Methanol → 1-(2,6-Difluorobenzyl)-5-methyl-6-(4-nitrophenyl)-3-phenylthieno[2,3-d]pyrimidine-2,4(1h, 3h)-dione

HRID 23253

反応式

HRID 23253 の反応式
CO.C[O-].[Na+].[CH3:6][C:7]1[C:8]([C:31]([O:33]CC)=O)=[C:9]([NH:21][C:22]([NH:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)=[O:23])[S:10][C:11]=1[C:12]1[CH:17]=[CH:16][C:15]([N+:18]([O-:20])=[O:19])=[CH:14][CH:13]=1.[F:36][C:37]1[CH:44]=[CH:43][CH:42]=[C:41]([F:45])[C:38]=1[CH2:39]Br>C(#N)C.O>[F:36][C:37]1[CH:44]=[CH:43][CH:42]=[C:41]([F:45])[C:38]=1[CH2:39][N:21]1[C:9]2[S:10][C:11]([C:12]3[CH:13]=[CH:14][C:15]([N+:18]([O-:20])=[O:19])=[CH:16][CH:17]=3)=[C:7]([CH3:6])[C:8]=2[C:31](=[O:33])[N:24]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:22]1=[O:23]

参加物

7

反応物 4

HCID 887MethanolHCID 5814352-(Bromomethyl)-1,3-difluorobenzeneHCID 10942334Sodium Methoxide2 回HCID 12132337Ethyl 4-methyl-5-(4-nitrophenyl)-2-(3-phenylureido)thiophene-3-carboxylate

生成物 1

HCID 109732041-(2,6-Difluorobenzyl)-5-methyl-6-(4-nitrophenyl)-3-phenylthieno[2,3-d]pyrimidine-2,4(1h, 3h)-dione収率 88.1%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6342Acetonitrile溶媒2 回

実験手順

Acetonitrile (240 ml), methanol (150 ml) and 28% sodium methoxide (15.24 g, 78.97 mmol) were added to ethyl 4-methyl-5-(4-nitrophenyl)-2-(3-phenylureido)thiophene-3-carboxylate (30.00 g, 70.51 mmol), and the mixture was stirred for 1 hour while refluxing under heating. 2,6-difluorobenzyl bromide (17.52 g, 84.61 mmol) was dissolved in acetonitrile (60 ml), and the solution was added to the previous reaction mixture under refluxing. After refluxing under heating for 5 hours, 28% sodium methoxide (1.36 g, 7.05 mmol) was added thereto under reflux, and the mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, water (150 ml) was added dropwise, which was stirred at room temperature for 1 hour. The crystals were filtered and washed with water (240 ml) and diisopropyl ether/ethanol=9/1 (240 ml). The resulting crystals were suspended in ethyl acetate (600 ml), and the suspension was stirred for 1 hour under reflux. The mixture was cooled to room temperature and, after stirred for 1 hour, the crystals were filtered, washed with ethyl acetate (60 ml) and dried under vacuum at 60° C. to give 1-(2,6-difluorobenzyl)-5-methyl-6-(4-nitrophenyl)-3-phenylthieno[2,3-d]pyrimidine-2,4(1H, 3H)-dione (31.4 g, 62.12 mmol, 88.1%).

後処理

  1. temperaturewhile refluxing
  2. temperatureunder heating
  3. additionthe solution was added to the previous reaction mixture
  4. temperatureunder refluxing
  5. temperatureAfter refluxing
  6. temperatureunder heating for 5 hours
  7. temperatureunder reflux
  8. stirringthe mixture was stirred for 1 hour
  9. stirringwhich was stirred at room temperature for 1 hour
  10. filtrationThe crystals were filtered
  11. washwashed with water (240 ml) and diisopropyl ether/ethanol=9/1 (240 ml)
  12. stirringthe suspension was stirred for 1 hour
  13. temperatureunder reflux
  14. temperatureThe mixture was cooled to room temperature
  15. stirringafter stirred for 1 hour
  16. filtrationthe crystals were filtered
  17. washwashed with ethyl acetate (60 ml)
  18. customdried under vacuum at 60° C.

出典と根拠

ORDレコード
ord-e08afe6de2284d92a4677b6bb3884039
出典データセット
uspto-grants-2005_02
特許番号
US06849738B2

関連ノート

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