Diethyl Ether → 4-(Trimethylsilyl)but-3-yn-2-ol

A solution of 107.1 parts by weight of 3-butyne-2-ol (I) in 1000 parts by volume of dry ethyl ether is chilled to -50° C. (internal temperature) and 1390 parts by volume of 2.17 M n-butyl lithium in hexane is added over a 2 hour period. The internal temperature is allowed to reach 10° C. during the latter part of the addition to facilitate stirring. The mixture is then cooled again to -30° C. (internal) and 400 parts by volume of chlorotrimethylsilane in 200 parts by volume of ethyl ether is added over a 15 minute period. The mixture is allowed to warm slowly to room temperature overnight. After a brief period of reflux the mixture is again cooled to 25° C. and 100 parts by volume of water is added causing the internal temperature to rise to 37° C. After stirring for 1 hour, more water is added. The organic layer is separated and washed with 5% aqueous hydrochloric acid and water. The solution is dried over sodium sulfate, then concentrated to approximately 400 parts by volume. After adding 500 parts per volume of methanol and 200 parts per volume of 5% hydrochloric acid the solution is stirred at room temperature for one hour then diluted with 1000 parts per volume of water and extracted with ether. The ether extract is washed with water, dried over sodium sulfate and concentrated to afford 4-(trimethylsilyl)-3-butyn-2-ol (II) which distills at 49°-50° C./0.25 mm and has the following structural formula ##STR8##

1. additionis added over a 2 hour period
2. additionto reach 10° C. during the latter part of the addition
3. additionis added over a 15 minute period
4. temperatureAfter a brief period of reflux the mixture
5. temperatureis again cooled to 25° C.
6. customto rise to 37° C
7. stirringAfter stirring for 1 hour
8. customThe organic layer is separated
9. washwashed with 5% aqueous hydrochloric acid and water
10. dry with materialThe solution is dried over sodium sulfate
11. concentrationconcentrated to approximately 400 parts by volume
12. additionAfter adding 500 parts per volume of methanol and 200 parts per volume of 5% hydrochloric acid the solution
13. stirringis stirred at room temperature for one hour
14. additionthen diluted with 1000 parts per volume of water
15. extractionextracted with ether
16. extractionThe ether extract
17. washis washed with water
18. dry with materialdried over sodium sulfate
19. concentrationconcentrated

ORD 기록

ord-3bad084721b24cf9ba14366933282212

출처 데이터셋

uspto-grants-1979_07

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US04161480