Methyl Methacrylate → 10-bromo-2-methoxy-5-methyl-4H-pyrido [3,2,1-jk]carbazole-4-one

HRID 850753Notes

Reaction equation

HRID 850753 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:6][C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][C:10]([O:15][CH3:16])=[CH:9][CH:8]=3.[C:17](OC)(=[O:21])[C:18]([CH3:20])=[CH2:19]>O1CCCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[N:6]3[CH:19]=[C:18]([CH3:20])[C:17](=[O:21])[C:8]4[CH:9]=[C:10]([O:15][CH3:16])[CH:11]=[C:12]([C:13]=2[CH:14]=1)[C:7]3=4

Participants

4

Reactant 2

HCID 6658Methyl MethacrylateHCID 15886922HCID 15886922, compound

Product 1

HCID 2125282210-bromo-2-methoxy-5-methyl-4H-pyrido [3,2,1-jk]carbazole-4-oneYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

3-bromo-6-methoxycarbazole (20 g) produced in Example 1, step 1 was dissolved in anhydrous tetrahydrofuran (200 ml), and to the solution were added methyl methacrylate (77.6 ml), then Triton B (0.7 ml). The mixture was heated under reflux in an argon atmosphere for 2 hours, and the solvent was evaporated under reduced pressure. The resulting residue was suspended in methanol (60 ml), and sodium hydroxide (6.4 g) dissolved in water (80 ml) was added dropwise at room temperature, and the mixture was stirred at room temperature for 12 hours. The solvent was evaporated under reduced pressure, and water and ether were added for phase separation. The aqueous layer was rendered acidic by addition of 4N hydrochloric acid, and ethyl acetate was added for further phase separation. The ethyl acetate layer was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The residual crude crystals were washed with hexane and ether and recovered by filtration to obtain the title compound (25.0 g, 95%).

Workup

  1. temperatureThe mixture was heated
  2. temperatureunder reflux in an argon atmosphere for 2 hours
  3. customthe solvent was evaporated under reduced pressure
  4. dissolutionsodium hydroxide (6.4 g) dissolved in water (80 ml)
  5. additionwas added dropwise at room temperature
  6. customThe solvent was evaporated under reduced pressure, and water and ether
  7. additionwere added for phase separation
  8. additionThe aqueous layer was rendered acidic by addition of 4N hydrochloric acid, and ethyl acetate
  9. additionwas added for further phase separation
  10. washThe ethyl acetate layer was washed with water and saturated aqueous solution of sodium chloride
  11. dry with materialdried over anhydrous sodium sulfate
  12. customthe solvent was evaporated under reduced pressure
  13. washThe residual crude crystals were washed with hexane and ether
  14. filtrationrecovered by filtration

Sources & evidence

ORD record
ord-e039dae022f94c45b83846407354480c
Source dataset
uspto-grants-2000_01
Patent number
US06018046

Reaction notes

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