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

HRID 1449564

반응식

HRID 1449564 반응식
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(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Pd]>[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

참가 물질

6

반응물 3

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

생성물 1

HCID 18929843Dimethyl 7-chloroquinoline-2,3-dicarboxylate수율 134.8%

시약·촉매·용매 2

HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 6228Dimethylformamide용매

실험 절차

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(O) (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(O) (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). 300-MHz 1H NMR (DMSO d6), 9.15 (s, 1H), 8.33 (d, 1H, J=9 Hz), 8.25 (d, 1H, J=2 Hz), 7.86 (dd, 1H, J=9 Hz, 2 Hz), 3.93 (s, 3H), 3.92 (s, 3H).

후처리

  1. temperaturewas heated at 90°-95° C. for 7 hr
  2. customwas degassed
  3. additionan additional quantity of tetrakis(triphenylphosphine)palladium(O) (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

출처 및 근거

ORD 기록
ord-f6907b34b0c342fcb7ba55f380ddb031
출처 데이터셋
uspto-grants-1997_02
특허 번호
US05599814

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