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CAS No. : | 201227-39-6 | MDL No. : | MFCD07371567 |
Formula : | C8H4BrN3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | QIULWQLXNFSZJG-UHFFFAOYSA-N |
M.W : | 222.04 | Pubchem ID : | 24728911 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
60% | To a cooled solution of (2-amino-5-bromophenyl)acetonitrile (11 g, 52 mmol) in concentrated hydrochloric acid (110 mL) at -50 C., a solution of sodium nitrite (3.9 g, 57 mmol) in water (20 mL) was added slowly. After the addition, the mixture was stirred at -50 C. for 2 h. The mixture was neutralized with 33% ammonium hydroxide at 0 C. and extracted with ethyl acetate (3*100 mL). The combined organic layers were washed with saturated sodium chloride (100 mL), dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by column chromatography (100-200 mesh silica gel) using 10% ethyl acetate in petroleum ether as eluent to afford 5-bromo-3-cyanoindazole (7 g, 60%) as a solid. 1HNMR (CDCl3) δ ppm 10.7 (br, 1H), 8.1 (s, 1H), 7.64 (d, 1H), 7.5 (d, 1H). | |
60% | With hydrogenchloride; sodium nitrite; In water; at -50℃; for 2h; | To a cooled solution of (2-amino-5-bromophenyl)acetonitrile (11 g, 52 mmol) in concentrated hydrochloric acid (110 mL) at -50 C, a solution of sodium nitrite (3.9 g, 57 mmol) in water (20 mL) was added slowly. After the addition, the mixture was stirred at-50 C for 2h. The mixture was neutralized with 33% ammonium hydroxide at 0 C and extracted with ethyl acetate (3x100 mL). The combined organic layers were washed with saturated sodium chloride (100 mL), dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by column chromatography (100-200 mesh silica gel) using 10% ethyl acetate in petroleum ether as eluent to afford 5-bromo-3-cyanoindazole (7 g, 60%) as a solid. 1HNMR (CDCIs) ppm 10.7 (br, 1 H), 8.1 (s, 1 H), 7.64 (d, 1 H), 7.5 (d, 1 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With sodium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In water; N,N-dimethyl-formamide; at 80℃; under 4137.29 Torr; for 16h;autoclave; | A suspension of 5-bromo-3-cyanoindazole (3 g, 13.51 mmol), palladium dichloride 1,1'-bis(diphenylphosphino)ferrocene (1.76 g, 2.16 mmol), sodium acetate (3.32 g, 40.5 mmol), dimethylformamide (1 mL) in methanol (100 mL) was degassed, and kept under carbon monoxide (80 psi) pressure at 80 C. in a autoclave for 16 hours. The mixture was diluted with water (50 mL), filtered through Celite bed and the filtrate was concentrated. The obtained residue was acidified with 10% citric acid solution and extracted with ethyl acetate (2*100 mL). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulfate and concentrated. The obtained crude product was purified by column chromatography (100-200 mesh silica gel) using 10% ethyl acetate in chloroform as eluent to afford methyl 3-cyano-1H-indazole-5-carboxylate (1.8 g, 68%) as a solid. 1HNMR (CDCl3) δ ppm 10.8 (s, 1H), 8.7 (s, 1H), 8.22 (d, 1H), 7.64 (d, 1H), 4.0 (s, 3H). |
68% | With sodium acetate;1,1'-bis-(diphenylphosphino)ferrocene; palladium dichloride; In N,N-dimethyl-formamide; at 80℃; under 4137.29 Torr; for 16h;Autoclave; | A suspension of 5-bromo-3-cyanoindazole (3 g, 13.51 mmol), palladium dichloride 1,1'-bis(diphenylphosphino)ferrocene (1.76 g, 2.16 mmol), sodium acetate (3.32 g, 40.5 mmol), dimethylformamide (1 mL) in methanol (100 mL) was degassed, and kept under carbon monoxide (80 psi) pressure at 80 C in a autoclave for 16 hours. The mixture was diluted with water (50 mL), filtered through Celite bed and the filtrate was concentrated. The obtained residue was acidified with 10% citric acid solution and extracted with ethyl acetate (2 x 100mL). The combined organic layers were washed with brine (50 mL), dried over anhydrous sodium sulfate andconcentrated. The obtained crude product was purified by column chromatography (100-200 mesh silica gel) using 10% ethyl acetate in chloroform as eluent to afford methyl 3-cyano-1H-indazole-5-carboxylate (1 .8 g, 68%) as a solid. 