Ethyl Acetate → 3-Chloro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)benzenamine

HRID 1713888ノート

反応式

HRID 1713888 の反応式
C(=O)([O-])[O-].[K+].[K+].CC1(C)C(C)(C)OB([C:15]2[CH2:24][CH2:23][C:18]3([O:22][CH2:21][CH2:20][O:19]3)[CH2:17][CH:16]=2)O1.Br[C:27]1[CH:33]=[CH:32][C:30]([NH2:31])=[CH:29][C:28]=1[Cl:34].C(OCC)(=O)C>C(COC)OC.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[Cl:34][C:28]1[CH:29]=[C:30]([CH:32]=[CH:33][C:27]=1[C:15]1[CH2:24][CH2:23][C:18]2([O:19][CH2:20][CH2:21][O:22]2)[CH2:17][CH:16]=1)[NH2:31]

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 888884-Bromo-3-chloroanilineHCID 36970768-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro(4.5)dec-7-ene

生成物 1

HCID 594640703-Chloro-4-(1,4-dioxaspiro[4.5]dec-7-en-8-yl)benzenamine収率 62.1%

試薬・触媒・溶媒 2

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
80 °C

実験手順

A 2N aqueous solution of potassium carbonate (26.5 mL) and tetrakis(triphenylphosphine) palladium(0) (1.23 g, 1.06 mmol) were added sequentially, each in one portion, to a stirred solution of 8-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-dioxaspiro[4.5]dec-7-ene (Intermediate 78ii, 5.65 g, 21.2 mmol) and 4-bromo-3-chloro aniline (4.39 g, 21.2 mmol) in dimethoxyethane (80 mL) at room temperature under an argon atmosphere. The reaction mixture was then heated at 80° C. for 24 h under an argon atmosphere. The reaction mixture was cooled to room temperature and ethyl acetate was added and then the mixture was washed twice with H2O and then brine. The organic layer was dried (MgSO4) and concentrated in vacuo to leave an oil, which was purified by column chromatography, using a gradient of 20-50% ethyl acetate:isohexane as eluent, to give the title compound (3.5 g, 62%) as a solid; 1H NMR δ 1.7-1.8 (2H, m), 2.26-2.43 (4H, m), 3.91 (4H, s), 5.28 (2H, s), 5.4-5.47 (1H, m), 6.45 (1H, dd), 6.59 (1H, d), 6.86 (1H, d).

後処理

  1. customat room temperature
  2. temperatureThe reaction mixture was cooled to room temperature
  3. washthe mixture was washed twice with H2O
  4. dry with materialThe organic layer was dried (MgSO4)
  5. concentrationconcentrated in vacuo
  6. customto leave an oil, which
  7. customwas purified by column chromatography

出典と根拠

ORDレコード
ord-9e9f2dcf38cc4f148be2902f56c0fde7
出典データセット
uspto-grants-2010_09
特許番号
US07795283B2

反応ノート

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