4-(2-Chlorophenyl)-9-methoxy-4,5,6,10c-tetrahydropyrrolo[3,4-c]carbazole-1,3(2H,3aH)-dione → 4-(2-Chlorophenyl)-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

HRID 11059Notes

Reaction equation

HRID 11059 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]1[CH:20]2[C:21](=[O:25])[NH:22][C:23](=[O:24])[CH:19]2[C:18]2[C:17]3[CH:16]=[C:15]([O:26][CH3:27])[CH:14]=[CH:13][C:12]=3[NH:11][C:10]=2[CH2:9]1.[Si](OCCCN1C2CC(C3C=CC=CC=3OC)C3C(=O)NC(=O)C3C=2C2C=C(OC)C=CC1=2)(C(C)(C)C)(C)C>O1CCOCC1.[O-2].[O-2].[Mn+4]>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]1[C:20]2[C:21](=[O:25])[NH:22][C:23](=[O:24])[C:19]=2[C:18]2[C:17]3[CH:16]=[C:15]([O:26][CH3:27])[CH:14]=[CH:13][C:12]=3[NH:11][C:10]=2[CH:9]=1

Participants

5

Reactant 2

HCID 118439604-(2-Chlorophenyl)-9-methoxy-4,5,6,10c-tetrahydropyrrolo[3,4-c]carbazole-1,3(2H,3aH)-dione2×HCID 867601946-(3-{[Tert-butyl(dimethyl)silyl]oxy}propyl)-9-methoxy-4-(2-methoxyphenyl)-4,5,6,10c-tetrahydropyrrolo[3,4-c]carbazole-1,3(2h, 3ah)-dione

Product 1

HCID 118444834-(2-Chlorophenyl)-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 312751,4-DioxaneSolvent

Procedure

Manganese dioxide (12.0 g) was added to a solution of 4-(2-Chlorophenyl)-9-methoxy-4,5,6,10c-tetrahydropyrrolo[3,4-c]carbazole-1,3(2H,3aH)-dione (IV; Ar=2-chlorophenyl, R10═H (32) prepared as described in example 68 (2.1 g, 5.51 mmol) in dioxane (100 mL) and the mixture was refluxed with stirring for 16 h. The mixture was filtered hot through a plug of Celite, washing through with more dioxane and then 10% methanol/dioxane. The combined filtrate and washings were concentrated to dryness and the residue was adsorbed onto silica and chromatographed. Elution with ethyl acetate/petroleum ether (3:7) gave 4-(2-Chlorophenyl)-9-methoxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione (V; Ar=2-chlorophenyl, R10═H (33) in a yield of 1.66 g, 79% which crystallised from THF/petroleum ether as a yellow powder, mp 170–175° C. (dec). 1H NMR δ [(CD3)2SO 11.96 (br s, 1H), 11.08 (br s, 1H), 8.46 (d, J=2.6 Hz, 1H), 7.60–7.55 (m, 3H), 7.51–7.42 (m, 3H), 7.24 (dd, J=8.9, 2.6 Hz, 1H), 3.89 (s, 3H). Found: C, 65.64; H, 3.63; N, 7.12. C21H13ClN2O3.1/2H2O requires C, 65.37; H, 3.66; N, 7.26.

Workup

  1. temperaturethe mixture was refluxed
  2. filtrationThe mixture was filtered hot through a plug of Celite
  3. washwashing through with more dioxane
  4. concentrationThe combined filtrate and washings were concentrated to dryness
  5. customchromatographed
  6. washElution with ethyl acetate/petroleum ether (3:7)

Sources & evidence

ORD record
ord-624945cdd7dc40bf82e1a9c34cf99862
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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