2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 2,4-Dichloro-5-methoxy-6-vinylpyrimidine

HRID 332917

반응식

HRID 332917 반응식
[Cl:1][C:2]1[NH:3][C:4](Cl)([CH:10]=[CH2:11])[C:5]([O:8][CH3:9])=[CH:6][N:7]=1.[Cl:13]C1N=CC(OC)=C(Cl)N=1.C([Mg]Br)=C.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCCC1>[Cl:1][C:2]1[N:3]=[C:4]([CH:10]=[CH2:11])[C:5]([O:8][CH3:9])=[C:6]([Cl:13])[N:7]=1

참가 물질

6

반응물 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 6014012,4-Dichloro-5-methoxypyrimidineHCID 178418507HCID 178418507, 화합물HCID 178436990HCID 178436990, 화합물

생성물 1

HCID 866893262,4-Dichloro-5-methoxy-6-vinylpyrimidine수율 60%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

실험 절차

2,6-Dichloro-5-methoxy-6-vinyl pyrimidine may be prepared using 2,6-dichloro-5-methoxy pyrimidine, which is commercially available. To a solution of 2,6-dicholoro-5-methoxy pyrimidine (100 g, 0.55 mol) in dry tetrahydrofuran (THF) solvent was added, dropwise, 1M vinyl magnesium bromide in THF solvent (124 g, 0.94 mol) for one hour at room temperature. The mixture was then stirred for 4 h at room temperature. Excess Grignard reagent was quenched by addition of acetone (200 mL) while the temperature of the mixture was maintained at a temperature below 20° C. Thereafter, 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) (151 g, 0.67 mol) was added at once and stirred overnight. A yellow solid precipitated out. The solid was filtered and washed with ethyl acetate (500 mL). The filtrate was concentrated under reduced pressure and the resulting crude compound was diluted with ethyl acetate (2 L). The resulting undissolved, dark, semi-solid was separated by filtration using ethyl acetate. It was further concentrated under reduced pressure to provide a crude compound, which was purified by column chromatography. The compound was eluted with 5% to 10% ethyl acetate in hexane mixture to provide the title compound (70 g, 60% yield): mp 60-61° C.; 1H NMR (CDCl3) δ 3.99 (s, 3H), 5.85 (d, 1H). 6.75 (d, 1H), 6.95 (dd, 1H).

후처리

  1. customExcess Grignard reagent was quenched by addition of acetone (200 mL) while the temperature of the mixture
  2. temperaturewas maintained at a temperature below 20° C
  3. stirringstirred overnight
  4. customA yellow solid precipitated out
  5. filtrationThe solid was filtered
  6. washwashed with ethyl acetate (500 mL)
  7. concentrationThe filtrate was concentrated under reduced pressure
  8. additionthe resulting crude compound was diluted with ethyl acetate (2 L)
  9. customThe resulting undissolved, dark, semi-solid was separated by filtration
  10. concentrationIt was further concentrated under reduced pressure
  11. customto provide a crude compound, which
  12. customwas purified by column chromatography
  13. washThe compound was eluted with 5% to 10% ethyl acetate in hexane mixture

출처 및 근거

ORD 기록
ord-3c085cd3d6dc421f9bafcda1732b2fac
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08877925B2

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