p-Toluenesulfonic acid → 4-methyl-2-(methylthio)-6-(1H-pyrazol-4-ylamino)-5-pyrimidinecarbonitrile

HRID 390053ノート

反応式

HRID 390053 の反応式
Cl[C:2]1[C:7]([C:8]#[N:9])=[C:6]([CH3:10])[N:5]=[C:4]([S:11][CH3:12])[N:3]=1.C1(S([N:22]2[CH:26]=[C:25]([NH2:27])[CH:24]=[N:23]2)(=O)=O)C=CC=CC=1.CC1C=CC(S(O)(=O)=O)=CC=1>O1CCOCC1>[CH3:10][C:6]1[C:7]([C:8]#[N:9])=[C:2]([NH:27][C:25]2[CH:26]=[N:22][NH:23][CH:24]=2)[N:3]=[C:4]([S:11][CH3:12])[N:5]=1

参加物

5

反応物 3

HCID 6101p-Toluenesulfonic acidHCID 582963084-Chloro-6-methyl-2-(methylthio)pyrimidine-5-carbonitrileHCID 582963261-(phenylsulfonyl)-1H-pyrazol-4-amine

生成物 1

HCID 672232944-methyl-2-(methylthio)-6-(1H-pyrazol-4-ylamino)-5-pyrimidinecarbonitrile収率 45.4%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

反応条件

温度
90 °C

実験手順

To a solution of 4-chloro-6-methyl-2-(methylthio)pyrimidine-5-carbonitrile (6.45 g, 32.2 mmol) and 1-(phenylsulfonyl)-1H-pyrazol-4-amine (7.2 g, 32.2 mmol) in 1,4-dioxane (150 mL) was added 4-methylbenzenesulfonic acid (3.06 g, 16.1 mmol). The reaction mixture was stirred overnight at 90° C. After cooling to room temperature, the precipitate was filtered, washed with saturated NaHCO3 solution and then water, dried and washed with petroleum and the mixture solvent (petroleum ether:ethyl acetate=4:1) successively to give 4-methyl-2-(methylthio)-6-(1H-pyrazol-4-ylamino)-5-pyrimidinecarbonitrile (intermediate 30, 3.6 g) as a pale solid. MS: M(C10H10N6S)=246.30, (M+1)+=247.1; 1HNMR (300 mHz, DMSO-d6) δ ppm 12.69 (1H, s), 9.87 (1H, s), 7.97 (1H, s), 3.33 (3H, m), 2.42 (3H, s). The organic eluents were concentrated under reduced pressure and the residue was treated with the same method above to afford 4-methyl-2-(methylthio)-6-{[1-(phenylsulfonyl)-1H-pyrazol-4-yl]amino}-5-pyrimidinecarbonitrile (intermediate 29, 4.26 g, 34.4% yield) as a yellow solid.

後処理

  1. temperatureAfter cooling to room temperature
  2. filtrationthe precipitate was filtered
  3. washwashed with saturated NaHCO3 solution
  4. dry with materialwater, dried
  5. washwashed with petroleum

出典と根拠

ORDレコード
ord-4d9cac57ee3d42fa829e969158e40b08
出典データセット
uspto-grants-2013_02
特許番号
US08383635B2

反応ノート

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