Sulfuric Acid → HCID 11450791, compound

Temperature

0 °C

Under N2-atmosphere, methyl tert-butyl ether (MTBE, 80 mL) was added to lithium aluminum hydride (0.67 g, 17.60 mmol) and the suspension was stirred under cooling with an ice-water bath (0° C.). A solution of 2,2,16,16-tetramethyl-9-oxoheptadecanedioic acid diethyl ester (3.0 g, 7.04 mmol) in MTBE (20 mL) was added dropwise, followed by additional MTBE (40 mL). After 2 h at 0° C., the reaction mixture was carefully quenched by addition of ethyl acetate (8 mL, 80 mmol) and allowed to warm to room temperature overnight. The mixture was cooled with an ice-water bath and carefully hydrolyzed by addition of crushed ice (15 g) and water (15 mL). The pH was adjusted to 1 by addition of 2 N sulfuric acid (28 mL) and the solution was stirred at room temperature for 15 min. The layers were separated and the aqueous layer was extracted with MTBE (40 mL). The combined organic layers were washed with deionized water (50 mL), saturated NaHCO3 solution (40 mL), brine (40 mL), dried over MgSO4, concentrated in vacuo and dried in high vacuo to yield a crude product (2.65 g). The crude product was purified by recrystallization from hot CH2Cl2 (20 mL), which was cooled to room temperature and then kept at −5° C. The crystals were filtered, washed with ice-cold CH2Cl2 (20 mL) and dried in high vacuo. This process was repeated to furnish 2,2,16,16-tetramethylheptadecane-1,9,17-triol (1.59 g, 65%) as a white solid. Mp 75-77° C. 1H NMR (300 MHz, CDCl3/TMS): δ (ppm): 3.57 (m, 1H), 3.30 (s, 4H), 1.72 (br, 2H), 1.50-1.16 (m, 25H), 0.85 (s, 12H). 13C NMR (75 MHz, CDCl3/TMS): δ (ppm): 72.09, 38.79, 37.61, 35.21, 30.70, 29.85, 25.78, 24.06, 23.92. HRMS (LSIMS, gly): Calcd for C21H45O3 (MH+): 345.3369. found: 345.3364. HPLC: 95% pure.

1. temperatureto warm to room temperature overnight
2. temperatureThe mixture was cooled with an ice-water bath
3. stirringthe solution was stirred at room temperature for 15 min
4. customThe layers were separated
5. extractionthe aqueous layer was extracted with MTBE (40 mL)
6. washThe combined organic layers were washed with deionized water (50 mL), saturated NaHCO3 solution (40 mL), brine (40 mL)
7. dry with materialdried over MgSO4
8. concentrationconcentrated in vacuo
9. customdried in high vacuo
10. customto yield a crude product (2.65 g)
11. customThe crude product was purified by recrystallization from hot CH2Cl2 (20 mL), which
12. temperaturewas cooled to room temperature
13. customkept at −5° C
14. filtrationThe crystals were filtered
15. washwashed with ice-cold CH2Cl2 (20 mL)
16. customdried in high vacuo

ORD record

ord-612da127f3094cfaa3a9b5ceeafa1ce9

Source dataset

uspto-grants-2015_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09000041B2