Bromide ion → 1,1-Diphenyl-hex-5-en-2-ol

HRID 78893

反応式

HRID 78893 の反応式
II.[Br-].[C:4]1([CH:10]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH:11]=[O:12])[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.C([O-])(O)=O.[Na+]>C(OCC)C.BrCCC=C>[C:13]1([CH:10]([C:4]2[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=2)[CH:11]([OH:12])[CH2:6][CH2:5][CH:4]=[CH2:9])[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

参加物

7

反応物 4

HCID 259Bromide ionHCID 807Iodine2 回HCID 13696DiphenylacetaldehydeHCID 516892Sodium Bicarbonate

生成物 1

HCID 643145171,1-Diphenyl-hex-5-en-2-ol収率 165.3%

試薬・触媒・溶媒 2

HCID 21241Homoallyl bromide触媒HCID 3283Diethyl Ether溶媒3 回

実験手順

A dry three-neck, round-bottom flask fitted with a reflux condensor, air-balance drop funnel and nitrogen inlet was charged with Mg (0.11 g, 4.44 mmol) and a crystal of I2. The flask was warmed (heat gun) to volatilize the I2 under vacuum, and then was allowed to cool. Dry ethyl ether (10 ml) was added next followed by introduction of catalytic neat 4-bromo-1-butene (0.02 g). The reaction was initiated by brief warming and then the rest of total amount of bromide (0.4 g, 2.96 mmol) in dry ethyl ether (5 ml) was added dropwise over 5 minutes. The mixture was refluxed for 30 minutes and then was allowed to reach 0° C. Into the stirred Grignard reagent solution was added dropwise a solution of diphenylacetaldehyde 1 (0.64 g, 3.26 mmol) in dry ethyl ether (5 ml), and the reaction mixture was stirred for an additional 3.5 hr at room temperature. Saturated aqueous NaHCO3 was added to the reaction mixture at 0° C., the organic phase was separated and the aqueous phase was extracted with ethyl ether (3×20 ml). The combined organic phases were washed with brine and water, then dried over anhydrous Na2SO4. The solvent was removed under reduced pressure, and flash chromatography of the crude residue (SiO2, hexane/Ethyl Acetate 9:1) gave 1,1-diphenyl-hex-5-en-2-ol 8 (0.68 g, 91%) as a liquid.

後処理

  1. customA dry three-neck, round-bottom flask fitted with a reflux condensor, air-balance drop funnel and nitrogen inlet
  2. temperatureThe flask was warmed
  3. temperature(heat gun)
  4. temperatureto cool
  5. temperatureby brief warming
  6. temperatureThe mixture was refluxed for 30 minutes
  7. customto reach 0° C
  8. customthe organic phase was separated
  9. extractionthe aqueous phase was extracted with ethyl ether (3×20 ml)
  10. washThe combined organic phases were washed with brine and water
  11. dry with materialdried over anhydrous Na2SO4
  12. customThe solvent was removed under reduced pressure, and flash chromatography of the crude residue (SiO2, hexane/Ethyl Acetate 9:1)

出典と根拠

ORDレコード
ord-9bbd26a8f01e4c04b52a61e9ef3b41d6
出典データセット
uspto-grants-2014_09
特許番号
US08841464B2

関連ノート

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