2-((Acetyloxy)methoxy)ethyl acetate → 2-((2,6-Dichloro-9H-purin-9-yl)methoxy)ethyl acetate

HRID 2050020

反応式

HRID 2050020 の反応式
[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([NH:6][CH:7]=[N:8]2)=[C:4]([Cl:11])[N:3]=1.C(O[CH2:16][O:17][CH2:18][CH2:19][O:20][C:21](=[O:23])[CH3:22])(=O)C>>[Cl:1][C:2]1[N:10]=[C:9]2[C:5]([N:6]=[CH:7][N:8]2[CH2:16][O:17][CH2:18][CH2:19][O:20][C:21](=[O:23])[CH3:22])=[C:4]([Cl:11])[N:3]=1

参加物

3

反応物 2

HCID 1009992-((Acetyloxy)methoxy)ethyl acetateHCID 53244122,6-Dichloropurine

生成物 1

HCID 3876662-((2,6-Dichloro-9H-purin-9-yl)methoxy)ethyl acetate収率 64%

反応条件

温度
138 °C

実験手順

2,6-dichloro purine 5.5 g and 2-oxa-1,4-butanediol diacetate 513 g were placed in a flask and partially evacuated and then heated to 138° C., initially the mixture was too thick to stir but gradually gave rise to a melt which was stirred, and after 20 minutes was completely melted and the reaction mixture heated for 10 minutes more (total heat time=30 minutes). The mixture was then cooled to room temperature and para-toluenesulphonic acid 150 mg was added, the vacuum reapplied and heating resumed with stirring. After 20 minutes heating vigorous bubbling was noted, cooled to room temperature, chloroform was added and the solution extracted once with saturated aqueous sodium bicarbonate and once with water. The chloroform phase was dried over anhydrous sodium sulphate and evaporated. The residual oil dissolved in benzene applied to column of 200 g. of silica gel in benzene. Benzene elution removed acetate by products. Ether elution gave 9 isomer yield of 64%. Recrystallisation from benzene to give lustrous white flakes m.p. 96°-99° C.

後処理

  1. custompartially evacuated
  2. stirringgradually gave rise to a melt which was stirred
  3. temperaturethe reaction mixture heated for 10 minutes more (total heat time=30 minutes)
  4. temperatureThe mixture was then cooled to room temperature
  5. additionpara-toluenesulphonic acid 150 mg was added
  6. temperatureheating
  7. stirringwith stirring
  8. temperatureAfter 20 minutes heating vigorous
  9. custombubbling
  10. temperaturecooled to room temperature
  11. additionchloroform was added
  12. extractionthe solution extracted once with saturated aqueous sodium bicarbonate and once with water
  13. dry with materialThe chloroform phase was dried over anhydrous sodium sulphate
  14. customevaporated
  15. dissolutionThe residual oil dissolved in benzene
  16. washBenzene elution
  17. customremoved acetate by products
  18. washEther elution
  19. customgave 9 isomer yield of 64%
  20. customRecrystallisation from benzene
  21. customto give lustrous white flakes m.p. 96°-99° C.

出典と根拠

ORDレコード
ord-ba8f9122ae224cec99f0e2480af27e48
出典データセット
uspto-grants-1980_04
特許番号
US04199574

関連ノート

読み込み中…