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

HRID 1492996

반응식

HRID 1492996 반응식
[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]

참가 물질

5

반응물 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

생성물 1

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

시약·촉매·용매 1

HCID 22007288Pyridine toluene용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-402093f87c3b4d58803c6ae32c442f15
출처 데이터셋
uspto-grants-1994_12
특허 번호
US05376670

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