Methyl 4-(chlorocarbonyl)benzoate → HCID 67356193, compound

HRID 2405092Notes

Reaction equation

HRID 2405092 reaction equation
[Br:1][C:2]1[C:6]2[CH:7]=[N:8][C:9]([NH:11][C:12](=[O:18])OC(C)(C)C)=[CH:10][C:5]=2[N:4]([CH2:19][CH3:20])[CH:3]=1.ClC([C:24]1[CH:33]=[CH:32][C:27]([C:28]([O:30][CH3:31])=[O:29])=[CH:26][CH:25]=1)=O>Cl.O1CCOCC1>[Br:1][C:2]1[C:6]2[CH:7]=[N:8][C:9]([NH:11][C:12]([C:24]3[CH:33]=[CH:32][C:27]([C:28]([O:30][CH3:31])=[O:29])=[CH:26][CH:25]=3)=[O:18])=[CH:10][C:5]=2[N:4]([CH2:19][CH3:20])[CH:3]=1

Participants

5

Reactant 2

HCID 81850Methyl 4-(chlorocarbonyl)benzoateHCID 67357244HCID 67357244, compound

Product 1

HCID 67356193HCID 67356193, compoundYield 87.9%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of tert-butyl 3-bromo-1-ethyl-1H-pyrrolo[3,2-c]pyridin-6-ylcarbamate (3C, 340 mg, 0.99 mmol) in 4M HCl in dioxane (3 ml) was stirred at room temperature for 1 h and 70° C. for 2 h. The mixture was concentrated in vacuo and dissolved in pyridine (3 ml). To the mixture, methyl 4-(chlorocarbonyl)benzoate (220 mg, 1.1 mmol) was added and stirred at room temperature for 3 h. The mixture was extracted with EtOAc/H2O. The organic layer was washed with brine, dried over MgSO4 and concentrated in vacuo. The crude mixture was purified by chromatography (basic-SiO2, hexanes:EtOAc=3:1) to give methyl 4-(3-bromo-1-ethyl-1H-pyrrolo[3,2-c]pyridin-6-ylcarbamoyl)benzoate (3D, 350 mg, 0.87 mmol, 87% yield) as a white powder. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.40 (t, J=1.00 Hz, 3H) 3.90 (s, 3H) 4.21 (q, J=7.16 Hz, 2H) 7.72 (s, 1H) 7.99-8.11 (m, 2H) 8.11-8.20 (m, 2H) 8.35 (d, J=0.76 Hz, 1H) 8.52 (d, J=1.01 Hz, 1H) 10.96 (s, 1H).

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. dissolutiondissolved in pyridine (3 ml)
  3. stirringstirred at room temperature for 3 h
  4. extractionThe mixture was extracted with EtOAc/H2O
  5. washThe organic layer was washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo
  8. customThe crude mixture was purified by chromatography (basic-SiO2, hexanes:EtOAc=3:1)

Sources & evidence

ORD record
ord-935809593eee49e79f20b6b1bee7467b
Source dataset
uspto-grants-2014_08
Patent number
US08802695B2

Reaction notes

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