122.1 (35), 107.1 (17), 91.1 (23), 90.1 (10), 79.1 (8), 63.1 (20), 52.1 (9). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 9; Preparation of (3-{3-Chloro-5-[4-(2-fluoro-phenyl)-piperazine-1-sulfonyl]- phenyl}-4-cyano-pyrrol-1-yl)-acetic acid , sodium salt; a) 3-Chloro-5-nitro-benzoic acid methyl ester; To a solution of commercially available <strong>[23218-93-1]3-amino-5-nitro-benzoic acid methyl ester</strong> (32.0 g, 0.163mol) in cone HCI (332 ml) and AcOH (464 ml) at 00C is added NaNO2 (11.28 g, 0.163 mol) in water (20 ml) dropwise over 20 minutes, maintaining, the reaction temperature below O0C . The reaction mixture is stirred at 00C for 1 hour. The reaction mixture is added dropwise to a stirred solution of copper(l)chloride (19.4 g, 0.1956 mmol) in water (200 ml) over 45 minutes and the maximum temperature is kept at 210C. After 70 minutes at room temperature, the reaction mixture is poured slowly into stirring water and extracted with EtOAc. The combined organic layers are stirred with saturated sodium bicarbonate solution. The organic layer is separated, is washed with water, brine, dried over MgSO* After filtration the solvent is evaporated under reduced pressure to give a crude product which is purified by flash chromatography (gradient from isohexane to 47:3 isohexane:EtOAc) to give the titled compound as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45.2% | In N,N-dimethyl-formamide; at 120℃; for 0.333333h;Microwave irradiation; | Example 77 methyl 3-(benzylamino)-5-((3-carbamoyl-7-(2,4-dimethoxypyrimidin-5-yl)quinolin-4 yl)amino)benzoate a) methyl 3-(benzylamino)-5-nitrobenzoate. To a solution of methyl 3-amino-5- nitrobenzoate (500 mg, 2.55 mmol) in N,N-dimethylformamide (5 ml.) was added (bromomethyl)benzene (436 mg, 2.55 mmol). The reaction was heated in a microwave reactor at 120 C for 20 minutes. After cooling, the organic solvent was removed under reduced pressure. The resulting oil was purified by flash chromagraphy (silica gel, 0-100% ethyl acetate in hexanes) to afford methyl 3- (benzylamino)-5-nitrobenzoate (330 mg, 1.153 mmol, 45.2 % yield) as a yellow solid. 1H NMR (400 MHz, DMSO-d6) delta ppm 3.86 (s, 3 H) 4.41 (d, J=5.81 Hz, 2 H) 7.23 - 7.29 (m, 1 H) 7.33 - 7.40 (m, 5 H) 7.56 (d, J=1 .77 Hz, 2 H) 7.78 (t, J=1.77 Hz, 1 H). LCMS (ES+) m/e 287 [M+H]+. |
45.2% | In N,N-dimethyl-formamide; at 120℃; for 0.333333h;Microwave irradiation; | a) methyl 3-(benzylamino)-5-nitrobenzoate. To a solution of methyl 3-amino-5- nitrobenzoate (500 mg, 2.55 mmol) in N,N-dimethylformamide (5 mL) was added (bromomethyl)benzene (436 mg, 2.55 mmol). The reaction was heated in a microwave reactor at 120 C for 20 minutes. After cooling, the organic solvent was removed under reduced pressure. The resulting oil was purified by flash chromagraphy (silica gel, 0-100% ethyl acetate in hexanes) to afford methyl 3- (benzylamino)-5-nitrobenzoate (330 mg, 1.153 mmol, 45.2 % yield) as a yellow solid. 1H NMR (400 MHz, DMSO-d6) delta ppm 3.86 (s, 3 H) 4.41 (d, J=5.81 Hz, 2 H) 7.23 - 7.29 (m, 1 H) 7.33 - 7.40 (m, 5 H) 7.56 (d, J=1 .77 Hz, 2 H) 7.78 (t, J=1.77 Hz, 1 H). LCMS (ES+) m/e 287 [M+H]+. |
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