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CAS No. : | 59237-53-5 | MDL No. : | MFCD01928341 |
Formula : | C7H5ClN2O4 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | BRPREIDVQXJOJH-UHFFFAOYSA-N |
M.W : | 216.58 | Pubchem ID : | 346961 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-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 |
---|---|---|
With sodium methylate; In methanol; water; sodium thiomethoxide; | REFERENCE EXAMPLE 44 A solution of sodium methoxide in methanol (82.65 ML; 1 M) is added slowly to a stirred solution of <strong>[59237-53-5]methyl 6-chloro-5-nitronicotinate</strong> (17 g) in anhydrous methanol (250 ML) and the mixture is stirred for 8 hours. The mixture is concentrated, and the residue is treated with water and extracted with ethyl acetate. The extract is washed with water, treated with decolourising charcoal, and dried over magnesium sulphate. Concentration gives methyl 6-methoxy-5-nitronicotinate (9.8 g), in the form of an orange solid. Recrystallization from cyclohexane gives white needles, m.p.118-119°C. By proceeding in a similar manner using sodium thiomethoxide instead of sodium methoxide as the starting material, there is prepared methyl 6-methylthio-5-nitronicotinate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In dichloromethane; at 20℃; for 1h; | A solution of 6-chloro-5-nitro-nicotinic acid methyl ester [(L.] [OG)] [prepared as described by A. H. Berne et [AL. J. CHEM. SOC.] 2590-2594 (1951)] in dichloromethane (10 mL) containing triethylamine (0.76 mL) was treated with mercapto-acetic acid methyl ester (0.44 mL) and the solution was stirred at room temperature for 1 hour and evaporated to dryness. Sodium bicarbonate solution was added and the mixture was extracted with dichloromethane, dried (anhydrous sodium sulfate) and evaporated to afford a solid [(L.] [OG).] MS (+ve ion electrospray) m/z 287 (MH+). | |
With triethylamine; In dichloromethane; at 20℃; for 1h; | A solution of 6-chloro-5-nitro-nicotinic acid methyl ester (l. Og) [prepared as described by A. H. Berrie et al. J. Chem. Soc. 2590-2594 (1951)] in dichloromethane (lOmL) containing triethylamine (0.76mL) was treated with mercapto-acetic acid methyl ester (0.44mL) and the solution was stirred at room temperature for 1 hour and evaporated to dryness. Sodium bicarbonate solution was added and the mixture was extracted with dichloromethane, dried (anhydrous sodium sulfate) and evaporated to afford a solid (l. Og). MS (+ve ion electrospray) m/z 287 (MH+). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With N-ethyl-N,N-diisopropylamine; In methanol; at 20℃; | To a solution of 6-chloro-5-nitro-nicotinic acid methyl ester (216mg, 1. OMMOL) and 4- benzyloxyaniline hydrochloride (280mg, 1. 2MMOL) in MEOH (LOML) was added PR2NET (0.35mL, 2. 0MMOL). The resulting mixture was stirred at rt overnight, a red solid precipitated from the mixture, which was collected by filtration. MS (ES, Pos. ) : m/z 380 [MH+]. 1H NMR (CDC13, 400 MHz) : 8 = 3.94 (s, 3H), 5.10 (s, 2H), 7.03 (d, J= 8. 8 Hz, 2H), 7.38-7. 46 (M, 5H), 7.50 (d, J= 8. 8 Hz, 2H), 9.01 (d, J= 2.0 Hz, 1H), 9.08 (d, J= 2.0 Hz, 1H), 10.2 (br s, 1H). | |
With N-ethyl-N,N-diisopropylamine; In methanol; at 20℃; | 6-(4-Benzyloxyphenylamino)-5-nitronicotinic acid methyl ester (XXIV): To a solution of 6-chloro-5-nitro-nicotinic acid methyl ester (216 mg, 1.0 mmol) and 4-benzyloxyaniline hydrochloride (280 mg, 1.2 mmol) in MeOH (10 mL) was added iPr2NEt (0.35 mL, 2.0 mmol). The resulting mixture was stirred at rt overnight, a red solid precipitated from the mixture, which was collected by filtration. MS (ES, Pos.): m/z 380 [MH+]. 1H NMR (CDCl3, 400 MHz): delta=3.94 (s, 3H), 5.10 (s, 2H), 7.03 (d, J=8.8 Hz, 2H), 7.38-7.46 (m, 5H), 7.50 (d, J=8.8 Hz, 2H), 9.01 (d, J=2.0 Hz, 1H), 9.08 (d, J=2.0 Hz, 1H), 10.2 (br s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A suspension of 6- hydroxy-5-nitro-nicotinic acid (1. 1 g, 6. 0MMOL) and PC15 (3.75g, 18. 0MMOL) in POC13 (5 mL) was stirred at 100°C for 2H. Excessive phosphorus oxychloride was evaporated under reduced pressure. The residue was dissolved in 1 OML of anhydrous ether and cooled to 0°C, then 10mL of methanol was added dropwise. L OMIN later, the ether was evaporated under reduced pressure at rt. The remaining methanol solution was diluted with water (40ML), and the light-yellow solid was collected by filtration. 1H NMR (CDC13, 400 MHz): 8 = 4.03 (s, 3H), 8.77 (d, J= 2.1 Hz, 1H), 9.18 (d, J= 2.1 Hz, 1H). | ||
