Benzene, 1-azido-4-chloro- → (S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate

HRID 57409ノート

反応式

HRID 57409 の反応式
[CH3:1][C@H:2]([NH:5][C:6](=[O:12])[O:7][C:8]([CH3:11])([CH3:10])[CH3:9])[C:3]#[CH:4].[N:13]([C:16]1[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=1)=[N+:14]=[N-:15].C(N(C(C)C)C(C)C)C>C(#N)C.[Cu]I>[C:8]([O:7][C:6](=[O:12])[NH:5][C@H:2]([C:3]1[N:15]=[N:14][N:13]([C:16]2[CH:21]=[CH:20][C:19]([Cl:22])=[CH:18][CH:17]=2)[CH:4]=1)[CH3:1])([CH3:11])([CH3:10])[CH3:9]

参加物

6

反応物 3

HCID 76803Benzene, 1-azido-4-chloro-HCID 81531DiisopropylethylamineHCID 10986677tert-Butyl (2S)-but-3-yn-2-ylcarbamate

生成物 1

HCID 90451725(S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate収率 90%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 6342Acetonitrile溶媒

実験手順

A solution of (S)-tert-butyl but-3-yn-2-ylcarbamate (250 mg, 1.48 mmol), 1-azido-4-chlorobenzene (227 mg, 1.48 mmol, 1.0 equiv), and N-ethyl-N-isopropylpropan-2-amine (0.77 mL, 4.43 mmol, 3.0 equiv) in anhydrous acetonitrile (14.8 mL) was stirred at room temperature for 10 min. Copper(I) iodide (563 mg, 2.95 mmol, 2.0 equiv) was then added in portions. The mixture was stirred at room temperature for 30 min. The reaction was quenched with saturated aqueous ammonium chloride (50 mL) and diluted with water (50 mL). The mixture was extracted with ethyl acetate (3×30 mL) and the combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL), dried over Na2SO4, filtered and concentrated. Silica gel column chromatography (EtOAc/Heptane) provided (S)-tert-butyl(1-(1-(4-chlorophenyl)-1H-1,2,3-triazol-4-yl)ethyl)carbamate (0.428 g, white solid) in 90% yield. 1H NMR (400 MHz, CDCl3) δ 7.86 (s, 1H), 7.68 (d, J=8.8 Hz, 2H), 7.50 (d, J=8.8 Hz, 2H), 5.02 (m, 1H), 1.63 (d, J=6.8 Hz, 3H), 1.46 (s, 9H). MS m/z 323.1 (M+H)+; Rt-0.92 min.

後処理

  1. customThe reaction was quenched with saturated aqueous ammonium chloride (50 mL)
  2. additiondiluted with water (50 mL)
  3. extractionThe mixture was extracted with ethyl acetate (3×30 mL)
  4. washthe combined organic extracts were washed with water (30 mL), saturated aqueous sodium chloride (30 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated

出典と根拠

ORDレコード
ord-5e4a89ed03e442eba8dfb26719092096
出典データセット
uspto-grants-2016_09
特許番号
US09434719B2

反応ノート

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