Sulfuric Acid → cis-2-oxo-1,3-dibenzyl-hexahydro-1H-thieno[3,4-d]imidazol-4-ylidenepentanoic acid

HRID 980328Notes

Reaction equation

HRID 980328 reaction equation
[CH2:1]([N:8]1[C@H:12]2[CH2:13][S:14][C:15](=[CH:16][CH2:17][CH2:18][CH2:19]C34CC5CC(OC(O5)O3)C4)[C@H:11]2[N:10]([CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[C:9]1=[O:37])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.S(=O)(=O)(O)O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[OH-:54].[Na+].[O:56]1[CH2:61]COCC1>>[O:37]=[C:9]1[N:8]([CH2:1][C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)[C@H:12]2[CH2:13][S:14][C:15](=[C:16]([CH2:17][CH2:18][CH3:19])[C:61]([OH:56])=[O:54])[C@H:11]2[N:10]1[CH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

Participants

6

Reactant 5

HCID 1118Sulfuric AcidHCID 6101p-Toluenesulfonic acidHCID 14798Sodium HydroxideHCID 312751,4-DioxaneHCID 86741215HCID 86741215, compound

Product 1

HCID 86591115cis-2-oxo-1,3-dibenzyl-hexahydro-1H-thieno[3,4-d]imidazol-4-ylidenepentanoic acidYield 89%

Procedure

839 mg (1.62 mmol) of cis-1,3-dibenzyl-4-(4-(2,4,10-trioxaadamantyl)-butylidene)-hexahydro-1H-thieno[3,4-d]imidazol-2-one (prepared in accordance with Example 3) are treated with 4.6 ml of dioxan, 4.6 ml of 0.2N sulphuric acid as well as 20 mg of p-toluenesulphonic acid and the mixture is heated to boiling under an argon atmosphere for 2.5 hours. The mixture is subsequently made alkaline with 1.54 ml of 2N sodium hydroxide solution and boiled under reflux for a further 45 minutes. After cooling to room temperature the solution is extracted with ethyl acetate and the extract is discarded. The aqueous phase is acidified with dilute hydrochloric acid and again extracted with a total of 200 ml of ethyl acetate. The combined extracts are washed once with saturated sodium chloride solution and dried over sodium sulphate. After removing the solvent there are obtained 622 mg (89% of theory) of cis-2-oxo-1,3-dibenzyl-hexahydro-1H-thieno[3,4-d]imidazol-4-ylidenepentanoic acid.

Workup

  1. temperaturethe mixture is heated
  2. temperatureunder reflux for a further 45 minutes
  3. extractionis extracted with ethyl acetate
  4. extractionagain extracted with a total of 200 ml of ethyl acetate
  5. washThe combined extracts are washed once with saturated sodium chloride solution
  6. dry with materialdried over sodium sulphate
  7. customAfter removing the solvent there

Sources & evidence

ORD record
ord-ef2e00b60a534c1286079f7421300df2
Source dataset
uspto-grants-1987_01
Patent number
US04636566

Reaction notes

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