Diisopropylamine → 5-[2-(2,4-Difluorophenyl)ethenyl]-2,2-dimethyl-3(2H)-furanone

HRID 1085562Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1085562
C(NC(C)C)(C)C.C([Li])CCC.[CH3:13][C:14]1([CH3:21])[C:18](=[O:19])[CH:17]=[C:16]([CH3:20])[O:15]1.[F:22][C:23]1[CH:30]=[C:29]([F:31])[CH:28]=[CH:27][C:24]=1[CH:25]=O.FC(F)(F)C(OC(=O)C(F)(F)F)=O>O1CCCC1.CCCCCC.C(N(CC)CC)C.CN(C)P(N(C)C)(N(C)C)=O>[F:22][C:23]1[CH:30]=[C:29]([F:31])[CH:28]=[CH:27][C:24]=1[CH:25]=[CH:20][C:16]1[O:15][C:14]([CH3:21])([CH3:13])[C:18](=[O:19])[CH:17]=1

Komponenten

10

Edukt 5

HCID 7912DiisopropylamineHCID 9845Trifluoroacetic anhydrideHCID 737702,4-DifluorobenzaldehydeHCID 1370803(2H)-Furanone, 2,2,5-trimethyl-HCID 178418339Butyllithium

Produkt 1

HCID 539726665-[2-(2,4-Difluorophenyl)ethenyl]-2,2-dimethyl-3(2H)-furanoneAusbeute 65 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 8028TetrahydrofuranLösungsmittel3×HCID 8058HexaneLösungsmittelHCID 8471TriethylamineLösungsmittelHCID 12679HexamethylphosphoramideLösungsmittel

Versuchsvorschrift

To a solution of dry diisopropylamine (3.3 mL, 24 mM) in dry tetrahydrofuran (25 mL) at -78° C., was added dropwise 2.3N solution of n-butyllithium in hexane (10.4 mL, 24 mM). After the reaction solution was stirred 15 minutes, a solution of 2,2,5-trimethyl-3(2H)-furanone (2.0 g, 16 mM) in tetrahydrofuran (10 mL) was added dropwise. Hexamethylphosphoramide (4.4 mL, 24 mM) was then added dropwise after 30 minutes. Finally, 2,4-difluorobenzaldehyde (3.5 mL, 31.8 mM) in tetrahydrofuran (10 mL) was added in one portion. The reaction solution was stirred 10 minutes when trifluoroacetic anhydride (11.87 g, 55.7 mM) was added in one portion. Again, the reaction solution was stirred 15, minutes when triethylamine (5.6 g, 55.7 mM) was added and was allowed to warm to room temperature. The reaction solution was partitioned between saturated aqueous sodium chloride (50 mL) and diethyl ether (50 mL). The layers were separated. The organic layers were then washed with saturated aqueous sodium chloride (2×25 mL), dried over MgSO4, filtered and concentrated under reduced pressure to give an orange liquid. The crude product was purified by chromatography (silica gel, pet. ether-ethyl acetate) to afford a yellow crystalline solid (2.6 g, 65% yield), m.p. 98.5°-100° C.

Aufarbeitung

  1. additionwas added in one portion
  2. additionwas added
  3. customThe reaction solution was partitioned between saturated aqueous sodium chloride (50 mL) and diethyl ether (50 mL)
  4. customThe layers were separated
  5. washThe organic layers were then washed with saturated aqueous sodium chloride (2×25 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give an orange liquid
  10. customThe crude product was purified by chromatography (silica gel, pet. ether-ethyl acetate)

Quellen und Nachweise

ORD-Eintrag
ord-341c1c0277084dc49337d5a5c78539d3
Quelldatensatz
uspto-grants-1991_04
Patentnummer
US05010102

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