Sodium Carbonate → 3-(4-Nitrophenyl)-1h-pyrrolo[3,2-c]pyridin4-amine

HRID 230760Notes

Reaction equation

HRID 230760 reaction equation
I[C:2]1[C:6]2[C:7]([NH:11]C(=O)OCC)=[N:8][CH:9]=[CH:10][C:5]=2[NH:4][CH:3]=1.C(=O)([O-])[O-].[Na+].[Na+].[N+:23]([C:26]1[CH:31]=[CH:30][C:29](B(O)O)=[CH:28][CH:27]=1)([O-:25])=[O:24]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O1CCOCC1.O>[N+:23]([C:26]1[CH:31]=[CH:30][C:29]([C:2]2[C:6]3[C:7]([NH2:11])=[N:8][CH:9]=[CH:10][C:5]=3[NH:4][CH:3]=2)=[CH:28][CH:27]=1)([O-:25])=[O:24]

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 27735524-Nitrophenylboronic acidHCID 68825648Ethyl 3-iodo-1h-pyrrolo[3,2-c]pyridin-4-ylcarbamate

Product 1

HCID 577631603-(4-Nitrophenyl)-1h-pyrrolo[3,2-c]pyridin4-amineYield 26%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
80 °C

Procedure

Tetrakis(triphenylphosphine)palladium(0) (0.011 g, 0.009 mmol, 0.1 eq) was added to ethyl 3-iodo-1H-pyrrolo[3,2-c]pyridin-4-ylcarbamate (0.031 g, 0.094 mmol, 1.0 eq), sodium carbonate (0.07g, 0.66 mmol, 7.0 eq) and 4-nitrophenyl boronic acid (0.055g, 0.33 mmol, 3.5 eq) in a degassed solution of 1/1 dioxane/water (1 mL) at room temperature. The reaction mixture was heated to 80° C. for 5 h. The reaction mixture was cooled to room temperature and concentrated in vacuo. The residue was dissolved in water and the pH adjusted to 7.0 with dilute aqueous HCl. The solution was extracted with 10/1 CHCl3/MeOH, the combined organic extracts dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by loading it onto a 1.5 g Varian SCX cationic exchange cartridge (eluting sequentially with 1/1 DCM/MeOH, MeOH, 0.1N NH3 in MeOH, and to elute the product 1.0 N NH3 in MeOH) and the appropriate fractions were isolated and concentrated in vacuo to afford the product (0.006 g, 26%) as a solid. MS(ESI+) m/z 255 (M+H)+. Calculated: 255.0882, found: 255.0887.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. concentrationconcentrated in vacuo
  3. dissolutionThe residue was dissolved in water
  4. extractionThe solution was extracted with 10/1 CHCl3/MeOH
  5. dry with materialthe combined organic extracts dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified
  9. washeluting sequentially with 1/1 DCM/MeOH, MeOH, 0.1N NH3 in MeOH
  10. washto elute the product 1.0 N NH3 in MeOH) and the appropriate fractions
  11. customwere isolated
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-37564edbbf9142349386762d3cfaef8e
Source dataset
uspto-grants-2009_07
Patent number
US07566784B2

Reaction notes

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