Water → 2,5-Diamino-4,6-dichloropyrimidine

HRID 650225ノート

反応式

HRID 650225 の反応式
[ClH:1].[NH2:2][C:3]1[N:8]=[C:7](O)[C:6]([NH2:10])=[C:5](O)[N:4]=1.[Cl:12]CC(Cl)CCl.O=P(Cl)(Cl)Cl.[OH-].[Na+].O.CCCCCC>[Cl-].C[N+](C)(C)C.C(OCC)(=O)C.O1CCCC1>[NH2:2][C:3]1[N:8]=[C:7]([Cl:1])[C:6]([NH2:10])=[C:5]([Cl:12])[N:4]=1

参加物

10

反応物 6

HCID 962WaterHCID 72851,2,3-TrichloropropaneHCID 8058HexaneHCID 14798Sodium HydroxideHCID 24813Phosphorus oxychlorideHCID 178479162HCID 178479162、化合物

生成物 1

HCID 3010392,5-Diamino-4,6-dichloropyrimidine収率 65%

試薬・触媒・溶媒 3

HCID 6379Tetramethylammonium chloride触媒HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒2 回

反応条件

温度
115 °C

実験手順

2,5-Diamino-4,6-dihydroxypyrimidine hydrochloride (0.14 mol, 25 g) was filled into a dry reactor. Dry 1,2,3-trichloropropane (51.96 ml) was then added and the whole was stirred. Subsequently, tetramethylammonium chloride (0.29 mol, 31.25 g) and then POCl3 (0.54-0.81 mol, 124.9-83.28 g, 50.6-75.9 ml) were added. The reaction was heated at reflux temperature (about 115° C.) for 24 h. The reaction was then cooled to below 50° C., ice water (24.44 mol, 440.44 g) was added and the whole was kept below 55° C. Subsequently, the reaction was adjusted to a pH of between 6.5 and 7.0 using 50% strength NaOH (3.12 mol, 124.92 g, 163.3 ml) and the temperature was kept below 55° C. The reaction was stirred at between 50 and 60° C. for 30 min. Tetrahydrofuran (3.7 mol, 267.0 g, 300 ml) was then added. In order to remove undesired material, the whole mixture was filtered through Celite and the filter cake was then washed with ethyl acetate (20.5 mol, 1806.58 g, 2002.86 ml) for subsequent extraction. The organic phase (tetrahydrofuran and ethyl acetate) was washed 3 times with water (5.57 mol, 100.32 g, 100.32 1), dried over NaHCO3 and filtered. Ethyl acetate was removed by vacuum distillation. Hexane (0.77 mol, 66.14 g, 100.36 ml) was then added to the residual organic material, and the whole was cooled to below 10° C., filtered and then dried at 50° C. in vacuo. The title product (0.09 mol, 15.71 g) was obtained as a slightly brownish solid, corresponding to a yield of about 65% based on 2,5-diamino-4,6-dihydroxypyrimidine employed.

後処理

  1. temperatureThe reaction was heated
  2. temperatureThe reaction was then cooled to below 50° C.
  3. customwas kept below 55° C
  4. customwas kept below 55° C
  5. stirringThe reaction was stirred at between 50 and 60° C. for 30 min
  6. customIn order to remove undesired material
  7. filtrationthe whole mixture was filtered through Celite
  8. dry with materialdried over NaHCO3
  9. filtrationfiltered
  10. customEthyl acetate was removed by vacuum distillation
  11. temperaturethe whole was cooled to below 10° C.
  12. filtrationfiltered
  13. customdried at 50° C. in vacuo

出典と根拠

ORDレコード
ord-63d28297242d43a0a89991df4a21eaa3
出典データセット
uspto-grants-2001_08
特許番号
US06271376B1

反応ノート

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