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Beta-Lapachone → 5-(acetyloxy)-2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromen-6-yl N-(tert-butoxycarbonyl)glycinate

HRID 1914987
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Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1914987
[CH3:1][C:2]1([CH3:18])[CH2:11][CH2:10][C:9]2[C:8](=[O:12])[C:7](=[O:13])[C:6]3[CH:14]=[CH:15][CH:16]=[CH:17][C:5]=3[C:4]=2[O:3]1.[O-]S(S([O-])=O)=O.[Na+].[Na+].[C:27]([O:31][C:32]([NH:34][CH2:35][C:36]([OH:38])=O)=[O:33])([CH3:30])([CH3:29])[CH3:28].C(N([CH2:44][CH3:45])CC)C.CN(C([O:53]N1N=NC2C=CC=CC1=2)=[N+](C)C)C.F[P-](F)(F)(F)(F)F>[Zn].CCOC(C)=O.CN(C=O)C>[C:27]([O:31][C:32]([NH:34][CH2:35][C:36]([O:13][C:7]1[C:8]([O:12][C:44](=[O:53])[CH3:45])=[C:9]2[C:4](=[C:5]3[CH:17]=[CH:16][CH:15]=[CH:14][C:6]=13)[O:3][C:2]([CH3:18])([CH3:1])[CH2:11][CH2:10]2)=[O:38])=[O:33])([CH3:28])([CH3:29])[CH3:30]
KomponentenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

9

Edukt 5

HCID 3885Beta-LapachoneHCID 8471TriethylamineHCID 24489Sodium DithioniteHCID 78288N-(tert-butoxycarbonyl)glycineHCID 2733084Methanaminium, N-((1H-benzotriazol-1-yloxy)(dimethylamino)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)

Produkt 1

HCID 59514379
5-(acetyloxy)-2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromen-6-yl N-(tert-butoxycarbonyl)glycinate
Ausbeute 60 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 23994ZincKatalysator2×HCID 6228DimethylformamideLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A mixture of zinc dust (6.0 g, 91.7 mmol), 2,2-dimethyl-3,4-dihydro-2H-benzo[h]chromene-5,6-dione (6.0 g, 24.8 mmol), Na2S2O4 (17.26 g, 99.1 mmol), N-(tert-butoxycarbonyl)glycine (8.77 g, 49.6 mmol), triethylamine (3.1 mL, 22.3 mmol), HBTU (18.79 g, 49.6 mmol) and DMF (100 mL) is stirred for 16 hours at room temperature. To the reaction mixture is then added EtOAc (300 mL). The reaction is filtered and the filtrate washed with H2O (4×200 mL). The organic extract is dried with Na2SO4 and concentrated under reduced pressure. The residue is dissolved in acetic anhydride (30 mL) followed by the addition of zinc dust (3.0 g, 45.9 mmol) and thriethylamine (3.35 mL, 24.0 mmol). The reaction is heated at 90° C. with vigorous stirring and held for 2 hours. The reaction is allowed to cool and the solvent removed under reduced pressure. The residue is dissolved in EtOAc (200 mL) and washed with water (2×100 mL). The organic extract is dried with Na2SO4 and concentrated under reduced pressure. The crude product is purified by flash column chromatography (SiO2, 2% EtOAc in dichloromethane) to afford about 60% pure final product. Crystallization of the partly pure solid from EtOAc/Hexane gives the desired product as pure white solid (3.2 g, 31%). M.p.=177° C.; 400 MHz 1H NMR (CDCl3) δ: 8.21 (d, J=8.4 Hz, 1H), 7.67 (d, J=8.4 Hz, 1H), 7.46 (m, 2H), 5.13 (br. s, 1H), 4.30 (d, J=5.6 Hz, 2H), 2.68 (t, J=6.6 Hz, 2H), 2.38 (s, 3H), 1.87 (t, J=6.6 Hz, 2H), 1.48 (s, 9H), 1.42 (s, 6H); LCMS: 444 [M+H]; Calc. for C24H29NO7: C, 64.94; H, 6.59; N, 3.16; Found C 64.98, H 6.51, N 3.15.

Aufarbeitung

  1. filtrationThe reaction is filtered
  2. washthe filtrate washed with H2O (4×200 mL)
  3. extractionThe organic extract
  4. dry with materialis dried with Na2SO4
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe residue is dissolved in acetic anhydride (30 mL)
  7. temperatureThe reaction is heated at 90° C.
  8. stirringwith vigorous stirring
  9. waitheld for 2 hours
  10. temperatureto cool
  11. customthe solvent removed under reduced pressure
  12. dissolutionThe residue is dissolved in EtOAc (200 mL)
  13. washwashed with water (2×100 mL)
  14. extractionThe organic extract
  15. dry with materialis dried with Na2SO4
  16. concentrationconcentrated under reduced pressure
  17. customThe crude product is purified by flash column chromatography (SiO2, 2% EtOAc in dichloromethane)

Quellen und Nachweise

ORD-Eintrag
ord-4b8987146a4f41d2af4325c7ea2369ca
Quelldatensatz
uspto-grants-2013_12
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08614228B2

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