2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 476293, compound

HRID 1586590Notes

Reaction equation

HRID 1586590 reaction equation
[C:1]([CH2:3][CH2:4][N:5]1[C:13]2[C:8](=[CH:9][C:10]([O:14][CH3:15])=[CH:11][CH:12]=2)[C:7]([C:16]2[C:17](=[O:32])[NH:18][C:19](=[O:31])[C:20]=2[C:21]2[C:29]3[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=3)[N:23]([CH3:30])[CH:22]=2)=[CH:6]1)#[N:2].O.C1(C)C=CC(S(O)(=O)=O)=CC=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C(OC(C)C)(C)C>C1(C)C=CC=CC=1>[C:1]([CH2:3][CH2:4][N:5]1[C:6]2[C:22]3[N:23]([CH3:30])[C:24]4[C:29]([C:21]=3[C:20]3[C:19](=[O:31])[NH:18][C:17](=[O:32])[C:16]=3[C:7]=2[C:8]2[CH:9]=[C:10]([O:14][CH3:15])[CH:11]=[CH:12][C:13]1=2)=[CH:28][CH:27]=[CH:26][CH:25]=4)#[N:2]

Participants

6

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 7914Diisopropyl EtherHCID 521998p-Toluenesulfonic acid monohydrateHCID 21216885HCID 21216885, compound

Product 1

HCID 476293HCID 476293, compoundYield 54.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

500 mg (1.18 mmol) 3-[1-(2-cyanoethyl)-5-methoxy-3-indolyl]-4-(1-methyl-3-indolyl)-1H-pyrrole-2,5-dione in 50 ml toluene are heated under reflux for 30 minutes with 225 mg (1.18 mmol) p-toluenesulphonic acid hydrate and 315 mg (1.39 mmol) 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ). After cooling, the reaction mixture is evaporated in a vacuum and the residue is stirred with 100 ml 0.1N sodium hydroxide solution. The aqueous suspension is saturated with sodium chloride and extracted twice with, in each case, 100 ml tetrahydrofuran. The tetrahydrofuran solutions are washed twice with, in each case, 100 ml saturated sodium chloride solution. The residue is chromatographed on silica gel with toluene/acetone (4:1 v/v). The fraction with the Rf 0.3 is isolated, stirred up with diisopropyl ether and the crystals formed are filtered off. There are obtained 270 mg (54% of theory) 13-(2-cyanoethyl)-6,7,12,13-tetrahydro-3-methoxy-12-methyl-5,7-dioxo-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole in the form of yellow crystals which decompose from about 260° C. with the evolution of gas.

Workup

  1. temperatureAfter cooling
  2. customthe reaction mixture is evaporated in a vacuum
  3. extractionextracted twice with, in each case, 100 ml tetrahydrofuran
  4. washThe tetrahydrofuran solutions are washed twice with, in each case, 100 ml saturated sodium chloride solution
  5. customThe residue is chromatographed on silica gel with toluene/acetone (4:1 v/v)
  6. customThe fraction with the Rf 0.3 is isolated
  7. customthe crystals formed
  8. filtrationare filtered off

Sources & evidence

ORD record
ord-71780c2f224a4c028b4fa13c9197e655
Source dataset
uspto-grants-1999_08
Patent number
US05945440

Reaction notes

Loading…