Potassium Carbonate → 2-t-Butoxycarbonylamino-4-ethynyl-thiophene-3-carboxylic acid ethyl ester

HRID 1244160ノート

反応式

HRID 1244160 の反応式
[CH2:1]([O:3][C:4]([C:6]1[C:10]([CH:11]=O)=[CH:9][S:8][C:7]=1[NH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[O:5])[CH3:2].[C:21](=O)([O-])[O-].[K+].[K+].COP(C(=[N+]=[N-])C(=O)C)(=O)OC>CCO>[CH2:1]([O:3][C:4]([C:6]1[C:10]([C:11]#[CH:21])=[CH:9][S:8][C:7]=1[NH:13][C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])=[O:5])[CH3:2]

参加物

5

反応物 3

HCID 11430Potassium CarbonateHCID 86596546HCID 86596546、化合物HCID 136023029(1E)-1-diazo-1-dimethoxyphosphorylpropan-2-one

生成物 1

HCID 865965472-t-Butoxycarbonylamino-4-ethynyl-thiophene-3-carboxylic acid ethyl ester収率 93.1%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

実験手順

2-t-Butoxycarbonylamino-4-formyl-thiophene-3-carboxylic acid ethyl ester (6.35 g, 21.31 mmol) from example 240d was dissolved in absolute EtOH (325 mL). This was treated with potassium carbonate (%.89 g, 42.62 mmol) followed by (1-diazo-2-oxopropyl)-phosphonic acid dimethyl ester (4.91 g, 25.57 mmol). The reaction was stirred at room temperature for 14 hr. The reaction was concentrated to 12 volume then poured into sat. NaHCO3 (250 mL) and then extracted with EtOAc (3×250 mL). The combined extracts were washed with brine (2×250 mL). They were dried (Na2SO4), filtered and the solvent removed in vacuo. The crude product was purified by flash chromatography (SiO2, 1 EtOAc/9 hexanes) to afford the title compound (5.86 g, 93%). MS m/e (CI) 296.0 (M+H), 313.1 (M+NH4); 1H NMR (300 MHz, CDCl3): δ ppm 1.41 (t, 3H), 1.53 (s, 9H), 3.11 (s, 1H), 4.37 (q, 2H), 6.98 (s, 1H), 10.30 (s, 1H).

後処理

  1. concentrationThe reaction was concentrated to 12 volume
  2. additionthen poured into sat. NaHCO3 (250 mL)
  3. extractionextracted with EtOAc (3×250 mL)
  4. washThe combined extracts were washed with brine (2×250 mL)
  5. dry with materialThey were dried (Na2SO4)
  6. filtrationfiltered
  7. customthe solvent removed in vacuo
  8. customThe crude product was purified by flash chromatography (SiO2, 1 EtOAc/9 hexanes)

出典と根拠

ORDレコード
ord-3c097bc778484801af3d008c07685cc9
出典データセット
uspto-grants-2006_10
特許番号
US07119205B2

反応ノート

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