Water → 3-[(5-Chloro-1,3-benzodithiol-2-ylidene)amino]propanoic acid, ethyl ester

HRID 2419133Notes

Reaction equation

HRID 2419133 reaction equation
[I-].[Cl:2][C:3]1[CH:19]=[CH:18][C:6]2[S:7][C:8](=[N+](C)C3C=CC=CC=3)[S:9][C:5]=2[CH:4]=1.Cl.[NH2:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25].C(=O)([O-])[O-].[Na+].[Na+].O>CN(C)C=O>[Cl:2][C:3]1[CH:19]=[CH:18][C:6]2[S:7][C:8](=[N:21][CH2:22][CH2:23][C:24]([O:26][CH2:27][CH3:28])=[O:25])[S:9][C:5]=2[CH:4]=1

Participants

6

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 458475beta-Alanine, ethyl ester, hydrochlorideHCID 203138445-Chloro-N-methyl-N-phenyl-1,3-benzodithiol-2-iminium iodide

Product 1

HCID 867358813-[(5-Chloro-1,3-benzodithiol-2-ylidene)amino]propanoic acid, ethyl esterYield 15.3%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of 5-chloro-N-methyl-N-phenyl-1,3-benzodithiol-2-iminium iodide (9.97g), 3-aminopropanoic acid, ethyl ester, hydrochloride (3.68g) and anhydrous sodium carbonate (2.54g) in 250 ml of anhydrous dimethylformamide is heated at 120° C under nitrogen for three hours, then left stirring at room temperature for 2 days. The reaction mixture is poured into water (1400 ml) and extracted with three 200 ml portions of dichloromethane. The combined dichloromethane extracts are washed with three 100 ml portions of water, dried over sodium sulfate, and concentrated in vacuo. The resultant oil is chromatographed on silica gel (1000 ml), eluting with dichloromethane/pentane (1:1). The fractions containing product with Rf =0.25 (silica gel, dichloromethane) are concentrated and the resultant solid recrystallized twice from pentane to yield 1.1g of the title compound, melting point 64°-65° C.

Workup

  1. waitleft
  2. extractionextracted with three 200 ml portions of dichloromethane
  3. washThe combined dichloromethane extracts are washed with three 100 ml portions of water
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe resultant oil is chromatographed on silica gel (1000 ml)
  7. washeluting with dichloromethane/pentane (1:1)
  8. additionThe fractions containing product with Rf =0.25 (silica gel, dichloromethane)
  9. concentrationare concentrated
  10. customthe resultant solid recrystallized twice from pentane

Sources & evidence

ORD record
ord-6f6d28f34dcc48d28a3386f8ab65402f
Source dataset
uspto-grants-1978_08
Patent number
US04104467

Reaction notes

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