Acetic Anhydride → HCID 66546825, compound

HRID 1746928Notes

Reaction equation

HRID 1746928 reaction equation
[C:1]([C:4]1[O:8][C:7]2[C:9](=[O:18])[C:10]3[C:15]([C:16](=[O:17])[C:6]=2[CH:5]=1)=[CH:14][CH:13]=[CH:12][CH:11]=3)(=[O:3])[CH3:2].S(S([O-])=O)([O-])=O.[Na+].[Na+].[C:27](OC(=O)C)(=[O:29])[CH3:28].[C:34](OCC)(=[O:36])[CH3:35]>CN(C=O)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.[Zn]>[C:1]([C:4]1[O:8][C:7]2[C:9]([O:18][C:34](=[O:36])[CH3:35])=[C:10]3[C:15](=[C:16]([O:17][C:27](=[O:29])[CH3:28])[C:6]=2[CH:5]=1)[CH:14]=[CH:13][CH:12]=[CH:11]3)(=[O:3])[CH3:2]

Participants

8

Reactant 4

HCID 7918Acetic AnhydrideHCID 8857Ethyl AcetateHCID 24489Sodium DithioniteHCID 103318442-Acetylfuro-1,4-naphthoquinone

Product 1

HCID 66546825HCID 66546825, compoundYield 50.7%

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 6228DimethylformamideSolvent

Procedure

In a 500 ml round-bottom flask, 8 grams (33.3 mmoles) of 2-acetyl-naphtho[2,3-b]furan-4,9-dione (prepared in example 2 or 3) was dissolved in 150 ml of DMF with heating. To the solution, added 14 ml of TEA, 8 grams of zinc powder, 1 gram of tetrabutylammonium bromide and 29 grams (166.7 mmoles) of sodium hydrosulfite. The mixture was sealed or isolated from air. Then 17 grams (166.7 mmoles) of acetic anhydride was added with syringe, and the resulting mixture had been stirred vigorously at room temperature for 3 hours. After addition of 300 ml of ethyl acetate, the reaction mixture was filtered, and the solid was washed with 200 ml of ethyl acetate. The filtrates were combined, extracted with 300 ml of ice-cooled aqueous 3% citric acid solution twice, and dried with anhydrous sodium sulfate. The organic phase was evaporated to dryness. The residue was washed with 60 ml of ice-cooled ethanol, and then filtered solid was crystallized in 250 ml of ethanol. 5.5 grams (16.9 mmoles, yield 50.7%) of product was obtained and characterized by 1H NMR and mass spectrum. 1H NMR (in CDCl3) δ 2.59 (s, 3H), 2.62 (s, 3H), 2.66 (s, 3H), 7.50 (s, 1H), 7.53-7.62 (m, 2H), 8.00-8.03 (m, 2H). Mass (M+H) is 327, Mass (M+Na) is 349.

Workup

  1. temperaturewith heating
  2. customThe mixture was sealed
  3. customisolated from air
  4. filtrationthe reaction mixture was filtered
  5. washthe solid was washed with 200 ml of ethyl acetate
  6. extractionextracted with 300 ml of ice-
  7. temperaturecooled aqueous 3% citric acid solution twice
  8. dry with materialdried with anhydrous sodium sulfate
  9. customThe organic phase was evaporated to dryness
  10. washThe residue was washed with 60 ml of ice-
  11. temperaturecooled ethanol
  12. filtrationfiltered solid
  13. customwas crystallized in 250 ml of ethanol

Sources & evidence

ORD record
ord-e8bc43fac1a24cd6b5ffcb10b0145849
Source dataset
uspto-grants-2015_10
Patent number
US09150530B2

Reaction notes

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