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CAS No. : | 42237-85-4 | MDL No. : | MFCD00227745 |
Formula : | C7H6BrNO2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RQSXRGSPGHZKFT-UHFFFAOYSA-N |
M.W : | 216.03 | Pubchem ID : | 11569604 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H317-H319 | Packing Group: | N/A |
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 |
---|---|---|
94% | Concentrated hydrochloric acid (30 ml) was gradually added to a solution of the title compound of Preparation 49 (7.02 g, 28.54 mmols) and ethanol (150 ml), the solution was stirred at room temperature during five minutes. Then Tin (II) chloride was added and the solution was stirred at 50C for two hours. The solution was cooled at room temperature. The solution basified to pH 9 with 8M sodium hydroxide precipitating a solid. The solid was collected by filtration and discarded. The filtrate was acidified with hydrochloric acid to pH 5 and precipitation from this solution gave 5.8 g (94%) of the title compound. HPLC/MS (10 min) retention time 4.67 min LRMS: m/z 216 (M-1) | |
94% | PREPARATION 21; 3-Amino-5-bromobenzoic acid [Show Image] Concentrated hydrochloric acid (30 mL) was gradually added to a solution of the title compound of Preparation 20 (7.02 g, 28.54 mmols) and ethanol (150 mL), the solution was stirred at room temperature during five minutes. Then Tin (II) chloride was added and the solution was stirred at 50C for two hours. The solution was cooled at room temperature. The solution basified to pH 9 with 8M sodium hydroxide precipitating a solid. The solid was collected by filtration and discarded. The filtrate was acidified with hydrochloric acid to pH 5 and precipitation from this solution gave 5.8 g (94%) of the title compound. HPLC/MS (10 min) retention time 4.67 min LRMS: m/z 216 (M-1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With toluene-4-sulfonic acid; In acetonitrile; at 160℃; for 0.166667h;Microwave irradiation; | [1- [5-CHLORO-2- (4-BROMO-2-FLUORO-BENZYLOXY)-PHENYL]-PENTANE-1,] 4-dione (150mg, 0. [363MMOL),] <strong>[42237-85-4]3-amino-5-bromobenzoic acid</strong> (79mg, 0. [363MMOL)] and [PTSA] (5mg) were heated in acetonitrile (2ml) at [160C] for 10 minutes in the microwave. Upon cooling, the mixture was diluted with DCM and washed with 2M HCI, dried [(NA2SO4),] filtered and concentrated. The residue was purified by chromatography, on silica, with cyclohexane containing a gradient of EtOAc (10-20%) to give the title compound (45mg, 21 %). 1H NMR [(400MHZ,] CDCI3) 2.17 (3H, s), 4.76 (2H, s), 6.13 (1H, d, J=4. [0HZ),] 6.28 (1H, d, J=3.5Hz), 6.64 (1H, d, J=8.8Hz), 6.89-6. 95 (1H, m), 7.13 (1H, dd, J=2.5Hz, J=8.8Hz), 7.24-7. 28 (3H, m's excess), 7.33-7. 36 (1H, m), 7.63-7. 66 (1H, m), 8.09 (1H, t, J=1.5Hz). LC/MS t=4.49 min, [MH+] 594 and 596, [MH-] 592 and 594. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
11% | With toluene-4-sulfonic acid; In acetonitrile; at 160℃; for 0.166667h;Microwave irradiation; | [1- [5-CHLORO-2- (2, 6-DIFLUORO-BENZYLOXY)-PHENYL]-PENTANE-1,] 4-dione (131mg, 0. [37MMOL),] 3- amino-5-bromobenzoic acid (80mg, 0. [37MMOL)] and [PTSA] (5mg) were heated in acetonitrile [(2ML)] at [160C] for 10 minutes in the microwave. Upon cooling, the mixture was diluted with DCM and washed with [2M] HCI, dried [(NA2SO4),] filtered and concentrated. The residue was purified by chromatography, on silica, with cyclohexane containing a gradient of EtOAc (10-20%) to give the title compound (21 mg, [11 %).] 'H NMR [(400MHZ,] [MEOD)] 2.07 (3H, s), 4.81 (2H, s), 6.00 (1H, d, J=2.8Hz), 6.12 (1H, d, J=3.5Hz), 6.89-6. 99 (3H, m), 7.12-7. 21 (2H, m), 7.23 (1H, s), 7.32-7. 42 (1H, m), 7.52 [(1H,] s), 7.97 (1 H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
