Di-tert-butyl azodicarboxylate → (S)-3-methoxy-1-(1-methylpyrrolidin-3-yl)-4-nitro-1H-pyrazole

HRID 928216ノート

反応式

HRID 928216 の反応式
[CH3:1][O:2][C:3]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][NH:5][N:4]=1.[CH3:11][N:12]1[CH2:16][CH2:15][C@@H:14]([OH:17])[CH2:13]1.N(C(OC(C)(C)C)=O)=NC(OC(C)(C)C)=O>C1COCC1.CCOC(C)=O>[NH3:4].[CH3:15][CH2:14][O:17][C:3]([CH3:7])=[O:2].[CH3:1][O:2][C:3]1[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][N:5]([C@H:14]2[CH2:15][CH2:16][N:12]([CH3:11])[CH2:13]2)[N:4]=1

参加物

7

反応物 3

HCID 97268Di-tert-butyl azodicarboxylateHCID 69513321-Methyl-3-pyrrolidinol, (-)-HCID 178494320HCID 178494320、化合物

生成物 2

HCID 18464838Ammonia ethyl acetate収率 10%HCID 118073571(S)-3-methoxy-1-(1-methylpyrrolidin-3-yl)-4-nitro-1H-pyrazole収率 150.9%

試薬・触媒・溶媒 2

HCID 8028Tetrahydrofuran溶媒2 回HCID 8857Ethyl Acetate溶媒

実験手順

To a suspension of 3-methoxy-4-nitro-1H-pyrazole (2.00 g, 14.0 mmol, 1.00 eq), (R)-1-methyl-pyrrolidin-3-ol (1.56 g, 15.4 mmol, 1.10 eq), and polystyrene bound triphenylphosphine (6.53 g, 19.6 mmol, 1.40 eq, 3 mmol/gram) in THF (140 mL) was added a solution of di-tert-butyl azodicarboxylate (4.51 g, 19.6 mmol, 1.40 eq) in THF (25 mL) in a drop-wise manner over 5 min. The reaction mixture was allowed to stir for 18 hr. The reaction mixture was then diluted with EtOAc (100 mL), filtered and the filtrate concentrated. The crude reaction mixture was purified via flash chromatography on silica gel eluting with a gradient of 50-100% EtOAc in heptane then to 10% 7 N methanolic ammonia/EtOAc to give the title compound (2.39 g, 80% yield) as a white solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.69 (s, 1H), 4.84-4.72 (m, 1H), 3.94 (s, 3H), 2.86-2.75 (m, 2H), 2.72 (dd, J=7.0, 10.0 Hz, 1H), 2.40 (dt, J=6.2, 8.4 Hz, 1H), 2.36-2.29 (m, 1H), 2.28 (s, 3H), 2.16-2.06 (m, 1H). m/z (APCI+) for C9H15N4O3 227.2 (M+H)+.

後処理

  1. filtrationfiltered
  2. concentrationthe filtrate concentrated
  3. customThe crude reaction mixture
  4. customwas purified via flash chromatography on silica gel eluting with a gradient of 50-100% EtOAc in heptane

出典と根拠

ORDレコード
ord-f931de4d914445848767c7c3d305e090
出典データセット
uspto-grants-2016_03
特許番号
US09290496B2

反応ノート

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