Phosphorus oxychloride → 6-Chloro-3-methoxy-5,10-diaza-benzo[c]fluoren-7-one

HRID 496737Notes

Reaction equation

HRID 496737 reaction equation
COC1C=CC2C3C4C=CN=CC=4C(=O)C=3C(=O)NC=2C=1.[CH3:22][O:23][C:24]1[CH:25]=[CH:26][C:27]2[C:39]3[C:38]4[CH:37]=[N:36][CH:35]=[CH:34][C:33]=4[C:32](=[O:40])[C:31]=3[C:30](=O)[NH:29][C:28]=2[CH:42]=1.P(Cl)(Cl)([Cl:45])=O>>[Cl:45][C:30]1[C:31]2[C:32](=[O:40])[C:33]3[CH:34]=[CH:35][N:36]=[CH:37][C:38]=3[C:39]=2[C:27]2[CH:26]=[CH:25][C:24]([O:23][CH3:22])=[CH:42][C:28]=2[N:29]=1

Participants

4

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 111501193-methoxy-5H-5,9-diaza-benzo[c]fluorene-6,7-dioneHCID 114259203-methoxy-5H-5,10-diaza-benzo[c]fluorene-6,7-dione

Product 1

HCID 113923176-Chloro-3-methoxy-5,10-diaza-benzo[c]fluoren-7-one

Conditions

Temperature
60 °C

Procedure

The mixture of 3-methoxy-5H-5,9-diaza-benzo[c]fluorene-6,7-dione and 3-methoxy-5H-5,10-diaza-benzo[c]fluorene-6,7-dione (8.77 g) obtained above was suspended in phosphorus oxychloride (359 g) and stirred at 60° C. for three days. Excess phosphorus oxychloride was evaporated under reduced pressure. The residue was treated with ice water and saturated sodium hydrogen carbonate to adjust the pH about 7. Black precipitate was collected with suction and washed water. The precipitate was purified by silica gel column chromatography developed by dichloromethane-methanol-trifluoroacetic acid (200:2:1) and by dichloromethane-methanol-trifluoroacetic acid (200:4:1). This chromatography gave two yellow bands. The first band was collected and evaporated. The residue was treated with methanol to give less polar isomer (1.72 g), 6-chloro-3-methoxy-5,10-diaza-benzo[c]fluoren-7-one (Reference Example 1c-1) as a yellow powder. The second band was collected and evaporated. The residue was treated with methanol to give more polar isomer (1.86 g), 6-chloro-3-methoxy-5,9-diaza-benzo[c]fluoren-7-one (Reference Example 1c-2) as a yellow powder.

Workup

  1. customobtained
  2. customExcess phosphorus oxychloride was evaporated under reduced pressure
  3. additionThe residue was treated with ice water and saturated sodium hydrogen carbonate
  4. customBlack precipitate was collected with suction
  5. washwashed water
  6. customThe precipitate was purified by silica gel column chromatography
  7. customThis chromatography gave two yellow bands
  8. customThe first band was collected
  9. customevaporated
  10. additionThe residue was treated with methanol

Sources & evidence

ORD record
ord-bba64c31e9b94dd18d601821ee27a922
Source dataset
uspto-grants-2005_09
Patent number
US06946472B2

Reaction notes

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