Sulfuric Acid → Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(tert-butoxy)acetate

HRID 2406399ノート

反応式

HRID 2406399 の反応式
[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:6]=1[C:12]1[C:17]([CH:18]([OH:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[C:16]([CH3:25])[N:15]=[C:14]2[S:26][C:27]3[CH2:32][CH2:31][CH2:30][CH2:29][C:28]=3[C:13]=12)[CH:2]=[CH2:3].C(O[C:37]([CH3:40])([CH3:39])[CH3:38])(=O)C.S(=O)(=O)(O)O>ClCCl>[CH2:1]([O:4][C:5]1[CH:10]=[C:9]([CH3:11])[CH:8]=[CH:7][C:6]=1[C:12]1[C:17]([CH:18]([O:24][C:37]([CH3:40])([CH3:39])[CH3:38])[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[C:16]([CH3:25])[N:15]=[C:14]2[S:26][C:27]3[CH2:32][CH2:31][CH2:30][CH2:29][C:28]=3[C:13]=12)[CH:2]=[CH2:3]

参加物

5

反応物 3

HCID 1118Sulfuric AcidHCID 10908tert-Butyl acetateHCID 69672380Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetate

生成物 1

HCID 67890974Ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(tert-butoxy)acetate収率 45%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

To a stirred solution of ethyl {4-[2-(allyloxy)-4-methylphenyl]-2-methyl-5,6,7,8-tetrahydro[1]benzothieno[2,3-b]pyridin-3-yl}(hydroxy)acetate (Step 7, 720 mg, 1.59 mmol) in dichloromethane (2.5 mL) was added tert-butyl acetate (2.5 mL) followed by concentrated sulphuric acid (244 μL, 4.78 mmol) and the reaction was stirred at room temperature for 2 hours. The reaction mixture was quenched by addition of a 1 M aqueous sodium hydroxide solution until the solution was at pH 5. The volatile solvents were removed in vacuo, and the remaining aqueous layer was extracted with ethyl acetate (30 mL). The organic layer was washed with brine (10 mL), dried over MgSO4 and concentrated in vacuo. The residue was purified using ISCO Companion with a Redisep silica gel 12 g cartridge and a gradient of heptane and ethyl acetate (0% to 40%). Product containing fractions were concentrated in vacuo to give a mixture of diastereoisomers of the title compound as a colourless oil, 370 mg, in a 45% yield. Material is shown to be a mixture of diastereomers, in an approximately 80:20 ratio.

後処理

  1. customThe reaction mixture was quenched by addition of a 1 M aqueous sodium hydroxide solution until the solution
  2. customThe volatile solvents were removed in vacuo
  3. extractionthe remaining aqueous layer was extracted with ethyl acetate (30 mL)
  4. washThe organic layer was washed with brine (10 mL)
  5. dry with materialdried over MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified
  8. additionProduct containing fractions
  9. concentrationwere concentrated in vacuo
  10. customto give

出典と根拠

ORDレコード
ord-4b2a88d622974301bead207c624959cb
出典データセット
uspto-grants-2014_08
特許番号
US08809363B2

反応ノート

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