Structure of 59216-77-2
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CAS No. : | 59216-77-2 |
Formula : | C8H7NO5 |
M.W : | 197.15 |
SMILES Code : | O=C(OC)C1=CC(O)=CC=C1[N+]([O-])=O |
MDL No. : | MFCD00100487 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P264-P270-P271-P280-P301+P312-P302+P352-P304+P340-P305+P351+P338-P330-P332+P313-P337+P313-P362-P403+P233-P405-P501 |
* 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 |
---|---|---|
94% | With sulfuric acid; for 10.0h;Cooling with ice; Reflux; | 5-Hydroxy-2-nitrobenzoic acid (28.05 g, 0.153 mol) was dissolved in methanol in a 1000 ml single-necked flask,An ice bath was added dropwise with concentrated sulfuric acid (30.05 g, 0.306 mol)Reflux 10h. The reaction is completed,The reaction solution was poured into the ice solid precipitation, filtration,The filter cake was collected to obtain 28.39 g of methyl 5-hydroxy-2-nitrobenzoate, yield 94.0%. |
79% | With thionyl chloride; at 20℃;Reflux;Product distribution / selectivity; | At RT, SOCL2 (13.0 g, 0.109 mol) was added gradually to a solution of commercially available <strong>[610-37-7]3-hydroxy-5-nitrobenzoic acid</strong> (20.0 g, 0.109 mol) in MeOH (500 mL). The reaction was warmed at reflux for 72 h. The reaction was cooled to RT and evaporated to dryness in vacuo. The residue was dissolved in EtOAc (200 mL) and washed with aq. saturated NaHCO3 (200 mL). The aqueous-layer was extracted with EtOAc (2×200 mL). The combined EtOAc-extracts were washed with brine (1×200 mL). The organic layer was dried (Na2SO4), filtered, and evaporated to dryness to obtain <strong>[610-37-7]3-hydroxy-5-nitrobenzoic acid</strong> methyl ester (16.9 g, 79%, purity (LC)>95%).MS: [M-H]-=196. |
74% | With thionyl chloride; for 3.0h;Reflux; | [00971 Step 1. Methyl 5-hydroxy-2-nitrobenzoate (20). Thionyl chloride (13.0 g, 109 mmol) was added slowly at room temperature to a solution of <strong>[610-37-7]3-hydroxy-5-nitrobenzoic acid</strong> (20?) (20.0 g, 109 mmol) in methanol (500 mL). The reaction was heated at reflux for 3 hours, cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in ethyl acetate (200 mL), washed with saturated sodium bicarbonate (200 mL) and saturated sodium chloride (200 mL). The organic layer was dried over sodium sulfate, filtered and concentrated to afford (20) as a white solid (16 g, 74%). |
72% | With thionyl chloride; for 5.0h;Reflux; | Step 2: (0334) Thionyl chloride (26.8 mmol) and methanol (10 ml) were added into compound 11-b (4.1 g, 22.4 mmol) and the mixture was stirred at reflux for 5 hours. The reaction solution was concentrated, extracted with ethyl acetate and water, washed with brine, dried, and concentrated to give the target 11-c (3.19 g, yield: 72%). |
With sulfuric acid; for 12.0h;Heating / reflux; | EXAMPLE 10APreparation of intermediate 10a6Step 1 :A mixture of carboxylic acid 10a1 (5.0 g, 27 mmol) and concentrated H2SO4 (4 mL) in MeOH (80 mL) is stirred at reflux for 12 hours. The mixture is concentrated under reduced pressure and poured onto a mixture of ice and saturated aqueous NaHCO3. The aqueous mixture is acidified with citric acid and extracted twice with EtOAc. The combined organic extracts are washed with water and brine, dried with MgSO4, filtered, and concentrated under reduced pressure. Purification by flash chromatography (3:7 EtOAc/Hexane) affords ester 10a2. | |
With sulfuric acid; for 12.0h;Heating / reflux; | A mixture of carboxylic acid 27a (5.0 g, 27 mmol) and concentrated H2SO4 (4 mL) inMeOH (80 mL) is stirred at reflux for 12 hours. The mixture is concentrated under reduced pressure and poured onto a mixture of ice and saturated aqueous NaHCO3.The aqueous mixture is acidified with citric acid and extracted twice with EtOAc. The combined organic extracts are washed with water and brine, dried with MgSO4, filtered, and concentrated under reduced pressure. Purification by flash chromatography (3:7 EtOAc/Hexane) affords ester 27b. | |
