Sodium Hydroxide → HCID 67338376, compound

HRID 910126Notes

Reaction equation

HRID 910126 reaction equation
[CH2:1]1[C:11]2=[C:12]3[C:7](=[CH:8][CH:9]=[CH:10]2)[C:6](=O)[CH2:5][CH2:4][N:3]3[CH2:2]1.[N-:14]=[N+]=[N-].[Na+].[OH-:18].[Na+]>>[CH2:4]1[N:3]2[C:12]3[CH:7]([CH2:8][C:9](=[O:18])[CH2:10][C:11]=3[CH:1]=[CH:2]2)[NH:14][CH2:6][CH2:5]1.[CH2:4]1[N:3]2[C:12]3[CH:7]([CH2:8][CH2:9][C:10](=[O:18])[C:11]=3[CH:1]=[CH:2]2)[CH2:6][NH:14][CH2:5]1

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 33557Sodium AzideHCID 12524226HCID 12524226, compound

Product 2

HCID 67338376HCID 67338376, compoundYield 68%HCID 67340437HCID 67340437, compoundYield 18%

Conditions

Temperature
90 °C

Procedure

Add 1,2,5,6-tetrahydropyrrolo[3,2,1-ij]quinolin-6-one (15.49 g, 89.43 mmol) to polyphosphoric acid (512 g) at 67-70° C. and stir vigorously. Add three portions of sodium azide (2.43 g (37.4 mmol), 2.42 g (37.2 mmol) and 2.42 g (37.2 mmol)) at 20 minute intervals then heat to 90° C. and stir for 3.5 hours. Pour into ice (511.6 g). Add, with cooling, 50% aqueous sodium hydroxide (500 mL) 40 minutes. Extract with chloroform (3×500 mL). Wash the combined organic phases with water (500 mL) and saturated aqueous sodium chloride (500 mL). Dry over sodium sulfate and concentrate under reduced pressure. Subject the residue to chromatography (pre-packed silica gel), eluting with a gradient 98:2-97:3-96:4 chloroform/methanol to provide 1,2,4,5-tetrahydro-7H-[1,4]diazepino[3,2,1-hi]indol-6-one (2.95 g, 18%) and 1,2,4,5-tetrahydro-6H-[1,4]diazepino[6,7,1-hi]indol-7-one (11.51 g, 68%) as beige solids.

Workup

  1. stirringstir for 3.5 hours
  2. additionAdd
  3. temperaturewith cooling
  4. extractionExtract with chloroform (3×500 mL)
  5. washWash the combined organic phases with water (500 mL) and saturated aqueous sodium chloride (500 mL)
  6. dry with materialDry over sodium sulfate
  7. concentrationconcentrate under reduced pressure
  8. washeluting with a gradient 98:2-97:3-96:4 chloroform/methanol

Sources & evidence

ORD record
ord-01d2162207054eb38afcec3c70eed9ff
Source dataset
uspto-grants-2011_09
Patent number
US08022065B2

Reaction notes

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