Ethanol → 2-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetic acid

HRID 591065Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 591065
Br[C:2]1[C:3]([C:9](=[O:15])[C:10]([O:12]CC)=[O:11])=[C:4]([CH3:8])[S:5][C:6]=1[CH3:7].C(=O)([O-])[O-].[Na+].[Na+].CC1(C)C(C)(C)OB([C:30]2[CH:31]=[C:32]3[C:37](=[CH:38][CH:39]=2)[O:36][CH2:35][CH2:34][CH2:33]3)O1.C(O)C>C1(C)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].O>[O:36]1[C:37]2[CH:38]=[CH:39][C:30]([C:2]3[C:3]([C:9](=[O:15])[C:10]([OH:12])=[O:11])=[C:4]([CH3:8])[S:5][C:6]=3[CH3:7])=[CH:31][C:32]=2[CH2:33][CH2:34][CH2:35]1

Komponenten

8

Edukt 4

HCID 702EthanolHCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70818387Ethyl (4-bromo-2,5-dimethyl-thiophen-3-yl)-oxo-acetate

Produkt 1

HCID 708551932-[4-(3,4-dihydro-2H-1-benzopyran-6-yl)-2,5-dimethyl thiophen-3-yl]-2-oxoacetic acidAusbeute 100 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 962WaterLösungsmittel2×HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

A solution of ethyl 2-(4-bromo-2,5-dimethylthiophen-3-yl)-2-oxoacetate (17c) (1.0 g, 3.43 mmol), sodium carbonate (1.46 g, 13.7 mmol), and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (1.16 g, 4.46 mmol) in a mixture of toluene (9 mL), ethanol (3 mL) and water (3.5 mL) was bubbled with nitrogen for 5 minutes. Palladium tetrakis(triphenylphosphine) (0.2 g, 0.17 mmol) was added and the reaction mixture was heated at 95° C. overnight. Water (5 mL) was added and the organic layer was extracted with 1N sodium hydroxide (5 mL). The combined aqueous layers were washed with ethyl acetate (10 mL), acidified with 1M hydrochloric acid until pH 2 and extracted with dichloromethane (2×10 mL). The organic layer was dried over sodium sulfate and concentrated in vacuo to provide the desired product (42a) (1.09 g, 3.43 mmol, 100%) which was used without further purification.

Aufarbeitung

  1. customwas bubbled with nitrogen for 5 minutes
  2. extractionthe organic layer was extracted with 1N sodium hydroxide (5 mL)
  3. washThe combined aqueous layers were washed with ethyl acetate (10 mL)
  4. extractionextracted with dichloromethane (2×10 mL)
  5. dry with materialThe organic layer was dried over sodium sulfate
  6. concentrationconcentrated in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-b53374957af946358cd3c222fe4ba0bb
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09238026B2

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