Structure of 38240-29-8
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CAS No. : | 38240-29-8 |
Formula : | C5H4N2O2S |
M.W : | 156.16 |
SMILES Code : | SC1=NC=CC=C1[N+]([O-])=O |
MDL No. : | MFCD00661369 |
InChI Key : | LKNPLDRVWHXGKZ-UHFFFAOYSA-N |
Pubchem ID : | 819358 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 potassium hydroxide; thiourea; In ethanol; water; | Example 98A 3-nitropyridine-2-thiol 2-mercapto-3-nitropyridine was prepared by treating 3-nitro-2-chloro-pyridine (50 g, 0.0317 mol) with thiourea (24 g, 0.0317 mol) in 200 mL of ethanol at reflux for several hours. After the reaction mixture was allowed to cool, 7.19 mL solution of KOH (42.8 g in 115 mL of water) was added and the resulting mixture was heated at reflux for 3 hours. The crude reaction mixture was cooled to room temperature and then concentrated to 50% of its volume in vacuo. | |
2-mercapto-3-nitropyridine was prepared by treating 3-nitro-2-chloro-pyridine (50 g, 0.0317 mol) with thiourea (24 g, 0.0317 mol) in 200 ML of ethanol at reflux for several hours.After the reaction mixture was allowed to cool, 7.19 ML solution of KOH (42.8 g in 115 ML of water) was added and the resulting mixture was heated at reflux for 3 hours.The crude reaction mixture was cooled to room temperature and then concentrated to 50% of its volume in vacuo.After diluting with 300 ML of water, the product was isolated by vacuum filtration as an orange solid that was used without further purification. MS (DCI/NH3) m/z 157 (M+H)+. 1H NMR (300 MHz, DMSO-d6) delta 5.76 (m, 1H), 7.67 (dd, J=8.46, 4.78 Hz, 1H), 8.63 (dd, J=8.46, 1.47 Hz, 1H), 8.73 (dd, J=4.60, 1.65 Hz, 1H). | ||
3-nitropyridine-2-thiol 2-mercapto-3-nitropyridine was prepared by treating 3-nitro-2-chloro-pyridine (50 g, 0.0317 mol) with thiourea (24 g, 0.0317 mol) in 200 ML of ethanol at reflux for several hours.After the reaction mixture was allowed to cool, 7.19 ML solution of KOH (42.8 g in 115 ML of water) was added and the resulting mixture was heated at reflux for 3 hours.The crude reaction mixture was cooled to room temperature and then concentrated to 50% of its volume in vacuo.After diluting with 300 ML of water, the product was isolated by vacuum filtration as an orange solid that was used without further purification. MS (DCI/NH3) m/z 157 (M+H)+. 1H NMR (300 MHz, DMSO-d6) delta 5.76 (m, 1H), 7.67 (dd, J=8.46, 4.78 Hz, 1H), 8.63 (dd, J=8.46, 1.47 Hz, 1H), 8.73 (dd, J=4.60, 1.65 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The reaction was stirred for 2 h, diluted with 250 ml of H2 O and evaporated in vacuo. The resulting solid was filtered off and discarded. The solution was then acidified with acetic acid to pH=4.5 and yellowish-red crystals formed. The title compound was filtered off, washed with water and dried under vacuum over a dessicant to provide 1.1 g (m.p.=185-7 C. (dec.)) NMR: (300 mHz, CDCl3) delta 6 8.09 (d, J =7Hz, 1H), 7.89 (d, J =7Hz, 1H), 6.84 (dd, J =6, 3Hz, 1H). IR: (KBr cm-1) 3119, 2872, 1611, 1577, 1527, 1349, 1330, 1240, 1141 MS: EI MS m/e 126 (M+) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In toluene; | Example 101D N-[2-(aminosulfonyl)pyridin-3-yl]-5-chloro-4-hydroxy-1-(3-methylbutyl)-2-oxo-1,2-dihydroquinoline-3-carboxamide The product of Example 101C (0.170 g, 0.50 mmol) was reacted with the product of Example 98A (0.086 g, 0.50 mmol) in toluene (6 mL) at reflux for 16 hours. The reaction was cooled and the resulting precipitate was collected by filtration and dried to give the title compound (0.200 g, 86%). MS (DCI) m/z 465 (M+H)+. 1 1H NMR (300 MHz, DMSO-d6) delta 0.99 (d, J=6.62 Hz, 6H), 1.51 (m, 2H), 1.76 (m, 1H), 4.32 (m, 2H), 7.45 (d, J=7.35 Hz, 1H), 7.61 (d, J=8.82 Hz, 1H), 7.71 (s, 2H), 7.77 (m, 2H), 8.45 (dd, J=8.46, 1.47 Hz, 1H), 8.53 (dd, J=4.60, 1.29 Hz, 1H), 12.84 (s, 1H), 17.22 (s, 1H). |
