Trimethylsilylacetylene → HCID 53930074, compound

Temperature

-20 °C

n-Butyllithium (18.5 ml, 1.6M in hexane) was added dropwise with stirring under nitrogen, to a solution of trimethylsilylacetylene (4.2 ml) in dry tetrahydrofuran (60 ml) whilst maintaining the temperature below -60° C. After a further thirty minutes, the mixture was treated, dropwise with stirring at<-60° C. with a solution of 1-trityl-1,2,4-triazole 3-carboxaldehyde (10.0 g, prepared as described in Example 3) in dry dichloromethane (30 ml). After a further fifteen minutes at -60° C., the mixture was allowed to warm to -20° C. over thirty minutes, then quenched into a mixture of saturated ammonium chloride solution (100 ml) and ethyl acetate (200 ml). The organic layer was washed with water (50 ml) and brine (100 ml), dried over magnesium sulphate, and evaporated under reduced pressure to give crude 1-trimethylsilyl-3(1-trityl-1,2,4-triazol-3-yl)-prop-1-yn-3-ol as a brown oil. A solution of this material and potassium fluoride (3.5 g) in methanol (200 ml) was allowed to stand at room temperature for eighteen hours, evaporated under reduced pressure and the residue partitioned between dichloromethane (200 ml) and brine (100 ml). The organic layer was dried over magnesium sulphate, evaporated under reduced pressure and the residue chromatographed on silica, using dichloromethane-ether (3:1) as eluant, to give 3(1-trityl-1,2,4-triazol-3-yl)prop-1-yn-3-ol (5.9 g, m.p. 138°-139° C.). NMR (CDCl3): δ2.59(1H,d), 4.35(1H,d), 5.68(1H,dd), 7.1-7.4(15H,m), 7.95(1H,s).

1. temperaturewhilst maintaining the temperature below -60° C
2. waitAfter a further thirty minutes
3. additionthe mixture was treated
4. waitAfter a further fifteen minutes at -60° C.
5. customquenched into a mixture of saturated ammonium chloride solution (100 ml) and ethyl acetate (200 ml)
6. washThe organic layer was washed with water (50 ml) and brine (100 ml)
7. dry with materialdried over magnesium sulphate
8. customevaporated under reduced pressure
9. customto give crude 1-trimethylsilyl-3(1-trityl-1,2,4-triazol-3-yl)-prop-1-yn-3-ol as a brown oil
10. waitto stand at room temperature for eighteen hours
11. customevaporated under reduced pressure
12. customthe residue partitioned between dichloromethane (200 ml) and brine (100 ml)
13. dry with materialThe organic layer was dried over magnesium sulphate
14. customevaporated under reduced pressure
15. customthe residue chromatographed on silica

ORD record

ord-b3f194a1830243bdbdd162ec565dcb52

Source dataset

uspto-grants-1995_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05393732