Methanol → 5-Diethoxymethyl-3-methyl-thiophene-2-carboxylic acid methyl ester

HRID 1952561노트

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HRID 1952561 반응식
[CH2:1]([O:3][CH:4]([O:10][CH2:11][CH3:12])[C:5]#[C:6][C:7](=O)[CH3:8])[CH3:2].[C:13]([O:17][CH3:18])(=[O:16])[CH2:14][SH:15].CO.C([O-])([O-])=O.[Cs+].[Cs+].[O-]S([O-])(=O)=O.[Mg+2]>C1COCC1>[CH3:18][O:17][C:13]([C:14]1[S:15][C:5]([CH:4]([O:10][CH2:11][CH3:12])[O:3][CH2:1][CH3:2])=[CH:6][C:7]=1[CH3:8])=[O:16]

참가 물질

6

반응물 4

HCID 887MethanolHCID 16907Methyl ThioglycolateHCID 414415,5-Diethoxy-3-pentyn-2-oneHCID 86671257Cs2CO3 MgSO4

생성물 1

HCID 682264465-Diethoxymethyl-3-methyl-thiophene-2-carboxylic acid methyl ester수율 83%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

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온도
0 °C

실험 절차

A solution of 5,5-diethoxy-pent-3yne-2-one (3.51 g, 20.6 mmol) in THF (30 ml) was cooled to 0° C. (ice bath). Methyl thioglycolate (1.84 ml, 20.6 mmol) was added in one portion and the mixture was stirred at 0° C. for 2 h. Methanol (10 ml) and Cs2CO3/MgSO4 (7 g/14 g, pre-dried at 200° C. in vacuum) were added at 0° C. The mixture was stirred at 0° C. for 15 min and then at rt for 2.5 h. The reaction mixture was quenched by pouting into ice and 1M NaH2PO4 (100 ml), then extracted with EtOAc. The layers were separated. The organic layer was washed with brine, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by flash chromatography with 5-15% EtOAc in hexane to afford the desired product (4.41 g, 83% yield).

후처리

  1. stirringThe mixture was stirred at 0° C. for 15 min
  2. waitat rt for 2.5 h
  3. customThe reaction mixture was quenched
  4. extractionextracted with EtOAc
  5. customThe layers were separated
  6. washThe organic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography with 5-15% EtOAc in hexane

출처 및 근거

ORD 기록
ord-4200bff8eafe493e86abaa78457b377b
출처 데이터셋
uspto-grants-2013_03
특허 번호
US08404859B2

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