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CAS No. : | 89283-92-1 | MDL No. : | MFCD12828485 |
Formula : | C5H4BrClN2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | KAJRLYHBOIPDLW-UHFFFAOYSA-N |
M.W : | 207.46 | Pubchem ID : | 53418432 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302 | 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 |
---|---|---|
72% | With iron; ammonium chloride; In ethanol; water; at 80℃; for 2.0h; | To a solution of 3-bromo-4-chloro-5-nitropyridine (9.50 g, 40.01 mmol) in EtOH (500 mL) was added NH4CI (13.27 g, 248 mmol), water (50 ml), and Fe (22.39 g, 401 mmol) at room temperature. The resulting mixture was stirred for 2 h at 80°C. Whenthe reaction was done, the solids were filtered off. The resulting mixture was concentrated under reduced pressure and the residue was purified by flash chromatography eluting with 0percent to 60percent EtOAc in petrol ether to yield 5-bromo-4- chloropyridin-3-amine as a yellow oil (5.94 g, 72percent). MS: m/z = 209.2 [M+H]. |
With ammonium chloride; zinc; In tetrahydrofuran; at 40℃; for 1.0h; | 5-bromo-4-chloro-3-nitropyridine (5.0 g, 0.021 mol)Was dissolved in 50 mL of tetrahydrofuran,150 mL of saturated ammonium chloride solution and zinc dust (13 g, 0.21 mol) were added,Heated at 40 ° C for 1 hour,Cold to room temperature,Dispensing,The aqueous phase was washed with 100 mL of ethyl acetate,Combine organic phase,Washed with water (100 mL * 2 times) and saturated brine (50 mL * 2 times)Organic phase concentration,4.1 g of crude oil,Yield 92percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine; In tetrahydrofuran; at 0 - 20℃; for 1.0h; | 5-Bromo-4-chloro-3-aminopyridine (4.1 g, 0.020 mol)Was dissolved in 100 mL of tetrahydrofuran,Triethylamine (2.4 g, 0.024 mol) was added,The system was placed in an ice bath at 0 ° C,A solution of oxalyl chloride monoethyl ester (3.0 g, 0.022 mol)In tetrahydrofuran solution,Reaction at room temperature for 1 hour,Concentrated under reduced pressure,Ethyl acetate (100 mL) was added,Washed with saturated sodium bicarbonate solution (50 mL * 2 times)Dispensing,The organic phase was dried over anhydrous sodium sulfate,Concentrated under reduced pressure to dry,To give 5.5 g of crude solid,Yield 90.0percent. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10 mg | With tris-(dibenzylideneacetone)dipalladium(0); sodium carbonate; tricyclohexylphosphine; In water; isopropyl alcohol; at 100℃; for 2.0h;Inert atmosphere; | To a solution of 21 .3 (70 mg, 0.174 mmol), <strong>[89283-92-1]5-bromo-4-chloropyridin-3-amine</strong> (36.2 mg, 0.174 mmol), Na2C03 (37.0 mg, 0.349 mmol), Pd2(dba)3 (8 mg, 8.72 muetaiotaomicronIota) and tricyclophexylphosphine (10 mg, 0.035 mmol) in 2-Propanol (10 mL) was added water (3 mL). The mixture was stir at 100 °C for 2 hr under nitrogen protection. Remove most organic solvent in vacuum, then the residue was re-dissolved in DCM, washed with water; the organic layer was dried over magnesium sulfate, filtered and concentrated in vacuum. The residue was purified by CombiFlash, eluted with methanol in DCM (0-5percent, 30 min). Collected the desired fraction to afford 40 mg brown syrup, it was further purified by basic Prep-HPLC (0.1 percent NH4OH/ACN/H20).Collected the desired fraction and lyophilized to afford 10 mg title compound as off-white powder. 1 H NMR (400 MHz, Methanol-^) delta 8.22 - 8.05 (m, 3H), 7.96 (d, J= 15.9 Hz, 1 H), 7.87 (s, 2H), 7.79 - 7.71 (m, 2H), 7.65 (d, J = 0.9 Hz, 1 H), 2.63 (d, J= 0.8 Hz, 3H). LC-MS: [M+H]+ = 401 .8, 402.8. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | With potassium phosphate; chloro(2-dicyclohexylphosphino-2?,4?,6?-triisopropyl-1,1?-biphenyl)[2-(2?-amino-1,1?-biphenyl?)]palladium(II); In 1,4-dioxane; water; at 80℃; for 5.0h;Inert atmosphere; | In a 25 mL round-bottomed flask were added K3P04 (63.2 mg, 0.298 mmol), 25.2 (65 mg, 0.149 mmol), xphos Pd G2( 20mg, 0.025mmol) and R1 (30.9 mg, 0.149 mmol) . The reaction was evacuated and filled with N2 for three times. Dioxane (4 mL) and water (1 mL) were added. The reaction was heated to 80 °C for 5h under N2 protection. The reaction was cooled to r.t. and quenched with NH4CI (aq). The combined organic phase was washed with brine and dried over Na2S04, concentrated and purified by column chromatography on silica gel (eluent: PE/EA=10:1 -2:1 ) to give the title compound (30mg, 46percent) as a yellow solid. LC-MS: [M+H]+= 436.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.8% | With bis-triphenylphosphine-palladium(II) chloride; sodium carbonate; In water; isopropyl alcohol; at 100℃; for 3.0h;Inert atmosphere; | A solution of 37.4 (170 mg, 0.278 mmo), Na2C03 (58.9 mg, 0.556 mmol) 5- bromo-4-chloropyridin-3-amine (57.6 mg, 0.278 mmol), Pd(PPh3)2CI2 (19.50 mg, 0.028 mmol) in 2-Propanol (3 mL) was added water (1 mL). The mixture was degassed with nitrogen three times. Then the mixture was stirred at 100 °C for 1 hr under nitrogen protection. The mixture was diluted with ethyl acetate, washed with water; the organic layer was dried over magnesium sulfate, filtered and concentrated in vacuum. The residue purified with basic Prep-HPLC (0.1 percent NH4OH/ACN/H20). Collected the desired fraction and lyophilized to afford the title compound (8.2 mg, 6.8percent) as white powder. 1 H NMR (400 MHz, Methanol-^) delta 8.06 (s, 1 H), 7.86 (s, 1 H), 7.78 (s, 1 H), 7.73 (s, 1 H), 7.59 (s, 1 H), 5.17 (p, J= 7.4 Hz, 1 H), 4.08 - 3.87 (m, 1 H), 3.01 (s, 3H), 2.76 (ddd, J= 13.8, 7.8, 5.4 Hz, 1 H), 2.65 (s, 3H), 2.53 - 2.12 (m, 5H). LC-MS: [M+H]+ = 428.9, 430.9. |
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