3-Fluorophenol → 4-(3-Fluoro-phenoxy)-thiophen-2-yl-[1,3]dioxolane

HRID 2080072ノート

反応式

HRID 2080072 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:7]2[O:11][CH2:10][CH2:9][O:8]2)[S:5][CH:6]=1.[F:12][C:13]1[CH:14]=[C:15]([OH:19])[CH:16]=[CH:17][CH:18]=1.CC(C)(C(=O)CC(=O)C(C)(C)C)C.C(=O)([O-])[O-].[Cs+].[Cs+]>CN1CCCC1=O.[Cu]Cl.C(OCC)(=O)C.CCCCCC>[F:12][C:13]1[CH:14]=[C:15]([CH:16]=[CH:17][CH:18]=1)[O:19][C:2]1[CH:3]=[C:4]([CH:7]2[O:11][CH2:10][CH2:9][O:8]2)[S:5][CH:6]=1

参加物

9

反応物 4

HCID 97433-FluorophenolHCID 10796Cesium carbonateHCID 707002,2,6,6-Tetramethyl-3,5-heptanedione2 回HCID 38572552-(4-Bromothiophen-2-yl)-1,3-dioxolane

生成物 1

HCID 231305304-(3-Fluoro-phenoxy)-thiophen-2-yl-[1,3]dioxolane収率 24.4%

試薬・触媒・溶媒 4

HCID 62652Cuprous chloride触媒HCID 8058Hexane溶媒HCID 8857Ethyl Acetate溶媒HCID 13387N-methyl-2-pyrrolidone溶媒

反応条件

温度
120 °C

実験手順

2-(4-Bromo-thiophen-2-yl)-[1,3]dioxolane (1.0 g, 4.3 mmol), 3-fluorophenol (0.95 g, 8.6 mmol), 2,2,6,6-tetramethyl-3,5-heptanedione (0.078 g, 0.43 mmol), copper(I) chloride (0.21 g, 2.7 mmol) and cesium carbonate (2.8 g, 8.6 mmol) were suspended in N-methylpyrrolidone (10 mL) under a nitrogen stream, and the mixture was stirred for 4.5 hours at 120° C. To this suspension was added 2,2,6,6-tetramethyl-3,5-heptanedione (0.12 g, 0.65 mmol), and the solution was further stirred for 8 hours at 140° C. The reaction mixture was filtered through Celite pad, then, water and ethyl acetate were added for partitioning, and the organic layer was washed with water twice. NH silica gel was added to the organic layer, the solvent was evaporated in vacuo for adsorption to NH silica gel, purification was carried out by NH silica gel column chromatography (hexane, then hexane:ethyl acetate=30:1), and the title compound (280 mg, 1.05 mmol, 24.4%) was obtained as a colorless oil.

後処理

  1. stirringthe solution was further stirred for 8 hours at 140° C
  2. filtrationThe reaction mixture was filtered through Celite pad
  3. additionwater and ethyl acetate were added
  4. customfor partitioning
  5. washthe organic layer was washed with water twice
  6. additionNH silica gel was added to the organic layer
  7. customthe solvent was evaporated in vacuo for adsorption to NH silica gel, purification

出典と根拠

ORDレコード
ord-5dd2f031dc8d49ec98c9c4095b7f81f6
出典データセット
uspto-grants-2011_04
特許番号
US07932272B2

反応ノート

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