Triphenylphosphine → HCID 25247753, compound

HRID 546112Notes

Reaction equation

HRID 546112 reaction equation
[N+:1]([C:4]1[CH:8]=[CH:7][NH:6][N:5]=1)([O-:3])=[O:2].[CH:9]1([CH2:12]O)[CH2:11][CH2:10]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1.C(OCC)(=O)C>[CH:9]1([CH2:12][N:6]2[CH:7]=[CH:8][C:4]([N+:1]([O-:3])=[O:2])=[N:5]2)[CH2:11][CH2:10]1

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 75644CyclopropanemethanolHCID 178526745HCID 178526745, compound

Product 1

HCID 25247753HCID 25247753, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

The 3-Nitro-1H-pyrazole (prepared in example 3, 255 mg, 2.26 mmol) was dissolved in tetrahydrofuran (11 mL) and cyclopropyl-methanol (163 mg, 2.26 mmol) was added followed by triphenylphosphine (592 mg, 2.26 mmol). While stirring, diisopropyl azodicarboxylate (667 μL, 3.39 mmol) was added dropwise. A mild exotherm was observed. The reaction continued to stir for 30 min. The solution was diluted with ethyl acetate (100 mL), washed with water (2×35 mL), 1.0 M aqueous hydrochloric acid solution (35 mL), saturated aqueous brine solution (35 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification by flash column chromatography (Merck silica gel 60, 40-63 μm; 5% ethyl acetate/hexanes to 50% ethyl acetate/hexanes) afforded 1-cyclopropylmethyl-3-nitro-1H-pyrazole (217 mg, 58%) as a yellow oil: H1-NMR (400 MHz, CDCl3) δ 0.44 (2H, qt, J=5.6 Hz), 0.73 (2H, qt, J=6.8 Hz), 1.30-1.40 (1H, m), 4.07 (2H, d, J=7.6 Hz), 6.89 (1H, d, J=2.8 Hz), 7.57 (1H, d, J=2.4 Hz).

Workup

  1. stirringto stir for 30 min
  2. washwashed with water (2×35 mL), 1.0 M aqueous hydrochloric acid solution (35 mL), saturated aqueous brine solution (35 mL)
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customPurification by flash column chromatography (Merck silica gel 60, 40-63 μm; 5% ethyl acetate/hexanes to 50% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-c278713da57b44bab2d118f42fecf6cb
Source dataset
uspto-grants-2011_05
Patent number
US07935699B2

Reaction notes

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