2-Methyl-3-butyn-2-ol → 2-Methyl-4-(5-methyl-3-phenyl-isoxazol-4-yl)-but-3-yn-2-ol

HRID 1984647

反応式

HRID 1984647 の反応式
I[C:2]1[C:3]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[N:4][O:5][C:6]=1[CH3:7].C(N(CC)CC)C.[CH3:21][C:22]([OH:26])([C:24]#[CH:25])[CH3:23]>CN(C)C=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:21][C:22]([OH:26])([C:24]#[C:25][C:2]1[C:3]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[N:4][O:5][C:6]=1[CH3:7])[CH3:23]

参加物

7

反応物 3

HCID 82582-Methyl-3-butyn-2-ol2 回HCID 8471Triethylamine2 回HCID 27761504-Iodo-5-methyl-3-phenylisoxazole

生成物 1

HCID 688532502-Methyl-4-(5-methyl-3-phenyl-isoxazol-4-yl)-but-3-yn-2-ol収率 78%

試薬・触媒・溶媒 3

HCID 812191,3-Bis(diphenylphosphino)propane触媒2 回HCID 167845palladium(II) acetate触媒2 回HCID 6228Dimethylformamide溶媒

反応条件

温度
90 °C

実験手順

A mixture of 4-iodo-5-methyl-3-phenylisoxazole (5.73 g, 20.1 mmol), palladium(II) acetate (135 mg, 0.60 mmol), 1,3-bis(diphenylphosphino)propane (249 mg, 0.60 mmol), triethylamine (7.0 mL, 50.2 mmol) and 2-methyl-3-butyn-2-ol (3.0 mL, 30.7 mmol) in N,N-dimethylformamide (40 mL) was evaporated and flushed with argon. Cuprous iodide (77 mg, 0.40 mmol) was added and the reaction mixture was stirred for 23 h at 90° C. (after 1.75 h and 4.5 h, respectively, further palladium(II) acetate (135 mg, 0.60 mmol), 1,3-bis(diphenylphosphino)propane (249 mg, 0.60 mmol), triethylamine (7.0 mL, 50.2 mmol), 2-methyl-3-butyn-2-ol (3.0 mL, 30.7 mmol) and cuprous iodide (77 mg, 0.40 mmol) were added) before cooled to ambient temperature and separated between aqueous sodium hydroxide (1 M, 600 mL) and ethyl acetate (1000 mL). The aqueous layer was extracted with ethyl acetate (1000 mL) and washed with aqueous sodium hydroxide (1 M, 600 mL). The combined organic layers were dried over sodium sulfate and concentrated. Purification by chromatography (SiO2, heptane:ethyl acetate=67:33) afforded the title compound (3.77 g, 78%) as a yellow oil. MS: m/e=242.2 [M+H]+.

後処理

  1. customwas evaporated
  2. customflushed with argon
  3. temperaturebefore cooled to ambient temperature
  4. customseparated between aqueous sodium hydroxide (1 M, 600 mL) and ethyl acetate (1000 mL)
  5. extractionThe aqueous layer was extracted with ethyl acetate (1000 mL)
  6. washwashed with aqueous sodium hydroxide (1 M, 600 mL)
  7. dry with materialThe combined organic layers were dried over sodium sulfate
  8. concentrationconcentrated
  9. customPurification by chromatography (SiO2, heptane:ethyl acetate=67:33)

出典と根拠

ORDレコード
ord-eef96f50c0cd4a6a8e30c86abe2d91d4
出典データセット
uspto-grants-2009_06
特許番号
US07544704B2

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