Ammonium Chloride → 4-Methoxy-3-(3,3,3-trifluoropropyl)benzaldehyde dimethyl acetal

HRID 989277

反応式

HRID 989277 の反応式
[Mg].I[CH2:3][CH2:4][C:5]([F:8])([F:7])[F:6].[Cl-].[NH4+].[CH3:11][O:12][CH:13]([O:22][CH3:23])[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1>C1COCC1.[Cu]I.C(OCC)(=O)C>[CH3:11][O:12][CH:13]([O:22][CH3:23])[C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[C:16]([CH2:3][CH2:4][C:5]([F:8])([F:7])[F:6])[CH:15]=1

参加物

8

反応物 4

HCID 25517Ammonium ChlorideHCID 75140p-(Dimethoxymethyl)anisoleHCID 1561651,1,1-Trifluoro-3-iodopropaneHCID 5462224Magnesium2 回

生成物 1

HCID 225748774-Methoxy-3-(3,3,3-trifluoropropyl)benzaldehyde dimethyl acetal

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

A solution of 229A (15.8 g, 60 mmol) in dry THF (120 ml) was added to magnesium turnings (4.1 g, 170 mmol) at RT. The mixture was heated to 60° C. for 5 min, which initiated an exothermic reaction. The heating bath was removed and the mixture was allowed to reflux gently. Upon subsidence of the reaction (approximately 5 min), the mixture was heated to reflux for an additional 20 min and then was allowed to cool to RT. The clear green supernatant was transferred via canula away from excess magnesium and into a separate flask containing copper (I) iodide (575 mg, 3.0 mmol) under a nitrogen atmosphere. To this mixture was added 1-iodo-3,3,3-trifluoropropane (15 g, 67 mmol) and the resulting mixture was allowed to stir for 16 h, during which time a thick white precipitate developed. Aqueous ammonium chloride solution, ethyl acetate, and hexanes were added, and the organic layer was dried over sodium sulfate. Evaporation followed by silica gel chromatography of the residue using 3:1 hexanes/ethyl acetate as eluant provided 7.7 g of a mobile, slightly yellow oil, which was a 6:1 (mol ratio) mixture of 229B and 4-methoxybenzaldehyde dimethyl acetal, as determined by proton NMR. This mixture was used without further purification.

後処理

  1. customan exothermic reaction
  2. customThe heating bath was removed
  3. temperatureto reflux gently
  4. customUpon subsidence of the reaction (approximately 5 min)
  5. temperaturethe mixture was heated
  6. temperatureto reflux for an additional 20 min
  7. temperatureto cool to RT
  8. dry with materialthe organic layer was dried over sodium sulfate
  9. customEvaporation
  10. customprovided 7.7 g of a mobile, slightly yellow oil, which
  11. customThis mixture was used without further purification

出典と根拠

ORDレコード
ord-0c1fac6778a247d2846b4f3cf468722c
出典データセット
uspto-grants-2003_10
特許番号
US06638937B2

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