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Chemical Structure| 115378-21-7 Chemical Structure| 115378-21-7

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Chemical Structure| 115378-21-7

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Product Details of [ 115378-21-7 ]

CAS No. :115378-21-7
Formula : C9H10BrNO3
M.W : 260.09
SMILES Code : O=C(OC)C1=CC(Br)=CC(OC)=C1N
MDL No. :MFCD20040042

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Application In Synthesis of [ 115378-21-7 ]

* 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.

  • Downstream synthetic route of [ 115378-21-7 ]

[ 115378-21-7 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 5121-34-6 ]
  • [ 115378-21-7 ]
YieldReaction ConditionsOperation in experiment
95% With N-Bromosuccinimide; In DMF (N,N-dimethyl-formamide); at 5℃; for 0.5h; Step 3; The crude product (18.80 g) obtained in Step 2 was dissolved in dimethylformamide (200 ml) and N-bromosuccinimide (17.98 g, 0.10 mol) was added by portions at 5C. After the completion of the addition, the mixture was stirred at the same temperature for 30 min. The reaction mixture was poured into water (500 ml) and extracted twice with ethyl acetate (300 ml). The organic layer was washed with water (300 ml), saturated aqueous sodium hydrogen carbonate and saturated brine in this order, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and the obtained residue was purified by silica gel chromatography (chloroform) to give the object product (25.11 g, yield 95%) as a yellow oil. ¹H NMR(CDC13 300MHz) (No.) ppm: 3.86 (6H, s) , 6.02 (2H, brs) , 6.90 (lH, s), 7.60 (lH, s)
95% With N-Bromosuccinimide; In DMF (N,N-dimethyl-formamide); at 5℃; for 0.5h; The crude product (18.80 g) obtained in Step 2 was dissolved in dimethylformamide (200 ml), and N-bromosuccinimide (17.98 g, 0.10 mol) was added by portions at 5C. After completion of the addition, the mixture was stirred at the same temperature for 30 min. The reaction mixture was poured into water (500 ml) and extracted twice with ethyl acetate (300 ml). The organic layer was washed successively with water (300 ml), saturated aqueous sodium hydrogen carbonate and saturated brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure and the obtained residue was purified by silica gel chromatography (chloroform) to give an object product (25.11 g, yield 95%) as a yellow oil.1H NMR (CDCl3 300MHz) (delta) ppm: 3.86 (6H, s), 6.02 (2H, brs), 6.90 (1H, s), 7.60 (1H, s)
89% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 20℃; for 2h; Step A:; To a solution of 2-amino-3-methoxybenzoate (1.62 g, 8.97 mmol) in DMF (15 mL) was added N-bromosuccinimide (1.76 g, 9.87 mmol). The resulting mixture was stirred at room temperature for 2 h. The reaction mixture was diluted with ether and water. The aqueous layer was isolated and extracted with ether (2×100 mL). The combined organic layers were washed with water (2×100 mL), brine, dried over Na2SO4, filtered and concentrated to afford a brown solid. The crude material was purified by column chromatography (silica gel, 95:5 hexanes/ethyl acetate) to afford the desired product (2.08 g, 89%) as a light orange solid: 1H NMR (300 MHz, CDCl3) delta 7.60 (d, J=2.1 Hz, 1H), 6.90 (d, J=2.1 Hz, 1H), 6.03 (br s, 2H), 3.86 (s, 6H); MS (ESI+) m/z 259 (M+H).
88.1% With N-Bromosuccinimide; In N,N-dimethyl-formamide; for 1.25h;Cooling with ice; [Step b] To a solution of compound 2 (86.7 g, 473 mmol) in N,N-dimethylformamide (430 mL) was added N-bromosuccinimide over 15 min under ice-cooling, and the mixture was stirred for 1 hr. To the reaction solution were added saturated aqueous sodium hydrogen carbonate solution (500 mL) and water (500 mL), and the mixture was extracted with ethyl acetate (1.0 L). The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated. The residue was purified by silica gel chromatography, and suspended and washed in n-hexane (120 mL) to give compound 3 (108 g, 88.1 %). 1H-NMR (400 MHz, CDCl3)delta: 3.87(6H, s), 6.03(2H, brs), 6.90(1H, d, J=2.0Hz), 7.26(1H,s), 7.60(1H, d, J=2.4Hz).
86% With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 0.5h; To a solution of 15 <strong>[5121-34-6]methyl 2-amino-3-methoxybenzoate</strong> (22.4 g 123 mmol) in 7 DMF (250 mL) was added 17 N-bromosuccinimide (21.9 g, 123 mmol) portionwise at 0 C. The mixture was stirred at 0 C. for 0.5 h. To the mixture was added 9 water and extracted with EtOAc (500 mL×2). The combined organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography to provide the 18 title compound (27.5 g, 86%) as a white solid. 1H NMR (400 MHz, CDCl3) delta 7.60 (d, J=2.2 Hz, 1H), 6.90 (d, J=2.2 Hz, 1H), 6.03 (brs, 1H), 3.87 (s, 3H); [M+H]+ 260.
63% With bromine; In acetic acid; at 0 - 20℃; for 1h; Step 4: Methyl 2-amino-5-bromo-3-methoxybenzoateTo a stirred solution of <strong>[5121-34-6]methyl 2-amino-3-methoxybenzoate</strong> (22 g, 0.121 mol) in acetic acid (220 mL) was added bromine (7.5 mL, 0.145 mol) dropwise at 0C. The reaction mixture was stirred at room temperature for 1 h. After the completion, the reaction mixture was poured into 1 L of cold water and stirred for 30 min at room temperature and extracted with ethyl acetate (2x500 mL). The combined organic layers were washed with saturated sodium bicarbonate solution (2x1 L) followed by brine solution, then dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure and the crude product was purified using column chromatography (100-200 mesh silica gel, 10% EtOAc in hexane) to afford the title compound as a white solid (20 g, 63% yield).XH NMR (400 MHz, DMSO-d6) : delta 7.42 (d, J = 2.0 Hz, 1H), 7.09 (d, J = 2.0 Hz, 1H), 6.47 (brs, 2H), 3.85 (s, 3H), 3.81 (s, 3H) ; ESI-MS: Calculated mass: 258.98; Observed mass: 260.10 [M+H]+.
27.5 g With N-Bromosuccinimide; In N,N-dimethyl-formamide; at 0℃; for 0.5h; To a solution of compound 53 (22.4 g 123 mmol) in DMF (250 mL) was added N-bromosuccinimide (21.9 g, 123 mmol) portionwise at 0 C. The mixture was stirred at 0 C for 0.5 h. To the mixture was added water and extracted with EtOAc (500 mL x 2). The combined organic layer was dried over MgSO4, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography to provide the desired compound 54 (27.5 g, 86%) as a white solid.

 

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