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CAS No. : | 602-00-6 | MDL No. : | MFCD00017003 |
Formula : | C7H5NO5 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | KPDBKQKRDJPBRM-UHFFFAOYSA-N |
M.W : | 183.12 | Pubchem ID : | 293291 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
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 |
---|---|---|
100% | SOCI2 (0.6 mL) was added dropwise to anhydrous MeOH (10 mL) at O0C. The mixture was stirred at this temperature for 0.5 h, then 3-hydroxy-2-nitrobenzoic acid (0.6 g, 3.2 mmol) was added to the mixture. The resulting mixture was heated at reflux for 4 h. TLC (petroleum ether: ethyl acetate = 1 :1) showed the <n="74"/>reaction was complete. The resulting mixture was concentrated in vacuo to give the title compound (0.63 g 100%) as a brown solid. | |
With thionyl chloride; In methanol; | Step 1 To a methanol solution (15 mL) at 0 C. was dropwise added thionyl chloride (6.4 mL, 0.088 mol). After 15 minutes, 3-hydroxy-2-nitrobenzoic acid (4 g, 0.022 mol) was added and the resulting mixture was stirred at room temperature for 72 hours. Volatile was removed under vacuo and the residue was partitioned between water and ethyl acetate. The organic layer was separated, washed with water and saturated sodium chloride, and was dried over sodium sulfate. After concentration, the crude product was recrystallized from dichloromethane and hexane to gave 4.5 g of methyl 3-hydroxy-2-nitrobenzoate. | |
With hydrogenchloride; sodium chloride; sodium hydrogencarbonate; In methanol; dichloromethane; water; | 1st Stage Preparing Methyl (3-Hydroxy-2-nitro)benzoate 3-hydroxy-2-nitrobenzoic acid (5 g; 27.32 mM) was dissolved in anhydrous methanol (200 ml). Anhydrous hydrogen chloride gas was bubbled through the solution until saturated. The mixture was then refluxed for 20 hours (reaction followed by T.L.C.: 10% methanol/90% dichloromethane). Next, the solvent was removed under vacuum to yield a brown solid. The solid was dissolved in water (100 ml) and sodium bicarbonate was added until effervescence stopped. Sodium chloride (15 g) was added to the aqueous solution, and the product was extracted into ethyl acetate (3*50 ml). The pooled aliquots were dried over magnesium sulphate and the solvent removed under vacuum to yield a malty brown solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Intermediate A-15B: Methyl 3-hydroxy-2-nitrobenzoate To a 100 mL flask containing MeOH (60 mL) at 0 C. was slowly added thionyl chloride (9.96 mL, 137 mmol). The solution was stirred at 0 C. for 30 minutes, and then Intermediate A-15A (10 g, 54.6 mmol) was added. The reaction solution was heated to reflux for 6 hrs. The reaction mixture was concentrated to dryness to give a bright yellow residue. The crude product mixture was purified via silica gel chromatography (0% to 100% of EtOAC/heptane over 15 minutes, 80 g column) giving the desired product (10.2 g, 95% yield). HPLC: RT=1.75 min (H2O/MeOH with TFA, Sunfire C18 3.5 mum, 2.1*30 mm, gradient=4 min, wavelength=220 nm); MS (ES): m/z=220 [M+Na]+; 1H NMR (400 MHz, chloroform-d) delta 7.60 (dd, J=8.5, 7.4Hz, 1H), 7.33-7.22 (m, 5H), 7.10 (dd, J=7.5, 1.3Hz, 1H), 3.96 (s, 3H). | |
93% | With thionyl chloride; at 20℃; for 9h;Heating / reflux; | To a stirred mixture of methanol (55 mL) and thionyl chloride (3.19 mL, 43.7 mmol) was added 3-hydroxy-2-nitrobenzoic acid (5.0 g, 27.3 mmol). The reaction mixture was stirred at room temperature for 2 h, refluxed for 7 h then evaporated. Purification by flash chromatography (2.5×10 cm column, 1:3 EtOAc/hexane) gave the title compound as a light yellow solid (5.03 g, 93% yield), mp 114-116 C. LC/MS gave the correct molecular ion [(M-H)-=196] for the desired compound. |
64% | With hydrogenchloride; In water; for 8h;Reflux; | Methyl 3-hydroxy 2-nitrobenzoate (1): Dry HCl was bubbled through the refluxing solution of 3-hydroxy 2-nitro benzoic acid (10 g, 0.055 mol) in 150 ml MeOH for 8 h. The solution was concentrated in high vacuum. Addition of H2O to the concentrated solution precipitated the methyl 3-hydroxy 2-nitro benzoic ester(64% yield, 6.9 g, 0.035 mol). 1H NMR delta = 7.07 (dd, 1H), 7.26 (m,1H), 7.58 (d, 1H), 3.94 (CO2CH3, s, 3H). |
With sulfuric acid; for 48h;Reflux; | Example 113 Bmethyl 3-hydroxy-2-nitrobenzoate; A solution of 3-hydroxy-2-nitrobenzoic acid (51 g) and con.H2SO4 (5 mL) in anhydrous methanol (450 mL) was heated to reflux for 48 hr. The mixture was concentrated to remove methanol, and the residue was partitioned between water (500 mL) and ethyl acetate (800 mL). The organic layer was washed with brine (300 mL), dried over anhydrous sodium sulfate, and concentrated to give crude compound. The crude product was purified by chromatography (silica gel, petroleum ether/ethyl acetate=40:1 to 5:1) to give methyl 3-hydroxy-2-nitrobenzoate (28 g) 1H-NMR (400 MHz, CDCl3) delta 3.8 (s, 3H), 7.32-7.34 (d, J=8.4 Hz, 1H), 7.39-7.41 (d, J=8.0 Hz, 1H), 7.48-7.52 (t, J=8.0 Hz, 1H), 11.37 (s, 1H); LC-MS (m/z) 198 [M+1]+. | |
With thionyl chloride; at 60℃; | General procedure: 3-Hydroxybenzoic acid (10 mmol) and anhydrous methanol (20 mL) were added to a 100 mL dry eggplant-shaped flask. With stirring, thionyl chloride (25 mmol) was added dropwise 5-12 h at 60 C, and the reaction progress was tracked using TLC. After the reaction completion, excess thionyl chloride was removed under reduced pressure, and the system was slowly poured into 100 mL of icewater. The mixture was extracted with ethyl acetate (30 mL 3),the combined organic layer was dried over Na2SO4, concentrated under vaccum. The crude product 1 was used in the next step without further purification. |
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