Imidazole → 1-(2-methyl-2-triethylsilanyloxy-propyl)-3-nitro-1H-pyrazole

HRID 546125

反応式

HRID 546125 の反応式
[CH3:1][C:2]([OH:13])([CH3:12])[CH2:3][N:4]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[N:5]1.CN(C)C=O.[CH2:19]([Si:21](Cl)([CH2:24][CH3:25])[CH2:22][CH3:23])[CH3:20].N1C=CN=C1>C(OCC)(=O)C>[CH3:12][C:2]([O:13][Si:21]([CH2:24][CH3:25])([CH2:22][CH3:23])[CH2:19][CH3:20])([CH3:1])[CH2:3][N:4]1[CH:8]=[CH:7][C:6]([N+:9]([O-:11])=[O:10])=[N:5]1

参加物

6

反応物 4

HCID 795ImidazoleHCID 6228DimethylformamideHCID 13819ChlorotriethylsilaneHCID 545944402-methyl-1-(3-nitro-1H-pyrazol-1-yl)propan-2-ol

生成物 1

HCID 584370871-(2-methyl-2-triethylsilanyloxy-propyl)-3-nitro-1H-pyrazole収率 72%

試薬・触媒・溶媒 1

HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

In a round bottomed flask was placed 2-methyl-1-(3-nitro-pyrazol-1-yl)-propan-2-ol (170 mg, 0.92 mmol) and N,N-dimethylformamide (5 mL) and it was placed in an ice bath and cooled to 0° C. To this stirred solution was added triethylsilyl chloride (169 mL, 1.01 mmol) and imidazole (156 mg, 2.30 mmol) and it was stirred at 0° C. and slowly warmed to 25° C. and stirred for two days. The reaction was then diluted with ethyl acetate (15 mL) and washed with a saturated aqueous brine solution (10 mL). The aqueous layer was then extracted with ethyl acetate (2×15 mL). The organic layers were then combined and dried over sodium sulfate, filtered and concentrated in vacuo. Purification by AnaLogix Intelliflash system (4 g column, 5% ethyl acetate/hexanes to 20% ethyl acetate/hexanes) afforded 1-(2-methyl-2-triethylsilanyloxy-propyl)-3-nitro-1H-pyrazole (197 mg, 72%) as a clear colorless oil: ES-HRMS m/e calcd for C13H25N3O3Si (M+H)+ 300.1738, observed 300.1737; 1H NMR (300 MHz, CDCl3) δ ppm 0.58 (q, J=8.0 Hz, 6H, 3×SiCH2), 0.92 (t, J=8.0 Hz, 9H, 3×CH3), 1.26 (s, 6H, 2×CH3), 4.12 (s, 2H, NCH2), 6.89 (d, J=2.5 Hz, 1H, Ar), 7.56 (d, J=2.5 Hz, 1H, Ar).

後処理

  1. customIn a round bottomed flask was placed
  2. temperatureslowly warmed to 25° C.
  3. stirringstirred for two days
  4. washwashed with a saturated aqueous brine solution (10 mL)
  5. extractionThe aqueous layer was then extracted with ethyl acetate (2×15 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification by AnaLogix Intelliflash system (4 g column, 5% ethyl acetate/hexanes to 20% ethyl acetate/hexanes)

出典と根拠

ORDレコード
ord-07f93e8159424fbdaba54902de951462
出典データセット
uspto-grants-2011_05
特許番号
US07935699B2

関連ノート

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