反应详情

To a 250 mL rb flask containing MeOH (50 mL) was added 4-bromo-1-(3-chloro-2-methylbenzyl)-2-(difluoromethyl)-6-nitro-1H-benzo[d]imidazole (4.0 g, 9.29 mmol), tin(II) chloride dihydrate (12.58 g, 55.7 mmol) and concentrated hydrochloric acid (6.97 ml, 84 mmol). The resultant suspension was heated to 50° C. and monitored by LC/MS. By LC/MS the reaction was complete in 45 minutes. After the reaction had cooled to room temperature and was filtered to remove insoluble tin salts, 6N NaOH (0.8 ml, 4.00 mmol) was added to adjust the pH to about 11 and the mixture was concentrated to remove any MeOH. The sticky mixture was extracted with EtOAC; however, because it was difficult to extract from the tin-salt containing aqueous the entire mixture of two phases was filtered then the layers were separated. The organic was dried over MgSO4 and concentrated in vacuo to provide and the organic was washed with H2O and brine and dried over MgSO4 and filtered. The solvent was removed in-vacuo leaving light brown solid 4-bromo-1-(3-chloro-2-methylbenzyl)-2-(difluoromethyl)-1H-benzo[d]imidazol-6-amine (2.25 g, 5.62 mmol, 60.5% yield) as crude material. LC/MS: MS (ES+) m/e 402.4 [M+H]+; 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.33 (d, J=7.83 Hz, 1H), 6.80-7.13 (m, 3H), 6.33 (d, J=7.83 Hz, 1H), 6.25 (d, J=2.02 Hz, 1H), 5.46 (s, 2H), 3.81 (s, 2H), 2.49 (s, 3H)

1. filtrationwas filtered
2. additionwas added
3. concentrationthe mixture was concentrated
4. customto remove any MeOH
5. extractionThe sticky mixture was extracted with EtOAC
6. extractionto extract from the tin-salt containing aqueous
7. additionthe entire mixture of two phases
8. filtrationwas filtered
9. customthe layers were separated
10. dry with materialThe organic was dried over MgSO4
11. concentrationconcentrated in vacuo
12. customto provide
13. washthe organic was washed with H2O and brine
14. dry with materialdried over MgSO4
15. filtrationfiltered
16. customThe solvent was removed in-vacuo