Water → Dimethyl 7-chloroquinoline-2,3-dicarboxylate

HRID 3116

Reaktionsgleichung

Reaktionsgleichung von HRID 3116
Cl[C:2]1[C:11]2[C:6](=[CH:7][C:8]([Cl:12])=[CH:9][CH:10]=2)[N:5]=[C:4]([C:13]([O:15][CH3:16])=[O:14])[C:3]=1[C:17]([O:19][CH3:20])=[O:18].C([O-])=O.[Na+].O>CN(C)C=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:12][C:8]1[CH:7]=[C:6]2[C:11]([CH:2]=[C:3]([C:17]([O:19][CH3:20])=[O:18])[C:4]([C:13]([O:15][CH3:16])=[O:14])=[N:5]2)=[CH:10][CH:9]=1

Komponenten

6

Edukt 3

HCID 962WaterHCID 2723810Sodium FormateHCID 18929951Dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate

Produkt 1

HCID 18929843Dimethyl 7-chloroquinoline-2,3-dicarboxylateAusbeute 134,8 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418397HCID 178418397, VerbindungKatalysatorHCID 6228DimethylformamideLösungsmittel

Versuchsvorschrift

A stirred mixture of dimethyl 4,7-dichloroquinoline-2,3-dicarboxylate (5.00 g, 15.9 mM), sodium formate (1.63 g, 23.9 mM) and tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) in anhydrous dimethylformamide (75 mL) under a nitrogen atmosphere was heated at 90°-95° C. for 7 hr. No reaction occurred so the reaction mixture was degassed and an additional quantity of tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) was added and the reaction mixture again heated at 90°-95° C. for 6 hr. The cooled reaction mixture was poured into water and the resulting mixture extracted with ethyl acetate. The combined extracts were dried (MgSO4), filtered and concentrated to leave an gummy solid (6.0 g). Trituration of this residue with ethyl acetate and subsequent filtration separated a crystalline solid which was shown to be dimethyl 7-chloro-4-hydroxyquinoline-2,3-dicarboxylate. The filtrate was concentrated and the residue was flash chromatographed over silica gel (eluant: hexane/ethyl acetate, 3/2) to provide the title diester (1.13 g, 25.4%) as a light yellow crystalline solid; MS(CI): 280 (M+H).

Aufarbeitung

  1. temperaturewas heated at 90°-95° C. for 7 hr
  2. customwas degassed
  3. additionan additional quantity of tetrakis(triphenylphosphine)palladium(0) (0.92 g, 0.80 mM) was added
  4. temperaturethe reaction mixture again heated at 90°-95° C. for 6 hr
  5. customThe cooled reaction mixture
  6. extractionthe resulting mixture extracted with ethyl acetate
  7. dry with materialThe combined extracts were dried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-e1f559619b474a8e8ddc858df147e65a
Quelldatensatz
uspto-grants-1998_03
Patentnummer
US05733910

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