Triphenylphosphine → tert-butyl-3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyrrolidine-1-carboxylate

HRID 928199ノート

反応式

HRID 928199 の反応式
[CH3:1][C:2]1[C:6]([N+:7]([O-:9])=[O:8])=[CH:5][NH:4][N:3]=1.[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH:19](O)[CH2:18]1)=[O:16])([CH3:13])([CH3:12])[CH3:11].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C1COCC1>[C:10]([O:14][C:15]([N:17]1[CH2:21][CH2:20][CH:19]([N:4]2[CH:5]=[C:6]([N+:7]([O-:9])=[O:8])[C:2]([CH3:1])=[N:3]2)[CH2:18]1)=[O:16])([CH3:13])([CH3:11])[CH3:12]

参加物

6

反応物 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 44169391-Boc-3-pyrrolidinolHCID 178434564HCID 178434564、化合物

生成物 1

HCID 69092482tert-butyl-3-(3-methyl-4-nitro-1H-pyrazol-1-yl)pyrrolidine-1-carboxylate収率 35.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

実験手順

To a solution of 3-methyl-4-nitro-1H-pyrazole (3.0 g, 23.6 mmol, 1.00 eq), tert-butyl-3-hydroxypyrrolidine-1-carboxylate (4.42 g, 23.6 mmol, 1.00 eq), and triphenylphosphine (6.19 g, 23.6 mmol, 1.00 eq) in THF (60 mL) was added a solution of diethyl azodicarboxylate (4.34 mL, 23.6 mmol, 1.00 eq) in THF (10 mL) in a drop-wise manner over 30 min. The reaction mixture was allowed to stir at ambient temperature for 20 hr and then concentrated. The crude reaction mixture was purified via repeated flash chromatography on silica gel eluting with a gradient of 0-35% EtOAc in heptane to give the title compound (2.48 g, 35% yield) as a colorless oil that was the early eluting of two structural isomers. 1H NMR (400 MHz, CDCl3) δ ppm 8.15 (s, 1 H) 4.80 (quin, J=5.7 Hz, 1 H) 3.83 (dd, J=6.0, 12.0 Hz, 1 H) 3.79-3.45 (m, 3 H) 2.52 (s, 3 H) 2.38 (q, J=7.0 Hz, 2 H) 1.46 (s, 9 H). m/z (APCI+) for C13H21N4O4 197.2 (M+H)+.

後処理

  1. concentrationconcentrated
  2. customThe crude reaction mixture
  3. customwas purified

出典と根拠

ORDレコード
ord-133731aeda354787b31bb7314cbd0ffe
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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