Water → Ethyl 3-methyl-1-(2-methylpropyl)-2,4-dioxo-1,2,3,4-tetrahydro-thieno[2,3-d]pyrimidine-5-carboxylate

HRID 131551ノート

反応式

HRID 131551 の反応式
[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[CH2:16][C:17](=O)[C:18]([O:20][CH2:21][CH3:22])=[O:19].C(=O)([O-])[O-].[K+].[K+].O>CN(C=O)C.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][CH2:21][CH3:22])=[O:19])=[CH:16][S:1][C:2]=2[N:7]([CH2:8][CH:9]([CH3:11])[CH3:10])[C:6]1=[O:12]

参加物

8

反応物 4

HCID 962WaterHCID 11430Potassium CarbonateHCID 66144Ethyl bromopyruvateHCID 52825676-Mercapto-3-methyl-1-(2-methylpropyl)-2,4(1H,3H)-pyrimidinedione

生成物 1

HCID 5282568Ethyl 3-methyl-1-(2-methylpropyl)-2,4-dioxo-1,2,3,4-tetrahydro-thieno[2,3-d]pyrimidine-5-carboxylate

試薬・触媒・溶媒 3

HCID 24193Titanium Tetrachloride触媒HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

6-Mercapto-3-methyl-1-(isobutyl)-pyrimidine-2,4(1H,3H)-dione (49.5 g) was dissolved in dry DMF (900 ml) and ethyl bromopyruvate (30 ml) was added, and then with stirring anhydrous potassium carbonate (15.95 g) was also added. The mixture was stirred at room temperature for 5 h, and then poured into water (5 L). The aqueous solution was acidified with dil hydrochloric acid, and then extracted thoroughly with ethyl acetate. The organic extract was dried (MgSO4) and evaporated at high vacuum to leave a semisolid mass. A portion of this semisolid mass (24 g) was dissolved in methylene chloride (500 ml) and cooled in an ice-bath under an atmosphere of nitrogen. With efficient stirring titanium tetrachloride (13.5 ml) was slowly added. The reaction mixture was stirred 1 hr in the ice-bath and then 3 hr at room temperature. The reaction mixture was poured slowly into vigorously stirred ice-water (1.5 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 as a pale yellow solid 15 g. δ 1HCDCl3 1.0 (6H, d), 1.4 (3H, t), 2.31-2.45 (1H, m), 3.4 (3H, s), 3.8 (2H, d), 4.4 (2H, q), 7.28 (1H, s).

後処理

  1. extractionextracted thoroughly with ethyl acetate
  2. extractionThe organic extract
  3. dry with materialwas dried (MgSO4)
  4. customevaporated at high vacuum
  5. customto leave a semisolid mass
  6. temperaturecooled in an ice-bath under an atmosphere of nitrogen
  7. additionwas slowly added
  8. custom3 hr
  9. customat room temperature
  10. extractionthe resulting suspension was extracted into methylene chloride
  11. customAfter drying the organic solvent
  12. customwas removed in vacuo
  13. customthe residue was chromatographed (SiO2/1:1 ethyl acetate-isohexane)

出典と根拠

ORDレコード
ord-625d21e85c9649edb21d1d3b3e1fb6b6
出典データセット
uspto-grants-2008_06
特許番号
US07384950B2

反応ノート

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