Citric Acid → HCID 21713169, compound

HRID 650710Notes

Reaction equation

HRID 650710 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([C:7]([C:9]2[CH:14]=[CH:13][C:12]([S:15]([O-:17])=[O:16])=[CH:11][CH:10]=2)=[O:8])=[CH:3][CH:2]=1.[Na+].II.[CH2:21]([C:24](=[CH2:28])[C:25]([OH:27])=[O:26])[CH2:22][CH3:23].C(N(CC)CC)C.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>O.ClCCl>[CH2:21](/[C:24](=[CH:28]\[S:15]([C:12]1[CH:11]=[CH:10][C:9]([C:7]([C:4]2[CH:5]=[CH:6][N:1]=[CH:2][CH:3]=2)=[O:8])=[CH:14][CH:13]=1)(=[O:17])=[O:16])/[C:25]([OH:27])=[O:26])[CH2:22][CH3:23]

Participants

8

Reactant 5

HCID 311Citric AcidHCID 807IodineHCID 8471TriethylamineHCID 51650432-Propylacrylic acidHCID 23717811HCID 23717811, compound

Product 1

HCID 21713169HCID 21713169, compoundYield 24%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Sodium 4-(pyridine-4-carbonyl)benzenesulfinate (3.33 g, 14.04 mmol) was dissolved in water (60 ml). This solution was shaken with iodine (3.56 g, 34.29 mmol) in dishloromethane (40 ml). The dichloromethane layer turned from deep pink to orange. The dishloromethane layer was dried over magnesium sulfate and filtered into a flask containing 2-propylacrylic acid (0.8 g, 7.02 mmol). The solution was stirred overnight at room temperature and then cooled to 0° C. Triethylamine (4.0 ml, 28.08 mmol) was added and the solution was allowed to warm to room temperature over 2 hours. The mixture was acidified to pH 4 by addition of 10% citric acid. The layers were separated and the product was extracted with 2M sodium hydroxide (3×50 ml). The combined aqueous phase was washed with ethyl acetate (50 ml), the acidified to pH 4 with citric acid. The product was extracted into ethyl acetate (2×50 ml), then back into 1M hydrochloric acid (100 ml). The aqueous layer was washed with ethyl acetate (2×50 ml), then solid sodium hydrogen carbonate was added to pH 4. The product was extracted into dichloromethane (2×50 ml) and the combined organic layers were washed with brine (20 ml), dried over magnesium sulfate, filtered and evaporated to give the title compound (0.60 g, 24%).

Workup

  1. dry with materialThe dishloromethane layer was dried over magnesium sulfate
  2. filtrationfiltered into a flask
  3. temperaturecooled to 0° C
  4. temperatureto warm to room temperature over 2 hours
  5. customThe layers were separated
  6. extractionthe product was extracted with 2M sodium hydroxide (3×50 ml)
  7. washThe combined aqueous phase was washed with ethyl acetate (50 ml)
  8. extractionThe product was extracted into ethyl acetate (2×50 ml)
  9. washThe aqueous layer was washed with ethyl acetate (2×50 ml)
  10. additionsolid sodium hydrogen carbonate was added to pH 4
  11. extractionThe product was extracted into dichloromethane (2×50 ml)
  12. washthe combined organic layers were washed with brine (20 ml)
  13. dry with materialdried over magnesium sulfate
  14. filtrationfiltered
  15. customevaporated

Sources & evidence

ORD record
ord-2bb800cd7d224ae69536f4027900fb4f
Source dataset
uspto-grants-2001_08
Patent number
US06274758B1

Reaction notes

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