Potassium Iodide → Ethyl 2-(6-chloro-4-oxo-1,4-dihydropyrimidin-2-yl)acetate

HRID 2278539ノート

反応式

HRID 2278539 の反応式
[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C:6]1[N:11]=[C:10]([Cl:12])[CH:9]=[C:8]([O:13]C)[N:7]=1)[CH3:2].C(#N)C.[I-].[K+].C[Si](C)(C)Cl>O>[CH2:1]([O:3][C:4](=[O:15])[CH2:5][C:6]1[NH:7][C:8](=[O:13])[CH:9]=[C:10]([Cl:12])[N:11]=1)[CH3:2]

参加物

6

反応物 4

HCID 4875Potassium IodideHCID 6342AcetonitrileHCID 6397ChlorotrimethylsilaneHCID 86699270Ethyl 2-(4-chloro-6-methoxypyrimidin-2-yl)acetate

生成物 1

HCID 136378677Ethyl 2-(6-chloro-4-oxo-1,4-dihydropyrimidin-2-yl)acetate収率 81%

試薬・触媒・溶媒 1

HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

33 g of (4-chloro-6-methoxypyrimidin-2-yl)acetic acid ethyl ester (example 8b, step 2b) and 750 ml of acetonitrile are placed in a 1000 ml autoclave and then 71.2 g of potassium iodide and 55.85 ml of trimethylchlorosilane are added; an orangey-colored heterogeneous solution is obtained, which is stirred while heating under an argon pressure of 10 bar at 100° C. for 2 hours. The reaction medium is drawn off and then the insoluble material is filtered off and washed with 3 times approximately 100 ml of EtOAc, and the filtrate is concentrated until a pasty residue is obtained, which is taken up in 500 ml of water. After stirring and extraction with 3 times approximately 350 ml of ethyl acetate, the combined organic extracts are washed with 500 ml of saturated NaCl solution, dried over MgSO4, filtered through a VF filter, and concentrated under vacuum. The compound obtained is purified by chromatography on silica gel (40-63 μm), elution being carried out with a mixture of 2/8 v/v EtOAc/n-heptane. The fractions containing the expected compound are combined and evaporated. A solid is isolated, which is triturated from diisopropyl ether, filtered through sintered glass and dried. (4-Chloro-6-oxo-1,6-dihydropyrimidin-2-yl)acetic acid ethyl ester is isolated in the form of a beige solid: 25.2 g; yield 81%

後処理

  1. customan orangey-colored heterogeneous solution is obtained
  2. filtrationthe insoluble material is filtered off
  3. washwashed with 3 times approximately 100 ml of EtOAc
  4. concentrationthe filtrate is concentrated until a pasty residue
  5. customis obtained
  6. stirringAfter stirring
  7. extractionextraction with 3 times approximately 350 ml of ethyl acetate
  8. washthe combined organic extracts are washed with 500 ml of saturated NaCl solution
  9. dry with materialdried over MgSO4
  10. filtrationfiltered through a VF
  11. filtrationfilter
  12. concentrationconcentrated under vacuum
  13. customThe compound obtained
  14. customis purified by chromatography on silica gel (40-63 μm), elution
  15. additionbeing carried out with a mixture of 2/8 v/v EtOAc/n-heptane
  16. additionThe fractions containing the expected compound
  17. customevaporated
  18. customA solid is isolated
  19. customwhich is triturated from diisopropyl ether
  20. filtrationfiltered through sintered glass
  21. customdried

出典と根拠

ORDレコード
ord-d1186a4f9bf044a6b1ce9fd7a73155e1
出典データセット
uspto-grants-2015_09
特許番号
US09133168B2

反応ノート

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