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CAS No. : | 170229-98-8 | MDL No. : | MFCD00672914 |
Formula : | C8H8BrNO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | ZPFPOZMNEKPBIF-UHFFFAOYSA-N |
M.W : | 214.06 | Pubchem ID : | 7020869 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P301+P312-P302+P352-P304+P340-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
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* 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 |
---|---|---|
36% | With polyphosphoric acid; at 170℃; for 3h; | A mixture of 4-Bromo-3-methyl-benzamide (1 g, 4.67 mmol) and vinylene carbonate (0.4 ml, 6.30 mmol) in PPA (15 ml) was heated to 170 C. for 3 h. Upon completion, the reaction was cooled, quenched with water, and extracted with EtOAc. The organic phase was washed with brine, dried over Na2SO4, and concentrated. The crude material was purified by column chromatography to give 2-(4-Bromo-3-methyl-phenyl)-oxazole (400 mg, 36%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With hydrogenchloride; BH3; borane; In tetrahydrofuran; methanol; water; | (A)4-Bromo-3 -methylbenzylamine.HCl To a solution of borane (1.0 M BH3 in THF, 42 mL) was added a solution of <strong>[170229-98-8]4-bromo-3-methylbenzamide</strong> (1.3 g, 6.0 mmol) in anhydrous THF (20 mL) and the mixture stirred for 6 h at rt. To this was sequentially added dropwise 6N HCl (30 mL), water (30 mL), and MeOH (150 mL) and the mixture stirred for 12 h. After the resulting mixture was concentrated to 50 mL, the precipitates were filtered off and the filtrate concentrated in vacuo. The residue was purified by column chromatography (EtOAc: n-hexane, 1:4) to give the title compound as a yellow oil (0.81 g, 57%). 1H NMR (CD3OD) δ7.60 (d, 1H), 7.37 (s, 2H), 7.18 (d, 1H), 4.04 (s, 2H), 2.41 (s, 3H). FAB MS: 201 [M+1]+ |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
8.9g (89%) | In N-methyl-acetamide; methanol; dichloromethane; water; | EXAMPLE 21 N- (3, 4-Dimethyl-5-isoxazolyl) -2'-?(formylamino)[methyl]-4'-(2-oxazolyl)?1,1'-[biphenyl]-2-sulfonamide STR48 A. 4-Bromo-3-methylbenzamide To a solution of 10 g (46.5 mmol) of 4-bromo-3-methyl benzoic acid in 200 mL of dichloromethane under argon, 30 mL of 2M solution of oxalyl chloride in dichloromethane w as added. Four drops of dimethylformamide was then added and the mixture was stirred at room temperature for 1 hour. The soltion was evaporated and dried in vacuo. The residue was dissolved in 100 mL of methanol, and 25 mL of 28% aqueous ammonium hydroxide was added to the mixture. The solution was stirred at room temperature for 3 hours, and then diluted with 500 mL of water. The resulting white solid was filtered, washed with water and dried to afford 8.9g (89%) of compound A. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
6.8 g (100%) | With ammonium chloride; In methanol; dichloromethane; toluene; | A. 4-Bromo-3-methylbenzenecarboxamidamide To a suspension of 2.73 g (51.0 mmol) of ammonium chloride in 40 mL of toluene at 0 C., a 2.0M solution of trimethyl aluminum (25.5 mL) was added over 5 minutes. The mixture was then slowly warmed to room temperature and stirred for an additional 2 hrs. This mixture was then added to a solution of 5.0 g (25.5 mmol) of 4-bromo-3-methyl benzonitrile in 15 mL of toluene under argon, and the mixture was heated at 80 C. for 6 days. The mixture was then cooled to room temperature and added to a slurry of silica gel (100 g) in 200 mL of CH2 Cl2 and filtered. The silica was washed with 400 mL of methanol and the combined filtrate was evaporated to provide 6.8 g (100%) of the title compound of this step as a white solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium carbonate; triethylamine;PdCl2(PPh3)2; In 1,4-dioxane; ethyl acetate; | Example 225 3'-(5-Carbamimidoyl-2-methylsulfanyl-thiophene-3-sulfonyl)-2-methyl-biphenyl-4-carboxylic acid amide trifluoroacetate Following the same procedure as in Example 220, step a, reaction of 4-bromo-3-methyl-benzamide (200 mg, 0.93 mmol), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (0.41 mL, 2.8 mmol, Aldrich Chemical Company), PdCl2(PPh3)2 (65 mg, 0.093 mmol, Strem Chemicals Inc, Newburyport, Mass.), Et3N (700 μL, 46 mmol), and dioxane (5 mL) afforded 140 mg of a brown oil (58%) after purification (SiO2, flash elution: 30% EtOAc in hexanes. The above boronate ester (140 mg, 0.54 mmol) was reacted according to the procedure used in Example 1, step c, with [4-(3-bromo-benzenesulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester (88 mg, 0.18 mmol, as prepared in Example 27, step c), tetrakis(triphenylphosine)palladium(0) (52 mg, 0.05 mmol, Strem Chemicals Inc, Newburyport, Mass.), Na2CO3 (0.7 mL, 2 M), and toluene/EtOH mixture (2:1, 2.1 mL) to afford [4-(4'-Carbamoyl-2'-methyl-biphenyl-3-sulfonyl)-5-methylsulfanyl-thiophen-2-yl]-imino-methyl}-carbamic acid tert-butyl ester after purification (preparative TLC, 1:3 EtOAc/hexanes, 3*1000μ SiO2 plate). ESI-MS (m/z): Calcd. for C25H27N3O5S3: 545.7; found: 446.1 (M-Boc). |