Chloroform → HCID 70569626, compound

HRID 1680233Notes

Reaction equation

HRID 1680233 reaction equation
[CH:1]1([CH2:4][N:5]2[CH2:23][CH2:22][C@@:12]34[C:13]5[CH:14]=[C:15]([O:20]C)[CH:16]=[CH:17][C:18]=5[CH2:19][C@@H:6]2[C@:7]3([O:26][CH3:27])[C@H:8]([CH3:25])[CH2:9][C:10](=[O:24])[CH2:11]4)[CH2:3][CH2:2]1.B(Br)(Br)Br.[OH-].[NH4+].C(Cl)(Cl)[Cl:35]>CO.C(OCC)C>[ClH:35].[CH:1]1([CH2:4][N:5]2[CH2:23][CH2:22][C@@:12]34[C:13]5[CH:14]=[C:15]([OH:20])[CH:16]=[CH:17][C:18]=5[CH2:19][C@@H:6]2[C@:7]3([O:26][CH3:27])[C@H:8]([CH3:25])[CH2:9][C:10](=[O:24])[CH2:11]4)[CH2:2][CH2:3]1

Participants

7

Reactant 4

HCID 6212Chloroform2×HCID 14923Ammonium HydroxideHCID 25134Boron tribromideHCID 70567185HCID 70567185, compound

Product 1

HCID 70569626HCID 70569626, compound

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 3283Diethyl EtherSolvent

Procedure

A solution of 17-cyclopropylmethyl-3,14-dimethoxy -8α-methylmorphinan-6-one (30) (0.323 g, 0.874 mmol) in chloroform (5 ml) was slowly added over a 2 to 3 minute period to a solution of boron tribromide (1.266 g, 5.053 mmol) in chloroform. A tan colored precipitate formed, and the mixture was stirred for an additional 20 minutes. The mixture was then poured carefully into a mixture of ice (8 g) and ammonium hydroxide (4 ml). After stirring the mixture at 0° to 5° C. for 40 minutes, the layers were separated and the aqueous layer was extracted with chloroform (2×20 ml). The organic extracts were combined, washed with water, dried over NaSO4, filtered and concentrated under reduced pressure to give a gummy solid. The product was purified by column chromatography on silica gel using graded methanol/chloroform mixtures as eluant. Upon removal of the solvent a gum was obtained which was dissolved in a small volume of methanol whereupon dry diethyl ether was added and insoluble material was removed by filtration. To the clear solution was added a saturated solution of HCl in ether and the salt precipitated. The precipitated solid was separated by decantantion and dissolved in a small volume of methanol. Addition of dry diethyl ether to this methanolic solution gave pure 17-cyclopropylmethyl-3-hydroxy-14-methoxy-8α-methylmorphinan-6-one hydrochloride (31) as a cream colored solid (0.064 g, 19% theory).

Workup

  1. customA tan colored precipitate formed
  2. stirringAfter stirring the mixture at 0° to 5° C. for 40 minutes
  3. customthe layers were separated
  4. extractionthe aqueous layer was extracted with chloroform (2×20 ml)
  5. washwashed with water
  6. dry with materialdried over NaSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give a gummy solid
  10. customThe product was purified by column chromatography on silica gel using graded methanol/chloroform mixtures as eluant
  11. customUpon removal of the solvent a gum
  12. customwas obtained which
  13. additionwas added
  14. custominsoluble material was removed by filtration
  15. additionTo the clear solution was added a saturated solution of HCl in ether
  16. customthe salt precipitated
  17. customThe precipitated solid was separated by decantantion
  18. dissolutiondissolved in a small volume of methanol
  19. additionAddition of dry diethyl ether to this methanolic solution

Sources & evidence

ORD record
ord-dac5853e43f64fea932f5dc6d62c225c
Source dataset
uspto-grants-1981_06
Patent number
US04272540

Reaction notes

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