HCID 12260467, compound → HCID 71087757, compound

HRID 1478893Notes

Reaction equation

HRID 1478893 reaction equation
CN(C)[CH:3]=[C:4]([N:9]=[CH:10]N(C)C)[C:5]([O:7][CH3:8])=[O:6].[CH2:15]([N:17]1[CH:21]=[CH:20][C:19]([CH3:22])=[CH:18]1)[CH3:16]>C(O)(=O)C.C(O)(C(F)(F)F)=O>[CH2:15]([N:17]1[C:21]2[CH:3]=[C:4]([C:5]([O:7][CH3:8])=[O:6])[N:9]=[CH:10][C:20]=2[C:19]([CH3:22])=[CH:18]1)[CH3:16]

Participants

5

Reactant 2

HCID 12260467HCID 12260467, compoundHCID 86674845HCID 86674845, compound

Product 1

HCID 71087757HCID 71087757, compoundYield 46%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

In a 500 ml round bottom flask, methyl 3-(dimethylamino)-2-((dimethylamino)methyleneamino)acrylate (1A, 12 g, 61 mmol) was dissolved in acetic acid (45 ml) and TFA (15 ml). 1-Ethyl-3-methyl-1H-pyrrole (6.7 g, 61 mmol) was added and the mixture was stirred at room temperature for an hour and then at 110° C. for 4 hours. Volatiles were then evaporated from the reaction mixture, the residue was cooled in an ice bath and ice cold saturated K2CO3 solution (˜200 ml) was slowly added to it. The mixture was extracted with EtOAc (3×250 ml). Combined organic layers were then washed with brine, dried over sodium sulfate, filtered and evaporated. The crude product was purified on a silica column using hexane-EtOAc (0-100%). Pure fractions were combined and evaporated to give the product methyl 1-ethyl-3-methyl-1H-pyrrolo[3,2-c]pyridine-6-carboxylate (1N, 6.1 g, 46% yield). 1H NMR (400 MHz, DMSO-d6) d ppm 1.34 (t, J=7.20 Hz, 3 H) 2.34 (d, J=1.01 Hz, 3 H) 3.88 (s, 3 H) 4.26 (q, J=7.24 Hz, 2 H) 7.48 (d, J=1.01 Hz, 1 H) 8.20 (d, J=1.01 Hz, 1 H) 8.85 (d, J=1.01 Hz, 1 H).

Workup

  1. customVolatiles were then evaporated from the reaction mixture
  2. temperaturethe residue was cooled in an ice bath
  3. additionice cold saturated K2CO3 solution (˜200 ml) was slowly added to it
  4. extractionThe mixture was extracted with EtOAc (3×250 ml)
  5. washCombined organic layers were then washed with brine
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe crude product was purified on a silica column
  10. customevaporated

Sources & evidence

ORD record
ord-51f3a605fa614e07a97028f29e1df6c7
Source dataset
uspto-grants-2016_08
Patent number
US09403819B2

Reaction notes

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