Water → 2-(Cyclopropylamino)-5-methyl-3,4-thiophenedicarboxylic acid, 3-ethyl 4-methyl ester

HRID 131625

反応式

HRID 131625 の反応式
[CH2:1]([O:3][C:4](=[O:25])[CH:5]=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[CH3:2].[N:26]([CH:29]1[CH2:31][CH2:30]1)=[C:27]=[S:28].[CH3:32][O:33][C:34](=[O:40])[C:35](=O)[CH:36](Br)[CH3:37].O>O1CCCC1>[CH:29]1([NH:26][C:27]2[S:28][C:36]([CH3:37])=[C:35]([C:34]([O:33][CH3:32])=[O:40])[C:5]=2[C:4]([O:3][CH2:1][CH3:2])=[O:25])[CH2:31][CH2:30]1

参加物

6

反応物 4

HCID 962WaterHCID 70670Acetic acid, 2-(triphenylphosphoranylidene)-, ethyl esterHCID 92463Cyclopropyl isothiocyanateHCID 11183175Methyl 3-bromo-2-oxobutanoate

生成物 1

HCID 866035742-(Cyclopropylamino)-5-methyl-3,4-thiophenedicarboxylic acid, 3-ethyl 4-methyl ester収率 61.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of (triphenylphosphoranylidene)-acetic acid ethyl ester (15 g) in anhydrous tetrahydrofuran (100 ml) was added isothiocyanato-cyclopropane (4.4 g) and the mixture was refluxed under a nitrogen atmosphere for 20 hr. After allowing to cool to ambient temperature the reaction mixture was cooled to −78° C. and then a solution of 3-bromo-2-oxo-butanoic acid methyl ester (8.7 g) in anhydrous tetrahydrofuran (10 ml) was added. The resulting mixture was allowed to warm to ambient temperature and then refluxed for 20 hr., then ambient temperature for 2 days. The reaction was poured into water and extracted with diethyl ether. The collected organic extract was dried over magnesium sulfate, filtered and evaporated under reduced pressure. The residue was purified by column chromatography over silica, eluting with i-hexane/ethyl acetate (95:5) then triturated with i-hexane/diethyl ether (8:2) to give the sub-title compound as a solid (7.5 g).

後処理

  1. temperaturethe mixture was refluxed under a nitrogen atmosphere for 20 hr
  2. temperaturewas cooled to −78° C.
  3. temperatureto warm to ambient temperature
  4. temperaturerefluxed for 20 hr
  5. extractionextracted with diethyl ether
  6. extractionThe collected organic extract
  7. dry with materialwas dried over magnesium sulfate
  8. filtrationfiltered
  9. customevaporated under reduced pressure
  10. customThe residue was purified by column chromatography over silica
  11. washeluting with i-hexane/ethyl acetate (95:5)
  12. customthen triturated with i-hexane/diethyl ether (8:2)

出典と根拠

ORDレコード
ord-a0516163ebdb43e2bcca83e1983a1e95
出典データセット
uspto-grants-2008_06
特許番号
US07384951B2

関連ノート

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