Potassium Carbonate → 1-((R)-2,2-dimethyl-[1,3]dioxolan-4-ylmethyl)-3-nitro-1H-pyrazole

HRID 19016ノート

反応式

HRID 19016 の反応式
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].[CH3:9][C:10]1([CH3:27])[O:14][C@H:13]([CH2:15]OS(C2C=CC(C)=CC=2)(=O)=O)[CH2:12][O:11]1.C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O.C(OCC)(=O)C>[CH3:9][C:10]1([CH3:27])[O:14][C@H:13]([CH2:15][N:6]2[CH:7]=[CH:8][C:4]([N+:1]([O-:3])=[O:2])=[N:5]2)[CH2:12][O:11]1

参加物

6

反応物 3

HCID 11430Potassium CarbonateHCID 2723760(S)-(+)-2,2-Dimethyl-1,3-dioxolan-4-ylmethyl p-ToluenesulfonateHCID 178526745HCID 178526745、化合物

生成物 1

HCID 593449371-((R)-2,2-dimethyl-[1,3]dioxolan-4-ylmethyl)-3-nitro-1H-pyrazole収率 72%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
90 °C

実験手順

A solution of 3-nitro-1H-pyrazole (prepared as in Example 5, 12.0 g, 106 mmol) in N,N-dimethylformamide (150 mL) was treated with toluene-4-sulfonic acid (S)-2,2-dimethyl-[1,3]dioxolan-4-yl-methyl ester (25.5 g, 89.0 mmol), and potassium carbonate (24.5 g, 178 mmol). The reaction mixture was stirred for 6 h at 90° C., under nitrogen. The reaction mixture was diluted with ethyl acetate, washed with water twice, a saturated sodium chloride solution and dried over sodium sulfate. The organic layer was concentrated, and the crude product was purified by ISCO flash chromatography (Teledyne Isco RediSep Flash Column 330 g, 5% to 30% ethyl acetate/hexanes) to afford 1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl-methyl)-3-nitro-1H-pyrazole (14.5 g, 72%) as light yellow oil: LR-ES-MS m/z calculated for C9H13N3O4 [M]+ 227, observed [M+H]+ 228. 1H NMR (300 MHz, CDCl3) δ ppm 1.35 (s, 3H), 1.40 (s, 3H), 3.77 (dd, J=8.8, 5.7 Hz, 1H), 4.13 (dd, J=8.8, 6.6 Hz, 1H), 4.27 (dd, J=14.0, 6.6 Hz, 1H), 4.39 (dd, J=14.0, 3.6 Hz, 1H), 4.45-4.59 (m, 1H), 6.92 (d, J=2.4 Hz, 1H), 7.59 (d, J=2.4 Hz, 1H)

後処理

  1. washwashed with water twice
  2. dry with materiala saturated sodium chloride solution and dried over sodium sulfate
  3. concentrationThe organic layer was concentrated
  4. customthe crude product was purified by ISCO flash chromatography (Teledyne Isco RediSep Flash Column 330 g, 5% to 30% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-7cc451c997fb4548876b2a95ef76272b
出典データセット
uspto-grants-2010_06
特許番号
US07741327B2

反応ノート

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