Hydrogen Peroxide → HCID 13826445, compound

HRID 1906929Notes

Reaction equation

HRID 1906929 reaction equation
C(B(CC)CC)C.[Cl:8][C:9]1[C:18]2[C:13](=[CH:14][C:15]([Cl:19])=[CH:16][CH:17]=2)[C:12]([CH2:20][CH2:21][CH:22]([OH:31])[CH2:23][C:24](=[O:30])[CH2:25][C:26]([O:28][CH3:29])=[O:27])=[C:11]([CH3:32])[CH:10]=1.[BH4-].[Na+].OO>C1COCC1.CO>[Cl:8][C:9]1[C:18]2[C:13](=[CH:14][C:15]([Cl:19])=[CH:16][CH:17]=2)[C:12]([CH2:20][CH2:21][CH:22]([OH:31])[CH2:23][CH:24]([OH:30])[CH2:25][C:26]([O:28][CH3:29])=[O:27])=[C:11]([CH3:32])[CH:10]=1

Participants

7

Reactant 4

HCID 784Hydrogen PeroxideHCID 7357TriethylboraneHCID 4311764Sodium borohydrideHCID 13826444HCID 13826444, compound

Product 1

HCID 13826445HCID 13826445, compoundYield 49.4%

Reagents, catalysts & solvents 2

HCID 887MethanolSolvent2×HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-100 °C

Procedure

A 1M solution of triethylborane (3.75 ml, 3.75 mmoles) was added to a solution of methyl 7-(4,7-dichloro-2-methylnaphthalen-1-yl)-5-hydroxy-3-oxo-heptanoate (0.96 g, 2.5 mmoles) in dry THF (9 ml). Air (7.5 ml) was bubbled slowly into the solution at room temperature with stirring. Stirring was continued at room temperature for 15 minutes then cooled in frozen methanol bath (-100° C.). Sodium borohydride (0.142 g, 3.75 mmoles) was added followed by the slow addition by syringe through a septum of methanol (2.7 ml) in about 10 minutes at -100° C. The reaction was stirred at -100° C. for 30 minutes. The frozen methanol bath was replaced by an ice-salt water bath and stirred for 10 minutes. Then added slowly a 30% solution of hydrogen peroxide (6.0 ml) dropwise so that the internal temperature does not exceed 5° C. Removed cooling bath and stirred at ambient temperature for 30 minutes. Made slightly acidic by the addition of 1N HCl then extracted with ethyl acetate three times. Washed the combined ethyl acetate extracts with water two times then brine, dried (MgSO4), filtered and the solvent evaporated in vacuo to leave 0.968 g of crude product which was flash chromatographed on 50×180 mm silica column eluting with 50% ethyl acetate in hexane to give 0.476 g of title compound, exact mass calc. for C18H18Cl2O3 (M-CH3OH): 352.0633; Found: 352.0638.

Workup

  1. customAir (7.5 ml) was bubbled slowly into the solution at room temperature
  2. stirringStirring
  3. stirringThe reaction was stirred at -100° C. for 30 minutes
  4. stirringstirred for 10 minutes
  5. customdoes not exceed 5° C
  6. customRemoved
  7. temperaturecooling bath
  8. stirringstirred at ambient temperature for 30 minutes
  9. additionMade slightly acidic by the addition of 1N HCl
  10. extractionthen extracted with ethyl acetate three times
  11. washWashed the combined ethyl acetate
  12. dry with materialbrine, dried (MgSO4)
  13. filtrationfiltered
  14. customthe solvent evaporated in vacuo
  15. customto leave 0.968 g of crude product which
  16. customchromatographed on 50×180 mm silica column
  17. washeluting with 50% ethyl acetate in hexane

Sources & evidence

ORD record
ord-1c31a895fb7e43db91bcd45224ad16a8
Source dataset
uspto-grants-1987_03
Patent number
US04654363

Reaction notes

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