6-Mercapto-3-methyl-1-(2-methylpropyl)-2,4(1H,3H)-pyrimidinedione → Methyl 1-isobutyl-3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidine-5-carboxylate

HRID 131554

반응식

HRID 131554 반응식
[SH:1][C:2]1[N:7]([CH2:8][CH:9]([CH3:11])[CH3:10])[C:6](=[O:12])[N:5]([CH3:13])[C:4](=[O:14])[CH:3]=1.Br[CH:16]([CH3:23])[C:17](=O)[C:18]([O:20][CH3:21])=[O:19]>C([O-])(=O)C.[Na+].O.C(Cl)Cl.[Ti](Cl)(Cl)(Cl)Cl>[CH3:13][N:5]1[C:4](=[O:14])[C:3]2[C:17]([C:18]([O:20][CH3:21])=[O:19])=[C:16]([CH3:23])[S:1][C:2]=2[N:7]([CH2:8][CH:9]([CH3:11])[CH3:10])[C:6]1=[O:12]

참가 물질

7

반응물 2

HCID 52825676-Mercapto-3-methyl-1-(2-methylpropyl)-2,4(1H,3H)-pyrimidinedioneHCID 11183175Methyl 3-bromo-2-oxobutanoate

생성물 1

HCID 5282532Methyl 1-isobutyl-3,6-dimethyl-2,4-dioxo-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidine-5-carboxylate수율 59.2%

시약·촉매·용매 4

HCID 24193Titanium Tetrachloride촉매HCID 962Water용매HCID 6344Dichloromethane용매HCID 517045Sodium Acetate용매

실험 절차

6-Mercapto-3-methyl-1-(isobutyl)-pyrimidine-2,4(1H,3H)-dione (50 g) was dissolved in a solution of sodium acetate (95.6 g) in water (1.5 L), and methyl 3-bromo-2-oxo-butanoate (44.6 g) was added dropwise with stirring. After stirring 1 h at room temperature the mixture was extracted into ethyl acetate. The organic solution was washed with brine, dried (MgSO4) and evaporated to leave an oil. The oil (75.1 g) was dissolved in methylene chloride (800 ml) and cooled in an ice-bath under an atmosphere of nitrogen. With efficient stirring titanium tetrachloride (43.3 ml) was slowly added dropwise. The reaction mixture was stirred 1 h in the ice-bath and then 3 h at room temperature. The reaction mixture was poured slowly into vigorously stirred ice-water (2 L), and then the resulting suspension was extracted into methylene chloride. After drying, the organic solvent was removed in vacuo, and the residue was chromatographed (SiO2/1:1 ethyl acetate-isohexane) to afford the sub-title compound 42 g. Trituration with isohexane gave a white powder. δ 1HCDCl3—0.98(6H,d), 2.23-2.41 (1H,m), 2.46 (3H,s), 3.4 (3H,s), 3.75 (2H,d), 3.96 (3H,s).

후처리

  1. additionwas added dropwise
  2. stirringAfter stirring 1 h at room temperature the mixture
  3. extractionwas extracted into ethyl acetate
  4. washThe organic solution was washed with brine
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customto leave an oil
  8. temperaturecooled in an ice-bath under an atmosphere of nitrogen
  9. additionwas slowly added dropwise
  10. custom3 h
  11. customat room temperature
  12. extractionthe resulting suspension was extracted into methylene chloride
  13. customAfter drying
  14. customthe organic solvent was removed in vacuo
  15. customthe residue was chromatographed (SiO2/1:1 ethyl acetate-isohexane)

출처 및 근거

ORD 기록
ord-3a1efdf513794b83a6209311974c4226
출처 데이터셋
uspto-grants-2008_06
특허 번호
US07384950B2

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