Acetyl chloride → HCID 15157280, compound

HRID 2051434Notes

Reaction equation

HRID 2051434 reaction equation
[OH:1][C:2]1[C:3]([CH:18]([CH3:21])[CH:19]=[CH2:20])=[CH:4][C:5]([CH3:17])=[C:6]2[C:14]=1C(NC)C1[CH:7]2[CH2:8][CH2:9][CH2:10][CH2:11]1.[CH2:22]([N:24]([CH2:27][CH3:28])[CH2:25][CH3:26])C.C(Cl)(=[O:31])C>C(Cl)(Cl)Cl>[OH:1][C:2]1[C:3]([CH:18]([CH3:21])[CH:19]=[CH2:20])=[CH:4][C:5]([CH3:17])=[C:6]2[C:14]=1[CH:25]([N:24]([CH3:22])[C:27](=[O:31])[CH3:28])[CH:26]1[CH:7]2[CH2:8][CH2:9][CH2:10][CH2:11]1

Participants

5

Reactant 3

HCID 6367Acetyl chlorideHCID 8471TriethylamineHCID 15157264HCID 15157264, compound

Product 1

HCID 15157280HCID 15157280, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

25.00 Grams of 8-hydroxy-5-methyl-9-methylamino-7-(1-methyl-2-propenyl)-1,2,3,4,4a,9a-hexahydrofluorene was dissolved in 250 ml of chloroform. Under ice-cooling and stirring, to the solution were added 24.4 ml of triethylamine and then 14.95 ml of acetyl chloride, followed by stirring at room temperature for 1 hour. Extraction was carried out with addition of water and the organic layer was concentrated. The resulting residue was dissolved in 250 ml of methanol and thereto was added an aqueous solution containing 1.36 g of sodium bicarbonate in 50 ml of water, followed by refluxing for 2 hours. The reaction mixture was rendered weakly acidic with addition of dilute hydrochloric acid and extracted with chloroform. The organic layer was dried with magnesium sulfate, filtered and concentrated. The resulting residue was purified by a silica gel column chromatography (eluent: chloroform:methanol:ethyl acetate=100:1:5). The component of Rf value 0.29 in the eluate was recrystallized from ethanol to obtain 1.66 g of 8-hydroxy-5-methyl-9-(N-methyl-N-acetylamino)-7-(1-methyl-2-propenyl)-1,2,3,4,4a,9a-hexahydrofluorene (diastereomer B) having a melting point of 143°-145° C. and of colorless powdery crystal and the component of Rf value 0.21 was recrystallized from ethanol to obtain 16.43 g of 8-hydroxy-5-methyl-9-(N-methyl-N-acetylamino)-7-(1-methyl-2-propenyl)-1,2,3,4,4a,9a-hexahydrofluorene (diastereomer A) having a melting point of 166°-168° C. and of colorless granular crystal.

Workup

  1. temperatureUnder ice-cooling
  2. stirringby stirring at room temperature for 1 hour
  3. extractionExtraction
  4. additionwas carried out with addition of water
  5. concentrationthe organic layer was concentrated
  6. dissolutionThe resulting residue was dissolved in 250 ml of methanol
  7. additionwas added an aqueous solution
  8. additioncontaining 1.36 g of sodium bicarbonate in 50 ml of water
  9. temperatureby refluxing for 2 hours
  10. additionThe reaction mixture was rendered weakly acidic with addition of dilute hydrochloric acid
  11. extractionextracted with chloroform
  12. dry with materialThe organic layer was dried with magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated
  15. customThe resulting residue was purified by a silica gel column chromatography (eluent: chloroform:methanol:ethyl acetate=100:1:5)
  16. customThe component of Rf value 0.29 in the eluate was recrystallized from ethanol

Sources & evidence

ORD record
ord-3cb1d530898f456999616ed0eeb75741
Source dataset
uspto-grants-1991_05
Patent number
US05017724

Reaction notes

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