Benzene, 1-azido-4-chloro- → HCID 90451725, compound

HRID 57409Notes

Reaction equation

HRID 57409 reaction equation
[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]

Participants

6

Reactant 3

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

Product 1

HCID 90451725HCID 90451725, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6342AcetonitrileSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-5e4a89ed03e442eba8dfb26719092096
Source dataset
uspto-grants-2016_09
Patent number
US09434719B2

Reaction notes

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