p-Toluenesulfonic acid → HCID 18425436、化合物

HRID 1280552ノート

反応式

HRID 1280552 の反応式
[CH3:1][NH:2][C:3]1[C:8]([CH:9]=S)=[CH:7][N:6]=[C:5](C)[N:4]=1.[Cl:12][C:13]1[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[C:14]=1[NH2:15].C1(C)C=C[C:24]([S:27](O)(=O)=O)=CC=1.[BH4-].[Na+]>C1(C)C=CC=CC=1.O>[Cl:12][C:13]1[CH:19]=[CH:18][CH:17]=[C:16]([Cl:20])[C:14]=1[NH:15][CH2:9][C:8]1[C:3]([NH:2][CH3:1])=[N:4][C:5]([S:27][CH3:24])=[N:6][CH:7]=1

参加物

7

反応物 4

HCID 6101p-Toluenesulfonic acidHCID 118462,6-DichloroanilineHCID 4311764Sodium borohydrideHCID 865928692-Methyl-4-(methylamino)pyrimidine-5-carbothialdehyde

生成物 1

HCID 18425436HCID 18425436、化合物収率 298%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 1140Toluene溶媒

反応条件

温度
75 °C

実験手順

A mixture of 4-methylamino-2-methylthiopyrimidine-5-carboxaldehyde (6 g, 32.8 mmol), 2,6-dichloroaniline (5.5 g, 33.9 mmol) and 4-toluene-sulfonic acid (1 g, 5.3 mmol) in 70 mL of toluene was heated under reflux with azeotropic removal of water for 17 hours. The mixture was concentrated to a volume of about 10 mL under reduced pressure and then treated with 120 mL of ethanol. The suspension obtained was heated to 75° C. and treated over a period of 15 minutes with 6.2 g (160 mmol) of sodium borohydride pellets. The mixture was stirred for a further 15 minutes and cooled to room temperature. The solvent was evaporated under reduced pressure and the residue was stirred in a mixture of 200 mL of 2M sodium hydroxide solution and 200 mL of ethyl acetate for 1 hour. The phases were separated and the organic phase was dried over magnesium sulfate and filtered. Evaporation of the filtrate under reduced pressure and flash chromatography of the residue using 3:7 diethyl ether/hexane for the elution gave 5.2 g (48%) of 5-(2,6-dichlorophenyl)aminomethyl-4-methylamino-2-methylthio-pyrimidine as a white solid.

後処理

  1. temperaturewas heated
  2. concentrationThe mixture was concentrated to a volume of about 10 mL under reduced pressure
  3. additiontreated with 120 mL of ethanol
  4. customThe suspension obtained
  5. temperaturecooled to room temperature
  6. customThe solvent was evaporated under reduced pressure
  7. stirringthe residue was stirred in a mixture of 200 mL of 2M sodium hydroxide solution and 200 mL of ethyl acetate for 1 hour
  8. customThe phases were separated
  9. dry with materialthe organic phase was dried over magnesium sulfate
  10. filtrationfiltered
  11. customEvaporation of the filtrate under reduced pressure and flash chromatography of the residue
  12. washfor the elution

出典と根拠

ORDレコード
ord-af3f1183d80e4ac0801c178266ad1aaa
出典データセット
uspto-grants-2002_09
特許番号
US06451804B1

反応ノート

読み込み中…