Water → 9,10-Dihydro-9,10-methano-9-anthracenecarboxylic acid

HRID 1490227Notes

Reaction equation

HRID 1490227 reaction equation
[CH:1]([C:3]12[CH2:17][CH:10]([C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][C:16]=31)[C:9]1[C:4]2=[CH:5][CH:6]=[CH:7][CH:8]=1)=[O:2].CC(C)=[O:20].OS(O)(=O)=O.O=[Cr](=O)=O.O>CC(C)=O.[O-2].[O-2].[O-2].[Cr+6]>[CH:5]1[C:4]2[C:3]3([C:1]([OH:20])=[O:2])[CH2:17][CH:10]([C:11]4[C:16]3=[CH:15][CH:14]=[CH:13][CH:12]=4)[C:9]=2[CH:8]=[CH:7][CH:6]=1

Participants

6

Reactant 3

HCID 962WaterHCID 124041419,10-Dihydro-9,10-methanoanthracene-9-carboxaldehydeHCID 131709961Jones' reagent

Product 1

HCID 125071199,10-Dihydro-9,10-methano-9-anthracenecarboxylic acidYield 80%

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 180AcetoneSolvent

Procedure

To a cooled solution (0° C.) of 9-formyl-9,10-dihydro-9,10-methanoanthracene (literature preparation: M. Sunagawa, et al.; Chem. Pharm. Bull. Vol. 27 (1979) pp 1806-1812; U.S. Pat. No. 4,224,344 Sunagawa et al., Sumitomo, Ltd.; Sep. 23, 1980; U.S. Pat. No. 4,358,620 Sunagawa et al., Sumitomo, Ltd.; Nov. 9, 1982) (78.5 mmol) in acetone (260 mL) was added Jones reagent (24 mL; 27 g chromium trioxide, 23 mL water diluted up to 100 mL of reagent solution) in portions. The reagent was added until an orange color persists. The reaction, containing a significant amount of reduced chromium salts, was warmed to room temperature. The solvents were removed in vacuo and replaced with water (300 mL) and saturated with sodium chloride. The aqueous phase was extracted with ethyl acetate (3×300 mL). Combined organic extracts were extracted with 2.5N NaOH (3×400 mL). The basic aqueous extracts were acidified with 3N HCl, saturated with sodium chloride, and extracted with ethyl acetate (4×300 mL). Combined organic extracts were dried over anhydrous magnesium sulfate, filtered, and reduced to a white solid. The title compound was formed in 80% yield as a white solid. MS (Cl CH4) m/z 237 (M+1,100), 265 (m+29,10), 219 (22), 209 (15), 193 (20)

Workup

  1. additionThe reagent was added until an orange color persists
  2. customThe reaction
  3. customThe solvents were removed in vacuo
  4. extractionThe aqueous phase was extracted with ethyl acetate (3×300 mL)
  5. extractionCombined organic extracts were extracted with 2.5N NaOH (3×400 mL)
  6. extractionextracted with ethyl acetate (4×300 mL)
  7. dry with materialCombined organic extracts were dried over anhydrous magnesium sulfate
  8. filtrationfiltered

Sources & evidence

ORD record
ord-4b9053a1883840b79e26cbcd8002ee8a
Source dataset
uspto-grants-1997_10
Patent number
US05681840

Reaction notes

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