Pyridine → Matairesinol Methylsuccinate

HRID 490785노트

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HRID 490785 반응식
[C:1]([O:8]C)(=[O:7])[CH2:2][CH2:3][C:4]([O-:6])=[O:5].[CH3:10][O:11][C:12]1[CH:13]=[C:14]([CH2:19][C@@H:20]2[C@@H:25]([CH2:26][C:27]3[CH:28]=[CH:29][C:30]([OH:35])=[C:31]([O:33][CH3:34])[CH:32]=3)[C:23](=[O:24])[O:22][CH2:21]2)[CH:15]=[CH:16][C:17]=1[OH:18].N1C=CC=C[CH:37]=1>C(Cl)Cl>[CH3:10][O:11][C:12]1[CH:13]=[C:14]([CH2:19][C@@H:20]2[C@@H:25]([CH2:26][C:27]3[CH:28]=[CH:29][C:30]([OH:35])=[C:31]([O:33][CH3:34])[CH:32]=3)[C:23](=[O:24])[O:22][CH2:21]2)[CH:15]=[CH:16][C:17]=1[OH:18].[CH3:37][CH:3]([CH2:2][C:1]([O-:8])=[O:7])[C:4]([O-:6])=[O:5]

참가 물질

5

반응물 3

HCID 1049PyridineHCID 119205(-)-Matairesinol3회HCID 6930703Mono-Methyl Succinate

생성물 1

HCID 86597912Matairesinol Methylsuccinate

시약·촉매·용매 1

HCID 6344Dichloromethane용매

반응 조건

온도
60 °C

실험 절차

Monomethyl succinate (1 g, 7.56 mmol) was stirred in a flame dried round bottomed flask. Thionyl chloride was added (30 ml, 4.5 g) dropwise and the mixture was heated to 60° C. for 3 h. Then, excess thionyl chloride was remowed under reduced pressure and the residue was analysed by NMR spectroscopy. The fully chlorinated product was dissolved in 20 ml dry CH2Cl2 and dropwise added to a solution of matairesinol (1 g) in 40 ml CH2Cl2 and 1.8 g pyridine (8 eqv.) at 0° C. The mixture was stirred and allowed to warm to room temp over night. The mixture was then extracted with 2×50 ml water and the organic phase was dried and concentrated. The residue was chromatographed on a silica column (eluent EtOAc:PE 1:1) to yield a fraction containing the product. Yield 1.1 g (purity 80%, NMR, some other components present). The product was rechromatographed with CHCl3 to yield 0.92 g (70%) of a pure fraction containing two components, totally coeluting. The mixture was analysed with LC-MS (ESI-ion trap) and the components were identified as free matairesinol and matairesinol bis methylsuccinate (product). According to NMR analyses the product contained approximately 15% free matairesinol. It seems unlikely that the components can be separated by normal column chromatography. However, pure product can probably be obtained by varying the ratio of reagents (excess of acid chloride).

후처리

  1. customdried round bottomed flask
  2. additionThionyl chloride was added (30 ml, 4.5 g) dropwise
  3. dissolutionThe fully chlorinated product was dissolved in 20 ml dry CH2Cl2
  4. temperatureto warm to room temp over night
  5. extractionThe mixture was then extracted with 2×50 ml water
  6. customthe organic phase was dried
  7. concentrationconcentrated
  8. customThe residue was chromatographed on a silica column (eluent EtOAc:PE 1:1)
  9. customto yield a fraction
  10. additioncontaining the product
  11. customThe product was rechromatographed with CHCl3
  12. customto yield 0.92 g (70%) of a pure fraction
  13. additioncontaining two components
  14. customcan be separated by normal column chromatography
  15. customHowever, pure product can probably be obtained

출처 및 근거

ORD 기록
ord-facdda0d6eea42bca4da3b154804ff72
출처 데이터셋
uspto-grants-2009_05
특허 번호
US07528166B2

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