Sodium Hydroxide → (DIPHENYLPHOSPHINO)METHANETHIOL

HRID 2250861ノート

反応式

HRID 2250861 の反応式
[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

参加物

4

反応物 2

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

生成物 1

HCID 11230015(DIPHENYLPHOSPHINO)METHANETHIOL収率 94%

試薬・触媒・溶媒 1

HCID 887Methanol溶媒

実験手順

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, 4H), 7.33-7.26 (m, 6H), 3.02 (d, J=7.8 Hz, 2H), 1.38 (t, J=7.5 Hz, 1H) 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) 6-7/94 ppm; MS (ESI) m/z 232.05 (MH+=233.0, fragments at 183.0, 155.0, 139.0, 91.2).

後処理

  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)

出典と根拠

ORDレコード
ord-140f803d39f8491fb007352b28259673
出典データセット
uspto-grants-2008_01
特許番号
US07317129B2

反応ノート

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