Triphenylphosphine → 4-(Benzoylthiomethyl)-1-methylpyrazole

HRID 992685Notes

Reaction equation

HRID 992685 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.O[CH2:33][C:34]1[CH:35]=[N:36][N:37]([CH3:39])[CH:38]=1.[C:40]([OH:48])(=[S:47])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1.C(=O)(O)[O-].[K+]>C1COCC1.C(OCC)(=O)C.O>[C:40]([S:47][CH2:33][C:34]1[CH:35]=[N:36][N:37]([CH3:39])[CH:38]=1)(=[O:48])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

9

Reactant 5

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 516893Potassium BicarbonateHCID 11961423(1-methyl-1H-pyrazol-4-yl)methanolHCID 178526132HCID 178526132, compound

Product 1

HCID 184116014-(Benzoylthiomethyl)-1-methylpyrazole

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Under nitrogen atmosphere, 78.7 g of triphenylphosphine (300 m mol) and 47.2 ml of diethyl azodicarboxylate (300 m mol) were added to a stirred solution of 22.4 g of 4-hydroxymethyl-1-methylpyrazole (200 m mol) in THF (250 ml) at 5° C. After stirring for 1 hour at the same temperature, 42.3 ml of thiobenzoic acid (360 m mol) was added slowly to the mixture. The mixture was poured into a mixture of water and ethyl acetate, while Ph was adjusted to 9.5 with 30% potassium bicarbonate. Aqueous layer was separated, the organic layer was washed with brine, dried over magnesium sulfate. After filtration of the mixture, the filtrate was concentrated in vacuo, and the residue was purified on silica gel (eluent: n-hexane-ethyl acetate) to afford 4-(benzoylthiomethyl)-1-methylpyrazole (18.3 g).

Workup

  1. additionwas added slowly to the mixture
  2. customAqueous layer was separated
  3. washthe organic layer was washed with brine
  4. dry with materialdried over magnesium sulfate
  5. filtrationAfter filtration of the mixture
  6. concentrationthe filtrate was concentrated in vacuo
  7. customthe residue was purified on silica gel (eluent: n-hexane-ethyl acetate)

Sources & evidence

ORD record
ord-1973982b4d134b29b792487866876acc
Source dataset
uspto-grants-2002_10
Patent number
US06468995B1

Reaction notes

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