p-Toluenesulfonic acid → 5-(4-(4-Methoxybenzylamino)-5-nitropyridin-2-ylamino)pyrazine-2-carbonitrile

HRID 40653

反応式

HRID 40653 の反応式
[NH2:1][C:2]1[CH:7]=[N:6][C:5]([C:8]#[N:9])=[CH:4][N:3]=1.CC(C)([O-])C.[Na+].[CH3:16][O:17][C:18]1[CH:35]=[CH:34][C:21]([CH2:22][NH:23][C:24]2[C:29]([N+:30]([O-:32])=[O:31])=[CH:28][N:27]=[C:26](Br)[CH:25]=2)=[CH:20][CH:19]=1.CC1C=CC(S(O)(=O)=O)=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.CN(C=O)C.C1(C)C=CC=CC=1>[CH3:16][O:17][C:18]1[CH:19]=[CH:20][C:21]([CH2:22][NH:23][C:24]2[C:29]([N+:30]([O-:32])=[O:31])=[CH:28][N:27]=[C:26]([NH:1][C:2]3[N:3]=[CH:4][C:5]([C:8]#[N:9])=[N:6][CH:7]=3)[CH:25]=2)=[CH:34][CH:35]=1

参加物

8

反応物 4

HCID 6101p-Toluenesulfonic acidHCID 139252945-Aminopyrazine-2-carbonitrileHCID 23676156Sodium t-butoxideHCID 56926468N-(4-Methoxybenzyl)-2-bromo-5-nitropyridin-4-amine

生成物 1

HCID 670174595-(4-(4-Methoxybenzylamino)-5-nitropyridin-2-ylamino)pyrazine-2-carbonitrile収率 73.5%

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
140 °C

実験手順

A mixture of palladium (II) acetate (38 mg, 0.17 mmol) and (±)-2,2″-bis(diphenylphosphino)-1,1″-binaphthalene (318 mg, 0.51 mmol) a mixture of toluene and DMF (1:1, 10 mL) was degassed under a stream of nitrogen gas with stirring for 30 minutes. After addition of 2-amino-5-cyanopyrazine (245 mg, 2.04 mmol), sodium tert-butoxide (196 mg, 2.04 mmol) and N-(4-methoxybenzyl)-2-bromo-5-nitropyridin-4-amine (575 mg, 1.70 mmol), the mixture was degassed for a further 5 minutes and then heated at 140° C. for 30 minutes in a microwave reactor. Upon cooling, the mixture was diluted with methanol and isolated by SPE using 3×2.5 g MP-TsOH cartridges, washing with methanol and then eluting with 2 M ammonia in methanol. The basic fractions were concentrated in vacuo to give the title compound (470 mg, 1.25 mmol, 73%) which was used without further purification. LCMS (2) Rt=2.18 min; m/z (ESI−) 376 (M−H); (ESI+) 378 (MH+).

後処理

  1. customwas degassed under a stream of nitrogen gas
  2. customthe mixture was degassed for a further 5 minutes
  3. temperatureUpon cooling
  4. additionthe mixture was diluted with methanol
  5. customisolated by SPE
  6. washwashing with methanol
  7. washeluting with 2 M ammonia in methanol
  8. concentrationThe basic fractions were concentrated in vacuo

出典と根拠

ORDレコード
ord-6d62885f688b441e9b69920bbe819d35
出典データセット
uspto-grants-2013_09
特許番号
US08530468B2

関連ノート

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