Tetrahydrofuran → 1-Chloro-2-fluoro-4-vinylbenzene

HRID 1774143ノート

反応式

HRID 1774143 の反応式
[H-].[Na+].[Cl:3][C:4]1[CH:11]=[CH:10][C:7]([CH:8]=O)=[CH:6][C:5]=1[F:12].[CH2:13]1COCC1>[Br-].C[P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:3][C:4]1[CH:11]=[CH:10][C:7]([CH:8]=[CH2:13])=[CH:6][C:5]=1[F:12]

参加物

5

反応物 3

HCID 8028TetrahydrofuranHCID 24758Sodium hydrideHCID 27249854-Chloro-3-Fluorobenzaldehyde

生成物 1

HCID 199564661-Chloro-2-fluoro-4-vinylbenzene収率 47%

試薬・触媒・溶媒 1

HCID 74505Methyltriphenyliphosphonium bromide触媒

実験手順

Sodium hydride (8.549 g, 213.7 mmol, 60% suspension in mineral oil) was added portionwise to a cold (0° C.) solution of 4-chloro-3-fluorobenzaldehyde (26.07 g, 164.4 mmol) and methyltriphenylphosphonium bromide (70.48 g, 197.3 mmol) in THF (400 mL). The reaction mixture was allowed to warm up to room temperature overnight. The solids were removed by filtration, and the filter cake was washed with ether. The filtrate was concentrated (water bath about 20° C.), and the residue was suspended in hexanes and stirred for 30 minutes. The solids (mostly PPh3O) were removed by filtration, and the filter cake was washed with hexanes. The filtrate was concentrated, and the crude product was purified by column chromatography, eluting with hexanes/ethyl acetate (25:1) to give 1-chloro-2-fluoro-4-vinylbenzene (12.1 g, 47%) as an oil. 1H NMR (400 MHz, CDCl3) δ 7.33 (m, 1H), 7.18 (m, 1H), 7.10 (m, 1H), 6.63 (m, 1H), 5.74 (d, J=17.4 Hz, 1H), 5.32 (d, J=10.8 Hz, 1H).

後処理

  1. customThe solids were removed by filtration
  2. washthe filter cake was washed with ether
  3. concentrationThe filtrate was concentrated (water bath about 20° C.)
  4. customThe solids (mostly PPh3O) were removed by filtration
  5. washthe filter cake was washed with hexanes
  6. concentrationThe filtrate was concentrated
  7. customthe crude product was purified by column chromatography
  8. washeluting with hexanes/ethyl acetate (25:1)

出典と根拠

ORDレコード
ord-558fd8993d494693b5fec7a33af882ac
出典データセット
uspto-grants-2016_02
特許番号
US09259470B2

反応ノート

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