Hydrochloric Acid → HCID 10449991, Verbindung

HRID 1453993Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1453993
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](I)=[C:5]([O:10][CH3:11])[C:4]=1[O:12][CH3:13].C([Li])CCC.[CH3:19][N:20]([CH3:32])[C:21]1[CH:30]=[C:29]2[C:24]([C:25](=O)[CH2:26][CH2:27][O:28]2)=[CH:23][CH:22]=1.[NH4+].[Cl-].Cl>C1COCC1.CCOC(C)=O.C(O)C>[CH3:19][N:20]([CH3:32])[C:21]1[CH:30]=[C:29]2[C:24]([C:25]([C:7]3[CH:8]=[C:3]([O:2][CH3:1])[C:4]([O:12][CH3:13])=[C:5]([O:10][CH3:11])[CH:6]=3)=[CH:26][CH2:27][O:28]2)=[CH:23][CH:22]=1

Komponenten

9

Edukt 5

HCID 313Hydrochloric AcidHCID 25517Ammonium ChlorideHCID 2569311-Iodo-2,3,4-trimethoxybenzeneHCID 20312680HCID 20312680, VerbindungHCID 178418339Butyllithium

Produkt 1

HCID 10449991HCID 10449991, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 702EthanolLösungsmittelHCID 8028TetrahydrofuranLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel2×

Versuchsvorschrift

To a solution of trimethoxyiodobenzene (159 mg, 0.54 mmol) in THF (2.5 mL) at −78° C. was added n-butyl lithium solution (1.6 M in hexane, 0.34 mL). The reaction mixture was stirred 10 min, then a solution of 7-dimethylamino-chroman-4-one (103 mg, 0.54 mmol) in THF (2.5 mL) was added and stirring continued at −78° C. for 1 h followed by room temperature overnight. The reaction became orange, NH4Cl saturated solution (1 mL) was added and the mixture was diluted with EtOAc (25 mL). The organic layer was washed with water (25 mL), brine (25 mL), dried over magnesium sulfate and concentrated to yield a yellow oil. The residue was dissolved in ethanol (6 mL) and treated with concentrated hydrochloric acid (2 mL). The mixture was heated to reflux for 90 min, allowed to cool, diluted with EtOAc (25 mL) and washed with water (2×25 mL), 10% sodium thiosulfate (25 mL) and water (25 mL). The organic layer was dried over MgSO4 and concentrated to yield a yellow oil. Purification by Biotage flash chromatography using 50% EtOAc/hexane gave a mixture of compounds. Another purification was done using 20% EtOAc/hexane and yielded 30 mg (16%) as a green oil. 1H NMR (CDCl3): 6.97 (d, J=8.5 Hz, 1H), 6.59 (s, 2H), 6.35-6.25 (2m, 2H), 5.61 (s, 1H), 4.82 (d, J=4.0 Hz, 2H), 3.91 (s, 3H), 3.87 (s, 3H), 2.99 (s, 3H).

Aufarbeitung

  1. stirringstirring
  2. waitcontinued at −78° C. for 1 h
  3. waitfollowed by room temperature overnight
  4. washThe organic layer was washed with water (25 mL), brine (25 mL)
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated
  7. customto yield a yellow oil
  8. temperatureThe mixture was heated
  9. temperatureto reflux for 90 min
  10. temperatureto cool
  11. washwashed with water (2×25 mL), 10% sodium thiosulfate (25 mL) and water (25 mL)
  12. dry with materialThe organic layer was dried over MgSO4
  13. concentrationconcentrated
  14. customto yield a yellow oil
  15. customPurification by Biotage flash chromatography
  16. customgave
  17. additiona mixture of compounds
  18. customAnother purification
  19. customyielded 30 mg (16%) as a green oil

Quellen und Nachweise

ORD-Eintrag
ord-2f4874dca1984af3ba25f2d3e823186f
Quelldatensatz
uspto-grants-2009_01
Patentnummer
US07476741B2

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