Phosphoric Acid → ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-hydroxyethyl)amino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate

温度

100 °C

To a sealable vial was added ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate (0.156 g, 0.278 mmol), ethylene bromohydrin (0.059 mL, 0.833 mmol), potassium iodide (0.138 g, 0.833 mmol), and phosphoric acid, potassium salt (0.295 g, 1.388 mmol). The mixture was diluted with acetonitrile (2 mL), was flushed with nitrogen, then was sealed and heated to 100° C. After 15 h of heating, the mixture was cooled to rt. LC/MS still showed starting material present, so an additional 0.059 mL of ethylene bromohydrin was added, the mixture was diluted with 1 mL of acetonitrile, and it was sealed and heated to 120° C. After heating the mixture for an additional 20 h, it was cooled to rt, and diluted with 10 mL of water. The solids that formed were collected by filtration and were washed with water to give ethyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-((2-hydroxyethyl)amino)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)cyclohex-3-enecarboxylate (0.145 g, 0.239 mmol, 86% yield) as an off-white solid. LCMS: m/e 606.7 (M+H)+, 2.18 min (method 1).

1. customwas flushed with nitrogen
2. customwas sealed
3. temperatureAfter 15 h of heating
4. temperaturethe mixture was cooled to rt
5. additionso an additional 0.059 mL of ethylene bromohydrin was added
6. additionthe mixture was diluted with 1 mL of acetonitrile, and it
7. customwas sealed
8. temperatureheated to 120° C
9. temperatureAfter heating the mixture for an additional 20 h
10. temperatureit was cooled to rt
11. additiondiluted with 10 mL of water
12. customThe solids that formed
13. filtrationwere collected by filtration
14. washwere washed with water

ORDレコード

ord-835d9c578bc84153a9278ae6d2521a79

出典データセット

uspto-grants-2014_12

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US08906889B2