Hydrochloric Acid → HCID 67119193, compound

After an aqueous solution (7.5 ml) of sodium chlorite (1.28 g, 14.2 mmol) and sodium dihydrogenphosphate monohydrate (1.28 g, 9.28 mmol) was added dropwise to a solution of methyl (4′-([3-(allyloxy)-2-formyl-4-(trifluoromethyl)benzyl]oxy)-1,1′-biphenyl-4-yl)acetate (1.71 g, 3.53 mmol) obtained in Example (6-8) in a mixture of tert-butyl alcohol (15 ml), 1,4-dioxane (3.5 ml) and 2-methyl-2-butene (4.5 ml), the mixture was stirred at room temperature for 4 hours. After a 5% aqueous sodium thiosulfate solution was added to the reaction mixture, the mixture was poured into 0.5N hydrochloric acid and extracted with ethyl acetate (twice). The organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The solvent was removed under reduced pressure to give a residue. After the obtained residue was dissolved in toluene (12 ml), N,N-dimethylformamide di-tert-butyl acetal (3.39 ml, 14.1 mmol) was added thereto and the mixture was heated under reflux for 4 hours. After the reaction mixture was poured into water and the mixture was extracted with ethyl acetate (three times), the organic layer was successively washed with water (twice) and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. Pyrrolidine (0.500 ml, 5.99 mmol) and tetrakis(triphenylphosphine)palladium (81.6 mg, 70.6 mmol) were added to a solution of the residue obtained by removing the solvent under reduced pressure in a mixture of 1,4-dioxane-water (30:1, 12 ml), and the mixture was stirred at room temperature for 4 hours. After water was poured into the reaction mixture and the mixture was extracted with ethyl acetate, the organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The mixture was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=98/2-85/15) to give the title compound as a pale yellow powder (1.08 g, yield: 59%).

1. extractionextracted with ethyl acetate (twice)
2. washThe organic layer was successively washed with water
3. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
4. customThe solvent was removed under reduced pressure
5. customto give a residue
6. temperaturethe mixture was heated
7. temperatureunder reflux for 4 hours
8. extractionthe mixture was extracted with ethyl acetate (three times)
9. washthe organic layer was successively washed with water (twice) and a saturated aqueous NaCl solution
10. dry with materialdried with anhydrous sodium sulfate
11. customobtained
12. customby removing the solvent under reduced pressure
13. additionin a mixture of 1,4-dioxane-water (30:1, 12 ml)
14. stirringthe mixture was stirred at room temperature for 4 hours
15. additionAfter water was poured into the reaction mixture
16. extractionthe mixture was extracted with ethyl acetate
17. washthe organic layer was successively washed with water
18. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
19. customThe mixture was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=98/2-85/15)

ORD record

ord-6e1b329a31a74692acf0bc37c7033266

Source dataset

uspto-grants-2011_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07923573B2