Piperidine → 5-[2-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-vinyl]-2,4-dihydro-[1,2,4]triazole-3-thione

HRID 1657063

Reaktionsgleichung

Reaktionsgleichung von HRID 1657063
[S:1]=[C:2]1[NH:6][N:5]=[C:4]([CH2:7][C:8](O)=O)[NH:3]1.[CH3:11][C:12]([C:15]1[CH:16]=[C:17]([CH:20]=[C:21]([C:24]([CH3:27])([CH3:26])[CH3:25])[C:22]=1[OH:23])C=O)([CH3:14])[CH3:13].N1CCCCC1>C1(C)C=CC=CC=1.N1C=CC=CC=1>[OH:23][C:22]1[C:21]([C:24]([CH3:26])([CH3:25])[CH3:27])=[CH:20][C:17](/[CH:8]=[CH:7]/[C:4]2[NH:3][C:2](=[S:1])[NH:6][N:5]=2)=[CH:16][C:15]=1[C:12]([CH3:14])([CH3:13])[CH3:11]

Komponenten

5

Edukt 3

HCID 8082PiperidineHCID 732193,5-Di-tert-butyl-4-hydroxybenzaldehydeHCID 1785252602-(5-thioxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)acetic acid

Produkt 1

HCID 1784408285-[2-(3,5-Di-tert-butyl-4-hydroxy-phenyl)-vinyl]-2,4-dihydro-[1,2,4]triazole-3-thioneAusbeute 33 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 22007288Pyridine tolueneLösungsmittel

Versuchsvorschrift

A solution of 2-(5-thioxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)acetic acid (prepared by the method described in Aust. J. Chem., 1979, 32, 161-5, Nowel W. Jacobsen, Bruce L. McCarthy, Stephanie Smith) (3.3 g, 0.021 mole) and 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzaldehyde (4.9 g, 0.021 mole) in a 2:1 mixture of toluene/pyridine (300 ml) is treated with piperidine (0.021 mole). The resulting mixture is stirred at reflux for 48 hours. The mixture is concentrated in vacuo and the residue dissolved in ether, the product is extracted from the organic phase with aqueous 1M NaOH. The combined aqueous layers are made acidic by treatment with aqueous 2M HCl, and the product extracted with a 1:1 mixture of ethyl acetate/ether. The organic layer is washed with saturated aqueous NaCl and dried over MgSO4. Filtration and concentration gives a solid which is triturated in hot isopropyl ether and filtered to provide 2.3 g (6.9 g theor., 33%) of desired (E)-2,4-dihydro-5-[2-[4-hydroxy-3,5-bis(1,1-dimethylethyl)phenyl]ethenyl]-3H-1,2,4-triazole-3-thione, mp 243° C.

Aufarbeitung

  1. temperatureat reflux for 48 hours
  2. concentrationThe mixture is concentrated in vacuo
  3. dissolutionthe residue dissolved in ether
  4. extractionthe product is extracted from the organic phase with aqueous 1M NaOH
  5. extractionthe product extracted with a 1:1 mixture of ethyl acetate/ether
  6. washThe organic layer is washed with saturated aqueous NaCl
  7. dry with materialdried over MgSO4
  8. filtrationFiltration and concentration
  9. customgives a solid which
  10. customis triturated in hot isopropyl ether
  11. filtrationfiltered

Quellen und Nachweise

ORD-Eintrag
ord-ebdc466cc8bf41e1a0395a91f2a12e6d
Quelldatensatz
uspto-grants-1993_10
Patentnummer
US05256680

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