Hydrochloric Acid → 2-Fluoro-6-(1-methyleneethyl)anisole

HRID 1362464

반응식

HRID 1362464 반응식
Br[CH2:2]Br.[F:4][C:5]1[C:6]([O:14][CH3:15])=[C:7]([C:11](=O)[CH3:12])[CH:8]=[CH:9][CH:10]=1.Cl>C1COCC1.ClCCl.C(OCC)C.[Zn].[Ti](Cl)(Cl)(Cl)Cl.[Pb](Cl)Cl>[F:4][C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([C:11](=[CH2:2])[CH3:12])[C:6]=1[O:14][CH3:15]

참가 물질

10

반응물 3

HCID 313Hydrochloric AcidHCID 3024DibromomethaneHCID 112522251-(3-Fluoro-2-methoxyphenyl)ethanone

생성물 1

HCID 669694642-Fluoro-6-(1-methyleneethyl)anisole수율 70.7%

시약·촉매·용매 6

HCID 23994Zinc촉매HCID 24193Titanium Tetrachloride촉매HCID 24459Lead chloride촉매HCID 3283Diethyl Ether용매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매2회

반응 조건

온도
0 °C

실험 절차

41.8 g (639 mmol) of zinc dust and 874 mg (3.1 mmol) of lead(II) chloride are suspended in 557 ml of THF and at room temperature 39 ml (556 mmol) of dibromomethane are added. The mixture is stirred for a further 30 minutes and at 0° C. 68.8 ml (68.8 mmol) of a 1 M titanium(IV) chloride solution in dichloromethane are added dropwise. The cooling bath is removed and after 30 minutes at room temperature 13.6 g (80.8 mmol) of 1-(3-fluoro-2-methoxyphenyl)ethan-1-one (Chem. Commun. 2000, 14, 1323-4) in 139 ml of THF are added dropwise. The reaction mixture is stirred for a further 1.5 hours at room temperature. It is diluted with diethyl ether and cautiously poured onto a mixture of 4 M hydrochloric acid and ice. The phases are separated and subjected to extraction with diethyl ether, the extracts are washed with water and dried over sodium sulphate and the solvent is removed. The crude product is purified by column chromatography on silica gel (hexane/isopropyl ether 0-5%) to give 9.5 g of 2-fluoro-6-(1-methyleneethyl)anisole.

후처리

  1. additionare added
  2. additionare added dropwise
  3. stirringThe reaction mixture is stirred for a further 1.5 hours at room temperature
  4. customThe phases are separated
  5. extractionsubjected to extraction with diethyl ether
  6. washthe extracts are washed with water
  7. dry with materialdried over sodium sulphate
  8. customthe solvent is removed
  9. customThe crude product is purified by column chromatography on silica gel (hexane/isopropyl ether 0-5%)

출처 및 근거

ORD 기록
ord-e239d1eb86ec481b83b76f703ea5ae4f
출처 데이터셋
uspto-grants-2011_02
특허 번호
US07880042B2

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