Potassium Iodide → HCID 131719173, compound

HRID 399090Notes

Reaction equation

HRID 399090 reaction equation
C([O:8][C:9]1[CH:14]=[C:13]([O:15][CH2:16][CH2:17][CH2:18]Cl)[C:12]([CH2:20][CH3:21])=[CH:11][C:10]=1[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)C1C=CC=CC=1.[C:28]([C:33]1[CH:46]=[C:45]2[C:36]([O:37][C:38]3[C:39](CCC(OCC)=O)=[C:40]([OH:48])[CH:41]=[CH:42][C:43]=3[C:44]2=[O:47])=[CH:35][CH:34]=1)(OCC)=[O:29].[C:56](=[O:59])([O-])[O-:57].[K+].[K+].[I-].[K+].[OH-:64].[Na+:65].[C:66](OCC)(=O)[CH3:67]>CO.O1CCCC1.CS(C)=O>[OH2:8].[Na+:65].[Na+:65].[C:28]([C:33]1[CH:46]=[C:45]2[C:36]([O:37][C:42]3[C:41]([CH2:66][CH2:67][C:56]([O-:57])=[O:59])=[C:40]([O:48][CH2:18][CH2:17][CH2:16][O:15][C:13]4[CH:14]=[C:9]([OH:8])[C:10]([C:22]5[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=5)=[CH:11][C:12]=4[CH2:20][CH3:21])[CH:39]=[CH:38][C:43]=3[C:44]2=[O:47])=[CH:35][CH:34]=1)([OH:29])=[O:64].[C:28]([C:33]1[CH:46]=[C:45]2[C:36]([O:37][C:42]3[C:41]([CH2:66][CH2:67][C:56]([O-:57])=[O:59])=[C:40]([O:48][CH2:18][CH2:17][CH2:16][O:15][C:13]4[CH:14]=[C:9]([OH:8])[C:10]([C:22]5[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=5)=[CH:11][C:12]=4[CH2:20][CH3:21])[CH:39]=[CH:38][C:43]=3[C:44]2=[O:47])=[CH:35][CH:34]=1)([OH:29])=[O:64]

Participants

9

Reactant 6

HCID 4875Potassium IodideHCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 10786055HCID 10786055, compoundHCID 15718086HCID 15718086, compound

Product 1

HCID 131719173HCID 131719173, compoundYield 56%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

A mixture of 2-benzyloxy-1-phenyl-5-ethyl-4-(3-chloro-1-propyloxy)benzene (749 mg, 1.97 mmol), ethyl 7-carboethoxy-3-hydroxy-9-oxo-9H-xanthene-4-propanoate (729 mg, 1.97 mmol), potassium carbonate (1.36 g, 9.85 mmol) and potassium iodide (33 mg, 0.20 mmol) was refluxed for 24 hours. Dimethylsulfoxide (2 mL) was added and heating continued for 24 hours. The reaction mixture was cooled to room temperature, diluted with ethyl acetate, and washed once with water. The organic layer was dried over sodium sulfate, filtered and concentrated in vacuo to reveal a tan solid. This material was dissolved in ethyl acetate (30 mL) and the resulting solution purged with nitrogen. To this solution was added 10% palladium on carbon (120 mg) and the resulting suspension hydrogenated at 1 atmosphere of pressure. The solution was filtered and concentrated in vacuo to provide a colorless oil. This material was dissolved in a solution of 1:1 methanol/tetrahydrofuran (30 mL) and treated with 5N sodium hydroxide solution (2 mL) at room temperature for 18 hours. The resulting solution was extracted once with diethyl ether and the aqueous layer acidified with 5N hydrochloric acid solution. The resulting precipitate was collected via suction filtration. This material was converted to the di-sodium salt and purified as described above for the preparation of Example 1(D) to provide 390 mg (56%) of the desired title product as a fluffy white solid: NMR (DMSO-d6) 12.65 (s, 1H, --OH), 8.65 (s, 1H), 8.28 (dd, J 8.5, 2.0 Hz, 1H), 8.01 (d, J=8.9 Hz, 1H), 7.50 (m, 3H), 7.29 (t, J 7.8 Hz, 2H), 7.17 (m, 2H), 6.93 (s, 1H), 6.89 (s, 1H), 4.26 (m, 4H), 3.12 (m, 2H), 2.47 (m, 2H), 2.23 (m, 2H), 1.10 (t, J=7.4 Hz, 3H); MS-FAB m/e 627 (24, p), 605 (40), 583 (24), 331 (24), 309 (100); IR (KBr, cm-1) 3419 (b), 2962, 1612, 1558, 1443, 1390, 1277, 1084.

Workup

  1. temperaturewas refluxed for 24 hours
  2. temperatureheating
  3. washwashed once with water
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. dissolutionThis material was dissolved in ethyl acetate (30 mL)
  8. customthe resulting solution purged with nitrogen
  9. additionTo this solution was added 10% palladium on carbon (120 mg)
  10. filtrationThe solution was filtered
  11. concentrationconcentrated in vacuo
  12. customto provide a colorless oil
  13. extractionThe resulting solution was extracted once with diethyl ether
  14. filtrationThe resulting precipitate was collected via suction filtration
  15. custompurified
  16. customas described above for the preparation of Example 1(D)

Sources & evidence

ORD record
ord-f793337b52a14328a7a26c5701c82701
Source dataset
uspto-grants-1998_10
Patent number
US05817684

Reaction notes

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