Acetic Acid → HCID 13491249, compound

HRID 1719622Notes

Reaction equation

HRID 1719622 reaction equation
[BH4-].[Na+].[C:3]([NH:6][CH:7]1[CH:14]2[C:15](=O)[C:16]3[CH:21]=[CH:20][C:19]([O:22]C(=O)C)=[CH:18][C:17]=3[C:8]1([CH3:27])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]2)(=[O:5])[CH3:4].C(O)(=O)C>C(OCC)C.O.[Cl-].[Zn+2].[Cl-].[BH4-].[Zn+2].[BH4-]>[C:3]([NH:6][CH:7]1[C:14]2=[CH:15][C:16]3[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][C:17]=3[C:8]1([CH3:27])[CH2:9][CH2:10][CH2:11][CH2:12][CH2:13]2)(=[O:5])[CH3:4]

Participants

8

Reactant 3

HCID 176Acetic AcidHCID 4311764Sodium borohydrideHCID 13491246HCID 13491246, compound

Product 1

HCID 13491249HCID 13491249, compoundYield 80.9%

Reagents, catalysts & solvents 4

HCID 3007855ZincchlorideCatalystHCID 12838295ZINC;boranuideCatalystHCID 962WaterSolventHCID 3283Diethyl EtherSolvent3×

Procedure

Zinc chloride (5 g., 0.03 mole) was dissolved in 60 mL of diethyl ether and the insoluble material was filtered. The ethereal solution was added dropwise to sodium borohydride (3.5 g., 0.009 mole) in 150 mL of ether. The reaction mixture was stirred overnight at room temperature. The separated solid was allowed to settle and the supernatent liquid was removed by decantation. This ethereal solution of zinc borohydride was added to a solution of 4 g. (0.01 mole) of 13-acetylamino-6,7,8,9,10,11-hexahydro-3-acetyloxy-5-methyl-5,11-methanobenzocyclodecen-12(5H)-one in 50 mL of diethyl ether and the reaction mixture was stirred at room temperature for 48 hours. Excess zinc borohydride was decomposed by adding 3 mL of glacial acetic acid in 15 mL of water. The reaction mixture was filtered and the layer was washed with water, dried (anhydrous Na2SO4) and evaporated under reduced pressure. The separated solid was slurred in methanol and was heated while adding a few drops of dilute hydrochloric acid. The solvent was evaporated under vacuo and the solid was chromatographed on silica gel using ethyl acetate as eluent which afforded 2.3 g. (80.9% yield) of the title compound, mp 246°-249° C.

Workup

  1. filtrationthe insoluble material was filtered
  2. customthe supernatent liquid was removed by decantation
  3. additionThis ethereal solution of zinc borohydride was added to a solution of 4 g
  4. filtrationThe reaction mixture was filtered
  5. washthe layer was washed with water
  6. dry with materialdried (anhydrous Na2SO4)
  7. customevaporated under reduced pressure
  8. temperaturewas heated
  9. additionwhile adding a few drops of dilute hydrochloric acid
  10. customThe solvent was evaporated under vacuo
  11. customthe solid was chromatographed on silica gel
  12. customafforded 2.3 g

Sources & evidence

ORD record
ord-90cefe010a70494bbe7d5394cbd38ef1
Source dataset
uspto-grants-1985_09
Patent number
US04540806

Reaction notes

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