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Hydrochloric Acid → 4-((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)-9-bromo-7-isopropoxy-6-methyl-3,4-dihydrobenzo[f][1,4]oxazepin-5(2H)-one

HRID 577558
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 577558
[CH2:1]([O:8][C:9]1[C:14]([CH2:15][NH:16][CH2:17][CH2:18][O:19][C:20]2[C:30]([Br:31])=[CH:29][C:28]([O:32]S(C)(=O)=O)=[C:27]([CH3:37])[C:21]=2[C:22]([O:24]CC)=O)=[C:13]([CH3:38])[CH:12]=[C:11]([CH3:39])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[OH-].[Na+].Cl.[CH:43](N(CC)C(C)C)([CH3:45])[CH3:44].F[P-](F)(F)(F)(F)F.N1(OC(N(C)C)=[N+](C)C)C2N=CC=CC=2N=N1.C(=O)([O-])[O-].[Cs+].[Cs+].IC(C)C>CO.O>[CH2:1]([O:8][C:9]1[C:14]([CH2:15][N:16]2[C:22](=[O:24])[C:21]3[C:27]([CH3:37])=[C:28]([O:32][CH:43]([CH3:45])[CH3:44])[CH:29]=[C:30]([Br:31])[C:20]=3[O:19][CH2:18][CH2:17]2)=[C:13]([CH3:38])[CH:12]=[C:11]([CH3:39])[N:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

10

Edukt 7

HCID 313Hydrochloric AcidHCID 6362Isopropyl iodideHCID 10796Cesium carbonateHCID 14798Sodium HydroxideHCID 81531DiisopropylethylamineHCID 9886157Methanaminium, N-((dimethylamino)(3H-1,2,3-triazolo(4,5-b)pyridin-3-yloxy)methylene)-N-methyl-, hexafluorophosphate(1-) (1:1)
HCID 86723784
Ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)amino)ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate

Produkt 1

HCID 867237854-((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)-9-bromo-7-isopropoxy-6-methyl-3,4-dihydrobenzo[f][1,4]oxazepin-5(2H)-oneAusbeute 25.003,4 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittel3×

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

To a solution of ethyl 2-(2-(((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)amino)-ethoxy)-3-bromo-6-methyl-5-((methylsulfonyl)oxy)benzoate (116f, 0.54 g, 0.86 mmol) in methanol (2 mL) was added sodium hydroxide solution (50% in water, 0.73 g, 9.2 mmol). The reaction mixture was heated at 120° C. in the microwave for 1 hour then diluted with water and acidified with concentrated hydrochloric acid to pH ˜4. The resulting precipitate was collected by vacuum filtration then taken up in N,N-dimethylacetamide (5 mL). N,N-diisopropylethyl amine (0.38 mL, 2.2 mmol) and O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium hexafluorophosphate (HATU, 0.39 g, 1.0 mmol) were added and the reaction was stirred at room temperature overnight. The crude reaction was diluted with water (10 mL) and extracted with dichloromethane (2×15 mL). The combined organic layers were washed with brine (15 mL), dried over magnesium sulfate and concentrated under vacuum. The residue was dissolved in N,N-dimethylacetamide (5 mL) and cesium carbonate (0.51 g, 1.6 mmol) and 2-iodopropane (0.12 mL, 1.2 mmol) were added. The mixture was heated at 75° C. for 1 hour, cooled to room temperature then diluted with water (10 mL) and extracted with ethyl acetate (2×15 mL). The combined organic layers were washed with brine (15 mL), dried over magnesium sulfate, concentrated under vacuum, and purified by column chromatography (30% EtOAc/Heptane) to give 4-((2-(benzyloxy)-4,6-dimethylpyridin-3-yl)methyl)-9-bromo-7-isopropoxy-6-methyl-3,4-dihydrobenzo[f][1,4]oxazepin-5(2H)-one (116 g, 242 mg, 48% yield) as a clear sticky solid.

Aufarbeitung

  1. filtrationThe resulting precipitate was collected by vacuum filtration
  2. customThe crude reaction
  3. extractionextracted with dichloromethane (2×15 mL)
  4. washThe combined organic layers were washed with brine (15 mL)
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated under vacuum
  7. dissolutionThe residue was dissolved in N,N-dimethylacetamide (5 mL)
  8. temperatureThe mixture was heated at 75° C. for 1 hour
  9. temperaturecooled to room temperature
  10. extractionextracted with ethyl acetate (2×15 mL)
  11. washThe combined organic layers were washed with brine (15 mL)
  12. dry with materialdried over magnesium sulfate
  13. concentrationconcentrated under vacuum
  14. custompurified by column chromatography (30% EtOAc/Heptane)

Quellen und Nachweise

ORD-Eintrag
ord-5d67d62296544f6f819c3d965d5d65be
Quelldatensatz
uspto-grants-2015_05
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US09040515B2

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