Iodine → (E)-3-(Methoxybenzenesulfonyl)-2-[(3,4,4-trimethyl-2,5-dioxoimidazolidin-1-yl)propyl]acrylic acid

HRID 650711Notes

Reaction equation

HRID 650711 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6](S([O-])=O)=[CH:5][CH:4]=1.[Na+].II.[C:15]([C:18]([CH2:23][CH2:24][CH2:25][N:26]1[C:30](=[O:31])[C:29]([CH3:33])([CH3:32])[N:28]([CH3:34])[C:27]1=[O:35])=[CH:19][S:20]([O-:22])=[O:21])([OH:17])=[O:16].[Na+].C(N(CC)CC)C.S(=O)(=O)(O)O>O.ClCCl>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[S:20](/[CH:19]=[C:18](\[CH2:23][CH2:24][CH2:25][N:26]1[C:30](=[O:31])[C:29]([CH3:32])([CH3:33])[N:28]([CH3:34])[C:27]1=[O:35])/[C:15]([OH:17])=[O:16])(=[O:22])=[O:21]

Participants

8

Reactant 5

HCID 807IodineHCID 1118Sulfuric AcidHCID 8471TriethylamineHCID 23680956Sodium 4-methoxybenzene-1-sulfinateHCID 70247321Sodium 2-carboxy-5-(3,4,4-trimethyl-2,5-dioxoimidazolidin-1-yl)pent-1-ene-1-sulfinate

Product 1

HCID 70247073(E)-3-(Methoxybenzenesulfonyl)-2-[(3,4,4-trimethyl-2,5-dioxoimidazolidin-1-yl)propyl]acrylic acidYield 88%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

Sodium 4-methoxyphenylsulfinate (10.0 g, 51.49 mmol) was dissolved in water (100 ml). This solution was shaken with iodine (9.8 g, 36.61 mmol) in dichloromethane (100 ml). The dichloromethane layer turned from deep pink to orange. The dichloromethane layer was dried over magnesium sulfate and filtered into a flask containing sodium 2-carboxy-5-(3,4,4-trimethyl-2,5-dioxoimidazolidin-1-yl)pent-1-ene-1-sulfinate (6.47 g, 25.74 mmol). The solution was stired overnight at room temperature and then cooled to 0° C. Triethylamine (11.0 ml, 77.23 mmol) was added and the solution was allowed to warm to room temperature over 2 hours. Sulfuric acid (2M, 50 ml) was added to quench the reaction. The organic phase was washed with 10% aqueous sodium bisulfite (50 ml), then extracted with sodium hydroxide (2M, 3×50 ml). The aqueous layer was washed with dichloromethane (50 ml) and the acidifed with sulfuric acid (2M) to pH 1. The product was extracted into dichloromethane (3×50 ml) and the combined organic layers were washed with brine (20 ml), dried over magnesium sulfate, filtered and evaporaed to give the title compound in 88% yield. This yellow oil was crystallised from MTBE/DCM 40:1 to give the title compound as a white solid (5.6 g, 51%).

Workup

  1. dry with materialThe dichloromethane layer was dried over magnesium sulfate
  2. filtrationfiltered into a flask
  3. temperatureto warm to room temperature over 2 hours
  4. customto quench
  5. customthe reaction
  6. washThe organic phase was washed with 10% aqueous sodium bisulfite (50 ml)
  7. extractionextracted with sodium hydroxide (2M, 3×50 ml)
  8. washThe aqueous layer was washed with dichloromethane (50 ml)
  9. extractionThe product was extracted into dichloromethane (3×50 ml)
  10. washthe combined organic layers were washed with brine (20 ml)
  11. dry with materialdried over magnesium sulfate
  12. filtrationfiltered

Sources & evidence

ORD record
ord-1a0fc2fa3ef94549bc3e5236139a2c19
Source dataset
uspto-grants-2001_08
Patent number
US06274758B1

Reaction notes

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