Hydrochloric Acid → HCID 14401081, Verbindung

HRID 1033698

Reaktionsgleichung

Reaktionsgleichung von HRID 1033698
[OH-].[K+].CC([O:11]S(C1C=CC(C)=CC=1)(=O)=O)CCCCCC.Cl.[F:23][C:24]1[CH:25]=[C:26]([CH:29]=[CH:30][C:31]=1[O:32][CH:33]([CH3:40])[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39])[CH:27]=[O:28]>CO.C(O)(=O)C.O.C1(C)C=CC=CC=1>[F:23][C:24]1[CH:25]=[C:26]([CH:29]=[CH:30][C:31]=1[O:32][CH:33]([CH3:40])[CH2:34][CH2:35][CH2:36][CH2:37][CH2:38][CH3:39])[C:27]([OH:11])=[O:28]

Komponenten

9

Edukt 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 3912199p-Toluenesulfonic acid 1-methylheptyl esterHCID 144010803-Fluoro-4-(1-methyl-heptyloxy)-benzaldehyde

Produkt 1

HCID 14401081HCID 14401081, VerbindungAusbeute 39 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 176Acetic AcidLösungsmittel2×HCID 887MethanolLösungsmittelHCID 962WaterLösungsmittelHCID 1140TolueneLösungsmittel

Versuchsvorschrift

On the other hand, o-fluorophenol (500 g, 4.46 mols) was added to a solution of NaOH (1,250 g, 31.26 mols) dissolved in water (2 l), followed by dropwise adding chloroform (1,230 g), agitating the mixture at about 60° C. for 2 hours, acidifying it with sulfuric acid, filtering off the residue on heating, and recrystallizing the deposited crystals from a mixed solvent of water-methanol to obtain 3-fluoro-4-hydroxybenzaldehyde (35.3 g) having a m.p. of 119.5°~123.5° C. This product (30 g, 0.21 mol) was dissolved in methanol (300 ml), followed by adding and dissolving KOH (12 g, 0.21 mol), dropwise adding optically active p-toluenesulfonic acid 1-methyl-heptyl ester (65 g, 0.23 mol) prepared above, keeping the mixture under reflux for 4 hours, cooling, adding toluene (200 ml) and 6N-HCl (100 ml), washing the resulting toluene layer with 2N-NaOH aqueous solution, further washing with water till the washing layer became neutral, and distilling off toluene to obtain as residue, optically active 3-fluoro-4-(1-methyl-heptyloxy)-benzaldehyde (14.7 g). This product (10 g, 0.04 mol) was dissolved in acetic acid (200 ml), followed by dropwise adding a solution of chromic anhydride (4 g, 0.04 mol) dissolved in acetic acid (50 ml) and water (40 ml), agitating the mixture at 40°~50° C. for about 6 hours, pouring the resulting reaction material in ice water and filtering off the deposited crystals to obtain optically active 3-fluoro-4-(1-methyl-heptyloxy)-benzoic acid (6.1 g) having a m.p. of 57.2°~59.2° C., adding thionyl chloride (4.2 g, 0.035 mol) to the above product (6 g, 0.022 mol), heating the mixture under reflux with stirring for one hour, and distilling off excess thionyl chloride to obtain optically active 3-fluoro-4-(1-methyl-heptyloxy)-benzoic acid chloride (6.1 g).

Aufarbeitung

  1. additionby adding
  2. customprepared above,
  3. temperatureunder reflux for 4 hours
  4. temperaturecooling
  5. washwashing the resulting toluene layer with 2N-NaOH aqueous solution
  6. washfurther washing with water till the washing layer
  7. distillationdistilling off toluene
  8. customto obtain as residue
  9. additionpouring
  10. filtrationfiltering off the deposited crystals

Quellen und Nachweise

ORD-Eintrag
ord-839259f049244bed9c25e8754ce3ccd3
Quelldatensatz
uspto-grants-1994_05
Patentnummer
US05312564

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