N-Methylaniline → HCID 14390358, compound

HRID 2351729Notes

Reaction equation

HRID 2351729 reaction equation
C(Cl)(=O)C([Cl:4])=O.[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[N:22]([CH2:23][CH2:24][C:25]([OH:27])=O)[C:17]3=[N:18][CH:19]=[CH:20][CH:21]=[C:16]3[N:15]=2)=[CH:10][CH:9]=1.[CH3:28][NH:29][C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1.C(N(CC)CC)C>CN(C)C=O>[ClH:4].[Cl:7][C:8]1[CH:9]=[CH:10][C:11]([C:14]2[N:22]([CH2:23][CH2:24][C:25]([N:29]([CH3:28])[C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)=[O:27])[C:17]3=[N:18][CH:19]=[CH:20][CH:21]=[C:16]3[N:15]=2)=[CH:12][CH:13]=1

Participants

6

Reactant 4

HCID 7515N-MethylanilineHCID 8471TriethylamineHCID 65578Oxalyl chloride2×HCID 15617213HCID 15617213, compound

Product 1

HCID 14390358HCID 14390358, compoundYield 27.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Under nitrogen atmosphere, oxalyl chloride (2.18 g, 0.0172 mole) was added dropwise, slowly, to a stirred and chilled (10° C.) suspension of 2-(4-chlorophenyl)-3H-imidazo[4,5-b]pyridine-3-propanoic acid (5.0 g, 0.0166 mole) in anhydrous dimethylformamide (75 ml). The reaction mixture was stirred at room temperature for 1.5 hours and then additional oxalyl chloride (0.73 g, 0.00573 mole) was added. After stirring at room temperature for 0.5 hour, the reaction mixture was cooled in ice and methylaniline (1.91 g, 0.0178 mole) was added. The reaction mixture was stirred at room temperature for 2.25 hours and then poured into ice water (400 ml) with stirring. Addition of triethylamine (6 ml) precipitated a solid. The solution was decanted from the gum and the gum was dissolved in hot isopropyl alcohol, treated with charcoal and filtered hot. Attempts to crystallize the free base failed. The product, in isopropyl alcohol, was treated with hydrogen chloride in isopropyl alcohol until acidic. Addition of isopropyl ether caused a tan solid to precipitate. The solid was filtered, rinsed with isopropyl ether and dried under high vacuum to give 1.93 g of title compound, mp. 178°-182° C.

Workup

  1. temperaturechilled
  2. stirringThe reaction mixture was stirred at room temperature for 1.5 hours
  3. stirringAfter stirring at room temperature for 0.5 hour
  4. temperaturethe reaction mixture was cooled in ice
  5. stirringThe reaction mixture was stirred at room temperature for 2.25 hours
  6. stirringwith stirring
  7. customprecipitated a solid
  8. customThe solution was decanted from the gum
  9. dissolutionthe gum was dissolved in hot isopropyl alcohol
  10. additiontreated with charcoal
  11. filtrationfiltered hot
  12. customto crystallize the free base
  13. additionThe product, in isopropyl alcohol, was treated with hydrogen chloride in isopropyl alcohol until acidic
  14. additionAddition of isopropyl ether
  15. customto precipitate
  16. filtrationThe solid was filtered
  17. washrinsed with isopropyl ether
  18. customdried under high vacuum

Sources & evidence

ORD record
ord-4eb5c2e4c0944c8aa68fae42fcd7501e
Source dataset
uspto-grants-1989_10
Patent number
US04873251

Reaction notes

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