Ammonium Chloride → HCID 86663264, compound

In an oven-dried 250-mL round bottom flask, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyltrichlorosilane (8.7 g, 15 mmol) was dissolved in anhydrous THF (10 mL). In a separate oven-dried 100-mL round bottom flask, (trimethylsilyl)acetylene (1.7 g, 18 mmol) was dissolved in anhydrous THF (15 mL) and cooled in an ice bath, followed by the dropwise addition of n-butyllithium (6.0 mL, 15 mmol, 2.5 M in hexane). This second solution was stirred for 1 hr, then added to the first solution dropwise over a period of 45 min. The resulting solution was stirred for 5 hr, then cooled in an ice bath. Isopropyllithium (43 mL, 30 mmol, 0.7 M in pentane) was added slowly, then stirring was continued for 12 hr. The reaction mixture was poured into 100 mL of a dilute ammonium chloride solution, then rinsed in with hexane (40 mL). The organic layer was separated, and the aqueous layer was extracted a second time (30 mL hexane). The organic layers were combined, washed with water (3×20 mL), dried over magnesium sulfate, filtered, and concentrated under vacuum to yield the crude product mixture. The product was isolated using chromatography on silica gel with hexane as an eluant (Rf˜0.6 in hexane) and was concentrated to yield a colorless liquid (3.9 g, 6.0 mmol). To remove the trimethylsilyl-endcap, the product was taken up in THF (˜15 mL) and methanol (˜5 mL) and purged vigorously for 15 minutes. Purging was continued after the addition of 4 drops of a 15% aqueous sodium hydroxide solution. The reaction was allowed to stir with continued (but less vigorous) purging for 45 minutes. The mixture was extracted into hexane with the addition of water, washed with 10% hydrochloric acid solution (<5 mL) and water (3×20 mL), dried over magnesium sulfate, filtered, and concentrated under vacuum, to yield the product (3.4 g, 5.9 mmol, 39%) as a colorless liquid. Analysis of the colorless product provided the following data: 1H-NMR (200 MHz, CDCl3) δ=2.4 (s, 1H), 2.2 (m, 2H), 1.0 (m, 14H), 0.8 (m, 2H).

1. customIn a separate oven-dried 100-mL round bottom flask
2. temperaturecooled in an ice bath
3. additionadded to the first solution dropwise over a period of 45 min
4. stirringThe resulting solution was stirred for 5 hr
5. temperaturecooled in an ice bath
6. stirringstirring
7. waitwas continued for 12 hr
8. washrinsed in with hexane (40 mL)
9. customThe organic layer was separated
10. extractionthe aqueous layer was extracted a second time (30 mL hexane)
11. washwashed with water (3×20 mL)
12. dry with materialdried over magnesium sulfate
13. filtrationfiltered
14. concentrationconcentrated under vacuum
15. customto yield the crude product mixture
16. customThe product was isolated
17. concentrationwas concentrated

ORD record

ord-62b6ff2859784d19b0bc078a42b44534

Source dataset

uspto-grants-2014_12

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08920679B2