Sodium hydride → methyl 4-(2-trimethylsilanyl-ethoxymethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate

HRID 1363267

反応式

HRID 1363267 の反応式
[S:1]1[C:8]2[CH:7]=[C:6]([C:9]([O:11][CH3:12])=[O:10])[NH:5][C:4]=2[CH:3]=[CH:2]1.[H-].[Na+].[CH3:15][Si:16]([CH2:19][CH2:20][O:21][CH2:22]Cl)([CH3:18])[CH3:17]>C1COCC1>[CH3:15][Si:16]([CH3:18])([CH3:17])[CH2:19][CH2:20][O:21][CH2:22][N:5]1[C:6]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:8]2[S:1][CH:2]=[CH:3][C:4]1=2

参加物

5

反応物 3

HCID 24758Sodium hydrideHCID 27242712-Chloromethyl 2-(trimethylsilyl)ethyl etherHCID 4058811methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate

生成物 1

HCID 59648515methyl 4-(2-trimethylsilanyl-ethoxymethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate収率 312.9%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

Methyl 4H-thieno[3,2-b]pyrrole-5-carboxylate (2.8 g, 15.45 mmol) was dissolved in 150 mL anhydrous THF. NaH (3.0 g, 60% oil dispersion, 75 mmol) was added and the reaction stirred for 15 min at rt. SEMCl [(2-trimethylsilyl)-ethoxymethyl chloride] (0.7 mL, 3.95 mmol) was added dropwise over 5 min. The reaction was stirred 1 h at rt and then CAUTIOUSLY poured onto 25 g crushed ice with stirring. The aqueous was extracted with EtOAc, dried (Na2SO4), filtered and evaporated in vacuo to give a green residue. The residue was chromatographed over silica gel (EtOAc in heptane, 3%-10%, 3 h, TLC visualized with KMnO4 with heat) to give methyl 4-(2-trimethylsilanyl-ethoxymethyl)-4H-thieno[3,2-b]pyrrole-5-carboxylate (3.85 g, 80% yield). 1H NMR (400 MHz, (CD3)2CO) δ ppm −0.08 (s, 9H) 0.84 (t, J=7.83 Hz, 2H) 3.54 (t, J=7.88 Hz, 2H) 3.83 (s, 3H) 5.94 (s, 2H) 7.21-7.25 (m, 1H) 7.26 (s, 1H) 7.55 (d, J=5.37 Hz, 1H).

後処理

  1. stirringThe reaction was stirred 1 h at rt
  2. additionCAUTIOUSLY poured onto 25 g
  3. customcrushed ice
  4. stirringwith stirring
  5. extractionThe aqueous was extracted with EtOAc
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customto give a green residue
  10. customThe residue was chromatographed over silica gel (EtOAc in heptane, 3%-10%, 3 h, TLC visualized with KMnO4 with heat)

出典と根拠

ORDレコード
ord-32b805ff17ce4ef39c46f1ae063fd20a
出典データセット
uspto-grants-2011_02
特許番号
US07884124B2

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