Dimethyl Sulfoxide → Tert-butyl 2-hydroxy-6-[({4'-[2-hydroxy-1-(methoxycarbonyl)ethyl]-1,1'-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate

HRID 2076651ノート

反応式

HRID 2076651 の反応式
[CH3:1]S(C)=O.[CH2:5]=[O:6].[C:7](=[O:10])([O-])[OH:8].[Na+].[OH:12][C:13]1[C:25]([C:26]([F:29])([F:28])[F:27])=[CH:24][CH:23]=[C:22]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35]([C:38]3[CH:43]=[CH:42][C:41]([CH2:44][C:45]([O:47][CH3:48])=[O:46])=[CH:40][CH:39]=3)=[CH:34][CH:33]=2)[C:14]=1[C:15]([O:17][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:16]>C(OCC)(=O)C>[OH:12][C:13]1[C:25]([C:26]([F:28])([F:29])[F:27])=[CH:24][CH:23]=[C:22]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35]([C:38]3[CH:43]=[CH:42][C:41]([CH:44]([C:45]([O:47][CH3:48])=[O:46])[CH2:7][OH:8])=[CH:40][CH:39]=3)=[CH:34][CH:33]=2)[C:14]=1[C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16].[OH:12][C:13]1[C:25]([C:26]([F:28])([F:29])[F:27])=[CH:24][CH:23]=[C:22]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35]([C:38]3[CH:43]=[CH:42][C:41]([C:44]([C:45]([O:47][CH3:48])=[O:46])=[CH2:1])=[CH:40][CH:39]=3)=[CH:34][CH:33]=2)[C:14]=1[C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16].[OH:12][C:13]1[C:25]([C:26]([F:28])([F:29])[F:27])=[CH:24][CH:23]=[C:22]([CH2:30][O:31][C:32]2[CH:37]=[CH:36][C:35]([C:38]3[CH:43]=[CH:42][C:41]([C:44]([CH2:7][OH:10])([C:45]([O:47][CH3:48])=[O:46])[CH2:5][OH:6])=[CH:40][CH:39]=3)=[CH:34][CH:33]=2)[C:14]=1[C:15]([O:17][C:18]([CH3:19])([CH3:20])[CH3:21])=[O:16]

参加物

8

反応物 4

HCID 679Dimethyl SulfoxideHCID 712FormaldehydeHCID 516892Sodium BicarbonateHCID 67119193HCID 67119193、化合物

生成物 3

HCID 67119106Tert-butyl 2-hydroxy-6-[({4'-[1-(methoxycarbonyl)vinyl]-1,1'-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate収率 9%HCID 67119108Tert-butyl 2-hydroxy-6-[({4'-[2-hydroxy-1-hydroxymethyl-1-(methoxycarbonyl)ethyl]-1,1'-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate収率 25%HCID 67119119Tert-butyl 2-hydroxy-6-[({4'-[2-hydroxy-1-(methoxycarbonyl)ethyl]-1,1'-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate収率 58%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

反応条件

温度
60 °C

実験手順

Dimethyl sulfoxide (3 ml), paraformaldehyde (90% purity, 300 mg) and sodium hydrogencarbonate (300 mg, 3.57 mmol) were added to tert-butyl 2-hydroxy-6-[({4′-[(methoxycarbonyl)methyl]-1,1′-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate (400 mg, 0.77 mmol) obtained in Example (6-9), and the mixture was stirred at 60° C. for 3 hours. After the reaction mixture was cooled to room temperature, it was diluted with ethyl acetate. The organic layer was successively washed with water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate. The residue obtained by removing the solvent under reduced pressure was purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=4/1-1/3) to give tert-butyl 2-hydroxy-6-[({4′-[2-hydroxy-1-(methoxycarbonyl)ethyl]-1,1′-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate as a colorless solid (246 mg, yield: 58%), tert-butyl 2-hydroxy-6-[({4′-[1-(methoxycarbonyl)vinyl]-1,1′-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate (37 mg, yield: 9%) and tert-butyl 2-hydroxy-6-[({4′-[2-hydroxy-1-hydroxymethyl-1-(methoxycarbonyl)ethyl]-1,1′-biphenyl-4-yl}oxy)methyl]-3-(trifluoromethyl)benzoate (112 mg, yield: 25%).

後処理

  1. temperatureAfter the reaction mixture was cooled to room temperature
  2. washThe organic layer was successively washed with water
  3. dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate
  4. customThe residue obtained
  5. customby removing the solvent under reduced pressure
  6. customwas purified by silica gel column chromatography (eluting solvent: n-hexane/ethyl acetate=4/1-1/3)

出典と根拠

ORDレコード
ord-d412cc83c9d84c65895fafcc1aa2b3d8
出典データセット
uspto-grants-2011_04
特許番号
US07923573B2

反応ノート

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