Triphenylphosphine → HCID 178420541, compound

HRID 1169020Notes

Reaction equation

HRID 1169020 reaction equation
[C:1]1([P:7]([C:14]2C=C[CH:17]=[CH:16][CH:15]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li].Cl.ClCC1C=C[NH:26][N:25]=1>O1CCCC1>[C:1]1([P:7]([CH2:14][C:15]2[CH:16]=[CH:17][NH:26][N:25]=2)[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 3

HCID 11776TriphenylphosphineHCID 3028194Lithium2×HCID 178478564HCID 178478564, compound

Product 1

HCID 178420541HCID 178420541, compoundYield 77%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of tetrahydrofuran (100 ml) and triphenylphosphine (3.56 g, 13.6 mmol) at room temperature is added lithium (0.100 g, 14.5 mmol). The reaction mixture is stirred at room temperature for 2 hours at which time the lithium has dissolved. The bright red solution is cooled to 0° C., and 3-(chloromethyl)pyrazole hydrochloride (0.960 g, 6.8 mmol) is added at once. The ice bath is removed and the reaction solution is allowed to stir an additional 2 hours. Degassed ethanol (40 ml) is added to the reaction mixture followed by diethyl ether (100 ml). The organic phase is separated and the aqueous phase extracted with diethyl ether (2×25 ml). The organic phases are combined and dried over magnesium sulfate, filtered and concentrated. The crude residue is purified by chromatography (SiO2, 50% ethyl acetate/petroleum ether) to give purified 3-(diphenylphosphinomethyl)pyrazole as a cloudy white oil in 77% yield (2.81 g, 10.6 mmol). This material is characterized as follows: 1H NMR (CDCl3, 500 MHz) δ7.43 (m,4H), 7.41 (d, J=2.0 Hz, 1H), 7.34 (m, 6H), 5.99 (d, J=2.0 Hz, 1H), 3.47 (s, 2H); 13C{1H} NMR (CDCl3, 125 MHz) δ138.16 (d, 14.3 Hz), 132.97 (d, J=18.6 Hz), 129.11, 128.73 (d, J=6.6 Hz), 105.18 (d, J=5.1 Hz), 27.14 (d, J=6.2 Hz) MS m/z 265.9, 182.9 (M—C4H3N2).

Workup

  1. dissolutionhas dissolved
  2. customThe ice bath is removed
  3. additionDegassed ethanol (40 ml) is added to the reaction mixture
  4. customThe organic phase is separated
  5. extractionthe aqueous phase extracted with diethyl ether (2×25 ml)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude residue is purified by chromatography (SiO2, 50% ethyl acetate/petroleum ether)
  10. customto give
  11. custompurified 3-(diphenylphosphinomethyl)pyrazole as a cloudy white oil in 77% yield (2.81 g, 10.6 mmol)

Sources & evidence

ORD record
ord-d75217f7de404d8eaeb9c1b0c01418aa
Source dataset
uspto-grants-2003_09
Patent number
US06627758B2

Reaction notes

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