Benzene → trans-5-phenyl-2,3,4,4a,5,9b-hexahydro-1H-pyrido[4,3-b]indole

A solution of ethyl chloroformate (22 g., 0.2 mole) in 100 ml. dry benzene was added to a solution of (±)-trans-2-cyclopropylmethyl-2,3,4,4a,5,9b-hexahydro-5-phenyl-1H-pyrido[4,3-b]indole (16 g. crude material, prepared as described above, 0.047 moles in theory) in 400 ml. anhydrous benzene with stirring. The resulting mixture was refluxed for three hours. As the mixture was refluxing, a whitish solid precipitated. After refluxing, the mixture was cooled and filtered to remove the precipitate, then the filtrate was evaporated to dryness under vacuum, yielding a yellow oil. This oil was dissolved in 400 ml. n-butanol, 40 g. of KOH pellets were added, and the resulting mixture was refluxed with stirring for one hour. After refluxing, the mixture was cooled, and concentrated under vacuum. Water and toluene were added and the mixture was placed in a separatory funnel. The toluene layer was removed and washed with water until the waste water was neutral to litmus. The toluene layer was then extracted four times with 125 ml. of 1 molar tartaric acid. The combined extracts were then washed once with ether, made basic by addition of 50% aqueous NaOH, cooled, and extracted two times with 75 ml. CHCl3. The CHCl3 extract was washed with water until the wash water was neutral to litmus, dried with K2CO3, filtered, and evaporated to dryness under vacuum, yielding 9.7 g. of an oil. This was left in a refrigerator overnight, then was triturated with hexane, yielding a solid. Recrystallization from hexane yielded 4.9 g. of the title compound, m.p. 94°-94.7° C.

1. temperatureThe resulting mixture was refluxed for three hours
2. temperatureAs the mixture was refluxing
3. customa whitish solid precipitated
4. temperatureAfter refluxing
5. temperaturethe mixture was cooled
6. filtrationfiltered
7. customto remove the precipitate
8. customthe filtrate was evaporated to dryness under vacuum
9. customyielding a yellow oil
10. dissolutionThis oil was dissolved in 400 ml
11. temperaturethe resulting mixture was refluxed
12. temperatureAfter refluxing
13. temperaturethe mixture was cooled
14. concentrationconcentrated under vacuum
15. additionWater and toluene were added
16. customthe mixture was placed in a separatory funnel
17. customThe toluene layer was removed
18. washwashed with water until the waste water
19. extractionThe toluene layer was then extracted four times with 125 ml
20. washThe combined extracts were then washed once with ether
21. additionmade basic by addition of 50% aqueous NaOH
22. temperaturecooled
23. extractionextracted two times with 75 ml
24. extractionThe CHCl3 extract
25. washwas washed with water until the wash water
26. dry with materialdried with K2CO3
27. filtrationfiltered
28. customevaporated to dryness under vacuum
29. customyielding 9.7 g
30. waitThis was left in a refrigerator overnight
31. customwas triturated with hexane
32. customyielding a solid
33. customRecrystallization from hexane
34. customyielded 4.9 g

ORD 기록

ord-b30999b7a49242f8a586f395b5568120

출처 데이터셋

uspto-grants-1979_11

DOI

10.6084/m9.figshare.5104873.v1

특허 번호

US04174453