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Potassium Carbonate → Tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinate

HRID 1641075
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 1641075
Br[C:2]1[N:7]=[C:6]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=1.[CH3:15][N:16]1[C:25]2[C:20](=[CH:21][C:22](B3OC(C)(C)C(C)(C)O3)=[CH:23][CH:24]=2)[NH:19][CH2:18][CH2:17]1.C([O-])([O-])=O.[K+].[K+]>O1CCOCC1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[CH3:15][N:16]1[C:25]2[C:20](=[CH:21][C:22]([C:2]3[N:7]=[C:6]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:5]=[CH:4][CH:3]=3)=[CH:23][CH:24]=2)[NH:19][CH2:18][CH2:17]1
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Komponenten

8

Edukt 3

HCID 11430Potassium CarbonateHCID 23432991tert-Butyl 6-bromopicolinateHCID 594187141-Methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoxaline

Produkt 1

HCID 59418755Tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinateAusbeute 38,3 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 74236
Tetrabutylammonium Bromide
Katalysator
HCID 178418476HCID 178418476, VerbindungKatalysator
HCID 962WaterLösungsmittel2×
HCID 312751,4-DioxaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Tert-butyl 6-bromopicolinate (25A) (157 mg, 0.61 mmol) in 1,4-dioxane (1.0 mL) was added dropwise to 1-methyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,4-tetrahydroquinoxaline (25F) (167 mg, 0.61 mmol), K2CO3 (207 mg, 1.52 mmol), tetrabutylammonium bromide (19.5 mg, 0.061 mmol), and dichlorobis(triphenylphosphine)palladium(II) (17.9 mg, 0.024 mmol) in 1,4-dioxane (2.0 mL) and water (1.0 mL) at rt. The mixture was microwave (150W) heated to 100° C. for 50 minutes, cooled to 20° C., diluted with water and extracted with EtOAc. The organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE:EtOAc 100:0-70:30, to provide 76 mg (38%) of the desired product tert-butyl 6-(1-methyl-1,2,3,4-tetrahydroquinoxalin-6-yl)picolinate (25G): 1H NMR (300 MHz, MeOD) δ 7.84-7.78 (3H, m), 7.35 (1H, d), 7.30 (1H, d), 6.62 (1H, d), 3.41 (2H, t), 3.31 (2H, t), 2.92 (3H, bs), 1.64 (9H, s).

Aufarbeitung

  1. temperaturecooled to 20° C.
  2. extractionextracted with EtOAc
  3. washThe organic phases were washed with brine
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE

Quellen und Nachweise

ORD-Eintrag
ord-d0149dbee3e44f219f2fcf4cfe49d03b
Quelldatensatz
uspto-grants-2012_02
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08114893B2

Notizen zur Reaktion

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