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CAS No. : | 1544-75-8 | MDL No. : | MFCD05663528 |
Formula : | C7H5FN2O | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | DZRTZDURJKZGSP-UHFFFAOYSA-N |
M.W : | 152.13 | Pubchem ID : | 10329453 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-H335 | 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 |
---|---|---|
83% | With sodium hydrogen sulfide; In 1-methyl-pyrrolidin-2-one; at 90℃; under 22502.3 Torr; for 24h; | General procedure: Add in a 15ml Teflon-lined reactor216 mg (2 mmol) of o-phenylenediamine, 56 mg (1 mmol)NaHS (molar ratio of o-phenylenediamine to NaHS is 1:2),Add 1 mL of NMP as the reaction solvent.Put the magnets and tighten the reactor.Then charge 3MPa of carbon dioxide,The reaction was stirred at 90 C for 24 hours.After cooling the reactor to room temperature,Extracted with ethyl acetate,Washed with saturated saline,After drying the organic layer, the solvent is removed under reduced pressure to give a crude material;The crude product is separated by recrystallization or column chromatography (200-300 mesh silica gel,Petroleum ether and ethyl acetate as eluent)99% white powder benzimidazolone 116mg,The yield was 88%. |
(4) 3-(2-(benzoxazyl))-6-fluorobenzimidazol-2-(1H)-one; (Compound 14); mp: 295-296 C. | ||
(10) 3-(2-(7-fluorobenzoxazyl))-5-fluorobenzimidazol-2-(1H)-one; (Compound 18); mp: 268-270 C. |
(5) 3-(2-(6-fluorobenzoxazyl))-6-fluorobenzimidazol-2-(1H)-one; (Compound: 4); mp 284-285 C. | ||
(9) 3-(2-(7-fluorobenzoxazyl))-6-fluorobenzimidazol-2-(1H)-one; (Compound 3); mp: 284-285 C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | b) A solution of <strong>[1544-75-8]5-fluoro-1H-benzo[d]imidazol-2(3H)-one</strong> (1.25 g, 8.22 mmol) in phosphorus oxychloride (25.2 ml, 270.34 mmol) was heated for 18 hours at 100 C. The reaction mixture was cooled to RT and excess of POCl3 was evaporated in vacuo. The residue was neutralized with saturated NaHCO3 solution (10 ml) and extracted with EtOAc (3×20 ml). The organic phase was washed with brine and then dried over MgSO4, filtered and concentrated under reduced pressure to afford 2-chloro-6-fluoro-1H-benzo[d]imidazole (1.146 g, 82%); 1H NMR (400 MHz, DMSO-d6) 7.09 (1H, ddd), 7.36 (1H, dd), 7.53 (1H, dd); m/z: (ES+) MH+, 171.34. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | In tetrahydrofuran; at 20℃;Inert atmosphere; Cooling with ice; | A stirred solution of 4-fluorobenzene-1 ,2-diamine (15.1 g, 120 mmol) in THF (120 mL) under nitrogen was cooled using an ice-bath and then was treated with di(1 -/-imidazol-1 - yl)methanone (23.4 g, 144 mmol) portion-wise over 15 min. The resulting mixture was slowly warmed to room temperature then was concentrated in vacuo after 2.5 h. The residue was suspended in a mixture of water and DCM (250 mL each) and filtered off. This residue was then washed with water (50 mL) and DCM (50 mL), before being dried at 40 C under vacuum for 16 h to give the title compound (16.0 g, 105 mmol, 88%) as a brown solid. LCMS (high pH): Rt 0.57 min; [M-H+]" = 151.1 deltaEta NMR (400 MHz, DMSO-d6) ppm 10.73 (br s, 1 H), 10.61 (br s, 1 H), 6.91-6.84 (m, 1 H), 6.78-6.70 (m, 2H). |
