Potassium Permanganate → Phosphoric acid, bis(1,1-dimethylethyl) ester

A solution of di-tert-butyl phosphite (175 g), potassium bicarbonate (54.2 g), and deionized water (788 mL) was cooled to 0° C. Potassium permanganate (99.7 g) was divided into three equal portions of 33.2 g and each portion was added over one hour. During the addition, the maximum temperature observed was 21.6° C. Once the addition was complete, the reaction was allowed to warm to room temperature and was stirred for thirty minutes. Decolorizing carbon (13.4 g) was added and the reaction was heated to 60° C. for fifteen minutes. The suspension was filtered (very slowly) and washed with deionized water (250 mL). The filtrate was again heated to 60° C. with decolorizing carbon (22.4 g) for 20 min. The suspension was filtered and the filter cake was washed with deionized water (250 mL). The filtrate was cooled to 0° C. in an ice/water bath. The pH of the solution was 8-9. Concentrated HCl (157.2 mL) was added to acidify the solution to pH=1. A white precipitate immediately formed. The slurry was continued to stir at 0° C. for ten minutes. The white solid was filtered and washed with cold deionized water (219 mL). The filter cake was dissolved in chloroform (500 mL) and was dried over sodium sulfate. The dried solution was filtered, washed with chloroform, and concentrated in vacuo to afford a white solid (87.4 g, 46.2% yield). NMR analysis indicated pure product. 1H NMR (300 MHz): δ 1.45 (s, 18H); 31P NMR (121 MHz): δ −604.30.

1. additioneach portion was added over one hour
2. additionDuring the addition
3. customobserved was 21.6° C
4. additionOnce the addition
5. additionDecolorizing carbon (13.4 g) was added
6. temperaturethe reaction was heated to 60° C. for fifteen minutes
7. filtrationThe suspension was filtered (very slowly) and
8. washwashed with deionized water (250 mL)
9. temperatureThe filtrate was again heated to 60° C. with decolorizing carbon (22.4 g) for 20 min
10. filtrationThe suspension was filtered
11. washthe filter cake was washed with deionized water (250 mL)
12. temperatureThe filtrate was cooled to 0° C. in an ice/water bath
13. additionConcentrated HCl (157.2 mL) was added
14. customA white precipitate immediately formed
15. stirringto stir at 0° C. for ten minutes
16. filtrationThe white solid was filtered
17. washwashed with cold deionized water (219 mL)
18. dissolutionThe filter cake was dissolved in chloroform (500 mL)
19. dry with materialwas dried over sodium sulfate
20. filtrationThe dried solution was filtered
21. washwashed with chloroform
22. concentrationconcentrated in vacuo

ORD record

ord-41a04136629a4127a3e67735b6658c5c

Source dataset

uspto-grants-2014_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08735376B2