Sulfuric Acid → HCID 67126958, compound

HRID 2406874Notes

Reaction equation

HRID 2406874 reaction equation
S(=O)(=O)(O)O.[CH3:6][C:7]1([CH2:16][OH:17])[C:13]2([CH2:15][CH2:14]2)[CH:11]2[CH2:12][CH:8]1[CH2:9][CH2:10]2.S(=O)(O)[O-:19].[Na+]>O.CC(C)=O.C(OCC)(=O)C.[O-2].[O-2].[O-2].[Cr+6]>[CH3:6][C:7]1([C:16]([OH:19])=[O:17])[C:13]2([CH2:15][CH2:14]2)[CH:11]2[CH2:12][CH:8]1[CH2:9][CH2:10]2

Participants

8

Reactant 3

HCID 1118Sulfuric AcidHCID 23665763Sodium BisulfiteHCID 67127054HCID 67127054, compound

Product 1

HCID 67126958HCID 67126958, compoundYield 58%

Reagents, catalysts & solvents 4

HCID 10219390chromium (VI) trioxideCatalystHCID 180AcetoneSolventHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a stirred solution of chromium trioxide (8.0 g, 76 mmol) in water (30 mL) cooled in an ice bath, was added carefully 96% sulfuric acid (6.9 mL, 120 mmol). While continuing to cool and stir the oxidant solution in an ice bath, a solution of (3-methylspiro[bicyclo[2.2.1]heptane-2.1′-cyclopropane]-3-yl)methanol (9.5 g; 57 mmol) in acetone (115 mL) was added over a 20 min period. After complete addition, the reaction mixture was stirred for 3 h while warming to ambient temperature. The reaction was then diluted with water (45 mL) and ethyl acetate (200 mL). Slowly, sodium bisulfite powder was added until the brown color dissipated and the aqueous layer became blue. The phases were then separated, and the aqueous layer was washed with ethyl acetate (2×100 mL). The organic layers were combined and dried over anhydrous magnesium sulfate. The drying agent was removed by filtration, and the filtrate was concentrated to yield a green oil. The oil as purified by silica gel (200 g) column chromatography, using a 0-50% ethyl acetate in hexanes gradient. Selected fractions were combined and concentrated to yield 6.0 g of 3-methylspiro[bicyclo[2.2.1]heptane-2,1′-cyclopropane]-3-carboxylic acid as a white solid (58%).

Workup

  1. temperatureto cool
  2. additionAfter complete addition
  3. stirringthe reaction mixture was stirred for 3 h
  4. customThe phases were then separated
  5. washthe aqueous layer was washed with ethyl acetate (2×100 mL)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customThe drying agent was removed by filtration
  8. concentrationthe filtrate was concentrated
  9. customto yield a green oil
  10. customThe oil as purified by silica gel (200 g) column chromatography
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-df038771e0464bac95ea20f2c21ccab2
Source dataset
uspto-grants-2014_08
Patent number
US08809397B2

Reaction notes

Loading…