21% | With toluene-4-sulfonic acid; In acetonitrile; at 160℃; for 0.166667h;Microwave irradiation; | [1- [5-CHLORO-2- (2, 3-DIFLUORO-BENZYLOXY)-PHENYL]-PENTANE-1,] 4-dione (150mg, 0. [43MMOL),] 3- amino-5-bromobenzoic acid (92mg, 0. 43mmol) and [PTSA] (5mg) were heated in acetonitrile (2ml) at [160C] for 10 minutes in the microwave. Upon cooling, the mixture was diluted with DCM and washed with 2M HCI, dried [(NA2SO4),] filtered and concentrated. The residue was purified by chromatography, on silica, with cyclohexane containing a gradient of EtOAc (10-20%) to give the title compound (48mg, 21 %). 'H NMR [(400MHZ, CDCI3)] 2.17 (3H, s), 4.82 (2H, s), 6.14 (1H, d, J=2.5Hz), 6.30 (1H, d, J=3.5Hz), 6.66 (1H, d, J=8.8Hz), 6.75-6. 82 (1H, m), 6. [98-7.] [18] (4H, m), 7.34 (1H, s), 7.65 (1 H, s), 8.10 (1 H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With thionyl chloride; at 20℃;Cooling with ice; | 3-Bromo-5-aminobenzoic acid 12 (1.0 g, 4.62 mmol) was stirred in methanol (15mL) with ice cooling, and the yellow solution was treated with thionyl chloride (4.00 mL, 55.0 mmol) dropwise over 20 mm. The resulting mixture was allowed to warm up to room temperature and left stirring overnight. The reaction mixture was quenched with aqueous saturated NaHCO3 solution at 0 C. The solvent was then removed under vacuum, and the residue was suspended in ethyl acetate (200 mL). The organic phase was washed with brine (100 mL), dried (Na2504) and concentrated to afford the title compound as a yellow solid (1.08 g, 98%). ?H NMR (400 MHz, Methanol-d) oe 7.10 (t, J 1.6 Hz, 1H), 6.83 (t, J 1.6 Hz, 1H), 6.57 (t, J= 1.6 Hz, 1H), 3.46 (s, 3H). 13C NMR (100 MHz, CDC13) oe: 52.3, 114.6, 121.6, 122.3, 122.9, 132.6, 147.7, 166.0. m/z (ESI, MH) 231. ESI-HRMS (MH) calcd. for C8H8BrNO2 229.9817, found 229.9818. HPLC purity 98.8 % (R= 12.3 mm). |
98% | With thionyl chloride; at 20℃; for 15h;Cooling with ice; | 3-Bromo-5-aminobenzoic acid (61a, 1.01 g, 4.62 mmol) was stirred in methanol ( 15 mL) with ice cooling, and the yellow solution was treated with thionyl chloride (4.00 mL, 55.0 mmol) dropwise over 20 min. The resulting mixture was warm up to room temperature and left stirring for 15 h. The reaction mixture was quenched with aqueous saturated (0564) NaHCOs solution at 0 C. The solvent was then removed under vacuum, and the residue was suspended in ethyl acetate (200 mL). The organic phase was washed with brine (100 mL), dried (Na2SOi) and concentrated in vacuo to afford the title compound 61b (1.08 g, 98%) as a yellow solid; NMR (400 MHz, DMS0 ) d 7.16 (dd, J =1.48, 2.12 Hz, 1H), 7.13 (t, J =1.64 Hz, 1H), 6.96 (t, J =2.00 Hz, 1H), 5.74 (s, 2H), 3.81 (s, 3H); MS (ESI, m/z) 231 (0565) [M+l]+; ESI-HRMS calcd. m/z for C8H8BrN02 229.9817, found 229.9818 [M+l]+ |
91% | With thionyl chloride; at 0℃; for 24h;Reflux; | General procedure: A solution of the appropriate 2-aminobenzoic acid (1equiv) in MeOH was cooled to 0C followed by a dropwise addition of thionyl chloride (2.5equiv). The mixture was refluxed for 24h. After evaporation of the solvent and neutralization by addition of a saturated aqueous NaHCO3 solution, the mixture was extracted with EtOAc and the combined organic layers were dried over MgSO4. Purification by CC (n-hexane/EtOAc) provided the title compounds. |
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