Acetyl chloride → Methyl 5-bromo-2-(methylsulfanyl)pyrimidine-4-carboxylate

HRID 556332

반응식

HRID 556332 반응식
[C:1](Cl)(=O)C.[Br:5][C:6]1[C:7]([C:14]([OH:16])=[O:15])=[N:8][C:9]([S:12][CH3:13])=[N:10][CH:11]=1.C(=O)([O-])O.[Na+]>CO>[CH3:1][O:15][C:14]([C:7]1[C:6]([Br:5])=[CH:11][N:10]=[C:9]([S:12][CH3:13])[N:8]=1)=[O:16]

참가 물질

5

반응물 3

HCID 6367Acetyl chlorideHCID 2917865-Bromo-2-(methylthio)pyrimidine-4-carboxylic AcidHCID 516892Sodium Bicarbonate

생성물 1

HCID 2794729Methyl 5-bromo-2-(methylsulfanyl)pyrimidine-4-carboxylate수율 58.3%

시약·촉매·용매 1

HCID 887Methanol용매

반응 조건

온도
2.5 °C

실험 절차

Acetyl chloride (6.26 ml, 0.088 mol) was added dropwise at 0-5° C. to methanol (100 ml). The mixture was stirred at 0-5° C. for 5 min. 5-Bromo-2-methylsulfanylpyrimidine-4-carboxylic acid (20 g, 0.08 mol) was added in portions at 0-5° C. then the mixture was heated under reflux for 1 h, during which time the slurry dissolved, then it was cooled to ambient temperature and poured into saturated aqueous sodium hydrogencarbonate solution (100 ml). The product was extracted into dichloromethane (3×100 ml), the extracts were washed with water (100 ml), dried (MgSO4) and evaporated in vacuo. The residual solid was crystallised from hexane to give 5-bromo-2-methylsulfanylpyrimidine-4-carboxylic acid methyl ester (12.27 g) as an off white crystalline solid, m.pt. 67-70° C.; 250 MHz 1H-NMR (CDCl3) δ (ppm): 2.6 (s, 3H) (—SCH3), 4.05 (s, 3H) (—OCH3), 8.7 (s, 1H) (ArH); m/z (M+H)+. 249; HPLC purity 96%; HPLC retention time 1.58 min.

후처리

  1. temperaturethe mixture was heated
  2. temperatureunder reflux for 1 h, during which time the slurry
  3. dissolutiondissolved
  4. temperatureit was cooled to ambient temperature
  5. extractionThe product was extracted into dichloromethane (3×100 ml)
  6. washthe extracts were washed with water (100 ml)
  7. dry with materialdried (MgSO4)
  8. customevaporated in vacuo
  9. customThe residual solid was crystallised from hexane

출처 및 근거

ORD 기록
ord-bdf0ccf7a6a84f80aab90ba338cca542
출처 데이터셋
uspto-grants-2011_11
특허 번호
US08058283B2

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