Methane → Sarsagenin

HRID 1438957Notes

Reaction equation

HRID 1438957 reaction equation
[CH3:1][C@@H:2]1[CH2:73][O:72][C@@:5]2([O:9][C@H:8]3[CH2:10][C@H:11]4[C@@H:16]5[CH2:17][CH2:18][C@@H:19]6[CH2:24][C@@H:23]([O:25][C@@H]7O[C@H](CO[C@@H]8O[C@H](CO)[C@@H](O)[C@H](O)[C@H]8O)[C@@H](O[C@@H]8O[C@@H](C)[C@H](O)[C@@H](O)[C@H]8O)[C@H](O)[C@H]7O[C@@H]7O[C@H](CO)[C@@H](O)[C@H](O)[C@H]7O)[CH2:22][CH2:21][C@:20]6([CH3:69])[C@H:15]5[CH2:14][CH2:13][C@:12]4([CH3:70])[C@H:7]3[C@@H:6]2[CH3:71])[CH2:4][CH2:3]1.C(O)(C)C.Cl.C>O.C1(C)C=CC=CC=1.CCCCCC>[CH3:1][C@@H:2]1[CH2:73][O:72][C@@:5]2([O:9][C@H:8]3[CH2:10][C@H:11]4[C@@H:16]5[CH2:17][CH2:18][C@@H:19]6[CH2:24][C@@H:23]([OH:25])[CH2:22][CH2:21][C@:20]6([CH3:69])[C@H:15]5[CH2:14][CH2:13][C@:12]4([CH3:70])[C@H:7]3[C@@H:6]2[CH3:71])[CH2:4][CH2:3]1

Participants

8

Reactant 4

HCID 297MethaneHCID 313Hydrochloric Acid2×HCID 3776IsopropanolHCID 19797719057-61-5

Product 1

HCID 92095SarsageninYield 89%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent3×HCID 1140TolueneSolventHCID 8058HexaneSolvent

Procedure

A mixture of 1004 parts of crude sarsasaponin, 1560 parts of isopropanol, 225 parts of water and 298 parts of concentrated hydrochloric acid is heated at reflux for 2 hours. Then, an additional 166 parts of concentrated hydrochloric acid dissolved in 400 parts of water is added and refluxing continued for a further 1.5 hour. The reaction mixture is diluted to 12,000 parts by volume with water and ice and the resulting precipitate collected, washed with water and air-dried to afford crude sarsasapogenin in an 89% yield. This crude material is dissolved in toluene with warming, treated with 190 parts of alumina, 45 parts of charcoal, and filtered hot. The toluene solution is then cooled to room temperature and refiltered. The toluene is removed in vacuo to leave a volume of about 1,000 parts. This solution is diluted with n-hexane to about 3,500 parts by volume causing the separation of a dark precipitate. The solution is filtered, treated with charcoal, warmed to about 60° C., and filtered through diatomaceous earth under vacuum. Cooling affords crystals which are separated, washed successively with 1,500 parts by volume of the mother liquors and 1,000 parts of n-hexane and dried in a steam oven. Recrystallization from a mixture of acetone and n-hexane affords sarsasapogenin, identical to the product of Example 1.

Workup

  1. temperatureis heated
  2. temperatureat reflux for 2 hours
  3. additionis added
  4. temperaturerefluxing
  5. customthe resulting precipitate collected
  6. washwashed with water
  7. customair-dried
  8. customto afford crude sarsasapogenin in an 89% yield
  9. temperaturewith warming
  10. filtrationfiltered hot
  11. customThe toluene is removed in vacuo
  12. customto leave a volume of about 1,000 parts
  13. customthe separation of a dark precipitate
  14. filtrationThe solution is filtered
  15. additiontreated with charcoal
  16. temperaturewarmed to about 60° C.
  17. filtrationfiltered through diatomaceous earth under vacuum
  18. temperatureCooling
  19. customaffords crystals which
  20. customare separated
  21. washwashed successively with 1,500 parts by volume of the mother liquors and 1,000 parts of n-hexane
  22. customdried in a steam oven
  23. customRecrystallization
  24. additionfrom a mixture of acetone and n-hexane

Sources & evidence

ORD record
ord-d861ae7b18d446b8b607efda1a93ac85
Source dataset
uspto-grants-1977_11
Patent number
US04057543

Reaction notes

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