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 63962노트

반응식

HRID 63962 반응식
[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]

참가 물질

5

반응물 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

생성물 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)acetate수율 45%

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-fe06a355f6cb4346b565ec4ab1198ca8
출처 데이터셋
uspto-grants-2016_09
특허 번호
US09447116B2

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