4-Toluenesulfonyl chloride → 5-Bromo-3-(5-tert-butyl-1,3,4-oxadiazol-2-yl)pyrazin-2-amine

HRID 1749672ノート

反応式

HRID 1749672 の反応式
C1(C)C=CC(S(Cl)(=O)=O)=CC=1.[NH2:12][C:13]1[C:14]([C:20]([NH:22][NH:23][C:24](=[O:29])[C:25]([CH3:28])([CH3:27])[CH3:26])=O)=[N:15][C:16]([Br:19])=[CH:17][N:18]=1.C(N(CC)C(C)C)(C)C>C(#N)C>[Br:19][C:16]1[N:15]=[C:14]([C:20]2[O:29][C:24]([C:25]([CH3:26])([CH3:27])[CH3:28])=[N:23][N:22]=2)[C:13]([NH2:12])=[N:18][CH:17]=1

参加物

5

反応物 3

HCID 73974-Toluenesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 867276593-amino-6-bromo-N'-pivaloylpyrazine-2-carbohydrazide

生成物 1

HCID 867276555-Bromo-3-(5-tert-butyl-1,3,4-oxadiazol-2-yl)pyrazin-2-amine収率 87.4%

試薬・触媒・溶媒 1

HCID 6342Acetonitrile溶媒

反応条件

温度
70 °C

実験手順

p-Toluenesulfonyl chloride (164 g, 861.60 mmol) was added portion wise to a suspension of 3-amino-6-bromo-N′-pivaloylpyrazine-2-carbohydrazide (227 g, 718.00 mmol) and N,N-diisopropylethylamine (297 mL, 1795.01 mmol) in acetonitrile (2200 mL). The mixture was stirred for 2 hours at 70° C. The reaction was left to cool to room temperature overnight. The reaction mixture was partitioned between ethyl acetate (2 L) and sodium bicarbonate solution (2 L). The organic layer was washed with saturated brine, dried with magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting brown/beige solid was triturated with hot MTBE (1000 mL) and isolated by filtration and dried to afford 5-bromo-3-(5-tert-butyl-1,3,4-oxadiazol-2-yl)pyrazin-2-amine as a yellow solid (187 g, 87%). The mother liquors were evaporated to dryness. The crude solid was triturated with MTBE (500 mL) filtered and washed with 100 mL of MTBE. The resulting solid was air dried overnight to afford a second crop of 5-bromo-3-(5-tert-butyl-1,3,4-oxadiazol-2-yl)pyrazin-2-amine (36 g, 17%): 1H NMR Spectrum: (DMSO-d6) 1.43 (9H, s), 7.70 (2H, s), 8.39 (1H, s); Mass Spectrum [M+H]+=298.

後処理

  1. waitThe reaction was left
  2. temperatureto cool to room temperature overnight
  3. customThe reaction mixture was partitioned between ethyl acetate (2 L) and sodium bicarbonate solution (2 L)
  4. washThe organic layer was washed with saturated brine
  5. dry with materialdried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe resulting brown/beige solid was triturated with hot MTBE (1000 mL)
  9. customisolated by filtration
  10. customdried

出典と根拠

ORDレコード
ord-e24d121fd5bb45448efabb0dbd0dd691
出典データセット
uspto-grants-2015_10
特許番号
US09156831B2

反応ノート

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