Hydrochloric Acid → 6,6,7,7,7-Pentafluoroheptan-1-ol

温度

60 °C

A solution of potassium hydroxide (370 g, 6.6 mol) in water (500 ml) was added to a solution of diethyl 2-(4,4,5,5,5-pentafluoropentyl)malonate (105.3 g, 0.33 mol) in ethanol (1000 ml), followed by stirring for 16 hours at 60° C. The reaction mixture was adjusted to pH 5 by slowly adding 1N hydrochloric acid dropwise, and then extracted twice with ethyl acetate. The combined organic layers were washed with saturated aqueous sodium chloride and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was dissolved in dimethyl sulfoxide (500 ml) and stirred for 18 hours at 170° C. Water was added to the reaction mixture, which was then extracted three times with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was dissolved in anhydrous tetrahydrofuran (300 ml) and cooled to −30° C. Borane-methyl sulfide complex (10 M in THF, 55 ml, 0.55 mol) was slowly added dropwise to the solution, followed by stirring for 3 hours at room temperature. After treatment with methanol at 0° C., water was added to the reaction mixture, which was then extracted twice with ethyl acetate. The combined organic layers were washed with water and saturated aqueous sodium chloride, and then dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/20) to give 6,6,7,7,7-pentafluoroheptan-1-ol (39 g, Yield 57%).

1. extractionextracted twice with ethyl acetate
2. washThe combined organic layers were washed with saturated aqueous sodium chloride
3. dry with materialdried over anhydrous magnesium sulfate
4. distillationAfter distilling off the solvent
5. dissolutionthe residue was dissolved in dimethyl sulfoxide (500 ml)
6. stirringstirred for 18 hours at 170° C
7. additionWater was added to the reaction mixture, which
8. extractionwas then extracted three times with ethyl acetate
9. washThe combined organic layers were washed with water and saturated aqueous sodium chloride
10. dry with materialdried over anhydrous magnesium sulfate
11. distillationAfter distilling off the solvent
12. dissolutionthe residue was dissolved in anhydrous tetrahydrofuran (300 ml)
13. temperaturecooled to −30° C
14. stirringby stirring for 3 hours at room temperature
15. extractionwas then extracted twice with ethyl acetate
16. washThe combined organic layers were washed with water and saturated aqueous sodium chloride
17. dry with materialdried over anhydrous magnesium sulfate
18. distillationAfter distilling off the solvent
19. customthe residue was purified by silica gel column chromatography (eluent: ethyl acetate/hexane=1/20)

ORDレコード

ord-8cdf7318f62a4be0bee0f18c02005795

出典データセット

uspto-grants-2003_04

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US06552068B1