86% | In toluene; for 16.0h;Heating / reflux; | The product of Example 101C (0.170 g, 0.50 mmol) was reacted with the product of Example 98A (0.086 g, 0.50 mmol) in toluene (6 ML) at reflux for 16 hours.The reaction was cooled and the resulting precipitate was collected by filtration and dried to give the title compound (0.200 g, 86%). MS (DCI) m/z 465 (M+H)+. 11H NMR (300 MHz, DMSO-d6) delta 0.99 (d, J=6.62 Hz, 6H), 1.51 (m, 2H), 1.76 (m, 1H), 4.32 (m, 2H), 7.45 (d, J=7.35 Hz, 1H), 7.61 (d, J=8.82 Hz, 1H), 7.71 (s, 2H), 7.77 (m, 2H), 8.45 (dd, J=8.46, 1.47 Hz, 1H), 8.53 (dd, J=4.60, 1.29 Hz, 1H), 12.84 (s, 1H), 17.22 (s, 1H). |
86% | In toluene; for 16.0h;Heating / reflux; | Example 101D N-[2-(aminosulfonyl)pyridin-3-yl]-5-chloro-4-hydroxy-1-(3-methylbutyl)-2-oxo-1,2-dihydroquinoline-3-carboxamide The product of Example 101C (0.170 g, 0.50 mmol) was reacted with the product of Example 98A (0.086 g, 0.50 mmol) in toluene (6 ML) at reflux for 16 hours.The reaction was cooled and the resulting precipitate was collected by filtration and dried to give the title compound (0.200 g, 86%). MS (DCI) m/z 465 (M+H)+. 1 1H NMR (300 MHz, DMSO-d6) delta 0.99 (d, J=6.62 Hz, 6H), 1.51 (m, 2H), 1.76 (m, 1H), 4.32 (m, 2H), 7.45 (d, J=7.35 Hz, 1H), 7.61 (d, J=8.82 Hz, 1H), 7.71 (s, 2H), 7.77 (m, 2H), 8.45 (dd, J=8.46, 1.47 Hz, 1H), 8.53 (dd, J=4.60, 1.29 Hz, 1H), 12.84 (s, 1H), 17.22 (s, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With potassium carbonate; In water; acetonitrile; | STR60 7.0 g (0.05 mol) of 3,5-dichloro-1,2,4-oxadiazole in 25 ml of anhydrous acetonitrile are added dropwise to 7.8 g (0.05 mol) of <strong>[38240-29-8]3-nitro-2-mercaptopyridine</strong> (compare Int. J. Pept. Prot. Res. 16, 392 (180)) and 6.9 g (0.05 mol) of potassium carbonate in 100 ml of anhydrous acetonitrile at room temperature, with stirring. When the addition has ended, the mixture is heated to the reflux temperature for 1 hour, and after cooling, 300 ml of water are added, the mixture is extracted three times with 200 ml of methylene chloride each time and the combined organic phases are washed with 200 ml of water, dried over sodium sulphate and concentrated in vacuo. The residue crystallizes from diisopropyl ether. 10.2 g (79% of theory) of 3-chloro-5-(3-nitro-2-pyridylthio)-1,2,4-oxadiazole of melting point 84 C. are obtained. The following 3-chloro-1,2,4-oxadiazoles of the general formula (I) are obtained in a corresponding manner and in accordance with the general statements on the preparation: |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Example 98B 3-aminopyridine-2-sulfonamide The title compound, (3-aminopyrid-2-yl)sulfonamide was prepared in 3 steps (80% yield) from <strong>[38240-29-8]2-mercapto-3-nitropyridine</strong> according to the procedure of R. Lejeune and co-workers as described in Jpharm. Belg., 39, 217-224, 1984. MS (DCI/NH3) m/z 174 (M+H)+. 1H NMR (300 MHz, DMSO-d6) delta 6.00 (s, 2H), 7.25 (m, 2H), 7.34 (s, 2H), 7.82 (dd, J=4.04, 1.47 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Example 102C N-[2-(aminosulfonyl)pyridin-3-yl]-1-benzyl-4-hydroxy-5-methyl-2-oxo-1,2-dihydroquinoline-3-carboxamide The title compound was prepared according to the procedure of Example 84C substituting the product of Example 102B for the product of Example 84B and substituting the product of Example 98A for 2-amino-5-bromobenzenesulfonamide (0.163 g, 41%). MS (ESI+) m/z 465 (M+H)-; 1H NMR (300 MHz, DMSO-d6) delta 2.82 (s, 3H), 5.59 (s, 2H), 7.15 (d, J=7.35 Hz, 1H), 7.24 (m, 3H), 7.33 (m, 3H), 7.56 (t, J=7.91 Hz, 1H), 7.72 (m, 3H), 8.51 (m, 1H), 8.53 (s, 1H), 12.93 (s, 1H), 17.16 (m, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 1 3-chloromethylbenzoic acid (5. 