Sodium Hydroxide → HCID 25179063, compound

To a 3-necked, 500 mL round bottomed flask equipped with an overhead stirrer, digital thermometer and a 125 mL constant-pressure addition funnel with a nitrogen inlet was added 27 mL (0.27 mol) of borane-dimethylsulfide complex (10.0M in THF). The addition funnel was charged with a solution of 50 g (0.23 mol) of 1,1,1-trifluoro-2-trifluoromethyl-4-methyl-pent-4-en-2-ol (1) in 140 mL of anhydrous THF. The flask was cooled and the olefin was added slowly with stirring while maintaining a temperature below 15° C. The mixture was stirred at room temperature overnight after which time it was recooled and 100 mL (0.3 mol) of 3M NaOH (aq) was added carefully. The reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether. The resulting heavy oil was taken up in 50 mL of THF and the solution transferred to a 250 mL 3-necked round bottomed flask equipped with a 125-mL addition funnel, a digital thermometer, and a magnetic stirbar. The addition funnel was charged with 70 mL of 30% hydrogen peroxide. The flask was cooled and the hydrogen peroxide added slowly with stirring. After stirring overnight at room temperature, the solution was diluted with 500 mL of diethyl ether and adjusted to pH 6 (wet litmus) with 5% HCl. The ether layer was separated and the aqueous layer was extracted with 2×250 mL of ether. The combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine, dried over MgSO4, and evaporated to a yellow oil. The oil was purified by distillation through a Vigreux column, bp 57° [email protected] mm Hg to yield 46 g (85%) of (2) as a low melting solid. The identity of the product was confirmed using 1H NMR spectroscopy and HRMS.

1. customTo a 3-necked, 500 mL round bottomed flask equipped with an overhead stirrer
2. additiondigital thermometer and a 125 mL constant-pressure addition funnel with a nitrogen inlet
3. temperatureThe flask was cooled
4. temperaturewhile maintaining a temperature below 15° C
5. stirringThe mixture was stirred at room temperature overnight after which time it
6. customThe reaction mixture was reduced in volume on a rotary evaporator and subsequently co-evaporated with two 500 mL portions of diethyl ether
7. customthe solution transferred to a 250 mL 3-necked round bottomed flask
8. customequipped with a 125-mL addition funnel
9. additionThe addition funnel was charged with 70 mL of 30% hydrogen peroxide
10. temperatureThe flask was cooled
11. additionthe hydrogen peroxide added slowly
12. stirringwith stirring
13. stirringAfter stirring overnight at room temperature
14. additionthe solution was diluted with 500 mL of diethyl ether
15. customThe ether layer was separated
16. extractionthe aqueous layer was extracted with 2×250 mL of ether
17. washThe combined organic phases were washed with 2×500 mL of saturated ammonium chloride and brine
18. dry with materialdried over MgSO4
19. customevaporated to a yellow oil
20. distillationThe oil was purified by distillation through a Vigreux column, bp 57° C.

ORD record

ord-57518296d3d74b2fa6eeab3846281bb5

Source dataset

uspto-grants-2008_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07442828B2