Water → HCID 59769753、化合物

HRID 2220357ノート

反応式

HRID 2220357 の反応式
[OH-].[Na+].[Cl:3][C:4]1[CH:5]=[C:6]([OH:11])[CH:7]=[C:8]([Cl:10])[CH:9]=1.[CH2:12]([C@H:15]1[O:17][C@@H:16]1[CH2:18][OH:19])[CH2:13][CH3:14].O>C1COCC1.[Cl-].[Na+].O.ClCCl>[Cl:3][C:4]1[CH:5]=[C:6]([CH:7]=[C:8]([Cl:10])[CH:9]=1)[O:11][C@@H:15]([CH2:12][CH2:13][CH3:14])[C@H:16]([OH:17])[CH2:18][OH:19]

参加物

8

反応物 4

HCID 962WaterHCID 115713,5-DichlorophenolHCID 14798Sodium HydroxideHCID 11073386(2R,3R)-(+)-3-PROPYLOXIRANEMETHANOL, 97% (94% EE/GLC)

生成物 1

HCID 59769753HCID 59769753、化合物収率 26%

試薬・触媒・溶媒 3

HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒2 回HCID 57417360Sodium chloride; water溶媒

反応条件

温度
75 °C

実験手順

Add sodium hydroxide (1N, 9 mL) to a stirred solution of 3,5-dichlorophenol in THF (9 mL) followed by a solution of (R,R)-(3-propyl-oxiranyl)-methanol in THF (5 mL). Heat the reaction mixture at 75° C. overnight, cool to room temperature, add water, brine and dichloromethane, and separate the layers. The aqueous layer is extracted with dichloromethane, the combined organic extracts are washed successively with 1N sodium hydroxide and water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Analysis of the crude reaction mixture by 1H NMR reveals a ˜2:1 mixture of the C-3:C-1 adducts. Purification of the crude residue on silica gel eluting with 0-25% EtOAc/hexanes gives the major title compound (332 mg, 26%). 1H NMR (DMSO-d6): 0.86 (dd, 3H, J=4, 4 Hz), 1.21-1.48 (m, 2H), 1.52-1.72 (m, 2H), 3.28-3.45 (m, 2H), 3.60-3.67 (m, 2H), 4.37-4.44 (m, 1H), 4.69 (dd, 1H, J=6, 6 Hz), 4.88 (d, 1H, J=5 Hz), 7.01-7.10 (m, 3H).

後処理

  1. temperaturecool to room temperature
  2. customseparate the layers
  3. extractionThe aqueous layer is extracted with dichloromethane
  4. washthe combined organic extracts are washed successively with 1N sodium hydroxide and water
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customAnalysis of the crude reaction mixture by 1H NMR
  8. additiona ˜2:1 mixture of the C-3
  9. customPurification of the crude residue on silica gel eluting with 0-25% EtOAc/hexanes

出典と根拠

ORDレコード
ord-f5c6ff974c5041ab892c980c12cc4f98
出典データセット
uspto-grants-2008_08
特許番号
US07417064B2

反応ノート

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