9mmol) was dissolved in DMF and [CARBONYLDIIMIDAZOLE] (6. 2mmol) added. After 5 minutes the amine (5. 8mmol) was added and the reaction stirred at room temperature for 4h. The reaction mixture was diluted with water and extracted with [DICHLOROMETHANE.] The combined organics were dried over [MGS04,] filtered, and the solvent removed. The crude residue was purified by flash chromatography. Step 2 The product from step 1 (1. [6MMOL)] was dissolved in DMF along with the nitrothiopyridine (1. [6MMOL).] To this solution was added Hunig's base (3. 1 mmol) and the reaction stirred at room temperature overnight. The reaction mixture was treated with acetic acid solution and the product extracted with [DICHLOROMETHANE.] The combined organics were dried [OVER MGS04, FILTERED,] and the solvent removed. The crude residue was purified by flash chromatography. Step 3 The product from step 2 (0. [36MMOL)] was dissolved in ethanol and tin chloride dihydrate added. The reaction mixture was heated at [70C] for 2h. The residue was diluted with water and the product extracted with DCM. The combined organics were dried over MgS04, filtered, and the solvent removed. The crude product was used in the next reaction. Step 4 The product from step 3 (0. [07MMOL)] was dissolved in DCM and the acid chloride [(0.] [08MMOL)] added. To this was added [PS-DIEA] and PS-DMAP and the reaction stirred at RT overnight. The crude product was filtered and the solvent removed. The product was purified by flash chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
66% | With potassium carbonate; In N,N-dimethyl-formamide; at 60℃; for 4.0h; | a) Synthesis of 3-nitro-2-(2-phenylsulfanyl-ethylsulfanyl)pyridine3.44 g (20.0 mmol) (2-chloroethyl)(phenyl)sulfane and 5.53 g (40.0 mmol) potassium carbonate were added to a solution of 1.56 g (10.0 mmol) <strong>[38240-29-8]2-mercapto-3-nitropyridine</strong> in DMF (30 ml) and heated for 4 h at 60 C. Then the mixture was diluted with EE and washed with brine. The organic phase was separated off, dried over Na2SO4, filtered and concentrated to small volume under vacuum. Column chromatography (hexane/EE 9:1) of the residue yielded 1.93 g (6.6 mmol, 66%) 3-nitro-2-(2-phenylsulfanyl-ethylsulfanyl)pyridine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | With potassium carbonate; In acetone; at 20 - 60℃; | a) Synthesis of 3-nitro-2-[2-[[3-(trifluoromethyl)phenyl]sulfonyl]-ethylsulfanyl]pyridine4.15 g (30.0 mmol) potassium carbonate and 2.59 g (9.5 mmol) (1-(3-chloroethylsulfonyl)-3-(trifluoromethyl)benzene were added to a solution of 1.56 g (10.0 mmol) <strong>[38240-29-8]3-nitro-2-mercaptopyridine</strong> in acetone (50 ml) at room temperature and then heated for 16 h at 60 C. Then the mixture was concentrated to small volume under vacuum and the residue was taken up with water and EE. The phases were separated and the organic phase was washed with water and brine, dried over Na2SO4, filtered and concentrated to small volume under vacuum. The crude product was washed repeatedly with hexane to produce 2.35 g (6.0 mmol, 63%) 3-nitro-2-[2-[[3-(trifluoromethyl)phenyl]sulfonyl]-ethylsulfanyl]pyridine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 2.0h; | Intermediate 6 2-(benzylthio)-3-nitropyridine [0133] <strong>[38240-29-8]3-nitropyridine-2-thiol</strong> (0.50 g, 3.2 mmol) in DMF (4 ml) was added benzyl bromide (0.38 ml, 3.2 mmol) and K2CO3 (0.89 g, 6.4 mmol). The mixture was stirred at room temperature for 2 hours, diluted with H2O, extracted with EtOAc. The organic layer was washed with brine, dried over Na2SO4, and concentrated in vacuo. The crude product was purified by