Benzyl Bromide → 3-benzyl-5-bromo-2-(methylthio)pyrimidin-4(3H)-one

HRID 2246473노트

반응식

HRID 2246473 반응식
[Br:1][C:2]1[C:3](=[O:10])[NH:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=1.[CH2:11](Br)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>C1COCC1>[CH2:11]([N:4]1[C:3](=[O:10])[C:2]([Br:1])=[CH:7][N:6]=[C:5]1[S:8][CH3:9])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

참가 물질

4

반응물 2

HCID 7498Benzyl Bromide2회HCID 2405655-Bromo-2-(methylsulfanyl)pyrimidin-4(3H)-one

생성물 1

HCID 592183763-benzyl-5-bromo-2-(methylthio)pyrimidin-4(3H)-one수율 12.6%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매

실험 절차

5-bromo-2-(methylthio)pyrimidin-4(3H)-one (3.63 g, 16.4 mmol) was suspended in THF (80 ml) and CaH2 powder (1.29, 32.3 mmol) and benzyl bromide (2.6 ml, 22 mmol) were added. The reaction flask was fitted with a reflux condenser and placed in a preheated oil bath (65 C-70 C) and stirred overnight. After 15.5 hours, more benzyl bromide (0.7 ml, 6 mmol) was added, and the temperature of the oil bath was raised to 87 C to achieve reflux. After 19 more hours, the reaction was cooled to 0 C and quenched cautiously with ice water first, and then with water (40 ml). The reaction was warmed to room temperature and stirred as more water (40 ml) and then brine (30 ml) were added. The reaction was extracted with a DCM/MeOH mixture, and the organic extractions were combined, dried over sodium sulfate, filtered, and concentrated. The crude residue was filtered through silica gel (˜3 inches, DCM) to afford the desired 3-benzyl-5-bromo-2-(methylthio)pyrimidin-4(3H)-one (642 mg, 2.06 mmol, 90% purity, 11% yield). MS (ESI pos. ion) m/z: 311 (MH+), 313 (MH+). Calc'd exact mass for C12H11BrN2OS: 310, 312. 1HNMR (400 MHz, CDCl3): 8.09 (s, 1H), 7.42-7.29 (m, 5H), 5.34 (s, 2H), 2.54 (s, 3H).

후처리

  1. customThe reaction flask was fitted with a reflux condenser
  2. customplaced in a preheated oil bath
  3. waitAfter 15.5 hours
  4. temperaturethe temperature of the oil bath was raised to 87 C
  5. temperatureto achieve reflux
  6. temperatureAfter 19 more hours, the reaction was cooled to 0 C
  7. customquenched cautiously with ice water first
  8. stirringstirred as more water (40 ml)
  9. additionbrine (30 ml) were added
  10. extractionThe reaction was extracted with a DCM/MeOH mixture
  11. extractionthe organic extractions
  12. dry with materialdried over sodium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated
  15. filtrationThe crude residue was filtered through silica gel (˜3 inches, DCM)

출처 및 근거

ORD 기록
ord-7572c229b84d472cb70e6b6df3655560
출처 데이터셋
uspto-grants-2010_03
특허 번호
US07687522B2

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