Methanol → HCID 10480216, compound

HRID 1742840Notes

Reaction equation

HRID 1742840 reaction equation
[CH3:1][C:2]([OH:29])([C:4]#[C:5][CH2:6][C@H:7]([C:9]1[C@:26]2([CH3:27])[C@H:12]([C:13]3[C@H:23]([CH2:24][CH2:25]2)[C@:21]2([CH3:22])[C:16]([CH2:17][C@@H:18]([OH:28])[CH2:19][CH2:20]2)=[CH:15][CH:14]=3)[CH2:11][CH:10]=1)[CH3:8])[CH3:3].[C:30](OC(=O)C)(=[O:32])[CH3:31].C(N([CH2:42][CH3:43])CC)C.C[OH:45]>ClCCl.CN(C)C1C=CN=CC=1>[C:30]([O:28][C@H:18]1[CH2:19][CH2:20][C@@:21]2([CH3:22])[C:16](=[CH:15][CH:14]=[C:13]3[C@@H:23]2[CH2:24][CH2:25][C@@:26]2([CH3:27])[C@H:12]3[CH2:11][CH:10]=[C:9]2[C@H:7]([CH3:8])[CH2:6][C:5]#[C:4][C:2]([O:29][C:42](=[O:45])[CH3:43])([CH3:3])[CH3:1])[CH2:17]1)(=[O:32])[CH3:31]

Participants

7

Reactant 4

HCID 887MethanolHCID 7918Acetic AnhydrideHCID 8471TriethylamineHCID 10340621(3beta)-Cholesta-5,7,16-trien-23-yne-3,25-diol

Product 1

HCID 10480216HCID 10480216, compoundYield 89.8%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Conditions

Temperature
2 °C

Procedure

To a cold suspension of 75.3 g (191 mmol) (3β)-cholesta-5,7,16-trien-23-yne-3,25-diol in 450 mL of dichloromethane was added 107 mL (1.14 mol) acetic anhydride and 160 mL (1.14 mol) triethylamine. After the suspension was cooled to 2° C., 4.6 g (38 mmol) 4-dimethylaminopyridine was added. After 10 min, the cold bath was removed and the mixture was stirred at room temperature overnight. After cooling again with an ice-water bath, 30.7 mL (758 mmol) methanol was added, and the mixture was stirred at room temperature for 1.5 hr. The mixture was washed with water and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed with 200 mL 1N HCl, and the aqueous layer was extracted with dichloromethane. The combined organic layers were washed with saturated aqueous NaHCO3, dried over Na2SO4, and concentrated to dryness. The residue was dissolved in 700 mL of warm 95 % methanol. After a seed crystal was added, the suspension was stored in a refrigerator overnight. The precipitate was filtered and washed with 700 mL of cold 90% methanol. After being dried under high vacuum, 82.05 g (89.8%) of (3β)-cholesta-5,7,16-trien-23-yne-3,25-diol diacetate was obtained as a white solid: mp 98°-101° C. Anal Calcd for C31H42O4 : C, 77.79; H, 8.84. Found C, 77.74; H, 8.88.

Workup

  1. customthe cold bath was removed
  2. temperatureAfter cooling again with an ice-water bath
  3. stirringthe mixture was stirred at room temperature for 1.5 hr
  4. washThe mixture was washed with water
  5. extractionthe aqueous layer was extracted with dichloromethane
  6. washThe combined organic layers were washed with 200 mL 1N HCl
  7. extractionthe aqueous layer was extracted with dichloromethane
  8. washThe combined organic layers were washed with saturated aqueous NaHCO3
  9. dry with materialdried over Na2SO4
  10. concentrationconcentrated to dryness
  11. dissolutionThe residue was dissolved in 700 mL of warm 95 % methanol
  12. additionAfter a seed crystal was added
  13. customwas stored in a refrigerator overnight
  14. filtrationThe precipitate was filtered
  15. washwashed with 700 mL of cold 90% methanol
  16. customAfter being dried under high vacuum

Sources & evidence

ORD record
ord-1fcecac6ffb745fa8a1d0091884b02e4
Source dataset
uspto-grants-1994_08
Patent number
US05342833

Reaction notes

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