Sodium Dithionite → HCID 66546822, compound

HRID 1746929Notes

Reaction equation

HRID 1746929 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].[C:19]([O:23][C:24]([NH:26][CH2:27][C:28](O)=[O:29])=[O:25])([CH3:22])([CH3:21])[CH3:20].F[P-](F)(F)(F)(F)F.C[N+](C)=C(N(C)C)ON1C2C=CC=CC=2N=N1.S(S([O-])=O)([O-])=O.[Na+].[Na+]>CN(C=O)C.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.[Zn].C(OCC)(=O)C>[C:1]([C:4]1[O:8][C:7]2[C:9]([O:18][C:28](=[O:29])[CH2:27][NH:26][C:24]([O:23][C:19]([CH3:21])([CH3:20])[CH3:22])=[O:25])=[C:10]3[C:15](=[C:16]([OH:17])[C:6]=2[CH:5]=1)[CH:14]=[CH:13][CH:12]=[CH:11]3)(=[O:3])[CH3:2]

Participants

9

Reactant 4

HCID 24489Sodium DithioniteHCID 78288N-(tert-butoxycarbonyl)glycineHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)HCID 103318442-Acetylfuro-1,4-naphthoquinone

Product 1

HCID 66546822HCID 66546822, compoundYield 49.4%

Reagents, catalysts & solvents 4

HCID 23994ZincCatalystHCID 74236Tetrabutylammonium BromideCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

In a 250 ml round-bottom flask, 2 grams (8.3 mmoles) of 2-acetyl-naphtho[2,3-b]furan-4,9-dione (prepared in example 2 or 3) was dissolved in 50 ml of DMF with heating. To the solution, added 3.5 ml of TEA, 2 grams of zinc powder, 0.3 gram of tetrabutylammonium bromide, 2.33 grams (13.3 mmoles) of [(tert-butoxycarbonyl)amino]acetic acid, 5.04 grams (13.3 mmoles) of N,N,N′,N′-Tetramethyl-O-(1H-benzotriazol-1-yl)uronium hexafluorophosphate (HBTU) and 7.25 grams (41.7 mmoles) of sodium hydrosulfite. The mixture was sealed or isolated from air, and then had been stirred vigorously at room temperature overnight. After addition of 100 ml of ethyl acetate, the reaction mixture was filtered, and the solid was washed with 50 ml of ethyl acetate. The filtrates were combined, extracted with 100 ml of ice-cooled aqueous 3% citric acid solution twice, and dried with anhydrous sodium sulfate. The organic phase was evaporated to dryness. Product was purified by silica gel chromatograph using dichloromethane/ethyl acetate (4:1) as elution solvent. 1.64 gram (4.1 mmoles) of product was obtained with yield of 49.4% and characterized by 1H NMR and mass spectrum. 1H NMR (in DMSO) δ 1.44 (s, 9H), 2.59 (s, 3H), 4.28 (d, J=6, 2H), 7.49-7.65 (m, 3H), 7.97 (m, 1H), 8.20-8.35 (m, 2H), 11.4 (s, 1H). Mass (M+H) is 400, Mass [M-(tert-butyl)+2H] is 344.

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 50 ml of ethyl acetate
  6. extractionextracted with 100 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. customProduct was purified by silica gel chromatograph
  11. washas elution solvent

Sources & evidence

ORD record
ord-c6d433455e0941ab8b4048c632d1ac28
Source dataset
uspto-grants-2015_10
Patent number
US09150530B2

Reaction notes

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