Imidazole → 1,3-Dibenzyltetrahydro-1H-thieno[3,4-d]imidazole-2,4-dione

HRID 597599Notes

Reaction equation

HRID 597599 reaction equation
C(N(CC)CC)C.P12(SP3(SP(SP(S3)(S1)=S)(=S)S2)=S)=[S:9].[CH2:22]([N:29]1[C@H:33]2[CH2:34][O:35][C:36](=O)[C@H:32]2[N:31]([CH2:38][C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C:30]1=[O:45])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1.N1C=CN=C1>N1C=CC=CC=1C.O.C(OCC)(=O)C>[CH2:22]([N:29]1[C@H:33]2[CH2:34][S:9][C:36](=[O:35])[C@H:32]2[N:31]([CH2:38][C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C:30]1=[O:45])[C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1

Participants

8

Reactant 4

HCID 795ImidazoleHCID 8471TriethylamineHCID 14817Phosphorus sulfide (P2S5)HCID 119819(3AS,6aR)-1,3-dibenzyltetrahydro-1H-furo(3,4-d)imidazole-2,4-dione

Product 1

HCID 1198171,3-Dibenzyltetrahydro-1H-thieno[3,4-d]imidazole-2,4-dioneYield 85%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 79752-MethylpyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

Triethylamine (300 ml) and phosphorus pentasulfide (41 g) are added to a solution of 10.0 g of cis-1,3-dibenzyl-hexahydrofuro[3,4-d]imidazole-2,4-dione ([α]D20 + 62° (C = 2 in CHCl3)) and imidazole (21 g) in 150 ml of α-picoline. The mixture is stirred at room temperature for 1 hour and refluxed at about 100° C for 48 hours. Ethyl acetate (300 ml) and Celite-535 (5 g) are added to the reaction mixture cooled in an ice water bath, followed by addition of water (150 ml) and a saturated solution of sodium chloride (100 ml) and filtration of the resulting mixture. The organic layer is washed with water and concentrated in vacuo. The resulting residue is dissolved in 200 ml of toluene, followed by the addition of 7 % hydrochloric acid (100 ml) and zinc powder (10 g). The mixture is stirred and warmed at 60° to 65° C for 2 hours. The reaction mixture is cooled to room temperature and filtered off. The toluene layer is washed with water and concentrated in vacuo. The residue is triturated with ether, and the precipitate is filtered to give cis-1,3-dibenzyl-hexahydrothieno[-3,4-d]imidazole-2,4-dione (8.9 g, 85 %). M.P. 124° to 126° C. [α]D20 + 86° (C = 2 in CHCl3).

Workup

  1. temperaturerefluxed at about 100° C for 48 hours
  2. temperaturecooled in an ice water bath
  3. filtrationa saturated solution of sodium chloride (100 ml) and filtration of the resulting mixture
  4. washThe organic layer is washed with water
  5. concentrationconcentrated in vacuo
  6. dissolutionThe resulting residue is dissolved in 200 ml of toluene
  7. additionfollowed by the addition of 7 % hydrochloric acid (100 ml) and zinc powder (10 g)
  8. stirringThe mixture is stirred
  9. temperaturewarmed at 60° to 65° C for 2 hours
  10. temperatureThe reaction mixture is cooled to room temperature
  11. filtrationfiltered off
  12. washThe toluene layer is washed with water
  13. concentrationconcentrated in vacuo
  14. customThe residue is triturated with ether
  15. filtrationthe precipitate is filtered

Sources & evidence

ORD record
ord-3cffcc4f21384ce6ae97a8586d788a56
Source dataset
uspto-grants-1977_03
Patent number
US04014895

Reaction notes

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