4-Bromo-2,6-di-tert-butylphenol → 2,6-Bis(1,1-dimethylethyl)-4-[[5-(methylthio)-1,3,4-thiadiazol-2-yl]thio]phenol

HRID 1029541Notes

Reaction equation

HRID 1029541 reaction equation
Br[C:2]1[CH:7]=[C:6]([C:8]([CH3:11])([CH3:10])[CH3:9])[C:5]([OH:12])=[C:4]([C:13]([CH3:16])([CH3:15])[CH3:14])[CH:3]=1.[CH3:17][S:18][C:19]1[S:23][C:22]([SH:24])=[N:21][N:20]=1.N12CCCN=C1CCCC=C2>CN(C)C=O.CCOCC>[CH3:9][C:8]([C:6]1[CH:7]=[C:2]([S:24][C:22]2[S:23][C:19]([S:18][CH3:17])=[N:20][N:21]=2)[CH:3]=[C:4]([C:13]([CH3:16])([CH3:15])[CH3:14])[C:5]=1[OH:12])([CH3:11])[CH3:10]

Participants

6

Reactant 3

HCID 708294-Bromo-2,6-di-tert-butylphenolHCID 219795291,8-Diazabicyclo(5.4.0)undecen-7-eneHCID 1785036205-methylsulfanyl-1,3,4-thiadiazole-2-thiol

Product 1

HCID 199006582,6-Bis(1,1-dimethylethyl)-4-[[5-(methylthio)-1,3,4-thiadiazol-2-yl]thio]phenolYield 18.1%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

A solution of 4-bromo-2,6-di-t-butylphenol (3.0 g, 10.5 mmol), 5-methylthio-1,3,4-thiadiazole-2-thiol (2.0 g, 12.2 mmol), and 1,8-diazabicyclo-[5.4.0]undecen-7-ene (1.8 mL, 12.0 mmol) in dimethylformamide (120 mL) is stirred at 55° to 70° C. for 48 hours. The reaction mixture is cooled and diluted with ether then washed four times with water and once with brine. Drying the organic phase over magnesium sulfate and evaporation gives a solid residue which is crystallized from ethyl acetate/hexane yielding 2.4 g (63%) of analytically pure light brown platelets; mp 144.0°-145.0° C. The mother liquor is chromatographed on silica gel eluting with 1:9 then 2:8 ethyl acetate:hexane to yield an additional 0.7 g (18%) of 2,6-bis(1,1-dimethylethyl)-4-[[5-(methylthio)-1,3,4-thiadiazol-2-yl]thio]phenol.

Workup

  1. temperatureThe reaction mixture is cooled
  2. washthen washed four times with water
  3. customDrying the organic phase
  4. customover magnesium sulfate and evaporation
  5. customgives a solid residue which
  6. customis crystallized from ethyl acetate/hexane yielding 2.4 g (63%) of analytically pure light brown platelets
  7. customThe mother liquor is chromatographed on silica gel eluting with 1:9

Sources & evidence

ORD record
ord-dc7916bb8f1a43a7a0df1a7ec229bc90
Source dataset
uspto-grants-1992_04
Patent number
US05102897

Reaction notes

Loading…