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CAS No. : | 55687-34-8 | MDL No. : | MFCD09834132 |
Formula : | C8H5BrN2O | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | BDBWPIXISLYKEG-UHFFFAOYSA-N |
M.W : | 225.04 | Pubchem ID : | 12686394 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302-H315-H319-H332-H335 | 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 |
---|---|---|
87% | With trichlorophosphate; at 60℃; | [001023] Part C. Preparation of 6-bromo-2-chloroquinoxaline.; [001024] To a flask containing phosphorus oxychloride (3.4ml, 36.5mmol) was added the product fromPart B (255mg, l.lmmol) and the solution was heated at 6O0C overnight. The solution was cooled to room temperature, poured over ice and the resulting solid collected by filtration to give the title compound (239mg, 87%). |
70% | With N,N-dimethyl-aniline; trichlorophosphate; at 15℃; for 0.25h;Reflux; | Compound 39 (600 mg, 2.66 mmol) was added to cold phosphorous oxychloride (4 mL) in portions wise to give a slurry. To the resulting slurry was added drop wise N,N- dimethylaniline (0.4 ml, 2.93 mmol) below 15C. The brick red mixture was refluxed for 15 min, and the resulting dark brown clear solution was then cooled to ambient temperature. It was added to ice cold water (40 mL) , and the mixture was basified slowly with 40% aq. NaOH to pH 8. The solid was collected by filtration, washed with water (2x10 mL) and dried to give the title compound 40 (70%) . |
51% | With trichlorophosphate; In N,N-dimethyl-formamide; at 50℃; for 2h; | 6-bromoquinoxalin-2(1 H)-one (9.0 g, 40 mmol) was dissolved in POCI3 (50 mL) and DMF (2 mL) was added at RT. The mixture was heated at 50C for 2 hours. After completion of the reaction it was cooled to RT and was poured slowly into ice cold water. The mixture was stirred for 30 minutes and then filtered to afford crude product.The crude product was purified by column chromatography using neutral silica gel of 60- 120 mesh size. A gradient of 8-9 % DCM in hexane was used to elute the title compound (5.O g, 51%).1H NMR (d6-DMSO) D 9.03 (s, 1 H), 8.42 (d, 1H), 8.08 (dd, 1 H), 7.98 (d, 1H). |
With trichlorophosphate; In N,N-dimethyl-formamide; at 120℃; for 1.5h;Product distribution / selectivity; | To a stirred solution of the compound obtained from Preparation 29 (2 g, 8.89 mmol) in phosphorus oxychloride (15 mL), was added DMF (1 mL). The mixture was stirred at 120C for 1.5 hours then allowed to cool to room temperature. The dark solution was concentrated in vacuo and cautiously quenched with crushed ice. The aqueous suspension was neutralised with 10% potassium carbonate solution and extracted with DCM (2 x 30 mL). The combined organic phases were dried (Na2SO4), filtered and concentrated to give 1.94 g of the title compound as a brown solid.1H-NMR (400 MHz, DMSOd6): delta= 9.02(1 H, s), 8.40(1 H, d), 8.06(1 H, dd), 7.98(1 H, d). LCMS (run time = 2min): R4 = 1.69 min; m/z 243; 245 [M+H]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | With bromine; silver sulfate; In tetrachloromethane; sulfuric acid; at 20 - 50℃; | The quinoxalin-2(1H)-one (14.6 g, 0.1 mol, Aldrich, cat. no. 260517) and silver sulphate (15.6 g, 0.05 mol) were dissolved in cone. Sulfuric acid (100 ml) at 200C. Bromine (5.2 ml, 0.1 mol) was added and the reaction mixture was stirred vigorously for 24 hours. The reaction mass was then diluted with carbon tetrachloride (100 ml_), and this was heated at 5O0C. The reaction mass was then filtered and the filtrate was poured into ice cold water and stirred for 30 minutes to obtain a precipitate. The precipitate was filtered and the solid material was dried in vacuo to afford the title product (9.0 g, 40%). |
With bromine; silver sulfate; In sulfuric acid; at 20℃;Inert atmosphere;Product distribution / selectivity; | Quinoxalin-2(1H)-one (5 g, 34.2 mmol) was stirred in sulphuric acid (50 ml_) and silver sulphate was added (5.3 g, 17.1 mmol). The mixture was vigorously stirred until complete dissolution, whereupon bromine (1.76 ml_, 34.2 mmol) was added dropwise. The resulting mixture was stirred at room temperature under nitrogen overnight. Carbon tetrachloride (50 ml_) was added and the mixture was heated to 500C for 30 minutes, then filtered. The solid was washed with carbon tetrachloride and the filtrate was collected. This was poured into a beaker of crushed ice and slurried to give a thick off-white suspension. The crude material was filtered and the resulting solid was triturated in methanol and re-filtered. The solid pulled dry to give 5.44 g of the title compound as a pale brown solid.1H-NMR (400 MHz, DMSOd6): delta=12.52(1 H, bs), 8.17(1 H, s), 7.94(1 H, d), 7.68(1 H, dd), 7.22(1 H, d). LCMS (run time = 6 min): R4 = 2.29 min; m/z 225; 227 [M+H]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | [001021] Part B. Preparation of 6-bromoquinoxalin-2(leta)-one.; [001022] To a solution of sodium hydroxide (337mg, 8.4mmol) in H2O (2.1ml) was added the product from Part A (423mg, 1.4mmol) and stirring was continued at 650C for Ih. The cooled solution was diluted with H2O (4ml) and sodium borohydride (31.9mg, 0.84mmol) was added and stirring was continued at room temperature for 1.5h. Ice was added to the solution followed by dropwise addition of6nu HCl until acidic. The resulting solid was collected by filtration, washed with H2O, and dried in a vacuum oven to give the title compound (273mg, 86%). |
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