Carbon Disulfide → 2,6-Di-tert-butyl-4-(5-mercapto-[1,3,4]oxadiazol-2-yl)-phenol

HRID 466045Notes

Reaction equation

HRID 466045 reaction equation
[OH-].[K+].[CH3:3][C:4]([C:7]1[CH:8]=[C:9]([CH:14]=[C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:16]=1[OH:17])[C:10]([NH:12][NH2:13])=[O:11])([CH3:6])[CH3:5].[C:22](=S)=[S:23]>C(O)C>[CH3:6][C:4]([C:7]1[CH:8]=[C:9]([C:10]2[O:11][C:22](=[S:23])[NH:13][N:12]=2)[CH:14]=[C:15]([C:18]([CH3:21])([CH3:20])[CH3:19])[C:16]=1[OH:17])([CH3:3])[CH3:5]

Participants

5

Reactant 3

HCID 6348Carbon DisulfideHCID 14797Potassium HydroxideHCID 104229343,5-Di-tert-butyl-4-hydroxybenzohydrazide

Product 1

HCID 1354128192,6-Di-tert-butyl-4-(5-mercapto-[1,3,4]oxadiazol-2-yl)-phenolYield 38%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
0 °C

Procedure

Potassium hydroxide (1.1 g, 0.019 mole) is added in one portion to a stirred 0° C. solution of 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzoic acid hydrazide (5.0 g, 0.019 mole) and carbon disulfide (3.4 g, 0.044 mole) in absolute ethanol (60 ml). The resulting mixture is stirred 30 minutes at 0° C. before warming to room temperature and stirring one hour. The solution is then heated to reflux for 2.5 hours. The solvent is removed in vacuo and the residue dissolved in water (100 ml) and washed with ether. The aqueous layer is made acidic with 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 recrystallized from ethyl acetate/isopropyl ether to give 2.2 g (5.8 g theor., 38%) desired 5-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1,3,4-oxadiazole2(3H)-thione, mp 253.5° C.

Workup

  1. temperaturebefore warming to room temperature
  2. stirringstirring one hour
  3. temperatureThe solution is then heated
  4. temperatureto reflux for 2.5 hours
  5. customThe solvent is removed in vacuo
  6. dissolutionthe residue dissolved in water (100 ml)
  7. washwashed with ether
  8. extractionthe product extracted with a 1:1 mixture of ethyl acetate/ether
  9. washThe organic layer is washed with saturated aqueous NaCl
  10. dry with materialdried over MgSO4
  11. filtrationFiltration and concentration
  12. customgives a solid which
  13. customis recrystallized from ethyl acetate/isopropyl ether

Sources & evidence

ORD record
ord-3471bb8ea0364ebd8375ab685a34a303
Source dataset
uspto-grants-1992_10
Patent number
US05155122

Reaction notes

Loading…