Hydrochloric Acid → Ethyl 3-methyl-2,4-dioxo-1-propyl-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidine-5-carboxylate

HRID 131572ノート

反応式

HRID 131572 の反応式
[CH3:1][N:2]1[C:7](=[O:8])[CH:6]=[C:5]([SH:9])[N:4]([CH2:10][CH2:11][CH3:12])[C:3]1=[O:13].C(=O)([O-])[O-].[K+].[K+].Br[CH2:21][C:22](=O)[C:23]([O:25][CH2:26][CH3:27])=[O:24].Cl>CN(C)C=O.ClCCl.[Ti](Cl)(Cl)(Cl)Cl.O>[CH3:1][N:2]1[C:7](=[O:8])[C:6]2[C:22]([C:23]([O:25][CH2:26][CH3:27])=[O:24])=[CH:21][S:9][C:5]=2[N:4]([CH2:10][CH2:11][CH3:12])[C:3]1=[O:13]

参加物

9

反応物 4

HCID 313Hydrochloric AcidHCID 11430Potassium CarbonateHCID 66144Ethyl bromopyruvateHCID 866227106-Mercapto-3-methyl-1-propyl-pyrimidine-2,4(1H,3H)-dione

生成物 1

HCID 17974732Ethyl 3-methyl-2,4-dioxo-1-propyl-1,2,3,4-tetrahydrothieno[2,3-d]pyrimidine-5-carboxylate

試薬・触媒・溶媒 4

HCID 24193Titanium Tetrachloride触媒HCID 962Water溶媒2 回HCID 6228Dimethylformamide溶媒HCID 6344Dichloromethane溶媒

実験手順

The product of step b) (6.95 g) in dry dimethylformamide (100 ml) was added potassium carbonate (2.4 g) and stirred for 10 min. Ethyl bromopyruvate (5 ml) was added and was stirred under nitrogen at room temperature for 2 h. The reaction was poured into water (1 L), acidified (2M HCl) and extracted with ethyl acetate. The organic extracts were washed with brine (100 ml). Drying and evaporation afforded an oil. The oil was dissolved in dichloromethane (100 ml) and cooled in ice whilst stirring. Titanium tetrachloride (7.58 ml) was added and stirring continued under nitrogen for 2 h. The reaction was poured into water (1 L) and extracted with dichloromethane. The organics were dried and evaporated in vacuo. The residue was purified by chromatography (SiO2/ethyl acetate-dichloromethane 0-8%) to afford the subtitle compound as an orange oil, 4.64 g. δ 1HCDCl3 1.02 (3H, t), 1.83 (2H, sextet), 3.42 (3H, s), 3.95 (2H, t), 4.41 (2H, q), 7.30 (1H, s). MS (APCI) 297.1 (M++H)

後処理

  1. stirringwas stirred under nitrogen at room temperature for 2 h
  2. extractionextracted with ethyl acetate
  3. washThe organic extracts were washed with brine (100 ml)
  4. customDrying
  5. customevaporation
  6. customafforded an oil
  7. temperaturecooled in ice
  8. stirringwhilst stirring
  9. stirringstirring
  10. waitcontinued under nitrogen for 2 h
  11. extractionextracted with dichloromethane
  12. customThe organics were dried
  13. customevaporated in vacuo
  14. customThe residue was purified by chromatography (SiO2/ethyl acetate-dichloromethane 0-8%)

出典と根拠

ORDレコード
ord-ee08f61483ce4b388c418c3d2681ec37
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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