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

HRID 496737ノート

反応式

HRID 496737 の反応式
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

参加物

4

反応物 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

生成物 1

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

反応条件

温度
60 °C

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-bba64c31e9b94dd18d601821ee27a922
出典データセット
uspto-grants-2005_09
特許番号
US06946472B2

反応ノート

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