Ethanol → 2-Amino-4-anilino-6-methylaminopyrimidine

HRID 539435ノート

反応式

HRID 539435 の反応式
[NH2:1][C:2]1[N:7]=[C:6](Cl)[CH:5]=[C:4]([NH:9][CH3:10])[N:3]=1.NC1[N:17]=[C:16](Cl)[CH:15]=[C:14](Cl)N=1.[CH3:20]N.[CH2:22](O)[CH3:23]>>[NH2:1][C:2]1[N:7]=[C:6]([NH:17][C:16]2[CH:15]=[CH:14][CH:23]=[CH:22][CH:20]=2)[CH:5]=[C:4]([NH:9][CH3:10])[N:3]=1

参加物

5

反応物 4

HCID 702EthanolHCID 6329MethylamineHCID 655222-Amino-4,6-dichloropyrimidine2 回HCID 2354466-Chloro-n4-methylpyrimidine-2,4-diamine

生成物 1

HCID 807680532-Amino-4-anilino-6-methylaminopyrimidine

反応条件

温度
70 °C

実験手順

2-Amino-4-anilino-6-methylaminopyrimidine was synthesized, via 2-amino-4-chloro-6-methylaminopyrimidine, with 2-amino-4,6-dichloropyrimidine as a starting material. 2-Amino-4,6-dichloropyrimidine (32.8 g), a 40% aqueous methylamine solution (34.5 mL), and ethanol (300 mL) were mixed, followed by stirring at an internal temperature of 70° C. for 4 hours. Subsequently, the solvent was concentrated under reduced pressure, and crystallization from acetonitrile was performed. The product was collected by filtration and was used without purification for the subsequent step. The crude product of 2-amino-4-chloro-6-methylaminopyrimidine, aniline (27.4 mL), methoxyethanol (100 mL), and hydrochloric acid (0.2 mL) were mixed, followed by stirring with heating at 120° C. for 3 hours. After cooling, the reaction solution was added to sodium bicarbonate water (500 mL)/ethyl acetate under ice cooling to extract the product with ethyl acetate. After concentration, purification by column chromatography (ethyl acetate/methanol) was performed to yield 18 g of 2-amino-4-anilino-6-methylaminopyrimidine. Synthesis was performed as in Synthetic example 1a-1 with 2-amino-4-anilino-6-methylaminopyrimidine, methyl m-methylbenzoate, and sodium methoxide. The product was purified by silica gel column chromatography using ethyl acetate/n-hexane and recrystallization from ethyl acetate/n-hexane to yield compound (6-14).

後処理

  1. concentrationSubsequently, the solvent was concentrated under reduced pressure, and crystallization from acetonitrile
  2. filtrationThe product was collected by filtration
  3. customwas used without purification for the subsequent step
  4. additionThe crude product of 2-amino-4-chloro-6-methylaminopyrimidine, aniline (27.4 mL), methoxyethanol (100 mL), and hydrochloric acid (0.2 mL) were mixed
  5. stirringby stirring
  6. temperaturewith heating at 120° C. for 3 hours
  7. temperatureAfter cooling
  8. additionthe reaction solution was added to sodium bicarbonate water (500 mL)/ethyl acetate under ice cooling
  9. extractionto extract the product with ethyl acetate
  10. concentrationAfter concentration, purification by column chromatography (ethyl acetate/methanol)

出典と根拠

ORDレコード
ord-8170324a271a45eb93e0c255e6663fee
出典データセット
uspto-grants-2014_10
特許番号
US08871314B2

反応ノート

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