1 HNMR (CDCI3) ppm 10.8 (s, 1 H), 8.7 (s, 1 H), 8.22 (d, 1 H), 7.64 (d, 1 H), 4.0 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20.8% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; potassium acetate; In 1,4-dioxane; at 90℃; for 16h;Inert atmosphere; | Step A: 5-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)-lH-indazole-3-carbonitrile [0449] To a mixture of 5-bromo-lH-indazole-3-carbonitrile (475 mg, 2.139 mmol), 1,4- dioxane (15 mL), potassium acetate (735 mg, 7.49 mmol), and bis(pinacolato)diboron (652 mg, 2.57 mmol), was added PdCl2(dppf) (78 mg, 0.107 mmol). The mixture was purged with N2 and then heated at 90C for 16 hours. The mixture was subsequently cooled and purified by column chromatography, eluting with a gradient of MeOH (0-10%) in DCM. The relevant fractions were collected and concentrated to give the title compound as an off-white solid (120 mg, 20.8%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sulfuric acid; trifluoroacetic acid; at 20℃; for 4h; | A mixture of 5-Bromo-1H-indazole-3-carbonitrile 110 (10 g) in trifluoroacetic acid (160 mL) and sulfuric acid (40 mL) was stirred at rt for 4 h. The reaction mixture was then poured into ice, and the precipitated solid was filtered, washed with water, and dried under high vacuum to give 5-bromo-1H-indole-3-carboxamide (111). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37.1% | In tetrahydrofuran; at 0 - 20℃; for 16h;Inert atmosphere; | To a stirred solution of scheme 6-6 compound S1 (10 g, 57.5 mmol) in THF (150 mL) under nitrogen was added methyl magnesium bromide solution (63.2 mL, 126.5 mmol) dropwise at 0 oC under N2 atmosphere. The reaction mixture was stirred at room temperature for 16 h. The mixture was quenched with saturated aqeuous NH4Cl solution and extracted with EtOAc (200 mL). The organic phase was washed with brine, dried with anhydrous Na2SO4 and concentrated. The residue was purified by silica gel cloumn chromatography (eluted with petroleum ether: ethyl acetate =10:1 to 5:1) to afford the title compound (5.1 g, 37.1 % yield) as a white solid. |
100 g | In tetrahydrofuran; diethyl ether; at 20℃; for 3h;Cooling with ice; | Step 1 : l-(5-Bromo-lH-indazol-3-yl)ethan-l-one (223) [0711] To an ice cold solution of 5-bromo-lH-indazole-3-carbonitrile (110 g) in a mixture of 1.1 L THF and 3.3 I, diethyl ether, methyl magnesium bromide (1 M in THF, 1.48 L, 3 equiv) was added dropwise. After completion of addition, the reaction mixture was brought to rt and stirred for 3 h (monitored by UPLC). Then the reaction was cooled to 0 nC and the pH was adjusted to 5 using 1 ,5 N HC1 (pH ~ 5). Then the reaction mass was stirred at rt for another 30 min. The reaction mixture was diluted with EtOAc and the layers were separated. The aqueous layer was again extracted with EtOAc. The combined organic layer was washed with water, washed with brine, dried over Na?.SQ4, and concentrated. The crude residue was recrystallized with a mixture of DCM:hexane (1 :2, total 10 volume based on crude weight) to afford brown solid (100 g). |
100 g | In tetrahydrofuran; diethyl ether; at 20℃; for 3h;Cooling with ice; | To an ice-cold solution of <strong>[201227-39-6]5-bromo-1H-indazole-3-carbonitrile</strong> (110 g) in a mixture of 1.1 L THF and 3.3 L diethyl ether, methyl magnesium bromide (1 M in THF, 1.48 L, 3 equiv) was added dropwise. After completion of addition, the reaction mixture was brought to room temperature and stirred for 3 h. Then the reaction was cooled to 0 C. and the pH was adjusted to 5 using 1.5 N HCl (pH≈5). Then the reaction mass was stirred at room temperature for another 30 min. The reaction mixture was diluted with EtOAc and the layers were separated. The aqueous layer was again extracted with EtOAc. The combined organic layer was washed with water, washed with brine, dried over Na2SO4, and concentrated. The crude residue was recrystallized with a mixture of DCM:hexane (1:2, total 10 volume based on crude weight) to afford brown solid (100 g). |
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