Potassium Iodide → 3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid

HRID 1586314

Reaktionsgleichung

Reaktionsgleichung von HRID 1586314
Cl[C:2]1[CH:27]=[CH:26][C:5]2=[N:6][N:7]([C:9]3[CH:10]=[C:11]([CH:18]=[C:19]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:20]=3[OH:21])[CH2:12][CH2:13][C:14]([O:16]C)=[O:15])[N:8]=[C:4]2[CH:3]=1.[OH-].[Na+].[I-].[K+].[C:32]1([SH:38])[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>CN(C)C=O>[C:32]1([S:38][C:2]2[CH:27]=[CH:26][C:5]3=[N:6][N:7]([C:9]4[CH:10]=[C:11]([CH:18]=[C:19]([C:22]([CH3:25])([CH3:24])[CH3:23])[C:20]=4[OH:21])[CH2:12][CH2:13][C:14]([OH:16])=[O:15])[N:8]=[C:4]3[CH:3]=2)[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1

Komponenten

6

Edukt 4

HCID 4875Potassium IodideHCID 7969Thiophenol2×HCID 14798Sodium HydroxideHCID 30191402-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole

Produkt 1

HCID 212181283-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acidAusbeute 72,3 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6228DimethylformamideLösungsmittel2×

Reaktionsbedingungen

Temperatur
77.5 °C

Versuchsvorschrift

To a 1 liter, 4 necked, round-bottomed flask equipped with mechanical stirring and a nitrogen atmosphere is charged 100.0 g (0.258 mol) of methyl 3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, 350 mL of N,N-dimethylformamide, and 61.9 g (0.773 mol) of 50% aqueous sodium hydroxide solution. The mixture is heated at 75-80° C. for 3 hours at which point the ester hydrolysis is complete. A catalytic amount of potassium iodide (5.0 g) is added. Thiophenol (32.2 g, 0.258 mol) is then added over a 20 minute period while the temperature remains at 75-80° C. An additional portion of N,N-dimethylformamide (200 mL) is added during the addition of thiophenol to facilitate stirring. A 25 mL fraction of water/methanol is removed and the solution is refluxed for 48 hours. The reaction mixture is cooled, then partitioned between 1.0 L of 1N hydrochloric acid and 1.0 L of ethyl acetate. The phases are separated and the organic phase is dried over anhydrous magnesium sulfate, and the solvent is then removed under reduced pressure until the total volume is 500 mL. To this is added 200 mL of heptane and the solution is allowed to sit overnight. The resultant crystals are collected by vacuum filtration, washed with 9:1 heptane:ethyl acetate, and dried to afford 83.5 g (72% yield) of the title compound; mp 154-156° C.

Aufarbeitung

  1. customTo a 1 liter, 4 necked, round-bottomed flask equipped
  2. customremains at 75-80° C
  3. stirringto facilitate stirring
  4. customA 25 mL fraction of water/methanol is removed
  5. temperaturethe solution is refluxed for 48 hours
  6. temperatureThe reaction mixture is cooled
  7. custompartitioned between 1.0 L of 1N hydrochloric acid and 1.0 L of ethyl acetate
  8. customThe phases are separated
  9. dry with materialthe organic phase is dried over anhydrous magnesium sulfate
  10. customthe solvent is then removed under reduced pressure until the total volume is 500 mL
  11. additionTo this is added 200 mL of heptane
  12. filtrationThe resultant crystals are collected by vacuum filtration
  13. washwashed with 9:1 heptane
  14. dry with materialethyl acetate, and dried

Quellen und Nachweise

ORD-Eintrag
ord-2321fe09e5494f7eb11be82a4966be86
Quelldatensatz
uspto-grants-1999_08
Patentnummer
US05942626

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