Triethylamine → HCID 66760143, compound

HRID 1402798Notes

Reaction equation

HRID 1402798 reaction equation
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([NH2:9])=[C:4]([NH2:10])[CH:3]=1.[CH2:11](N(CC)CC)[CH3:12].[Cl:18][C:19]1[CH:24]=[CH:23][C:22]([CH:25]2[CH2:31][C:30](=[O:32])[O:29][C:27](=O)[CH2:26]2)=[CH:21][CH:20]=1>O1CCOCC1>[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]2[N:9]=[C:11]([CH2:12][CH:25]([C:22]3[CH:21]=[CH:20][C:19]([Cl:18])=[CH:24][CH:23]=3)[CH2:31][C:30]([O:29][CH2:27][CH3:26])=[O:32])[NH:10][C:4]=2[CH:3]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 792974,5-Dichloro-1,2-phenylenediamineHCID 1046394-(4-Chlorophenyl)dihydro-2H-pyran-2,6(3H)-dione

Product 1

HCID 66760143HCID 66760143, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent2×

Conditions

Temperature
40 °C

Procedure

The solution of commercial 4,5-dichloro-1,2-phenylenediamine (0.36 g) and triethyl amine (0.32 ml) in 1,4-dioxane (1.5 ml) was added to a solution of 3-(4-chlorophenyl)glutaric anhydride (0.45 g) in 1,4-dioxane (1 ml) with ice cooling. The resulting mixture was stirred at rt for 0.5 h and at 40° C. for 0.5 h. Again under ice cooling 1M HCl (3 ml) was added dropwise. A gummy precipitate is formed. After 0.5 h of cooling the aqueous layer is removed by decantation and the residue is dissolved in methanol. The dark solution is decolorized with activated carbon, filtered, and the filtrate concentrated in vacuo. The amorphous solid is redissolved in ethanol (6 ml) and conc. HCl (2 ml) and stirred at reflux for 16 h. After cooling to rt the pH is adjusted to 8 by addition of first NaOH solution, then sat. sodium bicarbonate solution. The aqueous layer is extracted with dichloromethane (40 ml) and the organic layer is washed with sat. sodium chloride solution and dried (sodium sulfate). After concentration the crude (0.46 g) is purified by flash chromatography ((dichloromethane/2% methanol/1% triethyl amine) on silica gel to afford ethyl 4-(5,6-dichloro-2-benzimidazolyl)-3-(4-chlorophenyl)butanoate (0.33 g) as yellowish, amorphous solid.

Workup

  1. customA gummy precipitate is formed
  2. temperatureAfter 0.5 h of cooling the aqueous layer
  3. customis removed by decantation
  4. dissolutionthe residue is dissolved in methanol
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated in vacuo
  7. dissolutionThe amorphous solid is redissolved in ethanol (6 ml)
  8. stirringconc. HCl (2 ml) and stirred
  9. temperatureat reflux for 16 h
  10. temperatureAfter cooling to rt the pH
  11. additionis adjusted to 8 by addition of first NaOH solution
  12. extractionThe aqueous layer is extracted with dichloromethane (40 ml)
  13. washthe organic layer is washed with sat. sodium chloride solution
  14. dry with materialdried (sodium sulfate)
  15. concentrationAfter concentration the crude (0.46 g)
  16. customis purified by flash chromatography ((dichloromethane/2% methanol/1% triethyl amine) on silica gel

Sources & evidence

ORD record
ord-0cc1b4e009ad4d7e8cd85fdb52a0e628
Source dataset
uspto-grants-2014_12
Patent number
US08912186B2

Reaction notes

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