6-Chloro-5-nitronicotinic acid methyl ester (XXIII): A suspension of 6-hydroxy-5-nitro-nicotinic acid (1.1 g, 6.0 mmol) and PCl5 (3.75 g, 18.0 mmol) in POCl3 (5 mL) was stirred at 100° C. for 2 h. Excessive phosphorus oxychloride was evaporated under reduced pressure. The residue was dissolved in 10 mL of anhydrous ether and cooled to 0° C., then 10 mL of methanol was added dropwise. 10 min later, the ether was evaporated under reduced pressure at rt. The remaining methanol solution was diluted with water (40 mL), and the light-yellow solid was collected by filtration. 1H NMR (CDCl3, 400 MHz): delta=4.03 (s, 3H), 8.77 (d, J=2.1 Hz, 1H), 9.18 (d, J=2.1 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With hydrazine; In 1,4-dioxane; at 15 - 25℃; for 3h; | B. 6-Hydrazino-5-nitro-nicotinic acid methyl ester; To a at 15°C cooled solution of 30.0 g (0.14 mol) 6-chloro-5-nitro-nicotinic acid methyl ester in dioxane (600mi) is added hydrazine hydrate (21.5 ml). During the addition the reaction mixture is warmed up to 25°C and is stirred for further 3 h. The reaction is quenched by pouring the reaction mixture into a saturated aqueous ammonium chloride solution. The precipitated solid is filtered off and dried under vacuo at 50°C to give 26.5 g (0.12 mol/90 percent) of the title compound as a red solid. |
90% | With hydrazine; In 1,4-dioxane; at 15 - 25℃; for 3h; | To a at 15°C cooled solution of 30.0 g (0.14 mol) 6-chloro-5-nitro-nicotinic acid methyl ester in dioxane (600ml) is added hydrazine hydrate (21.5 ml) During the addition the reaction mixture is warmed up to 25°C and is stirred for further 3 h. The reaction is quenched by pouring the reaction mixture into a saturated aqueous ammonium chloride solution. The precipitated solid is filtered off and dried under vacuo at 50°C to give 26.5 g (0.12 mol/90 percent) of the title compound as a red solid. 'H-NMR (200MHz, d"-DMSO) : 8 = 3.85 (s, 3 H), 8.69 (d, 1 H), 8.90 (d, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 0℃; | To a suspension of 49.0 g (0.27 mol) 6-hydroxy-5-nitro-nicouenic acid in thionyl chloride (240 mi) are added 2 ml of DMF. This mixture is stirred at 60°C until the evolution of gaz has ended. Then it is stirred at 80°C for further 18 h. Residual thionyl chloride is removed under vacuo and the resulting residue is coevaporated three times with toluene. Subsequently this reaction mixture is dissolved in dichloromethane (100 mi) and cooled to 0°C before methanol (55.5 ml) is dropwise added. The precipitated solid is filtered off and dried under vacuo at 50°C to give 27.6 g (13.7 mmol/52 percent) of the title compound as a light yellow solid with a melting point of 78°C (dichloromethane/methanol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium methylate; In methanol; water; | REFERENCE EXAMPLE 17 Sodium methoxide in methanol (82.65 mL of a 1 M solution) is added slowly to a stirred solution of <strong>[59237-53-5]methyl 6-chloro-5-nitronicotinate</strong> (17 g) in anhydrous methanol (250 mL) and the mixture stirred for 8 hours. The mixture is concentrated, the residue treated with water and then extracted into ethyl acetate. The extracts are washed with water, treated with decolourising charcoal and dried (MgSO4). Concentration afforded methyl 6-methoxy-5-nitronicotinate (9.8 g) as an orange solid. Recrstallisation from cyclohexane afforded white needles, m.p.118-9° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; sodium hydrogensulfide; In methanol; di-isopropyl ether; | Production Example 105 Methyl 5-amino-6-mercaptonicotinate To a solution of 6 g of <strong>[59237-53-5]methyl 6-chloro-5-nitronicotinate</strong> in methanol (100 ml) was added 6.7 g of sodium hydrogensulfide and the resulting mixture was heated under reflux for 2 hours. After distilling off the solvent under reduced pressure, dilute hydrochloric acid was added to the residue followed by extraction with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. Diisopropyl ether was added to the residue and the crystals thus precipitated were taken up by filtration to thereby give 24.7 g of the title compound as yellow crystals. 1H-NMR(DMSO-d6) delta ppm: 3.78(s, 3H),5.91-6.00(br.s, 2H), 7.12(d, J=2.0 Hz, 1H), 7.53(dd, J=2.0, 6.4 Hz, 1H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In methylamine; | a Methyl 6-methylamino-5-nitro-nicotinate 1.6 g (7.4 mMol) of methyl 6-chloro-5-nitro-nicotinate (see Bernie et al. in J. Chem. Soc. 1951, 2590) were stirred in 20 ml of 40percent aqueous methylamine solution at room temperature for 30 minutes. The reaction mixture was then diluted with ice water, the yellow precipitate formed was filtered off and dried. Yield: 1.2 g (80percent of theory), Rf value: 0.66 (silica gel; ethyl acetate/ethanol/glacial acetic acid=90:5:5) |
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