Ethyl Acetate → 2-(3,4-Dimethyl-phenyl)-malonic acid dimethyl ester

HRID 8598

反応式

HRID 8598 の反応式
[O-]P([O-])([O-])=O.[K+].[K+].[K+].Br[C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[C:12]([CH3:17])[CH:11]=1.[CH3:18][C:19](=[O:23])[O:20][CH2:21]C>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2].C(P(C(C)(C)C)C1C=CC=CC=1C1C=CC=CC=1)(C)(C)C>[CH3:21][O:20][C:19](=[O:23])[CH:18]([C:10]1[CH:15]=[CH:14][C:13]([CH3:16])=[C:12]([CH3:17])[CH:11]=1)[C:19]([O:20][CH3:21])=[O:23]

参加物

7

反応物 3

HCID 8857Ethyl AcetateHCID 62657Potassium Phosphate, TribasicHCID 685044-Bromo-o-xylene

生成物 1

HCID 688978002-(3,4-Dimethyl-phenyl)-malonic acid dimethyl ester

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 27342152-(Di-tert-butylphosphino)biphenyl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 (455 mg), 2-(di-tert.-butylphosphino)-biphenyl (1.21 g) and K3PO4 (39.6 g) in THF (200 ml) dimethylmalonate (12.85 g) and 1-bromo-3,4-dimethyl-benzene 15.0 g) was added under argon. The mixture was refluxed for 16 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 to give 2-(3,4-dimethyl-phenyl)-malonic acid dimethyl ester (16.2 g) as a colourless oil which slowly crystallises. 1H-NMR (300 MHz, CDCl3): 2.25(s, 3H), 2.26(s, 3H), 3.75(s, 6H), 4.59(s, 1H), 7.10–7.20(m, 3H).

後処理

  1. additionwas added under argon
  2. temperatureThe mixture was refluxed for 16 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

出典と根拠

ORDレコード
ord-a49db3e4ff1840bf80f49c0406a40f8c
出典データセット
uspto-grants-2006_08
特許番号
US07091201B2

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