Sodium Hydroxide → (DIPHENYLPHOSPHINO)METHANETHIOL

HRID 488894Notes

Reaction equation

HRID 488894 reaction equation
[C:1]1([P:7]([CH2:14][S:15]C(=O)C)[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.[OH-].[Na+]>CO>[C:1]1([P:7]([CH2:14][SH:15])[C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 14798Sodium HydroxideHCID 11266196Ethanethioic acid, S-[(diphenylphosphino)methyl] ester

Product 1

HCID 11230015(DIPHENYLPHOSPHINO)METHANETHIOLYield 94%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Compound 11b (17.27 g, 63.0 mmol) was dissolved in anhydrous methanol and Ar(g) was bubbled through the solution for 1 h. Sodium hydroxide (2.52 g, 63 mmol) was then added, and the mixture was stirred under Ar(g) for 2 h. Solvent was then removed under reduced pressure, and the residue was dissolved in methylene chloride. This solution was washed twice with 2 N HCl and once with brine. The organic layer was dried over MgSO4(s) and filtered, and the solvent was removed under reduced pressure. The residue was purified by chromatography (alumina, 25% v/v ethyl acetateinhexanes) to afford 1b as a clear oil in 94% yield. Alternatively, phosphinothiol 1b can be used in its crude form for formation of phosphinothioesters. Spectral data. 1H NMR (CDCl3, 300 MHz) δ 7.41-7.38 (m, 4 H), 7.33-7.26 (m, 6 H), 3.02 (d, J=7.8 Hz, 2 H), 1.38 (t, J=7.5 Hz, 1 H) ppm; 13C NMR (CDCl3, 75 MHz) δ 132.54 (d, J=17.1 Hz), 128.86, 128.36, 128.14, 20.60 (d, J=21.7 Hz) ppm; 31P NMR (CDCl3, 121 MHz) δ—7/94 ppm; MS (EST) m/z 232.05 (MH+=233.0, fragments at 183.0, 155.0, 139.0, 91.2).

Workup

  1. customAr(g) was bubbled through the solution for 1 h
  2. customSolvent was then removed under reduced pressure
  3. dissolutionthe residue was dissolved in methylene chloride
  4. washThis solution was washed twice with 2 N HCl and once with brine
  5. dry with materialThe organic layer was dried over MgSO4(s)
  6. filtrationfiltered
  7. customthe solvent was removed under reduced pressure
  8. customThe residue was purified by chromatography (alumina, 25% v/v ethyl acetateinhexanes)

Sources & evidence

ORD record
ord-53f20d50d5f84e94a98920eeea3c9d1b
Source dataset
uspto-grants-2005_12
Patent number
US06974884B2

Reaction notes

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