Formaldehyde → Diethyl 1H-pyrrole-2,4-dicarboxylate

HRID 877657ノート

反応式

HRID 877657 の反応式
[N+:1]([CH2:3][C:4]([O:6][CH2:7][CH3:8])=[O:5])#[C-:2].[CH2:9]1[CH2:19][CH2:18]N2C(=NCCC2)CC1.C=[O:21].C1C[O:25][CH2:24][CH2:23]1>>[NH:1]1[CH:2]=[C:19]([C:18]([O:25][CH2:24][CH3:23])=[O:21])[CH:9]=[C:3]1[C:4]([O:6][CH2:7][CH3:8])=[O:5]

参加物

5

反応物 4

HCID 712FormaldehydeHCID 8028TetrahydrofuranHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 533707Ethyl isocyanoacetate

生成物 1

HCID 12711558Diethyl 1H-pyrrole-2,4-dicarboxylate収率 26%

反応条件

温度
0 °C

実験手順

To a round bottom flask under argon was added ethyl 2-isocyanoacetate (100 g, 0.884 mol), dry THF (1.0 L) followed by DBU (132 g, 0.867 mol). The reaction was cooled to 0° C. and formaldehyde (16 g) was added portionwise into the reaction mixture. The reaction was then stirred at room temperature overnight. Then THF was removed under high vacuum and the residue as dissolved with water and extracted with EtOAc (2×1 L). The combined organic layer was washed with water and brine and concentrated. The residue was purified by flash silica gel column chromatography to yield 40 g (26%) of a white solid as the title compound. H1 NMR (400 MHz, CDCl3) δ ppm: 9.85 (1H, br s), 7.54 (1H, m), 7.30 (1H, m), 4.36-4.6 (4H, merging quartets), 1.37-1.26 (6H, merging triplets). LCMS (condition A): m/z=210.2 −ve.

後処理

  1. customThen THF was removed under high vacuum
  2. dissolutionthe residue as dissolved with water
  3. extractionextracted with EtOAc (2×1 L)
  4. washThe combined organic layer was washed with water and brine
  5. concentrationconcentrated
  6. customThe residue was purified by flash silica gel column chromatography

出典と根拠

ORDレコード
ord-11fbd9db6a15480bad372e32908916e9
出典データセット
uspto-grants-2015_03
特許番号
US08987268B2

反応ノート

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