Pyridine → 2-[1-(5-Methyl-furan-2-yl)-ethylidene]-malonic acid dimethyl ester

HRID 1807019Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1807019
[C:1]([O:8][CH3:9])(=[O:7])[CH2:2][C:3]([O:5][CH3:6])=[O:4].[C:10]([C:13]1[O:14][C:15]([CH3:18])=[CH:16][CH:17]=1)(=O)[CH3:11].N1C=CC=CC=1.ClCCl>O1CCCC1.Cl[Ti](Cl)(Cl)Cl.O>[CH3:6][O:5][C:3](=[O:4])[C:2](=[C:10]([C:13]1[O:14][C:15]([CH3:18])=[CH:16][CH:17]=1)[CH3:11])[C:1]([O:8][CH3:9])=[O:7]

Komponenten

8

Edukt 4

HCID 1049PyridineHCID 6344DichloromethaneHCID 7943Dimethyl malonateHCID 145142-Acetyl-5-Methylfuran

Produkt 1

HCID 143572882-[1-(5-Methyl-furan-2-yl)-ethylidene]-malonic acid dimethyl esterAusbeute 32 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24193Titanium TetrachlorideKatalysatorHCID 962WaterLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

Step A To a solution of dimethyl malonate (6.5 g, 49 mmol), 2-acetyl-5-methylfuran (6.1 g, 49 mmol) and pyridine (16 g, 200 mmol) in anhydrous tetrahydrofuran (300 mL) at 0° C. was added a dichloromethane solution (1 M) of TiCl4 (100 mL, 100 mmol) during a period of 1 h. After the addition was finished, the reaction mixture was gradually warmed room temperature and stirred for 18 h. Water was added to quench the reaction. The mixture was extracted with ethyl ether. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined, concentrated. The residue was purified by chromatography (EtOAc:hexanes=1:10) to give 2-[1-(5-methyl-furan-2-yl)-ethylidene]-malonic acid dimethyl ester as a yellow oil (3.7 g, 32%).

Aufarbeitung

  1. additionAfter the addition
  2. customwas gradually warmed room temperature
  3. customto quench
  4. customthe reaction
  5. extractionThe mixture was extracted with ethyl ether
  6. customThe organic layer was separated
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. concentrationconcentrated
  9. customThe residue was purified by chromatography (EtOAc:hexanes=1:10)

Quellen und Nachweise

ORD-Eintrag
ord-62edc8134eb2433e82f62edd527c5580
Quelldatensatz
uspto-grants-2013_01
Patentnummer
US08354444B2

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