Bromoacetic Acid → 5-[3,5-Bis(1,1-dimethyl-ethyl)-4-hydroxyphenyl]-1,3,4-thiadiazole-2-yl[thio]acetic acid

HRID 466062Notes

Reaction equation

HRID 466062 reaction equation
[OH-].[Na+].[CH3:3][C:4]([C:7]1[CH:8]=[C:9]([C:18]2[S:22][C:21](=[S:23])[NH:20][N:19]=2)[CH:10]=[C:11]([C:14]([CH3:17])([CH3:16])[CH3:15])[C:12]=1[OH:13])([CH3:6])[CH3:5].Br[CH2:25][C:26]([OH:28])=[O:27]>CO>[CH3:6][C:4]([C:7]1[CH:8]=[C:9]([C:18]2[S:22][C:21]([S:23][CH2:25][C:26]([OH:28])=[O:27])=[N:20][N:19]=2)[CH:10]=[C:11]([C:14]([CH3:15])([CH3:16])[CH3:17])[C:12]=1[OH:13])([CH3:3])[CH3:5]

Participants

5

Reactant 3

HCID 6227Bromoacetic AcidHCID 14798Sodium HydroxideHCID 30370185-(3,5-Di-tert-butyl-4-hydroxyphenyl)-1,3,4-thiadiazole-2(3H)-thione

Product 1

HCID 1360083465-[3,5-Bis(1,1-dimethyl-ethyl)-4-hydroxyphenyl]-1,3,4-thiadiazole-2-yl[thio]acetic acid

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Aqueous 1M NaOH (12.4 ml, 0.0124 mole) is added to 0° C. solution of 5-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1,3,4-thiadiazole-2(3H)-thione (2.0 g, 0.0062 mole) in methanol (20 ml). This is followed by addition of 2-bromoacetic acid (0.95 g, 0.0068 mole) in one portion. The resulting mixture is allowed to stir four hours with periodic warming. The solution is concentrated in vacuo and the residue is partitioned between ether and water. The layers are separated and the aqueous phase is made acidic with aqueous 6M HCl. The aqueous layer is extracted with 1:1 ethyl acetate/ether (2×). The combined organic layers are washed with saturated aqueous NaCl, and dried over MgSO4. Filtration and concentration in vacuo provides a solid which is recrystallized from ethyl acetate/hexane to give 1.6 g (2.4 g theor., 68%) of [[5-[3,5-bis(1,1-dimethyl-ethyl)-4-hydroxyphenyl]-1,3,4-thiadiazole-2-yl[thio]acetic acid, mp 187.5° C.

Workup

  1. concentrationThe solution is concentrated in vacuo
  2. customthe residue is partitioned between ether and water
  3. customThe layers are separated
  4. extractionThe aqueous layer is extracted with 1:1 ethyl acetate/ether (2×)
  5. washThe combined organic layers are washed with saturated aqueous NaCl
  6. dry with materialdried over MgSO4
  7. filtrationFiltration and concentration in vacuo
  8. customprovides a solid which
  9. customis recrystallized from ethyl acetate/hexane

Sources & evidence

ORD record
ord-4fb952043afc4d5a8fc656d7b410d806
Source dataset
uspto-grants-1992_10
Patent number
US05155122

Reaction notes

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