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

HRID 1492996

反応式

HRID 1492996 の反応式
[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]

参加物

5

反応物 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

生成物 1

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

試薬・触媒・溶媒 1

HCID 22007288Pyridine toluene溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-402093f87c3b4d58803c6ae32c442f15
出典データセット
uspto-grants-1994_12
特許番号
US05376670

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