Sodium Hydroxide → Fumaric Acid

HRID 1447041Notes

Reaction equation

HRID 1447041 reaction equation
[OH-:1].[Na+].[C:3](O)(=O)[C:4]([OH:6])=[O:5].[Cl:9][C:10]1[CH:15]=[C:14]([Cl:16])[CH:13]=[CH:12][C:11]=1[CH:17]([S:24][C:25]([O:27][CH2:28][CH3:29])=[S:26])[CH2:18][N:19]1[CH:23]=[CH:22][N:21]=[CH:20]1.ClCS[CH2:33][C:34]1[CH:39]=[CH:38][C:37]([Cl:40])=[CH:36][CH:35]=1>C(O)C>[C:28]([OH:1])(=[O:27])/[CH:29]=[CH:3]/[C:4]([OH:6])=[O:5].[C:28]([OH:1])(=[O:27])/[CH:29]=[CH:3]/[C:4]([OH:6])=[O:5].[Cl:40][C:37]1[CH:38]=[CH:39][C:34]([CH2:33][S:26][CH2:25][S:24][CH:17]([C:11]2[CH:12]=[CH:13][C:14]([Cl:16])=[CH:15][C:10]=2[Cl:9])[CH2:18][N:19]2[CH:23]=[CH:22][N:21]=[CH:20]2)=[CH:35][CH:36]=1

Participants

6

Reactant 3

HCID 14798Sodium HydroxideHCID 12806890HCID 12806890, compoundHCID 86738243HCID 86738243, compound

Product 2

HCID 444972Fumaric AcidHCID 86738242HCID 86738242, compound

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

To a stirred solution of sodium hydroxide (2.02 g, 0.05 mole) in ethanol (180 ml) at 25° under a blanket of nitrogen, was added 1-[2-(2,4-dichlorophenyl)-2-(ethoxythiocarbonylthio)ethyl]1-H-imidazole hydrogen oxalate* (4.51 g, 0.01 mole). After stirring at 25° for 0.75 hour a solution of 4-chlorobenzyl chloromethyl sulfide (2.07 g, 0.01 mole) in ethanol (2 ml) was added. The mixture was refluxed for twenty hours and concentrated to dryness. The residue was partitioned between diethyl ether and water. The ethereal layer was washed successively with H2O, Na2Co3 -H2O, H2O, brine and dried (Na2SO4). Removal of the ether left the free base (3.3 g) as a viscous brown oil. Treatment of a solution of the free base (3.3 g) in acetonitrile with fumaric acid (0.78 g) provided 2.5 g of the title compound, mp 120°-125°. Recrystallization from ethyl acetate gave colorless crystals, mp 121°-123°, of the analytical sample.

Workup

  1. additionwas added
  2. temperatureThe mixture was refluxed for twenty hours
  3. concentrationconcentrated to dryness
  4. customThe residue was partitioned between diethyl ether and water
  5. washThe ethereal layer was washed successively with H2O, Na2Co3 -H2O, H2O, brine
  6. dry with materialdried (Na2SO4)
  7. customRemoval of the ether
  8. waitleft the free base (3.3 g) as a viscous brown oil

Sources & evidence

ORD record
ord-122296cddb8f4585b0aad6eb727633aa
Source dataset
uspto-grants-1982_02
Patent number
US04315023

Reaction notes

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