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

HRID 556332

反応式

HRID 556332 の反応式
[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]

参加物

5

反応物 3

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

反応条件

温度
2.5 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-bdf0ccf7a6a84f80aab90ba338cca542
出典データセット
uspto-grants-2011_11
特許番号
US08058283B2

関連ノート

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