Water → HCID 12766836, compound

HRID 2049018Notes

Reaction equation

HRID 2049018 reaction equation
[CH2:1]([O:3][C:4]([C:6]1([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH2:23][C:22]2[C:21]([O:24][CH3:25])=[C:20]3[C:11]([CH:12]=[C:13]4[C:18](=[C:19]3[OH:26])[CH:17]=[CH:16][CH:15]=[C:14]4[O:27][CH3:28])=[C:10]([O:29][CH3:30])[C:9]=2[CH2:8][CH2:7]1)=[O:5])[CH3:2].[Cr](O)(O)(=O)=[O:37].S(=O)(=O)(O)O.O>C(Cl)Cl.C(OC(=O)C)C.[O-2].[O-2].[O-2].[Cr+6]>[CH2:34]([O:33][C:31]([C:6]1([C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH2:23][C:22]2[C:21]([O:24][CH3:25])=[C:20]3[C:11]([C:12](=[O:37])[C:13]4[C:14]([O:27][CH3:28])=[CH:15][CH:16]=[CH:17][C:18]=4[C:19]3=[O:26])=[C:10]([O:29][CH3:30])[C:9]=2[CH2:8][CH2:7]1)=[O:32])[CH3:35]

Participants

7

Reactant 4

HCID 962WaterHCID 1118Sulfuric AcidHCID 24425Chromic Acid2×HCID 12766835HCID 12766835, compound

Product 1

HCID 12766836HCID 12766836, compoundYield 62%

Reagents, catalysts & solvents 2

HCID 10219390chromium (VI) trioxideCatalystHCID 21226138Dichloromethane ethylacetateSolvent

Procedure

The product of the principal reaction of example VII (compound VI) has added thereto ice (3 g) and there is added thereto a chromic acid solution of (4 ml.) from a previously prepared solution comprising chromium trioxide (24 g.), concentrated sulfuric acid 30 g, and water to 100 ml. The chromic acid solution is added dropwise with agitation while holding the mixture at 0° C. Thirty minutes after reaction is complete the reaction mixture is removed from the cooling bath and permitted to warm to ambient temperature at which it remains for 2 hours. The reaction mixture is then diluted with distilled water (20 ml.) and extracted with ethyl acetate (20 ml.). The aqueous phase is further extracted with ethyl acetate (20 ml.) and the organic phases iare combined. To the organic phase is added zinc dust (1 g) and the mixture shaken briefly, the zinc dust is removed by filtration and the organic filtrate washed successively with dilute aqueous hydrochloric acid (3 N. 20 ml.) saturated aqueous sodium bicarbonate (20 ml.) and distilled water (20 ml.) The organic extract is dried over anhydrous magnesium sulfate, filtered, and the solvent removed from the filtrate by evaporation under reduced pressure to yield an orange residue which was taken up in methylene-chloride/ethylacetate (17:3, 20 ml.) and passed through a silica gel column: (20 g). The solvent is removed from the eluate under reduced pressure and the residue recrystallized (from aqueous methanol) to give 9,9-Bis(ethoxycarbonyl-4,6,11-trimethoxy-7,8,9,10-tetrahydronaphthacene-5,-12-quinone (VII) (860 mg., 0.017 moles 62%) as yellow needle crystals m.p. 123°-125° C.

Workup

  1. additionhas added
  2. customat 0° C
  3. customThirty minutes after reaction
  4. customis removed from the cooling bath
  5. additionThe reaction mixture is then diluted with distilled water (20 ml.)
  6. extractionextracted with ethyl acetate (20 ml.)
  7. extractionThe aqueous phase is further extracted with ethyl acetate (20 ml.)
  8. additionTo the organic phase is added zinc dust (1 g)
  9. customthe zinc dust is removed by filtration
  10. washthe organic filtrate washed successively with dilute aqueous hydrochloric acid (3 N. 20 ml.) saturated aqueous sodium bicarbonate (20 ml.)
  11. distillationdistilled water (20 ml.) The
  12. extractionorganic extract
  13. dry with materialis dried over anhydrous magnesium sulfate
  14. filtrationfiltered
  15. customthe solvent removed from the filtrate by evaporation under reduced pressure
  16. customto yield an orange residue which
  17. customThe solvent is removed from the eluate under reduced pressure
  18. customthe residue recrystallized (from aqueous methanol)

Sources & evidence

ORD record
ord-e1e9faf7089c4f8398548486e55018f6
Source dataset
uspto-grants-1980_04
Patent number
US04196127

Reaction notes

Loading…