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Chemical Structure| 852330-31-5 Chemical Structure| 852330-31-5

Structure of 852330-31-5

Chemical Structure| 852330-31-5

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Product Details of [ 852330-31-5 ]

CAS No. :852330-31-5
Formula : C8H5BrF3NO3S
M.W : 332.09
SMILES Code : O=C(C1=C(NC(C(F)(F)F)=O)C=C(Br)S1)OC
MDL No. :MFCD19441860

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Application In Synthesis of [ 852330-31-5 ]

* 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 [ 852330-31-5 ]

[ 852330-31-5 ] Synthesis Path-Downstream   1~2

  • 1
  • [ 79128-68-0 ]
  • [ 852330-31-5 ]
YieldReaction ConditionsOperation in experiment
41% To a solution of N- (1-methylethyl) propan-2-amine (20 mL, 142 mmol) in THF (200 mL) was added 1.6 M n-butyl lithium in hexane (84.2 mL, 132 mmol) at 00C. After stirring at this temperature for 15 min, the mixture was cooled to - 78C. Then, a solution of methyl 3-[ (trifluoroacetyl) amino] thiophene-2-carboxylate (10.1 g, 40.0 mmol) in THF (50 itiL) was added slowly. After additional stirring at -780C for 1 h, 1, 2-dibromoethane (20.6 inL, 238 mmol) was added at once. The mixture was stirred at -78C for 30 min and at room temperature for 30 min. The mixture was poured into saturated aqueous NaHCO3 (600 mL) and extracted with EtOAc. The combined extracts were washed with brine, and then dried over Na2SO4. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, hexane to 10:90 hexane/EtOAc) to give the title compound (5.30 g, 41%) as a yellow solid: 1H NMR (300 MHz, CDCl3) delta 3.94 (3H, s) , 8.11 (IH, s) , 11.15 (IH, br s) .
Step 9B: To THF (100 mL) at-78C was added diisopropylamine (10 mL) and butyllithium (26.4 mL; 2.5 M in hexanes). The reaction mixture was warmed to 0C and stirred for 10 minutes. The reaction mixture was cooled to-78C and 9a (5.06 g) in THF (20 mL) was transferred via canula. The reaction was stirred at-78C for 1 hour, and then treated with 1,2-dibromoethane (10.3 mL) in one portion. The reaction mixture was stirred at-78C for 30 minutes, then at room temperature for 30 minutes. Saturated sodium bicarbonate solution was added and the aqueous layer was extracted with three times with ethyl acetate. The combined organic layers were washed with water and brine. The organic layer was dried over MgS04, concentrated under reduced pressure, and purified by silica gel chromatography (2.5 % ethyl acetate in hexanes) to give compound 9b (2.88 g).
Preparation of 5-bromo-<strong>[79128-68-0]3-(2,2,2-trifluoracetamido)thiophene-2-carboxylic acid methyl ester</strong>: To THF (100 mL) at -78 C. is added diisopropylamine (10 mL) and butyllithium (26.4 mL, 2.5 Min hexanes). The reaction mixture is allowed to warm ot 0 C. and stir for 10 minutes. The reaction mixture is re-cooled to -78 C. and <strong>[79128-68-0]3-(2,2,2-trifluoracetamido)thiophene-2-carboxylic acid methyl ester</strong> (5.06 g) dissolved in THF (20 mL) is added via cannula. The reaction is stirred at -78 C. for 1 hour and then treated with 1,2-dibromoethane (10.3) added in one portion. The reaction is stirred an additional 30 minutes at -78 C. then allowed to warm to room temperature for 30 minutes. NaHCO3 (sat. solution) is added and the aqueous layer extracted with EtOAc (*3). The combined organic layers are washed with water and brine. The organic layer is dried and concentrated under reduced pressure and purified over silica (2.5% EtOAc in hexanes) to afford 2.88 g of the desired product.
B) Production of methyl 5-bromo-3-[(trifluoroacetyl)amino]thiophene-2-carboxylate To a solution of diisopropylamine (20 mL) in tetrahydrofuran (200 mL) was added 1.6M n-butyllithium/hexane solution (82.4 mL) while stirring under ice-cooling, and the mixture was stirred at 0C for 15 min. After stirring, the reaction system was cooled to -78C, and a solution of <strong>[79128-68-0]methyl 3-[(trifluoroacetyl)amino]thiophene-2-carboxylate</strong> (10 g) in tetrahydrofuran (50 mL) was added dropwise. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 1 hr, and 1,2-dibromoethane (20.6 mL) was added. After stirring at the same temperature for 30 min, the reaction system was allowed to warm to room temperature, and further stirred for 30 min. The reaction system was poured into saturated aqueous sodium hydrogen carbonate (600 mL), and the mixture was extracted with ethyl acetate, washed with brine, and dried over anhydrous sodium sulfate. Insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (5.3 g) as a yellow solid. 1H-NMR(CDCl3) delta 3.94(3H,s), 8.11(1H,s), 11.15(1H,brs).

  • 2
  • [ 79128-68-0 ]
  • [ 852330-31-5 ]
  • [ 22288-78-4 ]
YieldReaction ConditionsOperation in experiment
To stirred tetrahydrofuran (100 inL) at -78C were added dropwise diisopropylamine (9.00 mL, 63.9 mmol) and n-butyl lithium (37.1 mL, 59.4 mmol, 1.6 M solution in n-hexane) successively. The reaction mixture was allowed to warm to 00C and stirred for additional 10 min. The mixture was cooled to -78C again and methyl 3- (2,2, 2- trifluoroacetamido) thiophene-2-carboxylate (4.56 g, 18.0 mmol) was added to the mixture. After 1 h, bromine (2.78 mL, 54.0 mmol) was added to the mixture, and stirring was continued at -78C for 2 h and at room temperature for 30 min. The mixture was then poured into sat. aqueous sodium hydrogen carbonate (180 mL) . Extraction with ethyl acetate (150 mL) , washing with brine, drying over magnesium sulfate, filtration and concentration at reduced pressure gave an oil. The oil was purified by column chromatography (Combiflash, 12 g silica gel, hexanes to 90:10 hexanes/ethyl acetate) to afford a mixture of the title compound and methyl 3-aminothiophene-2-carboxylate (1.86 g) as a white solid. The ratio was about 2:1 estimated by 1H NMR analysis:1H NMR (300 MHz, DMSO-d6) delta 3.84 (3H, s) , 7.79 (IH, s) , 11.22 (IH, br s) .
 

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