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

HRID 2080072노트

반응식

HRID 2080072 반응식
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

참가 물질

9

반응물 4

HCID 97433-FluorophenolHCID 10796Cesium carbonateHCID 707002,2,6,6-Tetramethyl-3,5-heptanedione2회HCID 38572552-(4-Bromothiophen-2-yl)-1,3-dioxolane

생성물 1

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

시약·촉매·용매 4

HCID 62652Cuprous chloride촉매HCID 8058Hexane용매HCID 8857Ethyl Acetate용매HCID 13387N-methyl-2-pyrrolidone용매

반응 조건

온도
120 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-5dd2f031dc8d49ec98c9c4095b7f81f6
출처 데이터셋
uspto-grants-2011_04
특허 번호
US07932272B2

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