recrystallization from MeOH and minimal amount of CH2Cl2 to yield the title compound (0.72 g, 91%). [0135] 1H NMR (CDCl3) delta: 8.72 (dd, J=4.5, 1.6 Hz, 1H), 8.49 (dd, J=8.2, 1.8 Hz, 1H), 7.43 (d, J=7.3 Hz, 2H), 7.20-7.34 (m, 4H), 4.48 (s, 2H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With cytochrome b5; P450 reductase; recombinant cytochrome P450 2C19; NADPH; at 37℃; for 2.0h;Enzymatic reaction; | In a typical reaction, 50 nmoles of CYP2C19, 150 nmoles of P450 reductase and 250 nmoles of cytochrome b5 were reconstituted in phospholipid vesicles to form active protein complexes. 2-oxoclopidogrel and 3-nitropyrine-2-thiol were added at final concentrations of 0.05 and 0.3 mM respectively. Bio-synthesis of clop<strong>[38240-29-8]NPT</strong> was initiated by the addition of 1 mM NADPH. The reaction was incubated at 37oC for 2 hours.To purify clop<strong>[38240-29-8]NPT</strong>, the reaction mixture containing clop<strong>[38240-29-8]NPT</strong> was first filtered through a membrane with a cutoff of 10 kDa to remove all protein components. The filtrate containing clop<strong>[38240-29-8]NPT</strong> was then enriched on solid phase extraction (SPE) cartridges. Clop<strong>[38240-29-8]NPT</strong> was eluted from the SPE cartridges with 80% methanol/20% water. The eluent was concentrated to ~ 5ml at 50oC under vacuum. The concentrated mixture was loaded on a preparative reverse phase C18 column and Clop<strong>[38240-29-8]NPT</strong> was purified using high pressure liquid chromatography (HPLC). Clop<strong>[38240-29-8]NPT</strong> was eluted from the preparative C18 column at a flow rate of 3 ml/min with isocratic mobile phase consisting of 42% methanol/35%acetonitrile/22.9% water/0.1% formic acid. The HPLC fractions containing clop<strong>[38240-29-8]NPT</strong> were pooled and dried under vacuum. The final yield was ~25%. The purity of clop<strong>[38240-29-8]NPT</strong> estimated with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was > 90% as shown in Figure 8 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
60% | With scandium(III) chloride; 3-butyl-1-methyl-1H-imidazol-3-ium hexafluorophosphate; at 40℃; for 5.0h;Inert atmosphere; Ionic liquid; Sealed tube; Microwave irradiation; | Weigh 0.30 g ScCl3, 0.33 g of tetraacetylated fucose, 0.155 g of <strong>[38240-29-8]3-nitro-2-mercaptopyridine</strong> ,In parallel reaction tube. Under an atmosphere of nitrogen ionic liquid PFIL-5 [R1, R2 = ethoxy, n = 3, X = (CF3SO2) 2N] 2mL and the general ionic liquid 3-butyl-1-methylimidazolium hexafluorophosphate 2mL, Closed reaction tube, Stirring reaction, Microwave irradiation using intermittent, Power 350W, Each irradiation for 5 minutes, Stop irradiation for 1 minute. Reaction for 5 hours, Temperature control at 40 degrees Celsius. The reaction was terminated by adding water. After silica gel column separation, 0.256 g of glycoside 1-1 was obtained, Yield 60% .Ionic liquids can be reused, Yield no significant change. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With Bi4Cl16(4-)*2C90H80N4Se2(2+); L-proline; sodium t-butanolate; In acetonitrile; at 85℃; for 16.0h; | General procedure: To a stirred solution of thiophenol (1 mmol), aryl halide (1. 2mmol), L -proline (10 mol%) andBi(III) catalyst (10 mol%) in acetonitrile (5mL) at 85 C. The reaction mixture was monitored byTLC until all thiophenol was found consumed. The reaction mixture was extracted with ethylacetate and water, the organic layer was separated then washed with NaCl and dried withanhydrous Na2SO4. The solvent was removed under reduced pressure using the rotatory evaporator.The crude product was purified by coloumn chromatography (5:95 of ethyl acetate and hexane) toisolate the yellow solid |