Ethyl bromopyruvate → Ethyl 2-(trifluoromethyl)-1,3-thiazole-4-carboxylate

HRID 625089ノート

反応式

HRID 625089 の反応式
[F:1][C:2]([F:7])([F:6])[C:3]([NH2:5])=O.COC1C=CC(P2(SP(C3C=CC(OC)=CC=3)(=S)S2)=[S:17])=CC=1.Br[CH2:31][C:32](=O)[C:33]([O:35][CH2:36][CH3:37])=[O:34]>C1COCC1>[F:1][C:2]([F:7])([F:6])[C:3]1[S:17][CH:31]=[C:32]([C:33]([O:35][CH2:36][CH3:37])=[O:34])[N:5]=1

参加物

5

反応物 3

HCID 66144Ethyl bromopyruvateHCID 67717TrifluoroacetamideHCID 87949Lawesson's reagent

生成物 1

HCID 20079591Ethyl 2-(trifluoromethyl)-1,3-thiazole-4-carboxylate収率 52.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

A mixture of 2,2,2-trifluoroacetamide (7.12 g, 63 mmol) and Lawesson's reagent (15.3 g, 37.8 mmol) in THF (60 mL) was heated at reflux for 18 hours. The reaction was then cooled down to RT and treated with ethyl bromopyruvate (8.0 mL, 63 mmol). The reaction was stirred at reflux for an additional 18 hours, then concentrated under vacuum and diluted with ethyl acetate. This mixture was washed with water (1×) and brine (1×), dried over anhydrous magnesium sulfate, filtered and concentrated. The residue was purified by silica gel chromatography (8×11 cm, toluene, then second time with 120 g silica gel, hexane/ethyl acetate) to give the title material (4.47 g, 32%) as a pale yellow solid. 1H NMR (CDCl3, 400 MHz) δ 8.37 (s, 1H), 4.45 (q, J=7.0 Hz, 2H), 1.41 (t, J=7.0 Hz, 1H).

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 18 hours
  3. temperatureat reflux for an additional 18 hours
  4. concentrationconcentrated under vacuum
  5. additiondiluted with ethyl acetate
  6. washThis mixture was washed with water (1×) and brine (1×)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe residue was purified by silica gel chromatography (8×11 cm, toluene

出典と根拠

ORDレコード
ord-009e8501044f409db673bc005f1e1143
出典データセット
uspto-grants-2016_04
特許番号
US09303065B2

反応ノート

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