With boron trifluoride diethyl etherate; at 20℃;Reflux; | BF3-Et20 (110 mL, 870 mmol) is added to <strong>[610-37-7]5-hydroxy-2-nitrobenzoic acid</strong> (15 g, 81.3 mmol) in MeOH (250 mL) at RT. Et20 is distilled off until the temperature reaches 70 C and the reaction mixture is heated to reflux overnight. BF3-Et20 (50 mL) is added to complete the reaction with an additional 24 h at reflux. MeOH is removed under vacuum and the residue is diluted in DCM (300 mL), washed with water, brine, dried over Na2S04 and concentrated under vacuum to afford methylester 70a1. | |
With thionyl chloride; for 3.5h;Heating / reflux;Product distribution / selectivity; | To a mixture of <strong>[610-37-7]5-hydroxy-2-nitrobenzoic acid</strong> 1a1 (50 g, 0.273 mol) in MeOH (500 mL), is added SOCl2 (40 mL, 65.2 g, 0.55 mol) dropwise over about 30 minutes and the mixture is heated at reflux for 2 hours. Excess SOCl2 (20 mL, 32.6 g, 0.27 mol) is carefully added and heating at reflux is continued overnight. Further SOCl2 (20 mL, 32.6 g, 0.27 mol) is added and heating at reflux is continued for 1 hour. The reaction mixture is cooled to room temperature and concentrated under reduced pressure. The residue is diluted with EtOAc (600 mL), washed with saturated aqueous NaHCO3 and brine, dried over MgSO4, filtered and concentrated to dryness. The methyl ester 1a2 is recovered as a solid from CH2Cl2 and hexane. | |
With sulfuric acid; for 12.0h;Heating / reflux;Product distribution / selectivity; | A mixture of carboxylic acid 15a1 (5.0 g, 27 mmol) and concentrated H2SO4 (4 mL) in MeOH (80 mL) is stirred at reflux for 12 hours. The mixture is concentrated under reduced pressure and poured onto a mixture of ice and saturated aqueous NaHCO3. The aqueous mixture is acidified with citric acid and extracted twice with EtOAc. The combined organic extracts are washed with water and brine, dried with MgSO4, filtered, and concentrated under reduced pressure. Purification by flash chromatography (3:7 EtOAc/Hexane) affords ester 15a2. | |
With thionyl chloride; at 76℃; for 21.0h; | Exam ple BA: Com pounds 2003, 2001, 200S and 2022Step 1" Add thonyl chloride (40 m L, 0.55 r?ol) dropwtse to 5-hydroxy"2"n'rtrobenzoic acid 8a1 (50.0 g, 0.270 m ol) in MeOH (500 m L). Heat to 76C for about 2 h. Add a further portion of thionyl chloride {20 m L, 0,27 m ol) dropwse and continue healing for about 13 h. Add a flnal portion of thionyl chloride (20 m L, 0.2? m olj and continue heating for about 1 h. Allow the m ixture to cool to RT and concentrate under reduced pressure. Dilute wrth EtOAc. Wash with saturated NaHCOj (aqueous) and bnne, dry over MgSO4, filter and concentrate to dryness. Crystallize the residue with DCM and hexa?es to provide 8a2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With sulfuric acid; magnesium sulfate; In methanol; | Step 1 Methyl 5-hydroxy-2-nitrobenzoate To a stirred suspension of <strong>[610-37-7]5-hydroxy-2-nitrobenzoic acid</strong> (5.1 g, 28 mmol) in methanol (20 ml) was added sulfuric acid (95%, 8 ml) at room temperature. The solution was stirred at 90 C. for 1 hour after which it was allowed to reach room temperature and carefully poured into saturated sodium bicarbonate. Subsequent extraction with dichloromethane, drying of the organic phase using magnesium sulfate and concentration in vacuo gave the title compound (2.8 g, 52%) as a yellow solid. 1H NMR (DMSO) delta 11.40 (br s, 1H), 8.04 (d, J=8.97 Hz 1H), 7.05-6.98 (m, 2H), 3.82 (s, 3H); MS m/z (M-1) 196. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methanol; water; | Step 2. Methyl 5-hydroxy-2-nitrobenzoate. 5-Hydroxy-2-nitrobenzoic acid (47 g) in 750 ml methanol was treated with 160 ml BF3 -ether, ether distilled off until pot temperature reached 60, and refluxed overnight. The procedure was repeated with 100 ml BF3 -ether. The mixture was poured into 3 volumes of water, extracted with ethyl acetate, the ethyl acetate washed with water, KHCO3 solution, water, dried and concentrated to give 48.4 g product. |
Tags: 59216-77-2 synthesis path| 59216-77-2 SDS| 59216-77-2 COA| 59216-77-2 purity| 59216-77-2 application| 59216-77-2 NMR| 59216-77-2 COA| 59216-77-2 structure
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