Ammonium Chloride → HCID 86660363, compound

HRID 1749365Notes

Reaction equation

HRID 1749365 reaction equation
[I-].[CH:2]([P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([CH3:4])[CH3:3].C([Li])CCC.[CH3:29][N:30]1[C:34]([CH3:35])=[CH:33][C:32]([CH:36]=O)=[N:31]1.[Cl-].[NH4+]>C1COCC1>[CH3:29][N:30]1[C:34]([CH3:35])=[CH:33][C:32]([CH:36]=[C:2]([CH3:4])[CH3:3])=[N:31]1

Participants

6

Reactant 4

HCID 25517Ammonium ChlorideHCID 2723783Isopropyltriphenylphosphonium iodideHCID 70171011,5-dimethyl-1H-pyrazole-3-carbaldehydeHCID 178418339Butyllithium

Product 1

HCID 86660363HCID 86660363, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A suspension of isopropyltriphenylphosphonium iodide (5.23 g, 12.1 mmol) in THF (35 ml) at −20° C. was treated dropwise with a 1.6 M solution of butyllithium in hexanes (7.5 ml, 12 mmol). The mixture was stirred at −20° C. for 45 minutes before a solution of 1,5-dimethyl-1H-pyrazole-3-carboxaldehyde (1.20 g, 9.68 mmol) in THF (50 ml) was added. The thick suspension was allowed to warm to room temperature and stirred for 24 hours. The reaction mixture was treated with saturated aqueous ammonium chloride (150 ml) and the phases separated. The aqueous phase was back-extracted with ethyl acetate (3×50 ml) and the combined organic phases were dried (Na2SO4) and concentrated. The residue was extracted with petroleum ether (2×100 ml) and the combined extracts were concentrated to afford a yellow oil which was purified by chromatography (SiO2, 0-100% EtOAc-petroleum ether) to give the title compound as a colourless solid (1.56 g, 9.68 mmol). δH (CDCl3, 300K) 6.15 (1H, m), 6.01 (1H, s), 3.75 (3H, s), 2.26 (3H, s), 1.96 (3H, d J 0.8 Hz), 1.89 (3H, d J 1.2 Hz). m/z (ES+, 70V) 151.1 (MH+).

Workup

  1. additionwas added
  2. customthe phases separated
  3. extractionThe aqueous phase was back-extracted with ethyl acetate (3×50 ml)
  4. dry with materialthe combined organic phases were dried (Na2SO4)
  5. concentrationconcentrated
  6. extractionThe residue was extracted with petroleum ether (2×100 ml)
  7. concentrationthe combined extracts were concentrated
  8. customto afford a yellow oil which
  9. customwas purified by chromatography (SiO2, 0-100% EtOAc-petroleum ether)

Sources & evidence

ORD record
ord-97649f531bb54ac1b0809951475aa35e
Source dataset
uspto-grants-2015_10
Patent number
US09156811B2

Reaction notes

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