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

HRID 1362464

反応式

HRID 1362464 の反応式
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]

参加物

10

反応物 3

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

生成物 1

HCID 669694642-Fluoro-6-(1-methyleneethyl)anisole収率 70.7%

試薬・触媒・溶媒 6

HCID 23994Zinc触媒HCID 24193Titanium Tetrachloride触媒HCID 24459Lead chloride触媒HCID 3283Diethyl Ether溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
0 °C

実験手順

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.

後処理

  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%)

出典と根拠

ORDレコード
ord-e239d1eb86ec481b83b76f703ea5ae4f
出典データセット
uspto-grants-2011_02
特許番号
US07880042B2

関連ノート

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