78% | In tetrahydrofuran; at 150℃; for 0.333333h;Microwave irradiation; | Intermediate 15: 5-Fluoro-1 ,3-dihvdro-2H-benzimidazol-2-one; A mixture of 4-fluoro-1 ,2-diaminobenzene (commercially available, 1.0 g, 7.9 mmol), carbonyldiimidazole (1.4 g) and THF (4 ml) was heated to 150 0C in a microwave reactor and stirred for 10 minutes. The mixture was heated to 150 0C and stirred for a further 10 <n="38"/>minutes. The mixture was cooled to room temperature and concentrated under vacuum. The residue was suspended in dilute hydrochloric acid and filtered. The filter-cake was washed with water and cyclohexane then dried under vacuum to give the title compound as a dark grey solid (0.95 g, 78%). 1 H-NMR (400 MHz, DMSO-d6): delta 10.73 (1 H, br s), 10.62 (1 H, br s), 6.87 (1 H, dd, J 8.5, 5 Hz), 6.78-6.70 (2H, m). UPLC-MS: 0.47 min, m/z 153 [M+H]+. |
52% | In tetrahydrofuran; at 20℃; | a) 4-Fluorobenzene-1,2-diamine (2 g, 15.86 mmol) was dissolved in THF (49.4 ml) and 1,1'-Carbonyldiimidazole (2.83 g, 17.44 mmol) was added at RT. The reaction mixture was stirred overnight at RT. To this was added concentrated ammonia solution (1.5 ml) and the mixture stirred for 30 minutes and then diluted with water (100 ml). The resultant solid was collected by filtration, washed with water, followed by Et2O and then dried in vacuo to afford 5-fluoro-1H-benzo[d]imidazol-2(3H)-one (1.250 g, 52%); 1H NMR (400 MHz, DMSO-d6) 6.66-6.79 (2H, m), 6.81-6.94 (1H, m), 10.64 (1H, s), 10.76 (1H, s); m/z: (ES+) MH+, 151.19. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With trichlorophosphate; at 100℃; for 18h; | 10279] A solution of 5-fluoro- 1 ,3-dihydro-2H-benzo[d] imidazol-2-one 2b (1.562 g, 10.3 mmol) in phosphorus oxychloride (14 mE, 154.5 mmol) was heated for 18 hours at 100 C. The reaction mixture was cooled to room temperature and excess of P0C13 was evaporated in vacuo. The residue was neutralized with saturated NaHCO3 solution (10 mE) and extracted with EtOAc (3x20 mE). The organic phase was washed with brine and then dried over Mg504, filtered, and concentrated under reduced pressure to afford 2-chloro-6-fluoro-l H-benzo[d]imidazole 3b (1.552 g, 88%). ?H NMR (400 MHz, DMSO-d5) oe 7.51 (s, 1H), 7.34 (d, J=7.6 Hz, 1H), 7.08 (m, 1H); MS (ESI): mlz 171.0 [M+l] |
Intermediate 14: 2-Chloro-5-fluoro-1 H-benzimidazole; A mixture of 5-fluoro-1 ,3-dihydro-2H-benzimidazol-2-one (Intermediate 15, 0.75 g, 4.1 mmol) and phosphorus oxychloride (2.1 ml) was heated to 110 0C and stirred for 5 hours.The mixture was cooled to room temperature and quenched by addition of ice. The mixture was left to stand 30 minutes, then basified to pH 9 with aqueous ammonium hydroxide solution. The resulting precipitate was filtered off, washed with water and dried under vacuum. The residue was dissolved in ethyl acetate, and filtered. The filtrate was concentrated under vacuum to give the title compound (0.49 g). 1 H-NMR (400 MHz,DMSO-d6): delta 7.52 (1 H, dd, J 9, 5 Hz), 7.35 (1 H, dd, J 9, 2.5 Hz) and 7.08 (1 H, ddd, J 10,9, 2.5 Hz). UPLC-MS: 0.55 min, m/z 171 [M+H]+.(Alternatively, 5-fluoro-2-chloro-1 H-benzimidazole is commercially available) |
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