Methanol → HCID 178418388, Verbindung

HRID 355661

Reaktionsgleichung

Reaktionsgleichung von HRID 355661
C1([PH+](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(CO[C:25]1[CH:30]=[CH:29][C:28]([CH3:31])=[CH:27][CH:26]=1)(O)=O.[CH:32]([C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][C:35]=1[S:40]([OH:43])(=[O:42])=[O:41])=O.[Na].[CH3:45][O-:46].[Na+:47].[CH3:48][OH:49]>CS(O)(=O)=O>[Na:47][C:27]1[CH:26]=[CH:25][CH:30]=[CH:29][C:28]=1/[CH:31]=[CH:32]/[C:34]1[CH:39]=[CH:38][C:37]([C:45]([O:49][CH3:48])=[O:46])=[CH:36][C:35]=1[S:40]([OH:43])(=[O:42])=[O:41]

Komponenten

7

Edukt 5

HCID 887MethanolHCID 70492-Formylbenzenesulfonic acidHCID 5360545SodiumHCID 10942334Sodium MethoxideHCID 86752270Triphenylphosphonium (4-carboxymethoxyphenyl)methane

Produkt 1

HCID 178418388HCID 178418388, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6395Methanesulfonic AcidKatalysator

Versuchsvorschrift

To 146 gm (0.327 mol) of the adduct prepared in Example 10 in a 2L, 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 arc 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.

Aufarbeitung

  1. temperatureThe solution is heated
  2. temperatureto reflux under argon
  3. temperatureThe solution is heated
  4. temperatureat reflux for 8 hrs
  5. customMost of the methanol is removed on the rotary evaporator (~60° C.)
  6. customforming a milky suspension
  7. temperatureThe mixture is cooled in an ice bath
  8. filtrationfiltered
  9. concentrationThe mother liquor is concentrated to ~800 mL on the rotary evaporator and refrigerated overnight
  10. customThe crystals which form arc
  11. filtrationfiltered
  12. customdried
  13. concentrationThe water layer is concentrated

Quellen und Nachweise

ORD-Eintrag
ord-37a61dd4f384488498902bfb0587b22a
Quelldatensatz
uspto-grants-1998_11
Patentnummer
US05834412

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