Chlorotrimethylsilane → 3-TETRAHYDROPYRANYLOXY-1-TRIMETHYLSILYL-1-PROPYNE

Temperature

-20 °C

To a stirred -20° C. solution of 125 g. (0.89 mol.) of 3-tetraydropyranyloxy-1-propyne (Example 1) in 450 ml. of ether, under a nitrogen atmosphere, is added dropwise, over one hour, a solution of 45 ml. (0.89 mol.) of 2.0 N n-butyllithium in hexane. After 150 ml. of dry ether is added and the mixture stirred at -20° C. for 30 minutes, a solution of 98 g. (0.89 mol.) of trimethylchlorosilane in 73 ml. of ether is added dropwise, stirring is continued for 30 minutes at -20° C., and at ambient temperature for 18 hours. The reaction mixture is again cooled to -20° C., and a solution of 90 ml. of acetic acid in 300 ml. of ether is added dropwise, followed by 90 ml. of water. It is then diluted with 500 ml. of water, and extracted 3 times with 300 ml. of a 5% sodium bicarbonate solution. The organic phase is separated, washed with 500 ml. of a saturated brine solution, dried over sodium sulfate, and evaporated at 40° C. under vacuum (12 mm.). The crude product is fractionally distilled, b.p. 120°-125° C. (18 mm.), to yield 120 g. of an oil.

1. customTo a stirred -20° C.
2. stirringstirring
3. waitis continued for 30 minutes at -20° C.
4. waitat ambient temperature for 18 hours
5. temperatureThe reaction mixture is again cooled to -20° C.
6. additionIt is then diluted with 500 ml
7. extractionof water, and extracted 3 times with 300 ml
8. customThe organic phase is separated
9. washwashed with 500 ml
10. dry with materialof a saturated brine solution, dried over sodium sulfate
11. customevaporated at 40° C. under vacuum (12 mm.)
12. distillationThe crude product is fractionally distilled
13. customb.p. 120°-125° C. (18 mm.), to yield 120 g

ORD record

ord-bf9616a659f84efcb2a6debfaae36c9a

Source dataset

uspto-grants-1980_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04219664