Thiophene → 2-Chloro-4-methyl-6-(2-thienyl)pyrimidine

HRID 1872030노트

반응식

HRID 1872030 반응식
[S:1]1[CH:5]=[CH:4][CH:3]=[CH:2]1.C([Li])CCC.[Cl:11][C:12]1[N:17]=[C:16]([CH3:18])[CH:15]=[CH:14][N:13]=1>CCOCC>[Cl:11][C:12]1[N:17]=[C:16]([CH3:18])[CH:15]=[C:14]([C:2]2[S:1][CH:5]=[CH:4][CH:3]=2)[N:13]=1

참가 물질

5

반응물 3

HCID 8030ThiopheneHCID 116296072-Chloro-4-methylpyrimidineHCID 178418339Butyllithium

생성물 1

HCID 183237602-Chloro-4-methyl-6-(2-thienyl)pyrimidine수율 12.8%

시약·촉매·용매 1

HCID 3283Diethyl Ether용매2회

반응 조건

온도
0 °C

실험 절차

Part B: To thiophene (0.66 g) in dry ether (25 mL) at 0° C. was added n-butyl lithium in hexanes (1.6 M, 2.7 mL) and the reaction was stirred at 0° C. for 15 minutes. After cooling to -30° C., a solution of 2-chloro-4-methylpyrimidine (1.0 g) in ether (10 mL) was slowly added and the reaction was stirred at -30° C. for 30 minutes and at 0° C. an additional 30 minutes before quenching with a mixture of acetic acid (glacial, 0.45 mL), water (0.5 mL) and tetrahydrofuran (1.0 mL). 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (1.77 g) in tetrahydrofuran (5 mL) was added and the reaction mixture was stirred at room temperature for 5 minutes, then cooled to 0° C. before aq. sodium hydroxide solution (3 M, 50 mL) was added. The organic layer was separated, washed with water, and dried with magnesium sulfate. The solvent was evaporated and the resultant crude oil was chromatographed on silica gel (30% ethyl acetate in hexanes; Rf 0.55) to yield 2-chloro-4-methyl-6-(2-thienyl)pyrimidine (0.21 g). Anal. Calc.: % C: 51.46: % H: 3.33: % N: 13.33. Found: % C: 51.77: % H: 3.35; % N: 12.97.

후처리

  1. temperatureAfter cooling to -30° C.
  2. stirringthe reaction was stirred at -30° C. for 30 minutes and at 0° C. an additional 30 minutes
  3. custombefore quenching with a mixture of acetic acid (glacial, 0.45 mL), water (0.5 mL) and tetrahydrofuran (1.0 mL)
  4. addition2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (1.77 g) in tetrahydrofuran (5 mL) was added
  5. stirringthe reaction mixture was stirred at room temperature for 5 minutes
  6. temperaturecooled to 0° C. before aq. sodium hydroxide solution (3 M, 50 mL)
  7. additionwas added
  8. customThe organic layer was separated
  9. washwashed with water
  10. dry with materialdried with magnesium sulfate
  11. customThe solvent was evaporated
  12. customthe resultant crude oil was chromatographed on silica gel (30% ethyl acetate in hexanes; Rf 0.55)

출처 및 근거

ORD 기록
ord-cbf078d734094537822dc354e67b9a36
출처 데이터셋
uspto-grants-2000_08
특허 번호
US06107301

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