반응 #2074

ord-73770e6874334f60888ff4ce1f4e06f1

반응 방정식

Cc1ccc(OCC(=O)O)cc1.c1ccc([PH+](c2ccccc2)c2ccccc2)cc1
adduct
Cc1ccc(OCC(=O)O)cc1.c1ccc([PH+](c2ccccc2)c2ccccc2)cc1
Triphenylphosphonium (4-carboxymethoxyphenyl)methane
O=Cc1ccccc1S(=O)(=O)O
2-formylbenzenesulfonic acid
[Na]
sodium
CO
methanol
C[O-].[Na+]
sodium methoxide
COC(=O)c1ccc(/C=C/c2cccc[c]2[Na])c(S(=O)(=O)O)c1
white powder
COC(=O)c1ccc(/C=C/c2cccc[c]2[Na])c(S(=O)(=O)O)c1
Trans-methyl 2'-Sodiosulfostilbene-4-carboxylate

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도The solution is heated
  2. 2
    온도to reflux under argon
  3. 3
    온도The solution is heated
  4. 4
    온도at reflux for 8 hrs
  5. 5
    기타Most of the methanol is removed on the rotary evaporator (~60° C.)
  6. 6
    기타forming a milky suspension
  7. 7
    온도The mixture is cooled in an ice bath
  8. 8
    여과filtered
  9. 9
    농축The mother liquor is concentrated to ~800 mL on the rotary evaporator and refrigerated overnight
  10. 10
    여과The crystals which form are filtered
  11. 11
    기타dried
  12. 12
    농축The water layer is concentrated

실험 절차

To 146 gm (0.327 mol) of the adduct prepared in Example 10 in a 2 L, three-neck round bottom flask equipped with a magnetic stirring bar, condenser, addition funnel, and thermometer connected to a temperature controlling device (Thermowatch, I2R), is added 2-formylbenzenesulfonic acid, sodium salt, hydrate (Aldrich, 80 gm, ~0.35 mol), and methanol (Baker, ~900 gm). The solution is heated to reflux under argon, and sodium methoxide (Aldrich, 80.8 gm of 25% solution in methanol, 0.374 mol) is added from the addition funnel over ~15 min. The solution is heated at reflux for 8 hrs. A 13 C-NMR (DMSO-d6) shows the disappearance of the peaks for starting material at ~28.5 ppm and 29 ppm [--CH2P(C6 H5)3 ]. Most of the methanol is removed on the rotary evaporator (~60° C.). The remaining material is taken up in ~500 mL water, forming a milky suspension. The mixture is adjusted to pH 7 with a few drops of methanesulfonic acid (Aldrich). The mixture is cooled in an ice bath and filtered. A 13C-NMR (DMSO-d6) shows the isolated solid to be mainly triphenylphosphine oxide. The mother liquor is concentrated to ~800 mL on the rotary evaporator and refrigerated overnight. The crystals which form are filtered, dried, and stirred vigorously in hot 50:50 water:toluene. The water layer is concentrated to afford 20 gm of white powder. The combination of 13C-NMR, 1 H-NMR, C.O.S.Y. and N.O.E. indicates that the material is a 60:40 mixture of trans:cis isomers of the substituted stilbene compound.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US05728671uspto-grants-1998_03