Ethyl Acetate → 2-(2,4-Dimethyl-phenyl)-malonic acid dimethyl ester

HRID 8599

反応式

HRID 8599 の反応式
[O-]P([O-])([O-])=O.[K+].[K+].[K+].Br[C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][C:11]=1[CH3:17].[CH3:18][C:19](=[O:23])[O:20][CH2:21]C>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:21][O:20][C:19](=[O:23])[CH:18]([C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[CH:12][C:11]=1[CH3:17])[C:19]([O:20][CH3:21])=[O:23]

参加物

6

反応物 3

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 68503Benzene, 1-bromo-2,4-dimethyl-

生成物 1

HCID 688971052-(2,4-Dimethyl-phenyl)-malonic acid dimethyl ester

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 8028Tetrahydrofuran溶媒

実験手順

(In analogy to a procedure given in J. Am. Chem. Soc. 122 (2000), 1360–1370.) To a suspension of Pd(OAc)2 (758 mg), 2-(di-tert.-butlylphosphino)-biphenyl (2.02 g) and K3PO4 (65.95 g) in THF (350 ml) dimethylmalonate (21.42 g) and 1-bromo-2,4-dimethyl-benzene (25 g) was added under argon. The mixture was refluxed for 96 h, cooled to rt and diluted with EA (300 ml) and filtered. The filtrate was evaporated and the resulting brown oil was purified on silica gel eluting with heptane:EA 4:1 to 1:1 followed by distillation (bp 95–100° C. at 0.064 mbar) to give 2-(2,4-dimethyl-phenyl)-malonic acid dimethyl ester (5.66 g) as a colourless oil. 1H-NMR(300 MHz, CDCl3): 2.30(s, 6H), 3.75(s, 6H), 4.87(s, 1H), 6.98–7.05(m, 2H), 7.25–7.28(m, 1H).

後処理

  1. additionwas added under argon
  2. temperatureThe mixture was refluxed for 96 h
  3. filtrationfiltered
  4. customThe filtrate was evaporated
  5. customthe resulting brown oil was purified on silica gel eluting with heptane:EA 4:1 to 1:1
  6. distillationfollowed by distillation (bp 95–100° C. at 0.064 mbar)

出典と根拠

ORDレコード
ord-82f8576a87f140efbfe729c5f4cccf25
出典データセット
uspto-grants-2006_08
特許番号
US07091201B2

関連ノート

読み込み中…