Hydrochloric Acid → 4-(5-amino-2-methoxyphenyl)-9-hydroxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

HRID 11058Notes

Reaction equation

HRID 11058 reaction equation
[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=[C:8]([C:15]4[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=4[O:24][CH3:25])[C:7]4[C:26](=[O:30])[NH:27][C:28](=[O:29])[C:6]=4[C:5]=3[C:4]=2[CH:3]=1.C1COCC1.Cl>CO.B#[Ni]>[NH2:21][C:19]1[CH:18]=[CH:17][C:16]([O:24][CH3:25])=[C:15]([C:8]2[C:7]3[C:26](=[O:30])[NH:27][C:28](=[O:29])[C:6]=3[C:5]3[C:4]4[CH:3]=[C:2]([OH:1])[CH:14]=[CH:13][C:12]=4[NH:11][C:10]=3[CH:9]=2)[CH:20]=1.[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=[C:8]([C:15]4[CH:20]=[C:19]([N+:21]([O-:23])=[O:22])[CH:18]=[CH:17][C:16]=4[O:24][CH3:25])[C:7]4[C:26](=[O:30])[NH:27][C:28](=[O:29])[C:6]=4[C:5]=3[C:4]=2[CH:3]=1

Participants

7

Reactant 3

HCID 313Hydrochloric Acid2×HCID 8028TetrahydrofuranHCID 697128459-hydroxy-4-(2-methoxy-5-nitrophenyl)pyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

Product 2

HCID 118428424-(5-amino-2-methoxyphenyl)-9-hydroxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dioneHCID 697128459-hydroxy-4-(2-methoxy-5-nitrophenyl)pyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

Reagents, catalysts & solvents 2

HCID 82791nickel boride (NiB)CatalystHCID 887MethanolSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 9-hydroxy-4-(2-methoxy-5-nitrophenyl)pyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione (VI; Ar=2-methoxy-5-nitrophenyl, R10═H) (38) (64 mg, 0.159 mmol) prepared according to example 72 in methanol (10 mL) and THF (1 mL) was added 2N HCl (1 mL) Freshly prepared nickel boride (˜0.50 g) was added and the mixture was warmed at 60° C. After 1 h HCl (1 mL) and Ni2B (−0.50 g) were added and the reaction mixture was maintained at 60° C. a total of 4 h. The solvents were removed in vacuo and the residue was partitioned between ethyl acetate and 2N HCl. The aqueous layer was basified with conc. ammonia solution and extracted with ethyl acetate. The organic phase was dried, the drying agent was removed and the solvent concentrated to dryness gave a solid which when crystallised from THF/petroleum ether gave 4-(5-Amino-2-methoxyphenyl)-9-hydroxypyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione (VI; Ar=5-amino-2-methoxyphenyl, R10═H (39) in a yield of 49.7 mg, 84% as a yellow powder; mp 246–250° C. 1H NMR δ [(CD3)2SO] 11.67 (s, 1H), 10.87 (s, 1H), 9.21 (s, 1H), 8.30)d, J=2.4 Hz, 1H), 7.44 (s, 1H), 7.42 (d, J=8.7 Hz, 1H), 7.05 (dd, J=8.6, 2.5 Hz, 1H), 6.80 (d, J=8.7 Hz, 1H), 6.61 (dd, J=8.6, 2.7 Hz, 1H), 6.55 (d, J=2.8 Hz, 1H), 4.68 (br, 2H), 3.53 (s, 3H). FABMS found [M+H]+: 373.1056. C21H15N3O4 requires 373.1062.

Workup

  1. additionwas added
  2. temperaturethe reaction mixture was maintained at 60° C. a total of 4 h
  3. customThe solvents were removed in vacuo
  4. customthe residue was partitioned between ethyl acetate and 2N HCl
  5. extractionextracted with ethyl acetate
  6. customThe organic phase was dried
  7. customthe drying agent was removed
  8. concentrationthe solvent concentrated to dryness
  9. customgave a solid which when
  10. customcrystallised from THF/petroleum ether

Sources & evidence

ORD record
ord-94ffd459294f4be38a5e0da8180f5b07
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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