Triphenyl phosphite → HCID 58324498, compound

HRID 69749Notes

Reaction equation

HRID 69749 reaction equation
C[O:2][C:3]([C:5]1[N:6]([C:10]2[C:19]([N+:20]([O-])=O)=[CH:18][C:13]([C:14]([O:16][CH3:17])=[O:15])=[CH:12][N:11]=2)[CH:7]=[CH:8][CH:9]=1)=O.P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1>ClCCl.[NH4+].[O-][V](=O)=O.[Pt]>[O:2]=[C:3]1[NH:20][C:19]2[CH:18]=[C:13]([C:14]([O:16][CH3:17])=[O:15])[CH:12]=[N:11][C:10]=2[N:6]2[CH:7]=[CH:8][CH:9]=[C:5]12

Participants

6

Reactant 2

HCID 7540Triphenyl phosphiteHCID 58324515methyl 6-(2-(methoxycarbonyl)-1H-pyrrol-1-yl)-5-nitronicotinate

Product 1

HCID 58324498HCID 58324498, compoundYield 54%

Reagents, catalysts & solvents 3

HCID 23939PlatinumCatalystHCID 516859Ammonium metavanadateCatalystHCID 6344DichloromethaneSolvent

Procedure

Methyl 6-(2-(methoxycarbonyl)-1H-pyrrol-1-yl)-5-nitronicotinate (5.00 g, 16.38 mmol) was dissolved in dichloromethane (Volume: 82 ml) and to this solution was added triphenyl phosphite (0.051 g, 0.164 mmol), ammonium metavanadate (0.115 g, 0.983 mmol) and Pt/C (5% wt.) (0.639 g, 0.164 mmol). The reaction mixture was hydrogenated at 100 psi at 25° C. for 36 h. The reaction mixture was filtered through a short plug of celite and the plug and precipitate were washed well with methanol (100 mL) and then MeOH:DCM (100 mL, 1:1). The solids (celite and Pt/C) were continuously extracted with MeOH/DCM mixture (1:1) in a Soxlet extractor for 2d. The extracts were combined with the earlier filtrates, concentrated in vacuo, crystallized with MeOH (100 mL) and the resulting solid was filtered off and suspended in ethyl ether (200 mL). The solid were filtered off and dried in vacuum to afford methyl 6-oxo-5,6-dihydropyrido[3,2-e]pyrrolo[1,2-a]pyrazine-3-carboxylate (2.15 g, 8.84 mmol, 54.0% yield) as a grey solid. 1H NMR (DMSO-d6) δ 11.49 (s, 1 H), 8.69 (s, 1 H), 8.15 (br. s., 1 H), 8.11 (s, 1 H), 7.16 (d, J=2.5 Hz, 1 H), 6.78 (t, J=3.0 Hz, 1 H), 3.91 (s, 3 H). [M+H] calc'd for C12H9N3O3, 244; found, 244.

Workup

  1. filtrationThe reaction mixture was filtered through a short plug of celite
  2. washthe plug and precipitate were washed well with methanol (100 mL)
  3. extractionThe solids (celite and Pt/C) were continuously extracted with MeOH/DCM mixture (1:1) in a Soxlet extractor for 2d
  4. concentrationconcentrated in vacuo
  5. customcrystallized with MeOH (100 mL)
  6. filtrationthe resulting solid was filtered off
  7. filtrationThe solid were filtered off
  8. customdried in vacuum

Sources & evidence

ORD record
ord-1f8a26852400477c8a8c715459f84e1d
Source dataset
uspto-grants-2014_09
Patent number
US08822470B2

Reaction notes

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