Triethylamine → rac-3,4-dihydro-2,5,7,8-tetramethyl-2-[(2-thienyl) ethynyl]-2H-1-benzopyran-6ol

HRID 256834

Reaktionsgleichung

Reaktionsgleichung von HRID 256834
[C:1]([C:3]1([CH3:17])[CH2:8][CH2:7][C:6]2[C:9]([CH3:16])=[C:10]([OH:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=2[O:4]1)#[CH:2].I[C:19]1[S:20][CH:21]=[CH:22][CH:23]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(N(CC)CC)C>C(#N)C>[CH3:17][C:3]1([C:1]#[C:2][C:19]2[S:20][CH:21]=[CH:22][CH:23]=2)[CH2:8][CH2:7][C:6]2[C:9]([CH3:16])=[C:10]([OH:15])[C:11]([CH3:14])=[C:12]([CH3:13])[C:5]=2[O:4]1

Komponenten

6

Edukt 4

HCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 189212-IodothiopheneHCID 14478563rac-3,4-dihydro-2-ethynyl-2,5,7,8-tetramethyl-2H-1-benzopyran-6ol

Produkt 1

HCID 9904883rac-3,4-dihydro-2,5,7,8-tetramethyl-2-[(2-thienyl) ethynyl]-2H-1-benzopyran-6olAusbeute 56 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

A mixture of 4.6 g (20 mmol) of rac-3,4-dihydro-2-ethynyl-2,5,7,8-tetramethyl-2H-1-benzopyran-6-ol, 6.3 g (30 mmol) of 2-iodothiophene, 0.8 g of triphenylphosphine, 0.19 g of cuprous iodide, 6 ml of triethylamine and 200 ml of acetonitrile was stirred and degassed with argon for 15 minutes. Palladium acetate, 220 mg, was then added and stirring under argon was continued for 4 hours. The solvent was removed under reduced pressure and the residue was partitioned between methylene chloride and saturated aqueous sodium bicarbonate solution. The organic phase was separated, dried and evaporated. The residue was chromatographed over 200 g of silica gel (Merck 70-230 mesh) using methylene chloride. Crystallization of the combined clean fractions from ether/hexane yielded 3.5 g (56%) of rac-3,4-dihydro-2,5,7,8-tetramethyl-2-[(2-thienyl)ethynyl]-2H-1-benzopyran-6-ol with m.p. 112°-114° C.

Aufarbeitung

  1. customdegassed with argon for 15 minutes
  2. additionPalladium acetate, 220 mg, was then added
  3. stirringstirring under argon
  4. customThe solvent was removed under reduced pressure
  5. customthe residue was partitioned between methylene chloride and saturated aqueous sodium bicarbonate solution
  6. customThe organic phase was separated
  7. customdried
  8. customevaporated
  9. customThe residue was chromatographed over 200 g of silica gel (Merck 70-230 mesh)
  10. customCrystallization of the combined clean fractions from ether/hexane

Quellen und Nachweise

ORD-Eintrag
ord-58fb5437469d4d75b9e401de862d0846
Quelldatensatz
uspto-grants-1993_11
Patentnummer
US05260294

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