Toluene → 3,4-Di(t-butylperoxycarbonyl)-1,2,5-thiadiazole

HRID 260539

Reaction equation

HRID 260539 reaction equation
[S:1]1[N:5]=[C:4]([C:6]([OH:8])=[O:7])[C:3]([C:9]([OH:11])=[O:10])=[N:2]1.N/C(/C#N)=C(\N)/C#N.C1(C)C=CC(S(Cl)(=O)=[O:27])=CC=1.[C:31]([O:35]O)([CH3:34])([CH3:33])[CH3:32].[C:37]1([CH3:43])[CH:42]=CC=C[CH:38]=1>N1C=CC=CC=1.O>[C:31]([O:35][O:10][C:9]([C:3]1[C:4]([C:6]([O:8][O:27][C:37]([CH3:43])([CH3:42])[CH3:38])=[O:7])=[N:5][S:1][N:2]=1)=[O:11])([CH3:34])([CH3:33])[CH3:32]

Participants

8

Reactant 5

HCID 1140TolueneHCID 6410tert-Butyl hydroperoxideHCID 73974-Toluenesulfonyl chlorideHCID 2700161,2,5-Thiadiazole-3,4-dicarboxylic acid2×HCID 2723951Diaminomaleonitrile

Product 1

HCID 199776523,4-Di(t-butylperoxycarbonyl)-1,2,5-thiadiazole

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1049PyridineSolvent2×

Procedure

The preparation described in Warren, J. D., et al, J. Heterocyclic Chem. 16, 1817 (1979) was used to prepare 1,2,5-thiadiazole-3,4-dicarboxylic acid from diaminomaleonitrile. At room temperature, 4.30 g of p-toluenesulfonyl chloride was added to a solution of 0.990 g of 1,2,5-thiadiazole-3,4-dicarboxylic acid in 10 mL of pyridine. The solution was cooled in an ice bath and 1.09 g of t-butylhydroperoxide (90% solution in water) was added. The solution was stirred for one hour during which it was cooled with an ice bath such that the temperature was as low as possible without freezing the pyridine. The solution was then poured into a mixture of water and toluene. The toluene layer was separated and washed twice with a 10% aqueous sodium hydroxide solution. The toluene solution was then dried over sodium sulfate and the solvents removed giving rise to 1.414 g of a yellow liquid. The yellow liquid was purified by column chromatography to give a colorless solid with a melting point of 39°-41° C.; 1H NMR (CDCl3) δ 1.42 (s); IR (coated on a thin polymer film) 1784, 1132, 1019 cm-1. ##STR17##

Workup

  1. temperatureThe solution was cooled in an ice bath
  2. temperaturewas cooled with an ice bath such that the temperature
  3. customThe toluene layer was separated
  4. washwashed twice with a 10% aqueous sodium hydroxide solution
  5. dry with materialThe toluene solution was then dried over sodium sulfate
  6. customthe solvents removed

Sources & evidence

ORD record
ord-22b50df7327346b88708c74ba16c6802
Source dataset
uspto-grants-1996_06
Patent number
US05527921

Linked notes

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