Methanol → HCID 67995435, compound

HRID 2361412Notes

Reaction equation

HRID 2361412 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[C:14](=[O:15])[NH:13][CH:12]=[CH:11][C:7]=3[NH:8][C:9]=2[CH:10]=1.[C:16]([O-:19])(=[O:18])C.[Na+].[CH3:21]O>CC(N(C)C)=O.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:21][O:19][C:16]([C:2]1[CH:3]=[CH:4][C:5]2[C:6]3[C:14](=[O:15])[NH:13][CH:12]=[CH:11][C:7]=3[NH:8][C:9]=2[CH:10]=1)=[O:18]

Participants

7

Reactant 3

HCID 887MethanolHCID 517045Sodium AcetateHCID 67995189HCID 67995189, compound

Product 1

HCID 67995435HCID 67995435, compoundYield 85%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
95 °C

Procedure

A stirred mixture of 7-bromo-2,5-dihydro-1H-pyrido[4,3-b]indol-1-one (1.000 g, 3.80 mmol), 1,1′-Bis(diphenylphosphino)ferrocene (0.319 g, 0.57 mmol), Palladium (II) acetate (0.128 g, 0.57 mmol) and Sodium acetate (0.623 g, 7.600) in a mixture of Methanol (30 mL) and DMA (10 mL) was degassed under vacuum and pressurized with Carbon Monoxide gas [CO] from a lecture bottle to approx. 55 psi in a sealed Steel Reaction vessel. The sealed vessel was heated at 95° C. overnight behind a protective shield. LC-MS showed complete reaction. The reaction mixture was filtered through a pad of CELITE® and the filtrate concentrated under vacuum. The residue was diluted with dichloromethane, filtered and the filtrate concentrated to give methyl-1-oxo-2,5-dihydro-1H-pyrido[4,3-b]indole-7-carboxylate as a tan solid. [0.732 g product, 3.02 mmol, 85% yield]. The product had an HPLC Retention Time=2.192 min [4 min grad, 10% MeOH/water to 90% MeOH/water, 0.1% TFA, YMC COMBISCREEN® ODS-A, 4.6×50 mm, 220 nM]; LC/MS+1 243.06

Workup

  1. customwas degassed under vacuum
  2. custompressurized with Carbon Monoxide gas [CO] from a lecture bottle to approx. 55 psi in a sealed Steel Reaction vessel
  3. customreaction
  4. filtrationThe reaction mixture was filtered through a pad of CELITE®
  5. concentrationthe filtrate concentrated under vacuum
  6. additionThe residue was diluted with dichloromethane
  7. filtrationfiltered
  8. concentrationthe filtrate concentrated

Sources & evidence

ORD record
ord-fe84fb4bd13540dfb6339cefa905be68
Source dataset
uspto-grants-2014_04
Patent number
US08685969B2

Reaction notes

Loading…